KR102485692B1 - Polyimide-based adhesive - Google Patents

Abstract

＜Tasks＞
A polyimide-based adhesive having good low dielectric properties and excellent adhesion to copper is provided.
<Solution>
A polyimide (A) containing aromatic tetracarboxylic anhydride (a1) and diamine (a2) containing 30 mol% or more of dimerdiamine as constituent components, a hydrogenated petroleum resin (B), a crosslinking agent (C), and an organic solvent A polyimide-based adhesive comprising (D). This adhesive is useful for manufacturing flexible printed wiring boards, printed circuit boards, and multilayer wiring boards using them.

Description

Polyimide-based adhesive {POLYIMIDE-BASED ADHESIVE}

The present invention relates to polyimide-based adhesives. This adhesive is useful for manufacturing flexible printed wiring boards, printed circuit boards, and multilayer wiring boards using them.

Flexible Printed Wiring Boards (FPWBs), Printed Circuit Boards (PCBs), and Multi-Layer Boards (MLBs) using them are used for mobile communication devices such as mobile phones and smartphones, and their base station devices. , it is used in products such as network-related electronic devices such as servers and routers, and large computers.

In recent years, in these products, high-frequency electrical signals are used to transmit and process large amounts of information at high speed. However, since high-frequency signals are very easily attenuated, a device for suppressing transmission loss is required for the multilayer wiring board and the like.

Transmission loss can be divided into "dielectric loss" derived from the insulating material around the dielectric, that is, the conductor (copper circuit), and "conductor loss" derived from the copper circuit itself, and both must be suppressed.

The dielectric loss depends on the frequency and the dielectric constant and dielectric loss tangent of the insulating material around the copper circuit. And, as the frequency is higher, it is necessary to use a material having a low dielectric constant and a low dielectric loss tangent as the insulating material.

On the other hand, conductor loss is due to the skin effect, that is, a phenomenon in which the AC current density on the surface of a copper circuit increases and its resistance increases, and becomes remarkable when the frequency exceeds GHz. The main countermeasure against conductor loss is the smoothing of the copper circuit surface.

In order to suppress dielectric loss, as described above, it is good to use a material having a low dielectric constant and low dielectric loss as an insulating material, and as such a material, a specific polyimide has been conventionally used (see Patent Documents 1 and 2).

However, since such an insulating material does not have a polar group, that is, a functional group such as a hydroxyl group, a carboxyl group, and a nitrile group, or has a small amount, it is difficult to adhere to a smooth copper circuit. Conversely, a material having many such functional groups tends to have high dielectric constant and high dielectric loss tangent even though its adhesion is high.

Japanese Patent Laid-Open No. 2009-299040 Japanese Patent Laid-Open No. 2014-045076

The present invention is a novel polyimide having both a low dielectric constant and a dielectric loss tangent (hereinafter, both are collectively referred to as dielectric properties) and having good adhesion to copper, particularly copper having a smooth surface (hereinafter also referred to simply as copper adhesion). The main problem is to provide a system adhesive.

As a result of intensive studies, the present inventors have found that an adhesive capable of solving the above problems can be obtained by combining a polyimide containing dimerdiamine as a constituent component and a hydrogenated petroleum resin.

That is, the present invention is a polyimide (A) containing aromatic tetracarboxylic anhydride (a1) and diamine (a2) containing 30 mol% or more of dimerdiamine as constituent components, a hydrogenated petroleum resin (B), and a crosslinking agent (C) And, it relates to a polyimide-based adhesive containing an organic solvent (D).

The polyimide-based adhesive of the present invention has good compatibility and can be used as a homogeneous varnish free from insoluble matter. Further, the adhesive layer composed of the adhesive has excellent both low dielectric properties and copper adhesion, and also has good solder heat resistance.

The adhesive of the present invention can be used for the production of flexible printed wiring boards and printed circuit boards and multilayer wiring boards using them. These are very suitable for products that handle high-frequency signals such as mobile communication devices represented by smartphones and mobile phones, their base station devices, network-related electronic devices such as servers and routers, and large computers.

The polyimide-based adhesive of the present invention is a predetermined polyimide (A) (hereinafter also referred to as component (A)), a hydrogenated petroleum resin (B) (hereinafter also referred to as component (B)), and a crosslinking agent (C) (hereinafter referred to as ( It is also referred to as component C) and an organic solvent (D) (hereinafter also referred to as component (D)).

Component (A) is composed of an aromatic tetracarboxylic anhydride (a1) (hereinafter also referred to as component (a1)) and a diamine (a2) containing 30 mol% or more of dimerdiamine (hereinafter also referred to as component (a2)). it is a polymer

As the component (a1), various known aromatic tetracarboxylic acid anhydrides can be used. Specifically, for example, pyromellitic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 3,3',4,4' -diphenyl ether tetracarboxylic acid dianhydride, 3,3',4,4'-diphenylsulfonetetracarboxylic acid dianhydride, 1,2,3,4-benzenetetracarboxylic acid anhydride, 1,4,5,8-naphthalene tetra Carboxylic acid anhydride, 2,3,6,7-naphthalenetetracarboxylic acid anhydride, 3,3',4,4'-biphenyltetracarboxylic acid dianhydride, 2,2',3,3'-biphenyltetracarboxylic acid dianhydride, 2, 3, 3', 4'-biphenyltetracarboxylic dianhydride, 2, 3, 3', 4'-benzophenonetetracarboxylic dianhydride, 2, 3, 3', 4'-diphenyl ether tetracarboxylic dianhydride Water, 2,3,3',4'-diphenylsulfonetetracarboxylic dianhydride, 2,2-bis(3,3',4,4'-tetracarboxyphenyl)tetrafluoropropane dianhydride, 2,2 '-bis(3,4-dicarboxyphenoxyphenyl)sulfone dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl) Propane dianhydride and 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]diphthalic dianhydride, etc. are mentioned, You may combine 2 or more types. Among these, 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-[propane-2,2-diylbis(1,4- Phenyleneoxy)] at least one selected from the group consisting of diphthalic dianhydride and 4,4'-oxydiphthalic anhydride is preferred. In one embodiment, component (a1) is represented by the following structure.

(In the formula, X is a single bond, -SO ₂ -, -CO-, -O-, -O-C ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O- or COO-Y-OCO- (Y represents -(CH ₂ ) _l -(l = 1 to 20) or -H ₂ C-HC (-O-C(=O)-CH ₃ )-CH ₂ -)

Dimerdiamine, an essential component of component (a2), is a compound derived from dimer acid, which is a dimer of unsaturated fatty acids such as oleic acid (see Japanese Patent Laid-Open No. 1997-12712, etc.), and various known dimerdiamines can be used without particular limitation. can (a2) Examples of commercially available components include Versamin 551 (manufactured by BASF Japan Co., Ltd.), Versamin 552 (manufactured by Cognix Japan Co., Ltd.; hydrogenated product of Versamine 551), PRIAMINE 1075, PRIAMINE 1074 (both Kuroda Japan Co., Ltd. product) etc. are mentioned.

The content of the dimerdiamine in component (a2) is usually 30 moles from the viewpoint of the low dielectric properties, copper adhesion and solder heat resistance of the adhesive of the present invention, and the solubility of component (A) in component (D) described later. % or more, preferably about 100 to 50 mol%.

(a2) You may also include various well-known diaminopolysiloxane in the range of less than 70 mol% in component (a2). Specific examples 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, α,ω-bis[3-(4-aminophenyl)propyl]polydimethyl Siloxane etc. are mentioned. By including the diaminopolysiloxane in the component (a2), the flexibility of the adhesive layer and the surface smoothness of the coating film are improved, and the adhesion of the adhesive of the present invention to copper is improved. From this point of view, the content of the diaminopolysiloxane in the component (a2) is preferably about 0.1 to 10.0 mol%.

Component (a2) may further contain diamines other than the above dimer diamine and the above diaminopolysiloxane. Specific examples include diaminocyclohexane, diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, tetramethyldiaminodicyclohexylmethane, diaminodicyclohexylpropane, and diaminobicyclo[2. 2. 1] heptane, bis(aminomethyl)-bicyclo[2. 2. 1] heptane, 3(4), 8(9)-bis(aminomethyl)tricyclo[5. 2. Alicyclic diamines such as 1.02,6]decane, 1,3-bisaminomethylcyclohexane, and isophoronediamine; 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2, Bisaminophenoxyphenylpropanes such as 2-bis[4-(4-aminophenoxy)phenyl]propane; 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4, Diaminodiphenyl ethers such as 4'-diaminodiphenyl ether; Phenylenediamines such as p-phenylenediamine and m-phenylenediamine; 3,3'-diaminodiphenyl sulfide, 3,4 Diaminodiphenyl sulfides such as '-diaminodiphenyl sulfide and 4,4'-diaminodiphenyl sulfide; 3,3'-diaminodiphenyl sulfone, 3,4'-diaminodiphenyl Diaminodiphenylsulfones such as sulfone and 4,4'-diaminodiphenylsulfone; 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, and 3,4'-diaminobenzophenone Diaminobenzophenones such as the like; Diaminodiphenylmethanes such as 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, and 3,4'-diaminodiphenylmethane; Diaminophenyl propanes such as 2-di(3-aminophenyl)propane, 2,2-di(4-aminophenyl)propane, and 2-(3-aminophenyl)-2-(4-aminophenyl)propane 2,2-di(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-di(4-aminophenyl)-1,1,1,3, Diaminophenylhexafluoro, such as 3,3-hexafluoropropane, 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane Lopropanes; 1,1-di(3-aminophenyl)-1-phenylethane, 1,1-di(4-aminophenyl)-1-phenylethane, 1-(3-aminophenyl)-1-( Diaminophenylphenylethanes such as 4-aminophenyl)-1-phenylethane; 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4 -Bisaminophenoxybenzenes such as 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-a bisaminobenzoylbenzenes such as minobenzoyl)benzene; 1,3-bis(3-amino-α,α-dimethylbenzyl)benzene, 1,3-bis(4-amino-α,α-dimethylbenzyl)benzene; Bisaminodimethylbenzenes such as 1,4-bis(3-amino-α,α-dimethylbenzyl)benzene and 1,4-bis(4-amino-α,α-dimethylbenzyl)benzene; 1,3-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1, 3-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 1, 4-bis (3-amino -Bisaminoditrifluoromethylbenzenes such as α,α-ditrifluoromethylbenzyl)benzene and 1,4-bis(4-amino-α,α-ditrifluoromethylbenzyl)benzene; 2 , 6-bis(3-aminophenoxy)benzonitrile, 2,6-bis(3-aminophenoxy)pyridine, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis Aminophenoxybiphenyls such as (4-aminophenoxy)biphenyl; Aminophenox such as bis[4-(3-aminophenoxy)phenyl]ketone and bis[4-(4-aminophenoxy)phenyl]ketone Cyphenyl ketones; Aminophenoxyphenyl sulfides such as bis[4-(3-aminophenoxy)phenyl]sulfide and bis[4-(4-aminophenoxy)phenyl]sulfide; Bis[4-( Aminophenoxyphenyl sulfones such as 3-aminophenoxy)phenyl]sulfone, bis[4-(4-aminophenoxy)phenyl]sulfone; bis[4-(3-aminophenoxy)phenyl] ether, bis[ Aminophenoxyphenyl ethers such as 4-(4-aminophenoxy)phenyl]ether; 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(3) -aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3 , Aminophenoxyphenylpropanes such as 3,3-hexafluoropropane; other 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, 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, 4,4'-bis[4-(4-aminophenoxy)benzoyl]diphenyl ether, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]benzophenone , 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenylsulfone, 4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenyl Sulfone, 3,3'-diamino-4,4'-diphenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 3,3'-diamino-4- Phenoxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 6,6'-bis(3-aminophenoxy)3,3,3,'3,'-tetramethyl-1, 1'-spirobiindan, 6,6'-bis(4-aminophenoxy)3,3,3,'3,'-tetramethyl-1,1'-spirobiindan, 1,3-bis(3 -aminopropyl) tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldisiloxane, 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) ethyl Toxy)ethane, 1,2-bis(2-aminoethoxy)ethane, 1,2-bis[2-(aminomethoxy)ethoxy]ethane, 1,2-bis[2-(2-aminoethoxy) ) Ethoxy] ethane, ethylene glycol bis(3-aminopropyl) ether, diethylene glycol bis(3-aminopropyl) ether, triethylene glycol bis(3-aminopropyl) ether, ethylenediamine, 1,3-diamino Propane, 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. may be mentioned, and you may combine 2 or more types. Although content of these other diamines in component (a2) is not specifically limited, It is usually less than 50 mol%.

The molar ratio [(a1)/(a2)] of the component (a1) and the component (a2) is not particularly limited, but is usually 1.0 to 1.0 in view of the balance of low dielectric properties and copper adhesion of the adhesive of the present invention, compatibility, and the like. It is about 1.5.

(A) component can be manufactured by various well-known methods. Specifically, for example, components (a1) and (a2), and other reaction components as necessary, are usually heated at a temperature of about 60 to 120°C (preferably 80 to 100°C), usually about 0.1 to 2 hours. (Preferably 0.1 to 0.5 hours) The central portion is allowed to react. Next, the obtained polyadduct may be subjected to an imidization reaction, that is, a dehydration ring closure reaction, at a temperature of about 80 to 250° C., preferably about 100 to 200° C., for about 0.5 to 50 hours (preferably 1 to 20 hours). . In addition, at the time of these reactions, component (D) mentioned later, especially an aprotic polar solvent can be used as a reaction solvent.

In the imidation reaction, various known reaction catalysts, dehydrating agents, and solvents described later can be used. 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. good night. Moreover, as a dehydrating agent, aromatic acid anhydrides, such as aliphatic acid anhydrides, such as acetic anhydride, and benzoic acid anhydride, etc. are mentioned, for example, You may combine 2 or more types.

The imide closure rate of component (A) is not particularly limited, but is usually 70% or more, preferably 85 to 100%. Here, "imide closure rate" means the content of cyclic imide bonds in component (A) (hereinafter the same), and can be determined by various spectroscopic means such as NMR and IR analysis, for example.

The physical properties of component (A) are not particularly limited, but in terms of balance of compatibility, low dielectric properties and copper adhesion, the number average molecular weight (gel permeation chromatography) refers to the value in terms of polystyrene. The same below) is about 5000 to 50000, and the softening point is usually about 30 to 160 ° C.

Although the terminal acid anhydride group concentration of component (A) is not particularly limited, it is usually about 2000 to 40000 eq/g. In addition, for the purpose of adjusting the heat resistance of the adhesive layer of the adhesive according to the present invention and the melt viscosity of the adhesive layer, various known primary alkyl monoamines may be imide-reacted with the terminal acid anhydride group. Specific examples of the amine include, for example, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, sec-butylamine, tert-butylamine, pentylamine, isopentylamine, and tert-pentyl. Amine, n-octylamine, n-decylamine, isodecylamine, n-tridecylamine, n-laurylamine, n-cetylamine, n-stearylamine, etc. are mentioned, and among these, the carbon number of an alkyl group is It is preferable that it is about 4-15.

(B) As a component, various well-known hydrogenated petroleum resins can be used. Specifically, at least one hydride selected from the group consisting of C5-based petroleum resins, C9-based petroleum resins, and C5/C9-based petroleum resins is exemplified. The C5-based petroleum resin is a petroleum resin obtained from a C5 fraction of naphtha, and examples of the C5 fraction include cyclopentadiene, pentene, pentadiene, and isoprene. The C9-based petroleum resin is a petroleum resin obtained from the C9 fraction of naphtha, and examples of the C9 fraction include indene, methylindene, vinyltoluene, styrene, α-methylstyrene, and β-methylstyrene. The C5/C9 petroleum resin is a petroleum resin obtained from the C5 fraction and the C9 fraction. These petroleum resins may also contain olefins such as coumaron, dicyclopentadiene, butene, pentene, hexene, heptene, octene, butadiene, pentadiene, cyclopentadiene, and octadiene as constituent components.

Petroleum resin is obtained by cationic polymerization of the oil as a raw material in the presence of a Friedelcrafts catalyst such as aluminum chloride or boron trifluoride. And the objective (B) component is obtained by hydrogenating the obtained cationic polymer in presence of various well-known hydrogenation catalysts. Examples of the hydrogenation catalyst include metals such as nickel, palladium, cobalt, ruthenium, platinum, and rhodium, and oxides of these metals. In addition, the hydrogenation conditions are not particularly limited, and the temperature is usually about 200 to 300°C and the pressure is about 10 to 300 kg/cm ² . (B) Component may be a commercial product, and examples thereof include Arcon P series and Arcon M series manufactured by Arakawa Chemical Industry Co., Ltd.

The physical properties of the component (B) are not particularly limited, but from the viewpoint of compatibility, copper adhesion, etc., it is usually preferable that the softening point is about 80 to 160°C.

In addition, the present inventor's investigation revealed that the content of the aromatic ring contained in component (B) affects the copper adhesion and low dielectric properties of the adhesive of the present invention. By setting the content to less than 50% by weight, preferably less than 30% by weight, it is possible to lower dielectric properties while maintaining copper adhesion. The content is the reciprocal of the hydrogenation rate of component (B), and the hydrogenation rate can be obtained through the following equation using the ^H -spectrum area of the aromatic ring appearing around 7 ppm of 1H-NMR of component (B).

Hydrogenation rate = [1-[spectral area of component (B) / spectral area of raw petroleum resin]] × 100 (%)

The amount of component (B) used is not particularly limited, but is usually 1 to 30 parts by weight based on 100 parts by weight of component (A) in view of the compatibility of the adhesive of the present invention, low dielectric properties, copper adhesion and solder heat resistance, etc. It is about negative (in terms of solid content).

As the component (C), various known thermosetting resins can be used without particular limitation as long as they function as a crosslinking agent for polyimide. Specifically, at least one selected from the group consisting of epoxy compounds, benzoxazine compounds, bismaleimide compounds, and cyanate ester compounds is preferable.

Examples of the epoxy compound include phenol novolak type epoxy compounds, cresol novolak type epoxy compounds, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, hydrogenated bisphenol A type epoxy compounds, hydrogenated bisphenol F type epoxy Compound, stilbene-type epoxy compound, triazine skeleton-containing epoxy compound, fluorene skeleton-containing epoxy compound, linear aliphatic epoxy compound, alicyclic epoxy compound, glycidylamine-type epoxy compound, triphenolmethane-type epoxy compound, alkyl-modified triphenol Methane-type epoxy compounds, biphenyl-type epoxy compounds, dicyclopentadiene skeleton-containing epoxy compounds, naphthalene skeleton-containing epoxy compounds, arylalkylene-type epoxy compounds, tetraglycidylxylylenediamine, obtained by modifying these epoxy compounds with dimer acids A modified epoxy compound, dimer acid diglycidyl ester, etc. are mentioned, You may combine 2 or more types. In addition, as commercially available products, for example, "jER828", "jER834", "jER807" manufactured by Mitsubishi Chemical Corporation, "ST-3000" manufactured by Nippon Chemical Co., Ltd., "Daicel Chemical Industry Co., Ltd." Ceroxide 2021P", Nippon Chemical Co., Ltd. product "YD-172-X75", Mitsubishi Gas Chemical Co., Ltd. product "TETRAD-X", etc. are mentioned. Among these, bisphenol A type epoxy compounds, bisphenol F type epoxy compounds, hydrogenated bisphenol A type epoxy compounds and alicyclic epoxy compounds are selected from the viewpoint of the compatibility of the adhesive of the present invention and the balance of low dielectric properties, copper adhesion and solder heat resistance. At least one selected from the group consisting of is preferred, and tetraglycidylxylylenediamine having the following structure is particularly preferred.

When using an epoxy compound as a thermosetting resin, various well-known hardening|curing agents for epoxy compounds can be used together. Specifically, for example, succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, Or a mixture of 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, norbornane-2,3-dicarboxylic acid anhydride, methyl Acid anhydride-based curing agents such as norbornane-2,3-dicarboxylic acid anhydride, methylcyclohexenedicarboxylic acid anhydride, 3-dodecenylsuccinic anhydride, and octenylsuccinic anhydride; dicyandiamide (DICY), aromatic diamine (trade name "Lonzacure M -DEA”, “Lonzacure M-DETDA”, etc. (all manufactured by Lonza Japan Co., Ltd.), amine curing agents such as aliphatic amines; Phenolic curing agents such as novolak resins and phenolic hydroxyl group-containing phosphazenes (trade name "SPH-100" manufactured by Otsuka Chemical Co., Ltd.), cyclic phosphazene compounds, rosins such as maleic acid-modified rosin and hydrides thereof A crosslinking agent etc. are mentioned, You may combine 2 or more types. Among these, a phenol-based curing agent, particularly a phenolic hydroxyl group-containing phosphazene-based curing agent is preferred. The amount of these curing agents used is not particularly limited, but is usually about 0.1 to 120% by weight, preferably about 10 to 40% by weight, when the solid content of the adhesive of the present invention is 100% by weight.

When using the said epoxy compound, you may use the catalyst for accelerating the reaction of this and a hardening|curing agent. Specifically, for example, 1,8-diaza-bicyclo[5. 4.0] tertiary amines such as undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris(dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole , 2-phenyl-4-methylimidazole, imidazoles such as 2-heptadecylimidazole; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine, etc. Organic phosphines of; tetraphenyl boron salts such as tetraphenylphosphonium tetraphenyl borate, 2-ethyl-4-methylimidazole tetraphenyl borate, and N-methylmorpholine tetraphenyl borate; You may combine 2 or more types. In addition, the amount of the sugar catalyst used is not particularly limited, but is usually about 0.01 to 5% by weight when the solid content of the adhesive of the present invention is 100% by weight.

Examples of the benzoxazine compound 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. are mentioned, You may combine 2 or more types. A phenyl group, a methyl group, a cyclohexyl group or the like may be bonded to the nitrogen of the oxazine ring. In addition, commercially available products include, for example, "benzoxazine F-a type" and "benzoxazine P-d type" manufactured by Shikoku Chemical Industry Co., Ltd., and "RLV-100" manufactured by Air Water Co., Ltd. there is.

Examples of the bismaleimide compound include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenylether bismaleimide, 3,3'-dimethyl-5,5'- Diethyl-4,4'-diphenylmethanebismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide (2,2,4-trimethyl)hexane, 4, 4'-diphenyl ether bismaleimide, 4,4'-diphenylsulfone bismaleimide, etc. are mentioned, You may combine 2 or more types. Moreover, as a commercial item, "BAF-BMI" by JFE Chemical Co., Ltd., etc. are mentioned, for example.

Examples of the cyanate ester compound include 2-allylphenol cyanate ester, 4-methoxyphenol cyanate ester, 2,2-bis(4-cyanatophenol)-1, 1, 1, 3, 3, 3 -Hexafluoropropane, bisphenol A cyanate ester, diallylbisphenol A cyanate ester, 4-phenylphenol cyanate ester, 1,1,1-tris(4-cyanatophenyl)ethane, 4-cumylphenol cyanate ester, 1,1-bis(4-cyanatophenyl)ethane, 4,4'-bisphenol cyanate ester, and 2,2-bis(4-cyanatophenyl)propane; and the like, combinations of two or more You can do it. Moreover, as a commercial item, "PRIMASET BTP-6020S (made by Lonza Japan Co., Ltd.)" etc. are mentioned, for example.

The amount of component (C) used is not particularly limited, but is usually 1 to 30 based on 100 parts by weight of component (A) in view of the compatibility of the adhesive of the present invention and the balance of low dielectric properties, copper adhesion and solder heat resistance. It is about parts by weight (in terms of solid content).

The polyimide adhesive of the present invention may further contain an organic solvent (D) (hereinafter also referred to as component (D)). Specifically, aprotic polar compounds such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylcaprolactam, methyltriglyme, and methyldiglyme solvents, alicyclic solvents such as cyclohexanone and methylcyclohexane, alcohol solvents such as methanol, ethanol, propanol, benzyl alcohol and cresol, and aromatic solvents such as toluene.

Although the amount of component (D) used is not particularly limited, it is usually about 1 to 500 parts by weight with respect to 100 parts by weight of component (A) from the viewpoint of the compatibility of the adhesive of the present invention.

The adhesive of the present invention has the general formula: Z-Si(R ¹ ) _a (OR ² ) _{3 -a} (wherein Z is a group containing an acid anhydride group and a reactive functional group, R ¹ is hydrogen or a hydrocarbon having 1 to 8 carbon atoms) The group may further include a reactive alkoxysilyl compound (E) represented by R ² is a hydrocarbon group having 1 to 8 carbon atoms and a represents 0, 1 or 2 (hereinafter, also referred to as component (E)). By component (E), the melt viscosity of the adhesive layer made of the adhesive of the present invention can be adjusted while maintaining the low dielectric properties. As a result, it is possible to suppress the exudation of the cured layer from the end of the substrate while increasing the interfacial adhesion between the adhesive layer and the substrate (a so-called anchor effect).

An amino group, an epoxy group, a thiol group, etc. are mentioned as a reactive functional group contained in Z of general formula. As a compound in which Z contains an amino group, for example, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, 3- Aminopropyl trimethoxysilane, 3-aminopropyl triethoxysilane, 3-ureidopropyl trialkoxysilane, etc. are mentioned. Examples of the compound in which Y contains an epoxy group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, and 3-glycidoxypropyltrimethoxysilane. , 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc. are mentioned. As a compound in which Y contains a thiol group, for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldie Toxysilane etc. are mentioned. Among these, a compound in which Y contains an amino group is preferable because it reacts rapidly with the component (A) and has a good flow control effect.

The amount of component (E) used is not particularly limited, but is usually about 0.01 to 5 parts by weight, preferably about 0.1 to 3 parts by weight, based on 100 parts by weight of component (A).

The polyimide-based adhesive of the present invention may further contain a flame retardant (F) (hereinafter also referred to as component (F)). Specifically, phosphorus-based flame retardants and/or phosphazene-based flame retardants, such as polyphosphoric acid and phosphate ester, etc. are mentioned. Examples of the phosphorus-based flame retardant include Exolit OP935 manufactured by Clariant Japan Co., Ltd., and examples of the phosphazene-based flame retardant include Labitol FP-300 manufactured by Fushimi Pharmaceutical Co., Ltd. and the like.

Although the amount of component (F) used is not particularly limited, it is usually about 1 to 100 parts by weight with respect to 100 parts by weight of component (A).

The polyimide-based adhesive of the present invention may further contain an inorganic filler (G) (hereinafter also referred to as component (G)). Specifically, for example, aluminum hydroxide, magnesium hydroxide, calcium carbonate, magnesium carbonate, calcium silicate, magnesium silicate, calcium oxide, magnesium oxide, aluminum oxide, aluminum nitride, aluminum borate whisker, boron nitride, crystalline silica, amorphous Silica, graphite powder, boehmite, etc. are mentioned.

Although the amount of component (G) used is not particularly limited, it is usually about 1 to 300 parts by weight with respect to 100 parts by weight of component (A).

In addition, the adhesive of the present invention, if necessary, the ring-opening esterification reaction catalyst, dehydrating agent, plasticizer, weathering agent, antioxidant, heat stabilizer, lubricant, antistatic agent, brightener, colorant, conductive agent, release agent, surface treatment agent, viscosity modifier etc. can be combined.

The polyimide-based adhesive of the present invention consists of the above components (A), (B), (C) and (D), and, if necessary, the above (E), (F) and (G) components. At least one selected from the group is mixed to obtain a varnish-like solution.

The polyimide-based adhesive of the present invention can be used as a film-like adhesive material (adhesive film) by applying to a support film to be described later, semi-curing, and peeling from the support film. Although the thickness of the adhesive material is not particularly limited, it is usually about 0.5 to 80 μm.

The polyimide-based adhesive and the film-like adhesive of the present invention can be used for production of a multilayer wiring board. Specifically, the adhesive or the adhesive material may be brought into contact with at least one side of a printed wiring board serving as a core substrate, laminated with another printed wiring board or printed circuit board thereon, and then pressed under heating and pressure. The heating temperature and pressing time are not particularly limited, but usually (a) after bringing the polyimide-based adhesive or film-like adhesive of the present invention into contact with at least one side of a printed wiring board as a core substrate, it is usually heated to about 70 to 200 ° C., After the curing reaction is carried out over about 1 to 10 minutes, (b) in order to advance the curing reaction, it is preferable to heat treatment at about 150 ° C. to 250 ° C. for about 10 minutes to 3 hours. Also, the pressure is not particularly limited, but is usually about 0.5 to 20 MPa, preferably about 1 to 8 MPa through steps (a) and (b).

The polyimide-based adhesive may be applied to a support film and processed into an adhesive sheet. Examples of the supporting film include polyester, polyimide, polyimide-silica hybrid, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate resin, polystyrene resin, polycarbonate resin, and acrylonitrile. －Plastics such as butadiene-styrene resins, aromatic polyester resins obtained from ethylene terephthalate, phenol, phthalic acid, hydroxynaphthoic acid, etc., and para-hydroxybenzoic acid (so-called liquid crystal polymers; Kuraray Co., Ltd., "Bexstar", etc.) film can be taken. In addition, the application means is not particularly limited, either, and a curtain coater, a roll coater, a laminator, and the like can be cited. Also, the thickness of the coating layer is not particularly limited, but the thickness after drying may be in the range of usually about 1 to 100 μm, preferably about 3 to 50 μm. Moreover, you may protect the adhesive layer of the said adhesive sheet with various protective films.

The polyimide-based adhesive or film-like adhesive may be processed into a resin portion copper foil by applying or bonding them to copper foil. As the said copper foil, a rolled copper foil and an electrolytic copper foil are mentioned, for example. Also, the thickness is not particularly limited, and is usually about 1 to 100 μm, preferably about 2 to 38 μm. Further, the copper foil may be subjected to various surface treatments (roughening, rust prevention, etc.). Examples of the anti-rust treatment include a plating treatment using a plating solution containing Ni, Zn, Sn, and the like, a so-called mirror surface treatment such as a chromate treatment, and the like. Moreover, the above method is mentioned as an application|coating means. Moreover, the adhesive layer of the resin part copper foil may be uncured, and may be partially cured or completely cured under heating. The partially cured adhesive layer is in a so-called B-stage state. Also, the thickness of the adhesive layer is not particularly limited, and is usually about 0.5 to 30 μm. Moreover, it is also possible to bond copper foil to the adhesive surface of the said resin part copper foil, and it can also be set as a double-sided resin part copper foil.

The said copper-clad laminate is an article formed by bonding the resin part copper foil of this invention, and a copper foil or an insulating sheet, and is also called CCL (Copper Clad Laminate). Specifically, the resin portion copper foil of the present invention is pressed under heating on at least one side or both sides of various known insulating sheets. Moreover, in the case of one surface, you may crimp a thing different from the resin part copper foil of this invention to the other surface. In addition, the number of resin portion copper foils and insulating sheets in the copper clad laminate is not particularly limited. Moreover, as the said insulating sheet, a prepreg is preferable. 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), and the resin is usually polyimide resin, phenol resin, epoxy resin, polyester resin, liquid crystal polymer, An insulating resin such as aramid resin is used. In addition, the thickness of the prepreg is not particularly limited and is usually about 20 to 500 μm. In addition, the heating and pressing conditions are not particularly limited, and are usually about 150 to 280°C (preferably about 170°C to 240°C) and about 0.5 to 20 MPa (preferably about 1 to 8 MPa).

The copper clad laminate can be used as a printed wiring board by forming a circuit pattern on the copper foil surface. As a patterning means, a subtractive method and a semiadditive method are mentioned, for example. As a semi-additive method, for example, after patterning the copper foil surface of the copper-clad laminate of the present invention with a resist film, electrolytic copper plating is performed, the resist is removed, and a method of etching with an alkali solution is exemplified. Moreover, the thickness of the circuit pattern layer in the said printed wiring board is not specifically limited. Moreover, a multilayer board|substrate can also be obtained by using the said printed wiring board as a core base material, and laminating|stacking the same printed wiring board, another well-known printed wiring board, or a printed circuit board on it. During lamination, other known polyimide-based adhesives may be used as well as the polyimide-based adhesive of the present invention. Moreover, the number of laminated layers in a multi-layer board is not particularly limited. Further, via holes may be inserted for each lamination, and the inside may be plated.

[Example]

Hereinafter, the present invention will be specifically described through Examples and Comparative Examples, but the scope of the present invention is not limited thereto. In addition, parts and % in each case are based on weight unless otherwise specified.

The number average molecular weight is a value obtained using a commercially available measuring device ("High-Speed GPC HLC-8220", manufactured by TOSOH).

The softening point is the temperature at which the stiffness starts to decrease in the viscoelasticity profile measured using a commercially available measuring device ("ARES-2KSTD-FCO-STD", manufactured by Rheometric Scientific).

manufacturing example One

A commercially available aromatic tetracarboxylic dianhydride (trade name "BTDA-UP", manufactured by Evonik Japan Co., Ltd.; 3, 3', Content of 4,4'-benzophenone tetracarboxylic dianhydride was 99.9% or more) 210.0 g, 1008.0 g of cyclohexanone, and 201.6 g of methylcyclohexane were put, and the solution was heated to 60 degreeC. Next, 341.7 g of hydrogenated dimerdiamine (trade name "PRIAMINE 1075", manufactured by Kuroda Japan Co., Ltd.) was added dropwise, followed by an imidation reaction at 140°C for 10 hours, and a solution of polyimide resin (A-1) Volatile content 30.2%) was obtained. Moreover, the molar ratio of acid component/amine component was 1.03. Moreover, the number average molecular weight of the said component (A-1) was 15,000, and the softening point was about 80 degreeC.

manufacturing example 2

Into the same reaction vessel as in Production Example 1, commercially available aromatic tetracarboxylic dianhydride (trade name "BisDA1000", manufactured by Evonik Japan Co., Ltd.; 4,4'-[propane-2,2-diylbis(1,4- 297.8 g of phenyleneoxy)] diphthalic dianhydride (98.0%), 818.95 g of cyclohexanone, and 136.49 g of methylcyclohexane were placed, and the solution was heated to 60°C. Next, 200.28 g of PRIAMINE 1075 and 24.83 g of 1,3-bisaminomethylcyclohexane were added dropwise, followed by an imidization reaction at 140° C. over 10 hours to obtain a polyimide (A-2) solution (29.7% non-volatile content). ) was obtained. The molar ratio of the acid component/amine component of the polyimide resin was 1.05. Moreover, the number average molecular weight of the said component (A-2) was 15,000, and the softening point was about 100 degreeC.

manufacturing example 3

200.00 g of BisDA1000, 700.00 g of cyclohexanone, and 175.00 g of methylcyclohexane were placed in a reaction container similar to that in Production Example 1, and the solution was heated to 60°C. Next, after dripping 190.54 g of PRIAMINE 1075, an imidation reaction was carried out at 140°C over 10 hours to obtain a polyimide (A-3) solution (30.1% of non-volatile content). The molar ratio of the acid component/amine component of the polyimide resin was 1.09.

manufacturing example 4

In the same reaction container as in Production Example 1, (trade name "BTDA-PF", manufactured by Evonik Japan Co., Ltd.; content of 3,3',4,4'-benzophenonetetracarboxylic dianhydride is 98%) 190.0g, 277.5 g of cyclohexanone and 182.4 g of methylcyclohexane were added, and the solution was heated to 60°C. Next, 277.5 g of PRIAMINE 1075 and commercially available α,ω-bis(3-aminopropyl)polydimethylsiloxane (trade name “KF-8010”, manufactured by Shin-Etsu Chemical Co., Ltd.) 23.8 g were added dropwise, followed by 140° C. The polyimide (A-4) solution (30.5% of non-volatile content) was obtained by imidation reaction over 10 hours. The molar ratio of the acid component/amine component of the polyimide resin was 1.09. Moreover, the number average molecular weight of the said component (A-4) was 10,000, and the softening point was about 70 degreeC.

Comparative Manufacturing Example One

1300.0 g of BisDA1000, 364.0 g of methylcyclohexane, and 2184.0 g of diethylacetamide were placed in a reaction container similar to that in Production Example 1, and the solution was heated to 60°C. Next, after 323.27 g of 1,3-bisaminomethylcyclohexane was dripped, an imidation reaction was carried out at 140°C over 10 hours to obtain a polyimide (A-5) solution (37.7% of non-volatile content). In addition, the molar ratio of the acid component/amine component was 1.10.

Comparative Manufacturing Example 2

297.8 g of BisDA1000, 818.95 g of cyclohexane, 136.49 g of methylcyclohexane, and 245.63 g of diethylacetamide were placed in a reaction vessel similar to that in Production Example 1, and the solution was heated to 60°C. Next, 73.51 g of PRIAMINE 1075 and 58.19 g of 1,3-bisaminomethylcyclohexane were added dropwise, followed by an imidization reaction at 140°C for 10 hours to obtain a polyimide (A-6) solution (37.7% of non-volatile content) got In addition, the molar ratio of the acid component/amine component was 1.10.

Example One

3.93 g of solution of component (A-1), 4.00 g of solution of component (A-2), 1.95 g of solution of component (A-3), and hydrogenated petroleum resin as component (B) (trade name "Arcon P-100", Arakawa Chemical Industry Co., Ltd., softening point 100°C, aromatic ring content 10% by weight) 0.17 g, N,N-diglycidyl-4-glycidyloxyaniline as component (C) (trade name "jER630", Mitsubishi Chemical Co., Ltd.) 0.08 g and phenol novolak resin (trade name "Tamanol 759" Arakawa Chemical Industry Co., Ltd.) 0.08 g, (D) 0.67 g of toluene as component, 0.08 g of methyl ethyl ketone, and ( E) As a component, 0.01 g of a commercially available amino group-containing silane coupling agent (trade name "KBM603", manufactured by Shin-Etsu Chemical Co., Ltd.; N-2-(aminoethyl)-3-aminopropyltrimethoxysilane) was mixed, and A resin composition (adhesive composition) containing 30.1% of volatile matter was obtained.

Example 2 to 10 and comparative example 1-7

It was manufactured in the same manner as in Example 1 except that the composition was changed to that described in Table 1.

<Manufacture of adhesive sheet>

After applying the adhesive of Example 1 to a polyimide film (trade name "Kapton 100EN", film thickness of 25 μm) with a gap coater so that the thickness after drying is 12 μm, and then drying at 150 ° C. for 5 minutes, the adhesive sheet got An adhesive sheet was obtained in the same manner for the adhesive composition of Comparative Example 1.

<Manufacture of copper-clad laminate>

Next, a 12 μm thick rolled copper foil (trade name “GHF5-93F-HA-V2”, manufactured by JX Metal Co., Ltd., 10-point average roughness (Rz): 0.45 μm) was applied to the adhesive surface of each adhesive sheet on the mirror surface side. were piled up and hot-pressed under conditions of a pressure of 5 MPa, 170°C, and 30 minutes to prepare a laminate. A laminate was obtained in the same manner for the adhesive composition of Comparative Example 1.

<Measurement of dielectric constant and dielectric loss tangent of adhesive layer>

About 7 g of the adhesives of Examples and Comparative Examples were poured into a fluorine resin PFA flat dish (diameter 75 mm, manufactured by Sanghoi Chemical Co., Ltd.), 30 ° C × 10 hours, 70 ° C × 10 hours, 100 ° C × 6 hours, By curing under the conditions of 120°C x 6 hours, 150°C x 6 hours, and 180°C x 12 hours, a cured product sheet having a film thickness of about 300 µm was obtained. Next, the dielectric constant and dielectric loss tangent at 10 GHz of the cured product sheet were measured according to JIS C2565 using a commercially available dielectric constant measuring device (cavity resonator type, manufactured by AT).

<Adhesion test>

For each laminate of Examples and Comparative Examples, the peel strength (N/cm) was measured according to JIS C-6481 (Test method for copper-clad laminates for flexible printed wiring boards).

<Solder heat resistance test>

For each laminate of Examples and Comparative Examples, after curing, the copper foil side was floated in a solder bath at 288° C. for 30 seconds, and the presence or absence of a change in appearance was confirmed. No change was marked as ○, and the case where there was foaming or swelling was marked as ×.

<Manufacture of bonding sheet>

The adhesive of Example 1 was applied to a release film (trade name "WH52-P25CM (bag)", manufactured by San-Ai Kayon Co., Ltd.) with a gap coater so that the thickness after drying was about 25 μm, and then dried at 150 ° C. for 5 minutes By doing so, a bonding sheet was obtained. Bonding sheets were obtained in the same manner for the adhesive compositions of other Examples and Comparative Examples.

<Manufacture of printed wiring board>

A resist pattern having line/space = 0.2/0.2 (mm) was formed on the copper foil on both sides of the copper clad laminate according to Example 1, and immersed in a 40% concentration ferric chloride aqueous solution to etch and form a copper circuit. did In this way, a printed wiring board was obtained.

<Manufacture of multilayer wiring board>

The obtained printed wiring board was used as a core material, and the copper foil with the resin part according to Example 1 was overlaid on both sides thereof, and the outer layer untreated copper foil was bonded under conditions of a pressure of 4.5 MPa, 200 ° C. and 30 minutes, line / space = 0.2 / A resist pattern of 0.2 (mm) was formed. Next, a copper circuit was formed by etching the obtained substrate by immersion in an aqueous ferric chloride solution having a concentration of 40%. The adhesive sheet was overlaid on the surface layer on which the copper circuit was formed, and laminated by hot pressing under conditions of a pressure of 1 MPa, 180° C., and 30 minutes. In this way, a multilayer wiring board having four circuit pattern layers was obtained.

<Manufacture of multi-layer wiring board 2>

A resist pattern of line/space = 0.2/0.2 (mm) was formed on the copper foil of the one-sided copper-clad laminate according to Example 1, and immersed in a 40% concentration ferric chloride aqueous solution to etch it to form a copper circuit. . The same thing was prepared, and the bonding sheet was sandwiched between the substrate sides without a copper circuit, and laminated by hot pressing under conditions of a pressure of 1 MPa, 180° C., and 30 minutes. Thereafter, the adhesive sheet was overlaid on the surface layer on which the copper circuit of the laminate was formed, and laminated by hot pressing under conditions of a pressure of 1 MPa, 180° C., and 30 minutes. In this way, a multilayer wiring board having four circuit pattern layers was obtained.

Claims (9)

A polyimide (A) containing an aromatic tetracarboxylic anhydride (a1) and a diamine (a2) containing 30 mol% or more of dimer diamine as constituent components;
A hydrogenated petroleum resin (B);
A crosslinking agent (C);
an organic solvent (D);
General formula: Z-Si(R ¹ ) _a (OR ² ) _3-a (wherein Z is a group containing an acid anhydride group-reactive functional group, R ¹ is hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R ² is A polyimide-based adhesive containing a reactive alkoxysilyl compound (E) represented by a hydrocarbon group having 1 to 8 carbon atoms, and a represents 0, 1 or 2). According to claim 1,
A polyimide-based adhesive wherein the component (a1) is represented by the following structure.

(In the formula, X is a single bond, -SO ₂ -, -CO-, -O-, -O-C ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O- or COO-Y-OCO- (Y represents -(CH ₂ ) _l -(l = 1 to 20) or -H ₂ C-HC (-O-C(=O)-CH ₃ )-CH ₂ -) According to claim 1 or 2,
A polyimide-based adhesive characterized in that the component (a2) contains diaminopolysiloxane in an amount of less than 70 mol%. According to claim 1 or 2,
A polyimide-based adhesive characterized in that component (B) is at least one hydride selected from the group consisting of C5-based petroleum resins, C9-based petroleum resins, and C5/C9-based petroleum resins. According to claim 1 or 2,
A polyimide-based adhesive characterized in that the content of aromatic rings contained in component (B) is less than 50% by weight. According to claim 1 or 2,
A polyimide-based adhesive characterized in that component (C) is at least one selected from the group consisting of epoxy compounds, benzoxazine compounds, bismaleimide compounds and cyanate ester compounds. According to claim 1 or 2,
A polyimide-based adhesive further comprising a flame retardant (F). According to claim 1 or 2,
A polyimide-based adhesive further comprising an inorganic filler (G). delete