JP3111441B2 - Substrate for printed wiring board - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION The present invention relates to a low dielectric constant
The present invention relates to a printed wiring board substrate (laminate and metal-clad laminate) having excellent workability, particularly flexibility and adhesiveness.

[0002]

2. Description of the Related Art Conventionally, as a substrate having a low dielectric constant, 1,2-
Japanese Patent Application Laid-Open No. 62-1877 discloses an example of a copper-clad laminate comprising a composition containing a polybutadiene modified with a terminal carboxy group containing a polybutadiene unit or an epoxidized polybutadiene as one component.
No. 36, JP-A-63-280721, examples of heat-resistant copper-clad laminates comprising a composition comprising a combination of a bismaleimide-based compound, a diamine and a phenol are disclosed in JP-A-1-271235 and JP-A-1-271235. 1-271236
No., published in Japanese Unexamined Patent Publication No.

However, in recent years, in order to cope with a higher speed of an electronic device in a printed wiring board substrate, an improvement in dielectric characteristics for increasing a transmission speed of an electric signal, a workability, etc.
There is a strong need for improved adhesiveness and heat resistance and cost reduction.

[0004]

SUMMARY OF THE INVENTION It is an object of the present invention to provide the above-described dielectric characteristics (low dielectric constant and low dielectric loss tangent), heat resistance, and workability, particularly for adapting to a higher transmission speed of an electric signal.
An object of the present invention is to provide a printed wiring board substrate having excellent flexibility and adhesiveness.

[0005]

Means for Solving the Problems The inventors of the present invention have conducted intensive studies with the aim of improving the difficulties of conventional printed wiring board substrates, and have found that a thermosetting resin containing a polyimide siloxane, an epoxy compound and an epoxy curing agent is used. Laminated resinous composition on a polyimide film-based substrate, the printed wiring board substrate cured by bonding copper foil on both sides or one side, to meet the increase in the speed of transmission of electrical signals The inventors of the present invention have learned that a substrate for a printed wiring board is excellent in dielectric properties (low dielectric constant, low dielectric loss tangent), heat resistance, workability, adhesiveness, and the like.

The present invention relates to (a) an aromatic tetracarboxylic acid component containing a biphenyltetracarboxylic acid as a main component and a compound represented by the general formula (1):

[0007]

Embedded image

(Where 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 is an integer of 3 to 60) And a diamine component consisting of 10 to 80 mol% of a diaminopolysiloxane represented by the following formula) and 20 to 90 mol% of an aromatic diamine.
/ Mm ² or less soluble polyimide siloxane 100
Parts by weight, 20 to 80 parts by weight of an epoxy compound, and (c) a thermosetting resin composition layer having a thickness of about 1 to 20 μm comprising an epoxy curing agent.
A laminate obtained by laminating one side or both sides of a polyimide film having a thickness of 25 μm or less , and further joining a copper foil thereon, wherein the dielectric constant after curing of the thermosetting resin composition layer (frequency: 50 Hz and 12.5 GHz, measurement temperature: 2
(5 ° C.) is 3.3 or less, and the peel strength (90 °, 25 ° C.) measured for the laminate is 1.4 kg / cm or more. Flexible printed circuit board.

In the present invention, the aromatic tetracarboxylic acid component mainly composed of biphenyltetracarboxylic acids includes 3,3 ′, 4,4′-biphenyltetracarboxylic acid, 2,3,
An aromatic tetracarboxylic acid component containing 60% by mole or more, especially 80 to 100% by mole of 3 ', 4'-biphenyltetracarboxylic acid or biphenyltetracarboxylic acids such as acid dianhydride and esterified product is used. Is done. Among these, in particular, 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride is preferable because the polyimidesiloxane is excellent in solubility in an organic polar solvent, compatibility with an epoxy compound, and the like. .

In the present invention, the aromatic tetracarboxylic acid component which can be used together with the biphenyltetracarboxylic acids includes, for example, 3,3 ′, 4,4′-benzophenonetetracarboxylic acid, 3,3 ′, 4, 4'-diphenylethertetracarboxylic acid, bis (3,4-dicarboxyphenyl) methane, 2,2-bis (3,4-dicarboxyphenyl) propane, pyromellitic acid, or their acid dianhydrides or esters And the like can be suitably mentioned. However, if the amount of these is too large, the polyimide siloxane becomes insoluble in an organic polar solvent or the compatibility with an 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 selected from "a plurality of methylene groups" having 2 to 6 carbon atoms, particularly 3 to 5 carbon atoms, or phenylene group. A divalent hydrocarbon residue represented by R ₁
-R ₄ has 1 carbon atom such as a methyl group, an ethyl group and a propyl group
It is preferable that n is an integer of 3 to 60, particularly 5 to 20, more preferably 5 to 15. R, R
₁ or too large number of carbon atoms of to R _4, or the number becomes poor heat resistance may decrease the reactivity too large of n, solubility in an organic solvent or lower the molecular weight of the resulting polyimide siloxane is reduced Or the above-mentioned degree is appropriate since compatibility with other organic compounds is deteriorated.

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,
ω, ω′-bis (4-amino-3-methylphenyl) polydimethylsiloxane, ω, ω′-bis (3-aminopropyl) polydiphenylsiloxane, and the like can be preferably mentioned.

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

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

In the present invention, the diaminopolysiloxane and the aromatic diamine are preferably 10 to 80 mol%, preferably 12 to 75 mol%, more preferably 13 to 70 mol%, and the latter 90 to 20 mol%. Is 88-25
Mol%, more preferably 87 to 30 mol%. If either component is too large or too small to deviate from these ranges, the solubility of the polyimidesiloxane in the organic solvent will be reduced, or the compatibility with other organic compounds will be poor.

In the present invention, the polyimidesiloxane (a) is produced by the following method. (A ₁ ) An aromatic tetracarboxylic acid component and a diamine component of diaminopolysiloxane and aromatic diamine are polymerized and imidized continuously at a temperature of 15 to 250 ° C. in an organic polar solvent using substantially equimolar amounts. To obtain polyimide siloxane.

(A ₂ ) The diamine component is separated, and an excess amount of an 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 a terminal having a degree of about 1 to 10 is prepared, and an aromatic tetracarboxylic acid component and an excess amount of an aromatic diamine are separately placed in an organic polar solvent at a temperature of 15 to 250.
Polymerization and imidization at ° C., average polymerization degree 1-10
An imide oligomer having an amino group at an end thereof is prepared, and then both are mixed so that the acid component and the diamine component are substantially equimolar, and reacted at a temperature of 15 to 60 ° C. A method of obtaining a block type polyimide siloxane by raising the temperature to ~ 250 ° C.

(A ₃ ) An aromatic tetracarboxylic acid component, a diaminopolysiloxane component and an aromatic diamine component are used in approximately equimolar amounts and are first heated to 20 to 80 ° C. in an organic polar solvent.
There is a method in which a polyamic acid is once obtained by polymerization with C and then imidized to obtain a polyimide siloxane.

Examples of the organic polar solvent used in the production of 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, dimethylsulfoxide, diethylsulfoxide, dimethylsulfone, diethylsulfone, solvents containing a sulfur atom such as hexamethylsulfonamide, cresol, phenol, phenolic solvents such as xylenol, Acetone, methanol,
Examples of the solvent include a solvent having an oxygen atom in the molecule such as ethanol, ethylene glycol, dioxane, and tetrahydrofuran, and other solvents such as pyridine and tetramethylurea. Further, if necessary, benzene, toluene,
It is also possible to use an aromatic hydrocarbon solvent such as xylene, or another kind of organic solvent such as solvent naphtha or benzonitrile.

In the present invention, as the polyimide siloxane, those obtained by any of the above-mentioned methods (a ₁ ) to (a ₃ ) may be used. At least 3% by weight, 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 imidation ratio of the polyimide siloxane was determined to be 90% by an infrared absorption spectrum analysis method.
% Or more, particularly preferably 95% or more. In the infrared absorption spectrum analysis, a high imidation ratio is obtained in which substantially no absorption peak relating to the amide-acid bond of the polymer is found and only the absorption peak relating to the imide ring bond is observed. Is preferred.

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

Further, the above-mentioned polyimidesiloxane has an elastic modulus of 250 kg / m2 when formed into a film.
m ² or less, especially 0.5 to 200 kg / mm ² ,
The thermal decomposition onset temperature is 250 ° C. or higher, particularly 300 ° C. or higher, and the secondary rearrangement temperature is −10 ° C. or higher, especially 30 ° to
About 250 ° C, or a softening temperature of -10 ° C or more,
In particular, the temperature is preferably 5 ° C. or more, more preferably about 5 to 250 ° C.

The proportion of the epoxy compound (b) used in the present invention is from 20 to 80 parts by weight, preferably from 30 to 80 parts by weight, based on 100 parts by weight of the polyimide siloxane. Since the uncured resin composition is sticky and lacks flexibility after curing, or the softening point of the uncured resin composition is too high, or the lamination properties after curing are deteriorated, so that the above range is not satisfied. It is desirable to do.

The epoxy compound used in the present invention may be any epoxy compound having at least one epoxy group. Specific examples thereof include a bisphenol A type or a bisphenol F type epoxy resin (oiled shell). Epoxy Co., Ltd., epoxy coat 807, 828, etc., phenol novolak type epoxy resin, alkyl polyphenol type epoxy resin (Nippon Kayaku Co., Ltd., RE701, RE550S, etc.), polyfunctional epoxy resin (Sumitomo Chemical) Industrial Co., Ltd., ELM-1
00), a glycidyl ether type epoxy resin, a glycidyl ester type epoxy resin, a glycidylamine type epoxy resin (trade name: Tetrad X, etc., manufactured by Mitsubishi Gas Chemical Co., Ltd.) or 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 uncured resin composition increases, so that the melting point is 90 ° C. or less, especially about 0 to 80 ° C., or at a temperature of 30 ° C. or less. Those that are liquid are preferred.

Further, (c) used in the present invention
As the type of the epoxy curing agent of the component, curing agents known per se, for example, curing catalysts such as imidazoles, tertiary amines, and triphenylphosphines, dicyandiamides, hydrazines, aromatic diamines, and hydroxyl groups can be used. Polyaddition type curing agents such as phenol novolak type curing agents (Phenol Novolak: H-1, H-5, etc., manufactured by Meiwa Kasei Co., Ltd.), 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 per 100 parts by weight of the epoxy compound,
Particularly, it is preferable to use 0.03 to 80 parts by weight.

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

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

The concentration of the above solution composition is suitably from 3 to 50% by weight, preferably from 5 to 40% by weight, and the solution viscosity (30 ° C.) is from 0.1 to 10,000 poise, especially from 0.1 to 10,000 poise.
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 (temperature at which softening starts on a hot plate) of an uncured resin component alone of 150 ° C. or less, particularly 140 ° C. Hereinafter, the temperature is more preferably about 0 to 130 ° C.

The thermosetting resin composition according to the present invention is obtained by mixing a solution composition in which all of the above resin components are dissolved in an organic polar solvent with a suitable metal foil, aromatic polyimide film, aromatic polyester or the like. On a heat-resistant film surface or a film surface of a thermoplastic resin such as polyethylene, and apply the applied layer at a temperature of 80 to 200 ° C. for 20 seconds to 10 seconds.
A dry film having a thickness of about 1 to 20 μm from which the solvent has been substantially removed to a level of 1% by weight or less, preferably 0.5% by weight or less, by drying for 0 minutes. It can be formed as a thin film of the thermosetting resin composition in a state.

The thus-prepared thin film of the uncured thermosetting resin composition has a 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 further laminate a laminated sheet in which a thin layer of an uncured thermosetting resin composition is formed on the heat-resistant or thermoplastic film and a metal foil or heat-resistant film for transfer destination. The sheet layer of the thermosetting resin composition is transferred onto a transfer destination metal foil or heat-resistant film by passing between a pair of rolls (lamination rolls) heated to a temperature of about 20 to 200 ° C. It is also possible.

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

The printed wiring board of the present invention has a thickness of 25
It can be obtained by laminating a thermosetting resin composition layer having a thickness of about 1 to 20 μm on one side or both sides of a polyimide film of μm or less , and further joining a copper foil thereon.
Further, the thermosetting resin composition of the thermosetting resin composition layer may contain a small proportion of other thermosetting resin such as bismaleimide resin as a resin component.

[0036]

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

The softening temperature of the polyimide siloxane film is a value obtained by measuring a tan δ (high temperature side) of a viscoelastic peak in a viscoelastic test using a mechanical spectrometer RDS-2 manufactured by Rheometrics.

The modulus of elasticity of the polyimide siloxane is a result of a measurement using a tensile tester manufactured by Intesco Corporation at a tensile speed of 5 mm / min.

The peel strength was measured using a tensile tester manufactured by Intesco Corporation at a peeling speed of 50 mm / min and a measurement temperature of 25 ° C.
90 ° peel test, and 1 at 180 ° C
It is a result measured by performing an 80 ° peel test.

The dielectric constant is JIS-C-64 at 50 Hz.
81, and a microwave molecular orientation meter (manufactured by KS Systems, MOA-2012 at 12.5 GHz).
In A), the copper foil of the laminate having the thermosetting resin composition layer provided on one side of the copper foil was removed by etching on the entire surface, and the thermosetting resin composition layer after thermosetting was measured. 340 ° C
The solder heat resistance after 10 seconds is judged by the usual method
When swelling occurs, no abnormality is observed.
If it did occur, it was considered abnormal .

[Production of Imidosiloxane Oligomer] Reference Example 1 2,3,3 ′, 4′-biphenyltetracarboxylic dianhydride was placed in a 500-ml glass flask equipped with a thermometer, a charging / discharging port, and a stirrer. Product (a-BPDA) 0.04
5 mol, ω, ω'-bis (3-aminopropyl) polydimethylsiloxane (X-22-1 manufactured by Shin-Etsu Silicon Co., Ltd.)
61AS, n: 9) 0.030 mol, and N-methyl-2
-160 g of pyrrolidone (NMP) are charged, heated to a temperature of 50 ° C. in a stream of nitrogen and stirred at this temperature for 2 hours,
An amic acid oligomer was formed, and then the reaction solution was heated to 200 ° C. and stirred at that temperature for 3 hours to give an imide siloxane oligomer having a terminal anhydride group (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
In the same manner as in Reference Example 1 except that each of P was used, an imidosiloxane oligomer having an anhydride group at a terminal (B-
One component, average degree of polymerization: 2) was produced.

Reference Example 3 An imide oligomer having a terminal amino group (component B-2, average polymerization) was prepared in the same manner as in Reference Example 1 except that the amounts of a-BPDA, BAPP and NMP shown in Table 1 were used. Degree: 5) was produced.

[0044]

[Table 1]

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

Reference Example 5 Reference Example 4 was repeated except that the oligomers prepared in Reference Examples 1 and 2 were used in the amounts and reaction conditions shown in Table 2.
In the same manner as in the above, polyimide siloxane (block polymer) was produced. Table 2 shows the logarithmic viscosities of each of the produced polyimide siloxanes, the modulus of elasticity when molded into a film, the softening temperature, and the dielectric properties.

Reference Example 6 A 500-ml glass flask equipped with a thermometer, a charging / discharging port, and a stirrer was charged with a-BPDA 0.1.
054 mol, diaminopolysiloxane (X-22-16)
1AS) 0.012 mol, 0.042 mol of BAPP and 175 g of NMP were charged, heated to a temperature of 50 ° C. in a stream of nitrogen, and stirred at this temperature for 3 hours to form an amic acid oligomer. Was heated to 200 ° C. and stirred at that temperature for 3 hours to produce a polyimidesiloxane (random polymer, logarithmic viscosity: 0.59, siloxane unit content: 22.2 mol%). Table 2 shows the physical properties of these polyimide siloxanes.

[0048]

[Table 2]

Example 1 [Preparation of solution composition of thermosetting resin] In a glass flask having a capacity of 500 ml, 55 g of the polyimidesiloxane (A-1-B-2) produced in Reference Example 4 was added.
30 g of bisphenol F type epoxy resin (manufactured by Yuka Shell Epoxy Co., Epicoat 807) as an epoxy resin
And glycidylamine type epoxy resin (Mitsubishi Gas Chemical,
10 g of Tetrad X), 18 g of a phenol novolak-type curing agent (H-1 manufactured by Meiwa Kasei Co., Ltd.), 0.1 g of 2-phenylimidazole, and 200 g of THF as a curing agent, 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 one week.

[Preparation of thermosetting resin composition sheet] A doctor blade is applied on a glossy surface (untreated surface) of a copper foil (35 μm) with a thickness of 125 μm, and then the coating layer is applied. The film was heated at 50 ° C. for 10 minutes, at 100 ° C. for 10 minutes, and further heated and cured at 180 ° C. for 4 hours. The copper foil of the laminate of the obtained copper foil and the thermosetting resin composition layer was entirely etched to obtain a thermosetting resin composition sheet (20 μm). to this
Then, the dielectric constant was measured .

[Production of Laminated Board from Thermosetting Resin Composition Sheet] A solution composition of the above thermosetting resin composition was applied to a polyimide film (trade name: UPI manufactured by Ube Industries, Ltd.).
LEX-S, 20 μm thick) with a doctor blade
25 μm thickness, then apply the coating layer at 50 °
C for 10 minutes and dried by heating to form a laminate having a thermosetting resin composition layer having a thickness of about 20 μm (the uncured layer had a softening point of 80 ° C.) on the polyimide film. Furthermore, a solution composition of the above-mentioned thermosetting resin composition is similarly applied on the uncoated polyimide film surface of the obtained laminated board on the layer, dried, and dried on both surfaces of the polyimide film. A laminate having layers was formed.

[Peel strength with metal foil , solder characteristics of laminate
Properties ] A treated surface of copper foil (35 μm) is superimposed on both surfaces of a polyimide film having the above-mentioned thermosetting resin composition layer on both surfaces, and the laminate is passed while applying pressure between a laminator roll heated to 130 ° C. The laminate was pressed at 100 ° C. for 1 hour, at 120 ° C. for 1 hour,
Heat treatment was performed in a nitrogen stream at a temperature of 5 ° C. for 5 hours to cure the thermosetting resin composition, thereby producing a laminate. With respect to the obtained laminate, the peel strength from the copper foil and the solder characteristics were measured. Previous
Dielectric properties, solder properties, peel strength measured as described above
Table 3 summarizes the degrees.

Examples 2 to 3 Example 1 was repeated except that the polyimidesiloxanes prepared in Reference Examples 4 and 5 as shown in Table 3 were used and the composition of each component was as shown in Table 3. In the same manner as in the above, solution compositions of the thermosetting resin composition were respectively prepared. In the same manner as in Example 1, each laminated plate was manufactured, and the performance of the laminated plate was evaluated.

Example 4 Using the polyimidesiloxane prepared in Reference Example 6,
Except that 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 Example 1. In the same manner as in Example 1, each laminated plate was manufactured, and the performance of the laminated plate was evaluated.

Comparative Example 1 Commercially available laminated board [manufactured by Dupont, trade name: Pyralux copper-clad board; copper foil (thickness: 35 μm) / Pilalux (thickness: 25 μm) / Dupont polyimide film;
Table 3 shows the results of evaluation of the product name: KAPTON (thickness: 25 μm)] in the same manner as in the present invention.

The printed wiring board substrate obtained by the present invention has a low dielectric constant and a low dielectric loss tangent as compared with a commercially available laminate, and has excellent dielectric properties, by containing the thermosetting resin composition. Also, the thermosetting resin composition is excellent in adhesiveness and solder heat resistance. The results are shown in Table 3.

[0057]

[Table 3]

[0058]

According to the printed wiring board using the laminated board (printed wiring board substrate) of the present invention, the heat resistance and the adhesiveness are improved, and the dielectric properties of the laminated board are improved. It is suitable for use as a base film and makes it possible to form a multilayer laminate by improving the workability, adhesion, and heat resistance as a base film.

────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁷ Identification code FI C08L 79/08 C08L 79/08 Z (56) References JP-A-5-25453 (JP, A) JP-A-3-82195 ( JP, A) JP-A-63-141737 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) H05K 1/03 610-630 B32B 15/08

Claims (1)

(57) [Claims] 1. An aromatic tetracarboxylic acid component comprising (a) a biphenyltetracarboxylic acid as a main component and a compound represented by the following general formula (1): H ₂ N—R— [Si (R ₁ ) (R ₂ ) —O—] n —Si (R ₃ ) (R ₄ ) —R—NH ₂ (I) (where R represents a divalent hydrocarbon residue, and R ₁ ,
R ₂ , R ₃ and R _{4 each} 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 polyimide siloxane having an elastic modulus of 250 kg / mm ² or less when formed into a film, obtained from a diamine component consisting of 〜90 mol%, (b) 20-80 parts by weight of an epoxy compound, and ( c) A laminate obtained by laminating a thermosetting resin composition layer having a thickness of about 1 to 20 μm comprising an epoxy curing agent on one or both sides of a polyimide film having a thickness of 25 μm or less , and further joining a copper foil thereon. The dielectric constant after curing of the thermosetting resin composition layer (frequency: 50 Hz and 12.5 GHz, measurement temperature: 2
(5 ° C.) is 3.3 or less, and the peel strength (90 °, 25 ° C.) measured for the laminate is 1.4 kg / cm or more. Flexible printed circuit board.