JP2007302822A - Polyphenylene sulfide resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To obtain a polyphenylene sulfide resin composition suitable for injection molding, balancing excellent weld characteristics, epoxy adhesiveness, chemical resistance and thermal conductivity in a high level, and also having excellent retention stability at molding. <P>SOLUTION: The polyphenylene sulfide resin composition is composed of (A) 50-99 wt.% polyphenylene sulfide with (B) 50-1 wt.% copolymer containing an aromatic vinyl monomer component and a vinyl cyanide monomer component. In the copolymer (B), the composition ratio of the aromatic vinyl monomer component over the vinyl cyanide monomer component in the copolymer, is 77/23-90/10 wt.%. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polyphenylene sulfide resin composition suitable for injection molding, which has excellent weld properties, epoxy adhesion, chemical resistance, and thermal conductivity at a high balance and excellent retention stability during molding. is there.

  Polyphenylene sulfide has excellent heat resistance, flame retardancy, chemical resistance, electrical insulation and moist heat resistance, and therefore has suitable properties as engineering plastics. Widely used in applications such as electrical / electronic parts, machine parts and automobile parts. However, polyphenylene sulfide is not always satisfactory for electric and electronic parts such as sensors and covers, LEDs and lamp sockets that require weld strength and epoxy adhesion. While electrical and electronic parts are becoming smaller and modular, measures to dissipate heat from electrical parts have come to be demanded. However, thermoplastic resins such as polyphenylene sulfide are generated due to their low thermal conductivity. In reality, heat cannot be diffused efficiently, and some developments are limited due to the recent trend toward higher output of electrical and electronic components. In order to solve these problems, various improvement methods have been proposed so far.

  For example, a method of blending a styrene / maleic anhydride copolymer with an epoxy-modified polyphenylene sulfide (see Patent Document 1), an aromatic vinyl compound having a specific intrinsic viscosity and a weight average molecular weight / number average molecular weight ratio / cyan in a thermoplastic resin A method of blending a copolymer of a vinyl fluoride compound (see Patent Document 2), a method of blending a high-filler-containing thermoplastic resin with a styrene resin having a specific viscosity (see Patent Document 3), and the like have been proposed. The copolymerization ratio of the aromatic vinyl compound / vinyl cyanide compound described in Patent Document 2 is 63/27 to 70/30 wt%, and the aromatic vinyl compound / vinyl cyanide described in Patent Document 3 The copolymerization ratio of the compound was 74/26% by weight, and the characteristics when paying out to a thermoplastic resin such as polyphenylene sulfide were not sufficient.

In Patent Document 1, although epoxy adhesion is improved by epoxy-modifying polyphenylene sulfide, it cannot be said to be sufficient, and it is not possible to obtain an improvement effect on characteristics such as weld characteristics and thermal conductivity. Further, although Patent Document 2 improves weld characteristics, it cannot be said that epoxy adhesion and chemical resistance are sufficient, and Patent Document 3 also cannot be said to have sufficient epoxy adhesion, weld characteristics, etc. It was not satisfactory.
Japanese Patent Laid-Open No. 6-340809 (first and second items, examples) Japanese Patent Laid-Open No. 11-80470 (first and second items, examples) Japanese Unexamined Patent Publication No. 2004-83867 (first and second items, examples)

  The present invention eliminates the above-mentioned conventional problems and maintains excellent weld characteristics, epoxy adhesion, chemical resistance, and thermal conductivity while maintaining the product design freedom and productivity that are the characteristics of thermoplastic resins. It is an object of the present invention to provide a polyphenylene sulfide resin composition suitable for injection molding, which is balanced at a high level and also has excellent residence stability during molding and is excellent.

  As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.

That is, the present invention
(1) The copolymer composition ratio of (A) polyphenylene sulfide 50 to 99% by weight and (B) aromatic vinyl monomer component and vinyl cyanide monomer component is 77/23 to 90/10% by weight. A polyphenylene sulfide resin composition comprising 50 to 1% by weight of a copolymer containing an aromatic vinyl monomer component and a vinyl cyanide monomer component;
(2) The polyphenylene sulfide resin composition according to (1), wherein 5 to 300 parts by weight of (C) filler is blended with respect to a total of 100 parts by weight of (A) and (B).
(3) (A) The polyphenylene sulfide resin composition according to (1) or (2), wherein the polyphenylene sulfide resin temperature is 310 ° C. and the melt viscosity at a shear rate of 1000 / sec is 100 Pa · s or more,
(4) The polyphenylene sulfide resin according to any one of (2) to (3), wherein D50 (cumulative particle size distribution) obtained by the laser diffraction scattering method of (C) filler is in the range of 5 to 60 μm. Composition,
(5) The polyphenylene sulfide resin composition according to any one of (2) to (4), wherein D90 (cumulative particle size distribution) obtained by the laser diffraction scattering method of (C) filler is 10 to 150 μm ,
(6) The polyphenylene sulfide resin composition according to any one of (2) to (5), wherein the filler (C) includes a thermally conductive filler having a thermal conductivity of 20 W / mk or more measured by a laser flash method. The polyphenylene sulfide resin composition according to any one of (2) to (6), wherein the product and (7) (C) filler are surface-treated with an organic titanate coupling agent.

  The present invention is required because it has a high balance of weld properties, epoxy adhesion, chemical resistance, and thermal conductivity, and also has excellent retention stability during molding processing. It can be particularly practically used for applications such as electric / electronic parts or automobile parts.

  Hereinafter, the present invention will be described in detail. In the present invention, “weight” means “mass”.

  The polyphenylene sulfide (A) in the present invention is a polymer containing a repeating unit represented by the following structural formula, preferably 70 mol% or more, more preferably 90 mol% or more. When the repeating unit is 70 mol% or more, Is preferable in terms of excellent heat resistance.

  Further, such polyphenylene sulfide can be composed of 30 mol% or less of the repeating unit with a repeating unit having the following structural formula, and may be a random copolymer or a block copolymer. A mixture thereof may also be used.

  Such polyarylene sulfide can be obtained by a generally known method, that is, a method for obtaining a polymer having a relatively small molecular weight described in JP-B-45-3368, or JP-B-52-12240 and JP-A-61-7332. Can be produced by, for example, a method for obtaining a polymer having a relatively large molecular weight.

  In the present invention, the polyphenylene sulfide obtained as described above is subjected to crosslinking / polymerization by heating in air, heat treatment in an inert gas atmosphere such as nitrogen or under reduced pressure, organic solvent, hot water, acid aqueous solution. Of course, it is also possible to use after performing various treatments such as washing with acid anhydride, amine, isocyanate, activation with a functional group-containing compound such as a functional group-containing disulfide compound.

  As a specific method for crosslinking / polymerizing polyphenylene sulfide by heating, it can be performed in an oxidizing gas atmosphere such as air or oxygen or in a mixed gas atmosphere of the oxidizing gas and an inert gas such as nitrogen or argon. A method of heating until a desired melt viscosity is obtained at a predetermined temperature in a heating container can be exemplified. In this case, the heat treatment temperature is preferably 150 to 280 ° C., more preferably 200 to 270 ° C., and the treatment time is preferably 0.5 to 100 hours, more preferably 2 A range of ˜50 hours is selected, but by controlling both, a target viscosity level can be obtained. Such a heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary or stirring blade. However, in the case of efficient and more uniform treatment, a heating apparatus with a rotary or stirring blade is used. Is more preferable.

As a specific method for heat-treating polyphenylene sulfide under an inert gas atmosphere such as nitrogen or under reduced pressure, heat treatment is performed under an inert gas atmosphere such as nitrogen or under reduced pressure (preferably 7,000 Nm ^-2 or less). Examples thereof include a method of heat treatment under conditions of a temperature of 150 to 280 ° C, preferably 200 to 270 ° C, and a heating time of 0.5 to 100 hours, preferably 2 to 50 hours. Such a heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary or stirring blade. However, in the case of efficient and more uniform treatment, a heating apparatus with a rotary or stirring blade is used. Is more preferable.

  When polyphenylene sulfide is washed with an organic solvent, the organic solvent used for washing is not particularly limited as long as it does not have an action of decomposing polyphenylene sulfide. For example, nitrogen-containing polar solvents such as N-methylpyrrolidone, dimethylformamide, dimethylacetamide, sulfoxide sulfone solvents such as dimethyl sulfoxide, dimethylsulfone, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, dimethyl ether, dipropyl ether , Ether solvents such as tetrahydrofuran, halogen solvents such as chloroform, methylene chloride, trichloroethylene, ethylene chloride, dichloroethane, tetrachloroethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, Alcohol / phenolic solvents such as cresol and polyethylene glycol, benzene and toluene Ene, and aromatic hydrocarbon solvents such as xylene may be used. Of these organic solvents, N-methylpyrrolidone, acetone, dimethylformamide, chloroform and the like are particularly preferably used. These organic solvents are used alone or in combination of two or more.

  As a specific method of washing with such an organic solvent, there is a method of immersing polyphenylene sulfide in an organic solvent, and if necessary, stirring or heating can be appropriately performed. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning polyphenylene sulfide with an organic solvent, Arbitrary temperature of about normal temperature-about 300 degreeC can be selected. Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect is usually obtained at a cleaning temperature of room temperature to 150 ° C. The polyphenylene sulfide that has been washed with an organic solvent is preferably washed several times with water or warm water in order to remove the remaining organic solvent. The water washing temperature is preferably 50 to 90 ° C, and preferably 60 to 80 ° C.

  The following method can be illustrated as a specific method when treating polyphenylene sulfide with hot water. That is, it is preferable that the water used is distilled water or deionized water in order to express the effect of preferable chemical modification of polyphenylene sulfide by hot water washing. The operation of the hot water treatment is usually performed by adding a predetermined amount of polyphenylene sulfide to a predetermined amount of water, and heating and stirring at normal pressure or in a pressure vessel. The ratio of polyphenylene sulfide to water should be high, and preferably used at a bath ratio of 200 g or less of polyphenylene sulfide with respect to 1 liter of water.

  The following method can be illustrated as a specific method in the case of acid-treating polyphenylene sulfide. That is, there is a method of immersing polyphenylene sulfide in an acid or an aqueous solution of acid, and stirring or heating can be performed as necessary. The acid used is not particularly limited as long as it does not have the action of decomposing polyphenylene sulfide, and is saturated with aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, and halo substitution such as chloroacetic acid and dichloroacetic acid. Aliphatic unsaturated carboxylic acids such as aliphatic saturated carboxylic acids, acrylic acids and crotonic acids, aromatic carboxylic acids such as benzoic acid and salicylic acid, and dicarboxylic acids such as oxalic acid, malonic acid, succinic acid, phthalic acid and fumaric acid , And inorganic acidic compounds such as sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid, and silicic acid. Of these acids, acetic acid and hydrochloric acid are particularly preferably used. The polyphenylene sulfide subjected to the acid treatment is preferably washed several times with water in order to remove the remaining acid or salt. The water washing temperature is preferably 50 to 90 ° C, and preferably 60 to 80 ° C. The water used for washing is preferably distilled water or deionized water in the sense that it does not impair the preferable chemical modification effect of polyphenylene sulfide by acid treatment.

  The melt viscosity of the polyphenylene sulfide (A) used in the present invention is a copolymer containing a styrene monomer component and a vinyl cyanide monomer component necessary for exhibiting the effects of the present invention with high efficiency, and (C) In order to control the dispersion state of the filler in the PPS system, 100 Pa · s or more is preferable, and 200 Pa · s or more is more preferable. The upper limit of the melt viscosity is preferably 500 Pa · s or less in consideration of productivity. In addition, the measuring method of the melt viscosity of polyphenylene sulfide uses a capillograph (manufactured by Toyo Seiki Co., Ltd.) using an orifice having a hole diameter of 1.0 mm × length of 10 mm, a resin temperature of 310 ° C., and a shear rate of 1000. Measured according to the conditions per second.

  In the present invention, (B) a copolymer containing an aromatic vinyl monomer component and a vinyl cyanide monomer component is a copolymer of an aromatic vinyl monomer component and a vinyl cyanide monomer component. Specific examples of aromatic vinyl monomer components that are polymers include styrene, α-methylstyrene, p-methylstyrene, vinyltoluene, t-butylstyrene, o-ethylstyrene, o-chlorostyrene And o, p-dichlorostyrene and the like, and styrene and α-methylstyrene are particularly preferable, and these may be used alone or in combination of two or more.

  Specific examples of the vinyl cyanide monomer component include acrylonitrile, methacrylonitrile, ethacrylonitrile, and the like. Among these, acrylonitrile is particularly preferable, and one or more of these can be used.

The copolymer composition ratio of (B) aromatic vinyl monomer component and vinyl cyanide monomer component of the present invention is 77 in order to balance the residence stability and chemical resistance at the time of molding. / 23 to 90/10% by weight, preferably 79/21 to 82/18% by weight. Here, it is a unit in which the total amount of the aromatic vinyl monomer component and the vinyl cyanide monomer component is 100% by weight.
This copolymer composition ratio was determined by the cast method (solvent: methyl ethyl ketone), and the obtained thin film was converted into an aromatic vinyl type using a Fourier transform infrared spectrophotometer (FTIR-8100A; manufactured by Shimadzu Corporation). It can be confirmed from the intensity ratio of the IR spectrum between 700 cm ⁻¹ derived from the monomer component and 2240 cm ⁻¹ derived from the vinyl cyanide monomer component. It should be noted that five different types of copolymer having different copolymer composition ratios of the aromatic vinyl monomer component alone and the aromatic vinyl monomer component and the vinyl cyanide monomer component in the same manner as described above. Create a calibration curve for the polymer.
(B) When the aromatic vinyl monomer component and the vinyl cyanide monomer component have a copolymer composition in the above range, when the filler (C) is added, the filler is unevenly distributed on the surface of the molded product. The characteristics of the present invention can be exhibited with high efficiency.

  In order to further improve the weld characteristics in the present invention, (B) another copolymerizable monomer component is added to the copolymer of the aromatic vinyl monomer component and the vinyl cyanide monomer component. It may be added. Examples of such other copolymerizable monomer components include esters of acrylic acid, methacrylic acid and monohydric alcohols having 1 to 10 carbon atoms, and methyl methacrylate is particularly preferably used. Can do. (B) The amount of the other copolymerizable monomer component added to 100 parts by weight of the copolymer of the aromatic vinyl monomer component and the vinyl cyanide monomer component is a characteristic of the present invention. Is preferably 0.1 to 10 parts by weight, and more preferably 0.5 to 5 parts by weight.

  (B) There is no restriction | limiting in particular about the manufacturing method of the copolymer containing an aromatic vinyl-type monomer component and a vinyl cyanide-type monomer component, It can manufacture by a conventionally well-known method. That is, it can be produced by any of emulsion polymerization, solution polymerization, bulk polymerization, and suspension polymerization, but industrially bulk polymerization is advantageous. In addition, as a preferable shape of the copolymer containing (B) the aromatic vinyl monomer component and the vinyl cyanide monomer component, a bead shape and the like can be mentioned.

  In the present invention, the blending ratio (A) / (B) of the copolymer containing (A) polyphenylene sulfide, (B) aromatic vinyl monomer component, and vinyl cyanide monomer component is the weld characteristics, epoxy In order to develop properties such as adhesiveness, (A) / (B) is 50/50 to 99/1% by weight with respect to 100% by weight of the total amount of components (A) and (B), A) / (B) is preferably 70/30 to 95/5% by weight, and (A) / (B) is more preferably 75/25 to 90/10% by weight.

  In the present invention, in order to further improve the properties such as weld properties and epoxy adhesion, (C) filler or non-fiber (plate, scale, granular, irregular shape, crushed product, etc.) is added as filler. For example, as specific examples of fibrous fillers, glass fibers, PAN-based and pitch-based carbon fibers, stainless steel fibers, metal fibers such as aluminum fibers and brass fibers, organic fibers such as aromatic polyamide fibers, Gypsum fiber, ceramic fiber, asbestos fiber, zirconia fiber, alumina fiber, silica fiber, titanium oxide fiber, silicon carbide fiber, rock wool, potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, etc. The type of glass fiber or carbon fiber is generally There is no particular limitation if those used for reduction, for example, long fiber type and short fiber type, chopped strands, may be selected from such milled fiber. The filler may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer or a thermosetting resin such as an epoxy resin.

  Moreover, iron, copper, stainless steel, aluminum, brass, etc. can be illustrated as a specific example of the metal seed | species of the said metal fiber.

  Specific examples of non-fibrous fillers include mica, talc, kaolin, silica, calcium carbonate, glass beads, glass flakes, glass microballoons, clay, molybdenum disulfide, wollastonite, calcium polyphosphate, graphite, metal powder, metal flakes, Examples thereof include metal ribbons, metal oxides (alumina, zinc oxide, titanium oxide, etc.), carbon powder, graphite, carbon flakes, scaly carbon, carbon nanotubes and the like. Moreover, silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, tin etc. can be illustrated as a specific example of the metal seed | species of metal powder, metal flakes, and a metal ribbon.

Here, specific examples of metal species of the metal powder, metal flake and metal ribbon include specific examples of metal oxides such as silver, nickel, copper, zinc, aluminum, magnesium, stainless steel, iron, brass, chromium and tin. Specific examples of nitrides such as SnO ₂ (antimony dope), In ₂ O ₃ (antimony dope) and ZnO (aluminum dope) include AlN (aluminum nitride), BN (boron nitride), Si ₃ N ₄ Examples thereof include (silicon nitride).

  In the present invention, (C) D50 (cumulative particle size distribution) obtained by the laser diffraction scattering method of the filler is in the range of 5 to 60 μm in order to exhibit the properties such as epoxy adhesion by adding the filler (C) with high efficiency. It is preferably in the range of 7 to 55 μm, more preferably in the range of 10 to 50 μm, and (C) D90 (cumulative particle size distribution) obtained by the laser diffraction scattering method of filler. ) Is preferably 10 to 150 μm, more preferably 15 to 140 μm, and even more preferably 25 to 130 μm.

  As described above, it is presumed that the effect of the present invention is further improved by controlling the particle size distribution of the filler so as to control the dispersion state in the resin.

  The method for measuring the particle size (D50, D90) of the filler (C) used in the present invention is usually calculated by a laser diffraction scattering method (volume distribution). Specifically, the non-fibrous filler is used as an aqueous slurry, and the dispersion medium and After sufficiently dispersing by ultrasonic treatment, measurement is performed using a laser diffraction particle size distribution analyzer SALD-3100 (manufactured by Shimadzu Corporation). The dispersion medium used for the above measurement varies depending on the type of filler and cannot be generally specified. However, a liquid in which the filler is not agglomerated and can be uniformly dispersed with primary particles, such as a surfactant, is used.

  (C) When the filler is a fibrous filler, the fiber length is long, and measurement by the laser diffraction / scattering method is difficult, the value obtained by the laser diffraction / scattering method is measured indirectly by a method capable of measurement. use. Specifically, 100 mg of fibrous filler was collected and dispersed in a 100 cc dispersion medium, and then the dispersion was observed and photographed with a scanning electron microscope (manufactured by HORIBA). As D50 and D90 (cumulative particle size distribution) obtained by the laser diffraction scattering method assuming that the average fiber length and the maximum fiber length calculated by measuring 1000 fiber lengths of the filler are the maximum values of the particle diameters. Can be used.

  In order to impart further high thermal conductivity in the present invention, the component (C) preferably contains a thermal conductive filler having a thermal conductivity of 20 W / mK or more. It is preferable that at least a part or all of the component (C) has a thermal conductivity of 20 W / mK or more. (C) The upper limit of the thermal conductivity of the filler is preferably 1000 W / mk in consideration of productivity and versatility. Specifically, the heat conductive filler having a thermal conductivity of 20 W / mK or more is preferably 30% by weight or more, more preferably 60% by weight or more with respect to 100% by weight of the component (C).

  Specific examples of such heat conductive fillers include metal powder, metal flake, metal ribbon, metal fiber, beryllia, alumina, zinc oxide, magnesium oxide and other metal oxides, aluminum nitride, boron nitride, silicon nitride and other nitrides And inorganic fillers coated with a thermally conductive material, carbon powder, graphite, pitch-based carbon fiber, or PAN-based carbon fiber with a relatively high degree of graphitization, scaly carbon, and carbon nanotube. The thermal conductivity of the filler is a value measured by the laser flash method in principle. However, when the filler cannot be directly measured by the laser flash method, such as when the filler is a carbon-based material, it is indirectly measured by a method that can be measured. Measured and converted to the laser flash method. For example, in the case of 100% by volume filler based on a calibration curve showing the relationship between the filler filling amount and the thermal conductivity prepared by measuring the thermal conductivity by the optical alternating current method using a sample in which the filler is hardened with an epoxy thermosetting resin. The value obtained by calculating the thermal conductivity and converting it into the numerical value of the laser flash method can be used. Further, when measurement by such a method is not suitable, it was measured by wide-angle X-ray using a pseudo sample in which a filler (a filler having the same quality and a measurable form) was hardened with an epoxy thermosetting resin. From an X-ray parameter obtained from the graphite interlayer distance (d002) and the crystallite diameter (Lc) and a calibration curve obtained in advance from the thermal conductivity by the laser flash method, from the measurement sample d002 and Lc measured by wide-angle X-rays A value converted into the thermal conductivity of the laser flash method using the calibration curve can be used.

  In the present invention, (A) a polyphenylene sulfide, (B) a copolymer containing an aromatic vinyl monomer component and a vinyl cyanide monomer component, and (C) a weld characteristic by improving the affinity of the filler, epoxy In order to exhibit properties such as adhesiveness and thermal conductivity with high efficiency, it is preferable that the (C) filler used is surface-treated with an organic titanate coupling agent. Specific examples include, for example, isopropyl tris stearoyl titanate, isopropyl tris (dioctyl pyrophosphate) titanate, tetraisopropyl bis (dioctyl pyrophosphite) titanate, tetraoctyl bis (ditridecyl phosphite). ) Titanate, tetraisopropyl bis (ditridecyl phosphite) titanate, tetra (2,2-diallyloxymethyl-1-butyl) bis (ditridecyl) phosphite titanate, bis (dioctyl pyrophosphate) ) Oxyacetate titanate, bis (dioctyl pyrophosphate) ethylene titanate, isopropyl trioctanoyl titanate, isopropyl tridecylbenzenesulfonyl titanate, isopropyl tri (dioctyl phosphate) titanate G Sopropyl dimethacrylic isostearoyl titanate, isopropyl isostearoyl diacrylic titanate, isopropyl tricumyl phenyl titanate, dicumyl phenyl oxyacetate titanate, diisostearoyl ethylene titanate etc. It can be illustrated.

  The addition amount of the organic titanate coupling agent as a surface treatment agent to the filler (C) is preferably 0.1 to 3 parts by weight, and preferably 0.5 to 1 from the viewpoint of retention stability and handling property during molding. Part by weight is more preferred. As a surface treatment method, a surface treatment agent is diluted with an organic solvent in a fluid tank such as a Henschel mixer or added dropwise to a filler in a stock solution, or a surface treatment agent is diluted with an organic solvent or the like in a fluid tank or remains as a stock solution. The method of spraying the filler using a spray gun, or the filler is put into a dispersion liquid in which the surface treatment agent is preliminarily adjusted to the required concentration with water or an organic solvent, once in a slurry state, and then dried and recovered. In particular, from the viewpoint of productivity and homogeneity of the surface treatment, a method of spraying the surface treatment agent on the filler using a spray gun in a fluidized tank is preferable.

  In the present invention, the amount of (C) filler added is (A) polyphenylene sulfide and (B) aromatic vinyl-based monomer component from the viewpoint of the balance between the property development and melt processability of the present invention in the filler addition used. Is preferably 5 to 300 parts by weight, more preferably 7 to 250 parts by weight, more preferably 10 to 200 parts by weight based on 100 parts by weight of the total amount of the copolymer containing the vinyl cyanide monomer component. More preferably, it is part by weight.

  Furthermore, (D) any one or more additives of (D) fatty acid metal salt, ester compound, amide group-containing compound, epoxy compound, and phosphate ester, as exemplified below, within a range not impairing the characteristics of the present invention (C) It is preferable to add from the viewpoint of filler bondability and fluidity during processing. Specifically, (D) fatty acid metal salt, ester compound, amide group-containing compound, epoxy compound, phosphate ester When the amount of any one or more additives added is too much larger than the range of the present invention, it bleeds out to the surface of the obtained molded product, thereby causing peeling of the interface between the resin and the filler, resulting in a decrease in mechanical properties. Tend to.

  Specific examples of such (D) fatty acid metal salts, ester compounds, amide group-containing compounds, epoxy compounds, and phosphate esters include sodium stearate, calcium stearate, magnesium stearate. , Potassium stearate, lithium stearate, zinc stearate, barium stearate, aluminum stearate, sodium montanate, calcium montanate, magnesium montanate, potassium montanate, lithium montanate, zinc montanate, barium montanate, montan Fatty acid metal salts such as aluminum acid, and derivatives thereof, stearic acid ester such as methyl stearate and stearic acid stearate, myristic acid ester such as myristyl myristate, montanic acid Steryl, methacrylate esters such as behenyl methacrylate, pentaerythritol monostearate, cetyl 2-ethylhexanoate, methyl coconut fatty acid, methyl laurate, isopropyl myristate, octyldodecyl myristate, butyl stearate, 2-ethylhexyl stearate , Fatty acids such as isotridecyl stearate, methyl caprate, methyl myristate, methyl oleate, octyl oleate, lauryl oleate, oleyl oleate, 2-ethylhexyl oleate, decyl oleate, octidodecyl oleate, isobutyl oleate Monohydric alcohol esters and derivatives thereof, distearyl phthalate, distearyl trimellirate, dimethyl adipate, dioleyl adipate, adipate es , Polytriacids such as ditridecyl phthalate, diisobutyl adipate, diisodecyl adipate, dibutyl glycol adipate, 2-ethylhexyl phthalate, diisononyl phthalate, didecyl phthalate, tri-2-ethylhexyl trimellitic acid, triisodecyl trimellitic acid Fatty acid esters, stearic acid monoglyceride, palmitic acid / stearic acid monoglyceride, stearic acid mono / diglyceride, stearic acid / oleic acid / mono / diglyceride, fatty acid esters of glycerin such as behenic acid monoglyceride and their derivatives, sorbitan tristearate, Sorbitan monostearate, sorbitan monostearate, sorbitan distearate, sorbitan monopalmitate, sorbitan monostearate , Polyethylene glycol monostearate, polyethylene glycol distearate, polypropylene glycol monostearate, pentaerythritol monostearate, sorbitan monolaurate, sorbitan trioleate, sorbitan monooleate, sorbitan sesquioleate, sorbitan monolaurate, poly Oxymethylene sorbitan monolaurate, polyoxymethylene sorbitan monopalinate, polyoxymethylene sorbitan monostearate, polyoxymethylene sorbitan monooleate, polyoxymethylene sorbitan tetraoleate, polyethylene glycol, polyethylene glycol monolaurate, polyethylene glycol monooleate , Polyoxyethylene bisphenol A laurate, pe Fatty acid esters of polyhydric alcohols such as taerythritol and pentaerythritol monooleate, and derivatives thereof, ethylene bisstearylamide, ethylenebisoleylamide, stearyl erucamide, ethylenebisoctamide, ethylenebisdecanamide, and mixtures thereof Amide group-containing compounds, novolac phenyl type, bisphenol type monofunctional and polyfunctional epoxy compounds, aromatic phosphate esters such as triphenyl phosphate, and phosphate esters such as aromatic condensed phosphate esters.

  (D) As addition amount of one or more additives of fatty acid metal salt, ester compound, amide group-containing compound, epoxy compound, and phosphate ester, (A), (B) and (C) component A range of usually 0.1 to 10 parts by weight, preferably 0.3 to 8 parts by weight, and more preferably 0.5 to 6 parts by weight is selected for a total amount of 100 parts by weight.

  In the polyphenylene sulfide resin composition in the present invention, other components, such as antioxidants and heat stabilizers (hindered phenol-based, hydroquinone-based, phosphite-based, and substituted products thereof) are further included within the range not impairing the effects of the present invention. Etc.), weathering agents (resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.), release agents and lubricants, pigments (cadmium sulfide, phthalocyanine, coloring carbon black, etc.), dyes (nigrosine, etc.), Crystal nucleating agent (talc, silica, kaolin, clay, etc.), plasticizer (octyl p-oxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agent (alkyl sulfate type anionic antistatic agent, quaternary ammonium salt Type cationic antistatic agent, polyoxyethylene sorbita Nonionic antistatic agents such as monostearate, betaine-based amphoteric antistatic agent, etc.), can be added a flame retardant, other polymers.

  The polyphenylene sulfide resin composition of the present invention is usually produced by a known method. For example, it is prepared by premixing other necessary additives such as component (A), component (B), and component (C) with or without being supplied to an extruder, etc. Is done. In addition, when adding the filler (C), in order to suppress the breakage of the fiber of the fibrous filler, preferably, the component (A) and other necessary additives are introduced from the extruder, and (B) and (C) It adjusts by supplying a component to an extruder using a side feeder.

  When producing a resin composition, for example, melt-kneading at 180 to 350 ° C. using a single-screw extruder, twin-screw, three-screw extruder and kneader-type kneader equipped with a “unimelt” (R) type screw. To obtain a composition.

  In addition, when a large amount of (C) filler is added, for example, the filler is highly filled resin in which the amount of addition exceeds 300 parts by weight with respect to 100 parts by weight of the total amount of components (A) and (B). As a method for obtaining the composition, for example, as disclosed in JP-A-8-1663, the head portion of the extruder is removed and extruded, coarsely pulverized, uniformly blended, or the raw material is compression-molded into a tablet. Is mentioned. In particular, the method of tableting by compressing the raw material is preferable from the viewpoint of the quality stability of the obtained composition.

  The molding method of the polyphenylene sulfide resin composition of the present invention can be melt-molded by an ordinary molding method (injection molding, press molding, injection press molding, etc.), and in particular, injection molding from the viewpoint of mass productivity. Injection press molding is preferred.

  The polyphenylene sulfide resin composition of the present invention is useful for high heat dissipation applications, metal replacement applications, ceramic replacement applications, electromagnetic wave shielding applications, high precision parts (low dimensional change), high conductivity applications, and the like. 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 panel frames, power modules and their housings , Plastic magnets, semiconductors, LCD display parts, lamp covers for projectors, FDD carriages, FDD chassis, actuators, HDD parts such as chassis, electrical and electronic parts represented by computer-related parts; VTR parts, TV parts, Iron, hair Home, office work such as ryers, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser disc (registered trademark) / compact disc / digital video disc, lighting parts, refrigerator parts, air conditioner parts Representative products such as electrical product parts, office computer related parts, telephone related parts, facsimile related parts, printer head and copier related parts such as print heads and transfer rolls, cleaning jigs, motor parts, microscopes, binoculars, cameras, watches, etc. Optical equipment, precision machine parts: alternator terminal, alternator connector, IC regulator, light dimmer potentiometer base, motor core sealant, insulator member, power seat gear housing, air conditioner thermostat Shielding of chip antennas, electromagnetic waves, etc. in automotive / vehicle-related parts such as automobile bases, air conditioner panel switch boards, horn terminals, electrical component insulation plates, lamp housings, ignition device cases, personal computer housings, mobile phone housings A wide range of applications such as housing applications such as components such as installed antennas, etc., as well as partition plates that require high dimensional accuracy, electromagnetic shielding properties, and barrier properties such as gas and liquid, heat and electrical conductivity are required Useful for automotive equipment, electrical / electronic parts, thermal equipment parts, etc. Useful

  Hereinafter, although an example is given and the present invention is explained in detail, the gist of the present invention is not limited only to the following examples.

Reference Example 1 Polyphenylene sulfide PPS-1: Sodium sulfide nonahydrate 6.005 kg (25 mol), sodium acetate 0.11 kg (1.35 mol) and N-methyl-2-pyrrolidone (NMP) in an autoclave equipped with a stirrer 5 kg was charged, the temperature was gradually raised to 205 ° C. through nitrogen, and 3.6 liters of water was distilled. Next, after cooling the reaction vessel to 180 ° C., 3.756 kg (25.55 mol) of 1,4-dichlorobenzene and 3.7 kg of NMP were added, sealed under nitrogen, heated to 270 ° C., heated at 270 ° C. Reacted for 2.5 hours. After cooling, the reaction product was washed 5 times with warm water, then heated to 100 ° C., poured into 10 kg of NMP, stirred for about 1 hour, filtered, and washed several times with hot water. This was put into 25 liters of an acetic acid aqueous solution of pH 4 heated to 90 ° C., and stirred for about 1 hour, filtered, washed with ion-exchanged water of about 90 ° C. until the pH of the filtrate reached 7, Drying under reduced pressure at 80 ° C. for 24 hours gave dry PPS-1. When using a capillograph (manufactured by Toyo Seiki Co., Ltd.) with an orifice having a hole diameter of 1.0 mm × length of 10 mm and measuring at a resin temperature of 310 ° C. and a shear rate of 1000 / sec, PPS-1 The melt viscosity was 30 Pa · s.

  PPS-2: Sodium sulfide nonahydrate 6.005 kg (25 mol), sodium acetate 0.656 kg (8 mol) and N-methyl-2-pyrrolidone (NMP) 5 kg were charged into an autoclave equipped with a stirrer and gradually fed through nitrogen. The temperature was raised to 205 ° C. and 3.6 liters of water was distilled off. Next, after cooling the reaction vessel to 180 ° C, 3.727 kg (25.35 mol) of 1,4-dichlorobenzene and 3.7 kg of NMP were added, sealed under nitrogen, heated to 225 ° C and reacted for 5 hours. Thereafter, the temperature was raised to 270 ° C. and reacted for 3 hours. After cooling, the reaction product was washed 5 times with warm water. Next, the solution was put into 10 kg of NMP heated to 100 ° C., stirred for about 1 hour, filtered, and further washed several times with hot water. This was poured into 25 liters of an acetic acid aqueous solution of pH 4 heated to 90 ° C., and stirred for about 1 hour, filtered, washed with ion-exchanged water at about 90 ° C. until the pH of filtration became 7, It dried under reduced pressure at 80 degreeC for 24 hours, and obtained dry PPS-2. Using a capillograph (manufactured by Toyo Seiki Co., Ltd.) and an orifice having a hole diameter of 1.0 mm × length of 10 mm and measuring at a resin temperature of 310 ° C. and a shear rate of 1000 / sec, PPS-2 The melt viscosity was 200 Pa · s.

Reference Example 2 Copolymer Containing Aromatic Vinyl Monomer Component and Vinyl Cyanide Monomer Component B-1: A unit comprising 70 parts by weight of styrene and 30 parts by weight of acrylonitrile in a polymerization tank equipped with a stirrer The polymer was subjected to suspension polymerization in the temperature range of 65 ° C. to 85 ° C. for 5 hours, and the obtained bead-shaped resin was sufficiently dried, and then the intrinsic viscosity was measured. As a result, it was 0.50 dl / g.

  B-2: A bead resin obtained by suspension polymerization of a monomer comprising 80 parts by weight of styrene and 20 parts by weight of acrylonitrile in a polymerization tank equipped with a stirrer at a temperature range of 65 ° C. to 85 ° C. for 5 hours. After sufficiently drying, the intrinsic viscosity was measured and found to be 0.35 dl / g.

  The above intrinsic viscosity is obtained by completely dissolving 0.4 g of the suspension-polymerized bead-like resin in 100 ml of methyl ethyl ketone to make 5 points having different concentrations, and using an Ubbelohde viscosity tube, each concentration in a constant temperature bath at 30 ° C. It is the value calculated | required from the result of having measured the reduced viscosity.

Reference Example 3 Filler C-1: Carbon fiber (CF), MLD300 (fibrous filler, fiber diameter 7 μm, manufactured by Toray Industries, Inc.), average fiber length 150 μm, maximum fiber length 255 μm, thermal conductivity 3 W / mk
D50 and D90 (cumulative particle size distribution) of the above C-1 filler were obtained by collecting 100 mg of C-1 filler and dispersing it in 100 cc soapy water, and then observing the dispersion with a scanning electron microscope (made by HORIBA). D50 and D90 (cumulative particle size distribution) obtained by laser diffraction scattering method with average fiber length and maximum fiber length calculated by taking a photograph and measuring 1000 fiber lengths of the fibrous filler photographed in the photograph It is the value converted into.

  The thermal conductivity is a calibration that shows the relationship between the filling amount and the thermal conductivity of a filler prepared by measuring the thermal conductivity by the optical alternating current method using a sample obtained by solidifying the C-1 filler with an epoxy thermosetting resin. The thermal conductivity in the case of a filler capacity of 100% is calculated from the line, and is a value converted into a numerical value of the laser flash method.

C-2: Graphite (KS), KS5-25 (flaky filler, manufactured by Timcal Japan) D50: 15 μm, D90: 30 μm, thermal conductivity 200 W / mk
D50 and D90 (cumulative particle size distribution) of the above C-2 filler were prepared by adding about 0.05 g of C-2 filler in 50 cc of water and stirring them, and using a dropper, “My Pet” (manufactured by Kao) 2 After adding 3 drops of 100 cc of diluted surfactant solution (to the extent that bubbles do not form) and dispersing with ultrasonic cleaner, laser diffraction particle size distribution analyzer SALD-3100 (manufactured by Shimadzu Corporation) is used. It is the value measured using.

  The thermal conductivity is 100% by volume of filler based on a calibration curve that shows the relationship between the filler filling amount and the thermal conductivity by measuring the thermal conductivity by the optical alternating current method using a sample in which the filler is hardened with an epoxy-based thermosetting resin. In this case, the thermal conductivity is calculated and converted into the value of the laser flash method.

C-3: Graphite (CFW), CFW50A (flaky filler, manufactured by Chuetsu Graphite) D50: 50 μm, D90: 124 μm, thermal conductivity 200 W / mk
D50 and D90 (cumulative particle size distribution) of the above-mentioned C-3 filler were prepared by adding about 0.05 g of C-3 filler in 50 cc of water and stirring them, and using a dropper, “My Pet” (manufactured by Kao) 2 After adding 3 drops of 100 cc of diluted surfactant solution (to the extent that bubbles do not form) and dispersing with ultrasonic cleaner, laser diffraction particle size distribution analyzer SALD-3100 (manufactured by Shimadzu Corporation) is used. It is the value measured using.

  The thermal conductivity is 100% by volume of filler based on a calibration curve that shows the relationship between the filler filling amount and the thermal conductivity by measuring the thermal conductivity by the optical alternating current method using a sample in which the filler is hardened with an epoxy-based thermosetting resin. In this case, the thermal conductivity is calculated and converted into the value of the laser flash method.

C-4: Alumina, Al-33 (crushed alumina, manufactured by Sumitomo Chemical Co., Ltd.) D50: 12 μm, D90: 39 μm, thermal conductivity 26 W / mk
D50 and D90 (cumulative particle size distribution) of the above C-4 filler were prepared by adding about 0.05 g of C-4 filler into 50 cc of water and stirring them, and using a dropper, “My Pet” (manufactured by Kao) 2 After adding 3 drops of 100 cc of diluted surfactant solution (to the extent that bubbles do not form) and dispersing with ultrasonic cleaner, laser diffraction particle size distribution analyzer SALD-3100 (manufactured by Shimadzu Corporation) is used. It is the value measured using.

  The thermal conductivity is 100% by volume of filler based on a calibration curve that shows the relationship between the filler filling amount and the thermal conductivity by measuring the thermal conductivity by the optical alternating current method using a sample in which the filler is hardened with an epoxy-based thermosetting resin. In this case, the thermal conductivity is calculated and converted into the value of the laser flash method.

  C-5: A filler of 3000 g of C-4 was put into a 20 L Henschel mixer (Mitsui Mining Co., Ltd.) and stirred, and 50% KR138S (bis (dioctylpyrophosphate) oxyacetate titanate diluted with isopropyl alcohol, Ajinomoto After spraying 60 g of the solution (manufactured by Fine Techno Co., Ltd.) with a spray gun, heat treatment was performed for 3 hours with a hot air dryer at 120 ° C.

Reference Example 4 Additive (uses 42 mesh pass through sieve)
D-1: “PX-200” (powdered aromatic condensed phosphate ester, CAS No. 139189-30-3, manufactured by Daihachi Chemical Industry Co., Ltd.).

Examples 1-12, Comparative Examples 1-7
The polyphenylene sulfide of Reference Example 1, the copolymer of aromatic vinyl monomer / vinyl cyanide monomer of Reference Example 2, the filler of Reference Example 3 and the additive shown in Reference Example 4 in a ribbon blender are shown in Table 1 and The mixture was blended in the amounts shown in 2, and melt-kneaded at the resin temperatures shown in Tables 1 and 2 using a PCM30 with a 3-hole strand die head (2-screw extruder; manufactured by Ikegai Iron Works Co., Ltd.) to obtain pellets. Subsequently, after drying with a 130 degreeC hot-air dryer for 4 hours, the evaluation mentioned later was performed.

(1) Weld characteristics Using an injection molding machine UH1000 (80t) (manufactured by Nissei Plastic Industrial Co., Ltd.), gates are provided at both ends in the longitudinal direction of the test piece under the resin temperature and mold temperature conditions shown in Table 1, respectively. An ASTM No. 1 test piece (thickness 3.2 mm) is obtained in which a weld is obtained near the center of the test piece by flowing resin from the test piece, and the obtained test piece is used with a thermal shock absorber (TSA-70L manufactured by ESPEC). A cold cycle test was conducted. Then, tensile strength was measured based on ASTM D638 using Autograph AG-2000C (manufactured by Shimadzu Corporation). And the weld strength retention was calculated by the following formula. It can be said that the larger this value, the better the weld strength.
Weld strength retention rate (%) = weld strength after cooling test / weld strength before cooling test × 100

  The conditions of the cold test were 500 cycles, where normal temperature (23 ° C.) → temperature drop at 5 minutes → hold at −10 ° C. for 30 minutes → temperature rise at 5 minutes → hold at 30 ° C. for 30 minutes for one cycle.

(2) Epoxy Adhesion Using an injection molding machine UH1000 (80t) (manufactured by Nissei Plastic Industry Co., Ltd.), an ASTM No. 1 tensile test piece (thickness 3.2 mm) is molded under the resin temperature and mold temperature conditions shown in Table 1. did. Thereafter, it is divided into two equal parts and fixed with a spacer (thickness 1 mm) and an epoxy resin (manufactured by Nagase Ciba Co., Ltd., one-pack type epoxy resin, XNR3506) so that the adhesion area is 50 mm ^2. It was cured under the conditions of 30 ° C. for 30 minutes. Using Autograph AG-2000C (manufactured by Shimadzu Corporation), the tensile strength of this sample was measured under the conditions of a strain rate of 1 mm / min and a fulcrum distance of 80 mm, and the value obtained by dividing the maximum value of the strength by the adhesion area. The epoxy adhesive strength was used. It can be said that the larger this value, the better the epoxy adhesiveness.

(3) Thermal conductivity Using an injection molding machine UH1000 (80t) (manufactured by Nissei Plastic Industry Co., Ltd.), a square-shaped product (50 mm long x 50 mm wide x 3 mm thick) under the resin temperature and mold temperature conditions shown in Table 1 Film gate), and both surfaces of the molded product were cut to a depth of 0.5 mm to obtain a test piece having a thickness of 2 mm. Laser flash method constant measuring apparatus LF / TCM-FA8510B (manufactured by Rigaku Corporation) Was used to measure the thermal conductivity. It can be said that the larger this value, the better the thermal conductivity.

(4) Stability during molding (MFR change rate)
With a measurement temperature of 315.5 ° C. and a load of 5000 g, a MFR (MF5) having a residence time of 5 minutes and an MFR (MF30) having a residence time of 30 minutes were obtained from a melt indexer (in accordance with ASTM D1238-86). The MFR change rate (%) was calculated by the following equation. It can be said that the smaller the rate of change, the better the retention stability during molding.
MFR change rate (%) = (MF30−MF5) / MF5 × 100

(5) Chemical resistance Using an injection molding machine UH1000 (80t) (manufactured by Nissei Plastic Industry Co., Ltd.), an ASTM No. 1 tensile test piece (thickness: 3.2 mm) was molded under the resin temperature and mold temperature conditions shown in Table 1. Then, after being immersed in 50% antifreeze solution at 100 ° C. for 1000 hours, the change in weight was measured, and the weight increase rate was calculated by the following formula as a chemical resistance index. In addition, it can be said that it is excellent in chemical resistance, so that this value is small.
Weight change rate (%) = (weight after 50% antifreeze immersion−weight before 50% antifreeze immersion) / weight before 50% antifreeze immersion × 100

  As is apparent from the results in Table 1, the molded product obtained from the resin composition of the present invention is excellent in retention stability and chemical resistance at the time of molding, and weld characteristics and epoxy adhesive properties that have not been obtained in the past. It can be seen that the thermal conductivity can be balanced at a high level. Moreover, since the stability at the time of melting is good, the yield during production is improved, and the productivity can be greatly improved.

Claims (7)

(A) Aromatic polyphenylene sulfide of 50 to 99% by weight and (B) Aromatic vinyl monomer component and vinyl cyanide monomer component having a copolymer composition ratio of 77/23 to 90/10% by weight A polyphenylene sulfide resin composition comprising 50 to 1% by weight of a copolymer containing a vinyl monomer component and a vinyl cyanide monomer component. The polyphenylene sulfide resin composition according to claim 1, wherein 5 to 300 parts by weight of (C) filler is blended with 100 parts by weight of the total of (A) and (B). (A) The polyphenylene sulfide resin composition according to claim 1 or 2, wherein the polyphenylene sulfide resin has a melt viscosity of not less than 100 Pa · s at a resin temperature of 310 ° C and a shear rate of 1000 / sec. (C) The polyphenylene sulfide resin composition according to claim 2, wherein D50 (cumulative particle size distribution) obtained by a laser diffraction scattering method of the filler is in the range of 5 to 60 μm. (C) The polyphenylene sulfide resin composition according to any one of claims 2 to 4, wherein D90 (cumulative particle size distribution) obtained by a laser diffraction scattering method of the filler is 10 to 150 µm. (C) The polyphenylene sulfide resin composition according to any one of claims 2 to 5, wherein the filler contains a thermally conductive filler having a thermal conductivity of 20 W / mk or more measured by a laser flash method. The polyphenylene sulfide resin composition according to any one of claims 2 to 6, wherein (C) the filler is surface-treated with an organic titanate coupling agent.