Adhesive composition, cured product, adhesive sheet, copper foil with resin, copper-clad laminate, and printed wiring board

Abstract

The present invention provides an adhesive composition which provides a cured product that exhibits excellent solder heat resistance while exhibiting high adhesive strength and low dielectric properties. The 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. The adhesive composition includes a polyimide (A) which is a reaction product of a monomer group including an aromatic tetracarboxylic acid anhydride (a1) and a diamine (a2) including a dimer diamine, an amine type epoxy resin (B) having three or more glycidyl groups, and a polyamine (C) having three or more amino groups and not having a glycidyl group.

Description

Technical Field

[0001] 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. Background Art

[0002] Polyimide is generally obtained by reacting tetracarboxylic anhydride with diamine, and has various properties such as heat resistance, adhesion, and mechanical properties, and is used, for example, as an adhesive for flexible printed wiring boards, printed circuit boards, and the like.

[0003] In addition, in recent years, high-frequency electrical signals are used to transmit and process large amounts of information at high speed, but high-frequency signals are very easy to attenuate. Therefore, the multilayer wiring board is also required to be designed to suppress transmission losses as much as possible. Polyimide with low dielectric properties (low dielectric constant, low dielectric loss tangent) is useful in this regard.

[0004] As such technology, the applicant discloses an adhesive composition (patent document 1) comprising a polyimide having a tetracarboxylic acid residue and a diamine residue derived from a dimer acid and a crosslinking component, or a polyimide as a reaction product of a monomer group comprising a specific amount of aromatic tetracarboxylic anhydride, and dimer diamine and trimer triamine, and an adhesive composition (patent document 2) comprising the polyimide, so as to form an adhesive layer in a copper-clad laminate having an insulating film, an adhesive layer and copper foil, wherein the polyimide has an aromatic ring and thus exhibits excellent solder heat resistance. However, in patent document 1, a cyanate ester is included in the thermoplastic polyimide composition in the copper-clad laminate, and when making the copper-clad laminate, a high temperature of more than 280°C is required, and in patent document 2, low dielectric properties and poor solder heat resistance are obtained. [Prior art literature] [Patent Document]

[0005] [Patent Document 1] Japanese Patent Application Publication No. 2017-121807 [Patent Document 2] Japanese Patent Application Publication No. 2017-186551 Summary of the invention [Problems to be solved by the invention]

[0006] The present invention provides an adhesive composition that provides a cured product that exhibits high adhesive strength and low dielectric properties and also exhibits excellent solder heat resistance. [Technical means to solve the problem]

[0007] The present inventors have conducted intensive studies and have found that the above-mentioned problems can be solved, thereby completing the present invention. That is, the present invention can provide the following.

[0008] 1. An adhesive composition comprising: a polyimide (A) which is a reaction product of a monomer group comprising an aromatic tetracarboxylic anhydride (a1) and a diamine (a2) containing a dimer diamine, an amine-type epoxy resin (B) having three or more glycidyl groups, and A polyamine (C) having no glycidyl group and having three or more amino groups.

[0009] 2. The adhesive composition according to the above item 1, wherein the component (C) is one or more selected from the group consisting of polyamide polyamine, polyether polyamine and trimer triamine.

[0010] 3. The adhesive composition according to the above item 1 or 2, which does not contain an inorganic filler.

[0011] 4. A cured product, which is a cured product of the adhesive composition according to the above item 1.

[0012] 5. An adhesive sheet comprising the cured product according to the above 4 on at least one surface of a support film.

[0013] 6. A copper foil with resin, comprising the cured product according to the above item 4 or the adhesive sheet according to the above item 5, and a copper foil.

[0014] 7. A copper-clad laminate comprising the copper foil with resin according to 6 above, and a copper foil or an insulating sheet.

[0015] 8. A printed wiring board having a circuit pattern on the copper foil surface of the copper-clad laminate according to 7 above. [Effects of the Invention]

[0016] The adhesive composition of the present invention provides a cured product that exhibits high adhesive strength and low dielectric properties and excellent solder heat resistance. In addition, when manufacturing a copper-clad laminate, the adhesive composition can be cured at a relatively low temperature. DETAILED DESCRIPTION

[0017] The adhesive composition of the present invention comprises: a polyimide (A) (hereinafter also referred to as component (A)) which is a reaction product of a monomer group comprising an aromatic tetracarboxylic anhydride (a1) (hereinafter also referred to as component (a1)) and a diamine (a2) (hereinafter also referred to as component (a2)) containing a dimer diamine, an amine-type epoxy resin (B) having three or more glycidyl groups (hereinafter also referred to as component (B)), and a polyamine (C) having no glycidyl group and having three or more amino groups (hereinafter also referred to as component (C)).

[0018] The component (A) is a polyimide and is a component for allowing the cured layer of the adhesive composition (hereinafter also referred to as an adhesive layer) to exhibit a low dielectric constant and a low dielectric loss tangent.

[0019] 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-diylbis(1,4- [phenyloxy)] diphthalic acid dianhydride, 2,2',3,3'-benzophenone tetracarboxylic acid dianhydride, 2,3,3',4'-benzophenone tetracarboxylic acid dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride, 2,3',3,4'-diphenyl ether tetracarboxylic acid 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, ,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 may be used alone or in combination of two or more.

[0020] Among them, the component (a1) is preferably a component represented by the following general formula (1) from the viewpoint that the adhesive layer easily exhibits flexibility and solder heat resistance. (In formula (1), X represents a single bond, -SO 2 -、-CO-、-O-、-OC 6 H 4 -C(CH 3 ) 2 -C 6 H 4 -O-, -C(CH 3 ) 2 -、-OC 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(-OC(=O)-CH 3 )-CH 2 -OCO-, p represents an integer from 1 to 20)

[0021] Examples of the component represented by the general formula (1) include 2,2',3,3'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4'-diphenylethertetracarboxylic dianhydride, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane Dianhydride, 2,2-bis(3,3',4,4'-tetracarboxylphenyl)tetrafluoropropane dianhydride, 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)] diphthalic acid dianhydride, 2,2-bis(2,3-dicarboxylphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxylphenyl)propane dianhydride, 2,2'-bis(3,4-dicarboxylphenoxyphenyl)sulfone dianhydride, etc. They can be used alone or in combination of two or more. Among them, in terms of making the (A) component easily and well dissolved in an organic solvent, preferably 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)] diphthalic acid dianhydride.

[0022] The usage-amount of the (a1) component in 100 mol% of the monomer group which comprises (A) component is 10 mol% - 90 mol% normally, Preferably it is 25 mol% - 75 mol%.

[0023] The usage-amount of the tetracarboxylic anhydride represented by the general formula (1) in 100 mol% of the monomer group constituting the component (A) is usually 10 to 90 mol%, preferably 25 to 75 mol%.

[0024] The usage-amount of the tetracarboxylic anhydride represented by General Formula (1) in 100 mol% of the component (a1) is 10 mol% to 100 mol% normally, Preferably it is 50 mol% to 100 mol%.

[0025] The component (a2) is a diamine including a dimer diamine.

[0026] The so-called dimer diamine is a compound in which all carboxyl groups of a dimer acid are substituted 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 a monomer acid having 18 carbon atoms, a trimer acid having 54 carbon atoms, and a polymerized fatty acid having 20 to 90 carbon atoms, depending on the degree of purification of the dimer acid. In addition, the dimer acid contains a double bond, and the unsaturation degree can be reduced by, for example, a hydrogenation reaction.

[0027] Examples of the dimer diamine include dimer diamines represented by the following general formula (2): In general formula (2), m+n=6 to 17 is preferred, p+q=8 to 19 is preferred, and the dotted line portion indicates a carbon-carbon single bond or a carbon-carbon double bond.

[0028]

[0029] In addition, commercial products of dimer diamines include: "Versamine 551", "Versamine 552" (both manufactured by Cognis Japan Co., Ltd.); "PRIAMINE 1073", "PRIAMINE 1074", "PRIAMINE 1075" (both manufactured by Croda Japan Co., Ltd.), etc. Among these commercial products, "Versamine 551" and "PRIAMINE 1074" are dimer diamines containing a compound represented by the following formula (2-1), and "Versamine 552", "PRIAMINE 1073", and "PRIAMINE 1075" are dimer diamines containing a compound represented by the following formula (2-2).

[0030]

[0031]

[0032] Furthermore, the dimer diamine may also contain amines derived from the monomeric acid, trimer acid and / or polymerized fatty acid, and their content in the dimer diamine is usually 30 wt % or less, preferably 10 wt % or less, more preferably 5 wt % or less, further preferably 3 wt % or less, and particularly preferably 2 wt % or less.

[0033] Furthermore, as the dimer diamine, a commercially available product may be used as it is, or a dimer diamine subjected to a purification treatment such as distillation may be used.

[0034] The usage-amount of the dimer diamine in 100 mol% of the monomer group which comprises (A) component is 5 mol% or more normally, Preferably it is 25 mol% - 75 mol%.

[0035] 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 %.

[0036] Moreover, as (a2)component, you may contain the diamine (a2-1) other than dimer diamine (hereinafter referred to as (a2-1) component).

[0037] As the component (a2-1), for example, aliphatic diamines, alicyclic diamines, aromatic diamines, diamino ethers, and diamino polysiloxanes may be included. In addition, regarding these amines, dimer diamines are excluded.

[0038] 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.

[0039] Examples of the alicyclic diamine include diaminomonoalkanes such as diaminocyclohexane, 1,2-bis(aminomethyl)cyclohexane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, and isophoronediamine; Diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, diaminodicyclohexylpropane, tetramethyldiaminodicyclohexylmethane, bis(4-aminocyclohexyl)methane and other diaminodicycloalkylalkanes; Diaminobicycloalkanes such as diaminobicyclo[2.2.1]heptane and bis(aminomethyl)-bicyclo[2.2.1]heptane; 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0(2,6)]decane, etc.

[0040] 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; Bisaminophenoxyphenylpropanes such as 2,2-bis[4-(3-aminophenoxy)phenyl]propane and 2,2-bis[4-(4-aminophenoxy)phenyl]propane; Diaminodiphenyl ethers such as 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, and 4,4'-diaminodiphenyl ether; Phenylenediamines such as p-phenylenediamine and m-phenylenediamine; Diaminodiphenyl sulfides such as 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, and 4,4'-diaminodiphenyl sulfide; Diaminodiphenyl sulfones such as 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl sulfone; Diaminobenzophenones such as 3,3'-diaminobenzophenone, 3,4'-diaminobenzophenone, and 4,4'-diaminobenzophenone; Diaminodiphenylmethanes such as 3,3'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, and bis[4-(3-aminophenoxy)phenyl]methane; Diaminophenylpropanes such as 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, and 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, and 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane; Diaminophenylethanes such as 1,1-bis(3-aminophenyl)-1-phenylethane, 1,1-bis(4-aminophenyl)-1-phenylethane, and 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, and 1,4-bis(4-aminophenoxy)benzene; 1,3-bis(3-aminobenzoyl)benzene, 1,3-bis(4-aminobenzoyl)benzene, 1,4-bis(3-aminobenzoyl)benzene, 1,4-bis(4-aminobenzoyl)benzene and other bisaminobenzoylbenzenes; 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; Aminophenoxyphenyl sulfones such as bis[4-(3-aminophenoxy)phenyl]sulfone and bis[4-(4-aminophenoxy)phenyl]sulfone; 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)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 and other bis(aminophenoxybenzoyl)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 and other bis(aminophenoxy-α,α-dimethylbenzyl)benzenes; 4,4'-bis[4-(4-aminophenoxy)benzoyl]diphenyl ether and other bis[(aminoaryloxy)benzoyl]diphenyl ethers; 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone and other bis(amino-α,α-dimethylbenzylphenoxy)benzophenone; 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenyl sulfone and other bis[amino-α,α-dimethylbenzylphenoxy]diphenyl sulfone; 4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenyl sulfone and other bis[aminophenoxyphenoxy]diphenyl sulfones; 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.

[0041] 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.

[0042] Examples of the diaminopolysiloxane 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.

[0043] These components (a2-1) may be used alone or in combination of two or more. Among them, alicyclic diamines and aromatic diamines are preferred, and diaminomonoalkane, diaminobiphenyl, and 9,9-bis(4-aminophenyl)fluorene are more preferred.

[0044] The amount of the component (a2-1) used in 100 mol% of the monomer group constituting the component (A) is usually 90 mol% or less, preferably 50 mol% or less.

[0045] The amount of the component (a2-1) used in 100 mol % of the component (a2) is usually 90 mol % or less, preferably 70 mol % or less.

[0046] The component (A) of the present invention can be obtained by various known production methods. As its production method, for example, a method including the following steps can be cited: a step of subjecting a monomer group including the component (a1) and the component (a2) to an addition polymerization reaction under the conditions of preferably about 30°C to 120°C, more preferably about 40°C to 100°C, and preferably about 0.1 hour to 2 hours, more preferably about 0.1 hour to 0.5 hours, to obtain an addition polymer; and a step of subjecting the obtained addition polymer to an imidization reaction, i.e., a dehydration ring-closure reaction, preferably about 0.5 hours to 50 hours, more preferably about 1 hour to 20 hours, at a temperature of preferably about 80°C to 250°C, more preferably about 100°C to 170°C. In addition, the method and order of mixing the component (a1) and the component (a2) are not particularly limited.

[0047] In the imidization reaction step, various known reaction catalysts, dehydrating agents, and organic solvents may be used alone or in combination of two or more.

[0048] Examples of the reaction catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline, etc. Examples of the dehydrating agent include aliphatic carboxylic anhydrides such as acetic anhydride, and aromatic carboxylic anhydrides such as benzoic anhydride.

[0049] 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, n-butyl propionate, etc.; 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, 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; dimethyl sulfoxide, etc. These may be used alone or in combination of two or more.

[0050] 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.

[0051] The imide ring closure rate of the component (A) is preferably 90% to 100%, more preferably about 95% to 100%, in order to obtain the component (A) having both high softening point and flexibility. It is speculated that when the imide ring closure rate of the component (A) is within the above range, the hard segment and soft segment structures are easily formed in the component (A), and the softening point and flexibility are easily increased. Here, the so-called "imide ring closure rate" refers to the content of cyclic imide bonds in the polyimide of the component (A), which can be determined by various spectroscopic means such as nuclear magnetic resonance (NMR) or infrared (IR) analysis.

[0052] 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 can be obtained as polystyrene conversion values ​​measured by gel permeation chromatography (GPC), for example.

[0053] The softening point of the 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 begins to decrease in the distribution of the storage elastic modulus measured using a commercially available measuring device (device name: "ARES-2KSTD-FCO-STD", manufactured by Rheometric Scientific Co., Ltd.) or the like.

[0054] The component (B) is an amine-type epoxy resin having three or more glycidyl groups, and is a component used to make the adhesive layer easily show high peel strength and excellent solder heat resistance. In addition, the so-called glycidyl group refers to the group represented by the general formula (3). In addition, if there are three or more glycidyl groups and one or more amino groups, it can be used even if there are one or more epoxy groups inside. Among them, in terms of the fact that the cured product easily shows excellent solder heat resistance, as the component (B), an amine-type epoxy resin having one or more N,N-diglycidyl groups is preferred.

[0055]

[0056] Examples of such component (B) include: Aliphatic amine type epoxy resins having three glycidyl groups such as N,N,N-triglycidylamine; Alicyclic amine type epoxy resins having four glycidyl groups, such as 1,2-bis(N,N-diglycidylaminomethyl)cyclohexane, 1,3-bis(N,N-diglycidylaminomethyl)cyclohexane, and 1,4-bis(N,N-diglycidylaminomethyl)cyclohexane; Aromatic amine-type epoxy resins having three glycidyl groups, such as N,N-diglycidyl-2-glycidyloxyaniline, N,N-diglycidyl-3-glycidyloxyaniline, and N,N-diglycidyl-4-glycidyloxyaniline; Aromatic amine type epoxy resins having four glycidyl groups, such as N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylsulfone, N,N,N',N'-tetraglycidyl-o-xylylenediamine, N,N,N',N'-tetraglycidyl-m-xylylenediamine, and N,N,N',N'-tetraglycidyl-p-xylylenediamine; Triglycidyl isocyanurate, etc. These may be used alone or in combination of two or more.

[0057] Among these, in terms of excellent solder heat resistance exhibited by the adhesive layer, preferred are aromatic amine-type epoxy resins having three glycidyl groups and aromatic amine-type epoxy resins having four glycidyl groups, and more preferred are N,N-diglycidyl-4-glycidyloxyaniline, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and N,N,N',N'-tetraglycidyl-m-xylylenediamine.

[0058] Examples of commercially available products of the component (B) include: "Sumiepoxy ELM-100 series", "Sumiepoxy ELM-434 series" (all manufactured by Sumitomo Chemical Co., Ltd.), "jER604", "jER630", "jER630LSD" (all manufactured by Mitsubishi Chemical Co., Ltd.), "TETRAD-C", "TETRAD-X" (all manufactured by Mitsubishi Gas Chemical Co., Ltd.), "TEPIC-S", "TEPIC-L" (all manufactured by Nissan Chemical Co., Ltd.), etc. These may be used alone or in combination of two or more.

[0059] The content of component (B) is preferably 0.1 to 8 parts by weight, more preferably 0.5 to 5 parts by weight, and further preferably 1 to 3 parts by weight, relative to 100 parts by weight of component (A), in terms of the excellent solder heat resistance of the cured product and the low dielectric properties (low dielectric constant, low dielectric loss tangent) calculated as non-volatile components. In addition, the so-called non-volatile component refers to the component remaining after removing volatile components such as water and organic solvents.

[0060] The adhesive composition of the present invention may also contain an epoxy resin (B') other than the component (B) (hereinafter also referred to as the component (B')). As the molecular structure of the component (B'), a molecular structure having one or more epoxy groups at a molecular terminal, a molecular structure having one or more epoxy groups inside a molecule, or a molecular structure having one or more epoxy groups at a molecular terminal and inside a molecule can be used.

[0061] Examples of the component (B') include phenol novolac epoxy resins, cresol novolac epoxy resins, bisphenol A epoxy resins, bisphenol F epoxy resins, bisphenol S epoxy resins, hydrogenated bisphenol A epoxy resins, hydrogenated bisphenol F epoxy resins, distilbene epoxy resins, epoxy resins containing triazine skeletons, epoxy resins containing fluorene skeletons, linear aliphatic epoxy resins, alicyclic epoxy resins, trisphenol methane epoxy resins, alkyl-modified trisphenol methane epoxy resins, biphenyl epoxy resins, epoxy resins containing dicyclopentadiene skeletons, epoxy resins containing naphthalene skeletons, epoxy resins containing anthracene skeletons, aryl alkylene epoxy resins, dimer acid-modified epoxides which are dimer acid-modified products of the above epoxy resins, and dimer acid diglycidyl esters. In addition, aromatic amine epoxy resins having two glycidyl groups such as N,N-diglycidyl aniline, N,N-diglycidyl-o-toluidine, N,N-diglycidyl-m-toluidine, and N,N-diglycidyl-p-toluidine; monoglycidyl isocyanurate, diglycidyl isocyanurate, etc. can also be used. These can be used alone or in combination of two or more.

[0062] Examples of commercially available products of the component (B') include: "jER828", "jER834", "jER807", "jER871", and "jER872" (all manufactured by Mitsubishi Chemical Co., Ltd.), "ST-3000", and "YD-172-X75" (all manufactured by NIPPON STEEL Chemical & Material Co., Ltd.), "Celloxide 2021P" (manufactured by Daicel Co., Ltd.), "NC-513", "NC-514S", and "NC-547" (all manufactured by Cardolite Corp.), "NC-2000-L", "NC-3000", "NC-3000-L", and "NC-3100" (all manufactured by Nippon Kayaku Co., Ltd.), and "Sanso Nishizawa". cizer) E-2000H, "Sansocizer E-9000H" (all manufactured by Shin Nippon Rika Co., Ltd.), "Adeka resin EP-4000", "Adeka resin EP-4005", "Adeka resin EP-4100", "Adekaresin EP-4100G", "Adeka resin EP-4100E", "Adeka resin EP-4901", "Adeka cizer O-130P", "Adeka cizer O-180P" (all manufactured by ADEKA Co., Ltd.), etc.

[0063] The content of the component (B′) is preferably 5 parts by weight or less, more preferably 2 parts by weight or less, based on 100 parts by weight of the component (A) in terms of high adhesiveness of the cured product, in terms of nonvolatile matter.

[0064] The component (C) is a polyamine having no glycidyl group and having three or more amino groups, and refers to a compound having no glycidyl group and having three or more amino groups in the molecule. If the component (C) is used, the support film and the copper foil are bonded via the adhesive layer, and the adhesive layer is easy to show excellent solder heat resistance.

[0065] Examples of the component (C) include aliphatic polyamines such as diethylenetriamine, N,N-bis(2-aminoethyl)methylamine, 3,3'-diaminopropylamine, bis(tetraethylene)triamine, bis(pentaethylene)triamine, bis(hexylene)triamine, triethylenetetramine, and tetraethylenepentamine; Alicyclic polyamines such as 1,2,3-triaminocyclohexane, 1,2,4-triaminocyclohexane, 1,3,5-triaminocyclohexane, and trimer triamine; Aromatic polyamines such as 1,2,3-triaminobenzene, 1,2,4-triaminobenzene, 1,3,5-triaminobenzene, 1,3,5-tris(4-aminophenoxy)benzene; Polyamide polyamine, polyether polyamine, polyester triamine, etc. In addition, the "polyamine" here refers to a compound having three or more amino groups. They can be a single type or a combination of two or more types.

[0066] Among these, polyamide polyamine, polyether polyamine, and trimer triamine are preferred, and polyamide polyamine and / or polyether polyamine are more preferred, because the adhesive layer exhibits excellent solder heat resistance.

[0067] Examples of commercially available products of polyamide polyamine 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 Co., Ltd.), “Luckamide TD-960,” “Luckamide TD-984,” and “Luckamide TD-982” (all manufactured by DIC Corporation).

[0068] Examples of commercially available products of polyether polyamine include: “PEG#1000 diamine” (manufactured by NOF Corporation), “JAFFAMINE T-403” and “JAFFAMINE T-5000” (manufactured by HUNTSMAN), and “BAXXODUR EC310” and “BAXXODUR EC311” (manufactured by BASF).

[0069] Trimer triamine is a compound in which all carboxyl groups of a trimer acid (see Japanese Patent Publication No. 2013-505345, etc.) which is a trimer of an unsaturated fatty acid such as oleic acid are replaced by primary amino groups. Commercially available products include "PRIAMINE 1071" and "PRIAMINE 1073" (both manufactured by Croda Japan Co., Ltd.).

[0070] The content of the component (C) is preferably 0.1 to 8 parts by weight, more preferably 0.5 to 5 parts by weight, and even more preferably 1 to 3.5 parts by weight, based on non-volatile content, relative to 100 parts by weight of the component (A), in terms of excellent solder heat resistance of the cured product.

[0071] The adhesive composition of the present invention may further contain other curing agents such as benzoxazine, bismaleimide, cyanate, polyisocyanate, phosphorus compound, acid anhydride, amine other than component (C), imidazole, guanidine, phenol resin, active ester, and the like.

[0072] Examples of benzoxazine 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). In addition, a phenyl group, a methyl group, a cyclohexyl group, or the like may be bonded to the nitrogen of the oxazine ring.

[0073] Examples of commercially available benzoxazine include "benzoxazine Fa type" and "benzoxazine Pd type" (each manufactured by Shikoku Chemical Industries, Ltd.) and "RLV-100" (manufactured by Air Water Co., Ltd.).

[0074] Examples of the bismaleimide include N,N'-ethylenebismaleimide, N,N'-trimethylenebismaleimide, N,N'-tetramethylenebismaleimide, N,N'-pentamethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N'-hexamethylenebismethylmaleimide, N,N-heptamethylenebismaleimide, N,N-octamethylenebismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, and N,N'-alkylenebismaleimides such as 1,1'-(decane-1,10-diyl)bis(1H-pyrrole-2,5-dione); Bismaleimides having 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); Phenylene bismaleimides such as N,N'-xylene bismaleimide, N,N'-tolylene bismaleimide, N,N'-xylylene 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); 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'-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-maleimide phenoxy)benzene, 1,3-bis(3-maleimide phenoxy)benzene, 1,3-bis(4-maleimide phenoxy)benzene, N,N'-3,3'-diphenyl sulfone bismaleimide, N,N'-4,4'-diphenyl sulfone bismaleimide, N,N'-dichlorodiphenyl bismaleimide, 1,1'-[2,2'-bis(trifluoromethyl){1,1'-biphenyl}-4,4'-diyl]bis[1H-pyrrole-2,5-dione] and other N,N'-diphenyl bismaleimides; Bis(phenoxyphenyl)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]hexafluoropropane, and the like. These may be used alone or in combination of two or more.

[0075] In addition, commercially available products of bismaleimide include: "BMI", "BMI-70", "BMI-80" (all manufactured by KI Chemical Industry 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" (all manufactured by Yamato Chemical Industry Co., Ltd.), etc.

[0076] In addition, as bismaleimide, bismaleimide derived from the dimer diamine (hereinafter referred to as maleimides having a dimer diamine skeleton) can also be used. Commercially available products of the bismaleimide 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 (Solution)", "BMI-5000P", "BMI-5000T", "BMI-6000", "BMI-6100" (all manufactured by Designer Molecule Inc.) and the like.

[0077] Examples of the cyanate ester 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.

[0078] Examples of commercially available products of cyanate esters include "PRIMASET BTP-6020S" (manufactured by Lonza Japan Co., Ltd.).

[0079] Examples of the polyisocyanate 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 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; Aromatic polyisocyanates such as xylylene diisocyanate, toluene diisocyanate, phenylene diisocyanate, tetramethylxylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, m-tetramethylxylylene diisocyanate and naphthalene diisocyanate.

[0080] In addition, as the polyisocyanate, a biuret form, an isocyanurate form, an allophanate form, or an adduct form of the above-mentioned polyisocyanate may be used. These polyisocyanates may be used alone or in combination of two or more.

[0081] Regarding commercially available polyisocyanates, for example, Examples of the biuret body include "Duranate 24A-100", "Duranate 22A-75P", "Duranate 21S-75E" (all manufactured by Asahi Kasei Co., Ltd.), and "Desmodur N3200A" (all manufactured by Sumitomo Bayer Urethane Co., Ltd.). Examples of isocyanurate bodies include "Duranate TPA-100", "Duranate TKA-100", "Duranate MFA-75B", "Duranate MHG-80B" (all manufactured by Asahi Kasei Co., Ltd.), "Coronate HXR" (manufactured by Tosoh Co., Ltd.), "Takenate D-131N", "Takenate D204EA-1", "Takenate D-127N" (all manufactured by Mitsui Chemicals Co., Ltd.), and "VESTANAT T1890 / 100" (manufactured by Evonik Japan Co., Ltd.). Examples of allophanate bodies include "Takenate D-178N" (manufactured by Mitsui Chemicals Co., Ltd.), Examples of the adductor include "Duranate P301-75E" (manufactured by Asahi Kasei Co., Ltd.), "Takenate D110N", "Takenate D160N" (both manufactured by Mitsui Chemicals Co., Ltd.), and "Coronate L" (manufactured by Tosoh Co., Ltd.).

[0082] 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, butyltriphenylphosphonium thiocyanate, etc. These may be used alone or in combination of two or more.

[0083] Examples of the acid anhydride include succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, norbornane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 3-dodecenyl succinic anhydride, octenyl succinic anhydride, etc. These may be used alone or in combination of two or more.

[0084] Examples of amines other than the component (C) include aliphatic amines such as trimethylamine, triethylamine, tributylamine, ethylenediamine, and triethylenediamine; Amino alcohols such as triethanolamine and dimethylaminoethanol; Oxyalkylenediamines such as polyoxyethylenediamine and polyoxypropylenediamine; Alicyclic amines such as cyclopentylamine, cyclohexylamine, 1,2-diaminocyclopentane, 1,3-diaminocyclopentane, 1,2-diaminocyclohexane, 1,3-diaminocyclohexane, and 1,4-diaminocyclohexane; Aromatic amines such as 1,3-aminobenzene, benzyldimethylamine, and 1,3-bis(aminomethyl)benzene; 4-dimethylaminopyridine, N-aminoethylpiperazine, heterocyclic amines such as 1,8-diazabicyclo[5,4,0]-undecene, etc. These may be used alone or in combination of two or more.

[0085] Examples of imidazoles 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'-methylimidazole] 2,4-diamino-6-[2'-undecylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-ethyl-4'-methylimidazolyl-(1')]-ethyl-s-triazine, 2,4-diamino-6-[2'-methylimidazolyl-(1')]-ethyl-s-triazine, 2-phenylimidazole isocyanuric acid adduct, 2-phenyl-4,5-dihydroxymethylimidazole, 2-phenyl-4-methyl-5-hydroxymethylimidazole, 2,3-dihydro-1H-pyrrolo[1,2-a]benzimidazole, 1-dodecyl-2-methyl-3-benzylimidazolium chloride, 2-methylimidazoline, 2-phenylimidazoline, etc. These may be used alone or in combination of two or more.

[0086] 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.

[0087] Examples of the phenol resin include phenol novolac resins, cresol novolac resins, bisphenol A novolac resins, triazine-modified phenol novolac resins, and phosphazenes containing a phenolic hydroxyl group. These may be used alone or in combination of two or more.

[0088] As active esters, for example, compounds containing a dicyclopentadienyl diphenol structure, compounds containing a naphthalene structure, acetylated products of phenol novolac, benzoylated products of phenol novolac, etc., described in Japanese Patent Laid-Open No. 2019-183071, can be cited. These may be a single type or a combination of two or more types.

[0089] Regarding commercially available active esters, for example, Examples of the compound containing a dicyclopentadienyl diphenol structure 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" (all manufactured by DIC Corporation of America). Examples of the compound containing a naphthalene structure include "EXB9416-70BK" (manufactured by DIC Corporation); Examples of acetylated phenol novolacs include "DC808" (manufactured by Mitsubishi Chemical Corporation); Examples of the benzoylated product of phenol novolac include "YLH1026", "YLH1030" and "YLH1048" (all manufactured by Mitsubishi Chemical Corporation).

[0090] As the active ester, compounds produced by various known methods may be used, and examples thereof include compounds produced by reacting a polyfunctional phenol compound with an aromatic carboxylic acid as described in Japanese Patent No. 5152445.

[0091] The content of the other curing agent is preferably 0.5 parts by weight or less, more preferably 0.1 parts by weight or less, and even more preferably 0.01 parts by weight or less, based on 100 parts by weight of the component (A), in terms of nonvolatile matter.

[0092] The adhesive composition of the present invention may further contain a phosphorus-based flame retardant.

[0093] Phosphorus flame retardants include polyphosphoric acid or phosphoric acid esters, phosphazene derivatives without phenolic hydroxyl groups, etc. Among the phosphazene derivatives, cyclic phosphazene derivatives are preferred in terms of flame retardancy, heat resistance, and anti-bleeding properties. Commercially available products of cyclic phosphazene derivatives include "SPB-100" (manufactured by Otsuka Chemical Co., Ltd.), "Rabitle FP-300B" (manufactured by Fushimi Pharmaceutical Co., Ltd.), etc.

[0094] 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 nonvolatile matter.

[0095] The adhesive composition of the present invention may contain a general formula: W-Si(R 1 ) a (OR 2 ) 3-a (wherein, W represents a group containing a functional group that reacts with an acid anhydride group, R 1 represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R 2 A reactive alkoxysilyl compound represented by (a) represents a hydrocarbon group having 1 to 8 carbon atoms, and a represents 0, 1 or 2. The reactive alkoxysilyl compound can adjust the melt viscosity of the adhesive layer while maintaining low dielectric properties. As a result, the interfacial adhesion between the adhesive layer and the support (so-called anchoring effect) can be improved while suppressing the oozing of the adhesive layer from the end of the support.

[0096] Examples of the reactive functional group contained in W of the general formula include an amino group, an epoxy group, and a thiol group. In addition, the reactive alkoxysilyl compound having an amino group does not belong to the amines exemplified in the component (C) and other curing agents.

[0097] The compound containing amino group in W includes: N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and 3-ureidopropyltrialkoxysilane. As the compound containing epoxy group in W, for example, 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxypropyltrimethoxysilane, 3-glycidyloxypropylmethyldiethoxysilane and 3-glycidyloxypropyltriethoxysilane can be listed. As the compound containing thiol group in W, for example, 3-mercaptopropyltrimethoxysilane or 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropylmethyldiethoxysilane can be listed. Among these, compounds containing an amino group are preferred because of good reactivity and flow rate control effects.

[0098] As content of a reactive alkoxysilyl compound, it is preferable that it is 0.01 weight part - 5 weight part with respect to 100 weight part of (A) components in conversion of a non-volatile matter.

[0099] The adhesive composition of the present invention may contain an inorganic filler, but preferably contains no inorganic filler from the viewpoint of making it easy for the adhesive layer to exhibit excellent solder heat resistance.

[0100] Examples of inorganic fillers include silica fillers, phosphorus fillers, fluorine fillers, inorganic ion exchanger fillers, etc. In addition, silica fillers whose surfaces have been modified with a treatment agent such as a silane coupling agent may be used. These may be used alone or in combination of two or more.

[0101] Commercially available products of inorganic fillers include, for example, “FB-3SDC”, “SFP-20M” (all manufactured by Denka Co., Ltd.), “SC-2500-SPJ”, “SC-2500-SXJ”, “SC-2500-SVJ”, “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.).

[0102] The adhesive composition of the present invention may further contain the organic solvent. The content of the organic solvent may be adjusted so that the non-volatile component concentration of the adhesive composition is preferably 15 to 40 wt %, more preferably 20 to 35 wt %.

[0103] The adhesive composition of the present invention may contain, as an additive, a compound other than component (A), component (B), component (C), other curing agents, phosphorus-based flame retardants, reactive alkoxysilyl compounds, inorganic fillers, and organic solvents.

[0104] Examples of the additives include ring-opening esterification catalysts, dehydrating agents, plasticizers, weathering agents, antioxidants, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents, mold release agents, surface treatment agents, viscosity modifiers, inorganic pigments, organic pigments, and the like.

[0105] The content of the additive 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, based on 100 parts by weight of the component (A), as calculated as a nonvolatile component.

[0106] The adhesive composition of the present invention can be obtained by adding the components (A), (B) and (C), other curing agents as required, phosphorus-based flame retardants, reactive alkoxysilane compounds, organic solvents and additives, and dissolving them while mixing.

[0107] [Hardened material] In the present invention, the cured product of the adhesive composition is also one of the embodiments. As a method for manufacturing the cured product, there can be cited a process including applying the adhesive composition to a suitable support, a process of curing by volatilizing an organic solvent by heating, a process of peeling off the support, etc. In addition, the thickness of the cured product is preferably 3μm to 40μm. As a support, there can be cited: release paper, release film, support film described later, etc. In addition, when manufacturing the cured product, the adhesive composition and various known adhesive compositions other than the adhesive composition can also be used together. Furthermore, the cured product obtained can also be used as a resin film by peeling off the support.

[0108] [Adhesive sheet] The adhesive sheet of the present invention comprises the cured product of the present invention on at least one surface of a support film.

[0109] The adhesive sheet can be obtained, for example, by applying the adhesive 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.

[0110] As the support film, for example, polyimide, polyester, polyimide-silicon oxide mixture, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin, aromatic polyester resin obtained from polyethylene terephthalate, phenol, phthalic acid, hydroxynaphthoic acid, etc. and p-hydroxybenzoic acid (so-called liquid crystal polymer; "Vecstar" (manufactured by Kuraray (co., Ltd.)), cycloolefin polymer (cycloolefin polymer, COP), fluorine resin (polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PerfluoroalkoxyAlkane, PFA), polyvinylidene fluoride (Polyvinylidene Fluoride, PVDF), etc.) etc. Polyimide includes the polyimide film of the present invention.

[0111] When the adhesive composition of the present invention is applied to a support film, as a coating method, for example, a coating machine such as a notch wheel coater, a die coater, a knife coater, a lip coater, etc. can be cited. As the thickness of the coating layer, after drying, it is preferably about 1 μm to 100 μm, and 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.

[0112] [Copper foil with resin] The resin-bearing copper foil of the present invention comprises the cured product or adhesive sheet of the present invention and the copper foil. Specifically, the adhesive composition of the present invention is applied to the copper foil and heat-cured, or the cured product of the present invention is bonded to the copper foil. As the copper foil, for example, rolled copper foil or electrolytic copper foil can be cited, and copper foil subjected to various surface treatments (roughening, rustproofing, etc.) can also be used. The rustproofing treatment can be cited as a so-called mirror treatment such as a plating treatment using a plating solution containing Ni, Zn, Sn, etc., and a chromate treatment.

[0113] The thickness of the copper foil is preferably about 1 μm to 100 μm, and more preferably about 2 μm to 38 μm. In addition, the above-mentioned method can be cited as the coating means.

[0114] In addition, the layer (or cured product) of the adhesive composition before curing of the copper foil with resin can also be partially cured or completely cured under heating. The partially cured adhesive layer or cured product is in a state called the so-called B stage. In addition, the thickness of the adhesive layer or cured product is preferably about 0.5μm to 30μm. In addition, the cured product can be further attached to the copper foil of the copper foil with resin to make a double-sided copper foil with resin.

[0115] [Copper Clad Laminated Board] The copper-clad laminate of the present invention comprises the copper foil with resin and copper foil or insulating sheet of the present invention. The copper-clad laminate is also called copper foil substrate (Copper Clad Laminate, CCL). Specifically, the copper-clad laminate is formed by pressing the copper foil with resin to at least one or both sides of various known copper foils or insulating sheets under heating. In the case of laminating to one side, a copper foil different from the copper foil with resin can also be pressed 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.

[0116] As an insulating sheet, a prepreg or the support film is preferred. A prepreg refers to a sheet material (Japanese Industrial Standards (JIS) C 5603) in which a resin is impregnated in a reinforcing material such as glass cloth and hardened to the B stage. The resin can use insulating resins such as the adhesive composition of the present invention, phenolic resins, epoxy resins, polyester resins, liquid crystal polymers, and aromatic polyamide resins. As the thickness of the insulating sheet, it is preferably about 20 μm to 500 μm. As heating / compression bonding conditions, it is preferably about 150°C to 280°C (more preferably about 170°C to 240°C) and preferably about 0.5MPa to 20MPa (more preferably about 1MPa to 8MPa).

[0117] [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. The means of patterning the circuit pattern on the copper foil surface of the copper-clad laminate can be subtractive method and semi-additive method. As a semi-additive method, the method of electrolytic copper plating, removing the resist, and etching with alkali solution after patterning the copper foil surface of the copper-clad laminate can be cited. In addition, the thickness of the circuit pattern layer in the printed wiring board is not particularly limited. In addition, it is also possible to obtain a multilayer substrate by setting the printed wiring board as a core and stacking the same printed wiring board or other known printed wiring boards or printed circuit boards thereon. When stacking, the adhesive composition and other known adhesive compositions other than the adhesive composition can be used in combination. In addition, the number of stacking in the multilayer substrate is not particularly limited. In addition, each time the stacking is performed, a through hole can also be inserted and the inside can be plated. The line / space ratio of the circuit pattern is preferably about 1μm / 1μm to 100μm / 100μm. In addition, the height of the circuit pattern is preferably about 1 μm to 50 μm. [Example]

[0118] Hereinafter, the present invention will be specifically described with reference to Examples, but the present invention is not particularly limited thereto. In addition, "%" is based on weight unless otherwise specified.

[0119] Production Example 1 A reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen inlet tube was charged with 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, hereinafter referred to as BisDA-1000), 806.32 g of toluene, and 345.57 g of 1,2-dimethoxyethane, and heated to 40° C. Subsequently, 20.34 g of 4,4'-diaminophenyl ether (trade name: "ODA", manufactured by Wakayama Seika Industries, hereinafter referred to as ODA) was added, and heated again to 70° C. Then, 219.45 g of dimer diamine (trade name: "PRIAMINE 1075", manufactured by Croda Japan Co., Ltd.) was gradually added, and imidization reaction was performed at 110° C. for 14 hours to obtain a solution of polyimide (A-1) (nonvolatile content 30%).

[0120] Production Example 2 280.00 g of BisDA-1000, 864.24 g of toluene and 370.39 g of 1,2-dimethoxyethane were placed in the same reaction container as in Production Example 1 and heated to 75° C. Then, 275.35 g of dimer diamine (PRIAMINE 1075) was slowly added, and imidization reaction was performed at 110° C. for 14 hours to obtain a solution of polyimide (A-2) (non-volatile content 30%).

[0121] Production Example 3 In the same reaction container as in Production Example 1, 280.00 g of BisDA-1000, 749.94 g of toluene and 321.40 g of 1,2-dimethoxyethane were placed and heated to 40° C. Subsequently, 40.69 g of ODA was added and heated again to 70° C. Then, 164.59 g of dimer diamine (PRIAMINE 1075) was slowly added and imidization reaction was performed at 110° C. for 14 hours to obtain a solution of polyimide (A-3) (non-volatile content 30%).

[0122] Production Example 4 Into the same reaction container as in Production Example 1, 280.00 g of BisDA-1000, 721.75 g of toluene and 309.32 g of 1,2-dimethoxyethane were placed and heated to 40° C. Subsequently, 50.86 g of ODA was added and heated again to 70° C. Then, 137.16 g of dimer diamine (PRIAMINE 1075) was slowly added and imidization reaction was performed at 110° C. for 14 hours to obtain a solution of polyimide (A-4) (non-volatile content 30%).

[0123] Production Example 5 Into the same reaction container as in Production Example 1, 280.00 g of BisDA-1000 and 739.57 g of cyclohexanone were placed and heated to 60° C. Subsequently, 187.77 g of dimer diamine (PRIAMINE 1075) was placed and heated to 100° C. again. Subsequently, 23.28 g of 1,3-bisaminomethylcyclohexane was added dropwise, the mixture was cooled to 80° C., 222.30 g of 1,2-dimethoxyethane and 122.54 g of methylcyclohexane were added, and an imidization reaction was carried out at 140° C. for 14 hours to obtain a solution of polyimide (A-5) (non-volatile content 30%).

[0124] Production Example 6 Into the same reaction container as in Production Example 1, 280.00 g of BisDA-1000, 1050.04 g of toluene and 450.02 g of 1,2-dimethoxyethane were placed and heated to 85° C. Subsequently, 181.73 g of dimer diamine (PRIAMINE 1075) and 63.14 g of 9,9-bis(4-aminophenyl)fluorene (trade name: "BAFL", manufactured by JFE Chemical Co., Ltd., hereinafter referred to as BAFL) were added, and imidization reaction was carried out at 110° C. for 14 hours to obtain a solution of polyimide (A-6) (non-volatile content 30%).

[0125] Production Example 7 Into the same reaction container as in Production Example 1, 280.00 g of 3,3',4,4'-biphenyltetracarboxylic dianhydride (trade name: "BPDA", manufactured by Mitsubishi Chemical Co., Ltd.; hereinafter referred to as BPDA) and 1776.32 g of cyclohexanone were placed and heated to 90° C. Subsequently, 276.58 g of dimer diamine (PRIAMINE 1075), 146.02 g of BAFL and 197.37 g of methylcyclohexane were added, and imidization reaction was carried out at 140° C. for 14 hours to obtain a solution of polyimide (A-7) (non-volatile content 25%).

[0126] Production Example 8 Into the same reaction container as in Production Example 1, 280.00 g of BPDA and 1728.16 g of cyclohexanone were placed and heated to 90° C. Subsequently, 226.29 g of dimer diamine (PRIAMINE 1075), 178.47 g of BAFL and 192.02 g of methylcyclohexane were added, and imidization reaction was carried out at 140° C. for 15 hours to obtain a solution of polyimide (A-8) (non-volatile content 25%).

[0127] Example 1 302.11 g of component (A-1) (100.0 g of non-volatile matter), 5.85 g of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane (trade name: "jER604", manufactured by Mitsubishi Chemical Co., Ltd.) (1.17 g of non-volatile matter), 6.07 g of polyether polyamine (trade name: "JAFFAMINE T-403", manufactured by Huntsman Co., Ltd.) (1.52 g of non-volatile matter), and 96.71 g of toluene as an organic solvent were mixed and stirred thoroughly to obtain an adhesive composition having a non-volatile matter content of 25%.

[0128] Example 2 to Example 14, Comparative Example 1 to Comparative Example 7 The compositions shown in Table 1 were changed to those shown in Table 1, and the same method as in Example 1 was used to obtain adhesive compositions.

[0129] <Cured product (adhesive layer)> The adhesive composition of each embodiment and comparative example was applied to a release paper (manufactured by Sun A Kaken Co., Ltd.) using a gap coater to a thickness of 5 μm after drying, and then dried at 150° C. for 5 minutes, and then the release paper was peeled off to obtain a cured product (adhesive layer) (hereinafter referred to as the adhesive layer). In addition, in the adhesive composition of Comparative Example 6, a gap was generated between the copper foil and the adhesive layer when the copper-clad laminate described later was produced, so the cured product was not produced.

[0130] <Relative dielectric constant and dielectric loss tangent> The adhesive layer was placed on a pressing support, and then hardened by heating and pressing at a pressure of 6 MPa and 220° C. for 30 seconds with the same pressing support interposed on the adhesive layer side, thereby preparing a heat-hardened adhesive sheet (support / adhesive layer / support). The pressing support was removed from the adhesive layer, and the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the adhesive layer were calculated using the following method. The resonance frequency and peak Q value of a resonator unit without any components inserted were measured using a network analyzer (Keysight Technologies, device name: "P5003A") and split postdielectric resonators (SPDR) with a measurement frequency of 10.124 GHz (QWED). Next, the adhesive layer was cut into 4 cm×5 cm pieces to prepare test pieces, and a plurality of test pieces were stacked so as to have a total thickness of 100 μm or more and inserted into the resonator. The resonance frequency and Q value when the test pieces were inserted were measured. The relative dielectric constant (Dk) is calculated from the difference in resonant frequency between the resonator alone and when the test piece is inserted, and the dielectric loss tangent (Df) is calculated from the difference in Q value and resonant frequency between the resonator alone and when the test piece is inserted. When the relative dielectric constant is 3.0 or less and the dielectric loss tangent is 0.004 or less, it indicates low dielectric properties. The results are shown in Table 1.

[0131] <Adhesive sheet> The adhesive composition 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 a manner such that the thickness after drying was 4 μm, and then dried at 150°C for 5 minutes to obtain adhesive sheets (Kapton / adhesive layer).

[0132] <Copper clad laminate> The adhesive layer side of the adhesive sheet (Kapton / adhesive 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 / adhesive layer / electrolytic copper foil). Then, it is placed on a pressing support, and the support obtained from the same raw material is heated and pressed from above at a pressure of 6 MPa and a temperature of 220°C for 30 seconds to produce copper-clad laminates. In addition, in the adhesive composition of Comparative Example 6, a gap is generated between the copper foil and the adhesive layer, so the bonding strength and solder heat resistance are not evaluated.

[0133] <Fitting> The appearance of the copper-clad laminate was confirmed and evaluated based on the following criteria. The results are shown in Table 2. ○: No gaps or expansion on the copper-clad laminate △: Slight gap or expansion on the copper-clad laminate ×: There are gaps or expansions in the copper-clad laminate

[0134] <Adhesion Strength> The peel strength (N / mm) of the copper-clad laminate was measured in accordance with JIS C 6481 (Testing methods for copper-clad laminates for flexible printed wiring boards).

[0135] <Solder Heat Resistance> The copper-clad laminate was placed in a thermostatic chamber at 23° C. and 50% humidity for 24 hours, and then floated in a solder bath at 288° C. with the copper foil facing downward to confirm the presence or absence of blistering and evaluate the results according to the following criteria. (Evaluation Criteria) ○: No change in appearance △: Half of the copper-clad laminate has foaming, expansion, and peeling ×: The copper-clad laminate has foaming, expansion, and peeling as a whole

[0136] [Table 1]

[0137] The symbols shown in Table 1 represent the following compounds, respectively. (Polyimide) A-1: Polyimide of Production Example 1 ·A-2: Polyimide of Production Example 2 ·A-3: Polyimide of Production Example 3 ·A-4: Polyimide of Production Example 4 ·A-5: Polyimide of Production Example 5 A-6: Polyimide of Production Example 6 ·A-7: Polyimide of Production Example 7 ·A-8: Polyimide of Production Example 8 (Epoxy resin) · B-1: N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane (trade name: "jER604", manufactured by Mitsubishi Chemical Co., Ltd.) · B-2: N,N,N',N'-tetraglycidyl-m-xylylenediamine (trade name: "TETRAD-X", manufactured by Mitsubishi Gas Chemical Co., Ltd.) · B-3: N,N-diglycidyl-4-glycidyloxyaniline (trade name: "jER630", manufactured by Mitsubishi Chemical Co., Ltd.) · E-1: Bisphenol A type epoxy resin (trade name: "jER828", manufactured by Mitsubishi Chemical Co., Ltd.) · E-2: Naphthalene type epoxy resin (trade name: "Epiclon HP-4710", manufactured by DIC Corporation) · E-3: Epoxy resin having a glycerol ester skeleton (trade name: "Sanso cizer E-2000H", manufactured by Shin Nippon Chemical Co., Ltd.) (amine) C-1: Polyether polyamine (trade name: "JAFFAMINE T-403", manufactured by HUNTSMAN) C-2: Polyamide polyamine (trade name: "Vegechem Green V140", manufactured by Chikuno Food Industry Co., Ltd.) C-3: trimer triamine (trade name: "PRIAMINE 1071", manufactured by Croda Japan Co., Ltd.) F-1: polyoxypropylene diamine (trade name: "JAFFAMINE D-400", manufactured by HUNTSMAN).

Claims

1. An adhesive composition comprising: a polyimide (A) which is a reaction product of a monomer group comprising an aromatic tetracarboxylic anhydride (a1) and a diamine (a2) containing a dimer diamine, an amine-type epoxy resin (B) having three or more glycidyl groups, and A polyamine (C) having no glycidyl group and having three or more amino groups.

2. The adhesive composition according to claim 1, wherein (C) Component is one or more selected from the group consisting of polyamide polyamine, polyether polyamine and trimer triamine. 3 . The adhesive composition according to claim 1 , which does not contain an inorganic filler. 4 . A cured product, which is a cured product of the adhesive composition according to claim 1 . 5 . An adhesive sheet comprising the cured product according to claim 4 on at least one surface of a support film. 6 . A copper foil with resin, comprising the cured product according to claim 4 or the adhesive sheet according to claim 5 , and a copper foil. 7 . A copper-clad laminate comprising the copper foil with resin according to claim 6 , and a copper foil or an insulating sheet. 8 . A printed wiring board having a circuit pattern on the copper foil surface of the copper-clad laminate according to claim 7 .

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