Resin composition

Abstract

The problem of the present invention is to provide a resin composition that can suppress viscosity to a low level despite a low amount of inorganic filler, and can obtain a cured product having excellent flexibility and excellent insulation reliability. The solution of the present invention is a resin composition, which is a resin composition comprising (A) an epoxy resin, (B) an inorganic filler, and (C) a polyimide resin, wherein the (A) component comprises (A-1) an epoxy resin containing a siloxane skeleton, and when the non-volatile component in the resin composition is set to 100% by mass, the content of the (B) component is 40% by mass or less.

Description

Technical Field

[0001] The present invention relates to a resin composition containing a polyimide resin and further to a cured product, a resin sheet, a multilayer flexible substrate and a semiconductor device obtained by using the resin composition. Background Art

[0002] In recent years, there has been an increasing demand for thinner and lighter semiconductor components with a higher mounting density. In order to meet this demand, the use of flexible substrates as base substrates used in semiconductor components has attracted attention. Compared with rigid substrates, flexible substrates can be thinner and lighter. In addition, since flexible substrates are soft and deformable, they can be bent and installed.

[0003] Generally, it is necessary to mix a flexible resin such as a polyimide resin with the insulating material of a flexible substrate, but if a polyimide resin is mixed, the tackiness (adhesion) sometimes increases and the handling property is poor. The tackiness can be suppressed by mixing an inorganic filler (Patent Document 1), but if the mixing ratio of the inorganic filler increases, it will be difficult to take into account flexibility.

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2014-95047. Summary of the invention

[0007] Problems to be solved by the invention

[0008] An object of the present invention is to provide a resin composition that can suppress viscosity to a low level despite a low blending amount of an inorganic filler and can produce a cured product having excellent flexibility and excellent insulation reliability.

[0009] Means for solving problems

[0010] In order to solve the problem of the present invention, the present inventors conducted intensive research and found that by using the following resin composition, even if the content of (B) inorganic filler is a low compounding amount of less than 40% by mass, the viscosity can be suppressed to a low level, and a cured product with excellent flexibility and excellent insulation reliability can be obtained, thereby completing the present invention; the resin composition is a resin composition comprising (A) epoxy resin, (B) inorganic filler and (C) polyimide resin, wherein the (A) component comprises (A-1) epoxy resin containing a siloxane skeleton.

[0011] That is, the present invention includes the following contents:

[0012] [1] A resin composition comprising (A) an epoxy resin, (B) an inorganic filler and (C) a polyimide resin,

[0013] The component (A) comprises: (A-1) an epoxy resin containing a siloxane skeleton, wherein the content of the component (B) is 40% by mass or less, based on 100% by mass of the nonvolatile component in the resin composition;

[0014] [2] The resin composition according to [1] above, wherein the component (A-1) is an epoxy resin containing a cyclic siloxane skeleton;

[0015] [3] The resin composition according to [1] or [2] above, wherein the component (A-1) is a compound represented by the formula (A1).

[0016] [Chemical formula 1]

[0017]

[0018] [Where R 1 Each independently represents an alkylene oxide; R 2 Each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group; R 3 and R 4 Each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group; or, R 3 and R 4 Together, they are bonded to each other in a manner that represents one -O- to form a cyclic siloxane skeleton; s represents an integer greater than 1.]

[0019] [4] The resin composition according to any one of [1] to [3] above, wherein the molecular weight of the component (A-1) is 800 or less;

[0020] [5] The resin composition according to any one of [1] to [4] above, wherein the epoxy equivalent of the component (A-1) is 150 g / eq. to 250 g / eq.;

[0021] [6] The resin composition according to any one of [1] to [5] above, wherein the content of the component (A-1) is 5% by mass or more, based on 100% by mass of the nonvolatile component in the resin composition;

[0022] [7] The resin composition according to any one of [1] to [6] above, wherein the content of the component (A-1) is 10% by mass or less when the non-volatile component in the resin composition is 100% by mass;

[0023] [8] The resin composition according to any one of [1] to [7] above, wherein the average particle size of component (B) is 1 μm or less;

[0024] [9] The resin composition according to any one of [1] to [8] above, wherein the component (B) is silica;

[0025]

[10] The resin composition according to any one of [1] to [9] above, wherein the weight average molecular weight of the component (C) is 1,000 to 100,000.

[0026]

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

[10] above, wherein the content of the component (C) is 20% by mass or more, based on 100% by mass of the nonvolatile component in the resin composition;

[0027]

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

[11] above, wherein the content of the component (C) is 30% by mass or less when the non-volatile component in the resin composition is 100% by mass;

[0028]

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

[12] above, further comprising (D) a curing agent;

[0029]

[14] The resin composition according to

[13] above, wherein the component (D) comprises an active ester curing agent;

[0030]

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

[14] above, which is used to form an insulating layer of a multi-layer flexible substrate;

[0031]

[16] A cured product, which is a cured product of the resin composition described in any one of [1] to

[15] above;

[0032]

[17] A resin sheet comprising a support and a resin composition layer formed from the resin composition described in any one of [1] to

[15] above and disposed on the support;

[0033]

[18] A multi-layer flexible substrate comprising an insulating layer formed by curing the resin composition described in any one of [1] to

[15] above;

[0034]

[19] A semiconductor device comprising the multilayer flexible substrate described in

[18] above.

[0035] Effects of the Invention

[0036] By using the resin composition of the present invention, it is possible to suppress viscosity to a low level despite a low blending amount of an inorganic filler, and to obtain a cured product having excellent flexibility and excellent insulation reliability. DETAILED DESCRIPTION

[0037] Hereinafter, the present invention will be described in detail according to its preferred embodiments. However, the present invention is not limited to the following embodiments and examples, and can be implemented with arbitrary changes within the scope of the claims of the present invention and their equivalents.

[0038] <Resin composition>

[0039] The resin composition of the present invention is a resin composition comprising (A) an epoxy resin, (B) an inorganic filler and (C) a polyimide resin, wherein the component (A) comprises (A-1) an epoxy resin containing a siloxane skeleton, and the content of the component (B) is 40% by mass or less. By using such a resin composition, the viscosity can be suppressed to a low level despite the low amount of the inorganic filler, and a cured product having excellent flexibility and excellent insulation reliability can be obtained.

[0040] For the resin composition of the present invention, in addition to (A) epoxy resin, (B) inorganic filler and (C) polyimide resin, any component may be further included. As any component, for example (D) curing agent, (E) curing accelerator, (F) other additives and (G) organic solvent can be cited. Hereinafter, each component included in the resin composition is described in detail.

[0041] <(A) Epoxy resin>

[0042] The resin composition of the present invention contains (A) an epoxy resin. (A) The epoxy resin refers to a curable resin having an epoxy group. (A) The epoxy resin also includes a modified epoxy resin.

[0043] The content of the epoxy resin (A) in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 25% by mass or more, and particularly preferably 30% by mass or more. The upper limit of the content of the epoxy resin (A) in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 70% by mass or less, more preferably 60% by mass or less, further preferably 50% by mass or less, and particularly preferably 40% by mass or less.

[0044] <(A-1) Epoxy resin containing siloxane skeleton>

[0045] (A) The epoxy resin includes (A-1) an epoxy resin containing a siloxane skeleton. (A-1) The epoxy resin containing a siloxane skeleton refers to a compound having two or more epoxy groups and a siloxane (Si—O—Si) bond.

[0046] (A-1) The epoxy resin containing a siloxane skeleton may be an epoxy resin containing a cyclic siloxane skeleton or an epoxy resin containing a chain siloxane skeleton, but is preferably an epoxy resin containing a cyclic siloxane skeleton.

[0047] The number of silicon atoms forming siloxane bonds in the epoxy resin (A-1) containing a siloxane skeleton is not particularly limited, and may be preferably 3 or more, 10 or less, more preferably 8 or less, further preferably 6 or less, further more preferably 5 or less, and particularly preferably 4 in one molecule.

[0048] The number of epoxy groups in the epoxy resin (A-1) containing a siloxane skeleton is not particularly limited, and is preferably 3 or more, preferably 10 or less, more preferably 8 or less, further preferably 6 or less, further more preferably 5 or less, and particularly preferably 4 in one molecule.

[0049] All substitutable sites of silicon atoms in the epoxy resin containing a siloxane skeleton (A-1) are preferably substituted with hydrocarbon groups such as alkyl, alkenyl, and aryl groups which may or may not have an epoxy group. The hydrocarbon group may have a substituent other than an epoxy group.

[0050] (A-1) The epoxy resin containing a siloxane skeleton is preferably a compound represented by formula (A1).

[0051] [Chemical formula 2]

[0052]

[0053] [Where R 1 Each independently represents an alkylene oxide; R 2 Each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group; R 3 and R 4 Each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, or R 3 and R 4 Together, they are bonded to each other in a manner that represents one -O- to form a cyclic siloxane skeleton; s represents an integer greater than 1. ].

[0054] The term "alkyl" refers to a linear, branched and / or cyclic monovalent aliphatic saturated hydrocarbon group. The "alkyl" is preferably an alkyl group having 1 to 10 carbon atoms. Examples of the "alkyl" include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, neopentyl, sec-pentyl, tert-pentyl, cyclopentyl, cyclohexyl, cyclopentylmethyl, 2-cyclohexylmethyl, 2-cyclopentylethyl, and 2-cyclohexylethyl.

[0055] The so-called "alkylene oxide" refers to a group in which two hydrogen atoms bonded to different carbon atoms of the alkyl group are replaced by one oxygen atom to form an oxirane (ethylene oxide) ring. The "alkylene oxide" is preferably an alkylene oxide having 2 to 10 carbon atoms. Examples of the "alkylene oxide" include straight-chain alkylene oxides such as 2,3-epoxypropyl, 3,4-epoxybutyl, 4,5-epoxypentyl, and 5,6-epoxyhexyl; branched alkylene oxides such as 2,3-epoxy-2-methylpropyl and 3,4-epoxy-3-methylbutyl; cyclic alkylene oxides such as 2,3-epoxycyclopentyl, 3,4-epoxycyclopentyl, 2,3-epoxycyclohexyl, and 3,4-epoxycyclohexyl; 2,3-epoxycyclopentylmethyl, 3,4-epoxycyclopentylmethyl, 2,3-epoxycyclohexylmethyl, 3,4-epoxycyclohexylmethyl, 2-(2,3-epoxycyclopentyl) The invention also includes a linear alkyl group having a cyclic alkylene oxide at the terminal, such as a 2-(3,4-epoxycyclopentyl)ethyl group, a 2-(2,3-epoxycyclohexyl)ethyl group, a 2-(3,4-epoxycyclohexyl)ethyl group, a 3-(2,3-epoxycyclopentyl)propyl group, a 3-(3,4-epoxycyclopentyl)propyl group, a 3-(2,3-epoxycyclohexyl)propyl group, a 3-(3,4-epoxycyclohexyl)propyl group, a 4-(2,3-epoxycyclopentyl)butyl group, a 4-(3,4-epoxycyclopentyl)butyl group, a 4-(2,3-epoxycyclohexyl)butyl group, and a 4-(3,4-epoxycyclohexyl)butyl group.

[0056] The so-called "alkenyl" refers to a linear, branched and / or cyclic monovalent aliphatic unsaturated hydrocarbon group having at least one carbon-carbon double bond. The "alkenyl" is preferably an alkenyl group having 2 to 10 carbon atoms. Examples of the "alkenyl" 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.

[0057] The substituents of the alkyl group in the "substituted or unsubstituted alkyl group" and the alkenyl group in the "substituted or unsubstituted alkenyl group" are not particularly limited, and examples thereof include halogen atoms, cyano groups, nitro groups, alkyl-oxy groups, alkyl-carbonyl groups, alkyl-oxy-carbonyl groups, alkyl-carbonyl-oxy groups, alkenyl-oxy groups, alkenyl-carbonyl groups, alkenyl-oxy-carbonyl groups, alkenyl-carbonyl-oxy groups, aryl groups, aryl-oxy groups, aryl-carbonyl groups, aryl-oxy-carbonyl groups, aryl-carbonyl-oxy groups, and combinations thereof. The number of substituents is preferably 1 to 3, and more preferably 1.

[0058] The term "aryl group" refers to a monovalent aromatic hydrocarbon group. The "aryl group" is preferably an aryl group having 6 to 14 carbon atoms. Examples of the "aryl group" include phenyl, 1-naphthyl, and 2-naphthyl.

[0059] The substituent of the aryl group in the "substituted or unsubstituted aryl group" is not particularly limited, and examples thereof include a halogen atom, a cyano group, a nitro group, an alkyl group, an alkyl-oxy group, an alkyl-carbonyl group, an alkyl-oxy-carbonyl group, an alkyl-carbonyl-oxy group, an alkenyl group, an alkenyl-oxy group, an alkenyl-carbonyl group, an alkenyl-oxy-carbonyl group, an alkenyl-carbonyl-oxy group, an aryl group, an aryl-alkyl group, an aryl-alkenyl group, an aryl-oxy group, an aryl-carbonyl group, an aryl-oxy-carbonyl group, an aryl-carbonyl-oxy group, and the like, or a combination thereof. The number of substituents is preferably 1 to 3, and more preferably 1.

[0060] Examples of the "halogen atom" include a fluorine atom, a chlorine atom, and a bromine atom.

[0061] In formula (A1), R 1 Each independently represents an alkylene oxide group, and is preferably a linear alkyl group having a cyclic alkylene oxide group at the terminal, more preferably a methyl group having a cyclic alkylene oxide group, or an ethyl group having a cyclic alkylene oxide group at the terminal, and particularly preferably a 2-(3,4-epoxycyclohexyl)ethyl group.

[0062] In formula (A1), R 2 Each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, preferably a substituted or unsubstituted alkyl group, more preferably an (unsubstituted) alkyl group, further preferably a methyl group, an ethyl group, a propyl group or an isopropyl group, and particularly preferably a methyl group.

[0063] In formula (A1), R 3 and R 4 Each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, or R 3 and R 4 Together, they are bonded to each other in a manner that represents one -O- to form a cyclic siloxane skeleton. 3 and R 4In particular, it is preferred that they are bonded to each other in a manner that represents one -O- to form a cyclic siloxane skeleton.

[0064] In formula (A1), s represents an integer of 1 or more, preferably an integer of 2 or more. s is preferably an integer of 9 or less, more preferably an integer of 7 or less, further preferably an integer of 5 or less, and further more preferably an integer of 4 or less. s is particularly preferably 3.

[0065] Specific examples of the epoxy resin (A-1) containing a siloxane skeleton include epoxy resins containing a chain siloxane skeleton such as 1,3,5-tris(2-(3,4-epoxycyclohexyl)ethyl)-1,1,3,5,5-pentamethyltrisiloxane; 2,4,6,8-tetra(4-(3,4-epoxycyclopentyl)butyl)-2,4,6,8-tetramethylcyclotetrasiloxane; 2,4,6,8-tetra(3-(3,4-epoxycyclopentyl)propyl)-2,4,6,8-tetramethylcyclotetrasiloxane; Epoxy resins containing a cyclic siloxane skeleton such as cyclotetrasiloxane, 2,4,6,8-tetrakis(2-(3,4-epoxycyclohexyl)ethyl)-2,4,6,8-tetramethylcyclotetrasiloxane, and 2,4,6,8,10-penta(2-(3,4-epoxycyclohexyl)ethyl)-2,4,6,8,10-pentamethylcyclopentasiloxane, among which 2,4,6,8-tetrakis(2-(3,4-epoxycyclohexyl)ethyl)-2,4,6,8-tetramethylcyclotetrasiloxane is particularly preferred.

[0066] Examples of commercially available products of the epoxy resin containing a siloxane skeleton (A-1) include “KR-470” (main component: 2,4,6,8-tetrakis(2-(3,4-epoxycyclohexyl)ethyl)-2,4,6,8-tetramethylcyclotetrasiloxane) and “X-40-2667” (main component: 1,3,5-tris(2-(3,4-epoxycyclohexyl)ethyl)-1,1,3,5,5-pentamethyltrisiloxane) manufactured by Shin-Etsu Chemical Co., Ltd.

[0067] The molecular weight of the epoxy resin (A-1) containing a siloxane skeleton is preferably 2,000 or less, more preferably 1,500 or less, further preferably 1,000 or less, and particularly preferably 800 or less. The lower limit may be, for example, 200 or more, 400 or more, or 600 or more.

[0068] The epoxy equivalent of the epoxy resin (A-1) containing a siloxane skeleton is preferably 1,000 g / eq. or less, more preferably 500 g / eq. or less, further preferably 300 g / eq. or less, and particularly preferably 250 g / eq. or less. The lower limit is preferably 50 g / eq. or more, more preferably 100 g / eq. or more, further preferably 130 g / eq. or more, and particularly preferably 150 g / eq. or more.

[0069] The viscosity (25° C.) of the siloxane skeleton-containing epoxy resin (A-1) is preferably 100 mPa·s to 10,000 mPa·s, and more preferably 1,000 mPa·s to 5,000 mPa·s.

[0070] The content of the epoxy resin containing a siloxane skeleton in (A-1) in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 4% by mass or more, and particularly preferably 5% by mass or more. The upper limit of the content of the epoxy resin containing a siloxane skeleton in (A-1) in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 30% by mass or less, more preferably 20% by mass or less, further preferably 15% by mass or less, and particularly preferably 10% by mass or less.

[0071] <Optional epoxy resin other than component (A-1)>

[0072] (A) The epoxy resin may further contain any other epoxy resin in addition to (A-1) the epoxy resin containing a siloxane skeleton.

[0073] As arbitrary epoxy resins other than component (A-1), for example, biphenylol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol novolac type epoxy resin, phenol novolac type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type epoxy resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, The epoxy resins include epoxy resins of the type having a cyclohexane structure, epoxy resins of the type having a cyclohexanedimethanol structure, epoxy resins of the type having a naphthylene ether, epoxy resins of the type having a trimethylol group, epoxy resins of the type having a tetraphenylethane group, epoxy resins of the type having an isocyanurate group, epoxy resins of the type having a glycidyl cyclohexane group, etc. Any epoxy resin may be used alone or in combination of two or more.

[0074] For the resin composition, as any epoxy resin other than component (A-1), an epoxy resin having two or more epoxy groups in one molecule is preferably included. The proportion of the epoxy resin having two or more epoxy groups in one molecule is preferably 50% by mass or more, more preferably 60% by mass or more, and particularly preferably 70% by mass or more relative to 100% by mass of the non-volatile component of any epoxy resin other than component (A-1).

[0075] 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 of the present invention may contain only a liquid epoxy resin or only a solid epoxy resin as any epoxy resin other than the component (A-1), and preferably contains a combination of a liquid epoxy resin and a solid epoxy resin.

[0076] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0077] As liquid epoxy resins, preferred are 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, cyclohexanedimethanol type epoxy resins, and epoxy resins having a butadiene structure.

[0078] Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene-type epoxy resins) manufactured by DIC Corporation; "828US", "828EL", "jER828EL", "825", and "EPIKOTE "828EL" (bisphenol A type epoxy resin); "jER807", "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (phenol novolac type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (glycidyloxy (Glycirol) type epoxy resin) manufactured by ADEKA Corporation; "EP-3950L", "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA Corporation; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA Corporation; "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Nippon Steel & Sumitomo Metal Chemical Corporation; Nagase "EX-721" (glycidyl ester type epoxy resin) manufactured by ChemteX; "Celloxide 2021P" (alicyclic epoxy resin with ester skeleton) manufactured by Daicel; "PB-3600" manufactured by Daicel, "JP-100" and "JP-200" (epoxy resin with butadiene structure) manufactured by Nippon Soda; "ZX1658" and "ZX1658GS" (cyclohexane type epoxy resin) manufactured by Nippon Steel & Sumitomo Chemical Co., Ltd., etc. They can be used alone or in combination of two or more.

[0079] As the solid epoxy resin, a solid epoxy resin having three or more epoxy groups in one molecule is preferred, and an aromatic solid epoxy resin having three or more epoxy groups in one molecule is more preferred.

[0080] As solid epoxy resins, preferred are biphenylol-type epoxy resins, naphthalene-type epoxy resins, naphthalene-type tetrafunctional epoxy resins, cresol novolac-type epoxy resins, dicyclopentadiene-type epoxy resins, trisphenol-type epoxy resins, naphthol-type epoxy resins, biphenyl-type epoxy resins, naphthylene ether-type epoxy resins, anthracene-type epoxy resins, bisphenol A-type epoxy resins, bisphenol AF-type epoxy resins, and tetraphenylethane-type epoxy resins.

[0081] Specific examples of solid epoxy resins include "HP4032H" (naphthalene-type epoxy resin) manufactured by DIC Corporation; "HP-4700" and "HP-4710" (naphthalene-type tetrafunctional epoxy resin) manufactured by DIC Corporation; "N-690" (cresol novolac-type epoxy resin) manufactured by DIC Corporation; "N-695" (cresol novolac-type epoxy resin) manufactured by DIC Corporation; "HP-7200", "HP-7200HH" and "HP-7200H" (dicyclopentadiene-type epoxy resin) manufactured by DIC Corporation; "EXA-7311" (dicyclopentadiene-type epoxy resin) manufactured by DIC Corporation; ”, “EXA-7311-G3”, “EXA-7311-G4”, “EXA-7311-G4S”, “HP6000” (naphthyl ether type epoxy resin); “EPPN-502H” (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; “NC7000L” (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; “NC3000H”, “NC3000”, “NC3000L”, “NC3000FH”, “NC3100” (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "ESN475V" (naphthalene type epoxy resin) manufactured by Nihon Steel Chemical & Material Co., Ltd.; "ESN485" (naphthol type epoxy resin) manufactured by Nihon Steel Chemical & Material Co., Ltd.; "ESN375" (dihydroxynaphthalene type epoxy resin) manufactured by Nihon Steel Chemical & Material Co., Ltd.; "YX4000H", "YX4000", "YX4000HK", "YL7890" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" (biphenyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX "8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX7700" (phenolic varnish type epoxy resin containing xylene structure) manufactured by Mitsubishi Chemical Corporation; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1010" (solid bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation, etc. They can be used alone or in combination of two or more.

[0082] When a liquid epoxy resin and a solid epoxy resin are used together as any epoxy resin other than the component (A-1), the mass ratio of these (liquid epoxy resin:solid epoxy resin) is preferably in the range of 100:1 to 1:100, more preferably in the range of 10:1 to 1:40, and even more preferably in the range of 1:1 to 1:20.

[0083] The epoxy equivalent of any epoxy resin other than the component (A-1) is preferably 50 g / eq. to 5,000 g / eq., more preferably 60 g / eq. to 2,000 g / eq., further preferably 70 g / eq. to 1,000 g / eq., and further more preferably 80 g / eq. to 500 g / eq. The epoxy equivalent is the mass of the resin per 1 equivalent of epoxy group. The epoxy equivalent can be measured in accordance with JIS K7236.

[0084] The weight average molecular weight (Mw) of any epoxy resin other than the component (A-1) is preferably 100 to 5,000, more preferably 250 to 3,000, and even more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured as a value in terms of polystyrene by gel permeation chromatography (GPC).

[0085] When the resin composition includes any epoxy resin other than (A-1) component, the content of any epoxy resin other than (A-1) component in the resin composition is not particularly limited, and when the non-volatile component in the resin composition is set to 100% by mass, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and particularly preferably 20% by mass or more. The upper limit of the content of any epoxy resin other than (A-1) component in the resin composition is not particularly limited, and when the non-volatile component in the resin composition is set to 100% by mass, it is preferably 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, and particularly preferably 30% by mass or less.

[0086] When the resin composition contains any epoxy resin other than component (A-1), the content of the epoxy resin containing a siloxane skeleton (A-1) in the epoxy resin (A) is not particularly limited, and when the total amount of the epoxy resin (A) is set to 100% by mass, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and particularly preferably 20% by mass or more. The upper limit of the content of the epoxy resin containing a siloxane skeleton (A-1) in the epoxy resin (A) is not particularly limited, and when the total amount of the epoxy resin (A) is set to 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 30% by mass or less, and particularly preferably 25% by mass or less.

[0087] <(B) Inorganic fillers>

[0088] The resin composition of the present invention contains (B) an inorganic filler. The (B) inorganic filler is contained in the resin composition in the form of particles.

[0089] As the material of (B) inorganic filler, inorganic compounds are used. As the material of (B) inorganic filler, for example, silicon dioxide, aluminum oxide, glass, cordierite, silicon oxide, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, boehmite, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, magnesium oxide, boron nitride, aluminum nitride, manganese nitride, aluminum borate, strontium carbonate, strontium titanate, calcium titanate, magnesium titanate, bismuth titanate, titanium oxide, zirconium oxide, barium titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium phosphotungstate, etc., can be cited. Among these, silicon dioxide is particularly preferred. As silicon dioxide, for example, amorphous silicon dioxide, fused silica, crystalline silicon dioxide, synthetic silicon dioxide, hollow silica, etc. can be cited. In addition, as silicon dioxide, spherical silicon dioxide is preferred. (B) The inorganic filler may be used alone or in combination of two or more at any ratio.

[0090] Commercially available products of (B) inorganic fillers include, for example, "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Corporation; "YC100C", "YA050C", "YA050C-MJE", and "YA010C" manufactured by Admatechs Co., Ltd.; "Silfil NSS-3N", "Silfil NSS-4N", and "Silfil NSS-5N" manufactured by Tokuyama Co., Ltd.; "SC2500SQ", "SO-C4", "SO-C2", and "SO-C1" manufactured by Admatechs Co., Ltd.; and "UFP-30", "DAW-03", and "FB-105FD" manufactured by DENKA Corporation.

[0091] (B) The average particle size of the inorganic filler is not particularly limited, preferably 40 μm or less, more preferably 10 μm or less, further preferably 5 μm or less, further more preferably 3 μm or less, and particularly preferably 1 μm or less. (B) The lower limit of the average particle size of the inorganic filler is not particularly limited, preferably 0.005 μm or more, more preferably 0.01 μm or more, further preferably 0.05 μm or more, further preferably 0.1 μm or more, further more preferably 0.2 μm or more, and particularly preferably 0.3 μm or more. (B) The average particle size of the inorganic filler can be measured by a laser diffraction-scattering method based on Mie scattering theory. Specifically, it can be measured in the following manner: using a laser diffraction scattering particle size distribution measuring device, a particle size distribution of the inorganic filler is prepared on a volume basis, and the median particle size is used as the average particle size. The sample obtained by the following method can be used for the measurement: 100 mg of the inorganic filler and 10 g of methyl ethyl ketone are weighed into a vial and dispersed for 10 minutes using ultrasound. For the measurement sample, a laser diffraction particle size distribution measuring device is used, and the wavelength of the light source used is set to blue and red, and the volume-based particle size distribution of the inorganic filler is measured in a flow cell manner, and the average particle size is calculated as the median particle size from the obtained particle size distribution. As a laser diffraction particle size distribution measuring device, for example, "LA-960" made by Horiba, Ltd., etc. can be cited.

[0092] The specific surface area of ​​the inorganic filler (B) is not particularly limited, but is preferably 0.1 m 2 / g or more, more preferably 0.5m 2 / g or more, more preferably 1m 2 / g or more, particularly preferably 5 m 2 The upper limit of the specific surface area of ​​the inorganic filler (B) is not particularly limited, but is preferably 50 m 2 / g or less, more preferably 30m 2 / g or less, more preferably 20m 2 / g or less, particularly preferably 15m 2 The specific surface area of ​​the inorganic filler can be obtained by adsorbing nitrogen on the surface of the sample using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech Co., Ltd.) according to the BET method, and calculating the specific surface area by the BET multipoint method.

[0093] It is preferred that the (B) inorganic filler material is surface treated with an appropriate surface treatment agent. By performing the surface treatment, the moisture resistance and dispersibility of the (B) inorganic filler material can be improved. Examples of the surface treatment agent include vinyl-based silane coupling agents such as vinyltrimethoxysilane and vinyltriethoxysilane; epoxy-based silane coupling agents such as 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane; styrene-based silane coupling agents such as styryltrimethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyl Methacrylic silane coupling agents such as propyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxy silane, and 3-methacryloxypropyl triethoxy silane; acrylic silane coupling agents such as 3-acryloxypropyl trimethoxy silane; N-2-(aminoethyl)-3-aminopropyl methyl dimethoxy silane, N-2-(aminoethyl)-3-aminopropyl trimethoxy silane, 3-aminopropyl trimethoxy silane, 3-aminopropyl triethoxy silane, 3-triethoxy silyl-N-(1,3-dimethyl-butylidene) e) Amino silane coupling agents such as propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8-aminooctyltrimethoxysilane, and N-(vinylbenzyl)-2-aminoethyl-3-aminopropyltrimethoxysilane; isocyanurate silane coupling agents such as tris(trimethoxysilylpropyl)isocyanurate; urea silane coupling agents such as 3-ureidopropyltrialkoxysilane; mercapto silane coupling agents such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane; isocyanate silane coupling agents such as 3-isocyanatepropyltriethoxysilane; Alkane coupling agent; anhydride silane coupling agent such as 3-trimethoxysilylpropyl succinic anhydride; silane coupling agent; methyltrimethoxysilane, dimethyldimethoxysilane, phenyltrimethoxysilane, methyltriethoxysilane, dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyltriethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane and other non-silane coupling-alkoxysilane compounds. Among them, amino-based silane coupling agents are preferred. The surface treatment agent can be used alone or in combination of two or more in any ratio.

[0094] Commercially available products of the surface treatment agent include, for example, "KBM-1003", "KBE-1003" (vinyl silane coupling agent); "KBM-303", "KBM-402", "KBM-403", "KBE-402", "KBE-403" (epoxy silane coupling agent); "KBM-1403" (styrene silane coupling agent); "KBM-502", "KBM-503", "KBE-502", "KBE-503" (methacrylic silane coupling agent); "KBM-5103" (acrylic silane coupling agent); "KBM-602", "KBM-603", "KBM-903", "KBE-903", "KBE-9103P", "KBM-573", "KBM-575" (ammonia silane coupling agent); "KBM-9659" (isocyanurate silane coupling agent); "KBE-585" (urea silane coupling agent); "KBM-802", "KBM-803" (mercapto silane coupling agent); "KBE-9007N" (isocyanate silane coupling agent); "X-12-967C" (anhydride silane coupling agent); "KBM-13", "KBM-22", "KBM-103", "KBE-13", "KBE-22", "KBE-103", "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" (non-silane coupling-alkoxysilane compound), etc.

[0095] From the viewpoint of improving the dispersibility of the inorganic filler, the degree of surface treatment based on the surface treatment agent is preferably within a specified range. Specifically, for 100% by mass of the inorganic filler, it is preferred that 0.2% by mass to 5% by mass of the surface treatment agent be used for surface treatment, more preferably 0.2% by mass to 3% by mass, and further preferably 0.3% by mass to 2% by mass.

[0096] The degree of surface treatment by 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 preferably 0.02 mg / m 2 More preferably 0.1 mg / m 2 More preferably, 0.2 mg / m 2 On the other hand, from the viewpoint of preventing the increase in the melt viscosity of the resin composition and the melt viscosity in the form of a sheet, 1.0 mg / m 2Below, more preferably 0.8 mg / m 2 Below, more preferably 0.5 mg / m 2 the following.

[0097] (B) The amount of carbon per unit surface area of ​​the inorganic filler can be measured after washing the surface-treated inorganic filler with a solvent (e.g., methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent can be added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic washing is performed at 25°C for 5 minutes. The supernatant is removed, the solid component is dried, and then the amount of carbon per unit surface area of ​​the inorganic filler is measured using a carbon analyzer. As a carbon analyzer, "EMIA-320V" manufactured by Horiba, Ltd. can be used.

[0098] When the non-volatile component in the resin composition is set to 100% by mass, the content of the inorganic filler (B) in the resin composition is 40% by mass or less, preferably 38% by mass or less, more preferably 36% by mass or less, further preferably 34% by mass or less, and particularly preferably 32% by mass or less. The lower limit of the content of the inorganic filler (B) in the resin composition is not particularly limited, and when the non-volatile component in the resin composition is set to 100% by mass, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and particularly preferably 30% by mass or more.

[0099] <(C) Polyimide resin>

[0100] The resin composition of the present invention includes (C) a polyimide resin. (C) The polyimide resin is a resin having an imide bond in a repeating unit. (C) The polyimide resin generally includes: (1) a resin obtained by an imidization reaction of a diamine compound and tetracarboxylic anhydride, or (2) a resin obtained by an imidization reaction of a diisocyanate compound and tetracarboxylic anhydride. (C) The polyimide resin also includes modified polyimide resins such as siloxane-modified polyimide resins.

[0101] The (C) polyimide resin is not particularly limited and may include, for example, a structure represented by formula (C1).

[0102] [Chemical formula 3]

[0103]

[0104] [Wherein, X 1represents a tetravalent group obtained by removing two -CO-O-CO- from tetracarboxylic dianhydride, and may be, for example, an organic group formed of two or more (e.g., 2 to 3,000, 2 to 1,000, 2 to 100, or 2 to 50) backbone atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. 2 It means removing two -NH from the diamine compound. 2 The divalent group obtained by removing two -NCO groups from a diisocyanate compound, or the divalent group obtained by removing two -NCO groups from a diisocyanate compound, may be an organic group formed by two or more (e.g., 2 to 3,000, 2 to 1,000, 2 to 100, 2 to 50) backbone atoms selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. n represents an integer greater than 2.]

[0105] X in formula (C1) 1 and X 2 The organic group is not particularly limited as long as it is within the scope of a chemically stable structure, and can be a structure that can be appropriately selected by a person skilled in the art, for example, it can be a structure of a known polyimide resin. (C) When the polyimide resin contains the structure represented by formula (C1), it preferably contains 60% by mass or more of the structure represented by formula (C1), more preferably 80% by mass or more, further preferably 90% by mass or more, and particularly preferably 95% by mass or more.

[0106] (C) The diamine compound used for preparing the polyimide resin is not particularly limited, and examples thereof include aliphatic diamine compounds and aromatic diamine compounds.

[0107] 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-hexanediamine, 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-type diamines (hereinafter also referred to as “dimer diamines”).

[0108] The so-called dimer acid type diamine refers to the two terminal carboxyl groups (-COOH) of the dimer acid being replaced by aminomethyl groups (-CH 2 -NH 2 ) or amino (-NH 2) is replaced by a diamine compound. Dimer acid is a known compound obtained by dimerizing unsaturated fatty acids (preferably unsaturated fatty acids having 11 to 22 carbon atoms, and particularly preferably unsaturated fatty acids having 18 carbon atoms), and its industrial manufacturing process has been roughly standardized in the industry. For dimer acid, in particular, dimer acid with a carbon number of 36 obtained by dimerizing unsaturated fatty acids having 18 carbon atoms such as oleic acid and linoleic acid, which are cheap and easily available, as a main component can be easily obtained. In addition, for dimer acid, depending on the production method, the degree of purification, etc., it sometimes contains any amount of monomer acid, trimer acid, other polymerized fatty acids, etc. In addition, although double bonds remain after the polymerization reaction of unsaturated fatty acids, in this specification, hydrogenated products that are further hydrogenated to reduce the degree of unsaturation are also included in dimer acid. As for the dimer acid type diamine, commercial items are available, for example, "PRIAMINE 1073", "PRIAMINE 1074", and "PRIAMINE 1075" manufactured by Croda Japan Co., Ltd.; "VERSAMINE 551" and "VERSAMINE 552" manufactured by Cognis Japan Co., Ltd., etc. are mentioned.

[0109] Examples of the aromatic diamine compound include phenylenediamine compounds such as 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; naphthalene diamine compounds such as 1,5-diaminonaphthalene, 1,8-diaminonaphthalene, 2,6-diaminonaphthalene, and 2,3-diaminonaphthalene; 4,4'-diamino-2,2'-bis(trifluoromethyl)-1, 1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfide, 4-aminobenzoic acid 4-aminophenyl ester, 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)diphenylamine, 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)diphenylamine, 2,2-bis(3-methyl-4-aminophenyl)propane, 2, Diphenylamine compounds such as 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]-1,1,3-trimethylindane, and 4-aminobenzoic acid 5-amino-1,1'-biphenyl-2-yl ester.

[0110] As the diamine compound, a commercially available diamine compound may be used, or a diamine compound synthesized by a known method may be used. The diamine compound may be used alone or in combination of two or more.

[0111] The diisocyanate compound used for preparing the polyimide resin (C) is not particularly limited, and examples thereof include aliphatic diisocyanate compounds, aromatic diisocyanate compounds, and polyurethane having isocyanato groups at both ends.

[0112] Examples of the aliphatic diisocyanate compound include linear aliphatic diisocyanate compounds such as 1,4-butanediisocyanate, 1,6-hexamethylenediisocyanate, 1,8-octanediisocyanate, and 1,12-dodecanediisocyanate; branched aliphatic diisocyanate compounds such as 2,2,4-trimethyl-1,6-hexamethylenediisocyanate, 2,4,4-trimethyl-1,6-hexamethylenediisocyanate, and 2,2-dimethyl-1,5-pentamethylenediisocyanate; and isophorone diisocyanate (IPDI), Alicyclic diisocyanate compounds such as 1,4-cyclohexylene diisocyanate (CHDI), 4-methyl-1,3-cyclohexylene diisocyanate, 2-methyl-1,3-cyclohexylene diisocyanate, 2-methyl-1,4-cyclohexylene diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 3a,4,5,6,7,7a-hexahydro-4,7-bridged methyleneindan-1,8-ylidene diisocyanate; dimer acid type diisocyanate, etc.

[0113] The dimer acid type diisocyanate is a diisocyanate obtained by converting the amino group (-NH 2 ) is replaced by an isocyanate group (-NCO) to obtain a diisocyanate compound.

[0114] Examples of the aromatic diisocyanate compound include phenylene diisocyanate compounds such as 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate, toluene-2,6-diisocyanate, toluene-2,4-diisocyanate, and toluene-3,5-diisocyanate; naphthalene diisocyanate compounds such as 1,3-naphthalene diisocyanate, 1,6-naphthalene diisocyanate, 1,7-naphthalene diisocyanate, 1,8-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, and 2,7-naphthalene diisocyanate; and diisocyanatophenyl compounds such as 4,4'-diphenylmethane diisocyanate and 4,4'-diphenylether diisocyanate.

[0115] The isocyanate-containing polyurethane at both ends may be a product obtained by subjecting an aliphatic diisocyanate compound and / or an aromatic diisocyanate compound as listed above to a urethanization reaction with a hydroxyl-containing polymer at both ends. Examples of the hydroxyl-containing polymer at both ends include hydroxyl-containing polybutadiene at both ends, hydroxyl-containing hydrogenated polybutadiene at both ends, hydroxyl-containing polyisoprene at both ends, and hydroxyl-containing hydrogenated polyisoprene at both ends; and hydroxyl-containing polyethers such as hydroxyl-containing polyethylene glycol at both ends, hydroxyl-containing polypropylene glycol at both ends, and hydroxyl-containing poly-1,4-butanediol at both ends.

[0116] The number average molecular weight of the polymer with hydroxyl groups at both ends is not particularly limited, but is preferably 500 or more, more preferably 1,000 or more, and further preferably 2,000 or more. The upper limit of the number average molecular weight of the polymer with hydroxyl groups at both ends is not particularly limited, but is preferably 10,000 or less, and more preferably 8,000 or less. The number average molecular weight here is a value measured by gel permeation chromatography (GPC) (in terms of polystyrene).

[0117] The polyurethane having isocyanate groups at both ends is, for example, a polyurethane having isocyanate groups at both ends represented by formula (C2).

[0118] [Chemical formula 4]

[0119]

[0120] [Wherein, X 2a Each independently represents a divalent group obtained by removing two -NCO groups from an aliphatic diisocyanate compound or an aromatic diisocyanate compound, and may be, for example, an organic group consisting of 2 to 50 skeleton atoms selected from carbon atoms, oxygen atoms, nitrogen atoms and sulfur atoms. 2b Each independently represents a divalent group obtained by removing two -OH groups from a hydroxyl polymer at both ends, and may be, for example, an organic group formed by two or more (e.g., 2 to 1,000, 2 to 500) backbone atoms selected from carbon atoms and oxygen atoms. m represents an integer of 1 to 10.].

[0121] As the diisocyanate compound, a commercially available diisocyanate compound may be used, or a diisocyanate compound synthesized by a known method or a method based thereon may be used. The diisocyanate compound may be used alone or in combination of two or more.

[0122] (C) The tetracarboxylic anhydride used for preparing the polyimide resin is not particularly limited, and examples thereof include aliphatic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride.

[0123] Specific examples of the aliphatic tetracarboxylic dianhydride include 1,2,3,4-cyclobutanetetracarboxylic dianhydride, cyclopentanetetracarboxylic dianhydride, cyclohexane-1,2,3,4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic 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, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, etc.

[0124] Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 1,2,3,4-benzene tetracarboxylic dianhydride and the like; naphthalene tetracarboxylic dianhydride, 1,4,5,8-naphthalene tetracarboxylic dianhydride, 2,3,6,7-naphthalene tetracarboxylic dianhydride and the like; anthracene tetracarboxylic dianhydride, 2,3,6,7-anthracene tetracarboxylic dianhydride and the like; 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether ... -diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-diphenylether tetracarboxylic dianhydride, 2,3,3',4'-diphenylsulfone tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, methylene-4 ,4'-diphthalic anhydride, 1,1-ethylidene-4,4'-diphthalic anhydride, 2,2-propylidene-4,4'-diphthalic anhydride, 1,2-ethylene-4,4'-diphthalic anhydride, 1,3-trimethylene-4,4'-diphthalic anhydride, 1,4-tetramethylene-4,4'-diphthalic anhydride, 1,5-pentamethylene-4,4'-diphthalic anhydride, 1,3-bis(3, 1,4-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenoxy)phthalic anhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 4,4'-(4,4'-isopropylidene diphenoxy) diphthalic anhydride and the like.

[0125] As tetracarboxylic dianhydride, commercially available tetracarboxylic dianhydride may be used, or tetracarboxylic dianhydride synthesized by a known method or a method based thereon may be used. Tetracarboxylic dianhydride may be used alone or in combination of two or more.

[0126] The content of the structure derived from the aromatic tetracarboxylic dianhydride relative to the total structure derived from the tetracarboxylic dianhydride constituting the (C) polyimide resin is preferably 10 mol% or more, more preferably 30 mol% or more, further preferably 50 mol% or more, further preferably 70 mol% or more, further more preferably 90 mol% or more, and particularly preferably 100 mol%.

[0127] The weight average molecular weight of the polyimide resin (C) is not particularly limited, but is preferably 1,000 or more, more preferably 3,000 or more, further preferably 5,000 or more, and particularly preferably 7,000 or more. The upper limit of the weight average molecular weight of the polyimide resin (C) is not particularly limited, but is preferably 100,000 or less, more preferably 80,000 or less, particularly preferably 60,000 or less, and particularly preferably 50,000 or less.

[0128] The number average molecular weight of the polyimide resin (C) is not particularly limited, but is preferably 1,000 or more, more preferably 3,000 or more, further preferably 5,000 or more, and particularly preferably 7,000 or more. The upper limit of the number average molecular weight of the polyimide resin (C) is not particularly limited, but is preferably 100,000 or less, more preferably 80,000 or less, particularly preferably 60,000 or less, and particularly preferably 50,000 or less.

[0129] The content of (C) polyimide resin in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 15% by mass or more, and particularly preferably 20% by mass or more. The upper limit of the content of (C) polyimide resin in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, it is preferably 50% by mass or less, more preferably 40% by mass or less, further preferably 35% by mass or less, and particularly preferably 30% by mass or less.

[0130] <(D) Curing agent>

[0131] The resin composition of the present invention may further contain (D) a curing agent. The (D) curing agent has a function of curing the (A) epoxy resin.

[0132] The (D) curing agent is not particularly limited, and examples thereof include phenolic curing agents, naphthol curing agents, anhydride curing agents, active ester curing agents, benzoxazine curing agents, cyanate curing agents, and carbodiimide curing agents. The curing agent may be used alone or in combination of two or more. The (D) curing agent preferably includes a curing agent selected from phenolic curing agents, naphthol curing agents, and active ester curing agents, and particularly preferably includes an active ester curing agent.

[0133] As phenolic curing agent and naphthol curing agent, from the viewpoint of heat resistance and water resistance, preferably, the phenolic curing agent with novolac structure or the naphthol curing agent with novolac structure is used. In addition, from the viewpoint of adhesion with the adherend, preferably, the nitrogen-containing phenolic curing agent or the nitrogen-containing naphthol curing agent is used, and more preferably, the phenolic curing agent containing triazine skeleton or the naphthol curing agent containing triazine skeleton is used. Among them, from the viewpoint of highly satisfying heat resistance, water resistance and adhesion, preferably, the phenolic novolac resin containing triazine skeleton is used. Specific examples of phenol-based curing agents and naphthol-based curing agents include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemicals, "NHN", "CBN", and "GPH" manufactured by Nippon Kayaku Co., Ltd., "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495", "SN-375", and "SN-395" manufactured by Nippon Steel Chemicals Co., Ltd., and "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", "TD2090", and "TD-2090-60M" manufactured by DIC Corporation.

[0134] As the acid anhydride curing agent, there can be mentioned a curing agent having one or more acid anhydride groups in one molecule, preferably a curing agent having two or more acid anhydride groups in one molecule. Specific examples of the acid anhydride curing agent include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, methylhexahydrophthalic anhydride, methylnadic anhydride, hydrogenated methylnadic anhydride, trialkyltetrahydrophthalic anhydride, dodecenylsuccinic anhydride, 5-(2,5-dioxotetrahydro-3-furanyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, dicarboxylic anhydride, and the like. Benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic dianhydride, naphthalene tetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenylsulfone tetracarboxylic 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(trimellitic anhydride ester), styrene-maleic acid resin obtained by copolymerization of styrene and maleic acid, etc. Examples of commercially available acid anhydride curing agents include "HNA-100" and "MH-700" manufactured by Shin Nippon Rika Co., Ltd.

[0135] As active ester curing agent, there is no particular restriction, usually, preferably use phenolic esters, thiophenolic esters, N-hydroxylamine esters, heterocyclic hydroxy compounds and other esters with ester groups having more than 2 high reactive activities in 1 molecule. The active ester curing agent is preferably obtained by the condensation reaction of carboxylic acid compounds and / or thiocarboxylic acid compounds with hydroxy compounds and / or thiol compounds. Especially from the viewpoint of improving heat resistance, preferably the active ester curing agent obtained by carboxylic acid compounds and hydroxy compounds, more preferably the active ester curing agent obtained by carboxylic acid compounds and phenolic compounds and / or naphthol compounds. As carboxylic acid compounds, for example benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, pyromellitic acid etc. can be mentioned. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, methylated bisphenol S, phenol, o-cresol, m-cresol, p-cresol, catechol, α-naphthol, β-naphthol, 1,5-dihydroxynaphthalene, 1,6-dihydroxynaphthalene, 2,6-dihydroxynaphthalene, dihydroxybenzophenone, trihydroxybenzophenone, tetrahydroxybenzophenone, phloroglucinol, pyrogallol, dicyclopentadiene-type diphenol compounds, phenol novolac resins, etc. Here, the so-called "dicyclopentadiene-type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol on one molecule of dicyclopentadiene.

[0136] Specifically, active ester compounds containing a dicyclopentadiene-type diphenol structure, active ester compounds containing a naphthalene structure, active ester compounds containing acetylated products of phenol novolac, and active ester compounds containing benzoylated products of phenol novolac are preferred, and active ester compounds containing a naphthalene structure and active ester compounds containing a dicyclopentadiene-type diphenol structure are more preferred. The so-called "dicyclopentadiene-type diphenol structure" refers to a divalent structural unit composed of phenylene-dicyclopentalene-phenylene.

[0137] Commercially available active ester curing agents include "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65M", and "EXB-8000L-65TM" (manufactured by DIC Corporation), which are active ester compounds containing a dicyclopentadiene-type diphenol structure; "EXB-9416-70BK", "EXB-8150-65T", "EXB-8100L-65T", "EXB-8150L-65T" (manufactured by DIC Corporation); "DC808" (manufactured by Mitsubishi Chemical Corporation), which is an active ester curing agent for acetylated phenol novolac; "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), which are active ester curing agents for benzoylated phenol novolac; and the like.

[0138] Specific examples of the benzoxazine-based curing agent include “JBZ-OP100D” and “ODA-BOZ” manufactured by JFE Chemical Co., Ltd.; “HFB2006M” manufactured by Showa High Molecular Co., Ltd.; and “Pd” and “Fa” manufactured by Shikoku Chemical Industry Co., Ltd.

[0139] Examples of the cyanate curing agent include difunctional cyanate resins such as bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4′-methylenebis(2,6-dimethylphenylcyanate), 4,4′-ethylenediphenyl 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-(methylethylene))benzene, bis(4-cyanatephenyl)sulfide, and bis(4-cyanatephenyl)ether; polyfunctional cyanate resins derived from phenol novolac resins and cresol novolac resins; and prepolymers obtained by partially triazinizing these cyanate resins. Specific examples of cyanate curing agents include "PT30" and "PT60" manufactured by Lonza Japan Co., Ltd. (both are phenol novolac-type multifunctional cyanate resins), "BA230", "BA230S75" (prepolymers obtained by triazine-forming a part or all of bisphenol A dicyanate to form a trimer), etc.

[0140] Specific examples of the carbodiimide-based curing agent include "V-03" and "V-07" manufactured by Nisshinbo Chemical Co., Ltd.

[0141] When the resin composition contains (D) a curing agent, the amount ratio of (A) an epoxy resin to (D) a curing agent is preferably 1:0.2 to 1:2, more preferably 1:0.3 to 1:1.5, and even more preferably 1:0.4 to 1:1.4 in terms of the ratio of [number of epoxy groups of (A) an epoxy resin]: [number of reactive groups of (D) a curing agent]. Here, regarding the reactive group of the (D) curing agent, for example, when the curing agent is a phenolic curing agent or a naphthol curing agent, the reactive group is an aromatic hydroxyl group; when the curing agent is an active ester curing agent, the reactive group is an active ester group; the reactive group varies depending on the type of the curing agent.

[0142] (D) The reactive group equivalent of the curing agent is preferably 50 g / eq. to 3,000 g / eq., more preferably 100 g / eq. to 1,000 g / eq., further preferably 100 g / eq. to 500 g / eq., and particularly preferably 100 g / eq. to 300 g / eq. The reactive group equivalent is the mass of the curing agent per 1 equivalent of reactive groups.

[0143] When the (D) curing agent contains an active ester curing agent, the content thereof is not particularly limited, but is preferably 10% by mass or more, more preferably 20% by mass or more, further preferably 30% by mass or more, and particularly preferably 40% by mass or more, based on the total amount of the (D) curing agent being 100% by mass.

[0144] When the resin composition includes (D) curing agent, the content of (D) curing agent in the resin composition is not particularly limited, and when the non-volatile component in the resin composition is set to 100% by mass, it is preferably 1% by mass or more, more preferably 3% by mass or more, further preferably 4% by mass or more, and particularly preferably 5% by mass or more. The upper limit of the content of (D) curing agent in the resin composition is not particularly limited, and when the non-volatile component in the resin composition is set to 100% by mass, it is preferably 20% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less, and particularly preferably 8% by mass or less.

[0145] <(E) Curing accelerator>

[0146] The resin composition of the present invention may contain (E) a curing accelerator as an optional component. The (E) curing accelerator has a function of accelerating the curing of the (A) epoxy resin.

[0147] (E) curing accelerator is not particularly limited, and examples thereof include phosphorus curing accelerators, urea curing accelerators, amine curing accelerators, imidazole curing accelerators, guanidine curing accelerators, and metal curing accelerators. Among them, phosphorus curing accelerators, amine curing accelerators, imidazole curing accelerators, and metal curing accelerators are preferred, and imidazole curing accelerators are particularly preferred. One curing accelerator may be used alone, or two or more may be used in combination.

[0148] Phosphorus curing accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitic acid salt, tetrabutylphosphonium hexahydrophthalic acid hydrogen salt, tetrabutylphosphonium cresol novolac resin trimer salt, di-tert-butylmethylphosphonium tetraphenylborate and other aliphatic phosphonium salts; methyltriphenylphosphonium bromide, ethyltriphenylphosphonium bromide, propyltriphenylphosphonium bromide, butyltriphenylphosphonium bromide, benzyltriphenylphosphonium chloride, tetraphenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolylborate, Aromatic phosphonium salts such as tetraphenylphosphonium tetraphenylborate, tetraphenylphosphonium tetra-p-tolylborate, triphenylethylphosphonium tetraphenylborate, tris(3-methylphenyl)ethylphosphonium tetraphenylborate, tris(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate; aromatic phosphine-borane complexes such as triphenylphosphine-triphenylborane; aromatic phosphine-quinone addition reactants such as triphenylphosphine-p-benzoquinone addition reactants; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine, di-tert-butyl(2-butenyl)phosphine, Aliphatic phosphines such as di-tert-butyl (3-methyl-2-butenyl) phosphine and tricyclohexyl phosphine; dibutylphenyl phosphine, di-tert-butylphenyl phosphine, methyldiphenyl phosphine, ethyldiphenyl phosphine, butyldiphenyl phosphine, diphenylcyclohexyl phosphine, triphenyl phosphine, tri-o-tolyl phosphine, tri-m-tolyl phosphine, tri-p-tolyl phosphine, tri(4-ethylphenyl)phosphine, tri(4-propylphenyl)phosphine, tri(4-isopropylphenyl)phosphine, tri(4-butylphenyl)phosphine, tri(4-tert-butylphenyl)phosphine, tri(2,4-dimethylphenyl)phosphine, tri(2,5-dimethylphenyl)phosphine, tri(2,6-dimethylphenyl)phosphine Aromatic phosphines such as phosphine, tri(3,5-dimethylphenyl)phosphine, tri(2,4,6-trimethylphenyl)phosphine, tri(2,6-dimethyl-4-ethoxyphenyl)phosphine, tri(2-methoxyphenyl)phosphine, tri(4-methoxyphenyl)phosphine, tri(4-ethoxyphenyl)phosphine, tri(4-tert-butoxyphenyl)phosphine, diphenyl-2-pyridylphosphine, 1,2-bis(diphenylphosphino)ethane, 1,3-bis(diphenylphosphino)propane, 1,4-bis(diphenylphosphino)butane, 1,2-bis(diphenylphosphino)acetylene, and 2,2'-bis(diphenylphosphino)diphenyl ether, etc.

[0149] Examples of the urea curing accelerator include 1,1-dimethylurea; aliphatic dimethylureas such as 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1,1-dimethylurea, and 3-cyclooctyl-1,1-dimethylurea; 3-phenyl-1,1-dimethylurea, 3-(4-chlorophenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)-1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3-(3,4-dimethylphenyl)-1,1 -dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxyphenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethylurea) [toluenebisdimethylurea] and the like.

[0150] Examples of the amine curing accelerator include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6-tris(dimethylaminomethyl)phenol, and 1,8-diazabicyclo(5,4,0)-undecene, and 4-dimethylaminopyridine is preferred.

[0151] 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-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1') imidazole compounds such as 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, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, and 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins.

[0152] As the imidazole-based curing accelerator, a commercially available item may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0153] Examples of the guanidine-based curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine.

[0154] As metal curing accelerators, organic metal complexes or organic metal salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin can be cited. As specific examples of organic metal complexes, organic cobalt complexes such as cobalt acetylacetonate (II), cobalt acetylacetonate (III), organic copper complexes such as copper acetylacetonate (II), organic zinc complexes such as zinc acetylacetonate (II), organic iron complexes such as iron acetylacetonate (III), organic nickel complexes such as nickel acetylacetonate (II), and organic manganese complexes such as manganese acetylacetonate (II) can be cited. As organic metal salts, for example, zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, zinc stearate, etc. can be cited.

[0155] When the resin composition includes (E) curing accelerator, the content of (E) curing accelerator in the resin composition is not particularly limited, and when the non-volatile component in the resin composition is set to 100% by mass, it is preferably 0.001% by mass or more, more preferably 0.01% by mass or more, further preferably 0.05% by mass or more, and particularly preferably 0.1% by mass or more. The upper limit of the content of (E) curing accelerator in the resin composition is not particularly limited, and when the non-volatile component in the resin composition is set to 100% by mass, it is preferably 5% by mass or less, more preferably 3% by mass or less, further preferably 1% by mass or less, and particularly preferably 0.5% by mass or less.

[0156] <(F) Other additives>

[0157] The resin composition of the present invention may further contain any additive as a non-volatile component. Examples of such additives include organic fillers such as rubber particles, polyamide microparticles, and silicone particles; thermoplastic resins such as phenoxy resins, polyvinyl acetal resins, polyolefin resins, polysulfone resins, polyethersulfone resins, polyphenylene ether resins, polycarbonate resins, polyetheretherketone resins, and polyester resins; organic metal compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; colorants such as phthalocyanine blue, phthalocyanine green, iodine green, diazo yellow, crystal violet, titanium oxide, and carbon black; polymerization inhibitors such as hydroquinone, catechol, pyrogallol, and phenothiazine; homogenizers such as silicone homogenizers and acrylic polymer homogenizers; thickeners such as bentonite and montmorillonite; silicone dispersants; Defoamers such as foaming agents, acrylic defoamers, fluorine defoamers, and vinyl resin defoamers; UV absorbers such as benzotriazole UV absorbers; adhesion enhancers such as urea silane; adhesion imparting agents such as triazole adhesion imparting agents, tetrazole adhesion imparting agents, and triazine adhesion imparting agents; antioxidants such as hindered phenol antioxidants and hindered amine antioxidants; fluorescent whitening agents such as stilbene derivatives; surfactants such as fluorine surfactants and silicone surfactants; phosphorus flame retardants (such as phosphate compounds, phosphazene compounds, phosphinic acid compounds, red phosphorus), nitrogen flame retardants (such as melamine sulfate), halogen flame retardants, inorganic flame retardants (such as antimony trioxide), etc. The additives can be used alone or in combination of two or more in any ratio. (F) The content of other additives can be appropriately set by those skilled in the art.

[0158] <(G) Organic solvent>

[0159] The resin composition of the present invention may contain any organic solvent as a volatile component in addition to the above-mentioned non-volatile components. As the (G) organic solvent, a known organic solvent may be used appropriately, and the type thereof is not particularly limited. As the (G) organic solvent, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; ester solvents such as methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, isoamyl acetate, methyl propionate, ethyl propionate, and γ-butyrolactone; ether solvents such as tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether, dibutyl ether, and diphenyl ether; alcohol solvents such as methanol, ethanol, propanol, butanol, and ethylene glycol; 2-ethoxyethyl acetate, propylene glycol monomethyl ether acetate, diethylene glycol monoethyl ether acetate, and carbitol acetate (ethyldiglycolacetate) , γ-butyrolactone, methyl methoxypropionate and other ether ester solvents; methyl lactate, ethyl lactate, methyl 2-hydroxyisobutyrate and other ester alcohol solvents; 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol monobutyl ether (butyl carbitol) and other ether alcohol solvents; N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone and other amide solvents; dimethyl sulfoxide and other sulfoxide solvents; acetonitrile, propionitrile and other nitrile solvents; hexane, cyclopentane, cyclohexane, methylcyclohexane and other aliphatic hydrocarbon solvents; benzene, toluene, xylene, ethylbenzene, trimethylbenzene and other aromatic hydrocarbon solvents. (G) The organic solvent may be used alone or in combination of two or more in any ratio.

[0160] <Method for producing resin composition>

[0161] The resin composition of the present invention can be manufactured in the following manner, for example, in any reaction vessel, in any order and / or in part or in whole, simultaneously add (A) epoxy resin, (B) inorganic filler, (C) polyimide resin (preliminary imidized material), (D) curing agent as required, (E) curing accelerator as required, (F) other additives as required, and (G) organic solvent as required, and mix. In addition, in the process of adding each component and mixing, the temperature can be appropriately set, and heating and / or cooling can be performed temporarily or throughout. In addition, in the process of adding each component and mixing, stirring or vibration can be performed. In addition, when adding and mixing or subsequently, for example, stirring devices such as mixers can be used to stir the resin composition so that it is evenly dispersed.

[0162] <Characteristics of resin composition>

[0163] The resin composition of the present invention comprises (A) an epoxy resin, (B) an inorganic filler, and (C) a polyimide resin, wherein the component (A) comprises (A-1) an epoxy resin containing a siloxane skeleton. Therefore, even if the content of the inorganic filler (B) is a low compounding amount of 40% by mass or less, the viscosity can be suppressed to a low level, and a cured product having excellent flexibility and excellent insulation reliability can be obtained.

[0164] The cured product of the resin composition of the present invention has excellent flexibility. Therefore, for example, as in the following Test Example 1, for a layered cured product of the resin composition having a thickness of 40 μm, a width of 15 mm, and a length of 110 mm, the number of folding times when the MIT folding resistance test is performed in accordance with JIS C-5016 under the conditions of a load of 2.5 N, a bending angle of 90 degrees, a bending speed of 175 times / min, and a bending radius of 1.0 mm can be preferably 3,000 times or more, more preferably 5,000 times or more, further preferably 7,000 times or more, and particularly preferably 8,000 times or more.

[0165] The cured product of the resin composition of the present invention has excellent insulation reliability. Therefore, for example, the insulation resistance value of the insulation layer of the evaluation substrate measured by the method of Test Example 3 described below can be preferably 1.00×10 7 Ω or more, more preferably 1.00×10 8 Ω or more, more preferably 1.00×10 9 Ω or more, particularly preferably 1.00×10 10 Ω or more.

[0166] The resin composition of the present invention can suppress viscosity to a low level. Therefore, for example, as in the following Test Example 2, a glass probe having a diameter of 5 mm and a load of 1 kgf / cm 2 The adhesive force measured under the conditions of a contact speed of 0.5 mm / sec, a tensile speed of 0.5 mm / sec, a holding time of 10 seconds, and a temperature of 80°C is preferably 1.8 N or less, more preferably 1.6 N or less, further preferably 1.4 N or less, and particularly preferably 1.2 N or less.

[0167] <Application of resin composition>

[0168] The resin composition of the present invention can be used in a wide range of applications such as insulating materials such as printed wiring boards and multilayer flexible substrates, solder resists, underfill materials, chip bonding materials, semiconductor sealing materials, hole filling resins, and component embedding resins. Printed wiring boards, multilayer flexible substrates, etc. can be manufactured using sheet-like laminated materials such as resin sheets and prepregs.

[0169] <Resin Sheet>

[0170] 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.

[0171] The thickness of the resin composition layer is preferably 200 μm or less, more preferably 150 μm or less, further preferably 100 μm or less, and particularly preferably 70 μm or less. The lower limit of the thickness of the resin composition layer is not particularly limited, and can usually be 1 μm or more, 1.5 μm or more, 2 μm or more, etc.

[0172] Examples of the support include films made of plastic materials, metal foils, and release papers, and films made of plastic materials and metal foils are preferred.

[0173] When a film formed of a plastic material is used as a support, the plastic material includes polyesters such as polyethylene terephthalate (hereinafter, sometimes referred to as "PET") and polyethylene naphthalate (hereinafter, sometimes referred to as "PEN"), polycarbonate (hereinafter, sometimes referred to as "PC"), acrylic polymers such as polymethyl methacrylate (PMMA), cyclic polyolefins, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are preferred, and inexpensive polyethylene terephthalate is particularly preferred.

[0174] When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil, preferably copper foil. The copper foil may be a foil made of a single metal such as copper or an alloy of copper and other metals (e.g., tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.).

[0175] The surface of the support to be in contact with the resin composition layer may be subjected to matte treatment, corona treatment, or antistatic treatment.

[0176] In addition, as a support, a support with a release layer having a release layer on the surface bonded to the resin composition layer can be used. As a release agent used in the release layer of a support with a release layer, for example, one or more release agents selected from the group consisting of alkyd resins, polyolefin resins, polyurethane resins, and silicone resins can be cited. The support with a release layer can use a commercial product, for example, a PET film having a release layer with an alkyd resin-based release agent as the main component, i.e., "SK-1", "AL-5", "AL-7" made by Lintec, "Lumirror T60" made by Toray, "Purex" made by Teijin, "Unipeel" made by UNITIKA, etc.

[0177] The thickness of the support is not particularly limited, but is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. When a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above range.

[0178] In one embodiment, the resin sheet may further include other layers as needed. As the other layers, for example, a protective film selected according to the support and provided on the surface of the resin composition layer that is not bonded to the support (i.e., the surface on the opposite side of the support) can be cited. The thickness of the protective film is not particularly limited, for example, 1 μm to 40 μm. By laminating the protective film, dust and the like can be prevented from adhering to the surface of the resin composition layer or from being damaged on the surface of the resin composition layer.

[0179] The resin sheet can be produced by directly coating the resin composition on a support using a die coater or the like, or by preparing a resin varnish by dissolving the resin composition in an organic solvent and coating it on a support using a die coater or the like, followed by drying to form a resin composition layer.

[0180] Examples of the organic solvent that can be used when coating the support include the same organic solvents as those listed in the description of the organic solvent as a component of the resin composition. The organic solvent may be used alone or in combination of two or more.

[0181] Drying can be carried out by known methods such as heating and blowing hot air. The drying conditions are not particularly limited, and the drying is carried out in a manner such that the content of the organic solvent in the resin composition layer is 10% by mass or less, preferably 5% by mass or less. Although it varies depending on the boiling point of the organic solvent in the resin composition or resin varnish, for example, in the case of using a resin composition or resin varnish containing 30% by mass to 60% by mass of an organic solvent, the resin composition layer can be formed by drying at 50° C. to 150° C. for 3 minutes to 10 minutes.

[0182] The resin sheet can be stored in a roll. When the resin sheet has a protective film, the protective film can be peeled off before use.

[0183] <Laminated Sheet>

[0184] The laminated sheet is a sheet made by laminating and curing multiple layers of resin composition. The laminated sheet contains multiple layers of insulating layers as a cured product of the resin composition layer. Usually, the number of resin composition layers laminated to make the laminated sheet is consistent with the number of insulating layers contained in the laminated sheet. The number of specific insulating layers per laminated sheet is usually more than 2, preferably more than 3, particularly preferably more than 5, preferably less than 20, more preferably less than 15, and particularly preferably less than 10.

[0185] The laminated sheet can be a sheet used by bending one side thereof relative to the other. The minimum bending radius of the laminated sheet is not particularly limited, and is preferably 0.1 mm or more, more preferably 0.2 mm or more, further preferably 0.3 mm or more, preferably 5 mm or less, more preferably 4 mm or less, and particularly preferably 3 mm or less.

[0186] Each insulating layer included in the laminated sheet may have a hole formed therein, and the hole can function as a through hole or a through hole in the multilayer flexible substrate.

[0187] For the laminated sheet, in addition to the insulating layer, any element may be further included. For example, the laminated sheet may have a conductor layer as an arbitrary element. The conductor layer is usually formed partially on the surface of the insulating layer or between the insulating layers. The conductor layer usually functions as a wiring in the multilayer flexible substrate.

[0188] The conductor material used in the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer includes one or more metals selected from gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductor material may be a single metal or an alloy. As an alloy, for example, an alloy of two or more metals selected from the above metals (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) can be mentioned. Among them, from the viewpoint of versatility, cost, ease of patterning, etc. of the formation of the conductor layer, chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper as a single metal is preferred; and alloys such as nickel-chromium alloy, copper-nickel alloy, and copper-titanium alloy. Among them, single metals of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper are more preferred; and nickel-chromium alloy, and single metal of copper is further preferred.

[0189] The conductor layer may be a single-layer structure or a multi-layer structure including two or more single metal layers or alloy layers formed of different types of metals or alloys. When the conductor layer is a multi-layer structure, the layer in contact with the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of a nickel-chromium alloy.

[0190] In order to make the conductor layer function as wiring, it can be patterned.

[0191] The thickness of the conductor layer depends on the design of the multi-layer flexible substrate, and is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, further preferably 10 μm to 20 μm, and particularly preferably 15 μm to 20 μm.

[0192] The thickness of the laminated sheet is preferably 100 μm or more, more preferably 150 μm or more, particularly preferably 200 μm or more, and is preferably 2,000 μm or less, more preferably 1,000 μm or less, particularly preferably 500 μm or less.

[0193] <Method for producing laminated sheet>

[0194] The laminated sheet can be manufactured using a manufacturing method comprising the following steps: (a) a step of preparing a resin sheet, and (b) a step of using a resin sheet and laminating and curing a resin composition layer. The order of laminating and curing the resin composition layer is arbitrary, as long as the desired laminated sheet can be obtained. Depending on the components contained in the resin composition, for example, after all the multi-layer resin composition layers are laminated, the laminated multi-layer resin composition layers can be cured together. In addition, for example, each time other resin composition layers are laminated on a resin composition layer, the laminated resin composition layer can be cured.

[0195] A preferred embodiment of step (b) is described below. In the embodiments described below, for the purpose of distinction, the resin composition layers are appropriately numbered as "first resin composition layer" and "second resin composition layer", and further, similarly to the resin composition layers, the insulating layers obtained by curing these resin composition layers are also numbered as "first insulating layer" and "second insulating layer".

[0196] In a preferred embodiment, step (b) comprises the following steps:

[0197] (II) a step of curing the first resin composition layer to form a first insulating layer,

[0198] (VI) a step of laminating a second resin composition layer on the first insulating layer, and

[0199] (VII) a step of curing the second resin composition layer to form a second insulating layer. In addition, step (b) may include any of the following steps as required:

[0200] (I) a step of laminating a first resin composition layer on a sheet-like supporting substrate,

[0201] (III) a step of opening a hole in the first insulating layer,

[0202] (IV) a step of roughening the first insulating layer,

[0203] (V) forming a conductor layer on the first insulating layer;

[0204] Hereinafter, each step will be described.

[0205] Step (I) is a step of laminating the first resin composition layer on the sheet-like supporting substrate before step (II). The sheet-like supporting substrate is a removable member, and for example, a plate-like, sheet-like, or film-like member can be used.

[0206] The lamination of the sheet-like support substrate and the first resin composition layer can be implemented by vacuum lamination. In the vacuum lamination method, the heating and pressing temperature is preferably 60°C to 160°C, more preferably in the range of 80°C to 140°C, the heating and pressing pressure is preferably 0.098MPa to 1.77MPa, more preferably in the range of 0.29MPa to 1.47MPa, and the heating and pressing time is preferably 20 seconds to 400 seconds, more preferably in the range of 30 seconds to 300 seconds. The lamination is preferably implemented under reduced pressure conditions with a pressure of 26.7hPa or less.

[0207] Lamination can be performed using a commercially available vacuum laminator. Examples of commercially available vacuum laminators include a vacuum pressure laminator manufactured by Meiki Mfg. Co., Ltd., a vacuum applicator manufactured by Nikko-Materials Co., Ltd., and a batch vacuum pressure laminator.

[0208] When using a resin sheet, the lamination of the sheet-like support substrate and the first resin composition layer can be performed, for example, by pressing the resin sheet from the support body side, and the first resin composition layer of the resin sheet is heated and pressed to the sheet-like support substrate. As a member for heating and pressing the resin sheet to the sheet-like support substrate (hereinafter sometimes appropriately referred to as a "heating and pressing member"), for example, a heated metal plate (SUS end plate, etc.) or a metal roller (SUS roller) can be cited. Preferably, the heating and pressing member is not directly pressed to the resin sheet, but is pressed through an elastic material such as heat-resistant rubber so that the first resin composition layer fully follows the surface unevenness of the sheet-like support substrate.

[0209] After lamination, by pressing at normal pressure (under atmospheric pressure), for example, with a heating and pressing member, the first resin composition layer can be smoothed. For example, when a resin sheet is used, the first resin composition layer of the resin sheet can be smoothed by pressing the resin sheet with a heating and pressing member from the support side. The pressing conditions of the smoothing treatment can be set to the same conditions as the heating and pressing conditions of the above-mentioned lamination. The smoothing treatment can be performed using a commercially available laminator. The lamination and smoothing treatment can be performed continuously using the above-mentioned commercially available vacuum laminator.

[0210] Step (II) is a step of curing the first resin composition layer to form a first insulating layer. The curing conditions of the first resin composition layer are not particularly limited, and the conditions used when forming the insulating layer of the printed wiring board can be arbitrarily applied. The first resin composition layer can be cured by thermal curing.

[0211] Generally, specific heat curing conditions vary depending on the type of resin composition. For example, the curing temperature is preferably 120°C to 240°C, more preferably 150°C to 220°C, and further preferably 170°C to 210°C. In addition, the curing time is preferably 5 minutes to 120 minutes, more preferably 10 minutes to 110 minutes, and further preferably 20 minutes to 100 minutes.

[0212] The first resin composition layer may be preheated at a temperature lower than the curing temperature before the first resin composition layer is thermally cured. For example, the first resin composition layer may be preheated at a temperature of 50° C. or higher and lower than 120° C. (preferably 60° C. or higher and 115° C. or lower, more preferably 70° C. or higher and 110° C. or lower) for 5 minutes or more (preferably 5 minutes to 150 minutes, more preferably 15 minutes to 120 minutes, and further preferably 15 minutes to 100 minutes) before the first resin composition layer is thermally cured.

[0213] Step (III) is a step of opening a hole in the first insulating layer. Through this step (III), holes such as through holes and through holes can be formed in the first insulating layer. For opening a hole, for example, a drill, laser, plasma, etc. can be used, depending on the composition of the resin composition. The size and shape of the hole can be appropriately set according to the design of the multilayer flexible substrate.

[0214] Step (IV) is a step of roughening the first insulating layer. Usually, smear removal is also performed in step (IV). Therefore, the roughening treatment is sometimes called desmear treatment. As an example of the roughening treatment, a swelling treatment using a swelling solution, a roughening treatment using an oxidizing agent, and a neutralization treatment using a neutralizing solution can be cited in sequence.

[0215] There are no particular restrictions on the swelling liquid, and examples include alkaline aqueous solutions such as sodium hydroxide aqueous solution and potassium hydroxide aqueous solution. Examples of commercially available swelling liquids include "Swelling DipSecuriganth P" and "Swelling DipSecuriganth SBU" manufactured by Atotech Japan. The swelling treatment using the swelling liquid can be performed, for example, by immersing the cured body in a swelling liquid at 30°C to 90°C for 1 minute to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to an appropriate level, it is preferred to immerse the insulating layer in a swelling liquid at 40°C to 80°C for 5 minutes to 15 minutes.

[0216] As the oxidant, there is no particular limitation, and an alkaline permanganate solution formed by dissolving permanganate in an aqueous sodium hydroxide solution or an aqueous potassium hydroxide solution can be cited. The concentration of permanganate in the alkaline permanganate solution is preferably 5% by mass to 10% by mass. As commercially available oxidants, alkaline permanganate solutions such as "Concentrate Compact P", "Concentrate Compact CP", and "Dosing Solution Securiganth P" manufactured by Atotech Japan Co., Ltd. can be cited. The roughening treatment using the oxidant can be carried out by immersing the cured body in an oxidant solution heated to 60°C to 80°C for 10 minutes to 30 minutes.

[0217] In addition, an acidic aqueous solution can be used as a neutralizing solution. As a commercially available product, for example, "Reduction Solution Securiganth P" manufactured by Atotech Japan Co., Ltd. can be cited. The treatment with the neutralizing solution can be carried out by immersing the solidified body in a neutralizing solution at 30°C to 80°C for 5 minutes to 30 minutes. In consideration of operability, etc., it is preferred to immerse the solidified body in a neutralizing solution at 40°C to 70°C for 5 minutes to 20 minutes.

[0218] The arithmetic mean roughness (Ra) of the surface of the roughened first insulating layer is preferably 400 nm or less, more preferably 300 nm or less, and further preferably 200 nm or less. The lower limit is not particularly limited and may be 30 nm or more, 40 nm or more, or 50 nm or more.

[0219] Step (V) is a step of forming a conductor layer on the first insulating layer as needed. Regarding the method for forming the conductor layer, for example, a plating method, a sputtering method, a vapor deposition method, etc. can be cited, among which a plating method is preferred. As a preferred example, a method of plating on the surface of the first insulating layer using an appropriate method such as a semi-additive method and a full-additive method to form a conductor layer having a desired wiring pattern can be cited. Among them, from the viewpoint of simplicity of production, a semi-additive method is preferred.

[0220] The following is an example of forming a conductor layer using a semi-additive method. First, a plating seed layer is formed on the surface of a first insulating layer by electroless plating. Next, a mask pattern is formed on the formed plating seed layer to expose a portion of the plating seed layer corresponding to a desired wiring pattern. A metal layer is formed on the exposed plating seed layer by electrolytic plating, and then the mask pattern is removed. Then, the unnecessary plating seed layer is removed by etching or other treatments to form a conductor layer having a desired wiring pattern.

[0221] In step (II), the first insulating layer is obtained, and if necessary, after step (III), step (IV), and step (V), step (VI) is performed. Step (VI) is a step of laminating the second resin composition layer on the first insulating layer. The lamination of the first insulating layer and the second resin composition layer can be performed by the same method as the lamination of the sheet-like supporting substrate and the first resin composition layer in step (I).

[0222] However, when the first resin composition layer is formed using a resin sheet, the support of the resin sheet is removed before step (VI). The support may be removed between step (I) and step (II), between step (II) and step (III), between step (III) and step (IV), or between step (IV) and step (V).

[0223] After step (VI), step (VII) is performed. Step (VII) is a step of curing the second resin composition layer to form a second insulating layer. The curing of the second resin composition layer can be performed by the same method as the curing of the first resin composition layer in step (II). Thus, a laminated sheet including a multilayer insulating layer such as a first insulating layer and a second insulating layer can be obtained.

[0224] In addition, in the method according to the aforementioned embodiment, as necessary, a step (VIII) of opening a hole in the second insulating layer, a step (IX) of roughening the second insulating layer, and a step (X) of forming a conductor layer on the second insulating layer may be performed. The opening of the second insulating layer in step (VIII) may be performed by the same method as the opening of the first insulating layer in step (III). In addition, the roughening of the second insulating layer in step (IX) may be performed by the same method as the roughening of the first insulating layer in step (IV). Furthermore, the formation of the conductor layer on the second insulating layer in step (X) may be performed by the same method as the formation of the conductor layer on the first insulating layer in step (V).

[0225] In the aforementioned embodiment, the embodiment of manufacturing a laminated sheet by laminating and curing two layers of resin composition layers such as the first resin composition layer and the second resin composition layer is described, but a laminated sheet can also be manufactured by laminating and curing more than three layers of resin composition layers. For example, in the method related to the aforementioned embodiment, the laminating and curing of the resin composition layer based on process (VI) to process (VII), and the opening of the insulating layer based on process (VIII) to process (X) as needed, the roughening treatment of the insulating layer, and the formation of the conductor layer on the insulating layer can be repeatedly implemented to manufacture a laminated sheet. Thus, a laminated sheet comprising more than three insulating layers can be obtained.

[0226] Furthermore, the method according to the above-mentioned embodiment may further include any steps other than the above-mentioned steps. For example, when step (I) is performed, a step of removing the sheet-like supporting substrate may be performed.

[0227] <Multilayer flexible substrate>

[0228] The multilayer flexible substrate includes a laminated sheet. The multilayer flexible substrate may include only the laminated sheet, or may include an arbitrary member in combination with the laminated sheet. Examples of the arbitrary member include electronic components and cover films.

[0229] The multilayer flexible substrate can be manufactured using a manufacturing method including the above-mentioned method for manufacturing a laminated sheet. Therefore, the multilayer flexible substrate can be manufactured using a manufacturing method including the following steps: (a) a step of preparing a resin sheet, and (b) a step of using the resin sheet to laminate and cure a plurality of resin composition layers.

[0230] The method for manufacturing a multilayer flexible substrate may include not only the aforementioned steps but also any other steps. For example, the method for manufacturing a multilayer flexible substrate having an electronic component may include the step of bonding the electronic component to a laminated sheet. The bonding conditions between the laminated sheet and the electronic component may be any conditions that can connect the terminal electrodes of the electronic component to the conductor layer as wiring provided on the laminated sheet. In addition, for example, the method for manufacturing a multilayer flexible substrate having a cover film may include the step of laminating the laminated sheet and the cover film.

[0231] The aforementioned multi-layer flexible substrate can usually be used by being bent in a manner that one surface of the laminated sheet included in the multi-layer flexible substrate faces each other. For example, the multi-layer flexible substrate is accommodated in a housing of a semiconductor device in a state where the multi-layer flexible substrate is bent and reduced in size. In addition, for example, in a semiconductor device having a bendable movable portion, the multi-layer flexible substrate is provided in the movable portion.

[0232] <Semiconductor devices>

[0233] The semiconductor device includes the aforementioned multi-layer flexible substrate. The semiconductor device includes, for example, a multi-layer flexible substrate and a semiconductor chip mounted on the multi-layer flexible substrate. In most semiconductor devices, the multi-layer flexible substrate can be bent in a manner such that one surface of the laminated sheet included in the multi-layer flexible substrate faces each other and is accommodated in a housing of the semiconductor device.

[0234] Examples of the semiconductor device include various semiconductor devices that can be used in electrical products (eg, computers, mobile phones, digital cameras, and televisions) and vehicles (eg, motorcycles, cars, trains, ships, and airplanes).

[0235] The semiconductor device described above can be manufactured, for example, using a manufacturing method including the steps of preparing a multilayer flexible substrate, bending the multilayer flexible substrate so that one surface of a laminated sheet faces each other, and housing the bent multilayer flexible substrate in a housing.

[0236] Example

[0237] The present invention is specifically described below by way of examples. The present invention is not limited to these examples. It should be noted that, below, unless otherwise clearly stated, "parts" and "%" indicating amounts represent "parts by mass" and "% by mass", respectively. In addition, unless otherwise clearly stated, the operations described below are performed under normal temperature and pressure (25°C, 1 atm).

[0238] <Synthesis Example 1: Synthesis of polyimide resin 1>

[0239] In a reaction container, 50 g of G-3000 (bifunctional hydroxy-terminated polybutadiene, number average molecular weight = 5,047 (GPC method), hydroxyl equivalent = 1,798 g / eq., solid content 100 mass %: manufactured by Nippon Soda Co., Ltd.), 23.5 g of Ipsol 150 (aromatic hydrocarbon mixed solvent: manufactured by Idemitsu Petrochemical Co., Ltd.), and 0.005 g of dibutyltin laurate were mixed and uniformly dissolved. After becoming uniform, the temperature was raised to 50° C., and 4.8 g of toluene-2,4-diisocyanate (isocyanate equivalent = 87.08 g / eq.) was added while stirring, and the reaction was carried out for about 3 hours. Next, after the reaction product was cooled to room temperature, 8.96 g of benzophenonetetracarboxylic dianhydride (anhydride equivalent = 161.1 g / eq.), 0.07 g of triethylenediamine, and 40.4 g of ethyl diglycol acetate (diethylene glycol monoethyl ether acetate) (manufactured by Daicel Corporation) were added thereto, and the temperature was raised to 130° C. while stirring, and the reaction was carried out for about 4 hours. FTIR was used to analyze the reaction product at 2250 cm -1The disappearance of the NCO peak was confirmed. Based on the confirmation of the disappearance of the NCO peak, the reaction was regarded as the end point. After the reactants were cooled to room temperature, they were filtered with a 100-mesh filter cloth to obtain a polyimide resin 1 having an imide skeleton, a carbamate skeleton, and a butadiene skeleton.

[0240] Viscosity: 7.5 Pa·s (25°C, E-type viscometer)

[0241] Acid value: 16.9mgKOH / g

[0242] Solid content: 50% by mass

[0243] Number average molecular weight: 13,723

[0244] Glass transition temperature: -10℃

[0245] The content of the polybutadiene structural part: 50 / (50+4.8+8.96)×100=78.4 mass %.

[0246] <Synthesis Example 2: Synthesis of polyimide resin 2>

[0247] In a 500 ml separable flask equipped with a nitrogen inlet tube and a stirring device, 9.13 g (30 mmol) of 5-amino-1,1'-biphenyl-2-yl 4-aminobenzoate, 15.61 g (30 mmol) of 4,4'-(4,4'-isopropylidene diphenyloxy) diphthalic anhydride, 94.64 g of N-methyl-2-pyrrolidone, 0.47 g (6 mmol) of pyridine, and 10 g of toluene were added, and an imidization reaction was carried out for 4 hours at 180° C. under a nitrogen atmosphere while discharging toluene outside the system in the middle, thereby obtaining a polyimide solution (non-volatile component is 20% by mass) containing polyimide resin 2. In the polyimide solution, no precipitation of the synthesized polyimide resin 2 was observed. The weight average molecular weight of the polyimide resin 2 is 45,000.

[0248] <Synthesis Example 3: Synthesis of polyimide resin 3>

[0249] Into a reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen inlet tube, 65.0 g of aromatic tetracarboxylic dianhydride ("BisDA-1000" manufactured by SABIC Japan, 4,4'-(4,4'-isopropylidene diphenyloxy) diphthalic dianhydride), 266.5 g of cyclohexanone, and 44.4 g of methylcyclohexane were placed, and the solution was heated to 60°C. Next, 43.7 g of dimer diamine ("PRIAMINE 1075" manufactured by Croda Japan) and 5.4 g of 1,3-bis(aminomethyl)cyclohexane were added dropwise, and then an imidization reaction was carried out at 140°C for 1 hour. Thus, a polyimide solution (non-volatile component is 30% by mass) containing polyimide resin 3 was obtained. In addition, the weight average molecular weight of polyimide resin 3 is 25,000.

[0250] <Synthesis Example 4: Synthesis of polyimide resin 4>

[0251] Prepare a 500mL removable flask equipped with a water quantitative receiver connected to a reflux condenser, a nitrogen inlet tube, and a stirrer. Add 20.3g of 4,4'-oxydiphthalic anhydride (ODPA), 200g of γ-butyrolactone, 20g of toluene, and 29.6g of 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane to the flask, stir at 45°C for 2 hours under a nitrogen stream, and react. Next, the reaction solution is heated, and the condensation water is removed azeotropically with toluene under a nitrogen stream while being maintained at about 160°C. Confirm that a specified amount of water has accumulated in the water quantitative receiver and that water outflow is no longer observed. After confirmation, the reaction solution is further heated and stirred at 200°C for 1 hour. Then, the mixture was cooled to obtain a polyimide solution (non-volatile content: 20% by mass) containing a polyimide resin 4 having a 1,1,3-trimethylindane skeleton. The obtained polyimide resin 4 has a repeating unit represented by the following formula (X1) and a repeating unit represented by the following formula (X2). In addition, the weight average molecular weight of the polyimide resin 4 is 12,000.

[0252] [Chemical formula 5]

[0253]

[0254] [Chemical formula 6]

[0255]

[0256] <Example 1: Preparation of resin composition 1>

[0257] While stirring, 5 parts of a biphenylene epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185 g / eq.), 5 parts of a naphthalene epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent of about 332 g / eq.), 10 parts of a bisphenol AF epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238 g / eq.), 2 parts of a cyclohexane epoxy resin ("ZX1658GS" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 135 g / eq.), and 40 parts of the polyimide resin 1 obtained in Synthesis Example 1 (non-volatile content of 50% by mass) were heated and dissolved in 10 parts of cyclohexanone. After cooling to room temperature, 4 parts of a cresol novolac curing agent containing a triazine skeleton ("LA3018-50P" manufactured by DIC Corporation, a 2-methoxypropanol solution with a hydroxyl equivalent of about 151 g / eq. and a non-volatile content of 50%), 6 parts of an active ester curing agent ("EXB-8000L-65TM" manufactured by DIC Corporation, an MEK solution with an active group equivalent of about 220 g / eq. and a non-volatile content of 65% by mass), and spherical silica ("SC2500SQ" manufactured by Yaduma Co., Ltd., with an average particle size of 0.5 μm and a specific surface area of ​​11.2 m 2 / g, 100 parts of silica, a product surface-treated with 1 part of N-phenyl-3-aminopropyltrimethoxysilane (KBM573 manufactured by Shin-Etsu Chemical Co., Ltd.), 25 parts of an epoxy resin containing a siloxane skeleton (KR470 manufactured by Shin-Etsu Chemical Co., Ltd., with an epoxy equivalent of about 200 g / eq.), and 0.2 parts of an amine curing accelerator (4-dimethylaminopyridine (DMAP)) were uniformly dispersed with a high-speed rotary mixer and filtered with a cartridge filter (SHP020 manufactured by ROKITECHNO Co., Ltd.) to prepare a resin composition 1.

[0258] <Example 2: Preparation of resin composition 2>

[0259] Resin composition 2 was prepared by performing the same operation as in Example 1, except that 100 parts of polyimide resin 2 (non-volatile component: 20 mass %) obtained in Synthesis Example 2 was used instead of 40 parts of polyimide resin 1 (non-volatile component: 50 mass %) obtained in Synthesis Example 1.

[0260] <Example 3: Preparation of resin composition 3>

[0261] Resin composition 3 was prepared by performing the same operation as in Example 1 except that 66.7 parts of polyimide resin 3 (non-volatile component: 30 mass %) obtained in Synthesis Example 3 was used instead of 40 parts of polyimide resin 1 (non-volatile component: 50 mass %) obtained in Synthesis Example 1.

[0262] <Example 4: Preparation of resin composition 4>

[0263] Resin composition 4 was prepared by performing the same operation as in Example 1, except that 100 parts of polyimide resin 4 (non-volatile component: 20 mass %) obtained in Synthesis Example 4 was used instead of 40 parts of polyimide resin 1 (non-volatile component: 50 mass %) obtained in Synthesis Example 1.

[0264] <Comparative Example 1: Preparation of Resin Composition 5>

[0265] Resin composition 5 was prepared by the same operation as in Example 1 except that 6 parts of a siloxane skeleton-containing epoxy resin (manufactured by Shin-Etsu Chemical Co., Ltd., “KR470”, epoxy equivalent of about 200 g / eq.) was not used.

[0266] <Comparative Example 2: Preparation of Resin Composition 6>

[0267] Resin composition 6 was prepared by performing the same operations as in Example 1, except that 66 parts of phenoxy resin ("YX7553BH30" manufactured by Mitsubishi Chemical Corporation, solid content 30% by mass) was used instead of 40 parts of polyimide resin 1 (non-volatile component 50% by mass) obtained in Synthesis Example 1.

[0268] <Test Example 1: Evaluation of flexibility (MIT folding resistance)>

[0269] The resin composition of each example and comparative example was uniformly applied on the release-treated surface of a PET film (thickness 38 μm) treated with an alkyd release agent using a die coater so that the thickness of the resin composition layer after drying would be 40 μm, and dried at 80 to 120° C. (average 100° C.) for 6 minutes to obtain a resin sheet 1.

[0270] The obtained resin sheet 1 was laminated on a polyimide film (UPILEX S, manufactured by Ube Industries, Ltd.) using an intermittent vacuum press laminator (MVLP-500 manufactured by Meiki Seisakusho Co., Ltd.) to obtain a resin sheet with a protective film. For lamination, the pressure was reduced for 30 seconds to make the air pressure below 13 hPa, and then pressure bonding was performed at 120° C. and a pressure of 0.74 MPa for 30 seconds. Then, the PET film was peeled off, and the resin composition was cured under curing conditions of 190° C. and 90 minutes, and the polyimide film was peeled off to obtain a cured product sample.

[0271] The obtained cured product sample was cut into test pieces with a width of 15 mm and a length of 110 mm. The MIT test device (manufactured by Toyo Seiki Seisaku-sho, Ltd., MIT folding fatigue tester "MIT-DA") was used to measure the number of folding times until the cured product broke under the measurement conditions of a load of 2.5 N, a bending angle of 90 degrees, a bending radius of 1.0 mm, and a bending speed of 175 times / minute in accordance with JISC-5016. It should be noted that the measurement was performed on 5 samples, and the average value of the top 3 samples ranked from large to small was calculated. The case where the number of folding times was less than 8,000 times was evaluated as "×", and the case where the number of folding times was more than 8,000 times was evaluated as "○".

[0272] <Test Example 2: Evaluation of Tack (Adhesiveness)>

[0273] The protective film was peeled off from the resin sheet with a protective film obtained in Test Example 1, and the resin composition layer was subjected to a probe viscosity tester (TESTER Sangyo Co., Ltd., "TE-6002") using a glass probe with a diameter of 5 mm and a load of 1 kgf / cm 2 , contact speed 0.5 mm / sec, tensile speed 0.5 mm / sec, holding time 10 sec, temperature 80° C. The case where the adhesive force was greater than 1.6 N was evaluated as “×”, and the case where the adhesive force was less than 1.6 N was evaluated as “○”.

[0274] <Test Example 3: Evaluation of insulation reliability>

[0275] (1) Base treatment of inner layer circuit board

[0276] As the inner layer circuit board, a glass cloth-based epoxy resin double-sided copper-clad laminate (copper foil thickness of 3 μm, substrate thickness of 0.15 mm, "HL832NSFLCA" manufactured by Mitsubishi Gas Chemical Co., Ltd., size of 255×340 mm) having circuit conductors (copper) formed in a wiring pattern of L / S=10 μm / 10 μm on both sides was prepared. For both sides of the inner layer circuit board, the copper surface was treated with an organic film using "FlatBOND-FT" manufactured by MEC.

[0277] (2) Lamination of resin sheets

[0278] The protective film was peeled off from the resin sheet with protective film obtained in Test Example 1, and laminated on both sides of the inner layer circuit substrate using an intermittent vacuum pressurization laminator (Nikko-Materials Co., Ltd., 2-stage stacking laminator, CVP700) in a manner that the resin composition layer is in contact with the inner layer circuit substrate. Lamination was carried out in the following manner: decompression was performed for 30 seconds to make the air pressure below 13 hPa, and pressure bonding was performed at 130°C and a pressure of 0.74 MPa for 45 seconds. Next, hot pressing was performed at 120°C and a pressure of 0.5 MPa for 75 seconds.

[0279] (3) Thermal curing of resin composition layer

[0280] The inner layer circuit board laminated with the resin sheet was placed in an oven at 100° C. and heat cured for 30 minutes, and then transferred to an oven at 180° C. and heat cured for 30 minutes to form an insulating layer, and the release PET was peeled off.

[0281] (4) Roughening treatment

[0282] The inner layer circuit substrate with the insulating layer formed thereon is subjected to a desmear treatment as a roughening treatment. It should be noted that the desmear treatment is performed by the following wet desmear treatment;

[0283] Wet desmear treatment:

[0284] The substrate was immersed in a swelling solution ("Swelling Dip Securiganth P" manufactured by Atotech Japan, an aqueous solution of diethylene glycol monobutyl ether and sodium hydroxide) at 60°C for 5 minutes, then immersed in an oxidizing solution ("Concentrate Compact CP" manufactured by Atotech Japan, an aqueous solution of potassium permanganate concentration of about 6% and sodium hydroxide concentration of about 4%) at 80°C for 10 minutes, and finally immersed in a neutralizing solution ("Reduction Solution Securiganth P" manufactured by Atotech Japan, an aqueous solution of sulfuric acid) at 40°C for 5 minutes, and then dried at 80°C for 15 minutes. This was referred to as "roughened substrate A".

[0285] (5) Conductor layer formation

[0286] (5-1) Electroless plating

[0287] In order to form a conductor layer on the roughened surface of the roughened substrate A, a plating step including the following steps 1 to 6 (copper plating step using a chemical solution manufactured by Atotech Japan Co., Ltd.) was performed to form a conductor layer.

[0288] 1. Alkali cleaning (cleaning and charge adjustment of the surface of the insulating layer)

[0289] The surface of the roughened substrate A was cleaned at 60° C. for 5 minutes using Cleaning Cleaner Securiganth 902 (trade name);

[0290] 2. Soft etching (cleaning inside through-holes)

[0291] For roughening the surface of substrate A, a sulfuric acid-acidified sodium persulfate aqueous solution was used for treatment at 30° C. for 1 minute;

[0292] 3. Pre-preg (to provide Pd insulation layer surface charge regulation)

[0293] For roughening the surface of substrate A, use Pre.Dip Neoganth B (trade name) at room temperature for 1 minute;

[0294] 4. Activator application (applying Pd to the surface of the insulating layer)

[0295] The surface of the roughened substrate A was treated with Activator Neoganth 834 (trade name) at 35° C. for 5 minutes;

[0296] 5. Reduction (reduction of Pd that has been given to the insulating layer)

[0297] The surface of the roughened substrate A was treated at 30° C. for 5 minutes using a mixture of Reducer Neoganth WA (trade name) and Reducer Acceralator 810 mod. (trade name);

[0298] 6. Electroless copper plating (Cu is deposited on the surface of the insulating layer (Pd surface))

[0299] A mixed solution of Basic Solution Printganth MSK-DK (trade name), Copper Solution Printganth MSK (trade name), Stabilizer Printganth MSK-DK (trade name), and ReducerCu (trade name) was used to roughen the surface of the substrate A at 35° C. for 20 minutes to form an electroless copper plating layer. The thickness of the formed electroless copper plating layer was 0.8 μm.

[0300] (5-2) Electrolytic plating

[0301] Next, an electrolytic copper plating process was performed using a chemical solution made by Atotech Japan Co., Ltd. under the condition that the through hole was filled with copper. Then, as a resist pattern for patterning based on etching, a pad pattern with a diameter of 1 mm that was connected to the lower conductor and a circular conductor pattern with a diameter of 10 mm that was not connected to the lower conductor were used to form a conductor layer with a thickness of 10 μm on the surface of the insulating layer having a pad and a conductor pattern. Next, an annealing treatment was performed at 200°C for 90 minutes. This substrate was referred to as "evaluation substrate A".

[0302] (6) Evaluation of insulation reliability of insulation layer

[0303] The circular conductor side of the evaluation substrate A with a diameter of 10 mm was used as the positive (+) electrode, and the grid circuit conductor (copper) side of the inner layer circuit substrate connected to the pad with a diameter of 1 mm was used as the negative (-) electrode. A highly accelerated life tester ("PM422" manufactured by ETAC) and an electrochemical migration tester ("ECM-100" manufactured by J-RAS) were used to measure the insulation resistance value after 100 hours under the conditions of 110°C, 85% relative humidity, and 20V DC voltage application. This measurement was performed 6 times, and the resistance values ​​of all 6 test pieces were 1.00×10 8 Ω or more is evaluated as "○", and at least one resistance value is less than 1.00×10 8 The case of Ω was evaluated as "×", and the evaluation results and insulation resistance values ​​are shown in the following table. The insulation resistance value described in the following Table 1 is the lowest value of the insulation resistance values ​​of the six test pieces.

[0304] The amounts of nonvolatile components used in the resin compositions of Examples and Comparative Examples, the measurement results of Test Examples, the evaluation results, and the like are shown in Table 1 below.

[0305] [Table 1]

[0306]

[0307] It can be seen that by using the following resin composition, even if the content of (B) the inorganic filler is a low compounding amount of less than 40% by mass, the viscosity can be suppressed to a low level, and a cured product with excellent flexibility and excellent insulation reliability can be obtained; the resin composition is a resin composition comprising (A) an epoxy resin, (B) an inorganic filler and (C) a polyimide resin, wherein the (A) component comprises (A-1) an epoxy resin containing a siloxane skeleton.

Claims

1. A resin composition comprising (A) an epoxy resin, (B) an inorganic filler, (C) a polyimide resin and (D) a curing agent, in, The component (A) comprises: (A-1) an epoxy resin containing a siloxane skeleton, The component (A-1) is an epoxy resin containing a cyclic siloxane skeleton, The component (C) is (1) a resin obtained by an imidization reaction between a diamine compound and tetracarboxylic anhydride, or (2) a resin obtained by an imidization reaction between a diisocyanate compound and tetracarboxylic anhydride, (D) component is one or more curing agents selected from the group consisting of phenolic curing agents, naphthol curing agents, active ester curing agents, benzoxazine curing agents, cyanate curing agents and carbodiimide curing agents, When the nonvolatile component in the resin composition is 100 mass %, the content of the component (A) is 10 mass % or more and 70 mass % or less, When the total amount of the component (A) is 100% by mass, the content of the component (A-1) is 5% by mass or more and 50% by mass or less, When the nonvolatile components in the resin composition are set to 100% by mass, the content of the component (B) is 40% by mass or less. When the nonvolatile matter in the resin composition is 100 mass %, the content of the component (C) is 5 mass % or more and 50 mass % or less.

2. The resin composition according to claim 1, wherein The tetracarboxylic anhydride includes tetracarboxylic anhydride selected from aliphatic tetracarboxylic dianhydride and diphthalic dianhydride.

3. The resin composition according to claim 1, wherein The diamine compound includes a diamine compound selected from aliphatic diamine compounds and diphenylamine compounds, The diisocyanate compound includes a diisocyanate compound selected from aliphatic diisocyanate compounds, diisocyanatophenyl compounds, and polyurethane containing isocyanate groups at both ends.

4. The resin composition according to claim 3, wherein The diamine compound includes an aliphatic diamine compound, The diisocyanate compound includes a diisocyanate compound selected from aliphatic diisocyanate compounds and polyurethanes having isocyanate groups at both ends obtained by urethanization reaction of an aliphatic diisocyanate compound and a polymer having hydroxy groups at both ends.

5. The resin composition according to claim 1, wherein The component (A-1) is a compound represented by the formula (A1), In the formula, R 1 Each independently represents an alkylene oxide; R 2 each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group; R 3 and R 4 Each independently represents a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkenyl group, or a substituted or unsubstituted aryl group, or R 3 and R 4 Together, they are bonded to each other in a manner that represents one -O- to form a cyclic siloxane skeleton; s represents an integer greater than or equal to 1.

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

7. The resin composition according to claim 1, wherein The molecular weight of the component (A-1) is 800 or less.

8. The resin composition according to claim 1, wherein The epoxy equivalent of the component (A-1) is 50 g / eq. to 1000 g / eq.

9. The resin composition according to claim 1, wherein The epoxy equivalent of the component (A-1) is 150 g / eq. to 250 g / eq.

10. The resin composition according to claim 1, wherein The viscosity (25° C.) of the component (A-1) is 1000 to 5000 mPa·s.

11. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (A-1) is 1% by mass or more.

12. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (A-1) is 3% by mass or more.

13. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (A-1) is 5% by mass or more.

14. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (A-1) is 30% by mass or less.

15. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (A-1) is 20% by mass or less.

16. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (A-1) is 10% by mass or less.

17. The resin composition according to claim 1, wherein The average particle size of the component (B) is 1 μm or less.

18. The resin composition according to claim 1, wherein The average particle size of the component (B) is 0.3 μm or more.

19. The resin composition according to claim 1, wherein The component (B) is silicon dioxide.

20. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100 mass %, the content of the component (B) is 32 mass % or less.

21. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (B) is 5% by mass or more.

22. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100 mass %, the content of the component (B) is 20 mass % or more.

23. The resin composition according to claim 1, wherein When the nonvolatile components in the resin composition are set to 100% by mass, the content of the component (B) is 30% by mass or more. When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (A) is 60% by mass or less.

24. The resin composition according to claim 1, wherein The weight average molecular weight of the component (C) is 1,000 or more and 100,000 or less.

25. The resin composition according to claim 1, wherein The weight average molecular weight of the component (C) is 7,000 or more and 50,000 or less.

26. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (C) is 10% by mass or more.

27. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (C) is 20% by mass or more.

28. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (C) is 40% by mass or less.

29. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (C) is 30% by mass or less.

30. The resin composition according to claim 1, wherein The component (D) contains an active ester-based curing agent.

31. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100 mass %, the content of the component (D) is 1 mass % or more.

32. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100 mass %, content of the component (D) is 5 mass % or more.

33. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (D) is 20% by mass or less.

34. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100 mass %, the content of the component (D) is 8 mass % or less.

35. The resin composition according to claim 1, which is used to form an insulating layer of a multi-layer flexible substrate.

36. The resin composition according to claim 1, wherein When the resin composition is uniformly applied on the release-treated surface of a PET film treated with an alkyd-based release agent so that the thickness of the resin composition layer after drying becomes 40 μm, and dried at 80 to 120° C. for 6 minutes to form a sheet, the drying temperature is 100° C. on average, The diameter of the glass probe is 5 mm and the load is 1 kgf / cm 2 The adhesive force of the resin composition layer measured under the conditions of a contact speed of 0.5 mm / sec, a tensile speed of 0.5 mm / sec, a holding time of 10 seconds, and a temperature of 80° C. is 1.8 N or less.

37. A cured product, which is a cured product of the resin composition according to any one of claims 1 to 36.

38. A resin sheet comprising: Support body, and A resin composition layer formed from the resin composition according to any one of claims 1 to 36 and provided on the support.

39. A multi-layer flexible substrate comprising an insulating layer formed by curing the resin composition according to any one of claims 1 to 36. 40 . A semiconductor device comprising the multilayer flexible substrate according to claim 39 .

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