Resin composition

Abstract

To provide a resin composition capable of providing an isolation layer excellent in every characteristic of a dielectric loss tangent, a thermal expansion coefficient, a fracture point elongation, surface roughness and peel strength, in production of a printed wiring board.SOLUTION: A resin composition contains (A) an epoxy resin, (B) an active ester compound, (C) a carbodiimide compound, (D) a thermoplastic resin and (E) an inorganic filler. When expressing the content of a nonvolatile component in the resin composition as 100 mass%, the content of the (E) component is 40 mass% or more.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] A known manufacturing technique for printed wiring boards is a build-up method in which insulating layers and conductor layers are alternately stacked. In the build-up method, the insulating layer is generally formed by curing a resin composition. For example, Patent Document 1 discloses a technique for forming an insulating layer with a low dielectric tangent by curing a resin composition containing an epoxy resin, an active ester compound, and a carbodiimide compound.

[0003] Due to the recent trend towards lighter, thinner, shorter and smaller printed wiring boards, the number of layers in the build-up of the board tends to increase, but as the number of layers increases, problems arise in that cracks and circuit distortions occur due to the difference in thermal expansion between the insulating layer and the conductor layer. As a technique for suppressing such problems of cracks and circuit distortion, for example, Patent Document 2 discloses a technique for suppressing the thermal expansion coefficient of the formed insulating layer by increasing the content of an inorganic filler in a resin composition. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2006-335834 A [Patent Document 2] JP 2010-202865 A Summary of the Invention [Problem to be solved by the invention]

[0005] The present inventors attempted to blend a high content of inorganic filler into the resin composition described in Patent Document 1 in order to form an insulating layer with a low dielectric tangent and a low thermal expansion coefficient when manufacturing a printed wiring board. The present inventors found that while the resulting resin composition provides an insulating layer with a desired dielectric tangent and thermal expansion coefficient, the resulting insulating layer may be inferior in properties such as elongation at break, surface roughness, and peel strength.

[0006] An object of the present invention is to provide a resin composition capable of producing an insulating layer that is excellent in all of the properties, including dielectric tangent, thermal expansion coefficient, elongation at break, surface roughness, and peel strength, when used in the production of printed wiring boards. [Means for solving the problem]

[0007] As a result of extensive investigations into the above problems, the present inventors have found that the above problems can be solved by using the specific resin composition described below, and have thus completed the present invention.

[0008] That is, the present invention includes the following. [1] A resin composition comprising (A) an epoxy resin, (B) an active ester compound, (C) a carbodiimide compound, (D) a thermoplastic resin, and (E) an inorganic filler, wherein the content of component (E) is 40 mass% or more when the total amount of non-volatile components in the resin composition is 100 mass%. [2] The resin composition according to [1], wherein the weight average molecular weight of component (D) is 10,000 to 200,000. [3] The resin composition according to [1] or [2], wherein component (D) is a thermoplastic resin having a functional group containing one or more atoms selected from the group consisting of oxygen atoms, nitrogen atoms, and sulfur atoms, or a carbon-carbon double bond. [4] The resin composition according to any one of [1] to [3], wherein component (D) is a thermoplastic resin having one or more functional groups selected from the group consisting of a hydroxyl group, a carboxyl group, an acid anhydride group, an epoxy group, an amino group, a thiol group, an enol group, an enamine group, a urea group, a cyanate group, an isocyanate group, a thioisocyanate group, a diimide group, an alkenyl group, an allene group, and a ketene group. [5] The resin composition according to any one of [1] to [4], wherein the component (D) is one or more thermoplastic resins selected from the group consisting of phenoxy resins, polyvinyl acetal resins, acid anhydride group-containing vinyl resins, polyimide resins, polyamideimide resins, and styrene-based elastomer resins. [6] The resin composition according to any one of [1] to [5], wherein the weight average molecular weight of the component (C) is 500 to 5,000. [7] The resin composition according to any one of [1] to [6], wherein the NCO content of the component (C) is 5 mass % or less. [8] The resin composition according to any one of [1] to [7], wherein the content of the component (E) is 50 mass% or more, based on 100 mass% of the non-volatile components in the resin composition. [9] The resin composition according to any one of [1] to [8], wherein the average particle size of component (E) is 0.01 μm to 3 μm.

[10] The resin composition according to any one of [1] to [9], wherein the component (E) is silica.

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

[10] , further comprising (F) a curing accelerator.

[12] The resin composition according to

[11] , wherein the component (F) is 4-dimethylaminopyridine or 1-benzyl-2-phenylimidazole.

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

[12] , wherein the resin composition is cured to form an insulating layer, and the insulating layer has an arithmetic mean roughness (Ra) of 140 nm or less after a surface roughening treatment.

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

[13] , wherein the elongation at break of a cured product of the resin composition is 2% or more.

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

[14] , wherein the glass transition temperature (Tg) of a cured product of the resin composition is 165° C. or higher.

[16] An adhesive film comprising a support and a layer of the resin composition according to any one of [1] to

[15] bonded to the support.

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

[15] .

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

[17] . Effect of the Invention

[0009] According to the present invention, it is possible to provide a resin composition that can provide an insulating layer that is excellent in all of the properties, including dielectric tangent, thermal expansion coefficient, elongation at break, surface roughness, and peel strength, when producing a printed wiring board. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] The present invention will be described in detail below based on preferred embodiments thereof.

[0011] [Resin composition] The resin composition of the present invention is characterized in that it comprises (A) an epoxy resin, (B) an active ester compound, (C) a carbodiimide compound, (D) a thermoplastic resin, and (E) an inorganic filler, and the content of component (E) is 40 mass% or more when the total amount of non-volatile components in the resin composition is 100 mass%.

[0012] The present inventors have found that when a resin composition containing (A) an epoxy resin, (B) an active ester compound, and (C) a carbodiimide compound is blended with a high content of (E) an inorganic filler, the resulting resin composition provides an insulating layer exhibiting a low dielectric tangent and a low coefficient of thermal expansion, but may result in an insulating layer inferior in properties such as elongation at break, surface roughness, and peel strength. The resin composition of the present invention further contains (D) a thermoplastic resin, which makes it possible to provide an insulating layer that is excellent in elongation at break, surface roughness, and peel strength while maintaining a low dielectric tangent and a low coefficient of thermal expansion. In this regard, even if a thermoplastic resin (D) is added to a resin composition that does not contain an active ester compound (B), the desired elongation at break, surface roughness, and peel strength are not achieved. Also, even if a thermoplastic resin (D) is added to a resin composition that does not contain a carbodiimide compound (C), the desired elongation at break, surface roughness, and peel strength are not achieved. When (D) thermoplastic resin is added to a resin composition having a low content of (E) inorganic filler, the desired dielectric tangent and thermal expansion coefficient are not achieved in the first place. This will be clearly understood from the results of the comparative examples shown later. Thus, the effect of the resin composition of the present invention is a specific and synergistic effect brought about by using in combination (A) epoxy resin, (B) active ester compound, (C) carbodiimide compound, (D) thermoplastic resin, and a certain amount or more of (E) inorganic filler.

[0013] Each component contained in the resin composition of the present invention will be described below.

[0014] <(A) Epoxy resin> The resin composition of the present invention contains an epoxy resin as component (A).

[0015] Examples of epoxy resins include bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, bisphenol AF type epoxy resins, dicyclopentadiene type epoxy resins, trisphenol type epoxy resins, naphthol novolac type epoxy resins, phenol novolac type epoxy resins, alicyclic epoxy resins having an ester skeleton, tert-butyl-catechol type epoxy resins, naphthalene type epoxy resins, naphthol type epoxy resins, anthracene type epoxy resins, glycidylamine type epoxy resins, glycidyl ester 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 dimethanol type epoxy resins, naphthylene ether type epoxy resins, trimethylol type epoxy resins, tetraphenylethane type epoxy resins, etc. The epoxy resins may be used alone or in combination of two or more.

[0016] The epoxy resin preferably contains an epoxy resin having two or more epoxy groups in one molecule. When the non-volatile component of the epoxy resin is 100 mass%, it is preferable that at least 50 mass% of the epoxy resin has two or more epoxy groups in one molecule. Among them, it is preferable to contain an epoxy resin having two or more epoxy groups in one molecule and being liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resin") and an epoxy resin having three or more epoxy groups in one molecule and being solid at a temperature of 20°C (hereinafter referred to as "solid epoxy resin"). By using a liquid epoxy resin and a solid epoxy resin in combination as the epoxy resin, a resin composition having excellent flexibility can be obtained. In addition, the breaking strength of the cured product of the resin composition is also improved.

[0017] 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, phenol novolac type epoxy resin, alicyclic epoxy resin having an ester skeleton, and epoxy resin having a butadiene structure are preferred, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, alicyclic epoxy resin having an ester skeleton, and naphthalene type epoxy resin are more preferred, bisphenol A type epoxy resin and bisphenol AF type epoxy resin are even more preferred, and bisphenol AF type epoxy resin is particularly preferred from the viewpoint of excellent balance of physical properties of the cured product. Specific examples of liquid epoxy resins include "HP4032", "HP4032H", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC Corporation, "828US", "jER828EL" (bisphenol A type epoxy resin), "jER807" (bisphenol F type epoxy resin), "jER152" (phenol novolac type epoxy resin), and "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "ZX1059" (mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX Corporation, "Celloxide 2021P" (alicyclic epoxy resin having an ester skeleton) and "PB-3600" (epoxy resin having a butadiene structure) manufactured by Daicel Corporation. These may be used alone or in combination of two or more types.

[0018] As the solid 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, and tetraphenylethane-type epoxy resin are preferred, and naphthalene-type tetrafunctional epoxy resin, naphthol-type epoxy resin, and biphenyl-type epoxy resin are more preferred. Specific examples of solid epoxy resins include "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" (dicyclopentadiene-type epoxy resin), "EXA7311", "EXA7311-G3", "EXA7311-G4", "EXA7311-G4S", and "HP6000" (naphthylene ether-type epoxy resin), and "EPPN-502H" (trisphenol-type epoxy resin), "NC7000L" (naphthol novolac-type epoxy resin), "NC3000H", "NC3000", "NC3000L", and "NC3100" (manufactured by Nippon Kayaku Co., Ltd.). " (biphenyl type epoxy resin), "ESN475V" (naphthol type epoxy resin) and "ESN485" (naphthol novolac type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., "YX4000H", "YL6121" (biphenyl type epoxy resin), "YX4000HK" (bixylenol type epoxy resin (biphenyl type epoxy resin)), "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd., "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation, "jER1010" (solid bisphenol A type epoxy resin) and "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, and the like.

[0019] When liquid epoxy resin and solid epoxy resin are used in combination as epoxy resin, the ratio of the amounts (liquid epoxy resin: solid epoxy resin) is preferably in the range of 1:0.1 to 1:8 by mass. By setting the ratio of the amount of the liquid epoxy resin and the solid epoxy resin in this range, the following effects can be obtained: i) when used in the form of an adhesive film, appropriate adhesion is obtained; ii) when used in the form of an adhesive film, sufficient flexibility is obtained and handling is improved; and iii) a cured product having sufficient breaking strength can be obtained. From the viewpoint of the above effects i) to iii), the ratio of the amount of the liquid epoxy resin and the solid epoxy resin (liquid epoxy resin: solid epoxy resin) is more preferably in the range of 1:0.3 to 1:7 by mass, and even more preferably in the range of 1:0.6 to 1:6.

[0020] From the viewpoint of obtaining an insulating layer exhibiting good mechanical strength and insulating reliability, the content of the epoxy resin in the resin composition is preferably 3 mass% to 40 mass%, more preferably 5 mass% to 35 mass%, and even more preferably 10 mass% to 35 mass% or 10 mass% to 30 mass%. In the present invention, the content of each component in the resin composition is a value when the non-volatile components in the resin composition are taken as 100 mass %, unless otherwise specified.

[0021] The epoxy equivalent of the epoxy resin is preferably 50 to 5000, more preferably 50 to 3000, even more preferably 80 to 2000, and even more preferably 110 to 1000. Within this range, the crosslink density of the cured product is sufficient, and an insulating layer with small surface roughness can be obtained. The epoxy equivalent can be measured according to JIS K7236, and is the mass of a resin containing one equivalent of an epoxy group. The weight average molecular weight of the epoxy resin is preferably 100 to 5000, more preferably 250 to 3000, and further preferably 400 to 1500. Here, the weight average molecular weight of the epoxy resin is a polystyrene-equivalent weight average molecular weight measured by gel permeation chromatography (GPC).

[0022] <(B) Active ester compound> The resin composition of the present invention contains an active ester compound as the component (B).

[0023] The active ester compound is a compound having one or more active ester groups in one molecule. When used in combination with a (C) carbodiimide compound, (D) a thermoplastic resin, and a certain amount or more of (E) an inorganic filler, which will be described later, it is possible to obtain an insulating layer that is excellent in all of the properties, namely, dielectric tangent, thermal expansion coefficient, elongation at break, surface roughness, and peel strength.

[0024] The active ester compound is preferably a compound having two or more active ester groups in one molecule, and for example, a compound having two or more highly reactive ester groups in one molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, esters of heterocyclic hydroxy compounds, etc. The active ester compound may be used alone or in combination of two or more.

[0025] From the viewpoint of improving heat resistance, an active ester compound 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 is preferred. Among them, an active ester compound obtained by reacting a carboxylic acid compound with one or more selected from a phenol compound, a naphthol compound, and a thiol compound is more preferred, an aromatic compound having two or more active ester groups in one molecule obtained by reacting a carboxylic acid compound with an aromatic compound having a phenolic hydroxyl group is even more preferred, and an aromatic compound having two or more active ester groups in one molecule obtained by reacting a carboxylic acid compound having at least two or more carboxy groups in one molecule with an aromatic compound having a phenolic hydroxyl group is even more preferred. The active ester compound may be linear or branched. In addition, if the carboxylic acid compound having at least two or more carboxy groups in one molecule is a compound containing an aliphatic chain, it can increase the compatibility with the resin composition, and if it is a compound having an aromatic ring, it can increase the heat resistance.

[0026] Examples of the carboxylic acid compound include aliphatic carboxylic acids having 1 to 20 carbon atoms (preferably 2 to 10, more preferably 2 to 8) and aromatic carboxylic acids having 7 to 20 carbon atoms (preferably 7 to 10). Examples of the aliphatic carboxylic acids include acetic acid, malonic acid, succinic acid, maleic acid, and itaconic acid. Examples of the aromatic carboxylic acids include benzoic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Among them, from the viewpoint of heat resistance, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, and terephthalic acid are preferred, and isophthalic acid and terephthalic acid are more preferred.

[0027] The thiocarboxylic acid compound is not particularly limited, but examples thereof include thioacetic acid and thiobenzoic acid.

[0028] Examples of the phenolic compound include phenolic compounds having 6 to 40 carbon atoms (preferably 6 to 30, more preferably 6 to 23, and even more preferably 6 to 22). Suitable specific examples 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, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, and dicyclopentadiene-type diphenol. As the phenolic compound, phenol novolac and phosphorus atom-containing oligomers having phenolic hydroxyl groups described in JP-A-2013-40270 may also be used.

[0029] The naphthol compound may, for example, be a naphthol compound having 10 to 40 carbon atoms (preferably 10 to 30, more preferably 10 to 20), and suitable specific examples include α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, etc. As the naphthol compound, naphthol novolak may also be used.

[0030] Among these, bisphenol A, bisphenol F, bisphenol S, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenols, phenol novolac, and phosphorus atom-containing oligomers having phenolic hydroxyl groups are preferred, and catechol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenols, phenol novolac, and phenolic hydroxyl groups are preferred. More preferred are phosphorus atom-containing oligomers having an acid group, and still more preferred are 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, dicyclopentadiene-type diphenols, phenol novolac, and phosphorus atom-containing oligomers having a phenolic hydroxyl group, and still more preferred are 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene-type diphenols, phenol novolac, and phosphorus atom-containing oligomers having a phenolic hydroxyl group, and particularly preferred are 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dicyclopentadiene-type diphenols, and phosphorus atom-containing oligomers having a phenolic hydroxyl group, and particularly preferred are dicyclopentadiene-type diphenols.

[0031] The thiol compound is not particularly limited, but examples thereof include benzenedithiol and triazinedithiol.

[0032] Suitable specific examples of the active ester compound include an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetylated product of phenol novolac, an active ester compound containing a benzoylated product of phenol novolac, and an active ester compound obtained by reacting an aromatic carboxylic acid with a phosphorus-containing oligomer having a phenolic hydroxyl group, among which an active ester compound containing a dicyclopentadiene-type diphenol structure, an active ester compound containing a naphthalene structure, and an active ester compound obtained by reacting an aromatic carboxylic acid with a phosphorus-containing oligomer having a phenolic hydroxyl group are more preferred. In the present invention, the term "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit consisting of phenylene-dicyclopentylene-phenylene.

[0033] More specifically, the active ester compound containing a dicyclopentadiene-type diphenol structure includes the compound represented by the following formula (1).

[0034] [ka] (In the formula, R is a phenyl group or a naphthyl group, k is 0 or 1, and n is the average number of repeating units and is 0.05 to 2.5.)

[0035] From the viewpoint of lowering the dielectric tangent and improving the heat resistance, R is preferably a naphthyl group, k is preferably 0, and n is preferably 0.25 to 1.5.

[0036] As the active ester compound, the active ester compounds disclosed in JP-A-2004-277460 and JP-A-2013-40270 may be used, or commercially available active ester compounds may be used. Examples of commercially available active ester compounds include EXB9451, EXB9460, EXB9460S, and HPC-8000-65T (manufactured by DIC Corporation) as active ester compounds containing a dicyclopentadiene-type diphenol structure, EXB9416-70BK (manufactured by DIC Corporation) as active ester compounds containing a naphthalene structure, DC808 (manufactured by Mitsubishi Chemical Corporation) as active ester compounds containing an acetylated product of phenol novolac, YLH1026 (manufactured by Mitsubishi Chemical Corporation) as active ester compounds containing a benzoylated product of phenol novolac, and EXB9050L-62M (manufactured by DIC Corporation) as active ester compounds containing a phosphorus atom.

[0037] In combination with the (C) carbodiimide compound, (D) thermoplastic resin, and a certain amount or more of (E) inorganic filler, described later, from the viewpoint of obtaining an insulating layer excellent in all properties of dielectric tangent, thermal expansion coefficient, elongation at break, surface roughness, and peel strength, particularly from the viewpoint of obtaining an insulating layer having low surface roughness and high peel strength, the content of the active ester compound in the resin composition is preferably 1% by mass or more, more preferably 3% by mass or more, and even more preferably 5% by mass or more. The upper limit of the content of the active ester compound is not particularly limited, but is preferably 30% by mass or less, more preferably 20% by mass or less, and even more preferably 15% by mass or less.

[0038] In addition, when the number of epoxy groups in the epoxy resin (A) is 1, from the viewpoint of obtaining an insulating layer having good mechanical strength, the number of reactive groups in the active ester compound (B) is preferably 0.2 to 2, more preferably 0.3 to 1.5, and even more preferably 0.35 to 1. Here, the "number of epoxy groups in the epoxy resin" refers to the total value of the solid content mass of each epoxy resin present in the resin composition divided by the epoxy equivalent for all epoxy resins. In addition, the "reactive group" refers to a functional group that can react with an epoxy group, and the "number of reactive groups in the active ester compound" refers to the total value of all values ​​obtained by dividing the solid content mass of the active ester compounds present in the resin composition by the reactive group equivalent.

[0039] <(C) Carbodiimide compound> The resin composition of the present invention contains a carbodiimide compound as the component (C).

[0040] The carbodiimide compound is a compound having one or more carbodiimide groups (-N=C=N-) in one molecule, and by using it in combination with the above-mentioned (B) active ester compound, the below-mentioned (D) thermoplastic resin, and a certain amount or more of (E) inorganic filler, an insulating layer excellent in all properties of dielectric tangent, thermal expansion coefficient, elongation at break, surface roughness, and peel strength can be obtained. As the carbodiimide compound, a compound having two or more carbodiimide groups in one molecule is preferable. The carbodiimide compound may be used alone or in combination of two or more.

[0041] In one embodiment, the carbodiimide compound contained in the resin composition of the present invention contains a structural unit represented by the following formula (2).

[0042] [ka] (In the formula, X represents an alkylene group, a cycloalkylene group, or an arylene group, which may have a substituent. p represents an integer of 1 to 5. When there are multiple Xs, they may be the same or different. * represents a bond.)

[0043] The number of carbon atoms of the alkylene group represented by X is preferably 1 to 20, more preferably 1 to 10, and further preferably 1 to 6, 1 to 4, or 1 to 3. The number of carbon atoms does not include the number of carbon atoms of the substituent. Suitable examples of the alkylene group include a methylene group, an ethylene group, a propylene group, and a butylene group.

[0044] The number of carbon atoms of the cycloalkylene group represented by X is preferably 3 to 20, more preferably 3 to 12, and further preferably 3 to 6. The number of carbon atoms of the substituent is not included in the number of carbon atoms. Suitable examples of the cycloalkylene group include a cyclopropylene group, a cyclobutylene group, a cyclopentylene group, and a cyclohexylene group.

[0045] The arylene group represented by X is a group in which two hydrogen atoms on an aromatic ring are removed from an aromatic hydrocarbon. The number of carbon atoms in the arylene group is preferably 6 to 24, more preferably 6 to 18, even more preferably 6 to 14, and even more preferably 6 to 10. The number of carbon atoms does not include the number of carbon atoms of the substituent. Suitable examples of the arylene group include a phenylene group, a naphthylene group, and an anthracenylene group.

[0046] In order to realize an insulating layer having even more excellent dielectric tangent, thermal expansion coefficient, elongation at break, surface roughness and peel strength in combination with the (B) active ester compound, the (D) thermoplastic resin, and a certain amount or more of the (E) inorganic filler, X is preferably an alkylene group or a cycloalkylene group, which may have a substituent.

[0047] The alkylene group, cycloalkylene group or aryl group represented by X may have a substituent. The substituent is not particularly limited, but examples thereof include a halogen atom, an alkyl group, an alkoxy group, a cycloalkyl group, a cycloalkyloxy group, an aryl group, an aryloxy group, an acyl group and an acyloxy group. Examples of the halogen atom used as a substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. The alkyl group and the alkoxy group used as a substituent may be either linear or branched, and the number of carbon atoms is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6, 1 to 4, or 1 to 3. The number of carbon atoms of the cycloalkyl group and the cycloalkyloxy group used as a substituent is preferably 3 to 20, more preferably 3 to 12, and even more preferably 3 to 6. The aryl group used as a substituent is a group obtained by removing one hydrogen atom on the aromatic ring from an aromatic hydrocarbon, and the number of carbon atoms is preferably 6 to 24, more preferably 6 to 18, more preferably 6 to 14, and even more preferably 6 to 10. The number of carbon atoms in the aryloxy group used as a substituent is preferably 6 to 24, more preferably 6 to 18, further preferably 6 to 14, and further preferably 6 to 10. The acyl group used as a substituent is represented by the formula: -C(=O)-R 1 (wherein R 1 represents an alkyl group or an aryl group. 1 The alkyl group represented by the formula (I) may be either linear or branched, and preferably has 1 to 20 carbon atoms, more preferably 1 to 10 carbon atoms, and further preferably 1 to 6, 1 to 4, or 1 to 3 carbon atoms. 1 The number of carbon atoms of the aryl group represented by the formula: is preferably 6 to 24, more preferably 6 to 18, further preferably 6 to 14, and further preferably 6 to 10. The acyloxy group used as a substituent is represented by the formula: -OC(=O)-R 1 (wherein R 1 has the same meaning as above.) Among them, as the substituent, an alkyl group, an alkoxy group, and an acyloxy group are preferable, and an alkyl group is more preferable.

[0048] In formula (2), p represents an integer of 1 to 5. In order to realize an insulating layer having even more excellent dielectric tangent, thermal expansion coefficient, elongation at break, surface roughness and peel strength in combination with the (B) active ester compound, the (D) thermoplastic resin, and a certain amount or more of the (E) inorganic filler, p is preferably 1 to 4, more preferably 2 to 4, and even more preferably 2 or 3.

[0049] In formula (2), when there are a plurality of X's, they may be the same or different. In a preferred embodiment, at least one X is an alkylene group or a cycloalkylene group, which may have a substituent.

[0050] In a preferred embodiment, the carbodiimide compound contains the structural unit represented by formula (2) at preferably 50% by mass or more, more preferably 60% by mass or more, even more preferably 70% by mass or more, and even more preferably 80% by mass or more or 90% by mass or more, when the mass of the entire molecule of the carbodiimide compound is taken as 100% by mass. The carbodiimide compound may be substantially composed of the structural unit represented by formula (2) except for the terminal structure. The terminal structure of the carbodiimide compound is not particularly limited, but examples thereof include an alkyl group, a cycloalkyl group, and an aryl group, which may have a substituent. The alkyl group, cycloalkyl group, and aryl group used as the terminal structure may be the same as the alkyl group, cycloalkyl group, and aryl group described for the substituent that the group represented by X may have. In addition, the substituent that the group used as the terminal structure may have may be the same as the substituent that the group represented by X may have.

[0051] From the viewpoint of suppressing the generation of outgassing during curing of the resin composition, the weight average molecular weight of the carbodiimide compound is preferably 500 or more, more preferably 600 or more, even more preferably 700 or more, even more preferably 800 or more, and particularly preferably 900 or more or 1000 or more. In addition, from the viewpoint of obtaining good compatibility, the upper limit of the weight average molecular weight of the carbodiimide compound is preferably 5000 or less, more preferably 4500 or less, even more preferably 4000 or less, even more preferably 3500 or less, and particularly preferably 3000 or less. The weight average molecular weight of the carbodiimide compound can be measured, for example, by gel permeation chromatography (GPC) method (polystyrene equivalent).

[0052] In addition, the carbodiimide compound may contain an isocyanate group (-N=C=O) in the molecule due to its manufacturing method. From the viewpoint of obtaining a resin composition exhibiting good storage stability, and thus from the viewpoint of realizing an insulating layer exhibiting desired properties, the content of the isocyanate group in the carbodiimide compound (also referred to as "NCO content") is preferably 5% by mass or less, more preferably 4% by mass or less, even more preferably 3% by mass or less, even more preferably 2% by mass or less, and particularly preferably 1% by mass or less or 0.5% by mass or less.

[0053] The carbodiimide compound may be a commercially available product. Examples of commercially available carbodiimide compounds include Carbodilite (registered trademark) V-02B, V-03, V-04K, V-07, and V-09 manufactured by Nisshinbo Chemical Co., Ltd., and Stavaxol (registered trademark) P, P400, and Hi-Kasil 510 manufactured by Rhein Chemie.

[0054] In the combination of (B) active ester compound, (D) thermoplastic resin, and a certain amount or more of (E) inorganic filler, from the viewpoint of obtaining an insulating layer excellent in all of the properties of dielectric tangent, thermal expansion coefficient, elongation at break, surface roughness, and peel strength, the content of the carbodiimide compound in the resin composition is preferably 1 mass% or more, more preferably 2 mass% or more, even more preferably 3 mass% or more, 4 mass% or more, or 5 mass% or more. The upper limit of the content of the carbodiimide compound is not particularly limited, but is preferably 30 mass% or less, more preferably 20 mass% or less, and even more preferably 15 mass% or less.

[0055] <(D) Thermoplastic resin> The resin composition of the present invention contains a thermoplastic resin as component (D).

[0056] Examples of the thermoplastic resin include phenoxy resin, polyvinyl acetal resin, acid anhydride group-containing vinyl resin, polyolefin resin, polybutadiene resin, polyimide resin, polyamideimide resin, styrene-based elastomer resin, polyethersulfone resin, polyphenylene ether resin, and polysulfone resin. The thermoplastic resin may be used alone or in combination of two or more. The thermoplastic resin preferably has a glass transition temperature of 80° C. or higher.

[0057] Among these, from the viewpoint of obtaining an insulating layer having even more excellent dielectric tangent, thermal expansion coefficient, elongation at break, surface roughness and peel strength in combination with the (B) active ester compound, the (C) carbodiimide compound, and a certain amount or more of the (E) inorganic filler, the thermoplastic resin is preferably at least one selected from the group consisting of phenoxy resin, polyvinyl acetal resin, acid anhydride group-containing vinyl resin, polyimide resin, polyamideimide resin, and styrene-based elastomer resin.

[0058] From the viewpoint of obtaining an insulating layer having good mechanical strength, the weight average molecular weight of the thermoplastic resin is preferably 10,000 or more, more preferably 15,000 or more, even more preferably 20,000 or more, even more preferably 25,000 or more or 30,000 or more. From the viewpoint of obtaining good compatibility, the upper limit of the weight average molecular weight of the thermoplastic resin is preferably 200,000 or less, more preferably 180,000 or less, even more preferably 160,000 or less, even more preferably 150,000 or less. The weight average molecular weight of the thermoplastic resin can be measured, for example, by gel permeation chromatography (GPC). In detail, the weight average molecular weight (polystyrene equivalent) of the thermoplastic resin can be measured at a column temperature of 40°C using a measuring device LC-9A / RID-6A manufactured by Shimadzu Corporation, a column Shodex K-800P / K-804L / K-804L manufactured by Showa Denko K.K., and chloroform or the like as a mobile phase, and calculated using a calibration curve of standard polystyrene.

[0059] In the combination of (B) an active ester compound, (C) a carbodiimide compound, and a certain amount or more of (E) an inorganic filler, from the viewpoint of obtaining an insulating layer excellent in all of the properties of dielectric tangent, thermal expansion coefficient, elongation at break, surface roughness, and peel strength, and particularly from the viewpoint of obtaining an insulating layer having high peel strength, it is preferable that the thermoplastic resin has a functional group containing one or more atoms selected from the group consisting of oxygen atoms, nitrogen atoms, and sulfur atoms, or a carbon-carbon double bond. Such functional groups include one or more selected from the group consisting of hydroxyl groups, carboxy groups, acid anhydride groups, epoxy groups, amino groups, thiol groups, enol groups, enamine groups, urea groups, cyanate groups, isocyanate groups, thioisocyanate groups, diimide groups, alkenyl groups, allene groups, and ketene groups. As the acid anhydride group, a carboxylic anhydride group is preferable. Suitable examples of the alkenyl group include a vinyl group, an allyl group, and a styryl group. By using a thermoplastic resin having such a functional group, the glass transition temperature of the obtained insulating layer tends to be high, and an insulating layer exhibiting good heat resistance can also be realized. When the thermoplastic resin contains such a functional group, the functional group equivalent of the thermoplastic resin is preferably 100000 or less, more preferably 90000 or less, 80000 or less, 70000 or less, 60000 or less, 50000 or less, 40000 or less, 30000 or less, 20000 or less, 10000 or less, 8000 or less, 6000 or less, or 5000 or less. The lower limit of the functional group equivalent is not particularly limited, but it can usually be 50 or more, 100 or more, etc.

[0060] Suitable thermoplastic resins are described in more detail below, but thermoplastic resins in which the above-mentioned functional groups have been further added to the thermoplastic resins shown below in accordance with known procedures can also be suitably used in the present invention.

[0061] Examples of the phenoxy resin include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A skeleton, bisphenol F skeleton, bisphenol S skeleton, bisphenolacetophenone skeleton, novolac skeleton, biphenyl skeleton, fluorene skeleton, dicyclopentadiene skeleton, norbornene skeleton, naphthalene skeleton, anthracene skeleton, adamantane skeleton, terpene skeleton, and trimethylcyclohexane skeleton. The terminal of the phenoxy resin may be any functional group such as a phenolic hydroxyl group or an epoxy group. Specific examples of phenoxy resins include "1256" and "4250" (both of which are phenoxy resins containing a bisphenol A skeleton), "YX8100" (phenoxy resin containing a bisphenol S skeleton), and "YX6954" (phenoxy resin containing a bisphenol acetophenone skeleton), all manufactured by Mitsubishi Chemical Corporation. Other examples include "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and "YL7553", "YL6794", "YL7213", "YL7290", and "YL7482" manufactured by Mitsubishi Chemical Corporation.

[0062] Specific examples of polyvinyl acetal resins include Denka Butyral 4000-2, 5000-A, 6000-C, and 6000-EP manufactured by Denki Kagaku Kogyo Co., Ltd., and S-LEC BH series, BX series, KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemical Co., Ltd.

[0063] The acid anhydride group-containing vinyl resin can be obtained, for example, by copolymerizing an acid anhydride group-containing monomer (d1) with another monomer (d2). Examples of the acid anhydride group-containing monomer (d1) include maleic anhydride, itaconic anhydride, citraconic anhydride, and aconitic anhydride. The other monomer (d2) is not particularly limited as long as it can be copolymerized with the acid anhydride group-containing monomer (d1), and an ethylenically unsaturated monomer such as (meth)acrylic acid, (meth)acrylic acid ester, or styrene may be used. Specific examples of the acid anhydride group-containing vinyl resin include "EF-30", "EF-40", "EF-60", and "EF-80" manufactured by CRAY VALLEY HSC.

[0064] Specific examples of polyimide resins include "RIKACOAT SN-20" and "RIKACOAT PN-20" manufactured by New Japan Chemical Co., Ltd., and "UNIDIC V-8000" manufactured by DIC Corp. Specific examples of polyimide resins also include modified polyimides such as linear polyimides obtained by reacting bifunctional hydroxyl-terminated polybutadiene, a diisocyanate compound, and a tetrabasic acid anhydride (JP 2006-37083 A), and polysiloxane skeleton-containing polyimides (JP 2002-12667 A, JP 2000-319386 A, WO2010 / 53186, etc.).

[0065] Specific examples of polyamide-imide resins include "Viromax HR11NN" and "Viromax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamide-imide resins also include modified polyamide-imides such as polysiloxane skeleton-containing polyamide-imides "KS9100" and "KS9300" manufactured by Hitachi Chemical Co., Ltd.

[0066] Examples of styrene-based elastomer resins include block copolymers containing a block of styrene or an analog thereof as at least one terminal block and an elastomer block of a conjugated diene or a hydrogenated product thereof as at least one intermediate block.Specific examples include styrene-butadiene diblock copolymers, styrene-butadiene triblock copolymers, styrene-isoprene diblock copolymers, styrene-isoprene triblock copolymers, hydrogenated styrene-butadiene diblock copolymers, hydrogenated styrene-butadiene triblock copolymers, hydrogenated styrene-isoprene diblock copolymers, hydrogenated styrene-isoprene triblock copolymers, and hydrogenated styrene-butadiene random copolymers.Specific examples of styrene-based elastomer resins include Asaprene, Tufprene, and Asaflex manufactured by Asahi Chemical Industry Co., Ltd.; and Hybra and Septon manufactured by Kuraray Co., Ltd.

[0067] A specific example of the polyethersulfone resin is "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0068] Specific examples of polysulfone resins include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers, Inc.

[0069] In the combination of (B) active ester compound, (C) carbodiimide compound, and a certain amount or more of (E) inorganic filler, from the viewpoint of obtaining an insulating layer excellent in all of the properties of dielectric tangent, thermal expansion coefficient, elongation at break, surface roughness, and peel strength, the content of thermoplastic resin in the resin composition is preferably 0.5 mass% or more, more preferably 1 mass% or more, even more preferably 1.5 mass% or more, and even more preferably 2 mass% or more. The upper limit of the content of thermoplastic resin is not particularly limited, but is preferably 40 mass% or less, more preferably 30 mass% or less, even more preferably 20 mass% or less, and even more preferably 15 mass% or less.

[0070] <(E) Inorganic filler> The resin composition of the present invention contains at least a certain amount of an inorganic filler as component (E).

[0071] In the combination of (B) active ester compound, (C) carbodiimide compound, and (D) thermoplastic resin, from the viewpoint of obtaining an insulating layer excellent in all of the properties of dielectric tangent, thermal expansion coefficient, elongation at break, surface roughness, and peel strength, particularly from the viewpoint of obtaining an insulating layer with low dielectric tangent and low thermal expansion coefficient, the content of inorganic filler in the resin composition layer is 40% by mass or more, preferably 45% by mass or more, more preferably 50% by mass or more, and even more preferably 55% by mass or more or 60% by mass or more. In the present invention in which an inorganic filler is used in combination with (B) active ester compound, (C) carbodiimide compound, and (D) thermoplastic resin, the content of inorganic filler can be further increased without decreasing the elongation at break, surface roughness, and peel strength. For example, the content of inorganic filler in the resin composition may be increased to 62% by mass or more, 64% by mass or more, 66% by mass or more, 68% by mass or more, 70% by mass or more, 72% by mass or more, or 74% by mass or more.

[0072] The upper limit of the content of the inorganic filler in the resin composition is preferably 90% by mass or less, more preferably 85% by mass or less, and even more preferably 80% by mass or less, from the viewpoint of the mechanical strength of the resulting insulating layer.

[0073] The material of the inorganic filler is not particularly limited, and examples thereof 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, and silica is particularly preferred. Examples of silica include amorphous silica, fused silica, crystalline silica, synthetic silica, and hollow silica. Moreover, spherical silica is preferred as the silica. The inorganic filler may be used alone or in combination of two or more. Commercially available spherical fused silica includes "SO-C2" and "SO-C1" manufactured by Admatechs Co., Ltd.

[0074] The average particle size of the inorganic filler is not particularly limited, but from the viewpoint of obtaining an insulating layer on which fine wiring can be formed, it is preferably 3 μm or less, more preferably 2 μm or less, and even more preferably 1 μm or less, 0.7 μm or less, 0.5 μm or less, 0.4 μm or less, or 0.3 μm or less. On the other hand, from the viewpoint of obtaining a resin varnish having a suitable viscosity and good handling properties when forming a resin varnish using the resin composition, the average particle size of the inorganic filler is preferably 0.01 μm or more, more preferably 0.03 μm or more, and even more preferably 0.05 μm or more, 0.07 μm or more, or 0.1 μm or more. 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 particle size distribution measuring device, and the median diameter is used as the average particle size. The measurement sample can be preferably one in which the inorganic filler is dispersed in water by ultrasonic waves. As the laser diffraction type particle size distribution measuring device, "LA-500", "LA-750", "LA-950" or the like manufactured by Horiba Ltd. can be used.

[0075] From the viewpoint of improving moisture resistance and dispersibility, the inorganic filler is preferably treated with one or more surface treatment agents such as aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, organosilazane compounds, titanate coupling agents, etc. Commercially available surface treatment agents include, for example, 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), etc.

[0076] 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 varnish or the melt viscosity in the form of a sheet, it is more preferable that the melt viscosity is 1 mg / m 2 Less than 0.8 mg / m is preferred. 2 Less than 0.5 mg / m is more preferable. 2 The following is even more preferred:

[0077] 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.

[0078] <(F) Curing accelerator> The resin composition of the present invention may further contain a curing accelerator as the component (F).

[0079] The curing accelerator is not particularly limited, but examples thereof include amine-based curing accelerators, imidazole-based curing accelerators, phosphorus-based curing accelerators, guanidine-based curing accelerators, etc., and amine-based curing accelerators and imidazole-based curing accelerators are preferred. The curing accelerators may be used alone or in combination of two or more.

[0080] Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine, benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, with 4-dimethylaminopyridine and 1,8-diazabicyclo(5,4,0)-undecene being preferred.

[0081] Examples of the imidazole curing accelerator include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2, 4-Diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-furan Examples of the imidazole compounds include imidazole compounds such as 2-ethyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds and epoxy resins. Of these, 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

[0082] Examples of the phosphorus-based curing accelerator include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, and the like, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

[0083] Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene. Examples of such biguanide include o-[4.4.0]dec-5-ene, 1-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide. Of these, dicyandiamide and 1,5,7-triazabicyclo[4.4.0]dec-5-ene are preferred.

[0084] Among these, in terms of obtaining an insulating layer having even more excellent dielectric tangent, thermal expansion coefficient, elongation at break, surface roughness and peel strength in combination with the above components (A) to (E), 4-dimethylaminopyridine and 1-benzyl-2-phenylimidazole are particularly preferred as the curing accelerator.

[0085] The content of the curing accelerator in the resin composition is not particularly limited, but is preferably 0.005% by mass to 1% by mass, and more preferably 0.01% by mass to 0.5% by mass.

[0086] <Other ingredients> - Hardener - The resin composition of the present invention may further contain a curing agent (excluding component (B)). By containing a curing agent, the insulating reliability, peel strength, and mechanical strength of the obtained insulating layer can be improved. The curing agent is not particularly limited, but examples thereof include phenol-based curing agents, naphthol-based curing agents, cyanate ester-based curing agents, and benzoxazine-based curing agents. The curing agents may be used alone or in combination of two or more. Among these, in combination with the above components (A) to (E), phenol-based curing agents, naphthol-based curing agents, and cyanate ester-based curing agents are preferred from the viewpoint of obtaining an insulating layer having even more excellent dielectric tangent, thermal expansion coefficient, elongation at break, surface roughness, and peel strength.

[0087] 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 preferred. Also, from the viewpoint of peel strength, a nitrogen-containing phenol-based curing agent or a nitrogen-containing naphthol-based curing agent is preferred, and a triazine skeleton-containing phenol-based curing agent or a triazine skeleton-containing naphthol-based curing agent is more preferred. Among them, from the viewpoint of highly satisfying heat resistance, water resistance, and adhesion strength with a conductor layer, a triazine skeleton-containing phenol novolac resin is preferred. 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., "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", and "SN-395" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd., and "LA-7052", "LA-7054", "LA-3018", "LA-1356", and "TD2090" manufactured by DIC Corporation.

[0088] The cyanate ester curing agent is not particularly limited, but examples thereof include novolak type (phenol novolak type, alkylphenol novolak type, etc.) cyanate ester curing agents, dicyclopentadiene type cyanate ester curing agents, bisphenol type (bisphenol A type, bisphenol F type, bisphenol S type, etc.) cyanate ester curing agents, and prepolymers of these partially converted to triazine. Specific examples 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. Commercially available cyanate ester curing agents include "PT30" and "PT60" (both of which are phenol novolac type multifunctional cyanate ester resins) manufactured by Lonza Japan Co., Ltd., and "BA230" (a prepolymer in which part or all of bisphenol A dicyanate has been converted to triazine and formed into a trimer).

[0089] Specific examples of benzoxazine-based curing agents include "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemical Industries Co., Ltd.

[0090] The content of the curing agent in the resin composition is not particularly limited, but from the viewpoint of the mechanical strength of the resulting insulating layer, it is preferably 0.5% by mass to 10% by mass, and more preferably 1% by mass to 6% by mass.

[0091] -Flame retardants- The resin composition of the present invention may further contain a flame retardant. Examples of the flame retardant include organic phosphorus flame retardants, organic nitrogen-containing phosphorus compounds, nitrogen compounds, silicone flame retardants, metal hydroxides, etc. The flame retardants may be used alone or in combination of two or more. The content of the flame retardant in the resin composition is not particularly limited, but is preferably 0.5% by mass to 10% by mass, more preferably 1% by mass to 9% by mass.

[0092] -Organic filler- The resin composition of the present invention may further include an organic filler. As the organic filler, any organic filler that can be used when forming an insulating layer of a printed wiring board may be used, and examples thereof include rubber particles, polyamide fine particles, silicone particles, etc., and rubber particles are preferred.

[0093] The rubber particles are not particularly limited as long as they are fine particles of resin that is insoluble and infusible in organic solvents by chemically crosslinking a resin that exhibits rubber elasticity, and examples thereof include acrylonitrile butadiene rubber particles, butadiene rubber particles, acrylic rubber particles, etc. Specific examples of the rubber particles include XER-91 (manufactured by Japan Synthetic Rubber Co., Ltd.), Staphyloid AC3355, AC3816, AC3816N, AC3832, AC4030, AC3364, IM101 (all manufactured by Aica Kogyo Co., Ltd.), Paraloid EXL2655, EXL2602 (all manufactured by Kureha Chemical Industry Co., Ltd.), etc.

[0094] The average particle diameter of the organic filler is preferably in the range of 0.005 μm to 1 μm, more preferably in the range of 0.2 μm to 0.6 μm. The average particle diameter of the organic filler can be measured using a dynamic light scattering method. For example, the organic filler is uniformly dispersed in a suitable organic solvent by ultrasonic waves or the like, and a particle size distribution of the organic filler is prepared on a mass basis using a concentrated particle size analyzer (Otsuka Electronics Co., Ltd., "FPAR-1000"), and the median diameter is taken as the average particle diameter. The content of the organic filler in the resin composition is preferably 1 mass% to 10 mass%, more preferably 2 mass% to 5 mass%.

[0095] The resin composition of the present invention may further contain other components as necessary, such as organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds, as well as resin additives such as thickeners, defoamers, leveling agents, adhesion promoters, colorants, and curable resins.

[0096] 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.

[0097] The resin composition of the present invention can provide a cured product (insulating layer) with a low dielectric loss tangent. The dielectric loss tangent of the cured product of the resin composition of the present invention can be measured by the method described below in <Measurement of dielectric loss tangent>. Specifically, it can be measured at a frequency of 5.8 GHz and a measurement temperature of 23°C by a cavity resonator perturbation method. From the viewpoint of preventing heat generation at high frequencies and reducing signal delay and signal noise, the dielectric loss tangent is preferably 0.010 or less, more preferably 0.009 or less, and even more preferably 0.008 or less, 0.007 or less, or 0.006 or less. The lower limit of the dielectric loss tangent is preferably as low as possible, but can usually be 0.001 or more.

[0098] The resin composition of the present invention can provide a cured product (insulating layer) with a low thermal expansion coefficient. The linear thermal expansion coefficient of the cured product of the resin composition of the present invention can be measured by the method described below in <Measurement of glass transition temperature and linear thermal expansion coefficient>. Specifically, the average linear thermal expansion coefficient in the planar direction at 25 to 150°C can be measured by performing thermomechanical analysis using a tensile load method. The cured product of the resin composition of the present invention can exhibit a linear thermal expansion coefficient of preferably 40 ppm / °C or less, more preferably 35 ppm / °C or less, even more preferably 30 ppm / °C or less, even more preferably 25 ppm / °C or less, and particularly preferably 20 ppm / °C or less. The lower limit of the linear thermal expansion coefficient is not particularly limited, but is usually 1 ppm / °C or more.

[0099] The resin composition of the present invention can provide a cured product (insulating layer) exhibiting good elongation at break. The elongation at break of the cured product of the resin composition of the present invention can be measured by the method described below in <Measurement of elongation at break>. Specifically, it can be measured by a tensile test method in accordance with the Japanese Industrial Standards (JIS K7127). The cured product of the resin composition of the present invention can exhibit an elongation at break of preferably 2% or more, more preferably 2.1% or more, even more preferably 2.2% or more, even more preferably 2.3% or more, 2.4% or more, or 2.5% or more. The upper limit of the elongation at break is preferably 30% or less, more preferably 20% or less, and even more preferably 10% or less.

[0100] The resin composition of the present invention can provide a cured product (insulating layer) with low surface roughness. The arithmetic mean roughness (Ra) of the cured product of the resin composition of the present invention can be measured by the method described below in <Measurement of arithmetic mean roughness (Ra)>. It is desirable that the surface of the insulating layer after roughening treatment has small surface irregularities in order to reduce the loss of electrical signals. Specifically, the arithmetic mean roughness (Ra) of the insulating layer surface after the insulating layer is roughened by curing the resin composition to form an insulating layer is preferably 140 nm or less, more preferably 130 nm or less, even more preferably 120 nm or less, even more preferably 110 nm or less, and particularly preferably 100 nm or less. The lower limit of the arithmetic mean roughness (Ra) is preferably 5 nm or more, more preferably 10 nm or more, and even more preferably 15 nm or more, from the viewpoint of obtaining sufficient peel strength.

[0101] The resin composition of the present invention can provide a cured product (insulating layer) with high peel strength. The peel strength of the cured product of the resin composition of the present invention can be measured by the method described below in <Measurement of peel strength of plated conductor layer>. Specifically, when the resin composition is cured to form an insulating layer, and the surface of the insulating layer after roughening is plated to form a conductor layer, the peel strength between the resulting conductor layer and insulating layer is preferably 0.50 kgf / cm or more, more preferably 0.55 kgf / cm or more, and even more preferably 0.60 kgf / cm or more. The upper limit of the peel strength is not particularly limited, but can usually be 1.2 kgf / cm or less.

[0102] The resin composition of the present invention can also provide a cured product (insulating layer) with a high glass transition temperature (Tg). The glass transition temperature (Tg) of the cured product of the resin composition of the present invention can be measured by the method described below in <Measurement of elongation at break>. The cured product of the resin composition of the present invention can exhibit a glass transition temperature (Tg) of preferably 165°C or higher, more preferably 170°C or higher, 175°C or higher, or 180°C or higher. The upper limit of the glass transition temperature (Tg) is not particularly limited, but is usually 250°C or lower.

[0103] The resin composition of the present invention can be suitably used as a resin composition for forming an insulating layer of a printed wiring board (resin composition for insulating layer of printed wiring board), more suitably used as a resin composition for forming an interlayer insulating layer of a printed wiring board (resin composition for insulating layer of printed wiring board), and further suitably used as a resin composition for forming an interlayer insulating layer on which a conductor layer is formed by plating (resin composition for insulating layer of printed wiring board on which a conductor layer is formed by plating). The resin composition of the present invention can also be used in a wide range of applications requiring a resin composition, such as adhesive films, sheet-like laminate materials such as prepregs, solder resists, underfill materials, die bonding materials, semiconductor encapsulants, hole filling resins, and component embedding resins.

[0104] [Adhesive film] The resin composition of the present invention can be used in the form of a varnish, but is generally preferably used industrially in the form of an adhesive film.

[0105] The adhesive film comprises a support and a resin composition layer (adhesive layer) bonded to the support, and the resin composition layer (adhesive layer) is formed from the resin composition of the present invention.

[0106] From the viewpoint of thinning the printed wiring board, the thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, even more preferably 60 μm or less, and even more preferably 50 μm or less or 40 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, but is usually 5 μm or more or 10 μm or more.

[0107] 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.

[0108] 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.

[0109] 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.

[0110] The support may be subjected to a matte treatment or a corona treatment on the surface on the side to be bonded to the resin composition layer. In addition, a support with a release layer having a release layer on the surface on the side to be bonded to the resin composition layer may be used as the support. Examples of the release agent used in the release layer of the support with a release layer include one or more release agents selected from the group consisting of alkyd resins, olefin resins, urethane resins, and silicone resins. Examples of commercially available release agents include alkyd resin-based release agents such as "SK-1", "AL-5", and "AL-7" manufactured by Lintec Corporation.

[0111] 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 the support is a support with a release layer, the total thickness of the support with a release layer is preferably in the above range.

[0112] The adhesive film can be produced, for example, by preparing a resin varnish by dissolving the resin composition in an organic solvent, applying this resin varnish onto a support using a die coater or the like, and then drying it to form a resin composition layer.

[0113] Examples of the organic solvent include ketones such as acetone, methyl ethyl ketone (MEK), and cyclohexanone, acetates such as ethyl acetate, butyl acetate, cellosolve acetate, propylene glycol monomethyl ether acetate, and carbitol acetate, carbitols such as cellosolve and butyl carbitol, aromatic hydrocarbons such as toluene and xylene, and amide solvents such as dimethylformamide, dimethylacetamide (DMAc), and N-methylpyrrolidone. The organic solvents may be used alone or in combination of two or more.

[0114] Drying may be performed by a known method such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is performed so that the content of organic solvent in the resin composition layer becomes 10 mass % or less, preferably 5 mass % or less. Although it varies depending on the boiling point of the organic solvent in the resin varnish, for example, when a resin varnish containing 30 mass % to 60 mass % of organic solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 minutes to 10 minutes.

[0115] In the adhesive film, a protective film equivalent to the support can be further laminated 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, it is possible to prevent adhesion of dirt and the like to the surface of the resin composition layer and scratches. The adhesive film can be wound up in a roll and stored. When the adhesive film has a protective film, it can be used by peeling off the protective film.

[0116] The adhesive film of the present invention can be suitably used for forming an insulating layer of a printed wiring board (for an insulating layer of a printed wiring board), can be more suitably used for forming an interlayer insulating layer of a printed wiring board (for an interlayer insulating layer of a printed wiring board), and can be further suitably used as a resin composition for forming an interlayer insulating layer on which a conductor layer is formed by plating (for an interlayer insulating layer of a printed wiring board on which a conductor layer is formed by plating).

[0117] [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.

[0118] In one embodiment, the printed wiring board of the present invention can be produced using the above-mentioned adhesive film by a method including the following steps (I) and (II). (I) A step of laminating an adhesive film on an inner layer substrate so that a resin composition layer of the adhesive film is bonded to the inner layer substrate. (II) A step of thermally curing the resin composition layer to form an insulating layer

[0119] The "inner layer substrate" used in step (I) mainly refers to a substrate such as a glass epoxy substrate, a metal substrate, a polyester substrate, a polyimide substrate, a BT resin substrate, a thermosetting polyphenylene ether substrate, or a circuit substrate having a patterned conductor layer (circuit) formed on one or both sides of the substrate. In addition, the "inner layer substrate" of the present invention also includes an inner layer circuit substrate, which is an intermediate product on which an insulating layer and / or a conductor layer is to be formed when manufacturing a printed wiring board.

[0120] The lamination of the inner layer substrate and the adhesive film can be carried out, for example, by thermocompression bonding the adhesive film to the inner layer substrate from the support side. Examples of the member for thermocompression bonding the adhesive film 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 adhesive film but via an elastic material such as heat-resistant rubber so that the adhesive film can sufficiently follow the surface irregularities of the inner layer substrate.

[0121] The lamination of the inner layer substrate and the adhesive film 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.

[0122] The lamination can be performed by using a commercially available vacuum laminator, such as a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd. or a vacuum applicator manufactured by Nichigo-Morton Co., Ltd.

[0123] After lamination, the laminated adhesive film 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.

[0124] The support may be removed between step (I) and step (II) or after step (II).

[0125] In step (II), the resin composition layer is thermally cured to form an insulating layer.

[0126] 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.

[0127] For example, the thermal curing conditions for the resin composition layer will vary depending on the type of resin composition, etc., but the curing temperature can be in the range of 120°C to 240°C (preferably in the range of 150°C to 210°C, more preferably in the range of 170°C to 190°C) and the curing time can be in the range of 5 minutes to 90 minutes (preferably in the range of 10 minutes to 75 minutes, more preferably in the range of 15 minutes to 60 minutes).

[0128] 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 for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes) at a temperature of 50°C or more and less than 120°C (preferably 60°C or more and 110°C or less, more preferably 70°C or more and 100°C or less).

[0129] 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 on the surface of the insulating 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 and used in manufacturing printed wiring boards. When the support is removed after step (II), the removal of the support may be carried out between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V).

[0130] 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.

[0131] Step (IV) is a step of roughening the insulating layer. 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 is not particularly limited, but examples thereof include 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 and Swelling Dip Securigans SBU manufactured by Atotech Japan Co., Ltd. The swelling treatment with 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 minute to 20 minutes. The oxidizing agent is not particularly limited, and 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 80°C for 10 to 30 minutes. 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 Co., Ltd. The neutralizing solution is preferably an acidic aqueous solution, and an example of a commercially available product is Reduction Solution Securiganth P manufactured by Atotech Japan Co., Ltd. The treatment using the neutralizing solution can be performed by immersing the treated surface that has been roughened with the oxidizing agent solution in a neutralizing solution at 30°C to 80°C for 5 to 30 minutes.

[0132] Step (V) is a step of forming a conductor layer on the surface of the insulating layer.

[0133] 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 them, from the viewpoints of versatility, cost, ease of patterning, etc. of the conductor layer formation, 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.

[0134] 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.

[0135] The thickness of the conductor layer depends on the desired design of the printed wiring board, but is generally 3 μm to 35 μm, preferably 5 μm to 30 μm.

[0136] 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. An example of forming a conductor layer by a semi-additive method is shown below.

[0137] 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.

[0138] As described above, by producing a printed wiring board using the resin composition of the present invention, it is possible to advantageously produce a printed wiring board having an insulating layer that is excellent in all of the properties, including dielectric tangent, thermal expansion coefficient, elongation at break, surface roughness, and peel strength.

[0139] [Semiconductor Devices] The printed wiring board of the present invention can be used to manufacture a semiconductor device. Examples of the semiconductor device include various semiconductor devices used in electrical products (e.g., computers, mobile phones, digital cameras, televisions, etc.) and vehicles (e.g., motorcycles, automobiles, trains, ships, aircraft, etc.).

[0140] The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on the conductive portion of the printed wiring board of the present invention. The "conductive portion" is the "portion that transmits an electric signal on the printed wiring board", and the location 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.

[0141] The method of mounting the semiconductor chip when manufacturing the semiconductor device of the present invention 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 mounting method using a bumpless buildup layer (BBUL), a mounting method using an anisotropic conductive film (ACF), a mounting method using a non-conductive film (NCF), etc. Here, the "mounting method using a bumpless buildup layer (BBUL)" 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

[0142] The present invention will be described in more detail below with reference to examples, but the present invention is not limited to these examples. In addition, "parts" means parts by mass.

[0143] [Measurement and evaluation methods] First, the various measurement and evaluation methods will be explained.

[0144] <Preparation of samples for measuring peel strength and arithmetic mean roughness (Ra value)> (1) Surface preparation for inner layer circuit boards 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 Corporation's "R1515A") with an inner layer circuit formed were etched 1 μm deep using MEC Corporation's "CZ8101" to roughen the copper surface.

[0145] (2) Lamination of adhesive film The adhesive films prepared in the examples and comparative examples were laminated on both sides of the inner layer circuit board using a batch type vacuum pressure laminator ("MVLP-500" manufactured by Meiki Seisakusho Co., Ltd.) so that the resin composition layer was bonded to the inner layer circuit board. The lamination was performed by reducing the pressure for 30 seconds to 13 hPa or less, and then pressing at 100°C and a pressure of 0.74 MPa for 30 seconds.

[0146] (3) Hardening of the resin composition After lamination of the adhesive film, the resin composition layer was thermally cured at 100° C. for 30 minutes and then at 180° C. for 30 minutes to form an insulating layer. Thereafter, the support was peeled off to expose the insulating layer.

[0147] (4) Roughening treatment The inner layer circuit board with the exposed insulating layer was immersed in a swelling liquid (Atotech Japan's "Swelling Dip Securigant P", an aqueous solution of sodium hydroxide containing diethylene glycol monobutyl ether) at 60°C for 10 minutes, then immersed in an oxidizing agent (Atotech Japan's "Concentrate Compact CP", an aqueous solution of potassium permanganate at about 6 mass% and sodium hydroxide at about 4 mass%) at 80°C for 20 minutes, and finally immersed in a neutralizing liquid (Atotech Japan's "Reduction Solution Securigant P", an aqueous solution of hydroxylamine sulfate) at 40°C for 5 minutes. It was then dried at 80°C for 30 minutes. The obtained board is called "Evaluation Board a".

[0148] (5) Formation of the conductor layer A conductor layer was formed on the roughened surface of the insulating layer by a semi-additive method. That is, the substrate after the roughening treatment was treated with PdCl 2 The substrate was immersed in an electroless plating solution containing the compound at 40°C for 5 minutes, and then immersed in an electroless copper plating solution at 25°C for 20 minutes. Next, the substrate was heated at 150°C for 30 minutes for annealing, after which an etching resist was formed and a pattern was formed by etching. Then, copper sulfate electroplating was performed to form a conductor layer with a thickness of 30 μm, and annealing was performed at 200°C for 60 minutes. The obtained substrate is referred to as "evaluation substrate b".

[0149] <Measurement of arithmetic mean roughness (Ra)> For the evaluation board a, the Ra value was calculated using a non-contact surface roughness meter (Beeco Instruments' "WYKO NT3300") in VSI contact mode with a 50x lens over a measurement range of 121μm x 92μm. The Ra value was calculated by averaging 10 randomly selected points.

[0150] <Measurement of peel strength of plated conductor layer> The peel strength of the insulating layer and the conductor layer was measured for evaluation board b in accordance with the Japanese Industrial Standards (JIS C6481). Specifically, a 10 mm wide and 100 mm long cut was made in the conductor layer of evaluation board b, one end of which was peeled off and held with a gripper, and the load (kgf / cm) was measured when 35 mm was peeled off vertically at a speed of 50 mm / min at room temperature, to determine the peel strength. A tensile tester ("AC-50C-SL" manufactured by TSE Co., Ltd.) was used for the measurement.

[0151] <Measurement of elongation at break> The adhesive films prepared in the examples and comparative examples were heated at 200°C for 90 minutes to thermally cure the resin composition layer, and then the support was peeled off. The obtained cured product was referred to as "evaluation cured product c". For evaluation cured product c, a tensile test was performed using a Tensilon universal testing machine (manufactured by Orientec Co., Ltd., "RTC-1250A") in accordance with the Japanese Industrial Standards (JIS K7127) to measure the elongation at break.

[0152] <Measurement of glass transition temperature and linear thermal expansion coefficient> The cured product c for evaluation was cut into a test piece having a width of about 5 mm and a length of about 15 mm, and a thermomechanical analysis was performed by a tensile load method using a thermomechanical analyzer (Rigaku Corporation, "Thermo Plus TMA8310"). In detail, the test piece was mounted on the thermomechanical analyzer, and then measured twice consecutively under the measurement conditions of a load of 1 g and a heating rate of 5°C / min. In the second measurement, the glass transition temperature (Tg;°C) and the average coefficient of linear thermal expansion (CTE; ppm / °C) in the range from 25°C to 150°C were calculated.

[0153] <Measurement of dielectric tangent> The cured product c for evaluation was cut into a test piece having a width of 2 mm and a length of 80 mm. The dielectric tangent of the test piece was measured at a measurement frequency of 5.8 GHz and a measurement temperature of 23° C. by a cavity resonance perturbation method using an “HP8362B” manufactured by Agilent Technologies. The measurement was performed on two test pieces, and the average value was calculated.

[0154] <Example 1> 10 parts of bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 180), 25 parts of biphenyl type epoxy resin ("NC3000L" manufactured by Nippon Kayaku Co., Ltd., epoxy equivalent of about 269), 25 parts of bixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), and 20 parts of phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, 1:1 solution of MEK and cyclohexanone with a solid content of 30 mass%) were dissolved in 30 parts of solvent naphtha by heating with stirring. After cooling to room temperature, 15 parts of a triazine skeleton-containing phenolic curing agent (DIC Corporation's "LA-3018-50P", hydroxyl group equivalent of about 151, 2-methoxypropanol solution with solid content of 50%), 20 parts of an active ester compound (DIC Corporation's "HPC-8000-65T", active group equivalent of about 223, toluene solution with non-volatile content of 65% by mass), 20 parts of a carbodiimide compound (Nisshinbo Chemical Inc.'s "V-03", NCO A resin varnish was prepared by mixing 20 parts of a curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with 10% solids by mass), 3 parts of a curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with 10% solids by mass), and 275 parts of spherical silica (average particle size 0.5 μm, Admatechs Corporation's SO-C2) that had been surface-treated with an aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd.'s KBM573), and dispersing the mixture uniformly using a high-speed rotating mixer.

[0155] A PET film with an alkyd resin-based release layer ("AL5" manufactured by Lintec Corporation, thickness 38 μm) was prepared as a support. A resin varnish was uniformly applied onto the release layer of the support so that the thickness of the resin composition layer after drying was 30 μm, and the resin varnish was dried at 80°C to 120°C (average 100°C) for 4 minutes to prepare an adhesive film.

[0156] <Example 2> A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that the amount of the carbodiimide compound (Nisshinbo Chemical Inc.'s "V-03", a toluene solution with a non-volatile content of 50% by mass) was changed to 80 parts.

[0157] <Example 3> A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that the amount of spherical silica (average particle size 0.5 μm, Admatechs Co., Ltd. "SO-C2") surface-treated with an aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd. "KBM573") was changed to 100 parts.

[0158] <Example 4> A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that 275 parts of spherical silica (average particle size 0.5 μm, Admatechs Co., Ltd. "SO-C2") surface-treated with an aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd., "KBM573") was replaced with 275 parts of spherical silica (average particle size 0.3 μm, Admatechs Co., Ltd. "SO-C1") surface-treated with an aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd., "KBM573").

[0159] <Example 5> A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that 20 parts of an active ester compound (DIC Corporation's "HPC-8000-65T", active group equivalent of about 223, toluene solution with 65% by mass of non-volatile components) was changed to 21 parts of an active ester compound (DIC Corporation's "EXB9050L-62M", active group equivalent of about 334, MEK solution with 62% by mass of non-volatile components).

[0160] <Example 6> A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that 3 parts of the curing accelerator (4-dimethylaminopyridine (DMAP), MEK solution with 10% solids by mass) was replaced with 6 parts of the curing accelerator ("1B2PZ" manufactured by Shikoku Kasei Co., Ltd., 1-benzyl-2-phenylimidazole, MEK solution with 10% solids by mass).

[0161] <Example 7> A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that 20 parts of a carbodiimide compound (Nisshinbo Chemical Co., Ltd.'s "V-03", a toluene solution containing 50% by mass of non-volatile components) was replaced with 20 parts of a carbodiimide compound (Nisshinbo Chemical Co., Ltd.'s "V-07", a toluene solution containing 0.5% by mass of NCO and 50% by mass of non-volatile components).

[0162] <Example 8> A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that 20 parts of the phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass) was replaced with 40 parts of a polyvinyl butyral resin (glass transition temperature 105°C, "KS-1" manufactured by Sekisui Chemical Co., Ltd., a 1:1 solution of ethanol and toluene with a non-volatile content of 15% by mass).

[0163] <Example 9> A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that 20 parts of a phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass) was replaced with 12 parts of an acid anhydride group-containing vinyl resin ("EF-30" manufactured by CRAY VALLEY HSC, a cyclohexanone solution with a solid content of 50%).

[0164] <Example 10> A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that 20 parts of the phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass) was replaced with 30 parts of a polyimide resin ("SN-20" manufactured by New Japan Chemical Co., Ltd., an N-methyl-2-pyrrolidone (NMP) solution with a solid content of 20%).

[0165] <Example 11> A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that 20 parts of a phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass) was replaced with 15 parts of a polyimide resin ("Unidic V-8000" manufactured by DIC Corporation, an ethyl diglycol acetate solution with a non-volatile content of 40% by mass).

[0166] <Example 12> A resin varnish and an adhesive film were prepared in the same manner as in Example 2, except that 10 parts of a bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of approximately 180) was replaced with 10 parts of an alicyclic epoxy resin having an ester skeleton ("Celloxide 2021P" manufactured by Daicel Corporation).

[0167] <Example 13> A resin varnish and an adhesive film were prepared in the same manner as in Example 2, except that the amount of triazine skeleton-containing phenolic hardener (DIC Corporation's "LA-3018-50P", hydroxyl equivalent of about 151, 2-methoxypropanol solution with 50% solids) was changed to 5 parts, and 10 parts of a benzoxazine hardener (Shikoku Chemical Industry Co., Ltd.'s "Pd", cyclohexanone solution with 50% solids) was added.

[0168] <Example 14> A resin varnish and an adhesive film were prepared in the same manner as in Example 2, except that 20 parts of the phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass) was replaced with 10.9 parts of the siloxane skeleton-containing polyimide resin (solid content of 55% by mass) of Synthesis Example 1.

[0169] [Synthesis Example 1] In a 500 mL separable flask equipped with a water content receiver connected to a reflux condenser, a nitrogen inlet tube, and a stirrer, 20 parts of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (BTDA), 70.9 parts of γ-butyrolactone, 7 parts of toluene, 61.5 parts of diaminosiloxane ("X-22-9409" manufactured by Shin-Etsu Chemical Co., Ltd., amine equivalent 665), and 7.4 parts of 2,6-bis(1-hydroxy-1-trifluoromethyl-2,2,2-trifluoroethyl)-1,5-naphthalenediamine (HFA-NAP) were added and reacted by stirring at 45°C for 2 hours under a nitrogen stream. The reaction solution was then heated and maintained at about 160°C while azeotropically removing condensed water together with toluene under a nitrogen stream. After confirming that a predetermined amount of water had accumulated in the water content receiver and that no water was flowing out, the temperature was further raised and the mixture was stirred at 200°C for 1 hour. After that, the mixture was cooled to finish, and a varnish containing 55% by mass of a siloxane skeleton-containing polyimide resin having a hexafluoroisopropanol group (HFA group) was produced. In this case, the content of the siloxane structure in the resin was 70.9% by mass, and the HFA group equivalent was 2881 g / mol.

[0170] <Example 15> A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that 10 parts of bisphenol A type epoxy resin ("828US" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight approximately 180) was replaced with 10 parts of bisphenol AF type epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent weight approximately 235).

[0171] <Comparative Example 1> A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that 20 parts of a carbodiimide compound (Nisshinbo Chemical Inc.'s "V-03", a toluene solution containing 50% by mass of non-volatile components) was not used.

[0172] <Comparative Example 2> A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that 20 parts of an active ester compound (DIC Corporation's "HPC-8000-65T", active group equivalent of approximately 223, toluene solution with 65% by mass of non-volatile components) was not used.

[0173] <Comparative Example 3> A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that 20 parts of a phenoxy resin ("YL7553BH30" manufactured by Mitsubishi Chemical Corporation, a 1:1 solution of MEK and cyclohexanone with a solid content of 30% by mass) was not used.

[0174] <Comparative Example 4> A resin varnish and an adhesive film were prepared in the same manner as in Example 1, except that the amount of spherical silica (average particle size 0.5 μm, Admatechs Co., Ltd. "SO-C2") surface-treated with an aminosilane coupling agent (Shin-Etsu Chemical Co., Ltd., "KBM573") was changed to 40 parts.

[0175] The results are shown in Table 1.

[0176] [Table 1]

Claims

1. A resin composition comprising: (A) an epoxy resin; (B) an active ester compound; (C) a carbodiimide compound; (D) a thermoplastic resin; and (E) spherical silica surface-treated with an aminosilane coupling agent, wherein the component (D) is one or more thermoplastic resins selected from the group consisting of a phenoxy resin, a polyvinyl acetal resin, an acid anhydride group-containing vinyl resin, a polyimide resin, a polyamideimide resin, and a styrene-based elastomer resin, the content of the component (E) is 62% by mass or more when the total amount of non-volatile components in the resin composition is taken as 100% by mass, and the content of the component (A) is 3 to 30% by mass when the total amount of non-volatile components in the resin composition is taken as 100% by mass.

2. The resin composition according to claim 1, wherein the weight average molecular weight of the component (D) is 10,000 to 200,000.

3. The resin composition according to claim 1 or 2, wherein the component (D) is a thermoplastic resin having a functional group containing one or more atoms selected from the group consisting of oxygen atoms, nitrogen atoms, and sulfur atoms, or a carbon-carbon double bond.

4. The resin composition according to any one of claims 1 to 3, wherein the content of the component (D) is 0.5 to 30 mass% when the non-volatile components in the resin composition are 100 mass%.

5. The resin composition according to any one of claims 1 to 4, wherein the weight average molecular weight of the component (C) is 500 to 5,000.

6. The resin composition according to any one of claims 1 to 5, wherein the content of the component (C) is 1 to 30 mass% when the non-volatile components in the resin composition are 100 mass%.

7. The resin composition according to any one of claims 1 to 6, wherein the content of the component (C) is 4 mass% or more when the non-volatile components in the resin composition are 100 mass%.

8. The resin composition according to any one of claims 1 to 7, wherein the component (B) is selected from the group consisting of an active ester compound having a dicyclopentadiene-type diphenol structure, an active ester compound having a naphthalene structure, and a phosphorus atom-containing active ester compound.

9. The resin composition according to any one of claims 1 to 8, wherein the content of the (E) component is 66% by mass or more, and the content of the (D) component is 20% by mass or less, when the total amount of non-volatile components in the resin composition is 100% by mass.

10. The resin composition according to any one of claims 1 to 9, wherein the average particle size of the component (E) is 0.01 µm to 3 µm.

11. The resin composition according to any one of claims 1 to 10, further comprising (F) a curing accelerator.

12. The resin composition according to claim 11, wherein the component (F) is 4-dimethylaminopyridine or 1-benzyl-2-phenylimidazole.

13. The resin composition according to any one of claims 1 to 12, further comprising one or more selected from the group consisting of a phenol-based curing agent, a naphthol-based curing agent, a cyanate ester-based curing agent, and a benzoxazine-based curing agent.

14. The resin composition according to any one of claims 1 to 13, wherein the aminosilane coupling agent is N-phenyl-3-aminopropyltrimethoxysilane.

15. An adhesive film comprising a support and a layer of the resin composition according to any one of claims 1 to 14 bonded to the support.

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

17. A semiconductor device comprising the printed wiring board according to claim 16.

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