JP6201456B2 - Polyarylene sulfide resin composition, molded article, and production method thereof - Google Patents

Description

  The present invention relates to a polyarylene sulfide resin composition having conductivity, a molded article, and a method for producing them.

  Polyarylene sulfide resins (hereinafter sometimes abbreviated as PAS resins) represented by polyphenylene sulfide resins (hereinafter sometimes abbreviated as PPS resins) are thermoplastic polymers having excellent heat resistance and chemical resistance. Is used in the field of molding. In addition, by adding a conductive filler such as carbon black to polyarylene sulfide resin, conductivity and chargeability are imparted and applied to antistatic fuel tubes, antistatic or conductive sheets and films, dustproof plastic gears, etc. (For example, refer to Patent Documents 1 and 2). However, the amount of conductive filler such as carbon black necessary for obtaining the desired conductive properties is not so small, and thus the toughness of the resin composition is lowered, but these uses such as tubes, sheets and films, plastic gears, etc. Since toughness is required in terms of its properties, it is also required to reduce the number of foreign substances contained in the resin composition as much as possible in order to suppress breakage starting from the foreign substances. Furthermore, the appearance and smoothness of the surface of the molded product are also required from the viewpoints of design properties, slidability and wear properties. Tubes, sheets, and films are often manufactured by extrusion molding, but foreign matter is removed with a screen mesh to remove foreign matter. Etc. cannot be within the desired standard, and as a result, frequent replacement of the screen mesh is required, leading to a reduction in productivity such as a reduction in product yield.

  By the way, as a technique for imparting toughness to the polyarylene sulfide resin, it is known to use a polyarylene sulfide resin whose molecular weight is increased by heat treatment (thermal crosslinking). The resulting product becomes brittle and has the disadvantages that the polyarylene sulfide resin is liable to generate foreign matter due to the heat-crosslinking gel during the molding process. For example, Patent Document 2 proposes a method of improving toughness by adding carbon black by using a polyarylene sulfide resin and a thermoplastic resin other than the polyarylene sulfide resin in combination, but the polyarylene sulfide resin and the refractive index are proposed. Since the different thermoplastic resins are used together as a modifier, the surface gloss is greatly lowered, and the appearance is restricted.

  Therefore, as one method for imparting toughness without relying on thermal crosslinking or alloying with other thermoplastic resins, there is a method of adding a silane coupling agent such as epoxy silane. By adding a certain amount or more of alkali metal hydroxide to the alkali metal sulfide, and further by acid treatment after completion of the polymerization reaction, a polyarylene sulfide resin highly reactive with epoxysilane is produced, It is also known to improve mechanical properties by using in combination with a silane coupling agent (see Patent Document 3). Furthermore, a polyarylene sulfide resin composition containing a polyarylene sulfide resin containing a carboxyl group in the resin at a ratio of 50 to 100 μmol / g and a silane coupling agent having an epoxy group as essential components is known (patent) Reference 4). However, in both methods, since the silane coupling agents are condensed with each other to form a granular material, the effective amount of the silane coupling agent that reacts with the polyarylene sulfide resin is reduced, and a sufficient addition effect is not obtained. As a result, the mechanical strength of the polyarylene sulfide resin molded article and the molding continuity represented by extrusion molding were reduced.

JP 60-053560 A JP-A-10-230556 JP-A-6-256517 JP 2001-279097 A

  Therefore, the problem to be solved by the present invention is a fine particulate material obtained by molding a polyarylene sulfide resin composition containing a polyarylene sulfide resin, a coupling agent and a conductive filler, and derived from the coupling agent. Of polyarylene sulfide resin, which is excellent in continuous formability during molding, suppresses breakage due to foreign matter, and suppresses reduction in mechanical strength due to conductive filler, composition capable of molding the molded body And a method for producing the same, and further, the conductive material is molded into a tube shape, a sheet shape, a film shape, and a gear shape to obtain desired conductive characteristics, and a conductive tube, a film having excellent surface appearance and wear properties, To provide seats and gears.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention, when a polyarylene sulfide resin is melt-kneaded, when a coupling agent is directly added, a condensate of the coupling agent is likely to be generated. In order to solve the above-mentioned problem, the coupling agent is uniformly dissolved in an aqueous solution, and the polyarylene sulfide resin and the conductive filler are added and mixed to suppress the generation of the condensate of the coupling agent. It came.

  That is, the present invention relates to an aqueous solution (a) obtained by dissolving a coupling agent (a2) in water and an alcohol mixed solvent (a1) having an alcohol concentration in the range of 0.1 to 90 v / v%, and polyarylene. The present invention relates to a method for producing a polyarylene sulfide resin composition in which a sulfide resin (b) and a conductive filler (c) are melt-kneaded.

  The present invention also provides an aqueous solution (a) obtained by dissolving a coupling agent (a2) in water and an alcohol mixed solvent (a1) having an alcohol concentration in the range of 0.1 to 90 v / v%, and a polyarylene sulfide. The present invention relates to a method for producing a polyarylene sulfide resin molded article obtained by molding a polyarylene sulfide resin composition (c) obtained by melt-kneading a resin (b) and a conductive filler (c).

Furthermore, the present invention is a polyarylene sulfide resin composition in which a coupling agent (a2) and a conductive filler (c) are dispersed in a continuous phase comprising a polyarylene sulfide resin (b), and the composition is 1 μm or more. The present invention relates to a polyarylene sulfide resin composition in which the number of granules containing a coupling agent having an equivalent circle diameter is less than 5 per 1 mm ^{2 of} the composition surface.

Furthermore, the present invention provides a polyarylene sulfide resin in which the number of granules containing a coupling agent having an equivalent circle diameter of 1 μm or more obtained by molding the polyarylene sulfide resin composition is less than 5 per 1 mm ^{2 of} the molded body surface. It relates to a molded body.

  According to the present invention, it is obtained by molding a polyarylene sulfide resin composition containing a polyarylene sulfide resin, a coupling agent, and a conductive filler, and suppresses the generation of fine particles derived from the coupling agent, A polyarylene sulfide resin molded article having excellent mechanical strength, a composition capable of molding the molded article and a method for producing the same, a conductive material having excellent conductivity comprising the molded article, and forming the molded article into a sheet or It is possible to provide a conductive film and sheet excellent in surface appearance and wear resistance by suppressing variation in conductivity used by being formed into a film.

  The method for producing the polyarylene sulfide resin composition of the present invention is an aqueous solution obtained by dissolving the coupling agent (a2) in water and an alcohol mixed solvent (a1) having an alcohol concentration in the range of 0.1 to 90 v / v%. (A), polyarylene sulfide resin (b) and conductive filler (c) are melt-kneaded.

  As a solvent for dissolving the coupling agent (a2) used in the present invention, a mixed solvent of water and alcohol is used. Examples of the alcohol include alcohols such as methanol, ethanol, 2-propanol, and 2-methoxyethanol. Of these, ethanol is preferable. The lower limit of the alcohol concentration in the aqueous solution is in the range of 0.1 v / v% or more, but is preferably in the range of 15 v / v% or more from the viewpoint of excellent storage stability, and more preferably in the range of 30 v / v% or more. More preferred. On the other hand, the upper limit of the alcohol concentration in the aqueous solution is 90 v / v% or less, but is preferably in the range of 80 v / v% or less, and more preferably in the range of 70 v / v% or less from the viewpoint of excellent workability during kneading and melting. More preferred.

  In the mixed solvent, the coupling agent (a2) is stirred and mixed. The stirring and mixing conditions at that time are not particularly limited as long as the coupling agent dissolves in the mixed solvent. For example, the temperature during stirring and mixing is preferably in the range of 0 to 80 ° C. The temperature is more preferably 20 to 50 ° C., and the stirring and mixing time is preferably in the range of 0.1 to 6 hours, for example, and more preferably in the range of 0.5 to 2 hours. Moreover, it is preferable that the density | concentration of the coupling agent in aqueous solution (a) is the range of 5-75 mass%, and it is more preferable that it is the range of 10-50 mass%.

  As such a coupling agent (a2), a coupling agent such as silane or titanium is used. Among these, a silane coupling agent is preferable, and a silane coupling agent having a functional group that reacts with a carboxy group (for example, an epoxy group, an isocyanato group, an amino group, or a hydroxyl group) is preferable. Examples of such silane coupling agents include epoxy groups such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Containing alkoxysilane compound, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane , Γ-isocyanatopropylethyldiethoxysilane, isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropyltrichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- ( -Aminoethyl) Amino group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane and γ-aminopropyltrimethoxysilane, and hydroxyl group-containing alkoxysilane compounds such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane. It is done.

  The content of the coupling agent (a2) in the polyarylene sulfide resin composition is not particularly limited as long as it does not impair the effects of the present invention. However, the mechanical strength and the polyarylene sulfide resin are increased. From the viewpoint of imparting excellent moldability by sticking, the lower limit is preferably in the range of 0.01 parts by mass or more with respect to 100 parts by mass of the polyarylene sulfide resin (b), and further 0.1 mass More preferred is a range of at least 0.3 parts, and most preferred is a range of at least 0.3 parts by mass. On the other hand, the upper limit is preferably in the range of 5 parts by mass or less with respect to 100 parts by mass of the polyarylene sulfide resin (b) from the viewpoint that deterioration of the appearance of the molded product can be suppressed, and further 3 masses. More preferred is a range of not more than 1.5 parts, and most preferred is a range of not more than 1.5 parts by mass.

  The polyarylene sulfide resin (b) used in the present invention has a resin structure having a repeating unit of a structure in which an aromatic ring and a sulfur atom are bonded. Specifically, the polyarylene sulfide resin (b) is represented by the following formula (1):

（式中、Ｒ^１及びＲ^２は、それぞれ独立して水素原子、炭素原子数１〜４のアルキル基、ニトロ基、アミノ基、フェニル基、メトキシ基、エトキシ基を表す。）で表される構造部位を繰り返し単位とする樹脂である。

(Wherein, R ¹ and R ² each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group). It is a resin having a structural site as a repeating unit.

Here, in the structural site represented by the formula (1), R ¹ and R ² in the formula are preferably hydrogen atoms from the viewpoint of the mechanical strength of the polyarylene sulfide resin. And those bonded at the para position represented by the following formula (2) and those bonded at the meta position represented by the following formula (3).

これらの中でも、特に繰り返し単位中の芳香族環に対する硫黄原子の結合は前記構造式（２）で表されるパラ位で結合した構造であることが前記ポリアリーレンスルフィド樹脂の耐熱性や結晶性の面で好ましい。

Among these, in particular, the bond of the sulfur atom to the aromatic ring in the repeating unit is a structure bonded at the para position represented by the structural formula (2). In terms of surface.

  Further, the polyarylene sulfide resin is not only the structural portion represented by the formula (1), but also the following structural formulas (4) to (7).

で表される構造部位を、前記式（１）で表される構造部位との合計の３０モル％以下で含んでいてもよい。特に本発明では上記式（４）〜（７）で表される構造部位は１０モル％以下であることが、ポリアリーレンスルフィド樹脂の耐熱性、機械的強度の点から好ましい。前記ポリアリーレンスルフィド樹脂中に、上記式（４）〜（７）で表される構造部位を含む場合、それらの結合様式としては、ランダム共重合体、ブロック共重合体の何れであってもよい。
また、前記ポリアリーレンスルフィド樹脂は、その分子構造中に、下記式（８）

The structural site represented by the formula (1) may be included at 30 mol% or less of the total with the structural site represented by the formula (1). In particular, in the present invention, the structural site represented by the above formulas (4) to (7) is preferably 10 mol% or less from the viewpoint of heat resistance and mechanical strength of the polyarylene sulfide resin. In the case where the polyarylene sulfide resin contains a structural moiety represented by the above formulas (4) to (7), the bonding mode thereof may be either a random copolymer or a block copolymer. .
The polyarylene sulfide resin has the following formula (8) in its molecular structure.

で表される３官能性の構造部位、或いは、ナフチルスルフィド結合などを有していてもよいが、他の構造部位との合計モル数に対して、３モル％以下が好ましく、特に１モル％以下であることが好ましい。

May have a trifunctional structural site represented by the formula (1) or a naphthyl sulfide bond, but is preferably 3 mol% or less, particularly 1 mol%, based on the total number of moles with other structural sites. The following is preferable.

  Further, the melt viscosity of the polyarylene sulfide resin (b) used in the present invention is not particularly limited as long as it does not impair the effects of the present invention, but has excellent surface appearance, surface smoothness, and mechanical strength. The melt viscosity (V6) measured at 300 ° C. is preferably in the range of 2 to 1,000 [Pa · s], more preferably in the range of 20 to 500 [Pa · s]. However, the viscosity (V6) measured at 300 ° C. means that an orifice whose ratio of the former / the latter of the temperature / 300 ° C., the load 1.96 MPa, the orifice length and the orifice diameter is 10/1 by using a flow tester. It represents the melt viscosity after using and holding for 6 minutes.

  Further, the non-Newtonian index of the polyarylene sulfide resin is not particularly limited as long as the effects of the present invention are not impaired, but is preferably in the range of 0.90 to 2.00. When using a linear polyarylene sulfide resin, it is preferable to use a non-Newtonian index in the range of 0.90 to 1.25, more preferably in the range of 0.95 to 1.15. It is preferable to use one having a range of 0.95 to 1.10. Such a linear polyarylene sulfide resin having a non-Newtonian index is excellent in mechanical properties, fluidity, and wear resistance. However, the non-Newtonian index (N value) is measured by measuring the shear rate and shear stress using a capillograph at 300 ° C, the ratio of the orifice length (L) to the orifice diameter (D), and L / D = 40. These are values calculated using the following formula.

［ただし、ＳＲは剪断速度（秒^−１）、ＳＳは剪断応力（ダイン／ｃｍ^２）、そしてＫは定数を示す。］Ｎ値は１に近いほどポリアリーレンスルフィドは線状に近い構造であり、Ｎ値が高いほど分岐が進んだ構造であることを示す。

[Wherein SR represents a shear rate (second ⁻¹ ), SS represents a shear stress (dyne / cm ² ), and K represents a constant. The closer the N value is to 1, the closer the polyarylene sulfide is to a linear structure, and the higher the N value is, the more branched the structure is.

  The production method of the polyarylene sulfide resin (b) is not particularly limited. For example, 1) a method of polymerizing a dihalogenoaromatic compound and, if necessary, other copolymerization components in the presence of sulfur and sodium carbonate. 2) Self-condensation of p-chlorothiophenol with other copolymerization components if necessary, 3) In an organic polar solvent, sulfidizing agent and dihalogenoaromatic compound, and further if necessary Examples thereof include a method of reacting a copolymerization component and 4) a method of melt polymerization of a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor as required. Among these methods, the method 3) is versatile and preferable. In the reaction, an alkali metal salt of carboxylic acid or sulfonic acid or an alkali hydroxide may be added to adjust the degree of polymerization. Among the above methods 3), a hydrous sulfiding agent is introduced into a mixture containing a heated organic polar solvent and a dihalogenoaromatic compound at a rate at which water can be removed from the reaction mixture, and the dihalogenoaromatic compound and A method for producing a polyarylene sulfide resin by reacting with a sulfidizing agent and controlling the amount of water in the reaction system in the range of 0.02 to 0.5 mol relative to 1 mol of the organic polar solvent ( Japanese Patent Application Laid-Open No. 07-228699), a polyhaloaromatic compound, an alkali metal hydrosulfide and an organic acid alkali metal salt in the presence of a solid alkali metal sulfide and an aprotic polar organic solvent. 0.01-0.9 mol of organic acid alkali metal salt and 1 mol of water in the reaction system with respect to 1 mol of aprotic polar organic solvent A method of reacting while controlling the .02 mols (WO2010 / 058 713 pamphlet reference.) Is what is particularly preferably obtained by.

  Examples of the conductive filler (c) used in the present invention include carbon materials such as artificial graphite, natural graphite, glassy carbon, carbon black, acetylene black, ketjen black, carbon fiber, and carbon nanofiber, metal fiber, Metals or metal compounds such as silver and copper can be mentioned. Among them, carbon materials are preferable because they are lightweight and excellent in corrosion resistance, and these carbon materials can be used alone or in combination of two or more. it can. There is no restriction | limiting in particular in the shape of the granular material of these carbon materials, Any of plate shape, spherical shape, fibrous shape, an amorphous shape, etc. may be sufficient. Also, expanded graphite obtained by chemically treating graphite can be used. In view of conductivity, artificial graphite, natural graphite, expanded graphite and the like are preferable in that a material having high conductivity can be obtained in a smaller amount.

  The size of the conductive filler (c) is not particularly limited as long as it does not impair the effects of the present invention. However, the conductive filler (c) has excellent conductivity such as surface resistance and volume resistivity. When used for conductive materials such as tape, the average particle size is in the range of 1 μm or less from the viewpoint of excellent surface appearance and surface smoothness, and 0.5 μm or less from the viewpoint of excellent gloss (glossiness). It is preferable that it is the range of this, and it is more preferable that it is the range of 0.1 micrometer or less. Furthermore, uniform conductivity, that is, when the variation in electrical resistance depending on the location in the molded body is kept low, and the difference in surface appearance and surface smoothness such as conductivity, especially transfer belts, conductive trays, carrier tapes, etc. is remarkable. When it is used for a sheet-like or film-like conductive material appearing, it is preferably in the range of 100 nm or less. On the other hand, in terms of excellent wettability with the polyarylene sulfide resin and good moldability and dispersibility, the thickness is preferably in the range of 10 nm or more, and more preferably in the range of 20 nm or more.

  The content of the conductive filler (c) in the polyarylene sulfide resin composition is not particularly limited as long as it does not impair the effects of the present invention, but can impart excellent mechanical strength and conductivity. From the viewpoint, it is preferably in the range of 1 part by mass or more, more preferably in the range of 3 parts by mass or more, and further in the range of 5 parts by mass or more with respect to 100 parts by mass of the polyarylene sulfide resin (b). Most preferably. On the other hand, from the viewpoint of suppressing deterioration of the appearance of the molded product, the range is preferably 50 parts by mass or less and more preferably 40 parts by mass or less with respect to 100 parts by mass of the polyarylene sulfide resin (b). Is more preferable, and the range of 30 parts by mass or less is most preferable.

  In addition to the above components, the polyarylene sulfide resin composition of the present invention, in addition to the above-described components, further improves the performance of the present invention within the range that does not impair the effects of the present invention. May be included.

  Such additives include various additives such as colorants, heat stabilizers, UV stabilizers, foaming agents, rust preventives, flame retardants, lubricants, and polyesters, polyamides, polyimides, polyetherimides, depending on the application. , Polycarbonate, Polyphenylene ether, Polysulfone, Polyethersulfone, Polyetheretherketone, Polyetherketone, Polyarylene, Polyethylene, Polypropylene, Polytetrafluoroethylene, Polydifluoroethylene, Polystyrene, ABS resin, Epoxy resin, Silicone Synthetic resins such as resins, phenolic resins, urethane resins, and liquid crystal polymers, or elastomers such as fluorine rubber and silicone rubber, especially epoxy groups, amino groups, carboxy groups, isocyanato groups, or the following structural formulas (1) and ( 2)

（但し、構造式（１）、構造式（２）中、Ｒは炭素原子数１〜８のアルキル基を表す。）で表される部分構造からなる群から選ばれる少なくとも１種の官能基を有するポリオレフィンエラストマなどの樹脂が挙げられる。

(However, in Structural Formula (1) and Structural Formula (2), R represents an alkyl group having 1 to 8 carbon atoms.) At least one functional group selected from the group consisting of partial structures represented by Examples thereof include resins such as polyolefin elastomer.

  Examples of the filler include fillers of various shapes such as granular and fibrous, for example, glass fiber, silane glass fiber, ceramic fiber, aramid fiber, potassium titanate, silicon carbide, calcium sulfate, calcium silicate. Fiber fillers such as natural fibers such as wollastonite, barium sulfate, calcium sulfate, clay, pyrophyllite, bentonite, sericite, zeolite, mica, mica, talc, attapulgite, ferrite, silicic acid Examples include calcium, calcium carbonate, magnesium carbonate, and glass beads.

  The amount of these additives and fillers used varies depending on the purpose and cannot be specified in general. However, in the range of 0.01 to 1000 parts by mass with respect to 100 parts by mass of the polyarylene sulfide resin, What is necessary is just to adjust suitably according to the objective and the use so that the effect of this invention may not be impaired. Further, the size of the filler is not particularly limited as long as it does not impair the effects of the present invention, but from the viewpoint of surface appearance and surface smoothness, the average particle diameter is within a range of less than 1 μm. Preferably there is. On the other hand, it is preferably in the range of 10 nm or more from the viewpoint of excellent wettability with the polyarylene sulfide resin and good moldability and dispersibility.

  The method for producing the polyarylene sulfide resin composition of the present invention is not particularly limited as long as the effects of the present invention are not impaired. For example, the aqueous solution (a), polyarylene sulfide resin (b), and conductive material (raw materials) Examples thereof include a method in which c) is uniformly mixed with a tumbler or Henschel mixer, and then melt kneaded using a Banbury mixer, a mixing roll, a single or twin screw extruder, a kneader, and the like. In particular, a melt kneading method using a single or twin screw extruder having a sufficient kneading force is preferable.

  Specifically, the aqueous solution (a), the polyarylene sulfide resin (b), the conductive filler (c), and, if necessary, other blending components are mixed uniformly with a tumbler or Henschel mixer, A condition in which the ratio (discharge amount / screw rotation number) between the resin component discharge amount (kg / hr) and the screw rotation speed (rpm) is 0.02 to 2 (kg / hr / rpm). And a method of melt kneading. By producing under such conditions, a molded body in which the coupling agent (a) and the conductive filler (c) are finely dispersed can be produced using the polyarylene sulfide resin (b) as a matrix (continuous phase).

  More specifically, the above-described production method is preferably a method in which the above-described components are put into an extruder and melt-kneaded under temperature conditions of a set temperature of 300 ° C. and a resin temperature of about 320 ° C. At this time, the discharge amount of the resin component is preferably in the range of 4 to 400 kg / hr at a rotation speed of 200 rpm, and more preferably 10 to 250 kg / hr from the viewpoint of dispersibility. Accordingly, the ratio (discharge amount / screw rotation number) between the resin component discharge amount (kg / hr) and the screw rotation speed (rpm) is particularly 0.05 to 1.25 (kg / hr / rpm). Is preferred.

  The polyarylene sulfide resin composition melt-kneaded in this manner is then directly molded into a molded body using various known molding methods, or once molded as pellets, and then molded into various moldings. By subjecting to a machine and melt molding, it can be molded into a desired molded body. Known molding methods include injection molding, press molding, calendar molding, roll molding, extrusion molding, cast molding, and blow molding.

The molded body thus obtained is obtained by finely dispersing the coupling agent (a) and the conductive filler (c) in the continuous phase composed of the polyarylene sulfide resin (b). The ratio of the granular material originating in is suppressed low. For example, the ratio of the granular material containing a coupling agent having a circle-equivalent diameter of 1 μm or more is less than 5, preferably less than 2 and more preferably less than 1 per 1 mm ^{2 of} the molded body surface. For this reason, the molded object of this invention becomes the thing excellent in the external appearance surface property and surface smoothness, and the effect becomes remarkable especially when shape | molded in a sheet form or a film form. Furthermore, when it is formed into a sheet, film, strand, or fiber, it is possible to suppress a decrease in mechanical strength caused by the granular material, and breakage of the film or sheet, as well as strand breakage or fiber breakage. Can be suppressed.

  In order to form the target shape, the pellets of the polyarylene sulfide resin composition are further subjected to a molding machine, and known methods such as an extrusion molding method, an injection molding method, a compression molding method, a blow molding method, and an injection compression molding method. Apply to various molding methods to obtain a sheet or film (molding process).

  In particular, additives with a small amount may be added and mixed immediately before the molding step.

  The polyarylene sulfide resin molded article of the present invention utilizes various performances such as mechanical strength, heat resistance and dimensional stability inherent in the polyarylene sulfide resin, for example, sensors, LED lamps, connectors, sockets, resistors, Relay case, switch, coil bobbin, capacitor, variable capacitor case, oscillator, various terminal boards, transformer, plug, printed circuit board, tuner, speaker, microphone, headphones, small motor, magnetic head base, semiconductor, liquid crystal, FDD carriage, FDD Electrical / electronic parts such as chassis, motor brush holder, parabolic antenna, computer-related parts, VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio / laser discs / compacts Di Audio equipment parts such as mobile phone, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, home electrical appliance parts, office computer related parts, telephone related parts, facsimile related parts, copying Machine-related parts such as machine-related parts, cleaning jigs, motor parts, writers, typewriters, etc., optical equipment such as microscopes, binoculars, cameras, and watches, precision machine-related parts, and water taps , Mixing faucets, pump parts, pipe joints, water volume control valves, relief valves, hot water temperature sensors, water volume sensors, water meter housings and other water-related parts, valve alternator terminals, alternator connectors, IC regulators, light dial potentio Various valves such as meter base and exhaust gas valve, fuel Engagement / exhaust / intake system pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, throttle position sensor, crankshaft Position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, warm air flow control valve for heating, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, starter Relais, wire harness for transmission, window washer nozzle, air conditioner panel switch board, carp for fuel related electromagnetic valve Connector, fuse terminal, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device case, HEV condenser case, vehicle speed sensor, cable Various uses such as liners and plastic gears for automobiles and vehicle-related parts, bag filters, thermal insulation, non-woven fabrics and sewing fibers, adhesive films, release films, circuit boards, film capacitors, insulating films for motors and transformers They are widely useful as film materials, electromagnetic wave shielding materials, and the like, such as transfer belts, circuit boards, and fuel tubes.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention concretely, all parts and% are mass references | standards unless there is particular notice below.

[Comparative Example 1] Dry blend The coupling agent, polyarylene sulfide resin and conductive filler shown in Table 1 were uniformly mixed with a tumbler according to the blending ratio shown in Table 1, with a vent made by Nippon Steel Co., Ltd. A biaxial extruder “TEX-30α” is charged and the resin component discharge rate is 15 kg / hr, the screw rotation speed is 200 rpm, and the ratio of the resin component discharge rate (kg / hr) to the screw rotation rate (rpm) (discharge rate / Screw rotation number) = 0.075 (kg / hr / rpm), maximum torque 32 (A), melt kneading at a set resin temperature of 300 ° C. to obtain resin composition pellets. Next, after the pellets of the obtained resin composition were allowed to stand at room temperature for 24 hours, they were extruded using a T-die extruder at a set temperature of 300 ° C. and a roll temperature of 70 ° C. to produce a film having a thickness of 80 to 100 μm. .

(Examples 1-10, Comparative Examples 2-4)
The coupling agents shown in Tables 1 and 2 were stirred at 23 ° C. for 1 hour in 140 g of a water-ethanol mixed solvent having a predetermined alcohol concentration to prepare an aqueous solution.

  Subsequently, the prepared aqueous solution, polyarylene sulfide resin and conductive filler were uniformly mixed with a tumbler according to the blending ratios described in Tables 1 and 2, and a twin-screw extruder “TEX- The ratio Q / N (discharge amount / screw rotation number) (kg / hr / rpm) of the resin component discharge amount (kg / hr) and screw rotation speed (rpm) described in Tables 1 to 3 ), And melt-kneaded at a set resin temperature of 300 ° C. to obtain resin composition pellets. Next, after the pellets of the obtained resin composition were allowed to stand at room temperature for 24 hours, they were extruded using a T-die extruder at a set temperature of 300 ° C. and a roll temperature of 70 ° C. to produce a film having a thickness of 80 to 100 μm.

(Evaluation of surface appearance)
A mapping image of the film was prepared with an Si element using a SEM / EDS apparatus (“JSM-6360A” manufactured by JEOL Ltd.), and the number of granular materials having an equivalent circle diameter of 1 μm or more was counted from the image. The 30 visual fields were observed and averaged, and the surface appearance was judged according to the following criteria.
◎ ^+: 1mm ² in less than two ◎: 1mm ² to less than five two or more ○: 1mm ² to 5 or more less than 10 △: 1mm ² to 10 or more less than 100 ×: 1mm ² to 100 or more

(Measuring mechanical strength)
(Tensile properties)
The film was cut into 15 × 110 mm, and the tensile strength was measured with a tensile tester (AGS-5kNX: manufactured by Shimadzu Corporation) at a measurement temperature of 23 ° C., a distance between marked lines of 50 mm, and a test speed of 10 mm / min.

(Measurement of surface resistance)
<Surface resistivity, volume resistivity>
The surface resistivity (Ω / □) and the volume resistivity (Ω · cm) were measured in a 23 ° C. and 55% RH environment using a resistance measuring instrument “HIRESTA UP / URS probe” manufactured by Mitsubishi Chemical Corporation. The films produced in Examples 1 to 5 and Comparative Examples 1 and 2 were used as a sample in which the belt was cut to a length of 300 mm in the longitudinal direction, and a total of 3 locations at equal pitches in the width direction of the samples and 4 locations in the longitudinal direction. The surface resistivity and the volume resistivity were measured for 12 locations at an applied voltage of 100 V and 10 seconds later, respectively, and the average values were shown as common logarithmic values. The measurement sample was measured after being left for 24 hours in an environment of 23 ° C. and 55% RH.

(Gloss value measurement)
The gloss was measured with a gloss meter “VG2000” (manufactured by Nippon Denshoku), and the result was shown in gloss. The gloss measurement condition was an incident angle of 20 degrees.

<Method for evaluating carbon black dispersibility, coupling agent aggregate>
The composition and the dilution polypropylene resin are 1/1 in a mass ratio in a test machine in which a filtration tester is attached to the outlet side of a single screw extruder having a screw diameter of 30 mm and an L / D value of 30. The mixture of the composition and the polypropylene resin for dilution was extruded from the filtration tester. Here, the temperature of the jacket of the single screw extruder was set to 320 ° C. The configuration of the filter attached to the filtration pressure tester was # 80 μm × baked 20 μm × # 80 μm, and the screw rotation speed was 30 rpm.

  When extruding from the filtration pressure tester, the pressure when the material flows into the filter inlet side (resin pressure) and the pressure when discharged from the filter outlet side are measured, and the difference (filtration pressure, MPa) is obtained. This was used as a filtration pressure test value. The lower the filtration pressure test value, the smaller the formation of coarse particles such as carbon black aggregates and silane coupling agent condensates, which means that the surface appearance of the molded product is excellent.

＊発火
なお、表１〜２中の配合樹脂、材料は下記のものである。
Ｓｉ（Ａ１）：３−グリシドキシプロピルトリメトキシシラン（東レ・ダウコーニング社製「Ｚ−６０４０」）
Ｓｉ（Ａ２）：３−アミノプロピルトリメトキシシラン（東レ・ダウコーニング社製「Ｚ−６６１０」）
ＰＰＳ（Ｂ１）：ポリフェニレンスルフィド（ＤＩＣ株式会社製「ＭＡ−５２０」、溶融粘度（Ｖ６）１２０〔Ｐａ・ｓ〕）
ただし、ＰＰＳ樹脂の溶融粘度（Ｖ６）は以下の方法で測定した値である。
フローテスター（島津製作所製高化式フローテスター「ＣＦＴ−５００Ｄ型」）を用い
て、温度３００℃、荷重１．９６ＭＰａ、オリフィス長とオリフィス径との、前者／後者
の比が１０／１であるオリフィスを使用して６分間保持後の溶融粘度を測定した。

* Ignition In addition, the compounding resin and material in Tables 1-2 are the following.
Si (A1): 3-glycidoxypropyltrimethoxysilane (“Z-6040” manufactured by Dow Corning Toray)
Si (A2): 3-aminopropyltrimethoxysilane (“Z-6610” manufactured by Toray Dow Corning)
PPS (B1): Polyphenylene sulfide (“MA-520” manufactured by DIC Corporation, melt viscosity (V6) 120 [Pa · s])
However, the melt viscosity (V6) of the PPS resin is a value measured by the following method.
Using a flow tester (Shimadzu Corporation Koka-type flow tester “CFT-500D type”), the temperature / 300 ° C., the load 1.96 MPa, the orifice length / orifice diameter ratio is 10/1. The melt viscosity after holding for 6 minutes was measured using an orifice.

Conductive filler (C1): carbon (“Denka Black granular product” manufactured by Denki Kagaku Kogyo Co., Ltd., average particle size: 35 nm)
Conductive filler (C2): carbon (“DENKA BLACK HS-100” average particle size 48 nm, manufactured by Denki Kagaku Kogyo Co., Ltd.)
Conductive filler (C3): Artificial graphite (“UF-G30” average particle diameter 10 μm, manufactured by Showa Denko KK)

Claims (7)

An aqueous solution (a) obtained by dissolving the coupling agent (a2) in water and an alcohol mixed solvent (a1) having an alcohol concentration in the range of 0.1 to 90 v / v%, a polyarylene sulfide resin (b), A method for producing a polyarylene sulfide resin composition, comprising melt-kneading a conductive filler (c). The method for producing a polyarylene sulfide resin composition according to claim 1, wherein the concentration of the coupling agent in the aqueous solution (a) is in the range of 5 to 75 mass%. The method for producing a polyarylene sulfide resin composition according to claim 1 or 2, wherein the coupling agent (a2) is a silane coupling agent. The melt kneading uses a twin-screw kneading extruder, and the ratio (discharge amount / screw rotation number) between the discharge amount (kg / hr) of the resin component and the screw rotation number (rpm) is 0.02 to 2 (kg / The method for producing a polyarylene sulfide resin composition according to any one of claims 1 to 3, which is melt-kneaded under a condition of hr / rpm). The method for producing a polyarylene sulfide resin composition according to any one of claims 1 to 4, wherein the conductive filler (c) has an average particle diameter of 1 µm or less. The method for producing a polyarylene sulfide resin composition according to any one of claims 1 to 5, wherein the conductive filler (c) is a carbon material. The manufacturing method of the polyarylene sulfide resin molded object formed by shape | molding the polyarylene sulfide resin composition manufactured by the manufacturing method as described in any one of Claims 1-6.