JP2008031233A - Polyphenylene sulfide resin tube - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a tube of a polyphenylene sulfide (PPS) resin composition having excellent heat-resistance, hot-water resistance, chemical resistance and alcohol gasoline permeation resistance which are characteristic features of PPS and having excellent and balanced appearance, softness, electrical conductivity, etc., of the molded article. <P>SOLUTION: The polyphenylene sulfide tube is a tubular product composed of a resin composition containing (a) 100 pts.wt. of a polyphenylene sulfide resin and (b) 1-20 pts.wt. of a polyamide resin (excluding acid-modified ethylene/α-olefin copolymer), wherein the polyphenylene sulfide forms matrix phase. A fluid flows in and contacts with the tube. <P>COPYRIGHT: (C)2008,JPO&INPIT

Description

  The present invention relates to a polyphenylene sulfide resin composition tubular body having excellent balance of heat resistance, hot water resistance, chemical resistance, alcohol-resistant gasoline permeability, molded article appearance, flexibility, conductivity and the like.

  Polyphenylene sulfide (hereinafter abbreviated as PPS) resin has excellent properties as engineering plastics such as excellent heat resistance, barrier properties, chemical resistance, electrical insulation properties, and heat and humidity resistance, mainly for injection molding and extrusion molding. It is used for various electric / electronic parts, machine parts and automobile parts. For example, thermoplastic resin hollow molded products are manufactured by blow molding using polyamide resins, mainly in ducts in the engine room of automobiles, saturated polyester resins, polyamide resins, polyolefin resins, A technique for manufacturing by extrusion using thermoplastic polyurethane is widespread.

  However, conventional single-layer hollow molded products made of thermoplastic resins such as polyamide resins, saturated polyester resins, polyolefin resins and thermoplastic polyurethane resins have insufficient heat resistance, hot water resistance, chemical resistance, etc. Therefore, since the range to be applied is limited, a product having further improved heat resistance, hot water resistance, chemical resistance and the like is required.

  Especially for automobile fuel tubes, polyamide resins, especially flexible polyamide resins such as polyamide 11 and polyamide 12, are widely used. However, when the polyamide resin is used alone, it is required for environmental pollution problems and fuel consumption improvement. Concerns have been pointed out that the permeation-preventing properties of alcohol gasoline are not sufficient, and improvements are desired. Also, in applications where non-conductive liquids such as fuel flow through blow hollow molded bodies and tube molded bodies, the molded body may be charged, and to suppress this, conductivity can be simultaneously imparted to the hollow molded body. It may be required.

  Accordingly, in recent years, multilayer hollow molded articles utilizing fuel barrier properties such as high gasohol possessed by polyphenylene sulfide resin have been studied (Patent Documents 1 to 5). These are technologies that satisfy excellent gasohol resistance and toughness, but since both are laminates of PPS resin composition and resin composition other than PPS, when processing such as particularly strong bending is performed after lamination In addition, it has been recognized that the interlayer adhesion is insufficient.

On the other hand, Patent Document 6 discloses a barrier-resistant resin component in which PPS, polyamide and a specific olefin copolymer are blended. Patent Document 7 discloses a tubular body in which a specific olefin copolymer is blended with PPS. However, in any case, a specific olefin copolymer is essential, and it has become difficult to satisfy the high barrier properties that have recently been particularly demanded.
JP 10-138372 A (examination request), JP-A-10-180911 (examination request), JP-A-10-182970 (examination request), Japanese Patent Laid-Open No. 10-230556 (examination request), JP-A-10-296889 (examination request) Japanese Patent Laying-Open No. 2005-35576 (examination request) JP-A-2-200415 (examination request)

  The present invention eliminates the above-mentioned conventional problems, is excellent in heat resistance, hot water resistance, chemical resistance, and alcohol gasoline permeability, which are the characteristics of polyphenylene sulfide, and has a molded product appearance, flexibility, conductivity, etc. It is an object of the present invention to provide a balanced and excellent PPS resin composition tubular body.

As a result of intensive studies to solve the above problems, the present inventors have reached the present invention.
That is, the present invention is a PPS tubular body having the following configuration.
1. (A) 100 parts by weight of a polyphenylene sulfide resin, and (b) a polyphenylene sulfide containing 1 part by weight or more and less than 20 parts by weight of a polyamide resin (not including an acid-modified ethylene / α-olefin copolymer) forms a matrix phase. A tubular body made of a polyphenylene sulfide resin composition, wherein a fluid flows inside the tubular body, and the flowing fluid is in contact with the tubular body,
2. The tubular body according to 1, wherein the number average dispersed particle size of the (b) polyamide resin of the polyphenylene sulfide resin composition is less than 500 nm,
3. (B) After the polyphenylene sulfide resin composition is melt-retained at 300 ° C. for 30 minutes, the tubular body is formed of the polyphenylene sulfide resin composition according to any one of (1) to (2), wherein the number average dispersed particle diameter of the polyamide resin is less than 500 nm ,
4). The tubular body comprising the polyphenylene sulfide resin composition according to any one of 1 to 3, wherein (b) the polyamide resin is at least one selected from copolymer polyamide, nylon 610 and nylon 612,
5. The polyphenylene sulfide resin composition further comprises (c) a compound having one or more groups selected from an epoxy group, an amino group and an isocyanate group as a compatibilizing agent with respect to 100 parts by weight of the (a) polyphenylene sulfide resin. 5. 1 to 30 parts by weight of a tubular body according to any one of 1 to 4, (C) The tubular body according to claim 5, wherein the compatibilizer is an organosilane compound having one or more groups selected from an epoxy group, an amino group and an isocyanate group.
7). The tubular body according to any one of 1 to 6, wherein the polyphenylene sulfide resin composition is formed by blending 1 to 20 parts by weight of (d) conductive filler with respect to 100 parts by weight of (a) polyphenylene sulfide resin,
8). The tubular body according to any one of 1 to 7, wherein the polyphenylene sulfide resin composition contains (e) at least one selected from an olefin polymer, an olefin copolymer, and a thermoplastic elastomer,
9. 9. The tubular structure according to claim 8, wherein at least one selected from (e) an olefin polymer, an olefin copolymer and a thermoplastic elastomer is an olefin copolymer having a density of 880 kg / m ³ or less. body,
10. 8 or 9 wherein the content of at least one selected from (e) an olefin polymer, an olefin copolymer and a thermoplastic elastomer is 1 to 20 parts by weight with respect to 100 parts by weight of the (a) polyphenylene sulfide resin. The tubular body as described,
11. A tubular body according to any one of 1 to 10 and a tubular body according to any one of 12.1 to 11 obtained by an extrusion molding method, wherein the tubular body is a polyphenylene sulfide resin composition in which automobile fuel flows. is there.

  The polyphenylene sulfide resin tubular body of the present invention is excellent in heat resistance, hot water resistance, chemical resistance, alcohol-resistant gasoline permeability, which is characteristic of polyphenylene sulfide, and has a balanced appearance of molded product, flexibility, conductivity, etc. The present invention relates to an excellent PPS resin composition tubular body, and is particularly useful for automobile fuel system tubes and the like.

  Embodiments of the present invention will be described below. In the present invention, “weight” means “mass”.

  The PPS resin used in the (a) polyphenylene sulfide (hereinafter referred to as PPS) resin of the present invention is a polymer having a repeating unit represented by the following structural formula,

  From the viewpoint of heat resistance, a polymer containing 70 mol% or more, particularly 90 mol% or more, more preferably 98 mol% or more of the repeating unit represented by the above structural formula is preferable. Moreover, PPS resin can be comprised with the repeating unit etc. which have the following structure in less than 30 mol% of the repeating unit.

  The molecular weight of the PPS resin of the present invention is not particularly limited, but the weight average molecular weight is preferably 30,000 or more, and more preferably 35,000 or more. As an upper limit, the weight average molecular weight is preferably 90,000 or less, and more preferably 70,000 or less. If the weight average molecular weight is too low, the toughness tends to decrease, and if the weight average molecular weight is too high, the moldability is impaired.

  Hereinafter, a method for producing (a) PPS resin used in the present invention will be described. However, the method is not limited to the following method as long as (a) PPS resin satisfying the above structure and conditions is obtained.

  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 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 polyhalogenated aromatic compound is used in an amount of 0.9 to 2.0 mol, preferably 0.95, per mol of the sulfidizing agent from the viewpoint of obtaining (a) PPS resin having a molecular weight suitable for the purpose of the present invention. The range is from 1.5 to 1.5 mol, more preferably from 1.005 to 1.2 mol.

[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. At this stage, barium can be introduced into the PPS resin by using barium hydroxide.

  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 degree of polymerization 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, alkali metal carboxylates are preferable as organic carboxylates, and lithium chloride is preferable as alkali metal chlorides.

  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 to add at the start of the process or at the start of the polymerization from the viewpoint of easy addition.

  Next, the manufacturing method of (a) PPS resin used in the present invention will be specifically described in the order of a pre-process, a polymerization reaction process, a recovery process, and a post-treatment process.

[pre-process]
(A) In the method for producing a 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.
(I) 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. (A) Any known recovery method may be adopted for the PPS resin.

  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. There is no need for slow cooling at the same rate in the entire process of the slow cooling step, and a method of slow cooling at a rate of 0.1 to 1 ° C./minute until the polymer particles crystallize and then 1 ° C./minute or more is used. It may be adopted.

In addition, performing the above recovery under rapid cooling conditions is one method, and a preferable method of this recovery method is a flash method. 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 immersing (a) 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 the remaining 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 the (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 preferably 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 the 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 / sulfon solvents such as dimethyl sulfoxide, dimethyl sulfone, sulfolane, ketones such as acetone, methyl ethyl ketone, diethyl ketone, 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 an arikari 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 barium ions 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.

  (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.

  In the present invention, preferable (a) polyphenylene sulfide resins include M2088, M2588, GR01, L2120 manufactured by Toray Industries, Inc.

  Next, the (b) polyamide resin used in the present invention will be described. The blending of such components improves the toughness of the PPS resin, and is effective in imparting toughness to the tubular body without significantly impairing the chemical resistance of the PPS resin in forming a tubular body such as a tube.

  The polyamide resin used in the present invention is not particularly limited as long as it is a polyamide resin, but is generally a polyamide mainly composed of amino acid, lactam or diamine and dicarboxylic acid. Representative examples of the main component include amino acids such as 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and paraaminomethylbenzoic acid, lactams such as ε-aminocaprolactam and ω-laurolactam, tetramethylene Diamine, hexamethylenediamine, undecamethylenediamine, dodecamethylenediamine, 2,2,4- / 2,4,4-trimethylhexamethylenediamine, 5-methylnonamethylenediamine, metaxylenediamine, paraxylylenediamine, 1 , 3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, 1-amino-3-aminomethyl-3,5,5-trimethylcyclohexane, bis (4-aminocyclohexyl) methane, bis ( 3-methyl-4-aminocycle (Rohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine, aminoethylpiperazine, 2-methylpentamethylenediamine, and the like, aliphatic, alicyclic, aromatic diamines, and adipine Acid, peric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methylisophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid And aliphatic, alicyclic and aromatic dicarboxylic acids such as hexahydroisophthalic acid. In the present invention, polyamide homopolymers or copolymers derived from these raw materials are used alone or in the form of a mixture, respectively. Can do.

  In the present invention, useful polyamide resins include polycaproamide (nylon 6), polyhexamethylene adipamide (nylon 66), polyhexamethylene sebacamide (nylon 610), polyhexamethylene dodecamide (nylon 612). , Homopolyamide resins such as polydodecanamide (nylon 12), polyundecanamide (nylon 11), polyhexamethylene terephthalamide (nylon 6T), polyxylylene adipamide (nylon XD6) or a copolymer thereof. Copolyamides (nylon 6/66, nylon 6/10, nylon 6/66/610, 66 / 6T) and the like are mentioned. Among them, copolymer polyamide and nylon 610 are preferable. These polyamide resins can also be used as a mixture (“/” represents copolymerization; the same applies hereinafter).

  Among these, nylon 6 is used as a homopolyamide resin, and a copolymer obtained by copolymerizing nylon 6 with other polyamide components as a copolymerized polyamide is more preferably used for developing excellent toughness. A nylon 6/66 copolymer having a high toughness-producing effect and a nylon 6 copolymer amount higher than that of nylon 66 is particularly preferably used. The copolymerization ratio of the nylon 6/66 copolymer is particularly preferably in the range of nylon 6 component / nylon 66 component = 95/5 to 65/35 in weight ratio.

  Since nylon 610 and nylon 612 have excellent thermal stability and relatively high strength, they are also mentioned as preferred polyamides.

  On the other hand, in the case where the polyamide resin (b) is a repeating unit constituting the polyamide, a polyamide having 11 or more carbon atoms per amide group, for example, polyamide 11 or polyamide 12 is not particularly effective in expressing excellent toughness. Not good. This is presumed that the interaction between PPS and polyamide is presumed to be the interaction between PPS and amide groups, and that the affinity with PPS decreases if the amide group concentration is too low.

  In the present invention, it is not preferable to use nylon 46 as the polyamide. Although the reason is not clear, the effect of toughness development, which is the object of the present invention, is somewhat reduced.

  Therefore, the preferred polyamide resin (b) in the present invention preferably has 6 or more and less than 11 carbon atoms per amide group in the repeating unit constituting the polyamide.

  The degree of polymerization of the polyamide used in the present invention is not particularly limited, but from the standpoint of more excellent toughness, the relative viscosity measured in concentrated sulfuric acid at a concentration of 1% and 25 ° C. is 1.5 or more, more preferably It is preferable to use a polyamide having a relative viscosity of 1.8 to 5.5.

  In the present invention, the blending amount of the (b) polyamide resin is selected in the range of less than 1 to 20 parts by weight and more preferably in the range of 2 to 15 parts by weight with respect to 100 parts by weight of the (a) PPS resin. (B) When the blending amount of the polyamide resin is 20 parts by weight or more, the PPS resin has unfavorable characteristics such as heat and moisture resistance, fluidity, gasohole barrier properties, etc., and (b) the blending amount of the polyamide resin If it is less than 1 part by weight, the effect of toughness is significantly reduced, which is not preferable.

  The PPS resin composition used for the PPS tubular body of the present invention has (a) excellent toughness as well as excellent heat resistance, chemical resistance, and barrier properties inherently possessed by the PPS resin. In order to develop such characteristics, it is necessary that the PPS resin forms a sea phase (continuous phase or matrix), and (b) the polyamide resin forms an island phase (dispersed phase). Furthermore, (b) the number average dispersed particle size of the polyamide resin is preferably less than 500 nm, preferably 300 nm or less, more preferably 200 nm or less. The lower limit is preferably 1 nm or more from the viewpoint of productivity. (B) When the number average dispersed particle size of the polyamide resin is 500 nm or more, the barrier properties and toughness tend to be impaired.

  In addition, the average dispersion diameter here means that the ASTM 4 test piece is molded at the molding temperature of the melting peak temperature of the PPS resin + 20 ° C., and a thin piece of 0.1 μm or less from the center at −20 ° C. is a cross-sectional area of the dumbbell piece. First, measure the maximum and minimum diameters of any 100 (b) dispersed portions of polyamide resin when observed at a magnification of 20,000 times with a transmission electron microscope. It is the number average dispersed particle size determined and then averaged. In addition, the polyphenylene sulfide resin composition used for the PPS tubular body of the present invention further includes (c) a compound having one or more groups selected from an epoxy group, an amino group and an isocyanate group as a compatibilizing agent. Addition of 0.1 to 30 parts by weight, more preferably 0.2 to 5 parts by weight, with respect to 100 parts by weight promotes fine dispersion of (b) polyamide resin and develops excellent toughness. Preferred above.

  Specific examples of the (c) compatibilizer will be described below.

  Examples of the epoxy group-containing compound include bisphenol A, resorcinol, hydroquinone, pyrocatechol, bisphenol F, saligenin, 1,3,5-trihydroxybenzene, bisphenol S, trihydroxy-diphenyldimethylmethane, 4,4′-dihydroxybiphenyl, 1 , 5-dihydroxynaphthalene, cashew phenol, glycidyl ethers of bisphenols such as 2,2,5,5-tetrakis (4-hydroxyphenyl) hexane, those using halogenated bisphenol instead of bisphenol, diglycidyl of butanediol Glycidyl ether epoxy compounds such as ether, glycidyl ester compounds such as glycidyl phthalate, glycidyl amine compounds such as N-glycidyl aniline, etc. Glycidyl epoxy resins, epoxidized polyolefins, linear epoxy compounds such as epoxidized soybean oil, vinylcyclohexene dioxide, such as a non-glycidyl epoxy resins ring system such as dicyclopentadiene dioxide and the like.

  In addition, other novolac type epoxy resins are also included. The novolac type epoxy resin has two or more epoxy groups and is usually obtained by reacting a novolac type phenol resin with epichlorohydrin. Moreover, a novolac type phenol resin is obtained by a condensation reaction of phenols and formaldehyde. Although there is no restriction | limiting in particular as phenols of a raw material, Phenol, o-cresol, m-cresol, p-cresol, bisphenol A, resorcinol, p-tertiary butylphenol, bisphenol F, bisphenol S, and these condensates are mentioned.

  Moreover, the olefin copolymer which has an epoxy group is also mentioned. Examples of the olefin copolymer having an epoxy group (epoxy group-containing olefin copolymer) include an olefin copolymer obtained by introducing a monomer component having an epoxy group into an olefinic (co) polymer. . Moreover, the copolymer which epoxidized the double bond part of the olefin polymer which has a double bond in a principal chain can also be used.

  Examples of functional group-containing components for introducing a monomer component having an epoxy group into an olefinic (co) polymer include glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid, etc. And a monomer containing an epoxy group.

  The method for introducing these epoxy group-containing components is not particularly limited, and methods such as copolymerization with α-olefin and the like, or graft introduction to an olefin (co) polymer using a radical initiator can be used.

  The introduction amount of the monomer component containing an epoxy group is 0.001 to 40 mol%, preferably 0.01 to 35 mol% with respect to the whole monomer as a raw material of the epoxy group-containing olefin copolymer. It is appropriate to be within the range.

  As an epoxy group-containing olefin copolymer particularly useful in the present invention, an olefin copolymer having an α-olefin and a glycidyl ester of an α, β-unsaturated carboxylic acid as a copolymerization component is preferably exemplified. As said alpha olefin, ethylene is mentioned preferably. These copolymers further include α, β-unsaturated carboxylic acids such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and the like. It is also possible to copolymerize the alkyl ester, styrene, acrylonitrile and the like.

  Such an olefin copolymer may be any random, alternating, block, or graft copolymerization mode.

  An olefin copolymer obtained by copolymerizing an glycidyl ester of an α-olefin and an α, β-unsaturated carboxylic acid is, among others, a glycidyl ester 1 of 60 to 99% by weight of an α-olefin and an α, β-unsaturated carboxylic acid. An olefin copolymer obtained by copolymerizing ˜40% by weight is particularly preferable.

  Specific examples of the glycidyl ester of α, β-unsaturated carboxylic acid include glycidyl acrylate, glycidyl methacrylate, and glycidyl ethacrylate. Among them, glycidyl methacrylate is preferably used.

  As a specific example of an olefin copolymer having an α-olefin and a glycidyl ester of α, β-unsaturated carboxylic acid as an essential copolymerization component, an ethylene / propylene-g-glycidyl methacrylate copolymer ("g" Representing graft, the same applies hereinafter), ethylene / butene-1-g-glycidyl methacrylate copolymer, ethylene-glycidyl methacrylate copolymer-g-polystyrene, ethylene-glycidyl methacrylate copolymer-g-acrylonitrile-styrene copolymer Polymer, ethylene-glycidyl methacrylate copolymer-g-PMMA, ethylene / glycidyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / Glycidi methacrylate Copolymers thereof.

  Furthermore, the alkoxysilane which has an epoxy group is mentioned. Specific examples of such compounds include epoxy group-containing alkoxysilanes such as γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxysilane, and β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane. A compound etc. can be illustrated.

  Examples of the amino group-containing compound include alkoxysilanes having an amino group. Specific examples of such compounds include amino group-containing alkoxysilanes such as γ- (2-aminoethyl) aminopropylmethyldimethoxysilane, γ- (2-aminoethyl) aminopropyltrimethoxysilane, and γ-aminopropyltrimethoxysilane. Compound etc. are mentioned.

  Examples of the compound containing at least one isocyanate group include isocyanate compounds such as 2,4-tolylene diisocyanate, 2,5-tolylene diisocyanate, diphenylmethane-4,4′-diisocyanate, polymethylene polyphenyl polyisocyanate, and γ-isocyanate. Propyltriethoxysilane, γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylethyldimethoxysilane, γ-isocyanatopropylethyldiethoxysilane, γ-isocyanate An isocyanate group-containing alkoxysilane compound such as propyltrichlorosilane can be exemplified.

  Among them, an organosilane compound containing at least one isocyanate group, epoxy group, or amino group is particularly preferable from the viewpoint of excellent balance between toughness and barrier property in order to obtain a high toughness expression effect.

  Next, in the present invention, (d) the conductive PPS resin composition tubular body is blended with a conductive filler, which is particularly useful when automobile fuel such as gasoline and gasohol flows therein. This is because such automobile fuel is often flammable, and a non-conductive resin tube may be charged and sparked.

(D) The conductive filler used in the present invention is not particularly limited as long as it is a conductive filler that is usually used for conducting a resin. Specific examples thereof include metal powder, metal flakes, metal ribbons, metal fibers, and metals. Examples thereof include oxides, inorganic fillers coated with a conductive substance, carbon powder, graphite, carbon fiber, carbon flakes, and scaly carbon. Specific examples of metal species of metal powder, metal flakes, and metal ribbons include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin. Specific examples of the metal species of the metal fiber include iron, copper, stainless steel, aluminum, and brass. Such metal powders, metal flakes, metal ribbons, and metal fibers may be surface-treated with a surface treatment agent such as titanate, aluminum, or silane. Specific examples of the metal oxide include SnO ₂ (antimony dope), In ₂ O ₃ (antimony dope), ZnO (aluminum dope), etc., and these are surface treatment agents such as titanate, aluminum and silane. Surface treatment may be performed.

Specific examples of the conductive material in the inorganic filler coated with the conductive material include aluminum, nickel, silver, carbon, SnO ₂ (antimony doped), and In ₂ O ₃ (antimony doped). Examples of the inorganic filler to be coated include mica, glass beads, glass fiber, carbon fiber, potassium titanate whisker, barium sulfate, zinc oxide, titanium oxide, aluminum borate whisker, zinc oxide whisker, titanic acid whisker, Examples thereof include silicon carbide whiskers. Examples of the coating method include vacuum deposition, sputtering, electroless plating, and baking. These may be surface-treated with a titanate-based, aluminum-based or silane-based surface treatment agent.

Carbon powders are classified into acetylene black, gas black, oil black, naphthalene black, thermal black, furnace black, lamp black, channel black, roll black, disc black, etc., depending on the raw materials and production method. The carbon powder that can be used in the present invention is not particularly limited in its raw material and production method, but acetylene black and furnace black are particularly preferably used. In addition, various carbon powders having different characteristics such as particle diameter, surface area, DBP oil absorption, ash content and the like are manufactured. The carbon powder that can be used in the present invention is not particularly limited in these properties, but the average particle size is preferably 500 nm or less, particularly 5 to 100 nm, more preferably 10 to 70 nm, from the viewpoint of the balance between strength and electrical conductivity. . The surface area (BET method) is preferably 10 m ² / g or more, more preferably 30 m ² / g or more. The DBP oil supply amount is preferably 50 ml / 100 g or more, particularly preferably 100 ml / 100 g or more. The ash content is preferably 0.5% or less, particularly preferably 0.3% or less.

  Such carbon powder may be surface-treated with a surface treatment agent such as titanate, aluminum, or silane. It is also possible to use a granulated product to improve melt kneading workability.

  The innermost layer of the hollow body often requires surface smoothness. From this viewpoint, the conductive filler used in the present invention has a length / diameter ratio of 200 or less in a powdery, granular, plate-like, scale-like, or resin composition rather than a fibrous filler having a high aspect ratio. It is preferable that it is any form of the following.

  You may use the said conductive filler in combination of 2 or more types. Among these conductive fillers and conductive polymers, carbon black is particularly preferably used in terms of strength and cost.

  The content of the conductive filler used in the present invention varies depending on the type of the conductive filler to be used, and thus cannot be defined generally. However, from the viewpoint of balance between conductivity, fluidity, mechanical strength, etc., the PPS resin 100 A range of 1 to 20 parts by weight, preferably 2 to 15 parts by weight, is preferably selected with respect to parts by weight.

Such a conductive resin composition preferably has a volume resistivity of 10 ¹⁰ Ω · cm or less in order to obtain sufficient antistatic performance. However, the blending of the conductive filler generally tends to deteriorate strength and fluidity. Therefore, if the target conductivity level is obtained, it is desirable that the amount of the conductive filler and the conductive polymer is as small as possible. Although the target conductivity level varies depending on the application, the volume resistivity is usually in the range of more than ¹⁰⁰ Ω · cm and not more than 10 ¹⁰ Ω · cm.

  Moreover, when mix | blending this (d) electroconductive filler, the toughness of a PPS resin composition is easy to be impaired. In order to compensate for this, (e) an olefin polymer and / or an olefin copolymer and / or a thermoplastic elastomer may be used in combination.

  Examples of the (e) olefin polymer in the present invention include polyethylene, polypropylene, polybutene and the like.

  Next, examples of (e) the olefin copolymer include olefin elastomers, modified olefin elastomers, and styrene elastomers.

  As the olefin-based elastomer, (co) heavy obtained by polymerizing α-olefin alone or two or more types such as ethylene, propylene, butene-1, pentene-1, octene-1, 4-methylpentene-1, and isobutylene. And α, β-unsaturated acids such as acrylic acid, methyl acrylate, ethyl acrylate, butyl acrylate, methacrylic acid, methyl methacrylate, ethyl methacrylate, butyl methacrylate, and alkyl esters thereof. And the like. Specific examples of the olefin-based elastomer include an ethylene / propylene copolymer (“/” represents copolymerization, the same shall apply hereinafter), an ethylene / butene-1 copolymer, ethylene / hexene-1, ethylene / octene-1, Ethylene / methyl acrylate copolymer, ethylene / ethyl acrylate copolymer, ethylene / butyl acrylate copolymer, ethylene / methyl methacrylate copolymer, ethylene / ethyl methacrylate copolymer, ethylene / butyl methacrylate A copolymer etc. are mentioned.

  Moreover, in order to improve the compatibility of (e) component (e) with respect to (a) PPS resin as (e) olefin type copolymer, it is also possible to add a modified olefin type elastomer. As the modified olefin copolymer, a monomer component (functional group-containing component) having a functional group such as an epoxy group, an acid anhydride group, or an ionomer is added to the olefin polymer and / or the olefin copolymer. Examples of the functional group-containing component obtained by introduction include maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo [2.2.1] 5-heptene-2,3-dicarboxylic acid, Monomers containing acid anhydride groups such as endobicyclo- [2.2.1] 5-heptene-2,3-dicarboxylic anhydride, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate , Monomers containing epoxy groups such as glycidyl citraconic acid, and monomers containing ionomers such as metal carboxylates It is.

  The method for introducing these functional group-containing components is not particularly limited, and the same olefinic (co) polymer as that used as the olefinic (co) polymer may be copolymerized or (olefin) when (co) polymerizing. A method such as graft introduction into a system (co) polymer using a radical initiator can be used. 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.

  Specific examples of the olefin (co) polymer obtained by introducing a monomer component having a functional group such as an epoxy group, an acid anhydride group, or an ionomer into a particularly useful olefin polymer include ethylene / propylene-g- Glycidyl methacrylate copolymer (“g” represents graft, the same applies hereinafter), ethylene / butene-1-g-glycidyl methacrylate copolymer, ethylene / glycidyl acrylate copolymer, ethylene / glycidyl methacrylate copolymer Polymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / glycidyl methacrylate copolymer, ethylene / propylene-g-maleic anhydride copolymer, ethylene / butene-1-g-anhydrous Maleic acid copolymer, ethylene / methyl acrylate-g-maleic anhydride copolymer, Lene / ethyl acrylate-g-maleic anhydride copolymer, ethylene / methyl methacrylate-g-maleic anhydride copolymer, ethylene / ethyl methacrylate-g-maleic anhydride copolymer, ethylene / methacrylic acid copolymer In addition to zinc complexes of polymers, magnesium complexes of ethylene / methacrylic acid copolymers, sodium complexes of ethylene / methacrylic acid copolymers, or glycidyl esters of α-olefins and α, β-unsaturated acids such as ethylene and propylene In addition, an epoxy group-containing olefin copolymer having a monomer represented by the following general formula as an essential component is also preferably used.

(Wherein R ¹ represents hydrogen or a lower alkyl group, X represents one or more groups selected from —COOR ² groups, —CN groups or aromatic groups; and R ² represents 1 to ² carbon atoms. 10 alkyl groups).

  Preferred are ethylene / glycidyl methacrylate copolymer, ethylene / methyl acrylate / glycidyl methacrylate copolymer, ethylene / methyl methacrylate / glycidyl methacrylate copolymer, ethylene / butene-1-g-maleic anhydride. Examples thereof include an acid copolymer and an ethylene / ethyl acrylate-g-maleic anhydride copolymer.

  Particularly preferred are ethylene / glycidyl methacrylate copolymers, ethylene / methyl acrylate / glycidyl methacrylate copolymers, ethylene / methyl methacrylate / glycidyl methacrylate copolymers, and the like.

  On the other hand, specific examples of the styrene elastomer include styrene / butadiene copolymer, styrene / ethylene / butadiene copolymer, styrene / ethylene / propylene copolymer, styrene / isoprene copolymer, and the like. However, styrene / butadiene copolymers are preferred. More preferably, an epoxidized product of a styrene / butadiene copolymer is used.

In the present invention, as the (e) olefin polymer and / or olefin copolymer and / or thermoplastic elastomer, at least one kind of olefin copolymer having a density of 880 kg / m ³ or less is used. This is one of the preferred methods for developing higher toughness.

  Other examples include thermoplastic elastomers, elastomers composed of hard segments and soft segments such as polybutylene terephthalate / polytetraethylene glycol block copolymers and polyamide / polyethylene oxide block copolymers.

  The content of the (e) olefin polymer and / or olefin copolymer and / or thermoplastic elastomer is to impart toughness, and is (a) 1 part by weight or more with respect to 100 parts by weight of the polyphenylene sulfide resin. Preferably, 2 parts by weight or more is more preferable. Further, from the viewpoint of maintaining excellent barrier properties, the range is preferably 20 parts by weight or less, and more preferably 15 parts by weight.

  The outer layer of the PPS resin tubular body of the present invention may be coated with another PPS resin composition, another high toughness resin, an elastomer or the like in order to reinforce its strength.

  In the present invention, in order to maintain high heat resistance and thermal stability, it is also a preferred embodiment that the PPS resin composition contains one or more antioxidants selected from phenolic and phosphorus compounds. One. (A) With respect to 100 parts by weight of the PPS resin, the blending amount of the antioxidant is preferably 0.01 parts by weight or more from the viewpoint of the heat resistance improving effect, and from the viewpoint of gas components generated during molding. 5 parts by weight or less is preferable. In addition, the combined use of phenolic and phosphorus antioxidants is particularly preferable because of their large heat resistance and heat stability retention effects.

  As the phenolic antioxidant, a hindered phenolic compound is preferably used. Specific examples include triethylene glycol-bis [3-t-butyl- (5-methyl-4-hydroxyphenyl) propionate], N, N′-hexamethylenebis (3,5-di-t-butyl-4-hydroxy-hydrocinnamide), tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate ] Methane, pentaerythrityltetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], 1,3,5-tris (3,5-di-t-butyl- 4-hydroxybenzyl) -s-triazine-2,4,6- (1H, 3H, 5H) -trione, 1,1,3-tris (2-methyl-4 Hydroxy-5-tert-butylphenyl) butane, 4,4′-butylidenebis (3-methyl-6-tert-butylphenol), n-octadecyl-3- (3,5-di-tert-butyl-4-hydroxy-) Phenyl) propionate, 3,9-bis [2- (3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10 -Tetraoxaspiro [5,5] undecane, 1,3,5-trimethyl-2,4,6-tris- (3,5-di-t-butyl-4-hydroxybenzyl) benzene and the like.

  Among them, ester type polymer hindered phenol type is preferable. Specifically, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate] methane, pentaerythrityl. Tetrakis [3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], 3,9-bis [2- (3- (3-t-butyl-4-hydroxy-5- Methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane and the like are preferably used.

  Next, phosphorus antioxidants include bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol. -Di-phosphite, bis (2,4-di-cumylphenyl) pentaerythritol-di-phosphite, tris (2,4-di-t-butylphenyl) phosphite, tetrakis (2,4-di-t- Butylphenyl) -4,4′-bisphenylene phosphite, di-stearylpentaerythritol-di-phosphite, triphenyl phosphite, 3,5-dibutyl-4-hydroxybenzyl phosphonate diethyl ester, and the like.

  Among them, in order to reduce the volatilization and decomposition of the antioxidant in the PPS resin compound, those having a high melting point of the antioxidant are preferable. Specifically, bis (2,6-di-t-butyl-4- Methylphenyl) pentaerythritol-di-phosphite, bis (2,4-di-t-butylphenyl) pentaerythritol-di-phosphite, bis (2,4-di-cumylphenyl) pentaerythritol-di-phosphite, etc. Is preferably used.

  In the present invention, in order to further improve characteristics such as heat resistance and mechanical strength, the following reinforcing material can be blended within a range not impairing the effects of the present invention. Specific examples of such a reinforcing material include fibrous or non-fibrous fillers (which may be inorganic fillers or organic fillers) such as plate-like, scale-like, granular, amorphous, and crushed products. For example, organic fibers such as aromatic polyamide fibers, glass fibers, stainless fibers, aluminum fibers, metal fibers such as basalt fibers and brass fibers, gypsum fibers, ceramic fibers, asbestos fibers, zirconia fibers, alumina fibers, silica fibers, Titanium oxide fiber, silicon carbide fiber, rock wool, alumina hydrate (whisker / plate), potassium titanate whisker, barium titanate whisker, aluminum borate whisker, silicon nitride whisker, talc, kaolin, silica (crushed / spherical) ), Quartz, calcium carbonate, glass beads, glass flakes, crushed / non- Shape glass, glass microballoon, clay, molybdenum disulfide, wollastonite, aluminum oxide (crushed), titanium oxide (crushed), metal oxide such as zinc oxide, metal hydroxide such as aluminum hydroxide, aluminum nitride , Calcium polyphosphate, graphite, metal powder, metal flake, metal ribbon, metal oxide and the like. Specific examples of metal species of metal powder, metal flakes, and metal ribbons include silver, nickel, copper, zinc, aluminum, stainless steel, iron, brass, chromium, and tin.

  The surface of the filler used in the present invention can be used by treating the surface with a known coupling agent (for example, silane coupling agent, titanate coupling agent, etc.) or other surface treatment agents. .

In this invention, you may mix | blend resin other than (a) and (b) with the PPS resin composition which comprises a pipe | tube in the range which does not impair the effect of this invention. Examples of such resins include cycloolefin polymers, cycloolefin copolymers, polycarbonate resins, polyphenylene ether resins, polysulfone resins, polyether sulfone resins, polyarylate resins, polyetherimide resins, polyamideimide resins, polybutylene terephthalate resins, polyethylene terephthalate. Resin, modified polyphenylene ether resin, polyallyl sulfone resin, polyketone resin, polyarylate resin, liquid crystal polymer, polyetherketone resin, polythioetherketone resin, polyetheretherketone resin, polyimide resin, polyamideimide resin, tetrafluoropolyethylene Examples of the PPS resin composition in the present invention include other components such as a heat stabilizer (in the range not impairing the effects of the present invention). Hindered phenols, hydroquinones, phosphites and their substitutes), weathering agents (resorcinols, salicylates, benzotriazoles, benzophenones, hindered amines, etc.), mold release agents and lubricants (montanic acid and its) Metal salt, its ester, its half ester, stearyl alcohol, stearamide, various bisamides, bisurea and polyethylene wax, etc.), pigment (cadmium sulfide, phthalocyanine, carbon black for coloring, etc.), dye (such as nigrosine), plasticizer (p -Octyl oxybenzoate, N-butylbenzenesulfonamide, etc.), antistatic agents (alkyl sulfate type anionic antistatic agents, quaternary ammonium salt type cationic antistatic agents, non-polyoxyethylene sorbitan monostearate, etc. ON-type antistatic agent, betaine-type amphoteric antistatic agent, etc.), flame retardant (for example, red phosphorus, phosphate ester, melamine cyanurate, magnesium hydroxide, aluminum hydroxide, hydroxide, ammonium polyphosphate, brominated polystyrene Brominated polyphenylene ether, brominated polycarbonate, brominated epoxy resin, or a combination of these brominated flame retardants and antimony trioxide).

  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 polycondensate, release agents such as silicone compounds, anti-coloring agents such as hypophosphite, water, lubricants, UV protection agents, coloring agents, foaming A usual additive such as an agent can be blended.

  The production method of the PPS resin composition for PPS resin pipes of the present invention is usually produced by a known method. For example, (a) PPS resin, (b) component, (c) component, (d) component, (e) component, and other necessary additives may be supplied to an extruder or the like with or without premixing. And prepared by sufficiently melting and kneading. Moreover, the method of supplying a one part component from a main hopper and supplying the remaining component from a side feeder etc. is mentioned. Also, it may be melt-kneaded in two portions.

  When producing the fat composition of the present invention, for example, 180-350 ° C. using a single screw extruder, twin screw, three screw extruder and kneader kneader equipped with a “unimelt” (R) type screw. Can be melt kneaded into a composition.

  Next, although the tubular molded body which is an example of the manufacturing method of the hollow molded article of this invention is demonstrated to an example, of course, it is not limited to the following. That is, there is a method in which a molten resin extruded from an extruder is introduced into one tube die and extruded to obtain a tubular body.

  The PPS resin tubular body of the present invention thus obtained is excellent in heat resistance, hot water resistance, chemical resistance, abrasion resistance, appearance of molded products, toughness, and conductivity, and blow molding of bottles, tanks, ducts and the like. As an extruded product such as a product, pipe, tube, etc., it is effective for automobile parts, electrical / electronic parts, and chemicals. In particular, the PPS tubular body of the present invention is used for fuel tubes in which the above characteristics are sufficiently exhibited, In particular, it is preferably applied to applications in which automobile fuel flows inside.

Evaluation method [gasoline permeability]
One end of the tube cut into 30 cm was sealed, and an alcohol gasoline mixture in which commercial regular gasoline and methyl alcohol were mixed in a ratio of 85 to 15 was put inside, and the remaining end was also sealed. Thereafter, the entire weight was measured, and the test tube was placed in an oven at 40 ° C., and the alcohol gasoline permeability was evaluated by the change in weight.

[Tensile elongation]
ASTM No. 4 dumbbell pieces were molded at a resin temperature of 310 ° C. and a mold temperature of 150 ° C. using a Sumitomo-Nestal injection molding machine SG75. The measurement was performed using a Tensilon UTA 2.5T tensile tester at a distance between chucks of 64 mm and a tensile speed of 10 mm / min.

[Observation of morphology]
The tensile test piece was formed by injection molding. The central part of the test piece was cut in a direction perpendicular to the flow direction, and a thin piece of 0.1 μm or less was cut at −20 ° C. from the central part of the cross section, and an H-7100 transmission electron microscope manufactured by Hitachi, Ltd. The dispersion particle diameter of the polyetherimide resin and / or the polyamide resin was measured by enlarging the image to 10,000 to 20,000 times (resolution (particle image) 0.38 nm, magnification: 500 to 600,000 times).

Reference Example 1 Manufacture of PPS Manufacture of PPS-1 In an autoclave equipped with a rectifying tower with a filler, an aqueous solution of sodium hydrosulfide having a concentration of 48 wt% was 2.923 kg (25.0 mol in terms of sodium hydrosulfide), and a concentration of 48 wt. % Sodium hydroxide aqueous solution 2.188 kg (26.3 mol in terms of sodium hydroxide), NMP 4.090 kg (41.3 mol) and anhydrous sodium acetate 0.8 kg (9.8 mol) were charged at room temperature. While stirring through nitrogen at normal pressure, the mixture was gradually heated to 240 ° C. over about 2.5 hours to distill 2.658 kg of water. The hydrogen sulfide scattered at this time was 0.4 mol.

  Next, after cooling the autoclave to 180 ° C., 3.655 kg (25.4 mol) of 1,4-dichlorobenzene and 3.345 kg (33.8 mol) of NMP were added and sealed under nitrogen for 160 minutes to 270 ° C. The mixture was heated up and reacted at 270 ° C. for 80 minutes. After the reaction, 0.45 kg of water was cooled to 250 ° C. over 15 minutes while being charged into the autoclave, and then cooled to 220 ° C. over 75 minutes. Thereafter, the content was put into 12.5 liters of NMP, stirred at 85 ° C. for 30 minutes, and then filtered through an 80 mesh wire net to obtain a solid. The obtained solid was washed again with 12.5 liters of NMP and filtered. The resulting solid was then washed 3 times with 25 liters of water (70 ° C.) and filtered off. The solid obtained was adjusted to pH = 4.2 with acetic acid, washed with warm water at 70 ° C., and filtered. Further, the obtained solid was again washed with 25 liters of water (70 ° C.) and filtered.

  The solid thus obtained was dried under reduced pressure at 80 ° C. for 24 hours to obtain PPS-1 having an MFR of 100 g / 10 minutes (weight average molecular weight 70,000) and a melting peak temperature of 280 ° C.

Reference Example 2 Compounding Agent (B-1) Nylon 6/66 Copolymer A 50% aqueous solution of a salt of adipic acid and hexamethylenediamine (AH salt) and ε-caprolactam (CL) with 20 parts by weight of AH salt, CL Was mixed to 80 parts by weight and charged into a 30 liter autoclave. After the temperature was raised to 270 ° C. at an internal pressure of 10 kg / cm ² , the internal temperature was kept at 245 ° C., and the pressure was gradually reduced to 0.5 kg / cm ² while stirring to stop stirring. After returning to normal pressure with nitrogen, it was extracted as a strand, pelletized, and unreacted substances were extracted and removed using boiling water and dried. The copolymer polyamide 6/66 resin thus obtained (copolymerization ratio (weight ratio): nylon 6 component / nylon 66 component = 80/20) had a relative viscosity of 4.20 and a melting point of 193 ° C. .
(B-2): CM2001 (nylon 610) manufactured by Toray Industries, Inc.
(B-3): Toray Industries, Inc. E3001 (nylon 66)
(C-1) 3-isocyanatopropyltriethoxysilane (Shin-Etsu Silicone KBE9007)
(C-2) γ-glycidoxypropyltrimethoxysilane (KBM403 manufactured by Shin-Etsu Silicone Co., Ltd.)
(D-1) Conductive filler: carbon black (EC600JD manufactured by Ketjen Black International Co., Ltd., DBP oil absorption 495 ml / 100 g, BET method surface area 1270 m ² / g, average particle size 30 nm, ash content 0.2%
(E-1) Olefin copolymer ethylene / glycidyl methacrylate = 88/12 (% by weight) copolymer (E) containing α-olefin and glycidyl ester of α, β-unsaturated acid as main constituents -2) Ethylene / butene-1 = 88/12 MFR = 0.5 Density 885 kg / m ³
Molding method: As the molding apparatus, an apparatus having an extruder and comprising a die for molding the resin discharged from the extruder into a tube shape, a sizing die for cooling the tube to control the dimensions, and a take-up machine was used. The obtained tube had an outer diameter of 8 mm and an inner diameter of 6 mm.

[Examples 1-5, Comparative Examples 1-2]
The blended materials were dry blended in the proportions shown in Table 1 and premixed for 2 minutes with a tumbler, and then a TEX30α type twin screw extruder (L / D = 45.5, 3 kneading parts) manufactured by Nippon Steel Works. The temperature was set so that the cylinder discharge resin temperature was 330 ° C. at a screw rotation speed of 300 rpm, melt kneaded, and pelletized with a strand cutter. The pellets dried at 120 ° C. overnight were used for injection molding and extrusion tubular molding. The results of measuring the tensile elongation, gasoline permeability, and polyamide dispersion diameter of each sample are as shown in Table 1.

[Example 6]
The same pelletizing and evaluation as in Example 1 were performed except that melt kneading was performed at a set temperature of 300 ° C. and a screw rotation speed of 80 rpm using a 40 mmφ single screw extruder manufactured by Tanabe Plastics Machinery Co., Ltd. The results were as shown in Table 1.

Claims (12)

  (A) 100 parts by weight of a polyphenylene sulfide resin, and (b) a polyphenylene sulfide containing 1 part by weight or more and less than 20 parts by weight of a polyamide resin (not including an acid-modified ethylene / α-olefin copolymer) forms a matrix phase. A tubular body made of a polyphenylene sulfide resin composition, wherein a fluid flows inside the tubular body, and the flowing fluid is in contact with the tubular body. The tubular body according to claim 1, wherein the polyphenylene sulfide resin composition has a number average dispersed particle size of (b) polyamide resin of less than 500 nm. The polyphenylene sulfide resin composition according to any one of claims 1 to 2, wherein the polyphenylene sulfide resin composition has a number average dispersed particle diameter of less than 500 nm after (b) the polyamide resin is melt-retained at 300 ° C for 30 minutes. Tubular body. The tubular body comprising the polyphenylene sulfide resin composition according to any one of claims 1 to 3, wherein (b) the polyamide resin is at least one selected from copolymerized polyamide, nylon 610 and nylon 612. The polyphenylene sulfide resin composition further comprises (c) a compound having one or more groups selected from an epoxy group, an amino group and an isocyanate group as a compatibilizing agent with respect to 100 parts by weight of the (a) polyphenylene sulfide resin. The tubular body according to any one of claims 1 to 4, wherein 1 to 30 parts by weight are added.   6. The tubular body according to claim 5, wherein (c) the compatibilizing agent is an organosilane compound having one or more groups selected from an epoxy group, an amino group, and an isocyanate group. The tubular structure according to any one of claims 1 to 6, wherein the polyphenylene sulfide resin composition comprises (d) a conductive filler in an amount of 1 to 20 parts by weight per 100 parts by weight of the (a) polyphenylene sulfide resin. body. The tubular body according to any one of claims 1 to 7, wherein the polyphenylene sulfide resin composition contains (e) at least one selected from an olefin polymer, an olefin copolymer, and a thermoplastic elastomer. 9. The tubular structure according to claim 8, wherein at least one selected from (e) an olefin polymer, an olefin copolymer and a thermoplastic elastomer is an olefin copolymer having a density of 880 kg / m ³ or less. body. The content of at least one selected from (e) an olefin polymer, an olefin copolymer, and a thermoplastic elastomer is 1 to 20 parts by weight relative to 100 parts by weight of the (a) polyphenylene sulfide resin. Or the tubular body of 9. The tubular body according to any one of claims 1 to 10, obtained by an extrusion method. The tubular body according to any one of claims 1 to 11, wherein the tubular body is a polyphenylene sulfide resin composition in which automobile fuel flows.