TW202130736A - Resin composition for obtaining a cured product excellent in flexibility, halo phenomenon suppression properties, and heat resistance - Google Patents

Abstract

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

Description

Resin composition

The present invention relates to a resin composition containing polyimide resin. More specifically, it relates to a cured product, a resin sheet, a multilayer flexible substrate, and a semiconductor device obtained by using the resin composition.

In recent years, the demand for thinner, lighter, and high-density semiconductor components has been increasing. In response to this request, the use of flexible substrates as substrates for semiconductor components has attracted attention. The flexible substrate can be thinner and lighter than the rigid substrate. Furthermore, since the flexible substrate is flexible and deformable, it can be bent for assembly.

So far, a composition containing a carbodiimide resin has been known (Patent Document 1). [Prior Technical Literature] [Patent Literature]

[Patent Document 1] JP 2016-027097 A

[The problem to be solved by the invention]

In the insulating material of the flexible substrate, polyimide resin may be blended in order to improve flexibility. In this case, when the amount of inorganic filler contained in the insulating material is small, the halo phenomenon becomes significant. In addition, the heat resistance tends to decrease.

The subject of the present invention is to provide a resin composition for obtaining a cured product excellent in flexibility, halo phenomenon suppression properties, and heat resistance. [Means to solve the problem]

In order to achieve the subject of the invention, the inventors of the present invention have conducted in-depth studies and found that by using (A) polyimide resin, (B) carbodiimide resin, and (C) less than 40% by mass ) The resin composition of the inorganic filler can obtain a cured product excellent in flexibility, halo phenomenon suppression properties, and heat resistance, and the present invention has been completed.

That is, the present invention includes the following contents. [1] A resin composition containing (A) polyimide resin, (B) carbodiimide resin, and (C) inorganic filler, wherein When the non-volatile content in the resin composition is 100% by mass, the content of component (C) is less than 40% by mass. [2] The resin composition of [1] above, wherein the weight average molecular weight of the component (A) is 1,000 or more and 100,000 or less. [3] The resin composition of [1] or [2] above, wherein when the non-volatile content in the resin composition is 100% by mass, the content of the component (A) is 15% by mass or more. [4] The resin composition of any one of [1] to [3] above, wherein when the non-volatile content in the resin composition is 100% by mass, the content of component (A) is 35% by mass or less. [5] The resin composition according to any one of [1] to [4] above, wherein the component (B) is polycarbodiimide. [6] The resin composition according to any one of [1] to [5] above, wherein the content of the isocyanate group in the molecule of the component (B) is 0.2% by mass or less. [7] The resin composition according to any one of [1] to [6] above, wherein when the non-volatile content in the resin composition is 100% by mass, the content of component (B) is 3% by mass or more. [8] The resin composition of any one of [1] to [7] above, wherein when the non-volatile content in the resin composition is 100% by mass, the content of component (B) is 15% by mass or less. [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. [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. [11] The resin composition of any one of [1] to [10] above, wherein the component (C) is silica. [12] The resin composition according to any one of [1] to [11] above, wherein the average particle size of the component (C) is 1 μm or less. [13] The resin composition according to any one of [1] to [12] above, which further contains (D) epoxy resin. [14] The resin composition according to any one of [1] to [13] above, which further contains (E) a hardener. [15] The resin composition according to [14] above, wherein the component (E) contains an active ester curing agent. [16] The resin composition of any one of [1] to [15] above, which is used for forming the insulating layer of a multilayer flexible substrate. [17] A cured product of the resin composition of any one of [1] to [16] above. [18] A resin sheet comprising a support and a resin composition layer formed of the resin composition according to any one of [1] to [16] above provided on the support. [19] A multilayer flexible substrate comprising an insulating layer formed by curing the resin composition of any one of [1] to [16] above. [20] A semiconductor device including the multilayer flexible substrate as described in [19] above. [Effects of Invention]

According to the resin composition of the present invention, a cured product excellent in flexibility, halo phenomenon suppression properties, and heat resistance can be obtained.

Hereinafter, the present invention will be described in detail based on its suitable embodiments. However, the present invention is not limited to the following embodiments and exemplified materials, and can be implemented with arbitrarily changed without departing from the scope of the present invention and its equivalent scope.

＜Resin composition＞ The resin composition of the present invention is a resin composition containing (A) polyimide resin, (B) carbodiimide resin, and (C) inorganic filler, wherein the content of (C) component is less than 40 quality%. By using such a resin composition, a cured product with excellent flexibility, halo phenomenon suppression properties, and heat resistance can be obtained.

The resin composition of the present invention may further contain optional components in addition to (A) polyimide resin, (B) carbodiimide resin, and (C) inorganic filler. Examples of optional components include (D) epoxy resin, (E) hardener, (F) hardening accelerator, (G) other additives, and (H) organic solvent. Hereinafter, each component contained in the resin composition will be described in detail.

＜(A) Polyimide resin＞ The resin composition of the present invention contains (A) polyimide resin. (A) Polyimide resin is a resin having an imine bond in a repeating unit. (A) The polyimide resin is not particularly limited. For example, it may contain (1) a resin obtained by the imidization reaction of a diamine compound and tetracarboxylic anhydride, or (2) a resin obtained by a diisocyanate compound and A resin obtained by the imidization reaction of tetracarboxylic anhydride. (A) Polyimide resins, including modified polyimide resins such as silicone modified polyimide resins.

(A) Polyimide resin is not particularly limited, for example, it may contain formula (A1):

[In the formula, X ¹ represents a tetravalent group obtained by removing two -CO-O-CO- from tetracarboxylic dianhydride. For example, it may include 2 selected from carbon atoms, oxygen atoms, nitrogen atoms, and sulfur atoms. Organic groups with more than one (for example, 2 to 3,000, 2 to 1,000, 2 to 100, and 2 to 50) skeleton atoms. X ² _{represents a divalent group obtained by removing two -NH 2} from a diamine compound, or a divalent group obtained by removing two -NCO from a diisocyanate compound. For example, it may include a carbon atom, an oxygen atom, and a nitrogen atom. And 2 or more (for example, 2 to 3,000, 2 to 1,000, 2 to 100, 2 to 50) selected from among sulfur atoms. n represents an integer of 2 or more]. ^{The organic groups of X 1} and X ² in the formula (A1) are not particularly limited as long as they are within the range of a chemically stable structure, and are a structure appropriately selected by a person having ordinary knowledge in the technical field, and may be, for example, well-known The structure of polyimide resin. (A) When the polyimide resin contains the structure represented by formula (A1), it preferably contains 60% by mass or more of the structure represented by formula (A1), more preferably 80% by mass or more, and more preferably 90% by mass or more, Especially preferably, it contains more than 95% by mass.

The diamine compound used to prepare the (A) polyimide resin is not particularly limited, and examples thereof include aliphatic diamine compounds and aromatic diamine compounds.

Aliphatic diamine compounds, for example, 1,2-ethylenediamine, 1,2-diaminopropane, 1,3-diaminopropane, 1,4-diaminobutane, 1,6-hexa Linear aliphatic diamine compounds such as methylene diamine, 1,5-diaminopentane, 1,10-diaminodecane, etc.; 1,2-diamino-2-methylpropane, Branched chain aliphatic diamine compounds such as 2,3-diamino-2,3-butane and 2-methyl-1,5-diaminopentane; 1,3-bis(aminomethyl Yl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, 1,3-diaminocyclohexane, 1,4-diaminocyclohexane, 4,4'-methylene Alicyclic diamine compounds such as bis(cyclohexylamine); dimer acid-type diamine (hereinafter also referred to as "dimer diamine") and the like.

Dimer acid type diamine, which refers to the diamine obtained by substituting the two terminal carboxyl groups (-COOH) of the dimer acid by aminomethyl group (-CH ₂ -NH ₂ ) or amino group (-NH ₂₎ Compound. Dimer acid is a known compound obtained by dimerizing unsaturated fatty acids (preferably those with 11-22 carbons, particularly those with 18 carbons). The industrial manufacturing process has been roughly standardized in the industry. . Dimer acid can be easily obtained by dimerizing unsaturated fatty acids with 18 carbons, such as oleic acid and linoleic acid, which are particularly cheap and easy to obtain. The dimer acid with 36 carbons is The principal component. In addition, the dimer acid may contain any amount of monomer acid, trimer acid, other polymerized fatty acids, etc., depending on the production method, the degree of purification, and the like. In addition, the double bond remains after the polymerization reaction of the unsaturated fatty acid. However, in this specification, the hydride whose degree of unsaturation is further reduced by the hydrogenation reaction is also included in the dimer acid. The dimer acid-type diamine can be obtained from commercially available products, and examples thereof include "PRIAMINE 1073", "PRIAMINE 1074", "PRIAMINE 1075" manufactured by Croda Japan, "Versamine 551" and "Versamine 552" manufactured by Cognis Japan.

Examples of the aromatic diamine compound include 1,4-phenylenediamine, 1,2-phenylenediamine, 1,3-phenylenediamine, 2,4-diaminotoluene, 2,6-diaminotoluene, Phenylenediamine compounds such as 3,5-diaminobiphenyl, 2,4,5,6-tetrafluoro-1,3-phenylenediamine; 1,5-diaminonaphthalene, 1,8-diamine Naphthalene diamine compounds such as diaminonaphthalene, 2,6-diaminonaphthalene, and 2,3-diaminonaphthalene; 4,4'-diamino-2,2'-di-trifluorofluoromethyl-1 ,1'-biphenyl, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, 3,3'-diaminodiphenyl ether, 4,4' -Diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, 4-aminophenyl 4-aminobenzoate, 1,3-bis(3-aminophenoxy) Benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene, 2,2-bis(4-aminophenyl)propane , 4,4'-(hexafluoroisopropylidene)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-phenylene)diphenylamine, 2,2-bis(3-methyl -4-aminophenyl)propane, 2,2-bis(3-methyl-4-aminophenyl)benzene, 4,4'-diamino-3,3'-dimethyl-1, 1'-biphenyl, 4,4'-diamino-2,2'-dimethyl-1,1'-biphenyl, 9,9'-bis(3-methyl-4-aminophenyl) )Chrysanthemum, 5-(4-aminophenoxy)-3-[4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindane, 4-aminobenzene Diphenylamine compounds such as 5-amino-1,1'-biphenyl-2-yl formate, etc.

A commercially available diamine compound may be used, or a compound synthesized by a known method may be used. A diamine compound may be used individually by 1 type, and may be used in combination of 2 or more types.

The diisocyanate compound used to prepare the (A) polyimide resin is not particularly limited, and examples thereof include aliphatic diisocyanate compounds, aromatic diisocyanate compounds, and polyurethane at both ends of isocyanate groups.

The aliphatic diisocyanate compound includes, for example, linear aliphatic diisocyanate compounds such as tetramethylene diisocyanate, hexamethylene diisocyanate, octamethylene diisocyanate, and dodecamethylene diisocyanate; 2 , 2,4-trimethylhexamethylene diisocyanate, 2,4,4-trimethylhexamethylene diisocyanate, 2,2-dimethylpentamethylene diisocyanate, etc. Aliphatic diisocyanate compounds; isophorone diisocyanate (IPDI), cyclohexane-1,3-diisocyanate, cyclohexane-1,4-diisocyanate (CHDI), 4-methylcyclohexane-1, 3-diisocyanate, 2-methylcyclohexane-1,3-diisocyanate, 2-methylcyclohexane-1,4-diisocyanate, dicyclohexylmethane-4,4'-diisocyanate, bicyclic Hexyl ether-4,4'-diisocyanate, 1,4-bis(isocyanatomethyl)cyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane, 3a,4,5 ,6,7,7a-hexahydro-4,7-methylene indane-1,8-ylidene diisocyanate, 1,3-bis(isocyanatomethyl)cyclohexane, 1,4 -Alicyclic diisocyanate compounds such as bis(isocyanatomethyl)cyclohexane; dimer acid diisocyanate, etc.

The dimer acid diisocyanate means _{a diisocyanate compound obtained by substituting the amine group (-NH 2} ) of the dimer acid diamine described above with an isocyanate group (-NCO).

Aromatic diisocyanate compounds, for example, 1,4-benzene diisocyanate, 1,3-benzene diisocyanate, toluene-2,6-diisocyanate, toluene-2,4-diisocyanate, toluene-3,5-diisocyanate Isocyanate, 2-methyl-4,6-diisopropylbenzene-1,3-diisocyanate, 2,4,6-triethylbenzene-1,3-diisocyanate, 4,6-diethylbenzene -1,3-diisocyanate, 2,5-diethylbenzene-1,3-diisocyanate, 2,5-diethylbenzene-1,4-diisocyanate, 2,4,6-triisocyanate Benzene-1,3-diisocyanate, 4,6-diisopropylbenzene-1,3-diisocyanate, 2,5-diisopropylbenzene-1,3-diisocyanate, 2,5-diisocyanate Benzene-1,4-diisocyanate, m-xylene diisocyanate, p-xylene diisocyanate, tetramethyl-m-xylene diisocyanate, tetramethyl-p-xylene diisocyanate, etc. Compound; 1,3-naphthalenediyl diisocyanate, 1,6-naphthalenediyl diisocyanate, 1,7-naphthalenediyl diisocyanate, 1,8-naphthalenediyl diisocyanate, 2,6-naphthalenediyl diisocyanate Naphthalene diisocyanate compounds such as isocyanate and 2,7-naphthalenediyl diisocyanate; 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'-Dimethoxybisphenyl 4,4'-diisocyanate, 3,3'-dimethoxydiphenylmethane-4,4'-diisocyanate, 4,4'-dimethoxydiphenylmethane-3,3' -Bis(isocyanatobenzene) compounds such as diisocyanate, etc.

Polyurethane with two-terminal isocyanate groups can be aliphatic diisocyanate compound and/or aromatic diisocyanate compound as listed above, and a polymer with two-terminal hydroxyl groups to undergo a urethane reaction And the winner. The two-terminal hydroxyl polymer may be, for example, two-terminal hydroxyl polybutadiene, two-terminal hydroxyl hydrogenated polybutadiene, two-terminal hydroxyl polyisoprene, two-terminal hydroxyl hydrogenated polyisoprene, and the like. Olefins; two-terminal hydroxy polyethers such as polyethylene glycol with two-terminal hydroxy groups, polypropylene glycol with two-terminal hydroxy groups, and polytetramethylene glycol with two-terminal hydroxy groups.

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

The two-terminal isocyanate group polyurethane is, for example, according to formula (A2):

[In the formula, X ^2a represents independently a divalent group obtained by removing two -NCO from an aliphatic diisocyanate compound or an aromatic diisocyanate compound. For example, it may include a carbon atom, an oxygen atom, a nitrogen atom, and An organic group of 2 to 50 skeleton atoms selected from the sulfur atom. X ^2b represents a divalent group obtained by removing two -OH from a polymer with two terminal hydroxyl groups. For example, it may contain two or more selected from carbon atoms and oxygen atoms (e.g., 2 to 1,000, 2 ~500) the organic group of the skeleton atom. m represents an integer from 1 to 10] represents the two-terminal isocyanate group polyurethane.

As the diisocyanate compound, a commercially available one may be used, or a compound synthesized by a known method or a method based thereon may also be used. A diisocyanate compound may be used individually by 1 type, and may be used in combination of 2 or more types.

The tetracarboxylic anhydride used to prepare the (A) polyimide resin is not particularly limited, and examples include aliphatic tetracarboxylic dianhydride and aromatic tetracarboxylic dianhydride.

Aliphatic tetracarboxylic dianhydride, specifically, 1,2,3,4-cyclobutane tetracarboxylic dianhydride, cyclopentane tetracarboxylic dianhydride, cyclohexane-1,2,3, 4-tetracarboxylic dianhydride, cyclohexane-1,2,4,5-tetracarboxylic dianhydride, 3,3',4,4'-bicyclohexyltetracarboxylic dianhydride, carbonyl-4,4' -Bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, methylene-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, 1,2-ethylene oxide -4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, oxy-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfur -4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, sulfonyl-4,4'-bis(cyclohexane-1,2-dicarboxylic acid) dianhydride, etc. .

Aromatic tetracarboxylic dianhydride, for example, pyromellitic dianhydride such as pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, etc.; 1,4,5,8-naphthalene Tetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride and other naphthalene tetracarboxylic dianhydrides; 2,3,6,7-anthracene tetracarboxylic dianhydride and other anthracene tetracarboxylic dianhydrides Anhydride; 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4 '-Diphenyl tetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2',3,3'-biphenyltetracarboxylic dianhydride, 2, 3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether Tetracarboxylic dianhydride, 2,3,3',4'-diphenyl tetracarboxylic dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl) dianhydride, sub Methyl-4,4'-diphthalic dianhydride, 1,1-ethynylene-4,4'-diphthalic dianhydride, 2,2-propylene-4,4'- Diphthalic dianhydride, 1,2-ethylene-4,4'-diphthalic dianhydride, 1,3-trimethylene-4,4'-diphthalic dianhydride, 1,4-tetramethylene-4,4'-diphthalic dianhydride, 1,5-pentamethylene-4,4'-diphthalic dianhydride, 1,3-bis( 3,4-Dicarboxyphenyl)phthalic anhydride, 1,4-bis(3,4-dicarboxyphenyl)phthalic anhydride, 1,3-bis(3,4-dicarboxyphenoxy)phthalic anhydride 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 dianhydride and other diphthalic dianhydrides.

A commercially available tetracarboxylic dianhydride may be used, or a compound synthesized by a known method or a method based on it may be used. Tetracarboxylic dianhydride may be used singly or in combination of two or more kinds.

Relative to the total structure derived from the tetracarboxylic dianhydride constituting the polyimide resin (A), the content of the structure derived from the aromatic tetracarboxylic dianhydride is preferably 10 mol% or more, more preferably It is 30 mol% or more, more preferably 50 mol% or more, still more preferably 70 mol% or more, still more preferably 90 mol% or more, and particularly preferably 100 mol%.

(A) The weight average molecular weight of the polyimide resin is not particularly limited, but is preferably 1,000 or more, more preferably 3,000 or more, still more preferably 5,000 or more, particularly preferably 7,000 or more. (A) The upper limit of the weight average molecular weight of the polyimide resin is not particularly limited, but is preferably 100,000 or less, more preferably 80,000 or less, particularly preferably 60,000 or less, and particularly preferably 50,000 or less. (A) The number average molecular weight of the polyimide resin is not particularly limited, but is preferably 1,000 or more, more preferably 3,000 or more, still more preferably 5,000 or more, particularly preferably 7,000 or more. (A) The upper limit of the number average molecular weight of the polyimide resin is not particularly limited, but is preferably 100,000 or less, more preferably 80,000 or less, particularly preferably 60,000 or less, and particularly preferably 50,000 or less. The weight average molecular weight and number average molecular weight here can be the values measured by the gel permeation chromatography (GPC) method (in terms of polystyrene).

The content of (A) polyimide resin in the resin composition is not particularly limited. When the non-volatile content in the resin composition is 100% by mass, it is preferably 60% by mass or less, more preferably 50% by mass. Or less, more preferably 40% by mass or less, still more preferably 35% by mass or less, 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 content in the resin composition is 100% by mass, it is preferably 1% by mass or more, more preferably 5 Mass% or more, more preferably 10 mass% or more, still more preferably 15 mass% or more, particularly preferably 20 mass% or more.

＜(B)Carbodiimide resin＞ The resin composition of the present invention contains (B) carbodiimide resin. (B) Carbodiimide resin is a compound having more than one carbodiimide structure (-N=C=N-) in one molecule. (B) The carbodiimide resin is preferably a compound having two or more carbodiimide structures in one molecule, and particularly preferably a polycarbodiimide having a carbodiimide structure in the repeating unit. The polycarbodiimide may be cyclic or chain-like.

The polycarbodiimide is not particularly limited, and may include, for example, a polycarbodiimide obtained by intermolecular decarbonation condensation reaction of a diisocyanate compound. The polycarbodiimide obtained in this way has an isocyanate group (-N=C=O) in the molecule, part or all of which can also be subjected to monoisocyanate compounds, alcohol compounds, amine compounds, carboxylic acid compounds, epoxy Compounds and other known sealants are further processed. The diisocyanate compound used to prepare polycarbodiimide is, for example, the same as the "diisocyanate compound used to prepare (A) polyimide resin". (B) Carbodiimide resin may be used individually by 1 type, and may be used in combination of 2 or more types.

(B) The carbodiimide resin is not particularly limited. For example, it preferably contains the formula (B1):

[In the formula, X ³ represents a divalent group obtained by removing two -NCO from a diisocyanate compound, for example, it contains two or more selected from a carbon atom, an oxygen atom, a nitrogen atom, and a sulfur atom (for example, 2-50 1, 2~40, 2~30, 2~20) of the organic group of the skeleton atoms. In one embodiment, it can be an alkylene group, an aryl group, an aryl group substituted by an alkyl group, and the like的组合。 The combination. p represents an integer of 2 or more] represents the structure of polycarbodiimide.

"Alkane (base)" refers to a linear, branched and/or cyclic divalent aliphatic saturated hydrocarbon group. The number of carbon atoms of "alkylene (base)" may be 2-30, 2-20, etc., for example. Examples of "alkylene (base)" include linear alkylene groups such as ethylidene, trimethylene, tetramethylene, pentamethylene, hexamethylene, heptamethylene, and octamethylene; Ethylene, propylene, isopropylene, 1-methylethylene, 1-ethylethylene, trimethylene, 2-methyltrimethylene, 2-methyltetramethylene, 2 ,3-dimethyltetramethylene, 1,3-dimethyltetramethylene, 2-methylpentamethylene, 2,2-dimethylpentamethylene, 2,4-dimethyl Pentamethylene, 1,3,5-methylpentamethylene, 2-methylhexamethylene, 2,2-dimethylhexamethylene, 2,4-dimethylhexamethylene Branched alkylene group, 1,3,5-trimethylhexamethylene, 2,2,4-trimethylhexamethylene, 2,4,4-trimethylhexamethylene, etc. ; 1,3-cyclopentyl, 1,3-cyclohexyl, 1,4-cyclohexyl, 4-methyl-1,3-cyclohexyl, 2-methyl-1,3-cyclohexyl Cyclic alkylene such as hexyl, 2-methyl-1,4-cyclohexylene, etc.; Cyclic-straight-chain-cyclic alkylene such as methylenebis(4,1-cyclohexylene); Cyclic-branched-cyclic alkylenes such as isopropylidene bis(4,1-cyclohexylene); straight-chain-cyclic-linear alkylenes such as 1,4-cyclohexyldimethylene Alkylene; 1,4-cyclohexyl diisopropylidene, etc. branched-cyclic-branched alkylene, etc.

"Aromatic (base)" refers to a divalent aromatic hydrocarbon group. The number of carbon atoms of "Shenfang (base)" can be, for example, 6-14, 6-10, etc. Examples of "arylene (group)" include 1,3-phenylene, 1,4-phenylene, 1,5-naphthylene, 1,8-naphthylene, 2,6-naphthylene, etc. . "Aryl group substituted by an alkyl group" refers to an arylene group substituted with an alkyl group such as methyl, ethyl, propyl, isopropyl and the like. The number of carbon atoms of "an aryl group substituted with an alkyl group" can be, for example, 7-30, 7-20, and the like. "Anylidene (base) substituted by an alkyl group", for example, 2,6-tolylene, 2,4-tolylene, 3,5-tolylene, 2-methyl-4,6-di Isopropyl-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, 2,5-diisopropyl-1,4-phenylene, etc. Combinations of alkylene, arylene, and alkylene substituted arylene, for example, alkylene-arylene-alkylene, alkylene-alkylene substituted aryl-alkylene Group, aryl-alkylene-aryl-alkylene, aryl-alkylene substituted by alkyl-alkylene-aryl-alkylene substituted with alkyl, etc. Alkylene, aryl, and aryl substituted with alkyl may further have optional substituents.

^{The organic group of X 3} in the formula (B1) is not particularly limited as long as it is within the range of a chemically stable structure. It is a structure appropriately selected by a person with ordinary knowledge in the technical field. For example, it may be a well-known polycarbonate. The structure of imine.

In one embodiment, the (B) carbodiimide resin specifically includes polyhexamethylene carbodiimide, polytrimethylhexamethylene carbodiimide, and polycyclohexyl carbodiimide. Aliphatic polycarbodiimide such as amine, poly(methylene bis-cyclohexyl carbodiimide), poly(isophorone carbodiimide); or poly(phenylene carbodiimide), poly (Naphthyl carbodiimide), poly (tolyl carbodiimide), poly (methyl diisopropyl phenyl carbodiimide), poly (triethyl phenyl carbodiimide), Poly (diethyl phenylene carbodiimide), poly (triisopropyl phenylene carbodiimide), poly (diisopropyl phenylene carbodiimide), poly (xylylene carbodiimide) ), poly(tetramethylxylylene carbodiimide), poly(methylene diphenylene carbodiimide), poly[methylene bis(methylphenylene carbodiimide), etc. The aromatic polycarbodiimide of polycarbodiimide.

(B) The content of the isocyanate group (-N=C=O) in the molecule of the carbodiimide resin is preferably 10% by mass or less, more preferably 5% by mass or less, 3% by mass or less, and It is more preferably 2% by mass or less, 1% by mass or less, still more preferably 0.5% by mass or less, 0.2% by mass or less, particularly preferably 0% by mass, that is, (B) the carbodiimide resin does not contain isocyanic acid The base is particularly good.

(B) Commercial products of carbodiimide resin, for example, "Carbodilite (registered trademark) V-02B", "Carbodilite (registered trademark) V-03", "Carbodilite (registered trademark) V manufactured by Nisshinbo Chemical Co., Ltd. -04K", "Carbodilite (registered trademark) V-07" and "Carbodilite (registered trademark) V-09"; "Stabaxol (registered trademark) P", "Stabaxol (registered trademark) P400", "Carbodilite (registered trademark) V-09" manufactured by Rhein Chemie Hycasyl (registered trademark) 510" and so on.

The content of (B) carbodiimide resin in the resin composition is not particularly limited. When the non-volatile content in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably 30% by mass Below, it is more preferably 20% by mass or less, still 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 content in the resin composition is 100% by mass, it is preferably 0.1% by mass or more, more preferably 0.5 Mass% or more, more preferably 1 mass% or more, still more preferably 3 mass% or more, particularly preferably 5 mass% or more.

Relative to the (A) polyimide resin in the resin composition, the mass ratio of (B) carbodiimide resin ((B) carbodiimide resin/(A) polyimide resin), and There is no particular limitation, but it is preferably 5 or less, more preferably 1 or less, still more preferably 0.5 or less, and still more 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, still more preferably 0.1 or more, and more Preferably, it is 0.2 or more.

＜(C) Inorganic filler＞ The resin composition of the present invention contains (C) an inorganic filler. (C) The inorganic filler is contained in the resin composition in the form of particles.

(C) The material of the inorganic filler is an inorganic compound. (C) Materials for inorganic fillers, such as silica, alumina, glass, cordierite, silica, barium sulfate, barium carbonate, talc, clay, mica powder, zinc oxide, hydrotalcite, diaspore , 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, titanic acid Bismuth, titanium oxide, zirconium oxide, barium titanate, barium zirconate titanate, barium zirconate, calcium zirconate, zirconium phosphate, and zirconium tungstate phosphate, etc. Among these, silicon dioxide is particularly suitable. Examples of silicon dioxide include amorphous silicon dioxide, fused silicon dioxide, crystalline silicon dioxide, synthetic silicon dioxide, and hollow silicon dioxide. In addition, the silicon dioxide is preferably spherical silicon dioxide. (C) Inorganic fillers may be used singly, or two or more of them may be used in combination at any ratio.

(C) Commercial products of inorganic fillers, such as "SP60-05" and "SP507-05" manufactured by Nippon Steel & Sumikin Materials; "YC100C", "YA050C", "YA050C-MJE" manufactured by Admatechs ", "YA010C", "SC2500SQ", "SO-C4", "SO-C2", "SO-C1"; "Silfil NSS-3N", "Silfil NSS-4N", "Silfil NSS- 5N"; "UFP-30", "DAW-03", "FB-105FD" manufactured by Denka; "IMSIL A-8", "IMSIL A-10", "IMSIL A-15", " IMSIL A-25" etc.

(C) The average particle size of the inorganic filler is not particularly limited, but is preferably 40 μm or less, more preferably 10 μm or less, still more preferably 5 μm or less, still more preferably 3 μm or less, particularly preferably 1 μm or less. (C) The lower limit of the average particle size of the inorganic filler is not particularly limited. It is preferably 0.005 μm or more, more preferably 0.01 μm or more, still more preferably 0.03 μm or more, and still more preferably 0.05 μm or more. Preferably, it is 0.1 μm or more. (C) The average particle size of the inorganic filler can be measured by the laser diffraction/scattering method based on the Mie scattering theory. Specifically, a laser diffraction scattering type particle size distribution measuring device can be used to prepare the particle size distribution of the inorganic filler on a volume basis, and measure it by taking its median diameter as the average particle size. For the measurement sample, 100 mg of the inorganic filler and 10 g of methyl ethyl ketone can be weighed into a vial and dispersed by ultrasound for 10 minutes. Using a laser diffraction particle size distribution measuring device, set the wavelength of the light source to blue and red, measure the volume-based particle size distribution of the inorganic filler in the flow cell method, and use the obtained particle size distribution to The average particle size is calculated from the form of the median diameter. Examples of the laser diffraction particle size distribution measuring device include "LA-960" manufactured by Horiba Manufacturing Co., Ltd. and the like.

(C) The specific surface area of the inorganic filler is not particularly limited. It is preferably 0.1 m ² /g or more, more preferably 0.5 m ² /g or more, still more preferably 1 m ² /g or more, particularly ^{preferably 5 m 2} /g above. (C) The upper limit of the specific surface area of the inorganic filler is not particularly limited. It is preferably 50m ² /g or less, more preferably 30m ² /g or less, still more preferably 20m ² /g or less, particularly ^{preferably 15m 2} /g or less. The specific surface area of the inorganic filler can be obtained by following the BET method, using a specific surface area measuring device (Macsorb HM-1210 manufactured by Mountech) to adsorb nitrogen on the sample surface, and calculating the specific surface area using the BET multipoint method.

(C) The inorganic filler is preferably surface-treated with a suitable surface treatment agent. Surface treatment can improve the moisture resistance and dispersibility of (C) inorganic fillers. Examples of surface treatment agents include vinyl-based silane coupling agents such as vinyl trimethoxy silane and vinyl triethoxy silane; 2-(3,4-epoxycyclohexyl) ethyl trimethoxy silane, 3 -Glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxysilane Epoxy silane coupling agent such as propyl triethoxy silane; Styryl silane coupling agent such as p-styryl trimethoxy silane; 3-methacryloxy propyl methyl dimethoxy 3-methacryloxypropyltrimethoxysilane, 3-methacryloxypropylmethyldiethoxysilane, 3-methacryloxypropyltriethoxy Methacrylic silane coupling agent such as silane; Acrylic silane coupling agent such as 3-propenoxypropyltrimethoxysilane; N-2-(aminoethyl)-3-aminopropylmethyl Dimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane , 3-Triethoxysilyl-N-(1,3-dimethyl-butylene) propylamine, N-phenyl-3-aminopropyltrimethoxysilane, N-phenyl-8 -Amino octyl trimethoxysilane, N-(vinylbenzyl)-2-aminoethyl-3-aminopropyl trimethoxysilane and other amino-based silane coupling agents; see -(trimethoxy Silyl propyl) isocyanurate-based silane coupling agent such as isocyanurate; 3-ureidopropyl trialkoxy silane and other ureido-based silane coupling agent; 3-mercapto Mercapto-based silane coupling agents such as propyl methyl dimethoxy silane and 3-mercaptopropyl trimethoxy silane; isocyanate-based silane coupling agents such as 3-isocyanate propyl triethoxy silane; 3-trimethoxy silane Silane propyl succinic anhydride and other acid anhydrides are silane coupling agents such as silane coupling agents; methyl trimethoxy silane, dimethyl dimethoxy silane, phenyl trimethoxy silane, methyl triethoxy silane, Dimethyldiethoxysilane, phenyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, hexyltrimethoxysilane, hexyltriethoxysilane, octyl Non-silane coupling-alkoxysilane compounds such as triethoxysilane, decyltrimethoxysilane, 1,6-bis(trimethoxysilyl)hexane, trifluoropropyltrimethoxysilane, etc. Among them, amine-based silane coupling agents are particularly preferred. A surface treatment agent may be used individually by 1 type, and may be used combining two or more types in arbitrary ratios.

Commercial products of surface treatment agents include, for example, "KBM-1003", "KBE-1003" (vinyl silane coupling agent) manufactured by Shin-Etsu Chemical Co., Ltd.; "KBM-303", "KBM-402", and "KBE-1003". KBM-403", "KBE-402", "KBE-403" (epoxy silane coupling agent); "KBM-1403" (styrene-based 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" (amino-based silane coupling agent); "KBM-9659" (isocyanurate-based silane Coupling agent); "KBE-585" (ureido-based silane coupling agent); "KBM-802", "KBM-803" (mercapto-based silane coupling agent); "KBE-9007N" (isocyanate-based silane coupling agent); "X-12-967C" (anhydride silane coupling agent); "KBM-13", "KBM-22", "KBM-103", "KBE-13", "KBE-22", "KBE-103" , "KBM-3033", "KBE-3033", "KBM-3063", "KBE-3063", "KBE-3083", "KBM-3103C", "KBM-3066", "KBM-7103" (not Silane coupling-alkoxysilane compound) and so on.

In terms of the degree of surface treatment of the surface treatment agent, from the viewpoint of improving the dispersibility of the inorganic filler, it is preferable to fall within a specific range. Specifically, 100% by mass of the inorganic filler is preferably surface treated with a surface treatment agent of 0.2% to 5% by mass, more preferably 0.2% to 3% by mass surface treatment, and more preferably 0.3% to 2% by mass. Quality% surface treatment.

The degree of surface treatment with the surface treatment agent can be evaluated by the amount of carbon per unit surface area of the inorganic filler. The amount of carbon per unit surface area of the inorganic filler, from the viewpoint of improving the dispersibility of the inorganic filler, is preferably 0.02 mg/m ² or more, more preferably 0.1 mg/m ² or more, and still more preferably 0.2 mg/m ² or more. On the other hand, from the viewpoint of preventing the melt viscosity of the resin composition or the melt viscosity in the sheet form from rising, it is preferably 1.0 mg/m ² or less, more preferably 0.8 mg/m ² or less, and still more preferably 0.5 mg /m ² or less.

(C) The amount of carbon per unit surface area of the inorganic filler can be measured after the surface-treated inorganic filler is washed with a solvent (for example, methyl ethyl ketone (MEK)). Specifically, a sufficient amount of MEK as a solvent is added to the inorganic filler surface-treated with a surface treatment agent, and ultrasonic cleaning is performed at 25° C. for 5 minutes. After removing the supernatant and drying the solid content, the carbon content per unit surface area of the inorganic filler can be measured using a carbon analyzer. For the carbon analyzer, "EMIA-320V" manufactured by Horiba Manufacturing Co., Ltd. can be used.

The content of (C) inorganic filler in the resin composition is less than 40% by mass when the non-volatile content in the resin composition is 100% by mass. From the viewpoint of improving flexibility, it is preferably 39% by mass or less , 38% by mass or less, more preferably 37% by mass or less, still more preferably 35% by mass or less, particularly preferably 33% by mass or less. The lower limit of the content of (C) inorganic filler in the resin composition is not particularly limited. When the non-volatile content in the resin composition is 100% by mass, it is preferably 0.1% by mass or more, more preferably 1% by mass Above, more preferably 10% by mass or more, still more preferably 20% by mass or more, and particularly preferably 30% by mass or more.

＜(D)Epoxy resin＞ The resin composition of the present invention may contain (D) epoxy resin as an optional component. (D) Epoxy resin means a curable resin having an epoxy group.

(D) The epoxy resin includes, for example, bixylenol type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, bisphenol AF type epoxy resin, Dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol novolak type epoxy resin, phenol novolak type epoxy resin, tert-butyl-catechol type epoxy resin, naphthalene type ring Oxygen resin, naphthol type epoxy resin, anthracene type epoxy resin, glycidylamine type epoxy resin, glycidyl ester type epoxy resin, cresol novolak type epoxy resin, phenol aralkyl type epoxy resin, Biphenyl epoxy resin, linear aliphatic epoxy resin, epoxy resin with butadiene structure, alicyclic epoxy resin, heterocyclic epoxy resin, epoxy resin containing spiro ring, cyclohexane Type epoxy resin, cyclohexane dimethanol type epoxy resin, naphthyl ether type epoxy resin, trimethylol type epoxy resin, tetraphenylethane type epoxy resin, isocyanurate type ring Oxygen resin, phenol benzmetholamine type epoxy resin, phenolphthalein type epoxy resin, etc. (D) Epoxy resin may be used alone or in combination of two or more kinds.

The resin composition preferably contains an epoxy resin having two or more epoxy groups in one molecule as the (D) epoxy resin. The ratio of epoxy resin having 2 or more epoxy groups in one molecule relative to 100% by mass of the non-volatile content of the epoxy resin (D) is preferably 50% by mass or more, more preferably 60% by mass Above, 70% by mass or more is particularly preferred.

Epoxy resins are epoxy resins that are liquid at a temperature of 20°C (hereinafter referred to as "liquid epoxy resins"), and epoxy resins that are solid at a temperature of 20°C (hereinafter referred to as " "Solid epoxy resin"). The resin composition of the present invention may contain only a liquid epoxy resin as an epoxy resin, or may contain only a solid epoxy resin, or may contain a combination of a liquid epoxy resin and a solid epoxy resin. 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; more preferably a solid epoxy resin.

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

Liquid epoxy resin, preferably bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol AF type epoxy resin, naphthalene type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine Type epoxy resin, phenol novolac type epoxy resin, alicyclic epoxy resin with ester skeleton, cyclohexane type epoxy resin, cyclohexane dimethanol type epoxy resin, and ring with butadiene structure Oxy resin.

Specific examples of liquid epoxy resins include "HP4032", "HP4032D", and "HP4032SS" (naphthalene type epoxy resin) manufactured by DIC; "828US", "828EL", and "jER828EL" manufactured by Mitsubishi Chemical Corporation. , "825", "Epikote 828EL" (bisphenol A type epoxy resin); "jER807" and "1750" (bisphenol F type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "jER152" (made by Mitsubishi Chemical Corporation) Phenolic novolac type epoxy resin); "630", "630LSD", "604" (glycidylamine type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "ED-523T" (GLYCIROL type epoxy resin) manufactured by ADEKA ); "EP-3950L" and "EP-3980S" (glycidylamine type epoxy resin) manufactured by ADEKA; "EP-4088S" (dicyclopentadiene type epoxy resin) manufactured by ADEKA; New Japan "ZX1059" (a mixture of bisphenol A type epoxy resin and bisphenol F type epoxy resin) manufactured by Iron & Steel Chemical Corporation; "EX-721" (glycidyl ester type epoxy resin) manufactured by Nagase ChemteX; "Celloxide 2021P" (an alicyclic epoxy resin with an ester skeleton) manufactured by Daicel; "PB-3600" manufactured by Daicel, "JP-100" and "JP-200" manufactured by Soda Diene structure epoxy resin); "ZX1658", "ZX1658GS" (liquid 1,4-glycidyl cyclohexane type epoxy resin) manufactured by Nippon Steel & Sumikin Chemical Co., Ltd. These can be used individually by 1 type, and can also be used in combination of 2 or more types.

The solid epoxy resin is preferably a solid epoxy resin having 3 or more epoxy groups in a molecule, and more preferably an aromatic solid epoxy resin having 3 or more epoxy groups in a molecule Resin.

The solid epoxy resin is preferably dixylenol type epoxy resin, naphthalene type epoxy resin, naphthalene type tetrafunctional epoxy resin, naphthol novolak type epoxy resin, cresol novolak type epoxy resin, Dicyclopentadiene type epoxy resin, triphenol type epoxy resin, naphthol type epoxy resin, biphenyl type epoxy resin, naphthyl ether type epoxy resin, anthracene type epoxy resin, bisphenol A type ring Oxygen resins, bisphenol AF type epoxy resins, phenol aralkyl type epoxy resins, tetraphenylethane type epoxy resins, phenol benzalkonium type epoxy resins, phenolphthalein type epoxy resins.

Specific examples of solid epoxy resins include "HP4032H" (naphthalene type epoxy resin) manufactured by DIC; "HP-4700" and "HP-4710" (naphthalene type tetrafunctional epoxy resin) manufactured by DIC ; "N-690" (cresol novolac epoxy resin) made by DIC; "N-695" (cresol novolak epoxy resin) made by DIC; "HP-7200" made by DIC , "HP-7200HH", "HP-7200H", "HP-7200L" (dicyclopentadiene epoxy resin); "EXA-7311", "EXA-7311-G3", "EXA" manufactured by DIC -7311-G4", "EXA-7311-G4S", "HP6000" (naphthyl ether type epoxy resin); "EPPN-502H" (triphenol type epoxy resin) manufactured by Nippon Kayaku Co., Ltd.; Nippon Kayaku Co., Ltd. "NC7000L" made by the company (naphthol novolak type epoxy resin); "NC3000H", "NC3000", "NC3000L", "NC3000FH", "NC3100" (biphenyl type epoxy resin) made by Nippon Kayaku Co., Ltd. ; "ESN475V" (naphthalene type epoxy resin) made by Nippon Steel Chemical &Material; "ESN485" (naphthol type epoxy resin) made by Nippon Steel Chemical &Material; "ESN375" made by Nippon Steel Chemical & Material "(Dihydroxynaphthalene type epoxy resin); "YX4000H", "YX4000", "YX4000HK", "YL7890" (dixylenol type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL6121" manufactured by Mitsubishi Chemical Corporation (Biphenyl type epoxy resin); "YX8800" (anthracene type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YX7700" (phenol aralkyl type epoxy resin) manufactured by Mitsubishi Chemical Corporation; manufactured by Osaka Gas Chemical Corporation "PG-100", "CG-500"; "YL7760" (bisphenol AF type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "YL7800" (茀-type epoxy resin) manufactured by Mitsubishi Chemical Corporation; manufactured by Mitsubishi Chemical Corporation "JER1010" (bisphenol A type epoxy resin); "jER1031S" (tetraphenylethane type epoxy resin) manufactured by Mitsubishi Chemical Corporation; "WHR991S" (phenoxybenzylmethyl lactamide) manufactured by Nippon Kayaku Type epoxy resin) and so on. These can be used singly or in combination of two or more kinds.

As component (D), when liquid epoxy resin and solid epoxy resin are used in combination, the mass ratio of solid epoxy resin to liquid epoxy resin (solid epoxy resin/liquid epoxy resin) is combined There is no particular limitation, but it is preferably 0.1 or more, more preferably 0.5 or more, still more 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 more, more preferably 50 or more, still more preferably 30 or more, and particularly preferably 20 or less.

(D) The epoxy equivalent of epoxy resin is preferably 50g/eq.~5,000g/eq., more preferably 60g/eq.~2,000g/eq., and still more preferably 70g/eq.~1,000g /eq., and more preferably 80g/eq.~500g/eq. The epoxy equivalent is the mass of epoxy per equivalent of resin. The epoxy equivalent can be measured in accordance with JIS K7236.

(D) The weight average molecular weight (Mw) of the epoxy resin is preferably 100 to 5,000, more preferably 250 to 3,000, and still more preferably 400 to 1,500. The weight average molecular weight of the resin can be measured by gel permeation chromatography (GPC) as a value in terms of polystyrene.

The content of (D) epoxy resin in the resin composition is not particularly limited. When the non-volatile content in the resin composition is 100% by mass, it is preferably 60% by mass or less, more preferably 50% by mass or less, It is more preferably 40% by mass or less, still more preferably 35% by mass or less, and particularly preferably 30% by mass or less. The lower limit of the content of (D) epoxy resin in the resin composition is not particularly limited. When the non-volatile content in the resin composition is 100% by mass, for example, it is 0% by mass or more and 0.01% by mass or more; It is 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 10% by mass or more, still more preferably 20% by mass or more, particularly preferably 25% by mass or more.

＜(E) Hardener＞ The resin composition of the present invention may further contain (E) a curing agent. (E) Hardener has the function of hardening (D) epoxy resin. The (E) hardener here is a component that does not correspond to the (A) component ~ (D) component.

(E) Hardeners are not particularly limited. Examples include phenol hardeners, naphthol hardeners, acid anhydride hardeners, active ester hardeners, benzoxazine hardeners, and cyanate ester hardeners. Agent. The curing agent may be used alone or in combination of two or more kinds. (E) The hardener preferably includes a hardener selected from a phenol-based hardener, a naphthol-based hardener, and an active ester-based hardener; particularly preferably, an active ester-based hardener is included.

As the phenolic hardener and the naphthol hardener, from the viewpoint of heat resistance and water resistance, a phenol hardener having a novolak structure or a naphthol hardener having a novolak structure are preferred. In addition, from the viewpoint of adhesion to the adherend, a nitrogen-containing phenol hardener or a nitrogen-containing naphthol hardener is preferable, and a phenol hardener containing a triazine skeleton or a triazine skeleton-containing hardener is more preferable. Naphthol hardener. Among them, from the viewpoint of satisfying high heat resistance, water resistance, and adhesion, a phenol novolak resin containing a triazine skeleton is preferred. Specific examples of phenolic hardeners and naphthol hardeners include "MEH-7700", "MEH-7810", and "MEH-7851" manufactured by Meiwa Chemical Co., Ltd., "NHN" manufactured by Nippon Kayaku Co., Ltd., "CBN", "GPH", "SN-170", "SN-180", "SN-190", "SN-475", "SN-485", "SN-495" manufactured by Nippon Steel Chemical & Material Co., Ltd. ", "SN-375", "SN-395", "LA-7052", "LA-7054", "LA-3018", "LA-3018-50P", "LA-1356", manufactured by DIC Corporation "TD2090", "TD-2090-60M", etc.

The acid anhydride-based curing agent includes one having one or more acid anhydride groups in one molecule, and one having two or more acid anhydride groups in one molecule is preferable. Specific examples of acid anhydride hardeners include phthalic anhydride, tetrahydrophthalic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, and methylhexahydrophthalic anhydride. Acid anhydride, methyl norbornan dioic anhydride, hydrogenated methyl norbornan dioic anhydride, trialkyltetrahydrophthalic anhydride, dodecenyl succinic anhydride, 5-(2,5-di-side oxytetrahydro -3-furyl)-3-methyl-3-cyclohexene-1,2-dicarboxylic anhydride, trimellitic anhydride, pyromellitic anhydride, benzophenone tetracarboxylic dianhydride, biphenyl tetracarboxylic acid Acid dianhydride, naphthalenetetracarboxylic dianhydride, oxydiphthalic dianhydride, 3,3'-4,4'-diphenyl tetracarboxylic dianhydride, 1,3,3a,4,5 ,9b-hexahydro-5-(tetrahydro-2,5-dioxo-3-furyl)-naphtho[1,2-C]furan-1,3-dione, ethylene glycol bis( Dehydrated trimellitate), styrene and maleic acid copolymerized styrene/maleic acid resin and other polymer type acid anhydrides. Commercially available products of acid anhydride hardeners include "HNA-100" and "MH-700" manufactured by Nippon Rika Corporation.

The active ester curing agent is not particularly limited. Generally speaking, it is preferable to use phenol esters, thiophenol esters, N-hydroxy amine esters, esters of heterocyclic hydroxy compounds, etc., which have two or more reactions in one molecule. Highly active ester compound. The active ester curing agent is preferably obtained by a condensation reaction of a carboxylic acid compound and/or a thiocarboxylic acid compound and a hydroxy compound and/or a thiol compound. Particularly from the viewpoint of improving heat resistance, an active ester curing agent obtained from a carboxylic acid compound and a hydroxy compound is preferable; an active ester curing agent obtained from a carboxylic acid compound and a phenol compound and/or a naphthol compound is more preferable Agent. Examples of the carboxylic acid compound include benzoic acid, acetic acid, succinic acid, maleic acid, itaconic acid, phthalic acid, isophthalic acid, terephthalic acid, and pyromellitic acid. Examples of the phenol compound or naphthol compound include hydroquinone, resorcinol, bisphenol A, bisphenol F, bisphenol S, phenolphthalein, methylated bisphenol A, methylated bisphenol F, and 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, benzenetriol, dicyclopentadiene type diphenol compounds, phenol novolac Wait. Here, the "dicyclopentadiene type diphenol compound" refers to a diphenol compound obtained by condensing two molecules of phenol with one molecule of dicyclopentadiene.

Specifically, it is preferably an active ester compound containing a dicyclopentadiene type diphenol structure, an active ester compound containing a naphthalene structure, an active ester compound containing an acetate of a phenol novolak, and a benzyl containing a phenol novolak. Among the active ester compounds of the acyl compounds, the active ester compounds containing the naphthalene structure and the active ester compounds containing the dicyclopentadiene-type diphenol structure are particularly preferred. "Dicyclopentadiene-type diphenol structure" means a bivalent structural unit containing phenylene-dicyclopentadene-phenylene.

As a commercially available product of the active ester curing agent, the active ester compound containing the dicyclopentadiene-type diphenol structure includes "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", and "EXB9460S". HPC-8000H", "HPC-8000-65T", "HPC-8000H-65TM", "EXB-8000L", "EXB-8000L-65M", "EXB-8000L-65TM" (made by DIC); includes Examples of active ester compounds of naphthalene structure include "EXB-9416-70BK", "EXB-8150-65T", "EXB-8100L-65T", and "EXB-8150L-65T" (manufactured by DIC Corporation); For the active ester hardener of the acetyl compound of the varnish, "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.); for the active ester hardener of the phenol novolak benzoate compound, "YLH1026" (Mitsubishi Chemical Company), "YLH1030" (manufactured by Mitsubishi Chemical Corporation), "YLH1048" (manufactured by Mitsubishi Chemical Corporation), etc.

Specific examples of benzoxazine-based hardeners include "JBZ-OP100D" and "ODA-BOZ" manufactured by JFE Chemical Corporation; "HFB2006M" manufactured by Showa Polymer Corporation; and "Pd" manufactured by Shikoku Chemical Industry Co., Ltd. , "Fa", etc.

Cyanate-based curing agents, for example, bisphenol A dicyanate, polyphenol cyanate (oligo(3-methylene-1,5-phenylene cyanate)), 4,4'- Methylene bis(2,6-dimethylphenyl cyanate), 4,4'-ethylene diphenyl dicyanate, hexafluorobisphenol A dicyanate, 2,2-bis (4-cyanate ester) phenyl propane, 1,1-bis(4-cyanate phenylmethane), bis(4-cyanate ester-3,5-dimethylphenyl)methane, 1,3 -Bis (4-cyanate phenyl-1-(methyl ethylene)) benzene, bis (4-cyanate phenyl) sulfide, and bis (4-cyanate phenyl) ether, etc. Bifunctional cyanate resin; polyfunctional cyanate resin derived from phenol novolac and cresol novolac, prepolymer of which a part of these cyanate resins are triazineized, etc. Specific examples of cyanate ester curing agents include "PT30" and "PT60" (both phenol novolak type polyfunctional cyanate resin) manufactured by Lonza Japan, "BA230", and "BA230S75" (bisphenol A Part or all of the dicyanate is triazineized to become a trimer prepolymer) and so on.

When the resin composition contains (D) epoxy resin and (E) hardener, the ratio of the amount of (D) epoxy resin to (E) hardener is [(D) epoxy group number of epoxy resin]: [( E) The ratio of the reaction base of the hardener] is preferably 1:0.2~1:2, more preferably 1:0.3~1:1.5, and even more preferably 1:0.4~1:1.4. Here, (E) the reactive group of the hardening agent, for example, is an aromatic hydroxyl group in the case of a phenol-based hardener and a naphthol-based hardener, and in the case of an active ester-based hardener, it is an active ester group, which varies depending on the type of hardener.

(E) The reaction base equivalent of the hardener is preferably 50g/eq.~3,000g/eq., more preferably 100g/eq.~1,000g/eq., and still more preferably 100g/eq.~500g/eq. ., particularly preferably 100g/eq.~300g/eq. The equivalent of the reactive group is the mass of the hardener per equivalent of the reactive group.

(E) When the active ester hardener is contained in the hardener, its content is not particularly limited. When the total amount of (E) hardener is 100% by mass, it is preferably 10% by mass or more, more preferably 20% by mass Above, more preferably 30% by mass or more, particularly preferably 40% by mass or more.

The content of (E) hardener in the resin composition is not particularly limited. When the non-volatile content in the resin composition is 100% by mass, it is preferably 50% by mass or less, more preferably 30% by mass or less, and It is more preferably 20% by mass or less, still more preferably 15% by mass or less, and particularly preferably 10% by mass or less. The lower limit of the content of (E) hardener in the resin composition is not particularly limited. When the non-volatile content in the resin composition is 100% by mass, for example, 0% by mass or more and 0.01% by mass or more; preferably 0.1% by mass or more, more preferably 1% by mass or more, still more preferably 2% by mass or more, still more preferably 4% by mass or more, particularly preferably 5% by mass or more.

＜(F) Hardening accelerator＞ The resin composition of the present invention may contain (F) a hardening accelerator as an optional component. (F) Hardening accelerator has the function of accelerating the hardening of (D) epoxy resin.

(F) Hardening accelerators are not particularly limited. Examples include phosphorus hardening accelerators, urea hardening accelerators, amine hardening accelerators, imidazole hardening accelerators, guanidine hardening accelerators, and metal hardening accelerators. Wait. Among them, phosphorus-based hardening accelerators, amine-based hardening accelerators, imidazole-based hardening accelerators, and metal-based hardening accelerators are particularly preferred; particularly preferred are amine-based hardening accelerators and imidazole-based hardening accelerators. The hardening accelerator may be used singly or in combination of two or more kinds.

Phosphorus-based hardening accelerators include, for example, tetrabutylphosphonium bromide, tetrabutylphosphonium chloride, tetrabutylphosphonium acetate, tetrabutylphosphonium decanoate, tetrabutylphosphonium laurate, bis(tetrabutylphosphonium) Phosphonium) pyromellitate, tetrabutyl phosphonium hydrogen hexahydro phthalate, tetrabutyl phosphonium cresol novolac 3-mer salt, di-tert-butyl methyl phosphonium tetraphenyl borate and other fats Group phosphonium salt; methyl triphenyl phosphonium bromide, ethyl triphenyl phosphonium bromide, propyl triphenyl phosphonium bromide, butyl triphenyl phosphonium bromide, benzyl triphenyl phosphonium chloride, four Phenylphosphonium bromide, p-tolyltriphenylphosphonium tetra-p-tolyl borate, tetraphenylphosphonium tetraphenyl borate, tetraphenylphosphonium tetrap-tolyl borate, triphenylethyl Phosphonium tetraphenyl borate, ginseng (3-methylphenyl) ethyl phosphonium tetraphenyl borate, ginseng (2-methoxyphenyl) ethyl phosphonium tetraphenyl borate, (4-methylbenzene) Group) Aromatic phosphonium salts such as triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyl triphenylphosphonium thiocyanate, etc.; aromatic phosphonium salts such as triphenylphosphine/triphenylborane Phosphine/borane complex; aromatic phosphine/quinone addition reactant such as triphenylphosphine/p-benzoquinone addition reactant; tributylphosphine, tri-tert-butylphosphine, trioctylphosphine , Di-tert-butyl (2-butenyl) phosphine, di-tert-butyl (3-methyl-2-butenyl) phosphine, tricyclohexyl phosphine and other aliphatic phosphines; dibutyl benzene Phosphine, di-tert-butylphenylphosphine, methyldiphenylphosphine, ethyldiphenylphosphine, butyldiphenylphosphine, diphenylcyclohexylphosphine, triphenylphosphine, tri-o- Tolylphosphine, tris-m-tolylphosphine, tris-p-tolylphosphine, ginseng(4-ethylphenyl)phosphine, ginseng(4-propylphenyl)phosphine, ginseng(4-isopropylbenzene) Group) phosphine, ginseng (4-butylphenyl) phosphine, ginseng (4-tert-butylphenyl) phosphine, ginseng (2,4-dimethylphenyl) phosphine, ginseng (2,5-dimethyl phenyl) phosphine Phenyl)phosphine, ginseng(2,6-dimethylphenyl)phosphine, ginseng(3,5-dimethylphenyl)phosphine, ginseng(2,4,6-trimethylphenyl)phosphine, Ginseng (2,6-dimethyl-4-ethoxyphenyl) phosphine, ginseng (2-methoxyphenyl) phosphine, ginseng (4-methoxyphenyl) phosphine, ginseng (4-ethoxy) Phenyl)phosphine, ginseng (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) ) Aromatic phosphines such as diphenyl ether.

Urea-based hardening accelerators, for example, 1,1-dimethylurea; 1,1,3-trimethylurea, 3-ethyl-1,1-dimethylurea, 3-cyclohexyl-1, Aliphatic dimethylurea such as 1-dimethylurea, 3-cyclooctyl-1,1-dimethylurea, etc.; 3-phenyl-1,1-dimethylurea, 3-(4-chloro Phenyl)-1,1-dimethylurea, 3-(3,4-dichlorophenyl)-1,1-dimethylurea, 3-(3-chloro-4-methylphenyl)- 1,1-dimethylurea, 3-(2-methylphenyl)-1,1-dimethylurea, 3-(4-methylphenyl)-1,1-dimethylurea, 3 -(3,4-Dimethylphenyl)-1,1-dimethylurea, 3-(4-isopropylphenyl)-1,1-dimethylurea, 3-(4-methoxy Phenyl)-1,1-dimethylurea, 3-(4-nitrophenyl)-1,1-dimethylurea, 3-[4-(4-methoxyphenoxy)benzene Group]-1,1-dimethylurea, 3-[4-(4-chlorophenoxy)phenyl]-1,1-dimethylurea, 3-[3-(trifluoromethyl)benzene Group)-1,1-dimethylurea, N,N-(1,4-phenylene)bis(N',N'-dimethylurea), N,N-(4-methyl-1 ,3-phenylene) bis(N',N'-dimethylurea)[toluene dimethylurea] and other aromatic dimethylureas.

Examples of amine curing accelerators include trialkylamines such as triethylamine and tributylamine, 4-dimethylaminopyridine (DMAP), benzyldimethylamine, 2,4,6,- Ginseng (dimethylaminomethyl)phenol, 1,8-diazabicyclo(5,4,0)-undecene, etc., preferably 4-dimethylaminopyridine.

Examples of imidazole-based hardening accelerators include 2-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 1,2-Dimethylimidazole, 2-ethyl-4-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1- Benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4 -Methylimidazole, 1-cyanoethyl-2-phenylimidazole, 1-cyanoethyl-2-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenyl Imidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6 -[2'-Undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl -(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine heterotriazine Cyanate adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethyl Imidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazole Imidazole compounds such as morpholine and 2-phenylimidazoline, and adducts of imidazole compounds and epoxy resins.

As the imidazole-based hardening accelerator, commercially available products may also be used. For example, "P200-H50" manufactured by Mitsubishi Chemical Corporation can be cited.

Guanidine-based hardening accelerators, for example, dicyandiamine, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, metformin Guanidine, 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-methyl biguanide, 1-ethyl biguanide, 1-n-butyl biguanide, 1-n-octadecyl biguanide, 1,1-Dimethyl biguanide, 1,1-diethyl biguanide, 1-cyclohexyl biguanide, 1-allyl biguanide, 1-phenyl biguanide, 1-(o-tolyl) biguanide, etc.

Examples of the metal-based hardening accelerator include organometallic complexes or organometallic salts of metals such as cobalt, copper, zinc, iron, nickel, manganese, and tin. Specific examples of organometallic complexes include organic cobalt complexes such as cobalt(II) acetone, cobalt(III) acetone, organic copper complexes such as copper(II) acetone, zinc (II) Organozinc complexes such as acetone, organic iron complexes such as iron(III) acetone, organic nickel complexes such as nickel(II) acetone, manganese(II) acetone ) And other organic manganese complexes. Examples of the organic metal salt include zinc octoate, tin octoate, zinc naphthenate, cobalt naphthenate, tin stearate, and zinc stearate.

The content of (F) hardening accelerator in the resin composition is not particularly limited. When the non-volatile content in the resin composition is 100% by mass, it is preferably 10% by mass or less, more preferably 5% by mass or less, It is more preferably 3% by mass or less, still more preferably 1% by mass or less, and particularly preferably 0.5% by mass or less. The lower limit of the content of (F) hardening accelerator in the resin composition is not particularly limited. When the non-volatile content in the resin composition is 100% by mass, for example, it is 0% by mass or more and 0.0001% by mass or more; It is 0.001 mass% or more, more preferably 0.005 mass% or more, still more preferably 0.01 mass% or more, still more preferably 0.05 mass% or more, particularly preferably 0.1 mass% or more.

＜(G) Other additives＞ The resin composition of the present invention may further contain optional additives as non-volatile components. Such additives include, for example, organic fillers such as rubber particles, polyamide particles, and silicone particles; Thermoplastic resins such as polyphenylene ether resin, polycarbonate resin, polyether ether ketone resin, polyester resin, etc.; organometallic compounds such as organic copper compounds, organic zinc compounds, and organic cobalt compounds; phthalocyanine blue, phthalocyanine green Coloring agents for, iodo green, diazo yellow, crystal violet, titanium oxide, carbon black, etc.; polymerization inhibitors for hydroquinone, catechol, gallic phenol, phenothiazine, etc.; silicone-based leveling agent, acrylic polymerization Leveling agents such as material leveling agents; Tackifiers such as Benton (bentonite) and montmorillonite; silicone defoamers, acrylic defoamers, fluorine defoamers, vinyl resin defoamers Antifoaming agent for foaming agents; UV absorbers for benzotriazole-based UV absorbers; Adhesion enhancers for urea silanes, etc.; Triazole-based adhesiveness imparting agent, tetrazole-based adhesiveness imparting agent, triazine Adhesion-imparting agents such as adhesion-imparting agents; antioxidants such as hindered phenol-based antioxidants and hindered amine-based antioxidants; fluorescent brighteners such as stilbene derivatives; fluorine-based surfactants, poly Silicone-based surfactants and other surfactants; phosphorus-based flame retardants (such as phosphate esters, hypophosphites, phosphazene compounds, red phosphorus), nitrogen-based flame retardants (such as melamine sulfate), halogen-based flame retardants Flame retardant, inorganic flame retardant (for example, antimony trioxide) and other flame retardants. Additives may be used singly, or two or more of them may be used in combination at any ratio. (G) The content of other additives can be appropriately set by those skilled in the art.

＜(H)Organic solvent＞ The resin composition of the present invention may further contain an optional organic solvent as a volatile component in addition to the above-mentioned non-volatile component. (H) The known organic solvent can be suitably used, and the type is not particularly limited. (H) Organic solvents include, for example, ketone solvents such as acetone, methyl ethyl ketone, methyl isobutyl ketone, and cyclohexanone; methyl acetate, ethyl acetate, butyl acetate, isobutyl acetate, acetic acid Ester solvents such as isoamyl ester, methyl propionate, ethyl propionate, γ-butyrolactone, etc.; tetrahydropyran, tetrahydrofuran, 1,4-dioxane, diethyl ether, diisopropyl ether , Dibutyl ether, diphenyl ether and other ether solvents; methanol, ethanol, propanol, butanol, ethylene glycol and other alcohol solvents; 2-ethoxyethyl acetate, propylene glycol monomethyl ether ethyl Ether ester solvents such as acid ester, diethylene glycol monoethyl ether acetate, ethyl diethylene glycol acetate, γ-butyrolactone, methyl methoxypropionate, etc.; methyl lactate, ethyl lactate Ester alcohol solvents such as esters and methyl 2-hydroxyisobutyrate; 2-methoxypropanol, 2-methoxyethanol, 2-ethoxyethanol, propylene glycol monomethyl ether, diethylene glycol mono Ether alcohol solvents such as butyl ether (butyl carbitol); N,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-2-pyrrolidone, etc. Amine-based solvents; dimethyl sulfide and other sulfide-based solvents; acetonitrile, propionitrile, and other nitrile solvents; hexane, cyclopentane, cyclohexane, methylcyclohexane, and other aliphatic hydrocarbons Solvents: aromatic hydrocarbon solvents such as benzene, toluene, xylene, ethylbenzene, trimethylbenzene, etc. (H) An organic solvent may be used individually by 1 type, and may be used combining two or more types in arbitrary ratios.

＜Manufacturing method of resin composition＞ The resin composition of the present invention, for example, can be obtained by adding a part or all of (A) polyimide resin (preliminarily imidized), (B) in any reaction vessel in any order and/or at the same time Carbodiimide resin, (C) inorganic filler, (D) epoxy resin as required, (E) hardener as required, (F) hardening accelerator as required, (G) other additives as required , And (H) organic solvent as needed, and mixed to manufacture. In addition, in the process of adding and mixing each component, the temperature may be appropriately set, and heating and/or cooling may be performed temporarily or all the time. In addition, in the process of adding and mixing each component, stirring or shaking may be performed. In addition, at the time of addition and mixing or after that, the resin composition may be stirred using a stirring device such as a mixer to uniformly disperse it.

＜Characteristics of resin composition＞ The resin composition of the present invention contains (A) polyimide resin, (B) carbodiimide resin, and (C) inorganic filler. The content of (C) component is less than 40% by mass, therefore, it can be obtained A hardened product with excellent heat resistance and flexibility to suppress halo phenomenon.

The cured product of the resin composition of the present invention can suppress the halo phenomenon. Therefore, for example, the halo ratio calculated as in Test Example 1 below is preferably 40% or less, more preferably 35% or less, and More preferably, it may be 30% or less, and particularly preferably, it may be 25%.

Since the cured product of the resin composition of the present invention has excellent heat resistance, for example, as in Test Example 2 below, the rate of change in elongation at break of the cured product before and after high temperature treatment at 200°C for 5 hours (by Test Example 2 The formula (1) above) is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more, particularly preferably 80% or more.

The cured product of the resin composition of the present invention has excellent flexibility. Therefore, for example, the number of fold resistance after the MIT fold resistance test is carried out as in Test Example 3 below, preferably 3,000 times or more, more preferably 5,000 Times or more, more preferably 8,000 times or more, particularly preferably 10,000 times or more.

＜Use of resin composition＞ The resin composition of the present invention can be used in a wide variety of insulating materials such as printed circuit boards, multilayer flexible substrates, solder resists, primer materials, die bonding materials, semiconductor sealing materials, filling resins, and part embedding resins. Scope. Printed circuit boards, multilayer flexible substrates, etc., can be manufactured using, for example, sheet-like laminate materials such as resin sheets and prepregs.

＜Resin sheet＞ The resin sheet of the present invention includes a support and a resin composition layer formed of the resin composition of the present invention provided on the support.

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

Examples of the support include a film containing a plastic material, metal foil, and release paper, and a film containing a plastic material, and metal foil are preferred.

When a film containing a plastic material is used as a support, the plastic material may, for example, be polyethylene terephthalate (hereinafter abbreviated as "PET") and polyethylene naphthalate (hereinafter abbreviated as "PET"). PEN”); polycarbonate (hereinafter referred to as “PC”), polymethylmethacrylate (PMMA), acrylic, cyclic polyolefin, triacetyl cellulose (TAC), polyether sulfide (PES), polyether ketone, polyimide, etc. Among them, polyethylene terephthalate and polyethylene naphthalate are particularly preferred; particularly preferred is polyethylene terephthalate, which is inexpensive.

When a metal foil is used as a support, examples of the metal foil include copper foil and aluminum foil, and copper foil is preferred. As the copper foil, a single metal foil containing copper can be used, and a foil containing an alloy of copper and other metals (for example, tin, chromium, silver, magnesium, nickel, zirconium, silicon, titanium, etc.) can also be used.

The surface of the support body that is joined to the resin composition layer may be subjected to matting treatment, corona treatment, and antistatic treatment.

Moreover, as a support body, the support body with a mold release layer which has a mold release layer on the surface joined with a resin composition layer can also be used. The mold release agent used in the mold release layer of the support with the mold release layer includes, for example, one selected from the group consisting of alkyd resins, polyolefin resins, urethane resins, and silicone resins. The above release agent. The support with a release layer can also be a commercially available product. For example, "SK-1" made by Lintec Co., Ltd. is a PET film with a release layer mainly composed of an alkyd resin-based release agent. , "AL-5", "AL-7", "Lumirror T60" manufactured by Toray, "Purex" manufactured by Teijin, "Unipeel" manufactured by Unitika, etc.

The thickness of the support is not particularly limited, and is preferably in the range of 5 μm to 75 μm, more preferably in the range of 10 μm to 60 μm. Furthermore, when a support with a release layer is used, the thickness of the entire support with a release layer is preferably in the above-mentioned range.

In one embodiment, the resin sheet may further include other layers as needed. Such other layers include, for example, a protective film equivalent to the support provided on the surface of the resin composition layer that is not bonded to the support (that is, the surface on the opposite side of the support). The thickness of the protective film is not particularly limited, and is, for example, 1 μm to 40 μm. By laminating the protective film, it is possible to suppress the adhesion or scratches of dust and the like on the surface of the resin composition layer.

The resin sheet can be formed by directly dissolving the resin composition or, for example, a resin coating prepared by dissolving the resin composition in an organic solvent, coating it on the support using a die coater, etc., and further drying to form a resin composition layer To make.

Examples of the organic solvent that can be used for coating on the support are the same as those listed in the description of the organic solvent as a component of the resin composition. An organic solvent may be used individually by 1 type, and may be used in combination of 2 or more types.

Drying can be performed by well-known methods such as heating and hot air blowing. The drying condition is not particularly limited, and it is dried so that the content of the organic solvent in the resin composition layer becomes 10% by mass or less, preferably 5% by mass or less. Although it also depends on the boiling point of the organic solvent in the resin composition or resin coating, for example, when a resin composition or resin coating containing 30% to 60% by mass of organic solvent is used, it can be dried at 50°C to 150°C. Minutes to 10 minutes to form a resin composition layer.

The resin sheet can be wound into a roll for storage. When the resin sheet has a protective film, it can be used by peeling off the protective film.

＜Laminated sheet＞ The laminated sheet may be a sheet produced by laminating and curing a plurality of resin compositions. The laminated sheet includes a plurality of insulating layers that are cured products of the resin composition layer. Generally, the number of resin composition layers laminated in order to manufacture the laminated sheet is the same as the number of insulating layers included in the laminated sheet. The number of specific insulating layers per laminated sheet is usually 2 or more, preferably 3 or more, particularly preferably 5 or more; preferably 20 or less, more preferably 15 or less, particularly preferably 10 or less.

The laminated sheet may be a sheet that is bent and used so that one of its faces opposes each other. The minimum bending radius of the laminated sheet is not particularly limited. It is preferably 0.1mm or more, more preferably 0.2mm or more, and more preferably 0.3mm or more; preferably 5mm or less, more preferably 4mm or less, Particularly preferred is 3mm or less.

Holes may also be formed on each insulating layer included in the laminated sheet. The hole can function as a through hole or a through hole in the multilayer flexible substrate.

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

The conductor material used in the conductor layer is not particularly limited. In a suitable embodiment, the conductor layer includes one or more selected from the group consisting of gold, platinum, palladium, silver, copper, aluminum, cobalt, chromium, zinc, nickel, titanium, tungsten, iron, tin, and indium Metal. The conductor material can be a single metal or an alloy. Examples of the alloy include alloys of two or more metals selected from the above group (for example, nickel/chromium alloy, copper/nickel alloy, and copper/titanium alloy). Among them, in terms of the versatility, cost, and ease of patterning of the conductor layer, especially chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper as a single metal; and nickel/chromium alloys , Copper/nickel alloy, copper/titanium alloy and other alloys are preferred. Among them, a single metal of chromium, nickel, titanium, aluminum, zinc, gold, palladium, silver or copper; and a nickel/chromium alloy are particularly preferred; and a single metal of copper is more preferred.

The conductor layer may have a single-layer structure, or a multiple-layer structure containing two or more single metal layers or alloy layers containing different types of metals or alloys. When the conductor layer has a multi-layer structure, the layer adjacent to the insulating layer is preferably a single metal layer of chromium, zinc or titanium, or an alloy layer of nickel/chromium alloy.

The conductor layer may be patterned in order to function as wiring.

Although the thickness of the conductor layer varies depending on the design of the multilayer flexible substrate, it is preferably 3 μm to 35 μm, more preferably 5 μm to 30 μm, still more preferably 10 μm to 20 μm, particularly preferably 15 μm to 20 μm.

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

＜Manufacturing method of laminated sheet＞ The laminated sheet can be manufactured by a manufacturing method including (a) a step of preparing a resin sheet, and (b) a step of laminating and curing a plurality of resin composition layers using the resin sheet. The order of lamination and curing of the resin composition layer is arbitrary as long as the desired laminated sheet can be obtained. Depending on the components contained in the resin composition, for example, after all the plural resin composition layers are laminated, the laminated plural resin composition layers are cured at one time. In addition, for example, each time another resin composition layer is laminated on a certain resin composition layer, the laminated resin composition layer may be cured.

Hereinafter, a preferred embodiment of step (b) will be described. In the embodiments described below, for the sake of distinction, the resin composition layer is indicated by appropriately adding numbers such as "first resin composition layer" and "second resin composition layer". The insulating layer obtained by curing the resin composition layer is also represented by numbers such as "first insulating layer" and "second insulating layer" in the same way as the resin composition layer.

In a preferred embodiment, step (b) includes (II) The step of hardening the first resin composition layer to form the first insulating layer, (VI) the step of laminating the second resin composition layer on the first insulating layer, and (VII) A step of hardening the second resin composition layer to form a second insulating layer. In addition, step (b) can also include (I) The step of laminating the first resin composition layer on the sheet supporting substrate, (III) The step of opening holes in the first insulating layer, (IV) The step of roughening the first insulating layer, (V) Step of forming a conductor layer on the first insulating layer Any steps and so on. The steps are explained below.

Step (I) is a step of laminating the first resin composition layer on the sheet supporting substrate before step (II). The sheet supporting substrate is a peelable member, for example, a plate-shaped, sheet-shaped or film-shaped member is used.

The lamination of the sheet supporting substrate and the first resin composition layer can be implemented by a vacuum lamination method. In the vacuum stacking method, the heating and pressing temperature is preferably in the range of 60°C to 160°C, more preferably in the range of 80°C to 140°C, and the heating and pressing pressure is preferably 0.098MPa to 1.77MPa, more preferably 0.29MPa to 1.47MPa In the range, the heating and crimping time is preferably 20 seconds to 400 seconds, more preferably 30 seconds to 300 seconds. The lamination is preferably carried out under reduced pressure at a pressure of 26.7 hPa or less.

The lamination can be performed by a commercially available vacuum lamination machine. Commercially available vacuum laminators include, for example, vacuum pressure laminators manufactured by Meiji Seisakusho, Vacuum Applicator manufactured by Nikko Materials, and batch vacuum laminators.

When using a resin sheet, the sheet supports the lamination of the base material and the first resin composition layer. For example, the resin sheet can be pressed from the support side, and the first resin composition layer of the resin sheet can be heated and pressed onto the sheet support Base material. A member that heats and presses the resin sheet to the sheet support substrate (hereinafter also referred to as "heat and pressure bonding member" as appropriate), for example, a heated metal plate (SUS mirror plate, etc.) or metal roll (SUS roll), etc. . It is preferable that the first resin composition layer sufficiently follows the unevenness of the surface of the sheet support substrate and pressurize it through an elastic material such as heat-resistant rubber, rather than directly pressing the heat and pressure bonding member on the resin sheet.

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

Step (II) is a step of hardening 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 circuit board can be arbitrarily applied. When the first resin composition layer contains a thermosetting resin, for example, it can be cured by heat.

Generally, the specific thermosetting 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 even more 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 still more preferably 20 minutes to 100 minutes.

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

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

Step (IV) is a step of roughening the first insulating layer. Usually, in this step (IV), the sludge removal is also performed. Therefore, the roughening treatment is called a desmear treatment. Examples of the roughening treatment include a method of sequentially performing a swelling treatment with a swelling liquid, a roughening treatment with an oxidizing agent, and a neutralization treatment with a neutralization liquid.

The swelling liquid is not particularly limited, and examples include aqueous alkali solutions such as sodium hydroxide aqueous solution and potassium hydroxide aqueous solution. Examples of commercially available swelling fluids include "Swelling Dip Securiganth P" and "Swelling Dip Securiganth SBU" manufactured by Atotech Japan. The swelling treatment with a swelling liquid can be performed, for example, by immersing the hardened body in a swelling liquid at 30 to 90°C for 1 to 20 minutes. From the viewpoint of suppressing the swelling of the resin of the insulating layer to a moderate level, it is preferable to immerse the insulating layer in a swelling solution at 40°C to 80°C for 5 minutes to 15 minutes.

The oxidizing agent is not particularly limited, and examples thereof include an aqueous sodium hydroxide solution and an alkaline permanganic acid solution in which permanganate is dissolved in an aqueous potassium hydroxide solution. The concentration of permanganate in the alkaline permanganic acid solution is preferably 5 mass% to 10 mass %. Commercially available oxidants include, for example, alkaline permanganic acid solutions such as "Concentrate Compact P", "Concentrate Compact CP", and "Dosing solution Securiganth P" manufactured by Atotech Japan. The roughening treatment with oxidizing agent can be performed by immersing the hardened body in an oxidizing agent solution heated to 60°C to 80°C for 10 minutes to 30 minutes.

Moreover, an acidic aqueous solution can be used as a neutralization liquid. Commercial products include, for example, "Reduction solution Securiganth P" manufactured by Atotech Japan. The treatment with the neutralization solution can be performed by immersing the hardened body in the neutralization solution at 30°C to 80°C for 5 minutes to 30 minutes. From the viewpoint of workability and the like, it is preferable to immerse the hardened body in a neutral solution at 40°C to 70°C for 5 minutes to 20 minutes.

The arithmetic average roughness (Ra) of the surface of the first insulating layer after the roughening treatment is preferably 400 nm or less, more preferably 300 nm or less, and even more preferably 200 nm or less. The lower limit is not particularly limited, and can be 30 nm or more, 40 nm or more, or 50 nm or more.

Step (V) is a step of forming a conductor layer on the first insulating layer as needed. Examples of the method of forming the conductor layer include a plating method, a sputtering method, and an evaporation method. Among them, the plating method is particularly preferred. Suitable examples include a method of plating the surface of the first insulating layer by a suitable method such as a semi-additive method and a full-additive method to form a conductor layer with a desired wiring pattern. Among them, the semi-additive method is particularly preferred from the viewpoint of ease of manufacture.

The following shows an example of forming the conductor layer by the semi-additive method. First, on the surface of the first insulating layer, a plating seed layer is formed by electroless plating. Next, on the formed plating seed layer, a mask pattern is formed corresponding to the desired wiring pattern so that a part of the plating seed layer is exposed. After forming a metal layer by electrolytic plating on the exposed plating seed layer, the mask pattern is removed. After that, the unnecessary plating seed layer is removed by processing such as etching, and a conductor layer having a desired wiring pattern can be formed.

After the first insulating layer is obtained in step (II), step (III), step (IV), and step (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 support substrate and the first resin composition layer in step (I).

However, when a resin sheet is used to form the first resin composition layer, the support of the resin sheet is removed before step (VI). The removal of the support can be carried out between step (I) and step (II), can be carried out between step (II) and step (III), can be carried out between step (III) and step (IV), It can also be carried out between step (IV) and step (V).

After step (VI), proceed to step (VII). Step (VII) is a step of hardening 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). Thereby, a laminated sheet including a plurality of insulating layers including the first insulating layer and the second insulating layer can be obtained.

In addition, in the method of the foregoing embodiment, (VIII) the step of opening the second insulating layer, (IX) the step of roughening the second insulating layer, and (X) the second insulating layer The step of forming a conductor layer on the layer. The opening of the second insulating layer in step (VIII) can be performed by the same method as the opening of the first insulating layer in step (III). Furthermore, the roughening treatment of the second insulating layer in step (IX) can be performed by the same method as the roughening treatment of the first insulating layer in step (IV). Further, the formation of the conductor layer on the second insulating layer in step (X) can be performed by the same method as the formation of the conductor layer on the first insulating layer in step (V).

In the foregoing embodiment, the embodiment in which the laminated sheet is manufactured by laminating and curing the two resin composition layers of the first resin composition layer and the second resin composition layer has been described, but it can also be made by The lamination and curing of three or more resin composition layers produces a laminated sheet. For example, in the method of the foregoing embodiment, the lamination and curing of the resin composition layer of step (VI) to step (VII) can be repeated, and the insulation of step (VIII) to step (X) can be repeated as needed. The opening of the layer, the roughening of the insulating layer, and the formation of the conductor layer on the insulating layer to produce a laminated sheet. Thereby, a laminated sheet including three or more insulating layers can be obtained.

Furthermore, the method of the foregoing embodiment may also include any steps other than the above-mentioned steps. For example, when step (I) is performed, the step of removing the sheet supporting substrate may also be performed.

＜Multilayer flexible substrate＞ Multi-layer flexible substrates include laminated sheets. The multilayer flexible substrate may include only the laminate sheet, or may include any members to be combined with the laminate sheet. Examples of arbitrary members include electronic parts, coverlay films, and the like.

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

The manufacturing method of the multilayer flexible substrate may further include any steps to be combined with the foregoing steps. For example, the method of manufacturing a multilayer flexible substrate with electronic components may also include the step of bonding the electronic components with the laminated sheet. The bonding conditions between the laminate sheet and the electronic component can be any conditions under which the terminal electrode of the electronic component and the conductor layer as the wiring provided on the laminate sheet can be connected. In addition, for example, a method for manufacturing a multilayer flexible substrate provided with a cover film may also include a step of laminating a laminate sheet and a cover film.

The aforementioned multi-layer flexible substrate can generally be bent and used in such a way that one of the laminated sheets included in the multi-layer flexible substrate faces each other. For example, a multi-layer flexible substrate is housed in a case of a semiconductor device in a state where the size is reduced by bending. In addition, for example, a multilayer flexible substrate is provided in the movable portion of a semiconductor device having a movable portion that can be bent.

＜Semiconductor device＞ The semiconductor device includes the aforementioned multilayer flexible substrate. A semiconductor device includes, for example, a multi-layer flexible substrate and a semiconductor chip mounted on the multi-layer flexible substrate. In many semiconductor devices, the multi-layer flexible substrate can be bent and housed in the semiconductor device housing in such a manner that one of the laminated sheets included in the multi-layer flexible substrate faces each other.

Examples of semiconductor devices include various semiconductor devices used in power supply products (such as computers, mobile phones, digital cameras, televisions, etc.) and vehicles (such as locomotives, automobiles, trams, ships, and airplanes).

The aforementioned semiconductor device, for example, may include a step of preparing a multi-layer flexible substrate, a step of bending the multi-layer flexible substrate so that one of the laminated sheets faces each other, and a step of bending the multi-layer flexible substrate. The manufacturing method of the step of storing the flexible substrate in the case is manufactured. [Example]

The following examples illustrate the present invention in detail. The present invention is not limited to these embodiments. Furthermore, in the following, the "parts" and "%" that indicate the amount, unless otherwise specified, mean "parts by mass" and "% by mass" respectively. In addition, the operations described below are performed in an environment of normal temperature and pressure (25°C, 1 atm) unless otherwise specified.

<Synthesis example 1: Synthesis of polyimide resin 1> G-3000 (bifunctional hydroxyl-terminated polybutadiene, number average molecular weight = 5047 (GPC method), hydroxyl equivalent = 1798 g/eq. , Solid content 100% by mass: Nippon Soda Co., Ltd.) 50 g, Ipzole 150 (aromatic hydrocarbon-based mixed solvent: Idemitsu Petrochemical Co., Ltd.) 23.5 g, and 0.005 g of dibutyl tin laurate are uniformly dissolved. When it became uniform, it heated up to 50 degreeC, and while stirring further, 4.8g of toluene-2,4-diisocyanate (isocyanate group equivalent=87.08g/eq.) was added, and reaction was performed for about 3 hours. Next, after cooling the reactant to room temperature, 8.96 g of benzophenone tetracarboxylic dianhydride (anhydride equivalent = 161.1 g/eq.), 0.07 g of triethylenediamine, and ethyl diethylene glycol were added to it 40.4 g of acetate (made by Daicel) was heated to 130°C while stirring, and the reaction was carried out for about 4 hours. It was confirmed by FTIR that the NCO peak at ^{2250 cm -1 disappeared.} After confirming the disappearance of the NCO peak as the end of the reaction, the reactant was cooled to room temperature and filtered with a 100-mesh filter cloth to obtain a polyamide with an imine skeleton, a urethane skeleton, and a butadiene skeleton. Imine resin 1. Viscosity: 7.5Pa･s (25℃, E-type viscometer) Acid value: 16.9mgKOH/g Solid content: 50% by mass Number average molecular weight: 13723 Glass transition temperature: -10℃ Content rate of polybutadiene structural part: 50/(50+4.8+8.96)×100= 78.4 mass%

<Synthesis Example 2: Synthesis of Polyimide Resin 2> Put 9.13g (30 millimoles) of 4-aminobenzoic acid 5-amino-1,1'-biphenyl-2-yl ester into a 500ml separable flask equipped with a nitrogen introduction tube and a stirring device, 4,4'-(4,4'-isopropylidene diphenoxy) bisphthalic dianhydride 15.61g (30 millimoles), N-methyl-2-pyrrolidone 94.64g, pyridine 0.47g (6 millimoles), 10g of toluene, in a nitrogen environment, 180°C, while removing toluene to the outside of the system on the way, carry out an imidization reaction for 4 hours to obtain a polyimide resin 2 containing polyimide Imine solution (non-volatile content 20% by mass). In the polyimide solution, no precipitation of the synthesized polyimide resin 2 was seen. The weight average molecular weight of the polyimide resin 2 is 45,000.

<Synthesis Example 3: Synthesis of Polyimide Resin 3> The aromatic tetracarboxylic dianhydride (“BisDA-1000” manufactured by SABIC Japan, 4,4'-(4,4'-iso Propylene diphenoxy) diphthalic dianhydride) 65.0 g, cyclohexanone 266.5 g, and methylcyclohexane 44.4 g, 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 dropped, and the imine was carried out at 140°C for 1 hour.化反应。 Chemical reaction. Thereby, a polyimide solution (non-volatile content 30% by mass) containing polyimide resin 3 was obtained. In addition, the weight average molecular weight of the polyimide resin 3 is 25,000.

<Synthesis Example 4: Synthesis of Polyimide Resin 4> Prepare a 500mL separable flask with a moisture quantitative receiver connected with a circulating cooler, a nitrogen introduction tube, and a stirrer. Add 20.3 g of 4,4'-oxydiphthalic anhydride (ODPA), 200 g of γ-butyrolactone, 20 g of toluene, and 5-(4-aminophenoxy)-3- 29.6 g of [4-(4-aminophenoxy)phenyl]-1,1,3-trimethylindanane was stirred at 45°C for 2 hours under a nitrogen stream to perform the reaction. Next, the temperature of the reaction solution was raised and maintained at about 160°C while the condensation water was azeotropically removed with toluene under a nitrogen stream. Confirm that a certain amount of water is accumulated in the moisture quantitative receiver and that the water no longer flows out. After confirmation, the reaction solution was further heated, and stirred at 200°C for 1 hour. After that, it was cooled to obtain a polyimide solution (non-volatile content 20% by mass) containing polyimine 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 aforementioned polyimide resin 4 is 12,000.

<Example 1: Preparation of resin composition 1> Dixylenol type epoxy resin ("YX4000HK" manufactured by Mitsubishi Chemical Corporation, epoxy equivalent approximately 185) 5 parts, naphthalene type epoxy resin (Nippon Steel & Sumikin Chemical Co., Ltd.) Company's "ESN475V", epoxy equivalent of about 332) 5 parts, bisphenol AF type epoxy resin (Mitsubishi Chemical Corporation "YL7760", epoxy equivalent of about 238) 10 parts, cyclohexane type epoxy resin (Mitsubishi Chemical A mixed solvent of "ZX1658GS" manufactured by the company, epoxy equivalent of about 135) 2 parts, polyimide resin 1 (non-volatile content 50% by mass) obtained in Synthesis Example 1, 40 parts, and 10 parts of cyclohexanone are heated while stirring Dissolve. After cooling to room temperature, mix it with a cresol novolac hardener 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% ) 4 parts, active ester hardener (DIC company "EXB-8000L-65M", active base equivalent of about 220, non-volatile content 65% by mass MEK solution) 6 parts, spherical silica (Admatechs company "SC2500SQ "the average particle diameter of 0.5 m, a specific surface area 11.2m ² / g, in terms of silicon dioxide with respect to 100 parts by N- phenyl-3-aminopropyl trimethoxy Silane (by Shin-Etsu chemical Co., Ltd." KBM573 " ) 1 part of surface treatment) 25 parts, carbodiimide resin (Nisshinbo Corporation "V-03", polycarbodiimide, 50% non-volatile toluene solution) 10 parts, amine hardening accelerator (4 -0.2 parts of dimethylaminopyridine (DMAP), uniformly dispersed with a high-speed rotary mixer, and filtered with a filter cartridge ("SHP020" manufactured by ROKITECHNO) to prepare a resin composition 1.

<Example 2: Preparation of resin composition 2> Except for using 100 parts of polyimide resin 2 (non-volatile content 20% by mass) obtained in Synthesis Example 2 instead of using 40 parts of polyimide resin 1 (non-volatile content 50% by mass) obtained in Synthesis Example 1, The same operation as in Example 1 was performed to prepare a resin composition 2.

<Example 3: Preparation of resin composition 3> Except for using 66.7 parts of polyimide resin 3 (non-volatile content 30% by mass) obtained in Synthesis Example 3 instead of using 40 parts of polyimide resin 1 (non-volatile content 50% by mass) obtained in Synthesis Example 1, The same operation as in Example 1 was performed to prepare a resin composition 3.

<Example 4: Preparation of resin composition 4> Except for using 100 parts of polyimide resin 4 (non-volatile content 20% by mass) obtained in Synthesis Example 4 instead of using 40 parts of polyimide resin 1 (non-volatile content 50% by mass) obtained in Synthesis Example 1, The same operation as in Example 1 was performed to prepare a resin composition 4.

<Comparative example 1: Preparation of resin composition 5> Except that 10 parts of the carbodiimide resin of Example 1 ("V-03", polycarbodiimide, 50% non-volatile toluene solution made by Nisshinbo Co., Ltd.) was not used, the same operation as in Example 1 was performed, Prepare resin composition 5.

<Comparative Example 2: Preparation of Resin Composition 6> Except for using 66 parts of phenoxy resin (Mitsubishi Chemical Corporation "YX7553BH30", solid content 30% by mass), instead of using 40 parts of polyimide resin 1 (non-volatile content 50% by mass) obtained in Synthesis Example 1, The same operation as in Example 1 was performed to prepare a resin composition 6.

<Test Example 1: Evaluation of the suppression characteristics of halo phenomenon> (1) Copper clad laminate Prepare a glass cloth substrate epoxy resin double-sided copper-clad laminate with copper foil layers laminated on both sides (copper foil thickness 3μm, substrate thickness 0.15mm, Mitsubishi Gas Chemical Corporation "HL832NSF LCA", 255×340mm size), as Copper clad laminate.

(2) Laminating of resin sheet with support The resin sheets with supports produced in the examples (comparative examples are resin sheet A or resin sheet B) were applied to a batch-type vacuum press laminator (manufactured by Nikko Materials, 2-stage build-up laminator, CVP700), laminated on both sides of the copper-clad laminate in such a way that the resin composition layer is adjacent to the copper-clad laminate. The lamination was performed by reducing the pressure for 30 seconds to make the air pressure 13 hPa or less, and pressing at 130° C. and a pressure of 0.74 MPa for 45 seconds. Next, heat pressurization was performed at 120°C and a pressure of 0.5 MPa for 75 seconds.

(3) Thermal curing of resin composition layer Put the copper clad laminate laminated with the resin composition layer into an oven at 100°C for 30 minutes, then move it to an oven at 180°C for 30 minutes, and heat it to form an insulating layer. Let this be the hardened substrate A.

(4) Laser through hole processing (through hole formation) Using the CO ₂ laser processing machine "605GTWIII(-P)" manufactured by Mitsubishi Electric Corporation, the laser is irradiated from the support to form the top diameter (diameter) on the insulating layer 75μm through hole. The laser irradiation conditions are: mask diameter 1mm, pulse width 16μs, energy 0.2mJ/shot, shot number 2, burst mode (10 kHz).

(5) Coarse treatment After peeling the support of the hardened substrate A with the through-holes formed in the insulating layer, the desmear process is performed as a roughening process. Furthermore, as the desmear treatment, the following wet desmear treatment is implemented.

Wet Desmear Treatment In a swelling solution (Atotech Japan "Swelling Dip Securiganth P", diethylene glycol monobutyl ether, and an aqueous solution of sodium hydroxide) at 60°C for 10 minutes, and then in an oxidizing agent solution (Atotech Japan "Concentrate Compact CP" , Potassium permanganate concentration of about 6%, sodium hydroxide concentration of about 4% aqueous solution) in 80 ℃ for 20 minutes, and finally in the neutralization solution (Atotech Japan "Reduction solution Securiganth P", sulfuric acid aqueous solution) 40 ℃ 5 After immersing in minutes, it was dried at 80°C for 15 minutes. Let this be the roughened substrate A.

(6) Measurement of through hole diameter after desmear treatment The roughened substrate A was subjected to cross-sectional observation using a FIB-SEM composite device ("SMI3050SE" manufactured by SII NanoTechnology). Specifically, the vertical cross-section of the laser through hole is scraped by FIB (Clustered Ion Beam), and the diameter of the through hole after desmearing is measured from the cross-sectional SEM image. From the cross-sectional SEM images of 5 randomly selected locations for each sample, the diameter of the via top after the desmear treatment was measured, and the average value was the diameter Lt (μm) of the via top, as shown in the following table 1.

(7) Measurement of halo distance after roughening treatment The roughened substrate A was observed with an optical microscope (“KH8700” manufactured by Hirox Corporation). Specifically, the insulating layer around the through hole was observed from the upper part of the roughened substrate A using an optical microscope (CCD). The observation is performed by aligning the focal point of the optical microscope at the top of the through hole. As a result of observation, around the through hole, from the edge of the top of the through hole, the insulating layer was continuously seen to have a white donut-shaped halo. Therefore, from the observed image, measure the radius of the top of the through hole (corresponding to the inner radius of the halo portion) r1, and the outer radius of the halo portion r2, and calculate the difference r2 between the equal radius r1 and the radius r2 -r1, as the halo distance from the edge of the top of the through hole at the measurement location.

The aforementioned measurement was performed at 5 randomly selected through holes. Then, the average of the measured values of the measured values of the halo distances of the through-holes at the measured 5 locations 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.

The halo ratio Ht was calculated based on the diameter Lt of the top of the through hole and the halo distance Wt, and is shown in Table 1 below. The halo ratio Ht is the ratio of the halo distance Wt from the edge of the through hole top after the roughening treatment to the radius of the through hole top (Lt/2) after the roughening treatment (Wt/(Lt /2)). If the halo ratio Ht is 35% or less, it is judged as "○", and if the halo ratio Ht is greater than 35%, it is judged as "×".

<Test Example 2: Evaluation of Heat Resistance> (1) Preparation of hardened objects for evaluation The untreated surface of the mold-releasing PET film ("501010" made by Lindeco, thickness 38 μm, 240mm square) is adjacent to the glass cloth base epoxy resin double-sided copper-clad laminate ("R5715ES" made by Matsushita Electric Co., Ltd., thickness 0.7 mm, 255 mm square), set on the glass cloth base epoxy resin copper-clad laminate on both sides, and fix the four sides of the release PET film with polyimide adhesive tape (width 10mm).

The resin sheets (167×107mm square) with supports produced in the examples and comparative examples were applied to a batch vacuum press laminator (manufactured by Nikko Materials, 2-stage build-up laminator, CVP700), The layer of the resin composition is adjacent to the release surface of the release PET film, and the lamination process is performed in the center. The lamination process was performed by pressure-bonding at 100°C and 0.74 MPa for 30 seconds after reducing the pressure for 30 seconds to bring the air pressure to 13 hPa or less.

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

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

(2) Measurement of elongation (breaking elongation) The evaluation hardened objects A and B were cut out into a dumbbell-shaped No. 1 shape to obtain a test piece. The test piece was subjected to a tensile test of a cured product for evaluation using a Tensilon universal testing machine (manufactured by A&D) in accordance with Japanese Industrial Standards (JIS K7127), and the breaking elongation (%) at 23° C. was measured. This operation was performed 3 times, and the average values are shown in Table 1 below. The rate of change between the average value A of the elongation at break (%) of the evaluation hardened product A and the average value B of the elongation at break (%) of the evaluation hardened product B is obtained by the following formula (1). Change rate of elongation at break (%)=((B-A)/A)×100 (1) If the breaking elongation change rate was 80% or more, it was judged as "○", and if it was 80% or less, it was judged as "×".

<Test Example 3: Evaluation of Flexibility (MIT Folding Resistance)> The evaluation hardened product A obtained in Test Example 2 was cut into a test piece with a width of 15 mm and a length of 110 mm, and the MIT testing device (manufactured by Toyo Seiki Seisakusho Co., Ltd., MIT flexural fatigue testing machine "MIT-DA") was used, According to JIS C-5016, the number of bending resistances until the hardened body breaks is measured under the measurement conditions of a load of 2.5N, a bending angle of 90 degrees, a bending radius of 1.0mm, and a bending speed of 175 times/min. In addition, the measurement is performed on 5 samples, and preferably an average value of 3 points is calculated. When the number of folds is less than 8,000 times, it is evaluated as "×", and when it is more than 8,000 times, it is evaluated as "○".

The usage amount of the non-volatile components of the resin composition of the Examples and Comparative Examples, the measurement results of the test examples, the evaluation results, etc. are shown in Table 1 below.

It can be seen that by using a resin composition containing (A) polyimide resin, (B) carbodiimide resin, and (C) inorganic filler, in which the content of (C) component is less than 40% by mass, A cured product with excellent flexibility, halo phenomenon suppression properties, and heat resistance can be obtained.

Claims (20)

A resin composition containing (A) polyimide resin, (B) carbodiimide resin, and (C) inorganic filler, wherein When the non-volatile content in the resin composition is 100% by mass, the content of component (C) is less than 40% by mass. The resin composition of claim 1, wherein the weight average molecular weight of the component (A) is 1,000 or more and 100,000 or less. Such as the resin composition of claim 1, wherein when the non-volatile content in the resin composition is 100% by mass, the content of component (A) is 15% by mass or more. Such as the resin composition of claim 1, wherein when the non-volatile content in the resin composition is 100% by mass, the content of component (A) is 35% by mass or less. The resin composition of claim 1, wherein component (B) is polycarbodiimide. The resin composition of claim 1, wherein the content rate of the isocyanate group in the molecule of the component (B) is 0.2% by mass or less. Such as the resin composition of claim 1, wherein when the non-volatile content in the resin composition is 100% by mass, the content of the component (B) is 3% by mass or more. Such as the resin composition of claim 1, wherein when the non-volatile content in the resin composition is 100% by mass, the content of the component (B) is 15% by mass or less. The resin composition of claim 1, wherein the mass ratio of (B) component to (A) component ((B) component/(A) component) is 0.1 or more. The resin composition of claim 1, wherein the mass ratio of (B) component to (A) component ((B) component/(A) component) is 0.5 or less. Such as the resin composition of claim 1, wherein the component (C) is silica. The resin composition of claim 1, wherein the average particle size of the component (C) is 1 μm or less. The resin composition of claim 1, which further contains (D) epoxy resin. The resin composition of claim 1, which further contains (E) a hardener. The resin composition of claim 14, wherein the component (E) contains an active ester hardener. Such as the resin composition of claim 1, which is used for forming an insulating layer of a multilayer flexible substrate. A hardened product of the resin composition of any one of claims 1-16. A resin sheet comprising a support body and a resin composition layer formed of the resin composition according to any one of claims 1 to 16 provided on the support body. A multilayer flexible substrate comprising an insulating layer formed by curing the resin composition of any one of claims 1-16. A semiconductor device provided with a multilayer flexible substrate as claimed in claim 19.