TW201723027A - Resin composition, adhesive, film-like adhesive material, adhesive sheet, multilayer circuit board, resin-attached copper foil, copper-clad laminate, and printed circuit board having good adhesiveness, heat resistance and low dielectric properties - Google Patents

Abstract

The problem to be solved by this invention is to provide a novel polyimide adhesive which gives an adhesive layer having good adhesiveness, heat resistance and low dielectric properties. The means of this invention for solving the problem is a resin composition comprising polyimide (A1) formed by reaction of a monomer group (1) which contains an aromatic tetracarboxylic acid dianhydride, (a1) having a free carboxylic acid content of less than 1% by weight and a hydrogenated dimer diamine (a2), but does not contain diaminopolysiloxane (a3).

Description

Resin composition, adhesive, film-like adhesive material, adhesive sheet, multilayer wiring board, resin-attached copper foil, copper-clad laminate, printed wiring board

The present invention relates to a resin composition, an adhesive, a film-like adhesive material, an adhesive sheet, a multilayer wiring board, a copper foil with a resin, a copper-clad laminate, and a printed wiring 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, using a low dielectric material in a laminated printed circuit board or a printed circuit board, which not only has excellent adhesion but also has a small dielectric constant and dielectric loss tangent. Characteristics (hereinafter also referred to as low dielectric properties).

An adhesive composition which can be used as a low dielectric material, and a conventionally known polyimide-based adhesive comprising: an aromatic tetracarboxylic dianhydride and a dimer diamine A crosslinking agent such as a polyimide or an epoxy resin, and an organic solvent (see Patent Document 1) may have insufficient low dielectric properties.

On the other hand, as a polyimine-based adhesive excellent in low dielectric properties, a conventional polyimide-based adhesive has been known which comprises: polycondensing an aromatic tetracarboxylic dianhydride with a diamine group. A cross-linking agent such as a polyimide or an epoxy resin obtained by reacting a decane with an organic solvent (see Patent Document 2), but the low dielectric properties of the present inventors are still insufficient. [Previous Technical Literature] (Patent Literature)

Patent Document 1: Japanese Laid-Open Patent Publication No. 2013-199645 (Patent Document 2)

[Problems to be Solved by the Invention] A main problem to be solved by the present invention is to provide a novel polyimine-based adhesive which can obtain an adhesive layer having good adhesion, heat resistance and low dielectric properties. [Technical means to solve the problem]

The present inventors conducted research to improve the adhesion and dielectric properties of the polyimide-based adhesives described in Patent Documents 1 and 2.

First, attention is paid to the fact that the aromatic tetracarboxylic dianhydride actually contains a free carboxylic acid derived from a raw material as an impurity. Then, it is assumed that the carboxyl group of the free carboxylic acid directly increases the polarity of the polyimide, which is a major cause of the moisture absorption of the polyimide, and as a result, the low dielectric property of the adhesive is deteriorated.

In addition, attention is also paid to the structure of the dimer diamine. The dimer diamine is generally a polymer derived from a dimer of an unsaturated fatty acid such as oleic acid, that is, a dimer acid (refer to Japanese Laid-Open Patent Publication No. Hei 9-12712), and it is assumed that a large amount of molecules are contained in the molecule. When the double bond is conjugated, the π electrons of the double bonds increase the polarity of the polyimide, and as a result, the low dielectric properties of the adhesive become insufficient.

In addition, it has been newly discovered that diamine polyoxymethane, when used in combination with dimer diamine, adversely affects the low dielectric loss tangent of polyimine. Although the reason is not clear, we believe that the reason should be that the surface energy of the polyoxyalkylene is large and the repulsion is caused by the polar group (the quinone imine group or the like) in the polyimine.

The present invention has been completed in the light of the above studies. In other words, the present invention relates to a resin composition, an adhesive, a film-like adhesive material, an adhesive sheet, a multilayer wiring board, a resin-attached copper foil, a copper-clad laminate, and a printed wiring board.

A resin composition comprising a polyimine (A1) obtained by reacting a monomer group (1) comprising an aromatic tetracarboxylic acid Acid dianhydride (a1) and hydrogenated dimer diamine (a2) and free of diaminopolyoxyalkylene (a3), the free carboxylic acid content of the aromatic tetracarboxylic dianhydride (a1) is less than 1 weight%.

2. The resin composition according to the above item 1, wherein the aromatic tetracarboxylic dianhydride as the component (a1) is as shown in the following structure: 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 - wherein Y represents -(CH ₂ ) _l - or -H ₂ C-HC(-O-C(=O)-CH ₃ )-CH ₂ -, l = 1 to 20.

3. The resin composition according to the above item 1, wherein the (a1) component and the (a2) component have a molar ratio of (a1)/(a2) of from 1 to 1.5. .

The resin composition according to any one of the above items 1 to 3, further comprising a polyimine (A2) other than the component (A1).

5. The resin composition according to item 4, wherein the component (A2) is obtained by reacting a monomer group (2) comprising (a1) a component and/or an aromatic component. Tetracarboxylic dianhydride (a1'), and (a2) component and/or unhydrogenated dimer diamine (a2'), the content of free carboxylic acid of the aromatic tetracarboxylic dianhydride (a1') is 1 More than weight%.

6. The resin composition according to the above item 5, wherein the component (2) further comprises a component (a3).

The resin composition according to any one of the above items 4 to 6, wherein the weight ratio of the solid component of the component (A1) to the component (A2) is 40/60 to (A1)/(A2). 99/1.

The resin composition according to any one of the above items 1 to 7, further comprising a crosslinking agent (B).

The resin composition according to the above item 8, wherein the component (B) is a polyepoxy compound (B1) and/or a polyphenylene ether compound (B2).

10. The resin composition according to the above item 9, wherein the component (B1) is tetraglycidylbenzidine having the following structure: Wherein Z ¹ represents a phenyl or a cyclohexyl group.

The resin composition according to the above item 9, wherein the component (B2) is a hydroxyl group-containing polyphenylene ether having the following structure: 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 resin composition according to any one of the above items 1 to 11, further comprising an organic solvent (C).

The resin composition according to any one of the above items 1 to 12, further comprising a reactive alkoxy fluorenyl compound (D) represented by the following formula: In the formula, Q represents a group containing a functional group which will react with an acid anhydride 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 the resin composition according to any one of items 1 to 13 above.

A film-like adhesive material comprising the cured product of the adhesive according to item 14 above.

An adhesive sheet comprising the cured product of the adhesive according to item 14 above as an adhesive layer.

A multilayer wiring board which is selected from the group consisting of the adhesive according to the above item 14, the film-like adhesive material according to the above item 15, and the adhesive sheet according to item 16 above. At least one of them.

A copper foil with a resin comprising the adhesive according to the item 14, wherein the film-like adhesive material according to item 15 and the adhesive sheet according to item 16 are used. At least one selected from the group.

A copper clad laminate obtained by using the resin-attached copper foil according to item 18 above.

A printed wiring board obtained by using the copper clad laminate according to the above item 19. [efficacy]

The resin composition of the present invention has good initial adhesion to various substrates and good adhesion. Further, the cured product (adhesive layer) is low in viscosity and does not generate bubbles upon heating, and is not liable to generate residual glue, and is excellent in adhesion and low dielectric properties.

The resin composition and the cured product are used as an adhesive for the production of a printed circuit board (a build-up substrate or a flexible printed circuit board) and a copper-clad laminate for a flexible printed circuit board, and a tape-type automatic bonding ( TAB) tapes such as tape and flip chip (COF) tapes, and adhesives for carrying sheets, electrical insulating materials such as semiconductor interlayer materials, coating agents, and resist inks.

Further, the multilayer wiring board, the resin-attached copper foil, the copper-clad laminate, and the printed wiring board of the present invention each have the cured product (adhesive layer) of the adhesive of the present invention, and are excellent in adhesion and low dielectric properties. Therefore, there is a material for use as a product requiring a highly low dielectric property, such as a product for processing a high frequency signal, such as a mobile communication device such as a smart phone or a mobile phone, or a base station device, a server/router thereof. Network related electronic machines, large computers, etc. [Simple illustration] No

The resin composition of the present invention contains polyimine (A1) (hereinafter also referred to as (A1) component), and the polyimine (A1) is a monomer group (1) (hereinafter also referred to as (1) component). The monomer group (1) comprises an aromatic tetracarboxylic dianhydride (a1) (hereinafter also referred to as (a1) component) and a hydrogenated dimer diamine (a2) (hereinafter also referred to as ( A2) component) and does not contain diaminopolysiloxane (a3) (hereinafter also referred to as component (a3)), and the content of free carboxylic acid of the aromatic tetracarboxylic dianhydride (a1) is less than 1% by weight .

The component (a1) is a conventional aromatic tetracarboxylic dianhydride, and an aromatic tetracarboxylic dianhydride having a free carboxylic acid content of less than 1% by weight is used, and the content of the free carboxylic acid is 0.5% by weight or less. Preferably, it is preferably 0.2% by weight or less. By using the component (a1), it is possible to improve the low dielectric properties of the adhesive of the present invention while maintaining the adhesive strength of the adhesive of the present invention.

Examples of the aromatic tetracarboxylic dianhydride include pyromellitic dianhydride, 4,4'-oxydiphthalic dianhydride, and 3,3',4,4'-benzophenonetetracarboxylic acid II. Anhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenylphosphonium tetracarboxylic dianhydride, 1,2,3,4-benzene four Formic acid dianhydride, 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 acid Anhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenylstilbene 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- Dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, and 4,4'-[propane-2,2-diyl bis(1,4-stretch) Phenoxy)]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 - wherein Y represents -(CH ₂ ) _l - or -H ₂ C-HC(-O-C(=O)-CH ₃ )-CH ₂ -, l = 1 to 20.

From the viewpoint of the adhesive force and low dielectric properties of the adhesive of the present invention, the aforementioned aromatic tetracarboxylic dianhydride is derived from 3,3',4,4'-benzophenonetetracarboxylic dianhydride, 4 a group consisting of 4'-[propane-2,2-diylbis(1,4-phenylene))diphthalic dianhydride and 4,4'-oxydiphthalic dianhydride At least one selected from the group is preferred.

The free carboxylic acid may, for example, be an aromatic tetracarboxylic acid or an aromatic tetracarboxylic acid monoanhydride, an aromatic tricarboxylic acid, an aromatic tricarboxylic acid anhydride, an aromatic dicarboxylic acid or an aromatic dicarboxylic anhydride. For example, when it is 3,3',4,4'-benzophenonetetracarboxylic dianhydride, for example, 3,3',4,4'-benzophenonetetracarboxylic acid or its anhydride, and 3 3', 4-benzophenone tricarboxylic acid (see the following structure, molecular weight of about 356) and the like.

The content of the above-mentioned free carboxylic acid in the above component (a1) can be quantified by various conventional analytical means, for example, by high performance liquid chromatography (HPLC) or mass spectrometry (GC-MASS).

The component (a2) is a hydrogenated product derived from a dimer of a dimer of an unsaturated fatty acid such as oleic acid (see JP-A-9-12712, etc.), and the following is a dimer acid. Not a limited structural formula. 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 component (a2) is a compound in which at least one or all of the carbon-carbon double bonds become a single bond.

The commercially available product of the component (a2) may, for example, be PRIAMINE 1075 (all manufactured by Croda Japan Co., Ltd.). An example of a hydrogenated dimer diamine is given below.

The molar ratio (a1)/(a2) of the component (a1) and the component (a2) in the component (1) is not particularly limited, and is usually from the viewpoint of balance between adhesion and low dielectric properties. It is about 1 to 1.5, preferably about 1 to 1.2.

Further, in the present invention, the component (1) does not contain the component (a3) from the viewpoint of low dielectric properties. Specific examples of the component (a3) are as described later.

In the component (1), a diamine (hereinafter also referred to as a component (a4)) other than the components (a1) to (a3) may 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. From the viewpoint of low dielectric properties, in the above, the above alicyclic diamine is preferred. The amount of the component (a4) used is not particularly limited, and when all the diamine components are set to 100 mol%, it is usually less than 40 mol%.

The component (A1) can be produced by various conventional methods. Specifically, for example, the acid component and the diamine component which are respectively used are usually subjected to an addition polymerization reaction for about 0.1 to 2 hours at a temperature of usually about 60 to 120 °C. Further, the obtained addition polymer may be subjected to a ruthenium imidization 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. Moreover, when performing such a reaction, the component (C) mentioned later, especially an aprotic polar solvent can be used as a reaction solvent.

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 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 generally refer to a number average molecular weight (a value converted by polystyrene obtained by gel permeation chromatography) from the viewpoint of balance between adhesion and low dielectric properties. The same applies 5,000 to 50,000, preferably about 7,000 to 30,000, and the glass transition temperature (JIS-K7121) is about 30 to 160 ° C, preferably about 40 to 140 ° C. Further, the concentration of the terminal acid anhydride group of the component (A1) is not particularly limited, but is usually about 2,000 to 40,000 eq/g, preferably about 3,000 to 20,000 eq/g.

Further, the molecular terminal of the component (A1) can be modified (capped) by various low molecular weight primary alkyl monoamines. 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, etc., in particular, from the viewpoint of low dielectric properties, the carbon number of the alkyl group is preferred. It is about 4 to 15. Further, the amount of the primary alkyl monoamine used is not particularly limited, and is usually about 0.8 to 1.2 mol, preferably about 0.9 to 1.1 mol, based on the terminal acid anhydride group of the component (A1).

The resin composition of the present invention can contain a polyimine (A2) other than the component (A1) (hereinafter also referred to as a component (A2)).

When the (A2) component is a polyimine other than the component (A1), various conventional materials can be used, and preferably, for example, a polyimine (except for the compound corresponding to the component (A1)) The monomer group (2) (hereinafter also referred to as component (2)) is reacted, and the monomer group (2) comprises the component (a1) and/or an aromatic tetracarboxylic dianhydride ( A1') (hereinafter also referred to as (a1') component), and the above-mentioned (a2) component and/or unhydrogenated dimer diamine (a2') (hereinafter also referred to as (a2') component), the aromatic The content of the free carboxylic acid of the tetracarboxylic dianhydride (a1') is 1% by weight or more.

As the (a1') component, the aromatic tetracarboxylic dianhydride in which the content of the free carboxylic acid in the aromatic tetracarboxylic dianhydride is 1% by weight or more can be used, and various conventional materials can be used without particular limitation. . Further, it is also possible to use a compound as the component (a1') in which the free carboxylic acid is combined with the component (a1) so that the content thereof is 1% by weight or more. The upper limit of the content of the free carboxylic acid in the (a1') component is usually 5% by weight or less from the viewpoint of maintaining the low dielectric property of the adhesive of the present invention while maintaining the low dielectric property.

The (a2') component is, for example, a compound described in the above-mentioned Japanese Patent Publication No. 9-12712, and the like, and the commercially available product is exemplified by Versamine 551 (manufactured by BASF Japan Co., Ltd.) and PRIAMINE 1074 (Croda). Made by Japan Co., Ltd.).

The component (a3) can also be contained in the component (2). As the component (a3), for example, various conventional diaminopolyoxyalkylene oxides may be mentioned, and examples thereof include α,ω-bis(2-aminoethyl)polydimethyloxane, α,ω-double. (3-aminopropyl)polydimethyloxane, α,ω-bis(4-aminobutyl)polydimethyloxane, α,ω-bis(5-aminopentyl) Polydimethyloxane, α,ω-bis[3-(2-aminophenyl)propyl]polydimethyloxane, α,ω-bis[3-(4-aminophenyl) ) propyl] polydimethyl siloxane or the like.

Hereinafter, a representative example of the combination of the raw materials in the component (2) will be listed. A. (a1) component, (a2) component, and (a3) component B. (a1) component and (a2') component C. (a1) component, (a2') component, and (a3) component D. (a1' ) component and (a2) component pentane (a1') component, (a2) component, and (a3) component (a1') component and (a2') component g (a1') component, (a2') component And (a3) component xin. (a1) component, (a2) component, and (a4) component 壬.(a1') component, (a2) component, and (a4) component 癸.(a1) component, (a2') component And (a4) ingredients

(2) The molar ratio of the (a1) component and/or the (a1') component to the component (a2) and/or the (a2') component, that is, (a1, a1') / (a2, a2) ') is not particularly limited, and is usually about 1 to 1.5, preferably about 1 to 1.2.

Further, when the component (a3) is contained in the component (2), the amount thereof to be used is not particularly limited, and when all the diamine components are 100 mol%, it is usually about 0.1 to 5.0 mol%.

Further, the component (2) may also contain the component (a4). In this case, the amount of use of (a4) is not particularly limited, and when all the diamine components are set to 100 mol%, it is usually less than 40 mol%.

The method for producing the component (A2) is a method for producing the component (A1). The ring closure ratio of the quinone imine of the component (A2) is not particularly limited, but is usually 70% or more, and preferably 85 to 100%.

The physical properties of the component (A2) are not particularly limited, and generally refer to a number average molecular weight (a value converted by polystyrene obtained by gel permeation chromatography) from the viewpoint of balance between adhesion and low dielectric properties. The same applies 5,000 to 50,000, preferably about 7,000 to 30,000, and the glass transition temperature (JIS-K7121) is about 30 to 160 ° C, preferably about 40 to 140 ° C. Further, the concentration of the terminal acid anhydride group of the component (A2) is not particularly limited, and is usually about 2,000 to 40,000 eq/g, preferably about 3,000 to 20,000 eq/g.

Further, the molecular terminal of the component (A2) can be modified (capped) by the above-mentioned primary alkyl monoamine.

The weight ratio of the solid component of the component (A1) to the component (A2), that is, (A1)/(A2) is not particularly limited, and from the viewpoint that the low dielectric property of the cured product containing the both components is particularly low, usually It is about 30/70 to 90/10, and it is preferably about 40/60 to 99/1.

The resin composition of the present invention may further contain a crosslinking agent (B) (hereinafter also referred to as a component (B)).

The component (B) can be any conventionally used, and is not particularly limited, and examples thereof include a polyepoxy compound (B1) (hereinafter also referred to as a component (B1)) and a polyphenylene ether compound (B2) (hereinafter also referred to as B2) Component), and a crosslinking agent other than these (hereinafter also referred to as (B3) component). Among these, the component (B1) and/or the component (B2) are preferred.

The component (B1) may, for example, be 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, or a hydrogenation. Bisphenol A type epoxy compound, hydrogenated bisphenol F type epoxy compound, stilbene type epoxy compound, triazine skeleton-containing epoxy compound, fluorene-containing skeleton epoxy compound, linear aliphatic epoxy compound, alicyclic ring Epoxy compound, glycidylamine type epoxy compound, trisphenol methane type epoxy compound, alkyl modified trisphenol methane type epoxy compound, biphenyl type epoxy compound, dicyclopentadiene skeleton-containing epoxy compound, a naphthalene-containing epoxy compound, an arylalkylene type epoxy compound, tetraglycidylphthalic acid amine; a modified epoxy compound modified by a dimer acid to modify the epoxy compound Two or more types of acid diglycidyl ester can be combined. 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.

From the viewpoint of the compatibility and the heat resistance, the (B1) component is preferably a glycidyl phenyl dimethylamine having the following structure, and for example, "Tetrad-X" manufactured by Mitsubishi Gas Chemical Co., Ltd., etc., can be used. Commercially available.

Wherein Z ¹ represents a phenyl or a cyclohexyl group.

Further, when the component (B1) 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 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 (B1) 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 of the present invention is 100% by weight, it is usually about 0.01 to 5% by weight.

As the component (B2), 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 (B2) are not particularly limited, and from the viewpoint of adhesion 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 from about 800 to 2,000.

The component (B3) may, for example, be at least one selected from the group consisting of a benzoxazine compound, a bismaleimide compound, and a cyanate compound.

The aforementioned benzoxazine compound may, for example, be 6,6-(1-methylethylidene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6 Further, 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 above-mentioned bismaleimide compound may, for example, be 4,4'-diphenylmethane bismaleimide, meta-phenyl bismaleimide, bisphenol A diphenyl ether double mala Imine, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene double Maleimide, 1,6'-bis-maleimido-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether, bismaleimide, 4 4'-diphenylphosphonium bismaleimide or the like may be used 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-paran (4-cyanate benzene Ethylene, 4-cumenyl phenol cyanate, 1,1-bis(4-cyanylphenyl)ethane, 4,4'-bisphenol cyanate, and 2,2-dual ( 4-c-c-phenylphenylpropane 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.)".

The amount of the component (B) is not particularly limited, and is usually 3 to 30 parts by weight based on 100 parts by weight of the total of the components (A1) and (A2) (hereinafter, collectively referred to as the component (A)). It is preferably about 5 to 25 parts by weight.

The resin composition of the present invention can contain an organic solvent (C) (hereinafter also referred to as a component (C)).

The conventional component (C) can be used without any particular limitation. Specific examples include N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl hydrazine, N-methyl caprolactam, and triethylene glycol. Aprotic polar solvents such as dimethyl ether and diethylene glycol dimethyl ether; alicyclic solvents such as cyclohexanone and methylcyclohexane; alcohols such as methanol, ethanol, propanol, benzyl alcohol, and cresol A solvent, an aromatic solvent such as toluene, or the like may be used in combination of two or more. In particular, from the viewpoint of low dielectric properties, an aromatic solvent is preferred among these.

The amount of the component (C) to be used is not particularly limited, and is preferably about 0.1 to 10 parts by weight, preferably about 1 to 5 parts by weight, per 100 parts by weight of the component (A).

The resin composition of the present invention may further contain a reactive alkoxy fluorenyl compound (D) represented by the following formula (hereinafter also referred to as a component (D)). The reactive functional group contained in Q may, for example, be an amine group, an epoxy group or a thiol group. In the formula, Q represents a group containing a functional group which will react with an acid anhydride 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 (D) component can adjust the melt viscosity while maintaining the low dielectric properties of the hardened layer of the adhesive of the present invention. As a result, the interface adhesion force between the hardened layer and the substrate (that is, the so-called anchoring effect) can be increased, and the hardened layer can be prevented from oozing out from the substrate end (hereinafter, such an operation is sometimes referred to as flow control). ).

The compound in which the functional group in Q is an amine group may, for example, be N-2-(aminoethyl)-3-aminopropylmethyldimethoxydecane or N-2-(aminoethyl)- 3-aminopropyltrimethoxydecane, 3-aminopropyltrimethoxydecane, 3-aminopropyltriethoxydecane, 3-ureidopropyltrialkoxydecane, and the like.

The compound in which the functional group in Q is an epoxy group may, for example, be 2-(3,4-epoxycyclohexyl)ethyltrimethoxynonane or 3-glycidoxypropylmethyldimethoxydecane. 3-glycidoxypropyltrimethoxydecane, 3-glycidoxypropylmethyldiethoxydecane, 3-glycidoxypropyltriethoxydecane, and the like.

The compound having a thiol group in the Q may, for example, be 3-mercaptopropyltrimethoxydecane, 3-mercaptopropyltriethoxydecane, 3-mercaptopropylmethyldimethoxydecane, and 3 - Mercaptopropylmethyldiethoxydecane, and the like.

Since the reaction with the terminal acid anhydride group of the component (A) is rapidly carried out and the effect of the above-described flow control is good, the component (D) is preferably a compound having an amine group in which the functional group in Q is an amine group.

The amount of the component (D) to be used is not particularly limited, and is preferably from 0.01 to 5 parts by weight, preferably from 0.1 to 3 parts by weight, per 100 parts by weight of the component (A).

The adhesive of the present invention is composed of a resin composition, and the resin composition can be directly used, and the following may be formulated as needed: the above-mentioned ring-opening esterification reaction catalyst or dehydrating agent, plasticizer, weathering agent, and anti-drug Oxidizer, heat stabilizer, lubricant, antistatic agent, whitening agent, coloring agent, conductive agent, mold release agent, surface treatment agent, viscosity regulator, phosphorus flame retardant, flame retardant filler, cerium oxide filler and fluorine Additives such as fillers; or diluent solvents.

The film-like adhesive material of the present invention is obtained by hardening the adhesive of the present invention by a conventional means. Specifically, for example, a material obtained by applying the adhesive to various supports and heating to volatilize the component (C) and then peeling it off from the support can be used as a film-like adhesive. Material utilization. Further, the coating means is not particularly limited, and examples thereof include 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.

The adhesive sheet of the present invention is an article in which the cured product is an adhesive layer. Specifically, it is composed of the above-mentioned cured product and various conventional sheet base materials, and examples of the sheet base material include a polyester resin, a polyimide resin, a polyimide-ruthenium oxide mixed resin, and a polyethylene resin. Polypropylene resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polymethyl methacrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene a resin; an aromatic polyester resin obtained from ethylene terephthalate or phenols, phthalic acid, hydroxynaphthoic acid or the like and p-hydroxybenzoic acid (also known as liquid crystal polymer; manufactured by Kuraray Co., Ltd.) , "Vecstar", etc.) and other plastic films. The thickness of the adhesive layer is not particularly limited, and is usually in the range of about 1 to 100 μm, preferably about 3 to 50 μm.

The multilayer wiring board of the present invention is an article obtained by using at least one selected from the group consisting of the above-mentioned polyimide-based adhesive, the film-like adhesive, and the above-mentioned adhesive sheet. Specifically, it can be obtained by using the above to form an adhesive layer on at least one side of a core substrate, that is, a printed wiring board, and laminating other printed wiring boards or printed circuit boards thereon, and heating and Pressed under pressure. The heating temperature, the pressing time and the pressure are not particularly limited, but are usually about 70 to 200 ° C, about 1 minute to 3 hours, and about 0.5 to 20 MPa.

The resin-attached copper foil of the present invention is formed by forming an adhesive layer on a copper foil using at least one selected from the group consisting of the polyimine-based adhesive, the film-like adhesive, and the adhesive sheet. Items. The copper foil may, for example, be a rolled copper foil or an electrolytic copper foil, and may be subjected to various surface treatments (roughening, rust prevention, etc.). Further, the thickness of the copper foil is not particularly limited, but is usually about 1 to 100 μm, preferably about 2 to 38 μm. 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, the copper foil may be further bonded to the adhesive surface of the obtained resin-attached copper foil to form a copper foil having a resin coated on both sides.

The copper clad laminate of the present invention is an article obtained by laminating a resin-attached copper foil of the present invention with a copper foil or an insulating sheet, and is also called CCL (Copper Clad Laminate). Specifically, the resin-attached copper foil of the present invention is pressure-bonded to at least one side or both sides of various conventional insulating sheets under pressure. Further, when pressure-bonded to one side, a different material from the resin-attached copper foil of the present invention can be pressure-bonded to the other side under heating. Further, the number of the resin-attached copper foil and the insulating sheet in the copper clad laminate is not particularly limited. Further, the insulating sheet may be a prepreg. The prepreg is a sheet-like material obtained by impregnating a resin with a reinforcing material such as glass cloth and hardening it to the B stage (JIS C 5603). The resin is usually used: polyimine resin Insulating resins such as phenol resins, epoxy resins, polyester resins, liquid crystal polymers, and linaloamine resins. Further, the thickness of 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, but are usually about 150 to 280 ° C and about 0.5 to 20 MPa.

The printed wiring board of the present invention is formed by forming a circuit pattern on the copper foil surface of 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. Further, it is also possible to obtain a multilayer substrate by using the printed wiring board as a core substrate and laminating the same printed wiring board or other conventional printed wiring board or printed circuit board thereon. When the laminate is laminated, not only the polyimide-based adhesive of the present invention but also other conventional polyimide-based adhesives can be used. Further, the number of layers in the multilayer substrate is not particularly limited. Further, a through hole may be interposed at each time the lamination is performed, and the inside may be plated. [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.

[Production Example 1] A commercially available aromatic tetracarboxylic dianhydride (trade name "BTDA-UP", manufactured by EVONIK Japan Co., Ltd., was supplied to a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen gas introduction tube. The content of 3,3',4,4'-benzophenonetetracarboxylic dianhydride is 99.9% or more) 210.0 g, cyclohexanone 1008.0 g, methylcyclohexane 201.6 g, and the solution is 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 (A1-1) 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 2] A commercially available aromatic tetracarboxylic dianhydride (trade name "BisDA-2000", manufactured by SABIC Japan Co., Ltd., 4, 4'-[C-" was fed into the same reaction container as in Production Example 1. The content of 2,2-diylbis(1,4-phenoxy)diphthalic dianhydride is 99.5% or more, 60.0 g, cyclohexanone 165.0 g, methylcyclohexane 27.5 g, and The solution was heated to 60 °C. Then, after dropping 59.3 g of PRIAMINE 1075, the oxime imidization reaction was carried out at 140 ° C for 10 hours, thereby obtaining a polyimine resin (A1-2) having a softening point of about 90 ° C and a weight average molecular weight of about 30,000. Solution (non-volatile 31.9%). Further, the molar ratio of the acid component/amine component was 1.05.

[Comparative Production Example 1] In the same reaction vessel as in Production Example 1, a commercially available aromatic tetracarboxylic dianhydride (trade name "BisDA-1000", manufactured by SABIC Japan Co., Ltd., 4, 4'-[C -2,2-diylbis(1,4-phenoxy)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 (A2-1) 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.

[Comparative Production Example 2] Commercially available aromatic tetracarboxylic dianhydride (trade name "BTDA-PF", manufactured by EVONIK Japan Co., Ltd., 3, 3', 4) was fed to the same reaction vessel as in Production Example 1. The content of 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 31.93 g of PRIAMINE 1075, it was subjected to a hydrazine imidization reaction at 140 ° C for 10 hours, thereby obtaining a polyimine resin (A2-2) 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.

[Comparative Production Example 3] In the same reaction vessel as in Production Example 1, 190.0 g of BTDA-PF, 277.5 g of cyclohexanone, and 182.4 g of methylcyclohexane were fed, and the solution was heated to 60 °C. Then, PRIAMINE 1075 277.5 g and commercially available polydimethyl methoxy alkane (trade name "KF-8010", manufactured by Shin-Etsu Chemical Co., Ltd.) 23.8 were added dropwise, and then subjected to a time of 10 hours at 140 ° C. The amination reaction was carried out, whereby a solution (nonvolatile content: 29.8%) of a polyimine resin (A2-3) having a softening point of about 70 ° C and a weight average molecular weight of about 15,000 was obtained. Further, the molar ratio of the acid component/amine component was 1.09.

[Comparative Production Example 4] In the same reaction vessel as in Production Example 1, 190.0 g of BTDA-UP, 912.0 g of cyclohexanone, and 182.4 g of methylcyclohexane were fed, and the solution was heated to 60 °C. Then, after dropping KF-8010 476.0, it was subjected to a ruthenium imidization reaction at 140 ° C for 10 hours, thereby obtaining a polyimine resin (A2-4) having a softening point of about 20 ° C and a weight average molecular weight of about 35,000. Solution (non-volatile 36.7%). Further, the molar ratio of the acid component/amine component was 1.09.

[Comparative Production Example 5] In the same reaction vessel as in Production Example 1, 200.0 g of BTDA-UP, 960.0 g of cyclohexanone, and 192.0 g of methylcyclohexane were fed, and the solution was heated to 60 °C. Then, 319.2 g of a commercially available non-hydrogenated dimer diamine (trade name "PRIAMINE 1074", manufactured by Croda Japan Co., Ltd.) was added dropwise, and then subjected to a ruthenium iodization reaction at 140 ° C for 10 hours. A solution (non-volatile 29.8%) of a polyimine resin (A2-5) having a softening point of about 70 ° C and a weight average molecular weight of about 25,000 was obtained. Further, the molar ratio of the acid component/amine component was 1.05.

[Comparative Production Example 6] In the same reaction vessel as in Production Example 1, 200.0 g of BisDA-1000, 700.0 g of cyclohexanone, and 175.0 g of methylcyclohexane were fed, and the solution was heated to 60 °C. Then, 190.5 g of a commercially available non-hydrogenated dimer diamine (trade name "PRIAMINE 1075", manufactured by Croda Japan Co., Ltd.) was added dropwise, and then subjected to a ruthenium iodization reaction at 140 ° C for 10 hours. A solution (non-volatile 29.8%) of a polyimine resin (A2-6) having a softening point of about 80 ° C and a weight average molecular weight of about 35,000 was obtained. Further, the molar ratio of the acid component/amine component was 1.09.

<Measurement of Dielectric Constant and Dielectric Loss Tangent of Polyimine Film> The polyimine solution of the production example and the comparative production example was applied to NAFLON PTFE tape TOMBO No. 9001 (NICHIAS Co., Ltd.), respectively. After drying at room temperature for 12 hours, it was allowed to harden at 200 ° C for 1 hour, whereby a cured product sheet having a film thickness of 50 μm was obtained. 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 (Dk) and dielectric loss tangent of the cured product sheet at 10 GHz ( Df). The results are shown in Table 1.

[Table 1]

(Example 1) 100.00 g of a solution of the component (A1-1), tetraglycidylphenyldimethylamine ("Tetrad-X", manufactured by Mitsubishi Gas Chemical Co., Ltd.) as a component (B), 1.67 g and 1.67 g of hydroxy polyphenylene ether (trade name "SA90", manufactured by SABIC Co., Ltd.), 7.87 g of toluene as component (C), and a commercially available amino group-containing decane coupling agent (product name " as component (D) KBM603", manufactured by Shin-Etsu Chemical Co., Ltd., N-2-(aminoethyl)-3-aminopropyltrimethoxydecane) 0.07 g, and obtained a non-volatile 30.0% resin composition (adhesive) Agent).

(Example 2) 100.00 g of a solution of the component (A1-2), 1.78 g of Tetrad-X and 1.78 g of SA90, 14.78 g of toluene, and 0.07 g of KBM603 were mixed to obtain a resin composition having a nonvolatile content of 30.0% (adhesion) Agent).

(Example 3) A solution of 100.00 g of the component (A1-1) and a solution of the component (A2-3) 25.17 g, Tetrad-X 2.09 g, and SA90 2.09 g, toluene 9.59 g, and KBM603 0.08 g were obtained. Non-volatile 30.0% resin composition (adhesive).

(Example 4) A solution of 100.00 g of the component (A1-1) and 25.17 g of a component (A2-3), Tetrad-X 3.32 g, SA90 3.32 g, toluene 15.32 g, and KBM603 0.09 g were mixed. Non-volatile 30.0% resin composition (adhesive).

(Example 5) A solution of 100.00 g of the component (A1-2) and 26.76 g of a component (A2-3), Tetrad-X 2.21 g, and SA90 2.21 g, toluene 16.58 g, and KBM603 0.08 g were mixed. Non-volatile 30.0% resin composition (adhesive).

(Example 6) 30.00 g of a solution of the component (A1-1), a solution of 30.82 g of a component (A2-1), and a solution of a component (A2-3) of 15.10 g, a commercially available polyfunctional epoxy resin (commercial product) "jER630", manufactured by Mitsubishi Chemical Corporation, N, N-diglycidyl-4-glycidyloxyaniline) 1.20 g and phenol novolac resin (trade name "T759", manufactured by Arakawa Chemical Industry Co., Ltd. 1.30 g, toluene 3.81 g, methyl ethyl ketone 1.30 g, and KBM603 0.05 g were mixed to obtain a nonvolatile content of 30.0% of a resin composition (adhesive).

(Example 7) A solution of (A1-1) component 30.00 g, a solution of (A2-1) component 30.82 g, and a solution of (A2-3) component 15.10 g, jER630 0.57 g and T759 0.62 g, toluene 1.33 g Methyl ethyl ketone 0.62 g and KBM603 0.05 g were mixed to obtain a resin composition (adhesive) having a nonvolatile content of 30.0%.

(Example 8) 100.00 g of a solution of the component (A1-1), 1.67 g of Tetrad-X, and 3.90 g of toluene were mixed to obtain a resin composition (adhesive) having a nonvolatile content of 30.0%.

(Example 9) A solution of (A1-1) component 30.00 g, a solution of (A2-1) component 30.82 g, and a solution of (A2-6) component 15.05 g, jER630 0.57 g, and T759 0.62 g, toluene 1.37 g Methyl ethyl ketone 0.62 g and KBM603 0.05 g were mixed to obtain a resin composition (adhesive) having a nonvolatile content of 30.0%.

(Example 10) A solution of (A1-1) component 30.00 g, a solution of (A2-1) component 30.82 g, and a solution of (A2-6) component 15.05 g, jER630 3.30 g, and Bis-A type cyanate (trade name "CYTESTER TA", manufactured by Mitsubishi Gas Chemical Co., Ltd.) 2.34 g, toluene 8.96 g, methyl ethyl ketone 3.51 g, and KBM603 0.05 g were mixed to obtain a nonvolatile content of 30.0% of a resin composition (adhesive) Agent).

(Example 11) A solution of (A1-1) component 30.00 g, a solution of (A2-1) component 30.82 g, and a solution of (A2-6) component 15.05 g, jER630 0.07 g, and CYTESTER TA 0.49 g, toluene 1.39 g, methyl ethyl ketone 0.74 g, and KBM603 0.05 g were mixed to obtain a nonvolatile content of 30.0% of a resin composition (adhesive).

(Example 12) A solution of 100.00 g of the component (A1-1) and 25.17 g of a component (A2-3), Tetrad-X 0.58 g, SA90 0.58 g, toluene 2.54 g, and KBM603 0.08 g were mixed. Non-volatile 30.0% resin composition (adhesive).

(Comparative Example 1) 100.00 g of a solution of the component (A2-2), 1.75 g of Tetrad-X and 1.65 g of SA90, 7.05 g of toluene, and 0.07 g of KBM603 were mixed to obtain a resin composition having a nonvolatile content of 30.0% (adhesion) Agent).

(Comparative Example 2) 100.00 g of a solution of the component (A2-3), 1.75 g of Tetrad-X and 1.65 g of SA90, 7.05 g of toluene, and 0.07 g of KBM603 were mixed to obtain a resin composition having a nonvolatile content of 30.0% (adhesion) Agent).

(Comparative Example 3) A solution of 20.00 g of the component (A1-1) and 80.54 g of the component (A2-3), 1.67 g of Tetrad-X, 1.67 g of SA90, 7.47 g of toluene, and 0.07 g of KBM603 were obtained. Non-volatile 30.0% resin composition (adhesive).

(Comparative Example 4) A solution of 100.00 g of the component (A1-1) and 25.17 g of the component (A2-3), Tetrad-X 6.26 g, and SA90 6.26 g, toluene 29.00 g, and KBM603 0.09 g were mixed. Non-volatile 30.0% resin composition (adhesive).

(Comparative Example 5) A solution of 100.00 g of the component (A1-1) and 25.17 g of the component (A2-3), Tetrad-X 0.19 g, and SA90 0.19 g, toluene 0.71 g, and KBM603 0.08 g were mixed. Non-volatile 30.0% resin composition (adhesive).

(Comparative Example 6) 100.00 g of a solution of the component (A2-4), Tetrad-X 2.04 g and SA90 2.04 g, toluene 32.04 g, and KBM603 0.08 g were mixed to obtain a resin composition having a nonvolatile content of 30.0% (adhesion) Agent).

(Comparative Example 7) 100.00 g of a solution of the component (A2-5), 1.64 g of Tetrad-X and 1.66 g of SA90, 7.26 g of toluene, and 0.07 g of KBM603 were mixed to obtain a resin composition having a nonvolatile content of 30.0% (adhesion) Agent).

<Production of Adhesive Sheet> The adhesive of Example 1 was applied to a support sheet using a gap coater so that the thickness after drying was 10 μm (trade name "Kapton 100EN", limited stock of DU PONT-TORAY) The company made a film thickness of 25 μm and a coefficient of thermal expansion of 15 ppm/° C., and then dried at 180 ° C for 3 minutes, thereby obtaining an adhesive sheet. The adhesives of the other examples and comparative examples were also carried out to obtain an adhesive sheet.

Then, the mirror side of a 18 μm thick electrolytic copper foil (trade name "F2-WS", manufactured by Furukawa Circuit Foil Co., Ltd.) was laminated on the adhesive side of each adhesive sheet at a pressure of 1 MPa, 180 ° C, and 30 The laminate was produced by heating and pressing under the conditions of a minute. The adhesive of Comparative Example 1 was also carried out in the same manner to obtain a laminate.

<Measurement of dielectric constant and dielectric loss tangent of the adhesive layer> Into the fluororesin PFA flat disk (diameter 75 mm, manufactured by Mutual Chemicals Co., Ltd.), about 7 g of the adhesive of the examples and the comparative examples were respectively injected. And hardening 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 cured product having a film thickness of about 300 μm. Sheet. 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 (Dk) and dielectric loss tangent of the cured product sheet at 10 GHz ( Df).

<Adhesiveness Test> The peel strength (N/cm) of each of the laminates of the examples and the comparative examples was measured in accordance with JIS C-6481 (Test Method for Copper-clad Laminates for Flexible Printed Wiring Boards).

<Solder heat resistance test> Each of the laminates of the examples and the comparative examples was floated in a solder bath at 288 ° C for 30 seconds so that the copper foil side was below, and the presence or absence of appearance change was confirmed. The no change was set to ○, and the case where there was foaming or expansion was set to ×.

[Table 2]

<Production of Bonding Sheet> The adhesive of Example 1 was applied to a release film (trade name "WH52-P25CM (white)" by using a gap coater so that the thickness after drying was about 25 μm. After being manufactured by Sun A. Kaken Co., Ltd., it was dried at 150 ° C for 5 minutes, thereby obtaining a joined sheet. The adhesives of the other examples and comparative examples were also carried out to obtain a bonding sheet.

<Production of Printed Wiring Board> The double-sided copper foil of the copper clad laminate of Example 1 was formed into a resist pattern having a line/pitch of 0.2/0.2 (mm), and then immersed in an aqueous solution of ferric chloride having a concentration of 40%. Etching is performed to form a copper circuit. A printed wiring board is obtained as described above.

<Preparation of Multilayer Circuit Board> Using the obtained printed wiring board as a core material, the resin-attached copper foil of Example 1 was superposed on both sides thereof, and pressed at a pressure of 4.5 MPa, 200 ° C, and 30 minutes. Thereafter, the untreated copper foil on the outer layer of the obtained material was formed into a resist pattern of line/pitch = 0.2/0.2 (mm). Then, etching was performed by immersing the obtained substrate in a 40% aqueous solution of ferric chloride to form a copper circuit. The above-mentioned adhesive sheet was laminated on the surface layer on which the copper circuit was formed, and heated and pressurized under the conditions of a pressure of 1 MPa, 180 ° C and 30 minutes, thereby laminating. In this way, a multilayer wiring board having four circuit pattern layers is obtained.

<Production 2 of Printed Wiring Board> The copper foil of the single-sided copper-clad laminate of Example 1 was formed into a resist pattern having a line/pitch of 0.2/0.2 (mm), and then immersed in an aqueous solution of ferric chloride having a concentration of 40%. The etching is performed to form a copper circuit. The same was prepared, and the above-mentioned bonding sheets were sandwiched between the substrate sides of the copper-free circuit, and heated and pressurized under the conditions of a pressure of 1 MPa, 180 ° C, and 30 minutes, thereby laminating. Then, the above-mentioned bonding sheet was laminated on the surface layer of the laminated body on which the copper circuit was formed, and heated and pressurized under the conditions of a pressure of 1 MPa, 180 ° C, and 30 minutes, thereby laminating. In this way, a multilayer wiring board having four circuit pattern layers is obtained.

The printed wiring board and the multilayer wiring board were obtained by the same method for the adhesives of the other examples.

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Claims (20)

A resin composition comprising a polyimine (A1) obtained by reacting a monomer group (1), the monomer group (1) comprising an aromatic tetracarboxylic acid Anhydride (a1) and hydrogenated dimer diamine (a2) and free of diaminopolyoxyalkylene (a3), the aromatic carboxylic acid dianhydride (a1) having a free carboxylic acid content of less than 1% by weight . The resin composition according to claim 1, wherein the aromatic tetracarboxylic dianhydride as the component (a1) is as shown in the following structure: 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 - wherein Y represents -(CH ₂ ) _l - or -H ₂ C-HC(-O-C(=O)-CH ₃ )-CH ₂ -, l = 1 to 20. The resin composition according to claim 1 or 2, wherein the molar ratio of the (a1) component and the (a2) component in the component (1) is (a1)/(a2) is from 1 to 1.5. The resin composition according to any one of claims 1 to 3, further comprising a polyimine (A2) other than the component (A1). The resin composition according to claim 4, wherein the component (A2) is obtained by reacting a monomer group (2) comprising the component (a1) and/or an aromatic tetracarboxylic acid. a dianhydride (a1'), a component (a2) and/or an unhydrogenated dimer diamine (a2'), wherein the content of the free carboxylic acid of the aromatic tetracarboxylic dianhydride (a1') is 1% by weight or more . The resin composition according to claim 5, wherein the component (2) further comprises a component (a3). The resin composition according to any one of claims 4 to 6, wherein the weight ratio of the solid component of the component (A1) to the component (A2) is (A1)/(A2) is 40/60 to 99/1. . The resin composition according to any one of claims 1 to 7, further comprising a crosslinking agent (B). The resin composition according to claim 8, wherein the component (B) is a polyepoxy compound (B1) and/or a polyphenylene ether compound (B2). The resin composition according to claim 9, wherein the component (B1) is tetraglycidylphthalic acid amine having the following structure: Wherein Z ¹ represents a phenyl or a cyclohexyl group. The resin composition according to claim 9 or 10, wherein the component (B2) is a hydroxyl group-containing polyphenylene ether having the following structure: 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 resin composition according to any one of claims 1 to 11, further comprising an organic solvent (C). The resin composition according to any one of claims 1 to 12, further comprising a reactive alkoxy fluorenyl compound (D) represented by the following formula: In the formula, Q represents a group containing a functional group which will react with an acid anhydride 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 the resin composition according to any one of claims 1 to 13. A film-like adhesive material comprising the cured product of the adhesive of claim 14. An adhesive sheet which is an adhesive layer of the adhesive of the adhesive of claim 14. A multilayer wiring board obtained by using at least one selected from the group consisting of the adhesive of claim 14, the film-like adhesive material of claim 15, and the adhesive sheet of claim 16. . A resin-attached copper foil which is selected from the group consisting of the adhesive of claim 14, the film-like adhesive material of claim 15, and the adhesive sheet of claim 16. One kind. A copper clad laminate obtained by using the resin-attached copper foil described in claim 18. A printed wiring board obtained by using the copper clad laminate described in claim 19.