TW201718715A - Modified polyimide, adhesive composition, copper foil with resin, copper-clad laminate, printed circuit board and multilayer substrate having low transmission losses and low dielectric losses and excellent in heat-resistance - Google Patents

Abstract

The problem to be solved by the present invention is to provide a polyimide which can obtain an adhesive layer having excellent adhesiveness, heat-resistance adhesiveness, flow-controlling property and low dielectric property. The solution for the present invention is a modified polyimide (1) which is a reactant of an polyimide with terminal acid anhydride group (A1) and a reactive alkoxysilyl compound (A2) represented by the following general formula (1); the polyimide with terminal acid anhydride group (A1) is a reactant of the monomer group (1); said monomer group (1) comprises an aromatic tetracarboxylic acid anhydride (a1) and a dimer diamine (a2). In the general formula (1), X represents a group containing a primary amino group, R1 represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R2 represents a hydrocarbon group having 1 to 8 carbon atoms, and a represents 0, 1 or 2.

Description

Modified polyimine, adhesive composition, copper foil with resin, copper clad laminate, printed wiring board and multilayer substrate

The present invention relates to an improved polyimine, an adhesive composition, a resin-attached copper foil, a copper-clad laminate, a printed wiring board, and a multilayer substrate. The adhesive composition is particularly suitable for the production of a multilayer circuit board (MLB: Multi-Layer Board).

Flexible Printed Wiring Board (FPWB) and Printed Circuit Board (PCB) and multi-layer circuit boards using these have been widely used in the following products: mobile phones or smart phones. Type communication equipment or its base station equipment, network related electronic equipment such as servers/routers, and large computers.

In recent years, in these products, high-frequency electronic signals are used for transmitting/processing large-capacity information at high speed, but since high-frequency signals are easily attenuated, it is sought to suppress transmission loss as much as possible for the above-mentioned multilayer wiring board. method.

A means for suppressing transmission loss in a multilayer wiring board, for example, a laminated polyimide circuit board or a printed circuit board is a polyimide-based adhesive which is excellent in not only heat-resistant adhesiveness but also dielectric constant and dielectric loss tangent. The characteristics are small (hereinafter also referred to as low dielectric properties) (see, for example, Patent Documents 1 to 3).

On the other hand, with the miniaturization, thinning and weight reduction of the above-mentioned products, the electronic components and the semiconductor components have been further miniaturized, and the flexible circuit boards for mounting them have been further refined. High density.

In order to obtain such a high-definition/high-density substrate to obtain a multilayer wiring board having high adhesion reliability, it is necessary to make the polyimide-based adhesive and/or the polyimide film-like adhesive material half at a temperature of about 180 °C. After the molten state (B phase), it is ensured to be wet throughout the adherends, that is, the fine concavities and irregularities of the printed wiring board and the printed circuit board, and forms an adhesive having excellent heat-resistant adhesiveness and low dielectric properties after post-baking. Floor.

In order to improve the wettability of the B-stage polyimide-based adhesive and/or the polyimide-based adhesive material, it is only necessary to reduce the melt viscosity or the loss of the elastic modulus, for example, the main material may be aggregated. The quinone imine is reduced in molecular weight, or an ether bond or a branched structure or the like is introduced into the molecule, or the molecular end is covered with a low molecule. However, if the melt viscosity is lowered by such a means, the adhesive layer is excessively softened and liquidified, and sometimes the flow control is performed such that the adhesive oozes or flows out from the edge of the multilayer wiring board under heat and pressure (stage B). Sexual damage, or thermal adhesion of the adhesive layer and low dielectric properties. [Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Laid-Open Patent Publication No. JP-A No. Hei. No. Hei. No. Hei. No. Hei. No. Hei.

[The problem that the invention wants to solve]

The main problem to be solved by the present invention is to provide a novel polyimine which is capable of obtaining an adhesive layer which is excellent in adhesion, heat-resistant adhesiveness, flow control property and low dielectric property.

Further, the problem to be solved by the present invention is to provide a novel adhesive composition which has an adhesive layer, and the adhesive of the adhesive layer is less likely to bleed out or flow out at the B stage, and has heat-resistant adhesiveness and low dielectric properties. good.

Further, the problem to be solved by the present invention is to provide an adhesive sheet, a resin-attached copper foil, a copper-clad laminate, a printed wiring board, and a multilayer substrate, which are provided with the above-mentioned adhesive layer. [Technical means to solve the problem]

As a result of intensive studies, the present inventors have found that the above problems can be solved by a modified polyimine which is a reactive alkoxy group containing a primary amine group. The decyl compound is obtained by reacting with a given anhydride terminal polyimine. In other words, the present invention relates to an improved polyimine, an adhesive composition, a copper foil with a resin, a copper clad laminate, a printed wiring board, and a multilayer substrate.

An improved polyimine (1) which is a reactant of an acid anhydride-based terminal polyimine (A1) and a reactive alkoxyalkylalkyl compound (A2) represented by the following formula (1) The acid anhydride-based terminal polyimine (A1) is a reactant of the monomer group (1), and the monomer group (1) comprises an aromatic tetracarboxylic anhydride (a1) and a dimer diamine (a2). Formula 1): In the formula (1), X represents a group containing a primary amino group, R ¹ represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R ² represents a hydrocarbon group having 1 to 8 carbon atoms, and a represents 0, 1 or 2.

An adhesive composition comprising: (1) a component, a crosslinking agent (2), and an organic solvent (3).

An adhesive sheet obtained by using the adhesive composition according to item 2.

A copper foil with a resin obtained by using the adhesive composition according to item 2.

A copper clad laminate obtained by using the resin-attached copper foil according to item 4.

A printed wiring board obtained by using the copper clad laminate according to item 5.

A multilayer substrate obtained by using the printed wiring board according to item 6. [efficacy]

According to the modified polyimine (1) of the present invention, an adhesive layer can be formed, and the adhesive layer is excellent in adhesion, heat-resistant adhesiveness, flow control property, and low dielectric property. We believe that the reason should be that the alkoxy group at the end of the modified polyimine (1) has undergone a sol-gel reaction to form a crosslinked structure, and the modified polycondensation has been improved by performing such terminal modification. The compatibility of quinone imine (1) with other components.

The adhesive composition of the present invention has a low melt viscosity at the B stage, and can be satisfactorily wetted with an adherend, that is, a copper foil, a copper clad laminate, a printed wiring board, and a printed circuit board. Further, according to the composition, an adhesive layer can be obtained, and the adhesive of the adhesive layer is less likely to bleed out or flow out in the B-stage, and has good heat-resistant adhesiveness and low dielectric properties. The adhesive composition can be utilized by being applied to various support bodies (adhesive sheets) or by forming a film-like adhesive material (adhesive sheet).

The resin-attached copper foil and copper-clad laminate of the present invention are suitable for manufacturing, for example, printed wiring boards and multilayer wiring boards for processing high-frequency signals: mobile communication devices such as smart phones or mobile phones, or base station devices thereof , network-related electronic devices such as servers/routers, and large computers.

[Preferred form of implementing the invention]

The modified polyimine (1) (hereinafter also referred to as component (1)) of the present invention is a polymer which is a predetermined reactive alkoxyalkylalkyl compound (A2) (hereinafter also referred to as (A2)) The component is obtained by sealing (endcapping) the terminal acid anhydride group of the predetermined anhydride terminal polyimine (A1) (hereinafter also referred to as (A1) component).

The component (A1) is preferably a reactant of the monomer group (1) (hereinafter also referred to as (component 1)), and the monomer group (1) contains an aromatic tetracarboxylic anhydride (a1) (hereinafter also referred to as In the case of the component (a1) and the dimer diamine (a2) (hereinafter also referred to as the component (a2)), various conventional materials can be used without particular limitation.

Examples of the component (a1) include pyromellitic dianhydride, 4,4′-oxydiphthalic dianhydride, and 3,3′,4,4′-benzophenonetetracarboxylic dianhydride. 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenylstilbene tetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic acid Anhydride, 1,4,5,8-naphthalenetetracarboxylic dianhydride, 2,3,6,7-naphthalenetetracarboxylic dianhydride, 3,3',4,4'-biphenyltetracarboxylic dianhydride, 2,2 ',3,3'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-biphenyltetracarboxylic dianhydride, 2,3,3',4'-benzophenonetetracarboxylic dianhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenylphosphonium tetracarboxylic dianhydride, 2,2-bis (3,3',4 , 4'-tetracarboxyphenyl)tetrafluoropropane dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl)ruthenium anhydride, 2,2-bis(2,3-dicarboxyl Phenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, and 4,4'-[propane-2,2-diylbis(1,4-phenylene oxide) The base)] diphthalic dianhydride or the like may be used in combination of two or more.

Wherein X represents a single bond, -SO ₂ -, -CO-, -O-, -O-C ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O- or -COO-Y-OCO -, Y represents -(CH ₂ ) _l - or -H ₂ C-HC(-O-C(=O)-CH ₃ )-CH ₂ -, l = 1 to 20.

The dimer diamine (a2) is a compound derived from a dimer of an unsaturated fatty acid such as oleic acid, that is, a dimer acid (see Japanese Patent Laid-Open Publication No. Hei 9-12712, etc.), and various conventional methods can be used. The dimer diamine is not particularly limited.

The structural formula of the component (a2) which is not limited is as follows. In each structural formula, m+n=6-17, p+q=8-19, and the dotted line means a carbon-carbon single bond or a carbon-carbon double bond.

The commercially available product of the component (a2) may, for example, be Versamine 551 (manufactured by BASF Japan Co., Ltd.); Versamine 552 (manufactured by Cognis Japan Co., Ltd., hydride of Versamine 551); PRIAMINE 1075, PRIAMINE 1074 (both Two or more types can be combined, such as Croda Japan Co., Ltd.). An example of a hydrogenated dimer diamine is given below.

(1) The component can contain various conventional diamine polyoxanes (hereinafter also referred to as (a3) components) as needed. Specific examples thereof include α,ω-bis(2-aminoethyl)polydimethyloxane, α,ω-bis(3-aminopropyl)polydimethyloxane, α. , ω-bis(4-aminobutyl)polydimethyloxane, α,ω-bis(5-aminopentyl)polydimethyloxane, α,ω-double [3-( 2-aminophenyl)propyl]polydimethyloxane, α,ω-bis[3-(4-aminophenyl)propyl]polydimethyloxane, etc. the above.

In the component (1), a diamine other than the component (a1) to the component (a3) (hereinafter also referred to as a component (a4)) can be contained as needed. Specific examples thereof include diaminocyclohexane, diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, tetramethyldiaminodicyclohexylmethane, and diaminodicyclohexyl. Propane, diaminobicyclo[2.2.1]heptane, bis(aminomethyl)bicyclo[2.2.1]heptane, 3(4),8(9)-bis(aminomethyl)tricyclo[ 5.2.1.0 ^2,6 ] alicyclic diamines such as decane, 1,3-bis(aminomethyl)cyclohexane, isophorone diamine; 2,2-bis[4-(3-amino group) Diaminophenoxyphenylpropanes such as phenoxy)phenyl]propane and 2,2-bis[4-(4-aminophenoxy)phenyl]propane; 3,3'-diamino Diaminodiphenyl ethers such as diphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether; p-phenylenediamine, m-phenylenediamine, etc. Phenylenediamines; diamines such as 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide Diphenyl sulfides; 3,3'-diaminodiphenyl fluorene, 3,4'-diaminodiphenyl fluorene, 4,4'-diaminodiphenyl hydrazine, etc. Phenylhydrazine; diamines such as 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone Benzophenones; diaminodiphenyl groups such as 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane Methane; 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-amine Diaminodiphenylpropanes such as phenyl)propane; 2,2-bis(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 Diaminophenyl hexafluoropropanes such as 1,3,3,3-hexafluoropropane; 1,1-di(3-aminophenyl)-1-phenylethane, 1,1-di ( Diaminophenylbenzene such as 4-aminophenyl)-1-phenylethane or 1-(3-aminophenyl)-1-(4-aminophenyl)-1-phenylethane Ethylene ethanes; 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy) Diaminophenoxybenzenes such as benzene, 1,4-bis(4-aminophenoxy)benzene; 1,3-bis(3-aminobenzimidyl)benzene, 1,3-double Diaminobenzene such as (4-aminobenzimidyl)benzene, 1,4-bis(3-aminobenzimidyl)benzene, 1,4-bis(4-aminobenzimidyl)benzene Mercaptobenzene; 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-di Diaminodimethylbenzenes such as methylbenzyl)benzene, 1,4-bis(4-amino-α,α-dimethylbenzyl)benzene; 1,3-bis(3-amine Base-α,α-bis(trifluoromethyl)benzyl)benzene, 1,3-bis(4-amino-α,α-bis(trifluoromethyl)benzyl)benzene, 1,4 - bis(3-amino-α,α-bis(trifluoromethyl)benzyl)benzene, 1,4-bis(4-amino-α,α-bis(trifluoromethyl)benzyl Di-aminobis(trifluoromethyl)benzylbenzenes such as benzene; 2,6-bis(3-aminophenoxy)benzonitrile, 2,6-bis(3-aminophenoxy) Pyridine; 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl, and the like, aminophenoxybiphenyls; Aminophenoxyphenyl ketones such as 4-(3-aminophenoxy)phenyl]one and bis[4-(4-aminophenoxy)phenyl]one; bis[4-(3 Aminophenoxyphenyl sulfides such as -aminophenoxy)phenyl] sulfide and bis[4-(4-aminophenoxy)phenyl] sulfide; bis[4-(3- Aminophenoxy)phenyl]anthracene, bis[4-(4-aminophenoxy)phenyl]anthracene and the like aminophenoxyphenyl anthracene; bis[4-(3-aminophenoxyl) Phenyl]ether Aminophenoxyphenyl ethers such as bis[4-(4-aminophenoxy)phenyl]ether; 2,2-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-amino) Aminophenoxyphenylpropanes such as phenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane; and 1,3-bis[4-(3-aminophenoxy) Benzobenzyl]benzene, 1,3-bis[4-(4-aminophenoxy)benzylidene]benzene, 1,4-bis[4-(3-aminophenoxy) Benzomethylene]benzene, 1,4-bis[4-(4-aminophenoxy)benzylidene]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-dimethylbenzene Methyl]benzene, 4,4'-bis[4-(4-aminophenoxy)benzylidene]diphenyl ether, 4,4'-bis[4-(4-amino-α, α-Dimethylbenzyl)phenoxy]benzophenone, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenyl Base, 4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenylanthracene, 3,3'-diamino-4,4'-diphenyl Benzophenone, 3,3'-diamino-4,4'-diphenoxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 3 , 3'-diamino-4-biphenoxybenzophenone, 6,6'-bis(3-aminophenoxy)3,3,3',3'-tetramethyl-1, 1'-6'-bis(3-aminophenoxy)3,3,3',3'-tetramethyl-1,1'-spirobiindane), 6,6'-bis(4-amino group Phenoxy) 3,3,3',3'-tetramethyl-1,1'-spirodecane, 1,3-bis(3-aminopropyl)tetramethyldioxane, 1 , 3-bis(4-aminobutyl)tetramethyldioxane, 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-(aminoethoxy)ethoxy]ethane, ethylene glycol bis(3-aminopropyl)ether, diethylene glycol bis (3) -aminopropyl)ether, triethylene glycol bis(3-aminopropyl)ether, ethylenediamine, 1,3-diaminopropane, 1,4-diaminobutane, 1,5- Diaminopentane, 1,6-diaminohexane 1,7-Diaminoheptane, 1,8-diaminooctane, 1,9-diaminodecane, 1,10-diaminodecane, 1,11-diaminoundecane Further, 1,12-diaminododecane or the like may be used in combination of two or more.

The molar ratio ((a1)/[(a2)+(a3)+(a4))])))) From the viewpoint of the balance between adhesion, heat resistance, flow controllability, and low dielectric properties, it is usually about 0.9 to 1.25, preferably about 0.9 to 1.1.

The ratio of each component in the component (a2) to the component (a4) is not particularly limited, and is generally as follows from the viewpoint of balance between heat-resistant adhesiveness, adhesiveness, flow control property, and low dielectric property. [(a2)/[(a2)+(a3)+(a4)]]] is usually about 10 mol% to 100 mol%, preferably about 30 mol% to 100 mol%. [(a3)/[(a2)+(a3)+(a4)]]] is usually from about 0 mol% to about 50 mol%, preferably from about 0 mol% to about 5 mol%. [(a4)/[(a2)+(a3)+(a4)]]] is usually from about 0 mol% to about 90 mol%, preferably from about 0 mol% to about 70 mol%.

The component (A1) can be produced by various conventional methods. For example, the components (a1) and (a2) and the components (a3) and (a4) which are used as needed are usually added at a temperature of usually about 60 to 120 ° C (preferably 80 to 100 ° C). The polymerization reaction is carried out for about 0.1 to 2 hours (preferably 0.1 to 0.5 hours). Further, the obtained addition polymer is further subjected to a ruthenium iodization reaction, that is, a dehydration ring closure reaction at a temperature of about 80 to 250 ° C, preferably 100 to 200 ° C, for about 0.5 to 50 hours (preferably 1 to 1). 20 hours). Moreover, when performing such a reaction, the component (3) mentioned later, especially an aprotic polar solvent can be used as a reaction solvent.

Further, when the ruthenium imidization reaction is carried out, various conventional reaction catalysts, dehydrating agents, and 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, methylpyridine and isoquinoline; Combine two or more. In addition, examples of the dehydrating agent include a fatty acid anhydride such as acetic anhydride or an aromatic acid anhydride such as benzoic anhydride, and two or more kinds thereof may be used in combination.

The ring closure ratio of the quinone imine of the component (A1) is not particularly limited, but is usually 70% or more, and preferably 85 to 100%. Here, the term "the ruthenium ring closure ratio" means the content of the cyclic quinone imine bond in the component (A1) (the same applies hereinafter), and can be various, for example, by nuclear magnetic resonance (NMR) or infrared (IR) analysis. The means of splitting is used to decide.

The physical properties of the component (A1) are not particularly limited, and are generally referred to as a number average molecular weight from the viewpoint of balance between adhesion, heat resistance, flow control property, and low dielectric property (obtained by gel permeation chromatography) The value converted by polystyrene is the same as 10,000 to 20,000, and the glass transition temperature (JIS-K7121) is about 20 to 200 °C.

Further, the concentration of the terminal acid anhydride group of the component (A1) is not particularly limited, but is usually about 5,000 to 20,000 eq/g.

The component (A2) is an essential component used for modifying the terminal acid anhydride group of the component (A1) to lower the melt viscosity of the adhesive composition of the present invention while maintaining the adhesion obtained by the adhesive. The adhesion of the layer and the heat-resistant adhesion maintain its low dielectric properties.

The component (A2) is a reactive alkoxy fluorenyl compound represented by the following formula (1). Specifically, for example, N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane, N-2-(aminoethyl)-3-aminopropyltrimethyl Oxaloxane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-ureidopropyltrialkoxydecane, and the like. General formula (1): In the formula (1), Z ¹ represents a group containing a primary amino group, R ¹ represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R ² represents a hydrocarbon group having 1 to 8 carbon atoms, and a represents 0, 1 or 2.

The amount of the component (A2) to be used is not particularly limited, and the adhesive layer of the present invention has a low melt viscosity or a low loss elastic modulus while maintaining the adhesion of the adhesive layer, heat-resistant adhesiveness, and low dielectric properties. The component (A2) is preferably about 0.2 to 1.5 mol, preferably about 0.3 to 1.2 mol, based on 1 mol of the terminal acid anhydride group of the component (A1).

Further, various conventional primary alkylamines can be used as a component for modifying the terminal acid anhydride group of the component (A1), and can be used in combination with the component (A2). Specific examples thereof include ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, secondary butylamine, tertiary butylamine, pentylamine, isoamylamine, tertiary pentylamine, and n-octylamine. N-decylamine, isodecylamine, n-tridecylamine, n-laurylamine, cetylamine, n-stearylamine, and the like. From the viewpoint of the melt viscosity characteristics, in these, it is preferred that the alkyl group has a carbon number of about 4 to 15. Further, it is usually used in an amount of less than 5 mol% based on the component (A2).

(1) The physical properties of the component are not particularly limited, and from the viewpoint of balance between heat-resistant adhesiveness, flow control property, and low dielectric property, the number average molecular weight is usually about 5,000 to 30,000, and the glass transition temperature (JIS-K7121) is 20 ~150 °C or so.

The adhesive composition of the present invention contains (1) a component, a crosslinking agent (2) (hereinafter also referred to as a component (2)), and an organic solvent (3) (hereinafter also referred to as a component (3)).

(2) The conventional components can be used, and are not particularly limited, and examples thereof include a polyphenylene ether compound (2-1) (hereinafter also referred to as a component (2-1)), and a polyepoxy compound (2-2). (hereinafter also referred to as component (2-2)), and a crosslinking agent other than these (hereinafter also referred to as component (2-3)).

As the component (2-1), various conventional materials can be used without particular limitation. Specifically, a compound represented by the following formula is preferred.

In the formula, Z ² represents an alkylene group or a single bond having 1 to 3 carbon atoms, m represents 0 to 20, n represents 0 to 20, and a total of m and n represents 1 to 30.

The physical properties of the component (2-2) are not particularly limited, and from the viewpoints of adhesion, heat-resistant adhesiveness, and low dielectric properties, it is preferred that the terminal hydroxyl group concentration is about 900 to 2,500 μmol/g, and the number average molecular weight is 800. ~ 2000 or so.

Examples of the component (2-2) include a phenol novolac type epoxy compound, a cresol novolak type epoxy compound, a bisphenol A type epoxy compound, a bisphenol F type epoxy compound, and a bisphenol S type ring. Oxygen compound, hydrogenated bisphenol A type epoxy compound, hydrogenated bisphenol F type epoxy compound, stilbene type epoxy compound, triazine skeleton-containing epoxy compound, ruthenium-containing skeleton epoxy compound, linear aliphatic epoxy Compound, alicyclic epoxy compound, glycidylamine type epoxy compound, trisphenol methane type epoxy compound, alkyl modified trisphenol methane type epoxy compound, biphenyl type epoxy compound, dicyclopentadiene skeleton Epoxy compound, naphthalene-containing epoxy compound, arylalkylene type epoxy compound, tetraglycidyl xylylenediamine; modified epoxy modified with dimer acid to modify these epoxy compounds A compound, a dimer acid diglycidyl ester, or the like may be used in combination of two or more. In addition, commercially available products include, for example, "jER828" and "jER834", "jER807" and "jER630" manufactured by Mitsubishi Chemical Corporation; "ST-3000" manufactured by Nippon Steel Chemical Co., Ltd.; DAICEL Chemical Industry "Celloxide 2021P" manufactured by Nippon Steel Co., Ltd.; "YD-172-X75" manufactured by Nippon Steel Chemical Co., Ltd., etc.

Among the components (2-2), the glycidyl phenyl dimethylamine which is preferably of the following structure can be used, for example, from Mitsubishi Gas Chemical Co., Ltd., from the viewpoint of the adhesiveness, the heat-resistant adhesiveness, and the flow control property. Commercial products such as "Tetrad-X".

Wherein Z ³ represents a phenyl or a cyclohexyl group.

Further, when the component (2-2) is used, various conventional curing agents for epoxy compounds can be used in combination. Specific examples thereof include succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, and 3-methyl-hexahydrophthalic acid. Anhydride, 4-methyl-hexahydrophthalic anhydride, 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, methylnorbornane-2,3-dicarboxylic anhydride, methylcyclohexene An acid anhydride hardener such as formic anhydride, 3-dodecenyl succinic anhydride or octenyl succinic anhydride; dicyandiamide (DICY) or aromatic diamine (trade name "Lonzacure M-DEA", "Lonzacure M-DETDA" Etc., all are amine-based curing agents such as Lonza Japan Co., Ltd., aliphatic amines; phenol novolac resin, cresol novolak resin, bisphenol A novolac resin, triazine modified phenol novolac resin, Phenolic curing agent such as phenolic hydroxy phosphazene (trade name "SPH-100" manufactured by Otsuka Chemical Co., Ltd.); cyclic phosphazene A rosin-based crosslinking agent such as a compound, a maleic acid-modified rosin or a hydride thereof may be used in combination of two or more. Among these, a phenolic curing agent is preferred, and a phenolic hydroxyphosphazene-based curing agent is particularly preferred. The amount of the curing agent to be used is not particularly limited. When the solid content of the adhesive composition of the present invention is 100% by weight, it is usually about 0.1 to 120% by weight, preferably about 10 to 40% by weight.

Further, when the component (2-2) is used, a hardening catalyst can also be used. Specific examples thereof include 1,8-diazabicyclo[5.4.0]undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, and ginseng ( Tertiary amines such as dimethylaminomethyl)phenol; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1- An imidazole such as cyanoethyl-2-undecylimidazole or 2-heptadecylimidazole; an organic phosphine such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine or phenylphosphine; Tetraphenylborate such as tetraphenylphosphonium tetraphenylborate, 2-ethyl-4-methylimidazolium tetraphenylborate, N-methylmorpholine tetraphenylboronic acid; octanoic acid, stearic acid, acetamidineacetone complex, ring An organic metal salt such as Zn, Cu or Fe which is an organic acid such as an alkanoic acid or an acid can be used in combination of two or more. Further, the amount of the catalyst used is not particularly limited, and when the solid content of the adhesive composition of the present invention is 100% by weight, it is usually about 0.01 to 5% by weight.

The component (2-3) may, for example, be at least one selected from the group consisting of a benzoxazine compound, a bismaleimide compound, and a cyanate compound.

The benzoxazine compound may, for example, be 6,6-(1-methylethylidene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6, 6-(1-methylethylidene)bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine) may be used in combination of two or more. Further, the nitrogen of the oxazine ring may be bonded to a phenyl group, a methyl group, a cyclohexyl group or the like. In addition, commercially available products include, for example, "Benzoxazine F-a type" and "Benzoxazine P-d type" manufactured by Shikoku Chemical Industry Co., Ltd.; "RLV-100" manufactured by AIR WATER Co., Ltd., and the like.

The bismaleimide compound may, for example, be 4,4'-diphenylmethane bismaleimide, m-phenylene bismaleimide, bisphenol A diphenyl ether double malayan Amine, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene double horse醯imine, 1,6'-bis-maleimido-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether, bismaleimide, 4, 4'-diphenylphosphonium bismaleimide, etc., may be combined in combination of two or more. Further, as a commercially available product, for example, "BAF-BMI" manufactured by JFE Chemical Co., Ltd., or the like can be mentioned.

The cyanate ester compound may, for example, be 2-allylphenol cyanate, 4-methoxyphenol cyanate, 2,2-bis(4-c-cyanophenol)-1,1,1,3. 3,3-hexafluoropropane, bisphenol A cyanate, diallyl bisphenol A cyanate, 4-phenylphenol cyanate, 1,1,1-cis (4-cyanylphenyl) Ethane, 4-cumenyl phenol cyanate, 1,1-bis(4-cyanylphenyl)ethane, 4,4'-bisphenol cyanate, and 2,2-bis (4) -Cyanatophenyl)propane or the like may be used in combination of two or more. In addition, the commercially available product may be, for example, "PRIMASET BTP-6020S" (manufactured by Lonza Japan Co., Ltd.) or "CYTESTER TA (manufactured by Mitsubishi Gas Chemical Co., Ltd.)".

(2) The amount of the component to be used is not particularly limited, and the adhesive layer and the adhesive sheet of the present invention have a low melt viscosity or a low loss elastic modulus while maintaining the adhesion of the adhesive layer obtained from the adhesive and the adhesive sheet. From the viewpoint of heat-resistant adhesiveness, flow controllability, and low dielectric properties, it is usually about 3 to 30 parts by weight, and 5 to 15 parts by weight, based on 100 parts by weight of the component (1). The left and right are better.

(3) The components can be used in various conventional solvents, and are not particularly limited. Specific examples thereof include N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl hydrazine, N-methyl caprolactam, and triethylene glycol. An aprotic polar solvent such as alcohol dimethyl ether or diethylene glycol dimethyl ether; an alicyclic solvent such as cyclohexanone or methylcyclohexane; an alcohol such as methanol, ethanol, propanol, benzyl alcohol or cresol A solvent, an aromatic solvent such as toluene, or the like may be used in combination of two or more.

Further, the adhesive composition of the present invention can be formulated with the following additives as needed: the above-mentioned ring-opening esterification reaction catalyst or dehydrating agent, plasticizer, weathering agent, antioxidant, heat stabilizer, lubricant, antistatic agent , brighteners, colorants, conductive agents, mold release agents, surface treatment agents, viscosity modifiers, phosphorus flame retardants, flame retardant fillers, cerium oxide fillers and fluorine fillers.

(3) The amount of the component to be used is not particularly limited, and in consideration of operability, it is preferably: (2) a component of 11 to 900 parts by weight, and (3) a component of 150 to 900 parts by weight based on 100 parts by weight of the component (1). Share.

The adhesive sheet of the present invention is a film-like adhesive material obtained by applying the adhesive composition of the present invention to the support sheet. The support sheet may, for example, be a polyester resin, a polyimide resin, a polyimide-ruthenium oxide mixed resin, a polyethylene resin, a polypropylene resin, a polyethylene terephthalate resin, or a polymethyl methacrylate. Ester resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene resin; ethylene terephthalate or phenols, phthalic acid, hydroxynaphthoic acid, etc. with p-hydroxybenzoic acid A plastic film such as the obtained aromatic polyester resin (that is, a so-called liquid crystal polymer; "Vecstar" manufactured by Kuraray Co., Ltd.). Further, the coating means is not particularly limited, and examples thereof include a gap coater, a curtain coater, a roll coater, and a laminator. Further, the thickness of the coating layer is not particularly limited, and the thickness after drying is usually in the range of about 1 to 100 μm, preferably about 3 to 50 μm. After coating, the adhesive composition is hardened under heating, and the component (3) is evaporated, whereby the intended adhesive sheet is obtained. Further, the adhesive layer peeled off from the support sheet can be used as a film-like adhesive material. The thickness thereof is not particularly limited and is usually about 3 to 40 μm.

The resin-attached copper foil of the present invention is an article composed of an adhesive layer and a copper foil, and the adhesive layer is composed of the adhesive composition of the present invention or the adhesive sheet of the present invention. The copper foil may, for example, be a rolled copper foil or an electrolytic copper foil. Further, the thickness thereof is not particularly limited, and is usually about 1 to 100 μm, preferably about 2 to 38 μm. Further, the copper foil may be subjected to various surface treatments (roughening, rust prevention, etc.). The rust-preventing treatment may be, for example, a so-called mirroring treatment using a plating treatment containing a plating solution of Ni, Zn, Sn or the like, and a chromate treatment. Further, the coating means may, for example, be the aforementioned method. Further, the adhesive layer of the resin-attached copper foil may be unhardened, and may be partially hardened or completely hardened by heating. The partially hardened adhesive layer is in the so-called B-stage state. Further, the thickness of the adhesive layer is not particularly limited, but is usually about 0.5 to 30 μm. Further, it is also possible to bond a copper foil to the adhesive surface of the resin-attached copper foil to form a copper foil with resin on both sides.

The copper clad laminate of the present invention is an article obtained by laminating a resin-attached copper foil, a copper foil or an insulating sheet of the present invention under heat and pressure; or heating the sheet under heat and pressure An article obtained by laminating a copper foil, which is obtained by applying the adhesive composition of the present invention to an insulating sheet, both of which are also referred to as CCL (Copper Clad Laminate). The number of sheets of the insulating sheet in the copper clad laminate is not particularly limited. The copper foil may, for example, be the aforementioned copper foil. The insulating sheet is preferably an insulating support or a prepreg in the support. The prepreg is a sheet-like material obtained by impregnating the insulating resin with a reinforcing material such as glass cloth and curing it to the B stage (JIS C 5603). For example, the insulating resin may be: Polyimine resin, polyimide-cerium oxide mixed resin, phenol resin, epoxy resin, polyester resin, liquid crystal polymer, linaloamine resin, and the like. The thickness of the insulating sheet and the prepreg is not particularly limited, but is usually about 20 to 500 μm. Further, the heating and pressure-bonding conditions are not particularly limited, and are usually about 150 to 280 ° C (preferably about 170 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 in which a circuit pattern is formed on the copper clad laminate. The patterning means may be, for example, a subtractive method or a semi-additive method. The semi-additive method may be, for example, a method in which a copper foil surface of a copper-clad laminate of the present invention is patterned with a resist film, and then electrolytic copper plating is performed, and the resist is removed, followed by etching with an alkaline solution. Further, the thickness of the circuit pattern layer in the printed wiring board is not particularly limited.

The multi-layer substrate of the present invention is characterized in that the printed wiring board is used as a core substrate, and the same printed wiring board or other conventional printed wiring board or printed circuit board is laminated thereon, and then heated and pressurized. Pressure sticking. When the laminate is laminated, not only the polyimide-based adhesive of the present invention but also other polyimide-based adhesives can be used. Further, the number of layers in the multilayer substrate is not particularly limited. [Examples]

The invention will be specifically described below by way of examples and comparative examples, but the scope of the invention is not limited by the examples. In addition, in each case, a part and % are a weight basis unless it mentions especially. In addition, the number average molecular weight is a value obtained by using a commercially available measuring machine ("HLC-8220GPC", manufactured by Tosoh Corporation), and the glass transition temperature is a commercially available measuring instrument ("DSC6200", Seiko). The value obtained by Instruments Co., Ltd.).

[Production Example 1-1] 3,3',4,4'-benzophenonetetracarboxylic dianhydride (trade name "BTDA" was fed to a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction tube. 50.0 g of DAICEL Chemical Industry Co., Ltd., 240.0 g of cyclohexanone, and 48.0 g of methylcyclohexane were heated to 60 °C. Then, the dimer diamine (trade name "PRIAMINE 1075", manufactured by Croda Japan Co., Ltd.) 75.8 g and α,ω-bis(3-aminopropyl)polydimethyloxime were slowly added over a period of 2 hours. After 6.5 g of alkane (trade name "KF-8010", manufactured by Shin-Etsu Chemical Co., Ltd.), it was subjected to a ruthenium reaction at 140 ° C for 3 hours, thereby obtaining a weight average molecular weight of about 25,000 and a softening point of about 80. A solution of the anhydride-based terminal polyimine (A1-1) at ° C (nonvolatile content 30.2%). Further, the molar ratio of the acid component/amine component of the component (A1-1) was 1.05.

[Production Example 1-2] Commercially available aromatic tetracarboxylic dianhydride (trade name "BTDA-UP", manufactured by EVONIK Japan Co., Ltd., 3, 3) was fed to the same reaction container as in Production Example 1-1. ',4,4'-benzophenone tetracarboxylic dianhydride content was 99.9% or more) 210.0 g, cyclohexanone 1008.0 g, methylcyclohexane 201.6 g, and the solution was heated to 60 °C. Then, 341.7 g of a hydrogenated dimer diamine (trade name "PRIAMINE 1075", manufactured by Croda Japan Co., Ltd.) was added dropwise thereto, and then subjected to a hydrazine imidization reaction at 140 ° C for 10 hours, thereby obtaining a softening point. A solution of a polyimine resin (A1-2) having a weight average molecular weight of about 35,000 at 80 ° C (nonvolatile content: 30.0%). Further, the molar ratio of the acid component/amine component was 1.03.

[Production Example 1-3] Commercially available aromatic tetracarboxylic dianhydride (trade name "BisDA-1000", manufactured by SABIC Japan Co., Ltd., 4, 4') was fed to the same reaction vessel as in Production Example 1-1. - [propane-2,2-diylbis(1,4-acetoxy)]diphthalic dianhydride content: 98.0%) 65.0 g, cyclohexanone 266.5 g, methylcyclohexane 44.4 g, and the solution was heated to 60 °C. Then, after instilling 5.4 g of PRIAMINE 1075 43.7 g and 1,3-bis(aminomethyl)cyclohexane, the oxime imidization reaction was carried out at 140 ° C for 10 hours, thereby obtaining a softening point of about 100 ° C. And a solution of a polyimine resin (A1-3) having a weight average molecular weight of about 30,000 (nonvolatile content: 29.2%). Further, the molar ratio of the acid component/amine component was 1.05.

[Production Example 1-4] Commercially available aromatic tetracarboxylic dianhydride (trade name "BTDA-PF", manufactured by EVONIK Japan Co., Ltd., 3, 3) was fed to the same reaction container as in Production Example 1-1. The content of ',4,4'-benzophenonetetracarboxylic dianhydride was 98%), 200.0 g, cyclohexanone 960.0 g, methylcyclohexane 192.0 g, and the solution was heated to 60 °C. Then, after dropping 319.3 g of PRIAMINE 1075, it was subjected to a hydrazide reaction at 140 ° C for 10 hours, thereby obtaining a polyimine resin (A1-4) having a softening point of about 80 ° C and a weight average molecular weight of about 25,000. Solution (non-volatile 29.8%). Further, the molar ratio of the acid component/amine component was 1.05.

[Production Example 2-1] In the same reaction vessel as in Production Example 1-1, 100.0 g of a solution of the component (A1-1) was added, and then N-2-(aminoethyl)-3-amine was further fed. A 1.03 g toluene solution (solid content: 10%) of propyl trimethoxy decane (trade name "KBM-603", manufactured by Shin-Etsu Chemical Co., Ltd.) was kept at 25 ° C for 6 hours, thereby obtaining a weight average molecular weight. A solution of modified polyimine (1-1) having a softening point of about 80 ° C (non-volatile 29.8%). Further, the number of moles of KBM-603 was 0.4 with respect to 1 mol of the terminal acid anhydride group of the component (A1-1).

[Production Example 2-2] In the same reaction vessel as in Production Example 1-1, 100.0 g of a solution of the component (A1-2) was added, and then a solution of KBM-603 in toluene (solid content: 10%) 1.00 g was further fed. And incubated at 25 ° C for 6 hours, thereby obtaining a solution (non-volatile 29.8%) of modified polyimine (1-2) having a weight average molecular weight of about 35,000 and a softening point of about 80 °C. Further, the number of moles of KBM-603 was 0.4 with respect to 1 mol of the terminal acid anhydride group of the component (A1-2).

[Production Example 2-3] In the same reaction vessel as in Production Example 1-1, 100.0 g of a solution of the component (A1-3) was added, and then a toluene solution (solid content: 10%) of 1.40 g of KBM-603 was further fed. And incubated at 25 ° C for 6 hours, thereby obtaining a solution (non-volatile portion 28.9%) of modified polyimine (1-3) having a weight average molecular weight of about 30,000 and a softening point of about 100 °C. Further, the number of moles of KBM-603 was 0.4 with respect to 1 mol of the terminal acid anhydride group of the component (A1-3).

[Production Example 2-4] In the same reaction vessel as in Production Example 1-1, 100.0 g of a solution of the component (A1-4) was added, and then a toluene solution of KBM-603 (solid content: 10%) was further fed. 1.60 g And incubated at 25 ° C for 6 hours, thereby obtaining a solution (non-volatile 29.5%) of modified polyimine (1-4) having a weight average molecular weight of about 25,000 and a softening point of about 80 °C. Further, the number of moles of KBM-603 was 0.4 with respect to 1 mol of the terminal acid anhydride group of the (A1-4) component.

[Production Example 2-5] In the same reaction vessel as in Production Example 1-1, 100.0 g of a solution of the component (A1-2) was added, and then a toluene solution (solid content: 10%) of 1.90 g of KBM-603 was further fed. And incubated at 25 ° C for 6 hours, thereby obtaining a solution (non-volatile 29.6%) of modified polyimine (1-5) having a weight average molecular weight of about 25,000 and a softening point of about 80 °C. Further, the number of moles of KBM-603 was 0.8 with respect to 1 mol of the terminal acid anhydride group of the component (A1-2).

[Production Example 2-6] In the same reaction vessel as in Production Example 1-1, 100.0 g of a solution of the component (A1-1) was added, and then 3-aminopropyltrimethoxydecane (trade name " KBM-903", Shin-Etsu Chemical Co., Ltd.) Toluene solution (solid content 10%) 1.70 g, and incubated at 25 ° C for 6 hours, thereby obtaining a weight average molecular weight of about 25,000 and a softening point of about 80 ° C A solution of polyimine (1-6) (non-volatile 29.9%). Further, the number of moles of KBM-903 was 0.4 with respect to 1 mol of the terminal acid anhydride group of the component (A1-1).

[Production Example 2-7] In the same reaction vessel as in Production Example 1-1, 100.0 g of a solution of the component (A1-1) was added, and then N-phenyl-3-aminopropyltrimethoxy group was further fed. A toluene solution (solid content: 10%) of 2.40 g of decane (trade name "KBM-573", manufactured by Shin-Etsu Chemical Co., Ltd.) was kept at 25 ° C for 6 hours, thereby obtaining a weight average molecular weight of about 25,000 and a softening point. A solution of modified polyimine (1-7) at 80 ° C (non-volatile 29.7%). Further, the number of moles of KBM-573 was 0.4 with respect to 1 mol of the terminal acid anhydride group of the component (A1-1).

[Production Example 2-8] In the same reaction vessel as in Production Example 1-1, 100.0 g of a solution of the component (A1-1) was added, and then 3-glycidoxypropyltrimethoxydecane was further fed (product The "KBM-403" (Shin-Etsu Chemical Co., Ltd.) toluene solution (solid content 10%) 2.10 g, and incubated at 25 ° C for 6 hours, thereby obtaining a weight average molecular weight of about 25,000 and a softening point of about 80 ° C A solution of the polyimine (1-8) was modified (non-volatile 29.8%). Further, the number of moles of KBM-403 was 0.4 with respect to 1 mol of the terminal acid anhydride group of the component (A1-1).

(Example 1) 100.00 g of a solution of the component (1-1), a bisphenol A type liquid epoxy resin ("jER828", manufactured by Mitsubishi Chemical Corporation) and a hydroxyl group-containing polycondensation as a component (2) A benzene ether (trade name "SA90", manufactured by SABIC Co., Ltd.) was mixed with a toluene solution (solid content: 50%) of 5.40 g, and 4.36 g of toluene as a component (3) to obtain a nonvolatile content of 30.0%. Things.

(Example 2) 100.00 g of a solution of the component (1-2), 0.61 g of a jER828 as a component (2), a toluene solution (solid content of 50%) of 5.40 g, and a toluene of 4.36 g as a component (3) The mixture was mixed to obtain a nonvolatile content of 30.0% of the adhesive composition.

(Example 3) 100.00 g of a solution of the component (1-3), a toluene solution (solid content: 50%) of 5.14 g as a component (2) of jER828, and a toluene solution (1.21 g) as a component (3) The mixture was mixed to obtain a nonvolatile content of 30.0% of the adhesive composition.

(Example 4) 100.00 g of a solution of the component (1-4), a toluene solution (solid content: 50%) of 5.35 g as a component (2) of jER828, 0.60 g and SA90, and 3.31 g of toluene as a component (3) The mixture was mixed to obtain a nonvolatile content of 30.0% of the adhesive composition.

(Example 5) 100.00 g of a solution of the component (1-5), 0.61 g of a jER828 as a component (2), a toluene solution (solid content of 50%) of 5.37 g, and a toluene of 3.66 g as a component (3) The mixture was mixed to obtain a nonvolatile content of 30.0% of the adhesive composition.

(Example 6) 100.00 g of a solution of the component (1-6), 0.61 g of a jER828 as a component (2), a toluene solution (solid content of 50%) of 5.42 g of a component, and 4.71 g of toluene as a component (3). The mixture was mixed to obtain a nonvolatile content of 30.0% of the adhesive composition.

(Example 7) 100.00 g of a solution of the component (1-1), a toluene solution (solid content: 50%) of 2.62 g of jER828 0.30 g and SA90 as component (2), and toluene 4.10 g as a component (3) The mixture was mixed to obtain a nonvolatile content of 30.0% of the adhesive composition.

(Example 8) 100.00 g of a solution of the component (1-1), a toluene solution (solid content: 50%) of 8.76 g as a component (2) of jER828, 0.99 g, and a toluene of 9.82 g as a component (3) The mixture was mixed to obtain a nonvolatile content of 30.0% of the adhesive composition.

(Example 9) 100.00 g of a solution of the component (1-1), 0.63 g of jER828 as a component (2), and a toluene solution (solid content: 50%) of 5.53 g of the component (3), and methyl group B as the component (3) The base ketone was mixed with 6.81 g to obtain a non-volatile 30.0% adhesive composition.

(Example 10) 100.00 g of a solution of the component (1-1), a commercially available polyfunctional epoxy resin as a component (2) ("jER630", manufactured by Mitsubishi Chemical Corporation, N, N-bi-diverted water) Methyl ethyl ketone solution (solid content 40%) of 1.98 g of glyceryl-4-glycidoxyaniline) and Bis-A type cyanate (trade name "CYTESTER TA", manufactured by Mitsubishi Gas Chemical Co., Ltd.) 3.51 g, and 7.46 g of toluene as the component (3) were mixed to obtain a nonvolatile content of 30.0% of the adhesive composition.

(Comparative Example 1) 100.00 g of a solution of the component (A1-1), 0.62 g of jER828, and 5.47 g of a toluene solution (solid content: 50%) of SA90 and 5.76 g of toluene were mixed to obtain a nonvolatile matter of 30.0% of an adhesive. Composition.

(Comparative Example 2) 100.00 g of the solution of the component (1-7), 0.61 g of the jER828 as the component (2), and a toluene solution (solid content: 50%) of 5.38 g of the component (3), and toluene 4.01 g as the component (3). The mixture was mixed to obtain a nonvolatile content of 30.0% of the adhesive composition.

(Comparative Example 3) 100.00 g of a solution of the component (1-8), 0.61 g of jER828, and 5.40 g of a toluene solution (solid content: 50%) of SA90 and 4.36 g of toluene were mixed to obtain a nonvolatile matter of 30.0% of an adhesive. Composition.

<Preparation of Adhesive Sheet> The adhesive compositions of Examples 1 to 11 and Comparative Examples 1 and 2 were coated with a gap applicator so that the thickness after drying became 20 μm and the left and right edges were 1 cm. After supporting a sheet (trade name "Kapton", manufactured by DU PONT-TORAY Co., Ltd., film thickness: 25 μm, thermal expansion coefficient: 15 ppm/°C), it was dried at 180 ° C for 3 minutes to obtain an adhesive sheet.

<Preparation of copper-clad laminate> A film sheet having a width of 10 cm and a length of 4 cm was cut out from the adhesive sheets of the examples and the comparative examples in a direction perpendicular to the direction in which the gap coating was applied. Then, the adhesive surface of the film sheet was superposed on a mirror side of a commercially available electrolytic copper foil (trade name "F2-WS", manufactured by Furukawa Circuit Foil Co., Ltd., having a thickness of 18 μm, a width of 10 cm, and a length of 5 cm). And make test samples. The outline of the test sample is as shown in Fig. 1.

Then, the test samples of the examples and the comparative examples were placed on a support for pressurization, and heated from above at a pressure of 5 MPa, 170 ° C, and 30 minutes, via a support made of the same material. Pressurization is performed to form a laminated film.

1. Adhesion test The peel strength (N/cm) of the copper clad laminates of the above examples and comparative examples was measured in accordance with JIS C 6481 (Test method for copper clad laminate for flexible printed wiring boards). The results are shown in Table 1.

2. Solder heat resistance test The copper clad laminates of the above-described Examples and Comparative Examples were floated in a solder bath at 288 ° C for 30 seconds so that the appearance of the copper foil was below. The no change was set to ○, and the case where there was foaming or expansion was set to ×. The results are shown in Table 1.

3. Evaluation of Flow Controllability It was confirmed with the naked eye whether or not the end position of the adhesive layer (hardened layer) in the laminated film of the above-mentioned Examples and Comparative Examples was not changed before and after heating and pressurization. The flow controllability was evaluated by the length of the outflow in the horizontal direction. When there is no outflow in the horizontal direction (best = no outflow = outflow length is 0 mm), it is judged that the flow control property is good. The results are shown in Table 1. Fig. 2 shows an appearance photograph of the evaluation sample of Example 1 as a good representative example (outflow length is 0 mm), and Fig. 3 shows an appearance photograph of the evaluation sample of Comparative Example 1 as a bad representative example (outflow The length is 5 mm).

<Preparation of a hardened material sample for dielectric constant and dielectric loss tangent measurement> The adhesive composition of the examples and the comparative examples was injected into a fluororesin PFA flat disk (diameter 75 mm, manufactured by Mutual Chemicals Co., Ltd.). About 7 g, and hardened at 30 ° C for 10 hours, 70 ° C for 10 hours, 100 ° C for 6 hours, 120 ° C for 6 hours, 150 ° C for 6 hours, and 180 ° C for 12 hours, thereby obtaining a film thickness of about 300 μm. The dielectric constant and dielectric loss tangent were measured for the hardened material sample.

Then, according to JIS C2565, a commercially available dielectric constant measuring device (cavity resonator type, manufactured by AET Co., Ltd.) was used to measure the dielectric constant and dielectric at 10 GHz for the cured samples of the examples and the comparative examples. Loss tangent. The results are shown in Table 1.

[Table 1]

no

Figure 1 is a schematic diagram of a sample for flow control testing. In the first drawing, reference numeral 1 denotes an insulating film (block copolymer polyimine-cerium oxide mixed film), 2 denotes an adhesive of the present invention, and 3 denotes a copper foil. Fig. 2 is a result (photograph) of a flow control test of a resin-attached copper foil obtained by using the adhesive composition of Example 2. Fig. 3 is a result (photograph) of a flow control test of a resin-attached copper foil obtained by using the adhesive composition of Comparative Example 1.

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Claims (7)

An improved polyimine (1) which is a reaction product of an acid anhydride-based terminal polyimine (A1) and a reactive alkoxyalkylene compound (A2) represented by the following formula (1), The acid anhydride-based terminal polyimine (A1) is a reactant of the monomer group (1), and the monomer group (1) comprises an aromatic tetracarboxylic anhydride (a1) and a dimer diamine (a2). 1): In the formula (1), X represents a group containing a primary amino group, R ¹ represents hydrogen or a hydrocarbon group having 1 to 8 carbon atoms, R ² represents a hydrocarbon group having 1 to 8 carbon atoms, and a represents 0, 1 or 2. An adhesive composition comprising: (1) a component, a crosslinking agent (2), and an organic solvent (3). An adhesive sheet obtained by using the adhesive composition of claim 2. A resin-attached copper foil obtained by using the adhesive composition of claim 2. A copper clad laminate obtained by using the resin-attached copper foil described in claim 4. A printed wiring board obtained by using the copper clad laminate described in claim 5. A multilayer substrate obtained by using the printed wiring board of claim 6.