JP3047474B2 - Laminated body and circuit board using the same - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a laminate and a circuit board using the same, and more particularly, to a laminate comprising a fiber sheet and an unstretched sheet mainly composed of poly-p-phenylene sulfide, and the laminate. The present invention relates to a circuit board having a body as a base material.

[0002]

2. Description of the Related Art In the electric and electronic industries, various characteristics such as heat resistance, thermal dimensional stability, low moisture absorption, flame retardancy, and high frequency characteristics are balanced from the viewpoint of miniaturization and high performance of equipment. There is an increasing demand for substrates that can be fused at a relatively low temperature (have self-fusing properties). If an adhesive is used for the bonding process, the above-mentioned various properties are deteriorated. Therefore, in order not to lower the various properties, self-fusing property is extremely important, and in particular, a circuit board (including a multilayer circuit board). In the field of (2), self-fusing property is strongly required for the production of high-frequency substrates and shield substrates.

The most noticeable substrates in this field are unstretched sheets of poly-p-phenylene sulfide and biaxially oriented films. As a laminated film or a laminated body using a biaxially oriented poly-p-phenylene sulfide film (hereinafter, may be abbreviated as a PPS film), there are (1) a laminated film with a polyester film (Japanese Patent Application Laid-Open No. 62-292431). JP-A-60-63158, (2) Laminated with aromatic polyamide fiber sheet via an adhesive, and (3) Infusible at a temperature of 300 ° C and at a temperature of 150 ° C Thermal expansion coefficient at 50 ×
Laminate with fiber sheet of 10 ^-6 1 / ° C or less
No. 95585) is known. Also, (4)
A laminate of an unstretched sheet of poly-p-phenylene sulfide (hereinafter sometimes abbreviated as a PPS sheet) and a PPS film is also known (Japanese Patent Application No. 63-19559).
No. 1).

[0004]

However, the above-mentioned PPS
Each of the sheet, the film and the laminate has the following problems.

A PPS sheet alone has a lower heat resistance temperature than a PPS film (it tends to be thermally deformed beyond the glass transition point), and the crystallization becomes more brittle as the number of heating steps increases. When used as a base of a printed circuit board, the crystal size and the like are controlled to satisfy the heat resistance and the fragility to some extent, but there is a problem that the heat is easily deformed when suddenly heated.

On the other hand, since the PPS film itself undergoes dimensional change due to thermal shrinkage, for example, if heat is applied in the process of manufacturing a circuit board, circuit misalignment is likely to occur. Further, there is a problem that the laminated circuit board is easily torn during through-hole processing. Further, in the laminating step, the heat fusion temperature is 26
Since the temperature is as high as 0 ° C. or higher, it is difficult to process in a field requiring such heat fusion (self-fusion).

In order to solve the problems in the PPS sheet and the film alone, various laminated films and laminates have been proposed as described above, but each has its own problems. The laminated film with the polyester film described in the above item (1) improves the tearability during through-hole processing, but does not improve the thermal dimensional stability and heat resistance. The laminate obtained by laminating the aromatic polyamide fiber sheet of (2) with an adhesive is improved in heat resistance,
The heat resistance of the adhesive adversely affects the substrate (that is, the heat resistance of the adhesive becomes the rule of the heat resistance of the substrate as a whole).
The excellent properties of PS film cannot be fully utilized. Also, P
The laminate of item (3), in which the PS film and the fiber sheet are laminated by heat fusion, has poor adhesive strength and easily peels off when a force such as bending is applied. In any case, the laminated film and the laminate of the above items (1) to (3) have no effect of improving the self-fusing property. Although the laminate of the above item (4) has a self-fusing property on the PPS sheet side, it lacks thermal dimensional stability and heat resistance as a whole of the laminate because the laminate is a PPS film.

The present invention solves the above-mentioned problems, balances various properties such as heat resistance, dimensional stability (heat and humidity), flame retardancy, and stability against high frequency, and furthermore, heat-fuses at a relatively low temperature. An object of the present invention is to provide a heat-resistant base material which has a function of attaching (self-fusing property) and is particularly suitable for use in a circuit board (including a multilayer circuit board).

[0009]

That is, according to the present invention, an unstretched sheet (B) containing poly-p-phenylene sulfide as a main component is formed on at least one surface of a fiber sheet (layer A).
Wherein the layer B) is fixed without an adhesive therebetween, wherein the residual crystallization energy ΔHt of the layer B is at least 20% of the crystallization energy ΔHq of the resin constituting the layer B. And a circuit board provided with an electric circuit provided on at least one surface of the laminate.

[0010] The fiber sheet in the present invention is a thin sheet composed of an aggregate of fibers, and is a cloth, cloth,
A generic term for felt, nonwoven fabric, paper, etc., with a thickness of 10 to 500
μm (preferably 10 to 300 μm). The fiber sheet may be processed such as easy adhesion and coloring, or may be a mixture or a laminate of two or more materials. Among the fiber sheets, cloths are preferable, and glass fiber cloths are particularly preferable in terms of heat resistance, dimensional stability, and workability, since the poly-p-phenylene sulfide polymer easily penetrates into the fiber sheet (easy to impregnate).

The above-mentioned fiber sheet preferably does not have a melting point up to a temperature of 400 ° C. The fiber sheet having no melting point means a fiber sheet which is infusible at a temperature of 400 ° C. Here, "infusible" means a state in which it is not melted or softened when exposed to a temperature of 400 ° C.
If the fiber sheet used in the present invention does not have the above properties,
When the laminate of the present invention is heated to a temperature around 300 ° C., the laminate is thermally deformed and the thermal dimensional change is increased.

In the present invention, poly-p-phenylene sulfide (hereinafter sometimes abbreviated as PPS) is
70 mol% or more of the repeating unit (preferably 85 mol%)
The above refers to a polymer comprising a structural unit represented by the following structural formula (Formula 1). When the content of such a component is less than 70 mol%, the crystallinity of the polymer, the heat transition temperature, and the like are low, and the heat resistance, dimensional stability, mechanical properties, and the like, which are characteristics of a film composed of a resin composition containing PPS as a main component, are impaired.

[0013]

Embedded image

In the above PPS, 30 units of the repeating unit
If it is less than mol%, preferably less than 15 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 sometimes abbreviated as a PPS-based composition) contains 60% by weight or more of poly-p-phenylene sulfide. Refers to a composition. PP
When the content of S is less than 60% by weight, mechanical properties such as tear strength, heat resistance, and the like of an unstretched sheet made of the composition are impaired. The remaining less than 40% by weight in the composition is P
Polymers other than PS, inorganic or organic fillers, lubricants,
Additives such as colorants can be included. Furthermore, PP
The melt viscosity of the S-based composition is as follows: temperature 300 ° C., shear rate 20
Under ⁰ sec ⁻¹ , the range of 700 to 20,000 poise is preferable in view of sheet formability.

The unstretched (non-oriented) polyphenylene sulfide sheet (PPS sheet) according to the present invention refers to the above-mentioned P
It is a general term for films, sheets and plates having a thickness of 700 μm or less obtained by melt-molding a PS-based composition, and refers to a substantially unstretched (non-oriented) film.

The laminate of the present invention comprises the above-described fiber sheet and P
A PS sheet is laminated without interposing an adhesive. When the adhesive is interposed, the adhesive has an adverse effect, and the heat resistance, electrical characteristics, and the like of the laminate are reduced. Here, the adhesive refers to a layer having a thickness of 1 μm or more other than a fiber sheet and a PPS sheet used for bonding each layer of the laminate.

In the laminate of the present invention, the bonding interface between the fiber sheet and the PPS sheet may be either bonded at the surface or the PPS sheet may enter the fiber sheet (impregnation). -When the hole processing is performed, it is preferable that the PPS sheet enters the inside of the fiber sheet from the viewpoint of the workability of the through-hole.

The residual crystallization energy ΔHt of the layer B of the laminate according to the present invention is the crystallization energy of the PPS sheet layer of the laminate (after lamination), and is observed by a microscope from a whole laminate or a microtome or the like. The PPS sheet can be taken out while taking it out, and the difference can be determined from the exothermic peak area of crystallization (Tcc) appearing when the temperature is raised by a differential scanning calorimeter (DSC).

The crystallization energy Δ of the resin constituting the B layer
Hq refers to the difference between a PPS sheet of a laminate and a differential scanning calorimeter (D
SC), the sample is heated to a temperature equal to or higher than the melting point, and once melted, the sample is quenched in a refrigerant such as liquid nitrogen.
It can be determined from the exothermic peak area of crystallization that appears when the temperature is raised in SC. It is necessary that the residual ratio of ΔHq after the formation of the laminate, that is, ΔHt / ΔHq × 100, is 20% or more in order to impart the self-fusing property as an object of the present invention.

The thickness structure of the laminate of the present invention is as follows: when the thickness of the fiber sheet is [A] and the thickness of the PPS sheet is [B], the fiber sheet / PPS sheet according to the first aspect of the present invention. In the two-layer laminate, the range of 0.3 ≦ A / B ≦ 3.0 is preferable in terms of impregnation, heat resistance, thermal dimensional stability, and workability. Further, the thickness of the entire laminate is preferably in the range of 20 to 500 μm.

Further, in a three-layer laminate (PPS sheet / fiber sheet / PPS sheet), which is the second embodiment of the laminate structure, when the thickness of each layer is [B], [A], and [B '], The range of 0.3 ≦ B + B ′ / A ≦ 3.0 is preferable for the same reason as the above two-layer laminate. Further, the thickness of the entire laminate is preferably in the range of 30 to 700 μm. The thickness ratio B / B 'of B and B' is preferably in the range of 0.5 to 2.0 from the viewpoint of workability. Further, the laminate may be oxidatively crosslinked by heat, ultraviolet rays, or the like.

The laminate of the present invention is particularly suitable as a base substrate of a circuit board (including a multilayer circuit board). The circuit board of the present invention is one in which an electric circuit is formed on at least one surface of the laminate. An electric circuit is an electric passage formed by patterning a conductor. As the conductor, a metal such as copper or aluminum, or a conductive paint containing copper, silver, carbon, or the like is usually used. Further, electric or electronic components may be mounted on the electric circuit. Further, two or more circuit boards may be laminated.

In order for the laminate of the present invention to have self-fusing properties, it is essential that the residual crystallization energy ΔHt of the B layer is 20% or more of the crystallization energy ΔHq constituting the resin of the B layer. However, in the circuit board of the present invention manufactured using the laminate, ΔHt is not necessarily 20% or more of ΔHq. That is, ΔHt of the B layer of the laminate when a final product is obtained after several heating steps as in the circuit board and the laminated circuit board.
May not always be 20% or more. However, even in this case, processing of a circuit board or a laminated circuit board,
In the production stage, the self-fusing property of the laminate according to the present invention has been fully utilized, and the effect of improving heat resistance and adhesive strength by using no adhesive in the final product can be obtained.

(Production Method) Next, a method for producing the laminate and the circuit board of the present invention will be described. First, the PPS used in the present invention is obtained by reacting an alkali sulfide and paradihalobenzene in a polar solvent at high temperature and high pressure. In particular, it is preferable to react sodium sulfide with paradichlorobenzene in an amide high boiling point polar solvent such as N-methylpyrrolidone. In this case, in order to adjust the degree of polymerization, it is most preferable to add a so-called polymerization aid such as a strong alkali or an alkali metal carboxylate and react at 230 to 280 ° C. The pressure and polymerization time in the polymerization system are appropriately determined depending on the type and amount of the auxiliary agent used, the desired degree of polymerization, and the like. The obtained powdery or granular polymer is mixed with water or / and
And washing with a solvent to separate by-product salts, polymerization aids, unreacted monomers and the like.

In order to form the polymer into the PPS sheet of the present invention, the polymer is supplied to a melt extruder typified by an extruder and is melted at a temperature higher than the melting point of the polymer (preferably 3 or more).
After heating the mixture to a temperature in the range of 00 to 350 ° C. and kneading it sufficiently, it is continuously extruded from a slit-shaped die, and rapidly cooled to a temperature below the glass transition point of the film to obtain a crystallization (Tcc) peak. A substantially non-oriented sheet having a temperature of 125 ° C or higher is obtained. If the extrusion temperature is low, the kneading state is insufficient, or the cooling rate is delayed, crystallization occurs, which is not preferable. The peak temperature (Tcc) of crystallization generated when the temperature is increased from 20 to 180 ° C. at a rate of 20 ° C./min in an inert gas atmosphere by a differential scanning calorimeter (DSC) is 125 ° C. or more (preferably 130 ° C.).
(In the range of 160 ° C. to 160 ° C.) is preferable in that it is difficult to crystallize when heat is applied as a laminate and that it is workable. On the other hand, if the extrusion temperature is too high, there are adverse effects such as the occurrence of firing on the sheet due to thermal decomposition.

The obtained PPS sheet is subjected to a surface treatment for easy adhesion such as a corona discharge treatment, a plasma treatment, and a primer treatment, if necessary.

Next, a method of manufacturing a laminate will be described. First, 2
Examples of the layer laminate include the following methods (1) to (4). (1) The PPS sheet and the fiber sheet are superimposed and the temperature is 1
Under conditions of 50 ° C. to 270 ° C. and a pressure of 1 to 30 kg / cm ² ,
A method comprising, after heat fixing with a hot roll press or a hot plate press, cooling through a cooling roll, a cooling plate, fresh air, or water to prevent crystallization of the PPS sheet of the laminate of the present invention. When the lamination temperature is lower than 150 ° C., the adhesiveness of the laminate is poor, and when it exceeds 270 ° C., the planarity of the laminate deteriorates, and it becomes difficult to control the thickness of the laminate. The hardly enters the inside of the fiber sheet PPS is less than lamination pressure 1 kg / cm ^2, exceeds 30kg / cm ² PP
The S sheet breaks or the flatness of the laminate deteriorates.

(2) The PPS sheet and the fiber sheet are stacked one on another under the conditions of a temperature of 80 ° C. to 130 ° C. and a pressure of 1 to 30 kg / cm ² , and further two layers by the method shown in (1). Method. In this case, if the lamination temperature of the single-stage lamination is lower than 80 ° C., there is no adhesiveness to the fiber sheet, and the workability of the subsequent step (1) is poor. If the temperature exceeds 130 ° C., the crystallization of the PPS sheet proceeds, and the self-fusing property and mechanical properties of the laminate obtained through the subsequent step (1) are reduced. If the pressure is less than 1 kg / cm ² , adhesion will not occur in the temperature range of the single-layer lamination, and if it exceeds 30 kg / cm ² , the flatness will deteriorate, and the workability in the subsequent step (1) will deteriorate.

(3) A method in which PPS is supplied to an extruder represented by an extruder, melted, extruded from a slit-shaped die, and integrated while being laminated on a lower fiber sheet.

(4) A method in which the laminate obtained by the method (3) is further laminated by the method (1). This is effective in causing PPS to enter the interior of the fiber sheet. The thickness of the two-layer laminate is preferably in the range of 20 to 500 μm from the viewpoint of securing flatness and controlling crystallization.

Next, a method for manufacturing a three-layered laminate will be described. (5) After obtaining a two-layer laminate by the method of (1) to (4), another PPS sheet is superimposed on the fiber sheet side of the two-layer laminate, and heat is applied under the condition of (1). How to stick and cool.

(6) PPS sheet, fiber sheet, PPS
A method in which the sheets are stacked in this order, and simultaneously heat-fixed and cooled under the condition (1).

(7) A method of forming a three-layer laminate by the method of (2), followed by heat fixing and cooling under the conditions of (1). And the like.

The thickness of the three-layer laminate is preferably in the range of 30 to 700 μm from the viewpoint of securing flatness and controlling crystallization.

Further, the laminate of the present invention uses a film (biaxially oriented film) obtained by biaxially stretching a PPS sheet by a well-known method and heat-treating the film, and using the film at a temperature equal to or higher than the melting point of the film (285 ° C.).
In the case where the PPS layer is melt-laminated by the method (1) or (6) at the above temperature, the requirement of the PPS layer is included in the scope of the present invention.

Next, a method of manufacturing a circuit board based on the laminate of the present invention will be described. A metal foil such as aluminum or copper is laminated on one or both sides of the above-mentioned laminate by heat fusion or an adhesive, or the above-mentioned metal is deposited on a metal layer by a method such as a vacuum deposition method, a plating method, or a sputtering method. And a desired circuit pattern is formed by etching using a ferric chloride aqueous solution or the like. Further, a circuit pattern is formed by a method such as a silk printing method using a conductive paint containing silver, copper, carbon, or the like, and the paint is cured by heat or ultraviolet rays as necessary. Further, if necessary, the above-mentioned circuit boards are laminated to form a multilayer circuit board, through-hole processing, and electric and electronic circuits are mounted.

[0038]

According to the present invention, the heat resistance, the dimensional stability (heat and humidity), the flame retardancy, the high frequency characteristics, and the like are balanced at a high level. A laminate was obtained. These characteristics are most suitable for circuit boards and laminated circuit boards.

(Application) In addition to the circuit board and the laminated circuit board, the laminate of the present invention may be used as a heat-resistant insulating material for transformers and motors, a covering material for cables used for high-temperature and high-pressure parts,
Ideal for heat-resistant adhesive tape, prepreg base, heat-resistant label base, speaker cone, shield base, etc.

Further, another material (metal, sheet, etc.) may be laminated on at least one surface of the laminate of the present invention,
Another resin or a coating agent may be coated or molded. Further, the laminate of the present invention may be oxidatively cross-linked by heat, ultraviolet light or the like.

(Characteristic Evaluation Method) Next, a characteristic evaluation method and evaluation criteria used in the description of the present invention will be described. (1) Residual crystallization energy (ΔHt) The PPS sheet of the surface layer of the laminate is taken out and PERKI
The exothermic peak area of crystallization (Tcc) which appears when the temperature is raised to 20 to 180 ° C. in an inert gas atmosphere under the following conditions using a DSC-2 type differential scanning calorimeter manufactured by N-ELMER is calculated by the following method. × height, base × height / 2) or by the gravimetric method, and the value determined from the peak area of indium as a reference substance, a constant K is calculated, and the crystallization energy ΔHt (unit: cal) of the laminate is calculated by the following equation. / G). ΔHt = (K × R × peak area (cm ² )) / (Ws × Vc (cm / sec))

(2) Crystallization Energy (ΔHq) A portion of the PPS sheet of the laminate is sampled, and the temperature is raised to 20 to 340 ° C. and melted by DSC in an inert gas atmosphere. Then, after quenching with a refrigerant such as liquid nitrogen to obtain a non-oriented sample, the crystallization energy ΔHq is determined again under the conditions when ΔHt was measured using DSC.

(3) Crystallization temperature (Tcc) The sample film was manufactured by PERKIN-ELMER (DSC
-2 type) differential scanning calorimeter, 20 to 18 under the following conditions:
The crystallization (Tcc) peak that appeared when the temperature was raised to 0 ° C. was represented by a read value.

(4) Heat resistance A 2 cm square sample was floated in a solder bath set at a temperature of 280 ° C. for 5 seconds, and evaluated according to the following criteria. : No change at all △: Softening, deformation, peeling, wrinkles, etc. are observed in part. ×: The entire surface is deformed or peeled, such as waving or bending, and the dimensional change of each layer is greatly different.

(5) Heat Shrinkage A sample is cut into a 100 mm square, and the length of each side is further accurately read with a microscope (α mm). Next, after aging for 5 minutes in a furnace (far-infrared ray method) heated to a temperature of 250 ° C., the length of each side is measured accurately (β mm). The heat shrinkage (%) was determined by the following equation, and expressed by the larger heat shrinkage. Heat shrinkage (%) = ((α−β) / α) × 100

(6) Adhesion The laminated body was bent five times at 180 degrees, and the bent portions were observed and evaluated according to the following criteria. : There is no peeling of the bent portion and no decrease in the peeling strength of the bent portion. Δ: The bent portion was partially peeled, and the peel strength was slightly reduced. ×: The bent portion peels off.

(7) Self-fusing force The laminate was thermally fused under the conditions of a temperature of 200 ° C. to 250 ° C. and a pressure of 1 kg / cm ² , and the peel strength (kg / cm) was measured by Tensilon.

(8) Circuit Displacement The circuit board was passed through a furnace (far-infrared ray system) set at a temperature of 200 ° C. for 5 seconds, and the circuit was deviated from the circuit not passing through the furnace.

(9) Through-Hole Property The through-hole portion of the through-hole processed sample was observed with a microscope, and the adhesion state of the conductive paint was examined.

(10) Dielectric Characteristics (Dielectric Loss) Changes in dielectric loss were examined by changing the frequency. (JIS-
It measured according to C-6481. )

(11) Bendability The laminate was cut into a 10 mm width and bent at 180 degrees for 20 times, and the degree of cracking at the bent portion was observed. : No crack is generated. Δ: Cracks of less than 5 mm occurred in the width direction. ×: Cracks of 5 mm or more occurred in the width direction.

[0052]

Next, the present invention will be described in detail with reference to examples. Example 1 (1) Preparation of unstretched PPS sheet used in the present invention. In an autoclave, 32.6 kg of sodium sulfide (250
Mol, containing 40% by weight of water of crystallization), sodium hydroxide 1
00g, 36.1 kg (250 mol) of sodium benzoate, and 79.2 kg of N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP), and after dehydration at 205 ° C, 1,4 dichlorobenzene was added. 5 kg (25
5 mol) and 20.0 kg of NMP, and reacted at 265 ° C. for 4 hours. The reaction product is washed with water, dried and p-
Consisting of 100 mol% of phenylene sulfide units,
21.1 kg (78% yield) of poly-p-phenylene sulfide having a melt viscosity of 3100 poise was obtained.

Into this composition was added 0.1% by weight of silica fine powder having an average particle size of 0.7 μm, and calcium stearate 0.1%.
The mixture was melted at 310 ° C. with an extruder having a diameter of 40 mm, filtered through a filter having a 95% cut hole diameter of 10 μm using a metal fiber, and then had a straight lip having a length of 400 mm and a gap of 0.5 mm. Extruded from the die, cast on a metal drum whose surface was kept at 25 ° C,
An unstretched sheet having a thickness of 25 μm was obtained (PPS sheet-1).
And).

(2) Preparation of fiber sheet 3 of glass cloth (EPC030 manufactured by Arisawa Seisakusho)
4 μm was used (referred to as “fiber sheet-1”).

(3) Formation of Laminate The above-mentioned PPS sheet-1 and fiber sheet-1 are superimposed, pressed on a hot plate at a temperature of 240 ° C. and a pressure of 8 kg / cm ² , and immediately after pressing for 1 minute. Cool the hot plate with water,
The temperature was lowered to a temperature of 00 ° C. to obtain a laminate (laminate-
1).

Example 2 A PPS sheet-1 was overlaid on both sides of the fiber sheet-1 of Example 1, and thermocompression bonded by a hot roll press method. The lamination conditions are a temperature of 230 ° C., a pressure of 10 kg / cm ² , and a line speed of 1.0 m / min. Furthermore, after lamination, it was cooled by a cooling roll (roll temperature: 20 ° C., water cooling) subsequent to the heating roll to obtain a three-layer laminate (laminate-2).

Example 3 The method of Example 2 was repeated except that the lamination conditions were a temperature of 120.degree.
kg / cm ² and lamination, temperature 200 ° C, pressure 10kg
/ Cm ² and then cooled again under the conditions of Example 2 (laminate-3).

Example 4 The PPS polymer used in Example 1 was melted at 310 ° C. with an extruder having a diameter of 30 mm and extruded from a T die having a length of 240 mm and a linear lip having a distance of 0.5 mm. On the other hand, a metal press roll whose surface temperature was kept at 90 ° C. was provided directly below the T die, and the fiber sheet-1 used in Example 1 was laminated with the extruded polymer while pressing at a speed of 1 m / min. Further, another PPS sheet-1 was laminated on the fiber sheet side of the laminate under the conditions of Example 1 (laminate-4).

Comparative Example 1 The PPS sheet was manufactured under the same conditions as in Example 1 except that the melting temperature was 29.
A PPS sheet was obtained under the same conditions as in Example 1 except that the method of cooling the cast film extruded from the T-die at 0 ° C. was changed (referred to as PPS sheet-2). Next, the PPS sheet-2 was overlaid on both sides of the fiber sheet-1 to obtain a three-layer laminate under the conditions of Example 1 (laminate-5).

Comparative Example 2 The laminated structure of Example 2 was used and laminated by the method of Example 1. The lamination conditions were the same as those in Example 1, but the material was cooled without quenching (Laminate-6).

Comparative Example 3 Under the conditions of Example 1, a PPS sheet having a thickness of 100 μm was obtained. Further, the sheet was heat-treated at a temperature of 250 ° C. for 5 minutes (referred to as PPS sheet-3).

Comparative Example 4 100 μl of “TORELINA” type 3000 manufactured by Toray Industries, Inc.
An m-thick biaxially oriented PPS film was prepared (referred to as PPS film-1).

Comparative Example 5 25 μm of “TORELLINA” type 3030 manufactured by Toray Industries, Inc.
A thickness was prepared (PPS film-2), and PPS film-2 was superimposed on both sides of fiber sheet-1 so that the corona-treated surface was in contact with the fiber sheet.
The layers were laminated by a heated roll press method at a temperature of 10 ° C. and a pressure of 10 kg / cm ² (Laminate-7).

Comparative Example 6 The laminated structure of Comparative Example 5 was laminated via an epoxy-based adhesive (“Chemit Epoxy” TE5920 (manufactured by Toray Industries, Inc.)). The adhesive was applied to the corona-treated surface of the PPS film-2 to a thickness of 10 μm (dry condition) by a gravure roll method, and laminated on both surfaces of the fiber sheet-1. The drying condition of the adhesive was 100 ° C. for 3 minutes, and the laminating condition was 12 minutes.
The pressing pressure was 3 kg / cm ² at a temperature of 0 ° C. 15 more
It was thermally cured at a temperature of 0 ° C. for 2 hours (laminate-8).

Comparative Example 7 The laminated structure of Example 2 was laminated by the method of Comparative Example 6 (laminate -9).

(Evaluation of Examples and Comparative Examples)
Tables 1 and 2 show the evaluation results of the laminates, sheets, and films of Comparative Examples 1 to 7. The laminates of Examples 1 to 4 of the present invention have a well-balanced combination of heat resistance, thermal dimensional stability, dielectric properties, adhesion and mechanical properties, and also have self-fusing properties. It can be seen that the purpose has been achieved.

On the other hand, since the laminates of Comparative Examples 1 and 2 have a residual crystallization energy ratio of less than 20% according to the present invention, they have poor bending properties and self-fusing properties and cannot achieve the object of the present invention.

The PPS sheet of Comparative Example 3 has poor heat resistance. The biaxially oriented PPS film of Comparative Example 4 has high thermal dimensional stability and lacks self-fusing properties.

The laminate of Comparative Example 5 has poor adhesion, and if heat is applied suddenly, the interface with the fiber sheet may peel off due to the stress during thermal contraction of the biaxially oriented PPS film. Further, since a biaxially oriented PPS film is used, self-fusing property is lacking.

In the laminates of Comparative Examples 6 and 7, the adhesive lowers the heat resistance and the dielectric properties because of the interposition of the adhesive. Further, since the laminate of Comparative Example 6 uses a biaxially oriented PPS film, the adhesive softens when heat is applied, and the biaxially oriented PPS film is used.
The PS film layer thermally contracts. Further, it lacks self-fusing properties.

Example 5 In the laminating method of Example 2, the laminating state and the characteristics of the laminated body were examined by changing the laminating temperature and the laminating pressure. The lamination temperature is
The range of 150 to 270 ° C was advantageous in terms of adhesiveness, flatness and workability. Also, if you a lamination temperature to 240 ° C. Experimenting with lamination ^{pressure, 1kg / cm 2 ~30kg / cm} 2 in the range of adhesion, impregnation of polymer to the fiber sheet, flatness, advantageous from the viewpoint of workability Met.

Example 6 An electric circuit was formed by patterning an electric circuit with a silver-containing conductive paint on one surface of the laminates of Examples 1 to 4 by a silk printing method and cured at a temperature of 150 ° C. for 10 minutes to prepare a circuit board. . The thickness of the paint was 10 μm. In all of the above four types of circuit boards, there was no deformation to 280 ° C. solder, and no circuit displacement occurred. Through-hole processing with a diameter of 0.5 mm was performed, but the adhesion of the conductive paint was also good. In addition, each of the above-mentioned circuit boards is made of four layers at a temperature of 24.
Lamination was performed under the conditions of 0 ° C. and a pressure of 1 kg / cm ² , but the self-fusing property was also good.

Comparative Example 8 An electric circuit was provided on one surface of the laminates, films and sheets of Comparative Examples 2 to 6 under the conditions of Example 6 to obtain five types of circuit boards. In the case of the laminate based on Comparative Example 2, the PPS layer is easily torn at the time of through-hole processing, and the self-fusing property in the case of multilayering is poor. PPS sheet-3 of Comparative Example 3
In the case of using, it is deformed when it floats on 280 ° C. solder. In the case of using the PPS film-1 of Comparative Example 4, the thermal dimensional change rate was large, and a circuit deviation occurred. In the case of using the laminate of Comparative Example 5, the adhesion to the fiber sheet PPS film was weak, and the laminate was peeled off during through-hole processing. In the laminate of Comparative Example 6, the adhesive softened when exposed to a high temperature,
The PPS film on the surface layer contracted by heat, and the circuit was shifted. In addition, high-frequency characteristics and the like are reduced by the influence of the adhesive.

[0074]

[Table 1]

[0075]

[Table 2]

────────────────────────────────────────────────── ─── Continuation of the front page (56) References JP-A-57-96588 (JP, A) JP-A-59-3991 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) B32B 1/00-35/00 H05K 1/03

Claims (4)

(57) [Claims] 1. A laminate in which an unstretched sheet (layer B) containing poly-p-phenylene sulfide as a main component is fixed to at least one surface of a fiber sheet (layer A) without using an adhesive. The residual crystallization energy ΔHt of the B layer is the crystallization energy ΔH of the resin constituting the B layer.
A laminate characterized by being 20% or more of q. 2. The laminate according to claim 1, wherein the fiber sheet has substantially no melting point up to 400 ° C. 3. The laminate according to claim 2, wherein said fiber sheet is a glass cloth. 4. A circuit board comprising an electrical circuit provided on at least one surface of the laminate according to claim 1.