JP2005248170A - Polyphenylene sulfide resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a PPS resin composition having an excellent strength and slidability, and particularly an excellent balance of an impact strength and flowability, while maintaining an excellent heat resistance, rigidity, dimensional stability and flame retardancy of a conventional polyphenylene sulfide resin. <P>SOLUTION: This polyphenylene sulfide resin composition is prepared by blending (D) 10-200 pts.wt. of an inorganic filler with 100 pts.wt. of the (A)-(C) compositions: (A) 20-96 wt.% of a polyphenylene sulfide resin, (B) 1-30 wt.% of a polyolefin copolymer copolymerized from ethylene and glycidyl methacrylate or glycidyl acrylate, and (C) 3-50 wt.% of at least one type of polyolefin resin selected from the group consisting of a polystyrene resin, polyacrylic ester resin, polymethacrylic acid ester resin, polyethylene resin and polypropylene resin, the weight ratio of (C)/(B) being 1 to 4.8. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

  The present invention relates to a reinforced polyphenylene sulfide resin from which a molded article having excellent impact resistance and fluidity can be obtained. More specifically, the present invention is excellent in impact resistance and fluidity, and has rigidity, heat resistance, and slidability. The present invention relates to a polyphenylene sulfide resin composition having an excellent balance of properties such as excellent dimensional stability, chemical resistance, barrier properties, and low water absorption.

  Since polyphenylene sulfide resin (hereinafter abbreviated as PPS resin) has suitable properties as engineering plastics such as excellent heat resistance, rigidity, dimensional stability, and flame retardancy, various types are mainly used for injection molding. Widely used in electrical / electronic parts, machine parts and automobile parts.

  However, when used for molded products that require impact resistance, an elastomer or the like is blended. However, the PPS resin has a high melting point, and the elastomer decomposes and gels during processing, resulting in a decrease in fluidity and toughness. there were. In addition, when a high melting point polymer having excellent thermal stability is blended, impact resistance is lowered, and it is difficult to achieve both impact resistance and good flow.

Several studies have been made for the purpose of improving impact resistance. For example, Patent Documents 1 and 2 disclose a composition in which an olefin copolymer composed of an unsaturated acid glycidyl ester is blended with a PPS resin. However, according to the study by the present inventors, it has been found that the fluidity is lowered only by blending an olefin copolymer comprising an unsaturated glycidyl ester. Patent Document 3 discloses a composition having a phase structure composed of a polyolefin resin and a PPS resin, the PPS resin as a matrix resin, and the polyolefin resin as a dispersion layer. However, in the specifically disclosed composition, The fluidity and tensile strength were still insufficient.
Japanese Patent Publication No. 2-382 (page 1-3) JP-A-5-239363 (page 1-5) JP 2001-302917 A (page 1-12)

  The present invention maintains the excellent heat resistance, rigidity, dimensional stability, flame retardancy, etc. of the above-mentioned conventional polyphenylene sulfide resin, and is excellent in chemical resistance, barrier properties, low water absorption, particularly excellent impact strength and An object of the present invention is to provide a PPS resin composition having both fluidity.

As a result of intensive studies to solve the above-mentioned problems, the present inventors have obtained a PPS resin composition containing a specific polyolefin resin and a copolymerized polyolefin obtained by copolymerizing ethylene and glycidyl methacrylate or glycidyl acrylate. The present inventors have found that the above problems can be solved and have arrived at the present invention.
That is, the present invention
(1) (A) 20 to 96% by weight of polyphenylene sulfide resin, (B) 1 to 30% by weight of copolymerized polyolefin obtained by copolymerizing ethylene and glycidyl methacrylate or glycidyl acrylate, (C) polystyrene resin, polyacrylic 3 to 50% by weight of one or more polyolefin resins selected from an acid ester resin, a polymethacrylic acid ester resin, a polyethylene resin and a polypropylene resin, and a weight ratio (C) / (B) of (B) and (C) ) Is a polyphenylene sulfide resin composition formed by blending 10 to 200 parts by weight of an inorganic filler with respect to 100 parts by weight of the composition of (A) to (C).
(2) (D) The polyphenylene sulfide resin composition according to (1), wherein the inorganic filler is glass fiber,
(3) The polyphenylene sulfide resin composition according to (1) or (2), wherein the (C) polyolefin resin is a polyethylene resin having a density of 900 to 950 kg / m ³ .
(4) The polyphenylene sulfide resin composition according to any one of (1) to (3), wherein the (C) polyolefin resin is a polyethylene resin having a melt flow rate (MFR) of 0.05 to 12 g / 10 min.
(5) (A) polyphenylene sulfide resin, (B) copolymer polyolefin, (C) polyolefin resin after melt kneading, (D) inorganic filler is added and melt kneading (1) to ( 4) The manufacturing method of the polyphenylene sulfide resin composition in any one.

  The present invention maintains the excellent heat resistance, rigidity, dimensional stability, flame retardancy, etc. of the above-mentioned conventional polyphenylene sulfide resin, and is excellent in chemical resistance, barrier properties, low water absorption, particularly excellent impact strength and An object of the present invention is to provide a PPS resin composition having both fluidity.

  The present invention will be described more specifically. In the present invention, “weight” means “mass”.

  The PPS resin used in the present invention is a polymer having a repeating unit represented by the following structural formula (I),

  From the viewpoint of heat resistance, the polymer preferably contains 70 mol% or more, more preferably 90 mol% or more of a polymer containing a repeating unit represented by the above structural formula. In addition, about 30 mol% or less of the repeating units of PPS may be composed of repeating units having the following structure.

  The PPS resin is obtained by a method for obtaining a polymer having a relatively small molecular weight obtained by a production method represented by Japanese Patent Publication No. 45-3368, or Japanese Patent Publication Nos. 52-12240 and 61-7332. It can be produced by a known method such as a method for obtaining a polymer having a relatively large molecular weight as described.

  The PPS resin obtained as described above may be used as it is, or it may be used for crosslinking / polymerization by heating in air, heat treatment under an inert gas atmosphere such as nitrogen or reduced pressure, organic solvent, hot water. It is also possible to use after washing with an acid aqueous solution or the like.

  The production method for obtaining the PPS resin having the above properties is not particularly limited as long as the above properties can be obtained, but the polymer is a substantially linear polymer with few impurities, and the desired properties are obtained. A method of washing with an organic solvent, hot water, an acid aqueous solution, or the like until is obtained.

  In the case of washing with an organic solvent, the organic solvent to be used is not particularly limited as long as it does not have an action of decomposing PPS. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformaldehyde, dimethylacetamide, 1,3-dimethylimidazolidinone, hexamethylphosphoramide, piperazinones, sulfoxides and sulfones such as dimethylsulfoxide, dimethylsulfone, and sulfolane Solvents, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, ether solvents such as dimethyl ether, dipropyl ether, dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene chloride, chloroethylene , Halogenated solvents such as monochloroethane, dichloroethane, tetrachloroethane, perchloroethane, chlorobenzene, methanol, ethanol, propanol, Alcohol, pentaol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol and other alcohol-phenol solvents, and benzene, Examples thereof include aromatic hydrocarbon solvents such as toluene and xylene.

  There is no restriction | limiting in particular also about washing | cleaning temperature, Usually, about normal temperature-about 300 degreeC are selected. In the case of washing with an acid aqueous solution, the acid to be used is not particularly limited as long as it does not have an action of decomposing PPS, and examples thereof include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid, and propyl acid. Moreover, it can also be used after performing various treatments such as activation with a functional group-containing compound such as an acid anhydride group, an epoxy group, or an isocyanate group. When used in the present invention, those washed with an aqueous acid solution are preferred.

  As the PPS resin used in the present invention, two or more kinds of PPS resins having different molecular weight distributions can be mixed and used. When two or more types having a molecular weight distribution are used in combination, a combination of one having a high molecular weight and one having a low molecular weight is used, so that the speed dependency at the time of molding becomes smaller than that of one type having the same average molecular weight. Suppressed and preferred.

  The MFR used as the base polymer of the PPS resin used in the present invention (although blended when two or more PPS resins are used in combination) is not particularly limited as long as it can be melt-kneaded. It is preferably 10000 g / 10 min or less as a measured value using a melt indexer under the condition of staying for 5 minutes and a load of 5000 g (orifice diameter 2.095 mm, length 8.00 mm), and 5000 g / 10 min or less. It is more preferable. Although there is no restriction | limiting in particular as a minimum, From the point of melt viscosity, it is good that it is 10 g / 10min or more, and it is more preferable that it is 50 g / 10min or more.

  When two or more types of molecular weight distributions are used in combination as the PPS resin, at least one type preferably has an MFR of 10 to 1000 g / 10 min, more preferably 50 to 800 g / 10 min. At least one kind of is preferably 500 to 10000 g / 10 minutes, and more preferably 800 to 8000 g / 10 minutes. When two or more molecular weight distributions are used in combination, the difference between at least two MFRs of the high molecular weight PPS resin and the low molecular weight PPS resin is preferably 50 to 8000 g / 10 minutes, More preferably, it is 6000 g / 10 minutes.

  In this invention, the usage-amount of (A) PPS resin is 20 to 96 weight% with respect to a total of 100 weight% of (A)-(C) component, and it is preferable that it is 40 to 85 weight%. (A) If the amount of the PPS resin is too small, the heat resistance and fluidity of the PPS resin composition are undesirably lowered. Conversely, if the amount is too large, the impact strength of the PPS resin composition is undesirably decreased.

  There is no particular limitation on the composition of the copolymerized polyolefin obtained by copolymerizing ethylene and glycidyl methacrylate or glycidyl acrylate used as the component (B) used in the present invention, but the total of ethylene and glycidyl methacrylate or glycidyl acrylate When it is 100% by weight, ethylene is preferably 99 to 50% by weight and glycidyl methacrylate or glycidyl acrylate is preferably 1 to 50% by weight, and ethylene is 99 to 60% by weight and glycidyl methacrylate or glycidyl acrylate is 1 to 40% by weight. % Is more preferable. If the amount of copolymerization is too small, the impact resistance of the PPS resin composition tends to be impaired. On the other hand, if the amount of copolymerization is too large, the PPS resin composition tends to exhibit a gelation tendency.

  The type of copolymerization of the copolymerized polyolefin comprising ethylene and glycidyl methacrylate or glycidyl acrylate as the main constituents is not limited, and any known method may be used, such as high-pressure radical copolymerization and graft copolymerization. Manufactured by polymerization or the like.

  The copolymer polyolefin of (B) is within a range that does not impair the properties of the resin composition of the present invention, preferably within a range of 30% by weight or less with respect to the copolymer polyolefin, and other olefin monomers such as methyl acrylate, methacryl Methyl acid, acrylonitrile, styrene or the like may be introduced by random, block or graft copolymerization in the form of a single substance or a mixture.

  The degree of polymerization of the copolymerized polyolefin (B) is not particularly limited, and those having an MFR in the range of 0.1 to 100 g / 10 min under the condition of 190 ° C./2160 g measured by the method defined in JISK6760 should be used. Can do. The MFR is more preferably 0.1 to 30 g / 10 minutes, and further preferably 0.1 to 20 g / 10 minutes.

  The ratio of the copolymerized polyolefin (A) to (C) to the total of 100% by weight is 1 to 30% by weight, preferably 5 to 20% by weight. If the amount of the copolymerized polyolefin is too small, the impact resistance of the PPS resin composition is insufficient, which is not preferable. Conversely, if the amount is too large, the fluidity of the PPS resin composition decreases, which is not preferable.

  The (C) polyolefin resin used in the present invention is used in combination as long as it is any one or more polyolefin resins selected from polystyrene resins, polyacrylate resins, polymethacrylate resins, polyethylene resins and polypropylene resins. Also good. Of these, polyethylene is particularly preferable.

Preferably the density of the (C) the polyolefin resin is 900~990kg / ^{m 3,} more preferably from 900~950kg / ^{m 3,} more preferably a 900~935kg / ^{m 3.} In particular, the effect of the present invention is remarkable when a polyethylene resin having the above density range is used.

  The density of the polyolefin can be measured according to ASTM D1505.

  The MFR of the above (C) is not particularly limited as long as melt kneading is possible, but it is preferably 70 g / 10 min or less as a measured value using a melt indexer under the conditions according to ASTM D1238. / 10 minutes or less is more preferable, and 12 g / 10 minutes or less is more preferable. If it exceeds 70 g / 10 minutes, the impact strength may be lowered depending on the product shape, which is not preferable. Although there is no restriction | limiting in particular as a minimum, It is preferable that it is 0.05 g / 10min or more from a fluid point. When a polyethylene resin is used, the MFR is preferably 0.05 to 70 g / 10 minutes and more preferably 0.05 to 12 g / 10 minutes as measured at 190 ° C. and a load of 2160 g. When a polypropylene resin is used, the MFR is preferably 0.05 to 70 g / 10 minutes, more preferably 0.05 to 12 g / 10 minutes, measured at 230 ° C. and a load of 2160 g.

  The method for producing the (C) polyolefin resin used in the present invention is not particularly limited, and any method such as radical polymerization, coordination polymerization using a Ziegler-Natta catalyst, anionic polymerization, or coordination polymerization using a metallocene catalyst may be used. Can be used.

  In the present invention, part or all of the (C) polyolefin resin can be modified with at least one compound selected from unsaturated carboxylic acids or derivatives thereof. When a modified polyolefin resin is used, the compatibility is improved.

  Examples of unsaturated carboxylic acids or derivatives thereof used as modifiers include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, methylmaleic acid, methyl fumaric acid, mesaconic acid, citraconic acid, Glutaconic acid and metal salts of these carboxylic acids, methyl hydrogen maleate, methyl hydrogen itaconate, methyl acrylate, ethyl acrylate, butyl acrylate, 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, methacrylic acid 2 -Ethylhexyl, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- (2,2,1) -5-heptene-2, 3-dicarboxylic acid Endobicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, glycidyl acrylate (but copolymerized with ethylene) Glycidyl methacrylate (except when copolymerized with ethylene), glycidyl itaconate, glycidyl citraconic acid, and 5-norbornene-2,3-dicarboxylic acid. Of these, unsaturated dicarboxylic acids and acid anhydrides thereof are preferred, and maleic acid and maleic anhydride are particularly preferred.

  The method for introducing these unsaturated carboxylic acid or its derivative component into the polyolefin resin is not particularly limited, and the olefin compound as the main component and the unsaturated carboxylic acid or its derivative compound may be copolymerized in advance, or may not be added to the unmodified polyolefin resin. A method such as introducing a saturated carboxylic acid or a derivative compound thereof by grafting using a radical initiator can be used. The amount of unsaturated carboxylic acid or its derivative component introduced is preferably within the range of 0.001 to 40 mol%, more preferably 0.01 to 35 mol%, based on the entire olefin monomer in the modified polyolefin. It is.

  The blending amount of the polyolefin resin (C) is 50 to 3% by weight, preferably 40 to 10% by weight, based on the total 100% by weight of (A) to (C). If the amount is too small, the balance between the impact strength and the fluidity is poor, which is not preferable. If the amount is too large, the strength and rigidity decrease, which is not preferable.

  There is no particular limitation on the ratio of the (C) polyolefin resin of the present invention to (B) a copolymerized polyolefin comprising ethylene and glycidyl methacrylate or glycidyl acrylate as the main constituent, but the ratio of (C) to (B) (C ) / (B) is preferably 1 to 4.8 from the balance of impact strength and fluidity, and the ratio (C) / (B) is more preferably 1.1 to 4.0.

  As the (D) inorganic filler used in the present invention, fillers such as fibers, plates, powders, and granules can be used. Specifically, for example, fiber fillers such as glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone koji fiber, metal fiber, calcium carbonate fiber, Silicate silicates such as wollastonite, sericite, kaolin, mica, clay, bentonite, asbestos, talc, alumina silicate, swellable layered silicates such as montmorillonite, synthetic mica, alumina, silicon oxide, magnesium oxide, zirconium oxide, oxidation Metal compounds such as titanium and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, ceramic beads, silica, wet white carbon, granular wollastonite, zeolite, water Calcium oxide, water Magnesium, hydroxides such as aluminum hydroxide, glass beads, boron nitride, silicon carbide, graphite, pyrophyllite, include non-fibrous fillers such as calcium phosphate. A glass fiber of a fibrous filler is preferable. These may be hollow, and two or more of these fillers can be used in combination.

  The particle diameter and average fiber diameter of (D) are not particularly limited, but the average fiber diameter of the fibrous filler is preferably 20 μm or less, and more preferably the average fiber diameter is 16 μm or less. There is no particular limitation on the lower limit, and it is preferable that the lower limit is as small as possible. When the average fiber diameter exceeds 20 μm, the strength tends to decrease. In general, the average fiber diameter is a weight average fiber diameter determined based on a diameter distribution measured according to a conventional method using a laser diffraction particle size distribution analyzer. However, the average fiber diameter of glass fiber, whisker, etc., which is not suitable for laser diffraction particle size distribution measurement, with a fiber length to fiber diameter ratio of 25 or more, is the average fiber diameter measured by an ordinary method using an electronic scanning microscope. . Moreover, there is no restriction | limiting in particular about purity.

  Furthermore, in the present invention, when it is desired to impart conductivity, it is possible to use a conductive filler as part or all of the inorganic filler, and the material is not particularly limited. The filler is not particularly limited as long as it is a conductive filler that is usually used for conducting a resin. Specific examples thereof include metal powder, metal flake, metal ribbon, metal fiber, metal oxide, and a conductive substance. Inorganic fillers, carbon powder, graphite, carbon fibers, carbon flakes, scale-like carbon, and the like.

  Specific examples of metal species of metal powder, metal flakes, and metal ribbons include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin.

  Specific examples of the metal species of the metal fiber include iron, copper, stainless steel, aluminum, and brass.

  Such metal powders, metal flakes, metal ribbons, and metal fibers may be subjected to surface treatment with a surface treatment agent such as titanate, aluminum, or silane.

Specific examples of the metal oxide include SnO ₂ (antimony dope), In ₂ O ₃ (antimony dope), ZnO (aluminum dope), etc., and these include the surface of titanate, aluminum, and silane coupling agents. Surface treatment may be performed with a treating agent.

Specific examples of the conductive material in the inorganic filler coated with the conductive material include aluminum, nickel, silver, carbon, SnO ₂ (antimony doped), and In ₂ O ₃ (antimony doped). Further, as the inorganic filler to be coated, mica, glass beads, glass fiber, carbon fiber, potassium titanate whisker, barium sulfate, zinc oxide, titanium oxide, aluminum borate whisker, zinc oxide whisker, titanic acid whisker, Examples thereof include silicon carbide whiskers. Examples of the coating method include vacuum deposition, sputtering, electroless plating, and baking. These may be surface-treated with a surface treatment agent such as a titanate, aluminum or silane coupling agent.

  Furthermore, it is possible to mix | blend carbon black as said electroconductive filler in this invention. As carbon black, C (carbon) is the main component, and its raw materials and manufacturing methods are used for acetylene black, gas black, oil black, naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, disc black, etc. being classified. The carbon powder that can be used in the present invention is not particularly limited in its raw material and production method, but acetylene black and furnace black are particularly preferably used. Such carbon powder may be surface-treated with a surface treatment agent such as titanate, aluminum, or silane. Carbon black is compounded (added by blending with raw materials during extrusion kneading), masterbatch added (added by blending carbon black master before molding such as injection molding), dry color ( You may use by any addition method of the method of adding by coating carbon black on the surface of a resin composition pellet.

  Two or more of the conductive fillers may be used in combination. Among such conductive fillers, carbon black is particularly preferably used in terms of strength and economy.

  The blending amount of the (D) inorganic filler is 10 to 200 parts by weight, preferably 20 to 180 parts by weight, preferably 25 to 150 parts by weight with respect to 100 parts by weight of the total of (A) to (C). Part by weight is particularly preferred. Too much is not preferable because the fluidity is lowered. If the amount is too small, the thermal rigidity is lowered, which is not preferable.

  The inorganic filler (D) can be subjected to a surface treatment within a range not impairing the effects of the present invention. Examples of the treatment agent include a surface treatment agent and a sizing agent. Compounds, isocyanate compounds, organic silane compounds, organic titanate compounds, and organic borane treatment.

  You may mix | blend another thermoplastic resin with the resin composition of this invention in the range which does not impair the effect in this invention. Specific examples include ABS resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyacetal resin, modified polyphenylene ether resin, polysulfone resin, polyallyl sulfone resin, polyketone resin, polyetherimide resin, polyarylate resin, liquid crystal Polymer, Polyethersulfone resin, Polyetherketone resin, Polythioetherketone resin, Polyetheretherketone resin, Polyimide resin, Polyamideimide resin, Polytetrafluoroethylene resin, Thermoplastic polyurethane resin, Polyester elastomer, Polyester resin, Polyphenylene ether Resin, SAN resin, acrylic resin, SBS, SEBS, various elastomers, etc. are blended as long as the effects of the present invention are not impaired. It is possible. Furthermore, these can also be used in combination of 2 or more types.

  Furthermore, a silane coupling agent can be used in the resin composition of the present invention as long as the effects of the present invention are not impaired, and the material is not particularly limited, but may be blended. Silane coupling agents are a type of coupling agent that is generally used as a surface treatment agent for various fillers, as a primer in adhesives and coatings, among which epoxy groups, amino groups, isocyanate groups, hydroxyl groups, mercapto groups, ureidos. An alkoxysilane having at least one functional group selected from a group, a vinyl group, and a methacryloxy group is preferably used. Specific examples include epoxy group-containing alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and γ-mercapto. Mercapto group-containing alkoxysilanes such as propyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-ureidopropyltriethoxysilane, γ- (2-ureidoethyl) aminopropyltrimethoxysilane, etc. Ureido group-containing alkoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiet Isocyanato group-containing alkoxysilane such as silane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, Hydroxy group-containing alkoxysilanes such as γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ-aminopropylmethyldimethoxysilane, and other amino group-containing alkoxysilanes, γ-hydroxypropyltrimethoxysilane, and γ-hydroxypropyltriethoxysilane , Vinyltrimethoxysilane, vinyltriethoxysilane, and other vinyl group-containing alkoxysilanes, and γ-methacryloxypropyltrimethoxysilane, etc., methacryloxy group-containing alkoxysilanes And the like. Of these, epoxy group-containing alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane are preferred.

  The silane coupling agent is preferably 0.05 to 5 parts by weight, and more preferably 0.1 to 2 parts by weight with respect to 100 parts by weight as a total of the components (A) to (C).

  Furthermore, a conductive polymer can be used in the resin composition of the present invention as long as the effects of the present invention are not impaired, and the material thereof is not particularly limited. Examples thereof include polyaniline, polypyrrole, polyacetylene, poly (paraphenylene), polythiophene, and polyphenylene vinylene.

  Two or more kinds of the conductive polymers may be used in combination.

  Further, in the resin composition of the present invention, a coupling agent such as an isocyanate compound, an organic titanate compound, an organic borane compound, and an epoxy compound, a polyalkylene oxide oligomer compound, a thioether, as long as the effects of the present invention are not impaired. Plasticizers such as organic compounds, ester compounds and organic phosphorus compounds, inorganic fine particles, organic phosphorus compounds, crystal nucleating agents such as metal oxides and polyetheretherketone, polyolefins such as polyethylene and polypropylene, waxes of montanic acid, stearin Metal soaps such as lithium acid, aluminum stearate, ethylenediamine / stearic acid / sebacic acid polycondensate, mold release agents such as silicone compounds, anti-coloring agents such as hypophosphite, hindered phenol antioxidants, Phosphorus antioxidant, sulfur oxidation Antioxidants such as stoppers, weathering agents and UV inhibitors (resorcinols, salicylates, benzotriazoles, benzophenones, hindered amines, etc.), heat stabilizers (hindered phenols, hydroquinones, phosphites, etc.) ), Heat stabilizers, lubricants (montanic acid and metal salts thereof, esters thereof, half esters thereof, stearyl alcohol, stearamide, various bisamides, bisureas and polyethylene waxes), foaming agents, pigments (cadmium sulfide, Phthalocyanine, carbon black, metallic pigments, etc.), dyes (eg, nigrosine), plasticizers (octyl p-oxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agents (alkyl sulfate type anionic antistatic agents, grade 4) Ammonium salt type cation Antistatic agent, nonionic antistatic agent such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agent, etc.), flame retardant (eg red phosphorus, melamine cyanurate, magnesium hydroxide, aluminum hydroxide) Normal additives such as hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin or a combination of these brominated flame retardants and antimony trioxide) Can be added.

  The method for preparing the resin composition used in the present invention is not particularly limited, but it can be obtained by melt-kneading the components (A) to (D) and other raw materials added as necessary. Specifically, the mixture of raw materials is supplied to a generally known melt mixer such as a single or twin screw extruder, Banbury mixer, kneader, or mixin gall, and kneaded at a temperature of 280 to 450 ° C. The method of doing can be given as an example. Also, the mixing order of the raw materials is not particularly limited, and all the raw materials are melt-kneaded by the above method, some raw materials are melt-kneaded by the above method, and the remaining raw materials are melt-kneaded, or one Any method may be used, such as a method in which the remaining raw materials are mixed using a side feeder during melt kneading of the raw materials of the part using a single-screw or twin-screw extruder. Preferably, the PPS resin, the copolymerized polyolefin and the polyolefin are melt-kneaded, then an inorganic filler is added, and melt-kneaded for production. Above all, supply PPS resin, copolymer polyolefin and polyolefin using a twin screw extruder, melt knead, supply and knead inorganic filler using a side feeder, and then remove the gas generated by exposure to vacuum. The method of doing can be mentioned preferably. By obtaining a PPS resin composition by such an extrusion process, it is possible to obtain good impact strength with less generated gas. As for the small amount additive component, other components may be kneaded and pelletized by the above-described method and then added before molding and used for molding.

  The MFR of the PPS resin composition obtained in the present invention is not particularly limited as long as it can be molded, but it is 315.5 ° C. for 5 minutes, the load is 5000 g (orifice diameter 2.095 mm, length 8.00 mm). The measured value using a melt indexer under the conditions is preferably 150 g / 10 min or less, more preferably 100 g / 10 min or less from the viewpoint of strength. The lower limit is preferably 0.5 g / 10 min or more from the viewpoint of fluidity, and more preferably 1 g / 10 min or more. The MFR of the PPS resin composition depends mainly on the amount of the MPS of the PPS resin to be used, the components (B) to (D), etc., and by using the PPS having a low MFR or the components (B) to (D) Since the MFR tends to decrease as the amount increases, a PPS resin composition having the above range can be obtained by appropriately adjusting these.

  The resin composition of the present invention is a known method (injection molding such as injection molding, injection compression molding, two-color molding, DSI molding, extrusion molding, blow molding, press molding). Etc.). Of these, molding by injection molding is preferred from the viewpoint of excellent mechanical strength. The molding temperature is usually selected from a temperature range 5 to 50 ° C. higher than the melting point of the thermoplastic resin other than the polyolefin resin, and is generally a single layer, but it is a two-color injection molding method or coextrusion molding. It may be a multilayer structure by a method such as the method.

  The resin composition of the present invention is excellent in impact strength, fluidity, low gasity, slidability, and particularly in parts that require toughness due to excellent impact strength and fluidity, particularly container parts such as tanks and cases. Suitable for structural parts such as housings and sliding parts. For example, exterior parts of automobiles such as fenders, doors, wheel caps, door mirror stays, sliding parts such as various gears, pistons, rollers, guides, engine covers for two-wheeled and four-wheeled automobiles, intake manifolds, cylinder head covers and their integrated parts Not only suitable for molded products such as housings, structural parts, fuel tanks, canisters, washer liquid tanks, oil reservoir tanks, various oil tanks, under hood parts, electrical component cases, other containers, relay blocks, There are automotive interior and exterior parts such as inhibitor switches and combination switch levers. Suitable for other structural materials. OA equipment parts such as notebook PC housings, printer housings, home appliance housings, covers, tanks, cut-off valves attached to bottles, valves and fittings such as ORVR valves, attached pump gauges, cases, etc. Parts, fuel filler underpipe, ORVR hose, reserve hose, vent hose and other fuel tube connection parts (connectors, etc.), oil tube connection parts, brake hose connection parts, nozzles for window washer fluid, hoses, tubes Connecting parts, connecting parts for floor heating pipes, hoses for fire extinguishers and fire extinguishing equipment, connecting parts and valves for tubes for medical cooling equipment, pipes and pump housings, valves, flanges, automotive parts, internal combustion engine applications, Mechanical parts such as power tool housings Because, electric and electronic parts, medical, food, home and office supplies, building materials-related parts, and parts for furniture Naga is.

  EXAMPLES Hereinafter, although an Example and a comparative example demonstrate this invention concretely, this invention is not limited by a following example.

  MFR, surface appearance, tensile strength, impact strength, and fluidity described in the examples and comparative examples were each measured according to the following methods.

[MFR of PPS mixture or composition]
Measurement was performed at 315.5 ° C. under a load of 5000 g in accordance with ASTM D1238.

[Surface appearance]
The appearance of the tensile test piece was visually observed to determine the appearance. Judgment: ○: good without roughening or peeling, x: rough or peeling, not practical level.

[Measurement of tensile strength]
A tensile test piece (1/8 inch (3.2 mm) thick) according to ASTM D638 was injection molded at a cylinder temperature of 320 ° C. and a mold temperature of 130 ° C., and measured under a temperature condition of 23 ° C. . If it is 100 MPa or more, it can be said that the product strength level has no practical problem, but the higher this value, the better the rigidity and the better.

[Measurement of impact strength]
An impact test piece (1/8 inch (3.2 mm) width, notched) according to ASTM D256 was injection molded at a cylinder temperature of 320 ° C. and a mold temperature of 130 ° C., and measured under a temperature condition of 23 ° C. Is. If it is 100 J / m or more, it can be said that the product strength level has no problem in practical use.

[Measurement of fluidity]
A spiral flow molded product (2 mm thickness × 10 mm width) was injection molded at an injection time of 10 seconds, a cooling time of 10 seconds, and an injection pressure of 100 MPa at a cylinder temperature of 320 ° C. and a mold temperature of 130 ° C.
The flow length of 10 shots is measured and averaged. If it is 40 cm or more, it can be said that a thin product can be used as a molded product, and the higher the value, the better the fluidity.

[Reference example]
(Production of PPS-1)
An autoclave equipped with a stirrer was charged with 2.98 kg (25 mol) of a 47% sodium hydrosulfide aqueous solution, 2.17 kg (26 mol) of 48% sodium hydroxide and 5 kg of N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP). The temperature was raised to 205 ° C., and 2.8 liters of extracted water containing 2.7 kg of water was removed. To the residual mixture, 3.75 kg (25.5 mol) of 1,4-dichlorobenzene and 2.5 kg of NMP were added and heated at 270 ° C. for 1 hour. The reaction product was washed twice with warm water and dried under reduced pressure at 120 ° C. for 24 hours to obtain MFR6000 (g / 10 min) of PPS-1. The MFR was measured using a melt indexer under conditions of 315.5 ° C., 5 minutes residence, and a load of 5000 g (orifice diameter 2.095 mm, length 8.00 mm). Further, the loss on heating of the PPS resin was 0.5% by weight. In addition, 1 g of PPS resin was put into an aluminum cup, preliminarily dried for 1 hour in an atmosphere of 150 ° C., and then the weight was measured. The weight loss was measured in air at 371 ° C. for 1 hour, and the weight was measured again. The weight loss due to the treatment at 371 ° C. was gradually expressed as a percentage by the weight before the treatment, and was regarded as the heat loss.

(Production of PPS-2)
An autoclave equipped with a stirrer was charged with 2.98 kg (25 mol) of a 47% aqueous sodium hydrosulfide solution, 2.17 kg (26 mol) of 48% sodium hydroxide, 656 g (8 mol) of sodium acetate and 5 kg of NMP, and the temperature was gradually raised to 205 ° C. Then, 2.8 liters of extracted water containing 2.7 kg of water was removed. To the residual mixture, 3.75 kg (25.5 mol) of 1,4-dichlorobenzene and 2.5 kg of NMP were added and heated at 270 ° C. for 1 hour. The reaction product was washed twice with warm water, dried under reduced pressure at 120 ° C. for 24 hours, and then heat-treated at 230 ° C. for 16 hours to obtain MFR120 (g / 10 min) of PPS-2.

  The MFR was measured using a melt indexer under conditions of 315.5 ° C., 5 minutes residence, and a load of 5000 g (orifice diameter 2.095 mm, length 8.00 mm). The heat loss of the PPS resin was 0.4% by weight. In addition, 1 g of PPS resin was put into an aluminum cup, preliminarily dried for 1 hour in an atmosphere of 150 ° C., and then the weight was measured. The weight loss was measured in air at 371 ° C. for 1 hour, and the weight was measured again. The weight loss due to the treatment at 371 ° C. was gradually expressed as a percentage by the weight before the treatment, and was regarded as the heat loss.

(Production of PPS-3)
An autoclave equipped with a stirrer was charged with 4.67 kg (25 mol) of an aqueous sodium hydrosulfide solution, 2.00 kg (25 mol) of 50% sodium hydroxide and 8 kg of NMP, and gradually heated to 205 ° C. while stirring, 4.1 liters of extracted water was removed. To the residual mixture, 3.75 kg (25.5 mol) of 1,4-dichlorobenzene and 2 kg of NMP were added and heated at 230 ° C. for 1 hour and further at 260 ° C. for 30 minutes. The reaction product was washed twice with warm water, dried under reduced pressure at 120 ° C. for 24 hours, and further heat-treated at 230 ° C. for 16 hours to obtain MFR550 (g / 10 min) of PPS-3. The MFR was measured using a melt indexer under conditions of 315.5 ° C., 5 minutes residence, and a load of 5000 g (orifice diameter 2.095 mm, length 8.00 mm). Further, the loss on heating of the PPS resin was 0.5% by weight. In addition, 1 g of PPS resin was put into an aluminum cup, preliminarily dried for 1 hour in an atmosphere of 150 ° C., and then the weight was measured. The weight loss was measured in air at 371 ° C. for 1 hour, and the weight was measured again. The weight loss due to the treatment at 371 ° C. was gradually expressed as a percentage by the weight before the treatment, and was regarded as the heat loss.

[Compounding materials used in Examples and Comparative Examples]
(Copolymerized polyolefin)
B-1: Ethylene / glycidyl methacrylate copolymer (E / GMA = 88/12% by weight), MFR = 3 g / 10 minutes B-2: Ethylene / methyl acrylate / glycidyl methacrylate copolymer (E / MA / GMA = 64/30/6 wt%), MFR = 8 g / 10 min MFR was measured by the method defined in JISK6760 (190 ° C., 2160 g load).
(Polyolefin resin)
C-1: Polyethylene Density 903kg ^/ cm 3, MFR4.0g ^/ 10 min C-2: Polyethylene Density 968kg ^/ cm 3, MFR4.5g ^/ 10 min C-3: Polypropylene Density 910kg ^/ cm 3, MFR0.5g ^/ 10 Minute C-4: Polypropylene density 910 kg / cm ³ , MFR 5.0 g / 10 minutes MFR was measured according to ASTM D1238 (polyethylene: 190 ° C., polypropylene: 230 ° C.) (2160 g load).
(Inorganic filler)
D-1: Glass fiber: “T-747” average fiber diameter 13 μm (manufactured by Nippon Electric Glass)
D-2: Wollastonite: “FPW # 400” average fiber diameter 9.5 μm (manufactured by Kinsei Matec)
In the above, the average fiber diameter of the glass fiber is an average fiber diameter measured by an ordinary method using an electron scanning microscope. The average fiber diameter of wollastonite is a weight average fiber diameter determined on the basis of a fiber diameter distribution measured according to a conventional method using a laser diffraction particle size distribution analyzer.
(Coupling agent)
β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane) was used.

Examples 1-10
A screw-type twin-screw extruder in which PPS (A), copolymerized polyolefin (B), and polyolefin (C) prepared as described above were dry blended in the proportions shown in Table 1 and then set to 350 ° C. extrusion conditions. (A)-(C) blended using (Nippon Steel Works "TEX-44") is supplied and supplied, and after melt-kneading, the inorganic filler (D) is supplied from the side feeder, and then in a vacuum state. The gas generated by exposure was removed and pelletized. After drying the obtained pellets, injection molding is carried out under the conditions of cylinder temperature 320 ° C. and mold temperature 130 ° C. by using an injection molding machine (“IS-100” manufactured by TOSHIBA MACHINE). A specimen was obtained. About the obtained test piece and pellet, surface appearance, tensile strength, impact strength, and fluidity were measured by the method described above. The results are shown in Table 1.

  The resin composition and the molded body obtained here had toughness and fluidity and were highly practical.

Comparative Example 1
Using a PPS resin and a polyolefin as a base without using a copolymerized polyolefin, dry blending was performed in the proportions shown in Table 1 in the same manner as in the Examples, and then melt-kneading, pelletizing, molding, and evaluation were performed. The results are shown in Table 1.

  When the copolymerized polyolefin was not blended, the impact strength was low and not practical.

Comparative Example 2
Using 220 parts by weight of glass fiber as a filler with respect to 100 parts by weight of the polymer, in the same manner as in the Examples, after dry blending at a ratio shown in Table 1, melt-kneading, pelletizing, molding, and evaluation were performed. The results are shown in Table 1.

  When 220 parts by weight of the filler was used, the fluidity and surface appearance were poor and not practical.

Comparative Example 3
Using a combination of a PPS resin and a copolymerized polyolefin as a base and a ratio of the copolymerized polyolefin of 40% by weight, in the same manner as in the examples, after dry blending in the proportions shown in Table 1, melt-kneading, pelletizing, molding, and evaluation Went. The results are shown in Table 1.

  When too much copolymerized polyolefin was added without adding polyolefin, a large amount of gas was generated during melt-kneading, the tensile strength was low, the fluidity and surface appearance were poor, and it was not at a practical level.

Comparative Example 4
Using a PPS resin and a filler without using a polyolefin resin and a copolymerized polyolefin, dry blending was carried out at the ratio shown in Table 1 in the same manner as in the Examples, and then melt-kneading, pelletizing, molding, and evaluation were performed. The results are shown in Table 1.

  When no polyolefin resin or copolymer polyolefin was used, the impact strength was low and it was not practical.

Comparative Example 5
Using a mixture of copolymerized polyolefin and other polyolefins at a ratio of 5 and PPS resin as a base, and dry blending in the ratios shown in Table 1 in the same manner as in the examples, melt kneading, pelletizing, molding, Evaluation was performed. The results are shown in Table 1.

  When only a small amount of copolymerized polyolefin was blended compared to polyethylene, both tensile strength and impact strength were low and not practical.

Comparative Example 6
Using a mixture of copolymerized polyolefin and other polyolefin at a ratio of 0.5 and PPS resin as a base, and dry blending at the ratio shown in Table 1 in the same manner as in the examples, melt kneading, pelletizing, Molding and evaluation were performed. The results are shown in Table 1.

  When the copolymerized polyolefin was blended twice compared with polyethylene, the tensile strength was low, the fluidity was poor, and it was not at a practical level.

Claims (5)

(A) 20 to 96% by weight of polyphenylene sulfide resin, (B) 1 to 30% by weight of copolymerized polyolefin obtained by copolymerizing ethylene and glycidyl methacrylate or glycidyl acrylate, (C) polystyrene resin, polyacrylate resin 3 to 50% by weight of one or more polyolefin resins selected from polymethacrylate resin, polyethylene resin and polypropylene resin, and the weight ratio (C) / (B) of (B) to (C) is 1. A polyphenylene sulfide resin composition comprising (D) 10 to 200 parts by weight of an inorganic filler with respect to 100 parts by weight of the composition of (A) to (C) which is ˜4.8. (D) The polyphenylene sulfide resin composition according to claim 1, wherein the inorganic filler is glass fiber. The polyphenylene sulfide resin composition according to claim 1 or 2, wherein (C) the polyolefin resin is a polyethylene resin having a density of 900 to 950 kg / m ³ . The polyphenylene sulfide resin composition according to any one of claims 1 to 3, wherein (C) the polyolefin resin is a polyethylene resin having a melt flow rate (MFR) of 0.05 to 12 g / 10 min. 5. (A) Polyphenylene sulfide resin, (B) copolymer polyolefin, and (C) polyolefin resin are melt-kneaded and then (D) an inorganic filler is added and melt-kneaded for production. The manufacturing method of the polyphenylene sulfide resin composition in any one.