TWI716524B - Copper clad laminate and printed circuit board - Google Patents

Abstract

The problem to be solved by the present invention is to provide a metal-clad laminate and a novel printed circuit board. The metal-clad laminate has excellent metal adhesion, heat resistance, low dielectric constant of insulating materials, and low dielectric loss tangent characteristics. The printed wiring board is characterized by using this metal-clad laminate to reduce transmission loss. The solution of the present invention is a copper-clad laminate comprising a copper foil (3) which is laminated on at least one side of the insulating film (1) via an adhesive layer (2), wherein , 　　 insulation film (1) has a thermal expansion coefficient of 4-30 ppm/°C, 　　 adhesive layer (2) contains acid anhydride group-terminated polyimide (A) and crosslinking component (B), the acid anhydride group-terminated polyimide (A) is the reactant of aromatic tetracarboxylic anhydride and diamine monomer, the diamine monomer contains dimer diamine, 　　, the surface of the copper foil (3) that is in contact with the adhesive layer (2) The ten-point average roughness Rz is 0.1 to 1.5 μm.

Description

Copper clad laminate and printed circuit board

The invention relates to 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) and multilayer circuit boards obtained using these are widely used in the following products: mobile phones and smart phones, etc. Mobile communication equipment or its base station equipment; network-related electronic equipment such as servers/routers; large computers, etc.

In recent years, in these products, high-frequency electronic signals are used for high-speed transmission/processing of large-capacity information. However, since high-frequency signals are very easy to attenuate, it is also sought to suppress transmission loss as much as possible for multilayer circuit boards. . Transmission loss includes conductor loss and dielectric loss. The conductor loss is that if the frequency of the electronic signal exceeds GHz, it will be due to the skin effect and will depend on the surface condition of the copper foil used in the circuit. On the other hand, the dielectric loss will greatly affect the dielectric properties of the insulating material near the circuit, especially the dielectric loss tangent.

As a means of suppressing the transmission loss in the multilayer circuit board, it is possible to consider, for example, the use of a flexible copper-clad laminate as a base material. The flexible copper-clad laminate is made of polyimide with excellent low dielectric properties. It is obtained with a liquid crystal polymer, etc. (for example, refer to Patent Documents 1 and 2).

However, these methods require a step of bonding copper foils at high temperatures (above 300°C), and problems such as poor yield are likely to occur, and solutions are being sought.

On the other hand, there is also the following method: using a copper-clad laminate formed by combining a low-roughness copper foil and a polyimide layer to suppress the conductor loss from the surface of the copper foil to suppress the transmission loss (for example, With reference to Patent Document 3), when bonding copper foil, a bonding step at a high temperature (300°C or higher) is still required, and problems such as poor yield are likely to occur, and solutions are being sought.

In addition, from the viewpoint of impedance control, it is preferable that the dielectric constant of the insulating material be low. In other words, the impedance (Z ₀ ) of the transmission circuit is determined by the following: the thickness and dielectric constant of the insulating material, and the width and thickness of the circuit. In recent years, the thinning of circuit boards is progressing. In order to coexist impedance control and thinning, it is necessary to (1) reduce the dielectric constant of insulating materials, or (2) thinner and narrower circuits. However, in the case of (2), the possibility of loss of circuit reliability is high and not good. Therefore, in the sense of expanding the degree of freedom of circuit design, the requirements for low-dielectric materials are higher. [Prior Art Document] (Patent Document)

Patent Document 1: Japanese Patent Application Publication No. 08-058024 　　 Patent Document 2: Japanese Patent Application Publication No. 2014-526399 　　 Patent Document 3: Japanese Patent Application Publication No. 2015-91644

[Problem to be solved by the invention] 　　 The main problem to be solved by the present invention is to provide a copper-clad laminate and a novel printed circuit board. The copper-clad laminate has copper adhesion, heat resistance, and low dielectric constant of insulating materials , Low dielectric loss and excellent tangent characteristics, the printed wiring board is characterized by the use of this copper clad laminate to reduce transmission loss. [Technical means to solve the problem]

After the inventors have devoted themselves to research, they have found the following facts to complete the present invention: a copper clad laminate is made by laminating an insulating film and a copper foil through a specific adhesive layer, resulting in low dielectric properties, heat resistance, The metal adhesion is excellent, and the printed wiring board produced by the metal laminate is excellent in low transmission loss.

In other words, the present invention is as shown in items 1 to 7 below. Item 1. A copper-clad laminate comprising a copper foil (3), which is laminated on at least one side of an insulating film (1) via an adhesive layer (2), wherein 　　 is insulated The thermal expansion coefficient of the film (1) is 4-30 ppm/°C, and the 　　 adhesive layer (2) contains anhydride group-terminated polyimide (A) and crosslinking component (B). The acid anhydride group-terminated polyimide (A) ) Is the reactant of aromatic tetracarboxylic anhydride and diamine monomer, the diamine monomer contains dimer diamine, 　　, ten points on the surface of the copper foil (3) that is in contact with the adhesive layer (2) The average roughness Rz is 0.1 to 1.5 μm.

Item 2. The copper-clad laminate as described in Item 1, wherein the content of the diamine diamine is 30 mol% or more in the diamine monomer.

式中，X表示單鍵、－SO₂ －、－CO－、－O－、－O－C₆ H₄ －C(CH₃ )₂ －C₆ H₄ －O－或－COO－Y－OCO－，且式中Y表示－(CH₂ )_l －或－H₂ C－HC(－O－C(＝O)－CH₃ )－CH₂ －，式中l表示1～20。Item 3. The copper clad laminate as described in Item 1 or 2, wherein the aromatic tetracarboxylic dianhydride 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 -, and Y in the formula represents -(CH ₂ ) _l -or -H ₂ C-HC(-O-C(=O)-CH ₃ )-CH ₂ -, where l represents 1-20.

Item 4. The copper-clad laminate according to any one of items 1 to 3, wherein the crosslinking component (B) is made of polyphenylene ether resin, epoxy resin, benzoxazine resin, and double At least one selected from the group consisting of maleimide resin and cyanate ester resin.

Item 5. The copper-clad laminate according to any one of items 1 to 4, wherein the adhesive layer (2) further contains a reactive alkoxysilyl compound (C).

Item 6. The copper clad laminate according to any one of items 1 to 5, wherein the dielectric constant of the adhesive layer (2) at 10 GHz is 3.0 or less, and the dielectric loss tangent It is less than 0.005.

Item 7. A printed wiring board obtained by performing circuit circuit processing on the copper foil of the copper-clad laminate according to any one of items 1 to 6. [effect]

According to the present invention, it is possible to obtain a copper-clad laminate that has good adhesion to copper foil, low dielectric properties, low water absorption, and excellent heat resistance, and therefore has high reliability. In addition, by using the copper-clad laminate of the present invention, a printed circuit board with low dielectric loss can be manufactured. The copper-clad laminate and printed circuit board of the present invention are suitable for manufacturing the following multi-layer circuit boards for products that process high-frequency signals: mobile communication devices represented by mobile phones and smart phones or their base station devices; servers/routers Internet-related electronic equipment; large computers, etc.

The copper-clad laminate of the present invention includes a copper foil (3) that is laminated on at least one side of the insulating film (1) via an adhesive layer (2). The insulating film (1) of the present invention is not particularly limited as long as the coefficient of thermal expansion is 4-30 ppm/°C. For example, a film obtained by fabricating a composite material into a film can be mentioned. The composite material is composed of: polyamide Imine, polyetherimine, aromatic polyamide, polyethylene terephthalate (PET), polyethylene naphthalate (PEN), liquid crystal polymer, or flexible epoxy/glass Weaving etc. When the coefficient of thermal expansion is less than 4 ppm/℃, or the coefficient of thermal expansion exceeds 30 ppm/℃, the difference between the coefficient of thermal expansion (16～18 ppm/℃) and the copper foil to be laminated will cause the occurrence of laminates. Problems such as warpage and decreased adhesion. The thermal expansion coefficient is preferably 13～23 ppm/℃. In addition, specifically, from the viewpoint of heat resistance, dimensional stability, and insulation, polyimide is preferred. In addition, in this specification, the so-called thermal expansion coefficient means the use of a thermomechanical analysis device (the distance between chucks is 20 mm, the width of the test piece is 4 mm, the load is 10 mg, and the heating rate is 10 ℃/min.) Measured value from 100°C to 200°C.

As mentioned above, as the insulating film (1), a polyimide film is the best. The manufacturing method can apply conventional manufacturing methods. In other words, it can be obtained by using one or two or more types of tetracarboxylic dianhydride components and one or more types of diamine components that are substantially equal to moles and polymerizing them in an organic polar solvent. After the polyamide acid polymer solution is obtained, the polyamide acid polymer solution is flow-expanded and coated on a support such as a glass plate or a stainless steel belt, and part of the solution is self-supporting. After imidization or partial drying to obtain a polyamide film (hereinafter referred to as a gel film), the polyamide film is peeled off the support, and the end is removed with a needle or paper clip. After fixing, further heating makes the polyamide acid completely imidized. Examples of commercially available polyimide films include: XENOMAX (trade name) manufactured by Toyobo Co., Ltd., POMIRAN T (trade name) manufactured by Arakawa Chemical Industry Co., Ltd., and Kapton manufactured by DU PONT-TORAY Co., Ltd. (Trade name), UPILEX (trade name) manufactured by Ube Industries Co., Ltd., APICAL (trade name) manufactured by Kaneka Co., Ltd., etc.

The thickness of the insulating film (1) is not limited, preferably 5 μm to 125 μm. In particular, in terms of ease of production and mechanical properties, the thickness is preferably 10 to 75 μm, and more preferably 10 to 50 μm.

As long as the adhesive layer (2) contains an acid anhydride group-terminated polyimide (A) (hereinafter also referred to as "(A) component") and a crosslinking component (B) (hereinafter also referred to as "(B) component"), There is no particular limitation. As long as the component (A) is preferably a reaction product of an aromatic tetracarboxylic anhydride (a1) (hereinafter also referred to as "component (a1)") and a diamine monomer, the diamine monomer includes a dimer diamine ( a2) (hereinafter also referred to as "(a2) component"), various conventional materials can be used without particular limitation.

(A1) The component includes, for example, pyromellitic dianhydride, 4,4'-oxydiphthalic dianhydride, 3,3',4,4'-benzophenone tetracarboxylic dianhydride , 3,3',4,4'-diphenyl ether tetracarboxylic dianhydride, 3,3',4,4'-diphenyl tetracarboxylic dianhydride, 1,2,3,4-benzenetetracarboxylic 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, 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-dicarboxyl) Phenyl) propane dianhydride, 2,2-bis(3,4-dicarboxyphenyl)propane dianhydride, and 4,4'-(propane-2,2-diylbis(1,4-phenoxy Base)] diphthalic dianhydride, etc., one kind or a combination of two or more kinds can be used.

式中，X表示單鍵、－SO₂ －、－CO－、－O－、－O－C₆ H₄ －C(CH₃ )₂ －C₆ H₄ －O－或－COO－Y－OCO－，且式中Y表示－(CH₂ )_l －或－H₂ C－HC(－O－C(＝O)－CH₃ )－CH₂ －，式中l表示1～20。From the viewpoint of solvent solubility, flexibility, adhesiveness, and heat resistance, the component (a1) is preferably represented by the following general formula.

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

(a2) The component is a compound derived from a dimer acid that is a dimer of unsaturated fatty acids such as oleic acid (see Japanese Patent Application Laid-Open No. 9-12712, etc.), and various conventional dimer diamines can be used, There are no special restrictions. (a2) Commercial products of the component include, for example: Versamine 551 (manufactured by BASF Japan Co., Ltd.); Versamine 552 (manufactured by BASF Japan Co., Ltd., a hydride of Versamine 551); PRIAMINE 1075, PRIAMINE 1074 (both Croda Japan) A company limited by shares) can combine two or more types. An example of hydrogenated dimer diamine is shown below.

From the viewpoint of solvent solubility, flexibility, adhesiveness, and heat resistance, the content of the component (a2) is preferably 30 mol% or more in the diamine monomer. Preferably, it is 50-100 mol%.

(A) The component can contain various conventional diaminopolysiloxanes (hereinafter also referred to as "(a3) component") as needed. Specifically, for example: 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., one kind or Combine two or more.

(A) The component may contain diamines other than the (a1) component-(a3) component (hereinafter also referred to as "(a4) component") as needed. Specifically, for example: diaminocyclohexane, diaminodicyclohexylmethane, 3,3'-dimethyl-4,4'-diaminodicyclohexylmethane, 3,3',5 ,5'-tetramethyl-4,4'-diaminodicyclohexylmethane, 4,4'-diaminodicyclohexylpropane, diaminobicyclo[2.2.1]heptane, bis(amino) Methyl)bicyclo[2.2.1]heptane, 3(4),8(9)-bis(aminomethyl)tricyclo[5.2.1.0 ^2,6 ]decane, 1,3-bis(amino) (Methyl) cyclohexane, isophorone diamine and other alicyclic diamines; 2,2-bis[4-(3-aminophenoxy)phenyl]propane, 2,2-bis[4-( 4-aminophenoxy)phenyl]propane and other diaminophenoxyphenylpropanes; 3,3'-diaminodiphenyl ether, 3,4'-diaminodiphenyl ether, 4,4'-diaminodiphenyl ether and other diaminodiphenyl ethers; p-phenylenediamine, m-phenylenediamine and other phenylenediamines; 3,3'-diaminodiphenyl sulfide , 3,4'-diaminodiphenyl sulfide, 4,4'-diaminodiphenyl sulfide and other diaminodiphenyl sulfide; 3,3'-diaminodiphenyl Diamino diphenyl ingots, 3,4'-diamino diphenyl ingot, 4,4'-diamino diphenyl ingot; 3,3'-diamino benzophenone, 4 ,4'-diaminobenzophenone, 3,4'-diaminobenzophenone and other diaminobenzophenones; 3,3'-diaminodiphenylmethane, 4,4 '-Diaminodiphenylmethane, 3,4'-Diaminodiphenylmethane and other diaminodiphenylmethanes; 2,2-bis(3-aminophenyl)propane, 2,2 -Diaminodiphenylpropanes such as bis(4-aminophenyl)propane and 2-(3-aminophenyl)-2-(4-aminophenyl)propane; 2,2-bis( 3-aminophenyl)-1,1,1,3,3,3-hexafluoropropane, 2,2-bis(4-aminophenyl)-1,1,1,3,3,3- Diaminophenylhexafluoropropane such as hexafluoropropane, 2-(3-aminophenyl)-2-(4-aminophenyl)-1,1,1,3,3,3-hexafluoropropane Class; 1,1-bis(3-aminophenyl)-1-phenylethane, 1,1-bis(4-aminophenyl)-1-phenylethane, 1-(3-amine Phenyl)-1-(4-aminophenyl)-1-phenylethane and other diaminophenyl phenylethanes; 1,3-bis(3-aminophenoxy)benzene, Diamines such as 1,3-bis(4-aminophenoxy)benzene, 1,4-bis(3-aminophenoxy)benzene, 1,4-bis(4-aminophenoxy)benzene Phenoxybenzenes; 1,3-bis(3-aminobenzyl)benzene, 1,3-bis(4-aminobenzyl)benzene, 1,4-bis(3-amine Bisaminobenzylbenzenes such as benzoyl)benzene, 1,4-bis(4-aminobenzyl)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-dimethyl) Benzyl)benzene, 1,4-bis(4 -Amino-α,α-dimethylbenzyl) benzene and other diaminodimethylbenzenes; 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) Fluoromethyl)benzyl)benzene, 1,4-bis(4-amino-α,α-bis(trifluoromethyl)benzyl)benzene and other diaminobis(trifluoromethyl)benzyl Benzenes; 2,6-bis(3-aminophenoxy)benzonitrile, 2,6-bis(3-aminophenoxy)pyridine; 4,4'-bis(3-aminobenzene Aminophenoxy biphenyls such as oxy)biphenyl and 4,4'-bis(4-aminophenoxy)biphenyl; 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] sulfide, bis[4- (4-Aminophenoxy)phenyl] sulfonate and other aminophenoxy phenyl sulfonates; bis[4-(3-aminophenoxy)phenyl]ether, bis[4-(4-amine) Aminophenoxyphenyl ethers such as phenyloxy)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) Yl)-α,α-dimethylbenzyl]benzene, 1,4-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl]benzene, 4,4 '-Bis[4-(4-aminophenoxy)benzyl]diphenyl ether, 4,4'-bis[4-(4-aminophenoxy)-α,α-dimethylbenzyl )Phenoxy]benzophenone, 4,4'-bis[4-(4-amino-α,α-dimethylbenzyl)phenoxy]diphenyl sulfide, 4,4'- Bis[4-(4-aminophenoxy)phenoxy]diphenyl sulfide, 3,3'-diamino-4,4'-diphenoxybenzophenone, 3,3'- Diamino-4,4'-diphenyloxybenzophenone, 3,3'-diamino-4-phenoxybenzophenone, 3,3'-diamino-4-linked Phenoxybenzophenone, 6,6'-bis(3-aminophenoxy) 3,3,3',3'-tetramethyl-1,1'-spiro Indane (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'-spirobiindanane, 1,3-bis(3-aminopropyl)tetramethyldisiloxane, 1,3-bis(4 -Aminobutyl)tetramethyldisiloxane, bis(aminomethyl)ether, bis(2-aminoethyl)ether, bis(3-aminopropyl)ether, bis(2-amine) Methoxy)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-diaminononane, 1,10-diaminodecane, 1 ,11-diaminoundecane, 1,12-diaminododecane, etc., can be a combination of two or more.

The molar ratio of (a1) component (acid component) and (a2) component to (a4) component (amine component)(a1)/[(a2)＋(a3)＋(a4)] is not particularly limited, from From the viewpoint of the balance between adhesiveness, heat-resistant adhesiveness, flow control properties, and low dielectric properties, it is usually about 0.9 to 1.25, preferably about 0.9 to 1.15.

(a2) Ingredients ~ (a4) The ratio of each ingredient is not particularly limited. From the viewpoint of the balance among heat-resistant adhesiveness, adhesiveness, flow control, and low dielectric properties, (a2)/[(a2 )＋(a3)＋(a4)] usually around 10 mol%～100 mol%, preferably around 30 mol%～100 mol%, (a3)/[(a2)＋(a3)＋(a4 )]Usually 0 mol%～50 mol%, preferably 0 mol%～5 mol%, (a4)/[(a2)＋(a3)＋(a4)] usually 0 mol% ~90 mol%, preferably 0 mol% ~ 70 mol%.

The component (A) can be produced by various conventional methods. For example: usually at a temperature of about 60 to 120°C (preferably 80 to 100°C), the (a1) component and (a2) component and the (a3) component and (a4) component used as needed are usually added The polymerization reaction is about 0.1 to 2 hours (preferably 0.1 to 0.5 hours). 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-closing reaction for about 0.5 to 50 hours (preferably 1 to 20 hours). Moreover, when performing these reactions, the solvent mentioned later, especially aprotic polar solvent can be used as a reaction solvent.

In addition, 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.

Examples of reaction solvents include: N-methyl-2-pyrrolidone, N,N-dimethylacetamide, γ-butyrolactone, cyclohexanone, methylcyclohexanone, toluene, xylene, methyl Organic polar solvents such as methyl isobutyl ketone, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and dipropylene glycol dimethyl ether. These organic polar solvents can be used alone or in a mixture of multiple types.

(A) The imine ring closure rate of the component 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 cyclic iminium bonds in component (A) (the same applies below), and it can be measured by various methods such as nuclear magnetic resonance (NMR) or infrared (IR) analysis. It is decided by spectroscopic means.

(A) The physical properties of the component are not particularly limited. From the viewpoint of the balance among adhesiveness, heat-resistant adhesiveness, flow control properties, and low dielectric properties, the number average molecular weight (polystyrene obtained by gel permeation chromatography) is usually The value converted to ethylene, the same below) is about 5000 to 50000, and the softening point (softening point is measured using a commercially available measuring device ("ARES-2KSTD-FCO-STD", manufactured by Rheometric Scientific)) The temperature at which the stiffness rate in the viscoelastic profile begins to decrease, the same below) is usually about 30 to 160°C.

In order for the (A) component to express higher adhesiveness, heat resistance, and dielectric properties, two or more (A) components with changed types and ratios of (a1) to (a4) components can be mixed and used. The number of (A) component types and mixing ratios to be mixed are arbitrary.

(B) Various conventional materials can be used for the component, and there is no particular limitation. Among them, polyphenylene ether resins, epoxy resins, benzoxazine resins, bismaleimide resins and cyanate ester resins are preferred on heat-resistant and adhesive surfaces. Among these, the dielectric In terms of characteristics, a combination of a multifunctional epoxy resin and a cyanate ester resin is preferred.

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的合計表示1～30。Various conventional materials can be used for the polyphenylene ether resin, and there is no particular limitation. Specifically, the compound represented by the following general formula is preferable. [Chemical formula 5]

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 properties of the polyphenylene ether resin are not particularly limited. From the viewpoint of adhesive strength and low dielectric properties, the terminal hydroxyl group concentration is preferably about 900 to 2500 μmol/g, and the number average molecular weight is preferably about 800 to 2000.

Examples of epoxy resins include: phenol novolak type epoxy resin, cresol novolak type epoxy resin, bisphenol A type epoxy resin, bisphenol F type epoxy resin, bisphenol S type epoxy resin, hydrogenated Bisphenol A type epoxy resin, hydrogenated bisphenol F type epoxy resin, stilbene type epoxy resin, epoxy resin containing triazine skeleton, epoxy resin containing stilbene skeleton, linear aliphatic epoxy resin, alicyclic Formula epoxy resin, glycidylamine epoxy resin, triphenolmethane epoxy resin, alkyl modified triphenolmethane epoxy resin, biphenyl epoxy resin, epoxy resin containing dicyclopentadiene skeleton, Naphthalene skeleton epoxy resin, aryl alkylene type epoxy resin, tetraglycidylxylylenediamine; modified epoxy resin, dimerized epoxy resin modified by dimer acid 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 Co., Ltd.; "YD-172-X75" manufactured by Nippon Steel Chemical Co., Ltd.

式中，Z³ 表示伸苯基或環己烯基。Among these, from the viewpoints of adhesiveness, heat-resistant adhesiveness, and flow control properties, tetraglycidylxylylenediamine having the following structure is preferred, and "Tetrad-X" manufactured by Mitsubishi Gas Chemical Co., Ltd. can be used. Sale.

In the formula, Z ³ represents a phenylene group or a cyclohexenyl group.

In addition, when epoxy resin is used, various conventional hardeners for epoxy resins can be used together. Specifically, in addition to the various polyphenylene ether resins, benzoxazine resins, bismaleimide resins, and cyanate ester resins described below, examples include succinic anhydride, phthalic anhydride, maleic anhydride, Trimellitic anhydride, pyromellitic anhydride, hexahydrophthalic anhydride, 3-methyl-hexahydrophthalic anhydride, 4-methyl-hexahydrophthalic anhydride, or 4-methyl -Mixture of hexahydrophthalic anhydride and hexahydrophthalic anhydride, tetrahydrophthalic anhydride, methyl-tetrahydrophthalic anhydride, nadic anhydride, methyl nadic anhydride, norbornyl Alkane-2,3-dicarboxylic anhydride, methylnorbornane-2,3-dicarboxylic anhydride, methylcyclohexene dicarboxylic anhydride, 3-dodecenyl succinic anhydride, octenyl succinic anhydride and other acid anhydrides Hardener; Dicyandiamide (DICY), aromatic diamine (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, phenolic hydroxyphosphazene (phosphazene) (trade name "SPH manufactured by Otsuka Chemical Co., Ltd." -100" etc.) and other phenolic hardeners; cyclic phosphazene compounds; rosin-based crosslinking agents such as maleic acid modified rosin or its hydrogenated products. Among these, cyanate ester resin is preferred. The amount of hardener for epoxy resin is not particularly limited. When the solid content of the adhesive composition of the present invention is 100% by weight, it is usually about 0.1-50% by weight, and about 1-40% by weight. Better.

In addition, as the curing agent for epoxy resin, the polyphenylene ether compound represented by the above-mentioned chemical formula 5 can also be used.

Examples of the benzoxazine resin 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 a phenyl group, a methyl group, a cyclohexyl group, and 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., and "RLV-100" manufactured by AIR WATER.

Examples of the bismaleimide resin include: 4,4'-diphenylmethane bismaleimide, meta-phenyl bismaleimide, bisphenol A diphenyl ether bismaleimide Amine, 3,3'-dimethyl-5,5'-diethyl-4,4'-diphenylmethane bismaleimide, 4-methyl-1,3-phenylene bisma Leximine, 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 types. In addition, examples of commercially available products include "BAF-BMI" manufactured by JFE Chemical Co., Ltd. and the like.

Examples of the cyanate resin 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-ginseng (4-cyanatophenyl ) Ethane, 4-cumenyl phenol cyanate, 1,1-bis(4-cyanatophenyl) ethane, 4,4'-bisphenol cyanate, and 2,2-bis(4 -Cyanatophenyl) propane, etc., two or more types can be combined. In addition, examples of commercially available products include "PRIMASET BTP-6020S" and "PRIMASET PT-30" (manufactured by Lonza Japan Co., Ltd.).

In addition, it is also possible to use a hardening catalyst together with the (B) component. 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 tetraphenyl borate, tetraphenyl borate 2-ethyl-4-methylimidazole, tetraphenyl borate N-methylmorpholine and other tetraphenyl boron salts; caprylic acid, stearic acid, acetone, naphthenic acid, Zn, Cu, Fe and other organic metal salts of organic acids such as salicylic acid; benzyl peroxide, methyl ethyl ketone peroxide, cyclohexanone peroxide, lauryl peroxide, di( Free radical initiators such as tertiary butyl peroxide, tertiary butyl peroxybenzoate, cumene hydroperoxide, dicumenyl peroxide, etc., can be combined with two or more. "In addition, the amount of the catalyst used is not particularly limited, but when the solid content of the adhesive composition of the present invention is 100% by weight, it is usually about 0.01 to 5% by weight.

The use amount of the (B) component is not particularly limited, but it is usually about 3 to 30 parts by weight, preferably about 5 to 15 parts by weight, in terms of solid content based on 100 parts by weight of the (A) component.

The adhesive composition for forming the adhesive layer (2) may contain an organic solvent in addition to the above-mentioned (A) component and (B) component. As the organic solvent, various conventional solvents can be used without 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 the adhesive composition used to form the adhesive layer (2), the following can be formulated according to needs: the aforementioned ring-opening esterification reaction catalyst and dehydrating agent, plasticizer, weathering agent, antioxidant, heat stabilizer, Lubricants, antistatic agents, brighteners, colorants, conductive agents, mold release agents, surface treatment agents, viscosity regulators, phosphorus-based flame retardants, flame retardant fillers, silica fillers, and fluorine fillers.

式中，Q表示包含會與酸酐基進行反應的官能基的基，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 adhesive composition may further include a reactive alkoxysilyl compound (C) (hereinafter also referred to as (C) component). (C) The component is not particularly limited, and examples thereof include silyl compounds represented by the following general formulas. 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 can react 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 (C), 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 base material (the so-called anchoring effect) while suppressing the occurrence of the hardened layer oozing from the end of the base material (this operation is sometimes referred to as Flow control).

Examples of compounds in which the functional group in Q is an amino group include: 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 an 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.

The dielectric constant of the adhesive layer (2) at 10 GHz is not particularly limited, and is usually 3.0 or less, and preferably the dielectric loss tangent is 0.005 or less. Thereby, the copper clad laminate of the present invention can be preferably used for suppressing transmission loss. More preferably, the dielectric constant is 1.5 to 2.9, and the dielectric loss tangent is 0.0005 to 0.004 or less.

The copper foil (3) is not particularly limited as long as the ten-point average roughness Rz of the surface in contact with the adhesive layer (2) is 0.1 to 1.5 μm, and examples include rolled copper foil and electrolytic copper foil. The ten-point average roughness Rz here refers to the part remaining after removing only the reference length from the profile curve. The average value of the elevation from the highest peak to the fifth peak and the depth from the deepest are expressed in microns. The difference between the average values of the elevation from the bottom of the valley to the fifth valley and its value. In addition, the thickness is not particularly limited, but is usually about 1 to 10 μm, preferably about 2 to 38 μm. In addition, the copper foil can be subjected to various surface treatments (roughening, rust prevention, etc.). Examples of the anti-corrosion treatment include the following so-called mirror finish treatment: plating treatment using a plating solution containing Ni, Zn, Sn, etc.; and chromate treatment.

The copper-clad laminate of the present invention is obtained by applying the aforementioned adhesive composition to a substrate and drying to form an adhesive layer (2) in an uncured or partially cured state, and then attaching another substrate After bonding, the adhesive layer (2) is post-cured. The base material to be coated with the adhesive composition and the base material to be subsequently bonded can be any of insulating film (1) and copper foil (3).

The following methods can be used for the coating method of the adhesive layer (2): brush coating, dip coating, spray coating, comma coating, knife coating, die coating, lip coating Coating, roll coater coating, curtain coating, etc. As the drying method, the following methods of passing through the furnace body can be used: hot air drying at 40 to 250°C, more preferably 70 to 170°C, far infrared heating, high frequency induction heating for about 2 to 15 minutes, etc. As the bonding method, the following method can be used: preferably at a temperature of 40 to 250°C, more preferably 50 to 200°C, using a roll laminator and hot pressing. "Post-curing" can use the following method of passing through the furnace body: hot air drying at a temperature of 120 to 250 degrees, preferably 70 to 200 degrees Celsius, far infrared heating, high frequency induction heating for about 30 minutes to 48 hours, etc.　　In consideration of adhesion, heat resistance, ease of application, and risk of solvent residue, the thickness of the adhesive layer (2) is preferably about 1 to 70 μm.

The printed circuit board is also a kind of the present invention, and the printed circuit board is formed by forming a circuit pattern on the copper foil surface of a copper clad laminate. The method of forming the circuit pattern can be, for example, a subtractive method or a semi-additive method. The semi-additive method includes, for example, a method of patterning the copper foil surface of the copper-clad laminate of the present invention with a resist film, electrolytic copper plating, removing the resist, and etching with an alkaline solution. In addition, the thickness of the circuit pattern layer in this printed wiring board is not specifically limited. [Example]

Hereinafter, the present invention will be specifically explained through examples and comparative examples, 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. In addition, the number average molecular weight is a value obtained using a commercially available measuring machine ("HLC-8220GPC", manufactured by TOSOH Corporation). The glass transition temperature is a value obtained by using a commercially available measuring device ("DSC6200", manufactured by Seiko Instruments Co., Ltd.).

<The non-volatile content of (A) component> First weigh out 1g of the solution of (A) component, and dry it with a circulating air dryer at 180°C for 60 minutes. From the weight before and after drying, calculate the non-volatile content according to Formula 1. . (Formula 1)=(weight after drying (g))/(weight before drying (g)) × 100 (%)

[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 trap, a thermometer, and a nitrogen inlet pipe. The content of 3,3',4,4'-benzophenone tetracarboxylic dianhydride is 99.8% 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 (A-1) with a weight average molecular weight of about 35,000 at 80°C (non-volatile content 33.9%). Furthermore, the content of dimer diamine in all diamine monomers is 100 mol%, and the molar ratio of acid component/amine component is 1.03.

[Manufacturing Example 2] 　　 In the same reaction vessel as in Manufacturing Example 1, a commercially available aromatic tetracarboxylic dianhydride (trade name "BisDA1000", manufactured by EVONIK Japan Co., Ltd., 4,4'-[PP-2 The content of ,2-diylbis(1,4-phenoxy)]diphthalic dianhydride is 98.0%) 297.8 g, cyclohexanone 818.95 g, methylcyclohexane 136.49 g, and the solution Heat up to 60°C. Then, after dropping 200.28 g of PRIAMINE 1075 and 24.83 g of 1,3-bis(aminomethyl)cyclohexane, it took 10 hours to carry out the imidization reaction at 140°C to obtain a softening point of about 100°C. And a solution of polyimide (A-2) with a weight average molecular weight of about 28,000 (non-volatile content 32.2%). In addition, the content of dimer diamine in all diamine monomers was 68 mol%, and the molar ratio of acid component/amine component was 1.05.

[Manufacturing Example 3] 　　 A commercially available aromatic tetracarboxylic dianhydride (trade name "BisDA1000", manufactured by EVONIK Japan Co., Ltd., 4,) was fed into a reaction vessel equipped with a stirrer, a water trap, a thermometer, and a nitrogen inlet pipe. 4'-[Propyl-2,2-diylbis(1,4-phenoxy)]diphthalic dianhydride content is 98.0%) 200.0 g, cyclohexanone 700.00 g, methylcyclohexane Alkane 175.00 g, and the solution was heated to 60°C. Then, after 190.54 g of hydrogenated dimer diamine (trade name "PRIAMINE 1075", manufactured by Croda Japan Co., Ltd.) was dropped, it was subjected to an imidization reaction at 140°C for 10 hours to obtain a softening point of about A solution of polyimide resin (A-3) with a weight average molecular weight of about 22,000 at 80°C (non-volatile content 30.2%). Furthermore, the content of dimer diamine in all diamine monomers is 100 mol%, and the molar ratio of acid component/amine component is 1.03.

[Manufacturing Example 4] 　　 In the same reaction vessel as in Manufacturing 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%) 190.0 g, cyclohexanone 277.5 g, and methylcyclohexane 182.4 g, and the solution is heated to 60°C. Then, drop 277.5 g of PRIAMINE 1075 and 23.8 g of α,ω-bis(3-aminopropyl) polydimethylsiloxane (trade name "KF-8010", manufactured by Shin-Etsu Chemical Co., Ltd.), It took 10 hours to carry out an imidization reaction at 140°C, thereby obtaining a polyimide (A-4) solution (non-volatile content 30.8%) with a softening point of about 70°C and a weight average molecular weight of about 18,000. Furthermore, the content of dimer diamine in all diamine monomers was 95 mol%, and the molar ratio of acid component/amine component was 1.09.

[Formulation example 1] 　　 10.20 g of component (A-1) solution, 10.74 g of component (A-2) solution, 5.72 g of component (A-3) solution, and N,N-two as component (B) Glycidyl-4-glycidoxyaniline (trade name "jER630", manufactured by Mitsubishi Chemical Co., Ltd.) 0.27 g and cyanate ester resin (trade name "TA", manufactured by Mitsubishi Gas Chemical Co., Ltd.) MEK solution (non-volatile content 40%)) 0.48 g, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane (trade name "KBM-603", Shin-Etsu Chemical Industry 0.18 g of toluene (Tol) solution (non-volatile content 10%) manufactured by Co., Ltd., and 2.81 g of toluene as a dilution solvent, to obtain an adhesive composition with a non-volatile content of 30.0%. Furthermore, the content of dimer diamine in all diamine monomers used in the synthesis of component (A) is 87.2 mol%

[Formulation Examples 2 to 13, Comparative Formulation Example 1] 　　The adhesive composition was obtained with the composition shown in Table 1 or Table 2.

[Comparative Formulation Example 2] "Carboxy NBR (trade name "XER-32C", manufactured by JSR Co., Ltd.) was used as the adhesive composition.

[Comparative Formulation Example 3] "Acrylic elastomer (trade name "SG-708-6", manufactured by Nagase ChemteX Co., Ltd.) was used as the adhesive composition.

<Production of a copper-clad laminate> [Examples 1 to 13, Comparative Examples 1 to 3] 　　 The preparation examples 1 to 13 and the comparative preparation example 1 were combined using a gap coater so that the thickness after drying became 12 μm The adhesive composition of ~3 was applied to rolled copper foil (trade name "GHF5", manufactured by JX Metal Co., Ltd., ten-point average roughness Rz: 0.45 μm), and dried at 150°C for 10 minutes to obtain the adhesive Copper foil with resin. Using two pieces of this resin-coated copper foil, dehumidify the polyimide film (trade name "Kapton 100EN", DU PONT-TORAY Co., Ltd.) at 120°C for 10 minutes so that the adhesive surface is inside. The film thickness is 25 μm, the thermal expansion coefficient is 15 ppm/°C) is sandwiched between them, and the laminate is heated at 170°C and 3 MPa for 30 minutes to obtain a copper-clad laminate.

[Comparative Example 4] 　　 P-F705 (made by laminating rolled copper foil on both sides of LCP "Vecstar" manufactured by Kuraray Co., Ltd.) at 300°C was used as a copper-clad laminate without an adhesive layer. .

[Comparative Example 5] 　　 P-F775 manufactured by Panasonic (Laminated a rolled copper foil at 300°C on a polyimide "Upilex-VT" manufactured by Ube Industries Co., Ltd. (with thermoplastic polyimide layer/non-thermoplastic Polyimide layer/thermoplastic polyimide layer (three-layered polyimide layer/thermoplastic polyimide layer) is a double-sided copper-clad laminate without an adhesive layer.

<Measurement of the dielectric constant and dielectric loss tangent of the adhesive layer> 　　Pour the adhesive composition of formulation examples 1 to 13 into a fluororesin PFA flat plate (diameter 75 mm, made by Mutual Rika Glass Manufacturing Co., Ltd.) 7 g, 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 film thickness of about 300 μm Hardened material flakes. Then, in accordance with JIS C2565, a commercially available dielectric constant measuring device (cavity resonator type, manufactured by AET Corporation) was used to measure the dielectric constant and dielectric loss tangent at 10 GHz for the cured product sheet. The physical property values of Comparative Blending Examples 1 to 5 are reference catalog values. The results are shown in Table 1 and Table 2 (the same applies below).

<Adhesiveness test> 　　 According to JIS C-6481 (test method of copper-clad laminate for flexible printed wiring boards), the peel strength (N/mm) of the copper-clad laminates of Examples 1-13 was measured. The physical property values of the comparative example are reference catalog values.

<Solder heat resistance test> "The copper-clad laminates of Examples 1 to 13 and Comparative Examples 1 to 5 were floated in a solder bath at 288°C for 30 seconds so that the copper foil side was down, and the appearance change was confirmed. The case where there is no change is regarded as ○, and the case where there is foaming and swelling is regarded as ×.

<Preparation of printed wiring board for circuit evaluation> 　　 The copper clad laminates of Examples 1 to 13 and Comparative Examples 1 to 5 were formed with resist patterns. Then, the copper foil was etched by being immersed in a 40% ferric chloride aqueous solution to form a copper circuit with a wire length of 10 cm.

＜Measurement of transmission loss＞ 　　 A network analyzer (trade name "E8363B", manufactured by Keysight Technologies) was used, and the impedance was adjusted to 50Ω, and the printed wiring boards for circuit evaluation of Examples 1-13 and Comparative Examples 1-5 were used The insertion (transmission) loss S21 at 10 GHz is measured.

[Table 1]

※表中的各成分的使用量以數值來表示(單位：g) ※1：(A)成分的重量平均分子量：(A-1)－35000、(A-2)－28000、(A-3)－22000、(A-4)－18000 ※2：GHF5－JX金屬股份有限公司製，十點平均粗糙度Rz：0.45 μm       BHFX改－JX金屬股份有限公司製，十點平均粗糙度Rz：0.90 μm ※3：在實施例1～13中是表示黏著劑層的介電常數及介電耗損正切[Table 2]

※The usage amount of each component in the table is expressed as a numerical value (unit: g) ※1: The weight average molecular weight of (A) component: (A-1)-35000, (A-2)-28000, (A-3 )-22000, (A-4)-18000 ※2: GHF5-JX Metal Co., Ltd., ten-point average roughness Rz: 0.45 μm BHFX changed-JX Metal Co., Ltd., ten-point average roughness Rz: 0.90 μm ※3: In Examples 1-13, it means the dielectric constant and dielectric loss tangent of the adhesive layer

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Claims (6)

A copper-clad laminate comprising a copper foil (3) which is laminated on at least one side of an insulating film (1) via an adhesive layer (2), wherein the insulating film (1) The thermal expansion coefficient is 4~30ppm/℃, the adhesive layer (2) contains anhydride group-terminated polyimine (A) and cross-linking component (B), and the acid anhydride group-terminated polyimide (A) is an aromatic four The reactant of carboxylic anhydride and diamine monomer, the diamine monomer contains dimer diamine, and the ten-point average roughness Rz of the surface of the copper foil (3) that is in contact with the adhesive layer (2) is 0.1~1.5μm, the content of the dimer diamine is 50~100 mol% of the diamine monomer, the adhesive layer (2) further contains a reactive alkoxysilyl compound (C), the component (C) is as follows The general formula is: Q-Si(R ¹ ) _a (OR ² ) _{3-a In the} formula, Q represents a group containing a functional group that can react with an acid anhydride group, and R ¹ represents hydrogen or a carbon number of 1-8 Hydrocarbyl group, R ² represents a hydrocarbon group having 1 to 8 carbon atoms, and a represents 0, 1, or 2. The copper-clad laminate according to claim 1, wherein the aromatic tetracarboxylic anhydride is represented by the following general formula:

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-, And in the formula, Y represents -(CH ₂ ) ₁ -or -H ₂ C-HC(-OC(=O)-CH ₃ )-CH ₂ -, where l represents 1-20. The copper-clad laminate according to claim 1 or 2, wherein the crosslinking component (B) is made of polyphenylene ether resin, epoxy resin, benzoxazine resin, bismaleimide resin, and cyanic acid At least one selected from the group consisting of ester resins. The copper clad laminate according to claim 1 or 2, wherein the dielectric constant at 10 GHz of the adhesive layer (2) is 3.0 or less, and the dielectric loss tangent is 0.005 or less. The copper clad laminate according to claim 3, wherein the dielectric constant at 10 GHz of the adhesive layer (2) is 3.0 or less, and the dielectric loss tangent is 0.005 or less. A printed circuit board is obtained by performing circuit circuit processing on the copper foil of the copper-clad laminate according to any one of claims 1 to 5.