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

Abstract

To provide an adhesive composition for producing an adhesive layer that exhibits high adhesive strength through enhanced bonding to hard-to-bond substrates such as fluorine-based resin, along with superior solder heat resistance, while maintaining low dielectric properties (low dielectric constant and low dielectric loss tangent).SOLUTION: An adhesive composition includes a polyimide resin (A), which is a product of reaction components including an aromatic tetracarboxylic dianhydride (a1) and a diamine (a2) including dimer diamine, an epoxy resin (B), a bismaleimide with a dimer diamine skeleton (C), and a diene-based polymer (D) with a 1,2-vinyl group in its side chain.SELECTED DRAWING: None

Description

[Technical field]

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

[0002] Polyimide resins are generally obtained by reacting tetracarboxylic anhydrides with diamines. They have various properties such as heat resistance, adhesion, and mechanical properties, and are often used as protective films and insulating sealing films for semiconductors, and adhesive compositions for flexible printed wiring boards and printed circuit boards.

[0003] In recent years, high-frequency electrical signals have come to be used to transmit and process large volumes of information at high speed. However, because high-frequency signals are highly susceptible to attenuation, there is a demand for methods to minimize transmission loss in the multilayer wiring boards. In this regard, polyimide resins, which have low dielectric properties (low dielectric constant, low dielectric tangent), are useful.

[0004] As such a technique, the present applicant has disclosed an adhesive composition containing a polyimide having a tetracarboxylic acid residue and a diamine residue derived from a 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 adheres to the insulating film such as polyimide and the copper foil, respectively, and exerts high adhesive strength. Meanwhile, in recent years, in order to meet the demand for further high frequencies, there has been a movement to use fluorine-based resins such as polytetrafluoroethylene (PTFE) and perfluoroalkoxyalkane (PFA) as insulating films with lower dielectric properties. However, when a fluorine-based resin was used, the adhesive layer did not adhere sufficiently, and the adhesive strength was reduced. Furthermore, the solder heat resistance was also poor. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2018-121807 A Summary of the Invention [Problem to be solved by the invention]

[0006] The present invention aims to provide an adhesive composition which maintains low dielectric properties (low dielectric constant and low dielectric tangent), exhibits high adhesive strength by improving adhesion to poorly adherent substrates such as fluororesins, and further provides an adhesive layer which is excellent in solder heat resistance. [Means for solving the problem]

[0007] The present inventors have conducted extensive research and have found a solution to the above problems, thereby completing the present invention.

[0008] 1. A polyimide resin (A) which is a product of reaction components including an aromatic tetracarboxylic dianhydride (a1) and a diamine (a2) including a dimer diamine, and an epoxy resin (B); Bismaleimide (C) having a dimer diamine skeleton, and An adhesive composition comprising a diene polymer (D) having a 1,2-vinyl group in the side chain.

[0009] 2. The adhesive composition according to item 1 above, further comprising an active ester (E).

[0010] 3. A cured product comprising the adhesive composition described in the preceding item 1.

[0011] 4. An adhesive sheet having the cured product described in item 3 above on at least one side of a support film.

[0012] 5. A resin-coated copper foil comprising the cured product described in the preceding paragraph 3 or the adhesive sheet described in the preceding paragraph 4, and a copper foil.

[0013] 6. A copper-clad laminate comprising the resin-coated copper foil according to the preceding paragraph 5 and a copper foil or an insulating sheet.

[0014] 7. A printed wiring board having a circuit pattern on the copper foil surface of the copper-clad laminate described in the preceding paragraph 6. Effect of the Invention

[0015] The adhesive composition of the present invention maintains low dielectric properties (low dielectric constant and low dielectric tangent), and when made into a copper-clad laminate, provides an adhesive layer that exhibits high adhesive strength due to improved adhesion to difficult-to-adhere substrates such as fluororesins, and also has excellent solder heat resistance. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0016] 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) (hereinafter referred to as component (a2)), an epoxy resin (B) (hereinafter referred to as component (B)), a bismaleimide (C) (hereinafter referred to as component (C)) having a dimer diamine skeleton, and a diene-based polymer (D) (hereinafter referred to as component (D)) having a 1,2-vinyl group in the side chain.

[0017] Component (A) is a polyimide resin, and is a component used to provide a layer of the adhesive composition (hereinafter referred to as the adhesive layer) with a low dielectric constant and a low dielectric loss tangent.

[0018] 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-phenyleneoxy)]diphthalic dianhydride, 2,2',3,3'-Benzophenonetetracarboxylic dianhydride, 2,3,3',4'-Benzophenonetetracarboxylic dianhydride, 3,3',4,4'-Benzophenonetetracarboxylic dianhydride, 2,3',3,4'-Diphenyl ether 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 anhydride, 2,3,6,7-naphthalenetetracarboxylic anhydride, 2,3,6,7-anthracenetetracarboxylic anhydride Acid dianhydrides, 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.

[0019] Among these, from the viewpoints of the flexibility of the adhesive layer and the solder heat resistance, the component (a1) is preferably one represented by the following general formula (1): [ka] (In formula (1), X is 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 represents -OCO-, and p represents an integer of 1 to 20.

[0020] Examples of compounds 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)hexafluoropropanetetracarboxylic dianhydride, and 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropanetetracarboxylic dianhydride. Examples of suitable dianhydrides include tetrafluoropropane 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, and 2,2'-bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride. These may be used alone or in combination of two or more. Among these, 2,2-bis(3,4-dicarboxyphenyl)hexafluoropropane dianhydride and 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride are preferred because the component (A) is well soluble in an organic solvent.

[0021] The amount of the component (a1) used in 100 mol % of the monomers constituting the component (A) is usually 10 to 90 mol %, and preferably 25 to 75 mol %.

[0022] The amount of the tetracarboxylic acid anhydride represented by the general formula (1) used in 100 mol % of the monomers constituting the component (A) is usually 10 to 90 mol %, and preferably 25 to 75 mol %.

[0023] The amount of the tetracarboxylic acid anhydride represented by the general formula (1) used in 100 mol % of the component (a1) is usually 10 to 100 mol %, and preferably 50 to 100 mol %.

[0024] The component (a2) is a diamine containing a dimer diamine.

[0025] Dimer diamine is a dimer acid in which all carboxyl groups have been replaced with primary amino groups or primary aminomethyl groups (see, for example, JP-A-9-12712). Here, dimer acid mainly includes a dibasic acid having 36 carbon atoms obtained by dimerizing unsaturated fatty acids such as oleic acid, linoleic acid, and 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. The dimer acid includes a double bond, and the degree of unsaturation may be reduced by, for example, a hydrogenation reaction.

[0026] The dimer diamine may, for example, be one represented by the following general formula (2): In general formula (3), m+n is preferably 6 to 17, p+q is preferably 8 to 19, and the dashed line represents a carbon-carbon single bond or a carbon-carbon double bond.

[0027] [ka]

[0028] Commercially available dimer diamines include "VERSAMINE 551" and "VERSAMINE 552" (both manufactured by Cognics Japan, Inc.), "PRIAMINE 1073", "PRIAMINE 1074", and "PRIAMINE 1075" (all manufactured by Croda Japan, Inc.). Of these commercially available 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).

[0029] [ka]

[0030] [ka]

[0031] The dimer diamine may contain amines derived from the monomer acid, trimer acid and / or polymerized fatty acid, and the content thereof 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.

[0032] Furthermore, the dimer diamine may be used as it is, or may be used after being subjected to a purification treatment such as distillation.

[0033] The amount of dimer diamine used in 100 mol % of the monomers constituting the component (A) is usually 5 mol % or more, and preferably 25 to 75 mol %.

[0034] The amount of dimer diamine used in 100 mol % of the component (a2) is usually 10 mol % or more, and preferably 30 to 100 mol %.

[0035] The component (a2) may also contain a diamine (a2') other than dimer diamine (hereinafter referred to as component (a2'). The component (a2') may also contain, for example, an aliphatic diamine, an alicyclic diamine, an aromatic diamine, a diaminoether, or a diaminopolysiloxane. Note that these amines exclude dimer diamine.

[0036] 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.

[0037] Examples of alicyclic diamines include diaminocyclohexane, diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, diaminodicyclohexylpropane, tetramethyldiaminodicyclohexylmethane, 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, diaminobicyclo[2.2.1]heptane, bis(aminomethyl)-bicyclo[2.2.1]heptane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0(2,6)]decane, and isophoronediamine.

[0038] Examples of aromatic diamines 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-di(3-aminophenyl)propane, 2,2-di(4-aminophenyl)propane, and 2-(3-aminophenyl)-2-(4-aminophenyl)propane; diaminophenylhexafluoropropanes such as 2,2-di(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-di(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, and 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane; Diaminophenylphenylethanes such as 1,1-di(3-aminophenyl)-1-phenylethane, 1,1-di(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; Bisaminobenzoylbenzenes such as 1,3-bis(3-aminobenzoyl)benzene, 1,3-bis(4-aminobenzoyl)benzene, 1,4-bis(3-aminobenzoyl)benzene, and 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, and 1,4-bis(4-amino-α,α-dimethylbenzyl)benzene; bisaminoditrifluoromethylbenzylbenzenes such as 1,3-bis(3-amino-α,α-ditrifluoromethylbenzyl)benzene, 1,3-bis(4-amino-α,α-ditrifluoromethylbenzyl)benzene, 1,4-bis(3-amino-α,α-ditrifluoromethylbenzyl)benzene, and 1,4-bis(4-amino-α,α-ditrifluoromethylbenzyl)benzene; 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; 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, and 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, and 1,4-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]benzene; Bis[(aminoaryloxy)benzoyl]diphenyl ethers 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]diphenyl sulfones such as 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenyl sulfone; Bis[aminophenoxyphenoxy]diphenyl sulfones such as 4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenyl sulfone; Diaminodiaryloxybenzophenones such as 3,3'-diamino-4,4'-diphenoxybenzophenone and 3,3'-diamino-4,4'-dibiphenoxybenzophenone; Diaminoaryloxybenzophenones such as 3,3'-diamino-4-phenoxybenzophenone and 3,3'-diamino-4-biphenoxybenzophenone; Examples thereof include 1-(4-aminophenyl)-2,3-dihydro-1,3,3-trimethyl-1H-inden-5-amine and 9,9-bis(4-aminophenyl)fluorene.

[0039] Examples of diamino ethers 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-aminoprotoxy)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.

[0040] Examples of diaminopolysiloxanes include α,ω-bis(2-aminoethyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane, α,ω-bis(4-aminobutyl)polydimethylsiloxane, α,ω-bis(5-aminopentyl)polydimethylsiloxane, α,ω-bis[3-(2-aminophenyl)propyl]polydimethylsiloxane, and α,ω-bis[3-(4-aminophenyl)propyl]polydimethylsiloxane.

[0041] These (a2') components may be used alone or in combination of two or more. Among them, alicyclic diamines and aromatic diamines are preferred, and aromatic diamines are more preferred, in that the adhesive layer exhibits excellent solder heat resistance.

[0042] The amount of the component (a2') used in 100 mol % of the monomers constituting the component (A) is usually 90 mol % or less, and preferably 50 mol % or less.

[0043] The amount of the component (a2') used in 100 mol % of the component (a2) is usually 90 mol % or less, and preferably 70 mol % or less.

[0044] The (A) component of the present invention can be obtained by various known production methods. Examples of the production method include a step of polyaddition reacting a monomer group including the (a1) component and the (a2) component at a temperature of preferably about 30 to 120°C, more preferably about 60 to 100°C, for a time of preferably about 0.1 to 2 hours, more preferably about 0.1 to 0.5 hours to obtain a polyaddition product, and a step of imidizing the obtained polyaddition product, i.e., dehydration ring-closing reaction, at a temperature of preferably about 80 to 250°C, more preferably about 100 to 170°C, for preferably about 0.5 to 50 hours, more preferably about 1 to 20 hours. The method and order of mixing the monomer group such as the (a1) component and the (a2) component are not particularly limited.

[0045] In the imidization reaction step, various known reaction catalysts, dehydrating agents, and organic solvents may be used, and these may be used alone or in combination of two or more kinds.

[0046] 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, picoline, and isoquinoline. Examples of the dehydrating agent include aliphatic carboxylic acid anhydrides such as acetic anhydride, and aromatic carboxylic acid anhydrides such as benzoic anhydride.

[0047] 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-propyl alcohol, isopropyl alcohol, 1-methoxy-2-propyl alcohol, t-butyl alcohol, etc.; aliphatic hydrocarbons such as 2-methylpentane, 3-ethylpentane, n-hexane, 2-methylhexane, 3-methylhexane, 3-ethylhexane, n-heptane, 2-methylheptane, 3-methylheptane, 4-methylheptane, 3-ethylheptane, n-octane, 2-methyloctane, 3-methyloctane, and 4-methyloctane; Alicyclic hydrocarbons such as methylcyclopentane, ethylcyclopentane, n-propylcyclopentane, isopropylcyclopentane, n-butylcyclopentane, isobutylcyclopentane, cyclohexane, methylcyclohexane, ethylcyclohexane, 1,1-dimethylcyclohexane, 1-ethyl-3-methylcyclohexane, and cycloheptane; Examples of the solvent include aromatic hydrocarbons such as benzene, toluene, and xylene; dimethyl sulfoxide, etc. These may be used alone or in combination of two or more kinds.

[0048] The amount of the organic solvent used is adjusted so that the reaction concentration is 5 to 60% by mass, preferably 20 to 50% by mass.

[0049] The imide ring closure rate of the component (A) is preferably from 90 to 100%, and more preferably from about 95 to 100%, in order to obtain a component (A) that has both a high softening point and flexibility. It is presumed that when the imide ring closure rate of component (A) is within the above range, component (A) is more likely to form a hard segment and soft segment structure, and thus has a higher softening point and flexibility. Here, the "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 NMR or IR analysis.

[0050] As for the physical properties of the component (A), for example, the weight average molecular weight is preferably 10,000 to 100,000. Also, the number average molecular weight of the component (A) is preferably 5,000 to 50,000. The weight average molecular weight and number average molecular weight are determined, for example, as polystyrene-equivalent values ​​measured by gel permeation chromatography (GPC).

[0051] The softening point of the component (A) of the present invention is preferably about 50 to 250° C., more preferably about 80 to 200° C., from the viewpoint of facilitating processing by press hardening during the production of laminates such as copper-clad laminates. The softening point refers to the temperature at which the storage modulus begins to decrease in the profile of the storage modulus measured using a commercially available measuring device (device name: "ARES-2KSTD-FCO-STD", manufactured by Rheometric Scientific Co., Ltd.) or the like.

[0052] Component (B) is an epoxy resin, and is a component that contributes to excellent solder heat resistance of the adhesive layer.

[0053] Examples of the component (B) include novolac type epoxy resins such as phenol novolac type epoxy resins and cresol novolac type epoxy resins; bisphenol type epoxy resins such as bisphenol A type epoxy resins, bisphenol F type epoxy resins, bisphenol S type epoxy resins, hydrogenated bisphenol A type epoxy resins, and hydrogenated bisphenol F type epoxy resins; polyphenol alkane type epoxy resins such as triphenol methane type epoxy resins and alkyl-modified triphenol methane type epoxy resins; dicyclopentadiene phenol type epoxy resins, (3',4'-epoxycyclohexane)methyl-3,4-epoxycyclo alicyclic epoxy resins such as hexyl carboxylate; glycidylamine-type epoxy resins such as N,N,N',N'-tetraglycidylxylylenediamine, N,N-diglycidylaniline, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylsulfone; isocyanurate-type epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; aromatic hydrocarbon epoxy resins such as biphenyl-type epoxy resins, stilbene-type epoxy resins, fluorene-type epoxy resins, and aryl alkylene-type epoxy resins;Ether type epoxy resins (reaction products of epichlorohydrin with polyols such as glycerin, 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), ester type epoxy resins (phthalic acid, methylphthalic acid, isophthalic acid, Examples of the epoxy resins include polycarboxylic acids such as p-oxyphthalic acid, terephthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid, trimellitic acid, and / or polymerized fatty acid, and epichlorohydrin), ether ester type epoxy resins (reaction products of hydroxycarboxylic acids such as p-oxyphthalic acid and β-oxynaphthophthalic acid with epichlorohydrin), epoxidized polyolefins, epoxidized polybutadienes, epoxidized soybean oil, aliphatic epoxy resins, dimer acid modified epoxy resins which are dimer acid modified products of these epoxy resins, and dimer acid diglycidyl esters. These may be used alone or in combination of two or more. Among them, glycidylamine type epoxy resins and ether type epoxy resins are preferred because they improve the adhesion of the adhesive layer to difficult-to-adhere substrates such as fluorine-based resins, show high adhesive strength, and are also excellent in solder heat resistance.;

[0054] Commercially available epoxy resins include "jER828", "jER834", "jER807", "jER604", "jER630", "jER871", "jER872", and "jER1031S" (all manufactured by Mitsubishi Chemical Corporation), "ST-3000", and "YD-172-X75" (all manufactured by Nippon Steel Chemical & Material Co., Ltd.), "Celloxide 2021P" (manufactured by Daicel Corporation), "TETRAD-X" (manufactured by Mitsubishi Gas Chemical Co., Ltd.), "NC-513", "NC-514S", and "NC-547" (all manufactured by Cardolite Corp.).

[0055] From the viewpoint of excellent solder heat resistance of the adhesive layer, the content of the (B) component 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% by weight, calculated as non-volatile content, relative to 100 parts by weight of the (A) component, where the non-volatile content refers to the components remaining after removing volatile components such as water and organic solvents.

[0056] The component (C) is a bismaleimide having a dimer diamine skeleton, which is highly compatible with the component (A) and exhibits high adhesive strength by improving adhesion to poorly adherent substrates such as fluorine-based resins. Commercially available products of the component (C) include, for example, "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" (all manufactured by Designer Molecule Inc.), and "SLK-2600" (manufactured by Shin-Etsu Chemical Co., Ltd.). These may be used alone or in combination of two or more.

[0057] These commercially available products are bismaleimides represented by the formula (3) according to their trade names. In formula (3), n in the BMI series represents an integer of 1 to 10, and m=1 and n=5 for SLK-526.

[0058] [ka]

[0059] The content of the (C) component, calculated as non-volatile content, is preferably 0.1 to 10 parts by weight, more preferably 0.3 to 5 parts by weight, and even more preferably 0.5 to 3 parts by weight, per 100 parts by weight of the (A) component, in order to improve the adhesion of the adhesive layer to poorly adherent substrates, thereby exhibiting high adhesive strength, and also to have excellent solder heat resistance.

[0060] The adhesive composition of the present invention may further contain a maleimide (C') other than the component (C) (hereinafter also referred to as component (C')).

[0061] Examples of the component (C') include maleimide; N-alkyl monomaleimides such as N-methylmaleimide, N-ethylmaleimide, Nn-propylmaleimide, N-isopropylmaleimide, Nn-butylmaleimide, N-isobutylmaleimide, N-tert-butylmaleimide, Nn-pentylmaleimide, Nn-hexylmaleimide, Nn-heptylmaleimide, Nn-octylmaleimide, Nn-nonylmaleimide, Nn-decylmaleimide, Nn-dodecylmaleimide, Nn-tetradecylmaleimide, Nn-hexadecylmaleimide, and Nn-octadecylmaleimide; N-cycloalkyl monomaleimides such as N-cyclopentylmaleimide and N-cyclohexylmaleimide; N-aryl monomaleimides such as N-phenylmaleimide, N-(2-methylphenyl)maleimide, N-(4-methylphenyl)maleimide, N-(2,6-diethylphenyl)maleimide, N-phenylmethylmaleimide, N-(4-hydroxyphenyl)maleimide, N-(4-carboxyphenyl)maleimide, N-(4-acetylphenyl)maleimide, N-(4-methoxyphenyl)maleimide, N-(4-ethoxyphenyl)maleimide, N-(4-chlorophenyl)maleimide, and N-(4-bromophenyl)maleimide; N,N'-alkylene bismaleimides such as N,N'-ethylene bismaleimide, N,N'-trimethylene bismaleimide, N,N'-tetramethylene bismaleimide, N,N'-pentamethylene bismaleimide, N,N'-hexamethylene bismaleimide, N,N-heptamethylene bismaleimide, N,N-octamethylene bismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, and 1,1'-(decane-1,10-diyl)bis(1H-pyrrole-2,5-dione); bismaleimides having a cycloalkane such as N,N'-dicyclohexylmethane bismaleimide, 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, 1,1'-(1,3-phenylene)]bis(1H-pyrrole-2,5-dione, etc.; 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'-diphenylethylene N,N'-diphenyl bismaleimide such as 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, and 1,1'-[2,2'-bis(trifluoromethyl){1,1'-biphenyl}-4,4'-diyl]bis[1H-pyrrole-2,5-dione]; Examples of bis(maleimidophenoxyphenyl)alkanes include 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, and 2,2-bis[3-ethyl-4-(4-maleimidophenoxy)phenyl]hexafluoropropane. These may be used alone or in combination of two or more.

[0062] Commercially available products of component (C') include, for example, "BMI", "BMI-70", and "BMI-80" (all manufactured by K.I. Chemical Co., Ltd.), "BMI-1000", "BMI-1000H", "BMI-1100", "BMI-1100H", "BMI-2000", "BMI-2300", "BMI-3000", "BMI-3000H", "BMI-4000", "BMI-5100", "BMI-7000", "BMI-7000H", and "BMI-TMH" (all manufactured by Yamato Chemical Co., Ltd.).

[0063] The content of component (C') is preferably not more than 2.5 parts by weight, and more preferably not more than 1.5 parts by weight, per 100 parts by weight of component (A), calculated as non-volatile content.

[0064] The component (D) is a diene polymer having a 1,2-vinyl group in the side chain, and is a component that improves the adhesion of the adhesive layer to poorly adherent substrates and exhibits high adhesive strength.

[0065] Examples of the (D) component include diene homopolymers such as polyisoprene, polybutadiene, and 1,2-butadiene homopolymer; diene copolymers such as butadiene-isoprene polymer, isobutylene-isopropylene polymer, butadiene-acrylonitrile polymer, ethoxylated polybutadiene, epoxidized polybutadiene, butadiene-styrene polymer, and styrene-butadiene-styrene polymer. These may be used alone or in combination of two or more. Examples of commercially available products include "RICON100", "RICON150", "RICON154", "RICON156", "RICON181", and "RICON184" (all manufactured by CRAY VALLEY), "NISSO-PB JP-200", and "NISSO-PB B-1000" (all manufactured by Nippon Soda Co., Ltd.).

[0066] Among these, diene copolymers are preferred, and butadiene-styrene polymers are more preferred, in that they improve the adhesion of the adhesive layer to poorly adherent substrates and exhibit high adhesive strength.

[0067] The content of the component (D), calculated as the nonvolatile content, is preferably 5 to 40 parts by weight, more preferably 7.5 to 20 parts by weight, and even more preferably 10 to 15 parts by weight, per 100 parts by weight of the component (A).

[0068] The adhesive composition of the present invention may further contain an active ester (E) (hereinafter referred to as component (E)).

[0069] Examples of the component (E) include those containing a dicyclopentadienyldiphenol structure described in JP-A-2019-183071, those containing a naphthalene structure, acetylated phenol novolac, benzoylated phenol novolac, etc. These may be used alone or in combination of two or more.

[0070] Examples of commercially available products of component (E) include: Those containing a dicyclopentadienyldiphenol 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", and "EXB-8150-65T" (all manufactured by DIC Corporation); Those containing a naphthalene structure include "EXB9416-70BK" (DIC Corporation); An acetylated phenol novolac, "DC808" (Mitsubishi Chemical Corporation); Benzoyl compounds of phenol novolak include "YLH1026", "YLH1030", and "YLH1048" (all manufactured by Mitsubishi Chemical Corporation).

[0071] The component (E) may be produced by any of a variety of known methods. Examples include the reaction of a polyfunctional phenol compound with an aromatic carboxylic acid, as described in Japanese Patent No. 5152445.

[0072] The content of the component (E), calculated as nonvolatile content, is preferably 1 to 10 parts by weight, more preferably 1.5 to 8 parts by weight, and even more preferably 2 to 5 parts by weight, per 100 parts by weight of the component (A).

[0073] The adhesive composition of the present invention may further contain a curing component such as benzoxazine, cyanate ester, polyisocyanate, phosphorus compound, acid anhydride, amine, imidazole, guanidine, phenol resin, etc. These may be used alone or in combination of two or more kinds.

[0074] 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. A phenyl group, a methyl group, a cyclohexyl group, etc. may be bonded to the nitrogen of the oxazine ring.

[0075] Commercially available benzoxazine products include "benzoxazine Fa type" and "benzoxazine Pd type" (both manufactured by Shikoku Chemical Industry Co., Ltd.), and "RLV-100" (manufactured by Air Water Inc.).

[0076] Examples of cyanate esters 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, diallyl bisphenol 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, and 2,2-bis(4-cyanatophenyl)propane.

[0077] Commercially available cyanate esters include "PRIMASET BTP-6020S" (manufactured by Lonza Japan Co., Ltd.).

[0078] Examples of polyisocyanates 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 isocyanate; 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, norbornenemethane diisocyanate, adamantane diisocyanate, cyclohexane-1,4-diylbis(methylene) diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, tricyclodecylene diisocyanate, hydrogenated xylylene diisocyanate, hydrogenated tolylene diisocyanate, hydrogenated tetramethylxylylene diisocyanate, hydrogenated diphenylmethane diisocyanate, hydrogenated dimethyldiphenylmethane diisocyanate, and hydrogenated naphthalene diisocyanate; Examples of the aromatic polyisocyanates include xylylene diisocyanate, tolylene diisocyanate, phenylene diisocyanate, tetramethyl xylylene diisocyanate, diphenylmethane diisocyanate, dimethyldiphenylmethane diisocyanate, m-tetramethyl xylylene diisocyanate, and naphthalene diisocyanate.

[0079] As the polyisocyanate, a biuret, an isocyanurate, an allophanate, or an adduct of the above polyisocyanate can also be used. These polyisocyanates can be used alone or in combination of two or more kinds.

[0080] Commercially available polyisocyanates include, for example: Examples of biuret compounds include "Duranate 24A-100", "Duranate 22A-75P", and "Duranate 21S-75E" (all manufactured by Asahi Kasei Corporation), 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", and "Duranate MHG-80B" (all manufactured by Asahi Kasei Corporation), "Coronate HXR" (manufactured by Tosoh Corporation), "Takenate D-131N", "Takenate D204EA-1", and "Takenate D-127N" (all manufactured by Mitsui Chemicals, Inc.), and "VESTANAT T1890 / 100" (manufactured by Evonik Japan Co., Ltd.), etc. Examples of allophanate compounds include "Takenate D-178N" (manufactured by Mitsui Chemicals, Inc.). Examples of the adduct include "Duranate P301-75E" (manufactured by Asahi Kasei Corporation), "Takenate D110N", and "Takenate D160N" (all manufactured by Mitsui Chemicals, Inc.), and "Coronate L" (manufactured by Tosoh Corporation).

[0081] Examples of phosphorus compounds 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.

[0082] Examples of acid anhydrides 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.

[0083] Examples of the amine include the above-mentioned dimer diamine, component (a2-1), aliphatic amines such as triethylamine, tributylamine, triethylenediamine, diethylenetriamine, triethylenetetramine, and tetraethylenepentamine; Amino alcohols such as triethanolamine and dimethylaminoethanol; Alicyclic amines such as trimer triamine; Aromatic amines such as 1,3-aminobenzene, benzyldimethylamine, 1,3-bis(aminomethyl)benzene, and 2,4,6-tris(dimethylaminomethyl)phenol; Heterocyclic amines such as 4-dimethylaminopyridine, N-aminoethylpiperazine, and 1,8-diazabicyclo[5,4,0]-undecene; Examples of the polyamine include polyamide polyamine, polyether polyamine, polyester polyamine, etc. These may be used alone or in combination of two or more kinds.

[0084] Examples of the imidazole include 2-methylimidazole, 1,2-dimethylimidazole, 2-ethyl-4-methylimidazole, 2-undecylimidazole, 2-heptadecylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 1-benzyl-2-methylimidazole, 1-benzyl-2-phenylimidazole, 1-cyanoethyl-2-methylimidazole, 1-cyanoethyl-2-undecylimidazole, 1-cyanoethyl-2-ethyl-4-methylimidazole, 1-cyanoethyl-2-phenylimidazole, 2-ethyl-4-methylimidazole tetraphenylborate, 1-cyanoethyl-2-undecylimidazole, 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 addition Examples of the compound include 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.

[0085] 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-methylbiguanide, 1-ethylbiguanide, 1-n-butylbiguanide, 1-n-octadecylbiguanide, 1,1-dimethylbiguanide, 1,1-diethylbiguanide, 1-cyclohexylbiguanide, 1-allylbiguanide, 1-phenylbiguanide, and 1-(o-tolyl)biguanide. These may be used alone or in combination of two or more.

[0086] Examples of the phenol resin include phenol novolac resin, cresol novolac resin, bisphenol A type novolac resin, triazine modified phenol novolac resin, phenolic hydroxyl group-containing phosphazene, etc. These may be used alone or in combination of two or more kinds.

[0087] The content of the curing component, calculated as the non-volatile content, is preferably 0.5 to 5 parts by weight, and more preferably 0.5 to 2 parts by weight, per 100 parts by weight of the component (A).

[0088] The adhesive composition of the present invention may further contain an inorganic filler.

[0089] Examples of inorganic fillers include silica fillers, phosphorus-based fillers, fluorine-based fillers, and inorganic ion exchanger fillers. The silica filler may be one whose surface has been modified with a treatment agent such as a silane coupling agent. These may be used alone or in combination of two or more.

[0090] Commercially available silica fillers include, for example, "FB-3SDC" and "SFP-20M" (all manufactured by Denka Co., Ltd.), "SC-2500-SPJ", "SC-2500-SXJ", "SC-2500-SVJ", and "SC-2500-SEJ" (all manufactured by Admatechs Co., Ltd.), "Exolit OP935" (manufactured by Clariant Chemicals Co., Ltd.), "KTL-500F" (manufactured by Kitamura Co., Ltd.), and "IXE" (manufactured by Toagosei Co., Ltd.).

[0091] The content of the inorganic filler, calculated as the nonvolatile content, is preferably 1 to 150 parts by weight per 100 parts by weight of the component (A).

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

[0093] Examples of phosphorus-based flame retardants include polyphosphoric acid, phosphoric acid esters, and phosphazene derivatives that do not have a phenolic hydroxyl group. Among the phosphazene derivatives, cyclic phosphazene derivatives are preferred in terms of flame retardancy, heat resistance, bleed-out resistance, etc. Commercially available cyclic phosphazene derivatives include "SPB-100" (manufactured by Otsuka Chemical Co., Ltd.) and "Ravitol FP-300B" (manufactured by Fushimi Pharmaceutical Co., Ltd.).

[0094] The content of the phosphorus-based flame retardant is preferably 1 to 150 parts by weight per 100 parts by weight of the component (A), calculated as the non-volatile content.

[0095] The adhesive composition of the present invention includes a compound having the general formula: W-Si(R 1 ) a (OR 2 ) 3-a (Wherein, W represents a group containing a functional group reactive with an acid anhydride group, R 1 represents a hydrogen atom or a hydrocarbon group having 1 to 8 carbon atoms; R 2represents 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 composition layer while maintaining the low dielectric properties. As a result, the adhesive layer can be prevented from bleeding out from the edge of the support while increasing the interfacial adhesion between the adhesive composition layer and the support (the so-called anchor effect).

[0096] Examples of the reactive functional group contained in W in the above general formula include an amino group, an epoxy group, and a thiol group.

[0097] Examples of compounds 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. Examples of compounds in which W contains an epoxy group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, and 3-glycidoxypropyltriethoxysilane. Examples of compounds in which W contains a thiol group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane. Among these, compounds in which W contains an amino group are preferred because of their good reactivity and flow control effects.

[0098] The content of the reactive alkoxysilyl compound is preferably 0.01 to 5 parts by weight based on 100 parts by weight of the component (A), calculated as the non-volatile content.

[0099] The adhesive composition of the present invention may further contain the above-mentioned organic solvent. The content of the organic solvent is adjusted so that the non-volatile content of the adhesive composition is preferably 5 to 60% by weight, more preferably 20 to 50% by weight.

[0100] The adhesive composition of the present invention may contain an additive other than any of the following: component (A), component (B), component (C), component (D), component (E), a curing component, an inorganic filler, a phosphorus-based flame retardant, a reactive alkoxysilyl compound, and an organic solvent.

[0101] 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, release agents, surface treatment agents, viscosity modifiers, inorganic pigments, and organic pigments.

[0102] The content of the additive, calculated as non-volatile content, per 100 parts by weight of component (A), 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.

[0103] The adhesive composition of the present invention can be obtained by adding component (A), component (B), component (C), and component (D), and optionally component (E), a curing component, an inorganic filler, a flame retardant, a reactive alkoxysilyl compound, an organic solvent, and additives, and dissolving them while mixing.

[0104] [Cured product] The cured product of the present invention contains the adhesive composition. Examples of a method for producing the cured product include a method including a step of applying the adhesive composition to a suitable support, a step of curing the adhesive composition by heating to volatilize the organic solvent, and a step of peeling off the support. The thickness of the cured product is preferably 3 to 40 μm. Examples of the support include release paper, release film, and a support film described below. When producing the cured product, the adhesive composition may be used in combination with various known adhesive compositions other than the adhesive composition.

[0105] [Adhesive sheet] The adhesive sheet of the present invention comprises a support film and the cured product of the present invention on at least one surface of the support film.

[0106] The adhesive sheet can be obtained, for example, by applying the adhesive composition of the present invention onto a support film and curing it by heating, or by laminating the cured product of the present invention onto a support film.

[0107] Examples of the support film include polyimide, polyester, polyimide-silica hybrid, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin, ethylene terephthalate, aromatic polyester resin obtained from phenol, phthalic acid, hydroxynaphthoic acid, etc. and parahydroxybenzoic acid (so-called liquid crystal polymer; "Vexstar" (manufactured by Kuraray Co., Ltd.), etc.), cycloolefin polymer, fluorine-based resin (polytetrafluoroethylene (PTFE), perfluoroalkoxyalkane (PFA), polyvinylidene fluoride (PVDF), etc.), etc. Polyimide includes the polyimide film of the present invention.

[0108] When the adhesive composition of the present invention is applied to the support film, examples of the application method include a coater such as a comma coater, a die coater, a knife coater, a lip coater, etc. The thickness of the coating layer after drying is preferably about 1 to 100 μm, more preferably about 3 to 50 μm. The adhesive layer of the adhesive sheet may be protected with various protective films.

[0109] [Resin-coated copper foil] The resin-coated copper foil of the present invention includes the cured product or adhesive sheet of the present invention and a copper foil. Specifically, the adhesive composition of the present invention is applied to a copper foil and then heat-cured, or the cured product or adhesive sheet of the present invention is laminated to the copper foil. Examples of the copper foil include rolled copper foil and electrolytic copper foil, and those that have been subjected to various surface treatments (roughening, rust prevention, etc.) can also be used. Examples of the rust prevention treatment include so-called mirror-finishing treatments such as plating treatment using a plating solution containing Ni, Zn, Sn, etc., and chromate treatment.

[0110] The thickness of the copper foil is preferably about 1 to 100 μm, more preferably about 2 to 38 μm. Examples of the coating method include the above-mentioned methods.

[0111] The cured product or adhesive sheet of the resin-coated copper foil may be partially or completely cured under heating. The partially cured cured product or adhesive sheet is in a state called B stage. The thickness of the cured product or adhesive sheet is preferably about 0.5 to 30 μm. A cured product or adhesive sheet may be further laminated to the copper foil of the resin-coated copper foil to produce a double-sided resin-coated copper foil.

[0112] [Copper-clad laminate] The copper-clad laminate of the present invention includes the resin-coated copper foil of the present invention and a copper foil or insulating sheet. The copper-clad laminate is also called CCL (Copper Clad Laminate). Specifically, the copper-clad laminate is a laminate in which the resin-coated copper foil is pressed under heat onto at least one or both sides of various known copper foils or insulating sheets. When laminating onto one side, a material different from the resin-coated copper foil may be pressed onto the other side. In addition, the number of resin-coated copper foils, copper foils, and insulating sheets in the copper-clad laminate is not particularly limited.

[0113] In one embodiment, the insulating sheet is preferably a prepreg or the support film. The prepreg refers to a sheet-like material in which a reinforcing material such as glass cloth is impregnated with a resin and cured to the B stage (JIS C 5603). The resin used may be an insulating resin such as the adhesive composition of the present invention, a phenol resin, an epoxy resin, a polyester resin, a liquid crystal polymer, or an aramid resin. The thickness of the insulating sheet is preferably about 20 to 500 μm. Heating and pressing conditions are preferably about 150 to 280° C. (more preferably about 170 to 240° C.) and preferably about 0.5 to 20 MPa (more preferably about 1 to 8 MPa).

[0114] [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 patterning means for forming a circuit pattern on the copper foil surface of the copper-clad laminate include a subtractive method and a semi-additive method. As the semi-additive method, a method in which the copper foil surface of the copper-clad laminate is patterned with a resist film, electrolytic copper plating is performed, the resist is removed, and etching is performed with an alkaline solution is exemplified. In addition, the thickness of the circuit pattern layer in the printed wiring board is not particularly limited. In addition, a multilayer board can be obtained by laminating the same printed wiring board or other known printed wiring boards or printed circuit boards on the printed wiring board as a core. When laminating, the adhesive composition and other known adhesive compositions other than the adhesive composition can be used in combination. In addition, the number of layers in the multilayer board is not particularly limited. In addition, a via hole may be inserted and the inside may be plated each time lamination is performed. The line / space ratio of the circuit pattern is not particularly limited, but is preferably about 1 μm / 1 μm to 100 μm / 100 μm. The height of the circuit pattern is not particularly limited, but is preferably about 1 to 50 μm. EXAMPLES

[0115] The present invention will be described in detail below with reference to examples, but is not limited thereto. Unless otherwise specified, all "%" is by mass.

[0116] <Weight average molecular weight> The weight average molecular weight of the polyimide was measured under the following conditions. (Measurement conditions) Model: HLC-8320GPC (Tosoh Corporation) Column: TSKgel SuperHZM-M (Tosoh Corporation) Developing solvent: Tetrahydrofuran Flow rate: 0.35mL / min Measurement temperature: 40℃ Detector: RI Standard: Polystyrene Sample concentration: 0.4wt%

[0117] Manufacturing Example 1 In a reaction vessel equipped with a stirrer, a water divider, a thermometer, and a nitrogen gas inlet tube, 70.0 g of 4,4'-(hexafluoroisopropylidene)diphthalic anhydride (6FDA, manufactured by Daikin Co., Ltd.), 100.82 g of ethylene glycol dimethyl ether, and 235.24 g of toluene were charged and heated to 70°C. Next, 81.8 g of dimer diamine (trade name: "PRIAMINE1075", manufactured by Croda Japan Co., Ltd., hereinafter referred to as PRIAMINE1075) was gradually added, and the mixture was heated to 110°C and subjected to an imidization reaction for 15 hours to obtain a solution of polyimide resin (A-1) (non-volatile content 35%).

[0118] Manufacturing Example 2 In a reaction vessel similar to that of 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, LLC. 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. Next, 197.8 g of PRIAMINE 1075 was gradually added, and the mixture was heated to 110 ° C. and subjected to an imidization reaction for 10 hours to obtain a solution of polyimide resin (A-2) (non-volatile content 30%).

[0119] Production Example 3 In a reaction vessel similar to that of 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. Next, 14.53 g of 4,4′-diaminophenyl ether (trade name: “ODA”, manufactured by Wakayama Seika Kogyo Co., Ltd.) and 156.75 g of PRIAMINE 1075 were gradually added, and the mixture was heated to 110° C. and subjected to an imidization reaction for 10 hours to obtain a solution of polyimide resin (A-3) (non-volatile content 30%).

[0120] Example 1 As the component (A), 271.74 g of the component (A-1) (100.0 g of nonvolatile content) were used. As the component (B), 1.0 g of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane (trade name: "jER604", manufactured by Mitsubishi Gas Chemical Co., Inc.) (1.0 g of nonvolatile content) were used. As the component (C), 1.7 g of a bismaleimide represented by the following formula (4) (trade name: "BMI-689", manufactured by Designer Molecule Inc.) (1.7 g of nonvolatile content) were used. As the component (D), a butadiene-styrene polymer (trade name: "RICON100", manufactured by CRAY As a component (E), 11.5 g (non-volatile content: 11.5 g) of an active ester (product name: "HPC-8000L", manufactured by DIC Corporation) was mixed (product name: "HPC-8000L", manufactured by DIC Corporation) (product number: 2.2 g) and 75.7 g of methyl ethyl ketone was mixed and thoroughly stirred to obtain an adhesive composition with a non-volatile content of 30%.

[0121] [ka]

[0122] Examples 2 to 11, Comparative Examples 1 to 4 The same procedure as in Example 1 was carried out except that the compositions were changed as shown in Table 1, to obtain adhesive compositions.

[0123] <Preparation of adhesive sheet> The adhesive composition of each Example and Comparative Example was applied to a release paper (manufactured by San-A Chemical Co., Ltd.) using a gap coater so that the thickness after drying was 25 μm, and then dried at 150° C. for 5 minutes. The release paper was then peeled off to obtain each adhesive sheet.

[0124] <Measurement of relative dielectric constant and dielectric tangent> The adhesive sheet was placed on a support for pressing, and the same support for pressing was placed on the adhesive sheet side and cured by hot pressing at a pressure of 5 MPa and 180° C. for 90 minutes to produce a laminate (support / adhesive sheet / support) after thermal curing. The support for pressing was removed from the adhesive sheet, and the dielectric constant (Dk) and dielectric loss tangent (Df) of the adhesive sheet were calculated using the following method. Using a network analyzer (Keysight Technologies, device name: "P5003A") and a split post dielectric resonator (QWED) with a measurement frequency of 10.124 GHz, the resonant frequency and peak Q value of the resonator alone with nothing inserted were measured. Next, the adhesive layer was cut into 4 cm x 5 cm pieces to prepare test pieces, and then multiple test pieces were stacked together so that the total thickness was 100 μm or more and inserted into a resonator. After that, the resonant frequency and Q value were measured when the test pieces were inserted. The dielectric constant (Dk) was calculated from the difference in resonance frequency between the resonator alone and when the test piece was inserted, and the dielectric loss tangent (Df) was calculated from the difference in Q value and the difference in resonance frequency between the resonator alone and when the test piece was inserted. The results are shown in Table 1 (same below).

[0125] <Preparation of copper-clad laminate> The adhesive composition of each Example and Comparative Example was applied to a release paper (manufactured by San-A Chemical Co., Ltd.) using a gap coater so that the thickness after drying would be 25 μm, and then dried at 150° C. for 5 minutes to obtain an adhesive sheet (release paper / adhesive layer). A double-sided copper-clad laminate (product name: "Pyralux TK125012R", Dupont; film thickness 75 μm) in which copper foil / fluororesin was laminated on both sides of a polyimide film was etched with a 40% aqueous solution of iron (III) chloride to remove the copper foil. Next, each adhesive sheet was placed on one side of the exposed fluororesin, and a commercially available electrolytic copper foil (product name: "F2-WS", Furukawa Circuit Foil Co., Ltd.; 18 μm thick) was placed on top of that to produce a laminate (fluororesin layer / polyimide film / fluororesin layer / adhesive sheet / electrolytic copper foil). Next, the laminate was placed on a pressing support with the copper foil surface in contact with the support, and cured from above in a hot press at a pressure of 10 MPa and a temperature of 180°C for 90 minutes via a support made of the same material, to produce a copper-clad laminate.

[0126] <Adhesive strength> The peel strength (N / mm) of the copper-clad laminate was measured in accordance with JIS C 6481 (Test method for copper-clad laminates for flexible printed wiring boards).

[0127] <Solder heat resistance> The copper-clad laminate (1) was left in a thermostatic chamber at a temperature of 23°C and a humidity of 50% for 24 hours, and then floated in a solder bath at 288°C with the copper foil side facing down to check for the presence or absence of bubbles, and evaluated according to the following criteria. (Evaluation Criteria) ○: No change in appearance. ×: The copper-clad laminate exhibited foaming, swelling, and peeling.

[0128] [Table 1] *The "g" for each component is expressed as the non-volatile weight.

[0129] The symbols shown in Table 1 represent the following compounds. <Polyimide resin> A-1: Polyimide resin of Production Example 1 A-2: Polyimide resin of Production Example 2 A-3: 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'-Tetraglycidylxylylenediamine (product name: "TETRAD-X", manufactured by Mitsubishi Gas Chemical Co., Ltd.) B-3: Ether type epoxy resin (product name: "jER1031S", reaction product of tetrahydroxyphenylethane and epichlorohydrin, manufactured by Mitsubishi Chemical Corporation) <Bismaleimide> C-1: Bismaleimide represented by the above formula (4) (product name: "BMI-689", manufactured by Designer Molecule Inc.) F-1: N,N'-(4,4'-diphenylmethane)bismaleimide (product name: "BMI-1000H", manufactured by Daiwa Kasei Co., Ltd.) <Diene polymer> D-1: Butadiene-styrene polymer (product name: "RICON100", manufactured by CRAY VALLEY) <Other> E-1: Activated ester (product name: "HPC-8000L", manufactured by DIC Corporation)

Claims

1. A polyimide resin (A) which is a product of reaction components including an aromatic tetracarboxylic dianhydride (a1) and a diamine (a2) including a dimer diamine, an epoxy resin (B), Bismaleimide (C) having a dimer diamine skeleton, and An adhesive composition comprising a diene polymer (D) having a 1,2-vinyl group in a side chain.

2. The adhesive composition according to claim 1 , further comprising an active ester (E).

3. A cured product comprising the adhesive composition of claim 1.

4. An adhesive sheet having the cured product according to claim 3 on at least one surface of a support film.

5. A resin-coated copper foil comprising the cured product according to claim 3 or the adhesive sheet according to claim 4, and a copper foil.

6. A copper-clad laminate comprising the resin-coated copper foil according to claim 5 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 claim 6.

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