CN112011308A

CN112011308A - Composition, adhesive material, adhesive layer, adhesive sheet, copper foil, copper-clad laminate, wiring board, and method for producing same

Info

Publication number: CN112011308A
Application number: CN202010474829.0A
Authority: CN
Inventors: 杦本启辅; 山口贵史; 盐谷淳; 田崎崇司
Original assignee: Arakawa Chemical Industries Ltd
Current assignee: Arakawa Chemical Industries Ltd
Priority date: 2019-05-31
Filing date: 2020-05-29
Publication date: 2020-12-01
Anticipated expiration: 2040-05-29
Also published as: TW202110947A; KR102659897B1; TWI810459B; CN112011308B; KR20200138669A; JP2020196876A; JP7283441B2

Abstract

The invention relates to a composition, an adhesive material, an adhesive layer, an adhesive sheet, a copper foil, a copper-clad laminate, a wiring board and a method for manufacturing the same. The invention provides a composition, a reaction product, an adhesive, a film-shaped adhesive material, an adhesive layer, an adhesive sheet, a copper foil with resin, a copper-clad laminate, a printed wiring board, a multilayer wiring board, and a method for manufacturing the same. Provided is a composition comprising a polyimide which is a reaction product of a monomer group containing an aromatic tetracarboxylic anhydride and a dimer diamine, and one or more selected from the group consisting of a polyisocyanate, a trimer triamine, and a silane-modified epoxy resin.

Description

Composition, adhesive material, adhesive layer, adhesive sheet, copper foil, copper-clad laminate, wiring board, and method for producing same

Technical Field

The present invention relates to a composition, a reaction product, an adhesive, a film-like adhesive material, an adhesive layer, an adhesive sheet, a copper foil with resin, a copper-clad laminate, a printed wiring board, and a multilayer wiring board and a method for producing the same.

Background

Various known resins are used for manufacturing mobile communication devices such as mobile phones and smartphones, base station devices thereof, network-related electronic devices such as servers and routers, printed wiring boards included in large-sized computers, and the like.

Disclosure of Invention

Problems to be solved by the invention

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

Further, the composition used in the production of a printed wiring board is required to have good solder heat resistance when subjected to preliminary drying.

The present invention addresses the problem of providing a composition having a low dielectric constant and a low dielectric loss tangent and having good solder heat resistance when subjected to pre-drying.

Means for solving the problems

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

The present invention provides the following items.

(item 1)

A composition, comprising:

a polyimide that is a reaction product of a monomer group containing an aromatic tetracarboxylic anhydride and a dimer diamine; and

one or more selected from the group consisting of polyisocyanates, triamines, and silane-modified epoxy resins.

(item 2)

A reaction product of polyimide, which is a reaction product of a monomer group containing aromatic tetracarboxylic anhydride and dimer diamine, and one or more selected from the group consisting of polyisocyanate, triamine and silane-modified epoxy resin.

(item 3)

An adhesive comprising the composition of the above item, a crosslinking agent and an organic solvent.

(item 4)

A film-like adhesive material comprising a heat-cured product of the composition described in the above item and/or a heat-cured product of the adhesive described in the above item.

(item 5)

An adhesive layer comprising one or more selected from the group consisting of the composition described in the above item, the adhesive described in the above item, and the film-like adhesive material described in the above item.

(item 6)

An adhesive sheet comprising the adhesive layer described in the above item and a support film.

(item 7)

A copper foil with resin, comprising the adhesive layer and the copper foil.

(item 8)

A copper-clad laminate comprising:

the adhesive sheet according to the above item and/or the resin-attached copper foil according to the above item; and

at least one selected from the group consisting of copper foil, insulating sheet and support film.

(item 9)

A copper-clad laminate having a copper-clad layer on the adhesive sheet or the resin-coated copper foil described in the above item.

(item 10)

The copper-clad laminate as described in the above item, wherein the copper-clad layer is an electroless copper-clad layer or a vacuum copper-clad layer.

(item 11)

A printed wiring board having a circuit pattern on a copper foil surface of the copper-clad laminate described in the above item.

(item 12)

A multilayer wiring board, comprising:

a printed wiring board (1) or a printed circuit board (1);

the adhesive layer described in the above item; and

a printed wiring board (2) or a printed circuit board (2).

(item 13)

A method of manufacturing a multilayer wiring board, comprising the following steps 1 and 2:

step 1: a step of obtaining a base material with an adhesive layer by bringing at least one or more selected from the group consisting of the adhesive described in the above item, the film-like adhesive material described in the above item, and the adhesive sheet described in the above item into contact with at least one surface of a printed wiring board (1) or a printed circuit board (1);

and a step 2: and a step of laminating a printed wiring board (2) or a printed wiring board (2) on the base material with the adhesive layer and pressing the same under heat and pressure.

In the present invention, one or more of the above-described features may be provided in further combination in addition to the combinations explicitly described.

Effects of the invention

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

Detailed Description

Throughout the specification of the present invention, ranges of numerical values such as physical property values and contents may be appropriately set (for example, selected from upper and lower limits described in the following items). Specifically, as for the numerical value α, when the upper limit and the lower limit of the numerical value α are exemplified by a1, a2, A3, A4 (a 1 > a2 > A3 > A4), etc., the range of the numerical value α may be exemplified by a1 or less, 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, A3 to A4, etc.

[ composition ]

The present invention provides a composition comprising a polyimide which is a reaction product of a monomer group containing an aromatic tetracarboxylic anhydride and a dimer diamine, and one or more selected from the group consisting of a polyisocyanate, a trimer triamine and a silane-modified epoxy resin.

< polyimide >

The polyimide is a reaction product containing a monomer group including an acid anhydride such as an aromatic tetracarboxylic acid anhydride and a diamine such as a dimer diamine. The polyimide may be used alone or in combination of two or more.

< aromatic tetracarboxylic anhydride >

The aromatic tetracarboxylic anhydride may be used alone or in combination of two or more. Examples of the aromatic tetracarboxylic anhydride include symmetrical aromatic tetracarboxylic anhydrides.

(symmetrical aromatic tetracarboxylic acid anhydride)

In the present invention, the term "symmetrical aromatic tetracarboxylic anhydride" refers to an aromatic tetracarboxylic anhydride having an axis of symmetry (e.g., C2 axis of symmetry) in the molecule. Examples of the symmetrical aromatic tetracarboxylic anhydride include symmetrical aromatic tetracarboxylic anhydrides represented by the following general formulae.

(wherein X represents a single bond or-SO₂-、-CO-、-O-、-O-C₆H₄-C(CH₃)₂-C₆H₄-O-、-COO-(CH₂)_p-OCO-or-COO-H₂C-HC(-O-C(＝O)-CH₃)-CH₂-OCO-, p represents an integer of 1 to 20. )

Examples of the symmetric aromatic tetracarboxylic acid anhydride represented by the above general formula include 3,3 ', 4, 4' -biphenyltetracarboxylic acid dianhydride, 3,3 ', 4, 4' -diphenylsulfonetetracarboxylic acid dianhydride, 3,3 ', 4, 4' -benzophenonetetracarboxylic acid dianhydride, 3,3 ', 4, 4' -diphenylethertetracarboxylic acid dianhydride, 4,4 '- [ propane-2, 2-diylbis (1, 4-phenyleneoxy) ] bisphthalic acid dianhydride, 2-bis (3, 3', 4,4 '-tetracarboxyphenyl) tetrafluoropropane dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, 2' -bis (3, 4-dicarboxyphenoxyphenyl) sulfone dianhydride, 2 ', 3, 3' -biphenyltetracarboxylic acid dianhydride, 2, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, pyromellitic dianhydride, 1,2,3, 4-benzenetetracarboxylic anhydride, 1,4,5, 8-naphthalenetetracarboxylic anhydride, 2,3,6, 7-naphthalenetetracarboxylic anhydride, and the like.

Among the symmetric aromatic tetracarboxylic acid anhydrides, at least one selected from the group consisting of 3,3 ', 4, 4' -benzophenonetetracarboxylic dianhydride, 4,4 '- [ propane-2, 2-diylbis (1, 4-phenyleneoxy) ] bisphthalic dianhydride and 4, 4' -oxydiphthalic anhydride is preferable from the viewpoint of compatibility of the aromatic tetracarboxylic acid anhydride with diamine, room temperature adhesiveness, heat-resistant adhesiveness and the like.

Examples of the upper limit and the lower limit of the content of the symmetric aromatic tetracarboxylic anhydride in 100 mol% of the aromatic tetracarboxylic anhydride include 100 mol%, 90 mol%, 80 mol%, 70 mol%, 60 mol%, 55 mol%, 50 mol%, 40 mol%, 30 mol%, 20 mol%, 10 mol%, 0 mol%. In one embodiment, the content of the symmetrical aromatic tetracarboxylic anhydride in 100 mol% of the aromatic tetracarboxylic anhydride is preferably from about 0 mol% to about 100 mol%, more preferably from about 50 mol% to about 100 mol%.

Examples of the upper limit and the lower limit of the content of the symmetric aromatic tetracarboxylic anhydride in 100 mass% of the aromatic tetracarboxylic anhydride include 100 mass%, 90 mass%, 80 mass%, 70 mass%, 60 mass%, 55 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass%, 10 mass%, 0 mass%, and the like. In one embodiment, the content of the symmetrical aromatic tetracarboxylic anhydride in 100% by mass of the aromatic tetracarboxylic anhydride is preferably from about 0% by mass to about 100% by mass, more preferably from about 50% by mass to about 100% by mass.

Examples of the upper limit and the lower limit of the content of the symmetric aromatic tetracarboxylic anhydride in 100 mol% of the monomer group include 75 mol%, 70 mol%, 60 mol%, 50 mol%, 40 mol%, 30 mol%, 20 mol%, 10 mol%, 5 mol%, 0 mol% and the like. In one embodiment, the content of the symmetrical aromatic tetracarboxylic anhydride in 100 mol% of the monomer group is preferably from about 0 mol% to about 75 mol%.

Examples of the upper limit and the lower limit of the content of the symmetric aromatic tetracarboxylic anhydride in 100% by mass of the monomer group include 75% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, and 0% by mass. In one embodiment, the content of the symmetrical aromatic tetracarboxylic anhydride in 100% by mass of the monomer group is preferably from about 0% by mass to about 75% by mass.

(other aromatic tetracarboxylic acid anhydrides)

In one embodiment, the monomer group may contain an aromatic tetracarboxylic anhydride (also referred to as other aromatic tetracarboxylic anhydride) which is neither the above-described tetracarboxylic anhydride containing a fluorene skeleton nor a symmetric aromatic tetracarboxylic anhydride.

In one embodiment, the content of the other acid anhydride in 100 mol% of the aromatic tetracarboxylic anhydride may be, for example, less than 5 mol%, less than 4 mol%, less than 1 mol%, less than 0.9 mol%, less than 0.5 mol%, less than 0.1 mol%, or about 0 mol%.

In one embodiment, the content of the other acid anhydride in 100% by mass of the aromatic tetracarboxylic anhydride may be, for example, less than 5% by mass, less than 4% by mass, less than 1% by mass, less than 0.9% by mass, less than 0.5% by mass, less than 0.1% by mass, or about 0% by mass.

In one embodiment, the content of the other acid anhydride in 100 mol% of the monomer group may be exemplified by less than 5 mol%, less than 4 mol%, less than 1 mol%, less than 0.9 mol%, less than 0.5 mol%, less than 0.1 mol%, about 0 mol%, and the like.

In one embodiment, the content of the other acid anhydride in 100% by mass of the monomer group may be exemplified by less than 5% by mass, less than 4% by mass, less than 1% by mass, less than 0.9% by mass, less than 0.5% by mass, less than 0.1% by mass, about 0% by mass, and the like.

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

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

< diamine >

The diamine may be used alone or in combination of two or more. Examples of the diamine include dimer diamine, carboxyl group-containing diamine, and diamino polysiloxane.

(dimer diamine)

In the present invention, the dimer diamine is obtained by substituting all carboxyl groups of a dimer acid which is a dimer of an unsaturated fatty acid such as oleic acid with primary amino groups (see, for example, japanese patent application laid-open No. 9-12712), and various known dimer diamines can be used without particular limitation. Hereinafter, a non-limiting general formula of the dimer diamine is shown (in each formula, m + n is preferably 6 to 17, p + q is preferably 8 to 19, and the dotted line portion represents a carbon-carbon single bond or a carbon-carbon double bond).

Commercially available dimer diamine includes バ - サミン 551(コグニクスジャパン), バ - サミン 552(コグニクスジャパン; バ - サミン 551 hydride), PRIAMINE1075 and PRIAMINE1074 (all manufactured by Kagaku Kogyo Co., Ltd.).

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

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

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

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

(aromatic diamine)

In one embodiment, the aromatic diamine is represented by the following general formula.

(wherein Y represents a single bond, -SO₂-、-CO-、-O-、-O-C₆H₄-O-、-O-C₆H₄-C(CH₃)₂-C₆H₄-O-、-COO-(CH₂)_q-OCO-, or-COO-H₂C-HC(-O-C(＝O)-CH₃)-CH₂-OCO-, q represents an integer of 1 to 20. )

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

The upper limit of the content of the aromatic diamine in 100 mol% of the diamine may be, for example, 80 mol%, 70 mol%, 60 mol%, 50 mol%, 40 mol%, 30 mol%, 25 mol%, etc., and the lower limit thereof may be, for example, 75 mol%, 70 mol%, 60 mol%, 50 mol%, 40 mol%, 30 mol%, 25 mol%, 20 mol%, etc. In one embodiment, the content of the aromatic diamine in 100 mol% of the diamine is preferably 20 to 80 mol% from the viewpoints of solvent solubility, workability, and flexibility.

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

Examples of the upper limit of the content of the aromatic diamine in 100 mol% of the monomer group include 50 mol%, 40 mol%, 30 mol%, 20 mol%, 10 mol%, 8 mol%, etc., and examples of the lower limit thereof include 40 mol%, 30 mol%, 20 mol%, 10 mol%, 8 mol%, 5 mol%, etc. In one embodiment, the content of the aromatic diamine in 100 mol% of the monomer group is preferably 5 to 50 mol%.

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

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

(diaminopolysiloxane)

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

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

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

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

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

(other diamines)

In one embodiment, the monomer group may contain a diamine other than those described above (also referred to as other diamines). Examples of the other diamines include alicyclic diamines, bisaminophenoxyphenylpropane, diaminodiphenyl ether, phenylenediamine, diaminodiphenyl sulfide, diaminodiphenyl sulfone, diaminobenzophenone, diaminodiphenylmethane, diaminophenylpropane, diaminophenylhexafluoropropane, diaminophenylphenylethane, bisaminophenoxybenzene, bisaminobenzoylbenzene, bisaminodimethylbenzylbenzene, bisaminobistrifluoromethylbenzylbenzene, aminophenoxybiphenyl, aminophenoxyphenylketone, aminophenoxyphenylsulfide, aminophenoxyphenylsulfone, aminophenoxyphenylether, aminophenoxyphenylpropane, 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 ' -bis [ aminophenoxyphenoxy ] diphenylsulfone, diaminodiaryloxybenzophenone, diaminoaryloxybenzophenone, 6 ' -bis (aminoaryloxy) -3,3,3 ', 3 ' -tetramethyl-1, 1 ' -spirobiindane, bis (aminoalkyl) ether, bis (aminoalkoxyalkyl) ether, bis (aminoalkoxy) alkane, bis [ (aminoalkoxy) alkoxy ] alkane, (poly) ethylene glycol bis (aminoalkyl) ether, bis (aminoaryloxy) pyridine, alkylenediamine, and the like.

Examples of the alicyclic diamine include 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' -diaminodicyclohexylmethane, and 1, 3-bisaminomethylcyclohexane.

Examples of bisaminophenoxyphenylpropane 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.

The phenylenediamine may, for example, be a phenylenediamine such as p-phenylenediamine or 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 ' -diaminobenzophenone, and 3,4 ' -diaminobenzophenone.

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

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

Examples of the diaminophenylhexafluoropropane include 2, 2-bis (3-aminophenyl) -1,1,1,3,3, 3-hexafluoropropane, 2-bis (4-aminophenyl) -1,1,1,3,3, 3-hexafluoropropane and 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3, 3-hexafluoropropane.

Examples of the diaminophenylphenylethane include 1, 1-bis (3-aminophenyl) -1-phenylethane, 1-bis (4-aminophenyl) -1-phenylethane and 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane.

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

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

Examples of the bisaminodimethylbenzyl benzene include 1, 3-bis (3-amino- α, α -dimethylbenzyl) benzene, 1, 3-bis (4-amino- α, α -dimethylbenzyl) benzene, 1, 4-bis (3-amino- α, α -dimethylbenzyl) benzene, and 1, 4-bis (4-amino- α, α -dimethylbenzyl) benzene.

Examples of the bisaminobistrifluoromethylbenzyl benzene include 1, 3-bis (3-amino- α, α -bistrifluoromethylbenzyl) benzene, 1, 3-bis (4-amino- α, α -bistrifluoromethylbenzyl) benzene, 1, 4-bis (3-amino- α, α -bistrifluoromethylbenzyl) benzene, 1, 4-bis (4-amino- α, α -bistrifluoromethylbenzyl) benzene, and the like.

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

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, bis [4- (4-aminophenoxy) phenyl ] sulfide and the like.

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.

Examples of the aminophenoxyphenylpropane include 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane, 2-bis [3- (3-aminophenoxy) phenyl ] -1,1,1,3,3, 3-hexafluoropropane, and 2, 2-bis [4- (4-aminophenoxy) phenyl ] -1,1,1,3,3, 3-hexafluoropropane.

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

Examples of bis (aminophenoxy- α, α -dimethylbenzyl) benzene include 1, 3-bis [4- (3-aminophenoxy) - α, α -dimethylbenzyl ] benzene, 1, 3-bis [4- (4-aminophenoxy) - α, α -dimethylbenzyl ] benzene, 1, 4-bis [4- (3-aminophenoxy) - α, α -dimethylbenzyl ] benzene, and 1, 4-bis [4- (4-aminophenoxy) - α, α -dimethylbenzyl ] benzene.

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

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

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

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

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

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

Examples of 6,6 '-bis (aminoaryloxy) -3,3, 3', 3 '-tetramethyl-1, 1' -spirobiindane include 6,6 '-bis (3-aminophenoxy) -3,3, 3', 3 '-tetramethyl-1, 1' -spirobiindane, 6 '-bis (4-aminophenoxy) -3,3, 3', 3 '-tetramethyl-1, 1' -spirobiindane, and the like.

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

Examples of the bis (aminoalkoxyalkyl) ether include bis [2- (aminomethoxy) ethyl ] ether, bis [2- (2-aminoethoxy) ethyl ] ether, and bis [2- (3-aminopropoxy) ethyl ] ether.

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

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

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

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

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

In one embodiment, the content of the other diamine in 100 mol% of the diamine may be, for example, less than 5 mol%, less than 4 mol%, less than 1 mol%, less than 0.9 mol%, less than 0.5 mol%, less than 0.1 mol%, or about 0 mol%.

In one embodiment, the content of the other diamine in 100% by mass of the diamine may be exemplified by less than 5% by mass, less than 4% by mass, less than 1% by mass, less than 0.9% by mass, less than 0.5% by mass, less than 0.1% by mass, about 0% by mass, and the like.

In one embodiment, the content of the other diamine in 100 mol% of the monomer group may be exemplified by less than 5 mol%, less than 4 mol%, less than 1 mol%, less than 0.9 mol%, less than 0.5 mol%, less than 0.1 mol%, about 0 mol%, and the like.

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

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

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

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

Examples of the upper limit and the lower limit of the mass ratio of the aromatic tetracarboxylic anhydride to the diamine [ aromatic tetracarboxylic anhydride/diamine ] include 1.5, 1.4, 1.2, 1.0, 0.9, 0.7, 0.6, 0.5 and the like. In one embodiment, the mass ratio of the aromatic tetracarboxylic anhydride to the diamine [ aromatic tetracarboxylic anhydride/diamine ] is preferably 0.5 to 1.5.

< other monomers >

In one embodiment, the monomer set may contain monomers (also referred to as other monomers) that are neither aromatic tetracarboxylic anhydrides nor diamines. Examples of the other monomer include aliphatic tetracarboxylic acid anhydrides.

In one embodiment, the content of the other monomer in the monomer group may be exemplified by less than 5 mol%, less than 4 mol%, less than 1 mol%, less than 0.9 mol%, less than 0.5 mol%, less than 0.1 mol%, about 0 mol%, and the like.

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

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

< physical Properties of polyimide, etc. >

Examples of the upper limit and the lower limit of the weight average molecular weight of the polyimide include 50000, 40000, 30000, 20000, 10000, 7500, 5500, and 5000. In one embodiment, the polyimide preferably has a weight average molecular weight of 5000 to 50000 in terms 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 include 40000, 30000, 20000, 10000, 7500, 5000, 3000, 2000 and the like. In one embodiment, the polyimide preferably has a number average molecular weight of 2000 to 40000 from the viewpoints of dielectric properties, solvent solubility, and flexibility.

The weight average molecular weight and the number average molecular weight can be determined as values converted to polystyrene measured by Gel Permeation Chromatography (GPC), for example.

Examples of the upper and lower limits of the softening point of the polyimide include 220 ℃, 200 ℃, 150 ℃, 100 ℃, 50 ℃, 25 ℃, 20 ℃ and the like. In one embodiment, the softening point of the polyimide is preferably 20 to 220 ℃ from the viewpoints of workability, heat resistance, and solvent solubility.

The softening point can be obtained by using a commercially available measuring instrument ("ARES-2 KSTD-FCO-STD", manufactured by Rheometric Scientific Co., Ltd.).

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

The acid value can be determined by JIS K0070: 1992, the procedures described in the specification.

< method for producing polyimide, etc. >

The polyimide can be produced by various known methods. The method for producing polyimide may be exemplified by: comprising a step of obtaining an addition polymer by subjecting a monomer group containing an aromatic tetracarboxylic acid anhydride and a diamine such as a dimer diamine to an addition polymerization reaction at a temperature of preferably from about 60 ℃ to about 120 ℃, more preferably from about 80 ℃ to about 100 ℃, for preferably from about 0.1 hour to about 2 hours, more preferably from about 0.1 hour to about 0.5 hour; and a step of subjecting the resulting addition polymer to an imidization reaction, i.e., a dehydration ring-closure reaction, at a temperature of preferably about 80 to about 250 ℃ and more preferably about 100 to about 200 ℃ for preferably about 0.5 to about 50 hours and more preferably about 1 to about 20 hours.

In the step of conducting the imidization reaction, various known reaction catalysts, dehydrating agents and organic solvents described later can be used. The various known reaction catalysts, dehydrating agents and organic solvents described later may be used singly 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-closing ratio of the polyimide is not particularly limited. The "imide ring-closure ratio" refers to the content of cyclic imide bonds in polyimide, and can be determined by various spectroscopic methods such as NMR and IR analysis. The imide ring-closing ratio of the polyimide is preferably about 70% or more, and more preferably about 85% to about 100%, from the viewpoint of improving the room-temperature adhesiveness and the heat-resistant adhesiveness.

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

Examples of the upper limit and the lower limit of the content of one or more selected from the group consisting of polyisocyanate, triamine and silane-modified epoxy resin in 100% by mass of the composition include 50% by mass, 45% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 2% by mass, 1% by mass, 0.5% by mass, 0.2% by mass, 0.1% by mass and the like. In one embodiment, the content of one or more selected from the group consisting of polyisocyanate, triamine and 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 the polyimide to one or more selected from the group consisting of polyisocyanate, triamine and silane-modified epoxy resin (polyimide/one or more selected from the group consisting of polyisocyanate, triamine and silane-modified epoxy resin) may be exemplified by 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 and the like. In one embodiment, the mass ratio of the polyimide to one or more selected from the group consisting of polyisocyanate, triamine and silane-modified epoxy resin (polyimide/one or more selected from the group consisting of polyisocyanate, triamine and silane-modified epoxy resin) is preferably 1 to 1000.

< polyisocyanate >

In the present invention, the "polyisocyanate" refers to a compound having 2 or more isocyanate groups (-N ═ C ═ O). Examples of the polyisocyanate include a linear aliphatic polyisocyanate, a branched aliphatic polyisocyanate, an alicyclic polyisocyanate, an aromatic polyisocyanate, and biuret, isocyanurate, allophanate, and adduct thereof. 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 and the like. The linear alkylene group is represented by the general formula: - (CH)₂)_n(n is an integer of 1 or more). Examples of the linear alkylene group include 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, and an n-decylene group.

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

Examples of the branched aliphatic group include a branched alkylene group and the like. Branched alkylene is a group in which at least 1 hydrogen atom of a linear alkylene group is substituted with an alkyl group. Examples of the branched alkylene group include diethylpentylene, trimethylbutylene, trimethylpentylene, trimethylhexylene (trimethylhexamethylene), and the like.

Examples of the branched aliphatic polyisocyanate include diethylpentamethylenediisocyanate, trimethylbutylenediisocyanate, trimethylpentamethylenediisocyanate, trimethylhexamethylenediisocyanate, and the like.

Examples of the alicyclic group include cycloalkylene and the like. Examples of the cycloalkylene group include monocyclic cycloalkylene group, bridged cycloalkylene group, fused cycloalkylene group and the like. In addition, in the cycloalkylene group, 1 or more hydrogen atoms may be substituted with a straight-chain or branched-chain alkyl group.

In the present invention, a monocyclic ring refers to a cyclic structure formed by covalent bonds of carbon and having no internal bridge structure. In addition, a fused ring refers to a cyclic structure in which 2 or more monocyclic rings share 2 atoms (i.e., only 1 side of each ring shares (is fused) with each other). A bridged ring is a cyclic structure in which 2 or more monocyclic rings share 3 or more atoms.

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

Examples of the bridged cycloalkylene group include tricyclodecylene, adamantylene, norbornylene and the like.

Examples of the fused ring cycloalkylene group include bicyclodecenylene and the like.

Examples of the alicyclic polyisocyanate include monocyclic alicyclic polyisocyanate, bridged alicyclic polyisocyanate, and condensed alicyclic polyisocyanate.

Examples of the monocyclic alicyclic polyisocyanate include hydrogenated xylene diisocyanate, isophorone diisocyanate, cyclopentylene diisocyanate, cyclohexylene diisocyanate, cycloheptylene diisocyanate, cyclodecylene diisocyanate, 3,5, 5-trimethylcyclohexylene diisocyanate, dicyclohexylmethane diisocyanate and the like.

Examples of the bridged alicyclic polyisocyanate include tricyclodecanediisocyanate, adamantane diisocyanate, norbornane diisocyanate and the like.

Examples of the fused ring alicyclic polyisocyanate include dicyclodedecylidene diisocyanate and the like.

Examples of the aromatic group include monocyclic aromatic group and fused ring aromatic group. In addition, in the aromatic group, 1 or more hydrogen atoms may be substituted with a linear or branched alkyl group.

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

Examples of the aromatic polyisocyanate include monocyclic aromatic polyisocyanate and fused aromatic polyisocyanate.

Examples of the monocyclic aromatic polyisocyanate include dialkyldiphenylmethane diisocyanate such as 4,4 '-diphenyldimethylmethane diisocyanate, tetraalkyldiphenylmethane diisocyanate such as 4, 4' -diphenyltetramethylmethane diisocyanate, 4 '-diphenylmethane diisocyanate, 4' -dibenzyl isocyanate, 1, 3-phenylene diisocyanate, 1, 4-phenylene diisocyanate, toluene diisocyanate, xylylene diisocyanate, and m-tetramethylxylylene diisocyanate.

Examples of the fused aromatic polyisocyanate include 1, 5-naphthalene diisocyanate and the like.

The biuret product of the polyisocyanate may be exemplified by a compound represented by the following structural formula.

[ in the formula, n^bIs an integer of 1 or more, R^bA～R^bEEach independently is alkylene, arylene, or a combination of alkylene and arylene, R^bα～R^bβEach independently is an isocyanate group or

(n^b1Is an integer of 0 or more, R^b1～R^b5Each independently is alkylene, arylene, or a combination of alkylene and arylene, R^b’～R^b"are each independently an isocyanate group or R^bα～R^bβA group per se. R^b4～R^b5、R^b"the groups may be different in each constituent unit. ).

R^bD～R^bE、R^bβThe groups may be different in each constituent unit.]

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

The alkylenearylenealkylene group being-R^alkylene-R^arylene-R^alkylene- (in the formula, R^alkyleneRepresents an alkylene group, R^aryleneRepresents an arylene group).

Examples of the biuret products of the polyisocyanates include デュラネート 24A-100, デュラネート 22A-75P, デュラネート 21S-75E (manufactured by Asahi Kasei Co., Ltd.), デスモジュール N3200A (biuret product of hexamethylene diisocyanate) (manufactured by Sumitomo バイエルウレタン Co., Ltd.).

The isocyanurate compound of the polyisocyanate may be exemplified by a compound represented by the following structural formula.

[ in the formula, nⁱIs an integer of 0 or more, R^iA～R^iEEach independently is alkylene, arylene, or a combination of alkylene and arylene, R^iα～R^iβEach independently is an isocyanate group or

(nⁱ¹Is an integer of 0 or more, Rⁱ¹～Rⁱ⁵Each independently is alkylene, arylene, or a combination of alkylene and arylene, Rⁱ’～Rⁱ"are each independently an isocyanate group or R^iα～R^iβA group per se. Rⁱ⁵、Rⁱ"the groups may be different in each constituent unit. ).

R^iD～R^iE、R^iβThe groups may be different in each constituent unit.]

The isocyanurate body of the polyisocyanate may be exemplified by デュラネート TPA-100, デュラネート TKA-100, デュラネート MFA-75B, デュラネート MHG-80B (manufactured by Asahi Kasei Co., Ltd.), コロネート HXR (isocyanurate body of hexamethylene diisocyanate) (manufactured by Tosoh Kasei Co., Ltd.), タケネート D-131N (isocyanurate of xylylene diisocyanate), タケネート D204EA-1 (isocyanurate of tolylene diisocyanate), タケネート D-127N (isocyanurate of hydrogenated xylylene diisocyanate) (manufactured by Mitsui chemical Co., Ltd.), VESTANAT T1890/100 (isocyanurate of isophorone diisocyanate) (manufactured by Nippon corporation, Ltd.), and the like.

Examples of the allophanate of the polyisocyanate include compounds represented by the following structural formulae.

[ in the formula, n^aIs an integer of 0 or more, R^aAIs alkyl or aryl, R^aB～R^aGEach independently is alkylene, arylene, or a combination of alkylene and arylene, R^aα～R^aγEach independently is an isocyanate group or

(n^a1Is an integer of 0 or more, R^a1～R^a6Each independently being alkylene or arylene, R^a’～R^a"' are each independently an isocyanate group or R^aα～R^aγA group per se. R^a1～R^a4、R^a’～R^a"' the groups may be different in each constituent unit. ).

R^aB～R^aE、R^aα～R^aγThe groups may be different in each constituent unit.]

Examples of commercially available allophanate products of polyisocyanates include タケネート D-178N (manufactured by Mitsui chemical Co., Ltd.).

The adduct of polyisocyanate may be exemplified by:

an adduct of trimethylolpropane and polyisocyanate represented by the following structural formula,

[ in the formula, n^adIs an integer of 0 or more, R^adA～R^adEEach independently is alkylene, arylene, or a combination of alkylene and arylene, R^ad1～R^ad2Each independently is

(in the formula, n^ad’Is an integer of 0 or more, R^ad’～R^ad"independently of one another are alkylene, arylene or a combination of alkylene and arylene, R^ad”^’Is R^ad1～R^ad2Radical of itself, R^ad’～R^ad”^’The groups may be different in each constituent unit. ),

R^adD～R^adE、R^ad2the groups may be different in each constituent unit.]；

An adduct of glycerin and a polyisocyanate represented by the following structural formula,

[ in the formula, n^ad1Is an integer of 0 or more, R^adα～R^adEach independently being alkylene or arylene, R^adA～R^adBEach independently is

(in the formula, n^ad1’Is an integer of 0 or more, R^ad’～R^ad’Each independently is alkylene, arylene, or a combination of alkylene and arylene, R^adB’Is R^adA～R^adBRadical of itself, R^ad’～R^ad’、R^adB’The groups may be different in each constituent unit. ),

R^ad～R^adthe groups may be different in each constituent unit.](ii) a And the like.

Examples of the adduct of the polyisocyanate include デュラネート P301-75E (manufactured by Asahi Kasei Co., Ltd.), タケネート D110N, タケネート D160N (manufactured by Mitsui chemical Co., Ltd.), コロネート L (manufactured by Tosoh Kasei Co., Ltd.).

Examples of the upper limit and the lower limit of the content of the polyisocyanate in 100% by mass of the composition include 50% by mass, 45% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 2% by mass, 1% by mass, 0.5% by mass, 0.2% by mass, 0.1% by mass and the like. In one embodiment, the content of the polyisocyanate in 100% by mass of the composition is preferably 0.1 to 50% by mass.

Examples of the upper limit and the lower limit of the mass ratio of polyimide to polyisocyanate (polyimide/polyisocyanate) include 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 and the like. In one embodiment, the mass ratio of the polyimide to the polyisocyanate (polyimide/polyisocyanate) is preferably 1 to 1000.

< Tritriamine >

The trimer is obtained by substituting all carboxyl groups of a trimer acid (see japanese patent publication No. 2013-505345) which is a trimer of an unsaturated fatty acid such as oleic acid with primary amino groups, and various publicly known trimers can be used without particular limitation. The following non-limiting general formula of the trimeric triamines is shown (the dotted line part represents a carbon-carbon single bond or a carbon-carbon double bond, and R represents ethylene (-CH)₂CH₂-) or vinylidene (-CH ═ CH-)).

Examples of commercially available products of the triamine include PRIAMINE1071 (manufactured by Takara Japan K.K.). The content of the triamine component in the commercially available products is usually about 15 to about 20% by mass, and the dimer diamine may be contained in an amount exceeding 80% by mass as the rest.

Examples of the upper limit and the lower limit of the content of the trimeric triamine in 100% by mass of the composition include 50% by mass, 45% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 2% by mass, 1% by mass, 0.5% by mass, 0.2% by mass, 0.1% by mass, and the like. In one embodiment, the content of the triamine in 100% by mass of the composition is preferably 0.1 to 50% by mass.

Examples of the upper limit and the lower limit of the mass ratio of polyimide to triamine (polyimide/triamine) include 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 and the like. In one embodiment, the mass ratio of the polyimide to the triamine is preferably 1 to 1000 (polyimide/triamine).

< silane-modified epoxy resin >

The silane-modified epoxy resin is the reaction product of a hydroxyl-containing epoxy resin and a partial condensate of an alkoxysilane.

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

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

The alkoxysilane partial condensate may be exemplified by the general formula: r¹ _pSi(OR²)_4-p(wherein p is an integer of 0 to 2, R¹Is a substituted or unsubstituted alkyl, aryl or alkenyl group having 6 or less carbon atoms, R²An alkyl group having 6 or less carbon atoms. ) Alkoxysilanes and condensates thereof.

Examples of the alkyl group having 6 or less carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, a neopentyl group, an isopentyl group, a sec-pentyl group, a 3-pentyl group, a tert-pentyl group, a hexyl group, an isohexyl group, a 3-methylpentyl group, a2, 3-dimethylbutyl group and a2, 2-dimethylbutyl group.

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

Examples of the aryl group include phenyl and naphthyl.

Examples of the alkenyl group include vinyl and allyl.

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

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

Examples of the trialkoxysilane include alkyltrialkoxysilanes, aryltrialkoxysilanes, trialkoxysilanes containing functional groups, and the like.

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

Examples of the aryltrialkoxysilane include phenyltrimethoxysilane and phenyltriethoxysilane.

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

Examples of the functional group-containing trialkoxysilane include 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3, 4-epoxycyclohexylethyltrimethoxysilane and 3, 4-epoxycyclohexylethyltrimethoxysilane.

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

The silane-modified epoxy resin is produced by esterifying a hydroxyl group-containing epoxy resin with a partial condensate of alkoxysilane by dealcoholization. Although not particularly limited, the reaction is preferably carried out at a reaction temperature of 50 to 130 ℃ for 1 to 15 hours so that the mass of the alkoxysilane partial condensate in terms of silica (mass ratio) to the mass of the hydroxyl group-containing epoxy resin is 0.01 to 1.2.

Examples of the upper limit and the lower limit of the content of the silane-modified epoxy resin in 100% by mass of the composition include 50% by mass, 45% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, 2% by mass, 1% by mass, 0.5% by mass, 0.2% by mass, 0.1% by mass, and the like. 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.

Examples of the upper limit and the lower limit of the mass ratio of the polyimide to the silane-modified epoxy resin (polyimide/silane-modified epoxy resin) include 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 and the like. In one embodiment, the mass ratio of the polyimide to the 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 or a composition for a plating primer (for example, a composition for a copper plating primer).

[ reaction product ]

The present invention provides a reaction product of a polyimide, which is a reaction product of a monomer group containing an aromatic tetracarboxylic anhydride and a dimer diamine, and at least one selected from the group consisting of polyisocyanates, trimesamines, and silane-modified epoxy resins.

Examples of the aromatic tetracarboxylic anhydride and the like include those described above.

The reaction conditions for producing the reaction product are not particularly limited, and heating and pressure bonding conditions for producing a copper-clad laminate described later can be exemplified.

In one embodiment, the reaction product described above may be used as a thermoplastic polyimide layer, a plating primer layer (e.g., a copper plating primer layer).

[ Adhesives ]

The invention provides an adhesive comprising the composition, a crosslinking agent and an organic solvent.

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

< crosslinking agent >

The crosslinking agent is not particularly limited, and any known crosslinking agent can be used as long as it functions as a crosslinking agent for polyimide. The crosslinking agent may be used alone or in combination of two or more.

Examples of the crosslinking agent include epoxy compounds and benzophenones

Oxazines, bismaleimides, cyanate esters, polyisocyanates, and the like. In one embodiment, the crosslinking agent is preferably selected from the group consisting of epoxy compounds, benzophenones

At least one member selected from the group consisting of oxazines, bismaleimides, and cyanate esters.

(epoxy compound)

Examples of the epoxy compound include phenol novolac type epoxy compounds, cresol novolac type epoxy compounds, bisphenol a type epoxy compounds, bisphenol F type epoxy compounds, bisphenol S type epoxy compounds, hydrogenated bisphenol a type epoxy compounds, hydrogenated bisphenol F type epoxy compounds, stilbene type epoxy compounds, triazine skeleton-containing epoxy compounds, fluorene skeleton-containing epoxy compounds, linear aliphatic epoxy compounds, alicyclic epoxy compounds, glycidyl amine type epoxy compounds, triphenol methane type epoxy compounds, alkyl-modified triphenol methane type epoxy compounds, biphenyl type epoxy compounds, dicyclopentadiene skeleton-containing epoxy compounds, naphthalene skeleton-containing epoxy compounds, arylalkylene type epoxy compounds, tetraglycidyl xylylenediamine, dimer acid-modified epoxy compounds which are dimer acid-modified products of the above epoxy compounds, bisphenol a type epoxy compounds, a bisphenol F type epoxy compounds, a bisphenol a epoxy compounds, a triazine skeleton-containing epoxy compounds, a fluorene skeleton, Dimer acid diglycidyl ester, silane-modified epoxy resin, and the like. Examples of commercially available epoxy compounds include "jER 828", "jER 834" and "jER 807" manufactured by mitsubishi chemical corporation, "ST-3000" manufactured by new hitachi chemical corporation, "セロキサイド 2021P" manufactured by macyol chemical industry co., ltd-172-X75 "manufactured by new hitachi chemical corporation, and" tetra d-X "manufactured by mitsubishi gas chemical corporation. Among them, from the viewpoint of the balance among heat-resistant adhesiveness, moisture-absorbing solder heat resistance, and low dielectric characteristics, at least one selected from the group consisting of bisphenol a type epoxy compounds, bisphenol F type epoxy compounds, hydrogenated bisphenol a type epoxy compounds, and alicyclic epoxy compounds is preferable.

In particular, tetraglycidyl diamine having the following structure has good compatibility with the polyimide. In addition, when this component is used, the loss elastic modulus of the adhesive layer is easily lowered, and the heat-resistant adhesive property and the low dielectric characteristics thereof are also improved.

(wherein Y represents a phenylene group or a cyclohexylene group.)

When an epoxy compound is used as the crosslinking agent, various known curing agents for epoxy compounds may be used in combination. The epoxy compound curing agent may be used alone or in combination of two or more. Examples of the curing agent for epoxy compounds include: anhydride curing agents such as succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexahydrophthalic anhydride, or a mixture of 4-methylhexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyltetrahydrophthalic anhydride, nadic anhydride, methylnadic anhydride, norbornane-2, 3-dicarboxylic anhydride, methylnorbornane-2, 3-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 3-dodecenyl succinic anhydride, octenyl succinic anhydride, and the like; dicyandiamide (DICY), aromatic diamines (trade names "lonzacure m-DEA", "lonzacure m-DETDA", and the like, all of which are manufactured by losa japan), and amine curing agents such as aliphatic amines; phenol curing agents such as phenol novolak resins, cresol novolak resins, bisphenol A novolak resins, triazine-modified phenol novolak resins, phosphazene curing agents such as a phosphazene containing a phenolic hydroxyl group (trade name "SPH-100" manufactured by Otsuka chemical Co., Ltd.), cyclic phosphazene compounds, and rosin crosslinking agents such as maleic acid-modified rosin and hydrogenated products thereof. Among these, phenol curing agents are preferable, and phosphazene curing agents containing a phenolic hydroxyl group are particularly preferable. The amount of the curing agent to be used is not particularly limited, and is preferably from about 0.1 to about 120% by mass, and more preferably from about 10 to about 40% by mass, when the solid content of the adhesive is 100% by mass.

In the case of using an epoxy compound and a curing agent for an epoxy compound in combination as a crosslinking agent, a reaction catalyst may be further used in combination. The reaction catalyst may be used alone or in combination of two or more. The reaction catalyst may be exemplified by: 1, 8-diaza-bicyclo [5.4.0]Tertiary amines such as undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and tris (dimethylaminomethyl) phenol; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole and 2-heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine; tetraphenyl radical

Tetraphenylborate, 2-ethyl-4-methylimidazotetraphenylborate, N-methylmorpholinebetraphenylborate and the likeTetraphenylboron salts and the like. The amount of the reaction catalyst used is not particularly limited, but is preferably from about 0.01% by mass to about 5% by mass, assuming that the solid content of the binder is 100% by mass.

(benzo

Oxazines

Benzo (b) is

Examples of the oxazine include 6,6- (1-methylethylidene) bis (3, 4-dihydro-3-phenyl-2H-1, 3-benzo

Oxazine), 6- (1-methylethylidene) bis (3, 4-dihydro-3-methyl-2H-1, 3-benzo

Oxazines), and the like. It should be noted that, in the following description,

the nitrogen of the oxazine ring may have a phenyl group, a methyl group, a cyclohexyl group, or the like bonded thereto. In addition, benzene

Examples of commercially available oxazines include "benzo" manufactured by four national chemical industries, Ltd

Oxazine F-a type and benzo

And "RLV-100" manufactured by エア & ウォ - タ, and the like, oxazine P-d type.

(bismaleimide)

Examples of bismaleimides include 4,4 ' -diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol a diphenyl ether bismaleimide, 3 ' -dimethyl-5, 5 ' -diethyl-4, 4 ' -diphenylmethane bismaleimide, 4-methyl-1, 3-phenylene bismaleimide, 1,6 ' -bismaleimide- (2,2, 4-trimethyl) hexane, 4 ' -diphenyl ether bismaleimide, and 4,4 ' -diphenylsulfone bismaleimide. Further, examples of commercially available bismaleimides include "BAF-BMI" manufactured by JFE chemical Co.

(cyanate ester)

Cyanate ester includes 2-allylphenol cyanate ester, 4-methoxyphenol cyanate ester, 2-bis (4-cyanatoxyphenol) -1,1,1,3,3, 3-hexafluoropropane, bisphenol A cyanate ester, diallylbisphenol A cyanate ester, 4-phenylphenol cyanate ester, 1,1, 1-tris (4-cyanatophenyl) ethane, 4-cumylphenol cyanate ester, 1, 1-bis (4-cyanatophenyl) ethane, 4' -biphenol cyanate ester, and 2, 2-bis (4-cyanatophenyl) propane. Examples of commercially available cyanate esters include "PRIMASET BTP-6020S (manufactured by Longsha Japan K.K.)" and the like.

Examples of the upper limit and the lower limit of the content of the crosslinking agent in the adhesive agent with respect to 100 parts by mass (in terms of solid content) of the polyimide include 900 parts by mass, 800 parts by mass, 700 parts by mass, 600 parts by mass, 500 parts by mass, 400 parts by mass, 300 parts by mass, 200 parts by mass, 100 parts by mass, 50 parts by mass, 20 parts by mass, 10 parts by mass, and 5 parts by mass. In one embodiment, the content of the crosslinking agent is preferably about 5 parts by mass to about 900 parts by mass with respect to 100 parts by mass (in terms of solid content) of the polyimide.

Examples of the upper limit and the lower limit of the content of the crosslinking agent in 100% by mass of the adhesive include 80% by mass, 70% by mass, 60% by mass, 50% by mass, 40% by mass, 30% by mass, 20% by mass, 10% by mass, 5% by mass, and 2% by mass. In one embodiment, the content of the crosslinking agent in 100% by mass of the adhesive is preferably about 2% by mass to about 80% by mass.

< organic solvent >

The organic solvent may be used alone or two or more of various known organic solvents may be used. Examples of the organic solvent include aprotic polar solvents such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethylsulfoxide, N-methylcaprolactam, triethylene glycol dimethyl ether (methylglyme) and diethylene glycol dimethyl ether (methylglyme), alicyclic solvents such as cyclohexanone and methylcyclohexane, 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, and examples of the upper limit and the lower limit of the mass of the organic solvent with respect to 100 mass% of the solid content of the adhesive include 60 mass%, 50 mass%, 40 mass%, 30 mass%, 20 mass%, 10 mass%, and the like. In one embodiment, the organic solvent is preferably 10 to 60% by mass of the solid content per 100% by mass of the adhesive.

Examples of the upper limit and the lower limit of the content of the organic solvent in the adhesive agent with respect to 100 parts by mass (in terms of solid content) of the polyimide include 900 parts by mass, 800 parts by mass, 700 parts by mass, 600 parts by mass, 500 parts by mass, 400 parts by mass, 300 parts by mass, 200 parts by mass, and 150 parts by mass. In one embodiment, the content of the organic solvent in the adhesive is preferably 150 to 900 parts by mass per 100 parts by mass (in terms of solid content) of the polyimide.

< flame retardant >

In one embodiment, the adhesive contains a flame retardant. The flame retardant may be used alone or in combination of two or more. Examples of the flame retardant include phosphorus flame retardants and inorganic fillers.

(phosphorus flame retardant)

Examples of the phosphorus flame retardant include polyphosphoric acid, phosphoric acid esters, and phosphazene derivatives containing no phenolic hydroxyl group. Among these phosphazene derivatives, cyclic phosphazene derivatives are preferable from the viewpoint of flame retardancy, heat resistance, bleed-out resistance, and the like. Examples of commercially available products of the cyclic phosphazene derivative include SPB-100 manufactured by Otsuka chemical Co., Ltd, ラビトル FP-300B manufactured by Kotsuka pharmaceutical Co., Ltd.

(inorganic Filler)

In one embodiment, the inorganic filler may be exemplified by silica filler, phosphorus-based filler, fluorine-based filler, inorganic ion exchanger filler, and the like. Examples of commercially available products include FB-3SDC manufactured by Kagaku K.K., Exolit OP935 manufactured by Kelaien chemical Co., Ltd, KTL-500F manufactured by Kyomura, and IXE manufactured by Toyo chemical Co., Ltd.

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

< reactive alkoxysilyl Compound >

In one embodiment, the adhesive further comprises a compound of the formula: Z-Si (R)¹)_a(OR²)_3-a(wherein Z represents a group having a functional group reactive with an acid anhydride group, and R¹Represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R²Represents a hydrocarbon group having 1 to 8 carbon atoms, and a represents 0, 1 or 2. ) A reactive alkoxysilyl compound as shown. With the reactive alkoxysilyl compound, it is possible to maintain the low dielectric characteristics and adjust the melt viscosity of the adhesive layer including the adhesive of the present invention. As a result, the bleeding of the cured layer from the end of the substrate can be suppressed while improving the interfacial adhesion (so-called anchor effect) of the adhesive layer to the substrate.

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

Examples of the compound in which Z has an amino group include N-2- (aminoethyl) -3-aminopropylmethyldimethoxysilane, N-2- (aminoethyl) -3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, and 3-ureidopropyltrialkoxysilane. Examples of the compound having an epoxy group in Z include 2- (3, 4-epoxycyclohexyl) ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane and 3-glycidoxypropyltriethoxysilane. Examples of the compound in which Z has a thiol group include 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropylmethyldiethoxysilane. Among them, a compound in which Z contains an amino group is preferable from the viewpoint of good reactivity and flow rate control effect.

Examples of the upper limit and the lower limit of the content of the reactive alkoxysilyl compound in the adhesive agent with respect to 100 parts by mass (in terms of solid content) of the polyimide include 5 parts by mass, 2.5 parts by mass, 1 part by mass, 0.5 part by mass, 0.1 part by mass, 0.05 part by mass, and 0.01 part by mass. In one embodiment, the content of the reactive alkoxysilyl compound in the adhesive is preferably 0.01 to 5 parts by mass per 100 parts by mass (in terms of solid content) of the polyimide.

The adhesive may contain, as an additive, one or more other than the polyimide, the crosslinking agent, the organic solvent, the flame retardant, and the reactive alkoxysilyl compound.

Examples of the additives include a ring-opening esterification catalyst, a dehydrating agent, a plasticizer, a weather resistant agent, an antioxidant, a heat stabilizer, a lubricant, an antistatic agent, a whitening agent, a colorant, a conductive agent, a mold release agent, a surface treatment agent, a viscosity modifier, a silica filler, and a fluorine filler.

In one embodiment, the content of the additive may be less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, or the like, with respect to 100 parts by mass of the adhesive.

In another embodiment, the content of the additive may be less than 1 part by mass, less than 0.1 part by mass, less than 0.01 part by mass, 0 part by mass, or the like, based on 100 parts by mass (in terms of solid content) of the polyimide.

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

[ film-like adhesive Material ]

The present invention provides a film-like adhesive material comprising a heat-cured product of the composition and/or a heat-cured product of the adhesive. Examples of the method for producing the film-like adhesive material include a method including a step of applying the adhesive to an appropriate support, a step of volatilizing an organic solvent by heating to cure the adhesive, a step of peeling the adhesive from the support, and the like. The thickness of the adhesive material is not particularly limited, but is preferably about 3 μm to about 40 μm. The support may be made of the following materials.

[ adhesive layer ]

The present invention provides an adhesive layer containing one or more selected from the group consisting of the composition, the adhesive and the film-like adhesive material. In the production of the adhesive layer, the adhesive may be used in combination with various known adhesives other than the adhesive. Similarly, the film-like adhesive material may be used in combination with various known film-like adhesive materials other than the film-like adhesive material.

[ adhesive sheet ]

The present invention provides an adhesive sheet comprising the above adhesive layer and a support film.

The support film may be exemplified by a plastic film. Examples of the plastic include polyester, polyimide-silica hybrid, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin, and aromatic polyester resins (so-called liquid crystal polymers, ベクスター, manufactured by Kokukukukukai Co., Ltd.) obtained from ethylene terephthalate, phenol, phthalic acid, hydroxynaphthoic acid, and the like and p-hydroxybenzoic acid.

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

[ copper foil with resin ]

The present invention provides a resin-coated copper foil comprising the adhesive layer and a copper foil. Specifically, the resin-coated copper foil is obtained by applying or bonding the adhesive or the film-like adhesive material to a copper foil. Examples of the copper foil include rolled copper foil and electrolytic copper foil. The thickness is not particularly limited, but is preferably from about 1 μm to about 100. mu.m, more preferably from about 2 μm to about 38 μm. The copper foil may be one subjected to various surface treatments (roughening, rust prevention, etc.). Examples of the rust-proofing treatment include plating treatment using a plating solution containing Ni, Zn, Sn, or the like, and so-called mirror-surface treatment such as chromate treatment. The above-described method can be exemplified as the coating means.

The adhesive layer of the resin-coated copper foil may be an uncured adhesive layer, or may be an adhesive layer partially cured or completely cured by heating. The partially cured adhesive layer is in a state called a so-called B-stage. The thickness of the adhesive layer is also not particularly limited, but is preferably about 0.5 μm to about 30 μm. Further, a resin may be further bonded to the copper foil with the resin to form a copper foil with a resin on both sides.

[ copper-clad laminate ]

The present invention provides a copper-clad laminate comprising the adhesive sheet and/or the resin-attached copper foil, and at least one selected from the group consisting of a copper foil, an insulating sheet, and a support film. The copper Clad laminate is also called ccl (copper Clad laminate). In one embodiment, the copper-clad laminate is obtained by bonding various known copper foils to one or both surfaces of the adhesive sheet, or by bonding the resin-attached copper foil to one or both surfaces of at least one selected from the group consisting of various known copper foils, insulating sheets, and support films under heating. When the resin-attached copper foil is bonded to one surface, a material different from the resin-attached copper foil may be pressure-bonded to the other surface. The number of resin-coated copper foils and insulating sheets in the copper-clad laminate is not particularly limited.

In one embodiment, the insulating sheet is preferably a prepreg. The prepreg is a sheet material (JIS C5603) obtained by impregnating a reinforcing material such as glass cloth with a resin and curing the resin to the B stage. As the resin, an insulating resin such as polyimide resin, phenol resin, epoxy resin, polyester resin, liquid crystal polymer, or aramid resin can be used. The thickness of the prepreg is not particularly limited, and is preferably about 20 μm to about 500 μm. The heating and pressure bonding conditions are not particularly limited, and may be set to 300 ℃ or higher. The heating, crimping conditions are preferably from about 150 ℃ to about 280 ℃ (more preferably from about 170 ℃ to about 240 ℃), and preferably from about 0.5MPa to about 20MPa (more preferably from about 1MPa to about 8 MPa).

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

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, and sodium hypophosphite. When the electroless copper plating solution contains a reducing agent, the content thereof is preferably about 0.1g/L to about 100g/L, more preferably about 1g/L to about 30 g/L.

The electroless copper plating solution may contain a complexing agent. One kind of complexing agent may be used alone, or two or more kinds may be used in combination. Examples of the complexing agent include citric acid, tartaric acid, malic acid, lactic acid, gluconic acid, alkali metal salts thereof (e.g., rochelle salt), carboxylic acids (salts) such as ammonium salts, amino acids such as glycine, amines such as ethylenediamine and alkylamine, and ammonium, EDTA, pyrophosphoric acid (salts) and the like. When the electroless copper plating solution contains a complexing agent, the content thereof is preferably from about 1g/L to about 100g/L, more preferably from about 10g/L to about 100 g/L.

The solution temperature at the time of electroless copper plating is preferably about 0 ℃ or higher, and more preferably about 20 to about 80 ℃.

The electroless copper plating can be repeated as many as 2 times or more as necessary.

Examples of the vacuum copper plating include copper sputtering.

The copper sputtering can be performed by using various known sputtering apparatuses.

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

The vacuum copper plating can be repeated for more than 2 times as required.

[ printed Wiring Board ]

The present invention provides a printed wiring board having a circuit pattern on a 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 a subtractive method and a semi-additive method. The semi-additive method may be exemplified by the following method: after patterning the copper foil surface of the copper-clad laminate with a resist film, electrolytic copper plating is performed to remove the resist, and etching is performed with an alkali solution. The thickness of the circuit pattern layer in the printed wiring board is not particularly limited. Further, a multilayer substrate can be obtained by laminating the same printed wiring board or other known printed wiring boards or printed wiring boards on the printed wiring board as a core base material. In the lamination, the adhesive and other known adhesives than the adhesive may be used in combination. The number of layers in the multilayer substrate is not particularly limited. In addition, each time the layers are stacked, a through hole may be inserted to perform plating treatment on the inside. The line width/pitch ratio of the circuit pattern is not particularly limited, and is usually about 1 μm/1 μm to about 100 μm/100 μm. The height of the circuit pattern is not particularly limited, and is usually about 1 μm to about 50 μm.

[ multilayer Wiring Board ]

The invention provides a multilayer wiring board comprising 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) to (2) may be the printed wiring board, or may be various known printed wiring boards. Similarly, the printed circuit boards (1) to (2) may be the above-described printed circuit boards, or may be various known printed circuit boards. 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.

[ method for manufacturing multilayer Wiring Board ]

The present invention provides a method for manufacturing a multilayer wiring board including the following steps 1 and 2:

step 1: a step of producing a base material with an adhesive layer by bringing at least one or more selected from the group consisting of the adhesive, the film-like adhesive material, and the adhesive sheet into contact with at least one surface of a printed wiring board (1) or a printed circuit board (1);

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

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

The heating temperature and the pressure-bonding time in step 2 are not particularly limited, (i) after the adhesive or the film-like adhesive material of the present invention is brought into contact with at least one surface of the core substrate, the core substrate is heated to about 70 to about 200 ℃ and subjected to a curing reaction for about 1 to about 10 minutes, and then (ii) in order to allow the curing reaction of the crosslinking agent to proceed, it is preferable to further subject the core substrate to a heating treatment at about 150 to about 300 ℃ for about 10 to about 3 hours. The pressure is also not particularly limited, but is preferably from about 0.5MPa to about 20MPa, more preferably from about 1MPa to about 8MPa, throughout the steps (i) and (ii).

Examples

The present invention will be specifically described below with reference to examples and comparative examples. However, the description of the preferred embodiments and the examples below are provided for illustrative purposes only and are not provided for the purpose of limiting the present invention. Therefore, the scope of the present invention is not limited to the embodiments and examples specifically described in the present specification, but is defined only by the claims. In the examples and comparative examples, the numerical values of parts,% and the like are based on mass unless otherwise specified.

Production example 1 production of polyimide

4, 4' - [ propane-2, 2-diylbis (1, 4-phenyleneoxy) ] bisphthalic dianhydride (trade name "BisDA-1000", manufactured by SABIC Innovative plastics Japan contract Co., Ltd.; hereinafter abbreviated as BisDA.) 350.00g, cyclohexanone 993.30g, and methylcyclohexane 198.66g were charged into a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen introduction pipe, and heated to 60 ℃. Subsequently, 89.85g of 4, 4' -diaminodiphenyl ether (trade name "ODA", manufactured by JFE chemical Co., Ltd., hereinafter abbreviated as ODA ") and 103.85g of a commercially available dimer diamine (trade name" PRIAMINE1075 ", manufactured by Kagaku Co., Ltd.) were added dropwise thereto, and then imidization was performed at 140 ℃ for 12 hours to obtain a solution (nonvolatile content: 32.9%) of the polyimide (1-1). The polyimide had a molar ratio of acid component/amine component of 1.05 and a softening point of 180 ℃.

Example 1-1:

a composition was prepared by mixing 10.0g of the polyimide obtained in preparation example 1 with 0.07g of タケネート D-110N (manufactured by Mitsui chemical Co., Ltd.).

The production was carried out in the same manner as in example 1-1 except that the components in examples and comparative examples other than example 1-1 were changed as shown in the following table.

[ Table 1]

	Polyimide, polyimide resin composition and polyimide resin composition
			Examples 1 to 1	Preparation example 110.0 g	タケネートD-110N 0.07g
Examples 1 to 2	Preparation example 110.0 g	タケネートD-131N 0.07g
			Examples 1 to 3	Preparation example 110.0 g	タケネートD-204EA-1 0.10g
Examples 1 to 4	Preparation example 110.0 g	P1071 0.12g
			Examples 1 to 5	Preparation example 110.0 g	P1071 0.05g
Examples 1 to 6	Preparation example 110.0 g	タケネートD-110N 0.15g
			Examples 1 to 7	Preparation example 110.0 g	VESTANAT T1890/100 0.05g
Comparative example 1-1	Preparation example 110.0 g	—

タケネート D-110N: trimethylolpropane adduct of xylylenediisocyanate (manufactured by Mitsui chemical Co., Ltd.)

タケネート D-131N: isocyanurate body of xylylene diisocyanate (manufactured by Mitsui chemical Co., Ltd.)

タケネート D-204 EA-1: isocyanurate body of tolylene diisocyanate (manufactured by Mitsui chemical Co., Ltd.)

P1071: PRIAMINE1071, TRIAMINE/DIMENSIONAL DIAMINE (20/80) (manufactured by HEDA JAPONICA JUNK Co., Ltd.)

VESTANAT T1890/100: isocyanurate body of isophorone diisocyanate (product of Yingchuang Co., Ltd.)

Example 2

< preparation of adhesive sheet >

The compositions of example 1 and comparative example 1 were applied to a polyimide film (trade name: カプトン 100EN, manufactured by tokyo dupont) using a gap coater so that the thickness after drying was 10 μm, and then dried at 200 ℃ for 3 minutes, thereby obtaining an adhesive sheet.

Production of copper-clad laminate (1) Using copper foil

The adhesive surface of the obtained adhesive sheet was overlaid on the low roughness side of a commercially available rolled copper foil (trade name "BHM-102F-HA-V2", manufactured by JX Metal Co., Ltd., thickness of 12 μm) to prepare a copper foil with a resin.

Next, the obtained resin-attached copper foil was placed on a support for pressing, and heated and pressed from above through a support made of the same material under a pressure of 2MPa, 180 to 300 ℃, and 10 minutes, thereby producing a copper-clad laminate.

1. Adhesion test

The peel strength (N/mm) of the obtained copper-clad laminate was measured at room temperature in accordance with JIS C6481 (test method for copper-clad laminates for flexible printed wiring boards).

2. Dielectric constant and dielectric loss tangent measurements

< preparation of resin for measurement and cured product sample >

The compositions of examples and comparative examples were applied to release paper (trade name: WH52-P25CM, manufactured by サンエー Kagaku Kogyo Co., Ltd.) so that the cured film thickness was 10 μm, and dried at 200 ℃ for 3 minutes. And peeling off, and heating and pressing under the conditions of pressure of 1.5MPa, 250 ℃ and 10 minutes to cure the film so that the film thickness after pressing is about 300 μm, thereby obtaining a resin for measuring dielectric constant with a film thickness of about 300 μm and a cured product sample.

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

3. Heat resistance test of solder (with predrying)

After curing, the copper clad laminate (1) using the copper foil was floated in a solder bath at 288 ℃ for 30 seconds with the copper foil side down, and pre-dried at 120 ℃ for 5 minutes to confirm the presence or absence of appearance change. The case where there was no change was indicated as "O", and the case where there was foaming or swelling was indicated as "X".

[ Table 2]

Evaluation production example 1

The production was carried out in the same manner as in example 1-1 except that the components in the evaluation production examples and the comparative evaluation production examples were changed as shown in the following table.

[ Table 3]

	Polyimide, polyimide resin composition and polyimide resin composition
			Evaluation production example A	Preparation example 14.6 g	P1071 0.04g
Evaluation of production example B	Production example 17.0 g	タケネートD-131N 0.49g
			Comparative evaluation production example A	Preparation example 11.48 g	—

< production of copper-clad laminate (2) by electroless copper plating >

An adhesive sheet obtained using the composition of the evaluation production example by the same method as in example 2 was subjected to electroless copper plating by the following procedure, thereby producing a copper-clad laminate.

(1) Degreasing: 60 ℃ for 2 minutes (クリーナー 160, made by Meltex corporation)

(2) Pre-dipping: 20 ℃ for 2 minutes

(3) Chemical copper plating: 50 ℃ for 10 minutes (copper sulfate 0.04mol/L, EDTA 0.25.25 mol/L, formalin 0.13mol/L, triphenylphosphine 2ppm)

(4) Washing with water: 20 ℃ for 2 minutes

(5) The dried thickness of the dried copper-plated part was 5 μm

< production 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 thick) by a gap coater so that the thickness after drying was 5 μm, and then dried at 180 ℃ for 2 hours, thereby obtaining a copper foil with a resin.

The resin-attached copper foil was subjected to vacuum copper plating (sputtering) by the following procedure, thereby producing a copper-clad laminate.

(1) Plasma treatment: vacuumizing until the pressure in the vacuum device reaches 1 x 10^-4Pa or less, then argon gas was introduced so that the pressure in the apparatus became 0.3Pa, and plasma treatment was performed.

(2) Sputtering: the reaction was carried out using UHSP-OP2060 (manufactured by Shimadzu corporation).

(3) Copper electroplating: at a current density of 2A/dm²Copper electroplating (plating solution: copper sulfate solution) is performed.

Evaluation example 1: adhesion test

[ Table 4]

Evaluation production example 2

[ Table 5]

コンポセラン E103D: silane-modified epoxy resin (manufactured by Mitsukawa chemical industries, Ltd.)

コロネート HXR: isocyanurate compound of hexamethylene diisocyanate (manufactured by Tosoh corporation)

Evaluation example 2

The compositions of production examples 2-1 to 2-5 and comparative 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 thick) by a gap coater so that the thickness after drying was 20 μm, and then dried at 150 ℃ for 5 minutes and then dried at 180 ℃ for 120 minutes to obtain a copper Foil with a resin.

Adhesion test

The resin surface of the obtained resin-coated copper foil and the resin surface of another obtained resin-coated copper foil were brought into contact with each other, and heated and pressed under a pressure of 2.5MPa, 180 ℃ and 90 seconds, thereby producing a copper-clad laminate.

The sample whose surface after pressing was easily peeled was rated as "o", and the sample whose surface after pressing was not peeled was rated as "x".

[ Table 6]

	Evaluation of blocking
		Evaluation production example 2-1	○
Evaluation of production example 2-2	○
		Evaluation of production examples 2 to 3	○
Comparative evaluation production example 2-1	×

Heat resistance test of solder (No predrying)

After curing, the copper clad laminate was allowed to float in a solder bath at 288 ℃ for 30 seconds with the copper foil side down, and the presence or absence of change in appearance was confirmed without predrying. The case where there was no change was indicated as "O", and the case where there was foaming or swelling was indicated as "X".

[ Table 7]

	Heat resistance of solder (No predrying)
		Evaluation of production examples 2 to 4	○
Evaluation of production examples 2 to 5	○
		Comparative evaluation production example 2-1	×

Claims

1. A composition, comprising:

2. A reaction product of polyimide, which is a reaction product of a monomer group containing aromatic tetracarboxylic anhydride and dimer diamine, and one or more selected from the group consisting of polyisocyanate, triamine and silane-modified epoxy resin.

3. An adhesive comprising the composition of claim 1, a crosslinking agent, and an organic solvent.

4. A film-like adhesive material 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.

5. An adhesive layer comprising one or more selected from the group consisting of the composition of claim 1, the adhesive of claim 3, and the film-like adhesive material of claim 4.

6. An adhesive sheet comprising the adhesive layer of claim 5 and a support film.

7. A resin-coated copper foil comprising the adhesive layer according to claim 5 and a copper foil.

8. A copper-clad laminate comprising:

the adhesive sheet of claim 6 and/or the resin-coated copper foil of claim 7; and

9. A copper-clad laminate having a copper-clad layer on the adhesive sheet according to claim 6 or the resin-coated copper foil according to claim 7.

10. The copper-clad laminate according to claim 9, wherein the copper-clad layer is an electroless copper-clad layer or a vacuum copper-clad layer.

11. A printed wiring board having a circuit pattern on the copper foil side of the copper-clad laminate according to claim 8.

12. A multilayer wiring board, comprising:

a printed wiring board (1) or a printed circuit board (1);

an adhesive layer according to claim 5; and

a printed wiring board (2) or a printed circuit board (2).

13. A method of manufacturing a multilayer wiring board, comprising the following steps 1 and 2:

step 1: a step of producing a base material with an adhesive layer by bringing at least one or more selected from the group consisting of the adhesive according to claim 3, the film-like adhesive material according to claim 4, and the adhesive sheet according to claim 6 into contact with at least one surface of a printed wiring board (1) or a printed circuit board (1);