JP2006002105A - Polyarylene sulfide composition and case containing it - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyarylene sulfide composition having an excellent mechanical property, heat resistance and molding, and improving an adhesion property to an epoxy resin, urethane resin and silicone resin, and a case having an excellent adhesion property containing it. <P>SOLUTION: The polyarylene sulfide composition comprises 60-99.3% by weight of thermosetting polyarylene sulfide in which a melting viscosity, measured under the conditions that measurement temperature is 315°C and load is 10 kg in the Koka-type flow tester with dies of 1 mm in diameter, 2 mm length, is 300-30,000 poises, 0.5-30% by weight of a bisphenol A type epoxy resin in which an epoxy equivalent is 450-2,300 and a melting point is 50-135°C, and 0.2-10% by weight of carnauba wax. The case comprises it. <P>COPYRIGHT: (C)2006,JPO&NCIPI

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. The present invention relates to a sulfide composition and a case comprising the sulfide composition and excellent in adhesiveness.

  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).

JP 63-089544 A

JP 63-118342 A Japanese Patent Laid-Open No. 02-272063 JP 59-05944 A

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

  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 and carnauba wax has mechanical properties, heat resistance, molding processability, epoxy resin, urethane resin, and silicone. The present inventors have found that the adhesiveness to the resin is excellent and completed the present invention.

  That is, the present invention is a thermosetting type having a melt viscosity of 300 to 30000 poise measured under the conditions of a measurement temperature of 315 ° C. and a load of 10 kg using a Koka flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm. It is composed of 0.5 to 30% by weight of a bisphenol A type epoxy resin having a PAS of 60 to 99.3% by weight, an epoxy equivalent of 450 to 2300, and a melting point of 50 to 135 ° C. and 0.2 to 10% by weight of carnauba wax. A PAS composition characterized by the above, and a case comprising the same.

  The present invention is described in detail below.

  The PAS used in the present invention is a heat having a melt viscosity of 300 to 30000 poise measured at a temperature of 315 ° C. and a load of 10 kg with a Koka flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm. Examples of the PAS include p-phenylene sulfide units, m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfide sulfone units, phenylene sulfides represented by the following general formulas (1) to (8). A homopolymer or a copolymer comprising a ketone unit, a phenylene sulfide ether unit, a biphenyl sulfide unit, or a substituent-containing phenylene sulfide unit can be exemplified. Specific examples of these homopolymers or copolymers include poly ( p-phenylene sulfide), polyphenylene sulfide Hydrosulfone, 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 polyphenylenes In particular, poly (p-phenylene sulfide) and amino group-substituted poly (p-phenylene sulfide) are preferable because a PAS composition having excellent heat resistance and adhesiveness can be obtained. .

（ここで、式中Ｒはアルキル基、フェニル基、ニトロ基、カルボキシル基、ニトリル基、アミノ基、アルコキシル基、ヒドロキシル基又はスルホン酸基を示し、ｎは１〜４の整数を示す。）
さらに、本発明に用いられる熱硬化型ＰＡＳは、酸素存在下高温で処理する加熱硬化により架橋・分岐構造を有するものであり、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３００〜３００００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３００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。

(Here, R represents an alkyl group, a phenyl group, a nitro group, a carboxyl group, a nitrile group, an amino group, an alkoxyl group, a hydroxyl group or a sulfonic acid group, and n represents an integer of 1 to 4).
Furthermore, the thermosetting PAS used in the present invention has a cross-linked / branched structure by heat curing processed at a high temperature in the presence of oxygen, and is applied to an elevated flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm. The melt viscosity measured under the conditions of a measurement temperature of 315 ° C. and a load of 10 kg is 300 to 30000 poise, preferably 500 to 20000 poise. Here, when the melt viscosity is less than 300 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.

  In addition, the thermosetting PAS used in the present invention is a non-oxidizing material such as nitrogen as a pretreatment even if a small amount of a polyhalogen compound of trihalogen or higher is added during polymerization to introduce a slight cross-linked or branched structure. The heat treatment may be performed in a natural inert gas, or a mixture of these structures may be used. 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 thermosetting PAS used in the present invention is a PAS composition with particularly improved toughness and weld strength. Therefore, the measurement temperature is measured with an elevated flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm. It is preferably obtained by heat-curing an uncured uncured PAS having a melt viscosity of 150 poise or higher, preferably 250 poise or higher, measured at 315 ° C. and a load of 10 kg.

  The blending amount of the PAS constituting the PAS composition of the present invention is 60 to 99.3% by weight, and particularly 75 to 95% by weight because the PAS composition is excellent in 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 99.3% 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 ° C. to 135 ° C. Among them, the epoxy equivalent is 700 to 2100 and the melting point is 80 to 131. An epoxy resin composed of bisphenol A at 0 ° C. is preferable, and the property is obtained when a solid bisphenol A type epoxy resin containing two or more epoxy groups is used and an epoxy resin other than the bisphenol A type epoxy resin is obtained. The PAS composition has poor 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 30% by weight, and it becomes a PAS composition having excellent mechanical properties, heat resistance and adhesiveness. It is preferably 0 to 15.0% 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 30% by weight, the molding processability of the obtained PAS composition is remarkably lowered.

  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 carnauba wax exceeds 5% 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 further comprises 1 to 200 parts by weight of a fibrous filler and / or an inorganic filler with respect to 100 parts by weight of the thermosetting PAS. Those are preferred.

  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 fibers include various inorganic fibers such as rock wool, zirconia, alumina silica, barium titanate, silicon carbide, alumina, silica, and blast furnace slag.

  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 crystal nucleating agent such as talc, kaolin and silica, which is conventionally known; a polyalkylene oxide oligomer compound, a thioether compound, an ester compound, an organic compound, and the like, within a range not impairing the effects of the present invention. It is also possible to add one or more usual additives such as plasticizers such as phosphorus compounds; antioxidants; heat stabilizers; lubricants;

  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. Mix and use one or more of polycarbonate, polysulfone, polyetherimide, polyethersulfone, polyetherketone, polyetheretherketone, polyamideimide, polyamide elastomer, polyolefin elastomer, polyester elastomer, polyalkylene oxide, etc. be able to.

  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. There is no particular restriction on the mixing order of the raw materials, and all the raw materials are blended and then melt kneaded by the above method. After a part of the raw materials is blended, melt kneaded by the above method and the remaining raw materials are blended. Any method may be used, such as a method of melt kneading, or a method of mixing a part of raw materials and mixing the remaining raw materials using a side feeder during melt kneading with a single or twin screw extruder. 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 product 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 and a case comprising it are 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 specimen.

  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 obtained PAS composition was molded into a test piece or case (100 mm × 100 mm × height 30 mm, wall thickness 1.5 mm), 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 1000 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 uncured 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 washed repeatedly with warm water and dried overnight at 100 ° C. to obtain uncured 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 thermosetting poly (p-phenylene sulfide))
The PPS (1) obtained in Synthesis Example 1 was further cured at 250 ° C. in an air atmosphere for 3 hours to obtain thermosetting poly (p-phenylene sulfide) (hereinafter referred to as PPS (2)).

  The melt viscosity of the obtained PPS (2) was 1800 poise.

Synthesis Example 3 (Synthesis of thermosetting poly (p-phenylene sulfide))
The PPS (2) obtained in Synthesis Example 2 was further cured at 250 ° C. for 8 hours in an air atmosphere to obtain thermosetting poly (p-phenylene sulfide) (hereinafter referred to as PPS (3)).

  The melt viscosity of the obtained PPS (3) was 29000 poise.

Synthesis Example 4 (Synthesis of uncured 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. Uncured poly (p-phenylene sulfide) (hereinafter referred to as PPS (4)) 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 thermosetting poly (p-phenylene sulfide))
The PPS (4) obtained in Synthesis Example 4 was further cured at 250 ° C. for 10 hours in an air atmosphere to obtain thermosetting poly (p-phenylene sulfide) (hereinafter referred to as PPS (5)).

  The melt viscosity of the obtained PPS (5) was 38000 poise.

Example 1
94.0% by weight of PPS (3) obtained in Synthesis Example 3, bisphenol A type epoxy resin (manufactured by Dainippon Ink & Chemicals, Inc., trade name Epicron 7050; epoxy equivalent 2000, melting point 125 ° C.) (hereinafter referred to as epoxy) Resin (1))) 5.5% by weight and 0.5% by weight of carnauba wax were uniformly mixed in advance using a Henschel mixer. 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.

  Then, 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 to a cylinder temperature of 310 ° C. and a mold temperature of 140 ° C. Sexuality etc. were evaluated. The results are shown in Table 1.

  Also, an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., trade name) equipped with a case mold (100 mm × 100 mm × height 30 mm, wall thickness 1.5 mm) and set to a cylinder temperature of 310 ° C. and a mold temperature of 140 ° C. By SE75S), a PPS composition case was molded, and the surface appearance of the molded product was evaluated and a heat cycle test was performed. The results are shown in Table 1.

Example 2
Instead of 94.0 wt% of PPS (3), 94.2 wt% of PPS (2) obtained in Synthesis Example 2, 0.3 wt% instead of 0.5 wt% of carnauba wax, and further PPS (2 ) According to the same method as in Example 1 except that 87 parts by weight of glass fiber having a fiber diameter of 10 μm and a fiber length of 3 mm was supplied from the side feeder of the twin screw extruder with respect to 100 parts by weight, Cases made of PPS compositions were obtained and evaluated. The results are shown in Table 1.

Example 3
PPS (2) 97.6 wt% instead of 94.2 wt%, Epoxy resin (1) 2.0 wt% instead of 5.5 wt%, Carnauba wax 0.4 wt% instead of 0.3 wt% 80% by weight instead of 87 parts by weight of glass fiber, and 18.4 parts by weight of calcium carbonate (product name Whiten P-30, manufactured by Shiroishi Calcium Co., Ltd.) with respect to 100 parts by weight of PPS (2). A PPS composition, a test piece, and a case made of a PPS composition were obtained in the same manner as in Example 2 except that they were evaluated. The results are shown in Table 1.

Example 4
PPS (2) 81.6 wt% instead of 97.6 wt%, Epoxy resin (1) 2.0 wt% instead of bisphenol A type epoxy resin (Dainippon Ink Chemical Co., Ltd., trade name Epicron) 3050; epoxy equivalent 780, melting point 95 ° C. (hereinafter referred to as epoxy resin (2)) 18% by weight, and 36.8 instead of 18.4 parts by weight of calcium carbonate with respect to 100 parts by weight of PPS (2) A PPS composition, a test piece, and a case made of a PPS composition were obtained and evaluated by the same method as in Example 3 except that 86 parts by weight was used instead of 80 parts by weight and glass fiber. The results are shown in Table 1.

Comparative Example 1
The PPS composition was obtained in the same manner as in Example 1 except that 94.5% by weight of PPS (5) obtained in Synthesis Example 5 was used instead of 94.0% by weight of PPS (3), and no carnauba wax was used. The thing and the test piece were obtained and those evaluation was performed. The case made of the PPS composition could not be molded. The results are shown in Table 2.

  The test piece of the obtained PPS composition was inferior in surface appearance.

Comparative Example 2
Instead of the epoxy resin (1), a cresol novolac type epoxy resin (manufactured by Dainippon Ink and Chemicals, trade name: Epicron N-695; epoxy equivalent 230, melting point 95 ° C.) (hereinafter referred to as epoxy resin (3)). The PPS composition and the test piece were obtained and evaluated in the same manner as in Example 1 except that the above was changed. 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 3
PPS (3) 99.6 wt% instead of PPS (2) 99.6 wt%, carnauba wax 0.5 wt% instead of 0.4 wt%, except that the epoxy resin (1) was not used, By the same method as in Example 1, a PPS composition, a test piece, and a PPS composition-made case 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 epoxy resin (1), bisphenol A type epoxy resin (manufactured by Dainippon Ink & Chemicals, Inc., trade name Epicron 855; epoxy equivalent 185, liquid at room temperature (25 ° C.)) (hereinafter referred to as epoxy resin (4) and A PPS composition, a test piece, and a case made of a PPS composition were obtained and evaluated in the same manner as in Example 2 except that the above was changed. The results are shown in Table 2.

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

Comparative Example 5
PPS (2) 67.1% by weight instead of 94.2% by weight, Epoxy resin (1) 32.0% by weight instead of 5.5% by weight, Carnauba wax 0.3% by weight Instead, PPS compositions were obtained and evaluated in the same manner as in Example 2 except that the content was 0.9% by weight. Note that the test piece and the case made of the PPS composition could not be molded. The results are shown in Table 2.

  The obtained PPS composition was inferior in moldability.

Claims (4)

Thermosetting polyarylene sulfide 60 to 99 having a melt viscosity of 300 to 30000 poise measured at a temperature of 315 ° C. and a load of 10 kg using a Koka flow tester equipped with a die having a diameter of 1 mm and a length of 2 mm. It is characterized by comprising 0.5 to 30% by weight of a bisphenol A type epoxy resin having an epoxy equivalent of 450 to 2300 and a melting point of 50 to 135 ° C. and 0.2 to 10% by weight of carnauba wax. A polyarylene sulfide composition. Uncured polyarylene sulfide with a melt viscosity of 150 poise or more measured at a temperature of 315 ° C and a load of 10 kg can be thermally cured with a Koka flow tester equipped with a die with a diameter of 1 mm and a length of 2 mm. The polyarylene sulfide composition according to claim 1, which is a thermosetting polyarylene sulfide obtained. 3. The poly according to claim 1, further comprising 10 to 200 parts by weight of a fibrous filler and / or an inorganic filler with respect to 100 parts by weight of the thermosetting polyarylene sulfide. Arylene sulfide composition. A case obtained by injection-molding the polyarylene sulfide composition according to claim 1.