TWI810459B - Composition, reactant, adhesive, film-like adhesive material, adhesive layer, adhesive sheet, copper foil with resin, copper-clad laminate, printed wiring board, multilayer wiring board, and manufacturing method thereof - Google Patents

Abstract

The problem to be solved by the present invention is to provide a composition, reactant, adhesive, film adhesive material, adhesive layer, adhesive sheet, copper foil with resin, copper clad laminate, printed circuit board and multilayer circuit board and its method of manufacture. In order to solve the above problems, there is provided a composition comprising: a polyimide which is a reactant of a monomer group containing an aromatic tetracarboxylic anhydride and a dimer diamine; More than one of the group consisting of isocyanate, trimer triamine, and silane-modified epoxy resin.

Description

Composition, reactant, adhesive, film-like adhesive material, adhesive layer, adhesive sheet, copper foil with resin, copper-clad laminate, printed wiring board, multilayer wiring board, and manufacturing method thereof

The present invention relates to a composition, a reactant, an adhesive, a film-like adhesive material, an adhesive layer, an adhesive sheet, a resin-coated copper foil, a copper-clad laminate, a printed circuit board, a multilayer circuit board, and a manufacturing method thereof.

Various known resins are used in the manufacture of mobile communication equipment such as mobile phones and smart phones or their base station devices, network-related electronic equipment such as servers/routers, and printed circuit boards included in large computers.

[Problem to be Solved by the Invention] In recent years, in the above-mentioned network-related electronic devices, it is necessary to transmit and process large-capacity information with low loss and high speed, and the electronic signals processed by printed circuit boards of these products are also developing at high frequencies. High-frequency electronic signals are prone to attenuation. Therefore, it is necessary to further reduce the transmission loss in the printed circuit board. Therefore, low dielectric constant and low dielectric loss tangent (also referred to as low dielectric characteristics) are required for compositions used in the manufacture of printed wiring boards.

In addition, the composition used in the manufacture of printed wiring boards is also required to have good solder heat resistance when pre-dried.

The problem to be solved by the present invention is to provide a composition having a low dielectric constant and a low dielectric loss tangent, and having good solder heat resistance when pre-dried. [method used to solve the problem]

As a result of intensive studies, the present inventors have found that the above-mentioned problems can be solved with a predetermined composition.

The present invention provides the following items. (item 1) A composition comprising: a polyimide that is a reactant of a monomer group comprising an aromatic tetracarboxylic anhydride and a dimer diamine; and, At least one selected from the group consisting of polyisocyanate, trimer triamine, and silane-modified epoxy resin. (item 2) A reactant, which is polyimide and more than one reactant selected from the group consisting of polyisocyanate, trimer triamine and silane-modified epoxy resin, the polyimide is aromatic Reactant of the monomeric group of tetracarboxylic acid anhydride and dimer diamine. (item 3) An adhesive comprising the composition described in the above item, a crosslinking agent and an organic solvent. (item 4) A film-like adhesive material comprising a heat-cured product of the composition described in the above item and/or a heat-cured product of the adhesive described in the above item. (item 5) An adhesive layer comprising at least one selected from the group consisting of the composition described in the above item, the adhesive agent described in the above item, and the film-like adhesive material described in the above item. (item 6) An adhesive sheet comprising the adhesive layer described in the above items and a supporting film. (item 7) A resin-coated copper foil comprising the adhesive layer described in the above items and copper foil. (item 8) A copper clad laminate comprising: The adhesive sheet mentioned in the above item and/or the resin-attached copper foil mentioned in the above item; and, One or more types selected from the group consisting of copper foil, insulating sheet, and support film. (item 9) A copper-clad laminate having a copper-plated layer on the adhesive sheet described in the above item or the resin-coated copper foil described in the above item. (item 10) The copper-clad laminate as described in the above item, wherein the copper plating layer is an electroless copper plating layer or a vacuum copper plating layer. (item 11) A printed wiring board having a circuit pattern on the copper foil surface of the copper-clad laminate described in the above item. (item 12) A multilayer circuit board comprising: a printed circuit board (1) or a printed circuit board (1); the adhesive layer described in the preceding items; and, A printed circuit board (2) or a printed circuit board (2). (item 13) A kind of manufacture method of multilayer circuit board, it comprises following steps 1 and 2: Step 1: By combining one or more selected from the group consisting of the adhesive described in the above item, the film-like adhesive material described in the above item, and the adhesive sheet described in the above item with a printed circuit board (1) or a printed circuit board (1) or a printed circuit board (1) A step of contacting at least one side of the circuit board (1) to obtain a substrate with an adhesive layer; Step 2: A step of laminating a printed wiring board (2) or a printed circuit board (2) on the adhesive layer-attached substrate and crimping under heat and pressure.

In the present invention, one or more of the above-mentioned features may be provided in further combinations other than the explicit combinations. [Invention effect]

The composition of the present invention has a low dielectric constant and a low dielectric loss tangent, and is excellent in high-temperature heat resistance and solder heat resistance during pre-drying. Therefore, the composition of the present invention can be used as a thermoplastic polyimide composition.

Throughout the specification of the present invention, the range of numerical values such as each physical property value and content can be appropriately set (for example, selected from the upper limit and lower limit values described in the following items). Specifically, regarding the value α, when the upper and lower limits of the value α can be exemplified by A1, A2, A3, A4 (set to A1>A2>A3>A4), etc., the range of the value α can be exemplified below A1, A2 Below, below A3, above A2, above A3, above A4, A1~A2, A1~A3, A1~A4, A2~A3, A2~A4, A3~A4, etc.

[composition] The present invention provides a composition comprising: a polyimide which is a reactant of a monomer group comprising an aromatic tetracarboxylic anhydride and a dimer diamine; More than one of the group consisting of polymer triamine and silane-modified epoxy resin.

＜Polyimide＞ The above-mentioned polyimide is a reactant containing a monomer group including acid anhydrides such as aromatic tetracarboxylic acid anhydrides and diamines such as dimer diamines. The above polyimides may be used alone or in combination of two or more.

＜Aromatic Tetracarboxylic Anhydride＞ Aromatic tetracarboxylic anhydrides can be used alone or in combination of two or more. Aromatic tetracarboxylic anhydrides can, for example, be symmetric aromatic tetracarboxylic anhydrides or the like.

(Symmetrical aromatic tetracarboxylic anhydride) In the present invention, the "symmetrical aromatic tetracarboxylic anhydride" means an aromatic tetracarboxylic anhydride having a symmetry axis (for example, a C2 symmetry axis) in the molecule. As a symmetrical aromatic tetracarboxylic anhydride, the symmetrical aromatic tetracarboxylic anhydride represented by the following general formula etc. can be illustrated. (wherein, X represents a single bond, -SO ₂ -, -CO-, -O-, -OC ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O-, -COO-(CH ₂ ) _p -OCO- or -COO-H ₂ C-HC (-OC(=O)-CH ₃ )-CH ₂ -OCO-, p represents an integer of 1 to 20.)

The symmetrical aromatic tetracarboxylic anhydride represented by the above general formula can be exemplified by 3,3',4,4'-biphenyltetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dicarboxylic acid anhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 4,4'-[propane- 2,2-diylbis(1,4-phenyleneoxy)]bisphthalic dianhydride, 2,2-bis(3,3',4,4'-tetracarboxyphenyl)tetrafluoro Propanediandianhydride, 2,2-bis(3,4-dicarboxyphenyl)propanedianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)pyridinedianhydride, 2,2' ,3,3'-biphenyltetracarboxylic dianhydride, 2,2-bis(2,3-dicarboxyphenyl)propane dianhydride, pyromellitic dianhydride, 1,2,3,4-benzenetetra Carboxylic anhydride, 1,4,5,8-naphthalene tetracarboxylic anhydride, 2,3,6,7-naphthalene tetracarboxylic anhydride, etc.

Among the above-mentioned symmetrical aromatic tetracarboxylic anhydrides, from the viewpoint of the compatibility between the aromatic tetracarboxylic anhydride and diamine, the adhesion at room temperature, and the heat-resistant adhesion, etc., it is preferable to select from the group consisting of 3,3', 4,4' - Benzophenone tetracarboxylic dianhydride, 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]bisphthalic dianhydride and 4,4' - at least one member of the group consisting of oxybisphthalic anhydride.

The upper and lower limits of the content of the symmetrical aromatic tetracarboxylic anhydride in 100 mol% of the aromatic tetracarboxylic anhydride can be exemplified by 100 mol%, 90 mol%, 80 mol%, 70 mol%, 60 mol%, 55 mol%, 50 mol%, 40 mol%, 30 mol%, 20 mol%, 10 mol%, 0 mol%, etc. In one embodiment, the content of symmetrical aromatic tetracarboxylic anhydride in 100 mol% of aromatic tetracarboxylic anhydride is preferably about 0 mol% to about 100 mol%, more preferably about 50 mol% to about 100 mole %.

The upper and lower limits of the content of the symmetrical aromatic tetracarboxylic anhydride in 100% by mass of the aromatic tetracarboxylic anhydride can be exemplified as 100% by mass, 90% by mass, 80% by mass, 70% by mass, 60% by mass, 55% by mass, and 50% by mass. %, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 0% by mass, etc. In one embodiment, the content of the symmetrical aromatic tetracarboxylic anhydride in 100% by mass of the aromatic tetracarboxylic anhydride is preferably about 0% by mass to 100% by mass, more preferably about 50% by mass to 100% by mass.

The upper and lower limits of the content of the symmetrical aromatic tetracarboxylic anhydride in 100 mol% of the monomer group can be exemplified by 75 mol%, 70 mol%, 60 mol%, 50 mol%, 40 mol%, and 30 mol%. Ear %, 20 Mole %, 10 Mole %, 5 Mole %, 0 Mole %, etc. In one embodiment, the content of the symmetrical aromatic tetracarboxylic anhydride in 100 mol% of the monomer group is preferably about 0 mol% to about 75 mol%.

The upper and lower limits of the content of the symmetrical aromatic tetracarboxylic anhydride in 100% by mass of the monomer group can be exemplified by 75% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 0% by mass, etc. In one embodiment, the content of the symmetrical aromatic tetracarboxylic anhydride in 100% by mass of the monomer group is preferably about 0% by mass to 75% by mass.

(other aromatic tetracarboxylic anhydrides) In one embodiment, the monomer group may contain aromatic tetracarboxylic anhydrides (also referred to as other aromatic tetracarboxylic anhydrides) that are neither the above-mentioned fluorene skeleton-containing tetracarboxylic anhydrides nor symmetrical aromatic tetracarboxylic anhydrides.

In one embodiment, the content of other acid anhydrides in 100 mol% of aromatic tetracarboxylic acid anhydrides can be exemplified as less than 5 mol%, less than 4 mol%, less than 1 mol%, and less than 0.9 mol%. , less than 0.5 mol%, less than 0.1 mol%, about 0 mol%, etc.

In one embodiment, the content of other acid anhydrides in 100% by mass of aromatic tetracarboxylic acid anhydrides can be exemplified as less than 5% by mass, less than 4% by mass, less than 1% by mass, less than 0.9% by mass, and less than 0.5% by mass. %, less than 0.1% by mass, approximately 0% by mass, etc.

In one embodiment, the content of other acid anhydrides in 100 mol% of the monomer group can be exemplified as less than 5 mol%, less than 4 mol%, less than 1 mol%, less than 0.9 mol%, less than 0.9 mol%. At 0.5 mol%, less than 0.1 mol%, about 0 mol%, etc.

In one embodiment, the content of other acid anhydrides in 100% by mass of the monomer group can be exemplified as less than 5% by mass, less than 4% by mass, less than 1% by mass, less than 0.9% by mass, less than 0.5% by mass, Less than 0.1% by mass, approximately 0% by mass, etc.

The upper and lower limits of the aromatic tetracarboxylic anhydride content in 100 mol% of the monomer group can be exemplified by 75 mol%, 70 mol%, 65 mol%, 60 mol%, 55 mol%, and 50 mol%. %wait. In one embodiment, the content of the aromatic tetracarboxylic anhydride in 100 mol% of the monomer group is preferably about 50 mol% to about 75 mol%.

The upper limit and the lower limit of the content of the aromatic tetracarboxylic anhydride in 100 mass % of a monomer group can illustrate 75 mass %, 70 mass %, 65 mass %, 60 mass %, 55 mass %, 50 mass % etc. In one embodiment, the content of the aromatic tetracarboxylic anhydride in 100% by mass of the monomer group is preferably about 50% by mass to 75% by mass.

＜Diamine＞ Diamines can be used alone or in combination of two or more. As diamine, dimer diamine, carboxyl group-containing diamine, diamino polysiloxane, etc. can be illustrated.

(Dipolymer diamine) In the present invention, the dimer diamine is a substance obtained by substituting all the carboxyl groups of the dimer acid, which is a dimer of unsaturated fatty acids such as oleic acid, with primary amine groups (refer to JP (Kaihei No. 9-12712, etc.), various known dimer diamines can be used without particular limitation. The non-limiting general formulas of dimer diamines are shown below (in each formula, m+n=6-17 is preferred, p+q=8-19 is preferred, and the dotted line represents the carbon-carbon single bond or carbon-carbon double bond).

Examples of commercially available dimer diamines include VERSAMINE 551 (manufactured by Cognis Japan Co., Ltd.), VERSAMINE 552 (manufactured by Cognis Japan Co., Ltd.; a hydrogenated product of VERSAMINE 551); manufacturing), etc.

The upper and lower limits of the content of the dimer diamine component in 100 mol % of diamine can be exemplified by 100 mol %, 90 mol %, 80 mol %, 70 mol %, 60 mol %, and 50 mol % %, 40 mol%, 30 mol%, 25 mol%, 20 mol%, etc. In one embodiment, from the viewpoint of improving flexibility, adhesiveness, and solvent solubility, the content of the dimer diamine component in 100 mol% of diamine is preferably about 20 mol% to about 80 mol%. .

The upper and lower limits of the content of the dimer diamine component in 100% by mass of diamine can be exemplified as 100% by mass, 90% by mass, 80% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, and 30% by mass. % by mass, 25% by mass, 20% by mass, etc. In one embodiment, from the viewpoint of improving flexibility, adhesiveness, and solvent solubility, the content of the dimer diamine component in 100% by mass of diamine is preferably about 30% by mass to 95% by mass.

The upper and lower limits of the dimer diamine content in 100 mol % of the monomer group can be exemplified by 50 mol %, 40 mol %, 30 mol %, 20 mol %, 10 mol %, and 8 mol % %, 5 mol%, etc. In one embodiment, the content of dimer diamine in 100 mol% of the monomer group is preferably 5-50 mol%.

The upper limit and the lower limit of the dimer diamine content in 100 mass % of a monomer group can illustrate 50 mass %, 40 mass %, 30 mass %, 20 mass %, 10 mass %, 8 mass %, 5 mass % etc. In one embodiment, the content of dimer diamine in 100% by mass of the monomer group is preferably 5 to 50% by mass.

(Aromatic diamine) In one embodiment, the aromatic diamine is represented by the following general formula. (wherein, Y represents a single bond, -SO ₂ -, -CO-, -O-, -OC ₆ H ₄ -O-, -OC ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O -, -COO-(CH ₂ ) _q -OCO-, or -COO-H ₂ C-HC (-OC(=O)-CH ₃ )-CH ₂ -OCO-, q represents an integer of 1 to 20.)

Examples of the aromatic diamine include 4,4'-diaminobiphenyl, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, 4,4'-(4 , 4'-isopropylidene diphenyl-1,1'-diyldioxy) diphenylamine, etc.

The upper limit of the aromatic diamine content in 100 mol % of diamines can be exemplified by 80 mol %, 70 mol %, 60 mol %, 50 mol %, 40 mol %, 30 mol %, 25 mol % mol%, etc., the lower limit can be exemplified by 75 mol%, 70 mol%, 60 mol%, 50 mol%, 40 mol%, 30 mol%, 25 mol%, 20 mol%, etc. In one embodiment, from the viewpoint of solvent solubility, workability, and flexibility, the content of the aromatic diamine in 100 mol % of diamine is preferably 20 to 80 mol %.

The upper limit of the aromatic diamine content in 100 mass % of diamines can be illustrated as 80 mass %, 70 mass %, 60 mass %, 50 mass %, 40 mass %, 30 mass %, 25 mass % etc., and the lower limit can be illustrated as 75 mass %. % by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 25% by mass, 20% by mass, etc. In one embodiment, from the viewpoint of solvent solubility, workability, and flexibility, the content of the aromatic diamine in 100% by mass of diamine is preferably 20 to 80% by mass.

The upper limit of the aromatic diamine content in 100 mol % of the monomer group can be exemplified by 50 mol %, 40 mol %, 30 mol %, 20 mol %, 10 mol %, 8 mol %, etc., Examples of the lower limit include 40 mol%, 30 mol%, 20 mol%, 10 mol%, 8 mol%, 5 mol%, and the like. In one embodiment, the content of the aromatic diamine in 100 mol% of the monomer group is preferably 5-50 mol%.

The upper limit of the aromatic diamine content in 100% by mass of the monomer group can be exemplified by 50% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 8% by mass, etc., and the lower limit can be exemplified by 40% by mass, 30% by mass, 20% by mass, 10% by mass, 8% by mass, 5% by mass, etc. In one embodiment, the content of the aromatic diamine in 100% by mass of the monomer group is preferably 5 to 50% by mass.

The upper limit of the ratio of the amount of aromatic diamine to the amount of dimer diamine (aromatic diamine/dimer diamine) can be exemplified by 4.0, 3.0, 2.0, 1.0, 0.50, etc., and the lower limit can be exemplified 4.0, 3.0, 2.0, 1.0, 0.50, 0.25, etc. In one embodiment, from the viewpoint of solvent solubility, workability, flexibility, adhesiveness, and dielectric properties, the ratio of the amount of aromatic diamine to the amount of dimer diamine (aromatic diamine Amine/dipolymer diamine) is preferably from 0.25 to 4.0.

(Diaminopolysiloxane) Examples of diaminopolysiloxane include α,ω-bis(2-aminoethyl)polydimethylsiloxane, α,ω-bis(3-aminopropyl)polydimethylsiloxane , α,ω-bis(4-aminobutyl)polydimethylsiloxane, α,ω-bis(5-aminopentyl)polydimethylsiloxane, α,ω-bis[3 -(2-aminophenyl)propyl]polydimethylsiloxane, α,ω-bis[3-(4-aminophenyl)propyl]polydimethylsiloxane, 1,3 - Bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldisiloxane and the like.

The upper and lower limits of the content of diaminopolysiloxane in 100 mol % of diamine can be exemplified by 5 mol %, 4 mol %, 3 mol %, 2 mol %, 1 mol %, and 0 mol %. Ear% and so on. In one embodiment, from the viewpoint of improving flexibility, the content of diaminopolysiloxane in 100 mol % of diamine is preferably about 0 mol % to about 5 mol %.

5 mass %, 4 mass %, 3 mass %, 2 mass %, 1 mass %, 0 mass % etc. can be illustrated as the upper limit and the lower limit of content of the diaminopolysiloxane in 100 mass % of diamines. In one embodiment, from the viewpoint of improving flexibility, the content of diaminopolysiloxane in 100% by mass of diamine is preferably about 0% by mass to 5% by mass.

The upper and lower limits of the diaminopolysiloxane content in 100 mol% of the monomer group can be exemplified by 5 mol%, 4 mol%, 3 mol%, 2 mol%, 1 mol%, 0 mol%, Mole% and so on. In one embodiment, from the viewpoint of improving flexibility, the content of diaminopolysiloxane in 100 mol % of the monomer group is preferably about 0 mol % to about 5 mol %.

The upper and lower limits of the diaminopolysiloxane content in 100% by mass of the monomer group can be exemplified by 5% by mass, 4% by mass, 3% by mass, 2% by mass, 1% by mass, and 0% by mass. In one embodiment, from the viewpoint of improving flexibility, the content of diaminopolysiloxane in 100% by mass of the monomer group is preferably about 0% by mass to 5% by mass.

(other diamines) In one embodiment, the monomer group may contain diamines (also referred to as other diamines) other than the above. Examples of other diamines include alicyclic diamine, bis(aminophenoxyphenyl)propane, diaminodiphenyl ether, phenylenediamine, diaminodiphenylsulfide, diaminodiphenyl Diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenylphenylethane, bis(aminophenoxy phenyl) benzene, bis(aminobenzoyl)benzene, bis(aminodimethylbenzyl)benzene, bis(aminobis(trifluoromethyl)benzyl)benzene, aminophenoxybiphenyl , aminophenoxy phenyl ketone, amino phenoxy phenyl sulfide, amino phenoxy phenyl sulfide, amino phenoxy phenyl ether, amino phenoxy phenyl propane, bis(amine phenylphenoxybenzoyl)benzene, bis(aminophenoxy-α,α-dimethylbenzyl)benzene, bis[(aminoaryloxy)benzoyl]diphenylether , bis(amino-α,α-dimethylbenzylphenoxy)benzophenone, bis[amino-α,α-dimethylbenzylphenoxy]diphenylphenone, 4,4 '-bis[aminophenoxyphenoxy]diphenylphenone, diaminodiaryloxybenzophenone, diaminoaryloxybenzophenone, 6,6'-bis( Aminoaryloxy)-3,3,3',3'-tetramethyl-1,1'-spirobiindane, bis(aminoalkyl)ether, bis(aminoalkoxyalkyl ) ether, bis(aminoalkoxy)alkane, bis[(aminoalkoxy)alkoxy]alkane, (poly)ethylene glycol bis(aminoalkyl)ether, bis(aminoaryloxy base) pyridine, alkylenediamine, etc.

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

Examples of bis(aminophenoxyphenyl)propane include 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy base) phenyl] propane, etc.

Examples of diaminodiphenyl ether include 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether, and the like.

As phenylenediamine, phenylenediamines, such as p-phenylenediamine and m-phenylenediamine, etc. are illustrated.

Examples of diaminodiphenylsulfide include 3,3'-diaminodiphenylsulfide, 3,4'-diaminodiphenylsulfide, 4,4'-diaminodiphenylsulfide Ether etc.

Examples of diaminodiphenylrone include 3,3'-diaminodiphenylrone, 3,4'-diaminodiphenylrone, 4,4'-diaminodiphenylrone, and the like.

Examples of diaminobenzophenone include 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone, and the like.

Examples of diaminodiphenylmethane include 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane, and the like.

Examples of diaminophenylpropane include 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2-(3-aminophenyl)-2 -(4-Aminophenyl)propane and the like.

Examples of diaminophenylhexafluoropropane include 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-amino Phenyl)-1,1,1,3,3,3-hexafluoropropane, 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3, 3,3-hexafluoropropane, etc.

Examples of diaminophenylphenylethane include 1,1-bis(3-aminophenyl)-1-phenylethane, 1,1-bis(4-aminophenyl)-1-phenyl Ethane, 1-(3-aminophenyl)-1-(4-aminophenyl)-1-phenylethane, etc.

Examples of bis(aminophenoxy)benzene include 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3 -aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene and the like.

Examples of bis(aminobenzoyl)benzene include 1,3-bis(3-aminobenzoyl)benzene, 1,3-bis(4-aminobenzoyl)benzene, 1,4- Bis(3-aminobenzoyl)benzene, 1,4-bis(4-aminobenzoyl)benzene, etc.

Examples of bis(aminodimethylbenzyl)benzene include 1,3-bis(3-amino-α,α-dimethylbenzyl)benzene, 1,3-bis(4-amino-α,α -Dimethylbenzyl)benzene, 1,4-bis(3-amino-α,α-dimethylbenzyl)benzene, 1,4-bis(4-amino-α,α-dimethyl Benzyl) benzene, etc.

Bis(aminobis(trifluoromethyl)benzyl)benzene can be exemplified by 1,3-bis(3-amino-α,α-bis(trifluoromethyl)benzyl)benzene, 1,3-bis( 4-Amino-α,α-bis(trifluoromethyl)benzyl)benzene, 1,4-bis(3-amino-α,α-bis(trifluoromethyl)benzyl)benzene, 1, 4-bis(4-amino-α,α-bis(trifluoromethyl)benzyl)benzene, etc.

Examples of aminophenoxybiphenyl include 2,6-bis(3-aminophenoxy)benzonitrile, 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'- Bis(4-aminophenoxy)biphenyl and the like.

As the aminophenoxyphenyl ketone, bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]ketone and the like can be exemplified.

Examples of aminophenoxyphenyl sulfide include bis[4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfide, and the like.

Examples of the aminophenoxyphenylphenone include bis[4-(3-aminophenoxy)phenyl]phenone, bis[4-(4-aminophenoxy)phenyl]phenone, and the like.

Examples of aminophenoxyphenyl ether include bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-aminophenoxy)phenyl]ether, and the like.

Aminophenoxyphenylpropane can be exemplified by 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[3-(3-aminophenoxy)benzene Base]-1,1,1,3,3,3-hexafluoropropane, 2,2-bis[4-(4-aminophenoxy)phenyl]-1,1,1,3,3, 3-hexafluoropropane, etc.

Examples of bis(aminophenoxybenzoyl)benzene include 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-amino Phenoxy) benzoyl] benzene and the like.

Bis(aminophenoxy-α,α-dimethylbenzyl)benzene can be exemplified by 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, etc.

Examples of bis[(aminoaryloxy)benzoyl]diphenyl ether include 4,4'-bis[4-(4-aminophenoxy)benzoyl]diphenyl ether and the like.

Bis(amino-α,α-dimethylbenzylphenoxy)benzophenone can be exemplified by 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)benzene Oxygen] benzophenone etc.

Bis[amino-α,α-dimethylbenzylphenoxy]diphenylphenone can be exemplified by 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)benzene Oxygen] diphenylsulfone etc.

Examples of 4,4'-bis[aminophenoxyphenoxy]diphenylsulfone include 4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenylsulfone and the like.

Examples of diaminodiaryloxybenzophenone include 3,3'-diamino-4,4'-diphenoxybenzophenone, 3,3'-diamino-4,4' - bisphenoxybenzophenone and the like.

Examples of diaminoaryloxybenzophenone include 3,3'-diamino-4-phenoxybenzophenone and 3,3'-diamino-4-biphenoxybenzophenone Ketones etc.

6,6'-bis(aminoaryloxy)-3,3,3',3'-tetramethyl-1,1'-spirobiindane can be exemplified by 6,6'-bis(3-amine ylphenoxy)-3,3,3',3'-tetramethyl-1,1'-spirobiindane, 6,6'-bis(4-aminophenoxy)-3,3, 3',3'-Tetramethyl-1,1'-spirobiindane etc.

As bis(aminoalkyl)ether, bis(aminomethyl)ether, bis(2-aminoethyl)ether, bis(3-aminopropyl)ether, etc. can be illustrated.

Examples of bis(aminoalkoxyalkyl) ethers include bis[2-(aminomethoxy)ethyl]ether, bis[2-(2-aminoethoxy)ethyl]ether, bis[2 -(3-Aminopropoxy)ethyl]ether, etc.

Examples of the bis(aminoalkoxy)alkane include 1,2-bis(aminomethoxy)ethane, 1,2-bis(2-aminoethoxy)ethane, and the like.

Examples of the bis[(aminoalkoxy)alkoxy]alkane include 1,2-bis[2-(aminomethoxy)ethoxy]ethane, 1,2-bis[2-(2-amine ethoxy) ethoxy] ethane and the like.

Examples of (poly)ethylene glycol bis(aminoalkyl)ether include ethylene glycol bis(3-aminopropyl)ether, diethylene glycol bis(3-aminopropyl)ether, triethylene glycol bis(aminopropyl)ether, (3-Aminopropyl) ether, etc.

Examples of bis(aminoaryloxy)pyridine include 2,6-bis(3-aminophenoxy)pyridine and the like.

Examples of the alkylene diamine include ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-Diaminoheptane, 1,8-Diaminooctane, 1,9-Diaminononane, 1,10-Diaminodecane, 1,11-Diaminoundecane , 1,12-diaminododecane, etc.

In one embodiment, the content of other diamines in 100 mol % of diamines can be exemplified as less than 5 mol %, less than 4 mol %, less than 1 mol %, less than 0.9 mol %, low At 0.5 mol%, less than 0.1 mol%, about 0 mol%, etc.

In one embodiment, the content of other diamines in 100% by mass of diamine can be exemplified as less than 5% by mass, less than 4% by mass, less than 1% by mass, less than 0.9% by mass, less than 0.5% by mass, Less than 0.1% by mass, approximately 0% by mass, etc.

In one embodiment, the content of other diamines in 100 mol% of the monomer group can be exemplified as less than 5 mol%, less than 4 mol%, less than 1 mol%, less than 0.9 mol%, Less than 0.5 mol%, less than 0.1 mol%, about 0 mol%, etc.

In one embodiment, the content of other diamines in 100% by mass of the monomer group can be exemplified as less than 5% by mass, less than 4% by mass, less than 1% by mass, less than 0.9% by mass, and less than 0.5% by mass , less than 0.1% by mass, about 0% by mass, etc.

The upper limit and the lower limit of the diamine content in 100 mol % of a monomer group can illustrate 50 mol %, 45 mol %, 40 mol %, 35 mol %, 30 mol %, 25 mol %, etc. In one embodiment, the content of diamine in 100 mol% of the monomer group is preferably about 25 mol% to about 50 mol%.

50 mass %, 45 mass %, 40 mass %, 35 mass %, 30 mass %, 25 mass % etc. can be illustrated as the upper limit and the lower limit of content of the diamine in 100 mass % of monomer groups. In one embodiment, the content of the diamine in 100 mol % of the monomer group is preferably about 25 mass % to about 50 mass %.

1.5, 1.4, 1.3, 1.2, 1.1, 1.0 etc. can be illustrated as the upper limit and the lower limit of the molar ratio [aromatic tetracarboxylic anhydride/diamine] of an aromatic tetracarboxylic anhydride and diamine. In one embodiment, the molar ratio [aromatic tetracarboxylic anhydride/diamine] of aromatic tetracarboxylic anhydride to diamine is preferably about 1.0 to about 1.5 from the viewpoint of solvent solubility and solution stability.

1.5, 1.4, 1.2, 1.0, 0.9, 0.7, 0.6, 0.5 etc. can be illustrated as the upper limit and the lower limit of the mass ratio [aromatic tetracarboxylic anhydride/diamine] of an aromatic tetracarboxylic anhydride and diamine. In one embodiment, the mass ratio [aromatic tetracarboxylic anhydride/diamine] of an aromatic tetracarboxylic anhydride to a diamine is preferably 0.5 to 1.5.

＜Other monomers＞ In one embodiment, the monomer group may contain a monomer (also referred to as another monomer) that is neither an aromatic tetracarboxylic acid anhydride nor a diamine. Examples of other monomers include aliphatic tetracarboxylic anhydrides and the like.

In one embodiment, the content of other monomers in the monomer group can be exemplified as less than 5 mol %, less than 4 mol %, less than 1 mol %, less than 0.9 mol %, less than 0.5 mol % ear%, less than 0.1 mole%, about 0 mole%, etc.

In one embodiment, the content of other monomers in the monomer group can be exemplified as less than 5% by mass, less than 4% by mass, less than 1% by mass, less than 0.9% by mass, less than 0.5% by mass, less than 0.1% by mass, about 0% by mass, etc.

In one embodiment, the above-mentioned aromatic tetracarboxylic acid anhydride is 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]bisphthalic dianhydride and the above-mentioned The diamine of the carboxyl group is 3,5-diaminobenzoic acid, or the above-mentioned aromatic tetracarboxylic acid anhydride is 3,3',4,4'-benzophenone tetracarboxylic dianhydride and the above-mentioned carboxyl-containing diamine is 5,5'-Methylenebis(2-aminobenzoic acid).

＜Physical properties of polyimide, etc.＞ 50000, 40000, 30000, 20000, 10000, 7500, 5500, 5000 etc. can be illustrated as the upper limit and the lower limit of the weight average molecular weight of the said polyimide. In one embodiment, the polyimide has a weight average molecular weight of 5,000 to 50,000 from the viewpoint of dielectric properties, solvent solubility, and flexibility.

40000, 30000, 20000, 10000, 7500, 5000, 3000, 2000 etc. can be illustrated as the upper limit and the lower limit of the number average molecular weight of the said polyimide. In one embodiment, the polyimide has a number average molecular weight of 2,000 to 40,000 from the viewpoint of dielectric properties, solvent solubility, and flexibility.

The weight average molecular weight and number average molecular weight can be calculated|required as the polystyrene conversion value measured by gel permeation chromatography (GPC), for example.

220°C, 200°C, 150°C, 100°C, 50°C, 25°C, 20°C, etc. can be illustrated as the upper limit and the lower limit of the softening point of the polyimide. In one embodiment, the softening point of the polyimide is preferably 20 to 220° C. from the viewpoint of workability, heat resistance, and solvent solubility.

The softening point can be obtained using a commercially available measuring device (“ARES-2KSTD-FCO-STD”, manufactured by Rheometric Scientific Co., Ltd.) or the like.

The upper and lower limits of the acid value of the polyimide can be exemplified by 300 mgKOH/g, 275 mgKOH/g, 250 mgKOH/g, 225 mgKOH/g, 200 mgKOH/g, 175 mgKOH/g, 150 mgKOH/g, 125 mgKOH/g, 100 mgKOH/g, 75mgKOH/g, 50mgKOH/g, 25mgKOH/g, 20mgKOH/g, etc. In one embodiment, the acid value of the polyimide is preferably 20-300 mgKOH/g.

The acid value can be determined by the procedure described in JIS K 0070:1992.

<Manufacturing method of polyimide, etc.> The above polyimide can be produced by various known methods. A method for producing polyimide can be exemplified: including a monomer group including an aromatic tetracarboxylic anhydride and a diamine including a dimer diamine at a temperature of preferably about 60° C. to about 120° C., more preferably about 80° C. ° C to about 100 ° C, preferably at a temperature of about 0.1 hours to about 2 hours, more preferably about 0.1 hours to about 0.5 hours of addition polymerization to obtain the addition polymer; The polymer is preferably subjected to a temperature of about 80°C to about 250°C, more preferably about 100°C to about 200°C, preferably for about 0.5 hours to about 50 hours, more preferably about 1 hour to about 20 hours Imidization reaction, that is, the method of the step of dehydration ring closure reaction, etc.

In addition, in the step of carrying out the imidization reaction, various known reaction catalysts, dehydrating agents, and organic solvents described later can be used. Various known reaction catalysts, dehydrating agents, and organic solvents described below can be used alone or in combination of two or more. Examples of the reaction catalyst include aliphatic tertiary amines such as triethylamine; aromatic tertiary amines such as dimethylaniline; heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline; and the like. In addition, examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride, aromatic acid anhydrides such as benzoic anhydride, and the like.

The imide ring closure rate of the polyimide is not particularly limited. Here, the "imide ring closure rate" refers to the content of cyclic imide bonds in polyimide, and can be determined by various spectroscopic methods such as nuclear magnetic resonance (NMR) and infrared (IR) analysis. In addition, the imide ring closure rate of the above-mentioned polyimide is preferably about 70% or more, more preferably about 85% to about 100%, from the viewpoint of improving room temperature adhesiveness and heat-resistant adhesiveness.

The upper and lower limits of the polyimide content in 100% by mass of the composition can be exemplified by 99.9% by mass, 99.8% by mass, 99.5% by mass, 99% by mass, 98% by mass, 95% by mass, 90% by mass, and 80% by mass , 70% by mass, 60% by mass, 55% by mass, 50% by mass, etc. In one embodiment, the polyimide content in 100% by mass of the composition is preferably 50 to 99.9% by mass.

The upper and lower limits of the content of at least one selected from the group consisting of polyisocyanate, trimer triamine, and silane-modified epoxy resin in 100% by mass of the composition can be exemplified by 50% by mass, 45% by mass, 40% by mass, % by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 2% by mass, 1% by mass, 0.5% by mass, 0.2% by mass, 0.1% by mass, etc. In one embodiment, the content of at least one selected from the group consisting of polyisocyanate, trimer triamine, and silane-modified epoxy resin in 100% by mass of the composition is preferably 0.1 to 50% by mass.

The mass ratio of polyimide to more than one selected from the group consisting of polyisocyanate, trimer triamine and silane-modified epoxy resin (polyimide/selected from polyisocyanate, trimer triamine and silane-modified epoxy resin) the upper and lower limits can be illustrated as 1000, 900, 800, 700, 600, 500, 400, 300, 200, 190, 175, 150, 145, 140 , 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 83, 80, 75, 70, 67, 65, 60, 55, 50, 45, 40, 35, 30, 29 , 25, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 7, 5, 4, 3, 2, 1, etc. In one embodiment, the mass ratio of polyimide to more than one selected from the group consisting of polyisocyanate, trimer triamine and silane-modified epoxy resin (polyimide/selected from polyisocyanate , terpolymer triamine and silane-modified epoxy resin) is preferably 1-1000.

＜Polyisocyanate＞ In the present invention, "polyisocyanate" refers to a compound having two or more isocyanate groups (-N=C=O). Examples of the polyisocyanate include straight-chain aliphatic polyisocyanate, branched-chain aliphatic polyisocyanate, alicyclic polyisocyanate, aromatic polyisocyanate, and their biuret, isocyanurate, allophanate, Additives, etc. In the above composition, polyisocyanates may be used alone or in combination of two or more.

Examples of straight-chain aliphatic groups include straight-chain alkylene groups and the like. The linear alkylene group is represented by the general formula: -(CH ₂ ) _n - (n is an integer of 1 or more). Examples of straight-chain alkylene include methylene, ethylene, propylenyl, n-butylene, n-pentyl, n-hexyl, n-heptyl, n-octyl, n-nonyl, n-decyl and the like.

Examples of linear aliphatic polyisocyanates include methylene diisocyanate, dimethylene diisocyanate, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptaethylene Methyl diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, decamethylene diisocyanate, etc.

As a branched aliphatic group, a branched chain alkylene group etc. are illustrated. A branched alkylene group is a group in which at least one hydrogen atom of a straight chain alkylene group is substituted with an alkyl group. Examples of the branched alkylene group include diethylpentylene, trimethylbutylene, trimethylpentylene, trimethylhexylene (trimethylhexamethylene), and the like.

As branched-chain aliphatic polyisocyanate, diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, trimethylhexamethylene diisocyanate, etc. can be illustrated.

As an alicyclic group, a cycloalkylene group etc. are illustrated. The cycloalkylene group can be exemplified by a monocyclic cycloalkylene group, a bridged ring cycloalkylene group, a condensed ring cycloalkylene group, and the like. In addition, in the cycloalkylene group, one or more hydrogen atoms may be substituted by straight-chain or branched-chain alkyl groups.

In the present invention, a monocyclic ring refers to a ring structure that does not have a bridge structure inside formed by a carbon covalent bond. In addition, a condensed ring refers to a ring structure in which two or more monocyclic rings share two atoms (that is, only one side of each ring is shared (fused) with each other). A bridged ring refers to a ring structure in which two or more monocyclic rings share three or more atoms.

Examples of the monocyclic cycloalkylene group include cyclopentylene, cyclohexylene, cycloheptylene, cyclodecylene, 3,5,5-trimethylcyclohexylene and the like.

As the bridged cycloalkylene group, tricyclodecanyl group, adamantyl group, norbornyl group and the like can be exemplified.

As the fused ring cycloalkylene group, a bicyclodecyl group and the like can be exemplified.

As the alicyclic polyisocyanate, monocyclic alicyclic polyisocyanate, bridged alicyclic polyisocyanate, condensed ring alicyclic polyisocyanate, etc. can be illustrated.

Examples of monocyclic alicyclic polyisocyanates include hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptyl diisocyanate, cyclodecylene diisocyanate, 3 , 5,5-trimethylcyclohexyl diisocyanate, dicyclohexylmethane diisocyanate, etc.

Examples of bridged cycloaliphatic polyisocyanates include tricyclodecanyl diisocyanate, adamantane diisocyanate, norbornene diisocyanate, and the like.

Examples of the condensed ring alicyclic polyisocyanate include dicyclodecanyl diisocyanate and the like.

As an aromatic group, a monocyclic aromatic group, a condensed ring aromatic group, etc. are illustrated. In addition, in the aromatic group, one or more hydrogen atoms may be substituted by straight-chain or branched-chain alkyl groups.

Examples of the monocyclic aromatic group include phenyl (phenylene), tolyl (cresyl), mesityl (mesityl), and the like. In addition, examples of the condensed ring aromatic group include naphthyl (naphthyl) and the like.

As aromatic polyisocyanate, a monocyclic aromatic polyisocyanate, a condensed ring aromatic polyisocyanate, etc. can be illustrated.

Examples of monocyclic aromatic polyisocyanate include dialkyl diphenylmethane diisocyanate such as 4,4'-diphenyldimethylmethane diisocyanate and tetraalkane such as 4,4'-diphenyltetramethylmethane diisocyanate. Diphenylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-dibenzyl isocyanate, 1,3-benzenediisocyanate, 1,4-benzenediisocyanate, toluene diisocyanate, Xylylene diisocyanate, m-tetramethylxylylene diisocyanate, etc.

As the condensed ring aromatic polyisocyanate, 1,5-naphthalene diisocyanate and the like can be illustrated.

The biuret body of polyisocyanate can illustrate the compound etc. which are represented by the following structural formula. [In the formula, n ^b is an integer of 1 or more, R ^bA to R ^bE are each independently an alkylene group, an arylylene group, or a group formed by a combination of an alkylene group and an arylylene group, and R ^bα to R ^bβ are each independently isocyanate or (n ^b1 is an integer of 0 or more, R ^b1 to R ^b5 are each independently an alkylene group, an arylylene group, or a group formed by a combination of an alkylene group and an arylylene group, and each of R ^b ' to R ^b '' is independently are isocyanate groups or R ^bα to R ^bβ groups themselves. R ^b4 to R ^b5 and R ^b '' may be different in each constituent unit.). R ^bD to R ^bE and R ^bβ may have different groups in each constituent unit. ]

The group which combined an alkylene group and an arylene group is exemplified by an alkylene arylylene group and the like.

The alkylene arylylene group is a group represented by -R ^alkylene -R ^arylene -R ^alkylene - (wherein R ^alkylene represents an alkylene group and R ^arylene represents an arylene group).

Examples of biurets of polyisocyanates include DURANATE 24A-100, DURANATE 22A-75P, and DURANATE 21S-75E (manufactured by Asahi Kasei Co., Ltd. above); Desmodur N3200A (biurets of hexamethylene diisocyanate) (above manufactured by Sumitomo Bayer Urethane Co., Ltd.), etc.

As an isocyanurate body of polyisocyanate, the compound etc. which are represented by the following structural formula can be illustrated. [wherein, n ⁱ is an integer of 0 or more, R ^iA to R ^iE are each independently an alkylene group, an arylylene group, or a group formed by a combination of an alkylene group and an arylylene group, and R ^iα to R ^iβ are each independently isocyanate or (n ⁱ¹ is an integer of 0 or more, R ⁱ¹ to R ⁱ⁵ are each independently an alkylene group, an arylylene group, or a group formed by a combination of an alkylene group and an arylylene group, and each of R ⁱ ' to R ⁱ '' is independently are isocyanate groups or the groups of R ^iα to R ^iβ themselves. R ⁱ⁵ and R ⁱ '' may be different in each constituent unit.). The groups of R ^iD to R ^iE and R ^iβ may be different in each constitutional unit. ]

The isocyanurate body of polyisocyanate can illustrate DURANATE TPA-100, DURANATE TKA-100, DURANATE MFA-75B, DURANATE MHG-80B (the above are manufactured by Asahi Kasei Co., Ltd.); Coronate HXR (hexamethylene diisocyanate Isocyanurate body) (the above are manufactured by Tosoh Co., Ltd.); TAKENATE D-131N (isocyanurate body of xylene diisocyanate), TAKENATE D204EA-1 (isocyanurate body of toluene diisocyanate body), TAKENATE D-127N (isocyanurate body of hydrogenated xylene diisocyanate) (manufactured by Mitsui Chemicals Co., Ltd. above); VESTANAT T1890/100 (isocyanurate body of isophorone diisocyanate ) (the above are manufactured by Evonik Japan Co., Ltd.), etc.

The allophanate body of a polyisocyanate can illustrate the compound etc. which are represented by the following structural formula. [wherein, n ^a is an integer of 0 or more, R ^aA is an alkyl group or an aryl group, and R ^aB to R ^aG are each independently an alkylene group, an arylylene group, or a combination of an alkylene group and an arylylene group. group, R ^aα ~ R ^aγ are each independently an isocyanate group or (n ^a1 is an integer of 0 or more, R ^a1 to R ^a6 are each independently an alkylene group or an arylylene group, and R ^a ' to R ^a ''' are each independently an isocyanate group or a group of R ^aα to R ^aγ itself group. R ^a1 to R ^a4 , R ^a ' to R ^a ''' may be different in each constituent unit.). R ^aB to R ^aE and R ^aα to R ^aγ may have different groups in each constituent unit. ]

As a commercial item of the allophanate body of a polyisocyanate, Takenate D-178N (made by Mitsui Chemicals Co., Ltd.) etc. can be illustrated.

The adduct of polyisocyanate can be illustrated: The adduct of trimethylolpropane and polyisocyanate represented by the following structural formula, [wherein, n ^ad is an integer of 0 or more, R ^adA to R ^adE are each independently an alkylene group, an arylylene group or a group formed by a combination of an alkylene group and an arylylene group, and R ^ad1 to R ^ad2 are each independently ground for (In the formula, n ^ad 'is an integer of 0 or more, R ^ad '～R ^ad '' are each independently an alkylene group, an arylylene group, or a group formed by a combination of an alkylene group and an arylylene group, and R ^ad ''' is the group of R ^ad1 ～ ^Rad2 itself, and the groups of R ^ad '～R ^ad ''' can be different in each constituent unit.), R ^adD ～R ^adE , R ^ad2 can be grouped in each constituent unit different. ]; The adduct of glycerol and polyisocyanate represented by the following structural formula, [wherein, n ^ad1 is an integer of 0 or more, R ^adα to R ^adε are each independently an alkylene group or an arylylene group, and R ^adA to R ^adB are each independently (In the formula, n ^ad1 ' is an integer of 0 or more, R ^adδ '～R ^adε ' are each independently an alkylene group, an arylylene group or a group formed by a combination of an alkylene group and an arylylene group, and R ^adB ' is The groups of R ^adA to R ^adB itself, the groups of R ^adδ ' to R ^adε ', R ^adB ' may be different in each constituent unit.), and the groups of R ^adδ to R ^adε may be different in each constituent unit. ];wait.

Examples of polyisocyanate adducts include DURANATE P301-75E (the above are manufactured by Asahi Kasei Co., Ltd.); TAKENATE D110N, TAKENATE D160N (the above are manufactured by Mitsui Chemicals Co., Ltd.); Coronate L (the above are manufactured by Tosoh Co., Ltd.) wait.

The upper and lower limits of the polyisocyanate content in 100% by mass of the composition can be exemplified by 50% by mass, 45% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 2% by mass, 1 % by mass, 0.5% by mass, 0.2% by mass, 0.1% by mass, etc. In one embodiment, the content of the polyisocyanate in 100% by mass of the composition is preferably 0.1 to 50% by mass.

The upper and lower limits of the mass ratio of polyimide to polyisocyanate (polyimide/polyisocyanate) can be exemplified as 1000, 900, 800, 700, 600, 500, 400, 300, 200, 190, 175, 150, 145 , 140, 135, 130, 125, 120, 115, 110, 105, 100, 95, 90, 85, 83, 80, 75, 70, 67, 65, 60, 55, 50, 45, 40, 35, 30 , 29, 25, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 7, 5, 4, 3, 2, 1, etc. In one embodiment, the mass ratio of polyimide to polyisocyanate (polyimide/polyisocyanate) is preferably 1-1000.

<Trimer triamine> Tripolymer triamine is a trimer acid (refer to JP 2013-505345 A, etc.) which is a trimer of unsaturated fatty acids such as oleic acid, and substitutes primary amino groups for all carboxyl groups. As the obtained substance, various known terpolymer triamines can be used without particular limitation. Hereinafter, non-limiting structural formulas of terpolymer triamines are shown (dashed lines represent carbon-carbon single bonds or carbon-carbon double bonds, R represents ethylidene (-CH ₂ CH ₂ -) or vinylene ( -CH=CH-)).

As a commercial item of a trimer triamine, PRIAMINE1071 (made by CRODA Japan Co., Ltd.) etc. can be illustrated. In addition, content of the trimer triamine component in a commercial item is about 15 mass % - about 20 mass % normally, and may contain the dimer diamine exceeding 80 mass % as a balance.

The upper and lower limits of the content of the trimer triamine in 100% by mass of the composition can be exemplified by 50% by mass, 45% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, and 2% by mass %, 1% by mass, 0.5% by mass, 0.2% by mass, 0.1% by mass, etc. In one embodiment, the content of the trimer triamine in 100% by mass of the composition is preferably 0.1 to 50% by mass.

The upper and lower limits of the mass ratio of polyimide to trimer triamine (polyimide/trimer triamine) can be exemplified as 1000, 900, 800, 700, 600, 500, 400, 300, 200, 190 ,175,150,145,140,135,130,125,120,115,110,105,100,95,90,85,83,80,75,70,67,65,60,55,50,45 , 40, 35, 30, 29, 25, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 7, 5, 4, 3, 2, 1, etc. In one embodiment, the mass ratio of polyimide to trimer triamine (polyimide/trimer triamine) is preferably 1-1000.

＜Silane Modified Epoxy Resin＞ Silane-modified epoxy resin is the reactant of hydroxyl-containing epoxy resin and partial condensation product of alkoxysilane.

Examples of the hydroxyl group-containing epoxy resin include bisphenol-type epoxy resins, novolak-type epoxy resins, and the like.

5000, 4000, 3000, 2000, 1000, 900, 800, 750, 500, 450, 400, 300, 250, 200, 180 etc. can be illustrated as the upper limit and the lower limit of the epoxy equivalent of a hydroxyl group-containing epoxy resin. In one embodiment, the epoxy equivalent of the hydroxyl-containing epoxy resin is preferably 180-5000, more preferably 450-500.

The partial condensate of alkoxysilane can be exemplified by the general formula: R ¹ _p Si(OR ² ) _4-p (wherein, p is an integer from 0 to 2, R ¹ is a substituted or unsubstituted alkane having 6 or less carbon atoms group, aryl group or alkenyl group, R ² is an alkyl group with 6 or less carbon atoms.) represented by alkoxysilane or their condensate, etc.

Examples of alkyl groups having 6 or less carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, secondary butyl, isobutyl, tertiary butyl, n-pentyl, neopentyl, iso Pentyl, secondary pentyl, 3-pentyl, tertiary pentyl, hexyl, isohexyl, 3-methylpentyl, 2,3-dimethylbutyl, 2,2-dimethylbutyl.

As a substituent, a glycidyl group, a mercapto group, an epoxy group etc. can be illustrated.

As the aryl group, phenyl, naphthyl and the like can be exemplified.

Examples of alkenyl include vinyl, allyl and the like.

As an alkoxysilane, a tetraalkoxysilane, a trialkoxysilane, a dialkoxysilane, etc. are illustrated.

As tetraalkoxysilane, tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, tetrabutoxysilane, etc. are illustrated.

As trialkoxysilane, an alkyltrialkoxysilane, an aryltrialkoxysilane, a functional group-containing trialkoxysilane, etc. are illustrated.

Examples of alkyltrialkoxysilane include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltrimethoxysilane, and ethyltrimethoxysilane. Ethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, isopropyltrimethoxysilane, isopropyltriethoxysilane, etc.

The aryltrialkoxysilane can be exemplified by phenyltrimethoxysilane, phenyltriethoxysilane, and the like.

Examples of alkenyltrialkoxysilane include vinyltrimethoxysilane, vinyltriethoxysilane, and the like.

Examples of functional group-containing trialkoxysilanes include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercapto Propyltriethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, 3,4-epoxycyclohexylethyltrimethoxysilane, etc.

As dialkoxysilane, dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, diethyldiethoxysilane, etc. are illustrated.

Silane-modified epoxy resins are produced by esterifying partial condensates of hydroxyl-containing epoxy resins and alkoxysilanes through dealcoholization. Although not particularly limited, it is preferable to conduct the reaction at a reaction temperature of 50 to 130° C. so that the silica equivalent mass of the alkoxysilane partial condensate/the mass (mass ratio) of the hydroxyl group-containing epoxy resin is 0.01 to 1.2. The reaction was carried out for 1 to 15 hours.

The upper and lower limits of the content of the silane-modified epoxy resin in 100% by mass of the composition can be exemplified by 50% by mass, 45% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 2 % by mass, 1% by mass, 0.5% by mass, 0.2% by mass, 0.1% by mass, etc. In one embodiment, the content of the silane-modified epoxy resin in 100% by mass of the composition is preferably 0.1-50% by mass.

The upper and lower limits of the mass ratio of polyimide to silane-modified epoxy resin (polyimide/silane-modified epoxy resin) can be exemplified as 1000, 900, 800, 700, 600, 500, 400, 300, 200 ,190,175,150,145,140,135,130,125,120,115,110,105,100,95,90,85,83,80,75,70,67,65,60,55,50 , 45, 40, 35, 30, 29, 25, 20, 19, 18, 17, 16, 15, 14, 13, 12, 11, 10, 9, 7, 5, 4, 3, 2, 1, etc. In one embodiment, the mass ratio of polyimide to silane-modified epoxy resin (polyimide/silane-modified epoxy resin) is preferably 1-1000.

In one embodiment, the composition described above can be used as a thermoplastic polyimide composition or a plating primer composition (for example, a copper plating primer composition).

[Reactant] The invention provides a reactant, which is polyimide and more than one reactant selected from the group consisting of polyisocyanate, trimer triamine and silane-modified epoxy resin, the polyimide It is a reactant of a monomer group containing aromatic tetracarboxylic anhydride and dimer diamine.

Components, such as an aromatic tetracarboxylic acid anhydride, can illustrate what was mentioned above, etc.

The reaction conditions at the time of manufacturing the said reactant are not specifically limited, The heating, pressure bonding conditions, etc. at the time of manufacturing the copper-clad laminated board mentioned later are mentioned.

In one embodiment, the above-mentioned reactant can be used as a thermoplastic polyimide layer or a plating primer layer (for example, a copper plating primer layer).

[adhesive] The present invention provides an adhesive, which comprises the above composition, a crosslinking agent and an organic solvent.

The upper and lower limits of the polyimide content in 100% by mass of the above-mentioned adhesive can be exemplified by 90% by mass, 80% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 20% by mass, Mass%, 10 mass%, 5 mass%, etc. The content of the polyimide in 100% by mass of the adhesive is preferably about 5% by mass to 90% by mass.

＜Crosslinking agent＞ As the crosslinking agent, various known crosslinking agents can be used without particular limitation as long as they function as a polyimide crosslinking agent. The crosslinking agent can be used alone or in combination of two or more.

Examples of the crosslinking agent include epoxy, benzoxazine, bismaleimide, cyanate, polyisocyanate and the like. In one embodiment, the crosslinking agent is preferably at least one selected from the group consisting of epoxy, benzoxazine, bismaleimide and cyanate.

(epoxide) Epoxides can be exemplified by phenol novolak type epoxy, cresol novolak type epoxy, bisphenol A type epoxy, bisphenol F type epoxy, bisphenol S type epoxy, hydrogenated bisphenol A Type epoxy, hydrogenated bisphenol F type epoxy, stilbene type epoxy, triazine skeleton-containing epoxy, fluorene skeleton-containing epoxy, linear aliphatic epoxy, alicyclic ring Oxides, glycidylamine-type epoxides, trisphenolmethane-type epoxides, alkyl-modified trisphenolmethane-type epoxides, biphenyl-type epoxides, dicyclopentadiene-skeleton-containing epoxides, Naphthalene-skeleton-containing epoxides, arylalkylene-type epoxides, tetraglycidylxylylenediamine, dimer acid-modified epoxides that are dimer acid-modified products of the above-mentioned epoxides, di Polymer acid diglycidyl ester, silane modified epoxy resin, etc. In addition, examples of commercially available epoxy oxides include "jER828", "jER834", and "jER807" manufactured by Mitsubishi Chemical Co., Ltd.; "ST-3000" manufactured by Nippon Steel Chemical Co., Ltd.; "CELLOXIDE 2021P" manufactured by Nippon Steel Chemical Co., Ltd.; "YD-172-X75" manufactured by Nippon Steel Chemical Co., Ltd.; "TETRAD-X" manufactured by Mitsubishi Gas Chemical Co., Ltd., etc. Among them, from the viewpoint of the balance between heat-resistant adhesiveness, moisture-absorbing solder heat resistance, and low dielectric properties, preferred are bisphenol A-type epoxides, bisphenol F-type epoxides, and hydrogenated bisphenol-A-type epoxides. At least one of the group consisting of oxides and alicyclic epoxides.

In particular, tetraglycidyldiamine having the following structure has good compatibility with the aforementioned polyimide. In addition, when this component is used, the loss elastic modulus of the adhesive layer is easily reduced, and the heat-resistant adhesive properties and low dielectric properties are also improved. (In the formula, Y represents a phenylene group or a cyclohexylene group.)

In the case of using an epoxy as a crosslinking agent, various known curing agents for epoxy can be used in combination. The curing agent for epoxy can be used alone or in combination of two or more. The curing agent for epoxy can be exemplified: succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-Methylhexahydrophthalic anhydride, or a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride Formic anhydride, Nadic anhydride, Methyl Nadic anhydride, Norbornane-2,3-dicarboxylic anhydride, Methylnorbornane-2,3-dicarboxylic anhydride, Methylcyclohexene dicarboxylic anhydride, 3- Dodecenyl succinic anhydride, octenyl succinic anhydride and other acid anhydride curing agents; dicyandiamide (DICY), aromatic diamine (trade names "LonzacureM-DEA", "LonzacureM-DETDA", etc. Sand Co., Ltd.), aliphatic amine and other amine curing agents; phenol novolac resin, cresol novolak resin, bisphenol A novolac resin, triazine modified phenol novolak resin, phosphazene containing phenolic hydroxyl group (Trade name "SPH-100" manufactured by Otsuka Chemical Co., Ltd., etc.) and other phenolic curing agents, cyclic phosphazene compounds, rosin-based crosslinking agents such as maleic acid-modified rosin or its hydrogenated product, and the like. Among them, phenolic curing agents are preferred, and phosphazene curing agents containing phenolic hydroxyl groups are particularly preferred. The amount of the curing agent used is not particularly limited, and is preferably about 0.1% by mass to about 120% by mass, more preferably about 10% by mass to about 40% by mass, when the solid content of the above-mentioned adhesive is 100% by mass. %.

In the case of using an epoxy and a curing agent for epoxy in combination as a crosslinking agent, a reaction catalyst may be further used in combination. The reaction catalysts may be used alone or in combination of two or more. The reaction catalyst can be exemplified: 1,8-diaza-bicyclo[5.4.0]undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tri (Dimethylaminomethyl)phenol and other tertiary amines; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole and other imidazoles; Tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine and other organic phosphines; tetraphenyl tetraphenyl borate, 2-ethyl-4-methylimidazole tetra Tetraphenylboron salts such as phenyl borate, N-methylmorpholine tetraphenyl borate, and the like. In addition, the usage-amount of this reaction catalyst is not specifically limited, When the solid content of the said adhesive is 100 mass %, Preferably it is about 0.01 mass % - about 5 mass %.

(benzoxazine) As benzoxazine, 6,6-(1-methylethylene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6,6-( 1-methylethylene)bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine), etc. In addition, a phenyl group, a methyl group, a cyclohexyl group or the like may be bonded to the nitrogen of the oxazine ring. In addition, examples of commercially available benzoxazine include "Benzoxazine F-a type" and "Benzoxazine P-d type" manufactured by Shikoku Chemical Industry Co., Ltd.; "RLV-100" manufactured by Air Water Co., Ltd., etc. .

(bismaleimide) Examples of bismaleimide include 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3 ,3'-Dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bismaleimide Amine, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4,4'-bismaleimide Phenyl bismaleimide, etc. Moreover, "BAF-BMI" by JFE Chemical Co., Ltd. etc. can be illustrated as a commercial item of bismaleimide.

(cyanate) Examples of cyanate esters include 2-allylphenol cyanate, 4-methoxyphenol cyanate, 2,2-bis(4-cyanatophenol)-1,1,1,3,3,3 - Hexafluoropropane, bisphenol A cyanate, diallyl bisphenol A cyanate, 4-phenylphenol cyanate, 1,1,1-tris(4-cyanatophenyl)ethane , 4-cumenylphenol cyanate, 1,1-bis(4-cyanatophenyl)ethane, 4,4'-bisphenol cyanate and 2,2-bis(4-cyanato Phenyl) propane, etc. Moreover, "PRIMASET BTP-6020S (made by Lonza Co., Ltd.)" etc. can be illustrated as a commercial item of cyanate ester.

In the above-mentioned adhesive, the upper limit and the lower limit of the content of the crosslinking agent with respect to 100 parts by mass (solid content conversion) of the above-mentioned polyimide can be exemplified as 900 parts by mass, 800 parts by mass, 700 parts by mass, 600 parts by mass, and 500 parts by mass parts by mass, 400 parts by mass, 300 parts by mass, 200 parts by mass, 100 parts by mass, 50 parts by mass, 20 parts by mass, 10 parts by mass, 5 parts by mass, etc. In one embodiment, the content of the crosslinking agent is preferably from about 5 parts by mass to about 900 parts by mass relative to 100 parts by mass (solid content conversion) of the above-mentioned polyimide.

The upper and lower limits of the content of the crosslinking agent in 100% by mass of the above adhesive can be exemplified as 80% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 20% by mass, and 10% by mass. , 5% by mass, 2% by mass, etc. In one embodiment, the content of the crosslinking agent in 100% by mass of the adhesive is preferably about 2% by mass to about 80% by mass.

＜Organic solvent＞ As the organic solvent, various known organic solvents may be used alone or in combination of two or more. Examples of organic solvents include N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfide, N-methylcaprolactam, triethylene glycol dimethyl ether ( Aprotic polar solvents such as methyltriglyme) and diethylene glycol dimethyl ether (methyldiglyme); alicyclic solvents such as cyclohexanone and methylcyclohexane; alcohols such as methanol, ethanol, propanol, benzyl alcohol, and cresol Solvents; aromatic solvents such as toluene, etc.

In addition, the content of the organic solvent in the adhesive is not particularly limited, and the upper and lower limits of the organic solvent relative to 100% by mass of the solid content of the adhesive can be exemplified by 60% by mass, 50% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, etc. In one embodiment, the solid content of the organic solvent relative to 100% by mass of the adhesive is preferably 10 to 60% by mass.

In the above-mentioned adhesive, the upper limit and the lower limit of the content of the organic solvent relative to 100 parts by mass (solid content conversion) of the above-mentioned polyimide can be exemplified as 900 parts by mass, 800 parts by mass, 700 parts by mass, 600 parts by mass, and 500 parts by mass , 400 parts by mass, 300 parts by mass, 200 parts by mass, 150 parts by mass, etc. In one embodiment, the content of the organic solvent in the adhesive is preferably 150 to 900 parts by mass relative to 100 parts by mass (solid content conversion) of the polyimide.

＜Flame retardant＞ In one embodiment, the above-mentioned adhesive contains a flame retardant. The flame retardants can be used alone or in combination of two or more. As the flame retardant, phosphorus-based flame retardants, inorganic fillers, and the like can be exemplified.

(Phosphorus Flame Retardant (Phosphorus Flame Retardant)) Examples of phosphorus-based flame retardants include polyphosphoric acid, phosphoric acid ester, and phosphazene derivatives that do not contain a phenolic hydroxyl group. Among the phosphazene derivatives, cyclic phosphazene derivatives are preferable from the viewpoint of flame retardancy, heat resistance, bleeding resistance, and the like. Commercially available products of cyclic phosphazene derivatives include SPB-100 manufactured by Otsuka Chemical Co., Ltd., Rabitle FP-300B manufactured by Fushimi Pharmaceutical Co., Ltd., and the like.

(inorganic filler) In one embodiment, examples of inorganic fillers include silica fillers, phosphorus fillers, fluorine fillers, inorganic ion exchanger fillers, and the like. Examples of commercially available products include FB-3SDC manufactured by Denka Co., Ltd., Exolit OP935 manufactured by Clariant Chemicals Co., Ltd., KTL-500F manufactured by Kitamura Co., Ltd., IXE manufactured by Toagosei Co., Ltd., and the like.

The upper limit and the lower limit of the content of the flame retardant in the above adhesive with respect to 100 parts by mass of the polyimide (in terms of solid content) can be exemplified as 150 parts by mass, 100 parts by mass, 50 parts by mass, 10 parts by mass, and 5 parts by mass , 1 part by mass, etc. In one embodiment, the content of the flame retardant in the adhesive is preferably 1 to 150 parts by mass relative to 100 parts by mass (solid content conversion) of the polyimide.

<Reactive alkoxysilane compound> In one embodiment, the above-mentioned adhesive further contains a general formula: Z-Si(R ¹ ) _a (OR ² ) _3-a (wherein, Z represents Reactive functional group group, R ¹ represents hydrogen or a hydrocarbon group with 1 to 8 carbon atoms, R ² represents a hydrocarbon group with 1 to 8 carbon atoms, and a represents 0, 1 or 2.) Reactive alkoxy group represented by Silane compounds. By using the reactive alkoxysilyl compound, it is possible to maintain the low dielectric properties and adjust the melt viscosity of the adhesive layer comprising the adhesive of the present invention. As a result, bleeding of the cured layer from the edge of the substrate can be suppressed while enhancing the interface adhesion between the adhesive layer and the substrate (so-called anchoring effect).

The reactive functional group contained in Z of the said general formula can illustrate an amine group, an epoxy group, a thiol group, etc.

Examples of compounds containing amino groups in Z include N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyl Trimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane and 3-ureidopropyltrialkoxysilane, etc. Examples of compounds where Z contains an epoxy group include 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidyloxypropylmethyldimethoxysilane, 3-glycidyloxycyclohexyl Glyceryloxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane, etc. As a compound containing a thiol group in Z, for example, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyl Methyldiethoxysilane, etc. Among these, compounds in which Z contains an amine group are preferred from the viewpoint of good reactivity and flow control effects.

The upper and lower limits of the content of the reactive alkoxysilyl compound relative to 100 parts by mass (solid content conversion) of the polyimide in the above-mentioned adhesive can be exemplified by 5 parts by mass, 2.5 parts by mass, 1 part by mass, and 0.5 parts by mass parts, 0.1 parts by mass, 0.05 parts by mass, 0.01 parts by mass, etc. In one embodiment, the content of the reactive alkoxysilyl compound in the adhesive is preferably 0.01 to 5 parts by mass relative to 100 parts by mass (solid content conversion) of the polyimide.

The above-mentioned adhesive agent may contain any one of the above-mentioned polyimide, cross-linking agent, organic solvent, flame retardant, and reactive alkoxysilyl compound as an additive.

Examples of additives include ring-opening esterification catalysts, dehydrating agents, plasticizers, weather-resistant agents, antioxidants, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents, release agents, and surface treatments. Agents, viscosity modifiers, silica fillers and fluorine fillers, etc.

In one embodiment, the content of the additive can be, for example, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, or 0 part by mass relative to 100 parts by mass of the adhesive.

In another embodiment, the content of the additive can be, for example, less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, or 0 part by mass relative to 100 parts by mass of the polyimide (solid content conversion).

The above-mentioned adhesive can be obtained by dissolving the above-mentioned polyimide, crosslinking agent, and if necessary, a flame retardant, a reactive alkoxysilyl compound, and additives in an organic solvent.

[Film Adhesive Material] The present invention provides a film-like adhesive material comprising a heat-cured product of the above-mentioned composition and/or a heat-cured product of the above-mentioned adhesive. The method for producing a film-like adhesive can be exemplified by a method including a step of applying the above-mentioned adhesive to a suitable support, a step of volatilizing and curing an organic solvent by heating, and a step of peeling off the support. The thickness of the adhesive material is not particularly limited, and is preferably about 3 μm to about 40 μm. As a support body, the following material etc. can be illustrated.

[adhesive layer] The present invention provides an adhesive layer comprising one or more selected from the group consisting of the above-mentioned composition, the above-mentioned adhesive, and the above-mentioned film-like adhesive material. When producing the above-mentioned adhesive layer, the above-mentioned adhesive can be used in combination with various known adhesives other than the above-mentioned adhesive. Similarly, the above-mentioned film-form adhesive may be used in combination with various known film-form adhesives other than the above-mentioned film-form adhesive.

[adhesive sheet] The present invention provides an adhesive sheet, which comprises the above adhesive layer and a supporting film.

As the support film, a plastic film can be exemplified. Examples of plastics include polyester, polyimide, polyimide-silicon dioxide hybrid, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polymethyl Methyl acrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin; composed of ethylene terephthalate, phenol, phthalic acid, hydroxynaphthoic acid, etc. and p-hydroxy Aromatic polyester resins obtained from benzoic acid (so-called liquid crystal polymers; "Vecstar" manufactured by Kuraray Co., Ltd., etc.) and the like.

In addition, when the above-mentioned adhesive is applied to the support film, the above-mentioned coating means can be used. The thickness of the coating is also not particularly limited, and the thickness after drying is preferably about 1 μm to about 100 μm, more preferably about 3 μm to about 50 μm. In addition, the adhesive layer of the adhesive sheet can be protected with various protective films.

[Copper foil with resin] The present invention provides a resin-attached copper foil, which includes the above-mentioned adhesive layer and copper foil. Specifically, the resin-coated copper foil is a material obtained by applying or bonding the adhesive or the film-like adhesive material to copper foil. Examples of this copper foil include rolled copper foil and electrolytic copper foil. The thickness is not particularly limited, but is preferably about 1 μm to about 100 μm, more preferably about 2 μm to about 38 μm. In addition, this copper foil may be copper foil subjected to various surface treatments (roughening, rust prevention, etc.). The antirust treatment may, for example, be a plating treatment using a plating solution containing Ni, Zn, Sn, or the like, or a so-called mirror treatment such as chromate treatment. Moreover, as a coating means, the method mentioned above can be illustrated.

In addition, the adhesive layer of the resin-coated copper foil may be an uncured adhesive layer, or may be an adhesive layer that is partially cured or fully cured under heating. A partially cured adhesive layer is in what is called a so-called B-staged state. In addition, the thickness of the adhesive layer is not particularly limited, but is preferably about 0.5 μm to about 30 μm. Moreover, resin may be bonded further to the copper foil of this resin-coated copper foil, and it may be set as the copper foil with resin coated on both surfaces.

[Copper Clad Laminate Board] The present invention provides a copper-clad laminate comprising: the adhesive sheet and/or the resin-coated copper foil; and at least one selected from the group consisting of copper foil, an insulating sheet, and a supporting film. Copper Clad Laminate is also called CCL (Copper Clad Laminate). In one embodiment, the copper-clad laminate is a material obtained by laminating various known copper foils on one or both sides of the above-mentioned adhesive sheet, or bonding the above-mentioned resin-coated copper foil under heat to pressure bonding selected from various types. A material obtained on one or more sides of a group consisting of known copper foils, insulating sheets, and support films. In the case of bonding to one side, a material different from the resin-coated copper foil described above can be crimped on the other side. In addition, the number of resin-coated copper foils and insulating sheets in the copper-clad laminate is not particularly limited.

In one embodiment, the insulating sheet is preferably a prepreg. Prepreg refers to a sheet-like material (JIS C 5603) obtained by impregnating a resin into a reinforcing material such as glass cloth and curing it to the B stage. As the resin, insulating resins such as polyimide resins, phenol resins, epoxy resins, polyester resins, liquid crystal polymers, and aramid resins can be used. The thickness of the prepreg is not particularly limited, but is preferably about 20 μm to about 500 μm. The heating and pressure-bonding conditions are not particularly limited, and may be set to conditions of 300° C. or higher. The heating and pressure bonding conditions are preferably about 150°C to about 280°C (more preferably about 170°C to about 240°C), and preferably about 0.5MPa to about 20MPa (more preferably about 1MPa to about 8MPa).

The present invention also provides a copper-clad laminate having a copper-plated layer on the above-mentioned adhesive sheet or the above-mentioned resin-coated copper foil.

In one embodiment, the above-mentioned copper plating layer is preferably an electroless copper plating layer or a vacuum copper plating layer.

Electroless copper plating can be performed using various known electroless copper plating solutions.

The electroless copper plating solution may contain a reducing agent. One kind of reducing agent may be used alone, or two or more kinds may be used in combination. Examples of reducing agents include sodium phosphinate, dimethylamine borane, formalin, glyoxylic acid, tetrahydroboric acid, hydrazine, and sodium hypophosphite. When the electroless copper plating solution contains a reducing agent, its content is preferably about 0.1 g/L~about 100 g/L, more preferably about 1 g/L~about 30 g/L.

The electroless copper plating solution may contain complexing agents. A complexing agent may be used alone or in combination of two or more. Examples of complexing agents include citric acid, tartaric acid, malic acid, lactic acid, gluconic acid, or alkali metal salts thereof (such as Rochelle salts, etc.), carboxylic acids (salts) such as ammonium salts, and amino acids such as glycine. , amines such as ethylenediamine and alkylamine, other ammonium, ethylenediaminetetraacetic acid (EDTA), pyrophosphate (salt), etc. In the case that the electroless copper plating solution contains a complexing agent, its content is preferably about 1 g/L to about 100 g/L, more preferably about 10 g/L to about 100 g/L.

The liquid temperature when performing electroless copper plating is preferably about 0°C or higher, more preferably about 20°C to about 80°C.

Electroless copper plating can be repeated two or more times as needed.

As vacuum copper plating, copper sputtering etc. can be illustrated.

Copper sputtering can be performed using various known sputtering devices.

In one embodiment, the input power to the sputtering electrode is preferably 10 kW or more, more preferably 30 kW or more. In one embodiment, it is preferable to set the pressure in the chamber during sputtering to about 0.5 Pa to about 5 Pa.

Vacuum copper plating can be repeated more than 2 times as needed.

[Printed Circuit Board] The present invention provides a printed wiring board having a circuit pattern on the copper foil surface of the above-mentioned copper-clad laminate. Examples of the patterning means for forming a circuit pattern on the copper foil surface of a copper-clad laminate include a subtractive method and a semi-additive method. An example of the semi-additive method is a method of patterning the copper foil surface of a copper-clad laminate with a resist film, performing electrolytic copper plating, removing the resist, and etching with an alkaline solution. In addition, the thickness of the circuit pattern layer in this printed wiring board is not specifically limited. Alternatively, a multilayer board can be obtained by using the printed wiring board as a core base material and laminating the same printed wiring board or other known printed wiring boards or printed wiring boards thereon. When laminating, the above-mentioned adhesive and other known adhesives other than the above-mentioned adhesive may be used in combination. In addition, the number of laminated layers in the multilayer substrate is not particularly limited. In addition, it is possible to insert through-holes and perform plating treatment on the inside every time a layer is built up. The line width/space ratio of the circuit pattern is not particularly limited, but is generally about 1 μm/1 μm to about 100 μm/100 μm. In addition, the height of the above-mentioned circuit pattern is not particularly limited, but is usually about 1 μm to about 50 μm.

[Multilayer circuit board] The invention provides a multilayer circuit board, which comprises: a printed circuit board (1) or a printed circuit board (1); the above-mentioned adhesive layer; and a printed circuit board (2) or a printed circuit board (2). The above-mentioned printed wiring boards (1) to (2) may be the above-mentioned printed wiring boards, or may be various known printed wiring boards. Likewise, the printed circuit boards (1) to (2) may be the above-mentioned printed circuit boards, or may be various known printed circuit boards. In addition, the printed wiring board (1) and the printed wiring board (2) may be the same or different. Likewise, the printed circuit board (1) and the printed circuit board (2) can also be the same or different.

[Manufacturing method of multilayer circuit board] The present invention provides a kind of manufacturing method of multilayer circuit board, it comprises following steps 1 and 2: Step 1: Manufactured by bringing one or more selected from the group consisting of the above-mentioned adhesive, the above-mentioned film-like adhesive material, and the above-mentioned adhesive sheet into contact with the printed wiring board (1) or at least one side of the printed wiring board (1) the step of attaching the substrate with the adhesive layer; Step 2: A step of laminating a printed wiring board (2) or a printed circuit board (2) on the adhesive layer-attached substrate and crimping under heat and pressure.

The above-mentioned printed wiring boards (1) to (2) may be the above-mentioned printed wiring boards, or may be various known printed wiring boards. Likewise, the printed circuit boards (1) to (2) may be the above-mentioned printed circuit boards, or may be various known printed circuit boards.

In step 1, the means for bringing the above-mentioned adhesive or film-like adhesive into contact with the adherend is not particularly limited, and various known coating means can be exemplified, such as curtain coater, roll coater, laminator, press machine, and the like.

The heating temperature and crimping time in step 2 are not particularly limited, (i) After bringing the adhesive or film-like adhesive material of the present invention into contact with at least one side of the core substrate, heat to about 70°C to about 200°C, and use The curing reaction is carried out for about 1 minute to about 10 minutes, and then (ii) in order to advance the curing reaction of the crosslinking agent, it is preferable to further perform a heat treatment at about 150° C. to about 300° C. for about 10 minutes to about 3 hours. . In addition, the pressure is not particularly limited, but it is preferably about 0.5 MPa to about 20 MPa, more preferably about 1 MPa to about 8 MPa during the entire period of steps (i) and (ii). [Example]

Hereinafter, the present invention will be specifically described by way of examples and comparative examples. However, the description in the above-mentioned preferred embodiment and the following examples are provided for the purpose of illustration only, and are not provided for the purpose of limiting the present invention. Therefore, the scope of the present invention is not limited to the embodiments and examples specifically described in this specification, but is limited only by the claims. In addition, in each Example and a comparative example, unless otherwise stated, the numerical value of a part, %, etc. is a mass basis.

Production Example 1 Production of polyimide Put 4,4'-[propane-2,2-diylbis(1,4-phenyleneoxy)]bisphthalic acid into the reaction vessel equipped with mixer, water separator, thermometer and nitrogen inlet pipe Dianhydride (trade name "BisDA-1000", manufactured by SABIC Innovative Plastic Co., Ltd. Japan. Hereinafter abbreviated as BisDA.) 350.00g, cyclohexanone 993.30g and methylcyclohexane 198.66g, heated to 60°C. Next, 89.85 g of 4,4'-diaminodiphenyl ether (trade name "ODA", manufactured by JFE Chemical Co., Ltd., hereinafter abbreviated as ODA) and commercially available dimer diamine (trade name "PRIAMINE1075", manufactured by CRODA Japan Co., Ltd.) 103.85 g, and then imidization reaction was carried out at 140° C. for 12 hours to obtain a solution of polyimide (1-1) (non-volatile content 32.9% ). In addition, the molar ratio of the acid component/amine component of this polyimide was 1.05, and the softening point was 180 degreeC.

Example 1-1: A composition was produced by mixing 10.0 g of the polyimide of Production Example 1 and 0.07 g of Takenate D-110N (manufactured by Mitsui Chemicals Co., Ltd.).

Examples and comparative examples other than Example 1-1 were produced in the same manner as in Example 1-1 except that the components were changed as shown in the following table.

[Table 1] polyimide Example 1-1 Production Example 1 10.0g TAKENATE D-110N 0.07g Example 1-2 Production Example 1 10.0g TAKENATE D-131N 0.07g Example 1-3 Production Example 1 10.0g TAKENATE D-204EA-1 0.10g Example 1-4 Production Example 1 10.0g P1071 0.12g Example 1-5 Production Example 1 10.0g P1071 0.05g Examples 1-6 Production Example 1 10.0g TAKENATE D-110N 0.15g Example 1-7 Production Example 1 10.0g VESTANAT T1890/100 0.05g Comparative example 1-1 Production Example 1 10.0g — TAKENATE D-110N: Trimethylolpropane adduct product of xylene diisocyanate (manufactured by Mitsui Chemicals Co., Ltd.) TAKENATE D-131N: Isocyanurate body of xylene diisocyanate (manufactured by Mitsui Chemicals Co., Ltd.) TAKENATE D-204EA-1: Isocyanurate body of toluene diisocyanate (manufactured by Mitsui Chemicals Co., Ltd.) P1071: PRIAMINE1071, trimer triamine/dimer diamine mass ratio=20/80 (CRODA Japan stock Co., Ltd.) VESTANAT T1890/100: Isocyanurate form of isophorone diisocyanate (manufactured by Evonik)

Example 2 ＜Preparation of adhesive sheet＞ The composition of Example 1 and Comparative Example 1 was coated on a polyimide film (trade name "Kapton 100EN", manufactured by Toray DuPont Co., Ltd.) with a gap coater so that the thickness after drying was 10 μm, Then, it was dried at 200° C. for 3 minutes, thereby obtaining an adhesive sheet.

＜Production of copper-clad laminates (1) using copper foil＞ The adhesive surface of the obtained adhesive sheet was laminated on the low-roughness side of a commercially available rolled copper foil (trade name "BHM-102F-HA-V2", manufactured by JX Metal Co., Ltd., 12 μm thick) to produce a resin-coated copper foil.

Next, the obtained resin-attached copper foil was placed on a support for pressing, and heated and pressed at a pressure of 2 MPa and 180 to 300° C. for 10 minutes through a support obtained from the same raw material from above. This makes copper clad laminates.

1. Adhesion test About the obtained copper-clad laminated board, peeling strength (N/mm) was measured at room temperature based on JIS C 6481 (copper-clad laminated board test method for flexible printed wiring boards).

2. Determination of dielectric constant and dielectric loss tangent ＜Preparation of resin for measurement and cured product sample＞ The compositions of Examples and Comparative Examples were coated on release paper (trade name "WH52-P25CM", manufactured by Sun A Kaken Co., Ltd.) so that the film thickness after curing was 10 μm, and dried at 200°C for 3 minute. Peeling, so that the film thickness after pressing is about 300 μm film thickness, heating and pressing under the conditions of pressure 1.5 MPa, 250° C., and 10 minutes to cure, thereby obtaining a resin for measuring dielectric constant with a film thickness of about 300 μm and cured samples.

Next, with respect to the resin and cured product samples, the dielectric constant and dielectric loss tangent at 10 GHz were measured using a commercially available dielectric constant measuring device (cavity resonator type, manufactured by AET) based on JIS C2565.

3. Solder heat resistance test (with pre-drying) After curing, the copper-clad laminate (1) using the above-mentioned copper foil was floated in a solder bath at 288°C for 30 seconds with the copper foil side down, and pre-dried at 120°C for 5 minutes. Check for changes in appearance. The case where there was no change was marked as ◯, and the case where foaming and swelling occurred was marked as ×.

[Table 2] Peel strength of copper clad laminate (1) (N/mm) Solder heat resistance of copper clad laminates (1) (with pre-drying) Dielectric constant (Dk) Dielectric loss tangent (Df) Example 2-1 1.07 ○ 2.19 0.00223 Example 2-2 1.02 ○ 2.29 0.00214 Example 2-3 1.00 ○ 2.52 0.00246 Example 2-4 0.99 ○ 2.20 0.00218 Example 2-5 1.09 ○ 2.27 0.00149 Example 2-6 1.09 ○ 2.23 0.00205 Example 2-7 1.01 ○ 2.43 0.00157 Comparative example 2-1 0.89 x 2.30 0.00216

Evaluation manufacturing example 1 In the evaluation manufacturing example and comparative evaluation manufacturing example, it manufactured similarly to Example 1-1 except having changed the component as shown in the following table|surface. [table 3] polyimide Evaluation Manufacturing Example A Production Example 1 4.6g P1071 0.04g Evaluation Manufacturing Example B Production Example 1 7.0g TAKENATE D-131N 0.49g Comparative Evaluation Manufacturing Example A Production Example 1 1.48g —

＜Production of copper-clad laminates (2) by electroless copper plating＞ The adhesive sheet obtained by the method similar to Example 2 using the composition of the evaluation production example was electroless copper-plated by the following procedure, and the copper-clad laminated board was produced. (1) Degreasing: 60°C, 2 minutes (CLEANER 160, manufactured by Meltex Co., Ltd.) (2) Pre-dipping: 20°C, 2 minutes (3) Electroless copper plating: 50°C, 10 minutes (copper sulfate 0.04mol/L, EDTA 0.25mol/L, formalin 0.13mol/L, triphenylphosphine 2ppm) (4) Washing: 20°C, 2 minutes (5) After drying, the thickness of the copper-plated part after drying is 5 μm

<Preparation of copper-clad laminate (3) by vacuum copper plating (sputtering)> The composition of the evaluation production example was applied to a commercially available electrolytic copper foil ( Product name "F2-WS", manufactured by Furukawa Circuit Foil Co., Ltd., 18 μm thick), and then dried at 180° C. for 2 hours to obtain a resin-attached copper foil. This resin-coated copper foil was subjected to vacuum copper plating (sputtering) in the following procedure to produce a copper-clad laminate. (1) Plasma treatment: evacuate until the pressure in the vacuum device reaches below 1×10 ^-4 Pa, then introduce argon gas to make the pressure in the device 0.3 Pa, and perform plasma treatment. (2) Sputtering: performed using UHSP-OP2060 (manufactured by Shimadzu Corporation). (3) Copper electroplating: Copper electroplating was performed at a current density of 2A/dm ² (plating solution: copper sulfate solution).

Evaluation example 1: Adhesion test The peel strength (N/mm) was measured at room temperature based on JIS C 6481 (copper-clad laminate test method for flexible printed wiring boards) about the obtained copper-clad laminated board. [Table 4] Peel strength of copper clad laminate (2) (N/mm) Peel strength of copper clad laminate (3) (N/mm) Evaluation Manufacturing Example A 0.40 0.5 Evaluation Manufacturing Example B — 0.72 Comparative Evaluation Manufacturing Example A 0.04

Evaluation manufacturing example 2 In the production example for evaluation and the production example for comparative evaluation, it produced similarly to Example 1-1 except having changed the component as shown in the following table|surface.

[table 5] polyimide Evaluation Manufacturing Example 2-1 Production Example 1 10.5g TAKENATE D-204EA-1 0.36g Evaluation manufacturing example 2-2 Production Example 1 10.0g COMPOCERAN E103D 0.61g Evaluation Manufacturing Example 2-3 Production Example 1 9.5g COMPOCERAN E103D 0.67g P1071 0.14g Evaluation Manufacturing Example 2-4 Production Example 1 10.0g Coronate HXR 0.05g Evaluation Manufacturing Examples 2-5 Production Example 1 10.0g Coronate HXR 0.08g Comparative Evaluation Manufacturing Example 2-1 Production Example 1 1.48g — TAKENATE D-204EA-1: Isocyanurate form of toluene diisocyanate (manufactured by Mitsui Chemicals Co., Ltd.) COMPOCERAN E103D: Silane-modified epoxy resin (manufactured by Arakawa Chemical Co., Ltd.) Coronate HXR: Hexamethylene Isocyanurate body of diisocyanate (manufactured by Tosoh Co., Ltd.)

Evaluation example 2 The composition of Evaluation Production Examples 2-1 to 2-5 and Comparative Evaluation Production Example 2-1 was applied to a commercially available electrodeposited copper foil (trade name "F2- WS", manufactured by Furukawa Circuit Foil Co., Ltd., 18 μm thick), and then dried at 150° C. for 5 minutes and then at 180° C. for 120 minutes to obtain a resin-coated copper foil.

Blocking test The resin surface of the obtained resin-attached copper foil and the resin surface of another obtained resin-attached copper foil are brought into contact with each other under the conditions of pressure 2.5MPa, 180°C and 90 seconds Hot pressing is performed to produce a copper-clad laminate. A sample whose surface was easily peeled after pressing was marked as ◯, and a sample whose surface was not peeled after pressing was marked as x. [Table 6] Adhesion evaluation Evaluation Manufacturing Example 2-1 ○ Evaluation manufacturing example 2-2 ○ Evaluation Manufacturing Example 2-3 ○ Comparative Evaluation Manufacturing Example 2-1 x

Solder heat resistance test (without pre-drying) After curing, the copper-clad laminate was floated in a solder bath at 288° C. for 30 seconds with the copper foil side down without pre-drying, and the presence or absence of changes in appearance was checked. The case where there was no change was marked as ◯, and the case where foaming and swelling occurred was marked as ×. [Table 7] Solder heat resistance (without pre-drying) Evaluation Manufacturing Example 2-4 ○ Evaluation Manufacturing Examples 2-5 ○ Comparative Evaluation Manufacturing Example 2-1 x

Domestic deposit information (please note in order of depositor, date, and number) none Overseas storage information (please note in order of storage country, institution, date, and number) none

Claims (13)

A composition comprising: a polyimide which is a reactant of a monomer group comprising an aromatic tetracarboxylic anhydride and a dimer diamine; and a polyisocyanate and a trimer triamine More than one of the group consisting of amines; the aforementioned polyisocyanate is more than one selected from the group consisting of structural formulas 1, 2, 3, 4 and 5; in the case of including the aforementioned trimer triamine, The mass ratio (the aforementioned polyimide/the aforementioned trimer triamine) is 100 to 400;

In structural formula 1, n ^b is an integer greater than 1, R ^bA ~ R ^bE are each independently an alkylene group, an arylylene group or a group formed by a combination of an alkylene group and an arylylene group, and R ^bα ~ R ^bβ are each independently are independently isocyanate groups or

n ^b1 is an integer greater than or equal to 0, R ^b1 ~ R ^b5 are each independently an alkylene group, an arylylene group or a group formed by a combination of an alkylene group and an arylylene group, and R ^b ' ~ R ^b " are each independently The isocyanate group or the group of R ^bα ~ R ^bβ itself, the groups of R ^b4 ~ R ^b5 , R ^b ” can be different in each constituent unit, and the groups of R ^bD ~ R ^bE , R ^bβ can be different in each constituent unit;

In structural formula 2, n ⁱ is an integer greater than 0, R ^iA ~ R ^iE are each independently an alkylene group, an arylylene group or a group formed by a combination of an alkylene group and an arylylene group, and R ^iα ~ R ^iβ are each independently are independently isocyanate groups or

n ⁱ¹ is an integer of 0 or more, R ⁱ¹ ~R ⁱ⁵ are each independently an alkylene group, an arylylene group or a group formed by a combination of an alkylene group and an arylylene group, and R ⁱ '~R ⁱ "are each independently The isocyanate group or the group of R ^iα ~R ^iβ itself, the groups of R ⁱ⁵ and R ⁱ ” can be different in each constituent unit, and the groups of R ^iD ~R ^iE , R ^iβ can be different in each constituent unit;

In structural formula 3, n ^a is an integer greater than 0, R ^aA is an alkyl group or an aryl group, and R ^aB ~ R ^aG are each independently an alkylene group, an arylylene group, or a combination of an alkylene group and an arylylene group. group, R ^aα ~ R ^aγ are each independently isocyanate group or

n ^a1 is an integer of 0 or more, R ^a1 ~R ^a6 are each independently an alkylene group or an arylylene group, and R ^a '~R ^a ''' are each independently an isocyanate group or a group of R ^aα ~R ^aγ itself , R ^a1 ~R ^a4 , R ^a '~R ^a ''' may have different groups in each constituent unit, R ^aB ~R ^aE , R ^aα ~R ^aγ may have different groups in each constituent unit; according to the structural formula The adduct of trimethylolpropane and polyisocyanate represented by 4,

In the formula, n ^ad is an integer of 0 or more, R ^adA ~ R ^adE are each independently an alkylene group, an arylylene group or a group formed by a combination of an alkylene group and an arylylene group, and R ^ad1 ~ R ^ad2 are each independently for

In the formula, n ^ad ' is an integer of 0 or more, R ^ad '~R ^ad " are each independently an alkylene group, an arylylene group or a group formed by a combination of an alkylene group and an arylylene group, and R ^ad ''' It is the group of R ^ad1 ~R ^ad2 itself, R ^ad '~R ^ad ''' can be different in each constituent unit, and R ^adD ~R ^adE , ^Rad2 can be different in each constituent unit;

In the formula, n ^ad1 is an integer of 0 or more, R ^adα ~ R ^adε are each independently an alkylene group or an arylylene group, and R ^adA ~ R ^adB are each independently

In the formula, n ^ad1 ' is an integer of 0 or more, R ^adδ '~R ^adε ' are each independently an alkylene group, an arylylene group or a group formed by a combination of an alkylene group and an arylylene group, and R ^adB ' is R The groups of ^adA ~R ^adB itself, R ^adδ '~R ^adε ', R ^adB ' may be different in each constituent unit, and R ^adδ ~R ^adε may be different in each constituent unit. A reactant, which is polyimide and more than one reactant selected from the group consisting of polyisocyanate and trimer triamine, said polyimide containing aromatic tetracarboxylic anhydride and dimer A reactant of a monomer group of a diamine, wherein the aforementioned polyisocyanate is one or more selected from the group consisting of structural formulas 1, 2, 3, 4 and 5; in the case of comprising the aforementioned trimer triamine Below, the mass ratio (aforesaid polyimide/aforementioned terpolymer triamine) is 100～400;

In structural formula 1, n ^b is an integer greater than 1, R ^bA ~ R ^bE are each independently an alkylene group, an arylylene group or a group formed by a combination of an alkylene group and an arylylene group, and R ^bα ~ R ^bβ are each independently are independently isocyanate groups or

n ^b1 is an integer greater than or equal to 0, R ^b1 ~ R ^b5 are each independently an alkylene group, an arylylene group or a group formed by a combination of an alkylene group and an arylylene group, and R ^b ' ~ R ^b " are each independently The isocyanate group or the group of R ^bα ~ R ^bβ itself, the groups of R ^b4 ~ R ^b5 , R ^b ” can be different in each constituent unit, and the groups of R ^bD ~ R ^bE , R ^bβ can be different in each constituent unit;

In structural formula 2, n ⁱ is an integer greater than 0, R ^iA ~ R ^iE are each independently an alkylene group, an arylylene group or a group formed by a combination of an alkylene group and an arylylene group, and R ^iα ~ R ^iβ are each independently are independently isocyanate groups or

n ⁱ¹ is an integer of 0 or more, R ⁱ¹ ~R ⁱ⁵ are each independently an alkylene group, an arylylene group or a group formed by a combination of an alkylene group and an arylylene group, and R ⁱ '~R ⁱ "are each independently The isocyanate group or the group of R ^iα ~R ^iβ itself, the groups of R ⁱ⁵ and R ⁱ ” can be different in each constituent unit, and the groups of R ^iD ~R ^iE , R ^iβ can be different in each constituent unit;

In structural formula 3, n ^a is an integer greater than 0, R ^aA is an alkyl group or an aryl group, and R ^aB ~ R ^aG are each independently an alkylene group, an arylylene group, or a combination of an alkylene group and an arylylene group. group, R ^aα ~ R ^aγ are each independently isocyanate group or

n ^a1 is an integer of 0 or more, R ^a1 ~R ^a6 are each independently an alkylene group or an arylylene group, and R ^a '~R ^a ''' are each independently an isocyanate group or a group of R ^aα ~R ^aγ itself , R ^a1 ~R ^a4 , R ^a '~R ^a ''' may have different groups in each constituent unit, R ^aB ~R ^aE , R ^aα ~R ^aγ may have different groups in each constituent unit; according to the structural formula The adduct of trimethylolpropane and polyisocyanate represented by 4,

In the formula, n ^ad is an integer of 0 or more, R ^adA ~ R ^adE are each independently an alkylene group, an arylylene group or a group formed by a combination of an alkylene group and an arylylene group, and R ^ad1 ~ R ^ad2 are each independently for

In the formula, n ^ad ' is an integer of 0 or more, R ^ad '~R ^ad " are each independently an alkylene group, an arylylene group or a group formed by a combination of an alkylene group and an arylylene group, and R ^ad ''' It is the group of R ^ad1 ~R ^ad2 itself, R ^ad '~R ^ad ''' can be different in each constituent unit, and R ^adD ~R ^adE , ^Rad2 can be different in each constituent unit;

In the formula, n ^ad1 is an integer of 0 or more, R ^adα ~ R ^adε are each independently an alkylene group or an arylylene group, and R ^adA ~ R ^adB are each independently

In the formula, n ^ad1 ' is an integer of 0 or more, R ^adδ '~R ^adε ' are each independently an alkylene group, an arylylene group or a group formed by a combination of an alkylene group and an arylylene group, and R ^adB ' is R The groups of ^adA ~R ^adB itself, R ^adδ '~R ^adε ', R ^adB ' may be different in each constituent unit, and R ^adδ ~R ^adε may be different in each constituent unit. An adhesive comprising the composition described in claim 1, a crosslinking agent and an organic solvent. A film-like adhesive material comprising a heat-cured product of the composition described in Claim 1 and/or a heat-cured product of the adhesive described in Claim 3. An adhesive layer comprising at least one selected from the group consisting of the composition described in Claim 1, the adhesive described in Claim 3, and the film-like adhesive material described in Claim 4. An adhesive sheet comprising the adhesive layer described in claim 5 and a supporting film. A resin-attached copper foil, which comprises the adhesive layer described in claim 5 and copper foil. A copper-clad laminate comprising: the adhesive sheet described in claim 6 and/or the resin-attached copper foil described in claim 7; and, selected from the group consisting of copper foil, an insulating sheet, and a support film More than one of the group. A copper-clad laminate having a copper-plated layer on the adhesive sheet according to claim 6 or the resin-coated copper foil according to claim 7 . The copper-clad laminate according to claim 9, wherein the copper plating layer is an electroless copper plating layer or a vacuum copper plating layer. A printed circuit board having a circuit pattern on the copper foil surface of the copper-clad laminate described in Claim 8. A multilayer circuit board, comprising: a printed circuit board (1) or a printed circuit board (1); the adhesive layer described in claim 5; and a printed circuit board (2) or a printed circuit board (2). A method for manufacturing a multilayer circuit board, which includes the following steps 1 and 2: Step 1: by making the adhesive selected from the adhesive described in claim 3, the film-like adhesive material described in claim 4, and the adhesive described in claim 6 The step of manufacturing a base material with an adhesive layer by contacting at least one side of the printed circuit board (1) or at least one side of the printed circuit board (1) in the group consisting of adhesive sheets; step 2: on the attached A step of laminating a printed wiring board (2) or a printed circuit board (2) on a layered base material and performing crimping under heat and pressure.