JPH0245144A - Laminate and manufacture thereof - Google Patents

Abstract

PURPOSE:To obtain a laminate combining each characteristic of heat resistance, chemical resistance, flame-retardant properties, shock resistance, resistance to moist heat, workability, etc., in a balanced manner by laminating a biaxially oriented polyphenylene sulfide layer on at least one side of a non-oriented polyphenylene sulfide layer without through adhesives. CONSTITUTION:A biaxially oriented polyphenylene sulfide layer is laminated on at least one side of a non-oriented polyphenylene sulfide layer without through adhesives. A film or a sheet or the like in 1mm or less manufactured by melting and molding a composition containing not less than 60wt.% polyphenylene sulfide is used as a non-oriented sheet. A film obtained by melting and molding a resin composition including not less than 90wt.% polyphenylene sulfide, forming the resin composition to a sheet shape and biaxially orienting and thermally treating the sheet-like resin composition is employed as a biaxially oriented polyphenylene sulfide film. Both the sheet and the film are thermocompression-bonded at a high temperature and high pressure or PPS is melt-extruded and laminated directly onto the biaxially oriented film as a laminating method. The former method is executed by a roll press, a hot plate pres, etc., under the conditions of a temperature of 180-270 deg.C and a pressure of 1-20kg/cm<2>.

Description

DETAILED DESCRIPTION OF THE INVENTION [Industrial Field of Application] The present invention relates to a laminate. More specifically, the present invention relates to a laminate of an unstretched sheet containing poly-p-phenylene sulfide as a main component and a biaxially oriented poly-p-phenylene sulfide film, and a method for producing the laminate.

[Prior Art] As a conventional film, (1) a biaxially oriented poly-p-phenylene sulfide film (hereinafter sometimes abbreviated as a biaxially oriented PPS film) is used as an electrically insulating material. It is known from JP-A No. 55-35459. (2) Sheets of unstretched poly-p-phenylene sulfide are also available in JP-A-56-34426 and JP-A-57-
It is known from Publication No. 121052 and the like.

On the other hand, (3) laminating biaxially oriented PPS films with each other via an adhesive is also known from Japanese Patent Application Laid-Open No. 61-241142. In addition, (4) a laminated film of a biaxially oriented PPS film and a biaxially oriented polyester film (Japanese Unexamined Patent Publication No. 62-292431, etc.); (5) a biaxially oriented PPS film and a biaxially oriented polyester film;
Laminated body of PS film and 81i fiber sheet of aromatic polymer (Japanese Patent Application Laid-Open No. 60-63158), (6) Biaxially oriented PPS film and tetrafluoroethylene/hexafluoropropylene copolymer film Laminated film (Japanese Patent Application Laid-Open No. 62-29
No. 2432) and the like are also known.

[Problems to be Solved by the Invention] However, the above films, sheets, laminate films, and laminates have the following problems.

The film described in item (1) has poor impact resistance and tear strength, and when used, for example, as a slot liner or wedge for a motor, there is a problem that the film may tear or delaminate.

The unstretched sheet described in item (2) has high tear strength, but low tensile elongation, and when exposed to temperatures near the melting point, the strength rapidly decreases and shape retention deteriorates significantly.

Although the laminated film in item (3) has improved impact resistance and tear strength compared to the film in item (1), it is insufficient.
Further, since the adhesive is present, there is a risk that the excellent properties such as heat resistance and chemical resistance of the biaxially oriented PPS film will be deteriorated.

The laminated film described in item (4) cannot take advantage of the excellent properties of the biaxially oriented PPS film because the biaxially oriented polyester film on which it is laminated has poor heat resistance, chemical resistance, and heat and humidity resistance.

The laminate described in item (5) has excellent heat resistance and impact resistance, but
Since they are laminated with an adhesive interposed, the adhesive has poor heat resistance and chemical resistance, which deteriorates the properties of the laminate. Further, since the fiber sheets of the laminate have very high hygroscopicity, the dimensional change of the laminate under moist heat becomes large. Also,
The fiber sheets of the laminate come loose and chips are generated during slitting, which limits its application as an insulating material for motors that require precision (for example, Hermedec motors for refrigerators).

Roughly speaking, the laminated film of item (6) has excellent heat resistance and chemical resistance, and since it is laminated without an intervening adhesive, there is no fear that the adhesive will have an adverse effect on the laminated film. The laminated film also has high tear strength. but,
In order to manufacture this laminated film, each film requires special surface treatment, and because the adhesive strength of the laminated interface of this laminated film is poor, it may peel off if a sudden impact force is applied to one part. , there is a problem that the biaxially oriented PPS film is torn.

The present invention solves these problems and is a stand-alone PPS that provides a good balance of properties such as heat resistance, chemical resistance, flame retardance, impact resistance, heat and humidity resistance, and workability without using an adhesive. The purpose is to provide a laminate of.

[Means for Solving the Problem] The present invention provides a laminate in which a biaxially oriented polyphenylene sulfide layer (B) is laminated on at least one side of an unstretched polyphenylene sulfide layer (A) without using an adhesive, and the production thereof. This is about the method.

In the present invention, poly-p-phenylene sulfide (hereinafter sometimes abbreviated as PPS) is one in which 70 mol% or more (preferably 85 mol% or more) of repeating units are represented by the structural formula -+@=S) A polymer consisting of structural units. If the content of such components is less than 70 mol%, the crystallinity, thermal transition temperature, etc. of the polymer will be low, impairing the heat resistance, dimensional stability, mechanical properties, etc., which are characteristics of a film made of a resin composition containing PPS as a main component.

Less than 30 mol% of repeating units, preferably 15 mol%
If the amount is less than 1, there is no problem even if a unit containing a copolymerizable sulfide bond is included.

Further, the method of copolymerization of the polymer does not matter whether it is random or block type.

In the present invention, a resin composition containing poly-p-phenylene sulfide as a main component (hereinafter sometimes abbreviated as PPS-based composition) refers to a composition containing 60 or more poly-p-phenylene sulfides. To tell.

If the PPS content M is less than 60% by weight, the mechanical properties such as tear strength and heat resistance of the unstretched sheet made of the composition will be impaired.

The remaining less than 40% by weight of the composition can include additives such as polymers other than PPS, inorganic or organic fillers, lubricants, colorants, and the like.

The melt viscosity of the resin composition was determined at a temperature of 300°C and a shear rate of 2.
001/sec, a range of 700 to 20,000 voids is preferred from the viewpoint of sheet formability.

The unstretched sheet referred to in the present invention (hereinafter referred to as PP5-N).

It can be abbreviated as . ) is a general term for films, sheets, and plates having a thickness of 1 mm or less formed by melt-molding the above-mentioned PPS composition, and refers to substantially non-oriented films.

Biaxially oriented poly-p-phenylene sulfide film (hereinafter sometimes abbreviated as PP5-BO) in the present invention.

) is a film obtained by melt-molding a resin composition containing 90% by weight or more of poly-p-phenylene sulfide into a sheet, biaxially stretching it, and heat-treating it. If the content of PPS is less than 90% by weight, the crystallinity, thermal transition degree, etc. of the composition will be low, and the characteristics of the film made of the composition, such as heat resistance, dimensional stability, and mechanical properties, will be impaired.

The remaining less than 10% by weight of the composition can include additives such as polymers other than PPS, inorganic or organic fillers, lubricants, colorants, UV absorbers, and the like.

The melt viscosity of the resin composition was determined at a temperature of 300°C and a shear rate of 2.
Under 0Q 1/sec, a range of 500 to 12,000 poise (more preferably 700 to 10,000 poise) is preferable from the viewpoint of film formability.

The melt viscosity of the resin composition is equal to the melt viscosity of the final 1q biaxially oriented PP, S film.

The thickness of the film is preferably in the range of 3 to 300 μm.

In the present invention, PP, 5-No and PP5-BO are laminated without using an adhesive. The tip of the lamination is [Putte, PP
5-No may be subjected to heat treatment or oxidative crosslinking. Furthermore, the present invention also includes subjecting the surfaces of PP5-No and PP5-BO to corona discharge treatment or plasma treatment.

The first aspect of the possible laminated structure of the laminated body of the present invention is:
It is a two-layer structure in which PP5-No (A> and PP5-BO (B) are laminated, and the thickness ratio of A and B is A/B.
A range of 0.1 to 10 is preferable in terms of the balance between heat resistance when heat is applied, shape retention, and impact resistance. Moreover, the thickness of the entire laminate is preferably in the range of 20 to 700 μm.

A second aspect of the possible laminated structure of the laminated body of the present invention is:
PP5-BO (A), PP5-No (B), PP5-
BO (A”) is laminated in this order, A, A=
, B satisfies the formula % from the viewpoint of heat resistance when heat is applied, shape retention, and impact resistance.

Further, the thickness ratio A/Δ- between A and A' is preferably in the range of 0.5 to 2.0 from the viewpoint of workability during processing. Furthermore, the thickness of the entire laminate is preferably in the range of 30 to 1000 μm.

Moreover, the laminate of the present invention does not include an adhesive layer,
PP5-No and PP5-BO are joined by fusion.

Next, the laminate of the present invention! I! I will explain how to make it.

PPS used in the present invention is obtained by reacting an alkali sulfide and a baladihalobenzene in a polar solvent at high temperature and high pressure. In particular, sodium sulfide and balajichlorobenzene are
- The reaction is preferably carried out in an amide high boiling polar solvent such as 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 carboxylic acid salt, and to carry out the reaction at 230 to 280'C. The pressure within the polymerization system and the polymerization time are appropriately determined depending on the type and amount of the auxiliary agent used, the desired degree of polymerization, and the like. The resulting powdered or granular polymer is washed with water and/or a solvent to separate by-product salts, polymerization aids, unreacted additives, and the like.

To form this polymer into an unstretched sheet, it is supplied to a melt extruder such as an extruder, heated to a temperature higher than the melting point of the polymer, melted, and continuously extruded through a slit-shaped die to form the film. By rapid cooling to a temperature below the glass transition point, the unoriented sheet becomes 1
be qed.

Further, a biaxially oriented PPS film is obtained by biaxially stretching and heat treating the above-mentioned sheet by a well-known method.

Stretching is 3.0 to 90 to 110°C in both longitudinal and width directions.
Do this in a 4.5x range. The heat treatment is carried out at a temperature of 180°C to melting point, at a constant length or under limited shrinkage of 15% or less, from 1 to 60°C.
Do it for seconds. Additionally, the film may be relaxed in one or two directions to improve its thermal dimensional stability.

Next, PP5-NO and PP5-BO can be laminated by thermocompression bonding them together under high temperature and high pressure, or by directly melt-extruding PPS onto a biaxially oriented film.

In the former method, the temperature is 180-270'C.

This is carried out using a roll press, hot plate press, etc. under pressure conditions of 1 to 20 kg/cm.

When laminating three layers, a two-layer body is first created under the above conditions, and a biaxially oriented PPS film is further laminated on the unstretched sheet side of the two-layer body, or three layers can be laminated at the same time. .

On the other hand, when laminating PPS by directly melting and extruding it onto a biaxially oriented PPS film, the PPS is supplied to an extruder, heated to a temperature above its melting point, and continuously extruded through a slit-shaped die. 2 on press roll
It is laminated on the axially oriented PPS film while being pressed.

In addition, when laminating three layers, PPS can be extruded between two layers of biaxially oriented PPS films and laminated under the above conditions. Yet another method is to use the method 1 above.
Another biaxially oriented PPS film can be laminated on the unstretched PPS side of the 2-layer laminate by thermocompression bonding.

[Effects of the Invention] Since the laminate of the present invention has the above-described structure, it has excellent heat resistance (long-term heat resistance, high-temperature short-term heat resistance), moist heat resistance, impact resistance, and flame retardance, which are particularly important properties as an electrical insulating material. It has become a material with a high level of balance in properties such as gender.

Furthermore, since the laminate of the present invention does not contain an adhesive, deterioration of the adhesive will not deteriorate the properties of the laminate.

[Applications] The laminate of the present invention is most suitable for insulating materials for motors, transformers, etc. that require heat resistance, moisture and heat resistance, etc. For example, it can be used as an insulating material for various motors such as hermetic motors, servo motors, and vehicle motors that are used while immersed in refrigerating machine oil, various transformers such as gas transformers, oil transformers, and mold transformers, and generators.

Furthermore, since it has excellent radiation resistance and low-temperature properties, it is ideal as an electrical insulating material for equipment that requires radiation resistance, such as nuclear power plants, and as a coating material for superconducting materials.

We also provide coating materials for electric wires, printed circuit boards, belts and interior materials,
Also suitable for diaphragms, acoustic diaphragms, etc.

Further, the laminate of the present invention may be laminated with another film, a heat-resistant fiber sheet, or a metal, or may be coated with another resin.

Next, methods for measuring characteristics and evaluation criteria used to describe the present invention will be described.

(1) Initial temperature of heat-resistant sample film and 2 at 180℃ in hot air oven
The tensile strength after aging for 000 hours was determined by ASTM-D-
638-72 method, and if the strength after aging is 70% or more of the initial value, the heat resistance Q is 10 to 70.
Less than % was rated △, and less than 10% was rated X.

(2) Tear strength Measured according to J l5-P8116-1960, (j
Expressed in /mm.

(3) Cut out an impact-resistant sample to a width of 20 mm and a length of 100 mm, loop it in the length direction, fix the end, and insert a weight weighing 1 kq from a height of 20 cm from the tip of the sample in the width direction. The samples were dropped and ranked according to the following criteria.

○: The sample is not damaged at all.

△: Part of the tip is torn.

×: The tip is largely delaminated or torn.

(4) Heat resistance at high temperatures A sample with a width of 10 mm and a length of 50 mm was heated to 260°C ± 2°C.
After 10 seconds of soldering, both ends of the sample were held in the solder with tweezers and pulled by hand, and the heat resistance was judged based on the following criteria.

○: Does not stretch even when stretched.

△: Slightly stretches when pulled.

×: When pulled, the elongation is large and the film breaks.

(5) Humid and heat resistance Test II was placed in a 200CC autoclave, a small amount of water was added and the container was sealed, and the tensile elongation after aging at 120℃ for 100 hours was measured according to the ASTM-D-638-72 method. If the elongation is 70% or more of the initial value, heat and humidity resistance is 01.
The value less than the value was defined as X.

(6>ti A flammable sample was cut out to a width of 20 mm, the tip was exposed to a flame, and when the sample was moved away from the flame, the combustion state of the sample was evaluated based on the following criteria.

○: The fire goes out immediately.

△: Burns for a while and then disappears.

X: The fire won't go out.

(7) Adhesive Strength Peeled at 90 degrees using a shopper. The width of the sample is 10
mm, and the peeling speed was 200 mm/min.

(8) Breaking elongation Measured according to ASTM-D-638-72 method.

[Example] Next, the present invention will be explained in detail by giving examples.

Example 1 (1) Preparation of PPS unstretched sheet used in the present invention In an autoclave, 32.6 kq of sodium sulfide (250 mol, containing 40 wt% of crystal water) and 100 kq of sodium hydroxide were added.
q, sodium benzoate 36.1 kg (250 mol),
After charging 79.2 kCl of
5 mol) and 20.0 kg of NMP were added, and the mixture was reacted at 265°C for 4 hours. The reaction product was washed with water, dried, and p-
Consists of 100 mol% of phenylene sulfide units,
21.1 kl of poly-p-phenylene sulfide having a melt viscosity of 3100 poise was obtained (yield: 78%).

This composition contains 0 silica fine powder with an average particle size of 0.7 μm.
．． Added 1wt% and calcium stearate 0゜05W↑% and heated to 310℃ using a 4-layer mm diameter extruder.
95% cut hole diameter 10/, using metal fiber melted with
(Length 400 mm after filtering with m filter, interval Q
, extruded from a T-die with a 5 mm straight lip and cast onto a metal drum whose surface was kept at 25 °C.
An unstretched sheet with a thickness of 100 μm was obtained. (PPS-NO
-1. ) (2) Adjustment of PPS-BO A 50 μm thick PP5-BO manufactured by Toshi ■ “Torelina” type 3000 was used. (This is referred to as PPS-BO-1.) (3) Creation of laminate PP5-No-1 and PP5-BO-1 were heated at 230°C.
PP5-80/P with press roll at pressure 1Qkg/cm
Three layers were stacked and laminated to have a configuration of P5-NO/PP5-BO.

(Laminated body-1) Example 2 (1) Creation of laminate PP5-No-1 used in Example 1 and 100 μm thick PP5-80 of Torelina type 3000 manufactured by Toshi ■
(referred to as PPS-BO-2) were laminated under the conditions of Example 1 to create a two-layer body of PP5-No/PP5-BO. (This is referred to as laminate-2.) An unstretched sheet having a thickness of 150 μm was prepared under the conditions of Example 1. Further, the sheet was subjected to roll heat treatment at a temperature of 230° C. for 5 seconds. (PPS-NO-2, Comparative Example 1) An unstretched sheet with a thickness of 2.5 mm was created using the method of Example 1 with the interval between linear lips set to 1.5 mm under the same conditions, and this sheet was further rolled into a group of rolls. By a longitudinal stretching device consisting of
Stretched 3.9 times lengthwise at a temperature of 98°C and a stretching speed of 30,000%/min, then transversely stretched 3.5 times at a temperature of 100°C and a stretching speed of 1,000%/min using a tenter, and further stretched in the same tenter. A subsequent heat treatment was performed at 270° C. for 10 seconds in a heat treatment chamber to obtain PPS-808 with a thickness of 150 μm. (PPS-B
It is set as O-3. Comparative Example 2) One side of PPS-80-2 used in Example 2 was subjected to corona discharge treatment, and a two-layer body of PP5-BO was created using the following adhesive. (Laminated Film-1, Comparative Example 3) Adhesive: Urethane adhesive, "ATCODE'6P1" The mixing ratio of the main component and curing agent of the above adhesive is the main component/curing agent =
100/8, adjusted the solid content concentration to 32 wt% with ethyl acetate, and added PP5-BO-3 using the gravure roll method.
It was applied to the corona discharge treated surface of Drying conditions are 80℃ and 3.
The coating thickness was adjusted to 8 μm after drying.Then, the other PP5-BO-2 was laminated using a roll laminator.The lamination conditions were a temperature of 80°C and a pressure of 3 kq/cm. The laminated film was further cured at a temperature of 60'C for 50 hours.

25 μm of “Torelina” type 3000 made by Toshi ■ (P
PS-BO-4. ) and “Lumirror” 81 made by Toshi ■
Prepare 100μm of PP5-BO-4 (referred to as PET-80-1), and corona-treat both sides of PP5-BO-4 and PET-BO-1 at 6000 J/bottom using the following adhesive. PP5-BO-4/PET-B'O-1/P
PS-80-4 was laminated in this order. (Laminated film-2. Comparative example 4) Adhesive 2 “Chemit Eboxy” TE5920 (manufactured by Toshi U) Solid content concentration 3Qwt% Adhesive formulation: Part A/Part B - 15/100 The above adhesive was applied using a gravure roll method, drying conditions were 100° C. for 3 minutes, and the coating thickness of the adhesive was adjusted to 8 μm after drying. The lamination conditions were a temperature of 120° C. and a pressure of 3 kQ/C. Further, the curing conditions for the adhesive of the laminated film were 150° C. for 1 hour.

Table 1 shows the evaluation results of the samples obtained in Evaluation Example 1.2 and Comparative Examples 1 to 4.

The laminate of the present invention has heat resistance, moist heat resistance,
It can be seen that the impact resistance and tear strength, which were rare problems in the past, have been significantly improved without reducing flame retardancy. In addition, the heat resistance and elongation at break at high temperatures, which are rare problems of PP5-No, have also been improved.

Furthermore, although the tear strength of a laminated film of PP5-BO is improved compared to PP5-BO alone due to the cushioning effect of the adhesive, it did not reach a practical level and had poor resistance to sudden impact force. Further, since the laminate includes an adhesive, thermal deterioration of the adhesive adversely affects the properties such as heat resistance and flame retardance of PP5-BO.

In addition, the laminated film of PP5-BO and PET-BO has high impact resistance and tear strength, but the PET film in the center layer has poor heat resistance, moist heat resistance, and flame retardancy. There are problems with heat resistance and flame retardancy.

Example 3 In the same manner as in Example 1, a three-layer laminate having the thickness structure of each layer as shown in Table 2 was prepared.

In addition, "Torelina" manufactured by Toshi ■ was used for all PP5-BO. The evaluation results of these laminates are shown in Table 2.

When the thickness composition ratio (A+A-)/B becomes small, the elongation at break and the heat resistance at high temperatures tend to decrease, and conversely, when the composition ratio becomes large, the tear strength and impact resistance decrease. There is a tendency.

Using PP5-No-1 and PP5-BO-1 of Song Lushuang-Yu Example 1, the lamination temperature and pressure were changed under the conditions of Example 1, and the lamination state was observed. The results are shown in Table 3. If the lamination temperature is less than 180'C, adhesion will not occur, and if it exceeds 270°C, the flatness of the laminate will suddenly deteriorate, making it difficult to control the thickness and thickness unevenness of the laminate.

On the other hand, if the pressure is less than 1.0 kg/cm, no adhesion will occur even if the lamination temperature is high, and if it exceeds 20 kg/cm, the flatness will suddenly deteriorate and the PP5-No in the center layer will break. Therefore, it becomes difficult to control the thickness and thickness unevenness of the laminate.

Example 5 PP5-No-1 and PP5-BO-1 of Example 1 were overlapped and laminated under the conditions of Example 1.

Furthermore, PP5-BO-1 is added to the PP5-No-1 side of the two-layer body.
The laminate-3) was laminated with the strip f4 at a temperature of 250° C. and a pressure of 10 kg/CTd, and the difference in manufacturing method was compared with that of the laminate-1 of Example 1.

The evaluation results for Laminate-3 are shown in Table 4. It can be seen that the physical properties are the same as those of laminates-1 and 2 in Table 1. That is, 'I!' of the three-layer laminate of PP5-BO/PP5-No/PP5-80! For A structure, the above three layers can be stacked and laminated at the same time, or PP5-No.
It is also possible to create a two-layer body of /PP5-BO and then laminate PP5-BO on the PP5-No side of the laminate.

Example 6 The PPS polymer used in Example 1 was melted at 310°C using an extruder with a diameter of 30 mm, and the length was 200 mm.
It was extruded through a T-die with straight lips with a spacing Q of 5 mm.

On the other hand, a metal press roll whose surface temperature was kept at 25°C was installed directly below the T-die, and the PP5-BO used in Example 2 was
-2 was run while being pressed at a speed of 2 m/min, and the above polymers were continuously laminated to a thickness of 100 μm. The distance between T-die and PPS-80-2 is IQmm
The press pressure was 2 kg/cm. The obtained laminate is referred to as laminate-4.

Example 7 Similar to Example 6, PPS polymer was extruded between two layers of PPS-80-1 to form PP5-BO/PP5-N.
A three-layer laminate of o/PP5-BO was created. The lamination conditions were the same as in Example 5.

The obtained laminate is referred to as laminate-5.

Example 8 Under the conditions of Example 6, a PPS polymer was laminated onto PP5-BO-1 while extruding to create a two-layered body. Further, on the PP5-No side of the laminate, a temperature of 230°C and a pressure of 10kch were applied.
Another layer of PP5-BO-1 was laminated by thermocompression bonding under the condition of /cm. The three-layer laminate obtained by 1q is referred to as laminate-6.

As a result of evaluating the laminates 4 to 6 prepared in Evaluation Examples 6 to 8, they showed the same physical property values as laminates 1 and 2 shown in Table 1, and all achieved the purpose of the present invention. .

Comparative Example 5 PP5-BO-'l and PP5No- used in Example 1
1 through the adhesive used in Comparative Example 3, PP5-BO/
A three-layer laminate was created in the order of PP5-No/PP5-BO. The lamination conditions were the same as in Comparative Example 3. (Laminated body-
7) The evaluation results of laminate-7 are shown in Table 5.

Thermal deterioration of the adhesive affects the heat resistance of the laminate. 18
When the strength retention rate after aging at 0° C. for 2000 hours was compared with that of Laminated Film-1 of Comparative Example 3, Laminated Film-1 was 60%, while Laminate-7 was as low as 40%.

Claims (6)

[Claims] (1) A biaxially oriented polyphenylene sulfide layer (B) on at least one side of the unstretched polyphenylene sulfide layer (A).
) are laminated without using an adhesive. (2) Layer an unstretched polyphenylene sulfide sheet and a biaxially oriented polyphenylene sulfide film at a temperature of 180°C to 270°C and a pressure of 1 to 20kg/cm^
A method for producing a two-layer laminate, characterized by thermocompression bonding under the conditions of 2. (3) A method for producing a two-layer laminate, which comprises melting polyphenylene sulfide, extruding it from a slit-shaped die onto a biaxially oriented polyphenylene sulfide film, and integrating the film. (4) Polyphenylene sulfide is melted and extruded from a slit-shaped die between two biaxially oriented polyphenylene sulfide films to integrate them.
Method for manufacturing layer laminate. (5) Following the method described in claim 2 or 3, a biaxially oriented polyphenylene sulfide film is superimposed on the A layer side of the two-layer laminate, and the temperature is increased to 180°C.
A method for producing a three-layer laminate, comprising thermocompression bonding at 270°C and a pressure of 1 to 20 kg/cm^2. (6) Biaxially oriented polyphenylene sulfide film, unstretched polyphenylene sulfide sheet, and biaxially oriented polyphenylene sulfide film are stacked in this order at a temperature of 180°C to 270°C and a pressure of 1 to 20kg/cm.
A method for producing a three-layer laminate, characterized by thermocompression bonding under the conditions of ^2.