Resin composition

Abstract

To provide a resin composition or the like, capable of yielding a cured product with high elongation at break, high etch rate, enhanced fine processability, and reduced cure shrinkage.SOLUTION: A resin composition comprises (A) an epoxy resin, (B) a curing agent, (C) boron nitride, and (D) an inorganic filler having a thermal conductivity of 10 W / m K or less.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a resin composition, and further to a resin sheet, a printed wiring board, a method for producing a printed wiring board, and a semiconductor device obtained 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. For example, Patent Document 1 discloses a resin composition as an insulating material for such insulating layers of printed wiring boards. [Prior art documents] [Patent documents]

[0003] [Patent Document 1] Patent Publication No. 2022-60800 Summary of the Invention [Problem to be solved by the invention]

[0004] 2. Description of the Related Art Insulating layers of printed wiring boards may have recesses such as trenches and via holes formed therein. One method for forming recesses is to use plasma treatment.

[0005] To form recesses by plasma treatment, the insulating layer must have excellent mechanical strength, which requires the insulating layer to have high breaking elongation. Furthermore, the processing speed of the recesses by plasma treatment must be fast, i.e., the etching rate must be high. However, it has been technically difficult to achieve both high breaking elongation and high etching rate.

[0006] In recent years, there has been a demand for finer wiring due to improved functionality of electronic components. Therefore, it is necessary to reduce the diameter of recesses formed by plasma treatment, and fine processing of recesses by plasma treatment is required. Furthermore, resin compositions undergo cure shrinkage when cured, and to achieve further miniaturization, it is also required that the degree of cure shrinkage of the resin composition is low.

[0007] The present invention has been devised in view of the above-mentioned problems, and aims to provide a resin composition that has a high etching rate and is capable of giving a cured product that is excellent in breaking elongation, fine processability, and cure shrinkage; a resin sheet containing the resin composition; and a printed wiring board and a semiconductor device that have an insulating layer formed using the resin composition. [Means for solving the problem]

[0008] As a result of extensive research into the above-mentioned problems, the present inventors have found that the above-mentioned problems can be solved by incorporating a combination of (C) boron nitride and (D) an inorganic filler having a thermal conductivity of 10 W / m K or less in addition to (A) an epoxy resin and (B) a curing agent, and have thus completed the present invention.

[0009] That is, the present invention includes the following. [1] (A) epoxy resin, (B) a curing agent; (C) boron nitride, and (D) A resin composition containing an inorganic filler having a thermal conductivity of 10 W / m·K or less. [2] The resin composition according to [1], wherein the component (B) contains an active ester curing agent. [3] The resin composition according to [2], wherein b1 is the content (volume %) of the active ester curing agent when the nonvolatile components in the resin composition are taken as 100% by volume, and c is the content (volume %) of component (C) when the nonvolatile components in the resin composition are taken as 100% by volume, and b1 / c is 0.01 or more and 10 or less. [4] The resin composition according to any one of [1] to [3], wherein the content of component (A) is 1% by mass or more and 50% by mass or less, when the resin components in the resin composition are taken as 100% by mass. [5] The resin composition according to any one of [1] to [4], wherein the content (volume %) of component (C) is 10% by volume or more, where the total amount of components (C) and (D) is 100% by volume. [6] The resin composition according to any one of [1] to [5], wherein the thermal conductivity of the cured product obtained by thermally curing the resin composition at 200°C for 90 minutes is 5 W / m·K or less. [7] The resin composition according to any one of [1] to [6], which is a resin composition for forming recesses in an insulating layer by a dry process. [8] The resin composition according to any one of [1] to [7], which is a resin composition for forming recesses in an insulating layer by plasma treatment. [9] The resin composition according to [8], wherein the gas to be converted into plasma in the plasma treatment is at least one selected from the group consisting of O2, a fluorine-based gas, and an inert gas.

[10] The resin composition according to [8] or [9], wherein the gas to be converted into plasma in the plasma treatment is a mixed gas containing O2, a fluorine-based gas, and an inert gas.

[11] The resin composition according to [9] or

[10] , wherein the amount of O2 relative to 100% of the total gas amount is 1% or more and 90% or less on a sccm basis.

[12] The resin composition according to any one of [9] to

[11] , wherein the amount of the fluorine-based gas relative to 100% of the total amount of gas is 5% or more and 95% or less on the basis of sccm.

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

[12] , wherein the resin composition is heat-cured at 190°C for 90 minutes to produce a cured product having an elongation at break of more than 0.7%.

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

[13] , wherein the cured product obtained by thermally curing the resin composition at 190°C for 90 minutes has a degree of cure shrinkage of 0.18% or less.

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

[14] .

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

[14] .

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

[16] .

[18] forming an insulating layer on the inner layer substrate; a step of subjecting the insulating layer to a plasma treatment to form a recess; A method for producing a printed wiring board, wherein an insulating layer comprises a cured product of the resin composition according to any one of [1] to

[14] .

[19] The method for producing a printed wiring board according to

[18] , wherein the gas to be converted into plasma in the plasma treatment is at least one selected from the group consisting of O2, a fluorine-based gas, and an inert gas.

[20] The method for manufacturing a printed wiring board according to

[18] or

[19] , wherein the gas to be converted into plasma in the plasma treatment is a mixed gas containing O2, a fluorine-based gas, and an inert gas.

[21] The method for producing a printed wiring board according to any one of

[18] to

[20] , wherein the amount of O2 relative to 100% of the total gas amount is 1% or more and 90% or less on a sccm basis.

[22] The method for producing a printed wiring board according to any one of

[18] to

[21] , wherein the amount of fluorine-based gas relative to 100% of the total amount of gas is 5% or more and 95% or less on the basis of sccm. [Effects of the Invention]

[0010] According to the present invention, it is possible to provide a resin composition that can give a cured product having a high etching rate and excellent elongation at break, fine processability, and cure shrinkage, as well as a resin sheet, a printed wiring board, and a semiconductor device that use the resin composition. DETAILED DESCRIPTION OF THE INVENTION

[0011] The present invention will be described in detail below with reference to preferred embodiments thereof. However, the present invention is not limited to the following embodiments and examples, and can be implemented with any modifications within the scope of the claims of the present invention and their equivalents.

[0012] [Resin composition] The resin composition of the present invention contains (A) an epoxy resin, (B) a curing agent, (C) boron nitride, and (D) an inorganic filler having a thermal conductivity of 10 W / m·K or less. In the present invention, by incorporating components (A), (B), (C), and (D) in combination, a cured product having a high etching rate and excellent elongation at break, micromachinability, and cure shrinkage can be obtained. It is also usually possible to obtain a cured product having a low dielectric constant and dielectric dissipation factor, and high thermal conductivity.

[0013] The resin composition of the present invention may further contain optional components in combination with components (A) to (D). Examples of optional components include a polymer component (E), a curing accelerator (F), other additives (G), and a solvent (H). Each component contained in the resin composition of the present invention will be described in detail below.

[0014] <(A) Epoxy resin> The resin composition contains an epoxy resin (A) as component (A). By including the epoxy resin (A) in the resin composition, a cured product having excellent elongation at break and insulating reliability can be obtained. The epoxy resin (B) may be used alone or in combination of two or more.

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

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

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

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

[0019] Preferred liquid epoxy resins include biphenyl-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol AF-type epoxy resins, naphthalene-type epoxy resins, glycidyl ester-type epoxy resins, glycidyl amine-type epoxy resins, phenol novolac-type epoxy resins, alicyclic epoxy resins having an ester skeleton, cyclohexane-type epoxy resins, cyclohexane dimethanol-type epoxy resins, glycidyl amine-type epoxy resins, and epoxy resins having a butadiene structure, glycidyl cyclohexane-type epoxy resins, phenolphthalimidine-type epoxy resins, and alkyl diglycidyl ether-type epoxy resins; more preferred are biphenyl-type epoxy resins, alicyclic epoxy resins having an ester skeleton, bisphenol A-type epoxy resins, and bisphenol F-type epoxy resins; and even more preferred are bisphenol A-type epoxy resins and bisphenol F-type epoxy resins.

[0020] Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resins) manufactured by DIC Corporation; "828US", "jER828EL", "825", and "Epikote 828EL" (bisphenol A type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER807" and "1750" (bisphenol F type epoxy resins) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630" and "630LSD" (glycidyl amine type epoxy resins) manufactured by Mitsubishi Chemical Corporation; and "ZX1" manufactured by Nippon Steel Chemical & Material Co., Ltd. Examples of epoxy resins that can be used include "EX-721" (a glycidyl ester epoxy resin) manufactured by Nagase ChemteX Corporation, "Celloxide 2021P" (an alicyclic epoxy resin having an ester skeleton) manufactured by Daicel Corporation, "PB-3600" (an epoxy resin having a butadiene structure) manufactured by Daicel Corporation, "ZX1658" and "ZX1658GS" (liquid 1,4-glycidylcyclohexane epoxy resins) manufactured by Nippon Steel Chemical & Material Co., Ltd., and "YED216D" (an alkyl diglycidyl ether epoxy resin) manufactured by Mitsubishi Chemical Corporation. These may be used alone or in combination of two or more.

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

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

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

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

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

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

[0027] From the viewpoint of obtaining a cured product that exhibits good elongation at break and insulation reliability, the content of component (A) is preferably 1% by mass or more, more preferably 3% by mass or more, even more preferably 5% by mass or more, or 10% by mass or more, and is preferably 50% by mass or less, more preferably 45% by mass or less, even more preferably 40% by mass or less, 35% by mass or less, 30% by mass or less, 25% by mass or less, or 20% by mass or less, based on 100% by mass of non-volatile components in the resin composition.

[0028] From the viewpoint of obtaining a cured product exhibiting good elongation at break and insulation reliability, the content of component (A), when the resin component in the resin composition is taken as 100% by mass, is preferably 10% by mass or more, more preferably 15% by mass or more, even more preferably 20% by mass or more, 25% by mass or more, or 30% by mass or more, and is preferably 80% by mass or less, more preferably 75% by mass or less, even more preferably 70% by mass or less, 65% by mass or less, 60% by mass or less, 50% by mass or less, or 40% by mass or less.

[0029] In the present invention, unless otherwise specified, the content of each component in the resin composition is the value when the nonvolatile components in the resin composition are 100 mass %, and the nonvolatile components refer to all components constituting the resin composition other than the solvent. Furthermore, the resin components in the resin composition refer to all nonvolatile components in the resin composition excluding boron nitride and inorganic fillers with a thermal conductivity of 10 W / m K or less.

[0030] <(B) Hardener> The resin composition contains a (B) curing agent as component (B). This (B) curing agent as component (B) does not include those corresponding to the above-mentioned component (A). Component (B) usually has the function of reacting with component (A) to cure the resin composition. Component (B) may be used alone or in combination of two or more types in any ratio.

[0031] As the component (B), a compound capable of reacting with the component (A) to cure the resin composition can be used, and examples thereof include active ester curing agents, phenolic curing agents, benzoxazine curing agents, carbodiimide curing agents, acid anhydride curing agents, amine curing agents, cyanate ester curing agents, maleimide curing agents, etc. Among these, the component (A) preferably contains any one of an active ester curing agent, phenolic curing agent, cyanate ester curing agent, maleimide curing agent, and carbodiimide curing agent, more preferably any one of an active ester curing agent, phenolic curing agent, and carbodiimide curing agent, and further preferably contains an active ester curing agent from the viewpoint of further improving the elongation at break.

[0032] Examples of active ester curing agents include curing agents having one or more active ester groups per molecule. Among these, preferred active ester curing agents are compounds having two or more highly reactive ester groups per molecule, such as phenol esters, thiophenol esters, N-hydroxyamine esters, and esters of heterocyclic hydroxy compounds. The active ester curing agent is preferably one obtained by a condensation reaction between a carboxylic acid compound and / or a thiocarboxylic acid compound and a hydroxy compound and / or a thiol compound. In particular, from the viewpoint of improving heat resistance, active ester curing agents obtained from a carboxylic acid compound and a hydroxy compound are preferred, and active ester curing agents obtained from a carboxylic acid compound and a phenol compound and / or a naphthol compound are more preferred.

[0033] Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid.

[0034] Examples of phenol compounds or naphthol compounds include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalene, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucin, benzenetriol, dicyclopentadiene-type diphenol compounds, and phenol novolak. Here, "dicyclopentadiene-type diphenol compounds" refers to diphenol compounds obtained by condensing one dicyclopentadiene molecule with two phenol molecules.

[0035] Preferred specific examples of active ester curing agents include active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing an acetylated product of phenol novolac, and active ester compounds containing a benzoylated product of phenol novolac. Among these, active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred. The "dicyclopentadiene-type diphenol structure" refers to a divalent structure consisting of phenylene-dicyclopentylene-phenylene.

[0036] Commercially available active ester curing agents include, for example, "EXB9451", "EXB9460", "EXB9460S", "HPC-8000L-65TM", "HPC-8000-65T", "EXB-8000H", and "EXB-8000L-65TM" (manufactured by DIC Corporation) as active ester resins containing a dicyclopentadiene-type diphenol structure; and "EXB-9416-70BK", "EXB-8100L-65T", "HPC-8150-62T", "EXB-8150L-65T", "EXB-8100L-65T", and "EXB-8" (manufactured by DIC Corporation) as active ester curing agents containing a naphthalene structure. Examples of such curing agents include "EXB9401" (manufactured by DIC Corporation) as a phosphorus-containing active ester curing agent, "DC808" (manufactured by Mitsubishi Chemical Corporation) as an active ester curing agent containing an acetylated phenol novolac, "YLH1026," "YLH1030," and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) and "EXB-8500-65T" (manufactured by DIC Corporation) as active ester curing agents containing a benzoylated phenol novolac, and "PC1300-02-65T" and "PC1300-02-65MA" (manufactured by Air Water Inc.) as active ester curing agents containing a styryl group and a naphthalene structure.

[0037] When component (B) contains an active ester curing agent, the content (mass%) of the active ester curing agent, relative to 100 mass% of the non-volatile components in the resin composition, is preferably 1 mass% or more, more preferably 1.5 mass% or more, and even more preferably 2 mass% or more, and is preferably 30 mass% or less, more preferably 25 mass% or less, and even more preferably 20 mass% or less, or 15 mass% or less.

[0038] When component (B) contains an active ester curing agent, the content (mass%) of the active ester curing agent, when the resin component in the resin composition is taken as 100 mass%, is preferably 3 mass% or more, more preferably 10 mass% or more, even more preferably 15 mass% or more, or 20 mass% or more, and is preferably 60 mass% or less, more preferably 55 mass% or less, even more preferably 50 mass% or less, 45 mass% or less, 40 mass% or less, 35 mass% or less, or 30 mass% or less.

[0039] When component (B) contains an active ester curing agent, the content (volume %) of the active ester curing agent, based on 100 volume % of the nonvolatile components in the resin composition, is preferably 1 volume % or more, more preferably 3 volume % or more, even more preferably 4 volume % or more, or 5 volume % or more, particularly preferably 7 volume % or more, and is preferably 50 volume % or less, more preferably 40 volume % or less, even more preferably 35 volume % or less, particularly preferably 30 volume % or less.

[0040] Examples of phenolic curing agents include curing agents having one or more, preferably two or more, hydroxyl groups bonded to an aromatic ring (such as a benzene ring or a naphthalene ring) per molecule. Among these, compounds having a hydroxyl group bonded to a benzene ring are preferred. Furthermore, from the viewpoint of heat resistance and water resistance, phenolic curing agents having a novolac structure are preferred. Furthermore, from the viewpoint of adhesion, nitrogen-containing phenolic curing agents are preferred, and triazine skeleton-containing phenolic curing agents are more preferred. In particular, from the viewpoint of achieving high levels of heat resistance, water resistance, and adhesion, triazine skeleton-containing phenolic novolac curing agents are preferred.

[0041] Specific examples of phenol-based curing agents and naphthol-based curing agents include "MEH-7700," "MEH-7810," "MEH-7851," and "MEH-8000H" manufactured by Meiwa Kasei Co., Ltd.; "NHN," "CBN," and "GPH" manufactured by Nippon Kayaku Co., Ltd.; and "SN-170," "SN-180," "SN-190," "SN-475," "SN-485," "SN-495," "SN-495V," and "SN-375" manufactured by Nippon Steel Chemical & Material Co., Ltd. and "SN-395" manufactured by DIC Corporation; "TD-2090", "TD-2090-60M", "LA-7052", "LA-7054", "LA-1356", "LA-3018", "LA-3018-50P", "EXB-9500", "HPC-9500", "KA-1160", "KA-1163", and "KA-1165" manufactured by Gun-ei Chemical Co., Ltd.; and "GDP-6115L", "GDP-6115H", and "ELPC75" manufactured by Gun-ei Chemical Co., Ltd.

[0042] Specific examples of benzoxazine curing agents include "ODA-BOZ" manufactured by JFE Chemical Corporation, "HFB2006M" manufactured by Showa Polymer Co., Ltd., and "Pd" and "Fa" manufactured by Shikoku Chemicals Corporation.

[0043] Specific examples of carbodiimide curing agents include "V-03", "V-05", and "V-07" manufactured by Nisshinbo Chemical Inc.; and Stavaxol (registered trademark) P manufactured by Lanxess AG.

[0044] Examples of acid anhydride curing agents include curing agents having one or more acid anhydride groups in one molecule. Specific examples of acid anhydride curing agents include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, and benzophenone. Examples of suitable curing agents include tetracarboxylic dianhydrides, biphenyltetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,3,3a,4,5,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furanyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis(anhydrotrimellitate), and polymeric acid anhydrides such as styrene-maleic acid resins (copolymers of styrene and maleic acid). Commercially available acid anhydride curing agents are also available, such as "MH-700" manufactured by New Japan Chemical Co., Ltd.

[0045] Examples of the amine curing agent include curing agents having one or more amino groups in one molecule, such as aliphatic amines, polyether amines, alicyclic amines, and aromatic amines. Among these, aromatic amines are preferred from the viewpoint of achieving the desired effects of the present invention. The amine curing agent is preferably a primary amine or a secondary amine, and more preferably a primary amine. Specific examples of amine-based curing agents include 4,4'-methylenebis(2,6-dimethylaniline), diphenyldiaminosulfone, 4,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylsulfone, 3,3'-diaminodiphenylsulfone, m-phenylenediamine, m-xylylenediamine, diethyltoluenediamine, 4,4'-diaminodiphenyl ether, 3,3'-dimethyl-4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 3,3'-dihydroxybenzidine, and 2,2-bis(3-amino-4-hydroxybenzoyl). Examples of suitable amine curing agents include 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)propane, 3,3-dimethyl-5,5-diethyl-4,4-diphenylmethanediamine, 2,2-bis(4-aminophenyl)propane, 2,2-bis(4-(4-aminophenoxy)phenyl)propane, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 4,4'-bis(4-aminophenoxy)biphenyl, bis(4-(4-aminophenoxy)phenyl)sulfone, and bis(4-(3-aminophenoxy)phenyl)sulfone. Commercially available amine curing agents may be used, such as "KAYABOND C-200S," "KAYABOND C-100," "KAYAHARD AA," "KAYAHARD AB," and "KAYAHARD AS" manufactured by Nippon Kayaku Co., Ltd., and "Epicure W" manufactured by Mitsubishi Chemical Corporation.

[0046] Examples of cyanate ester curing agents include bifunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate, oligo(3-methylene-1,5-phenylene cyanate), 4,4'-methylenebis(2,6-dimethylphenyl cyanate), 4,4'-ethylidene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis(4-cyanate)phenylpropane, 1,1-bis(4-cyanatephenylmethane), bis(4-cyanate-3,5-dimethylphenyl)methane, 1,3-bis(4-cyanatephenyl-1-(methylethylidene))benzene, bis(4-cyanatephenyl)thioether, and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolac, cresol novolac, etc.; and prepolymers in which these cyanate resins are partially converted to triazine. Specific examples of cyanate ester curing agents include "PT30" and "PT60" manufactured by Arxada (both are phenol novolac type multifunctional cyanate ester resins); "ULL-950S" (multifunctional cyanate ester resin); "BA230" and "BA230S75" (prepolymers in which part or all of bisphenol A dicyanate has been triazine converted to a trimer); and the like.

[0047] The maleimide curing agent is a curing agent having one or more (preferably two or more) maleimide groups (2,5-dihydro-2,5-dioxo-1H-pyrrol-1-yl groups) in one molecule. Examples of maleimide-based curing agents include bismaleimide resins such as the "SLK-2000" series, "SLK-6895" (including bismaleimides such as "SLK-6895-M90"), and "SLK-3000" (all manufactured by Shin-Etsu Chemical Co., Ltd.); maleimide resins containing an indane skeleton, as described in the Japan Institute of Invention and Innovation's Disclosure Technical Bulletin No. 2020-500211; and maleimide resins containing an aromatic ring skeleton directly bonded to the nitrogen atom of the maleimide group, such as "MIR-3000-70MT" and "MIR-5000-60T" (both manufactured by Nippon Kayaku Co., Ltd.), "BMI-4000" (manufactured by Daiwa Kasei Co., Ltd.), and "BMI-80" (manufactured by Keiai Kasei Co., Ltd.).

[0048] When the number of epoxy groups in component (A) is taken as 1, the number of active groups in the (B) curing agent is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, and preferably 10 or less, more preferably 5 or less, and even more preferably 3 or less. Here, "the number of epoxy groups in component (A)" refers to the total value obtained by dividing the mass of the non-volatile components of component (A) present in the resin composition by the epoxy equivalent. Furthermore, "the number of active groups in (B) curing agent" refers to the total value obtained by dividing the mass of the non-volatile components of the (B) curing agent present in the resin composition by the active group equivalent. When the number of epoxy groups in component (A) is taken as 1, the desired effects of the present invention can be significantly achieved by having the number of active groups in the (B) curing agent within the above range.

[0049] The content of the (B) curing agent is preferably 1% by mass or more, more preferably 5% by mass or more, and even more preferably 10% by mass or more, and is preferably 40% by mass or less, more preferably 38% by mass or less, and even more preferably 30% by mass or less, or 25% by mass or less, assuming that the non-volatile components in the resin composition are 100% by mass.

[0050] The content of the (B) curing agent, when the resin component in the resin composition is taken as 100% by mass, is preferably 20% by mass or more, more preferably 25% by mass or more, even more preferably 30% by mass or more, and is preferably 70% by mass or less, more preferably 65% ​​by mass or less, even more preferably 60% by mass or less.

[0051] The content (vol %) of component (B) is preferably 10% by volume or more, more preferably 15% by volume or more, and even more preferably 20% by volume or more, and is preferably 50% by volume or less, more preferably 45% by volume or less, and even more preferably 40% by volume or less, assuming that the non-volatile components in the resin composition account for 100% by volume.

[0052] <(C) Boron nitride> The resin composition contains boron nitride (C) as component (C). By incorporating component (C) in combination with component (D), which will be described later, into the resin composition, it becomes possible to obtain a cured product with excellent micro-processability, excellent cure shrinkage, and an improved etching rate, as well as a low dielectric constant, low dielectric loss tangent, and excellent elongation at break. Component (C) is usually contained in the resin composition in the form of particles. Component (C) may be used singly or in a combination of two or more types in any ratio.

[0053] The shape of (C) boron nitride may be any of flake, spherical, plate, and fibrous. However, from the viewpoint of obtaining a cured product with a high etching rate, either flake or spherical shape is preferred, with flake shape being preferred.

[0054] When component (C) is scaly, the aspect ratio of the scaly shape is preferably at least 1, more preferably at least 2, and even more preferably at least 3, and is preferably at most 10, more preferably at most 8, and even more preferably at most 5. The aspect ratio is the ratio of the long side of the scaly boron nitride to the short side of the scaly boron nitride, and can be determined, for example, by measuring with a scanning electron microscope and calculating the average from multiple samples.

[0055] The crystal structure of (C) boron nitride may be any of hexagonal, cubic, and wurtzite types, but is preferably hexagonal from the viewpoint of obtaining a cured product with excellent thermal conductivity.

[0056] (C) Boron nitride may be in the form of thin single particles, thick single particles, or large particle size aggregated particles, but large particle size aggregated particles are preferred from the viewpoint of obtaining a cured product with excellent thermal conductivity.

[0057] (C) The thermal conductivity of boron nitride varies depending on the orientation of the boron nitride particles, but is usually 50 to 300 W / m·K.

[0058] The average particle size of (C) boron nitride is preferably 0.01 μm or more, more preferably 0.1 μm or more, particularly preferably 0.3 μm or more, and preferably 5 μm or less, more preferably 4 μm or less, particularly preferably 3 μm or less.

[0059] The average particle size can be measured using a laser diffraction / scattering method based on Mie scattering theory. Specifically, a particle size distribution based on volume is created using a laser diffraction / scattering particle size distribution analyzer, and the median diameter is used as the average particle size. A boron nitride measurement sample can be prepared by weighing 100 mg of boron nitride and 10 g of methyl ethyl ketone into a vial and dispersing the mixture ultrasonically for 10 minutes. The measurement sample is then measured using a laser diffraction particle size distribution analyzer with blue and red wavelength light sources using a flow cell system to measure the volumetric particle size distribution of boron nitride. The median diameter can then be calculated from the resulting particle size distribution to determine the average particle size. Examples of laser diffraction particle size distribution analyzers include the LA-960 manufactured by Horiba, Ltd.

[0060] (C) The BET specific surface area of ​​the boron nitride is preferably 1 m 2 / g or more, more preferably 2m 2 / g or more, particularly preferably 5m 2 / g or more, preferably 100m 2 / g or less, more preferably 50m 2 / g or less, particularly preferably 30m 2 The BET specific surface area of ​​the particles can be measured in accordance with the BET method by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) and calculating the specific surface area using the BET multipoint method.

[0061] (C) The true specific gravity of boron nitride is preferably 1 g / m 2 More preferably, 1.5 g / m 2 More preferably, 2 g / m 2 or more, preferably 5 g / m 2 Less than 4g / m, more preferably 2Less than 3 g / m, more preferably 2 The true specific gravity can be measured by the pycnometer method.

[0062] (C) boron nitride may be a commercially available product, such as "UHP-S2" manufactured by Resonac Corporation, "Spherical Nano BN" manufactured by Denka Corporation, or "BN-B" manufactured by Yingkou Corporation.

[0063] The content (mass%) of (C) boron nitride, based on 100 mass% of non-volatile components in the resin composition, is preferably 3 mass% or more, more preferably 5 mass% or more, even more preferably 10 mass% or more, 20 mass% or more, or 25 mass% or more, and is preferably 50 mass% or less, more preferably 45 mass% or less, and even more preferably 40 mass% or less.

[0064] The content (vol %) of (C) boron nitride, assuming that the non-volatile components in the resin composition are 100% by volume, is preferably 3% by volume or more, more preferably 5% by volume or more, even more preferably 7% by volume or more, particularly preferably 9% by volume or more, and is preferably 50% by volume or less, more preferably 45% by volume or less, even more preferably 40% by volume or less, particularly preferably 35% by volume or less.

[0065] The content (volume %) of (C) boron nitride, when the total amount of components (C) and (D) is taken as 100 volume %, is preferably 10 volume % or more, more preferably 15 volume % or more, even more preferably 20 volume % or more, and particularly preferably 25 volume % or more, from the viewpoint of obtaining a cured product with a high etching rate and thermal conductivity. The upper limit is preferably 95 volume % or less, more preferably 90 volume % or less, even more preferably 85 volume % or less, particularly preferably 80 volume % or less, or 75 volume % or less, from the viewpoint of obtaining a cured product with a low dielectric constant and excellent elongation at break.

[0066] When the resin composition contains an active ester curing agent as component (B), where b1 is the content (volume %) of the active ester curing agent when the non-volatile components in the resin composition are taken as 100 volume %, and c is the content (volume %) of component (C) when the non-volatile components in the resin composition are taken as 100 volume %, from the viewpoint of obtaining a cured product with a low dielectric tangent and excellent elongation at break, b1 / c is preferably 0.01 or more, more preferably 0.05 or more, even more preferably 0.1 or more, 0.15 or more, 0.2 or more, 0.25 or more, or 0.3 or more, and is preferably 10 or less, more preferably 5 or less, even more preferably 4 or less, 3 or less, or 2 or less.

[0067] <(D) Inorganic filler with thermal conductivity of 10 W / m·K or less> The resin composition contains, as component (D), an inorganic filler (D) with a thermal conductivity of 10 W / m·K or less. This inorganic filler (D) with a thermal conductivity of 10 W / m·K or less as component (D) does not include the aforementioned component (C). By incorporating component (D) in combination with component (C) into the resin composition, it becomes possible to improve the etching rate and obtain a cured product with excellent dielectric constant and elongation at break. The component (D) may be used alone, or two or more types may be combined in any ratio.

[0068] The thermal conductivity of component (D) is 10 W / m K or less, preferably 5 W / m K or less, and more preferably 2 W / m K or less. There is no particular lower limit, but it can be 0.001 W / m K or more.

[0069] Component (D) is typically contained in the resin composition in the form of particles. Component (D) is typically an inorganic compound with a thermal conductivity of 10 W / m·K or less. Examples of component (D) include silica, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate. Among these, silica is particularly preferred. Examples of silica include amorphous silica, fused silica, synthetic silica, and hollow silica. Spherical silica is preferred.

[0070] Commercially available products of component (D) include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel Chemical & Material Co., Ltd.; "YC100C," "YA050C," "YA050C-MJE," "YA010C," "SC2500SQ," "SO-C4," "SO-C2," and "SO-C1" manufactured by Admatechs Co., Ltd.; "UFP-30" and "FB-105FD" manufactured by Denka Company, Limited; "Silfil NSS-3N," "Silfil NSS-4N," and "Silfil NSS-5N" manufactured by Tokuyama Corporation; and "CellSpheres MGH-005" manufactured by Taiheiyo Cement Corporation.

[0071] The average particle size of component (D) is preferably 0.01 μm or more, more preferably 0.1 μm or more, even more preferably 0.3 μm or more, 0.4 μm or more, or 0.5 μm or more, and is preferably 10 μm or less, more preferably 5 μm or less, and even more preferably 3 μm or less. The average particle size of component (D) can be measured using the same method as that for measuring the average particle size of component (C).

[0072] The BET specific surface area of ​​component (D) is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, preferably 100m 2 / g or less, more preferably 70m 2 / g or less, more preferably 40m 2 The specific surface area of ​​component (D) can be measured in accordance with the BET method by adsorbing nitrogen gas onto the surface of a sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) and calculating the specific surface area using the BET multipoint method.

[0073] From the viewpoint of improving moisture resistance and dispersibility, component (D) is preferably treated with a surface treatment agent. Examples of surface treatment agents include fluorine-containing silane coupling agents, aminosilane coupling agents, epoxysilane coupling agents, mercaptosilane coupling agents, silane coupling agents, alkoxysilanes, organosilazane compounds, and titanate coupling agents. One type of surface treatment agent may be used alone, or two or more types may be used in any combination.

[0074] Examples of commercially available surface treatment agents include Shin-Etsu Chemical Co., Ltd.'s "KBM403" (3-glycidoxypropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM803" (3-mercaptopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBE903" (3-aminopropyltriethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM573" (N-phenyl-3-aminopropyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "SZ-31" (hexamethyldisilazane), Shin-Etsu Chemical Co., Ltd.'s "KBM103" (phenyltrimethoxysilane), Shin-Etsu Chemical Co., Ltd.'s "KBM-4803" (long-chain epoxy-type silane coupling agent), and Shin-Etsu Chemical Co., Ltd.'s "KBM-7103" (3,3,3-trifluoropropyltrimethoxysilane).

[0075] The degree of surface treatment with the surface treatment agent preferably falls within a specific range from the viewpoint of improving the dispersibility of the inorganic filler. Specifically, 100% by mass of the inorganic filler is preferably surface-treated with 0.2% to 5% by mass of the surface treatment agent, more preferably with 0.2% to 3% by mass of the surface treatment agent, and even more preferably with 0.3% to 2% by mass of the surface treatment agent.

[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 composition, it is more preferable that the content be 1.0 mg / m 2 Less than 0.8 mg / m is preferred 2 Less than 0.5 mg / m is more preferable. 2 The following is even more preferred:

[0077] The carbon content per unit surface area of ​​component (D) 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. The supernatant is removed, the solid content is dried, and then the carbon content per unit surface area of ​​the inorganic filler can be measured using a carbon analyzer. An "EMIA-320V" manufactured by Horiba, Ltd., or the like can be used as the carbon analyzer.

[0078] The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit mass of component (D). The amount of carbon per unit mass of component (D) is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, and even more preferably 0.1% by mass or more, and is preferably 1.0% by mass or less, more preferably 0.8% by mass or less, and even more preferably 0.5% by mass or less. The amount of carbon per unit mass of component (D) can be measured using a carbon analyzer, just like the amount of carbon per unit surface area of ​​component (D).

[0079] To achieve the most significant effects of the present invention, the components (C) and (D) are preferably combined so that the thermal conductivity of the cured resin composition is less than 12 W / m·K, more preferably 5 W / m·K or less. The thermal conductivity of the cured resin composition obtained by thermally curing the resin composition at 200°C for 90 minutes is preferably less than 12 W / m·K, more preferably 10 W / m·K or less, even more preferably 8 W / m·K or less, 5 W / m·K or less, less than 5 W / m·K, or 3 W / m·K or less. There is no particular lower limit, but the lower limit is preferably 0.6 W / m·K or more, more preferably 0.8 W / m·K or more, and even more preferably 1 W / m·K or more. Thermal conductivity can be measured by the method described in the Examples below.

[0080] The content (mass %) of component (D) is preferably 5 mass % or more, more preferably 10 mass % or more, even more preferably 15 mass % or more, 20 mass % or more, or 25 mass % or more, and is preferably 60 mass % or less, more preferably 55 mass % or less, and even more preferably 50 mass % or less, assuming that the non-volatile components in the resin composition are 100 mass %.

[0081] The content (vol %) of component (D) is preferably 1 vol % or more, more preferably 3 vol % or more, even more preferably 5 vol % or more, particularly preferably 7 vol % or more, or 9 vol % or more, and is preferably 60 vol % or less, more preferably 50 vol % or less, even more preferably 40 vol % or less, particularly preferably 30 vol % or less, assuming that the non-volatile components in the resin composition are 100 vol %.

[0082] The content (vol %) of component (D), when the total amount of components (C) and (D) is taken as 100% by volume, is preferably 90% by volume or less, more preferably 88% by volume or less, even more preferably 86% by volume or less, and particularly preferably 80% by volume or less, and is preferably 12% by volume or more, more preferably 14% by volume or more, and even more preferably 16% by volume or more.

[0083] The total content (mass%) of components (C) and (D) is preferably 5% by mass or more, more preferably 10% by mass or more, even more preferably 20% by mass or more, 30% by mass or more, 40% by mass or more, or 50% by mass or more, based on 100% by mass of the nonvolatile components in the resin composition. From the viewpoint of obtaining a cured product with a high etching rate, a low dielectric constant, and excellent elongation at break, the upper limit is preferably 85% by mass or less, more preferably 80% by mass or less, even more preferably 75% by mass or less, and particularly preferably 70% by mass or less or 65% by mass or less.

[0084] The total volume of the components (C) and (D) is preferably 10% by volume or more, more preferably 20% by volume or more, even more preferably 30% by volume or more, and particularly preferably 35% by volume or more, based on 100% by volume of the nonvolatile components in the resin composition. From the viewpoint of obtaining a cured product with a high etching rate, a low dielectric constant, and excellent elongation at break, the upper limit is preferably 80% by volume or less, more preferably 70% by volume or less, even more preferably 60% by volume or less, and particularly preferably 55% by volume or less, or 50% by volume or less.

[0085] The ratio of the content (% by mass) of the (D) component when the nonvolatile components in the resin composition are taken as 100% by mass to the content (% by mass) of the (C) component when the nonvolatile components in the resin composition are taken as 100% by mass (content of the (C) component / content of the (D) component) is preferably 0.1 or more, more preferably 0.2 or more, even more preferably 0.5 or more, or 1 or more, and is preferably 8 or less, more preferably 6 or less, even more preferably 3 or less.

[0086] When the content (volume %) of component (D) is defined as d and the content (volume %) of component (C) is defined as c when the nonvolatile components in the resin composition are taken as 100% by volume, c / d is preferably 0.05 or more, more preferably 0.15 or more, even more preferably 0.25 or more, particularly preferably 0.5 or more, or 1.0 or more, and is preferably 8 or less, more preferably 6 or less, and even more preferably 3 or less.

[0087] <(E) Polymer component> The resin composition may contain a polymer component (E) as the component (E). The polymer component (E) as the component (E) does not include components (A) to (D) described above. The polymer component (E) may be used alone or in combination of two or more.

[0088] Component (E) can be one having a high weight-average molecular weight, such as polyimide resin, phenoxy resin, polyimide resin, polyvinyl acetal resin, polyolefin resin, polybutadiene resin, polyamideimide resin, polyetherimide resin, polysulfone resin, polyethersulfone resin, polyphenylene ether resin, polycarbonate resin, polyetheretherketone resin, polyester resin, etc.

[0089] The weight average molecular weight (Mw) of component (E) is preferably greater than 5,000, more preferably 8,000 or more, even more preferably 10,000 or more, and particularly preferably 20,000 or more; and is preferably 100,000 or less, more preferably 70,000 or less, even more preferably 60,000 or less, and particularly preferably 50,000 or less.

[0090] The polyimide resin (E) may be a resin having an imide bond in the repeating unit, and preferably has an ester bond in order to increase the glass transition temperature of the cured product. Polyimide resins generally include those obtained by the imidization reaction of a diamine compound with an acid anhydride.

[0091] The diamine compound for preparing the polyimide resin is not particularly limited, but examples thereof include aliphatic diamine compounds and aromatic diamine compounds. Among them, aromatic diamine compounds are preferred as the diamine compound. From the viewpoint of increasing the glass transition temperature of the cured product, the diamine compound preferably has an ester bond, and more preferably an aromatic diamine compound having an ester bond.

[0092] Examples of the aliphatic diamine compound include linear aliphatic diamine compounds such as 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexamethylenediamine, 1,5-diaminopentane, and 1,10-diaminodecane; branched aliphatic diamine compounds such as 1,2-diamino-2-methylpropane, 2,3-diamino-2,3-butane, and 2-methyl-1,5-diaminopentane; alicyclic diamine compounds such as 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,4-diaminocyclohexane, and 4,4′-methylenebis(cyclohexylamine); and dimer acid diamines (hereinafter also referred to as “dimer diamines”), with dimer acid diamines being preferred.

[0093] Dimer acid diamines refer to diamine compounds obtained by substituting the two terminal carboxylic acid groups (—COOH) of a dimer acid with aminomethyl groups (—CH—NH) or amino groups (—NH). Dimer acids are known compounds obtained by dimerizing unsaturated fatty acids (preferably those with 11 to 22 carbon atoms, particularly preferably those with 18 carbon atoms), and their industrial production processes are largely standardized in the industry. Dimer acids are particularly readily available, primarily consisting of 36-carbon dimer acids obtained by dimerizing 18-carbon unsaturated fatty acids such as oleic acid and linoleic acid, which are inexpensive and readily available. Depending on the production method, degree of purification, and other factors, dimer acids may contain arbitrary amounts of monomer acids, trimer acids, other polymerized fatty acids, and the like. Although double bonds remain after the polymerization reaction of unsaturated fatty acids, in this specification, hydrogenated products obtained by further hydrogenation to reduce the degree of unsaturation are also included in the term dimer acids. Dimer acid type diamines are commercially available, for example, "PRIAMINE 1073," "PRIAMINE 1074," and "PRIAMINE 1075" manufactured by Croda Japan; "VERSAMINE 551" and "VERSAMINE 552" manufactured by Cognis Japan; and the like.

[0094] Examples of the aromatic diamine compound include phenylenediamine compounds, naphthalenediamine compounds, and dianiline compounds, with dianiline compounds being preferred.

[0095] The phenylenediamine compound refers to a compound consisting of a benzene ring having two amino groups, and further, the benzene ring here may have any of 1 to 3 substituents. Specific examples of the phenylenediamine compound include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, 3,5-diaminobiphenyl, and 2,4,5,6-tetrafluoro-1,3-phenylenediamine.

[0096] The substituent is not particularly limited, and examples thereof include a halogen atom, -OH, and -OC. 1-6An alkyl group, -N(C 1-10 alkyl group)2, C 1-20 alkyl group, C 2-30 alkenyl group, C 2-30 alkynyl group, C 6-10 aryl group, -NH2, -CN, -C(O)O-C 1-10 alkyl group, -COOH, -C(O)H, -NO2, etc. are exemplified. Here, the term "C p-q " (p and q are positive integers and p < q is satisfied.) represents that the number of carbon atoms of the organic group described immediately after this term is p to q. For example, the expression "C 1-10 alkyl group" indicates an alkyl group having 1 to 10 carbon atoms. These substituents may be bonded to each other to form a ring, and the ring structure includes spiro rings and condensed rings.

[0097] A naphthalenediamine compound means a compound composed of a naphthalene ring having two amino groups, and further, the naphthalene ring here may optionally have 1 to 3 substituents. The substituents are the same as those that a phenylenediamine compound may have. Specific examples of the naphthalenediamine compound include 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, 2,3-diaminonaphthalene, etc.

[0098] A dianiline compound means a compound containing two aniline structures in the molecule, and further, the two benzene rings in the two aniline structures may each optionally have 1 to 3 substituents. The substituents are the same as those that a phenylenediamine compound may have. The two aniline structures in the dianiline compound may be bonded directly and / or via one or two linker structures having 1 to 100 backbone atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms. The dianiline compound includes those in which the two aniline structures are bonded by two bonds.

[0099] Specific examples of the "linker structure" in the dianiline compound include -NHCO-, -CONH-, -OCO-, -COO-, -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH(CH3)-, -C(CH3)2-, -C(CF3)2-, -CH=CH-, -O-, -S-, -CO-, -SO2-, -NH-, -Ph-, -Ph-Ph-, - Examples of such alkyl groups include C(CH3)2-Ph-C(CH3)2-, -O-Ph-O-, -O-Ph-Ph-O-, -O-Ph-SO2-Ph-O-, -O-Ph-C(CH3)2-Ph-O-, -Ph-CO-O-Ph-, -C(CH3)2-Ph-C(CH3)2-, -Ph-O-Ph-CH(CH3)2-Ph-CH(CH3)2-Ph-O-Ph-, groups represented by the following formulas (I) and (II), and groups consisting of combinations thereof. In this specification, "Ph" represents a 1,4-phenylene group, a 1,3-phenylene group, or a 1,2-phenylene group. Among these, the linker structure is preferably -COO-, -Ph-CO-O-Ph-, or -Ph-O-Ph-CH(CH3)2-Ph-CH(CH3)2-Ph-O-Ph-.

[0100] [ka]

[0101] In one embodiment, the diamine compound is preferably a diamine compound represented by the following formula (E-1). [ka] (In formula (E-1), R 1 ~R 8 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X 9 -R 9 , or -X 10 -R 10 indicates R 1 ~R 8 At least one of the -X 10 -R 10 and X 9are each independently a single bond, -NR 9’ -, -O-, -S-, -CO-, -SO2-, -NR 9’ CO-, -CONR 9’ -, -OCO-, or -COO-, and R 9 each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group, R 9’ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group; X 10 each independently represents a single bond, -(substituted or unsubstituted alkylene group), -NH-, -O-, -S-, -CO-, -SO2-, -NHCO-, -CONH-, -OCO-, or -COO-; R 10 each independently represents a substituted or unsubstituted aryl group, or a substituted or unsubstituted heteroaryl group.

[0102] R in formula (E-1) 9 and R 9’ The alkyl group represented by the formula (I) refers to a linear, branched, or cyclic monovalent aliphatic saturated hydrocarbon group. As the alkyl group, an alkyl group having 1 to 6 carbon atoms is preferred, and an alkyl group having 1 to 3 carbon atoms is more preferred. Examples of such alkyl groups include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group, a cyclopentyl group, and a cyclohexyl group.

[0103] R in formula (E-1) 9 and R 9’The alkenyl group represented by the formula (I) refers to a linear, branched, or cyclic monovalent unsaturated hydrocarbon group having at least one carbon-carbon double bond. The alkenyl group is preferably an alkenyl group having 2 to 6 carbon atoms, and more preferably an alkenyl group having 2 or 3 carbon atoms. Examples of such alkenyl groups include vinyl, 1-propenyl, 2-propenyl, 2-methyl-1-propenyl, 1-butenyl, 2-butenyl, 3-butenyl, 3-methyl-2-butenyl, 1-pentenyl, 2-pentenyl, 3-pentenyl, 4-pentenyl, 4-methyl-3-pentenyl, 1-hexenyl, 3-hexenyl, 5-hexenyl, and 2-cyclohexenyl. The substituent of the alkenyl group in the "substituted or unsubstituted alkenyl group" is not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkoxy group, an aryl group, a heteroaryl group, an amino group, a nitro group, a hydroxy group, a carboxy group, a sulfo group, etc. The number of substituents is preferably 1 to 3, and more preferably 1.

[0104] The substituent of the alkyl group in the "substituted or unsubstituted alkyl group" and the substituent of the alkenyl group in the "substituted or unsubstituted alkenyl group" are not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkoxy group, an amino group, a nitro group, a hydroxy group, a carboxy group, a sulfo group, etc. The number of substituents is preferably 1 to 3, and more preferably 1.

[0105] An alkoxy group refers to a monovalent group (alkyl-O-) formed by bonding an alkyl group to an oxygen atom. As the alkoxy group, an alkoxy group having 1 to 6 carbon atoms is preferable, and an alkoxy group having 1 to 3 carbon atoms is more preferable. Examples of such alkoxy groups include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, and a pentyloxy group.

[0106] X in formula (E-1) 10The alkylene group represented by refers to a straight-chain, branched-chain, or cyclic divalent aliphatic saturated hydrocarbon group, preferably an alkylene group having 1 to 6 carbon atoms, and more preferably an alkylene group having 1 to 3 carbon atoms. Examples of the alkylene group include -CH-, -CH-CH-, -CH(CH)-, -CH-CH-CH-, -CH-CH(CH)-, -CH(CH)-CH-, -C(CH)-, -CH-CH-CH-CH-, -CH-CH-CH(CH)-, -CH-CH(CH)-CH-, -CH(CH)-CH-CH-, -CH-C(CH)-, and -C(CH)-CH-. The substituent of the alkylene group in the "substituted or unsubstituted alkylene group" is not particularly limited, and examples thereof include a halogen atom, a cyano group, an alkoxy group, an aryl group, a heteroaryl group, an amino group, a nitro group, a hydroxy group, a carboxy group, a sulfo group, etc. The number of substituents is preferably 1 to 3, and more preferably 1.

[0107] R in formula (E-1) 10 The aryl group represented by is preferably an aryl group having 6 to 14 carbon atoms, more preferably an aryl group having 6 to 10 carbon atoms. Examples of such aryl groups include a phenyl group, a 1-naphthyl group, and a 2-naphthyl group, and preferably a phenyl group. The substituent of the aryl group in the "substituted or unsubstituted aryl group" is not particularly limited, and examples include a halogen atom, a cyano group, an alkyl group, an alkoxy group, an aryl group, a heteroaryl group, an amino group, a nitro group, a hydroxy group, a carboxy group, and a sulfo group. The number of substituents is preferably 1 to 3, and more preferably 1.

[0108] R in formula (E-1) 10The heteroaryl group represented by the formula (I) is an aromatic heterocyclic group having 1 to 4 heteroatoms selected from an oxygen atom, a nitrogen atom, and a sulfur atom. The heteroaryl group is preferably a 5- to 12-membered (preferably 5- or 6-membered) monocyclic, bicyclic, or tricyclic (preferably monocyclic) aromatic heterocyclic group. Examples of such heteroaryl groups include a furyl group, a thienyl group, a pyrrolyl group, an oxazolyl group, an isoxazolyl group, a thiazolyl group, an isothiazolyl group, an imidazolyl group, a pyrazolyl group, a 1,2,3-oxadiazolyl group, a 1,2,4-oxadiazolyl group, a 1,3,4-oxadiazolyl group, a furazanyl group, a 1,2,3-thiadiazolyl group, a 1,2,4-thiadiazolyl group, a 1,3,4-thiadiazolyl group, a 1,2,3-triazolyl group, a 1,2,4-triazolyl group, a tetrazolyl group, a pyridyl group, a pyridazinyl group, a pyrimidinyl group, a pyrazinyl group, a triazinyl group, etc. Substituents of the heteroaryl group in the "substituted or unsubstituted heteroaryl group" are the same as the substituents of the aryl group in the "substituted or unsubstituted aryl group".

[0109] R 1 ~R 8 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X 9 -R 9 , or -X 10 -R 10 Indicates R 1 ~R 8 are preferably each independently a hydrogen atom or -X 10 -R 10 is.

[0110] R 1 ~R 8 At least one of the -X 10 -R 10 Preferably, R 1 ~R 8 One or two of them are -X 10 -R 10 and more preferably, R 5 ~R 8 One or two of them are -X 10 -R 10and more preferably, R 5 and R 7 One or two of them are -X 10 -R 10 is.

[0111] In one embodiment, preferably, R 1 ~R 8 One or two of them are -X 10 -R 10 and R 1 ~R 8 The other is a hydrogen atom, and more preferably, R 5 ~R 8 One or two of them are -X 10 -R 10 and R 1 ~R 8 The other is a hydrogen atom, and more preferably, R 5 and R 7 One or two of them are -X 10 -R 10 and R 1 ~R 8 The rest are hydrogen atoms.

[0112] X 9 are each independently a single bond, -NR 9’ -, -O-, -S-, -CO-, -SO2-, -NR 9’ CO-, -CONR 9’ -, -OCO-, or -COO-. R 9 X each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group. 9 is preferably a single bond.

[0113] R 9’ R each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group. 9 is preferably a substituted or unsubstituted alkyl group.

[0114] X 10X each independently represents a single bond, -(substituted or unsubstituted alkylene group), -NH-, -O-, -S-, -CO-, -SO2-, -NHCO-, -CONH-, -OCO-, or -COO-. 10 is preferably a single bond.

[0115] R 10 R each independently represents a substituted or unsubstituted aryl group or a substituted or unsubstituted heteroaryl group. 10 is preferably a substituted or unsubstituted aryl group.

[0116] In one embodiment, the diamine compound represented by formula (E-1) is preferably a compound represented by formula (E-2) below, and more preferably a compound represented by formula (E-3) below (4-aminobenzoic acid 5-amino-1,1'-biphenyl-2-yl(5-amino-2-biphenyl)-4-aminobenzoate: PHBAAB). [ka] (In the formula, R 1 ~R 6 and R 8 are each independently a hydrogen atom, a halogen atom, a cyano group, a nitro group, -X 9 -R 9 and the other symbols are the same as in formula (E-1). [ka]

[0117] In another embodiment, the diamine compound is specifically 4,4'-diamino-2,2'-ditrifluoromethyl-1,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl 4-aminobenzoate, 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy) Benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)propane, 4,4'-(hexafluoroisopropylidene)dianiline, 2,2-bis[4-(4-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]hexafluoropropane, α,α-bis[4-(4-aminophenoxy)phenyl]-1,3-diisopropylbenzene, α,α-bis[4-(4-aminophenoxy)phenyl]-1,4- Diisopropylbenzene, 4,4'-(9-fluorenylidene)dianiline, 2,2-bis(3-methyl-4-aminophenyl)propane, 2,2-bis(3-methyl-4-aminophenyl)benzene, 4,4'-diamino-3,3'-dimethyl-1,1'-biphenyl, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis(3-methyl-4-aminophenyl)fluorene, 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl] 4,4'-(m-phenylenediisopropylidene)dianiline (Bisaniline-M), 4,4'-[1,4-phenylenebis[(1-methylethylidene)-4,1-phenyleneoxy]]bisbenzenamine (BPPAN), and the like. Of these, 4,4'-(m-phenylenediisopropylidene)dianiline and 4,4'-[1,4-phenylenebis[(1-methylethylidene)-4,1-phenyleneoxy]]bisbenzenamine are preferred.Note that 4,4'-(m-phenylenediisopropylidene)dianiline (Bisaniline-M; a compound represented by the following formula (I)) and 4,4'-[1,4-phenylenebis[(1-methylethylidene)-4,1-phenyleneoxy]]bisbenzenamine (BPPAN; a compound represented by the following formula (II)) are compounds represented by the following formula: [ka]

[0118] The diamine compound may be a commercially available product or may be synthesized by a known method. For example, the diamine compound represented by formula (E-1) can be synthesized by the synthesis method described in Japanese Patent No. 6240798 or a method equivalent thereto. The diamine compound may be used alone or in combination of two or more.

[0119] The acid anhydride used to prepare the polyimide resin is not particularly limited, but in a preferred embodiment, it is an aromatic tetracarboxylic dianhydride, such as benzenetetracarboxylic dianhydride, naphthalenetetracarboxylic dianhydride, anthracenetetracarboxylic dianhydride, or diphthalic dianhydride, preferably diphthalic dianhydride.

[0120] Benzenetetracarboxylic dianhydride means a dianhydride of benzene having four carboxy groups, and further, the benzene ring here may have 1 to 3 optional substituents, such as a halogen atom, a cyano group, and -X 13 -R 13 (The same definition as in the following formula (E-4)) Specific examples of the benzenetetracarboxylic dianhydride include pyromellitic dianhydride and 1,2,3,4-benzenetetracarboxylic dianhydride.

[0121] Naphthalenetetracarboxylic dianhydride refers to a dianhydride of naphthalene having four carboxy groups, and the naphthalene ring here may optionally have 1 to 3 substituents, such as halogen atoms, cyano groups, and -X 13 -R 13 (The same definition as in formula (E-4) below.) Specific examples of naphthalenetetracarboxylic dianhydride include 1,4,5,8-naphthalenetetracarboxylic dianhydride and 2,3,6,7-naphthalenetetracarboxylic dianhydride.

[0122] Anthracenetetracarboxylic dianhydride refers to a dianhydride of anthracene having four carboxy groups, and the anthracene ring here may optionally have 1 to 3 substituents, such as halogen atoms, cyano groups, and -X 13 -R 13 (The same definition as in the following formula (E-4)) is preferred. Specific examples of the anthracenetetracarboxylic dianhydride include 2,3,6,7-anthracenetetracarboxylic dianhydride.

[0123] Diphthalic dianhydride refers to a compound containing two phthalic anhydrides in the molecule, and each of the two benzene rings in the two phthalic anhydrides may have one to three optional substituents. The substituents include halogen atoms, cyano groups, and -X 13 -R 13 (the same as the definition of formula (E-4) below). The two phthalic anhydrides in the diphthalic dianhydride may be bonded to each other by a direct bond or via a linker structure having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms.

[0124] An example of the diphthalic dianhydride is a compound represented by formula (E-4). [ka] (In the formula, R 11 and R12 are each independently a halogen atom, a cyano group, a nitro group, or -X 13 -R 13 indicates, X 13 are each independently a single bond, -NR 13’ -, -O-, -S-, -CO-, -SO2-, -NR 13’ CO-, -CONR 13’ -, -OCO-, or -COO-; R 13 each independently represents a substituted or unsubstituted alkyl group or a substituted or unsubstituted alkenyl group, R 13’ each independently represents a hydrogen atom, a substituted or unsubstituted alkyl group, or a substituted or unsubstituted alkenyl group, Y represents a single bond or a linker structure having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms; n1 and m1 each independently represent an integer of 0 to 3.

[0125] Y is preferably a linker structure having 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms. n1 and m1 are preferably 0.

[0126] The "linker structure" in Y has 1 to 100 skeletal atoms selected from carbon atoms, oxygen atoms, sulfur atoms, and nitrogen atoms. The "linker structure" is preferably -[A-Ph] a -A-[Ph-A] b - (wherein each A independently represents a single bond, -(substituted or unsubstituted alkylene group)-, -O-, -S-, -CO-, -SO2-, -CONH-, -NHCO-, -COO-, or -OCO-, and each a and b independently represents an integer of 0 to 2 (preferably 0 or 1).)

[0127] Specific examples of the "linker structure" for Y include -CH2-, -CH2CH2-, -CH2CH2CH2-, -CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH2CH2CH2CH2CH2-, -CH(CH3)-, -C(CH3)2-, -O-, -CO-, -SO2-, -Ph-, -O-Ph-O-, -O-Ph-SO2-Ph-O-, -O-Ph-C(CH3)2-Ph-O-, etc., with -O-Ph-C(CH3)2-Ph-O- being preferred.

[0128] Specific examples of diphthalic dianhydrides include 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-diphenylethertetracarboxylic dianhydride, 2,3,3',4'-diphenylsulfonetetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, methylene-4,4'-diphthalic dianhydride, and 1,1-ethynylidene-4,4'-diphthalic dianhydride. , 2,2-propylidene-4,4'-diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 1,3-bis(3,4-dicarboxyphenyl)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenyl) Examples include benzene dianhydride, 1,3-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 1,4-bis(3,4-dicarboxyphenoxy)benzene dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, and 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic dianhydride (BPADA).

[0129] In one embodiment, the diphthalic acid compound represented by formula (E-4) is preferably a compound represented by formula (E-5) below, and more preferably a compound represented by formula (E-6) below (4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic dianhydride: BPADA). [ka] (In the formula, R 11 and R 12 are each independently a halogen atom, a cyano group, a nitro group, or -X 13 -R 13 wherein n1 and m1 each independently represent an integer of 0 to 3, and other symbols are the same as in formula (E-4). [ka]

[0130] The aromatic tetracarboxylic dianhydride may be a commercially available product, or may be synthesized by a known method or a method similar thereto. The aromatic tetracarboxylic dianhydride may be used alone or in combination of two or more.

[0131] In one embodiment, the acid anhydride for preparing the polyimide resin may include other acid anhydrides in addition to the aromatic tetracarboxylic dianhydride.

[0132] Specific examples of other acid anhydrides include aliphatic tetracarboxylic acid dianhydrides such as 1,2,3,4-cyclobutanetetracarboxylic acid dianhydride, cyclopentanetetracarboxylic acid dianhydride, cyclohexane-1,2,3,4-tetracarboxylic acid dianhydride, cyclohexane-1,2,4,5-tetracarboxylic acid dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic acid dianhydride, carbonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, thio-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, and sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride.

[0133] The content of structures derived from aromatic tetracarboxylic dianhydrides in all structures derived from acid anhydrides constituting the polyimide resin is preferably 10 mol% or more, more preferably 30 mol% or more, even more preferably 50 mol% or more, still more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 100 mol%.

[0134] The polyimide resin preferably has a structural unit represented by the following general formula (E). [ka] In the formula, R 51 represents a single bond or a residue derived from an acid anhydride, and R 52 represents a single bond or a residue derived from a diamine compound.

[0135] R 51 represents a single bond or a residue derived from an acid anhydride, and is preferably a residue derived from an acid anhydride. 51The residue derived from an acid anhydride represented by the formula (I) refers to a divalent group obtained by removing two oxygen atoms from an acid anhydride. The acid anhydride is as described above.

[0136] R 52 represents a single bond or a residue derived from a diamine compound, and is preferably a residue derived from a diamine compound. 52 The residue derived from a diamine compound represented by the formula (I) refers to a divalent group obtained by removing two amino groups from a diamine compound. The diamine compound is as described above.

[0137] The polyimide resin as component (E) can be prepared by a conventionally known method. For example, a method of heating a mixture of a diamine compound, an acid anhydride, and a solvent to cause the mixture to react is exemplified. The amount of the diamine compound added is typically 0.5 to 1.5 molar equivalents, preferably 0.9 to 1.1 molar equivalents, relative to the acid anhydride.

[0138] Examples of solvents used in preparing the polyimide resin (component E) include amide-based solvents such as N,N-dimethylacetamide, N,N-diethylacetamide, N,N-dimethylformamide, and N-methyl-2-pyrrolidone; ketone-based solvents such as acetone, methyl ethyl ketone (MEK), and cyclohexanone; ester-based solvents such as γ-butyrolactone; and hydrocarbon-based solvents such as cyclohexane and methylcyclohexane. Furthermore, in preparing the polyimide resin, an imidization catalyst, an azeotropic dehydrating solvent, an acid catalyst, and the like may be used as needed. Examples of imidization catalysts include tertiary amines such as triethylamine, triisopropylamine, triethylenediamine, N-methylpyrrolidine, N-ethylpyrrolidine, N,N-dimethyl-4-aminopyridine, and pyridine. Examples of azeotropic dehydrating solvents include toluene, xylene, and ethylcyclohexane. Examples of acid catalysts include acetic anhydride. The amounts of the imidization catalyst, azeotropic dehydrating solvent, acid catalyst, and the like can be appropriately determined by those skilled in the art. The reaction temperature for preparing the polyimide resin is usually 100 to 250°C.

[0139] Examples of phenoxy resins include phenoxy resins having one or more skeletons selected from the group consisting of bisphenol A, bisphenol F, bisphenol S, bisphenolacetophenone, novolac, biphenyl, fluorene, dicyclopentadiene, norbornene, naphthalene, anthracene, adamantane, terpene, and trimethylcyclohexane. 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" manufactured by Mitsubishi Chemical Corporation (both of which are phenoxy resins containing a bisphenol A skeleton); "YX8100" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol S skeleton); "YX6954" manufactured by Mitsubishi Chemical Corporation (phenoxy resin containing a bisphenol acetophenone skeleton); "FX280" and "FX293" manufactured by Nippon Steel & Sumikin Chemical Co., Ltd.; and "YL7500BH30," "YX6954BH30," "YX7553," "YX7553BH30," "YL7769BH30," "YL6794," "YL7213," "YL7290," "YL7482," and "YL7891BH30" manufactured by Mitsubishi Chemical Corporation.

[0140] Examples of polyvinyl acetal resins include polyvinyl formal resins and polyvinyl butyral resins, with polyvinyl butyral resins being preferred. Specific examples of polyvinyl acetal resins include S-LEC BH series, BX series (e.g., BX-5Z), KS series (e.g., KS-1), BL series, and BM series manufactured by Sekisui Chemical Co., Ltd.

[0141] Examples of polyolefin resins include ethylene copolymer resins such as low-density polyethylene, very low-density polyethylene, high-density polyethylene, ethylene-vinyl acetate copolymer, ethylene-ethyl acrylate copolymer, and ethylene-methyl acrylate copolymer; and polyolefin polymers such as polypropylene and ethylene-propylene block copolymer.

[0142] Examples of polybutadiene resins include hydrogenated polybutadiene skeleton-containing resins, hydroxy group-containing polybutadiene resins, phenolic hydroxy group-containing polybutadiene resins, carboxy group-containing polybutadiene resins, acid anhydride group-containing polybutadiene resins, epoxy group-containing polybutadiene resins, isocyanate group-containing polybutadiene resins, urethane group-containing polybutadiene resins, and polyphenylene ether-polybutadiene resins.

[0143] Specific examples of polyamide-imide resins include "Vylomax HR11NN" and "Vylomax HR16NN" manufactured by Toyobo Co., Ltd. Specific examples of polyamide-imide resins also include modified polyamide-imides such as "KS9100" and "KS9300" (polysiloxane skeleton-containing polyamide-imides) manufactured by Resonac Corporation.

[0144] A specific example of the polyethersulfone resin is "PES5003P" manufactured by Sumitomo Chemical Co., Ltd.

[0145] Specific examples of polysulfone resins include polysulfones "P1700" and "P3500" manufactured by Solvay Advanced Polymers.

[0146] A specific example of the polyphenylene ether resin is NORYL SA90 manufactured by SABIC, etc. A specific example of the polyetherimide resin is ULTEM manufactured by GE, etc.

[0147] Examples of polycarbonate resins include hydroxyl group-containing carbonate resins, phenolic hydroxyl group-containing carbonate resins, carboxyl group-containing carbonate resins, acid anhydride group-containing carbonate resins, isocyanate group-containing carbonate resins, and urethane group-containing carbonate resins. Specific examples of polycarbonate resins include "FPC0220" manufactured by Mitsubishi Gas Chemical Company, Inc., "T6002" and "T6001" (polycarbonate diols) manufactured by Asahi Kasei Corporation, and "C-1090," "C-2090," and "C-3090" (polycarbonate diols) manufactured by Kuraray Co., Ltd. Specific examples of polyether ether ketone resins include "Sumiploy K" manufactured by Sumitomo Chemical Co., Ltd.

[0148] Examples of polyester resins include polyethylene terephthalate resin, polyethylene naphthalate resin, polybutylene terephthalate resin, polybutylene naphthalate resin, polytrimethylene terephthalate resin, polytrimethylene naphthalate resin, and polycyclohexane dimethyl terephthalate resin.

[0149] The content of component (E) is preferably 0.1% by mass or more, more preferably 1% by mass or more, and even more preferably 1.5% by mass or more, and is preferably 10% by mass or less, more preferably 8% by mass or less, and even more preferably 5% by mass or less, assuming that the non-volatile components in the resin composition are 100% by mass.

[0150] The content of component (E) is preferably 0.5% by mass or more, more preferably 1% by mass or more, and even more preferably 3% by mass or more, and is preferably 20% by mass or less, more preferably 15% by mass or less, and even more preferably 13% by mass or less, or 10% by mass or less, when the resin component in the resin composition is taken as 100% by mass.

[0151] <(F) Curing accelerator> The resin composition may contain a (F) curing accelerator as an optional component. The (F) curing accelerator as component (F) excludes those corresponding to components (A) to (E). Examples of the (F) curing accelerator include phosphorus-based curing accelerators, amine-based curing accelerators, imidazole-based curing accelerators, guanidine-based curing accelerators, and metal-based curing accelerators. Amine-based curing accelerators, imidazole-based curing accelerators, and metal-based curing accelerators are preferred, and either amine-based curing accelerators or imidazole-based curing accelerators are more preferred. One type of curing accelerator may be used alone, or two or more types may be used in combination.

[0152] Examples of phosphorus-based curing accelerators include triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate, with triphenylphosphine and tetrabutylphosphonium decanoate being preferred.

[0153] 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.

[0154] 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-undecylimidazole, 1-cyanoethyl-2-phenylimidazolium 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-phenyl-4,5-dihydroxymethylimidazole, Examples of the imidazole compound include imidazole compounds such as 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, as well as adducts of imidazole compounds with epoxy resins, and 2-ethyl-4-methylimidazole and 1-benzyl-2-phenylimidazole are preferred.

[0155] As the imidazole-based curing accelerator, commercially available products may be used, for example, "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0156] Examples of guanidine-based curing accelerators include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, and 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene. Examples of suitable biguanide include 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.

[0157] Examples of metal-based curing accelerators include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt(II) acetylacetonate and cobalt(III) acetylacetonate, organic copper complexes such as copper(II) acetylacetonate, organic zinc complexes such as zinc(II) acetylacetonate, organic iron complexes such as iron(III) acetylacetonate, organic nickel complexes such as nickel(II) acetylacetonate, and organic manganese complexes such as manganese(II) acetylacetonate. Examples of organometallic salts include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

[0158] The content of the (F) curing accelerator, when the non-volatile components in the resin composition are taken as 100% by mass, is preferably 0.01% by mass or more, more preferably 0.05% by mass or more, particularly preferably 0.1% by mass or more, and is preferably 3% by mass or less, more preferably 1% by mass or less, and even more preferably 0.5% by mass or less.

[0159] The content of the (F) curing accelerator, when the resin component in the resin composition is taken as 100% by mass, is preferably 0.1% by mass or more, more preferably 0.2% by mass or more, even more preferably 0.3% by mass or more, and is preferably 3% by mass or less, more preferably 2% by mass or less, even more preferably 1% by mass or less.

[0160] <(G) Other additives> In addition to the components described above, the resin composition may further contain other additives as optional components. Examples of the (G) other additives include polymerization initiators; organometallic compounds such as organocopper compounds, organozinc compounds, and organocobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; leveling agents such as silicone-based leveling agents and acrylic polymer-based leveling agents; thickeners such as bentone and montmorillonite; antifoaming agents such as silicone-based antifoaming agents, acrylic-based antifoaming agents, fluorine-based antifoaming agents, and vinyl resin-based antifoaming agents; ultraviolet absorbers such as benzotriazole-based ultraviolet absorbers; adhesion improvers such as urea silanes; adhesion promoters such as triazole-based adhesion promoters, tetrazole-based adhesion promoters, and triazine-based adhesion promoters; and hindered phenol-based antioxidants. surfactants such as fluorine-based surfactants and silicone-based surfactants; flame retardants such as phosphorus-based flame retardants (e.g., phosphate ester compounds, phosphazene compounds, phosphinic acid compounds, and red phosphorus), nitrogen-based flame retardants (e.g., melamine sulfate), halogen-based flame retardants, and inorganic flame retardants (e.g., antimony trioxide); dispersants such as phosphate ester-based dispersants, polyoxyalkylene-based dispersants, acetylene-based dispersants, silicone-based dispersants, anionic dispersants, and cationic dispersants; stabilizers such as borate-based stabilizers, titanate-based stabilizers, aluminate-based stabilizers, zirconate-based stabilizers, isocyanate-based stabilizers, carboxylic acid-based stabilizers, and carboxylic anhydride-based stabilizers; photopolymerization initiation aids such as tertiary amines; and photosensitizers such as pyrarizones, anthracenes, coumarins, xanthones, and thioxanthones. (G) Other additives may be used singly or in combination of two or more.

[0161] <(H) Solvent> The resin composition may further contain an arbitrary solvent as a volatile component in addition to the non-volatile components described above. As the (H) solvent, any known solvent can be used appropriately, and the type is not particularly limited, but an organic solvent is preferred. Examples of the (H) solvent include ketone-based solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester-based solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether-based solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, and anisole; alcohol-based solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, ethyl diglycol acetate, γ-butyrolactone, and methyl methoxypropionate. Examples of suitable solvents include ether ester solvents such as ethyl acetate; ester alcohol solvents such as methyl lactate, ethyl lactate, and methyl 2-hydroxyisobutyrate; ether alcohol solvents such as 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, and diethylene glycol monobutyl ether (butyl carbitol); amide solvents such as N,N-dimethylformamide, N,N-dimethylacetamide, and N-methyl-2-pyrrolidone; sulfoxide solvents such as dimethyl sulfoxide; nitrile solvents such as acetonitrile and propionitrile; aliphatic hydrocarbon solvents such as hexane, cyclopentane, cyclohexane, and methylcyclohexane; and aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, and trimethylbenzene. The (H) solvent may be used alone or in combination of two or more in any ratio.

[0162] From the viewpoint of significantly achieving the effects of the present invention, the resin composition preferably contains 0.5% by mass or more and 3% by mass or less of (H) solvent, relative to 100% by mass of all components of the resin composition. Specifically, the (H) solvent is preferably contained in an amount of 3% by mass or less, more preferably 2% by mass or less, and even more preferably 1.5% by mass or less, relative to 100% by mass of all components of the resin composition, and is preferably contained in an amount of 0.5% by mass or more, more preferably 0.8% by mass or more, and even more preferably 1% by mass or more.

[0163] 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.

[0164] <Physical properties and applications of resin compositions> A cured product obtained by thermally curing the resin composition at 190°C for 90 minutes exhibits excellent mechanical strength. This results in an insulating layer with excellent mechanical strength. Mechanical strength can be evaluated by elongation at break. The elongation at break is preferably greater than 0.7%, more preferably greater than 1.5%, and even more preferably greater than 1.5%, or 1.6% or greater. There is no particular upper limit, but it can be 50% or less. The elongation at break can be measured by the method described in the examples below.

[0165] The resin composition is thermally cured at 100°C for 30 minutes, then at 180°C for 30 minutes, to produce a cured product that can rapidly form recesses using the plasma treatment described below. This results in an insulating layer with a high etching rate (processing speed). The etching rate represents the thickness of the insulating layer removed per unit time, and can be calculated by dividing the depth of the recesses formed by the plasma irradiation time. The etching rate is preferably higher than 0.30 μm / min, more preferably higher than 0.4 μm / min, and even more preferably 0.4 μm / min or greater. There is no particular upper limit, but it can be set to 10 μm / min or less. The etching rate can be measured by the method described in the Examples described below.

[0166] A cured product obtained by thermally curing a resin composition at 200°C for 90 minutes typically exhibits excellent thermal conductivity. This results in an insulating layer with excellent thermal conductivity. The thermal conductivity is preferably 0.6 W / m·K or more, more preferably greater than 0.8 W / m·K, and even more preferably 0.8 W / m·K or more, or 0.9 W / m·K or more. There is no particular upper limit, but it is preferably less than 12 W / m·K, more preferably 10 W / m·K or less, and even more preferably 8 W / m·K or less, 5 W / m·K or less, or 3 W / m·K or less. Thermal conductivity can be measured by the method described in the Examples below.

[0167] A cured product obtained by thermally curing the resin composition at 190°C for 90 minutes exhibits the characteristic of low cure shrinkage. Therefore, an insulating layer with low cure shrinkage is obtained. The cure shrinkage is preferably 0.18% or less, more preferably 0.15% or less, and even more preferably 0.14% or less. There is no particular lower limit, but it may be 0% or more, or 0.001% or more, for example. The cure shrinkage can be measured by the method described in the examples below.

[0168] The resin composition is thermally cured at 100°C for 30 minutes, then at 180°C for 30 minutes, resulting in an insulating layer capable of forming small-diameter recesses. The microfabrication property is measured by forming multiple recesses with a diameter of 20 μm using plasma treatment, and then determining the defect rate of the recesses using a FIB-SEM composite device. The defect rate is preferably less than 60%, more preferably 40% or less, and even more preferably less than 40%. There is no particular lower limit, but it can be 0% or more, or 0.001% or more, for example. The microfabrication property can be measured by the method described in the examples below.

[0169] A cured product obtained by thermally curing a resin composition at 190°C for 90 minutes typically exhibits the characteristic of a low dielectric constant. This results in an insulating layer with a low dielectric constant. The dielectric constant is preferably 3.8 or less, more preferably 3.5 or less, and even more preferably 3.4 or less. There is no particular lower limit, but it may be 0.01 or more. The dielectric constant can be measured by the method described in the Examples below.

[0170] A cured product obtained by thermally curing a resin composition at 190°C for 90 minutes typically exhibits the characteristic of a low dielectric loss tangent. This results in an insulating layer with a low dielectric loss tangent. The dielectric loss tangent is preferably 0.020 or less, more preferably 0.014 or less, and even more preferably 0.013 or less. There is no particular lower limit, but it can be 0.001 or more. The dielectric loss tangent can be measured by the method described in the examples below.

[0171] The resin composition of the present invention has a high etching rate and can give a cured product having excellent elongation at break, fine processability, and cure shrinkage. Therefore, the resin composition of the present invention can be suitably used as a resin composition for insulation applications. Specifically, the resin composition can be suitably used as a resin composition for forming an insulating layer (a resin composition for forming an insulating layer) to form a conductor layer (including a rewiring layer) formed on the insulating layer.

[0172] Furthermore, in the multilayer printed wiring boards described below, the resin composition can be suitably used as a resin composition for forming an insulating layer of a multilayer printed wiring board (a resin composition for forming an insulating layer of a multilayer printed wiring board), a resin composition for forming an interlayer insulating layer of a printed wiring board (a resin composition for forming an interlayer insulating layer of a printed wiring board), a resin composition for forming a recess in an insulating layer by a dry process, and a resin composition for forming a recess in an insulating layer by plasma treatment.

[0173] Furthermore, for example, when a semiconductor chip package is manufactured through the following steps (1) to (6), the resin composition of the present invention can be suitably used as a resin composition for a rewiring formation layer (resin composition for forming a rewiring formation layer) as an insulating layer for forming a rewiring layer, and as a resin composition for encapsulating a semiconductor chip (resin composition for encapsulating a semiconductor chip). When a semiconductor chip package is manufactured, a rewiring layer may be further formed on the encapsulating layer. (1) a step of laminating a temporary fixing film on a substrate; (2) a step of temporarily fixing a semiconductor chip on a temporary fixing film; (3) forming an encapsulation layer on the semiconductor chip; (4) peeling the substrate and the temporary fixing film from the semiconductor chip; (5) forming a rewiring formation layer as an insulating layer on the surface of the semiconductor chip from which the base material and the temporary fixing film have been peeled off; and (6) A step of forming a rewiring layer as a conductor layer on the rewiring formation layer.

[0174] [Resin sheet] The resin sheet of the present invention includes a support and a resin composition layer formed from the resin composition of the present invention and provided on the support.

[0175] The thickness of the resin composition layer is preferably 100 μm or less, more preferably 80 μm or less, and even more preferably 50 μm or less, from the viewpoint of making the printed wiring board thinner and being able to provide a cured product of the resin composition that has excellent insulating properties even when the cured product is thin. The lower limit of the thickness of the resin composition layer is not particularly limited, but can usually be 5 μm or more.

[0176] 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.

[0177] 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, with inexpensive polyethylene terephthalate being particularly preferred.

[0178] When a metal foil is used as the support, examples of the metal foil include copper foil and aluminum foil, with copper foil being preferred. The copper foil may be 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.).

[0179] The surface of the support that is to be bonded to the resin composition layer may be subjected to a matte treatment, a corona treatment, or an antistatic treatment.

[0180] The support may also be a support with a release layer, which has a release layer on the surface that bonds to the resin composition layer. 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, polyolefin resins, urethane resins, and silicone resins. Commercially available products may also be used as the support with a release layer, including, for example, "SK-1," "AL-5," and "AL-7" manufactured by Lintec Corporation, "Lumirror T60" manufactured by Toray Industries, Inc., "Purex" manufactured by Teijin Limited, and "Uni-Peel" manufactured by Unitika Limited, which are PET films having a release layer primarily composed of an alkyd resin-based release agent.

[0181] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably 10 μm to 60 μm. When a support with a release layer is used, it is preferable that the thickness of the entire support with a release layer is in the above range.

[0182] In one embodiment, the resin sheet may further include other layers as necessary. Examples of such other layers include a protective film conforming to the support and provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface opposite the support). The thickness of the protective film is not particularly limited, but is, for example, 1 μm to 40 μm. By laminating the protective film, adhesion of dust and the like to the surface of the resin composition layer and scratches can be suppressed.

[0183] The resin sheet can be produced, for example, by preparing a resin varnish by dissolving a resin composition in a solvent, applying the resin varnish to a support using a die coater or the like, and then drying the applied resin varnish to form a resin composition layer. The solvent is as described above.

[0184] Drying may be carried out by known methods such as heating or hot air blowing. Drying conditions are not particularly limited, but drying is carried out so that the solvent content in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although this varies depending on the boiling point of the solvent in the resin varnish, for example, when a resin varnish containing 30% by mass to 60% by mass of solvent is used, the resin composition layer can be formed by drying at 50°C to 150°C for 3 to 10 minutes.

[0185] The resin sheet can be stored in a rolled state. When the resin sheet has a protective film, it can be used by peeling off the protective film.

[0186] [Printed wiring board and its manufacturing method] 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.

[0187] The printed wiring board can be produced, for example, by using the above-mentioned resin composition or resin sheet by a method including the following steps (I) and (III). (I) A step of forming an insulating layer on an inner layer substrate (III) A step of forming recesses by subjecting the insulating layer to plasma treatment.

[0188] <Step (I): Step of forming an insulating layer on an inner layer substrate> Step (I) is a step of forming an insulating layer on an inner layer substrate, and the insulating layer contains a cured product of the resin composition of the present invention, and preferably consists of only a cured product of the resin composition of the present invention. Step (I) usually includes step (I-1) of forming a resin composition layer containing the resin composition on the inner layer substrate, and step (I-2) of curing the resin composition layer.

[0189] In step (I-1), a resin composition layer is typically formed on a main surface of the inner layer substrate. The main surface of the inner layer substrate refers to the surface of the inner layer substrate on which an insulating layer is provided. For example, the resin composition layer may include applying a resin composition to the inner layer substrate and drying the resin composition as necessary. In step (I-1), it is preferable to laminate the inner layer substrate and a resin sheet to form a resin composition layer on the inner layer substrate.

[0190] The "inner layer substrate" used in step (I) is a member that will become the substrate of a printed wiring board, and examples thereof include glass epoxy substrates, metal substrates, polyester substrates, polyimide substrates, BT resin substrates, and thermosetting polyphenylene ether substrates. The substrate may have a conductor layer on one or both sides, and this conductor layer may be patterned. An inner layer substrate having a conductor layer (circuit) formed on one or both sides of the substrate may be referred to as an "inner layer circuit board." Furthermore, the "inner layer substrate" of the present invention also includes intermediate products on which an insulating layer and / or a conductor layer is to be further formed during the production of a printed wiring board. When the printed wiring board is a circuit board with built-in components, an inner layer substrate with built-in components may be used.

[0191] The inner layer substrate and the resin sheet can be laminated, for example, by thermocompression bonding the resin sheet to the inner layer substrate from the support side. Examples of a member for thermocompression bonding the resin sheet to the inner layer substrate (hereinafter also referred to as a "thermocompression bonding member") include a heated metal plate (such as a SUS end plate) or a metal roll (SUS roll). Note that rather than pressing the thermocompression bonding member directly onto the resin sheet, it is preferable to press it via an elastic material such as heat-resistant rubber so that the resin sheet can sufficiently conform to the surface irregularities of the inner layer substrate.

[0192] The lamination of the inner layer substrate and the resin sheet may be carried out by a vacuum lamination method. In the vacuum lamination method, the thermocompression temperature is preferably in the range of 60°C to 160°C, more preferably 80°C to 140°C, the thermocompression pressure is preferably in the range of 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa, and the thermocompression time is preferably in the range of 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure conditions of 26.7hPa or less.

[0193] The lamination can be performed using a commercially available vacuum laminator, such as a vacuum pressure laminator manufactured by Meiki Seisakusho Co., Ltd., a vacuum applicator manufactured by Nikko Materials Co., Ltd., or a batch vacuum pressure laminator.

[0194] After lamination, the laminated resin sheets 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 lamination. The smoothing treatment may be performed using a commercially available laminator. Note that lamination and smoothing treatment may be performed consecutively using the commercially available vacuum laminator.

[0195] When the resin composition is applied to the inner layer substrate, the method for applying the resin composition may be the same as the method for applying a resin varnish to a support in the production of a resin sheet, and the drying of the applied resin composition may be the same as the drying in the production of a resin sheet.

[0196] In step (I-2), the resin composition layer is cured. By curing the resin composition layer, an insulating layer containing a cured product of the resin composition can be obtained. Usually, the obtained insulating layer contains only a cured product of the resin composition. Curing of the resin composition layer is usually carried out by thermal curing.

[0197] In the step (I-2), 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.

[0198] For example, although the thermal curing conditions for the resin composition layer vary depending on the type of resin composition, the curing temperature is preferably 120° C. to 240° C., more preferably 150° C. to 220° C., and even more preferably 170° C. to 210° C. The curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 100 minutes, and even more preferably 15 minutes to 100 minutes.

[0199] Before thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature lower than the curing temperature. For example, prior to thermally curing the resin composition layer, the resin composition layer may be preheated at a temperature of 50°C or higher but lower than 120°C (preferably 60°C or higher but 115°C or lower, more preferably 70°C or higher but 110°C or lower) for 5 minutes or longer (preferably 5 to 150 minutes, more preferably 15 to 120 minutes, and even more preferably 15 to 100 minutes).

[0200] When the insulating layer is formed using a resin sheet having a support, the support may be removed between step (I-1) and step (I-2), or may be removed after step (I).

[0201] <Step (II): Step of forming a mask layer on an insulating layer> The method for manufacturing a printed wiring board may include, after step (I), step (II) of forming a mask layer on the insulating layer, if necessary. This step (II) is usually performed before step (III). The mask layer is generally formed so as to selectively cover the portions of the insulating layer other than the portions where recesses are to be formed. Therefore, the mask layer is absent in the portions of the insulating layer where recesses are to be formed, and the insulating layer may be exposed. Therefore, the plasma treatment in step (III) selectively removes the portions of the insulating layer where the mask layer is absent, thereby forming recesses having an appropriate pattern shape in those portions. Unless otherwise specified, the "pattern shape" refers to the shape as viewed from the thickness direction.

[0202] The mask layer can usually be formed using a photosensitive resist. The mask layer may be formed using, for example, a dry film provided with a resist layer containing the resist. When the mask layer is formed using a dry film, step (II) may include step (II-1) of laminating the dry film on the insulating layer, and step (II-2) of exposing and developing the dry film using a photomask to form the mask layer.

[0203] The dry film used in step (II-1) may be a film having a resist layer. The resist layer may be one that can form holes having a pattern corresponding to the recesses by exposure and development. Among these, a resist layer that is resistant to plasma treatment is preferred. Examples of such resist layers include resist layers containing resins such as novolac resins and acrylic resins. From the viewpoint of improving the processability of the recesses, the thickness of the resist layer is preferably 10 μm or more, more preferably 15 μm or more, and even more preferably 20 μm or more, and is preferably 100 μm or less, more preferably 70 μm or less, and even more preferably 50 μm or less. The dry film may optionally be provided with a protective layer such as a plastic film layer.

[0204] The insulating layer and the dry film are usually laminated so that the insulating layer and the resist layer are bonded together. The lamination conditions for the insulating layer and the dry film can be the same as the lamination conditions for the inner layer substrate and the resin sheet in step (I-1).

[0205] After step (II-1), step (II-2) is performed, in which the dry film is exposed and developed. The exposure in step (II-2) usually involves irradiating the dry film with active energy rays through a photomask. The photomask generally comprises a member having a light-transmitting portion that can transmit active energy rays and a light-shielding portion that can block the active energy rays. In this case, one of the light-transmitting portion and the light-shielding portion (usually the light-shielding portion) has a pattern shape identical to the pattern shape of the recesses to be formed in the insulating layer. When the dry film is irradiated with active energy rays through this photomask, the portions of the resist layer corresponding to the light-shielding portions (non-exposed portions) are not irradiated with the active energy rays, but the other portions (exposed portions) are irradiated with the active energy rays through the light-transmitting portions. Thus, a latent image having the same pattern shape as the pattern shape of the recesses is formed in the resist layer by one of the exposed and non-exposed portions (usually the non-exposed portions).

[0206] Examples of active energy rays include ultraviolet rays, visible light, electron beams, and X-rays, with ultraviolet rays being preferred. The dose and duration of ultraviolet light irradiation can be appropriately set depending on the resist layer. Examples of exposure methods include contact exposure, in which a photomask is placed in close contact with the dry film for exposure, and non-contact exposure, in which a photomask is not placed in close contact with the dry film for exposure using parallel light. When the dry film has a protective layer, the protective layer is usually peeled off before the development described below.

[0207] After exposure, development is performed to remove either the exposed or unexposed portions of the resist layer (usually the unexposed portions), thereby forming a mask layer that selectively covers the portions of the insulating layer other than the portions where recesses are to be formed. Development may be performed by either wet development or dry development. Examples of development methods include a dipping method, a puddle method, a spray method, a brushing method, and a scraping method.

[0208] <Step (III): Step of forming recesses by subjecting the insulating layer to plasma treatment> Step (III) is a step of forming a recess by subjecting the insulating layer to plasma treatment. In step (III), the insulating layer is scraped by the plasma treatment, thereby forming a recess in the insulating layer. The recess formed is a recessed portion formed on the surface of the insulating layer opposite the inner layer substrate, and may be a portion formed to be recessed relative to the surrounding surface. Therefore, the recess has an opening on the surface of the insulating layer opposite the inner layer substrate. This recess may not penetrate the insulating layer, or may penetrate the insulating layer. An example of a recess that does not penetrate the insulating layer is a trench. An example of a recess that penetrates the insulating layer is a via hole. There is no limitation on the shape of this recess when viewed from the thickness direction, and it may be, for example, circular or groove-shaped.

[0209] The plasma treatment can be carried out by treating the surface of the insulating layer with plasma generated by introducing a gas into a plasma generator. Since the insulating layer contains the resin composition of the present invention, it has the characteristic of a high etching rate, i.e., a fast processing speed of the plasma treatment. Examples of methods for generating plasma include microwave plasma, which generates plasma using microwaves, high-frequency plasma, atmospheric pressure plasma, which is generated under atmospheric pressure, and vacuum plasma, which is generated under vacuum. Vacuum plasma, which is generated under vacuum, is preferred.

[0210] The gas to be converted into plasma can be one that can form recesses in the insulating layer. Examples of such gases include O2; fluorine-based gases; and inert gases such as Ar, He, and N2. Fluorine-based gases refer to gases containing fluorine atoms, and include fluorocarbon gases such as CF4, C3F8, C4F6, C4F8, CH2F2, and CHF3; SF6, NF3, and the like. These gases may be used alone or in combination of two or more. Among these, gases containing one or more selected from the group consisting of O2, fluorine-based gases, and inert gases are preferred. Furthermore, mixed gases containing O2, fluorine-based gases, and inert gases are more preferred. Among these, mixed gases containing O2, CF4, and He; and mixed gases containing O2, CF4, C3F8, and Ar are even more preferred.

[0211] When plasma is generated using a mixed gas containing two or more types of gases, it is preferable to adjust the mixing ratio of these gases within an appropriate range.

[0212] For example, when a mixed gas containing O2 is used, the amount of O2 relative to 100% of the total gas amount is preferably 1% or more, more preferably 5% or more, and even more preferably 10% or more, based on sccm. The upper limit is preferably 90% or less, more preferably 80% or less, even more preferably 70% or less, and may even be 50% or less. In one example, in a mixed gas containing a combination of O2 and a fluorine-based gas, and a mixed gas containing a combination of O2, a fluorine-based gas, and an inert gas, the amount of O2 is preferably within the above range.

[0213] For example, when a mixed gas containing a fluorine-based gas is used, the amount of the fluorine-based gas relative to 100% of the total gas amount is preferably 5% or more, more preferably 10% or more, even more preferably 20% or more, and may be 30% or more, 40% or more, 50% or more, or 60% or more, based on sccm. The upper limit is preferably 95% or less, more preferably 90% or less. In one example, in a mixed gas containing a combination of O2 and a fluorine-based gas, and a mixed gas containing a combination of O2, a fluorine-based gas, and an inert gas, the amount of the fluorine-based gas is preferably within the above range.

[0214] For example, when a mixed gas containing an inert gas is used, the amount of the inert gas relative to 100% of the total gas amount is preferably 1% or more, more preferably 2% or more, and even more preferably 5% or more, and is preferably 40% or less, more preferably 30% or less, and even more preferably 20% or less, based on sccm. In one example, in a mixed gas containing O, a fluorine-based gas, and an inert gas in combination, the amount of the inert gas is preferably within the above range.

[0215] For example, in a mixed gas containing O2 and a fluorine-based gas, the mixture ratio "fluorine-based gas / O2" based on sccm is preferably 0.01 or more, more preferably 0.1 or more, even more preferably 1.0 or more, and is preferably 30 or less, more preferably 20 or less, even more preferably 10 or less.

[0216] Here, "sccm" is a unit of gas flow rate, and is the amount of gas flowing per minute expressed as the volume (cm) of the gas at 0°C and 1 atm. 3 ) is indicated.

[0217] The pressure inside the chamber during plasma treatment is preferably 50 Pa or more, more preferably 75 Pa or more, even more preferably 100 Pa or more, and is preferably 300 Pa or less, more preferably 250 Pa or less, even more preferably 200 Pa or less.

[0218] The irradiation time in the plasma treatment is preferably 1 minute or more, more preferably 2 minutes or more, and even more preferably 3 minutes or more. The upper limit is not particularly limited, but is preferably 20 minutes or less, more preferably 15 minutes or less, and more preferably 10 minutes or less.

[0219] Plasma treatment can form recesses with small opening dimensions. The opening dimensions of a recess refer to the opening dimensions of the recess formed on the surface of the insulating layer opposite the inner layer substrate. For example, if the recess is a trench having a groove-like pattern, the opening dimensions refer to the width of the opening of the trench. Also, for example, if the recess is a circular via hole, the opening dimensions refer to the diameter of the opening of the via hole. The specific range of the opening dimensions is preferably 50 μm or less, more preferably 40 μm or less, even more preferably 30 μm or less, and even more preferably 20 μm or less. The lower limit is not particularly limited, but can be 1 μm or more.

[0220] <Step (IV): Step of Removing Mask Layer> If a mask layer is formed on the insulating layer in step (II), the mask layer may be removed by the plasma treatment in step (III), but a portion of the mask layer may remain on the insulating layer. If the mask layer remains on the insulating layer that has been subjected to the plasma treatment in step (III), the method for manufacturing a printed wiring board may include step (IV) of removing the mask layer. The method for removing the mask layer may be an appropriate method depending on the type of mask layer. For example, the mask layer may be removed using an alkaline stripping solution such as a sodium hydroxide solution.

[0221] <Step (V): Step of forming a conductor layer> The method for producing a printed wiring board preferably includes a step (V) of forming a conductor layer on an insulating layer. Step (V) may be performed after step (III). When the method for producing a printed wiring board includes step (IV), step (V) may be performed after step (IV).

[0222] The conductive 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. Examples of alloy layers include layers formed from an alloy of two or more metals selected from the above group (e.g., nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy). Among these, from the viewpoints of versatility in forming the conductor layer, cost, ease of patterning, etc., single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or alloy layers of nickel-chromium alloy, copper-nickel alloy, or copper-titanium alloy are preferred. Single metal layers of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver, or copper, or alloy layers of nickel-chromium alloy are more preferred, and single metal layers of copper are even more preferred.

[0223] The conductor layer may have a single layer structure or a multi-layer structure in which two or more single metal layers or alloy layers made of different types 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.

[0224] 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.

[0225] In one embodiment, the conductor layer may be formed by plating. For example, a conductor layer having a desired wiring pattern can be formed by plating the surface of the insulating layer using a conventionally known technique such as a semi-additive method or a full-additive method. From the viewpoint of ease of production, it is preferable to form the conductor layer by a semi-additive method. An example of forming the conductor layer by a semi-additive method will be described below.

[0226] 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, exposing a portion of the plating seed layer corresponding to the 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, thereby forming a conductor layer having the desired wiring pattern.

[0227] In another embodiment, the conductor layer may be formed by sputtering. When forming a conductor layer by sputtering, typically, a conductor seed layer is formed on an insulating layer by sputtering, and then a conductor sputter layer is formed on the conductor seed layer by further sputtering. Furthermore, before forming the conductor seed layer by sputtering, the surface of the insulating layer may be cleaned by reverse sputtering. Gases used for reverse sputtering are preferably Ar gas, O2 gas, or N2 gas. When the conductor seed layer is Cu or a Cu alloy, Ar gas, O2 gas, or a mixed gas of Ar and O2 are preferred. When the conductor seed layer is Ti, Ar gas, N2 gas, or a mixed gas of Ar and N2 are preferred. When the seed layer is Cr or a Cr alloy (such as nichrome), Ar gas, O2 gas, or a mixed gas of Ar and O2 are preferred. Sputtering can be performed using various sputtering devices such as magnetron sputtering and mirror tron ​​sputtering. Examples of metals that form the conductor seed layer include Cr, Ni, Ti, and nichrome. Cr and Ti are particularly preferred. The thickness of the conductive seed layer is preferably 5 nm or more, more preferably 10 nm or more, and preferably 1000 nm or less, more preferably 500 nm or less. Examples of metals that form the conductive sputtered layer include Cu, Pt, Au, and Pd. Cu is particularly preferred. The thickness of the conductive sputtered layer is preferably 50 nm or more, more preferably 100 nm or more, and preferably 3000 nm or less, more preferably 1000 nm or less.

[0228] The method for producing a printed wiring board may involve repeating the above steps. For example, steps (I) to (V) may be repeated to produce a multilayer printed wiring board (multilayer printed wiring board) having alternating insulating layers and conductor layers.

[0229] The method for producing a printed wiring board may further include any other step in combination with the above steps. For example, the method for producing a printed wiring board may include a step of roughening the surface of the insulating layer after forming the insulating layer in step (III). Examples of the roughening treatment include a method including contacting the surface of the insulating layer with an oxidizing agent solution.

[0230] [Semiconductor Devices] The semiconductor device of the present invention includes the printed wiring board of the present invention. The semiconductor device of the present invention can be manufactured using the printed wiring board of the present invention.

[0231] Examples of semiconductor devices include various semiconductor devices used in electrical appliances (for example, computers, mobile phones, digital cameras, and televisions) and vehicles (for example, motorcycles, automobiles, trains, ships, and aircraft).

[0232] The semiconductor device of the present invention can be manufactured by mounting a component (semiconductor chip) on a conductive portion of a printed wiring board. The "conductive portion" refers to a portion of the printed wiring board that transmits an electrical signal, and the portion may be either on the surface or embedded. The semiconductor chip is not particularly limited as long as it is an electrical circuit element made of a semiconductor material.

[0233] The method of mounting a semiconductor chip when manufacturing a semiconductor device is not particularly limited as long as the semiconductor chip functions effectively, but specific examples include wire bonding mounting, flip chip mounting, bumpless buildup layer (BBUL) mounting, anisotropic conductive film (ACF) mounting, non-conductive film (NCF) mounting, etc. Here, the "bumpless buildup layer (BBUL) mounting method" refers to "a mounting method in which a semiconductor chip is directly embedded in a recess in a printed wiring board and the semiconductor chip is connected to the wiring on the printed wiring board." [Example]

[0234] The present invention will be described in more detail below with reference to examples. The present invention is not limited to these examples. In the following, "parts" and "%" representing amounts mean "parts by mass" and "% by mass", respectively, unless otherwise specified.

[0235] <Synthesis Example 1: Synthesis of Polyimide 1> A 1000 ml separable flask equipped with a nitrogen inlet tube and a stirrer was charged with 62.46 g (120 mmol) of 4,4'-(4,4'-isopropylidenediphenoxy)bisphthalic dianhydride (BPADA), 12.17 g (40 mmol) of (5-amino-2-biphenyl)-4-aminobenzoate (PHBAAB), 27.56 g (80 mmol) of 4,4'-(m-phenylenediisopropylidene)dianiline (Bisaniline-M), 303 g of γ-butyrolactone (GBL), 1.90 g (24 mmol) of pyridine, and 34 g of toluene. The mixture was reacted under a nitrogen atmosphere at 180°C for 10 hours while removing the toluene from the system, thereby obtaining a 26.7 mass % polyimide solution.

[0236] <Production of resin varnish> Each component was weighed out in the number of parts by mass shown in the table below, and then mixed with 10 parts of MEK and 10 parts of cyclohexanone. The mixture was uniformly dispersed using a high-speed rotating mixer to obtain a resin varnish. [Table 1] [Table 2] *1: Indicates the content when the non-volatile components in the resin composition are taken as 100% by mass. *2: Indicates the content when the non-volatile components in the resin composition are taken as 100% by volume. *3: The content when the total amount of components (C) and (D) is taken as 100% by volume.

[0237] Details of each component listed in the table are as follows: Component (A) YX4000HK: Bixylenol-type epoxy resin, epoxy equivalent 193g / eq., manufactured by Mitsubishi Chemical Corporation HP6000: Naphthylene ether type epoxy resin, epoxy equivalent 213g / eq., manufactured by DIC Corporation ZX-1059: 1:1 mixture of bisphenol A epoxy resin and bisphenol F epoxy resin, epoxy equivalent 169g / eq., manufactured by Nippon Steel Chemical & Material Co., Ltd. 2021P: Alicyclic epoxy resin, epoxy equivalent 120g / eq., manufactured by Daicel Corporation (B) Component SLK-6895-M90: Maleimide compound containing an aliphatic skeleton, manufactured by Shin-Etsu Chemical Co., Ltd. HPC-8000-65T: Active ester resin containing dicyclopentadiene-type diphenol structure, functional group equivalent weight 229g / eq., manufactured by DIC Corporation SN485: Naphthol aralkyl phenolic curing agent, manufactured by Nippon Kayaku Co., Ltd., phenol equivalent: approx. 215g / eq. LA3018-50P: 1-methoxy-2-propanol solution with functional group equivalent of 151 g / eq. and non-volatile content of 50% by mass, manufactured by DIC Corporation V-03: Functional group equivalent weight 216 g / eq., toluene solution with non-volatile content of 50% by mass, manufactured by Nisshinbo Chemical Inc. (C) Component UHP-S2: Scaly boron nitride. Manufactured by Resonac. Average particle size: 0.7 μm, thermal conductivity 60 W / mK, specific gravity 2.2-2.3 Spherical nano BN: Spherical boron nitride. Manufactured by Denka Co., Ltd., average particle size: 0.5 μm, thermal conductivity 60 W / mK, specific gravity 2.3 BN-B: Flake boron nitride. Manufactured by Yingkou. Average particle size: 1.7 μm, thermal conductivity 60 W / mK, specific gravity 2.2-2.3 (D) Component SO-C2: Spherical silica surface-treated with an amine-based alkoxysilane compound ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), average particle size 0.5 μm, specific surface area 5.8 m 2 / g, manufactured by Admatechs Co., Ltd. UFP-30: Spherical silica surface-treated with an amine-based alkoxysilane compound (Shin-Etsu Chemical Co., Ltd.'s "KBM573"), with an average particle size of 0.3 μm and a specific surface area of ​​30.7 m 2 / g, manufactured by Denka (G) Component DAW-01: Spherical alumina. Manufactured by Denka. Average particle size: 1.9 μm, thermal conductivity: 30 W / mK, specific gravity: 3.7 (E) Component YX7553BH30: Phenoxy resin, 1:1 solution of MEK and cyclohexanone with 30% non-volatile content, manufactured by Mitsubishi Chemical Corporation Polyimide 1: Polyimide synthesized in Synthesis Example 1 (F) Component DMAP: Amine-based curing accelerator, manufactured by Tokyo Chemical Industry Co., Ltd. 1B2PZ: Imidazole-based reaction accelerator, manufactured by Shikoku Chemicals Corporation

[0238] <Measurement of dielectric constant, dielectric dissipation factor, and elongation at break (mechanical strength)> (1) Preparation of a resin sheet having a resin composition layer thickness of 40 μm A polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, thickness 38 μm) with a release layer was prepared as a support. The resin varnishes obtained in the Examples and Comparative Examples were uniformly applied onto the release layer of this support so that the thickness of the resin composition layer after drying would be 40 μm. Thereafter, the resin composition layer was dried at 80°C to 100°C (average 90°C) for 2 minutes to obtain a resin sheet including the support and the resin composition layer.

[0239] (2) Preparation of hardened product The resin sheets obtained in the examples and comparative examples were cured for 90 minutes in an oven at 190° C. The resin sheets were taken out of the oven and the support was peeled off to obtain cured resin composition layers.

[0240] (3) Measurement of dielectric constant and dielectric loss tangent The cured product was cut into a piece of 80 mm long and 2 mm wide, and the dielectric constant and dielectric loss tangent (Dk and Df values) were measured using an Agilent Technologies HP8362B cavity resonance perturbation method at a measurement frequency of 5.8 GHz and measurement temperatures of 23°C and 90°C. Measurements were performed on two test pieces, and the average was calculated. The calculated dielectric constant was evaluated according to the following criteria. 〇: Dielectric constant is 3.5 or less. △: Dielectric constant is greater than 3.5 and less than 3.8 ×: Dielectric constant is greater than 3.8 Good: Dielectric tangent is 0.014 or less. △: Dielectric tangent is 0.014 or greater, and is 0.020 or less ×: Dielectric tangent is greater than 0.020

[0241] (4) Measurement of mechanical strength (breaking elongation) The tensile strength of the cured product was measured using an Orientec tensile testing machine "RTC-1250A" to measure the breaking elongation at 23°C. The measurement was carried out in accordance with JIS K7127. The measurement was carried out five times, and the average of the top three points was calculated. The calculated average mechanical strength value was evaluated according to the following criteria. ◯: Breaking elongation is greater than 1.5%. △: Breaking elongation is greater than 0.7% and 1.5% or less. ×: Breaking elongation is 0.7% or less.

[0242] <Measurement of thermal conductivity> (1) Preparation of hardened sample The resin compositions prepared in the examples and comparative examples were applied using a die coater onto a PET film ("Lumirror R80" manufactured by Toray Industries, Inc., thickness 38 μm, softening point 130°C) that had been release-treated with an alkyd resin-based release agent ("AL-5" manufactured by Lintec Corporation) so that the thickness of the resin composition layer after drying would be 100 μm. The resin composition layer was then dried at 80°C to 100°C (average 90°C) for 7 minutes to obtain a resin composition layer.

[0243] Three resin composition layers were stacked on top of each other using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., two-stage build-up laminator "CVP700"), and then laminated. The resin composition layers were cured at 200°C for 90 minutes to obtain a cured sample. Lamination was performed by reducing the pressure to 13 hPa or less for 30 seconds, and then pressing for 20 seconds at 100°C and a pressure of 0.4 MPa.

[0244] (2) Measurement of thermal diffusivity α For the cured sample, the thermal diffusivity α (m 2 / s) was measured by thermal wave analysis using the "ai-Phase Mobile 1u" manufactured by ai-Phase Co., Ltd. Measurements were taken three times for the same sample, and the average value was calculated.

[0245] (3) Measurement of specific heat capacity Cp The cured samples were measured using a differential scanning calorimeter (DSC7020 manufactured by SII Nano Technology Co., Ltd.) by heating from -40°C to 80°C at a rate of 10°C / min, and the specific heat capacity Cp (J / kg·K) of the cured samples at 25°C was calculated.

[0246] (4) Measurement of density ρ Density of the hardened sample (kg / m 3 ) was measured using an analytical balance (Mettler-Toledo "XP105" (using a specific gravity measurement kit)).

[0247] (5) Calculation of thermal conductivity λ The thermal diffusivity α(m 2 / s), specific heat capacity Cp (J / kg K), and density ρ (kg / m 3 ) was substituted into the following formula (I) to calculate the thermal conductivity λ (W / m·K) of the cured product. λ=α×Cp×ρ (I)

[0248] The calculated thermal conductivity was evaluated according to the following criteria. Good: Thermal conductivity is greater than 0.8 W / m K and less than 5 W / m K. △: Thermal conductivity is 0.6 W / m·K or more and 0.8 W / m·K or less. ×: Thermal conductivity is less than 0.6 W / m·K or greater than 5 W / m·K.

[0249] <Etching rate measurement> (1) Preparation of copper clad laminate As the inner layer substrate, a glass cloth-based epoxy resin double-sided copper-clad laminate with copper foil layers on both sides (copper foil thickness 18 μm, substrate thickness 0.8 mm, Panasonic "R-1515A", 255 × 340 mm size) was prepared.

[0250] (2) Laminating resin sheets The resin sheet was laminated onto both sides of the inner layer substrate using a batch-type vacuum pressure laminator (a two-stage build-up laminator "CVP700" manufactured by Nikko Materials Co., Ltd.) so that the resin composition layer of the resin sheet contacted the inner layer substrate. Lamination was performed by reducing the pressure to 13 hPa or less for 30 seconds, and then pressing the resin sheet at 100°C and a pressure of 0.74 MPa for 30 seconds. The resin sheet was then heat-pressed at 100°C and a pressure of 0.5 MPa for 60 seconds.

[0251] (3) Fabrication of laminated plates The inner layer substrate laminated with the resin sheet was placed in an oven at 100°C and heated for 30 minutes, then transferred to an oven at 180°C and heated for 30 minutes. The heating caused the resin composition layer to thermally cure, forming an insulating layer. The support was then peeled off to obtain a laminate having a layer structure of insulating layer / inner layer substrate / insulating layer.

[0252] (4) Dry film pattern formation A dry film (manufactured by Nikko Materials Co., Ltd., "ALPHO 20A263") was prepared, comprising a resist layer (20 μm thick) and a protective layer formed of a polyethylene terephthalate film. The dry film was laminated onto the surface of the insulating layer of the laminate, so that the insulating layer and the resist layer were bonded. The lamination was carried out using a batch-type vacuum pressure laminator (manufactured by Meiki Seisakusho Co., Ltd., "MVLP-500"), with the pressure reduced for 30 seconds to 13 hPa or less, followed by pressure application at 0.1 MPa and a temperature of 70°C for 20 seconds. A glass mask with a transparent portion corresponding to the trench pattern to be formed in the resist layer was then placed on the protective layer of the dry film. A UV lamp was used to irradiate the resist layer through the glass mask at an irradiation intensity of 150 mJ / cm. 2UV irradiation was performed at 1000 K. After UV irradiation, the protective layer was peeled off. The resist layer was developed by spraying a 1% aqueous sodium carbonate solution at 30°C at a spray pressure of 0.15 MPa for 30 seconds. After that, the resist layer was washed with water to form a mask layer as a resist layer having a trench pattern with a wiring width of 20 μm. Here, the "trench pattern" refers to holes formed in the resist layer in accordance with the planar shape of the trench to be formed in the insulating layer. Therefore, the resist layer did not cover the insulating layer in the areas where the trench pattern was formed, but selectively covered the insulating layer in areas other than the trench pattern.

[0253] (5) Plasma processing A 20 μm wide trench was formed in the insulating layer by plasma treatment using a vacuum plasma etching device (M120W manufactured by Nissin Co., Ltd.), to obtain a printed wiring board. The gas to be converted into plasma in the plasma treatment was five mixed gases with the following specified mixing ratios (expressed in sccm), and the treatment was carried out under the conditions of a pressure of 120 Pa and a processing time of 10 minutes. [Table 3] *The units in the table are sccm

[0254] (6) Evaluation of etching rate (processing speed) of plasma treatment The cross section of the obtained printed wiring board was observed using a FIB-SEM composite device ("SMI3050SE" manufactured by SII Nano Technology Co., Ltd.), and the trench depth was measured. The measured depth was divided by the processing time to calculate the etching rate (μm / min). The calculated etching rate was evaluated according to the following criteria. A higher etching rate indicates more efficient trench formation. ◯: Etching rate is 0.40 μm / min or more. △: Etching rate is higher than 0.30 μm / min and less than 0.40 μm / min. ×: Etching rate is 0.30 μm / min or less.

[0255] <Measurement and evaluation of the degree of cure shrinkage of the insulating layer> (1) Preparation of a resin sheet having a resin composition layer thickness of 40 μm A polyethylene terephthalate film ("AL5" manufactured by Lintec Corporation, thickness 38 μm) with a release layer was prepared as a support. The resin varnishes obtained in the Examples and Comparative Examples were uniformly applied onto the release layer of this support so that the thickness of the resin composition layer after drying would be 40 μm. Thereafter, the resin composition layer was dried at 80°C to 100°C (average 90°C) for 2 minutes to obtain a resin sheet including the support and the resin composition layer.

[0256] (2) Preparation of resin sheet with copper foil A resin sheet with copper foil was obtained by laminating a resin composition layer of a resin sheet to the glossy surface of copper foil (Mitsui Mining & Smelting Co., Ltd., "MT18FL"). This lamination was performed using a batch-type vacuum pressure laminator (Nikko Materials Co., Ltd., two-stage build-up laminator "CVP700"). The pressure was reduced for 30 seconds to adjust the air pressure to 13 hPa or less, followed by pressure bonding at 120°C and a pressure of 0.74 MPa for 30 seconds. The laminated resin sheet was then heat-pressed at 100°C and a pressure of 0.5 MPa for 60 seconds to obtain a resin sheet with copper foil. Two holes were randomly drilled on the resin sheet with copper foil, and the distance between the two holes was measured.

[0257] (3) Hardening of copper foil-attached resin sheet The copper foil-attached resin sheet was cured for 90 minutes in an oven at 190° C. The copper foil-attached resin sheet was taken out of the oven and the support was peeled off to obtain a copper foil-attached cured product.

[0258] (4) Removal of copper foil The copper foil of the copper foil-attached cured product was removed by etching using an etching solution such as a copper chloride etching solution or an iron chloride etching solution, thereby obtaining a cured product.

[0259] (5) Evaluation of cure shrinkage The distance between any two holes in the cured product (the two holes are the same as the two holes on the resin sheet with copper foil) was measured, and the degree of cure shrinkage of the cured product was calculated using the following formula. The measurement was carried out three times, and the average value of the calculated degrees of cure shrinkage was evaluated according to the following criteria. Cure shrinkage % = {(difference in distance between two points before and after curing) / (distance between two points before curing)} x 100 Good: Cure shrinkage of 0.15% or less △: Cure shrinkage is greater than 0.15% and less than 0.18% ×: Cure shrinkage greater than 0.18%

[0260] <Evaluation of microfabrication> The printed wiring board obtained in the above <Measurement of Etching Rate> section "(5) Plasma Processing" was subjected to cross-sectional observation using a FIB-SEM composite device ("SMI3050SE" manufactured by SII Nano Technology Co., Ltd.), and the micromachining properties were evaluated according to the following criteria. ○: The rate of defective trench formation is less than 40% △: The rate of defective trench formation is less than 60% and is 40% or more ×: The rate of defective trench formation is 60% or more.

[0261] [Table 4] [Table 5]

Claims

1. (A) an epoxy resin, (B) a curing agent, (C) boron nitride, and (D) a resin composition containing an inorganic filler having a thermal conductivity of 10 W / m·K or less.

2. The resin composition according to claim 1 , wherein the component (B) comprises an active ester curing agent.

3. 3. The resin composition according to claim 2, wherein b1 is the content (volume %) of the active ester-based curing agent when the nonvolatile components in the resin composition are taken as 100% by volume, and c is the content (volume %) of the component (C) when the nonvolatile components in the resin composition are taken as 100% by volume, and b1 / c is 0.01 or more and 10 or less.

4. The resin composition according to claim 1, wherein the content of the component (A) is 1% by mass or more and 50% by mass or less, when the resin component in the resin composition is 100% by mass.

5. 2. The resin composition according to claim 1, wherein the content (vol %) of component (C) is 10% by volume or more, where the total amount of components (C) and (D) is 100% by volume.

6. 2. The resin composition according to claim 1, wherein the cured product obtained by thermally curing the resin composition at 200°C for 90 minutes has a thermal conductivity of 5 W / m·K or less.

7. The resin composition according to claim 1, which is a resin composition for forming recesses in an insulating layer by a dry process.

8. The resin composition according to claim 1, which is a resin composition for forming recesses in an insulating layer by plasma treatment.

9. The gas to be converted into plasma in the plasma treatment is O ２ 9. The resin composition according to claim 8, wherein the gas is at least one selected from the group consisting of a fluorine-based gas and an inert gas.

10. The gas to be converted into plasma in the plasma treatment is O ２ The resin composition according to claim 8, wherein the mixed gas contains a fluorine-based gas and an inert gas.

11. O relative to 100% of total gas volume ２ The resin composition according to claim 9, wherein the amount of is 1% or more and 90% or less on a sccm basis.

12. The resin composition according to claim 9, wherein the amount of the fluorine-based gas relative to 100% of the total amount of gas is 5% or more and 95% or less on the basis of sccm.

13. The resin composition according to claim 1, wherein the resin composition is heat-cured at 190°C for 90 minutes and the cured product has an elongation at break of greater than 0.7%.

14. 2. The resin composition according to claim 1, wherein the cured product obtained by thermally curing the resin composition at 190°C for 90 minutes has a cure shrinkage of 0.18% or less.

15. A resin sheet comprising a support and a resin composition layer provided on the support, the resin composition comprising the resin composition according to any one of claims 1 to 14.

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.

18. forming an insulating layer on the inner layer substrate; a step of subjecting the insulating layer to a plasma treatment to form a recess; A method for producing a printed wiring board, wherein the insulating layer comprises a cured product of the resin composition according to any one of claims 1 to 14.

19. The gas to be converted into plasma in the plasma treatment is O ２ 19. The method for producing a printed wiring board according to claim 18, wherein the gas is at least one selected from the group consisting of a fluorine-based gas and an inert gas.

20. The gas to be converted into plasma in the plasma treatment is O ２ 19. The method for producing a printed wiring board according to claim 18, wherein the gas is a mixed gas containing a fluorine-based gas and an inert gas.

21. O relative to 100% of total gas volume ２ The method for manufacturing a printed wiring board according to claim 18, wherein the amount of is 1% or more and 90% or less on an sccm basis.

22. 19. The method for producing a printed wiring board according to claim 18, wherein the amount of the fluorine-based gas relative to 100% of the total amount of gas is 5% or more and 95% or less on the basis of sccm.

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