JP2009274411A - Laminated film and method of manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a PPS laminated film having excellent moldability, particularly thermal moldability. <P>SOLUTION: The laminated film has an outermost layer comprising a biaxially oriented polyarylene sulfide, wherein at least a layer except the outermost layer comprises a biaxially oriented copolymerized polyarylene sulfide. The biaxially oriented polyarylene sulfide film of the outermost layer is adjacent to the biaxially oriented copolymerized polyarylene sulfide. The room temperature elongation at fructure (Er) and a 200°C elongation at fructure (E200) of the laminated film satisfy expression: 1≤E200/Er≤1.5. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a laminated film having excellent moldability, particularly thermoformability, and more specifically, a drive motor, a car air conditioner compressor motor, or a hot water supply used in a hybrid vehicle currently being developed by an automobile manufacturer. The present invention relates to a laminated film suitable for various motor insulating molding materials such as a motor, and further suitable as a thermoforming member such as mold molding, vacuum molding, vacuum pressure molding, and in-mold molding.

  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 electrically 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). Further, (5) a thick laminate film in which a copolymerized polyphenylene sulfide laminate film is laminated by thermal lamination is known (Patent Document 6).

However, the above-described conventional films and sheets, laminated films, and laminates have the following problems. That is, when the film of the above item (1) is used as a slot liner or wedge of a motor, there is a problem that the film is torn or the film is torn. 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. Moreover, although the laminated body of the said (3) term is rich in impact resistance without using an adhesive agent, there was a problem that the tensile elongation was not sufficient and film cracking occurred in motor processing. Furthermore, the laminated film using the copolymerized polyphenylene sulfide of the items (4) and (5) as an adhesive layer has a problem that the moldability by heating is not sufficient, and the film is broken by vacuum / pressure forming.
JP 55-35456 A JP-A-56-34426 JP-A-2-45144 Japanese Patent No. 2956254 JP-A-4-319436 JP 2007-089441 A

  Therefore, the present invention aims to solve these problems and provide a laminated film having excellent moldability, particularly thermoformability.

The laminated film of the present invention has the following configuration in order to solve the above problems. That is, the laminated film of the present invention is a laminated film in which the outermost layer is a biaxially oriented polyarylene sulfide film, and at least one layer other than the outermost layer is made of a biaxially oriented copolymerized polyarylene sulfide film. The biaxially oriented polyarylene sulfide film and the biaxially oriented copolymerized polyarylene sulfide film are adjacent to each other, and the room temperature breaking elongation (Er) and the 200 ° C. breaking elongation (E200) of the laminated film satisfy the following formulas: It is a laminated film.
1 ≦ E200 / Er ≦ 1.5

According to the present invention, a laminated film having excellent thermoformability can be obtained as described below. The laminated film of the present invention is suitable for electric insulation molding materials for various motors such as a drive motor for a hybrid vehicle, a car air conditioner compressor motor, or a water heater motor, and further, mold molding, vacuum molding, and vacuum / pneumatic molding. It can be suitably used as a thermoforming member.

  In the laminated film of the present invention, the outermost layer is a biaxially oriented polyarylene sulfide film. The polyarylene sulfide used in the present invention is a homopolymer or 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. It is preferable that the resin be greater than mol%, more preferably 95 mol% or more. When the poly-p-phenylene sulfide unit 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 film used in the present invention is a resin composition containing 80% by weight or more, preferably 90% by weight or more of the above polyarylene sulfide, melt-molded into a sheet, biaxially stretched and heat-treated. If the polyarylene sulfide content of the film is less than 80% by weight, the crystallinity of the composition is lowered, and the heat resistance, thermal dimensional stability, hydrolysis resistance, etc. of the film may be impaired. Less than 20% by weight of the composition can contain other thermoplastic resins other than polyarylene sulfide.

  In order to obtain the thermoformability of the present invention, the thermoplastic resin other than polyarylene sulfide preferably has a glass transition temperature of 150 ° C. or higher and not higher than the melting point of polyarylene sulfide. The glass transition temperature is more preferably 170 ° C. or higher and 250 ° C. or lower, and further preferably 190 ° C. or higher and 230 ° C. or lower. When the glass transition temperature is less than 150 ° C., the heat resistance of the biaxially oriented polyarylene sulfide may be impaired, and when the glass transition temperature exceeds the melting point of PPS, the film forming property may be deteriorated. Examples of the thermoplastic resin having a glass transition temperature of 150 ° C. or higher include various polymers such as polyarylate, polyetherimide, polyethersulfone, polysulfone, polyphenylene ether, polyamideimide, polycarbonate, and polycycloolefin, and polymers of these polymers. A blend containing at least one kind can be used. In the present invention, at least one or more selected from polyetherimide, polyethersulfone, and polysulfone are preferably selected from the viewpoint of the mixing property of polyarylene sulfide and the manifestation of the effects of the present invention, and polyetherimide is particularly preferably used.

  The polyetherimide used as the other thermoplastic resin contained in the biaxially oriented polyarylene sulfide film of the present invention is not particularly limited. For example, as shown by the following general formula, the polyimide component contains an ether bond. The polymer which is a structural unit can be mentioned preferably.

In the above formula, R1 is a divalent organic group selected from the group consisting of a divalent aromatic or aliphatic group having 2 to 30 carbon atoms, and an alicyclic group, It is the same divalent organic group as R.
Examples of R1 and R2 include aromatic groups represented by the following formula groups:

Can be mentioned.

  In the present invention, when a polyetherimide having a glass transition temperature of 250 ° C. or lower is used, the effects of the present invention can be easily obtained. From the viewpoint of compatibility with polyarylene sulfide, melt moldability, and the like, the structural unit represented by the following formula is used. A condensate of 2,2-bis [4- (2,3-dicarboxyphenoxy) phenyl] propane dianhydride with m-phenylenediamine or p-phenylenediamine is preferred.

  A polyetherimide having this structural unit is available from Subic Innovative Plastics (formerly GE Plastics) under the trade name “Ultem” (registered trademark). For example, “Ultem 1000” and “Ultem 1010” may be mentioned as polyetherimide having a structural unit (former formula) containing a unit derived from m-phenylenediamine. Moreover, “Ultem CRS5000” is mentioned as a polyetherimide having a structural unit (the latter formula) containing a unit derived from p-phenylenediamine.

  As a compatibilizer from the viewpoint of improving the dispersibility of other thermoplastic resins contained in the biaxially oriented polyarylene sulfide film of the present invention, a compound having one or more groups selected from an epoxy group, an amino group, and an isocyanate group is used as a compatibilizing agent. It is preferable to add 0.1 to 3 parts by weight with respect to 100 parts by weight of the total of the arylene sulfide and the thermoplastic resin.

  Specific examples of such compatibilizers include bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, 1,3,5-trihydroxybenzene, bisphenol S, trihydroxy-diphenyldimethylmethane, 4,4′- Dihydroxybiphenyl, 1,5-dihydroxynaphthalene, cashew phenol, 2.2.5.5. -Glycidyl ethers of bisphenols such as tetrakis (4-hydroxyphenyl) hexane, those using halogenated bisphenol instead of bisphenol, glycidyl ether type epoxy compounds such as diglycidyl ether of butanediol, glycidyl such as glycidyl phthalate Glycidyl epoxy resins such as ester compounds, glycidylamine compounds such as N-glycidylaniline, linear epoxy compounds such as epoxidized polyolefin and epoxidized soybean oil, cyclic systems such as vinylcyclohexene dioxide and dicyclopentadiene dioxide Non-glycidyl epoxy resin etc. are mentioned. In addition, other novolac type epoxy resins are also included. The novolac type epoxy resin has two or more epoxy groups and is usually obtained by reacting a novolac type phenol resin with epichlorohydrin. Moreover, a novolac type phenol resin is obtained by a condensation reaction of phenols and formaldehyde. Although there is no restriction | limiting in particular as phenols of a raw material, A phenol, o-cresol, m-cresol, p-cresol, bisphenol A, resorcinol, p-tertiary butylphenol, bisphenol F, bisphenol S, and these condensates are mentioned.

  Moreover, the olefin copolymer which has another epoxy group is also mentioned. Examples of the olefin copolymer having an epoxy group (epoxy group-containing olefin copolymer) include an olefin copolymer obtained by introducing a monomer component having an epoxy group into an olefinic (co) polymer. . Moreover, the copolymer which epoxidized the double bond part of the olefin polymer which has a double bond in a principal chain can also be used.

Examples of functional group-containing components for introducing a monomer component having an epoxy group into an olefinic (co) polymer include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid, etc. And a monomer containing an epoxy group.
The method for introducing these epoxy group-containing components is not particularly limited, and methods such as copolymerization with α-olefin and the like, or graft introduction to an olefin (co) polymer using a radical initiator can be used.

  The introduction amount of the monomer component containing an epoxy group is 0.001 to 40 mol%, preferably 0.01 to 35 mol% with respect to the whole monomer as a raw material of the epoxy group-containing olefin copolymer. It is appropriate to be within the range.

  As an epoxy group-containing olefin copolymer particularly useful in the present invention, an olefin copolymer having an α-olefin and a glycidyl ester of an α, β-unsaturated carboxylic acid as a copolymerization component is preferably exemplified. As said alpha olefin, ethylene is mentioned preferably. These copolymers further include α, β-unsaturated carboxylic acids such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like. It is also possible to copolymerize the alkyl ester, styrene, acrylonitrile and the like. Such an olefin copolymer may be any random, alternating, block, or graft copolymerization mode.

  An olefin copolymer obtained by copolymerizing an glycidyl ester of an α-olefin and an α, β-unsaturated carboxylic acid is, among others, a glycidyl ester 1 of 60 to 99% by weight of an α-olefin and an α, β-unsaturated carboxylic acid. An olefin copolymer obtained by copolymerizing ˜40% by weight is particularly preferable. Specific examples of the glycidyl ester of α, β-unsaturated carboxylic acid include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Among them, glycidyl methacrylate is preferably used.

  As a specific example of an olefin copolymer having an α-olefin and a glycidyl ester of α, β-unsaturated carboxylic acid as an essential copolymerization component, an ethylene / propylene-g-glycidyl methacrylate copolymer ("g" Representing graft, the same applies hereinafter), ethylene / butene-1-g-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate copolymer-g-polystyrene, ethylene-glycidyl methacrylate copolymer-g-acrylonitrile-styrene copolymer Polymer, ethylene-glycidyl methacrylate copolymer-g-PMMA, ethylene / glycidyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / Glycidi methacrylate Copolymers thereof.

  Furthermore, specific examples of the compatibilizing agent include alkoxysilanes having one or more functional groups selected from epoxy groups, amino groups, and isocyanate groups. Specific examples of such compounds include epoxy group-containing alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Compounds, ureido group-containing alkoxysilane compounds such as γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldisilane Isocyanato group-containing alkoxysilane compounds such as toxisilane, γ-isocyanatopropyltrichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-amino Examples include amino group-containing alkoxysilane compounds such as propyltrimethoxysilane.

  An alkoxysilane having one or more functional groups selected from the above epoxy group, amino group, and isocyanate group is preferable as the compatibilizing agent of the present invention, and among them, the alkoxysilane having an isocyanate group is biaxially oriented including a thermoplastic resin. It is most preferable because it is easy to reduce the coarse dispersion due to poor dispersion of the disperse phase of the polyarylene sulfide film, the average dispersion diameter can be easily controlled within the preferred range of the present invention, and the effects of the present invention can be easily obtained.

In addition, when an alkoxysilane having one or more functional groups selected from an epoxy group, an amino group, and an isocyanate group is used, a siloxane bond is easily formed between the polyarylene sulfide and the thermoplastic resin, and in the vicinity of the interface of the dispersed phase. In this case, siloxane bonds are likely to exist. Silicon atoms can be detected in the vicinity of the interface of the dispersed phase using a TEM-EDX method or the like. In the present invention, it is preferable that silicon (Si) atoms derived from siloxane bonds are included at the interface of the dispersed phase made of the thermoplastic resin.
The content of the compatibilizer having one or more functional groups selected from the epoxy group, amino group, and isocyanate group is 0 when the sum of the polyarylene sulfide and the thermoplastic resin content is 100 parts by weight. 0.05 to 3 parts by weight, preferably 0.1 to 1 part by weight, and more preferably 0.2 to 0.5 part by weight. When the content of the compatibilizer is less than 0.05 parts by weight, the dispersibility of the thermoplastic resin is deteriorated, and the elongation at break by heating of the present invention may not be obtained. When the amount exceeds 3 parts by weight, gas may be generated due to the reaction of the unreacted end groups of the compatibilizer during film formation, and film formation may occur frequently or the elongation at break of the film may decrease. is there.
The preferable average dispersion diameter of the thermoplastic resin is 50 to 500 nm, more preferably 70 to 300 nm, and still more preferably 100 to 200 nm. By setting the average dispersion diameter within the above range, it is possible to obtain a biaxially oriented polyarylene sulfide film having an excellent balance between heat resistance and moldability improvement. When the average dispersion diameter of the dispersed phase is less than 50 nm, the heat moldability of the present invention may not be sufficiently provided. On the other hand, if the average dispersion diameter is larger than 500 nm, the heat resistance may be deteriorated or the film may be broken during the film-forming stretch.

  The biaxially oriented polyarylene sulfide film of the present invention includes a heat stabilizer, an antioxidant, an ultraviolet absorber, an antistatic agent, a flame retardant, a pigment, a dye, a fatty acid ester, and a wax within a range that does not impair the effects of the present invention. Other components such as organic lubricants may be added. In addition, inorganic particles, organic particles, and the like can be added to the biaxially oriented polyarylene sulfide film in order to impart easy slipping, abrasion resistance, scratch resistance, and the like to the film surface. Examples of such additives include clay, mica, titanium oxide, calcium carbonate, kaolin, talc, wet or dry silica, colloidal silica, calcium phosphate, barium sulfate, alumina, zirconia, and other inorganic particles, acrylic acids, styrene And so-called internal particles, surfactants and the like which are precipitated by a catalyst added during the polymerization reaction of polyarylene sulfide.

  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 film. 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 such a 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 cannot be sufficiently improved, and the thermoformability may not be sufficient.

  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. If the copolymerization component is less than 8 mol%, the interfacial adhesion of the laminated film cannot be sufficiently improved, and the thermoformability may not be sufficiently improved. 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 260 ° C. or lower, and further preferably 230 ° C. or higher and 260 ° C. or lower. When the melting point of the copolymerized polyarylene sulfide is less than 210 ° C, the heat resistance may be remarkably deteriorated. When the melting point exceeds 260 ° C, the interfacial adhesion may not be sufficiently improved, and the thermoformability may be deteriorated. is there. The melting point of the copolymer polyarylene sulfide can be appropriately adjusted depending on the molar ratio of the copolymer components.

  The biaxially oriented copolymer polyarylene sulfide film used in the present invention is a sheet formed by melt-molding a resin composition containing 80% by weight or more, preferably 90% by weight or more of the copolymerized polyarylene sulfide. A film formed by heat treatment. When the content of the copolymerized polyarylene sulfide is less than 80% by weight, the interfacial adhesion may be impaired. Less than 20% by weight of 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.

  The thickness of the biaxially oriented copolymer polyarylene sulfide film of the present invention is preferably 5 μm or more and 50 μm or less, more preferably 10 μm or more and 30 μm or less, and further preferably 10 μm or more and 20 μm or less. When the thickness of the biaxially oriented copolymerized polyarylene sulfide film is less than 5 μm, the interfacial adhesion may not be sufficiently obtained, and when it exceeds 50 μm, the heat resistance of the laminated film may be lowered.

  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.

  In the laminated structure of the laminated film of the present invention, the outermost layer is a biaxially oriented polyarylene sulfide film (A layer), and at least one layer other than the outermost layer is a biaxially oriented copolymerized polyarylene sulfide film (B layer), The biaxially oriented polyarylene sulfide film and the biaxially oriented copolymerized polyarylene sulfide film are not particularly limited except that they are adjacent to each other. However, the biaxially oriented polyarylene sulfide film (A layer) / biaxially oriented copolymerized polyarylene sulfide film ( B layer) / biaxially oriented polyarylene sulfide film (A layer), A / B / A / B / A may be laminated. The laminated structure can be changed as appropriate.

  The thickness of the laminated film of the present invention is preferably from 125 μm to 500 μm, more preferably from 200 μm to 400 μm, and even more preferably from 250 μm to 350 μm. If the thickness is less than 125 μm, the electrical insulation as a motor insulation film may not be sufficient, and if the thickness exceeds 500 μm, the laminate processability of the laminated film may be reduced, and the interfacial adhesion may be reduced, and thermoforming. Sexuality may worsen.

  In the laminated film of the present invention, each layer constituting the laminated film needs to be biaxially oriented. The orientation of each layer can be determined by measuring the cross section of the laminated film by laser Raman spectroscopy. That the biaxially oriented polyarylene sulfide film is oriented preferably has an orientation parameter obtained by laser Raman spectroscopy in the range of 2.0 to 8.0, more preferably 2.5 to 6. 0. When the orientation parameter exceeds 8.0, the molecular chain orientation may proceed excessively or the crystallization may proceed excessively, resulting in damage during processing or use of the film, or in practical use. On the other hand, when the orientation parameter is less than 2.0, the molecular chain orientation may be insufficient or the progress of crystallization may be insufficient, which may reduce the heat resistance of the structure. On the other hand, it can be said that the biaxially oriented copolymerized polyarylene sulfide film is oriented if the orientation parameter obtained by laser Raman spectroscopy is 1.3 or more.

  In order to set the orientation parameters of the biaxially oriented polyarylene sulfide film and the biaxially oriented copolymerized polyarylene sulfide film within the above range, for example, the stretching temperature and stretching ratio in longitudinal stretching, the preheating temperature before transverse stretching, It can be obtained by setting the stretching temperature, the stretching ratio, and the heat setting temperature after stretching within the preferred range of the present invention.

  The measurement method by the laser Raman spectroscopy is not particularly limited. For example, a laser Raman apparatus (PDP320 (manufactured by Photon Design)) is used, the microprobe objective lens is 100 times, and the objective lens is in the near infrared region (1064 to 1300 nm). ) Having transparency, NA of 0.95, and chromatic aberration correction can be used. Cross slit 1 mm, spot diameter 1 μm, light source Nd-YAG (wavelength 1064 nm, output: 1 W), diffraction grating Spectrograph 300 g / mm, slit: 100 μm, detector InGaAs (Roper Scientific 512) is preferably used.

The film used for the measurement was sampled and embedded in an epoxy resin, and a film cross section was prepared with a microtome. The film cross-section was adjusted to be parallel to the film longitudinal direction or the width direction, and the average value was calculated by measuring 5 samples for each of the longitudinal direction and the width direction with the central point of each sample as the measurement point. . Measurement is performed through a polarizer placed in a polarization direction parallel to the polarization direction of incident light, the sample is rotated, and a polarization direction perpendicular to the polarization direction parallel to the film surface is obtained with respect to the polarization direction of the laser light. A spectrum was obtained. The orientation parameter was calculated by the following formula.
(Orientation parameter) = (I1575 / I740) (Parallel) / (I1575 / I740) (Vertical)
I1575 / I740 (parallel): in the Raman spectrum measured in a parallel polarization direction to the film surface, obtained by dividing the Raman band near 1575 cm ^-1 in the Raman band intensity near 740 cm ^-1.
I1575 / I740 (vertical): in the Raman spectrum measured with polarization direction perpendicular to the film surface, obtained by dividing the Raman band near 1575 cm ^-1 in the Raman band intensity near 740 cm ^-1.

  The breaking elongation at room temperature of the laminated film of the present invention is preferably 100% or more and 160% or less in order to obtain the workability of the present invention. More preferably, they are 120% or more and 160% or less, More preferably, they are 130% or more and 160% or less. When the elongation at break at room temperature is less than 100%, film breakage may occur in the motor processing step, and film breakage may occur in thermoforming such as die molding or vacuum / pressure forming. The upper limit of the elongation at break is not particularly provided, but if it exceeds 160%, the strength of the film is lowered and the heat resistance of the film may be lowered. The room temperature breaking elongation of the laminated film of the present invention is an average breaking elongation in the film longitudinal direction and width direction. In order to set the room temperature breaking elongation of the laminated film of the present invention within the above range, the biaxially oriented polyarylene sulfide film and the biaxially oriented copolymerized polyarylene sulfide film before lamination are subjected to the draw ratio and heat treatment conditions specified in the present application. The biaxially oriented film obtained after film formation is heat-laminated under the lamination conditions specified in the present application, and voids in the laminated film can be obtained within the range specified in the present application.

  Further, the elongation at break of the laminated film of the present invention at 200 ° C. is preferably 120% or more and 200% or less, more preferably 130% or more and 200% or less, further preferably 150% or more and 200% or less. It is. When the breaking elongation at 200 ° C. is less than 120%, film cracking may occur by thermoforming such as die molding or vacuum / pressure forming, and a film having a breaking elongation at 200 ° C. exceeding 200% may be generated. In order to obtain, although it is necessary to reduce a draw ratio in a extending process, film flatness may deteriorate or the heat resistance of a film may become insufficient. The 200 degreeC breaking elongation of the laminated | multilayer film of this invention is an average breaking elongation of a film longitudinal direction and the width direction. In order to set the breaking elongation at 200 ° C. of the laminated film of the present invention in the above range, the biaxially oriented polyarylene sulfide film and the biaxially oriented copolymerized polyarylene sulfide film before lamination are subjected to the draw ratio and heat treatment conditions specified in the present application. The obtained biaxially oriented film is heat-laminated under the lamination conditions specified in this application, and the voids in the laminated film can be obtained within the range specified in this application. Moreover, when polyether imide is added as another thermoplastic resin in polyarylene sulfide, the elongation at break at 200 ° C. is preferably used.

  The laminated film of the present invention exhibits the thermoformability of the present invention when the ratio (E200 / Er) of the room temperature breaking elongation (Er) to the 200 ° C. breaking elongation (E200) is 1 or more and 1.5 or less. Is the most important to do. A more preferable ratio is 1.1 or more and 1.5 or less, and further preferably 1.2 or more and 1.5 or less. When the ratio of E200 / Er is less than 1, the thermoformability of the present invention may not be improved, and it is substantially difficult for the ratio of E200 / Er to exceed 1.5. In order to make the ratio of E200 / Er within the above range, a biaxially oriented polyarylene sulfide film and a biaxially oriented copolymerized polyarylene sulfide film before lamination are formed according to the draw ratio and heat treatment conditions specified in the present application. The biaxially oriented film can be heat-laminated under the lamination conditions specified in this application, and the voids in the laminated film can be obtained within the range specified in this application. In addition, it is preferable to add polyetherimide as another thermoplastic resin in the polyarylene sulfide.

  The laminated film of the present invention preferably has no voids of 1.5 μm or more in the laminated film. The method for measuring voids in the laminated film is not particularly limited, but can be observed by a transmission method using an optical microscope. The observation magnification is not particularly limited, but it can be observed at 50 to 200 times. More preferably, the voids in the laminated film are free of voids of 1.0 μm or more, and more preferably no voids of 0.5 μm or more are present. When voids of 1.5 μm or more are present in the laminated film, the room temperature breaking elongation of the laminated film may be lower than the room temperature breaking elongation of the biaxially oriented film before lamination, and the laminated film breaks at 200 ° C. The elongation may be lower than the room temperature breaking elongation. In order to set the voids in the laminated film within the above range, the biaxially oriented polyarylene sulfide film and the biaxially oriented copolymerized polyarylene sulfide film before lamination are formed according to the draw ratio and heat treatment conditions specified in this application, It can be obtained by the laminating conditions.

  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 thermoformability, a method of laminating without an adhesive is preferred. As a specific method of laminating without using an adhesive, a heat laminating method 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.

  Although the use of the laminated film of the present invention is not particularly limited, various motor insulating materials such as a drive motor, an air conditioner compressor motor, or a water heater motor used in a hybrid vehicle, mold molding, vacuum molding, vacuum compressed air, etc. It is suitable for various thermoforming materials such as molding and in-mold molding.

  Next, regarding the method for producing the laminated film of the present invention, a poly-p-phenylene sulfide resin (hereinafter sometimes abbreviated as PPS resin) is used as the polyarylene sulfide, and a small amount of m- is added to the PPS as the copolymerized polyarylene sulfide. The production of a laminated film using a poly-m-phenylene sulfide resin copolymerized with phenylene sulfide units (hereinafter sometimes abbreviated as m-PPS resin) will be described as an example. Of course, it is not limited to the description.

  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.

  As a manufacturing method of m-PPS resin, there exists the following method, for example. 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. When the above PPS resin alone or m-PPS resin is used, the PPS resin and m-PPS resin 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 a single layer, two layers, 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 single-layer, or two-layer or three-layer laminate sheet. The lamination structure is not particularly limited, but in the case of a two-layer lamination, a two-layer lamination of a PPS layer / m-PPS layer is preferable, and in the case of a three-layer lamination, a three-layer lamination of m-PPS layer / PPS layer / m-PPS layer 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.

  Subsequently, the amorphous single layer, or the two-layer or three-layer laminated sheet thus obtained is subjected to a conventionally known sequential biaxial stretching machine in the range of the glass transition temperature of the PPS to the cold crystallization temperature or less. After biaxial stretching with a simultaneous biaxial stretching machine, heat treatment is performed at a temperature in the range of 240 to 280 ° C. to obtain a biaxially oriented film. Stretching methods include sequential biaxial stretching methods (stretching methods that combine stretching in each direction, such as a method of stretching in the width direction after stretching in the longitudinal direction), and simultaneous biaxial stretching methods (in the longitudinal direction and the width direction). The method of extending | stretching simultaneously), or the method which combined them can be used. Here, a sequential biaxial stretching method in which stretching in the longitudinal direction and then in the width direction is performed first is used. First, an unstretched polyphenylene sulfide film is heated with a heating roll group, and is 3 to 4 times, preferably 3.0 to 3.8 times, more preferably 3.0 to 3.7 times in the longitudinal direction (MD direction). The film is stretched in one or two or more stages (MD stretching). The stretching temperature ranges from Tg (glass transition temperature of PPS) to (Tg + 40) ° C., preferably (Tg + 5) to (Tg + 30) ° C. Here, Tg represents the glass transition temperature of polyphenylene sulfide, but in the case of a laminated film, it is preferably stretched in the above range according to the Tg of polyphenylene sulfide having a high Tg. Thereafter, it is cooled by a cooling roll group of 20 to 50 ° C.

  As a stretching method in the width direction (TD direction) following MD stretching, for example, a method using a tenter is common. The both ends of this film are gripped with clips, guided to a tenter, and stretched in the width direction (TD stretching). The stretching temperature is preferably Tg to (Tg + 40) ° C., more preferably (Tg + 5) to (Tg + 30) ° C. Here, Tg represents the glass transition temperature of polyphenylene sulfide as described above. In the case of a laminated film, it is preferably stretched in the above range according to the Tg of polyphenylene sulfide having a high Tg. The draw ratio is in the range of 3 to 4 times, preferably 3.0 to 3.6 times, more preferably 3.0 to 3.5 times from the viewpoint of improving the breaking elongation, and the area ratio (MD direction ratio). Product of magnification in the TD direction) is preferably 14 times or less, more preferably 13.5 times or less, and still more preferably 13 times or less.

  Next, this stretched film is heat-set under tension. The preferable heat setting temperature in the case of one-stage heat setting is 240 to 280 ° C., and the total time of the heat setting step and the relaxation treatment step is 1 to 60 seconds, preferably 5 to 30 seconds. A more preferable heat treatment is multistage heat setting. In this case, the heat setting temperature at the first stage is 160 to 220 ° C., preferably 180 to 220 ° C., and the treatment time is 1 to 30 seconds, preferably 1 to 15 seconds. The maximum temperature of the subsequent two-stage heat setting is 240 to 280 ° C, preferably 260 to 280 ° C. Furthermore, this film is subjected to a relaxation treatment in the width direction at 240 to 280 ° C, more preferably 260 to 280 ° C. The relaxation rate is preferably 0.1 to 8%, more preferably 2 to 5%. The total time of the two-stage heat fixation and relaxation treatment at 240 ° C. or higher is preferably 1 to 60 seconds, more preferably 5 to 30 seconds. Further, the film is cooled and wound up to room temperature, if necessary, while being subjected to relaxation treatment in the longitudinal and width directions to obtain a desired biaxially oriented film.

  The biaxially oriented film obtained by the above method is, for example, a biaxially oriented two-layer laminated film of biaxially oriented PPS film / biaxially oriented m-PPS film arranged so that the m-PPS layer is on the inside Then, thermal lamination is performed to obtain a laminated film of (PPS layer / m-PPS layer) / (m-PPS layer / PPS layer). Further, the biaxially oriented two-layer laminated film and the biaxially oriented PPS single film can be formed into a laminated film such as (PPS layer / m-PPS layer) / PPS layer. Further, (PPS layer / m-PPS layer) / PPS layer / (m-PPS layer / PPS layer) may be laminated. Also, a biaxially oriented three-layer laminated film of m-PPS layer / PPS layer / m-PPS layer was prepared, and a biaxially oriented PPS single film and PPS layer / (m-PPS layer / PPS layer / m-PPS layer) ) / PPS layer 5 layer laminated film. From the viewpoint of stability in film formation and improvement in planarity in lamination, a laminated structure of (PPS layer / m-PPS layer) / PPS layer / (m-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 film, for example, a method of heat laminating under high temperature and high pressure is preferable. The laminating temperature is preferably 230 to 260 ° C, more preferably 235 to 255 ° C, and further preferably 240 to 250 ° C. 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. When the surface temperature of the metal roll is less than 230 ° C., the interfacial adhesion of the laminated film may not be sufficiently improved, and the high temperature breaking elongation of the present invention may be reduced. On the other hand, when the surface temperature of the metal roll exceeds 260 ° C., the occurrence of wrinkles due to thermal shrinkage of the biaxially oriented film increases during lamination, and a laminated film having excellent flatness may not be obtained. The nip roll is not particularly limited, but a metal roll, a ceramic roll, a rubber material roll or the like can be used, and a rubber material roll is preferable from the viewpoint of uniform pressure load in the roll width direction, such as fluoro rubber and silicon rubber. However, it is not limited to these. The nip roll is preferably heated to exhibit the thermoformability of the present invention, and the roll surface temperature is preferably 180 ° C to 240 ° C, more preferably 190 ° C to 240 ° C, Preferably, it is 200 degreeC-240 degreeC. When the surface temperature of the nip roll is less than 180 ° C., the interfacial adhesion of the laminated film may not be sufficiently improved, and the high temperature breaking elongation of the present invention may be reduced. On the other hand, when the nip roll surface temperature exceeds 240 ° C., it is difficult to use in a mass production facility from the viewpoint of heat resistance of a rubber adhesive used for the nip roll surface. The lamination 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 thermoformability of the present invention. Therefore, it is preferable. The method for laminating the biaxially oriented film is not particularly limited, but a metal roll so that the PPS layer side of the biaxially oriented bilayer laminated film of the biaxially oriented PPS film / biaxially oriented m-PPS film is the outermost layer, From the viewpoint of reducing voids in the present invention, it is preferable that the biaxially oriented two-layer laminated film on the metal roll side is placed on the nip roll and then laminated on the metal roll. In the present invention, the outermost layer is a biaxially oriented PPS film from the viewpoint of improving the productivity of the thermal laminate, and when the biaxially oriented m-PPS film is the outermost layer, the outermost layer is thermally fused to a metal roll. , Productivity may deteriorate. The angle held by the metal roll is preferably 10 to 180 degrees, more preferably 30 to 150 degrees, and still more preferably 60 to 120 degrees. By placing a two-layer laminated biaxially oriented film of PPS layer / m-PPS layer on a metal roll before lamination, wrinkles due to thermal shrinkage of the film can be eliminated before lamination, and the void suppression specified in this application can be suppressed. Can be achieved. In addition, it is preferable to preheat and laminate the biaxially oriented bilayer laminated film of the PPS layer / m-PPS layer on the nip roll side in advance from the viewpoint of improving the adhesiveness of the interface. -180 degree | times are preferable, More preferably, it is 60-180 degree | times, More preferably, it is 90-180 degree | times.

  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.

  From the viewpoint of improving the interfacial adhesion, the biaxially oriented m-PPS film and the biaxially oriented PPS film used in the present invention are also included in a preferred embodiment of the present invention by subjecting the adhesive layer side to corona discharge treatment or plasma treatment. . 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. In the present invention, surface treatment is performed by NE treatment. Is more preferable from the viewpoint of improving adhesiveness. Moreover, in this invention, unless the effect of this invention is prevented, another sheet layer, a nonwoven fabric, etc. 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) In accordance with the following method prescribed in room temperature and 200 ° C. breaking elongation ASTM-D882, a sample film having a width of 10 mm was prepared using an Instron type tensile tester (Orientec AMF / RTA-100). The chuck is set to have a length of 50 mm, and a tensile test is performed at a temperature of 25 ° C. or 200 ° C. and a tensile speed of 300 mm / min. For the elongation at break, the average value in the film longitudinal direction n = 5 and the average value in the width direction n = 5 are calculated, and the obtained average value in the longitudinal direction and the average value in the width direction are used.
Measuring device: Orientec Co., Ltd. film strong elongation automatic measuring device “Tensilon AMF / RTA-100”
Sample size: 10mm width x 100mm length
Tensile speed: 300 mm / min Measurement environment: room temperature, 200 ° C.

(2) The void observation sample of the laminated film was arbitrarily cut into 10 cm square and n = 30 pieces, and the presence or absence of voids in the laminated film was determined according to the following criteria by the transmission method of an optical microscope. In Examples and Comparative Examples to be described later, observation was performed at a magnification of 50 times.
A: No void of 0.5 μm or more exists. ○: A void of 1 μm or more does not exist. Δ: A void of 1.5 μm or more does not exist. X: A void of 1.5 μm or more exists.

(3) Using a thermoformable vacuum / pressure forming machine (manufactured by Asano Seisakusho), the material is cut into a width of 22 cm and a length of 30 cm (A4 size), preheated to a sheet temperature of 255 ° C., φ20 mm, height It heat-formed with the 10-mm cylindrical metal mold | die, and the presence or absence of the generation | occurrence | production of a film crack was determined visually according to the following reference | standard. The number of processed samples was 100 samples.
A: Defect rate is less than 5%. O: Defect rate is over 5% and 10% or less. Δ: Defect rate is over 10% and 20% or less. X: Defect rate is over 20%.

(4) Melt viscosity
Using a flow tester CFT-500 (manufactured by Shimadzu Corporation), the base length was 10 mm, the base diameter was 1.0 mm, the preheating time was set to 5 minutes, and the measurement was performed at 310 ° C.
The melt viscosity at a shear rate of 1000 / s is a correlation line obtained by measuring the melt viscosities at shear rates of 500 to 1000 / s and 1000 to 2000 / s with n = 2, respectively, and linearly approximating them on a log-log plot. The value at a shear rate of 1000 / s.

Example 1
(1) Production of m-PPS resin An autoclave was charged with 100 moles of sodium sulfide nonahydrate, 45 moles of sodium acetate and 25 liters of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP). While stirring, the temperature was gradually raised to a temperature of 220 ° C., and the contained water was removed by distillation. In the system after dehydration, 5 liters of 91 mol of p-dichlorobenzene as a main component monomer, 10 mol of m-dichlorobenzene as a secondary component monomer, and 0.2 mol of 1,2,4-trichlorobenzene were added. Nitrogen was added together with NMP, 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 250 ° 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 and dispersed and blended uniformly, and extruded at a temperature of 320 ° C. with a 30 mmφ twin screw extruder to obtain m-PPS pellets. It was.

(2) Production of PPS resin The PPS resin was prepared in the same manner as in the production of m-PPS in (1) except that 101 mol of p-dichlorobenzene was used as the main monomer and no subcomponent monomer was used. Manufactured. The melt viscosity of the PPS resin was 3000 poise and the melting point was 283 ° C.

(3) Film formation The m-PPS resin and PPS resin obtained in the above (1) and (2) were each 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 pipe type laminating device at the upper part of the die is led to have two layers, and subsequently discharged from the T-die die, which is rapidly cooled with a cooling drum having a temperature of 25 ° C. A two-layer laminated sheet of m-PPS layer / PPS layer was obtained. Next, the obtained laminated sheet was caused to travel in contact with a plurality of heating rolls having a surface temperature of 95 ° C., and 3.7 ° in the longitudinal direction between the heating rolls and the 30 ° C. cooling rolls having different peripheral speeds. The film was stretched twice. The uniaxially stretched sheet thus obtained was stretched 3.5 times (area stretch ratio: 12.95 times) at a temperature of 100 ° C. in a direction perpendicular to the longitudinal direction using a tenter, and subsequently at a temperature of 200 ° C. Heat treatment for 10 seconds (1 step heat fixation), followed by 260 ° C., 10 seconds heat treatment (2 step heat fixation), followed by 5% relaxation treatment for 10 seconds in the 260 ° C. relaxation treatment zone. After cooling to room temperature, the film edge was removed to obtain a biaxially oriented two-layer laminated film (A) of m-PPS / PPS (15/60 μm). Further, a single PPS resin was separately formed and heat-treated under the above film forming conditions to obtain a biaxially oriented PPS single film (B) having a thickness of 100 μm.

(4) Lamination A biaxially oriented two-layer laminated film (A) and a biaxially oriented PPS single film (B) obtained by the above-mentioned film-forming method have an m-PPS layer on the inside as in A / B / A. Heat laminated so that Lamination conditions were such that a metal roll (HCr roll) was heated as a heating roll so that the roll surface temperature was 240 ° C., and the nip roll was heated using a fluororubber roll so that the roll surface temperature was 200 ° C. The laminating pressure was 20 kg / cm ² and the laminating speed was 1 m / min. The holding angle of the biaxially oriented two-layer laminated film (A) was 60 ° on the metal roll side and 90 ° on the nip roll side, and the biaxially oriented PPS single film in the central layer was inserted 30 ° into the metal roll. After laminating, it was immediately cooled and wound up. Table 1 shows the evaluation results of the 5-layer laminated film having a thickness of 250 μm obtained as described above.

(Example 2)
A five-layer laminated film was produced in the same manner as in Example 1 except that the temperature of the metal roll was set to 235 ° C. in Example 1. The evaluation results of the obtained five-layer laminated film are shown in Table 1.

(Example 3)
A five-layer laminated film was produced in the same manner as in Example 1 except that the temperature of the metal roll was changed to 230 ° C. in Example 1. The evaluation results of the obtained five-layer laminated film are shown in Table 1.

Example 4
A 5-layer laminated film was produced in the same manner as in Example 1 except that the laminating speed was 3 m / min in Example 1. The evaluation results of the obtained five-layer laminated film are shown in Table 1.

(Example 5)
A five-layer laminated film was produced in the same manner as in Example 1 except that the laminating speed was 5 m / min in Example 1. The evaluation results of the obtained five-layer laminated film are shown in Table 1.

(Example 6)
A five-layer laminated film was produced in the same manner as in Example 1 except that the holding angle of the metal roll was 30 degrees in Example 1. The evaluation results of the obtained five-layer laminated film are shown in Table 1.

(Example 7)
A five-layer laminated film was produced in the same manner as in Example 1 except that the holding angle of the metal roll was set to 10 degrees in Example 1. The evaluation results of the obtained five-layer laminated film are shown in Table 1.

(Example 8)
Example 1 except that the stretching ratio of the biaxially oriented two-layer laminated film and the biaxially oriented single film used in Example 1 is 3.8 × 3.5 times (area stretching ratio is 13.3 times). Similarly, a five-layer laminated film was produced. The evaluation results of the obtained five-layer laminated film are shown in Table 1.

Example 9
Example 1 except that the stretching ratio of the biaxially oriented two-layer laminated film and the biaxially oriented single film used in Example 1 is 3.9 × 3.5 times (area stretching ratio is 13.65 times). Similarly, a five-layer laminated film was produced. The evaluation results of the obtained five-layer laminated film are shown in Table 1.

(Example 10)
95 parts by weight of the PPS resin prepared in Example 1 and 5 parts by weight of polyetherimide resin (“Ultem 1010” (registered trademark) (PEI) manufactured by GE Plastics) were dried under reduced pressure at 120 ° C. for 3 hours, and further PPS resin and PEI After adding 0.5 parts by weight of γ-isocyanatopropyltriethoxysilane (manufactured by Shin-Etsu Chemical Co., Ltd., “KBE9007” (registered trademark)) as a compatibilizing agent to 100 parts by weight of the resin, the resin was heated to 310 ° C. In addition, the kneading paddle kneading section was placed in a vented co-rotating twin-screw kneading extruder (manufactured by Nippon Steel Co., Ltd., screw diameter 30 mm, screw length / screw diameter = 45.5), and the residence time 90 seconds, melt extrusion at a screw speed of 300 revolutions / minute, discharge into a strand, cool with water at a temperature of 25 ° C, and immediately cut To obtain a PPS resin composition of PPS resin / PEI (95/5 wt%) Te.

  The PPS resin composition and the m-PPS resin used in Example 1 were each dried at 180 ° C. for 3 hours under a reduced pressure of 1 mmHg, and then supplied to separate extruders. It is led so as to have two layers by a heavy tube type laminating apparatus, then discharged from a T-die die provided, rapidly cooled by a cooling drum at a temperature of 25 ° C., and substantially m-PPS / PPS resin composition A two-layer laminated sheet was obtained. Next, the laminated sheet was brought into contact with a plurality of heating rolls having a surface temperature of 115 ° C., and stretched 3.0 times in the longitudinal direction between the heating rolls and the 30 ° C. cooling rolls having different peripheral speeds. . The uniaxially stretched sheet thus obtained was stretched 3.5 times (area stretch ratio 10.5 times) at a temperature of 125 ° C. in a direction perpendicular to the longitudinal direction using a tenter, and subsequently at a temperature of 200 ° C. Heat treatment was performed for 10 seconds (one-stage heat setting) followed by heat treatment at 260 ° C. for 10 seconds (two-stage heat setting), followed by a 5% relaxation treatment in the transverse direction for 10 seconds in a 260 ° C. relaxation treatment zone. Then, after cooling to room temperature, the film edge was removed to obtain a biaxially oriented two-layer laminated film of m-PPS / PPS resin composition (15/60 μm). In addition, the PPS resin composition alone was separately formed and heat-treated under the above film forming conditions to obtain a biaxially oriented single film having a thickness of 100 μm.

  The obtained biaxially oriented two-layer laminated film and biaxially oriented single film were thermally laminated in the same manner as in Example 1 to produce a five-layer laminated film. The evaluation results of the obtained five-layer laminated film are shown in Table 1.

Example 11
Example 10 except that the stretching ratio of the biaxially oriented two-layer laminated film and the biaxially oriented single film used in Example 10 is 3.2 × 3.5 times (area stretching ratio 11.2 times). Similarly, a five-layer laminated film was produced. The evaluation results of the obtained five-layer laminated film are shown in Table 1.

(Comparative Example 1)
A five-layer laminated film was produced in the same manner as in Example 1 except that the metal roll temperature was 200 ° C. and the nip roll temperature was 150 ° C. in Example 1. The evaluation results of the obtained five-layer laminated film are shown in Table 1.

(Comparative Example 2)
A five-layer laminated film was produced in the same manner as in Example 1 except that the holding angle of the metal roll was set to 5 degrees in Example 1. The evaluation results of the obtained five-layer laminated film are shown in Table 1.

(Comparative Example 3)
A five-layer laminated film was produced in the same manner as in Example 1 except that the laminating speed was 7 m / min in Example 1. The evaluation results of the obtained five-layer laminated film are shown in Table 1.

(Comparative Example 4)
Example 1 except that the stretching ratio of the biaxially oriented two-layer laminated film and the biaxially oriented single film used in Example 1 is 4.2 × 3.6 times (area stretching ratio is 15.12 times). Similarly, a five-layer laminated film was produced. The evaluation results of the obtained five-layer laminated film are shown in Table 1.

(Comparative Example 5)
Example 1 was the same as Example 1 except that the first heat setting was 260 ° C., 10 seconds, the second heat setting was 260 ° C., 10 seconds, and the relaxation treatment was 260 ° C., 10 seconds. A five-layer laminated film was produced. The evaluation results of the obtained five-layer laminated film are shown in Table 1.

(Comparative Example 6)
Example 11 is the same as Example 10 except that the first heat setting is 260 ° C., 10 seconds, the second heat setting is 260 ° C., 10 seconds, and the relaxation treatment is 260 ° C., 10 seconds. A five-layer laminated film was produced. The evaluation results of the obtained five-layer laminated film are shown in Table 1.

  The laminated film of the present invention is a laminated film excellent in moldability, particularly thermoformability, and is used for a drive motor, an air conditioner compressor motor, or a water heater used in a hybrid vehicle currently being developed by an automobile manufacturer. It is suitable for various motor insulating molding materials such as motors, and further suitable as a member for thermoforming such as die molding, vacuum molding, vacuum / pressure air molding, and in-mold molding.

Claims (6)

The outermost layer is a laminated film composed of a biaxially oriented polyarylene sulfide film, and at least one layer other than the outermost layer is composed of a biaxially oriented copolymerized polyarylene sulfide film. A laminated film in which an axially oriented copolymer polyarylene sulfide film is adjacent, and the laminated film has a room temperature breaking elongation (Er) and a 200 ° C. breaking elongation (E200) satisfying the following formulas.
1 ≦ E200 / Er ≦ 1.5 The laminated film according to claim 1, wherein voids of 1.5 μm or more are not present in the laminated film. 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. A method for producing a laminated film in which heat setting after biaxial stretching of the biaxially oriented polyarylene sulfide film constituting the laminated film according to any one of claims 1 to 4 is performed at two or more different temperatures. A method for producing a laminated film, wherein the first stage of heat setting temperature is 160 ° C. or more and 220 ° C. or less, and the highest temperature of heat setting performed after the second stage is 240 ° C. or more and 280 ° C. or less. The method for producing a laminated film according to claim 5, wherein the total time of the heat setting step of 240 ° C or higher and the relaxation treatment step to be further performed is 1 second or more and 60 seconds or less.