Resin composition

Abstract

To provide a resin composition with which it is possible to obtain a cured matter that has low dielectric properties and high adhesion to a conductor layer, and is capable of inhibiting occurrence of cracks after desmear treatment.SOLUTION: A resin composition contains (A) an epoxy resin, (B) an active ester compound, and (C) a compound represented by formula (C-1).SELECTED DRAWING: None

Description

[Technical field]

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

[0002] 2. Description of the Related Art A known manufacturing technique for printed wiring boards is a build-up method in which insulating layers and conductor layers are alternately stacked.

[0003] As an insulating material for a printed wiring board used in such an insulating layer, for example, Patent Document 1 discloses a resin composition. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] International Publication No. 2023 / 008079 Summary of the Invention [Problem to be solved by the invention]

[0005] In recent years, with the increasing functionality of printed wiring boards, there is a demand for further improvement in dielectric properties such as the dielectric loss tangent of the insulating layer and further improvement in adhesion to plating. In addition, with the increasing functionality of printed wiring boards, there is also a demand for a resin composition with a lower melt viscosity so that fine wiring can be embedded with the resin composition.

[0006] Furthermore, when an insulating layer is formed using a conventional resin composition that contributes to good dielectric properties, the resulting insulating layer tends to easily develop cracks after a desmear treatment.

[0007] The present invention has been devised in view of the above-mentioned problems, and aims to provide a resin composition having a low melt viscosity and capable of giving a cured product which has low dielectric properties, high adhesion (peel strength) to a conductor layer, and is capable of suppressing the occurrence of cracks after a desmear treatment; a resin sheet containing the resin composition; and a printed wiring board and a semiconductor device which are provided with an insulating layer formed using the resin composition. [Means for solving the problem]

[0008] As a result of intensive investigations into the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by incorporating a combination of (A) an epoxy resin, (B) an active ester compound, and (C) a compound represented by formula (C-1), and have thus completed the present invention.

[0009] That is, the present invention includes the following. [1] (A) epoxy resin, (B) an active ester compound, and (C) A resin composition containing a compound represented by formula (C-1). [ka] In the formula, X's each independently represent an n-valent hydrocarbon group which may have a substituent, Y's each independently represent a monovalent group containing a double bond which may have a substituent, Ar's each independently represent a divalent aromatic hydrocarbon group having two alkyl groups which may be the same or different as substituents, and Z's each independently represent a single bond or a divalent aromatic hydrocarbon group which may have a substituent, n' represents an integer of 1 to 3, and m' represents an integer of 1 to 100. [2] The resin composition according to [1], wherein Y represents any one of an acryloyl group, a methacryloyl group, and a vinylbenzyl group. [3] The resin composition according to [1] or [2], wherein the component (C) contains a compound represented by formula (C-2). [ka] In the formula, R 1and R 2 each independently represents a monovalent group containing a double bond; R 3 and R 4 represents a divalent aromatic hydrocarbon group having two alkyl groups, which may be the same or different, as substituents, each independently; R 5 each independently represents a divalent aromatic hydrocarbon group; R 6 represents a single bond or a divalent aromatic hydrocarbon group which may have a substituent. m1 represents an integer of 1 to 100. [4] The resin composition according to any one of [1] to [3], wherein the component (C) contains a compound represented by formula (C-3): [ka] In the formula, R 11 and R 12 each independently represents a monovalent group containing a double bond; R 13 and R 14 represents a divalent aromatic hydrocarbon group having two alkyl groups, which may be the same or different, as substituents, each independently; R 15 represents a single bond or a divalent aromatic hydrocarbon group which may have a substituent. m2 represents an integer of 1 to 100. [5] The resin composition according to any one of [1] to [4], wherein the content of the component (C) is 1% by mass or more and 25% by mass or less, when the resin component in the resin composition is taken as 100% by mass. [6] The resin composition according to any one of [1] to [5], further comprising (D) an inorganic filler. [7] The resin composition according to any one of [1] to [6], further comprising (E) a compound having a double bond. [8] The resin composition according to [7], wherein the content of the (E) component is 1% by mass or more and 25% by mass or less, when the resin component in the resin composition is 100% by mass. [9] The resin composition according to any one of [1] to [8], further comprising (F) a curing agent.

[10] 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 [9].

[11] A printed wiring board comprising an insulating layer formed from a cured product of the resin composition according to any one of [1] to [9].

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

[11] . Effect of the Invention

[0010] According to the present invention, it is possible to provide a resin composition having a low melt viscosity and capable of giving a cured product which has low dielectric properties, high adhesion to a conductor layer, and is capable of suppressing the occurrence of cracks after a desmear treatment; a resin sheet containing the resin composition; a printed wiring board including an insulating layer formed using the resin composition, and a semiconductor device. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] 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.

[0012] [Resin composition] The resin composition of the present invention contains (A) an epoxy resin, (B) an active ester compound, and (C) a compound represented by formula (C-1). In the present invention, by containing the components (A), (B), and (C) in combination, it is possible to obtain a resin composition with low melt viscosity that can obtain a cured product having low dielectric properties, high adhesion to a conductor layer, and capable of suppressing the occurrence of cracks after desmearing. In addition, it is usually possible to obtain a cured product having a high glass transition temperature. [ka] In the formula, X's each independently represent an n-valent hydrocarbon group which may have a substituent, Y's each independently represent a monovalent group containing a double bond which may have a substituent, Ar's each independently represent a divalent aromatic hydrocarbon group having two alkyl groups which may be the same or different as substituents, and Z's each independently represent a single bond or a divalent aromatic hydrocarbon group which may have a substituent, n' represents an integer of 1 to 3, and m' represents an integer of 1 to 100.

[0013] The resin composition may further contain optional components in combination with the components (A) to (C). Examples of the optional components include (D) an inorganic filler, (E) a compound having a double bond, (F) a curing agent, (G) an organic filler, (H) a curing accelerator, (I) other additives, and (J) a solvent. Each component contained in the resin composition will be described in detail below.

[0014] <(A) Epoxy resin> The resin composition contains an epoxy resin (A) as component (A). By including the epoxy resin (A) in the resin composition, a cured product exhibiting good mechanical strength and insulation reliability can be obtained. The epoxy resin (A) may be used alone or in combination of two or more kinds.

[0015] Examples of the epoxy resin (A) include bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type Examples of the epoxy resin include epoxy resins, glycidyl cyclohexane type epoxy resins, alkyl diglycidyl ether type epoxy resins, cresol novolac type epoxy resins, biphenyl type epoxy resins, linear aliphatic epoxy resins, epoxy resins having a butadiene structure, alicyclic epoxy resins, heterocyclic epoxy resins, spiro ring-containing epoxy resins, cyclohexane type epoxy resins, cyclohexane dimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, tetraphenylethane type epoxy resins, phenolphthalimidine type epoxy resins, etc. The epoxy resins may be used alone or in combination of two or more.

[0016] The resin composition preferably contains, as component (A), an epoxy resin having two or more epoxy groups in one molecule. From the viewpoint of significantly obtaining the desired effects of the present invention, the proportion of the epoxy resin having two or more epoxy groups in one molecule relative to 100% by mass of the epoxy resin (A) is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more.

[0017] Epoxy resins include epoxy resins that are liquid at a temperature of 20° C. (hereinafter sometimes referred to as "liquid epoxy resins") and epoxy resins that are solid at a temperature of 20° C. (hereinafter sometimes referred to as "solid epoxy resins"). The resin composition may contain only a liquid epoxy resin as component (A), may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin. Of these, from the viewpoint of achieving the effects of the present invention significantly, it is preferable to contain a combination of a liquid epoxy resin and a solid epoxy resin.

[0018] The liquid epoxy resin is preferably a liquid epoxy resin having two or more epoxy groups in one molecule.

[0019] As the liquid epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, glycidyl amine type epoxy resin, epoxy resin having a butadiene structure, glycidyl cyclohexane type epoxy resin, phenolphthalimidine type epoxy resin, alkyl diglycidyl ether type epoxy resin are preferred, and bisphenol A type epoxy resin, bisphenol F type epoxy resin, and naphthalene type epoxy resin are more preferred.

[0020] Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "825", and "Epikote 828EL" (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" and "630LSD" (glycidylamine type epoxy resins) manufactured by Mitsubishi Chemical Corporation; and "ZX1" manufactured by Nippon Steel Chemical & Material Co., Ltd. Examples of epoxy resins include "EX-721" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nagase ChemteX Corporation, "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation, "PB-3600" (epoxy resin having a butadiene structure) manufactured by Daicel Corporation, "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane type epoxy resin) manufactured by Nippon Steel Chemical & Material Corporation, and "YED216D" (alkyl diglycidyl ether type epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used alone or in combination of two or more types.

[0021] As the solid epoxy resin, a solid epoxy resin having two or more epoxy groups in one molecule is preferable, a solid epoxy resin having three or more epoxy groups in one molecule is more preferable, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is even more preferable.

[0022] As the solid epoxy resin, bixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, and tetraphenylethane type epoxy resin are preferred, and biphenyl type epoxy resin is more preferred.

[0023] Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin), "HP-4700", "HP-4710" (naphthalene type tetrafunctional epoxy resin), "N-690" (cresol novolac type epoxy resin), "N-695" (cresol novolac type epoxy resin), "HP-7200", "HP-7200HH", "HP-7200H" (dicyclopentadiene type epoxy resin), "EXA-7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000", "HP6000L" (naphthylene ether type epoxy resin), and "EPPN-502H" (trisphenol type epoxy resin), "NC7000L" (naphthol novolac type epoxy resin), "NC3000H", "NC3000", "NC3000L" manufactured by Nippon Kayaku Co., Ltd. Examples of epoxy resins include "NC3100" (biphenyl type epoxy resin); "ESN475V" (naphthalene type epoxy resin) and "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin), and "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin), "YL7800" (fluorene type epoxy resin), "jER1010" (solid bisphenol A type epoxy resin), and "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; and "WHR-991S" (phenolphthalimidine type epoxy resin) manufactured by Nippon Kayaku Co., Ltd. These may be used alone or in combination of two or more.

[0024] When a liquid epoxy resin and a solid epoxy resin are used in combination as component (A), the ratio by mass (liquid epoxy resin:solid epoxy resin) is preferably 1:0.1 to 1:20, more preferably 1:0.15 to 1:10, and particularly preferably 1:0.2 to 1:5. When the ratio by mass of the liquid epoxy resin and the solid epoxy resin is within this range, the desired effects of the present invention can be significantly obtained.

[0025] The epoxy equivalent of the (A) component is preferably 50 g / eq. to 5000 g / eq., more preferably 50 g / eq. to 3000 g / eq., even more preferably 80 g / eq. to 2000 g / eq., and even more preferably 110 g / eq. to 1000 g / eq. Within this range, a cured product of the resin composition can be obtained with sufficient crosslink density. The epoxy equivalent is the mass of an epoxy resin containing one equivalent of epoxy groups. This epoxy equivalent can be measured according to JIS K7236.

[0026] From the viewpoint of significantly obtaining the desired effects of the present invention, the weight average molecular weight (Mw) of the component (A) is preferably 100 to 5000, more preferably 150 to 3000, and even more preferably 200 to 1500. The weight average molecular weight of the epoxy resin is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

[0027] From the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, the content of the (A) component is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, based on 100% by mass of the non-volatile components in the resin composition. The upper limit is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly preferably 10% by mass or less.

[0028] In the present invention, unless otherwise specified, the content of each component in the resin composition is a value when the non-volatile components in the resin composition are 100 mass %, and the non-volatile components mean all non-volatile components in the resin composition excluding the solvent.

[0029] From the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, the content of the (A) component, relative to 100 mass% of the resin component in the resin composition, is preferably 15 mass% or more, more preferably 20 mass% or more, even more preferably 25 mass% or more, and is preferably 45 mass% or less, more preferably 40 mass% or less, even more preferably 35 mass% or less.

[0030] In the present invention, the resin component in the resin composition refers to the non-volatile components of the resin composition excluding the inorganic filler (D).

[0031] <(B) Active ester curing agent> The resin composition contains an active ester curing agent (B) as the component (B). The active ester curing agent (B) as the component (B) does not include those corresponding to the above-mentioned component (A). The active ester curing agent (B) can usually form a bond by reacting with the epoxy resin (A) to cure the resin composition. By incorporating a combination of the component (A) and the active ester curing agent (B) in the resin composition, a cured product with excellent peel strength can be obtained. The component (B) may be used alone or in combination of two or more.

[0032] As the (B) active ester curing agent, generally, a compound 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, is 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.

[0033] Specifically, the (B) component may include dicyclopentadiene-type active ester curing agents, naphthalene-type active ester curing agents containing a naphthalene structure, active ester curing agents containing an acetylated product of phenol novolac, active ester curing agents containing a benzoylation product of phenol novolac, active ester curing agents which are acetylated products of phenol novolac, phosphorus-containing active esters, active ester curing agents containing a styryl group and a naphthalene structure, etc., and dicyclopentadiene-type active ester curing agents and naphthalene-type active ester curing agents containing a naphthalene structure are preferred. As the dicyclopentadiene-type active ester curing agent, active ester curing agents containing a dicyclopentadiene-type diphenol structure are preferred. The "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

[0034] Commercially available products of component (B) include active ester-based curing agents containing a dicyclopentadiene-type diphenol structure, such as "EXB9451", "EXB9460", "EXB9460S", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM", "HPC-8000L-65TM", "HPC-8000", "HPC-8000-65T", "HPC-8000H", HPC-8000H-65TM (DIC); Naphthalene-type active ester curing agents containing naphthalene structures; HP-B-8151-62T, EXB-8100L-65T, EXB-8150-60T, EXB-8150-62T, EXB-9416-70BK, HPC-815060T, HPC-815062T, EXB-8 (DIC); Phosphorus-containing active ester Examples of the ester-based hardener include "EXB9401" (manufactured by DIC Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based hardener containing an acetylated product of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based hardener containing a benzoylated product of phenol novolac; "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester-based hardener which is an acetylated product of phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) as active ester-based hardeners which are benzoylated products of phenol novolac; "EXB-8500-65T" (manufactured by DIC Corporation); and "PC1300-02-65MA" (manufactured by Air Water Corporation) as an active ester-based hardener containing a styryl group and a naphthalene structure.

[0035] From the viewpoint of being able to reduce the dielectric tangent and obtaining a cured product with excellent peel strength, the active ester group equivalent of the component (B) is preferably 50 g / eq. to 500 g / eq., more preferably 50 g / eq. to 400 g / eq., and even more preferably 100 g / eq. to 300 g / eq. The active ester group equivalent is the mass of an active ester-based curing agent containing one equivalent of an active ester group.

[0036] The ratio of the amount of the epoxy resin (A) to the active ester curing agent (B) is preferably 0.01 or more, more preferably 0.3 or more, and even more preferably 0.5 or more, and is preferably 5 or less, more preferably 4 or less, and even more preferably 3 or less, in terms of the ratio of [total number of active groups of the active ester curing agent] / [total number of epoxy groups of the epoxy resin]. Here, the "number of epoxy groups of the epoxy resin" refers to the total value of all values ​​obtained by dividing the mass of the non-volatile components of the epoxy resin present in the resin composition by the epoxy equivalent. In addition, the "number of active groups of the active ester curing agent" refers to the total value of all values ​​obtained by dividing the mass of the non-volatile components of the active ester curing agent present in the resin composition by the active ester group equivalent. By setting the ratio of the amount of the epoxy resin to the active ester curing agent within this range, it is possible to obtain the effects of the present invention remarkably.

[0037] From the viewpoint of obtaining a cured product having excellent peel strength, the content of the (B) component is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more, based on 100% by mass of the non-volatile components in the resin composition, and the upper limit is preferably 25% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0038] From the viewpoint of obtaining a cured product with excellent peel strength, the content of the (B) component, relative to 100 mass% of the resin component in the resin composition, is preferably 20 mass% or more, more preferably 30 mass% or more, even more preferably 35 mass% or more, and is preferably 55 mass% or less, more preferably 50 mass% or less, even more preferably 45 mass% or less.

[0039] <(C) Compound represented by formula (C-1)> The resin composition contains a compound represented by formula (C-1) as component (C). The compound represented by formula (C-1) as component (C) does not include those corresponding to the above-mentioned components (A) to (B). By including component (C) in the resin composition, it is possible to obtain a cured product that has low dielectric properties, high adhesion to the conductor layer, and can suppress the occurrence of cracks after desmearing. The component (C) may be used alone or in combination of two or more in any ratio. [ka] In the formula, X's each independently represent an n-valent hydrocarbon group which may have a substituent, Y's each independently represent a monovalent group containing a double bond which may have a substituent, Ar's each independently represent a divalent aromatic hydrocarbon group having two alkyl groups which may be the same or different as substituents, and Z's each independently represent a single bond or a divalent aromatic hydrocarbon group which may have a substituent, n' represents an integer of 1 to 3, and m' represents an integer of 1 to 100.

[0040] n represents an integer of 1 to 3, preferably 2 or 3, and more preferably 2.

[0041] Each X independently represents an n-valent hydrocarbon group which may have a substituent, and the n-valent hydrocarbon group refers to a group obtained by removing n hydrogen atoms from a hydrocarbon compound. Specifically, it represents a monovalent hydrocarbon group, a divalent hydrocarbon group, or a trivalent hydrocarbon group. In detail, the monovalent hydrocarbon group refers to a group obtained by removing one hydrogen atom from a hydrocarbon compound, the divalent hydrocarbon group refers to a group obtained by removing two hydrogen atoms from a hydrocarbon compound, and the trivalent hydrocarbon group refers to a group obtained by removing three hydrogen atoms from a hydrocarbon compound. Examples of the hydrocarbon group include aliphatic groups and aromatic groups which contain only carbon atoms and hydrogen atoms, which will be described later. In this specification, an aliphatic group containing only carbon atoms and hydrogen atoms may be referred to as an "aliphatic hydrocarbon group", and an aromatic group containing only carbon atoms and hydrogen atoms may be referred to as an "aromatic hydrocarbon group".

[0042] The number of carbon atoms in the n-valent hydrocarbon group is preferably 2 or more, more preferably 5 or more, and even more preferably 10 or more, and is preferably 50 or less, more preferably 40 or less, and even more preferably 30 or less, or 20 or less. The number of carbon atoms does not include the number of carbon atoms of substituents.

[0043] The aliphatic hydrocarbon group may be linear, branched, or cyclic. Examples of the aliphatic hydrocarbon group include monovalent aliphatic hydrocarbon groups such as an alkyl group which may have a substituent, an alkenyl group which may have a substituent, and divalent aliphatic hydrocarbon groups such as an alkylene group which may have a substituent, an alkenylene group which may have a substituent. The number of carbon atoms of the aliphatic hydrocarbon group is the same as that of the n-valent hydrocarbon group, and does not include the number of carbon atoms of the substituent.

[0044] Examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, a decyl group, and a cyclohexyl group.

[0045] Examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, a butenyl group, a sec-butenyl group, an isobutenyl group, a tert-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, an octenyl group, a nonenyl group, and a decenyl group.

[0046] Examples of the alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a pentylene group, and a hexylene group.

[0047] Examples of the alkenylene group include an ethenylene group, a propenylene group, a butenylene group, a pentenylene group, and a hexenylene group.

[0048] Examples of the aromatic hydrocarbon group include monovalent aromatic hydrocarbon groups such as aryl groups which may have a substituent; and divalent aromatic hydrocarbon groups such as arylene groups which may have a substituent. The number of carbon atoms in the aromatic hydrocarbon group is preferably 5 or more, more preferably 10 or more, and preferably 50 or less, more preferably 40 or less, and even more preferably 30 or less, or 20 or less. The number of carbon atoms does not include the number of carbon atoms of the substituent.

[0049] Examples of the aryl group include a phenyl group, a naphthyl group, and an anthracenyl group.

[0050] Examples of the arylene group include a phenylene group, a naphthylene group, an indandiyl group, a group consisting of indandiyl-phenylene, a group represented by formula (c1), a group represented by formula (c2), etc., of which an indandiyl group, a group consisting of indandiyl-phenylene, a group represented by formula (c1), and a group represented by formula (c2) are preferred, a group consisting of indandiyl-phenylene, a group represented by formula (c1), and a group represented by formula (c2) are more preferred, and a group represented by formula (c2) is even more preferred. In the formula, "*" represents a bond. [ka]

[0051] The n-valent hydrocarbon group may have a substituent. Examples of the substituent include a halogen atom, -OH, -OC 1-6 Alkyl group, -N(C 1-10 Alkyl group) 2, C 1-20 Alkyl group, C 2-30 Alkenyl group, C 2-30 Alkynyl group, C 6-10 Aryl groups, -NH2, -CN, -C(O)OC 1-10 Examples of the substituents include alkyl groups, -COOH, -C(O)H, and -NO2. 1-20 Alkyl groups are preferred, C 1-10 Alkyl groups are more preferred, C 1-3 An alkyl group is more preferred, and a methyl group is particularly preferred. p-qThe term "」(where p and q are positive integers and p < q)" indicates that the number of carbon atoms in the organic group described immediately after this term is from p to q. For example, "C 1-10 alkyl group" represents an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure includes spiro rings and fused rings.

[0052] X in formula (C-1) preferably represents a divalent aromatic hydrocarbon group which may have a substituent, more preferably represents an arylene group, still more preferably represents an indandiy group, a group composed of indandiy-phenylene, a group represented by formula (c1), or a group represented by formula (c2), even more preferably represents an indandiy group, a group represented by formula (c1), or a group represented by formula (c2), and particularly preferably represents a group represented by formula (c2).

[0053] Y each independently represents a monovalent group containing a double bond which may have a substituent. As the monovalent group containing a double bond, a carbon-carbon double bond, a carbon-oxygen double bond, and a group having two or more of these can be used. A plurality of carbon-carbon double bonds and carbon-oxygen double bonds may be present.

[0054] Examples of the monovalent group containing a double bond include a vinyl group, an allyl group, a vinylbenzyl group, a styryl group, an acryloyl group, a methacryloyl group, a fumaroyl group, a maleoyl group, a carbonyl group, etc. The vinylbenzyl group is preferably any one of an o-vinylbenzyl group, an m-vinylbenzyl group, and a p-vinylbenzyl group, and a p-vinylbenzyl group is preferred. The monovalent group containing a double bond may have a substituent. The substituents are the same as those that the n-valent hydrocarbon group represented by X may have.

[0055] Among them, Y preferably represents any one of an acryloyl group, a methacryloyl group, and a vinylbenzyl group, and more preferably represents a methacryloyl group.

[0056] Each Ar independently represents a divalent aromatic hydrocarbon group having two alkyl groups, which may be the same or different, as a substituent. The divalent aromatic hydrocarbon group preferably has 6 to 20 carbon atoms, more preferably 6 to 15 carbon atoms, and even more preferably 6 to 10 carbon atoms. The number of carbon atoms does not include the number of carbon atoms of the alkyl groups as the substituents.

[0057] Examples of the divalent aromatic hydrocarbon group include an arylene group, etc. Examples of the arylene group include a phenylene group, a naphthylene group, an indandiyl group, and a group consisting of an indandiyl-phenylene group, etc., and the phenylene group is preferable.

[0058] The two alkyl groups which may be the same or different as the substituents are preferably alkyl groups having 1 to 12 carbon atoms, more preferably alkyl groups having 1 to 10 carbon atoms, even more preferably alkyl groups having 1 to 6 carbon atoms, even more preferably alkyl groups having 1 to 3 carbon atoms, and particularly preferably a methyl group. The substituents may be the same or different, but are preferably the same from the viewpoint of obtaining the effects of the present invention significantly.

[0059] The bonding positions of the two alkyl groups that Ar has as substituents may be any of the ortho, meta, and para positions based on the position bonding to the oxygen atom in formula (C-1). From the viewpoint of significantly obtaining the effects of the present invention, however, it is preferable that both of the two alkyl groups are bonded at the ortho positions.

[0060] Each Z independently represents a single bond or a divalent aromatic hydrocarbon group which may have a substituent. The divalent aromatic hydrocarbon group preferably has 6 to 20 carbon atoms, more preferably has 6 to 15 carbon atoms, and further preferably has 6 to 10 carbon atoms. The number of carbon atoms does not include the number of carbon atoms as a substituent.

[0061] Examples of the divalent aromatic hydrocarbon group include an arylene group. Examples of the arylene group include a phenylene group and a naphthylene group, and a phenylene group is preferred. The divalent aromatic hydrocarbon group may have a substituent. The substituent is the same as the substituent that the n-valent hydrocarbon group represented by X may have.

[0062] When n is 2 or 3, it is preferable that at least one of the multiple Z's represents a divalent aromatic hydrocarbon group which may have a substituent.

[0063] m represents an integer of 1 to 100, preferably an integer of 1 to 50, more preferably an integer of 1 to 30, and even more preferably an integer of 1 to 20.

[0064] The compound represented by formula (C-1) is preferably a compound represented by formula (C-2). [ka] In the formula, R 1 and R 2 each independently represents a monovalent group containing a double bond; R 3 and R 4 represents a divalent aromatic hydrocarbon group having two alkyl groups, which may be the same or different, as substituents, each independently; R 5 each independently represents a divalent aromatic hydrocarbon group; R 6 represents a single bond or a divalent aromatic hydrocarbon group which may have a substituent. m1 represents an integer of 1 to 100.

[0065] R 1 and R 2 each independently represents a monovalent group containing a double bond, and is the same as Y in formula (C-1).

[0066] R 3 and R 4each independently represents a divalent aromatic hydrocarbon group having two alkyl groups, which may be the same or different, as substituents, and is the same as Ar in formula (C-1).

[0067] R 5 each independently represents a divalent aromatic hydrocarbon group. The divalent aromatic hydrocarbon group may have a substituent. The substituent is the same as the substituent that X in formula (C-1) may have. The number of carbon atoms in the divalent aromatic hydrocarbon group is preferably 5 or more, more preferably 10 or more, and preferably 50 or less, more preferably 40 or less, even more preferably 30 or less, or 20 or less. The number of carbon atoms does not include the number of carbon atoms of the substituent.

[0068] Examples of the divalent aromatic hydrocarbon group include an arylene group. Examples of the arylene group include a phenylene group, a naphthylene group, an indandiyl group, a group consisting of indandiyl-phenylene, a group represented by formula (c1), and a group represented by formula (c2). Among these, an indandiyl group, a group consisting of indandiyl-phenylene, a group represented by formula (c1), and a group represented by formula (c2) are preferred, an indandiyl group and a group represented by formula (c2) are more preferred, and a group represented by formula (c2) is even more preferred.

[0069] R 6 represents a single bond or a divalent aromatic hydrocarbon group which may have a substituent, and is the same as Z in formula (C-1).

[0070] m1 represents an integer of 1 to 100 and is the same as m in formula (C-1).

[0071] The compound represented by formula (C-1) is preferably a compound represented by formula (C-3). [ka] In the formula, R 11 and R 12 each independently represents a monovalent group containing a double bond; R 13 and R 14represents a divalent aromatic hydrocarbon group having two alkyl groups, which may be the same or different, as substituents, each independently; R 15 represents a single bond or a divalent aromatic hydrocarbon group which may have a substituent. m2 represents an integer of 1 to 100.

[0072] R 11 and R 12 each independently represents a monovalent group containing a double bond, and is the same as Y in formula (C-1).

[0073] R 13 and R 14 each independently represents a divalent aromatic hydrocarbon group having two alkyl groups, which may be the same or different, as substituents, and is the same as Ar in formula (C-1).

[0074] R 15 represents a single bond or a divalent aromatic hydrocarbon group which may have a substituent, and is the same as the divalent aromatic hydrocarbon group represented by Z in formula (C-1).

[0075] m2 represents an integer of 1 to 100 and is the same as m in formula (C-1).

[0076] Specific examples of the component (C) include the following compounds (Ca) to (Cb). However, the component (C) is not limited to these specific examples. In the formulae, each m independently represents an integer of 1 to 100. [ka]

[0077] The component (C) may be synthesized by a known method. The component (C) can be synthesized by, for example, the method described in WO 2023 / 008079.

[0078] From the viewpoint of obtaining the effects of the present invention remarkably, the weight average molecular weight of the (C) component is preferably 500 or more, more preferably 1000 or more, and even more preferably 1500 or more, and is preferably 50000 or less, more preferably 10000 or less, and even more preferably 5000 or less.

[0079] From the viewpoint of obtaining the effects of the present invention remarkably, the content of the (C) component is preferably 1% by mass or more, more preferably 2% by mass or more, and even more preferably 2.5% by mass or more, based on 100% by mass of the non-volatile components in the resin composition. The upper limit is preferably 10% by mass or less, more preferably 8% by mass or less, and particularly preferably 5% by mass or less.

[0080] From the viewpoint of obtaining a cured product exhibiting good mechanical strength and insulation reliability, the content of the (C) component, relative to 100 mass% of the resin component in the resin composition, is preferably 1 mass% or more, more preferably 5 mass% or more, even more preferably 10 mass% or more, and is preferably 25 mass% or less, more preferably 20 mass% or less, even more preferably 15 mass% or less.

[0081] When the content of the (C) component when the resin component in the resin composition is taken as 100% by mass is c1, and the content of the (B) component when the resin component in the resin composition is taken as 100% by mass is b1, b1 / c1 is preferably 0.5 or more, more preferably 1 or more, and even more preferably 1.5 or more, and is preferably 10 or less, more preferably 8 or less, and even more preferably 5 or less. By adjusting the contents of the (B) component and the (C) component so that b1 / c1 falls within this range, it becomes possible to obtain the effects of the present invention significantly.

[0082] <(D) Inorganic filler> The resin composition may further contain an inorganic filler (D) as an optional component. By including the inorganic filler (D) in the resin composition, a cured product with low dielectric properties can be obtained. The inorganic filler (D) is usually included in the resin composition in the form of particles. The component (D) may be used alone or in combination of two or more types.

[0083] (D) An inorganic compound is used as the material of the inorganic filler. (D) Examples of the material of the inorganic filler include silica, alumina, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly suitable. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. In addition, spherical silica is preferable as the silica.

[0084] (D) Commercially available inorganic fillers include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs Co., Ltd.; "UFP-30", "DAW-03", and "FB-105FD" manufactured by Denka Co., Ltd.; "Silfill NSS-3N", "Silfill NSS-4N", and "Silfill NSS-5N" manufactured by Tokuyama Corporation; and "Cellspheres" and "MGH-005" manufactured by Taiheiyo Cement Corporation.

[0085] The average particle size of the (D) inorganic filler is preferably 0.01 μm or more, more preferably 0.1 μm or more, even more preferably 0.3 μm or more, and is preferably 10 μm or less, more preferably 5 μm or less, even more preferably 3 μm or less.

[0086] (D) 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 prepared on a volume basis using a laser diffraction / scattering particle size distribution measuring device, and the median diameter is used as the average particle size. The measurement sample can be prepared by weighing 100 mg of the 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 can be 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 can be measured using a flow cell method, and the average particle size can be 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.

[0087] (D) The BET specific surface area of ​​the inorganic filler is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, preferably 100m 2 / g or less, more preferably 70m 2 / g or less, more preferably 40m 2 / g or less.

[0088] (D) The specific surface area of ​​the inorganic filler can be measured according to the BET method by adsorbing nitrogen gas onto the surface of the sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) and calculating the specific surface area using the BET multipoint method.

[0089] (D) The inorganic filler is preferably treated with a surface treatment agent from the viewpoint of improving moisture resistance and dispersibility. Examples of the surface treatment agent include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, titanate coupling agents, etc. The surface treatment agent may be used alone or in any combination of two or more.

[0090] 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), and Shin-Etsu Chemical Co., Ltd.'s "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane).

[0091] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment with the surface treatment agent is preferably within a specific range. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2% to 5% by mass of the surface treatment agent, more preferably with 0.2% to 3% by mass of the surface treatment agent, and even more preferably with 0.3% to 2% by mass of the surface treatment agent.

[0092] 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 preventing an increase in the melt viscosity of the resin composition, it is more preferable that the content is 1.0 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:

[0093] (D) 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.

[0094] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit mass of the inorganic filler. The amount of carbon per unit mass of the inorganic filler is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, and is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.5% by mass or less. The amount of carbon per unit mass of the (D) inorganic filler can be measured using a carbon analyzer in the same manner as the amount of carbon per unit surface area of ​​the (D) inorganic filler.

[0095] The content of the (D) inorganic filler, relative to 100 mass% of the non-volatile components in the resin composition, is preferably 60 mass% or more, more preferably 65 mass% or more, and particularly preferably 70 mass% or more, and is preferably 90 mass% or less, more preferably 85 mass% or less, and particularly preferably 80 mass% or less.

[0096] <(E) Compounds Having a Double Bond> The resin composition may contain a compound having a double bond (E) as an optional component. The compound having a double bond (E) as the component (E) does not include those corresponding to the above-mentioned components (A) to (D). The component (E) may be used alone or in combination of two or more kinds in any ratio.

[0097] The component (E) may be a compound having a carbon-carbon double bond, and the component (E) may have a plurality of carbon-carbon double bonds. The carbon-carbon double bond is preferably present as a radically polymerizable unsaturated group. Therefore, the component (E) is preferably a radically polymerizable compound having a radically polymerizable unsaturated group. Examples of the radically polymerizable unsaturated group include a group containing an ethylenic double bond.

[0098] Examples of the radically polymerizable unsaturated group include a vinyl group, an allyl group, a vinylphenyl group, an acryloyl group, a methacryloyl group, a fumaroyl group, and a maleoyl group. The number of radically polymerizable unsaturated groups contained in the component (E) is usually 1 or more, and preferably 2 or more. When the component (E) contains two or more radically polymerizable unsaturated groups, the two or more radically polymerizable unsaturated groups may be the same or different.

[0099] Examples of the component (E) include allyl radical polymerizable compounds, (meth)acrylic radical polymerizable compounds, styrene radical polymerizable compounds, maleimide radical polymerizable compounds, etc. Among these, styrene radical polymerizable compounds and maleimide radical polymerizable compounds are preferred.

[0100] The allyl radical polymerizable compound is, for example, a compound having one or more, preferably two or more, allyl groups. Examples of allyl radical polymerizable compounds include aromatic carboxylic acid allyl ester compounds such as diallyl diphenate, triallyl trimellitate, diallyl phthalate, diallyl isophthalate, diallyl terephthalate, diallyl 2,6-naphthalenedicarboxylate, and diallyl 2,3-naphthalenecarboxylate; isocyanuric acid allyl ester compounds such as 1,3,5-triallyl isocyanurate and 1,3-diallyl-5-glycidyl isocyanurate; epoxy-containing aromatic allyl compounds such as 2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane; benzoxazine-containing aromatic allyl compounds such as bis[3-allyl-4-(3,4-dihydro-2H-1,3-benzoxazin-3-yl)phenyl]methane; ether-containing aromatic allyl compounds such as 1,3,5-triallyl ether benzene; allyl silane compounds such as diallyl diphenyl silane; and resins containing a plurality of benzene rings and allyl groups. Commercially available allyl radical polymerizable compounds include, for example, "TAIC" (1,3,5-triallyl isocyanurate) manufactured by Nippon Kasei Chemical Industry Co., Ltd., "DAD" (diallyl diphenate) manufactured by Nisshoku Techno Fine Chemical Co., Ltd., "TRIAM-705" (triallyl trimellitate) manufactured by Fujifilm Wako Pure Chemical Industries, Ltd., "DAND" (diallyl 2,3-naphthalene carboxylate) manufactured by Nisshoku Techno Fine Chemical Co., Ltd., and "ALP-d" (bis[3 Examples of such compounds include "RE-810NM" (2,2-bis[3-allyl-4-(glycidyloxy)phenyl]propane) manufactured by Nippon Kayaku Co., Ltd., "DA-MGIC" (1,3-diallyl-5-glycidyl isocyanurate) manufactured by Shikoku Kasei Corporation, and "NE-V-1100-70T" (a resin containing multiple benzene rings and multiple allyl groups) manufactured by DIC Corporation.

[0101] The (meth)acrylic radical polymerizable compound is, for example, a compound having one or more, preferably two or more, acryloyl groups and / or methacryloyl groups. Examples of the (meth)acrylic radical polymerizable compound include cyclohexane-1,4-dimethanol di(meth)acrylate, cyclohexane-1,3-dimethanol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, 1,2-diphenylmethane di(meth)acrylate, 1,3-diphenylmethane di(meth)acrylate, 1,4-diphenylmethane di(meth)acrylate, 1,5-diphenylmethane di(meth)acrylate, 1,6-diphenylmethane di(meth)acrylate, 1,8-diphenylmethane di(meth)acrylate, 1,9-diphenylmethane ...5-diphenylmethane di(meth)acrylate, 1,5-diphenylmethane di(meth)acrylate, 1,6-diphenylmethane di(meth)acrylate, 1,8-diphenylmethane di(meth)acrylate, 1,9-diphenylmethane di(meth)acrylate, 1,5-diphenylmethane di(meth)acrylate, 1,5-diphenylmethane di(meth)acrylate, 1,5-diphenylmethane di(meth)acrylate, 1,5-diphenylmethane aliphatic (meth)acrylic acid ester compounds with low molecular weight (molecular weight less than 1000), such as dioxane glycol di(meth)acrylate, 3,6-dioxa-1,8-octanediol di(meth)acrylate, 1,10-decanediol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolethane tri(meth)acrylate, glycerin tri(meth)acrylate, and pentaerythritol tetra(meth)acrylate; Examples of the ether-containing (meth)acrylic acid ester compound include low molecular weight (molecular weight less than 1000) ether-containing (meth)acrylic acid ester compounds such as 9,9-bis[4-(2-acryloyloxyethoxy)phenyl]fluorene, ethoxylated bisphenol A di(meth)acrylate, and propoxylated bisphenol A di(meth)acrylate; low molecular weight (molecular weight less than 1000) isocyanurate-containing (meth)acrylic acid ester compounds such as tris(3-hydroxypropyl)isocyanurate tri(meth)acrylate, tris(2-hydroxyethyl)isocyanurate tri(meth)acrylate, and ethoxylated isocyanuric acid tri(meth)acrylate; and high molecular weight (molecular weight 1000 or more) acrylic acid ester compounds such as (meth)acrylic modified polyphenylene ether resin.Examples of commercially available (meth)acrylic radically polymerizable compounds include "A-DOG" (dioxane glycol diacrylate) manufactured by Shin-Nakamura Chemical Co., Ltd., "DCP-A" (tricyclodecane dimethanol diacrylate) and "DCP" (tricyclodecane dimethanol dimethacrylate) manufactured by Kyoeisha Chemical Co., Ltd., "KAYARAD R-684" (tricyclodecane dimethanol diacrylate) and "KAYARAD R-604" (dioxane glycol diacrylate) manufactured by Nippon Kayaku Co., Ltd., and "SA9000" and "SA9000-111" (methacrylic-modified polyphenylene ether) manufactured by SABIC.

[0102] The styrene radical polymerizable compound is, for example, a compound having one or more, preferably two or more, vinyl groups directly bonded to an aromatic carbon atom. Examples of the styrene radical polymerizable compound include low molecular weight (molecular weight less than 1000) styrene compounds such as divinylbenzene, 2,4-divinyltoluene, 2,6-divinylnaphthalene, 1,4-divinylnaphthalene, 4,4'-divinylbiphenyl, 1,2-bis(4-vinylphenyl)ethane, 2,2-bis(4-vinylphenyl)propane, and bis(4-vinylphenyl)ether; high molecular weight (molecular weight 1000 or more) styrene compounds such as vinylbenzyl-modified polyphenylene ether resin and styrene-divinylbenzene copolymer. Examples of commercially available styrene-based radically polymerizable compounds include "ODV-XET(X03)", "ODV-XET(X04)", and "ODV-XET(X05)" (styrene-divinylbenzene copolymers) manufactured by Nippon Steel Chemical & Material Co., Ltd., and "OPE-2St 1200" and "OPE-2St 2200" (vinylbenzyl-modified polyphenylene ether resins) manufactured by Mitsubishi Gas Chemical Co., Inc.

[0103] The maleimide radical polymerizable compound is, for example, a compound having one or more, preferably two or more, maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl groups). The maleimide radical polymerizable compound may be an aliphatic maleimide compound containing an aliphatic amine skeleton, or an aromatic maleimide compound containing an aromatic amine skeleton. Examples of commercially available maleimide radical polymerizable compounds include "BMI-3000J", "BMI-5000", "BMI-1400", "BMI-1500", "BMI-1700", "BMI-689" (all manufactured by Designer Molecules Inc.), "SLK6895-T90", "SLK-6895", "SLK-1500" (all manufactured by Shin-Etsu Chemical Co., Ltd.), "MIR-3000-70MT" (manufactured by Nippon Kayaku Co., Ltd.), "BMI-4000" (manufactured by Yamato Kasei Co., Ltd.), and "BMI-80" (manufactured by Keiai Kasei Co., Ltd.). In addition, as a maleimide radical polymerizable compound, a maleimide resin (indan ring skeleton-containing maleimide compound) disclosed in the Japan Institute of Invention and Innovation Disclosure Technical Journal No. 2020-500211 may be used.

[0104] The ethylenically unsaturated bond equivalent of the component (E) is preferably 20 g / eq. to 3,000 g / eq., more preferably 50 g / eq. to 2,500 g / eq., still more preferably 70 g / eq. to 2,000 g / eq., and particularly preferably 90 g / eq. to 1,500 g / eq. The ethylenically unsaturated bond equivalent represents the mass of the radical polymerizable compound per equivalent of the ethylenically unsaturated bond.

[0105] The weight average molecular weight of the (E) component is preferably 40,000 or less, more preferably 10,000 or less, even more preferably 5,000 or less, and particularly preferably 3,000 or less. The lower limit is not particularly limited, but may be, for example, 150 or more. The weight average molecular weight can be measured as a polystyrene-equivalent value by gel permeation chromatography (GPC).

[0106] From the viewpoint of significantly obtaining the desired effects of the present invention, the content of the (E) component is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 1.5% by mass or more, when the non-volatile components in the resin composition are taken as 100% by mass, and the upper limit is preferably 8% by mass or less, more preferably 5% by mass or less, and even more preferably 3% by mass or less.

[0107] From the viewpoint of significantly obtaining the desired effects of the present invention, for example, from the viewpoint of obtaining a cured product having a high glass transition temperature, the content of the (E) component, relative to 100 mass% of the resin component in the resin composition, is preferably 1 mass% or more, more preferably 3 mass% or more, even more preferably 5 mass% or more, and is preferably 25 mass% or less, more preferably 20 mass% or less, even more preferably 15 mass% or less, or 10 mass% or less.

[0108] <(F) Hardener> The resin composition may further contain a (F) curing agent as an optional component. The (F) curing agent as the (F) component does not include those corresponding to the above-mentioned (A) to (E) components. As the (F) curing agent, a compound having a function of reacting with the (A) component to cure the resin composition can be used, and examples thereof include phenol-based curing agents, naphthol-based curing agents, carbodiimide-based curing agents, benzoxazine-based curing agents, and cyanate ester-based curing agents. Among them, the (F) curing agent preferably contains a phenol-based curing agent from the viewpoint of obtaining the effects of the present invention significantly. The (F) curing agent may be used alone or in combination of two or more kinds.

[0109] As the phenol-based curing agent and naphthol-based curing agent, from the viewpoint of heat resistance and water resistance, a phenol-based curing agent having a novolac structure or a naphthol-based curing agent having a novolac structure is preferable. Also, from the viewpoint of adhesion to the conductor layer, a nitrogen-containing phenol-based curing agent is preferable, and a triazine skeleton-containing phenol-based curing agent is more preferable.

[0110] 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", "LA3018-50P", "EXB-9500", and "KA-1163" manufactured by DIC Corporation.

[0111] The carbodiimide curing agent is a compound having one or more carbodiimide groups (-N=C=N-) in one molecule, and the carbodiimide curing agent is preferably a compound having two or more carbodiimide groups in one molecule.

[0112] Specific examples of the carbodiimide-based curing agent include commercially available carbodiimide-based curing agents such as Carbodilite V-03 (carbodiimide group equivalent: 216 g / eq., V-05 (carbodiimide group equivalent: 262 g / eq.), V-07 (carbodiimide group equivalent: 200 g / eq.), V-09 (carbodiimide group equivalent: 200 g / eq.), and Stavaxol P (carbodiimide group equivalent: 302 g / eq.), all manufactured by Nisshinbo Chemical Co., Ltd.

[0113] Specific examples of benzoxazine-based curing agents include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemical Industry Co., Ltd.

[0114] 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 arxada's "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 triazine-converted into a trimer).

[0115] The ratio of the amount of the (A) component to the (F) component is preferably 1:0.01 to 1:10, more preferably 1:0.05 to 1:8, and even more preferably 1:0.08 to 1:5, in terms of the ratio of [total number of epoxy groups in the (A) component] to [total number of active groups in the (F) component]. Here, the "total number of epoxy groups in the epoxy resin" refers to the total value obtained by dividing the mass of the non-volatile components of the (A) component present in the resin composition by the epoxy equivalent. In addition, the "total number of active groups in the (F) component" refers to the total value obtained by dividing the mass of the non-volatile components of the (F) component present in the resin composition by the active group equivalent. By setting the ratio of the amount of the (F) component to the (A) component within this range, the effects of the present invention can be obtained significantly.

[0116] The ratio of the amount of the (A) component to the (B) and (F) components is preferably 1:0.01 to 1:10, more preferably 1:0.3 to 1:5, and even more preferably 1:0.4 to 1:4, in terms of the ratio of [total number of epoxy groups in the (A) component] to [total number of active groups in the (B) and (F) components]. Here, the "total number of active groups in the (B) and (F) components" refers to the total value of the mass of the non-volatile components of the (B) and (F) components present in the resin composition divided by the active group equivalent. By setting the ratio of the amount of the (A) component to the (B) and (F) components within this range, the effects of the present invention can be obtained significantly.

[0117] From the viewpoint of obtaining the desired effect of the present invention remarkably, the content of the (F) component is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 1.5% by mass or more, based on 100% by mass of the non-volatile components in the resin composition. The upper limit is preferably 5% by mass or less, more preferably 4% by mass or less, and even more preferably 3% by mass or less.

[0118] From the viewpoint of significantly obtaining the desired effects of the present invention, the content of the (F) component, relative to 100 mass% of the resin component in the resin composition, is preferably 1 mass% or more, more preferably 3 mass% or more, even more preferably 5 mass% or more, and is preferably 20 mass% or less, more preferably 15 mass% or less, even more preferably 10 mass% or less.

[0119] <(G)Organic filler> The resin composition may further contain an organic filler as an optional component (G). The organic filler as component (G) does not include those corresponding to the above-mentioned components (A) to (F). The component (G) may be used alone or in combination of two or more.

[0120] The (G) component is present in the resin composition in the form of particles. Examples of the (G) component include rubber particles, polyamide fine particles, silicone particles, and core-shell type particles. In the present invention, from the viewpoint of significantly obtaining the desired effects of the present invention, it is preferable to use either the rubber particles or the core-shell type particles, and it is more preferable to use the rubber particles.

[0121] Examples of the rubber component contained in the rubber particles include polybutadiene, polyisoprene, polychlorobutadiene, ethylene-vinyl acetate copolymer, styrene-butadiene copolymer, styrene-isoprene copolymer, styrene-isobutylene copolymer, acrylonitrile-butadiene copolymer, isoprene-isobutylene copolymer, isobutylene-butadiene copolymer, ethylene-propylene-diene terpolymer, ethylene-propylene-butene terpolymer, and other olefin-based thermoplastic elastomers; poly(propyl meth)acrylate, poly(butyl meth)acrylate, poly(cyclohexyl meth)acrylate, poly(octyl meth)acrylate, and other acrylic thermoplastic elastomers, and preferably olefin-based thermoplastic elastomers, and more preferably styrene-butadiene copolymers. Furthermore, the rubber component may be mixed with silicone-based rubbers such as polyorganosiloxane rubber. The rubber component contained in the rubber particles has a glass transition temperature of, for example, 0° C. or lower, preferably −10° C. or lower, more preferably −20° C. or lower, and even more preferably −30° C. or lower.

[0122] As the rubber particles, commercially available products may be used, for example, "EXL2655" manufactured by Dow Chemical Japan, "AC3401N" and "AC3816N" manufactured by Aica Kogyo Co., Ltd.

[0123] The core-shell type particles are particulate organic fillers consisting of a core particle containing a rubber component as described above and one or more shell layers covering the core particle. Furthermore, the core-shell type particles are preferably core-shell type graft copolymer particles consisting of a core particle containing a rubber component as described above and a shell portion obtained by graft copolymerization of a monomer component copolymerizable with the rubber component contained in the core particle. The core-shell type as used herein does not necessarily refer only to particles in which the core particle and the shell portion are clearly distinguishable, but also includes particles in which the boundary between the core particle and the shell portion is unclear, and the core particle does not necessarily have to be completely covered with the shell portion.

[0124] The rubber component is preferably contained in the core-shell graft copolymer particles in an amount of 40% by mass or more, more preferably 50% by mass or more, and even more preferably 60% by mass or more. The upper limit of the rubber component content in the core-shell graft copolymer particles is not particularly limited, but is preferably, for example, 95% by mass or less, and more preferably 90% by mass, from the viewpoint of sufficiently covering the core particles with the shell portion.

[0125] Examples of monomer components forming the shell portion of the core-shell type graft copolymer particles include (meth)acrylic acid esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, cyclohexyl (meth)acrylate, octyl (meth)acrylate, and glycidyl (meth)acrylate; (meth)acrylic acid; N-substituted maleimides such as N-methylmaleimide and N-phenylmaleimide; maleimide; α,β-unsaturated carboxylic acids such as maleic acid and itaconic acid; aromatic vinyl compounds such as styrene, 4-vinyltoluene, and α-methylstyrene; and (meth)acrylonitrile. Of these, (meth)acrylic acid esters are preferred, and methyl (meth)acrylate is more preferred.

[0126] Examples of commercially available core-shell type graft copolymer particles include "CHT" manufactured by Cheil Industries; "B602" manufactured by Techno UMG; "Paraloid EXL2602", "Paraloid EXL2603", "Paraloid EXL2655", "Paraloid EXL2311", "Paraloid EXL2313", "Paraloid EXL2315", "Paraloid KM330", "Paraloid KM336P", and "Paraloid KCZ201" manufactured by Dow Chemical Japan; "Metabrene C-223A", "Metabrene E-901", "Metabrene S-2001", "Metabrene W-450A", and "Metabrene SRK-200" manufactured by Mitsubishi Rayon; and "Kane Ace M-511", "Kane Ace M-600", "Kane Ace M-400", "Kane Ace M-580", and "Kane Ace MR-01" manufactured by Kaneka Corporation. These may be used alone or in combination of two or more.

[0127] The average particle size (average primary particle size) of the core-shell graft copolymer particles is not particularly limited, but is preferably 20 nm or more, more preferably 50 nm or more, even more preferably 80 nm or more, particularly preferably 100 nm or more, preferably 5,000 nm or less, more preferably 2,000 nm or less, even more preferably 1,000 nm or less, particularly preferably 500 nm or less. The average particle size (average primary particle size) of the core-shell graft copolymer particles can be measured using a zeta potential particle size distribution measuring device or the like.

[0128] From the viewpoint of obtaining the effects of the present invention prominently, the content of the (G) component, when the non-volatile components in the resin composition are taken as 100 mass%, is preferably 0.1 mass% or more, more preferably 0.2 mass% or more, even more preferably 0.3 mass% or more, and is preferably 3 mass% or less, more preferably 1.5 mass% or less, even more preferably 1 mass% or less.

[0129] From the viewpoint of obtaining the effects of the present invention prominently, the content of the (G) component, when the resin component in the resin composition is taken as 100 mass%, is preferably 1 mass% or more, more preferably 2 mass% or more, even more preferably 3 mass% or more, and is preferably 10 mass% or less, more preferably 8 mass% or less, even more preferably 5 mass% or less.

[0130] <(H) Curing accelerator> The resin composition may further contain a curing accelerator as an optional component (H). The curing accelerator (H) as the component (H) does not include those corresponding to the above-mentioned components (A) to (G). By including the component (H), it becomes possible to further accelerate the curing of the component (A). The component (H) may be used alone or in combination of two or more kinds.

[0131] Examples of the component (H) include phosphorus-based curing accelerators, urea-based curing accelerators, guanidine-based curing accelerators, imidazole-based curing accelerators, metal-based curing accelerators, amine-based curing accelerators, etc. Among these, curing accelerators selected from amine-based curing accelerators and metal-based curing accelerators are preferred, and amine-based curing accelerators are particularly preferred.

[0132] Examples of the phosphorus-based curing accelerator include aliphatic phosphonium salts such as tetrabutyl phosphonium bromide, tetrabutyl phosphonium chloride, tetrabutyl phosphonium acetate, tetrabutyl phosphonium decanoate, tetrabutyl phosphonium laurate, bis(tetrabutyl phosphonium)pyromellitate, tetrabutyl phosphonium hydrogenhexahydrophthalate, tetrabutyl phosphonium 2,6-bis[(2-hydroxy-5-methylphenyl)methyl]-4-methylphenolate, and di-tert-butyldimethylphosphonium tetraphenylborate; methyl triphenyl phosphonium bromide, ethyl triphenyl phosphonium bromide, propyl triphenyl phosphonium bromide, butyl triphenyl phosphonium bromide, benzyl triphenyl phosphonium chloride, tetraphenyl phosphonium bromide, p-tolyl triphenyl phosphonium tetra-p-tolylborate, tetraphenyl phosphonium bromide, and the like. aromatic phosphonium salts such as 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; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone adducts such as triphenylphosphine-p-benzoquinone adduct; 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, tris(2,5-dimethylphenyl)phosphine, tris(2,6-dimethylphenyl)phosphine Examples of aromatic phosphines include tris(3,5-dimethylphenyl)phosphine, tris(2,4,6-trimethylphenyl)phosphine, tris(2,6-dimethyl-4-ethoxyphenyl)phosphine, tris(2-methoxyphenyl)phosphine, tris(4-methoxyphenyl)phosphine, tris(4-ethoxyphenyl)phosphine, tris(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether.

[0133] Examples of the urea-based curing accelerator include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, and 3-(3,4-dimethylphenyl)-1,1-dimethylurea. aromatic dimethylureas such as butylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), and N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluene bisdimethylurea].

[0134] 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, 7-methyl-1,5,7-triazabicyclo[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.

[0135] Examples of the imidazole-based 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, and 1-benzyl-2-methylimidazole. 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 imidazole compounds such as 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds and epoxy resins.

[0136] As the imidazole-based curing accelerator, commercially available products may be used, for example, "1B2PZ", "2MZA-PW", "2PHZ-PW", and "C11Z-A" manufactured by Shikoku Chemical Industry Co., Ltd., and "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0137] 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.

[0138] 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.

[0139] As the amine-based curing accelerator, a commercially available product may be used, for example, "MY-25" manufactured by Ajinomoto Fine-Techno Co., Ltd.

[0140] From the viewpoint of obtaining the effects of the present invention prominently, the content of the (H) component is preferably 0.1 mass% or more, more preferably 0.5 mass% or more, and even more preferably 0.1 mass% or more, and is preferably 1.5 mass% or less, more preferably 1 mass% or less, and even more preferably 0.8 mass% or less, based on 100 mass% of the non-volatile components in the resin composition.

[0141] From the viewpoint of obtaining the effects of the present invention prominently, the content of the (H) component, when the resin component in the resin composition is taken as 100 mass%, is preferably 0.5 mass% or more, more preferably 1 mass% or more, even more preferably 1.5 mass% or more, and is preferably 5 mass% or less, more preferably 4 mass% or less, even more preferably 3 mass% or less.

[0142] <(I) Other additives> The resin composition may further contain other additives as optional components in addition to the above-mentioned components. (I) Other additives include, for example, thermoplastic resins; elastomers; polymerization initiators; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentone and montmorillonite; defoamers such as silicone-based defoamers, acrylic defoamers, fluorine-based defoamers, and vinyl resin-based defoamers; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silane; adhesion imparters such as triazole-based adhesion imparters, tetrazole-based adhesion imparters, and triazine-based adhesion imparters; hindered pheno fluorescent brightening agents 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); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; 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; photopolymerization initiation assistants such as tertiary amines; and photosensitizers such as pyrarizones, anthracenes, coumarins, xanthones, and thioxanthones. (I) Other additives may be used alone or in combination of two or more kinds.

[0143] <(J) Solvent> The resin composition may further contain an arbitrary solvent as a volatile component in addition to the non-volatile components described above. As the (J) solvent, a known solvent may be appropriately used, and the type is not particularly limited, and an organic solvent is preferable. As the (J) 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, anisole, 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 solvent include ether ester solvents such as ethyl acetate, ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate, ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butylcarbitol), 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 (J) solvent may be used alone or in combination of two or more in any ratio.

[0144] From the viewpoint of obtaining the effect of the present invention significantly, the resin composition preferably contains 0.5% by mass or more and 3% by mass or less of the (J) solvent, based on 100% by mass of all the components of the resin composition. Specifically, the (J) solvent is preferably contained in an amount of 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1.5% by mass or less, based on 100% by mass of all the components of the resin composition, and is preferably contained in an amount of 0.5% by mass or more, more preferably 0.8% by mass or more, and even more preferably 1% by mass or more.

[0145] The method for preparing the resin composition of the present invention is not particularly limited, and examples thereof include a method in which the blending components are mixed and dispersed using a rotary mixer or the like, with the addition of a solvent or the like as necessary.

[0146] <Physical properties and applications of resin compositions> The resin composition contains a combination of components (A), (B), and (C), and therefore can provide a cured product that has low dielectric properties, high adhesion to the conductor layer, and can suppress the occurrence of cracks after desmearing. The resin composition also exhibits the property of low melt viscosity. In addition, it is usually possible to provide a cured product with a high glass transition temperature.

[0147] The cured product obtained by thermally curing the resin composition at 190°C for 90 minutes exhibits the characteristic of a low dielectric loss tangent. Thus, the cured product provides an insulating layer with a low dielectric loss tangent. The dielectric loss tangent is preferably 0.005 or less, more preferably 0.004 or less, and even more preferably 0.003 or less. The lower limit of the dielectric loss tangent may be 0.0001 or more. The dielectric loss tangent can be measured according to the method described in the examples below.

[0148] The cured product obtained by thermally curing the resin composition at 190°C for 90 minutes exhibits the characteristic of a low relative dielectric constant. Thus, the cured product provides an insulating layer with a low relative dielectric constant. The relative dielectric constant is preferably 4.0 or less, more preferably 3.8 or less, and even more preferably 3.6 or less. The lower limit of the relative dielectric constant may be 2.0 or more. The relative dielectric constant can be measured according to the method described in the examples below.

[0149] The cured product obtained by thermally curing the resin composition at 130°C for 30 minutes and then at 170°C for 30 minutes exhibits the characteristic of high peel strength between the resin composition and the plated conductor layer. Thus, the cured product provides an insulating layer with excellent peel strength between the resin composition and the plated conductor layer. The peel strength is preferably 0.1 kgf / cm or more, more preferably 0.2 kgf / cm or more, and even more preferably 0.3 kgf / cm or more. The upper limit of the peel strength may be 10 kgf / cm or less. The peel strength can be measured according to the method described in the examples below.

[0150] The cured product obtained by thermally curing the resin composition at 130°C for 30 minutes and then at 175°C for 40 minutes exhibits the property of excellent crack resistance after desmearing. Thus, the cured product provides an insulating layer with excellent crack resistance. Specifically, a layer made of the cured product of the resin composition is formed on both sides of a core material in which circular copper pads with a diameter of 350 μm are formed in a lattice shape at intervals of 400 μm so that the residual copper ratio is 60%. The layer made of the cured product is subjected to a roughening treatment. 100 copper pads after the roughening treatment are observed, and the number of cracks is preferably 10 or less. The crack resistance can be measured by the method described in the examples described below.

[0151] The resin composition contains a combination of the (A), (B) and (C) components, and therefore usually exhibits the characteristic of a low melt viscosity (minimum melt viscosity). Therefore, for example, when a resin composition layer is formed on a substrate having wiring on its surface, the wiring on the substrate surface can be satisfactorily embedded in the resin composition layer. The melt viscosity of the resin composition is preferably 2000 poise or less, more preferably 1900 poise or less, even more preferably 1800 poise or less, and particularly preferably 1700 poise or less. The lower limit can be, for example, 1000 poise or more. The melt viscosity can be measured according to the method described in the examples below.

[0152] The resin composition contains a combination of components (A), (B), and (C), and therefore usually exhibits the characteristic of a high glass transition temperature (Tg). Thus, the cured product provides an insulating layer with a high glass transition temperature. The glass transition temperature is preferably 130°C or higher, more preferably 140°C or higher, and even more preferably 150°C or higher. There is no particular upper limit, but it may be 500°C or lower. The glass transition temperature can be measured according to the method described in the examples below.

[0153] The resin composition of the present invention can obtain a cured product that has low dielectric properties, high adhesion to a conductor layer, and can suppress the occurrence of cracks after desmearing. Furthermore, the resin composition of the present invention exhibits a property of low melt viscosity, and can also obtain a cured product that usually has a high glass transition temperature. 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) for forming a conductor layer (including a rewiring layer) formed on an insulating layer.

[0154] Furthermore, in the multilayer printed wiring board described below, 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).

[0155] In addition, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as a resin composition for a rewiring formation layer (resin composition for forming a rewiring formation layer) as an insulating layer for forming a rewiring layer, and as a resin composition for sealing a semiconductor chip (resin composition for sealing a semiconductor chip). When a 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.

[0156] [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.

[0157] The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 50 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.

[0158] 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.

[0159] 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.

[0160] 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.

[0161] 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.

[0162] 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.

[0163] 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.

[0164] 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.

[0165] The resin sheet can be produced, for example, by preparing a resin varnish by dissolving the resin composition in a solvent, applying the resin varnish onto a support using a die coater or the like, and then drying the varnish to form a resin composition layer. The solvent is as described above.

[0166] 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 the 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 solvent in the resin varnish, for example, when a resin varnish containing 30 mass % to 60 mass % of the solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0167] 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.

[0168] [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.

[0169] 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

[0170] 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.

[0171] 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.

[0172] 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.

[0173] 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.

[0174] 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.

[0175] The support may be removed between step (I) and step (II) or after step (II).

[0176] 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.

[0177] 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.

[0178] 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).

[0179] 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.

[0180] 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.

[0181] 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.

[0182] 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.

[0183] 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.

[0184] 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.

[0185] 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.

[0186] 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.

[0187] 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.

[0188] [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 by using the printed wiring board of the present invention.

[0189] Examples of the semiconductor device include various semiconductor devices used in electric appliances (eg, computers, mobile phones, digital cameras, televisions, etc.) and vehicles (eg, motorcycles, automobiles, trains, ships, aircraft, etc.).

[0190] 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.

[0191] 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

[0192] The present invention will be described in more detail below using examples, but the present invention is not limited to these examples. In the following description, unless otherwise specified, "parts" and "%" mean "parts by mass" and "% by mass", respectively.

[0193] <Synthesis Example 1: Synthesis of Compound Ca> In a 1L flask equipped with a thermometer, a cooling tube, a Dean-Stark trap, and a stirrer, 48.9g (0.4mol) of 2,6-dimethylphenol, 272.0g (1.4mol) of α,α'-dihydroxy-1,3-diisopropylbenzene, 220g of xylene, and 70g of activated clay were charged and heated to 120°C while stirring. The temperature was raised to 210°C while removing the distillate water with a Dean-Stark tube, and the reaction was carried out for 3 hours. After that, the mixture was cooled to 140°C, and 146.69g (1.2mol) of 2,6-dimethylphenol was charged, and the temperature was raised to 220°C and the reaction was carried out for 3 hours. After the reaction, the mixture was air-cooled to 100°C, diluted with 300g of toluene, filtered to remove the activated clay, and the solvent and low molecular weight substances such as unreacted substances were distilled off under reduced pressure to obtain 365.3g of intermediate phenol compound (a). The hydroxyl equivalent (phenol equivalent) of the obtained intermediate phenol compound (a) was 299.

[0194] In a 2L flask equipped with a thermometer, a condenser, and a stirrer, 365.3 g of the intermediate phenol compound (a) and 700 g of toluene were charged and stirred at about 85°C. Next, 29.9 g (0.24 mol) of dimethylaminopyridine was charged, and when it was thought that all the solids had dissolved, 277.5 g (1.8 mol) of methacrylic anhydride was added dropwise over 1 hour. After the dropwise addition was completed, the reaction was continued for another 3 hours at 85°C. The reaction liquid was added dropwise over 1 hour to 4000 g of methanol in a 5L beaker that was vigorously stirred with a magnetic stirrer. The resulting precipitate was filtered under reduced pressure with a membrane filter and then dried to obtain a compound Ca having an indane skeleton of the following structural formula and a weight average molecular weight of 1500. The structure of compound Ca is shown below. In the formula, m represents an integer of 1 to 100. [ka]

[0195] <Synthesis Example 2: Synthesis of Compound Cb> In a 1L flask equipped with a thermometer, a cooling tube, a Dean-Stark trap, and a stirrer, 48.9g (0.4mol) of 2,6-dimethylphenol, 272.0g (1.4mol) of α,α'-dihydroxy-1,3-diisopropylbenzene, 280g of xylene, and 70g of activated clay were charged and heated to 120°C while stirring. The temperature was raised to 210°C while removing the distillate water with a Dean-Stark tube, and the reaction was carried out for 3 hours. After that, the mixture was cooled to 140°C, and 146.6g (1.2mol) of 2,6-dimethylphenol was charged, and the temperature was raised to 220°C and the reaction was carried out for 3 hours. After the reaction, the mixture was air-cooled to 100°C, diluted with 300g of toluene, and the activated clay was removed by filtration. The solvent and low molecular weight substances such as unreacted substances were distilled off under reduced pressure to obtain 365.3g of an intermediate phenol compound. The hydroxyl equivalent (phenol equivalent) of the intermediate phenol compound obtained was 299. 365.3 g of the intermediate phenol compound obtained, 0.184 g (0.001 mol) of 2,4-dinitrophenol (2,4-DNP), 23.5 g (0.073 mol) of tetrabutylammonium bromide (TBAB), 209 g (1.37 mol) of chloromethylstyrene, and 400 g of methyl ethyl ketone were added to a 2 L flask equipped with a thermometer, a cooling tube, and a stirrer, and the temperature was raised to 75 ° C. while stirring. Next, 48%-NaOHaq was added dropwise to the reaction vessel kept at 75 ° C. over 20 minutes. After the dropwise addition, stirring was continued for another 4 hours at 75 ° C. After 4 hours, the mixture was cooled to room temperature, 100 g of toluene was added, and 10% HCl was added for neutralization. The aqueous phase was then separated by liquid separation, and further washed three times with 300 m of water. The organic phase was concentrated by distillation, and methanol was added to reprecipitate the product. The precipitate was filtered and dried to obtain compound Cb with the following structural formula and a weight average molecular weight of 1,500. [ka]

[0196] <Synthesis Example 3: Synthesis of active ester compound A> In a flask equipped with a thermometer, dropping funnel, condenser, distillation tube, and stirrer, 320g (2.0 mol) of 2,7-dihydroxynaphthalene, 184g (1.7 mol) of benzyl alcohol, and 5.0g of paratoluenesulfonic acid monohydrate were charged and stirred at room temperature while blowing in nitrogen. The temperature was then raised to 150°C, and the mixture was stirred for 4 hours while distilling off the water produced. After the reaction was completed, 900g of methyl isobutyl ketone and 5.4g of 20% aqueous sodium hydroxide solution were added to neutralize the mixture, and the aqueous layer was removed by separation. The mixture was washed three times with 280g of water, and methyl isobutyl ketone was removed under reduced pressure to obtain 460g of benzyl-modified naphthalene compound (A-1). The obtained benzyl-modified naphthalene compound (A-1) was a black solid, and had a hydroxyl equivalent of 180g / equivalent.

[0197] In a flask equipped with a thermometer, a dropping funnel, a cooling tube, a fractionating tube, and a stirrer, 203.0 g of isophthalic acid chloride (molar number of acid chloride groups: 2.0 mol) and 1400 g of toluene were charged, and the system was purged with reduced pressure and nitrogen to dissolve. Next, 113.9 g (0.67 mol) of orthophenylphenol and 240 g of benzyl-modified naphthalene compound (A-1) (molar number of phenolic hydroxyl groups: 1.33 mol) were charged, and the system was purged with reduced pressure and nitrogen to dissolve. Then, 0.70 g of tetrabutylammonium bromide was dissolved, and while applying nitrogen gas purge, the system was controlled to 60°C or less, and 400 g of 20% aqueous sodium hydroxide solution was dropped over 3 hours. Then, stirring was continued under these conditions for 1.0 hour. After the reaction was completed, the mixture was left to stand for liquid separation, and the aqueous layer was removed. Further, water was added to the toluene layer in which the reactant was dissolved, and the mixture was stirred and mixed for 15 minutes, and the mixture was allowed to stand and separated to remove the aqueous layer. This operation was repeated until the pH of the aqueous layer reached 7. Thereafter, water was removed by decanting to obtain an active ester compound (B-2) in a toluene solution state with a non-volatile content of 65% by mass. The active ester equivalent of the obtained active ester compound A was 238 g / eq.

[0198] <Synthesis Example 4: Synthesis of vinyl resin B> According to Example 1 of WO 2017 / 115813, 3.0 mol (390.6 g) of divinylbenzene, 1.8 mol (229.4 g) of ethylvinylbenzene, 10.2 mol (1066.3 g) of styrene, and 15.0 mol (1532.0 g) of n-propyl acetate were charged into a 5.0 L reactor, and 600 mmol of a diethyl ether complex of boron trifluoride was added at 70 ° C. and reacted for 4 hours. After the polymerization solution was stopped with an aqueous sodium bicarbonate solution, the oil layer was washed three times with pure water, and the polymer was recovered by degassing at 60 ° C. The obtained product was weighed, and it was confirmed that 896.7 g of vinyl resin B was obtained. The weight average molecular weight (Mw) of vinyl resin B was 41300.

[0199] <Production of resin varnish> Each component was weighed out in the number of parts by mass shown in the table, and then mixed with 10 parts of MEK and 10 parts of cyclohexanone, and dispersed uniformly using a high-speed rotating mixer to obtain a resin varnish.

[0200] [Table 1] [Table 2] *In the table, the contents of components (A), (B), (C), and (E) represent the contents when the resin components in the resin composition are taken as 100% by mass. The content of component (D) represents the content when the non-volatile components in the resin composition are taken as 100% by mass.

[0201] The details of each component listed in the table are as follows. Component (A) ZX1059: "ZX1059" manufactured by Nippon Steel Chemical & Material Co., Ltd. (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin, functional group equivalent weight 170g / eq.) HP-4032-SS: DIC's "HP4032SS" (naphthalene type epoxy resin, functional group equivalent weight 144g / eq.) NC-3000L: "NC3000L" manufactured by Nippon Kayaku Co., Ltd. (biphenyl type epoxy resin, functional group equivalent weight 272g / eq.) (B) Component HPC-8150-62T: DIC's "HPC-8150-62T" (functional group equivalent weight 223g / eq., non-volatile content 61.5% by mass in toluene solution) HPC-8000-65T: DIC's "HPC-8000-65T" (functional group equivalent weight 229g / eq., non-volatile content 65% by mass in toluene solution) Compound A: Active ester compound A synthesized in Synthesis Example 3 (C) Component Ca: Compound Ca synthesized in Synthesis Example 1 Cb: Compound Cb synthesized in Synthesis Example 2 (D) Component SO-C2: Spherical silica surface-treated with an amine-based alkoxysilane compound (Shin-Etsu Chemical Co., Ltd.'s "KBM573"), with an average particle size of 0.5 μm and a specific surface area of ​​5.8 m 2 / g, manufactured by Admatechs (E) Component Maleimide compound A: a compound represented by the following formula (1) (Mw / Mn = 1.81, t'' = 1.47 (mainly 1, 2 or 3)) synthesized by the method described in Synthesis Example 1 of the Japan Institute of Invention and Innovation's Technical Journal Publication No. 2020-500211, MEK solution with 62% non-volatile components [ka] MIR-3000-70MT: "MIR-3000-70MT" manufactured by Nippon Kayaku Co., Ltd. (toluene-MEK solution with 70% non-volatile content by mass) SLK-6985: "SLK-6985" manufactured by Shin-Etsu Chemical Co., Ltd. SLK-1500: "SLK-1500" manufactured by Shin-Etsu Chemical Co., Ltd. OPE-2St-1200: "OPE-2St-1200" manufactured by Mitsubishi Gas Chemical Co., Ltd. (toluene solution with 65% non-volatile content) Vinyl resin B: Vinyl resin B synthesized in Synthesis Example 4 NE-V-1100-70T: DIC's "NE-V-1100-70T" (toluene solution with 70% non-volatile content) Ingredient (F) LA-3018-50P: DIC's "LA-3018-50P" (functional group equivalent weight 151g / eq., 1-methoxy-2-propanol solution with non-volatile content of 50% by mass) (G) Component EXL-2655: Dow Chemical Japan (H) Component 1B2PZ: Shikoku Chemical Industry Co., Ltd.

[0202] <Measurement of dielectric constant (dielectric constant) and dielectric loss tangent> (1) Preparation of resin sheet A having a resin composition layer thickness of 40 μm A polyethylene terephthalate film with a release layer ("AL5" manufactured by Lintec Corporation, thickness 38 μm) was prepared as a support. On the release layer of this support, the resin varnish obtained in the examples and comparative examples was uniformly applied so that the thickness of the resin composition layer after drying was 40 μm. Thereafter, the resin composition was dried at 80°C to 100°C (average 90°C) for 2 minutes to obtain a resin sheet A including a support and a resin composition layer.

[0203] (2) Preparation of cured material for evaluation Resin sheet A was cured in an oven at 190° C. for 90 minutes. The support was peeled off from resin sheet A taken out of the oven to obtain a cured product of the resin composition layer. The cured product was cut into a length of 80 mm and a width of 2 mm to be used as a cured product for evaluation.

[0204] (3) Measurement of dielectric constant and dielectric tangent For each of the cured evaluation products, the dielectric constant and dielectric tangent (Dk value and Df value) were measured by the cavity resonance perturbation method using an Agilent Technologies "HP8362B" at a measurement frequency of 5.8 GHz and measurement temperatures of 23°C and 90°C. Measurements were performed on two test pieces, and the average was calculated.

[0205] <Measurement of peel strength of plated conductor layer> (1) Preparation of resin sheet A having a resin composition layer thickness of 40 μm A polyethylene terephthalate film with a release layer ("AL5" manufactured by Lintec Corporation, thickness 38 μm) was prepared as a support. On the release layer of this support, the resin varnish obtained in the examples and comparative examples was uniformly applied so that the thickness of the resin composition layer after drying was 40 μm. Thereafter, the resin composition was dried at 80°C to 100°C (average 90°C) for 4 minutes to obtain a resin sheet A including a support and a resin composition layer.

[0206] (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.

[0207] (3) Lamination of resin sheet A Using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., 2-stage build-up laminator "CVP700"), resin sheet A was laminated on both sides of the inner layer substrate so that the resin composition layer was in contact with the inner layer substrate. 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. Next, heat pressing was performed at 100°C and a pressure of 0.5 MPa for 60 seconds.

[0208] (4) Thermal curing of the resin composition layer Thereafter, the inner layer substrate laminated with the resin sheet A was placed in an oven at 130°C and heated for 30 minutes, and then transferred to an oven at 170°C and heated for 30 minutes to thermally cure the resin composition layer and form an insulating layer. Thereafter, the support was peeled off to obtain a cured substrate A having the insulating layer, the inner layer substrate, and the insulating layer in this order.

[0209] (5) Roughening treatment A desmear treatment was carried out as a roughening treatment on the cured substrate A. The desmear treatment was the following wet desmear treatment.

[0210] The cured substrate A was immersed in a swelling solution (Atotech Japan's "Swelling Dip Securigant P", an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 5 minutes, then immersed in an oxidizing agent solution (Atotech Japan's "Concentrate Compact CP", an aqueous solution of potassium permanganate at about 6% and sodium hydroxide at about 4%) at 80°C for 20 minutes, then immersed in a neutralizing solution (Atotech Japan's "Reduction Solution Securigant P", an aqueous solution of sulfuric acid) at 40°C for 5 minutes, and then dried at 80°C for 15 minutes.

[0211] (6) Formation of the conductor layer A conductor layer was formed on the roughened surface of the insulating layer according to the semi-additive method. That is, the substrate after the roughening treatment was immersed in an electroless plating solution containing PdCl2 at 40°C for 5 minutes, and then immersed in an electroless copper plating solution at 25°C for 20 minutes. Next, an annealing treatment was performed by heating at 150°C for 30 minutes, and then an etching resist was formed and a pattern was formed by etching. Then, copper sulfate electrolytic plating was performed to form a conductor layer having a thickness of 25 μm, and an annealing treatment was performed at 190°C for 60 minutes. The obtained substrate is called "evaluation substrate A".

[0212] (7) Measurement of peel strength of plated conductor layer The peel strength of the insulating layer and the conductor layer was measured in accordance with the Japanese Industrial Standard (JIS C6481). Specifically, a cut was made in the conductor layer of evaluation board A, measuring 10 mm wide and 100 mm long, and one end of the cut was peeled off and held with a gripper. The load (kgf / cm) was measured when 35 mm was peeled off vertically at a speed of 50 mm / min at room temperature, and the peel strength was calculated. A tensile tester (TSE's "AC-50C-SL") was used for the measurement.

[0213] <Evaluation of crack resistance after desmear treatment> A polyethylene terephthalate film with a release layer ("AL5" manufactured by Lintec Corporation, thickness 38 μm) was prepared as a support. On the release layer of this support, the resin varnish obtained in the examples and comparative examples was uniformly applied so that the thickness of the resin composition layer after drying was 25 μm, and dried at 70°C to 80°C (average 75°C) for 2.5 minutes to obtain a resin sheet B including a support and a resin composition layer.

[0214] Resin sheet B was laminated on both sides of the inner layer substrate using a batch type vacuum pressure laminator (Nikko Materials Co., Ltd. 2-stage build-up laminator "CVP700") on both sides of a core material (Resonac Co., Ltd. "E705GR", thickness 400 μm) in which circular copper pads (copper thickness 35 μm) with a diameter of 350 μm were formed in a grid pattern at intervals of 400 μm so that the residual copper rate was 60%. This lamination was performed by depressurizing for 30 seconds to an atmospheric pressure of 13 hPa or less, and then pressing at a temperature of 100 ° C and a pressure of 0.74 MPa for 30 seconds. This was placed in a 130 ° C oven and heated for 30 minutes, and then transferred to a 175 ° C oven and heated for 40 minutes. The support was then peeled off, and the resulting circuit board was immersed in a swelling liquid, Swelling Dip Securigant P, manufactured by Atotech Japan, at 60°C for 10 minutes. Next, the circuit board was immersed in a roughening liquid, Concentrate Compact P (aqueous solution of KMnO4: 60g / L, NaOH: 40g / L), manufactured by Atotech Japan, at 80°C for 30 minutes. Finally, the circuit board was immersed in a neutralizing liquid, Reduction Solution Securigant P, manufactured by Atotech Japan, at 40°C for 5 minutes. 100 copper pads of the circuit board after the roughening treatment were observed, and the presence or absence of cracks in the resin composition layer was evaluated according to the following criteria. Good: 10 or fewer cracks. △: More than 10 and less than 20 cracks. ×: More than 20 cracks.

[0215] <Melt Viscosity Measurement> Resin sheet A was peeled off from the support film and measured using a dynamic viscoelasticity measuring device G-3000 manufactured by UBM at a frequency of 1 Hz, a strain of 5 degrees, a load of 100 g, a heating rate of 5°C / min, and a temperature range of 60°C to 180°C.

[0216] <Measurement of glass transition temperature (Tg)> Resin sheet A was cured in an oven at 190°C for 90 minutes, and the support was peeled off to obtain a cured film. This cured film was cut into a length of 20 mm and a width of 6 mm to obtain a cured sample for measuring the linear thermal expansion coefficient. The Tg of this cured sample was measured using a TMA device (thermomechanical analyzer, manufactured by Rigaku Corporation). In detail, after mounting the cured sample on the device, measurements were performed twice in succession under the measurement conditions of a load of 1 g and a temperature increase rate of 5°C / min (the first measurement was performed by increasing the temperature from 25°C to 220°C, and the second measurement was performed by increasing the temperature from 25°C to 250°C), and the second value was recorded.

[0217] [Table 3] [Table 4]

Claims

1. (A) Epoxy resin, (B) Active ester compounds, and A resin composition containing (C) a compound represented by formula (C-1). 【Chemistry 1】 In the formula, X independently represents an n-valent hydrocarbon group which may have substituents, Y independently represents a monovalent group which may have substituents and contains a double bond, Ar independently represents a divalent aromatic hydrocarbon group which may have two identical or different alkyl groups as substituents, and Z independently represents a single bond or a divalent aromatic hydrocarbon group which may have substituents. n represents an integer from 1 to 3, and m represents an integer from 1 to 100.

2. The resin composition according to claim 1, wherein Y represents any of an acryloyl group, a methacryloyl group, and a vinylbenzyl group.

3. The resin composition according to claim 1, wherein component (C) contains a compound represented by formula (C-2). 【Chemistry 2】 In the formula, R １ and R ２ Each of these independently represents a monovalent group containing a double bond, R ３ and R ４ Each represents a divalent aromatic hydrocarbon group having two alkyl groups as substituents, which may be the same or different, and R ５ Each of these independently represents a divalent aromatic hydrocarbon group, R ６ represents a divalent aromatic hydrocarbon group which may have a single bond or substituent. m1 represents an integer from 1 to 100.

4. The resin composition according to claim 1, wherein component (C) contains a compound represented by formula (C-3). 【Transformation 3】 In the formula, R １２ represents a monovalent group containing a double bond, R １３ and R １４ each independently represent a divalent aromatic hydrocarbon group having two alkyl groups which may be the same or different as substituents, and R １５ represents a single bond or a divalent aromatic hydrocarbon group which may have a substituent. m2 represents an integer of 1 to 100.

5. The content of component (C) is 1% by mass or more and 25% by mass or less, when the total amount of resin components in the resin composition is taken as 100% by mass. The resin composition according to claim 1.

6. Furthermore, the resin composition according to claim 1, further comprising (D) an inorganic filler.

7. Furthermore, the resin composition according to claim 1, further comprising (E) a compound having a double bond.

8. The resin composition according to claim 7, wherein the content of component (E) is 1% by mass or more and 25% by mass or less, when the total amount of resin components in the resin composition is 100% by mass.

9. Furthermore, the resin composition according to claim 1, further comprising (F) a curing agent.

10. A resin sheet comprising a support and a resin composition layer provided on the support, the layer comprising the resin composition according to any one of claims 1 to 9.

11. A printed circuit board comprising an insulating layer formed from a cured product of the resin composition according to any one of claims 1 to 9.

12. A semiconductor device comprising a printed circuit board as described in claim 11.

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