JP4983163B2 - LAMINATED FILM AND METHOD FOR PRODUCING LAMINATED FILM - Google Patents

Description

  The present invention relates to a laminated film particularly excellent in motor processability. More specifically, the present invention relates to a drive motor, a car air conditioner motor for carbon dioxide refrigerant, or the like used in a hybrid car currently being developed by an automobile manufacturer, The present invention relates to a laminated film suitable for an electrical insulating material of a water heater motor for gas refrigerant.

  Polyarylene sulfide film has excellent properties such as heat resistance, flame retardancy, rigidity, chemical resistance, electrical insulation and low moisture absorption, especially for electrical / electronic equipment, mechanical parts and automotive parts. It is preferably used.

  In recent years, polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) films have been applied to electrical insulating materials by taking advantage of their high electrical insulation and low hygroscopicity. For example, it is known that (1) a biaxially oriented film is used as an electrical insulating material (see Patent Document 1). In addition, (2) non-oriented PPS sheets are also known (Patent Document 2).

  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 3 and Patent Document 4). Moreover, in order to provide (4) heat-sealing property, the laminated film which laminated | stacked the layer which consists of copolymer polyphenylene sulfide 5 micrometers or less is known (refer 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, there is a problem that the film is torn or the film is broken. . 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. In addition, the laminate of the above item (3) is rich in impact resistance without using an adhesive, but has insufficient interface adhesiveness, causing delamination in motor processing and increasing film cracking. It was. Furthermore, the laminated film of item (4) did not have sufficient interfacial adhesion.
JP 55-35456 A JP-A-56-34426 JP-A-2-45144 Japanese Patent No. 2956254 JP-A-4-319436

  Therefore, the present invention aims to solve these problems, and to provide a laminated film excellent in interfacial adhesion of the laminated film, further having a large tensile elongation of the laminated film, and excellent in motor processability. is there.

The laminated film of the present invention has the following configuration in order to solve the above problems. That is, the outermost layer is a laminated film made of biaxially oriented polyarylene sulfide, and at least one layer other than the outermost layer is made of biaxially oriented copolymerized polyarylene sulfide, and the outermost layer of biaxially oriented polyarylene sulfide and biaxial The laminated film is characterized in that the oriented copolymerized polyarylene sulfide is adjacent to each other, the tensile elongation at break is 100 to 150%, and the number of stagnation until film rupture by a sag test is 90 times or more.

According to the present invention, as will be described below, it is possible to obtain a laminated film that is excellent in interfacial adhesion of the laminated film, has a large tensile elongation of the laminated film, and is excellent in motor processability.

  The laminated film of the present invention is particularly suitable as an electrical insulating material for a drive motor, a car air-conditioner motor for carbon dioxide refrigerant, or a water heater motor for carbon dioxide refrigerant used in a hybrid car.

  In the laminated film of the present invention, the outermost layer is composed of biaxially oriented polyarylene sulfide. The polyarylene sulfide used in the present invention is a homopolymer or a copolymer having a repeating unit of-(Ar-S)-. Examples of Ar include units represented by the following formulas (A) to (K).

(R1 and R2 are substituents selected from hydrogen, an alkyl group, an alkoxy group, and a halogen group, and R1 and R2 may be the same or different.)
As the repeating unit of polyarylene sulfide used in the present invention, the structural formula represented by the above formula (A) is preferable, and representative examples thereof include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone, and random thereof. Examples thereof include copolymers, block copolymers, and mixtures thereof. Particularly preferred polyarylene sulfide is preferably polyphenylene sulfide (PPS) from the viewpoint of film properties and economy, and a poly-p-phenylene sulfide unit represented by the following structural formula is preferably used as the main structural unit of the polymer. A resin containing more than 95% by mole, more preferably 95% by mole or more. When the poly-p-phenylene sulfide component is 92 mol% or less, the crystallinity and thermal transition temperature of the polymer are low, and the heat resistance, dimensional stability, mechanical properties, dielectric properties, etc., which are the characteristics of PPS, may be impaired. .

  A unit containing a copolymerizable sulfide bond may be contained as long as it is preferably less than 8 mol% of the repeating unit. Examples of such repeating units include trifunctional units, ether units, sulfone units, ketone units, meta bond units, aryl units having substituents such as alkyl groups, biphenyl units, terphenylene units, vinylene units, carbonate units. These are given as specific examples, and one or more of them can coexist. In this case, the structural unit may be in any form of random copolymerization or block copolymerization.

  The biaxially oriented polyarylene sulfide used 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, and heat-treating. When the content of poly-p-phenylene sulfide is less than 90% by weight, the crystallinity as a composition is lowered, and the heat resistance, thermal dimensional stability, hydrolysis resistance and the like of the film may be impaired. Less than 10% by weight of the composition can contain polymers other than poly-p-phenylene sulfide. Examples of polymers other than poly-p-phenylene sulfide include various polymers such as polyamide, polyetherimide, polyethersulfone, polysulfone, polyphenylene ether, polyester, polyarylate, polyamideimide, polycarbonate, polyolefin, polyetheretherketone, and the like. Mention may be made of blends comprising at least one of the following polymers. It can also contain additives such as inorganic or organic fillers, lubricants, colorants, ultraviolet absorbers, compatibilizers and the like.

  In the case of the present invention, it is necessary to have the biaxially oriented polyarylene sulfide in the outermost layer of the laminated sheet in order to have the elongation at break of the laminated film of the present invention, and film cracking due to bending during motor processing, etc. It is necessary to suppress this. Furthermore, it is of course necessary to improve the heat resistance of the polyarylene sulfide.

  Moreover, the said biaxially oriented polyarylene sulfide film may perform arbitrary processes, such as heat processing, shaping | molding, surface treatment, lamination, coating, printing, embossing, and etching, as needed.

  In the laminated film of the present invention, at least one layer other than the outermost layer is composed of a biaxially oriented copolymer polyarylene sulfide. The copolymerized polyarylene sulfide used in the present invention is preferably composed of a poly-p-phenylene sulfide unit having 80 to 92 mol% as a main component. If the main component is less than 80 mol%, the heat resistance of the film may be significantly reduced. If it exceeds 92 mol%, the interfacial adhesion may not be sufficiently improved.

  As the copolymer unit, a poly-m-phenylene sulfide unit represented by the following formula,

(Here, X represents an alkylene, CO, or SO ₂ unit.)

(Wherein R represents an alkyl, nitro, phenylene, or alkoxy group), and these complex units may be present. A preferred copolymer unit is a poly-m-phenylene sulfide unit. The copolymerization amount of these units is preferably 8 mol% or more and 20 mol% or less, more preferably 10 mol% or more and 18 mol% or less, and still more preferably 12 mol% or more and 15 mol% or less. If the copolymerization component is less than 8 mol%, the interfacial adhesion may not be sufficiently improved, and film cracking may occur in motor processing. When it exceeds 20 mol%, the heat resistance may be significantly lowered.

  The mode of copolymerization of the main component and copolymer component of the copolymerized polyarylene sulfide used in the present invention is not particularly limited, but is preferably a random copolymer.

  In the present invention, the remaining part of the repeating unit of the copolymer constituting the copolymer polyarylene sulfide may be further composed of other copolymerizable structural units. For example, it is represented by the following formula: The trifunctional phenyl sulfide is preferably 1 mol% or less of the entire copolymer.

  The melting point of the copolymerized polyarylene sulfide of the present invention is preferably 210 ° C. or higher and 260 ° C. or lower, more preferably 220 ° C. or higher and 250 ° C. or lower, and further preferably 230 ° C. or higher and 240 ° C. or lower. When the melting point of such copolymerized polyarylene sulfide is less than 210 ° C, the heat resistance may be significantly reduced. When the melting point exceeds 260 ° C, the interfacial adhesion may not be sufficiently improved, and film cracking in motor processing occurs. There is a case. The melting point of the copolymer polyarylene sulfide can be appropriately adjusted depending on the molar ratio of the copolymer components. For example, when the melting point of the copolymerized polyarylene sulfide is 210 ° C., it can be obtained by setting the molar ratio of the copolymerization component to 20 mol%.

  The biaxially oriented copolymer polyarylene sulfide used in the present invention is a film formed by melt-molding a resin composition containing 90% by weight or more of the copolymerized polyarylene sulfide into a sheet, biaxially stretching, and heat-treating. . When the content of the copolymerized polyarylene sulfide is less than 90% by weight, the interfacial adhesion may be impaired. Less than 10% by weight in the composition can contain polymers other than the copolymerized polyarylene sulfide. Polymers other than copolymerized polyarylene sulfides include, for example, various polymers such as polyamide, polyetherimide, polyethersulfone, polysulfone, polyphenylene ether, polyester, polyarylate, polyamideimide, polycarbonate, polyolefin, polyetheretherketone, and the like. Mention may be made of blends comprising at least one polymer. It can also contain additives such as inorganic or organic fillers, lubricants, colorants, ultraviolet absorbers, compatibilizers and the like.

  In the laminated structure of the laminated film of the present invention, the outermost layer is a biaxially oriented polyarylene sulfide, and at least one layer other than the outermost layer is composed of a biaxially oriented copolymerized polyarylene sulfide, and the biaxially oriented polyarylene sulfide and the biaxially oriented There is no particular limitation except that the copolymerized polyarylene sulfide is adjacent, but the biaxially oriented polyarylene sulfide layer (A layer) / biaxially oriented copolymerized polyarylene sulfide layer (B layer) / biaxially oriented polyarylene sulfide layer ( A layer) or A / B / A / B / A may be laminated. The laminated structure can be appropriately changed depending on the thickness of the laminated film.

  The thickness of the biaxially oriented copolymer polyarylene sulfide layer of the present invention is preferably 5 μm or more and 50 μm or less, more preferably 10 μm or more and 50 μm or less, further preferably 15 μm or more and 30 μm or less, and most preferably 20 μm. It is 25 μm or less. When the thickness of the biaxially oriented copolymerized polyarylene sulfide layer is less than 5 μm, the orientational relaxation of the copolymerized polyarylene sulfide layer may not proceed sufficiently, and sufficient interfacial adhesion may not be obtained. The heat resistance of may decrease. Here, the thickness of the biaxially oriented copolymerized polyarylene sulfide layer is the thickness of each laminated biaxially oriented copolymerized polyarylene sulfide layer.

  The biaxially oriented copolymer polyarylene sulfide film may be subjected to any processing such as heat treatment, molding, surface treatment, laminating, coating, printing, embossing and etching as necessary.

  The thickness of the laminated film of the present invention is 125 μm or more and 500 μm or less, more preferably 200 μm or more and 400 μm or less, and further preferably 250 μm or more and 350 μm or less. When the thickness is less than 125 μm, the electric insulation as the motor insulating film may not be sufficient. When the thickness exceeds 500 μm, the laminate processability of the laminated film may be deteriorated and the interfacial adhesion may be deteriorated.

  Each of the polyarylene sulfide layer and the copolymerized polyarylene sulfide layer of the present invention needs to be biaxially oriented in order to improve the motor processability of the laminated film. The orientation of each layer can be determined by measuring the cross section of the laminated film by Raman spectroscopy. 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 film breaking strength.

  In the laminated film of the present invention, the peak temperature of tan δ in the dynamic viscoelasticity measurement is 115 ° C. or more and 123 ° C. or less, more preferably 115 ° C. or more and 120 ° C. or less, and further preferably 115 ° C. or more and 118 ° C. or less. When the peak temperature of tan δ is less than 115 ° C, the heat resistance of the laminated film may decrease due to an increase in molecular chain mobility. When the temperature exceeds 123 ° C, the orientation of the biaxially oriented copolymerized polyarylene sulfide layer may be reduced. The interfacial adhesion may decrease because of the increase.

  The peak temperature of tan δ here is the peak temperature of the tan δ curve in the temperature change of the dynamic viscoelasticity measurement, and corresponds to the glass transition temperature of the stretched film, and is called the α dispersion peak. Since α dispersion changes depending on the degree of elongation of the molecular chain, the higher the stretching orientation and the stronger the elongation constraint of the amorphous chain, the higher the shift. The peak temperature of tan δ of the laminated film of the present invention is preferably in the above range in the film longitudinal direction and / or the width direction. In order to set the tan δ peak temperature of the laminated film of the present invention in the above range, it can be obtained by weakening the elongation constraint of the amorphous chain. For example, the laminated thickness of the biaxially oriented copolymer polyarylene sulfide to be laminated The film can be obtained by increasing the thickness, decreasing the film-forming stretch ratio, or increasing the heat treatment temperature.

  In order to obtain the motor processability of the present invention, the breaking elongation of the laminated film of the present invention is preferably 100% or more and 150% or less. More preferably, they are 120% or more and 150% or less, More preferably, they are 130% or more and 150% or less. If the elongation at break is less than 100%, film cracking may occur in the motor processing step, and there is no particular upper limit for the elongation at break, but if it exceeds 150%, the strength of the film is reduced and the heat resistance of the film is reduced. May decrease. The breaking elongation of the laminated film of the present invention is preferably in the above range in the film longitudinal direction and / or in the width direction, and in particular, in order to obtain the workability of the motor that the breaking elongation in the width direction is in the above range. preferable. In order to set the breaking elongation of the laminated film in the above range, the breaking elongation of the biaxially oriented polyarylene sulfide film and the copolymerized polyarylene sulfide film before lamination according to the film-forming stretching conditions and heat treatment conditions specified in the present application is set as above. It becomes possible to obtain by making it into the range and making the number of stagnation of the laminated film into the range specified in the present application. When the number of stagnation of the laminated film of the present invention is small, the interfacial adhesiveness of the laminated film is not sufficient, and the elongation at break of the laminated film may decrease due to interfacial peeling.

  The number of stagnation until film breakage in the stagnation test of the laminated film of the present invention does not particularly set an upper limit, but is 90 times or more in order to suppress the occurrence of film cracking in the motor processing step. More preferably, it is 100 times or more, More preferably, it is 120 times or more, Most preferably, it is 140 times or more. When the number of stagnations is less than 90 times, the interfacial adhesion is not sufficient, and the breaking elongation of the laminated film is reduced due to interfacial peeling, and film cracking may occur in the motor processing step. Moreover, in order to make the number of stagnations 140 times or more, it is preferable to increase the heat laminating temperature, but the film flatness may be deteriorated. In order to set the number of stagnation by the stagnation test within the above range, it is necessary to improve the interfacial adhesion of the laminated film. In order to obtain interfacial adhesion that achieves the number of stagnation of the present invention, the laminated thickness of the biaxially oriented copolymer polyarylene sulfide to be laminated, the area stretch ratio in film-forming stretching, and the heat treatment conditions are within the specified range of the present invention. As a result, the amorphous chain orientation of the biaxially oriented copolymer polyarylene sulfide can be relaxed and the interfacial adhesion can be improved. Furthermore, by setting the laminating temperature in the thermal laminating to the range specified in the present application, it is possible to improve the interfacial adhesion and obtain the number of stagnation of the laminated film. The number of stagnations used here refers to a stagnation tester (for example, a Scott Scratch Resistance Tester (manufactured by Toyo Seiki)), a sample having a width of 10 mm and a length of 200 mm, a load of 2.5 kg, a distance between chucks of 30 mm, and a stroke distance. It is measured at 50 mm and a speed of 120 times / minute, and the number of times until the film breaks is obtained.

  Although the method of laminating the laminated film of the present invention is not particularly limited, a method of laminating without using an adhesive or a method of laminating with an adhesive can be used. From the viewpoint of interfacial adhesion, a method of laminating without an adhesive is preferred. As a specific method for laminating without using an adhesive, heat laminating by heat fusion is preferably used. The method of thermal lamination is not particularly limited, but thermal lamination using a heating roll is particularly preferable from the viewpoint of processability.

  The use of the laminated film of the present invention is not particularly limited, but is used for various insulating materials such as electrical insulating materials, molding materials, circuit board materials and process / release materials, and particularly used in hybrid cars and the like. It is suitably used as an electrical insulating material for a driving motor, a car air conditioner motor for carbon dioxide refrigerant, or a water heater motor for carbon dioxide refrigerant.

  Next, regarding a method for producing a laminated film, a poly-p-phenylene sulfide resin (hereinafter sometimes abbreviated as PPS) is used as the polyarylene sulfide resin, and a small amount of m-phenylene sulfide is added to the PPS as the copolymerized polyarylene sulfide resin. An example of the production of a laminated film using a poly-m-phenylene sulfide resin (hereinafter sometimes abbreviated as “meta-copolymerized PPS”) that has been copolymerized with styrene will be described. Of course, it is not limited.

  Examples of the method for producing the PPS resin include the following methods. Sodium sulfide and p-dichlorobenzene are reacted in an amide polar solvent such as N-methyl-2-pyrrolidone (NMP) under high temperature and high pressure. 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. to form a by-product salt, a polymerization aid, and Separate unreacted monomers. If necessary, an inorganic or organic additive or the like is added to the above-obtained polymer to the extent that the object of the present invention is not hindered to obtain a PPS resin.

  Examples of the method for producing the meta-body copolymerized PPS resin include the following methods. Sodium sulfide, p-dichlorobenzene, and the accessory component monomer are blended in the ratios referred to in the present invention, and in the presence of a polymerization aid in an amide polar solvent such as N-methyl-2-pyrrolidone (NMP) under high temperature and high pressure. React. As an accessory component monomer,

(Here, X represents an alkylene, CO, or SO ₂ unit.)

(Wherein R represents an alkyl, nitro, phenylene, or alkoxy group), and a plurality of these subcomponent monomers may be present. A preferred accessory component monomer is

  Next, the manufacturing method of the laminated | multilayer film of this invention is demonstrated. The PPS raw material and the meta-copolymerized PPS raw material are supplied to separate melt extrusion apparatuses and heated to the melting point or more of each raw material. 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. Such a molten laminate is cooled on the cooling drum to below the glass transition point of PPS to obtain a substantially amorphous two-layer or three-layer laminate sheet. The laminated structure is not particularly limited, but in the case of a two-layer laminate, a two-layer laminate of a PPS layer / meta body copolymerized PPS layer is preferable, and in the case of a three-layer laminate, a metabody copolymer PPS layer / PPS layer / meta body copolymer A three-layer stack of PPS layers is preferred. 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 or simultaneous biaxial stretching in the range of the glass transition temperature of the PPS to the cold crystallization temperature or less. After biaxial stretching by a machine, heat treatment is performed at a temperature in the range of 240 to 280 ° C. to obtain a biaxially oriented 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 biaxially oriented film having sufficient film planarity may not be obtained. When the draw ratio exceeds 4.0 times, the elongation at break of the present invention may be reduced. In some cases, interfacial adhesion cannot be obtained. Then, it is preferably stretched 2.8 to 3.5 times at 90 ° C. to 120 ° C. in the width direction. More preferably, it is 2.8 to 3.3 times, and still more preferably 2.8 to 3.0 times. In the present invention, when the draw ratio is less than 2.8 times, a biaxially oriented film having sufficient film flatness may not be obtained. When the draw ratio exceeds 3.5 times, the elongation at break of the present invention is not achieved. You may not get the degree.

  In the present invention, the area stretch ratio is preferably from 8 times to 12.5 times in order to obtain the breaking elongation and interfacial adhesion of the present invention, more preferably from 8 times to 12 times, and even more preferably. Is 8 to 11 times. When the area stretch ratio is less than 8 times, a biaxially oriented film having sufficient film flatness may not be obtained, and when it exceeds 12 times, the elongation at break and interfacial adhesion may be lowered.

  The heat treatment temperature is preferably 240 ° C. or higher and 280 ° C. or lower, more preferably 250 ° C. or higher and 280 ° C. or lower, and still more preferably 260 ° C. or higher and 280 ° C. or lower. Thereby, the orientation of the biaxially oriented meta-copolymer PPS layer can be relaxed, and the interfacial adhesion can be improved. Furthermore, it is preferable because the relaxation of the orientation of the meta-copolymerized PPS layer can be promoted and the interfacial adhesion can be improved by restricting (relaxing) each in the range of 1 to 20% in the longitudinal direction and / or the width direction. . More preferably, it is 3-15%, More preferably, it is 5-10%.

  The biaxially oriented two-layer laminated film obtained by the above method is superposed with a meta-copolymer PPS layer as an adhesive layer so that the PPS layer is the outermost layer (PPS layer / meta-copolymer PPS layer) / (meta A three-layer laminated film of body copolymerized PPS layer / PPS) is obtained. Further, a biaxially oriented PPS single film may be laminated to form a three-layer laminated film such as (PPS layer / meta-copolymerized PPS layer) / PPS. Moreover, it can also be set as (PPS layer / meta body copolymerization PPS layer) / PPS layer / (meta body copolymerization PPS layer / PPS layer). Also, a biaxially oriented three-layer laminated film of a meta-body copolymerized PPS layer / PPS layer / meta-body copolymerized PPS layer was prepared, and a biaxially oriented PPS single film and (PPS layer) / (meta-body copolymerized PPS layer) / PPS layer / meta body copolymerized PPS layer) / (PPS layer) may also be used. From the viewpoint of stability in film formation and improvement in flatness in the laminate, (PPS layer / meta body copolymerized PPS layer) / PPS layer / (meta body copolymerized PPS layer / PPS layer) is preferable. Of course, the laminated structure is not limited to these.

In the present invention, as a method for laminating the biaxially oriented laminated film, for example, a method of laminating under high temperature and high pressure is preferable. The laminating temperature is preferably 245 to 265 ° C, more preferably 250 to 265 ° C, still more preferably 255 to 265 ° C, and is preferable for obtaining the interfacial adhesiveness of the present invention. The lamination temperature here is the surface temperature of the metal roll, and can be measured with a non-contact thermometer or a contact thermometer. The nip roll is preferably made of a rubber material from the viewpoint of improving the surface properties of the laminate film, and fluorine rubber, silicon rubber, or the like can be used, but is not limited thereto. Moreover, the surface temperature of a nip roll becomes like this. Preferably it is 180 to 240 degreeC, More preferably, it is 190 to 240 degreeC, More preferably, it is 200 to 240 degreeC. The laminating pressure is preferably 1 to 20 kg / cm ² , more preferably 5 to 20 kg / cm ² , and even more preferably 10 to 20 kg / cm ² to obtain the interfacial adhesion of the present invention. Therefore, it is preferable. For the lamination of the biaxially oriented laminated film, the meta-body copolymerized PPS layer is laminated as an adhesive layer, but it is preferable to laminate the meta-body copolymerized PPS layer after preheating in advance. As a method for preheating the meta-copolymerized PPS layer, a metal roll or a nip roll was held on a heating roll at a holding angle of 50 to 180 degrees, preferably 60 to 180 degrees, and more preferably 90 to 180 degrees. Post-lamination is a preferred embodiment for obtaining the interfacial adhesion of the present invention. The laminating speed is 0.1 to 10 m / min, preferably 0.5 to 5 m / min, more preferably 1 to 7 m / min, and further preferably 3 to 5 m / min. From the viewpoint of productivity. In a preferred embodiment, the laminate is cooled immediately below the glass transition point of PPS from the viewpoint of maintaining the flatness and interfacial adhesion of the laminate film and the elongation at break.

  The biaxially oriented meta-body copolymerized PPS layer and the biaxially oriented PPS layer used in the present invention may be subjected to corona discharge treatment or plasma treatment in order to impart stronger heat sealability. include. As the atmospheric gas during the corona discharge treatment, at least one gas selected from air (EC treatment), oxygen (OE treatment), nitrogen (NE treatment), carbon dioxide gas (CE treatment), and the like can be given. Among these, it is preferable to use EC treatment from the viewpoint of economy, and it is preferable to perform surface treatment by NE treatment or CE treatment from the viewpoint of improving adhesiveness as described above. In the present invention, surface treatment is performed by NE treatment. It is more preferable from the viewpoint of improving adhesiveness. Moreover, in this invention, unless the effect of this invention is prevented, another sheet layer can be laminated | stacked as needed.

  Moreover, in this invention, in order to improve the handleability and workability of a laminated | multilayer film, an inert particle 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).

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

  The elongation at break is determined by measuring and averaging both the film longitudinal direction and the width direction at n = 5.

(2) Melting temperature (Tm)
Specific heat was measured with the following apparatus and conditions by the pseudo-isothermal method, and determined according to JIS K7121. The number of samples was measured for each sample, and the average value was taken.

Apparatus: Temperature modulation DSC manufactured by TA Instrument
Measurement condition:
Heating temperature: 270-570K (RCS cooling method)
Temperature calibration: Melting point of high purity indium and tin Temperature modulation amplitude: ± 1K
Temperature modulation period: 60 seconds Temperature rising step: 5K
Sample weight: 5mg
Sample container: Aluminum open container (22 mg)
Reference container: Aluminum open container (18mg)
In addition, using a Seiko Instruments DSC (RDC220) as the suggested scanning calorimeter and a disk station (SSC / 5200) manufactured by Seiko Instruments as a data analysis device, 5 mg of the sample was melted and held at 300 ° C. for 5 minutes on an aluminum saucer. After rapid solidification, the temperature was raised from room temperature at a heating rate of 20 ° C./min. At that time, the peak temperature of the endothermic peak of melting observed was defined as the melting temperature (Tm).

(3) Stagnation test Measures according to JIS-K-6328 using a Scott Scratch Resistance Tester (manufactured by Toyo Seiki). The sample size is measured at a width of 10 mm, a length of 200 mm, a load of 2.5 kg, a distance between chucks of 30 mm, a stroke distance of 50 mm, and a speed of 120 times / minute, and the number of times until the film breaks visually is determined. Judgment was made according to the following criteria.

◎ 140 times or more ○: 120 times or more and less than 140 times Δ: 90 times or more and less than 120 times ×: less than 90 times.

(4) tan δ
A sample having a sample width of 5 mm and a sample length (distance between chucks) of 20 mm was measured using DMS6100 (manufactured by Seiko Instruments Inc.) as a dynamic viscoelasticity (DMA) measuring apparatus. Detailed measurement conditions are shown below.

Measurement temperature range: -150 ° C to 200 ° C
Vibration frequency: 1Hz
Vibration displacement (strain): 5 μm, initial load: 50 mN
Temperature increase rate: 2 ° C / min, Gain: 1.5
Initial value of force amplitude: 100 mN.

(5) Motor processability Using a motor slot processing machine (Odawara Engineering Co., Ltd.), a sample was processed into a slot with a width of 24 mm and a length of 39 mm at a processing speed of 2 / sec. Defective products were evaluated according to the following criteria. The number of processed samples is 100 for each sample.
A: Defect rate is 0%
○: The defect rate exceeds 0% and 5% or less. Δ: The defect rate exceeds 6% and 20% or less. X: The defect rate exceeds 20%.

(6) Melt Viscosity Using a flow tester CFT-500 (manufactured by Shimadzu Corporation), 310 ° C., shear rate 200 sec ⁻¹ , base length is 10 mm, base diameter is 1.0 mm, preheating time is set to 5 minutes. Measured.

Example 1
(1) Production of meta-copolymerized PPS resin 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 89 mol of p-dichlorobenzene as a main component monomer, 12 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, and nitrogen was pressurized and sealed at 3 kg / cm ² at a temperature of 170 ° C. After completion of the polymerization, the mixture was cooled, the polymer was precipitated in distilled water, and a small block polymer was collected with a wire mesh having a 150 mesh opening. The small block polymer thus obtained was washed 5 times with distilled water at 90 ° C. and then dried under reduced pressure at a temperature of 120 ° C. so that the melt viscosity was 1000 poise and the melting point was 240 ° C. A copolymerized PPS resin was obtained. Next, 0.3% by weight of calcium carbonate powder having an average particle size of 1.2 μm was added, uniformly dispersed and blended, and extruded in a gut shape at a temperature of 320 ° C. with a 30 mmφ twin-screw extruder, and pellets of a meta-body copolymerized PPS Got.

(2) Production of PPS resin All the steps except for using 101 moles of p-dichlorobenzene as a main component monomer and not using a subcomponent monomer, were carried out in the same manner as in the production of the meta-copolymerized PPS in (1) above. A PPS resin was produced. The melt viscosity of the PPS resin was 3000 poise and the melting point was 283 ° C.

(3) Film formation The meta-copolymerized PPS resin and PPS resin obtained in (1) and (2) above were dried at a temperature of 180 ° C. for 3 hours under a reduced pressure of 1 mmHg, and then supplied to separate extruders. In a molten state, the double tube type laminating device at the upper part of the die leads to two layers, and then is discharged from the T-die die provided and rapidly cooled with a cooling drum having a temperature of 25 ° C. Thus, a two-layer laminated sheet of meta-body copolymerized PPS / PPS was obtained. Next, each obtained laminated sheet is caused to travel in contact with a plurality of heating rolls having a surface temperature of 95 ° C., and in the longitudinal direction between 30 ° C. cooling rolls having different peripheral speeds provided next to the heating roll. The film was stretched 3 times. The uniaxially stretched sheet thus obtained was stretched 2.8 times (area stretch ratio 9.2 times) at a temperature of 100 ° C. in a direction perpendicular to the longitudinal direction using a tenter, and subsequently 265 ° C. After heat treatment at a temperature for 10 seconds, 5% limited shrinkage (relaxation) treatment was performed in the direction perpendicular to the longitudinal direction of the film, and after intermediate cooling at a temperature of 100 ° C. for 5 seconds, the mixture was cooled to room temperature and meta-copolymerized PPS / PPS (20 / 105 μm) was obtained.

  Further, the single PPS resin was separately formed and heat-treated under the above film forming conditions to obtain a single film having a thickness of 125 μm.

(4) Lamination A biaxially oriented laminated film and a PPS single film obtained by the above film forming method were heat laminated using a meta-body copolymerized PPS layer as an adhesive layer. Lamination conditions were as follows: an HCr roll as a heating roll was heated to a temperature of 255 ° C., and a nip roll was heated to 240 ° C. using a fluoro rubber roll. The laminating pressure was 20 kg / cm ² and the laminating speed was 2 m / min. The biaxially oriented laminated film was preheated on a nip roll at a holding angle of 90 degrees and then laminated. After laminating, it was immediately cooled and wound up. Table 1 shows the evaluation results of the three-layer laminated film obtained as described above.

(Example 2)
A three-layer laminated film was produced in the same manner as in Example 1 except that the biaxially oriented laminated film used in Example 1 was 3.5 × 3.0 times (area stretch ratio 10.5 times). Table 1 shows the evaluation results of the obtained three-layer laminated film.

Example 3
A three-layer laminated film was produced in the same manner as in Example 1 except that the biaxially oriented laminated film used in Example 1 was 3.6 × 3.3 times (area stretch ratio 11.9 times). Table 1 shows the evaluation results of the obtained three-layer laminated film.

Example 4
A three-layer laminated film was produced in the same manner as in Example 1 except that the biaxially oriented laminated film used in Example 1 was 3.5 × 3.5 times (area stretch ratio 12.2 times). Table 1 shows the evaluation results of the obtained three-layer laminated film.

(Example 5)
A three-layer laminated film was produced in the same manner as in Example 1 except that the biaxially oriented laminated film used in Example 1 was heat-treated at 260 ° C. Table 1 shows the evaluation results of the obtained three-layer laminated film.

(Example 6)
A three-layer laminated film was produced in the same manner as in Example 1 except that the biaxially oriented laminated film used in Example 1 was heat-treated at 240 ° C. Table 1 shows the evaluation results of the obtained three-layer laminated film.

(Example 7)
A three-layer laminated film was produced in the same manner as in Example 1 except that the biaxially oriented laminated film used in Example 1 was subjected to 4% limiting shrinkage (relaxation) treatment. Table 1 shows the evaluation results of the obtained three-layer laminated film.

(Example 8)
A three-layer laminated film was produced in the same manner as in Example 1 except that the biaxially oriented laminated film used in Example 1 was subjected to 3% limiting shrinkage (relaxation) treatment. Table 1 shows the evaluation results of the obtained three-layer laminated film.

Example 9
A three-layer laminated film was produced in the same manner as in Example 1 except that the biaxially oriented laminated film used in Example 1 and the PPS single film were laminated at a temperature of 265 ° C. Although the evaluation result of the obtained three-layer laminated film is shown in Table 1, since the film flatness is deteriorated, the motor processability is lowered.

(Example 10)
A three-layer laminated film was produced in the same manner as in Example 1 except that the biaxially oriented laminated film used in Example 1 and the PPS single film were laminated at a temperature of 250 ° C. Table 1 shows the evaluation results of the obtained three-layer laminated film.

(Example 11)
A three-layer laminated film was produced in the same manner as in Example 1 except that the biaxially oriented laminated film used in Example 1 and the PPS single film were laminated at a temperature of 245 ° C. Table 1 shows the evaluation results of the obtained three-layer laminated film.

(Example 12)
A three-layer laminated film was produced in the same manner as in Example 1 except that 10 mol% of m-dichlorobenzene was added as a subsidiary component monomer in Example 1 to obtain a meta-copolymer PPS having a melting point of 250 ° C. Table 1 shows the evaluation results of the obtained three-layer laminated film.

(Example 13)
A three-layer laminated film was produced in the same manner as in Example 1 except that 8 mol% of m-dichlorobenzene was added as a subsidiary component monomer in Example 1 to obtain a meta-copolymer PPS having a melting point of 255 ° C. Table 1 shows the evaluation results of the obtained three-layer laminated film.

(Example 14)
A three-layer laminated film was produced in the same manner as in Example 1 except that a biaxially oriented laminated film of meta-body copolymerized PPS / PPS (15/110 μm) was used in Example 1. Table 1 shows the evaluation results of the obtained three-layer laminated film.

(Example 15)
A three-layer laminated film was produced in the same manner as in Example 1 except that a biaxially oriented laminated film of meta-body copolymerized PPS / PPS (10/115 μm) was used in Example 1. Table 1 shows the evaluation results of the obtained three-layer laminated film.
(Example 16)
The NE treatment is performed on the meta-copolymerization PPS side of the biaxially oriented laminated film of the meta-copolymerization PPS / PPS (20/105) obtained in Example 3 and is in contact with the PPS simple substance meta-copolymerization PPS. A three-layer laminated film was produced in the same manner as in Example 3 except that the side was subjected to EC treatment. Table 1 shows the evaluation results of the obtained three-layer laminated film.
(Example 17)
A three-layer laminated film was produced in the same manner as in Example 16 except that the lamination speed was 5 m / min in Example 16. Table 1 shows the evaluation results of the obtained three-layer laminated film.

( Comparative Example 12 )
A three-layer laminated film was produced in the same manner as in Example 1 except that a biaxially oriented laminated film of meta-body copolymerized PPS / PPS (50/75 μm) was used in Example 1. Table 1 shows the evaluation results of the obtained three-layer laminated film.

(Example 19)
The meta-body-copolymerized PPS resin and PPS resin obtained in Example 1 are formed into three layers of meta-body-copolymerized PPS / PPS / meta-body-copolymerized PPS in a triple tube type laminating device at the top of the die in a molten state Thus, in the same manner as in Example 1, a biaxially oriented three-layer laminated film of a meta body copolymerized PPS / PPS / meta body copolymerized PPS (20/80/20 μm) was obtained.

  At this time, the PPS composition alone was formed and heat-treated under the above-mentioned film forming conditions to obtain a single film having a thickness of 115 μm.

The biaxially oriented three-layer laminated film and the PPS monolayer film obtained above were heat-sealed so that the meta-body copolymerized PPS layer and the PPS monolayer film overlapped, and PPS / (meta-body copolymer PPS / PPS / A meta-layer copolymerized PPS) / PPS five-layer laminated film was prepared. The evaluation results of the obtained five-layer laminated film are shown in Table 1.
(Example 20)
A biaxially oriented laminated film was produced in the same manner as in Example 1 except that the meta-body copolymerized PPS / PPS (10/65 μm) was used. In addition, a 100 μm PPS resin simple substance was produced in the same manner as in Example 1. The biaxially oriented laminated film and the PPS single film obtained above were laminated so as to be (PPS / meta-copolymerized PPS) / PPS / (meta-copolymerized PPS / PPS), and laminated in the same manner as in Example 1. To prepare a five-layer laminated film. The evaluation results of the obtained five-layer laminated film are shown in Table 1.
(Example 21)
A five-layer laminated film was produced in the same manner as in Example 20 except that the biaxially oriented laminated film used in Example 20 was 3.5 × 3.0 times (area stretch ratio 10.5 times). The evaluation results of the obtained five-layer laminated film are shown in Table 1.

(Example 22)
A five-layer laminated film was produced in the same manner as in Example 20, except that the biaxially oriented laminated film used in Example 20 was 3.6 × 3.3 times (area stretch ratio: 11.9 times). The evaluation results of the obtained five-layer laminated film are shown in Table 1.
(Example 23)
A five-layer laminated film was produced in the same manner as in Example 20 except that 10 mol% of m-dichlorobenzene was added as an accessory component monomer in Example 20 to obtain a meta-body copolymerized PPS having a melting point of 250 ° C. The evaluation results of the obtained five-layer laminated film are shown in Table 1.
(Example 24)
A five-layer laminate film was produced in the same manner as in Example 23 except that the biaxially oriented laminate film used in Example 23 was 3.5 × 3.0 times (area stretch ratio 10.5 times). The evaluation results of the obtained five-layer laminated film are shown in Table 1.

(Example 25)
A five-layer laminated film was produced in the same manner as in Example 23 except that the biaxially oriented laminated film used in Example 23 was 3.6 × 3.3 times (area stretch ratio: 11.9 times). The evaluation results of the obtained five-layer laminated film are shown in Table 1.
(Example 26)
The NE treatment is performed on the meta-copolymerization PPS side of the biaxially oriented laminated film of the meta-copolymerization PPS / PPS (10/65) obtained in Example 25, and EC treatment is performed on both sides of the 100 μm PPS single body. Produced a 5-layer laminated film in the same manner as in Example 25. The evaluation results of the obtained five-layer laminated film are shown in Table 1.
(Example 27)
A five-layer laminated film was produced in the same manner as in Example 26 except that the lamination speed was 5 m / min in Example 26. The evaluation results of the obtained five-layer laminated film are shown in Table 1.

(Comparative Example 1)
A three-layer laminated film was produced in the same manner as in Example 1 except that the biaxially oriented laminated film used in Example 1 was set to 3.8 × 3.6 times (area stretch ratio: 13.7 times). Table 1 shows the evaluation results of the obtained three-layer laminated film.

(Comparative Example 2)
In Example 1, 10 mol% of m-dichlorobenzene was added as an accessory component monomer to obtain a meta-copolymer PPS having a melting point of 250 ° C., and the biaxially oriented laminated film was 3.5 × 3.5 times (area stretch ratio). 12.2), a biaxially oriented laminated film was produced in the same manner as in Example 1 except that the heat treatment temperature was 260 ° C. and the meta-body copolymerized PPS / PPS (10/115 μm).

  A three-layer laminated film was produced in the same manner as in Example 1 except that the biaxially oriented laminated film and the PPS single film obtained above were laminated at 240 ° C. Table 1 shows the evaluation results of the obtained three-layer laminated film.

(Comparative Example 3)
A three-layer laminated film was produced in the same manner as in Example 1 except that the biaxially oriented laminated film used in Example 1 and the PPS single film were laminated at a temperature of 240 ° C. Table 1 shows the evaluation results of the obtained three-layer laminated film.

(Comparative Example 4)
A three-layer laminated film was produced in the same manner as in Example 1 except that the biaxially oriented laminated film used in Example 1 was subjected to a 0% limiting shrinkage (relaxation) treatment. Table 1 shows the evaluation results of the obtained three-layer laminated film.

(Comparative Example 5)
A three-layer laminated film was produced in the same manner as in Example 1 except that the nip roll was not heated in Example 1. Table 1 shows the evaluation results of the obtained three-layer laminated film.

(Comparative Example 6)
A three-layer laminated film was produced in the same manner as in Example 1 except that 5 mol% of m-dichlorobenzene was added as a subcomponent monomer in Example 1 to obtain a meta-copolymer PPS having a melting point of 265 ° C. Table 1 shows the evaluation results of the obtained three-layer laminated film.

(Comparative Example 7)
A three-layer laminated film was produced in the same manner as in Example 1 except that the biaxially oriented laminated film of meta-body copolymerized PPS / PPS (5/120 μm) was used in Example 1. Table 1 shows the evaluation results of the obtained three-layer laminated film.

(Comparative Example 8)
A five-layer laminate film was produced in the same manner as in Example 15 except that a biaxially oriented three-layer laminate film of meta-body copolymerized PPS / PPS / meta-body copolymerized PPS (5/110/5 μm) was used. did. The evaluation results of the obtained five-layer laminated film are shown in Table 1.

(Comparative Example 9)
The single PPS resin used in Example 1 was formed and heat-treated under the same film forming conditions as in Example 1 to produce a single PPS film having a thickness of 75 μm. In addition, a non-oriented film having a thickness of 100 μm made of the PPS resin alone was produced. The obtained PPS biaxially oriented film and non-oriented film were laminated in the order of biaxially oriented film / non-oriented film / biaxially oriented film and laminated in the same manner as in Example 1 to produce a three-layer laminated film. Table 1 shows the evaluation results of the obtained three-layer laminated film.

(Comparative Example 10)
A five-layer laminated film was produced in the same manner as in Example 25 except that the surface treatment was not performed in Example 25. The evaluation results of the obtained five-layer laminated film are shown in Table 1.

(Comparative Example 11)
A five-layer laminated film was produced in the same manner as in Example 25 except that the nip roll was not heated in Example 25. The evaluation results of the obtained five-layer laminated film are shown in Table 1.

  The laminated film of the present invention combines PPS's excellent heat resistance, chemical resistance, flame resistance, impact resistance, and moist heat resistance, and has excellent interfacial adhesion of the laminated film, resulting in greatly improved tensile elongation. Therefore, it is particularly suitable as an electrical insulating material for a drive motor, a car air conditioner motor for carbon dioxide refrigerant, or a water heater motor for carbon dioxide refrigerant used in a hybrid car, and is industrially useful.

Claims (9)

The outermost layer is a laminated film made of biaxially oriented polyarylene sulfide, and at least one layer other than the outermost layer is made of biaxially oriented copolymerized polyarylene sulfide, and the outermost layer of biaxially oriented polyarylene sulfide and biaxially oriented A laminated film comprising polymerized polyarylene sulfides adjacent to each other, having a tensile elongation at break of 100 to 150%, and the number of stagnation until film rupture by a sag test is 90 or more. The laminated film according to claim 1, wherein the number of stagnation until the film breaks by a stagnation test is 100 times or more. The laminated film according to claim 1 or 2, wherein the outermost polyarylene sulfide is poly-p-phenylene sulfide. The laminated film according to any one of claims 1 to 3, wherein the copolymerized polyarylene sulfide is a copolymerized polyphenylene sulfide. The laminated film according to any one of claims 1 to 4, wherein the copolymerized polyarylene sulfide layer is 10 to 50 µm. The copolymerized polyarylene sulfide layer is composed of units represented by the following structural formula 1 in which 80 mol% or more and 92 mol% or less of repeating units are represented, and 8 mol% or more and 20 mol% or less of repeating units are represented by the following structural formula 2 The laminated film according to any one of claims 1 to 5, wherein the laminated film is mainly composed of a random copolymer comprising the units represented.

The laminated film according to any one of claims 1 to 6, wherein the peak temperature of tan δ in the dynamic viscoelasticity measurement of the laminated film is 115 ° C or higher and 123 ° C or lower. The method for producing a laminated film according to any one of claims 1 to 7 , wherein an area stretch ratio of the laminated film is 8 to 12.5 times. Method for producing a laminated film according to any one of laminating temperature of the laminated film is 245-265 ° C. claims 1-8.