Adhesive composition, cured material, adhesive sheet, resin-coated copper foil, copper-clad laminate, and printed circuit board.

Abstract

This invention provides an adhesive composition that provides an adhesive layer that maintains low dielectric properties (low dielectric constant and low dielectric loss tangent), exhibiting high adhesive strength by improving adhesion to difficult-to-bond substrates such as fluorinated resins, and consequently, excellent solder heat resistance. An adhesive composition comprises: a polyimide resin (A) as a product of a reaction component comprising an aromatic tetracarboxylic dianhydride (a1) and a diamine containing a dimerized diamine (a2); an epoxy resin (B); a bismaleimide having a dimerized diamine backbone (C); and a diene polymer (D) having 1,2-vinyl groups in its side chains.

Description

Adhesive composition, cured product, adhesive sheet, copper foil with resin, copper-clad laminate, and printed wiring board The present invention relates to an adhesive composition, a cured product, an adhesive sheet, a copper foil with resin, a copper-clad laminate, and a printed wiring board. Polyimide resins are usually obtained by reacting tetracarboxylic anhydrides with diamines, and have various properties such as heat resistance, adhesion, and mechanical properties. They are often used as adhesive compositions for protective films or insulating sealing films for semiconductors, and flexible printed wiring boards or printed circuit boards. In recent years, in order to transmit and process large-capacity information at high speed, high-frequency electrical signals are used. However, high-frequency signals are very prone to attenuation. Therefore, for the multilayer wiring board, a design that can suppress transmission loss as much as possible is also required. In this regard, polyimide resins with low dielectric properties (low dielectric constant, low dielectric loss tangent) are useful. As such a technique, the applicant has disclosed an adhesive composition containing a polyimide having a tetracarboxylic acid residue and a diamine residue derived from dimer acid and a crosslinking component, in order to form an adhesive layer in a copper-clad laminate having an insulating film, an adhesive layer, and a copper foil (Patent Document 1). In this technique, the polyimide resin of the adhesive layer is respectively bonded to an insulating film such as polyimide and a copper foil, and exhibits the effect of exerting high adhesive strength. On the other hand, in recent years, in order to meet the requirements of further high-frequencyization, a trend has been found to use fluorine-based resins such as polytetrafluoroethylene (PTFE) or perfluoroalkoxy alkane (PFA) as insulating films having lower dielectric properties. However, in the case of using a fluorine-based resin, the adhesive layer cannot be sufficiently bonded, resulting in a decrease in adhesive strength. Furthermore, the solder heat resistance is also poor. [Prior Art Documents] [Patent Documents] [Patent Document 1] Japanese Patent Application Laid-Open No. 2017-121807 [Problems to be Solved by the Invention] The present invention provides an adhesive composition that provides an adhesive layer that maintains low dielectric properties (low dielectric constant and low dielectric loss tangent), exhibits high adhesive strength by improving the adhesion to poorly adherent substrates such as fluorine-based resins, and further has excellent solder heat resistance. [Technical Means for Solving the Problems] The present inventors have conducted intensive studies and as a result, found a solution to the above problems, thereby completing the present invention. That is, in the present invention, the following can be provided. 1. An adhesive composition, comprising: a polyimide resin (A) which is a product of reaction components including an aromatic tetracarboxylic dianhydride (a1) and a diamine (a2) containing a dimer diamine, an epoxy resin (B), a bismaleimide (C) having a dimer diamine skeleton, and a diene polymer (D) having 1,2-vinyl in the side chain. 2. The adhesive composition according to item 1 above, further comprising an active ester (E). 3. A cured product, comprising the adhesive composition according to item 1 above. 4. An adhesive sheet having the cured product according to item 3 above on at least one side of a support film. 5. A copper foil with resin, comprising the cured product according to item 3 above or the adhesive sheet according to item 4 above, and a copper foil. 6. A copper-clad laminate, comprising the copper foil with resin according to item 5 above, and a copper foil or an insulating sheet. 7. A printed wiring board having a circuit pattern on the copper foil surface of the copper-clad laminate according to item 6 above. [Effects of the Invention] The adhesive composition of the present invention provides an adhesive layer that maintains low dielectric properties (low dielectric constant and low dielectric loss tangent), shows high adhesive strength by improving the adhesion to poorly adherent substrates such as fluorine-based resins when made into a copper-clad laminate, and further has excellent solder heat resistance. The adhesive composition of the present invention comprises: a polyimide resin (A) (hereinafter referred to as component (A)), which is a product of reaction components including an aromatic tetracarboxylic dianhydride (a1) (hereinafter referred to as component (a1)) and a diamine (a2) containing a dimer diamine (hereinafter referred to as component (a2)), an epoxy resin (B) (hereinafter referred to as component (B)), a bismaleimide (C) having a dimer diamine skeleton (hereinafter referred to as component (C)), and a diene polymer (D) having 1,2-vinyl in the side chain (hereinafter referred to as component (D)). Component (A) is a polyimide resin and is a component for making the layer of the adhesive composition (hereinafter referred to as the adhesive layer) show a low dielectric constant and a low dielectric loss tangent. As the component (a1), examples 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'-diphenylsulfone tetracarboxylic dianhydride, 4,4'-oxydiphthalic anhydride, 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride, 2,2',3,3'-benzophenone tetracarboxylic dianhydride, 2,3,3',4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 2,3',3,4'-diphenylether tetracarboxylic 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. They can be used alone or in combination of two or more. Among them, as the component (a1), in terms of the flexibility of the adhesive layer and the heat resistance to solder, the component represented by the following general formula (1) is preferred. (In formula (1), X represents a single bond, -SO 2 -, -CO-, -O-, -O-C 6 H 4 -C(CH 3 ) 2 -C 6 H 4 -O-, -C(CH 3 ) 2-, -O-C 6 H 4 -SO 2 -C 6 H 4 -O-, -C(CHF 2 ) 2 -, -C(CF 3 ) 2 -, -COO-(CH 2 ) p -OCO- or -COO-H 2 C-HC(-O-C(=O)-CH 3 )-CH 2 -OCO-, where p represents an integer from 1 to 20) As the component represented by the general formula (1), examples include: 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfone tetracarboxylic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenylether tetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride, 2,2-bis(3,3',4,4'-tetracarboxyphenyl)tetrafluoropropane dianhydride, 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, etc. They can be used alone or in combination of two or more. Among them, in terms of the good solubility of component (A) in an organic solvent, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride and 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride are preferred. The usage amount of component (a1) in 100 mol% of the monomer group constituting component (A) is usually 10 mol% to 90 mol%, preferably 25 mol% to 75 mol%. In addition, the amount of the tetracarboxylic anhydride represented by the general formula (1) used in 100 mol% of the monomer group constituting the component (A) is usually 10 mol% to 90 mol%, preferably 25 mol% to 75 mol%. The amount of the tetracarboxylic anhydride represented by the general formula (1) used in 100 mol% of the component (a1) is usually 10 mol% to 100 mol%, preferably 50 mol% to 100 mol%. The component (a2) is a diamine containing a dimer diamine. The so-called dimer diamine is a compound 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). Here, the so-called dimer acid mainly includes a dibasic acid having 36 carbon atoms obtained by dimerizing unsaturated fatty acids such as oleic acid, linoleic acid, or linolenic acid, and includes monomer acids having 18 carbon atoms, trimer acids having 54 carbon atoms, and polymer fatty acids having 20 to 90 carbon atoms depending on the purification degree of the dimer acid. In addition, double bonds are included in the dimer acid, and for example, the degree of unsaturation can be reduced by a hydrogenation reaction. Examples of the dimer diamine include the dimer diamine represented by the following general formula (2). In addition, in the general formula (2), preferably m + n = 6 to 17, preferably p + q = 8 to 19, and the dotted line portion indicates a carbon-carbon single bond or a carbon-carbon double bond. In addition, examples of commercially available products of dimer diamine include: "Versamine 551", "Versamine 552" (manufactured by Cognis Japan Co., Ltd. above); "PRIAMINE 1073", "PRIAMINE 1074", "PRIAMINE 1075" (manufactured by Croda Japan Co., Ltd. above), etc. Among these commercially available products, "Versamine 551" and "PRIAMINE 1074" are dimer diamines containing the compound represented by the following formula (2-1), and "Versamine 552", "PRIAMINE 1073", and "PRIAMINE 1075" are dimer diamines containing the compound represented by the following formula (2-2). In addition, amines derived from the monomer acid, trimer acid, and / or polymer fatty acid may also be included in the dimer diamine, and their content in the dimer diamine is 10% by weight or less, preferably 5% by weight or less, more preferably 3% by weight or less, and even more preferably 2% by weight or less. Furthermore, the dimer diamine can be used directly or a dimer diamine subjected to purification treatment such as distillation can be used. The amount of the dimer diamine used in 100 mol% of the monomer group of the component (A) is usually 5 mol% or more, preferably 25 mol% to 75 mol%. In addition, the amount of the dimer diamine used in 100 mol% of the component (a2) is usually 10 mol% or more, preferably 30 mol% to 100 mol%. In addition, as the component (a2), diamines (a2') other than the dimer diamine may be included (hereinafter referred to as the component (a2')). As the component (a2'), for example, aliphatic diamines, alicyclic diamines, aromatic diamines, diamino ethers, and diamino polysiloxanes can be included. In addition, regarding these amines, the dimer diamine is excluded. 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, 1,12-diaminododecane, etc. 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, isophorone diamine, etc. As the aromatic diamine, for example, the following can be enumerated: diamino biphenyls such as 2,2'-diaminobiphenyl, 3,3'-diaminobiphenyl, 4,4'-diaminobiphenyl, 2,2'-dimethyl-4,4'-diaminobiphenyl, 2,2'-diethyl-4,4'-diaminobiphenyl, 2,2'-di-n-propyl-4,4'-diaminobiphenyl; bisaminophenoxyphenylpropanes such as 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane; diaminodiphenyl ethers such as 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether; phenylenediamines such as p-phenylenediamine, m-phenylenediamine; diaminodiphenyl sulfides such as 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide; diaminodiphenyl sulfones such as 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, 4,4'-diaminodiphenyl sulfone; diaminobenzophenones such as 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, 4,4'-diaminobenzophenone; diaminodiphenyl methanes such as 3,3'-diaminodiphenyl methane, 3,4'-diaminodiphenyl methane, 4,4'-diaminodiphenyl methane, bis[4-(3-aminophenoxy)phenyl]methane; diaminophenylpropanes such as 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl)propane; diaminophenylhexafluoropropanes 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, 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane; diaminophenylphenylethanes such as 1,1-bis(3-aminophenyl)-1-phenylethane, 1,1-bis(4-aminophenyl)-1-phenylethane, 1-(3-aminophenyl)-1-(4-aminophenyl)-1-phenylethane; bisaminophenoxybenzenes such as 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene; bisaminobenzoylbenzenes such as 1,3-bis(3-aminobenzoyl)benzene, 1,3-bis(4-aminobenzoyl)benzene, 1,4-bis(3-aminobenzoyl)benzene, 1,4-bis(4-aminobenzoyl)benzene; bisaminodimethylbenzylbenzenes such as 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;Bis(aminoditrifluoromethylbenzyl)benzenes such as 1,3-bis(3-aminobenzyl-α,α-ditrifluoromethyl)benzene, 1,3-bis(4-aminobenzyl-α,α-ditrifluoromethyl)benzene, 1,4-bis(3-aminobenzyl-α,α-ditrifluoromethyl)benzene, 1,4-bis(4-aminobenzyl-α,α-ditrifluoromethyl)benzene; Aminophenoxybiphenyls such as 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, bis[1-(3-aminophenoxy)]biphenyl; Aminophenoxyphenylketones such as bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]ketone; Aminophenoxyphenylsulfides such as bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfide; Aminophenoxyphenylsulfones such as bis[4-(3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone; Aminophenoxyphenylethers such as bis[4-(3-aminophenoxy)phenyl]ether, 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, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane; Bis(aminophenoxybenzoyl)benzenes such as 1,3-bis[4-(3-aminophenoxy)benzoyl]benzene, 1,3-bis[4-(4-aminophenoxy)benzoyl]benzene, 1,4-bis[4-(3-aminophenoxy)benzoyl]benzene, 1,4-bis[4-(4-aminophenoxy)benzoyl]benzene; Bis(aminophenoxy-α,α-dimethylbenzyl)benzenes such as 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; Bis[(aminoaryloxy)benzoyl]diphenylethers such as 4,4'-bis[4-(4-aminophenoxy)benzoyl]diphenyl ether; Bis(amino-α,α-dimethylbenzylphenoxy)benzophenones such as 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone; Bis[amino-α,α-dimethylbenzylphenoxy]diphenylsulfones such as 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenylsulfone; Bis[aminophenoxyphenoxy]diphenylsulfones such as 4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenylsulfone; Diaminodiaryloxydibenzophenones such as 3,3'-diamino-4,4'-diphenoxydibenzophenone, 3,3'-diamino-4,4'-dibiphenyloxydibenzophenone;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-indene-5-amine, 9,9-bis(4-aminophenyl)fluorene, etc. As the diamino ether, for example, 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, triethylene glycol bis(3-aminopropyl) ether, etc. can be cited. As the diamino polysiloxane, for example, 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, α,ω-bis[3-(4-aminophenyl)propyl] polydimethylsiloxane, etc. can be cited. These (a2') components can be a single type or a combination of two or more. Among them, in terms of the adhesive layer showing excellent solder heat resistance, alicyclic diamines and aromatic diamines are preferred, and aromatic diamines are more preferred. The usage amount of the (a2') component in 100 mol% of the monomer group constituting the (A) component is usually 90 mol% or less, preferably 50 mol% or less. In addition, the usage amount of the (a2') component in 100 mol% of the (a2) component is usually 90 mol% or less, preferably 70 mol% or less. The component (A) of the present invention can be obtained by various known manufacturing methods. As its manufacturing method, for example, a method including the following steps can be cited: a step of obtaining an addition polymer by subjecting a monomer group containing the component (a1) and the component (a2) to an addition polymerization reaction under conditions where the temperature is preferably about 30°C to 120°C, more preferably about 60°C to 100°C, and the time is preferably about 0.1 hour to 2 hours, more preferably about 0.1 hour to 0.5 hour; and a step of subjecting the obtained addition polymer to an imidization reaction, that is, a dehydration ring-closure reaction, at a temperature preferably about 80°C to 250°C, more preferably about 100°C to 170°C for preferably about 0.5 hour to 50 hours, more preferably about 1 hour to 20 hours. In addition, the method, order, etc. of mixing the monomer groups such as the component (a1) and the component (a2) are not particularly limited. In addition, in the step of the imidization reaction, various known reaction catalysts, dehydrating agents, and organic solvents can also be used, and they can be a single kind or a combination of two or more kinds. Examples of the reaction catalyst include aliphatic tertiary amines such as triethylamine; aromatic tertiary amines such as dimethylaniline; and heterocyclic tertiary amines such as pyridine, methylpyridine, and isoquinoline. Examples of the dehydrating agent include aliphatic carboxylic anhydrides such as acetic anhydride or aromatic carboxylic anhydrides such as benzoic anhydride. 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; alcohols such as methanol, ethanol, n-propanol, isopropanol, 1-methoxy-2-propanol, and tert-butanol; 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; and dimethyl sulfoxide. They may be used alone or in combination of two or more. In addition, the amount of the organic solvent used is adjusted so that the reaction concentration becomes 5% by mass to 60% by mass, preferably 20% by mass to 50% by mass. In terms of obtaining component (A) with high softening point and flexibility, the imide ring closure rate of component (A) is preferably 90% to 100%, more preferably about 95% to 100%. It is speculated that the reason is that when the imide ring closure rate of component (A) is within the above range, in component (A), it is easy to form the structure of hard segments and soft segments, and both the softening point and flexibility become high. Here, the so-called "imide ring closure rate" refers to the content of cyclic imide bonds in the polyimide of component (A), and can be determined by various spectroscopic means such as Nuclear Magnetic Resonance (NMR) or Infrared (IR) analysis, for example. As the physical properties of component (A), for example, the weight average molecular weight is preferably 10,000 to 100,000. In addition, the number average molecular weight of component (A) is preferably 5,000 to 50,000. The weight average molecular weight and the number average molecular weight can be obtained, for example, as polystyrene conversion values measured by Gel Penetration Chromatography (GPC). In terms of being easily processed by press hardening during the manufacture of laminates such as copper-clad laminates, the softening point of component (A) of the present invention is preferably about 50°C to 250°C, more preferably about 80°C to 200°C. In addition, the softening point refers to the temperature at which the storage elastic modulus starts to decrease in the distribution of the storage elastic modulus measured using a commercially available measuring instrument (device name: "ARES-2KSTD-FCO-STD", manufactured by Rheometric Scientfic) and the like. Component (B) is an epoxy resin and is a component that contributes to the excellent solder heat resistance of the adhesive layer. As the component (B), examples include: novolak type epoxy resins such as phenol novolak type epoxy resin and cresol novolak type epoxy resin; bisphenol type epoxy resins such as bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated bisphenol A type epoxy resin, and hydrogenated bisphenol F type epoxy resin; polyphenylene alkane type epoxy resins such as triphenol methane type epoxy resin and alkyl-modified triphenol methane type epoxy resin; alicyclic epoxy resins such as dicyclopentadienyl phenol type epoxy resin and (3',4'-epoxycyclohexyl)methyl-3,4-epoxycyclohexanecarboxylate; glycidyl amine type epoxy resins such as N,N,N',N'-tetraglycidyl phthalylenediamine, N,N-diglycidylaniline, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenyl sulfone; isocyanurate type epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; aromatic hydrocarbon epoxy resins such as biphenyl type epoxy resin, stilbene type epoxy resin, fluorene type epoxy resin, and aryl alkylene type epoxy resin; ether type epoxy resins (reaction products of polyhydric alcohols such as glycerol, neopentyl glycol, ethylene glycol, propylene glycol, butylene glycol, 1,5-pentanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, hydroquinone, naphthol, trihydroxybiphenyl, bisresorcinol, bisxylenol, binaphthol, trihydroxyphenylmethane, and tetrahydroxyphenylethane with epichlorohydrin), ester type epoxy resins (reaction products of polycarboxylic acids such as phthalic acid, methylphthalic acid, isophthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, trimellitic acid, and / or polymeric fatty acids with epichlorohydrin), ether ester type epoxy resins (reaction products of hydroxycarboxylic acids such as p-oxyphthalic acid and β-oxynaphthoic acid with epichlorohydrin), epoxidized polyolefins, epoxidized polybutadiene, epoxidized soybean oil, aliphatic epoxy resins, dimer acid-modified epoxy resins as dimer acid modifiers of these epoxy resins, and diglycidyl dimer acid esters. They can be a single type or a combination of two or more types. Among them, in terms of improving the adhesion of the adhesive layer to difficult-to-bond substrates such as fluororesins and showing high adhesive strength, and further having excellent solder heat resistance, glycidyl amine type epoxy resins and ether type epoxy resins are preferred. Examples of commercially available epoxy resins include "jER828", "jER834", "jER807", "jER604", "jER630", "jER871", "jER872", "jER1031S" (manufactured by Mitsubishi Chemical Corporation), "ST-3000", "YD-172-X75" (manufactured by NIPPON STEEL Chemical & Material Co., Ltd.), "Celloxide 2021P" (manufactured by Daicel Corporation), "TETRAD-X" (manufactured by Mitsubishi Gas Chemical Company, Inc.), "NC-513", "NC-514S", "NC-547" (manufactured by Cardolite Corp.), and the like. In terms of the excellent solder heat resistance of the adhesive layer, the content of component (B) is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, and even more preferably 0.8 to 2.5 parts by weight, in terms of non-volatile components, relative to 100 parts by weight of component (A). In addition, the non-volatile components refer to the components remaining after removing volatile components such as water and organic solvents. Component (C) is a bismaleimide having a dimer diamine skeleton, and is a component that is sufficiently compatible with component (A) and is used to improve the adhesion to a poorly adherent substrate such as a fluororesin and exhibits high adhesive strength. Examples of commercially available products of component (C) include "BMI-689", "BMI-689C", "BMI-1400", "BMI-1500", "BMI-1550", "BMI-1700", "BMI-3000 COMMERCIAL GRADE", "BMI-3000J", "BMI-3000 Solution", "BMI-5000P", "BMI-5000T" (manufactured by Designer Molecule Inc.), "SLK-2600" (manufactured by Shin-Etsu Chemical Co., Ltd.), and the like. They may be used alone or in combination of two or more. These commercially available products are bismaleimides represented by formula (3) by their trade names. In addition, in formula (3), n of the BMI series represents an integer of 1 to 10, and for SLK-526, m = 1 and n = 5. In terms of showing high adhesive strength for improving the adhesion of the adhesive layer to a poorly adherent substrate and further having excellent solder heat resistance, the content of the (C) component in terms of non-volatile component is preferably 0.1 part by weight to 10 parts by weight, more preferably 0.3 part by weight to 5 parts by weight, and still more preferably 0.5 part by weight to 3 parts by weight with respect to 100 parts by weight of the (A) component. In the adhesive composition of the present invention, a maleimide (C') other than the (C) component (hereinafter, also referred to as the (C') component) may also be contained. As the (C') component, examples include: maleimide; N-alkyl mono-maleimides such as N-methyl maleimide, N-ethyl maleimide, N-n-propyl maleimide, N-isopropyl maleimide, N-n-butyl maleimide, N-isobutyl maleimide, N-tert-butyl maleimide, N-n-pentyl maleimide, N-n-hexyl maleimide, N-n-heptyl maleimide, N-n-octyl maleimide, N-n-nonyl maleimide, N-n-decyl maleimide, N-n-dodecyl maleimide, N-n-tetradecyl maleimide, N-n-hexadecyl maleimide, N-n-octadecyl maleimide; N-cycloalkyl mono-maleimides such as N-cyclopentyl maleimide, N-cyclohexyl maleimide; N-aryl mono-maleimides such as N-phenyl maleimide, N-(2-methylphenyl) maleimide, N-(4-methylphenyl) maleimide, N-(2,6-diethylphenyl) maleimide, N-phenylmethyl maleimide, N-(4-hydroxyphenyl) maleimide, N-(4-carboxyphenyl) maleimide, N-(4-acetylphenyl) maleimide, N-(4-methoxyphenyl) maleimide, N-(4-ethoxyphenyl) maleimide, N-(4-chlorophenyl) maleimide, N-(4-bromophenyl) maleimide; N,N'-alkylene bis-maleimides such as N,N'-ethylene bis-maleimide, N,N'-trimethylene bis-maleimide, N,N'-tetramethylene bis-maleimide, N,N'-pentamethylene bis-maleimide, N,N'-hexamethylene bis-maleimide, N,N-heptamethylene bis-maleimide, N,N-octamethylene bis-maleimide, 1,6'-bis-maleimide-(2,2,4-trimethyl)hexane, 1,1'-(decane-1,10-diyl)bis(1H-pyrrole-2,5-dione); bis-maleimides with cycloalkanes such as N,N'-dicyclohexylmethane bis-maleimide, 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), 1,1'-[4,4'-methylenebis(cyclohexane-1,4-diyl)]bis(1H-pyrrole-2,5-dione); phenylene bis-maleimides such as N,N'-xylene bis-maleimide, N,N'-methylenephenylene bis-maleimide, N,N'-xylylene bis-maleimide, N,N'-m-phenylene bis-maleimide, N,N'-p-phenylene bis-maleimide, 4-methyl-1,3-phenylene bis-maleimide;Bis-phenylene 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), 1,1'-(1,3-phenylene)bis(1H-pyrrole-2,5-dione); N,N'-diphenylmethane bismaleimides such as 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, N,N'-(4,4'-diphenylmethane)bismaleimide, N,N'-4,4'-[3,3'-dimethyldiphenylmethane]bismaleimide, N,N'-4,4'-[3,3'-diethyldiphenylmethane]bismaleimide, N,N'-(4,4'-diphenylpropane)bismaleimide, N,N'-diphenylcyclohexane bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, N,N'-diphenyl ether bismaleimide, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(3-maleimidophenoxy)benzene, 1,3-bis(4-maleimidophenoxy)benzene, N,N'-3,3'-diphenylsulfone bismaleimide, N,N'-4,4'-diphenylsulfone bismaleimide, N,N'-dichlorodiphenyl bismaleimide, 1,1'-[2,2'-bis(trifluoromethyl){1,1'-biphenyl}-4,4'-diyl]bis[1H-pyrrole-2,5-dione]; Bis(maleimidophenoxyphenyl)alkanes such as 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-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, 2,2-bis[3-ethyl-4-(4-maleimidophenoxy)phenyl]hexafluoropropane. They can be a single type or a combination of two or more types.; Examples of commercially available products as component (C') include: "BMI", "BMI-70", "BMI-80" (manufactured by KI Kasei 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", "BMI-TMH" (manufactured by Daiwa Kasei Co., Ltd.), etc. The content of component (C'), in terms of non-volatile components, is preferably 2.5 parts by weight or less, more preferably 1.5 parts by weight or less, relative to 100 parts by weight of component (A). Component (D) is a diene polymer having 1,2-vinyl in the side chain, and is a component that shows high adhesive strength for improving the adhesion of the adhesive layer to a difficult-to-bond substrate. Examples of component (D) include: diene homopolymers such as polyisoprene, polybutadiene, 1,2-butadiene homopolymer; diene copolymers (diene copolymers) such as butadiene-isoprene polymer, isobutene-isopropene polymer, butadiene-acrylonitrile polymer, ethoxylated polybutadiene, epoxidized polybutadiene, butadiene-styrene polymer, styrene-butadiene-styrene polymer, etc. They can be a single type or a combination of two or more. Examples of commercially available products include: "RICON 100", "RICON 150", "RICON 154", "RICON 156", "RICON 181", "RICON 184" (manufactured by CRAY VALLEY); "NISSO-PB JP-200", "NISSO-PB B-1000" (manufactured by Nippon Soda Co., Ltd.), etc. Among them, in terms of improving the adhesion of the adhesive layer to a difficult-to-bond substrate and showing high adhesive strength, diene copolymers (diene copolymers) are preferred, and butadiene-styrene polymers are more preferred. The content of component (D), in terms of non-volatile components, is preferably 5 parts by weight to 40 parts by weight, more preferably 7.5 parts by weight to 20 parts by weight, and even more preferably 10 parts by weight to 15 parts by weight, relative to 100 parts by weight of component (A). The adhesive composition of the present invention may also contain an active ester (E) (hereinafter referred to as component (E)). Examples of the component (E) include components containing a dicyclopentadienyl diphenol structure, components containing a naphthalene structure, acetylated products of phenol novolac, benzoylated products of phenol novolac, etc. described in JP-A-2019-183071. They may be used alone or in combination of two or more. Examples of commercially available products of the component (E) include components containing a dicyclopentadienyl diphenol structure such as "EXB9451", "EXB9460", "EXB9460S", "HPC-8000", "HPC-8000H", "HPC-8000L", "HPC-8000-65T", "HPC-8150-62T", "HPC-8000H-65MT", "HPC-8000L-65MT", "EXB-8000L", "EXB-8000L-65MT", "EXB-8150-65T" (manufactured by DIC Corporation); components containing a naphthalene structure such as "EXB9416-70BK" (manufactured by DIC Corporation); acetylated products of phenol novolac such as "DC808" (manufactured by Mitsubishi Chemical Corporation); benzoylated products of phenol novolac such as "YLH1026", "YLH1030", "YLH1048" (manufactured by Mitsubishi Chemical Corporation), etc. As the component (E), components produced by various known methods may also be used. Examples thereof include components obtained by reacting a polyfunctional phenol compound with an aromatic carboxylic acid described in JP No. 5152445. The content of the component (E) in terms of nonvolatile components is preferably 1 to 10 parts by weight, more preferably 1.5 to 8 parts by weight, and still more preferably 2 to 5 parts by weight with respect to 100 parts by weight of the component (A). The adhesive composition of the present invention may further contain curing components such as benzoxazine, cyanate ester, polyisocyanate, phosphorus compound, acid anhydride, amine, imidazole, guanidine, and phenol resin. They may be used alone or in combination of two or more. Examples of benzoxazine include 6,6-(1-methylethylidene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6,6-(1-methylethylidene)bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine), etc. In addition, a phenyl group, a methyl group, a cyclohexyl group, etc. may be bonded to the nitrogen of the oxazine ring. Examples of commercially available products of benzoxazine include "Benzoxazine F-a type", "Benzoxazine P-d type" (manufactured by Shikoku Kasei Kogyo Co., Ltd.), "RLV-100" (manufactured by AIR WATER Inc.), etc. Examples of the cyanate ester include 2-allylphenol cyanate ester, 4-methoxyphenol cyanate ester, 2,2-bis(4-isocyanatophenyl)-1,1,1,3,3,3-hexafluoropropane, bisphenol A cyanate ester, diallylbisphenol A cyanate ester, 4-phenylphenol cyanate ester, 1,1,1-tris(4-cyanatophenyl)ethane, 4-cumylphenol cyanate ester, 1,1-bis(4-cyanatophenyl)ethane, 4,4'-bisphenol cyanate ester, 2,2-bis(4-cyanatophenyl)propane, and the like. Examples of commercially available products of the cyanate ester include "PRIMASET BTP-6020S" (manufactured by Lonza Japan Co., Ltd.). Examples of the polyisocyanate include linear 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 aliphatic polyisocyanates such as trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, and trimethylhexamethylene diisocyanate; alicyclic polyisocyanates such as dicyclohexylmethane-4,4'-diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, 1,4-cyclohexylene diisocyanate, cycloheptylene diisocyanate, norbornene diisocyanate, norbornene methane diisocyanate, adamantane diisocyanate, cyclohexane-1,4-diylbis(methylene)diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, tricyclodecylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated toluene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated dimethyldiphenylmethane diisocyanate, and hydrogenated naphthalene diisocyanate; and aromatic polyisocyanates such as xylylene diisocyanate, toluene diisocyanate, phenyl diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, m-tetramethylxylylene diisocyanate, and naphthalene diisocyanate. In addition, as the polyisocyanate, a biuret body, an isocyanurate body, a urethane body, or an adduct body of the polyisocyanate may be used. These polyisocyanates may be used alone or in combination of two or more. Regarding commercially available polyisocyanates, for example, for biuret type, examples include "Duranate 24A-100", "Duranate 22A-75P", "Duranate 21S-75E" (manufactured by Asahi Kasei Corporation), "Desmodur N3200A" (manufactured by Sumitomo Bayer Urethane Co., Ltd.), etc.; for isocyanurate type, examples include "Duranate TPA-100", "Duranate TKA-100", "Duranate MFA-75B", "Duranate MHG-80B" (manufactured by Asahi Kasei Corporation), "Coronate HXR" (manufactured by Tosoh Corporation), "Takenate D-131N", "Takenate D204EA-1", "Takenate D-127N" (manufactured by Mitsui Chemicals, Inc.), "VESTANAT T1890 / 100" (manufactured by Evonik Japan Co., Ltd.), etc.; for urethane type, examples include "Takenate D-178N" (manufactured by Mitsui Chemicals, Inc.), etc.; for adduct type, examples include "Duranate P301-75E" (manufactured by Asahi Kasei Corporation), "Takenate D110N", "Takenate D160N" (manufactured by Mitsui Chemicals, Inc.), "Coronate L" (manufactured by Tosoh Corporation), etc. As the phosphorus compound, for example, examples include: tributylphosphine, phenylphosphine, diphenylphosphine, methyldiphenylphosphine, triphenylphosphine, phosphonium borate compound, tetraphenylphosphonium tetraphenylborate, n-butylphosphonium tetraphenylborate, tetrabutylphosphonium decanoate, (4-methylphenyl)triphenylphosphonium thiocyanate, tetraphenylphosphonium thiocyanate, butyltriphenylphosphonium thiocyanate, etc. They may be a single kind or a combination of two or more kinds. As the acid anhydride, for example, examples include: succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic dianhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, norbornane-2,3-dicarboxylic anhydride, methyl norbornane-2,3-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 3-dodecenyl succinic anhydride, octenyl succinic anhydride, etc. They may be a single kind or a combination of two or more kinds. As amines, for example, the following can be mentioned: aliphatic amines such as the dimer diamine, component (a2'), triethylamine, tributylamine, triethylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, etc.; amino alcohols such as triethanolamine, dimethylaminoethanol, etc.; alicyclic amines such as the trimer triamine, etc.; aromatic amines such as 1,3-aminobenzene, benzyldimethylamine, 1,3-bis(aminomethyl)benzene, 2,4,6-tris(dimethylaminomethyl)phenol, etc.; heterocyclic amines such as 4-dimethylaminopyridine, N-aminoethylpiperazine, 1,8-diazabicyclo[5,4,0]-undecene, etc.; polyamide polyamines, polyether polyamines, polyester polyamines, etc. They can be a single kind or a combination of two or more kinds. As imidazoles, for example, the following can be mentioned: 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-undecylimidazolium trimellitate, 1-cyanoethyl-2-phenylimidazolium trimellitate, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine isocyanuric acid adduct, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, etc. They can be a single kind or a combination of two or more kinds. As guanidines, for example, the following can be mentioned: 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-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, 1-(o-tolyl)biguanide, etc. They can be a single kind or a combination of two or more kinds. As the phenolic resin, examples thereof include: phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, triazine-modified phenol novolak resin, phosphazene containing phenolic hydroxyl group, and the like. They may be used alone or in combination of two or more. The content of the curing component in terms of non-volatile component is preferably 0.5 parts by weight to 5 parts by weight, more preferably 0.5 parts by weight to 2 parts by weight, relative to 100 parts by weight of the component (A). The adhesive composition of the present invention may also contain an inorganic filler. Examples of the inorganic filler include: silica filler, phosphorus-based filler, fluorine-based filler, inorganic ion exchanger filler, and the like. In addition, as the silica filler, a filler whose surface is modified with a treating agent such as a silane coupling agent may also be used. They may be used alone or in combination of two or more. Examples of commercially available products of the silica filler include: "FB-3SDC", "SFP-20M" (manufactured by Denka Co., Ltd.), "SC-2500-SPJ", "SC-2500-SXJ", "SC-2500-SVJ", "SC-2500-SEJ" (manufactured by Admatechs Co., Ltd.), "Exolit OP935" (manufactured by Clariant Chemicals Co., Ltd.), "KTL-500F" (manufactured by Kitamura Co., Ltd.), "IXE" (manufactured by Toagosei Co., Ltd.), and the like. The content of the inorganic filler in terms of non-volatile component is preferably 1 part by weight to 150 parts by weight, relative to 100 parts by weight of the component (A). The adhesive composition of the present invention may also contain a phosphorus-based flame retardant. Examples of the phosphorus-based flame retardant include polyphosphoric acid or phosphate ester, phosphazene derivative without phenolic hydroxyl group, and the like. Among the phosphazene derivatives, a cyclic phosphazene derivative is preferred in terms of flame retardancy, heat resistance, exudation resistance, and the like. Examples of commercially available products of the cyclic phosphazene derivative include "SPB-100" (manufactured by Otsuka Chemical Co., Ltd.), "Rabitle FP-300B" (manufactured by Fushimi Pharmaceutical Co., Ltd.), and the like. The content of the phosphorus-based flame retardant in terms of non-volatile component is preferably 1 part by weight to 150 parts by weight, relative to 100 parts by weight of the component (A). The adhesive composition of the present invention may contain the general formula: W-Si(R 1 ) a (OR 2 ) 3-a (In the formula, W represents a group containing a functional group reactive with an acid anhydride group, R 1 represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, and R 2 represents a hydrocarbon group having 1 to 8 carbon atoms, and a represents 0, 1, or 2) a reactive alkoxysilyl compound. By means of the reactive alkoxysilyl compound, the low dielectric constant characteristics of the layer of the adhesive composition can be maintained while adjusting its melt viscosity. As a result, while improving the interfacial adhesion (so-called anchoring effect) between the layer of the adhesive composition and the support, the seepage of the adhesive layer from the end of the support can be suppressed. Examples of the reactive functional group contained in W of the general formula include: amino group, epoxy group, and mercapto group, etc. Examples of the compound in which W contains an amino group include: N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-ureidopropyltrialkoxysilane, etc. As the compound in which W contains an epoxy group, for example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane, etc. can be cited. As the compound in which W contains a mercapto group, for example, 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane, etc. can be cited. Among these, in terms of good reactivity and flow control effect, the compound in which W contains an amino group is preferred. The content of the reactive alkoxysilyl compound, in terms of non-volatile component conversion, is preferably 0.01 parts by weight to 5 parts by weight relative to 100 parts by weight of the component (A). In addition, the organic solvent may also be contained in the adhesive composition of the present invention. As the content of the organic solvent, the non-volatile component concentration of the adhesive composition can be adjusted to preferably 5% by weight to 60% by weight, more preferably 20% by weight to 50% by weight. The adhesive composition of the present invention may contain, as an additive, a substance other than any one of the component (A), component (B), component (C), component (D), component (E), curing component, inorganic filler, phosphorus-based flame retardant, reactive alkoxysilyl compound, and organic solvent. Examples of the additives include: ring-opening esterification reaction catalysts, dehydrating agents, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, brightening agents, colorants, conductive agents, mold release agents, surface treatment agents, viscosity regulators, inorganic pigments, organic pigments, and the like. Examples of the content of the additive include less than 1 part by weight, less than 0.1 part by weight, less than 0.01 part by weight, 0 part by weight, etc., in terms of non-volatile components, relative to 100 parts by weight of the component (A). The adhesive composition of the present invention can be obtained by adding the component (A), the component (B), the component (C), the component (D), the component (E) as needed, a curing component, an inorganic filler, a flame retardant, a reactive alkoxysilyl compound, an organic solvent, and an additive, and dissolving them while mixing. [Cured product] The cured product of the present invention contains the above-mentioned adhesive composition. Examples of the method for producing the cured product include a method including steps of coating the adhesive composition on a suitable support, hardening by volatilizing the organic solvent by heating, peeling the support, and the like. In addition, the thickness of the cured product is preferably 3 μm to 40 μm. Examples of the support include release paper, release film, and the support film described below. In addition, when producing the cured product, various known adhesive compositions other than the above-mentioned adhesive composition and the above-mentioned adhesive composition can also be used in combination. [Adhesive sheet] The adhesive sheet of the present invention contains the cured product of the present invention on at least one side of a support film. The above-mentioned adhesive sheet can be obtained, for example, by coating the adhesive composition of the present invention on a support film and hardening it by heating; or by laminating the cured product of the present invention on a support film. Examples of the support film include polyimide, polyester, polyimide-silica mixture, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin, aromatic polyester resins obtained from ethylene terephthalate, phenol, phthalic acid, hydroxy naphthoic acid, etc. and p-hydroxybenzoic acid (so-called liquid crystal polymers; "Vecstar" (manufactured by Kuraray Co., Ltd.) etc.), cycloolefin polymers, fluorine-based resins (polytetrafluoroethylene (PTFE), perfluoroalkoxy alkane (PFA), polyvinylidene fluoride (PVDF), etc.). The polyimide includes the above-mentioned polyimide film of the present invention. When applying the adhesive composition of the present invention to the support film, examples of the application method include applicators such as a notch wheel coater, a die coater, a knife coater, and a lip coater. As the thickness of the coating layer, after drying, it is preferably about 1 μm to 100 μm, more preferably about 3 μm to 50 μm. In addition, the adhesive layer of the adhesive sheet can also be protected by various protective films. [Copper foil with resin] The copper foil with resin of the present invention includes the cured product or adhesive sheet of the present invention and a copper foil. Specifically, it is formed by applying the adhesive composition of the present invention to a copper foil and heating and curing it, or by laminating the cured product or adhesive sheet of the present invention to a copper foil. Examples of the copper foil include a rolled copper foil or an electrolytic copper foil, and a copper foil subjected to various surface treatments (roughening, rust prevention, etc.) can also be used. Examples of the rust prevention treatment include plating treatment using a plating solution containing Ni, Zn, Sn, etc., and so-called mirror finishing treatment such as chromate treatment. As the thickness of the copper foil, it is preferably about 1 μm to 100 μm, more preferably about 2 μm to 38 μm. In addition, as the coating means, the above method can be cited. In addition, the cured product or adhesive sheet of the copper foil with resin can also be the cured product or adhesive sheet of the copper foil with resin that is partially cured or completely cured under heating. The partially cured cured product or adhesive sheet is in a state called the so-called B-stage. In addition, as the thickness of the cured product or adhesive sheet, it is preferably about 0.5 μm to 30 μm. In addition, a double-sided copper foil with resin can also be formed by further laminating a cured product or adhesive sheet on the copper foil of the copper foil with resin. [Copper-clad laminate] The copper-clad laminate of the present invention includes the copper foil with resin of the present invention and a copper foil or an insulating sheet. The copper-clad laminate is also called a copper foil substrate (Copper Clad Laminate, CCL). Specifically, the copper-clad laminate is formed by thermocompression bonding the copper foil with resin to at least one side or both sides of various known copper foils or insulating sheets. In the case of laminating on one side, a copper foil different from the copper foil with resin can also be thermocompression bonded to the other side. In addition, the number of copper foils with resin, copper foils, and insulating sheets in the copper-clad laminate is not particularly limited. In one embodiment, the insulating sheet is preferably a prepreg or the support film. A prepreg is a sheet material obtained by impregnating a reinforcing material such as glass cloth with a resin and hardening it to the B-stage (Japanese Industrial Standards (JIS) C 5603). As the resin, insulating resins such as the adhesive composition of the present invention, phenolic resin, epoxy resin, polyester resin, liquid crystal polymer, and aromatic polyamide resin can be used. The thickness of the insulating sheet is preferably about 20 μm to 500 μm. As the heating / pressing conditions, it is preferably about 150°C to 280°C (more preferably about 170°C to 240°C) and preferably about 0.5 MPa to 20 MPa (more preferably about 1 MPa to 8 MPa). [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. Examples of the patterning means for forming a circuit pattern on the copper foil surface of the copper-clad laminate include the subtractive method and the semi-additive method. As the semi-additive method, a method can be cited in which, on the copper foil surface of the copper-clad laminate, after patterning using a resist film, electrolytic copper plating is performed, the resist is removed, and etching is performed using an alkaline solution. In addition, the thickness of the circuit pattern layer in the printed wiring board is not particularly limited. In addition, a multilayer substrate can be obtained by using the printed wiring board as a core and laminating the same printed wiring board or other known printed wiring boards or printed circuit boards thereon. At the time of lamination, the adhesive composition of the present invention and other known adhesive compositions other than the adhesive composition of the present invention can be used in combination. In addition, the number of laminations in the multilayer substrate is not particularly limited. In addition, through holes can be inserted and internal plating treatment can be performed each time of lamination. The line / space ratio of the circuit pattern is not particularly limited, and is preferably about 1 μm / 1 μm to 100 μm / 100 μm. In addition, the height of the circuit pattern is not particularly limited, and is preferably about 1 μm to 50 μm. [Examples] Hereinafter, examples will be given to specifically illustrate the present invention, but the present invention is not particularly limited to these. In addition, unless otherwise specified, "%" is based on mass. <Weight Average Molecular Weight> The weight average molecular weight of polyimide is measured under the following conditions. (Measurement Conditions) Model: HLC-8320GPC (manufactured by Tosoh Corporation) Column: TSKgel SuperHZM-M (manufactured by Tosoh Corporation) Developing Solvent: Tetrahydrofuran Flow Rate: 0.35 mL / minute Measurement Temperature: 40°C Detector: RI Standard: Polystyrene Sample Concentration: 0.4 wt% Production Example 1 In a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen inlet tube, 70.0 g of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA, manufactured by Daikin Industries, Ltd.)), 100.82 g of ethylene glycol dimethyl ether, and 235.24 g of toluene were charged and heated to 70°C. Subsequently, 81.8 g of a dimer diamine (trade name: "PRIAMINE 1075", manufactured by Croda Japan Co., Ltd., hereinafter referred to as PRIAMINE 1075) was slowly added, and then heated to 110°C, and an imidization reaction was carried out for 15 hours to obtain a solution of polyimide resin (A-1) (non-volatile component: 35%). Production Example 2 In the same reaction vessel as in Production Example 1, 200.0 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), 265.27 g of ethylene glycol dimethyl ether, and 618.97 g of toluene were charged and heated to 70°C. Subsequently, 197.8 g of PRIAMINE 1075 was slowly added, and then heated to 110°C, and an imidization reaction was carried out for 10 hours to obtain a solution of polyimide resin (A-2) (non-volatile component: 30%). Production Example 3 In the same reaction vessel as in Production Example 1, 200.0 g of BisDA, 246.83 g of ethylene glycol dimethyl ether, and 575.95 g of toluene were charged and heated to 40°C. Subsequently, 14.53 g of 4,4'-diaminodiphenyl ether (trade name: "ODA", manufactured by Wakayama Seika Kogyo Co., Ltd.) and 156.75 g of PRIAMINE 1075 were slowly added, and then heated to 110°C, and an imidization reaction was carried out for 10 hours to obtain a solution of polyimide resin (A-3) (non-volatile component: 30%). Example 1 271.74 g (non-volatile component: 100.0 g) of component (A-1) as component (A), 1.0 g (non-volatile component: 1.0 g) of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane (trade name: "jER604", manufactured by Mitsubishi Gas Chemical Co., Inc.) as component (B), 1.7 g (non-volatile component: 1.7 g) of the bismaleimide represented by the following formula (4) (trade name "BMI-689", manufactured by Designer Molecule Inc.) as component (C), 11.5 g (non-volatile component: 11.5 g) of a butadiene-styrene polymer (trade name: "RICON 100", manufactured by CRAY VALLEY) as component (D), 2.2 g (non-volatile component: 2.2 g) of an active ester (trade name: "HPC-8000L", manufactured by DIC Corporation) as component (E), and 75.7 g of methyl ethyl ketone as an organic solvent were mixed and stirred well to obtain an adhesive composition having a non-volatile component of 30%. Examples 2 to 11, Comparative Examples 1 to 4 The composition was changed to that shown in Table 1, and the same method as in Example 1 was used to obtain adhesive compositions respectively. <Production of Adhesive Sheet>Each adhesive composition of Examples and Comparative Examples was applied to a release paper (manufactured by Sun A Kaken Co., Ltd.) using a gap coater so that the thickness after drying was 25 μm, dried at 150°C for 5 minutes, and then the release paper was peeled off to obtain adhesive sheets respectively. <Measurement of Relative Dielectric Constant and Dielectric Loss Tangent> The adhesive sheet is placed on a pressing support. Further, by heating and pressing at 5 MPa and 180 °C for 90 minutes with the same pressing support interposed on the adhesive sheet side, it is hardened to produce a heat-hardened laminate (support / adhesive sheet / support). The pressing support is removed from the adhesive sheet, and for the adhesive sheet, the relative dielectric constant (Dk) and dielectric loss tangent (Df) are calculated using the following method. A network analyzer (manufactured by Keysight Technologies, device name: "P5003A") and a split post dielectric resonator (SPDR) with a measurement frequency of 10.124 GHz (manufactured by QWED) are used to measure the resonance frequency of the resonator alone without inserting any components and the Q value of its peak. Next, after cutting the adhesive layer into test pieces of 4 cm × 5 cm, multiple test pieces are stacked so that the total thickness is 100 μm or more and inserted into the resonator, and then the resonance frequency and Q value when the test pieces are inserted are measured. The relative dielectric constant (Dk) is calculated based on the difference in resonance frequency between the resonator alone and when the test pieces are inserted, and the dielectric loss tangent (Df) is calculated based on the difference in Q value and the difference in resonance frequency between the resonator alone and when the test pieces are inserted. The results are shown in Table 1 (the same applies hereinafter). <Fabrication of Copper-Clad Laminate> The adhesive compositions of each example and comparative example are applied to release paper (manufactured by Sun A Kaken Co., Ltd.) with a dry thickness of 25 μm using a gap coater, and then dried at 150 °C for 5 minutes to obtain an adhesive sheet (release paper / adhesive layer). A double-sided copper-clad laminate (trade name: "Pyralux TK125012R", manufactured by Dupont; film thickness 75 μm) with copper foil / fluororesin layers laminated on both sides of a polyimide film is etched with a 40% aqueous solution of iron(III) chloride to remove the copper foil. Next, each adhesive sheet is overlapped on one side of the exposed fluororesin layer, and further, a commercially available electrolytic copper foil (trade name: "F2-WS", manufactured by Furukawa Circuit Foil Co., Ltd., 18 μm thick) is overlapped thereon to produce a laminate (fluororesin layer / polyimide film / fluororesin layer / adhesive sheet / electrolytic copper foil). Subsequently, the laminate is placed on a pressing support with the copper foil side in contact, and a support obtained from the same raw material is interposed from above and heated and pressed at 10 MPa and a temperature of 180 °C for 90 minutes to harden it, thereby fabricating a copper-clad laminate. <接着强度> For the copper-clad laminate, the peel strength (N / mm) is measured in accordance with JIS C 6481 (Test Methods for Copper-Clad Laminates for Flexible Printed Wiring Boards). <Solder Heat Resistance> After placing the copper-clad laminate (1) in a thermostatic chamber at a temperature of 23°C and a humidity of 50% for 24 hours, with the copper foil side facing down, it is floated in a solder bath at 288°C, and the presence or absence of foaming is confirmed and evaluated according to the following criteria. (Evaluation Criteria) ○: No change in appearance. ×: The copper-clad laminate has foaming, swelling, or peeling. [Table 1] The symbols shown in Table 1 respectively represent the following compounds. <Polyimide Resin> ‧A-1: The polyimide resin of Production Example 1 ‧A-2: The polyimide resin of Production Example 2 ‧A-3: The polyimide resin of Production Example 3 <Epoxy Resin> ‧B-1: N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane (trade name: "jER604", manufactured by Mitsubishi Chemical Corporation) ‧B-2: N,N,N',N'-tetraglycidyl phthalic diamine (trade name: "TETRAD-X", manufactured by Mitsubishi Gas Chemical Company, Inc.) ‧B-3: Ether-type epoxy resin (trade name: "jER1031S", reaction product of tetrahydroxyphenylethane and epichlorohydrin, manufactured by Mitsubishi Chemical Corporation) <Bismaleimide> ‧C-1: The bismaleimide represented by the formula (4) (trade name: "BMI-689", manufactured by Designer Molecule Inc.) ‧F-1: N,N'-(4,4'-diphenylmethane) bismaleimide (trade name: "BMI-1000H", manufactured by Daiwa Kasei Co., Ltd.) <Diene-based Polymer> ‧D-1: Butadiene-styrene polymer (trade name: "RICON 100", manufactured by CRAY VALLEY) <Others> ‧E-1: Active ester (trade name: "HPC-8000L", manufactured by DIC Corporation) None None

Claims

1. An adhesive composition comprising: a polyimide resin (A), an epoxy resin (B), a bismaleimide having a dimerized diamine backbone (C), and a diene polymer (D) having 1,2-vinyl groups in its side chains, as a product comprising an aromatic tetracarboxylic dianhydride (a1) and a diamine containing a dimerized diamine (a2), wherein, Based on the conversion of non-volatile components, relative to 100 parts by weight of component (A), the content of component (B) is 0.1 parts by weight to 5 parts by weight, the content of component (C) is 0.1 parts by weight to 10 parts by weight, and the content of component (D) is 5 parts by weight to 40 parts by weight.

2. The adhesive composition as claimed in claim 1, further comprising an active ester (E).

3. A hardened material comprising the adhesive composition as described in claim 1.

4. An adhesive sheet having a hardened material as described in claim 3 on at least one side of a support membrane.

5. A resin-coated copper foil, comprising a hardened material as described in claim 3 or an adhesive sheet as described in claim 4, and a copper foil.

6. A copper-clad laminate comprising a resin-coated copper foil as described in claim 5, and a copper foil or insulating sheet.

7. A printed wiring board having a circuit pattern on the copper foil side of a copper-clad laminate as claimed in claim 6.