JP2017186551A - Polyimide, polyimide-based adhesive, film-like adhesive material, adhesive layer, adhesive sheet, copper foil with resin, copper-clad laminate and printed wiring board, and multilayer wiring board and method for manufacturing the same - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a new polyimide exhibiting high storage modulus of rigidity even on a B-stage temperature condition; a new polyimide-based adhesive which is a composition using the polyimide and provides an adhesive layer having good adhesion, heat-resistant adhesiveness, flow controllability and low dielectric characteristics; and a film-like adhesive material obtained by the adhesive.SOLUTION: There are provided polyimide (1) which is a reactant of a monomer group containing an aromatic tetracarboxylic acid anhydride (A) and diamine (B) containing dimer diamine (b1) and trimer triamine (b2) so that a mass ratio [(b1)/(b2)] is in a range of 97/3 to 70/30; a polyimide-based adhesive containing the (1) component, a crosslinking agent (2) and an organic solvent (3); and a film-like adhesive material obtained from the polyimide-based adhesive.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a polyimide, a polyimide-based adhesive, a film adhesive, 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.

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

  In recent years, these products use high-frequency electrical signals to transmit and process large amounts of information at high speed. However, high-frequency signals are very susceptible to attenuation, so transmission loss is also caused in the multilayer wiring boards. Ingenuity to suppress this is required.

  As a means for suppressing transmission loss in a multilayer wiring board, for example, when laminating a printed wiring board or a printed circuit board, not only is it excellent in heat-resistant adhesion, but also has a characteristic that both dielectric constant and dielectric loss tangent are small (hereinafter, It is conceivable to use a polyimide-based adhesive having low dielectric properties (see, for example, Patent Documents 1 to 3).

JP 2009-299040 A JP, 2014-045076, A JP 2014-086591 A

  On the other hand, as the products have become smaller, thinner, and lighter, electronic components and semiconductor components have become even smaller, and the finer and higher density of the flexible wiring board on which these components are mounted has progressed. ing.

  In order to laminate such high-definition and high-density substrates and obtain a multilayer wiring board with high adhesion reliability, a polyimide adhesive and / or a polyimide film adhesive is in a semi-molten state (B Stage) and spread over the fine irregularities and gaps of the printed circuit boards and printed circuit boards, which are adherends, to ensure wetting and to form an adhesive layer with excellent heat resistance and low dielectric properties after post-curing Must be.

  In order to increase the wettability of the B-stage polyimide adhesive and / or polyimide film adhesive, the melt viscosity may be reduced. For example, the main material polyimide may be reduced in molecular weight or ether in the molecule. It is conceivable to introduce a bond or a branched structure or to cap the molecular end with a low molecule. However, if the melt viscosity is lowered by such means, the flow control such that the adhesive layer is excessively softened or liquefied under heating press (B stage 180 ° C) and the adhesive oozes out or flows out from the edge of the multilayer wiring board. In some cases, the heat resistance and low dielectric properties of the adhesive layer may be deteriorated.

  An object of the present invention is to provide a novel polyimide exhibiting a high storage rigidity even under a B-stage temperature condition.

  The present invention is a composition comprising the above polyimide, and is obtained from a novel polyimide adhesive that provides an adhesive layer with good adhesiveness, heat resistant adhesiveness, flow controllability and low dielectric properties, and the adhesive. Another object of the present invention is to provide a film-like adhesive, 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 manufacturing method thereof.

  As a result of intensive studies, the present inventor has obtained a high storage rigidity even under the temperature condition of the B stage as long as it is a predetermined polyimide using a diamine component containing not only dimeramine amine but also a predetermined amount of trimer triamine as a diamine component. Found to show. Moreover, it discovered that the adhesive agent and film adhesive which the said subject was solved by using this polyimide are obtained.

  That is, the present invention relates to the following polyimide, polyimide adhesive, film adhesive, adhesive layer, adhesive sheet, copper-clad laminate and printed wiring board, multilayer wiring board, and manufacturing method thereof.

(Item 1)
Aromatic tetracarboxylic acid anhydride (A) and a diamine containing dimer diamine (b1) and trimer triamine (b2) in a mass ratio [(b1) / (b2)] of 97/3 to 70/30 ( Polyimide (1) which is a reaction product of a monomer group including B).
(Item 2)
(A) Polyimide (1) of any one of the above items, wherein the component is represented by the following structure.
(In the formula, X is a single bond, —SO ₂ —, —CO—, —O—, —O—C ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ —O— or —COO—X ^1. —OCO— (X ¹ represents — (CH ₂ ) ₁ — (1 = 1 to 20) or —H ₂ C—HC (—O—C (═O) —CH ₃ ) —CH ₂ —). Represents.)
(Item 3)
The polyimide (1) according to any one of the above items, wherein the molar ratio of the component (A) to the component (B) 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 diaminopolysiloxane (b3).
(Item 5)
The polyimide (1) according to any one of the above items, wherein the molar ratio of the component (A) to the component (B) is 0.6 <[(A) / (B)] <1.4.
(Item 6)
The molar ratio of the component (b1) and the component (b2) to the component (b1), the component (b2) and the component (b3) is 0.3 <[[(b1) + (b2)] / [(b1) + (B2) + (b3)]] <1 Polyimide (1) according to any one of the above items.
(Item 7)
A polyimide-based adhesive containing the polyimide (1), the crosslinking agent (2) and the organic solvent (3) according to any one of the above items.
(Item 8)
The polyimide adhesive according to any one of the above items, wherein the crosslinking agent (2) is at least one selected from the group consisting of an epoxy compound, a benzoxazine compound, a bismaleimide compound, and a cyanate ester compound.
(Item 9)
The polyimide adhesive according to any one of the above items, wherein the epoxy compound is tetraglycidyldiamine having the following structure.
(In the formula, Y represents a phenylene group or a cyclohexylene group.)
(Item 10)
(1) Polyimide according to any one of the above items, wherein (2) component is 11 to 900 parts by mass and (3) component is 150 to 900 parts by mass with respect to 100 parts by mass (in terms of solid content) Adhesives.
(Item 11)
A film adhesive obtained from the polyimide adhesive according to any one of the above items.
(Item 12)
An adhesive layer obtained from the polyimide adhesive according to any one of the above items or the film adhesive according to any one of the above items.
(Item 13)
An adhesive sheet comprising the adhesive layer according to any one of the above items and a support film.
(Item 14)
The copper foil with resin containing the contact bonding layer and copper foil of any one of the said items.
(Item 15)
The copper clad laminated board containing the copper foil with resin of any one of the said items, and one copper foil.
(Item 16)
The copper clad laminated board containing the copper foil with resin of any one of the said items, and the one insulating sheet.
(Item 17)
A printed wiring board obtained by forming a circuit pattern on the copper foil surface of the copper clad laminate according to any one of the above items.
(Item 18)
One printed wiring board or one printed circuit board as a core substrate;
The adhesive layer of any one of the above items;
One printed wiring board or one printed circuit board as another substrate;
including,
Multilayer wiring board.
(Item 19)
A method for producing a multilayer wiring board, comprising the following steps 1 and 2.
Step 1: The polyimide adhesive according to any one of the above items or the film-like adhesive according to any one of the above items is applied to at least one surface of one printed wiring board or one printed circuit board as a core substrate. Step 2 for producing a base material with an adhesive layer by bringing it into contact: Step of laminating one printed wiring board or one printed circuit board on the base material with an adhesive layer and press-bonding it under heat and pressure

  The polyimide (1) of the present invention exhibits a high storage rigidity even under B-stage temperature conditions. Therefore, the adhesive obtained by using the polyimide (1) and the film-like adhesive obtained from the adhesive have less leaching or outflow of the adhesive in the B stage, and have heat resistant adhesiveness and low dielectric properties. Is particularly suitable for high-frequency printed wiring board applications. The high-frequency printed wiring board manufactured using the adhesive and the adhesive has a small transmission loss of high-frequency electrical signals, and therefore, for example, mobile communication devices represented by smartphones and mobile phones, base station devices thereof, server routers It is suitable for applications such as network-related electronic devices such as large computers.

It is a graph showing the temperature change of the storage rigidity of the polyimide (1-1) of manufacture example 1 and the polyimide (1-2) of comparative example 1. It is the schematic of the sample for flow control tests. In FIG. 2, 1 is an insulating film (block copolymerized polyimide-silica hybrid film), 2 is an adhesive layer according to the present invention, and 3 is a copper foil.

  The polyimide (1) of the present invention (hereinafter referred to as component (1)) includes aromatic tetracarboxylic acid anhydride (A) (hereinafter referred to as component (A)), and dimer diamine (b1) (hereinafter referred to as component (b1)). And the diamine (B) (hereinafter referred to as the component (B)) containing the trimer triamine (b2) (hereinafter referred to as the component (b2)) in a range where the mass ratio [(b1) / (b2)] is 97/3 to 70/30. ) As a reaction component.

As the component (A), various known aromatic tetracarboxylic acid anhydrides can be used. Specifically, those shown by the following structure can be used.
(In the formula, X is a single bond, —SO ₂ —, —CO—, —O—, —O—C ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ —O— or —COO—X ^1. —OCO— (X ¹ represents — (CH ₂ ) ₁ — (1 = 1 to 20) or —H ₂ C—HC (—O—C (═O) —CH ₃ ) —CH ₂ —). Represents.)

  Specific examples of the component (A) include, for example, pyromellitic dianhydride, 4,4′-oxydiphthalic dianhydride, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, 3, 3 ′, 4,4′-diphenyl ether tetracarboxylic dianhydride, 3,3 ′, 4,4′-diphenylsulfone tetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic anhydride, 1,4,5,8-naphthalenetetracarboxylic acid anhydride, 2,3,6,7-naphthalenetetracarboxylic acid anhydride, 3,3 ′, 4,4′-biphenyltetracarboxylic acid dianhydride, 2, 2 ', 3,3'-biphenyltetracarboxylic dianhydride, 2,3,3', 4'-biphenyltetracarboxylic dianhydride, 2,3,3 ', 4'-benzophenonetetracarboxylic dianhydride Things, a few 3 ′, 4′-diphenyl ether tetracarboxylic dianhydride, 2,3,3 ′, 4′-diphenylsulfone tetracarboxylic dianhydride, 2,2-bis (3,3 ′, 4,4′-tetra Carboxyphenyl) tetrafluoropropane dianhydride, 2,2′-bis (3,4-dicarboxyphenoxyphenyl) sulfone dianhydride, 2,2-bis (2,3-dicarboxyphenyl) propane dianhydride, 2,2-bis (3,4-dicarboxyphenyl) propane dianhydride, 4,4 ′-[propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic dianhydride, and the like These may be used in combination of two or more. Among these, 3,3 ′, 4,4′-benzophenone tetracarboxylic dianhydride, from the viewpoint of compatibility between the components (A) and (B), room temperature adhesion, heat resistance adhesion, and the like, At least one selected from the group consisting of 4 ′-[propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic dianhydride and 4,4′-oxydiphthalic anhydride is preferable.

Component (b1) is obtained by substituting all the carboxyl groups of dimer acid, which is a dimer of unsaturated fatty acid such as oleic acid, with primary amino groups (see JP-A-9-12712, etc.), and various known ones. Can be used without particular limitation. Hereinafter, non-limiting structural formulas of dimeramine are shown (in each formula, m + n = 6 to 17, p + q = 8 to 19, and a broken line portion represents a carbon-carbon single bond or a carbon-carbon double bond. means.).

  Examples of the commercially available component (b1) include Versamine 551 (manufactured by BASF Japan), Versamine 552 (manufactured by Cognix Japan); Etc.). In addition, the dimer diamine component in these commercial products is about 95-98 mass% normally, and the below-mentioned trimer triamine may be normally contained in 2 mass% or less as a remainder.

The component (b2) is obtained by substituting all carboxyl groups of trimer acid (see JP 2013-505345 A, etc.), which is a trimer of unsaturated fatty acids such as oleic acid, with primary amino groups. Can be used without particular limitation. Hereinafter, non-limiting structural formulas of trimer triamines are shown (in each formula, m + n = 6 to 17, p + q = 8 to 19, and a broken line portion represents a carbon-carbon single bond or a carbon-carbon double bond. And R represents an ethylene group (—CH ₂ CH ₂ —) or an ethenylene group (—CH═CH—).

  Examples of the commercially available component (b2) include PRIAMINE 1071 (manufactured by Croda Japan Co., Ltd.). In addition, the trimer triamine component in a commercial item is about 15-20 mass% normally, and the said dimer diamine may be contained exceeding 80 mass% as remainder.

  The mass ratio [(b1) / (b2)] of the (b1) component and the (b2) component in the component (B) is about 97/3 to 70/30. By being in this range, the balance between the flow control property and the heat-resistant adhesiveness 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 93/7 to 83/17.

  The method for preparing the component (B) is not particularly limited. For example, the component (b1) and the component (b2) produced by various known methods are mixed so that the mass ratio is achieved, or a commercial product of the component (b1) and a commercial product of the component (b2) And the like so that the molar ratio is achieved.

  The molar ratio of the component (A) to the component (B) is not particularly limited, but usually 1 <[(A) / (B)] <1 from the viewpoint of maintaining a high storage rigidity at a high temperature. About 0.5, preferably about 1.03 <[(A) / (B)] <1.4, more preferably from the viewpoint of gelation and the like, 1.07 <[(A) / (B)] < About 1.4, and most preferably about 1.09 <[(A) / (B)] <1.16.

  In the present invention, diaminopolysiloxane (hereinafter referred to as component (b3)) may be included in the monomer group including component (A) and component (B). 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 diaminocyclohexane, diaminodicyclohexylmethane, dimethyl-diaminodicyclohexylmethane, diaminobicyclo [2.2.1] heptane, and bis (aminomethyl) -bicyclo. [2.2.1] heptane, 3 (4), 8 (9) -bis (aminomethyl) tricyclo [5.2.1.02,6] decane, isophoronediamine, 4,4′-diaminodicyclohexylmethane and Cycloaliphatic diamines such as 1,3-bisaminomethylcyclohexane; 2,2-bis [4- (3-aminophenoxy) phenyl] propane, 2,2-bis [4- (4-aminophenoxy) phenyl] propane Bisaminophenoxyphenylpropanes such as 3,3′-diaminodiphenyl ether, 3,4′-dia Diaminodiphenyl ethers such as nodiphenyl ether and 4,4′-diaminodiphenyl ether; phenylenediamines such as p-phenylenediamine and m-phenylenediamine; 3,3′-diaminodiphenyl sulfide, 3,4′-diaminodiphenyl sulfide, 4 Diaminodiphenyl sulfides such as 3,4′-diaminodiphenylsulfide; diaminodiphenylsulfones such as 3,3′-diaminodiphenylsulfone, 3,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenylsulfone; Diaminobenzophenones such as' -diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone; 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane Diaminodiphenylmethanes such as 3,4'-diaminodiphenylmethane; 2,2-di (3-aminophenyl) propane, 2,2-di (4-aminophenyl) propane, 2- (3-aminophenyl) -2- Diaminophenylpropanes such as (4-aminophenyl) propane; 2,2-di (3-aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2,2-di (4- Aminophenyl) -1,1,1,3,3,3-hexafluoropropane, 2- (3-aminophenyl) -2- (4-aminophenyl) -1,1,1,3,3,3- Diaminophenyl hexafluoropropanes such as hexafluoropropane; 1,1-di (3-aminophenyl) -1-phenylethane, 1,1-di (4-aminophenyl) -1-phenylethane; Diaminophenylphenylethanes such as-(3-aminophenyl) -1- (4-aminophenyl) -1-phenylethane; 1,3-bis (3-aminophenoxy) benzene, 1,3-bis (4- Bisaminophenoxybenzenes such as aminophenoxy) benzene, 1,4-bis (3-aminophenoxy) benzene, 1,4-bis (4-aminophenoxy) benzene; 1,3-bis (3-aminobenzoyl) benzene Bisaminobenzoylbenzenes such as 1,3-bis (4-aminobenzoyl) benzene, 1,4-bis (3-aminobenzoyl) benzene, 1,4-bis (4-aminobenzoyl) benzene; -Bis (3-amino-α, α-dimethylbenzyl) benzene, 1,3-bis (4-amino-α, α-dimethylbenzyl) benzene Bisaminodimethylbenzylbenzenes such as 1,4-bis (3-amino-α, α-dimethylbenzyl) benzene and 1,4-bis (4-amino-α, α-dimethylbenzyl) benzene; Bis (3-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,3-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene, 1,4-bis (3-amino-α, bisaminoditrifluoromethylbenzylbenzenes such as α-ditrifluoromethylbenzyl) benzene and 1,4-bis (4-amino-α, α-ditrifluoromethylbenzyl) benzene; 2,6-bis (3-aminophenoxy) ) Amino such as benzonitrile, 4,4′-bis (3-aminophenoxy) biphenyl, 4,4′-bis (4-aminophenoxy) biphenyl Enoxybiphenyls; aminophenoxyphenyl ketones such as bis [4- (3-aminophenoxy) phenyl] ketone and bis [4- (4-aminophenoxy) phenyl] ketone; bis [4- (3-aminophenoxy) ) Phenyl] sulfide, aminophenoxyphenyl sulfides such as bis [4- (4-aminophenoxy) phenyl] sulfide; bis [4- (3-aminophenoxy) phenyl] sulfone, bis [4- (4-aminophenoxy) Aminophenoxyphenyl sulfones such as phenyl] sulfone; aminophenoxyphenyl ethers such as bis [4- (3-aminophenoxy) phenyl] ether and bis [4- (4-aminophenoxy) phenyl] ether; Bis [4- (3-aminophenoxy) phenyl] propane 2,2-bis [3- (3-aminophenoxy) phenyl] -1,1,1,3,3,3-hexafluoropropane, 2,2-bis [4- (4-aminophenoxy) phenyl] Examples include aminophenoxyphenylpropanes such as -1,1,1,3,3,3-hexafluoropropane, and examples of the component (B) other than the components (b1) to (b3) other than the above are 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, 1,3-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,3-bis [4 -(4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- (3-aminophenoxy) -α, α-dimethylbenzyl] benzene, 1,4-bis [4- ( 4-aminophenoxy) -α, α-dimethylbenzyl] benzene, 4,4′-bis [4- (4-aminophenoxy) benzoyl] diphenyl ether, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] benzophenone, 4,4′-bis [4- (4-amino-α, α-dimethylbenzyl) phenoxy] diphenylsulfone, 4,4′-bis [4- (4-aminophenoxy) Phenoxy] diphenylsulfone, 3,3′-diamino-4,4′-diphenoxybenzophenone, 3,3′-diamino-4,4′-dibiphenoxybenzophenone 3,3′-diamino-4-phenoxybenzophenone, 3,3′-diamino-4-biphenoxybenzophenone, 6,6′-bis (3-aminophenoxy) 3,3,3 ′, 3′-tetramethyl -1,1'-spirobiindane, 6,6'-bis (4-aminophenoxy) 3,3,3,3,3'-tetramethyl-1,1'-spirobiindane, 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- Aminoprotoxy) 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 Rubis (3-aminopropyl) ether, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5-diaminopentane, 1,6-diaminohexane, 1,7-diaminoheptane, 1,8- Examples include diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diaminododecane, 2,6-bis (3-aminophenoxy) pyridine and the like. Two or more of these may be combined.

  Even when the component (b3) is used, the amount of the component (A) and the component (B) used is not particularly limited. When the component (b3) is used, from the viewpoint of the solubility of the component (1) in the organic solvent described later and the balance between room temperature adhesion, heat-resistant adhesion and low dielectric properties, the component (A) and ( The molar ratio with the component B) is about 0.6 <[(A) / (B)] <1.4, preferably about 0.8 <[(A) / (B)] <1.2. It is good.

  The use ratio of the components (b1) to (b3) is not particularly limited, but usually the molar ratio of the components (b1) and (b2) to the components (b1), (b2) and (b3) is 0.3 <[[(b1) + (b2)] / [(b1) + (b2) + (b3)]] <1, preferably 0.6 <[[(b1) + (b2)] / [(B1) + (b2) + (b3)]] <1, more preferably 0.6 <[[(b1) + (b2)] / [(b1) + (b2) + (b3)]] It should be <0.96.

  (1) A component can be manufactured by various well-known methods. For example, the component (A), the component (B1) including the component (b1), the component (b2), and the component (b3) as necessary, are usually about 60 to 120 ° C (preferably about 80 to 100 ° C). At the temperature, the polyaddition reaction is usually performed for about 0.1 to 2 hours (preferably about 0.1 to 0.5 hours). Subsequently, the obtained polyaddition product is further subjected to imidation reaction, that is, dehydration ring closure, at a temperature of about 80 to 250 ° C., preferably about 100 to 200 ° C., for about 0.5 to 50 hours (preferably about 1 to 20 hours). By reacting, the desired component (1) is obtained.

  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. Two or more kinds may be combined. Examples of the dehydrating agent include aliphatic acid anhydrides such as acetic anhydride and aromatic acid anhydrides such as benzoic anhydride, and these may be used in combination of two or more.

  (1) The imide cyclization rate of a component is not specifically limited. Here, the “imide ring closure rate” means 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. And the normal temperature adhesiveness and heat-resistant adhesiveness become favorable by making the imide cyclization rate of (1) component into 70% or more normally, Preferably it is about 85-100%.

  The physical properties of the component (1) thus obtained are not particularly limited, but examples of the upper limit of the glass transition temperature include 250, 200, 150, 100 ° C., and examples of the lower limit include 90, 80, 70, 60, 50, 40, 30, 20 ° C. and the like. The range of the glass transition temperature can be appropriately set by selecting from the above upper limit and lower limit values, but the glass transition temperature is usually 20 to 20 from the viewpoint of the balance between room temperature adhesion, heat resistance adhesion and low dielectric properties. It is about 250 degreeC, Preferably it is about 30-200 degreeC. The weight average molecular weight is not particularly limited, but examples of the upper limit include 60000, 50000, 40000, 30000, 20000, 10000, 9000, 8000, 7000, 6000, 5000, etc. 50000, 40000, 30000, 20000, 10000, 9000, 8000, 7000, 6000, 5000, 4000, 3000 and the like. The range of the weight average molecular weight can be selected and set, for example, from the above upper limit and lower limit values, and is usually about 3000 to 60000, preferably about 6000 to 40000, from the same viewpoint as described above. A weight average molecular weight can be calculated | required as a polystyrene conversion value measured, for example by gel permeation chromatography (GPC).

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

  As the component (2), various known materials can be used without particular limitation as long as they function as a crosslinking agent for polyimide. Specifically, for example, at least one selected from the group consisting of an epoxy compound, a benzoxazine compound, a bismaleimide compound, and a cyanate ester compound is preferable.

  Examples of the epoxy compound include a phenol novolac type epoxy compound, a cresol novolac type epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, a bisphenol S type epoxy compound, a hydrogenated bisphenol A type epoxy compound, and a 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, glycidylamine-type epoxy compounds, triphenolmethane-type epoxy compounds, alkyl-modified triphenols Methane-type epoxy compounds, biphenyl-type epoxy compounds, dicyclopentadiene skeleton-containing epoxy compounds, naphthalene skeleton-containing epoxy compounds, allies Alkylene type epoxy compounds, tetraglycidyl xylylenediamine, modified epoxy compound comprising modified with these epoxy compounds dimer acid, and dimer acid diglycidyl ester and the like, may be in combination of two or more. Examples of commercially available products include “jER828”, “jER834”, “jER807” manufactured by Mitsubishi Chemical Corporation, “ST-3000” manufactured by Nippon Steel Chemical Co., Ltd., and manufactured by Daicel Chemical Industries, Ltd. “Celoxide 2021P”, “YD-172-X75” manufactured by Nippon Steel Chemical Co., Ltd., “TETRAD-X” manufactured by Mitsubishi Gas Chemical Co., Ltd., and the like. Among these, from the viewpoint of the balance of heat-resistant adhesiveness, moisture-absorbing solder heat resistance and low dielectric properties, 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 At least one selected is preferable.

In particular, tetraglycidyldiamine having the following structure has good compatibility with the component (1). In addition, when this is used, it is easy to reduce the elastic modulus of the adhesive layer, and the heat resistant adhesiveness and low dielectric properties are also improved.
(In the formula, Y represents a phenylene group or a cyclohexylene group.)

  (2) When using an epoxy compound as a component, various well-known hardening | curing agents for epoxy compounds can be used together. Specifically, for example, succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride Acid, or a mixture of 4-methyl-hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, norbornane-2,3-dicarboxylic anhydride Acid anhydride-based curing agents such as methylnorbornane-2,3-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 3-dodecenyl succinic anhydride, octenyl succinic anhydride; dicyandiamide (DICY), aromatic diamine ( Product name "Lonacure M-" EA ”,“ Lonacure M-DETDA ”, etc., all manufactured by Lonza Japan Co., Ltd.), amine curing agents such as aliphatic amines; phenol novolac resins, cresol novolac resins, bisphenol A type novolac resins, triazine-modified phenol novolac resins Phenolic hydroxyl group-containing phosphazenes (trade name “SPH-100” manufactured by Otsuka Chemical Co., Ltd.), etc., phenolic curing agents, cyclic phosphazene compounds, rosin crosslinking agents such as maleic acid-modified rosin and hydrides thereof, etc. 2 or more types may be combined. Of these, phenol-based curing agents, particularly phenolic hydroxyl group-containing phosphazene-based curing agents are preferred. The amount of these curing agents used is not particularly limited, but is usually about 0.1 to 120% by mass, preferably about 10 to 40% by mass when the solid content of the adhesive of the present invention is 100% by mass. is there.

  (2) When an epoxy compound is used as the component and the curing agent is used, a reaction catalyst can be used. Specifically, for example, 1,8-diaza-bicyclo [5.4.0] undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, tris (dimethylaminomethyl) phenol and the like. Secondary amines; imidazoles such as 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-heptadecylimidazole; tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, phenyl Organic phosphines such as phosphine; tetraphenylphosphonium / tetraphenylborate, 2-ethyl-4-methylimidazole / tetraphenylborate, N-methylmorpholine / tetraphenylborate, etc. Niruboron salts and the like, may be in combination of two or more. Moreover, the usage-amount of the said reaction catalyst in particular is although it does not restrict | limit, Usually, when the solid content of the adhesive agent of this invention is 100 mass%, it is about 0.01-5 mass%.

  Examples of the benzoxazine compound include 6,6- (1-methylethylidene) bis (3,4-dihydro-3-phenyl-2H-1,3-benzoxazine) and 6,6- (1-methylethylidene). ) Bis (3,4-dihydro-3-methyl-2H-1,3-benzoxazine) and the like, and two or more of them may be combined. Note that a phenyl group, a methyl group, a cyclohexyl group, or the like may be bonded to nitrogen of the oxazine ring. In addition, examples of commercially available products include “benzoxazine Fa type” and “benzoxazine Pd type” manufactured by Shikoku Kasei Kogyo Co., Ltd., “RLV-100” manufactured by Air Water Co., etc. Is mentioned.

  Examples of the bismaleimide compound include 4,4′-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether bismaleimide, 3,3′-dimethyl-5,5′-diethyl-4,4′-diphenylmethane. Bismaleimide, 4-methyl-1,3-phenylenebismaleimide, 1,6′-bismaleimide- (2,2,4-trimethyl) hexane, 4,4′-diphenyl ether bismaleimide, 4,4′-diphenylsulfone A bismaleimide etc. are mentioned, You may combine 2 or more types. Examples of commercially available products include “BAF-BMI” manufactured by JFE Chemical Co., Ltd.

  Examples of the cyanate ester compound include 2-allylphenol cyanate ester, 4-methoxyphenol cyanate ester, and 2,2-bis (4-cyanatophenol) -1,1,1,3,3,3-hexafluoro. Propane, bisphenol A cyanate ester, diallyl bisphenol A cyanate ester, 4-phenylphenol cyanate ester, 1,1,1-tris (4-cyanatophenyl) ethane, 4-cumylphenol cyanate ester, 1,1-bis ( 4-cyanatophenyl) ethane, 4,4′-bisphenol cyanate ester, 2,2-bis (4-cyanatophenyl) propane, and the like may be used, and two or more thereof may be combined. Moreover, as a commercial item, "PRIMASET BTP-6020S (Lonza Japan Co., Ltd. product)" etc. are mentioned, for example.

  As the component (3), various known organic solvents can be used. Specific examples include aprotic polar solvents such as N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfoxide, N-methylcaprolactam, methyltriglyme and methyldiglyme, and fats such as cyclohexanone and methylcyclohexane. Examples include cyclic solvents, alcohol solvents such as methanol, ethanol, propanol, benzyl alcohol, and cresol, aromatic solvents such as toluene, and the like. The amount of the organic solvent used is not particularly limited, but is usually in the range where the solid content mass of the resin composition according to the present invention is usually about 10 to 60% by mass.

  Although the usage-amount of (1) component, (2) component, and (3) component in the polyimide-type adhesive of this invention is not specifically limited, (2) with respect to 100 mass parts (solid content conversion) of (1) component. Examples of the upper limit of the component include 60, 50, 40, 30, 20, 10 parts by mass, and examples of the lower limit include 50, 40, 30, 20, 10, 5, 3, 2 parts by mass, and the like. Examples of the upper limit of the component (3) include 900, 800, 700, 600, 500, 400, 300 parts by mass, and examples of the lower limit include 300, 250, 200, 150 parts by mass. Etc. The range of the component (2) and the component (3) can be selected and set from the upper and lower limit values, for example, and adhesives such as handling property at the time of coating, heat resistance, electrical characteristics, adhesiveness, etc. From the viewpoint of the balance of physical properties, the component (2) is usually about 2 to 60 parts by mass, preferably about 3 to 40 parts by mass with respect to 100 parts by mass (in terms of solid content) of the component (1), and The component (3) is about 150 to 900 parts by mass, preferably about 200 to 500 parts by mass.

  The polyimide adhesive of the present invention can be obtained, for example, by dissolving the component (1) and the component (2) in the component (3). If necessary, the ring-opening esterification reaction catalyst, dehydrating agent, plasticizer, weathering agent, antioxidant, heat stabilizer, lubricant, antistatic agent, whitening agent, colorant, conductive agent, mold release Additives such as an agent, a surface treatment agent, a viscosity modifier, a phosphorus flame retardant, a flame retardant filler, a silica filler, and a fluorine filler can be blended.

  The film adhesive of the present invention is an article obtained from the polyimide adhesive of the present invention. Specifically, for example, the adhesive is applied to a suitable support, heated, and cured by volatilizing the component (3), and then peeled off from the support. Although the thickness of this adhesive material is not specifically limited, Usually, it is about 3-40 micrometers. Examples of the support include the following.

  The adhesive sheet of the present invention is an article including, as components, an adhesive layer obtained from the polyimide adhesive according to the present invention or the film adhesive according to the present invention. Examples of the support include polyester, polyimide, polyimide-silica hybrid, polyethylene, polypropylene, polyethylene terephthalate, polyethylene naphthalate, polymethyl methacrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin, ethylene terephthalate, and the like. Examples thereof include plastic films such as aromatic polyester resins obtained from phenol, phthalic acid, hydroxynaphthoic acid and the like and parahydroxybenzoic acid (so-called liquid crystal polymer; “Kexar” manufactured by Kuraray Co., Ltd.). Moreover, the said coating means is employable when apply | coating the polyimide-type adhesive which concerns on this invention to this support body. The thickness of the coating layer is not particularly limited as long as the thickness after drying is usually about 1 to 100 μm, preferably about 3 to 50 μm. The adhesive layer of the adhesive sheet may be protected with various protective films.

  The copper foil with resin of the present invention is an article including the adhesive layer and the copper foil according to the present invention as constituent elements. Specifically, the polyimide adhesive or the film adhesive is applied or bonded to a copper foil. Examples of the copper foil include rolled copper foil and electrolytic copper foil. The thickness is not particularly limited, and is usually about 1 to 100 μm, preferably about 2 to 38 μm. The copper foil may be subjected to various surface treatments (roughening, rust prevention, etc.). Examples of the rust prevention treatment include so-called mirror finishing treatment such as plating treatment using a plating solution containing Ni, Zn, Sn and the like, and chromate treatment. Moreover, the above-mentioned method is mentioned as a coating means. The adhesive layer of the resin-coated copper foil may be uncured, or may be partially cured or completely cured under heating. The partially cured adhesive layer is in a state called a so-called B stage. Further, the thickness of the adhesive layer is not particularly limited, and is usually about 0.5 to 30 μm. Further, a copper foil can be further bonded to the adhesive surface of the resin-attached copper foil to form a double-sided resin-attached copper foil.

  The copper-clad laminate of the present invention is an article formed by bonding the resin-coated copper foil of the present invention and a copper foil or an insulating sheet, and is also called CCL (Copper Clad Laminate). Specifically, the copper foil with resin of the present invention is bonded to at least one surface or both surfaces of various known copper foils or insulating sheets under heating. When bonding to one side, you may crimp | bond the thing different from the resin-coated copper foil of this invention to the other side. Moreover, the number of the resin-coated copper foil and the insulating sheet in the copper-clad laminate is not particularly limited. The insulating sheet is preferably a prepreg. A prepreg means a sheet-like material obtained by impregnating a reinforcing material such as glass cloth with a resin and curing it to the B stage (JIS C 5603). As the resin, an insulating resin such as a polyimide resin, a phenol resin, an epoxy resin, a polyester resin, a liquid crystal polymer, or an aramid resin is usually used. The thickness of the prepreg is not particularly limited, and is usually about 20 to 500 μm. The heating and pressure bonding conditions are not particularly limited, and are usually about 150 to 280 ° C. (preferably about 170 ° C. to 240 ° C.) and about 0.5 to 20 MPa (preferably about 1 to 8 MPa).

  The printed wiring board of the present invention is an article formed 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-additive method include a method of patterning a copper foil surface of the copper-clad laminate of the present invention with a resist film, performing electrolytic copper plating, removing the resist, and etching with an alkaline solution. Further, the thickness of the circuit pattern layer in the printed wiring board is not particularly limited. Moreover, a multilayer substrate can also be obtained by using the printed wiring board as a core base material and laminating the same printed wiring board or other known printed wiring boards or printed circuit boards thereon. In the lamination, not only the polyimide adhesive of the present invention but also other known polyimide adhesives can be used. Further, the number of stacked layers in the multilayer substrate is not particularly limited. Moreover, a via hole may be inserted and the inside may be plated each time it is laminated. The line / space ratio of the circuit pattern is not particularly limited, but is usually about 1 μm / 1 μm to 100 μm / 100 μm. The height of the circuit pattern is not particularly limited, but is usually about 1 to 50 μm.

  The multilayer wiring board according to the present invention includes one printed wiring board or one printed circuit board as a core substrate, an adhesive layer according to the present invention, and one printed wiring board or one print as another substrate. An article including a circuit board as a component. Such one printed wiring board or one printed circuit board may be those according to the present invention, and may be various known ones.

The multilayer wiring board according to the present invention can be obtained by a manufacturing method including the following step 1 and step 2.
Process 1: A base material with an adhesive layer is produced by bringing the polyimide adhesive or film adhesive according to 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. Step 2: Step of laminating one printed wiring board or one printed circuit board on the base material with the adhesive layer, and press-bonding under heat and pressure

  Such one printed wiring board or one printed circuit board may be those according to the present invention, and may be various known ones.

  In step 1, means for bringing the polyimide adhesive or film adhesive of the present invention into contact with the adherend is not particularly limited, and various known coating means such as curtain coater, roll coater, laminator, press, etc. Can be used.

  The heating temperature and the pressure bonding time in step 2 are not particularly limited. Usually, (a) after bringing the polyimide adhesive or film adhesive of the present invention into contact with at least one surface of the core substrate, usually about 70 to 200 ° C. In order to allow the curing reaction of component (2) (2) to proceed, it is usually further heated at about 150 ° C. to 250 ° C. for about 10 minutes to 3 hours. It is good to do. Further, the pressure is not particularly limited, but is usually about 0.5 to 20 MPa, preferably about 1 to 8 MPa through the steps (a) and (b).

  EXAMPLES Hereinafter, although this invention is demonstrated concretely through an Example and a comparative example, the scope of the present invention is not limited by them. In each example, parts and% are based on mass unless otherwise specified.

<Manufacture of polyimide>
Production Example 1
4,4 '-[propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic dianhydride (commercial product) in a reaction vessel equipped with a stirrer, a water separator, a thermometer and a nitrogen gas introduction pipe The name “BisDA-1000”, manufactured by SABIC Innovative Plastics Japan G.K. (hereinafter abbreviated as “BisDA”) 300.00 g, cyclohexanone 1042.73 g, and methylcyclohexane 208.55 g were charged and heated to 60 ° C. Next, after dropping 289.36 g of a commercially available trimmer triamine (trade name “PRIAMINE 1071”, trimer triamine / dimeramine amine mass ratio = 20/80, manufactured by Croda Japan Co., Ltd.), an imidization reaction at 140 ° C. for 12 hours. As a result, a solution of polyimide (1-1) (non-volatile content: 31.9%) was obtained. The molar ratio of acid component / amine component of the polyimide was 1.13.

  Manufacture examples and comparative manufacture examples other than manufacture example 1 were performed by the same method as manufacture example 1 except having changed the composition of the resin solution as described in Table 1, and obtained polyimide. For example, Comparative Production Example 1 was performed according to the following procedure.

Comparative production example 1
A reaction vessel similar to Production Example 1 was charged with 310.00 g of BisDA, 992.00 g of cyclohexanone and 124.00 g of methylcyclohexane, and heated to 60 ° C. Next, after gradually adding 306.59 g of a commercially available dimer diamine (trade name “PRIAMINE 1075”, trimer triamine / dimer diamine mass ratio = 2/98, manufactured by Croda Japan Co., Ltd.), the mixture was heated to 140 ° C. for 12 hours. The imidization reaction was carried out to obtain a polyimide (2-1) solution (nonvolatile content: 35.7%). The molar ratio of acid component / amine component of the polyimide was 1.05.

BisDA-1000 ... 4,4 '-[propane-2,2-diylbis (1,4-phenyleneoxy)] diphthalic dianhydride. Made by SABIC Innovative Plastics Japan GK.
PRIAMINE 1071... Trimer triamine / dimeramine mass ratio = 20/80, manufactured by Croda Japan Co., Ltd.
PRIAMINE 1075: Trimmer triamine / dimeramine amine mass ratio = 2/98, manufactured by Croda Japan Co., Ltd.

<Measurement of storage rigidity>
The solutions of Production Example 1 and Comparative Production Example 1 were mixed with Naflon PTFE tape TOMBO No. It was coated on 9001 (Nichias Co., Ltd.), dried at room temperature for 12 hours, and then dried at 150 ° C. for 5 minutes to prepare an adhesive sheet of about 20 μm.

  Next, the adhesive sheet is folded to prepare a sheet having a thickness of about 300 μm, and the temperature dependence of the storage rigidity is measured using a commercially available viscoelasticity measuring device (ARES-2KSTD-FCO-STD, manufactured by Rheometric Scientific, Inc.). Was measured. The temperature rising rate was 10 ° C./min. The results are shown in FIG.

Example 1
100.0 g of polyimide resin (1-1) solution, 22.34 g of polyimide (2-1) solution, (2) bisphenol A type epoxy resin (manufactured by Japan Epoxy Resin Co., Ltd., trade name “jER828”, Epoxy equivalent 190 g / eq) 0.82 g, hydroxyl group-containing polyphenylene ether (trade name “SA90” SABIC Innovative Plastics Japan GK, hydroxyl group equivalent 840 g / eq) 3.61 g, and (3) 21.11 g of toluene as an organic solvent. Were mixed and stirred well to obtain a resin composition having a nonvolatile content of 30.0%.

  Examples and Comparative Examples other than Example 1 were performed in the same manner as in Example 1 except that the composition of the adhesive was changed as described in Table 2. For example, Comparative Example 1 was performed according to the following procedure.

Comparative Example 1
100.0 g of polyimide (2-1) solution, bisphenol A type epoxy resin (made by Japan Epoxy Resin Co., Ltd., trade name “jER828”, epoxy equivalent 190 g / eq) 0.73 g, hydroxyl group-containing polyphenylene as component (2) By mixing 3.24 g of ether (trade name “SA90” manufactured by SABIC Innovative Plastics Japan G.K., hydroxyl equivalent 840 g / eq) and 28.24 g of toluene as an organic solvent and stirring well, the non-volatile content is 30.0% A resin composition was obtained.

In addition, the organic solvent (3) can also contain the organic solvent used when manufacturing a polyimide.
SG-708-6: (manufactured by Nagase ChemteX Corporation: acrylic elastomer)

<Preparation of adhesive sheet>
The adhesive composition of Example 1 was prepared from a block copolymerized polyimide-silica hybrid film (trade name “Pomilan N25”, manufactured by Arakawa Chemical Industries, Ltd .; thermal expansion coefficient = 18 ppm, tensile modulus = 5.9 GPa, film thickness 25 μm, width 10 cm, length 15 cm) was applied with a gap coater so that the thickness after drying was 20 μm and the left and right margins were each 1 cm, and then dried at 180 ° C. for 3 minutes to obtain an adhesive sheet.

<Preparation of copper-clad laminate>
From the adhesive sheet, a film piece having a width of 10 cm and a length of 4 cm was cut in a direction perpendicular to the direction of the gap coat. Next, a test sample in which the adhesive surface of the film piece was superimposed on the mirror surface side of a commercially available electrolytic copper foil (trade name “F2-WS”, manufactured by Furukawa Circuit Foil Co., Ltd., 18 μm thickness, width 10 cm, length 5 cm). Was made. A schematic diagram of the test sample is shown in FIG.

  Next, the test sample was placed on a support for pressing, and a laminated film was produced by heating and pressing under conditions of pressure 5 MPa, 170 ° C. and 30 minutes through a support obtained from the same material from above. .

1. Adhesion test About the said copper clad laminated board, peeling strength (N / cm) was measured according to JISC6481 (copper clad laminated board test method for flexible printed wiring boards). The results are shown in Table 3.

2. Solder heat resistance test The copper-clad laminate was floated in a 288 ° C solder bath with the copper foil side down for 30 seconds, and the presence or absence of changes in appearance was confirmed. The case where there was no change was marked with ○, and the case where there was foaming or swelling was marked with ×. The results are shown in Table 3.

3. Evaluation of Flow Control Property When the right end of the adhesive layer (cured layer) in the laminated film was visually observed, it was confirmed that there was no change in the end position before and after the hot press. That is, the hardened layer did not flow out in the horizontal direction even when heated and pressed (0 mm), and it was found that the flow controllability was good. The results are shown in Table 3.

<Preparation of Cured Sample for Measuring Dielectric Constant>
About 7 g of the adhesive composition of Example 1 was poured into a fluororesin PFA flat plate (diameter 75 mm, manufactured by Mutual Chemical Glass Co., Ltd.), 30 ° C. × 10 hours, 70 ° C. × 10 hours, 100 ° C. × 6 hours, Curing was performed under the conditions of 120 ° C. × 6 hours, 150 ° C. × 6 hours, 180 ° C. × 12 hours to obtain a cured product sample for dielectric constant measurement having a film thickness of about 300 μm.

  Next, according to JIS C2565, the dielectric constant and dielectric loss tangent of the cured product sample at 10 GHz were measured using a commercially available dielectric constant measuring device (cavity resonator type, manufactured by AET). The results are shown in Table 3.

  Tests 1 to 3 were performed 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 undulating shape about 2 mm in the horizontal direction of Pomilan N25 in the test laminate film.

Claims (19)

Aromatic tetracarboxylic acid anhydride (A) and a diamine containing dimer diamine (b1) and trimer triamine (b2) in a mass ratio [(b1) / (b2)] of 97/3 to 70/30 ( Polyimide (1) which is a reaction product of a monomer group including B). The polyimide (1) of Claim 1 whose (A) component is shown by the following structure.
(In the formula, X is a single bond, —SO ₂ —, —CO—, —O—, —O—C ₆ H ₄ —C (CH ₃ ) ₂ —C ₆ H ₄ —O— or —COO—X ^1. —OCO— (X ¹ represents — (CH ₂ ) ₁ — (1 = 1 to 20) or —H ₂ C—HC (—O—C (═O) —CH ₃ ) —CH ₂ —). Represents.) The polyimide (1) according to claim 1 or 2, wherein the molar ratio of the component (A) to the component (B) is 1 <[(A) / (B)] <1.5. The polyimide (1) according to any one of claims 1 to 3, wherein the monomer group further contains diaminopolysiloxane (b3). The polyimide (1) of Claim 4 whose molar ratio of (A) component and (B) component is 0.6 <[(A) / (B)] <1.4. The molar ratio of the component (b1) and the component (b2) to the component (b1), the component (b2) and the component (b3) is 0.3 <[[(b1) + (b2)] / [(b1) + The polyimide (1) according to claim 4 or 5, wherein (b2) + (b3)]] <1. The polyimide-type adhesive agent containing the polyimide (1) of any one of Claims 1-6, a crosslinking agent (2), and the organic solvent (3). The polyimide adhesive according to claim 7, wherein the crosslinking agent (2) is at least one selected from the group consisting of an epoxy compound, a benzoxazine compound, a bismaleimide compound, and a cyanate ester compound. The polyimide adhesive according to claim 8, wherein the epoxy compound is tetraglycidyldiamine having the following structure.
(In the formula, Y represents a phenylene group or a cyclohexylene group.) The component (2) is 11 to 900 parts by mass and the component (3) is 150 to 900 parts by mass with respect to 100 parts by mass (in terms of solid content) of the component (1). Polyimide adhesive. The film adhesive obtained from the polyimide-type adhesive agent in any one of Claims 7-10. The contact bonding layer obtained from the polyimide adhesive agent in any one of Claims 7-10, or the film adhesive of Claim 11. An adhesive sheet comprising the adhesive layer of claim 12 and a support film. A copper foil with resin comprising the adhesive layer of claim 12 and a copper foil. The copper clad laminated board containing the copper foil with resin of Claim 14, and one copper foil. The copper clad laminated board containing the copper foil with resin of Claim 15, and the one insulating sheet. A printed wiring board formed by forming a circuit pattern on the copper foil surface of the copper clad laminate of claim 15 or 16. One printed wiring board or one printed circuit board as a core substrate;
The adhesive layer of claim 12;
One printed wiring board or one printed circuit board as another substrate;
including,
Multilayer wiring board. A method for producing a multilayer wiring board, comprising the following steps 1 and 2.
Step 1: Contacting at least one surface of one printed wiring board or one printed circuit board as a core substrate with the polyimide-based adhesive according to any one of claims 7 to 10 or the film adhesive according to claim 11. Step 2 for producing a base material with an adhesive layer: Step of laminating one printed wiring board or one printed circuit board on the base material with an adhesive layer and press-bonding it under heat and pressure