JP2020090613A - Polyarylene sulfide film - Google Patents

Abstract

To provide a polyarylene sulfide film having both of high electrical insulation properties and high thermal resistance.SOLUTION: A polyarylene sulfide film has a polyarylene-sulfide-based resin (A) as a main constituent, and contains inorganic particles (α) mainly constituted by metalloid or base metal oxide and with an average primary particle size of 5 nm or more and 150 nm or less, and has an orientation parameter of 2 or more.SELECTED DRAWING: None

Description

The present invention relates to a polyarylene sulfide film having excellent heat resistance/electrical insulation/mechanical properties.

Polyarylene sulfide (hereinafter sometimes abbreviated as PPS) film has excellent properties as an engineered plastic such as excellent heat resistance, electrical insulation, and moist heat resistance. Therefore, a capacitor dielectric, a copper-clad laminate, It is widely used in flexible printed circuit boards, electronic parts such as insulating tape, and automobile parts such as motor insulators. However, in recent years, electronic devices have been downsized and their capacities have increased, and due to an increase in electric power to be handled and an increase in generated heat, a higher electrical insulation property and heat resistance are desired for PPS films.

Here, Patent Document 1 proposes a resin composition containing magnesium hydroxide, glass fibers and a PPS resin in syndiotactic polystyrene for the purpose of improving flame retardancy. Further, Patent Document 2 proposes a biaxially stretched PPS film in which the content of a sodium metal element is set to a specific amount or less and an antioxidant is added to improve electric insulation. However, it has been difficult to achieve a PPS film that achieves both electrical insulation and a low coefficient of thermal expansion simply by combining the above.

JP, 2010-260963, A JP, 2005-74725, A

The present invention is to provide a PPS film that can be suitably used for capacitors, insulating tapes and motor insulation, and that has both high electrical insulation and high heat resistance.

The film of the present invention has the following constitution in order to solve the above problems. That is,
[I] Orientation containing polyarylene sulfide resin (A) as a main constituent, inorganic particles (α) having a semimetal or base metal oxide as a main constituent and an average primary particle diameter of 5 nm or more and 150 nm or less A polyarylene sulfide film having a parameter of 2 or more.
[Ii] The polyarylene sulfide film according to [i], wherein the content of the inorganic particles (α) is 0.01% by volume or more and 5% by volume or less. [iii] The inorganic particles (α) include a metalloyl group, an epoxy group, and an amino group. The polyarylene sulfide film according to [i] or [ii], which is treated with a silane coupling agent having any of a group and an isocyanate group.
[Iv] The polyarylene sulfide film according to any one of [i] to [iii], which has a porosity of 5% by volume or less.
[V] The thickness of the film is T (μm), the content of the inorganic particles (α) in the range from the surface of the film to the thickness 0.1T is Vfa (volume %), and the thickness 0.1T to the thickness 0. Vfα/Vfα satisfying 0≦Vfa/Vfα<1 of at least one surface, when the content of the inorganic particles (α) in the range of up to 0.9 T is Vfα (volume %), [i] to [iv] The polyarylene sulfide film according to any one of claims.
[Vi] The polyarylene sulfide film according to any one of [i] to [v], which has the highest glass transition temperature of 200° C. or higher in DSC measurement [vii] a thermoplastic resin different from the resin (A) ( The polyarylene sulfide film according to any one of [i] to [vi], which has a layer (Pa layer) containing B), and the thermoplastic resin (B) has any of the following chemical formulas.

(However, each of R _{1 to} R ₆ in the formula is any of H, OH, a methoxy group, an ethoxy group, a trifluoromethyl group, an aliphatic group having 1 to 13 carbon atoms, and an aromatic group having 6 to 10 carbon atoms. It is.)
[Viii] The polyarylene sulfide film according to [vii], wherein the Pa layer is a layer in which the thermoplastic resin (B) is present as a dispersed phase in the polyarylene sulfide resin (A).
[Ix] The polyarylene sulfide film according to any one of [vii] to [viii], wherein the thermoplastic resin (B) has a sulfonyl group.
[X] The total of the content WA1 (volume%) of the polyarylene sulfide resin (A) in the Pa layer and the content WB1 (volume%) of the thermoplastic resin (B) different from the resin (A) is 100% by weight. The polyarylene sulfide film according to any one of [vii] to [ix], in which the content WB1 of the thermoplastic resin (B) is 0.1 volume% or more and less than 50 volume% when it is defined as parts.
[Xi] The polyarylene sulfide film according to any one of [vii] to [x], wherein the ratio of the major axis to the minor axis in the dispersion diameter of the thermoplastic resin (B) is 1.05 or more.

According to the present invention, it is possible to provide a polyarylene sulfide film having both high electrical insulation and high heat resistance. In particular, it can be suitably used for automobile parts such as electronic parts such as motor/rotor insulators, capacitor dielectrics, copper-clad laminates, flexible printed boards, and insulating tapes.

The polyarylene sulfide film of the present invention will be described in detail below with reference to specific examples.
The polyarylene sulfide film of the present invention comprises the polyarylene sulfide resin (A) as a main constituent component, the semi-metal or base metal oxide as a main component, and the inorganic particles having an average primary particle diameter of 5 nm or more and 150 nm or less ( α) and the orientation parameter is 2 or more. Here, the main constituent component means that it accounts for 50% by mass or more of the raw materials constituting the film. The term “main component” means that the oxide of a semimetal or a base metal accounts for 50% by mass or more. With the above structure, when the polyarylene sulfide film is exposed to high temperature, the inorganic particles (α) trap radicals generated by thermal decomposition of the polyarylene sulfide resin (A), It is possible to suppress reactions that cause thermal deterioration of the polyarylene sulfide resin (A) such as thermal decomposition reaction and oxidative crosslinking reaction, and as a result, it is possible to obtain a polyarylene sulfide film having high heat resistance. It was done.
Further, the polyarylene sulfide film of the present invention not only suppresses the reaction that causes the thermal deterioration of PPS by suppressing the mobility of the molecular chain by setting the orientation parameter to 2 or more, but also with time. By suppressing the structural change of, higher heat resistance can be imparted. The orientation parameter here is obtained by the Raman method described later. The orientation parameter is more preferably 4 or more, still more preferably 6 or more. The upper limit of the orientation parameter is not particularly limited, but is substantially 15 or less. In the polyarylene sulfide film of the present invention, in order to obtain the degree of orientation of 2 or more, it can be obtained by forming the film under the following raw materials and conditions.
The polyarylene sulfide-based resin (A) in the polyarylene sulfide film of the present invention has a repeating unit of —(Ar—S)— as a main constituent unit, and preferably a homopolymer or copolymer containing 80 mol% or more of the repeating unit. Is. Ar is a group containing an aromatic ring having a bond in an aromatic ring, and is exemplified by divalent repeating units represented by the following formulas (V) to (XVI) and the like. The repeating unit represented by V) is particularly preferable.

(However, R1 and R2 in the formula 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 may be the same or different. Good too.)
As long as this repeating unit is the main constitutional unit, it can contain a small amount of branching units or crosslinking units represented by the following formulas (XIX) to (XX). The copolymerization amount of these branching units or crosslinking units is preferably in the range of 0 mol% or more and 5 mol% or less, and 0 mol% or more and 1 mol% or less with respect to 1 mol of the -(Ar-S)- unit. The range is more preferably.

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

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

Typical examples of these polyarylene sulfide resins (A) include polyphenylene sulfide resins, polyphenylene sulfide sulfone resins, polyphenylene sulfide ketone resins, random copolymers thereof, block copolymers and mixtures thereof. Can be mentioned. As a particularly preferred polyarylene sulfide resin (A), a p-phenylene sulfide unit represented by the following formula (XXI) as a main constitutional unit of the polymer is preferably 80 mol% or more, more preferably 85 mol%, and further preferably Examples thereof include polyphenylene sulfide-based resin containing 90 mol% or more. When 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., which are features of the polyarylene sulfide resin (A), are impaired. There is.

The method for producing the polyarylene sulfide resin (A) is not particularly limited, but contains an alkaline earth metal such as Ca as disclosed in, for example, JP-A-3-74433 and JP-A-2002-332351. It is preferable to include a step of treating with an aqueous solution in order to reduce the crystallization rate of polyarylene sulfide. The polyarylene sulfide-based resin (A) containing a group having an aromatic ring other than the 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.

The polyarylene sulfide-based resin (A) used in the polyarylene sulfide film of the present invention is, as long as the characteristics of the present invention are not impaired, cross-linked/polymerized by heating in air, in an inert gas atmosphere such as nitrogen or After various treatments such as heat treatment under reduced pressure, washing with organic solvents, hot water and aqueous acid solutions, activation with functional group-containing compounds such as acid anhydrides, amines, isocyanates and functional group disulfide compounds. It is also possible to use.

The polyarylene sulfide film of the present invention needs to contain inorganic particles (α) containing a semimetal or base metal oxide as a main component and having an average primary particle diameter of 5 nm or more and 150 nm or less. The semimetal here is selected from the group consisting of boron, silicon, germanium, arsenic, antimony, tellurium, and anstatin. Further, the base metal is selected from the group consisting of aluminum, gallium, indium, tin, thallium, lead, bismuth, boronium, and fullerobium. More preferably, it is composed of a semimetal, and particularly preferably is silicon. In addition, the main component means that the above-mentioned oxide of a semimetal or a base metal accounts for 50% by mass or more as a substance constituting the inorganic particles (α). These have the ability to trap radicals generated by thermal decomposition of the polyarylene sulfide-based resin (A), but particularly as in the present invention, the average primary particle size of the inorganic particles (α) is 5 nm or more and 150 nm or less. When the content is in the range, the polyarylene sulfide resin (A) can be contacted with high efficiency, and as a result, the radical trapping ability is further increased, and the heat resistance can be improved. As a result, even if added in a small amount, high heat resistance can be obtained, so that the mechanical properties of the film also become high. If the average primary particle size of the inorganic particles (α) is less than 5 nm, the dispersibility in the polyarylene sulfide resin (A) is reduced and the particles are present as coarse aggregates in the film, resulting in poor mechanical properties. On the other hand, when it exceeds 150 nm, the contact efficiency between the inorganic particles (α) and the polyarylene sulfide resin (A) is lowered, the efficiency of radical trap is lowered and the heat resistance is lowered. It is more preferably 10 nm or more and 120 nm or less, further preferably 20 nm or more and 100 nm or less, and further preferably 20 nm or more and 80 nm or less. In the polyarylene sulfide film of the present invention, by setting the average primary particle size of the inorganic particles (α) to 5 nm or more and 150 nm or less, both high heat resistance and mechanical properties can be achieved.
In the polyarylene sulfide film of the present invention, the content of the inorganic particles (α) is preferably 0.01% by volume or more and 5% by volume or less. It is more preferably 0.1% by volume or more and 3% by volume or less, and even more preferably 0.1% by volume or more and 2% by volume or less. When the content of the inorganic particles (α) is less than 0.01% by volume, the addition amount is too small, the radical trap effect becomes insufficient, and the heat resistance may decrease. If it exceeds 5% by volume, the mechanical properties of the film may deteriorate. In the polyarylene sulfide film of the present invention, when the content of the inorganic particles (α) is 0.01% by volume or more and 5% by volume or less, both high heat resistance and mechanical properties can be achieved.
In the polyarylene sulfide film of the present invention, the inorganic particles (α) are preferably treated with a compound having any of a metalloyl group, an epoxy group, an amino group and an isocyanate group. By being treated with these compounds, the affinity with the polyarylene sulfide-based resin (A) is increased, the dispersibility is increased, and the heat resistance of the film is improved. Furthermore, since the adhesiveness at the interface becomes high, it becomes possible to suppress the formation of voids during orientation in the stretching process described later, and it becomes possible to improve the mechanical properties and the insulating property. More preferred are silane coupling agents and titanium coupling agents having any of metalloyl group, epoxy group, amino group and isocyanate group. More preferably, it is treated with a silane coupling agent having any of a metalloyl group, an epoxy group, an amino group, and an isocyanate group, in that it is inexpensive, can be easily treated, and has high durability of a treated film. preferable. More preferably, it is a silane coupling agent having a metalloyl group and an epoxy group.
The polyarylene sulfide film of the present invention has a layer (Pa layer) containing a thermoplastic resin (B) different from the polyarylene sulfide resin (A), and the thermoplastic resin (B) has one of the following chemical formulas. It is preferable to have.

(However, each of R _{1 to} R ₆ in the formula is any of H, OH, a methoxy group, an ethoxy group, a trifluoromethyl group, an aliphatic group having 1 to 13 carbon atoms, and an aromatic group having 6 to 10 carbon atoms. It is.)
The thermoplastic resin (B) used in the polyarylene sulfide film of the present invention contains at least one structure of the following chemical formulas, more preferably the chemical formulas (A), (B) and (C), and It is preferable to include the chemical formula (A). In particular, when the chemical formula (A) is included, it contributes to improvement of electric insulation and heat resistance, which is preferable. It is presumed that this is because the thermoplastic resin (B) containing the chemical formula (A) and the polyarylene sulfide resin (A) interact with each other to further suppress the mobility of the molecular chain. When the thermoplastic resin (B) does not contain the structure of the following chemical formula, not only sufficient heat resistance and electric insulation cannot be obtained, but also when the resin kneaded with the polyarylene sulfide is filmed and stretched, Peeling may occur at the interface with the plastic resin B, which may cause breakage of the film, which is not preferable.

(However, each of R _{1 to} R ₆ in the formula is any of H, OH, a methoxy group, an ethoxy group, a trifluoromethyl group, an aliphatic group having 1 to 13 carbon atoms, and an aromatic group having 6 to 10 carbon atoms. It is.)
The thermoplastic resin (B) is, for example, a polyamide resin, a polyetherimide resin, a polyethersulfone resin, a polyphenylsulfone resin, a polysulfone resin, a polyphenylene ether resin, a polyester resin, a polyarylate resin. Various polymers such as resins, polyamide-imide resins, polycarbonate resins, polyether ether ketone resins, and blends containing at least one of these polymers can be used. In particular, when the polyarylene sulfide resin (A) is a polyphenylene resin, the thermoplastic resin (B) is more preferably a polyphenyl sulfone resin, a polyphenylene ether resin, or a polysulfone resin from the viewpoint of heat resistance and electric insulation. Resins such as resins having a sulfonyl group, and resins selected from polyetherimides are preferable, and resins having a sulfonyl group are more preferable, and polyphenylsulfone-based resins are particularly preferable.
The polyarylene sulfide film of the present invention has a content WA1 (volume%) of the polyarylene sulfide resin (A) in the Pa layer and a content WB1 (volume%) of the thermoplastic resin (B) different from the resin (A). ), the total content WB1 of the thermoplastic resin (B) is preferably 0.1% by volume or more and less than 50% by volume. More preferably, the content WB1 of the thermoplastic resin (B) is 0.1 volume% or more and less than 30 volume %, and further preferably the content WB1 of the thermoplastic resin (B) is 0.1 volume% or more 15 It is less than volume %. When the content of the thermoplastic resin (B) is 50% by volume or more, tearing frequently occurs during stretching and stable film formation may not be possible, which is not preferable. Further, if the content of the thermoplastic resin (B) is less than 0.1% by volume, heat resistance may be deteriorated, which is not preferable.
In the polyarylene sulfide film of the present invention, the Pa layer is preferably a layer in which the thermoplastic resin (B) is present as a dispersed phase in the polyarylene sulfide resin (A). The dispersed phase as used herein means an island component having a sea-island structure composed of the polyarylene sulfide resin (A) and the thermoplastic resin (B). In addition, the shape means that the thermoplastic resin (B) exists in the polyarylene sulfide film of the present invention in a circular, spindle-shaped, or amorphous state, and the cross section of the film is a transmission electron microscope (TEM). The form can be confirmed by observation or scanning electron microscope (SEM) observation.

In the polyarylene sulfide film of the present invention, when the Pa layer is a layer in which the thermoplastic resin (B) is present as a dispersed phase in the polyarylene sulfide resin (A), the major axis is the major axis in the dispersed diameter of the thermoplastic resin (B). It is preferable that the ratio of the minor axis to 1.05 or more. It is more preferably 2.0 or more, still more preferably 3.5 or more, and most preferably 4.0 or more. When the ratio of the major axis to the minor axis is less than 1.05, peeling may occur at the interface between the polyarylene sulfide resin (A) and the thermoplastic resin (B) during film stretching, and tearing may occur or the obtained stretching may occur. The mechanical properties of the film may be deteriorated and the heat resistance may be decreased. It is considered that the larger the ratio of the major axis to the minor axis is, the stronger the interaction between the polyarylene sulfide-based resin (A) and the thermoplastic resin (B) is, which contributes to the improvement of heat resistance, which is preferable. Therefore, although the upper limit value is not particularly set, the substantial upper limit of the ratio of the major axis to the minor axis is about 20 in view of the stretching ratio. The polyarylene sulfide film of the present invention is obtained by using the above-mentioned raw materials, and the polyarylene sulfide resin (A) is the main constituent component, and the layer (P1 layer) alone containing the inorganic particles (α) may be a single substance. It is good, but any of them is preferably used when it has a laminated structure with another layer (P2 layer). In the case of a laminated structure, the ratio of the P1 layer is preferably 50% by volume or more of the entire film in order to exert the effects of low dielectric property and high heat resistance of the P1 layer. It is more preferably at least 60% by volume, and even more preferably at least 70% by volume.

In the case of a laminated structure, a P2 layer is provided on one side of the P1 layer, a P2 layer is provided on both sides, a P1 layer is provided on both sides of the P2 layer, etc., depending on the desired effect. Is possible.

When the polyarylene sulfide film of the present invention has a Pa layer, it is preferable that the inorganic particles (α) are also included in the Pa layer, that is, the Pa layer is the P1 layer. With this structure, a film having higher heat resistance can be obtained.
The polyarylene sulfide film of the present invention preferably has a porosity of 5% by volume or less. The porosity referred to here is obtained by the ratio of the area of voids in the cross-sectional area of the film in the cross-sectional SEM image. It is more preferably 3% by volume or less, further preferably 2% by volume or less, and the practical lower limit is 0% by volume. In the polyarylene sulfide film of the present invention, by setting the porosity to 5% by volume or less, it becomes possible to further improve the mechanical properties.
In the polyarylene sulfide film of the present invention, the thickness of the film is T (μm), the content of the inorganic particles (α) in the range from the surface of the film to 0.1 T is Vfa (volume %), and the thickness is 0. When the content of the inorganic particles (α) in the range from 1 T to 0.9 T is Vfα (volume %), Vfa/Vfα satisfies 0≦Vfa/Vfα<1 on at least one surface. preferable. More preferably, both surfaces have Vfa/Vfα satisfying 0≦Vfa/Vfα<1. In the present invention, Vfa/Vfα is obtained by the method described below, and the smaller Vfa/Vfα indicates that the surface layer of the film has a smaller content of inorganic particles (α). As a result, it is possible to prevent the inorganic particles (α) from slipping off the film surface and the interfacial peeling at the interface between the inorganic particles (α) and the resin, and to handle the same as a normal polyarylene sulfide film. Is possible. In particular, a remarkable effect is exhibited in applications such as adhering a film to a smooth surface, and it is preferable that the slippage of the filler and the interfacial separation at the interface between the filler and the resin are less likely to occur, because the adhesion to the smooth surface becomes higher. .. More preferably, 0.1≦Vfa/Vfα≦0.8, and even more preferably 0.1≦Vfa/Vfα≦0.7. When Vfa/Vfα is 1 or more, a large amount of inorganic particles (α) are present on the film surface, and the inorganic particles (α) slip off from the film surface, resulting in process contamination or inorganic particles (α). Interfacial peeling may occur at the interface between and. The lower limit of Vfa is 0. In order to satisfy 0≦Vfa/Vfα<1, a laminated structure in which a layer containing a small amount of the inorganic particles (α) and a layer containing a large amount of the inorganic particles (α) are laminated after controlling the type and surface activity of the inorganic particles (α) It is preferable to provide a layer containing a small amount of inorganic particles (α) on at least one surface.

The polyarylene sulfide film of the present invention preferably has the highest glass transition temperature of 180° C. or higher in DSC measurement. The glass transition temperature referred to here is, in accordance with JIS K-7122 (1987), heating the resin from 25° C. to 350° C. at a temperature rising rate of 20° C./min according to JIS K-7122 (1987) (1st Run). After maintaining in that state for 5 minutes, it was then rapidly cooled to 25° C. or lower, and again heated from 25° C. to 350° C. at a heating rate of 20° C./min (2nd Run) to obtain 2nd RUN. In the differential scanning calorimetry chart, it is the midpoint glass transition temperature determined based on the method described in JIS K-7121 (1987), and is the highest glass transition temperature among them. The temperature is more preferably 200° C. or higher, further preferably 210° C. or higher, and particularly preferably 220° C. or higher. When the highest glass transition temperature is lower than 180° C., the heat resistance of the obtained polyarylene sulfide film may decrease, which is not preferable. Although the upper limit of Tg2 is not particularly set, if it exceeds the extrusion temperature of the polyarylene sulfide resin (A), the melt viscosity may become too high and melt film formation may be impossible. It is preferably below the extrusion temperature of A). Specifically, when a polyphenylene sulfide resin is used as the polyarylene sulfide resin (A), the upper limit of the highest glass transition temperature is preferably 340°C or lower.

The polyarylene sulfide film of the present invention preferably has a strength retention at break of 65% or more after being heated in an oven at 220° C. for 72 hours. It is more preferably 80% or more, still more preferably 85% or more. The strength retention at break here is a value represented by the following formula. When the strength retention at break is less than 65%, the heat resistance as a film is low, and when used for a long time in a high temperature environment. The film may break. In addition, it is possible to achieve the breaking strength retention rate within the above range by including the inorganic particles (α). Further, it is possible to obtain higher heat resistance by including the thermoplastic resin (B) having any one of the structures described in the chemical formula (1).
Breaking strength retention (%)=(breaking strength after heating)/(breaking strength before heating)×100
The polyarylene sulfide film in the present invention preferably has a dielectric breakdown voltage Pd per unit thickness of 100 kV/mm or more. By setting Pd to 100 kV/mm or more, it becomes possible to use even in the application of higher voltage. It is more preferably 150 kV/mm or more, further preferably 170 kV/mm or more, further preferably 200 kV/mm or more, and particularly preferably 220 kV/mm or more. The upper limit of Pd is not particularly limited, but is substantially around 500 kV/mm. In order to further increase the value of Pd, as described above, the inorganic particles (α) are set within the above range, the inorganic particles (α) are surface-treated to increase the affinity, and the thermoplastic resin (B ) Are mixed, and the stretching conditions for biaxial stretching are controlled to the conditions described below.
In the polyarylene sulfide film of the present invention, other components such as heat-resistant stabilizers (hindered phenol-based, hydroquinone-based, phosphite-based and substitution products thereof, etc.), weather-resistant agent (in the range that does not impair the effects of the present invention) Resorcinol-based, salicylate-based, benzotriazole-based, benzophenone-based, hindered amine-based), mold release agents and lubricants (montanic acid and its metal salts, their esters, their half esters, stearyl alcohol, stearamide, various bisamides, bisurea and polyethylene) Wax, etc.), pigment (cadmium sulfide, phthalocyanine, carbon black for coloring, etc.), dye (nigrosine, etc.), plasticizer (octyl p-oxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agent (alkyl sulfate type) Anionic antistatic agent, quaternary ammonium salt type cationic antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agent, etc., flame retardant (eg red phosphorus And phosphates, melamine cyanurate, magnesium hydroxide, hydroxides such as aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin or brominated flame retardants thereof. Other polymers (for example, elastomers) can be added.
The method for producing the polyarylene sulfide film of the present invention will be described.

As the polyarylene sulfide-based resin (A) of the present invention, a method for producing a polyphenylene sulfide-based resin in which the main structural unit of the polymer is a p-phenylene sulfide unit will be described. Sodium sulfide and p-dichlorobenzene are mixed and reacted in an amide polar solvent such as N-methyl-2-pyrrolidone (NMP) at high temperature and high pressure. If necessary, a copolymerization component such as m-dichlorobenzene or trihalobenzene can be included. A caustic potash, an alkali metal salt of a carboxylic acid, or the like is added as a polymerization degree adjusting agent, and a polymerization reaction is performed at 230 to 290°C. After the polymerization, the polymer is cooled, and the polymer is made into a water slurry and filtered with a filter to obtain a wet granular polymer. An amide-based polar solvent is added to this granular polymer, and the mixture is washed by stirring at a temperature of 30 to 100°C, washed several times with ion-exchanged water at 30 to 80°C, and washed several times with an aqueous metal salt solution such as calcium acetate. After washing, it is dried to obtain a granular polymer of polyarylene sulfide resin.
The granular polymer and the inorganic particles (α) are mixed at an arbitrary ratio, charged into an extruder with a vent set to 300 to 350° C., melt-extruded in a strand form, cooled with water at a temperature of 25° C., and then cut. Make a chip. At this time, the addition concentration of the inorganic particles is preferably 0.01 parts by mass or more and 10 parts by mass or less, and more preferably 0.05 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the granular polymer.

In addition, if necessary, only the above-mentioned granular polymer, or the granular polymer and the inorganic particles (α), the thermoplastic resin (B), the additive, and the like are mixed at an arbitrary ratio, and the vent is set to 300 to 350°C. It is put in an attached extruder, melt-extruded in a strand shape, cooled with water at a temperature of 25° C., and then cut to produce chips.
In the present invention, when the polyarylene sulfide-based resin (A) and the thermoplastic resin (B) are mixed, the mixing timing is not particularly limited, but before the melt extrusion, the polyarylene sulfide-based resin (A) and the polyarylene sulfide-based resin (A) are mixed. There are a method of pre-melting and kneading (pelletizing) the mixture of the thermoplastic resin (B) to form master pellets, and a method of mixing and melt-kneading at the time of melt extrusion. Of these, a method of forming a master pellet by using a device such as a twin-screw extruder to which shear stress is applied is preferable. In this case, in the kneading section, it is preferable to carry out the kneading so that the melting point of the polyarylene sulfide resin (A) is within the resin temperature range of +5° C. to 80° C., more preferably the melting point of the polyarylene sulfide resin (A) +10. C. or higher and 80.degree. C. or lower, and more preferably the melting point of the polyarylene sulfide resin (A)+15.degree. C. or higher and 70.degree. C. or lower. The screw rotation speed is preferably in the range of 100 rpm or more and 500 rpm or less, and more preferably 150 rpm or more and 400 rpm or less. The dispersion diameter of the dispersed phase can be controlled by setting the resin temperature and the screw rotation speed within the preferable ranges. The ratio of (screw shaft length/screw shaft diameter) of the twin-screw extruder is preferably in the range of 20 or more and 60 or less, and more preferably in the range of 30 or more and 50 or less.
When the polyarylene sulfide resin (A) and the inorganic particles (α) are mixed with the thermoplastic resin (B), heat is added when the polyarylene sulfide resin (A) and the inorganic particles (α) are mixed. It is also preferable to add the plastic resin (B).
The chips thus obtained were dried under reduced pressure at 180° C. for 3 hours, and then mixed and fed to an extruder having a melting portion set at 300 to 350° C. so as to have a predetermined concentration, and then discharged from a T-die type die. Then, they are brought into close contact with each other while being applied with an electrostatic charge on a cooling drum having a surface temperature of 20 to 70° C. to be rapidly cooled and solidified to obtain a substantially unoriented unstretched film.

Next, in the case of biaxial stretching, the unstretched film obtained above is uniaxially stretched in the range of the glass transition point (Tg) or more of the polyarylene sulfide resin (A) to the cold crystallization temperature (Tcc) or less, Alternatively, biaxial stretching is performed. In order to improve the heat resistance which is the object of the present invention, it is more preferable that the orientation parameter is high. As a method for obtaining a film by biaxial stretching, a sequential biaxial stretching method (a stretching method in which stretching in the longitudinal direction is followed by stretching in the width direction, which is a combination of stretching in each direction) and a simultaneous biaxial stretching method are used. (A method of stretching in the longitudinal direction and the width direction at the same time), or a method of combining them can be used. Here, a sequential biaxial stretching method in which stretching is first performed in the longitudinal direction and then in the width direction is illustrated.
The unstretched film is heated by a heating roll group and stretched in the longitudinal direction (MD direction) by 2.4 to 4.5 times, more preferably 2.8 to 4.0 times in a single stage or in multiple stages of two or more stages. (MD stretching). The stretching temperature is in the range of Tg to Tcc, preferably (Tg+5) to (Tcc-10)°C. Then, it cools with a 20-50 degreeC cooling roll group.

Then, as a stretching method in the width direction (TD direction), for example, a method using a tenter is generally used. Both ends of this film are gripped by clips, guided to a tenter, and stretched in the width direction (TD stretching). The stretching temperature is preferably Tg to Tcc, more preferably (Tg+5) to (Tcc-10)°C. The stretching ratio is preferably 2.5 to 5.0 times, more preferably 3.0 to 4.5 times from the viewpoint of the flatness of the film.
At this time, with respect to the stretching ratio of the film, the ratio of the MD ratio to the TD ratio (stretch ratio: MD ratio/TD ratio) is preferably 1.05 or less, more preferably 1.0 or less, and 0.95 or less. More preferable.
Next, an operation (heat setting treatment) of heat setting the stretched film under tension is performed. The heat setting temperature is the same throughout the heat treatment zone, either at the same temperature, or in one stage heat setting or in multi-stage heat setting at different temperatures in the first half and the second half of the heat treatment zone. .. The heat setting temperature is preferably 160° C. to the melting point (Tm), and is preferably 180 to (Tm-10)° C. from the viewpoint of suppressing heat shrinkage of the film. After the heat setting treatment, the film is cooled to room temperature and, if necessary, subjected to a relaxation treatment of 1 to 20% in the longitudinal and width directions, the film is cooled and wound to obtain a biaxially stretched thermoplastic resin film.
The production method when the polyarylene sulfide film of the present invention has a laminated structure including a P1 layer and another layer (hereinafter referred to as P2 layer) is as follows. When the material of each layer to be laminated is mainly composed of thermoplastic resin, two different materials are respectively put into two extruders, melted and coextruded from the die onto the cast drum to form a sheet. Processing method (coextrusion method), coating layer raw material into a sheet made of a single film into an extruder, melt extrusion and extrusion from a die (melt laminating method), P1 layer and P2 layer to be laminated separately Prepared by the method of thermocompression bonding with a heated roll group (thermal laminating method), bonding with an adhesive (adhesion method), and other materials for P2 layer dissolved in a solvent, It is possible to use a method of coating on the P1 layer that has been prepared in advance (coating method), a method of combining these, or the like. Among them, the co-extrusion method is particularly preferable from the viewpoint of enhancing the adhesiveness at the laminated interface between the P1 layer and the P2 layer and enhancing the handleability as an insulating material.

When the P2 layer mainly contains a material other than a thermoplastic resin, the P2 layer to be laminated with the P1 layer is separately prepared and bonded by an adhesive or the like (adhesion method) or curing. In the case of a conductive material, a method in which it is applied on the P1 layer and then cured by electromagnetic wave irradiation, heat treatment, or the like can be used. In addition to the methods such as the coextrusion method, the melt laminating method, the solution laminating method, and the thermal laminating method described above, a dry method such as a vapor deposition method and a sputtering method, a wet method such as a plating method, and the like can be preferably used. I can.

The polyarylene sulfide film of the present invention can be produced by the steps described above, and the obtained film has high heat resistance. According to the present invention, it is possible to provide a polyarylene sulfide film having both high electrical insulation and high heat resistance. In particular, it can be suitably used for automobile parts such as electronic parts such as motor/rotor insulators, capacitor dielectrics, copper-clad laminates, flexible printed boards, and insulating tapes.

Hereinafter, the present invention will be described more specifically with reference to examples.

The method of measuring physical properties and the method of evaluating effects in the present invention were performed according to the following methods.

(1) Orientation parameter A sample of which a cross section was cut using a microtome was measured with a near infrared Raman spectroscope manufactured by Photon Design Co., Ltd. in a measurement mode micro Raman, objective lens: 100 times, beam diameter: 1 μm, light source: Second harmonic (wavelength 532 nm) of YAG laser, laser power: 1000 mW, diffraction grating: Single 3000 gr/mm, slit: 100 μm, detector: InGaAs/Nippon Rover 1024×256 under the following conditions (A1). ~ (A3) was measured. In addition, when there are a plurality of peaks having a strong sensitivity to anisotropy such as when a plurality of resins are mixed, the orientation parameter was determined using the peak having the highest peak intensity.
(A1) The Raman band in the case of irradiating polarized light in a direction parallel to the in-plane direction of the film is obtained.
(A2) of the Raman band obtained, the peak intensity _{I 745} of the out-of-plane deformation vibration of 1080cm peak intensity of the stretching vibration of ^-1 vicinity of the phenyl ring -S _I 1080, 745cm ^-1 near the phenyl ring -S The orientation parameters were determined by the ratio of I ₁₀₈₀ and I ₇₄₅ , I ₁₀₈₀ /I ₇₄₅ , respectively.
In the cross section cut in parallel with the longitudinal direction of the film (the direction defined by the measurement of elongation at break), the above measurement was performed while changing the position by 0.1×T in the thickness direction by μm from one surface side. The orientation parameter was determined by the average value. Further, the position was changed in five positions in the film surface direction. In addition, the same measurement was performed on a cross section parallel to the film width direction (the direction defined by the measurement of elongation at break). The lower value of the orientation parameter obtained in the longitudinal direction and the orientation parameter obtained in the width direction was used as the orientation parameter.

(2) Content of inorganic particles (α) in film, average primary particle size Content of inorganic particles (α) in film, average primary particle size were determined by the following procedures (B1) to (B7). .. In addition, the measurement was performed 5 times in total by changing the cut position of the film at random, and from the one surface side of the film to the other surface side, changing the position by 0.02×T in the thickness direction. The content (volume %) of the inorganic particles (α) and the average primary particle diameter (nm) were determined by their arithmetic mean values.
(B1) Using a microtome, the film cross section is cut perpendicularly to the film surface direction and parallel to the film longitudinal direction (direction defined by measurement of elongation at break) without crushing in the thickness direction.
(B2) Next, the cut cross section is observed using a scanning electron microscope to obtain an image magnified and observed at 50,000 times. It should be noted that although the observation place is randomly determined, the vertical direction of the image is parallel to the thickness direction of the film, and the horizontal direction of the image is parallel to the longitudinal direction of the film.
(B3) In the image obtained in the above (B2), the area of the film (the total area including the areas of voids and inorganic particles existing in the film) is measured and designated as A.
(B4) After performing the energy dispersive X-ray analysis in the image to determine the inorganic particles (α) whose main component is a metal oxide or base metal oxide, the area of all the inorganic particles (α) in the image Is measured and the total area is B. Here, what is to be measured is not limited to those in which the whole of the inorganic particles (α) is contained in the image, but also includes the inorganic particles (α) in which only a part thereof appears in the image.
(B5) B was divided by A (B/A) and multiplied by 100 to obtain the area ratio of the inorganic particles (α). Based on this value, the content (volume %) of the inorganic particles (α) was defined.
In (B6) and (B4), the number of all the inorganic particles (α) observed was calculated to obtain the number Nα of the inorganic particles (α).
In (B7) and (B4), the observed area B of the inorganic particles (α) is divided by the number Nα of the inorganic particles obtained in (B6) (B/Nα), and a true circle of the same area is drawn. In this case, the diameter of the perfect circle was calculated and used as the average primary particle size (nm).

(3) Inorganic particle (α) content Vfa (volume %) in the thickness 0 to 0.1×T portion from the surface, and inorganic particle (α) content 0.1×T to 0.9×T portion in the thickness from the surface Amount Vfα
From the value obtained in the above (3), the arithmetic average value of the content of the inorganic particles (α) in the thickness 0 to 0.1×T portion from the surface, the thickness 0.1×T to 0.9×T from the surface The arithmetic average value of the inorganic particle (α) content of the part is determined, and the thickness is 0 to 0.1×T from the surface, and the inorganic particle (α) content Vfa (volume %) of the part, the thickness is 0.1× from the surface. The content of the inorganic particles (α) in the T to 0.9×T portion was defined as Vfα.

(4). Porosity V, content of thermoplastic resin (B) WB1, ratio of major axis and minor axis of dispersed phase Porosity, content of thermoplastic resin (B), ratio of major axis and minor axis of dispersed phase are as follows: It was determined by the procedure of (C1) to (C10). In addition, the measurement was performed 10 times in total by randomly changing the film cut portion, and the porosity V in the film, the porosity Va1 (volume %) in the P1 layer, and the thermoplasticity in the film by the arithmetic mean value thereof. The content of the resin, the content WB1 (volume %) of the thermoplastic resin (B) in the Pa layer, and the ratio of the major axis and the minor axis of the dispersed phase were used. Further, in order to obtain the porosity V in the film and the content of the thermoplastic resin (B), in (C2), the observation position is moved in the thickness direction, and it is continuously measured from one surface to the other surface. The prepared images were prepared and similarly obtained according to the procedures of (C3) to (C8).
(C1) Using a microtome, the film cross section is cut perpendicularly to the film surface direction and parallel to the film longitudinal direction (direction defined by measurement of elongation at break) without crushing in the thickness direction.
(C2) Next, the cut cross section is observed using a scanning electron microscope, and an image magnified 2000 times is obtained. The observation location is randomly determined in the film, but the vertical direction of the image is parallel to the thickness direction of the film, and the horizontal direction of the image is parallel to the longitudinal direction of the film.
(C3) The area of the P1 layer in the image obtained in (C2) (the total area including the areas of voids and inorganic particles existing in the P1 layer) is measured, and this is designated as C. If the interface between the P1 layer and other layers is difficult to discern in the image, the cross section of the same sample is observed by polarized light using a differential interference microscope to determine the interface position of the P1 layer, and the area of the P1 layer is estimated. ..
(C4) The area of all voids existing in the P1 layer in the image is measured, and the total area is defined as D. Here, what is to be measured is not limited to the one in which the entire void is contained in the image, but includes the bubbles in which only a part of the void appears in the image.
(C5) D was divided by C (D/C) and multiplied by 100 to obtain the area ratio of voids in the P1 layer, and this value was taken as the void ratio Va1 (volume %).
(C7) The area of the Pa layer in the image obtained in (C2) (the total area including the areas of voids and inorganic particles existing in the Pa layer) is measured, and this is designated as E. When it is difficult to distinguish the interface between the Pa layer and the other layers in the image, polarization of the cross section of the same sample is observed using a differential interference microscope to determine the interface position of the Pa layer, and the area of the Pa layer is estimated. ..
(C8) After performing energy dispersive X-ray analysis in the image to determine the thermoplastic resin (B), the areas of all dispersed phases in the image are measured, and the total area is set to F. Here, what is to be measured is not limited to one in which the entire dispersed phase is contained in the image, but includes one in which only a part of the dispersed phase appears in the image.
(C9) F was divided by E (F/E) and multiplied by 100 to obtain the area ratio of the thermoplastic resin (B) in the Pa layer. Based on this value, the content WB1 (volume%) of the thermoplastic resin (B) was defined.
(C10) Further, any 20 disperse phases were selected, the circumscribed circle of each disperse phase was taken, and the average value of the diameters thereof was taken as the major axis of the disperse phase. Further, the inscribed circle of each dispersed phase was taken and the diameter was taken as the single diameter of the dispersed phase. The ratio of the obtained major axis and minor axis was calculated.

(5) Glass transition temperature (Tg), cold crystallization temperature (Tcc), melt crystallization temperature (Tmc)
According to JIS K-7121 (1987) and JIS K-7122 (1987), the film was measured by a differential scanning calorimeter “Robot DSC-RDC220” manufactured by Seiko Instruments Inc. for data analysis. The measurement was performed using a disk session "SSC/5200" in the following manner.

(A) 1st Run measurement A sample of film was weighed in 5 mg increments in a sample pan, and the resin was heated from 25°C to 350°C at a temperature increase rate of 20°C/min at a temperature increase rate of 20°C/min. It was kept for 5 minutes, and then rapidly cooled to 25°C or lower.

(B) 2nd Run
Immediately after the completion of the 1st Run measurement, the temperature was raised again from 25°C to 350°C at a heating rate of 20°C/min, and the state was held for 5 minutes for measurement. In the obtained 2ndRUN differential scanning calorimetry chart, the glass transition temperature (Tg) was obtained by determining the midpoint glass transition temperature based on the method described in JIS K-7121 (1987) (extended straight line of each baseline). From the point where the straight line at the same distance in the vertical axis intersects with the curve of the step change of the glass transition). When there were a plurality of glass transition temperatures, the above treatment was carried out for all of them, and the lowest glass transition temperature was Tg1 and the highest glass transition temperature was Tg2.

(6) Breaking point strength/breaking point elongation The breaking point strength and breaking point of the film are cut into a size of 1 cm×20 cm based on ASTM-D882 (1997), the distance between chucks is 5 cm, and the pulling speed is 300 mm. The strength at break and the elongation at break when pulled at /min were measured. Here, the measurement was carried out with 0° in either direction of the film, the sample was cut out by changing the direction from −90° to 90° in steps of 10°, and the direction in which the elongation at break was the smallest It was defined as the longitudinal direction of the film. The breaking point strength and the breaking point elongation of the film were defined as the average values of the breaking point strength and the breaking point elongation in the longitudinal direction and the breaking strength in the direction orthogonal to the longitudinal direction.

(7) Heat resistance The film was allowed to stand for 72 hours in an oven (DRV420DA) manufactured by ADVANTEK set at 220° C., and the strength at break of the heat-treated film was measured by the same method as in (7). The breaking strength retention was calculated by the following formula in each of the longitudinal direction and the width direction, and the average value was used as the breaking strength retention.
Breaking strength retention (%)=(breaking strength after heating)/(breaking strength before heating)×100.

(8) Dielectric breakdown voltage Pd
The film was cut into a square of size 25 cm x 25 cm, and the humidity was controlled in a room at 23°C and 65% Rh for 24 hours, and then based on JIS C2151 (2006), an AC breakdown tester (Kasuga Denki KK, AC30 kV) ) Was used to measure the dielectric breakdown voltage (kV) per unit thickness at a frequency of 60 Hz and a boosting rate of 1000 V/sec. Then, the thickness (μm) of the peripheral portion of the portion where the dielectric breakdown occurred and the hole was formed was measured. Next, the obtained breakdown voltage was divided by the thickness (μm) to calculate the breakdown voltage per unit thickness (kV/mm). The measurement was performed 10 times, and the average value was used as the dielectric breakdown voltage Pd (kV/mm) per unit thickness.

Reference Example 1 Preparation of Polyarylene Sulfide Resin (A) In an autoclave, 47% sodium hydrosulfide 9.44 kg (80 mol), 96% sodium hydroxide 3.43 kg (82.4 mol), N-methyl- 2-Pyrrolidone (NMP) 13.0 kg (131 mol), sodium acetate 2.86 kg (34.9 mol), and ion-exchanged water 12 kg were charged, and the pressure was gradually increased to 235° C. over about 3 hours while nitrogen was passed under normal pressure. After heating and distilling 17.0 kg of water 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 sub-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 raised 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. Then, 1.60 kg (88.8 mol) of water was injected again into the system, cooled to 240° C., 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 then the solvent and solids were filtered off with a sieve (80 mesh). The obtained particles were washed again with 38 liters of NMP at 85°C. After that, it was washed 5 times with 67 liters of warm water and filtered, and then washed 5 times with 70,000 g of 0.05% by weight calcium acetate aqueous solution and filtered to obtain PPS polymer particles. This was dried with 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) Surface treatment with methacryloyl group-containing silane coupling agent (treatment A)
Silica particles with a particle diameter of 50 nm (Admatex Co., Ltd., YA050C) were placed in a Henschel mixer and stirred, and in that state, the particles and the methacryloyl group-containing silane coupling agent (Shin-Etsu Chemical Co., Ltd., KBM-503) were added together. It is treated with the methacryloyl group-containing silane coupling agent by spray-spraying so as to be 0.5% by mass with respect to 100% by weight, heating and stirring at 70° C. for 2 hours, and then taking out. Silica particles (particle A) were obtained.

(Reference Example 3) Surface treatment with epoxy group-containing silane coupling agent (treatment B)
Silica treated with an epoxy group-containing silane coupling agent in the same manner as in Reference Example 2 except that the silane coupling agent used was an epoxy group-containing silane coupling agent (KBM-403, manufactured by Shin-Etsu Chemical Co., Ltd.). Particles (particles B) were obtained.

(Example 1)
99 parts by mass of the polyarylene sulfide-based resin (A) obtained in Reference Example 1 and 1 part by mass of silica particles (YA050C manufactured by Admatechs Co., Ltd.) having a particle diameter of 50 nm as inorganic particles (α) were mixed, and then mixed at 320°C. It is supplied to a vented twin-screw kneading extruder of the same direction rotation type heated to a temperature, melt-kneaded, discharged in a strand shape, cooled with water at a temperature of 25° C., and immediately cut to give 1 mass of silica particles. % Containing chips were made.
The obtained chips were vacuum dried at 180° C. for 3 hours, then fed to an extruder, melted at a temperature of 320° C. in a nitrogen atmosphere, and introduced into a T die die. Then, from the inside of the T-die die, extruded into a sheet form to form a molten single-layer sheet, and the molten single-layer sheet is cast on a cast drum kept at a surface temperature of 25° C. while being closely cooled and solidified by an electrostatic application method, An unstretched film was obtained. The obtained unstretched film was stretched in the longitudinal direction of the film at a stretching ratio of 3.5 times at a stretching temperature of 102° C. by using a longitudinal stretching machine composed of a plurality of heated roll groups and utilizing the peripheral speed difference of the rolls. .. Then, both ends of the film were supported by clips, introduced into a tenter, and stretched at a stretching temperature of 100° C. in the width direction of the film at a draw ratio of 3.4 times. Subsequently, heat treatment was performed at 280° C., relaxation treatment was performed at 5%, and after cooling to room temperature, the film edge was removed to obtain a polyarylene sulfide film having a thickness of 50 μm. Table 1 shows the physical properties and characteristics of the obtained film. It was confirmed that higher heat resistance than that of the comparative example was obtained.

(Examples 2 to 6)
As the inorganic particles (α), in Example 2, silica particles having a particle diameter of 100 nm (manufactured by Admatex Co., Ltd., YA050C), and in Example 3, silica particles having a particle diameter of 10 nm (manufactured by Admatex Corp., YA010C) were used. In Example 4, except that alumina particles having a particle diameter of 50 nm (132DL manufactured by Corefront Co., Ltd.), in Example 5 were used as particles A described in Reference Example 2 and in Example 6 were used as particles B described in Reference Example 3 A polyarylene sulfide film having a thickness of 50 μm was obtained in the same manner as in Example 1. Table 1 shows the physical properties and characteristics of the obtained film. In Example 3, heat resistance equivalent to that of Example 1, in Examples 2 and 4, heat resistance slightly higher than that of Example 1 but higher than that of Comparative Example, and in Examples 5 and 6, higher heat resistance than Example 1. It was confirmed that

(Examples 7 to 10)
A polyarylene sulfide film having a thickness of 50 μm was obtained in the same manner as in Example 1 except that the content of the inorganic particles (α) was changed as shown in Table 1. Table 1 shows the physical properties and characteristics of the obtained film. Example 7 is slightly inferior to Example 1, but higher in heat resistance than Comparative Example, Examples 8 and 9 are equivalent in heat resistance to Example 1, and Example 10 is slightly inferior to Example 1 in mechanical strength. It was confirmed that the same heat resistance as in Example 1 was obtained.

(Example 11)
A polyarylene sulfide film having a thickness of 50 μm was obtained in the same manner as in Example 1 except that the stretching ratio was changed as shown in Table 1. Table 1 shows the physical properties and characteristics of the obtained film. It was confirmed that the heat resistance was slightly inferior to that of Example 1, but higher than that of Comparative Example.

(Example 12)
98 parts by mass of the polyarylene sulfide-based resin obtained in Reference Example 1, 1 part by mass of silica particles (YA050C manufactured by Admatex Co., Ltd.) having a particle diameter of 50 nm as inorganic particles (α), and a thermoplastic resin (B) A polyarylene sulfide film having a thickness of 50 μm was prepared in the same manner as in Example 1 except that polyphenyl sulfone (PPSU: manufactured by Solvay Advanced Polymers Co., Ltd., Radel (registered trademark) R5800-NT) was supplied in an amount of 1 part by mass. Obtained. In addition, in Example 12, the P1 layer was a Pa layer. The obtained film characteristics are shown in Table 1. It was confirmed that higher heat resistance than that of Example 1 was obtained.

(Examples 13 to 15)
As the thermoplastic resin (B), in Examples 13 and 14, the amount of PPSU was changed as shown in Table 1, and in Example 15, polysulfone (PSU: manufactured by Solvay Advanced Polymers Co., Ltd., Radel (registered) was used instead of PPSU. A polyarylene sulfide film having a thickness of 50 μm was obtained in the same manner as in Example 12 except that (trademark) P1700 NT11) was used. In addition, in Examples 13 to 15, the P1 layer was a Pa layer. The characteristics of the obtained film are shown in Table 1. It was confirmed that higher heat resistance than that of Example 1 was obtained.

(Example 16)
As the P1 layer, the same raw material as described in Example 1 was prepared, and as the P2 layer, a raw material obtained by chipping the polyarylene sulfide resin as described in Reference Example 1 was prepared and prepared. After vacuum-drying for a period of time, they were separately supplied to two extruders heated to 320° C., and three layers were formed in a molten state on the upper part of the die by a laminating device (the laminating constitution is P2 layer/P1 layer/P2 layer= 1/8/1), then discharged from a T-die type die, and rapidly solidified by applying an electrostatic charge to a cast drum having a surface temperature of 25° C. to rapidly solidify to obtain an unstretched laminated sheet. .. Then, a polyarylene sulfide film having a thickness of 50 μm was obtained in the same manner as in Example 1. The characteristics of the obtained film are shown in Table 2. It was confirmed that a film having higher mechanical strength than that of Example 1 was obtained.

(Examples 17 to 20)
A polyarylene sulfide film having a thickness of 50 μm was obtained in the same manner as in Example 16 except that the raw material and laminated constitution of the P1 layer were changed to those shown in Table 2. The characteristics of the obtained film are shown in Table 2. In addition, in Example 20, the P1 layer was a Pa layer. It was confirmed that the films of Examples 17 to 19 had higher mechanical strength than Example 1 and Example 20 had higher mechanical strength than Example 13.

(Comparative Example 1)
A polyarylene sulfide film having a thickness of 50 μm was obtained in the same manner as in Example 1 except that silica particles were not added. The characteristics of the obtained film are shown in Table 1. The film was inferior in heat resistance to the examples.

(Comparative examples 2 and 3)
As the inorganic particles (α), in Comparative Example 2, silica particles having an average primary particle size of 200 nm (QCB-100 manufactured by Shin-Etsu Chemical Co., Ltd.), and in Comparative Example 3, calcium carbonate particles having an average primary particle size of 100 nm (Shiraishi Calcium Co., Ltd. In the same manner as in Example 1, except for using Vigot 10), a polyarylene sulfide film having a thickness of 50 μm was obtained. The characteristics of the obtained film are shown in Table 1. The film was inferior in heat resistance to the examples.

(Comparative example 4)
A polyarylene sulfide film having a thickness of 50 μm was obtained in the same manner as in Example 1 except that the stretching ratio was changed as shown in Table 1. The characteristics of the obtained film are shown in Table 1. The film was inferior in heat resistance to the examples.

(Comparative example 5)
An attempt was made to obtain a film by the same method as in Example 1 except that the addition amount of the inorganic particles (α) was changed as shown in Table 1, but the film could not be obtained due to breakage in the stretching step.

According to the present invention, it is possible to provide a polyarylene sulfide film having both high electrical insulation and high heat resistance. Such a polyarylene sulfide film can be suitably used especially for automobile parts such as electric parts such as an insulator of a motor/rotating machine, a dielectric of a capacitor, a copper-clad laminate, a flexible printed board, and an insulating tape.

Claims (11)

Includes inorganic particles (α) having a polyarylene sulfide resin (A) as a main constituent, a semimetal or base metal oxide as a main constituent, and an average primary particle diameter of 5 nm or more and 150 nm or less, and having an orientation parameter of 2 The above polyarylene sulfide film. The polyarylene sulfide film according to claim 1, wherein the content of the inorganic particles (α) is 0.01% by volume or more and 5% by volume or less. The polyarylene sulfide film according to claim 1 or 2, wherein the inorganic particles (α) are treated with a compound having any of a metalloyl group, an epoxy group, an amino group and an isocyanate group. The polyarylene sulfide film according to claim 1, which has a porosity of 5% by volume or less. The thickness of the film is T (μm), the content of the inorganic particles (α) in the range from the surface of the film to the thickness 0.1T is Vfa (volume %), and the thickness 0.1T to the thickness 0.9T. When the content of the inorganic particles (α) in the range is Vfα (volume %), Vfa/Vfα satisfies 0≦Vfa/Vfα<1 on at least one surface. Polyarylene sulfide film. The polyarylene sulfide film according to any one of claims 1 to 5, which has a highest glass transition temperature of 180°C or higher as measured by DSC. It has a layer (Pa layer) containing a thermoplastic resin (B) different from the resin (A), and the thermoplastic resin (B) has any one of the following chemical formulas. Polyarylene sulfide film.

(However, each of R _{1 to} R ₆ in the formula is any of H, OH, a methoxy group, an ethoxy group, a trifluoromethyl group, an aliphatic group having 1 to 13 carbon atoms, and an aromatic group having 6 to 10 carbon atoms. It is.)
The polyarylene sulfide film according to claim 7, wherein the Pa layer is a layer in which the thermoplastic resin (B) is present as a dispersed phase in the polyarylene sulfide resin (A). The polyarylene sulfide film according to claim 7, wherein the thermoplastic resin (B) has a sulfonyl group. The total of the content WA1 (volume %) of the polyarylene sulfide resin (A) in the Pa layer and the content WB1 (volume%) of the thermoplastic resin (B) different from the resin (A) was set to 100 volume %. In this case, the content (WB1) of the thermoplastic resin (B) is 0.1% by volume or more and less than 50% by volume, and the polyarylene sulfide film according to any one of claims 7 to 9. The polyarylene sulfide film according to any one of claims 7 to 10, wherein the ratio of the major axis to the minor axis in the dispersed diameter of the thermoplastic resin (B) is 1.05 or more.