JP7067052B2 - Polyphenylene sulfide resin compositions and articles - Google Patents

Description

The present invention relates to a polyphenylene sulfide resin composition having excellent hydraulic fracturing strength. More specifically, the present invention relates to molded products having excellent hydraulic fracturing strength, particularly casing parts for liquid pumps and piping parts for water circulation.

Polyphenylene sulfide resin (hereinafter sometimes abbreviated as PPS resin) belongs to high heat resistant super engineering plastics and is excellent in mechanical strength, rigidity, flame retardancy, chemical resistance, electrical characteristics and dimensional stability. It is widely used in various electrical and electronic parts, home appliance parts, automobile parts and mechanical parts.

On the other hand, metal parts such as housing equipment piping parts and water heater piping parts that are used by passing water have been mainly made of metal, but they have a high specific weight and are flexible in terms of workability and shape. Since it is inferior, there is a demand for a resin material that can replace it. However, in the case of resin-made water-related parts, it is difficult to obtain excellent hydraulic fracturing strength similar to that of metal, and there is an insufficient problem from the viewpoint of reliability.

In Patent Document 1 and Patent Document 2, when a crystal nucleating agent is blended with a polyphenylene sulfide resin, the temperature is raised to 340 ° C. by a differential scanning calorimeter and melted, and then the temperature is lowered at a rate of 20 ° C./min. Disclosed is a PPS resin composition having an increased exothermic peak temperature (Tmc) associated with crystallization observed in.

Japanese Unexamined Patent Publication No. 2005-15792 Japanese Unexamined Patent Publication No. 2009-275197

Since hot water flows through the water-related parts made of the PPS resin composition and a large water pressure equivalent to the direct pressure of water services or a large water pressure by a water hammer is applied, it is essential to improve the pressure resistance fracture strength. However, since the conventional molded product made of PPS resin composition has insufficient such characteristics, its application to water-related parts has been limited.

The molded product made of the PPS resin composition disclosed in Patent Document 1 and Patent Document 2 has a certain degree of improvement in the strength of the molded product due to the addition of the crystal nucleating agent, but hot water flows and high water pressure is applied. It was still insufficient to apply in such places.

The present inventors have reached the present invention as a result of repeated diligent studies to solve the above problems. That is, the present invention provides the following.
(1) 20 to 300 parts by weight of (B) inorganic filler and 0.06 to 0.19 parts by weight of polyether ether ketone as an organic crystal nucleating agent with respect to 100 parts by weight of (A) polyphenylene sulfide resin. A polyphenylene sulfide resin composition characterized by being blended.
(2) The polyphenylene sulfide resin composition is heated to 340 ° C. by a differential scanning calorimeter, melted, and then cooled at a rate of 20 ° C./min. The polyphenylene sulfide resin composition according to (1), wherein the temperature (Tmc) is 215 ° C. or higher and 260 ° C. or lower.
( 3 ) Further, any of (1) to ( 2 ), wherein 0.01 to 20 parts by weight of the (D) olefin-based copolymer is blended with 100 parts by weight of the (A) polyphenylene sulfide resin. The polyphenylene sulfide resin composition according to the above.
( 4 ) Creep in which an internal water pressure of 0.5 MPa is applied to a T-shaped joint having an outer diameter of 21.7 mm and a wall thickness of 2.8 mm obtained by molding the polyphenylene sulfide resin composition in warm water at 95 ° C. for 1000 hours. The polyphenylene sulfide resin composition according to any one of (1) to ( 3 ), wherein the water pressure resistance strength measured after carrying out the test is 7 MPa or more.
( 5 ) The (A) polyphenylene sulfide resin is a polyphenylene sulfide resin that has been subjected to a thermal oxidation treatment, and (a) the amount of gas generated when heated and melted at 320 ° C. for 2 hours under vacuum is 0.3 weight by weight. % Or less, (b) After dissolving in 20 times the weight of 1-chloronaphthalene at 250 ° C. for 5 minutes, the residual amount after hot pressure filtration with a PTFE membrane filter having a pore size of 1 μm is 4.0% by weight. The polyphenylene sulfide resin composition according to any one of (1) to ( 4 ), which is characterized by the following.
( 6 ) A molded product comprising the polyphenylene sulfide resin composition according to any one of (1) to ( 5 ).
( 7 ) The molded product according to ( 6 ), wherein the molded product is a casing component for a liquid pump or a piping component for water circulation.

According to the present invention, by adding an organic crystal nucleating agent in a specific range, the water pressure breaking resistance, moisture heat resistance, and torque tightening strength of the molded product are improved, and the direct pressure and water of water supply, which have been difficult to use in the past, are improved. It is possible to provide a polyphenylene sulfide resin composition and a molded product applicable to water-related parts to which internal water pressure is applied by a hammer.

It is external drawing of the molded product which has the screw part which measured the torque strength of a screw in an Example. It is a perspective view of the molded product which has a screw part which measured the torque strength of a screw in an Example. It is sectional drawing of the molded product which has the screw part which measured the torque strength of a screw in an Example.

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

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

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

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

[Polyhalogenated aromatic compounds]
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 aromatics such as chlorobenzene, 2,5-dichlorotoluene, 2,5-dichloro-p-xylene, 1,4-dibromobenzene, 1,4-diiodobenzene, 1-methoxy-2,5-dichlorobenzene. Group compounds are mentioned, preferably p-dichlorobenzene. Further, although it is possible to combine two or more different polyhalogenated aromatic compounds into a copolymer, 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 from the viewpoint of obtaining a PPS resin having a viscosity suitable for processing. More preferably, the range of 1.005 to 1.2 mol can be exemplified.

[Sulfidating agent]
Examples of the sulfidizing agent include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfides.

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

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

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

The amount of the charged sulfidating agent shall mean the residual amount obtained by subtracting the loss from the actual charging amount when a partial loss of the sulfidizing agent occurs before the start 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 in combination with the sulfide agent. Specific examples of the alkali metal hydroxide include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, rubidium hydroxide, cesium hydroxide, and a mixture of two or more thereof, and alkaline earth can be mentioned as preferable. Specific examples of the metal hydroxide include calcium hydroxide, strontium hydroxide, barium hydroxide and the like, and sodium hydroxide is preferably used.

When alkali metal hydrosulfide is used as the sulfidizing agent, it is particularly preferable to use alkali metal hydroxide at the same time, but the amount used is 0.95 to 1. per 1 mol of alkali metal hydrosulfide. The range of 20 mol, preferably 1.00 to 1.15 mol, more preferably 1.005 to 1.100 mol can be exemplified.

[Polymerization solvent]
It is preferable to use an organic polar solvent as the polymerization solvent. Specific examples include N-alkylpyrrolidones such as N-methyl-2-pyrrolidone and N-ethyl-2-pyrrolidone, caprolactams such as N-methyl-ε-caprolactum, and 1,3-dimethyl-2-imidazolidi. Examples thereof include aprotic organic solvents typified by non, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric acid triamide, dimethylsulfone, tetramethylenesulfonate, etc., and mixtures thereof, all of which are used. It is preferably used because of its high reaction stability. Among these, N-methyl-2-pyrrolidone (hereinafter, may be abbreviated as NMP) is particularly preferably used.

The amount of the organic polar solvent used is selected in the range of 2.0 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]
A monohalogen compound (not necessarily an aromatic compound) is used in combination with the above polyhalogenated aromatic compound in order to form the terminal of the PPS resin to be produced, or to adjust the polymerization reaction or the molecular weight. Can be done.

[Polymerization aid]
It is also one of the preferable 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 polymerization aids include, for example, organic carboxylates, water, alkali metal chlorides, organic sulfonates, alkali metal sulfates, alkaline earth metal oxides, alkali metal phosphates and alkaline soils. Examples include metal phosphates. These may be used alone or in combination of two or more at the same time. Of these, organic carboxylates and / or water are preferably used.

The alkali metal carboxylate is a general formula R (COMM) _n (in the formula, R is an alkyl group, a cycloalkyl group, an aryl group, an alkylaryl group or an arylalkyl group having 1 to 20 carbon atoms. M is an alkali metal selected from lithium, sodium, potassium, rubidium and cesium. N is a compound represented by an integer of 1 to 3). The alkali metal carboxylate can also be used as a hydrate, anhydrate 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-tolurate, and mixtures thereof. Can be mentioned.

The alkali metal carboxylate is a reaction in which an organic acid and one or more compounds selected from the group consisting of alkali metal hydroxide, alkali metal carbonate and alkali metal bicarbonate are added in approximately equal chemical equivalents and reacted. May be formed by. Among the above alkali metal carboxylates, the lithium salt has high solubility in the reaction system and has a large auxiliary effect, but is expensive, and the potassium, rubidium and cesium salts have insufficient solubility in the reaction system. Therefore, sodium acetate, which is inexpensive and has an appropriate solubility in a 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 with respect to 1 mol of the charged alkali metal sulfide, and is 0.1 to 0.1 in the sense of obtaining a higher degree of polymerization. The range of 0.6 mol is preferable, and the range of 0.2 to 0.5 mol is more preferable.

Further, the use of water as a polymerization aid is one of the effective means for obtaining a resin composition having a highly balanced fluidity and high toughness. In that case, the amount to be added is usually in the range of 0.5 mol to 15 mol, preferably in the range of 0.6 to 10 mol in order to obtain a higher degree of polymerization, with respect to 1 mol of the charged alkali metal sulfide. The range of 1-5 mol is more preferred.

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

[Polymerization stabilizer]
Polymerization stabilizers can also be used to stabilize the polymerization reaction system and prevent side reactions. The polymerization stabilizer contributes to the stabilization of the polymerization reaction system and suppresses undesired side reactions. One guideline for side reactions is the production of thiophenols, and the addition of a polymerization stabilizer can suppress the production of thiophenols. 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. Since the above-mentioned alkali metal carboxylate also acts as a polymerization stabilizer, it is included in one of the polymerization stabilizers used in the present invention. Further, 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 here, the alkali metal water which is excessive with respect to the sulfidizing agent is used. Oxides can also be polymerization stabilizers.

These polymerization stabilizers can be used alone or in combination of two or more. The ratio of the polymerization stabilizer to 1 mol of the charged alkali metal sulfide is usually 0.02 to 0.2 mol, preferably 0.03 to 0.1 mol, and more preferably 0.04 to 0.09 mol. It is preferable to use in. 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 it may be added at any time of the pre-process, the start of polymerization, and the middle of polymerization, which will be described later, or it may be added in a plurality of times. It is more preferable to add them at the same time at the start of the process or the start of polymerization.

Next, the pre-step, the polymerization reaction step, and the recovery step will be specifically described step by step.

[pre-process]
The sulfidizing agent is usually used in the form of a hydrate, but before adding the polyhalogenated aromatic compound, the mixture containing the organic polar solvent and the sulfidizing agent is heated to remove an excess amount of water. It is preferable to remove it. If too much water is removed by this operation, it is preferable to add the insufficient water to replenish the water.

Further, as described above, as the sulfidizing agent, an alkali metal sulfide prepared from alkali metal hydrosulfide and alkali metal hydroxide in situ in the reaction system or in a tank separate from the polymerization tank is also used. be able to. Although this method is not particularly limited, it is desirable to use alkali metal hydrosulfide and alkali metal hydroxide as an organic polar solvent in a temperature range of normal temperature to 150 ° C., preferably normal temperature to 100 ° C. in an inert gas atmosphere. In addition, a method of distilling off water by raising the temperature to at least 150 ° C. or higher, preferably 180 to 245 ° C. under normal pressure or reduced pressure can be mentioned. A polymerization aid may be added at this stage. Further, in order to promote the distillation 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 the amount obtained by subtracting the amount of water removed from the outside of 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, and water of crystallization.

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

When the polymerization reaction step is started, a sulfidizing agent and a polyhalogenated aromatic compound are added to the organic polar solvent in a temperature range of preferably room temperature to 215 ° C., preferably 100 to 215 ° C. in an inert gas atmosphere. A polymerization aid may be added at this stage. The order of charging these raw materials may be random or simultaneous.

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

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

A method of reacting at 200 ° C. to 245 ° C. for a certain period of time and then raising the temperature to 270 to 290 ° C. before reaching the final temperature is effective in obtaining a higher degree of polymerization. At this time, the reaction time at 200 ° C. to 245 ° 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 a plurality of steps. When the polymerization is carried out in a plurality of steps, 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% or more.

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

The most preferable recovery method for the PPS resin is to carry out under quenching conditions, and one preferred method of this recovery method is the flash method. In the flash method, the polymerization reaction product is flushed from a high temperature and high pressure (usually 250 ° C. or higher, 8 kg / cm ² or higher) into an atmosphere of normal pressure or reduced pressure, and the polymer is made into powder or granular material at the same time as the solvent is recovered. It is a method of recovery, and the term “flash” as used herein means that the polymerization reaction product is ejected from a nozzle. Specific examples of the atmosphere to be flushed include nitrogen or water vapor 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 the solid matter can be recovered at the same time as the solvent recovery and the recovery time can be relatively short. In this recovery method, ionic compounds typified by Na and organic low-polymerization products (oligomers) 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 not unreasonable to use a method of slowly cooling to recover the particulate polymer (quenching method). However, from the viewpoint 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, as the PPS resin, for example, it is preferable to use a PPS resin obtained through the above-mentioned polymerization reaction step and recovery step, which has been subjected to thermal oxidation treatment. It is preferable to include a hot water treatment and an acid treatment step 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 does not have an 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 PPS resins such as nitric acid are not preferable.

When using an aqueous acid solution, the water is preferably distilled water or deionized water. The aqueous acid solution is preferably pH 1 to 7, more preferably pH 2 to 4. If the pH is larger than 7, the metal content of the PPS resin increases, which is not preferable, and if the pH is smaller than 1, the volatile components of the PPS resin increase, which is not preferable.

As a method of acid treatment, it is preferable to immerse the PPS resin in an acid or an aqueous solution of an acid, and if necessary, stirring and heating can be performed as appropriate. The temperature at the time of heating is preferably 80 to 250 ° C, more preferably 120 to 200 ° C, still more preferably 150 to 200 ° C. Below 80 ° C, the acid treatment effect is small, the metal content increases, and above 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 acid solution for treatment is preferably less than 8 by the acid treatment, and more preferably pH 2 to 8. When the pH is higher than 8, the metal content of the obtained PPS resin increases, which is not preferable.

The acid treatment time is preferably a time during which 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 treated in a state where the PPS resin is sufficiently immersed in the acid or the aqueous solution of the acid, and the acid or the acid is preferably treated with respect to 500 g of the PPS resin. 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 an increase in the metal content of the PPS resin, which is not preferable. Further, if the amount of 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 to the PPS resin becomes large excessive and the production efficiency is significantly lowered, which is not preferable.

These acid treatments are carried out by a method of 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 treated solution after the acid treatment, filtration using a sieve or a filter is convenient, and methods such as natural filtration, pressure filtration, vacuum filtration, and centrifugal filtration can be exemplified. In order to remove acids 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 cleaning method include a method of filtering while sprinkling water on the PPS resin on the filtration device, and a method of separating the aqueous solution and the PPS resin by a method such as adding the separated PPS resin to the water prepared in advance and then filtering again. 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 acid treatment step, 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, and even more preferably 150 to 200 ° C. If the temperature is lower than 80 ° C, the effect of hot water treatment is small and the amount of volatile gas generated increases, and if the temperature exceeds 250 ° C, the pressure becomes too high, which is not preferable for safety.

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

The ratio of PPS resin to water in the hot water treatment is preferably treated in a state where the PPS resin is sufficiently immersed in water, preferably 0.5 to 500 L of water with respect to 500 g of PPS resin, and 1 to 100 L. 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 the PPS resin, the PPS resin is not sufficiently immersed in the water, resulting in poor cleaning and an increase in the amount of volatile gas generated, which is not preferable. Further, if the amount of water exceeds 500 L with respect to 500 g of the PPS resin, the amount of water with respect to the PPS resin becomes large and the production efficiency is significantly lowered, which is not preferable.

The operation of these hot water treatments is not particularly limited, and is performed by a method of putting a predetermined amount of PPS resin in 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 PPS resin from the treatment solution after hot water treatment, but filtration using a sieve or filter is convenient, and methods such as natural filtration, pressure filtration, vacuum filtration, and centrifugal filtration are available. Can be exemplified. 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. The cleaning method is not particularly limited, but the aqueous solution and the PPS resin can be filtered by sprinkling water on the PPS resin on the filtration device, or by adding the separated PPS resin to the water prepared in advance and then filtering again. Can be exemplified as a method for separating the above. The water used for washing is preferably distilled water or deionized water.

Further, since decomposition of the PPS end group during these acid treatments and hot water treatments is not preferable, it is desirable that the acid treatments and hot water treatments be carried out under an inert atmosphere. Examples of the inert atmosphere include nitrogen, helium, and argon, but a nitrogen atmosphere is preferable from the viewpoint of economy.

The present invention may include a step of washing with an organic solvent before the step of acid treatment and the step of hot water treatment, and the method is as follows. The organic solvent used for cleaning 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, for example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, 1,3. -Nitrogen-containing polar solvents such as dimethylimidazolidinone, hexamethylphosphorasamide and piperazinones, sulfoxide-sulfone solvents such as dimethylsulfoxide, dimethylsulfone and sulfolane, ketone solvents such as acetone, methylethylketone, diethylketone and 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 chlorbenzene. , Methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol and other alcohol-phenolic solvents and benzene, toluene, xylene and other aromatic hydrocarbon solvents. Can be mentioned. Among these organic solvents, the use of N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform and the like is particularly preferable. In addition, these organic solvents are used in one kind or a mixture of two or more kinds.

As a method of cleaning with an organic solvent, there is a method such as immersing the PPS resin in the organic solvent, and it is also possible to appropriately stir or heat as necessary. The cleaning temperature when cleaning the PPS resin with an organic solvent is not particularly limited, and any temperature of about room temperature to 300 ° C. can be selected. The higher the cleaning temperature, the higher the cleaning efficiency tends to be, but usually, a sufficient effect can be obtained at a cleaning temperature of room temperature to 150 ° C. It is also possible to wash under pressure in a pressure vessel at a temperature above the boiling point of the organic solvent. In addition, there is no particular limitation on the cleaning time. Although it depends on the cleaning conditions, in the case of batch type cleaning, a sufficient effect is usually obtained by washing for 5 minutes or more. It is also possible to wash continuously.

These acid treatment, hot water treatment, or washing with an organic solvent can be performed by appropriately combining them.

The PPS resin used in the present invention may preferably be obtained by performing the above-mentioned acid treatment, hot water treatment or washing with an organic solvent and then thermal oxidation treatment. _The thermal oxidation treatment is to heat the PPS resin in an oxygen atmosphere or by adding a peroxide such as _H2O2 or a vulcanizing agent such as S to the treatment. 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 a normal hot air dryer or a rotary type or a heating device with a stirring blade, but in the case of efficient and more uniform processing, a rotary type is used. Alternatively, it is more preferable to use a heating device with a stirring blade. It is desirable that the oxygen concentration in the atmosphere during the thermal oxidation treatment is 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 product 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. It is preferable to carry out the thermal oxidation treatment at 270 ° C. or lower because the thermal oxidation treatment does not proceed rapidly and the toughness of the molded product containing the PPS resin subjected to the thermal oxidation treatment is not impaired. On the other hand, by performing the thermal oxidation treatment at a temperature of 160 ° C. or higher, the thermal oxidation treatment can be advanced at an appropriate speed, 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, still more preferably 2 to 20 hours. It is preferable that the treatment time is 0.5 hours or more because sufficient thermal oxidation treatment can be performed and a PPS resin having a small amount of volatile components can be obtained. By setting the treatment time to 30 hours or less, the cross-linking reaction by the thermal oxidation treatment can be controlled, and the toughness of the molded product containing the PPS resin subjected to the thermal oxidation treatment is not impaired, which is preferable.

The difference in melt flow rate (measured at a temperature of 315.5 ° C. and a load of 5000 g according to ASTM D-1238-70) before and after the thermal oxidation treatment of the PPS resin preferably used in the present invention is 100 to 300 g / g. It is preferably 10 minutes. By performing the thermal oxidation treatment in which the difference between the melt flow rate before the thermal oxidation treatment and the melt flow rate after the thermal oxidation treatment is 100 g / 10 minutes or more, the moisture and heat resistance of the obtained composition containing the PPS resin can be improved. preferable. By setting the difference in melt flow rate between before the thermal oxidation treatment and after the thermal oxidation treatment to 300 g / 10 minutes or less, it is possible to obtain a molded product having excellent water pressure resistance of the obtained composition containing the PPS resin, which is preferable.

The melt flow rate of the PPS resin preferably used in the present invention before thermal oxidation treatment (measured according to ASTM D-1238-70 at a temperature of 315.5 ° C. and a load of 5000 g) 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.

It is more preferable that the PPS resin used in the present invention has a gas generation amount of 0.3% by weight or less when it is heated and melted at 320 ° C. for 2 hours under vacuum. If the amount of gas generated exceeds 0.3% by weight, the volatile components adhering to the mold and the mold vent portion increase, and transfer defects and gas burning may easily occur, which is not preferable. The lower limit of the amount of gas generated is not particularly limited, but it is economically disadvantageous if the time required for polymer cleaning or thermal oxidation treatment, which is mentioned as a method for reducing the amount of gas generated, becomes long.

The amount of gas generated means the amount of the adhesive component in which the gas volatilized 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. It is measured by heating the ample in a tube furnace. The shape of the glass ampoule is 100 mm × 25 mm for the abdomen, 255 mm × 12 mm for the neck, and 1 mm for the wall thickness. As a specific measurement method, only the body of a glass ampoule vacuum-enclosed with PPS resin is inserted into a tube furnace at 320 ° C. and heated for 2 hours, so that the ampoule is volatile at the neck of the ampoule that has not been heated by the tube furnace. The gas is cooled and adheres. After cutting out the neck and weighing it, the attached gas is dissolved in chloroform and removed. The neck is then dried and then weighed again. The amount of gas generated is calculated from the weight difference between the ampoule necks before and after the gas is removed.

The PPS resin used in the present invention preferably has an ash content of 0.3% by weight or less when incinerated at 550 ° C. When the ash content exceeds 0.3% by weight, it means that the metal content of the PPS resin is high. If the metal content is high, not only the electrical insulation is inferior, but also the melt fluidity is lowered and the moisture and heat resistance is lowered, which is not preferable.

The PPS resin used in the present invention is dissolved in 1-chloronaphthalene having a pore size of 1 μm in 20 times the weight at 250 ° C. over 5 minutes, and the residual amount when hot pressure filtration is performed with a PTFE membrane filter having a pore size of 1 μm is 4.0 weight by weight. % Or less is preferable. When the residual amount exceeds 4.0% by weight, it means that the thermal oxidative cross-linking of the PPS resin proceeds excessively and the gelled product in the resin increases. It is not preferable because the toughness of the PPS resin is lowered and the water pressure resistance strength is lowered by excessively advancing the thermal oxidative cross-linking of the PPS resin. The lower limit of the residual amount is not particularly limited, but is 1.5% or more, preferably 1.7% or more. If the amount of the residue is less than 1.5%, the degree of thermal oxidative cross-linking is too slight, so that the volatile components at the time of melting do not decrease so much, and the effect of reducing the volatile content may be small.

The amount of the residue is measured by using a PPS resin pressed film to a thickness of about 80 μm as a sample and using a SUS test tube equipped with a high-temperature filtration device, a pneumatic cap and a collection 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 made into a press film having a thickness of about 80 μm and 1-chloronaphthalene having a weight of 20 times are weighed and sealed. This is set in a high temperature filtration device at 250 ° C. and heated and shaken for 5 minutes. Next, a syringe containing air is connected to the pneumatic cap, and then the piston of the syringe is pushed out to perform thermal filtration by pneumatic pressure. As a specific method for quantifying the amount of the residue, 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 composition used in the present invention has a heat-generating peak temperature associated with crystallization observed when the temperature is raised to 340 ° C., melted, and then lowered at a rate of 20 ° C./min with a differential scanning calorimeter. (Tmc) is preferably 215 ° C. or higher and 260 ° C. or lower, more preferably 220 ° C. or higher and 250 ° C. or lower, and even more preferably 230 ° C. or higher and 240 ° C. or lower. If the temperature is 215 ° C or lower, the effect of adding the organic crystal nucleating agent is poor, so there is a concern that the spherulite size will not be uniform and the molded product will be fragile. There is a concern that it will be vulnerable.

The (B) inorganic filler used in the present invention includes glass fiber, carbon fiber, potassium titanate whiskers, calcium carbonate whiskers, wallastenite whiskers, aluminum borate whiskers, aramid fibers, alumina fibers, silicon carbide fibers, asbestos fibers, and stones. Examples include whiskers, and these can be used in combination of two or more. Further, it is more excellent mechanical strength to pre-treat these fibrous fillers with a coupling agent such as an isocyanate-based compound, an organic silane-based compound, an organic titanate-based compound, an organic borane-based compound and an epoxy compound. It is preferable in the sense of obtaining. It is essential that the inorganic filler is blended in an amount of 20 to 300 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin. The range of 30 to 150 parts by weight is more preferable, and the range of 40 to 120 parts by weight is more preferable. If it is less than 20 parts by weight, the mechanical strength may not be developed, and if it is more than 300 parts by weight, the hydraulic fracturing strength may not be developed.

In the present invention, it is important to add (C) an organic crystal nucleating agent in a specific amount. The (C) organic crystal nucleating agent used in the present invention includes a sorbitol compound and a metal salt thereof; a phosphoric acid ester metal salt; a rosin compound; an oleic acid amide, an acrylic acid amide, a stearic acid amide, a decandicarboxylic acid dibenzoylhydrazide, and a hexanedicarbonate. Acid dibenzoylhydrazide, 1,4-cyclohexanedicarboxylic acid dicyclohexylamide, trimesic acid amide, anilide compound, 2,6-naphthalenedicarboxylic acid dicyclohexylamide, N, N'-dibenzoyl-1,4-diaminocyclohexane, N, N' -Dicyclohexanecarbonyl-1,5-diaminonaphthalene, amide compounds such as octanedicarboxylic acid dibenzoylhydrazide, ethylenediamine / stearic acid / sebacic acid polycondensate, montanic acid waxes, aliphatic carboxylic acid metal salt, aromatic carboxylic acid metal Salts, aromatic phosphonic acids and metal salts, aromatic phosphoric acid metal salts, aromatic sulfonic acid metal salts, β-diketone metal salts, carboxyl group compound metal salts, organic phosphorus compounds, polyethylene, polypropylene, polybutadiene , Polystyrene, AS resin, ABS resin, poly (acrylic acid), poly (acrylic acid ester), poly (methacrylic acid), poly (methacrylic acid ester), polyamide 6, polyamide 46, polyamide 66, polyamide 6T, polyamide 9T, Examples thereof include organic compounds such as polyamide 10T, polyether ether ketones and polyether ketones, and polymer compounds. Among them, a compound having a carbonyl group is preferable, and a polyetheretherketone is more preferable. It is essential to add 0.06 to 0.19 parts by weight of the organic crystal nucleating agent to 100 parts by weight of the polyphenylene sulfide resin. The range of 0.07 to 0.15 parts by weight is more preferable, and the range of 0.08 to 0.12 parts by weight is more preferable. When the amount of the organic crystal nucleating agent is less than 0.06 parts, the Tmc increases, but the water pressure resistance strength decreases because it is not uniformized to the spherulite size, and when it exceeds 0.19 parts, the Tmc increases, but the organic crystal nucleating agent The water pressure fracture strength decreases due to the effect of foreign matter.

In the present invention, it is possible to blend (D) an olefin-based copolymer. As the (D) olefin-based copolymer used in the present invention, α-olefin alone or two kinds such as ethylene, propylene, 1-butene, 1-pentene, 1-octene, 4-methyl-1-pentene and isobutylene The (co) copolymer obtained by polymerizing the above, α-olefin and acrylic acid, α, β-unsaturated acids such as acrylic acid ester, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like and the same. Copolymers with alkyl esters, such as ethylene / propylene copolymers (“/” stands for copolymer, 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, ethylene / methacrylic acid It can be obtained by introducing a monomer component (functional group-containing component) having an epoxy group into a butyl copolymer or the like. Examples of the functional group-containing component are glycidyl acrylate, glycidyl methacrylate, and glycidyl etacrilate. , A monomer containing an epoxy group such as glycidyl itaconate and glycidyl citracone. 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 grafted into the olefin-based (co) polymer using a radical initiator. It is possible to use a method such as making a radical. The amount of the functional group-containing component introduced is preferably in the range of 0.001 to 40 mol%, preferably 0.01 to 35 mol% with respect to all the monomers constituting the modified olefin-based (co) polymer. Appropriate. Specific examples of the olefin-based polymer having a glycidyl group obtained by introducing a monomer component having an epoxy group into a particularly useful olefin-based (co) polymer include ethylene / propylene-g-glycidyl methacrylate. Polymer (“g” stands for graft, the same applies hereinafter), ethylene / 1-butene-g-glycidyl methacrylate copolymer, ethylene / glycidyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / In addition to methyl acrylate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / glycidyl methacrylate copolymer, or α-olefins such as ethylene and propylene and glycidyl esters of α, β-unsaturated acids, and others. An epoxy group-containing olefin-based copolymer containing the above-mentioned monomer as an essential component is also preferably used.

Among them, preferred examples include ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / glycidyl methacrylate copolymer and the like. Particularly preferred are ethylene / methyl acrylate / glycidyl methacrylate copolymers.

Further, as the olefin-based elastomer resin, an olefin-based copolymer having a (D-1) epoxy group and an olefin-based copolymer having no (D-2) polar functional group may be used in combination. These ratios are not particularly limited, but the range of (D-1) / (D-2) = 5/95 weight ratio to 95/5 weight is more preferable because it has an excellent balance between formability and water pressure resistance. ..

On the other hand, examples of the (D-2) olefin-based copolymer having no polar functional group include ethylene, propylene, acrylic acid ester, 1-butene, 1-pentene, 1-octene, 4-methyl-1-pentene and isobutylene. (Co) polymers obtained by polymerizing α-olefin alone or two or more of them, for example, ethylene / propylene copolymer (“/” indicates copolymer, the same applies hereinafter), ethylene / 1-butene. Examples thereof include polymers, ethylene / 1-hexene copolymers, and ethylene / 1-octene copolymers. The olefin-based copolymer is preferably blended in an amount of 0.01 to 20 parts by weight based on 100 parts by weight of the polyphenylene sulfide resin. The range of 1 to 15 parts by weight is more preferable, and the range of 2 to 12 parts by weight is more preferable. If it is less than 0.01 parts by mass, toughness due to the effect of adding the elastomer is not exhibited, and if it is blended in excess of 20 parts by weight, there is a concern that the processability and moldability may be deteriorated due to gas generation during extrusion processing or molding, which is not preferable.

Further, 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 for the purpose of improving mechanical strength, toughness, etc., as long as the effects of the present invention are not impaired. A silane compound having at least one functional group selected from the groups may be blended. 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 Ureid group-containing alkoxysilane compounds such as propyltrimethoxysilane, γ-isocyanatepropyltriethoxysilane, γ-isocyanappropyltrimethoxysilane, γ-isocyanatepropylmethyldimethoxysilane, γ-isocyanapropylmethyldiethoxysilane, γ-isocyanatepropyl Isocyanate group-containing alkoxysilane compounds such as ethyldimethoxysilane, γ-isoxapropylethyldiethoxysilane, γ-isoxapropyltrichlorosilane, γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) Contains 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 an alkoxysilane compound. Of these, an epoxysilane having an epoxy group, an amino group, an isocyanate group, and a hydroxyl group is particularly suitable for obtaining excellent weld strength. The suitable blending amount of the silane compound is selected in the range of 0.01 to 5 parts by weight with respect to 100 parts by weight of the PPS resin.

Further, the PPS resin composition used in the present invention may be further blended with 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 polyester resins such as polyethylene terephthalate, polybutylene terephthalate, polycyclohexyldimethylene terephthalate, and polynaphthalene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene, and poly. Ether ester elastomer, polyether amide elastomer, polyamide imide, polyacetal, polyimide, polyetherimide, polyether sulfone, polysulfone resin, polyallyl sulfone resin, polyketone resin, polyallylate resin, liquid crystal polymer, polythioether ketone resin, polyamideimide Examples thereof include resin and tetrafluoride polyethylene resin.

The PPS resin composition used in the present invention includes other components such as antioxidants, heat-resistant stabilizers (hydroquinone-based), and weather-resistant agents (resorcinol-based, salicylate-based) other than the above, as long as the effects of the present invention are not impaired. , Benzotriazole-based, benzophenon-based, hindered amine-based, etc.), mold release agents and lubricants (stearyl alcohol, stearamide, bisurea, polyethylene wax, etc.), pigments (cadmium sulfide, phthalocyanine, carbon black for coloring, etc.), dyes (niglosin, etc.) ), Plastics (octyl p-oxybenzoate, N-butylbenzenesulfonamide, etc.), Antistatic agents (alkylsulfate-type anionic antistatic agents, quaternary ammonium salt-type cationic antistatic agents, polyoxyethylene sorbitanmono Nonionic antistatic agents such as stearate, betaine amphoteric antistatic agents, etc., flame retardants (eg, red phosphorus, phosphoric acid esters, melamine cyanurates, magnesium hydroxides, hydroxides such as aluminum hydroxide, polycarbonates, etc. Ammonium acid, brominated polystyrene, brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin or a combination of these brominated flame retardants and antimony trioxide, etc.), heat stabilizer, calcium stearate, aluminum stearate, stearic acid Lubricants such as lithium, bisphenol epoxy resins such as bisphenol A type, strength-enhancing materials such as novolak phenol type epoxy resin, cresol novolak type epoxy resin, and usual additives such as UV inhibitors, colorants, flame retardants and foaming agents. Can be added.

The method for producing the PPS resin composition of the present invention 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, and 280. A typical example is a method of kneading at a temperature of about 380 ° C. The mixing order of the raw materials is not particularly limited, and all the raw materials are blended and then melt-kneaded by the above method, some raw materials are blended and then melt-kneaded by the above method, and the remaining raw materials are blended and melt-kneaded. Either method may be used, or a method of mixing the remaining raw materials using a side feeder during melt-kneading by a single-screw or twin-screw extruder after mixing some of the raw materials may be used. Further, as for the small amount additive component, it is of course possible to knead other components by the above method or the like to pelletize them, and then add them before molding and use them for molding.
Above all, in order to finely disperse the blended crystal nucleating agent in the PPS resin, the temperature of the PPS resin composition at the time of melt-kneading is preferably 310 ° C. or higher, more preferably 320 ° C. or higher, and 330 ° C. or higher. Is the most preferable.

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 fracture resistance and moisture 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 supply or a large water pressure by a water hammer is applied. It can be applied to the piping parts to be used. The piping component is any 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 decompression type water heater, a large water pressure is not applied to the piping parts that come into contact with high temperature water, and it was possible to use the conventional piping parts made of PPS resin composition, but the decompression type hot water supply There was a problem with the vessel that the water pressure dropped when hot water was discharged from multiple faucets all at once. On the other hand, in the case of a water supply direct pressure type water heater in which the water pressure of hot water and unevenness of hot water temperature at the time of hot water are improved, the high temperature liquid comes into contact with the piping parts at high water pressure, so the piping made of the conventional PPS resin composition. The parts could not be used. The piping component made of the PPS resin composition of the present invention can be applied to a piping component of a water supply direct pressure type water heater or the like in which a liquid of 70 ° C. or higher comes into contact with a pressure of 0.3 MPa or higher. It can also be used for screw-shaped piping parts due to the improved tightening torque strength.

The liquid flowing through the piping component may be an antifreeze liquid containing alcohols, glycols, glycerin and the like in addition to water, and the type and concentration thereof are not particularly limited.

It can also be applied to water faucet parts with low water pressure load, liquid pump casing parts, piping parts such as mixing faucets, and water-related parts such as water meter parts with high water pressure load but high temperature water does not flow. can.

As described above, since the piping component made of the PPS resin composition of the present invention is excellent in water pressure breaking strength and moisture heat resistance, a place where a high temperature liquid flows and a large water pressure equivalent to the direct pressure of water is applied. Can be used for.

When the PPS resin composition of the present invention is made into a molded product, the water pressure fracture resistance (water pressure resistance) and the moisture heat resistance can be measured by the following methods. The pellet made of the PPS resin composition of the present invention is supplied to an injection molding machine (SE100DU) manufactured by Sumitomo Heavy Industries, Ltd., which has a cylinder temperature of 305 ° C and a mold temperature of 130 ° C. Injection molding is performed with a holding pressure of 50% to obtain a test piece of a T-shaped pipe type joint having an outer diameter of 21.7 mm and a wall thickness of 2.8 mm specified by JIS G3452. A rubber pipe connected to a pump (T-300N) manufactured by Kiyowa Co., Ltd. is connected to one of the test pieces, and a sealing plug and a ball valve are connected to the other two sides. After that, with the ball valve open, water is passed through the test piece, the air inside the test piece is evacuated, and then the ball valve is closed. Water pressure is applied using a pump, and the pressure indicated by the pressure gauge when the test piece is destroyed is taken as the water pressure resistance strength. Further, a method for evaluating the moisture resistance and heat resistance will be described below. Prepare a test piece similar to that used in the measurement of water pressure resistance strength. A metal pipe connected to a pump (T-100K) manufactured by Kiyowa Co., Ltd. is connected to one of the test pieces, and a sealing plug and a ball valve are connected to the other two sides. With the ball valve open, let water pass through the test piece, bleed the air inside the test piece, and then close the ball valve. The test piece is immersed in warm water at 95 ° C. and subjected to a moisture-resistant heat treatment in which an internal water pressure of 0.5 MPa is applied for 1000 hours. After that, the T-shaped joint test piece is taken out from the hot water, the ball valve is opened to release the water pressure, and water is passed through the test piece to check for water leakage. Then, the water pressure resistance strength of the test piece subjected to the moisture resistance heat treatment is measured by the same method as the measurement of the water pressure resistance strength.

In the T-shaped pipe type joint using the PPS resin composition of the present invention, the water pressure resistance strength can be 7 MPa or more when the water pressure resistance strength of the test piece without water leakage is measured. Further, it is possible to obtain a molded product having a water pressure resistance strength of preferably 7.5 MPa or more, particularly preferably 8.0 MPa or more. When the water pressure resistance strength measured by this method is 7 MPa or less, the durability is inferior, and it becomes difficult to use it in a hot water environment.

Since the molded product made of the PPS resin composition of the present invention also improves the tightening torque strength, it can also be used for screw-shaped piping parts. The torque strength of the molded product made of the PPS resin composition of the present invention can be measured by the following method. The PPS resin composition pellet of the present invention is supplied to an injection molding machine (SE100DU) manufactured by Sumitomo Heavy Industries, Ltd., which has a cylinder temperature of 310 ° C. and a mold temperature of 130 ° C., and is filled with a filling time of 2 seconds and a filling pressure of 70. Injection molding is performed with a holding pressure of% and a cooling time of 50 seconds, and the taper screw for pipes according to JIS B 0203 (1999) has a nominal diameter of R1 / 2 and a hollow inner diameter of the threaded portion of φ11. -Obtain the joint test piece shown in FIG. 3 (the unit of the numerical value in FIG. 3 is mm). Fix this test piece with a vise, and tighten a brass female screw cap with a nominal diameter of Rc1 / 2 for the taper screw for pipes according to JIS B 0203 (1999) to the male screw part of the test piece with a torque wrench. The torque strength was defined as the strength when the male screw of the test piece broke. The torque strength of the molded product made of the PPS resin composition of the present invention is preferably 70 N · m or more, more preferably 80 N · m or more, and most preferably 85 N · m or more. If the torque strength is less than 70 Nm, it is not preferable because there is a risk of cracking when tightening to a metal pipe.

Other applicable uses of the molded product 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 condenser cases, and the like. Oscillators, 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 Electrical and electronic parts such as VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave parts, acoustic parts, audio equipment parts such as audio / laser discs (registered trademarks) and compact discs, lighting It can also be applied to household and office electrical product parts such as parts, refrigerator parts, air conditioner parts, typewriter parts, and word processor parts. Other machine-related parts such as office computer-related parts, telephone equipment-related parts, facsimile-related parts, copying machine-related parts, cleaning jigs, motor parts, writers, typewriters, etc .: microscopes, binoculars, cameras, watches, etc. Optical equipment represented by, precision machinery related parts; valve alternator terminal, alternator connector, IC regulator, potential meter base for light dial, 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 Sensor, thermostat base for air conditioner, heating hot air flow control valve, brush holder for radiator motor, water pump impeller, turbine vane, wiper motor related parts, distributor, starter switch, starter relay, wire harness for transmission, window washer nozzle , Air conditioner panel switch board, fuel-related electromagnetic valve coil, fuse connector, horn terminal, electrical component insulation plate, step motor rotor, lamp socket, lamp reflector, lamp housing, brake piston, solenoid bobbin, engine oil filter, ignition device Various applications such as cases, vehicle speed sensors, automobile / vehicle-related parts such as cable liners, etc. can be exemplified.

Examples are shown below, and the present invention will be described in more detail, but the present invention is not limited to the description of these examples.

[Evaluation method of PPS resin manufactured in the reference example]
(1) Amount of gas generated 3 g of PPS resin was weighed into a glass ampoule having an abdomen of 100 mm × 25 mm, a neck of 255 mm × 12 mm, and a wall thickness of 1 mm, and then vacuum-sealed. Only the body of this glass ampoule was inserted into a ceramic electric tube furnace ARF-30K manufactured by Asahi Rika Seisakusho and heated at 320 ° C. for 2 hours. After removing the ampoule, the neck of the ampoule, which was not heated by the tube furnace and had volatile gas attached, was cut out with a file and weighed. Then, the adhering gas was dissolved in 5 g of chloroform and removed, dried in a glass dryer at 60 ° C. for 1 hour, and then weighed again. The difference in weight between the ampoule necks before and after the gas was removed was defined as the amount of gas generated (% by weight).

(2) Amount of residue A PTFE membrane filter with a pore size of 1 μm, which was weighed in advance, was set in a SUS test tube manufactured by Senshu Kagaku equipped with a pneumatic cap and a collection funnel, and 100 mg of PPS resin made into a press film to a thickness of about 80 μm. And 1-chloronaphthalene (2 g) was weighed and sealed. This was inserted into a high temperature filtration device SSC-9300 manufactured by Senshu Kagaku, and the PPS resin was dissolved in 1-chloronaphthalene by heating and shaking at 250 ° C. for 5 minutes. A 20 mL syringe containing air was connected to the pneumatic cap, then the piston was extruded and the solution was filtered through a membrane filter. The membrane filter was taken out, vacuum dried at 150 ° C. for 1 hour, and then weighed. The difference in the weight of the membrane filter before and after filtration was defined as the residual amount (% by weight).

(3) Melt flow rate (MFR)
The measurement temperature was 315.5 ° C. and a load of 5000 g, and the measurement was performed by a method according to ASTM-D1238-70.

[Reference Example 1] Preparation of PPS-1 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide and 2.91 kg (69) of 96% sodium hydroxide in a 70-liter autoclave with a stirrer and a bottom plug valve. .80 mol), 11.45 kg (115.50 mol) of N-methyl-2-pyrrolidone (NMP), 1.89 kg (23.10 mol) of sodium acetate, and 10.5 kg of ion-exchanged water were charged at normal pressure. The reaction vessel was cooled to 200 ° C. after distilling 14.78 kg of water and 0.28 kg of NMP by gradually heating to 245 ° C. over about 3 hours while passing through nitrogen. 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 reaction vessel was stirred at 240 rpm to 0. 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 container with a stirrer for 15 minutes while pressurizing with nitrogen, and the contents were stirred at 250 ° C. for a while to remove most of NMP. ..

The obtained solid matter 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 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.

90 liters of the obtained cake and ion-exchanged water were placed in 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 held for 30 minutes. After that, the autoclave was cooled and the contents were taken out.

After suction-filtering the contents 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 a dried PPS, and then subjected to thermal oxidation treatment at an oxygen concentration of 2%, 215 ° C., and 12 hours. The gas generation amount of the obtained polymer was 0.15% by weight, the residue amount was 1.9% by weight, and the MFR was 400 g / 10 minutes.

[Reference Example 2] Preparation of PPS-2 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide and 2.96 kg (70.97 mol) of 96% sodium hydroxide were placed in a 70-liter autoclave equipped with a stirrer. , 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, and 245 while passing nitrogen under normal pressure. The reaction vessel was cooled to 160 ° C. after gradually heating to ° C. over about 3 hours and distilling 14.78 kg of water and 0.28 kg of NMP. 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 reaction vessel was stirred at 240 rpm at 0.6 ° C./. The temperature was raised to 238 ° C. at the rate of minutes. After the reaction was carried out at 238 ° C. for 95 minutes, the temperature was raised to 270 ° C. at a rate of 0.8 ° C./min. After the reaction was carried out at 270 ° C. for 100 minutes, 1260 g (70 mol) of water was press-fitted over 15 minutes and cooled to 250 ° C. at a rate of 1.3 ° C./min. Then, it was cooled to 200 ° C. at a rate of 1.0 ° C./min and then rapidly cooled to near room temperature.

The contents were taken out, diluted with 2.63 kg of NMP, the solvent and the solid matter were filtered off by a sieve (80 mesh), and the obtained particles were washed with 31.90 kg of NMP and filtered off. This was washed with 56.00 kg of ion-exchanged water several times and filtered off, and then washed with 70000 g of a 0.05 wt% acetic acid aqueous solution and filtered off. After washing with 70.00 kg of ion-exchanged water and filtering, the obtained hydrous PPS particles were dried with hot air at 80 ° C. and dried under reduced pressure at 120 ° C.

The gas generation amount of the obtained polymer was 0.18% by weight, the residue amount was 2.0% by weight, and the MFR was 600 g / 10 minutes.

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

(C) Organic crystal nucleating agent polyetheretherketone: "PEEK450-PF" (manufactured by Victrex MC)

(C') Inorganic crystal nucleating agent Talc: "Hytron" (manufactured by Takehara Chemical Industry Co., Ltd.)

(D) Olefin Elastomer Olefin Elastomer: "Bond First 7M" (manufactured by Sumitomo Chemical Co., Ltd.)

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

(Measurement of weld strength)
The PPS resin composition pellets were supplied to an injection molding machine (SE50DUZ-C160) manufactured by Sumitomo Heavy Industries, Ltd., which had a cylinder temperature of 310 ° C and a mold temperature of 145 ° C. Injection molding was performed with a holding pressure of% to obtain a type A1 test piece specified in ISO 20753. Using this test piece, measurements were performed in accordance with ISO527-1, -2 under the conditions of an atmosphere of 23 ° C. and a relative humidity of 50%, a distance between gripping tools: 114 mm, and a test speed of 5 mm / s.

(Measurement of temperature-decreasing crystallization temperature)
Approximately 10 mg of the pellet of the PPS resin composition was collected as a sample, heated at a heating rate of 20 ° C./min using a differential scanning calorimeter DSC-7 manufactured by PerkinElmer, held at 340 ° C. for 5 minutes, and then 20. The crystallization peak (exothermic peak) temperature when the temperature was lowered at a rate of ° C./min was measured and used as the temperature-decreased crystallization temperature (Tmc (° C.)).

(Measurement of water pressure resistance)
The PPS resin composition pellets are supplied to an injection molding machine (SE100DU) manufactured by Sumitomo Heavy Industries, Ltd., which has a cylinder temperature of 305 ° C and a mold temperature of 130 ° C. A test piece of a T-shaped pipe type joint having an outer diameter of 21.7 mm and a wall thickness of 2.8 mm specified by JIS G3452 was obtained. A rubber pipe connected to a pump (T-300N) manufactured by Kiyowa Co., Ltd. was connected to one of the test pieces, and a sealing plug and a ball valve were connected to the other two sides. Water is passed through the test piece with the ball valve open, the air inside the test piece is evacuated, the ball valve is closed, water pressure is applied using a pump, and the pressure indicated by the pressure gauge when the test piece is destroyed is the water pressure resistance strength. And said.

(Measurement of water pressure resistance after 1000 hours hot water immersion creep test)
The PPS resin composition pellets are supplied to an injection molding machine (SE100DU) manufactured by Sumitomo Heavy Industries, Ltd., which has a cylinder temperature of 305 ° C and a mold temperature of 130 ° C. A test piece of a T-shaped pipe type joint having an outer diameter of 21.7 mm and a wall thickness of 2.8 mm specified by JIS G3452 was obtained. Next, a metal pipe connected to a pump (T-100K) manufactured by Kiyowa Co., Ltd. was connected to one of the test pieces, and a sealing plug and a ball valve were connected to the other two sides. Water was passed through the test piece with the ball valve open, the air inside the test piece was evacuated, and then the ball valve was closed. The test piece is immersed in warm water at 95 ° C., an internal water pressure of 0.5 MPa is applied for 1000 hours, then the T-shaped joint test piece is taken out from hot water, the ball valve is opened to release the water pressure, and then the test piece is passed through. Water was added to check for cracks. The test was carried out at n = 10, and the number of test pieces in which cracks occurred was defined as the number of fractures. After that, a rubber pipe connected to a pump (T-300N) manufactured by Kiyowa Co., Ltd. was connected to one of the test pieces in which cracks did not occur, and a sealing plug and a ball valve were connected to the other two sides. Water was passed through the test piece with the ball valve open, the air inside the test piece was evacuated, and then the ball valve was closed. Water pressure was applied using a pump, and the pressure indicated by the pressure gauge at the time of rupture of the test piece was taken as the water pressure resistance strength after the hot water immersion creep test for 1000 hours.

(Measurement of torque strength)
The PPS resin composition pellets are supplied to an injection molding machine (SE100DU) manufactured by Sumitomo Heavy Industries, Ltd., which has a cylinder temperature of 310 ° C and a mold temperature of 130 ° C. Injection molding is performed with a pressure and a cooling time of 50 seconds, and the taper screw for pipes according to JIS B 0203 (1999) has a nominal diameter of R1 / 2 and a hollow inner diameter of the thread portion of φ11, FIGS. 1 to 3. The joint test piece shown by (1) was obtained (the unit of the numerical value in FIG. 3 is mm). Fix this test piece with a vise, and tighten a brass female screw cap with a nominal diameter of Rc1 / 2 for the taper screw for pipes according to JIS B 0203 (1999) to the male screw part of the test piece with a torque wrench. The torque strength was defined as the strength when the male screw of the test piece broke.

(Manufacturing of PPS resin composition)
100 parts by weight of PPS resin (A) using a twin-screw extruder (TEM-26SS manufactured by Toshiba Machine Co., Ltd.) having an intermediate addition port with a diameter of 26 mm, in which the cylinder temperature is set to 300 ° C. and the screw rotation speed is set to 350 rpm. And (C) the organic crystal nucleating agent is added from the raw material supply port at the weight ratio shown in Table 1 to make it in a molten state, and (B) the fibrous filler is supplied from the intermediate addition port at the weight ratio shown in Table 1 and discharged. Pellets were obtained by melt-kneading at an amount of 30 kg / hour. Each of the above characteristics was evaluated using this pellet. The results are shown in Table 1.

[Examples 1 to 9]
In Examples 1 to 9 shown in Table 1, the water pressure resistance, the moist heat resistance, and the torque strength of the molded product were improved by adding the organic crystal nucleating agent and setting the addition amount to a specific amount. From this result, the piping parts made of the resin compositions of Examples 1 to 9 are suitable for piping parts to which hot water flows and high water pressure is applied.

[Comparative Example 1]
In Comparative Example 1 shown in Table 1, although the Tmc was high because the amount of the organic crystal nucleating agent added was too large, the weld strength, the water pressure resistance strength, and the moist heat resistance were inferior due to the foreign matter effect.

[Comparative Example 2]
In Comparative Example 2 shown in Table 1, although the Tmc was relatively high at 230 ° C., the amount of the organic crystal nucleating agent added was small and the spherulite size was non-uniform, resulting in inferior water pressure resistance and moist heat resistance. there were.

[Comparative Example 3]
In Comparative Example 3 shown in Table 1, since the crystal nucleating agent was not added, the Tmc was low, and the results were inferior in water pressure resistance and moisture heat resistance.
[Comparative Example 4]
In Comparative Example 4 shown in Table 1, an inorganic crystal nucleating agent was added, but the effect of the crystal nucleating agent was inferior, so that the results were inferior in water pressure resistance and moisture heat resistance.

The PPS resin composition of the present invention has excellent water pressure resistance and moisture heat resistance, in addition to water faucet parts, liquid pump casing parts, and mixing faucets, which have a low water pressure load. It can be suitably used as a water-related part to which a large water pressure or a large water pressure is applied by a water hammer, particularly a water-related part in which a liquid of 70 ° C. or higher comes into contact with a pressure of 0.3 MPa or higher.

10 Nut shape part 20 Taper male thread part (nominal diameter R1 / 2)

Claims (7)

With respect to 100 parts by weight of (A) polyphenylene sulfide resin, 20 to 300 parts by weight of (B) an inorganic filler and 0.06 to 0.19 parts by weight of polyether ether ketone as an organic crystal nucleating agent are blended. A polyphenylene sulfide resin composition characterized by becoming. The exothermic peak temperature associated with crystallization observed when the polyphenylene sulfide resin composition is heated to 340 ° C. by a differential scanning calorimeter, melted, and then lowered at a rate of 20 ° C./min ( The polyphenylene sulfide resin composition according to claim 1, wherein Tmc) is 215 ° C. or higher and 260 ° C. or lower. The polyphenylene according to any one of claims 1 to 2 , wherein 0.01 to 20 parts by weight of the (D) olefin-based copolymer is blended with 100 parts by weight of the (A) polyphenylene sulfide resin. Sulfide resin composition. A creep test was conducted in which a T-shaped joint having an outer diameter of 21.7 mm and a wall thickness of 2.8 mm obtained by molding the polyphenylene sulfide resin composition was subjected to a creep test in which an internal water pressure of 0.5 MPa was applied for 1000 hours in warm water at 95 ° C. The polyphenylene sulfide resin composition according to any one of claims 1 to 3 , wherein the water pressure resistance strength measured after the execution is 7 MPa or more. The (A) polyphenylene sulfide resin is a polyphenylene sulfide resin that has been subjected to a thermal oxidation treatment, and (a) the amount of gas generated when heated and melted at 320 ° C. for 2 hours under vacuum is 0.3% by weight or less. (B) After dissolving in 20 times the weight of 1-chloronaphthalene at 250 ° C. for 5 minutes, the residual amount after hot pressure filtration with a PTFE membrane filter having a pore size of 1 μm is 4.0% by weight or less. The polyphenylene sulfide resin composition according to any one of claims 1 to 4 . A molded product comprising the polyphenylene sulfide resin composition according to any one of claims 1 to 5 . The molded product according to claim 6 , wherein the molded product is a casing component for a liquid pump or a piping component for water circulation.

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