JP2013181044A - Polyarylene sulfide resin composition, and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide: a polyarylene sulfide resin composition having only a small amount of chlorine atoms, excellent in melt flowability, and excellent in dimensional stability and low warpage in repeated molding; and a molding thereof.SOLUTION: A polyarylene sulfide resin composition is prepared by melting and kneading a polyarylene sulfide resin, a non-fibrous filler, and a fibrous filler, wherein the polyarylene sulfide resin has a melt viscosity (320°C, shearing rate: 1,000/s) of <100 Pa-s, and a chlorine content of ≤2,000 ppm; the total amount of the non-fibrous filler and the fibrous filler is 100 to 300 pts.mass based on 100 pts.mass of resin components in the polyarylene sulfide resin composition; the content of the non-fibrous filler is higher than the content of the fibrous filler; and the content of chlorine atom in the polyarylene sulfide resin composition is ≤900 ppm. A molding is made of the polyarylene sulfide resin composition.

Description

  The present invention relates to a polyarylene sulfide resin composition having a reduced chlorine atom content and a molded article thereof.

  Polyarylene sulfide (hereinafter abbreviated as PAS) resin represented by polyphenylene sulfide (hereinafter abbreviated as PPS) resin has high heat resistance, mechanical properties, chemical resistance, dimensional stability, and flame retardancy. Therefore, it is widely used as an alternative material for metal materials mainly in automobile parts, electrical and electronic parts, and housing equipment parts, and the amount of use is also increasing. Among them, from the viewpoint of environmental protection in the use of electrical and electronic parts, the movement of halogen regulation has expanded rapidly, and the halogen content in a composition containing PAS resin (hereinafter abbreviated as PAS resin composition) is 900 ppm or less. It is in a situation that is regulated by.

  Since the PAS resin is obtained by polymerization using p-dichlorobenzene and alkali metal sulfide or alkali metal hydrosulfide as raw materials, a chlorine atom, which is one of halogen atoms, inevitably remains at the polymer terminal. As mentioned above, from the viewpoint of environmental problems, PAS resins with a lower chlorine atom content are demanded from the market. However, the chlorine atom content is reduced without impairing the excellent properties of the PAS resin, and molding processability is reduced. It has been demanded to provide a PAS resin having excellent resistance.

  Therefore, by combining a low chlorine atom content PAS resin with a specific proportion of non-fibrous fillers and fibrous fillers, the total amount of fillers relative to the PAS resin is in the range of 2 to 3 times by mass ratio, A PAS resin composition having a low content, excellent melt fluidity, and excellent dimensional stability during repeated molding and an injection-molded product thereof have been proposed (Patent Document 1).

  However, since the PAS resin having a low chlorine atom content used in the resin composition is obtained by reducing the amount of low molecular weight substances such as oligomers in the washing step, the melt viscosity of the PAS resin is high, Therefore, it was necessary to reduce the melt viscosity of the entire composition by using it together with a low-viscosity general-purpose PAS resin. For this reason, if the chlorine atom content of the composition is further reduced, the melt viscosity of the composition is increased, which causes a problem in the dimensional stability of the molded product. Along with this, a reduction in the thickness of the molded body has been demanded, and there has been a problem in low warpage when the molded product is thinned.

JP 2010-053356 A

  Therefore, the problem to be solved by the present invention is a polyarylene sulfide resin composition having a low chlorine atom content, excellent melt flowability, and excellent dimensional stability and low warpage during repeated molding, and a molded article thereof Is to provide.

  As a result of intensive studies to solve the above-mentioned problems, the inventors of the present invention blended with a filler using a PAS resin having a low melt viscosity and a low chlorine atom content, so that the chlorine atom content is low and the melt is reduced. The present inventors have found that a polyarylene sulfide resin composition excellent in fluidity, dimensional stability during repeated molding, and low warpage can be provided, and a molded product thereof, and has completed the present invention.

That is, the present invention is a polyarylene sulfide resin composition obtained by melt-kneading (α) polyarylene sulfide resin, (β) non-fibrous filler and (γ) fibrous filler,
The (α) polyarylene sulfide resin has a melt viscosity (320 ° C., shear rate 1000 / s) in a range of less than 100 [Pa · s] and a chlorine atom content in a range of 2000 ppm or less. The total amount of the fibrous filler and (γ) fibrous filler is 100 to 300 parts by mass with respect to 100 parts by mass of the resin component in the polyarylene sulfide resin composition, and (β) non-fibrous filling A polyarylene sulfide resin composition characterized in that the content of the material is not less than the content of the (γ) fibrous filler and the chlorine atom content in the polyarylene sulfide resin composition is in the range of 900 ppm or less, and The present invention relates to a molded product obtained by molding the polyarylene sulfide resin composition.

  According to the present invention, it is possible to provide a polyarylene sulfide resin composition having a low chlorine atom content, excellent melt fluidity, excellent dimensional stability and low warpage during repeated molding, and a molded product thereof. it can.

The polyarylene sulfide resin composition of the present invention is a polyarylene sulfide resin composition obtained by melt-kneading (α) polyarylene sulfide resin, (β) non-fibrous filler and (γ) fibrous filler. The (α) polyarylene sulfide resin has a melt viscosity (320 ° C., shear rate 1000 / s) in the range of less than 100 [Pa · s] and a chlorine atom content in the range of 2000 ppm or less, and the polyarylene sulfide resin The chlorine atom content of the composition is 900 ppm or less.

  The (α) PAS resin used in the present invention has a melt viscosity (320 ° C., shear rate 1000 / s) in the range of less than 100 [Pa · s], and contains the chlorine atom in the (α) polyarylene sulfide resin. The amount is 2000 ppm or less. Such a PAS resin can be obtained by, for example, reacting an alkali metal sulfide (A) with a dihaloaromatic compound (B) in a polar solvent to produce polyarylene sulfide. One or more compounds (C) selected from the group consisting of mercapto compounds, metal salts of mercapto compounds, phenol compounds, metal salts of phenol compounds and disulfide compounds are added when the reaction rate is 0 to 40%. (Hereinafter, it may be called the manufacturing method of PAS resin used for this invention.). By adding the compound (C) when the reaction rate of the dihaloaromatic compound (B) is 0 to 40%, polyarylene sulfide having a low halogen content can be easily obtained for the first time even when the viscosity is the same. There is an excellent effect. The timing when the compound (C) is added is that when the reaction rate of the dihaloaromatic compound (B) is 0 to 40%, the effect of reducing the amount of chlorine atoms is high, but a higher effect of reducing the amount of chlorine atoms is obtained. The time when the reaction rate of the dihaloaromatic compound (B) is 0 to 20% is preferable, and 0 to 10% is more preferable. The “reaction rate of the dihaloaromatic compound (B)” in the present invention is a decrease in the dihaloaromatic compound (B) from the charged amount that can be judged from the remaining amount of the dihaloaromatic compound (B) at a certain time. Refers to the percentage of

  As a polar solvent used in the method for producing a PAS resin used in the present invention, for example, an organic amide compound, a lactam compound, a urea compound, a cyclic organic phosphorus compound, or the like can be used. Specific examples of the polar solvent include N, N-dimethylformamide, N, N-dimethylacetamide, N, N-diethylacetamide, N, N-dipropylacetamide, N, N-dimethylbenzoic acid amide, caprolactam, N- Methylcaprolactam, N-ethylcaprolactam, N-isopropylcaprolactam, N-isobutylcaprolactam, N-normalpropylcaprolactam, N-normalbutylcaprolactam, N-cyclohexylcaprolactam, N-methyl-2-pyrrolidone, N-ethyl-2-pyrrolidone N-isopropyl-2-pyrrolidone, N-isobutyl-2-pyrrolidone, N-normalpropyl-2-pyrrolidone, N-normalbutyl-2-pyrrolidone, N-cyclohexyl-2-pyrrolidone, N-methyl-3-methyl -2-pyrrolidone, N-ethyl-3-methyl-2-pyrrolidone, N-methyl-3,4,5-trimethyl-2-pyrrolidone, N-methyl-2-piperidone, N-isopropyl-2-piperidone, N -Ethyl-2-piperidone, N-methyl-6-methyl-2-piperidone, N-methyl-3-ethyl-2-piperidone, tetramethylurea, N, N'-dimethylethyleneurea, N, N'-dimethyl Propylene urea, 1-methyl-1-oxosulfolane, 1-ethyl-1-oxosulfolane, 1-phenyl-1-oxosulfolane, 1-methyl-1-oxophosphorane, 1-normalpropyl-1-oxophosphorane And 1-phenyl-1-oxophosphorane. These solvents may be used alone or in combination of two or more. Among the polar solvents, aprotic organic amides or lactams are preferable, and N-alkyl lactam and N-alkylpyrrolidone are preferable, and N-methylpyrrolidone is particularly preferable.

  Examples of the alkali metal sulfide (A) include lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and a mixture thereof. These hydrates and aqueous solutions may also be used. In addition, hydrosulfides and hydrates corresponding to these can be used by neutralizing with the corresponding hydroxides, and inexpensive sodium sulfide is preferable.

  Examples of the dihaloaromatic compound (B) include p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 2,5-dichlorotoluene, p-dibromobenzene, 1,4-dichloronaphthalene, 1-methoxy. -2,5-dichlorobenzene, 4,4'-dichlorobiphenyl, 4,4'-dibromobiphenyl, 2,4-dichlorobenzoic acid, 2,5-dichlorobenzoic acid, 3,5-dichlorobenzoic acid, 2, Aromatic dihalogen compounds such as 4-dichloroaniline, 2,5-dichloroaniline, 3,5-dichloroaniline, 4,4′-dichlorophenyl ether, 4,4′-dichlorodiphenyl sulfoxide, 4,4′-dichlorophenyl ketone, Aromatic trihalogens such as 1,3,5-trichlorobenzene and 1,2,4-trichlorobenzene Compounds, 1,2,4,5 aromatic tetracarboxylic halogen compounds tetra chlorobenzene, and as well as similar thereto can be mixtures thereof. Among them, those containing an aromatic dihalogen compound substituted at the para position represented by p-dichlorobenzene as a main component are preferable, and p-dichlorobenzene is more preferable.

  The amount of the dihaloaromatic compound (B) used in the present invention is preferably 0.90 to 1.10 molar ratio with respect to the molar amount of the alkali metal sulfide (A) for reasons of high molecular weight. A 95 to 1.05 molar ratio is more preferred.

  The compound (C) used in the present invention is one or more compounds selected from the group consisting of mercapto compounds, metal salts of mercapto compounds, phenol compounds, metal salts of phenol compounds, and disulfide compounds. Examples of the mercapto compound include thiophenol, o-thiocresol, m-thiocresol, p-thiocresol, 1-naphthalenethiol, 2-naphthalenethiol, 3,4-dimercaptotoluene, 1-hexanethiol, 1 -Heptanethiol, 1-octanethiol, mercaptocyclopentane, mercaptocyclohexane, mercaptoacetic acid, α-mercaptopropionic acid, β-mercaptopropionic acid, mercaptosuccinic acid, thiosalicylic acid, 2-mercaptoethanol, 3-mercapto-2-butanol, 3-mercapto-1,2-propanediol, 2-mercaptoethylamine, β-mercaptovaline, 2-mercaptobenzimidazole, 2-mercaptobenzothiazole, 2-mercaptobenzoxazole, -Mercapto-1-methyltetrazole, 2-mercapto-4-methylpyrimidine, 2-mercapto-4,6-dimethylpyromidine, 5-mercapto-1-methyltetrazole, 3-mercapto-4-methyl-4H-1,2,4-triazole, 2-mercaptonicotinic acid, 6-mercaptopurine, 2-mercapto-6-hydroxypurine, 6-mercapto-2-aminopurine, 2-mercaptopyridine, 4-mercaptopyridine, 2-mercaptopyridine-N-oxide, 2-mercaptothiazoline 3-mercapto 1H-1,2,4-triazole, 2,5-dimercapto-1,3,4-thiadiazole, 5-mercapto-2-amino-1,3,4-thiadiazole, 1,3,5-triazine-2,4 6-trithiol, 2-merca Toimidazorin, 2-mercapto 4-pyrimidone, 2- mercapto-5-thiazolidone, and the like. Examples of the metal salt of the mercapto compound include sodium salt, lithium salt, potassium salt and the like of the mercapto compound.

  As the phenol compound, for example, phenol, cresol, ethylphenol, isopropylphenol, t-butylphenol and the like are preferably used. Examples of the metal salt of the phenol compound include sodium salt, lithium salt, potassium salt and the like of the phenol compound.

  Examples of the disulfide compound include diphenyl disulfide, p, p'-ditolyl disulfide, dibenzyl disulfide, dibenzoyl disulfide, dithiobenzoyl disulfide, and the like.

  Among the compounds (C), a mercapto compound and a metal salt of a mercapto compound are preferable, a mercapto compound is more preferable, and a thiophenol is more preferable because it can easily react with a PAS end.

The amount of the compound (C) used is preferably from 0.1 to 2.0 mol% for the reason of the chlorine atom reducing effect with respect to the molar amount of the alkali metal sulfide (A). Is more preferable.

  In the method for producing a PAS resin used in the present invention, the polyhaloaromatic compound (D) other than the dihaloaromatic compound (B) can be used as a part of the raw material as necessary. As the polyhaloaromatic compound, for example, 1,2,4-trichlorobenzene, 1,3,5-trichlorobenzene and 1,4,6-trichloronaphthalene are preferable, and 1,2,4-trichlorobenzene, 1 3,5-trichlorobenzene is particularly preferred.

  The amount of the polyhaloaromatic compound (D) used is preferably from 0.01 to 1.5 mol%, preferably from 0.05 to 1.0 mol, based on the molar amount of the alkali metal sulfide (A) because of the effect of increasing the viscosity. % Is more preferable.

  As a method for producing the above-mentioned (α) polyarylene sulfide resin, a method of polymerizing a dihaloaromatic compound such as p-dichlorobenzene with sodium sulfide or sodium hydrogen sulfide and sodium hydroxide in a polar solvent is generally used. Is. Among them, a method in which sodium sulfide and p-dichlorobenzene are reacted in an amide solvent such as N-methylpyrrolidone or dimethylacetamide or a sulfone solvent such as sulfolane is suitable.

  However, the above production method is not particularly limited as long as it can be obtained by a known method. For example, US Pat. No. 2,513,188, Japanese Patent Publication No. 44-27671, Japanese Patent Publication No. 45-3368. JP-B-52-12240, JP-A-61-225217 and U.S. Pat. No. 3,274,165, British Patent No. 1160660, JP-B-46-27255, Belgian Patent No. 29437, JP-A-5 -222196 and the prior art methods exemplified in these patents. For example, in the method disclosed in Japanese Patent Publication No. 45-3368, a nucleophilic substitution reaction between a dihaloaromatic compound and an alkali metal compound such as hydrous sodium sulfide in an organic amide solvent such as N-methylpyrrolidone. In the desalination polycondensation by the above, after dehydration from the hydrous sulfide to obtain a dehydrated mixture, the dihaloaromatic compound (B) is added to the dehydrated mixture, polymerized at a suitable temperature at a suitable time, PAS In the obtained method, if the compound (C) is added when the reaction rate of the dihaloaromatic compound (B) is 0 to 40%, the desired low chlorine atom-containing PAS can be obtained.

  The reaction slurry containing PAS obtained by the polymerization reaction is separated from liquid and solid by filtration under normal pressure or reduced pressure, and the solvent is recovered from the liquid part. By-products such as salt and unreacted from the solid part In order to remove the raw materials and the like, it is usually performed by repeatedly washing with water and solvent, and finally drying to take out PAS.

Specific examples of the post-treatment method of the slurry containing PAS after the polymerization reaction include the following methods.
(1) After the completion of the polymerization reaction, the reaction slurry is first added as it is, or an acid or a base is added, and then the solvent is distilled off under reduced pressure or normal pressure. Then, the solid after the solvent is removed is washed with water, acetone, methyl ethyl ketone, A method in which PAS is separated and removed by washing once or twice with a solvent such as alcohol, and further neutralizing, washing with water, filtering and drying.

(2) After completion of the polymerization reaction, the reaction slurry is mixed with a solvent such as water, acetone, methyl ethyl ketone, alcohols, ethers, halogenated hydrocarbons, aromatic hydrocarbons, aliphatic hydrocarbons (the organic polar solvent used in the present invention). Soluble and at least a solvent that is a poor solvent for PAS) is added as a precipitating agent to precipitate solid-state products such as PAS and inorganic salts, and these are filtered to obtain a solid content containing PAS. The PAS is separated and obtained by separating, washing and drying.

  (3) After completion of the polymerization reaction, the same organic polar solvent (or an organic solvent having the same solubility as that of the low molecular weight PAS) added to the reaction slurry is added and stirred, and then filtered to obtain a low molecular weight PAS. After removing the organic polar solvent and its dissolved product, the solid containing PAS is washed once or twice with a solvent such as water, acetone, methyl ethyl ketone, alcohols, etc., and then neutralized, washed with water, filtered and dried. To take out PAS.

  In the post-treatment methods as exemplified in the above (1) to (3), the PAS may be dried in a vacuum, or in an inert gas atmosphere such as air or nitrogen. Good, no limitation.

  The polyarylene fried resin thus obtained can be used as it is for various molding materials, but it can increase the melt viscosity by heat treatment in air or oxygen-enriched air or under reduced pressure conditions. If necessary, such a thickening operation (usually such operation is referred to as “crosslinking”) may be used for various molding materials. This cross-linking temperature varies depending on the target cross-linking treatment time and the atmosphere to be treated. In addition, when crosslinking is performed with an extruder or the like, it may be performed in a molten state that is higher than the melting point of the polyarylene sulfide resin. preferable.

  The (α) polyarylene fide resin used in the present invention has a melt viscosity (V6) measured at 300 ° C. of 1 [Pa · s] or more from the PAS resin obtained by the above method, more preferably 2 [Pa · s] or more, more preferably 5 [Pa · s] or more, and less than 100 [Pa · s], more preferably less than 40 [Pa · s], still more preferably 20 [Pa · s]. [Pa · s] is used. In particular, in the case of a polyarylene sulfide resin not subjected to crosslinking treatment, it is preferable to use a resin having a melt viscosity (V6) of less than 40 [Pa · s]. However, the melt viscosity (V6) measured at 300 ° C. is an orifice having a temperature / 300 ° C., a load of 1.96 MPa and an orifice length / orifice diameter ratio of 10/1 using a flow tester. Represents the melt viscosity after holding for 6 minutes.

  The (α) polyarylene fide resin used in the present invention has a chlorine atom content of 2000 ppm or less, more preferably 1500 ppm or less, and still more preferably 1200 ppm or less. On the other hand, the lower the lower limit of the amount of chlorine atoms contained, the better and not particularly limited, but according to the above production method, it is 500 ppm or more, preferably 900 ppm or more, more preferably 1000 ppm or more.

From the viewpoint of obtaining excellent strength and low chlorination, the (α) polyarylene sulfide resin used in the present invention preferably has a small amount of chloroform extraction, but if it is too small, the melt viscosity tends to increase. 0.0 mass% or more, more preferably 1.5 mass% or more, and even more preferably 2.0 mass% or more. On the other hand, when the amount of chloroform is too high, the amount of adhesive gas generated tends to increase. Therefore, 5.0 mass% or less, More preferably, it is 4.0 mass% or less, More preferably, 3.0 mass% or less is preferable.
The amount of chloroform extracted may be appropriately adjusted by a method of washing with an organic solvent in the washing step when producing the polyarylene fide resin. The amount of chloroform extracted in the present invention was extracted with a Soxhlet extractor using a PPS sample amount of about 10 g and chloroform of 200 ml for 5 hours, and the extract was dried at 50 ° C. It is a percentage notation multiplied by 100.

  In the present invention, although it depends on the type and blending amount of the amorphous resin, non-fibrous filler, and fibrous filler other than (α) polyarylene fide resin, it can be used for fluidity, toughness, variability. In order to balance the chlorine atom weight and low warpage, it is preferable to use two or more polyarylene sulfide resins in combination. In particular, when an amorphous resin, a non-fibrous filler, or a fibrous filler is blended, the melt viscosity of the polyarylene sulfide resin to be used is important because the fluidity is deteriorated.

  The polyarylene sulfide resin composition of the present invention contains (β) non-fibrous filler and (γ) fibrous filler as essential components together with (α) polyarylene sulfide resin. mass

  Specific examples of such (β) non-fibrous fillers include silicates such as talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, bentonite, asbestos, alumina silicate, silicon oxide, oxidation Metal compounds such as magnesium, alumina, zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, calcium hydroxide, magnesium hydroxide and aluminum hydroxide Such as hydroxide, glass beads, glass flakes, glass powder, ceramic beads, boron nitride, silicon carbide, carbon black and silica, graphite, etc., and these may be hollow, and further these fillers Two or more types can be used together A. These fillers may be used after pretreatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound. Of these, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfates such as calcium sulfate and barium sulfate, silicates such as kaolin, clay and talc, alumina and graphite are particularly preferable.

  In the measurement of the chlorine atom content of the polyarylene sulfide resin composition of the present invention, it is preferable to blend a non-fibrous filler in order to stabilize the measured value of the chlorine atom content. In the present invention, calcium carbonate is particularly preferable from the viewpoints of cost, dimensional stability, and stabilization of the measured value of the chlorine atom content. The blending amount of the (β) non-fibrous filler in the present invention is not particularly limited as long as it does not impair the effects of the present invention, but the resin component 100 in the polyarylene sulfide resin composition of the present invention. More than 50 mass parts and 150 mass parts or less are preferable with respect to a mass part.

  Specific examples of the (γ) fibrous filler include glass fiber, carbon fiber, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, A ceramic fiber, asbestos fiber, a stone fiber, a metal fiber, etc. are mentioned, These can also be used together 2 or more types. In addition, using these fillers with a pretreatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound can provide better mechanical strength. Preferred in meaning. Of these, glass fiber and carbon fiber are more preferably used. A silane compound having at least one functional group selected from an epoxy group, amino group, isocyanate group, hydroxyl group, mercapto group and ureido group is preferred as the coupling agent. Furthermore, a binder made of a synthetic resin emulsion such as epoxy resin, urethane resin, acrylic resin, vinyl acetate, the above-mentioned coupling agent, and other surfactants is applied to the fibrous filler, and several hundred to several thousand. It is further preferable to use the bunched chopped strand or the like in the sense of obtaining higher mechanical strength. In this invention, since the content rate of PAS resin with low chlorine atom content in a composition is high, compatibility with ((gamma)) fibrous filler improves. For this reason, adhesiveness with a matrix improves and it becomes what was excellent in heat-and-moisture resistance. This tendency becomes more prominent when (γ) fibrous filler is pretreated with a coupling material.

  In the present invention, the total amount of (β) non-fibrous filler and (γ) fibrous filler is 100 parts by mass or more and 300 parts by mass with respect to 100 parts by mass of the resin component in the polyarylene sulfide resin composition of the present invention. It is necessary to contain it by mass part or less, the range of 135 mass parts or more and 250 mass parts or less is preferable, and the range of 170 mass parts or more and 200 mass parts or less is more preferably selected.

When the total amount of (β) non-fibrous filler and (γ) fibrous filler is less than 100 parts by mass with respect to 100 parts by mass of the resin component in the polyarylene sulfide resin composition of the present invention, mechanical strength When the amount is 300 parts by mass or more, the melt fluidity and heat-and-moisture resistance are impaired.

  In the present invention, the ratio of the content of (β) non-fibrous filler and the content of (γ) fibrous filler is not particularly limited as long as it does not impair the effects of the present invention, but dimensional stability In particular, from the viewpoint of low warpage, the content of (β) non-fibrous filler is preferably equal to or greater than the content of (γ) fibrous filler.

  Furthermore, in the polyarylene sulfide resin composition of the present invention, (δ) an amorphous resin having a glass transition temperature of 110 ° C. or higher is contained in an amount of 3 to 50 parts by mass with respect to 100 parts by mass of (α) polyarylene sulfide resin. Is preferable, the range of 5-40 mass parts is more preferable, and the range of 8-30 mass parts is still more preferable. Here, the glass transition temperature is a value obtained by increasing the temperature at a rate of 20 ° C./min using a differential scanning calorimeter (DSC).

  Specific examples of the amorphous resin having a glass transition temperature of 110 ° C. or higher (δ) include polycarbonate resins, polyphenylene ether resins, polysulfone resins, polyethersulfone resins, polyarylate resins, polyetherimide resins. Examples thereof include resins and polyamideimide resins, among which polyphenylene ether resins, polyetherimide resins, polysulfone resins and polyethersulfone resins are particularly suitable, and polyphenylene ether resins are particularly preferred.

  The polyarylene sulfide resin composition of the present invention may further be blended with other resins as long as the effects of the present invention are not impaired. The blendable resin is not particularly limited, and specific examples thereof include nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, polyamide such as aromatic nylon, polyethylene terephthalate, polybutylene terephthalate, poly Polyester resins such as cyclohexyldimethylene terephthalate and polynaphthalene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene, olefin copolymers having functional groups such as carboxyl groups, carboxylic ester groups, acid anhydride groups, and epoxy groups, polyolefin elastomers , Polyetherester elastomer, polyetheramide elastomer, polyacetal, polyimide, polyketone resin, liquid crystal polymer, polyetherketone resin, poly Oh ether ketone resin, polyether ether ketone resins, polyethylene tetrafluoride resins, epoxy group-containing polyolefin copolymer, polystyrene, etc. Shinji O tack tick polystyrene.

  However, in order to sufficiently exhibit the effects of the present invention, it is preferable that 70% by mass or more of the resin component constituting the polyarylene sulfide resin composition of the present invention is (α) polyarylene sulfide resin. Furthermore, the PPS resin composition of the present invention has an epoxy group, an amino group, an isocyanate group, a hydroxyl group, a mercapto group, and a ureido group for the purpose of improving mechanical strength, toughness and the like within a range not impairing the effects of the present invention. A silane compound having at least one functional group selected from among them may be added. Specific examples of such compounds include epoxy group-containing alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. Compounds, mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) ) Ureido group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, Isocyanato group-containing alkoxysilane compounds such as γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ- (2- Amino group-containing alkoxysilane compounds such as aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, and γ-hydroxypropyltrimethoxysilane, γ- Examples thereof include a hydroxyl group-containing alkoxysilane compound such as hydroxypropyltriethoxysilane. Among these, an alkoxysilane having an epoxy group, an amino group, an isocyanate group, or a hydroxyl group is particularly suitable for obtaining an excellent weld strength.

  A suitable addition amount of the silane compound is selected in a range of 0.05 to 3 parts by mass with respect to 100 parts by mass of the polyphenylene sulfide resin.

  In the polyarylene sulfide resin composition of the present invention, other components such as antioxidants and heat stabilizers (hindered phenol-based, hydroquinone-based, phosphite-based, and these) can be used as long as the effects of the present invention are not impaired. Substitutes, etc.), weathering agents (resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.), release agents and lubricants (montanic acid and its metal salts, esters, half esters, stearyl alcohol, stearamide) , Various bisamides, bisureas, polyethylene waxes, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black for coloring, etc.), dyes (eg nigrosine), crystal nucleating agents (talc, silica, kaolin, clays, etc.), plasticizers (p -Octyl oxybenzoate, N-butylbenze Sulfonamides, etc.), antistatic agents (alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type cationic antistatic agents, nonionic antistatic agents such as polyoxyethylene sorbitan monostearate, betaine amphoteric charging Inhibitors), flame retardants (eg, red phosphorus, phosphate esters, melamine cyanurate, magnesium hydroxide, aluminum hydroxide and other hydroxides, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, Brominated epoxy resins or combinations of these brominated flame retardants and antimony trioxide), heat stabilizers, lubricants such as calcium stearate, aluminum stearate, lithium stearate, UV inhibitors, colorants, flame retardants and foaming Normal additives such as agents It can be added.

  The method for preparing the polyarylene sulfide resin composition of the present invention is not particularly limited, but each raw material is supplied to a generally known melt mixer such as a single or twin screw extruder, a Banbury mixer, a kneader and a mixing roll. As a representative example, a method of kneading at a temperature of 280 to 380 ° C. can be given. There are no particular restrictions on the mixing order of the raw materials, a method in which all raw materials are blended and melt kneaded by the above method, a part of the raw materials are melted and kneaded by the above method, and the remaining raw materials are further blended and melt kneaded. Any method may be used, such as a method of mixing a part of raw materials or a method of mixing the remaining raw materials using a side feeder during melt kneading by a single-screw or twin-screw extruder after compounding. As for the small amount additive component, other components may be kneaded and pelletized by the above-described method and then added before molding and used for molding.

  Among them, a preferable method for preparing the polyarylene sulfide resin composition of the present invention is a method of melt-kneading with a twin-screw extruder. When melt-kneading with such a twin-screw extruder, the screw rotation speed is preferably controlled to 200 to 400 rpm, more preferably 230 to 350 rpm.

  Usually, from the viewpoint of increasing the discharge amount per unit time and increasing the productivity, a method of increasing the screw rotation speed is adopted as long as the torque capacity of the extruder allows. However, since the resin composition of the present invention contains a large amount of filler, when the screw rotation speed is increased too much, decomposition of the resin is promoted by shearing heat generation. When adjusting the polyarylene sulfide resin composition of the present invention by a method of melt kneading with a biaxial extruder, it is more preferable to control the screw rotation speed to 400 rpm or less, preferably less than 350 rpm. However, even if the screw rotation speed is less than 200 rpm, the effect of suppressing the decomposition of the resin due to shearing heat generation is small, and it is preferable to set it to 200 rpm or more in consideration of productivity.

  The polyarylene sulfide resin composition of the present invention thus obtained can be used for various moldings such as injection molding, extrusion molding, blow molding and transfer molding, and is particularly suitable for injection molding applications.

A molded product obtained by melt-molding the polyarylene sulfide resin composition of the present invention obtained as described above (hereinafter, abbreviated as the molded product of the present invention) has a low chlorine atom content and has high melt fluidity. Excellent dimensional stability during repeated molding, especially low warpage when the molded product is thinned, and also excellent in heat and moisture resistance.
Therefore, the polyarylene sulfide resin composition of the present invention includes, for example, a sensor, an LED lamp, a connector, a connector component, a capacitor component socket, a resistor, a relay case, a switch, a coil bobbin, a capacitor, a variable capacitor case, an oscillator, and various terminals. Board, transformer, plug, printed circuit board, tuner, speaker, microphone, headphones, small motor, magnetic head base, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor brush holder, parabolic antenna, computer related parts Electrical / electronic parts: VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser disks / compact disks, light Houses, office electrical product parts, office computer parts, telephone equipment parts, facsimiles, such as backup parts, optical pickup parts for both reproduction and recording, lighting parts, refrigerator parts, air conditioner parts, typewriter parts, word processor parts, etc. Machine-related parts represented by related parts, copier-related parts, cleaning jigs, motor parts, lighters, typewriters, etc .: Optical equipment represented by microscopes, binoculars, cameras, watches, precision machine-related parts; Faucet piece, mixing faucet, pump parts, pipe joint, water volume control valve, relief valve, hot water temperature sensor, water volume sensor, water meter housing and other water-related parts; valve alternator terminal, alternator connector, IC regulator, for light dial Potentiometer Various valves such as base, exhaust gas valve, fuel-related / exhaust system / intake system pipes, air intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor , Oil temperature sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor Related parts, distributor, starter switch, starter relay, transmission wire harness, c Wind washer nozzle, air conditioner panel switch board, fuel-related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil It can be used for various applications such as automobiles and vehicle-related parts such as filters, ignition device cases, vehicle speed sensors, and cable liners.

  EXAMPLES Hereinafter, although an Example is shown and this invention is demonstrated further more concretely, this invention is not limited to description of these Examples.

[Melt viscosity]
Using a flow tester (Shimadzu Corporation Koka-type flow tester “CFT-500D type”), the temperature / 300 ° C., the load 1.96 MPa, the orifice length / orifice diameter ratio is 10/1. The melt viscosity after holding for 6 minutes was measured using an orifice.

[Bending strength]
Measurements were performed according to ISO 178. Specifically, the measurement was performed as follows. Test pieces were obtained by injection molding using an ISO type A mold. A test piece having a central part width of 10 mm, a length of 80 mm and a thickness of 4 mm was cut out and measured under conditions of a span of 64 mm and a strain rate of 5 mm / min in an atmosphere of 23 ° C. and a relative humidity of 50%.

[Spiral flow length]
Using a 1.6 mm thick spiral flow mold, the flow length was measured when molding was performed at a cylinder temperature of 330 ° C., a mold temperature of 150 ° C., and an injection speed of 60 mm / sec.

[Amount of chlorine atom contained]
The gas generated by burning the polymer with a Dia Instruments combustion gas absorption device was absorbed into pure water, and the chlorine ions in the absorption solution were quantified and converted by a Dionex ion chromatograph.

[Low warpage]
Injection molding was performed using an ISO type D1 mold (film gate mold having a thickness of 1 mm, a width of 60 mm and a length of 60 mm). After molding, the molded product was left in a desiccator under no load for 24 hours. When the molded product was placed on a horizontal desk in an upward direction and the two vertexes on the gate side were fixed on the desk, the distance between the vertex farthest from the desk and the desk was measured.

[Synthesis Example 1]
In a 4 liter autoclave made of titanium-lined stainless steel with stirring blades connected to a temperature sensor, cooling tower, dropping tank, and dropping pump, 586.0 g of sodium hydrofluoride (hereinafter abbreviated as NaSH · 3.4H ₂ O) 586.0 g (5.0 Mol), 416 g (5.0 mol) of 48% sodium hydroxide and 1586 g (16 mol) of N-methylpyrrolidone (hereinafter abbreviated as NMP) at room temperature, and heated to 205 ° C. in a nitrogen atmosphere while stirring. , 522.0 g of water was distilled off. Thereafter, the reaction system was sealed, and the temperature was further raised to 220 ° C., and 1.10 g (0.010 mol) of 0.2 mol% of thiophenol with respect to NaSH, p-dichlorobenzene (hereinafter abbreviated as p-DCB). A mixed solution of 735.0 g (5.0 mol) and NMP 396 g (4 mol) was added dropwise over 1 hour, and the mixture was stirred at 220 ° C. for 6 hours, then heated to 250 ° C. and stirred for 1 hour. Here, thiophenol is added when the reaction rate of p-dichlorobenzene is 0%.

After completion of the reaction, the reaction mixture was cooled to obtain a reaction slurry. 20 liters of water was added to the resulting slurry, stirred at 80 ° C. for 1 hour, and then filtered.
The obtained cake was redispersed in 5 liters of water, stirred at 80 ° C. for 1 hour, and then filtered. The cake obtained by repeating this operation three times was dried overnight at 120 ° C. in a hot air dryer to obtain 515 g (yield 95%) of white powdery PAS. The melt viscosity was 37 Pa · S. The chlorine atom content in PAS was 1800 ppm. Hereinafter, the obtained PAS is referred to as PAS (A1).

[Synthesis Example 2]
The same operation as in Example 1 was performed except that 2.75 g (0.025 mol) of 0.5 mol% of thiophenol was added to NaSH immediately after dropwise addition of the mixed solution of p-DCB and NMP in 1 hour. went. The reaction rate of p-DCB when thiophenol was added was 25%. The melt viscosity of the obtained PAS was 28 Pa · S. The chlorine atom content of PAS was 1900 ppm. Hereinafter, the obtained PAS is referred to as PAS (A2).

[Synthesis Example 3]
Except that 5.50 g (0.050 mol) of 1.0 mol% of thiophenol was added to NaSH and stirred for 6 hours at 220 ° C., then the temperature was raised to 250 ° C. and stirred for 3 hours. The same operation as 1 was performed. The melt viscosity of the obtained PAS was 10 Pa · S. The chlorine atom content of PAS was 1200 ppm. Hereinafter, the obtained PAS is referred to as PAS (A3).

[Comparative Synthesis Example 1]
PAS was produced according to Synthesis Example 1 of JP 2010-53356. That is, in a 70 liter autoclave equipped with a stirrer, 8267.37 g (70.00 mol) of 47.5% sodium hydrosulfide, 2957.21 g (70.97 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone (NMP) 11434.50 g (115.50 mol), sodium acetate 1722.00 g (21.00 mol), and ion-exchanged water 10500 g were charged and gradually heated to 245 ° C. over about 3 hours through nitrogen at normal pressure. After distilling 14780.1 g of water and 280 g of NMP, the reaction vessel was cooled to 160 ° C. The residual water content in the system per 1 mol of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.

  Next, 10235.46 g (69.63 mol) of p-dichlorobenzene and 900.00 g (91.00 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and stirred at 240 rpm while stirring at 0.6 ° C. / The temperature was raised to 238 ° C. at a rate of minutes. After reacting at 238 ° C. for 95 minutes, the temperature was raised to 270 ° C. at a rate of 0.8 ° C./min. After reacting at 270 ° C. for 100 minutes, 1260 g (70 mol) of water was injected over 15 minutes and cooled to 250 ° C. at a rate of 1.3 ° C./minute. Thereafter, it was cooled to 200 ° C. at a rate of 1.0 ° C./min, and then rapidly cooled to near room temperature.

  The contents were taken out, diluted with 26300 g of NMP, the solvent and solid matter were filtered off with a sieve (80 mesh), and the resulting particles were washed with 31900 g of NMP and filtered off. This was washed several times with 56000 g of ion-exchanged water and filtered, then washed with 70000 g of 0.05 wt% aqueous acetic acid and filtered. After washing with 70000 g of ion-exchanged water and filtering, the resulting hydrous PPS particles were dried with hot air at 80 ° C. and dried under reduced pressure at 120 ° C. The obtained PPS was linear, had a melt viscosity of 100 Pa · s and a chlorine atom content of 1300 ppm. Hereinafter, the obtained PAS is referred to as PAS (A4).

[Comparative Synthesis Example 2]
PAS was produced according to Synthesis Example 3 of Patent Document 1 (Japanese Patent Laid-Open No. 2010-53356). M3910 manufactured by Toray Industries, Inc. was treated in a hot air oven at 210 ° C. for 1 hour. The obtained PPS was a crosslinking type, and had a melt viscosity of 15 Pa · s and a chlorine atom content of 3000 ppm. Hereinafter, the obtained PAS is referred to as PAS (A5).

Examples 1-5 / Comparative Examples 1-3
Each component was dry blended at the ratio shown in the table, and then melt-kneaded at a screw rotation speed of 250 rpm and a cylinder set temperature of 320 ° C. using a TEM-35B twin screw extruder manufactured by Toshiba Machine Co., Ltd., and pelletized with a strand cutter. The pellets dried for 3 hours at 140 ° C. were used for molding and evaluation.

In Tables 1 and 2, numerical values in parentheses of components (A) to (D) represent parts by mass, and abbreviations are as follows.
Non-fibrous filler (B1): Calcium carbonate “Calcium carbonate grade 1” manufactured by Maruo Calcium
Glass fiber (C1): Glass fiber chopped strand (fiber length 3 mm, average fiber diameter 10 μm)
Amorphous resin (D1): Mitsubishi Engineering Plastics polyphenylene ether “PX-100L”

Claims (6)

(Α) a polyarylene sulfide resin, (β) a non-fibrous filler, and (γ) a polyarylene sulfide resin composition obtained by melt-kneading a fibrous filler,
The (α) polyarylene sulfide resin has a melt viscosity (320 ° C., shear rate 1000 / s) in a range of less than 100 [Pa · s] and a chlorine atom content in a range of 2000 ppm or less. The total amount of the fibrous filler and (γ) fibrous filler is 100 to 300 parts by mass with respect to 100 parts by mass of the resin component in the polyarylene sulfide resin composition, and (β) non-fibrous filling A polyarylene sulfide resin composition, wherein the content of the material is not less than the content of (γ) fibrous filler and the chlorine atom content in the polyarylene sulfide resin composition is 900 ppm or less. In the method for producing polyarylene sulfide by reacting the (α) polyarylene sulfide resin with an alkali metal sulfide (A) and a dihaloaromatic compound (B) in a polar solvent, the dihaloaromatic compound (B ) In which the reaction rate of 0 to 40% is added, one or more compounds (C) selected from the group consisting of mercapto compounds, metal salts of mercapto compounds, phenol compounds, metal salts of phenol compounds and disulfide compounds are added. The polyarylene sulfide resin composition according to claim 1, which is obtained by: The polyarylene sulfide resin composition according to claim 1 or 2, wherein 70% by mass or more of the resin component constituting the polyarylene sulfide resin composition is (A) a polyarylene sulfide resin. The polyarylene sulfide resin composition according to any one of claims 1 to 3, further comprising (δ) an amorphous resin having a glass transition temperature of 110 ° C or higher in addition to the component. 5. The poly according to claim 4, wherein the amorphous resin is a polycarbonate resin, a polyphenylene ether resin, a polysulfone resin, a polyether sulfone resin, a polyarylate resin, a polyetherimide resin, or a polyamideimide resin. Arylene sulfide resin composition. A molded article obtained by melt-molding the polyarylene sulfide resin composition according to any one of claims 1 to 5.