WO2015030138A1 - Corps moulé multicouche, et élément de carburant l'utilisant - Google Patents

Corps moulé multicouche, et élément de carburant l'utilisant Download PDF

Info

Publication number
WO2015030138A1
WO2015030138A1 PCT/JP2014/072637 JP2014072637W WO2015030138A1 WO 2015030138 A1 WO2015030138 A1 WO 2015030138A1 JP 2014072637 W JP2014072637 W JP 2014072637W WO 2015030138 A1 WO2015030138 A1 WO 2015030138A1
Authority
WO
WIPO (PCT)
Prior art keywords
group
polyarylene sulfide
resin
sulfide resin
multilayer
Prior art date
Application number
PCT/JP2014/072637
Other languages
English (en)
Japanese (ja)
Inventor
芳野　泰之
渡辺　創
俊男 檜森
Original Assignee
Dic株式会社
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dic株式会社 filed Critical Dic株式会社
Priority to JP2015534309A priority Critical patent/JP6210341B2/ja
Priority to KR1020167007668A priority patent/KR20160048129A/ko
Priority to CN201480048068.5A priority patent/CN105517797B/zh
Publication of WO2015030138A1 publication Critical patent/WO2015030138A1/fr

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/16—Articles comprising two or more components, e.g. co-extruded layers
    • B29C48/18—Articles comprising two or more components, e.g. co-extruded layers the components being layers
    • B29C48/21—Articles comprising two or more components, e.g. co-extruded layers the components being layers the layers being joined at their surfaces
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B1/00—Layered products having a non-planar shape
    • B32B1/08—Tubular products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • B32B27/286—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42 comprising polysulphones; polysulfides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/15—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state
    • B32B37/153—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer being manufactured and immediately laminated before reaching its stable state, e.g. in which a layer is extruded and laminated while in semi-molten state at least one layer is extruded and immediately laminated while in semi-molten state
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
    • B29C48/03—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the shape of the extruded material at extrusion
    • B29C48/09—Articles with cross-sections having partially or fully enclosed cavities, e.g. pipes or channels
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/003—PET, i.e. poylethylene terephthalate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2077/00—Use of PA, i.e. polyamides, e.g. polyesteramides or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2081/00—Use of polymers having sulfur, with or without nitrogen, oxygen or carbon only, in the main chain, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2081/00—Use of polymers having sulfur, with or without nitrogen, oxygen or carbon only, in the main chain, as moulding material
    • B29K2081/04—Polysulfides, e.g. PPS, i.e. polyphenylene sulfide or derivatives thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2009/00—Layered products
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2023/00—Tubular articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
    • B29L2031/00—Other particular articles
    • B29L2031/712—Containers; Packaging elements or accessories, Packages
    • B29L2031/7172—Fuel tanks, jerry cans
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2274/00—Thermoplastic elastomer material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2439/00—Containers; Receptacles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2597/00—Tubular articles, e.g. hoses, pipes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles

Definitions

  • the present invention relates to a multilayer molded body suitable for piping members, containers, and tubes used for fluid transportation of organic substances such as fuel.
  • 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.
  • 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.
  • polyphenylene sulfide resin has attracted attention as a resin material having a very high barrier property against alcohol-containing gasoline.
  • 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).
  • the multilayer structure has a problem that the barrier property is remarkably lowered due to easy peeling between layers.
  • the barrier property is remarkably lowered due to easy peeling between layers.
  • 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).
  • Patent Document 3 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.
  • 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.
  • a multilayer structure in which a polyphenylene sulfide resin layer containing 10 to 150 parts by weight of at least one of the above and a polyamide layer are multilayered without using an adhesive layer (see, for example, Patent Document 4) .
  • 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.
  • 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.
  • 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.
  • the present invention relates to a polyarylene sulfide resin composition
  • 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 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.
  • 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.
  • 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.
  • 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”).
  • 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.
  • 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 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 in the range of 0.001 to 1% by 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 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.
  • the polymerization inhibitor may have the functional group, or the functional group may be generated by a polymerization termination reaction or the like.
  • polymerization inhibitor having a hydroxy group or an amino group for example, a compound represented by the following formula (1) or (2) can be used as the polymerization inhibitor.
  • a monovalent group represented by the following formula (1-1) is introduced as a terminal group of the main chain.
  • Y in the formula (1-1) is a hydroxy group, an amino group or the like derived from a polymerization inhibitor.
  • 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.
  • the disulfide bond that is 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.
  • polymerization inhibitor having a carboxyl group for example, one or more compounds selected from the compounds represented by the following general formula (3), (4) or (5) may be used.
  • 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).
  • Z represents an iodine atom or a mercapto group
  • R 3 represents a monovalent group represented by the following General Formula (a), (b), or (c).
  • R 4 represents a monovalent group represented by General Formula (a), (b), or (c).
  • 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.
  • the alkali metal atom include sodium, lithium, potassium, rubidium, and cesium, and sodium is preferable.
  • R 10 represents an alkyl group having 1 to 6 carbon atoms.
  • R 11 represents a hydrogen atom or an alkyl group having 1 to 3 carbon atoms
  • R 12 represents an alkyl group having 1 to 5 carbon atoms.
  • a monovalent group represented by the following formula (6) or (7) is introduced as a terminal 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).
  • R 5 represents a monovalent group represented by the general formula (a), (b) or (c)).
  • R 6 represents a monovalent group represented by the general formula (a), (b) or (c)).
  • 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 moles, more preferably in the range of 0.8 to 1.2 moles per mole 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 of adding the polymerization inhibitor is not particularly limited, but the temperature of the mixture is preferably 200 ° C. to 320 ° C. by heating the mixture containing the diiodo aromatic compound, elemental sulfur and the catalyst to be added as necessary.
  • the polymerization inhibitor can be added when the temperature is within the range, more preferably within the range of 250 to 320 ° C.
  • the polymerization rate can be adjusted by adding a nitro compound as a catalyst to the molten mixture.
  • a nitro compound as a catalyst
  • various nitrobenzene derivatives can be usually used.
  • 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 is preferably in the range of 0.01 to 20 parts by mass with respect to 100 parts by mass of elemental sulfur, for example.
  • 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 polyarylene sulfide resin to be formed + 100 ° C. or lower, more preferably 180 to 350 ° C.
  • the melt polymerization is carried out with an absolute pressure of preferably 1 [cPa] to 100 [kPa], more preferably 13 [cPa] to 60 [kPa].
  • the conditions for melt polymerization need not be constant.
  • 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 higher, the melting point of the polyarylene sulfide resin to be produced + 100 ° C. or lower, more preferably 300 to 350 ° C.,
  • the polymerization can be carried out at an absolute pressure in the range of 1 [cPa] to 6 [kPa].
  • the melting point of the resin means a value measured in accordance with JIS K 7121 using a differential scanning calorimeter (Perkin Elmer DSC device Pyris Diamond).
  • 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.
  • 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.
  • a melt kneader equipped with a heating device, a decompression device, and a stirring device.
  • the melt kneader include a Banbury mixer, a kneader, a continuous kneader, a single screw extruder, and a twin screw extruder.
  • the molten mixture for melt polymerization does not substantially contain a 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.
  • 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.
  • 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.
  • 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 used for preparing the dissolved product in which the reaction product dissolves is preferably in the range of 90 to 1000 parts by mass with respect to 100 parts by mass of the reaction product containing polyarylene sulfide resin.
  • the range is preferably 200 to 400 parts by mass.
  • a solvent used as a polymerization reaction solvent in solution polymerization such as a Philips method
  • preferable solvents include N-methyl-2-pyrrolidone (hereinafter abbreviated as NMP), N-cyclohexyl-2-pyrrolidone, 2-pyrrolidone, 1,3-dimethyl-2-imidazolidinone, and ⁇ -caprolactam.
  • Aliphatic cyclic amide compounds such as N-methyl- ⁇ -caprolactam, amide compounds such as hexamethylphosphoric triamide (HMPA), tetramethylurea (TMU), dimethylformamide (DMF), and dimethylacetamide (DMA), polyethylene
  • 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-d
  • 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.
  • 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.
  • the polyarylene sulfide resin may be dried in a vacuum or in an inert gas atmosphere such as air or nitrogen. May be. It is also possible to oxidatively crosslink the polyarylene sulfide resin by performing heat treatment in an oxidizing atmosphere having an oxygen concentration in the range of 5 to 30% by volume or under reduced pressure conditions.
  • 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
  • Reaction formula (1) is a reaction in which the —SS— bond in the polymerization inhibitor undergoes radical cleavage at the melting temperature.
  • 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.
  • 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 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 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 concentration of iodine atoms in the mixture is, for example, in the range of 0.01 to 10,000 ppm, preferably in the range of 10 to 5000 ppm with respect to the polyarylene sulfide resin. It is also possible to keep the iodine atom concentration low by utilizing the sublimability of iodine molecules.
  • the range 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 includes an iodine atom. It can be clearly distinguished from polyarylene sulfides obtained by legal methods.
  • 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):
  • the repeating unit represented by the formula (10) has the following formula (10a) bonded at the para position:
  • 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):
  • R 20 and R 21 each independently represents 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).
  • 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 arylene sulfide units, but usually derived from the elemental sulfur of the raw material, the following formula (20):
  • a structural unit related to a disulfide bond represented by the formula is also included in the main chain.
  • 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 the present embodiment is preferably in the range of 0.80 to 1.70, more preferably in the range of 0.90 to 1.30.
  • Mw represents the weight average molecular weight measured by gel permeation chromatography
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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.
  • 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].
  • 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.
  • thermoplastic elastomer examples 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).
  • 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)
  • R (CO) O (CO)-or R (CO) O- wherein R is from 1 to 8 carbon atoms)
  • the thermoplastic elastomer having such a functional group can be obtained, for example, by copolymerization of an ⁇ -olefin and a vinyl polymerizable compound having a functional group.
  • Examples of the ⁇ -olefin include ⁇ -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 ⁇ , ⁇ -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. And ⁇ , ⁇ -unsaturated dicarboxylic acids having 4 to 10 carbon atoms and derivatives thereof (mono- or diesters and acid anhydrides thereof), and glycidyl (meth) acrylates.
  • 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 groups represented are preferable 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. .
  • the balance between fuel barrier properties and adhesion is excellent.
  • thermoplastic elastomer varies depending on the type and application, it cannot be specified unconditionally. It is in the range of ⁇ 100 parts by mass, more preferably in the range of 5 to 45 parts by mass. 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.
  • aromatic epoxy resin used in the present embodiment examples 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.
  • cresol novolac type epoxy resin bisphenol A novolac 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 type epoxy resin, naphthol-phenol co-condensed novolac type epoxy resin, naphthol-cresol co-condensed novolac type epoxy resin Resin, aromatic hydrocarbon formaldehyde resin-modified phenol resin type epoxy resin, and biphenyl novolak type epoxy resins.
  • aromatic epoxy resins can be used alone or in combination of two or more.
  • 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.
  • 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.
  • 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.
  • thermoplastic resin coextruded with the polyarylene sulfide resin composition examples 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.
  • polycarbonate resin examples include polymer carbonates of bifunctional phenol compounds.
  • 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′-dihydroxybiphenyls
  • 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.
  • the dicarboxylic acid component other than terephthalic acid include azelaic acid, sebacic acid, adipic acid, and dodecanedicarboxylic acid.
  • examples of the aliphatic diol include ethylene glycol, propylene glycol, 1,4-butanediol, trimethylene glycol, hexamethylene glycol, and cyclohexene dimethanol.
  • polyester resin examples include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexene dimethylene terephthalate, and the like.
  • polyethylene terephthalate and polybutylene terephthalate are particularly preferable from the viewpoint of adhesion to the polyarylene sulfide resin composition.
  • Polyurethane resin is obtained from polyisocyanate and diol.
  • the polyisocyanate include 2,4-tolylene diisocyanate, hexamethylene diisocyanate, metaxylene diisocyanate, 4,4'-diphenylmethane diisocyanate, and the like.
  • the diol include ethylene glycol, propylene glycol, 1,4-butanediol, trimethylene glycol, hexamethylene glycol, cyclohexene dimethanol and the like.
  • 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. .
  • polyolefin containing an epoxy group examples include a copolymer of glycidyl (meth) acrylate such as glycidyl acrylate and glycidyl methacrylate and an ⁇ -olefin.
  • a carboxyl group or an acid anhydride group may be used.
  • the polyolefin to be contained include those obtained by reacting a polyolefin resin with maleic acid, succinic acid, phthalic acid or acid anhydrides thereof.
  • ⁇ -olefin examples include ethylene, propylene, butene-1,4-methylpentene-1, hexene 1, decene-1, octene-1, and the like.
  • polyamide resin examples include a polymer of an amino acid compound, a lactam compound, or a polycondensate of a diamine compound and a dicarboxylic acid compound.
  • amino acid compounds include 6-aminocaproic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, paraaminomethylbenzoic acid, and the like.
  • lactam compound examples include ⁇ -aminocaprolactam and ⁇ -laurolactam.
  • the diamine compound used in the polycondensate of diamine compound and 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 pipette Alicyclic diamines such as gin; metaxylene diamine
  • dicarboxylic acid compounds include 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.
  • 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
  • polycaproamide polyamide 6
  • polyhexamethylene adipamide polyamide 66
  • polytetramethylene adipamide polyamide 46
  • Polyhexamethylene sebamide polyamide 610
  • polyhexamethylene dodecanamide polyamide 612
  • polydodecanamide polyamide 12
  • polyundecanamide polyamide 11
  • polyhexamethylene terephthalamide polyamide 6T
  • poly Xylylene adipamide polyamide XD6
  • polyamide 6, polyamide 66, and polyamide 12 are particularly preferred.
  • 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%. From the point of being excellent in property.
  • 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.
  • 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.
  • dye which can be made to contact is mentioned.
  • 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.
  • 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.
  • 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.
  • the total thickness of the tubular molded body is preferably 0.8 to 1.2 mm.
  • 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.
  • a roll stretching method or a tenter stretching method is used.
  • the stretch blow method, etc. it can be produced by shaping by a forming method such as deep drawing or vacuum forming.
  • 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.
  • 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.
  • 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.
  • 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 (sulfur (powder) manufactured by Kanto Chemical Co., Inc.) 27.00 g, 4,4′- Dithiobisbenzoic acid (4,4′-dithiobisbenzoic acid, Technical Grade, manufactured by Wako Pure Chemical Industries, Ltd.) (2.0 g) was heated to 180 ° C. in a nitrogen atmosphere, and these were dissolved and mixed.
  • PPS resin Polyphenylene sulfide resin
  • 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.
  • 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.
  • 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.
  • 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.
  • 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 for a shear rate of 100 to 1000 (sec ⁇ 1 ). Is a value calculated from the slope of the logarithm plot.
  • 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 analyzer ("SSC-7000" manufactured by Senshu Kagaku Co., Ltd.) Column: UT-805L (made by Showa Denko KK) Column temperature: 210 ° C Solvent: 1-chloronaphthalene Measurement method: UV detector (360 nm)
  • PPS compound Polyphenylene sulfide resin composition
  • Epoxy resin Cresol novolac type epoxy resin (manufactured by DIC Corporation, “Epiclon N-695”, epoxy equivalent 214 g / eq, softening point 94 ° C.)
  • Epoxy resin Cresol novolac type epoxy resin (manufactured by DIC Corporation, “Epiclon N-695”, epoxy equivalent 214 g / eq, softening point 94 ° C.)
  • 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.)
  • 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.
  • the fuel barrier property was evaluated according to the following criteria from the value of the gas permeability coefficient obtained by the measurement.
  • the take-up speed was adjusted to produce a two-layer tube having an outer diameter of 8 mm ⁇ and an inner diameter of 6 mm ⁇ .
  • These two-layer tubes had an inner layer thickness of 0.3 mm and an outer layer thickness of 0.8 mm.
  • 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. ⁇ : 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.
  • 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.

Landscapes

  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polymers With Sulfur, Phosphorus Or Metals In The Main Chain (AREA)
  • Laminated Bodies (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Rigid Pipes And Flexible Pipes (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention porte sur un corps moulé multicouche utilisé comme élément de tuyauterie, comme récipient ou comme tube, ou analogue, qui est utilisé pour transporter des substances organiques fluides telles que des carburants, et qui est apte à éliminer la quantité de gaz générés en résultat d'un chauffage, lequel corps moulé multicouche présente des propriétés adhésives supérieures à celles d'autres éléments en résine, sans compromettre les excellentes propriétés de barrière intrinsèque d'une résine de poly(sulfure d'arylène) par rapport aux substances organiques fluides. Plus précisément, la présente invention porte sur un corps moulé multicouche pourvu d'une structure multicouche obtenue par moulage par co-extrusion de : une composition de résine de poly(sulfure d'arylène) ayant, comme éléments essentiels de cette dernière, une résine de poly(sulfure d'arylène), une résine époxy aromatique, et un élastomère thermoplastique ; et une résine thermoplastique ayant un groupe fonctionnel spécifique. Le corps moulé multicouche peut être obtenu à l'aide d'un procédé comprenant une étape dans laquelle la résine de poly(sulfure d'arylène) est soumise à une réaction dans un mélange fondu comprenant un composé di-iodo-aromatique, du soufre élémentaire, et un inhibiteur de polymérisation.
PCT/JP2014/072637 2013-08-30 2014-08-28 Corps moulé multicouche, et élément de carburant l'utilisant WO2015030138A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP2015534309A JP6210341B2 (ja) 2013-08-30 2014-08-28 多層成形体及びそれを用いた燃料用部品
KR1020167007668A KR20160048129A (ko) 2013-08-30 2014-08-28 다층 성형체 및 그것을 사용한 연료용 부품
CN201480048068.5A CN105517797B (zh) 2013-08-30 2014-08-28 多层成形体和使用了其的燃料用部件

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013-179655 2013-08-30
JP2013179655 2013-08-30

Publications (1)

Publication Number Publication Date
WO2015030138A1 true WO2015030138A1 (fr) 2015-03-05

Family

ID=52586686

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/072637 WO2015030138A1 (fr) 2013-08-30 2014-08-28 Corps moulé multicouche, et élément de carburant l'utilisant

Country Status (4)

Country Link
JP (2) JP6210341B2 (fr)
KR (1) KR20160048129A (fr)
CN (1) CN105517797B (fr)
WO (1) WO2015030138A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10822457B2 (en) 2015-11-23 2020-11-03 Sk Chemicals Co., Ltd. Polyarylene sulfide resin and preparation method thereof

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP6718232B2 (ja) * 2013-09-26 2020-07-08 Dic株式会社 ポリアリーレンスルフィド樹脂組成物及びその成形品、並びに表面実装電子部品
KR20210134346A (ko) * 2019-03-15 2021-11-09 디아이씨 가부시끼가이샤 절연 필름, 접착 필름 및 플랫 케이블
JP7262272B2 (ja) * 2019-03-28 2023-04-21 株式会社オートネットワーク技術研究所 コネクタ装置

Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03506047A (ja) * 1988-07-15 1991-12-26 イーストマン ケミカル カンパニー 末端停止コポリ（アリーレンスルフィド）
JPH04506228A (ja) * 1989-06-12 1992-10-29 イーストマン コダック カンパニー 低分子量の反応停止コポリ（アリーレンスルフィド）
JP2001278951A (ja) * 2000-03-31 2001-10-10 Dainippon Ink & Chem Inc ポリアリーレンスルフィド組成物
JP2010501661A (ja) * 2006-08-24 2010-01-21 エスケー ケミカルズ カンパニー リミテッド ポリ（アリーレンスルフィド）の製造方法
JP2010515781A (ja) * 2007-01-04 2010-05-13 エスケー ケミカルズ カンパニー リミテッド 明るさに優れたポリアリーレンスルフィド樹脂及びその製造方法
JP2011020401A (ja) * 2009-07-17 2011-02-03 Dic Corp 多層成形体及びそれを用いた燃料用部品
JP2012514068A (ja) * 2008-12-31 2012-06-21 エスケー ケミカルズ カンパニー リミテッド 遊離ヨウ素が低減されたポリアリーレンスルフィドの製造方法

Family Cites Families (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CA1311874C (fr) * 1987-10-19 1992-12-22 Joseph John Watkins Procede pour la preparation de copoly(sulfure d'arylene)
JP2003082122A (ja) * 2001-09-07 2003-03-19 Toray Ind Inc ポリフェニレンスルフィドフィルムとその製造方法およびそれからなるコンデンサー
US9249263B2 (en) * 2010-03-09 2016-02-02 Sk Chemicals Co., Ltd. Recyclable polyarylene sulfide and preparation method thereof
WO2011111983A2 (fr) * 2010-03-10 2011-09-15 에스케이케미칼주식회사 Sulfure de polyarylène à faible dégazage et son procédé de préparation
KR101944898B1 (ko) * 2012-06-11 2019-02-01 에스케이케미칼 주식회사 폴리아릴렌 설파이드 수지 조성물 및 이의 제조 방법
JP6237773B2 (ja) * 2013-08-30 2017-11-29 Dic株式会社 水回り部品用樹脂組成物及び流体用配管
KR20160049537A (ko) * 2013-08-30 2016-05-09 디아이씨 가부시끼가이샤 개스킷용 수지 조성물, 그 제조 방법 및 이차전지용 개스킷

Patent Citations (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH03506047A (ja) * 1988-07-15 1991-12-26 イーストマン ケミカル カンパニー 末端停止コポリ（アリーレンスルフィド）
JPH04506228A (ja) * 1989-06-12 1992-10-29 イーストマン コダック カンパニー 低分子量の反応停止コポリ（アリーレンスルフィド）
JP2001278951A (ja) * 2000-03-31 2001-10-10 Dainippon Ink & Chem Inc ポリアリーレンスルフィド組成物
JP2010501661A (ja) * 2006-08-24 2010-01-21 エスケー ケミカルズ カンパニー リミテッド ポリ（アリーレンスルフィド）の製造方法
JP2010515781A (ja) * 2007-01-04 2010-05-13 エスケー ケミカルズ カンパニー リミテッド 明るさに優れたポリアリーレンスルフィド樹脂及びその製造方法
JP2012514068A (ja) * 2008-12-31 2012-06-21 エスケー ケミカルズ カンパニー リミテッド 遊離ヨウ素が低減されたポリアリーレンスルフィドの製造方法
JP2011020401A (ja) * 2009-07-17 2011-02-03 Dic Corp 多層成形体及びそれを用いた燃料用部品

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US10822457B2 (en) 2015-11-23 2020-11-03 Sk Chemicals Co., Ltd. Polyarylene sulfide resin and preparation method thereof
TWI723082B (zh) * 2015-11-23 2021-04-01 南韓商Ｓｋ化學公司 聚芳硫醚及其製備方法
US11390714B2 (en) 2015-11-23 2022-07-19 Hdc Polyall Co., Ltd. Polyarylene sulfide resin and preparation method thereof

Also Published As

Publication number Publication date
CN105517797B (zh) 2018-04-03
KR20160048129A (ko) 2016-05-03
JP2017052285A (ja) 2017-03-16
JP6210341B2 (ja) 2017-10-11
JP6365637B2 (ja) 2018-08-01
JPWO2015030138A1 (ja) 2017-03-02
CN105517797A (zh) 2016-04-20

Similar Documents

Publication Publication Date Title
JP6365637B2 (ja) 多層成形体及びそれを用いた燃料用部品
JP5454877B2 (ja) 多層成形体及びそれを用いた燃料用部品
JP6836490B2 (ja) ブロー成形された熱可塑性組成物
JP5051428B2 (ja) 多層成形体
US10359129B2 (en) Automotive fuel lines including a polyarylene sulfide
US20150170788A1 (en) Conductive Thermoplastic Compositions for Use in Tubular Applications
JP6655392B2 (ja) ポリアリーレンスルフィド樹脂組成物及びその成形品
EP2836552B1 (fr) Constituants de sulfure de polyarylène pour applications automobiles
TW201418365A (zh) 聚芳硫醚樹脂組合物及其形成之物件
JP2019194341A (ja) 炭化水素取り込みの低い熱可塑性組成物
CN105492538B (zh) 用水部件用树脂组合物及流体用配管
JP2004300272A (ja) 燃料系部品
JP6107959B2 (ja) ポリアリーレンスルフィドフィルム及びその製造方法
TW201510088A (zh) 聚芳硫醚樹脂組成物及其成形品
JP4807175B2 (ja) ポリフェニレンスルフィド樹脂製中空成形体
JP5055922B2 (ja) 多層中空成形体
JP2008173881A (ja) 多層中空成形体
JP4452921B2 (ja) 多層成形体
JP2001221378A (ja) 積層チューブ

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14839290

Country of ref document: EP

Kind code of ref document: A1

ENP Entry into the national phase

Ref document number: 2015534309

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

ENP Entry into the national phase

Ref document number: 20167007668

Country of ref document: KR

Kind code of ref document: A

122 Ep: pct application non-entry in european phase

Ref document number: 14839290

Country of ref document: EP

Kind code of ref document: A1