Polyarylene sulfide resin composition and molded article obtained by molding therefrom

Abstract

The present invention provides a polyarylene sulfide resin composition exhibiting excellent tracking resistance, flame retardancy, and mechanical properties, as well as a molded article obtained by molding it. [Solution] A polyarylene sulfide resin composition characterized by containing, in 100 parts by weight of polyarylene sulfide resin (component A), which consists of 10 to 90 parts by weight of polyarylene sulfide resin (component A-1) containing mercapto groups at the ends and 10 to 90 parts by weight of polyarylene sulfide resin (component A-2) containing phenyl groups at the ends, (B) 51 to 80 parts by weight of semi-aromatic polyamide resin (component B), (C) 70 to 175 parts by weight of metal hydroxide (component C), and (D) fibrous filler (component D).

Description

Technical Field

[0001] The present invention relates to a resin composition excellent in tracking resistance, flame retardancy, and mechanical properties.

Background Art

[0002] Polyarylene sulfide resin is an engineering plastic excellent in heat resistance, flame retardancy, and mechanical properties. Therefore, polyarylene sulfide resin is widely used as electrical and electronic components, vehicle-related components, aircraft components, and housing equipment components. In recent years, with the spread of electric vehicles, efforts have been made to reduce the weight of the vehicle body for the purpose of extending the cruising range, and the demand for resin materials has been expanding. Some of them are used in a high-voltage environment, and from the viewpoint of ensuring safety when a voltage is applied, they are required to have tracking resistance. However, since polyarylene sulfide resin has low tracking resistance, there is a situation where its use in a high-voltage environment is limited as it is.

[0003] As a means of solving this problem, Patent Document 1 discloses a resin composition consisting of polyphenylene sulfide resin, polyamide resin, and metal hydroxide for the purpose of improving tracking resistance, heat resistance, and arc resistance. However, while it mentions tracking resistance and the rate of decrease in tensile strength after heat treatment, it does not mention the magnitude of the mechanical strength itself or the flame retardancy which is thought to worsen by incorporating polyamide resin. Patent Document 2 discloses a resin composition consisting of polyphenylene sulfide resin, polyamide resin, and metal hydroxide, in which the metal hydroxide is dispersed in the composition with an average secondary particle diameter of 5 μm or less, for the purpose of improving mechanical properties and tracking resistance and reducing the amount of generated gas. However, while it mentions tracking resistance, tensile strength, and flexural strength, the mechanical strength is not sufficient, and it does not mention the flame retardancy which is a characteristic of polyarylene sulfide resin. Patent Document 3 discloses a composition comprising polyphenylene sulfide resin, polyamide resin, magnesium hydroxide, and elastomer, with specified viscosity number and structure of the polyamide resin, for the purpose of improving tracking resistance and mechanical properties and suppressing mold contamination. However, while it mentions tracking resistance, flexural strength, flexural modulus, and weld strength, it does not mention flame retardancy, which is a concern as it may worsen with the addition of polyamide resin and elastomer. Patent Document 4 discloses a resin composition comprising a thermoplastic aromatic polymer with a melting temperature of approximately 250°C or higher, polyamide resin, and aluminum hydroxide, for the purpose of improving tracking resistance and mechanical properties. However, while it mentions tracking resistance, tensile strength, tensile modulus, and notched Charpy impact strength, it does not mention flame retardancy. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 5-271542 [Patent Document 2] Patent No. 5273321 [Patent Document 3] Patent No. 7238429 [Patent Document 4] Special Publication No. 2024-506017 [Overview of the project] [Problems that the invention aims to solve]

[0005] The object of the present invention is to provide a polyarylene sulfide resin composition that is excellent in tracking resistance, flame retardancy, and mechanical properties, and a molded article made therefrom. [Means for solving the problem]

[0006] As a result of diligent research, the inventors have discovered that by blending a polyarylene sulfide resin, consisting of a polyarylene sulfide resin containing mercapto groups at the ends and a polyarylene sulfide resin containing phenyl groups at the ends, with a semi-aromatic polyamide resin, a metal hydroxide, and a fibrous filler, a resin composition with excellent tracking resistance, flame retardancy, and mechanical properties can be obtained, thus solving the above-mentioned problems.

[0007] In other words, the present invention is as follows. 1. A polyarylene sulfide resin composition characterized by containing, per 100 parts by weight of polyarylene sulfide resin (component A), which consists of 10 to 90 parts by weight of (A) a polyarylene sulfide resin containing mercapto groups at the terminals (component A-1) and 10 to 90 parts by weight of polyarylene sulfide resin containing phenyl groups at the terminals (component A-2), 51 to 80 parts by weight of (B) a semi-aromatic polyamide resin (component B), 70 to 175 parts by weight of (C) a metal hydroxide (component C), and 75 to 250 parts by weight of (D) a fibrous filler (component D). 2. The B component is at least one semi-aromatic polyamide resin selected from the group consisting of a semi-aromatic polyamide resin (B-1 component) composed of a dicarboxylic acid component having terephthalic acid as a main component and an aliphatic diamine component having an aliphatic diamine with 10 carbon atoms as a main component, and a semi-aromatic polyamide resin (B-2 component) composed of a dicarboxylic acid component having terephthalic acid as a main component and an aliphatic diamine component having an aliphatic diamine with 9 carbon atoms as a main component. The polyarylene sulfide resin composition according to item 1 above is characterized by this. 3. The polyarylene sulfide resin composition according to item 1 or 2 above is characterized in that the C component is magnesium hydroxide. 4. The polyarylene sulfide resin composition according to any one of items 1 to 3 above is characterized in that the D component is glass fiber. 5. A molded article obtained by molding the polyarylene sulfide resin composition according to any one of items 1 to 4 above.

Advantages of the Invention

[0008] According to the present invention, it is possible to provide a polyarylene sulfide resin composition excellent in tracking resistance, flame retardancy, and mechanical properties, and a molded article obtained by molding the same.

Modes for Carrying Out the Invention

[0009] Hereinafter, the details of the present invention will be described.

[0010] <Regarding the A component> The polyarylene sulfide resin used as component A in this invention is a polyarylene sulfide resin comprising 10 to 90 parts by weight of a polyarylene sulfide resin containing mercapto groups at the ends (component A-1) and 10 to 90 parts by weight of a polyarylene sulfide resin containing phenyl groups at the ends (component A-2). The content of component A-1 is 10 to 90 parts by weight per 100 parts by weight of component A, preferably 20 to 80 parts by weight, more preferably 20 to 50 parts by weight, and even more preferably 30 to 50 parts by weight. If the content of component A-1 is less than 10 parts by weight, the extrudeability deteriorates and pelletization becomes difficult if the content of component C is high, and pelletization is possible if the content of component C is low, but the mechanical properties and tracking resistance deteriorate. On the other hand, if it exceeds 90 parts by weight, the mechanical properties and flame retardancy deteriorate. Furthermore, the content of polyarylene sulfide resin containing phenyl groups at the ends is 10 to 90 parts by weight, preferably 20 to 80 parts by weight, more preferably 50 to 80 parts by weight, and even more preferably 50 to 70 parts by weight, because it has excellent tracking resistance, flame retardancy, and mechanical properties.

[0011] Examples of polyarylene sulfide resins include those whose constituent units consist of, for example, p-phenylene sulfide units, m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfide sulfone units, phenylene sulfide ketone units, phenylene sulfide ether units, diphenylene sulfide units, substituent-containing phenylene sulfide units, branched structure-containing phenylene sulfide units, etc. Among these, those containing 70 mol% or more, particularly 90 mol% or more, of p-phenylene sulfide units are preferred, and poly(p-phenylene sulfide) is even more preferred.

[0012] The degree of dispersion (Mw / Mn), expressed as the weight-average molecular weight (Mw) and number-average molecular weight (Mn) of the polyarylene sulfide resin, is preferably 2.7 or higher, more preferably 2.8 or higher, and even more preferably 2.9 or higher. If the degree of dispersion is less than 2.7, there may be an increase in burr generation during molding. There is no particular upper limit for the degree of dispersion (Mw / Mn), but it is preferably 10 or lower. Here, the weight-average molecular weight (Mw) and number-average molecular weight (Mn) are values ​​calculated in polystyrene equivalent by gel permeation chromatography (GPC). The solvent used was 1-chloronaphthalene, and the column temperature was 210°C.

[0013] The method for producing polyarylene sulfide resins containing mercapto groups at their ends is not particularly limited and can be polymerized by known methods. However, a particularly preferred polymerization method is one in which alkali metal sulfide salts and halogen-substituted aromatic compounds are polymerized in a polar organic solvent.

[0014] Typical polar organic solvents used in the above-mentioned manufacturing method include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, cyclohexylpyrrolidone, dimethylformamide, dimethylacetamide, and sulfolane.

[0015] Typical alkali metal sulfide salts used in the above-mentioned manufacturing method include, for example, anhydrous or hydrated sodium sulfide, rubidium sulfide, and lithium sulfide. Alternatively, the alkali metal sulfide salt may be obtained by reacting an alkali metal hydrosulfide with an alkali metal hydroxide.

[0016] Examples of typical halogen-substituted aromatic compounds used in the above-mentioned manufacturing method include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 4,4'-dichlorodiphenylsulfone, 4,4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl ether, and 4,4'-dichlorobiphenyl.

[0017] In the above manufacturing method, an alkali metal salt of carboxylic acid or sulfonic acid may be added to adjust the degree of polymerization, or an alkali hydroxide may be added.

[0018] In the above manufacturing method, washing may be performed after the acid treatment. The acid used in this acid treatment is not particularly limited as long as it has an effect of decomposing the polyarylene sulfide resin, and examples thereof include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, and propionic acid. Among them, acetic acid and hydrochloric acid are preferable. For this acid treatment, powder or granules of the polyarylene sulfide resin may be used, or the polyarylene sulfide resin in the slurry state after polymerization may be directly subjected to the acid treatment. As a method of the acid treatment, there is a method of immersing the polyarylene sulfide resin in an acid or an aqueous acid solution. The acid-treated polyarylene sulfide resin is preferably washed several times with water or warm water in order to physically remove the remaining acid or salt. The water used at this time is preferably distilled water or deionized water.

[0019] The manufacturing method of the polyarylene sulfide resin containing a phenyl group at the terminal is not particularly limited and is polymerized by a known method. Particularly preferred polymerization methods include those described in U.S. Registered Patent Nos. 4,746,758, 4,786,713, JP-T 2013-522385, JP-A 2012-233210, and Patent No. 5167276. These manufacturing methods are methods of directly heating a diiodoaryl compound and solid sulfur without a polar solvent for polymerization.

[0020] The above manufacturing method includes an iodination step and a polymerization step. In the iodination step, an aryl compound is reacted with iodine to obtain a diiodoaryl compound. In the subsequent polymerization step, a polymerization terminator is used to carry out a polymerization reaction of the diiodoaryl compound with solid sulfur to produce a polyarylene sulfide resin. Iodine is generated in a gaseous state in this step, and this is recovered and used again in the iodination step. Substantially, iodine is a catalyst.

[0021] Typical solid sulfur used in the above manufacturing method includes cyclo-octa sulfur form (S8) in which 8 atoms are linked at room temperature. However, the sulfur compound used in the polymerization reaction is not limited, and any form can be used as long as it is solid or liquid at normal temperature.

[0022] Typical diiodoaryl compounds used in the above manufacturing method include at least one selected from the group consisting of diiodobenzene, diiodonaphthalene, diiodobiphenyl, diiodobisphenol, and diiodobenzophenone. Also, derivatives of iodoaryl compounds with an alkyl group or a sulfone group bonded thereto, or oxygen or nitrogen introduced therein are used. Iodoaryl compounds are classified into isomers depending on the bonding position of the iodine atoms. Preferred examples among these isomers are compounds in which iodine is symmetrically located at both ends of the aryl compound molecule, such as p-diiodobenzene, 2,6-diiodonaphthalene, and p,p'-diiodobiphenyl. The content of the iodoaryl compound is preferably 500 to 10,000 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined in consideration of the formation of disulfide bonds.

[0023] As the polymerization terminator used in the above manufacturing method, diphenyl sulfide and diphenyl disulfide are preferred. By using these compounds as the polymerization terminator, a polyarylene sulfide resin containing a phenyl group at the terminal can be produced. The content of the polymerization terminator is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined in consideration of the formation of disulfide bonds.

[0024] In the above manufacturing method, a polymerization reaction catalyst may be used. Representative polymerization reaction catalysts include nitrobenzene-based catalysts. Preferred examples of nitrobenzene-based catalysts include at least one selected from the group consisting of 1,3-diiodo-4-nitrobenzene, 1-iodo-4-nitrobenzene, 2,6-diiodo-4-nitrophenol, iodonitrobenzene, and 2,6-diiodo-4-nitroamine. The content of the polymerization reaction catalyst is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined in consideration of the formation of disulfide bonds.

[0025] <Regarding Component B> The resin composition of the present invention contains a semi-aromatic polyamide resin as Component B. Any semi-aromatic polyamide resin may be used as long as it belongs to the category called semi-aromatic polyamide resin. A semi-aromatic polyamide resin is a polyamide resin having an aromatic ring skeleton and an aliphatic skeleton, and can be synthesized, for example, from an aromatic dicarboxylic acid and an aliphatic diamine as raw materials.

[0026] Examples of the dicarboxylic acid component include terephthalic acid, isophthalic acid, naphthalenedicarboxylic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, etc. Among them, terephthalic acid is preferred. The dicarboxylic acid component may be used alone or in combination of multiple kinds. Also, other dicarboxylic acids may be used as long as the effects of the present invention are not impaired.

[0027] Examples of diamine components include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 2-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, cyclohexanediamine, metaxylylenediamine, and benzenediamine, among which aliphatic diamines with 9 and 10 carbon atoms are preferred. These may be used individually or in combination.

[0028] Component B is preferably at least one semi-aromatic polyamide resin selected from the group consisting of a semi-aromatic polyamide resin (component B-1) comprising a dicarboxylic acid component mainly composed of terephthalic acid and an aliphatic diamine component mainly composed of a C10 aliphatic diamine, and a semi-aromatic polyamide resin (component B-2) comprising a dicarboxylic acid component mainly composed of terephthalic acid and an aliphatic diamine component mainly composed of a C9 aliphatic diamine.

[0029] In the present invention, component B preferably has a melting point higher than 300°C, which may further improve heat resistance. If there are multiple melting points, or if two or more types of semi-aromatic polyamide resins are used, the melting point may be 300°C or lower. Here, the melting point refers to the temperature of the endothermic peak that appears when approximately 10 mg of a pellet of semi-aromatic polyamide resin is taken and cooled to 20°C from a molten state at a rate of 20°C / min using a differential scanning calorimeter under a nitrogen atmosphere, held for 5 minutes, and then heated at a rate of 20°C / min. However, if two or more endothermic peaks are detected, the peak with the highest temperature is taken as the melting point.

[0030] The content of Component B is 51 to 80 parts by weight, preferably 51 to 70 parts by weight, and more preferably 51 to 60 parts by weight with respect to 100 parts by weight of Component A. When the content of Component B is less than 51 parts by weight, the mechanical properties deteriorate. On the other hand, when the content of Component B exceeds 80 parts by weight, the flame retardancy deteriorates.

[0031] <Regarding Component C> The resin composition of the present invention contains a metal hydroxide as Component C. As the metal hydroxide, any one belonging to the category called metal hydroxide may be used. Examples of the metal hydroxide include magnesium hydroxide, aluminum hydroxide, calcium hydroxide and the like. Among them, magnesium hydroxide is preferably used because of its excellent tracking resistance, flame retardancy and mechanical properties.

[0032] As the magnesium hydroxide, magnesium hydroxide with a relatively high purity having a content of hydroxide represented by the chemical formula Mg(OH)2 of 80% by weight or more is preferable, and magnesium hydroxide having a hydroxide content represented by the chemical formula Mg(OH)2 of 80% by weight or more, a CaO content of 5% by weight or less, and a chlorine content of 1% by weight or less is more preferable, and magnesium hydroxide having a hydroxide content represented by Mg(OH)2 of 95% by weight or more, a CaO content of 1% by weight or less, and a chlorine content of 0.5% by weight or less is further preferable, and high-purity magnesium hydroxide having a hydroxide content represented by Mg(OH)2 of 98% by weight or more, a CaO content of 0.1% by weight or less, and a chlorine content of 0.1% by weight or less is particularly preferable.

[0033] The shape of the magnesium hydroxide may be particulate, flaky or fibrous, but from the viewpoint of dispersibility and the like, particulate and flaky are preferable. The particle diameter of the magnesium hydroxide is preferably such that the average particle diameter (D 50 ) measured by the laser diffraction scattering method is 0.3 to 10 μm, and more preferably 0.5 to 3 μm. Further, as the specific surface area of the magnesium hydroxide, since it is particularly excellent in tracking resistance and mechanical strength, it is preferably 10 m 2 / g or less.

[0034] Examples of magnesium hydroxide include magnesium hydroxide without surface treatment, magnesium hydroxide surface-treated with higher fatty acids and / or metal salts of higher fatty acids, silane coupling agents, titanate coupling agents, aluminate coupling agents, etc. There is no particular limitation on the surface coating treatment agent for the surface-treated magnesium hydroxide. Examples of higher fatty acids and their metal salts include stearic acid, oleic acid, and their alkali metal salts, etc. Examples of anionic surfactants include sulfuric acid esters of higher alcohols, etc. Examples of phosphate esters include esters of orthophosphoric acid and higher alcohols, etc. Examples of silane coupling agents include vinyltriethoxysilane, γ-methacryloxypropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-glycidoxypropyltrimethoxysilane, γ-mercaptopropyltrimethoxysilane, etc. Examples of titanate coupling agents include isopropyltriisostearoyl titanate, etc. Examples of aluminate coupling agents include acetoxyalkoxyaluminum diisopropylate, etc. Examples of esters of polyhydric alcohols and fatty acids include glycerin monostearate, etc. Among them, magnesium hydroxide surface-treated with a silane coupling agent is preferred because of its excellent mechanical strength.

[0035] The content of Component C is 70 to 175 parts by weight, preferably 95 to 150 parts by weight, and more preferably 110 to 150 parts by weight with respect to 100 parts by weight of Component A. When the content of Component C is less than 70 parts by weight, the flame retardancy and tracking resistance deteriorate. On the other hand, when the content of Component C exceeds 175 parts by weight, the extrudability deteriorates and pelletization becomes difficult.

[0036] <Regarding Component D> The resin composition of the present invention contains a fibrous filler as component D. Any fibrous filler belonging to the category of fibrous fillers may be used, including glass fibers, carbon fibers, aramid fibers, alumina fibers, silicon carbide fibers, ceramic fibers, asbestos fibers, gypsum fibers, metal fibers, and fibrous fillers coated with conductive materials. Among these, glass fibers are preferred from the viewpoint of mechanical properties.

[0037] Suitable examples of glass fibers include glass fibers with a round cross-section, flattened cross-section glass fibers with an average major axis of the fiber length cross-section of 10 to 50 μm and an average major axis to minor axis ratio (major axis / minor axis) of 1.5 to 8, and glass milled fibers.

[0038] The glass composition of the glass fibers is not particularly limited and can be any of the various glass compositions represented by A glass, C glass, and E glass. Such glass fibers may contain components such as TiO2, SO3, and P2O5 as needed. Among these, E glass (alkali-free glass) is more preferred. Such glass fibers are preferably surface-treated with well-known surface treatment agents, such as silane coupling agents, titanate coupling agents, and aluminate coupling agents, in order to improve mechanical strength. Furthermore, it is preferable that the glass fibers are bundled with olefin resins, styrene resins, acrylic resins, polyester resins, epoxy resins, and urethane resins, with epoxy resins and urethane resins being particularly preferred in terms of mechanical strength. The amount of bundling agent adhering to the bundled glass fibers is preferably 0.1 to 3% by weight, more preferably 0.2 to 1% by weight, per 100% by weight of the glass fibers.

[0039] The content of component D is 75 to 250 parts by weight per 100 parts by weight of component A, preferably 110 to 190 parts by weight, and more preferably 125 to 190 parts by weight. If the content of component D is less than 75 parts by weight, the mechanical properties deteriorate. On the other hand, if the content of component D exceeds 250 parts by weight, the extrudeability deteriorates and pelletization becomes difficult.

[0040] <Other ingredients> The resin composition in the present invention may be used in combination with fillers other than metal hydroxides and fibrous fillers, as long as the effects of the present invention are not impaired. Examples of fillers include powdered fillers and plate-shaped fillers other than metal hydroxides. Examples of powdered fillers include carbon black, calcium carbonate, silica, titanium dioxide, graphite, carbon nanotubes, and metal powders, while examples of plate-shaped fillers include talc and mica.

[0041] The resin composition in the present invention may contain other thermoplastic resins as long as the effects of the present invention are not impaired. Examples of other thermoplastic resins include general-purpose plastics such as polyethylene resin, polypropylene resin, and polyalkyl methacrylate resin; engineering plastics such as polyphenylene ether resin, polyacetal resin, cyclic polyolefin resin, and polyarylate resin (amorphous polyarylate, liquid crystalline polyarylate); and so-called super engineering plastics such as polytetrafluoroethylene, polyetheretherketone, polyetherimide, polysulfone, and polyethersulfone.

[0042] The resin composition in this invention may contain, to the extent that it does not impair the effects of the present invention, antioxidants, heat stabilizers (hindered phenols, hydroquinones, phosphates and their derivatives, etc.), weathering agents (resorcinols, salicylates, benzotriazoles, benzophenones, hindered amines, etc.), mold release agents, lubricants (montanic acid and its metal salts, its esters, its half-esters, stearyl alcohol, stearamides, various bisamides, bisurea and polyethylene wax, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black, etc.), dyes (nigrosine, etc.), nucleating agents (talc, silica, kaolin, clay, etc.), and plasticizers. (e.g., octyl p-oxybenzoate, N-butylbenzenesulfonamide), antistatic agents (alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine-type amphoteric antistatic agents, etc.), flame retardants (e.g., red phosphorus, phosphate esters, melamine cyanurate, hydroxides such as aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin, or combinations of these brominated flame retardants with antimony trioxide, etc.), and other polymers can be added.

[0043] <Method for producing resin compositions> The resin composition of the present invention can be manufactured by mixing the above components simultaneously or in any order using a mixer such as a tumbler, V-type blender, Nauter mixer, Banbury mixer, kneading roll, or extruder. Preferably, melt kneading is performed using a twin-screw extruder, and if necessary, it is preferable to supply any component to the other molten components from a second supply port using a side feeder or the like.

[0044] As described above, the extruded resin is either directly cut and pelletized, or strands are formed and then cut in a pelletizer to form pellets. If it is necessary to reduce the influence of external dust and other contaminants during pelletization, it is preferable to clean the atmosphere around the extruder. The resulting pellets can take on common shapes such as cylinders, prismatics, and spheres, but cylinders are more preferable. The diameter of such cylinders is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and even more preferably 2 to 3.5 mm. On the other hand, the length of the cylinders is preferably 1 to 30 mm, more preferably 2 to 5 mm, and even more preferably 2.5 to 4 mm.

[0045] <Molded products> Molded articles made from the resin composition of the present invention can be obtained by molding pellets manufactured as described above. Preferably, they can be obtained by injection molding or extrusion molding. In injection molding, in addition to conventional molding methods, examples include injection compression molding, injection press molding, gas-assisted injection molding, foam molding (including the method of injecting supercritical fluid), insert molding, in-mold coating molding, heat-insulating mold molding, rapid heating and cooling mold molding, two-color molding, multi-color molding, sandwich molding, and ultra-high-speed injection molding. Furthermore, molding can be selected from either a cold runner system or a hot runner system. In extrusion molding, a molded body can be obtained by extruding a round bar and then cutting it into a disc shape, or by extruding a thick sheet and then punching it into a predetermined shape. [Examples]

[0046] The present invention will be described below based on examples. However, the present invention is not limited to the following examples, and the following examples can be modified or altered in accordance with the spirit of the invention, without excluding them from the scope of the invention.

[0047] (1) Bending strength Using the pellets obtained by the following method, test pieces (dimensions: length 80 mm × width 10 mm × thickness 4 mm) were prepared under the following conditions, and the flexural strength was measured by a method compliant with ISO 178. The larger this numerical value is, the more excellent the mechanical properties of the polyarylene sulfide resin composition are.

[0048] (2) Flame retardancy According to the method defined by Underwriters Laboratories Inc. of the United States (UL94), a vertical burning test was carried out and evaluated at a test piece thickness of 1.0 mm. For those that did not fall into any of the classifications of V-0, V-1, and V-2, they were denoted as not V. It is preferable that the classification is any of V-0, V-1, and V-2.

[0049] (3) Tracking resistance Using the pellets obtained by the following method, test pieces (dimensions: 75 mm × 75 mm × thickness 3 mm) were prepared under the following conditions, and the maximum voltage at which no tracking breakdown occurred was determined by a method compliant with IEC60112. The larger this numerical value is, the more excellent the tracking resistance of the polyarylene sulfide resin composition is. An aqueous solution of 0.1% ammonium chloride was used as the electrolyte.

[0050] In the examples and comparative examples of the present invention, the following materials were used. <Component A> A-1: Polyphenylene sulfide resin containing a mercapto group at the terminal obtained by Production Method 1 [Production Method 1] A 15-liter autoclave equipped with a stirrer was charged with 1814 g of flaky sodium sulfide (Na2S·2.9H2O), 8.7 g of granular caustic soda (100% NaOH: Wako Pure Chemical Industries, special grade), and 3232 g of N-methyl-2-pyrrolidone. While stirring under a nitrogen stream, the temperature was gradually raised to 200 °C, and 339 g of water was distilled off. After cooling to 190 °C, 2129 g of p-dichlorobenzene and 1783 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. This system was heated to 225 °C over 2 hours and polymerized at 225 °C for 1 hour. Then, the temperature was raised to 250 °C over 25 minutes and polymerization was carried out at 250 °C for 2 hours. Next, 509 g of distilled water was injected into this system at 250 °C, the temperature was raised to 255 °C, and the polymerization reaction was further carried out for 2 hours. After the polymerization was completed, it was cooled to room temperature, and the polymerization slurry was separated into solid and liquid by a centrifugal filter. The cake was successively washed 3 times with N-methyl-2-pyrrolidone and acetone under a nitrogen stream, and further successively washed with 0.2% hydrochloric acid and warm water under a nitrogen stream. The obtained poly(p-phenylene sulfide) was dried at 105 °C for one day and night to obtain a polyarylene sulfide resin containing a mercapto group at the terminal. A-2: Poly(p-phenylene sulfide) resin containing a phenyl group at the terminal obtained by Production Method 2 [Production Method 2] To 300.00 g of para-iodobenzene and 27.00 g of sulfur, 0.60 g of diphenyl disulfide (content of 0.65% by weight based on the weight of the finally polymerized PPS) as a polymerization terminator was added, heated to 180 °C to completely melt and mix them, then the temperature was raised to 220 °C and the pressure was reduced to 200 Torr. The obtained mixture was subjected to a polymerization reaction for 8 hours while gradually changing the temperature and pressure so that the final temperature and pressure were 320 °C and 1 Torr, respectively, to obtain a poly(p-phenylene sulfide) resin containing a phenyl group at the terminal.

[0051] <Component B> B-1: Polyamide 10T (a semi-aromatic polyamide resin composed of a dicarboxylic acid component mainly composed of terephthalic acid and an aliphatic diamine component mainly composed of an aliphatic diamine having 10 carbon atoms) (manufactured by Unitika Ltd., Zeconet XN300 (trade name)) B-2: Polyamide 9T (Semi-aromatic polyamide resin composed of a dicarboxylic acid component mainly containing terephthalic acid and an aliphatic diamine component mainly containing an aliphatic diamine with 9 carbon atoms) (Ultramid N4H (trade name) manufactured by BASF) <Component C> C-1: Magnesium hydroxide (Kisuma 5L (trade name) manufactured by Kyowa Chemical Industry Co., Ltd.) <Component D> D-1: Chopped glass fiber with circular cross-section (ECS10-4.5-584 (trade name) manufactured by Jushi Japan Co., Ltd.) (Preparation of test specimens)

[0052] [Examples 1 - 10, Comparative Examples 1 - 9] Component A, Component B, and Component C were each supplied from the first supply port, and Component D-1 was supplied from the second supply port using a side feeder, followed by melt extrusion and pelletization. Here, the first supply port refers to the root supply port, and the second supply port refers to the supply port located between the die of the extruder and the first supply port. The melt extrusion was carried out using a vented twin-screw extruder with a diameter of 30 mmφ equipped with a side screw [TEX30α-38.5BW-3V manufactured by Japan Steel Works, Ltd.]. Also, the extrusion temperature was set at C1 / C2 / C3~C11 / D = 50°C / 120°C / 280°C / 320°C, the main screw rotation speed was 200 rpm, the side screw rotation speed was 80 rpm, the discharge rate was 20 kg / h, and the vent vacuum degree was 3 kPa. The pellets were dried at 130°C for 6 hours using a hot air circulation dryer, and then test specimens for evaluation were molded using an injection molding machine [EC130SXII-4Y manufactured by Toshiba Machine Engineering Co., Ltd.] under the conditions of a cylinder temperature of 330°C and a mold temperature of 140°C.

[0053] For each example and comparative example, the above-mentioned evaluations of flexural strength, flame retardancy, and tracking resistance were carried out. The results are shown in Table 1.

[0054]

Table 1

[0055] <Examples 1-10> As a composition within the scope of these claims, it exhibited excellent tracking resistance, flame retardancy, and mechanical properties. <Comparative Examples 1 and 3> Comparative Example 1 had a lower-than-minimum content of component A-1 and a high content of component C, resulting in poor extrusion and the inability to obtain pellets. Comparative Example 3 showed improved extrusion due to a lower content of component C, but its mechanical properties and tracking resistance deteriorated because the content of component A-1 was below the minimum limit. <Comparative Example 2> Because the content of component A-2 fell below the lower limit, the mechanical properties and flame retardancy deteriorated. <Comparative Example 4> The mechanical properties deteriorated because the content of component B fell below the lower limit. <Comparative Example 5> The flame retardancy deteriorated because the amount of component B exceeded the upper limit. <Comparative Example 6> Because the C content fell below the lower limit, flame retardancy and tracking resistance deteriorated. <Comparative Example 7> Because the C content exceeded the upper limit, the extrusion properties deteriorated and pellets could not be obtained. <Comparative Example 8> The mechanical properties deteriorated because the content of component D fell below the lower limit. <Comparative Example 9> Because the content of component D exceeded the upper limit, the extrusion properties deteriorated and pellets could not be obtained.

Claims

1. A polyarylene sulfide resin composition characterized by containing, per 100 parts by weight of polyarylene sulfide resin (component A), which consists of 10 to 90 parts by weight of polyarylene sulfide resin (component A-1) containing mercapto groups at the terminals and 10 to 90 parts by weight of polyarylene sulfide resin (component A-2) containing phenyl groups at the terminals, 51 to 80 parts by weight of (B) semi-aromatic polyamide resin (component B), 70 to 175 parts by weight of (C) metal hydroxide (component C), and 75 to 250 parts by weight of (D) fibrous filler (component D).

2. The polyarylene sulfide resin composition according to claim 1, characterized in that component B is at least one semi-aromatic polyamide resin selected from the group consisting of a semi-aromatic polyamide resin (component B-1) comprising a dicarboxylic acid component mainly composed of terephthalic acid and an aliphatic diamine component mainly composed of a C10 aliphatic diamine, and a semi-aromatic polyamide resin (component B-2) comprising a dicarboxylic acid component mainly composed of terephthalic acid and an aliphatic diamine component mainly composed of a C9 aliphatic diamine.

3. The polyarylene sulfide resin composition according to claim 1 or 2, characterized in that component C is magnesium hydroxide.

4. The polyarylene sulfide resin composition according to claim 1 or 2, characterized in that component D is glass fiber.

5. A molded article obtained by molding the polyarylene sulfide resin composition according to claim 1 or 2.

Images