JP4725050B2 - Polyarylene sulfide composition - Google Patents

Description

  The present invention relates to a polyarylene sulfide composition. More specifically, the present invention relates to a polyarylene having excellent mechanical properties, heat resistance, molding processability, and improved adhesion to epoxy resins, urethane resins, silicone resins and the like. It relates to a sulfide composition.

  Polyarylene sulfide (hereinafter sometimes abbreviated as PAS) is excellent in mechanical strength, heat resistance, chemical resistance, molding processability, and dimensional stability. It is used as a material for automobile parts.

  In many cases, these parts are bonded to a part material made of epoxy resin, urethane resin, silicone resin or the like as the secondary processing. However, in the case of the PAS material, it is known that the bonding force obtained by the adhesive is relatively small. At this time, the component material composed of these epoxy resin, urethane resin, silicone resin, etc. and the component material composed of PAS Adhesion often becomes a problem.

  Therefore, as a method for improving the adhesion of such component materials, a method has been proposed in which the surface of a molded article is roughened mechanically or chemically, and the adhesion strength is improved by the anchor effect. For example, a mixed solution of chromic anhydride and sulfuric acid, a solution obtained by dissolving a Friedel-Crafts reaction catalyst in an organic solvent (see, for example, Patent Document 1), a treating agent comprising chlorosulfonic acid and dichloroethane (for example, a patent) Reference 2), and surface treatment methods using hydrofluoric acid-based etching solutions developed by Philips Oil. A method of corona discharge treatment of the surface of a molded product is also known. Furthermore, a method for improving the adhesion with an epoxy resin by adding carnauba wax to PAS has also been proposed (see, for example, Patent Document 3).

  However, the methods proposed in Patent Document 1, Patent Document 2, and the like often use powerful drugs that are toxic to the human body, and often leave environmental problems such as safety and hygiene and wastewater treatment. Also, the corona discharge treatment method often requires special equipment and has practical problems. Furthermore, although the method proposed in Patent Document 3 is effective in improving the adhesiveness of PAS, it is at a level that cannot be said to be sufficient for practical use in a severe use environment.

  Moreover, the composition which mix | blended the epoxy resin with specific polyarylene sulfide resin is disclosed as a composition which mix | blended the epoxy resin with the thermoplastic resin. However, the effect is to increase the melt viscosity, and there is no disclosure about the adhesive improvement effect (for example, see Patent Document 4).

  In addition, a composition in which a maleic anhydride-modified ethylene copolymer is blended with polyphenylene sulfide is disclosed. However, the effect is to improve the impact resistance and toughness, and no adhesive improvement effect is disclosed (for example, see Patent Documents 5 and 6).

JP 63-089544 A JP 63-118342 A Japanese Patent Laid-Open No. 02-272063 JP 59-05944 A Japanese Patent Laid-Open No. 10-237150 Japanese Patent Laid-Open No. 11-181283

  Therefore, the present invention provides a PAS composition that is excellent in mechanical properties, heat resistance, and moldability, and has improved adhesion to epoxy resins, urethane resins, and silicone resins.

  As a result of intensive studies on the above problems, the present inventors have found that a PAS composition comprising a specific PAS, a bisphenol A type epoxy resin, a maleic anhydride-modified ethylene copolymer, and carnauba wax has mechanical properties, heat resistance, and molding. It has been found that it has excellent workability and adhesion to epoxy resins, urethane resins, and silicone resins, and has completed the present invention.

  That is, the present invention is a PAS 60 to 98 having a melt viscosity of 200 to 30000 poise measured with a Koka flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm under a measurement temperature of 315 ° C. and a load of 10 kg. 0.5 wt% to 20 wt% bisphenol A type epoxy resin having an epoxy equivalent of 450 to 2300 and a melting point of 50 to 135 ° C, 1 to 30 wt% of maleic anhydride-modified ethylene copolymer, and carnauba The present invention relates to a PAS composition comprising 0.2 to 10% by weight of a wax.

  The present invention is described in detail below.

  The PAS composition of the present invention is a polysiloxane having a melt viscosity of 200 to 30000 poise measured with a Koka flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm under a measurement temperature of 315 ° C. and a load of 10 kg. Arylene sulfide 60 to 98.3% by weight, epoxy equivalent 450 to 2300, melting point 50 to 135 ° C. bisphenol A type epoxy resin 0.5 to 20% by weight, maleic anhydride modified ethylene copolymer 1 to 1 A PAS composition comprising 30% by weight and 0.2-10% by weight of carnauba wax.

  The PAS used in the present invention is a PAS having a melt viscosity of 200 to 30000 poise measured with a Koka flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm under a measurement temperature of 315 ° C. and a load of 10 kg. Examples of the PAS include p-phenylene sulfide units, m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfide sulfone units, phenylene sulfide ketone units represented by the following general formulas (1) to (8), A homopolymer or copolymer comprising a phenylene sulfide ether unit, a biphenyl sulfide unit, and a substituent-containing phenylene sulfide unit can be exemplified. Specific examples of these homopolymers or copolymers include poly (p-phenylene). Sulfide), polyphenylene sulfide Phon, polyphenylene sulfide ketone, polyphenylene sulfide ether, amino group substituted poly (p-phenylene sulfide), amino group substituted polyphenylene sulfide sulfone, amino group substituted polyphenylene sulfide ketone, amino group substituted polyphenylene sulfide ether, hydroxyl group substituted poly (p-phenylene) Sulfide), hydroxyl group substituted polyphenylene sulfide sulfone, hydroxyl group substituted polyphenylene sulfide ketone, hydroxyl group substituted polyphenylene sulfide ether, carboxyl group substituted poly (p-phenylene sulfide), carboxyl group substituted polyphenylene sulfide sulfone, carboxyl group substituted polyphenylene sulfide ketone, carboxyl Group-substituted polyphenylene sulfide Ether and the like, and among them, particularly heat resistance, since the PAS composition excellent in adhesion, poly (p- phenylene sulfide) is preferably an amino group substituted poly (p- phenylene sulfide).

さらに、本発明に用いられるＰＡＳとは、直径１ｍｍ、長さ２ｍｍのダイスを装着した高化式フローテスターにて、測定温度３１５℃，荷重１０ｋｇの条件下で測定した溶融粘度が２００〜３００００ポイズのものであり、好ましくは５００〜２００００ポイズのものである。ここで、溶融粘度が２００ポイズ未満である場合、得られるＰＡＳ組成物は靭性及びウエルド強度に劣るものとなる。一方、溶融粘度が３００００ポイズを越える場合、得られるＰＡＳ組成物は成形加工性に劣るものとなる。

Furthermore, PAS used in the present invention is a high viscosity flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm, and has a melt viscosity of 200 to 30000 poise measured at a measurement temperature of 315 ° C. and a load of 10 kg. Preferably 500 to 20000 poise. Here, when the melt viscosity is less than 200 poise, the obtained PAS composition is inferior in toughness and weld strength. On the other hand, when the melt viscosity exceeds 30000 poise, the PAS composition obtained is inferior in moldability.

  Further, the PAS used in the present invention may be linear, or may be prepared by adding a small amount of a trihalogen or higher polyhalogen compound during polymerization to introduce a slight cross-linked or branched structure. The heat treatment may be performed in a non-oxidizing inert gas such as nitrogen. Moreover, thermosetting PAS obtained by heat-curing linear PAS at high temperature in the presence of oxygen may be used. Further, it may be a mixture of these structures.

  Among these PAS, since it becomes a PAS composition with improved toughness and weld strength in particular, with a Koka flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm, the measurement temperature is 315 ° C. and the load is 10 kg. A thermosetting PAS obtained by heat-curing a linear PAS having a melt viscosity of 200 poise or more, preferably 300 poise or more at a high temperature in the presence of oxygen, is preferred.

  In addition, the PAS reduces impurities such as ions and oligomers by performing deionization treatment (acid washing, hot water washing, etc.) before or after heat curing, or washing treatment with an organic solvent such as acetone or methyl alcohol. It may be a thing.

  The blending amount of PAS constituting the PAS composition of the present invention is 60 to 98.3% by weight, and particularly 75 to 95% by weight because it becomes a PAS composition having excellent mechanical properties, heat resistance and adhesiveness. It is preferable. Here, when the blending amount of PAS is less than 60% by weight, the obtained PAS composition is inferior in heat resistance, molding processability, and mechanical properties. On the other hand, when it exceeds 98.3% by weight, the obtained PAS composition is inferior in adhesiveness.

  The epoxy resin used in the present invention is a bisphenol A type epoxy resin having an epoxy equivalent of 450 to 2300 and a melting point of 50 to 135 ° C. Among them, an epoxy equivalent of 700 to 2100 and a melting point of 80 to 131 ° C. The bisphenol A type epoxy resin is preferable, and as its properties, a solid bisphenol A type epoxy resin containing two or more epoxy groups is used, and when it is an epoxy resin other than the bisphenol A type epoxy resin, the resulting PAS composition Things are inferior in adhesion.

  Here, in the case of a bisphenol A type epoxy resin having an epoxy equivalent of less than 450, when the obtained PAS composition is used as a molded product, the mold contamination is remarkably deteriorated or the appearance of the molded product is inferior. . On the other hand, when the epoxy equivalent is a bisphenol A type epoxy resin exceeding 2300, the effect of improving the adhesive strength of the resulting PAS composition varies, making it difficult to handle. Further, in the case of a bisphenol A type epoxy resin having a melting point of less than 50 ° C., when the obtained PAS composition is formed into a molded product, the mold contamination is remarkably deteriorated or the appearance of the molded product is inferior. On the other hand, in the case of a bisphenol A type epoxy resin having a melting point exceeding 135 ° C., the effect of improving the adhesive strength of the obtained PAS composition varies, making it difficult to handle.

  The blending amount of the bisphenol A type epoxy resin constituting the PAS composition of the present invention is 0.5 to 20% by weight, and in particular, it becomes a PAS composition having excellent mechanical properties, heat resistance and adhesiveness. It is preferably 15% by weight. Here, when the blending amount of the bisphenol A type epoxy resin is less than 0.5% by weight, the effect of improving the adhesiveness of the obtained PAS composition does not appear. On the other hand, when the blending amount of the bisphenol A type epoxy resin exceeds 20% by weight, the molding processability of the obtained PAS composition is remarkably lowered.

  As the maleic anhydride-modified ethylene copolymer used in the present invention, any maleic anhydride-modified ethylene copolymer can be used. For example, maleic anhydride-modified polyethylene polymer, maleic anhydride-modified A copolymer such as a polypropylene polymer or a maleic anhydride-ethylene-acrylic acid ester copolymer; a copolymer obtained by grafting maleic anhydride on an ethylene or ethylene-propylene copolymer, or the like can be used. Among these, since it becomes a PAS composition having excellent adhesiveness, it is a maleic anhydride-modified ethylene copolymer having a melt flow rate [measurement method conforming to JIS K6730 (1980)] of 10 g / 10 min or less. It is preferable.

  Next, the blending amount of the maleic anhydride-modified ethylene copolymer used in the present invention is 1 to 30% by weight, and preferably 3 to 20 because gas generation is suppressed when the PAS composition is molded. % By weight. If the blending amount is less than 1% by weight, the PAS composition is inferior in adhesiveness, and if it exceeds 30% by weight, gas generation is remarkable when the PAS composition is molded.

  The PAS composition of the present invention contains 0.2 to 10% by weight of carnauba wax. Here, when the compounding amount of the carnauba wax is less than 0.2 parts by weight, the surface appearance of the molded product when the obtained PAS composition is used as a molded product is significantly reduced. On the other hand, when the carnauba wax exceeds 10% by weight, a problem that these components cause mold contamination or the like during molding is likely to occur. As the carnauba wax, a general commercial product can be used.

  Since the PAS composition of the present invention is particularly excellent in mechanical strength, it is preferable to further blend 10 to 200 parts by weight of a fibrous filler and / or an inorganic filler with respect to 100 parts by weight of PAS. .

  Examples of the fibrous filler include glass fiber, carbon fiber, graphitized fiber, whisker, metal fiber, inorganic fiber, organic fiber, and mineral fiber.

  As specific examples of glass fibers, glass fibers such as chopped strands, milled fibers, and rovings having an average fiber diameter of 6 to 14 μm; glass fibers coated with metal such as nickel and copper; silane fibers; aluminosilicate glass fibers; Hollow glass fiber; non-hollow glass fiber and the like.

  Specific examples of the carbon fiber include PAN-based carbon fiber using polyacrylonitrile as a raw material, pitch-based carbon fiber using pitch as a raw material, and the like.

  Specific examples of the inorganic fiber include various inorganic fibers such as rock wool, zirconia, alumina silica, barium titanate, silicon carbide, alumina, silica, blast furnace slag, and the like.

  Specific examples of mineral fibers include asbestos, wollastonite, magnesium oxysulfate, and the like.

  Specific examples of organic fibers include wholly aromatic polyamide fibers, phenol resin fibers, wholly aromatic polyester fibers, and the like.

  Specific examples of the whisker include silicon nitride whisker, basic magnesium sulfate whisker, barium titanate whisker, potassium titanate whisker, silicon carbide whisker, boron whisker, and zinc oxide whisker.

  The inorganic filler is a plate-like, powder-like inorganic substance such as calcium carbonate, lithium carbonate, magnesium carbonate, zinc carbonate, mica, silica, talc, clay, calcium sulfate, kaolin, wollastonite, zeolite, Glass powder, alumina, silicon oxide, magnesium oxide, zirconium oxide, iron oxide, tin oxide, magnesium silicate, calcium silicate, calcium phosphate, magnesium phosphate, graphite, carbon black, glass powder, glass balloon, glass flake, hydrotalcite, etc. Is mentioned. These inorganic fillers can be used in combination of two or more, and if necessary, a surface treated with a functional compound or polymer such as an epoxy compound, an isocyanate compound, a silane compound, or a titanate compound as necessary. It may be used.

  The fibrous filler and / or inorganic filler that can be used in some cases in the present invention is preferably treated with a silane coupling agent or a titanate coupling agent, particularly aminoalkoxylsilane or epoxyalkoxylsilane. It is preferable that it is surface-treated. In addition, the fibrous filler may be obtained by subjecting a bundle of glass fibers to a convergence treatment with an epoxy resin and / or a urethane resin in order to improve handling properties after performing the surface treatment in some cases.

  Furthermore, the PAS composition of the present invention is a plasticizer such as a polyalkylene oxide oligomer compound, a thioether compound, an ester compound, an organophosphorus compound, an antioxidant, and a heat stabilizer, as long as the effects of the present invention are not impaired. One or more usual additives such as a lubricant, an ultraviolet ray preventive agent, a coloring agent, a crystal nucleating agent, and a foaming agent may be added.

  Further, the PAS composition of the present invention can be used in various thermosetting resins and thermoplastic resins, for example, cyanate ester resin, polyimide, silicone resin, polyolefin, polyester, polyamide, polyphenylene oxide, without departing from the object of the present invention. Use a mixture of one or more of polycarbonate, polysulfone, polyetherimide, polyethersulfone, polyetherketone, polyetheretherketone, polyamideimide, polyamide elastomer, polyolefin elastomer, polyester elastomer, polyalkylene oxide, etc. Can do.

  As a method for producing the PAS composition of the present invention, a conventionally used hot melt kneading method can be used. For example, a heat melt kneading method using a single screw or twin screw extruder, a kneader, a mill, a Brabender or the like can be mentioned, and a melt kneading method using a twin screw extruder excellent in kneading ability is particularly preferable. Moreover, the kneading | mixing temperature in this case is not specifically limited, Usually, it can select arbitrarily from 280-370 degreeC. The mixing order of the raw materials is not particularly limited, and all the raw materials are mixed and then melt kneaded by the above method; after a part of the raw materials are mixed, melt kneaded by the above method and the remaining raw materials are further mixed Melting and kneading method: Any method may be used, such as a method of mixing a part of raw materials and mixing the remaining raw materials using a side feeder during melt kneading with a single or twin screw extruder. Moreover, about a small amount addition component, after kneading | mixing and pelletizing another component by said method etc., you may use it by adding before shaping | molding.

  The PAS composition obtained by the present invention retains properties such as chemical resistance, molding processability and dimensional stability, has good mechanical strength and heat resistance, and adheres to epoxy resins, urethane resins and silicone resins. It has the characteristic that the property is good. Furthermore, the obtained PAS composition can be formed into an arbitrary shape using an injection molding machine, an extrusion molding machine, a compression molding machine or the like. The molded products thus obtained can be various cases such as relay cases, variable capacitor cases, condenser cases, power module cases, intelligent power module cases, engine control unit cases, ignition device cases, lamp housings, etc. It can be widely used for electrical / electronic equipment members, automobile parts, office equipment parts, and the like.

  According to the present invention, it retains characteristics such as chemical resistance, molding processability and dimensional stability, and also has good mechanical strength and heat resistance, and has adhesion to epoxy resin, urethane resin and silicone resin. Since a good PAS composition is obtained, its industrial value is high.

  EXAMPLES The present invention will be specifically described below with reference to examples, but the present invention is not limited to these examples.

  The PAS and PAS composition used in the examples were evaluated and measured by the following methods.

~ Measurement of adhesive strength ~
The PAS composition obtained in the example was molded into ASTM No. 1 tensile test piece, the test piece was cut into two pieces and deburred, and then the surface was washed with acetone, with an adhesion area of 1.3 cm ² , A two-pack type epoxy adhesive (manufactured by Nagase Sangyo Co., Ltd .; main agent: XNR5002 (trade name) / curing agent: XNH5002 (trade name) = 100/90 (parts by weight)) was applied, and a binder clip (Lion Corporation) was applied. Manufactured, product name No. 155), cured at 100 ° C. for 1 hour, and further cured at 150 ° C. for 3 hours to prepare an adhesive strength measurement test piece.

  The obtained test specimen for measuring the adhesive strength was allowed to stand in an environment of 23 ° C. and 50 RH% for 24 hours, and then the binder clip was removed, and a low speed tensile tester (manufactured by Shimadzu Corporation: trade name Autograph AG-5000B) The tensile shear bond strength test was conducted at a tensile rate of minutes, and the result was taken as the bond strength.

~ Evaluation of mold contamination ~
The PAS composition obtained in the examples was molded into ASTM No. 1 tensile test pieces, and the contamination of the molding die after 50 shots of the tensile test pieces were visually observed.

The evaluation criteria are shown below.
○: No deposit on the mold surface.
X: Brown adhesion on the mold surface.

-Evaluation of appearance of molded product surface-
The PAS composition obtained in the examples was molded into ASTM No. 1 tensile test pieces, and the surface thereof was visually observed.

The evaluation criteria are shown below.
○: The surface is smooth and good.
X: Roughness is generated on the surface or molding is impossible.

~ Heat cycle test ~
In the obtained case (100 mm × 100 mm × height 30 mm, wall thickness 1.5 mm), a two-component epoxy adhesive (manufactured by Nagase Sangyo Co., Ltd .; main agent: XNR5002 (trade name) / curing agent: XNH5002 (trade name) ) = 100/90 (parts by weight)) and cured. Next, a heat cycle in which the case filled with the epoxy adhesive is held at −40 ° C. for 1 hour, then heated to 150 ° C., held for 1 hour, and cooled to −40 ° C. again is taken as one cycle. A heat cycle test was repeated 2000 times. After the test, the interface between the PAS composition case and the epoxy adhesive was observed.

The evaluation criteria are shown below.
○: No crack at the interface between the case made of the PAS composition and the epoxy adhesive.
X: Cracks occurred at the interface between the case made of the PAS composition and the epoxy adhesive.

~ Measurement of melt viscosity of PAS ~
The melt viscosity was measured under the conditions of a measurement temperature of 315 ° C. and a load of 10 kg with a Koka type flow tester (manufactured by Shimadzu Corporation, trade name CFT-500) equipped with a die having a diameter of 1 mm and a length of 2 mm.

Synthesis Example 1 (Synthesis of poly (p-phenylene sulfide))
A 15 liter autoclave equipped with a stirrer was charged with 1866 g of Na ₂ S · 2.9H ₂ O and 5 l of N-methyl-2-pyrrolidone, gradually heated to 205 ° C. with stirring under a nitrogen stream, and 407 g of water was added. Distilled off. After cooling this system to 140 ° C., 2150 g of p-dichlorobenzene and 1500 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. This system was heated to 225 ° C. over 2 hours and polymerized at 225 ° C. for 2 hours, then heated to 250 ° C. over 30 minutes, and further polymerized at 250 ° C. for 3.0 hours. After completion of the polymerization, the mixture was cooled to room temperature and the polymer was isolated using a centrifuge. The polymer was repeatedly washed with warm water and dried overnight at 100 ° C. to obtain poly (p-phenylene sulfide) (hereinafter referred to as PPS (1)).

  The melt viscosity of the obtained PPS (1) was 280 poise.

Synthesis Example 2 (Synthesis of poly (p-phenylene sulfide))
The PPS (1) obtained in Synthesis Example 1 was further cured at 250 ° C. for 10 hours in an air atmosphere to obtain poly (p-phenylene sulfide) (hereinafter referred to as PPS (2)).

  The obtained PPS (2) had a melt viscosity of 28,000 poise.

Synthesis Example 3 (Synthesis of poly (p-phenylene sulfide))
A 15 liter autoclave equipped with a stirrer is charged with 3.5 l of N-methyl-2-pyrrolidone and 2400 g of Na ₂ S · 5.0H ₂ O, and gradually heated to 205 ° C. with stirring over about 2 hours under a nitrogen stream. 970 g of water was distilled off. After cooling to 140 ° C., 1990 g of p-dichlorobenzene and 1.2 l of N-methyl-2-pyrrolidone were added, the temperature was raised to 250 ° C., and polymerization was performed at 250 ° C. for 3 hours to obtain a slurry. Next, 2100 g of n-decane was poured into the autoclave, heated to 250 ° C. and polymerized for 5 hours. After completion of the polymerization, the mixture was cooled to room temperature and the polymer was isolated using a centrifuge. The polymer was repeatedly washed with warm water and dried at 100 ° C. for a whole day and night to obtain poly (p-phenylene sulfide) (hereinafter referred to as PPS (3)). The melt viscosity of the obtained PPS (3) was 1600 poise.

Synthesis Example 4 (Synthesis of poly (p-phenylene sulfide))
A 15 liter autoclave equipped with a stirrer was charged with 1866 g of Na ₂ S · 2.9H ₂ O and 5 l of N-methyl-2-pyrrolidone, gradually heated to 205 ° C. with stirring under a nitrogen stream, and 407 g of water was added. Distilled off. After cooling the system to 140 ° C., 2280 g of p-dichlorobenzene and 1500 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. This system was heated to 225 ° C. over 2 hours and polymerized at 225 ° C. for 2 hours, then heated to 250 ° C. over 30 minutes, and further polymerized at 250 ° C. for 2.0 hours. After completion of the polymerization, the mixture was cooled to room temperature and the polymer was isolated using a centrifuge. Poly (p-phenylene sulfide) (hereinafter referred to as PPS (4)) is obtained by repeatedly washing the polymer with warm water and drying at 100 ° C. overnight.
The resulting PPS (4) had a melt viscosity of 110 poise.

Synthesis Example 5 (Synthesis of poly (p-phenylene sulfide))
The PPS (4) obtained in Synthesis Example 4 was further cured at 250 ° C. for 12 hours in an air atmosphere to obtain poly (p-phenylene sulfide) (hereinafter referred to as PPS (5)).

  The melt viscosity of the obtained PPS (5) was 36000 poise.

Example 1
PPS (3) 92.0% by weight obtained in Synthesis Example 3, bisphenol A type epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name: Epicron 7050; epoxy equivalent 2000, melting point 125 ° C.) (hereinafter referred to as epoxy) Resin (1).) 2.0% by weight, maleic anhydride-modified ethylene copolymer (manufactured by Atofina Japan, trade name Bondine AX-8390 [melt flow rate: 7 g / 10 min]) (hereinafter, Maleic anhydride-modified ethylene-based copolymer (1)) 5.5% by weight and carnauba wax (manufactured by Kanto Chemical Co., Ltd.) 0.5% by weight were previously prepared by Henschel mixer (manufactured by Mitsui Miike Chemical Co., Ltd.). , HENSCHEL FD20D / K). Then, using a twin screw extruder (trade name TEM-35B-102B, manufactured by Toshiba Machine Co., Ltd.) having a screw diameter of 37 mmφ, the poly (p-phenylene sulfide) composition was melt-kneaded and pelletized at a cylinder temperature of 300 ° C. (Hereinafter referred to as a PPS composition) was obtained, and the obtained PPS composition was dried at 175 ° C. for 5 hours.

  The obtained PPS composition was molded into a test piece by an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., trade name SE75S) set at a cylinder temperature of 310 ° C. and a mold temperature of 140 ° C. And the appearance of the molded product surface were evaluated. The results are shown in Table 1.

  In addition, the obtained PPS composition was mounted on a mold for a case (100 mm × 100 mm × height 30 mm, wall thickness 1.5 mm), and an injection molding machine (Sumitomo) set to a cylinder temperature of 310 ° C. and a mold temperature of 140 ° C. The product was molded into a case by a heavy machinery industry, trade name SE75S) and subjected to a heat cycle test. The results are shown in Table 1.

Example 2
PPS (3) 82.0 wt% obtained in Synthesis Example 2 instead of 92.0 wt%, Epoxy resin (1) 4.0 wt% instead of 2.0 wt%, anhydrous maleic Instead of 5.5% by weight of acid-modified ethylene copolymer (1), 10.0% by weight, and further for 100 parts by weight of PPS (2), a glass fiber having a fiber diameter of 10 μm and a fiber length of 3 mm (Japanese plate glass ( Co., Ltd. Chopped Strand: RES03-TP91) A PPS composition, a test piece, and a PPS case were obtained in the same manner as in Example 1 except that 28 parts by weight were supplied from the side feeder of the twin screw extruder. Was evaluated. The results are shown in Table 1.

Example 3
PPS (2) instead of 85.5 wt% PPS (3) obtained in Synthesis Example 3 64.0 wt%, epoxy resin (1) 5.0 wt% instead of 4.0 wt% anhydrous maleic anhydride Acid-modified ethylene copolymer (1) Instead of 10.0% by weight, maleic anhydride-modified ethylene copolymer (manufactured by Atofina Japan, trade name Bondine TX-8030 [melt flow rate: 3 g / 10 min] ) (Hereinafter referred to as maleic anhydride-modified ethylene copolymer (2)) 28.0 wt%, carnauba wax 0.5 wt% instead of 3.0 wt%, glass fiber 28 wt% instead of 80 parts by weight and the same method as in Example 2 except that 19.0 parts by weight of calcium carbonate (product name: Whiten P-30, manufactured by Shiraishi Calcium Co., Ltd.) is added to 100 parts by weight of PPS (3). P A PS composition, a test piece, and a case made of PPS were obtained and evaluated. The results are shown in Table 1.

Example 4
Instead of PPS (3) 64.0 wt%, PPS (1) 71.0 wt% obtained in Synthesis Example 1 and epoxy resin (1) 5.0 wt% instead of bisphenol A type epoxy resin (Dainippon Ink Chemical Industries, Ltd., trade name: Epicron 3050; epoxy equivalent 780, melting point 95 ° C.) (hereinafter referred to as epoxy resin (2)) 18% by weight, maleic anhydride-modified ethylene copolymer (2) 28 4.0 wt% instead of 0.0 wt%, 7.0 wt% instead of 3.0 wt% carnauba wax, and 100 wt% PPS (1) instead of 80.0 wt% glass fiber PPS composition was obtained in the same manner as in Example 3 except that 86.0 parts by weight and 37.0 parts by weight instead of 19.0 parts by weight of calcium carbonate were obtained, and a test piece, a PPS case was obtained. Perform those evaluations . The results are shown in Table 1.

Comparative Example 1
Instead of 92.0% by weight of PPS (3), 100% by weight of PPS (1) obtained in Synthesis Example 1 was used. Epoxy resin (1), maleic anhydride-modified ethylene copolymer (1) and carnauba wax were used. A test piece and a PPS case were obtained and evaluated in the same manner as in Example 1 except that they were not used. The results are shown in Table 2.

  The obtained PPS had low adhesive strength, the test piece was inferior in surface appearance, and the PPS case was inferior in heat cycleability.

Comparative Example 2
Except that PPS (3) was 97.5 wt% instead of PPS (3) 92.0 wt%, maleic anhydride-modified ethylene copolymer (1) was not used. By the same method as in Example 1, a PPS composition, a test piece, and a case made of a PPS composition were obtained and evaluated. The results are shown in Table 2.

  The obtained PPS composition had low adhesive strength, and the case made of PPS composition was inferior in heat cycle property.

Comparative Example 3
In the same manner as in Example 1 except that 94.0% by weight of PPS (3) was replaced by 94.0% by weight of PPS (1) obtained in Synthesis Example 1 and no epoxy resin (1) was used. A PPS composition, a test piece, and a case made of a PPS composition were obtained and evaluated. The results are shown in Table 2.

  The obtained PPS composition had low adhesive strength, and the case made of PPS composition was inferior in heat cycle property.

Comparative Example 4
Instead of 92.0% by weight of PPS (3), 96.0% by weight of PPS (5) obtained in Synthesis Example 5, and 2. 5% by weight of maleic anhydride-modified ethylene copolymer (1) A PPS composition and a test piece were obtained and evaluated in the same manner as in Example 1 except that the content was 0% by weight and no carnauba wax was used. The case made of the PPS composition could not be molded. The results are shown in Table 2.

  The obtained PPS composition had low adhesive strength, and the test piece was inferior in surface appearance.

Comparative Example 5
Instead of 92.0% by weight of PPS (3), 92.0% by weight of PPS (1) obtained in Synthesis Example 1, and cresol novolac type epoxy resin (3) instead of 2.0% by weight of epoxy resin (1) (Dainippon Ink & Chemicals, Inc., trade name: Epicron N-695; epoxy equivalent 230, melting point 95 ° C.) (hereinafter referred to as epoxy resin (3)) 2.0% by weight, as in Example 1 By the method, a PPS composition, a test piece, and a case made of a PPS composition were obtained and evaluated. The results are shown in Table 2.

  The obtained PPS composition had low adhesive strength, and the case made of PPS composition was inferior in heat cycle property.

Comparative Example 6
PPS (1) 68.0 wt% instead of 92.0 wt%, epoxy resin (3) 2.0 wt% instead of bisphenol A type epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name Epicron) 855; epoxy equivalent 185, liquid at room temperature (25 ° C.) (hereinafter referred to as epoxy resin (4)) 3.5 wt%, maleic anhydride modified ethylene copolymer (1) instead of 5.5 wt% The PPS composition, the test piece, and the case made of the PPS composition were obtained in the same manner as in Comparative Example 5 and evaluated. The results are shown in Table 2.

  The obtained PPS composition had low adhesive strength and severe mold contamination, and the PPS composition case was inferior in heat cycleability.

Claims (2)

Polyarylene sulfide having a melt viscosity of 200 to 30,000 poise measured at 315 ° C. under a load of 10 kg using a Koka type flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm. %, Bisphenol A type epoxy resin having an epoxy equivalent of 700 to 2100 and a melting point of 80 to 131 ° C. , 1 to 30% by weight of maleic anhydride-modified ethylene copolymer, and carnauba wax. A polyarylene sulfide composition comprising 2 to 10% by weight. 2. The composition according to claim 1, further comprising 10 to 200 parts by weight of an inorganic filler which is a fibrous filler and / or a plate-like or powdered inorganic substance with respect to 100 parts by weight of polyarylene sulfide. The polyarylene sulfide composition described.