JPH0645764A - Printed wiring board - Google Patents

Abstract

(57) [Abstract] [Purpose] Heat resistance, thermal dimensional stability, high-frequency characteristics, moisture absorption characteristics, etc. are well-balanced and excellent in adhesive strength and conductor resistance, and they are small (thin-walled) and multi-layered (higher). Density, high-speed signal processing, and high-frequency compatibility. [Structure] A sheet obtained by impregnating a fiber sheet (A) with a resin composition (B) containing poly-p-phenylene sulfide as a main component, and at least one copolymerized unit other than a p-phenylene sulfide unit. Laminated wiring board in which an electric circuit is provided on the surface of layer C of a layered body composed of a resin composition (C) layer composed of copolymerized polyphenylene sulfide, and C layer of a laminated film of poly-p-phenylene sulfide film and C A multilayer wiring board having a film wiring board having an electric circuit provided on the surface thereof.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a multilayer wiring board. More specifically, a multilayer wiring board including a wiring board having a resin-impregnated sheet obtained by impregnating a fiber sheet with poly-p-phenylene sulfide resin as an insulating base material and a wiring board having a poly-p-phenylene sulfide film as an insulating base material. It is about.

[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 multilayer wiring boards is increasing. Among them, high-speed signal processing, high frequency characteristics, low resistance circuit,
Workability and thinning of through-holes are being particularly demanded from the development of portable electronic devices.

As a multilayer wiring board in this field, a substrate in which a glass cloth is impregnated with an epoxy resin (hereinafter referred to as glass epoxy) is used to form an electric circuit with a metal foil such as copper to form a multilayer, a polyimide film, a fluorine-based film. There is a multilayer structure in which an electric circuit is formed. Furthermore, poly-p-
A multilayer wiring board using an unstretched film of phenylene sulfide (hereinafter referred to as PPS) (hereinafter referred to as unstretched PPS film) and a biaxially oriented film (hereinafter referred to as biaxially oriented PPS film) as an insulating base material has recently received special attention. Taking a bath. Also known is a multilayer wiring board (Japanese Patent Laid-Open No. 2-415004, etc.) in which a PPS resin reinforced with a fiber sheet such as glass fiber is used as an insulating base material.

[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 has high heat resistance, but has low hygroscopicity and poor 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 unstretched PPS film alone as an insulating substrate satisfies various characteristics such as thermal dimensional stability, low hygroscopicity, flame retardancy, and high frequency characteristics. In comparison, the heat resistance temperature is low (heat deformation tends to occur when the glass transition point is exceeded), and crystallization progresses and becomes brittle as the heating process increases. 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.

Further, a biaxially oriented 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 multilayer wiring board using an insulating base material obtained by reinforcing a PPS resin with glass fiber is excellent in heat resistance, thermal dimensional stability, high frequency characteristics, flame retardancy, moisture absorption characteristics, etc., but becomes an electric circuit. There is a problem that it is difficult to heat-fuse with a metal foil such as copper and 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 is a limit to the fine patterning of the circuit, and the circuit design may be limited to a part. A further serious problem is that since the fiber sheet is reinforced, the thickness of the fiber sheet is rate-determining, and it is difficult to reduce the thickness of the multilayer wiring board (the thickness of the insulating base material per layer is limited to 40 μm). The present invention is
Paying attention to the excellent low hygroscopicity, flame retardancy and high frequency characteristics of PS,
In addition, a sheet made by impregnating PPS resin into a fiber sheet that can significantly improve heat resistance and dimensional stability is used as an insulating substrate, and high frequency characteristics, dimensional stability, and heat resistance are maintained, and the resistance value of the circuit is small. The present invention aims to provide a multilayer wiring board which is capable of fine patterning, is ultra thin, and has a high number of layers, and is particularly suitable for high-speed signal processing and high-frequency application.

[0009]

Means for Solving the Problems That is, a sheet obtained by impregnating a fiber sheet (A) with a resin composition (B) containing poly-p-phenylene sulfide as a main component and at least 1 other than a p-phenylene sulfide unit. A laminate wiring board in which an electric circuit is provided on the surface of a C layer of a laminate comprising a resin composition (C) layer of a copolymerized polyphenylene sulfide containing at least one type of copolymerized unit (hereinafter referred to as copolymerized PPS); A multilayer wiring board having a poly-p-phenylene sulfide film and a film wiring board having an electric circuit provided on the surface of a C layer of a laminated film of C, wherein the laminated body wiring board and the film wiring board each have at least one layer each. It is a multilayer wiring board formed by stacking layers.

The fibrous sheet in the present invention is a thin sheet made of an aggregate of fibers, such as cloth, cloth,
Felt, non-woven fabric, paper, etc. generically thickness 10-500μ
m is preferable, and more preferably 10 to 300 μm. The fiber sheet may be processed for easy adhesion, coloring, etc., and two or more kinds of materials may be mixed or laminated. 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 does not have a 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 fibrous sheet used in the present invention does not have the above characteristics, the thermal dimensional stability becomes insufficient when the impregnated sheet of the present invention is exposed to a temperature near 300 ° C.

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 When the amount of such components is less than 80 mol%, the crystallinity of the polymer, the thermal transition temperature, etc. are low, and the heat resistance, dimensional stability, mechanical properties, etc., which are the characteristics 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 a main component (hereinafter referred to as PPS composition) means poly-p-phenylene sulfide.
A composition containing 0% by weight or more. PPS content is 60
If it is less than wt%, the mechanical properties of the laminate comprising 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, and more preferably in the range of 500 to 20000 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%.
When the content is less than 50 mol%, the heat resistance and thermal dimensional stability of the multilayer circuit board are poor, while when it exceeds 95 mol%, the adhesive strength with the electric circuit layer is reduced, or the sheet after impregnation is impregnated. The flatness is remarkably deteriorated.

As the copolymerization unit, 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 force with the electric circuit layer is lowered, and the flatness of the sheet after impregnation is significantly deteriorated. On the other hand, when it exceeds 50 mol%, heat resistance and thermal dimensional stability of the multilayer circuit board become poor. Copolymer P
The rest of the PS repeating units 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 first wiring board used in the multilayer wiring board of the present invention is copolymerized on the surface (at least the surface where an electric circuit is formed) of a resin-impregnated sheet obtained by impregnating a fiber sheet with the above PPS composition. Layers of PPS composition are laminated,
Further, an electric circuit is provided on the surface thereof (hereinafter referred to as a laminated wiring board). The impregnated state can be measured, for example, by the degree of ink penetration. The insulating layer (layers other than the electric circuit layer) of the laminate wiring board of the present invention is basically obtained by impregnating the fiber sheet (A) with the PPS composition (B), and the PPS composition of the resin-impregnated fiber sheet. The copolymerized PPS composition (C) layer is heat-sealed on the upper part of the layer, but part of the C layer may be impregnated with A together with B. That is, the basic structure of the insulating layer of the laminated wiring board of the present invention can be the following three modes.

(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 the 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 layer in the cross-sectional direction (thickness direction), the ink penetrates inside.
It is a value representing the impregnated length (the longest distance that the ink reaches from the position where the magic ink is applied) by the length (mm) measured from the surface of the sheet, which is a parameter indicating the degree of impregnation of the insulating layer. Is. The thickness of the insulating layer of the laminated wiring board of the present invention is preferably in the range of 20 to 1000 μm.

Next, in the second wiring board used for the multilayer wiring board of the present invention, the C layer is laminated on the surface of the PPS film (at least the surface on which the electric circuit is formed), and the electric circuit is further formed on the surface. It is formed (hereinafter referred to as a film wiring board). The PPS film, which is the main constituent of the insulating layer of the film wiring board, is an unstretched (non-oriented) film obtained by melt-molding the PPS resin composition (B), or uniaxially or biaxially stretched (oriented) and heat-treated. A film having a thickness of 4 to 300 μm. The insulating layer of the wiring board is formed by laminating the copolymerized PPS resin composition (C) layer on the film, and the ratio of the two is the PPS when the thickness of each layer is measured from the cross section of the insulating layer with a microscope or the like. When the thickness of the film is p and the thickness of the C layer is c, a range of c / p of 0.02 to 2 is particularly preferable in terms of the balance between adhesive strength and heat resistance. Further, the content (Pcop mol%) of the copolymerized PPS contained in the resin composition of the PPS film layer and C
Content of copolymerized PPS contained in the resin composition of the layer (C
It is particularly preferable that the relation of (cop mol%) is Pcop <Ccop in order to achieve the object of the present invention.

The electric circuit in the present invention refers to an electric passage in which a conductor such as a simple substance such as copper, aluminum or iron or a metal composed of two or more kinds of alloys or a conductor such as a paste containing these metals or carbon is patterned. , Thickness 1
It is formed of a layer having a thickness of 100 μm, preferably 1 to 80 μm. A metal layer circuit is preferable from the viewpoint of lowering the resistance of the circuit. Furthermore, the wiring board is one in which an electric circuit is formed on at least one surface of the insulating layer as described above, and electric and electronic parts may be mounted on the wiring board. The multilayer wiring board in the present invention is one in which a laminated wiring board and a film wiring board are laminated with at least one or more layers each interposed by a C layer, and each layer is electrically connected by a conductor. The number of layers of the multilayer circuit board of the present invention, the total thickness, and the composition ratio of the laminate wiring board and the film wiring board are not particularly limited, but the composition ratio is the number of layers of the film wiring board with respect to the total number of layers of the multilayer wiring board. The ratio of 0.1 to 0.7 is preferable in terms of thinning the multilayer wiring board, increasing the number of layers, and heat resistance. Further, the stacking mode of both wiring boards is not particularly limited. 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.

The joining of the insulating layer and the electric circuit layer of the present invention and the multi-layer joining of the wiring boards are all performed by the copolymerized PPS resin layer (no adhesive other than PPS is used).
Is important in maintaining various characteristics of PPS such as dielectric characteristics, moisture absorption characteristics, and heat resistance.

Next, a method of manufacturing the multilayer wiring board of the present invention will be described.

Method for Producing Copolymerized PPS and PPS Resin Composition First, the method for polymerizing the copolymerized PPS used in the present invention is as follows.
Although there are various methods, there is a method in which alkali sulfide, p-dihalobenzene (main component monomer) and auxiliary component monomer are blended in the proportions referred to in the present invention, and polymerization is carried out in a polar solvent at high temperature and high pressure in the presence of a polymerization aid. It is preferable that 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. p
-As the accessory component monomer in which the accessory component monomer coexists with 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 a plurality of 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.

Manufacturing Method of Insulating Base Material Various methods can be used for impregnating the fiber sheet with the above PPS polymer and laminating the copolymerized PPS, but the following method can be exemplified as a typical method. . (1) The above-mentioned PPS composition (B) and copolymerized PPS composition (C) are coextruded to prepare an unstretched and unoriented laminated film of B and C (hereinafter referred to as PPS laminated film),
A method for producing an insulating base material by aligning the surface B of the PPS laminated film with a fiber sheet and thermocompression bonding.

First, a method for manufacturing the above PPS laminated film (unstretched film) 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 melted at a temperature equal to or higher than the melting point of each composition, are in a molten state at a joining device provided between the extruder and the die or in the die. Are stacked and extruded from the die. By rapidly cooling such a molten laminate to a temperature below the glass transition point of the film, a substantially non-oriented PPS laminated film is obtained. Here, the merging device is in a molten state and is 2
It has a function of laminating one or more polymer compositions. Alternatively, after preparing only the PPS film under the above conditions in advance, an unstretched film of the copolymerized PPS composition (hereinafter referred to as the copolymerized PPS film) can be extruded from the die and laminated on the film.

The surface B of the non-oriented PPS laminated film thus obtained is laminated on a fiber sheet, and the pressure of 1 to 1 is applied at a temperature of 290 to 350 ° C. which is higher than the melting point of the PPS composition.
Under the condition of 30 kg / cm ² , thermocompression bonding is performed with a heating roll press or a hot plate press. Further, the film is cooled through a cooling roll, a cooling plate, fresh air, water or the like for the purpose of maintaining the flatness of the film. The above thermocompression bonding temperature is PPS
At temperatures below the melting point of the composition, impregnation is poor. If the pressure is less than 1 kg / cm ² , impregnation is poor and conversely 30
If it exceeds kg / 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 may be two layers of the fiber sheet and the PPS laminated film, or three layers of the PPS laminated film, the fiber sheet and the PPS laminated film may be superposed in this order. However, 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 film is b '+ c', the thickness ratio (b '+ c' / a ') is 0.3 to 3.0. It is preferable in terms of impregnation property.

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

The following two types of methods can be considered. 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 film 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) PPS film and copolymerized PPS
A method for producing an insulating substrate by thermocompression bonding a film to a fiber sheet.

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

(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 film of (1) uniaxially or biaxially stretched and oriented (hereinafter referred to as PPS laminated uniaxial (or biaxial) oriented laminated film) is superposed on a fiber sheet and subjected to thermocompression bonding. 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 film in the longitudinal direction or the width direction by a known method. The stretching conditions are usually 90 to 120 ° C. and 2.0 to 4.5 in both the longitudinal and width directions. The PPS laminated biaxially oriented film is obtained by biaxially stretching and orienting the PPS laminated film 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 copolymerization P of the PPS laminated biaxially oriented film
The PS composition layer 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 method for producing the PPS laminated uniaxially oriented or biaxially oriented film is obtained by stretching an unstretched sheet obtained by laminating a copolymerized PPS composition layer and a PPS composition layer between the extruder and the die or in the die. However, a monolayer of a copolymerized PPS film (unstretched film) was uniaxially or biaxially stretched and oriented (hereinafter referred to as a uniaxially or biaxially oriented PPS film).
A method in which the copolymerized PPS composition is subsequently extruded from another die and laminated with the uniaxially or biaxially oriented PPS film can also be used. Moreover, the embodiment of the laminated constitution of the insulating base material of the present invention includes two layers of the fiber sheet and the PPS laminated uniaxial or biaxially oriented film, and thermocompression bonding of the PPS laminated uniaxial or biaxially oriented film to both surfaces of the fiber sheet. Although it may be a layer, the latter embodiment is preferable from the viewpoint of resin impregnation property. 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 0.3 to 3.0. The range is preferable from the viewpoint 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 was heat-treated together with the single film of the uniaxially 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 film and a uniaxially or biaxially oriented copolymerized PPS film to a fiber sheet.

The fiber sheet (A), the PPS film (B), and the uniaxially or biaxially oriented PPS film (C) are superposed in the order of A / B / C or C / B / A / B / C ( Thermocompression bonding is performed under the condition of 4). The latter configuration is preferred from the viewpoint of impregnation property. Also, A / B (or B / A
/ B) impregnation step and subsequent step of C lamination (thermocompression bonding) 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.

Furthermore, 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 a final product. It does not matter if the product achieves the object of the present invention.

The laminated film obtained by laminating the copolymerized PPS layer on the PPS film may be the laminated film obtained by the above methods (1) and (4).

Method for Producing Multilayer Wiring Substrate A method for providing a metal layer on the surface of the insulating base material of the present invention is, for example, by superposing the copolymerized PPS resin layer of the insulating base material and the metal foil on each other at a temperature of 200 to 300 ° C. , Preferably copolymerized P
When the melting point of the PS composition is Tmk, Tmk-30 ° C
Thermal fusion is performed under the conditions of Tmk + 50 ° C. and pressure of 1 to 30 kg / cm ² . Further, the metal foils may be heat-fused and laminated at the same time as the production of the insulating base materials (1) to (6). Further, 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 vapor deposition, sputtering or 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 wiring board. A wiring board can also be obtained by forming an electric circuit with a conductive coating material containing a metal such as silver or copper and an alloy thereof or a conductor such as carbon by a method such as silk printing. In order to manufacture a multilayer wiring board from the wiring board thus obtained, the resin-impregnated sheet of the present invention in which a copolymerized PPS resin layer is laminated on both sides, and a wiring board in which an electric circuit is formed on one side of a laminated film And two or more layers are laminated so that the copolymerized PPS surface is in contact therewith, and the temperature is 200 to 300 ° C., preferably Tm
k-30 ° C to Tmk + 50 ° C, pressure 1 to 10 kg / cm
Laminate by heat fusion under the conditions of 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 layers are connected to each other by a method such as a plating method or a conductive paint printing method. In addition, electronic parts and the like are mounted by soldering or the like as necessary.

[0052]

[Physical property measuring method and effect evaluation method] The characteristic values of the present invention are based on the following evaluation 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 at all

Δ: Partly softened, deformed, peeled off 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) Thermal shrinkage ratio The direction in which the multilayer wiring board is present is set as a reference direction, and the reference direction and the 90 ° direction of the reference direction are each 100 mm × 10.
Cut out to mm, mark the conductor part of the circuit, and accurately read the distance between the marks in the longitudinal direction with a microscope (xm
m). 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 (ymm). Calculate the heat shrinkage rate (%) in each direction by the following formula,
The value is shown in the direction of higher heat shrinkage.

Thermal shrinkage (%) = (xy) / x100 (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 of a circuit is formed. Was peeled off with Tensilon (manufactured by Toyo Baldwin Co., Ltd.), and the peeling force was measured.
The sample width was 10 mm, the peeling speed was 50 mm / min, and it was expressed in kg / cm.

(5) Adhesion between layers after multilayering The adhesion between layers after bending the end surface of the multilayer wiring board 5 times was evaluated according to the following criteria.

◯: Peeling does not occur at all.

Δ: Partial peeling may occur.

X: Easy peeling.

(6) Dielectric Properties (Dielectric Loss) Changes in dielectric loss were examined by changing the frequency. (JIS-
It measured according to C-6481. (7) Displacement of Circuit The circuit board was passed through a furnace (far-infrared ray system) set at a temperature of 240 ° C. for 5 seconds, and the circuit was dislocated from that not passed through the furnace.

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

(9) 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.

(10) Thickness of multilayer wiring board Measured with a dial gauge.

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

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

[0070]

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 system after dehydration. Trichlorobenzene with 5 liters of N
Add with MP and add nitrogen at 170 ℃ 3kg / cm ²
After sealing under pressure, 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.
The nodular polymer was collected by a wire mesh having mesh openings.

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 10
Copolymerized PP with 00 poise and melting point of 253 ° C in the form of white particles
An S 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 to form pellets.

(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 It was discharged and cooled and solidified by a cooling rotary drum to obtain three kinds of two-layer laminated film (unoriented) of copolymerized PPS / PPS. The thickness of the laminated sheet is 25 μm,
Copolymerized PPS layer having a thickness (C) of 12 μm (PPS
Laminated film-1), wherein the thickness of the C layer is 7 μm (P
PS laminated film-2), and the thickness of the C layer is 17 μm.
m PPS laminated film-3 (PPS laminated film-3)
It was a laminated film.

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 film (unstretched film) of 25 μm.
An m-thick product was obtained (p-PPS film-1).

(4) Preparation of fiber sheet 3 pieces of glass cloth (EPC030 manufactured by Arisawa Manufacturing Co., Ltd.)
4 μm was used (fiber sheet).

(5) Production of Laminated Wiring Board of the Present Invention PPS laminated film-1 and p were laminated on both sides of the above fiber sheet.
-The PPS film-1 and the PPS composition layer were combined with each other (PPS laminated film-1 / fiber sheet / p-PPS film-1) and heat-sealed (laminated body-
1). The method of heat fusion is performed by superposing each of the above-mentioned three layers by a hot plate pressing method, the conditions are a temperature of 300 ° C., a pressure of 20 kg / cm ² , and a pressing time (heating hold time) of 1 hour, Then, it was rapidly cooled to 50 ° C. in the pressed state. The degree of ink penetration of the obtained impregnated sheet was 0.
The resin impregnating property was 2 mm, and the object of the present invention was sufficiently achieved. Further, in the same manner, a laminated body was produced using PPS laminated films-2 and 3 (laminated body-2, laminated body-in this order).
3).

A layer of rolled copper foil of 1 ounce (thickness of 36 μm) was placed on the surface of the copolymerized PPS composition layer of each of the laminates-1 to 3 at a temperature of 260.
Thermal fusion was performed by a hot plate pressing method under the conditions of ° C and a pressure of 10 kg / cm ² . The copper foil layer was etched into an electric circuit pattern with an aqueous solution of ferric chloride to form three types (a wiring board-1 using the laminated body-1, a laminated body-2, a wiring board-2, and a laminated body-
The wiring board of No. 3 was a wiring board-3).

(6) Production of Film Wiring Substrate of the Present Invention 1 ounce of rolled copper foil was heat-sealed on the surface of the copolymerized PPS composition layer of PPS laminated film-1 under the conditions of the above (5) to form an electric circuit. Was formed (wiring board-A).

(7) Production of Multilayer Wiring Board of the Present Invention Copolymerized PP by the same production method as p-PPS film-1
An unstretched film of S composition having a thickness of 25 μm was obtained (m−
PPS film). In addition, holes to be through holes were formed in wiring board-1 and wiring board-A. Four layers of wiring board-1 and three layers of wiring board-A were alternately laminated via the m-PPS film, and heat fusion was performed under the conditions of a temperature of 260 ° C and a pressure of 7 kg / cm ² . A hot plate pressing method was used for heat fusion. Further, through holes were processed by metal plating to obtain a 7-layered multilayer wiring board (Example 1). By the same method, a multilayer wiring board having a combination of the wiring board-2 and the wiring board-A and a combination of the wiring board-3 and the wiring board-A was manufactured (in the order of Example 2 and Example 3).

COMPARATIVE EXAMPLE 1 Wiring boards-1 of Example 1, Example 2 and Example 3 were produced using m-PP.
A 7-layered multilayer wiring board was produced under the conditions of Example 1, Example 2 and Example 3 through the S film.

Comparative Example 2 p-PPS Films of Examples 1, 2 and 3
1 was superposed on both sides of the fiber sheet 1 and heat-bonded under the conditions of Example 1, Example 2 and Example 3 to impregnate the sheet with only the PPS composition (ink penetration was 0.3). After that, a 1 ounce rolled copper foil was heat-sealed on one surface of the sheet under the same conditions to etch the copper foil into an electric circuit pattern (wiring board-4). Next, an electric circuit was formed on one surface of the p-PPS film-1 under the same conditions (wiring board-B). Four layers of the wiring board-4 and three layers of the wiring board-B were alternately laminated and heat-sealed under the conditions of a temperature of 300 ° C. and a pressure of 10 kg / cm ² .

COMPARATIVE EXAMPLE 3 PPS laminated film-2 was formed on one surface with Example 1, Example 2,
A wiring board was produced under the conditions of the wiring board-A of Example 3, and m-
Comparative Example 4 in which a 7-layered multilayer wiring board was manufactured via a PPS film PP obtained by the same method as in Example 1, Example 2 and Example 3
The S laminated film was biaxially stretched. As for the stretching conditions, the sequential biaxial stretching method is used, and the longitudinal direction is the roll stretching method and the stretching temperature is 90.
C., the draw ratio is 3.5 times, and the width direction is a drawing temperature of 100.degree. C. and the draw ratio is 3.5 times in the tenter method. Then, it heat-processed at 260 degreeC for 10 second in the same tenter. 200 more
Free relaxation was performed at ℃ for 3 minutes. The thickness of the film was 25 μm and the thickness of the copolymerized PPS layer was 7 μm. On the surface of the copolymerized PPS composition layer of the PPS laminated biaxially oriented film thus obtained, 1 ounce copper foil was heat-sealed by the method of Example 1, Example 2 and Example 3 to form an electric circuit pattern. .

Comparative Example 5 A seven-layered multilayer wiring board was prepared with the structure of Comparative Example 4 from the wiring board-4 and the wiring board-B of Comparative Example 2 with the following adhesive. The adhesive used was an epoxy adhesive ("Chemit" Epoxy TE5920 Toray Co., Ltd.), which was applied to the non-circuit surface of the wiring board with an applicator to a thickness of 15 μm / Dry. The drying condition is 100 ° C. for 3 minutes. 7 the wiring board
The layers were laminated and laminated at a temperature of 120 ° C. and a pressure of 3 kg / cm ² , and the adhesive was further cured at 150 ° C. for 1 hour.

Example 4, Example 5 Six layers of the wiring board-1 and one layer of the wiring board-A of Examples 1, 2, and 3 were arranged so that the wiring board-A was the central layer. A seven-layer multilayer wiring board was produced under the conditions of Example 1, Example 2 and Example 3 (Example 4). Similarly, two layers of the wiring board-1 and five layers of the wiring board-A were laminated so that the wiring board-1 was located at both ends to obtain a seven-layered multilayer wiring board (Example 5).

Example 6 Amount of p-dichlorobenzene as a 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 the auxiliary component monomer m-dichlorobenzene added was 5 mol%. The same PPS as in Example 1 was used. Further, a PPS laminated film was produced under the conditions of Example 1 to obtain a laminated body wiring board. The wiring board and the wiring board-A of Example 1 were used as a multilayer wiring board in the configuration of Example 1.

Example 7 Amount of p-dichlorobenzene as the main component monomer added 69.8
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 auxiliary component monomer m-dichlorobenzene was 30 mol%. The same PPS as that used in Examples 1, 2 and 3 was used. Further, in the same manner as in Example 6, a 7-layer multilayer wiring board was produced.

Example 8 Copolymerization P of laminate-1 of Examples 1, 2 and 3
An electrical circuit pattern was provided on the surface of the PS layer by silk printing with a silver paste (wiring board-5). The circuit thickness was 15 μm. Also, a similar circuit was formed on the side of the copolymerized PPS layer of PPS laminated film-1 (wiring board-B). The above-mentioned wiring board-5 and wiring board-B were laminated by the configurations and methods of Example 1, Example 2, and Example 3 to produce a 7-layer multilayer wiring board.

Evaluation of Examples and Comparative Examples Tables 1 and 2 show the evaluation results of the multilayer wiring boards of Examples 1-8 and Comparative Examples 1-5.

The multilayer wiring boards of Examples 1 to 8 of the present invention have high-dimensionally balanced characteristics such as heat resistance, thermal dimensional stability, and high frequency characteristics, and have a reduced thickness, reduced circuit resistance, and fine pattern. It can be seen that this is a high-performance wiring board that can also be used. A conductor layer and a PP to be a circuit of the multilayer wiring board of the present invention
Since the bonding of the insulating substrate containing the S resin composition as a main component and the bonding for forming the wiring boards into multiple layers are all PPS, various characteristics such as high frequency characteristics, low hygroscopicity, and flame retardancy of PPS are obtained. It became highly adhesive without deteriorating. Furthermore, since the degree of impregnation of the resin and the fiber sheet is high, the reliability of the through hole is also high.

When the cross sections of the wiring 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
The S resin composition layer was thick, and the copolymerized PPS resin composition layer was provided thereon. 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 in the thickness direction enters 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.

If the wiring board having the PPS film as the insulating base material is not included as in Comparative Example 1, it is difficult to reduce the total thickness of the multilayer wiring board (resin impregnation that contributes to heat resistance and thermal dimensional stability). Since the thickness of the fiber sheet is rate-limiting), it is difficult to meet the market needs of electronic equipment, which tends to be thinned as much as possible.

The multilayer wiring board of Comparative Example 2 was formed by joining the circuit board and forming a multilayer wiring board without interposing a copolymerized PPS resin composition layer. The interlayer bonding force of each subsequent wiring board is weak.

In Comparative Example 3, the PPS unstretched film alone was used as the insulating substrate, and the heat resistance was poor. In Comparative Example 4, the PPS biaxially oriented film alone was used as the insulating substrate,
It turns out that there is a problem in thermal dimensional stability.

The multilayer wiring board of Comparative Example 5 has the same laminated structure as that of Examples 1, 2 and 3, but since each layer has an adhesive other than PPS interposed, it is characterized by PPS. It can be seen that certain high frequency characteristics, moisture absorption characteristics, etc. are significantly impaired.

In addition, the laminated constitution ratio of the film wiring board (the one in which the film is used as an insulating base material) is 0.1 to 0.7 with respect to the total number of all layers in the multilayer wiring boards of the present invention from Examples 4 and 5. It is found that is preferable for achieving the object of the present invention. That is, Example 4 in which the laminated constitution ratio is small
It is difficult to achieve thinning (miniaturization) of the multilayer wiring board and high number of layers, which is one of the objects of the present invention, and conversely, in Example 5 in which the lamination constitution ratio is large, heat resistance and thermal dimensional stability are high. It tends to decrease.

In addition, from Examples 1, 2, 3, 6, and 7, the main component monomer and subcomponent monomer (copolymerization component) of the copolymerized PPS to be the adhesive layer of the circuit layer and the insulating base material and the interlayer adhesive layer of each wiring board are obtained. Although the object of the present invention can be achieved even if the addition ratio of) is changed, if the addition ratio of the copolymerization component exceeds 30 mol%, heat resistance and thermal dimensional stability decrease, and conversely if it becomes less than 5 mol%. The above adhesive force tends to decrease.

Further, since the multilayer wiring boards of the present invention from Examples 1, 2, 3 and 8 use the copolymerized PPS layer, the electric circuit can be formed by a metal layer or a conductive paste layer containing a metal. However, it is advantageous to form the circuit with a metal layer in terms of the conductive resistance of the circuit.

[Table 1]

[Table 2]

[0101]

EFFECTS OF THE INVENTION Since the multilayer wiring board of the present invention has the above-mentioned structure, it has a high level of balance of heat resistance, thermal dimensional stability, high frequency characteristics, moisture absorption characteristics, and is thin (small) and high in thickness. It has become a multilayer wiring board that can be multilayered (higher density). The multilayer wiring board of the present invention can reduce the resistance value of the circuit, and is particularly suitable for high-speed signal processing, high frequency compatibility, small size, light weight, high density, and the like.

Claims (3)

[Claims] 1. A sheet comprising a fibrous sheet (A) impregnated with a resin composition (B) containing poly-p-phenylene sulfide as a main component, and at least one copolymerized unit other than the p-phenylene sulfide unit. A laminate wiring board in which an electric circuit is provided on the surface of the layer C of a laminate comprising a resin composition (C) layer of a copolymerized polyphenylene sulfide containing C, and C of a laminate film of a poly-p-phenylene sulfide film and C A multilayer wiring board having a film wiring board having an electric circuit provided on a layer surface, wherein the laminated wiring board and the film wiring board are laminated with at least one or more layers each interposed by a C layer. Wiring board. 2. A multilayer wiring board, wherein the fiber sheet is infusible at a temperature of 400 ° C. 3. A multilayer wiring board, wherein the fiber sheet is glass fiber.