JP2018141074A - Polyphenylene sulfide resin composition and molding - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a polyphenylene sulfide resin composition characterized by excellent torque strength of a screw part and a molding thereof.SOLUTION: A polyphenylene sulfide resin composition contains (A) 100 pts.wt. of a polyphenylene sulfide resin, as well as (B) 10-100 pts.wt. of a fibrous filler surface treated with a bisphenol A epoxy resin and a cresol novolac epoxy resin.SELECTED DRAWING: None

Description

  The present invention relates to a polyphenylene sulfide resin composition excellent in mechanical strength, and is suitably used as a screw part. In addition, the screw component of the present invention is useful as a pipe screw component for water circulation, particularly a tapered male screw having a hollow structure, because the torque strength is dramatically improved.

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

  On the other hand, metal piping parts have conventionally been used for water-circulating parts such as housing piping parts and water heater piping parts through which water passes, but in recent years, molded products made of PPS resin compositions are used. It has become.

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

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

  On the other hand, metal (especially made of brass) is still the mainstream for screw parts of housing equipment pipe parts and water heater pipe parts because of fear of destruction when tightening the screw parts, but PPS resin is considered from the viewpoint of cost. It has become like this.

  Patent Document 3 describes a pipe joint having a thread portion as a pipe part of a PPS resin composition containing glass fiber.

  Patent Document 4 describes the contents that provide sufficient tightening torque even if it is made of resin by providing protrusions on the threaded portion, and prevents damage due to excessive tightening of the screw. PPS resin is mentioned as a resin that can be used.

JP 2011-153242 A JP 2007-308612 A Japanese Unexamined Patent Publication No. 2016-35313 Japanese Patent Laid-Open No. 2015-215070

  In recent years, molded products made of a PPS resin composition have come to be applied as piping parts for water circulation, but metal is still the mainstream for screw parts because of fear of breakage during tightening. As the structure of the screw around the water, a taper screw is generally used from the viewpoint of water-stopping, and conforms to the “taper taper screw for pipe” defined in JIS B 0203 (1999). Moreover, since the taper male screw for pipes has a hollow structure and the inner diameter is not defined in JIS B 0203 (1999), it can be arbitrarily designed. However, in order to ensure a sufficient flow rate, the larger inner diameter is more desirable. However, if the inner diameter is large, the thickness of the screw part becomes thin and there is a demerit that the strength is insufficient. Therefore, the hurdle for resinization becomes higher, and the torque strength of the screw part is still increased even in the molded product of the conventional PPS resin composition. Was insufficient.

  On the other hand, conventional metal screw parts have problems in terms of cost, such as heavy weight and a large number of parts, so that workability is poor. Against this background, there has been a demand for a screw component that is excellent in component workability and torque strength and that can replace metal.

  However, although the molded product made of the PPS resin composition disclosed in Patent Document 1 and Patent Document 2 is described for application to water-use applications, it is not disclosed at all that it is suitable for screw parts. .

  On the other hand, Patent Document 3 describes the content of a pipe joint having a threaded portion as a pipe part of the PPS resin composition, but it cannot be said that the torque strength is sufficient.

  Furthermore, Patent Document 4 mentions a PPS resin as a resin that can be improved and applied in terms of structure such as providing a protrusion on a screw portion, but does not disclose a specific effect of the PPS resin.

  As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.

That is, the present invention provides the following.
(1) A blend of 10 to 100 parts by weight of a fibrous filler surface-treated with (B) a bisphenol A type epoxy resin and a cresol novolac type epoxy resin with respect to 100 parts by weight of (A) polyphenylene sulfide resin. A polyphenylene sulfide resin composition characterized by the above.
(2) The amount of the residue when the (A) polyphenylene sulfide resin is melted in 1-chloronaphthalene 20 times weight at 250 ° C. for 5 minutes and filtered under pressure with a PTFE membrane filter having a pore size of 1 μm is 4 The polyphenylene sulfide resin composition as described in (1) above, which is 0.0% by weight or less.
(3) The (A) polyphenylene sulfide resin has been subjected to thermal oxidation treatment under conditions of 160 to 270 ° C. and 0.5 to 30 hours in an atmosphere having an oxygen concentration of 1 to 5% by volume. The polyphenylene sulfide resin composition according to any one of (1) to (2) above.
(4) The composition according to any one of (1) to (3), wherein 1 to 20 parts by weight of (C) an olefin elastomer resin is blended with 100 parts by weight of the (A) polyphenylene sulfide resin. Polyphenylene sulfide resin composition.
(5) A molded article comprising the polyphenylene sulfide resin composition according to any one of (1) to (4) above.
(6) The molded product according to (5) above, wherein the molded product has a threaded portion.
(7) The molded product according to (6), wherein the screw portion is a male screw.
(8) The molded product according to any one of (6) to (7), wherein the threaded portion has a tapered shape.
(9) The molded product according to any one of (6) to (8), wherein the screw portion is hollow.

  ADVANTAGE OF THE INVENTION According to this invention, the resin composition suitable for the polyphenylene sulfide resin composition and molded article excellent in mechanical strength, especially the screw component which torque intensity improved dramatically can be provided.

It is an external view of the molded article which has the thread part which performed the torque strength measurement of the screw in the Example. It is a perspective view of the molded product which has a screw part which performed torque intensity measurement of a screw in an example. It is sectional drawing of the molded article which has the thread part which performed the torque strength measurement of the screw in the Example.

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

  (A) 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, more preferably 90 mol% or more of a polymer containing a repeating unit represented by the above structural formula is preferred. Moreover, about 30 mol% or less of the repeating unit of the PPS resin may be composed of a repeating unit having the following structure.

  Below, the manufacturing method of PPS resin used by this invention is described. First, the contents of the polyhalogenated aromatic compound, sulfidizing agent, polymerization solvent, molecular weight regulator, polymerization aid and polymerization stabilizer used will be described.

[Polyhalogenated aromatic compounds]
A polyhalogenated aromatic compound refers to 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, 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, and preferably p-dichlorobenzene is used. Further, it is 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, 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.

[Sulfiding agent]
Examples of the sulfiding agent include alkali metal sulfides, alkali metal hydrosulfides, and hydrogen sulfide.

  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 of these, 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. Preferably used. These alkali metal hydrosulfides can be used as hydrates or aqueous mixtures or in the form of anhydrides.

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

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

  An alkali metal hydroxide and / or an alkaline earth metal hydroxide can be used in combination 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 thereof. Specific examples of the metal hydroxide include, for example, calcium hydroxide, strontium hydroxide, barium hydroxide, and sodium hydroxide is preferably used.

  When an alkali metal hydrosulfide is used as the sulfiding agent, it is particularly preferable to use an alkali metal hydroxide at the same time, but the amount used is 0.95 to 1. A 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-caprolactam, and 1,3-dimethyl-2-imidazolide. Non-, N, N-dimethylacetamide, N, N-dimethylformamide, hexamethylphosphoric acid triamide, dimethyl sulfone, tetramethylene sulfoxide and the like, and mixtures thereof, and the like are all included. It is preferably used because of its high reaction stability. 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 to 10 mol, preferably 2.25 to 6.0 mol, 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 polyhalogenated aromatic compound in order to form a terminal of the produced PPS resin or to adjust a polymerization reaction or a molecular weight. Can do.

[Polymerization aid]
In order to obtain a PPS resin having a relatively high degree of polymerization in a shorter time, it is also one of preferred embodiments to use a polymerization aid. Here, the polymerization assistant 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 earths. Metal phosphates and the like. These may be used alone or in combination of two or more. Of these, organic carboxylates 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). Alkali metal carboxylates can also be used as hydrates, anhydrides or aqueous solutions. Specific examples of the alkali metal carboxylate include, for example, lithium acetate, sodium acetate, potassium acetate, sodium propionate, lithium valerate, sodium benzoate, sodium phenylacetate, potassium p-toluate, and mixtures thereof. Can be mentioned.

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

  The amount used in the case of using these polymerization aids 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 0.1 to 0.1 in terms 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.

  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 mol to 15 mol with respect to 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.

  There is no particular designation as to the timing of addition of these polymerization aids, which may be added at any time during the previous step, polymerization start, polymerization in the middle to be described later, or may be added in multiple times. When using an alkali metal carboxylate as a polymerization aid, it is more preferable to add it 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 during the polymerization reaction after charging.

[Polymerization stabilizer]
A polymerization stabilizer can also be used to stabilize the polymerization reaction system and prevent side reactions. The polymerization stabilizer contributes to stabilization of the polymerization reaction system and suppresses undesirable side reactions. One measure of the side reaction is the generation of thiophenol, and the addition of a polymerization stabilizer can suppress the generation 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 these, alkali metal hydroxides such as sodium hydroxide, potassium hydroxide, and lithium hydroxide are preferable. Since the alkali metal carboxylate described above also acts as a polymerization stabilizer, it is one of the polymerization stabilizers used in the present invention. In addition, when an alkali metal hydrosulfide is used as a sulfidizing agent, it has been described above that it is particularly preferable to use an alkali metal hydroxide at the same time. Oxides can also be polymerization stabilizers.

  These polymerization stabilizers can be used alone or in combination of two or more. The polymerization stabilizer is usually in a proportion of 0.02 to 0.2 mol, preferably 0.03 to 0.1 mol, 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. Conversely, if it is too much, it is economically disadvantageous and the polymer yield tends to decrease.

  The addition timing of the polymerization stabilizer is not particularly specified, and may be added at any time during the previous step, at the start of polymerization, or during the polymerization described later, or may be added in multiple times. More preferably, it is added at the start of the process or at the start of the polymerization.

  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, but before adding the polyhalogenated aromatic compound, the temperature of the mixture containing the organic polar solvent and the sulfidizing agent is increased, and excess water is removed from the system. It is preferable to remove it. In addition, when water is removed excessively by this operation, it is preferable to add and replenish the deficient water.

  Further, as described above, 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 as the sulfidizing agent. be able to. Although there is no particular limitation on this method, desirably an alkali metal hydrosulfide and an alkali metal hydroxide are added to the organic polar solvent in an inert gas atmosphere at a temperature ranging from room temperature to 150 ° C., preferably from room temperature to 100 ° C. In addition, a method of raising the temperature to at least 150 ° C. or more, preferably 180 to 245 ° C. under normal pressure or reduced pressure, to distill off the water can be mentioned. A polymerization aid may be added at this stage. Moreover, in order to accelerate | stimulate distillation of a water | moisture content, you may react by adding toluene etc.

  The amount of water in the polymerization system in the polymerization reaction is preferably 0.5 to 10.0 moles per mole 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 from the polymerization system from the amount of water charged in the polymerization system. In addition, the water to be charged may be in any form such as water, an aqueous solution, and crystal water.

[Polymerization reaction step]
It is preferable to produce a PPS resin granule 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 starting the polymerization reaction step, a sulfidizing agent and a polyhalogenated aromatic compound are desirably added to an organic polar solvent in an inert gas atmosphere at room temperature to 215 ° C., preferably 100 to 215 ° C. A polymerization aid may be added at this stage. The order in which these raw materials are charged may be out of order or may be simultaneous.

  The mixture is usually heated to a temperature in the range of 200 ° C to 290 ° C. Although there is no restriction | limiting in particular in a temperature increase rate, Usually, the speed of 0.01-5 degreeC / min is selected, and the range of 0.1-3 degreeC / min is more preferable.

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

  For example, a method of raising the temperature to 270 to 290 ° C. after reacting at 200 ° C. to 245 ° C. for a certain period of time before reaching the final temperature is effective in obtaining a higher degree of polymerization. Under the present circumstances, as reaction time in 200 to 245 degreeC, the range of 0.25 to 20 hours is normally selected, Preferably the range of 0.25 to 10 hours is selected.

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

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

The most preferable method for recovering the PPS resin is to perform under a rapid cooling condition, and one preferable method for this recovery method is a flash method. In the flash method, the polymerization reaction product is flushed 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 simultaneously with solvent recovery, the polymer is turned into a granular form This is a recovery method, and the term “flush” here means that a polymerization reaction product is ejected from a nozzle. Specific examples of the atmosphere to be flushed include nitrogen or water vapor at normal pressure, and the temperature is usually selected from the range of 150 ° C to 250 ° C.

  The flash method is a recovery method that is excellent in economic efficiency because it can recover the solids simultaneously with the recovery of the solvent and the recovery time can be relatively short. In this recovery method, an ionic compound typified by Na or an organic low-polymerization product (oligomer) tends to be easily taken 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. If it is a method satisfying the requirements of the present invention, it is not easy to use a method (quenching method) of slow cooling to recover the particulate polymer. 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 a PPS resin that has been subjected to a thermal oxidation treatment after the polymerization reaction step and the recovery step, for example. Preferably, a hydrothermal treatment and an acid treatment step are preferably included before the thermal oxidation treatment step. Moreover, you may include the process wash | cleaned with the organic solvent before the process of acid-treating, and the process of hydrothermal 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 the PPS resin such as nitric acid are not preferable.

  The water when using the aqueous acid solution is preferably distilled water or deionized water. The acid aqueous solution preferably has a pH of 1 to 7, more preferably a pH of 2 to 4. A pH higher than 7 is not preferable because the metal content of the PPS resin increases, and a pH lower than 1 is not preferable because the volatile components of the PPS resin increase.

  As the acid treatment method, it is preferable to immerse the PPS resin in an acid or an aqueous solution of the acid, and it is also possible to appropriately stir and heat as 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 degreeC, an acid treatment effect is small, metal content will increase, and if it exceeds 250 degreeC, since a pressure will become high too much, it is unpreferable on safety. Moreover, it is preferable that pH at the time of processing by immersing a PPS resin in the aqueous solution of acid will be less than 8 by acid treatment, and pH 2-8 is more preferable. A pH higher than 8 is not preferable because the metal content of the obtained PPS resin increases.

  The time for the acid treatment is preferably a time at which the reaction between the PPS resin and the acid is sufficiently equilibrated, 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 performed in a state where the PPS resin is sufficiently immersed in the acid or the aqueous solution of the acid. 0.5-500L of aqueous solution is preferable, 1-100L is more preferable, and 2.5-20L is further more preferable. If 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. Moreover, 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 is excessively large and the production efficiency is remarkably lowered.

  These acid treatments are performed by a method in which a predetermined amount of PPS resin is added to a predetermined amount of water and acid, and the mixture is heated and stirred in a pressure vessel, or a method of continuously performing acid treatment. 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 simple, and methods such as natural filtration, pressure filtration, vacuum filtration, and centrifugal filtration can be exemplified. 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 several times with water or warm water. Examples of the cleaning method include a method of filtering while applying water to the PPS resin on the filtration device, and a method of separating the aqueous solution and the PPS resin by a method such as filtering again after putting the separated PPS resin into prepared water. it can. The water used for washing is preferably distilled water or deionized water.

  In the present invention, it is preferable to perform a hydrothermal 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 further preferably 150 to 200 ° C. If it is less than 80 ° C., the hydrothermal treatment effect is small, and the amount of gas that volatilizes increases. If it exceeds 250 ° C., the pressure becomes too high, which is not preferable for safety.

  The time for the hot water treatment is preferably a time sufficient for extraction treatment with PPS resin and hot water, 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 the PPS resin and water in the hot water treatment is preferably treated in a state in which the PPS resin is sufficiently immersed in water, preferably 0.5 to 500 L of water, and 1 to 100 L with respect to 500 g of PPS resin. Is more preferable, and 2.5 to 20 L is more preferable. When 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 water, resulting in poor cleaning and an increase in the amount of gas that volatilizes, 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 is excessively large, and the production efficiency is remarkably lowered.

  There are no particular restrictions on the operation of these hot water treatments, and a predetermined amount of PPS resin is charged into a predetermined amount of water and heated / stirred in a pressure vessel, or a continuous hot water treatment method is performed. . There is no particular limitation on the method for 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 methods such as 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 several times with water or warm water. There is no particular limitation on the washing method, but the aqueous solution and the PPS resin can be filtered using a method in which water is applied to the PPS resin on the filtration device, or a method in which the separated PPS resin is poured into prepared water and then filtered again. The method of isolate | separating can be illustrated. The water used for washing is preferably distilled water or deionized water.

  Moreover, since the decomposition of the PPS end groups during these acid treatments and hot water treatments is not preferable, it is desirable that the acid treatments and hot water treatments be performed 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.

  In the present invention, a step of washing with an organic solvent may be included before the step of acid treatment or the step of hydrothermal 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. For example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, 1, 3 -Nitrogen-containing polar solvents such as dimethylimidazolidinone, hexamethylphosphoramide, piperazinones, sulfoxide-sulfon solvents such as dimethyl sulfoxide, dimethyl sulfone, sulfolane, ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone, Ether solvents such as dimethyl ether, dipropyl ether, dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, teto Halogen solvents such as chloroethane, perchlorethane, chlorobenzene, alcohol / phenol solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol, and benzene, Examples thereof include aromatic hydrocarbon solvents such as toluene and xylene. Among these organic solvents, use of N-methyl-2-pyrrolidone, acetone, dimethylformamide, chloroform and the like is particularly preferable. These organic solvents are used alone or in combination of two or more.

  As a method of washing with an organic solvent, there is a method of immersing a PPS resin in an organic solvent, and if necessary, stirring or heating can be appropriately performed. There is no restriction | limiting in particular about the washing | cleaning temperature at the time of wash | cleaning PPS resin with an organic solvent, Arbitrary temperature of about normal temperature-about 300 degreeC can be selected. Although the cleaning efficiency tends to increase as the cleaning temperature increases, a sufficient effect is usually 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. There is no particular limitation on the cleaning time. Depending on the cleaning conditions, in the case of batch-type cleaning, a sufficient effect can be obtained usually by cleaning 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 them.

As the PPS resin used in the present invention, it is preferable to use a resin obtained by performing a thermal oxidation treatment after washing with the acid treatment, hot water treatment or organic solvent. Thermal oxidation treatment is to treat the PPS resin by heating in an oxygen atmosphere or by adding a peroxide such as H ₂ O ₂ or a vulcanizing agent such as S. Heating in an oxygen atmosphere is particularly preferred for simplicity.

  The heating device for the thermal oxidation treatment of the PPS resin may be a normal hot air dryer, a rotary type, or a heating device with a stirring blade, but if it is efficiently and more uniformly processed, it is 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, and 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 a 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 with less 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 perform 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, it is preferable to perform the thermal oxidation treatment at a temperature of 160 ° C. or higher because the thermal oxidation treatment can proceed at an appropriate rate and a PPS resin with a small amount of volatile components can be obtained.

  The treatment time for 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 hour or longer is preferable because a sufficient thermal oxidation treatment can be performed and a PPS resin with less volatile components can be obtained. By setting the treatment time to 30 hours or less, the crosslinking 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 thermal oxidation treatment of the PPS resin preferably used in the present invention is 100 to 300 g / 10 minutes is desirable. Since the thermal oxidation treatment in which the difference in melt flow rate before and after thermal oxidation treatment is 100 g / 10 min or more can be achieved, the moisture and heat resistance of the resulting composition containing the PPS resin can be improved. preferable. It is preferable that the difference between the melt flow rate before and after the thermal oxidation treatment is 300 g / 10 min or less because a molded product having excellent torque strength of the resulting composition containing the PPS resin can be obtained.

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

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

  The gas generation amount means the amount of an 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 is a glass in which the PPS resin is vacuum-sealed. It is measured by heating the ampule in a tubular furnace. As the shape of the glass ampule, the abdomen is 100 mm × 25 mm, the neck is 255 mm × 12 mm, and the wall thickness is 1 mm. As a specific measurement method, only the barrel of a glass ampoule in which PPS resin is vacuum-sealed is inserted into a 320 ° C. tubular furnace and heated for 2 hours, so that it becomes volatile at the neck of the ampule not heated by the tubular furnace. The gas is cooled and adheres. After the neck is cut out and weighed, the adhering gas is dissolved in chloroform and removed. The neck is then dried and weighed again. The amount of gas generated is determined from the difference in weight between the neck of the ampoule before and after removing the gas.

  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 large. If the metal content is large, not only the electrical insulation is inferior, but also the melt fluidity and the wet heat resistance are deteriorated.

  The PPS resin used in the present invention is dissolved in 20-fold weight 1-chloronaphthalene at 250 ° C. over 5 minutes, and the residual amount when heated and filtered through a PTFE membrane filter having a pore size of 1 μm is 4.0 weight. % Or less is preferable. When the residual amount exceeds 4.0% by weight, it means that the thermal oxidation crosslinking of the PPS resin proceeds excessively and the gelled product in the resin increases. Excessive thermal oxidation crosslinking of the PPS resin is not preferable because the toughness of the PPS resin is lowered and the torque strength is easily lowered. The lower limit of the residual amount 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 oxidation cross-linking is too slight, so that the volatile components at the time of melting do not decrease so much and the volatile matter reducing effect may be small.

  The residual amount is measured using a SUS test tube equipped with a high-temperature filtration device, a pneumatic cap, and a collecting funnel using a PPS resin formed into a press film of about 80 μm thickness as a sample. Specifically, a membrane filter having a pore size of 1 μm is first set in a SUS test tube, and then PPS resin formed into a press film to 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 filter at 250 ° C. and shaken for 5 minutes. Next, 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 quantification method of the remaining 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.

  Examples of the fibrous filler include glass fiber, carbon fiber, potassium titanate whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber, asbestos fiber, and stone koji fiber. Can be used in combination of two or more. In addition, using these fibrous fillers with a pretreatment with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound results in excellent mechanical strength. Preferred in terms of obtaining. In particular, in the present invention, it is indispensable to use a bisphenol A-type epoxy resin and a cresol novolac-type epoxy resin after being treated from the viewpoint of obtaining a screw-molded product having excellent torque strength. As the fibrous filler, glass fiber or carbon fiber is more preferably used.

  It is essential that the inorganic filler is blended in an amount of 10 to 100 parts by weight with respect to 100 parts by weight of the polyphenylene sulfide resin. The range of 30 to 90 parts by weight is more preferable, and the range of 40 to 80 parts by weight is more preferable. When the amount is less than 10 parts by weight, sufficient torque strength is not exhibited, and when it exceeds 100 parts by weight, an excellent torque strength is not exhibited, which is not preferable.

  In the present invention, 1 to 20 parts by weight of (C) olefin elastomer resin is preferably added to 100 parts by weight of polyphenylene sulfide resin from the viewpoint of obtaining a molded product having excellent torque strength of the PPS resin composition. The olefin elastomer resin preferably contains an α-olefin copolymer having an epoxy group, more preferably in the range of 4 to 14 parts by weight, and still more preferably in the range of 6 to 11 parts by weight. This is one of the particularly preferred aspects in achieving both moldability and moldability. (C) When the olefin elastomer resin is less than 1 part by weight, the toughness is not sufficiently exhibited and the torque strength is lowered. On the other hand, when the amount exceeds 20 parts by weight, although excellent toughness is exhibited, the strength tends to decrease and the amount of gas generated at the time of molding increases, which is not preferable.

  As an olefin copolymer having an epoxy group, an α-olefin such as ethylene, propylene, 1-butene, 1-pentene, 1-octene, 4-methyl-1-pentene, and isobutylene may be used alone or in combination. (Co) polymer, 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, such as 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 / Monomer component (functional group-containing component) having an epoxy group in butyl crylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / butyl methacrylate copolymer, etc. Examples of functional group-containing components that can be obtained by introduction include monomers containing epoxy groups such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, and glycidyl citraconic acid. It is done. The method for introducing these functional group-containing components is not particularly limited, and the olefinic (co) polymer is copolymerized when (co) polymerizing, or grafted using a radical initiator to the olefinic (co) polymer. Or the like. The amount of the functional group-containing component introduced is in the range of 0.001 to 40 mol%, preferably 0.01 to 35 mol%, based on all monomers constituting the modified olefinic (co) polymer. Is appropriate. As a specific example of the 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 shall apply 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 and α, β-unsaturated acid such as ethylene and propylene, other monomers Epoxy group-containing olefin copolymers having an essential component are also preferably used. .

  Preferable olefin elastomer resins 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.

  Furthermore, 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. This is preferable for obtaining high performance and torque strength. Although there is no restriction | limiting in particular in these ratios, (C-1) / (C-2) = 5/95 weight ratio-95/5 weight ratio are preferable, (C-1) / C-2) = 10/90 A range of weight ratio to 90/10 weight ratio is more preferable because of excellent balance between moldability and torque strength.

  On the other hand, (C-2) olefin copolymers having no polar functional group include 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 types, for example, ethylene / propylene copolymer ("/" represents copolymerization, the same applies hereinafter), ethylene / 1-butene copolymer, ethylene / 1 / hexene copolymer and ethylene / 1-octene copolymer.

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

  Furthermore, the PPS resin composition used in the present invention has 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 and the like within a range not impairing the effects of the present invention. A silane compound having at least one functional group selected from the group 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. Mercapto group-containing alkoxysilane compounds such as γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-ureidopropyltriethoxysilane, γ-ureidopropyltrimethoxysilane, γ- (2-ureidoethyl) amino Ureido group-containing alkoxysilane compounds such as propyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane , Γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanatopropyltrichlorosilane and other isocyanate group-containing alkoxysilane compounds, γ- (2-aminoethyl) Amino group-containing alkoxysilane compounds such as aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, and γ-hydroxypropyltri Examples thereof include hydroxyl group-containing alkoxysilane compounds such as methoxysilane and γ-hydroxypropyltriethoxysilane. Of these, an alkoxysilane having an epoxy group, amino group, isocyanate group or hydroxyl group is particularly suitable for obtaining an excellent weld strength. A 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 further blended with other resins as long as the effects of the present invention are not impaired. The blendable resin is not particularly limited, and specific examples thereof include nylon 6, nylon 66, nylon 610, nylon 11, nylon 12, polyamide such as aromatic nylon, polyethylene terephthalate, polybutylene terephthalate, poly Polyester resins such as cyclohexyldimethylene terephthalate and polynaphthalene terephthalate, polyethylene, polypropylene, polytetrafluoroethylene, polyolefin-based elastomer, polyetherester elastomer, polyetheramide elastomer, polyamideimide, polyacetal, polyimide, polyetherimide, polyethersulfone , Polysulfone resin, polyallylsulfone resin, polyketone resin, polyarylate resin, liquid crystal polymer, polyester Teruketon resin, polythioether ketone resin, polyether ether ketone resin, polyamide-imide resins, polyethylene tetrafluoride resins, and epoxy group-containing polyolefin copolymer.

In addition, in the PPS resin composition of the present invention, other components such as antioxidants and heat stabilizers other than those described above (hindered phenols, hydroquinones,
Phosphorus, phosphite, amine, sulfur, and substituted products thereof), weathering agents (resorcinol, salicylate, benzotriazole, benzophenone, hindered amine, etc.), mold release agents and lubricants (montanic acid and Its metal salt, its ester, its half ester, stearyl alcohol, stearamide, stearate, bisurea and polyethylene wax), pigment (cadmium sulfide, phthalocyanine, carbon black for coloring, etc.), dye (such as nigrosine), plasticizer ( octyl p-oxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agents (alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type cationic antistatic agents, polyoxyethylene sorbitan monostearate, etc. Nonionic belt Inhibitors, betaine amphoteric antistatic agents, etc.), flame retardants (eg red phosphorus, phosphate esters, melamine cyanurate, ammonium polyphosphate, brominated polystyrene, brominated polyphenylene ethers, brominated polycarbonates, brominated epoxy resins or these) A combination of brominated flame retardants and antimony trioxide), heat stabilizers, lubricants such as calcium stearate, aluminum stearate, lithium stearate, bisphenol epoxy resins such as bisphenol A type, novolak phenol type epoxy resins, cresol novolac Normal additives such as strength improvers such as type epoxy resins, UV inhibitors, colorants, flame retardants and foaming agents can be added, antioxidants and heat stabilizers (hindered phenols, hydroquinones, Phosphorus, ho Phosphite, amine, it is preferable to use sulfur-based and these substitution products).

More preferably, a phosphorus antioxidant and a hindered phenol antioxidant are used.
Specific examples thereof include, for example, tetrakis (2,4-di-t-butylphenyl) -4,4′-biphenylene phosphonite, bis (2,6-di) as the phosphorus-based and phosphite-based antioxidants. -T-butyl-4-methylphenyl) pentaerythritol-di-phosphite, 2,2-methylenebis (4,6-di-t-butylphenyl) octyl phosphite, triphenyl phosphite, tris (2,4- Di-t-butylphenyl) phosphite, diphenylisodecyl phosphite, phenyl diisodecyl phosphite, 4,4-butylidene-bis (3-methyl-6-tert-butylphenyl-di-tridecyl) phosphite, cyclic neo Pentanetetraylbis (octadecyl phosphite), cyclic neopenta Tetraylbis (2,6-di-t-butyl-4-methylphenyl) phosphite, tris (nonyl phenyl) phosphite, diisodecylpentaerythritol diphosphite, 9,10-dihydro-9-oxa-10- Phosphophenanthrene-10-oxide, 10- (3,5-di-t-butyl-4-hydroxybenzyl) -9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxide, 10-decyloxy Examples include -9,10-dihydro-9-oxa-10-phosphaphenanthrene and a mixture thereof.

  Examples of the hindered phenol antioxidant include triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate, 4,4′-butylidenebis (3-methyl-6- t-butylphenol), 1,6-hexanediol-bis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,4-bis- (n-octylthio) -6- (4 -Hydroxy-3,5-di-t-butylanilino) -1,3,5-triazine, pentaerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], 2 , 2-thio-diethylenebis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], octadecyl-3- (3 -Di-t-butyl-4-hydroxyphenyl) propionate, 2,2-thiobis (4-methyl-6-t-butylphenol), N, N'-hexamethylenebis (3,5-di-t-butyl- 4-hydroxy-hydrocinnamamide), 3,5-di-tert-butyl-4-hydroxy-benzylphosphonate-diethyl ester, 1,3,5-trimethyl-2,4,6-tris (3 , 5-Di-butyl-4-hydroxybenzyl) benzene, ethyl calcium bis (3,5-di-t-butyl-4-hydroxybenzylsulfonate, tris- (3,5-di-t-butyl-4- Hydroxybenzyl) -isocyanurate, 2,6-di-t-butyl-p-cresol, butylated hydroxyanisole, 2,6-di-t-butyl-4-ethylpheno , Stearyl-β- (3,5-di-t-butyl-4-hydroxyphenyl) propionate, 2,2′-methylenebis- (4-methyl-6-tert-butylphenol), 2,2′-methylene- Bis- (4-ethyl-6-tert-butylphenol), 4,4'-thiobis- (3-methyl-6-tert-butylphenol), octylated diphenylamine, 2,4-bis [(octylthio) methyl] -O -Cresol, isooctyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate, 4,4'-butylidenebis (3-methyl-6-tert-butylphenol, 3,9-bis [1, 1-dimethyl-2- [β- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] ethyl] 2,4,8,10-tetraoxy Spiro [5,5] undecane, benzenepropanoic acid, 3- (1,1-dimethylethyl) -4-hydroxy-5-methyl-, 2,4,8,10-tetraoxapyro [5.5] undecane- 3,9-diylbis (2,2-dimethyl-2,1-ethanediyl) ester, 1,1,3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5 -Trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, bis [3,3'-bis- (4'-hydroxy-3'-t-butylphenyl) ) Butyric acid] glycol ester, 1,3,5-tris (3 ′, 5′-di-t-butyl-4′-hydroxybenzyl) -sec-triazine-2,4,6- (1H, 3H, 5H) Trion, d -Α-tocopherol, 3,9-bis (2- (3- (3-tertiarybutyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl) -2,4,8 , 10-tetraoxaspiro [5.5] undecane and the like, or a mixture thereof.

  Examples of the amine antioxidant include dimethyl succinate-1- (2-hydroxyethyl) -4-hydroxy-2,2,6,6-tetramethylpiperidine polycondensate, poly [{6- (1,1 , 3,3, -tetramethylbutyl) amino-1,3,5-triazine-2,4-diyl} {(2,2,6,6, -tetramethyl-4-piperidyl) imino} hexamethylene {( 2,2,6,6, -tetramethyl-4-piperidyl) imino}], 2- (3,5-di-tert-butyl-4-hydroxybenzyl) -2-n-butylmalonate bis (1, 2,2,6,6-pentamethyl-4-piperidyl), tetrakis (2,2,6,6-tetramethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, bis-2,2 , 6,6-tetramethyl-4-pi Lysyl-sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, methyl (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, 1- [2- [ 3- (3.5-Di-t-butyl-4-hydroxyphenyl) propionyloxy] ethyl] -4- [3- (3,5-t-butyl-hydroxyphenyl) propionyloxy] 2,2,6 Examples thereof include 6-tetramethylpiperidine, 4-benzoyloxy-2,2,6,6-tetramethylpiperidine, and the like, or a mixture thereof.

  Examples of the sulfur-based antioxidant include 4,4′-thiobis (6-tert-butyl-3-methylphenol), dialkyl (C12-18) 3,3′-thiodipropionate, pentaerythrityl tetrakis (3 -Laurylthiopropionate) or a mixture thereof.

  Although there is no restriction | limiting in particular in the preparation method of a PPS resin composition, Each raw material is supplied to normally known melt mixers, such as a single screw or a twin screw extruder, a Banbury mixer, a kneader, and a mixing roll, 280-380 degreeC. A typical example is a method of kneading at the above temperature. There are no particular restrictions on the mixing order of the raw materials, 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. Any method may be used, such as a method of mixing a part of raw materials or a method of mixing the remaining raw materials using a side feeder during melt kneading by a single-screw or twin-screw extruder after compounding. As for the small amount additive component, other components may be kneaded and pelletized by the above-described method and then added before molding and used for molding.

  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 torque strength, it can be applied to screw parts. In particular, it is preferably applied to piping parts for water, and more preferably applied to a tapered male screw having a hollow structure. In addition, because of improved water pressure strength and heat and moisture resistance, the present invention can also be applied to piping parts that are used in locations where a high-temperature liquid flows and a large water pressure similar to the direct pressure of water supply or a large water pressure by a water hammer is applied. 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 decompression type water heater, a large water pressure is not applied to the piping parts that come into contact with high-temperature water, and the conventional piping parts made of the PPS resin composition can be used. There was a problem that the water pressure dropped when the hot water was discharged from multiple taps at the same time. On the other hand, in the case of water supply direct pressure type water heaters with improved hot water pressure and hot water temperature unevenness at the time of hot water, piping parts made of a conventional PPS resin composition because high-temperature liquid contacts the piping parts with high water pressure However, the piping component made of the PPS resin composition of the present invention can be applied to a piping component of a water direct pressure type water heater.

  The liquid flowing through the piping component may be an antifreeze containing alcohols, glycols, glycerin, etc. 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, piping parts such as liquid pump casing parts, mixing taps, and watering parts such as water meter parts that have high water pressure load but high temperature water does not flow. it can.

  As described above, since the polyphenylene sulfide resin composition of the present invention is excellent in torque strength, it can be applied to screw parts, and can be used particularly for a taper male screw having a hollow structure for water.

  Other applicable applications 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 capacitor cases, and oscillations. Child, various terminal boards, transformer, plug, printed circuit board, tuner, speaker, microphone, headphones, small motor, magnetic head base, semiconductor, liquid crystal, FDD carriage, FDD chassis, motor brush holder, parabolic antenna, computer related parts, etc. Electrical and electronic parts represented by: VTR parts, TV parts, irons, hair dryers, rice cooker parts, microwave oven parts, acoustic parts, audio equipment parts such as audio / laser discs (registered trademark) / compact discs, Akira parts, refrigerator parts, air conditioner parts, typewriter parts, home, a typical example of which is the word processor parts, it can also be applied to office electrical product 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, typewriters, etc .: microscopes, binoculars, cameras, watches, etc. Optical equipment, precision machinery-related parts represented by: valve alternator terminal, alternator connector, IC regulator, light meter potentiometer base, exhaust gas valve and other valves, fuel-related / exhaust / intake system pipes, air Intake nozzle snorkel, intake manifold, fuel pump, engine coolant joint, carburetor main body, carburetor spacer, exhaust gas sensor, coolant sensor, oil temperature sensor, throttle position sensor, clan Shaft 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, coil for fuel-related electromagnetic valve, 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 case, vehicle speed sensor, Various applications can be exemplified such as automotive-related components such as chromatography Bull liner.

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

[Evaluation method of manufactured PPS resin]
(1) Melt flow rate (MFR)
The measurement temperature was 315.5 ° C. and the load was 5000 g, and the measurement was performed by a method according to ASTM-D1238-70.

(2) Residue amount 100 mg of PPS resin formed into a press film of about 80 μm thickness by setting a pre-weighed PTFE membrane filter with a pore size of 1 μm in a SUS test tube made by Senshu Kagaku equipped with a pneumatic cap and a collecting funnel. And 2 g of 1-chloronaphthalene were weighed in 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. After connecting a 20 mL syringe containing air to the pneumatic cap, 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 membrane filter weight before and after filtration was defined as the amount of residue (% by weight).

[Reference Example 1]
In a 70 liter autoclave with a stirrer and bottom plug valve, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.91 kg (69.80 mol) of 96% sodium hydroxide, N-methyl-2 -Pyrrolidone (NMP) 11.45 kg (115.50 mol), sodium acetate 1.89 kg (23.10 mol), and 10.5 kg of ion-exchanged water were charged, and the temperature was increased to 245 ° C. over about 3 hours while passing nitrogen at normal pressure. After gradually heating and distilling out 14.78 kg of water and 0.28 kg of NMP, the reaction vessel was cooled to 200 ° C. The residual water content in the system per 1 mol of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.

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

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

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

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

  The obtained PPS had an MFR of 600 g / 10 min and a residue amount of 0.7% by weight.

[Reference Example 2]
In a 70 liter autoclave with a stirrer and bottom plug valve, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.94 kg (70.63 mol) of 96% sodium hydroxide, N-methyl-2 -Pyrrolidone (NMP) 11.45 kg (115.50 mol), sodium acetate 1.89 kg (23.1 mol), and ion-exchanged water 5.50 kg were charged to 245 ° C. over about 3 hours while passing nitrogen at normal pressure. After gradually heating and distilling 9.77 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., 10.42 kg (70.86 mol) of p-dichlorobenzene and 9.37 kg (94.50 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and stirred at 240 rpm. The temperature was raised from 200 ° C. to 270 ° C. at a rate of 6 ° C./min, and reacted at 270 ° C. for 140 minutes. Thereafter, 2.40 kg (133 mol) of water was injected while cooling from 270 ° C. to 250 ° C. over 15 minutes. Next, the mixture was gradually cooled from 250 ° C. to 220 ° C. over 75 minutes, and then rapidly cooled to near room temperature, and the contents were taken out.

  The contents were diluted with about 35 liters of NMP, stirred as a slurry at 85 ° C. for 30 minutes, and then filtered through an 80 mesh wire mesh (aperture 0.175 mm) to obtain a solid. The obtained solid was similarly washed and filtered with about 35 liters of NMP. The operation of diluting the obtained solid with 70 liters of ion-exchanged water, stirring at 70 ° C. for 30 minutes, and filtering through an 80 mesh wire net to collect the solid was repeated a total of 3 times. The obtained solid and 32 g of acetic acid were diluted with 70 liters of ion exchange water, stirred at 70 ° C. for 30 minutes, filtered through an 80 mesh wire mesh, and further obtained solids were diluted with 70 liters of ion exchange water. The mixture was stirred at 70 ° C. for 30 minutes and then filtered through an 80 mesh wire net to collect a solid. The solid material thus obtained was dried at 120 ° C. under a nitrogen stream to obtain dry PPS.

  The obtained PPS had an MFR of 300 g / 10 min and a residue amount of 0.8% by weight.

[Reference Example 3]
In a 70 liter autoclave with a stirrer and bottom plug valve, 8.27 kg (70.00 mol) of 47.5% sodium hydrosulfide, 2.94 kg (70.63 mol) of 96% sodium hydroxide, N-methyl-2 -Pyrrolidone (NMP) 11.45 kg (115.50 mol), sodium acetate 0.513 kg (6.25 mol), and ion-exchanged water 3.82 kg were charged to 245 ° C over about 3 hours while passing nitrogen at normal pressure. The mixture was gradually heated to distill out 8.09 kg of water and 0.28 kg of NMP, 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 stirred at 240 rpm. The temperature was raised from 200 ° C. to 270 ° C. at a rate of 6 ° C./min, and reacted at 270 ° C. for 140 minutes. Thereafter, 2.67 kg (148.4 mol) of water was injected while cooling from 270 ° C. to 250 ° C. over 15 minutes. Next, the mixture was gradually cooled from 250 ° C. to 220 ° C. over 75 minutes, and then rapidly cooled to near room temperature, and the contents were taken out.

  The contents were diluted with about 35 liters of NMP, stirred as a slurry at 85 ° C. for 30 minutes, and then filtered through an 80 mesh wire mesh (aperture 0.175 mm) to obtain a solid. The obtained solid was similarly washed and filtered with about 35 liters of NMP. The operation of diluting the obtained solid with 70 liters of ion-exchanged water, stirring at 70 ° C. for 30 minutes, and filtering through an 80 mesh wire net to collect the solid was repeated a total of 3 times. The obtained solid and 32 g of acetic acid were diluted with 70 liters of ion exchange water, stirred at 70 ° C. for 30 minutes, filtered through an 80 mesh wire mesh, and further obtained solids were diluted with 70 liters of ion exchange water. The mixture was stirred at 70 ° C. for 30 minutes and then filtered through an 80 mesh wire net to collect a solid. The solid material thus obtained was dried at 120 ° C. under a nitrogen stream to obtain dry PPS.

  The obtained PPS had an MFR of 600 g / 10 min and a residue amount of 0.9% by weight.

(A) PPS resin PPS-1: The PPS resin polymerized by the method described in Reference Example 1 was subjected to thermal oxidation treatment at an oxygen concentration of 2% and 220 ° C. for 12 hours. The obtained PPS had an MFR of 400 g / 10 min and a residue amount of 1.9% by weight.
PPS-2: PPS resin polymerized by the method described in Reference Example 2 PPS-3: PPS resin polymerized by the method described in Reference Example 3 PPS-4: PPS resin polymerized by the method described in Reference Example 1 Thermal oxidation treatment was performed at an oxygen concentration of 11% and 220 ° C. for 12 hours. The obtained PPS had an MFR of 100 g / 10 min and a residue amount of 13% by weight.

(B) Fibrous filler B-1: Chopped strand A (glass fiber surface-treated with bisphenol A type epoxy resin and cresol novolac type epoxy resin 3 mm long, average fiber diameter 10.5 μm).
B-2: Chopped strand B (glass fiber surface-treated with a cresol novolac type epoxy resin 3 mm long, average fiber diameter 10.5 μm).
B-3: Chopped strand C (glass fiber surface-treated with urethane resin 3 mm long, average fiber diameter 10.5 μm).
B-4: Chopped strand C (glass fiber without surface treatment 3 mm long, average fiber diameter 10.5 μm).

(C) Olefin copolymer C-1: ethylene / glycidyl methacrylate / methyl acrylate copolymer (Bond First E manufactured by Sumitomo Chemical Co., Ltd.)
C-2: Ethylene / 1-octene copolymer (engage 8842 manufactured by Dow Chemical Company).

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

(Screw torque strength measurement)
The resin composition pellets are supplied to an injection molding machine (SE100DU) manufactured by Sumitomo Heavy Industries, Ltd., set at a cylinder temperature of 310 ° C. and a mold temperature of 130 ° C., filled in 2 seconds, and maintained at 70% of the filling pressure. The joint shown in FIGS. 1 to 3 has a shape in which injection molding is performed with a cooling time of 50 seconds and the nominal diameter of the taper screw for the pipe according to JIS B 0203 (1999) is R1 / 2 and the hollow inner diameter of the threaded portion is Φ11. A specimen was obtained. (The unit of the numerical value in the figure is mm.) This test piece is fixed with a vise, and the nominal diameter of the taper screw for the pipe according to JIS B 0203 (1999) is Rc1 / 2 in the male screw portion of the test piece. The brass female screw cap was tightened with a torque wrench, and the strength when the male screw of the test piece was broken was defined as torque strength.

(Production 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 and having a cylinder temperature set to 300 ° C. and a screw rotation speed set to 300 rpm And (C) the elastomer is added from the raw material supply port at the weight ratio shown in Table 1 to be 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 the discharge amount is 40 kg / Pellets were obtained by melting and kneading with time. The above characteristics were evaluated using this pellet. The results are shown in Table 1.

[Examples 1-8]
In Examples 1 to 8 shown in Table 1, it is understood that the torque strength of the screw of the molded product is excellent by using a fibrous filler surface-treated with a bisphenol A type epoxy resin and a cresol novolac type epoxy resin. From this result, the molded article which consists of a resin composition of Examples 1-8 is suitable for the component which has a thread part.

[Example 7, Comparative Example 1]
When Example 7 shown in Table 1 is compared with Comparative Example 1, fiber treated with bisphenol A type epoxy resin and cresol novolak type epoxy resin rather than a fibrous filler surface treated only with cresol novolak type epoxy resin. It can be seen that the torque strength of the screw of the molded product is superior when the shaped filler is used.

[Comparative Example 2 and Comparative Example 3]
Since Comparative Example 2 and Comparative Example 3 shown in Table 1 use a fibrous filler surface-treated with urethane and a fibrous filler not surface-treated, the torque strength of the screw of the molded product is inferior. You can see that

  Since the PPS resin composition of the present invention is excellent in mechanical strength, when it is formed into a molded product having a threaded portion, a threaded part having a greatly improved torque strength, particularly a male thread having a tapered shape, can be obtained.

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

Claims (9)

(A) 10 to 100 parts by weight of a fibrous filler surface-treated with (B) bisphenol A type epoxy resin and cresol novolac type epoxy resin is blended with 100 parts by weight of polyphenylene sulfide resin. A polyphenylene sulfide resin composition. The (A) polyphenylene sulfide resin was melted in 1-chloronaphthalene having a weight of 20 times at 250 ° C. over 5 minutes, and the amount of residue when hot pressure filtration was performed with a PTFE membrane filter having a pore size of 1 μm was 4.0. 2. The polyphenylene sulfide resin composition according to claim 1, wherein the polyphenylene sulfide resin composition is not more than wt%. The (A) polyphenylene sulfide resin has been subjected to a thermal oxidation treatment under conditions of 160 to 270 ° C and 0.5 to 30 hours in an atmosphere having an oxygen concentration of 1 to 5% by volume. The polyphenylene sulfide resin composition according to any one of 1 and 2. The polyphenylene sulfide resin composition according to any one of claims 1 to 3, wherein 1 to 20 parts by weight of (C) an olefin elastomer resin is blended with 100 parts by weight of the (A) polyphenylene sulfide resin. . A molded article comprising the polyphenylene sulfide resin composition according to any one of claims 1 to 4. The molded product according to claim 5, wherein the molded product has a threaded portion. The molded product according to claim 6, wherein the screw portion is a male screw. The molded product according to any one of claims 6 to 7, wherein the screw portion has a tapered shape. The molded product according to claim 6, wherein the screw portion is hollow.