JP6705209B2 - Piping parts made of polyphenylene sulfide resin composition - Google Patents

Description

TECHNICAL FIELD The present invention relates to a piping component made of a polyphenylene sulfide resin composition having excellent water pressure resistance and wet heat resistance.

Polyphenylene sulfide resin (hereinafter sometimes abbreviated as PPS resin) belongs to high heat-resistant super engineering plastics and has mechanical strength, rigidity, flame retardancy, chemical resistance, electrical characteristics and dimensional stability. Therefore, molded products obtained by injection molding the PPS resin composition are widely used for various electric/electronic parts, home electric appliance parts, automobile parts and machine parts.

On the other hand, metal parts have been used for water supply parts such as house equipment piping parts and water heater piping parts through which water passes, but in recent years, molded products made of PPS resin compositions have come to be used. Came.

Patent Document 1 discloses a PPS resin composition which is improved in toughness by blending a polyphenylene sulfide resin with an olefin resin and an alkoxysilane compound and is suitable for a water supply member.

Patent Document 2 discloses a molded product in which a volatile component is reduced without impairing the moldability by using a polyphenylene sulfide resin in which thermal oxidation treatment is optimized. I have listed.

JP, 2011-153242, A JP, 2007-308612, A

In recent years, molded products made of a PPS resin composition have been applied to piping parts for water circulation, but hot water flows and a large water pressure equivalent to the direct pressure of water or a large water pressure by a water hammer is applied. In the place, a molded product made of a conventional PPS resin composition has insufficient water pressure resistance and wet heat resistance, and metal (particularly brass) piping parts are used. The direct pressure of the water supply may be 0.3 to 0.7 MPa, and the water pressure generated by the water hammer may be up to 1.75 MPa. In such a place, in addition to having a water pressure resistance strength of at least 1.75 MPa in a pressure resistance test of the Ministry of Health and Welfare, it is also considered that the strength deterioration due to deterioration over time is taken into consideration, and the water pressure resistance strength at a higher level is considered. Therefore, the molded article made of the conventional PPS resin composition has insufficient water pressure resistance.

However, conventional metal pipe parts have problems that they are heavy and have poor workability due to the large number of parts. From such a background, regarding pipe parts, there has been a demand for a material which is excellent in workability of parts, which can substitute for metal and which can be used even in a place where hot water flows and high water pressure is applied.

However, although a molded article made of the PPS resin composition disclosed in Patent Document 1 or Patent Document 2 is described as being applied to a water application, it is applied to a place where hot water flows and a high water pressure is applied. Was insufficient to do so.

The present inventors arrived at the present invention as a result of intensive studies to solve the above problems.

That is, the present invention provides the following.
(1) (A) The range of the melt viscosity ratio R represented by the following formula (1) is 2 to 4, and the melt flow rate (according to ASTM D-1238-70, temperature 315.5° C., load 5000 g). 10 to 100 parts by weight of the (B) fibrous filler and 4 to 15 parts by weight of the (C) olefin elastomer resin, relative to 100 parts by weight of the polyphenylene sulfide resin having a range of (measurement) of 100 to 1000 g/10 minutes. A pipe component which is in contact with a liquid of a polyphenylene sulfide resin composition having a temperature of 70° C. or higher at a pressure of 0.3 MPa or higher , wherein the (C) olefin-based elastomer resin has an epoxy group α-olefin-based resin. Plumbing parts that are copolymers .

Melt viscosity ratio R=A/B (1)
Here, A is a temperature of 300° C., L/D=10, shear rate: 121.6 s ⁻¹ at melt viscosity (Pa·s), and B is a temperature of 300° C., L/D=10, shear rate: 6080 s. ^It is a melt viscosity (Pa·s) at ⁻¹ .
(2) The (B) fibrous filler is glass fiber, carbon fiber, potassium titanate whiskers, calcium carbonate whiskers, wollastonite whiskers, aluminum borate whiskers, aramid fibers, alumina fibers, silicon carbide fibers, asbestos fibers and stone powder. The piping component according to (1) above, which is at least one kind selected from fibers.
(3) The piping component according to (1) or (2) above, wherein the piping component is any one of a joint, a valve, a servo, a sensor, a pipe, and a pump.
(4) The polyphenylene sulfide resin is subjected to thermal oxidation treatment in an atmosphere having an oxygen concentration of 1 to 5% by volume under the conditions of 160 to 270° C. and 0.5 to 30 hours to obtain the (A) polyphenylene sulfide resin, and then (A). ) A method for producing a piping component according to any one of (1) to (3), wherein a polyphenylene sulfide resin composition is melt-kneaded to obtain a polyphenylene sulfide resin composition, and the polyphenylene sulfide resin composition is molded to obtain a piping component. ..
(5) The difference between the melt flow rate of the (A) polyphenylene sulfide resin before and after the thermal oxidation treatment (measured at a temperature of 315.5° C. and a load of 5000 g according to ASTM D-1238-70) is 100 to The method for manufacturing a piping component according to the above (4), which is 300 g/10 minutes.

According to the present invention, a piping component to which hot water flows and which is subjected to a large water pressure equivalent to the direct pressure of a water supply or a large water pressure by a water hammer can be a molded product made of a polyphenylene sulfide resin composition. It is possible to reduce the weight of a piping component which is in contact with a liquid having a temperature of 70° C. or more at a pressure of 0.3 MPa or more, and improve the workability of the piping component.

Hereinafter, embodiments of the present invention will be described in detail.

The PPS resin used in the present invention is a polymer having a repeating unit represented by the following structural formula (I),

From the viewpoint of heat resistance, a polymer containing 70 mol% or more, further 90 mol% or more, of a polymer containing the repeating unit represented by the above structural formula is preferable. Further, in the PPS resin, less than 30 mol% of its repeating unit may be composed of a repeating unit having the following structure.

The PPS resin used in the present invention has a gas generation amount of 0.3% by weight or less, preferably 0.28% by weight or less, more preferably 0% by weight when volatilized when heated and melted at 320° C. for 2 hours under vacuum. It is preferably 0.22% by weight or less. If the amount of gas generated after the thermal oxidation treatment exceeds 0.3% by weight, volatile components adhering to the mold or the mold vent portion increase, and transfer failure and gas burn are likely to occur, which is not preferable. The lower limit of the gas generation amount after the thermal oxidation treatment is not particularly limited, but it is economically disadvantageous if the time for the thermal oxidation treatment becomes long until the gas generation amount is reduced, and the time for the thermal oxidation treatment is prolonged. As a result, a gelled product is likely to be generated, which may be a cause of defective molding.

The above-mentioned gas generation amount means the amount of the adhesive component in which the gas that volatilizes when the PPS resin is heated and melted under vacuum is cooled and liquefied or solidified, and the glass in which the PPS resin is vacuum sealed is used. It is measured by heating the ampoule in a tubular furnace. As the shape of the glass ampoule, the abdomen is 100 mm×25 mm, the neck is 255 mm×12 mm, and the wall thickness is 1 mm. As a specific measuring method, by inserting only the body of a glass ampoule in which PPS resin is vacuum-sealed into a tubular furnace at 320° C. and heating for 2 hours, the volatility of the neck of the ampoule not heated by the tubular furnace is volatile. The gas cools and adheres. This neck is cut out and weighed, and then the attached gas is dissolved in chloroform and removed. The neck is then dried and weighed again. Calculate the amount of gas generated from the difference in weight of the neck of the ampoule before and after removing the gas.

The ash content of the PPS resin used in the present invention when ashed at 550° C. is 0.3% by weight or less, preferably 0.2% by weight or less, more preferably 0.1% by weight or less. .. An ash content of more than 0.3% by weight means that the PPS resin has a high metal content. A high metal content is not preferable because it not only causes poor electrical insulation, but also causes a decrease in melt fluidity and a decrease in wet heat resistance.

The PPS resin obtained by the production method of the present invention is dissolved in 20 times by weight of 1-chloronaphthalene at 250° C. for 5 minutes, and the residual amount when heated under pressure filtration with a PTFE membrane filter having a pore size of 1 μm is 4 It is necessary to be 0.0% by weight or less, preferably 3.5% by weight or less, and more preferably 3.0% by weight or less. When the amount of the residue is more than 4.0% by weight, it means that thermooxidative crosslinking of the PPS resin proceeds excessively and gelation in the resin increases. Even if the thermal oxidative crosslinking of the PPS resin is excessively advanced, the effect of reducing the volatile content is small, and on the other hand, it causes a decrease in melt fluidity, a molding failure due to a gelled product, etc., which is not preferable. The lower limit of the amount of residue is not particularly limited, but is 1.5% or more, preferably 1.7% or more. If the residual amount is less than 1.5%, the degree of thermal oxidative crosslinking is too slight, so the volatile components during melting do not decrease so much, and the effect of reducing volatile components may be small.

The above residual amount is measured by using a press-formed PPS resin having a thickness of about 80 μm as a sample and using a SUS test tube equipped with a high temperature filter, a pneumatic cap and a collecting funnel. Specifically, first, a membrane filter having a pore size of 1 μm is set in a SUS test tube, and then a PPS resin press-formed to a thickness of about 80 μm and 20 times the weight of 1-chloronaphthalene are weighed and sealed. This is set in a high temperature filtration device at 250° C. and shaken by heating for 5 minutes. Then, a syringe containing air is connected to the pneumatic cap, the piston of the syringe is pushed out, and hot filtration by pneumatic pressure is performed. As a specific method for quantifying the residual amount, it is determined from the weight difference between the membrane filter before filtration and the membrane filter vacuum-dried at 150° C. for 1 hour after filtration.

The PPS resin used in the present invention needs to have a melt flow rate (measured according to ASTM D-1238-70 at a temperature of 315.5° C. and a load of 5000 g) of 100 to 1000 g/10 minutes. When the melt flow rate is 100 g/10 minutes or less, the melt fluidity of the PPS resin composition is remarkably deteriorated and the molding becomes unstable, particularly when the filler is highly filled and used, which is not preferable. Further, when the melt flow rate is 1000 g/10 minutes or more, the strength of the molded article made of the PPS resin composition deteriorates, which is not preferable.

As the PPS resin used in the present invention, it is preferable to use a PPS resin obtained by performing a thermal oxidation treatment. By performing the thermal oxidation treatment, a PPS resin having a melt viscosity ratio R described below can be obtained, and a molded article made of a PPS resin composition containing such a PPS resin has high water pressure resistance and wet heat resistance. It has a characteristic of being excellent, and is suitable for a piping component with which a liquid having a temperature of 70° C. or higher contacts with a pressure of 0.3 MPa or higher.

In the present invention, the PPS resin before being subjected to the thermal oxidation treatment may be obtained by any method. Therefore, a commercially available PPS resin may be used, or it may be produced by polymerizing a monomer as described below. You can also

The method for producing the PPS resin before the thermal oxidation treatment used in the present invention will be described below. First, the contents of the polyhalogenated aromatic compound, sulfidizing agent, polymerization solvent, molecular weight modifier, polymerization aid and polymerization stabilizer used will be described.

[Polyhalogenated aromatic compound]
The polyhalogenated aromatic compound means a compound having two or more halogen atoms in one molecule. Specific examples include p-dichlorobenzene, m-dichlorobenzene, o-dichlorobenzene, 1,3,5-trichlorobenzene, 1,2,4-trichlorobenzene, 1,2,4,5-tetrachlorobenzene and hexa. Polyhalogenated aroma such as chlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene and 1-methoxy-2,5-dichlorobenzene Group compounds are mentioned, and preferably p-dichlorobenzene is used. It is also possible to combine two or more different polyhalogenated aromatic compounds into a copolymer, but it is preferable to use a p-dihalogenated aromatic compound as a main component.

The amount of the polyhalogenated aromatic compound used is 0.9 to 2.0 mol, preferably 0.95 to 1.5 mol, per mol of the sulfidizing agent, in order to obtain a PPS resin having a viscosity suitable for processing. More preferably, the range of 1.005 to 1.2 mol can be illustrated.

[Sulfidizing agent]
Sulfiding agents include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.

Specific examples of the alkali metal sulfide include, for example, lithium sulfide, sodium sulfide, potassium sulfide, rubidium sulfide, cesium sulfide, and a mixture of two or more thereof, and sodium sulfide is preferably used. These alkali metal sulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides.

Specific examples of the alkali metal hydrosulfide include sodium hydrosulfide, potassium hydrosulfide, lithium hydrosulfide, rubidium hydrosulfide, cesium hydrosulfide, and a mixture of two or more of these. It is preferably used. These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures or in the anhydrous form.

Further, a sulfidizing agent prepared in situ in the reaction system from an alkali metal hydrosulfide and an alkali metal hydroxide can also be used. Further, a sulfidizing agent can be prepared from an alkali metal hydrosulfide and an alkali metal hydroxide and transferred to a polymerization tank for use.

Alternatively, a sulfidizing agent prepared in situ in a reaction system from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide can also be used. In addition, a sulfidizing agent can be prepared from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide and transferred to a polymerization tank for use.

The amount of the sulfidizing agent charged means the residual amount obtained by subtracting the loss from the actual charged amount when a partial loss of the sulfiding agent occurs before the initiation of the polymerization reaction due to a dehydration operation or the like.

It is also possible to use an alkali metal hydroxide and/or an alkaline earth metal hydroxide together with the sulfidizing agent. Specific examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide and a mixture of two or more of these, and alkaline earth metals are preferable. Specific examples of the metal hydroxide include, for example, calcium hydroxide, strontium hydroxide, barium hydroxide and the like, of which sodium hydroxide is preferably used.

When an alkali metal hydrosulfide is used as the sulfidizing agent, it is particularly preferable to use the alkali metal hydroxide at the same time, but the amount used is 0.95 to 1.1 per mol of the alkali metal hydrosulfide. The range is 20 mol, preferably 1.00 to 1.15 mol, and more preferably 1.005 to 1.100 mol.

[Polymerization solvent]
It is preferable to use an organic polar solvent as the polymerization solvent. Specific examples include N-methyl-2-pyrrolidone, N-alkylpyrrolidones such as N-ethyl-2-pyrrolidone, caprolactams such as N-methyl-ε-caprolactam, and 1,3-dimethyl-2-imidazolidis. Examples thereof include aprotic organic solvents represented by non-, N,N-dimethylacetamide, N,N-dimethylformamide, hexamethylphosphoric triamide, dimethyl sulfone, tetramethylene sulfoxide, and the like, and mixtures thereof. It is preferably used because of high stability of the reaction. Of these, N-methyl-2-pyrrolidone (hereinafter sometimes abbreviated as NMP) is particularly preferably used.

The amount of the organic polar solvent used is selected in the range of 2.0 mol to 10 mol, preferably 2.25 to 6.0 mol, and more preferably 2.5 to 5.5 mol, per mol of the sulfidizing agent. ..

[Molecular weight regulator]
Use of a monohalogen compound (not necessarily an aromatic compound) in combination with the above polyhalogenated aromatic compound in order to form an end of the resulting PPS resin or to control a polymerization reaction or a molecular weight. You can

[Polymerization aid]
It is also one of the preferred embodiments to use a polymerization aid in order to obtain a PPS resin having a relatively high degree of polymerization in a shorter time. Here, the polymerization aid means a substance having an action of increasing the viscosity of the obtained PPS resin. Specific examples of such a polymerization aid include, for example, organic carboxylates, water, alkali metal chlorides, organic sulfonates, alkali metal sulfates, alkaline earth metal oxides, alkali metal phosphates and alkaline earth salts. Examples thereof include metal phosphates. These may be used alone or in combination of two or more. Among them, organic carboxylic acid salts and/or water are preferably used.

The alkali metal carboxylate is a general formula R(COOM)n (wherein R is an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group, an aryl group, an alkylaryl group or an arylalkyl group. M is an alkali metal selected from lithium, sodium, potassium, rubidium and cesium, and n is an integer of 1 to 3). The alkali metal carboxylate can also be used as a hydrate, an anhydride or an aqueous solution. Specific examples of the alkali metal carboxylate include lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, sodium benzoate, sodium phenylacetate, potassium p-toluate, and a mixture thereof. Can be mentioned.

The alkali metal carboxylate is obtained by adding an organic acid and one or more compounds selected from the group consisting of alkali metal hydroxides, alkali metal carbonates and bicarbonates, in approximately equal chemical equivalents and reacting with each other. You may form by. Among the above alkali metal carboxylates, the lithium salt is highly soluble in the reaction system and has a large auxiliary agent effect, but is expensive, and potassium, rubidium and cesium salts have insufficient solubility in the reaction system. Therefore, sodium acetate, which is inexpensive and has appropriate solubility in the polymerization system, is most preferably used.

When these polymerization aids are used, the amount used is usually in the range of 0.01 mol to 0.7 mol per 1 mol of the charged alkali metal sulfide, and in the sense of obtaining a higher degree of polymerization, 0.1 to 0.7 mol is used. The range of 0.6 mol is preferable, and the range of 0.2 to 0.5 mol is more preferable.

The use of water as a polymerization aid is one of the effective means for obtaining a resin composition in which fluidity and high toughness are highly balanced. In that case, the addition amount is usually in the range of 0.5 to 15 mol per 1 mol of the charged alkali metal sulfide, and in the sense of obtaining a higher degree of polymerization, the range of 0.6 to 10 mol is preferable, The range of 1-5 mol is more preferable.

The timing of addition of these polymerization aids is not particularly specified, and may be added at any time during the pre-process described later, at the start of polymerization, and during polymerization, or may be added in a plurality of times. When an alkali metal carboxylate is used as a polymerization aid, it is more preferable to add it simultaneously at the start of the previous step or at the start of the polymerization, from the viewpoint of easy addition. When water is used as a polymerization aid, it is effective to add the polyhalogenated aromatic compound in the course of the polymerization reaction after charging the polyhalogenated aromatic compound.

[Polymerization stabilizer]
A polymerization stabilizer may be used in order to stabilize the polymerization reaction system and prevent side reactions. The polymerization stabilizer contributes to stabilization of the polymerization reaction system and suppresses undesired side reactions. One measure of the side reaction is the formation of thiophenol, and the addition of a polymerization stabilizer can suppress the formation of thiophenol. Specific examples of the polymerization stabilizer include compounds such as alkali metal hydroxides, alkali metal carbonates, alkaline earth metal hydroxides and alkaline earth metal carbonates. Among them, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide and lithium hydroxide are preferable. The above-mentioned alkali metal carboxylic acid salt also acts as a polymerization stabilizer, and thus is one of the polymerization stabilizers used in the present invention. Further, when the alkali metal hydrosulfide is used as the sulfidizing agent, it is described above that it is particularly preferable to use the alkali metal hydroxide at the same time. Oxides can also be polymerization stabilizers.

These polymerization stabilizers may be used alone or in combination of two or more. The proportion of the polymerization stabilizer is usually 0.02 to 0.2 mol, preferably 0.03 to 0.1 mol, and more preferably 0.04 to 0.09 mol, relative to 1 mol of the charged alkali metal sulfide. Is preferably used. If this ratio is small, the stabilizing effect is insufficient, and conversely if it is too large, it is economically disadvantageous and the polymer yield tends to decrease.

The timing of addition of the polymerization stabilizer is not particularly specified, and may be added at the time of the following step described later, at the start of polymerization, at any time during the polymerization, or may be added in a plurality of times. It is more preferable to add them at the same time at the start of the step or at the start of the polymerization, because the addition is easy.

Next, the pre-process, the polymerization reaction process, and the recovery process will be specifically described in order.

[pre-process]
The sulfidizing agent is usually used in the form of a hydrate.Before adding the polyhalogenated aromatic compound, the mixture containing the organic polar solvent and the sulfiding agent is heated to remove excess water from the system. It is preferable to remove it. In addition, when water is removed too much by this operation, it is preferable to add and supplement the shortage of water.

As described above, as the sulfidizing agent, an alkali metal sulfide prepared from an alkali metal hydrosulfide and an alkali metal hydroxide in situ in the reaction system or in a tank different from the polymerization tank is also used. be able to. The method is not particularly limited, but it is desirable to add an alkali metal hydrosulfide and an alkali metal hydroxide to an organic polar solvent in an inert gas atmosphere at a temperature range of room temperature to 150°C, preferably room temperature to 100°C. In addition, there may be mentioned a method of evaporating water by elevating the temperature to at least 150° C. or higher, preferably 180 to 260° C. under normal pressure or reduced pressure. A polymerization aid may be added at this stage. Further, in order to accelerate the evaporation of water, toluene or the like may be added to carry out the reaction.

The amount of water in the polymerization system in the polymerization reaction is preferably 0.5 to 10.0 mol per mol of the charged sulfidizing agent. Here, the amount of water in the polymerization system is an amount obtained by subtracting the amount of water removed outside the polymerization system from the amount of water charged in the polymerization system. Further, the water to be charged may be in any form such as water, an aqueous solution, crystal water and the like.

[Polymerization reaction step]
It is preferable to produce the PPS resin powder by reacting the sulfidizing agent and the polyhalogenated aromatic compound in an organic polar solvent within a temperature range of 200° C. or higher and lower than 290° C.

When starting the polymerization reaction step, the sulfidizing agent and the polyhalogenated aromatic compound are added to the organic polar solvent in an inert gas atmosphere at a temperature in the range of room temperature to 220°C, preferably 100 to 220°C. A polymerization aid may be added at this stage. The order of charging these raw materials may be in any order or may be simultaneous.

Such a mixture is usually heated to a range of 200°C to 290°C. The rate of temperature increase is not particularly limited, but a rate of 0.01 to 5°C/min is usually selected, and a range of 0.1 to 3°C/min is more preferable.

Generally, the temperature is finally raised to a temperature of 250 to 290° C., and the reaction is usually performed at that temperature for 0.25 to 50 hours, preferably 0.5 to 20 hours.

A method of reacting at 200° C. to 260° C. for a certain period of time before reaching the final temperature and then raising the temperature to 270 to 290° C. is effective in obtaining a higher degree of polymerization. At this time, the reaction time at 200° C. to 260° C. is usually selected in the range of 0.25 hours to 20 hours, preferably in the range of 0.25 to 10 hours.

In order to obtain a polymer having a higher degree of polymerization, it is effective to carry out the polymerization in multiple stages. When carrying out the polymerization in multiple stages, it is effective that the conversion rate of the polyhalogenated aromatic compound in the system at 245° C. reaches 40 mol% or more, preferably 60 mol %.

[Collection process]
After the completion of the polymerization, the solid matter is recovered from the polymerization reaction product containing the polymer, the solvent and the like.

The most preferable method for recovering the PPS resin is to perform it under quenching conditions, and a flash method can be mentioned as one of the preferred methods for recovering the PPS resin. In the flash method, the polymerization reaction product is flashed from a high temperature and high pressure state (usually 250° C. or higher, 8 kg/cm ² or higher) into an atmosphere of normal pressure or reduced pressure, and at the same time when the solvent is recovered, the polymer is made into a granular form. It is a method of recovering, and the term "flash" as used herein means to eject the polymerization reaction product from a nozzle. Specific examples of the atmosphere for flashing include nitrogen or steam under normal pressure, and the temperature is usually selected in the range of 150°C to 250°C.

The flash method is an economical recovery method because it can recover the solid material at the same time as the solvent recovery and the recovery time can be relatively short. In this recovery method, an ionic compound represented by Na and an organic low-polymerization product (oligomer) tend to be easily incorporated into the polymer during the solidification process.

However, the method for recovering the PPS resin used in the present invention is not limited to the flash method. As long as the method satisfies the requirements of the present invention, it is no problem to use a method of slowly cooling and recovering a particulate polymer (quenching method). However, in view of economy and performance, it is more preferable to use the PPS resin recovered by the flash method in the production method of the present invention.

In the present invention, it is preferable to use, as the PPS resin, for example, a PPS resin obtained through the above-mentioned polymerization reaction step and recovery step, which has been subjected to thermal oxidation treatment. Preferably, a hot water treatment and an acid treatment step are preferably included before the thermal oxidation treatment step. Further, a step of washing with an organic solvent may be included before the step of acid treatment or the step of hot water treatment.

The acid used for the acid treatment in the present invention is not particularly limited as long as it has no action of decomposing the PPS resin, and examples thereof include acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid and propyl acid. Acetic acid and hydrochloric acid are more preferably used, but those that decompose and deteriorate the PPS resin such as nitric acid are not preferable.

Water used when the aqueous solution of acid is preferably distilled water or deionized water. The pH of the aqueous acid solution is preferably 1 to 7, more preferably 2 to 4. When the pH is higher than 7, the metal content of the PPS resin increases, which is not preferable, and when the pH is lower than 1, the volatile component of the PPS resin increases, which is not preferable.

As the method of acid treatment, it is preferable to immerse the PPS resin in an acid or an aqueous solution of an acid, and it is also possible to appropriately stir and heat if necessary. The temperature at the time of heating is preferably 80 to 250°C, more preferably 120 to 200°C, and further preferably 150 to 200°C. If it is less than 80°C, the acid treatment effect is small and the metal content increases, and if it exceeds 250°C, the pressure becomes too high, which is not preferable for safety. Further, the pH when the PPS resin is immersed in an aqueous solution of an acid for treatment is preferably less than 8 by acid treatment, and more preferably pH 2-8. When the pH is higher than 8, the metal content of the obtained PPS resin increases, which is not preferable.

The time of the acid treatment is preferably such that the reaction between the PPS resin and the acid is sufficiently in equilibrium, preferably 2 to 24 hours when treated at 80°C, and 0.01 to 5 hours when treated at 200°C. preferable.

The ratio of the PPS resin to the acid or the aqueous solution of the acid in the acid treatment is preferably such that the PPS resin is sufficiently immersed in the acid or the aqueous solution of the acid. The aqueous solution is preferably 0.5 to 500 L, more preferably 1 to 100 L, still more preferably 2.5 to 20 L. If the amount of the acid or the aqueous solution of the acid is less than 0.5 L with respect to 500 g of the PPS resin, the PPS resin is not sufficiently immersed in the aqueous solution, resulting in poor cleaning, and the metal content of the PPS resin increases, which is not preferable. Further, when the acid or the aqueous solution of the acid exceeds 500 L with respect to 500 g of the PPS resin, the amount of the solution with respect to the PPS resin becomes excessively large, and the production efficiency is significantly reduced, which is not preferable.

These acid treatments are performed by adding a predetermined amount of PPS resin to a predetermined amount of water and acid, heating and stirring in a pressure vessel, a method of continuously performing acid treatment, and the like. As a method for separating the aqueous solution and the PPS resin from the treatment solution after the acid treatment, filtration using a sieve or a filter is easy, and examples thereof include natural filtration, pressure filtration, vacuum filtration, and centrifugal filtration. In order to remove the acid and impurities remaining on the surface of the PPS resin separated from the treatment liquid, it is preferable to wash with water or warm water several times. Examples of the washing method include a method of filtering the PPS resin on the filtration device while applying water, and a method of separating the aqueous solution and the PPS resin by, for example, adding the separated PPS resin to water prepared in advance and then filtering again. it can. The water used for washing is preferably distilled water or deionized water.

In the present invention, it is preferable to perform hot water treatment before the step of acid treatment, and the method is as follows. The water used for the hot water treatment in the present invention is preferably distilled water or deionized water. The hot water treatment temperature is preferably 80 to 250°C, more preferably 120 to 200°C, still more preferably 150 to 200°C. If it is less than 80°C, the effect of hot water treatment is small and the amount of gas to be volatilized increases, and if it exceeds 250°C, the pressure becomes too high, which is not preferable for safety.

The hot water treatment time is preferably such that the extraction treatment with the PPS resin and hot water is sufficient, preferably 2 to 24 hours when treated at 80°C, and 0.01 to 5 hours when treated at 200°C. Is preferred.

The ratio of PPS resin to water in the hot water treatment is preferably such that the PPS resin is sufficiently immersed in water, and 0.5 to 500 L of water is preferable, and 1 to 100 L to 500 g of PPS resin. Is more preferable, and 2.5 to 20 L is even more preferable. If the amount of water is less than 0.5 L with respect to 500 g of PPS resin, the PPS resin will not be sufficiently immersed in water, resulting in poor cleaning and an increased amount of volatilized gas. Further, if the amount of water exceeds 500 L with respect to 500 g of PPS resin, the amount of water with respect to the PPS resin becomes excessively large and the production efficiency remarkably decreases, which is not preferable.

There is no particular limitation on the operation of these hot water treatments, and it is carried out by adding a predetermined amount of PPS resin to a predetermined amount of water, heating and stirring in a pressure vessel, a method of continuously performing hot water treatment, and the like. .. There is no particular limitation on the method of separating the aqueous solution and the PPS resin from the treatment solution after the hot water treatment, but filtration using a sieve or a filter is simple, and natural filtration, pressure filtration, vacuum filtration, centrifugal filtration, etc. Can be illustrated. In order to remove impurities remaining on the surface of the PPS resin separated from the treatment liquid, it is preferable to wash with water or warm water several times. There is no particular limitation on the washing method, but the PPS resin on the filtration device may be filtered while water is applied, or the separated PPS resin may be added to water prepared in advance and then filtered again, and the aqueous solution and the PPS resin may be filtered. The method of separating can be illustrated. The water used for washing is preferably distilled water or deionized water.

Further, since the decomposition of the PPS terminal group during the acid treatment or the hot water treatment is not preferable, it is desirable to carry out the acid treatment or the hot water treatment under an inert atmosphere. Examples of the inert atmosphere include nitrogen, helium, and argon, but from the viewpoint of economy, a nitrogen atmosphere is preferable.

The present invention may include a step of washing with an organic solvent before the step of acid treatment or the step of hot water treatment, and the method is as follows. The organic solvent used for washing the PPS resin in the present invention is not particularly limited as long as it does not have an action of decomposing the PPS resin, and for example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, 1,3 -Dimethylimidazolidinone, hexamethylphosphorus amide, nitrogen-containing polar solvents such as piperazinones, dimethyl sulfoxide, dimethyl sulfone, sulfoxide-sulfone solvents such as sulfolane, acetone, methyl ethyl ketone, diethyl ketone, ketone solvents such as acetophenone, Ether-based solvents such as dimethyl ether, dipropyl ether, dioxane and tetrahydrofuran, halogen-based solvents such as chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, tetrachloroethane, perchlorethane and chlorobenzene. , Alcohol such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol, and aromatic hydrocarbon solvents such as benzene, toluene, xylene, etc. Can be mentioned. Among these organic solvents, it is particularly preferable to use N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform and the like. Further, these organic solvents are used alone or in a mixture of two or more kinds.

As a method of washing with an organic solvent, there is a method of immersing a PPS resin in an organic solvent, and if necessary, it is possible to appropriately stir or heat. The washing temperature when washing the PPS resin with an organic solvent is not particularly limited, and any temperature from room temperature to 300° C. can be selected. The higher the cleaning temperature is, the higher the cleaning efficiency tends to be. However, normally, a sufficient cleaning effect can be obtained at a cleaning temperature of room temperature to 150°C. It is also possible to wash under pressure at a temperature above the boiling point of the organic solvent in a pressure vessel. Also, the washing time is not particularly limited. Although it depends on the washing conditions, in the case of batch type washing, a sufficient effect is usually obtained by washing for 5 minutes or more. It is also possible to wash in a continuous manner.

These acid treatment, hot water treatment or washing with an organic solvent can be carried out by appropriately combining these.

As the PPS resin used in the present invention, it is preferable to use the one obtained by subjecting the acid treatment, hot water treatment or washing with an organic solvent described above to a thermal oxidation treatment. The thermal oxidation treatment is to heat the PPS resin in an oxygen atmosphere or to heat by adding a peroxide such as H ₂ O ₂ or a vulcanizing agent such as S. Heating in an oxygen atmosphere is particularly preferable because of its simplicity.

The heating device for the thermal oxidation treatment of the PPS resin may be an ordinary hot air dryer or a rotary type or a heating device with stirring blades, but in the case of efficient and more uniform treatment, a rotary type Alternatively, it is more preferable to use a heating device with a stirring blade. The oxygen concentration in the atmosphere during the thermal oxidation treatment is preferably 1% by volume or more, more preferably 2% by volume or more. In order to exert the effect of the present invention, the upper limit of the oxygen concentration is preferably 5% by volume or less. By performing the thermal oxidation treatment at an oxygen concentration of 5% by volume or less, the thermal oxidation treatment does not proceed excessively, and the toughness of the molded article containing the PPS resin subjected to the thermal oxidation treatment is not impaired. On the other hand, it is preferable to perform the thermal oxidation treatment at an oxygen concentration of 1% by volume or more because a sufficient thermal oxidation treatment can be performed and a PPS resin having a small amount of volatile components can be obtained.

The thermal oxidation treatment temperature of the PPS resin is preferably 160 to 270°C, more preferably 160 to 230°C. By performing the thermal oxidation treatment at 270° C. or lower, the thermal oxidation treatment does not rapidly progress, and the toughness of the molded article containing the PPS resin subjected to the thermal oxidation treatment is not impaired, which is preferable. On the other hand, by performing the thermal oxidation treatment at a temperature of 160° C. or higher, the thermal oxidation treatment can proceed at an appropriate rate and a PPS resin with a small amount of volatile components generated can be obtained, which is preferable.

The treatment time of the thermal oxidation treatment is preferably 0.5 to 30 hours, more preferably 0.5 to 25 hours, and further preferably 2 to 20 hours. A treatment time of 0.5 hours or more is preferable because a sufficient thermal oxidation treatment can be performed and a PPS resin with a small amount of volatile components can be obtained. By setting the treatment time to 30 hours or less, the crosslinking reaction due to the thermal oxidation treatment can be controlled, and the toughness of the molded article containing the PPS resin subjected to the thermal oxidation treatment is not impaired, which is preferable.

The difference between the melt flow rate of the PPS resin preferably used in the present invention before and after the thermal oxidation treatment (measured at a temperature of 315.5° C. and a load of 5000 g according to ASTM D-1238-70) is 100 to 300 g/ 10 minutes is desirable. The range of 120 to 260 g/10 minutes is more preferable, and the range of 150 to 230 g/10 minutes is further preferable, and it is one of the particularly preferable modes for exhibiting toughness, water pressure resistance and moist heat resistance. By performing the thermal oxidation treatment such that the difference between the melt flow rates before the thermal oxidation treatment and after the thermal oxidation treatment is 100 g/10 minutes or more, the wet heat resistance of the obtained composition containing the PPS resin can be improved. preferable. When the difference between the melt flow rates before and after the thermal oxidation treatment is 300 g/10 minutes or less, it is possible to obtain a molded article excellent in water pressure resistance of the obtained composition containing the PPS resin, which is preferable.

The melt flow rate (measured at a temperature of 315.5° C. and a load of 5000 g according to ASTM D-1238-70) of the PPS resin preferably used in the present invention before the thermal oxidation treatment is preferably 200 to 1300 g/10 minutes. .. By using 200 g/10 minutes or more, a PPS resin having excellent moldability can be obtained, while by using 1200 g/10 minutes or less, a PPS resin having excellent mechanical properties can be obtained. Therefore, it is preferable.

The degree of crosslinking of the PPS resin used in the present invention can be represented by a melt viscosity ratio R represented by the following formula (1). The higher the value of the melt viscosity ratio R, the higher the degree of progress of crosslinking.

In the present invention, (A) it is essential to use a polyphenylene sulfide resin having a melt viscosity ratio R represented by the following formula (1) of 2 to 4, preferably 2 to 3.5, and more preferably Is 2.2 to 3. When the melt viscosity ratio R exceeds 4, the thermal oxidation treatment proceeds excessively, so that the toughness of the molded product is impaired and the water pressure resistance strength decreases. On the other hand, when the melt viscosity ratio R is less than 2, the wet heat resistance of the molded product is reduced.
Melt viscosity ratio R=A/B (1)

Here, A is a temperature of 300° C., L/D=10, shear rate: 121.6 s ⁻¹ at melt viscosity (Pa·s), and B is a temperature of 300° C., L/D=10, shear rate: 6080 s. ^It is a melt viscosity (Pa·s) at ⁻¹ .

Further, before and after the thermal oxidation treatment, it is possible to carry out dry heat treatment for the purpose of suppressing thermal oxidative crosslinking and removing water. The temperature is preferably 100 to 270°C, more preferably 120 to 200°C. In this case, the oxygen concentration is less than 1% by volume. The treatment time is preferably 0.2 to 50 hours, more preferably 0.5 to 10 hours, still more preferably 1 to 5 hours. The heat treatment apparatus may be an ordinary hot air dryer or a rotary type or a heating apparatus with a stirring blade, but for efficient and more uniform treatment, a heating apparatus with a rotary type or a stirring blade is used. Is more preferable.

In the present invention, (B) the fibrous filler is added to 100 parts by weight of the polyphenylene sulfide resin having a melt viscosity ratio R of 2 to 4 and an MFR of 100 to 1000 g/10 min. It is essential to mix 10 to 100 parts by weight. The range of 20 to 90 parts by weight is more preferable, the range of 30 to 80 parts by weight is further preferable, and it is particularly preferable in terms of achieving both mechanical strength and moldability.

Fibrous fillers include glass fibers, carbon fibers, potassium titanate whiskers, calcium carbonate whiskers, wallastonite whiskers, aluminum borate whiskers, aramid fibers, alumina fibers, silicon carbide fibers, asbestos fibers, stone fiber, and these. It is also possible to use two or more types together. In addition, pre-treatment of these fibrous fillers 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 gives a better mechanical strength Is preferred in the sense of obtaining As the fibrous filler, glass fiber and carbon fiber are more preferably used.

In the present invention, (A) an olefinic elastomer resin (C) is added to 100 parts by weight of a polyphenylene sulfide resin having a melt viscosity ratio R of 2 to 4 and an MFR of 100 to 1000 g/10 min. It is essential to mix 4 to 15 parts by weight. The olefin elastomer resin is preferably blended with an α-olefin copolymer having an epoxy group, more preferably in the range of 5 to 13 parts by weight, further preferably in the range of 6 to 10 parts by weight, and toughness. This is one of the particularly preferable aspects in achieving both the moldability and the moldability.

As the olefin copolymer having an epoxy group, ethylene, propylene, 1-butene, 1-pentene, 1-octene, 4-methyl-1-pentene, isobutylene and other α-olefins are polymerized alone or in combination of two or more. The (co)polymer obtained as a result, α-olefins such as α-olefin and acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc. Copolymers with saturated acids and their alkyl esters, for example, ethylene/propylene copolymers (“/” represents copolymerization, the same applies hereinafter), ethylene/1-butene copolymers, ethylene/1-hexene, ethylene /1-octene, ethylene/methyl acrylate copolymer, ethylene/ethyl acrylate copolymer, ethylene/butyl acrylate copolymer, ethylene/methyl methacrylate copolymer, ethylene/ethyl methacrylate copolymer, It can be obtained by introducing a monomer component (functional group-containing component) having an epoxy group into ethylene/butyl methacrylate copolymer or the like. Examples of the functional group-containing component include glycidyl acrylate and glycidyl methacrylate. , Glycidyl ethacrylic acid, glycidyl itaconic acid, glycidyl citraconic acid, and the like, and other monomers having an epoxy group. The method for introducing these functional group-containing components is not particularly limited, and the olefin-based (co)polymer may be copolymerized at the time of (co)polymerization, or the olefin-based (co)polymer may be graft-introduced by using a radical initiator. It is possible to use a method such as letting it occur. The introduced amount of the functional group-containing component is in the range of 0.001 to 40 mol %, preferably 0.01 to 35 mol %, based on all the monomers constituting the modified olefin (co)polymer. Appropriate. As a specific example of an olefin copolymer having a glycidyl group obtained by introducing a monomer component having an epoxy group into a particularly useful olefin polymer, an ethylene/propylene-g-glycidyl methacrylate copolymer (" g" represents a graft, the same hereinafter), ethylene/1-butene-g-glycidyl methacrylate copolymer, ethylene/glycidyl acrylate copolymer, ethylene/glycidyl methacrylate copolymer, ethylene/methyl acrylate/ In addition to glycidyl methacrylate copolymer, ethylene/methyl methacrylate/glycidyl methacrylate copolymer, or glycidyl ester of α-olefin such as ethylene and propylene and α,β-unsaturated acid, other monomer Epoxy group-containing olefin-based copolymers containing as an essential component are also preferably used.

Preferred examples of the olefin elastomer resin include ethylene/glycidyl methacrylate copolymer, ethylene/methyl acrylate/glycidyl methacrylate copolymer, ethylene/methyl methacrylate/glycidyl methacrylate copolymer and the like. Particularly preferred is an ethylene/methyl acrylate/glycidyl methacrylate copolymer.

Further, as the olefin elastomer resin, it is excellent to use (C-1) an olefin copolymer having an epoxy group and (C-2) an olefin copolymer having no polar functional group in combination. It is preferable from the standpoint of obtaining the properties and water pressure resistance. These ratios are not particularly limited, but (C-1)/(C-2)=5/95 weight ratio to 95/5 weight ratio is preferable, and (C-1)/C-2)=10/90. The range of the weight ratio to 90/10 weight ratio is more preferable because it has an excellent balance of moldability and water pressure resistance.

On the other hand, as the olefin copolymer (C-2) having no polar functional group, α-such as ethylene, propylene, 1-butene, 1-pentene, 1-octene, 4-methyl-1-pentene and isobutylene. (Co)polymer obtained by polymerizing olefin alone or two or more kinds, for example, ethylene/propylene copolymer (“/” means copolymerization, the same applies hereinafter), ethylene/1-butene copolymer, ethylene Examples include /1-hexene copolymer and ethylene/1-octene copolymer.

Preferred examples of the (C-2) olefin-based copolymer having no polar functional group include ethylene/1-butene copolymer and ethylene/1-octene copolymer. Particularly preferred are ethylene/1-octene copolymers.

Furthermore, the PPS resin composition used in the present invention contains 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, etc. within a range that does not impair the effects of the present invention. A silane compound having at least one functional group selected from the groups may be added. Specific examples of such compounds include epoxy group-containing alkoxysilane compounds such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane and β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane. , Γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane and other mercapto group-containing alkoxysilane compounds, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ-(2-ureidoethyl)amino Ureido group-containing alkoxysilane compounds such as propyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanatepropyltrimethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, γ-isocyanatepropylmethyldiethoxysilane, γ-isocyanatepropyl Isocyanate group-containing alkoxysilane compounds such as ethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane, γ-(2-aminoethyl)aminopropylmethyldimethoxysilane, γ-(2-aminoethyl) Amino group-containing alkoxysilane compounds such as aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane and γ-aminopropyltriethoxysilane, and hydroxyl groups such as γ-hydroxypropyltrimethoxysilane and γ-hydroxypropyltriethoxysilane Examples thereof include alkoxysilane compounds. Of these, alkoxysilanes having an epoxy group, an amino group, an isocyanate group, or a hydroxyl group are particularly suitable for obtaining excellent weld strength. The suitable addition amount of the silane compound is selected in the range of 0.05 to 3 parts by weight with respect to 100 parts by weight of the PPS resin.

The PPS resin composition used in the present invention may be used by blending another resin as long as the effect of the present invention is not impaired. The blendable resin is not particularly limited, and specific examples thereof include polyamides such as nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, aromatic nylon, polyethylene terephthalate, polybutylene terephthalate, poly Polyester resin such as cyclohexyl dimethylene terephthalate and polynaphthalene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene, polyolefin elastomer, polyether ester elastomer, polyether amide elastomer, polyamide imide, polyacetal, polyimide, polyether imide, polyether sulfone , Polysulfone resin, polyallylsulfone resin, polyketone resin, polyarylate resin, liquid crystal polymer, polyetherketone resin, polythioetherketone resin, polyetheretherketone resin, polyamideimide resin, tetrafluoropolyethylene resin, epoxy group-containing polyolefin Examples thereof include copolymers.

In the PPS resin composition used in the present invention, other components such as an antioxidant other than the above, a heat stabilizer (hydroquinone-based), a weathering agent (resorcinol-based, salicylate-based) may be used as long as the effects of the present invention are not impaired. , Benzotriazole-based, benzophenone-based, hindered amine-based), release agents and lubricants (montanic acid and its metal salts, their esters, their half esters, stearyl alcohol, stearamide, bisurea, polyethylene wax, etc.), pigments (cadmium sulfide) , Phthalocyanine, carbon black for coloring, etc., dyes (nigrosine etc.), crystal nucleating agents (talc, silica, kaolin, clay etc.), plasticizers (octyl p-oxybenzoate, N-butylbenzenesulfonamide etc.), electrification 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 antistatic agents, etc.), difficult Combustion agents (for example, red phosphorus, phosphoric acid ester, melamine cyanurate, hydroxides such as magnesium hydroxide and aluminum hydroxide, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin or these Combination of brominated flame retardant with antimony trioxide), heat stabilizer, lubricant such as calcium stearate, aluminum stearate, lithium stearate, bisphenol epoxy resin such as bisphenol A type, novolak phenol type epoxy resin, cresol novolak Strength-improving materials such as type epoxy resin, ordinary additives such as ultraviolet ray preventing agents, coloring agents, flame retardants and foaming agents can be added.

The method for preparing the PPS resin composition is not particularly limited, but each raw material is supplied to a commonly known melt mixer such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, and a mixing roll to obtain 280 to 380°C. A typical example is a method of kneading at the temperature of. The order of mixing the raw materials is not particularly limited, and a method in which all the raw materials are blended and melt-kneaded by the above method, a part of the raw materials are blended and melt-kneaded by the above method, and the remaining raw materials are blended and melt-kneaded Or a method of mixing the remaining raw materials using a side feeder during melt-kneading with a single-screw or twin-screw extruder after blending a part of the raw materials. In addition, as for the small amount additive component, it is of course possible to knead the other components by the above-mentioned method and the like to form pellets, and then add the components before molding to provide molding.

The PPS resin composition 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.

Since the PPS resin composition used in the present invention is excellent in water pressure resistance and wet heat resistance, it is used in a place where a high temperature liquid flows and a large water pressure equivalent to the direct pressure of water or a large water pressure applied by a water hammer is applied. It can be applied to piping parts. The piping component is any one of a joint, a valve, a servo, a sensor, a pipe and a pump, and is particularly preferably used for a water heater component. In the conventional depressurization type water heater, a large water pressure is not applied to the piping parts in contact with high temperature water, and the piping parts made of the conventional PPS resin composition can be used. There was a problem with the vessel such that the water pressure decreased when tap water was simultaneously discharged from multiple faucets. On the other hand, in the case of a water supply direct pressure type water heater in which water pressure and hot water temperature unevenness at the time of tapping are improved, a pipe part made of a conventional PPS resin composition because the hot liquid contacts the pipe part with high water pressure. Could not be used. The pipe part made of the PPS resin composition of the present invention can be applied to a pipe part of a direct water pressure type water heater in which a liquid at 70° C. or more comes into contact with a pressure of 0.3 MPa or more.

The liquid flowing in the piping component may be an antifreezing liquid containing alcohols, glycols, glycerin, etc. in addition to water, and its type and concentration are not particularly limited.

Further, the present invention can be applied to water faucet parts having a low water pressure load, pipe parts such as a mixed faucet, and water supply parts such as a water meter part having a high water pressure load but high temperature water does not flow.

As described above, the piping component made of the polyphenylene sulfide resin composition of the present invention is excellent in water pressure resistance and moist heat resistance, so that a high-temperature liquid flows and a large water pressure or water hammer equivalent to the direct pressure of water supply. It can be used in places where large water pressure is applied.

Other applicable applications of the molded article made of the PPS resin composition used in the present invention include, for example, sensors, LED lamps, consumer connectors, sockets, resistors, relay cases, switches, coil bobbins, capacitors, variable capacitor cases, and oscillations. Child, various terminal boards, transformers, plugs, printed circuit boards, tuners, speakers, microphones, headphones, small motors, magnetic head bases, semiconductors, liquid crystals, FDD carriages, FDD chassis, motor brush holders, parabolic antennas, computer related parts, etc. And electrical components; VTR components, TV components, irons, hair dryers, rice cooker components, microwave oven components, audio components, audio equipment components such as audio/laser disc (registered trademark)/compact discs, lighting components It can also be applied to household and office electrical product parts such as refrigerator parts, air conditioner parts, typewriter parts and word processor parts. Other machine-related parts such as office computer related parts, telephone related parts, facsimile related parts, copier related parts, cleaning jigs, motor parts, lighters and typewriters: microscopes, binoculars, cameras, watches, etc. , Optical parts, precision machinery related parts; valve alternator terminal, alternator connector, IC regulator, potentiometer base for light deer, various valves such as exhaust gas valve, fuel related exhaust system, intake system various pipes, air Intake nozzle snorkel, intake manifold, fuel pump, engine cooling water joint, carburetor main body, carburetor spacer, exhaust gas sensor, cooling water sensor, oil temperature sensor, throttle position sensor, crankshaft position sensor, air flow meter, brake pad wear Sensors, thermostat bases for air conditioners, heating hot air flow control valves, brush holders for radiator motors, water pump impellers, turbine vanes, wiper motor related parts, detributors, starter switches, starter relays, transmission wire harnesses, window washer nozzles. , Air conditioner panel switch board, coil for fuel related electromagnetic valve, connector for fuse, horn terminal, insulating plate for electrical components, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device Examples include various applications such as automobiles and vehicle-related parts such as cases, vehicle speed sensors, and cable liners.

Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the description of these examples.

[Reference Example 1] Preparation of PPS-1 In a 70 liter autoclave equipped with a stirrer and a bottom stopper valve, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide and 2.91 kg (69%) of sodium hydroxide 96% were added. 0.80 mol), N-methyl-2-pyrrolidone (NMP) 11.45 kg (115.50 mol), sodium acetate 1.89 kg (23.10 mol), and ion-exchanged water 10.5 kg were charged at normal pressure. The mixture was gradually heated to 245° C. over a period of about 3 hours while passing nitrogen, and 14.78 kg of water and 0.28 kg of NMP were distilled off, and then 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.

After that, 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 to give a 0.2. 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 for 15 minutes while pressurizing with nitrogen, and stirred at 250° C. for a while to remove most of NMP. ..

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

The resulting 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 became 7. After replacing the inside of the autoclave with nitrogen, the temperature was raised to 192° C. and kept for 30 minutes. Then, the autoclave was cooled and the contents were taken out.

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

The obtained PPS had an MFR of 600 g/10 minutes.

[Reference Example 2] Preparation of PPS-2 In a 70 liter autoclave equipped with a stirrer, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide and 2.96 kg (70.97 mol) of 96% sodium hydroxide. , N-methyl-2-pyrrolidone (NMP) 11.45 kg (115.50 mol), sodium acetate 0.86 kg (10.5 mol), and ion-exchanged water 10.5 kg were charged, and nitrogen was passed under normal pressure at 245. The mixture was gradually heated to 0°C over about 3 hours, 14.78 kg of water and 0.28 kg of NMP were distilled off, 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 1.06 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, 10.24 kg (69.63 mol) of p-dichlorobenzene and 9.01 kg (91.00 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and the mixture was stirred at 240 rpm to obtain 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/minute. After performing the reaction at 270° C. for 100 minutes, 1.26 kg (70 mol) of water was injected under pressure over 15 minutes while cooling to 250° C. at a rate of 1.3° C./minute. Then, it was cooled to 200° C. at a rate of 1.0° C./min, and then rapidly cooled to near room temperature.

The content was taken out, diluted with 2.63 kg of NMP, the solvent and the solid were filtered off with a sieve (80 mesh), and the obtained particles were washed with 31900 g of NMP and filtered off. This was washed several times with 5.60 kg of ion-exchanged water, filtered and then washed with 7.00 kg of a 0.05 wt% acetic acid aqueous solution and filtered. After washing with 70,000 g of ion-exchanged water and filtering, the obtained water-containing 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 1000 g/10 minutes.

[Reference Example 3] Preparation of PPS-3 In a 70 liter autoclave equipped with a stirrer and a bottom stopper valve, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide and 2.94 kg (70% of sodium hydroxide of 96% were used. .63 mol), N-methyl-2-pyrrolidone (NMP) 11.45 kg (115.50 mol), sodium acetate 0.513 kg (6.25 mol), and deionized water 3.82 kg were charged, and the mixture was kept at normal pressure. The mixture was gradually heated to 245°C over about 3 hours while passing nitrogen, and 8.09 kg of water and 0.28 kg of NMP were distilled off, and then 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., 10.34 kg (70.32 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 to give a 0.2. The temperature was raised from 200°C to 270°C at a rate of 6°C/minute, and the reaction was performed at 270°C for 140 minutes. Then, 2.67 kg (148.4 mol) of water was injected under pressure while cooling from 270°C to 250°C over 15 minutes. Then, after gradually cooling from 250° C. to 220° C. over 75 minutes, it was rapidly cooled to around room temperature and the contents were taken out.

The content was diluted with about 35 liters of NMP, stirred as a slurry for 30 minutes at 85° C., and then filtered with an 80 mesh wire mesh (opening 0.175 mm) to obtain a solid. The obtained solid matter was similarly washed and filtered with about 35 liters of NMP. The solid obtained was diluted with 70 liters of ion-exchanged water, stirred at 70° C. for 30 minutes, and then filtered through an 80-mesh wire net to collect the solid, which was repeated three times in total. The obtained solid matter and 32 g of acetic acid were diluted with 70 liters of ion-exchanged water, stirred at 70° C. for 30 minutes, filtered through an 80-mesh wire net, and the obtained solid matter was diluted with 70 liters of ion-exchanged water. After stirring at 70° C. for 30 minutes, the solid matter was collected by filtration through an 80 mesh wire net. The solid matter thus obtained was dried at 120° C. under a nitrogen stream to obtain dried PPS.

The obtained PPS had an MFR of 500 g/10 minutes.

[Reference Example 4] Preparation of PPS-4 In a 70 liter autoclave equipped with a stirrer, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide and 2.96 kg (70.97 mol) of 96% sodium hydroxide. , N-methyl-2-pyrrolidone (NMP) 11.43 kg (115.50 mol), sodium acetate 2.58 kg (31.50 mol), and ion-exchanged water 10.50 kg were charged, and nitrogen was passed under normal pressure at 245. The mixture was gradually heated to 0°C over about 3 hours, 14.78 kg of water and 0.28 kg of NMP were distilled off, 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 1.06 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, 10.24 kg (69.63 mol) of p-dichlorobenzene and 9.01 kg (91.00 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and the mixture was stirred at 240 rpm to obtain 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/minute. After reacting at 270° C. for 100 minutes, 1260 g (70 mol) of water was injected over 15 minutes while cooling to 250° C. at a rate of 1.3° C./minute. Then, it was cooled to 200° C. at a rate of 1.0° C./min, and then rapidly cooled to near room temperature.

The content was taken out, diluted with 2.63 kg of NMP, the solvent and the solid were filtered off with a sieve (80 mesh), and the obtained particles were washed with 31.90 kg of NMP and filtered off. This was washed several times with 56.00 kg of ion-exchanged water, filtered and then washed with 70,000 g of a 0.05 wt% acetic acid aqueous solution and filtered. After washing with 70.00 kg of ion-exchanged water and separating by filtration, the obtained water-containing 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 300 g/10 minutes.

[Reference Example 5] Preparation of PPS-5 In a 70 liter autoclave equipped with a stirrer and a bottom stopper valve, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide and 2.92 kg (70% of sodium hydroxide of 96%) were prepared. .20 mol), N-methyl-2-pyrrolidone (NMP) 13.86 kg (140.00 mol), sodium acetate 2.19 kg (26.67 mol), and ion-exchanged water 10.50 kg were charged, and at normal pressure. The mixture was gradually heated to 240° C. over about 3 hours while passing nitrogen, and 14.74 kg of water and 0.28 kg of NMP were distilled off, and then the reaction vessel was cooled to 160° C. The amount of residual water in the system per 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 charged alkali metal sulfide.

Next, p-dichlorobenzene 10.25 kg (69.76 mol) and NMP 6.45 kg (65.17 mol) were added, the reaction vessel was sealed under nitrogen gas, and the mixture was stirred at 240 rpm to give a temperature of 0.8° C./min. The temperature was raised from 200° C. to 250° C. at a rate of and held at 250° C. for 70 minutes. Then, 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 bottom valve of the autoclave was opened, the contents were flushed into a vessel equipped with a stirrer over 15 minutes while pressurizing with nitrogen, and most of NMP was removed by stirring at 250°C for a while.

The obtained solid matter and 76 liters of ion-exchanged water were put into an autoclave equipped with a stirrer, washed at 70° C. for 30 minutes, and then suction-filtered with a glass filter. Then, 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, the inside of the autoclave was replaced with nitrogen, and then the temperature was raised to 192° C. and kept for 30 minutes. Then, the autoclave was cooled and the contents were taken out.

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

The obtained PPS had an MFR of 200 g/10 minutes.

[Reference Example 6] Preparation of PPS-6 In a 70 liter autoclave equipped with a stirrer and a bottom stopper valve, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide and 2.91 kg (69%) of sodium hydroxide 96%. .80 mol), N-methyl-2-pyrrolidone (NMP) 11.45 kg (115.50 mol), and ion-exchanged water 10.5 kg were charged, and gradually passed through nitrogen at atmospheric pressure to 245° C. over about 3 hours. After heating to 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., 10.48 kg (71.27 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 to give a 0.2. 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 for 15 minutes while pressurizing with nitrogen, and stirred at 250° C. for a while to remove most of NMP. ..

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

The resulting 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 became 7. After replacing the inside of the autoclave with nitrogen, the temperature was raised to 192° C. and kept for 30 minutes. Then, the autoclave was cooled and the contents were taken out.

After the contents were suction-filtered with a glass filter, 76 liters of ion-exchanged water at 70° C. was poured into the contents and suction-filtered to obtain a cake. The obtained cake was dried at 120° C. under a nitrogen stream to obtain dried PPS. The obtained PPS had an ER of 90 g/10 minutes and had an MFR of 6,257 g/10 minutes.

(A) PPS resin PPS-7: PPS-1 polymerized by the method described in Reference Example 1 was subjected to thermal oxidation treatment at 220° C. for 12 hours at an oxygen concentration of 1%.
PPS-8: PPS-1 polymerized by the method described in Reference Example 1 was subjected to a thermal oxidation treatment at an oxygen concentration of 2% at 220° C. for 12 hours.
PPS-9: PPS-2 polymerized by the method described in Reference Example 2 was subjected to thermal oxidation treatment at 220° C. for 12 hours at an oxygen concentration of 1.5%.
PPS-10: PPS-3 polymerized by the method described in Reference Example 3 was subjected to thermal oxidation treatment at an oxygen concentration of 5% and 220° C. for 12 hours.
PPS-11: PPS-5 polymerized by the method described in Reference Example 5 was subjected to thermal oxidation treatment at an oxygen concentration of 0.8% at 220° C. for 12 hours.
PPS-12: PPS-1 polymerized by the method described in Reference Example 1 was subjected to thermal oxidation treatment at an oxygen concentration of 11% and 220° C. for 12 hours.
PPS-13: PPS-6 polymerized by the method described in Reference Example 6 was subjected to thermal oxidation treatment at an oxygen concentration of 11% and 220° C. for 15 hours.
PPS-14: PPS-3 polymerized by the method described in Reference Example 3 was subjected to thermal oxidation treatment at an oxygen concentration of 6% and 220° C. for 12 hours.

(B) Fibrous filler B-1: Chopped strand (T-760H manufactured by Nippon Electric Glass Co., Ltd. 3 mm long average fiber diameter 10.5 μm).

(C) Olefin Copolymer C-1: Ethylene/Glycidyl Methacrylate/Methyl Acrylate Copolymer (Sumitomo Chemical Co., Ltd. Bond First E)
C-2: ethylene/1-octene copolymer (Engage 8842 manufactured by Dow Chemical Co.).

[Measurement evaluation method]
The measurement and evaluation methods in this example and the comparative example are as follows.

(Measurement of melt viscosity ratio R of polyphenylene sulfide resin)
Using Toyo Seiki Capirograph 1C, using a die with a hole length of 10.00 mm and a hole diameter of 1 mm, a shear rate of 300° C.: a melt viscosity (Pa·s) of 121.6 s ⁻¹ , and a shearing temperature of 300° C. The melt viscosity (Pa·s) at a speed of 6070 s ⁻¹ was defined as B, and the melt viscosity ratio R was calculated by the following formula (1).
Melt viscosity ratio R=A/B (1)

(Measurement of MFR of polyphenylene sulfide resin)
The polyphenylene sulfide resin was measured using F-B01 manufactured by Toyo Seiki in accordance with ASTM-D1238-70 under the condition of 315.5° C. and a load of 5000 g.

(Measurement of ER of polyphenylene sulfide resin)
Regarding the polyphenylene sulfide resin having a low viscosity, the MFR was calculated by the following method. The polyphenylene sulfide resin was measured using F-B01 manufactured by Toyo Seiki in accordance with ASTM-D1238-70 under the conditions of 315.5° C. and a load of 345 g. The relational expression between MFR and ER can be expressed by the following expression (2).
Formula (2) MFR=15.8×4.4×ER

(Measurement of water pressure resistance strength)
The resin composition pellets are supplied to an injection molding machine (SE100DU) manufactured by Sumitomo Heavy Industries, Ltd., in which the cylinder temperature is 305°C and the mold temperature is 130°C, and the filling time is 1 s, and the holding pressure is 50% of the filling pressure. Injection molding was performed to obtain a T-shaped joint test piece having an outer diameter of 21.7 mm and a wall thickness of 2.8 mm. Using this test piece, the water pressure resistance strength was measured with a pump (T-300N) manufactured by Kyowa. The water pressure resistance strength was the water pressure when the test piece was broken by applying water pressure using this pump.

(Measurement of flexural modulus)
The measurement was performed according to ISO178. Specifically, the measurement was performed as follows. The resin composition pellets were supplied to an injection molding machine (SE50DUZ-C160) manufactured by Sumitomo Heavy Industries, Ltd., in which the cylinder temperature was 310° C. and the mold temperature was 145° C., and the filling time was 0.8 s, and the filling pressure was 75%. Injection molding was performed under a holding pressure of No. 2 to obtain a type B2 test piece shape specified in ISO 20753. This test piece was conditioned for 16 hours under the conditions of 23° C. and 50% relative humidity, and then measured under the conditions of 23° C. and 50% relative humidity, with a span of 64 mm and a strain rate of 2 mm/min. ..

(Measurement of tensile strength)
The measurement was performed according to ISO527-1,-2. Specifically, the measurement was performed as follows. The resin composition pellets were supplied to an injection molding machine (SE50DUZ-C160) manufactured by Sumitomo Heavy Industries, Ltd., in which the cylinder temperature was 310° C. and the mold temperature was 145° C., and the filling time was 0.8 s, and the filling pressure was 75%. Injection molding was performed under a holding pressure of No. 1 to obtain a type A1 test piece specified by ISO 20753. Using this test piece, in an atmosphere of 23° C. and 50% relative humidity, the test piece was conditioned for 16 hours under the conditions of 23° C. and 50% relative humidity, and then in an atmosphere of 23° C. and 50% relative humidity. The measurement was performed under the conditions of the distance between the grips: 114 mm and the test speed: 5 mm/s.

(PCT processing)
The type A1 test piece specified in ISO 20753 is processed under pressure conditions of 121°C, 100% RH, 2 atm, and 100 hours using a Davai Espec's advanced accelerated life test equipment (EHS-221M). ) Was performed, and the tensile strength of the treated test piece was measured. Further, the strength retention rate was calculated from the tensile strength before the treatment, and this was used as an index of wet heat resistance.

(Production of PPS resin composition)
Using a twin-screw extruder (TEM-26SS manufactured by Toshiba Machine Co., Ltd.) having a 26 mm diameter intermediate addition port in which the cylinder temperature was 300° C. and the screw rotation speed was 300 rpm, 100 parts by weight of PPS resin (A) was used. And (C) an elastomer at a weight ratio shown in Table 1 from a raw material supply port to be in a molten state, and (B) a fibrous filler at a weight ratio shown in Table 1 from an intermediate addition port, and a discharge rate of 40 kg/ Melt kneading was carried out for a time to obtain pellets. The pellets were used to evaluate the above properties. The results are shown in Table 1.

[Examples 1 to 4]
In Examples 1 to 4 shown in Table 1, by using a PPS resin having a melt viscosity ratio R of 2 to 4 and an MFR of 100 to 1000 g/10, the water pressure resistance and the moist heat resistance of the molded product are excellent. Recognize. From these results, the piping parts made of the resin compositions of Examples 1 to 4 are suitable for piping parts to which hot water flows and high water pressure is applied.

[Comparative Examples 5 and 6]
Since Comparative Examples 5 and 6 shown in Table 1 use the PPS resin having the melt viscosity ratio R lower than 2, it is understood that the water pressure resistance is excellent, but the moist heat resistance is poor.

[Comparative Examples 7 to 9]
Since Comparative Examples 7 to 9 shown in Table 1 use the PPS resin having the melt viscosity ratio R higher than 4, it is clear that the wet heat resistance is excellent, but the water pressure resistance is poor.

The pipe part made of the PPS resin composition of the present invention is excellent in water pressure resistance and moist heat resistance, so that hot water flows and a temperature of 70° C. or higher to which a large water pressure equivalent to the direct pressure of water or a large water pressure applied by a water hammer is applied. It can be preferably applied to a piping component which a liquid comes into contact with at a pressure of 0.3 MPa or more.

Claims (5)

(A) The range of the melt viscosity ratio R represented by the following formula (1) is 2 to 4, and the melt flow rate (measured at a temperature of 315.5° C. and a load of 5000 g in accordance with ASTM D-1238-70). 10 to 100 parts by weight of the (B) fibrous filler and 4 to 15 parts by weight of the (C) olefinic elastomer resin are mixed with 100 parts by weight of the polyphenylene sulfide resin having a range of 100 to 1000 g/10 minutes. Is a pipe component which is in contact with a liquid having a temperature of 70[deg.] C. or higher made of the polyphenylene sulfide resin composition at a pressure of 0.3 MPa or higher , wherein the (C) olefin-based elastomer resin has an epoxy group-[alpha]-olefin-based copolymer. Is a plumbing component .
Melt viscosity ratio R=A/B (1)
Here, A is a temperature of 300° C., L/D=10, shear rate: 121.6 s ⁻¹ at melt viscosity (Pa·s), and B is a temperature of 300° C., L/D=10, shear rate: 6080 s. ^It is a melt viscosity (Pa·s) at ⁻¹ . The (B) fibrous filler is selected from glass fiber, carbon fiber, potassium titanate whiskers, calcium carbonate whiskers, wollastonite whiskers, aluminum borate whiskers, aramid fibers, alumina fibers, silicon carbide fibers, asbestos fibers and stone fibers. The piping component according to claim 1 , wherein the piping component is at least one kind. The piping component according to claim 1 or 2 , wherein the piping component is a joint, a valve, a servo, a sensor, a pipe, or a pump. The polyphenylene sulfide resin is subjected to a thermal oxidation treatment under an atmosphere of oxygen concentration of 1 to 5% by volume at 160 to 270° C. for 0.5 to 30 hours to obtain the (A) polyphenylene sulfide resin, and then (A) polyphenylene sulfide. The method for manufacturing a piping component according to claim 1 , wherein the resin is melt-kneaded to obtain a polyphenylene sulfide resin composition, and the polyphenylene sulfide resin composition is molded to obtain a piping component. The difference between the melt flow rates of the (A) polyphenylene sulfide resin before and after the thermal oxidation treatment (measured at a temperature of 315.5° C. and a load of 5000 g according to ASTM D-1238-70) is 100 to 300 g/10. The method for manufacturing a piping component according to claim 4 , which is a minute.