JP3077857B2 - Metal base circuit board - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

This invention relates to metal-based circuit boards.

[0002]

2. Description of the Related Art In the field of electric and electronic components, various characteristics such as heat resistance, thermal dimensional stability, low moisture absorption, flame retardancy, high frequency characteristics, etc. have been taken to a high degree from the viewpoint of miniaturization and high performance of equipment. There is an increasing demand for balanced metal-based circuit boards.

As a circuit board in this field, a sheet obtained by impregnating a polyimide film, a fluorine-based film, or a glass cloth impregnated with an epoxy resin (hereinafter referred to as "glass epoxy") with a metal foil or the like is used. What was laminated | stacked on the metal plate via the adhesive agent was used. Further, poly-p-phenylene sulfide (hereinafter referred to as P
It is called PS. )), A circuit board using an unstretched sheet (hereinafter, referred to as a PPS sheet) and a biaxially oriented film (hereinafter, referred to as a PPS film) as an insulating base material has recently received particular attention, and these circuit layers and a metal plate are laminated. The following has been proposed (JP-A-1-95586).

[0004]

However, the above-mentioned metal-based circuit board has the following problems.

(1) A metal-based circuit board using a circuit board made of a polyimide film has high heat resistance, but has a high moisture absorption and is inferior in high frequency characteristics.

(2) A film using a fluorine-based film has poor adhesion workability.

(3) Those using a glass epoxy substrate have a high moisture absorption rate and are inferior in high frequency characteristics. Further, the thickness is increased in consideration of the multilayered circuit board.

(4) A conventional circuit board using a PPS sheet or a PPS film is excellent in heat resistance, low moisture absorption, high-frequency characteristics, and the like. The excellent characteristics of PPS were degraded and satisfactory characteristics could not be maintained.

On the other hand, it has been proposed that a surface treatment such as a plasma treatment is performed without using an adhesive, and the laminate is formed by heat fusion with a metal plate. However, there is a problem that the adhesive strength is insufficient and, for example, the metal plate and the circuit layer are easily peeled off when placed in a solder bath. An object of the present invention is to provide a metal-based circuit board that pays attention to the excellent moisture absorption properties, high-frequency properties, heat resistance, and the like of PPS, and that has excellent adhesion to a metal plate while maintaining these properties.

[0010]

That is, the present invention provides a sheet (A) comprising a resin composition containing poly-p-phenylene sulfide as a main component and an electric circuit (A) layer,
A metal which is laminated on a metal (C) layer via a resin composition (B) layer comprising a copolymerized polyphenylene sulfide containing at least one or more copolymer units other than a p-phenylene sulfide unit. It is a base circuit board.

In the present invention, PPS means that at least 80 mol%, preferably at least 90 mol% of the repeating unit is a structural formula.

Embedded image Means a polymer comprising the structural unit represented by If the content of such a component is less than 80 mol%, the crystallinity of the polymer, the heat transition temperature, and the like are low, and the heat resistance, dimensional stability, mechanical properties, and the like, which are features of the resin composition containing PPS as a main component, are impaired.

In the above PPS, the repeating unit 20
If the amount is less than mol%, preferably less than 10 mol%, a unit containing a copolymerizable sulfide bond may be contained. The method of copolymerization may be random or block.

In the present invention, a resin composition containing poly-p-phenylene sulfide as a main component (hereinafter referred to as a PPS composition) refers to a poly-p-phenylene sulfide of 6%.
A composition containing 0% by weight or more. PPS content is 60
If it is less than 10% by weight, the mechanical properties of a sheet comprising the composition,
Impairs heat resistance, heat fusibility, etc. The remaining less than 40% by weight of the composition may contain additives other than PPS, such as polymers, inorganic or organic fillers, lubricants, and coloring agents. Further, the melt viscosity of the PPS composition is 30 ° C.
At 0 ° C. and a shear rate of 200 sec ⁻¹ , 100 to 5
0000 poise, more preferably in the range of 500 to 20,000 poise, is preferable in view of sheet and film processability.

The layer (A) referred to in the present invention is a circuit layer comprising a sheet containing a PPS composition and an electric circuit. Here, the sheet containing the PPS composition is at least a sheet containing the PPS composition, and is not particularly limited as long as the object of the present invention is not impaired. For example, a PPS unstretched sheet or biaxially stretched film, a laminate of the sheet or the film with a sheet or film made of another resin composition, or an inorganic or organic fiber sheet (nonwoven fabric, cloth,
Paper, felt, etc.), and resin-impregnated ones. The thickness of the A layer is 5 to 300 μm
Is preferred.

In the present invention, a copolymerized polyphenylene sulfide (hereinafter, referred to as a copolymerized PPS) is defined as a p-phenylene sulfide unit having a main repeating unit of 1
It refers to one formed by copolymerizing two or more kinds of copolymerized units. The content of p-phenylene sulfide unit in the copolymerized polyphenylene sulfide is from 50 to 95 mol%, preferably from 70 to 92 mol%, based on all repeating units.
Range. If the content is less than 50 mol%, the heat resistance and thermal dimensional stability of a metal-based circuit board will be poor, and if it exceeds 95 mol%, the adhesion of the circuit layer to the metal layer will deteriorate. I do.

As the copolymer unit, m-phenylene sulfide unit,

Embedded image

Embedded image (Where X represents an alkylene, CO, or SO ₂ unit)

Embedded image

Embedded image (Where R represents an alkyl, nitro, phenylene, or alkoxy group), and a complex unit of these may be present. Preferred copolymerized units are m-phenylene sulfide units. The copolymerization amount of these units is such that the number of copolymer units, which is the second largest after the p-phenylene sulfide unit, which is the main repeating unit of the copolymerized PPS, is 3 to 50 mol%, preferably 5 to 30 mol%, based on all repeating units. Range. If the content is less than 3 mol%, the adhesive strength with the circuit layer of the circuit board will deteriorate. Conversely, if it exceeds 50 mol%, the heat resistance and thermal dimensional stability of the circuit board will be poor. The remaining part of the repeating unit of the copolymerized PPS may be composed of other copolymerizable units,

Embedded image Is preferably 1 mol% or less of the whole copolymer.

The mode of copolymerization of the copolymerized PPS of the present invention may be random or block, but is preferably random. The copolymer composition can be determined by any means depending on the composition.

Further, the resin composition comprising copolymerized PPS (hereinafter referred to as copolymerized PPS composition) (B) means that the above-mentioned copolymerized PPS is 80% by weight or more, preferably 90% by weight, of the resin component. It means what occupies above. If the remaining amount is less than 20% by weight, organic and inorganic additives other than the copolymerized PPS, inert particles and the like may be contained.

The melting point of the copolymerized PPS composition of the present invention is 2
The range of 00-285 degreeC is preferable. Melt viscosity is 30
At 0 ° C. and a shear rate of 200 sec ⁻¹ , preferably 50 to 20,000 poise, more preferably 100 to ¹ poise
0000 poise.

The electric circuit in the present invention is an electric passage formed by patterning a conductor. Examples of the conductor include metals such as copper, aluminum, and iron; alloys of two or more kinds; metals such as copper and silver; and carbon. And a paste containing the above conductor. Further, the circuit layer of the present invention may be formed by laminating two or more circuit layers. In this case, within the scope of the present invention, two or more types of circuit layers (for example, those having different insulating base materials, different types of circuit conductors)
May be mixed. Further, the size of each circuit layer may be different.

The metal (C) layer in the present invention is a metal plate having a thickness of 0.2 to 5.0 mm. The type of metal is not particularly limited, but usually a steel plate, a silicon steel plate, an aluminum plate, or the like is used.

The metal-based circuit board of the present invention is PPS
A sheet comprising a composition and an electric circuit (A)
The layer and the metal (C) layer are joined by thermocompression bonding via the copolymerized PPS composition (B) layer. The thickness of the layer B is preferably in the range of 2 to 100 μm, and more preferably in the range of 2 to 70 μm, on the balance between adhesiveness and heat resistance. Further, the thickness of the sheet containing the PPS composition of layer A, which can be measured from a cross-sectional photograph of the metal base circuit board of a polarizing microscope, is defined as a (μ)
m), and the thickness of the B layer is b (μm), b / a is 0.1.
The range of 02 to 1.2 is particularly preferable in terms of balance of adhesiveness, heat resistance, moisture absorption characteristics, high frequency characteristics, and the like. The content of the copolymerized PPS contained in the resin composition of the layer A (Aco
The relation between p) and the content (Bcop) of the copolymerized PPS contained in the resin composition of the B layer is preferably Bcop> Acop, and the melting point of the resin composition of the A layer and the melting point of the resin composition of the B layer It is particularly preferable that the difference in the melting points is in the range of 5 to 90 ° C. in terms of processability and easy achievement of the object of the present invention. The layer B may or may not have molecules oriented.

Next, a method for manufacturing a metal-based circuit board according to the present invention will be described.

First, there are various polymerization methods for the copolymerized PPS used in the present invention, but alkali sulfide, p-dihalobenzene (main component monomer) and auxiliary component monomer are blended in the ratio according to the present invention, and a polar solvent is prepared. In the presence of a polymerization aid, a method of polymerizing at a high temperature and a high pressure is preferable because the polymerization degree of the obtained polymer is easily increased. In particular, it is preferable to use sodium sulfide as an alkali sulfide, p-dichlorobenzene as a main component monomer, and N-methylpyrrolidone as a solvent. As the sub-component monomer which coexists with the p-dihalobenzene (main component monomer),

Embedded image

Embedded image

Embedded image (Here, X represents an alkylene, CO, or SO ₂ unit.)

Embedded image

Embedded image (Where R represents an alkyl, nitro, phenylene, or alkoxy group), and a plurality of subcomponent monomers may be present. Preferred subcomponent monomers are

Embedded image It is.

If necessary, an inorganic or organic additive is added to the copolymerized PPS thus obtained to form the copolymerized PPS.
It is a PS resin composition.

Next, the copolymerized PPS resin composition is formed into a sheet. When producing an unstretched or non-oriented sheet, the resin composition melted by an extruder is quantitatively cast from a die onto a metal drum and rapidly cooled. In the case of producing an oriented film, the unstretched and non-oriented sheet is uniaxially or biaxially stretched by a known method, and heat-treated if necessary. Stretching is 85 to 110 in both the longitudinal and width directions.
It is usually carried out in the range of 2 to 4.5 times at ° C. The heat treatment is performed at a fixed temperature or a limited shrinkage of 20% or less for 1 to 60 seconds in the range of 180 ° C. to the melting point.

On the other hand, the PPS of the present invention is polymerized in the same manner as the copolymerized PPS, but does not include or reduces the amount of the auxiliary component monomer as described in the present invention.

Of course, for the purpose of adjusting the melt viscosity of the copolymerized PPS and PPS,

Embedded image You may mix | blend a trifunctional monomer like this.

If necessary, an inorganic or organic additive is added to the PPS thus obtained to obtain a PPS resin composition.

In the present invention, the sheet of the PPS resin composition used for the layer A includes an unstretched sheet of the PPS resin composition, a biaxially stretched film, the unstretched sheet, an unstretched sheet different from the biaxially stretched film, A laminate sheet with a biaxially stretched film, a laminate with a fiber sheet, a resin impregnated body, and the like are used. The method for producing the unstretched sheet and the biaxially stretched film of the PPS resin composition may be the same as that for the copolymerized PPS resin composition. The laminated sheet is formed by laminating a PPS sheet or PPS film with another unstretched sheet or biaxially stretched film other than PPS by means of an adhesive or by heat fusion (thermocompression bonding). Lamination by heat fusion is preferred in that the object of the present invention is easily achieved.

As the method of heat fusion, a hot roll press method and a hot plate press method are usually used. The lamination conditions differ depending on the type of sheet other than PPS, but the lamination temperature is in the range of Tma ± 50 ° C. when the melting point of the PPS resin composition is Tma, the lamination pressure is in the range of 1 to 30 kg / cm ² , It is preferable in terms of sheet flatness and adhesiveness. Further, for the production of a laminate with a fiber sheet and a resin impregnated body, a hot roll press method or a hot plate press method can be used. Here, the resin impregnation refers to a state in which the resin has penetrated around the elementary fibers of the fiber sheet, and is a particularly preferable characteristic in the case of a circuit board.

An electric circuit is formed on the sheet thus obtained. The electric circuit can be formed by providing a metal layer by a known method, for example, lamination, vapor deposition, plating, or the like, and etching the electric circuit pattern.
For the etching, a ferric chloride aqueous solution or the like is usually used. In addition, a circuit pattern can be formed from a conductive paste containing a conductor such as metal or carbon by a method such as a silk printing method. Further, a method of manufacturing a multilayer circuit board is as follows: a hole for electrically connecting between the layers is formed in the above-mentioned circuit layer, if necessary, two or more layers are overlapped, and each circuit layer is thickened with plating, conductive paste or the like through the hole. Connect in the direction.

The circuit layer (multilayer circuit board) obtained as described above and a steel plate, a silicon steel plate, and an aluminum plate are laminated via a sheet or film of a copolymerized PPS composition to form a metal-based circuit board of the present invention. To manufacture. The laminating method is performed by laminating the above three layers in the order of A / B / C by a hot press roll method, a hot plate press method or the like. Lamination conditions are 200 ° C ~
The temperature of the melting point of the PPS resin composition of the A layer is 1 to 40 kg.
/ Cm ² is preferable in view of workability, adhesiveness and the like.

The thermocompression bonding of the electric circuit and the sheet of the PPS resin composition may be performed via the copolymerized PPS composition. The order of lamination is the electric circuit / copolymerized PPS composition (B)
/ PPS resin composition / copolymerized PPS composition (B) / metal plate (C).

In the method of manufacturing a metal-based circuit board according to the present invention, the above order is not essential. For example, an electric circuit may be provided after laminating an insulating sheet of a circuit layer and a metal plate. Alternatively, the composite PPS resin composition and the PPS resin composition may be co-extruded to prepare a composite sheet or composite film of both, and the metal-based circuit board may be manufactured by the above method. Of course, a laminated sheet, a laminated body, and a resin-impregnated body referred to in the present invention may be prepared using the composite sheet or the composite film, and a metal-based circuit board may be manufactured by the above method.

[0036]

[Method for measuring physical properties and method for evaluating effects] The characteristic values of the present invention are determined according to the following measuring methods and evaluation criteria.

(1) Solder Heat Resistance Temperature The metal base circuit board is immersed for 30 seconds so that the electric circuit is in contact with the solder liquid surface set at each temperature (accuracy of ± 5 ° C. or less) and taken out. At that time, the change of the insulating film, the change of the state of the circuit, the peeling of the metal plate and the circuit board, etc. were observed, and the result was expressed by the limit solder temperature. Electric circuit 5mm at 5mm intervals
Adjusted to the width and the grid.

(2) Adhesive Strength A metal plate of a metal base circuit board having a width of 10 mm and a length of 100 mm was fixed using a shopper, and the insulating substrate was pulled to measure the peel strength (g / cm). Peeling speed is 50mm
At / min, the peel angle is 180 degrees.

(3) Frequency Characteristics of Dielectric Loss Measured according to JIS-C-6481.

The change in dielectric loss was examined by changing the frequency.

(4) Measurement of Thickness of Layer A and Layer B The cross section of the metal base circuit board was observed with a deflection microscope, and the thickness of each layer was calculated from the photograph of the cross section.

(5) Thermal dimensional change rate 75 m at each corner of the metal base circuit board at 85 mm square
Markings at m intervals were provided. The dimensions were accurately measured with a microscope (α mm). Next, after aging for 30 seconds in a solder bath set at 250 ° C. so that the metal plate was in contact with the solder, the distance between the markings was measured with a microscope (βm
m). The thermal dimensional change was calculated by the following equation.

Thermal dimensional change rate (%) = (α−β) / α × 100

[0044]

Next, the present invention will be described in detail with reference to examples.

Example 1 (1) Preparation of Copolymerized PPS Composition An autoclave was charged with 100 mol of sodium sulfide nonahydrate, 45 mol of sodium hydroxide and 25 l of N
-Methyl-pyrrolidone (hereinafter referred to as NMP) was charged, the temperature was gradually raised to 220 ° C. while stirring, and the contained water was removed by distillation.

Into the dehydrated system, 91 mol% of p-dichlorobenzene as a main component monomer, 10 mol% of m-dichlorobenzene as a sub component monomer, and 0.2 mol% of 1,2,4 5 liters of NM with trichlorobenzene
It was added together with P, and nitrogen was added under a pressure of 3 kg / cm ² at 170 ° C., followed by heating and polymerization at 260 ° C. for 4 hours. After the completion of the polymerization, the mixture was cooled, the polymer was precipitated in distilled water, and a small block polymer was collected by a wire mesh having a 150 mesh opening.

The polymer was washed five times with distilled water at 90 ° C., and then dried at 120 ° C. under reduced pressure to give a melt viscosity of 1
000 poise, white particulate copolymer P having a melting point of 253 ° C
A PS composition was obtained.

Next, 50 g of spherical silica having a diameter of 0.5 μm was blended with 10 kg of the copolymerized PPS, and the mixture was extruded at 320 ° C. into a gut shape using a 30 mm φ twin screw extruder to form pellets.

(2) Preparation of PPS composition PPS was prepared in the same manner as in the preparation of the copolymerized PPS composition (1) except that 101 mol of p-diclebenzene was used as the main component monomer and no subcomponent monomer was used. A composition was prepared. The melt viscosity of the PPS composition was 300
The melting point was 0 poise and the melting point was 285 ° C.

(3) Production of Laminated Sheet of Copolymerized PPS and PPS The copolymerized PPS composition and PPS composition obtained in (1) and (2) were each subjected to 1 mm at 180 ° C. for 3 hours.
After drying under a reduced pressure of Hg, the mixture was supplied to a separate extruder, and in a molten state, the above-mentioned polymers were guided to be laminated by a double-tube laminating apparatus located above the die.
Discharged from the die die, cooled and solidified by the cooling rotary drum,
A 20 μm-thick (unoriented) film of a two-layer laminated sheet of copolymerized PPS / PPS was obtained (the thickness of the copolymerized PPS layer was 8 μm, P
The thickness of the PS layer was 12 μm. ).

(4) Preparation of Circuit Layer Copper was plated on the PPS layer of the two-layer laminated sheet of (3), and a desired electric circuit was formed with an aqueous ferric chloride solution. The PPS layer was previously subjected to a corona discharge treatment of 6000 J / m ² . The thickness of the copper plating layer was 1 μm.

(5) Preparation of Metal-Based Circuit Board The copolymerized PPS layer of the circuit layer obtained in (4) and an aluminum plate having a thickness of 1.6 mm were thermocompression bonded. The thermocompression bonding method is a hot plate pressing method under conditions of a temperature of 255 ° C. and a pressure of 5 kg /.
cm ² . The obtained metal-based circuit board was used in Example 1.
And

Example 2 The PPS layer of the two-layer laminated sheet obtained in Example 1
A corona discharge treatment of 0 J / m ² was performed, an electric circuit was formed on the surface of the PPS layer by using a silver-containing conductive paste by a silk printing method, and further, electroless plating of copper was performed on the surface of the electric circuit. Next, a metal-based circuit board was prepared by the method of Example 1.

Comparative Example 1 The PPS composition of Example 1 was supplied to an extruder having a hole diameter of 40 mm, discharged from a T-die die, cooled and solidified by a cooling rotary drum, and the PPS composition sheet (unstretched sheet) was 25 μm thick. Got something. An electric circuit was formed on the PPS composition sheet by the method of Example 1 to prepare a metal-based circuit board. However, the thermocompression bonding temperature with a metal plate (aluminum plate) was 280 ° C.

Comparative Example 2 The copolymerized PPS composition of Example 1 was supplied to an extruder having a hole diameter of 40 mm, discharged from a T-die die, cooled and solidified by a cooling rotary drum, and then cooled to 25% of a copolymerized PPS sheet (unstretched sheet).
A μm thick one was obtained. An electric circuit was formed on the copolymerized PPS sheet by the method of Example 1 to prepare a metal-based circuit board. However, the thermocompression bonding temperature with a metal plate (aluminum plate) was 255 ° C.

Example 3 Biaxial stretching of a laminate of the PPS composition obtained under the conditions of Example 1 and the copolymerized PPS composition in three layers (copolymerized PPS composition / PPS composition / copolymerized PPS composition) And heat treated. The stretching conditions were a temperature of 98 ° C. in both the longitudinal direction and the width direction, and the stretching ratio was 3.9 times in the longitudinal direction and 3.7 times in the width direction. Further, in a subsequent heat treatment chamber in the same tenter, heat treatment is performed at 265 ° C. for 10 seconds, and a three-layer biaxially oriented film having a thickness of 30 μm (PPS layer thickness: 18 μm, copolymerized PP)
(S layer thickness 6 μm / one side) was obtained. The film is
C., 2 minutes free relaxation.

The aluminum plate used in Example 1 was applied to the obtained three-layer laminated biaxially oriented film, and 18 μm
(1 oz.) Rolled copper foil was thermocompression bonded. The conditions for thermocompression bonding were a temperature of 265 ° C. and a pressure of 10 kg / cm ² . Further, the copper foil surface of the laminate was etched with a ferric chloride aqueous solution to form a desired electric circuit, thereby producing a metal-based circuit board.

Comparative Example 3 "TORELINA" type 30 as a biaxially oriented PPS film
00 (manufactured by Toray Industries, Inc.) 25 μm was used. Further, both surfaces of the film were subjected to a plasma treatment (applied voltage: 0.6 kV, processing speed: 0.25 m / min) in an argon gas stream, an electric circuit was formed under the conditions of Example 2, and a metal-based circuit board was formed. .

Comparative Example 4 The aluminum plate and rolled copper foil of Example 3 were laminated on both sides of the biaxially oriented PPS film used in Comparative Example 3 with the following adhesive. A heat-resistant urethane-based adhesive “Adcoat” 76P1 (manufactured by Toyo Morton Co., Ltd.) was used as the adhesive. The method of applying the adhesive is as follows using a gravure roll coater.
It was applied to a thickness of 5 μm / Dry. The drying condition of the solvent for the adhesive was 120 ° C. for 1 minute. The laminating method is a pressure of 3 kg at a temperature of 100 ° C. by a hot press roll method.
/ Cm, and the adhesive was cured at 80 ° C. for 50 hours. Next, an electric circuit was formed under the conditions of Example 2,
A metal-based circuit board was created.

Example 4 The amount of the main component monomer, p-dichlorobenzene, added was 94.8.
The copolymerized PPS was polymerized under the same conditions as in Example 1 except that the mol% and the addition amount of the auxiliary component monomer m-dichlorobenzene were 5 mol% (melting point: 263 ° C.). Further, the same PPS as in Example 1 was used. Further, a three-layer laminated biaxially oriented film was prepared under the conditions of Example 3, and an electric circuit was formed under the conditions of Example 3, thereby preparing a metal-based circuit board. However, the thermocompression bonding temperature at that time was 265 ° C.

Example 5 Amount of addition of p-dichlorobenzene as a main component monomer was 69.8.
Mol%, the amount of the additional component monomer m-dichlorobenzene was 30 mol%, and the other conditions were the same as in Example 1.
Was polymerized (melting point: 201 ° C.). In addition, PPS is used in the first embodiment.
The same one as described above was used. Further, a three-layer laminated biaxially oriented film was produced under the conditions of Example 3, and an electric circuit was formed under the conditions of Example 3, to produce a metal-based circuit board. However, the thermocompression bonding temperature at that time was 230 ° C.

Example 6 A glass cloth (EPC030, 34 μm, manufactured by Arisawa Seisakusho) was impregnated with resin using the PPS composition sheet prepared in Comparative Example 1. The above glass cloth was sandwiched between two PPS composition sheets, and hot-pressed by a hot plate press method. The temperature is 300 ° C., the pressure is 10 kg / cm ² ,
Was 1 hour. Further, rapid cooling (water cooling) was performed. The thickness of the obtained resin-impregnated sheet was 60 μm. An electric circuit was formed on both surfaces of the resin-impregnated sheet under the conditions of Example 3 via the 12 μm-thick copolymerized PPS composition sheet prepared under the conditions of Comparative Example 2 to prepare a metal-based circuit board.

Evaluation of Examples and Comparative Examples Table 1 shows the evaluation results of the metal-based circuit boards of Examples 1 to 6 and Comparative Examples 1 to 3.

The circuit boards of the present invention of Examples 1 to 6 may be metal-based circuit boards excellent in solder heat resistance, adhesiveness, high frequency characteristics (frequency characteristics of dielectric loss) and thermal dimensional stability. I understand.

The metal-based circuit boards of Examples 1 to 3 are particularly excellent in adhesiveness and thermal dimensional stability as compared with conventional ones, and maintain the high-frequency characteristics of PPS.

The objects of the present invention can be achieved even if the addition ratio of the main component monomer and the auxiliary component monomer (copolymer component) of the copolymerized PPS used for the adhesive layer is changed in the metal base circuit boards of Examples 4 and 5. However, it can be seen that when the addition ratio of the copolymer component exceeds 30 mol%, heat resistance and thermal dimensional stability decrease, and when it is less than 5 mol%, the adhesiveness to the circuit layer decreases.

The metal base circuit board of the sixth embodiment is made of PP
It uses an S-resin impregnated fiber sheet, further improves heat resistance and thermal dimensional change rate, and sufficiently satisfies the object of the present invention in high-frequency characteristics.

On the other hand, the metal-based circuit board of Comparative Example 1
Since it is a substrate using only the unstretched sheet of the PS composition, the adhesive strength to a metal plate is poor, and peeling occurs in a solder bath due to the effect, and the soldering heat resistance temperature is lowered.

Since the metal base circuit board of Comparative Example 2 is a board using only an unstretched sheet of the copolymerized PPS composition, the heat resistance of the insulating layer is poor and the object of the present invention cannot be achieved.

Further, the metal base circuit board of Comparative Example 3 uses only the biaxially oriented PPS film, and has a poor adhesion as in Comparative Example 1. In addition, a dimensional change due to heat is large.

The metal base circuit board of Comparative Example 4 uses only a biaxially oriented PPS film, and is formed by laminating a circuit and a metal plate via an adhesive other than PPS. The properties of the adhesive degrade the heat resistance and high frequency characteristics of PPS.

[0072]

[Table 1] Example 7 The circuit layer of Example 3 (electric circuit / copolymerized PPS composition / P
The PS composition / copolymerized PPS composition) was superposed on six layers to form a multilayer, and each layer was connected by copper plating to form a six-layer multilayer wiring board. The thermocompression bonding of each layer was performed under the conditions of Example 3. Furthermore, the copolymerized PPS of the lowermost layer of the multilayer wiring board
The layer and a 1 mm thick silicon steel sheet were laminated by thermocompression bonding. The conditions of Example 3 were used as the lamination conditions.

As a result of evaluating the characteristics of the obtained multilayer-type metal-based circuit board, the heat resistance, high-frequency characteristics, adhesive strength, and thermal dimensional change rate sufficiently satisfied the object of the present invention.

[0074]

According to the present invention, a metal-based circuit board having excellent heat resistance, high-frequency characteristics, thermal dimensional stability, and the like is obtained because of the above-mentioned structure. It was possible to improve the adhesive force without deteriorating the characteristics of PPS.

The metal base circuit board of the present invention is most suitable for a heat dissipation board, a magnetic circuit board, an electromagnetic wave shielding board, and the like.

Continuation of the front page (58) Field surveyed (Int. Cl. ⁷ , DB name) B32B 27/00 B32B 15/08 H05K 1/05

Claims (2)

(57) [Claims] 1. A sheet comprising a resin composition containing poly-p-phenylene sulfide as a main component and a layer (A) comprising an electric circuit are copolymerized with at least one or more kinds other than p-phenylene sulfide units. A metal-based circuit board, which is laminated on a metal (C) layer via a resin composition (B) layer made of copolymerized polyphenylene sulfide containing units. 2. The method according to claim 1, wherein the layer (A) is poly-p.
-A resin composition (B) layer comprising a copolymerized polyphenylene sulfide containing at least one or more copolymerized units other than p-phenylene sulfide units in a sheet containing a resin composition containing phenylene sulfide as a main component; A metal-based circuit board comprising an electric circuit formed therethrough.