TWI701272B - Resin composition, adhesive, film-like adhesive material, adhesive sheet, multilayer circuit board, copper foil with resin, copper clad laminate, printed circuit board - Google Patents

Abstract

The problem to be solved by the present invention is to provide a novel polyimide-based adhesive, which can obtain an adhesive layer with good adhesiveness, heat resistance and low dielectric properties. The solution of the present invention is a resin composition comprising polyimide (A1), the polyimide (A1) is formed by reacting monomer group (1), and monomer group (1) includes Aromatic tetracarboxylic dianhydride (a1) and hydrogenated dimer diamine (a2) without diamino polysiloxane (a3), the free carboxylic acid of the aromatic tetracarboxylic dianhydride (a1) The content is less than 1% by weight.

Description

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

The invention relates to a resin composition, an adhesive, a film-like adhesive material, an adhesive sheet, a multilayer circuit board, a copper foil with resin, a copper clad laminate, and a printed circuit board.

Flexible printed circuit boards (FPWB: Flexible Printed Wiring Board) and printed circuit boards (PCB: Printed Circuit Board), as well as multilayer circuit boards using these, have been widely used in the following products: mobile phones or smartphones, etc. Type communication equipment or its base station equipment, server/router and other network-related electronic equipment, large computers, etc.

In recent years, in these products, in order to transmit/process large-capacity information at high speeds, high-frequency electronic signals are used. However, because high-frequency signals are very easy to attenuate, it is sought to suppress transmission loss as much as possible for the aforementioned multilayer circuit boards. method.

A means to suppress transmission loss in multilayer circuit boards, for example: a low-dielectric material is used in multilayer printed circuit boards or printed circuit boards, which not only has excellent adhesion, but also has low dielectric constant and dielectric loss tangent Characteristics (hereinafter also referred to as low dielectric characteristics).

An adhesive composition that can be used as a low-dielectric material. There is a polyimide-based adhesive in the prior art, which contains: a reaction between an aromatic tetracarboxylic dianhydride and a dimer diamine Crosslinking agents such as polyimide and epoxy resins, and organic solvents (see Patent Document 1), but sometimes low dielectric properties are insufficient.

On the other hand, as a polyimine-based adhesive with excellent low-dielectric properties, there is a conventional polyimine-based adhesive, which contains: polyimide-based dianhydride and diamine group Crosslinking agents such as polyimide and epoxy resins, and organic solvents (refer to Patent Document 2) formed by the reaction of siloxanes, but within the scope of the inventors' knowledge, the low dielectric properties are still insufficient. [Prior Art Document] (Patent Document)

Patent Document 1: Japanese Patent Application Publication No. 2013-199645 　　 Patent Document 2: Japanese Patent Application Publication No. 7-154042

[Problem to be solved by the invention] 　　 The main problem to be solved by the present invention is to provide a novel polyimide-based adhesive, which can obtain an adhesive layer with good adhesion, heat resistance and low dielectric properties. [Technical means to solve the problem]

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

First, attention was paid to the fact that aromatic tetracarboxylic dianhydride actually contains free carboxylic acid derived from raw materials as impurities. Then, it is assumed that the carboxyl group of the free carboxylic acid directly increases the polarity of the polyimide, which becomes the main reason for the moisture absorption of the polyimide, and as a result, the low dielectric properties of the adhesive deteriorate.

In addition, it also focuses on the structure of dimer diamine. Dimer diamines are generally polymers derived from dimer acids, which are dimers of unsaturated fatty acids such as oleic acid (refer to Japanese Patent Laid-Open No. 9-12712), and it is assumed that the molecule contains a large amount of When double bonds are conjugated, the π electrons of the double bonds will increase the polarity of the polyimide, and as a result, the low dielectric properties of the adhesive will become insufficient.

In addition, the following facts have been newly discovered: when diamine-based polysiloxanes are used in combination with dimer diamines, they will adversely affect the low dielectric loss tangent of polyimides. Although the reason is not clear, we believe that the reason should be: the surface energy of polysiloxane is large and it repels the polar group (imine group, etc.) in polyimine.

The present invention was completed based on the above-mentioned research. In other words, the present invention relates to the following resin composition, adhesive, film-like adhesive material, adhesive sheet, multilayer wiring board, copper foil with resin, copper clad laminate, and printed wiring board.

1. A resin composition comprising polyimide (A1), the polyimide (A1) is formed by reacting a monomer group (1), and the monomer group (1) contains aromatic tetracarboxylic acid Acid dianhydride (a1) and hydrogenated dimer diamine (a2) without diamino polysiloxane (a3), the content of free carboxylic acid in the aromatic tetracarboxylic dianhydride (a1) is less than 1 weight%.

式中，X表示單鍵、－SO₂ －、－CO－、－O－、－O－C₆ H₄ －C(CH₃ )₂ －C₆ H₄ －O－或－COO－Y－OCO－，其中，Y表示－(CH₂ )_l －或－H₂ C－HC(－O－C(＝O)－CH₃ )－CH₂ －，l＝1～20。2. The resin composition according to item 1 above, wherein the aromatic tetracarboxylic dianhydride as the component (a1) has the following structure:

In the formula, 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 -, where Y represents -(CH ₂ ) _l -or -H ₂ C-HC(-O-C(=O)-CH ₃ )-CH ₂ -, l=1-20.

3. The resin composition according to item 1 or 2, wherein the molar ratio of (a1) component and (a2) component in component (1), that is, (a1)/(a2) is 1 to 1.5 .

4. The resin composition according to any one of items 1 to 3 above, which further contains polyimide (A2) other than the component (A1).

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

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

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

8. The resin composition according to any one of items 1 to 7, which further contains a crosslinking agent (B).

9. 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).

式中，Z¹ 表示伸苯基或伸環己基。10. The resin composition according to item 9 above, wherein the component (B1) is tetraglycidylxylylenediamine of the following structure:

In the formula, Z ¹ represents phenylene or cyclohexylene.

式中，Z² 表示碳數1～3的伸烷基或單鍵，m表示0～20，n表示0～20，m與n之合計表示1～30。11. The resin composition according to item 9 or 10, wherein the component (B2) is a hydroxyl-containing polyphenylene ether having the following structure:

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

12. The resin composition according to any one of items 1 to 11 above, which further contains an organic solvent (C).

式中，Q表示包含會與酸酐基進行反應的官能基之基，R¹ 表示氫或碳數1～8的烴基，R² 表示碳數1～8的烴基，a表示0、1或2。13. The resin composition according to any one of items 1 to 12, which further comprises a reactive alkoxysilyl compound (D) represented by the following general formula:

In the formula, Q represents a group containing a functional group that reacts with an acid anhydride group, R ¹ represents hydrogen or a hydrocarbon group having 1 to 8 carbons, R ² represents a hydrocarbon group having 1 to 8 carbons, and a represents 0, 1, or 2.

14. An adhesive composed of the resin composition described in any one of items 1 to 13 above.

15. A film-like adhesive material composed of a cured product of the adhesive described in item 14.

16. An adhesive sheet in which the cured product of the adhesive described in item 14 is used as an adhesive layer.

17. A multilayer wiring board that is selected from the group consisting of the adhesive described in item 14 above, the film-like adhesive material described in item 15 and the adhesive sheet described in item 16 At least one of.

18. A resin-coated copper foil using the group consisting of the adhesive described in item 14 above, the film-like adhesive material described in item 15 and the adhesive sheet described in item 16 At least one selected from the group.

19. A copper-clad laminated board obtained by using the resin-attached copper foil described in item 18.

20. A printed wiring board obtained by using the copper-clad laminated board described in item 19. [effect]

The resin composition of the present invention not only has good initial adhesion to various substrates, but also has good adhesion. In addition, the hardened product (adhesive layer) has low viscosity, does not generate bubbles when heated, and is not easy to produce residual glue, and has excellent adhesion and low dielectric properties.

The resin composition and the cured product are used as adhesives for the manufacture of printed circuit boards (build-up substrates, flexible printed circuit boards, etc.) and copper clad laminates for flexible printed circuit boards, and tape-type automatic bonding ( TAB) tape and chip-on-film (COF) tape and other carrier tapes, as well as electrical insulating materials such as adhesives for carrying sheets, semiconductor interlayer materials, coating agents, resist inks, etc.

In addition, the multilayer wiring board of the present invention, the copper foil with resin, the copper clad laminate and the printed wiring board of the present invention all have a cured product (adhesive layer) of the adhesive of the present invention, and have excellent adhesion and low dielectric properties. Therefore, it is used as a material for products that require high and low dielectric properties, such as the following products that process high-frequency signals: mobile communication devices such as smart phones or mobile phones or their base station devices, servers/routers Such as network-related electronic equipment, large computers, etc. [Illustration brief description] None

The resin composition of the present invention contains polyimide (A1) (hereinafter also referred to as (A1) component), and the polyimide (A1) is made from monomer group (1) (hereinafter also referred to as (1) component) ), and the monomer group (1) contains aromatic tetracarboxylic dianhydride (a1) (hereinafter also referred to as (a1) component) and hydrogenated dimer diamine (a2) (hereinafter also referred to as ( a2) component) and does not contain diamino polysiloxane (a3) (hereinafter also referred to as (a3) component), the content of free carboxylic acid in the aromatic tetracarboxylic dianhydride (a1) is less than 1% by weight .

(a1) The component is a variety of conventional aromatic tetracarboxylic dianhydrides, and the free carboxylic acid content is less than 1% by weight. The free carboxylic acid content is 0.5% by weight or less. Preferably, 0.2% by weight or less is best. By using the component (a1), the adhesive of the present invention can be maintained while improving its low dielectric properties.

Examples of the aforementioned aromatic tetracarboxylic dianhydride include: pyromellitic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic acid dianhydride Anhydride, 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic acid dianhydride 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 dianhydride Anhydride, 2,3,3',4'-diphenyl ether tetracarboxylic dianhydride, 2,3,3',4'-diphenyl tetracarboxylic dianhydride, 2,2-bis(3,3' ,4,4'-tetracarboxyphenyl)tetrafluoropropane dianhydride, 2,2'-bis(3,4-dicarboxyphenoxyphenyl) dianhydride, 2,2-bis(2,3- Dicarboxyphenyl)propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, and 4,4'-(propan-2,2-diylbis(1,4-extension) Phenoxy)] diphthalic dianhydride, etc., two or more types may be combined.

式中，X表示單鍵、－SO₂ －、－CO－、－O－、－O－C₆ H₄ －C(CH₃ )₂ －C₆ H₄ －O－或－COO－Y－OCO－，其中，Y表示－(CH₂ )_l －或－H₂ C－HC(－O－C(＝O)－CH₃ )－CH₂ －，l＝1～20。

In the formula, 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 -, where Y represents -(CH ₂ ) _l -or -H ₂ C-HC(-O-C(=O)-CH ₃ )-CH ₂ -, l=1-20.

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

Examples of the free carboxylic acid include aromatic tetracarboxylic acid or aromatic tetracarboxylic acid monoanhydride, aromatic tricarboxylic acid, aromatic tricarboxylic acid anhydride, aromatic dicarboxylic acid, and aromatic dicarboxylic acid anhydride. For example, when it is 3,3',4,4'-benzophenonetetracarboxylic dianhydride, for example: 3,3',4,4'-benzophenonetetracarboxylic acid or its monoanhydride, and 3 ,3',4-benzophenone tricarboxylic acid (refer to the following structure, molecular weight about 356), etc.

The content of the aforementioned free carboxylic acid in the aforementioned component (a1) can be quantified by various conventional analysis methods, such as high-performance liquid chromatography (HPLC) or mass spectrometry (GC-MASS).

The aforementioned component (a2) is a hydride of a polymer derived from a dimer of unsaturated fatty acids such as oleic acid, that is, a dimer acid (see Japanese Patent Application Laid-Open No. 9-12712, etc.). The following are examples of dimer acids Not a limited structure. In each structural formula, m+n=6-17, p+q=8-19, and the dotted line means carbon-carbon single bond or carbon-carbon double bond. (a2) The component is a compound in which at least one or all of the carbon-carbon double bonds become single bonds.

(A2) Commercially available products of the component include, for example, PRIAMINE 1075 (all manufactured by Croda Japan Co., Ltd.). An example of hydrogenated dimer diamine is listed below.

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

Furthermore, in the present invention, from the viewpoint of low dielectric properties, the aforementioned component (1) does not contain the aforementioned component (a3). The specific example of this (a3) component is mentioned later.

The aforementioned (1) component can contain diamines other than the aforementioned (a1) component to (a3) component (hereinafter also referred to as (a4) component) as needed. Specifically, for example: diaminocyclohexane, diaminodicyclohexylmethane, dimethyldiaminodicyclohexylmethane, tetramethyldiaminodicyclohexylmethane, diaminodicyclohexyl Propane, diaminobicyclo[2.2.1]heptane, bis(aminomethyl)bicyclo[2.2.1]heptane, 3(4),8(9)-bis(aminomethyl)tricyclic[ 5.2.1.0 ^2,6 ]Decane, 1,3-bis(aminomethyl)cyclohexane, isophoronediamine and other alicyclic diamines; 2,2-bis[4-(3-amino) Phenoxy)phenyl]propane, 2,2-bis[4-(4-aminophenoxy)phenyl]propane and other diaminophenoxyphenylpropanes; 3,3'-diamino Diaminodiphenyl ethers such as diphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether; p-phenylenediamine, m-phenylenediamine, etc. Phenylenediamines; 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide and other diamino groups Diphenyl sulfides; 3,3'-diaminodiphenyl sulfide, 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide, etc. Phenyl chloride; 3,3'-diaminobenzophenone, 4,4'-diaminobenzophenone, 3,4'-diaminobenzophenone and other diaminobenzophenones Class; 3,3'-diaminodiphenylmethane, 4,4'-diaminodiphenylmethane, 3,4'-diaminodiphenylmethane and other diaminodiphenylmethanes; 2,2-bis(3-aminophenyl)propane, 2,2-bis(4-aminophenyl)propane, 2-(3-aminophenyl)-2-(4-aminophenyl) ) Diaminodiphenylpropanes such as propane; 2,2-bis(3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4- Aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1, 3,3,3-hexafluoropropane and other diaminophenyl hexafluoropropanes; 1,1-bis(3-aminophenyl)-1-phenylethane, 1,1-bis(4-amine) Phenyl)-1-phenylethane, 1-(3-aminophenyl)-1-(4-aminophenyl)-1-phenylethane and other diaminophenylphenylethanes Class; 1,3-bis(3-aminophenoxy)benzene, 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene and other diaminophenoxybenzenes; 1,3-bis(3-aminobenzyl)benzene, 1,3-bis(4- Diaminobenzyl)benzene, 1,4-bis(3-aminobenzyl)benzene, 1,4-bis(4-aminobenzyl)benzene and other diaminobenzyl groups Benzene; 1,3-bis(3-amino-α,α-dimethylbenzyl)benzene, 1,3-bis(4-amino-α,α-dimethylbenzyl)benzene , 1,4-bis(3-amino-α,α-dimethylbenzyl)benzene, 1,4-bis(4-amino-α,α-dimethylbenzyl)benzene, etc. Amino dimethylbenzenes; 1,3-bis (3-Amino-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)benzene and other bisaminobis(trifluoromethyl)benzylbenzenes; 2,6-bis(3-aminophenoxy)benzonitrile, 2,6-bis(3-amine Phenoxy) pyridine; 4,4'-bis(3-aminophenoxy)biphenyl, 4,4'-bis(4-aminophenoxy)biphenyl and other aminophenoxybiphenyls Class; Bis[4-(3-aminophenoxy)phenyl]ketone, bis[4-(4-aminophenoxy)phenyl]ketone and other aminophenoxyphenyl ketones; Bis[ 4-(3-aminophenoxy)phenyl]sulfide, bis[4-(4-aminophenoxy)phenyl]sulfide and other aminophenoxyphenyl sulfides; bis[4 -(3-Aminophenoxy) phenyl] ash, bis[4-(4-aminophenoxy) phenyl] ash and other aminophenoxy phenyl ash; bis[4-(3- Aminophenoxyphenyl ethers such as aminophenoxy)phenyl]ether and 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-aminophenoxy)phenyl]-1,1,1,3,3,3-hexafluoropropane and other aminophenoxyphenylpropanes; and 1,3- Bis[4-(3-aminophenoxy)benzyl]benzene, 1,3-bis[4-(4-aminophenoxy)benzyl]benzene, 1,4-bis[ 4-(3-Aminophenoxy)benzyl]benzene, 1,4-bis[4-(4-aminophenoxy)benzyl]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) Yl)-α,α-dimethylbenzyl]benzene, 4,4'-bis[4-(4-aminophenoxy)benzyl]diphenyl ether, 4,4'-bis [4-(4-Amino-α,α-dimethylbenzyl)phenoxy]benzophenone, 4,4'-bis[4-(4-amino-α,α-dimethyl Benzyl)phenoxy]diphenyl sulfide, 4,4'-bis[4-(4-aminophenoxy)phenoxy]diphenyl sulfide, 3,3'-diamino- 4,4'-diphenoxybenzophenone, 3,3'-diamino-4,4'-dibiphenoxybenzophenone, 3,3'-diamino-4-benzene Oxybenzophenone, 3,3'-diamino-4-biphenoxybenzophenone, 6,6'-bis(3-aminophenoxy)3,3,3',3 '-Tetramethyl-1,1'-spirobiindane (6,6'-bis(3-aminophenoxy)3,3, 3',3'-tetramethyl-1,1'-spirobiindane), 6,6'-bis(4-aminophenoxy)3,3,3',3'-tetramethyl-1,1'- Spirobiindane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4-aminobutyl)tetramethyldisiloxane, bis(amine Methyl)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)ethane Oxy]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-diamino Heptane, 1,8-diaminooctane, 1,9-diaminononane, 1,10-diaminodecane, 1,11-diaminoundecane, 1,12-diamine Two or more types of dodecane and the like can be combined. From the viewpoint of low dielectric properties, among these, the aforementioned alicyclic diamine is preferred. (a4) The usage amount of the component is not particularly limited. When all the diamine components are set to 100 mol%, it is usually less than 40 mol%.

(A1) The component can be produced by various conventional methods. Specifically, for example, the acid component and the diamine component used separately are subjected to addition polymerization reaction usually for about 0.1 to 2 hours at a temperature of usually about 60 to 120°C. Then, further at a temperature of about 80 to 250°C, preferably 100 to 200°C, the resulting addition polymer is subjected to an imidization reaction, that is, a dehydration ring-closure reaction for about 0.5 to 50 hours. In addition, when performing these reactions, the component (C) described later, particularly an aprotic polar solvent, can be used as the reaction solvent.

When performing the imidization reaction, various conventional reaction catalysts, dehydrating agents, and solvents described later can be used. Examples of reaction catalysts include: aliphatic tertiary amines such as triethylamine; aromatic tertiary amines such as dimethylaniline; heterocyclic tertiary amines such as pyridine, picoline, and isoquinoline. Combine two or more. In addition, examples of the dehydrating agent include fatty acid anhydrides such as acetic anhydride, aromatic acid anhydrides such as benzoic anhydride, and the like, and two or more types may be combined.

The ring closure rate of imine is not particularly limited, but it is usually 70% or more, preferably 85 to 100%. Here, the "imine ring closure rate" means the content of the cyclic imine bond in the component (A1) (the same applies below), which can be measured by various methods such as nuclear magnetic resonance (NMR) or infrared (IR) analysis. It is decided by spectroscopic means.

(A1) The physical properties of the component are not particularly limited. From the viewpoint of the balance between adhesion and low dielectric properties, it usually refers to the number average molecular weight (value obtained by gel permeation chromatography in terms of polystyrene, The same below) is about 5000 to 50000, preferably about 7000 to 30000, and the glass transition temperature (JIS-K7121) is about 30 to 160°C, preferably about 40 to 140°C. In addition, the concentration of the terminal acid anhydride group of the component (A1) is not particularly limited, but it is usually about 2000 to 40000 eq/g, preferably about 3000 to 20000 eq/g.

Furthermore, the molecular end of the component (A1) can be modified (capped) by various low molecular weight primary alkyl monoamines. Specifically, for example, ethylamine, n-propylamine, isopropylamine, n-butylamine, isobutylamine, secondary butylamine, tertiary butylamine, pentylamine, isoamylamine, tertiary pentylamine, n-octylamine, N-decylamine, isodecylamine, n-tridecylamine, n-laurylamine, n-cetylamine, n-stearylamine, etc. Especially, from the viewpoint of low dielectric properties, the carbon number of the alkyl group is preferred It is about 4-15. In addition, the amount of the primary alkyl monoamine used is not particularly limited, and it is usually about 0.8 to 1.2 mol, preferably about 0.9 to 1.1 mol, relative to the terminal anhydride group of the component (A1).

The resin composition of the present invention may contain polyimide (A2) other than the aforementioned (A1) component (hereinafter also referred to as (A2) component).

(A2) As long as the component is a polyimide other than the aforementioned (A1) component, various conventional materials can be used, and preferably one type of polyimide (except for the compound corresponding to the aforementioned (A1) component) , Which is formed by reacting the monomer group (2) (hereinafter, also referred to as (2) component), and the monomer group (2) contains the aforementioned (a1) component and/or aromatic tetracarboxylic dianhydride ( a1') (hereinafter also referred to as (a1') component), and the aforementioned (a2) component and/or unhydrogenated dimer diamine (a2') (hereinafter also referred to as (a2') component), the aromatic The free carboxylic acid content of the tetracarboxylic dianhydride (a1') is 1% by weight or more.

As the component (a1'), as long as it is an aromatic tetracarboxylic dianhydride in which the content of the free carboxylic acid in the aromatic tetracarboxylic dianhydride is 1% by weight or more, various conventional materials can be used, and there is no particular limitation. . In addition, 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 of the free carboxylic acid becomes 1% by weight or more. From the viewpoint of maintaining the adhesive force of the adhesive of the present invention and improving its low dielectric properties, the upper limit of the content of the free carboxylic acid in the (a1') component is usually 5% by weight or less.

The component (a2') includes, for example, the compounds described in the aforementioned Japanese Patent Application Laid-Open No. 9-12712 and the like. Examples of commercially available products include Versamine 551 (manufactured by BASF Japan Co., Ltd.) and PRIAMINE 1074 (Croda Japan Co., Ltd. system).

(2) The component (a3) can also be contained in the component. The component (a3) includes, for example, various conventional diaminopolysiloxanes, such as α,ω-bis(2-aminoethyl)polydimethylsiloxane, α,ω-bis (3-Aminopropyl) polydimethylsiloxane, α,ω-bis(4-aminobutyl) polydimethylsiloxane, α,ω-bis(5-aminopentyl) Polydimethylsiloxane, α,ω-bis[3-(2-aminophenyl)propyl]polydimethylsiloxane, α,ω-bis[3-(4-aminophenyl) ) Propyl] polydimethylsiloxane etc.

Hereinafter, representative examples of the combination of the raw materials in the component (2) are given. 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 E. (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. (a1') component, (a2) component, and (a4) component. (a1) component, (a2') component And (a4) component

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

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

In addition, (2) component can also contain (a4) component. At this time, the amount of (a4) used is not particularly limited, and when all diamine components are set to 100 mol%, it is usually less than 40 mol%.

The manufacturing method of (A2) component is in accordance with the manufacturing method of (A1) component. (A2) The oximine ring closure rate of the component is also not particularly limited, but is usually 70% or more, preferably 85 to 100%.

(A2) The physical properties of the component are not particularly limited. From the viewpoint of the balance between adhesive force and low dielectric properties, it usually refers to the number average molecular weight (value obtained by gel permeation chromatography and converted to polystyrene, The same below) is about 5000 to 50000, preferably about 7000 to 30000, and the glass transition temperature (JIS-K7121) is about 30 to 160°C, preferably about 40 to 140°C. In addition, the concentration of the terminal acid anhydride group of the component (A2) is not particularly limited, but it is usually about 2000 to 40000 eq/g, preferably about 3000 to 20000 eq/g.

Furthermore, the molecular end of the component (A2) can be modified (capped) by the aforementioned primary alkyl monoamine.

The weight ratio of the solid content of the component (A1) to the component (A2), that is, (A1)/(A2) is not particularly limited. From the viewpoint that the low dielectric properties of the cured product of the composition containing both are particularly low, generally It is about 30/70～90/10, preferably about 40/60～99/1.

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

(B) The component can use various conventional materials, and is not particularly limited. For example, polyepoxy compound (B1) (hereinafter also referred to as (B1) component), polyphenylene ether compound (B2) (hereinafter also referred to as ( B2) component), and other crosslinking agents (hereinafter also referred to as (B3) component). Among these, the (B1) component and/or (B2) component are preferable.

(B1) The component may include, for example: phenol novolak type epoxy compound, cresol novolak type epoxy compound, bisphenol A type epoxy compound, bisphenol F type epoxy compound, bisphenol S type epoxy compound, hydrogenated Bisphenol A type epoxy compound, hydrogenated bisphenol F type epoxy compound, stilbene type epoxy compound, triazine skeleton-containing epoxy compound, stilbene skeleton-containing epoxy compound, linear aliphatic epoxy compound, alicyclic Formula epoxy compounds, glycidylamine epoxy compounds, triphenolmethane epoxy compounds, alkyl modified triphenolmethane epoxy compounds, biphenyl epoxy compounds, epoxy compounds containing dicyclopentadiene skeleton, Epoxy compound containing naphthalene skeleton, aryl alkylene type epoxy compound, tetraglycidylxylylenediamine; modified epoxy compound, dimerized epoxy compound modified by dimer acid to modify these epoxy compounds Two or more types of diglycidyl acid etc. 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 a company limited by shares; "YD-172-X75" manufactured by Nippon Steel Chemical Corporation, etc.

From the viewpoint of compatibility and heat resistance, among the components (B1), tetraglycidylxylylenediamine of the following structure is preferred. For example, "Tetrad-X" manufactured by Mitsubishi Gas Chemical Co., Ltd. can be used. Commercially available.

式中，Z¹ 表示伸苯基或伸環己基。

In the formula, Z ¹ represents phenylene or cyclohexylene.

In addition, when the component (B1) is used, various conventional curing agents for epoxy compounds can be used in combination. Specifically, for example: succinic anhydride, phthalic anhydride, maleic anhydride, trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride 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, methyl norbornane-2,3-dicarboxylic anhydride, methylcyclohexene dicarboxylic acid Acid anhydride hardeners such as formic anhydride, 3-dodecenyl succinic anhydride, and octenyl succinic anhydride; dicyandiamide (DICY), aromatic diamines (trade names "Lonzacure M-DEA", "Lonzacure M-DETDA" Etc., all manufactured by Lonza Japan Co., Ltd.), aliphatic amines and other amine hardeners; phenol novolak resin, cresol novolak resin, bisphenol A novolak resin, triazine-modified phenol novolak resin, containing Phenolic hydroxyphosphazene (phosphazene) (trade name "SPH-100" manufactured by Otsuka Chemical Co., Ltd.) and other phenolic hardeners; cyclic phosphazene compounds, maleic acid modified rosin or its hydride and other rosins A crosslinking agent, etc., can be combined with two or more types. Among these, phenolic hardeners are preferred, and phenolic hydroxyphosphazene-containing hardeners are particularly preferred. The usage amount of these curing agents 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, and preferably about 10 to 40% by weight.

In addition, when the component (B1) is used, a curing catalyst can also be used. Specifically, for example: 1,8-diazabicyclo[5.4.0]undecene-7, triethylenediamine, benzyldimethylamine, triethanolamine, dimethylaminoethanol, ginseng ( Dimethylaminomethyl) phenol and other tertiary amines; 2-methylimidazole, 2-phenylimidazole, 2-phenyl-4-methylimidazole, 2-ethyl-4-methylimidazole, 1- Imidazoles such as cyanoethyl-2-undecylimidazole and 2-heptadecylimidazole; organic phosphines such as tributylphosphine, methyldiphenylphosphine, triphenylphosphine, diphenylphosphine, and phenylphosphine; Tetraphenyl phosphonium tetraphenylborate, 2-ethyl-4-methylimidazole tetraphenylborate, N-methylmorpholine tetraphenylborate and other tetraphenylborate salts; caprylic acid, stearic acid, acetone acetone complex, ring Organic metal salts such as Zn, Cu and Fe of organic acids such as alkanoic acid and salicylic acid can be combined with two or more kinds. In addition, 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 (B2) component, various conventional materials can be used, and there is no restriction|limiting in particular. Specifically, the compound represented by the following general formula is preferable.

式中，Z² 表示碳數1～3的伸烷基或單鍵，m表示0～20，n表示0～20，m與n之合計表示1～30。

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

(B2) The physical properties of the component are not particularly limited. From the viewpoint of adhesion and low dielectric properties, it is generally preferable that the terminal hydroxyl group concentration is about 900-2500 μmol/g and the number average molecular weight is about 800-2000.

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

Examples of the aforementioned benzoxazine compound include: 6,6-(1-methylethylene)bis(3,4-dihydro-3-phenyl-2H-1,3-benzoxazine), 6 ,6-(1-methylethylene)bis(3,4-dihydro-3-methyl-2H-1,3-benzoxazine), etc., can be combined with two or more types. Furthermore, the nitrogen of the oxazine ring may be bonded to phenyl, methyl, cyclohexyl, etc. In addition, commercially available products include, for example, "Benzoxazine F-a type" and "Benzoxazine P-d type" manufactured by Shikoku Chemical Industry Co., Ltd., and "RLV-100" manufactured by AIR WATER.

The aforementioned bismaleimide compound may include, for example, 4,4'-diphenylmethane bismaleimide, metaphenyl bismaleimide, and bisphenol A diphenyl ether bismaleimide. Imine, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bis Maleimide, 1,6'-bismaleimide-(2,2,4-trimethyl)hexane, 4,4'-diphenyl ether bismaleimide, 4 ,4'-Diphenyl bismaleimide, etc., can be combined with two or more. In addition, examples of commercially available products include "BAF-BMI" manufactured by JFE Chemical Co., Ltd. and the like.

Examples of the cyanate compound include: 2-allylphenol cyanate, 4-methoxyphenol cyanate, 2,2-bis(4-cyanatophenol)-1,1,1,3 ,3,3-hexafluoropropane, bisphenol A cyanate, diallyl bisphenol A cyanate, 4-phenylphenol cyanate, 1,1,1-parameter (4-cyanatobenzene Yl)ethane, 4-cumenylphenol cyanate, 1,1-bis(4-cyanatophenyl)ethane, 4,4'-bisphenol cyanate, and 2,2-bis( 4-cyanatophenyl) propane, etc., two or more types may be combined. In addition, examples of commercially available products include "PRIMASET BTP-6020S" (manufactured by Lonza Japan Co., Ltd.), "CYTESTER TA (manufactured by Mitsubishi Gas Chemical Co., Ltd.)" and the like.

(B) The amount of component used is not particularly limited. It is usually 3 to 30 parts by weight relative to 100 parts by weight of the total of (A1) and (A2) components (hereinafter sometimes referred to as (A) component) About 5 to 25 parts by weight is preferred.

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

(C) Various conventional solvents can be used for the component, and there is no particular limitation. Specific examples include: N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, dimethyl sulfide, N-methylcaprolactone, 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 Solvent: Aromatic solvents such as toluene, etc., two or more types can be combined. In particular, from the viewpoint of low dielectric properties, among these, aromatic solvents are preferred.

The amount of (C) component used is not particularly limited, but it is about 0.1 to 10 parts by weight, preferably about 1 to 5 parts by weight, based on 100 parts by weight of (A) component.

式中，Q表示包含會與酸酐基進行反應的官能基之基，R¹ 表示氫或碳數1～8的烴基，R² 表示碳數1～8的烴基，a表示0、1或2。The resin composition of the present invention can further contain a reactive alkoxysilyl compound (D) represented by the following general formula (hereinafter also referred to as (D) component). Examples of the reactive functional group contained in Q include an amino group, an epoxy group, and a thiol group.

In the formula, Q represents a group containing a functional group that reacts with an acid anhydride group, R ¹ represents hydrogen or a hydrocarbon group having 1 to 8 carbons, R ² represents a hydrocarbon group having 1 to 8 carbons, and a represents 0, 1, or 2.

With the component (D), it is possible to adjust the melt viscosity while maintaining the low dielectric properties of the hardened layer of the adhesive of the present invention. As a result, it is possible to improve the interface adhesion between the hardened layer and the substrate (the so-called anchoring effect) while suppressing the hardened layer from exuding from the end of the substrate (hereinafter sometimes referred to as flow control ).

Examples of compounds in which the functional group in Q is an amino group: N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)- 3-aminopropyltrimethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, 3-ureidopropyltrialkoxysilane, etc.

Examples of compounds in which the functional group in Q is epoxy group include: 2-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, etc.

Examples of compounds whose functional groups in Q are thiol groups include: 3-mercaptopropyltrimethoxysilane, 3-mercaptopropyltriethoxysilane, 3-mercaptopropylmethyldimethoxysilane, and 3 -Mercaptopropylmethyl diethoxysilane, etc.

Since it reacts quickly with the terminal acid anhydride group of the component (A) and the aforementioned flow control effect is good, the component (D) is preferably a compound in which the functional group in Q is an amine group.

The amount of (D) component used is not particularly limited, but it is 0.01 to 5 parts by weight, preferably about 0.1 to 3 parts by weight, relative to 100 parts by weight of (A) component.

The adhesive of the present invention is composed of a resin composition. The resin composition can be used directly, or the following can be prepared according to the needs: the aforementioned ring-opening esterification reaction catalyst or dehydrating agent, plasticizer, weathering agent, Oxidizing agent, heat stabilizer, lubricant, antistatic agent, brightener, coloring agent, conductive agent, release agent, surface treatment agent, viscosity regulator, phosphorus flame retardant, flame retardant filler, silica filler and fluorine Additives such as fillers; or diluting solvents.

The film-like adhesive material of the present invention is formed by curing the adhesive of the present invention by conventional means. Specifically, for example, the adhesive is applied to various supports and heated to volatilize component (C) to harden and peel from the support. This material can be used as a film-like adhesive Material utilization. In addition, the coating means is not particularly limited, and examples thereof include curtain coaters, roll coaters, and laminators. In addition, 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 aforementioned hardened substance is used as an adhesive layer. Specifically, it is composed of the aforementioned cured material and various conventional sheet substrates. Examples of the sheet substrate include polyester resins, polyimide resins, polyimide-silica hybrid resins, polyethylene resins, Polypropylene resin, polyethylene terephthalate resin, polyethylene naphthalate resin, polymethyl methacrylate resin, polystyrene resin, polycarbonate resin, acrylonitrile-butadiene-styrene Resin; Aromatic polyester resin obtained from ethylene terephthalate or phenols, phthalic acid, hydroxynaphthoic acid, etc. 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 also not particularly limited, but it is usually 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 polyimide-based adhesive, the film-like adhesive material, and the adhesive sheet. Specifically, it can be obtained by the following method: using these to form an adhesive layer on at least one side of the core substrate, that is, a printed circuit board, and laminate other printed circuit boards or printed circuit boards on it, and then heat and Press and stick under pressure. The heating temperature, pressure bonding time, and pressure are not particularly limited, but they are usually about 70 to 200°C, about 1 minute to 3 hours, and about 0.5 to 20 MPa.

The copper foil with resin of the present invention is formed by using at least one selected from the group consisting of the polyimide adhesive, the film-like adhesive material, and the adhesive sheet to form an adhesive layer on the copper foil Of items. Examples of the copper foil include rolled copper foil and electrolytic copper foil, and various surface treatments (roughening, rust prevention, etc.) can be applied. In addition, the thickness of the copper foil is not particularly limited, but it is usually about 1 to 100 μm, preferably about 2 to 38 μm. The adhesive layer of the resin-attached copper foil may not be hardened, and it may be partially hardened or completely hardened under heating. The partially hardened adhesive layer is in the so-called B-stage state. In addition, the thickness of the adhesive layer is not particularly limited, but is usually about 0.5 to 30 μm. In addition, it is also possible to further bond copper foil to the adhesive surface of the obtained copper foil with resin to produce copper foil with resin on both sides.

The copper clad laminate of the present invention is an article formed by laminating the resin-coated copper foil of the present invention and copper foil or an insulating sheet, and is also called CCL (Copper Clad Laminate). Specifically, the resin-coated copper foil of the present invention is press-bonded to at least one side or both sides of various conventional insulating sheets under pressure. In addition, when pressure-bonded on one side, something different from the resin-attached copper foil of the present invention can be pressure-bonded on the other side under heating. In addition, the number of resin-attached copper foils and insulating sheets in the copper-clad laminate is not particularly limited. In addition, the insulating sheet may be a prepreg. The so-called prepreg refers to a sheet-like material, which is made by impregnating a resin in a reinforcing material such as glass cloth and hardening it to the B stage (JIS C 5603). The resin is usually used: polyimide resin , Phenol resin, epoxy resin, polyester resin, liquid crystal polymer and aramid resin and other insulating resins. In addition, the thickness of the prepreg is not particularly limited, but it is usually about 20 to 500 μm. In addition, heating and pressure bonding conditions are not particularly limited, and are usually about 150 to 280°C and about 0.5 to 20 MPa.

The printed circuit board of the present invention is formed by forming a circuit pattern on the copper foil surface of the aforementioned copper clad laminate. The patterning means can be, for example, subtractive or semi-additive. The semi-additive method may include, for example, the following method: after patterning the copper foil surface of the copper clad laminate of the present invention with a resist film, electrolytic copper plating is performed, and the resist is removed, and then etching with an alkaline solution. In addition, the thickness of the circuit pattern layer in the printed wiring board is not particularly limited. In addition, it is also possible to obtain a multilayer substrate by using the printed circuit board as a core substrate and laminating the same printed circuit board or other conventional printed circuit boards or printed circuit boards on it. When laminating, not only the polyimide-based adhesive of the present invention, but also other conventional polyimide-based adhesives can be used. In addition, the number of layers in the multilayer substrate is not particularly limited. In addition, through holes can be inserted every time the layer is stacked, and the interior can be plated. [Example]

The following examples and comparative examples illustrate the present invention in detail, but the scope of the present invention is not limited by these examples. In addition, in each example, parts and% are based on weight unless otherwise stated.

[Manufacturing Example 1] 　　 A commercially available aromatic tetracarboxylic dianhydride (trade name "BTDA-UP", manufactured by EVONIK Japan Co., Ltd.) was fed into a reaction vessel equipped with a stirrer, a water separator, a thermometer, and a nitrogen introduction tube. The content of 3,3',4,4'-benzophenone tetracarboxylic dianhydride is 99.9% or more) 210.0 g, cyclohexanone 1008.0 g, methylcyclohexane 201.6 g, and the solution is heated to 60℃ . Then, 341.7 g of hydrogenated dimer diamine (trade name "PRIAMINE 1075", manufactured by Croda Japan Co., Ltd.) was dropped, and it was subjected to an imidization reaction at 140°C for 10 hours to obtain a softening point of approximately A solution of polyimide resin (A1-1) with a weight average molecular weight of about 35,000 at 80°C (non-volatile content 30.0%). In addition, the molar ratio of the acid component/amine component was 1.03.

[Manufacturing Example 2] 　　 In the same reaction vessel as in Manufacturing Example 1, a commercially available aromatic tetracarboxylic dianhydride (trade name "BisDA-2000", manufactured by SABIC Japan Co., Ltd., 4,4'-[PP- 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 Heat the solution to 60°C. Then, after dropping 59.3 g of PRIAMINE 1075, it took 10 hours to carry out the imidization reaction at 140°C to obtain a polyimide resin (A1-2) with a softening point of about 90°C and a weight average molecular weight of about 30,000.的 solution (non-volatile content 31.9%). In addition, the molar ratio of 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'-[PP The content of -2,2-diylbis(1,4-phenoxy)]diphthalic dianhydride is 98.0%) 65.0 g, cyclohexanone 266.5 g, methylcyclohexane 44.4 g, and Heat the solution to 60°C. Then, 43.7 g of PRIAMINE 1075 and 5.4 g of 1,3-bis(aminomethyl)cyclohexane were dropped, and it took 10 hours at 140°C to carry out the imidization reaction, thereby obtaining a softening point of about 100°C. And a solution of polyimide resin (A2-1) with a weight average molecular weight of about 30,000 (non-volatile content 29.2%). In addition, the molar ratio of acid component/amine component was 1.05.

[Comparative Production Example 2] 　　 In the same reaction vessel as in Production Example 1, a commercially available aromatic tetracarboxylic dianhydride (trade name "BTDA-PF", manufactured by EVONIK Japan Co., Ltd., 3, 3', 4 The content of 4'-benzophenone tetracarboxylic dianhydride is 98%) 200.0 g, cyclohexanone 960.0 g, methylcyclohexane 192.0 g, and the solution is heated to 60°C. Then, 319.2 g of PRIAMINE 1075 was dropped, and it was subjected to an imidization reaction at 140°C for 10 hours to obtain a polyimide resin (A2-2) with a softening point of about 80°C and a weight average molecular weight of about 25,000.的 solution (non-volatile content 29.8%). In addition, the molar ratio of acid component/amine component was 1.05.

[Comparative Manufacturing Example 3] "In the same reaction vessel as in Manufacturing 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, 277.5 g of PRIAMINE 1075 and 23.8 of commercially available polydimethylsiloxane (trade name "KF-8010", manufactured by Shin-Etsu Chemical Co., Ltd.) were added dropwise, and it took 10 hours to carry out treatment at 140°C. The amination reaction obtains a polyimide resin (A2-3) solution (non-volatile content 29.8%) with a softening point of about 70°C and a weight average molecular weight of about 15,000. In addition, the molar ratio of 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 took 10 hours to carry out the imidization reaction at 140°C to obtain a polyimide resin (A2-4) with a softening point of about 20°C and a weight average molecular weight of about 35,000.的 solution (non-volatile 36.7%). In addition, the molar ratio of 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 dropped, and it was subjected to an imidization reaction at 140°C for 10 hours. A solution of polyimide resin (A2-5) with a softening point of about 70°C and a weight average molecular weight of about 25,000 (non-volatile content 29.8%) was obtained. In addition, the molar ratio of acid component/amine component was 1.05.

[Comparative Manufacturing Example 6] "In the same reaction vessel as in Manufacturing 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 dropped, and it was subjected to an imidization reaction at 140°C for 10 hours. A solution of polyimide resin (A2-6) with a softening point of about 80°C and a weight average molecular weight of about 35,000 (non-volatile content 29.8%) was obtained. In addition, the molar ratio of acid component/amine component was 1.09.

<Measurement of the dielectric constant and the dielectric loss tangent of the polyimide film> 　　 The polyimide solution of the production example and the comparative production example were respectively coated on NAFLON PTFE tape TOMBO No.9001 (NICHIAS Co., Ltd.), After drying at room temperature for 12 hours, it was cured at 200°C for 1 hour to obtain a cured product sheet with a film thickness of 50 μm. Then, in accordance with JIS C2565, a commercially available dielectric constant measuring device (cavity resonator type, manufactured by AET) was used to measure the dielectric constant (Dk) and dielectric loss tangent ( Df). The results are shown in Table 1.

[Table 1]

(Example 1) 　　 100.00 g of a solution of (A1-1) component, 1.67 g of tetraglycidylxylylenediamine ("Tetrad-X", manufactured by Mitsubishi Gas Chemical Co., Ltd.) as component (B) and containing Hydroxy polyphenylene ether (trade name "SA90", manufactured by SABIC Co., Ltd.) 1.67 g, toluene 7.87 g as component (C), and a commercially available amino-containing silane coupling agent (trade name) as component (D) KBM603", manufactured by Shin-Etsu Chemical Co., Ltd., 0.07 g of N-2-(aminoethyl)-3-aminopropyltrimethoxysilane) is mixed to obtain a resin composition with a non-volatile content of 30.0% (adhesive Agent).

(Example 2) 　　 100.00 g of a solution of (A1-2) components, 1.78 g of Tetrad-X, 1.78 g of SA90, 14.78 g of toluene, and 0.07 g of KBM603 were mixed to obtain a resin composition (adhesive) with a non-volatile content of 30.0% Agent).

(Example 3) 　　 The (A1-1) component solution 100.00 g and the (A2-3) component solution 25.17 g, Tetrad-X 2.09 g, SA90 2.09 g, toluene 9.59 g, and KBM603 0.08 g were mixed to obtain 30.0% non-volatile resin composition (adhesive).

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

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

(Example 6) ``30.00 g of (A1-1) component solution, 30.82 g of (A2-1) component solution and 15.10 g of (A2-3) component solution, commercially available multifunctional epoxy resin (commercial Name "jER630", manufactured by Mitsubishi Chemical Corporation, N,N-diglycidyl-4-glycidoxyaniline) 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 are mixed to obtain a resin composition (adhesive) with a non-volatile content of 30.0%.

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

(Example 8) "(A1-1) component solution 100.00 g, Tetrad-X 1.67 g, and toluene 3.90 g were mixed, and the resin composition (adhesive) with a non-volatile content of 30.0% was obtained.

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

(Example 10) ``(A1-1) component solution 30.00 g, (A2-1) component solution 30.82 g, and (A2-6) component solution 15.05 g, jER630 3.30 g, and Bis-A cyanate ester (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 resin composition with a non-volatile content of 30.0% (adhesive Agent).

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

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

(Comparative Example 1) 　　 100.00 g of (A2-2) component solution, Tetrad-X 1.65 g and SA90 1.65 g, toluene 7.05 g, and KBM603 0.07 g were mixed to obtain a resin composition with a non-volatile content of 30.0% (adhesive Agent).

(Comparative Example 2) 　　 100.00 g of a solution of (A2-3) component, 1.65 g of Tetrad-X, 1.65 g of SA90, 7.05 g of toluene, and 0.07 g of KBM603 were mixed to obtain a resin composition with a non-volatile content of 30.0% (adhesive Agent).

(Comparative Example 3) 　　 Mix 20.00 g of (A1-1) component solution and 80.54 g of (A2-3) component solution, Tetrad-X 1.67 g, SA90 1.67 g, toluene 7.47 g, and KBM603 0.07 g to obtain 30.0% non-volatile resin composition (adhesive).

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

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

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

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

<Preparation of Adhesive Sheet> 　　The adhesive of Example 1 was applied to the support sheet (trade name "Kapton 100EN", DU PONT-TORAY Co., Ltd.) using a gap coater so that the thickness after drying became 10 μm It is manufactured by the company, with a film thickness of 25 μm and a thermal expansion coefficient of 15 ppm/°C), and then dried at 180°C for 3 minutes to obtain an adhesive sheet. The same was done for the adhesives of other examples and comparative examples to obtain adhesive sheets.

Then, the mirror side of 18 μm thick electrolytic copper foil (trade name "F2-WS", manufactured by Furukawa Circuit Foil Co., Ltd.) was superimposed on the adhesion surface of each adhesive sheet, and the pressure was 1 MPa, 180°C and 30°C. Heat and press under the condition of minutes to produce a laminate. The same was done for the adhesive of Comparative Example 1 to obtain a laminate.

<Measurement of the dielectric constant and dielectric loss tangent of the adhesive layer> 　　Pour about 7 g of the adhesive of the example and the comparative example into a fluororesin PFA flat plate (diameter 75 mm, made by Mutual Chemical Glass Manufacturing Co., Ltd.) And cured under the conditions of 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 to obtain a cured product with a thickness of about 300 μm Thin slices. Then, in accordance with JIS C2565, a commercially available dielectric constant measuring device (cavity resonator type, manufactured by AET) was used to measure the dielectric constant (Dk) and dielectric loss tangent ( Df).

<Adhesion Test> 　　 According to JIS C-6481 (Test Method for Copper Clad Laminate Boards for Flexible Printed Wiring Boards), the peel strength (N/cm) of each laminate of the Examples and Comparative Examples was measured.

<Solder heat resistance test> 　　The laminates of the Examples and Comparative Examples were floated in a solder bath at 288°C for 30 seconds with the copper foil side down, and the appearance was checked for changes. Set no change to ○, and set blistering and swelling to ×.

[Table 2]

<Production of bonding sheet> 　　The adhesive of Example 1 was applied to the release film (trade name "WH52-P25CM (white)" using a gap coater so that the thickness after drying became approximately 25 μm. Sun A. Kaken Co., Ltd.) was dried at 150°C for 5 minutes to obtain a bonded sheet. The adhesives of other examples and comparative examples were also performed in the same way to obtain bonding sheets.

<Production of Printed Wiring Board> 　　 After forming a resist pattern with line/spacing = 0.2/0.2 (mm) from the double-sided copper foil of the copper-clad laminate of Example 1, it was immersed in a 40% iron chloride aqueous solution To perform etching to form a copper circuit. In this way, a printed wiring board is obtained.

＜Production of multilayer circuit board＞ 　　Using the obtained printed circuit board as the core material, overlay the copper foil with resin of Example 1 on both sides of it, and press-bond under the conditions of 4.5 MPa, 200°C and 30 minutes After that, a resist pattern of line/space = 0.2/0.2 (mm) was formed on the untreated copper foil of the outer layer of the resultant. Then, the obtained substrate was immersed in a 40% iron chloride aqueous solution to perform etching, thereby forming a copper circuit. The aforementioned 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 was obtained.

<Production of Printed Wiring Board 2> 　　 After forming a resist pattern with line/spacing = 0.2/0.2 (mm) from the copper foil of the single-sided copper-clad laminate of Example 1, it was immersed in a 40% iron chloride aqueous solution It is etched to form a copper circuit. The same thing is prepared, the aforementioned bonding sheet is 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 to laminate. Then, the aforementioned bonding sheet was laminated on the surface layer of the laminate on which the copper circuit was formed, and heated and pressed under the conditions of a pressure of 1 MPa, 180° C., and 30 minutes to laminate. In this way, a multilayer wiring board having four circuit pattern layers was obtained.

The adhesives of other embodiments are also used to obtain printed circuit boards and multilayer circuit boards by the same method.

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Claims (19)

A resin composition comprising polyimide (A1) and polyimide (A2) other than the component (A1), and the polyimide (A1) is formed by reacting monomer group (1) , The monomer group (1) contains aromatic tetracarboxylic dianhydride (a1) and hydrogenated dimer diamine (a2) and does not contain diamine-based polysiloxane (a3), the aromatic tetracarboxylic dianhydride (a1) The free carboxylic acid content of the anhydride (a1) is less than 1% by weight. The resin composition according to claim 1, wherein the aromatic tetracarboxylic dianhydride as the component (a1) has the following structure:

In the formula, X represents a single bond, -SO ₂ -, -CO-, -O-, -OC ₆ H ₄ -C(CH ₃ ) ₂ -C ₆ H ₄ -O- or -COO-Y-OCO-, Wherein, Y represents -(CH ₂ ) ₁ -or -H ₂ C-HC(-OC(=O)-CH ₃ )-CH ₂ -, 1=1 to 20. The resin composition according to claim 1 or 2, wherein the molar ratio of (a1) component and (a2) component in component (1), that is, (a1)/(a2) is 1 to 1.5. The resin composition according to claim 1, wherein the component (A2) is formed by reacting the monomer group (2), and the monomer group (2) contains the component (a1) and/or aromatic tetracarboxylic acid The dianhydride (a1'), and the component (a2) and/or unhydrogenated dimer diamine (a2'), the aromatic tetracarboxylic dianhydride The content of free carboxylic acid in (a1') is 1% by weight or more. The resin composition according to claim 4, wherein the component (2) further contains the component (a3). The resin composition according to claim 1 or 2, wherein the weight ratio of the solid content of the (A1) component to the (A2) component, that is, (A1)/(A2) is 40/60 to 99/1. The resin composition according to claim 1, which further contains a crosslinking agent (B). The resin composition according to claim 7, wherein the component (B) is a polyepoxy compound (B1) and/or a polyphenylene ether compound (B2). The resin composition according to claim 8, wherein the component (B1) is tetraglycidylxylylenediamine of the following structure:

In the formula, Z ¹ represents phenylene or cyclohexylene. The resin composition according to claim 8 or 9, wherein the component (B2) is a hydroxyl-containing polyphenylene ether having the following structure:

In the formula, Z ² represents an alkylene group having 1 to 3 carbon atoms or a single bond, m represents 0 to 20, n represents 0 to 20, and the total of m and n represents 1 to 30. The resin composition described in claim 1 or 2, which , Further contains an organic solvent (C). The resin composition according to claim 1 or 2, which further contains a reactive alkoxysilyl compound (D) represented by the following general formula: Q-Si(R ¹ ) _a (OR ² ) _{3- In the} formula a, Q represents a group containing a functional group that can react with an acid anhydride group, R ¹ represents hydrogen or a hydrocarbon group with 1 to 8 carbons, R ² represents a hydrocarbon group with 1 to 8 carbons, and a represents 0, 1, or 2 . An adhesive composed of the resin composition described in any one of claims 1 to 12. A film-like adhesive material, which is composed of a hardened product of the adhesive described in claim 13. An adhesive sheet in which the cured product of the adhesive described in claim 13 is used as an adhesive layer. A multilayer circuit board using at least one selected from the group consisting of the adhesive described in claim 13, the film-like adhesive material described in claim 14, and the adhesive sheet described in claim 15 . A resin-attached copper foil using at least one selected from the group consisting of the adhesive described in claim 13, the film-like adhesive material described in claim 14, and the adhesive sheet described in claim 15 One kind. A copper-clad laminated board obtained by using the resin-attached copper foil described in claim 17. A printed circuit board obtained by using the copper-clad laminated board described in claim 18.