JP2006009957A - Resin hose for fuel system, and method for manufacturing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a resin hose for a fuel system, capable of achieving excellent interlayer adhesion performance between a layer of metal foil and an inner and an outer layer, and restricting penetration of fuel from a margin part of the metal foil. <P>SOLUTION: On the outer circumference of the inner layer 1 in the form of a cylinder for fuel to flow, an intermediate barrier layer 2 comprising a metal laminate film is wound to form an intermediate barrier layer 2, and on the outer circumference of the intermediate barrier layer 2, the outer layer 3 is formed in this resin hose for a fuel system. The inner layer 1 is formed by using at least either aliphatic polyamide resin or fluorine resin, the intermediate barrier layer 2 is formed by using the metal laminate film comprising a modified tetrafluoroethylene copolymer laminated on one surface or both surfaces of the metal foil, and the outer layer 3 is formed by using aliphatic polyamide resin. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a fuel-based resin hose, and in particular, gasoline, alcohol-mixed gasoline (gasohol), alcohol, hydrogen, light oil, dimethyl ether, diesel fuel, CNG (compressed natural gas), LPG (liquefied petroleum gas), and the like. The present invention relates to a fuel-based resin hose used for transportation of a vehicle fuel and a method for manufacturing the same.

  Due to the increasing global environmental awareness, regulations on the evaporation of hydrocarbons from fuel hoses for automobiles and the like have been strengthened, and in particular, strict transpiration regulations have been legislated in the United States. Under such circumstances, in order to comply with the regulation of hydrocarbon transpiration, a multi-layered hose with improved fuel low permeability by wrapping a metal vapor deposition film or metal foil in a spiral shape has been proposed. Yes.

  As such a hose, the thing of the following structures is proposed, for example.

(1) An inner layer made of rubber and / or a thermoplastic elastomer, a barrier layer made of a vapor-deposited film on which the metal provided via the hot melt layer is deposited on the outer side of the inner layer, and a hot melt on the outer side of the barrier layer A low-permeability hose comprising an outer layer made of rubber and / or a thermoplastic elastomer provided via a layer (see Patent Document 1).

(2) On the outer periphery of the rubber layer (inner layer), a refrigerant barrier layer made of a laminated film having a structure in which a metal foil is laminated between resin layers is formed, a reinforcing layer is formed on the outer periphery, and a rubber layer (outer layer) is further formed on the outer periphery. ) Is formed with a low permeability hose (see Patent Document 2). As the laminated film, for example, a laminated film having a five-layer structure of adhesive layer / polyamide layer / aluminum foil / polyamide layer / adhesive layer is described.
Japanese Patent Laid-Open No. 2001-235068 JP 2001-165358 A

  However, the hoses described in (1) and (2) have the following disadvantages.

(1) Hose: Since a laminated film formed by forming a polyolefin-based hot-melt adhesive such as polypropylene on both surfaces of a barrier layer made of a vapor-deposited film is formed by spirally winding the outer periphery of the inner layer, There is a problem that ethanol-added gasoline is likely to permeate from the interface of the laminated film wound in a spiral (overlap hot melt adhesive layer portion).

(2) Hose: The refrigerant barrier layer made of a laminated film is formed by spirally winding the laminated film around the surface of the rubber layer (inner layer). There is a problem that fuel leaks from the stacking allowance part). The hose has a laminated structure of a rubber layer and a resin layer, and an adhesive layer is formed at the interface because the adhesion between the rubber layer and the resin layer is poor. However, the barrier property is low, and there is a high possibility that the fuel permeates from the adhesion interface.

  The present invention has been made in view of such circumstances, and is a fuel system that is excellent in interlayer adhesion between the metal foil and the inner layer and the outer layer, and can suppress fuel permeation from the overlapping portion of the metal foil. An object is to provide a resin hose and a manufacturing method thereof.

In order to achieve the above object, according to the present invention, an intermediate barrier layer formed by winding a metal laminate film is formed on the outer periphery of a tubular inner layer through which fuel flows, and an outer layer is formed on the outer periphery of the intermediate barrier layer. The inner layer is formed using the following (A), the intermediate barrier layer is formed using the following (B), and the outer layer is the following (C) ) Is a fuel-based resin hose formed using
(A) At least one of an aliphatic polyamide resin and a fluororesin.
(B) A metal laminate film in which a layer made of a modified tetrafluoroethylene copolymer is laminated on one side or both sides of a metal foil.
(C) Aliphatic polyamide resin.

  Further, in the method for producing the fuel-based resin hose, a tubular inner layer is formed by hot-melt extrusion molding the inner layer material mainly composed of (A), and then the metal laminate film is formed on the outer periphery of the inner layer. (B) is wound, and then the outer layer material mainly composed of the above (C) is hot melt-extruded on the outer periphery of the metal laminate film (B), thereby forming the metal laminate film on the outer periphery of the tubular inner layer. A method for producing a fuel-based resin hose in which an intermediate barrier layer made of (B) is formed and a fuel-based resin hose having an outer layer formed on the outer periphery of the intermediate barrier layer is a second gist.

  In order to obtain a fuel-based resin hose that is excellent in interlayer adhesion between the metal foil and the inner layer and the outer layer and that can suppress fuel permeation from the overlapping portion of the metal foil, the present inventors have conducted earnest research. Piled up. As a result, an intermediate barrier layer is formed by winding a metal laminate film in which a layer made of a modified tetrafluoroethylene copolymer (modified TFE copolymer layer) is laminated on one or both sides of a metal foil around the outer periphery of a tubular inner layer In addition, the present inventors have found that the intended purpose can be achieved by the fuel-based resin hose in which the outer layer is formed on the outer periphery of the intermediate barrier layer, and the present invention has been achieved. That is, as described above, an intermediate barrier layer is formed by winding a metal laminate film in which a modified TFE copolymer layer is laminated on one side or both sides of a metal foil. In addition, the modified TFE copolymer layer can suppress fuel permeation from the overlapping portion of the metal foil. In addition, the modified TFE copolymer layer formed on one or both sides of the metal foil is excellent in adhesion to other layers, and therefore, the interlayer adhesion between the modified TFE copolymer layer and the inner and outer layers in contact with the modified TFE copolymer layer. Will be improved.

  Thus, the fuel-based resin hose of the present invention forms the intermediate barrier layer by winding the metal laminate film in which the modified TFE copolymer layer is laminated on one or both surfaces of the metal foil. The foil provides an excellent barrier property against fuel, and the modified TFE copolymer layer can suppress fuel permeation from the overlapping portion of the metal foil. In addition, the modified TFE copolymer layer formed on one or both sides of the metal foil is excellent in adhesion to other layers, and therefore the interlayer adhesion between the modified TFE copolymer layer and the inner and outer layers in contact with the modified TFE copolymer layer. Will improve. Therefore, the metal foil of the metal laminate film can follow the elongation and compression of the inner layer and the outer layer, so that no cracks are generated in the metal foil, and fuel leakage or the like can be prevented.

  Further, according to the method for producing a fuel-based resin hose of the present invention, after forming the inner layer material by hot-melt extrusion molding the inner layer material mainly composed of the above (A), the metal is formed on the outer periphery of the inner layer. The laminate film (B) is wound, and then the outer layer material containing the above (C) as a main component is hot melt-extruded on the outer periphery of the metal laminate film (B), thereby forming the metal on the outer periphery of the tubular inner layer. An intermediate barrier layer made of the laminate film (B) is formed, and a fuel-based resin hose having an outer layer formed on the outer periphery of the intermediate barrier layer can be produced. Thus, the production method of the present invention requires only a resin extrusion process and a metal laminate film (B) winding process, and does not require a conventional adhesive layer forming process. Since a sulfur process or the like is not required, a fuel system resin hose having a multilayer structure can be manufactured very easily.

  In the present invention, the main component means most of the meaning, but includes the case where the whole consists of only the main component.

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

  In the fuel-based resin hose of the present invention, for example, as shown in FIG. 1, an intermediate barrier layer 2 formed by winding a metal laminate film is formed on the outer periphery of a tubular inner layer 1 through which fuel flows. An outer layer 3 is formed on the outer periphery of 2.

In the present invention, the inner layer 1 is formed using the following (A), the intermediate barrier layer 2 is formed using the following (B), and the outer layer 3 is formed using the following (C). This is the biggest feature.
(A) At least one of an aliphatic polyamide resin and a fluororesin.
(B) A metal laminate film in which a layer made of a modified tetrafluoroethylene copolymer is laminated on one side or both sides of a metal foil.
(C) Aliphatic polyamide resin.

  The aliphatic polyamide resin (A) used as a material for forming the inner layer 1 (material for the inner layer) is not particularly limited. For example, polyamide 6 (PA6), polyamide 66 (PA66), polyamide 99 (PA99) ), Polyamide 610 (PA610), polyamide 612 (PA612), polyamide 11 (PA11), polyamide 912 (PA912), polyamide 12 (PA12), a copolymer of polyamide 6 and polyamide 66 (PA6 / 66), polyamide 6 And a copolymer of polyamide 12 (PA 6/12) and the like. These may be used alone or in combination of two or more. Among these, polyamide 6 (PA6), polyamide 11 (PA11), and polyamide 12 (PA12) are preferable from the viewpoints of flexibility and low-temperature impact properties.

  Moreover, there is no limitation in particular as a fluororesin of (A) used as a formation material (inner layer material) of the said inner layer 1, For example, a polytetrafluoroethylene (PTFE), a polyvinylidene fluoride (PVDF), a poly Chlorotrifluoroethylene (CTFE), ethylene-chlorotrifluoroethylene copolymer (ECTFE), ethylene-tetrafluoroethylene copolymer (ETFE), hexafluoropropylene-tetrafluoroethylene copolymer (FEP), tetrafluoroethylene -Perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoroethylene-hexafluoropropylene-vinylidene fluoride copolymer (THV), vinylidene fluoride-hexafluoropropylene copolymer, vinylidene fluoride Chlorotrifluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene copolymer, vinylidene fluoride-tetrafluoroethylene-hexafluoropropylene-perfluoroalkoxy vinyl ether copolymer, tetrafluoroethylene-vinylidene fluoride-hexafluoropropylene -Perfluoroalkoxy vinyl ether copolymer and the like. These may be used alone or in combination of two or more. Among these, ETFE, THV, and PVDF are preferably used in terms of excellent workability.

  The fluororesin may be used in combination with the modified fluororesin or may be used alone.

  In the present invention, the above-mentioned modified fluororesin means the main component of the fluororesin by copolymerizing or graft copolymerizing a comonomer containing a functional group (usually a vinyl compound) or the like during synthesis of the fluororesin, A functional group (modified group) or the like introduced into a chain or a side chain to modify the fluorocarbon resin in the range that does not impair the original characteristics.

  The functional group introduced into the fluororesin is not particularly limited as long as interlayer adhesion is improved. For example, carbonate group, carboxylic acid halide group, carboxyl group, acid anhydride, epoxy group, hydroxyl group, chloro Examples thereof include a methyl group, an isocyanate group, an amino group, and an aldehyde group.

  In the present invention, as the material for the inner layer, an elastomer, a plasticizer, an antiaging agent, and a flame retardant may be appropriately blended together with the specific resin (A). In this case, it is preferable to prepare the inner layer material so that the fuel-based resin hose has calcium chloride (salt cal) resistance and creep resistance and has a tensile elongation of 50% or more, preferably 200% or more. .

  Examples of the elastomer include polyester-based thermoplastic elastomer (TPEE), polyolefin-based thermoplastic elastomer (TPO), polyamide-based thermoplastic elastomer (TPAE), and polystyrene-based thermoplastic elastomer (TPS).

  In the present invention, when the fluororesin is used as the inner layer material, a conductive agent such as carbon black may be added to impart conductivity to the inner layer 1. Thus, when the inner layer 1 is made conductive, even if the fuel flowing through the hose is contact-charged by static electricity generated by a fuel pump or the like, it is possible to prevent the occurrence of fire due to sparks, etc. It can be improved further.

  Next, in the present invention, as a material for forming the intermediate barrier layer 2, a layer (modified TFE copolymer layer) made of a modified tetrafluoroethylene copolymer (modified TFE copolymer) is formed on one or both sides of the metal foil. A laminated metal film is used.

  In addition, in this invention, a film is literally not limited to a planar film, but also means a tape formed by cutting a film into a predetermined width (strip shape, etc.).

  The constituent material of the metal foil in the metal laminate film (B) is not particularly limited. For example, aluminum, aluminum alloy, iron, iron alloy (including stainless steel), copper, copper alloy (including brass and phosphor bronze). ), Nickel, nickel alloy, titanium, titanium alloy and the like. Among these, aluminum, SUS, copper alloy, and the like are preferably used from the viewpoint of corrosion resistance. In addition, in order to improve adhesiveness, for example, pre-bonding treatment such as chromate treatment or embossing may be performed.

  In the present invention, the modified TFE copolymer is a functional group (modified group) such as a carbonyl group introduced into the main chain terminal or side chain terminal of a fluororesin having tetrafluoroethylene (TFE) as the main skeleton. Thus, those modified within the range not impairing the original characteristics of the fluororesin are preferred.

  Examples of the fluororesin having tetrafluoroethylene (TFE) as the main skeleton include those obtained by copolymerizing tetrafluoroethylene (TFE) with a fluorovinyl compound or other fluorine-containing monomer. In addition to these fluorine-containing monomers, monomers obtained by copolymerizing monomers such as ethylene, propylene, 1-butene, 2-butene, vinyl chloride, and vinylidene chloride may be used.

  Examples of the fluorovinyl compound include those represented by the following general formula (1).

  In the fluorovinyl compound represented by the general formula (1), among the fluoroalkyl groups represented by Rf, a perfluoroalkyl group, ω-hydro or ω-chloroperfluoroalkyl group is preferable from the viewpoint of heat resistance. preferable.

  Among the fluorovinyl compounds represented by the above general formula (1), in particular, from the viewpoint of copolymerizability, economic efficiency during production of the monomer, and physical properties of the obtained fluororesin, the following formula (2) The fluorovinyl compound is preferably used.

  Among the fluorovinyl compounds represented by the general formula (2), a fluorovinyl compound in which n is an integer of 3 to 5 is particularly preferably used.

  The fluorine-containing monomer other than the fluorovinyl compound is not particularly limited. For example, hexafluoropropylene (HEP), vinylidene fluoride, chlorotrifluoroethylene (CTFE), hexafluoroisobutylene, hexafluoroacetone, penta Examples include fluoropropylene, trifluoroethylene, and fluoro (alkyl vinyl ether).

  Here, the modified TFE copolymer is composed of tetrafluoroethylene (TFE) 30 to 81 mol% and at least one other monomer 70 to 19 mol%, and the polymer chain end is a carbonate end. Is preferred.

  Among the modified TFE copolymers, tetrafluoroethylene (TFE), ethylene, hexafluoropropylene, and the fluorovinyl compound were polymerized by introducing di-n-propyl peroxydicarbonate. Those are preferred. In such a modified TFE copolymer, the molar ratio of tetrafluoroethylene (TFE) to ethylene is preferably in the range of 40/60 to 90/10, and the content of the fluorovinyl compound is 10 in the entire copolymer. The mol% or less is preferable, and the content of hexafluoropropylene is preferably in the range of 10 to 30 mol% of the entire copolymer.

  Here, the said metal laminated film (B) can be produced with the following two types of manufacturing methods, for example.

(First manufacturing method)
A metal laminate in which a modified TFE copolymer layer composed of the modified TFE copolymer is laminated on one or both sides of a metal foil by melt-extrusion of the modified TFE copolymer on one or both sides of the metal foil A method for producing a film (B).

(Second manufacturing method)
A modified TFE copolymer is melt-extruded in advance to produce a modified TFE copolymer film, and then the film is heat laminated on one or both sides of the metal foil, whereby the modified TFE is formed on one or both sides of the metal foil. A method for producing a metal laminate film (B) comprising a copolymer film laminated thereon.

  In the metal laminate film (B) thus obtained, the thickness of the metal foil is preferably in the range of 3 to 100 μm, particularly preferably in the range of 5 to 50 μm. That is, when the thickness of the metal foil is less than 3 μm, depending on the metal material, when the metal laminate film (B) is produced or when the intermediate barrier layer 2 is formed by winding the metal laminate film (B). This is because the tension may cause the film to break, and conversely, if it exceeds 100 μm, it tends to be difficult to wind the metal laminate film (B) in terms of handling and the like.

  The thickness of the modified TFE copolymer layer in the metal laminate film (B) is preferably in the range of 5 to 500 μm, particularly preferably in the range of 20 to 300 μm. That is, when the thickness of the modified TFE copolymer layer is less than 5 μm, it is difficult to laminate the metal laminate film (B) on the metal foil, and when it exceeds 500 μm, the cost tends to increase. Because it is. In the present invention, the thickness of the modified TFE copolymer layer refers to the film itself when the modified TFE copolymer layer comprises a modified TFE copolymer film as shown in the second production method. The thickness of

  Next, in the present invention, the aliphatic polyamide resin (C) is used as a material for forming the outer layer 3 (outer layer material). The aliphatic polyamide resin is not particularly limited. For example, polyamide 6 (PA6), polyamide 66 (PA66), polyamide 99 (PA99), polyamide 610 (PA610), polyamide 612 (PA612), polyamide 11 (PA11) ), Polyamide 912 (PA912), polyamide 12 (PA12), a copolymer of polyamide 6 and polyamide 66 (PA6 / 66), a copolymer of polyamide 6 and polyamide 12 (PA6 / 12), and the like. These may be used alone or in combination of two or more. Among these, polyamide 11 (PA11) and polyamide 12 (PA12) are preferably used from the viewpoints of flexibility, low temperature impact resistance, weather resistance, and the like.

  Here, as a manufacturing method of the fuel system resin hose of the present invention as shown in FIG. 1, for example, the following three manufacturing methods can be mentioned. That is, a manufacturing method (first manufacturing method) in the case of using a double-sided metal laminate film in which the modified TFE copolymer layer is laminated on both sides of the metal foil, and the modified TFE copolymer layer only on one side of the metal foil. Can be broadly classified into production methods (second production method, third production method) in the case of using a single-sided metal laminate film laminated. In addition, when using the single-sided metal laminate film, interposing an adhesive layer using the modified TFE copolymer described above between the metal foil side of the single-sided metal laminate film and the inner layer or the outer layer, It is preferable from the point of adhesiveness.

(First manufacturing method)
A double-sided metal laminate film in which a modified TFE copolymer layer is laminated on both sides of a metal foil, an inner layer material mainly composed of (A), and an outer layer mainly composed of (C) Prepare each material. Next, the inner layer material is hot melt extruded from an extruder into a hose shape to form a tubular inner layer 1, and then the double-sided metal laminate film is wound around the outer peripheral surface of the inner layer 1 to produce a laminated hose body. To do. Next, the outer layer 3 is formed on the outer peripheral surface of the laminated hose body by subjecting the outer layer material to hot melt extrusion molding from an extruder. Thereby, the fuel hose by which the intermediate | middle barrier layer 2 which consists of a double-sided metal laminate film is formed in the outer peripheral surface of the inner layer 1, and the outer layer 3 is formed in the outer peripheral surface can be produced.

(Second manufacturing method)
A single-sided metal laminate film is produced in which a modified TFE copolymer layer is laminated only on one side of a metal foil. In addition, an inner layer material mainly composed of (A), an outer layer material mainly composed of (C), and an adhesive layer material mainly composed of the modified TFE copolymer are prepared. Next, the forming material of each layer is co-extruded in a hose shape from the extruder for the inner layer and the extruder for the adhesive layer, and an adhesive layer is formed on the outer peripheral surface of the tubular inner layer 1. Subsequently, the laminated hose body is manufactured by winding the outer peripheral surface of the adhesive layer with the modified TFE copolymer layer side of the single-sided metal laminate film as the outer peripheral side (the metal foil side is the inner peripheral side). Next, the outer layer 3 is formed on the outer peripheral surface of the modified TFE copolymer layer of the laminated hose body by subjecting the outer layer material to hot melt extrusion from an extruder. As a result, an intermediate barrier layer 2 made of a single-sided metal laminate film (metal foil on the inner peripheral side and modified TFE copolymer layer on the outer peripheral side) is formed on the outer peripheral surface of the inner layer 1 via the adhesive layer. A fuel hose in which the outer layer 3 is formed can be produced.

(Third production method)
In the same manner as in the second production method, a single-sided metal laminate film is prepared, and an inner layer material, an outer layer material, and an adhesive layer material are prepared. Next, the inner layer material is hot-melt extruded from an extruder into a hose shape to form a tubular inner layer 1. Then, the metal foil side of the single-sided metal laminate film is placed on the outer peripheral side of the inner layer 1. A modified hose body is prepared by winding the modified TFE copolymer layer side on the inner peripheral side. Next, the forming material of each layer is co-extruded on the outer peripheral surface of the metal foil of the laminated hose body from the adhesive layer extruder and the outer layer extruder, and the outer layer 3 is formed on the outer peripheral surface of the adhesive layer. Form. Thereby, on the outer peripheral surface of the inner layer 1, an intermediate barrier layer 2 composed of a single-sided metal laminate film (the inner peripheral side is a modified TFE copolymer layer and the outer peripheral side is a metal foil) is formed, and an adhesive layer is formed on the outer peripheral surface via an adhesive layer. A fuel hose in which the outer layer 3 is formed can be produced.

  The winding method of the metal laminate film (B) is not particularly limited, and examples thereof include a spiral winding method and a vertical winding method (so-called sushi winding).

  In the present invention, when the intermediate barrier layer 2 is formed by winding the metal laminate film (B) in a spiral shape or the like as described above, the overlap margin width of the metal laminate film (B) is from the viewpoint of low fuel permeability. The hose is preferably 1 mm or more after bending. The width of the metal laminate film (B) used for forming the intermediate barrier layer 2 is not particularly limited, but is preferably about 10 mm.

  In the present invention, after the fuel hose is manufactured, it can be bent into a desired shape as necessary. In this bending process, for example, a straight pipe hose is put in a mold having a predetermined shape and heated at a temperature of 200 ° C. or lower (preferably 160 to 200 ° C.) to be melted or heated, or 200 ° C. or lower (preferably It can be carried out by melting and heating with hot air at a temperature of 160 to 200 ° C. If the heat treatment is performed at a temperature of 200 ° C. or less, preferably 160 to 200 ° C. during bending of the hose without performing the heat treatment when winding the metal laminate film (B), the inner layer 1 and the outer layer 3 The metal foil of the metal laminate film (B) can follow the elongation, compression, etc. of the metal foil, so that cracks are not generated in the metal foil, and fuel leakage and the like can be prevented.

  In the fuel-based resin hose of the present invention, the inner diameter of the hose is preferably in the range of 4 to 40 mm, particularly preferably in the range of 6 to 33 mm, and the outer diameter of the hose is preferably in the range of 6 to 50 mm, particularly preferably 8 to. Within the range of 40 mm. The thickness of the inner layer 1 is preferably in the range of 0.1 to 0.5 mm, particularly preferably in the range of 0.1 to 0.3 mm. The thickness of the outer layer 3 is preferably in the range of 0.1 to 0.8 mm, particularly preferably in the range of 0.1 to 0.5 mm. In addition, the thickness of the intermediate barrier layer 2 is appropriately set according to the thickness of the metal foil or modified TFE copolymer layer. When the intermediate barrier layer 2 is formed using a single-sided metal laminate film, the thickness of the adhesive layer interposed between the metal foil side of the single-sided metal laminate film and the inner layer or the outer layer is usually 0.02. Within the range of ~ 0.3 mm.

  Note that the fuel-based resin hose of the present invention is not limited to the three-layer structure as shown in FIG. 1. For example, a conductive innermost layer may be formed on the inner peripheral surface of the inner layer 1. . As the material for forming the conductive innermost layer, for example, a material obtained by blending a predetermined amount of a conductive agent such as carbon black with the above-described fluororesin is used. The conductive innermost layer can be formed by co-extruding a material in a hose shape from an extruder for the conductive innermost layer. In this case, the thickness of the conductive innermost layer is preferably 0.1 mm or less.

  The fuel-based resin hose of the present invention transports automobile fuels such as gasoline, alcohol-mixed gasoline (gasohol), alcohol, hydrogen, light oil, dimethyl ether, diesel fuel, CNG (compressed natural gas), and LPG (liquefied petroleum gas). It can use suitably for etc.

  Next, examples will be described together with comparative examples.

  First, prior to the examples and comparative examples, materials for forming the following layers were prepared.

[PA11]
Lilsan BESN NOIR P20TL, manufactured by Atofina

[PA12]
Ubesta 3030JLX2 made by Ube Industries

[Fluororesin A]
Acid-modified ETFE (Asahi Glass Co., Ltd., Fullon LM-ETFE AH2000)

[Fluororesin B]
ETFE (Asahi Glass Co., Ltd., Full-on C88AP)

[Fluororesin C]
Acid-modified conductive ETFE (Asahi Glass Co., Ltd., Fullon LM-ETFE AH3000)

[Modified TFE Copolymer]
Carbonate modified TFE copolymer (manufactured by Daikin Industries, Neoflon EFEP RP4020, melting point 165 ° C.)

  Next, the fuel hose was produced using the said material.

[Example 1]
A fuel hose was produced using a double-sided metal laminate film according to the first production method. That is, a carbonate-modified TFE copolymer (Daikin Kogyo Co., Ltd., NEOFLON EFEP RP4020, melting point 165 ° C.), which is a modified TFE copolymer, was melt-extruded on one side of a metal foil (SUS304) using a T-die extruder. Then, it was applied to a predetermined thickness with a laminator. Next, a modified TFE copolymer was applied to the other surface of the metal foil (SUS304) to a predetermined thickness in the same manner as described above, and then cut into a 1.2 cm width with a slit, thereby providing a double-sided metal laminate film. Was made. Next, the inner layer material was hot melt extruded from an extruder into a hose shape to form a tubular inner layer, and then a laminated hose body was prepared by winding the double-sided metal laminate film around the outer peripheral surface of the inner layer. Next, the outer layer material was formed on the outer peripheral surface of the laminated hose body by hot melt extrusion molding from an extruder. This produced a fuel hose (inner diameter 6 mm, outer diameter 8 mm) in which an intermediate barrier layer made of a double-sided metal laminate film was formed on the outer peripheral surface of the inner layer, and an outer layer was formed on the outer peripheral surface.

[Examples 2, 3, 5, 6]
A fuel hose (inner diameter 6 mm, outer diameter 8 mm) was prepared in the same manner as in Example 1 except that the material for forming each layer was changed to the material shown in Table 1 below.

Example 4
A fuel hose was produced using a single-sided metal laminate film according to the second production method. That is, a carbonate-modified TFE copolymer (Daikin Kogyo Co., Ltd., NEOFLON EFEP RP4020, melting point 165 ° C.), which is a modified TFE copolymer, was melt-extruded on one side of a metal foil (SUS304) using a T-die extruder. Then, it was applied to a predetermined thickness with a laminator. Next, this was cut into a width of 1.2 cm with a slit to prepare a single-sided metal laminate film. Next, an extruder for the inner layer and an extruder for the adhesive layer A are prepared, and the forming material of each layer is co-extruded in a hose shape from each extruder, and the adhesive layer A is formed on the outer peripheral surface of the tubular inner layer. Formed. Next, the laminated hose body was fabricated by winding the outer peripheral surface of the adhesive layer A with the modified TFE copolymer layer side of the single-sided metal laminate film on the outer peripheral side (the metal foil side being the inner peripheral side). Next, the outer layer material is hot melt extruded from an extruder on the outer peripheral surface of the modified TFE copolymer layer of the laminated hose body to form an outer layer. As a result, an intermediate barrier layer made of a single-sided metal laminate film (metal foil on the inner peripheral side and modified TFE copolymer layer on the outer peripheral side) is formed on the outer peripheral surface of the inner layer via the adhesive layer A, and the outer layer is formed on the outer peripheral surface. A fuel hose (inner diameter 6 mm, outer diameter 8 mm) was formed.

Example 7
The fuel hose (inner diameter: 6 mm, outer diameter: 8 mm) was changed in accordance with Example 1 except that the material for forming each layer was changed to the material shown in Table 1 below and the innermost layer was formed on the inner peripheral surface of the inner layer. Produced.

Example 8
In accordance with the third production method, a fuel hose was produced using a single-sided metal laminate film. That is, a carbonate-modified TFE copolymer (Daikin Kogyo Co., Ltd., NEOFLON EFEP RP4020, melting point 165 ° C.), which is a modified TFE copolymer, was melt-extruded on one side of a metal foil (SUS304) using a T-die extruder. Then, it was applied to a predetermined thickness with a laminator. Next, this was cut into a width of 1.2 cm with a slit to prepare a single-sided metal laminate film. Next, the inner layer material is hot-melt extruded from an extruder into a hose shape to form a tubular inner layer, and the metal foil side of the single-sided metal laminate film is placed on the outer peripheral side (modified TFE) on the outer peripheral surface of the inner layer. The laminated hose body was produced by winding the copolymer layer side on the inner circumference side). Next, an extruder for the adhesive layer B and an extruder for the outer layer are prepared, and the forming material of each layer is co-extruded on the outer peripheral surface of the metal foil of the laminated hose body, An outer layer was formed on the outer peripheral surface of the adhesive layer B. As a result, an intermediate barrier layer made of a single-sided metal laminate film (the inner peripheral side is a modified TFE copolymer layer and the outer peripheral side is a metal foil) is formed on the outer peripheral surface of the inner layer, and the outer layer is formed on the outer peripheral surface via the adhesive layer B. A fuel hose (inner diameter 6 mm, outer diameter 8 mm) was formed.

[Comparative Examples 1 and 2]
A fuel hose was produced according to Example 1 except that an intermediate barrier layer made of a metal laminate film was not formed. That is, the inner layer material, the adhesive layer A material, and the outer layer material shown in Table 2 below were prepared. Next, a forming material for each layer is co-extruded from each extruder into a hose shape, an adhesive layer A is formed on the outer peripheral surface of the tubular inner layer, and an outer layer is formed on the outer peripheral surface. An outer diameter of 8 mm) was produced.

  Using the fuel hoses of Examples and Comparative Examples thus obtained, each characteristic was evaluated according to the following criteria. These results are shown in Tables 3 and 4 below.

[Gasoline permeation]
Both ends of a 10 m long fuel hose (inner diameter 6 mm) were expanded using a conical jig so that the inner diameter of the fuel hose end was 10 mm. In addition, two metal pipes having an outer diameter of 8 mm whose outer periphery is R-treated (but having two bulge-processed portions expanded to an outer diameter of 10 mm) are prepared. Press-fitted one by one. A screw type blind plug was attached to one metal pipe, and a metal valve was attached to the other metal pipe. Next, indole gasoline containing 10% by volume of ethanol is sealed in the fuel hose from the side of the metal pipe fitted with the metal valve, and treated at 40 ° C. for 3000 hours (note that 10% by volume of ethanol is contained every week). Changed the indren gasoline). Then, the gasoline permeation amount was measured for 3 days by the CARB SHED method DBL pattern, and the gasoline permeation amount per 1 m of the fuel hose was calculated on the day when the gasoline permeation amount was the maximum. In the above measurement method, since 0.1 mg / m / day is the measurement limit, a value that was less than 0.1 mg / m / day was expressed as “<0.1”.

(Interlayer adhesion)
Each fuel hose (inner diameter 6 mm) was divided into two in the longitudinal direction, and one of them was used to peel the interface of each layer, and the adhesion (N / cm) was calculated. In the evaluation of interlayer adhesion, a case where the adhesion force was 20 N / cm or more was evaluated as ◯, and a case where the adhesion force was less than 20 N / cm was evaluated as ×.

(Impact resistance)
After leaving each fuel hose at -40 ° C. for 4 hours, in accordance with JASO M317, a falling weight (round bar with a diameter of 32 mm whose tip is processed to R16 mm, weight 450 g) is placed on the fuel hose from a height of 305 mm. A falling weight test was performed. Thereafter, the hose was halved in the longitudinal direction, and the presence or absence of abnormality on the inner and outer surfaces of the fuel hose was checked. In the evaluation, “O” indicates that the inner and outer surfaces of the fuel hose are not cracked, and “X” indicates that the crack is present.

  From the above results, all of the Example products had a small gasoline permeation amount and excellent interlayer adhesion.

  In contrast, Comparative Examples 1 and 2 did not form an intermediate barrier layer made of a specific metal laminate film between the inner layer and the outer layer, so the gasoline permeation amount was very high and the gasoline low permeability. Was significantly inferior.

  The fuel-based resin hose of the present invention transports automobile fuels such as gasoline, alcohol-mixed gasoline (gasohol), alcohol, hydrogen, light oil, dimethyl ether, diesel fuel, CNG (compressed natural gas), and LPG (liquefied petroleum gas). It can use suitably for etc.

It is sectional drawing which shows an example of the fuel type | system | group resin hose of this invention.

Explanation of symbols

1 Inner layer 2 Intermediate barrier layer 3 Outer layer

Claims (9)

A fuel-based resin hose in which an intermediate barrier layer formed by winding a metal laminate film is formed on the outer periphery of a tubular inner layer through which fuel is circulated, and an outer layer is formed on the outer periphery of the intermediate barrier layer. It is formed using the following (A), the intermediate barrier layer is formed using the following (B), and the outer layer is formed using the following (C). Fuel resin hose.
(A) At least one of an aliphatic polyamide resin and a fluororesin.
(B) A metal laminate film in which a layer made of a modified tetrafluoroethylene copolymer is laminated on one side or both sides of a metal foil.
(C) Aliphatic polyamide resin.   The fuel resin hose according to claim 1, wherein the thickness of the metal foil in (B) is set in a range of 3 to 100 µm.   The metal foil in (B) is formed using at least one material selected from the group consisting of aluminum, aluminum alloy, iron, iron alloy, copper, copper alloy, nickel, nickel alloy, titanium and titanium alloy. The fuel-based resin hose according to claim 1 or 2.   The fuel resin hose according to any one of claims 1 to 3, wherein a thickness of the layer made of the modified tetrafluoroethylene copolymer in (B) is set in a range of 5 to 500 µm.   The fuel resin hose according to any one of claims 1 to 4, wherein the fluororesin in (A) is a modified fluororesin.   It is a manufacturing method of the fuel type | system | group resin hose as described in any one of Claims 1-5, Comprising: After forming a tubular inner layer by carrying out hot-melt extrusion molding of the material for inner layers which has said (A) as a main component. The metal laminate film (B) is wound around the outer periphery of the inner layer, and then the outer layer material mainly composed of (C) is heat-melted and extruded on the outer periphery of the metal laminate film (B). A fuel-based resin hose comprising a fuel-based resin hose in which an intermediate barrier layer made of the metal laminate film (B) is formed on the outer periphery of a tubular inner layer and an outer layer is formed on the outer periphery of the intermediate barrier layer. The manufacturing method.   The method for producing a fuel-based resin hose according to claim 6, further comprising a step of bending the fuel-based resin hose produced in claim 6 into a mold having a predetermined shape and heating it.   The method for producing a fuel-based resin hose according to claim 6 or 7, wherein the metal laminate film (B) is produced by melting and extruding a modified tetrafluoroethylene copolymer on one side or both sides of a metal foil.   Claims: The metal laminate film (B) is produced by melting and extruding the modified tetrafluoroethylene copolymer to produce a fluororesin film, and then heat laminating the fluororesin film on one or both sides of the metal foil. A method for producing a fuel-based resin hose according to 6 or 7.