JP5824909B2 - Composite film and manufacturing method thereof - Google Patents

Description

  The present invention relates to a composite film using polyphenylene sulfide, and more particularly to a composite film suitable for use in electric insulation of a motor.

  Polyphenylene sulfide film has excellent properties such as heat resistance, hydrolysis resistance, chemical resistance, flame retardancy, and electrical insulation, and is particularly suitable for electrical and electronic equipment, mechanical parts, automotive parts, etc. It is used.

  In recent years, polyphenylene sulfide films have been applied to electrical insulating materials by taking advantage of their high electrical insulation and heat resistance. In addition, a composite film composed of polyphenylene sulfide / copolymerized polyphenylene sulfide / polyphenylene sulfide in which a polyphenylene sulfide film is combined to improve electrical insulation is disclosed (see Patent Documents 1 and 2). This is because when a certain thickness is required for electrical insulation applications, polyphenylene sulfide resin has a higher crystallization speed than polyester resin such as polyethylene terephthalate and polyethylene naphthalate, so that a thick polyphenylene sulfide film is uniaxial or biaxial. When the axial stretching is performed, the film is torn and the production efficiency is deteriorated. Therefore, the copolymer polyphenylene sulfide film is interposed in the polyphenylene sulfide film and heat-sealed to obtain the thickness. However, the above-mentioned conventional composite film has a high heating temperature in the heating roll in order to achieve heat fusion in a short time, but a dent is generated on the film surface on the cooling roll or the conveyance roll. There were cases where tearing occurred and physical properties such as elongation were lowered. Such dents can cause quality defects when used for motor insulation applications. In addition, when the heat fusion temperature is lowered to eliminate such dents, the adhesive strength between layers is not sufficient, and there is a limit to the use of an electrical insulating material in severe conditions such as motor insulation.

JP 2007-98941 A JP 2010-110898 A

  Accordingly, the object of the present invention is to provide a composite film excellent in appearance and physical properties by eliminating this problem without impairing electrical insulation, motor processability, and interfacial adhesion between layers. .

(1) A biaxially oriented film (for convenience, also referred to as film A) having a layer substantially composed of polyparaphenylene sulfide in the outermost layer (for convenience, also referred to as film A), and substantially one of the outermost layers Consists of polyphenylene sulfide having a layer composed of polyparaphenylene sulfide (also referred to as layer A ′ for convenience) and having a melting point 20 ° C. lower than the substantial polyparaphenylene sulfide constituting layer A in the opposite outermost layer A biaxially oriented film (also referred to as film B for convenience) having a formed layer (also referred to as layer B for convenience) is bonded between layer A of film A and layer B of film B without using an adhesive. A composite film having a thickness of 120 μm or more and 500 μm or less and a breaking elongation of 80% or more, wherein the adhesive strength between the layer A and the layer B is 100 g / 15 mm or less. A composite film characterized by having a surface dent having a major axis of 100 μm or more and a depth of 0.5 μm or more on the surface of the composite film of 1 piece / 100 cm ² or less.
(2) The composite film according to claim 1, wherein the thickness of the layer B is 10 µm or more and 30 µm or less, and the melting point of the copolymerized polyphenylene sulfide constituting the layer B is 230 to 265 ° C.
(3) The composite film according to claim 1 or 2, wherein a defect rate in motor processability of the composite film is 20% or less.
<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 pcs / sec, and film cracking or delamination occurred visually. Were evaluated as defective, and the rate of defective products was evaluated according to the following criteria. The number of processed samples is 100 for each sample.
( 4) A biaxially oriented film (for convenience, also referred to as film A) having a layer (for convenience, referred to as layer A) consisting essentially of polyparaphenylene sulfide in the outermost layer; Polyphenylene sulfide having a layer made of polyparaphenylene sulfide (also referred to as layer A ′ for convenience) and having a melting point of 20 ° C. or more lower than the substantial polyparaphenylene sulfide constituting layer A on the opposite outermost layer A heat-sealing step of thermocompression bonding the layer A of the film A and the layer B of the film B of a biaxially oriented film (also referred to as a film B for convenience) having a structured layer (also referred to as a layer B for convenience); A step of cooling the film after heat fusion, and a step of winding the cooled film through at least one transport roll, and the heat fusion step, Method for producing a composite film retirement process is characterized by satisfying the following (i) ~ (ii).
( I ) In a heating roll and a pressure-bonding roll for heat-bonding the layer A and the layer B in the heat-sealing step, the surface temperature of the heating roll is (Tmb-10) (° C.) or more and (Tma-20) (° C.) or less. In addition, the heat-sealed body is peeled off from the heating roll along the outer periphery of the heating roll in the range of 90 ° or more and 270 ° or less from the pressure-bonded point. here,
Tma: Melting point of resin constituting layer A (° C.)
Tmb: Melting point of resin constituting layer B (° C.)
( Ii ) In the step of cooling the film after heat-sealing, the heat-fused composite film between the heating roll and the first transport roll is substantially at a rate of 15 ° C./s to 30 ° C./s in a gas atmosphere. To cool below the glass transition temperature of the layer made of polyparaphenylene sulfide (layer A).

  ADVANTAGE OF THE INVENTION According to this invention, the composite film excellent in electrical insulation, motor workability, interface adhesiveness, and external appearance can be provided.

  The present invention relates to a biaxially oriented film (film A) having a layer (layer A) consisting essentially of polyparaphenylene sulfide in the outermost layer, and a layer (layer consisting essentially of polyparaphenylene sulfide in one outermost layer. A ′), and a biaxial orientation having a layer (layer B) composed of polyarylene sulfide whose melting point is 20 ° C. or more lower than that of substantial polyparaphenylene sulfide constituting layer A in the opposite outermost layer Film (B) is used.

  Here, substantially consisting of polyparaphenylene sulfide (hereinafter, polyparaphenylene sulfide may be abbreviated as PPS) means that 85 mol% of the paraphenylene sulfide unit represented by the following structural formula is used as the main repeating unit of the polymer. The above-mentioned polymer is referred to, preferably 90 mol% or more, more preferably 98 mol% or more is a paraphenylene sulfide unit. If this component is less than 85 mol%, the crystallinity, softening point, etc. of the polymer may be lowered, and heat resistance, dimensional stability, mechanical properties, etc. may be impaired.

  In the polymer substantially composed of polyparaphenylene sulfide, the repeating unit other than paraphenylene sulfide is preferably a repeating unit containing a phenylene sulfide structure other than the paraphenylene sulfide structure, as long as the object of the present invention is not impaired. Other repeating units may be used. The mode of copolymerization may be random copolymerization or block copolymerization.

  The polyarylene sulfide having a melting point of 20 ° C. or more lower than the substantial polyparaphenylene sulfide constituting the layer A, which is the layer B, is polyarylene sulfide having a phenylene sulfide unit as a main repeating unit, The melting point is 20 ° C. or more lower than the substantial polyparaphenylene sulfide constituting A. The main meaning is that the polyarylene sulfide is preferably a repeating unit containing 100 mol% of a phenylene sulfide structure, but other repeating units are not more than about 10 mol% as long as the object of the present invention is not impaired. It means that it may be included. The melting point of the polyarylene sulfide constituting the layer B can be adjusted by copolymerizing repeating units other than the paraphenylene sulfide unit. The polyarylene sulfide constituting the layer B should have a melting point of 20 ° C. or more lower than the substantial polyparaphenylene sulfide constituting the layer A, but if the melting point difference is too large, the heat resistance of the film may be impaired. Therefore, the melting point difference is preferably within 90 ° C, desirably within 60 ° C, and more desirably within 40 ° C. On the other hand, when the melting point difference is less than 20 ° C., the interfacial adhesion between the layer A and the layer B cannot be sufficiently increased, and a dent may be generated on the surface of the composite film.

  Specific examples of structural units other than the paraphenylene sulfide units used for the polyarylene sulfide constituting the layer B include biphenylene sulfide units, biphenylene ether sulfide units, biphenylene sulfone sulfide units, biphenylene carbonyl sulfide units, naphthalene sulfide units, and the like. However, it is preferable that a metaphenylene sulfide unit represented by the following formula is copolymerized. The copolymerization amount of the metaphenylene sulfide unit is preferably 5 mol% or more and 20 mol% or less, more preferably 5 mol% or more and 15 mol% or less. By using 5 mol% or more of the metaphenylene sulfide unit, high interfacial adhesion can be obtained, and the flexibility of the film is improved, so that the composite film is hardly broken in the motor processing step. In addition, as the structural unit other than the paraphenylene sulfide unit, a plurality of types of structural units may be used. Further, it may be a block copolymer or a random copolymer.

  In the layer A and the layer A ′ substantially composed of polyparaphenylene sulfide and the layer B composed of polyarylene sulfide whose melting point is 20 ° C. or more lower than that of the substantially polyparaphenylene sulfide constituting the layer A, respectively, It is desirable that it is constituted by the substantially polyparaphenylene sulfide or polyarylene sulfide described in the above, but other components in a range of less than 10% by mass of the total mass of each layer within the range not impairing the object of the present invention, For example, polymers other than polyarylene sulfide, inorganic or organic fillers, lubricants, colorants, ultraviolet absorbers, compatibilizers, and other additives can be included. Examples of polymers other than polyarylene sulfide include various polymers such as polyamide, polyetherimide, polyethersulfone, polysulfone, polyphenylene ether, polyester, polyarylate, polyamideimide, polycarbonate, polyolefin, polyetheretherketone, and these polymers. In addition, examples of the inorganic filler include silica, alumina, calcium carbonate, barium carbonate, barium titanate, barium sulfate, calcium silicate, magnesium oxide, titanium oxide, and zinc oxide. Examples of such inorganic fillers and organic fillers include fillers of organic polymer compounds that do not melt at 300 ° C. (eg, crosslinked polystyrene).

  Further, the layer A and the layer B may be subjected to arbitrary processing such as heat treatment and surface treatment as necessary.

  The substantial melting point (Tma) of the polyparaphenylene sulfide constituting the layer A or the layer A ′ is preferably 260 ° C. or higher and 300 ° C. or lower, more preferably 270 ° C. or higher and 300 ° C. or lower, and further preferably 280 ° C. or higher. It is 290 degrees C or less. If Tma is less than 260 ° C., the heat resistance of the composite film may not be sufficient, and if it exceeds 300 ° C., the load on the extruder during melt film formation may increase.

  The thickness of the layer B is preferably 10 μm or more and 50 μm or less, more preferably 10 μm or more and 40 μm or less, and further preferably 10 μm or more and 30 μm or less. When the thickness of the layer B is less than 10 μm, the orientation relaxation of the layer B may not proceed sufficiently, and the adhesive strength between the layer A and the layer B may not be obtained sufficiently. When the thickness exceeds 50 μm, the heat resistance of the composite film decreases. Sometimes. Here, the thickness of the layer B is the thickness per layer of the layer B present in the composite film.

  The composite film of the present invention needs to have a thickness of 120 μm to 500 μm, preferably 150 μm to 350 μm, and more preferably 200 μm to 350 μm. When the thickness is less than 120 μm, the electric insulation as the motor insulating film is not sufficient, and when the thickness exceeds 500 μm, the heat fusion processability of the composite film is lowered, and the interfacial adhesion and the motor processability are lowered.

The composition of the composite film of the present invention consists of a biaxially oriented film (film A) having a layer (layer A) consisting essentially of polyparaphenylene sulfide in the outermost layer, and substantially polyparaphenylene sulfide in one outermost layer. A layer (layer B) composed of polyarylene sulfide having a melting point of 20 ° C. or more lower than the substantial polyparaphenylene sulfide constituting layer A in the opposite outermost layer. A biaxially oriented film (film B) having a structure including a layer A of film A and a layer B of film B joined without using an adhesive. As an example of the simplest configuration, a single-layer biaxially oriented film (corresponding to the layer A) substantially composed of polyparaphenylene sulfide as the film A and a substantially polyparaphenylene sulfide layer (layer A) as the film B And a biaxially oriented film composed of two layers of a polyarylene sulfide layer (corresponding to layer B) whose melting point is 20 ° C. or more lower than the substantial polyparaphenylene sulfide of film A. A film is mentioned.
As another example, as the film A, a two-layer film of (a layer substantially consisting of polyparaphenylene sulfide (corresponding to the A layer)) / (a layer consisting of another polyphenylene sulfide) or substantially polyparaphenylene Three layers consisting of sulfide (corresponding to layer A) / (layer consisting of one or more other polyphenylene sulfides) / (layer consisting essentially of polyparaphenylene sulfide (corresponding to layer A)) The above-mentioned films are mentioned, and the film B can also be a film of two layers or three or more layers. In addition to film A / film B bonding, the film B can be further heat-sealed to the film B side or the film A side of this composite film (the outermost layer of the composite film as the adherend is a layer) Because it is A or layer A ′).

  In the present invention, a layer substantially composed of polyparaphenylene sulfide (layer A (or layer A ′)) and a layer composed of polyarylene sulfide whose melting point is 20 ° C. or more lower than that of the substantially polyparaphenylene sulfide (layer B). ) Are bonded without using an adhesive, and a specific method is preferably a heat fusion method described later. Although the method of heat sealing | fusion is not specifically limited, From the point of process property, the heat sealing | fusion with a heating roll is preferable. As described above, it is difficult to obtain a film having a certain thickness or more with polyphenylene sulfide. When trying to obtain the thickness of the composite film of the present invention by the co-extrusion method, poly (para) phenylene sulfide crystallizes and stretches in the biaxial direction while cooling in the casting process during film formation is insufficient. Attempting to do so will tear the membrane. On the other hand, if the stretching is insufficient, sufficient orientation cannot be obtained and the elongation at break is low. For this reason, the present invention is a composite film in which a plurality of biaxially oriented films (film A and film B) are joined.

  In order to obtain motor processability, the elongation at break of the composite film of the present invention is 60% or more. Preferably it is 70% or more, More preferably, it is 80% or more. When the elongation at break is less than 60%, the composite film may break during the motor processing. In addition, no particular upper limit is set for the breaking elongation, but in order to increase the breaking elongation, the stretching ratio in the film longitudinal direction and / or the width direction during film formation, which will be described later, is lowered. And the flatness of the film B may deteriorate, or the interfacial adhesion may decrease. For this reason, it is practical that the breaking elongation of the composite film of the present invention is usually about 200% or less. In order to obtain good motor processability, the breaking elongation of the composite film is preferably 60% or more in both the film longitudinal direction and the width direction.

  In the composite film of the present invention, the adhesive strength between the layer A and the layer B is required to be 70 g / 15 mm so that the composite film does not break in the motor processing step, preferably 100 g / 15 mm or more, More preferably, it is 150 g / 15 mm or more. When the adhesive strength is less than 70 g / 15 mm, the rupture elongation of the composite film may decrease due to interfacial peeling, and the composite film may break in the motor processing step. The upper limit of the adhesive strength is not particularly limited, but is generally about 400 g / 15 mm in relation to the flatness described later. In order to make the adhesive strength within the above range, it is necessary to improve the interfacial adhesion between the layer A and the layer B. In order to improve the interfacial adhesion, it is preferable to raise the heat fusion temperature, but the flatness of the composite film deteriorates, the load when inserting the composite film into the motor by machine increases, and the insertability deteriorates. As a result, an extra force is applied to the composite film, buckling occurs, and motor processability may be reduced. Here, the adhesive strength means that the interface between layer A and layer B of a sample having a width of 15 mm is partially peeled off with a cutter or the like to produce a grip allowance, and this grip allowance is grasped with a chuck of a tensile tester. The strength was measured when the film was pulled and peeled so that the angle formed by the layer A and the layer B to be peeled was 180 ° at 200 mm / min.

  As a method for setting the breaking elongation of the composite film within the above range, the film A and the film B are formed under the film-forming stretching conditions and heat treatment conditions described later, and are fused under the heat-bonding conditions described later. To obtain.

The surface dent of the composite film of the present invention needs to be 1 piece / 100 cm ² or less, and preferably has substantially no surface dent. If the surface dent exceeds 1 piece / 100 cm ² , the appearance of the composite film will be impaired, and the electrical insulation may be deteriorated. The surface depression referred to here is a depression that can be confirmed with the naked eye on the surface of the composite film directly under the fluorescent lamp, using the surface structure analyzer (NewView 100) manufactured by ZYGO, and the major axis of the depression by the scanning white interference method. Depth is measured, and it refers to a recess having a major axis of 100 μm or more and a depth of 0.5 μm or more.

  By setting the thickness and surface dent of the composite film within the above ranges, the partial discharge start voltage of the composite film can be set to 800 V or more, and it can be preferably used as a motor insulating film. The partial discharge start voltage is more preferably 1000 V or higher, and still more preferably 1300 V or higher.

As a method of setting the surface dents to 1 piece / 100 cm ² or less, it is mentioned that the cooling rate after thermally fusing layers A and B to be described later is within a preferable range. Adopting such a method is preferable because both surface dent and flatness can be achieved.

  Although the use of the composite film of the present invention is not particularly limited, it can be used for various industrial materials such as electrical insulating materials, circuit board materials, and process / release materials. It is suitably used as an electrical insulating material for drive motors and car air conditioner compressor motors used in automobiles.

  Next, the method for producing the composite film of the present invention will be described in detail with specific examples.

  As a manufacturing method of polyparaphenylene sulfide resin, the following method is mentioned, for example. Sodium sulfide and p-dichlorobenzene are reacted under high temperature and high pressure in an amide polar solvent such as N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as 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. Separate unreacted monomers. 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.

  As a method for producing a copolymerized polyphenylene sulfide resin, a monomer that gives a phenylene sulfide unit such as m-dichlorobenzene is blended in place of p-dichlorobenzene in the method for producing a polyparaphenylene sulfide resin, and a similar polymerization reaction is carried out. There is a way to do it. The same applies when units other than phenylene sulfide units are introduced.

  Next, the obtained resin is supplied to an extruder, preferably an extruder having one or more vent holes, melted and kneaded at a temperature of 290 to 360 ° C., extruded from a suitable die, and melt-formed into a gut shape. Further, it may be cut into a length of about 2 to 10 mm to form a pellet. The obtained resin is dried with a heating dryer under vacuum at a temperature of 100 to 180 ° C. for about 1 to 5 hours.

  When adding additives such as other resins, inorganic or organic fillers, lubricants, colorants, ultraviolet absorbers, compatibilizers, etc., if necessary, Henschel mixer etc. together with the resin obtained by the above method And extrusion molding or melt molding in the same manner as described above, and can be used as a resin composition.

  In the film forming process to be described later, a plurality of types of resin pellets can be used. For example, it is an aspect which uses together the pellet to which the particle | grains were added, and the pellet without an addition.

  Next, a biaxially oriented film (film A) having a layer (layer A) consisting essentially of polyparaphenylene sulfide in the outermost layer of the present invention, and a layer consisting essentially of polyparaphenylene sulfide in one outermost layer A biaxially oriented film having a layer (layer B) having (layer A ′) and a polyarylene sulfide having a melting point lower by 20 ° C. or more than the polyparaphenylene sulfide constituting layer A in the opposite outermost layer A method for producing (Film B) will be described.

  The film A may have a single-layer structure or a multi-layer structure as long as the outermost layer is substantially made of polyparaphenylene sulfide. As a method for obtaining the film A, the above PPS resin or resin composition is supplied to a melt extrusion apparatus and heated to the melting point or higher. The resin composition melted by heating is pushed out from the slit-shaped die outlet. Such a melt is cooled on the cooling drum below the glass transition point to obtain an unstretched film. A well-known apparatus can be used as the melt extrusion apparatus, but a single-screw or twin-screw extruder is simple and preferably used.

  Film B has a layer (layer A ′) consisting essentially of polyparaphenylene sulfide in one outermost layer, and the opposite outermost layer, in order to reduce the number of heat fusion required to obtain a composite film. And a layer (layer B) composed of copolymer polyarylene sulfide whose melting point is lower by 20 ° C. or more than polyparaphenylene sulfide constituting the layer (layer A) consisting essentially of polyparaphenylene sulfide of the film to be joined Have As a method for obtaining such a film B, a coextrusion method in which the resin constituting the layer A and the resin constituting the layer B are laminated in a melting step so as to be the outermost layer, and discharged and cooled is preferably used. Each resin was supplied to a separate melt extrusion apparatus and heated above the melting point of each resin or resin composition, and each resin composition melted by heating was provided between the melt extrusion apparatus and the die outlet. Laminate in two or more layers in a molten state in a confluence apparatus. The laminated resin flow is extruded from the slit-shaped base outlet, and the obtained molten composite is cooled on the cooling drum below the glass transition point of the resin or resin composition constituting the layer B, and the layer A ′ and An unstretched film in which layer B is disposed as the outermost layer is obtained.

  Next, each unstretched film obtained as described above is biaxially stretched to obtain a biaxially oriented film. As a stretching method of an unstretched film that can orient the films A and B biaxially, a sequential biaxial stretching method in which stretching in the longitudinal direction and the width direction is sequentially performed using a roll group and a tenter, the longitudinal direction, and Examples thereof include a simultaneous biaxial stretching method in which stretching in the width direction is simultaneously performed. Among them, the sequential biaxial stretching method is preferable.

  When using the sequential biaxial stretching method, it is preferable to stretch in the longitudinal direction at 90 to 120 ° C. in the range of 3.0 to 4.0 times. 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, the adhesive strength between layer A and layer B may not be obtained. In the width direction, the film is preferably stretched 2.8 to 3.5 times at 90 to 120 ° C. 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. This is because the degree may not be obtained.

  After transverse stretching, the biaxially oriented film can be further heat treated. By applying heat treatment, the crystal structure is fixed, and it is possible to obtain the strength and heat resistance preferable as a motor insulating film. Also, by reducing the heat shrinkage rate, the width shrinkage in the heat fusion process described later is suppressed. I can do it. As the heat treatment, a one-step heat treatment or a two-step heat treatment is preferably used, and a two-step heat treatment is more preferably used. In the case of the one-step heat treatment, the heat treatment temperature is preferably 240 to 280 ° C, more preferably 260 to 280 ° C or less, and the treatment time is preferably 1 to 60 seconds, more preferably 5 to 30 seconds. In the case of two-stage heat treatment, the heat treatment temperature of the first stage is preferably 160 to 220 ° C, more preferably 180 to 220 ° C or less, and the treatment time is preferably 1 to 30 seconds, more preferably 1 to 15 seconds. It is. The heat treatment temperature of the second stage is preferably 240 to 280 ° C, more preferably 260 to 280 ° C or less, and the treatment time is preferably 1 to 30 seconds, more preferably 1 to 15 seconds. Further, after the heat treatment, relaxation treatment can be performed in the range of 1 to 20%, more preferably 3 to 15%, and still more preferably 3 to 10% in the longitudinal direction and / or the width direction. By doing so, the orientation relaxation of the layer B can be promoted and the adhesive strength between the layer A and the layer B can be improved, which is preferable.

  Next, bonding is performed between the layer A of the film A and the layer B of the film B. As a bonding method, a heat fusion method is simple. As a method of heat fusion, for example, a method of heat fusion (thermocompression bonding) using a heating roll and a pressure roll is preferable. The surface temperature of the heating roll is not less than (Tmb-10) ° C. and not more than (Tma-20) ° C. with respect to the melting point (Tma) of the resin constituting the layer A and the melting point (Tmb) of the resin constituting the layer B. It is preferably (Tmb-5) ° C. or higher and (Tma-20) ° C. or lower. When the temperature of the heating roll is less than (Tmb-10) ° C., a sufficient amount of heat for heat fusion cannot be obtained, and the interfacial adhesiveness may decrease. Moreover, when it exceeds (Tma-20) degreeC, the resin which comprises the layer A may fuse | melt on the surface of a heating roll, and a surface dent may generate | occur | produce. The surface temperature of the heating roll can be measured with a non-contact thermometer or a contact thermometer.

  In addition, the pressure-bonding roll is preferably made of a rubber material from the viewpoint of improving the surface properties of the composite film, and fluorine rubber, silicon rubber, or the like can be used, but is not limited thereto. Moreover, the surface temperature of the crimping roll is preferably 180 ° C to 240 ° C, more preferably 190 ° C to 240 ° C, and further preferably 200 ° C to 240 ° C.

  The pressure during pressure bonding is preferably a linear pressure of 50 to 400 N / cm, more preferably 130 to 400 N / cm, and still more preferably 180 to 400 N / cm between layers A and B. It is preferable for obtaining adhesive strength.

  When the layers A and B are heat-sealed, it is preferable that the films A and B be preheated and then heat-sealed. As a method for preheating the film A and the film B, the film A and the film B are put on the outer periphery of the heating roll or the pressure-bonding roll at a holding angle of 50 to 180 °, preferably 60 to 180 °, more preferably 90 to 180 °, followed by pressure bonding, In order to obtain sufficient adhesive strength between the layer A and the layer B, it is preferable to fuse them.

  It is preferable that the heat-fused body after the pressure bonding is heat-bonded along the outer periphery of the heating roll at an angle of 90 ° or more and 270 ° or less from the point where the heat-bonded body is pressure-bonded to the heating roll. More preferably, the angle is 120 ° to 240 °, and still more preferably 150 ° to 210 °. If the angle of the composite film along the outer circumference of the heating roll is less than 90 ° from the point where it is crimped, the tension balance on the heating roll will be insufficient and the tension balance on the unwinding side and the winding side will become unstable. In some cases, air may be caught between the heating roll and the biaxially oriented PPS film in contact with the heating roll at the crimping point, and a surface dent may be generated on the surface of the composite film. If the angle of the composite film along the outer circumference of the heating roll exceeds 270 ° from the point where it is crimped, the film on the unwinding side and the winding side are likely to interfere spatially. It is not preferable because the direction needs to be changed and wrinkles or flatness deteriorates.

  The interface of the present invention has a heat fusion rate of 0.1 to 10 m / min, preferably 0.5 to 5 m / min, more preferably 1 to 7 m / min, and further preferably 2 to 5 m / min. It is preferable from the viewpoint of adhesiveness and productivity.

  It is a preferable aspect that the composite film after heat-sealing is immediately cooled and wound up via one or more transport rolls from the viewpoint of maintaining the flatness and interfacial adhesion of the composite film.

  As a method of cooling the composite film, there is a method of cooling using roll cooling or air cooling between the heating roll and the first transport roll. In the present invention, cooling is performed in a gas atmosphere using air cooling. Is a preferred embodiment. When roll cooling is used, air may be caught between the composite film and the cooling roll, and surface dents may be generated on the surface of the composite film. Moreover, it is preferable that the temperature of the composite film between a heating roll and the 1st conveyance roll cools below the glass transition temperature of the substantial polyparaphenylene sulfide used for this invention. When the temperature of the composite film is higher than the glass transition temperature of the substantially polyparaphenylene sulfide used in the present invention, air between the composite film and the first transport roll can cause surface dents on the surface of the composite film. .

  The cooling rate between the heating roll and the first transport roll is in the range of 15 ° C./s to 30 ° C./s. Preferably they are 20 degreeC / s or more and 25 degrees C / s or less. When the cooling rate is less than 15 ° C./s, thermal crystallization of the composite film proceeds, and the interfacial adhesiveness and elongation at break of the composite film may decrease. On the other hand, when the cooling rate exceeds 30 ° C./s, wrinkles in the longitudinal direction are generated in the composite film due to rapid cooling, so that the flatness of the composite film is deteriorated and the motor processability is deteriorated.

  A preferable embodiment of the present invention includes performing corona discharge treatment or plasma treatment on the bonding surfaces of the layer A and the layer B used in the present invention in order to impart stronger interface adhesion. 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, in the present invention, surface treatment by EC treatment is more preferable from the viewpoint of economy.

[Measurement methods of physical properties and characteristics]
(1) Melting point As a differential scanning calorimeter, 10 mg of a sample was heated from room temperature at a heating rate of 20 ° C./minute on a DS tray (Q-100) manufactured by TA Instruments. At that time, the peak temperature of the endothermic peak of melting observed was defined as the melting point. When the melting point of the composite film is measured without separating the layers, of the two endothermic peaks observed, the higher endothermic peak is the melting point (Tma) of layer A, and the lower endothermic endotherm. The melting point (Tmb) of the layer B of the peak was used.

(2) Elongation at break A sample having a width of 10 mm and a length of 250 mm using an Instron type tensile tester (Orientech AMF / RTA-1210) according to the following method defined in JIS-C-2151. The film is set so that the length between chucks is 100 mm, and a tensile test is performed at a temperature of 23 ° C. and an atmospheric condition of 65% RH at a tensile speed of 200 mm / min.

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

(3) Adhesive strength Using an Instron type tensile tester (Orientec AMF / RTA-1210), the interface between layer A and layer B of a sample with a width of 15 mm was partially peeled off with a cutter or the like. A grip allowance is prepared, and this grip allowance is grasped with a chuck of a tensile tester, and the strength when the layer A and the layer B are pulled and peeled so that the angle formed by the layer A and the layer B becomes 180 ° at a speed of 200 mm / min is measured. did.

  The adhesive strength is obtained by measuring and averaging n = 3 for each interface where layer A and layer B in the composite film are joined.

  When measuring the adhesive strength, the layer A or the layer B may break before the bonded interface peels off. In this case, since the adhesive strength was higher than the breaking strength of the film, the adhesive strength was deemed acceptable.

(4) Surface depression The sample is placed on a 10 cm square sample at a position 2 m directly below a fluorescent lamp with an illuminance of 500 lx so that the angle between the sample surface and the ground is 30 °. The placed sample is visually observed from a distance of 30 cm, and a portion where a dent can be confirmed is marked. Using a surface structure analyzer (NewView 100) manufactured by ZYGO, measure the major axis and depth of the dent by the scanning white interference method. The major axis is 100 μm or more and the depth is 0.5 μm or more. Count the number of dents.

(5) Partial discharge voltage Using a partial discharge tester (KPD2050, manufactured by Kikusui Electronics), an AC voltage with a frequency of 50 Hz and a voltage of 2.0 kV was applied at a temperature of 35 ° C. under an atmospheric condition of 24% RH, and a starting voltage The charge threshold was measured as 10 pC.

(6) Motor processability Using a motor slot processing machine (Odawara Engineering Co., Ltd.), the sample was processed into a slot with a width of 24 mm and a length of 39 mm at a processing speed of 2 pcs / sec, and film cracking or delamination occurred visually. The product was regarded as a defective product, and the defective product occurrence rate was evaluated according to the following criteria. The number of processed samples is 100 for each sample.
○: The defect rate is 5% or less. Δ: The defect rate exceeds 6% and is 20% or less. X: The defect rate exceeds 20%.

(7) Heat resistance Using an Espec hot air gear oven (GPHH-200), a sample film having a width of 10 mm and a length of 250 mm was treated in an atmosphere of 260 degrees for 1 hour, and the breaking elongation of the treated sample film was Is measured by the method described in (1). When the value obtained by dividing the breaking elongation after the treatment by the breaking elongation before the treatment was taken as the breaking elongation retention, the breaking elongation retention was evaluated according to the following criteria.
○: Breaking elongation retention is 80% or more Δ: Breaking elongation retention is 50% or more and less than 80% ×: Breaking elongation retention is less than 50%

  EXAMPLES Next, although an Example is given and this invention is demonstrated further in detail, it is not limited to a present Example.

(1) Production of polyparaphenylene sulfide resin composition 1 An autoclave was charged with 100 mol parts of sodium sulfide nonahydrate, 45 mol parts of sodium acetate and 259 mol parts of N-methyl-2-pyrrolidone, and gradually while stirring. The temperature was raised to 220 ° C. and the contained water was removed by distillation. To the system after the dehydration, 101 mol parts of p-dichlorobenzene as a main component monomer and 0.2 mol parts of 1,2,4-trichlorobenzene as an accessory component together with 52 mol parts of NMP were added, and 170 ° C. After pressurizing nitrogen at a temperature of 3 kg / cm ² , the temperature was raised and polymerization was carried out 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 five times with distilled water at 90 ° C. and then dried at 120 ° C. under reduced pressure to obtain a resin having a melting point of 280 ° C. and a glass transition temperature of 91 ° C. It was. Next, 0.7% by weight of calcium carbonate powder having an average particle size of 1.0 μm was added to the resin and uniformly dispersed and blended, and extruded into a gut shape at a temperature of 320 ° C. with a 30 mmφ twin-screw extruder, to obtain polyparaphenylene sulfide. A resin composition 1 was obtained.

(2) Production of copolymerized polyphenylene sulfide resin [Copolymerized polyphenylene sulfide resin composition 1]
All of the above except that 91 mole parts p-dichlorobenzene was used as the main component monomer, 10 mole parts m-dichlorobenzene and 0.2 mole part 1,2,4-trichlorobenzene were used as the accessory monomer. The copolymerized polyphenylene sulfide resin composition 1 was produced in the same manner as in the production of the polyparaphenylene sulfide resin composition 1 in 1). The resin composition had a melting point of 250 ° C. and a glass transition temperature of 86 ° C.
[Copolymerized polyphenylene sulfide resin composition 2]
All of the above except that 95 mole parts p-dichlorobenzene was used as the main component monomer, 6 mole parts m-dichlorobenzene and 0.2 part mole 1,2,4-trichlorobenzene were used as the accessory monomer. The copolymerized polyphenylene sulfide resin composition 2 was produced in the same manner as in the production of the polyparaphenylene sulfide resin composition 1 in 1). The resin composition had a melting point of 260 ° C. and a glass transition temperature of 88 ° C.
[Copolymerized polyphenylene sulfide resin composition 3]
All of the above except that 87 mole parts p-dichlorobenzene was used as the main component monomer, 15 mole parts m-dichlorobenzene and 0.2 mole part 1,2,4-trichlorobenzene were used as the accessory monomer. The copolymerized polyphenylene sulfide resin composition 3 was produced in the same manner as in the production of the polyparaphenylene sulfide resin composition 1 in 1). The resin composition had a melting point of 225 ° C. and a glass transition temperature of 85 ° C.
[Copolymerized polyphenylene sulfide resin composition 4]
All of the above except that 85 mole parts p-dichlorobenzene was used as the main component monomer, 17 mole parts m-dichlorobenzene and 0.2 mole part 1,2,4-trichlorobenzene were used as the accessory monomer. The copolymerized polyphenylene sulfide resin composition 4 was produced in the same manner as in the production of the polyparaphenylene sulfide resin composition 1 in 1). The resin composition had a melting point of 220 ° C. and a glass transition temperature of 84 ° C.
[Copolymerized polyphenylene sulfide resin composition 5]
All of the above except that 97 mole parts p-dichlorobenzene was used as the main component monomer, 4 mole parts m-dichlorobenzene and 0.2 mole part 1,2,4-trichlorobenzene were used as the accessory monomer. The copolymerized polyphenylene sulfide resin composition 5 was produced in the same manner as in the production of the polyparaphenylene sulfide resin composition 1 of 1). The resin composition had a melting point of 265 ° C. and a glass transition temperature of 89 ° C.

(3) Production of biaxially oriented film [biaxially oriented polyparaphenylene sulfide film 1]
The polyparaphenylene sulfide resin composition 1 obtained in the above (1) was dried at 180 ° C. for 4 hours under a reduced pressure of 3 mmHg using a rotary vacuum dryer. The dried resin composition was supplied to a single screw extruder and melted at 310 ° C. The melted resin composition was filtered through a stainless steel sintered filter having an average aperture of 14 μm, and then discharged from a T-die die having a width of 940 mm and a lip gap of 3 mm, and extruded into a sheet shape. Subsequently, this sheet was wound around a casting drum having a surface temperature of 25 ° C. by using an electrostatic application casting method and cooled and solidified to produce an unstretched film having a thickness of about 1250 μm.

Using sequential biaxial stretching, the unstretched film obtained was run in contact with a plurality of heating rolls having a surface temperature of 97 ° C., and the length was between a cooling roll of 25 ° C. having a different peripheral speed provided next to the heating roll. The film was stretched 3.7 times in the direction. The uniaxially stretched film thus obtained was stretched 3.4 times at a temperature of 100 ° C. in the direction perpendicular to the longitudinal direction using a tenter, followed by a temperature of 200 ° C. for 10 seconds and a temperature of 265 ° C. After 10 seconds of heat treatment at a temperature of 260 ° C. in the direction perpendicular to the longitudinal direction of the film, 5.0% limited shrinkage treatment is performed for 10 seconds, and further 115% limited shrinkage treatment is performed at 115 ° C. for 9 seconds. Then, the film was cooled to room temperature to obtain a film having a thickness of 100 μm. The obtained film had a melting point of 285 ° C., a glass transition temperature of 91 ° C., and a breaking elongation of 105%.
[Biaxially oriented polyparaphenylene sulfide film 2]
A film was obtained in the same manner as the biaxially oriented polyparaphenylene sulfide film 1 except that the draw ratio in the longitudinal direction was 4.3 times. The obtained film had a melting point of 285 ° C., a glass transition temperature of 93 ° C., and a breaking elongation of 70%.
[Biaxially oriented polyparaphenylene sulfide film 3]
A film was obtained in the same manner as the biaxially oriented polyparaphenylene sulfide film 1 except that the draw ratio in the longitudinal direction was 4.1 times. The obtained film had a melting point of 285 ° C., a glass transition temperature of 92 ° C., and a breaking elongation of 90%.
[Biaxially oriented polyparaphenylene sulfide film 4]
A film was obtained in the same manner as the biaxially oriented polyparaphenylene sulfide film 1 except that the thickness was 75 μm. The obtained film had a melting point of 285 ° C., a glass transition temperature of 91 ° C., and a breaking elongation of 102%.
[Biaxially oriented polyparaphenylene sulfide film 5]
A film 5 was obtained in the same manner as the biaxially oriented polyparaphenylene sulfide film 1 except that the thickness was 115 μm. The obtained film had a melting point of 285 ° C., a glass transition temperature of 91 ° C., and a breaking elongation of 105%.

(4) Production of biaxially oriented laminated film [biaxially oriented laminated polyphenylene sulfide film 1]
The polyparaphenylene sulfide resin composition 1 and the copolymerized polyphenylene sulfide resin composition 1 obtained in the above (1) and (2) were respectively heated at 180 ° C. under a reduced pressure of 3 mmHg using a rotary vacuum dryer. And dried for 4 hours. The dried polyparaphenylene sulfide resin composition 1 was supplied to a single screw extruder and melted at 310 ° C. Moreover, the dried copolymer polyphenylene sulfide resin composition 1 was supplied to another vent type biaxial kneading extruder and melted at 280 ° C. The two melted resin compositions are each filtered through a stainless fiber sintered filter having an average opening of 8 μm, and then combined in a two-layer merge block having a rectangular composite part, and a T die having a 940 mm width and a lip gap of 3 mm. From the die, it was made to discharge so that the ratio of discharge amount might be polyparaphenylene sulfide resin composition 1: copolymer polyphenylene sulfide resin composition 1 = 85: 15, and it extruded to the sheet form. Subsequently, this sheet was wound around a casting drum having a surface temperature of 25 ° C. by using an electrostatic application casting method, and solidified by cooling to produce an unstretched two-layer laminated film having a thickness of about 1250 μm.

Using sequential biaxial stretching, the obtained unstretched film was run in contact with a plurality of heating rolls having a surface temperature of 92 ° C., and longitudinally between 25 ° C. cooling rolls with different peripheral speeds provided next to the heating roll. The film was stretched 3.7 times in the direction. The uniaxially stretched sheet thus obtained was stretched 3.4 times at a temperature of 100 ° C. in the direction perpendicular to the longitudinal direction using a tenter, and then at a temperature of 200 ° C. for 10 seconds and further at a temperature of 250 ° C. After 10 seconds of heat treatment at 245 ° C in the direction perpendicular to the longitudinal direction of the film, 4.5% limiting shrinkage treatment is performed for 10 seconds at a temperature of 115 ° C, followed by intermediate cooling at 115 ° C for 9 seconds, followed by cooling to room temperature. A film having a thickness of 85 μm by the paraphenylene sulfide resin composition 1, a thickness of 15 μm by the copolymerized polyphenylene sulfide resin composition 1, and a total thickness of 100 μm was obtained. The breaking elongation of the obtained film was 100%, the melting point of the polyparaphenylene sulfide resin composition 1 in each layer was 285 ° C., and the melting point of the copolymerized polyphenylene sulfide resin composition 1 was 255 ° C.
[Biaxially oriented laminated polyphenylene sulfide film 2]
A film was obtained in the same manner as the biaxially oriented laminated polyphenylene sulfide film 1 except that the polyparaphenylene sulfide resin composition 1 and the copolymerized polyphenylene sulfide resin composition 2 obtained in the above (1) and (2) were used. . The breaking elongation of the obtained film was 100%, the melting point of the polyparaphenylene sulfide resin composition 1 in each layer was 285 ° C., and the melting point of the copolymer polyphenylene sulfide resin composition 2 was 265 ° C.
[Biaxially oriented laminated polyphenylene sulfide film 3]
The ratio of the discharge amounts of the polyparaphenylene sulfide resin composition 1 and the copolymerized polyphenylene sulfide resin composition 1 obtained in the above (1) and (2) is the polyparaphenylene sulfide resin composition 1: copolymerized polyphenylene sulfide resin composition. A film was obtained in the same manner as the biaxially oriented laminated polyphenylene sulfide film film 1 except that the product 1 = 91: 9. In the obtained film, the layer thickness of the polyparaphenylene sulfide resin composition 1 is 91 μm, the layer thickness of the copolymerized polyphenylene sulfide resin composition 1 is 9 μm, the total thickness is 100 μm, the elongation at break is 100%, The melting point of the polyparaphenylene sulfide resin composition 1 was 285 ° C., and the melting point of the copolymerized polyphenylene sulfide resin composition 1 was 255 ° C.
[Biaxially oriented laminated polyphenylene sulfide film 4]
The ratio of the discharge amounts of the polyparaphenylene sulfide resin composition 1 and the copolymerized polyphenylene sulfide resin composition 1 obtained in the above (1) and (2) is the polyparaphenylene sulfide resin composition 1: copolymerized polyphenylene sulfide resin composition. A film was obtained in the same manner as the biaxially oriented laminated polyphenylene sulfide film 1 except that the product 1 = 60: 40. In the obtained film, the layer thickness of the polyparaphenylene sulfide resin composition 1 is 60 μm, the layer thickness of the copolymerized polyphenylene sulfide resin composition 1 is 40 μm, the total thickness is 100 μm, the elongation at break is 100%, The melting point of the polyparaphenylene sulfide resin composition 1 was 285 ° C., and the melting point of the copolymerized polyphenylene sulfide resin composition 1 was 255 ° C.
[Biaxially oriented laminated polyphenylene sulfide film 5]
The ratio of the discharge amounts of the polyparaphenylene sulfide resin composition 1 and the copolymerized polyphenylene sulfide resin composition 1 obtained in the above (1) and (2) is the polyparaphenylene sulfide resin composition 1: copolymerized polyphenylene sulfide resin composition. A film 5 was obtained in the same manner as the biaxially oriented laminated polyphenylene sulfide film 1 except that the product 1 = 45: 55. In the obtained film, the layer thickness of the polyparaphenylene sulfide resin composition 1 is 45 μm, the layer thickness of the copolymerized polyphenylene sulfide resin composition 1 is 55 μm, the total thickness is 100 μm, the elongation at break is 100%, The melting point of the polyparaphenylene sulfide resin composition 1 was 285 ° C., and the melting point of the copolymerized polyphenylene sulfide resin composition 1 was 255 ° C.
[Biaxially oriented laminated polyphenylene sulfide film 6]
A film was obtained in the same manner as the biaxially oriented laminated polyphenylene sulfide film 1 except that the polyparaphenylene sulfide resin composition 1 and the copolymerized polyphenylene sulfide resin composition 3 obtained in the above (1) and (2) were used. . The film obtained had a breaking elongation of 100%, and in each layer, the melting point of the polyparaphenylene sulfide resin composition 1 was 285 ° C., and the melting point of the copolymerized polyphenylene sulfide resin composition 3 was 230 ° C.
[Biaxially oriented laminated polyphenylene sulfide film 7]
A film was obtained in the same manner as the biaxially oriented laminated polyphenylene sulfide film 1 except that the polyparaphenylene sulfide resin composition 1 and the copolymerized polyphenylene sulfide resin composition 4 obtained in the above (1) and (2) were used. . The film had an elongation at break of 100%, and in each layer, the melting point of the polyparaphenylene sulfide resin composition 1 was 285 ° C., and the melting point of the copolymerized polyphenylene sulfide resin composition 4 was 225 ° C.
[Biaxially oriented laminated polyphenylene sulfide film 8]
The ratio of the discharge amounts of the polyparaphenylene sulfide resin composition 1 and the copolymerized polyphenylene sulfide resin composition 1 obtained in the above (1) and (2) is the polyparaphenylene sulfide resin composition 1: copolymerized polyphenylene sulfide resin composition. Biaxially oriented stacking except that the product 1 = 80: 20, the layer thickness of the polyparaphenylene sulfide resin composition 1 is 60 μm, the layer thickness of the copolymerized polyphenylene sulfide resin composition 1 is 15 μm, and the total thickness is 75 μm A film 8 was obtained in the same manner as the polyphenylene sulfide film 1. The resulting film had a breaking elongation of 100%, and in each layer, the melting point of the polyparaphenylene sulfide resin composition 1 was 285 ° C., and the melting point of the copolymer polyphenylene sulfide resin composition 1 was 255 ° C.
[Biaxially oriented laminated polyphenylene sulfide film 9]
The ratio of the discharge amounts of the polyparaphenylene sulfide resin composition 1 and the copolymerized polyphenylene sulfide resin composition 1 obtained in the above (1) and (2) is the polyparaphenylene sulfide resin composition 1: copolymerized polyphenylene sulfide resin composition. Biaxially oriented stacking except that the product 1 = 87: 13, the layer thickness of the polyparaphenylene sulfide resin composition 1 is 100 μm, the layer thickness of the copolymerized polyphenylene sulfide resin composition 1 is 15 μm, and the total thickness is 115 μm. Two films were obtained in the same manner as polyphenylene sulfide film 1. The resulting film had a breaking elongation of 100%, and in each layer, the melting point of the polyparaphenylene sulfide resin composition 1 was 285 ° C., and the melting point of the copolymer polyphenylene sulfide resin composition 1 was 255 ° C.
[Biaxially oriented laminated polyphenylene sulfide film 10]
A film was obtained in the same manner as the biaxially oriented laminated polyphenylene sulfide film 1 except that the polyparaphenylene sulfide resin composition 1 and the copolymer polyphenylene sulfide resin composition 5 obtained in the above (1) and (2) were used. . The resulting film had a breaking elongation of 100%, and in each layer, the melting point of the polyparaphenylene sulfide resin composition 1 was 285 ° C., and the melting point of the copolymerized polyphenylene sulfide resin composition 5 was 270 ° C.
[Biaxially oriented laminated polyphenylene sulfide film 11]
A film was obtained in the same manner as the biaxially oriented laminated polyphenylene sulfide film 1 except that the draw ratio in the longitudinal direction was 4.1 times. The resulting film had a breaking elongation of 85%, and in each layer, the melting point of the polyparaphenylene sulfide resin composition 1 was 285 ° C., and the melting point of the copolymerized polyphenylene sulfide resin composition 1 was 255 ° C.
Example 1
The biaxially oriented polyparaphenylene sulfide film 1 and the biaxially oriented laminated polyphenylene sulfide film 1 obtained by the film-forming methods (3) and (4) above are copolymerized polyphenylene sulfide resin composition 1 on the bonding surface side. Thus, heat fusion was performed. The heat fusion rate was 2.5 m / min. A hard chrome roll heated to a surface temperature of 250 ° C. is used as the heating roll, and the biaxially oriented laminated polyphenylene sulfide film 1 is arranged so as to be in direct contact with the heating roll, and the holding angle to the pressure bonding point is 90 Preheat along the outer circumference of the heating roll so Also, a fluororubber roll heated to a surface temperature of 200 ° C. is used as the pressure roll, and the outer circumference of the pressure roll is adjusted so that the holding angle of the biaxially oriented polyparaphenylene sulfide film 1 to the pressure bonding point is 180 degrees. Preheated along. The biaxially oriented laminated polyphenylene sulfide film 1 and the biaxially oriented polyparaphenylene sulfide film 1 preheated by the above method were pressure-bonded at a pressure of 230 N / cm between a heating roll and a pressure-bonding roll. The bonded composite film is heat-sealed along the outer periphery of the heating roll so that the angle from the pressing point is 180 degrees, and then the composite film is pulled away from the heating roll. Immediately after that, 25 ° C. cooling air was blown onto the composite film at a speed of 5 m / sec between the heating roll and the first transport roll, and the composite film was cooled at a speed of 23 ° C./sec to cool the temperature of the composite film to 60 ° C. Then, it wound up via the conveyance roll and obtained the composite film.

(Example 2)
The biaxially oriented polyparaphenylene sulfide film 1 and the biaxially oriented laminated polyphenylene sulfide film 1 obtained by the film-forming methods of (3) and (4) above were converted into a biaxially oriented laminated polyphenylene sulfide film 1 / biaxially oriented polyparaffin. The phenylene sulfide film 1 was laminated with a biaxially oriented laminated polyphenylene sulfide film, but heat-sealed so that the copolymerized polyphenylene sulfide resin composition 1 was on the bonding surface side. The heat fusion rate was 2.5 m / min. A hard chrome roll heated to a surface temperature of 250 ° C. is used as a heating roll, and the biaxially oriented laminated polyphenylene sulfide film 1 is arranged so as to be in direct contact with the heating roll, and the holding angle up to the crimping point is 90 Preheat along the outer circumference of the heating roll so In addition, a fluororubber roll heated to a surface temperature of 200 ° C. is used as a pressure-bonding roll, and another biaxially oriented laminated polyphenylene sulfide film 1 is disposed so as to be in direct contact with the pressure-bonding roll. Preheating was performed along the outer periphery of the pressure-bonding roll so that the holding angle was 180 degrees. A biaxially oriented polyparaphenylene sulfide film 1 is arranged between the biaxially oriented laminated polyphenylene sulfide film 1 on the heating roll side preheated by the above method and the biaxially oriented laminated polyphenylene sulfide film 1 on the pressure roll side, Crimping was performed between the crimping rolls at a pressure of 230 N / cm. The bonded composite film is heat-sealed along the outer periphery of the heating roll so that the angle from the pressing point is 180 degrees, and then the composite film is pulled away from the heating roll. Immediately after that, cooling air of 25 ° C. was blown onto the composite film at a speed of 5 m / sec between the heating roll and the first transport roll, and the temperature of the composite film was cooled to 80 ° C. at a speed of 23 ° C./sec. Then, it wound up via the conveyance roll and obtained the composite film.

(Example 3)
A composite film was obtained in the same manner as in Example 2 except that the angle for causing the composite film to follow the outer periphery of the heating roll from the pressure bonding point was 90 °.

Example 4
A composite film was obtained in the same manner as in Example 2 except that the angle at which the composite film was placed along the outer periphery of the heating roll from the pressure bonding point was 270 °.

(Example 5)
A composite film was obtained in the same manner as in Example 2 except that the cooling rate was 15 ° C./second.

(Example 6)
A composite film was obtained in the same manner as in Example 2 except that the cooling rate was 30 ° C./second.

(Example 7)
A composite film was obtained in the same manner as in Example 2 except that the biaxially oriented laminated polyphenylene sulfide film 1 was used instead of the biaxially oriented laminated polyphenylene sulfide film 1.

(Example 8)
A composite film was obtained in the same manner as in Example 2 except that the biaxially oriented polyparaphenylene sulfide film 1 was used instead of the biaxially oriented polyparaphenylene sulfide film 1.

Example 9
A composite film was obtained in the same manner as in Example 2 except that the biaxially oriented polyparaphenylene sulfide film 1 was used instead of the biaxially oriented polyparaphenylene sulfide film 1.

(Example 10)
A composite film was obtained in the same manner as in Example 2 except that the biaxially oriented laminated polyphenylene sulfide film 3 was used in place of the biaxially oriented laminated polyphenylene sulfide film 1 and the surface temperature of the heating roll was set to 260 ° C.

(Example 11)
A composite film was obtained in the same manner as in Example 2 except that the biaxially oriented laminated polyphenylene sulfide film 1 was used instead of the biaxially oriented laminated polyphenylene sulfide film 1.

(Example 12)
A composite film was obtained in the same manner as in Example 2 except that the biaxially oriented laminated polyphenylene sulfide film 1 was used instead of the biaxially oriented laminated polyphenylene sulfide film 1.

(Example 13)
A composite film was obtained in the same manner as in Example 2 except that the biaxially oriented laminated polyphenylene sulfide film 1 was used instead of the biaxially oriented laminated polyphenylene sulfide film 1.

(Example 14)
A composite film was obtained in the same manner as in Example 2 except that the biaxially oriented laminated polyphenylene sulfide film 1 was used instead of the biaxially oriented laminated polyphenylene sulfide film 1.

(Example 15)
Implemented except that the biaxially oriented polyparaphenylene sulfide film 1 was used instead of the biaxially oriented polyparaphenylene sulfide film 1, and the biaxially oriented laminated polyphenylene sulfide film 1 was used instead of the biaxially oriented laminated polyphenylene sulfide film 1. A composite film was obtained in the same manner as in Example 1.

(Example 16)
Implemented except that the biaxially oriented polyparaphenylene sulfide film 1 was used instead of the biaxially oriented polyparaphenylene sulfide film 1, and the biaxially oriented laminated polyphenylene sulfide film 1 was used instead of the biaxially oriented laminated polyphenylene sulfide film 1. A composite film was obtained in the same manner as in Example 2.

(Example 17)
A composite film was obtained in the same manner as in Example 2 except that the composite film immediately after being separated from the heating roll was cooled to 85 ° C. between the heating roll and the first transport roll.

(Comparative Example 1)
A composite film was obtained in the same manner as in Example 2 except that the surface temperature of the heating roll was 270 ° C.

(Comparative Example 2)
A composite film was obtained in the same manner as in Example 2 except that the surface temperature of the heating roll was 240 ° C.

(Comparative Example 3)
A composite film was obtained in the same manner as in Example 2 except that the angle for causing the composite film to follow the outer periphery of the heating roll from the pressure bonding point was 85 °.

(Comparative Example 4)
A composite film was obtained in the same manner as in Example 2 except that the angle at which the composite film was placed along the outer periphery of the heating roll from the pressure-bonding point was 275 °.

(Comparative Example 5)
A composite film was obtained in the same manner as in Example 2 except that the cooling rate was 35 ° C./second.

(Comparative Example 6)
A composite film was obtained in the same manner as in Example 2 except that the cooling rate was 10 ° C./second.

(Comparative Example 7)
A composite film was obtained in the same manner as in Example 2 except that the biaxially oriented laminated polyphenylene sulfide film 1 was used instead of the biaxially oriented laminated polyphenylene sulfide film 1.

(Comparative Example 8)
The biaxially oriented polyparaphenylene sulfide film 1 was replaced with the biaxially oriented polyparaphenylene sulfide film 2, and the biaxially oriented laminated polyphenylene sulfide film 1 was replaced with the biaxially oriented laminated polyphenylene sulfide film 11. A composite film was obtained in the same manner as in Example 2.

(Comparative Example 9)
A composite film was obtained in the same manner as in Example 2 except that the biaxially oriented laminated polyphenylene sulfide film 1 was used instead of the biaxially oriented laminated polyphenylene sulfide film 1.

(Comparative Example 10)
A composite film was obtained in the same manner as in Example 2 except that the composite film immediately after being separated from the heating roll was cooled to 100 ° C. between the heating roll and the first transport roll.

(Comparative Example 11)
A composite film was obtained in the same manner as in Example 2 except that the composite film immediately after being separated from the heating roll was cooled along a cooling roll having a surface temperature of 25 ° C. between the heating roll and the first transport roll.

(Comparative Example 12)
The polyparaphenylene sulfide resin composition 1 and the copolymerized polyphenylene sulfide resin composition 1 obtained in the above (1) and (2) were respectively heated at 180 ° C. under a reduced pressure of 3 mmHg using a rotary vacuum dryer. And dried for 4 hours. The dried polyparaphenylene sulfide resin composition 1 was supplied to a single screw extruder and melted at 310 ° C. Moreover, the dried copolymer polyphenylene sulfide resin composition 1 was supplied to another vent type biaxial kneading extruder and melted at 280 ° C. The melted two resin compositions are each filtered with high precision using a stainless fiber sintered filter having an average mesh size of 8 μm, and then combined with a three-layer confluence block having a rectangular composite part, with a 940 mm width and a lip gap of 3 mm. From the T die die, the discharge amount ratio was polyparaphenylene sulfide resin composition 1: copolymer polyphenylene sulfide resin composition 1: polyparaphenylene sulfide resin composition 1 = 44: 12: 44, Extruded into a sheet. Subsequently, this sheet was wound around a casting drum having a surface temperature of 25 ° C. by using an electrostatic application casting method, and solidified by cooling to produce an unstretched three-layer laminated film having a thickness of about 1570 μm. Using sequential biaxial stretching, the unstretched film obtained was run in contact with a plurality of heating rolls having a surface temperature of 97 ° C., and the length was between a cooling roll of 25 ° C. having a different peripheral speed provided next to the heating roll. The film was stretched 3.7 times in the direction. The uniaxially stretched sheet thus obtained was stretched 3.4 times at a temperature of 100 ° C. in the direction perpendicular to the longitudinal direction using a tenter, but the film was broken and a composite film could not be obtained.

(Comparative Example 13)
The polyparaphenylene sulfide resin composition 1 and the copolymerized polyphenylene sulfide resin composition 1 obtained in the above (1) and (2) were respectively heated at 180 ° C. under a reduced pressure of 3 mmHg using a rotary vacuum dryer. And dried for 4 hours. The dried polyparaphenylene sulfide resin composition 1 was supplied to a single screw extruder and melted at 310 ° C. Moreover, the dried copolymer polyphenylene sulfide resin composition 1 was supplied to another vent type biaxial kneading extruder and melted at 280 ° C. The melted two resin compositions are each filtered with high precision using a stainless fiber sintered filter having an average mesh size of 8 μm, and then combined with a three-layer confluence block having a rectangular composite part, with a 940 mm width and a lip gap of 3 mm. From the T die die, the discharge amount ratio is polyparaphenylene sulfide resin composition 1: copolymer polyphenylene sulfide resin composition 1: polyparaphenylene sulfide resin composition 1 = 43: 14: 43 Extruded into a sheet. Next, this sheet was wound around a casting drum having a surface temperature of 25 ° C. by using an electrostatic application casting method and solidified by cooling to produce an unstretched three-layer laminated film having a thickness of about 1450 μm. Using sequential biaxial stretching, the unstretched film obtained was run in contact with a plurality of heating rolls having a surface temperature of 97 ° C., and the length was between a cooling roll of 25 ° C. having a different peripheral speed provided next to the heating roll. The film was stretched 3.7 times in the direction. The uniaxially stretched sheet thus obtained was stretched 3.4 times at a temperature of 100 ° C. in a direction perpendicular to the longitudinal direction using a tenter, followed by a temperature of 200 ° C. for 10 seconds and a temperature of 265 ° C. After 10 seconds of heat treatment at a temperature of 260 ° C. in the direction perpendicular to the longitudinal direction of the film, 5.0% limited shrinkage treatment is performed for 10 seconds, and further 115% limited shrinkage treatment is performed at 115 ° C. for 9 seconds. After cooling, it was cooled to room temperature to obtain a composite film in which the thickness of layer A was 50 μm, the thickness of layer B was 15 μm, and the total thickness was 115 μm.
Examples 3, 7, 8, 9, 10, 11, 12, and 16 are read as Comparative Examples 14, 15, 16, 17, 18, 19, 20, and 21, respectively.

  The film according to the present invention can be suitably used as a film for motor insulation.

Claims (4)

A biaxially oriented film (also referred to as film A for the sake of convenience) having a layer consisting of polyparaphenylene sulfide (referred to as convenience for the sake of convenience) as the outermost layer, and A layer made of polyphenylene sulfide having a layer made of sulfide (also referred to as layer A ′ for convenience) and having a melting point of 20 ° C. or more lower than the substantial polyparaphenylene sulfide constituting layer A in the opposite outermost layer A biaxially oriented film (also referred to as film B for convenience) having a biaxially oriented film (also referred to as layer B for convenience) is joined between layer A of film A and layer B of film B without using an adhesive. comprising a thickness of 120μm or more 500μm or less, a composite film elongation at break above 80%, der adhesive strength 100 g / 15 mm or more between the layer a and the layer B And composite films, characterized in that the major diameter 100μm or more at the surface of the composite film, the depth is 0.5μm or more surfaces depressions is one / 100 cm ² or less. 2. The composite film according to claim 1, wherein the thickness of the layer B is 10 μm or more and 30 μm or less, and the melting point of the copolymerized polyphenylene sulfide constituting the layer B is 230 to 265 ° C. 3. The composite film according to claim 1, wherein a defect rate in motor processability of the composite film is 20% or less.
<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 pcs / sec, and film cracking or delamination occurred visually. Were evaluated as defective, and the rate of defective products was evaluated according to the following criteria. The number of processed samples is 100 for each sample. A biaxially oriented film (also referred to as film A for the sake of convenience) having a layer consisting of polyparaphenylene sulfide (referred to as convenience for the sake of convenience) as the outermost layer, and It has a layer made of sulfide (also referred to as layer A ′ for convenience), and the opposite outermost layer is made of polyphenylene sulfide whose melting point is 20 ° C. or more lower than that of substantial polyparaphenylene sulfide constituting layer A. A heat fusion step of heat-pressing the layer A of the film A and the layer B of the film B of a biaxially oriented film (also referred to as a film B for convenience) having a layer (also referred to as a layer B for convenience), A step of cooling the film after being attached, and a step of winding the cooled film through at least one transport roll, and the heat fusion step and the cooling step. Satisfies the following (1) to (2): A method for producing a composite film.
(1) In the heating roll and the pressure-bonding roll for heat-bonding the layer A and the layer B in the heat-sealing step, the surface temperature of the heating roll is (Tmb-10) (° C.) or more and (Tma-20) (° C.) or less. In addition, the heat-sealed body is peeled off from the heating roll along the outer periphery of the heating roll in the range of 90 ° or more and 270 ° or less from the pressure-bonded point. here,
Tma: Melting point of resin constituting layer A (° C.)
Tmb: Melting point of resin constituting layer B (° C.)
(2) In the step of cooling the film after heat sealing, the composite film heat-sealed between the heating roll and the first transport roll is substantially at a rate of 15 ° C./s to 30 ° C./s in a gas atmosphere. To cool below the glass transition temperature of the layer made of polyparaphenylene sulfide (layer A).