JP2010053350A - Polyarylene sulfide resin composition, tablet of polyarylene sulfide resin composition and molded article of the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyarylene sulfide resin composition excellent in flowability, heat conductivity while retaining excellent stiffness, dimensional stability, and having all of low anisotropy of the linear expansion coefficient and heat cycle resistance and tap-strength durability. <P>SOLUTION: The polyarylene sulfide resin composition comprises (A) 20-40 wt.% of the polyarylene sulfide resin and (B) 60-80 wt.% of inorganic fillers to 100 wt.% of the total amount of the components (A) and (B), wherein the total amount of (B1) a platy filler and (B2) a granular filler in the (B) inorganic filler is ≥70 wt.%, and the compounding ratio (weight ratio) of the (B1) platy filler to (B2) the granular filler, (B1)/(B2) is 0.7/1 to 8/1, and has a thermal conductivity of ≥0.5 W/m×K. <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a polyarylene sulfide resin from which a molded article having an excellent linear expansion coefficient low anisotropy, heat cycle resistance and tap strength durability can be obtained, and more specifically, thermal conductivity, rigidity, The present invention relates to a polyarylene sulfide resin composition and / or a polyarylene sulfide resin composition tablet excellent in dimensional stability and excellent property balance such as excellent fluidity, and a molded article comprising the same.

  Polyarylene sulfide resin (hereinafter abbreviated as PPS resin) has suitable properties for engineer plastics such as excellent heat resistance, rigidity, dimensional stability, and flame retardancy. It is widely used in various electrical / electronic parts, machine parts and automobile parts. In recent years, PPS resin has been widely used as a material that replaces metals and ceramics from the viewpoints of its excellent properties, from the viewpoint of reducing the weight of various members and reducing manufacturing costs by simplifying the process. Furthermore, it is desired that a member using PPS resin is applied to a very thin portion or a member having a complicated shape. In addition, there are those that repeatedly heat and cool the electrical and electronic parts in the surrounding environment and nearby parts of the applied members, and there is also a sudden increase due to an increase in the amount of heat generated by improving the output of various electrical and electronic parts. A PPS resin excellent in heat dissipation capable of withstanding temperature rise / fall and excellent heat cycle resistance is desired. In addition, as a material that replaces metal or ceramics, a joint is fixed with a screw in order to combine a molded product with a molded product, or a molded product with a different material such as metal or ceramic. At that time, there is a demand for a PPS with excellent durability that can be repeatedly screwed in the assembly process.

  However, PPS resin is inferior in toughness compared to other engineer plastics. Furthermore, the thermal conductivity is low. Further, in applications where metal is inserted, there is a problem that it is brittle with respect to a thermal cycle by repeated low and high temperatures or thermal shock, is inferior in thermal properties, and is inferior in durability for screwing screws repeatedly.

  Under such circumstances, some studies have been made so far for the purpose of improving heat cycle resistance, dimensionality, and thermal conductivity of PPS resins.

  For example, Patent Document 1 proposes a thermally conductive resin composition characterized by blending alumina and a plate-like filler into a PPS resin, and discloses that thermal conductivity and dimensionality are improved. In such a composition, the amount of the plate-like filler is small, and the coefficient of linear expansion and rigidity are insufficient, so that the heat cycle resistance may be insufficient.

  Further, in Patent Document 2, glass fiber, olefin resin, epoxy resin, glass flake and / or calcium carbonate is blended with PPS resin, and PPS resin composition having excellent heat resistance, low warpage, and epoxy resin adhesion. Is disclosed. However, the blending ratio of the plate-like filler and the granular filler contained in the inorganic filler is low, and there is a possibility that the linear expansion anisotropy is large, and the heat cycle resistance with a wide temperature range from low temperature to high temperature has characteristics. It may be insufficient.

  Patent Document 3 discloses a PPS resin composition that is excellent in low gas properties, cooling properties, and low warpage by blending glass flakes, inorganic fillers other than glass flakes, and olefin resins into PPS resins. However, the mixing ratio of the plate-like filler and the granular filler contained in the inorganic filler is low, and the linear expansion anisotropy may be large. It may be insufficient.

  Patent Document 4 discloses a sealing PPS resin composition comprising silica and / or hydrophobized magnesium oxide and elastomer blended in a PPS resin. However, since the plate-like filler is not blended with the inorganic filler, the heat cycle resistance having a large temperature range from low temperature to high temperature may have insufficient characteristics. Moreover, since the rigidity is low, the shape of the molded product may be limited.

  Patent Document 5 discloses a PPS resin composition for encapsulating electronic components, characterized by blending silica, elastomer, and epoxysilane into a PPS resin. However, since the plate-like filler is not blended with the inorganic filler, the heat cycle resistance having a large temperature range from low temperature to high temperature may have insufficient characteristics. Moreover, since the rigidity is low, the shape of the molded product may be limited.

  Patent Document 6 discloses a PPS resin composition that is excellent in fluidity, low warpage, low anisotropy of linear expansion coefficient, and heat cycle resistance by blending copolymer polyolefin, glass fiber, and mica with PPS resin. Has been. However, the mixing ratio of the plate-like filler and the granular filler contained in the inorganic filler is low, and the linear expansion anisotropy may be large. It may be insufficient.

JP 2002-256147 A (page 9, example) Japanese Patent Laying-Open No. 2005-306926 (Page 15, Example) JP 2002-129014 A (Page 9, Example) Japanese Patent Laid-Open No. 2002-53752 (Page 7, Example) JP 2000-186209 A (Page 7, Example) Japanese Patent Laying-Open No. 2008-75049 (Page 17, Example)

  The present invention maintains the excellent rigidity and dimensional stability of the above-mentioned conventional polyarylene sulfide resin, and is excellent in fluidity and thermal conductivity, and particularly excellent in low anisotropy of linear expansion coefficient and heat cycle resistance. It is an object of the present invention to provide a PPS resin composition in which both tap strength and durability are compatible, and a molded product comprising the same.

  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) Polyarylene sulfide obtained by blending (A) 20 to 40% by weight of polyarylene sulfide resin and (B) 60 to 80% by weight of inorganic filler, with the total of (A) and (B) being 100% by weight It is a resin composition, and the total amount of (B1) plate-like filler and (B2) granular filler in the (B) inorganic filler is more than 70% by weight, and (B1) plate-like filling The blending ratio (weight ratio) of the material and (B2) granular filler is (B1) / (B2) = 0.7 / 1 to 8/1, and was measured by the laser flash method of the polyarylene sulfide resin composition. A polyarylene sulfide resin composition having a thermal conductivity of 0.5 W / m · K or more,
(2) (B1) The polyarylene sulfide resin composition according to (1), wherein the plate-like filler has a Mohs hardness of 2 or more,
(3) (B1) The polyarylene sulfide resin composition according to (1) or (2), wherein the plate-like filler is glass flakes,
(4) The polyarylene sulfide resin composition according to (3), wherein the glass flakes have an average thickness of 0.1 to 10 μm and an average particle diameter (D50) of 50 to 700 μm.
(5) (B2) The polyarylene sulfide resin composition according to any one of (1) to (4), wherein the particulate filler is a thermally conductive filler having a thermal conductivity of 10 W / m · K or more,
(6) (B2) The polyarylene sulfide resin composition according to any one of (1) to (5), wherein the particulate filler is alumina.
(7) The polyarylene sulfide resin composition according to any one of (1) to (6), wherein (A) 2 to 40 parts by weight of the olefin-based resin is blended with 100 parts by weight of the total polyarylene sulfide resin. ,
(8) A polyarylene sulfide resin composition tablet obtained by tableting the powder of the polyarylene sulfide resin composition according to any one of (1) to (7) in a solid phase,
(9) A molded article obtained by injection-molding the polyarylene sulfide resin composition according to any one of (1) to (7) or the polyarylene sulfide resin composition tablet according to (8),
It is.

  The present invention maintains the excellent rigidity and dimensional stability of the above-described conventional PPS resin, is excellent in thermal conductivity and fluidity, and has particularly excellent low anisotropy of linear expansion coefficient, heat cycle resistance and tap. Because it has the characteristics of both strength and durability, it is particularly useful for electrical parts such as electrical / electronic parts or automotive electrical parts. Especially, it requires a low temperature and high temperature cycle and is required for assembly. It can be very practically used for a molded product having a screw insertion portion. In addition, the present invention can be applied to various other fields.

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

  Typical examples of the (A) PPS resin used in the present invention include polyarylene sulfide, polyarylene sulfide sulfone, polyarylene sulfide ketone, random copolymers thereof, block copolymers, and mixtures thereof. Polyarylene sulfide is particularly preferably used. Such polyarylene sulfide is a polymer preferably containing 70 mol% or more, more preferably 90 mol% or more of a repeating unit represented by the following structural formula. When the repeating unit is 70 mol% or more, Is preferable in that it is excellent.

  In addition, such polyarylene sulfide resin 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. It may be a mixture thereof.

  Such polyarylene sulfide resins are generally known in the art, 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. It can be produced by a method for obtaining a polymer having a relatively large molecular weight described in the publication.

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

  Specific methods for crosslinking / high molecular weight polyarylene sulfide resin by heating include an atmosphere of an oxidizing gas such as air or oxygen, or a mixed gas atmosphere of the oxidizing gas and an inert gas such as nitrogen or argon. Below, 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 drier or a heating apparatus with a rotary or stirring blade. However, in the case of efficient and more uniform treatment, heating with a rotary or stirring blade is possible. More preferably, an apparatus is used.

The polyarylene sulfide resin as a specific method when the heat treatment at or reduced pressure under an inert gas atmosphere such as nitrogen, inert gas atmosphere or reduced pressure such as nitrogen (preferably 7,000Nm ^-2 or less) below, Examples of the heat treatment method include a heat treatment 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 drier or a heating apparatus with a rotary or stirring blade. However, in the case of efficient and more uniform treatment, heating with a rotary or stirring blade is possible. More preferably, an apparatus is used.

  When the polyarylene sulfide resin 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 the polyarylene sulfide resin. 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 a polyarylene sulfide resin 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 polyarylene sulfide resin 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 polyarylene sulfide resin 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 the polyarylene sulfide resin is treated with hot water. That is, the water used is preferably distilled water or deionized water in order to exhibit a preferable chemical modification effect of the polyarylene sulfide resin by hot water washing. The operation of the hot water treatment is usually performed by adding a predetermined amount of polyarylene sulfide resin to a predetermined amount of water, and heating and stirring at normal pressure or in a pressure vessel. The ratio of the polyarylene sulfide resin and water is preferably as much as possible, and is preferably used at a bath ratio of 200 g or less of polyarylene sulfide resin with respect to 1 liter of water.

  The following method can be illustrated as a specific method in the case of acid-treating a polyarylene sulfide resin. That is, there is a method of immersing a polyarylene sulfide resin in an acid or an aqueous solution of an acid, and stirring or heating can be appropriately performed as necessary. The acid used is not particularly limited as long as it does not have the action of decomposing the polyarylene sulfide resin, such as aliphatic saturated monocarboxylic acids such as formic acid, acetic acid, propionic acid and butyric acid, chloroacetic acid and dichloroacetic acid. Halo-substituted aliphatic saturated carboxylic acids, aliphatic unsaturated monocarboxylic acids such as acrylic acid and crotonic acid, aromatic carboxylic acids such as benzoic acid and salicylic acid, oxalic acid, malonic acid, succinic acid, phthalic acid, fumaric acid, etc. Dicarboxylic acid and inorganic acidic compounds such as sulfuric acid, phosphoric acid, hydrochloric acid, carbonic acid and silicic acid are used. Of these acids, acetic acid and hydrochloric acid are particularly preferably used. The polyarylene sulfide resin 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 the effect of the preferred chemical modification of the polyarylene sulfide resin by acid treatment is not impaired.

  The polyarylene sulfide resin used in the present invention has a melt viscosity of 300 ° C. and a shear rate of 1000/1000 in order to reduce distortion of a molded product at the time of molding and to eliminate composition unevenness (characteristic variation) in the obtained resin composition. It is preferably 80 Pa · s or less, more preferably 50 Pa · s or less, and further preferably 30 Pa · s or less under the condition of seconds. Although there is no restriction | limiting in particular about the minimum of melt viscosity, It is preferable that it is 5 Pa.s or more. Two or more polyarylene sulfide resins having different melt viscosities may be used in combination.

  The melt viscosity of the polyarylene sulfide resin can be measured using a capilograph (manufactured by Toyo Seiki Co., Ltd.) apparatus under conditions of a die length of 10 mm and a die hole diameter of 0.5 to 1.0 mm.

  Examples of the (B) inorganic filler used in the present invention include (B1) plate-like filler and (B2) granular filler or (B3) fibrous filler.

  (B1) The plate-like filler may be any material as long as the shape thereof has a plate shape, and specific examples thereof include glass flakes, mica, talc, alumina flakes, kaolin, and carbon. Examples include flakes, metal flakes, scaly carbon, graphite, and clay. Specific examples of metal flakes include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium and tin. Two or more of these fillers can be used in combination. Among these, glass flakes and mica are particularly preferably used in terms of dimensional stability and mechanical properties, and among these, glass flakes are particularly preferable.

  In the present invention, the gas flakes preferably have an average glass flake thickness of 0.1 to 10.0 μm, more preferably 0.2 to 7.0 μm, in order to achieve a high balance between rigidity and dimensional stability. 0.5 to 3.0 μm is more preferable.

  In addition, the thickness of the said glass flakes ashed the composition, and made the average thickness the average of the thickness of 50 glass flake particles measured by scanning electron microscope observation.

  Further, in the present invention, the glass flake is a cumulative particle size distribution measured by a laser diffraction method in view of the balance between the thin-wall flowability at the time of melt molding of the polyarylene sulfide resin composition and the strength and dimensional stability of the molded product. The 50% cumulative particle size (D50) obtained from the curve is the average particle size (D50), and the average particle size (D50) of the glass flakes is preferably 50 to 700 μm, more preferably 100 to 600 μm, and more preferably 150 to 500 μm. Is more preferable.

  What can be used for the plate-like filler is surface treatment with a surface treatment agent such as thermoplastic resin such as ethylene / vinyl acetate copolymer, thermosetting resin such as epoxy resin, silane compound titanate compound, aluminum compound and the like. It may be given.

  (B2) The particulate filler may be any material as long as the shape thereof is granular. Specific examples include silica, calcium carbonate, glass beads, glass microballoons, molybdenum disulfide, Examples include wollastonite, calcium polyphosphate, metal powder, metal oxide (alumina, magnesium oxide, zinc oxide, titanium oxide, boehmite, etc.), carbon powder, graphite, and the like. Specific examples of the metal species of the metal powder include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium and tin.

  Also possible for particulate fillers are surface treatments with surface treatment agents such as thermoplastic resins such as ethylene / vinyl acetate copolymers, thermosetting resins such as epoxy resins, silane compounds, titanate compounds, and aluminum compounds. May be given.

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

The carbon powder is classified into acetylene black, gas black, oil black, naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, disc black, and the like based on the raw materials and the production method. The carbon powder that can be used in the present invention is not particularly limited in terms of its raw material and production method, and among them, acetylene black and furnace black are particularly preferably used. Further, as the carbon powder, various carbon powders having different characteristics such as particle diameter, surface area, DBP (dibutyl phthalate) oil absorption and ash content are manufactured and commercially available. The carbon powder that can be used in the present invention is not particularly limited with respect to these properties, but from the viewpoint of the balance between strength and electrical conductivity, the average primary particle size is 500 nm or less, particularly 5 to 100 nm, It is preferable that it exists in the range of 10-70 nm. The surface area (BET method) is preferably in the range of 10 m ² / g or more, more preferably 30 m ² / g or more. Furthermore, the DBP oil supply amount is preferably 50 ml / 100 g or more, particularly preferably 100 ml / 100 g or more. Furthermore, it is preferable that the ash content is 0.5% or less, particularly 0.3% or less.

  Such carbon powder may be surface-treated with a surface treatment agent such as titanate, aluminum, and silane. Moreover, it is also possible to use what was granulated in order to improve melt-kneading workability | operativity with resin.

  (B3) Specifically, the fibrous filler is, for example, glass fiber, PAN-based or pitch-based carbon fiber, stainless steel fiber, metal fiber such as aluminum fiber or brass fiber, 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, barium strontium titanate whisker, aluminum borate whisker, silicon nitride whisker, zinc oxide whisker, etc. The type of glass fiber or carbon fiber is not particularly limited as long as it is generally used for resin reinforcement, and can be selected from, for example, long fiber type, short fiber type chopped strand, milled fiber, and the like. The filler may be coated or focused with a thermoplastic resin such as an ethylene / vinyl acetate copolymer, a thermosetting resin such as an epoxy resin, a silane compound, a titanate compound, or an aluminum compound.

  In the present invention, the ratio of the (A) polyarylene sulfide resin and the (B) inorganic filler is blended from the viewpoint of exhibiting the characteristics of the inorganic filler used and the balance with melt processability. The total amount of the arylene sulfide resin and (B) inorganic filler is 100% by weight, and (A) the polyarylene sulfide resin is 20 to 40% by weight, and (B) the inorganic filler is 60 to 80% by weight, preferably (A ) 22-38 wt% polyarylene sulfide resin, (B) 62-78 wt% inorganic filler, more preferably, (A) 25-35 wt% polyarylene sulfide resin, (B) 65-75 wt% inorganic filler. % Is preferred.

  Furthermore, in the present invention, the orientation of the inorganic filler is relaxed, and the filling property of the plate-like filler and the granular filler is maximized, so that the flow direction of the molded product of the polyarylene sulfide resin composition is perpendicular to the flow direction. Melt processability to reduce anisotropy in linear expansion, especially to suppress cracking due to distortion of the molded product due to temperature changes, and durability of tap strength when a screw is repeatedly inserted into the screw hole of the molded product In view of the balance of (B), the blended (B) inorganic filler includes (B1) plate-like filler and (B2) granular filler, and the total of (B1) component, (B2) component and (B3) component The component (B1) and the component (B2) are more than 70% by weight, preferably 80% by weight or more, more preferably 90% by weight, and (B) the (B1) plate-like filler of the inorganic filler and (B2) grain The blending ratio of the filler is (B1) / (B2) = 0.7 / 1 to 8/1, preferably (B1) / (B2) = 0.8 / 1 to 7/1, more preferably (B1) / (B2) = 1/1 to 6/1 is preferable. When the total of (B1) plate-like filler and (B2) granular filler is 70% by weight or less, the anisotropy in the linear expansion of the molded product increases, and the heat cycle resistance tends to decrease. Moreover, when the ratio of (B1) plate-like filler is too small in the ratio of (B1) plate-like filler and (B2) granular filler, there is a tendency that the mechanical property reinforcement effect is lowered and the tap strength durability is lowered. If the ratio of the plate-like filler is too large, the melt processability tends to decrease.

  Further, from the viewpoint of the effect of reinforcing the rigidity and mechanical properties of the polyarylene sulfide resin composition, it is preferable that the (B1) plate-like filler has a Mohs hardness of 2 or more, and a Mohs hardness of 3 or more. Preferably, the Mohs hardness is 4 or more. When the Mohs hardness is lower than the above range, the reinforcing effect of rigidity and mechanical properties tends to be lowered. The Mohs hardness referred to here is the old Mohs hardness.

  In addition, the thermal conductivity difference between materials in the ambient temperature change with a material with high thermal conductivity, such as a metal material that comes into contact with the molded article of the polyarylene sulfide resin composition, is alleviated, and cracks due to distortion of the molded article due to temperature change are maximized. In order to suppress to the limit, (B2) the granular filler is preferably a thermally conductive filler having a thermal conductivity of 10 W / m · K or more, more preferably a thermal conductivity of 15 W / m · K or more, and thermal conductivity. 20 W / m · K or more is more preferable. When the thermal conductivity is less than 10 W / m · K, the effect of suppressing cracking due to temperature change in the molded article of the polyarylene sulfide resin composition tends to be low.

  Examples of the thermally conductive filler having a thermal conductivity of 10 W / m · K or more used in the present invention include metal powder, metal oxides such as beryllia, alumina, zinc oxide, and magnesium oxide, and nitride such as aluminum nitride and silicon nitride. Products, inorganic fillers coated with a heat conductive material, carbon powder, and the like.

  Here, specific examples of the metal species of the metal powder include silver, nickel, copper, zinc, aluminum, magnesium, stainless steel, iron, brass, chromium and tin.

  Any of these metal powders may be surface-treated with a surface treatment agent such as titanate, aluminate and silane.

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

Specific examples of the heat conductive material in the inorganic filler coated with the heat conductive material include aluminum, nickel, silver, carbon, SnO ₂ (antimony doped) and In ₂ O ₃ (antimony doped). be able to. Examples of the inorganic filler to be coated include glass beads, barium sulfate, zinc oxide, and titanium oxide. Examples of the coating method include a vacuum deposition method, a sputtering method, an electroless plating method, and a baking method. The inorganic filler coated with these thermally conductive materials may also be subjected to surface treatment with a surface treatment agent such as titanate, aluminate and silane.

The carbon powder is classified into acetylene black, gas black, oil black, naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, disc black, and the like based on the raw materials and the production method. The carbon powder that can be used in the present invention is not particularly limited in terms of its raw material and production method, and among them, acetylene black and furnace black are particularly preferably used. Further, as the carbon powder, various carbon powders having different characteristics such as particle diameter, surface area, DBP oil absorption amount and ash content are produced. The carbon powder that can be used in the present invention is not particularly limited in terms of these characteristics, but from the viewpoint of the balance between strength and thermal conductivity, the average particle size is 500 nm or less, particularly 5 to 100 nm, more preferably 10 to 70 nm. It is preferable to be in the range. The surface area (BET method) is preferably in the range of 10 m ² / g or more, more preferably 30 m ² / g or more. Furthermore, the DBP oil supply amount is preferably 50 ml / 100 g or more, particularly preferably 100 ml / 100 g or more. Furthermore, it is preferable that the ash content is 0.5% or less, particularly 0.3% or less.

  Such carbon powder may be surface-treated with a surface treatment agent such as titanate, aluminate, and silane. Moreover, it is also possible to use what was granulated in order to improve melt-kneading workability | operativity with resin.

  In the present invention, two or more kinds of the above heat conductive fillers can be used in combination.

  Among these, magnesium oxide, alumina, zinc oxide, aluminum nitride, silicon nitride, carbon powder and the like are preferable in that the molded product can be reduced in weight. Among these, it is particularly preferable to use alumina in order to further improve the tap strength durability.

  The thermal conductivity of the filler is a value measured by the laser flash method in principle. However, when the filler cannot be measured directly by the laser flash method, such as when the filler is a particulate 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.

  The polyarylene sulfide resin composition of the present invention can have a thermal conductivity of 0.5 W / m · K or more measured by a laser flash method by blending an inorganic filler as described above. Here, the thermal conductivity was obtained by creating a square-shaped product (50 mm × 50 mm × 3 mm thickness, film gate) made of a polyarylene sulfide resin composition, and cutting both surfaces of this molded product to a depth of 0.5 mm. This is a value measured with a laser flash method constant measuring device (LF / TCM-FA8510B manufactured by Rigaku Corporation) using a test piece of length × width (20 mm × 20 mm) which was further cut to a length of 2 mm.

  The thermal conductivity of the polyarylene sulfide resin composition of the present invention reduces the difference in thermal conductivity between materials in the ambient temperature change with a material having a high thermal conductivity such as a metal material in contact with the molded article, and molding due to temperature change. In order to suppress cracking due to product distortion to the maximum, the thermal conductivity is preferably 0.5 W / m · K or more, more preferably 0.7 W / m · K or more, and the thermal conductivity is 1.0 W. / M · K or more is more preferable. When the thermal conductivity is less than 0.5 W / m · K, the heat dissipation effect due to temperature change is low, and the crack suppression effect in the molded product of the polyarylene sulfide resin composition tends to be low. Further, in the present invention, from the viewpoint of further improving heat cycle resistance by imparting toughness of the polyarylene sulfide resin, 2 to 40 parts by weight of the (C) olefin-based resin with respect to a total of 100 parts by weight of the polyarylene sulfide resin. It is preferable to mix.

  The (C) olefin resin of the present invention is a polymer obtained by (co) polymerizing olefins, specifically, olefin (co) polymers, and epoxy groups, acid anhydride groups, ionomers and the like. Examples thereof include an olefinic (co) polymer (modified olefinic (co) polymer) obtained by introducing a monomer component having a functional group (hereinafter abbreviated as a functional group-containing component).

  In the present invention, the olefinic resins may be used alone or in combination of two or more.

  Examples of the olefin polymer include ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, α-olefin such as isobutylene, or a polymer obtained by polymerizing two or more kinds, α-olefin, Examples include acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate and other α, β-unsaturated acids and their copolymers with alkyl esters. .

  Preferred specific examples of the olefin polymer include polyethylene, polypropylene, ethylene / propylene copolymer, ethylene / butene-1 copolymer, ethylene / ethyl acrylate copolymer, ethylene / butyl acrylate copolymer, Examples thereof include ethylene / methyl methacrylate copolymer and ethylene / butyl methacrylate copolymer.

  Examples of functional group-containing components for introducing a monomer component having a functional group such as an epoxy group, an acid anhydride group, or an ionomer into the modified olefinic (co) polymer include maleic anhydride, itaconic anhydride, Citraconic anhydride, endobicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic acid, endobicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic acid anhydride, etc. Monomers containing an acid anhydride group, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl itaconate, ionomers such as carboxylic acid metal complexes The monomer to contain is mentioned.

  The method for introducing these functional group-containing components is not particularly limited, and a method such as copolymerization or graft introduction to an olefin polymer using a radical initiator can be used. The amount of the functional group-containing component introduced is suitably in the range of 0.001 to 40 mol%, preferably 0.01 to 35 mol%, based on the whole modified olefin polymer.

  Specific examples of the olefin (co) polymer obtained by introducing a monomer component having a functional group such as an epoxy group, an acid anhydride group, or an ionomer into an olefin polymer particularly useful in the present invention include ethylene / propylene- g-glycidyl methacrylate copolymer (“g” represents graft, the same applies hereinafter), ethylene / butene-1-g-glycidyl methacrylate copolymer, ethylene / glycidyl acrylate copolymer, ethylene / glycidyl methacrylate Copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / glycidyl methacrylate copolymer, ethylene / propylene-g-maleic anhydride copolymer, ethylene / butene-1-g -Maleic anhydride copolymer, ethylene / methyl acrylate-g-maleic anhydride copolymer , Ethylene / ethyl acrylate-g-maleic anhydride copolymer, ethylene / methyl methacrylate-g-maleic anhydride copolymer, ethylene / ethyl methacrylate-g-maleic anhydride copolymer, ethylene / methacrylic acid Examples thereof include a zinc complex of a copolymer, a magnesium complex of an ethylene / methacrylic acid copolymer, and a sodium complex of an ethylene / methacrylic acid copolymer.

  Preferred are ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / glycidyl methacrylate copolymer, ethylene / butene-1-g-maleic anhydride. Examples thereof include an acid copolymer and an ethylene / ethyl acrylate-g-maleic anhydride copolymer.

  Particularly preferred are ethylene / glycidyl methacrylate copolymers, ethylene / methyl acrylate / glycidyl methacrylate copolymers, ethylene / methyl methacrylate / glycidyl methacrylate copolymers, and the like.

  The blending amount of the (C) olefin resin is 2 to 40 parts by weight, preferably 3 to 30 parts by weight, more preferably 4 to 20 parts by weight with respect to 100 parts by weight of the total of (A) polyarylene sulfide resin. is there. If the olefin-based resin is less than 2 parts by weight, it is difficult to obtain the effect of improving the flexibility and impact resistance, and the heat cycle resistance tends to be insufficient, and conversely if it is more than 40 parts by weight, the polyarylene sulfide resin. This is not preferable because not only the original thermal stability is impaired, but also the viscosity increase during melt-kneading tends to be impaired and the injection moldability tends to be impaired. Furthermore, in the polyarylene sulfide resin composition of the present invention, a plasticizer such as a polyalkylene oxide oligomeric compound, an ester compound, an organic phosphorus compound, inorganic fine particles, an organic phosphorus compound, and the like within a range not impairing the effects of the present invention. Crystal nucleating agents such as metal oxides and polyether ether ketones, polyolefins such as polyethylene and polypropylene, montanic acid waxes, montanic acid and its metal salts, their esters, their half esters, stearyl alcohol, stearamide, various bisamides, bisureas , Metal soaps such as polyethylene wax, lithium stearate, aluminum stearate, ethylenediamine, stearic acid / sebacic acid polycondensate, mold release agents such as silicone compounds, anti-coloring agents such as hypophosphite, phosphorous oxidation Inhibitor, sulfur Antioxidants such as antioxidants, weathering agents and ultraviolet light inhibitors (resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.), heat stabilizer (hindered phenol, hydroquinone, phosphite) And substitution products thereof), foaming agents, pigments (cadmium sulfide, phthalocyanine, carbon black, metallic pigments, etc.), dyes (such as nigrosine), antistatic agents (alkyl sulfate type anionic antistatic agents, quaternary ammonium salt types) Cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine amphoteric antistatic agents, etc.), flame retardants (eg red phosphorus, melamine cyanurate, magnesium hydroxide, hydroxylated) Aluminum hydroxide, polyphosphate ammonium Um, brominated polystyrene, brominated polyphenylene ether, can be added conventional additives such as brominated polycarbonate, brominated epoxy resin or combination of these brominated flame retardants and antimony trioxide).

  Furthermore, in the polyarylene sulfide resin composition of the present invention, it is preferable to tablet the polyarylene sulfide resin composition powder in a solid state from the viewpoint of stabilizing the biting property of the molding machine during measurement. A tablet refers to a granular material obtained by compacting a raw material containing a powdery raw material in a solid phase. Such a tablet can be obtained by compression molding a raw material containing a powdery raw material in a solid phase. . In the above, the solid phase state means that the thermoplastic resin component contained in the raw material is not melted. For the compression molding, it is preferable to use a molding machine having a compression roll such as a tableting machine (rotary, single-shot, double, triple) or briquette machine. Examples of the powdery raw material include polyarylene sulfide resin powder (polyarylene sulfide resin powder), inorganic filler, and the like that should be contained in the resin composition. Polyarylene sulfide resin powder and inorganic filler are included in advance. Further, a powder of a composition obtained by melt-kneading components such as an olefin resin and other additives can be used, and one or more of these can be appropriately selected and used so as to have a desired composition.

  The method for producing the polyarylene sulfide resin composition of the present invention includes, for example, uniformly blending polyarylene sulfide resin powder and an inorganic filler in a solid state using a Banbury mixer, a kneader, a roll, a uniaxial or biaxial extruder, etc. It can be obtained by tableting with a tableting machine or a molding machine having a compression roll. In addition, polyarylene sulfide resin, inorganic filler, and olefin resin are pre-dry blended using a Banbury mixer, kneader, or roll, or do not dry blend, and once melt kneaded using a single or twin screw extruder, etc. Then, after cooling and pulverizing to form a powder, it is possible to form a tablet by using a tableting machine or a molding machine having a compression roll. In this case, the polyarylene sulfide resin to be used for melt kneading is not particularly limited as long as it can be melt kneaded, but it is not limited in the form of powder or pellet, but it is a powder from the viewpoint of reducing variation in characteristics due to poor dispersion of the inorganic filler. Preferably, it is in the form of a pulverized product. In addition, when a melt-kneaded composition is powdered using a single-screw or twin-screw extruder, if the amount of inorganic filler used is large, the fluidity deteriorates, so extrusion from the die cannot be performed. In some cases, pelletization may be difficult. In such a case, as described in JP-A-8-1663, kneading and extrusion may be performed with the head portion of the extruder open. When the amount of the inorganic filler is large, a flaky composition may be obtained. In the present invention, if necessary, a pellet or flake composition obtained by melt-kneading in advance by these methods is cooled and pulverized to form a powder and then tableted. In addition, these methods can be combined into tablets. That is, the composition powder obtained by melt-kneading the polyarylene sulfide resin and the inorganic filler and the polyarylene sulfide resin powder and / or the inorganic filler are adjusted so as to have a desired content and tableted. Is also possible. Among the above methods, a method in which the process is simple, and the mixture obtained by uniformly blending polyarylene sulfide resin powder and inorganic filler in a solid phase is formed into a tablet by using a tableting machine or a molding machine having a compression roll. Is preferable from the viewpoint of the quality stability of the obtained composition.

  The 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), or without supplying them to an extruder or the like and sufficiently melt-kneading them. Is done. Specific examples include a method of kneading a mixture of raw materials at a temperature of 260 to 400 ° C. using a commonly known melt kneader such as a single or twin screw extruder, a Banbury mixer, a kneader, and a mixing roll. be able to. Further, the mixing order of the raw materials is not particularly limited, and a method in which all raw materials are melt-kneaded by the above method, a method in which some raw materials are melt-kneaded by the above method, and the remaining raw materials are melt-kneaded, or Any method may be used, such as a method in which the remaining raw materials are mixed using a side feeder during melt kneading of a part of raw materials with a single-screw or twin-screw extruder. Preferably, the polyarylene sulfide resin and the olefin resin are melt-kneaded, an inorganic filler is added, and the mixture is melt-kneaded for production. In particular, using a twin screw extruder, polyarylene sulfide resin and olefin resin are supplied, melt-kneaded, inorganic filler is supplied using a side feeder, kneaded, and then gas generated by exposure to vacuum is removed. A method can be mentioned preferably. By obtaining a polyarylene sulfide resin composition by such an extrusion process, a material in which each component is well dispersed can be obtained. As for the small amount additive component, other components may be kneaded and pelletized by the above-described method and then added before molding and used for molding.

  The resin composition molding method of the present invention can be melt-molded by an ordinary molding method (injection molding, press molding, injection press molding, etc.), and in particular, from the point of mass production, injection molding and injection are possible. Press molding is preferred.

  Since the polyarylene sulfide resin composition of the present invention is excellent in heat cycle resistance and tap strength durability, a protective article for electrical / electronic component integrated modules, a support member, and a molded article into which a metal such as a motor is inserted, between members It is suitable for a member that needs to be repeatedly screwed in the assembly process when fixing the joint with a screw, and can be preferably used for a molded product that is subject to repeated environmental changes between low and high temperatures. There is no particular limitation on the temperature change, but preferably the resin composition has excellent heat cycle property and tap strength durability for those having a temperature change of 20 ° C. or higher and those in which the members are fixed with screws. Can demonstrate.

  The polyarylene sulfide resin composition of the present invention is excellent in rigidity, dimensional stability, thermal conductivity, fluidity, and particularly excellent in low anisotropy of linear expansion, heat cycle resistance, and tap strength durability. It is particularly useful for parts that require heat cycle resistance, box-shaped electrical / electronic component integrated module protection / support members and molded products with metal inserts such as motors, structural parts such as housings, and electrical parts Suitable for cases. Sensor, LED lamp, connector, socket, resistor, relay case, switch, coil bobbin, capacitor, variable capacitor case, optical pickup, oscillator, various terminal boards, transformer, plug, printed circuit board, tuner, speaker, microphone, headphones, Electrical / electronic parts represented by magnetic head case, power module, terminal block, semiconductor, liquid crystal, FDD carriage, FDD chassis, parabolic antenna, computer-related parts, etc .; VTR parts, TV parts, irons, hair dryers, rice cooker parts Represented by parts such as microwave oven parts, acoustic parts, audio equipment parts such as audio / laser discs / compact discs, lighting parts, refrigerator parts, air conditioner parts, or water heater parts such as water heaters and bath water / temperature sensors. Household, office electrical product parts; office computer-related parts, telephone-related parts, facsimile-related parts, copier-related parts, cleaning jigs, lighter, and other machine-related parts; microscopes, binoculars, cameras, watches, etc. High-priced equipment represented by: precision machinery-related parts: alternator terminals, alternator connectors, IC regulators, light meter potential meter bases, relay blocks, inhibitor switches, exhaust gas valves and other valves, fuel-related / exhaust systems / intake systems Various pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, hot water temperature sensor, brake pad -Sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating hot air flow control valve, water pump impeller, turbine vane, dust distributor, starter switch, ignition coil and its Bobbin, starter relay, transmission wire harness, window washer nozzle, air conditioner panel switch board, coil for fuel-related electromagnetic valve, fuse connector, horn terminal, electrical component insulation plate, lamp socket, lamp reflector, lamp housing, brake piston, Solenoid bobbin, engine oil filter, ignition device case, motor related parts It can also be applied to automotive and vehicle-related parts such as par movable parts, power window movable parts, brush holders for radiator motors, insulators, rotors, motor cores, bus rings), and other various uses. In particular, the degree of freedom in product design due to miniaturization and the suppression of cracks in molded parts due to rapid temperature changes in molded parts, as well as excellent mechanical strength and fluidity. It is useful for automotive parts, electric / electronic parts, thermal equipment parts, etc.

  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 (A) Polyarylene sulfide resin PPS-1 (Polyarylene sulfide): Sodium sulfide 9-hydrate 6.005 kg (25 mol), sodium acetate 0.11 kg (1.35 mol) 5 kg of N-methyl-2-pyrrolidone (NMP) was charged, the temperature was gradually raised to 205 ° C. while passing 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. and poured into 10 kg of NMP, stirred for about 1 hour, filtered, and 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 of about 90 ° C. until the pH of the filtrate reached 7, Drying under reduced pressure at 80 ° C. for 24 hours yielded dry PPS. Using a capillograph (manufactured by Toyo Seiki Co., Ltd.) with an orifice having a hole diameter of 1.0 mm and a length of 10 mm and measuring the resin temperature at 310 ° C. and a shear rate of 1000 / sec, the melt viscosity of PPS Was 270 Pa · s. This PPS was designated as PPS-1.
PPS-2 (polyarylene sulfide): M2100 (manufactured by Toray Industries, Inc.), melt viscosity 130 Pa · s

Reference Example 2 (B1) Plate-like filler MIC (mica): MK-300 (manufactured by Corp Chemical) thickness 0.7 μm, average particle diameter (D50) 20 μm, Mohs hardness 2.8
GFL-1 (glass flake): REFG-112 (manufactured by Nippon Sheet Glass) non-alkali glass, average thickness 5 μm, average particle diameter (D50) 600 μm, Mohs hardness 4
GFL-2 (glass flake): MT1160FYX (manufactured by Nippon Sheet Glass Co., Ltd.) low alkali glass, average thickness 1.3 μm, average particle diameter (D50) 160 μm, Mohs hardness 4
GFL-3 (glass flake): MT160FYX (manufactured by Nippon Sheet Glass Co., Ltd.) low alkali glass, average thickness 0.4 μm, average particle diameter (D50) 160 μm, Mohs hardness 4
GFT (graphite): CFW-50A (manufactured by Chuetsu Graphite) Average particle diameter (D50) 48 μm, Mohs hardness 1

  The average particle diameter (D50) was as follows. (B1) About 0.05 g of a plate-like filler was placed in 50 cc of water and stirred, and then a few drops of “My Pet” (manufactured by Kao Corporation) in 100 cc in advance. After adding a few drops of surfactant dilute solution (to the extent that bubbles do not form) and dispersing with an ultrasonic cleaner, particles in each particle size section using a laser diffraction particle size distribution analyzer SALD-3100 manufactured by Shimadzu Corporation The amount (%) was plotted, and the 50% cumulative particle size (D50) was determined from the accumulated distribution curve.

Reference Example 3 (B2) Particulate filler AL-1 (alumina): LT-200 (manufactured by Nippon Light Metal Co., Ltd.) Average particle diameter (D50) 2 μm, thermal conductivity 20 W / m · K
AL-2 (alumina): AL-43PC (manufactured by Showa Denko KK) Average particle size (D50) 4 μm, thermal conductivity 20 W / m · K
MGO (magnesium oxide): CF2-100 (manufactured by Tateho Chemical Industry Co., Ltd.) average particle size 28 μm, thermal conductivity 30 W / m · K
SI (silica): FB-74 (manufactured by Denki Kagaku Kogyo) average particle size (D50) 30 μm, thermal conductivity 2 W / m · K

  (B2) The thermal conductivity of the particulate filler is determined by using a sample in which the filler is hardened with an epoxy-based thermosetting resin and measuring the thermal conductivity by the optical alternating current method. The thermal conductivity in the case of a filler capacity of 100% is calculated from a calibration curve showing the relationship, and is a value converted into a numerical value of the laser flash method.

  The average particle size (D50) was (B2) about 0.05 g of the particulate filler was put in 50 cc of water and stirred, and then with a dropper, a few drops of “My Pet” (manufactured by Kao) were added to 100 cc in advance. After adding a few drops of surfactant dilute solution (to the extent that bubbles do not form) and dispersing with an ultrasonic cleaner, particles in each particle size section using a laser diffraction particle size distribution analyzer SALD-3100 manufactured by Shimadzu Corporation The amount (%) was plotted, and the 50% cumulative particle size (D50) was determined from the accumulated distribution curve.

Reference Example 4 (B3) Fibrous filler MLD (milled fiber): EPDM70M10A (manufactured by Nippon Electric Glass Co., Ltd.) E glass, milled fiber, 65 mesh pass with sieve, 400 mesh on used, fiber diameter 10 μm, average Fiber length 70μm
GF (glass fiber): JAFT523 (manufactured by Owens Corning) chopped strand glass fiber, fiber diameter 10 μm, average fiber length 3000 μm

  Average fiber length (B3) 100 mg of fibrous filler was sampled, observed with a scanning electron microscope (S2100A, manufactured by Hitachi, Ltd.), photographed at a magnification of 10000 times, randomly sampled 500 pieces, and each fiber (particle) The length of the longest part was measured, and the average value was determined as the average fiber length.

Reference Example 5 (C) Olefin resin OR-1: BF-E (manufactured by Sumitomo Chemical Co., Ltd.), ethylene / glycidyl methacrylate = 88/12% by weight copolymer OR-2: Toughmer A4085 (manufactured by Mitsui Chemicals), Ethylene / butene-1 = 82/18% by weight copolymer

Examples 1-14, Examples 16-18, Comparative Examples 1-8
(A) polyarylene sulfide resin of Reference Example 1, (B1) plate-like filler of Reference Example 2, (B2) granular filler of Reference Example 3, (B3) fibrous filler of Reference Example 4 and Reference Example 5 (C) Screw type twin screw extruder (manufactured by Nippon Steel Works, Ltd.) blended in the amounts shown in Table 1, Table 2, Table 3, and Table 4 with a ribbon blender and set to an extrusion condition of 320 ° C .; After supplying (A) and (C) blended using TEX-44), melt-kneading at a screw rotation speed of 200 rpm, and supplying (B1), (B2), and (B3) from the side feeder, The gas generated by exposure to vacuum was removed to obtain pellets. Subsequently, after drying for 5 hours with a 130 degreeC hot-air dryer, evaluation mentioned later was performed.

(1) Tensile strength An ASTM No. 1 dumbbell test piece was prepared using an injection molding machine UH1000 (80t) (manufactured by Nissei Plastic Industry Co., Ltd.) under the temperature conditions of a cylinder temperature of 320 ° C and a mold temperature of 140 ° C. ASTM D638 Evaluated in accordance with. The higher this value, the better the rigidity.

(2) Coefficient of linear expansion Using an injection molding machine UH1000 (80t) (manufactured by Nissei Plastic Industry Co., Ltd.), and with a temperature condition of a cylinder temperature of 320 ° C. and a mold temperature of 150 ° C., a square-shaped product (80 mm × 80 mm × 3.0 thickness) , A film gate), and a test piece (10 mm × 4 mm × 3 mm) in the flow direction of the resin and in a direction perpendicular to the resin flow direction is cut out from the central portion. Using a thermomechanical analyzer TMA (manufactured by Seiko Instruments Inc.), a linear expansion coefficient of 30 ° C. to 180 ° C. in the longitudinal direction of the test piece was measured. The smaller the value of the linear expansion coefficient and the closer the ratio (anisotropy) of the flow direction (MD) to the perpendicular direction (TD) is to 1.0, the smaller the linear expansion anisotropy and the better the heat cycle resistance.

(3) Thermal conductivity Using an injection molding machine UH1000 (80t) (manufactured by Nissei Plastic Industry Co., Ltd.), a corner-shaped product (50 mm x 50 mm x 3 mm thickness, film) under the temperature conditions of a cylinder temperature of 320 ° C and a mold temperature of 150 ° C Gate), both surfaces of this molded product were cut to a depth of 0.5 mm and used as a test piece having a thickness of 2 mm, using a laser flash method constant measuring apparatus (LF / TCM-FA8510B manufactured by Rigaku Corporation). The thermal conductivity was measured.

(4) Heat cycle resistance-1
Using an injection molding machine UH1000 (80t) (manufactured by Nissei Plastic Industrial Co., Ltd.), a metal piece having a length of 47.0 mm, a width of 47.0 mm and a height of 28.6 mm under the temperature conditions of a cylinder temperature of 320 ° C. and a mold temperature of 150 ° C. Was fixed in a mold, and a resin having a thickness of 1.2 mm was overmolded to produce a heat cycle resistance evaluation test piece. Evaluation is THERMAL SHOCK CHANBER TSA-100S-W type (manufactured by Tabai Co., Ltd.), after treatment at 140 ° C. × 1 hr, treatment at −40 ° C. × 1 hr as a cycle, cooling cycle treatment, every 5 cycles The presence or absence of cracks was confirmed visually. The number of cold heat treatments in which cracks were observed was defined as heat cycle resistance-1. The more processing cycles until the occurrence of cracks, the better the heat resistance. Those in which no cracks were observed for 2000 cycles or more were described as> 2000.

(5) Heat cycle resistance-2
Using an injection molding machine UH1000 (80t) (manufactured by Nissei Plastic Industrial Co., Ltd.), a metal piece having a length of 47.0 mm, a width of 47.0 mm and a height of 28.6 mm under the temperature conditions of a cylinder temperature of 320 ° C. and a mold temperature of 150 ° C. Was fixed in a mold, and a resin having a thickness of 1.2 mm was overmolded to produce a heat cycle resistance evaluation test piece. Evaluation uses THERMAL SHOCK CHANBER TSA-100S-W type (manufactured by Tabai Co., Ltd.), after treating at 160 ° C. × 1 hr and then treating at −40 ° C. × 1 hr as a cycle, cooling cycle treatment is performed every 5 cycles The presence or absence of cracks was confirmed visually. The number of cold heat treatments in which cracks were observed was defined as heat cycle resistance-2. The more processing cycles until the occurrence of cracks, the better the heat resistance.

(6) Impact strength Using an injection molding machine UH1000 (80t) (manufactured by Nissei Plastic Industry Co., Ltd.), a corner forming product (63 mm × 12.5 mm × 3 mm thickness) under the temperature conditions of a cylinder temperature of 320 ° C. and a mold temperature of 150 ° C. The V notch was processed and measured according to ASTM D-256 under a temperature condition of 23 ° C. The larger the value, the better the toughness.

(7) Fluidity Using an injection molding machine UH1000 (80t) (manufactured by Nissei Plastic Industry Co., Ltd.), measuring the rod flow length of 10mm in width and 0.5mm in thickness under the temperature conditions of cylinder temperature 330 ° C and mold temperature 150 ° C. Twenty strip-shaped molded articles were prepared with a mold at an injection speed of 100 mm / s and a pressure of 98 MPa. Subsequently, the length to the fluid end of the obtained molded product was measured, and the average value was defined as fluidity. The larger the value, the better the fluidity.

(8) Screw-in torque Using an injection molding machine UH1000 (80t) (manufactured by Nissei Plastic Industrial Co., Ltd.), a slide base molded product for optical parts (inner diameter 1.0 mm) under the temperature conditions of cylinder temperature 320 ° C. and mold temperature 150 ° C. Form a 30 mm x 30 mm x 3 mm thick flat plate outer periphery with two screw holes with a diameter of 5 mm in height and 1 mm in thickness with a vertical wall) using an umbrella type torque driver (Nakamura Seisakusho) Insert the tapping screw (BIT SPH1.2 × 3.0 rough) into the hole of the molded product with “Canon idling torque driver” 1.5LTDK), and torque of the torque driver 3cN ・ m, 4cN ・ m, 5cN -Set to m and evaluated whether screwing is possible. The lower the set torque, the better the workability when fixing the parts with screws (◎ 3cN ・ m setting if screwing is possible ◎ 4cN ・ m is screwing possible ○ 5cN -△ if m can be screwed in, x if neither is possible).

(9) Durability of tap strength Using an injection molding machine UH1000 (80t) (manufactured by Nissei Plastic Industry Co., Ltd.), a slide base molded product for an optical component (inner diameter: 1.) under the temperature conditions of a cylinder temperature of 320 ° C. and a mold temperature of 150 ° C. Form a 5 mm high x 1 mm thick walled product on a 30 mm x 30 mm x 3 mm thick flat plate outer periphery with two 0 mm diameter screw holes and use an umbrella type torque driver (Nakamura Seisakusho Co., Ltd.) Insert a tapping screw (BIT SPH1.2 × 3.0 rough tip) into the hole of the molded product with “Canon idling torque driver” 1.5LTDK), and torque of the torque driver is 3 cN · m, 4 cN · m, Set to 5 cN · m, apply torque from the screwed position to the torque driver set position (until idling), and then remove the screw. Insert the screw into the same hole again, apply torque from the screwed position to the torque driver setting position (until idling), and then remove the screw. This was repeated 5 times and the tap strength durability was measured. If the tapping screw does not slip or cracks occur in the molded product screw hole even if it is repeated 5 times at each set torque, the tapping screw runs idle or cracks occur in the molded product screw hole Is x. When the screw can be repeatedly screwed in at each set torque, the workability and the durability of the component are excellent when the component is retightened with the screw.

Example 15
(A) polyarylene sulfide resin of Reference Example 1, (B1) plate-like filler of Reference Example 2, (B2) granular filler of Reference Example 3, (B) inorganic filler of Reference Example 4 and Reference Example 5 (C) The head portion of a screw type twin screw extruder (Ikegai Iron Works Co., Ltd .; PCM30), which was blended in the amount shown in Example 11 of Table 2 with a ribbon blender and set to an extrusion condition of 320 ° C., was removed. In this state, melt kneading was performed at a screw rotation speed of 150 rpm to obtain an amorphous composition. Next, the irregularly shaped composition was pulverized using a pulverizer (manufactured by Horai Iron Works Co., Ltd .; UC-210S) until it passed through a screen having a diameter of 3 mm, and then the obtained powder was rotary equipped with an automatic supply feeder. Tableting was performed at room temperature using a tableting machine to obtain a cylindrical tablet of 6.5 mm diameter × 3.5 mm length. Next, after drying with a hot air dryer at 130 ° C. for 3 hours, using a injection molding machine UH1000 (manufactured by Nissei Plastic Industry Co., Ltd.), a measurement time when measuring 10 shots at a screw temperature of 50 rpm under a temperature condition of a cylinder temperature of 320 ° C. Was measured. The variation at that time was defined as the variation in measurement time, and was obtained from the following equation. (Measurement time variation) = (maximum value of measurement time during 10 shots) − (minimum value of measurement time during 10 shots). The measurement time variation of Example 8 was 3 seconds, and the measurement time variation of Example 11 was 1.5 seconds.

  As is apparent from the results of Tables 1 to 4, the molded product obtained from the polyarylene sulfide resin composition of the present invention has rigidity, dimensional stability, thermal conductivity, fluidity and heat cycle resistance, and tap strength durability. It can be seen that it has excellent properties. Therefore, heat cycle resistance, a member that needs to be repeatedly screwed in the assembly process when fixing the joint portion between the members with screws, and the reliability of the characteristics for automobiles are particularly required It is useful for electrical component-related and electrical / electronic component-related, particularly for insulators used for housings, motors, etc. In addition, it can be applied to various other fields.

Claims (9)

A polyarylene sulfide resin composition comprising (A) 20 to 40% by weight of polyarylene sulfide resin and (B) 60 to 80% by weight of an inorganic filler, where the total of (A) and (B) is 100% by weight. And the total amount of (B1) plate-like filler and (B2) granular filler in the (B) inorganic filler is more than 70% by weight, and (B1) plate-like filler ( B2) The blending ratio (weight ratio) of the granular filler is (B1) / (B2) = 0.7 / 1 to 8/1, and the thermal conductivity measured by the laser flash method of the polyarylene sulfide resin composition Is 0.5 W / m · K or more, a polyarylene sulfide resin composition. (B1) The polyarylene sulfide resin composition according to claim 1, wherein the plate-like filler has a Mohs hardness of 2 or more. (B1) The polyarylene sulfide resin composition according to claim 1 or 2, wherein the plate-like filler is glass flakes. The polyarylene sulfide resin composition according to claim 3, wherein the glass flake has an average thickness of 0.1 to 10 µm and an average particle diameter (D50) of 50 to 700 µm. (B2) The polyarylene sulfide resin composition according to any one of claims 1 to 4, wherein the particulate filler is a thermally conductive filler having a thermal conductivity of 10 W / m · K or more. (B2) A granular filler is an alumina, The polyarylene sulfide resin composition in any one of Claims 1-5. The polyarylene sulfide resin composition according to any one of claims 1 to 6, wherein 2 to 40 parts by weight of (C) an olefin resin is blended with 100 parts by weight of (A) polyarylene sulfide resin. A polyarylene sulfide resin composition tablet obtained by tableting the powder of the polyarylene sulfide resin composition according to any one of claims 1 to 7 in a solid phase. A molded article obtained by injection molding the polyarylene sulfide resin composition according to any one of claims 1 to 7 or the polyarylene sulfide resin composition tablet according to claim 8.