JP2013139532A - Polyarylene sulfide film - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyarylene sulfide film capable of being made as a film stably even if having a large thickness.SOLUTION: The polyarylene sulfide film is composed of a polyarylene sulfide resin composition containing: 100 pts.wt. of a polyarylene sulfide resin; and 1 to 20 pts.wt. of a siloxane-modified polyetherimide resin, wherein the melt crystallization temperature (Tmc)(°C) of the polyarylene sulfide resin composition and the melt crystallization temperature (Tmc')(°C) of the polyarylene sulfide resin before the siloxane-modified polyetherimide resin is blended have a relation of (Tmc-Tmc')≤-5(°C).

Description

  The present invention relates to electric insulating materials and molding materials such as motors, transformers, and insulated cables, circuit board materials, process / release films and protective films for circuits and optical members, lithium ion battery materials, fuel cell materials, speaker diaphragms The present invention relates to a polyarylene sulfide film that can be preferably used for, for example.

  Polyarylene sulfide films represented by polyphenylene sulfide films (hereinafter abbreviated as PPS films) are excellent in heat resistance, hydrolysis resistance, flame resistance, chemical resistance, electrical insulation, etc. It is suitably used for electrical / electronic equipment parts, machine parts, automobile parts and the like that require durability.

  However, since the polyarylene sulfide resin has a feature that the crystallization in the cooling process from the molten state is faster than the polyester resin or the like, for example, a thick biaxial film having a thickness after biaxial stretching of 150 μm or more. When the stretched polyarylene sulfide film is collected, cooling spots in the thickness direction are generated in the extrusion casting process, and subsequent stretching is not performed uniformly. As a result, there is a problem that tearing frequently occurs during stretching.

  The polyarylene sulfide film is also suitably used as a release film. However, when an unstretched polyarylene sulfide film is used at a high temperature exceeding 140 ° C., thermal crystallization proceeds rapidly. In some cases, the film was not easily used when it was peeled off.

  As described above, polyarylene sulfide films have a problem of rapid crystallization due to cooling from a molten state or heating from room temperature, and development of a PPS film in which crystallization is suppressed is strongly desired. It was. As a method for modifying various physical properties of the polyarylene sulfide film, for example, a method of alloying a polyetherimide resin (Patent Documents 1 and 2) is known, but studies focusing on crystallization behavior have been made. The problem has not been solved.

JP 2001-261959 A International Publication No. 2007/129721 Pamphlet

  The object of the present invention is to solve the above-mentioned conventional problems and provide a polyarylene sulfide film that has good stretchability even when the thickness is large, and that can withstand use as a release film even with an unstretched film. There is to do.

  In the present invention, it has been found that the crystallization of the PPS film can be suppressed by alloying the siloxane-modified polyetherimide resin with respect to the polyarylene sulfide resin, and thus the above-mentioned problems have been solved.

  That is, a polyarylene sulfide film comprising a polyarylene sulfide resin composition containing 1 to 20 parts by weight of a siloxane-modified polyetherimide resin with respect to 100 parts by weight of a polyarylene sulfide resin, wherein the polyarylene sulfide resin composition is melted The crystallization temperature (Tmc) (° C.) and the melt crystallization temperature (Tmc ′) (° C.) of the polyarylene sulfide resin before containing the siloxane-modified polyetherimide resin are (Tmc−Tmc ′) ≦ −5 (° C.) It is a biaxially oriented polyarylene sulfide film characterized by having a relationship.

  According to the present invention, it is possible to provide a polyarylene sulfide film having good film forming stability and uniform stretchability even when the film thickness is increased. In addition, since the unstretched polyarylene sulfide film obtained by the present invention is suppressed in crystallization even when heated to a high temperature, embrittlement due to crystallization hardly occurs even when used as a release film.

  The present invention will be described below.

Polyarylene sulfide resin The polyarylene sulfide resin used in the present invention is a homopolymer or copolymer having a repeating unit of-(Ar-S)-as a main constituent unit, preferably containing 80 mol% or more of the repeating unit. Ar is a group containing an aromatic ring in which a bond is present in an aromatic ring, and examples thereof include divalent repeating units represented by the following formulas (A) to (L), among which a formula ( The repeating unit represented by A) is particularly preferred.

(In the formula, R1 and R2 are substituents selected from hydrogen, an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms and a halogen group, and R1 and R2 are the same or different. May be good.)
As long as this repeating unit is a main structural unit, it can contain a small amount of branching units or crosslinking units represented by the following formulas (M) to (P). The amount of copolymerization of these branched units or cross-linked units is preferably in the range of 0 to 5 mol%, preferably in the range of 0 to 1 mol%, with respect to 1 mol of-(Ar-S)-units. More preferred.

  Further, the polyarylene sulfide resin used in the present invention may be any of a random copolymer having the above repeating unit, a block copolymer, and a mixture thereof.

  In the present invention, the melt viscosity of the polyarylene sulfide resin is not particularly limited, but may be in the range of 100 to 2,000 Pa · s at a temperature of 310 ° C. and a shear rate of 1,000 (1 / sec). Preferably, it is in the range of 200 to 1,000 Pa · s.

  Typical examples of these polyarylene sulfide resins include polyphenylene sulfide (hereinafter sometimes abbreviated as PPS), polyphenylene sulfide sulfone, polyphenylene sulfide ketone, random copolymers, block copolymers, and mixtures thereof. Can be mentioned. As a particularly preferred polyarylene sulfide resin, the p-phenylene sulfide unit represented by the following formula (Q) is preferably 80 mol% or more, more preferably 85 mol%, still more preferably 90 mol% or more as the main structural unit of the polymer. Examples thereof include polyphenylene sulfide. If the p-phenylene sulfide unit is less than 80 mol%, the crystallinity and thermal transition temperature of the polymer are low, and the heat resistance, dimensional stability, mechanical properties, etc. that are characteristic of the polyarylene sulfide resin may be impaired.

  The method for producing the polyarylene sulfide resin is not particularly limited. For example, as disclosed in JP-A-3-74433 and JP-A-2002-332351, the polyarylene sulfide resin is treated with an aqueous solution containing an alkaline earth metal such as Ca. It is preferable to include a step in order to reduce the crystallization rate of polyarylene sulfide. The polyarylene sulfide resin containing a group having an aromatic ring other than a phenylene group can be obtained by using a monomer in which the phenylene group is replaced with an aromatic ring other than the phenylene group.

  As long as the polyarylene sulfide resin used in the present invention is within the range not impairing the characteristics of the present invention, crosslinking / high molecular weight by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or reduced pressure, an organic solvent, It can also be used after various treatments such as washing with hot water and aqueous acid solution, activation with functional group-containing compounds such as acid anhydrides, amines, isocyanates and functional disulfide compounds.

Siloxane-modified polyetherimide resin The siloxane-modified polyetherimide resin used in the present invention is a copolymer having a repeating unit represented by the following formula (R). The mode of copolymerization is not particularly limited, but is preferably an alternating copolymer or a block copolymer.

  In formula (R), R3 is an arylene group or a bis (alkyldimethylsiloxane) group represented by the following formula (S). The arylene group is preferably selected from the group consisting of an m-phenylene group and a p-phenylene group. However, not all R3 in the copolymer is an arylene group. In the bis (alkyldimethylsiloxane) group represented by the formula (S), the average number of repeating units x of siloxane units in the siloxane-modified polyetherimide resin is preferably 5 to 50, and more preferably 8 to 12. . Moreover, it is preferable that the repeating number y of an alkyl group is 2-10, and what is 3 is the most preferable. The molar ratio of the repeating unit (repeating unit A) in which R3 is an arylene group in formula (R) and the repeating unit (repeating unit B) in which R3 is a group represented by formula (S) in formula (R) Is preferably repeating unit A: repeating unit B = 10: 90 to 90:10, more preferably 40:60 to 60:40.

  As the siloxane-modified polyetherimide resin as described above, for example, several grades are commercially available from SABIC Innovative Plastics under the trademark SILTEM, and these can be preferably used.

Polyarylene sulfide resin composition The polyarylene sulfide resin composition used in the present invention is a polyarylene sulfide resin composition containing 1 to 20 parts by weight of the siloxane-modified polyetherimide resin with respect to 100 parts by weight of the polyarylene sulfide resin. It is a thing. If the content of the siloxane-modified polyetherimide resin is less than 1 part by weight relative to 100 parts by weight of the polyarylene sulfide resin, a sufficient crystallization suppression effect cannot be obtained. On the other hand, when the blending amount of the siloxane-modified polyetherimide resin exceeds 20 parts by weight with respect to 100 parts by weight of the polyarylene sulfide resin, the original stretchability of the polyarylene sulfide resin is inhibited and stable film formation cannot be performed. Therefore, the addition of the siloxane-modified polyetherimide resin is performed in the range of 1 to 20 parts by weight with respect to 100 parts by weight of the polyarylene sulfide resin, and the addition amount of the polyarylene sulfide resin is preferably 3 to 15 parts by weight, more preferably 5 to 10 parts by weight. It is desirable that the polyarylene sulfide resin and the siloxane-modified polyetherimide resin are compatible.

  The polyarylene sulfide resin composition 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, a wax and the like within a range that does not impair the object of the present invention. Other ingredients may be added. In addition, a small amount of resin other than polyarylene sulfide resin and siloxane-modified polyetherimide resin may be contained as long as the object of the present invention is not impaired. In addition, inorganic particles, organic particles, and the like can be added to impart easy slipping, abrasion resistance, scratch resistance, and the like to the film surface after film formation. 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 present invention, the time when the siloxane-modified polyetherimide resin is mixed with the polyarylene sulfide resin is not particularly limited. However, prior to melt extrusion, the polyarylene sulfide resin and the siloxane-modified polyetherimide resin are pre-melted and kneaded (pelletized). There are a method of forming a master chip and a method of mixing and melt-kneading during melt extrusion. Of these, a method of pre-kneading into a master chip using a high-shear mixer with high shear stress such as a twin screw extruder is preferably exemplified. In that case, it is preferable to prepare a blend raw material in which the weight fraction of the polyarylene sulfide resin and the siloxane-modified polyetherimide resin is 99/1 to 60/40. When mixing with a twin screw extruder, from the viewpoint of reducing poor dispersion, a screw equipped with a triple twin screw type or a double twin screw type is preferable. In the kneading part, the melting temperature of the polyarylene sulfide resin is Tm. In this case, a resin temperature range of Tm + 5 to Tm + 70 (° C.) is preferable in order to improve dispersibility during kneading. Also, there is no particular limitation on the mixing order of the raw materials, and a method in which the polyarylene sulfide resin, the siloxane-modified polyetherimide resin and other additives as necessary are dry-blended in a lump and then melt-kneaded by the above-described method or the like. Alternatively, two or three of the polyarylene sulfide resin, the siloxane-modified polyetherimide resin and other additives as required are dry blended and melt-kneaded, and the remaining one or two are melt-kneaded. The method of doing is mentioned.

  In the present invention, the melt crystallization temperature (Tmc) (° C.) of the polyarylene sulfide resin composition is the melt crystallization temperature (Tmc ′) (° C.) of the polyarylene sulfide resin before containing the siloxane-modified polyetherimide resin. It is important that it is 5 ° C. or more lower than That is, the melt crystallization temperature (Tmc) (° C.) of the polyarylene sulfide resin composition and the melt crystallization temperature (Tmc ′) (° C.) of the polyarylene sulfide resin before blending the siloxane-modified polyetherimide resin are ( Tmc−Tmc ′) ≦ −5 (° C.) is preferable. More preferably, (Tmc−Tmc ′) ≦ −10 (° C.). When (Tmc−Tmc ′)> − 5 (° C.), the cooling caused by the difference in the cooling rate between the cast contact surface and the non-contact surface during cast cooling after extrusion due to the high melt crystallization temperature of the resin composition Spots are likely to occur, and film breakage may occur in the stretching process. In particular, when the film is thick, cooling spots are likely to occur, and tearing during film formation may occur frequently. The melt crystallization temperature is measured by the measuring method described in the section of the examples.

Method for producing polyarylene sulfide film Next, the method for producing the polyarylene sulfide film of the present invention will be described by exemplifying the case of biaxial stretching. However, the present invention is limited and interpreted by the following description. is not.

  The polyarylene sulfide resin composition pellets obtained by the above-mentioned method are appropriately mixed with a polyarylene sulfide resin at a certain ratio as necessary, and vacuum-dried at 180 ° C. for 3 hours or more. It puts into the extruder heated at 280-330 degreeC, Preferably it is 290-310 degreeC. Thereafter, the molten polymer passed through the extruder is passed through a filter, and the molten polymer is discharged into a sheet form using a die of a T die. The set temperature of the filter part and the die is preferably 3 to 20 ° C higher than the temperature of the melting part of the extruder, more preferably 5 to 15 ° C. This sheet-like material is closely adhered to a cooling drum having a surface temperature of 10 to 70 ° C. to be cooled and solidified to obtain a substantially unoriented film. The thickness of the unstretched film is not particularly limited, but is preferably 500 μm or more, more preferably 600 μm or more in order to exhibit the effect of suppressing crystallization more remarkably.

  Next, this unstretched film is biaxially stretched and biaxially oriented. 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). A method of stretching simultaneously) or a method of combining them can be used. Here, an example using a sequential biaxial stretching method in which stretching in the longitudinal direction first and then in the width direction will be described.

  After heating an unstretched polyphenylene sulfide film with a heated roll group, it is 2.5 to 4.5 times in the longitudinal direction (MD direction), preferably 3.0 to 4.0 times in one or more stages. Stretch (MD stretching). The stretching temperature is preferably 70 to 130 ° C, more preferably 80 to 110 ° 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 70 to 130 ° C, more preferably 80 to 110 ° C. The draw ratio is in the range of 2.5 to 4.5 times, preferably 3.0 to 4.0 times.

  Next, this biaxially stretched film is heat-treated under tension. The heat treatment temperature is preferably in the range of 160 to 280 ° C., and the heat treatment is performed in one or more stages. At this time, it is preferable in terms of thermal dimensional stability that the relaxation treatment is performed in the range of 0 to 10% in the film width direction at the heat treatment temperature. After the heat treatment, the film is cooled to room temperature.

The physical property value measurement method and the effect evaluation method are as follows.
(1) Glass transition temperature of resin It measured according to JIS K7121-1987. Using a differential scanning calorimeter DSC (RDC220) manufactured by Seiko Instruments Inc. and a disk station (SSC / 5200) manufactured by Seiko Instruments Inc. as a data analysis device, 5 mg of the sample was melted and held at 350 ° C. for 5 minutes on an aluminum tray, and rapidly cooled and solidified. The temperature was raised from room temperature at a heating rate of 20 ° C./min. The glass transition temperature (Tg) was calculated by the following formula.
Glass transition temperature = (extrapolated glass transition start temperature + extrapolated glass transition end temperature) / 2
(2) Melting temperature of resin In the same manner as in (1) above, a differential scanning calorimeter DSC (RDC220) manufactured by Seiko Instruments Inc. is used according to JIS K7121-1987, and a disk station (SSC / 5200) manufactured by the same company is used as a data analyzer. Then, 5 mg of the sample was heated from room temperature to 340 ° C. at a heating rate of 20 ° C./min on an aluminum tray, melted and held at 340 ° C. for 5 minutes, rapidly solidified and held for 5 minutes, and then heated from room temperature. The temperature was raised at a rate of 20 ° C./min. At that time, the peak temperature of the endothermic peak of melting observed was defined as the melting temperature (Tm).
(3) Melt crystallization temperature of resin and resin composition In the same manner as in (2) above, a differential scanning calorimeter DSC (RDC220) manufactured by Seiko Instruments in accordance with JIS K7121-1987, a disk station manufactured by the same company as a data analyzer ( Using SSC / 5200), 5 mg of the sample was heated from room temperature to 340 ° C. at a heating rate of 20 ° C./min on an aluminum pan, melted and held at 340 ° C. for 5 minutes, rapidly solidified and held for 5 minutes. Thereafter, the temperature was raised again from room temperature at a heating rate of 20 ° C./min, and melted and held at 340 ° C. for 5 minutes. Thereafter, the peak temperature of the crystallization exothermic peak observed when cooling from 340 ° C. to room temperature at 20 ° C./min was defined as the melt crystallization temperature. Melt crystallization temperature (Tmc ') of polyarylene sulfide resin before blending siloxane-modified polyetherimide resin by this method, melt crystallization temperature of polyarylene sulfide resin composition after blending siloxane-modified polyetherimide resin (Tmc) was measured respectively.

Further, the change in the melt crystallization temperature due to the inclusion of the siloxane-modified polyetherimide resin with respect to the polyarylene sulfide resin is represented by a value of Tmc-Tmc ′, and when the sign of the value is positive, the siloxane-modified polyetherimide It shows that Tmc increases due to the blending of the resin. When the sign is negative, it indicates that Tmc decreases due to the inclusion of the siloxane-modified polyetherimide resin.
(4) Film-forming stability Film-forming stability at the time of biaxial stretching film formation was determined based on the following criteria by performing continuous film formation over a total time of 24 hours using the obtained polyarylene sulfide resin composition. .

○: No film break
Δ: Film tear 1 to 5 times ×: Film tear 6 times or more (5) Uniform stretchability In the middle of film formation, press the film so that a circular stamp with a diameter of 1 cm is spread over the entire surface of the unstretched film, and then stretched film An arbitrary 200 stamp traces were selected. At this time, selection was made without deviation from a range of 50 cm in width and 5 m in length. For each of the selected 200 stamp marks, the diameter of the longest portion in the width direction was measured with a caliper, and the standard deviation of the 200 data was obtained. The uniform stretchability of the film was determined based on the following criteria.

○: Standard deviation is less than 0.2 Δ: Standard deviation is 0.2 to 0.5
X: The standard deviation exceeds 0.5.

(Reference Example 1)
Preparation of polyphenylene sulfide resin (PPS-1) In an autoclave, 9.44 kg (80 mol) of 47% sodium hydrosulfide, 3.43 kg (82.4 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone (NMP) ) 13.0 kg (131 mol), 2.86 kg (34.9 mol) of sodium acetate, and 12 kg of ion-exchanged water, gradually heated to 235 ° C. over about 3 hours while passing nitrogen at normal pressure, After distilling 0.0 kg and 0.3 kg (3.23 mol) of NMP, the reaction vessel was cooled to 160 ° C. The amount of hydrogen sulfide scattered was 2 mol.
Next, 11.5 kg (78.4 mol) of p-dichlorobenzene (p-DCB) as a main monomer and 0.007 kg (0.04 mol) of 1,2,4-trichlorobenzene as a secondary component monomer were added, 22.2 kg (223 mol) of NMP was additionally added, the reaction vessel was sealed under nitrogen gas, and the temperature was increased from 200 ° C. to 270 ° C. at a rate of 0.6 ° C./min while stirring at 400 rpm. After 30 minutes at 270 ° C., 1.11 kg (61.6 mol) of water was injected into the system over 10 minutes, and the reaction was further continued at 270 ° C. for 100 minutes. Thereafter, 1.60 kg (88.8 mol) of water was again injected into the system, cooled to 240 ° C., then cooled to 210 ° C. at a rate of 0.4 ° C./min, and then rapidly cooled to near room temperature. The contents were taken out, diluted with 32 liters of NMP, and the solvent and solid matter were filtered off with a sieve (80 mesh). The resulting particles were washed again at 85 ° C. with 38 liters of NMP. Thereafter, it was washed 5 times with 67 liters of warm water and filtered, washed 5 times with 70,000 g of 0.05 wt% aqueous calcium acetate solution and filtered to obtain PPS polymer particles. This was dried in hot air at 60 ° C. and dried under reduced pressure at 120 ° C. for 20 hours to obtain white polyphenylene sulfide powder. The obtained polyphenylene sulfide resin had a glass transition temperature of 91 ° C., a melting point of 280 ° C., and a melt crystallization temperature of 188 ° C.

(Reference Example 2)
Preparation of Metaphenylene Sulfide Copolymer Polyphenylene Sulfide Resin (PPS-2) 70.6 mol of p-dichlorobenzene as the main monomer, 7.8 mol of m-dichlorobenzene as the accessory monomer, and 0.04 mol of 1, A polyphenylene sulfide resin was produced in the same manner as in Reference Example 1 except that 2,4-trichlorobenzene was used. The obtained polyphenylene sulfide resin had a glass transition temperature of 85 ° C., a melting point of 251 ° C., and a melt crystallization temperature of 150 ° C.

(Example 1)
70 parts by weight of the polyphenylene sulfide resin obtained in Reference Example 1 and 30 parts by weight of a siloxane-modified polyetherimide resin (Siltem 1700 manufactured by SABIC Innovative Plastics) were blended, dried at 180 ° C. under reduced pressure for 3 hours, and then kneaded. It is put into a co-rotating twin-screw kneading extruder with a vacuum vent provided with three paddle kneading parts (manufactured by Nippon Steel Works, screw diameter 30 mm, screw length / screw diameter = 45.5), and the residence time is 90 seconds. The melt was extruded at 330 ° C. at a screw rotation speed of 300 rpm and discharged into a strand shape, cooled with water at a temperature of 25 ° C., and then immediately cut to produce a blend chip.

  The resulting polyphenylene sulfide / siloxane-modified polyetherimide (70/30 parts by weight) blend chip and the polyphenylene sulfide resin prepared in Reference Example 1 were blended at a blending ratio of 16:84 and dried under reduced pressure at 180 ° C. for 3 hours. The melted portion was supplied to a full flight single screw extruder heated to 320 ° C., filtered through a filter set at a temperature of 330 ° C., melt-extruded from a T die die set at a temperature of 320 ° C., and surface temperature 25 While applying an electrostatic charge to a cast drum at 0 ° C., it was closely cooled and solidified to produce an unstretched film. The obtained film had a glass transition temperature of 91 ° C., a melting point of 280 ° C., and a melt crystallization temperature of 167 ° C.

  This unstretched film is 3.3 times in the longitudinal direction of the film at a film temperature of 104 ° C. using a difference in peripheral speed of the roll after preheating using a longitudinal stretching machine composed of a plurality of heated roll groups. Stretched at a magnification. Thereafter, both ends of the film are gripped with a clip, guided to a tenter, stretched in the width direction of the film at a stretching temperature of 100 ° C. and a stretching ratio of 3.5 times, and subsequently heat treated at a temperature of 280 ° C. for 10 seconds. It was. During the heat treatment, a relaxation treatment of 5% was performed in the film width direction. After the film was cooled to room temperature, the film edge was removed to prepare a biaxially oriented polyphenylene sulfide film having a thickness of 200 μm.

  The measurement and evaluation results for the configuration and properties of the obtained biaxially oriented polyphenylene sulfide film are as shown in Table 1. This biaxially oriented polyphenylene sulfide film has almost no film breakage during film formation, and is stable. A film could be formed.

(Example 2)
Biaxially oriented polyphenylene sulfide in the same manner as in Example 1 except that the blend ratio of polyphenylene sulfide / siloxane modified polyetherimide (70/30 parts by weight) and polyphenylene sulfide resin was 3:97 in Example 1. A film was prepared. The measurement and evaluation results on the configuration and properties of the obtained biaxially oriented polyphenylene sulfide film are as shown in Table 1. This biaxially oriented polyphenylene sulfide film was excellent in film formation stability. .

(Example 3)
A biaxially oriented polyphenylene sulfide film was prepared in the same manner as in Example 1 except that Siltem 1600 manufactured by SABIC Innovative Plastics was used as the siloxane-modified polyetherimide resin in Example 1. The measurement and evaluation results on the configuration and properties of the obtained biaxially oriented polyphenylene sulfide film are as shown in Table 1. This biaxially oriented polyphenylene sulfide film was excellent in film formation stability. .

Example 4
A biaxially oriented polyphenylene sulfide film was produced in the same manner as in Example 1 except that the metacopolymerized polyphenylene sulfide resin (PPS-2) produced in Reference Example 2 was used as the polyphenylene sulfide resin in Example 1. The measurement and evaluation results on the configuration and properties of the obtained biaxially oriented polyphenylene sulfide film are as shown in Table 1. This biaxially oriented polyphenylene sulfide film was excellent in film formation stability. .

(Comparative Example 1)
A biaxially oriented polyphenylene sulfide film was produced in the same manner as in Example 1 except that the polyphenylene sulfide resin was used without blending the siloxane-modified polyetherimide resin in Example 1. The measurement and evaluation results for the configuration and properties of the obtained biaxially oriented polyphenylene sulfide film are as shown in Table 1. This biaxially oriented polyphenylene sulfide film is frequently broken and stable during film formation. The film could not be continuously formed.

(Comparative Example 2)
A biaxially oriented polyphenylene sulfide was prepared in the same manner as in Example 1 except that a siloxane-modified polyetherimide resin (Ultem 1010A manufactured by SABIC Innovative Plastics) was used instead of the siloxane-modified polyetherimide resin in Example 1. A film was prepared. The measurement and evaluation results for the configuration and properties of the obtained biaxially oriented polyphenylene sulfide film are as shown in Table 1. This biaxially oriented polyphenylene sulfide film is frequently broken and stable during film formation. The film could not be continuously formed.

  The polyarylene sulfide film of the present invention has few stretch spots even if it is a thick material, and is an electrical insulating material such as a motor, a transformer, an insulated cable, a molding material, a circuit board material, a process / release material such as a circuit / optical member, etc. In various industrial material applications such as lithium ion battery materials, fuel cell materials, speaker diaphragms, etc., they can be suitably used.

Claims (2)

A polyarylene sulfide film comprising a polyarylene sulfide resin composition containing 1 to 20 parts by weight of a siloxane-modified polyetherimide resin with respect to 100 parts by weight of a polyarylene sulfide resin, the molten crystal of the polyarylene sulfide resin composition Relationship between the crystallization temperature (Tmc) (° C.) and the melt crystallization temperature (Tmc ′) (° C.) of the polyarylene sulfide resin before containing the siloxane-modified polyetherimide resin is (Tmc−Tmc ′) ≦ −5 (° C.) A polyarylene sulfide film characterized by the above. The melt crystallization temperature (Tmc) (° C.) of the polyarylene sulfide resin composition and the melt crystallization temperature (Tmc ′) (° C.) of the polyarylene sulfide resin before blending the siloxane-modified polyetherimide resin are (Tmc). The polyarylene sulfide film according to claim 1, wherein the relationship is −Tmc ′) ≦ −10 (° C.).