CN107325285B

CN107325285B - Polyimide, polyimide-based adhesive, adhesive material, adhesive layer, adhesive sheet, laminate, wiring board, and method for producing same

Info

Publication number: CN107325285B
Application number: CN201710202444.7A
Authority: CN
Inventors: 杦本启辅; 中村太阳; 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: 2016-03-30
Filing date: 2017-03-30
Publication date: 2021-05-18
Anticipated expiration: 2037-03-30
Also published as: KR102211591B1; TWI777950B; JP2017186551A; TW201805337A; KR20170113348A; CN107325285A; JP6939017B2

Abstract

The present invention relates to a polyimide, a polyimide-based adhesive, an adhesive material, an adhesive layer, an adhesive sheet, a laminated board, a wiring board, and a method for producing the same. Provided are a novel polyimide exhibiting a high storage rigidity even under temperature conditions of B-stage, a novel polyimide-based adhesive which is a composition comprising the polyimide and is capable of forming an adhesive layer having excellent adhesiveness, heat-resistant adhesiveness, flow control properties and low dielectric characteristics, and a film-like adhesive material obtained from the adhesive. A polyimide (1) which is a reaction product of a monomer group containing an aromatic tetracarboxylic acid anhydride (A) and a diamine (B) containing a dimer diamine (B1) and a trimer triamine (B2) in a mass ratio [ (B1)/(B2) ] of 97/3 to 70/30; and a polyimide-based adhesive comprising the component (1), a crosslinking agent (2), and an organic solvent (3); and a film-like adhesive material obtained from the polyimide-based adhesive.

Description

Polyimide, polyimide-based adhesive, adhesive material, adhesive layer, adhesive sheet, laminate, wiring board, and method for producing same

Technical Field

The present invention relates to a polyimide, a polyimide-based 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, a multilayer wiring board, and a method for producing the multilayer wiring board.

Background

Flexible Printed Wiring Boards (FPWB) and Printed Wiring Boards (PWB) and multilayer Wiring boards (MLB) using the same are widely used in mobile communication devices such as mobile phones and smart phones, base stations thereof, network-related electronic devices such as servers and routers, and products such as large computers.

In recent years, in these products, high-frequency electric signals are used for transmitting and processing large-capacity information at high speed, but the high-frequency signals are extremely easily attenuated, and therefore, the multilayer wiring board and the like are also required to be designed to suppress transmission loss.

As a means for suppressing the transmission loss in a multilayer wiring board, for example, when a printed wiring board or a printed circuit board is laminated, it is considered to use a polyimide-based adhesive which is excellent in heat-resistant adhesiveness and has characteristics of having both a low dielectric constant and a low dielectric loss tangent (hereinafter also referred to as low dielectric characteristics) (for example, see patent documents 1 to 3).

Documents of the prior art

Patent document

Patent document 1: japanese laid-open patent publication No. 2009-299040

Patent document 2: japanese patent laid-open No. 2014-045076

Patent document 3: japanese patent laid-open No. 2014-086591

Disclosure of Invention

Problems to be solved by the invention

On the other hand, electronic parts and semiconductor parts have been further miniaturized with the miniaturization, thinning and weight reduction of the above products, and further higher definition and higher density have been carried out also for flexible wiring boards on which these parts are mounted.

In order to obtain such a multilayer wiring board having a high-definition, high-density substrate laminated thereon and high adhesion reliability, it is necessary to form a polyimide-based adhesive and/or a polyimide-based film-like adhesive material in a semi-molten state (B stage) at a temperature of about 180 ℃, to ensure wettability over fine irregularities and gaps of a printed wiring board and a printed circuit board as an adherend, and to form an adhesive layer having excellent heat-resistant adhesion and low dielectric characteristics after post-curing.

In order to improve the wettability of the polyimide-based adhesive and/or the polyimide-based film-like adhesive material in the B-stage and to reduce the melt viscosity, for example, a method of reducing the molecular weight of polyimide as a main component, introducing an ether bond or a branched structure into the molecule, or blocking the molecular end with a low molecule may be considered. However, when the melt viscosity is reduced by such means, the adhesive layer is excessively softened or liquefied under heat pressing (about 180 ℃ in the B stage), and the flow rate control property such as bleeding or flowing out of the adhesive from the edge of the multilayer wiring board is impaired, or the heat resistant adhesiveness and the low dielectric characteristic of the adhesive layer are sometimes lowered.

The present invention addresses the problem of providing a novel polyimide that exhibits a high storage rigidity even under temperature conditions in the B-stage.

The present invention addresses the problem of providing a novel polyimide-based adhesive that is a composition formed using the above polyimide and that can form an adhesive layer having excellent adhesiveness, heat-resistant adhesiveness, flow rate control properties, and low dielectric characteristics, and also providing 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 obtained using the adhesive, and a method for producing the multilayer wiring board.

Means for solving the problems

As a result of intensive studies, the present inventors have found that a predetermined polyimide containing, as a raw material, not only a dimer diamine component but also a predetermined amount of a diamine component containing a trimer triamine exhibits a high storage rigidity even under the temperature conditions of the above-mentioned B stage. Further, it has been found that an adhesive and a film-like adhesive material which can solve the above problems can be obtained by using the polyimide.

That is, the present invention relates to a polyimide, a polyimide-based adhesive, a film-like adhesive material, an adhesive layer, an adhesive sheet, a copper-clad laminate, a printed wiring board, a multilayer wiring board, and a method for producing the same, as described below.

(item 1)

A polyimide (1) which is a reaction product of a monomer group containing an aromatic tetracarboxylic acid anhydride (A) and a diamine (B) containing a dimer diamine (B1) and a trimer triamine (B2) in a mass ratio [ (B1)/(B2) ] of 97/3 to 70/30.

(item 2)

The polyimide (1) according to the above item, wherein the component (A) has the following structure.

(wherein X represents a single bond or-SO₂-、-CO-、-O-、-O-C₆H₄-C(CH₃)₂-C₆H₄-O-or-COO-X¹-OCO-(X¹Is represented by- (CH)₂)_l- (1-20) or-H₂C-HC(-O-C(＝O)-CH₃)-CH₂-))

(item 3)

The polyimide (1) as described in any one of the above items, wherein the molar ratio of the (A) component to the (B) component is 1< [ (A)/(B) ] < 1.5.

(item 4)

The polyimide (1) according to any one of the above items, wherein the monomer group further comprises a diaminopolysiloxane (b 3).

(item 5)

The polyimide (1) as described in any one of the above items, wherein the molar ratio of the (A) component to the (B) component is 0.6< [ (A)/(B) ] < 1.4.

(item 6)

The polyimide (1) according to any one of the above items, wherein the molar ratio of the (b1) component and the (b2) component to the (b1) component, the (b2) component and the (b3) component is 0.3 [ (b1) + (b2) ]/[ (b1) + (b2) + (b3) ] ] <1.

(item 7)

A polyimide-based adhesive comprising the polyimide (1) according to any one of the above items, a crosslinking agent (2), and an organic solvent (3).

(item 8)

The polyimide-based adhesive according to any one of the above items, wherein the crosslinking agent (2) is selected from the group consisting of epoxy compounds and benzols

At least one member selected from the group consisting of an oxazine compound, a bismaleimide compound and a cyanate ester compound.

(item 9)

The polyimide-based adhesive according to any one of the above items, wherein the epoxy compound is tetraglycidyl diamine having the following structure.

(wherein Y represents phenylene or cyclohexylene)

(item 10)

The polyimide-based adhesive according to any one of the above items, wherein the amount of the component (2) is 11 to 900 parts by mass and the amount of the component (3) is 150 to 900 parts by mass based on 100 parts by mass of the component (1) (in terms of solid content).

(item 11)

A film-like adhesive material obtained from the polyimide-based adhesive according to any one of the above items.

(item 12)

An adhesive layer obtained from the polyimide-based adhesive according to any one of the above items or the film-like adhesive material according to any one of the above items.

(item 13)

An adhesive sheet comprising the adhesive layer as defined in any one of the above items and a support film.

(item 14)

A copper foil with resin, comprising the adhesive layer according to any one of the above items and a copper foil.

(item 15)

A copper-clad laminate comprising the resin-coated copper foil according to any one of the above items and one copper foil.

(item 16)

A copper-clad laminate comprising the resin-coated copper foil according to any one of the above items and one insulating sheet.

(item 17)

A printed wiring board obtained by forming a circuit pattern on a copper foil surface of the copper-clad laminate as defined in any one of the above items.

(item 18)

A multilayer wiring board, comprising:

a printed wiring board or a printed wiring board as a core base material,

The adhesive layer as described in any one of the above items, and

a printed wiring board or a printed wiring board as another base material.

(item 19)

A method for 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 the polyimide-based adhesive according to any one of the above items or the film-like adhesive material according to any one of the above items into contact with at least one surface of one printed wiring board or one printed circuit board as a core base material;

and a step 2: and laminating a printed wiring board or a printed wiring board on the adhesive layer-attached base material, and pressure-bonding the laminated layers under heat and pressure.

Effects of the invention

The polyimide (1) of the present invention exhibits a high storage rigidity ratio even under the temperature condition of the B stage. Therefore, the adhesive obtained using the polyimide (1) and the film-like adhesive material obtained from the adhesive show little bleeding or bleeding of the adhesive in the B stage, and have good heat-resistant adhesiveness and low dielectric characteristics, and thus are particularly suitable for high-frequency printed wiring board applications. Since a high-frequency printed wiring board produced using the adhesive or the adhesive material has a small transmission loss of high-frequency electric signals, it is suitably used for applications such as mobile communication devices including smart phones and cellular phones, network-related electronic devices including base station devices thereof, servers and routers, and large-scale computers.

Drawings

FIG. 1 is a graph showing changes in storage rigidity ratios with temperature between the polyimide (1-1) of production example 1 and the polyimide (1-2) of comparative example 1.

FIG. 2 is a schematic view of a sample for flow rate control test. In fig. 2, 1 denotes an insulating film (block copolymerized polyimide-silica hybrid film), 2 denotes an adhesive layer of the present invention, and 3 denotes a copper foil.

Detailed Description

The polyimide (1) (hereinafter referred to as the component (1)) of the present invention is a polymer comprising, as reaction components, an aromatic tetracarboxylic acid anhydride (a) (hereinafter referred to as the component (a)), and a diamine (B) (hereinafter referred to as the component (B2)) containing a dimer diamine (B1) (hereinafter referred to as the component (B1)) and a trimer (B2) (hereinafter referred to as the component (B2)), wherein the mass ratio [ (B1)/(B2) ] is within a range of 97/3 to 70/30.

As the component (A), various known aromatic tetracarboxylic acid anhydrides can be used. Specifically, an aromatic tetracarboxylic anhydride represented by the following structure can be used.

Specific examples of the component (A) include pyromellitic dianhydride, 4,4 ' -oxydiphthalic dianhydride, 3,3 ', 4,4 ' -benzophenonetetracarboxylic dianhydride, 3,3 ', 4,4 ' -diphenyl ether tetracarboxylic dianhydride, 3,3 ', 4,4 ' -diphenylsulfonetetracarboxylic dianhydride, 1,2,3, 4-benzenetetracarboxylic anhydride, 1,4,5, 8-naphthalenetetracarboxylic anhydride, 2,3,6, 7-naphthalenetetracarboxylic anhydride, 3,3 ', 4,4 ' -biphenyltetracarboxylic dianhydride, 2 ', 3,3 ' -biphenyltetracarboxylic dianhydride, 2,3,3 ', 4 ' -benzophenonetetracarboxylic dianhydride, 2,3,3 ', 4 ' -diphenyl ether tetracarboxylic dianhydride, 2,3 ', 4 ' -diphenyl ether tetracarboxylic dianhydride, 2,3,3 ', 4' -diphenylsulfone tetracarboxylic dianhydride, 2-bis (3,3 ', 4, 4' -tetracarboxyphenyl) tetrafluoropropane dianhydride, 2 '-bis (3, 4-dicarboxyphenoxyphenyl) sulfone dianhydride, 2-bis (2, 3-dicarboxyphenyl) propane dianhydride, 2-bis (3, 4-dicarboxyphenyl) propane dianhydride, and 4, 4' - [ propane-2, 2-diylbis (1, 4-phenyleneoxy) ] bisphthalic dianhydride, and the like, and two or more of these dianhydrides may be combined. Among them, from the viewpoint of compatibility of the component (a) and the component (B), room-temperature adhesion, heat-resistant adhesion, and the like, 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.

(b1) Component (C) is a dimer acid which is a dimer of unsaturated fatty acids such as oleic acid and the like, in which all carboxyl groups are substituted with primary amino groups (see Japanese patent application laid-open No. 9-12712 and the like), and various known dimer diamines can be used without particular limitation. Hereinafter, a non-limiting structural formula of the dimer diamine is shown (in the formulae, m + n is 6 to 17, p + q is 8 to 19, and the dotted line portion represents a carbon-carbon single bond or a carbon-carbon double bond).

Commercially available products of component (b1) include, for example, バ - サミン 551 (manufactured by BASF Japan K.K.), バ - サミン 552 (manufactured by コグニクス Japan K.K.; hydrogenated product of バ - サミン 551), PRIAMINE1075, PRIAMINE1074 (both manufactured by Kagaku Japan K.K.), and the like. The dimer diamine component in these commercially available products is usually about 95 to 98% by mass, and the remaining amount is usually 2% by mass or less, and the trimer triamine described later may be contained.

(b2) The component (A) is a trimer acid which is a trimer of an unsaturated fatty acid such as oleic acid (see Japanese patent application laid-open No. 2013-505345) in which all carboxyl groups are substituted with primary amino groups, and various publicly known trimeric triamines can be used without particular limitation. The following non-limiting structural formula of the triamine is shown (formula, m + n is 6-17, p + q is 8-19, dotted line part represents a carbon-carbon single bond or a carbon-carbon double bond, R represents ethylene-CH₂CH₂-) or vinylidene (-CH ═ CH-)).

Examples of the commercially available product of component (b2) include PRIAMINE1071 (manufactured by Dai Japan Co., Ltd.). 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.

(B) The mass ratio [ (b1)/(b2) ] of the component (b1) to the component (b2) in the components is about 97/3 to 70/30. When the amount is within this range, the balance between the flow rate control property and the heat-resistant tackiness becomes good. From this viewpoint, the ratio is preferably about 96/4 to 75/25, more preferably about 95/5 to 75/25, still more preferably about 93/7 to 75/25, and most preferably about 93/7 to 83/17.

(B) The method for producing the component (c) is not particularly limited. For example, the following methods can be cited: mixing the above-mentioned component (b1) and component (b2) produced by various known methods so as to attain the above-mentioned mass ratio; alternatively, the commercially available product of the component (b1) and the commercially available product of the component (b2) may be mixed so as to achieve the above molar ratio.

(A) The molar ratio of the component (A) to the component (B) is not particularly limited, but is usually about 1< [ (A)/(B) ] <1.5, preferably about 1.03< [ (A)/(B) ] <1.4, from the viewpoint of maintaining the storage rigidity ratio at a high value at high temperature, etc., and is more preferably about 1.07< [ (A)/(B) ] <1.4, and most preferably about 1.09< [ (A)/(B) ] <1.16, from the viewpoint of gelation, etc.

In the present invention, the monomer group containing the component (a) and the component (B) may contain a diaminopolysiloxane (hereinafter, referred to as the component (B3)). Examples of the component (b3) include: α, ω -bis (2-aminoethyl) polydimethylsiloxane, α, ω -bis (3-aminopropyl) polydimethylsiloxane, α, ω -bis (4-aminobutyl) polydimethylsiloxane, α, ω -bis (5-aminopentyl) polydimethylsiloxane, α, ω -bis [3- (2-aminophenyl) propyl ] polydimethylsiloxane, α, ω -bis [3- (4-aminophenyl) propyl ] polydimethylsiloxane, 1, 3-bis (3-aminopropyl) tetramethyldisiloxane, 1, 3-bis (4-aminobutyl) tetramethyldisiloxane, and the like. Examples of the component (B) other than the components (B1) to (B3) include: alicyclic diamines such as diaminocyclohexane, diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, diaminobicyclo [2.2.1] heptane, bis (aminomethyl) -bicyclo [2.2.1] heptane, 3(4),8(9) -bis (aminomethyl) tricyclo [5.2.1.02,6] decane, isophoronediamine, 4' -diaminodicyclohexylmethane, and 1, 3-bisaminomethylcyclohexane; bisaminophenoxyphenylpropanes such as 2, 2-bis [4- (3-aminophenoxy) phenyl ] propane and 2, 2-bis [4- (4-aminophenoxy) phenyl ] propane; diaminodiphenyl ethers such as 3,3 ' -diaminodiphenyl ether, 3,4 ' -diaminodiphenyl ether and 4,4 ' -diaminodiphenyl ether; phenylenediamines such as p-phenylenediamine and m-phenylenediamine; diaminodiphenyl sulfides such as 3,3 ' -diaminodiphenyl sulfide, 3,4 ' -diaminodiphenyl sulfide and 4,4 ' -diaminodiphenyl sulfide; diaminodiphenyl sulfones such as 3,3 ' -diaminodiphenyl sulfone, 3,4 ' -diaminodiphenyl sulfone and 4,4 ' -diaminodiphenyl sulfone; diaminobenzophenones such as 3,3 ' -diaminobenzophenone, 4 ' -diaminobenzophenone, and 3,4 ' -diaminobenzophenone; diaminodiphenylmethane such as 3,3 ' -diaminodiphenylmethane, 4 ' -diaminodiphenylmethane, and 3,4 ' -diaminodiphenylmethane; diaminophenylpropanes such as 2, 2-bis (3-aminophenyl) propane, 2-bis (4-aminophenyl) propane and 2- (3-aminophenyl) -2- (4-aminophenyl) propane; diaminophenylhexafluoropropanes such as 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; diaminophenylethanes such as 1, 1-bis (3-aminophenyl) -1-phenylethane, 1-bis (4-aminophenyl) -1-phenylethane and 1- (3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane; bisaminophenoxybenzenes such as 1, 3-bis (3-aminophenoxy) benzene, 1, 3-bis (4-aminophenoxy) benzene, 1, 4-bis (3-aminophenoxy) benzene, and 1, 4-bis (4-aminophenoxy) benzene; bis-aminobenzoylbenzenes such as 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; bisaminodimethylbenzylbenzenes such as 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; bisaminobistrifluoromethylbenzyl benzenes such as 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, and 1, 4-bis (4-amino- α, α -bistrifluoromethylbenzyl) benzene; aminophenoxy biphenyls such as 2, 6-bis (3-aminophenoxy) benzonitrile, 4 '-bis (3-aminophenoxy) biphenyl, and 4, 4' -bis (4-aminophenoxy) biphenyl; aminophenoxyphenyl ketones such as bis [4- (3-aminophenoxy) phenyl ] ketone and bis [4- (4-aminophenoxy) phenyl ] ketone; aminophenoxyphenyl sulfides such as bis [4- (3-aminophenoxy) phenyl ] sulfide and bis [4- (4-aminophenoxy) phenyl ] sulfide; aminophenoxy phenyl sulfones such as bis [4- (3-aminophenoxy) phenyl ] sulfone and bis [4- (4-aminophenoxy) phenyl ] sulfone; aminophenoxy phenyl ethers such as bis [4- (3-aminophenoxy) phenyl ] ether and bis [4- (4-aminophenoxy) phenyl ] ether; aminophenoxyphenylpropanes such as 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 (B) component other than the above-mentioned (B1) to (B3) components 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, and mixtures thereof, 1, 4-bis [4- (4-aminophenoxy) benzoyl ] benzene, 1, 3-bis [4- (3-aminophenoxy) - α, α -dimethylbenzyl ] benzene, 1, 3-bis [4- (4-aminophenoxy) - α, α -dimethylbenzyl ] benzene, 1, 4-bis [4- (3-aminophenoxy) - α, α -dimethylbenzyl ] benzene, 1, 4-bis [4- (4-aminophenoxy) - α, α -dimethylbenzyl ] benzene, 4 '-bis [4- (4-aminophenoxy) benzoyl ] diphenyl ether, 4' -bis [4- (4-amino- α, α -dimethylbenzyl) phenoxy ] benzophenone, and a pharmaceutically acceptable salt thereof, 4,4 ' -bis [4- (4-amino-. alpha.,. alpha. -dimethylbenzyl) phenoxy ] diphenylsulfone, 4 ' -bis [4- (4-aminophenoxy) phenoxy ] diphenylsulfone, 3,3 ' -diamino-4, 4 ' -diphenoxybenzophenone, 3,3 ' -diamino-4, 4 ' -biphenoxybenzophenone, 3,3 ' -diamino-4-phenoxybenzophenone, 3,3 ' -diamino-4-diphenoxybenzophenone, 6 ' -bis (3-aminophenoxy) 3,3,3 ', 3, ' -tetramethyl-1, 1 ' -spiroindane, 6 ' -bis (4-aminophenoxy) 3,3,3, ' 3, ' tetramethyl-1, 1 ' -spiroindane, bis (aminomethyl) ether, bis (2-aminoethyl) ether, bis (3-aminopropyl) ether, bis (2-aminomethoxy) ethyl ] ether, bis [2- (2-aminoethoxy) ethyl ] ether, bis [2- (3-aminopropoxy) ethyl ] ether, 1, 2-bis (aminomethoxy) ethane, 1, 2-bis (2-aminoethoxy) ethane, 1, 2-bis [2- (aminomethoxy) ethoxy ] ethane, 1, 2-bis [2- (2-aminoethoxy) ethoxy ] ethane, ethylene glycol bis (3-aminopropyl) ether, diethylene glycol bis (3-aminopropyl) ether, triethylene glycol bis (3-aminopropyl) ether, ethylene glycol bis (3-aminoethoxy) ether, ethylene glycol bis (2-aminoethoxy) ethyl ] ethane, ethylene glycol bis (3-aminopropoxy) ethyl) ether, ethylene glycol bis (3-aminoethoxy) ethane, ethylene glycol bis (3-aminoethoxy, Ethylenediamine, 1, 3-diaminopropane, 1, 4-diaminobutane, 1, 5-diaminopentane, 1, 6-diaminohexane, 1, 7-diaminoheptane, 1, 8-diaminooctane, 1, 9-diaminononane, 1, 10-diaminodecane, 1, 11-diaminoundecane, 1, 12-diaminododecane, 2, 6-bis (3-aminophenoxy) pyridine, and the like. These components may be combined in two or more kinds.

Even when the component (B3) is used, the amounts of the component (a) and the component (B) are not particularly limited. When the component (B3) is used, the molar ratio of the component (a) to the component (B) may be usually about 0.6< [ (a)/(B) ] <1.4, preferably about 0.8< [ (a)/(B) ] <1.2, from the viewpoint of the balance among solubility of the component (1) in an organic solvent to be described later, room-temperature adhesion, heat-resistant adhesion, and low dielectric characteristics.

(b1) The ratio of the components (a) to (b3) used is not particularly limited, and the molar ratio of the component (b1) to the component (b2) to the component (b1), the component (b2) to the component (b3) may be usually about 0.3 [ (b1) + (b2) ]/[ (b1) + (b2) + (b3) ] ] <1, preferably about 0.6 [ (b1) + (b2) ]/[ (b1) + (b2) + (b3) ] <1, and more preferably about 0.6 [ (b1) + (b2) ]/[ (b1) + (b2) + (b3) ] < 0.96.

(1) The component (b) can be produced by various known methods. For example, the addition polymerization reaction of the component (A) and the component (B) containing the components (B1), (B2) and, if necessary, the component (B3) is usually carried out at a temperature of about 60 ℃ to about 120 ℃ (preferably about 80 ℃ to about 100 ℃) for about 0.1 hour to about 2 hours (preferably about 0.1 hour to about 0.5 hour). Then, the obtained addition polymer is further subjected to imidization, i.e., a dehydration ring-closure reaction, at a temperature of about 80 to about 250 ℃ and preferably 100 to 200 ℃ for about 0.5 to about 50 hours (preferably about 1 to about 20 hours), thereby obtaining the target component (1).

In the imidization reaction, various known reaction catalysts, dehydrating agents and organic solvents described later can be used. Examples of the reaction catalyst include aliphatic tertiary amines such as triethylamine, aromatic tertiary amines such as dimethylaniline, and heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline, and two or more of these may be used in combination. Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic anhydride, and two or more of them may be combined.

(1) The imide ring-closing ratio of the component (B) is not particularly limited. The "imide ring-closure ratio" herein refers to the content of the cyclic imide bond in the component (1), and can be determined by various spectroscopic means such as NMR and IR analysis. Further, the imide ring-closure ratio of the component (1) is usually 70% or more, preferably about 85% to about 100%, whereby the room-temperature adhesion and the heat-resistant adhesion are excellent.

The physical properties of the component (1) thus obtained are not particularly limited, and examples of the upper limit of the glass transition temperature include 250 ℃, 200 ℃, 150 ℃, 100 ℃ and the like, and examples of the lower limit include 90 ℃, 80 ℃, 70 ℃, 60 ℃, 50 ℃, 40 ℃, 30 ℃, 20 ℃ and the like. The glass transition temperature range is appropriately selected from the above upper and lower values, and the like, and is usually from about 20 ℃ to about 250 ℃, preferably from about 30 ℃ to about 200 ℃ from the viewpoint of the balance between the room-temperature adhesion, the heat-resistant adhesion, and the low dielectric characteristics. The weight average molecular weight is not particularly limited, and examples of the upper limit thereof include 60000, 50000, 40000, 30000, 20000, 10000, 9000, 8000, 7000, 6000, and 5000, and examples of the lower limit thereof include 50000, 40000, 30000, 20000, 10000, 9000, 8000, 7000, 6000, 5000, 4000, and 3000. The range of the weight average molecular weight can be set, for example, by selecting from the above upper and lower limits, and is usually about 3000 to 60000, preferably about 6000 to 40000, from the same viewpoint as above. The weight average molecular weight can be determined as a polystyrene equivalent value measured by Gel Permeation Chromatography (GPC), for example.

The polyimide-based adhesive of the present invention is a composition containing the above-mentioned component (1), a crosslinking agent (2) (hereinafter, referred to as component (2)), and an organic solvent (3) (hereinafter, referred to as component (3)).

As the component (2), any known crosslinking agent can be used without particular limitation as long as it functions as a crosslinking agent for polyimide. Specifically, for example, it is preferably selected from the group consisting of epoxy compounds and benzols

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, modified epoxy compounds obtained by modifying these epoxy compounds with a dimer acid, epoxy compounds obtained by reacting a compound with a compound having a fluorene skeleton with a fluorene skeleton, epoxy compounds obtained by reacting a compound having a fluorene skeleton with a diol compound having a cyclopentadiene skeleton with a diol skeleton, epoxy compounds obtained by reacting a, Dimer acid diglycidyl ester, and the like, and two or more of them may be combined. Examples of the commercially available products include "jER 828" and "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 maclea chemical industry corporation, "YD-172-X75" manufactured by new hitachi chemical corporation, and "tetra-X" manufactured by mitsubishi gas chemical corporation. Among them, from the viewpoint of the balance among heat-resistant adhesive property, moisture-absorption brazing 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 component (1). 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 phenylene or cyclohexylene)

When an epoxy compound is used as the component (2), various known curing agents for epoxy compounds can be used in combination. Specific examples thereof include acid 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, etc.; 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; two or more kinds of curing agents may be used in combination, for example, a phenol curing agent such as a phenol novolac resin, a cresol novolac resin, a bisphenol a novolac resin, a triazine-modified phenol novolac resin, or a phosphazene containing a phenolic hydroxyl group (trade name "SPH-100" manufactured by ottasha chemical co., Ltd.), a cyclic phosphazene compound, and a rosin crosslinking agent such as a maleic acid-modified rosin or a hydride thereof. Among them, phenol curing agents, particularly phosphazene curing agents containing a phenolic hydroxyl group are preferable. The amount of the curing agent to be used is not particularly limited, and is usually about 0.1 to about 120% by mass, preferably about 10 to about 40% by mass, when the solid content of the adhesive of the present invention is set to 100% by mass.

In the case of using an epoxy compound as the (2) component and using the above curing agent, a reaction catalyst may be used. Specifically, examples thereof include: 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

Tetraphenylboron salts such as tetraphenylboron salt, 2-ethyl-4-methylimidazotetraphenylboron salt and N-methylmorpholinebetraphenylboron salt, and two or more of them may be combined. The amount of the reaction catalyst to be used is not particularly limited, and is usually about 0.01 to about 5% by mass when the solid content of the adhesive of the present invention is set to 100% by mass.

As above-mentioned benzo

Examples of the oxazine compound 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

Oxazine), etc., two or more of which may be combined. 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. Further, examples of commercially available products 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.

Examples of the bismaleimide compound include 4,4 ' -diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol a diphenylether 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 ' -diphenylether bismaleimide, 4 ' -diphenylsulfone bismaleimide, and two or more kinds of them may be combined. Further, examples of commercially available products include "BAF-BMI" manufactured by JFE chemical Co.

Examples of the cyanate ester compound include 2-allylphenol cyanate, 4-methoxyphenol cyanate, 2-bis (4-cyanatoxyphenol) -1,1,1,3,3, 3-hexafluoropropane, bisphenol a cyanate, diallylbisphenol a cyanate, 4-phenylphenol cyanate, 1,1, 1-tris (4-cyanatophenyl) ethane, 4-cumylphenol cyanate, 1, 1-bis (4-cyanatophenyl) ethane, 4' -biphenol cyanate, and 2, 2-bis (4-cyanatophenyl) propane, and two or more of these cyanate ester compounds may be combined. Examples of commercially available products include "PRIMASET BTP-6020S (manufactured by Longsha Japan K.K.)" and the like.

As the component (3), various known organic solvents can be used. Specific examples thereof 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, and two or more of them may be combined. The amount of the organic solvent used is not particularly limited, and is usually within a range of from about 10 to about 60 mass% based on the mass of the solid content of the resin composition of the present invention.

The amount of the component (1), the component (2), and the component (3) in the polyimide-based adhesive of the present invention is not particularly limited, and the upper limit of the component (2) is, for example, 60 parts by mass, 50 parts by mass, 40 parts by mass, 30 parts by mass, 20 parts by mass, or 10 parts by mass with respect to 100 parts by mass of the component (1) (in terms of solid content), the lower limit thereof is, for example, 50 parts by mass, 40 parts by mass, 30 parts by mass, 20 parts by mass, 10 parts by mass, 5 parts by mass, 3 parts by mass, or 2 parts by mass, the upper limit of the component (3) is, for example, 900 parts by mass, 800 parts by mass, 700 parts by mass, 600 parts by mass, 500 parts by mass, 400 parts by mass, or 300 parts by mass, and the lower limit thereof is, for example, 300 parts by mass, 250 parts by mass, 200 parts by mass, or 150 parts by mass. The ranges of the above-mentioned components (2) and (3) can be set, for example, by selecting from the values of the above-mentioned upper limit and lower limit, and from the viewpoint of balance of physical properties of the adhesive such as handling property, heat resistance, electrical characteristics, adhesiveness, and the like at the time of coating, usually, the amount of the component (2) is about 2 to about 60 parts by mass, preferably about 3 to about 40 parts by mass, and the amount of the component (3) is about 150 to about 900 parts by mass, preferably about 200 to about 500 parts by mass, relative to 100 parts by mass of the component (1) (in terms of solid content).

The polyimide-based adhesive of the present invention can be obtained, for example, by dissolving the components (1) and (2) in the component (3). Further, additives such as the above ring-opening esterification catalyst, dehydrating agent, plasticizer, weather resistant agent, antioxidant, heat stabilizer, lubricant, antistatic agent, whitening agent, colorant, conductive agent, mold release agent, surface treatment agent, viscosity modifier, phosphorus flame retardant, flame retardant filler, silicon filler, fluorine filler and the like may be added as necessary.

The film-like adhesive material of the present invention is an article obtained from the polyimide-based adhesive of the present invention. Specifically, for example, the adhesive is obtained by applying the adhesive to an appropriate support, heating the adhesive, volatilizing and curing the component (3), and then peeling the adhesive from the support. The thickness of the adhesive material is not particularly limited, and is usually about 3 μm to about 40 μm. The support may be made of the following materials.

The adhesive sheet of the present invention is an article comprising, as components, an adhesive layer obtained from the polyimide-based adhesive of the present invention or the film-like adhesive material of the present invention, and a support film. Examples of the support include plastic films such as polyesters, polyimides, polyimide-silica hybrids, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate resins, polystyrene resins, polycarbonate resins, acrylonitrile-butadiene-styrene resins, aromatic polyester resins obtained from p-hydroxybenzoic acid and ethylene terephthalate, phenol, phthalic acid, hydroxynaphthoic acid, etc. (so-called liquid crystal polymers, and "ベクスター" manufactured by kohly corporation). In addition, the above-mentioned coating means can be used when the polyimide-based adhesive of the present invention is coated on the support. The thickness of the coating layer is also not particularly limited, and the thickness after drying may be generally in the range of about 1 μm to about 100 μm, preferably about 3 μm to about 50 μm. In addition, the adhesive layer of the adhesive sheet may be protected with various protective films.

The resin-coated copper foil of the present invention is an article comprising the adhesive layer of the present invention and a copper foil as constituent elements. Specifically, the adhesive is obtained by applying or bonding the polyimide-based 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 usually about 1 μm to about 100. mu.m, preferably about 2 μm to about 38 μm. The copper foil may be subjected to various surface treatments (roughening, rust prevention, etc.). Examples of the rust-preventive treatment include a plating treatment using a plating solution containing Ni, Zn, Sn, or the like, a so-called mirror surface treatment such as a chromate treatment, and the like. The coating means may be the above-mentioned methods. 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, and is usually about 0.5 μm to about 30 μm. Further, a copper foil may be further bonded to the adhesive surface of the resin-coated copper foil to form a resin-coated copper foil on both sides.

The copper-Clad laminate of the present invention is formed by laminating the resin-coated copper foil of the present invention with a copper foil or an insulating sheet, and is also referred to as ccl (copper Clad laminate). Specifically, the copper foil with resin of the present invention is obtained by bonding the copper foil with resin to at least one surface or both surfaces of various known copper foils or insulating sheets under heating. When the copper foil is bonded to one surface, a material different from the resin-attached copper foil of the present invention 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. 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 a polyimide resin, a phenol resin, an epoxy resin, a polyester resin, a liquid crystal polymer, and an aramid resin is generally used. The thickness of the prepreg is not particularly limited, and is usually about 20 μm to about 500 μm. The conditions for heating and pressure bonding are not particularly limited, but are usually about 150 ℃ to about 280 ℃ (preferably about 170 ℃ to about 240 ℃), and about 0.5MPa to about 20MPa (preferably about 1MPa to about 8 MPa).

The printed wiring board of the present invention is an article obtained by forming a circuit pattern on the copper foil surface of the copper-clad laminate of the present invention. Examples of the patterning means include a subtractive method and a semi-additive method. Examples of the semi-addition method include the following methods: the copper foil surface of the copper-clad laminate of the present invention is patterned with a resist film, and then electrolytic copper plating is performed to remove the resist, followed by etching 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, not only the polyimide-based adhesive of the present invention but also other known polyimide-based adhesives may be used. 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 100 μm/100 μm. The height of the circuit pattern is not particularly limited, and is usually about 1 μm to about 50 μm.

The multilayer wiring board of the present invention is an article comprising a single printed wiring board or a single printed wiring board as a core base material, the adhesive layer of the present invention, and a single printed wiring board or a single printed wiring board as another base material as constituent elements. The single printed wiring board or the single printed wiring board may be the printed wiring board or the printed wiring board of the present invention, or may be various known printed wiring boards or printed wiring boards.

The multilayer wiring board of the present invention can be obtained by a manufacturing method including the following

steps

1 and 2.

Step 1: a step of producing a base material with an adhesive layer by bringing the polyimide-based adhesive or the film-like adhesive material of the present invention into contact with at least one surface of one printed wiring board or one printed circuit board as a core base material;

The single printed wiring board or the single printed wiring board may be the printed wiring board or the printed wiring board of the present invention, or may be various known printed wiring boards or printed wiring boards.

In the step 1, means for bringing the polyimide-based adhesive or film-like adhesive material of the present invention into contact with an 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 used.

The heating temperature and the pressure-bonding time in step 2 are not particularly limited, and usually, (i) after the polyimide-based adhesive or the film-like adhesive material of the present invention is brought into contact with at least one surface of the core base material, the curing reaction is carried out at usually about 70 to about 200 ℃ for about 1 to about 10 minutes, and then, (ii) in order to allow the curing reaction of the component (2) to proceed, heating treatment usually about 150 to about 250 ℃ for about 10 minutes to about 3 hours may be further carried out. The pressure is also not particularly limited, and is usually about 0.5MPa to about 20MPa, preferably 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, but the scope of the present invention is not limited to these examples. In each example, unless otherwise specified, parts and% are based on mass.

< production of polyimide >

Production example 1

In a reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen gas inlet tube, 300.00g of 4, 4' - [ propane-2, 2-diylbis (1, 4-phenyleneoxy) ] bisphthalic dianhydride (trade name "BisDA-1000", manufactured by SABIC innovative plastics japan contract corporation, hereinafter abbreviated as BisDA), 1042.73g of cyclohexanone and 208.55g of methylcyclohexane were charged and heated to 60 ℃. Then, 289.36g of commercially available triamine (trade name "PRIAMINE 1071", triamine/dimer diamine mass ratio of 20/80, manufactured by Seda Nippon Co., Ltd.) was added dropwise thereto, and then imidization was performed at 140 ℃ for 12 hours to obtain a solution of polyimide (1-1) (nonvolatile content: 31.9%). The molar ratio of the acid component/amine component of the polyimide was 1.13.

Polyimide was obtained in the same manner as in production example 1, except that the composition of the resin solution was changed as described in table 1 for the production examples other than production example 1 and comparative production examples. For example, comparative production example 1 was carried out by the following procedure.

Comparative production example 1

In a reaction vessel similar to that of production example 1, BisDA 310.00g, cyclohexanone 992.00g and methylcyclohexane 124.00g were charged, and the mixture was heated to 60 ℃. Then, 306.59g of commercially available dimer diamine (trade name "PRIAMINE 1075", weight ratio of triamine/dimer diamine 2/98, manufactured by Seda Nippon Co., Ltd.) was slowly added thereto, and then the mixture was heated to 140 ℃ to conduct imidization for 12 hours, thereby obtaining a solution of polyimide (2-1) (nonvolatile content: 35.7%). The molar ratio of the acid component/amine component of the polyimide was 1.05.

< measurement of storage rigidity ratio >

The solutions of production example 1 and comparative production example 1 were applied to nylon PTFE tape TOMBO No.9001 (neon corporation), dried at room temperature for 12 hours, and then dried at 150 ℃ for 5 minutes to produce an adhesive sheet of about 20 μm.

Subsequently, the adhesive sheet was folded to prepare a sheet having a thickness of about 300 μm, and the temperature dependence of the storage rigidity was measured using a commercially available viscoelasticity measuring apparatus (ARES-2KSTD-FCO-STD, manufactured by Rheometric Scientific, Inc.). The temperature increase rate was 10 ℃/min. The results are shown in fig. 1.

Example 1

A resin composition having a nonvolatile content of 30.0% was obtained by mixing and stirring thoroughly 100.0g of a solution of the polyimide resin (1-1), 22.34g of a solution of the polyimide (2-1), 0.82g of a bisphenol A type epoxy resin (trade name "JeR 828" manufactured by Nippon epoxy resin Co., Ltd., epoxy equivalent 190g/eq), 3.61g of a hydroxyl group-containing polyphenylene ether (trade name "SA 90" manufactured by SABIC Innovative plastics Japan contract Ltd., hydroxyl equivalent 840g/eq) as the component (2), and 21.11g of toluene as the organic solvent (3).

Examples and comparative examples other than example 1 were carried out in the same manner as in example 1, except that the composition of the adhesive was changed as shown in table 2. For example, comparative example 1 was performed by the following procedure.

Comparative example 1

A resin composition containing 30.0% of nonvolatile component was obtained by mixing and stirring 100.0g of a solution of polyimide (2-1), 0.73g of bisphenol A type epoxy resin (trade name "JeR 828", epoxy equivalent 190g/eq, manufactured by Nippon epoxy resin Co., Ltd.), 3.24g of hydroxyl group-containing polyphenylene ether (trade name "SA 90", manufactured by SABIC Innovative plastics Japan contract Ltd., hydroxyl equivalent 840g/eq) and 28.24g of toluene as an organic solvent.

[ Table 2]

The organic solvent (3) may contain an organic solvent used in the production of polyimide.

SG-708-6: (ナガセケムテックス type company: acrylic elastomer)

< preparation of adhesive sheet >

The adhesive composition of example 1 was applied to a block copolymerized polyimide-silica hybrid film (trade name "ポミラン N25", manufactured by seikagawa chemical industries co., ltd.; coefficient of thermal expansion 18ppm, tensile elastic modulus 5.9GPa, film thickness 25 μm, width 10cm, length 15cm) by a gap coater so that the thickness after drying was 20 μm and the left and right edges were 1cm, respectively, and then dried at 180 ℃ for 3 minutes, thereby obtaining an adhesive sheet.

< production of copper-clad laminate >

From the adhesive sheet, a sheet having a width of 10cm and a length of 4cm was cut in a direction perpendicular to the direction of the gap coater. Then, the adhesive surface of the film was superimposed on the mirror surface side of a commercially available electrolytic copper foil (trade name "F2-WS", manufactured by Kogawa copper foil Co., Ltd., 18 μm thick, 10cm wide and 5cm long) to prepare a test sample. A schematic diagram of the test sample is shown in fig. 1.

Next, the test sample was placed on a support for pressing, and heated and pressed from above through a support obtained from the same raw material under a pressure of 5MPa, 170 ℃, and 30 minutes, thereby producing a laminated film.

1. Adhesion test

The peel strength (N/cm) of the copper-clad laminate was measured in accordance with JIS C6481 (test method for copper-clad laminates for flexible printed wiring boards). The results are shown in table 3.

2. Heat resistance test of brazing

The copper-clad laminate was allowed to float in a solder bath at 288 ℃ for 30 seconds with the copper foil side facing downward, and the presence or absence of a change in appearance was confirmed. The case where no change was observed was indicated as "good", and the case where foaming or swelling was observed was indicated as "x". The results are shown in table 3.

3. Evaluation of flow Rate control

Copper foil the right end of the adhesive layer (cured layer) in the above laminated film was confirmed to have not changed in the end position before and after heating and pressing. It was found that the solidified layer did not flow out in the horizontal direction (0mm) even when the heating and pressing were performed, and the flow rate control property was good. The results are shown in table 3.

< preparation of cured product sample for measuring dielectric constant >

About 7g of the adhesive composition of example 1 was poured onto a fluororesin PFA plate (diameter 75mm, manufactured by Nippon chemical Co., Ltd.) and cured under conditions of 30 ℃ X10 hours, 70 ℃ X10 hours, 100 ℃ X6 hours, 120 ℃ X6 hours, 150 ℃ X6 hours, and 180 ℃ X12 hours, thereby obtaining a cured product sample for dielectric constant measurement having a film thickness of about 300. mu.m.

Then, the dielectric constant and the dielectric loss tangent at 10GHz were measured with respect to the cured product sample by using a commercially available dielectric constant measuring apparatus (cavity resonator type, manufactured by AET) in accordance with JIS C2565. The results are shown in table 3.

Tests 1 to 3 were also carried out in the same manner for the adhesive composition of comparative example 1. In test 3, it was confirmed that: the cured layer flowed out in a gentle wave shape to an extent of 2mm in the horizontal direction of ポミラン N25 in the laminate film for testing.

[ Table 3]

Claims

1. A polyimide (1) which is a reaction product of a monomer group comprising an aromatic tetracarboxylic acid anhydride (A) and a diamine (B) containing a dimer diamine (B1) and a trimer triamine (B2) in a mass ratio [ (B1)/(B2) ] of 97/3 to 70/30,

the component (A) is represented by the following structure,

wherein X represents a single bond, -SO₂-, -CO-, -O-or-O-C₆H₄-C(CH₃)₂-C₆H₄-O-。

2. The polyimide (1) according to claim 1, wherein the molar ratio of the (A) component to the (B) component is 1< [ (A)/(B) ] < 1.5.

3. The polyimide (1) according to claim 1 or 2, wherein the monomer set further comprises a diaminopolysiloxane (b 3).

4. The polyimide (1) according to claim 3, wherein the molar ratio of the (A) component to the (B) component is 0.6< [ (A)/(B) ] < 1.4.

5. The polyimide (1) according to claim 3, wherein the molar ratio of the (b1) component and the (b2) component to the (b1) component, the (b2) component and the (b3) component is 0.3< [ [ (b1) + (b2) ]/[ (b1) + (b2) + (b3) ] ] <1.

6. A polyimide-based adhesive comprising the polyimide (1) according to any one of claims 1 to 5, a crosslinking agent (2), and an organic solvent (3).

7. The polyimide-based adhesive according to claim 6, wherein the crosslinking agent (2) is selected from the group consisting of epoxy compounds, benzophenones

8. The polyimide-based adhesive according to claim 7, wherein the epoxy compound is tetraglycidyl diamine having the following structure,

wherein Y represents a phenylene group or a cyclohexylene group.

9. The polyimide-based adhesive according to any one of claims 6 to 8, wherein the amount of the component (2) is 11 to 900 parts by mass and the amount of the component (3) is 150 to 900 parts by mass, based on 100 parts by mass of the component (1) in terms of solid content.

10. A film-like adhesive material obtained from the polyimide-based adhesive according to any one of claims 6 to 9.

11. An adhesive layer obtained from the polyimide-based adhesive according to any one of claims 6 to 9 or the film-like adhesive material according to claim 10.

12. An adhesive sheet comprising the adhesive layer of claim 11 and a support film.

13. A resin-coated copper foil comprising the adhesive layer of claim 11 and a copper foil.

14. A copper-clad laminate comprising the resin-coated copper foil according to claim 13 and one copper foil.

15. A copper-clad laminate comprising the resin-coated copper foil according to claim 13 and an insulating sheet.

16. A printed wiring board obtained by forming a circuit pattern on the copper foil surface of the copper-clad laminate according to claim 14 or 15.

17. A multilayer wiring board, comprising:

a printed wiring board or a printed wiring board as a core base material,

An adhesive layer as defined in claim 11, and

a printed wiring board or a printed wiring board as another base material.

18. A method for 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 the polyimide-based adhesive according to any one of claims 6 to 9 or the film-like adhesive material according to claim 10 into contact with at least one surface of a single printed wiring board or a single printed wiring board as a core base material;