JPH0691812A - Metal base printed circuit board - Google Patents

Abstract

PURPOSE:To provide a metal base circuit board excellent in the bonding strength with a metal plate while holding the excellent hygroscopic characteristic, high frequency characteristic or heat-resistance of PPS. CONSTITUTION:A layer (A) consisting of a sheet composed of a resin compsn. based on poly-p-phenylene sulfide and an electric circuit is laminated to a metal layer (C) through a layer (B) of a resin compsn. composed of copolymerized polyphenylene sulfide containing at least one or more kind of a copolymerizable unit other than a p-phenylene sulfide unit.

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to metal-based circuit boards.

[0002]

2. Description of the Related Art In the fields of electric and electronic parts, various characteristics such as heat resistance, thermal dimensional stability, low hygroscopicity, flame retardancy, and high frequency characteristics are highly dimensional from the viewpoint of miniaturization and high functionality of equipment. The demand for balanced metal-based circuit boards is increasing.

As a circuit board in this field, a polyimide film, a fluorine-based film, a sheet of glass cloth impregnated with an epoxy resin (hereinafter referred to as glass epoxy) on which an electric circuit is formed with a metal foil is used. A metal plate laminated with an adhesive was used. Furthermore, poly-p-phenylene sulfide (hereinafter P
It is called PS. (2) 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 been particularly attracting attention in recent years, and these circuit layers and metal plates are laminated. There are also proposals (Japanese Patent Laid-Open No. 1-95586, etc.).

[0004]

However, the above metal base circuit board has the following problems.

(1) A metal base circuit board using a circuit board made of a polyimide film has high heat resistance, but has a high moisture absorption rate and poor high frequency characteristics.

(2) The one using a fluorine-based film has poor adhesive workability.

(3) The one using a glass epoxy substrate has a large moisture absorption rate and is inferior in high frequency characteristics. Further, when considering the multilayering of the circuit board, the thickness becomes thicker.

(4) A conventional circuit board using a PPS sheet or PPS film is excellent in heat resistance, low hygroscopicity, high frequency characteristics, etc. However, when a metal base circuit board is manufactured using an adhesive, Satisfactory properties could not be maintained because the excellent properties of PPS were degraded.

On the other hand, it has been proposed to carry out a surface treatment such as plasma treatment and heat-bond it to a metal plate for lamination without using an adhesive. However, there is a problem in that the adhesive force is insufficient and, for example, when the metal plate is placed in a solder bath, the metal plate and the circuit layer are easily separated from each other. It is an object of the present invention to provide a metal base circuit board which has excellent moisture absorption characteristics, high frequency characteristics, heat resistance, etc. of PPS, and which has excellent adhesion to a metal plate while maintaining these characteristics.

[0010]

That is, according to the present invention, a sheet containing a resin composition containing poly-p-phenylene sulfide as a main component and an (A) layer comprising an electric circuit,
A metal characterized by being laminated on a metal (C) layer via a resin composition (B) layer consisting of a copolymerized polyphenylene sulfide containing at least one copolymerized unit other than a p-phenylene sulfide unit. It is a base circuit board.

In the present invention, PPS is a constitutional unit in which 80 mol% or more, preferably 90 mol% or more of the repeating unit is represented.

[Chemical 1] A polymer comprising a structural unit represented by If the amount of such a component is less than 80 mol%, the crystallinity of the polymer, the heat transition temperature, etc. are low, and the heat resistance, dimensional stability, mechanical properties, etc., which are the features of the resin composition containing PPS as a main component, are impaired.

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

In the present invention, the resin composition containing poly-p-phenylene sulfide as a main component (hereinafter referred to as "PPS composition") means poly-p-phenylene sulfide of 6%.
A composition containing 0% by weight or more. PPS content is 60
If less than wt%, the mechanical properties of the sheet made of the composition,
The heat resistance and heat fusion properties are impaired. Further, the remaining less than 40% by weight in the composition may contain additives such as polymers other than PPS, inorganic or organic fillers, lubricants and colorants. Further, the melt viscosity of the PPS composition has a temperature of 30
100 to 5 at 0 ° C. and a shear rate of 200 sec ^−1.
0000 poise, more preferably in the range of 500 to 20000 poise, is preferable from the viewpoint of sheet and film processability.

The layer (A) in the present invention is a circuit layer comprising a sheet containing the PPS composition and an electric circuit. Here, the sheet containing the PPS composition is a sheet containing at least the PPS composition, and is not particularly limited as long as the object of the present invention is not impaired. For example, a non-stretched sheet of PPS or a biaxially stretched film, a sheet obtained by laminating the sheet or a sheet with a film made of another resin composition, or an inorganic or organic fiber sheet (nonwoven fabric, cloth,
A general term for paper, felt, etc.), laminated with resin, and impregnated with resin can be mentioned. The thickness of layer A is 5 to 300 μm
Is preferred.

In the present invention, a copolymerized polyphenylene sulfide (hereinafter referred to as a copolymerized PPS) means a p-phenylene sulfide unit as a main repeating unit.
It refers to one formed by copolymerizing at least one copolymerized unit. The content of the p-phenylene sulfide unit in the copolymerized polyphenylene sulfide is 50 to 95 mol%, preferably 70 to 92 mol% based on all repeating units.
Is the range. If the content is less than 50 mol%, the heat resistance and thermal dimensional stability when used as a metal-based circuit board will be poor, while if it exceeds 95 mol%, the adhesion of the circuit layer to the metal layer will deteriorate. To do.

As the copolymerization unit, m-phenylene sulfide unit,

[Chemical 2]

[Chemical 3] (Where X represents an alkylene, CO or SO ₂ unit)

[Chemical 4]

[Chemical 5] (Wherein R represents an alkyl group, a nitro group, a phenylene group, or an alkoxy group), and a unit of these composites may be present. Preferred copolymerized units are m-phenylene sulfide units. The copolymerization amount of these units is 3 to 50 mol%, preferably 5 to 30 mol%, based on the total repeating units, of the copolymerizing units which are the second largest after the p-phenylene sulfide unit which is the main repeating unit of the copolymerized PPS. It is a range. When the content is less than 3 mol%, the adhesive strength with the circuit layer of the circuit board deteriorates. On the other hand, when it exceeds 50 mol%, the heat resistance and thermal dimensional stability of the circuit board become poor. The rest of the repeating units of the copolymerized PPS may be composed of other copolymerizable units,

[Chemical 6] The trifunctional phenylene sulfide unit represented by is preferably 1 mol% or less of the whole copolymer.

The copolymerization mode 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, a resin composition comprising copolymerized PPS (hereinafter referred to as a copolymerized PPS composition) (B) means that the copolymerized PPS in the resin component is 80% by weight or more, preferably 90% by weight. What is occupied above. If the remaining amount is less than 20% by weight, there is no problem to include organic and inorganic additives other than copolymerized PPS, inert particles and the like.

The melting point of the copolymerized PPS composition of the present invention is 2
The range of 00 to 285 ° C 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
It is 0000 poise.

The electric circuit in the present invention is an electric passage in which a conductor is patterned, and the conductor is a metal such as copper, aluminum, or iron, or an alloy of two or more kinds, a metal such as copper or silver, or carbon. Examples of the paste include the conductor of (1). Further, the circuit layer of the present invention may be a laminate of two or more of the above circuit layers. In this case, within the scope of the present invention, two or more types of circuit layers (for example, 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. Although the kind of metal is not particularly limited, a steel plate, a silicon steel plate, an aluminum plate or the like is usually used.

The metal-based circuit board of the present invention means PPS.
A sheet containing the 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 B layer is preferably in the range of 2 to 100 μm, and more preferably 2 to 70 μm in terms of the balance between adhesiveness and heat resistance. Further, the thickness of the sheet containing the PPS composition of the A layer, which can be measured from the cross-sectional photograph of the metal base circuit board of the polarization microscope, is a (μ
m), and the thickness of the B layer is b (μm), b / a is 0.
The range of 02 to 1.2 is particularly preferable in terms of the balance of adhesiveness, heat resistance, moisture absorption characteristics, high frequency characteristics and the like. Further, the content of copolymerized PPS contained in the resin composition of the layer A (Aco
p) and the content (Bcop) of the copolymerized PPS contained in the resin composition of the B layer are preferably Bcop> Acop, and the melting point of the resin composition of the A layer and the resin composition of the B layer of It is particularly preferable that the difference in melting point is in the range of 5 to 90 ° C. from the viewpoint of workability and easy achievement of the object of the present invention. The B layer may or may not have molecules oriented.

Next, a method of manufacturing the metal base circuit board of the present invention will be described.

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

[Chemical 7]

[Chemical 8]

[Chemical 9] (Here, X represents an alkylene, CO or SO ₂ unit.)

[Chemical 10]

[Chemical 11] (Wherein R represents an alkyl group, a nitro group, a phenylene group, or an alkoxy group), and plural accessory component monomers may be present. Preferred subcomponent monomers are

[Chemical 12] Is.

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

Next, the copolymerized PPS resin composition is molded into a sheet. In the case of producing an unstretched, non-oriented sheet, the resin composition melted by an extruder is quantitatively cast from a die onto a metal drum and rapidly cooled. Further, in the case of producing an oriented film, an unstretched or 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 2-4.5 times at ° C. The heat treatment is performed in the range of 180 ° C. to the melting point for 1 to 60 seconds under a constant length or a restricted shrinkage of 20% or less.

On the other hand, the PPS of the present invention is polymerized in the same manner as the copolymerized PPS, but as described in the present invention, the accessory component monomer is not blended or its blending is reduced.

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

[Chemical 13] You may mix | blend the trifunctional monomer like this.

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

The sheet of the PPS resin composition used for the layer A in the present invention 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 laminated sheet with a biaxially stretched film, a laminated body with a fiber sheet, a resin-impregnated body, or the like is used. The unstretched sheet and biaxially stretched film of the PPS resin composition can be produced by the same method as in the case of the copolymerized PPS resin composition. The above-mentioned laminated sheet is obtained by laminating a PPS sheet or PPS film and another unstretched sheet other than PPS or a biaxially stretched film through an adhesive or by heat fusion (thermocompression bonding). Laminating by heat fusion is preferable because the object of the present invention can be easily achieved.

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

An electric circuit is formed on the sheet thus obtained. A method for forming an electric circuit can be formed by providing a metal layer by a known method, for example, a method such as laminating, vapor deposition, plating or the like, and etching the pattern of the electric circuit.
A ferric chloride aqueous solution or the like is usually used for etching. A circuit pattern can also be formed by a method such as silk printing using a conductive paste containing a conductor such as metal or carbon. Further, a method for manufacturing a multilayer circuit board is such that a hole for electrically connecting the layers is opened in the above-mentioned circuit layer if necessary, and two or more layers are superposed, and each circuit layer is thickened by plating, a conductive paste or the like through the hole. Connect in the vertical 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 obtain the metal base circuit board of the present invention. To manufacture. As the laminating method, the above three layers are superposed in the order of A / B / C, and are carried out by a heating press roll method, a hot plate pressing method or the like. Laminating condition is 200 ℃ ~
1 to 40 kg at the temperature of the melting point of the PPS resin composition of layer A
A pressure range of / cm ² is preferable in terms of workability and adhesiveness.

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

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

[0036]

[Measurement methods of physical properties and evaluation methods of effects] The characteristic values of the present invention are based on the following measurement methods and evaluation criteria.

(1) Soldering heat resistance temperature The metal base circuit board is soaked for 30 seconds so that the electric circuit may come into contact with the solder liquid surface set at each temperature (accuracy of ± 5 ° C. or less) and taken out. At that time, changes in the insulating film, changes in the state of the circuit, peeling of the metal plate and the circuit board, etc. were observed and expressed as the temperature of the limit solder. The electrical circuit is 5mm apart, 5mm
Adjusted to the width and the size of the board.

(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 base material was pulled to measure the peel strength (g / cm). Peeling speed is 50 mm
The peel angle is 180 degrees in / min.

(3) Frequency characteristic of dielectric loss It was measured according to JIS-C-6481.

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

(4) Thickness measurement 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 cross section photograph.

(5) Thermal dimensional change rate: 85 mm square, 75 m at each corner of the metal base circuit board
Markings at m intervals were provided. Its dimensions were accurately measured with a microscope (αmm). Next, the metal plate was aged in a solder bath set at 250 ° C. for 30 seconds so as to come into contact with the solder, and then the distance between the markings was measured with a microscope (βm.
m). The thermal dimensional change rate was calculated by the following formula.

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

[0044]

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

Example 1 (1) Preparation of Copolymerized PPS Composition In an autoclave, 100 mol of sodium sulfide nonahydrate, 45 mol of sodium hydroxide and 25 liter of N 2 were added.
-Methyl-pyrrolidone (hereinafter referred to as NMP) was charged, the temperature was gradually raised to 220 ° C with stirring, and the contained water was removed by distillation.

91 mol% of p-dichlorobenzene as a main component monomer, 10 mol% of m-dichlorobenzene as a minor component monomer, and 0.2 mol% of 1,2,4 into the system after dehydration. 5 liters of trichlorobenzene NM
P was added together with P, nitrogen was pressure-filled at 170 ° C. under 3 kg / cm ² , and then the temperature was raised and polymerization was carried out at 260 ° C. for 4 hours. After the completion of the polymerization, the mixture was cooled and the polymer was precipitated in distilled water, and a small block polymer was collected with a wire net having a 150 mesh opening.

This polymer was washed 5 times with distilled water at 90 ° C. and then dried at 120 ° C. under reduced pressure to obtain a melt viscosity of 1
Copolymer P in the form of white particles having a melting point of 253 ° C.
A PS composition was obtained.

Then, 50 g of spherical silica having a diameter of 0.5 μm was mixed with 10 kg of the copolymerized PPS, and extruded into a gut form at 320 ° C. with a 30 mmφ twin-screw extruder, and pelletized.

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

(3) Formation of Laminated Sheet of Copolymerized PPS and PPS The copolymerized PPS composition and the PPS composition obtained in (1) and (2) were heated at 180 ° C. for 3 hours and 1 mm, respectively.
After being dried under reduced pressure of Hg, they were supplied to separate extruders, and in a molten state, the above two polymers were guided to be laminated by a double-tube type laminating device on the upper part of the die, and the T
It is discharged from the die-type die and cooled and solidified by a cooling rotary drum.
A 20 μm thickness (unoriented) 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 The PPS layer of the two-layer laminated sheet of (3) was plated with copper to form a desired electric circuit 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 base circuit board The copolymerized PPS layer of the circuit layer obtained in (4) and a 1.6 mm thick aluminum plate were thermocompression bonded. The thermocompression bonding method is a hot plate pressing method, the conditions are a temperature of 255 ° C. and a pressure of 5 kg /
cm ² . The obtained metal base circuit board is used in Example 1.
And

Example 2 The PPS layer of the two-layer laminated sheet obtained in Example 1 had 600
A corona discharge treatment of 0 J / m ² was performed, an electric circuit was formed on the surface of the PPS layer by a silk printing method using a conductive paste containing silver, and electroless plating of copper was performed on the surface of the electric circuit. Next, a metal base circuit board was prepared by the method of Example 1.

Comparative Example 1 A PPS composition sheet (unstretched sheet) having a thickness of 25 μm was prepared by supplying the PPS composition of Example 1 to an extruder having a hole diameter of 40 mm, discharging it from a T-die type die and cooling and solidifying it by a cooling rotary drum. Got one. An electric circuit was formed on this PPS composition sheet by the method of Example 1 to prepare a metal base circuit board. However, the thermocompression bonding temperature with the 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 type die, cooled and solidified by a cooling rotary drum, and a copolymerized PPS sheet (unstretched sheet) of 25 was obtained.
It was obtained with a thickness of μm. An electric circuit was formed on this copolymerized PPS sheet by the method of Example 1 to prepare a metal base circuit board. However, the thermocompression bonding temperature with the metal plate (aluminum plate) was 255 ° C.

Example 3 A PPS composition and a copolymerized PPS composition obtained under the conditions of Example 1 were laminated in three layers (copolymerized PPS composition / PPS composition / copolymerized PPS composition) and biaxially stretched. 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 to obtain a 3-layer laminated biaxially oriented film of 30 μm (PPS layer thickness 18 μm, copolymerized PP.
S layer thickness 6 μm / one side) was obtained. 200 the film
Free relaxation was performed at ℃ for 2 minutes.

The three-layer laminated biaxially oriented film obtained was coated with the aluminum plate used in Example 1 and the opposite surface thereof was 18 μm thick.
A (1 ounce) 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 an aqueous solution of ferric chloride to form a desired electric circuit, and a metal base circuit board was prepared.

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

Comparative Example 4 The aluminum plate of Example 3 and rolled copper foil were laminated on both sides of the biaxially oriented PPS film used in Comparative Example 3 with the following adhesive. As the adhesive, a heat-resistant urethane adhesive "Adcoat" 76P1 (manufactured by Toyo Morton Co., Ltd.) was used. A gravure roll coater is used to apply the adhesive.
It was applied to a thickness of 5 μm / Dry. The solvent for the adhesive was dried at a temperature of 120 ° C. for 1 minute. The lamination method is a heating press roll method at a temperature of 100 ° C. and a pressure of 3 kg.
/ 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 base circuit board was created.

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

Example 5 Amount of p-dichlorobenzene as a main component monomer added 69.8
Copolymerized PPS under the same conditions as in Example 1, except that the amount of the secondary component monomer m-dichlorobenzene added was 30 mol%.
Was polymerized (melting point 201 ° C.). The PPS is the first embodiment.
The same as was used. Furthermore, 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 to prepare a metal base circuit board. However, the thermocompression bonding temperature at that time was 230 ° C.

Example 6 A glass cloth (34 μm manufactured by EPC030 Arisawa Seisakusho) was impregnated with 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 pressing method. The temperature is 300 ° C, the pressure is 10 kg / cm ² , and the temperature is 300 ° C.
Hold time was 1 hour. Further, it was rapidly cooled (water cooled). 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 through the 12 μm-thick copolymerized PPS composition sheet prepared under the conditions of Comparative Example 2 to prepare a metal base circuit board.

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

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

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

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

The metal base circuit board of the sixth embodiment is made of PP.
Since the S resin-impregnated fiber sheet is used, the heat resistance and the thermal dimensional change rate are further improved, and the high frequency characteristics sufficiently satisfy the object of the present invention.

On the other hand, the metal base circuit board of Comparative Example 1 is P
Since it is a substrate using only an unstretched sheet of the PS composition, it has poor adhesion to a metal plate, and due to this, peeling occurs in the solder bath and the solder heat resistance temperature becomes low.

Since the metal base circuit board of Comparative Example 2 is a board using only the 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.

The metal base circuit board of Comparative Example 3 uses only the biaxially oriented PPS film and has a poor adhesive strength as in Comparative Example 1. Also, the 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 laminated with a circuit and a metal plate via an adhesive other than PPS. The characteristics of the adhesive deteriorate the heat resistance and high frequency characteristics of PPS.

[0072]

[Table 1] Example 7 The circuit layer of Example 3 (electrical circuit / copolymerized PPS composition / P
The PS composition / copolymerized PPS composition) was laminated in 6 layers to form a multilayer, and the respective layers were connected by copper plating to prepare a 6-layer multilayer wiring board. Thermocompression bonding of each layer was performed under the conditions of Example 3. Further, the copolymerized PPS of the bottom layer of the multilayer wiring board
The layers and a 1 mm thick silicon steel plate were laminated by thermocompression bonding. The lamination conditions used were those of Example 3.

As a result of evaluating the characteristics of the obtained multi-layered metal base circuit board, the heat resistance, the high frequency characteristics, the adhesive strength and the thermal dimensional change rate were sufficiently satisfied with the object of the present invention.

[0074]

EFFECTS OF THE INVENTION The present invention provides a metal base circuit board having excellent heat resistance, high frequency characteristics, thermal dimensional stability and the like because of the above-mentioned constitution, and the conventional problems (without using an adhesive that deteriorates the characteristics of PPS). It has become possible to improve the adhesive strength without deteriorating the characteristics of PPS which was manufactured in (1).

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

Claims (2)

[Claims] 1. A (A) layer consisting of a sheet containing a resin composition containing poly-p-phenylene sulfide as a main component and an electric circuit is copolymerized with at least one kind other than a p-phenylene sulfide unit. A metal base circuit board, which is laminated on a metal (C) layer via a resin composition (B) layer composed of a copolymerized polyphenylene sulfide containing units. 2. The (A) layer according to claim 1 is poly-p.
A resin composition (B) layer composed of a copolymerized polyphenylene sulfide containing at least one copolymerized unit other than a p-phenylene sulfide unit on a sheet containing the resin composition containing phenylene sulfide as a main component; A metal base circuit board having an electric circuit formed therethrough.