JPH0645714A - Circuit substrate and multilayer circuit substrate - Google Patents

Abstract

(57) [Abstract] [Purpose] Heat resistance, thermal dimensional stability, high-frequency characteristics, moisture absorption characteristics, etc. are balanced in a high dimension, and the adhesion to the circuit layer and the conductor resistance of the circuit are small. A circuit board (including a multilayer circuit board) suitable for high-speed processing and high-frequency compatibility is provided. [Structure] A fiber sheet is impregnated with a resin composition containing poly-p-phenylene sulfide as a main component, and at least one unit other than p-phenylene sulfide units is formed on the surface of the sheet.
A circuit board in which an electric circuit made of a metal layer is formed via a resin composition layer made of a copolymerized polyphenylene sulfide containing one or more copolymerized units, and a multilayer circuit board in which the circuit board is laminated.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a circuit board using a resin-impregnated sheet obtained by impregnating a fiber sheet with poly-p-phenylene sulfide resin as an insulating base material.

[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 circuit boards is increasing. Furthermore, there are demands for higher-speed signal processing, lower circuit resistance, through-hole processability, and thinner walls.

As a circuit board in this field, a base material (hereinafter referred to as glass epoxy) in which glass cloth is impregnated with an epoxy resin is used to form an electric circuit with a metal foil such as copper, a polyimide film, a fluorine-based film or the like. Is formed. Furthermore, an unstretched sheet of poly-p-phenylene sulfide (hereinafter referred to as PPS) (hereinafter referred to as PP)
It is called S sheet. ) And a biaxially oriented film (hereinafter PPS)
It is called a film. Recently, a circuit board using) as an insulating base material has attracted particular attention. Also known is a circuit board in which an electric circuit is formed by reinforcing a PPS resin with a fiber sheet such as glass fiber (Japanese Patent Laid-Open No. 2-415004, etc.).

[0004]

However, each of the above-mentioned films and laminates has the following problems.

Those using glass epoxy as an insulating base material are inferior in low hygroscopicity and high frequency characteristics, and it is difficult to reduce the wall thickness. The one using a polyimide film is rich in heat resistance, but easily absorbs moisture,
Inferior high frequency characteristics. Further, the one using a fluorine-based film has poor adhesiveness, and it is difficult for conductive paste or plating to be applied when processing a through hole.

On the other hand, the PPS sheet alone as an insulating base material satisfies various characteristics such as thermal dimensional stability, low hygroscopicity, flame retardancy, and high frequency characteristics, but compared with the biaxially oriented film. The heat-resistant temperature is low (heat deformation tends to occur when it exceeds the glass transition point), and as the heating process increases, crystallization progresses and becomes brittle. When used as a printed circuit board, the crystal size and the like are controlled to satisfy heat resistance and brittleness to some extent, but there is a problem that thermal deformation easily occurs when heat is rapidly applied.

In addition, a PPS film alone as an insulating base material causes a dimensional change due to thermal contraction, and therefore, when heat is applied in the manufacturing process of a circuit board, for example, a circuit shift easily occurs. Further, there is a problem that the laminated circuit board is easily torn during processing of through holes.

A circuit board using a PPS resin reinforced with glass fiber as an insulating base material has excellent heat resistance, thermal dimensional stability, high frequency characteristics, flame retardancy, moisture absorption characteristics, etc. However, there is a problem that it is difficult to heat-fuse with a metal foil or metal plating, and the adhesive strength is weak. On the other hand, although it is possible to stack metal foils via an adhesive, the high-frequency characteristics and moisture absorption characteristics of the adhesive adversely affect the circuit board (that is, the characteristics of the adhesive control the characteristics of the circuit board as a whole). However, the excellent characteristics of PPS cannot be fully utilized. It is also proposed to form a circuit with conductive paste, but the conductor resistance of the circuit is large (for example, 20 times that of copper),
There was a limit to the fine patterning of circuits, and circuit design was limited to special ones.

The present invention pays attention to the excellent low hygroscopicity, flame retardancy and high frequency characteristics of PPS, and is a sheet obtained by impregnating a fiber sheet with PPS resin, which can remarkably improve heat resistance and dimensional stability. Uses as an insulating base material, maintains high-frequency characteristics, dimensional stability, and heat resistance, has a small circuit resistance value, enables fine patterning, and is especially suitable for high-frequency applications. It is intended to be provided.

[0010]

[Means for Solving the Problems] That is, at least one or more kinds of units other than p-phenylene sulfide units are present on the surface of a sheet obtained by impregnating a fiber sheet with a resin composition containing poly-p-phenylene sulfide as a main component. A circuit board comprising an electric circuit formed of a metal layer formed through a resin composition layer of a copolymerized polyphenylene sulfide (hereinafter referred to as a copolymerized PPS) containing a polymerized unit, and the circuit board are laminated. It is a multilayer circuit board characterized by being formed.

The fibrous sheet in the present invention is a thin sheet composed of an aggregate of fibers, such as cloth, cloth,
A general term for felt, non-woven fabric, paper, etc., thickness 10-100
The thickness is preferably 0 μm, more preferably 10 to 700 μm. The fiber sheet is processed for easy adhesion, coloring, etc.
It is possible to mix or stack materials of one or more kinds. Among the fiber sheets, a cloth is preferable, and a glass fiber cloth is particularly preferable in terms of heat resistance, dimensional stability and processability.
Here, the impregnation means that the resin has entered into the surroundings of the elemental fibers constituting the fiber sheet, and has adhered and solidified with the elemental fibers.

It is preferable that the fiber sheet has no melting point up to a temperature of 400 ° C.
A fiber sheet that is infusible at a temperature of 00 ° C. Here, infusible means a state in which it does not melt or soften when exposed to a temperature of 400 ° C. If the fiber sheet used in the present invention does not have the above characteristics, the thermal dimensional stability becomes insufficient when the circuit board of the present invention is exposed to a temperature of around 300 ° C.

In the present invention, PPS is a constitutional formula 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, the repeating unit of 20
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 copolymerizing the polymer may be random or block type.

In the present invention, the resin composition containing poly-p-phenylene sulfide as the 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 it is less than 5% by weight, mechanical properties, heat resistance, heat fusion property and the like of the impregnated sheet made of the composition 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. Furthermore, the melt viscosity of the PPS composition is 100 at a temperature of 300 ° C. and a shear rate of 200 sec ^−1.
~ 50,000 poise, more preferably 500-2000
The range of 0 poise is preferable from the viewpoint of workability of lamination.

In the present invention, copolymerized PPS means p-
A phenylene sulfide unit is a main repeating unit, and is formed by copolymerizing one or more copolymerized units. The content of p-phenylene sulfide unit in the copolymerized PPS is 50 to 9 based on all repeating units.
It is in the range of 5 mol%, preferably 70 to 92 mol%.
If the content is less than 50 mol%, the heat resistance and thermal dimensional stability when formed into a circuit board will be poor, while if it exceeds 95 mol%, the adhesive strength with the circuit layer of the circuit board will deteriorate.

As the copolymerization unit, an m-phenylene sulfide unit,

[Chemical 2]

[Chemical 3] (Here, 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) means that the above copolymerized PPS accounts for 80% by weight or more, preferably 90% by weight or more, of the resin component. Say If the remaining amount is less than 20% by weight, organic or inorganic additives other than copolymerized PPS,
It may contain 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
50 to 20 at 0 ° C. and a shear rate of 200 sec ⁻¹
000 poise, preferably 100-10,000 poise.

The insulating base material (hereinafter referred to as the insulating base material) of the circuit board of the present invention is the same as the surface (at least the surface on which the circuit is formed) of the resin-impregnated sheet obtained by impregnating the fiber sheet with the PPS composition. It is formed by stacking layers of a polymerized PPS composition. The impregnated state can be measured, for example, by the degree of ink penetration. In the insulating base material of the present invention, the PPS composition (B) is basically impregnated in the fiber sheet (A), and the copolymerized PPS composition (C) is provided on the PPS composition layer of the resin-impregnated fiber sheet. Although the layers are heat-sealed, part of the C layer may be impregnated in A together with B. That is, the basic constitution of the insulating base material of the present invention is as follows.
One mode is possible.

(1) An insulating base material in which a C layer is heat-sealed on at least one surface of a structure having the same thickness A and thickness B in a resin-impregnated fiber sheet in which A is impregnated with B.

(2) An insulating base material in which a C layer is heat-sealed to at least one surface of a structural body in which B is thicker than A in a resin-impregnated fiber sheet in which A is impregnated with B.

(3) A part of the C layer enters into at least one surface of the resin-impregnated fiber sheet in which A is impregnated with B (a part of the C layer is impregnated with A together with B). Means an insulating base material.

The C layer in the insulating base material of the present invention may be substantially non-oriented or may be uniaxially or biaxially oriented. Here, the ratio of the thicknesses of A, B, and C is not particularly limited, but when the thickness of each layer is measured from the cross section of the resin-impregnated fiber sheet with a microscope or the like, the thickness of B after resin impregnation is b, and the thickness of A is a. Then, b / a in the range of 0.25 to 2.5 is preferable from the viewpoint of impregnation property and thermal dimensional stability. In addition, A of the present invention
The layer does not necessarily have to be present at the center of the resin-impregnated fiber sheet in the thickness direction, and may be at a displaced position.

The thickness of the layer C of the present invention is 1 to 100 μm.
Is preferable, and when the thickness of C is c, a range of c / b of 0.01 to 2.5 is particularly preferable in terms of the balance of adhesive strength, heat resistance, and dimensional stability. The thicknesses of the B layer and the C layer can be measured, for example, from a cross-sectional photograph of the insulating base material with a polarization microscope due to the difference in the crystallization behavior of the resin compositions. The relationship between the content of copolymerized PPS (Bcop mol%) contained in the resin composition of layer B and the content of copolymerized PPS contained in the resin composition of layer C (Ccop mol%) is Bco
It is preferable that p <Ccop, and it is preferable that the difference between the melting point of the resin composition of B and the melting point of the resin composition of C is in the range of 5 to 90 ° C. from the viewpoint of workability and easy achievement of the object of the present invention. Further, the insulating substrate of the present invention has an ink penetration degree described below of 2.0 or less, more preferably 1.5 or less. If the degree of penetration exceeds 2.0, the thermal dimensional change rate becomes large and through hole processing becomes difficult, making it difficult to achieve the object of the present invention. Here, the degree of penetration of ink means that when a magic ink is applied to the surface of the insulating substrate in the cross-sectional direction (thickness direction), the ink soaks into the interior, but the length of the penetration (position at which the magic ink is applied) Is the value represented by the length (mm) measured from the surface of the sheet, which is the parameter representing the degree of impregnation of the insulating base material. Further, the thickness of the insulating base material of the present invention is preferably in the range of 20 to 1500 μm.

The metal layer in the present invention refers to a layer having a thickness of 1 to 100 μm, preferably 1 to 80 μm, which is made of a single metal such as copper, aluminum or iron or an alloy of two or more kinds. Further, an electric circuit is an electric passage in which the above-mentioned metal layer is patterned. In addition, the circuit board is one in which an electric circuit is formed on at least one surface of the above-mentioned insulating base material, and electric and electronic parts may be mounted thereon. A multilayer circuit board is a circuit board in which two or more layers are laminated and each layer is electrically connected by a conductor. The number of layers and the total thickness of the multilayer circuit board of the present invention are not particularly limited. It may be a multi-layer circuit board laminated in combination with a circuit board on which a circuit is formed of a conductor (for example, a conductive paste) other than the metal layer. That is, any multilayer circuit board including at least the circuit board of the present invention may be used as long as the object of the present invention is achieved. Further, the sizes of the circuit boards of the respective layers of the multilayer circuit board do not have to be the same, and for example, some circuit boards may protrude from the multilayer circuit board.

In the circuit board and the multilayer circuit board of the present invention, the bonding of the insulating base material and the electric circuit layer and the multilayer bonding of each wiring board are all performed by the copolymerized PPS resin layer (an adhesive other than PPS is used. Is not important) for maintaining various characteristics of PPS such as dielectric characteristics, moisture absorption characteristics, and heat resistance.

Next, a method of manufacturing the insulating base material 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.

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.

The PPS and copolymerized PP thus obtained
If necessary, an inorganic or organic additive is added to S,
A PPS composition and a copolymerized PPS composition.

Various methods can be used for impregnating a fiber sheet with this polymer, and the following method can be exemplified as a typical method.

(1) The above PPS composition (B) and copolymerized PPS composition (C) are coextruded to prepare an unstretched and unoriented laminated sheet of B and C (hereinafter referred to as PPS laminated sheet). A method for producing an insulating base material by aligning the B side of the PPS laminated sheet with a fiber sheet and thermocompression bonding.

First, a method for manufacturing the above PPS laminated sheet will be described. The composition of B and the composition of C are merged and laminated in a polymer channel between a melt extrusion device typified by an extruder and a die (slit die), or they are merged and laminated in a die. That is, the composition of B and the composition of C, which are supplied to separate extruders and are melted at a temperature equal to or higher than the melting points of the individual compositions, are combined between the extruder and the die or a joining device provided in the die. They are stacked in a molten state and extruded from the die. By rapidly cooling such a molten laminate to a temperature below the glass transition point of the sheet, a substantially non-oriented PPS laminated sheet is obtained. Here, the merging device has a function of laminating two or more polymer compositions in a molten state. Alternatively, only the PPS sheet may be prepared in advance under the above conditions, and then an unstretched sheet of the copolymerized PPS composition (hereinafter referred to as the copolymerized PPS sheet) may be extruded from the die and laminated.

The surface B of the non-oriented PPS laminated sheet thus obtained is laminated on the fiber sheet, and the pressure is 1 to 3 at a temperature of 290 to 350 ° C. which is higher than the melting point of the PPS composition.
Under the condition of 0 kg / cm ² , thermocompression bonding is performed with a heating roll press or a hot plate press. Further, the sheet is cooled through a cooling roll, a cooling plate, fresh air, water or the like for the purpose of maintaining the flatness of the sheet. When the thermocompression bonding temperature is lower than the melting point of the PPS composition, impregnation property is poor. Also the pressure is 1
If it is less than kg / cm ² , impregnation is poor, and conversely 30 kg /
When it exceeds cm ² , the flatness of the obtained insulating base material tends to deteriorate. In addition, the embodiment of the laminated constitution of the insulating base material of the present invention is the case of two layers of the fiber sheet and the PPS laminated sheet,
The PS laminated sheet, the fiber sheet, and the PPS laminated sheet may be laminated in this order in some cases, but the latter is preferable from the viewpoint of impregnation property. When the thickness of the fiber sheet before thermocompression bonding is a'and the thickness of the PPS laminated sheet is b '+ c', the thickness ratio (b '+ c' / a ') is 0.3 to 3.0.
Is preferable in terms of resin impregnation property.

(2) While melt extruding the resin composition,
A method for producing an insulating base material by thermocompression bonding to a fiber sheet.

This method can be considered in the following two types. That is, according to the method (1), the PPS laminated sheet is co-extruded while being laminated on the lower fiber sheet and thermocompression bonded. In this case, thermocompression bonding may be performed at the same time as the lamination, or may be performed in another step after the lamination. The conditions for thermocompression bonding are the same as in (1). Still another method is to laminate the PPS composition on the lower fiber sheet while extruding the PPS composition, and then laminate the copolymerized PPS sheet in the subsequent thermocompression bonding step. Also in this case, thermocompression bonding may be performed at the same time as the lamination, or may be performed in another step after the lamination. The conditions for thermocompression bonding are the same as in (1).

(3) A method for producing an insulating substrate by thermocompression bonding a PPS sheet and a copolymerized PPS sheet to a fiber sheet.

First, a PPS sheet and a copolymerized PPS sheet are produced by the method and conditions of (1). The obtained sheet is a fiber sheet / PPS sheet / copolymerized PPS sheet or copolymerized PPS sheet / PPS sheet / fiber sheet /
The PPS sheet / copolymerized PPS sheet is superposed in this order and thermocompression bonded under the condition (1). The latter configuration is preferred from the viewpoint of impregnation property. Alternatively, the fiber sheet and the PPS sheet may be thermocompression-bonded and impregnated first, and then the copolymerized PPS sheet may be thermocompressed in advance. It may be impregnated by thermocompression bonding.

(4) A method for producing the insulating base material of the present invention from the oriented laminated film.

The PPS surface of the PPS laminated sheet of (1) is uniaxially or biaxially stretched and oriented (hereinafter referred to as PPS laminated uniaxial (or biaxial) oriented laminated film), and the PPS surface is superposed on the fiber sheet and thermocompression bonded. To do. The thermocompression bonding method and conditions are the same as in (1). Here, a method for producing a PPS laminated uniaxially or biaxially oriented film will be described. The uniaxially oriented film is obtained by uniaxially stretching and orienting the PPS laminated sheet in the longitudinal direction or the width direction by a known method. The stretching conditions are 90 to 120 ° C. in both the longitudinal and width directions and 2.0 to 2.0.
It is usually performed in the range of 4.5. The PPS laminated biaxially oriented film is obtained by biaxially stretching and orienting a PPS laminated sheet by a known method. For example, when the sequential biaxial stretching method is used, the stretching conditions can be the same as those for the uniaxial stretching both in the longitudinal direction and the width direction. Then, heat treatment is performed if necessary. The tenter method is used as the heat treatment method. The heat treatment condition is usually carried out in the temperature range of 200 to 290 ° C. under a fixed length or a restricted shrinkage of 15% or less. In this case, the copolymerized PPS composition layer of the PPS laminated biaxially oriented film may or may not be oriented. In addition, both directions may be relaxed to improve the thermal dimensional stability of the film. In order to make the present invention effective, it is preferable to use the latter biaxially stretched film. The above PPS
The method for producing a laminated uniaxially oriented or biaxially oriented film is obtained by stretching an unstretched sheet in which a copolymerized PPS composition layer and a PPS composition layer are laminated between an extruder and a die or in a die. A single film of a sheet (unstretched sheet) is uniaxially or biaxially stretched and oriented (hereinafter referred to as a uniaxially or biaxially oriented PPS film), and then the copolymerized PPS composition is extruded from another die to obtain the uniaxially or biaxially oriented film. Orientation PP
A method of laminating with an S film can also be used. In addition, the embodiment of the laminated constitution of the insulating base material of the present invention is a fiber sheet
In the case of two layers of PS laminated uniaxial or biaxially oriented film,
In some cases, the PPS laminated uniaxially or biaxially oriented film is thermocompression bonded to both surfaces of the fiber sheet in three layers, but the latter mode is preferred from the viewpoint of resin impregnation. If the thickness of the fiber sheet before thermocompression bonding is a ', and the thickness of the PPS laminated uniaxially or biaxially oriented film is b' + c ', the thickness ratio (b' + c '/ a')
Is preferably in the range of 0.3 to 3.0 in terms of resin impregnation property.

(5) While melt extruding the resin composition,
A method for producing an insulating substrate by thermocompression bonding to a fiber sheet or a uniaxially or biaxially oriented film.

While extruding the PPS composition in the manner of (1) and laminating it on the lower fiber sheet, the PPS composition is heat-treated together with the monolayer film of the uniaxially stretched or biaxially stretched copolymerized PPS film previously produced in the manner of (4). Crimp. The thermocompression bonding may be performed at the same time as the lamination or after the lamination. The conditions for thermocompression bonding are the same as in (1). Further, the step of impregnating the fiber sheet with the PPS composition and the step of laminating (thermocompression bonding) the above-mentioned film may be performed separately.

(6) A method for producing an insulating substrate by thermocompression bonding a PPS sheet and a uniaxially or biaxially oriented copolymerized PPS film to a fiber sheet.

Fiber sheet (A), PPS sheet (B),
A / A biaxially oriented PPS film (C)
B / C or C / B / A / B / C are superposed in this order and thermocompression bonded under the condition (4). The latter configuration is preferred from the viewpoint of impregnation property. In addition, an A / B (or B / A / B) impregnation step and a subsequent C layer lamination (thermocompression bonding) step, or B
/ C lamination (thermocompression bonding) and thermocompression bonding to the A layer may be performed separately.

Further, powdery, granular or pelletized PP
The S composition is brought into direct contact with the fiber sheet to produce the above (1).
After impregnation under the conditions of (6) to (6), a copolymerized PPS sheet,
There is also a method of laminating (thermocompression bonding) uniaxially oriented or biaxially oriented copolymerized PPS films.

Further, after the laminated structure of the present invention is formed by the above-mentioned method or other methods, the surface of the insulating base material may be polished or etched by a physical or chemical method to obtain the final product. It does not matter if the product achieves the object of the present invention.

Next, a method of manufacturing the circuit board will be described.

The method of providing a metal layer on the surface of the insulating base material of the present invention is carried out by, for example, superposing a metal foil on the copolymerized PPS resin layer of the insulating base material, and at a temperature of 200 to 300 ° C., preferably the copolymerized PPS. When the melting point of the composition is Tmk, Tm
k-30 ° C to Tmk + 50 ° C, pressure 1 to 30 kg / cm
Heat fusion is performed under the conditions of ² . Also, the above (1) to (6)
The metal foil may be heat-fused and laminated simultaneously with the production of the insulating base material. Furthermore, metal deposition method, sputtering method,
A metal layer may be provided on the surface of the copolymerized PPS resin layer of the insulating base material by a method such as plating.

The metal layer of the insulating base material thus obtained is formed into a desired circuit pattern by an etching method (for example, with an aqueous ferric chloride solution) to obtain a circuit board. Further, in a multilayer circuit board, two or more layers of a circuit board having an electric circuit formed on one surface of the insulating base material of the present invention in which a copolymerized PPS resin layer is laminated on both sides are laminated so that the circuit surface and the copolymerized PPS surface are in contact with each other and the temperature is increased. 200-300 ° C, preferably Tmk-30 ° C-Tmk
Laminating is performed by heat fusion under the conditions of + 50 ° C. and pressure of 1 to 10 kg / cm ² . Further, circuit boards provided with electric circuits on both sides of the insulating base material of the present invention may be laminated via a copolymerized PPS resin sheet. Further, the electric circuit may be combined with a conductor other than metal, for example, a circuit board provided with silk-screen printing of a conductive paste or the like, and heat-bonded under the above conditions to produce a multilayer circuit board. Further, the layers are connected to each other by a method such as a plating method. In addition, electronic parts and the like are mounted by soldering or the like as necessary.

[0053]

[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) Heat resistance A 2 cm square circuit board sample was floated in a solder bath set at a temperature of 260 ° C. and evaluated according to the following criteria.

◯: No change

Δ: Partly softened, deformed, peeled off the circuit, and wrinkled.

X: Deformation such as waviness or bending on the entire surface or peeling of the circuit, and a large dimensional change rate.

(2) Permeation of Ink When a magic ink (the ink portion of the magic) is brought into contact with the surface of the insulating substrate in the cross-sectional direction (thickness direction) for 3 seconds, the ink permeates inside. The soaked length (the longest distance that the ink reached from the position where the magic ink came into contact) was expressed by the length (mm) measured from the surface of the sheet. The magic used was from Pentel Co., Ltd. (oiliness of Penterpene medium letter N50).

(3) Heat shrinkage ratio With the circuit board in a certain direction as a reference direction, 100 mm × 10 mm is cut out in each of the reference direction and the 90 ° direction of the reference direction, and a mark is attached to the conductor portion of the circuit to provide a space between the marks in the longitudinal direction. Accurately read the distance (xmm) with a microscope.
Then, after aging for 30 minutes in a furnace (hot air method) heated to a temperature of 240 ° C., the above distance is accurately measured (y
mm). The heat shrinkage rate (%) in each direction was calculated by the following formula, and the value was shown in the direction of the larger heat shrinkage rate.

Thermal shrinkage (%) = (x−y) / x × 100 (4) Adhesive strength An insulating base material is fixed to a 1.5 mm thick aluminum plate with a double-sided adhesive tape, and a metal layer is applied to Tensilon. (Made by Toyo Baldwin Co., Ltd.), and the peeling force was measured. The sample width is 10 mm, the peeling speed is 50 mm / min, and k
It was expressed in g / cm.

(5) Dielectric property (dielectric loss) The frequency was changed to examine the change in dielectric loss. (JIS-
It measured according to C-6481. (6) Displacement of Circuit The circuit board was passed through a furnace (far-infrared ray method) set at a temperature of 240 ° C. for 5 seconds, and the circuit was dislocated from that not passed through the furnace.

(7) Conductor resistance value of the circuit It was measured using ACP-TESTER, LORESTA-FP (manufactured by Mitsubishi Petrochemical Co., Ltd.).

(8) Copolymerization P with PPS resin layer of insulating base material
Thickness measurement of PS resin layer A cross section was observed with a polarizing microscope and a photograph was taken, and the thickness of each layer was determined from the photograph.

(9) Melt viscosity The melt viscosity was measured by a high flow tester method.

(10) Melting point It was measured using a differential scanning calorimeter (DSC-2 type).

[0066]

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

Example 1, Example 2, Example 3 (1) Preparation of Copolymerized PPS Composition In an autoclave, 100 mol of sodium sulfide nonahydrate, 45 mol of sodium hydroxide and 25 liters of N 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 dehydrated system. 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.

Next, 10 g of the copolymerized PPS was mixed with 50 g of spherical silica having a diameter of 0.5 μm, and the mixture was extruded in a gut shape at 320 ° C. with a 30 mmφ twin-screw extruder to be pelletized.

(2) Preparation of PPS composition PPS composition 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) Film Formation of Laminated Sheet of Copolymerized PPS and PPS The copolymerized PPS composition and the PPS composition obtained in the above (1) and (2) were heated at 180 ° C. for 3 hours, respectively.
After drying under reduced pressure of mmHg, they are fed to separate extruders, and in a molten state, the above two polymers are laminated by a double-tube type laminating device on the upper part of the die, and the T-die type die provided subsequently Discharged, cooled and solidified with a cooling rotary drum, and a two-layer laminated sheet of copolymerized PPS / PPS (unoriented)
3 types were obtained. The laminated sheet has a thickness of 25 μm, the copolymerized PPS layer has a thickness (C) of 12 μm (PPS laminated sheet-1), the thickness of C is 7 μm (PPS laminated sheet-2), and the C Thickness of 17μm (P
It was three types of PPS laminated sheets of PS laminated sheet-3).

Next, the PPS composition was supplied to an extruder having a hole diameter of 40 mm, discharged from a T-die type die and cooled and solidified by a cooling rotary drum to obtain a PPS sheet (unstretched sheet) having a thickness of 25 μm (p -PPS sheet-1).

(4) Preparation of fiber sheet 3 of glass cloth (EPC030 Arisawa Seisakusho)
4 μm was used (fiber sheet).

(5) Production of Insulating Base Material PPS laminated sheet-1 and p- are provided on both sides of the fiber sheet.
Each of the PPS sheet-1 and the fiber sheet surface and the PPS composition layer are combined (PPS laminated sheet-1 / fiber sheet / p-
PPS sheet-1) Heat-sealed (insulating substrate-1). As the method of heat fusion, three sheets were superposed on the above structure and heat fusion was performed by a hot plate pressing method. The heat fusion condition is a temperature of 300.
° C., a pressure 20 kg / cm ^2, pressing time (hold time) and 1 h, and then quenched to 50 ° C. Thereafter while pressing. Further similarly, PPS laminated sheet-2, 3
To prepare an insulating base material (insulating base material-2, insulating base material-3 in this order).

(6) Manufacture of circuit board A rolled copper foil of 1 ounce (36 μm in thickness) was prepared as described in (5) above.
A type of insulating substrate was heat fused to the copolymerized PPS composition side.
The heat fusion method is a hot plate pressing method, and the heat fusion condition is temperature 2
65 ° C., pressure 10 kg / cm ² , press time 1
It was cooled to 50 ° C. in the pressed state for a certain period of time. Next, the copper foil was etched into an electric circuit pattern with an aqueous ferric chloride solution to obtain three types of circuit boards (Example 1, Example 2, and Example 3 in order).

Comparative Example 1 and Comparative Example 2 An insulating base material was prepared by using p-PPS sheet-1 under the condition of insulating base material-1, and 1 ounce copper foil was heated at a temperature of 290 ° C. and a pressure of 1 kg / cm ² . Heat-bonding under the conditions of Example 1, Example 2,
An electric circuit was formed by the method of Example 3 to manufacture a circuit board (Comparative Example 1).

An unstretched sheet (m-PPS sheet) of the copolymerized PPS composition prepared by the method for producing p-PPS sheet-1.
And a circuit board was manufactured under the manufacturing conditions of Comparative Example 1 (Comparative Example 2).

Examples 4, 5 and 6 (1) Production of insulating base material PP obtained by the same method as in Examples 1, 2 and 3
The S laminated sheet was biaxially stretched. As for the stretching conditions, a sequential biaxial stretching method is used, and a stretching temperature of 90 is obtained by a roll stretching method in the longitudinal direction.
C., a draw ratio of 3.7 times, a tenter method in the width direction, a draw temperature of 100.degree. C., and a draw ratio of 3.5. Then, it heat-processed at 260 degreeC for 10 second in the same tenter. The obtained PPS laminated biaxially oriented film had a thickness of 25 μm, and the copolymerized PPS layer had a thickness of 13 μm. The film was laminated on both sides of the fiber sheet so that the surface of the PPS composition was in contact with the fiber sheet, and heat fusion was performed by a heating press roll method. Temperature is 285 ° C and 310 ° C, and pressure is 10 kg / cm ²
And the line speed was 0.5 m / min. 28
What was heat-sealed at 5 ° C. is an insulating base material-4, and what was heat-sealed at 310 ° C. was an insulating base material-5.

(2) Production of Circuit Board 1 ounce rolled copper foil was heat-sealed on both surfaces of the two types of insulating base materials obtained in the above (1). The method of heat fusion is described in Example 1,
The insulating base material-4 was heated to a temperature of 26 by the method of Examples 2 and 3.
The temperature was 5 ° C., and the insulating base material-5 was 240 ° C. and 265 ° C. under two conditions, the pressure was 10 kg / cm ² , and the pressing time was 1 hour. Further, Example 1, Example 2,
Electric circuits were formed on both sides by the method of Example 3 (a circuit board using the insulating base material-4 was used in Example 4 and an insulating base material-5 was used in Example 5 and Example 6, respectively). .

Example 7 Amount of p-dichlorobenzene as a main component monomer added 94.
8 mol%, the amount of the sub-component monomer m-dichlorobenzene added was 5 mol%, and the others were Example 1, Example 2, and Example 3.
The copolymerized PPS was polymerized under the conditions (melting point: 263 ° C.). Moreover, the same PPS as that used in Example 1, Example 2, and Example 3 was used. Further, a PPS laminated sheet was prepared under the conditions of PPS laminated sheet-2 of Example 2. An insulating base material was produced under the conditions of Example 1, Example 2, and Example 3, and further a circuit board was produced.

Example 8 Amount of p-dichlorobenzene as a main component monomer added 69.
The copolymerized PPS was polymerized (melting point: 201 ° C.) under the conditions of Example 1, Example 2, and Example 3 except that the amount of the sub-component monomer m-dichlorobenzene was 30 mol%.
The same PPS as that used in Examples 1, 2 and 3 was used. Furthermore, a PPS laminated sheet was produced under the production conditions of PPS laminated sheet-2 of Example 2 to obtain an insulating base material, and then a circuit board was produced.

Comparative Example 3 An electric circuit was formed by silk printing on one surface of the insulating base material-2 of Example 2 using a silver paste as a conductor to obtain a circuit board.

Comparative Example 4 A 1 ounce rolled copper foil was laminated on one surface of the insulating base material-2 of Example 2 with the following adhesive, and the circuit was formed by the method of Example 1, Example 2 and Example 3. A substrate was produced. The adhesive used was an epoxy adhesive ("Chemit" Epoxy Toray Co., Ltd.).
Then, it was applied to a thickness of 15 μm / dry with a gravure roll coater, and the solvent was dried at 100 ° C. for 3 minutes. Next, 1 ounce copper foil was laminated by the hot press roll method. The lamination conditions are a temperature of 125 ° C. and a pressure of 3 kg / cm ² . 1 more
The adhesive was cured under the condition of 50 ° C. for 1 hour.

Comparative Example 5 An unstretched sheet having a thickness of 100 μm was prepared under the manufacturing conditions of p-PPS sheet-1, and Example 1, Example 2 and Example 3 were prepared.
A 1 ounce copper foil was heat-sealed on the surface of the sheet by the method of 1. to form an electric circuit.

Comparative Example 6 Biaxially Oriented PPS Film (“Torelina” Type 303)
A copper foil was laminated on the easy-adhesion surface of 0,100 μm thick Toray Co., Ltd. by the method of Comparative Example 4 to form an electric circuit.

Evaluation of Examples and Comparative Examples Tables 1 and 2 show the evaluation results of the circuit boards of Examples 1 to 8 and Comparative Examples 1 to 6.

The circuit boards of the present invention of Examples 1 to 8 are excellent in heat resistance, thermal dimensional stability and dielectric properties. That is, since the PPS sheet reinforced with the heat-resistant fiber sheet is used as the insulating base material, it has excellent heat resistance and thermal dimensional stability, resistance to solder, and no circuit deviation even when the circuit board is heated. Further, since the conductor is adhered through the copolymerized PPS composition layer having a high adhesiveness and a melting point lower than that of the PPS resin composition, the PPS characteristics such as dielectric characteristics and moisture absorption characteristics are not deteriorated. Furthermore, a metal foil such as copper can be directly fused as a conductor to reduce the conductor resistance value of the circuit, and it is also possible to use fine patterns. In addition, since the resin and the fiber sheet are highly impregnated, the reliability of the through hole is high.

When the cross sections of the circuit boards of Examples 1 to 3 were observed with a microscope, the laminated constitution of the insulating base material was distinguished by the mode of the present invention. That is, in Example 1, the layer of the fiber sheet was impregnated with the PPS composition and the layer of the PPS composition had the same thickness, and the layer of the copolymerized PPS composition was provided thereon. In Example 2, the resin impregnated layer was replaced with PPS.
The resin composition layer was thick, and the copolymerized PPS resin composition layer was provided thereon. Further, in Example 3, the thickness of the PPS resin composition layer is smaller than that of the resin impregnated layer, and a part of the copolymerized PPS resin composition layer provided on the resin impregnated layer enters in the resin impregnated layer. As can be seen from Tables 1 and 2, these three types of characteristics all achieve the object of the present invention.

Further, the heat fusion temperature at the time of manufacturing the insulating base material from Examples 4 and 6 is effective above the melting point of the PPS resin composition for resin impregnation, and a temperature of 300 ° C. or higher is particularly preferable. I understand. On the other hand, from the results of Examples 5 and 6, it is advantageous in terms of adhesion that the fusion temperature between the copolymerized PPS layer of the insulating base material and the metal foil is higher than the melting point of the copolymerized PPS. When the melting point (Tmk) is -30 ° C or lower, the adhesive strength is 1.0 kg / cm or lower, which makes it difficult to make the circuit fine.

Even if the addition ratio of the main component monomer and the subcomponent monomer (copolymerization component) of the copolymerized PPS forming the adhesive layer between the circuit layer and the insulating base material is changed from Examples 1, 2, 3, 7, and 8. Although the object of the present invention can be achieved, when the addition ratio of the copolymerization component exceeds 30 mol%, heat resistance and thermal dimensional stability decrease, and when it is less than 5 mol%, adhesion to the circuit layer decreases. I understand that

Since Comparative Example 1 uses an insulating base material composed only of the PPS resin composition, it has a poor adhesion to the circuit layer,
Comparative Example 2 uses an insulating base material composed only of the copolymerized PPS resin composition, and therefore has poor heat resistance and thermal dimensional stability.

Further, in Comparative Example 3, since the conductive paste is used for the conductor of the circuit layer, the conductor resistance value is large and the object of the present invention cannot be achieved. In Comparative Example 4, since the copolymerized PPS layer is not provided and another adhesive is used, the dielectric characteristics (high frequency characteristics) and the moisture absorption characteristics, which are the characteristics of PPS, are deteriorated and the object of the present invention cannot be achieved. Furthermore, the circuit board of Comparative Example 5 is PPS.
Since the unstretched sheet of No. 1 is used as an insulating base material, the heat resistance is poor, and the one using the biaxially oriented PPS film of Comparative Example 6 as an insulating base material has a large thermal dimensional change rate, and a circuit layer is laminated with another adhesive. Therefore, there is a problem similar to that of the circuit board of Comparative Example 4.

[0094]

[Table 1]

[Table 2] Next, a multilayer circuit board in which the circuit boards of the present invention are laminated will be described in detail with reference to examples.

Example 9 The circuit board of Example 1 was heat-sealed through an m-PPS sheet having a thickness of 25 μm to prepare a 5-layer multilayer circuit board, which was through-hole processed. The conditions for heat fusion are hot plate pressing, temperature 265 ° C., and pressure 10 kg / cm ² . As a result of mounting various electronic components on this circuit board with solder and attempting to simulate high-speed processing of signals and high-frequency characteristics, the characteristics were suitable for applications requiring high-speed processing of signals and high-frequency characteristics.

Example 10 The circuit boards of Comparative Example 3 were superposed in three layers, and the circuit boards of Example 1 were heat-sealed on both sides (outermost layers) under the conditions of Example 9 to form through holes, thereby forming a multilayer circuit. A substrate was produced. As a result of performing the same evaluation as that of Example 9, the object of the present invention was achieved although it was somewhat inferior to the multilayer circuit board of Example 9.

Comparative Example 7 Five layers of the circuit board of Comparative Example 3 were superposed on each other, heat-bonded in an autoclave under conditions of a temperature of 295 ° C. and a pressure of 10 kg / cm ² and through-hole processed to produce a multilayer circuit board.
As a result of performing the same evaluation as that of Example 9, the signal response and the like were inferior to those of the multilayer circuit board of Example 9, and it could only be used for limited applications, and the object of the present invention was not achieved. It was

[0098]

EFFECTS OF THE INVENTION The circuit board of the present invention, having the above-mentioned structure, has a high-dimensional balance of heat resistance, thermal dimensional stability, high frequency characteristics, moisture absorption characteristics, etc., and has an adhesive force with the circuit layer and a conductor resistance of the circuit. It becomes a circuit board and a multilayer circuit board with a low mine value,
In particular, it has become a circuit board (including multi-layer circuit boards) suitable for high-speed signal processing and high-frequency compatibility.

The circuit board of the present invention is most suitable for a circuit board of a computer, a memory card, OA equipment, portable electric equipment, electronic equipment and the like.

Claims (4)

[Claims] 1. A copolymer containing at least one copolymerized unit other than a p-phenylene sulfide unit on the surface of a sheet obtained by impregnating a fiber sheet with a resin composition containing poly-p-phenylene sulfide as a main component. A circuit board, wherein an electric circuit made of a metal layer is formed via a resin composition layer made of polymerized polyphenylene sulfide. 2. The circuit board according to claim 1, wherein the fiber sheet is infusible at a temperature of 400 ° C. 3. The circuit board according to claim 1, wherein the fiber sheet is glass fiber. 4. A multilayer circuit board comprising the circuit boards according to claim 1 laminated.