JPH07154042A - PCB for printed wiring board - Google Patents

Abstract

(57) [Summary] [Object] A printed wiring board substrate based on a polyimide film on which a thermosetting resin composition of the present invention is laminated is used for increasing the transmission speed of signals in high frequencies in electronic devices and the like. A laminate having improved dielectric properties, workability, adhesiveness, and heat resistance can be obtained. [Structure] A thermosetting resin containing a soluble polyimidesiloxane obtained from an aromatic tetracarboxylic acid component containing biphenyltetracarboxylic acid as a main component and a diamine component containing diaminopolysiloxane and aromatic diamine, an epoxy compound and an epoxy curing agent. The resin composition is laminated on a substrate having a polyimide film as a base, and copper foil is laminated on one side or both sides, and the dielectric constant after curing is low.

Description

Detailed Description of the Invention

[0001]

This invention relates to a low dielectric constant, heat resistance,
The present invention relates to a printed wiring board substrate (laminate and metal-clad laminate) having excellent adhesiveness.

[0002]

2. Description of the Related Art Conventionally, 1,2-
JP-A-62-1877 is an example of a copper-clad laminate made of a composition containing a polybutadiene unit-containing modified polycarbodil terminal modified polybutadiene and an epoxidized polybutadiene as one component.
36 and JP-A-63-280721, examples of heat-resistant copper-clad laminates made of a composition comprising a combination of a bismaleimide compound, a diamine, and a phenol are disclosed in JP-A 1-271235 and JP-A 1-271235. 1-271236
It is described in Japanese Patent Publication No.

However, in recent years, in order to cope with the speeding up of electronic devices in printed wiring board substrates, in order to speed up the transmission speed of electrical signals, the dielectric characteristics are improved and the workability and
There is a strong demand for improvements in adhesiveness and heat resistance and cost reduction.

[0004]

SUMMARY OF THE INVENTION The object of the present invention is to meet the above-mentioned dielectric characteristics (low dielectric constant, low dielectric loss tangent), heat resistance, workability, and adhesiveness in order to adapt to high speed transmission of electric signals. It is to provide an excellent printed wiring board substrate.

[0005]

DISCLOSURE OF THE INVENTION The inventors of the present invention have conducted diligent research for the purpose of improving the drawbacks of conventional printed wiring board substrates, and have conducted a thermosetting process including a polyimide siloxane, an epoxy compound and an epoxy curing agent. For a printed wiring board obtained by laminating a conductive resin composition on a base material having a polyimide film as a base, and bonding and curing a copper foil on both surfaces or one surface of the base material for adapting to a higher electric signal transmission speed. The inventors have come to the present invention by knowing that they have excellent dielectric properties (low dielectric constant, low dielectric loss tangent), heat resistance, processability, adhesiveness, etc., and can be used as substrates for printed wiring boards.

This invention relates to (a) an aromatic tetracarboxylic acid component containing biphenyltetracarboxylic acid as a main component and a general formula (1)

[0007]

[Chemical 2]

(Wherein R represents a divalent hydrocarbon residue, R ₁ , R ₂ , R ₃ and R ₄ represent a lower alkyl group or a phenyl group, and n represents an integer of 3 to 60). 100 parts by weight of a soluble polyimidesiloxane obtained from a diamine component consisting of 10 to 80 mol% of diaminopolysiloxane and 90 to 20 mol% of an aromatic diamine,
(B) 20 to 250 parts by weight of an epoxy compound, (c), and a thermosetting resin composition containing an epoxy curing agent are laminated on a base material based on a polyimide film, and a copper foil is bonded to one side or both sides, A printed wiring board substrate, wherein the thermosetting resin composition has a cured dielectric constant of 3.3 (12.5 GHz, 25 ° C.) or less.

In the present invention, as the aromatic tetracarboxylic acid component containing biphenyltetracarboxylic acids as a main component, 3,3 ', 4,4'-biphenyltetracarboxylic acid, 2,3,
Aromatic tetracarboxylic acid components containing 3 ', 4'-biphenyltetracarboxylic acid or biphenyltetracarboxylic acids such as acid dianhydrides and esterified products thereof in an amount of 60 mol% or more, particularly 80 to 100 mol% are used. To be done. Among these, particularly, 2,3,3 ', 4'-biphenyltetracarboxylic dianhydride is preferable because it has excellent solubility in the organic polar solvent of the polyimidesiloxane, compatibility with an epoxy compound, and the like. .

In the present invention, examples of the aromatic tetracarboxylic acid component that can be used together with the biphenyl tetracarboxylic acids include, for example, 3,3 ', 4,4'-benzophenone tetracarboxylic acid, 3,3', 4, 4'-diphenyl ether tetracarboxylic acid, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, pyromellitic acid, or their acid dianhydrides or ester compounds And the like can be preferably mentioned. However, if the amount of these used is too large, the polyimide siloxane becomes insoluble in the organic polar solvent or the compatibility with the epoxy resin deteriorates, which is not suitable.

In the present invention, as the diaminopolysiloxane represented by the general formula (1), R in the formula is a "plurality of methylene groups" having 2 to 6 carbon atoms, particularly 3 to 5 carbon atoms, or a phenylene group. R ₁ is a divalent hydrocarbon residue
~ R ₄ has 1 carbon atom such as methyl group, ethyl group, propyl group, etc.
Is preferably a lower alkyl group or a phenyl group of 5 to 5, and n is an integer of 3 to 60, particularly 5 to 20, and more preferably 5 to 15. R, R
_If the carbon number of _{1 to} R ₄ is too large, or if the number of n is too large, the reactivity or heat resistance deteriorates, the molecular weight of the resulting polyimidesiloxane decreases, and the solubility in organic solvents decreases. Or, the compatibility with other organic compounds may deteriorate, so that the above-mentioned level is suitable.

Specific examples of the diaminopolysiloxane represented by the general formula (1) include ω, ω'-bis (2-aminoethyl) polydimethylsiloxane and ω, ω'-bis (3
-Aminopropyl) polydimethylsiloxane, ω, ω '
-Bis (4-aminophenyl) polydimethylsiloxane,
Preferable examples include ω, ω'-bis (4-amino-3-methylphenyl) polydimethylsiloxane and ω, ω'-bis (3-aminopropyl) polydiphenylsiloxane.

The aromatic diamine used together with the diaminopolysiloxane is generally an aromatic diamine compound having two or more aromatic rings such as benzene rings, especially 2 to 5 aromatic rings, such as biphenyl-based diamine compounds and diphenyl ethers. Diamine compounds, benzophenone diamine compounds, diphenyl sulfone diamine compounds,
Diphenylmethane-based diamine compound, diphenylpropane-based diamine compound, diphenylthioether-based diamine compound, bis (phenoxy) benzene-based diamine compound, bis (phenoxyphenyl) sulfone-based diamine compound, bis (phenoxy) diphenylsulfone-based diamine compound, bis (phenoxyphenyl) ) Hexafluoropropane-based diamine compounds, bis (phenoxyphenyl) propane-based diamine compounds, and the like,
They can be used alone or as a mixture.

Specific examples of the aromatic diamine include diphenyl ether type diamine compounds such as 4,4'-diaminodiphenyl ether and 3,3'-diaminodiphenyl ether, 1,3-bis (3-aminophenoxy) benzene,
Bis (phenoxy) benzene-based diamine compounds such as 1,4-bis (4-aminophenoxy) benzene, 2,2-bis [4- (4-
Aminophenoxy) phenyl] propane, 2,2-bis [4-
(3-Aminophenoxy) phenyl] propane and other bis (
(Phenoxyphenyl) propane-based diamine compound, bis
[4- (4-aminophenoxy) phenyl] sulfone, bis
Aromatic diamine compounds having 2 to 5 aromatic rings, such as bis (phenoxyphenyl) sulfone-based diamine compounds such as [4- (3-aminophenoxy) phenyl] sulfone, can be preferably mentioned.

In the present invention, the former of diaminopolysiloxane and the aromatic diamine is 10 to 80 mol%, preferably 12 to 75 mol%, more preferably 13 to 70 mol%, and the latter 90 to 20 mol%. 88 to 25
It is used in a proportion of mol%, more preferably 87 to 30 mol%. If either component is too much or too little and is out of these ranges, the solubility of the polyimide siloxane in an organic solvent is lowered, or the compatibility with other organic compounds is deteriorated, which is not suitable.

In the present invention, the component (a) polyimide siloxane is produced by the following method. (A ₁ ) Aromatic tetracarboxylic acid component and diamine polysiloxane and diamine component of aromatic diamine are used in approximately equimolar amounts to continuously polymerize and imidize in an organic polar solvent at a temperature of 15 to 250 ° C. To obtain polyimide siloxane.

(A ₂ ) The diamine component is divided, and first, an excess amount of the aromatic tetracarboxylic acid component and diaminopolysiloxane are polymerized and imidized in an organic polar solvent at a temperature of 15 to 250 ° C. to obtain an average polymerization. An imide siloxane oligomer having an acid or acid anhydride group at the end of about 1 to 10 is prepared, and an aromatic tetracarboxylic acid component and an excess amount of aromatic diamine are separately added in an organic polar solvent at a temperature of 15 to 250.
Polymerization and imidization at ° C, average degree of polymerization 1-10
An imide oligomer having an amino group at the terminal is prepared, and then both are mixed so that the acid component and the diamine component are approximately equimolar and reacted at a temperature of 15 to 60 ° C. A method of obtaining a block-type polyimide siloxane by elevating the temperature to ˜250 ° C.

(A ₃ ) Using an aromatic tetracarboxylic acid component, a diaminopolysiloxane and an aromatic diamine component in substantially equimolar amounts, first in an organic polar solvent at a temperature of 20 to 80 °.
There is a method of polymerizing with C to obtain a polyamic acid once and then imidizing it to obtain a polyimidesiloxane.

Examples of the organic polar solvent used in the production of the polyimidesiloxane in the present invention include N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dimethylformamide, N, N-diethylformamide, Amide solvents such as N-methyl-2-pyrrolidone, dimethyl sulfoxide, diethyl sulfoxide, dimethyl sulfone, diethyl sulfone, solvents containing a sulfur atom such as hexamethyl sulfolamide, cresol, phenol, phenolic solvents such as xylenol, Acetone, methanol,
Examples thereof include solvents having an oxygen atom in the molecule such as ethanol, ethylene glycol, dioxane, and tetrahydrofuran, and other solvents such as pyridine and tetramethylurea. Furthermore, if necessary, benzene, toluene,
It is also possible to use together an aromatic hydrocarbon solvent such as xylene, another type of organic solvent such as solvent naphtha, and benzonitrile.

In the present invention, the polyimide siloxane may be obtained by any of the above methods (a ₁ ) to (a ₃ ), but it is as high in molecular weight as possible and has a high imidization ratio, and an organic polar solvent. At least 3% by weight or more, especially 5
What can be dissolved at a high concentration of about 40% by weight is preferable because a laminated plate having good laminating operation and laminating performance can be obtained.

The imidization ratio of polyimidesiloxane is 90 as measured by infrared absorption spectrum analysis.
% Or more, particularly 95% or more is preferable, and in the infrared absorption spectrum analysis, the absorption peak related to the amide-acid bond of the polymer is not substantially found and only the absorption peak related to the imide ring bond is observed, and the imidization ratio is high. It is preferable.

Polyimide siloxane has a logarithmic viscosity (measurement concentration: 0.5 g / 100 ml solution, solvent: N-methyl-2-pyrrolidone, measurement temperature:
30 ° C, viscometer: Canon Fenske type viscometer)
0.05-7, especially 0.07-4, more preferably 0.
It is suitable to be about 1 to 3.

Further, the above-mentioned polyimide siloxane has an elastic modulus of 250 kg / m when formed into a film.
m ² or less, particularly 0.5 to 200 kg / mm ² ,
The thermal decomposition starting temperature is 250 ° C. or higher, particularly 300 ° C. or higher, and the secondary dislocation temperature is −10 ° C. or higher, particularly 30 ° to
About 250 ° C or a softening temperature of -10 ° C or higher,
Particularly, it is preferably 5 ° C or higher, more preferably about 5 to 250 ° C.

The proportion of the (b) epoxy compound used in the present invention is 20 to 250 parts by weight, preferably 30 to 2 parts by weight, based on 100 parts by weight of the polyimidesiloxane.
If it is too much or too little, the uncured resin composition becomes sticky and lacks flexibility after curing, or the uncured resin composition has a too high softening point to cure. It is desirable to set the content within the above range because the subsequent lamination characteristics may be deteriorated.

The epoxy compound used in the present invention may be an epoxy compound having one or more epoxy groups, and specific examples thereof include bisphenol A type or bisphenol F type epoxy resin (oiled shell Epoxy Co., Ltd., trade name: Epicoat 807, 828, etc.), phenol novolac type epoxy resin, alkyl polyhydric phenol type epoxy resin (Nippon Kayaku Co., Ltd., RE701, RE550S, etc.), polyfunctional epoxy resin (Sumitomo Chemical Co., Ltd. ELM-1 manufactured by Kogyo Co., Ltd.
00), glycidyl ether type epoxy resin, glycidyl ester type epoxy resin, glycidyl amine type epoxy resin (trade name: Tetrad X etc., manufactured by Mitsubishi Gas Chemical Co., Inc.) and the like can be used alone or in combination. If the melting point of the epoxy compound is too high, the softening point of the resin composition in the uncured state becomes high, so that the melting point is 90 ° C. or lower, particularly about 0 to 80 ° C., or at a temperature of 30 ° C. or lower. Those in liquid form are preferred.

Also used in the present invention (c)
Examples of the epoxy curing agent as a component include known curing agents such as imidazoles, tertiary amines, curing catalysts such as triphenylphosphine, dicyandiamides, hydrazines, aromatic diamines, and hydroxyl groups. Examples thereof include polyaddition type curing agents such as phenol novolac type curing agents (Meiwa Kasei Co., Ltd., phenol novolac: H-1, H-5, etc.) and organic peroxides. The curing agent is appropriately used together with a known curing accelerator.

The amount of the epoxy curing agent used is generally 0.01 to 90 parts by weight, based on 100 parts by weight of the epoxy compound.
It is particularly preferable to use 0.03 to 80 parts by weight.

In the present invention, an inorganic filler, for example, silicon oxide manufactured by Nippon Aerosil Co., Ltd. (trade name: Aerosil 200, Aerosil 300, Aerosil R202,
Aerosil R972), silicon oxide manufactured by Shionogi Pharmaceutical Co., Ltd. (trade name; Carplex 80, etc.), silicon oxide manufactured by Cabot Corporation (trade name: CABOSEAL TS-72)
0) may be used.

The thermosetting resin composition of the present invention comprises the above-mentioned (a) polyimide siloxane, (b) epoxy compound,
It can be easily obtained by uniformly dispersing a predetermined amount of the epoxy curing agent (c) in a suitable organic polar solvent, stirring and mixing. When mixed with an organic polar solvent, a thermosetting resin solution composition is obtained. As the organic polar solvent, an organic polar solvent that can be used when obtaining the polyimidesiloxane, for example, a solvent having an oxygen atom in the molecule such as dioxane or tetrahydrofuran, or an amide solvent such as N-methyl-2-pyrrolidone is preferably used. To be done.

The concentration of the above-mentioned solution composition is suitably 3 to 50% by weight, preferably 5 to 40% by weight, and the solution viscosity (30 ° C.) is 0.1 to 10000 poises, particularly 0.1.
2 to 5000 poise, more preferably 0.3 to 1000
It is preferably about poise.

The thermosetting resin composition used in the present invention has a softening temperature of the composition containing only the uncured resin component (the temperature at which softening starts on the hot plate) is 150 ° C. or less, particularly 140 ° C. Hereafter, it is more preferably about 0 to 130 ° C.

The thermosetting resin composition of the present invention comprises a solution composition in which all of the above resin components are dissolved in an organic polar solvent, and a heat resistant resin composition such as a suitable metal foil, aromatic polyimide film or aromatic polyester. Of the solvent to 1% by weight or less by coating on the film surface of thermoplastic resin such as polyethylene or the like and drying the coating layer at a temperature of 80 to 200 ° C. for 20 seconds to 100 minutes. Can form a thin film (a dry film or sheet having a thickness of about 1 to 200 μm) of the uncured thermosetting resin composition in which the residual solvent ratio is substantially removed to 0.5% by weight or less. .

The uncured thermosetting resin composition thin film thus produced has suitable flexibility and is wound around a paper tube or the like, or punched by a punching method or the like. It is also possible to stack a laminated sheet on which a thin film layer of an uncured thermosetting resin composition is formed on the heat resistant or thermoplastic film, and a metal foil or a heat resistant film for a transfer destination. The sheet layer of the thermosetting resin composition is transferred onto the metal foil or the heat resistant film for the transfer destination by passing it between a pair of rolls (laminate rolls) heated to a temperature of about 20 to 200 ° C in total. It is also possible to do so.

In order to form a laminated plate such as a copper clad substrate by bonding a heat resistant film and a metal foil using the thermosetting resin composition of the present invention, it is formed, for example, as described above. The heat resistant film and the metal foil are placed at 80 to 200 ° C., particularly 100 to 18 through the thin film thermosetting resin composition layer.
Laminated (laminated) under pressure (0.2 to 8 kg / cm ² ) at a temperature of 0 ° C., and further laminating the product to 140 to 250 ° C., particularly 150 to 230 ° C.
By heating and curing the thermosetting resin composition layer for 30 minutes to 40 hours, particularly 1 to 30 hours at the temperature of 1, the laminated plate can be easily and continuously produced without any trouble. it can.

The thermosetting resin composition of the present invention comprises a heat resistant film such as an aromatic polyimide film, a polyamide film, a polyetheretherketone film and a polyethersulfone film, and a suitable metal foil such as copper, aluminum and iron. Can be suitably used for joining the Further, the thermosetting resin composition of the present invention may contain a small amount of other thermosetting resin such as bismaleimide resin as a resin component.

[0036]

EXAMPLES The present invention will be described in more detail below with reference to examples. In the following examples, the logarithmic viscosity (η) as a measure of the molecular weight is a solution prepared by uniformly dissolving polyimide siloxane in N-methyl-2-pyrrolidone so that the concentration becomes a solution of 0.5 g / 100 ml. Was prepared and measured at 30 ° C. using a Canon-Fenske viscometer.

The softening temperature of the polyimidesiloxane film is a value obtained by measuring the delta (high temperature side) of the viscoelasticity peak in the viscoelasticity test using a mechanical spectrometer RDS-2 manufactured by Rhemeric.

The elastic modulus of the polyimide siloxane is the result of measurement using a tensile tester manufactured by Intesco Co., Ltd. under the conditions of a tensile speed of 5 mm / min.

The peel strength was measured using a tensile tester manufactured by Intesco at a peel rate of 50 mm / min at a measurement temperature of 25 ° C.
90 degree peel test, and 1 at measurement temperature 180 degree
The results are obtained by performing an 80 ° peel test.

The dielectric constant is JIS-C-64 at 50 Hz.
81, measured at 12.5 GHz using a microwave molecular orientation meter (KS Systems, MOA-2012).
In A), after removing the copper foil of the laminate by front etching,
It was measured.

[Production of Imidosiloxane Oligomer] Reference Example 1 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride was placed in a glass flask having a capacity of 500 ml equipped with a thermometer, a charging / distilling outlet and a stirrer. Product (a-BPDA) 0.04
5 mol, ω, ω'-bis (3-aminopropyl) polydimethylsiloxane (Shin-Etsu Silicon Co., Ltd., X-22-1
61AS, n: 9) 0.030 mol, and N-methyl-2
-Charge 160 g of pyrrolidone (NMP), raise to a temperature of 50 ° C in a nitrogen stream, stir at this temperature for 2 hours,
Then, an amic acid oligomer is generated, and then the reaction solution is heated to 200 ° C. and stirred at that temperature for 3 hours to prepare an imidosiloxane oligomer (A-
One component, average degree of polymerization: 2) was produced.

Reference Example 2 The amounts of a-BPDA, 2,2-bis [4- (4-aminophenoxy) phenyl] propane (BAPP) and NM shown in Table 1 were used.
An imide siloxane oligomer having an anhydride group at the terminal (B-) was prepared in the same manner as in Reference Example 1 except that P was used.
One component, average degree of polymerization: 2) was produced.

Reference Example 3 The same procedure as in Reference Example 1 except that the amounts of a-BPDA, BAPP and NMP shown in Table 1 were used, respectively. Degree: 5) was manufactured.

[0044]

[Table 1]

[Production of Polyimide Siloxane] Reference Example 4 The imidosiloxane oligomer (A-
1 component) 14.14 g (0.0055 mol) of 20 wt% NMP solution and 2 of the imide oligomer (B-2 component) 24.33 g (0.0055 mol) prepared in Reference Example 3
A 0 wt% NMP solution was placed in a glass flask having a capacity of 500 ml, and heated in a nitrogen stream in the same manner as in Reference Example 1 and stirred at 50 ° C. for 1 hour to form a polyamic acid block polymer, and then, , Raise the temperature to 200
The mixture was stirred at ° C for 3 hours to form polyimide siloxane (block polymer). This polyimidesiloxane has an imidization ratio of 95% or more and an inherent viscosity of 0.4.
It was 9.

Reference Example 5 Reference Example 4 except that the oligomers prepared in Reference Examples 1 and 2 were used in the amounts and reaction conditions shown in Table 2.
Polyimide siloxane (block polymer) was produced in the same manner as in (1). Table 2 shows the logarithmic viscosity, elastic modulus when formed into a film, softening temperature, and dielectric property of each polyimide siloxane produced.

Reference Example 6 A glass flask having a capacity of 500 ml equipped with a thermometer, a charging / discharging outlet and a stirrer was charged with a-BPDA 0.
054 mol, diaminopolysiloxane (X-22-16
1AS) 0.012 mol, BAPP 0.042 mol and NMP175 g were charged, the temperature was raised to 50 ° C. in a nitrogen stream, and the mixture was stirred at this temperature for 3 hours to generate an amic acid oligomer, and then the reaction liquid Was heated to 200 ° C. and stirred at that temperature for 3 hours to produce polyimide siloxane (random polymer, logarithmic viscosity: 0.59, siloxane unit content: 22.2 mol%). Table 2 shows the physical properties of these polyimidesiloxanes.

[0048]

[Table 2]

Example 1 [Preparation of Solution Composition of Thermosetting Resin] 55 g of the polyimidesiloxane (A-1-B-2) prepared in Reference Example 4 was placed in a glass flask having a capacity of 500 ml.
30 g of bisphenol F type epoxy resin (Epicote 807, manufactured by Yuka Shell Epoxy Co., Ltd.) as an epoxy resin
And glycidyl amine type epoxy resin (manufactured by Mitsubishi Gas Chemical Co.,
Tetrad X) 10 g, phenol novolac type curing agent (manufactured by Meiwa Kasei Co., Ltd., H-1) 18 g as a curing agent, 2-phenylimidazole 0.1 g, and THF 200 g were charged, and the mixture was stirred at room temperature (25 ° C.) for about 2 hours. To prepare a uniform thermosetting resin solution composition (viscosity at 25 ° C .: 7 poise). This solution composition maintained a uniform solution (viscosity) state even when left at room temperature for 1 week.

[Preparation of Thermosetting Resin Composition Sheet] A copper foil (35 μm) was coated on a glossy surface (untreated surface) with a doctor blade at a thickness of 125 μm, and then the coating layer was coated with 5
Heat at 0 ° C for 10 minutes, 100 ° C for 10 minutes, then 1
Heated at 80 ° C for 4 hours. The entire surface of the obtained copper foil and the copper foil of the laminate of the thermosetting resin composition layer were etched to obtain a thermosetting resin composition sheet (20 μm).

[Production of Laminated Plate by Thermosetting Resin Composition Sheet] A solution composition of the thermosetting resin composition described above was used as a polyimide film (manufactured by Ube Industries, Ltd., trade name: UPI).
LEX-S, thickness 20μm) 1 with a doctor blade
Coating with a thickness of 25 μm, and then applying the coating layer at 50 °
The laminate was heated and dried at C for 10 minutes to form a laminate having a thermosetting resin composition layer having a thickness of about 20 μm (softening point of the uncured layer was 80 ° C.) on the polyimide film. Further, a solution composition of the thermosetting resin composition is similarly applied onto the layer on the uncoated polyimide film side of the obtained laminate, and dried to form a thermosetting resin composition on both sides of the polyimide film. A laminate having layers was formed.

[Peeling Strength from Metal Foil] The treated surface of the copper foil (35 μm) was superposed on both sides of the polyimide film having the thermosetting resin composition layer on both sides thereof, and the temperature was 130 °.
C is pressed by passing it between the laminated rolls heated to C while applying pressure,
1 hour at 0 ° C, 1 hour at 120 ° C, 5 at 180 ° C
A heat treatment was carried out in a nitrogen stream for a period of time to cure the thermosetting resin composition layer to produce a laminate. The peel strength with respect to the copper foil, the dielectric properties, and the solder properties of the obtained laminate were measured, and the results are shown in Table 3.

Examples 2 to 3 Example 1 was repeated except that the polyimide siloxanes produced in Reference Examples 4 to 5 as shown in Table 3 were used and the composition of each component was as shown in Table 3. A solution composition of the thermosetting resin composition was prepared in the same manner as in. Laminates were produced in the same manner as in Example 1, and the performance of the laminates was evaluated and shown in Table 3.

Example 4 Using the polyimide siloxane prepared in Reference Example 6,
A solution composition of the thermosetting resin composition was prepared in the same manner as in Example 1 except that the composition of each component was as shown in Table 3. Laminates were produced in the same manner as in Example 1, and the performance of the laminates was evaluated and shown in Table 3.

Comparative Example 1 Commercially available laminated plate [made by DuPont, trade name: Pyralux copper clad plate; copper foil (thickness: 35 μm) / Pyralux (thickness: 25 μm) / DuPont polyimide film,
The trade name: KAPTON (thickness; 25 μm)] evaluated by the same method as this invention is shown in Table 3.

The printed wiring board substrate obtained by the present invention contains a thermosetting resin composition, and thus has a lower dielectric constant and a lower dielectric loss tangent than that of a commercial grade laminate, and has excellent dielectric properties. Further, the thermosetting resin composition has excellent adhesiveness and solder heat resistance. The results are shown in Table 3.

[0057]

[Table 3]

[0058]

The printed wiring board using the laminated board (substrate for printed wiring board) of the present invention has improved heat resistance and adhesiveness and improved dielectric characteristics of the laminated board, so that the propagation speed of electric signals is high. It is suitable for use as a base film and has a good processability, adhesiveness, and heat resistance as a base film, which enables a multilayer laminate.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI Technical display location C08L 63/00 NKB (72) Inventor Kenji Sonoyama 3-10 Nakamiyakitacho, Hirakata-shi, Osaka Ube Industries Ltd. Company Hirakata Institute

Claims (1)

[Claims] 1. An aromatic tetracarboxylic acid component containing (a) a biphenyltetracarboxylic acid as a main component and a general formula (1): (However, R in the formula represents a divalent hydrocarbon residue, and R ₁ ,
R ₂ , R ₃ and R ₄ represent a lower alkyl group or a phenyl group, and n represents an integer of 3 to 60), and 10 to 80 mol% of diaminopolysiloxane and 2 of aromatic diamine
A thermosetting resin composition containing 100 parts by weight of a soluble polyimide siloxane obtained from a diamine component consisting of 0 to 90 mol%, (b) an epoxy compound of 20 to 250 parts by weight, (c), and an epoxy curing agent is a polyimide. It is laminated on a film-based substrate and copper foil is bonded on one side or both sides, and the dielectric constant after curing of the thermosetting resin composition is 3.3 (12.5 GHz, 25 °).
C) A printed wiring board substrate characterized by being: