Resin composition

Abstract

The object of the present invention is to provide a resin composition for obtaining a cured product having excellent flexibility, halo phenomenon suppression characteristics and heat resistance. The solution of the present invention is a resin composition comprising (A) a polyimide resin, (B) a carbodiimide resin and (C) an inorganic filler, wherein when the non-volatile component in the resin composition is set to 100% by mass, the content of the component (C) is less than 40% by mass.

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. Flexible substrates can be thinner and lighter than rigid substrates. Furthermore, since flexible substrates are soft and deformable, they can be bent and installed.

[0003] Heretofore, a composition containing a carbodiimide resin is known (Patent Document 1).

[0004] Prior art literature

[0005] Patent Literature

[0006] Patent Document 1: Japanese Patent Application Publication No. 2016-027097. Summary of the invention

[0007] Problems to be solved by the invention

[0008] In order to improve flexibility, a polyimide resin is sometimes blended into the insulating material of a flexible substrate. In this case, if the amount of inorganic filler contained in the insulating material is small, a haloing phenomenon occurs significantly and heat resistance tends to decrease.

[0009] An object of the present invention is to provide a resin composition for obtaining a cured product having excellent flexibility, halo phenomenon suppression characteristics, and heat resistance.

[0010] Means for solving problems

[0011] In order to solve the subject (technical problem) of the present invention, the present inventors conducted in-depth research and found that by using a resin composition comprising (A) a polyimide resin, (B) a carbodiimide resin, and less than 40% by mass of (C) an inorganic filler, a cured product with excellent flexibility, halo phenomenon suppression characteristics and heat resistance can be obtained, thereby completing the present invention.

[0012] That is, the present invention includes the following contents:

[0013] [1] A resin composition comprising (A) a polyimide resin, (B) a carbodiimide resin, and (C) an inorganic filler,

[0014] Wherein, when the non-volatile components in the resin composition are set to 100% by mass, the content of the component (C) is less than 40% by mass;

[0015] [2] The resin composition according to [1] above, wherein the weight average molecular weight of the component (A) is 1,000 to 100,000.

[0016] [3] The resin composition according to [1] or [2] above, wherein the content of the component (A) is 15% by mass or more, when the non-volatile component in the resin composition is 100% by mass;

[0017] [4] The resin composition according to any one of [1] to [3] above, wherein the content of the component (A) is 35% by mass or less when the non-volatile component in the resin composition is 100% by mass;

[0018] [5] The resin composition according to any one of [1] to [4] above, wherein the component (B) is polycarbodiimide;

[0019] [6] The resin composition according to any one of [1] to [5] above, wherein the content of isocyanato groups in the molecules of component (B) is 0.2% by mass or less;

[0020] [7] The resin composition according to any one of [1] to [6] above, wherein the content of the component (B) is 3% by mass or more, based on 100% by mass of the nonvolatile component in the resin composition;

[0021] [8] The resin composition according to any one of [1] to [7] above, wherein the content of the component (B) is 15% by mass or less when the non-volatile component in the resin composition is 100% by mass;

[0022] [9] The resin composition according to any one of [1] to [8] above, wherein the mass ratio of the component (B) to the component (A) (component (B) / component (A)) is 0.1 or more;

[0023]

[10] The resin composition according to any one of [1] to [9] above, wherein the mass ratio of the component (B) to the component (A) (component (B) / component (A)) is 0.5 or less;

[0024]

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

[10] above, wherein the component (C) is silica;

[0025]

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

[11] above, wherein the average particle size of component (C) is 1 μm or less;

[0026]

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

[12] above, further comprising (D) an epoxy resin;

[0027]

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

[13] above, further comprising (E) a curing agent;

[0028]

[15] The resin composition according to

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

[0029]

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

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

[0030]

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

[16] above;

[0031]

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

[16] above and disposed on the support;

[0032]

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

[16] above;

[0033]

[20] A semiconductor device comprising the multi-layer flexible substrate described in

[19] above.

[0034] Effects of the Invention

[0035] According to the resin composition of the present invention, a cured product having excellent flexibility, halo phenomenon suppression characteristics and heat resistance can be obtained. DETAILED DESCRIPTION

[0036] Hereinafter, the present invention will be described in detail according to the preferred embodiments of the present invention. However, the present invention is not limited to the following embodiments and examples, and can be implemented with any changes within the scope of the claims of the present invention and their equivalents.

[0037] <Resin composition>

[0038] The resin composition of the present invention is a resin composition comprising (A) a polyimide resin, (B) a carbodiimide resin and (C) an inorganic filler, wherein the content of the component (C) is less than 40% by mass. By using such a resin composition, a cured product having excellent flexibility, halo phenomenon suppression characteristics and heat resistance can be obtained.

[0039] For the resin composition of the present invention, in addition to comprising (A) polyimide resin, (B) carbodiimide resin and (C) inorganic filler, it can also include any component. As any component, for example (D) epoxy resin, (E) curing agent, (F) curing accelerator, (G) other additives and (H) organic solvent can be cited. Below, each component included in the resin composition is described in detail.

[0040] <(A) Polyimide resin>

[0041] The resin composition of the present invention comprises (A) a polyimide resin. (A) The polyimide resin is a resin having an imide bond in a repeating unit. (A) The polyimide resin is not particularly limited, and may include, for example: (1) a resin obtained by an imidization reaction of a diamine compound and a tetracarboxylic anhydride, or (2) a resin obtained by an imidization reaction of a diisocyanate compound and a tetracarboxylic anhydride. (A) The polyimide resin also includes modified polyimide resins such as siloxane-modified polyimide resins.

[0042] The (A) polyimide resin is not particularly limited and may include, for example, a structure represented by formula (A1).

[0043] [Chemical formula 1]

[0044] .

[0045] 〔In the formula, X 1 represents a tetravalent group obtained by removing two -CO-O-CO- from tetracarboxylic dianhydride, and may be, for example, an organic group composed of 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. 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. ]

[0046] X in formula (A1) 1 and X 2The organic group is not particularly limited as long as it is within the range of a chemically stable structure, and may be a structure that can be appropriately selected by a person skilled in the art, such as a structure of a known polyimide resin. (A) When the polyimide resin comprises the structure represented by formula (A1), it preferably comprises 60% by mass or more of the structure represented by formula (A1), more preferably 80% by mass or more, further 90% by mass or more, and particularly preferably 95% by mass or more.

[0047] (A) The diamine compound used for preparing the polyimide resin is not particularly limited, and examples thereof include aliphatic diamine compounds and aromatic diamine compounds.

[0048] 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, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, and 4,4′-methylenebis(cyclohexylamine); and dimer acid-type diamines (hereinafter also referred to as “dimer diamines”).

[0049] The so-called dimer acid type diamine refers to a dimer acid in which the two terminal carboxyl groups (-COOH) are replaced by aminomethyl groups (-CH 2 -NH 2 ) or amino group (-NH 2). 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 inexpensive and easily available, 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 have been 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.

[0050] 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, 2,2 - diphenylamine compounds such as 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 5-amino-1,1'-biphenyl-2-yl 4-aminobenzoate.

[0051] A commercially available diamine compound may be used, or a product synthesized by a known method may be used. The diamine compound may be used alone or in combination of two or more.

[0052] The diisocyanate compound used for preparing the polyimide resin (A) is not particularly limited, and examples thereof include aliphatic diisocyanate compounds, aromatic diisocyanate compounds, and polyurethane having isocyanate groups at both ends.

[0053] Examples of the aliphatic diisocyanate compound include linear aliphatic diisocyanate compounds such as 1,4-butanediisocyanate, 1,6-hexanediisocyanate, 1,8-octanediisocyanate, and 1,12-dodecanediisocyanate; branched aliphatic diisocyanate compounds such as 2,2,4-trimethyl-1,6-hexanediisocyanate, 2,4,4-trimethyl-1,6-hexanediisocyanate, and 2,2-dimethyl-1,5-pentanediisocyanate; and isophorone diisocyanate (IPDI), cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate (CHDI), 4-methylcyclohexane-1,3-diisocyanate. alicyclic diisocyanate compounds such as cyanate, 2-methylcyclohexane-1,3-diisocyanate, 2-methylcyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, dicyclohexyl ether-4,4'-diisocyanate, 1,4-bis(isocyanatomethyl)cyclohexane (1,4-bis(isocyanatomethyl)cyclohexane), 1,3-bis(isocyanatomethyl)cyclohexane, 3a,4,5,6,7,7a-hexahydro-4,7-endimethyleneindan-1,8-ylidene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4-bis(isocyanatomethyl)cyclohexane; dimer acid type diisocyanate, etc.

[0054] The dimer acid type diisocyanate is a diisocyanate obtained by converting the amino group (-NH 2 ) is replaced by an isocyanate group (-NCO).

[0055] Examples of the aromatic diisocyanate compound include 1,4-phenylene diisocyanate, 1,3-phenylene diisocyanate, toluene-2,6-diisocyanate, toluene-2,4-diisocyanate, toluene-3,5-diisocyanate, 2-methyl-4,6-diisopropylphenylene-1,3-diisocyanate, 2,4,6-triethylphenylene-1,3-diisocyanate, 4,6-diethylphenylene-1,3-diisocyanate, 2,5-diethylphenylene-1,3-diisocyanate, 2,5-diethylphenylene-1,4-diisocyanate, 2,4,6-triisopropylphenylene-1,3-diisocyanate, 4,6-diisopropylphenylene-1,3-diisocyanate, 2,5-diisopropylphenylene-1,3-diisocyanate, 2,5-diisopropylphenylene-1,4-diisocyanate, m-xylylene diisocyanate, p-xylylene diisocyanate, tetramethylm-xylylene diisocyanate, tetramethylp-xylylene diisocyanate and the like phenylene diisocyanate compounds; 1,3-naphthalene diisocyanate diisocyanate), naphthalene diisocyanate compounds such as 1,6-naphthalene diisocyanate, 1,7-naphthalene diisocyanate, 1,8-naphthalene diisocyanate, 2,6-naphthalene diisocyanate, and 2,7-naphthalene diisocyanate; bis(isocyanatobenzene) compounds such as diphenylmethane-4,4'-diisocyanate, diphenyl ether-4,4'-diisocyanate, diphenyl ether-2,4'-diisocyanate, biphenyl-4,4'-diisocyanate, 3,3'-dimethylbiphenyl-4,4'-diisocyanate, 3,3'-dimethoxybiphenyl-4,4'-diisocyanate, 3,3'-dimethoxydiphenylmethane-4,4'-diisocyanate, and 4,4'-dimethoxydiphenylmethane-3,3'-diisocyanate.

[0056] The isocyanate 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 polymer at both ends. Examples of the hydroxyl polymer at both ends include hydroxyl polybutadiene at both ends, hydroxyl hydrogenated polybutadiene at both ends, hydroxyl polyisoprene at both ends, hydroxyl polyolefins at both ends such as hydroxyl polybutadiene at both ends, hydroxyl hydrogenated polyisoprene at both ends, and hydroxyl polyethers at both ends such as hydroxyl polyethylene glycol at both ends, hydroxyl polypropylene glycol at both ends, and hydroxyl poly-1,4-butylene glycol at both ends.

[0057] 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 can be a value measured by gel permeation chromatography (GPC) (in terms of polystyrene).

[0058] The polyurethane with isocyanate groups at both ends is, for example, polyurethane with isocyanate groups at both ends represented by formula (A2).

[0059] [Chemical formula 2]

[0060] .

[0061] 〔In the formula, 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. 〕

[0062] A commercially available diisocyanate compound may be used, or a product 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.

[0063] (A) The tetracarboxylic anhydride used for preparing the polyimide resin is not particularly limited, and examples thereof include aliphatic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride.

[0064] Specific examples of aliphatic tetracarboxylic dianhydrides 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 tetracarboxylic dianhydride, -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.

[0065] 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 tetracarboxylic dianhydride, 3,3',4,4 '-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 ,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.

[0066] As tetracarboxylic dianhydride, commercially available products may be used, or products 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.

[0067] The content of the structure derived from aromatic tetracarboxylic dianhydride constituting the polyimide resin (A) relative to the total structure derived from tetracarboxylic dianhydride 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 preferably 90 mol % or more, particularly preferably 100 mol %.

[0068] The weight average molecular weight of the (A) polyimide resin is not particularly limited, and 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 (A) polyimide resin is not particularly limited, and 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. The number average molecular weight of the (A) polyimide resin is not particularly limited, and 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 (A) polyimide resin is not particularly limited, and 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. The weight average molecular weight and number average molecular weight herein may be values ​​measured by gel permeation chromatography (GPC) (in terms of polystyrene).

[0069] The content of (A) 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 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, further more preferably 35% by mass or less, and particularly preferably 30% by mass or less. The lower limit of the content of (A) 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 1% by mass or more, more preferably 5% by mass or more, further preferably 10% by mass or more, further more preferably 15% by mass or more, and particularly preferably 20% by mass or more.

[0070] <(B) Carbodiimide resin>

[0071] The resin composition of the present invention contains (B) a carbodiimide resin. (B) The carbodiimide resin is a compound having one or more carbodiimide structures (-N=C=N-) in one molecule. As the (B) carbodiimide resin, a compound having two or more carbodiimide structures in one molecule is preferred, and a polycarbodiimide having a carbodiimide structure in a repeating unit is preferred. The polycarbodiimide may be cyclic or chain-shaped.

[0072] There is no particular limitation on the polycarbodiimide, and for example, it may include a polycarbodiimide obtained by a decarboxylation condensation reaction (decarbonylation condensation reaction) between molecules of a diisocyanate compound. The polycarbodiimide obtained in the above manner has an isocyanate group (-N=C=O) in the molecule, and a part or all of it can be further treated with a known blocking agent such as a monoisocyanate compound, an alcohol compound, an amine compound, a carboxylic acid compound, an epoxy compound, etc. As the diisocyanate compound used to prepare the polycarbodiimide, for example, the same compound as the "diisocyanate compound used to prepare (A) polyimide resin" can be cited. (B) Carbodiimide resin can be used alone or in combination of two or more.

[0073] The (B) carbodiimide resin is not particularly limited, and is preferably, for example, a polycarbodiimide having a structure represented by formula (B1).

[0074] [Chemical formula 3]

[0075] .

[0076] 〔In the formula, X 3 It represents a divalent group obtained by removing two -NCO groups from a diisocyanate compound, for example, an organic group formed by two or more (for example, 2 to 50, 2 to 40, 2 to 30, 2 to 20) backbone atoms selected from carbon atoms, oxygen atoms, nitrogen atoms and sulfur atoms, and in one embodiment, it may be an alkylene group, an arylene group, an alkyl-substituted arylene group and a combination thereof. p represents an integer greater than 2. 〕

[0077] The term "alkylene group" refers to a linear, branched and / or cyclic divalent aliphatic saturated hydrocarbon group. The number of carbon atoms in the "alkylene group" may be, for example, 2 to 30, 2 to 20, or the like. Examples of the “alkylene group” include straight chain alkylene groups such as ethylene, 1,3-propylene, 1,4-butylene, 1,5-pentylene, 1,6-hexylene, 1,7-heptylene, and 1,8-octylene; and ethylidene, propylidene, isopropylidene, 1-methylethylene, 1-ethylethylene, 1,3-propylene, 2-methyl-1,3-propylene, 2-methyl-1,4-butylene, 2,3-dimethyl-1,4-butylene, 1,3-dimethyl-1,4-butylene, 2-methyl-1,5-pentylene, 2,2-dimethyl-1,5-pentylene, 2,4-dimethyl-1,5-pentylene, 1,3,5-methyl-1,5-pentylene, 2-methyl-1,6-hexylene, 2,2-dimethyl-1,6 -hexylene, 2,4-dimethyl-1,6-hexylene, 1,3,5-trimethyl-1,6-hexylene, 2,2,4-trimethyl-1,6-hexylene, 2,4,4-trimethyl-1,6-hexylene; branched alkylene groups such as 1,3-cyclopentylene, 1,3-cyclohexylene, 1,4-cyclohexylene, 4-methyl-1,3-cyclohexylene, 2-methyl-1,3 Cyclic alkylene groups such as methylenebis(4,1-cyclohexylene) and 2-methyl-1,4-cyclohexylene; cyclic-straight-chain-cyclic alkylene groups such as methylenebis(4,1-cyclohexylene); cyclic-branched-cyclic alkylene groups such as isopropylidenebis(4,1-cyclohexylene); straight-chain-cyclic-straight-chain alkylene groups such as 1,4-cyclohexylenedimethylene; branched-cyclic-branched-chain alkylene groups such as 1,4-cyclohexylenediisopropylidene, etc.

[0078] The so-called "arylene group" refers to a divalent aromatic hydrocarbon group. The number of carbon atoms of the "arylene group" can be, for example, 6 to 14, 6 to 10, etc. Examples of the "arylene group" include 1,3-phenylene, 1,4-phenylene, 1,5-naphthylene, 1,8-naphthylene, 2,6-naphthylene, etc. The so-called "alkyl-substituted arylene group" refers to an arylene group substituted with an alkyl group such as methyl, ethyl, propyl, isopropyl, etc. The number of carbon atoms of the "alkyl-substituted arylene group" can be, for example, 7 to 30, 7 to 20, etc. Examples of the “alkyl-substituted arylene group” include 2,6-tolyl, 2,4-tolyl, 3,5-tolyl, 2-methyl-4,6-diisopropyl-1,3-phenylene, 2,4,6-triethyl-1,3-phenylene, 4,6-diethyl-1,3-phenylene, 2,5-diethyl-1,3-phenylene, 2,5-diethyl-1,4-phenylene, 2,4,6-triisopropyl-1,3-phenylene, 4,6-diisopropyl-1,3-phenylene, 2,5-diisopropyl-1,3-phenylene and 2,5-diisopropyl-1,4-phenylene. Examples of combinations of an alkylene group, an arylene group, and an alkyl-substituted arylene group include an alkylene-arylene group-alkylene group, an alkylene-alkyl-substituted arylene group-alkylene group, an arylene-alkylene group-arylene group, an alkyl-substituted arylene group-alkyl-substituted arylene group, etc. The alkylene group, the arylene group, and the alkyl-substituted arylene group may further have an arbitrary substituent.

[0079] X in formula (B1) 3 The organic group is not particularly limited as long as it is within the range of a chemically stable structure, and may be a structure that can be appropriately selected by a person skilled in the art, for example, may be a known polycarbodiimide structure.

[0080] In one embodiment, the (B) carbodiimide resin specifically includes aliphatic polycarbodiimides such as polyhexamethylenecarbodiimide, polytrimethylhexamethylenecarbodiimide, polycyclohexylenecarbodiimide, poly(methylenebiscyclohexylenecarbodiimide), and poly(isophoronecarbodiimide); or polycarbodiimides containing aromatic polycarbodiimides such as poly(phenylenecarbodiimide), poly(naphthylenecarbodiimide), poly(toluenecarbodiimide), poly(methyldiisopropylphenylenecarbodiimide), poly(triethylphenylenecarbodiimide), poly(diethylphenylenecarbodiimide), poly(triisopropylphenylenecarbodiimide), poly(diisopropylphenylenecarbodiimide), poly(xylylenecarbodiimide), poly(tetramethylxylylenecarbodiimide), poly(methylenebisphenylenecarbodiimide), and poly[methylenebis(methylphenylene)carbodiimide].

[0081] The content of isocyanate groups (-N=C=O) in the molecules of the carbodiimide resin (B) is preferably 10% by mass or less, more preferably 5% by mass or less, 3% by mass or less, further preferably 2% by mass or less, 1% by mass or less, further more preferably 0.5% by mass or less, 0.2% by mass or less, and particularly preferably 0% by mass. That is, the carbodiimide resin (B) particularly preferably does not contain an isocyanate group.

[0082] Commercially available products of the (B) carbodiimide resin include, for example, "CARBODILITE (registered trademark) V-02B", "CARBODILITE (registered trademark) V-03", "CARBODILITE (registered trademark) V-04K", "CARBODILITE (registered trademark) V-07" and "CARBODILITE (registered trademark) V-09" manufactured by Nisshinbo Chemical Co., Ltd.; "Stabaxol (registered trademark) P", "Stabaxol (registered trademark) P400", and "Hycasyl (registered trademark) 510" manufactured by RheinChemie.

[0083] The content of (B) carbodiimide 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 30% by mass or less, further preferably 20% by mass or less, further more preferably 15% by mass or less, and particularly preferably 10% by mass or less. The lower limit of the content of (B) carbodiimide 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 0.1% by mass or more, more preferably 0.5% by mass or more, further preferably 1% by mass or more, further more preferably 3% by mass or more, and particularly preferably 5% by mass or more.

[0084] The mass ratio of the (B) carbodiimide resin to the (A) polyimide resin in the resin composition ((B) carbodiimide resin / (A) polyimide resin) is not particularly limited, and is preferably 5 or less, more preferably 1 or less, further preferably 0.5 or less, and further preferably 0.3 or less. The lower limit of the mass ratio ((B) carbodiimide resin / (A) polyimide resin) is not particularly limited, and is preferably 0.01 or more, more preferably 0.05 or more, further preferably 0.1 or more, and further preferably 0.2 or more.

[0085] <(C) Inorganic fillers>

[0086] The resin composition of the present invention contains (C) an inorganic filler. The (C) inorganic filler is contained in the resin composition in the form of particles.

[0087] As the material of (C) inorganic filling material, inorganic compounds are used. As the material of (C) inorganic filling material, 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. (C) The inorganic filler may be used alone or in combination of two or more at any ratio.

[0088] Examples of commercially available inorganic fillers (C) include "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumitomo Metal Materials Corporation; "YC100C", "YA050C", "YA050C-MJE", "YA010C", "SC2500SQ", "SO-C4", "SO-C2" and "SO-C1" manufactured by Admatechs; "Silfil NSS-3N", "Silfil NSS-4N" and "Silfil NSS-5N" manufactured by Tokuyama Co., Ltd.; "UFP-30", "DAW-03" and "FB-105FD" manufactured by Denka; and "IMSIL A-8", "IMSIL A-10", "IMSIL A-15" and "IMSIL A-25" manufactured by Unimin.

[0089] (C) 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. (C) 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 0.03 μm or more, further more preferably 0.05 μm or more, and particularly preferably 0.1 μm or more. (C) The average particle size of the inorganic filler can be measured using 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 can be measured using a sample obtained by the following method: weigh 100 mg of the inorganic filler and 10 g of methyl ethyl ketone into a vial and disperse it for 10 minutes using ultrasound. For the sample to be measured, 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 particle size distribution of the volume basis of the inorganic filler is measured in a flow cell (flow cell) mode, and the average particle size as the median particle size is calculated 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.

[0090] (C) The specific surface area of ​​the inorganic filler 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 (C) 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.

[0091] The (C) inorganic filler material is preferably surface treated with an appropriate surface treatment agent. By performing the surface treatment, the moisture resistance and dispersibility of the (C) inorganic filler material can be improved. As the surface treatment agent, for example, 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, 3-glycidoxypropyltriethoxysilane; styrene-based silane coupling agents such as styryltrimethoxysilane; 3-methacryloxypropylmethyldimethoxysilane, 3-methacryloxypropyltrimethoxysilane; Methacrylic silane coupling agents such as methyl propyl trimethoxysilane, 3-methacryloxypropyl methyl diethoxysilane, and 3-methacryloxypropyl triethoxysilane; acrylic silane coupling agents such as 3-acryloxypropyl trimethoxysilane; N-2-(aminoethyl)-3-aminopropyl methyl dimethoxysilane, N-2-(aminoethyl)-3-aminopropyl trimethoxysilane, 3-aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-triethoxysilyl-N-(1,3-dimethyl-butylidene) 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-ureapropyltrialkoxysilane; 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.

[0092] 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" ( "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-alkoxy silane compounds), etc.

[0093] From the viewpoint of improving the dispersibility of the inorganic filler, it is preferred that the degree of surface treatment based on the surface treatment agent is limited to a specified range. Specifically, for 100 mass % of the inorganic filler, it is preferred that the surface treatment agent be used to carry out surface treatment at 0.2 mass % to 5 mass %, more preferably at 0.2 mass % to 3 mass %, and further preferably at 0.3 mass % to 2 mass %.

[0094] 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. The amount of carbon per unit surface area of ​​the inorganic filler is preferably 0.02 mg / m2 from the viewpoint of improving the dispersibility of the inorganic filler. 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.

[0095] (C) 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.

[0096] For the content of (C) inorganic filler in resin combination, when the non-volatile component in resin combination is set to 100% by mass, it is less than 40% by mass, from the viewpoint of improving flexibility, preferably below 39% by mass, below 38% by mass, more preferably below 37% by mass, further preferably below 35% by mass, particularly preferably below 33% by mass. The lower limit of the content of (C) inorganic filler in resin combination is not particularly limited, when the non-volatile component in resin combination is set to 100% by mass, it is preferably more than 0.1% by mass, more preferably more than 1% by mass, further preferably more than 10% by mass, further more preferably more than 20% by mass, particularly preferably more than 30% by mass.

[0097] <(D) Epoxy resin>

[0098] The resin composition of the present invention may contain (D) an epoxy resin as an optional component. (D) The epoxy resin refers to a curable resin having an epoxy group.

[0099] Examples of the epoxy resin (D) include bixylenol epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, bisphenol AF epoxy resins, dicyclopentadiene epoxy resins, trisphenol epoxy resins, naphthol novolac epoxy resins, phenol novolac epoxy resins, tert-butyl-catechol epoxy resins, naphthalene epoxy resins, naphthol epoxy resins, anthracene epoxy resins, glycidylamine epoxy resins, glycidylester epoxy resins, cresol novolac epoxy resins, benzene epoxy resins. Phenol aralkyl type epoxy resin, biphenyl type epoxy resin, linear aliphatic epoxy resin, epoxy resin having a butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, spiro ring-containing epoxy resin, cyclohexane type epoxy resin, cyclohexanedimethanol type epoxy resin, naphthylene ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type epoxy resin, phenolphthalimidine type epoxy resin, phenolphthalein type epoxy resin, etc. (D) The epoxy resin may be used alone or in combination of two or more.

[0100] The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as the epoxy resin (D). 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 nonvolatile component of the epoxy resin (D).

[0101] 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"). For the resin composition of the present invention, as an epoxy resin, only a liquid epoxy resin may be included, or only a solid epoxy resin may be included, or a liquid epoxy resin and a solid epoxy resin may be included in combination. The epoxy resin in the resin composition of the present invention is preferably a solid epoxy resin, or a combination of a liquid epoxy resin and a solid epoxy resin, and more preferably a solid epoxy resin.

[0102] As the liquid epoxy resin, a liquid epoxy resin having two or more epoxy groups in one molecule is preferred.

[0103] 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.

[0104] 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 Corporation; "PB-3600" manufactured by Daicel Corporation, "JP-100" and "JP-200" (epoxy resin with butadiene structure) manufactured by Nippon Soda Co., Ltd.; "ZX1658" and "ZX1658GS" (liquid 1,4-glycidyl 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.

[0105] 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.

[0106] As the solid epoxy resin, preferred are biphenylol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolac type epoxy resin, cresol novolac type epoxy resin, dicyclopentadiene type epoxy resin, trisphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthylene ether type epoxy resin, anthracene type epoxy resin, bisphenol A type epoxy resin, bisphenol AF type epoxy resin, phenol aralkyl type epoxy resin, tetraphenylethane type epoxy resin, phenolphthalimidine type epoxy resin, and phenolphthalein type epoxy resin.

[0107] 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", "HP-7200H", and "HP-7200L" (dicyclopentadiene-type epoxy resin) manufactured by DIC Corporation; "EXA -7311", "EXA-7311-G3", "EXA-7311-G4", "EXA-7311-G4S", "HP6000" (naphthylene ether type epoxy resin); "EPPN-502H" (trisphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC7000L" (naphthol novolac type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; NIPPON STEEL Chemical & Material Co., Ltd. Ltd.)'s "ESN475V" (naphthalene type epoxy resin); Nippon Steel Chemicals' "ESN485" (naphthol type epoxy resin); Nippon Steel Chemicals' "ESN375" (dihydroxynaphthalene type epoxy resin); Mitsubishi Chemical's "YX4000H", "YX4000", "YX4000HK", "YL7890" (biphenyl type epoxy resin); Mitsubishi Chemical's "YL6121" (biphenyl type epoxy resin); Mitsubishi Chemical's "YX8800" (anthracene type epoxy resin); Mitsubishi Chemical "YX7700" (phenol aralkyl type epoxy resin) manufactured by Osaka Gas Chemical Co., Ltd.; "PG-100" and "CG-500" manufactured by Osaka Gas Chemical Co., Ltd.; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "YL7800" (fluorene type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "jER1010" (bisphenol A type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Co., Ltd.; "WHR991S" (phenol benzopyrrolidone type epoxy resin) manufactured by Nippon Kayaku Co., Ltd., etc. These can be used alone or in combination of two or more.

[0108] When a liquid epoxy resin and a solid epoxy resin are used together as the component (D), the mass ratio of the solid epoxy resin to the liquid epoxy resin (solid epoxy resin / liquid epoxy resin) is not particularly limited, but is preferably 0.1 or more, more preferably 0.5 or more, further preferably 1 or more, and particularly preferably 5 or more. The upper limit of the mass ratio of the solid epoxy resin to the liquid epoxy resin is not particularly limited, but is preferably 100 or less, more preferably 50 or less, further preferably 30 or less, and particularly preferably 20 or less.

[0109] The epoxy equivalent of the epoxy resin (D) 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 according to JIS K7236.

[0110] (D) The weight average molecular weight (Mw) of the epoxy resin 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).

[0111] The content of epoxy resin (D) 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 60% by mass or less, more preferably 50% by mass or less, further preferably 40% by mass or less, further more preferably 35% by mass or less, and particularly preferably 30% by mass or less. The lower limit of the content of epoxy resin (D) 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, for example, 0% by mass or more, 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 10% by mass or more, further more preferably 20% by mass or more, and particularly preferably 25% by mass or more.

[0112] <(E) Curing agent>

[0113] The resin composition of the present invention may further contain (E) a curing agent. The (E) curing agent has a function of curing the (D) epoxy resin. The (E) curing agent here is a component that does not belong to the (A) component to the (D) component.

[0114] The (E) curing agent is not particularly limited, and examples thereof include phenolic curing agents, naphthol curing agents, acid anhydride curing agents, active ester curing agents, benzoxazine curing agents, and cyanate curing agents. The curing agent may be used alone or in combination of two or more. The (E) 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.

[0115] As phenolic curing agents and naphthol curing agents, from the viewpoint of heat resistance and water resistance, phenolic curing agents having a novolac resin structure or naphthol curing agents having a novolac resin structure are preferred. In addition, from the viewpoint of adhesion to the adherend, nitrogen-containing phenolic curing agents or nitrogen-containing naphthol curing agents are preferred, and phenolic curing agents containing triazine skeletons or naphthol curing agents containing triazine skeletons are more preferred. Among them, from the viewpoint of highly satisfying heat resistance, water resistance and adhesion, phenolic novolac resins containing triazine skeletons are preferred. 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.

[0116] 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, 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.

[0117] As active ester curing agent, there is no particular restriction, usually, it is preferred to use phenolic esters, thiophenolic esters, N-hydroxylamine esters, esters of heterocyclic hydroxy compounds, etc., compounds having ester groups with high reactive activity of more than 2 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, it is preferred to obtain active ester curing agents from carboxylic acid compounds and hydroxy compounds, and more preferably from 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 cited. 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.

[0118] Specifically, preferred are 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 resins, and active ester compounds containing benzoylated products of phenol novolac resins. Among them, 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-dicyclopentylene-phenylene.

[0119] 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", "EXB-8000L-65TM" (manufactured by DIC Corporation), which are active ester compounds containing a dicyclopentadiene-type diphenol structure; "EXB-9416-7 As an active ester curing agent (the active ester curing agent is an acetylated product of phenol novolac resin), "DC808" (manufactured by Mitsubishi Chemical Corporation) is used; as an active ester curing agent (the active ester curing agent is a benzoylated product of phenol novolac resin), "YLH1026" (manufactured by Mitsubishi Chemical Corporation), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), and "YLH1048" (manufactured by Mitsubishi Chemical Corporation) are used; and the like.

[0120] Specific examples of the benzoxazine-based curing agent include “JBZ-OP100D” and “ODA-BOZ” manufactured by JFE Chemical Industry Co., Ltd.; “HFB2006M” manufactured by Showa High Molecular Co., Ltd.; and “Pd” and “Fa” manufactured by Shikoku Chemical Industry Co., Ltd.

[0121] 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.

[0122] When the resin composition contains (D) epoxy resin and (E) curing agent, the amount ratio of (D) epoxy resin to (E) 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 [number of epoxy groups of (D) epoxy resin]:[number of reactive groups of (E) curing agent]. Here, the reactive group of (E) curing agent varies depending on the type of curing agent. For example, if the curing agent is a phenol-based curing agent or a naphthol-based curing agent, the reactive group is an aromatic hydroxyl group, and if the curing agent is an active ester-based curing agent, the reactive group is an active ester group.

[0123] (E) 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.

[0124] When the (E) 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 (E) curing agent being 100% by mass.

[0125] The content of (E) curing agent 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 30% by mass or less, further preferably 20% by mass or less, further more preferably 15% by mass or less, and particularly preferably 10% by mass or less. The lower limit of the content of (E) curing agent in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, for example, 0% by mass or more, 0.01% by mass or more, preferably 0.1% by mass or more, more preferably 1% by mass or more, further preferably 2% by mass or more, further more preferably 4% by mass or more, and particularly preferably 5% by mass or more.

[0126] <(F) Curing accelerator>

[0127] The resin composition of the present invention may contain (F) a curing accelerator as an optional component. The (F) curing accelerator has a function of accelerating the curing of the (D) epoxy resin.

[0128] (F) 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 amine curing accelerators and imidazole curing accelerators are particularly preferred. One curing accelerator may be used alone, or two or more curing accelerators may be used in combination.

[0129] Phosphorus curing accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium)pyromellitic acid salt, tetrabutylphosphonium hexahydrophthalate, 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, tetraphenylphosphonium tetra- Aromatic phosphonium salts such as phenyl borate, tetraphenylphosphonium tetra-p-tolyl borate, triphenylethylphosphonium tetraphenylborate, tri(3-methylphenyl)ethylphosphonium tetraphenylborate, tri(2-methoxyphenyl)ethylphosphonium tetraphenylborate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, 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, di-tert-butyl aliphatic phosphines such as tri(3-methyl-2-butenyl)phosphine, tricyclohexylphosphine, dibutylphenylphosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, 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 , 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, 2,2'-bis(diphenylphosphino)diphenyl ether and the like aromatic phosphines and the like.

[0130] 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, Aromatic dimethyl urea such as 1-dimethyl urea, 3-(4-isopropylphenyl)-1,1-dimethyl urea, 3-(4-methoxyphenyl)-1,1-dimethyl urea, 3-(4-nitrophenyl)-1,1-dimethyl urea, 3-[4-(4-methoxyphenoxy)phenyl]-1,1-dimethyl urea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethyl urea, 3-[3-(trifluoromethyl)phenyl]-1,1-dimethyl urea, N,N-(1,4-phenylene)bis(N',N'-dimethyl urea), N,N-(4-methyl-1,3-phenylene)bis(N',N'-dimethyl urea) [toluenebisdimethyl urea], and the like.

[0131] 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.

[0132] 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, 2-phenylimidazoline, and adducts of imidazole compounds with epoxy resins.

[0133] As the imidazole-based curing accelerator, a commercially available item may be used, and examples thereof include "P200-H50" manufactured by Mitsubishi Chemical Corporation.

[0134] Examples of the guanidine curing accelerator include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-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.

[0135] 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.

[0136] The content of (F) curing accelerator 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 less than 10% by mass, more preferably less than 5% by mass, further preferably less than 3% by mass, further more preferably less than 1% by mass, and particularly preferably less than 0.5% by mass. The lower limit of the content of (F) curing accelerator in the resin composition is not particularly limited. When the non-volatile component in the resin composition is set to 100% by mass, for example, more than 0% by mass, more than 0.0001% by mass, preferably more than 0.001% by mass, more preferably more than 0.005% by mass, further preferably more than 0.01% by mass, further more preferably more than 0.05% by mass, particularly preferably more than 0.1% by mass.

[0137] <(G) Other additives>

[0138] 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; Defoamers such as silicone defoamers, 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; flame retardants such as phosphorus flame retardants (such as phosphates, phosphinates, phosphazene compounds, and red phosphorus), nitrogen flame retardants (such as melamine sulfate), halogen flame retardants, and inorganic flame retardants (such as antimony trioxide). The additives can be used alone or in combination of two or more in any ratio. (G) The content of other additives can be appropriately set by those skilled in the art.

[0139] <(H) Organic solvent>

[0140] The resin composition of the present invention may contain, in addition to the above-mentioned non-volatile components, any organic solvent as a volatile component. As the (H) organic solvent, a known organic solvent may be used appropriately, and the type thereof is not particularly limited. As the (H) organic solvent, for example: 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, carbitol acetate (ethyl diglycolacetate, diethylene glycol monoethyl ether acetate), γ-butyrolactone, methoxypropionic acid methyl ester and other ether ester solvents; methyl lactate, ethyl lactate, 2-hydroxyisobutyric acid methyl ester 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. (H) The organic solvent may be used alone or in combination of two or more in any ratio.

[0141] <Method for producing resin composition>

[0142] 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 part or all of the same time, add (A) polyimide resin (preliminary imidized material), (B) carbodiimide resin, (C) inorganic filler, (D) epoxy resin used as needed, (E) curing agent used as needed, (F) curing accelerator used as needed, (G) other additives used as needed, and (H) organic solvent used as needed, 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.

[0143] <Characteristics of resin composition>

[0144] The resin composition of the present invention comprises (A) a polyimide resin, (B) a carbodiimide resin and (C) an inorganic filler, wherein the content of the component (C) is less than 40% by mass, thereby suppressing the halo phenomenon and obtaining a cured product having excellent heat resistance and flexibility.

[0145] Since the cured product of the resin composition of the present invention can suppress the halo phenomenon, the halo ratio calculated, for example, according to the following Test Example 1 may be preferably 40% or less, more preferably 35% or less, further preferably 30% or less, and particularly preferably 25% or less.

[0146] Since the cured product of the resin composition of the present invention has excellent heat resistance, the change rate of the elongation at break of the cured product before and after high-temperature treatment at 200°C for 5 hours according to the following Test Example 2 (the value calculated using the formula (1) of Test Example 2) can be preferably 50% or more, more preferably 60% or more, further preferably 70% or more, and particularly preferably 80% or more.

[0147] Since the cured product of the resin composition of the present invention has excellent flexibility, the number of folding times in the MIT folding test according to the following Test Example 3 is preferably 3,000 times or more, more preferably 5,000 times or more, further preferably 8,000 times or more, and particularly preferably 10,000 times or more.

[0148] <Application of resin composition>

[0149] 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, filling resins, and component embedding resins. Printed wiring boards, multilayer flexible substrates, etc. can be produced using sheet-like laminated materials such as resin sheets and prepregs.

[0150] <Resin Sheet>

[0151] 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.

[0152] 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.

[0153] 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.

[0154] 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.

[0155] 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.).

[0156] 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.

[0157] 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 the support with a release layer, for example, one or more release agents selected from alkyd resins, polyolefin resins, polyurethane resins, and silicone resins can be cited. The support with a release layer can use commercial products, for example, as a PET film having a release layer with an alkyd resin-based release agent as the main component, "SK-1", "AL-5", "AL-7" made by Lintec, "Lumirror T60" made by Toray, "Purex" made by Teijin, "Unipeel" made by UNITIKA, etc.

[0158] 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.

[0159] 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 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.

[0160] The resin sheet can be produced by directly coating the resin composition on a support using a die coater or the like, or by coating a resin varnish prepared by dissolving the resin composition in an organic solvent on a support and drying the varnish to form a resin composition layer.

[0161] Examples of the organic solvent that can be used when coating the support include the same organic solvents as those mentioned 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.

[0162] 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. The drying conditions also vary 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% 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.

[0163] 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.

[0164] <Laminated Sheet>

[0165] The laminated sheet can be a sheet made by laminating and curing multiple layers of resin composition layers. The laminated sheet includes 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.

[0166] The laminated sheet can be a sheet used by bending one of its faces relative to each other. The minimum bending radius of the laminated sheet is not particularly limited, but 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.

[0167] Each insulating layer included in the laminated sheet may have a hole formed therein, and the hole can function as a via hole or a through hole in the multilayer flexible substrate.

[0168] For the laminated sheet, in addition to the insulating layer, it can further include any element. For example, the laminated sheet can 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.

[0169] The conductor material used in the conductor layer is not particularly limited. In a preferred embodiment, the conductor layer comprises one or more metals selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin and indium. The conductor 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 group (for example, nickel-chromium alloy, copper-nickel alloy and copper-titanium alloy) can be cited. Among them, from the viewpoint of versatility, cost, ease of patterning, etc. of forming 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 are preferred. 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.

[0170] 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.

[0171] In order to make the conductor layer function as wiring, it can be patterned.

[0172] 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.

[0173] 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.

[0174] <Method for producing laminated sheet>

[0175] The laminated sheet 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 and laminating and curing a plurality of resin composition layers. The order of laminating and curing the resin composition layers 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 another resin composition layer is laminated on a certain resin composition layer, the laminated resin composition layer can be cured.

[0176] 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 denoted with symbols in the form of "first resin composition layer" and "second resin composition layer", and further, the insulating layers obtained by curing these resin composition layers are also denoted with symbols in the form of "first insulating layer" and "second insulating layer" in the same manner as the resin composition layers.

[0177] In a preferred embodiment, step (b) comprises the following steps:

[0178] (II) a step of curing the first resin composition layer to form a first insulating layer;

[0179] (VI) a step of laminating a second resin composition layer on the first insulating layer; and

[0180] (VII) a step of curing the second resin composition layer to form a second insulating layer. In addition, step (b) may further include any of the following steps as required:

[0181] (I) a step of laminating a first resin composition layer on a sheet-like supporting substrate;

[0182] (III) a process of opening a hole in the first insulating layer;

[0183] (IV) a step of roughening the first insulating layer; and

[0184] (V) Step of forming a conductor layer on the first insulating layer Each step will be described below.

[0185] 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.

[0186] 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.

[0187] 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.

[0188] When a resin sheet is used, the lamination of the sheet-like support substrate and the first resin composition layer can be performed by, for example, pressing the resin sheet from the support body side, and heating and pressing the first resin composition layer of the resin sheet 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 "heating and pressing member"), for example, a heated metal plate (SUS end plate, etc.) or a metal roller (SUS roller) etc. can be cited. Preferably, the heating and pressing member is not directly pressed to the resin sheet, but is pressed across 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.

[0189] After lamination, the first resin composition layer can be smoothed by, for example, pressing with a heating and pressing member under normal pressure (under atmospheric pressure). For example, when a resin sheet is used, the resin sheet is pressed with a heating and pressing member from the support side, so that the first resin composition layer of the resin sheet can be smoothed. 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.

[0190] 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. For example, when the first resin composition layer contains a thermosetting resin, it can be cured by thermally curing it.

[0191] Generally, specific heat curing conditions vary depending on the type of thermosetting resin. 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.

[0192] 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.

[0193] 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.

[0194] Step (IV) is a step of roughening the first insulating layer. Usually, in step (IV), contamination (smear) is also removed. Therefore, the roughening treatment is sometimes referred to as desmear treatment. Examples of the roughening treatment include a swelling treatment using a swelling solution, a roughening treatment using an oxidant, and a neutralization treatment using a neutralizing solution.

[0195] The swelling liquid is not particularly limited, and examples thereof include alkaline aqueous solutions such as sodium hydroxide aqueous solution and potassium hydroxide aqueous solution. Examples of commercially available swelling liquids include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth 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.

[0196] 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 performed by immersing the cured body in an oxidant solution heated to 60°C to 80°C for 10 minutes to 30 minutes.

[0197] 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.

[0198] 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.

[0199] 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.

[0200] 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 corresponding to a desired wiring pattern to expose a portion of the plating seed layer. 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 the like, thereby forming a conductor layer having a desired wiring pattern.

[0201] In step (II), a first insulating layer is obtained, and steps (III), (IV), and (V) are performed as needed, and then step (VI) is performed. Step (VI) is a step of laminating a 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).

[0202] 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).

[0203] 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.

[0204] In addition, in the method according to the aforementioned embodiment, as necessary, a step (VIII) of opening a hole on 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).

[0205] In the aforementioned embodiment, the embodiment of manufacturing a laminated sheet by stacking and curing of 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 stacking and curing of more than three layers of resin composition layers. For example, in the method related to the aforementioned embodiment, the stacking and curing of the resin composition layer performed by steps (VI) to (VII), and the opening of the insulating layer performed by steps (VIII) to (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 layers of insulating layers can be obtained.

[0206] Furthermore, the method according to the above-mentioned embodiment may further include any steps other than the above-mentioned steps. For example, when the step (I) is performed, a step of removing the sheet-like supporting substrate may be performed.

[0207] <Multilayer flexible substrate>

[0208] The multilayer flexible substrate includes a laminated sheet. The multilayer flexible substrate may include only the laminated sheet, or may include not only the laminated sheet but also any other member. Examples of the other members include electronic components and cover films.

[0209] The multilayer flexible substrate can be manufactured by a manufacturing method including a method for manufacturing the above-mentioned laminated sheet. Therefore, the multilayer flexible substrate can be manufactured by a manufacturing method including the following steps: (a) a step of preparing a resin sheet, and (b) a step of using the resin sheet and laminating and curing a plurality of resin composition layers.

[0210] The method for manufacturing a multilayer flexible substrate includes 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 joining the electronic component to a laminated sheet. Regarding the joining conditions between the laminated sheet and the electronic component, any conditions may be adopted under which the terminal electrodes of the electronic component and the conductor layer as wiring provided on the laminated sheet can be connected to each other. 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 with the cover film.

[0211] The aforementioned multi-layer flexible substrate can be used by bending one side of the laminated sheet included in the multi-layer flexible substrate so that it faces each other. For example, the multi-layer flexible substrate can be bent and stored in a housing of a semiconductor device in a reduced size. In addition, for example, the multi-layer flexible substrate can be provided in a movable portion of a semiconductor device having a bendable movable portion.

[0212] <Semiconductor devices>

[0213] 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 stacked sheets included in the multi-layer flexible substrate faces each other and is accommodated in a housing of the semiconductor device.

[0214] 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).

[0215] The semiconductor device described above can be manufactured, for example, by 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. Example

[0216] 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 refer to "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).

[0217] <Synthesis Example 1: Synthesis of polyimide resin 1>

[0218] In a reaction container, 50 g of G-3000 (difunctional hydroxyl-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl equivalent = 1798 g / eq., solid content 100 mass %: manufactured by Nippon Soda Co., Ltd.), 23.5 g of Ipzole 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 further 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 (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 -1 The disappearance of the NCO peak was confirmed. The disappearance of the NCO peak was regarded as the end point of the reaction. 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 urethane skeleton, and a butadiene skeleton.

[0219] Viscosity: 7.5 Pa・s (25°C, E-type viscometer)

[0220] Acid value: 16.9mgKOH / g

[0221] Solid content: 50% by mass

[0222] Number average molecular weight: 13723

[0223] Glass transition temperature: -10℃

[0224] The content of the polybutadiene structural part is: 50 / (50+4.8+8.96)×100=78.4 mass %.

[0225] <Synthesis Example 2: Synthesis of polyimide resin 2>

[0226] In a 500 ml separable flask equipped with a nitrogen inlet pipe 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 halfway, 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.

[0227] <Synthesis Example 3: Synthesis of polyimide resin 3>

[0228] A reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen inlet tube was charged with 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, 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.

[0229] <Synthesis Example 4: Synthesis of polyimide resin 4>

[0230] 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.

[0231] [Chemical formula 4]

[0232] .

[0233] [Chemical formula 5]

[0234] .

[0235] <Example 1: Preparation of resin composition 1>

[0236] A mixed solvent of 5 parts of a biphenylol epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 185), 5 parts of a naphthalene epoxy resin ("ESN475V" manufactured by Nippon Steel & Sumitomo Metal Chemical Co., Ltd., epoxy equivalent of about 332), 10 parts of a bisphenol AF epoxy resin ("YL7760" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 238), 2 parts of a cyclohexane epoxy resin ("ZX1658GS" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent of about 135), 40 parts of the polyimide resin 1 obtained in Synthesis Example 1 (non-volatile component: 50% by mass), and 10 parts of cyclohexanone was heated and dissolved while stirring. 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 and a non-volatile content of 50%), 6 parts of an active ester curing agent ("EXB-8000L-65M" manufactured by DIC Corporation, an MEK solution with an active group equivalent of about 220 and a non-volatile content of 65% by mass), and spherical silica ("SC2500SQ" manufactured by Yaduma Corporation, 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 obtained by surface treatment with 1 part of N-phenyl-3-aminopropyltrimethoxysilane ("KBM573" manufactured by Shin-Etsu Chemical Co., Ltd.), 25 parts of carbodiimide resin ("V-03" manufactured by Nisshinbo Co., Ltd., polycarbodiimide, a toluene solution with a non-volatile content of 50%), and 0.2 parts of an amine-based 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.

[0237] <Example 2: Preparation of resin composition 2>

[0238] 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% by mass) obtained in Synthesis Example 2 was used instead of 40 parts of polyimide resin 1 (non-volatile component: 50% by mass) obtained in Synthesis Example 1.

[0239] <Example 3: Preparation of resin composition 3>

[0240] 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% by mass) obtained in Synthesis Example 3 was used instead of 40 parts of polyimide resin 1 (non-volatile component: 50% by mass) obtained in Synthesis Example 1.

[0241] <Example 4: Preparation of resin composition 4>

[0242] 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% by mass) obtained in Synthesis Example 4 was used instead of 40 parts of polyimide resin 1 (non-volatile component: 50% by mass) obtained in Synthesis Example 1.

[0243] <Comparative Example 1: Preparation of Resin Composition 5>

[0244] Resin composition 5 was prepared by the same operation as in Example 1 except that 10 parts of the carbodiimide resin (“V-03” manufactured by Nisshinbo Co., Ltd., polycarbodiimide, toluene solution containing 50% nonvolatile matter) of Example 1 was not used.

[0245] <Comparative Example 2: Preparation of Resin Composition 6>

[0246] 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.

[0247] <Test Example 1: Evaluation of the Halo Phenomenon Suppression Characteristics>

[0248] (1) Copper clad laminate

[0249] As a copper-clad laminate, a glass cloth-based epoxy resin double-sided copper-clad laminate with copper foil layers laminated on both sides (copper foil thickness: 3 μm, substrate thickness: 0.15 mm, “HL832NSF LCA” manufactured by Mitsubishi Gas Chemical Co., Ltd., size: 255×340 mm) was prepared.

[0250] (2) Lamination of resin sheets with support

[0251] Using an intermittent vacuum pressurized laminator (Nikko-Materials, 2-stage stacking laminator, CVP700), the resin sheets with supports prepared in the examples (resin sheet A or resin sheet B in the comparative example) were laminated on both sides of the copper-clad laminate in such a way that the resin composition layer was in contact with the copper-clad laminate. The lamination was performed by decompressing for 30 seconds to make the air pressure below 13 hPa, and pressing at 130°C with a pressure of 0.74 MPa for 45 seconds. Next, hot pressing was performed at 120°C with a pressure of 0.5 MPa for 75 seconds.

[0252] (3) Thermal curing of resin composition layer

[0253] The copper-clad laminate on which the resin composition layer was laminated was placed in an oven at 100° C. and heat-cured for 30 minutes, and then moved to an oven at 180° C. and heat-cured for 30 minutes to form an insulating layer. This was referred to as a cured substrate A.

[0254] (4) Laser through-hole processing (laser drilling processing) (formation of through-holes)

[0255] Use Mitsubishi Electric CO 2 The laser processing machine "605GTWIII(-P)" irradiates the laser from the support to form a through hole with a top diameter (diameter) of 75μm on the insulating layer. The laser irradiation conditions are: mask diameter 1mm, pulse width 16μs, energy 0.2mJ / shot, number of shots 2, burst mode (10kHz).

[0256] (5) Roughening treatment

[0257] The support of the cured substrate A with the through-hole formed in the insulating layer was peeled off, and then a desmear treatment as a roughening treatment was performed. It should be noted that the following wet desmear treatment was performed as the desmear treatment.

[0258] Wet decontamination treatment

[0259] 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 10 minutes, then immersed in an oxidant 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 20 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 used as a roughened substrate A.

[0260] (6) Determination of through-hole diameter after decontamination treatment

[0261] A cross-sectional observation of the roughened substrate A was performed using a FIB-SEM composite device (SII Nanotechnologies, Inc., "SMI3050SE"). Specifically, a cross section in the vertical direction of the laser through hole was cut using a FIB (focused ion beam), and the through hole diameter after decontamination treatment was measured from the cross-sectional SEM image. For each sample, the through hole top diameter after decontamination treatment was measured from the cross-sectional SEM images of 5 randomly selected locations, and the average value was taken as the through hole top diameter Lt (μm), which is shown in the following Table 1.

[0262] (7) Determination of halo distance after roughening treatment

[0263] The roughened substrate A was observed using an optical microscope ("KH8700" manufactured by HIROX Corporation). Specifically, an optical microscope (CCD) was used to observe the insulating layer around the through hole from the upper portion of the roughened substrate A. The observation was performed by focusing the optical microscope on the top of the through hole. As a result of the observation, around the through hole, an insulating layer was observed to be continuous from the edge of the through hole top of the through hole and discolored into a white annular halo portion. Therefore, from the observed image, the radius r1 of the through hole top (equivalent to the inner radius of the halo portion) and the outer radius r2 of the halo portion were measured, and the difference r2-r1 between these radii r1 and r2 was calculated as the halo distance from the edge of the through hole top at the measurement position.

[0264] The above measurement was performed on five randomly selected through-holes. The average value of the halo distances of the five through-holes was taken as the halo distance Wt (μm) from the edge of the through-hole top of the sample, and is shown in Table 1 below.

[0265] Based on the through-hole top diameter Lt and the halo distance Wt, the halo ratio Ht is calculated and shown in the following Table 1. The so-called halo ratio Ht represents the ratio (Wt / (Lt / 2)) of the halo distance Wt from the edge of the through-hole top after the roughening treatment to the radius (Lt / 2) of the through-hole top of the through-hole after the roughening treatment. When the halo ratio Ht is less than 35%, it is judged as "○", and when the halo ratio Ht is greater than 35%, it is judged as "×".

[0266] <Test Example 2: Evaluation of heat resistance>

[0267] (1) Preparation of cured product for evaluation

[0268] A release PET film ("501010" manufactured by Lintec Corporation, 38 μm thick, 240 mm square) was placed on a glass cloth-based epoxy resin double-sided copper-clad laminate ("R5715ES" manufactured by Matsushita Electric Works, 0.7 mm thick, 255 mm square) in such a way that the untreated surface of the release PET film was in contact with the glass cloth-based epoxy resin double-sided copper-clad laminate, and the four sides of the release PET film were fixed with polyimide tape (10 mm wide).

[0269] Each of the resin sheets with a support (167×107 mm square) prepared in the examples and comparative examples was laminated in the center using an intermittent vacuum pressurization laminator (Nikko-Materials, 2-stage stacking laminator, CVP700) in such a way that the resin composition layer was in contact with the release surface of the release PET film. The lamination process was carried out by reducing the pressure for 30 seconds to a pressure of 13 hPa or less, and then pressing at 100° C. for 30 seconds at a pressure of 0.74 MPa.

[0270] Next, the support was peeled off, and the resin composition layer was thermally cured under curing conditions of 180° C. and 90 minutes.

[0271] After thermal curing, the polyimide tape was peeled off and the cured layer was removed from the glass cloth substrate epoxy resin double-sided copper-clad laminate. The release PET film was then peeled off from the cured layer to obtain a sheet-like cured product (cured product A for evaluation). In addition, after the cured layer was further heated at 200°C for 5 hours, it was peeled off from the release PET film in the same manner as the cured product A for evaluation to obtain a sheet-like cured product (cured product B for evaluation).

[0272] (2) Determination of elongation (elongation at break)

[0273] The evaluation cured products A and B were cut into dumbbell No. 1 shapes to obtain test pieces. For the test pieces, a tensile test of the evaluation cured product was carried out in accordance with Japanese Industrial Standards (JIS K7127) using a Tensilon universal testing machine (manufactured by A&D Co.), and the elongation at break (%) at 23°C was measured. This operation was carried out 3 times, and the respective average values ​​are shown in the following Table 1. The change rate of the average value A of the elongation at break (%) of the evaluation cured product A and the average value B of the elongation at break (%) of the evaluation cured product B were calculated using the following formula (1);

[0274] Change rate of elongation at break (%) = {(BA) / A} × 100 (1)

[0275] When the breaking elongation change rate was 80% or more, it was judged as "○", and when it was 80% or less, it was judged as "×".

[0276] <Test Example 3: Evaluation of flexibility (MIT folding resistance)>

[0277] The evaluation cured product A obtained in Test Example 2 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. According to JIS C-5016, the number of folding times until the cured body broke was measured 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. It should be noted that the measurement was performed on 5 samples, and the average value of the top 3 samples from high to low 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 "○".

[0278] 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.

[0279] [Table 1]

[0280] .

[0281] It can be seen that by using the following resin composition, a cured product with excellent flexibility, halo phenomenon suppression characteristics and heat resistance can be obtained. The resin composition is a resin composition comprising (A) a polyimide resin, (B) a carbodiimide resin and (C) an inorganic filler, wherein the content of component (C) is less than 40% by mass.

Claims

1. A resin composition comprising (A) a polyimide resin, (B) a carbodiimide resin, (C) an inorganic filler, (D) an epoxy resin and (E) a curing agent, in, When the nonvolatile components in the resin composition are set to 100% by mass, The content of the component (A) is 5% by mass or more and 35% by mass or less, The content of the component (B) is 3% by mass or more and 20% by mass or less, The content of the component (C) is 10% by mass or more and less than 40% by mass, The content of the component (D) is 10% by mass or more and 50% by mass or less, The component (E) contains an active ester-based curing agent.

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

3. The resin composition according to claim 1, wherein The weight average molecular weight of the component (A) is 7,000 or more.

4. The resin composition according to claim 1, wherein The weight average molecular weight of the component (A) is 50,000 or less.

5. 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) is 15% by mass or more.

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

7. 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) is 30% by mass or less.

8. The resin composition according to claim 1, wherein The component (B) is polycarbodiimide.

9. The resin composition according to claim 1, wherein The content of the isocyanate group in the molecule of the component (B) is 10% by mass or less.

10. The resin composition according to claim 1, wherein The content of the isocyanate group in the molecule of the component (B) is 0.2% by mass or less.

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 (B) is 5% 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 (B) is 15% by mass or less.

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 (B) is 10% by mass or less.

14. The resin composition according to claim 1, wherein The mass ratio of the component (B) to the component (A) (component (B) / component (A)) is 0.01 or more.

15. The resin composition according to claim 1, wherein The mass ratio of the component (B) to the component (A) (component (B) / component (A)) is 0.1 or more.

16. The resin composition according to claim 1, wherein The mass ratio of the component (B) to the component (A) (component (B) / component (A)) is 0.2 or more.

17. The resin composition according to claim 1, wherein The mass ratio of the component (B) to the component (A) (component (B) / component (A)) is 5 or less.

18. The resin composition according to claim 1, wherein The mass ratio of the component (B) to the component (A) (component (B) / component (A)) is 0.5 or less.

19. The resin composition according to claim 1, wherein The mass ratio of the component (B) to the component (A) (component (B) / component (A)) is 0.3 or less.

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

21. The resin composition according to claim 1, wherein The average particle size of the component (C) is 40 μm or less.

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

23. The resin composition according to claim 1, wherein The average particle size of the component (C) is 0.005 μm or more.

24. The resin composition according to claim 1, wherein The average particle size of the component (C) is 0.1 μm or more.

25. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100 mass %, the content of the component (C) is 33 mass % 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 30% by mass or more.

27. 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 30 mass % or less.

28. 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 25 mass % or more.

29. The resin composition according to claim 1, wherein When the total amount of the component (E) is 100% by mass, the content of the active ester curing agent is 10% by mass or more.

30. The resin composition according to claim 1, wherein When the total amount of the component (E) is 100% by mass, the content of the active ester curing agent is 40% by mass or more.

31. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100 mass %, content of the component (E) is 50 mass % or less.

32. 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 (E) is 10% by mass or less.

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 (E) is 0.01% by mass or more.

34. The resin composition according to claim 1, wherein When the nonvolatile matter in the resin composition is 100 mass %, content of the (E) component is 5 mass % or more. 35 . The resin composition according to claim 1 , further comprising (F) a curing accelerator.

36. The resin composition according to claim 35, wherein When the nonvolatile matter in the resin composition is 100% by mass, the content of the component (F) is 10% by mass or less.

37. The resin composition according to claim 35, wherein When the nonvolatile matter in the resin composition is 100 mass %, content of the component (F) is 0.5 mass % or less.

38. The resin composition according to claim 35, wherein When the nonvolatile matter in the resin composition is 100 mass %, content of the component (F) is 0.0001 mass % or more.

39. The resin composition according to claim 35, wherein When the nonvolatile matter in the resin composition is 100 mass %, content of the component (F) is 0.1 mass % or more.

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

41. A cured product, which is a cured product of the resin composition according to any one of claims 1 to 40.

42. A resin sheet comprising: Support body, and A resin composition layer formed from the resin composition according to any one of claims 1 to 40 and provided on the support. 43 . A multi-layer flexible substrate comprising an insulating layer formed by curing the resin composition according to claim 1 . A semiconductor device comprising the multi-layer flexible substrate according to claim 43 .