JP6210341B2 - Multilayer molded body and fuel parts using the same - Google Patents

Description

  The present invention relates to a multilayer molded body suitable for piping members, containers, and tubes used for transporting organic substances such as fuel.

  In recent years, piping materials, containers, and tube products used to transport fluid organic substances such as solvents, fuels, liquefied gases, and other polymer raw materials, intermediates, and products have been replaced with metal materials and plastics have been promoted. For example, a polyamide resin having a high barrier performance against fuel such as gasoline is used for a fuel piping member and a container for a vehicle.

  However, for alcohol-containing gasoline that is rapidly spreading, the barrier property of polyamide resin is never sufficient, and even polyamide 12 having a relatively high barrier property against alcohol-containing gasoline can be released into the atmosphere. It is in a situation where it is not possible to obtain a high barrier property capable of complying with various laws and regulations for preventing fuel diffusion.

  On the other hand, polyphenylene sulfide resin has attracted attention as a resin material having a very high barrier property against alcohol-containing gasoline. However, although polyphenylene sulfide resin has excellent heat resistance and chemical resistance, it has insufficient impact resistance and is difficult to apply to a vehicle fuel tube or a fuel tank. Therefore, as a method of manufacturing a fuel tube or a fuel tank for a vehicle, a three-layer structure of a polyphenylene sulfide resin layer, an adhesive layer and a polyethylene layer is used, while maintaining the barrier property of the polyphenylene sulfide resin, and impact resistance. A molded container imparted with properties has been proposed (see, for example, Patent Documents 1 and 2).

  However, since the polyphenylene sulfide resin has low adhesiveness to other resin components, the multilayer structure has a problem that the barrier property is remarkably lowered due to easy peeling between layers. In particular, when it is used for a member used in an engine room that is in a high temperature environment, there may be a problem such as deformation due to significant softening of the polyethylene layer as the temperature rises.

  As a method for solving the problem of softening of the polyethylene layer in the multilayer structure using the polyphenylene sulfide resin, a layer made of a mixture of polyphenylene sulfide and an epoxy group-containing polyolefin, a polyolefin adhesive layer, and a layer made of polyamide are laminated. A multilayer structure having been proposed has been proposed (see, for example, Patent Document 3). However, since this multilayer structure uses a polyolefin-based adhesive layer, the peel strength between layers tends to be insufficient when used in a high temperature environment.

  A thermoplastic resin having one or more bonds or functional groups selected from polyamide, amide bond, ester bond, urethane bond, carboxyl group, acid anhydride group and epoxy group with respect to 100 parts by weight of polyphenylene sulfide resin. There has been proposed a multilayer structure in which a polyphenylene sulfide-based resin layer containing 10 to 150 parts by weight of a polyphenylene sulfide resin layer and a polyamide layer are multilayered without using an adhesive layer (see, for example, Patent Document 4). .) However, this multilayer structure needs to contain a large amount of polyamide and modified olefin resin in the polyphenylene sulfide resin in order to obtain adhesion to the polyamide resin layer, and the barrier property inherent in the polyarylene sulfide resin is impaired. May be.

  Furthermore, by co-extruding a resin component in which a polyisocyanate compound is blended with a polyarylene sulfide resin with a thermoplastic resin having a specific functional group, the adhesion between the layers can be reduced without reducing the performance of the polyarylene sulfide resin. Has been proposed (see, for example, Patent Document 5). However, when the polyvalent isocyanate compound is self-condensed or decomposed during melt-kneading, the interlayer adhesion may be lowered, and it tends to be difficult to maintain the level of adhesion required for the fuel piping member and the like.

JP-A-5-193060 JP-A-5-193061 JP-A-11-156970 JP 10-138372 A JP 2008-110561 A

  On the other hand, the polyarylene sulfide resin synthesized by the conventional method has a relatively large amount of gas generated by heating at the time of molding processing, and a bad odor is generated at the time of molding processing. The multilayer molded body may peel off due to adhesion between layers. Therefore, suppressing gas generation is very important for practical use as a molding material.

  The problem to be solved by the present invention is that the amount of gas generated by heating can be suppressed, and in the use of piping members, containers, tubes and the like used for fluid transportation of organic matter such as fuel, the organic matter fluid inherent to polyarylene sulfide resin An object of the present invention is to provide a multilayer molded article that exhibits excellent adhesion to other resin components without impairing excellent barrier properties against the above, and a fuel component using the same.

  As a result of various studies, the present inventors have found that a polyarylene sulfide resin obtained by melt polymerization of a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor, an aromatic epoxy resin, and a thermoplastic elastomer. The present inventors have found that the above-described problems can be solved by using the resin composition contained therein, and have completed the present invention.

  That is, the present invention relates to a polyarylene sulfide resin composition comprising a polyarylene sulfide resin, an aromatic epoxy resin and a thermoplastic elastomer as essential components, an amino group, an amide group, a hydroxyl group, a carboxyl group, an acid anhydride group, an isocyanate A multilayer molded body having a multilayer structure obtained by coextrusion molding of a thermoplastic resin having one or more functional groups selected from the group consisting of a group and an epoxy group, wherein the polyarylene sulfide resin is a diiodo aromatic A multilayer molded article that can be obtained by a method comprising reacting a group compound, elemental sulfur, and a polymerization inhibitor in a molten mixture containing a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor And a fuel component using the same.

  According to the present invention, the amount of gas generated by heating can be suppressed, and an excellent barrier against the original organic fluid of polyarylene sulfide resin in applications such as piping members, containers, and tubes used for transporting organic fluid such as fuel. It is possible to provide a multilayer molded article that exhibits excellent adhesion with other resin components without impairing the properties. The multilayer molded article of the present invention is optimal for fuel parts such as piping members, containers, and tubes used for transporting fuels such as gasoline, light oil, alcohol-containing gasoline, and alcohol fuel.

  Hereinafter, preferred embodiments of the present invention will be described in detail. However, the present invention is not limited to the following embodiments.

  The multilayer molded body according to this embodiment includes a polyarylene sulfide resin, an aromatic epoxy resin, and a polyarylene sulfide resin composition containing thermoplastic elastomer as essential components, an amino group, an amide group, a hydroxyl group, a carboxyl group, and an acid anhydride. A multilayer structure obtained by coextrusion molding of a thermoplastic resin having one or more functional groups selected from the group consisting of a physical group, an isocyanate group and an epoxy group (hereinafter abbreviated as “thermoplastic resin”). Have.

  The polyarylene sulfide resin used in the present embodiment is obtained by reacting a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor in a molten mixture containing the diiodo aromatic compound, elemental sulfur and the polymerization inhibitor. It can be obtained by the method of including. According to such a method, a polyarylene sulfide resin can be obtained as a polymer having a relatively high molecular weight as compared with conventional methods such as the Philips method.

  The diiodo aromatic compound has an aromatic ring and two iodine atoms directly bonded to the aromatic ring. Examples of diiodo aromatic compounds include, but are not limited to, diiodobenzene, diiodotoluene, diiodoxylene, diiodonaphthalene, diiodobiphenyl, diiodobenzophenone, diiododiphenyl ether, and diiododiphenyl sulfone. The substitution positions of the two iodine atoms are not particularly limited, but it is preferable that the two substitution positions are located as far as possible in the molecule. Preferred substitution positions are the para position and the 4,4'-position.

  Aromatic rings of diiodo aromatic compounds include phenyl groups, halogen atoms other than iodine atoms, hydroxy groups, nitro groups, amino groups, alkoxy groups having 1 to 6 carbon atoms, carboxy groups, carboxylates, aryl sulfones and aryl ketones. It may be substituted with at least one substituent selected from However, from the viewpoint of the crystallinity and heat resistance of the polyarylene sulfide resin, the ratio of the substituted diiodo aromatic compound to the unsubstituted diiodo aromatic compound is preferably in the range of 0.0001 to 5% by mass. More preferably, it is the range of 0.001-1 mass%.

The elemental sulfur means a substance (S ₈ , S ₆ , S ₄ , S _2, etc.) composed only of sulfur atoms, and its form is not limited. More specifically, the present invention may be used elemental sulfur which is commercially available as Tsuboneho medicament may be obtained generically, may be used a mixture containing S ₈ and S ₆ and the like. The purity of elemental sulfur is not particularly limited. The elemental sulfur may be in the form of particles or powder as long as it is solid at room temperature (23 ° C.). The particle size of the elemental sulfur is not particularly limited, but is preferably in the range of 0.001 to 10 mm, more preferably in the range of 0.01 to 5 mm, and still more preferably in the range of 0.01 to 3 mm.

  The polymerization inhibitor can be used without particular limitation as long as it is a compound that inhibits or stops the polymerization reaction in the polymerization reaction of the polyarylene sulfide resin. The polymerization inhibitor preferably contains a compound capable of introducing at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxyl group and a salt of a carboxyl group at the end of the main chain of the polyarylene sulfide resin. That is, the polymerization inhibitor is preferably a compound having one or more groups selected from the group consisting of a hydroxy group, an amino group, a carboxyl group, and a carboxyl group salt. Moreover, the polymerization inhibitor may have the functional group, or the functional group may be generated by a polymerization termination reaction or the like.

  As the polymerization inhibitor having a hydroxy group or an amino group, for example, a compound represented by the following formula (1) or (2) may be used as the polymerization inhibitor.

一般式（１）で表される化合物によれば、下記式（１−１）で表される一価の基が主鎖の末端基として導入される。式（１−１）中のＹは、重合禁止剤に由来するヒドロキシ基、アミノ基等である。

According to the compound represented by the general formula (1), a monovalent group represented by the following formula (1-1) is introduced as a terminal group of the main chain. Y in Formula (1-1) is a hydroxy group, an amino group, or the like derived from a polymerization inhibitor.

一般式（２）で表される化合物によれば、下記式（２−１）で表される一価の基が主鎖の末端基として導入される。一般式（１）で表される化合物に由来するヒドロキシ基が、例えば、式（２）中のカルボニル基の炭素原子と硫黄ラジカルと結合することによりポリアリーレンスルフィド樹脂中に導入され得る。

According to the compound represented by the general formula (2), a monovalent group represented by the following formula (2-1) is introduced as a terminal group of the main chain. A hydroxy group derived from the compound represented by the general formula (1) can be introduced into the polyarylene sulfide resin by, for example, bonding to a carbon atom of a carbonyl group in the formula (2) and a sulfur radical.

式（１−１）又は（２−１）で表される基は、ポリアリーレンスルフィド樹脂の主鎖中に原料（単体硫黄）に由来して存在するジスルフィド結合が溶融温度下でラジカル開裂して発生した硫黄ラジカルと、一般式（１）で表される化合物又は一般式（２）で表される化合物とが結合することによって、ポリアリーレンスルフィド樹脂中に導入されると考えられる。これら特定構造の構成単位の存在は、一般式（１）又は（２）で表される化合物を用いた溶融重合により得られたポリアリーレンスルフィド樹脂に特徴的である。

In the group represented by the formula (1-1) or (2-1), the disulfide bond derived from the raw material (single sulfur) in the main chain of the polyarylene sulfide resin is radically cleaved at the melting temperature. The generated sulfur radical and the compound represented by the general formula (1) or the compound represented by the general formula (2) are considered to be introduced into the polyarylene sulfide resin. The existence of these structural units having a specific structure is characteristic of the polyarylene sulfide resin obtained by melt polymerization using the compound represented by the general formula (1) or (2).

  Examples of the compound represented by the general formula (1) include 2-iodophenol and 2-aminoaniline. Examples of the compound represented by the general formula (2) include 2-iodobenzophenone.

  As the polymerization inhibitor having a carboxyl group, for example, one or more compounds selected from compounds represented by the following general formula (3), (4) or (5) may be used.

一般式（３）中、Ｒ^１及びＲ^２はそれぞれ独立に、水素原子、又は、下記一般式（ａ）、（ｂ）若しくは（ｃ）で表される一価の基を表し、Ｒ^１又はＲ^２の少なくともいずれか一方は一般式（ａ）、（ｂ）又は（ｃ）で表される一価の基である。一般式（４）中、Ｚは、ヨウ素原子又はメルカプト基を表し、Ｒ^３は、下記一般式（ａ）、（ｂ）又は（ｃ）で表される一価を表す。一般式（５）中、Ｒ^４は、一般式（ａ）、（ｂ）又は（ｃ）で表される一価の基を表す。

In the general formula (3), R ¹ and R ² each independently represent a hydrogen atom or a monovalent group represented by the following general formula (a), (b) or (c), and R ¹ or At least one of R ² is a monovalent group represented by the general formula (a), (b) or (c). In General Formula (4), Z represents an iodine atom or a mercapto group, and R ³ represents a monovalent group represented by the following General Formula (a), (b), or (c). In General Formula (5), R ⁴ represents a monovalent group represented by General Formula (a), (b), or (c).

一般式（ａ）〜（ｃ）中のＸは、水素原子又はアルカリ金属原子であるが、反応性が良好となる点から水素原子が好ましい。アルカリ金属原子としては、ナトリウム、リチウム、カリウム、ルビジウム、及びセシウムなどが挙げられるが、ナトリウムが好ましい。一般式（ｂ）中、Ｒ^１０は炭素原子数１〜６のアルキル基を表す。一般式（ｃ）中、Ｒ^１１は水素原子又は炭素原子数１〜３のアルキル基を表し、Ｒ^１２は炭素原子数１〜５のアルキル基を表す。

X in the general formulas (a) to (c) is a hydrogen atom or an alkali metal atom, and is preferably a hydrogen atom from the viewpoint of good reactivity. Examples of the alkali metal atom include sodium, lithium, potassium, rubidium, and cesium, and sodium is preferable. In general formula (b), R ¹⁰ represents an alkyl group having 1 to 6 carbon atoms. In general formula (c), R ¹¹ represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹² represents an alkyl group having 1 to 5 carbon atoms.

  According to the compound represented by the general formula (3), (4) or (5), a monovalent group represented by the following formula (6) or (7) is introduced as an end group of the main chain. The presence of the terminal structural unit of these specific structures is characteristic of the polyarylene sulfide resin obtained by melt polymerization using the compound represented by the general formula (3), (4) or (5).

（式中、Ｒ^５は、一般式（ａ）、（ｂ）又は（ｃ）で表される一価の基を表す。）

(In the formula, R ⁵ represents a monovalent group represented by the general formula (a), (b) or (c)).

（式中、Ｒ^６は、一般式（ａ）、（ｂ）又は（ｃ）で表される一価の基を表す。）

(In the formula, R ⁶ represents a monovalent group represented by the general formula (a), (b) or (c)).

  As the polymerization inhibitor, a compound having no functional group such as a carboxyl group may be used. Examples of such compounds include diphenyl disulfide, monoiodobenzene, thiophenol, 2,2′-dibenzothiazolyl disulfide, 2-mercaptobenzothiazole, N-cyclohexyl-2-benzothiazolylsulfenamide, 2 At least one compound selected from-(morpholinothio) benzothiazole and N, N'-dicyclohexyl-1,3-benzothiazole-2-sulfenamide can be used.

  The polyarylene sulfide resin according to this embodiment is obtained by performing melt polymerization in a melt mixture obtained by heating a mixture containing a diiodo aromatic compound, elemental sulfur, a polymerization inhibitor, and a catalyst as necessary. Generate. The ratio of the diiodo aromatic compound in the molten mixture is preferably in the range of 0.5 to 2 mol, more preferably in the range of 0.8 to 1.2 mol, with respect to 1 mol of elemental sulfur. The ratio of the polymerization inhibitor in the mixture is preferably in the range of 0.0001 to 0.1 mol, more preferably in the range of 0.0005 to 0.05 mol, with respect to 1 mol of solid sulfur. .

  The timing for adding the polymerization inhibitor is not particularly limited, but the mixture containing the diiodo aromatic compound, elemental sulfur and the catalyst added as necessary is heated, and the temperature of the mixture is preferably 200 ° C to 320 ° C. A polymerization inhibitor can be added when the temperature is in the range, more preferably in the range of 250 to 320 ° C.

  A nitro compound can be added to the molten mixture as a catalyst to control the polymerization rate. As this nitro compound, various nitrobenzene derivatives can be usually used. Examples of the nitrobenzene derivative include 1,3-diiodo-4-nitrobenzene, 1-iodo-4-nitrobenzene, 2,6-diiodo-4-nitrophenol and 2,6-diiodo-4-nitroamine. The amount of the catalyst is usually an amount added as a catalyst, and for example, it is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of elemental sulfur.

  The conditions for melt polymerization are appropriately adjusted so that the polymerization reaction proceeds appropriately. The temperature of the melt polymerization is preferably 175 ° C. or higher, the melting point of the resulting polyarylene sulfide resin + 100 ° C. or lower, more preferably 180 to 350 ° C. The melt polymerization is preferably carried out at an absolute pressure in the range of 1 [cPa] to 100 [kPa], more preferably in the range of 13 [cPa] to 60 [kPa]. The conditions for melt polymerization need not be constant. For example, at the initial stage of polymerization, the temperature is preferably in the range of 175 to 270 ° C., more preferably in the range of 180 to 250 ° C., and the absolute pressure is in the range of 6.7 to 100 [kPa], and then continuously or Polymerization is carried out while raising and lowering the temperature stepwise, and in the latter stage of polymerization, the temperature is preferably 270 ° C. or more, the melting point of the polyarylene sulfide resin to be produced + 100 ° C. or less, more preferably 300 to 350 ° C., And it can superpose | polymerize by making an absolute pressure into the range of 1 [cPa]-6 [kPa]. In this specification, melting | fusing point of resin means the value measured based on JISK7121 using the differential scanning calorimeter (DSC apparatus Pyris Diamond made from Perkin Elmer).

  The melt polymerization is preferably performed in a non-oxidizing atmosphere from the viewpoint of obtaining a high degree of polymerization while preventing oxidative crosslinking reaction. In the non-oxidizing atmosphere, the oxygen concentration in the gas phase is preferably in the range of less than 5% by volume, more preferably in the range of less than 2% by volume, and more preferably the gas phase is substantially free of oxygen. The non-oxidizing atmosphere is preferably an inert gas atmosphere such as nitrogen, helium and argon.

  The melt polymerization can be performed using, for example, a melt kneader equipped with a heating device, a decompression device, and a stirring device. Examples of the melt kneader include a Banbury mixer, a kneader, a continuous kneader, a single screw extruder, and a twin screw extruder.

  The melt mixture for melt polymerization is preferably substantially free of solvent. More specifically, the amount of the solvent contained in the molten mixture is preferably 10 masses with respect to a total of 100 mass parts of the diiodo aromatic compound, elemental sulfur, the polymerization inhibitor, and, if necessary, the catalyst. Part or less, more preferably 5 parts by weight or less, and even more preferably 1 part by weight or less. The amount of the solvent may be 0 part by mass or more, 0.01 part by mass or more, or 0.1 part by mass or more.

  After the melt mixture (reaction product) after the melt polymerization is cooled to obtain a solid state mixture, the mixture is heated under reduced pressure or atmospheric pressure in a non-oxidizing atmosphere to further advance the polymerization reaction. Also good. As a result, not only can the molecular weight be increased, but also the generated iodine molecules are sublimated and removed, so the iodine atom concentration in the polyarylene sulfide resin can be kept low. The solid state mixture can be obtained by cooling to a temperature of preferably 100 to 260 ° C, more preferably 130 to 250 ° C, and even more preferably 150 to 230 ° C. Heating after cooling to the solid state can be performed under the same temperature and pressure conditions as in melt polymerization.

  The reaction product containing the polyarylene sulfide resin obtained by the melt polymerization step can be directly produced in a melt-kneader to produce a resin composition. It is preferable to prepare a dissolved product by adding a solvent in which the reaction product is dissolved, and to take out the reaction product from the reaction apparatus in the dissolved state because not only the productivity is improved but also the reactivity is improved. The addition of the solvent in which the reaction product is dissolved is preferably performed after the melt polymerization, but it may be performed in the later stage of the reaction of the melt polymerization, or as described above, the molten mixture (reaction product) is cooled to form a solid state. After obtaining the mixture, the polymerization reaction may be further advanced by heating the mixture under pressure, reduced pressure, or atmospheric pressure in a non-oxidizing atmosphere. The step of preparing the lysate may be performed in a non-oxidizing atmosphere. In addition, the temperature for heating and dissolution may be in the range of the melting point of the solvent in which the reaction product dissolves, preferably in the range of 200 to 350 ° C, more preferably in the range of 210 to 250 ° C, under pressure. Preferably it is done.

  The mixing ratio of the solvent in which the reaction product is used for preparing the dissolved product is preferably in the range of 90 to 1000 parts by mass with respect to 100 parts by mass of the reaction product containing the polyarylene sulfide resin. Preferably it is the range of 200-400 mass parts.

  As a solvent in which the reaction product dissolves, for example, a solvent used as a polymerization reaction solvent in solution polymerization such as a Philips method can be used. Examples of preferred solvents include N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), N-cyclohexyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and ε-caprolactam. , Aliphatic cyclic amide compounds such as N-methyl-ε-caprolactam, amide compounds such as hexamethylphosphoric triamide (HMPA), tetramethylurea (TMU), dimethylformamide (DMF), and dimethylacetamide (DMA), polyethylene Examples include etherified polyethylene glycol compounds such as glycol dialkyl ether (having a degree of polymerization of 2000 or less and an alkyl group having 1 to 20 carbon atoms), and sulfoxide compounds such as tetramethylene sulfoxide and dimethyl sulfoxide (DMSO). It is done. Examples of other usable solvents include benzophenone, diphenyl ether, diphenyl sulfide, 4,4′-dibromobiphenyl, 1-phenylnaphthalene, 2,5-diphenyl-1,3,4-oxadiazole, 2,5- Diphenyloxazole, triphenylmethanol, N, N-diphenylformamide, benzyl, anthracene, 4-benzoylbiphenyl, dibenzoylmethane, 2-biphenylcarboxylic acid, dibenzothiophene, pentachlorophenol, 1-benzyl-2-pyrrolidione, 9- Fluorenone, 2-benzoylnaphthalene, 1-bromonaphthalene, 1,3-diphenoxybenzene, fluorene, 1-phenyl-2-pyrrolidinone, 1-methoxynaphthalene, 1-ethoxynaphthalene, 1,3-diphenylacetate 1,4-dibenzoylptane, phenanthrene, 4-benzoylbiphenyl, 1,1-diphenylacetone, o, o'-biphenol, 2,6-diphenylphenol, triphenylene, 2-phenylphenol, thianthrene, 3-phenoxy Benzyl alcohol, 4-phenylphenol, 9,10-dichloroanthracene, triphenylmethane, 4,4′-dimethoxybenzophenone, 9,10-diphenylanthracene, fluoranthene, diphenylphthalate, diphenyl carbonate, 2,6-dimethoxynaphthalene, 2,7-dimethoxynaphthalene, 4-bromodiphenyl ether, pyrene, 9,9'-bifluorene, 4,4'-isopropylidene-diphenol, epsilon-caprolactam, N-cyclohexyl 2-pyrrolidone, diphenyl isophthalate, one or more solvents thereof selected from diphenyl chromatography terpolymers phthalate and the group consisting of 1-chloronaphthalene.

The melted product taken out from the reaction apparatus is preferably post-treated and then melt-kneaded with the other components to prepare a resin composition because the reactivity becomes better. The method for post-treatment of the lysate is not particularly limited, and examples thereof include the following methods.
(1) The solvent is used as it is or after adding an acid or a base, and then the solvent is distilled off under reduced pressure or normal pressure. (Or an organic solvent having an equivalent solubility with respect to a low-molecular polymer), a method of washing once or twice or more with a solvent selected from acetone, methyl ethyl ketone and alcohols, and further neutralizing, washing with water, filtering and drying.
(2) Solvents such as water, acetone, methyl ethyl ketone, alcohol, ether, halogenated hydrocarbon, aromatic hydrocarbon and aliphatic hydrocarbon (soluble in the solvent of the solution and at least polyarylene) A solvent which is a poor solvent for sulfide resin) is added as a precipitating agent to precipitate a solid product containing polyarylene sulfide resin and inorganic salt, and the solid product is filtered, washed and dried. Method.
(3) After adding the solvent used for the dissolved material (or an organic solvent having an equivalent solubility with respect to the low molecular weight polymer) to the dissolved material, stirring, and filtering to remove the low molecular weight polymer, A method of washing once or twice or more with a solvent selected from water, acetone, methyl ethyl ketone and alcohol, and then neutralizing, washing with water, filtering and drying.

  In the post-treatment methods exemplified in the above (1) to (3), the polyarylene sulfide resin may be dried in a vacuum or in an inert gas atmosphere such as air or nitrogen. May be. The polyarylene sulfide resin can be oxidized and crosslinked by heat treatment in an oxidizing atmosphere having an oxygen concentration in the range of 5 to 30% by volume or under reduced pressure.

  The reaction that the polyarylene sulfide resin produces by melt polymerization is exemplified below.

反応式（１）〜（５）は、例えば一般式（ａ）、（ｂ）又は（ｃ）で表される基を含む置換基Ｒを有するジフェニルジスルフィドを重合禁止剤として用いた場合の、ポリフェニレンスルフィドが生成する反応の例である。反応式（１）は、重合禁止剤中の−Ｓ−Ｓ−結合が、溶融温度下でラジカル開裂する反応である。反応式（２）は、反応式（１）で発生した硫黄ラジカルが成長中の主鎖の末端ヨウ素原子の隣接炭素原子を攻撃し、ヨウ素原子が脱離することで、重合が停止するとともに、主鎖の末端に置換基Ｒが導入される反応である。反応式（３）は、ポリアリーレンスルフィド樹脂の主鎖中に原料（単体硫黄）に由来して存在するジスルフィド結合が溶融温度下でラジカル開裂する反応である。反応式（４）は、反応式（３）で発生した硫黄ラジカルと、反応式（１）で発生した硫黄ラジカルとの再結合によって、重合が停止するとともに、置換基Ｒが主鎖の末端に導入される反応である。脱離したヨウ素原子は遊離状態（ヨウ素ラジカル）にあるか、又は、反応式（５）のようにヨウ素ラジカル同士が再結合することで、ヨウ素分子が生成する。

Reaction formulas (1) to (5) are, for example, polyphenylene when diphenyl disulfide having a substituent R containing a group represented by general formula (a), (b) or (c) is used as a polymerization inhibitor. It is an example of reaction which sulfide produces | generates. Reaction formula (1) is a reaction in which the —S—S— bond in the polymerization inhibitor undergoes radical cleavage at the melting temperature. In the reaction formula (2), the sulfur radical generated in the reaction formula (1) attacks the adjacent carbon atom of the terminal iodine atom of the growing main chain, and the iodine atom is detached, so that the polymerization is stopped, In this reaction, a substituent R is introduced at the end of the main chain. Reaction formula (3) is a reaction in which a disulfide bond existing in the main chain of the polyarylene sulfide resin derived from the raw material (single sulfur) is radically cleaved at the melting temperature. In the reaction formula (4), the polymerization is stopped by recombination of the sulfur radical generated in the reaction formula (3) and the sulfur radical generated in the reaction formula (1), and the substituent R is at the end of the main chain. The reaction to be introduced. The detached iodine atom is in a free state (iodine radical), or iodine molecules are generated by recombination of iodine radicals as in reaction formula (5).

  The reaction product containing the polyarylene sulfide resin obtained by melt polymerization contains iodine atoms derived from the raw material. Therefore, the polyarylene sulfide resin is usually used for the preparation of a spinning resin composition in the form of a mixture containing iodine atoms. The density | concentration of the iodine atom in this mixture is the range of 0.01-10000 ppm with respect to polyarylene sulfide resin, for example, Preferably it is the range of 10-5000 ppm. It is also possible to keep the iodine atom concentration low by utilizing the sublimability of iodine molecules. In that case, it is possible to set the range to 900 ppm or less, preferably 100 ppm or less, and further 10 ppm or less. It is. Although it is possible to remove iodine atoms below the detection limit, it is not practical in view of productivity. The detection limit is, for example, about 0.01 ppm. The polyarylene sulfide resin of the present embodiment obtained by melt polymerization or the reaction product containing the same contains iodine atoms, so that, for example, a solution weight of a dichloroaromatic compound such as a Philips method in an organic polar solvent is used. It can be clearly distinguished from polyarylene sulfides obtained by legal methods.

  As can be understood from the above reaction formula, the polyarylene sulfide resin obtained by melt polymerization is mainly composed of an arylene sulfide unit composed of an aromatic ring derived from a diiodo aromatic compound and a sulfur atom directly bonded thereto. It includes a main chain and a predetermined substituent R bonded to the end of the main chain. The predetermined substituent R is bonded to the aromatic ring at the end of the main chain directly or via a partial structure derived from a polymerization inhibitor.

  The polyphenylene sulfide resin as the polyarylene sulfide resin according to one embodiment is, for example, the following general formula (10):

で表される繰り返し単位（アリーレンスルフィド単位）を含む主鎖を有する。式（１０）で表される繰り返し単位は、パラ位で結合する下記式（１０ａ）：

It has a main chain containing a repeating unit (arylene sulfide unit) represented by: The repeating unit represented by the formula (10) has the following formula (10a) bonded at the para position:

で表される繰り返し単位、及び、メタ位で結合する下記式（１０ｂ）：

And the following unit (10b) bonded at the meta position:

で表される繰り返し単位であることがより好ましい。これらの中でも、式（１０ａ）で表されるパラ位で結合した繰り返し単位が、樹脂の耐熱性及び結晶性の面で好ましい。

It is more preferable that it is the repeating unit represented by these. Among these, a repeating unit bonded at the para position represented by the formula (10a) is preferable in terms of heat resistance and crystallinity of the resin.

  The polyphenylene sulfide resin according to one embodiment has the following general formula (11):

（式中、Ｒ^２０及びＲ^２１は、それぞれ独立に水素原子、炭素原子数１〜４のアルキル基、ニトロ基、アミノ基、フェニル基、メトキシ基、又はエトキシ基を表す。）で表される、芳香族環に結合した側鎖としての置換基を有する繰り返し単位を含み得る。ただし、結晶化度及び耐熱性の低下の観点から、ポリフェニレンスルフィド樹脂は、一般式（１１）の繰り返し単位を実質的に含まないことが好ましい。より具体的には、式（１１）で表される繰り返し単位の割合は、式（１０）で表される繰り返し単位と式（１１）で表される繰り返し単位との合計に対して、好ましくは２質量％以下、より好ましくは０．２質量％以下である。

(Wherein R ²⁰ and R ²¹ each independently represent a hydrogen atom, an alkyl group having 1 to 4 carbon atoms, a nitro group, an amino group, a phenyl group, a methoxy group, or an ethoxy group). , May include a repeating unit having a substituent as a side chain bonded to an aromatic ring. However, it is preferable that the polyphenylene sulfide resin does not substantially contain the repeating unit of the general formula (11) from the viewpoints of crystallinity and heat resistance. More specifically, the ratio of the repeating unit represented by formula (11) is preferably based on the total of the repeating unit represented by formula (10) and the repeating unit represented by formula (11). It is 2 mass% or less, More preferably, it is 0.2 mass% or less.

  The polyarylene sulfide resin of the present embodiment is mainly composed of the above-mentioned arylene sulfide units, but usually derived from simple sulfur as a raw material, the following formula (20):

で表されるジスルフィド結合に係る構成単位も主鎖中に含む。耐熱性、機械的強度の点から、式（２０）で表される構成単位の割合は、アリーレンスルフィド単位と、式（２０）で表される構成部位との合計に対して、好ましくは２．９質量％以下の範囲、より好ましくは１．２質量％以下の範囲である。

A structural unit related to a disulfide bond represented by the formula is also included in the main chain. From the viewpoint of heat resistance and mechanical strength, the proportion of the structural unit represented by the formula (20) is preferably 2 with respect to the total of the arylene sulfide unit and the structural site represented by the formula (20). The range is 9% by mass or less, and more preferably 1.2% by mass or less.

  Mw / Mtop of the polyarylene sulfide resin according to this embodiment is preferably in the range of 0.80 to 1.70, more preferably in the range of 0.90 to 1.30. By setting Mw / Mtop in such a range, the processability of the polyarylene sulfide resin can be improved, and a multilayer molded article having a good appearance finish can be produced. In this specification, Mw represents the weight average molecular weight measured by gel permeation chromatography, and Mtop represents the average molecular weight (peak molecular weight) at the point where the detection intensity of the chromatogram obtained by the measurement is maximized. Mw / Mtop indicates the distribution of the molecular weight to be measured. Normally, when this value is close to 1, it indicates that the molecular weight distribution is narrow, and as this value increases, the molecular weight distribution is broad. The measurement conditions for gel permeation chromatography are the same as those in the examples of the present specification. However, it is possible to change the measurement conditions within a range that does not substantially affect the values of Mw and Mw / Mtop.

  The weight average molecular weight of the polyarylene sulfide resin according to this embodiment is not particularly limited as long as the effects of the present invention are not impaired, but the lower limit thereof is 28,000 or more from the viewpoint of excellent mechanical strength. Is more preferable, and the range of 30,000 or more is more preferable. On the other hand, the upper limit is preferably in the range of 100,000 or less, more preferably in the range of 60,000 or less, and further in the range of 55,000 or less from the viewpoint that a better cavity balance can be imparted. Most preferably, it is in the range. Furthermore, from the viewpoint of providing excellent cavity balance while being excellent in mechanical strength, a polyarylene sulfide resin in the range of 28,000 to 60,000, more preferably in the range of 30,000 to 55,000. A polyarylene sulfide resin having a weight average molecular weight in the range of more than 60,000 and 100,000 or less may be used together with the polyarylene sulfide resin.

The non-Newtonian index of the polyarylene sulfide resin is preferably in the range of 0.95 to 1.75, more preferably in the range of 1.00 to 1.70. By setting the non-Newtonian index in such a range, the processability of the polyarylene sulfide resin can be improved, and the appearance finish of the multilayer molded article becomes good. In the present specification, the non-Newtonian index means an index satisfying the following relational expression between the shear rate and the shear stress under the condition of a temperature of 300 ° C. The non-Newtonian index can be an index related to the molecular weight to be measured or the molecular structure such as linear, branched, or crosslinked. Usually, when this value is close to 1, it indicates that the resin molecular structure is linear. It shows that there are many branched and cross-linked structures as the value increases.
D = α × S ⁿ
(In the above formula, D represents shear rate, S represents shear stress, α represents a constant, and n represents a non-Newtonian index.)

  The polyarylene sulfide resin having the above-mentioned specific ranges of Mw / Mtop and non-Newtonian index includes, for example, a diiodo aromatic compound, elemental sulfur, a polymerization inhibitor, a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor. In a method of reacting (solution polymerization) in a molten mixture containing a polyarylene sulfide resin, it can be obtained by increasing the molecular weight of the polyarylene sulfide resin to some extent.

  The melting point of the polyarylene sulfide resin is preferably in the range of 250 to 300 ° C, more preferably in the range of 265 to 300 ° C. The melt viscosity (V6) at 300 ° C. of the polyarylene sulfide resin is preferably in the range of 1 to 2000 [Pa · s], more preferably in the range of 5 to 1700 [Pa · s]. Here, for the melt viscosity (V6), using a flow tester, an orifice having a temperature of 300 ° C., a load of 1.96 MPa, and a ratio of the orifice length to the orifice diameter (orifice length / orifice diameter) is 10/1. The melt viscosity after holding for 6 minutes.

  Examples of the thermoplastic elastomer used in the present embodiment include polyolefin elastomers, fluorine elastomers, and silicone elastomers.

  The thermoplastic elastomer preferably has a functional group capable of reacting with the group represented by the formula (1). Thereby, it is possible to obtain a resin composition that is particularly excellent in terms of adhesion and impact resistance. Such functional groups include epoxy groups, carboxy groups, isocyanate groups, oxazoline groups, and the formula: R (CO) O (CO)-or R (CO) O- (wherein R is from 1 to 8 carbon atoms). A group represented by the following formula: The thermoplastic elastomer having such a functional group can be obtained, for example, by copolymerization of an α-olefin and a vinyl polymerizable compound having a functional group. Examples of the α-olefin include α-olefins having 2 to 8 carbon atoms such as ethylene, propylene, and butene-1. Examples of the vinyl polymerizable compound having a functional group include α, β-unsaturated carboxylic acids such as (meth) acrylic acid and (meth) acrylic acid esters and alkyl esters thereof, maleic acid, fumaric acid, itaconic acid and others. Α, β-unsaturated dicarboxylic acid having 4 to 10 carbon atoms and derivatives thereof (mono- or diester and acid anhydrides thereof), glycidyl (meth) acrylate, and the like. Among these, an epoxy group, a carboxy group, and a formula: R (CO) O (CO)-or R (CO) O- (wherein R represents an alkyl group having 1 to 8 carbon atoms). An ethylene-propylene copolymer and an ethylene-butene copolymer having at least one functional group selected from the group consisting of the represented groups are preferred from the viewpoint of improving toughness and impact resistance.

  The blending ratio of the thermoplastic elastomer in the polyarylene sulfide resin composition is preferably 10 to 20% by mass, more preferably 12 to 18% by mass, and particularly preferably 16 to 18% by mass. . When the blending ratio of the thermoplastic elastomer is within this range, the balance between fuel barrier properties and adhesion is excellent.

  Since the content of the thermoplastic elastomer varies depending on the type and application, it cannot be specified unconditionally. For example, it is preferably in the range of 1 to 300 parts by mass, more preferably 3 to 100 parts by mass of the polyarylene sulfide resin. It is the range of -100 mass parts, More preferably, it is the range of 5-45 mass parts. When the content of the thermoplastic elastomer is within these ranges, a more excellent effect can be obtained in terms of ensuring the heat resistance and toughness of the molded product.

  Examples of the aromatic epoxy resin used in the present embodiment include a bisphenol A type epoxy resin, a bisphenol F type epoxy resin, a bisphenol S type epoxy resin, a biphenyl type epoxy resin, a tetramethylbiphenyl type epoxy resin, and a phenol novolac type epoxy. Resin, cresol novolac type epoxy resin, bisphenol A novolak type epoxy resin, triphenylmethane type epoxy resin, tetraphenylethane type epoxy resin, dicyclopentadiene-phenol addition reaction type epoxy resin, phenol aralkyl type epoxy resin, naphthol novolak type epoxy resin Resin, naphthol aralkyl epoxy resin, naphthol-phenol co-condensed novolac epoxy resin, naphthol-cresol co-condensed novolac epoxy Fat, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, and biphenyl novolak type epoxy resins. These aromatic epoxy resins can be used alone or in combination of two or more. Among these aromatic epoxy resins, a novolak type epoxy resin is preferable and a cresol novolak type epoxy resin is more preferable because it is excellent in adhesion to other resin components.

  The aromatic epoxy resin may have a halogen group, a hydroxyl group or the like, and may be used alone or as a mixture of two or more.

  The blending ratio of the aromatic epoxy resin in the polyarylene sulfide resin composition is preferably 0.1 to 5% by mass, more preferably 0.5 to 4% by mass, and 1 to 3% by mass. It is particularly preferred that If the blending ratio of the aromatic epoxy resin is within this range, the melt stability of the polyarylene sulfide resin composition will be good, and the adhesiveness with the thermoplastic resin when coextruded with the thermoplastic resin will be good. Become.

  In addition to the polyarylene sulfide resin, aromatic epoxy resin, and thermoplastic elastomer described above, the polyarylene sulfide resin composition according to the present embodiment includes various inorganic or organic types within the scope of the present invention. Reinforcing materials, fillers, lubricants, stabilizers and the like can be blended. It is preferable that these compounding quantities are 5 mass% or less in a polyarylene sulfide resin composition.

  A method for producing a polyarylene sulfide resin composition is obtained by mixing a polyarylene sulfide resin, an aromatic epoxy resin, a thermoplastic elastomer, and other compounding components in advance with a Henschel mixer or a tumbler, etc. Examples thereof include a method obtained by supplying to a kneader, kneading at 250 ° C. to 350 ° C., granulating and pelletizing. In particular, the kneader is preferably a biaxial extrusion kneader that rotates in the same direction and is equipped with a kneading disk for kneading from the viewpoint of good uniformity of the composition.

  Specific examples of the thermoplastic resin coextruded with the polyarylene sulfide resin composition include a polycarbonate resin having a hydroxyl group at a molecular end, a polyester resin having a hydroxyl group and a carboxyl group, a polyurethane resin having a hydroxyl group and an isocyanate group, and an epoxy group. , Modified polyolefin having a pendant carboxyl group or acid anhydride group, polyamide resin and the like.

  Specific examples of the polycarbonate resin include polymer carbonates of bifunctional phenol compounds. Examples of the bifunctional phenol compound include bis (4-hydroxyphenyl) methane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 4,4-bis (hydroxyphenyl) heptane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, bis ( 4-hydroxyphenyl) ether, bis (3,5-dichloro-4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, bis (4- Hydroxyphenyl) sulfoxide, bis (3,5-dibromo-4-hydroxyphenyl) sulfoxide Bisphenols; dihydroxybiphenyls such as p, p′-dihydroxybiphenyl and 3,3′-dichloro-4,4′-dihydroxybiphenyl; resorcinol, hydroquinone, 1,4-dihydroxy-2,5-dichlorobenzene, 1 , 4-dihydroxy-3-methylbenzene and the like.

  Examples of the carbonating agent to be reacted with a bifunctional phenol compound to produce a polycarbonate resin include carbonyl halides such as carbonyl bromide and carbonyl chloride, diphenyl carbonate, di (chlorophenyl) carbonate, di (tolyl carbonate, Examples thereof include carbonate esters such as dinaphthyl carbonate; haloformates such as hydroquinone bischloroformate and ethylene glycol haloformate.

  The polyester resin is preferably an aromatic polyester resin obtained from an aromatic dicarboxylic acid and an aliphatic diol, and in particular, obtained from a dicarboxylic acid and an aliphatic diol in which 60 mol% or more of the dicarboxylic acid component is terephthalic acid. Aromatic polyesters are preferred. Examples of the dicarboxylic acid component other than terephthalic acid include azelaic acid, sebacic acid, adipic acid, and dodecanedicarboxylic acid. On the other hand, examples of the aliphatic diol include ethylene glycol, propylene glycol, 1,4-butanediol, trimethylene glycol, hexamethylene glycol, and cyclohexene dimethanol.

  Specific examples of the polyester resin include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexene dimethylene terephthalate, and the like. Among these, polyethylene terephthalate and polybutylene terephthalate are particularly preferable from the viewpoint of adhesion to the polyarylene sulfide resin composition.

  The polyurethane resin is obtained from polyisocyanate and diol. Examples of the polyisocyanate include 2,4-tolylene diisocyanate, hexamethylene diisocyanate, metaxylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and the like. Examples of the diol include ethylene glycol, propylene glycol, 1,4-butanediol, trimethylene glycol, hexamethylene glycol, and cyclohexene dimethanol.

  Further, the modified polyolefin having an epoxy group, a carboxyl group or an acid anhydride group in a pendant form has a polyolefin as a main chain and has an epoxy group, a carboxyl group or an acid anhydride group in a pendant form on its side chain. .

  Specific examples of the polyolefin containing an epoxy group include a copolymer of glycidyl (meth) acrylate such as glycidyl acrylate and glycidyl methacrylate and an α-olefin, and a carboxyl group or an acid anhydride group. Examples of the polyolefin to be contained include those obtained by reacting a polyolefin resin with maleic acid, succinic acid, phthalic acid or acid anhydrides thereof.

  Examples of the α-olefin include ethylene, propylene, butene-1, 4-methylpentene-1, hexene 1, decene-1, octene-1, and the like.

  Examples of the polyamide resin include amino acid compounds, polymers of lactam compounds, or polycondensates of diamine compounds and dicarboxylic acid compounds. Examples of amino acid compounds include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, and the like. Examples of the lactam compound include ε-aminocaprolactam and ω-laurolactam.

  The diamine compound used in the polycondensate of the diamine compound and the dicarboxylic acid compound is tetramethylene diamine, hexamethylene diamine, undecamethylene diamine, dodecamethylene diamine, 2,2,4-trimethylhexamethylene diamine, 2, 4, Aliphatic diamines such as 4-trimethylhexamethylenediamine and 5-methylnonamethylenediamine; 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-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (aminopropyl) piperazine Aminoethyl pipera Alicyclic diamines such emissions; metaxylene diamine, and aromatic diamine para-xylylenediamine, and the like.

  On the other hand, dicarboxylic acid compounds are aliphatic dicarboxylic acids such as adipic acid, speric acid, azelaic acid, sebacic acid, dodecanedioic acid, terephthalic acid, isophthalic acid, 2-chloroterephthalic acid, 2-methylterephthalic acid, 5-methyl Aromatic dicarboxylic acids such as isophthalic acid, 5-sodium sulfoisophthalic acid, hexahydroterephthalic acid, hexahydroisophthalic acid and the like can be mentioned.

  Among these, polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polytetramethylene adipamide (polyamide 46) in particular because of its excellent barrier properties and impact resistance to fuels such as gasoline. ), Polyhexamethylene sebamide (polyamide 610), polyhexamethylene dodecanamide (polyamide 612), polydodecanamide (polyamide 12), polyundecanamide (polyamide 11), polyhexamethylene terephthalamide (polyamide 6T), poly Xylylene adipamide (polyamide XD6) is preferred, and polyamide 6, polyamide 66, and polyamide 12 are particularly preferred.

  These polyamide resins have an impact resistance in the range of 1.5 to 7.0, particularly 2.0 to 6.5 in terms of relative viscosity measured at 25 ° C. in a concentrated sulfuric acid solution having a degree of polymerization of 1%. It is preferable from the point which is excellent in property.

  Among the above-described thermoplastic resins, polyamide resin is preferable from the viewpoint of excellent impact resistance and fuel barrier properties particularly in the use of fuel piping members such as fuel tubes.

  The multilayer laminate according to this embodiment is obtained by coextrusion molding of a polyarylene sulfide resin composition and a thermoplastic resin. Here, as a method of co-extrusion molding, when obtaining a tubular molded body such as a fuel tube, the polyarylene sulfide resin composition and the thermoplastic resin are put into an extruder, melt-kneaded, and in a molten state. The method of shape | molding in a laminated tube using the die | dye which can be made to contact is mentioned. Here, the extruder is preferably a uniaxial or biaxial extruder, and is provided with a tube die capable of forming a resin plasticized by each cylinder in a die portion into one multilayer tube. The temperature in the cylinder when the polyarylene sulfide resin composition is melt-kneaded is preferably 280 to 320 ° C., and the temperature in the cylinder when the thermoplastic resin is melt-kneaded is 230 to 270 ° C. Is preferred.

  In the case of obtaining a tube molded body, the layer constitution is such that the inner layer is made of a polyarylene sulfide resin composition (A) layer (hereinafter abbreviated as “(A) layer”), and the outer layer is made of a thermoplastic resin ( B) may have a two-layer structure having a layer (hereinafter abbreviated as “(B) layer”), and further, a three-layer structure in which (A) layer is provided outside (B) layer, Further, a four-layer structure in which the (A) layer is provided outside the (A) layer may be employed. In the present embodiment, a two-layer structure is particularly preferable from the viewpoint of a good balance between impact resistance and fuel barrier properties.

  The thickness per layer in the multilayer laminate according to the present embodiment varies depending on the application. For example, when used for a fuel tube, the total thickness of the tubular molded body is preferably 0.8 to 1.2 mm. The ratio of the thickness of one layer of the (A) layer and the thickness of the one layer of the (B) layer is (A) layer / (B) layer = 10/90 to 40/60. From the point of balance with the nature.

  In order to obtain molded articles such as fuel tanks and containers as a multilayer laminate according to this embodiment, a polyarylene sulfide resin composition and a thermoplastic resin are coextruded into a multilayer sheet, and a roll stretching method or a tenter stretching method is used. In addition to the tubular stretching method, the stretch blow method, etc., it can be produced by shaping by a forming method such as deep drawing or vacuum forming. In applications such as fuel tanks and containers, it is preferable from the viewpoint of fuel barrier properties that the liquid contact surface side with the fuel or the like is the (A) layer and the outer side is the (B) layer.

  The multilayer molded body according to the present embodiment is suitable for piping members, containers, and fuel tubes used for fluid transportation of organic substances such as fuel. As specific applications, for example, pipes and lining pipes are used. , Cap nuts, pipe joints (elbow, header, cheese, reducer, joint, coupler, etc.), various valves, flow meters, gaskets (seal, packing), etc. Various parts; housings such as fuel pumps and canisters; and fuel tanks. Moreover, the multilayer molded body according to the present embodiment may be combined with other materials by combining with other materials, bonding, caulking, or the like.

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

1. Polyphenylene sulfide resin (PPS resin)
1-1. Synthesis of PPS-1 to 5 (Synthesis Example 1)
30-0.0 g of p-diiodobenzene (Tokyo Kasei Co., Ltd., p-diiodobenzene purity of 98.0% or more), solid sulfur (manufactured by Kanto Chemical Co., Inc., sulfur (powder)) 27.00 g, 4,4′- 2.0 g of dithiobisbenzoic acid (4,4′-dithiobisbenzoic acid, Technical Grade, manufactured by Wako Pure Chemical Industries, Ltd.) was heated to 180 ° C. in a nitrogen atmosphere, and these were dissolved and mixed. Next, the temperature was raised to 220 ° C., and the pressure was reduced to an absolute pressure of 26.6 kPa. Melt polymerization was carried out for 8 hours while heating the obtained molten mixture while changing the temperature and pressure stepwise so that the inside pressure was 320 ° C. and the absolute pressure was 133 Pa. After completion of the reaction, 200 g of NMP was added, and the mixture was heated and stirred at 220 ° C., and the resulting dissolved product was filtered. 320 g of NMP was added to the lysate after filtration, and cake washing filtration was performed. 1 L of ion-exchanged water was added to the obtained cake containing NMP, and the mixture was stirred in an autoclave at 200 ° C. for 10 minutes. Next, the cake was filtered, and 1 L of ion-exchanged water at 70 ° C. was added to the cake after filtration to wash the cake. 1 L of ion-exchanged water was added to the obtained water-containing cake and stirred for 10 minutes. Next, the cake was filtered, and 1 L of ion-exchanged water at 70 ° C. was added to the cake after filtration to wash the cake. After repeating this operation once more, the cake was dried at 120 ° C. for 4 hours to obtain 91 g of PPS resin.

(Synthesis Example 2)
91 g of PPS resin was obtained in the same manner as in Synthesis Example 1 except that “2-iodoaniline (manufactured by Tokyo Chemical Industry Co., Ltd.)” was used instead of “4,4′-dithiobisbenzoic acid”.

(Synthesis Example 3)
91 g of PPS resin was obtained in the same manner as in Synthesis Example 1 except that “diphenyl disulfide (DPDS)” was used instead of “4,4′-dithiobisbenzoic acid”.

(Synthesis Example 4)
30-0.0 g of p-diiodobenzene (manufactured by Tokyo Chemical Industry Co., Ltd., p-diiodobenzene purity of 98.0% or more), 29.15 g of solid sulfur (manufactured by Kanto Chemical Co., Ltd., sulfur (powder)), and 4-iodobiphenyl 1.48 g (manufactured by Tokyo Chemical Industry Co., Ltd.) was heated to 180 ° C. in a nitrogen atmosphere, and these were dissolved and mixed. Next, the temperature is raised to 220 ° C., the pressure is reduced to 46.7 kPa, and the temperature and pressure are changed stepwise so that the system has an absolute pressure of 320 Pa at 320 ° C., and the resulting molten mixture is heated. Then, melt polymerization was performed for 8 hours. After completion of the reaction, 200 g of NMP was added, and the mixture was heated and stirred at 220 ° C., and the resulting dissolved product was filtered. 320 g of NMP was added to the lysate after filtration, and cake washing filtration was performed. 1 L of ion-exchanged water was added to the obtained cake containing NMP, and the mixture was stirred in an autoclave at 200 ° C. for 10 minutes. Next, the cake was filtered, and 1 L of ion-exchanged water at 70 ° C. was added to the cake after filtration to wash the cake. 1 L of ion-exchanged water was added to the obtained water-containing cake and stirred for 10 minutes. Next, the cake was filtered, and 1 L of ion-exchanged water at 70 ° C. was added to the cake after filtration to wash the cake. After repeating this operation once more, the cake was dried at 120 ° C. for 4 hours to obtain 91 g of PPS resin.

(Comparative synthesis example)
An autoclave was charged with 600 g of NMP and 336.3 g (2.0 mol) of sodium sulfide pentahydrate, and the temperature was raised to 200 ° C. under a nitrogen atmosphere to distill off the water-NMP mixture. Next, a solution prepared by dissolving 292.53 g of p-dichlorobenzene and 1.62 g of 2,5-dichloroaniline in 230 g of NMP was added to this system, and reacted at 220 ° C. for 5 hours and further at 240 ° C. for 2 hours in a nitrogen atmosphere. After cooling the reaction vessel, the contents were taken out, a part was sampled, and unreacted 2,5-dichloroaniline was quantified with a gas chromatograph. The remaining slurry was washed several times with hot water, and the polymer cake was filtered off. This cake was dried under reduced pressure at 80 ° C. to obtain a powdery PPS resin. When an infrared absorption spectrum was measured, an absorption spectrum that was considered to be derived from an amino group was observed in the vicinity of 3380 cm ⁻¹ .

1-2. Melt viscosity The PPS resin was measured for 6 minutes using a flow tester manufactured by Shimadzu Corporation, CFT-500C at 300 ° C., load: 1.96 × 10 ⁶ Pa, L / D = 10/1, and then the melt viscosity was measured. .

1-3. Non-Newtonian index PPS resin was measured with a capillary rheometer at a temperature of 300 ° C. using a die having a diameter of 1 mm and a length of 40 mm, and a shear stress with respect to a shear rate of 100 to 1000 (sec ⁻¹ ). Is a value calculated from the slope of the logarithm plot.

1-4. Mw and Mw / Mtop (molecular weight distribution)
The weight average molecular weight and peak molecular weight of the PPS resin were measured under the following measurement conditions using gel permeation chromatography. Mw / Mtop was calculated from the obtained Mw and Mtop. Six types of monodisperse polystyrene were used for calibration.
Apparatus: Ultra-high temperature polymer molecular weight distribution measuring apparatus (“SSC-7000” manufactured by Senshu Scientific Co., Ltd.)
Column: UT-805L (made by Showa Denko KK)
Column temperature: 210 ° C
Solvent: 1-chloronaphthalene Measurement method: UV detector (360 nm)

  The characteristics of the synthesized PPS-1 to 5 are summarized in Table 1.

2. Polyphenylene sulfide resin composition (PPS compound)
2-1. Raw materials In order to prepare the PPS resin composition, the following materials were prepared.
(Aromatic epoxy resin)
Epoxy resin: Cresol novolac type epoxy resin (manufactured by DIC Corporation, “Epiclon N-695”, epoxy equivalent 214 g / eq, softening point 94 ° C.)
(Thermoplastic elastomer)
ELA-1: Acid-modified ethylene-butene copolymer (Tafmer MH-7020 manufactured by Mitsui Chemicals, Inc.)
ELA-2: Unmodified ethylene-butene copolymer (“Tuffmer A-4085” manufactured by Mitsui Chemicals, Inc.)

2-2. Compound preparation Each raw material was uniformly mixed using a tumbler with the composition shown in Table 2, and then melt-kneaded at 300 ° C using a twin-screw kneading extruder ("TEM-35B" manufactured by Toshiba Machine Co., Ltd.). Thus, a pellet-like compound was obtained.

3. Evaluation 3-1. Production of Test Piece for Gas Permeation Coefficient Measurement The polyarylene sulfide resin composition prepared above was molded by an injection molding machine to produce a plate 50 mm long × 100 mm wide × 2 mm thick. Next, this plate was thinly processed by a melt press to produce a film having a thickness of 0.3 mm. This film was used as a test piece for gas permeability coefficient measurement.

3-2. Fuel barrier property About the film produced above, the gas permeation coefficient (unit: mol · mol) of fuel C / ethanol = 90/10 (volume%), fuel C; toluene / isooctane = 50/50 (volume%)) m / m2 · s · Pa) in accordance with JIS K7126 A method, using a gas permeability / moisture permeability measuring device (“GTR-30VAD” manufactured by GTR Tech Co., Ltd.) as a measuring device, and a GC detecting unit as a corporation Measurement was performed by differential pressure GC detection using “GC-14A” manufactured by Shimadzu Corporation. Moreover, the fuel barrier property was evaluated according to the following criteria from the value of the gas permeability coefficient obtained by the measurement.
A: Gas permeability coefficient is less than 1.0 × 10 ⁻¹⁵ mol · m / m ² · s · Pa.
○: Gas permeability coefficient is 1.0 × 10 ⁻¹⁵ mol · m / m ² · s · Pa or more.

3-3.2 Production of two-layer tube A tube that has two plasticizing cylinders (inner diameter 20 mmφ, single-screw extrusion screw) and can unite the plasticized plastic in each cylinder at the die part into one two-layer tube Using a two-layer tube manufacturing apparatus having a die for production, polyamide 12 (“Grillamide L25W40” manufactured by Ms Chemie Japan Co., Ltd .; gas permeability coefficient 5.7 × 10 −14 mol · m / m 2 • s · Pa), the polyarylene sulfide resin composition prepared above is put into the plasticizing cylinder on the inner layer side, the tube is extruded at a temperature of 250 ° C. on the outer layer side and a temperature of 300 ° C. on the inner layer side, and wound. The take-up speed was adjusted to produce a two-layer tube having an outer diameter of 8 mmφ and an inner diameter of 6 mmφ. These two-layer tubes had an inner layer thickness of 0.3 mm and an outer layer thickness of 0.8 mm.

3-4. Adhesiveness Using the two-layer tube produced above, the tube was cut open in the length direction to form a sheet, and the sheet was cut to a width of 10 mm, and peel strength (unit: kN / m) was measured according to ISO-11339. Moreover, the adhesiveness was evaluated according to the following criteria from the peel strength value obtained by the measurement.
○: Peel strength is 2.0 kN / m or more.
Δ: Peel strength is 1.0 kN / m or more and less than 2.0 kN / m.
X: Peel strength is less than 1.0 kN / m.

3-5. Generated Gas Amount Using a gas chromatograph mass spectrometer, for a single PPS resin and a PPS compound, a predetermined amount of sample was heated at 325 ° C. for 15 minutes, and the amount of generated gas at that time was quantified as mass%.

  As is clear from the results shown in Table 2, the multilayer molded body produced in the example can suppress the generation of gas due to heating, and has high fuel barrier properties, and also has good adhesion between the layers of the multilayer molded body. Excellent.

Claims (13)

A polyarylene sulfide resin composition comprising a polyarylene sulfide resin, an aromatic epoxy resin and a thermoplastic elastomer as essential components, and an amino group, an amide group, a hydroxyl group, a carboxyl group, an acid anhydride group, an isocyanate group and an epoxy group. A multilayer molded body having a multilayer structure obtained by coextrusion molding with a thermoplastic resin having one or more functional groups selected from the group,
The polyarylene sulfide resin comprises reacting a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor in a molten mixture containing the diiodo aromatic compound, the elemental sulfur, and the polymerization inhibitor. A multilayer molded article that can be obtained by   The multilayer molded body according to claim 1, wherein the polyarylene sulfide resin has at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxyl group, and a carboxyl group salt derived from the polymerization inhibitor.   The polyarylene sulfide resin is
  In the main chain, the following general formula (20)

The multilayer molded article according to claim 1, which is a mixture containing iodine atoms at a ratio of 0.01 to 10,000 ppm with respect to the polyarylene sulfide resin having a disulfide bond represented by: . In the main chain, the following general formula (20)

A polyarylene sulfide resin having a disulfide bond represented by:
  The following general formula (1-1)

(Wherein Y is a hydroxy group or an amino group), or a monovalent group represented by the following general formula (2-1)

The multilayer molded body according to claim 3, which has a monovalent group represented by: In the main chain, the following general formula (20)

A polyarylene sulfide resin having a disulfide bond represented by:
  The following general formula (a)

A monovalent group represented by the following general formula (b)

Or a monovalent group represented by the following general formula (c)

  (However, X in the general formulas (a) to (c) is a hydrogen atom or an alkali metal atom. In the general formula (b), R is ¹⁰ Represents an alkyl group having 1 to 6 carbon atoms. In general formula (c), R ¹¹ Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹² Represents an alkyl group having 1 to 5 carbon atoms. The multilayer molded article according to claim 3, which has a monovalent group represented by The polyarylene sulfide resin has a non-Newtonian index of 0.95 to 1.75 at 300 ° C. and a Mw / Mtop of 0.80 to 1.70;
The multilayer molded article according to claim 1, wherein Mw and Mtop are respectively a weight average molecular weight and a peak molecular weight measured by gel permeation chromatography. The multilayer molded body according to claim 1, wherein the thermoplastic resin is an aliphatic polyamide. A fuel component comprising the multilayer molded article according to any one of claims 1 to 7 .   A polyarylene sulfide resin composition comprising a polyarylene sulfide resin, an aromatic epoxy resin, and a thermoplastic elastomer as essential components, and an amino group, an amide group, a hydroxyl group, a carboxyl group, an acid anhydride group, an isocyanate group, and an epoxy group. A method for producing a multilayer molded article having a multilayer structure, which comprises co-extrusion molding with a thermoplastic resin having one or more functional groups selected from the group,
  The polyarylene sulfide resin comprises reacting a diiodo aromatic compound, elemental sulfur, and a polymerization inhibitor in a molten mixture containing the diiodo aromatic compound, the elemental sulfur, and the polymerization inhibitor. A method for producing a multilayer molded article, characterized by being obtained by:   The multilayer molded body according to claim 9, wherein the polyarylene sulfide resin has at least one group selected from the group consisting of a hydroxy group, an amino group, a carboxyl group, and a carboxyl group salt derived from the polymerization inhibitor. Production method.   The polyarylene sulfide resin has a non-Newtonian index of 0.95 to 1.75 at 300 ° C. and a Mw / Mtop of 0.80 to 1.70;
  The method for producing a multilayer molded article according to claim 9, wherein Mw and Mtop are respectively a weight average molecular weight and a peak molecular weight measured by gel permeation chromatography.   The polymerization inhibitor is the following general formula (1) or the following general formula (2):

The manufacturing method of the multilayer molded object of Claim 9 which is a compound represented by (In formula, Y is a hydroxy group or an amino group.). The polymerization inhibitor is represented by the following general formula (3), (4) or (5)

[In formula, in general formula (3), R ¹ And R ² Each independently represents a hydrogen atom or a monovalent group represented by the following general formula (a), (b) or (c); ¹ Or R ² At least one of these is a monovalent group represented by the general formula (a), (b) or (c). In the general formula (4), Z represents an iodine atom or a mercapto group, and R ³ Represents the monovalent represented by the following general formula (a), (b) or (c). In general formula (5), R ⁴ Represents a monovalent group represented by the general formula (a), (b) or (c).

  (However, X in the general formulas (a) to (c) is a hydrogen atom or an alkali metal atom. In the general formula (b), R is ¹⁰ Represents an alkyl group having 1 to 6 carbon atoms. In general formula (c), R ¹¹ Represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms, and R ¹² Represents an alkyl group having 1 to 5 carbon atoms. The manufacturing method of the multilayer molded object of Claim 9 containing the compound represented by this.