JP2007197625A - Method for treating polyarylene sulfide resin - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for treating a polyarylene sulfide resin generating little gas and smell, and suitable for a lamp case part and a surrounding part of a printer, a projector, a rear projection TV or the like in which the generation of the smell is disliked, in home electric appliance products, OA (office automation) equipment or the like; to provide a polyarylene sulfide resin composition obtained by using the treated polyarylene sulfide resin; and to provide a molded product obtained by molding the composition. <P>SOLUTION: The method for treating the polyarylene sulfide resin involves heating a polyarylene sulfide resin so that the ratio (A)/(B) may be ≤0.6 [wherein, (A) is the rate of change of weight between the not-heat-treated polyarylene sulfide resin before heating and the not-heat-treated polyarylene sulfide resin after 4 hr heating at 200°C in a vacuum condition; and (B) is the rate of change of weight between the heat-treated polyarylene sulfide resin before heating and the heat-treated polyarylene sulfide resin after 4 hr heating at 200°C in a vacuum condition]. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a method for treating a polyarylene sulfide resin excellent in low gas properties and low odor, a polyarylene sulfide resin composition obtained by using the polyarylene sulfide resin, and a molded product formed by molding the same. It is about.

  Among thermoplastic resins, parts using polyphenylene sulfide resin are excellent in heat resistance, impact resistance, high rigidity, molding processability, and excellent in flame resistance, chemical resistance, dimensional stability, and electrical characteristics. It has attracted attention as a high-performance, high-performance engineering plastic. In recent years, these characteristics have attracted attention as lamp case parts such as printer parts, projectors and rear projection TVs, and their peripheral parts.

  However, materials using polyarylene sulfide resin have some drawbacks. For example, when used as a lamp case component of a projector, the temperature around the lamp becomes as high as about 200 ° C., and a odor is generated from the molded product of polyphenylene sulfide resin. Therefore, heat treatment must be performed before assembly. There was a problem of being up. Because of such problems, there is a demand for supply of resin material parts in which the odor of the polyphenylene sulfide resin molded product is reduced by a low cost method.

  Heat treatment of polyphenylene sulfide resin has been performed for some time. For example, Patent Document 1 discloses that the polymer viscosity is in the range of 5000 to 16000 poise (500 to 1600 Pa · s) (310 ° C., shear rate of 200 / sec), and the non-Newtonian coefficient is in the range of n to 1.5 to 2.1. An extruded product obtained by curing a polyphenylene sulfide resin so as to be inside and melt-extruding the resin is disclosed. However, 5000 poise is less than 100 g / 10 min in terms of melt flow rate, and since such a polyphenylene sulfide resin has a melt viscosity that is too high, the injection pressure becomes too high at the time of molding, and a molded product that requires good fluidity is used. Not suitable for molding.

  In Patent Document 2, PPS having a melt flow rate of 2000 g / 10 min or less is oxidized and crosslinked, the melt flow rate is 500 g / 10 min or less, and the ratio of the melt flow rate before and after the oxidation crosslinking is 1/2 to 1/30. A method for producing PPS is disclosed. However, when the thermal oxidation treatment is performed to a high degree such that the melt flow rate ratio before and after the oxidation crosslinking is 1/2 to 1/30, the injection pressure becomes too high at the time of molding, and molding of molded products that require good fluidity. Not suitable for.

  Patent Document 3 discloses a PPS curing method in which PPS having a melt flow rate before oxidative crosslinking of 500 g / 10 min or less is subjected to oxidative crosslinking until the melt flow rate reaches 100 g / 10 min or less. However, polyphenylene sulfide having a melt flow rate value of 100 g / 10 min or less has a melt viscosity that is too high, so that the injection pressure becomes too high at the time of molding and is not suitable for molding a molded product that requires good fluidity.

  Patent Document 4 discloses a method of thermally oxidizing granular polyphenylene sulfide having a weight average molecular weight of 30,000 or more and an average particle diameter of 50 μm or less. However, as described in Patent Document 4, in order to obtain a polyphenylene sulfide resin having a weight average molecular weight of 30,000 or more and an average particle size of 50 μm or less, a special polymerization apparatus or pulverization is required, and the cost is also reduced. It is not a general method. Furthermore, such fine polyphenylene sulfide particles are inferior in biting to the extruder during melt kneading and are economically disadvantageous because the amount of melt kneading extrusion per unit time is reduced.

Although Patent Document 5 discloses a method of curing polyphenylene sulfide in a low oxygen atmosphere, the thermal oxidation treatment technique disclosed in the Examples is too strong for thermal oxidation treatment, so that the injection pressure during molding is high. It becomes too high and is not suitable for molding of a molded product that requires good fluidity.
Japanese Patent Laid-Open No. 63-207827 (Claims) JP 62-197422 A (Claims) JP-A-5-43692 (Claims) JP-A-6-248078 (Claims) JP-A-1-121327 (Claims)

  Therefore, the present invention is a method for treating a polyarylene sulfide resin suitable for lamp case parts and peripheral parts such as printers, projectors, rear projection TVs, etc., which generate less odors in home appliances, OA equipment, etc. with less generated gas and odor. Another object of the present invention is to provide a polyarylene sulfide resin composition using the treated polyarylene sulfide resin, and a molded product formed by molding the polyarylene sulfide resin composition.

The present invention can solve the above-mentioned problems by treating the polyarylene sulfide resin by the following method and blending the treated polyarylene sulfide resin and inorganic fibers. That is, the present invention
(1) Vacuum state of polyarylene sulfide resin before heat treatment at 200 ° C., 4 hours after weight change rate (A), (A), vacuum state of polyarylene sulfide resin after heat treatment at 200 ° C., 4 hours later A method for treating a polyarylene sulfide resin, wherein the rate of weight change is (B), and the polyarylene sulfide resin is heated so that (B) / (A) is 0.6 or less,
(2) The polyarylene sulfide resin according to (1), wherein the polyarylene sulfide resin is produced by the Quench method, the heating temperature is 200 ° C. to 260 ° C., and the heating time is 0.5 hours to 6 hours. Resin treatment method,
(3) A polyarylene sulfide resin obtained by performing the method for treating a polyarylene sulfide resin according to (1) or (2), wherein the odor index equivalent value is 28 or less,
(4) Polyarylene sulfide obtained by blending 1 to 99% by weight of (C) polyarylene sulfide resin described in (3) and (D) 1 to 99% by weight of inorganic filler, with the total composition being 100% by weight. And a molded article formed by molding the polyarylene sulfide resin composition according to (5) and (4).

  If the polyarylene sulfide resin composition using the polyarylene sulfide resin of the present invention configured as described above is used, the resin composition is excellent in low gas property and low odor at the time of molding. A molded product obtained by injection-molding a square plate with a thickness of 80 mm and a thickness of 3 mm is cut into four equal parts and treated at 200 ° C. for 4 hours. It is possible to obtain a molded product having excellent properties and practicality. In particular, a molded article using the polyarylene sulfide resin composition of the present invention is useful for lamp case parts and peripheral parts of home appliances, printers for OA equipment, projectors, rear projection TVs, and the like.

  (A) As a polyarylene sulfide resin used by this invention, the polyphenylene sulfide resin which has a repeating unit shown by the following structural formula is mentioned preferably.

  A polyphenylene sulfide resin containing 70 mol% or more, particularly 90 mol% or more of the repeating unit represented by the above structural formula is more preferable from the viewpoint of heat resistance. Further, the polyphenylene sulfide resin may comprise less than 30 mol% of the repeating units composed of repeating units having the following structure.

  The method for producing the polyarylene sulfide resin is not particularly limited, and is generally a known method, for example, a method for obtaining a polymer having a relatively low molecular weight described in JP-B-45-3368 (hereinafter referred to as a flash method). Or a method for obtaining a polymer having a relatively large molecular weight (hereinafter referred to as Quench method) described in JP-B-52-12240.

  The difference between the flash method and the quench method is the presence or absence of an alkali metal carboxylate as a polymerization aid in the polymerization system.

  Since the polyarylene sulfide resin obtained by the flash method does not add an alkali metal carboxylate into the polymerization system, the degree of polymerization does not increase, the molecular weight is relatively small, and the mechanical strength is low. In addition, since the polymer contains a large amount of impurities, the effects of the invention are hardly exhibited even when the treatment method of the present invention is performed.

  The PPS resin obtained by the Quench method has an increased degree of polymerization, a relatively high molecular weight, and a high mechanical strength because an alkali metal carboxylate is added to the polymerization system. Moreover, since there is little content of impurities and the amount of gas generation can be suppressed, it is preferable as the polyarylene sulfide resin used in the present invention.

  In the present invention, the polyarylene sulfide resin obtained as described above is preferably used after being washed with an organic solvent, hot water, an aqueous acid solution or the like. Organic solvent cleaning is preferable because impurities that cause odor components can be removed.

  The organic solvent used for washing the polyarylene sulfide resin is not particularly limited as long as it does not have an action of decomposing the polyarylene sulfide resin. For example, N-methyl-2-pyrrolidone (hereinafter referred to as NMP), dimethyl Nitrogen-containing polar solvents such as formamide, dimethylacetamide, 1,3-dimethylimidazolidinone, hexamethylphosphoramide, piperazinones, sulfoxide and sulfone solvents such as dimethyl sulfoxide, dimethyl sulfone, sulfolane, acetone, methyl ethyl ketone, diethyl ketone , Ketone solvents such as acetophenone, ether solvents such as dimethyl ether, dipropyl ether, dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene Halogen solvents such as ethylene, monochloroethane, dichloroethane, tetrachloroethane, perchlorethane, chlorobenzene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol, etc. Alcohol-phenol solvents and aromatic hydrocarbon solvents such as benzene, toluene and xylene. Among these organic solvents, the use of NMP, acetone, dimethylformamide, chloroform and the like is particularly preferable. These organic solvents are used alone or in combination of two or more.

  As a method of washing with an organic solvent, there is a method of immersing a polyarylene sulfide resin in an organic solvent, and it is preferable to stir or heat for the purpose of making the effect of the present invention more remarkable. Although there is no restriction | limiting in particular in the usage-amount of the organic solvent with respect to polyarylene sulfide resin, It is preferable that it is 1-100 kg with respect to 1 kg of dried polyarylene sulfide resin, It is more preferable that it is 2-50 kg, 3-15 kg More preferably it is.

  There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning polyarylene sulfide resin with an organic solvent, Arbitrary temperature of about normal temperature-about 300 degreeC can be selected. However, since cleaning efficiency tends to increase as the cleaning temperature increases, it is preferable to perform cleaning at a high temperature of 100 to 300 ° C.

  It is also possible to wash in a pressure vessel under pressure (preferably 250 to 300 ° C.) at a temperature equal to or higher than the boiling point of the organic solvent. Also, the cleaning time is not particularly limited, but for the purpose of making the effect of the present invention more prominent, it is preferable to perform cleaning for 30 to 60 minutes or more in the case of batch cleaning. It is also possible to wash in a continuous manner.

  When the polyarylene sulfide resin produced by the polymerization is washed with an organic solvent, the organic solvent is preferably washed with water after the organic solvent, so that the remaining organic solvent can be removed relatively easily. The water used for these washings is preferably distilled water or deionized water. The water washing temperature is preferably 50 to 90 ° C, and preferably 60 to 80 ° C.

  Acid cleaning is possible for the purpose of improving the mechanical strength. Specific acid cleaning conditions will be described. The acid used for the acid treatment of the polyarylene sulfide resin is not particularly limited as long as it does not have an action of decomposing the polyarylene sulfide resin, but acetic acid, silicic acid, carbonic acid, and propyl acid are preferable, and acetic acid is more preferable. . Further, it is not preferable to decompose or deteriorate the polyarylene sulfide resin such as nitric acid.

  The acid treatment method includes a method of immersing the polyarylene sulfide resin in an acid or an aqueous solution of the acid, preferably stirring or heating, and the treatment time is preferably 30 to 60 minutes or more. The acid used for the acid treatment of the polyarylene sulfide resin preferably has a pH of 3.5 to 5.5, and the amount used is preferably 2 to 100 kg with respect to 1 kg of the dried polyarylene sulfide resin. It is more preferably 4 to 50 kg, and further preferably 5 to 15 kg. There is no restriction | limiting in particular in process temperature, Usually, it can carry out at room temperature, and when heating, it can carry out at 50-90 degreeC. For example, when using acetic acid, it is preferable to immerse the polyarylene sulfide resin powder in an aqueous solution of PH4 kept at room temperature and stir for 30 to 60 minutes or more. The polyarylene sulfide resin subjected to acid treatment is washed several times with water in order to physically remove remaining acid or salt. The water washing temperature is preferably 50 to 90 ° C, and preferably 60 to 80 ° C.

  As the water used for washing, distilled water or deionized water is used in the sense that the effect of chemical modification by acid treatment is not impaired. In the present invention, the above post-processing can be combined and can be repeated a plurality of times.

  In the heat treatment method of the present invention, the heat treatment temperature of the obtained polyarylene sulfide resin is preferably 200 to 260 ° C, and preferably 220 to 240 ° C. When the heat treatment temperature is lower than 200 ° C., the effect of the present invention cannot be obtained, which is not preferable. The oxygen concentration is preferably 2% by volume or more, more preferably 8% by volume or more. Although there is no restriction | limiting in particular in the upper limit of oxygen concentration, About 50 volume% is a limit and 25 volume% or less is more preferable. Examples of the treatment time include 0.5 to 50 hours, more preferably 0.5 to 20 hours, and further preferably 0.5 to 6 hours, but the treatment time needs to satisfy the range defined in the present invention. The heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary blade or a stirring blade. However, for efficient and more uniform treatment, a heating device with a rotary blade or a stirring blade is used. Is more preferable.

  Further, before and after the thermal oxidation treatment, it is possible to suppress thermal oxidation cross-linking and perform a dry heat treatment for the purpose of removing volatile components and moisture. The temperature is preferably 130 to 250 ° C, and more preferably 160 to 250 ° C. In this case, the oxygen concentration is preferably less than 2% by volume. The treatment time is preferably 0.5 to 50 hours, more preferably 1 to 20 hours, and even more preferably 1 to 10 hours, but is a time that satisfies the range defined in the present invention. The heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary blade or a stirring blade. However, for efficient and more uniform treatment, a heating device with a rotary blade or a stirring blade is used. Is more preferable.

  The polyarylene sulfide resin used in the present invention is a vacuum state of the polyarylene sulfide resin before the heat treatment, the weight change rate after 4 hours at 200 ° C. is (A), and the vacuum state of the polyarylene sulfide resin after the heat treatment. The polyarylene sulfide resin is treated so that the weight change rate after 4 hours at 200 ° C. is (B) and (B) / (A) is 0.6 or less. A polyarylene sulfide resin having (B) / (A) of 0.5 or less is preferable, and a polyarylene sulfide resin having 0.1 or less is more preferable. When (B) / (A) is larger than 0.6, the low odor property which is the effect of the present invention cannot be obtained, which is not preferable.

  The polyarylene sulfide resin treated in this manner has very little odor, and has an odor index equivalent value representing an odor concentration of 28 or less, and is extremely excellent in low odor. A preferable odor index equivalent value when the resin composition using the polyarylene sulfide resin is used as a molded product is 27 or less, more preferably 25 or less. If the odor equivalent index is greater than 28, the resin composition is formed into a molded product, and the odor emitted from the molded product tends to increase when heated to 200 ° C.

  The weight change rate was calculated by the following method before and after the heat treatment.

  The polyarylene sulfide resin (granular) was dried in a hot air oven at 130 ° C. for 3 hours, and 3 g of the polyarylene sulfide resin (granular) was vacuum sealed in a glass ampoule tube. One side of the glass ampule tube (the one with the polyphenylene sulfide resin) is left for 4 hours in a ceramic electric tubular furnace set at 200 ° C. (for example, ARF-30K manufactured by Asahi Rika Seisakusho). About 10 cm is cut off from the tip of the non-heated part (the one without the polyarylene sulfide resin (granular)). Due to the difference between the initial weight of the cut glass ampoule tube and the weight of the glass ampoule tube that has been agglomerated and adhered to the glass ampoule tube with 5 g of chloronaphthalene and then dried at room temperature for 12 hours or more, 200 ° C. in a vacuum state. The amount of substances generated from the polyarylene sulfide resin (granular) after 4 hours was calculated. Finally, a value obtained by dividing the obtained amount of the generated substance by the initial amount of the polyarylene sulfide resin (granular) 3 g was calculated as a weight change rate.

  The measurement method of the odor index equivalent value is a 500 mL gas cleaning bottle made of glass having 3 g of polyarylene sulfide resin (granular) with two entrances on the lid (for example, a gas cleaning bottle with a cylindrical filter, etc.). Listed). Silicon tubes were attached to the two mouths, and the tips were stopped with clips. The tube preferably does not generate odor at 200 ° C. It was placed in a hot air oven sized to accommodate all the gas cleaning bottle parts and left at 200 ° C. for 2 hours. After leaving, a 2.0 L bag was attached to one side of the silicon tube, 2.0 L of air was sent from the opposite direction, and the bag was plugged to obtain a gas sample. In addition, all the connection parts, such as a lid | cover and a silicon tube, took the countermeasure against leakage with the Teflon (trademark) tape so that gas might not leak.

  Nitrogen gas was added to the obtained gas sample to obtain a sample for measuring an odor index equivalent value by diluting the sample 10 times.

  Odor index equivalent value measurement sample is sucked into odor identification device FF-2A manufactured by Shimadzu Corporation, temperature is 25 ° C., gas suction time is 60 seconds, and measurement sequence is measured four times under ASmell condition. The average value of three times was used as measurement data. In addition, since it diluted 10 times, the data obtained by converting 10 times were made into the odor index equivalent value.

  Specifically, the odor index equivalent value of 10 means that if the sample is diluted 10 times, the odor is not felt, the odor index equivalent value 20 is 100 times that of the sample, and the odor index equivalent value 30 is 1000 times that of the sample. This is a value (odor concentration) indicating that no odor is felt when diluted twice.

The odor concentration is a numerical value calculated by 10 ^{X / 10,} where ^X is an odor index equivalent value, and this represents a magnification at which the odor is reduced until no odor is felt.

  The (D) inorganic filler used in the present invention is not particularly limited as long as it does not impair the effects of the present invention, and may be fibrous or non-fibrous. Such fibrous and / or non-fibrous fillers are glass fiber, glass milled fiber, carbon fiber, wollastonite fiber, potassium titanate whisker, calcium carbonate whisker, zinc oxide whisker, aluminum borate whisker, alumina fiber, silicon carbide fiber. Fibrous fillers such as ceramic fiber, asbestos fiber, masonry fiber, metal fiber, glass flake, wollastonite, zeolite, sericite, kaolin, mica, clay, pyrophyllite, bentonite, asbestos, talc, alumina silicate, etc. Silicate, alumina, silicon oxide, magnesium oxide, zirconium oxide, titanium oxide, iron oxide and other metal compounds, calcium carbonate, magnesium carbonate, dolomite and other carbonates, calcium sulfate, barium sulfate and other sulfuric acid Non-fibrous fillers such as hydroxides such as magnesium hydroxide, calcium hydroxide, aluminum hydroxide, glass beads, ceramic beads, boron nitride, silicon carbide, carbon black, metal powder and silica, It may be hollow, and two or more of these fillers may be used in combination. If it is fibrous, the average fiber diameter is preferably 5 to 14 μm, and the length of the fiber is preferably 1 mm to 6 mm in terms of supply stability during extrusion, or roving, if it is a short fiber. But it ’s okay. As the non-fibrous filler, those having a major axis L to minor axis D ratio (L / D) of 10 or less are particularly preferable.

  Such an inorganic filler can be used after being pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, or an epoxy compound. The amount of the coupling agent is not particularly limited as long as the effect of the present invention is not impaired. However, when the inorganic filler treated with the coupling agent is 100% by weight, the amount is 0.1% by weight to 10%. % By weight, preferably 0.5% by weight to 6% by weight, and more preferably 1% by weight to 3% by weight. If the amount of the coupling agent is less than 0.1% by weight, the adhesion effect with the polyarylene sulfide resin is hardly exhibited, and if it is 10% by weight or more, gas generation increases, which is not preferable.

  Among such inorganic fillers, it is particularly preferable to use glass fiber, carbon fiber, calcium carbonate, and talc in order to obtain a balance of mechanical properties.

  The blending amount of the (D) inorganic filler is 1 to 99 wt%, preferably 30 to 70 wt%, more preferably 35 to 65 wt% of the (D) inorganic filler when the total composition is 100 wt%. %. If the blending amount is too small, the heat resistance will be low, and it cannot be used for lamp case parts expected as an application of the present invention, and if the blending amount is too large, the mechanical properties tend to decrease, which is not preferable. .

  In the present invention, other types of polymers can be added in an amount that does not impair the effects of the present invention.

  Other polymers include polyethylene resin, polypropylene resin, polystyrene resin, ABS resin, polyamide resin, polycarbonate resin, polyethylene terephthalate resin, polybutylene terephthalate resin, polyacetal resin, modified polyphenylene ether resin, polysulfone resin, polyallyl sulfone resin, polyketone. Resin, polyetherimide resin, polyarylate resin, liquid crystal polymer, polyethersulfone resin, polyetherketone resin, polythioetherketone resin, polyetheretherketone resin, polyimide resin, polyamideimide resin, polytetrafluoroethylene resin, heat Mention may be made of thermoplastic resins such as plastic polyurethane resins, polyamide elastomers and polyester elastomers.

  In the present invention, a release agent, a crystal nucleating agent, and the like can be further blended in an amount that does not impair the effects of the present invention. Examples of the release agent include polyolefins such as polyethylene and polypropylene, or montanic acid waxes, or fatty acid amide polycondensates such as ethylenediamine / stearic acid polycondensate, ethylenediamine / stearic acid / sebacic acid polycondensate, and stearic acid. Examples thereof include metal soaps such as lithium and aluminum stearate. Examples of the crystal nucleating agent include polyether-terketone resin, nylon resin, talc, kaolin and the like.

  In addition, additives such as modifiers, anti-coloring agents, plasticizers, anticorrosives, antioxidants, heat stabilizers, thirstants, ultraviolet absorbers, coloring agents, flame retardants, antistatic agents, foaming agents, etc. It can add in the range which does not impair the effect of invention.

  Although there is no restriction | limiting in particular in the manufacturing method of the polyarylene sulfide resin composition of this invention, The mixture of a raw material is supplied to normally well-known melt mixers, such as a twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll, 280 degreeC ~ A typical example is a method of melt-kneading at a temperature of 380 ° C. Further, there is no particular limitation on the mixing order of the raw materials, and a method of blending by supplying the polyarylene sulfide resin, inorganic fibers and optional additives in advance to the melt mixer with or without dry blending is preferably mentioned. It is done.

  The thus obtained polyarylene sulfide resin composition of the present invention is generally molded by a known molding method for thermoplastic resins such as injection molding, extrusion molding, compression molding, blow molding, injection compression molding, transfer molding, vacuum molding and the like. Of these, injection molding is preferred.

  The odor index equivalent value of the polyarylene sulfide resin composition obtained in the present invention is 28 or less, and is extremely excellent in low odor. For parts that require low odor, the odor equivalent index is preferably 27 or less, and more preferably the odor index equivalent value is 25 or less. If the odor equivalent index is greater than 28, the resin composition is formed into a molded product, and the actual odor tends to increase when heated to 200 ° C.

  On the other hand, in a method for measuring the odor index equivalent value of a molded product obtained by injection molding a polyarylene sulfide resin composition, a square plate having a film gate of 80 mm in length, 80 mm in width, and 3 mm in thickness is clamped to 100 ton. Using an injection molding machine, molding was performed under conditions of a cylinder temperature of 320 ° C. and a mold temperature of 130 ° C., and the obtained square plate was cut into four equal parts with a band saw. The obtained molded product was sealed in the gas washing bottle, and a gas sample was obtained by the same gas sample preparation method as that for the polyarylene sulfide resin.

  Then, it measured by the same method as the measuring method of the odor index equivalent value of polyarylene sulfide resin.

  The polyarylene sulfide resin treated by the method for treating polyarylene sulfide resin of the present invention has very little odor, and the polyarylene sulfide resin composition using this polyarylene sulfide resin is excellent in low gas property and low odor property. Therefore, it is useful for parts such as printers for home appliances, OA equipment, projectors, rear projection TVs, and the like, and particularly useful for printer parts and projector lamp case parts whose operating environment is around 200 ° C.

  EXAMPLES Next, although an Example and a comparative example demonstrate this invention concretely, this invention is not restrict | limited at all by these.

  The weight change rate before and after the heat treatment, the odor index equivalent value, the odor concentration, and the tensile strength in the examples were measured according to the following methods.

<Rate of weight change before and after heat treatment>
The weight change rate was calculated by the following method before and after the heat treatment.

  The polyphenylene sulfide resin (granular) was dried in a hot air oven at 130 ° C. for 3 hours, and 3 g of the polyphenylene sulfide resin (granular) was vacuum sealed in a glass ampoule tube. One side of the glass ampule tube (the one with the polyphenylene sulfide resin (granular)) was left in a ceramic electric tubular furnace set at 200 ° C .: ARF-30K (Asahi Rika Seisakusho) for 4 hours, and then the glass ampule tube Cut about 10 cm from the tip of the non-heated portion (the one without polyphenylene sulfide resin (granular)). From the difference between the initial weight of the cut glass ampule tube and the aggregate and adhering components on the glass ampule tube, washed with 5 g of chloronaphthalene, and then dried at room temperature for 12 hours, the glass ampule tube was heated at 200 ° C., 4 ° C. The amount of substances generated from the polyphenylene sulfide resin (granular) after time was calculated. Finally, a value obtained by dividing the obtained amount of the generated substance by the initial amount of polyphenylene sulfide resin (granular) 3 g was calculated as a weight change rate.

<Odor index equivalent value, odor concentration>
In order to measure the odor index equivalent value, 3 g of polyarylene sulfide resin (granular) was placed in a glass 500 mL gas cleaning bottle (SIBATA, gas cleaning bottle with a cylindrical filter) having two openings on the lid. . Silicon tubes were attached to the two mouths, and the tips were stopped with clips. It was placed in a hot air oven sized to accommodate all the gas cleaning bottle parts and left at 200 ° C. for 2 hours. After leaving, a 2.0 L bag was attached to one side of the silicon tube, 2.0 L of air was sent from the opposite direction, and the bag was plugged to obtain a gas sample. In addition, all the connection parts, such as a lid | cover and a silicon tube, took the countermeasure against leakage with the Teflon (trademark) tape so that gas might not leak.

  On the other hand, in the method for measuring the odor index equivalent value of the polyphenylene sulfide resin composition, a cylinder plate having a film gate of 80 mm in length, 80 mm in width, and 3 mm in thickness is used with an injection molding machine having a mold clamping force of 100 ton, a cylinder temperature of 320 ° C., Molding was performed at a mold temperature of 130 ° C., and the obtained square plate was cut into four equal parts with a band saw. The obtained molded product was sealed in the gas cleaning bottle, and a gas sample was obtained by the same method.

  Nitrogen gas was added to the obtained gas sample to obtain a sample for measuring an odor index equivalent value by diluting the sample 10 times.

  Odor index equivalent value measurement sample is sucked into odor identification device FF-2A manufactured by Shimadzu Corporation, temperature is 25 ° C., gas suction time is 60 seconds, and measurement sequence is measured four times under ASmell condition. The average value of three times was used as measurement data. In addition, since it diluted 10 times, the data obtained by converting 10 times were made into the odor index equivalent value.

  Specifically, the odor index equivalent value of 10 means that if the sample is diluted 10 times, the odor is not felt, the odor index equivalent value 20 is 100 times that of the sample, and the odor index equivalent value 30 is 1000 times that of the sample. This is a value (odor concentration) indicating that no odor is felt when diluted twice.

The odor concentration is a numerical value calculated by 10 ^{X / 10,} where ^X is an odor index equivalent value, and this represents a magnification at which the odor is reduced until no odor is felt.

<Tensile strength>
In the tensile strength test, an ASTM No. 1 dumbbell piece having a gate on one side was molded using an injection molding machine with a clamping force of 100 ton at a cylinder temperature of 320 ° C. and a mold temperature of 130 ° C., and a tensile strain rate of 10 mm / min. A tensile strength test was performed according to ASTM-D638 under the condition of a distance between fulcrums of 114 mm. The tensile strength described in the examples is an average value of 5 times.

Examples 1-18, Comparative Examples 1-18
The prepared PPS-1 and PPS-2 were processed by the methods shown in Tables 1 and 2. The used PPS-1 and PPS-2 are shown below.

(Method for producing polyphenylene sulfide resin (PPS-1))
An autoclave equipped with a stirrer was charged with 6.005 kg (25 mol) of sodium sulfide 9 hydrate, 0.205 kg (2.5 mol) of sodium acetate and 5 kg of NMP. The temperature was gradually raised to 205 ° C. through nitrogen, and 3.6 liters of water Distilled. Next, after cooling the reaction vessel to 180 ° C., 3.719 kg (25.7 mol) of 1,4-dichlorobenzene and 3.7 kg of NMP were added, sealed under nitrogen, heated to 270 ° C., heated to 270 ° C. Reacted for 2.5 hours. After cooling, the reaction product was washed 5 times with warm water, then poured into 10 kg of NMP heated to 100 ° C., stirred for about 1 hour, filtered, and further washed several times with hot water. This was put into 25 liters of an acetic acid aqueous solution of pH 4 heated to 90 ° C., and stirred for about 1 hour. It was dried under reduced pressure at 80 ° C. for 24 hours to obtain PPS-1 having a cooling crystallization temperature of 220 ° C. and MFR of 1000 g / 10 min.

(Method for producing polyphenylene sulfide resin (PPS-2))
In an autoclave equipped with a stirrer, 6.005 kg (25 mol) of sodium sulfide 9 hydrate, 0.656 kg (8 mol) of sodium acetate and 5 kg of NMP were charged, and the temperature was gradually raised to 205 ° C. through nitrogen, and 3.6 liters of water was distilled. I put it out. Next, after cooling the reaction vessel to 180 ° C., 3.756 kg (25.55 mol) of 1,4-dichlorobenzene and 2.4 kg of NMP were added, sealed under nitrogen, heated to 270 ° C., heated at 270 ° C. Reacted for 2.5 hours. Next, the mixture was put into 10 kg of NMP heated to 100 ° C., stirred for about 1 hour, filtered, and further washed with hot water at 80 ° C. for 30 minutes three times. This was put into 25 liters of an acetic acid aqueous solution of pH 4 heated to 90 ° C., and stirred for about 1 hour, filtered, washed with ion-exchanged water of about 90 ° C. until the pH of the filtrate reached 7, It was dried under reduced pressure at 80 ° C. for 24 hours to obtain PPS-2 having a temperature-falling crystallization temperature of 215 ° C. and MFR of 300 g / 10 min.

  As is clear from Tables 1 and 2, Examples 1 to 10 each have a small odor index equivalent value (odor concentration), and Comparative Examples 1 to 9 all have a large odor index equivalent value.

Examples 1 and 2
PPS-1 was heat-treated in the atmosphere at 220 ° C. for 2 to 4 hours.

[Examples 3 and 4]
PPS-1 was heat-treated in the atmosphere at 240 ° C. for 1 to 2 hours.

Example 5
PPS-1 was heat-treated in the atmosphere at 260 ° C. for 1 hour.

[Examples 6, 7, and 8]
PPS-2 was heat-treated in the atmosphere at 200 ° C. for 2, 4, and 6 hours.

[Examples 9 and 10]
PPS-2 was heat-treated in the atmosphere at 220 ° C. for 2 to 4 hours.

[Comparative Example 1]
This is a case where PPS-1 is not heat-treated.

[Comparative Examples 2 and 3]
PPS-1 was heat-treated at 180 ° C. for 2 to 4 hours in the atmosphere.

[Comparative Example 4]
PPS-1 was heat-treated in air at 220 ° C. for 0.25 hours.

[Comparative Example 5]
PPS-1 was heat-treated in air at 240 ° C. for 0.25 hours.

[Comparative Example 6]
PPS-1 was heat-treated at 260 ° C. for 0.25 hours in the air.

[Comparative Example 7]
This is a case where PPS-2 is not heat-treated.

[Comparative Example 8]
PPS-2 was heat-treated in air at 220 ° C. for 0.25 hours.

[Comparative Example 9]
PPS-2 was heat-treated in the atmosphere at 240 ° C. for 0.25 hours.

  Examples 1 to 10 are all cases where the odor index equivalent value (odor concentration) is small, and Comparative Examples 1 to 9 are cases where the odor index equivalent value (odor concentration) is large.

  Next, the treated PPS-1, PPS-2 and inorganic filler were dry blended with the compositions shown in Tables 3 and 4. The used inorganic filler is shown below.

(Inorganic filler)
NSG Betrotex Co., Ltd. glass fiber EC13-3-910 Fiber length 3 mm, fiber diameter 10 mm (measurement method: JIS R3420)
The dry blend mixture thus obtained was set to a cylinder temperature of 320 ° C., supplied to a twin screw extruder (TEX-44 manufactured by Toshiba), melt kneaded with a twin screw extruder, pelletized, and polyphenylene sulfide resin. A composition was obtained.

[Examples 11 to 13]
PPS-1 treated under the conditions of Example 2 was dry blended with the composition shown in Table 3, and the dry blend mixture was set to a cylinder temperature of 320 ° C. and fed to a twin screw extruder (TEX-44 manufactured by Toshiba). The mixture was melt-kneaded with a twin-screw extruder and pelletized to obtain a polyphennin sulfide resin composition.

Example 14
A polyphenylene sulfide resin composition was obtained in the same manner as in Examples 11 to 13, except that PPS-1 treated under the conditions of Example 1 was dry blended with the composition shown in Table 3.

Example 15
A polyphenylene sulfide resin composition was obtained in the same manner as in Examples 11 to 13, except that PPS-1 treated under the conditions of Example 3 was dry blended with the composition shown in Table 3.

Example 16
A polyphenylene sulfide resin composition was obtained in the same manner as in Examples 11 to 13, except that PPS-1 treated under the conditions of Example 5 was dry blended with the composition shown in Table 3.

Example 17
A polyphenylene sulfide resin composition was obtained in the same manner as in Examples 11 to 13, except that PPS-2 treated under the conditions of Example 7 was dry blended with the composition shown in Table 3.

Example 18
A polyphenylene sulfide resin composition was obtained in the same manner as in Examples 11 to 13, except that PPS-2 treated under the conditions of Example 10 was dry blended with the composition shown in Table 3.

[Comparative Examples 10 and 16]
As shown in Comparative Examples 1 and 7, a polyphenylene sulfide resin composition was obtained by dry blending with the composition shown in Table 4 without treating the polyphenylene sulfide resin.

[Comparative Examples 11, 12, 15]
A polyphenylene sulfide resin composition was obtained by dry blending with the composition shown in Table 4 except that the polyphenylene sulfide resin was treated under conditions where the heating temperature was outside the scope of the claims.

[Comparative Examples 13, 14, 17, 18]
A polyphenylene sulfide resin composition was obtained by dry blending with the composition shown in Table 4 except that the polyphenylene sulfide resin was treated under conditions where the heating time was outside the scope of the claims.

  Examples 11 to 18 are cases where the odor index equivalent value (odor concentration) is small and the tensile strength is high, and Comparative Examples 10 and 13 are both high in odor index equivalent value (odor concentration) and tensile. This is the case when the strength is low. Comparative Examples 11, 12, and 14 to 18 are cases where the odor index equivalent value (odor concentration) is large.

Claims (5)

The vacuum state of the polyarylene sulfide resin before the heat treatment, 200 ° C., and the weight change rate after 4 hours are (A), and the polyarylene sulfide resin after the heat treatment is in the vacuum state, 200 ° C., 4 hours after the weight change rate. And (B), and the polyarylene sulfide resin is heated so that (B) / (A) is 0.6 or less. The treatment of polyarylene sulfide resin according to claim 1, wherein the polyarylene sulfide resin is produced by Quench method, the heating temperature is 200 ° C to 260 ° C, and the heating time is 0.5 hours to 6 hours. Method. A polyarylene sulfide resin which has been subjected to the method for treating a polyarylene sulfide resin according to claim 1 or 2 and has an odor index equivalent value of 28 or less. A polyarylene sulfide resin composition comprising 1 to 99% by weight of (C) polyarylene sulfide resin according to claim 3 and 1 to 99% by weight of (D) an inorganic filler, wherein the total composition is 100% by weight. . A molded article formed by molding the polyarylene sulfide resin composition according to claim 4.