JPWO2013176103A1 - Biaxially stretched polyarylene sulfide film for metal bonding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a biaxially stretched polyarylene sulfide film for metal adhesion excellent in adhesion to metal and adhesion durability. A biaxially stretched polyarylene sulfide film for metal bonding, comprising a biaxially stretched polyarylene sulfide film having a melting point of 260 ° C. or less and having a crystallinity of 10% or more and 30% or less. [Selection figure] None

Description

  The present invention relates to a biaxially stretched polyarylene sulfide film for metal bonding.

  Polyarylene sulfide has excellent properties such as heat resistance, flame retardancy, rigidity, chemical resistance, electrical insulation and low hygroscopicity, and is particularly suitable for electrical / electronic equipment, mechanical parts and automotive parts. It is used.

  In recent years, polyarylene sulfide films represented by polyphenylene sulfide (hereinafter sometimes abbreviated as PPS) have been applied to electrical insulating materials by taking advantage of their electrical insulating properties and low hygroscopicity. However, polyarylene sulfide films generally have the drawbacks of low adhesion and adhesion to metals and other resins, and low moldability.

  For example, polyphenylene sulfide is excellent in mechanical properties (Patent Document 1). However, although it was excellent in mechanical properties, it was not satisfactory in the adhesiveness of metals and the like. In addition, a technique for blending m-phenylene sulfide units is disclosed (Patent Document 2), which is a technique related to a film having excellent thickness unevenness, mechanical properties, and heat resistance, and is satisfactory in adhesiveness and moldability of metals and the like. It wasn't going to be good. In addition, a technique of a laminated film in which a biaxially stretched polyarylene sulfide film and a biaxially stretched copolymer polyarylene sulfide film are alternately laminated is disclosed (Patent Document 3). It is a technology related to crack improvement, and was not satisfactory in terms of adhesion of metals and the like, and formability during heating. In addition, a technique for heat-fixing a polyarylene sulfide resin in two stages is disclosed (Patent Document 4), which is a technique for improving the elongation at break and flatness, in the adhesiveness of metals and the moldability during heating. It was not satisfactory.

Japanese Patent Laid-Open No. 62-257941 JP-A-63-260426 JP 2011-213109 A International Publication No. 2008/139989

  Accordingly, an object of the present invention is to solve these problems and provide a biaxially stretched polyarylene sulfide film for metal bonding that is excellent in adhesion to metal, adhesion durability, and moldability.

(1) A biaxially stretched polyarylene sulfide film for metal bonding, comprising a polyarylene sulfide having a melting point of 260 ° C. or lower and a crystallinity of 10% or more and 30% or less,
(2) The biaxially stretched polyarylene sulfide film for metal bonding according to (1), wherein the Young's modulus of the film is 2.5 GPa or more and 3.5 GPa or less.
(3) The biaxially stretched polyarylene sulfide film for metal bonding according to (1) or (2), wherein the polyarylene sulfide is a polyarylene sulfide containing 5 to 15 mol% of m-phenylene sulfide units. ,
(4) The biaxially stretched polyarylene sulfide film for metal bonding according to any one of (1) to (3), wherein a 200 ° C. breaking elongation of the film is 150% or more.
(5) The biaxially stretched polyarylene sulfide film for metal bonding according to any one of (1) to (4), comprising two or more kinds of PPS having different melting points of the polyarylene sulfide.
(6) The biaxially stretched polyarylene sulfide film for metal bonding according to (1) to (5), wherein the melt viscosity of the polyarylene sulfide is 200 to 10000 poise,
It is.

  ADVANTAGE OF THE INVENTION According to this invention, the biaxially-stretched polyarylene sulfide film for metal adhesion excellent in the adhesiveness with metal, adhesion durability, and a moldability can be obtained, and can be used suitably as a metal sealing material of various components. .

  It is important that the polyarylene sulfide used in the biaxially stretched polyarylene sulfide film for metal bonding of the present invention has a melting point of 260 ° C. or lower, more preferably 250 ° C. or lower, and further preferably 248 ° C. or lower. Although there is no restriction | limiting in particular as a minimum, when utilizing the heat resistance of polyarylene sulfide, it is 230 degreeC or more.

  The polyarylene sulfide resin used in the present invention is a copolymer having a repeating unit of-(Ar-S)-. Examples of Ar include units represented by the following formulas (A) to (K).

(R1 and R2 are substituents selected from hydrogen, an alkyl group, an alkoxy group, and a halogen group, and R1 and R2 may be the same or different.)
As the repeating unit of the polyarylene sulfide resin used in the present invention, the structural formula represented by the above formula (A) is preferable, and typical examples thereof include polyphenylene sulfide, polyphenylene sulfide sulfone, polyphenylene sulfide ketone and the like. Particularly preferable polyarylene sulfide is preferably polyphenylene sulfide (PPS) from the viewpoint of film properties and economy. It is preferable that a p-phenylene sulfide unit represented by the following structural formula is composed of 85 mol% or more and 95 mol% or less of all repeating units as the main structural unit of PPS. More preferably, it is 88 mol% or more and 92 mol% or less. If the p-phenylene sulfide unit is less than 85 mol%, the heat resistance and chemical resistance may be deteriorated, and the required crystallinity may not be obtained. If it exceeds 95 mol%, the polyarylene sulfide is not obtained. In some cases, the melting point of the resin cannot be sufficiently lowered, and the moldability and the adhesion to the metal cannot be sufficiently improved.

  The melt viscosity of the polyarylene sulfide resin is not particularly limited as long as melt kneading is possible, but it is preferably in the range of 200 to 10000 poise at a temperature of 300 ° C. and a shear rate of 200 (1 / sec). Is preferable, more preferably 500 to 5000 poise, still more preferably 1000 to 3000 poise, and more preferably 1500 to 2500 poise. If the melt viscosity of the polyarylene sulfide resin is less than 200 poise, the fluidity at the time of melting the polyarylene sulfide resin is too high, so that the film-forming stability may be lowered. If the melt viscosity is greater than 10,000 poise, the fluidity of the molten resin May not be sufficiently secured, and adhesion to metal may not be sufficiently enhanced. The melt viscosity can be evaluated by the method described later.

Further, in the present invention, it is necessary to use polyarylene sulfide having a melting point of 260 ° C. or lower, but in order to make the melting point 260 ° C. or lower, it can be adjusted by introducing a copolymer component. For example, when p-phenylene sulfide is used as the main structural unit, from the viewpoint of setting the crystallinity described below to a predetermined range, 5 mol% or more and 20 mol% or less of the repeating unit, 5 mol% or more and 18 mol% or less. The melting point is obtained by copolymerizing constituent units other than the p-phenylene sulfide unit in the range of 5 mol% to 15 mol%, preferably 11 mol% to 15 mol%, preferably 8 mol% to 12 mol%. Can be within a predetermined range. If the copolymerized unit is less than 5 mol%, the melting point of the polyarylene sulfide resin cannot be sufficiently lowered, and the moldability and the adhesion to the metal may not be sufficiently improved. If it exceeds 20 mol%, the heat resistance, Chemical resistance may decrease.
In the present invention, the polyarylene sulfide used for the biaxially stretched polyarylene sulfide film for metal bonding may contain two or more polyarylene sulfides having different melting points. When the polyarylene sulfide contains two or more types of polyarylene sulfides having different melting points, the polyarylene sulfide having a melting point of 245 ° C. or less may be contained in an amount of 10 to 50% by mass in 100% by mass of the total content of polyarylene sulfides. Preferably, it is more preferable to contain 1-40 mass%. By including a polyarylene sulfide having a melting point of 245 ° C. or less, excellent adhesiveness can be exhibited by maintaining film forming stability and improving fluidity. When the content of polyarylene sulfide having a melting point of 245 ° C. or lower is smaller than 10% by mass, the adhesion to metal may be lowered. On the other hand, if it is larger than 50% by mass, the heat resistance and chemical resistance may decrease. The polyarylene sulfide having a melting point of 245 ° C. or less can be adjusted by copolymerizing constituent units other than p-phenylene sulfide units of 15 mol% or more of the repeating units.

  A preferred copolymer unit is a copolymer 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 m-phenylene sulfide units are preferred from the viewpoint of suppressing crystallization and improving adhesion to metal.

  The mode of copolymerization with the copolymerization component is not particularly limited, but is preferably a random copolymer.

  In the biaxially stretched polyarylene sulfide film for metal bonding of the present invention, it is important that the crystallinity is 10% or more and 30% or less from the viewpoint of adhesion to metal and adhesion durability. The lower limit is preferably 17% or more, more preferably 19% or more, and the upper limit is preferably 28% or less, more preferably 26% or less, more preferably 24% or less, and even more preferably 22% or less. When the crystallinity is less than 10%, the creep property of the film is deteriorated and the durability for adhesion to the metal is lowered. On the other hand, when the crystallinity is more than 30%, the moldability and the adhesion to the metal are inferior. It becomes. In order to make the crystallinity of the film within the scope of the present invention, it can be adjusted by controlling the film-forming conditions. For example, a film containing p-phenylene sulfide units and m-phenylene sulfide units can be adjusted. When it is a polymer, heat setting is performed in two or more steps with different temperatures, the first heat setting is performed at 150 ° C. or more and 170 ° C. or less, and the heat setting temperature at the latter stage is performed at 180 ° C. or more and 230 ° C. or less The film of the present invention can be obtained.

  From the viewpoint of adhesion durability, the biaxially stretched polyarylene sulfide film for metal bonding of the present invention preferably has a Young's modulus of 2.5 GPa or more and 3.5 GPa or less, more preferably 2.5 GPa or more and 3.0 GPa. Hereinafter, more preferably 2.5 GPa or more and 2.8 GPa or less. Here, the Young's modulus of the film is the average Young's modulus in the longitudinal direction and the width direction of the film. When the longitudinal direction and the width direction of the film are unknown, the longitudinal direction and the width direction are arbitrary points on the film surface. When the refractive index is measured over 360 ° in the plane, the direction with the highest refractive index and the direction perpendicular thereto are regarded as the longitudinal direction and the width direction, respectively. When the Young's modulus is less than 2.5 GPa, the creep property of the film is deteriorated, and the durability of adhesion to metal may be lowered. If the Young's modulus exceeds 3.5 GPa, moldability and adhesion to metal may be reduced. In order to make Young's modulus into the said range, it can achieve by using polyarylene sulfide resin whose melting | fusing point is 260 degrees C or less, and making area magnification into the range mentioned later.

  The biaxially stretched polyarylene sulfide film for metal bonding of the present invention preferably has a breaking elongation at 200 ° C. of 150% or more from the viewpoint of improving moldability with metal. More preferably, it is 200% or more, More preferably, it is 250% or more. Here, the breaking elongation of the film is an average breaking elongation in the longitudinal direction and the width direction of the film, and when the longitudinal direction and the width direction of the film are unknown, the longitudinal direction and the width direction are arbitrary on the film surface. When the refractive index is measured over an in-plane 360 ° with respect to the point, the direction having the highest refractive index and the direction perpendicular thereto are regarded as the longitudinal direction and the width direction, respectively. The 200 degreeC breaking elongation of the biaxially stretched polyarylene sulfide film for metal bonding of the present invention is an average breaking elongation in the film longitudinal direction and width direction. When the breaking elongation at 200 ° C. is less than 150%, film breakage may occur in the molding process with metal. The upper limit of breaking elongation is not particularly provided, but if it exceeds 400%, the heat resistance of the film may be lowered. In order to make the breaking elongation at 200 ° C. of the biaxially stretched polyarylene sulfide film for metal bonding of the present invention within the above range, the melting point is within the scope of the present invention, and the specific area magnification and heat setting described in the present specification. By the method, it becomes possible to obtain the crystallinity within the range of the present invention.

The biaxially stretched polyarylene sulfide film for metal bonding of the present invention preferably has a creep resistance of 3% or less, more preferably 2% or less, and still more preferably, from the viewpoint of durability for adhesion to metal. Is 1% or less. When the creep resistance exceeds 3%, the adhesion durability to metal may be deteriorated. Creep resistance is an index indicating the degree of deformation of the film under a constant load, and is preferably in the above range from the viewpoint of durability for adhesion to metal. In order to make the creep resistance of the biaxially stretched polyarylene sulfide film for metal bonding of the present invention within the above range, it can be achieved by using PPS having a specific melting point described in the present specification and setting the area magnification described later. . In the present invention, the amount of film change (elongation) after being treated for 65 hours in an oven heated to 70 ° C. by hanging a weight of 500 g on one side of a film obtained by cutting a 0.1 mm thick film to a size of 5 mm × 15 cm. Were measured and evaluated. When the film thickness is not 0.1 mm, the weight is applied so that the load per 1 mm ² of the cross-sectional area is 1 kg.

  The thickness of the biaxially stretched polyarylene sulfide film for metal bonding of the present invention is preferably 25 μm or more and 300 μm or less, more preferably 50 μm or more and 200 μm or less, from the viewpoint of durability for adhesion to metal. When film thickness is less than 25 micrometers, adhesiveness with a metal may deteriorate.

  The biaxially stretched polyarylene sulfide film for metal bonding of the present invention is used for metal bonding, and as the metal, a metal such as aluminum, SUS (stainless steel), copper, or an alloy of two or more metals may be used. it can. Two or more metal plates may be laminated. The surface of the metal may be subjected to surface treatment such as oxidation, addition of another metal atom, or chemical treatment. For bonding with metal, a method of thermal bonding is preferably used. Metal-bonded films include, for example, electronic / electrical sealing materials such as connectors, printed boards and sealing molded products, sealing materials for insulating materials for drive motors used in hybrid vehicles, electric vehicles, fuel cell vehicles, batteries, etc. Useful as a sealing material.

  The biaxially stretched polyarylene sulfide film for metal bonding of the present invention is a heat stabilizer, an antioxidant, an ultraviolet absorber, an antistatic agent, and a flame retardant, as long as the effects of the present invention are not impaired. In addition, inorganic particles, organic particles, and the like can also be included in order to impart slipperiness, abrasion resistance, scratch resistance, and the like to the sheet 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.

  It is also included in a preferable aspect of the present invention that the biaxially stretched polyarylene sulfide film for metal bonding of the present invention is subjected to corona discharge treatment or plasma treatment. The atmosphere gas at the time of corona discharge treatment is not particularly limited, and includes at least one gas selected from air (EC treatment), oxygen (OE treatment), nitrogen (NE treatment), carbon dioxide gas (CE treatment), and the like. .

  Next, regarding the method for producing a polyarylene sulfide film of the present invention, a copolymerized phenylene sulfide resin obtained by copolymerizing m-dichlorobenzene with p-phenylene sulfide as a polyarylene sulfide resin (hereinafter sometimes abbreviated as a copolymerized PPS resin). However, it is needless to say that the present invention is not limited to this example. That is, the present invention can be carried out without undue trial and error by referring to this example by changing the monomer used as appropriate.

  Examples of the method for producing the copolymerized PPS resin include the following methods. For example, there are the following methods. Sodium sulfide, p-dichlorobenzene, and m-phenylene sulfide 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 with. If necessary, a copolymerization component such as trihalobenzene can be used. 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 copolymerized 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 Unreacted monomers and the like are separated to obtain a copolymerized PPS resin. If necessary, an inorganic or organic additive or the like can be added to the polymer obtained as described above to the extent that the object of the present invention is not impaired.

  Thereafter, the molten polymer that has passed through the extruder is passed through a filter, and then the molten polymer is discharged into a sheet shape using a die of a T die. The sheet-like material is brought into close contact with a cooling drum having a surface temperature of 20 to 70 ° C. to be cooled and solidified to obtain a substantially non-oriented unstretched polyphenylene sulfide sheet.

  Subsequently, the single layer in the amorphous state thus obtained is subjected to two-stage stretching using a conventionally known sequential biaxial stretching machine or simultaneous biaxial stretching machine within the range of the glass transition point of the copolymerized PPS resin to the cold crystallization temperature. After axial stretching, multistage heat treatment is performed at a temperature in the range of 150 to 230 ° 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 by a group of heating rolls, and is 2.5 to 3.4 times, preferably 2.8 to 3.0 times, one stage or two or more stages in the longitudinal direction (MD direction). (MD stretching). The stretching temperature is in the range of Tg (glass transition temperature of copolymerized PPS) to (Tg + 40) ° C., preferably (Tg + 5) to (Tg + 30) ° C. 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 (glass transition temperature of copolymerized PPS) to (Tg + 40) ° C., more preferably in the range of (Tg + 5) to (Tg + 30) ° C. From the viewpoint of improving adhesion to metal, 2.5 to 3.4 times, preferably 2.8 to 3.0 times is preferable. In addition, the area magnification (product of the MD magnification and the TD magnification) is preferably 6 times or more, more preferably 12 times or less, and more preferably 12 times or less from the viewpoints of adhesion to metal, adhesion durability, and moldability. Is 7.5 to 9 times. By making it within the above range, the adhesion to metal by suppressing crystallization is improved and the orientation of the film is lowered without impairing the flatness and film-forming stability of the biaxially stretched polyarylene sulfide film for metal bonding. It is possible to achieve both improvement in formability by the above.

  Next, this stretched film is heat-set under tension. The preferred heat setting temperature for the first stage heat setting is 150 ° C to 170 ° C, preferably 160 ° C to 170 ° C. By setting the first stage heat fixing temperature within the above range, the film flatness can be maintained. The preferable heat setting temperature of the second stage heat setting is 180 to 230 ° C, preferably 190 to 220 ° C, and more preferably 200 to 210 ° C. By setting the second-stage heat fixing temperature within the above range, the crystallinity and the elongation at break at 200 ° C. can be easily set within a preferable range, and the adhesion strength when bonded to a metal is easily increased. When the second stage heat fixing temperature is less than 180 ° C., the crystallinity becomes too low, and thus the creep resistance may be deteriorated. And moldability may be reduced. It is possible to raise the first and second heat setting temperatures step by step to form microcrystals by the first heat setting, and to suppress orientation relaxation by the second heat setting. is important. The second stage heat setting temperature is preferably in the range of (melting point−70) ° C. to (melting point−20) ° C., and exhibits creep resistance and adhesion durability when bonded to metal by crystallization. In addition, it is possible to exhibit excellent adhesiveness with a metal by suppressing excessive crystallization. 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.

[Measurement method of characteristics]
(1) Melting point Using a Seiko Instruments DSC (RDC220) as a differential scanning calorimeter in accordance with JIS K7121-1987 and a disk station (SSC / 5200) as a data analyzer, 5 mg of a sample on an aluminum saucer at room temperature From 350 to 350 ° C. at a heating rate of 20 ° C./min. After the sample was taken out and rapidly cooled, the temperature was raised from room temperature to 350 ° C. at a rate of temperature rise of 20 ° C./min, and the peak temperature of the endothermic peak of melting observed at that time is defined as the melting point (Tm).

(2) Melt viscosity of PPS resin or PPS film Capillograph C1 manufactured by Toyo Seiki Co., Ltd. (die length 10 mm, die hole diameter (mm) was measured under the conditions of 300 ° C. or 320 ° C., and the shear rate was 200 / s. The melt viscosity was measured.

  When measuring the PPS resin, a powder-like or chip-like resin was directly used as a sample. Moreover, when measuring the viscosity of PPS which comprises a film, about 4g of films | membranes were extract | collected using the freeze pulverization apparatus (model name: Model 6770 made from SPEX) of a commercial machine, and it put into the container for freeze pulverization. Liquid nitrogen was used as a refrigerant for freeze pulverization, and the sample was freeze pulverized at -196 ° C.

(3) Crystallinity Using a differential scanning calorimeter DSC (RDC220) manufactured by Seiko Instruments in accordance with JIS K7121-1987 and a disk station (SSC / 5200) manufactured by the company as a data analyzer, 5 mg of a sample is placed on an aluminum tray. The temperature was raised from room temperature to 350 ° C. at a rate of temperature rise of 20 ° C./min, and melted and held at 350 ° C. for 5 minutes. At that time, the crystallinity was determined by the following calculation method.
Crystallinity (%) = (Endothermic peak heat amount ΔHm accompanying crystal melting−Hexothermic peak heat amount ΔHc accompanying crystal formation) / Heat amount of melting of completely crystalline polyarylene sulfide ΔHm ^{* 1} × 100
^{* 1 When the} polyarylene sulfide is PPS, the literature value of ΔHm = 146.44 J / g (Maemura E., Cakmak M., White JL, Polym. Eng. Sci, 29, 140 (1989)).

(4) Young's modulus In accordance with the following method defined in ASTM-D882 (1999), a sample film having a width of 10 mm is placed between chucks using an Instron type tensile tester (Orientec AMF / RTA-100). The length was set to 50 mm, and a tensile test was performed at a temperature of 25 ° C. and an atmospheric condition of 55% RH (relative humidity) at a tensile speed of 300 mm / min.

  The Young's modulus was obtained by the following equation by measuring 5 samples for each of the film longitudinal direction and the width direction.

Measuring device: Orientec Co., Ltd. film strong elongation automatic measuring device “Tensilon AMF / RTA-100”
Sample size: width 10mm x length 150mm
Tensile speed: 300 mm / min Measurement environment: 25 ° C., 55% RH
Young's modulus (GPa) = (total sum of Young's moduli of the film determined for the longitudinal direction (for 5 samples) + total sum of Young's moduli of the film determined for the width direction (for 5 samples)) / 10.

(5) 200 degreeC breaking elongation According to the following method prescribed | regulated to ASTM-D882 (1999), the sample film of width 10mm using the Instron type tensile tester (AMF / RTA-100 made by Orientec) Was set so that the length between chucks was 50 mm, and a tensile test was performed at a tensile speed of 300 mm / min under a temperature atmosphere condition of 200 ° C.

  The breaking elongation was determined by the following formula after measuring 5 samples in each of the film longitudinal direction and the width direction.

Measuring device: Orientec Co., Ltd. film strong elongation automatic measuring device “Tensilon AMF / RTA-100”
Sample size: width 10mm x length 150mm
Tensile speed: 300 mm / min Measurement environment: 200 ° C.
Elongation at break (%) = (total sum of breaking elongation of film determined for longitudinal direction (for 5 samples) + total sum of breaking elongation of film determined for width direction (for 5 samples)) / 10.

(6) Creep resistance A film with a thickness of 0.1 mm is cut to a size of 5 mm × 15 cm, a weight of 500 g is attached to a film with a measurement length of 5 cm, and heated in an oven at 70 ° C. for 65 hours. Calculated by the formula. The unit is%.
Creep resistance (%) = (measured length after heating−measured length before heating) / measured length before heating × 100.

(7) Using a vacuum / vacuum molding machine (manufactured by Asano Manufacturing Co., Ltd.), the sample is cut into a width of 22 cm and a length of 30 cm (A4 size), preheated to a sheet temperature of 200 ° C., φ20 mm, height 10 mm The film was heat-molded with a cylindrical mold, and the presence or absence of film cracking was visually determined according to the following criteria. The number of processed samples was 100 samples.
AA: The number of occurrences of film tears and cracks is less than 5% A: The number of occurrences of film tears and cracks is 5% or more and less than 10% B: The number of occurrences of film tears or cracks is 10% or more and less than 20% C: The number of film tears and cracks is 20% or more.

(8) Adhesive strength after endurance test A 30 mm x 70 mm size aluminum plate (thickness: 0.5 mm) is sandwiched between two 30 mm x 15 mm size samples, and the mold surface temperature is 250 ° C with a hot press. After preheating for 5 seconds, the sample was heated for 3 minutes under a pressure of 10 MPa to bond the sample and the aluminum plate. Using horizontal vise (made by Nabeya Co., Ltd.), the sample and the aluminum plate were bonded to each other with a horizontal vise sandwiched between 30 mm x 15 mm locations, and each aluminum plate was sandwiched between the horizontal vise It was bent so as to be 90 ° to the angle. The bent aluminum plate was 30 mm × 55 mm. One side of the aluminum plate was fixed to the oven ceiling, a binder clip was attached to the other aluminum plate, a 10 MPa weight was suspended in the hole at the binder clip handle, and heat treatment was performed in an oven at 70 ° C. for 65 hours. After the heat treatment, both ends of the aluminum plate are sandwiched between chucks of the tensile tester described in (5), and the maximum adhesive strength is obtained by pulling in a 180 ° direction at a distance between chucks of 10 mm and a tensile speed of 20 mm / min. The arithmetic average value was evaluated according to the following criteria.
AA: Adhesive strength after endurance test is 100 N / 30 mm or more A: Adhesive strength after endurance test is 50 N / 30 mm or more, less than 100 N / 30 mm B: Adhesive strength after endurance test is 30 N / 30 mm or more, 50 N / 30 mm Less than C: Adhesive strength after durability test is less than 30 N / 30 mm.

(9) Adhesive durability A 30 mm × 15 mm size aluminum plate (thickness: 0.5 mm) was sandwiched between two 30 mm × 70 mm size aluminum plates, and the mold surface temperature was 250 ° C. for 5 seconds with a hot press. Thereafter, the sample was heated for 3 minutes under a pressure of 10 MPa to bond the sample and the aluminum plate. In the same manner as in the above (8), the aluminum plate was folded at 90 ° at the 30 mm × 15 mm location where the sample was bonded to the aluminum plate. The bent aluminum plate was 30 mm × 55 mm. Both ends of the bent aluminum plate were sandwiched between the chucks of the tensile tester described in (5) and pulled in the 180 ° direction at a distance between chucks of 10 mm and a tensile speed of 20 mm / min to evaluate the adhesive strength before the durability test. From the adhesive strength before the durability test thus obtained and the adhesive strength after the durability test obtained in (8), the adhesion durability was calculated by the following formula.
Adhesive durability (%) = (Adhesive strength before durability test−Adhesive strength after durability test) / Adhesive strength before durability test × 100
AA: Decrease rate of adhesive strength is less than 10% A: Decrease rate of adhesive strength is 10% or more and less than 20% B: Decrease rate of adhesive strength is 20% or more and less than 30% C: Adhesion Strength reduction rate is 30% or more.

Reference Example 1 Production of Copolymerized PPS Resin 1 An autoclave was charged with 100 moles of sodium sulfide nonahydrate, 45 moles of sodium acetate and 25 liters of N-methyl-2-pyrrolidone, and gradually 220 with stirring. The temperature was raised to a temperature of 0 ° C., and the contained water was removed by distillation. In the system after dehydration, 90 mol of p-dichlorobenzene as a main component monomer and 10 mol of m-dichlorobenzene as a secondary component monomer were added together with 5 liters of NMP, and nitrogen was supplied at a temperature of 170 ° C. at 3 kg / cm 3. After pressurizing and sealing at ² , the temperature was raised and polymerization was carried out at 260 ° C. for 4 hours. 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 polymer thus obtained was washed five times with distilled water at 90 ° C. and then dried under reduced pressure at a temperature of 120 ° C. The melt viscosity at 300 ° C. was 2800 poise and the melting point was 250 ° C. A copolymerized PPS resin 1 was prepared.

(Reference Example 2) Production of PPS resin The same procedure as in Reference Example 1 was carried out except that 100 mol of p-dichlorobenzene was used as the main component monomer and no subcomponent monomer was used, and the melt viscosity at 320 ° C. was 4500 poise. A PPS resin having a melting point of 285 ° C. was produced.

Reference Example 3 Production of Copolymerized PPS Resin 2 The same procedure as in Reference Example 1 was carried out except that 85 mol of p-dichlorobenzene was used as the main component monomer and 15 mol of m-dichlorobenzene was used as the accessory component monomer. A copolymerized PPS resin 2 having a melt viscosity of 1400 poise at 300 ° C. and a melting point of 240 ° C. was produced.

Example 1
100 parts by weight of copolymerized PPS resin 1 produced in Reference Example 1 was heated to 280 ° C. with a vented co-rotating twin-screw kneading extruder (manufactured by Nippon Steel Works, screw diameter 30 mm, screw length / screw diameter = 45 5), melt-extruded at a residence time of 90 seconds and a screw speed of 300 revolutions / minute, discharged into a strand, cooled with water at a temperature of 25 ° C., and immediately cut to produce a copolymerized PPS chip. . The obtained chip was dried under reduced pressure at 180 ° C. for 3 hours, and then supplied to a full flight single screw extruder whose melting part was heated to 290 ° C.

  Next, after the polymer melted by the extruder is filtered through a 16 μm cut filter set at a temperature of 290 ° C., it is melt-extruded from a die of a T die set at a temperature of 290 ° C., and then an electrostatic charge is applied to a cast drum having a surface temperature of 25 ° C. Then, the obtained unstretched sheet was allowed to travel in contact with a plurality of heating rolls having a surface temperature of 94 ° C., and a 30 ° C. cooling roll having a different peripheral speed was provided next to the heating roll. The film was stretched 3.0 times in the longitudinal direction (MD direction). The uniaxially stretched sheet thus obtained was stretched 3.0 times (area stretch ratio 9.0 times) at a temperature of 95 ° C. in the longitudinal direction and the width direction (TD direction) using a tenter. The first heat setting was performed at 170 ° C. and the second heat setting was performed at 210 ° C. to prepare a biaxially oriented polyphenylene sulfide film having a thickness of 100 μm.

  The evaluation result of the obtained biaxially stretched film having a thickness of 100 μm is as shown in Table 1, and was a film excellent in adhesion durability with metal and moldability.

(Example 2)
A biaxially stretched polyphenylene sulfide film having a thickness of 100 μm was produced in the same manner as in Example 1 except that the second stage heat setting in Example 1 was set to 220 ° C.

  The evaluation result of the obtained biaxially stretched film having a thickness of 100 μm is as shown in Table 1, and was a film excellent in adhesion durability with metal and moldability.

(Example 3)
A biaxially stretched polyphenylene sulfide film having a thickness of 100 μm was produced in the same manner as in Example 1 except that the second-stage heat setting in Example 1 was 230 ° C.

  The evaluation result of the obtained biaxially stretched film having a thickness of 100 μm is as shown in Table 1, and was a film excellent in adhesion durability with metal and moldability.

Example 4
A biaxially stretched polyphenylene sulfide film having a thickness of 100 μm was produced in the same manner as in Example 1 except that the second stage heat setting in Example 1 was changed to 190 ° C.

  The evaluation result of the obtained biaxially stretched film having a thickness of 100 μm is as shown in Table 1, and was a film excellent in adhesion durability with metal and moldability.

(Example 5)
A biaxially stretched polyphenylene sulfide film having a thickness of 100 μm was produced in the same manner as in Example 1 except that the second stage heat setting in Example 1 was changed to 180 ° C.

  The evaluation result of the obtained biaxially stretched film having a thickness of 100 μm is as shown in Table 1, and was a film excellent in adhesion durability with metal and moldability.

(Example 6)
A biaxially stretched polyphenylene sulfide having a thickness of 100 μm was obtained in the same manner as in Example 1 except that the cast amount of the copolymerized PPS resin 1 was changed in Example 1 and the stretch ratio was 3.4 × 3.4. A film was prepared.

  The evaluation result of the obtained biaxially stretched film having a thickness of 100 μm is as shown in Table 1, and was a film excellent in adhesion durability with metal and moldability.

(Example 7)
A copolymerized PPS resin 1-1 was produced in the same manner as in Reference Example 1 except that 6 mol% of m-dichlorobenzene was used as the accessory component monomer. A biaxially stretched polyphenylene sulfide film having a thickness of 100 μm was produced in the same manner as in Example 1 using the copolymerized PPS resin 1-1 obtained above.

  The evaluation result of the obtained biaxially stretched film having a thickness of 100 μm is as shown in Table 1, and was a film excellent in adhesion durability with metal and moldability.

(Example 8)
A biaxially stretched polyphenylene sulfide film having a thickness of 100 μm was produced in the same manner as in Example 3 except that the first-stage heat setting in Example 3 was 230 ° C.

  The evaluation result of the obtained biaxially stretched film having a thickness of 100 μm is as shown in Table 1, and was a film excellent in adhesion durability with metal and moldability.

Example 9
A thickness of 100 μm was obtained in the same manner as in Example 1, except that 70 parts by mass of the copolymerized PPS resin 1 prepared in Reference Example 1 and 30 parts by mass of the copolymerized PPS resin 2 prepared in Reference Example 3 were blended. A biaxially stretched polyphenylene sulfide film was prepared. The viscosity of the blended raw material was 2000 poise.

  The evaluation result of the obtained biaxially stretched film having a thickness of 100 μm is as shown in Table 2, and was a film excellent in adhesion durability with metal and moldability.

(Example 10)
A biaxially stretched polyphenylene sulfide film having a thickness of 100 μm was produced in the same manner as in Example 9 except that the second stage heat setting in Example 9 was changed to 230 ° C.

  The evaluation result of the obtained biaxially stretched film having a thickness of 100 μm is as shown in Table 2, and was a film excellent in adhesion durability with metal and moldability.

Example 11
A biaxially stretched polyphenylene sulfide film having a thickness of 100 μm was produced in the same manner as in Example 10 except that the first-stage heat setting in Example 10 was 230 ° C.

  The evaluation result of the obtained biaxially stretched film having a thickness of 100 μm is as shown in Table 2, and was a film excellent in adhesion durability with metal and moldability.

(Comparative Example 1)
A biaxially stretched polyphenylene sulfide film having a thickness of 100 μm was produced in the same manner as in Example 1 except that the second-stage heat setting in Example 1 was 250 ° C.

  The evaluation results of the obtained biaxially stretched film having a thickness of 100 μm are as shown in Table 1, and the metal adhesiveness and formability deteriorated.

(Comparative Example 2)
An unstretched polyphenylene sulfide sheet was produced by setting the thickness of the unstretched sheet obtained in Example 1 to 100 μm.

  The evaluation results of the obtained unstretched sheet having a thickness of 100 μm are as shown in Table 1. Although the metal adhesion was excellent, the durability and formability were deteriorated.

(Comparative Example 3)
A biaxially stretched polyphenylene sulfide film having a thickness of 100 μm was prepared in the same manner as in Example 1 except that the single PPS resin of Reference Example 2 was used and the melting point was 285 ° C.

  The evaluation results of the obtained biaxially stretched film having a thickness of 100 μm are as shown in Table 1, and the metal adhesiveness and formability deteriorated.

(Comparative Example 4)
A biaxial film having a thickness of 100 μm was obtained in the same manner as in Example 1 except that the copolymerized PPS resin 1 prepared in Reference Example 1 was blended to 12 parts by mass and the PPS resin prepared in Reference Example 2 to 88 parts by mass. A stretched polyphenylene sulfide film was prepared.

  The evaluation results of the obtained biaxially stretched film having a thickness of 100 μm are as shown in Table 2, and the metal adhesiveness and formability deteriorated.

(Comparative Example 5)
A biaxially stretched polyphenylene sulfide film having a thickness of 100 μm was produced in the same manner as in Example 5 except that the PPS resin produced in Reference Example 2 was used.

  The evaluation results of the obtained biaxially stretched film having a thickness of 100 μm are as shown in Table 3, and the metal adhesiveness and formability deteriorated.

(Comparative Example 6)
A biaxially stretched polyphenylene sulfide film having a thickness of 100 μm was produced in the same manner as in Example 3 except that the PPS resin produced in Reference Example 2 was used.

  The evaluation results of the obtained biaxially stretched film having a thickness of 100 μm are as shown in Table 3, and the metal adhesiveness and formability deteriorated.

  Since the biaxially stretched polyarylene sulfide film for metal bonding of the present invention is excellent in adhesion to metal and adhesion durability, it can be suitably used as a metal sealing material for various parts.

Claims (6)

A biaxially stretched polyarylene sulfide film for metal bonding comprising a polyarylene sulfide having a melting point of 260 ° C. or less and a crystallinity of 10% or more and 30% or less. The biaxially stretched polyarylene sulfide film for metal bonding according to claim 1, wherein the Young's modulus of the film is 2.5 GPa or more and 3.5 GPa or less. 2. The biaxially stretched polyarylene sulfide film for metal bonding according to claim 1, wherein the polyarylene sulfide is a polyarylene sulfide containing 5 to 15 mol% of m-phenylene sulfide units. 2. The biaxially stretched polyarylene sulfide film for metal bonding according to claim 1, wherein the film has a 200 ° C. breaking elongation of 150% or more. 2. The biaxially stretched polyarylene sulfide film for metal bonding according to claim 1, comprising two or more types of PPS having different melting points of the polyarylene sulfide. The biaxially stretched polyarylene sulfide film for metal bonding according to claim 1, wherein the polyarylene sulfide has a melt viscosity of 200 to 10,000 poise.