JP2020196876A - Composition, reactant, adhesive, film-like adhesive, adhesive layer, adhesive sheet, copper foil with resin, copper-clad laminate, printed wiring board, and multilayer wiring board and method for producing the same - Google Patents

Abstract

To provide a composition that has low dielectric constants and low dielectric loss tangents, and has excellent solder heat resistance when pre-dried, and provide a reactant, an adhesive, a film-like adhesive, an adhesive layer, an adhesive sheet, a copper foil with a resin, a copper-clad laminate, a printed wiring board, and a multilayer wiring board and a method of producing the same.SOLUTION: A composition contains a polyimide that is a reactant between an aromatic tetracarboxylic acid anhydride and a monomer group containing a dimer diamine, and at least one selected from the group consisting of polyisocyanate, trimer-triamine, and silane-modified epoxy resin.SELECTED DRAWING: None

Description

The present disclosure relates to compositions, reactants, adhesives, film-like adhesives, adhesive layers, adhesive sheets, copper foils with resins, copper-clad laminates, printed wiring boards, and multilayer wiring boards and methods for manufacturing them.

Various known resins are used to manufacture mobile communication devices such as mobile phones and smartphones, their base station devices, network-related electronic devices such as servers and routers, and printed wiring boards included in large computers. ..

In recent years, in the above network-related electronic devices, it is necessary to transmit and process a large amount of information with low loss and high speed, and the electric signals handled by the printed wiring boards of these products are also becoming higher in frequency. Since high-frequency electric signals are easily attenuated, it is necessary to further reduce the transmission loss in the printed wiring board. Therefore, the composition used in manufacturing a printed wiring board is required to have a low dielectric constant and a low dielectric loss tangent (also referred to as low dielectric property).

Further, the composition used in manufacturing the printed wiring board is also required to have good solder heat resistance when pre-dried.

An object 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.

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

The disclosure provides the following items:
(Item 1)
A composition comprising one or more selected from the group consisting of a polyimide, which is a reaction product of a group of monomers containing an aromatic tetracarboxylic dianhydride and a dimer diamine, and a polyisocyanate, a trimertriamine, and a silane-modified epoxy resin.
(Item 2)
A reaction product of polyimide which is a reaction product of a monomer group containing an aromatic tetracarboxylic dianhydride and a dimer diamine and one or more selected from the group consisting of polyisocyanate, trimertriamine, and a silane-modified epoxy resin.
(Item 3)
An adhesive containing the composition, cross-linking agent and organic solvent according to the above item.
(Item 4)
A film-like adhesive comprising a heat-cured product of the composition according to the above item and / or a heat-cured product of the adhesive according to the above item.
(Item 5)
An adhesive layer comprising one or more selected from the group consisting of the composition according to the above item, the adhesive according to the above item, and the film-like adhesive according to the above item.
(Item 6)
An adhesive sheet comprising the adhesive layer and support film according to the above item.
(Item 7)
A copper foil with a resin, which comprises the adhesive layer and the copper foil described in the above items.
(Item 8)
A copper-clad laminate comprising one or more selected from the group consisting of the adhesive sheet according to the above item and / or the copper foil with resin according to the above item and the copper foil, an insulating sheet and a support film.
(Item 9)
A copper-clad laminate having a copper plating layer on the adhesive sheet according to the above item or the copper foil with resin according to the above item.
(Item 10)
The copper-clad laminate according to 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 according to the above item.
(Item 12)
Printed wiring board (1) or printed circuit board (1),
Including the adhesive layer according to the above item and a printed wiring board (2) or a printed circuit board (2).
Multi-layer wiring board.
(Item 13)
A method for manufacturing a multilayer wiring board including the following steps 1 and 2.
Step 1: One or more selected from the group consisting of the adhesive according to the above item, the film-like adhesive according to the above item, and the adhesive sheet according to the above item.
Process of manufacturing a base material with an adhesive layer by contacting at least one side of a printed wiring board (1) or a printed circuit board (1) Step 2: A printed wiring board (2) is placed on the base material with an adhesive layer. Alternatively, a process of laminating printed circuit boards (2) and crimping them under heating and pressure.

In the present disclosure, the above-mentioned one or more features may be provided in addition to the specified combinations.

The composition of the present invention has a low dielectric constant and a low dielectric loss tangent, and has good high-temperature heat resistance and good solder heat resistance when pre-dried. Therefore, the composition of the present invention can be used as a thermoplastic polyimide composition.

Throughout the present disclosure, the range of numerical values such as each physical property value and content can be set as appropriate (for example, by selecting from the upper and lower limit values described in the following items). Specifically, for the numerical value α, when A1, A2, A3, A4 (A1> A2> A3> A4) and the like are exemplified as the upper and lower limits of the numerical value α, the range of the numerical value α is A1 or less. Examples thereof include A2 or less, A3 or less, A2 or more, A3 or more, A4 or more, A1 to A2, A1 to A3, A1 to A4, A2 to A3, A2 to A4, and A3 to A4.

[Composition]
The present disclosure includes one or more selected from the group consisting of an aromatic tetracarboxylic acid anhydride, a polyimide which is a reaction product of a monomer group containing a dimer diamine, and a polyisocyanate, a trimertriamine, and a silane-modified epoxy resin. , The composition is provided.

<Polyimide>
The polyimide is a reaction product of a group of monomers containing an acid anhydride containing an aromatic tetracarboxylic dianhydride and the like and a diamine and the like such as a dimer diamine. The polyimide may be used alone or in combination of two or more.

<Aromatic tetracarboxylic dianhydride>
Aromatic tetracarboxylic dianhydrides can be used alone or in combination of two or more. Examples of the aromatic tetracarboxylic dianhydride include symmetric aromatic tetracarboxylic dianhydride.

(Symmetric aromatic tetracarboxylic dianhydride)
In the present disclosure, "symmetrical aromatic tetracarboxylic dianhydride" means an aromatic tetracarboxylic dianhydride having an axis of symmetry (for example, C2 axis of symmetry) in the molecule. The symmetric aromatic tetracarboxylic dianhydride has the following general formula.
(Wherein, X represents a single _{bond, -SO 2 -, - CO -} , - O -, - O-C 6 H 4 -C (CH 3) 2 -C 6 H 4 -O -, - COO- (CH ₂ ) _p- OCO- or -COO-H ₂ C-HC (-O-C (= O) -CH ₃ ) -CH _2- OCO-, p represents an integer of 1 to 20)
The ones shown in are exemplified.

The symmetric aromatic tetracarboxylic dianhydride represented by the above general formula is 3,3', 4,4'-biphenyltetracarboxylic dianhydride and 3,3', 4,4'-diphenylsulfonetetracarboxylic dianhydride. Anhydride, 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, 3,3', 4,4'-diphenylethertetracarboxylic dianhydride, 4,4'-[propane-2,2 -Diyl bis (1,4-phenyleneoxy)] diphthalic dianhydride, 2,2-bis (3,3', 4,4'-tetracarboxyphenyl) tetrafluoropropanedianhydride, 2,2-bis ( 3,4-dicarboxyphenyl) propane dianhydride, 2,2'-bis (3,4-dicarboxyphenoxyphenyl) sulfone dianhydride, 2,2', 3,3'-biphenyltetracarboxylic dianhydride , 2,2-bis (2,3-dicarboxyphenyl) propanedianhydride, pyromellitic acid dianhydride, 1,2,3,4-benzenetetracarboxylic dianhydride, 1,4,5,8 Examples thereof include −naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride and the like.

Among the above-mentioned symmetric aromatic tetracarboxylic acid anhydrides, 3,3', 4,4'-benzophenonetetra from the viewpoint of compatibility between aromatic tetracarboxylic acid anhydride and diamine, room temperature adhesion, heat adhesion, etc. Selected from the group consisting of carboxylic acid dianhydrides, 4,4'-[propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic acid dianhydrides, and 4,4'-oxydiphthalic acid anhydrides. At least one is preferable.

The upper and lower limits of the content of symmetric aromatic tetracarboxylic dianhydride in 100 mol% of aromatic dianhydride are 100, 90, 80, 70, 60, 55, 50, 40, 30, 20, 10 , 0 mol% and the like are exemplified. In one embodiment, the content of the symmetric aromatic tetracarboxylic dianhydride in 100 mol% of the aromatic tetracarboxylic dianhydride is preferably about 0 to 100 mol%, more preferably about 50 to 100 mol%.

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

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

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

(Other aromatic tetracarboxylic dianhydrides)
In one embodiment, the monomer group is an aromatic tetracarboxylic dianhydride (also referred to as another aromatic tetracarboxylic dianhydride) that is neither the fluorene skeleton-containing tetracarboxylic dianhydride nor the symmetric aromatic tetracarboxylic dianhydride. Can include.

In one embodiment, the content of the other acid anhydrides in 100 mol% of the aromatic tetracarboxylic acid anhydride is less than 5 mol%, less than 4 mol%, less than 1 mol%, less than 0.9 mol%, Examples thereof include less than 0.5 mol%, less than 0.1 mol%, and about 0 mol%.

In one embodiment, the content of the other acid anhydrides in 100% by weight of the aromatic tetracarboxylic acid anhydride is less than 5% by weight, less than 4% by weight, less than 1% by weight, less than 0.9% by weight, Examples thereof include less than 0.5% by mass, less than 0.1% by mass, and about 0% by mass.

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

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

Examples of the upper and lower limits of the content of aromatic tetracarboxylic dianhydride in 100 mol% of the monomer group are 75, 70, 65, 60, 55, 50 mol% and the like. In one embodiment, the content of aromatic tetracarboxylic dianhydride in 100 mol% of the monomer group is preferably about 50 to 75 mol%.

Examples of the upper and lower limits of the content of aromatic tetracarboxylic dianhydride in 100% by mass of the monomer group are 75, 70, 65, 60, 55, 50% by mass and the like. In one embodiment, the content of aromatic tetracarboxylic dianhydride in 100% by mass of the monomer group is preferably about 50 to 75% by mass.

<Diamine>
Diamines can be used alone or in combination of two or more. Examples of diamines include dimer diamines, carboxyl group-containing diamines, and diaminopolysiloxanes.

(Dimer diamine)
In the present disclosure, the dimerdiamine is obtained by substituting all the carboxyl groups of the dimer acid, which is a dimer of an unsaturated fatty acid such as oleic acid, with a primary amino group (see JP-A-9-12712, etc.). Various known substances can be used without particular limitation. Hereinafter, a non-limiting general formula of the dimer diamine is shown (in each formula, m + n = 6 to 17, p + q = 8 to 19 is preferable, and the broken line portion indicates a carbon-carbon single bond or a carbon-carbon double bond. means).

Commercially available dimer diamines are Versamine 551 (manufactured by Cognix Japan Co., Ltd.), Versamine 552 (manufactured by Cognix Japan Co., Ltd .; hydrogenated product of Versamine 551), PRIAMINE 1075, and PRIAMINE 1074 (all manufactured by Croda Japan Co., Ltd.) ) Etc. are exemplified.

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

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

Examples of the upper and lower limits of the content of dimer diamine in 100 mol% of the monomer group are 50, 40, 30, 20, 10, 8, 5 mol% and the like. In one embodiment, the content of dimer diamine in 100 mol% of the monomer group is preferably 5 to 50 mol%.

Examples of the upper and lower limits of the content of dimer diamine in 100% by mass of the monomer group are 50, 40, 30, 20, 10, 8, 5% by mass and the like. 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 has the following general formula,
(Wherein, Y represents a single _{bond, -SO 2 -, - CO -} , - O -, - O-C 6 H 4 -O -, - O-C 6 H 4 -C (CH 3) 2 -C 6 Represents H _4- O-, -COO- (CH ₂ ) _q- OCO-, or -COO-H ₂ C-HC (-O-C (= O) -CH ₃ ) -CH _2- OCO-, q Represents an integer from 1 to 20.)
Represented by.

Aromatic diamines are 4,4'-diaminobiphenyl, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenyl ether, 4,4'-(4,4'-isopropyridenediphenyl-1,1'-diyldioxy). ) Examples include dianiline.

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

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

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

The upper limit of the content of aromatic diamine in 100% by mass of the monomer group is exemplified by 50, 40, 30, 20, 10, 8% by mass, and the lower limit is 40, 30, 20, 10, 8, 5 mass. % Etc. are exemplified. In one embodiment, the content of 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 substance of aromatic diamine to the amount of substance of dimer diamine (aromatic diamine / dimer diamine) is exemplified by 4.0, 3.0, 2.0, 1.0, 0.50 and the like. , The lower limit is exemplified by 4.0, 3.0, 2.0, 1.0, 0.50, 0.25 and the like. In one embodiment, the ratio of the amount of substance of aromatic diamine to the amount of substance of dimer diamine (aromatic diamine / dimer diamine) is 0 from the viewpoint of solvent solubility, workability, flexibility, adhesiveness, and dielectric properties. 25-4.0 is preferable.

(Diaminopolysiloxane)
Diaminopolysiloxanes include α, ω-bis (2-aminoethyl) polydimethylsiloxane, α, ω-bis (3-aminopropyl) polydimethylsiloxane, α, ω-bis (4-aminobutyl) polydimethylsiloxane, α, ω-bis (5-aminopentyl) polydimethylsiloxane, α, ω-bis [3- (2-aminophenyl) propyl] polydimethylsiloxane, α, ω-bis [3- (4-aminophenyl) propyl) ] Polydimethylsiloxane, 1,3-bis (3-aminopropyl) tetramethyldisiloxane, 1,3-bis (4-aminobutyl) tetramethyldisiloxane and the like are exemplified.

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

Examples of the upper and lower limits of the content of diaminopolysiloxane in 100% by mass of diamine are 5, 4, 3, 2, 1, 0% by mass and the like. In one embodiment, the content of diaminopolysiloxane in 100% by mass of diamine is preferably about 0 to 5% by mass from the viewpoint of improving flexibility.

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

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

(Other diamines)
In one embodiment, the monomer group may include diamines other than the above (also referred to as other diamines). Other diamines include alicyclic diamine, bisaminophenoxyphenylpropane, diaminodiphenyl ether, phenylenediamine, diaminodiphenylsulfide, diaminodiphenylsulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, and diaminophenylphenylethane. , Bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, bisaminoditrifluoromethylbenzylbenzene, aminophenoxybiphenyl, aminophenoxyphenylketone, aminophenoxyphenyl sulfide, aminophenoxyphenylsulfone, aminophenoxyphenyl ether, amino Phenoxyphenylpropane, bis (aminophenoxybenzoyl) benzene, bis (aminophenoxy-α, α-dimethylbenzyl) benzene, bis [(aminoaryloxy) benzoyl] diphenyl ether, bis (amino-α, α-dimethylbenzylphenoxy) benzophenone , Bis [amino-α, α-dimethylbenzylphenoxy] diphenylsulfone, 4,4'-bis [aminophenoxyphenoxy] diphenylsulfone, diaminodiaryloxybenzophenone, diaminoaryloxybenzophenone, 6,6'-bis (aminoaryloxy) ) -3,3,3', 3'-tetramethyl-1,1'-spirobiindan, bis (aminoalkyl) ether, bis (aminoalkoxyalkyl) ether, bis (aminoalkoxy) alkane, bis [(aminoalkoxy) Alkanes] Alkanes, (poly) ethyleneglycolbis (aminoalkyl) ethers, bis (aminoaryloxy) pyridines, diaminoalkylenes and the like are exemplified.

The alicyclic diamines are diaminocyclohexane, diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, diaminobicyclo [2.2.1] heptane, bis (aminomethyl) -bicyclo [2.2.1] heptane, 3 (4). , 8 (9) -bis (aminomethyl) tricyclo [5.2.1.0 (2,6)] decane, isophoronediamine, 4,4'-diaminodicyclohexylmethane, 1,3-bisaminomethylcyclohexane, etc. Illustrated.

Examples of the bisaminophenoxyphenyl propane include 2,2-bis [4- (3-aminophenoxy) phenyl] propane and 2,2-bis [4- (4-aminophenoxy) phenyl] propane.

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

Examples of the phenylenediamine include phenylenediamines such as p-phenylenediamine and m-phenylenediamine.

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

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

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

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

The diaminophenyl propane includes 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane and the like. Is exemplified.

Diaminophenyl hexafluoropropane is 2,2-di (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-di (4-aminophenyl) -1,1. , 1,3,3,3-hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3,3-hexafluoropropane and the like are exemplified. To.

Diaminophenylphenylethane includes 1,1-di (3-aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) -1-phenylethane, 1- (3-aminophenyl) -1. -(4-Aminophenyl) -1-phenylethane and the like are exemplified.

Bisaminophenoxybenzene includes 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4-aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, and 1,4-bis. (4-Aminophenoxy) Benzene and the like are exemplified.

Bisaminobenzoylbenzene includes 1,3-bis (3-aminobenzoyl) benzene, 1,3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, and 1,4-bis. (4-Aminobenzoyl) benzene and the like are exemplified.

Bisaminodimethylbenzylbenzene includes 1,3-bis (3-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene, and 1,4-bis. Examples thereof include (3-amino-α, α-dimethylbenzyl) benzene and 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene.

Bisaminoditrifluoromethylbenzylbenzene includes 1,3-bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene and 1,3-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene. , 1,4-Bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene and the like are exemplified.

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. To.

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

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

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

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

Aminophenoxyphenyl propane includes 2,2-bis [4- (3-aminophenoxy) phenyl] propane and 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3. , 3-Hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane and the like.

Bis (aminophenoxybenzoyl) benzene is 1,3-bis [4- (3-aminophenoxy) benzoyl] benzene, 1,3-bis [4- (4-aminophenoxy) benzoyl] benzene, 1,4-bis. Examples thereof include [4- (3-aminophenoxy) benzoyl] benzene and 1,4-bis [4- (4-aminophenoxy) benzoyl] benzene.

Bis (aminophenoxy-α, α-dimethylbenzyl) benzene is 1,3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4- (4- (4-) Aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (4-aminophenoxy) ) -Α, α-dimethylbenzyl] benzene and the like are exemplified.

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

Examples of the bis (amino-α, α-dimethylbenzylphenoxy) benzophenone include 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone.

Bis [amino-α, α-dimethylbenzylphenoxy] diphenylsulfone
Examples thereof include 4,4'-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenyl sulfone.

Examples of 4,4'-bis [aminophenoxyphenoxy] diphenyl sulfone include 4,4'-bis [4- (4-aminophenoxy) phenoxy] diphenyl sulfone.

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

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

6,6'-bis (aminoaryloxy) -3,3,3', 3'-tetramethyl-1,1'-spirobiindane is 6,6'-bis (3-aminophenoxy) -3,3, 3', 3'-tetramethyl-1,1'-spirobiindan, 6,6'-bis (4-aminophenoxy) -3,3,3', 3'-tetramethyl-1,1'-spirobiindan, etc. Illustrated.

Examples of the bis (aminoalkyl) ether include bis (aminomethyl) ether, bis (2-aminoethyl) ether, and bis (3-aminopropyl) ether.

The bis (aminoalkoxyalkyl) ethers are bis [2- (aminomethoxy) ethyl] ether, bis [2- (2-aminoethoxy) ethyl] ether, and bis [2- (3-aminoprotoxy) ethyl]. Ether and the like are exemplified.

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-aminoethoxy) ethoxy] ethane and the like.

The (poly) ethylene glycol bis (aminoalkyl) ether includes ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) ether and the like. Is exemplified.

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

The diaminoalkylenes are ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8-diaminooctane, 1, Examples thereof include 9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, and 1,12-diaminododecane.

In one embodiment, the content of other diamines in 100 mol% diamine is less than 5 mol%, less than 4 mol%, less than 1 mol%, less than 0.9 mol%, less than 0.5 mol%, 0 . Examples include less than 1 mol% and about 0 mol%.

In one embodiment, the content of other diamines in 100% by weight of diamine is less than 5% by weight, less than 4% by weight, less than 1% by weight, less than 0.9% by weight, less than 0.5% by weight, 0. .Examples include less than 1% by mass and about 0% by mass.

In one embodiment, the content of other diamines in 100 mol% of the monomer group is less than 5 mol%, less than 4 mol%, less than 1 mol%, less than 0.9 mol%, less than 0.5 mol%, Examples thereof include less than 0.1 mol% and about 0 mol%.

In one embodiment, the content of other diamines in 100% by weight of the monomer group is less than 5% by weight, less than 4% by weight, less than 1% by weight, less than 0.9% by weight, less than 0.5% by weight, Examples thereof include less than 0.1% by mass and about 0% by mass.

Examples of the upper and lower limits of the diamine content in 100 mol% of the monomer group are 50, 45, 40, 35, 30, 25 mol% and the like. In one embodiment, the content of diamine in 100 mol% of the monomer group is preferably about 25 to 50 mol%.

Examples of the upper and lower limits of the diamine content in 100% by mass of the monomer group are 50, 45, 40, 35, 30, 25% by mass and the like. In one embodiment, the content of diamine in 100 mol% of the monomer group is preferably about 25 to 50% by mass.

The upper and lower limits of the molar ratio of aromatic tetracarboxylic dianhydride to diamine [aromatic tetracarboxylic dianhydride / diamine] are 1.5, 1.4, 1.3, 1.2, 1.1, 1.0 and the like are exemplified. In one embodiment, the molar ratio of aromatic tetracarboxylic dianhydride to diamine [aromatic tetracarboxylic dianhydride / diamine] is about 1.0 to 1.5 from the viewpoint of solvent solubility and solution stability. Is preferable.

The upper and lower limits of the mass ratio of aromatic tetracarboxylic dianhydride to diamine [aromatic tetracarboxylic dianhydride / diamine] are 1.5, 1.4, 1.2, 1.0, 0.9, 0.7, 0.6, 0.5 and the like are exemplified. In one embodiment, the mass ratio of aromatic tetracarboxylic dianhydride to diamine [aromatic tetracarboxylic dianhydride / diamine] is preferably 0.5 to 1.5.

<Other monomers>
In one embodiment, the monomer group may include monomers that are neither aromatic tetracarboxylic dianhydrides nor diamines (also referred to as other monomers). Examples of other monomers include aliphatic tetracarboxylic dianhydrides.

In one embodiment, the content of the other monomers in the monomer group is less than 5 mol%, less than 4 mol%, less than 1 mol%, less than 0.9 mol%, less than 0.5 mol%, 0.1. Examples include less than mol% and about 0 mol%.

In one embodiment, the content of the other monomers in the monomer group is less than 5% by weight, less than 4% by weight, less than 1% by weight, less than 0.9% by weight, less than 0.5% by weight, 0.1. Examples are less than mass%, about 0 mass%, and the like.

In one embodiment, the aromatic tetracarboxylic dianhydride is 4,4'-[propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic acid dianhydride and contains the carboxyl group. The diamine is 3,5-diaminobenzoic acid, or the aromatic tetracarboxylic dianhydride is 3,3', 4,4'-benzophenonetetracarboxylic dianhydride, and the carboxyl group-containing diamine is It is 5,5'-methylenebis (2-aminobenzoic acid).

<Physical properties of polyimide>
Examples of the upper and lower limits of the weight average molecular weight of the polyimide are 50,000, 40,000, 30,000, 20,000, 10,000, 7,500, 5,500, 5,000 and the like. In one embodiment, the weight average molecular weight of the polyimide is preferably 5000 to 50000 from the viewpoint of dielectric properties, solvent solubility, and flexibility.

Examples of the upper limit and the lower limit of the number average molecular weight of the polyimide are 40,000, 30,000, 20,000, 10,000, 7,500, 5,000, 3,000, 2000 and the like. In one embodiment, the number average molecular weight of the polyimide is preferably 2000 to 40,000 from the viewpoint of dielectric properties, solvent solubility, and flexibility.

The weight average molecular weight and the number average molecular weight can be determined, for example, as polystyrene-equivalent values measured by gel permeation chromatography (GPC).

Examples of the upper and lower limits of the softening point of the polyimide are 220, 200, 150, 100, 50, 25, 20 ° C. and the like. 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 by using a commercially available measuring instrument (“ARES-2KSTD-FCO-STD”, manufactured by Rheometric Scientific) or the like.

Examples of the upper and lower limits of the acid value of the polyimide are 300, 275, 250, 225, 200, 175, 150, 125, 100, 75, 50, 25, 20 mgKOH / g and the like. In one embodiment, the acid value of the polyimide is preferably 20 to 300 mgKOH / g.

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

<Polyimide manufacturing method, etc.>
The polyimide can be produced by various known methods. As a method for producing a polyimide, a group of monomers containing an aromatic tetracarboxylic acid anhydride and a diamine containing dimerdiamine and the like is preferably used at a temperature of preferably about 60 to 120 ° C, more preferably about 80 to 100 ° C, and preferably 0. A step of obtaining a polyadduct by subjecting it to a polyaddition reaction for about 1 to 2 hours, more preferably about 0.1 to 0.5 hours, and the obtained polyadduct is preferably about 80 to 250 ° C., more preferably. Is exemplified at a temperature of about 100 to 200 ° C., preferably about 0.5 to 50 hours, more preferably about 1 to 20 hours, including a step of imidization reaction, that is, a dehydration ring closure reaction.

In the step of imidizing 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 later 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, and heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline. Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic anhydride.

The imide ring closure rate of the polyimide is not particularly limited. Here, the "imide ring closure rate" means the content of the cyclic imide bond in the polyimide, and can be determined by various spectroscopic means such as NMR and IR analysis. From the viewpoint of good room temperature adhesion and heat resistance adhesion, the imide ring closure rate of the polyimide is preferably about 70% or more, more preferably about 85 to 100%.

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

The upper and lower limits of the content of one or more selected from the group consisting of polyisocyanate, trimertriamine, and silane-modified epoxy resin in 100% by mass of the composition are 50, 45, 40, 30, 20, 10, and 5. , 2, 1, 0.5, 0.2, 0.1% by mass and the like are exemplified. In one embodiment, the content of one or more selected from the group consisting of polyisocyanate, trimertriamine, and silane-modified epoxy resin in 100% by mass of the composition is preferably 0.1 to 50% by mass.

Mass ratio of polyimide to one or more selected from the group consisting of polyisocyanate, trimertriamine, and silane-modified epoxy resin (one selected from the group consisting of polyimide / polyisocyanate, trimertriamine, and silane-modified epoxy resin) The upper and lower limits of) are 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, Examples include 14, 13, 12, 11, 10, 9, 7, 5, 4, 3, 2, 1, and the like. In one embodiment, the mass ratio of polyimide to one or more selected from the group consisting of polyisocyanate, trimertriamine, and silane-modified epoxy resin (group consisting of polyimide / polyisocyanate, trimertriamine, and silane-modified epoxy resin). One or more selected from) is preferably 1 to 1000.

<Polyisocyanate>
In the present disclosure, "polyisocyanate" is a compound having two or more isocyanate groups (-N = C = O). Examples of the polyisocyanate include linear aliphatic polyisocyanates, branched aliphatic polyisocyanates, alicyclic polyisocyanates, aromatic polyisocyanates, and their biuret, isocyanurate, allophanate, and adduct bodies. In the above composition, the polyisocyanate may be used alone or in combination of two or more.

Examples of the linear aliphatic group include a linear alkylene group. The linear alkylene group is represented by the general formula: − (CH ₂ ) _n − (n is an integer of 1 or more). The linear alkylene group includes a methylene group, an ethylene group, a propylene group, an n-butylene group, an n-pentylene group, an n-hexylene group, an n-heptylene group, an n-octylene group, an n-nonylene group, an n-decamethylene group and the like. Is exemplified.

Examples of the linear aliphatic polyisocyanis include methylene diisocyanis, dimethylene diisocyanis, trimethylene diisocyanate, tetramethylene diisocyanate, pentamethylene diisocyanate, hexamethylene diisocyanate, heptamethylene diisocyanate, octamethylene diisocyanate, nonamethylene diisocyanate, and decamethylene diisocyanis. To.

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

Examples of the branched aliphatic polyisocyanate include diethylpentylene diisocyanate, trimethylbutylene diisocyanate, trimethylpentylene diisocyanate, and trimethylhexamethylene diisocyanate.

Examples of the alicyclic group include a cycloalkylene group. Examples of the cycloalkylene group include a monocyclic cycloalkylene group, a crosslinked cycloalkylene group, and a condensed ring cycloalkylene group. Further, the cycloalkylene group may have one or more hydrogen atoms substituted with a linear or branched alkyl group.

In the present disclosure, the monocyclic ring means a cyclic structure formed by covalent bonds of carbon and having no bridging structure inside. Further, the condensed ring means a cyclic structure in which two or more monocycles share two atoms (that is, only one side of each ring is shared (condensed) with each other). The crosslinked ring means a cyclic structure in which two or more monocycles share three or more atoms.

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

Examples of the crosslinked ring cycloalkylene group include a tricyclodecylene group, an adamantylene group, and a norbornene group.

Examples of the fused ring cycloalkylene group include a bicyclodecylene group.

Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanates, crosslinked alicyclic polyisocyanates, and condensed alicyclic polyisocyanates.

The monocyclic alicyclic polyisocyanate includes hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5,5-trimethylcyclohexylene diisocyanate, and dicyclohexylmethane. Examples thereof include diisocyanate.

Examples of the crosslinked alicyclic polyisocyanate include tricyclodecylene diisocyanate, adamantane diisocyanate, and norbornene diisocyanate.

Examples of the condensed ring alicyclic polyisocyanate include bicyclodecylene diisocyanate.

Examples of the aromatic group include a monocyclic aromatic group and a condensed ring aromatic group. Further, the aromatic group may have one or more hydrogen atoms substituted with a linear or branched alkyl group.

Examples of the monocyclic aromatic group include a phenyl group (phenylene group), a tolyl group (tolyl group), and a mesitylene group (mesitylene group). Examples of the fused ring aromatic group include a naphthyl group (naphthylene group) and the like.

Examples of the aromatic polyisocyanate include monocyclic aromatic polyisocyanate and condensed ring aromatic polyisocyanate.

The monocyclic aromatic polyisocyanate includes dialkyldiphenylmethane diisocyanate such as 4,4'-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate such as 4,4'-diphenyltetramethylmethane diisocyanate, 4,4'-diphenylmethane diisocyanate, 4, Examples thereof include 4'-dibenzyl isocyanate, 1,3-phenylenediocyanate, 1,4-phenylenediocyanate, tolylene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene diisocyanate.

Examples of the fused ring aromatic polyisocyanate include 1,5-naphthylene diisocyanate.

The biuret form of polyisocyanate is
The following structural formula:
[In the formula, n ^b is an integer of 1 or more, and R ^{bA to} R ^bE are independently alkylene groups, arylene groups, or groups in which an alkylene group and an isocyanate group are combined, and R ^{bα to} R. Each ^bβ is independently an isocyanate group or
^{(N b1} is an integer of 0 or ^more, in each of R b1 ^{to R b5} independently an alkylene group, an arylene group, or an alkylene group and an arylene group is combination group, ^{R b '~R b'} 'Is an isocyanate group or a group of R ^{bα to} R ^bβ itself. R ^{b4 to} R ^b5 and R ^b '' may have different groups for each constituent unit). The ^{groups of} R ^{bD to} R ^bE and R ^bβ may be different for each structural unit. ] Is exemplified.

Examples of the group formed by combining an alkylene group and an arylene group include an alkylene arylene alkylene group.

The alkylene arylene alkylene group is
−R ^alkylene −R ^allyrene −R ^alkylene −
(In the formula, R ^alkylene represents an alkylene group and R ^allylene represents an arylene group).
It is a group represented by.

The biuret form of polyisocyanate is Duranate 24A-100, Duranate 22A-75P, Duranate 21S-75E (manufactured by Asahi Kasei Corporation), Death Module N3200A (biuret form of hexamethylene diisocyanate) (manufactured by Sumitomo Bayer Urethane Co., Ltd.). ) Etc. are exemplified.

Isocyanurates of polyisocyanates are
The following structural formula:
Wherein, ^{n i} is an integer of 0 or ^more, are each R iA ^{to R iE} independently an alkylene group, an arylene group, or an alkylene group and an arylene group is combination group, ^{R i.alpha} to R ^iβ are independently isocyanate groups or
^{(N i1} is an integer of 0 or ^more, R i1 ^{to R i5} is independently an alkylene group, an arylene group, or an alkylene group and an arylene group is combination group, ^{R i} '~R ^i' 'are each independently an isocyanate group or R ^i.alpha to R ^i.beta own group .R ^{i5, R i'} 'is may be different groups in each constitutional unit.). The groups of R ^{iD to} R ^iE and R ^iβ may be different for each structural unit. ] Is exemplified.

The isocyanurates of polyisocyanate are Duranate TPA-100, Duranate TKA-100, Duranate MFA-75B, Duranate MHG-80B (manufactured by Asahi Kasei Co., Ltd.), Coronate HXR (Isocyanurate of hexamethylene diisocyanate) (Toso). Mitsui Chemicals, Inc.), Takenate D-131N (isocyanurate of xylene diisocyanate), Takenate D204EA-1 (isocyanurate of toluene diisocyanate), Takenate D-127N (isocyanurate of hydrogenated xylene diisocyanate) (Manufactured by Co., Ltd.), VESTANAT T1890 / 100 (isocyanurate form of isophorone diisocyanate) (all manufactured by Ebonic Japan Co., Ltd.) and the like are exemplified.

The allophanate form of polyisocyanate is
The following structural formula:
Wherein, ^{n a} is an integer of 0 or ^{more, R aA} is an alkyl group or an aryl ^group, in each of R aB ^{to R aG} independently, an alkylene group, an arylene group, or an alkylene group and an arylene group It is a group composed of a combination, and R ^{aα to} R ^aγ are independently isocyanate groups or groups.
^{(N a1} is an integer of 0 or ^more, in each of R a1 ^{to R a6} independently an alkylene group or an arylene ^{group, R a '~R a''} ' are each independently, an isocyanate group, or ^{R a.alpha} ~ R ^Eiganma is its own group ^{.R a1 ~R a4, R a '} ~R a''' is may be different groups in each constitutional unit.). The groups of R ^{aB to} R ^aE and R ^{aα to} R ^aγ may be different for each structural unit. ] Is exemplified.

Examples of commercially available products of allophanates of polyisocyanate include Takenate D-178N (manufactured by Mitsui Chemicals, Inc.).

The adduct body of polyisocyanate is
The following structural formula:
[In the formula, n ^ad is an integer of 0 or more, and R ^{adA to} R ^adE are independently alkylene groups, arylene groups, or groups in which an alkylene group and an arylene group are combined, and R ^{ad1 to} R ^ad2. Are independent of each other
(In the formula, n ^ad'is an integer of 0 or more, and R ^ad'to R ^{ad'is an} alkylene group, an arylene group, or a group formed by combining an alkylene group and an arylene group, respectively, and R ^{ad '''is} R ^ad1 to R ^ad2 own ^{group, R ad' ~R ad ''} ' may be different groups in each constitutional unit.)
The ^groups of R ^{adD to} R ^adE and R ^ad2 may be different for each structural unit. ]
Adducts of trimethylolpropane and polyisocyanate, indicated by
The following structural formula
[In the formula, n ^ad1 is an integer of 0 or more, R ^{adα to} R ^adε are independently alkylene groups or arylene groups, and R ^{adA to} R ^adB are independent.
(In the formula, n ^ad1'is an integer of 0 or more, and R ^adδ'to R ^adε' are independently alkylene groups, arylene groups, or groups in which an alkylene group and an arylene group are combined, respectively, and R ^{adB. '} Is a group of R ^{adA to} R ^adB itself, and R ^adδ'to R ^adε'and R ^adB'may have different groups for each constituent unit.)
R ^{ad δ to} R ^{ad ε} may have different groups for each constituent unit. ]
Examples thereof include glycerin and polyisocyanate adducts shown in.

Examples of polyisocyanate adducts include Duranate P301-75E (manufactured by Asahi Kasei Corporation), Takenate D110N, Takenate D160N (manufactured by Mitsui Chemicals, Inc.), Coronate L (manufactured by Tosoh Corporation), and the like. ..

The upper and lower limits of the content of polyisocyanate in 100% by mass of the composition are 50, 45, 40, 30, 20, 10, 5, 2, 1, 0.5, 0.2, 0.1% by mass and the like. Is exemplified. In one embodiment, the content of 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) are 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. are exemplified. In one embodiment, the mass ratio of polyimide to polyisocyanate (polyimide / polyisocyanate) is preferably 1 to 1000.

<Trimmer triamine>
Trimmer triamine is obtained by substituting all the carboxyl groups of trimeric acid (see JP-A-2013-505345, etc.), which is a trimer of unsaturated fatty acids such as oleic acid, with primary amino groups, and is known in various ways. Can be used without any particular restrictions. Hereinafter, a non-limiting structural formula of trimertriamine is shown (the broken line portion means a carbon-carbon single bond or a carbon-carbon double bond, and R is an ethylene group (-CH ₂ CH _2- ) or an ethenylene group (-CH ₂ CH _2- ). It means −CH = CH−).).

Examples of commercially available trimmer triamines include PRIAMINE1071 (manufactured by Croda Japan Co., Ltd.) and the like. The content of the trimertriamine component in the commercially available product is usually about 15 to 20% by mass, and the dimer diamine may be contained in excess of 80% by mass as the balance.

The upper and lower limits of the content of trimertriamine in 100% by mass of the composition are 50, 45, 40, 30, 20, 10, 5, 2, 1, 0.5, 0.2, 0.1% by mass and the like. Is exemplified. In one embodiment, the content of trimertriamine 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 trimertriamine (polyimide / trimertriamine) are 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. are exemplified. In one embodiment, the mass ratio of polyimide to trimertriamine (polyimide / trimertriamine) is preferably 1 to 1000.

<Silane-modified epoxy resin>
The silane-modified epoxy resin is a reaction product of a hydroxyl group-containing epoxy resin and an alkoxysilane partial condensate.

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

Examples of the upper and lower limits of the epoxy equivalent of the hydroxyl group-containing epoxy resin are 5000, 4000, 3000, 2000, 1000, 900, 800, 750, 500, 450, 400, 300, 250, 200, 180 and the like. In one embodiment, the epoxy equivalent of the hydroxyl group-containing epoxy resin is preferably 180 to 5000, more preferably 450 to 500.

The alkoxysilane partial condensate has a general formula: R ¹ _p Si (OR ² ) _4-p.
(In the formula, p is an integer of 0 to 2, R ¹ is a substituted or unsubstituted alkyl group having 6 or less carbon atoms, an aryl group, or an alkenyl group, and R ² is an alkyl group having 6 or less carbon atoms. An alkoxysilane represented by (there is) or a condensate thereof and the like can be exemplified.

Alkyl groups having 6 or less carbon atoms include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, s-butyl group, i-butyl group, t-butyl group, n-pentyl group, neopentyl group, and i. Examples thereof include −pentyl group, s-pentyl group, 3-pentyl group, t-pentyl group, hexyl group, isohexyl group, 3-methylpentyl group, 2,3-dimethylbutyl group and 2,2-dimethylbutyl group. ..

Examples of the substituent include a glycidyl group, a mercapto group, an epoxy group and the like.

Examples of the aryl group include a phenyl group and a naphthyl group.

Examples of the alkenyl group include a vinyl group and an allyl group.

Examples of the alkoxysilane include tetraalkoxysilane, trialkoxysilane, and dialkoxysilane.

Examples of the tetraalkoxysilane include tetramethoxysilane, tetraethoxysilane, tetrapropoxysilane, tetraisopropoxysilane, and tetrabutoxysilane.

Examples of the trialkoxysilane include alkyltrialkoxysilanes, aryltrialkoxysilanes, and functional group-containing trialkoxysilanes.

Alkyltrialkoxysilanes include methyltrimethoxysilane, methyltriethoxysilane, methyltripropoxysilane, methyltributoxysilane, ethyltrimethoxysilane, ethyltriethoxysilane, n-propyltrimethoxysilane, n-propyltriethoxysilane, Examples thereof include isopropyltrimethoxysilane and isopropyltriethoxysilane.

Examples of the aryltrialkoxysilane include phenyltrimethoxysilane and phenyltriethoxysilane.

Examples of the alkenyltrialkoxysilane include vinyltrimethoxysilane and vinyltriethoxysilane.

The functional group-containing trialkoxysilanes are 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, and 3,4-epoxycyclohexyl. Examples thereof include ethyltrimethoxysilane and 3,4-epylcyclohexylethyltrimethoxysilane.

Examples of the dialkoxysilane include dimethyldimethoxysilane, dimethyldiethoxysilane, diethyldimethoxysilane, and diethyldiethoxysilane.

The silane-modified epoxy resin is produced by esterifying a hydroxyl group-containing epoxy resin and an alkoxysilane partial condensate by a dealcohol reaction. Although not particularly limited, it is preferable to carry out the reaction at a reaction temperature of 50 to 130 ° C. for 1 to 15 hours with a silica-equivalent mass of the alkoxysilane partial condensate / mass (mass ratio) of the hydroxyl group-containing epoxy resin of 0.01 to 1.2. ..

The upper and lower limits of the content of the silane-modified epoxy resin in 100% by mass of the composition are 50, 45, 40, 30, 20, 10, 5, 2, 1, 0.5, 0.2, 0.1 mass. % Etc. are exemplified. In one embodiment, the content of the silane-modified epoxy resin 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 and silane-modified epoxy resin (polyimide / silane-modified epoxy resin) are 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. are exemplified. In one embodiment, the mass ratio of polyimide to silane-modified epoxy resin (polyimide / silane-modified epoxy resin) is preferably 1 to 1000.

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

[Reactant]
The present disclosure describes the reaction of polyimide, which is a reaction product of a group of monomers containing aromatic tetracarboxylic acid anhydride and dimer diamine, with one or more selected from the group consisting of polyisocyanate, trimertriamine, and silane-modified epoxy resin. Provide things.

Examples of components such as aromatic tetracarboxylic dianhydride include those described above.

The reaction conditions for producing the above-mentioned reactant are not particularly limited, and examples thereof include heating / crimping conditions for producing the copper-clad laminate described later.

In one embodiment, the reactant can be used as a thermoplastic polyimide layer, a plating primer layer (eg, a copper plating primer layer).

[adhesive]
The present disclosure provides an adhesive containing the above composition, a cross-linking agent and an organic solvent.

Examples of the upper and lower limits of the polyimide content in 100% by mass of the adhesive include 90, 80, 70, 60, 50, 40, 30, 20, 10, 5% by mass and the like. The content of the polyimide in 100% by mass of the adhesive is preferably about 5 to 90% by mass.

<Crosslinking agent>
As the cross-linking agent, various known ones can be used without particular limitation as long as they function as a cross-linking agent for polyimide. The cross-linking agent may be used alone or in combination of two or more.

Examples of the cross-linking agent include epoxides, benzoxazines, bismaleimides, cyanate esters, polyisocyanates and the like. In one embodiment, the cross-linking agent is preferably at least one selected from the group consisting of epoxides, benzoxazines, bismaleimides and cyanate esters.

(Epoxide)
The epoxides are phenol novolac type epoxide, cresol novolac type epoxide, bisphenol A type epoxide, bisphenol F type epoxide, bisphenol S type epoxide, hydrogenated bisphenol A type epoxide, hydrogenated bisphenol F type epoxide, stillben type epoxide, triazine skeleton containing epoxide. , Fluorene skeleton containing epoxide, linear aliphatic epoxide, alicyclic epoxide, glycidylamine type epoxide, triphenol methane type epoxide, alkyl modified triphenol methane type epoxide, biphenyl type epoxide, dicyclopentadiene skeleton containing epoxide, naphthalene skeleton containing Examples thereof include epoxides, arylalkylene-type epoxides, tetraglycidyl xylylene diamines, dimer acid-modified epoxides which are dimer acid-modified products of the epoxides, dimer acid diglycidyl esters, and silane-modified epoxy resins. Commercially available products of epoxide are "jER828", "jER834" and "jER807" manufactured by Mitsubishi Chemical Company, "ST-3000" manufactured by Nippon Steel Chemical Co., Ltd., and manufactured by Daicel Chemical Industry Co., Ltd. Examples thereof include "Selokiside 2021P", "YD-172-X75" manufactured by Nippon Steel Chemical Co., Ltd., and "TETRAD-X" manufactured by Mitsubishi Gas Chemical Company. Among these, at least one selected from the group consisting of bisphenol A type epoxide, bisphenol F type epoxide, hydrogenated bisphenol A type epoxide and alicyclic epoxide from the viewpoint of balance of heat resistance adhesiveness, moisture absorption solder heat resistance and low dielectric property. Seeds are preferred.

In particular, tetraglycidyl diamine having the following structure
(In the formula, Y represents a phenylene group or a cyclohexylene group.)
Has good compatibility with the above-mentioned polyimide. Further, when this is used, it becomes easy to reduce the loss elastic modulus of the adhesive layer, and its heat-resistant adhesiveness and low dielectric property are also improved.

When epoxide is used as the cross-linking agent, various known curing agents for epoxide can be used in combination. The epoxide curing agent can be used alone or in combination of two or more. Hardeners for epoxide are succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, phthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride. Or a mixture of 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadicic anhydride, methylnadic anhydride, norbornan-2,3-dicarboxylic acid anhydride , Methylnorbornan-2,3-dicarboxylic acid anhydride, methylcyclohexene dicarboxylic acid anhydride, 3-dodecenyl succinic anhydride, octenyl succinic anhydride and other acid anhydride-based curing agents; Names "LonzacureM-DEA", "LonzacureM-DETDA", etc. All are manufactured by Lonza Japan Co., Ltd., amine-based curing agents such as aliphatic amines; Phenolic novolak resin, phenolic hardeners such as phenolic hydroxyl group-containing phosphazene (trade name "SPH-100" manufactured by Otsuka Chemical Co., Ltd.), cyclic phosphazene compounds, maleic anhydride-modified rosin and rosin-based hydrides A cross-linking agent and the like are exemplified. Among these, a phenolic curing agent, particularly a phenolic hydroxyl group-containing phosphazene-based curing agent is preferable. The amount of the curing agent used is not particularly limited, but when the solid content of the adhesive is 100% by mass, it is preferably about 0.1 to 120% by mass, more preferably about 10 to 40% by mass.

When epoxide and a curing agent for epoxide are used in combination as the cross-linking agent, a reaction catalyst can be further used in combination. The reaction catalyst can be used alone or in combination of two or more. The reaction catalyst is a tertiary amine such as 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol; Imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; organics such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenylphosphine and the like. Hosphine; tetraphenylborone salts such as tetraphenylphosphonium / tetraphenylborate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholin / tetraphenylborate and the like are exemplified. The amount of the reaction catalyst used is not particularly limited, but is preferably about 0.01 to 5% by mass when the solid content of the adhesive is 100% by mass.

(Benzooxazine)
The benzoxazines are 6,6- (1-methylethylidene) bis (3,4-dihydro-3-phenyl-2H-1,3-benzoxazine) and 6,6- (1-methylethylidene) bis (3, 4-Dihydro-3-methyl-2H-1,3-benzoxazine) and the like are exemplified. A phenyl group, a methyl group, a cyclohexyl group, or the like may be bonded to the nitrogen of the oxazine ring. Commercially available products of benzoxazine are "benzoxazine FA type" and "benzoxazine Pd type" manufactured by Shikoku Chemicals Corporation, and "RLV-100" manufactured by Air Water Co., Ltd. Etc. are exemplified.

(Bismaleimide)
Bismaleimide is 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4- Examples thereof include methyl-1,3-phenylene bismaleimide, 1,6'-bismaleimide- (2,2,4-trimethyl) hexane, 4,4'-diphenyl ether bismaleimide, and 4,4'-diphenylsulphon bismaleimide. Will be done. Examples of commercially available bismaleimide products include "BAF-BMI" manufactured by JFE Chemical Corporation.

(Cyanate ester)
The cyanate ester is 2-allylphenol cyanate ester, 4-methoxyphenol cyanate ester, 2,2-bis (4-cyanatophenol) -1,1,1,3,3,3-hexafluoropropane, bisphenol A cyanate. Esters, diallyl bisphenol A cyanate esters, 4-phenylphenol cyanate esters, 1,1,1-tris (4-cyanatophenyl) ethane, 4-cumylphenol cyanate esters, 1,1-bis (4-cyanatophenyl) ) Ethan, 4,4'-bisphenol cyanate ester, 2,2-bis (4-cyanatophenyl) propane and the like are exemplified. Examples of commercially available cyanate esters include "PRIMASET BTP-6020S (manufactured by Lonza Japan Co., Ltd.)" and the like.

The upper and lower limits of the content of the cross-linking agent with respect to 100 parts by mass (solid content equivalent) of the polyimide in the adhesive are 900, 800, 700, 600, 500, 400, 300, 200, 100, 50, 20, 10 5, 5 parts by mass and the like are exemplified. In one embodiment, the content of the cross-linking agent with respect to 100 parts by mass (in terms of solid content) of the polyimide is preferably about 5 to 900 parts by mass.

Examples of the upper and lower limits of the content of the cross-linking agent in 100% by mass of the adhesive are 80, 70, 60, 50, 40, 30, 20, 10, 5, 2% by mass and the like. In one embodiment, the content of the cross-linking agent in 100% by mass of the adhesive is preferably about 2 to 80% by mass.

<Organic solvent>
As the organic solvent, various known organic solvents can be used alone or in combination of two or more. Organic solvents include aprotonic polar solvents such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylcaprolactam, methyltriglime, and methyldiglyme, and alicyclics such as cyclohexanone and methylcyclohexane. Examples thereof include formula solvents, alcohol solvents such as methanol, ethanol, propanol, benzyl alcohol and cresol, and aromatic solvents such as toluene.

The content of the organic solvent in the adhesive is not particularly limited, but the upper and lower limits of the solid content mass with respect to 100% by mass of the adhesive of the organic solvent are exemplified by 60, 50, 40, 30, 20, 10% by mass and the like. Will be done. In one embodiment, the solid content mass of the organic solvent with respect to 100% by mass of the adhesive is preferably 10 to 60% by mass.

Examples of the upper and lower limits of the content of the organic solvent with respect to 100 parts by mass (solid content equivalent) of the polyimide in the adhesive are 900, 800, 700, 600, 500, 400, 300, 200, 150 parts by mass and the like. To. In one embodiment, the content of the organic solvent in the adhesive with respect to 100 parts by mass (solid content equivalent) of the polyimide is preferably 150 to 900 parts by mass.

<Flame retardant>
In one embodiment, the adhesive comprises a flame retardant. The flame retardant can be used alone or in combination of two or more. Examples of the flame retardant include phosphorus-based flame retardants and inorganic fillers.

(Phosphorus flame retardant (phosphorus-containing flame retardant))
Examples of the phosphorus-based flame retardant include polyphosphoric acid, phosphoric acid ester, and phosphazene derivative containing no phenolic hydroxyl group. Among the phosphazene derivatives, the cyclic phosphazene derivative is preferable in terms of flame retardancy, heat resistance, bleed-out resistance and the like. Examples of commercially available cyclic phosphazene derivatives include SPB-100 manufactured by Otsuka Chemical Co., Ltd. and Ravitor FP-300B manufactured by Fushimi Pharmaceutical Co., Ltd.

(Inorganic filler)
In one embodiment, examples of the inorganic filler include silica filler, phosphorus-based filler, fluorine-based filler, and inorganic ion exchanger filler. 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., and IXE manufactured by Toagosei Co., Ltd.

Examples of the upper and lower limits of the content of the flame retardant with respect to 100 parts by mass (solid content equivalent) of polyimide in the adhesive are 150, 100, 50, 10, 5, 1 part by mass and the like. In one embodiment, the content of the flame retardant in 100 parts by mass (in terms of solid content) of the polyimide in the adhesive is preferably 1 to 150 parts by mass.

<Reactive alkoxysilyl compound>
In one embodiment, the adhesive further comprises a general formula: Z-Si (R ¹ ) _a (OR ² ) _3-a (where Z is a group containing a functional group that reacts with an acid anhydride group. , R ¹ represents a hydrocarbon or a hydrocarbon group having 1 to 8 carbon atoms, R ² represents a hydrocarbon group having 1 to 8 carbon atoms, and a represents 0, 1 or 2). Contains compounds. The reactive alkoxysilyl compound allows the melt viscosity of the adhesive layer of the present invention to be adjusted while maintaining the low dielectric properties. As a result, the exudation of the cured layer generated from the edge of the base material can be suppressed while increasing the interfacial adhesion between the adhesive layer and the base material (so-called anchor effect).

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

Compounds in which Z contains an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, and 3-aminopropyltrimethoxysilane. , 3-Aminopropyltriethoxysilane, 3-ureidopropyltrialkoxysilane and the like. Examples of the compound in which Z contains an epoxy group include 2- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, and 3-glyci. Examples thereof include sidoxylpropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane. Examples of the compound in which Z contains a thiol group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3-mercaptopropylmethyldiethoxysilane. .. Among these, compounds in which Z contains an amino group are preferable because they have good reactivity and flow control effects.

The upper and lower limits of the content of the reactive alkoxysilyl compound with respect to 100 parts by mass (solid content equivalent) of polyimide in the adhesive are 5, 2.5, 1, 0.5, 0.1, 0.05, 0. 0.01 parts by mass and the like are exemplified. In one embodiment, the content of the reactive alkoxysilyl compound with respect to 100 parts by mass (solid content equivalent) of polyimide in the adhesive is preferably 0.01 to 5 parts by mass.

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

Additives include ring-opening esterification reaction catalysts, dehydrators, plasticizers, weather resistant agents, antioxidants, heat stabilizers, lubricants, antistatic agents, whitening agents, colorants, conductive agents, mold release agents, and surface treatments. Examples thereof include agents, viscosity modifiers, silica fillers and fluorine fillers.

In one embodiment, the content of the additive is exemplified by less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc. with respect to 100 parts by mass of the adhesive.

In another embodiment, the content of the additive is exemplified by less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, etc. with respect to 100 parts by mass (solid content equivalent) of the polyimide. Will be done.

The adhesive can be obtained by dissolving the polyimide and the cross-linking agent and, if necessary, a flame retardant, a reactive alkoxysilyl compound and an additive in an organic solvent.

[Film-like adhesive]
The present disclosure provides a film-like adhesive containing a heat-cured product of the composition and / or a heat-cured product of the adhesive. The method for producing the film-like adhesive includes a step of applying the adhesive to an appropriate support, a step of curing by heating to volatilize an organic solvent, a step of peeling from the support, and the like. Illustrated. The thickness of the adhesive is not particularly limited, but is preferably about 3 to 40 μm. Examples of the support include the following.

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

[Adhesive sheet]
The present disclosure provides an adhesive sheet including the adhesive layer and a support film.

The support film is exemplified by a plastic film. Plastics include polyester, polyimide, polyimide-silica hybrid, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin, ethylene terephthalate, phenol, and phthalic acid. Examples thereof include aromatic polyester resins (so-called liquid crystal polymers; manufactured by Kuraray Co., Ltd., "Vexter", etc.) obtained from hydroxynaphthoic acid and the like and parahydroxybenzoic acid.

Further, when the adhesive is applied to the support film, the coating means can be adopted. The thickness of the coating layer is not particularly limited, but the thickness after drying is preferably about 1 to 100 μm, more preferably about 3 to 50 μm. Further, the adhesive layer of the adhesive sheet may be protected by various protective films.

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

Further, the adhesive layer of the resin-attached copper foil may be uncured, or may be partially cured or completely cured under heating. The partially cured adhesive layer is in a so-called B stage. Further, the thickness of the adhesive layer is not particularly limited, and is preferably about 0.5 to 30 μm. Further, a resin may be further attached to the copper foil of the copper foil with resin to obtain a copper foil with double-sided resin.

[Copper-clad laminate]
The present disclosure provides a copper-clad laminate comprising the adhesive sheet and / or the copper foil with resin, and one or more selected from the group consisting of copper foil, insulating sheet and support film. Copper-clad laminates are also called CCL (Copper Clad Laminate). In one embodiment, the copper-clad laminate is selected from the group consisting of various known copper foils bonded to one side or both sides of the adhesive sheet, or various known copper foils, insulating sheets and support films. The above-mentioned copper foil with resin is pressure-bonded to one or more sides or both sides under heating. When bonding to one side, a material different from the above-mentioned copper foil with resin may be crimped to the other side. Further, the number of resin-attached copper foils and insulating sheets in the copper-clad laminate is not particularly limited.

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

The present disclosure also provides a copper-clad laminate having a copper-plated layer on the adhesive sheet or the copper foil with resin.

In one embodiment, the 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. The reducing agent may be used alone or in combination of two or more. Examples of the reducing agent include sodium phosphinate, dimethylamine borane, formalin, glyoxylic acid, tetrahydroboric acid, hydrazine, sodium hypophosphite and the like. When the electroless copper plating solution contains a reducing agent, the content thereof is preferably about 0.1 to 100 g / L, more preferably about 1 to 30 g / L.

The electroless copper plating solution may contain a complexing agent. The complexing agent may be used alone or in combination of two or more. The complexing agent includes citric acid, tartaric acid, malic acid, lactic acid, gluconic acid or an alkali metal salt thereof (for example, Rochelle salt), carboxylic acid (salt) such as ammonium salt, amino acid such as glycine, ethylenediamine, alkylamine and the like. Examples include amines, other ammoniums, EDTA, pyrophosphate (salt) and the like. When the electroless copper plating solution contains a complexing agent, the content thereof is preferably about 1 to 100 g / L, more preferably about 10 to 100 g / L.

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

Electroless copper plating may be repeated twice or more, if necessary.

Examples of vacuum copper plating include copper sputtering and the like.

Copper sputtering can be performed using various known sputtering devices.

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

Vacuum copper plating may be repeated twice or more, if necessary.

[Printed circuit board]
The present disclosure provides a printed wiring board having a circuit pattern on the copper foil surface of the copper-clad laminate. Examples of the patterning means for forming a circuit pattern on the copper foil surface of the copper-clad laminate include the subtractive method and the semi-additive method. An example of the semi-additive method is a method in which the copper foil surface of a copper-clad laminate is patterned with a resist film, then electrolytically copper-plated to remove the resist, and then etched with an alkaline solution. Further, the thickness of the circuit pattern layer in the printed wiring board is not particularly limited. Further, a multilayer board can also be obtained by using the printed wiring board as a core base material and laminating the same printed wiring board or another known printed wiring board or printed circuit board on the printed wiring board. At the time of laminating, the above-mentioned adhesive and other known adhesives other than the above-mentioned adhesive can be used in combination. Further, the number of layers in the multilayer board is not particularly limited. Further, a via hole may be inserted each time the lamination is performed, and the inside may be plated. The line / space ratio of the circuit pattern is not particularly limited, but is preferably about 1 μm / 1 μm to 100 μm / 100 μm. The height of the circuit pattern is also not particularly limited, but is preferably about 1 to 50 μm.

[Multilayer wiring board]
The present disclosure provides a multilayer wiring board including a printed wiring board (1) or a printed circuit board (1), the adhesive layer, and a printed wiring board (2) or a printed circuit board (2). The printed wiring boards (1) and (2) may be the printed wiring boards, or may be various known ones. Similarly, the printed circuit boards (1) and (2) may be the printed circuit boards described above, or may be of various known ones. Further, the printed wiring board (1) and the printed wiring board (2) may be the same or different. Similarly, the printed circuit board (1) and the printed circuit board (2) may be the same or different.

[Manufacturing method of multilayer wiring board]
The present disclosure describes the following steps 1 and 2.
Step 1: By bringing one or more selected from the group consisting of the adhesive, the film-like adhesive, and the adhesive sheet into contact with at least one side of the printed wiring board (1) or the printed circuit board (1). Step 2: Producing a base material with an adhesive layer: A step of laminating a printed wiring board (2) or a printed circuit board (2) on the base material with an adhesive layer and crimping under heating and pressure is included. Provided is a method for manufacturing a multilayer wiring board.

The printed wiring boards (1) and (2) may be the printed wiring boards, or may be various known ones. Similarly, the printed circuit boards (1) and (2) may be the printed circuit boards described above, or may be of various known ones.

In step 1, the means for bringing the adhesive or film-like adhesive into contact with the adherend is not particularly limited, and various known coating means, curtain coaters, roll coaters, laminators, presses, and the like are exemplified.

The heating temperature and crimping time in step 2 are not particularly limited, but (a) the adhesive or film-like adhesive of the present invention is brought into contact with at least one surface of the core base material, and then heated to about 70 to 200 ° C. 1 After the curing reaction takes about 10 minutes to 10 minutes, it is preferable to further heat-treat at about 150 ° C. to 300 ° C. for about 10 minutes to 3 hours in order to (a) proceed with the curing reaction of the cross-linking agent. The pressure is also not particularly limited, but is preferably about 0.5 to 20 MPa, more preferably about 1 to 8 MPa throughout the steps (a) and (b).

Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. However, the above description of the preferred embodiment and the following examples are provided only for the purpose of illustration, 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 the present specification, but is limited only by the scope of claims. Further, in each Example and Comparative Example, unless otherwise specified, numerical values such as parts and% are based on mass.

Production Example 1 Polyimide production In a reaction vessel equipped with a stirrer, water divider, thermometer and nitrogen gas introduction tube, 4,4'-[propane-2,2-diylbis (1,4-phenyleneoxy)] diphthal Add 350.00 g of acid dianhydride (trade name "BisDA-1000", manufactured by SABIC Innovative Plastics Japan LLC; hereinafter abbreviated as BisDA), Cyclohexanone 993.30 g, and methylcyclohexane 198.66 g, up to 60 ° C. It was heated. 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 "PRIAMINE 1075", Croda Japan Co., Ltd.) A solution of polyimide (1-1) (nonvolatile content: 32.9%) was obtained by adding 103.85 g of (manufactured product) and then imidizing the mixture at 140 ° C. for 12 hours. The molar ratio of the acid component / amine component of the polyimide was 1.05, and the softening point was 180 ° C.

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, Inc.).

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 table below.

Takenate D-110N: Trimethylolpropane adduct of xylene diisocyanate (manufactured by Mitsui Chemicals, Inc.)
Takenate D-131N: Isocyanurate of xylene diisocyanate (manufactured by Mitsui Chemicals, Inc.)
Takenate D-204EA-1: Isocyanurate of toluene diisocyanate (manufactured by Mitsui Chemicals, Inc.)
P1071: PRIAMINE1071, trimertriamine / dimerdiamine mass ratio = 20/80 (manufactured by Croda Japan Co., Ltd.)
VESTANAT T1890 / 100: Isophorone diisocyanate isocyanurate (manufactured by Evonik)

Example 2
<Making an adhesive sheet>
The compositions of Example 1 and Comparative Example 1 were applied to a polyimide film (trade name "Kapton 100EN", manufactured by Toray Duupon Co., Ltd.) with a gap coater so that the thickness after drying was 10 μm, and then 200. An adhesive sheet was obtained by drying at ° C. for 3 minutes.

<Manufacturing of copper-clad laminate (1) using copper foil>
Copper with resin on which 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 Nippon Mining & Metals Co., Ltd., 12 μm thickness). A foil was made.

Next, the obtained copper foil with resin is placed on a support for pressing, and heat-pressed from above under the conditions of a pressure of 2 MPa, 180 to 300 ° C., and 10 minutes via a support obtained from the same material. To prepare a copper-clad laminate.

1. 1. Adhesiveness test The obtained copper-clad laminate was measured in peeling strength (N / mm) at room temperature according to JIS C 6481 (copper-clad laminate test method for flexible printed wiring boards).

2. 2. Dielectric constant and dielectric loss tangent measurement <Preparation of resin for measurement and cured product sample>
The compositions of Examples and Comparative Examples are coated on a paper pattern (trade name "WH52-P25CM", manufactured by Sun A. Kaken Co., Ltd.) so that the film thickness becomes 10 μm after curing, and dried at 200 ° C. for 3 minutes. .. The resin and cured product for dielectric constant measurement with a film thickness of about 300 μm are peeled off and cured by heat pressing under the conditions of pressure 1.5 MPa, 250 ° C. and 10 minutes so that the film thickness after pressing becomes about 300 μm. A sample was obtained.

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

3. 3. Solder heat resistance test (with pre-drying)
After curing, the copper-clad laminate (1) using the copper foil was floated in a solder bath at 288 ° C. with the copper foil side down for 30 seconds, and pre-dried at 120 ° C. for 5 minutes to change the appearance. The presence was confirmed. When there was no change, it was marked as ◯, and when there was foaming or swelling, it was marked as x.

Evaluation manufacturing example 1
Evaluation Production Example and Comparative Evaluation Production Example were produced in the same manner as in Example 1-1 except that the components were changed as shown in the table below.

<Manufacturing of copper-clad laminate (2) by electroless copper plating>
A copper-clad laminate was produced by electroless copper plating on an adhesive sheet obtained by the same method as in Example 2 using the composition of the evaluation production example in the following step.
(1) Solvent degreasing: 60 ° C, 2 minutes (Cleaner 160, manufactured by Meltex Co., Ltd.)
(2) Predip: 20 ° C, 2 minutes (3) Electroless copper plating: 50 ° C, 10 minutes (copper sulfate 0.04 mol / L, EDTA 0.25 mol / L, formalin 0.13 mol / L, triphenylphosphine 2 ppm )
(4) Washing with water: 20 ° C., 2 minutes (5) Drying, thickness of copper-plated part after drying is 5 μm

<Manufacturing 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 (trade name "F2-WS", manufactured by Furukawa Circuit Foil Co., Ltd., 18 μm thickness) with a gap coater so that the thickness after drying was 5 μm. Then, it was dried at 180 ° C. for 2 hours to obtain a copper foil with resin.
A copper-clad laminate was produced by vacuum copper plating (sputtering) on the resin-attached copper foil in the following steps.
(1) Plasma treatment: After evacuating until the pressure in the vacuum apparatus became 1 × 10 ^-4 Pa or less, argon gas was introduced to set the pressure in the apparatus to 0.3 Pa, and plasma treatment was performed.
(2) Sputtering: UHSP-OP2060 (manufactured by Shimadzu Corporation) was used. (3) Electrocopper plating: Electrocopper plating (plating solution: copper sulfate solution) was performed at a current density of 2 A / dm ² .

Evaluation Example 1: Adhesiveness Test The obtained copper-clad laminate was measured in peeling strength (N / mm) at room temperature according to JIS C 6481 (copper-clad laminate test method for flexible printed wiring boards).

Evaluation manufacturing example 2
Evaluation Production Example and Comparative Evaluation Production Example were produced in the same manner as in Example 1-1 except that the components were changed as shown in the table below.

Takenate D-204EA-1: Isocyanurate of toluene diisocyanate (manufactured by Mitsui Chemicals, Inc.)
Component E103D: Silane-modified epoxy resin (manufactured by Arakawa Chemical Industry Co., Ltd.)
Coronate HXR: Hexamethylene diisocyanate isocyanurate (manufactured by Tosoh Corporation)

Evaluation example 2
The compositions of Evaluation Production Example 2-1 to 2-5 and Comparative Evaluation Production Example 2-1 were applied to a commercially available electrolytic copper foil (trade name "F2-WS", manufactured by Furukawa Circuit Foil Co., Ltd., 18 μm thickness). A copper foil with resin was obtained by applying with a gap coater so that the thickness after drying was 20 μm, and then drying at 150 ° C. for 5 minutes and then at 180 ° C. for 120 minutes.

Blocking test By making the resin surface of the obtained copper foil with resin and the resin surface of another obtained copper foil with resin in contact with each other and heating and pressing under the conditions of pressure 2.5 MPa, 180 ° C. and 90 seconds. , A copper-clad laminate was produced.
A sample whose pressed surface can be easily peeled off is marked with ◯, and a sample which cannot be peeled off is marked with x.

Solder heat resistance test (without pre-drying)
After curing, the copper-clad laminate was floated in a solder bath at 288 ° C. with the copper foil side down for 30 seconds, and the presence or absence of a change in appearance was confirmed without pre-drying. When there was no change, it was marked as ◯, and when there was foaming or swelling, it was marked as x.

Claims (13)

A composition comprising one or more selected from the group consisting of a polyimide, which is a reaction product of a group of monomers containing an aromatic tetracarboxylic dianhydride and a dimer diamine, and a polyisocyanate, a trimertriamine, and a silane-modified epoxy resin. A reaction product of polyimide which is a reaction product of a monomer group containing an aromatic tetracarboxylic dianhydride and a dimer diamine and one or more selected from the group consisting of polyisocyanate, trimertriamine, and a silane-modified epoxy resin. An adhesive containing the composition, cross-linking agent and organic solvent according to claim 1. A film-like adhesive comprising a heat-cured product of the composition according to claim 1 and / or a heat-cured product of the adhesive according to claim 3. An adhesive layer comprising one or more selected from the group consisting of the composition according to claim 1, the adhesive according to claim 3, and the film-like adhesive according to claim 4. An adhesive sheet comprising the adhesive layer and support film according to claim 5. A copper foil with a resin, which comprises the adhesive layer and the copper foil according to claim 5. A copper-clad laminate comprising one or more selected from the group consisting of the adhesive sheet according to claim 6 and / or the copper foil with resin according to claim 7 and the copper foil, an insulating sheet and a support film. A copper-clad laminate having a copper plating layer on the adhesive sheet according to claim 6 or the copper foil with resin 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 wiring board having a circuit pattern on the copper foil surface of the copper-clad laminate according to claim 8. Printed wiring board (1) or printed circuit board (1),
The adhesive layer according to claim 5 and a printed wiring board (2) or a printed circuit board (2) are included.
Multi-layer wiring board. A method for manufacturing a multilayer wiring board including the following steps 1 and 2.
Step 1: One or more selected from the group consisting of the adhesive according to claim 3, the film-like adhesive according to claim 4, and the adhesive sheet according to claim 6.
Process of manufacturing a base material with an adhesive layer by contacting at least one side of a printed wiring board (1) or a printed circuit board (1) Step 2: A printed wiring board (2) is placed on the base material with an adhesive layer. Alternatively, a process of laminating printed circuit boards (2) and crimping them under heating and pressure.