Polyarylene sulfide resin composition and method for producing the same

Abstract

To provide a polyarylene sulfide resin composition which is excellent in tenacity such as impact resistance without damaging heat resistance, chemical resistance, flowability or the like, and to provide a production method of the same.SOLUTION: A polyarylene sulfide resin composition contains 1-50 pts.wt. of a thermoplastic elastomer (B) having a reactive functional group based on 100 pts.wt. of a polyarylene sulfide resin (A) and satisfies (a) and (b). (a) The polyarylene sulfide resin composition is turned into fine particles with a median size (D50) of 100 μm or less, then the fine particles are added to a solvent as large as 100 times by weight and stirred in a temperature range of 5-15°C lower than the boiling point of the solvent for 3 hours, and then the solution obtained after solid-liquid separation by filtration of 0.45 μm is dried and solidified. An amount of the residue at this time corresponds to 40 wt.% or less of the reactive thermoplastic elastomer (B) compounded with the polyarylene sulfide resin composition. (b) An MFR measured according to ISO 1133 is 10-200 g / 10 minutes.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a polyarylene sulfide resin composition that does not impair the inherent heat resistance, chemical resistance, and fluidity of polyarylene sulfide resin, and exhibits excellent toughness such as impact resistance. The present invention relates to a polyarylene sulfide resin composition that is particularly useful for applications such as hollow molded products like pipes and fittings manufactured by blow molding or extrusion molding. [Background technology]

[0002] Polyarylene sulfide resin is a resin that exhibits excellent properties such as heat resistance, chemical resistance, and fluidity, and due to these superior properties, it is widely used in electrical and electronic equipment components, automotive equipment components, and office automation equipment components. However, polyarylene sulfide resin has the drawback of poor toughness such as impact resistance and poor water pressure resistance when used in hollow molded products, so its use has been restricted in some applications.

[0003] Regarding attempts to improve the toughness of polyarylene sulfide resins, for example, a resin composition comprising (A) polyphenylene sulfide resin, (B) an amino group-containing compound, and (C) an elastomer containing epoxy groups, wherein the melting point of the resin composition is 225°C to 265°C, and in the morphology of a molded article made from the resin composition observed by transmission electron microscopy, (A) the polyphenylene sulfide resin forms a continuous phase, and (B) the amino group-containing compound and (C) the elastomer containing epoxy groups form a dispersed phase, and the tensile modulus of the resin composition is measured using an ASTM No. 1 dumbbell test specimen obtained by injection molding at a cylinder temperature of 300°C and a mold temperature of 150°C, with a chuck distance of 114 mm, a test distance of 100 mm, and a tensile speed of 10 mm / m. Proposals have been made for a polyphenylene sulfide resin composition having an elastic modulus (measured in a tensile test under the following conditions) of 1.0 MPa to 1000 MPa (see, for example, Patent Document 1), and a method for producing a resin composition for blow-molded articles, characterized by melt-mixing a polyarylene sulfide resin (A) having carboxyl groups at the ends in a ratio of 25 to 45 [μmol / g] in the resin, a non-Newtonian exponent of 0.90 to 1.15, and a melt viscosity measured at 300°C in the range of 1000 poise to 3000 poise, with an epoxy group-containing polyolefin (B) in a ratio of 5 to 30 parts by mass of the epoxy group-containing polyolefin (B) per 100 parts by mass of the polyarylene sulfide resin (A) (see, for example, Patent Document 2). [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2019-108537 [Patent Document 2] Patent No. 4936034 [Overview of the project] [Problems that the invention aims to solve]

[0005] However, the proposals in Patent Documents 1 and 2 concern polyarylene sulfide resin compositions or methods for producing the same, which are formulated by blending a thermoplastic elastomer having a functional group that can react with the polyarylene sulfide resin in order to improve the toughness of the polyarylene sulfide resin. However, there is no mention of verifying whether the polyarylene sulfide resin and the thermoplastic elastomer are actually reacting, and the basis for the reaction is not shown, so there were problems with the effect of the reaction on improving toughness being unclear and lacking stability.

[0006] Therefore, the present invention aims to provide a polyarylene sulfide resin composition that does not impair the inherent heat resistance, chemical resistance, and fluidity of polyarylene sulfide resin, and that exhibits excellent toughness such as impact resistance. More specifically, the present invention aims to provide a polyarylene sulfide resin composition that is particularly useful for applications such as hollow molded products like pipes and fittings manufactured by blow molding or extrusion molding. [Means for solving the problem]

[0007] As a result of diligent research to solve the above problems, the inventors of the present invention have found that a specific polyarylene sulfide resin composition can be made to have excellent toughness such as impact resistance and fluidity, and have completed the present invention.

[0008] In other words, the present invention relates to a polyarylene sulfide resin composition comprising 1 to 50 parts by weight of a thermoplastic elastomer (B) having reactive functional groups per 100 parts by weight of a polyarylene sulfide resin (A), characterized in that it satisfies the following (a) and (b). (a); Polyarylene sulfide resin composition with median diameter (D 50The fine particles are 100 μm or smaller, and the fine particles are added to a solvent at a ratio of 100 times their weight. The mixture is stirred for 3 hours at a temperature range 5 to 15°C lower than the boiling point of the solvent. The solution is then dried after solid-liquid separation by filtration through a 0.45 μm filter, and the amount of residue at this stage corresponds to 40% by weight or less of the reactive thermoplastic elastomer (B) blended into the polyarylene sulfide resin composition. (b) The MFR measured in accordance with ISO 1133 is 10-200 g / 10 min.

[0009] The present invention will be described in detail below.

[0010] The polyarylene sulfide resin composition of the present invention contains 1 to 50 parts by weight of a thermoplastic elastomer (B) having a reactive functional group per 100 parts by weight of a polyarylene sulfide resin (A). The polyarylene sulfide resin composition is (a); the polyarylene sulfide resin composition is divided into median diameter (hereinafter, D 50 (b) The requirements are met such that the particles are 100 μm or smaller, the particles are added to a solvent 100 times their weight, the mixture is stirred for 3 hours at a temperature range 5 to 15°C lower than the boiling point of the solvent, the solution is dried after solid-liquid separation by filtration through a 0.45 μm filter, and the amount of residue at that time is equivalent to 40% by weight or less of the thermoplastic elastomer (B) having reactive functional groups blended into the polyarylene sulfide resin composition, and (b) the MFR measured in accordance with ISO 1133 is 10 to 200 g / 10 min.

[0011] The polyarylene sulfide resin constituting the polyarylene sulfide resin composition of the present invention may be any polyarylene sulfide resin that generally belongs to the category referred to as polyarylene sulfide resin. Examples of such polyarylene sulfide resins include homopolymers or copolymers composed of p-phenylene sulfide units, m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfide sulfone units, phenylene sulfide ketone units, phenylene sulfide ether units, and biphenylene sulfide units. Specific examples of such polyarylene sulfide include poly(p-phenylene sulfide), polyphenylene sulfide sulfone, polyphenylene sulfide ketone, and polyphenylene sulfide ether. Among these, poly(p-phenylene sulfide) is particularly preferred because it results in a polyarylene sulfide resin component with excellent heat resistance and strength properties.

[0012] The polyarylene sulfide resin is preferably a polyarylene sulfide resin composition that has an excellent balance of toughness, such as impact resistance, and fluidity. It is preferable that the melt viscosity measured using a high-efficiency flow tester equipped with a die with a diameter of 1 mm and a length of 2 mm, under conditions of a measurement temperature of 315°C and a load of 10 kg, is 100 to 2500 poise, and particularly preferably 150 to 2000 poise.

[0013] The polyarylene sulfide resin can be produced by methods known for producing polyarylene sulfide resins, for example, by polymerizing an alkali metal sulfide salt and a polyhalo-aromatic compound in a polar solvent. Examples of polar organic solvents include N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone, cyclohexylpyrrolidone, dimethylformamide, and dimethylacetamide. Examples of alkali metal sulfide salts include anhydrous or hydrated sodium sulfide, rubidium sulfide, and lithium sulfide. Alternatively, the alkali metal sulfide salt may be obtained by reacting an alkali metal hydrosulfide salt with an alkali metal hydroxide. Examples of polyhalo-aromatic compounds include p-dichlorobenzene, p-dibromobenzene, p-diiodobenzene, m-dichlorobenzene, m-dibromobenzene, m-diiodobenzene, 4,4'-dichlorodiphenylsulfone, 4,4'-dichlorobenzophenone, 4,4'-dichlorodiphenyl ether, and 4,4'-dichlorodibiphenyl.

[0014] Furthermore, examples of polyarylene sulfide resins include linear polyarylene sulfide resins, polyarylene sulfide resins that have been heat-treated in oxygen to introduce crosslinked or branched structures, polyarylene sulfide resins that have been slightly crosslinked or branched by adding a small amount of trihalogen or greater polyhalogen compounds during polymerization, polyarylene sulfide resins in which part of the molecular chain and / or terminals have been modified with functional groups such as carboxyl groups, carboxymetal salts, alkyl groups, alkoxy groups, amino groups, and nitro groups, and polyarylene sulfide resins that have been heat-treated in a non-oxidizing inert gas such as nitrogen. Mixtures of these polyarylene sulfide resins are also acceptable. Among these, polyarylene sulfide resins in which part of the molecular chain has been modified with amino groups are preferred because they exhibit excellent reactivity with the reactive functional groups of thermoplastic elastomers and have excellent toughness such as impact resistance, making it easier to obtain such polyarylene sulfide resins. Furthermore, the polyarylene sulfide resin may be obtained by reducing impurities such as sodium atoms, polyarylene sulfide oligomers, sodium chloride, and sodium salt of 4-(N-methyl-chlorophenylamino)butanoate by acid washing, hot water washing, or washing with organic solvents such as acetone and methyl alcohol.

[0015] Examples of the reactive functional groups in the thermoplastic elastomer having a reactive functional group constituting the polyarylene sulfide resin composition of the present invention include epoxy groups, maleic anhydride groups, carboxylic acid groups, amino groups, isocyanate groups, etc. Examples of thermoplastic elastomers having such reactive groups include ethylene-α,β-unsaturated alkyl carboxylate-maleic anhydride copolymer, ethylene-α,β-unsaturated glycidyl carboxylate copolymer, ethylene-α,β-unsaturated glycidyl carboxylate-vinyl acetate copolymer, ethylene-α,β-unsaturated alkyl carboxylate copolymer, modified ethylene copolymers such as maleic anhydride graft-modified ethylene-α-olefin copolymer, and hydrogenated styrene-butadiene-styrene block copolymers. Examples include hydrogenated vinyl aromatic compound block copolymers modified with leic acid or its derivatives, hydrogenated styrene-butadiene block copolymers modified with maleic anhydride or its derivatives, hydrogenated styrene-isoprene block copolymers modified with maleic anhydride or its derivatives, and hydrogenated styrene-isoprene-styrene block copolymers modified with maleic anhydride or its derivatives. In addition, polyurethane thermoplastic elastomers, polyester thermoplastic elastomers, polyamide thermoplastic elastomers, acrylonitrile-butadiene rubber thermoplastic elastomers, ethylene-propylene copolymers, ethylene-propylene-diene copolymers, etc., can also be used as long as they have functional groups that can react with polyarylene sulfide resin. Among these, modified ethylene copolymers are preferred because they result in a polyarylene sulfide resin composition with particularly excellent toughness.

[0016] The amount of thermoplastic elastomer having the reactive functional group is preferably 1 part by weight or more and 50 parts by weight or less, and particularly preferably 5 parts by weight or more and 40 parts by weight or less, per 100 parts by weight of the polyarylene sulfide resin, in order to make it possible to create a polyarylene sulfide resin composition with an excellent balance between toughness such as impact resistance and fluidity. If the amount of thermoplastic elastomer having the reactive functional group is less than 1 part by weight, the polyarylene sulfide resin composition will have poor toughness, and if it exceeds 50 parts by weight, it will have poor fluidity.

[0017] The polyarylene sulfide resin composition of the present invention is (a) a polyarylene sulfide resin composition D 50 The material is defined as fine particles of 100 μm or less, the fine particles are added to a solvent at a ratio of 100 times their weight, the mixture is stirred for 3 hours at a temperature range 5 to 15°C lower than the boiling point of the solvent, and then the solution is dried after solid-liquid separation by filtration through a 0.45 μm filter, satisfying the requirement that the amount of residue at this stage corresponds to 40% by weight or less of the thermoplastic elastomer (B) having the combined reactive functional group.

[0018] Here, D of the polyarylene sulfide resin composition fine particles 50 If the particle size exceeds 100 μm, the solvent extraction of the thermoplastic elastomer component in the polyarylene sulfide resin composition fine particles becomes unstable. 50 The measurement method is not particularly limited, and known and publicly used methods such as microscopy, sieving, sedimentation, light scattering, inertia, and diffusion can be used, and in particular the D of polyarylene sulfide resin composition 50 Light scattering is preferred because it can measure accurately and easily. Also, when the polyarylene sulfide resin composition is a resin pellet or molded body, the pellet or molded body is D 50The method for making the fine particles 100 μm or less is not particularly limited, and known and commonly used methods such as dry grinding, wet grinding, and cryogenic grinding can be used. As the grinder, a roller mill, jet mill, hammer mill, pin mill, rotary mill, vibration mill, planetary mill, attritor, bead mill, etc. can be used.

[0019] Also, as the solvent at this time, there is no particular limitation as long as it is a solvent that dissolves the thermoplastic elastomer having a reactive functional group and does not dissolve the polyarylene sulfide resin. For example, toluene, xylene, dichlorobenzene, trichlorobenzene, chloronaphthalene, etc. can be used.

[0020] And the amount of the residue corresponds to 40% by weight or less of the thermoplastic elastomer (B) having a reactive functional group blended. That is, the weight of the residue is divided by the weight of the fine particles of the polyarylene sulfide resin composition to obtain the ratio of the residue, and then the ratio of the residue is divided by the constituent ratio of the thermoplastic elastomer in the polyarylene sulfide resin composition. When the ratio of the residue to the ratio of the thermoplastic elastomer blended in the polyarylene sulfide composition is 40% by weight or less, it becomes excellent in toughness such as impact resistance. Here, when it exceeds 40% by weight, the reaction between the polyarylene sulfide resin and the thermoplastic elastomer having a reactive functional group is insufficient, and the affinity and compatibility between the polyarylene sulfide resin and the thermoplastic elastomer having a reactive functional group are poor. Therefore, the polyarylene sulfide resin composition is poor in toughness such as impact resistance.

[0021] The polyarylene sulfide resin composition of the present invention satisfies the requirement that, as (b), the MFR measured in accordance with ISO 1133 is 10 to 200 g / 10 min. Here, when the MFR is less than 10 g / 10 min, the polyarylene sulfide resin composition has poor fluidity, and when it exceeds 200 g / 10 min, it has poor toughness.

[0022] The polyarylene sulfide resin composition of the present invention may contain non-fibrous fillers, to the extent that it does not depart from the objectives of the present invention. Examples of non-fibrous fillers include silicates such as wollastonite, zeolite, sericite, kaolin, mica, pyrophyllite, talc, and aluminasilicate; oxides such as aluminum oxide, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, zinc oxide, and iron oxide; carbonates such as calcium carbonate, magnesium carbonate, and dolomite; sulfates such as calcium sulfate and barium sulfate; nitrides such as silicon nitride, boron nitride, and aluminum nitride; and glass flakes and glass beads. Among these, mica, talc, calcium carbonate, glass flakes, and glass beads are preferred. Furthermore, the non-fibrous filler may be surface-treated with isocyanate compounds, silane coupling agents, titanate coupling agents, epoxy compounds, and the like.

[0023] Furthermore, the polyarylene sulfide resin composition of the present invention preferably contains a silane coupling agent (C) comprising a trialkoxysilane coupling agent having a glycidyl group and / or a trialkoxysilane coupling agent having an amino group, as this provides excellent toughness and other properties. The silane coupling agent (C) is not particularly limited as long as it is a trialkoxysilane coupling agent having a glycidyl group or an amino group. Specific examples of those belonging to this category include 3-glycidoxypropylmethyldimethoxysilane, 3-glycidoxypropyltrimethoxysilane, 3-glycidoxypropylmethyldiethoxysilane, 3-glycidoxypropyltriethoxysilane, 3-aminopropyltrimethoxysilane, 3-aminopropyltriethoxysilane, N-phenyl-3-aminopropyltrimethoxysilane, N-2-(aminoethyl)-3-aminopropylmethyldimethoxysilane, N-2-(aminoethyl)-3-aminopropyltrimethoxysilane, and the like. Furthermore, the amount of the silane coupling agent (C) is preferably 0.1 to 3 parts by weight per 100 parts by weight of the polyarylene sulfide resin.

[0024] Furthermore, the polyarylene sulfide resin composition of the present invention preferably contains a release agent (D) to improve mold release properties and appearance when forming molded articles. Suitable release agents (D) include, for example, polyethylene wax, polypropylene wax, and fatty acid amide wax. Commonly available commercially available polyethylene wax and polypropylene wax can be used. The fatty acid amide wax is a polycondensate composed of a higher aliphatic monocarboxylic acid, a polybasic acid, and a diamine; any product belonging to this category can be used. For example, a polycondensate composed of stearic acid, sebacic acid, and ethylenediamine, such as (trade name) Light Amid WH-255 (manufactured by Kyoeisha Chemical Co., Ltd.), can be cited.

[0025] The polyarylene sulfide resin composition of the present invention may be used in combination with various additives without departing from the objectives of the present invention. For example, one or more conventional additives such as plasticizers, antioxidants, heat stabilizers, UV inhibitors, and foaming agents, such as conventionally known polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, and organophosphorus compounds, may be added. Furthermore, it may be a mixture of one or more thermoplastic resins such as various thermosetting resins, thermoplastic elastomers without reactive functional groups, epoxy resins, cyanate ester resins, phenolic resins, polyimides, silicone resins, polyesters, polyamides, polyphenylene oxides, polycarbonates, polysulfones, polyetherimides, polyethersulfones, polyetherketones, polyetheretherketones, polyamideimides, and polyalkylene oxides.

[0026] Furthermore, the polyarylene sulfide resin composition of the present invention can be used in combination with a fibrous filler (E), and examples of such fibrous fillers include glass fibers; carbon fibers such as PAN-based carbon fibers and pitch-based carbon fibers; graphitized fibers; whiskers such as silicon nitride whiskers, basic magnesium sulfate whiskers, barium titanate whiskers, potassium titanate whiskers, silicon carbide whiskers, boron whiskers, and zinc oxide whiskers; metal fibers such as stainless steel fibers; inorganic fibers such as rock wool, zirconia, alumina silica, barium titanate, silicon carbide, alumina, silica, and blast furnace slag; organic fibers such as fully aromatic polyamide fibers, phenolic resin fibers, and fully aromatic polyester fibers; and mineral fibers such as wollastonite and magnesium oxysulfate. In particular, glass fibers are preferred as they result in a polyarylene sulfide resin composition with excellent mechanical strength and impact resistance. Any type of glass fiber that is generally referred to as glass fiber may be used. Specific examples of the glass fibers include chopped strands with an average fiber diameter of 6 to 14 μm, chopped strands made of flattened glass fibers with an aspect ratio of 2 to 4 in the fiber cross-section, milled fibers, roving, etc.; silane fibers; aluminosilicate glass fibers; hollow glass fibers; non-enamel glass fibers, etc. Among these, chopped strands with an average fiber diameter of 6 to 14 μm or chopped strands made of flattened glass fibers with an aspect ratio of 2 to 4 in the fiber cross-section are particularly preferred as they result in a polyarylene sulfide resin composition with excellent mechanical strength, impact resistance, and fluidity. Two or more of these fibrous fillers can be used in combination, and if necessary, they may be pre-surface-treated with functional compounds or polymers such as epoxy compounds, isocyanate compounds, silane compounds, titanate compounds, etc. The amount of the fibrous filler (E) is preferably 10 to 150 parts by weight, and particularly preferably 20 to 140 parts by weight, per 100 parts by weight of polyarylene sulfide resin, in order to obtain a polyarylene sulfide resin composition that has an excellent balance of toughness, mechanical strength, and fluidity.

[0027] As a method for producing the polyarylene sulfide resin composition of the present invention, conventionally used heating, melting, and kneading methods can be used. For example, heating, melting, and kneading methods using a single-screw or twin-screw extruder, kneader, mill, brabender, etc. are used, and a heating, melting, and kneading method using a twin-screw extruder, which has excellent kneading capacity, is particularly preferred. Furthermore, it is preferable that the screw used in the twin-screw extruder has two or more kneading zones. In addition, by ensuring a sufficient reaction time between the polyarylene sulfide resin and the thermoplastic elastomer having reactive functional groups, it becomes possible to efficiently produce a polyarylene sulfide resin composition with excellent toughness such as impact resistance. Therefore, the ratio of screw length L to screw diameter D (L / D) is preferably 30 or more, and particularly preferably 40 or more. Furthermore, in order to ensure a sufficient reaction between the polyarylene sulfide resin and the thermoplastic elastomer having reactive functional groups and to easily suppress the thermal decomposition of the thermoplastic elastomer, it is preferable to set the cylinder temperature of the kneading zone of the twin-screw extruder to 265°C to 320°C, and particularly preferably to 270°C to 310°C. Furthermore, to ensure good dispersibility and distribution of the thermoplastic elastomer phase having reactive functional groups within the polyarylene sulfide resin phase of the polyarylene sulfide resin composition, resulting in a polyarylene sulfide resin composition with excellent toughness such as impact resistance, the peripheral speed of the screw is preferably 50 to 400 mm / second, and particularly preferably 150 to 300 mm / second. In addition, the residence time of the molten resin in the extruder is preferably 30 to 100 seconds, and particularly preferably 30 to 80 seconds, in order to allow sufficient reaction time between the polyarylene sulfide resin and the thermoplastic elastomer having reactive functional groups, and to facilitate the suppression of thermal decomposition of the thermoplastic elastomer.

[0028] Furthermore, the polyarylene sulfide resin composition of the present invention can be molded into any shape using an injection molding machine, extrusion molding machine, transfer molding machine, compression molding machine, etc.

[0029] The polyarylene sulfide resin composition of the present invention possesses excellent toughness properties such as resistance to thermal shock, without impairing the heat resistance, chemical resistance, and fluidity inherent in polyarylene sulfide resins. It is therefore suitably used in applications requiring these properties, such as electrical and electronic components or automotive parts, and particularly in applications such as hollow molded products like pipes and fittings manufactured by blow molding or extrusion molding. [Effects of the Invention]

[0030] According to the present invention, a polyarylene sulfide resin composition is provided that is excellent in toughness such as resistance to thermal shock, as well as fluidity and mechanical strength, and is particularly useful for applications such as electrical and electronic components or automotive parts, and its industrial value is extremely high. [Examples]

[0031] The present invention will be described in detail below with reference to examples, but the present invention is not limited in any way thereto.

[0032] The polyarylene sulfide (A), thermoplastic elastomer (B), silane coupling agent (C), mold release agent (D), and fibrous filler (E) used in the examples and comparative examples are shown below.

[0033] <Polyarylene sulfide (A)> Poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-1)): Melt viscosity 470 poise. Poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-2)): Melt viscosity 820 poise. Poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-3)): Melt viscosity 1580 poise. Poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-4)): Melt viscosity 2520 poise. Poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-5)): Melt viscosity 80 poise.

[0034] <Thermoplastic elastomer (B)> Ethylene-α,β-unsaturated carboxylate alkyl ester-maleic anhydride copolymer (B-1) (hereinafter simply referred to as thermoplastic elastomer (B-1)); manufactured by SK global chemical, (product name) Bondine AX8390, reactive group: maleic anhydride, ethylene residue units: α,β-unsaturated carboxylate alkyl ester residue units: maleic anhydride residue units (weight ratio) = 69.7:29:1.3. Ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid methyl ester copolymer (B-2) (hereinafter simply referred to as thermoplastic elastomer (B-2)): Manufactured by Sumitomo Chemical Co., Ltd., (product name) Bondfast 7M, Reactive group: epoxy group, Ethylene residue unit: α,β-unsaturated carboxylic acid glycidyl ester residue unit: α,β-unsaturated carboxylic acid methyl ester residue unit (weight ratio) = 67:6:27. Ethylene-α,β-unsaturated carboxylate alkyl ester copolymer (B'-3) (hereinafter simply referred to as thermoplastic elastomer (B'-3)); manufactured by SK global chemical, (product name) LOTRYL 35BA40T, reactive groups: none, ethylene residue units: α,β-unsaturated carboxylate alkyl ester residue units (weight ratio) = 65:35.

[0035] <Silane coupling agent (C)> Trialkoxysilane coupling agent containing an amino group (C-1); manufactured by Shin-Etsu Chemical Co., Ltd., (product name) KBM-903; 3-aminopropyltrimethoxysilane. Trialkoxysilane coupling agent (C-2) containing a glycidyl group; manufactured by Shin-Etsu Chemical Co., Ltd., (product name) KBM-403; 3-glycidoxypropyltrimethoxysilane.

[0036] <Release agent (D)> Release agent (D-1); manufactured by Kyoeisha Chemical Co., Ltd., (product name) Light Amid WH-255.

[0037] <Fibrous filler (E)> Glass fiber (E-1); manufactured by Nippon Electric Glass Co., Ltd., (product name) T-760H; fiber diameter 10 μm, fiber length 3 mm. Glass fiber (E-2); chopped strand manufactured by Nitto Boseki Co., Ltd., (product name) CSG-3PA 830, aspect ratio of fiber cross-section 4.

[0038] Synthesis Example 1 In a 50-liter autoclave equipped with a stirrer, 6214 g of Na2S·2.9H2O and 17000 g of N-methyl-2-pyrrolidone were charged. The mixture was gradually heated to 205°C while stirring under a nitrogen stream, and 1355 g of water was removed by distillation. After cooling the system to 140°C, 7168 g of p-dichlorobenzene, 12 g of 3,5-dichloroaniline, and 5000 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. The system was heated to 225°C over 2 hours, polymerized at 225°C for 2 hours, then heated to 250°C over 30 minutes, and polymerized further at 250°C for 3 hours. After polymerization was complete, the system was cooled to room temperature, and the solid was isolated by centrifugation. The solid was washed with 180°C hot water and dried at 100°C overnight to obtain poly(p-phenylene sulfide).

[0039] The obtained poly(p-phenylene sulfide) was dried in a vacuum dryer under reduced pressure at 240°C for 4 hours to obtain linear amino group-containing poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-1)). The melt viscosity of PPS(A-1) was 470 poise.

[0040] Synthesis Example 2 In a 50-liter autoclave equipped with a stirrer, 6214 g of Na2S·2.9H2O and 17000 g of N-methyl-2-pyrrolidone were charged. The mixture was gradually heated to 205°C while stirring under a nitrogen stream, and 1355 g of water was removed by distillation. After cooling the system to 140°C, 7180 g of p-dichlorobenzene, 6 g of 3,5-dichloroaniline, and 5000 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. The system was heated to 225°C over 2 hours, polymerized at 225°C for 2 hours, then heated to 250°C over 30 minutes, and polymerized further at 250°C for 3 hours. After polymerization was complete, the system was cooled to room temperature, and the solid was isolated by centrifugation. The solid was washed with hot water at 180°C and dried at 100°C overnight to obtain poly(p-phenylene sulfide).

[0041] The obtained poly(p-phenylene sulfide) was dried in a vacuum dryer under reduced pressure at 240°C for 6 hours to obtain linear amino group-containing poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-2)). The melt viscosity of PPS(A-2) was 820 poise.

[0042] Synthesis Example 3 Poly(p-phenylene sulfide) was obtained by the same polymerization method as in Synthesis Example 1, except that 3,5-dichloroaniline was not used.

[0043] The obtained poly(p-phenylene sulfide) was cured at 250°C for 3 hours in an air atmosphere to obtain branched poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-3)). The melt viscosity of PPS(A-3) was 1580 poise.

[0044] Synthesis Example 4 Poly(p-phenylene sulfide) was obtained by the same polymerization method as in Synthesis Example 2, except that 3,5-dichloroaniline was not used.

[0045] The obtained poly(p-phenylene sulfide) was cured at 250°C for 5 hours in an air atmosphere to obtain branched poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-4)). The melt viscosity of PPS(A-4) was 2520 poise.

[0046] Synthesis Example 5 In a 15-liter autoclave equipped with a stirrer, 1814 g of Na2S·2.9H2O, 8.7 g of granular caustic soda (100% NaOH: Wako Pure Chemical Industries special grade), and 3232 g of N-methyl-2-pyrrolidone were charged. The mixture was gradually heated to 200°C while stirring under a nitrogen stream, and 339 g of water was distilled off. After cooling the system to 190°C, 2085 g of p-dichlorobenzene and 1783 g of N-methyl-2-pyrrolidone were added, and the system was sealed under a nitrogen stream. The system was heated to 225°C over 2 hours, polymerized at 225°C for 1 hour, then heated to 250°C over 25 minutes, and polymerized at 250°C for another 2 hours. After polymerization was complete, the mixture was cooled to room temperature, and the solid components were isolated by centrifugation. The solid was washed with hot water at 180°C and dried at 105°C overnight to obtain poly(p-phenylene sulfide).

[0047] The obtained poly(p-phenylene sulfide) was dried in a vacuum dryer under reduced pressure at 240°C for 6 hours to obtain linear poly(p-phenylene sulfide) (hereinafter referred to as PPS(A-5)). The melt viscosity of PPS(A-5) was 80 poise.

[0048] The evaluation and measurement methods for the obtained polyarylene sulfide resin composition are shown below.

[0049] ~Measuring the melt viscosity of polyarylene sulfide resin~ The melt viscosity was measured using a high-efficiency flow tester (manufactured by Shimadzu Corporation, product name CFT-500) equipped with a die with a diameter of 1 mm and a length of 2 mm, under conditions of a measurement temperature of 315°C and a load of 10 kg.

[0050] ~D 50 Measurement ~ The pellets of the polyarylene sulfide resin compositions obtained in the examples and comparative examples were cooled using liquid nitrogen and mechanically pulverized, and the fine particles of the polyarylene sulfide resin compositions thus obtained were used to measure D 50 by a laser scattering particle size distribution analyzer (manufactured by Horiba, Ltd., trade name: LA-500).

[0051] ~Ratio of residue to ratio of thermoplastic elastomer blended in polyarylene sulfide resin composition~ The pellets of the polyarylene sulfide compositions obtained in the examples and comparative examples were cooled using liquid nitrogen and mechanically pulverized. 3 g of the fine particles of the polyarylene sulfide resin composition were immersed in a glass container containing 300 g of toluene (boiling point: 110°C), stirred at a temperature of 100°C for 3 hours, then filtered through a 0.45-μm filter, and the filtrate was evaporated to dryness to recover the residue, and the weight was measured. Then, the weight was divided by the weight (3 g) of the fine particles of the obtained polyarylene sulfide composition to obtain the ratio of the residue. Then, the ratio of the residue was divided by the composition ratio of the thermoplastic elastomer in the polyarylene sulfide resin composition to obtain the ratio of the residue to the ratio of the thermoplastic elastomer blended in the polyarylene sulfide composition.

[0052] ~Evaluation of fluidity of polyarylene sulfide resin composition~ Using the obtained polyarylene sulfide resin composition, the MFR was measured in accordance with ISO 1133. Those with an MFR of 10 g / 10 min or more were considered to have excellent fluidity.

[0053] ~Measurement of Charpy impact strength (with notch) of polyarylene sulfide resin composition~ Test pieces were produced using an injection molding machine (manufactured by Sumitomo Heavy Industries, Ltd., trade name: SE-75S) and measured in accordance with ISO 179-1. Those with a Charpy impact strength of 5 kJ / m 2 or more were considered to have excellent impact resistance.

[0054] ~Evaluation of water pressure resistance~ A hollow molded body with a wall thickness of 2 mm, an outer diameter of 30 mm, and a length of 200 mm was fabricated using a suction blow molding machine. After connecting it to a hose of a manual test pump (manufactured by Kyowa) filled with water, the air inside the test part was removed, the test part was plugged, and water was injected into the test part using a manual handle. The maximum water pressure until the water pressure dropped due to the failure of the test part was measured. Parts with a maximum water pressure of 5 MPa or higher were considered to have excellent water pressure resistance.

[0055] Example 1 To 100 parts by weight of PPS(A-2) obtained in Synthesis Example 2, 10 parts by weight of thermoplastic elastomer (B-1) were uniformly mixed beforehand. This mixture was then fed into the hopper of a twin-screw extruder (manufactured by Japan Steel Works Ltd., product name TEX-25αIII, L / D=55) with four kneading zones. The mixture was melt-kneaded at a raw material supply rate of 25 kg / hr and a screw rotation speed of 200 rpm (peripheral speed: 258 mm / sec) with the cylinder temperature of the kneading zones heated to 285°C. After a residence time of 50 seconds, the molten composition flowing out of the die was cooled and cut to produce a pellet-shaped polyarylene sulfide resin composition. The composition of the polyarylene sulfide resin composition was 91% by weight of PPS(A-2) and 9% by weight of thermoplastic elastomer (B-1), and the MFR of the polyarylene sulfide resin composition was 150 g / 10 min.

[0056] Furthermore, the polyarylene sulfide resin composition pellets are mechanically crushed under the above conditions to obtain D 50 Fine particles of a polyarylene sulfide resin composition with a diameter of 30 μm were obtained. Next, the residue recovered by evaporating the filtrate using these fine particles of the polyarylene sulfide resin composition was measured and found to be 0.075 g (corresponding to 28 wt% of thermoplastic elastomer (B-1)).

[0057] Furthermore, the polyarylene sulfide resin composition was injection molded using an injection molding machine (Sumitomo Heavy Industries, Ltd., product name SE75) heated to a cylinder temperature of 300°C and a mold temperature of 140°C to produce test pieces for evaluating tensile fracture elongation and Charpy impact strength. The results of each evaluation are shown in Table 1.

[0058] The resulting polyarylene sulfide resin composition exhibited excellent tensile fracture elongation, impact resistance, fluidity, and hydrostatic pressure resistance.

[0059] Examples 2-8 A pelletized polyarylene sulfide resin composition was prepared using the same method as in Example 1, with the mixing ratios of polyarylene sulfide (A), thermoplastic elastomer (B), silane coupling agent (C), and mold release agent (D) and the melt-kneading conditions shown in Table 1. These polyarylene sulfide resin composition pellets were mechanically ground to obtain fine particles of the polyarylene sulfide resin composition D. 50 All samples were 100 μm or smaller. They were then evaluated using the same method as in Example 1. The evaluation results are shown in Table 1.

[0060] The percentage of residue in all obtained polyarylene sulfide resin compositions was 40% by weight or less, and they exhibited excellent impact resistance, fluidity, and water pressure resistance.

[0061] Examples 9-11 Polyarylene sulfide (A) and thermoplastic elastomer (B) were fed into the hopper of a twin-screw extruder (manufactured by Japan Steel Works Ltd., product name TEX-25αIII, L / D=55) under the mixing ratios shown in Table 1. Meanwhile, an inorganic filler (E) was fed into the hopper of the side feeder of the same twin-screw extruder, and a pelletized polyarylene sulfide resin composition was prepared in the same manner as in Example 1, under the melt-kneading conditions shown in Table 1. These polyarylene sulfide resin composition pellets were mechanically pulverized to obtain the fine particles of the polyarylene sulfide resin composition. 50 All samples were 100 μm or smaller. They were then evaluated using the same method as in Example 1. The evaluation results are shown in Table 1.

[0062] The percentage of residue in all obtained polyarylene sulfide resin compositions is 40%. below It possessed excellent impact resistance, fluidity, and water pressure resistance.

[0063] [Table 1]

[0064] Comparative Examples 1-8 A polyarylene sulfide resin composition in pellet form was prepared using the same method as in Example 1, with the blending ratio of polyarylene sulfide (A) and thermoplastic elastomer (B) and the melt-kneading conditions shown in Table 2. The polyarylene sulfide resin composition pellets were mechanically ground to obtain fine particles of the polyarylene sulfide resin composition. 50 All samples were 100 μm or smaller. They were then evaluated using the same method as in Example 1. The evaluation results are shown in Table 2.

[0065] The polyarylene sulfide resin compositions obtained from Comparative Examples 1, 2, 3, and 6 had a residue content exceeding 40% by weight, and exhibited poor impact resistance and hydrostatic pressure resistance. The polyarylene sulfide resin composition obtained from Comparative Example 4 exhibited poor impact resistance, fluidity, and hydrostatic pressure resistance. The polyarylene sulfide resin compositions obtained from Comparative Examples 5 and 8 exhibited poor impact resistance and hydrostatic pressure resistance. The polyarylene sulfide resin composition obtained from Comparative Example 7 exhibited poor fluidity and hydrostatic pressure resistance.

[0066] [Table 2] [Industrial applicability]

[0067] The present invention relates to a polyarylene sulfide resin composition that does not impair the inherent heat resistance, chemical resistance, and fluidity of polyarylene sulfide resins, and is excellent in toughness such as impact resistance, and is particularly useful for applications such as hollow molded products such as pipes and fittings manufactured by blow molding or extrusion molding.

Claims

1. A polyarylene sulfide resin composition for molding water pressure resistant parts, characterized in that it is a heated and melted kneaded mixture of 100 parts by weight of a polyarylene sulfide resin (A) having a melt viscosity of 150 to 2000 poise at a measurement temperature of 315°C and a load of 10 kg, measured using a high-efficiency flow tester equipped with a die of 1 mm in diameter and 2 mm in length, and 5 to 40 parts by weight of a thermoplastic elastomer (B) having at least one reactive functional group selected from the group consisting of epoxy groups, maleic anhydride groups, carboxylic acid groups, amino groups and isocyanate groups, wherein the composition satisfies the following (a) and (b) and is for use in water pressure resistant parts with a maximum water pressure of 5 MPa or more. (a) Prepare a solvent that dissolves the thermoplastic elastomer (B) having a reactive functional group but does not dissolve the polyarylene sulfide resin (A), and dissolve the polyarylene sulfide resin composition in a median diameter (D ５０ The fine particles are 100 μm or smaller, and the fine particles are added to the solvent at a ratio of 100 times their weight. The mixture is stirred for 3 hours at a temperature range 5 to 15°C lower than the boiling point of the solvent. The solution is then dried after solid-liquid separation by filtration through a 0.45 μm filter, and the amount of residue at this stage corresponds to 40% by weight or less of the thermoplastic elastomer (B) having reactive functional groups incorporated into the composition before heating, melting, and kneading. (b) The MFR measured in accordance with ISO 1133 and JIS K7315-1 Data Block 3 Code A5 is 10 to 200 g / 10 min.

2. The polyarylene sulfide resin composition for molding water pressure resistant parts according to claim 1, characterized in that the thermoplastic elastomer (B) having a reactive functional group is at least one modified ethylene copolymer selected from the group consisting of ethylene-α,β-unsaturated carboxylic acid alkyl ester-maleic anhydride copolymer, ethylene-α,β-unsaturated carboxylic acid glycidyl ester copolymer, ethylene-α,β-unsaturated carboxylic acid glycidyl ester-vinyl acetate copolymer, ethylene-α,β-unsaturated carboxylic acid glycidyl ester-α,β-unsaturated carboxylic acid alkyl ester copolymer, and maleic anhydride graft-modified ethylene-α-olefin copolymer.

3. Furthermore, the polyarylene sulfide resin composition for molding water pressure resistant parts according to claim 1 or 2 is characterized by comprising a silane coupling agent (C) comprising a trialkoxysilane coupling agent having a glycidoxy group and / or a trialkoxysilane coupling agent having an amino group.

4. Furthermore, the polyarylene sulfide resin composition for molding water pressure resistant parts according to any one of claims 1 to 3 is characterized by comprising at least one release agent (D) selected from the group consisting of polyethylene wax, polypropylene wax, and fatty acid amide wax.

5. Furthermore, the polyarylene sulfide resin composition for molding water pressure resistant parts according to any one of claims 1 to 4 is characterized by containing a fibrous filler (E).

6. A method for producing a polyarylene sulfide resin composition for molding water-resistant parts according to any one of claims 1 to 5, characterized by using a twin-screw extruder having a ratio of screw length L to screw diameter D (L / D) of 30 or more and two or more kneading zones, and melt-kneading and extruding a thermoplastic elastomer having at least one reactive functional group selected from the group consisting of epoxy groups, maleic anhydride groups, carboxylic acid groups, amino groups and isocyanate groups, under the conditions of a cylinder temperature of 270 to 310°C, a screw peripheral speed of 50 to 400 mm / second, and a residence time of 30 to 100 seconds in the kneading zone of the twin-screw extruder, at least a polyarylene sulfide resin and at least one reactive functional group selected from the group consisting of epoxy groups, maleic anhydride groups, carboxylic acid groups, amino groups and isocyanate groups.

7. A hollow molded article for water pressure resistant parts, characterized by being a blow-molded article of the polyarylene sulfide resin composition described in any one of claims 1 to 5.

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