JP2010195962A - Member for fluid piping comprising polyphenylene sulfide resin composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a member for fluid piping, having excellent low-temperature toughness and freezing resistance without largely damaging chemical resistance, heat resistance, creep resistance and mechanical strength. <P>SOLUTION: The member for the fluid piping comprises a polyphenylene sulfide resin composition obtained by compounding 0.1-10 pts.wt. of (c) an alkoxysilane compound having at least one or more kinds of functional groups selected from the group consisting of an amino group, an epoxy group and an isocyanate group with 100 pts.wt. of a resin composition comprising 99-60 wt.% of (a) a polyphenylene sulfide resin, and 1-40 wt.% of (b) an olefinic resin having at least one or more functional groups selected from the group consisting of a carboxy group, an acid anhydride group, an amino group, a hydroxy group and a mercapto group, and providing a resin molded product having ≥300 J/m of a notched Izod impact strength at -40°C (measured according to ASTM D256). <P>COPYRIGHT: (C)2010,JPO&INPIT

Description

  The present invention relates to a member for fluid piping comprising a polyphenylene sulfide resin composition that is extremely excellent in low-temperature toughness, particularly impact strength at −40 ° C., and has a high balance between freezing resistance and creep resistance under actual use conditions. It is.

  Among thermoplastic resins, polyphenylene sulfide (hereinafter abbreviated as PPS) resin is attracting attention as a high-performance, high-performance engineering plastic with excellent heat resistance, chemical resistance, creep resistance, high rigidity, and moldability. Yes. In recent years, PPS resins have been applied to water-circulating parts such as piping parts through which oil passes and water heater piping parts through which water passes, taking advantage of these characteristics. However, PPS alone has low low-temperature toughness, which is particularly important for watering parts, and therefore pipe breakage due to freezing is likely to occur, and a method of blending an olefin resin to prevent freeze cracking is used. However, in the conventional method of blending an olefin resin, it is necessary to blend a large amount of olefin resin in order to provide sufficient low temperature toughness. There was a problem that it could not be used for parts where hot water flowed and internal pressure was applied. Because of such problems, a fluid piping member having a low-temperature toughness and creep resistance balanced at a high level is desired.

  Heretofore, several studies have been made for the purpose of improving the low-temperature toughness of PPS fluid piping members.

  For example, Patent Document 1 discloses a resin composition comprising a polyarylene sulfide resin, an amorphous thermoplastic resin, an olefin polymer, and a silicon-containing compound. However, it has been difficult to achieve both high impact strength and low creep strain by the method disclosed in the present application.

  Patent Document 2 discloses a resin composition for water-borne parts comprising a polyarylene sulfide resin, an elastomer, and a polysiloxane compound. However, the impact strength and creep properties could not be satisfied.

Patent Document 3 discloses a resin composition containing a polyarylene sulfide resin and a thermoplastic elastomer and having a Charpy impact strength at −40 ° C. of 20 kJ / m ² or more. However, as in Patent Documents 1 and 2, the impact strength improvement effect is insufficient, and it is necessary to add a large amount of thermoplastic elastomer in order to impart sufficient low temperature toughness. was there.

  Patent Document 4 discloses a resin composition and a fluid piping member in which a thermoplastic elastomer is dispersed in a polyarylene sulfide resin phase. However, as in Patent Documents 1 to 3, the Izod impact strength at −40 ° C. is still insufficient, and it is necessary to add a large amount of thermoplastic elastomer to impart sufficient low temperature toughness. There was a problem that would increase.

  Patent Document 5 discloses a resin composition comprising a synthetic resin selected from the group consisting of polyolefin, polyarylene sulfide, polyamide, and polyvinyl chloride, and a fibrous filler. However, since the Izod impact strength at −40 ° C. is still insufficient, it is necessary to add a large amount of thermoplastic elastomer in order to give sufficient low temperature toughness, and there is a problem that the creep strain becomes large. .

  Thus, in any of the patent documents, a fluid piping member made of a polyphenylene sulfide resin composition having a dramatic improvement in impact strength at −40 ° C. and a high balance between low-temperature toughness and creep resistance is obtained. Not.

JP 2008-75034 A (Claims) JP 2001-1115020 A (Claims) JP 2006-63255 A (Claims) JP 2004-143372 A (Claims) JP 2001-304463 A (Claims)

  The present invention is extremely excellent in low-temperature toughness, particularly impact strength at −40 ° C., without significantly impairing the chemical resistance, heat resistance and mechanical strength inherent in the polyphenylene sulfide resin, and freezing resistance under actual use conditions, An object of the present invention is to obtain a fluid piping member made of a polyphenylene sulfide resin composition having a high balance of creep resistance.

  Therefore, as a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a polyphenylene sulfide resin, an alkoxysilane compound having a functional group such as an amino group, an epoxy group, an isocyanate group, a carboxyl group, an acid anhydride group, It has been found that by melting and kneading an olefin resin having a functional group such as an amino group, a hydroxyl group, or a mercapto group, the Izod impact strength at -40 ° C. is dramatically improved and is suitable for a member for fluid piping. Reached.

That is, the present invention is as follows.
1. The total of (a) and (b) is 100% by weight, and selected from the group consisting of (a) 99-60% by weight of polyphenylene sulfide resin, (b) carboxyl group, acid anhydride group, amino group, hydroxyl group, mercapto group And 100 parts by weight of a resin composition comprising 1 to 40% by weight of an olefin resin having at least one or more functional groups, (c) at least one or more selected from the group consisting of an amino group, an epoxy group and an isocyanate group A polyphenylene sulfide resin composition comprising 0.1 to 10 parts by weight of an alkoxysilane compound having a functional group, which is an Izod impact strength with a cut notch at −40 ° C. of a resin molded product (measured according to ASTM D256) A fluid piping comprising a polyphenylene sulfide resin composition having a JO of 300 J / m or more Member 2. In the morphology (phase structure), (a) a polyphenylene sulfide resin forms a continuous phase (sea phase), and (b) a dispersed phase (island phase) in which an olefin resin having a functional group is dispersed with a number average dispersed particle size of 500 nm or less. 2. The fluid piping member according to 1, wherein the fluid piping member has a sea-island structure.
3. In the molded piece obtained by pulverizing and injection-molding again after injection molding, the (b) functional group-containing olefin resin is dispersed with a number average dispersed particle diameter of 500 nm or less. The member for fluid piping as described in 2.
4). (B) An olefin resin having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amino group, a hydroxyl group, and a mercapto group is an ethylene-containing resin having a carboxyl group and / or an acid anhydride group. 4. The fluid piping member according to any one of 1 to 3, which is a butene copolymer.
5). (C) The alkoxysilane compound having at least one functional group selected from the group consisting of an amino group, an epoxy group, and an isocyanate group is an alkoxysilane compound having an epoxycyclohexyl group or an isocyanate group. The member for fluid piping according to any one of the above.
6). (A) The member for fluid piping according to any one of 1 to 5, wherein the polyphenylene sulfide resin is an acid-treated polyphenylene sulfide resin.
7). The total of (a) and (b) is 100% by weight, (a) 99 to 85% by weight of polyphenylene sulfide resin, (b) selected from the group consisting of carboxyl group, acid anhydride group, amino group, hydroxyl group and mercapto group The fluid piping member according to any one of 1 to 6, comprising 1 to 15% by weight of an olefinic resin having at least one functional group.
8). From the group consisting of (a) polyphenylene sulfide resin 99 to 60% by weight, (b) carboxyl group, acid anhydride group, amino group, hydroxyl group, and mercapto group, where the total of (a) and (b) is 100% by weight (C) At least one selected from the group consisting of an amino group, an epoxy group, and an isocyanate group with respect to 100 parts by weight of a resin composition consisting of 1 to 40% by weight of an olefin resin having at least one functional group selected A polyphenylene sulfide resin composition comprising 0.1 to 10 parts by weight of an alkoxysilane compound having a functional group, wherein (a) the polyphenylene sulfide resin and (c) the alkoxysilane compound having a functional group are previously melted After kneading, it is obtained by further melt-kneading with the olefin resin having the functional group (b). Fluid piping member according to any one of 1 to 7 consisting of that the polyphenylene sulfide resin composition.
9. A fluid piping member according to any one of 9.1 to 8, wherein the member is a pipe joint selected from toilet-related parts, water heater-related parts, bath-related parts, and pump-related parts. parts.
It is.

  According to the present invention, a fluid piping member made of a polyphenylene sulfide resin composition having excellent low-temperature toughness, particularly Izod impact strength at −40 ° C. can be obtained. In addition, because it is extremely excellent in toughness, high Izod impact strength is easily expressed even when the composition of the olefin resin is relatively small, so that the chemical resistance, heat resistance, creep resistance, and mechanical strength inherent in polyphenylene sulfide resin are improved. A fluid piping member made of a tough polyphenylene sulfide resin composition can be obtained without significant loss.

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

(A) Polyphenylene sulfide resin (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. In addition, (a) the PPS resin may be composed of a repeating unit having the following structure in an amount of less than 30 mol% of the repeating unit.

  Since the PPS copolymer having a part of such a structure has a low melting point, such a resin composition is advantageous in terms of moldability.

  Although there is no restriction | limiting in particular in the melt viscosity of (a) PPS resin used by this invention, The one with the higher melt viscosity is preferable from the meaning which obtains the more excellent toughness. For example, a range exceeding 80 Pa · s (310 ° C., shear rate 1000 / s) is preferable, 100 Pa · s or more is more preferable, and 150 Pa · s or more is more preferable. The upper limit is preferably 600 Pa · s or less from the viewpoint of maintaining melt fluidity.

  In addition, the melt viscosity in this invention is the value measured using the Toyo Seiki Co., Ltd. capilograph on the conditions of 310 degreeC and the shear rate of 1000 / s.

  Although the manufacturing method of (a) PPS resin used for this invention is demonstrated below, if (a) PPS resin of the said structure is obtained, it will not be limited to the following method.

  First, the contents of the polyhalogen aromatic compound, sulfidizing agent, polymerization solvent, molecular weight regulator, polymerization aid and polymerization stabilizer used in the production method 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 aroma 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 polyhalogenated aromatic compound is used in an amount of 0.9 to 2.0 mol, preferably 0.95 to 1. mol per mol of sulfidizing agent, from the viewpoint of obtaining a (a) PPS resin having a viscosity suitable for processing. A range of 5 moles, more preferably 1.005 to 1.2 moles 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.

  In addition, an alkali metal sulfide prepared in situ in a reaction system from an alkali metal hydrosulfide and an alkali metal hydroxide can also be used. Moreover, an alkali metal sulfide can be prepared from an alkali metal hydrosulfide and an alkali metal hydroxide and transferred to a polymerization tank for use.

  Alternatively, an alkali metal sulfide 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. Moreover, an alkali metal sulfide can be prepared from an alkali metal hydroxide such as lithium hydroxide or sodium hydroxide and hydrogen sulfide, and transferred to a polymerization tank for use.

  The amount of the sulfidizing agent charged means 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]
An organic polar solvent is preferably used 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) A monohalogen compound (not necessarily an aromatic compound) is combined with the polyhalogenated aromatic compound for the purpose of forming a terminal of the PPS resin or adjusting the polymerization reaction or the molecular weight. Can be used together.

[Polymerization aid]
In order to obtain a relatively high degree of polymerization (a) PPS resin in a shorter time, it is also one of preferred embodiments to use a polymerization aid. Here, the polymerization assistant means (a) a substance having an action of increasing the viscosity of the PPS resin to be obtained. 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, water, and alkali metal chlorides are preferable. Further, as the organic carboxylates, alkali metal carboxylates are preferable, and as the alkali metal chlorides, lithium chloride is preferable.

  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.

  When using these alkali metal carboxylates as polymerization aids, the amount used is usually in the range of 0.01 to 2 moles per mole of charged alkali metal sulfide, and in the sense of obtaining a higher degree of polymerization. The range of 0.1-0.6 mol is preferable, and the range of 0.2-0.5 mol is more preferable.

  Moreover, the addition amount in the case of using water as a polymerization aid is usually in the range of 0.3 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, 0.6 to The range of 10 mol is preferable, and the range of 1 to 5 mol is more preferable.

  Of course, two or more kinds of these polymerization aids can be used in combination. For example, when an alkali metal carboxylate and water are used in combination, a higher molecular weight can be obtained in a smaller amount.

  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. 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 the ratio is too large, it is economically disadvantageous or 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. It is more preferable because it is easy to add at the start of the process or at the start of the polymerization.

  Next, a preferred method for producing the (a) PPS resin used in the present invention will be described in detail in the order of a pre-process, a polymerization reaction process, a recovery process, and a post-treatment process. Of course, the process is limited to this process. It is not something.

[pre-process]
(A) In the production method of PPS resin, the sulfiding 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 sulfiding agent is increased. It is preferable to warm and remove excess water out of the system.

  As described above, a sulfidizing agent 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. Can do. 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, there is a method in which the temperature is raised to at least 150 ° C. or more, preferably 180 to 260 ° C. under normal pressure or reduced pressure, and water is distilled off. 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 0.3 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]
(A) A PPS resin is produced 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, the organic polar solvent, the sulfidizing agent, and the polyhalogenated aromatic compound are desirably mixed in an inert gas atmosphere at room temperature to 240 ° C., preferably 100 to 230 ° 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.

  In the stage before reaching the final temperature, for example, a method of reacting at 200 to 260 ° C. for a certain time and then raising the temperature to 270 to 290 ° C. is effective in obtaining a higher degree of polymerization. Under the present circumstances, as reaction time in 200 to 260 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 may be effective to perform polymerization in multiple 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%.

The conversion rate of the polyhalogenated aromatic compound (herein abbreviated as PHA) is a value calculated by the following formula. The residual amount of PHA can usually be determined by gas chromatography.
(A) When polyhalogenated aromatic compound is added excessively in a molar ratio with respect to the alkali metal sulfide, the conversion rate = [PHA charge (mol) −PHA remaining amount (mol)] / [PHA charge (mol) -PHA excess (mole)]
(B) In cases other than (A) above, conversion rate = [PHA charge (mol) −PHA remaining amount (mol)] / [PHA charge (mol)]

[Recovery process]
(A) In the method for producing a PPS resin, after the polymerization is completed, a solid is recovered from a polymerization reaction product containing a polymer, a solvent, and the like. Any known method may be adopted as the recovery method.

  For example, after completion of the polymerization reaction, a method of slowly cooling and recovering the particulate polymer may be used. Although there is no restriction | limiting in particular in the slow cooling rate in this case, Usually, it is about 0.1 degree-C / min-about 3 degree-C / min. It is not necessary to perform slow cooling at the same rate in the entire process of the slow cooling step, such as a method of gradually cooling at a rate of 0.1 to 1 ° C / min until the polymer particles are crystallized and precipitated, and then at a rate of 1 ° C / min or more. It may be adopted.

Moreover, it is also one of the preferable methods to perform said collection | recovery on quenching conditions, As a preferable method of this collection method, the flash method is mentioned. In the flash method, the polymerization reaction product is flushed from a high temperature and high pressure (usually 250 ° C. or more, 8 kg / cm ² or more) into an atmosphere of normal pressure or reduced pressure, and the polymer is recovered in the form of powder simultaneously with the solvent recovery This is a method, and the term “flash” 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 in the range of 150 ° C to 250 ° C.

[Post-processing process]
(A) The PPS resin may be produced through the above polymerization and recovery steps and then subjected to acid treatment, hot water treatment or washing with an organic solvent.

  When acid treatment is performed, it is as follows. (A) The acid used for the acid treatment of the PPS resin is not particularly limited as long as it does not have the function of decomposing the (a) PPS resin, such as acetic acid, hydrochloric acid, sulfuric acid, phosphoric acid, silicic acid, carbonic acid and propyl acid. Among them, acetic acid and hydrochloric acid are more preferably used, but (a) those that decompose and deteriorate the PPS resin such as nitric acid are not preferable.

  As the acid treatment method, there is a method of (a) immersing the PPS resin in an acid or an acid aqueous solution, and it is possible to appropriately stir or heat as necessary. For example, when acetic acid is used, a sufficient effect can be obtained by immersing the PPS resin powder in an aqueous PH4 solution heated to 80 to 200 ° C. and stirring for 30 minutes. The PH after processing may be 4 or more, for example, about PH 4-8. The acid-treated (a) PPS resin is preferably washed several times with water or warm water in order to remove residual acid or salt. The water used for washing is preferably distilled water or deionized water in the sense that it does not impair the effect of the preferred chemical modification of (a) PPS resin by acid treatment.

  When performing hot water treatment, it is as follows. (A) In the hot water treatment of the PPS resin, the temperature of the hot water is preferably 100 ° C. or higher, more preferably 120 ° C. or higher, further preferably 150 ° C. or higher, and particularly preferably 170 ° C. or higher. If it is less than 100 degreeC, since the effect of the preferable chemical modification | denaturation of (a) PPS resin is small, it is unpreferable.

  The water used is preferably distilled water or deionized water in order to exhibit the effect of preferable chemical modification of the (a) PPS resin by hot water washing. There is no particular restriction on the operation of the hot water treatment, and a predetermined amount of (a) PPS resin is put into a predetermined amount of water and heated and stirred in a pressure vessel, or a method of continuous hot water treatment is performed. Is called. (A) The ratio of the PPS resin and water is preferably larger, but usually a bath ratio of (a) 200 g or less of PPS resin is selected for 1 liter of water.

  Further, since the decomposition of the terminal group is not preferable, the treatment atmosphere is desirably an inert atmosphere in order to avoid this. Furthermore, it is preferable that the (a) PPS resin that has finished this hot water treatment operation is washed several times with warm water in order to remove the remaining components.

  When washing with an organic solvent, it is as follows. (A) The organic solvent used for washing the PPS resin is not particularly limited as long as it does not have an action of decomposing (a) the PPS resin. For example, N-methyl-2-pyrrolidone, dimethylformamide, dimethylacetamide, Nitrogen-containing polar solvents such as 1,3-dimethylimidazolidinone, hexamethylphosphoramide, piperazinones, sulfoxide / sulfone solvents such as dimethyl sulfoxide, dimethyl sulfone and sulfolane, ketones such as acetone, methyl ethyl ketone, diethyl ketone and acetophenone Solvents, ether solvents such as dimethyl ether, dipropyl ether, dioxane, tetrahydrofuran, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, Halogen solvents such as trachlorethane, perchlorethane, chlorobenzene, alcohol / phenol solvents such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol and the like Aromatic hydrocarbon solvents such as benzene, toluene, xylene and the like can be mentioned. 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 such as (a) 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 (a) 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.

  In the present invention, PPS obtained by introducing antari earth metal salt such as Ca into PPS may be used. As a method for introducing the alkaline earth metal salt, a method of adding an alkaline earth metal salt before, during, or after the previous step, before the polymerization step, during the polymerization step, after the polymerization step, in the polymerization vessel Or a method of adding an alkaline earth metal salt at the beginning, middle, or last stage of the washing step. Among them, the easiest method is a method of adding an alkaline earth metal salt after removing residual oligomers and residual salts by washing with an organic solvent or washing with warm water or hot water. The alkaline earth metal salt is preferably introduced into the PPS in the form of an alkaline earth metal ion such as acetate, hydroxide or carbonate. It is preferable to remove excess alkaline earth metal salt by washing with warm water. The alkaline earth metal ion concentration at the time of introducing the alkaline earth metal ion is preferably 0.001 mmol or more, more preferably 0.01 mmol or more with respect to 1 g of PPS. As temperature, 50 degreeC or more is preferable, 75 degreeC or more is more preferable, and 90 degreeC or more is especially preferable. Although there is no upper limit temperature, it is usually preferably 280 ° C. or lower from the viewpoint of operability. The bath ratio (the weight of the cleaning solution with respect to the dry PPS weight) is preferably 0.5 or more, more preferably 3 or more, and still more preferably 5 or more.

  In the present invention, from the viewpoint of obtaining a polyphenylene sulfide resin composition having extremely excellent toughness, after removing residual oligomers and residual salts by repeating organic solvent washing and hot water at about 80 ° C. or hot water washing described above several times Particularly preferred is an acid treatment method.

  (A) The PPS resin can be used after having been polymerized to have a high molecular weight by heating in an oxygen atmosphere and thermal oxidation crosslinking treatment by heating with addition of a crosslinking agent such as peroxide.

  When the dry heat treatment is performed for the purpose of increasing the molecular weight by thermal oxidation crosslinking, the temperature is preferably 160 to 260 ° C, more preferably 170 to 250 ° C. The oxygen concentration is preferably 5% by volume or more, more preferably 8% by volume or more. Although there is no restriction | limiting in particular in the upper limit of oxygen concentration, About 50 volume% is a limit. The treatment time is preferably 0.5 to 100 hours, more preferably 1 to 50 hours, and further preferably 2 to 25 hours. The heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary type or a stirring blade. However, for efficient and more uniform processing, a heating apparatus with a rotary type or a stirring blade is used. More preferably it is used.

  In addition, it is possible to carry out dry heat treatment for the purpose of suppressing thermal oxidative crosslinking and removing volatile matter. The temperature is preferably 130 to 250 ° C, and more preferably 160 to 250 ° C. In this case, the oxygen concentration is preferably less than 5% by volume, and more preferably less than 2% by volume. The treatment time is preferably 0.5 to 50 hours, more preferably 1 to 20 hours, and further preferably 1 to 10 hours. The heat treatment apparatus may be a normal hot air dryer or a heating apparatus with a rotary type or a stirring blade. However, for efficient and more uniform processing, a heating apparatus with a rotary type or a stirring blade is used. More preferably it is used.

  However, (a) the PPS resin is preferably a substantially linear PPS that does not undergo high molecular weight by thermal oxidation crosslinking treatment in order to achieve the toughness target. In addition, preferable (a) PPS resins used in the present invention include Toray Industries, Inc. M2588, M2888, M2088, T1881, L2120, L2480, M2100, M2900, E2080, E2180, E2280, etc. A plurality of different melt viscosities may be mixed and used.

(B) Olefin resin having at least one functional group selected from the group consisting of carboxyl group, acid anhydride group, amino group, hydroxyl group and mercapto group (b) carboxyl group and acid anhydride group used in the present invention An olefin resin having at least one functional group selected from the group consisting of an amino group, a hydroxyl group, and a mercapto group is an olefin polymer obtained by polymerizing or copolymerizing an olefin, a carboxyl group, an acid anhydride group, an amino group, Examples thereof include an olefin resin obtained by introducing a monomer component having a functional group such as a hydroxyl group or a mercapto group.

  Examples of olefin polymers or copolymers include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1- Dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4 dimethyl-1-hexene, 4,4 dimethyl-1-pentene, 4-ethyl-1-hexene, Α-Oleph such as 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene Polymers obtained by polymerizing single or two or more kinds, such as α-olefin and acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, etc. Examples include α, β-unsaturated carboxylic acids and copolymers thereof with alkyl esters. Preferable specific examples of the olefin polymer or copolymer include an ethylene / α-olefin copolymer using an α-olefin having 6 to 12 carbon atoms. Among these, an ethylene / 1-butene copolymer is more preferable.

The ethylene / α-olefin copolymer suitably used in the present invention preferably has a density of 0.880 g / cm ³ or less, more preferably in the range of 0.830 to 0.880 g / cm ^3. A range of 0.850 to 0.875 g / cm ³ is more preferable. The glass transition temperature (measured according to JISK7121) is preferably −40 ° C. or lower.

  (B) The functional group contained in the olefinic resin is preferably a carboxyl group or an acid anhydride group from the viewpoint of (a) high affinity with the PPS resin, and the olefin polymer or copolymer contains a carboxyl group. Examples of functional group-containing components for introducing a monomer component having a functional group such as a group and a salt thereof, an acid anhydride group include maleic anhydride, fumaric anhydride, itaconic anhydride, citraconic anhydride, endo And monomers containing an acid anhydride group such as bicyclo- (2,2,1) -5-heptene-2,3-dicarboxylic acid anhydride. The method for introducing these functional group-containing components is not particularly limited, and a method such as copolymerization or graft introduction using an olefin polymer or copolymer using a radical initiator can be used. The amount of the monomer component containing a functional group is suitably 0.001 to 40 mol%, preferably 0.01 to 35 mol%, relative to the olefin polymer or copolymer. is there.

(C) Alkoxysilane compound having at least one functional group selected from the group consisting of an amino group, an epoxy group and an isocyanate group At least one type selected from the group consisting of an amino group, an epoxy group and an isocyanate group used in the present invention. As an alkoxysilane compound having an amino group among the alkoxysilane compounds having a functional group of any one, any one can be used as long as it is a silane compound having one or more amino groups in one molecule and having two or three alkoxy groups. It is also effective with Examples thereof include γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane. As the alkoxysilane compound having an epoxy group, any silane compound having one or more epoxy groups and two or three alkoxy groups in one molecule is effective. Examples thereof include γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, and the like. Any alkoxysilane compound having an isocyanate group is effective as long as it is a silane compound having one or more isocyanate groups in one molecule and two or three alkoxy groups. For example, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatepropylethyldiethoxysilane Examples include silane and γ-isocyanatopropyltrichlorosilane. Among them, in order to obtain a stable and high toughness improving effect, an alkoxysilane compound having an epoxycyclohexyl group or an isocyanate group is preferable, and an alkoxysilane compound having an isocyanate group is more preferable.

  The blending ratio of (a) PPS resin and (b) olefin resin having at least one functional group selected from the group consisting of carboxyl group, acid anhydride group, amino group, hydroxyl group and mercapto group in the present invention is ( (a) / (b) = 99-60 wt% / 1-40 wt%, where (a) / (b) = 97-70 wt. % / 3 to 30% by weight is preferable, (a) / (b) = 95 to 80% by weight / 5 to 20% by weight is more preferable, and (a) / (b) = 93 to 85% by weight A range of / 7 to 15% by weight is more preferable. (A) When the PPS resin exceeds 99% by weight, the effect of improving low temperature toughness is poor, and when the (a) PPS resin is less than 60% by weight, rigidity, heat resistance, chemical resistance, creep resistance, and melt fluidity are poor. This is not preferable because it is significantly inhibited.

  In the present invention, the compounding amount of the alkoxysilane compound having at least one functional group selected from the group consisting of (c) amino group, epoxy group and isocyanate group is (a) polyphenylene sulfide resin, (b) carboxyl group and acid. 0.1 to 10 parts by weight with respect to 100 parts by weight of the total of olefinic resins having at least one functional group selected from the group consisting of an anhydride group, amino group, hydroxyl group and mercapto group; The range of 2 to 5 parts by weight is preferable, and the range of 0.3 to 3 parts by weight is more preferable. When the blending amount of the component (c) is less than 0.1 parts by weight, it is difficult to obtain stable high-temperature toughness and freezing resistance. When the blending amount of the component (c) exceeds 10 parts by weight, It is not preferable because the sex is inhibited.

  The PPS resin composition of the present invention has excellent toughness as well as excellent heat resistance, chemical resistance, and creep resistance inherent in (a) PPS resin. The attached Izod impact strength (measured according to ASTM D256) needs to be 300 J / m or more, preferably 350 J / m or more, and more preferably 400 J / m or more. An olefin having at least one functional group selected from the group consisting of (b) a carboxyl group, an acid anhydride group, an amino group, a hydroxyl group, and a mercapto group, wherein the total of (a) and (b) is 100% by weight. Even when the resin content is 15% by weight or less, the Izod impact strength with cut notch (measured according to ASTM D256) at −40 ° C. of the resin molded product needs to be 300 J / m or more.

  The PPS resin composition of the present invention has excellent toughness as well as (a) the excellent heat resistance, chemical resistance, and creep resistance inherent to the PPS resin. In order to develop such properties, in morphology, (a) the PPS resin forms a sea phase (continuous phase or matrix), and (b) consists of a carboxyl group, an acid anhydride group, an amino group, a hydroxyl group, and a mercapto group. It is preferable that an olefin resin having at least one functional group selected from the group forms an island phase (dispersed phase). Further, (b) the number average dispersed particle diameter of the olefin resin having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amino group, a hydroxyl group, and a mercapto group may be 500 nm or less. More preferably, it is 400 nm or less, more preferably 300 nm or less. The lower limit is preferably 1 nm or more from the viewpoint of productivity. (B) When the number average dispersed particle diameter of the olefin resin having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amino group, a hydroxyl group, and a mercapto group is in a range exceeding 500 nm, This is not preferable because the effect of improving toughness is significantly impaired.

  In addition, the PPS resin composition of the present invention stably exhibits excellent toughness even when the number of melt residences and time increase. In order to express such characteristics, even after the injection molding is performed once, the molded piece is pulverized and the injection molded again, (a) PPS resin forms a sea phase (continuous phase or matrix). (B) It is preferable that the olefin resin having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amino group, a hydroxyl group, and a mercapto group forms an island phase (dispersed phase). Further, (b) the number average dispersed particle size of the olefin resin having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amino group, a hydroxyl group, and a mercapto group may be 500 nm or less. Desirably, preferably 400 nm or less, more preferably 300 nm or less. The lower limit is preferably 1 nm or more from the viewpoint of productivity. (B) When the number average dispersed particle diameter of the olefin resin having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amino group, a hydroxyl group, and a mercapto group is in a range exceeding 500 nm, This is not preferable because the effect of improving toughness is significantly impaired.

  Here, the number average dispersed particle size is as follows: (a) ASTM No. 1 dumbbell test piece was molded at a molding temperature of PPS resin melting peak temperature + 20 ° C., and a thin piece of 0.1 μm or less at −20 ° C. from the center. Is cut in the direction of the cross-sectional area of the dumbbell piece, and observed with an H-7100 transmission electron microscope (resolution (particle image) 0.38 nm, magnification: 500 to 600,000 times) manufactured by Hitachi, Ltd. and magnified 10,000 times. The dispersed portion of the olefin resin having at least one functional group selected from the group consisting of 100 (b) carboxyl group, acid anhydride group, amino group, hydroxyl group and mercapto group is Each of the maximum diameter and the minimum diameter is measured and the average value is defined as the dispersed particle diameter, and then the average value is obtained.

Kneading process method Melt kneading is performed by supplying to a commonly known melt kneader such as a single-screw or twin-screw extruder, a Banbury mixer, a kneader, or a mixing roll. A typical example is a method of kneading at a temperature, but (b) an olefin having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amino group, a hydroxyl group, and a mercapto group. In order to make the dispersion of the resin finer, it is preferable to use a twin screw extruder and relatively increase the shearing force. Specifically, L / D (L: screw length, D: screw diameter) is 20 or more, a twin screw extruder having two or more kneading parts is used, and the screw rotation speed is 100 to 500 rotations. For example, a method of kneading so that the resin temperature at the time of mixing is (a) the melting peak temperature of the PPS resin +10 to 70 ° C. can be preferably used. Regarding the mixing order of the raw materials, (a) a PPS resin and (c) an alkoxysilane compound having at least one functional group selected from the group consisting of an amino group, an epoxy group, and an isocyanate group were blended and melt-kneaded in advance. Thereafter, (b) melting and kneading with an olefin resin having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amino group, a hydroxyl group, and a mercapto group is 300 J / m or more. It is indispensable for exhibiting −40 ° C. Izod impact strength, and (b) can be exemplified as a more preferable method from the viewpoint of finely dispersing the olefin resin. At this time, (a) a PPS resin and (c) an alkoxysilane compound having at least one functional group selected from the group consisting of an amino group, an epoxy group, and an isocyanate group were blended, melt-kneaded in advance, and pelletized. Thereafter, (b) an olefin resin having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amino group, a hydroxyl group, and a mercapto group can be blended and further melt-kneaded. And (a) a PPS resin and (c) an alkoxysilane compound having at least one functional group selected from the group consisting of an amino group, an epoxy group and an isocyanate group, and a side feeder is previously melt-kneaded. (B) less selected from the group consisting of carboxyl group, acid anhydride group, amino group, hydroxyl group and mercapto group Also it can be melt-kneaded by supplying the olefin resin from the middle of the extruder having one or more functional groups.

Inorganic filler Although not an essential component, the PPS resin composition of the present invention can be used by blending an inorganic filler as long as the effects of the present invention are not impaired. Specific examples of such inorganic fillers include glass fiber, carbon fiber, carbon nanotube, carbon nanohorn, potassium titanate whisker, zinc oxide whisker, calcium carbonate whisker, wollastonite whisker, aluminum borate whisker, aramid fiber, alumina fiber, silicon carbide fiber. , Ceramic filler, asbestos fiber, stone fiber, metal fiber, etc., or fullerene, talc, wollastonite, zeolite, sericite, mica, kaolin, clay, pyrophyllite, silica, bentonite, asbestos, alumina Silicates such as silicates, metal compounds such as silicon oxide, magnesium oxide, alumina, zirconium oxide, titanium oxide and iron oxide, carbonates such as calcium carbonate, magnesium carbonate and dolomite, sulfuric acid Sulfates such as lucium and barium sulfate, hydroxides such as calcium hydroxide, magnesium hydroxide and aluminum hydroxide, glass beads, glass flakes, glass powder, ceramic beads, boron nitride, silicon carbide, carbon black and silica, graphite Non-fibrous fillers such as glass fiber, silica, and calcium carbonate are preferable, and calcium carbonate and silica are particularly preferable from the viewpoint of the effects of the anticorrosive material and the lubricant. These inorganic fillers may be hollow, and two or more kinds may be used in combination. Further, these inorganic fillers may be used after being pretreated with a coupling agent such as an isocyanate compound, an organic silane compound, an organic titanate compound, an organic borane compound, and an epoxy compound. Of these, calcium carbonate, silica, and carbon black are preferable from the viewpoint of the anticorrosive material, the lubricant, and the effect of imparting conductivity.

  The blending amount of the inorganic filler is as follows: (a) a polyphenylene sulfide resin and (b) an olefin resin having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amino group, a hydroxyl group, and a mercapto group. The range of 30 parts by weight or less is selected with respect to the total of 100 parts by weight, preferably less than 10 parts by weight, more preferably less than 1 part by weight, and still more preferably 0.8 parts by weight or less. There is no particular lower limit, but 0.0001 parts by weight or more is preferable. While the blending of the inorganic filler is effective for improving the elastic modulus of the material, a large amount of blending exceeding 30 parts by weight is not preferable because it causes a large decrease in toughness. The content of the inorganic filler can be appropriately changed depending on the application from the balance between toughness and rigidity.

Other Additives Further, the PPS resin composition of the present invention is at least selected from the group consisting of (b) a carboxyl group, an acid anhydride group, an amino group, a hydroxyl group, and a mercapto group as long as the effects of the present invention are not impaired. A resin other than the olefin resin having one or more functional groups may be added and blended. Specific examples thereof include polyamide resin, polybutylene terephthalate resin, polyethylene terephthalate resin, modified polyphenylene ether resin, polysulfone resin, polyallyl sulfone resin, polyketone resin, polyarylate resin, liquid crystal polymer, polyether ketone resin, polythioether ketone. Olefin-based polymers that do not contain epoxy groups such as resins, polyether ether ketone resins, polyimide resins, polyether imide resins, polyether sulfone resins, polyamide imide resins, tetrafluoropolyethylene resins, ethylene / 1-butene copolymers And a copolymer.

  Moreover, the following compounds can be added for the purpose of modification. Plasticizers such as polyalkylene oxide oligomer compounds, thioether compounds, ester compounds, organophosphorus compounds, crystal nucleating agents such as organophosphorus compounds, polyetheretherketone, montanic acid waxes, lithium stearate, aluminum stearate Metal soaps such as ethylenediamine / stearic acid / sebacic acid polycondensates, release agents such as silicone compounds, anti-coloring agents such as hypophosphite, (3,9-bis [2- (3- (3 -T-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane) Antioxidants, phosphorus such as (bis (2,4-di-cumylphenyl) pentaerythritol-di-phosphite) Ordinary additives such as water-based antioxidants, water, lubricants, ultraviolet light inhibitors, colorants, foaming agents and the like can be blended. If any of the above compounds exceeds 20% by weight of the total composition, (a) the original properties of the PPS resin are impaired, which is not preferable, and it is preferable to add 10% by weight or less, more preferably 1% by weight or less.

  The member for fluid piping made of the PPS resin composition of the present invention refers to piping for conveying fluid and various parts attached to the piping. For example, pipes, lining pipes, cap nuts, pipe joints ( Elbow, header, cheese, reducer, joint, coupler, etc.), various valves, various valves, flow meters, gaskets (seal, packing). The fluid is a gas or a liquid, for example, city gas, propane gas, nitrogen, oxygen, hydrogen, carbon dioxide, helium, neon, argon, halogen gas, water vapor, cold water, hot water, boiling water, refrigerant, A heat medium and various organic solvents are mentioned. Among the fluid piping members, in particular, it is suitably used for water-circulating parts that are pipe joints selected from toilet-related parts, water heater-related parts, bath-related parts, and pump-related parts.

  The present invention will be described more specifically with reference to the following examples. However, the present invention is not limited to the following examples.

[Injection molding (first time)]
Using an Sumitomo-Nestal injection molding machine SG75, an ASTM No. 1 dumbbell test piece and an Izod impact test piece having a length of 60 mm, a width of 12.7 mm, and a thickness of 3.2 mm were molded at a resin temperature of 310 ° C. and a mold temperature of 130 ° C. .

[Injection molding (second time)]
The ASTM No. 1 dumbbell specimen once injection molded was pulverized to a size of about 1 to 5 mm square using a pulverizer. Using this as a raw material, an ASTM No. 1 dumbbell test piece was molded at a resin temperature of 310 ° C. and a mold temperature of 130 ° C. using a Sumitomo-Nestal injection molding machine SG75.

[-40 ° C cut notched Izod impact test]
The injection-molded Izod impact test piece having a length of 60 mm, a width of 12.7 mm, and a thickness of 3.2 mm was notched with a notch cutter, cooled in an ultra-low temperature bath at −40 ° C. for 120 minutes, and then in accordance with ASTM D256. The Izod impact strength with a cut notch at 40 ° C. was measured.

[Dispersed particle size]
The center part of the injection-molded ASTM No. 1 dumbbell test piece was cut in a direction perpendicular to the resin flow direction, and a thin piece of 0.1 μm or less was cut at −20 ° C. from the center part of the cross section. 100 arbitrary (b) olefins when observed at a magnification of 10,000 times with an H-7100 transmission electron microscope (resolution (particle image) 0.38 nm, magnification: 500 to 600,000 times) Regarding the dispersed portion of the resin, first, the maximum diameter and the minimum diameter were measured, and the average value was used as the dispersed particle diameter, and then the number average dispersed particle diameter, which was the average value thereof, was obtained.

(Creep resistance)
The injection molded ASTM No. 1 dumbbell test piece was subjected to a tensile creep test in accordance with ASTM-D2990 under a distance between fulcrums of 114 mm, an atmospheric temperature of 80 ° C., and a tensile stress of 20 MPa to measure tensile creep strain. The tensile creep strain is a value obtained by dividing the displacement amount by the distance between the fulcrums. The tensile creep strain described in the examples indicates a value after 50 hours from the start of the test, and uses an average value measured five times. It was. It can be said that the smaller this value is, the better the creep resistance is, and the molded product is less likely to be thermally deformed.

(Freezing resistance)
Using Sumitomo-Nestal injection molding machine SG75, 30 cylindrical molded products with outer diameter of 30mmφ x inner diameter of 26mmφ x length of 40mm that can be sealed with a screw structure on one side at a resin temperature of 310 ° C and mold temperature of 130 ° C Molded. The molded product was filled with pure water so as not to contain air and sealed, and then left in an ultra-low temperature thermostatic bath at -40 ° C. for 24 hours to completely freeze the water inside. Then, the molded product was taken out from the thermostat, and the number of defective products in which cracks occurred on the surface of the molded product was measured. The smaller the number of defective products, the better the freezing resistance, and it can be said that the molded product is not easily damaged by freezing.

[Reference Example 1] (a) Polymerization of PPS resin (PPS-1)
In a 70 liter autoclave equipped with a stirrer, 8267.37 g (70.00 mol) of 47.5% sodium hydrosulfide, 2957.21 g (70.97 mol) of 96% sodium hydroxide, N-methyl-2-pyrrolidone (NMP ) 11434.50 g (115.50 mol), sodium acetate 2583.00 g (31.50 mol), and ion-exchanged water 10500 g, gradually heated to 245 ° C. over about 3 hours under nitrogen at normal pressure, After distilling out 14780.1 g of water and 280 g of NMP, the reaction vessel was cooled to 160 ° C. The residual water content in the system per 1 mol of the charged alkali metal sulfide was 1.06 mol including the water consumed for the hydrolysis of NMP. The amount of hydrogen sulfide scattered was 0.02 mol per mol of the charged alkali metal sulfide.

  Next, 10235.46 g (69.63 mol) of p-dichlorobenzene and 900.00 g (91.00 mol) of NMP were added, the reaction vessel was sealed under nitrogen gas, and stirred at 240 rpm while stirring at 0.6 ° C. / The temperature was raised to 238 ° C. at a rate of minutes. After reacting at 238 ° C. for 95 minutes, the temperature was raised to 270 ° C. at a rate of 0.8 ° C./min. After performing the reaction at 270 ° C. for 100 minutes, 1260 g (70 mol) of water was injected over 15 minutes and cooled to 250 ° C. at a rate of 1.3 ° C./minute. Then, after cooling to 200 ° C. at a rate of 1.0 ° C./min, it was rapidly cooled to near room temperature.

  The contents were taken out, diluted with 26300 g of NMP, the solvent and solid matter were filtered off with a sieve (80 mesh), and the resulting particles were washed with 31900 g of NMP and filtered off. This was washed several times with 56000 g of ion-exchanged water and filtered, then washed with 70000 g of 0.05 wt% aqueous acetic acid and filtered. After washing with 70000 g of ion-exchanged water and filtering, the resulting hydrous PPS particles were dried with hot air at 80 ° C. and dried under reduced pressure at 120 ° C. The obtained PPS-1 had a melt viscosity of 200 Pa · s (310 ° C., shear rate of 1000 / s).

[Reference Example 2] (a) Polymerization of PPS resin (PPS-2)
Dehydration, polymerization, washing, and drying were performed in the same manner as in Reference Example 1 except that 0.05 wt% acetic acid aqueous solution at the time of PPS washing was used as ion exchange water. The obtained PPS-2 had a melt viscosity of 250 Pa · s (310 ° C., shear rate of 1000 / s).

[Reference Example 3] (b) Olefin resin b-1 having at least one functional group selected from the group consisting of carboxyl group, acid anhydride group, amino group, hydroxyl group and mercapto group b-1: modified with maleic anhydride Ethylene / 1-butene copolymer ("Tuffmer" MH5020 manufactured by Mitsui Chemicals, Inc.)
b-2: Ethylene / propylene copolymer modified with maleic anhydride (“Tuffmer” MP0610 manufactured by Mitsui Chemicals, Inc.)
b-3: ethylene / glycidyl methacrylate = 88/12 wt% copolymer b-4: ethylene / glycidyl methacrylate / methyl acrylate = 67/3/30 wt% copolymer

[Reference Example 4] Olefin-based resin b′-1 having no functional group: Unmodified ethylene / 1-butene copolymer (“Tuffmer” TX610 manufactured by Mitsui Chemicals, Inc.)

[Reference Example 5] (c) Alkoxysilane compound c-1: 2- (3,4 epoxycyclohexyl) ethyltrimethoxysilane having at least one functional group selected from the group consisting of an amino group, an epoxy group and an isocyanate group (KBM-303 manufactured by Shin-Etsu Chemical Co., Ltd.)
c-2: 3-isocyanatopropyltriethoxysilane (KBE-9007 manufactured by Shin-Etsu Chemical Co., Ltd.)
c-3: 3-glycidoxypropyltrimethoxysilane (KBM-403 manufactured by Shin-Etsu Chemical Co., Ltd.)

[Reference Example 6] Polyfunctional isocyanate compound c′-1: diphenylmethane diisocyanate-based polyfunctional isocyanate compound (“Millionate” MR-400 manufactured by Nippon Polyurethane Industry Co., Ltd.)

[Reference Example 7] Other resin a'-1: Cresol-novolak type epoxy resin (EPICLON N-695 manufactured by DIC Corporation)
a'-2: Polyphenylene ether resin (S202A manufactured by Asahi Kasei Chemicals Corporation)

[Examples 1 to 8]
After dry blending (a) PPS resin and (c) alkoxysilane compound shown in Table 1 at the ratio shown in Table 1, a TEX30α twin screw extruder (L / D = 45.5, 5 kneading sections), and at a screw rotation speed of 300 rpm, the cylinder temperature was set so that the die removal resin temperature would be 330 ° C. or less, and the mixture was melt-kneaded and pelletized by a strand cutter. The obtained pellets were dried at 130 ° C. overnight, dry blended with the (b) olefin resin shown in Table 1 so as to have the ratio shown in Table 1, and then TEX30α manufactured by Nippon Steel Works with a vacuum vent. Using a type twin screw extruder (L / D = 45.5, 5 kneading parts), melt kneading by setting the cylinder temperature so that the die extrusion resin temperature is 330 ° C. or less at a screw rotation speed of 300 rpm. And pelletized with a strand cutter.

  The pellets dried at 130 ° C. overnight were subjected to injection molding, and the -40 ° C. cut-notched Izod impact strength of the molded piece and (b) measurement of the number average dispersed particle size of the olefin resin, and resistance to creep and freezing. Sex assessment was performed. The results were as shown in Table 1.

[Comparative Examples 1-3, 8]
(A) PPS resin, (b) olefin resin, and (c) alkoxysilane compound shown in Table 2 were dry blended in the proportions shown in Table 2, and then a TEX30α type biaxial manufactured by Nippon Steel Co., Ltd. equipped with a vacuum vent. Using an extruder (L / D = 45.5, kneading part 5 locations), melt and knead by setting the cylinder temperature so that the resin temperature at which the die is discharged is 330 ° C. or less at a screw rotation speed of 300 rpm. Pelletized with a cutter.

  The pellets dried overnight at 130 ° C. were subjected to injection molding, and the molded piece was subjected to -40 ° C. cut notched Izod impact strength, (b) measurement of the number average dispersed particle size of the olefin resin, and resistance to creep and freezing. Sex assessment was performed. The results were as shown in Table 2.

[Comparative Example 4]
After dry blending the (a) PPS resin and (c) alkoxysilane compound shown in Table 2 at the ratio shown in Table 2, a TEX30α twin screw extruder (L / D = 45.5, 5 kneading sections), and at a screw rotation speed of 300 rpm, the cylinder temperature was set so that the die removal resin temperature would be 330 ° C. or less, and the mixture was melt-kneaded and pelletized by a strand cutter. The obtained pellets were dried at 130 ° C. overnight, dry blended with the (b) olefin resin shown in Table 2 so as to have the ratio shown in Table 2, and then TEX30α manufactured by Nippon Steel Works with a vacuum vent. Using a type twin screw extruder (L / D = 45.5, 5 kneading parts), melt kneading by setting the cylinder temperature so that the die extrusion resin temperature is 330 ° C. or less at a screw rotation speed of 300 rpm. And pelletized with a strand cutter.

  The pellets dried at 130 ° C. overnight were subjected to injection molding, and the Izod impact strength with a −40 ° C. cut notch of the molded piece was measured, and creep resistance and freeze resistance evaluation were performed. The results were as shown in Table 2.

[Comparative Example 5]
(B) Melt-kneading, injection molding, and evaluation were performed in the same manner as in Example 1 except that the olefin resin was an ethylene / 1-butene copolymer b′-1 having no functional group.

[Comparative Example 6]
After dry blending the (a) PPS resin and (c) alkoxysilane compound shown in Table 2 at the ratio shown in Table 2, a TEX30α twin screw extruder (L / D = 45.5, 5 kneading sections), and at a screw rotation speed of 300 rpm, the cylinder temperature was set so that the die removal resin temperature would be 330 ° C. or less, and the mixture was melt-kneaded and pelletized by a strand cutter. The obtained pellets were dried overnight at 130 ° C., dry blended with the (b) olefin resin shown in Table 2 to the ratio shown in Table 2, and then subjected to injection molding without melting and kneading. The Izod impact strength with a cut notch of −40 ° C. of the molded piece, (b) measurement of the number average dispersed particle size of the olefin resin, and creep resistance and freeze resistance evaluation were carried out. The results were as shown in Table 2.

[Comparative Example 7]
(C) Melt-kneading, injection molding, and evaluation were performed in the same manner as in Example 1 except that the alkoxysilane compound was a diphenylmethane diisocyanate polyfunctional isocyanate compound c′-1.

[Comparative Examples 9 to 13]
The raw materials shown in Table 3 were melt kneaded, injection molded and evaluated in the same manner as in Comparative Example 1. The results are shown in Table 3.

  The results of Examples 1-8 and Comparative Examples 1-8 will be described in comparison.

  In each of Examples 1 to 7, (a) a PPS resin and (c) an alkoxysilane compound were previously melt-kneaded, and then (b) an olefin-based resin was further melt-kneaded, whereby a high −40 of 300 J / m or more. Izod impact strength with cut notches at ℃ was developed, and excellent freezing resistance was exhibited. About the ASTM No. 1 dumbbell test piece obtained by the first injection molding, (b) The dispersion diameter of the olefin resin is finely dispersed to 500 nm or less, and the ASTM No. 1 dumbbell test piece obtained by the second injection molding As for (b), the olefin resin was finely dispersed to 500 nm or less. In Example 8 in which the amount of the olefinic resin in Example 3 (b) was reduced, an Izod impact strength with a high −40 ° C. cut notch of 300 J / m or more was exhibited, and excellent freezing resistance was exhibited. The creep strain was also smaller than that.

  On the other hand, as in Comparative Examples 1 to 3, when (a) PPS resin, (b) olefinic resin, and (c) alkoxysilane compound were kneaded together, the Izod impact strength with a cut notch of −40 ° C. was The value was significantly lower than 300 J / m, and the freezing resistance was reduced as compared with Examples 1 to 3. Moreover, about the ASTM No. 1 dumbbell test piece obtained by the first injection molding, the dispersed particle diameter of (b) olefin resin was coarsened as compared with the corresponding examples. Furthermore, for the ASTM No. 1 dumbbell test piece obtained by the second injection molding, (b) the dispersed particle diameter of the olefin-based resin is further coarsened compared to the ASTM No. 1 dumbbell test piece obtained by the first injection molding, All exceeded 500 nm. Unlike Example 1, in Comparative Example 4 in which (a) the PPS resin was a minor component and (b) the olefin resin was a major component, (a) the PPS resin and (c) the alkoxysilane compound were previously melt-kneaded, (B) Even if a method of further melt-kneading with an olefin resin was adopted, the Izod impact strength with a cut notch of −40 ° C. was lowered, being less than 300 J / m, and the freezing resistance was lower than that of Example 1. . Unlike Example 1, in Comparative Example 5 in which (b) an olefin resin having no functional group was used, (a) a PPS resin and (c) an alkoxysilane compound were previously melt-kneaded, and then (b) an olefin. Even when a method of further melt-kneading with a resin was adopted, the -40 ° C cut notched Izod impact strength was lowered, significantly lower than 300 J / m, and the freezing resistance was lowered as compared with Example 1. Unlike Example 1, (a) a PPS resin and (c) an alkoxysilane compound were previously melt-kneaded, and (b) an olefin-based resin was not further melt-kneaded, but was dry blended and directly subjected to injection molding In Example 6, the Izod impact strength with a cut notch at −40 ° C. was lower than 300 J / m, and the freezing resistance was lower than that in Example 1. Unlike Example 1, (c) In Comparative Example 7 in which the alkoxysilane compound was a polyfunctional isocyanate compound, the Izod impact strength with a −40 ° C. cut notch was lowered, greatly below 300 J / m, and the antifreezing property was an example. 1 compared to 1. Unlike Example 8, (a) a PPS resin, (b) an olefin resin, and (c) a method of kneading an alkoxysilane compound in a lump, and (b) the amount of olefin resin was reduced in Comparative Example 8, Although the strain was reduced, the Izod impact strength with a -40 ° C cut notch was lowered, being less than 300 J / m, and the freezing resistance was lower than that of Example 8.

[Example 9] Injection molding of piping for fluids Using pellets of the composition obtained in Example 8, using a Sumitomo-Nestal injection molding machine SG75 under conditions of a resin temperature of 310 ° C and a mold temperature of 130 ° C, A molded product of an L-shaped pipe joint including a cylindrical shape having an outer diameter of 26 mmφ × inner diameter of 20 mmφ × thickness of 3 mm having a flange portion was formed. Even if a large amount of hot water of 80 ° C. is flowed into the molded product of this L-shaped pipe joint, thermal deformation does not occur inside the molded product, and the molded product is filled with pure water at −40 ° C. Since it was not damaged by freezing even after being left in an ultra-low temperature constant temperature bath for 240 hours, it was found that it was useful as a member for fluid piping excellent in low temperature toughness and creep resistance.

Claims (9)

The total of (a) and (b) is 100% by weight, and selected from the group consisting of (a) 99-60% by weight of polyphenylene sulfide resin, (b) carboxyl group, acid anhydride group, amino group, hydroxyl group, mercapto group And 100 parts by weight of a resin composition comprising 1 to 40% by weight of an olefin resin having at least one or more functional groups, (c) at least one or more selected from the group consisting of an amino group, an epoxy group and an isocyanate group A polyphenylene sulfide resin composition comprising 0.1 to 10 parts by weight of an alkoxysilane compound having a functional group, which is an Izod impact strength with a cut notch at −40 ° C. of a resin molded product (measured according to ASTM D256) A fluid distribution comprising a polyphenylene sulfide resin composition having a JO of 300 J / m or more Use member In the morphology (phase structure), (a) a polyphenylene sulfide resin forms a continuous phase (sea phase), and (b) a dispersed phase (island phase) in which an olefin resin having a functional group is dispersed with a number average dispersed particle size of 500 nm or less. 2. The fluid piping member according to claim 1, wherein the fluid piping member has a sea-island structure. Even in a molded piece obtained by pulverizing and injection-molding again after injection molding, the (b) functional group-containing olefin resin is dispersed with a number average dispersed particle diameter of 500 nm or less. Item 3. The fluid piping member according to Item 2. (B) An olefin resin having at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, an amino group, a hydroxyl group, and a mercapto group is an ethylene-containing resin having a carboxyl group and / or an acid anhydride group. It is a butene copolymer, The member for fluid piping in any one of Claims 1-3 characterized by the above-mentioned. (C) The alkoxysilane compound having at least one functional group selected from the group consisting of an amino group, an epoxy group, and an isocyanate group is an alkoxysilane compound having an epoxycyclohexyl group or an isocyanate group. The member for fluid piping in any one of -4. 6. The fluid piping member according to claim 1, wherein the polyphenylene sulfide resin is a polyphenylene sulfide resin subjected to acid treatment. The total of (a) and (b) is 100% by weight, and selected from the group consisting of (a) 99 to 85% by weight of polyphenylene sulfide resin, (b) carboxyl group, acid anhydride group, amino group, hydroxyl group and mercapto group. The fluid piping member according to claim 1, comprising 1 to 15% by weight of an olefin-based resin having at least one or more functional groups. From the group consisting of (a) polyphenylene sulfide resin 99 to 60% by weight, (b) carboxyl group, acid anhydride group, amino group, hydroxyl group, and mercapto group, where the total of (a) and (b) is 100% by weight (C) At least one selected from the group consisting of an amino group, an epoxy group, and an isocyanate group with respect to 100 parts by weight of a resin composition consisting of 1 to 40% by weight of an olefin resin having at least one selected functional group. A polyphenylene sulfide resin composition comprising 0.1 to 10 parts by weight of an alkoxysilane compound having a functional group, wherein (a) the polyphenylene sulfide resin and (c) the alkoxysilane compound having a functional group are previously melted After kneading, it is obtained by further melt-kneading with the olefin resin having the functional group (b). Fluid piping member according to claim 1 consisting of that the polyphenylene sulfide resin composition. The fluid piping member according to any one of claims 1 to 8, wherein the member is a pipe joint selected from toilet-related parts, water heater-related parts, bath-related parts, and pump-related parts. parts.