JP2007246883A - Polyphenylene sulfide resin composition and molded article thereof - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyphenylene sulfide resin composition maintaining the excellent heat resistance, dimensional stability and flame retardancy possessed by a conventional polyphenylene sulfide resin, having excellent insulation properties, mechanical characteristics, impact resistance and fluidity, and especially having both of the excellent strength and heat-conductivity; and to provide a molded article thereof. <P>SOLUTION: The polyphenylene sulfide resin composition is obtained by compounding (A) 100 pts.wt. polyphenylene sulfide resin, (B) 50-300 pts.wt. magnesium carbonate and (C) 10-100 pts.wt. glass fiber. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a polyphenylene sulfide resin composition that has a good fluidity during molding and can provide a molded product having excellent thermal conductivity and strength, and more specifically, has excellent thermal conductivity and strength, In addition, the present invention relates to a polyphenylene sulfide resin composition having an excellent balance of properties such as excellent fluidity, insulating properties, mechanical properties, heat resistance, and impact resistance, and a molded article comprising the same.

  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.

  In recent years, various electrical components have been electronically controlled by computers in order to improve fuel efficiency, weight reduction or safety, and comfort in the automobile field. In the electric / electronic field, as well as improving the performance of personal computers, household electrical appliances such as refrigerators and washing machines are being electronically controlled by computers for the purpose of energy saving.

  Electronic devices such as LSIs and CPUs that perform electronic control have problems such as damage to electronic devices due to increased power consumption due to increased integration of computers and faster operation, and increased heat generation.

  Therefore, heat dissipation measures are necessary for computers, and conventionally heat sinks made of aluminum or die-casting have been used to dissipate heat in electronic component packages that are heat sources, but the heat dissipation characteristics with respect to the amount of heat generated are limited. It is reaching an area beyond.

  However, in the future, when parts are further reduced in size, weight, or complicated shape, metal such as die-casting is not productive and the shape is limited. Therefore, by adding fillers with high thermal conductivity such as graphite, alumina, and aluminum nitride to thermoplastic resins, studies are being made on improving productivity by resinization and balancing heat dissipation properties. However, the present situation is that a PPS resin composition that can satisfy the fluidity has not yet been obtained.

Several fillers have been studied so far for the purpose of improving this high heat dissipation. For example, Patent Document 1 discloses a resin composition in which anhydrous magnesium carbonate is blended with a PPS resin, but according to the study by the present inventors, it exhibits high thermal conductivity but is inferior in mechanical strength. understood. Patent Document 2 discloses a PPS resin composition in which magnesium carbonate and glass fiber are blended with a PPS resin. However, since this composition has a small amount of magnesium carbonate, its thermal conductivity is small and heat dissipation is poor. I understood. Patent Document 3 discloses a PPS resin composition in which a glass fiber and an olefin resin are blended with a PPS resin. However, it has been found that this resin composition has a low thermal conductivity and is inferior in heat dissipation.
Japanese Patent Laying-Open No. 2005-272752 (page 1-4) JP-A-2-191665 (page 1-4) Japanese Patent Laying-Open No. 2005-60454 (page 1-2)

  The present invention maintains the excellent heat resistance, dimensional stability, flame retardancy, etc. of the above-mentioned conventional polyphenylene sulfide resin, and is excellent in insulation, mechanical properties, impact resistance, fluidity, and particularly excellent strength and An object of the present invention is to provide a PPS resin composition having both thermal conductivity and a molded product thereof.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that the above problems can be solved by blending magnesium carbonate and glass fibers having a specific composition into the PPS resin, and have reached the present invention.

That is, the present invention
(1) A polyphenylene sulfide resin composition comprising (B) 50 to 300 parts by weight of magnesium carbonate and (C) 10 to 100 parts by weight of glass fibers, relative to 100 parts by weight of (A) polyphenylene sulfide resin,
(2) The polyphenylene sulfide resin composition according to the above (1), wherein (B) magnesium carbonate is anhydrous magnesium carbonate having an average particle diameter of 1 to 80 μm,
(3) Further described in (1) or (2) above, wherein (D) 2-50 parts by weight of an olefin resin having a density of 850-950 kg / m ³ is blended with 100 parts by weight of (A) polyphenylene sulfide resin. Polyphenylene sulfide resin composition,
(4) The polyphenylene sulfide resin composition according to any one of (1) to (3), further comprising (E) a coupling agent in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the (A) polyphenylene sulfide resin. ,
(5) Melt flow rate (measured using a melt indexer under the conditions of 315 ° C., 5 minutes residence, preload 1000 g, measurement load 2160 g (orifice diameter 2.095 mm, length 8.00 mm)) is 1 g / The polyphenylene sulfide resin composition according to any one of the above (1) to (4), which is 10 minutes to 100 g / 10 minutes,
(6) The volume resistivity of the molded body using the polyphenylene sulfide resin composition according to any one of (1) to (5) above is 10 ¹⁰ Ω · m or more and the thermal conductivity is 0.45 W / (m · K) A molded body that is equal to or higher than the above is provided.

  The polyphenylene sulfide resin composition of the present invention maintains the excellent heat resistance, dimensional stability, flame retardancy, etc. of the conventional polyphenylene sulfide resin, and is excellent in insulation, mechanical properties, impact resistance, fluidity, In particular, it is possible to provide a resin composition having both excellent strength and thermal conductivity and a molded body thereof.

  Next, the present invention will be described more specifically.

  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 unit of PPS may be composed of a repeating unit 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. Furthermore, it is also possible to use a mixture of two or more different molecular weight distributions.

  The melt flow rate (MFR) of the PPS resin used in the present invention is not particularly limited as long as it can be melt-kneaded. However, it stays at 315.5 ° C. for 5 minutes, and the load is 5000 g (orifice diameter 2.095 mm, length 8). The measured value using a melt indexer under the condition of (0.00 mm) is preferably 10,000 g / 10 min or less, and more preferably 8000 g / 10 min or less. Although there is no restriction | limiting in particular as a minimum, From the point of melt viscosity, it is good that it is 50 g / 10min or more, and it is more preferable that it is 100 g / 10min or more.

  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, perchlorethylene, monochloroethane, dichloroethane , Halogen solvents such as tetrachloroethane, perchlorethane, chlorobenzene, methanol, ethanol, propanol, Nord, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, alcohol phenol based solvents such as polypropylene glycol, and benzene, toluene, and aromatic hydrocarbon solvents such as 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.

  The magnesium carbonate (B) used in the present invention may be any of basic magnesium carbonate, neutral magnesium carbonate, hydroxy magnesium carbonate, and anhydrous magnesium carbonate, but preferably anhydrous magnesium carbonate is used.

  Although there is no restriction | limiting in particular in the average particle diameter of said (B), Preferably it is 1-80 micrometers, and 2-50 micrometers is more preferable. When the average particle size is less than 1 μm, the filler is poorly dispersed, and the fluidity and toughness may be lowered. If it exceeds 80 μm, the thermal conductivity and mechanical strength may decrease. An average particle diameter is an average particle diameter calculated | required based on the particle size distribution measured in accordance with the conventional method using the laser diffraction type particle size distribution analyzer. The purity is not particularly limited, but the higher the purity, the less the generated gas is preferable.

  The blending amount of (B) magnesium carbonate is 50 to 300 parts by weight, preferably 70 to 300 parts by weight, and more preferably 100 to 250 parts by weight with respect to 100 parts by weight of (A) PPS resin. Exceeding 300 parts by weight is not preferable because the fluidity and strength decrease. Further, in order to sufficiently obtain the effect of adding (B) magnesium carbonate, it is preferably 50 parts by weight or more, and more preferably 70 parts by weight or more.

  The magnesium carbonate (B) can be subjected to a surface treatment within a range that does not impair the effects of the present invention. Specifically, an epoxy compound, an isocyanate compound, a silane compound, a titanate compound, and a borane treatment. And ceramic coats. Of these, epoxy compounds or silane compounds are preferred.

  (C) Glass fiber used by this invention does not have a restriction | limiting in particular in an average fiber diameter, However, It is preferable that an average fiber diameter is 20 micrometers or less, More preferably, an average fiber diameter is 16 micrometers or less. The lower limit is not particularly limited and is preferably as small as possible. However, a sufficient effect can be obtained if it is usually 5 μm or more. It is preferable that the average fiber diameter is 20 μm or less because the strength is increased. Generally, the average fiber diameter is an average fiber diameter measured by an ordinary method using an electronic scanning microscope. Moreover, there is no restriction | limiting in particular about purity.

  The blending amount of the glass fiber (C) is 10 to 100 parts by weight, preferably 20 to 100 parts by weight, based on 100 parts by weight of (A). If the amount is too small, the rigidity and high-temperature mechanical strength are low, which is not preferable. If the amount is too large, the thermal conductivity is decreased, which is not preferable.

  The glass fiber of the above (C) can be subjected to a surface treatment within a range that does not impair the effects of the present invention, and examples of the treatment agent include a surface treatment agent and a sizing agent. Examples thereof include compounds, isocyanate compounds, organosilane compounds, organic titanate compounds, and organic borane treatment.

The resin composition of the present invention preferably further contains (D) an olefin resin having a density of 850 to 950 kg / m ³ .

  The (D) olefin resin used in the present invention is a (co) polymer obtained by (co) polymerizing olefins. Examples of the olefin (co) polymer include ethylene, propylene, 1-butene, 1-pentene, (Co) polymers obtained by (co) polymerizing α-olefins alone or in combination of two or more such as 4-methyl-1-pentene and isobutylene, α-olefins and acrylic acid, methyl acrylate, ethyl acrylate, acrylic Examples include α, β-unsaturated acids such as butyl acid, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and copolymers with alkyl esters thereof. Preferable specific examples of the olefinic (co) polymer include polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / 1-butene copolymer, ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer. Examples thereof include a polymer, an ethylene / butyl acrylate copolymer, an ethylene / methyl methacrylate copolymer, an ethylene / ethyl methacrylate copolymer, and an ethylene / butyl methacrylate copolymer.

  The olefin polymer is not more than 40% by weight and can be further copolymerized with other unsaturated monomers such as vinyl ether, vinyl acetate, vinyl propionate, acrylonitrile, and styrene within a range that does not impair the object of the present invention. Etc. may be copolymerized.

  In the present invention, an olefin copolymer (epoxy group-containing olefin copolymer) obtained by introducing a monomer component having an epoxy group into the olefin (co) polymer can also be preferably used. .

  In the present invention, the olefin resin may be used alone or in combination of two or more, and in particular, the following (d-1) epoxy group-containing olefin copolymer and (d-2) ethylene / α-olefin system. It is preferable to use a copolymer in combination.

  The (d-1) epoxy group-containing olefin copolymer used in the present invention is an olefin copolymer obtained by introducing a monomer component having an epoxy group into an olefinic (co) polymer.

  Examples of epoxy group-containing components for introducing a monomer component having an epoxy group into an olefinic (co) polymer include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid, etc. And a monomer containing an epoxy group.

  The method for introducing these epoxy group-containing components is not particularly limited, and it is possible to use a method such as copolymerization with the α-olefin as described above or graft introduction to the olefin (co) polymer using a radical initiator. it can.

  The introduction amount of the monomer component containing an epoxy group is suitably in the range of 0.001 to 40 mol%, preferably 0.01 to 35 mol%, based on the entire epoxy group-containing olefin copolymer. It is.

  As the (d-1) epoxy group-containing olefin copolymer particularly useful in the present invention, an olefin copolymer containing an α-olefin and a glycidyl ester of an α, β-unsaturated carboxylic acid as an essential copolymerization component is preferable. Can be mentioned. As said alpha olefin, ethylene is mentioned preferably. These copolymers further include α, β-unsaturated carboxylic acids such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like. It is also possible to copolymerize the alkyl ester and the like.

  In the present invention, it is particularly preferable to use an olefin-based copolymer containing an α-olefin and a glycidyl ester of an α, β-unsaturated carboxylic acid as essential components. Among them, 60 to 99% by weight of an α-olefin and α, β- An olefin copolymer having 1 to 40% by weight of an unsaturated carboxylic acid glycidyl ester as an essential copolymer component is particularly preferred.

  As the glycidyl ester of the α, β-unsaturated carboxylic acid,

(R represents a hydrogen atom or a lower alkyl group). Specific examples include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Among them, glycidyl methacrylate is preferably used. As a specific example of an olefin copolymer having an α-olefin and a glycidyl ester of α, β-unsaturated carboxylic acid as an essential copolymerization component, an ethylene / propylene-g-glycidyl methacrylate copolymer ("g" Represents graft, the same shall apply hereinafter), ethylene / 1-butene-g-glycidyl methacrylate copolymer, ethylene / glycidyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate Examples include copolymers and ethylene / methyl methacrylate / glycidyl methacrylate copolymers. Of these, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, and ethylene / methyl methacrylate / glycidyl methacrylate copolymer are preferably used.

  Further, (d-2) an ethylene / α-olefin copolymer comprising ethylene and an α-olefin having 3 to 20 carbon atoms, which is particularly useful in the present invention, is at least one or more having ethylene and 3 to 20 carbon atoms. It is a copolymer having the α-olefin as a constituent component. Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-undecene. 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1 -Pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl -1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and these Combinations are listed. Among these α-olefins, a copolymer using an α-olefin having 6 to 12 carbon atoms is more preferable because mechanical strength is improved and a reforming effect is further improved.

Density of (D) an olefin based resin of the present invention is 850~950kg / ^{m 3,} more preferably 850~930kg / ^{m 3.} If the density exceeds 950 kg / m ³ , it is difficult to develop toughness, and if it is less than 800 kg / m ³ , the handling property is lowered, which is not preferable. Density can be measured according to ASTM D1505.

  The melt flow rate (hereinafter abbreviated as MFR) of the (D) olefin resin of the present invention is preferably from 0.01 to 70 g / 10 min, more preferably from 0.0 to 70 g / 10 min. 03 to 60 g / 10 min. It is more preferable that the MFR is within this range because of excellent balance between fluidity and impact strength. The blending ratio of (A) PPS resin and (D) olefin resin of the present invention is 2 to 50 parts by weight of (D) olefin resin, preferably 2 to 30 parts per 100 parts by weight of (A) PPS resin. Parts by weight. Olefinic resins having this range are preferable because they can improve the flexibility and impact resistance, have little viscosity increase during melt-kneading, and are excellent in injection moldability. Furthermore, in the present invention, as described above, it is preferable to use (d-1) an epoxy group-containing olefin copolymer and (d-2) an ethylene / α-olefin copolymer in combination, and the combined ratio Is 5 to 40% by weight of component (d-1) and 95 to 60% by weight of component (d-2), preferably 10 to 30% by weight of component (d-1), based on the total of both. , (D-2) component is 90 to 70% by weight. When the component (d-1) is within this range, the desired morphology is obtained, and the viscosity during melt kneading is small and the injection moldability is excellent, which is preferable.

  In the present invention, it is preferable to further blend (E) a coupling agent.

  Although it does not specifically limit as (E) coupling agent used by this invention, The silane coupling agent which may be mix | blended is generally used as a surface treatment agent of various fillers, an adhesive agent, or a primer in coating. Among them, an alkoxysilane having at least one functional group selected from an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group, a ureido group, a vinyl group, and a methacryloxy group. 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 0.01 to 5 parts by weight and more preferably 0.1 to 3 parts by weight with respect to 100 parts by weight of the component (A). Addition of a coupling agent in this range is preferable because the strength is improved and the balance with fluidity is excellent. 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 polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, AS resin, polyamide 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, polyamide elastomer, polyester elastomer, polyester resin, polyphenylene ether resin, SA Resins, acrylic resins, SBS, SEBS, various elastomers, etc., can be blended in a range not impairing the effects of the present invention. Furthermore, these can also be used in combination of 2 or more types.

  In the resin composition of the present invention, inorganic fillers such as fibers, plates, powders and granules can be used as long as the effects of the present invention are not impaired. Specifically, for example, fibrous fillers such as carbon fiber, potassium titanate whisker, zinc oxide whisker, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, stone-cow fiber, wollastonite, phlogopite, mascobite, zeolite, Swelling layered silicates such as sericite, kaolin, mica, clay, bentonite, asbestos, talc, alumina silicate, montmorillonite, synthetic mica, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, oxidation Metal compounds such as iron, carbonates such as calcium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, ceramic beads, silica, wet white carbon, granular wollastonite, zeolite, calcium hydroxide, magnesium hydroxide, water Of hydroxides such as aluminum, glass beads, boron nitride, silicon carbide, graphite, pyrophyllite, calcium phosphate, non-fibrous fillers such as pyrophyllite and the like. These may be hollow, and two or more of these fillers can be used in combination.

  The particulate inorganic filler may be surface-treated within a range that does not impair the effects of the present invention, and examples of the treatment agent for performing the surface treatment include a surface modifier and a sizing agent. , Fatty acid, wax, nonionic surfactant, epoxy compound, isocyanate compound, silane compound, titanate compound, phosphorus compound, aluminum salt such as alumina, silicate such as silicon dioxide, titanium dioxide, etc. Examples thereof include titanium salts.

  Furthermore, it is possible to mix | blend carbon black with the resin composition of this invention in the range which does not impair the effect of this invention. The carbon black can be used in any kind such as for imparting conductivity and for a colorant as long as C (carbon) is a main component, but a channel type and a furnace type used as a colorant are preferable. 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.

  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 polypropylene, montanic acid waxes, lithium stearate , Metal soap such as aluminum stearate, ethylenediamine / stearic acid / sebacic acid polycondensate, release agent such as silicone compound, anti-coloring agent such as hypophosphite, hindered phenol antioxidant, phosphorus Oxidation of antioxidants, sulfur-based antioxidants, etc. Stopper, weathering agent and UV protection agent (resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.), heat stabilizer, lubricant (montanic acid and its metal salt, its ester, its half ester, stearyl alcohol) , Stearamide, various bisamides, bisureas, polyethylene waxes, etc.), foaming agents, pigments (cadmium sulfide, phthalocyanine, carbon black, iron black, metallic pigments, etc.), dyes (nigrosine, etc.), antistatic agents (alkyl sulfate type anions) General additives such as antistatic agents, quaternary ammonium salt type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agents), flame retardants, etc. Can be added.

  The method for preparing the resin composition used in the present invention is not particularly limited, but the components (A), (B), (C), (D), (E) and other raw materials added as necessary are melted. It is obtained by kneading. Specific examples include a method of supplying a mixture of raw materials to a commonly known melt mixer such as a single or twin screw extruder, a Banbury mixer, a kneader, a mixing roll, and kneading at a temperature of 280 to 450 ° C. be able to. In addition, there is no particular limitation on the mixing order of the raw materials, a method in which all the raw materials are blended and then melt-kneaded by the above method, a part of the raw materials are blended and then melt-kneaded by the above method, and the remaining raw materials are blended and melted. Any method may be used, such as a method of kneading or a method of mixing a part of raw materials and mixing the remaining raw materials using a side feeder during melt-kneading with a single or twin screw extruder. 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. In addition, it is more preferable to pre-blend (A) the PPS resin and (E) the coupling agent and then blend other raw materials because the reactivity of the PPS resin and the coupling agent is improved.

  The MFR of the PPS resin composition obtained in the present invention is not particularly limited as long as it can be molded. From the viewpoint of strength, the MFR stays at 315 ° C. for 5 minutes, the preload is 1000 g, the measurement load is 2160 g (the orifice diameter is 2.095 mm, The measured value using a melt indexer under the condition of length 8.00 mm is preferably 100 g / 10 min or less, and more preferably 80 g / 10 min or less. The lower limit is preferably 1 g / 10 min or more from the viewpoint of fluidity, and more preferably 5 g / 10 min or more. The MFR of the PPS resin composition depends mainly on the amount of the (A) PPS resin used (A), the components (B) to (E), etc., and by using the (A) PPS resin having a low MFR, or (B) Since the MFR tends to decrease as the amount of the component (E) increases, a PPS resin composition having the above range can be obtained by appropriately adjusting these.

  The PPS resin composition of the present invention is three-dimensionally molded by various known injection molding methods such as injection molding, injection compression molding, two-color molding, DSI molding, extrusion molding, blow molding, gas injection molding, mucell molding, and the like. Although it can be processed into products, sheets, cases (housings), etc., in consideration of productivity, injection molding or injection press molding is preferably employed. Moreover, when it has a welding part, it is possible to use general welding methods, such as a hot plate, a vibration, an ultrasonic wave, and a laser.

The molded product obtained by molding the PPS resin composition of the present invention preferably has a volume resistivity of 10 ¹⁰ Ω · m or more and a thermal conductivity of 0.45 W / (m · K) or more. The specific resistance is more preferably 10 ¹¹ Ω · m or more, and the thermal conductivity is more preferably 0.5 W / (m · K) or more. Utilizing these electrical characteristics, insulation and high heat dissipation are achieved, and it is suitable for components such as power modules in which metal terminals are inserted. The volume resistivity is a value measured according to IEC 60093 under a temperature condition of 23 ° C., and the thermal conductivity is in accordance with a conventional method (test piece: 20 mm × 20 mm × 4 mm thickness) using a steady-state thermal conductivity meter. The thermal conductivity was measured.

  The molded product thus obtained has good fluidity at the time of molding processing, and the filling density of the obtained molded product is increased, so that it has excellent mechanical properties and thermal conductivity, and under use conditions under high temperature and high humidity. It is advantageous for high heat dissipation applications, metal replacement applications, ceramic replacement applications, electromagnetic wave shielding applications, high precision parts (low dimensional change), high conductivity applications, etc. Specifically, various cases, gear cases, LED lamp related parts, connectors, relay cases, switches, variable capacitor cases, optical pickup lens holders, optical pickup slide bases, various terminal boards, transformers, printed wiring boards, liquid crystal panels Frame, power module and its housing, plastic magnet, semiconductor, liquid crystal display component, projector, etc. Lamp cover, FDD carriage, FDD chassis, actuator, HDD parts such as chassis, electrical / electronic parts such as computer related parts, VTR parts, TV parts, iron, hair dryer, rice cooker parts, microwave oven parts, acoustics Parts, audio equipment parts such as audio / laser discs (registered trademark) / compact discs / digital video discs, lighting parts, refrigerator parts, air conditioner parts, power module parts, home electric appliance parts, office computers Parts, telephone-related parts, facsimile-related parts, parts related to printers and copiers such as print heads and transfer rolls, cleaning jigs, motor parts, microscopes, binoculars, cameras, optical instruments represented by watches, precision machines Related parts Alternator terminal, alternator connector, IC regulator, light dimmer potentiometer base, motor core sealant, insulator member, power seat gear housing, air conditioner thermostat base, air conditioner panel switch board, horn terminal, electrical component insulation plate, relay block , Engine control units, lamp housings, lamp reflectors, ignition device cases, power modules, inverter cases, condenser cases and other automotive / vehicle-related parts, PC housings, mobile phone housings, and other devices such as chip antennas and shielding of electromagnetic waves In a wide range of fields such as housings such as parts such as installed antennas that require safety, etc., in addition, high dimensional accuracy, electromagnetic wave shielding, It is useful for partition plates that require barrier properties such as body and liquid, applications that require heat and electrical conductivity, equipment for outdoor installations, and building materials. Especially, it has heat dissipation, weight reduction, and freedom of shape. It is useful for cases such as sockets, covers, and housings of electrical and electronic parts that are required and are eager to replace metals.

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

  The MFR, tensile strength, Charpy impact strength, volume resistivity, and thermal conductivity described in the examples and comparative examples were each measured according to the following methods.

[Measurement of MFR of composition]
A value obtained by measuring a pellet according to JIS K7210 using a melt indexer under conditions of 315 ° C. for 5 minutes, a preload of 1000 g, and a measurement load of 2160 g (orifice diameter 2.095 mm, length 8.00 mm). The higher this value, the better the fluidity and the better.

[Measurement of tensile strength]
An ISO multipurpose tensile test piece (4 mm thickness) was molded at a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C., and measured according to ISO 527-1 and 527-2 under a temperature condition of 23 ° C. If it is 80 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 Charpy impact strength]
An ISO multipurpose tensile test piece (4 mm thickness) was molded at a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C., and measured according to ISO 179-1 under a temperature condition of 23 ° C. If the impact strength with V-notch is 3.5 kJ / m ² or more, it can be said that the product strength level has no practical problem, but the higher this value, the better the toughness and the better.

[Measurement of volume resistivity]
A square plate test piece (80 mm × 80 mm × 3 mm thickness, film gate) was molded at a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C., and measured according to IEC 60093 under a temperature condition of 23 ° C. If it is 10 ¹⁰ Ω · m or more, it can be said that the insulation level has no practical problem, but the higher this value, the better the insulation and the better.

[Measurement of thermal conductivity]
An ISO multipurpose tensile test piece (4 mm thickness) is molded at a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C., and a 20 mm × 20 mm test piece is cut out from this test piece, and heat conduction is performed using a steady-state thermal conductivity meter. The rate was measured. If it is 0.45 W / (m · K) or more, it can be said that it is a practical level, but the higher this value, the better the heat dissipation and the better.

[Reference example]
((A) Production of polyphenylene sulfide resin)
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 PPS with MFR of 6000 g / 10 min. 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 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]
(B-1) Magnesium carbonate: average particle size 8 μm, anhydrous magnesium carbonate (synthetic magnesium carbonate) purity 99% or more (manufactured by Kamishima Chemical Industries)
(B-2) Magnesium carbonate: average particle size 20 μm, anhydrous magnesium carbonate (synthetic magnesium carbonate) purity 99% or more (manufactured by Kamishima Chemical Industries)
(B-3) Magnesium carbonate: average particle size 5.5 μm, basic magnesium carbonate (manufactured by Kamishima Chemical Industries)
(B′-1) Magnesium oxide: “Cool Filler CF2-100A”, average particle size 30 μm, magnesium oxide purity 99% or more (with surface ceramic coating), manufactured by Tateho Chemical Industries
(B′-2) Alumina: “AL-43-KT” Fine low-soda alumina, average particle size 4.6 μm (made by Showa Denko)
In the above, the average particle diameter of magnesium carbonate, magnesium oxide, and alumina is an average particle diameter determined based on a particle diameter distribution measured according to a conventional method using a laser diffraction particle size distribution measuring machine.
(B′-3) Graphite: “Graphite (CFW), CFW50A”, scaly filler, average particle size 50 μm, (manufactured by Chuetsu Graphite Co., Ltd.)
In addition, an average particle diameter is the number average measured by the sieving test method based on JIS-K0069.
(B′-4) Calcium carbonate: “KS1300” average particle size 3.8 μm (manufactured by Dowa Calfine)
In addition, in the above, the average particle diameter of calcium carbonate is an average particle diameter calculated | required based on the particle size distribution measured in accordance with the conventional method using the laser diffraction type particle size distribution measuring machine.
(C) Glass fiber: “T747H” average fiber diameter 10.5 μm (manufactured by NEC Glass)
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.
(D-1): ethylene / glycidyl methacrylate = 88/12 (% by weight) copolymer, “BF-E” (manufactured by Sumitomo Chemical Co., Ltd.)
(D-2): MFR = 35 (190 ° C., 2.16 kg load), ethylene / 1-butene copolymer having a density of 860 kg / m ³ , “TX650” (manufactured by Mitsui Chemicals)
(E) Coupling agent: β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane)

Examples 1-10, Comparative Examples 1-7
(A) PPS resin prepared as described above, (B) magnesium carbonate or (B ′) component prepared as a comparative material, (C) glass fiber, (D) olefin resin, (E) coupling agent After dry blending at the ratio shown in Table 1, it was melt kneaded and pelletized by a screw type twin screw extruder set to an extrusion condition of 350 ° C. The obtained pellets were dried and then subjected to injection molding under the conditions of a cylinder temperature of 320 ° C. and a mold temperature of 140 ° C. using an injection molding machine to obtain predetermined test pieces for characteristic evaluation. About the obtained test piece and pellet, MFR, tensile strength, Charpy impact strength, volume resistivity, and thermal conductivity were measured by the method described above. The results are shown in Table 1.

From the results in Table 1, the following matters are clear.
(1) The PPS resin composition of the present invention and the molded product thereof have high thermal conductivity, strength, and insulation, and are highly practical (Examples 1 to 10).
(2) On the other hand, when only magnesium carbonate was used without using glass fiber, the tensile strength and Charpy impact strength were low and not practical (Comparative Example 1).
(3) Also, when magnesium oxide or alumina was used instead of magnesium carbonate, the tensile strength and Charpy impact strength were low and not at a practical level (Comparative Examples 2 and 3).
(4) Further, when graphite was used instead of magnesium carbonate, the volume resistivity and MFR were low and not at a practical level (Comparative Example 4).
(5) Further, when calcium carbonate was used instead of magnesium carbonate, the thermal conductivity was low and not at a practical level (Comparative Example 5).
(6) Further, when 10 parts by weight of magnesium carbonate, which is outside the scope of the present invention, was blended, the thermal conductivity was low and it was not at a practical level (Comparative Example 6).
(7) Moreover, when glass fiber and an olefin resin were used without using magnesium carbonate, the thermal conductivity was low and not at a practical level (Comparative Example 7).

Claims (6)

(A) Polyphenylene sulfide resin composition obtained by blending 50 to 300 parts by weight of magnesium carbonate and (C) 10 to 100 parts by weight of glass fiber with respect to 100 parts by weight of polyphenylene sulfide resin. (B) The polyphenylene sulfide resin composition according to claim 1, wherein the magnesium carbonate is anhydrous magnesium carbonate having an average particle diameter of 1 to 80 μm. The polyphenylene sulfide resin composition according to claim 1 or 2, further comprising (D) 2 to 50 parts by weight of an olefin resin having a density of 850 to 950 kg / m ³ to 100 parts by weight of (A) polyphenylene sulfide resin. The polyphenylene sulfide resin composition according to any one of claims 1 to 3, further comprising (E) a coupling agent in an amount of 0.01 to 5 parts by weight per 100 parts by weight of the (A) polyphenylene sulfide resin. Melt flow rate (measured using a melt indexer under conditions of 315 ° C., 5 minutes residence, preload 1000 g, measurement load 2160 g (orifice diameter 2.095 mm, length 8.00 mm)) from 1 g / 10 min The polyphenylene sulfide resin composition according to any one of claims 1 to 4, which is 100 g / 10 minutes. Molding using the polyphenylene sulfide resin composition according to any one of claims 1 to 5 having a volume resistivity of 10 ¹⁰ Ω · m or more and a thermal conductivity of 0.45 W / (m · K) or more. body.