JP2005319776A - Film for molding - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a film for molding which has heat resistance, chemical resistance, flame retardancy, impact resistance and moist heat resistance, and furthermore has a large tensile elongation and excellent processability. <P>SOLUTION: The film for molding is a three-layered laminated film in which a poly-p-phenylene sulfide layer (layer A1), a copolymerized polyphenylene sulfide layer (layer B) and a poly-p-phenylene sulfide layer (layer A2) are laminated in this order. Respective adjoining faces between the poly-p-phenylene sulfide layer (the layer A1) and the copolymerized polyphenylene sulfide layer (the layer B) and between the copolymerized polyphenylene sulfide layer (the layer B) and the poly-p-phenylene sulfide layer (the layer A2) are stuck together through no adhesive. In addition, the poly-p-phenylene sulfide layer (the layer A1), the copolymerized polyphenylene sulfide layer (the layer B) and the poly-p-phenylene sulfide layer (the layer A2) are all oriented. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a molding film that is particularly excellent in workability, and more specifically, to a car air conditioner motor or a drive motor used in a hybrid car or the like that is currently being developed by an automobile manufacturer, or an electric water heater. The present invention relates to a film for molding suitable for an insulating material.

  Conventionally, a polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) film has excellent properties such as heat resistance, flame retardancy, rigidity, chemical resistance, electrical insulation and low hygroscopicity. In particular, it is suitably used for electrical / electronic devices, machine parts, automobile parts and the like.

  In recent years, application of PPS films to electrical insulating materials has been promoted taking advantage of the high electrical insulation and low hygroscopicity. For example, it is known that (1) a biaxially oriented film is used as an electrically insulating material (see Patent Document 1). In addition, (2) non-oriented PPS sheets are also known (see Patent Document 2 and Patent Document 3).

  Furthermore, (3) a laminate in which a biaxially oriented PPS layer is laminated on an unoriented PPS layer without using an adhesive is known (see Patent Document 4 and Patent Document 5).

However, the above-described conventional films and sheets, laminated films, and laminates have the following problems. That is, the film of the above item (1) has poor impact resistance and tear strength. For example, when used as a slot liner or wedge of a motor, the film may be torn or the film may be delaminated. There was a problem. In addition, the non-oriented sheet of the above item (2) is rich in tearing strength, but has a low tensile elongation, and when exposed to a temperature near the melting point, the strength rapidly decreases and the shape retention is remarkably deteriorated. There was a problem that. Furthermore, the laminate of the above item (3) is rich in impact resistance without using an adhesive, but has a low tensile elongation and a problem in workability.
JP 55-35456 A JP-A-56-34426 JP 57-121052 A JP-A-2-45144 Japanese Patent No. 2956254

  Accordingly, the present invention provides a molding film that solves these problems, has heat resistance, chemical resistance, flame resistance, impact resistance, and heat and humidity resistance, and has a high tensile elongation and excellent workability. It is for the purpose.

  The film for molding of the present invention has the following configuration in order to solve the above problems. That is, the molding film of the present invention has a poly-p-phenylene sulfide layer (A1 layer) / copolymerized polyphenylene sulfide layer (B layer) / poly-p-phenylene sulfide layer (A2 layer) laminated in this order 3 A layer laminated film comprising the poly-p-phenylene sulfide layer (A1 layer), the copolymerized polyphenylene sulfide layer (B layer), the copolymerized polyphenylene sulfide layer (B layer), and the poly-p-phenylene sulfide layer Each adjacent surface of (A2 layer) is bonded without any adhesive, and the poly-p-phenylene sulfide layer (A1 layer), the copolymerized polyphenylene sulfide layer (B layer), and the poly A film for molding characterized in that each layer of the -p-phenylene sulfide layer (A2 layer) is oriented.

  Moreover, according to the preferable aspect of the film for shaping | molding of this invention, 70 mol% or more and less than 90 mol% of repeating units of said copolymerization polyphenylene sulfide layer (B layer) used by this invention are following Structural formula (1). ), And 8 to 30 mol% of repeating units are mainly composed of a random copolymer consisting of units represented by the following structural formula (2), and chloroform The extraction amount is 1.5 wt% or less.

  (1)

  (2)

According to the present invention, as described below, it is possible to obtain a molding film having heat resistance, chemical resistance, flame retardancy, impact resistance, and moist heat resistance, and having a high tensile elongation and excellent workability. .

  The film for molding of the present invention is particularly suitable as an electrical insulation material for motors for car air conditioners and water heaters used in hybrid cars.

  The film for molding of the present invention has a basic structure in which a poly-p-phenylene sulfide layer (A1 layer), a copolymerized polyphenylene sulfide layer (B layer), and a poly-p-phenylene sulfide layer (A2 layer) are laminated in this order. It is a three-layer laminated film.

  The poly-p-phenylene sulfide layer (A1 layer and A2 layer) used in the present invention is a film-like material composed of a poly-p-phenylene sulfide composition mainly composed of poly-p-phenylene sulfide. -P-phenylene sulfide refers to a film that occupies 80 wt% or more of the film, preferably 90 t% or more, more preferably 95 wt% or more. If the remaining amount is less than 20 wt%, preferably less than 10 wt%, more preferably less than 5 wt%, an organic or inorganic additive other than poly-p-phenylene sulfide, or inert particles may be included. The A1 layer and the A2 layer may have the same composition or different compositions.

  Examples of organic additives other than the poly-p-phenylene sulfide include the following polymers. That is, polymers other than poly-p-phenylene sulfide include, for example, various polymers such as polyamide, polyetherimide, polyethersulfone, polysulfone, polyphenylene ether, polyester, polyarylate, polyamideimide, polycarbonate, polyolefin, and polyetheretherketone. And blends containing at least one of these polymers. It can also contain additives such as inorganic or organic fillers, lubricants, colorants, ultraviolet absorbers, compatibilizers and the like.

The melt viscosity of the poly-p-phenylene sulfide layer (A1 layer and A2 layer) used in the present invention is in the range of 100 to 50000 poise under biaxial stretchability at 300 ° C. and a shear rate of 100 sec ^−1. Is preferable, and more preferably in the range of 500 to 20,000 poise.

  Examples of the method for producing the PPS resin include the following methods. Sodium sulfide and p-dichlorobenzene are reacted at high temperature and pressure in an amide polar solvent such as N-methyl-2-pyrrolidone (NMP). If necessary, a copolymer component such as trihalobenzene may be included. As a polymerization degree adjusting agent, caustic potash or alkali metal carboxylate is added, and a polymerization reaction is performed at a temperature of 230 to 280 ° C. After the polymerization, the polymer is cooled, and the polymer is filtered as a water slurry through a filter to obtain a granular polymer. This is stirred in an aqueous solution such as acetate at a temperature of 30 to 100 ° C. for 10 to 60 minutes, washed several times with ion exchange water at a temperature of 30 to 80 ° C. and dried to obtain a PPS granular polymer. The obtained granular polymer was washed with NMP at an oxygen partial pressure of 10 torr or less, preferably 5 torr or less, and then washed several times with ion-exchanged water at a temperature of 30 to 80 ° C. Unreacted monomers and the like are separated. If necessary, an inorganic or organic additive or the like is added to the polymer obtained above to the extent that the object of the present invention is not hindered to obtain a PPS resin.

  The copolymerized polyphenylene sulfide layer (B layer) used in the present invention is composed of p-phenylene sulfide units having 70 to 90 mol%, preferably 80 to 90 mol% of repeating units as a main component. ing. When the main component is less than 70 mol%, the heat resistance of the film is remarkably reduced, and when it is 90 mol% or more, the effect of improving heat sealability, impact resistance, and tear resistance is poor.

  In the copolymerized polyphenylene sulfide layer (B layer) used in the present invention, 70 to 92 mol%, preferably 80 to 92 mol% of repeating units are composed of p-phenylene sulfide units. Preferably it is. When such a component is less than 70 mol%, the heat resistance of the film is remarkably lowered, and when it exceeds 92 mol%, the effect of improving heat sealability, impact resistance and tear resistance is poor.

  A suitable p-phenylene sulfide unit is represented by the following structural formula (1).

  (1)

  Further, the repeating unit of the copolymerized polyphenylene sulfide layer (B layer) is 8 mol% or more and 30 mol% or less, preferably 8 mol% or more and 20 mol% or less, more preferably 8 mol% or more and 15 mol% or less. The copolymer component is preferably composed of units represented by the following structural formula (2). When the copolymerization component is less than 8 mol%, the effect of improving the heat sealability, impact resistance and tear resistance is not sufficient, and when it exceeds 30 mol%, the heat resistance is significantly lowered.

  (2)

  The copolymer constituting the copolymerized polyphenylene sulfide layer (B layer) used in the present invention is composed of the above main component and copolymer component, but the mode of copolymerization is random in terms of biaxial stretching properties. A copolymer is preferred.

  The copolymer composition of such a copolymer can be measured by NMR method.

  In the present invention, the remaining portion of the repeating unit of the copolymer constituting the copolymerized polyphenylene sulfide layer (B layer) may be further composed of other copolymerizable units. The trifunctional phenyl sulfide unit represented by the structural formula (3) is preferably 1 mol% or less of the entire copolymer.

  (3)

There are various methods for polymerizing the copolymer used in the present invention. For example, an alkali sulfide, p-dihalobenzene (main component monomer), and a subcomponent monomer coexist in a polar solvent, A method of polymerizing in the presence at high temperature and high pressure is a preferable method because the degree of polymerization of the resulting polymer is likely to increase. In particular, sodium sulfide is most preferably used as the alkali sulfide, p-dichlorobenzene as the main component monomer, and N-methylpyrrolidone as the solvent. As a secondary component monomer,
(4)

(However, Y represents a halogen.)
Etc. are used.

  In the present invention, any method can be adopted to adjust the amount of chloroform extracted to 1.5 wt% or less. For example, the copolymer obtained by the above polymerization method is prepared by changing the solvent and temperature conditions. A method of cleaning by selecting can be used.

The melt viscosity of the copolymerized polyphenylene sulfide used in the present invention is preferably in the range of 100 to 50,000 poise, more preferably 500 to 500 ° C. under a shear rate of 200 sec ⁻¹ from biaxial stretchability. The range is 20,000 poise.

  The copolymerized polyphenylene sulfide layer (B layer) used in the present invention means that the above-mentioned copolymer occupies 80 wt% or more, and the remaining less than 20 wt% contains an inorganic compound and / or an organic compound. be able to.

  The thickness of each layer of the three-layer laminated film of the present invention is preferably in the range of 5 to 300 μm for the poly-p-phenylene sulfide layer (A1 layer and A2 layer) from the viewpoint of mechanical properties, impact resistance and heat sealability. More preferably, it is in the range of 10-200 μm, and the thickness of the copolymerized polyphenylene sulfide layer (B layer) is preferably in the range of 0.1-200 μm, and the poly-p-phenylene sulfide layer (A1 layer) And the thickness of the poly-p-phenylene sulfide layer (A2 layer) may be the same or different as long as they are within the above thickness range.

  The thickness of the biaxially oriented copolymerized polyphenylene sulfide layer in the molding film of the present invention is preferably 1 μm or more and a lamination ratio of 45% or less, more preferably 5 μm or more and a lamination ratio of 20% or less, Preferably, it is 8 μm or more and the lamination ratio is 15% or less. If the thickness of the biaxially oriented copolymerized polyphenylene sulfide layer is less than 1 μm, the heat sealability at the lamination interface may not be obtained sufficiently, and if the lamination ratio exceeds 45%, the heat resistance of the laminated sheet may decrease. is there.

  Each of the poly-p-phenylene sulfide layer (A1 layer), the copolymerized polyphenylene sulfide layer (B layer) and the poly-p-phenylene sulfide layer (A2 layer) of the three-layer laminated film of the present invention has an impact resistance and an anti-resistance property. Both must be oriented from the tearability. The orientation of each layer can be determined by measuring the cross section by Raman spectroscopy. Alternatively, the orientation parameter obtained by Raman spectroscopy can be converted to birefringence, and the preferred birefringence is 0.01 to 0.2 in terms of strength.

  In order to obtain the effects of the present invention, the breaking elongation of the molded film of the present invention is preferably 80% or more and 150% or less. More preferably, they are 90% or more and 140% or less, More preferably, they are 100% or more and 130% or less. By making the breaking elongation of the laminated sheet within the above range, the moldability can be improved. If the breaking elongation is less than 80%, film cracking may occur in the molding process. The upper limit of the breaking elongation is not particularly provided, but if it exceeds 150%, the strength of the film is lowered, and a buckling defect may occur in the molding process. In order to set the breaking elongation of the molded film of the present invention within the above range, it is possible to obtain the laminated thickness and lamination ratio of the biaxially oriented copolymerized polyphenylene sulfide to be laminated within the range specified by the present invention.

  The impact strength of the molded film of the present invention is preferably 2 N / μm or more and 10 N / μm or less in order to suppress cracking of the film in the molding process, and more preferably 3 N / μm or more and 10 N / μm or less. is there. When the impact strength is less than 2 N / μm, the film may be cracked in the molding process. Moreover, although the upper limit of impact strength is not particularly provided, if it exceeds 10 N / μm, the stiffness of the film is lowered, and the moldability may be lowered.

  The thickness of the molding film of the present invention is preferably 150 μm or more and 450 μm or less as an electric insulation film for motor slots. More preferably, they are 200 micrometers or more and 350 micrometers or less, More preferably, they are 250 micrometers or more and 350 micrometers or less. When the film thickness is less than 150 μm, the electrical insulation of the film may be lowered. On the other hand, if it exceeds 450 μm, the workability of the slot and wedge may be deteriorated, and the film forming property may be deteriorated.

  The number of stagnation in the stagnation test of the molded film of the present invention is not particularly limited, but it is preferably 20 times or more in order to suppress the occurrence of film cracking in the molding process, more preferably 40 times or more. More preferably, it is 100 times or more. When the number of stagnations is less than 20, the heat sealability at the interface is not sufficient in the molding process, and film cracking may occur. In order to increase the number of stagnations to 100 times or more, it is important to increase the heat laminating temperature.

  In the present invention, the method of adhering without using an adhesive is not using an adhesive resin such as an adhesive, and specific examples thereof include heat fusion. The method of heat fusion is not particularly limited, but heat fusion with a heating roll is particularly preferred from the viewpoint of processability.

  Next, a method for producing a three-layered film for molding according to the present invention will be described. The above-described poly-p-phenylene sulfide raw materials for the A1 layer and A2 layer and the copolymerized polyphenylene sulfide raw material for the B layer are supplied to separate melt-extrusion apparatuses and heated to the melting point or more of the individual raw materials. Each raw material melted by heating is laminated in two or three layers in a molten state by a merging device provided between the melt extrusion device and the die outlet, and is extruded from the slit-like die outlet. The molten laminate is cooled on the cooling drum to below the glass transition point of poly-p-phenylene sulfide to obtain a substantially amorphous two-layer or three-layer laminate sheet. Although a well-known apparatus can be applied to the melt extrusion apparatus, a uniaxial or biaxial extruder is simple and preferably used.

  Next, the amorphous two-layer or three-layer laminated sheet thus obtained is subjected to a conventionally known sequential biaxial stretching machine in the range of the glass transition point of poly-p-phenylene sulfide to the cold crystallization temperature. Or after biaxial stretching with a simultaneous biaxial stretching machine, heat treatment is preferably performed at a temperature in the range of 220 to 290 ° C. to obtain a biaxially stretched two-layer or three-layer laminated film.

  It is preferable to perform extending | stretching in the range of 3.0-4.0 times at 90 to 120 degreeC in a longitudinal direction. In the case of this invention, a more preferable draw ratio is 3.0 to 3.7, More preferably, it is 3.0 to 3.5 times. In the present invention, when the draw ratio is less than 3.0 times, a polyphenylene sulfide film having sufficient film flatness may not be obtained, and when the draw ratio exceeds 4.0 times, the breaking elongation of the invention You may not get. Then, it is preferably stretched 3.0 to 4.0 times at 90 ° C. to 120 ° C. in the width direction. More preferably, it is 3.0-3.7 times, More preferably, it is 3.0-3.5 times. In the present invention, when the draw ratio is less than 3.0 times, a polyphenylene sulfide film having sufficient film flatness may not be obtained. When the draw ratio exceeds 4.0 times, the breaking elongation of the invention You may not get.

  In the biaxially stretched two-layer laminated film, the heat treatment temperature is preferably not less than the melting point of the copolymerized polyphenylene sulfide and not more than the melting point of the poly-p-phenylene sulfide in order to further improve the heat sealability. In addition, it is considered that a part of the polymer chain constituting the biaxially oriented copolymerized polyphenylene sulfide layer (B layer) is deoriented. Furthermore, if necessary, it is also a preferable embodiment to perform limited shrinkage (relaxation) in the range of 1 to 20% in the vertical and horizontal directions at a temperature not higher than the melting point of poly-p-phenylene sulfide.

  The three-layer laminated film obtained by the above method is used as it is, but the two-layer laminated film is composed of heated roll groups so that the copolymerized polyphenylene sulfide layers (B layers) overlap each other. A three-layer laminated film of poly-p-phenylene sulfide layer (A layer) / copolymerized polyphenylene sulfide layer (B layer) / poly-p-phenylene sulfide (A layer) is introduced into the heat-sealing device and heat-sealed. obtain. When the copolymerized polyphenylene sulfides are fused together, the entire fused copolymerized polyphenylene sulfide layer is regarded as one layer.

  Further, the copolymer polyphenylene sulfide layer (B layer) of the two-layer laminate film and a biaxially oriented poly-p-phenylene sulfide film single film are heat-sealed to obtain a poly-p-phenylene sulfide layer / copolymerized polyphenylene sulfide layer. A laminated film of / poly-p-phenylene sulfide can also be obtained.

  In the present invention, in order to improve the handleability and processability of the molding film, inert particles can be added to each layer. Examples of the inert particles used herein include inorganic fillers such as silica, alumina, calcium carbonate, barium carbonate, barium titanate, barium sulfate, calcium silicate, magnesium oxide, titanium oxide and zinc oxide, and do not melt at 300 ° C. Examples thereof include particles of an organic polymer compound (for example, crosslinked polystyrene).

  The film for molding in the present invention is a biaxially oriented two-layer laminated film obtained by the above method, or a biaxially oriented two-layer laminated film obtained by the above method and a single poly-p-phenylene sulfide. A biaxially oriented monolayer film biaxially stretched by the above method and laminated without an adhesive, and a poly-p-phenylene sulfide composition (A1 layer) / copolymerized polyphenylene sulfide layer (B Layer) / poly-p-phenylene sulfide composition (A2 layer).

In the present invention, as a method for laminating each layer, for example, a method of thermocompression bonding under high temperature and high pressure is preferable. The thermocompression bonding is preferably at a temperature in the range of 180 to 300 ° C., more preferably 200 to 300 ° C., further preferably 230 to 300 ° C., and the thermocompression bonding is preferably 1 to 20 kg / cm ² , more preferably, 5-20 kg / cm < ² >, More preferably, it can carry out by a roll press, a hot plate press, etc. on the pressure conditions of the range of 10-20 kg / cm < ² >. Immediate cooling after the thermocompression bonding below the glass transition point of the copolymerized polyphenylene sulfide is a preferred embodiment from the viewpoint of maintaining adhesive strength and tensile elongation. In addition, when thermocompression bonding is performed, it is necessary to superimpose so that the copolymerized polyphenylene sulfide layer (B layer) becomes an adhesive surface.

  In order to give stronger heat sealability to the copolymerized polyphenylene sulfide layer (B layer) and poly-p-phenylene sulfide raw material (A1 layer and A2 layer) used in the present invention, corona discharge treatment and plasma treatment are performed. It is also included in a preferred embodiment of the present invention. Moreover, in this invention, unless the effect of this invention is prevented, another sheet layer can be laminated | stacked as needed, and it is not excluded.

[Measurement method of characteristics]
(1) Elongation at break According to the following method prescribed in ASTM-D882, using an Instron type tensile tester (AMF / RTA-100 manufactured by Orientec Co., Ltd.), a sample film with a width of 10 mm is the length between chucks. Set to 50 mm, and perform a tensile test at a temperature of 25 ° C. and an atmospheric condition of 65% RH at a tensile speed of 300 mm / min.

The breaking elongation is determined by measuring both the film longitudinal direction and the width direction at n = 5 and averaging both directions. When the film longitudinal direction is unknown, the above-described measurement is performed in two directions orthogonal to each other in the film plane.
(2) Impact strength The following method can be illustrated as a specific method of measuring the impact strength of the molding film which is the laminate of the present invention. That is, the Charpy impact test was measured according to ASTM D256.
(3) Scratch test Measured in accordance with JIS-K-6328 using a Scott Scab Abrasion Tester (manufactured by Toyo Seiki). The sample size is measured with a width of 10 mm, a length of 200 mm, and a load of 2.5 kg, and the number of times until the cleavage can be confirmed visually is obtained. Judgment was made according to the following criteria.

◎: 100 times or more ○: 40 times or more and less than 100 times △: 20 times or more and less than 40 times ×: Less than 20 times

(Examples 1-9)
(1) Production of copolymer polyphenylene sulfide composition 100 moles of sodium sulfide nonahydrate, 45 moles of sodium acetate and 25 liters of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP) were added to the autoclave. While being charged and stirred, the temperature was gradually raised to a temperature of 220 ° C., and the contained water was removed by distillation. In the system after dehydration, 5 liters of 91 mol of p-dichlorobenzene as a main component monomer, 10 mol of m-dichlorobenzene as a secondary component monomer, and 0.2 mol of 1,2,4-trichlorobenzene were added. Nitrogen was added together with NMP at a temperature of 170 ° C. and pressurized and sealed at 3 kg / cm ² , and then heated and polymerized at 260 ° C. for 4 hours. After completion of the polymerization, the polymer was cooled, the polymer was precipitated in distilled water, and a small polymer was collected with a wire mesh having a 150 mesh opening. The small polymer thus obtained was washed 5 times with distilled water at 90 ° C. and then dried at a reduced pressure of 120 ° C. to obtain a white granular material having a melt viscosity of 1000 poise and a melting point of 253 ° C. The copolymer polyphenylene sulfide was obtained. Subsequently, 50 g of spherical silica having a diameter of 0.5 μm was blended with 10 kg of the obtained copolymer polyphenylene sulfide, and extruded into a gut shape at a temperature of 320 ° C. with a 30 mmφ twin-screw extruder to be pelletized.
(2) Production of poly-p-phenylene sulfide composition Production of copolymer polyphenylene sulfide composition of (1) above except that 101 mol of p-dichlorobenzene is used as the main component monomer and no secondary component monomer is used. In the same manner as described above, a poly-p-phenylene sulfide composition was produced. The poly-p-phenylene sulfide composition had a melt viscosity of 3000 poise and a melting point of 283 ° C.
(3) Film formation After the copolymerized polyphenylene sulfide composition and poly-p-phenylene sulfide composition obtained in the above (1) and (2) were each dried at a temperature of 180 ° C. for 3 hours under reduced pressure of 1 mmHg. , Supplied to separate extruders, led to a double-ply type laminating device at the top of the die in a molten state, and led to 2 layers (Example 9 is 3 layers), then discharged from the T-die die provided And quenched with a cooling drum at a temperature of 25 ° C. to obtain a laminated sheet of substantially amorphous copolymer polyphenylene sulfide composition / poly-p-phenylene sulfide composition (3 layers in Example 9). . Next, each of the obtained laminated sheets was brought into contact with a plurality of heating rolls having a surface temperature of 95 ° C., and 3 ° in the longitudinal direction between 30 ° C. cooling rolls having different peripheral speeds provided next to the heating rolls. The film was stretched 5 times. The uniaxially stretched sheet thus obtained was stretched 3.5 times at a temperature of 100 ° C. in the direction perpendicular to the longitudinal direction using a tenter, and subsequently heat treated at a temperature of 260 ° C. for 10 seconds, and then rolled. And laminated films (a to k) having the thickness structures shown in Table 1 were obtained. The thickness configuration was changed by changing the discharge amount of the extruder of each layer.

At this time, the poly-p-phenylene sulfide composition alone was formed and heat-treated under the above-mentioned film forming conditions to obtain a single film (h, i and j).
(4) Lamination Heat fusion of the two-layer laminated film obtained by the above film-forming method is prepared by preparing two rolls of the two-layer laminated film and heating at a temperature of 240 ° C. so that the copolymerized polyphenylene sulfide layer overlaps. The film was heat-sealed using a press roll and immediately cooled at a temperature of 50 ° C. and wound up. Table 2 shows the evaluation results of the three-layer laminated film (molding film) obtained as described above.

(Example 10)
A three-layer laminated film (for molding) was prepared in the same manner as in Example 4 except that 5 mol% of m-dichlorobenzene was added as an auxiliary component monomer in Example 4 to obtain a white granular copolymer polyphenylene sulfide having a melting point of 265 ° C. Film). The evaluation results are shown in Table 3.

(Example 11)
A three-layer laminated film (molding film) was produced in the same manner as in Example 8 except that the two-layer laminated film (g) used in Example 8 was laminated in the order of g / i and laminated. The evaluation results are shown in Table 3.

(Example 12)
A three-layer laminated film (molding film) was produced in the same manner as in Example 1 except that the two-layer laminated film (a) used in Example 1 was laminated in the order of a / k and laminated. The evaluation results are shown in Table 3.

(Example 13)
A three-layer laminated film (molding film) (200 μm) was produced in the same manner as in Example 4 except that the two-layer laminated film (d) used in Example 4 was laminated in the order of d / j and laminated. The evaluation results are shown in Table 3.

(Example 14)
A three-layer laminated film (molding film) (300 μm) was produced in the same manner as in Example 2 except that the two-layer laminated film (b) used in Example 2 was laminated in the order of b / b and laminated. The evaluation results are shown in Table 3.

(Example 15)
Three-layer lamination was carried out in the same manner as in Example 4 except that the copolymerized polyphenylene sulfide composition used in Example 4 was changed to 90 mol of p-dichlorobenzene as a main component monomer and 10 mol of m-dichlorobenzene as an auxiliary component monomer. A film (film for molding) was produced. The evaluation results are shown in Table 3.

(Comparative Example 1)
The 125 μm poly-p-phenylene sulfide single membrane films (i in Table 1) produced in Example (3) above were heat-bonded and wound up under the lamination conditions in Example (4) above. The obtained two-layer laminated film had a low adhesive force between the films, and could not be evaluated by peeling. The evaluation results are shown in Table 2.

(Comparative Example 2)
The 75 μm poly-p-phenylene sulfide biaxially oriented monolayer film (j in Table 1) produced in the example of (3) above was used as the non-oriented monolayer of poly-p-phenylene sulfide produced in (3) above. The film was heat-bonded and wound up under the lamination conditions of the above example (4). The resulting three-layer laminated film had a small breaking elongation of the molded film and a small number of firries. The evaluation results are shown in Table 2.

(Comparative Example 3)
The 75 μm poly-p-phenylene sulfide biaxially oriented monolayer film (j in Table 1) produced in the example of (3) above was used as the non-oriented monolayer of the copolymerized phenylene sulfide composition produced in (1) above. The film was heat-bonded and wound up under the lamination conditions of the above example (3). The resulting three-layer laminated film had a small breaking elongation of the molded film and a small number of firries. The evaluation results are shown in Table 2.

  The molding film of the present invention combines heat resistance, chemical resistance, flame retardancy, impact resistance, and moist heat resistance, and has a high tensile elongation and excellent workability. It is suitable as an electric insulation material for an air conditioner motor, a drive motor, or a water heater, and is industrially useful.

Claims (6)

  A poly-p-phenylene sulfide layer (A1 layer) / copolymerized polyphenylene sulfide layer (B layer) / poly-p-phenylene sulfide layer (A2 layer) are laminated in this order, Which of the adjacent surfaces of the p-phenylene sulfide layer (A1 layer) and the copolymerized polyphenylene sulfide layer (B layer) and the copolymerized polyphenylene sulfide layer (B layer) and the poly-p-phenylene sulfide layer (A2 layer) Are bonded without using an adhesive, and the poly-p-phenylene sulfide layer (A1 layer), the copolymerized polyphenylene sulfide layer (B layer) and the poly-p-phenylene sulfide layer (A2 layer) A film for molding, wherein each of the layers is oriented. The copolymerized polyphenylene sulfide layer (B layer) is composed of units represented by the following structural formula 1 in which 70 mol% or more and less than 90 mol% of repeating units are formed, and 8 mol% or more and 30 mol% or less of repeating units have the following structure. The film for molding according to claim 1, wherein the film is composed mainly of a random copolymer composed of units represented by Formula 2 and has a chloroform extraction amount of 1.5 wt% or less.
(1)

(2)

The copolymerized polyphenylene sulfide layer (B layer) contains 70 to 92 mol% of repeating units containing units represented by the following structural formula 1, and 8 to 30 mol% of repeating units have the following structure. The film for molding according to claim 1, wherein the film is made of a random copolymer containing a unit represented by Formula 2 and has a chloroform extraction amount of 1.5 wt% or less.
(1)

(2)

  The film for molding according to any one of claims 1 to 3, wherein a lamination thickness of the copolymerized polyarylene sulfide layer is 1 µm or more and a lamination ratio is 45% or less.   The film for molding according to any one of claims 1 to 4, wherein the tensile elongation at break is 80 to 150%.   The film for molding according to any one of claims 1 to 5, wherein the number of stagnation in the stagnation test is 20 to 100 times.