JP2009209185A - Polyphenylene sulfide resin composition and its manufacturing method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polyphenylene sulfide resin composition that is excellent in freeze resistance and creep resistance and is suitable for automobile parts, electric components and parts for fluid piping of common apparatuses, particularly for parts for fluid piping for water sections, and a molded article obtained by molding the same. <P>SOLUTION: The polyphenylene sulfide resin composition comprises (A) 100 pts.wt. of a polyphenylene sulfide resin having a non-Newtonian index of 1.3-1.7, and incorporated therewith, at least (B) 1-30 pts.wt. of an olefin polymer and (C) 0.1-5 pts.wt. of a compound containing a carboxylic anhydride. <P>COPYRIGHT: (C)2009,JPO&INPIT

Description

  The present invention relates to a polyphenylene sulfide resin composition excellent in tensile elongation characteristics and creep characteristics, a production method thereof, and a molded article comprising the polyphenylene sulfide resin composition.

  The polyphenylene sulfide resin composition has excellent heat resistance, impact resistance, high rigidity, molding processability, and high performance and high performance due to its excellent flame resistance, chemical resistance, dimensional stability and electrical properties. Has attracted attention as a performance engineering plastic. In recent years, polyphenylene sulfide resin compositions have been applied to piping parts through which oil passes, household water heater piping parts through which water passes, and peripheral parts by utilizing these characteristics.

  However, the composition containing the polyphenylene sulfide resin has some drawbacks. In particular, in the case of a composition containing a polyphenylene sulfide resin and an elastomer, when used as a piping part of a water heater, hot water heated to about 80 ° C. passes, so that the molded product is deformed and water leaks from the assembly part. That is, there is a problem that the creep characteristics are poor, and there are problems that the product design can be restricted, and that it cannot be used for a part in which a large amount of hot water flows and internal pressure is applied. Because of such problems, there is a demand for component supply using a resin composition with improved creep characteristics.

  On the other hand, improvements in toughness and impact properties have been made by modifying polyphenylene sulfide resins.

  Patent Document 1 discloses a polyphenylene sulfide resin composition comprising a partially crosslinked polyphenylene sulfide resin, an epoxy group-containing elastomer, and a maleic anhydride group-containing compound. However, the creep resistance attributed to the degree of cross-linking as in this case has not been studied, and the balance between the creep resistance and toughness has not been secured, and is not suitable for the intended use of this case.

  Patent Document 2 discloses a composition of polyarylene sulfide resin with improved impact resistance comprising polyarylene sulfide resin, polymer rubber, HDPE, and unsaturated carboxylic acid anhydride. It has not been examined, and the effect of this case cannot be obtained.

  Patent Document 3 discloses a polyarylene sulfide resin and a composition comprising an acidic compound having reactivity with the polyarylene sulfide resin, but an elastomer-containing system has not been studied, and the object of the present invention is High tensile elongation at break cannot be obtained.

Patent Document 4 discloses a composition comprising at least one thermoplastic resin selected from polyphenylene sulfide resin, polyamide, polyester, polycarbonate, polysulfone, and polyamideimide resin, and a carboxylic acid anhydride. The premise is a polyphenylene sulfide resin having a small index, and the intended creep resistance cannot be improved.
JP 05-239350 A (Claims) Japanese Patent Laid-Open No. 04-248872 (Claims) JP 04-314759 A (Claims) Japanese Patent Laid-Open No. 02-283963 (Claims)

  Accordingly, the present invention relates to a polyphenylene sulfide resin composition excellent in tensile elongation at break and creep characteristics, and a production method, and a molded product formed from the same, particularly an automobile part that requires tensile elongation at break and requires creep characteristics. It is an object of the present invention to provide electric parts and parts for fluid piping of general equipment, that is, parts for piping around water.

This invention can solve the said subject by setting it as the composition containing polyphenylene sulfide resin by the following methods. That is, the present invention
(1) (A) 1 to 30 parts by weight of an olefin polymer and (C) a carboxylic anhydride-containing compound 0.1 to 100 parts by weight of a polyphenylene sulfide resin having a non-Newtonian index of 1.3 to 1.7 A polyphenylene sulfide resin composition comprising ~ 5 parts by weight,
(2) The melt flow rate (according to ASTM D-1238-70, measured at a temperature of 315.5 ° C. and a load of 5 kg) of the polyphenylene sulfide resin of (A) non-Newtonian index 1.3 to 1.7 is 20 to The polyphenylene sulfide resin composition according to (1), wherein the composition is 300 g / 10 minutes.
(3) The polyphenylene sulfide resin composition according to any one of (1) and (2), wherein the (B) olefin polymer is an epoxy group-containing α-olefin copolymer,
(4) (A) A polyphenylene sulfide resin having a non-Newtonian index of 1.3 to 1.7 and (C) a carboxylic anhydride-containing compound are melt-kneaded, and then (B) an olefin polymer is melt-kneaded. A method for producing the polyphenylene sulfide resin composition according to any one of (1) to (3) above,
(5) A polyphenylene sulfide resin and (C) a carboxylic anhydride-containing compound are mixed and treated at a temperature of 170 ° C. or higher to give a polyphenylene sulfide resin having a non-Newtonian index of 1.3 to 1.7. (B) The method for producing a polyphenylene sulfide resin composition according to any one of (1) to (3), wherein the olefin polymer is melt-kneaded after the resin is formed,
(6) A molded article comprising the polyphenylene sulfide resin composition according to any one of (1) to (3),
(7) The molded product according to (6), wherein the molded product is a part having a circular cavity for fluid conveyance,
(8) The molded product according to any one of (6) and (7), wherein the molded product is a valve part for turning around water.

  If the polyphenylene sulfide resin composition of the present invention is used, it is excellent in tensile elongation characteristics, so that the medium remaining in the piping part is frozen and the medium is prevented from expanding and breaking the part (hereinafter referred to as freezing resistance). Can be called). At the same time, it has excellent creep characteristics at high temperatures, and therefore has the effect of preventing medium leakage from the assembly part of the piping parts due to the heat medium.

  In particular, a molded article using the polyphenylene sulfide resin composition of the present invention is useful for automobile parts, electrical parts and parts for fluid piping of general equipment, and particularly useful as a part for watering.

  (A) As a polyphenylene 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 polyphenylene sulfide resin is not particularly limited, and is generally a known method, for example, a method for obtaining a polymer having a relatively small 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.

  In the present invention, the polyphenylene sulfide resin obtained by the above method is preferably used after being washed with an organic solvent, hot water, an acid aqueous solution or the like. Organic solvent cleaning is preferred because it can reduce mechanical properties and remove impurities that impair compatibility with the olefin polymer.

  The polyphenylene sulfide resin in the resin composition of the present invention is preferably a polyphenylene sulfide resin having a non-Newtonian index of 1.3 to 1.7. When the non-Newton index is 1.3 or less, the effect of improving the creep characteristics is small, and when the non-Newton index is 1.7 or more, the tensile elongation at break is small, which is not preferable.

  The non-Newtonian index of the polyphenylene sulfide resin of the present invention is a value obtained by measuring the shear stress and shear rate under the conditions of 300 ° C. and L / D = 40 using Capillograph 1B, and obtaining the following formula.

SR = k · SS ⁿ
SR: Shear rate
SS: Shear stress
K: Constant
n: Non-Newtonian index.

The non-Newtonian index of the polyphenylene sulfide resin increases as the molecular chain has a branched or cross-linked structure and the entanglement between molecules increases. Therefore, it is considered that those with a high non-Newtonian index suppress the movement of molecules in the low stress region, resulting in improved creep resistance. On the other hand, if the non-Newtonian index is too high, the molecular constraint is too strong and the tensile elongation at break decreases.
The non-Newtonian index of the polyphenylene sulfide resin can be increased by a method of adding trichlorobenzene at the time of polymerization or a method of crosslinking a powdered or granular polyphenylene sulfide resin by heating to 170 to 270 ° C., but preferably by heating and crosslinking. Is the method.

  The melt flow rate (MFR) of the polyphenylene sulfide resin having a non-Newtonian index of 1.3 to 1.7 is preferably 20 to 300 g / 10 minutes, more preferably 30 to 200 g / 10 minutes. When the MFR is 20 g / 10 min or less, the fluidity is low and the injection moldability is low, and when it is 300 g / 10 min or more, the tensile elongation at break is small, which is not preferable.

  The melt flow rate (MFR) of the polyphenylene sulfide resin in the present invention is a value calculated by the following method.

  In accordance with ASTM-D1238, 10 g of polyphenylene sulfide resin was retained at 315.5 ° C. for 5 minutes using a melt indexer manufactured by Toyo Seiki Co., Ltd. The amount of polyphenylene sulfide resin coming out of the kusa was measured, and the melt flow rate was calculated.

The (B) olefin polymer used in the present invention is obtained by polymerizing an α-olefin such as ethylene, propylene, butene-1, pentene-1, 4-methylpentene-1, and isobutylene alone or in combination of two or more. Polymers, α-olefins and α, β-unsaturated acids such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and alkyl esters thereof; And monomers containing ionomers such as carboxylic acid metal complexes, and ethylene / α-olefin copolymers are preferred from the viewpoint of improving toughness.
A specific example of the ethylene / α-olefin copolymer is a copolymer containing ethylene and at least one α-olefin having 3 to 20 carbon atoms as constituent components. Specific examples of the α-olefin having 3 to 20 carbon atoms include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene and 1-undecene. 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1 -Pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl -1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and these See fit, and the like. Among these α-olefins, a copolymer using an α-olefin having 6 to 12 carbon atoms is more preferable because an improvement in toughness and a further improvement in the reforming effect can be seen.
The olefin copolymer is preferably a modified olefin copolymer having a functional group such as a carboxylic acid group, an amide group, or an epoxy group, and particularly preferably an epoxy group-containing α-olefin copolymer. The epoxy group-containing α-olefin copolymer is 50.0 to 99.5% by weight of α-olefin and 0.5 to 50.0% by weight of α, β-unsaturated glycidyl ester.

  (B) Content of an olefin type copolymer needs to be 1-30 weight part with respect to 100 weight part of polyphenylene sulfide resin which is (A) non-Newtonian index 1.3-1.7 of this invention. (B) When the olefin-based copolymer is 1 part by weight or less, good tensile elongation at break is not exhibited, and when it is 30 parts by weight or more, the creep characteristics are deteriorated.

  Furthermore, the preferable amount of (B) olefin-based copolymer is 3 to 20 parts by weight. By setting the amount within this range, a resin composition having a specific high tensile elongation at break can be obtained while maintaining high creep characteristics.

  (C) Carboxylic anhydride used in the present invention includes maleic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, endobicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic acid. Acid, endobicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic anhydride, and the like, and it is necessary to be 0.1 to 5% by weight in the thermoplastic resin of the present invention. . Particularly preferred (C) carboxylic acid anhydrides are maleic anhydride, itaconic anhydride, succinic anhydride, and citraconic anhydride.

  If (C) the carboxylic acid anhydride is less than 0.1 parts by weight, the dispersion of the (B) olefin copolymer is not sufficient, and if it is 5 parts by weight or more, the tensile elongation at break of the resulting composition is undesirably lowered.

  In the present invention, the (B) olefin polymer may be used alone or in combination of two or more.

  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 ether ketone 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.

  The method for producing the polyphenylene sulfide resin composition of the present invention is a method of melting and mixing a polyphenylene sulfide resin having a non-Newtonian index of 1.3 to 1.7 and a carboxylic acid anhydride, or heating a blend of the polyphenylene sulfide resin and the carboxylic acid anhydride. Thus, it is important to obtain a polyphenylene sulfide resin having a non-Newtonian index of 1.3 to 1.7 and then melt-knead the olefin resin composition.

The method of melt kneading is not particularly limited, but the mixture of raw materials is supplied to a commonly known melt mixer such as a twin screw extruder, Banbury mixer, kneader and mixing roll, and melted at a resin temperature of 290 ° C to 380 ° C. A typical example is a kneading method. At this time, the mixing order of the raw materials is not particularly limited, and after mixing all the raw materials, the method of melt kneading by the above method, or after blending some raw materials, the rest of the raw materials are mixed using the side feeder during the melt kneading. Any method such as a method of mixing raw materials may be used. Preferably, (A) a polyphenylene sulfide resin and (C) a carboxylic anhydride-containing compound are melt-kneaded and pelletized, and then (B) an olefin polymer is melt-kneaded. Moreover, the method of mixing (B) olefin polymer using a side feeder during melt kneading | mixing (A) polyphenylene sulfide resin and (C) carboxylic anhydride containing compound can also be illustrated as a preferable method.
In addition, as a method of heating a blend of polyphenylene sulfide resin and carboxylic acid anhydride to obtain a polyphenylene sulfide resin having a non-Newtonian index of 1.3 to 1.7, a carboxylic acid anhydride is added to a granular, powder or cake-like polyphenylene sulfide resin. The method of blending a thing and heat-processing in 190 degreeC-240 degreeC in air or nitrogen atmosphere is mentioned. In particular, it is desirable to blend a cake-like polyphenylene sulfide resin with a carboxylic acid anhydride and heat-treat with stirring. Further, the carboxylic acid anhydride may be dissolved in N-methyl-2-pyrrolidone or water and blended with the polyphenylene sulfide resin.

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

  The polyphenylene sulfide resin composition obtained in the present invention has a creep strain at 100 ° C. at 80 ° C. and 20 MPa of 3% or less, and a tensile elongation at 23 ° C. measured according to ASTM-D638 of 7% or more. It has been found that it can be used for molded articles in which high-temperature fluid flows and internal pressure is applied.

  The tensile elongation is a value measured by the following method.

  In the tensile 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 tons at a cylinder temperature of 320 ° C. and a mold temperature of 130 ° C., and a tensile strain rate of 10 mm / min, between fulcrums. Tensile elongation was measured according to ASTM-D638 under conditions of a distance of 114 mm and an ambient temperature of 23 ° C. In addition, the displacement amount until a fracture | rupture was measured 5 times, and the average value was made into tensile elongation.

  The tensile creep strain is a value measured by the following method.

  In the tensile 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 tons under conditions of a cylinder temperature of 320 ° C. and a mold temperature of 150 ° C., a fulcrum distance of 114 mm, and an ambient temperature of 80 ° C. A tensile creep test was performed in accordance with ASTM-D2990 under the condition of a tensile stress of 20 MPa. The tensile creep strain is a value obtained by dividing the displacement amount by the distance between the fulcrums, and the average value obtained by measuring the tensile creep strain after 100 hours from the start of the test five times is defined as the tensile creep strain.

  A molded article made of the polyphenylene sulfide resin composition of the present invention has excellent toughness and extremely excellent creep characteristics contrary to toughness. The molded article comprising the polyphenylene sulfide resin composition of the present invention is useful for automobile parts, electrical parts, and fluid piping parts for general equipment, and among them, the fluid piping parts are extremely useful for parts around water.

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

  The non-Newtonian index, melt flow rate (MFR), tensile test, and tensile creep test in the examples were measured according to the following methods.

<Non-Newtonian index>
Using a Capillograph 1B manufactured by Toyo Seiki Co., Ltd., shear stress and shear rate were measured under the conditions of 300 ° C. and L / D = 40, and the non-Newton index was measured by the following formula.

SR = k · SS ⁿ
SR: Shear rate
SS: Shear stress
K: Constant
n: Non-Newtonian index <Melt flow rate (MFR)>
In accordance with ASTM-D1238, 10 g of polyphenylene sulfide resin was retained at 315.5 ° C. for 5 minutes using a melt indexer manufactured by Toyo Seiki Co., Ltd. The amount of polyphenylene sulfide resin coming out of the kusa was measured, and the melt flow rate was calculated.

<Tensile test>
In the tensile 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 tons at a cylinder temperature of 320 ° C. and a mold temperature of 130 ° C., and a tensile strain rate of 10 mm / min, between fulcrums. Tensile elongation was measured according to ASTM-D638 under conditions of a distance of 114 mm and an ambient temperature of -20 ° C. In addition, the tensile elongation as described in the examples is measured five times with the amount of displacement until breakage as the tensile elongation, and the average value is described.

<Tensile creep test>
In the tensile test, an ASTM No. 4 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 150 ° C., a fulcrum distance of 65 mm, and an ambient temperature of 80 ° C. A tensile creep test was performed in accordance with ASTM-D2990 under the condition of a tensile stress of 20 MPa. The tensile creep strain is a value obtained by dividing the displacement by the distance between the fulcrums, and the tensile creep strain described in the examples is the tensile creep strain after 100 hours have elapsed from the start of the test, and is an average value measured five times. Is described.

Examples 1-19, Comparative Examples 1-13
The prepared polyphenylene sulfide resins (PPS-1, PPS-2, PPS-3, PPS-4) were thermally crosslinked under the conditions shown in Table 1, and the polyphenylene sulfide resins (PPS-5, PPS-6, PPS) of (A1) were obtained. -7, PPS-8, PPS-9, PPS-10). ,
(A1) (A2) Polyphenylene sulfide resin (B) Olefin polymer (B-1, B-2) (C) Carboxylic anhydride was dry blended with the composition shown in Table 2. The PPS-1, PPS-2, PPS-3, PPS-4, PPO, and olefin polymer (B-1, B-2) carboxylic acid anhydride used are shown below.

  (Manufacturing method of polyphenylene sulfide resin (PPS-1)) In a 70 liter autoclave equipped with a stirrer and a bottom plug valve, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.96% sodium hydroxide 91 kg (69.80 mol), N-methyl-2-pyrrolidone (NMP) 11.45 kg (115.50 mol), and 10.5 kg of ion-exchanged water were charged, and about 3 hours to 245 ° C. through nitrogen at normal pressure. After gradually distilling off 14.78 kg of water and 0.28 kg of NMP, the reaction vessel was cooled to 200 ° 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, 10.37 kg (70.52 mol) of p-dichlorobenzene and 9.37 kg (94.50 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and a rate of 0.6 ° C./min with stirring at 240 rpm. The temperature was raised from 200 ° C to 270 ° C. After reacting at 270 ° C. for 60 minutes, the bottom plug valve of the autoclave was opened, the contents were flushed into a vessel equipped with a stirrer over 15 minutes while being pressurized with nitrogen, and stirred for a while at 250 ° C. to remove most of NMP. .

  The obtained solid and 76 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 70 ° C. for 30 minutes, and then suction filtered through a glass filter. Next, 76 liters of ion-exchanged water heated to 70 ° C. was poured into a glass filter, and suction filtered to obtain a cake.

  The obtained cake and 90 liters of ion-exchanged water were charged into an autoclave equipped with a stirrer, and 2000 ppm of calcium acetate monohydrate was added. After replacing the inside of the autoclave with nitrogen, the temperature was raised to 192 ° C. and held for 30 minutes. Thereafter, the autoclave was cooled and the contents were taken out.

The contents were subjected to suction filtration with a glass filter, and then 76 liters of ion-exchanged water at 70 ° C. was poured into the contents, followed by suction filtration to obtain a cake. The obtained cake was dried at 120 ° C. under a nitrogen stream to obtain dry PPS.

The obtained PPS had an ER of 35 g / 10 min.

  (Manufacturing method of polyphenylene sulfide resin (PPS-2)) In a 70 liter autoclave equipped with a stirrer and a bottom plug valve, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.96% sodium hydroxide 91 kg (69.80 mol), N-methyl-2-pyrrolidone (NMP) 11.45 kg (115.50 mol), 1.89 kg (23.10 mol) sodium acetate, and 10.5 kg of ion-exchanged water were charged. The mixture was gradually heated to 245 ° C. over about 3 hours while flowing nitrogen at normal pressure, and after distilling out 14.78 kg of water and 0.28 kg of NMP, the reaction vessel was cooled to 200 ° 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.

  Thereafter, the mixture was cooled to 200 ° C., 10.45 kg (71.07 mol) of p-dichlorobenzene and 9.37 kg (94.50 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and the mixture was stirred at 240 rpm. The temperature was raised from 200 ° C. to 270 ° C. at a rate of 6 ° C./min. After reacting at 270 ° C. for 100 minutes, the bottom valve of the autoclave was opened, the contents were flushed into a vessel equipped with a stirrer while being pressurized with nitrogen, and stirred for a while at 250 ° C. to remove most of NMP. .

  The obtained solid and 76 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 70 ° C. for 30 minutes, and then suction filtered through a glass filter. Next, 76 liters of ion-exchanged water heated to 70 ° C. was poured into a glass filter, and suction filtered to obtain a cake.

  The obtained cake and 90 liters of ion-exchanged water were charged into an autoclave equipped with a stirrer, and acetic acid was added so that the pH was 7. After replacing the inside of the autoclave with nitrogen, the temperature was raised to 192 ° C. and held for 30 minutes. Thereafter, the autoclave was cooled and the contents were taken out.

The contents were subjected to suction filtration with a glass filter, and then 76 liters of ion-exchanged water at 70 ° C. was poured into the contents, followed by suction filtration to obtain a cake. The obtained cake was dried at 120 ° C. under a nitrogen stream to obtain dry PPS.

The obtained PPS had an MFR of 700 g / 10 min.

(Method for producing polyphenylene sulfide resin (PPS-3))
In a 70 liter autoclave equipped with a stirrer and a low-stop valve, 8267.37 g (70.00 mol) of 47.5% sodium hydrosulfide, 2924.98 g (70.20 mol) of 96% sodium hydroxide, N-methyl-2 -13860.00 g (140.00 mol) of pyrrolidone (NMP), 2187.11 g (26.67 mol) of sodium acetate, and 10500.00 g of ion-exchanged water were charged, and it took about 3 hours to 240 ° C. through nitrogen at normal pressure. The mixture was gradually heated to distill water 14743.16 g and NMP 280.00 g, and then 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 1.08 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.023 mol per mol of the alkali metal sulfide charged. Then, 10254.40 g (69.76 mol) of p-dichlorobenzene (p-DCB) and 65451.83 g (65.17 mol) of NMP are added, the reaction vessel is sealed under nitrogen gas, and stirred at 240 rpm. The temperature was raised from 0 ° C. to 250 ° C. at a rate of 0.8 ° C./min, and held at 250 ° C. for 70 minutes. Next, the temperature was raised from 250 ° C. to 278 ° C. at a rate of 0.8 ° C./min, and maintained at 278 ° C. for 78 minutes. The extraction valve at the bottom of the autoclave was opened, and the contents were flushed into a vessel equipped with a stirrer over 15 minutes while being pressurized with nitrogen, and stirred for a while at 250 ° C. to remove most of NMP.

  The obtained solid and 76 liters of ion-exchanged water were placed in an autoclave equipped with a stirrer, washed at 70 ° C. for 30 minutes, and then suction filtered through a glass filter. Next, 76 liters of ion-exchanged water heated to 70 ° C. was poured into a glass filter, and suction filtered to obtain a cake.

  The obtained cake and 90 liters of ion-exchanged water were charged into an autoclave equipped with a stirrer, and the interior of the autoclave was replaced with nitrogen, and then the temperature was raised to 192 ° C. and held for 30 minutes. Thereafter, the autoclave was cooled and the contents were taken out.

  The contents were subjected to suction filtration with a glass filter, and then 76 liters of ion-exchanged water at 70 ° C. was poured into the contents, followed by suction filtration to obtain a cake. The obtained cake was dried at 120 ° C. under a nitrogen stream to obtain dry PPS.

The obtained PPS had an MFR of 198 g / 10 min.

(Manufacturing method of polyphenylene sulfide resin (PPS-4)) In a 70 liter autoclave equipped with a stirrer, 8267.37 g (70.00 mol) of 47.5% sodium hydrosulfide and 2957.21 g (70. 97 mol), 1434.50 g (115.50 mol) of N-methyl-2-pyrrolidone (NMP), 2583.00 g (31.50 mol) of sodium acetate, and 10500 g of ion-exchanged water were charged under nitrogen at normal pressure. After gradually heating to 245 ° C. over about 3 hours and distilling out 14780.1 g of water and 280 g of NMP, the reaction vessel was cooled to 160 ° C. The amount of water remaining in the system per mole 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 performing the reaction 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. Then, after cooling to 200 ° C. at a rate of 1.0 ° C./min, it was 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 had an MFR of 100 g / 10 min.

(Olefin polymer)
B-1: Ethylene / glycidyl methacrylate = 88/12 (% by weight) copolymer BF-E manufactured by Sumitomo Chemical Co., Ltd.
B-2: Mitsui Chemicals Co., Ltd. ethylene / butene-1 = 82/18 (weight%) Co., Ltd. Toughmer TX610.

(Carboxylic anhydride)
C-1: Maleic anhydride manufactured by Wako Pure Chemical Industries, Ltd.

  In Examples 1 to 8, resin compositions were produced by the side feed method.

  In Example 9, a resin composition was produced by batch loading.

The components described in Tables 2 and 3 are dry blended at the ratios described in Tables 2 and 3, and the mixture is supplied to a twin screw extruder (TEX-30 manufactured by Nippon Steel) and discharged by the twin screw extruder. The subsequent resin temperature was melt kneaded at 330 ° C. and pelletized to obtain a polyphenylene sulfide resin composition. The tensile elongation and tensile creep strain of the molded product made of the obtained resin composition were measured, and the results are shown in Tables 2 and 3.

  Comparative Examples 1, 6, and 7 are cases where the non-Newtonian index is too small and inappropriate, and the tensile creep strain after 100 hours at 80 ° C. and 20 MPa deteriorates.

  In Comparative Example 2, the carboxylic acid anhydride is inappropriate and the tensile elongation at break is poor.

  Comparative Examples 3 to 5 are cases where the non-Newtonian index is too large and inappropriate, and the tensile elongation at break is poor.

  In Comparative Example 8, the timing of adding the carboxylic acid anhydride and the extrusion method are inappropriate, and the tensile elongation at break is poor.

  On the other hand, all of Examples 1 to 9 have a large tensile elongation and a small tensile creep strain, and are found to be useful for molded products for use around water.

Claims (8)

(A) 1 to 30 parts by weight of (B) olefin polymer and (C) 0.1 to 5 parts by weight of carboxylic anhydride-containing compound with respect to 100 parts by weight of polyphenylene sulfide resin having a non-Newtonian index of 1.3 to 1.7 A polyphenylene sulfide resin composition obtained by blending parts. (A) Melt flow rate of polyphenylene sulfide resin having a non-Newtonian index of 1.3 to 1.7 (according to ASTM D-1238-70, measured at a temperature of 315.5 ° C. and a load of 5 kg) is 20 to 300 g / 10. The polyphenylene sulfide resin composition according to claim 1, wherein the composition is a minute. The polyphenylene sulfide resin composition according to claim 1 or 2, wherein the (B) olefin polymer is an epoxy group-containing α-olefin copolymer. 2. (A) A polyphenylene sulfide resin having a non-Newtonian index of 1.3 to 1.7 and (C) a carboxylic anhydride-containing compound are melt-kneaded, and then (B) an olefin polymer is melt-kneaded. The manufacturing method of the polyphenylene sulfide resin composition in any one of -3. By mixing the polyphenylene sulfide resin and the (C) carboxylic anhydride-containing compound and treating at a temperature of 170 ° C. or higher, the polyphenylene sulfide resin was changed to (A) a polyphenylene sulfide resin having a non-Newton index of 1.3 to 1.7. 4. The method for producing a polyphenylene sulfide resin composition according to claim 1, wherein (B) the olefin polymer is melt-kneaded. A molded article comprising the polyphenylene sulfide resin composition according to any one of claims 1 to 3. The molded article according to claim 6, wherein the molded article is a part having a circular cavity for fluid conveyance. The molded article according to any one of claims 6 and 7, wherein the molded article is a water valve part.