JP6790816B2 - Polyimide adhesive - Google Patents

Description

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

Flexible Printed Wiring Board (FPWB), Printed Circuit Board (PCB), and Multi-Layer Board (MLB) using them are mobile communication such as mobile phones and smartphones. It is used in devices, their base station devices, network-related electronic devices such as servers and routers, and products such as large computers.

In recent years, high-frequency electric signals have been used in these products in order to transmit and process a large amount of information at high speed. However, since high-frequency signals are very easily attenuated, transmission loss is also transmitted to the multilayer wiring board and the like. Ingenuity is required to suppress.

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

The dielectric loss depends on the frequency and the permittivity and dielectric loss tangent of the insulating material around the copper circuit. The higher the frequency, the more 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, the conductor loss is caused by the skin effect, that is, the phenomenon that the AC current density on the surface of the copper circuit becomes high and the resistance becomes high, and becomes remarkable when the frequency exceeds GHz. The main countermeasure for conductor loss is smoothing of the copper circuit surface.

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

However, 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 even if it has a small amount, it is difficult to adhere to a smooth copper circuit. On the contrary, a material having many such functional groups tends to have a high dielectric constant and a high dielectric loss tangent even if the adhesion is high.

JP-A-2009-299040 JP-A-2014-045076

The present invention has low dielectric constant and dielectric loss tangent (hereinafter, both may be collectively referred to as dielectric properties), and has adhesion to copper, particularly copper having a smooth surface (hereinafter, also simply referred to as copper adhesion). The main subject is to provide a novel polyimide-based adhesive having a good quality.).

As a result of diligent studies, the present inventor has found that an adhesive capable of solving the above problems can be obtained by combining polyimide containing diamine diamine as a constituent component and hydrogenated petroleum resin.

That is, the present invention crosslinks a polyimide (A) containing an aromatic tetracarboxylic dianhydride (a1) and a diamine (a2) containing 30 mol% or more of dimerdiamine as constituents, and a hydride petroleum resin (B). The present invention relates to a polyimide adhesive containing an agent (C) and an organic solvent (D).

The polyimide-based adhesive of the present invention has good compatibility and can be used as a homogeneous varnish without insoluble matter. Further, the adhesive layer made of the adhesive is excellent in both low dielectric properties and copper adhesion, and also has good solder heat resistance.

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

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

The component (A) is an aromatic tetracarboxylic dianhydride (a1) (hereinafter, also referred to as a component (a1)), and a diamine (a2) containing 30 mol% or more of a dimer diamine (hereinafter, also referred to as a component (a2)). .) Is a constituent component.

As the component (a1), various known aromatic tetracarboxylic dianhydrides 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 dianhydride, 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 1,4,5 , 8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3', 4,4'-biphenyltetracarboxylic dianhydride, 2,2', 3, 3'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-benzophenonetetracarboxylic dianhydride, 2,3 , 3', 4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3', 4'-diphenylsulfonetetracarboxylic dianhydride, 2,2-bis (3,3', 4,4'- Tetetracarboxyphenyl) tetrafluoropropanedianhydride, 2,2'-bis (3,4-dicarboxyphenoxyphenyl) dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propanedianhydride , 2,2-bis (3,4-dicarboxyphenyl) propanedianhydride, and 4,4'-[propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic acid dianhydride and the like. Two or more types may be combined. Among these, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 4,4'-[propane-2,2-diylbis (1)" in terms of the balance between heat resistance and low dielectric properties. , 4-Phenyleneoxy)] At least one selected from the group consisting of diphthalic acid dianhydride and 4,4'-oxydiphthalic anhydride is preferable. In one embodiment, component (a1) has the following structure:
(In the equation, 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- It represents OCO- (Y represents − (CH ₂ ) _l − (l = 1 to 20) or −H ₂ C—HC (−O—C (= O) −CH ₃ ) −CH ₂₋ ). ).

Dimerdiamine, which is an essential component of the component (a2), is a compound derived from dimer acid, which is a dimer of unsaturated fatty acids such as oleic acid (see JP-A-9-12712, etc.), and is known in various ways. Dimer diamine can be used without any particular limitation. Commercially available products of the component (a2) include, for example, Versamine 551 (manufactured by BASF Japan Ltd.), Versamine 552 (manufactured by Cognix Japan Co., Ltd .; hydrogenated product of Versamine 551), PRIAMINE 1075, and PRIAMINE 1074 (all of which are Croda Japan (manufactured by Croda Japan). Made by Co., Ltd.) and the like.

The content of the dimer diamine in the component (a2) is in terms of the low dielectric property of the adhesive of the present invention, copper adhesion and solder heat resistance, and the solubility of the component (A) in the component (D) described later. , Usually 30 mol% or more, preferably about 50 to 100 mol%.

The component (a2) may contain various known diaminopolysiloxanes in the range of less than 70 mol%. 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) ] Polydimethylsiloxane and the like can be 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 adhesive force 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%.

The component (a2) can further include diamines other than the dimer diamine and the diaminopolysiloxane. Specific examples include diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, tetramethyl-diaminodicyclohexylmethane, diaminodicyclohexylpropane, diaminobicyclo [2.2.1] heptane, bis (aminomethyl) -bicyclo [2. 2.1] Alicyclic of heptane, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.02,6] decane, 1,3-bisaminomethylcyclohexane, isophoronediamine, etc. Formula diamine; bisaminophenoxyphenyl propanes such as 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane; 3,3 Diaminodiphenyl ethers such as'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether; phenylenediamines such as p-phenylenediamine, m-phenylenediamine; 3,3'-diaminodiphenylsulfide, Diaminodiphenyl sulfides such as 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide; 3,3'-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, 4,4′-diaminodiphenylsulfone Diaminodiphenylsulfone such as 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, diaminobenzophenone such as 3,4'-diaminobenzophenone; 3,3'-diaminodiphenylmethane, 4,4'-diamino Diaminodiphenylmethanes such as diphenylmethane, 3,4'-diaminodiphenylmethane; 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, 2- (3-aminophenyl)- Diaminophenyl propanes such as 2- (4-aminophenyl) propane; 2,2-di (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-di ( 4-Aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3 Diaminophenyl hexafluoropropanes such as 3-hexafluoropropane; 1,1-di (3-aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) -1-phenylethane , 1- (3-Aminophenyl) -1- (4-Aminophenyl) -1-phenylethane and other diaminophenylphenylethanes; 1,3-bis (3-aminophenoxy) benzene, 1,3-bis ( Bisaminophenoxybenzenes such as 4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 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) Bisaminodimethylbenzenes such as −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-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis Bisaminoditrifluoromethylbenzylbenzenes such as (4-amino-α, α-ditrifluoromethylbenzyl) benzene; 2,6-bis (3-aminophenoxy) benzonitrile, 2,6-bis (3-aminophenoxy) ) Aminophenoxybiphenyls such as pyridine, 4,4'-bis (3-aminophenoxy) biphenyl, 4,4'-bis (4-aminophenoxy) biphenyl; bis [4- (3-aminophenoxy) phenyl] ketone , Aminophenoxyphenyl ketones such as bis [4- (4-aminophenoxy) phenyl] ketone; bis [4- (3-aminophenoxy) phenyl] sulfide, bis [4- (4-aminophenoxy) phenyl] sulfide, etc. Aminophenoxyphenylsulfides; Aminophenoxyphenylsulfones such as bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) phenyl] sulfone; bis [4- (3-amino) Aminophenoxyphenyl ethers such as phenoxy) phenyl] ether and bis [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] -1,1,1,3,3,3-Aminophenoxyphenylpropanes such as hexafluoropropane; Others, 1,3-Bis [4- (3- (3-) 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] diphenylsulfone, 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'-spirobiindane, 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 Siloxane, 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, ethyleneglycolbis (3-aminopropyl) ether, diethyleneglycolbis (3-aminopropyl) ether, triethyleneglycolbis (3-aminopropyl) ether, 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 and the like, and two or more of them may be combined. The content of these other diamines in the component (a2) is not particularly limited, but is usually less than 50 mol%.

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

The component (A) can be produced by various known methods. Specifically, for example, the component (a1) and the component (a2) and, if necessary, other reaction components are usually 0.1 to 0.1 at a temperature of about 60 to 120 ° C. (preferably 80 to 100 ° C.). The double addition reaction is carried out for about 2 hours (preferably 0.1 to 0.5 hours). Then, the obtained heavy adduct is further subjected to an imidization reaction, that is, a dehydration ring closure reaction at a temperature of about 80 to 250 ° C., preferably 100 to 200 ° C. for about 0.5 to 50 hours (preferably 1 to 20 hours). Just let me do it. Further, in those reactions, the component (D) described later, particularly an aprotic polar solvent, can be used as the reaction solvent.

In the imidization 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. The above may be combined. Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic anhydride, and two or more kinds may be combined.

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

The physical properties of the component (A) are not particularly limited, but in terms of the balance between compatibility, low dielectric properties and copper adhesion, they usually have a number average molecular weight (a polystyrene-equivalent value obtained by gel permeation chromatography. The same applies hereinafter. ) Is about 5,000 to 50,000, and the softening point is usually about 30 to 160 ° C.

The concentration of the terminal acid anhydride group of the component (A) is not particularly limited, but is usually about 2000 to 40,000 eq / g. Further, 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, tert-pentylamine, n-octyl. Examples include amines, n-decylamines, isodecylamines, n-tridecylamines, n-laurylamines, n-cetylamines, n-stearylamines, etc. Among these, those having an alkyl group having about 4 to 15 carbon atoms preferable.

As the component (B), various known hydrogenated petroleum resins can be used. Specifically, at least one hydride selected from the group consisting of C5 petroleum resin, C9 petroleum resin and C5 / C9 petroleum resin can be mentioned. The C5 petroleum resin is a petroleum resin obtained from the 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, β-methylstyrene and the like. The C5 / C9 based petroleum resin is a petroleum resin obtained from the C5 fraction and the C9 fraction. In addition, these petroleum resins may contain olefins such as kumaron, dicyclopentadiene, butene, pentene, hexene, heptene, octene, butadiene, pentadiene, cyclopentadiene, and octadiene as constituents.

The petroleum resin is obtained by cationically polymerizing the distillate as a raw material in the presence of a Friedelcraft catalyst such as aluminum chloride or boron trifluoride. Then, by hydrogenating the obtained cationic polymer in the presence of various known hydrogenation catalysts, the desired component (B) can be obtained. Examples of the hydrogenation catalyst include metals such as nickel, palladium, cobalt, ruthenium, platinum and rhodium, and oxides of the metals. The hydrogenation conditions are not particularly limited, and usually, the temperature is about 200 to 300 ° C. and the pressure is about 10 to 300 kg / cm ² . The component (B) may be a commercially available product, and examples thereof include Archon P series and Archon 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 and the like, those having a softening point of about 80 to 160 ° C. are usually preferable.

Further, according to the study by the present inventor, it was found that the content of the aromatic ring contained in the component (B) affects the copper adhesion and the low dielectric property of the adhesive of the present invention. Then, by setting the content to less than 50% by weight, preferably less than 30% by weight, the low dielectric property can be lowered while maintaining the copper adhesion. The content is the reciprocal of the hydrogenation rate of the component (B), and the hydrogenation rate uses the H-spectral area of the aromatic ring appearing near 7 ppm of ¹ H-NMR of the component (B) as follows. It can be calculated through the formula.

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

The amount of the component (B) used is not particularly limited, but in terms of compatibility with the adhesive of the present invention, low dielectric properties, copper adhesion, solder heat resistance, etc., the component (A) is usually 100 parts by weight. On the other hand, it is about 1 to 30 parts by weight (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 cross-linking agent for polyimide. Specifically, for example, at least one selected from the group consisting of an epoxy compound, a benzoxazine compound, a bismaleimide compound and a cyanate ester compound is preferable.

Examples of the epoxy compound include phenol novolac type epoxy compound, cresol novolac type epoxy compound, bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, hydrogenated bisphenol A type epoxy compound, hydrogenated bisphenol F type epoxy compound. Compounds, Stilben-type epoxy compounds, triazine skeleton-containing epoxy compounds, fluorene skeleton-containing epoxy compounds, linear aliphatic epoxy compounds, alicyclic epoxy compounds, glycidylamine-type epoxy compounds, triphenolmethane-type epoxy compounds, alkyl-modified triphenolmethane Type epoxy compound, biphenyl type epoxy compound, dicyclopentadiene skeleton-containing epoxy compound, naphthalene skeleton-containing epoxy compound, arylalkylene type epoxy compound, tetraglycidyl xylylene diamine, modified epoxy compound obtained by modifying these epoxy compounds with dimer acid, Examples thereof include diglycidyl ester of dimer acid, and two or more kinds may be combined. Examples of commercially available products include "jER828", "jER834" and "jER807" manufactured by Mitsubishi Chemical Corporation, "ST-3000" manufactured by Nippon Steel Chemical Corporation, and Daicel Chemical Industry Co., Ltd. Examples thereof include "Selokiside 2021P", "YD-172-X75" manufactured by Nippon Steel Chemical Corporation, and "TETRAD-X" manufactured by Mitsubishi Gas Chemical Corporation. Among these, bisphenol A type epoxy compound, bisphenol F type epoxy compound, hydrogenated bisphenol A type epoxy compound in terms of compatibility of the adhesive of the present invention, low dielectric property, copper adhesion and solder heat resistance, etc. And at least one selected from the group consisting of an alicyclic epoxy compound is preferable, and tetraglycidyl xylylene diamine having the following structure is particularly preferable.

When an epoxy compound is used as the thermosetting resin, various known curing agents for epoxy compounds can be used in combination. Specifically, for example, succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride Acid, or a mixture of 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadicic anhydride, methylnadic anhydride, norbornan-2,3-dicarboxylic acid anhydride Acid anhydride-based curing agents such as methylnorbornan-2,3-dicarboxylic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, 3-dodecenyl phthalic anhydride, octenyl succinic anhydride; dicyandiamide (DICY), aromatic diamine ( Product names "LonzacureM-DEA", "LonzacureM-DETDA", etc. All are manufactured by Lonza Japan Co., Ltd., amine-based curing agents such as aliphatic amines; phenol novolac resin, cresol novolak resin, bisphenol A type novolak resin, triazine Modified phenol novolak resin, phenolic curing agent such as phenolic hydroxyl group-containing phosphazene (trade name "SPH-100" manufactured by Otsuka Chemical Co., Ltd.), cyclic phosphazene compound, maleic anhydride-modified rosin and rosin such as hydride thereof Examples include system cross-linking agents, and two or more types may be combined. Among these, a phenolic curing agent, particularly a phenolic hydroxyl group-containing phosphazene-based curing agent is preferable. 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. is there.

When the epoxy compound is used, a catalyst for accelerating the reaction between the epoxy compound and the curing agent can also be used. Specifically, for example, 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and the like. Class amines; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenyl Organic phosphines such as phosphine; tetraphenylborone salts such as tetraphenylphosphonium / tetraphenylborate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholin / tetraphenylborate, etc., and two or more of them. It may be combined. The amount of the 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) and 6,6- (1-methylethylidene). Examples thereof include bis (3,4-dihydro-3-methyl-2H-1,3-benzoxazine), and two or more of them may be combined. A phenyl group, a methyl group, a cyclohexyl group or the like may be bonded to the nitrogen of the oxazine ring. Examples of commercially available products include "benzoxazine FA type" and "benzoxazine Pd type" manufactured by Shikoku Chemicals Corporation, and "RLV-100" manufactured by Air Water Co., Ltd. Can be mentioned.

Examples of the bismaleimide compound include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, and 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethanebis. Maleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-diphenylsulphonbis Maleimide and the like can be mentioned, and two or more kinds may be combined. Examples of commercially available products include "BAF-BMI" manufactured by JFE Chemical Corporation.

Examples of the cyanate ester compound include 2-allylphenol cyanate ester, 4-methoxyphenol cyanate ester, and 2,2-bis (4-cyanatophenol) -1,1,1,3,3,3-hexafluoropropane. , Bisphenol A Cyanate Ester, Dialyl Bisphenol A Cyanate Ester, 4-Phenylphenol Cyanate Ester, 1,1,1-Tris (4-Cyanatophenyl) Ethan, 4-Cumylphenol Cyanate Ester, 1,1-Bis (4) -Cyanatophenyl) ethane, 4,4'-bisphenol cyanate ester, 2,2-bis (4-cyanatophenyl) propane and the like can be mentioned, and two or more of them may be combined. Moreover, as a commercial product, for example, "PRIMASET BTP-6020S (manufactured by Lonza Japan Co., Ltd.)" and the like can be mentioned.

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

The polyimide-based adhesive of the present invention may further contain an organic solvent (D) (hereinafter, also referred to as a component (D)). Specifically, for example, aprotonic polar solvents such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylcaprolactam, methyltriglime, and methyldiglyme, cyclohexanone, methylcyclohexane, and the like. Examples thereof include alicyclic solvents, alcohol solvents such as methanol, ethanol, propanol, benzyl alcohol and cresol, and aromatic solvents such as toluene.

The amount of the component (D) used is not particularly limited, but is usually about 1 to 500 parts by weight with respect to 100 parts by weight of the component (A) in terms of compatibility with the adhesive of the present invention.

The adhesive of the present invention further has a general formula: Z-Si (R ¹ ) _a (OR ² ) _3-a (in the formula, Z is a group containing a functional group that reacts with an acid anhydride group, and R ¹ is Reactive alkoxysilyl compound (E) represented by hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R ² represents a hydrocarbon group having 1 to 8 carbon atoms, and a represents 0, 1 or 2). (Hereinafter, also referred to as component (E)) can be included. The component (E) can adjust the melt viscosity of the adhesive layer made of the adhesive of the present invention while maintaining the low dielectric properties. As a result, it becomes possible to suppress the exudation of the cured layer generated from the edge of the base material while increasing the interfacial adhesion between the adhesive layer and the base material (so-called anchor effect).

Examples of the reactive functional group contained in Z of the general formula include an amino group, an epoxy group and a thiol group. Examples of the compound in which Z contains an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and 3-aminopropyl. Examples thereof include trimethoxysilane, 3-aminopropyltriethoxysilane and 3-ureidopropyltrialkoxysilane. Examples of the compound in which Z contains an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glyci. Examples thereof include sidoxylpropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane. Examples of the compound in which Z contains a thiol group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane. Among these, a compound in which Z contains an amino group is preferable because it reacts rapidly with the component (A) and has a good flow control effect.

The amount of the 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 the component (A).

The polyimide-based adhesive of the present invention may further contain a flame retardant (F) (hereinafter, also referred to as a component (F)). Specific examples thereof include phosphorus-based flame retardants such as polyphosphoric acid and phosphoric acid esters, and / or phosphazene-based flame retardants. 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 Rabbitl FP-300 manufactured by Fushimi Pharmaceutical Co., Ltd.

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

The polyimide-based adhesive of the present invention may further contain an inorganic filler (G) (hereinafter, also referred to as a 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, crystals. Examples thereof include sex silica, amorphous silica, graphite powder, and boehmite.

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

Further, the adhesive of the present invention includes the ring-opening esterification reaction catalyst, a dehydrating agent, a plasticizer, a weathering agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, and a coloring agent, if necessary. Agents, conductive agents, mold release agents, surface treatment agents, viscosity modifiers and the like can be blended.

The polyimide-based adhesive of the present invention comprises the components (A), (B), (C) and (D), and if necessary, the components (E), (F) and (G). It is a varnish-like solution obtained by mixing with at least one selected from the group consisting of.

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

The polyimide-based adhesive and the film-like adhesive of the present invention can be used in the production of a multilayer wiring board. Specifically, the adhesive or the adhesive is brought into contact with at least one surface of a printed wiring board which is a core base material, another printed wiring board or a printed circuit board is laminated on the adhesive, and then heated and pressurized. It may be crimped. The heating temperature and crimping time are not particularly limited, but usually (a) the polyimide adhesive or the film-like adhesive of the present invention is brought into contact with at least one surface of the printed wiring board as the core base material, and then usually 70 to 200. After heating to about 1 to 10 minutes and allowing the curing reaction to proceed, (a) in order to proceed with the curing reaction, it is usually further heat-treated at about 150 ° C. to 250 ° C. for about 10 minutes to 3 hours. Good. The pressure is also not particularly limited, but is usually about 0.5 to 20 MPa, preferably about 1 to 8 MPa throughout the steps (a) and (b).

The polyimide-based adhesive can also 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, acrylonitrile-butadiene-styrene resin, ethylene terephthalate and the like. Examples thereof include plastic films such as aromatic polyester resins (so-called liquid crystal polymers; manufactured by Kuraray Co., Ltd., "Vexter", etc.) obtained from phenol, phthalic acid, hydroxynaphthoic acid and the like and parahydroxybenzoic acid. Further, the coating means is not particularly limited, and examples thereof include a curtain coater, a roll coater, and a laminator. 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. Further, the adhesive layer of the adhesive sheet may be protected by various protective films.

The polyimide-based adhesive or film-like adhesive may be coated or bonded to a copper foil to be processed into a copper foil with a resin. Examples of the copper foil include rolled copper foil and electrolytic copper foil. The thickness thereof is also 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 rust preventive treatment include a plating treatment using a plating solution containing Ni, Zn, Sn and the like, and a so-called mirror surface treatment such as a chromate treatment. Moreover, the above-mentioned method can be mentioned as a coating means. Further, the adhesive layer of the resin-attached copper foil may be uncured, or may be partially cured or completely cured under heating. The partially cured adhesive layer is in a so-called B stage. Further, the thickness of the adhesive layer is not particularly limited, and is usually about 0.5 to 30 μm. Further, a copper foil may be further attached to the adhesive surface of the resin-attached copper foil to obtain a double-sided resin-attached copper foil.

The copper-clad laminate is an article obtained by laminating a copper foil with a resin of the present invention and a copper foil or an insulating sheet, and is also called CCL (Copper Clad Laminate). Specifically, the resin-coated copper foil of the present invention is pressure-bonded to at least one or both sides of various known insulating sheets under heating. Further, in the case of one side, a material different from the resin-attached copper foil of the present invention may be crimped to the other side. Further, the number of resin-attached copper foils and insulating sheets in the copper-clad laminate is not particularly limited. Further, as the insulating sheet, a prepreg is preferable. The prepreg is a sheet-like material obtained by impregnating a reinforcing material such as a glass cloth with a resin and curing it up to the B stage (JIS C 5603), and the resin is usually a polyimide resin, a phenol resin, an epoxy resin, or the like. Insulating resins such as polyester resin, liquid crystal polymer, and aramid resin are used. The thickness of the prepreg is not particularly limited, and is usually about 20 to 500 μm. The heating / crimping 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 made into a printed wiring board by forming a circuit pattern on the copper foil surface. Examples of the patterning means include a subtractive method and a semi-additive method. Examples of the semi-additive method include a method in which the copper foil surface of the copper-clad laminate is patterned with a resist film and then electrolytically copper-plated to remove the resist and etched with an alkaline solution. Further, the thickness of the circuit pattern layer in the printed wiring board is not particularly limited. Further, a multilayer board can also be obtained by using the printed wiring board as a core base material and laminating the same printed wiring board or another known printed wiring board or printed circuit board on the printed wiring board. At the time of laminating, not only the polyimide-based adhesive of the present invention but also other known polyimide-based adhesives can be used. Further, the number of layers in the multilayer board is not particularly limited. Further, a via hole may be inserted each time the lamination is performed, and the inside may be plated.

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 each example, parts and% are based on weight unless otherwise specified.

The number average molecular weight is a value obtained by using a commercially available measuring machine (“High-speed GPC HLC-8220”, manufactured by TOSOH).

The softening point is the temperature at which the rigidity begins to decrease in the viscoelastic profile measured using a commercially available measuring instrument (“ARES-2KSTD-FCO-STD”, manufactured by Rheometric Scientific).

Manufacturing example 1
A commercially available aromatic tetracarboxylic dianhydride (trade name "BTDA-UP", manufactured by Ebonic Japan Co., Ltd .; 3,3) is placed in a reaction vessel equipped with a stirrer, a water divider, a thermometer and a nitrogen gas introduction tube. 210.0 g of', 4,4'-benzophenone tetracarboxylic dianhydride content (99.9% or more), 1008.0 g of cyclohexanone, and 201.6 g of methylcyclohexane were charged, and the solution was heated to 60 ° C. Next, 341.7 g of hydrogenated dimer diamine (trade name "PRIAMINE 1075", manufactured by Crowder Japan Co., Ltd.) was added dropwise, and then the polyimide resin (A-1) was subjected to an imidization reaction at 140 ° C. for 10 hours. Solution (nonvolatile content 30.2%) was obtained. The molar ratio of the acid component / amine component was 1.03. The number average molecular weight of the component (A-1) was 15,000, and the softening point was about 80 ° C.

Manufacturing example 2
A commercially available aromatic tetracarboxylic dianhydride (trade name "BisDA1000", manufactured by Ebonic Japan Co., Ltd .; 4,4'-[Propane-2,2-diylbis (1,2)" is placed in the same reaction vessel as in Production Example 1. 4-Phenyleneoxy)] Diphthalic acid dianhydride content was 98.0%) 297.8 g, cyclohexanone 818.95 g, and methylcyclohexane 136.49 g were charged, 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, and then the imidization reaction was carried out at 140 ° C. for 10 hours to obtain a solution (nonvolatile component) of polyimide (A-2). 29.7%) was obtained. The molar ratio of the acid component / amine component of the polyimide resin was 1.05. The number average molecular weight of the component (A-2) was 15,000, and the softening point was about 100 ° C.

Manufacturing example 3
In the same reaction vessel as in Production Example 1, 200.00 g of BisDA1000, 700.00 g of cyclohexanone, and 175.00 g of methylcyclohexane were charged, and the solution was heated to 60 ° C. Then, after dropping 190.54 g of PRIAMINE 1075, an imidization reaction was carried out at 140 ° C. for 10 hours to obtain a solution of polyimide (A-3) (nonvolatile content 30.1%). The molar ratio of the acid component / amine component of the polyimide resin was 1.09.

Manufacturing example 4
In the same reaction vessel as in Production Example 1, (trade name "BTDA-PF", manufactured by Ebony Japan Co., Ltd .; content of 3,3', 4,4'-benzophenonetetracarboxylic dianhydride is 98%). 190.0 g, 277.5 g of cyclohexanone, and 182.4 g of methylcyclohexane were charged, and the solution was heated to 60 ° C. Then, after dropping 23.8 g of PRIAMINE 1075 277.5 g and commercially available α, ω-bis (3-aminopropyl) polydimethylsiloxane (trade name “KF-8010”, manufactured by Shin-Etsu Chemical Co., Ltd.). , The imidization reaction was carried out at 140 ° C. for 10 hours to obtain a solution of polyimide (A-4) (nonvolatile content: 30.5%). The molar ratio of the acid component / amine component of the polyimide resin was 1.09. The number average molecular weight of the component (A-4) was 10,000, and the softening point was about 70 ° C.

Comparative manufacturing example 1
In the same reaction vessel as in Production Example 1, 1300.0 g of BisDA1000, 364.0 g of methylcyclohexane and 2184.0 g of diethyl acetamide were charged, and the solution was heated to 60 ° C. Then, after dropping 323.27 g of 1,3-bisaminomethylcyclohexane, the imidization reaction was carried out at 140 ° C. for 10 hours to obtain a solution of polyimide (A-5) (nonvolatile content 37.7%). It was. The molar ratio of the acid component / amine component was 1.10.

Comparative manufacturing example 2
BisDA1000 297.8 g, cyclohexane 818.95 g, methylcyclohexane 136.49 g and diethyl acetamide 245.63 g were charged in the same reaction vessel as in Production Example 1, and the solution was heated to 60 ° C. Then, 73.51 g of PRIAMINE 1075 and 58.19 g of 1,3-bisaminomethylcyclohexane were added dropwise, and then the imidization reaction was carried out at 140 ° C. for 10 hours to carry out an imidization reaction with a solution of polyimide (A-6) (nonvolatile content 37. 7%) was obtained. The molar ratio of the acid component / amine component was 1.10.

Example 1
3.93 g of the solution of the component (A-1), 4.00 g of the solution of the component (A-2), 1.95 g of the solution of the component (A-3), and a hydride petroleum resin as the component (B) P-100 ", manufactured by 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 ”, 0.08 g of Mitsubishi Chemical Co., Ltd. and 0.08 g of phenol novolac resin (trade name“ Tamanol 759 ”manufactured by Arakawa Chemical Industry Co., Ltd.) .08 g, and a commercially available amino group-containing silane coupling agent (trade name "KBM603", manufactured by Shinetsu Chemical Industry Co., Ltd .; N-2- (aminoethyl) -3-aminopropyltrimethoxysilane 0) as a component (E). 0.01 g was mixed to obtain a resin composition (adhesive composition) having a non-volatile content of 30.1%.

Examples 2-10 and Comparative Examples 1-7
It was produced in the same manner as in Example 1 except that the composition was changed to that shown in Table 1.

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

<Manufacturing of copper-clad laminate>
Next, on the adhesive surface of each adhesive sheet, a 12 μm-thick rolled copper foil (trade name “GHF5-93F-HA-V2”, manufactured by JX Nippon Mining & Metals Co., Ltd., 10-point average roughness (Rz): 0.45 μm) The mirror surfaces were overlapped and heat-pressed under the conditions of a pressure of 5 MPa, 170 ° C. and 30 minutes to prepare a laminated body. A laminate was obtained in the same manner for the adhesive composition of Comparative Example 1.

<Measurement of permittivity and dielectric loss tangent of adhesive layer>
Approximately 7 g of the adhesives of Examples and Comparative Examples were poured into a fluororesin PFA flat plate (diameter 75 mm, manufactured by Mutual Rikagaku Glass Mfg. Co., Ltd.), and 30 ° C. A cured product sheet having a film thickness of about 300 μm was obtained by curing under the conditions of 120 ° C. × 6 hours, 150 ° C. × 6 hours, and 180 ° C. × 12 hours. Next, the dielectric constant and the dielectric loss tangent at 10 GHz of the cured product sheet were measured using a commercially available dielectric constant measuring device (cavity resonator type, manufactured by AET) according to JIS C2565.

<Adhesion test>
The peeling strength (N / cm) of each of the laminates of Examples and Comparative Examples was measured according to JIS C-6488 (copper-clad laminate test method for flexible printed wiring boards).

<Solder heat resistance test>
After curing, each of the laminates of Examples and Comparative Examples was floated in a solder bath at 288 ° C. with the copper foil side down for 30 seconds, and the presence or absence of a change in appearance was confirmed. No change was marked with ◯, and foaming and swelling were marked with x.

<Making a bonding sheet>
After applying the adhesive of Example 1 to a release film (trade name "WH52-P25CM (white)", manufactured by Sun A. Kaken Co., Ltd.) with a gap coater so that the thickness after drying is about 25 μm. A bonding sheet was obtained by drying at 150 ° C. for 5 minutes. Bonding sheets were obtained in the same manner for the adhesive compositions of the other examples and comparative examples.

<Manufacturing of printed wiring board>
A copper foil having a line / space = 0.2 / 0.2 (mm) resist pattern formed on the copper foils on both sides of the copper-clad laminate according to Example 1 was immersed in a ferric chloride aqueous solution having a concentration of 40%. Etching was performed by forming a copper circuit. In this way, a printed wiring board was obtained.

<Manufacturing of multilayer wiring board>
The obtained printed wiring board was used as a core material, and the copper foil with resin according to Example 1 was laminated on both sides thereof and crimped under the conditions of a pressure of 4.5 MPa, 200 ° C. and 30 minutes, and the untreated copper foil of the outer layer was formed. A resist pattern of line / space = 0.2 / 0.2 (mm) was formed in the above. Then, the obtained substrate was etched by immersing it in a ferric chloride aqueous solution having a concentration of 40% to form a copper circuit. The adhesive sheet was laminated on the surface layer on which the copper circuit was formed, and was laminated by heating and pressing under the 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.

<Manufacturing of multilayer wiring board 2>
A copper foil of a single-sided copper-clad laminate according to Example 1 having a resist pattern of line / space = 0.2 / 0.2 (mm) formed therein is immersed in a ferric chloride aqueous solution having a concentration of 40%. By etching, a copper circuit was formed. The same material was prepared, the bonding sheets were sandwiched between the base materials without a copper circuit, and heat-pressed under the conditions of a pressure of 1 MPa, 180 ° C., and 30 minutes for laminating. Then, the adhesive sheet was superposed on the surface layer on which the copper circuit of the laminated body was formed, and was laminated by heating and pressing under the 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 dianhydride (a1) and a diamine (a2) containing 30 mol% or more of a dimer diamine as a constituent component.
Hydrogenated petroleum resin (B) and
Cross-linking agent (C) and
Organic solvent (D) and
Polyimide-based adhesive containing. The polyimide adhesive according to claim 1, wherein the component (a1) has the following structure.
(In the equation, 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- It represents OCO- (Y represents − (CH ₂ ) _l − (l = 1 to 20) or −H ₂ C—HC (−OC (= O) −CH ₃ ) −CH ₂₋ ). ) (A2) The polyimide-based adhesive according to claim 1 or 2, wherein the component contains diaminopolysiloxane in a range of less than 70 mol%. The polyimide adhesive according to any one of claims 1 to 3, wherein the component (B) is at least one hydride selected from the group consisting of C5 petroleum resin, C9 petroleum resin and C5 / C9 petroleum resin. (B) The polyimide adhesive according to any one of claims 1 to 4, wherein the content of the aromatic ring contained in the component is less than 50% by weight. The polyimide adhesive according to any one of claims 1 to 5, wherein the component (C) is at least one selected from the group consisting of an epoxy compound, a benzoxazine compound, a bismaleimide compound and a cyanate ester compound. Further general formula: Z-Si (R ¹ ) _a (OR ² ) _3-a (In the formula, Z is a group containing a functional group that reacts with an acid anhydride group, and R ¹ is hydrogen or 1 to 8 carbon atoms. Claims 1 to 1, wherein R ² contains a hydrocarbon group having 1 to 8 carbon atoms, and a contains a reactive alkoxysilyl compound (E) represented by 0, 1 or 2). Any of 6 polyimide-based adhesives. The polyimide adhesive according to any one of claims 1 to 7, further comprising a flame retardant (F). The polyimide adhesive according to any one of claims 1 to 8, further comprising an inorganic filler (G).