Resin components, adhesives, coatings, curing agents, adhesive sheets, resin-coated copper foil, copper-clad laminates, and printed circuit boards

Abstract

This invention provides a resin composition that, when used as an adhesive, imparts excellent adhesion, solder heat resistance, damp heat resistance, and migration resistance to the cured material. Furthermore, when used as a resin film, the cured material also exhibits excellent solder heat resistance and high storage modulus. This invention relates to a resin composition, adhesive, coating agent, cured material, adhesive sheet, resin-coated copper foil, copper-clad laminate, and printed circuit board. The resin composition contains: polyimide (A), a crosslinking agent (B) represented by general formula (1), and a curing agent (C) other than component (B). The polyimide (A) is a reactant containing a monomer group comprising an aromatic tetracarboxylic anhydride (a1) and a diamine containing a dimer diamine (a2). (In formula (1), X1, X2, and X3 each independently represent a group having one or more epoxy backbones.)

Description

Technical Field

[0001] The present invention relates to a resin composition, an adhesive, a coating agent, a cured product, an adhesive sheet, a resin-coated copper foil, a copper-clad laminate, and a printed wiring board. Prior Art

[0002] Polyimides are typically produced by reacting tetracarboxylic anhydride with diamines. They possess various properties, including heat resistance, adhesion, and mechanical properties. Therefore, they are used in a variety of applications, including protective films for semiconductors, insulating and sealing films, and adhesives for flexible printed wiring boards and printed circuit boards.

[0003] Furthermore, in recent years, high-frequency electrical signals have been used to transmit and process large amounts of information at high speeds. However, since high-frequency signals are very susceptible to attenuation, even for the aforementioned multilayer wiring boards, it is necessary to minimize transmission losses. In this regard, polyimides with low dielectric properties (low dielectric constant and low dielectric loss tangent) are useful.

[0004] As a technique for forming an adhesive layer in a copper-clad laminate comprising an insulating film, an adhesive layer, and copper foil, the present inventors have disclosed an adhesive composition containing a polyimide having tetracarboxylic acid residues and a diamine residue derived from a dimer acid, and a crosslinking component (Patent Document 1). This polyimide exhibits excellent solder heat resistance due to its aromatic rings.

[0005] The following three are the current issues in each application. 1. This technology incorporates a multifunctional epoxy resin as one of the crosslinking components in the adhesive composition. However, this epoxy resin often contains chlorine as an impurity during the manufacturing process. When such a composition is used to manufacture wiring boards, applying voltage across the copper circuit terminals in high-humidity environments can cause copper to precipitate and dissolve from the anode side, leading to a phenomenon known as ion migration that can cause short circuits. 2. In this technology, isocyanate is used as a thermoplastic polyimide component in copper-clad laminates, and a high temperature of over 280°C is required to produce the copper-clad laminates. 3. A typical method for producing polyimide films is the casting method. In this method, a polyimide solution is applied to a support substrate, dried, and then imidized by heat treatment. The support substrate is then peeled off. However, imidization does not progress unless the heat treatment is at very high temperatures, such as 300-400°C. [Prior Art Literature] [Patent Document]

[0006] [Patent Document 1] Japanese Patent Application Laid-Open No. 2018-121807 Summary of the Invention

[0007] [Technical Problem to be Solved by the Invention]

[0008] An object of the present invention is to provide a resin composition which, when used as an adhesive, imparts a cured product having excellent adhesiveness, solder heat resistance, heat and humidity resistance, and migration resistance, and which also exhibits excellent solder heat resistance and high storage modulus when the cured product is used as a resin film. [Technical Means]

[0009] The present inventors conducted intensive studies and found that the above problems can be solved, thereby completing the present invention. That is, in the present invention, the following is provided.

[0010] 1. A resin composition comprising: polyimide (A), a crosslinking agent (B) represented by the general formula (1), and a curing agent (C) other than the component (B), wherein the polyimide (A) is a reactant of a monomer group containing an aromatic tetracarboxylic anhydride (a1) and a diamine (a2) containing a dimer diamine; [Chemical Formula 1] (In the formula (1), X1, X2 and X3 each independently represent a group having one or more epoxy skeletons.)

[0011] 2. The resin composition according to item 1 above, wherein the component (C) is one or more selected from the group consisting of polyamide polyamine, polyether polyamine and trimer triamine.

[0012] 3. The resin composition according to item 1 or 2 above, wherein the resin composition further contains an inorganic filler.

[0013] 4. An adhesive comprising the resin composition according to item 1 above.

[0014] 5. A coating agent comprising the resin composition according to item 1 above.

[0015] 6. A cured product containing one or more selected from the group consisting of the resin composition according to the previous item 1, the adhesive according to the previous item 4, and the coating agent according to the previous item 5.

[0016] 7. An adhesive sheet having the cured product according to the previous item 6 on at least one surface of a support film.

[0017] 8. A resin-coated copper foil containing the cured product according to the previous item 6 or the adhesive sheet according to the previous item 7, and a copper foil.

[0018] 9. A copper-clad laminate containing the resin-coated copper foil according to the previous item 8, and a copper foil or an insulating sheet.

[0019] 10. A printed wiring board having a circuit pattern on the copper foil surface of the copper-clad laminate according to the previous item 9. [Advantages of the Invention]

[0020] When the resin composition of the present invention is used as an adhesive, it imparts a cured product with excellent adhesiveness, solder heat resistance, heat and humidity resistance, and migration resistance. In addition, when the cured product is used as a resin film, it also exhibits excellent solder heat resistance and high storage modulus. In addition, the resin composition of the present invention can be cured at a lower temperature than before by using a combination of polyimide and a crosslinking agent. Embodiments

[0021] The resin composition of the present invention contains: polyimide (A) (hereinafter referred to as component (A)), a crosslinking agent (B) represented by the general formula (1) (hereinafter referred to as component (B)), and a curing agent (C) other than component (B) (hereinafter referred to as component (C)). The polyimide (A) is a reaction product of a monomer group containing an aromatic tetracarboxylic anhydride (a1) (hereinafter referred to as component (a1)) and a diamine (a2) containing a dimer diamine (hereinafter referred to as component (a2)). <​​​​​​​​​​(A) component is a polyimide and is a component for making the layer of the resin composition (hereinafter referred to as the cured product layer) exhibit a low dielectric constant and a low dielectric loss tangent.

[0024] Examples of the component (a1) include 2,2’,3,3’-biphenyltetracarboxylic dianhydride, 2,3’,3,4’-biphenyltetracarboxylic dianhydride, 3,3’,4,4’-biphenyltetracarboxylic dianhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 3,3’,4,4’-diphenylsulfonetetracarboxylic dianhydride, 4,4’-oxydiphthalic anhydride, 4,4’-[propane-2,2-diyldi(1,4-phenyleneoxy)]diphthalic dianhydride, 2,2’,3,3’-benzophenonetetracarboxylic dianhydride, 2,3,3’,4’-benzophenonetetracarboxylic dianhydride, 3,3’,4,4’-benzophenonetetracarboxylic dianhydride, 2,3’,3,4’-diphenylethertetracarboxylic dianhydride, bis(2,3-dicarboxyphenyl)ether dianhydride, bis(2,3-dicarboxyphenyl)methane dianhydride, bis(3,4-dicarboxyphenyl)methane dianhydride, 1,1-bis(2,3-dicarboxyphenyl)ethane dianhydride, 1,1-bis(3,4-dicarboxyphenyl)ethane dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, bis(2,3-dicarboxyphenoxyphenyl)sulfone dianhydride, bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 2,3,6,7-anthracenetetracarboxylic dianhydride, 1,2,5,6-naphthalenetetracarboxylic dianhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 4,8-dimethyl-1,2,3,5,6,7-hexahydronaphthalene-1,2,5,6-tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(3,3’,4,4’-tetracarboxyphenyl)tetrafluoropropane dianhydride, etc. These can be used alone or in combination of two or more.

[0025] Among them, as the component (a1), from the viewpoints of the flexibility and solder heat resistance of the cured product layer, a substance represented by the following general formula (2) is preferably used. [Chemical formula 2] (In formula (2), X represents a single bond, -SO 2-, -CO-, -O-, -OC 6H 4-C(CH 3) 2-C 6H 4-O-, -C(CH 3) 2-, -OC 6H 4-SO 2-C 6H 4-O-, -C(CHF 2) 2-, -C(CF 3) 2-, -COO-(CH 2) p-OCO-, or -COO-H 2C-HC(-OC(=O)-CH 3)-CH 2-OCO-, and p represents an integer from 1 to 20.)

[0026] Examples of the substance represented by general formula (2) include: 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonatetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane These may be used alone or in combination of two or more. Among these, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride and 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride are preferred because they allow component (A) to dissolve well in organic solvents.

[0027] The amount of component (a1) used in 100 mol% of the monomer group constituting component (A) is usually 10 to 90 mol%, preferably 25 to 75 mol%.

[0028] Furthermore, the amount of the tetracarboxylic anhydride represented by the general formula (2) used in 100 mol% of the monomer group constituting the component (A) is usually 10 to 90 mol%, preferably 25 to 75 mol%.

[0029] The amount of the tetracarboxylic anhydride represented by the general formula (2) used in 100 mol% of the component (a1) is usually 10 to 100 mol%, preferably 50 to 100 mol%.

[0030] The component (a2) is a diamine including a dimer diamine.

[0031] The dimer diamine refers to a product obtained by substituting all carboxyl groups of a dimer acid with primary amino groups or primary aminomethyl groups (for example, refer to Japanese Patent Laid-Open No. 9-12712). Herein, the dimer acid refers to a substance mainly containing a dibasic acid with 36 carbon atoms obtained by dimerizing unsaturated fatty acids such as oleic acid, linoleic acid, and linolenic acid, and contains monomeric acids with 18 carbon atoms, trimeric acids with 54 carbon atoms, and polymeric fatty acids with 20 to 90 carbon atoms depending on its purification degree. Also, although the aforementioned dimer acid contains double bonds, the degree of unsaturation can be reduced by, for example, a hydrogenation reaction.

[0032] As the aforementioned dimer diamine, for example, a substance represented by the following general formula (3) can be cited. Also, in general formula (3), it is preferable that m + n = 6 to 17, it is preferable that p + q = 8 to 19, and the dotted line part means a carbon-carbon single bond or a carbon-carbon double bond.

[0033] [Chemical Formula 3]

[0034] In addition, as commercially available products of dimer diamine, examples include: "Versamine 551", "Versamine 552" (both are manufactured by Cognis Japan Co., Ltd.), "PRIAMINE 1073", "PRIAMINE 1074", "PRIAMINE 1075" (both are manufactured by Croda Japan Co., Ltd.), etc. Among these commercially available products, "Versamine 551" and "PRIAMINE 1074" contain a compound represented by the following formula (3-1), and "Versamine 552", "PRIAMINE 1073", and "PRIAMINE 1075" are dimer diamines containing a compound represented by the following formula (3-2).

[0035] [Chemical Formula 4]

[0036] [Chemical Formula 5]

[0037] Also, in the dimer diamine, amines derived from the aforementioned monomeric acids, trimeric acids, and / or polymeric fatty acids may be contained, and as their content, it is 10% by weight or less in the dimer diamine, preferably 5% by weight or less, more preferably 3% by weight or less, and further preferably 2% by weight or less.

[0038] Furthermore, as the dimer diamine, a commercial product may be used as it is, or a product obtained by subjecting a commercial product to a purification treatment such as distillation may be used.

[0039] The amount of the dimer diamine used in 100 mol% of the monomer group constituting component (A) is usually 5 mol% or more, preferably 25 to 75 mol%.

[0040] The amount of the dimer diamine used in 100 mol% of the component (a2) is usually 10 mol% or more, and preferably 30 to 100 mol%.

[0041] Furthermore, the component (a2) may contain a diamine (a2-1) other than a dimer diamine (hereinafter referred to as the component (a2-1)). Examples of the component (a2-1) include aliphatic diamines, alicyclic diamines, aromatic diamines, diaminoethers, and diaminopolysiloxanes. However, these amines do not include dimer diamines.

[0042] Examples of the aliphatic diamine include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane.

[0043] Examples of the alicyclic diamine include diaminocyclohexane, diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, diaminodicyclohexylpropane, tetramethyldiaminodicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, diaminobicyclo[2.2.1]heptane, bis(aminomethyl)-bicyclo[2.2.1]heptane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0(2,6)]decane, and isophoronediamine.

[0044] Examples of the aromatic diamine include: Diaminobiphenyls such as 2,2'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, and 2,2'-di-n-propyl-4,4'-diaminobiphenyl; 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane and other bisaminophenoxyphenylpropanes; 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether and other diaminodiphenyl ethers; P-phenylenediamine, m-phenylenediamine and other phenylenediamines; 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide and other diaminodiphenyl sulfides; 3,3'-diaminodiphenylsulfone, 3,4'-diaminodiphenylsulfone, 4,4'-diaminodiphenylsulfone and other diaminodiphenylsulfones; Diaminobenzophenones such as 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, and 4,4'-diaminobenzophenone; 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, bis[4-(3-aminophenoxy)phenyl]methane and other diaminodiphenylmethanes; Diaminophenylpropanes such as 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, and 2-(3-aminophenyl)-2-(4-aminophenyl)propane; Diaminophenyl hexafluoropropanes such as 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, and 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane; 1,1-bis(3-aminophenyl)-1-phenylethane, 1,1-bis(4-aminophenyl)-1-phenylethane, 1-(3-aminophenyl)-1-(4-aminophenyl)-1-phenylethane and other diaminophenylphenylethanes; 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene and other bisaminophenoxybenzenes; 1,3-bis(3-aminobenzyl)benzene, 1,3-bis(4-aminobenzyl)benzene, 1,4-bis(3-aminobenzyl)benzene, 1,4-bis(4-aminobenzyl)benzene and other bisaminobenzylbenzenes; 1,3-bis(3-amino-α,α-dimethylbenzyl)benzene, 1,3-bis(4-amino-α,α-dimethylbenzyl)benzene, 1,4-bis(3-amino-α,α-dimethylbenzyl)benzene, 1,4-bis(4-amino-α,α-dimethylbenzyl)benzene and other bisaminodimethylbenzylbenzenes; 1,3-bis(3-amino-α,α-di-trifluoromethylbenzyl)benzene, 1,3-bis(4-amino-α,α-di-trifluoromethylbenzyl)benzene, 1,4-bis(3-amino-α,α-di-trifluoromethylbenzyl)benzene, 1,4-bis(4-amino-α,α-di-trifluoromethylbenzyl)benzene and other bisaminobis-trifluoromethylbenzylbenzenes; Aminophenoxybiphenyls such as 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, and bis[1-(3-aminophenoxy)]biphenyl; Aminophenoxyphenyl ketones such as bis[4-(3-aminophenoxy)phenyl]ketone and bis[4-(4-aminophenoxy)phenyl]ketone; Aminophenoxyphenyl sulfides such as bis[4-(3-aminophenoxy)phenyl]sulfide and bis[4-(4-aminophenoxy)phenyl]sulfide; Bis[4-(3-aminophenoxy)phenyl]sulfonium, bis[4-(4-aminophenoxy)phenyl]sulfonium and other aminophenoxyphenylsulfoniums; Aminophenoxyphenyl ethers such as bis[4-(3-aminophenoxy)phenyl]ether and bis[4-(4-aminophenoxy)phenyl]ether; Aminophenoxyphenylpropanes such as 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, and 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane; 1,3-bis[4-(3-aminophenoxy)benzyl]benzene, 1,3-bis[4-(4-aminophenoxy)benzyl]benzene, 1,4-bis[4-(3-aminophenoxy)benzyl]benzene, 1,4-bis[4-(4-aminophenoxy)benzyl]benzene, and other bis(aminophenoxybenzyl)benzenes; 1,3-bis[4-(3-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,3-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(3-aminophenoxy)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]benzene, etc. bis(aminophenoxy-α,α-dimethylbenzyl)benzene; 4,4'-bis[4-(4-aminophenoxy)benzyl]diphenyl ether and other bis[(aminoaryloxy)benzyl]diphenyl ethers; 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone and other bis(amino-α,α-dimethylbenzylphenoxy)benzophenones; 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenylsulfonium and other bis[amino-α,α-dimethylbenzylphenoxy]diphenylsulfonium; 4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenylsulfonium and other bis[aminophenoxyphenoxy]diphenylsulfonium; Diaminodiaryloxybenzophenones such as 3,3'-diamino-4,4'-diphenoxybenzophenone and 3,3'-diamino-4,4'-diphenyloxybenzophenone; Diaminoaryloxybenzophenones such as 3,3'-diamino-4-phenoxybenzophenone and 3,3'-diamino-4-biphenyloxybenzophenone; 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine, 9,9-bis(4-aminophenyl)fluorene, etc.

[0045] Examples of the diamino ether include bis(aminomethyl)ether, bis(2-aminoethyl)ether, bis(3-aminopropyl)ether, bis[(2-aminomethoxy)ethyl]ether, bis[2-(2-aminoethoxy)ethyl]ether, bis[2-(3-aminopropoxy)ethyl]ether, 1,2-bis(aminomethoxy)ethane, 1,2-bis(2-aminoethoxy)ethane, 1,2-bis[2-(aminomethoxy)ethoxy]ethane, 1,2-bis[2-(2-aminoethoxy)ethoxy]ethane, ethylene glycol bis(3-aminopropyl)ether, diethylene glycol bis(3-aminopropyl)ether, and triethylene glycol bis(3-aminopropyl)ether.

[0046] Examples of diaminopolysiloxanes include α,ω-bis(2-aminoethyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(4-aminobutyl)polydimethylsiloxane, α,ω-bis(5-aminopentyl)polydimethylsiloxane, α,ω-bis[3-(2-aminophenyl)propyl]polydimethylsiloxane, and α,ω-bis[3-(4-aminophenyl)propyl]polydimethylsiloxane.

[0047] These components (a2-1) may be used alone or in combination of two or more. Of these, alicyclic diamines and aromatic diamines are preferred, and aromatic diamines are more preferred, from the perspective of achieving excellent solder heat resistance in the cured layer.

[0048] The amount of component (a2-1) used in 100 mol% of the monomer group constituting component (A) is usually 90 mol% or less, preferably 50 mol% or less.

[0049] The amount of component (a2-1) used in 100 mol% of component (a2) is usually 90 mol% or less, preferably 70 mol% or less.

[0050] Component (A) of the present invention can be obtained by various conventional production methods. Examples of such production methods include: a step of subjecting a monomer group containing components (a1) and (a2) to a polyaddition reaction at a temperature of preferably about 30-120°C, more preferably about 60-100°C, for a time of preferably about 0.1-2 hours, more preferably about 0.1-0.5 hours, to obtain a polyadduct; and a step of subjecting the resulting polyadduct to an imidization reaction, i.e., a dehydration ring-closure reaction, at a temperature of preferably about 80-250°C, more preferably about 100-170°C, for a time of preferably about 0.5-50 hours, more preferably about 1-20 hours. The method and order of mixing components (a1) and (a2) are not particularly limited.

[0051] In the imidization step, various conventional reaction catalysts, dehydrating agents, and organic solvents can be used, and these can be used alone or in combination of two or more.

[0052] Examples of reaction catalysts include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline. Dehydrating agents include aliphatic carboxylic anhydrides such as acetic anhydride, and aromatic carboxylic anhydrides such as benzoic anhydride.

[0053] Examples of the organic solvent include: Nitrogen-based organic solvents such as N-methyl-2-pyrrolidone, N,N-dimethylformamide, N,N-diethylformamide, N,N-dimethylacetamide, N,N-diethylacetamide, and diazabicycloundecene; Aliphatic ketones such as methyl ethyl ketone, methyl n-propyl ketone, methyl isopropyl ketone, n-butyl methyl ketone, isobutyl methyl ketone, diethyl ketone, ethyl n-propyl ketone, ethyl isopropyl ketone, n-butyl ethyl ketone, and di-n-propyl ketone; Alicyclic ketones such as cyclopropyl methyl ketone, cyclobutanone, cyclobutyl methyl ketone, cyclopentanone, cyclohexanone, and methylcyclohexanone; Aliphatic esters such as n-propyl formate, isopropyl formate, n-butyl formate, isobutyl formate, n-pentyl formate, isopentyl formate, ethyl acetate, n-propyl acetate, isopropyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl acetate, isopentyl acetate, methyl propionate, ethyl propionate, n-propyl propionate, isopropyl propionate, and n-butyl propionate; Alkyl carbonates such as dimethyl carbonate, ethyl methyl carbonate, and diethyl carbonate; Alicyclic esters such as methyl cyclopropanecarboxylate, ethyl cyclopropanecarboxylate, and methyl cyclobutanecarboxylate; Aliphatic ethers such as ethyl n-propyl ether, di-n-propyl ether, diisopropyl ether, 1,2-dimethoxyethane, 1,1-diethoxyethane, 1,2-diethoxyethane, 1,2-dimethoxypropane, 2,2-dimethoxypropane, 1,1-diethoxypropane, and 2,2-diethoxypropane; Cyclic ethers such as tetrahydrofuran and dioxane; Methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, tertiary butyl alcohol, etc. Aliphatic hydrocarbons such as 2-methylpentane, 3-ethylpentane, n-hexane, 2-methylhexane, 3-methylhexane, 3-ethylhexane, n-heptane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 3-ethylheptane, n-octane, 2-methyloctane, 3-methyloctane, and 4-methyloctane; Alicyclic hydrocarbons such as methylcyclopentane, ethylcyclopentane, n-propylcyclopentane, isopropylcyclopentane, n-butylcyclopentane, isobutylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, 1,1-dimethylcyclohexane, 1-ethyl-3-methylcyclohexane, and cycloheptane; Aromatic hydrocarbons such as benzene, toluene, and xylene; dimethyl sulfoxide, etc. These may be used alone or in combination of two or more.

[0054] Furthermore, the amount of the organic solvent used is adjusted so that the reaction concentration is 5 to 60% by mass, preferably 20 to 50% by mass.

[0055] The imide ring closure rate of the component (A) is preferably 90 to 100%, more preferably about 95 to 100%, from the viewpoint of obtaining a component (A) having a high softening point and flexibility. It is presumed that this is because by making the imide ring closure rate of the component (A) within the above range, the component (A) easily forms a structure of hard segments and soft segments, resulting in both a high softening point and flexibility. Here, the "imide ring closure rate" refers to the content of cyclic imide bonds in the polyimide of the component (A), and can be determined by various spectroscopic means such as NMR and IR analysis.

[0056] As the physical properties of the component (A), for example, the weight average molecular weight is preferably 10,000 to 100,000. In addition, the number average molecular weight of the component (A) is preferably 5,000 to 50,000. The weight average molecular weight and the number average molecular weight are obtained, for example, in the form of polystyrene conversion values measured by gel permeation chromatography (GPC).

[0057] [[ID=�]] The softening point of the component (A) of the present invention is preferably about 50 to 250 °C, more preferably about 80 to 200 °C. Also, the softening point refers to the temperature at which the storage modulus starts to decrease in the curve of the storage modulus measured using a commercially available measuring instrument (device name: "ARES-2KSTD-FCO-STD", manufactured by Rheometric Scientific Company).

[0058] The component (B) is a crosslinking agent represented by the general formula (1), and by combining with the component (A) and the component (C) described later, it can exhibit any one or more of the following effects. (1) It can cause the resin composition to harden at low temperatures. (2) The hardened product exhibits excellent adhesion, solder heat resistance, and migration resistance. (3) It exhibits excellent solder heat resistance and a high storage modulus when using the hardened product as a resin film.

[0059] [Chemical Formula 1] (In the formula (1), X1, X2, and X3 each independently represent a group having one or more epoxy skeletons.)

[0060] In the formula (1), as the groups of X1, X2, and X3, examples that can be listed independently for each are: glycidyl group, 2,3-epoxypropyl group, 3,4-epoxybutyl group, 2-(3,4-epoxycyclohexyl)ethyl group, a group having a structure in which an alkyl group, an epoxy group, and an alkyl group are arranged in this order represented by the general formula (1-1), a group having a structure in which an alkyl group, an epoxy group, an alkyl group, an epoxy group, and an alkyl group are arranged in this order represented by the general formula (1-2), etc.

[0061] [Chemical Formula 6] (In formula (1-1), Y1 and Y2 are each independently an integer from 1 to 15.)

[0062] [Chemical Formula 7] (In formula (1-2), Z1, Z2, and Z3 are each independently an integer from 1 to 15.)

[0063] As commercially available products of component (B) (i.e., the crosslinking agent represented by general formula (1)), examples include "Sansocizer E-2000H", "Sansocizer E-9000H" (both manufactured by Shin Nippon Rika Co., Ltd.), "Adekacizer O-130P", "Adekacizer O-180P" (both manufactured by ADEKA Corporation), "Epocizer W-100-EL" (manufactured by DIC Corporation), "Kapox S-6" (manufactured by Kao Corporation), "Newcizer 510R" (manufactured by NOF Corporation), etc. "Sansocizer E-2000H" is an epoxy resin containing the compound represented by the following formula (1-3).

[0064] [Chemical Formula 8]

[0065] Regarding the content of component (B), from the aspect of easily exerting the aforementioned effects, in terms of non-volatile components, relative to 100 parts by weight of component (A), it is preferably 1 to 15 parts by weight, more preferably 3.5 to 10 parts by weight, and further preferably 3.5 to 7 parts by weight. Also, non-volatile components refer to the components remaining after removing volatile components such as water and organic solvents.

[0066] Component (C) is a curing agent other than component (B). Since it can promote the reaction between component (A) and component (B), it can be cured at a lower temperature, and the resulting cured product also exhibits excellent solder heat resistance. Here, a curing agent refers to a component having the function of curing, and can be classified into a curing agent (non-crosslinking curing agent) that cures while reacting with components other than the curing agent and a curing agent (crosslinking curing agent, crosslinking agent) that undergoes self-crosslinking between curing agents on the basis of the aforementioned curing.)

[0067] Examples of the component (C) include epoxy resins, benzoxazine, bismaleimide, cyanate, polyisocyanate, phosphorus compounds, acid anhydrides, amines, imidazoles, guanidines, phenolic resins, and active esters. These may be used alone or in combination of two or more.

[0068] Examples of the epoxy resin include phenol novolac-type epoxy resins, cresol novolac-type epoxy resins, bisphenol A-type epoxy resins, bisphenol F-type epoxy resins, bisphenol S-type epoxy resins, hydrogenated bisphenol A-type epoxy resins, hydrogenated bisphenol F-type epoxy resins, stilbene-type epoxy resins, epoxy resins containing a triazine skeleton, epoxy resins containing a fluorene skeleton, linear aliphatic epoxy resins, alicyclic epoxy resins, glycidylamine-type epoxy resins, trisphenolmethane-type epoxy resins, alkyl-modified trisphenolmethane-type epoxy resins, biphenyl-type epoxy resins, epoxy resins containing a dicyclopentadiene skeleton, epoxy resins containing a naphthalene skeleton, arylalkylene-type epoxy resins, tetraglycidylphenylenediamine, dimer acid-modified epoxides which are dimer acid-modified products of the aforementioned epoxides, and dimer acid diglycidyl ester.

[0069] Commercially available epoxy resins include jER828, jER834, jER807, jER604, jER630, jER871, and jER872 (all manufactured by Mitsubishi Chemical Corporation), ST-3000 and YD-172-X75 (all manufactured by Nippon Steel Chemical & Material Co., Ltd.), CELLOXIDE 2021P (manufactured by Daicel Corporation), TETRAD-X (manufactured by Mitsubishi Gas Chemical Co., Ltd.), and NC-513, NC-514S, and NC-547 (all manufactured by Cardolite Corp.).

[0070] Examples of benzoxazines include 6,6-(1-methylethylene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine) and 6,6-(1-methylethylene)bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine). Furthermore, a phenyl group, a methyl group, a cyclohexyl group, or the like may be bonded to the nitrogen of the oxazine ring.

[0071] Examples of commercially available benzoxazine include "Benzoxazine Fa type" and "Benzoxazine Pd type" (both manufactured by Shikoku Chemicals Co., Ltd.) and "RLV-100" (manufactured by Air Water Co., Ltd.).

[0072] Examples of bismaleimide include: N,N'-alkylene bismaleimides such as N,N'-ethylene bismaleimide, N,N'-trimethylene bismaleimide, N,N'-tetramethylene bismaleimide, N,N'-pentamethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N'-hexamethylene bismethyl maleimide, N,N-heptamethylene bismaleimide, N,N-octamethylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, and 1,1'-(decane-1,10-diyl)bis(1H-pyrrole-2,5-dione); Bismaleimides containing cycloalkanes, such as N,N'-dicyclohexylmethanebismaleimide, 1,1'-[(4-hexyl-3-octylcyclohexane-1,2-diyl)bis(octane-1,8-diyl)]bis(1H-pyrrole-2,5-dione), 1,1'-(cyclohexane-1,10-diyl)bis(1H-pyrrole-2,5-dione), and 1,1'-[4,4'-methylenebis(cyclohexane-1,4-diyl)]bis(1H-pyrrole-2,5-dione); Phenyl bismaleimides such as N,N'-xylene bismaleimide, N,N'-toluene bismaleimide, N,N'-phenylenedimethyl bismaleimide, N,N'-m-phenylene bismaleimide, N,N'-p-phenylene bismaleimide, and 4-methyl-1,3-phenylene bismaleimide; Bisphenylene bismaleimides such as 1,1'-[methylenebis(1,4-phenylene)]bis(1H-pyrrole-2,5-dione), 1,1'-[methylenebis(2-ethyl-6-methyl-1,4-phenylene)]bis(1H-pyrrole-2,5-dione), and 1,1'-(1,3-phenylene)bis(1H-pyrrole-2,5-dione); N,N'-(4,4'-diphenylmethane)bismaleimide, N,N'-4,4'-[3,3'-dimethyldiphenylmethane]maleimide, N,N'-4,4'-[3,3'-diethyldiphenylmethane]maleimide, N,N'-(4,4'-diphenylpropane)bismaleimide, N,N'-diphenylcyclohexanebismaleimide, 3,3 '-Dimethyl-5,5'-diethyl-4,4-diphenylmethane bismaleimide, N,N'-(4,4'-diphenylmethane) bismaleimide, N,N'-4,4'-[3,3'-dimethyldiphenylmethane] maleimide, N,N'-4,4'-[3,3'-diethyldiphenylmethane] maleimide, N,N'-(4,4'-diphenylmethane) propane) bismaleimide, N,N'-diphenylcyclohexane bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, N,N'-diphenylether bismaleimide, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(3-maleimidephenoxy)benzene, 1,3-bis(4-maleimidebenzene) N,N'-diphenylbismaleimides such as (1,1'-[2,2'-bis(trifluoromethyl){1,1'-biphenyl}-4,4'-diyl]bis[1H-pyrrole-2,5-dione])benzene, N,N'-3,3'-diphenylsulfonium bismaleimide, N,N'-4,4'-diphenylsulfonium bismaleimide, N,N'-dichlorodiphenylbismaleimide, and 1,1'-[2,2'-bis(trifluoromethyl){1,1'-biphenyl}-4,4'-diyl]bis[1H-pyrrole-2,5-dione]; 2,2-bis[4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[4-(4-maleimidophenoxy)phenyl]hexafluoropropane, 2,2-bis[3-methyl-4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[3-methyl-4-(4-maleimidophenoxy)phenyl]hexafluoropropane, 2,2-bis[3,5-dimethyl- Bis(phenoxyphenyl)alkanes such as 4-(4-maleimidophenoxy)phenyl]propane, 2,2-bis[3,5-dimethyl-4-(4-maleimidophenoxy)phenyl]hexafluoropropane, 2,2-bis[3-ethyl-4-(4-maleimidophenoxy)phenyl]propane, and 2,2-bis[3-ethyl-4-(4-maleimidophenoxy)phenyl]hexafluoropropane. These may be used alone or in combination of two or more.

[0073] In addition, commercially available products of bismaleimide include "BMI", "BMI-70", and "BMI-80" (all manufactured by KI Chemicals Co., Ltd.); "BMI-1000", "BMI-1000H", "BMI-1100", "BMI-1100H", "BMI-2000", "BMI-2300", "BMI-3000", "BMI-3000H", "BMI-4000", "BMI-5100", "BMI-7000", "BMI-7000H", and "BMI-TMH" (all manufactured by Yamato Chemicals Co., Ltd.).

[0074] Furthermore, bismaleimides derived from the aforementioned dimer diamines (hereinafter referred to as maleimides having a dimer diamine skeleton) can also be used as bismaleimides. Commercially available products of such maleimides include, for example, "BMI-689," "BMI-689C," "BMI-1400," "BMI-1500," "BMI-1550," "BMI-1700," "BMI-2500," "BMI-2560," "BMI-3000-C," "BMI-3000J," "BMI-3000 Solution," "BMI-5000P," "BMI-5000T," "BMI-6000," and "BMI-6100" (all manufactured by Designer Molecule Inc.).

[0075] Examples of the cyanate include 2-allylphenol cyanate, 4-methoxyphenol cyanate, 2,2-bis(4-isocyanatophenyl)-1,1,1,3,3,3-hexafluoropropane, bisphenol A cyanate, diallylbisphenol A cyanate, 4-phenylphenol cyanate, 1,1,1-tris(4-cyanatophenyl)ethane, 4-cumylphenol cyanate, 1,1-bis(4-cyanatophenyl)ethane, 4,4′-bisphenol cyanate, and 2,2-bis(4-cyanatophenyl)propane.

[0076] Examples of commercially available cyanate esters include "PRIMASET BTP-6020S" (manufactured by Lonza Japan Co., Ltd.).

[0077] Examples of polyisocyanates include: Straight-chain aliphatic diisocyanates such as methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and decamethylene diisocyanate; Branched-chain aliphatic polyisocyanates such as trimethylbutyl diisocyanate, trimethylpentyl diisocyanate, and trimethylhexamethylene diisocyanate; Alicyclic polyisocyanates such as dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, cyclopentyl diisocyanate, 1,4-cyclohexyl diisocyanate, cycloheptyl diisocyanate, norbornene diisocyanate, norbornene methane diisocyanate, adamantane diisocyanate, cyclohexane-1,4-diylbis(methylene) diisocyanate, 3,5,5-trimethylcyclohexyl diisocyanate, tricyclodecyl diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated dimethyldiphenylmethane diisocyanate, and hydrogenated naphthalene diisocyanate; Aromatic polyisocyanates such as xylylene diisocyanate, toluene diisocyanate, phenylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, m-tetramethylxylylene diisocyanate, and naphthalene diisocyanate.

[0078] In addition, as the polyisocyanate, biuret forms, isocyanurate forms, allophanate forms, and adducts of the aforementioned polyisocyanates can also be used. These polyisocyanates can be used alone or in combination of two or more.

[0079] Commercially available polyisocyanates include: Examples of biuret compounds include Duranate 24A-100, Duranate 22A-75P, and Duranate 21S-75E (all manufactured by Asahi Kasei Co., Ltd.), and Desmodur N3200A (all manufactured by Sumitomo Bayer Polyurethanes Co., Ltd.). Examples of isocyanurate compounds include Duranate TPA-100, Duranate TKA-100, Duranate MFA-75B, and Duranate MHG-80B (all manufactured by Asahi Kasei Corporation), Coronate HXR (manufactured by Tosoh Corporation), Takenate D-131N, Takenate D204EA-1, and Takenate D-127N (all manufactured by Mitsui Chemicals, Inc.), and Vestanate T1890 / 100 (manufactured by Evonik Japan Co., Ltd.). As for allophanate, "Takenate D-178N" (made by Mitsui Chemicals Co., Ltd.) and the like can be cited. Examples of adducts include "Duranate P301-75E" (manufactured by Asahi Kasei Corporation), "Takenate D110N", "Takenate D160N" (all manufactured by Mitsui Chemicals, Inc.), and "Coronate L" (manufactured by Tosoh Corporation).

[0080] Examples of the phosphorus compound include tributylphosphine, phenylphosphine, diphenylphosphine, methyldiphenylphosphine, triphenylphosphine, phosphonium borate compounds, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, and butyltriphenylphosphonium thiocyanate. These compounds may be used alone or in combination of two or more.

[0081] Examples of the acid anhydride include succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 3-dodecenylsuccinic anhydride, and octenylsuccinic anhydride. These may be used alone or in combination of two or more.

[0082] As amines, for example, the aforementioned dimer diamine, (a2-1) component, triethylamine, tributylamine, triethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine and other aliphatic amines can be cited; Aminols such as triethanolamine and dimethylaminoethanol; Alicyclic amines such as trimer triamine; Aromatic amines such as 1,3-aminobenzene, benzyldimethylamine, 1,3-bis(aminomethyl)benzene, and 2,4,6-tris(dimethylaminomethyl)phenol. Heterocyclic amines such as 4-dimethylaminopyridine, N-aminoethylpiperazine, and 1,8-diazabicyclo[5,4,0]-undecene; Polyamide polyamine, polyether polyamine, polyester polyamine, etc. These can be used alone or in combination of two or more.

[0083] Examples of imidazole include 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 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, 2-ethyl-4-methylimidazole tetraphenylborate, 1-cyanoethyl-2-undecylimidazole trimellitate, 1-cyanoethyl-2-phenylimidazole 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, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazole chloride, 2-methylimidazoline, 2-phenylimidazoline, etc. These may be used alone or in combination of two or more.

[0084] Examples of guanidine include dicyandiamide, 1-methylguanidine, 1-ethylguanidine, 1-cyclohexylguanidine, 1-phenylguanidine, 1-(o-tolyl)guanidine, dimethylguanidine, diphenylguanidine, trimethylguanidine, tetramethylguanidine, pentamethylguanidine, 1,5,7-triazabicyclo[4.4.0]dec-5-ene, 7-methyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene, 1-methylbiguanidine, 1-ethylbiguanidine, 1-n-butylbiguanidine, 1-n-octadecylbiguanidine, 1,1-dimethylbiguanidine, 1,1-diethylbiguanidine, 1-cyclohexylbiguanidine, 1-allylbiguanidine, 1-phenylbiguanidine, and 1-(o-tolyl)biguanidine. These may be used alone or in combination of two or more.

[0085] Examples of the phenol resin include phenol novolac resins, cresol novolac resins, bisphenol A novolac resins, triazine-modified phenol novolac resins, and phosphazenes containing phenolic hydroxyl groups. These resins may be used alone or in combination of two or more.

[0086] Examples of active esters include those containing a dicyclopentadienyldiphenol structure, those containing a naphthalene structure, acetylated phenol novolacs, and benzoylated phenol novolacs, as described in Japanese Patent Application Laid-Open No. 2019-183071. These may be used alone or in combination of two or more.

[0087] Examples of commercially available active esters include: EXB9451, EXB9460, EXB9460S, HPC-8000, HPC-8000H, HPC-8000-65T, HPC-8150-62T, HPC-8000H-65MT, HPC-8000L-65MT, EXB-8000L, EXB-8000L-65MT, and EXB-8150-65T, substances containing a biscyclopentadienyldiphenol structure (all manufactured by DIC Corporation); "EXB9416-70BK" (manufactured by DIC Corporation) as a substance containing a naphthalene structure; "DC808" (manufactured by Mitsubishi Chemical Co., Ltd.), an acetylated phenol novolac; "YLH1026", "YLH1030", "YLH1048" (all manufactured by Mitsubishi Chemical Corporation), etc., which are benzoyl compounds of phenol novolac.

[0088] Active esters produced by various conventional methods can be used. Examples thereof include those obtained by reacting a polyfunctional phenol compound with an aromatic carboxylic acid as described in Japanese Patent No. 5152445.

[0089] The aforementioned component (C) may be used alone or in combination of two or more. Among them, from the viewpoint of exhibiting excellent heat resistance in the cured product, amines are preferred, and polyamide polyamines, polyether polyamines, and trimer triamines are more preferred.

[0090] Examples of commercially available polyamide polyamines include "VEGECHEM GREEN V115", "VEGECHEM GREEN V125", "VEGECHEM GREEN V140", "VEGECHEM GREEN V150", "VEGECHEM GREEN V1460", "VEGECHEM GREEN V1480", "VEGECHEM GREEN G250", and "VEGECHEM GREEN G747" (all manufactured by Tsukino Foods Industries Co., Ltd.), "LUCKAMIDE TD-960", "LUCKAMIDE TD-984", and "LUCKAMIDE TD-982" (all manufactured by DIC Corporation).

[0091] Examples of commercially available polyether polyamines include "PEG #1000 Diamine" (manufactured by NOF Corporation), the "JEFFAMINE" series (e.g., "JAFFAMINE D-230," "JAFFAMINE T-403," etc.) (manufactured by HUNTSMAN), and the "Baxxodur" series (manufactured by BASF).

[0092] Trimer triamines are products obtained by replacing all carboxyl groups in trimer acid (see JP-A-2013-505345), a trimer of unsaturated fatty acids such as oleic acid, with primary amine groups. Commercially available products include "PRIAMINE 1071" and "PRIAMINE 1073" (both manufactured by Croda Japan Co., Ltd.).

[0093] The content of the component (C) is preferably 0.5 to 10 parts by weight, more preferably 0.9 to 7 parts by weight, and even more preferably 1 to 5 parts by weight, based on non-volatile content, relative to 100 parts by weight of the component (A), in order to facilitate the aforementioned effects.

[0094] The resin composition of the present invention may further contain an inorganic filler.

[0095] Examples of inorganic fillers include silica fillers, phosphorus-based fillers, fluorine-based fillers, and inorganic ion exchanger fillers. Silica fillers whose surfaces have been modified with a silane coupling agent or other treatment agent may also be used. These may be used alone or in combination of two or more.

[0096] Examples of commercially available inorganic fillers include "FB-3SDC" and "SFP-20M" (all manufactured by DENKA Co., Ltd.), "SC-2500-SPJ," "SC-2500-SXJ," "SC-2500-SVJ," and "SC-2500-SEJ" (all manufactured by ADMATECHS Co., Ltd.), "Exolit OP935" (manufactured by Clariant Chemicals Co., Ltd.), "KTL-500F" (manufactured by Kitamura Co., Ltd.), and "IXE" (manufactured by Toagosei Co., Ltd.).

[0097] The content of the inorganic filler is preferably 5 to 70 parts by weight, more preferably 10 to 60 parts by weight, and even more preferably 10 to 50 parts by weight, based on non-volatile content, relative to 100 parts by weight of component (A), from the viewpoint of facilitating a low dielectric loss tangent of the cured product and improving the storage elastic modulus when used as a resin film.

[0098] The resin composition of the present invention may further contain a phosphorus-based flame retardant.

[0099] Phosphorus-based flame retardants include polyphosphoric acid, phosphate esters, and phosphazene derivatives without phenolic hydroxyl groups. Among these phosphazene derivatives, cyclic phosphazene derivatives are preferred due to their flame retardancy, heat resistance, and bleed resistance. Commercially available cyclic phosphazene derivatives include "SPB-100" (manufactured by Otsuka Chemical Co., Ltd.) and "Rabitle FP-300B" (manufactured by Fushimi Pharmaceutical Co., Ltd.).

[0100] The content of the phosphorus-based flame retardant is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the component (A) in terms of non-volatile matter.

[0101] The resin composition of the present invention may also contain a reactive alkoxysilyl compound represented by the general formula: W-Si(R1)a(OR2)3-a (wherein W represents a group containing a functional group reactive with an acid anhydride group, R1 represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R2 represents a hydrocarbon group having 1 to 8 carbon atoms, and a represents 0, 1, or 2). The reactive alkoxysilyl compound can maintain low dielectric properties in the resin composition layer while adjusting its melt viscosity. This improves the interfacial adhesion between the resin composition layer and the support (the so-called anchoring effect) and suppresses bleeding of the cured layer from the edges of the support.

[0102] Examples of the reactive functional group contained in W in the general formula include amino groups, epoxy groups, and thiol groups.

[0103] Examples of compounds containing amino groups include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-ureidopropyltrialkoxysilane. Examples of compounds containing epoxy groups include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. Examples of compounds containing a thiol group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane. Among these, compounds containing an amine group are preferred due to their excellent reactivity and flow control effects.

[0104] The content of the reactive alkoxysilyl compound is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the component (A) in terms of non-volatile matter.

[0105] The resin composition of the present invention may further contain the aforementioned organic solvent. The content of the organic solvent is preferably adjusted to achieve a non-volatile component concentration of 20-40% by weight, more preferably 25-35% by weight.

[0106] The resin composition of the present invention may also contain, as an additive, a substance other than component (A), component (B), component (C), the inorganic filler, the phosphorus-based flame retardant, the reactive alkoxysilyl compound, or the organic solvent.

[0107] Examples of additives include ring-opening esterification catalysts, dehydrating agents, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents, release agents, surface treatment agents, viscosity modifiers, inorganic pigments, and organic pigments.

[0108] The content of the additives may be less than 1 part by weight, less than 0.1 part by weight, less than 0.01 part by weight, or 0 part by weight relative to 100 parts by weight of the component (A) in terms of non-volatile matter.

[0109] The resin composition of the present invention can be obtained by adding component (A), component (B), and component (C), and optionally, an inorganic filler, a phosphorus-based flame retardant, a reactive alkoxysilyl compound, an organic solvent, and additives, and then mixing and dissolving them.

[0110] [Adhesive] In the present invention, an adhesive containing the aforementioned resin composition is also one embodiment. Thus, the cured product becomes a product with excellent adhesion, solder heat resistance, and migration resistance.

[0111] [Coating agent] In the present invention, a coating agent containing the aforementioned resin composition is also one embodiment. This allows for low-temperature curing, and the cured product exhibits excellent adhesion, solder heat resistance, and low dielectric properties. Furthermore, when the cured product is used as a resin film, it exhibits excellent solder heat resistance and a high storage modulus.

[0112] [Hardened material] In the present invention, a cured product containing one or more selected from the group consisting of the aforementioned resin composition, the aforementioned adhesive, and the aforementioned coating agent is also an embodiment. Examples of methods for producing the cured product include a method comprising the following steps: applying the aforementioned resin composition to a suitable support; curing the resin composition by volatilizing the organic solvent by heating; and peeling off the support. The cured product preferably has a thickness of 3 to 40 μm. Examples of the support include release paper, release film, and the support film described below. Furthermore, when producing the cured product, the aforementioned resin composition may be used in combination with various conventional resin compositions other than the aforementioned resin composition. Furthermore, the resulting cured product may be peeled off the support and used as a resin film.

[0113] [Adhesive sheet] The bonding sheet of the present invention contains the cured product of the present invention on at least one surface of a support film.

[0114] The adhesive sheet can be obtained, for example, by coating the resin composition of the present invention on a support film and curing it by heating, or by laminating the cured product of the present invention on a support film.

[0115] Examples of the support film include polyimide, polyester, polyimide-silica blend, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin, aromatic polyester resins derived from ethylene terephthalate, phenol, phthalic acid, hydroxynaphthoic acid, and p-hydroxybenzoic acid (so-called liquid crystal polymers; "Vecstar" (manufactured by Kuraray Co., Ltd.), etc.), cycloolefin polymers, and fluororesins (polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), polyvinylidene fluoride (PVDF), etc.). The polyimide includes the polyimide film described above in the present invention.

[0116] When applying the resin composition of the present invention to the support film, coating methods include, for example, using a comma coater, die coater, knife coater, lip coater, or other coating machine. The thickness of the coating layer after drying is preferably approximately 1 to 100 μm, more preferably approximately 3 to 50 μm. Furthermore, the cured layer of the adhesive sheet may be protected by various protective films.

[0117] [Copper foil with resin] The resin-coated copper foil of the present invention comprises the cured product or adhesive sheet of the present invention and copper foil. Specifically, it is obtained by applying the resin composition of the present invention to copper foil and then heat-curing it, or by laminating the cured product of the present invention to copper foil. Examples of copper foil include rolled copper foil and electrolytic copper foil. Copper foils that have undergone various surface treatments (roughening, rust prevention, etc.) can also be used. Rust prevention treatments include plating using a plating solution containing Ni, Zn, Sn, etc., and mirror-finishing treatments such as chromate treatment.

[0118] The thickness of the copper foil is preferably about 1 to 100 μm, more preferably about 2 to 38 μm. In addition, as a coating means, the above-mentioned method can be cited.

[0119] The resin composition layer or cured product of the resin-coated copper foil can be partially or completely cured under heating. A partially cured resin composition layer or cured product is in a state known as the B-stage. The thickness of the resin composition layer or cured product is ideally approximately 0.5 to 30 μm. Furthermore, a resin composition layer can be further laminated to the copper foil of the resin-coated copper foil to create a double-sided resin-coated copper foil.

[0120] [Copper Clad Laminate] The copper-clad laminate of the present invention comprises the resin-coated copper foil of the present invention and copper foil or insulating sheet. Copper-clad laminates are also referred to as CCLs (copper clad laminates). Specifically, copper-clad laminates are made by heat-compression-bonding the resin-coated copper foil to at least one or both sides of various conventional copper foils or insulating sheets. When laminating to one side, a material different from the resin-coated copper foil may be pressed onto the other side. The number of resin-coated copper foil, copper foil, and insulating sheet in the copper-clad laminate is not particularly limited.

[0121] In one embodiment, the insulating sheet is preferably a prepreg or the aforementioned support film. A prepreg is a sheet material obtained by impregnating a reinforcing material such as glass cloth with a resin and curing it to the B stage (JIS C 5603). The resin used may be an insulating resin such as the resin composition of the present invention, a phenolic resin, an epoxy resin, a polyester resin, a liquid crystal polymer, or an aromatic polyamide resin. The thickness of the insulating sheet is preferably approximately 20 to 500 μm. Heating and pressing conditions are preferably approximately 150 to 280°C (more preferably approximately 170 to 240°C) and approximately 0.5 to 20 MPa (more preferably approximately 1 to 8 MPa).

[0122] [Printed wiring board] The printed wiring board of the present invention has a circuit pattern on the copper foil surface of the copper-clad laminate of the present invention. Patterning methods for forming the circuit pattern on the copper foil surface of the copper-clad laminate include a subtractive method and a semi-additive method. As a semi-additive method, the following method can be cited: after patterning the copper foil surface of the copper-clad laminate using a resist film, electrolytic copper plating is performed, the resist is removed, and etching is performed using an alkaline solution. Furthermore, the thickness of the circuit pattern layer in the printed wiring board is not particularly limited. Furthermore, a multilayer substrate can be obtained by using the printed wiring board as a core and laminating the same printed wiring board or other conventional printed wiring boards or printed circuit boards thereon. During lamination, the aforementioned resin composition and other conventional resin compositions other than the aforementioned resin composition can be used in combination. Furthermore, the number of layers in the multilayer substrate is not particularly limited. Furthermore, through holes can be inserted in each lamination, and the interior can be plated. The line width / space ratio of the circuit pattern is preferably about 1 μm / 1 μm to 100 μm / 100 μm. In addition, the height of the circuit pattern is also preferably about 1 to 50 μm. [Example]

[0123] The present invention is described in detail below using examples, but the present invention is not limited to these examples. Furthermore, unless otherwise specified, "%" is based on mass.

[0124] Production Example 1 In a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen inlet tube, 210.00 g of 3,3',4,4'-benzophenonetetracarboxylic dianhydride (trade name: "BTDA", manufactured by Evonik Industries, hereinafter referred to as BTDA), 1008.00 g of cyclohexanone, and 201.60 g of methylcyclohexane were placed and heated to 60°C. Subsequently, 318.41 g of dimer diamine (trade name: "PRIAMINE 1075", manufactured by Croda Japan Co., Ltd., hereinafter referred to as PRIAMINE 1075) and 27.31 g of polydimethylsiloxane (trade name: "KF-8010", manufactured by Shin-Etsu Chemical Co., Ltd.) were gradually added, and an imidization reaction was carried out at 120°C for 14 hours to obtain a solution of polyimide (A-1) (non-volatile content 30%).

[0125] Production Example 2 Into the same reaction vessel as in Production Example 1, 280.00 g of 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride (trade name: "BisDA-1000", manufactured by SABIC Innovative Plastics Japan Co., Ltd., hereinafter referred to as BisDA), 794.64 g of cyclohexanone, and 158.93 g of methylcyclohexane were placed and heated to 70°C. Subsequently, 71.88 g of 4,4'-diaminophenyl ether (trade name: "ODA", manufactured by Wakayama Seika Industries Co., Ltd.) and 83.08 g of dimer diamine (PRIAMINE 1075) were gradually added, and an imidization reaction was carried out at 110°C for 12 hours to obtain a solution of polyimide (A-2) (non-volatile content 30%).

[0126] Production Example 3 In the same reaction vessel as in Production Example 1, 210.00 g of BTDA, 1006.32 g of cyclohexanone, and 201.26 g of methylcyclohexane were placed and heated to 60°C. Subsequently, 340.02 g of dimer diamine (PRIAMINE 1075) was gradually added, and an imidization reaction was carried out at 120°C for 14 hours to obtain a solution of polyimide resin (A-3) (non-volatile content 30%).

[0127] Production Example 4 In the same reaction vessel as in Production Example 1, 280.00 g of BisDA-1000, 371.38 g of ethylene glycol dimethyl ether, and 866.56 g of toluene were placed and heated to 70°C. Subsequently, 276.92 g of dimer diamine (PRIAMINE 1075) was gradually added, and an imidization reaction was carried out at 140°C for 12 hours to obtain a solution of polyimide resin (A-4) (non-volatile content 30%).

[0128] Example 1-1 333.3 g (non-volatile content 100.0 g) of (A-1) as a polyimide, 5.3 g (non-volatile content 5.3 g) of a multifunctional epoxy resin having a triglyceride group (trade name: "Sansocizer E-2000H", manufactured by Shin Nippon Chemical Co., Ltd.) as a crosslinking agent of component (B), 1.6 g (non-volatile content 1.6 g) of a polyamide polyamine (trade name: "VEGECHEM GREEN V-150", manufactured by Tsukino Food Industry Co., Ltd.) as a curing agent, and 87.4 g of methyl ethyl ketone as an organic solvent were mixed and stirred thoroughly to obtain a resin composition (1) having a non-volatile content of 25%.

[0129] Examples 1-2 to 1-10, Comparative Examples 1-1 to 1-5 The composition was changed to that shown in Table 1, and the same operation as in Example 1-1 was performed to obtain resin composition (1).

[0130] <Preparation of the next sheet> The resin composition (1) of each embodiment and comparative example was applied to a commercially available polyimide film (trade name: "Kapton 100EN"; film thickness 25 μm, thermal expansion coefficient: 15 ppm / °C, manufactured by DuPont Toray Co., Ltd.) (hereinafter referred to as Kapton) using a gap coater in such a manner that the thickness after drying became 25 μm. The film was then dried at 150°C for 5 minutes to obtain bonding sheets (Kapton / hardened material layer).

[0131] <Production of Copper Clad Laminate (1)> The cured layer side of the aforementioned bonding sheet (Kapton / cured layer) is overlapped on the mirror side of a commercially available electrolytic copper foil (trade name "F2-WS", manufactured by Furukawa Electric Co., Ltd.) (film thickness 18 μm) to produce a laminate (Kapton / cured layer / electrolytic copper foil). Subsequently, the laminate is placed on a pressurizing support, and heated and pressed from above at a pressure of 10 MPa and a temperature of 100°C for 30 seconds through a support made of the same raw material, and then heat-cured at a temperature of 170°C for 30 minutes, thereby producing a copper-clad laminate (1).

[0132] <Adhesion Strength> The peel strength (N / mm) of the copper-clad laminate (1) was measured in accordance with JIS C 6481 (Test methods for copper-clad laminates for flexible printed wiring boards). The results are shown in Table 1.

[0133] <Solder Heat Resistance> The copper-clad laminate (1) was placed in a constant temperature room at 23°C and 50% humidity for 24 hours. It was then floated in a 288°C solder bath with the copper foil side facing downward. The presence of blistering was confirmed and evaluated according to the following criteria. The results are shown in Table 1. (Evaluation Criteria) ○: No change in appearance △: Foaming, expansion, and peeling occur on one half of the copper clad laminate. ×: The copper-clad laminate has foaming, expansion, or peeling.

[0134] <Moisture and heat resistance> The copper-clad laminate (1) was placed in a constant temperature and humidity chamber at 85°C and 85% humidity and removed after 1000 hours. The peel strength (N / mm) was measured according to JIS C 6481 (Test methods for copper-clad laminates for flexible printed wiring boards). The results are shown in Table 1.

[0135] <Migration resistance> A comb-shaped copper circuit with a circuit width / intercircuit distance (L / S) ratio of 20 μm / 40 μm was formed on a commercially available single-sided copper-clad polyimide film (trade name: "Pyralux TAS124500," manufactured by DUPONT) (hereinafter referred to as a PI-attached copper-clad laminate). The cured layer side of the aforementioned adhesive sheet (Kapton / cured layer) was superimposed on the copper circuit side of the PI-attached copper-clad laminate. The film was then placed on a pressurized support and heated and pressed from above at a pressure of 10 MPa and a temperature of 100°C for 30 seconds, through the support made of the same material. Afterwards, the film was heat-cured at 170°C for 30 minutes to produce an evaluation substrate. A voltage of 30 V was applied to the resulting evaluation substrate at a temperature of 85°C and a relative humidity of 85% for 500 hours, and the evaluation was performed according to the following criteria. The adhesive sheet with the resin composition of Comparative Example 1-1 was not evaluated. (Evaluation Criteria) ○: No short circuit was observed even after more than 500 hours ×: Short circuit observed in less than 500 hours

[0136] [Table 1] Polyimide (parts by weight) Crosslinking agent (parts by weight) Hardener (parts by weight) Adhesion strength (N / mm) Solder heat resistance Moisture and heat resistance Migration resistance Example 1-1 A-1 100 B-1 5.3 C-1 1.6 1.0 ○ 1.1 ○ Example 1-2 A-1 100 B-1 11.1 C-1 3.4 1.1 △ 1.0 ○ Examples 1-3 A-3 100 B-1 4.4 C-1 1.4 1.2 ○ 1.0 ○ Examples 1-4 A-3 100 B-1 8.8 C-1 2.7 1.1 ○ 1.1 ○ Examples 1-5 A-4 100 B-1 3.3 C-1 1.0 1.3 ○ 0.9 ○ Examples 1-6 A-4 100 B-1 6.6 C-1 2.0 1.2 ○ 1.0 ○ Examples 1-7 A-1 100 B-1 5.3 C-2 1.8 1.0 ○ 0.8 ○ Examples 1-8 A-1 100 B-1 5.3 C-3 3.3 0.9 ○ 0.9 ○ Examples 1-9 A-1 100 B-1 5.3 C-1 3.2 1.0 ○ 1.0 ○ Examples 1-10 A-1 100 B-1 5.3 C-1 4.9 1.0 ○ 0.8 ○ Comparative Example 1-1 E-1 100 B-1 11.1 C-1 3.4 0.1 × 0.1 - Comparative Example 1-2 A-1 100 F-1 2.2 C-1 1.6 0.6 ○ 0.3 × Comparative Examples 1-3 A-1 100 F-2 2.7 C-1 1.6 0.4 ○ 0.4 × Comparative Examples 1-4 A-1 100 B-1 5.3 - 0.9 × 0.3 ○ Comparative Examples 1-5 A-1 100 - C-1 1.6 0.9 × 0.2 ○ ※The weight of each component is expressed as the weight of the non-volatile component.

[0137] The symbols shown in Table 1 represent the following compounds. (Polyimide) ･A-1: Polyimide of Production Example 1 ･A-3: Polyimide of Production Example 3 ･A-4: Polyimide of Production Example 4 ･E-1: Hydrogenated styrene resin (trade name: Taftec H1062, manufactured by Asahi Kasei Co., Ltd.) (cross-linking agent) B-1: Polyfunctional epoxy resin with a glycerol ester backbone (trade name: "Sansocizer E-2000H," manufactured by Shin Nippon Chemical Co., Ltd.) ･F-1: Multifunctional epoxy resin (trade name: "TETRAD-X", manufactured by Mitsubishi Gas Chemical Co., Ltd.) ･F-2: Multifunctional epoxy resin (trade name: "jER604"), manufactured by Mitsubishi Chemical Corporation (hardener) ･C-1: Polyamide polyamine (trade name: "VEGECHEM GREEN V-150", manufactured by Tsukino Food Industry Co., Ltd.) ･C-2: Polyether polyamine (trade name: "JAFFAMINE T-403", manufactured by HUNTSMAN) ･C-3: Tripolymer triamine (trade name: "PRIAMINE 1071", manufactured by Croda Japan Co., Ltd.)

[0138] Example 2-1 333.3 g (non-volatile content 100.0 g) of (A-2) as a polyimide, 5.9 g (non-volatile content 5.9 g) of an epoxy resin having a triglyceride group (trade name: "Sansocizer E-2000H", manufactured by Shin Nippon Chemical Co., Ltd.) as a crosslinking agent of component (B), 3.6 g (non-volatile content 3.6 g) of trimer triamine (trade name: "PRIAMINE 1071", manufactured by Croda Japan Co., Ltd.) as a curing agent, and 204.7 g of cyclohexanone as an organic solvent were mixed and stirred thoroughly to obtain a resin composition (2) having a non-volatile content of 20%.

[0139] Examples 2-2 to 2-6, Comparative Examples 2-1 to 2-5 The compositions were changed to those shown in Table 2, and the same procedures as in Example 2-1 were followed to obtain resin compositions (2).

[0140] <Preparation of Hardened Layer (1)> The resin composition (2) of each example and comparative example was applied to release paper (manufactured by Sun A. Kaken Co., Ltd.) using a gap coater so that the thickness after drying was 4 μm. After drying at 150° C. for 5 minutes, the release paper was peeled off to obtain a cured layer (1).

[0141] <Determination of relative dielectric constant and dielectric loss tangent> The aforementioned hardened material layer (1) is placed on a pressurizing support, and further, the hardened material layer (1) is heated and pressed for 30 seconds under the conditions of a pressure of 6 MPa and 220°C through the same pressurizing support to be hardened, thereby producing a heat-cured bonded sheet (support / hardened material layer / support). The pressurizing support is removed from the hardened material layer (1), and the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the hardened material layer (1) are calculated using the following method. The resonant frequency and peak Q value of the resonator body without any insertion were measured using a network analyzer (Keysight Technologies, device name: "P5003A") and a split post dielectric resonator (QWED) with a measurement frequency of 10.124 GHz. Next, the adhesive layer was cut into 4 cm x 5 cm test pieces to prepare test pieces. Multiple test pieces were stacked to a total thickness of 100 μm or greater and inserted into the resonator. The resonant frequency and Q value of the inserted test pieces were measured. The relative dielectric constant (Dk) was calculated from the difference in resonant frequency between the resonator body and the test piece inserted. The dielectric loss tangent (Df) was calculated from the difference in Q value and resonant frequency between the resonator body and the test piece inserted. The results are shown in Table 2.

[0142] <Preparation of the next sheet> The resin composition (2) of each embodiment and comparative example was applied to a commercially available polyimide film (trade name: "Kapton 100EN", film thickness 25 μm, thermal expansion coefficient 15 ppm / °C, manufactured by DuPont Toray Co., Ltd.) (hereinafter referred to as Kapton) using a gap coater in such a manner that the thickness after drying became 4 μm. The film was then dried at 150°C for 5 minutes to obtain bonding sheets (Kapton / hardened material layer).

[0143] <Production of Copper Clad Laminate (2)> The cured layer side of the aforementioned bonding sheet (Kapton / cured layer) was overlapped on the mirror side of a commercially available electrolytic copper foil (trade name "F2-WS", manufactured by Furukawa Electric Co., Ltd.) (film thickness 18 μm) to produce a laminate (Kapton / cured layer / electrolytic copper foil). Subsequently, the laminate was placed on a pressurizing support and heated and pressed from above at a pressure of 6 MPa and a temperature of 220° C. for 30 seconds through a support made of the same raw material, thereby producing a copper-clad laminate (2).

[0144] <Fit> The appearance of the copper-clad laminate (2) was confirmed and evaluated according to the following criteria. The results are shown in Table 2. ○: No gaps or expansion on the copper clad laminate ×: There are gaps and expansions on the copper-clad laminate.

[0145] <Adhesion Strength> The peel strength (N / mm) of the copper-clad laminate (2) was measured using the same method as above. The results are shown in Table 2.

[0146] <Solder Heat Resistance> The solder heat resistance of the copper-clad laminate (2) was evaluated using the same method as above. The results are shown in Table 2.

[0147] [Table 2] polyimide (parts by weight) crosslinking agent (parts by weight) hardener (parts by weight) Inorganic fillers (parts by weight) Fit Relative dielectric constant Dk Dielectric loss tangent Df Adhesion strength (N / mm) Solder heat resistance Example 2-1 A-2 100 B-1 5.9 C-3 3.6 - ○ 2.8 0.0039 1.1 ○ Example 2-2 A-2 100 B-1 3.0 C-3 7.2 - ○ 2.8 0.0045 1.0 △ Example 2-3 A-2 100 B-1 5.9 C-3 7.2 - ○ 2.8 0.0044 0.7 ○ Examples 2-4 A-2 100 B-1 3.0 C-2 2.0 - ○ 2.8 0.0035 0.5 △ Examples 2-5 A-2 100 B-1 5.9 C-3 3.6 D-1 12.2 ○ 2.8 0.0040 1.1 ○ Examples 2-6 A-2 100 B-1 5.9 C-3 3.6 D-1 46.9 ○ 3.0 0.0036 1.2 ○ Comparative Example 2-1 A-2 100 F-1 1.3 C-3 3.6 - ○ 2.8 0.0044 0.2 △ Comparative Example 2-2 A-2 100 F-2 1.5 C-3 3.6 - ○ 2.7 0.0040 0.4 × Comparative Examples 2-3 A-2 100 - C-3 3.6 - ○ 2.9 0.0045 0.4 × Comparative Examples 2-4 A-2 100 B-1 3.0 - - × - Comparative Examples 2-5 A-2 100 F-1 1.3 C-2 2.0 - ○ 2.8 0.0038 0.4 × ※The weight of each component is expressed as the weight of the non-volatile component.

[0148] The symbols shown in Table 2 represent the following compounds, respectively. (Polyimide) ･A-2: Polyimide of Production Example 2 (cross-linking agent) B-1: Polyfunctional epoxy resin with a glycerol ester backbone (trade name: "Sansocizer E-2000H," manufactured by Shin Nippon Chemical Co., Ltd.) ･F-1: Multifunctional epoxy resin (trade name: "TETRAD-X", manufactured by Mitsubishi Gas Chemical Co., Ltd.) ･F-2: Multifunctional epoxy resin (trade name: "jER604", manufactured by Mitsubishi Chemical Corporation) (hardener) ･C-2: Polyether polyamine (trade name: "JAFFAMINE T-403", manufactured by HUNTSMAN) ･C-3: Tripolymer triamine (trade name: "PRIAMINE 1071", manufactured by Croda Japan Co., Ltd.) (Inorganic filler) ･D-1: Phenyl-modified silica (trade name: "ADMAFINE SC2500-SPJ", manufactured by Admatechs Co., Ltd.)

[0149] Example 3-1 333.3 g (non-volatile content 100.0 g) of (A-2) as a polyimide, 3.0 g (non-volatile content 3.0 g) of an epoxy resin having a triglyceride group (trade name: "Sansocizer E-2000H", manufactured by Shin Nippon Chemical Co., Ltd.) as a crosslinking agent of component (B), 1.6 g (non-volatile content 1.6 g) of a polyamide polyamine (trade name: "VEGECHEM GREEN V-150", manufactured by Tsukino Food Industry Co., Ltd.) as a curing agent, and 185.1 g of cyclohexanone as an organic solvent were mixed and stirred thoroughly to obtain a resin composition (3) having a non-volatile content of 20%.

[0150] Examples 3-2 to 3-9, Comparative Examples 3-1 to 3-2 The compositions were changed to those shown in Table 3, and the same procedures as in Example 3-1 were followed to obtain resin compositions (3).

[0151] <Preparation of Hardened Layer (2)> The resin composition (3) of each embodiment and comparative example was applied to release paper (manufactured by Sun A. Kaken Co., Ltd.) using a gap coater so that the thickness after drying was 12 μm. The coating was then dried at 150° C. for 5 minutes and then at 170° C. for 30 minutes. The release paper was then peeled off to obtain a cured layer (2).

[0152] <Solder Heat Resistance> The cured layer (2) was superimposed on the mirror surface of a commercially available electrolytic copper foil (trade name "F2-WS", manufactured by Furukawa Electric Co., Ltd.) (film thickness 18 μm). The copper foil side was used as the lower surface, and the layer was floated in a 288°C solder bath. The shape of the cured layer and its adhesion to the copper foil were confirmed and evaluated according to the following criteria. The results are shown in Table 3. (Evaluation Criteria) ○: No change in shape and no adhesion to copper foil △: Although there is no change in shape, there is adhesion to the copper foil ×: There is a change in shape and there is also adhesion to the copper foil

[0153] <Storage modulus> A dynamic viscoelasticity tester (DMA7100, manufactured by Hitachi High-Tech Science Co., Ltd.) was used to test the storage modulus (E') of a copper foil coated with resin, cut into 20 mm x 40 mm pieces. The test was conducted at a 20 mm gap, a heating rate of 10 mm / min, and a frequency of 1 Hz. Higher values ​​indicate better results. The results are shown in Table 3. A value of 1.0 × 10 5 Pa or higher was considered good.

[0154] [Table 3] polyimide (parts by weight) crosslinking agent (parts by weight) hardener (parts by weight) Inorganic filler (parts by weight) Solder heat resistance Storage modulus (Pa) Example 3-1 A-2 100 B-1 3.0 C-1 1.6 - ○ 3.0×10 6 Example 3-2 A-2 100 B-1 4.5 C-1 1.6 - ○ 4.5×10 6 Example 3-3 A-2 100 B-1 1.5 C-1 1.6 - △ 2.1×10 5 Examples 3-4 A-2 100 B-1 3.0 C-1 2.4 - ○ 4.0×10 6 Examples 3-5 A-2 100 B-1 3.0 C-1 0.8 - △ 1.0×10 5 Examples 3-6 A-2 100 B-1 3.0 C-2 2.0 - ○ 4.0×10 6 Examples 3-7 A-2 100 B-1 3.0 C-3 3.6 - ○ 2.2×10 6 Examples 3-8 A-2 100 B-1 3.0 C-4 2.8 - △ 2.9×10 6 Examples 3-9 A-2 100 B-1 3.0 C-1 1.6 D-2 26.1 ○ 5.5×10 6 Comparative Example 3-1 A-2 100 - C-1 1.6 - × 1.0×10 4 Comparative Example 3-2 A-2 100 B-1 3.0 - - × 2.1×10 5 ※The weight of each component is expressed as the weight of the non-volatile component.

[0155] The symbols shown in Table 3 represent the following compounds, respectively. (Polyimide) ･A-2: Polyimide of Production Example 2 (cross-linking agent) B-1: Polyfunctional epoxy resin with a glycerol ester skeleton (trade name: "Sansocizer E-2000H", manufactured by Shin Nippon Chemical Co., Ltd.) (hardener) ･C-1: Polyamide polyamine (trade name: "VEGECHEM GREEN V-150", manufactured by Tsukino Food Industry Co., Ltd.) ･C-2: Polyether polyamine (trade name: "JAFFAMINE T-403", manufactured by HUNTSMAN) ･C-3: Tripolymer triamine (trade name: "PRIAMINE 1071", manufactured by Croda Japan Co., Ltd.) ･C-4: Active ester (trade name: "EPICLON HPC-8000L", manufactured by DIC Corporation) (Inorganic filler) ･D-2: Fused silica (trade name: "FB-3SDC", manufactured by DENKA Co., Ltd.)

Claims

1. A resin composition characterized by comprising: a polyimide (A), a crosslinking agent (B) represented by general formula (1), and a curing agent (C), wherein the polyimide (A) is a reactant containing a group of monomers comprising an aromatic tetracarboxylic anhydride (a1) and a diamine containing a dimer diamine (a2), and the curing agent (C) is selected from one or more of the group consisting of benzoxazine, bismaleimide, cyanate ester, polyisocyanate, phosphorus compound, acid anhydride, amine, imidazole, guanidine, phenolic resin and active ester; [Chemical 1] (in formula (1), X1, X2 and X3 each independently represent a group having one or more epoxy skeletons).

2. The resin composition as described in claim 1, wherein, The component (C) is selected from one or more of the group consisting of polyamine polyamines, polyether polyamines and trimer triamines.

3. The resin composition as described in claim 1 or 2, wherein, The resin composition further contains inorganic fillers.

4. An adhesive characterized by containing a resin composition as described in claim 1.

5. A coating agent characterized by containing a resin composition as described in claim 1.

6. A cured material, characterized in that it contains one or more of the resin composition selected from the group consisting of the resin composition described in claim 1, the adhesive described in claim 4, and the coating agent described in claim 5.

7. An adhesive sheet characterized by having a hardened material as described in claim 6 on at least one side of a support membrane.

8. A resin-coated copper foil, characterized in that it comprises: a hardened material as described in claim 6 or an adhesive sheet as described in claim 7, and a copper foil.

9. A copper-clad laminate, characterized in that it comprises: a resin-coated copper foil as described in claim 8, and a copper foil or insulating sheet.

10. A printed wiring board, characterized in that a circuit pattern is present on the copper foil side of the copper-clad laminate as described in claim 9.