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

Abstract

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 present invention provides an adhesive composition that provides an adhesive layer that maintains low dielectric properties (low dielectric constant and low dielectric loss tangent), exhibits high adhesive strength by improving adhesion to a substrate that is difficult to adhere, such as a fluorine-based resin, and also has excellent solder heat resistance. The adhesive composition contains a polyimide resin (A) which is a product of a reaction component containing an aromatic tetracarboxylic dianhydride (a1) and a diamine (a2) containing a dimer diamine, an epoxy resin (B), a bismaleimide (C) having a dimer diamine skeleton, and a diene polymer (D) having a 1, 2-vinyl group in a side chain.

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

[0003] In recent years, high-frequency electrical signals have been used to transmit and process large amounts of information at high speed. However, 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 resins with low dielectric properties (low dielectric constant, low dielectric loss tangent) are useful in this regard.

[0004] As such technology, the applicant discloses a kind of adhesive composition comprising a polyimide having a tetracarboxylic acid residue and a diamine residue derived from a dimer acid and a crosslinking component, so as to form an adhesive layer (patent document 1) in a copper-clad laminate having an insulating film, an adhesive layer and copper foil. In the technology, the polyimide resin of the adhesive layer is respectively close to the insulating film and copper foil of polyimide etc., and bears the effect of exerting a high bonding strength. On the other hand, in recent years, in order to cope with the requirement of further high frequency, it is found that the trend of using fluorine resins such as polytetrafluoroethylene (PTFE) or perfluoroalkoxy alkane (PFA) as an insulating film with lower dielectric properties is used. However, when using fluorine resins, the adhesive layer cannot be fully close and the bonding strength is reduced. And then, the solder heat resistance is also poor. [Prior art literature] [Patent Document]

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

[0006] The present invention provides an adhesive composition that provides an adhesive layer that maintains low dielectric properties (low dielectric constant and low dielectric loss tangent), exhibits high bonding strength by improving adhesion to difficult-to-bond substrates such as fluorine-based resins, and also has 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 resin (A) as a product of reaction components comprising an aromatic tetracarboxylic dianhydride (a1) and a diamine (a2) containing a dimer diamine, an epoxy resin (B), Bismaleimide (C) having a dimer diamine skeleton, and A diene polymer (D) having a 1,2-vinyl group in a side chain.

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

[0010] 3. A cured product comprising the adhesive composition according to 1 above.

[0011] 4. An adhesive sheet comprising the cured product according to 3 above on at least one surface of a support film.

[0012] 5. A copper foil with resin, comprising the cured product according to the above Item 3 or the adhesive sheet according to the above Item 4, and a copper foil.

[0013] 6. A copper-clad laminate comprising the copper foil with resin according to the above 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 according to 6 above. [Effects of the Invention]

[0015] The adhesive composition of the present invention provides an adhesive layer that maintains low dielectric properties (low dielectric constant and low dielectric loss tangent) and, when made into a copper-clad laminate, exhibits high bonding strength by improving adhesion to difficult-to-bond substrates such as fluorine-based resins, and further has excellent solder heat resistance. DETAILED DESCRIPTION

[0016] The adhesive composition of the present invention comprises: a polyimide resin (A) (hereinafter referred to as the (A) component) which is a product of reaction components including an aromatic tetracarboxylic dianhydride (a1) (hereinafter referred to as the (a1) component) and a diamine (a2) containing a dimer diamine (hereinafter referred to as the (a2) component), an epoxy resin (B) (hereinafter referred to as the (B) component), a bismaleimide (C) having a dimer diamine skeleton (hereinafter referred to as the (C) component), and a diene polymer (D) having a 1,2-vinyl group in a side chain (hereinafter referred to as the (D) component).

[0017] The component (A) is a polyimide resin and is a component for allowing the layer of the adhesive composition (hereinafter referred to as an adhesive layer) to exhibit 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- [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.

[0019] Among them, the component (a1) is preferably a component represented by the following general formula (1) from the viewpoint of flexibility and solder heat resistance of the adhesive layer. (In formula (1), X represents a single bond, -SO2-, -CO-, -O-, -O-C6H4-C(CH3)2-C6H4-O-, -C(CH3)2-, -O-C6H4-SO2-C6H4-O-, -C(CHF2)2-, -C(CF3)2-, -COO-(CH2) p -OCO- or -COO-H2C-HC (-OC(=O)-CH3)-CH2-OCO-, p represents an integer of 1 to 20)

[0020] 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 good dissolution of component (A) in an organic solvent, preferably 2,2-bis (3,4-dicarboxylphenyl) hexafluoropropane dianhydride, 4,4'-[propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic acid dianhydride.

[0021] 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%.

[0022] 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%.

[0023] 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%.

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

[0025] 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.

[0026] 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.

[0027]

[0028] 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).

[0029]

[0030]

[0031] Furthermore, the dimer diamine may contain amines derived from the monomeric acid, trimer acid and / or polymerized fatty acid, and their content in the dimer diamine is 10 wt % or less, preferably 5 wt % or less, more preferably 3 wt % or less, and further preferably 2 wt % or less.

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

[0033] 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%.

[0034] 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 %.

[0035] In addition, as the component (a2), a diamine (a2') other than the dimer diamine may be included (hereinafter referred to as the component (a2')). As the component (a2'), for example, an aliphatic diamine, an alicyclic diamine, an aromatic diamine, a diamino ether, and a diamino polysiloxane may be included. In addition, regarding these amines, the dimer diamine is excluded.

[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, 1,12-diaminododecane, etc.

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

[0038] 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.

[0039] 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.

[0040] 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.

[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, from the viewpoint that the adhesive layer exhibits excellent solder heat resistance.

[0042] The usage-amount of the component (a2') in 100 mol% of the monomer group which comprises the component (A) is 90 mol% or less normally, Preferably it is 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, preferably 70 mol % or less.

[0044] 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 components (a1) and (a2) to an addition polymerization reaction at a temperature of preferably about 30°C to 120°C, more preferably about 60°C to 100°C, and a time of 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, at a temperature of preferably about 80°C to 250°C, more preferably about 100°C to 170°C, for preferably about 0.5 hours to 50 hours, more preferably about 1 hour to 20 hours. In addition, the method and order of mixing the monomer groups such as components (a1) and (a2) are not particularly limited.

[0045] 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.

[0046] 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.

[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, 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.

[0048] 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.

[0049] 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. The reason is presumably 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 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.

[0050] 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.

[0051] In terms of ease of processing by press hardening when manufacturing a laminate such as a copper-clad laminate, the softening point of the component (A) of the present invention is preferably about 50° C. to 250° C., and 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 instrument (device name: "ARES-2KSTD-FCO-STD", manufactured by Rheometric Scientific Co., Ltd.) or the like.

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

[0053] Examples of the component (B) include novolac epoxy resins such as phenol novolac epoxy resins and 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; polyphenol-alkane epoxy resins such as trisphenol methane epoxy resins and alkyl-modified trisphenol methane epoxy resins; dicyclopentadienol epoxy resins, (3',4'-epoxycyclohexane)methyl-3, Alicyclic epoxy resins such as 4-epoxycyclohexyl carboxylate; glycidylamine epoxy resins such as N,N,N',N'-tetraglycidylphenylenediamine, N,N-diglycidylaniline, N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane, and N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylsulfone; isocyanurate epoxy resins such as triglycidyl isocyanurate and monoallyl diglycidyl isocyanurate; biphenyl epoxy resins Aromatic hydrocarbon epoxy resins such as epoxy resins, stilbene epoxy resins, fluorene epoxy resins, and aryl alkylene epoxy resins; ether epoxy resins (reaction products of polyols such as glycerol, neopentyl glycol, ethylene glycol, propylene glycol, butylene glycol, 1,5-pentanediol, 1,6-hexanediol, polyethylene glycol, polypropylene glycol, hydroquinone, naphthol, trihydroxybiphenyl, diresorcinol, bis-xylenol, binaphthol, trihydroxyphenylmethane, and tetrahydroxyphenylethane with epichlorohydrin), ester epoxy resins (phthalic acid, methyl phthalate, phthalic acid ... The epoxy resin of the present invention is preferably a kind of epoxy resin, which is a kind of epoxy resin with a high bonding strength. The epoxy resin of the present invention is preferably a kind of epoxy resin with a high bonding strength. The epoxy resin of the present invention is preferably a kind of epoxy resin with a high bonding strength. The epoxy resin of the present invention is preferably a kind of epoxy resin with a high bonding strength. The epoxy resin of the present invention is preferably a kind of epoxy resin with a high bonding strength. The epoxy resin of the present invention is preferably a kind of epoxy resin with a high bonding strength. The epoxy resin of the present invention is preferably a kind of epoxy resin with a high bonding strength. The epoxy resin of the present invention is preferably a kind of epoxy resin with a high bonding strength. The epoxy resin of the present invention is preferably a kind of epoxy resin with a high bonding strength. The epoxy resin of the present invention is preferably a kind of epoxy resin with a high bonding strength. The epoxy resin of the present invention is preferably a kind of epoxy resin with a high bonding strength. The epoxy resin of the present invention is preferably a kind of epoxy resin with a high bonding strength.

[0054] Commercially available products of epoxy resins include: "jER828", "jER834", "jER807", "jER604", "jER630", "jER871", "jER872", and "jER1031S" (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.), "TETRAD-X" (manufactured by Mitsubishi Gas Chemical Co., Ltd.), "NC-513", "NC-514S", and "NC-547" (all manufactured by Cardolite Corp.), etc.

[0055] In terms of the excellent solder heat resistance of the adhesive layer, the content of the component (B) is preferably 0.1 to 5 parts by weight, more preferably 0.5 to 3 parts by weight, and further preferably 0.8 to 2.5 parts by weight, based on 100 parts by weight of the component (A) in terms of non-volatile components. In addition, the so-called non-volatile components refer to the components remaining after removing volatile components such as water and organic solvents.

[0056] (C) component is a bismaleimide with a dimer diamine skeleton, and is fully compatible with the (A) component and is used to improve the adhesion of the difficult-to-fit substrate for fluorine-based resins, etc. and show a component of high bonding strength. As a commercially available product of (C) component, for example, it can be listed: "BMI-689", "BMI-689C", "BMI-1400", "BMI-1500", "BMI-1550", "BMI-1700", "BMI-3000 commercial grade (COMMERCIAL GRADE)", "BMI-3000J", "BMI-3000 solution (Solution)", "BMI-5000P", "BMI-5000T" (more than for the manufacture of Special Molecule Co., Ltd. (Designer Molecule Inc.)), "SLK-2600" (Shin-Etsu Chemical Industry (stock) manufacture) etc. They can be a single one, and two or more can also be combined.

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

[0058]

[0059] In terms of improving the adhesion of the adhesive layer to difficult-to-bond substrates and showing high bonding strength, and also having excellent solder heat resistance, the content of component (C) 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, relative to 100 parts by weight of component (A), calculated as non-volatile matter.

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

[0061] Examples of the component (C') include maleimide; N-alkyl monomaleimides such as N-methylmaleimide, N-ethylmaleimide, N-n-propylmaleimide, N-isopropylmaleimide, N-n-butylmaleimide, N-isobutylmaleimide, N-tert-butylmaleimide, N-n-pentylmaleimide, N-n-hexylmaleimide, N-n-heptylmaleimide, N-n-octylmaleimide, N-n-nonylmaleimide, N-n-decylmaleimide, N-n-dodecylmaleimide, N-n-tetradecylmaleimide, N-n-hexadecylmaleimide and N-n-octadecylmaleimide; N-cyclopentylmaleimide, N-cyclohexylmaleimide and other N-cycloalkyl monomaleimides; 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'-ethylenebismaleimide, N,N'-trimethylenebismaleimide, N,N'-tetramethylenebismaleimide, N,N'-pentamethylenebismaleimide, N,N'-hexamethylenebismaleimide, N,N-heptamethylenebismaleimide, N,N-octamethylenebismaleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 1,1'-(decane-1,10-diyl)bis(1H-pyrrole-2,5-dione) and other N,N'-alkylenebismaleimides; 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] bismaleimide, N,N'-4,4'-[3,3'-diethyldiphenylmethane] bismaleimide, N,N'-(4,4'-diphenylpropane) bismaleimide, N,N'-diphenylcyclohexane bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, N , N'-diphenyl ether bismaleimide, 1,3-bis(3-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; 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-( Bis(maleimidephenoxyphenyl)alkanes such as bis(maleimidephenoxyphenyl)alkanes such as 2,2-bis[3,5-dimethyl-4-(4-maleimidephenoxy)phenyl]hexafluoropropane, 2,2-bis[3-ethyl-4-(4-maleimidephenoxy)phenyl]propane and 2,2-bis[3-ethyl-4-(4-maleimidephenoxy)phenyl]hexafluoropropane. These may be used alone or in combination of two or more.

[0062] Examples of commercially available products of component (C') include: "BMI", "BMI-70", "BMI-80" (all manufactured by KI Chemicals Co., Ltd.); "BMI-1000", "BMI-1000H", "BMI-1100", "BMI-1100H", "BMI-2000", "BMI-2300", "BMI-3000", "BMI-3000H", "BMI-4000", "BMI-5100", "BMI-7000", "BMI-7000H", "BMI-TMH" (all manufactured by Yamato Chemicals Co., Ltd.), etc.

[0063] The content of the component (C′) is preferably 2.5 parts by weight or less, more preferably 1.5 parts by weight or less, based on 100 parts by weight of the component (A), in terms of nonvolatile matter.

[0064] The component (D) is a diene polymer having a 1,2-vinyl group in a side chain, and is a component for improving the adhesion of the adhesive layer to a substrate with which adhesion is difficult to achieve, thereby achieving high adhesive strength.

[0065] As (D) component, for example, diene homopolymers such as polyisoprene, polybutadiene, and 1,2-butadiene homopolymers can be listed; butadiene-isoprene polymers, isobutylene-isopropylene polymers, butadiene-acrylonitrile polymers, ethoxylated polybutadiene, epoxidized polybutadiene, butadiene-styrene polymers, styrene-butadiene-styrene polymers and other diene copolymers (diene copolymers) and the like. They can be a single type or a combination of two or more. As commercial products, for example, "Ricoh (RICON) 100", "Ricoh (RICON) 150", "Ricoh (RICON) 154", "Ricoh (RICON) 156", "Ricoh (RICON) 181", "Ricoh (RICON) 184" (the above are manufactured by Cray Valley), "NISSO-PBJP-200", "NISSO-PB B-1000" (the above are manufactured by Nippon Soda (stock)), etc.

[0066] Among them, diene copolymers (diene interpolymers) are preferred, and butadiene-styrene polymers are more preferred, in that the adhesive layer improves adhesion to a substrate that is difficult to adhere to and exhibits high adhesive strength.

[0067] The content of the component (D) 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, based on 100 parts by weight of the component (A), in terms of nonvolatile matter.

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

[0069] As (E) component, for example, the component containing dicyclopentadienyl diphenol structure described in Japanese Patent Laid-Open No. 2019-183071, the component containing naphthalene structure, acetylated product of phenol novolac, benzoylated product of phenol novolac, etc. can be listed. They can be single or in combination of two or more.

[0070] As for commercially available products of the component (E), for example, Examples of components containing a dicyclopentadienyldiphenol structure include "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 of China); Examples of components 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).

[0071] As the component (E), components produced by various known methods may be used, and examples thereof include components produced by reacting a polyfunctional phenol compound and an aromatic carboxylic acid as described in Japanese Patent No. 5152445.

[0072] The content of the component (E) 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, based on 100 parts by weight of the component (A), in terms of nonvolatile matter.

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

[0074] 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.

[0075] 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.).

[0076] 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.

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

[0078] 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.

[0079] 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.

[0080] 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.).

[0081] 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.

[0082] 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.

[0083] Examples of the amine include aliphatic amines such as the dimer diamine, component (a2′), 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; Polyamide polyamine, polyether polyamine, polyester polyamine, etc. These may be used alone or in combination of two or more.

[0084] 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.

[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-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.

[0086] 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.

[0087] The content of the curing component is preferably 0.5 to 5 parts by weight, more preferably 0.5 to 2 parts by weight, based on 100 parts by weight of the component (A), in terms of nonvolatile matter.

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

[0089] 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.

[0090] Commercially available products of silica fillers include, for example, “FB-3SDC”, “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 is preferably 1 to 150 parts by weight 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 1 to 150 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 composition layer while maintaining low dielectric properties. As a result, the interfacial adhesion between the adhesive composition layer and the support (so-called anchoring effect) can be improved while suppressing the oozing of the adhesive layer generated from the end of the support.

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

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

[0099] 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 5 to 60 wt %, more preferably 20 to 50 wt %.

[0100] The adhesive composition of the present invention may contain, as an additive, a substance other than 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, or an organic solvent.

[0101] Examples of 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.

[0102] Examples of the content of the additive include less than 1 part by weight, less than 0.1 part by weight, less than 0.01 part by weight, and 0 part by weight based on 100 parts by weight of the component (A) in terms of nonvolatile matter.

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

[0104] [Hardened material] The hardened material of the present invention comprises the adhesive composition. As a method for manufacturing the hardened material, there can be cited a process comprising applying the adhesive composition to a suitable support, a process of hardening by volatilizing an organic solvent by heating, a process of peeling off the support, etc. In addition, the thickness of the hardened material 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 hardened material, the adhesive composition and various known adhesive compositions other than the adhesive composition can also be used in combination.

[0105] [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.

[0106] 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.

[0107] The supporting film may include 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 ethylene terephthalate, phenol, phthalic acid, hydroxynaphthoic acid, etc. and p-hydroxybenzoic acid (so-called liquid crystal polymer; "Vecstar" (manufactured by Kuraray Co., Ltd.), etc.), cycloolefin polymer, fluorine resin (polytetrafluoroethylene (PTFE), perfluoroalkoxy alkane (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, as the 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. The thickness of the coating layer is preferably about 1 μm to 100 μm after drying, 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.

[0109] [Copper foil with resin] The resin-bearing copper foil of the present invention comprises the hardened material or adhesive sheet of the present invention and copper foil. Specifically, the adhesive composition of the present invention is applied to the copper foil and heat-hardened, or the hardened material or adhesive sheet of the present invention is attached 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. Rustproofing treatment can be cited as a so-called mirror treatment such as plating treatment using a plating solution containing Ni, Zn, Sn, etc., chromate treatment, etc.

[0110] 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.

[0111] In addition, the cured product or adhesive sheet of the copper foil with resin may be a cured product or adhesive sheet of the copper foil with resin that is partially cured or completely cured under heating. The partially cured product or adhesive sheet is in a state called the so-called B stage. In addition, the thickness of the cured product or adhesive sheet is preferably about 0.5 μm to 30 μm. In addition, the cured product or adhesive sheet may be further attached to the copper foil of the copper foil with resin to make a double-sided copper foil with resin.

[0112] [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.

[0113] In one embodiment, the insulating sheet is preferably a prepreg or the support film. Prepreg refers to a sheet material (Japanese Industrial Standards (JIS) C 5603) formed by impregnating a resin in a reinforcing material such as glass cloth and hardening it to the B stage. The resin can use insulating resins such as the adhesive composition of the present invention, phenolic resin, epoxy resin, polyester resin, liquid crystal polymer, and aromatic polyamide resin. As the thickness of the insulating sheet, it is preferably about 20μm to 500μm. 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).

[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 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 patterning the copper foil surface of the copper-clad laminate using a resist film, electrolytic copper plating, removing the resist, and etching using an alkali solution can be cited. In addition, the thickness of the circuit pattern layer in the printed wiring board is not particularly limited. In addition, a multilayer substrate can also be obtained 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 stacks in the multilayer substrate is not particularly limited. In addition, each time a through hole is stacked, a through hole can also be inserted and the inside can be plated. The line / space ratio of the circuit pattern is not particularly limited, preferably about 1μm / 1μm to 100μm / 100μm. In addition, the height of the circuit pattern is not particularly limited, but is preferably about 1 μm to 50 μm. [Example]

[0115] 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 mass unless otherwise specified.

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

[0117] Production Example 1 In a reaction container equipped with a stirrer, a water separator, a thermometer and a nitrogen inlet tube, 70.0 g of 4,4'-(hexafluoroisopropylidene) diphthalic anhydride (6FDA, manufactured by Daikin Co., Ltd.), 100.82 g of ethylene glycol dimethyl ether and 235.24 g of toluene were placed and heated to 70° C. Then, 81.8 g of dimer diamine (trade name: "PRIAMINE 1075", manufactured by Croda Japan Co., Ltd., hereinafter referred to as PRIAMINE 1075) was slowly added, and the mixture was heated to 110° C. for 15 hours to carry out an imidization reaction, thereby obtaining a solution of a polyimide resin (A-1) (non-volatile content 35%).

[0118] Production Example 2 In the same reaction container as in Production Example 1, 200.0 g of 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride (trade name "BisDA-1000", manufactured by SABIC Innovative Plastics Japan Co., Ltd., hereinafter referred to as BisDA), 265.27 g of ethylene glycol dimethyl ether and 618.97 g of toluene were placed and heated to 70° C. Subsequently, 197.8 g of PRIAMINE 1075 was slowly added, and the mixture was heated to 110° C. for 10 hours to carry out an imidization reaction, thereby obtaining a solution of a polyimide resin (A-2) (30% non-volatile matter).

[0119] Production Example 3 In the same reaction container as in Production Example 1, 200.0 g of BisDA, 246.83 g of ethylene glycol dimethyl ether and 575.95 g of toluene were placed and heated to 40° C. Then, 14.53 g of 4,4′-diaminophenyl ether (trade name: “ODA”, manufactured by Wakayama Seika Industries Co., Ltd.) and 156.75 g of PRIAMINE 1075 were slowly added, and the mixture was heated to 110° C. and imidization reaction was carried out for 10 hours to obtain a solution of polyimide resin (A-3) (non-volatile content 30%).

[0120] Example 1 271.74 g (non-volatile component 100.0 g) of the component (A-1) as the component (A), 1.0 g (non-volatile component 1.0 g) of N,N,N',N'-tetraglycidyl-4,4'-diaminodiphenylmethane (trade name: "jER604", manufactured by Mitsubishi Gas Chemical Co., Ltd.) as the component (B), and bismaleimide represented by the following formula (4) (trade name: "BMI-689", manufactured by Designer Molecule Co., Ltd.) as the component (C) were mixed. Inc.) as the component (D) (trade name: "RICON 100", manufactured by Crayvalley Co., Ltd.) 11.5 g (non-volatile component: 11.5 g) of a butadiene-styrene polymer as the component (D) (trade name: "Ricoh (RICON) 100", manufactured by Crayvalley Co., Ltd.) 2.2 g (non-volatile component: 2.2 g) of an active ester as the component (E) (trade name: "HPC-8000L", manufactured by DIC (Co., Ltd.) 75.7 g of methyl ethyl ketone as an organic solvent are mixed and stirred thoroughly to obtain an adhesive composition having a non-volatile component of 30%.

[0121]

[0122] Example 2 to Example 11, Comparative Example 1 to Comparative Example 4 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.

[0123] <Adhesive Sheet Production> The adhesive composition of each example and comparative example was applied onto release paper (manufactured by Sun A Kaken Co., Ltd.) using a gap coater to a thickness of 25 μm after drying, and then dried at 150° C. for 5 minutes. The release paper was then peeled off to obtain an adhesive sheet.

[0124] <Measurement of relative dielectric constant and dielectric loss tangent> The adhesive sheet was placed on a pressing support, and then cured by heating and pressing at a pressure of 5 MPa and 180° C. for 90 minutes with the same pressing support interposed on the adhesive sheet side, thereby preparing a heat-cured laminate (support / adhesive sheet / support). The pressing support was removed from the adhesive sheet, and the relative dielectric constant (Dk) and dielectric loss tangent (Df) of the adhesive sheet 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) was calculated from the difference in resonant 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 resonant frequency between the resonator alone and when the test piece was inserted. The results are shown in Table 1 (the same applies below).

[0125] <Manufacturing of copper-clad laminates> The adhesive composition of each example and comparative example was applied onto release paper (manufactured by Sun A Kaken Co., Ltd.) using a gap coater to a thickness of 25 μm after drying, and then dried at 150° C. for 5 minutes to obtain an adhesive sheet (release paper / adhesive layer). A double-sided copper-clad laminate (trade name: "Pyralux TK125012R", manufactured by Dupont; film thickness 75 μm) having copper foil / fluororesin layers laminated on both sides of a polyimide film was etched using a 40% iron (III) chloride aqueous solution to remove the copper foil. Next, each adhesive sheet was overlapped on one side of the exposed fluororesin layer, and further, a commercially available electrolytic copper foil (trade name: "F2-WS", manufactured by Furukawa Circuit Foil (Co., Ltd.), 18 μm thick) was overlapped thereon 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 surfaces in contact, and was heated and pressed from above at a pressure of 10 MPa and a temperature of 180° C. for 90 minutes through a support made of the same raw material to cure, thereby producing a copper-clad laminate.

[0126] <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).

[0127] <Solder Heat Resistance> The copper-clad laminate (1) 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 of bubbling and evaluate according to the following criteria. (Evaluation Criteria) ○: No change in appearance. ×: The copper-clad laminate has foaming, expansion, and peeling.

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

[0129] The symbols shown in Table 1 represent the following compounds, respectively. <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 Co., Ltd.) · B-2: N,N,N',N'-tetraglycidylphenylenediamine (trade name: "TETRAD-X", manufactured by Mitsubishi Gas Chemical Co., Ltd.) B-3: Ether type epoxy resin (trade name: "jER1031S", reaction product of tetrahydroxyphenylethane and epichlorohydrin, manufactured by Mitsubishi Chemical Co., Ltd.) <Bismaleimide> C-1: Bismaleimide represented by the formula (4) (trade name: "BMI-689", manufactured by Designer Molecule Inc.) ·F-1: N,N'-(4,4'-diphenylmethane)bismaleimide (trade name: "BMI-1000H", manufactured by Yamato Chemical Co., Ltd.) <Diene polymer> D-1: Butadiene-styrene polymer (trade name: "RICON 100", manufactured by Crayvalley Corporation) <Other> · E-1: Active ester (trade name: "HPC-8000L", manufactured by DIC Corporation).

Claims

1. An adhesive composition comprising: a polyimide resin (A) as a product of reaction components comprising an aromatic tetracarboxylic dianhydride (a1) and a diamine (a2) containing a dimer diamine, an epoxy resin (B), Bismaleimide (C) having a dimer diamine skeleton, and 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 according to claim 1. 4 . An adhesive sheet comprising a support film having the cured product according to claim 3 on at least one surface thereof. 5 . A copper foil with resin, 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 copper foil with resin 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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