Polyarylene sulfide resin composition and molded article made therefrom

Abstract

To provide a polyarylene sulfide resin composition that is superior in terms of extrudability, reduced flash formation, high-temperature creep resistance, and flame retardancy.SOLUTION: A polyarylene sulfide resin composition comprises 100 pts.wt. of a resin component composed of (A) a polyarylene sulfide resin (component A) and (B) a thermoplastic resin (component B) in combination with 10 to 150 pts.wt. of (C) a fibrous reinforcing material (component C), 0.01 to 3 pts.wt. of (D) a silane compound having a reactive functional group (component D), and 1 to 30 pts.wt. of (E) boehmite (component E). The content of component B in 100 pts.wt. of the resin component is 10 to 50 pts.wt.SELECTED DRAWING: None

Description

Technical Field

[0001] The present invention relates to a resin composition comprising a polyarylene sulfide resin, a thermoplastic resin, a fibrous reinforcing material, a silane compound having a reactive functional group, and boehmite, and to a resin composition excellent in extrudability, low warpage property, high-temperature creep property, and flame retardancy, and a molded article made therefrom.

Background Art

[0002] Polyarylene sulfide resin is an engineering plastic excellent in chemical resistance, heat resistance, mechanical properties, etc. Therefore, polyarylene sulfide resin is widely used as electrical and electronic parts, vehicle-related parts, aircraft parts, and housing equipment parts. However, polyarylene sulfide resin has a problem that burrs are generated during molding. As a means to solve this problem, Patent Document 1 discloses a resin composition containing polyphenylene sulfide resin and polycarbonate resin. However, conventionally commercially available polyphenylene sulfide resins contain a certain amount of sodium as an impurity due to the constraints of the polymer polymerization method, so the polycarbonate resin decomposes significantly during molding and is inferior in practicality. Patent Document 2 discloses a resin composition composed of a polyphenylene sulfide resin and a polycarbonate resin with reduced chlorine content and sodium content. Patent Document 3 discloses a resin composition in which a hydrotalcite compound is added to a polyphenylene sulfide resin and a polycarbonate resin with reduced chlorine content and sodium content to suppress the decomposition of the polycarbonate resin. Although the resin compositions disclosed in Patent Document 2 and Patent Document 3 suppress the decomposition of the polycarbonate resin and show improvement in burrs, no evaluation has been made regarding the heat resistance and flame retardancy, which are characteristics of polyarylene sulfide resin. Patent Document 4 discloses a resin composition in which a compound having a reactive functional group and glass fiber are added to polyarylene sulfide resin and polycarbonate resin. The resin composition disclosed by Patent Document 4 improves the heat resistance by adjusting the morphology and dispersing glass fiber only in the polyarylene sulfide resin by using a compound having a reactive functional group, but no evaluation has been made regarding the flame retardancy, which is a characteristic of polyarylene sulfide resin.

Prior Art Documents

Patent Documents

[0003]

Patent Document 1

[0004] An object of the present invention is to provide a polyarylene sulfide resin composition excellent in extrudability, low burr property, high-temperature creep property, and flame retardancy, and a molded article made thereof. [Means for Solving the Problems]

[0005] As a result of intensive studies, the present inventors have found that by using a silane-based compound having a reactive functional group and boehmite in combination in a resin composition excellent in low burr property, which is composed of a polyarylene sulfide resin, a thermoplastic resin, and a fibrous reinforcing material, excellent high-temperature creep property and flame retardancy are exhibited, leading to the present invention. Although the mechanism is not clear, in addition to the high-temperature creep property being improved by the silane-based compound having a reactive functional group enhancing the adhesion between the polyarylene sulfide resin and the fibrous reinforcing material, the silane-based compound having a reactive functional group also acts on boehmite, and as a result, boehmite selectively exists in the polyarylene sulfide resin layer existing around the fibrous reinforcing material, so it is presumed that the flame retardancy is also improved because the combustible gas released out of the system along the fibrous reinforcing material is efficiently suppressed.

[0006] That is, the present invention is as follows. 1. 100 parts by weight of a resin component composed of (A) a polyarylene sulfide resin (component A) and (B) a thermoplastic resin (component B) contains 10 to 150 parts by weight of (C) a fibrous reinforcing material (component C), 0.01 to 3 parts by weight of (D) a silane-based compound having a reactive functional group (component D), and 1 to 30 parts by weight of (E) boehmite (component E), and the content of component B in 100 parts by weight of the resin component is 10 to 50 parts by weight. A polyarylene sulfide resin composition characterized by this. 2. The polyarylene sulfide resin composition according to item 1 above, wherein component B is at least one thermoplastic resin selected from the group consisting of a polycarbonate resin, a polyethersulfone resin, and a polyethylene naphthalate resin. 3. The polyarylene sulfide resin composition according to item 1 or 2 above, wherein the reactive functional group of component D is a mercapto group. 4. The polyarylene sulfide resin composition according to any one of items 1 to 3 above, wherein component E is cubic or granular boehmite. 5. The polyarylene sulfide resin composition according to any one of items 1 to 4 above, wherein component C is at least one fibrous reinforcing material selected from the group consisting of glass fiber and carbon fiber. 6. The polyarylene sulfide resin composition according to any one of items 1 to 5 above, wherein component A is a polyarylene sulfide resin having a total sodium content of 39 ppm or less. 7. A molded article comprising the polyarylene sulfide resin composition according to any one of items 1 to 6 above.

Advantages of the Invention

[0007] According to the present invention, it is possible to provide a polyarylene sulfide resin composition excellent in extrudability, low burr property, high-temperature creep property, and flame retardancy, and a molded article made therefrom. The molded article made of the polyarylene sulfide resin composition of the present invention is used for housings of personal computers, tablets, mobile phone housings, displays, office automation equipment, mobile phones, portable information terminals, facsimiles, compact discs, portable MDs, portable radio cassettes, PDAs (portable information terminals such as electronic notebooks), video cameras, digital still cameras, optical equipment, audio, air conditioners, lighting equipment, entertainment supplies, toy supplies, and other electrical and electronic equipment such as casings, internal members such as trays and chassis, cases, mechanical components, panels, etc. for building materials applications, motor components, alternator terminals, alternator connectors, IC regulators, potentiometer bases for light diyers, suspension components, various valves such as exhaust gas valves, fuel-related, exhaust system or intake system various pipes, air intake nozzle snorkels, intake manifolds, various arms, various frames, various hinges, various bearings, fuel pumps, gasoline tanks, CNG tanks, engine coolant joints, carburetor main bodies, carburetor spacers, exhaust gas sensors, coolant sensors, oil temperature sensors, brake pad wear sensors, throttle position sensors, crankshaft position sensors, air flow meters, brake pad wear sensors, thermostat bases for air conditioners, heating warm air flow control valves, brush holders for radiator motors, water pump impellers, turbine vanes, wiper motor-related components, distributors, starter switches, starter relays, wire harnesses for transmissions, window washer nozzles, air conditioner panel switch substrates, coils for fuel-related electromagnetic valves, connectors for fuses, battery trays, AT brackets, headlamp supports, pedal housings, steering wheels, door beams, protectors, chassis, frames, armrests, horn terminals, stepping motor rotors, lamp sockets, lamp reflectors, lamp housings, brake pistons, noise shields, radiator supports, spare tire covers, seat shells, solenoid bobbins,Automobile and motorcycle related parts, components and outer panels such as engine oil filters, ignition device cases, undercovers, scuff plates, pillar trims, propeller shafts, wheels, fenders, fascias, bumpers, bumper beams, bonnets, aerodynamic parts, platforms, cowl louvers, roofs, instrument panels, spoilers and various modules, as well as aircraft related parts, components and outer panels such as landing gear pods, winglets, spoilers, edges, ladders, elevators, fairings, ribs, etc., and windmill blades, etc. are widely useful. Among them, because of its excellent high-temperature creep properties, it can be preferably used as a member for cooling fan motors used in computers, notebooks, rack-mounted servers, hybrid vehicles, electric vehicles, etc.

[0008] Hereinafter, the details of the present invention will be described.

[0009] <Component A: Polyarylene sulfide resin> As the polyarylene sulfide resin used as Component A of the present invention, any resin belonging to the category called polyarylene sulfide resin may be used.

[0010] Examples of the polyarylene sulfide resin include those composed of, as its structural units, for example, p-phenylene sulfide units, m-phenylene sulfide units, o-phenylene sulfide units, phenylene sulfide sulfone units, phenylene sulfide ketone units, phenylene sulfide ether units, diphenylene sulfide units, substituent-containing phenylene sulfide units, branched structure-containing phenylene sulfide units, etc. Among them, those containing 70 mol% or more of p-phenylene sulfide units are preferred, those containing 90 mol% or more are more preferred, and poly(p-phenylene sulfide) is even more preferred.

[0011] The total chlorine content of the polyarylene sulfide resin used as Component A of the present invention is preferably 500 ppm or less, more preferably 450 ppm or less, still more preferably 300 ppm or less, and particularly preferably 50 ppm or less. When the total chlorine content exceeds 500 ppm, the thermoplastic resin may decompose and the mechanical strength may decrease. The lower limit of the total chlorine content is not particularly limited, but is preferably 10 ppm.

[0012] The total sodium content of the polyarylene sulfide resin used as Component A of the present invention is preferably 39 ppm or less, more preferably 30 ppm or less, still more preferably 10 ppm or less, and particularly preferably 8 ppm or less. When it exceeds 39 ppm, not only may the mechanical strength decrease due to the decomposition of the thermoplastic resin, but also in a high-temperature and high-humidity environment, the moisture resistance may decrease due to an increase in the water absorption of the resin caused by the coordination bond between sodium metal and water molecules. The lower limit of the total sodium content is not particularly limited, but is preferably 5 ppm. The total sodium content was measured by ICP emission spectrometry (ICP-AES method).

[0013] The method for producing the polyarylene sulfide resin is not particularly limited and is polymerized by a known method. Particularly preferred polymerization methods include those described in U.S. Registered Patents Nos. 4,746,758, 4,786,713, JP-T-2013-522385, JP-A-2012-233210, and Patent No. 5167276, etc. These production methods are methods in which a diiodoaryl compound and solid sulfur are directly heated and polymerized without a polar solvent.

[0014] The production method includes an iodination step and a polymerization step. In the iodination step, an aryl compound is reacted with iodine to obtain a diiodoaryl compound. In the subsequent polymerization step, a polymerization terminator is used to polymerize the diiodoaryl compound with solid sulfur to produce a polyarylene sulfide resin. Iodine is generated in a gaseous state in this step, and this is recovered and used again in the iodination step. Substantially, iodine is a catalyst.

[0015] As a typical solid sulfur used in the manufacturing method, cyclo-octa sulfur form (S8) in which eight atoms are linked at room temperature can be mentioned. However, the sulfur compound used in the polymerization reaction is not limited, and any form can be used as long as it is solid or liquid at normal temperature.

[0016] As a typical di-iodo aryl compound used in the manufacturing method, at least one selected from the group consisting of di-iodo benzene, di-iodo naphthalene, di-iodo biphenyl, di-iodo bisphenol and di-iodo benzophenone can be mentioned, and derivatives of iodo aryl compounds in which an alkyl group or a sulfone group is bonded or oxygen or nitrogen is introduced are also used. Iodo aryl compounds are classified into isomers depending on the bonding position of the iodine atoms, and preferred examples among these isomers are compounds in which iodine is symmetrically located at both ends of the aryl compound molecule, such as p-di-iodo benzene, 2,6-di-iodo naphthalene, and p,p'-di-iodo biphenyl. The content of the iodo aryl compound is preferably 500 to 10,000 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined in consideration of the formation of disulfide bonds.

[0017] Typical polymerization terminators used in the above manufacturing method include monoiodoaryl compounds, benzothiazoles, benzothiazole sulfenamides, thiurams, dithiocarbamates, aromatic sulfide compounds, etc. Preferred examples of monoiodoaryl compounds include at least one selected from the group consisting of iodobiphenyl, iodophenol, iodoaniline, and iodobenzophenone. Preferred examples of benzothiazoles include at least one selected from the group consisting of 2-mercaptobenzothiazole and 2,2'-dithiobisbenzothiazole. Preferred examples of benzothiazole sulfenamides include at least one selected from the group consisting of N-cyclohexylbenzothiazole 2-sulfenamide, N,N-dicyclohexyl-2-benzothiazole sulfenamide, 2-morpholinothiobenzothiazole, benzothiazole sulfenamide, dibenzothiazole disulfide, and N-dicyclohexylbenzothiazole 2-sulfenamide. Preferred examples of thiurams include at least one selected from the group consisting of tetramethylthiuram monosulfide and tetramethylthiuram disulfide. Preferred examples of dithiocarbamates include at least one selected from the group consisting of zinc dimethyldithiocarbamate and zinc diethyldithiocarbamate. Preferred examples of aromatic sulfide compounds include at least one selected from the group consisting of diphenyl sulfide, diphenyl disulfide, diphenyl ether, biphenyl, and benzophenone. Also, in any of the polymerization terminators, one or more functional groups may be substituted on the conjugated aromatic ring skeleton. Examples of the functional groups include hydroxy group, carboxy group, mercapto group, amino group, cyano group, sulfo group, nitro group, etc. Preferred examples include hydroxy group, amino group, and carboxy group. More preferred examples include, in the FT-IR spectrum, 3200~3600cm -1 , 1600~1800cm -1 and 3300~3500cm -1Examples of the peak include a hydroxy group, an amino group, and a carboxy group. The content of the polymerization terminator is preferably 1 to 30 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined in consideration of the formation of disulfide bonds.

[0018] In the above production method, a polymerization reaction catalyst may be used. Representative examples of the polymerization reaction catalyst include nitrobenzene-based catalysts. Preferred examples of the nitrobenzene-based catalysts include at least one selected from the group consisting of 1,3-diiodo-4-nitrobenzene, 1-iodo-4-nitrobenzene, 2,6-diiodo-4-nitrophenol, iodonitrobenzene, and 2,6-diiodo-4-nitroamine. The content of the polymerization reaction catalyst is preferably 0.01 to 20 parts by weight with respect to 100 parts by weight of the solid sulfur. This amount is determined in consideration of the formation of disulfide bonds.

[0019] By using this polymerization method, it is not necessary to substantially reduce the chlorine content and the sodium content, and a polyarylene sulfide resin excellent in cost performance can be obtained.

[0020] <Component B: Thermoplastic resin> Any thermoplastic resin other than the polyarylene sulfide resin can be used as the thermoplastic resin used in the present invention, but at least one thermoplastic resin selected from the group consisting of a polycarbonate resin, a polyethersulfone resin, and a polyethylene naphthalate resin is particularly preferably used. As the thermoplastic resin used as Component B, copolymers or modified products thereof may be used, and it is also possible to use two or more kinds in combination, not just alone.

[0021] The content of Component B is 10 to 50 parts by weight, preferably 15 to 45 parts by weight, and more preferably 20 to 40 parts by weight in 100 parts by weight in total of Component A and Component B. If the content is less than 10 parts by weight, the generation of burrs cannot be suppressed, and if it is more than 50 parts by weight, the drawability during extrusion is poor and pelletization becomes difficult.

[0022] As the polycarbonate resin used in the present invention, it is obtained by reacting a dihydric phenol with a carbonate precursor. Examples of the reaction method include an interfacial polymerization method, a melt transesterification method, a solid-phase transesterification method of a carbonate prepolymer, and a ring-opening polymerization method of a cyclic carbonate compound, etc., but the melt transesterification method is preferred. The polycarbonate resin may also be a branched polycarbonate resin obtained by polymerizing trifunctional phenols, and may further be a copolymer polycarbonate resin copolymerized with an aliphatic dicarboxylic acid, an aromatic dicarboxylic acid, or a divalent aliphatic or alicyclic alcohol.

[0023] The viscosity average molecular weight of the polycarbonate resin is preferably 1.3×10 4 ~4.0×10 4 and more preferably 1.5×10 4 ~3.8×10 4 . The viscosity average molecular weight (M) of the aromatic polycarbonate resin is determined by inserting the specific viscosity (η sp ) obtained at 20°C from a solution prepared by dissolving 0.7 g of the polycarbonate resin in 100 ml of methylene chloride into the following formula. Details of such polycarbonate resins are described in Japanese Patent Laid-Open No. 2002-129003. η sp / c = [η] + 0.45×[η] 2 c (where [η] is the intrinsic viscosity) [η] = 1.23×10 -4 M 0.83 c = 0.7

[0024] The polycarbonate resin used in the present invention may be various polycarbonate resins having high heat resistance or low water absorption, which are polymerized using other dihydric phenols in addition to the commonly used bisphenol A type polycarbonate resin. Specific examples of various polycarbonate resins having high heat resistance or low water absorption, which are polymerized using other dihydric phenols, are preferably exemplified as follows. (1) A copolymer polycarbonate resin in which, in 100 mol% of the diphenol component constituting the polycarbonate resin, the 4,4'-(m-phenylenediisopropylidene)diphenol (hereinafter abbreviated as "BPM") component is 20 to 80 mol% (more preferably 40 to 75 mol%, even more preferably 45 to 65 mol%), and the 9,9-bis(4-hydroxy-3-methylphenyl)fluorene (hereinafter abbreviated as "BCF") component is 20 to 80 mol% (more preferably 25 to 60 mol%, even more preferably 35 to 55 mol%). (2) A copolymer polycarbonate resin in which, in 100 mol% of the diphenol component constituting the polycarbonate resin, the bisphenol A component is 10 to 95 mol% (more preferably 50 to 90 mol%, even more preferably 60 to 85 mol%), and the BCF component is 5 to 90 mol% (more preferably 10 to 50 mol%, even more preferably 15 to 40 mol%). (3) A copolymer polycarbonate resin in which, in 100 mol% of the diphenol component constituting the polycarbonate resin, the BPM component is 20 to 80 mol% (more preferably 40 to 75 mol%, even more preferably 45 to 65 mol%), and the 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane component is 20 to 80 mol% (more preferably 25 to 60 mol%, even more preferably 35 to 55 mol%).

[0025] These special polycarbonate resins may be used alone, or two or more of them may be appropriately mixed and used. Also, they can be mixed and used with the commonly used bisphenol A type polycarbonate resin. The production methods and properties of these special polycarbonate resins are described in detail, for example, in JP-A-6-172508, JP-A-8-27370, JP-A-2001-55435, and JP-A-2002-117580. Furthermore, it is also possible to use a polycarbonate-polyorganosiloxane copolymer obtained by copolymerizing polyorganosiloxane units.

[0026] Polycarbonate resins can utilize not only virgin raw materials but also polycarbonate resins recycled from used products. Examples of such used products include containers typified by water bottles, optical discs, and automotive headlamps.

[0027] The polyethylene naphthalate resin used in the present invention preferably consists of naphthalenedicarboxylic acid or its ester derivative with a dicarboxylic acid component of 80 to 100 mol% and at least one selected from the group consisting of 0 to 20 mol% of terephthalic acid, isophthalic acid, and their ester derivatives, and has an ethylene glycol as the diol component. If the naphthalenedicarboxylic acid in the dicarboxylic acid component is less than 80 mol%, the heat resistance may be insufficient.

[0028] The naphthalenedicarboxylic acid component is mainly 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid, but other dicarboxylic acids can be used in combination as long as the properties are not impaired.

[0029] Examples of dicarboxylic acid components other than naphthalenedicarboxylic acid include aromatic dicarboxylic acids such as terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2,5-dichloroterephthalic acid, 2-methylterephthalic acid, 4,4-stilbenedicarboxylic acid, 4,4-biphenyldicarboxylic acid, orthophthalic acid, bisbenzoic acid, bis(p-carboxyphenyl)methane, anthracenedicarboxylic acid, 4,4-diphenyletherdicarboxylic acid, 4,4-diphenoxyethanedicarboxylic acid, 5-Na sulfoisophthalic acid, ethylene-bis-p-benzoic acid, and aliphatic dicarboxylic acids such as adipic acid, sebacic acid, azelaic acid, dodecanedioic acid, 1,3-cyclohexanedicarboxylic acid, and 1,4-cyclohexanedicarboxylic acid. Among them, terephthalic acid is preferred. These dicarboxylic acids can be used alone or in a mixture of two or more.

[0030] As the glycol component, ethylene glycol is the main component, but other glycol components can be used in combination as long as the properties are not impaired. As other glycol components, for example, one or more of alkylene glycols such as 1,4-butanediol, 1,3-propylene glycol, 1,2-propylene glycol, neopentylene glycol, hexamethylene glycol, decamethylene glycol, cyclohexanedimethanol, diethylene glycol, triethylene glycol, poly(oxy)ethylene glycol, poly(oxy)tetramethylene glycol, poly(oxy)methylene glycol, etc. may be used and can be arbitrarily selected according to the purpose. Further, a small amount of a polyhydric alcohol component such as glycerin may be used. Also, a small amount of an epoxy compound may be used. The usage amount of other glycol components is preferably 30 mol% or less, more preferably 20 mol% or less based on the total glycol components.

[0031] The above polyethylene naphthalate resin can be produced by a conventionally known production method. That is, it is produced by a direct esterification method in which a dicarboxylic acid component and a diol component are directly reacted to distill off water for esterification and then polycondensation is carried out under reduced pressure, or a transesterification method in which dimethyl dicarboxylate and a diol component are reacted to distill off methyl alcohol for transesterification and then polycondensation is carried out under reduced pressure. Further, solid-phase polymerization can be carried out to increase the limiting viscosity number.

[0032] During the above transesterification reaction, esterification reaction and polycondensation reaction, it is preferable to use a catalyst and a stabilizer. As the transesterification catalyst, Mg compounds, Mn compounds, Ca compounds, Zn compounds, etc. are used, and examples thereof include acetates, monocarboxylates, alcoholates and oxides of these. Also, the esterification reaction can be carried out only with dicarboxylic acid and diol without adding a catalyst, but it can also be carried out in the presence of the polycondensation catalyst described later. As the polycondensation catalyst, Ge compounds, Ti compounds, Sb compounds, etc. can be used, and examples thereof include germanium dioxide, germanium hydroxide, germanium alcoholate, titanium tetrabutoxide, titanium tetraisopropoxide and titanium oxalate. It is preferable to use a phosphorus compound as the stabilizer. Preferred phosphorus compounds include phosphoric acid and its esters, phosphorous acid and its esters, and hypophosphorous acid and its esters. Also, during the esterification reaction, a tertiary amine such as triethylamine, a quaternary ammonium hydroxide such as tetraethylammonium hydroxide, and a basic compound such as sodium carbonate can be added to suppress the by-production of diethylene glycol. Further, various stabilizers and modifiers can be blended into the obtained polyester resin.

[0033] The intrinsic viscosity of the polyethylene naphthalate resin is preferably 0.5 to 1.0 dl / g, more preferably 0.55 to 0.85 dl / g, and even more preferably 0.60 to 0.68 dl / g. If the intrinsic viscosity of the polyethylene naphthalate resin is less than 0.5 dl / g, the mechanical properties may be inferior, and if it exceeds 1.0 dl / g, the viscosity of the polyethylene naphthalate resin may be too high to be taken out of the polymerization furnace.

[0034] As the polyether sulfone resin used in the present invention, those obtained by polycondensing a dihalodiphenyl compound and a divalent phenol compound in the presence of an alkali metal compound in an organic solvent, or by polycondensing an alkali metal disalt of a divalent phenol and a dihalodiphenyl compound are preferably used. As the organic solvent, an organic polar solvent is preferred. For example, sulfoxide solvents such as dimethyl sulfoxide, amide solvents such as N,N-dimethylformamide and N,N-dimethylacetamide, pyrrolidone solvents such as N-methyl-2-pyrrolidone and N-vinyl-2-pyrrolidone, piperidone solvents such as N-methyl-2-piperidone, 2-imidazolinone solvents such as 1,3-dimethyl-2-imidazolidinone, hexamethylphosphorus amide, γ-butyrolactone, sulfolane, diphenyl ether, diphenyl sulfone and other ketone solvents such as diphenyl compounds or mixtures of two or more of these. Preferably, as the organic solvent, one or more compounds selected from the group consisting of N-methyl-2-pyrrolidone, N,N-dimethylacetamide, dimethyl sulfone, diphenyl sulfone, dimethyl sulfoxide, dimethylformamide, hexamethylphosphorus amide, γ-butyrolactone, sulfolane, 1,3-dioxolane and 1,3-dimethyl-2-imidazolidinone are used. Examples of the alkali metal compound include alkali metal carbonates, alkali metal hydroxides, alkali metal hydrides and alkali metal alkoxides. In particular, anhydrous alkali metal carbonates such as potassium carbonate and sodium carbonate are preferred. Examples of the dihalodiphenyl compound include dihalodiphenyl compounds having a sulfone group, such as dihalodiphenyl sulfones such as 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone, bis(halogenophenylsulfonyl)benzenes such as 1,4-bis(4-chlorophenylsulfonyl)benzene and 1,4-bis(4-fluorophenylsulfonyl)benzene, bis(halogenophenylsulfonyl)biphenyls such as 4,4'-bis(4-chlorophenylsulfonyl)biphenyl and 4,4'-bis(4-fluorophenylsulfonyl)biphenyl, and the like.Among them, since dihalodiphenyl sulfones are easily available, they are preferred, 4,4'-dichlorodiphenyl sulfone and 4,4'-difluorodiphenyl sulfone are more preferred, and particularly 4,4'-dichlorodiphenyl sulfone is preferred. These dihalodiphenyl compounds can also be used as a mixture of two or more kinds.

[0035] Examples of the divalent phenol compound include hydroquinone, catechol, resorcinol, 4,4'-biphenol, and in addition, bis(4-hydroxyphenyl)alkanes such as 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)methane, 2,2-bis(4-hydroxyphenyl)ethane, dihydroxydiphenyl sulfones such as 4,4'-dihydroxydiphenyl sulfone, dihydroxydiphenyl ethers such as 4,4'-dihydroxydiphenyl ether, or those in which at least one of the hydrogen atoms of their benzene rings is substituted with a lower alkyl group such as a methyl group, an ethyl group, or a propyl group, a lower alkoxy group such as a methoxy group, an ethoxy group, or a propyloxy group, or a halogen atom such as a chlorine atom, a bromine atom, or a fluorine atom. Particularly, from the viewpoints of price and availability, hydroquinone, 4,4'-biphenol, 2,2-bis(4-hydroxyphenylpropane), 4,4'-dihydroxydiphenyl ether, or 4,4'-dihydroxydiphenyl sulfone is preferred, and 4,4'-dihydroxydiphenyl sulfone is particularly preferred. The above divalent phenol compounds may be used as a mixture of two or more kinds.

[0036] The polyether sulfone resin that can be preferably used in the present invention is a polyether sulfone resin represented by the following formula (1).

[0037]

Chemical formula

[0038] <Component C: Fiber Reinforcement> The fibrous reinforcing material used in the present invention is not particularly limited as long as it is a fibrous reinforcing material. For example, it includes glass fiber, carbon fiber, aramid fiber, alumina fiber, silicon carbide fiber, ceramic fiber, asbestos fiber, wollastonite fiber, metal fiber, and a fibrous reinforcing material coated with a conductive substance. Among them, it is preferably at least one fibrous reinforcing material selected from the group consisting of glass fiber and carbon fiber from the viewpoints of mechanical strength and high-temperature creep characteristics.

[0039] As the glass fiber, glass fiber having a round cross-section, flat cross-section glass fiber having an average value of the major axis of the fiber length cross-section of 10 to 50 μm and an average value of the ratio of the major axis to the minor axis (major axis / minor axis) of 1.5 to 8, and glass milled fiber are preferably exemplified. In particular, flat cross-section glass fiber having an average value of the major axis of the fiber length cross-section of 10 to 50 μm and an average value of the ratio of the major axis to the minor axis (major axis / minor axis) of 1.5 to 8 is more preferable in terms of tensile strength and dimensional accuracy.

[0040] For the glass composition of the above glass fiber, various glass compositions typified by A glass, C glass, E glass, etc. are applicable and not particularly limited. Such glass fiber may contain components such as TiO2, SO3, and P2O5 as required. Among these, E glass (alkali-free glass) is more preferable. Such glass fiber is preferably surface-treated with a well-known surface treatment agent, such as a silane coupling agent, a titanate coupling agent, and an aluminate coupling agent, from the viewpoint of improving mechanical strength. Also, those subjected to a bundling treatment with an olefin-based resin, a styrene-based resin, an acrylic-based resin, a polyester-based resin, an epoxy-based resin, a urethane-based resin, etc. are preferable, and an epoxy-based resin and a urethane-based resin are particularly preferable from the viewpoint of mechanical strength. The amount of the bundling agent adhered to the bundled glass fiber is preferably 0.1 to 3% by weight, more preferably 0.2 to 1% by weight, based on 100% by weight of the glass fiber.

[0041] Examples of the carbon fiber include carbon fibers such as metal-coated carbon fiber, carbon milled fiber, and vapor-grown carbon fiber, and carbon nanotubes. The carbon nanotube may have a fiber diameter of 0.003 to 0.1 μm and may be any of single-layer, double-layer, and multi-layer, with multi-layer (so-called MWCNT) being preferred. Among these, carbon fiber is preferred in terms of excellent mechanical strength.

[0042] Any of cellulose-based, polyacrylonitrile-based, and pitch-based carbon fibers can be used. In addition, those obtained by a method of spinning without undergoing an infusibilization process typified by a method of spinning or molding a raw material composition composed of a polymer formed by a methylene-type bond of aromatic sulfonic acids or their salts and a solvent and then carbonizing can also be used. Furthermore, any of general-purpose type, medium modulus type, and high modulus type can be used. Among these, the high modulus type of polyacrylonitrile-based is particularly preferred. Also, the surface of the carbon fiber is preferably oxidized for the purpose of enhancing the adhesion to the matrix resin and improving the mechanical strength. The oxidation treatment method is not particularly limited, and examples thereof preferably include (1) a method of treating the carbon fiber with an acid, an alkali, their salts, or an oxidizing gas, (2) a method of firing a fiber capable of being carbonized or a carbon fiber at a temperature of 700°C or higher in the presence of an inert gas containing an oxygen-containing compound, and (3) a method of heat-treating the carbon fiber after oxidation treatment in the presence of an inert gas.

[0043] The metal-coated carbon fiber is obtained by coating a metal layer on the surface of a carbon fiber. Examples of the metal include silver, copper, nickel, and aluminum, and nickel is preferable from the viewpoint of the corrosion resistance of the metal layer. As the method for metal coating, known methods such as plating and vapor deposition can be mentioned, and among them, the plating method is preferably used. Also, in the case of such metal-coated carbon fibers, the carbon fibers mentioned above as the original carbon fibers can be used. The thickness of the metal coating layer is preferably 0.1 to 1 μm, more preferably 0.15 to 0.5 μm, and even more preferably 0.2 to 0.35 μm.

[0044] Such carbon fibers and metal-coated carbon fibers are preferably those subjected to a sizing treatment with an olefin resin, a styrene resin, an acrylic resin, a polyester resin, an epoxy resin, a urethane resin, or the like. In particular, carbon fibers treated with a urethane resin or an epoxy resin are suitable in the present invention because they have excellent mechanical strength.

[0045] The content of the C component is 10 to 150 parts by weight, more preferably 25 to 125 parts by weight, and even more preferably 40 to 100 parts by weight with respect to 100 parts by weight of the resin component composed of the A component and the B component. When the content of the C component is less than 10 parts by weight, the high-temperature creep characteristics deteriorate. On the other hand, when it exceeds 150 parts by weight, the flame retardancy deteriorates.

[0046] <D component: silane-based compound having a reactive functional group> The silane compound having a reactive functional group, which is the D component of the present invention, is a compound called a silane coupling agent having a reactive functional group. The reactive functional group can include an epoxy group, a methacrylic group, an isocyanurate group, an isocyanate group, a carboxy group, an amino group, and a mercapto group, with the mercapto group being most preferred. Specifically, mercapto-functional alkoxysilanes such as 3-mercaptopropylmethyldimethoxysilane and 3-mercaptopropyltrimethoxysilane can be mentioned. Such silane coupling agents having a mercapto group may be used alone or in combination of two or more. Among them, 3-mercaptopropyltrimethoxysilane is preferred from the viewpoint of high-temperature creep properties. Examples of such silane coupling agents are commercially available as KBM-803 and KBM-802 manufactured by Shin-Etsu Chemical Co., Ltd. and are easily available.

[0047] The content of the D component is 0.01 to 3 parts by weight, preferably 0.1 to 2 parts by weight, more preferably 0.2 to 1 part by weight, based on 100 parts by weight of the resin component composed of the A component and the B component. If the content of the D component is less than 0.01 part by weight, the adhesion between the polyarylene sulfide resin and the fibrous reinforcing material is poor, the high-temperature creep properties are deteriorated, and the flame retardancy is also deteriorated. On the other hand, if it exceeds 3 parts by weight, the resin composition is plasticized and it is difficult to stably draw out the strands during extrusion, making pelletization difficult.

[0048] <E component: Boehmite> The boehmite of the present invention is an alumina hydrate represented by the composition of AlOOH. The shape of the boehmite used in the present invention can be any of acicular, scaly, plate-like, and cubic shapes, but from the viewpoint of flame retardancy, plate-like or cubic boehmite is more preferred. The average particle diameter of the boehmite is preferably 1 μm or more and less than 8 μm, more preferably in the range of 1 μm to 6 μm, and still more preferably 2 μm to 5 μm. If the average particle diameter is less than 1 μm, the flame retardancy may be impaired, and if it is 8 μm or more, the mechanical strength may be reduced and the high-temperature creep properties may be reduced.

[0049] The content of Component E is 1 to 30 parts by weight, preferably 3 to 20 parts by weight, and more preferably 5 to 10 parts by weight with respect to 100 parts by weight of the resin component composed of Component A and Component B. When the content of Component E is less than 1 part by weight, the flame retardancy decreases. When it exceeds 30 parts by weight, the resin composition becomes brittle, the strand take-up property during extrusion becomes poor, and pelletization becomes difficult.

[0050] <Other components> The polyarylene sulfide resin composition of the present invention may contain additives such as antioxidants, impact modifiers, plasticizers, inorganic fillers other than Component C, flame retardants, colorants, light stabilizers, heat stabilizers, antistatic agents, antiblocking agents, lubricants, dispersants, flow modifiers, and crystal nucleating agents as necessary within a range not contrary to the gist of the present invention.

[0051] <Manufacture of resin composition> The resin composition of the present invention can be produced by mixing the above components simultaneously or in any order using a mixer such as a tumbler, V-type blender, Nauta mixer, Banbury mixer, kneading roll, extruder, etc. Preferably, melt-kneading by a twin-screw extruder is preferred. If necessary, it is preferable to supply any component from a second supply port using a side feeder or the like into the other melted and mixed components. As the extruder, one having a vent capable of degassing moisture in the raw material and volatile gases generated from the melt-kneaded resin can be preferably used. A vacuum pump is preferably installed at the vent to efficiently discharge the generated moisture and volatile gases to the outside of the extruder. It is also possible to install a screen for removing foreign substances mixed in the extrusion raw material in the zone before the extruder die part to remove the foreign substances from the resin composition. Examples of such a screen include a wire mesh, a screen changer, and a sintered metal plate (such as a disk filter). The screw used in a twin-screw extruder is configured as a single screw by inserting screw pieces of various shapes between the forward flight pieces for transportation and combining them in a complex manner and integrating them. Examples of screw pieces include forward flight pieces, forward kneading pieces, reverse kneading pieces, reverse flight pieces, forward flight pieces with notches, reverse flight pieces, etc., which are arranged and combined in an appropriate order and position considering the characteristics of the raw material to be processed. Examples of melt kneaders include a Banbury mixer, kneading rolls, a single-screw extruder, a multi-screw extruder with three or more shafts, etc. in addition to the twin-screw extruder.

[0052] The resin extruded as described above is directly cut and pelletized, or after forming a strand, the strand is cut by a pelletizer and pelletized. When it is necessary to reduce the influence of external dust, etc. during pelletization, it is preferable to clean the atmosphere around the extruder. The shape of the obtained pellets can take common shapes such as cylinders, prisms, and spheres, but more preferably a cylinder. The diameter of such a cylinder is preferably 1 to 5 mm, more preferably 1.5 to 4 mm, and even more preferably 2 to 3.5 mm. On the other hand, the length of the cylinder is preferably 1 to 30 mm, more preferably 2 to 5 mm, and even more preferably 2.5 to 4 mm.

[0053] <Regarding the molded body> The molded article obtained by using the polyarylene sulfide resin composition of the present invention can be obtained by molding the pellets produced as described above. Preferably, it can be obtained by injection molding or extrusion molding. In injection molding, not only ordinary molding methods but also injection compression molding, injection press molding, gas assist injection molding, foam molding (including the method of injecting supercritical fluid), insert molding, in-mold coating molding, adiabatic mold molding, rapid heating and cooling mold molding, two-color molding, multi-color molding, sandwich molding, and ultra-high speed injection molding can be mentioned. Also, either a cold runner system or a hot runner system can be selected for molding. In extrusion molding, a method of obtaining a molded article by extruding a round bar and then cutting it into a disk shape, or a method of obtaining a molded article by extruding a thick sheet and then punching it into a predetermined shape can be used.

Embodiments for Carrying Out the Invention

[0054] The form of the present invention that the present inventor currently considers to be the best is the aggregation of the preferable ranges of the above-mentioned respective requirements. For example, representative examples thereof are described in the following examples. Of course, the present invention is not limited to these forms.

Examples

[0055] [Evaluation of Polyarylene Sulfide Resin Composition] (1) Extrudability The extrudability when creating pellets by the following method was evaluated according to the following criteria. 〇: There is no problem with the strand take-up property, and continuous pelletization is possible. △: The strand is slightly surging, but pelletization is possible. ×: The strand cannot be continuously taken up, and pelletization is impossible.

[0056] (2) High-temperature creep properties A three-point bending creep test was conducted in accordance with JIS K7116 at a test temperature of 85 °C and a load stress of 90 MPa, and the creep displacement amount after 100 hours was determined. As the test piece, a dumbbell-shaped tensile test piece with a thickness of 4 mm conforming to the multi-purpose test piece type A1 of JIS K7139 was used. The obtained pellets were dried in a hot air circulation dryer at 130 °C for 6 hours and then molded by an injection molding machine (EC130SXII-4Y manufactured by Toshiba Machine Co., Ltd.) under the conditions of a cylinder temperature of 300 °C and a mold temperature of 120 °C. The smaller the value of the creep displacement amount, the better the high-temperature creep characteristics, and it is preferably 2.5 mm or less.

[0057] (3) Flame retardancy The vertical burning test at a test piece thickness of 0.8 mm was carried out and evaluated according to the method (UL94) defined by Underwriters Laboratories Inc., USA. In addition, those that did not fall into any of the V-0, V-1, and V-2 classifications were designated as not V. The classification is preferably any of V-0, V-1, and V-2.

[0058] (4) Low burr property The evaluation of burrs was carried out by measuring the length of the burrs at the part in contact with the gas vent of a dumbbell-shaped tensile test piece with a thickness of 4 mm conforming to the multi-purpose test piece type A1 of JIS K7139 described above. The thickness of the gas vent was 10 μm and the width was 5 mm. The smaller the measured burr length, the better the low burr property, and it is preferably 30 μm or less.

[0059] [Examples 1 to 29, Comparative Examples 1 to 8] According to the addition amounts shown in Table 1 and Table 2, each component was supplied from the first supply port to a vented twin-screw extruder. Here, the first supply port refers to the supply port at the base. Component C was supplied from the second supply port using a side feeder. A vented twin-screw extruder with a diameter of 30 mm Φ (manufactured by Nippon Steel Works, Ltd.: TEX30α-31.5BW-2V) was used, and melt kneading was performed at a screw rotation speed of 200 rpm, a discharge rate of 20 kg / h, and a vent vacuum degree of 3 kPa to obtain pellets. The extrusion temperature was 300 °C. The obtained pellets were dried in a hot air circulation dryer at 130 °C for 6 hours, and then test pieces for evaluation were molded using an injection molding machine (manufactured by Toshiba Machine Co., Ltd.: EC130SXII-4Y) under the conditions of a cylinder temperature of 300 °C and a mold temperature of 120 °C.

[0060] <Component A> A-1: Polyphenylene sulfide resin obtained by Production Method 1 [Production Method 1] To 300.00 g of paradibenzene and 27.00 g of sulfur, 0.60 g of diphenyldisulfide (content of 0.65% by weight based on the weight of the finally polymerized polyphenylene sulfide resin) was added as a polymerization terminator, and the mixture was heated to 180 °C to completely melt and mix them. Then, the temperature was raised to 220 °C, and the pressure was reduced to 200 Torr. The obtained mixture was subjected to a polymerization reaction for 8 hours while gradually changing the temperature and pressure so that the final temperature and pressure were 320 °C and 1 Torr, respectively, to produce a polyphenylene sulfide resin. The total sodium content was 7 ppm. Also, the dispersity (Mw / Mn) represented by the weight average molecular weight (Mw) and the number average molecular weight (Mn) was 4.7.

[0061] <Component B> B-1: Polycarbonate resin obtained by Production Method 2 [Production Method 2] Into a reactor equipped with a thermometer, a stirrer, and a reflux condenser, 219.4 parts of ion-exchanged water and 40.2 parts of a 48% aqueous sodium hydroxide solution were charged. To this, 57.5 parts of 2,2-bis(4-hydroxyphenyl)propane and 0.12 part of hydrosulfite were added and dissolved in 25 minutes. Then, 181 parts of methylene chloride were added in 5 minutes, and 27.8 parts of phosgene were blown in over 40 minutes with stirring at 15 - 25°C. After the phosgene blowing was completed, 7.2 parts of a 48% aqueous sodium hydroxide solution, 3.10 parts of p-tert-butylphenol, and 0.65 part of a solution prepared by dissolving 0.20 part of 2,2-bis(4-hydroxyphenyl)propane in 1 part of a 7.4% aqueous sodium hydroxide solution were added, emulsified with a homomixer, and then stirring was stopped. The mixture was allowed to stand at 28 - 33°C for 2.5 hours to complete the reaction. After the reaction was completed, 200 parts of methylene chloride were added to the product and mixed. Then, stirring was stopped, and the aqueous phase and the organic phase were separated to obtain an organic solvent solution containing 15% by weight of the polycarbonate resin. 200 parts of ion-exchanged water were added to this organic solvent solution, stirred and mixed, then stirring was stopped, and the aqueous phase and the organic phase were separated. This operation was repeated (4 times) until the conductivity of the aqueous phase became almost the same as that of ion-exchanged water. The obtained purified polycarbonate resin solution was filtered through a 1μm filter made of SUS304. Next, 100L of ion-exchanged water was charged into a 1000L kneader made of SUS316L with an inner wall provided with an isolation chamber having a foreign matter outlet at the bearing part. Methylene chloride was evaporated at a water temperature of 42°C to obtain a granular material. The mixture of the granular material and water was charged into a hot water treatment tank of a hot water treatment process having a stirrer-controlled hot water treatment tank with a water temperature controlled at 95°C, and stirred and mixed for 30 minutes at a mixing ratio of 25 parts of the granular material and 75 parts of water. The mixture of the granular material and water was separated by a centrifuge to obtain a granular material containing 0.5% by weight of methylene chloride and 45% by weight of water. Next, this granular material was continuously fed at 50 kg / Hr (in terms of polycarbonate resin) to a conduction-heated groove-type two-shaft continuous dryer made of SUS316L controlled at 140°C and dried under the condition of an average drying time of 6 hours to obtain a granular material with a viscosity-average molecular weight of 11,800. The obtained granular material was put into acetone, stirred for 30 minutes, and then the granular material slurry solution was taken out. After solid-liquid separation, it was dried at 140°C for 4 hours under a nitrogen atmosphere and extracted with acetone to obtain a granular material (powder) with a viscosity-average molecular weight of 12,500 and a hydroxyl group content of 13 eq / ton.

[0062] B-2: Polyethylene naphthalate resin obtained by Production Method 3 [Production Method 3] 100 parts by weight of dimethyl naphthalenedicarboxylate and 60 parts by weight of ethylene glycol were subjected to a transesterification reaction in the presence of 0.010 parts by weight (10 mmol%) of cobalt(II) acetate tetrahydrate and 0.030 parts by weight (30 mmol%) of manganese(II) acetate tetrahydrate by a conventional method. After 20 minutes of methanol distillation, 0.012 parts by weight (10 mmol%) of antimony trioxide was added, and 0.020 parts by weight (50 mmol%) of orthophosphoric acid was added before the completion of the transesterification reaction. Subsequently, a polycondensation reaction was carried out at 295°C under high vacuum to obtain a polyethylene naphthalate resin (b-2) having an intrinsic viscosity of 0.51 dl / g. The obtained polyethylene naphthalate resin (b-2) was subjected to solid-phase polymerization at a temperature of 227°C and a vacuum degree of 0.5 Torr for 8 hours to obtain a polyethylene naphthalate resin having an intrinsic viscosity of 0.68 dl / g. B-3: Polyethersulfone resin (Sumikaexcel 3600P (trade name) manufactured by Sumitomo Chemical Co., Ltd.)

[0063] <Component C> C-1: Chopped glass fiber with a circular cross-section (T-732H manufactured by Nippon Electric Glass Co., Ltd., diameter: 10.5 μm, cut length: 3 mm, urethane-epoxy-based sizing agent) C-2: Carbon fiber (IMC702 manufactured by Teijin Limited, major axis: 6 μm, cut length: 6 mm, tensile modulus of elasticity: 282 GPa, tensile strength: 5,490 MPa, urethane-based sizing agent)

[0064] <Component D> D-1: 3-Mercaptopropyltrimethoxysilane (KBM-803 manufactured by Shin-Etsu Chemical Co., Ltd.)

[0065] <Component E> E-1: Cubic boehmite (BMT-3LV manufactured by Kawaai Lime Industry Co., Ltd., center particle diameter: 2.7 μm) E-2: Cubic boehmite (BMB-2 manufactured by Kawaai Lime Industry Co., Ltd., center particle diameter: 1.5 μm) E-3: Cubic boehmite (BMB-07, manufactured by Kawaai Lime Industry Co., Ltd., center particle diameter 0.7 μm) E-4: Plate-like boehmite (BMT-33, manufactured by Kawaai Lime Industry Co., Ltd., center particle diameter 2.8 μm)

[0066]

Table 1

[0067]

Table 2

[0068] <Examples 1 to 29> Since it is a composition within the scope of the claims, a molded article excellent in extrudability, low burr property, high-temperature creep property, and flame retardancy could be obtained. <Comparative Example 1> Since the content of component B was less than the lower limit, the result was inferior in low burr property. <Comparative Example 2> Since the content of component B exceeded the upper limit, the result was inferior in extrudability. <Comparative Example 3> Since the content of component C was less than the lower limit, the result was inferior in high-temperature creep property. <Comparative Example 4> Since the content of component C exceeded the upper limit, the result was inferior in flame retardancy. <Comparative Example 5> Since the content of component D was less than the lower limit, the result was inferior in high-temperature creep property and flame retardancy. <Comparative Example 6> Since the content of component D exceeded the upper limit, the result was inferior in extrudability. <Comparative Example 7> Since the content of component E was less than the lower limit, the result was inferior in flame retardancy. <Comparative Example 8> Since the content of component E exceeded the upper limit, the result was inferior in extrudability.

Claims

1. (A) 100 parts by weight of a resin component composed of a polyarylene sulfide resin (component A) and (B) a thermoplastic resin (component B), (C) 10 to 150 parts by weight of a fibrous reinforcing material (component C), (D) 0.01 to 3 parts by weight of a silane-based compound having a reactive functional group (component D), and (E) 1 to 30 parts by weight of boehmite (component E), and the content of component B in 100 parts by weight of the resin component is 10 to 50 parts by weight. A polyarylene sulfide resin composition characterized by this.

2. The polyarylene sulfide resin composition according to claim 1, wherein component B is at least one thermoplastic resin selected from the group consisting of a polycarbonate resin, a polyethersulfone resin, and a polyethylene naphthalate resin.

3. The polyarylene sulfide resin composition according to claim 1 or 2, wherein the reactive functional group of component D is a mercapto group.

4. The polyarylene sulfide resin composition according to claim 1 or 2, wherein component E is cubic or plate-like boehmite.

5. The polyarylene sulfide resin composition according to claim 1 or 2, wherein component C is at least one fibrous reinforcing material selected from the group consisting of glass fiber and carbon fiber.

6. The polyarylene sulfide resin composition according to claim 1 or 2, wherein component A is a polyarylene sulfide resin having a total sodium content of 39 ppm or less.

7. A molded article comprising the polyarylene sulfide resin composition according to claim 1 or 2.

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