Fuel-contacting laminate

Abstract

To provide a laminate contacting fuel, wherein the fuel contains at least a compound (1) which is composed of only a carbon atom, a hydrogen atom and an oxygen atom, and has a carbonyl group or an ether bond, and the laminate includes at least a fluororesin layer containing a fluororesin containing a chlorotrifluoroethylene unit.SOLUTION: A laminate exhibits excellent fuel low permeability to fuel containing a compound which is composed of only a carbon atom, a hydrogen atom and an oxygen atom, and has a carbonyl group or an ether bond.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present disclosure relates to laminates that come into contact with fuel. [Background technology]

[0002] Patent Document 1 describes a laminate having a layer (C) made of a chlorotrifluoroethylene copolymer and a layer (K) made of a fluorine-free organic material, characterized in that the chlorotrifluoroethylene copolymer has a melt flow rate of 15.0 to 40.0 (g / 10 min) and contains chlorotrifluoroethylene units in an amount of 15.0 to 25.0 mol % of all monomer units.

[0003] Patent Document 2 describes a fluororesin material containing a fluororesin, the fluororesin having carbonyl groups, and the total number of carbonyl groups is 10 or less. 6 The document describes a laminate comprising a fluororesin layer containing a fluororesin material having 1 or more and less than 800 particles per unit, the fluororesin being a fluororesin material containing ethylene units and tetrafluoroethylene units, and having a thermal decomposition onset temperature of 390°C or higher at which the mass of the fluororesin material decreases by 1% by mass when the fluororesin material is heated at 10°C / min in an air atmosphere, and a non-fluororesin layer containing a non-fluororesin. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] JP 2010-030276 A [Patent Document 2] Patent Publication No. 2022-58284 Summary of the Invention [Problem to be solved by the invention]

[0005] An object of the present disclosure is to provide a laminate that exhibits excellent low fuel permeability to a fuel that is composed only of carbon atoms, hydrogen atoms, and oxygen atoms and contains a compound having a carbonyl group or an ether bond. [Means for solving the problem]

[0006] According to the present disclosure, there is provided a laminate to be in contact with a fuel, the fuel containing at least a compound (1) consisting only of carbon atoms, hydrogen atoms, and oxygen atoms and having a carbonyl group or an ether bond, the laminate including at least a fluororesin layer containing a fluororesin containing a chlorotrifluoroethylene unit. Effect of the Invention

[0007] According to the present disclosure, it is possible to provide a laminate that exhibits excellent low fuel permeability to a fuel that is composed only of carbon atoms, hydrogen atoms, and oxygen atoms and that contains a compound having a carbonyl group or an ether bond. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0008] Specific embodiments of the present disclosure will be described in detail below, but the present disclosure is not limited to the following embodiments.

[0009] 2. Description of the Related Art Laminates that exhibit low fuel permeability to gasoline or low fuel permeability to alcohol-containing gasoline are conventionally known.

[0010] For example, Patent Document 1 describes that the fuel permeability coefficient of a laminate having the above-mentioned configuration was measured for CE10 (a fuel consisting of a mixture of isooctane and toluene in a volume ratio of 50:50 mixed with 10% by volume of ethanol).

[0011] Furthermore, Patent Document 2 describes that the fuel permeation rate of the laminate having the above-mentioned configuration was measured for CE20, CE50, or CE85 (fuel containing 20, 50, or 80% by volume of ethanol).

[0012] However, there has been no sufficient study to date as to what kind of laminate structure is required to suppress the permeation of fuels that contain compounds that consist only of carbon atoms, hydrogen atoms, and oxygen atoms and have carbonyl groups or ether bonds.

[0013] It has now been found that by incorporating into the laminate a fluororesin layer containing a fluororesin containing chlorotrifluoroethylene units, the laminate exhibits surprisingly low fuel permeability to fuels that consist only of carbon, hydrogen and oxygen atoms and contain compounds having carbonyl groups or ether bonds.

[0014] That is, the laminate of the present disclosure is a laminate that comes into contact with a fuel that is composed only of carbon atoms, hydrogen atoms, and oxygen atoms and contains at least a compound (1) having a carbonyl group or an ether bond, and has at least a fluororesin layer that contains a fluororesin that contains chlorotrifluoroethylene units.

[0015] The configuration of the laminate of the present disclosure will be described in detail below.

[0016] (fuel) The laminate of the present disclosure is used in contact with a fuel that is composed only of carbon, hydrogen, and oxygen atoms and contains at least a compound (1) having a carbonyl group or an ether bond. In one embodiment, the laminate of the present disclosure is used to suppress the permeation of a fuel that is composed only of carbon, hydrogen, and oxygen atoms and contains at least a compound (1) having a carbonyl group or an ether bond. In one embodiment, the laminate of the present disclosure is a tube or hose, and is used to distribute and / or suppress the permeation of a fuel that is composed only of carbon, hydrogen, and oxygen atoms and contains at least a compound (1) having a carbonyl group or an ether bond. That is, the present disclosure includes the use of a laminate (tube or hose) for distributing a fuel containing at least a compound (1) consisting only of carbon atoms, hydrogen atoms, and oxygen atoms and having a carbonyl group or an ether bond, and / or for suppressing the permeation of the fuel. The present disclosure also includes a method for distributing a fuel containing at least compound (1) consisting only of carbon, hydrogen, and oxygen atoms and having a carbonyl group or an ether bond, comprising using a laminate (tube or hose) in contact with the fuel.

[0017] Compound (1) may be a compound synthesized from hydrogen and carbon dioxide. Compounds synthesized from hydrogen and carbon dioxide are also called synthetic fuels, and are expected to contribute to reducing carbon dioxide emissions. The inventors' studies have revealed that conventional laminates can suppress the permeation of conventional fuels such as gasoline, diesel fuel, and alcohol fuel, but cannot sufficiently suppress the permeation of such synthetic fuels. That is, compound (1) exhibits permeability different from that of conventional fuels such as gasoline, diesel fuel, and alcohol fuel. Therefore, conventional knowledge cannot be utilized when selecting the layer structure of a laminate used in contact with a fuel containing compound (1). However, as a result of the inventors' intensive studies, a laminate exhibiting low fuel permeability even to compound (1) has been found.

[0018] Compound (1) is preferably at least one selected from the group consisting of carbonate esters, linear ethers, and cyclic ethers, more preferably at least one selected from the group consisting of carbonate esters and cyclic ethers, and even more preferably carbonate esters.

[0019] Examples of the compound (1) include dimethyl carbonate, diethyl carbonate, dimethyl ether, methyl tert-butyl ether (MTBE), oxymethylene dimethyl ether, and 1-3 dioxolane. The fuel contains one or more of these compounds. Of these, at least one compound selected from the group consisting of dimethyl carbonate and diethyl carbonate is preferred as the compound (1).

[0020] The fuel may contain only compound (1), or may contain compound (1) and other fuels.

[0021] The fuel, for example, A fuel containing only compound (1); A fuel containing compound (1) and alcohol; A fuel containing compound (1) and gasoline; A fuel containing compound (1), alcohol and gasoline; Fuel containing compound (1) and diesel fuel etc.

[0022] The content of compound (1) in the fuel may be 0.1 to 100% by volume. The content of compound (1) in the fuel may be 1% by volume or more, 5% by volume or more, or 10% by volume or more. The content of compound (1) in the fuel may be 90% by volume or less, 80% by volume or less, 60% by volume or less, 40% by volume or less, or 20% by volume or less.

[0023] In one embodiment, the fuel contains the compound (1) and an alcohol. The laminate of the present disclosure also exhibits excellent low permeability to a fuel containing the compound (1) and an alcohol.

[0024] The alcohol is preferably an alcohol having 1 to 5 carbon atoms, more preferably at least one selected from the group consisting of methanol, ethanol, propanol and butanol, and further preferably at least one selected from the group consisting of methanol and ethanol.

[0025] The alcohol content in the fuel may be 10 to 99.9% by volume. The alcohol content in the fuel may be 20% by volume or more, 40% by volume or more, or 80% by volume or more. The alcohol content in the fuel may be 99% by volume or less, 95% by volume or less, or 90% by volume or less.

[0026] When the alcohol in the fuel is methanol, the content thereof may be 10 to 99.9% by volume. The content of methanol in the fuel may be 80% by volume or less, 50% by volume or less, 30% by volume or less, or 20% by volume or less.

[0027] In one embodiment, the fuel contains the compound (1) and gasoline. The laminate of the present disclosure also exhibits excellent low permeability to the fuel containing the compound (1) and gasoline.

[0028] The gasoline may be obtained by refining crude oil. The boiling point of gasoline is generally 30 to 220°C.

[0029] The gasoline content in the fuel may be 10 to 99.9% by volume. The gasoline content in the fuel may be 20% by volume or more, 40% by volume or more, or 80% by volume or more. The gasoline content in the fuel may be 99% by volume or less, 95% by volume or less, or 90% by volume or less.

[0030] In one embodiment, the fuel contains the compound (1) and diesel fuel (light oil). The laminate of the present disclosure also exhibits excellent low permeability to fuel containing the compound (1) and diesel fuel.

[0031] Diesel fuel may be obtained by refining crude oil. Diesel fuel generally has a boiling point greater than 220°C and less than or equal to 350°C.

[0032] The content of diesel fuel in the fuel may be 10 to 99.9% by volume. The content of diesel fuel in the fuel may be 20% by volume or more, 40% by volume or more, or 80% by volume or more. The content of diesel fuel in the fuel may be 99% by volume or less, 95% by volume or less, or 90% by volume or less.

[0033] (Fluororesin layer) The laminate of the present disclosure includes at least a fluororesin layer containing a fluororesin containing chlorotrifluoroethylene (CTFE) units.

[0034] Thus, the laminate of the present disclosure includes at least a fluororesin layer, and since the fluororesin layer contains a fluororesin containing a CTFE unit, it exhibits excellent low fuel permeability to a fuel that is composed of only carbon atoms, hydrogen atoms, and oxygen atoms and contains a compound having a carbonyl group or an ether bond. Surprisingly, when a fluororesin other than a CTFE unit-containing fluororesin, for example a fluororesin containing an ethylene unit and a tetrafluoroethylene unit, is used, sufficient low fuel permeability cannot be obtained.

[0035] The fluororesin is a partially crystalline fluoropolymer, and is not a fluororubber but a fluoroplastic. The fluororesin has a melting point and is thermoplastic. The fluororesin may be melt-processable or non-melt-processable, but is preferably a melt-processable fluororesin because it can be used to produce a tube with high productivity by melt extrusion molding.

[0036] In this disclosure, melt processable means that the polymer can be melted and processed using conventional processing equipment such as extruders, injection molding machines, etc. Thus, melt processable fluororesins typically have a melt flow rate of 0.01 g / 10 min or more and 500 g / 10 min or less.

[0037] The polymer containing CTFE units is preferably at least one selected from the group consisting of polychlorotrifluoroethylene [PCTFE] and CTFE copolymers.

[0038] The content of CTFE units in a polymer containing CTFE units is, relative to all monomer units, preferably 1.0 mol % or more, more preferably 5.0 mol % or more, even more preferably 10.0 mol % or more, particularly preferably 15.0 mol % or more, and is preferably 100 mol % or less, more preferably 75.0 mol % or less, even more preferably 50.0 mol % or less, and still more preferably 30.0 mol % or less, because low fuel permeability is further improved.

[0039] Examples of polymers containing CTFE units include ethylene / chlorotrifluoroethylene (CTFE) copolymers (ECTFE), polychlorotrifluoroethylene (PCTFE), CTFE / tetrafluoroethylene (TFE) copolymers, and TFE / vinylidene fluoride (VdF) / CTFE copolymers (VTC). At least one selected from the group consisting of PCTFE, ethylene / CTFE copolymers, and CTFE / TFE copolymers is preferred, and CTFE / TFE copolymers are more preferred from the viewpoint of low fuel permeability.

[0040] PCTFE includes CTFE homopolymers and polymers containing CTFE units and small amounts of comonomer units.

[0041] The melting point of PCTFE is preferably 150° C. or higher, more preferably 190° C. or higher, and preferably 230° C. or lower, more preferably 217° C. or lower. The melting point is the temperature corresponding to the maximum value in the heat of fusion curve when the temperature is increased at a rate of 10° C. / min using a differential scanning calorimeter [DSC].

[0042] The flow value of PCTFE is preferably 1×10 -4 (cm 3 / sec) or more, preferably 5 × 10 -1 (cm3 The flow value is the volume of resin extruded per second when PCTFE is melted at 230°C using a Koga type flow tester CFT-500D (manufactured by Shimadzu Corporation) and extruded from a nozzle with a diameter of 1 mm under a load of 100 kg.

[0043] The content of CTFE units in PCTFE is preferably 95 mol % or more, more preferably 98 mol % or more, further preferably 99 mol % or more, and preferably 100 mol % or less.

[0044] The comonomer constituting the comonomer unit that can be contained in PCTFE is not particularly limited as long as it is a monomer copolymerizable with CTFE, and examples thereof include TFE, ethylene, vinylidene fluoride, perfluoroalkyl vinyl ether, and hexafluoroethylene.

[0045] The ethylene / CTFE copolymer (ECTFE) is a copolymer containing ethylene units and CTFE units, and preferably contains 46 to 52 mol% of ethylene units and 54 to 48 mol% of CTFE units relative to the total of the ethylene units and CTFE units. ECTFE may be a binary copolymer consisting of only ethylene units and CTFE units, or may further contain polymerization units based on a monomer copolymerizable with ethylene and CTFE (e.g., a fluoroalkyl vinyl ether (PAVE) derivative).

[0046] The content of polymerization units based on monomers copolymerizable with ethylene and CTFE is preferably 0.01 mol % or more and 5 mol % or less based on the total of the ethylene units, CTFE units, and polymerization units based on the above-mentioned copolymerizable monomers.

[0047] The MFR (230°C) of ECTFE is preferably 0.5 g / 10 min or more and preferably 100 g / 10 min or less. The MFR of ECTFE is measured at a temperature of 230°C and a load of 2.16 kg.

[0048] The CTFE / TFE copolymer contains CTFE units and TFE units. Particularly preferred CTFE / TFE copolymers include those containing CTFE units, TFE units, and monomer (α) units derived from a monomer (α) copolymerizable with these units.

[0049] The monomer (α) is not particularly limited as long as it is a monomer copolymerizable with CTFE and TFE, and examples thereof include ethylene (Et), VdF, CF2=CF-ORf 1 (In the formula, Rf 1 Perfluoro(alkyl vinyl ether) (PAVE) represented by a perfluoroalkyl group having 1 to 8 carbon atoms, CX 3 X 4 =CX 5 (CF2) n X 6 (In the formula, X 3 , X 4 and X 5 are the same or different and are a hydrogen atom or a fluorine atom; X 6 is a hydrogen atom, a fluorine atom, or a chlorine atom; n is an integer of 1 to 10), 2 (In the formula, Rf 2 and alkyl perfluorovinyl ether derivatives represented by the formula (I) (a perfluoroalkyl group having 1 to 5 carbon atoms), among which at least one selected from the group consisting of PAVE, the vinyl monomers and alkyl perfluorovinyl ether derivatives is preferred, and at least one selected from the group consisting of PAVE and HFP is more preferred.

[0050] For PAVE, CF2=CF-ORf 3 (In the formula, Rf 3represents a perfluoroalkyl group having 1 to 5 carbon atoms.) is preferred, and examples thereof include perfluoro(methyl vinyl ether) [PMVE], perfluoro(ethyl vinyl ether) [PEVE], perfluoro(propyl vinyl ether) [PPVE], perfluoro(butyl vinyl ether), and the like. Among these, at least one selected from the group consisting of PMVE, PEVE, and PPVE is more preferred, and PPVE is even more preferred.

[0051] As the alkyl perfluorovinyl ether derivative, Rf 2 is preferably a perfluoroalkyl group having 1 to 3 carbon atoms, and CF2=CF-OCH2-CF2CF3 is more preferable.

[0052] The ratio of CTFE units to TFE units in the CTFE / TFE copolymer is preferably 15.0 to 90.0 mol % of CTFE units and 85.0 to 10.0 mol % of TFE units, more preferably 15.0 to 50.0 mol % of CTFE units and 85.0 to 50.0 mol % of TFE units, even more preferably 15.0 to 30.0 mol % of CTFE units and 85.0 to 70.0 mol % of TFE units, and particularly preferably 15.0 to 30.0 mol % of CTFE units and 85.0 to 70.0 mol % of TFE units.

[0053] The CTFE / TFE copolymer preferably contains 90.0 to 99.9 mol% of CTFE units and TFE units in total, and 0.1 to 10.0 mol% of monomer (α) units. If the monomer (α) units are less than 0.1 mol%, the moldability, environmental stress cracking resistance, and fuel cracking resistance tend to be poor, whereas if they exceed 10.0 mol%, the fuel barrier properties, heat resistance, and mechanical properties tend to be poor.

[0054] As the CTFE / TFE copolymer, a CTFE / TFE / PAVE copolymer is particularly preferred.

[0055] In the CTFE / TFE / PAVE copolymer, the above-mentioned PAVE may be perfluoro(methyl vinyl ether) [PMVE], perfluoro(ethyl vinyl ether) [PEVE], perfluoro(propyl vinyl ether) [PPVE], perfluoro(butyl vinyl ether), etc., and among these, at least one selected from the group consisting of PMVE, PEVE and PPVE is preferred, with PPVE being more preferred. In the CTFE / TFE / PAVE copolymer, the PAVE unit preferably accounts for 0.5 mol % or more and 5 mol % or less of the total monomer units.

[0056] The melting point of the CTFE / TFE copolymer is preferably 190°C or higher, more preferably 210°C or higher, even more preferably 220°C or higher, particularly preferably 230°C or higher, and most preferably 240°C or higher, and is preferably less than 324°C, more preferably 320°C or lower, even more preferably 270°C or lower, and most preferably 260°C or lower.

[0057] The MFR (297°C) of the CTFE / TFE copolymer is preferably 0.5 g / 10 min or more, more preferably 2.0 g / 10 min or more, even more preferably 5.0 g / 10 min or more, particularly preferably 7 g / 10 min or more, preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less, even more preferably 40 g / 10 min or less, particularly preferably 35 g / 10 min or less. The MFR of the CTFE / TFE copolymer is measured at a temperature of 297°C and a load of 5 kg.

[0058] The fluororesin layer is preferably conductive. When the fluororesin layer has conductivity, it can prevent the laminate from becoming charged even if static electricity is generated due to friction between the laminate and fuel.

[0059] The fluororesin layer preferably contains a conductive filler, which easily imparts electrical conductivity to the fluororesin layer, and prevents the laminate from becoming charged even if static electricity is generated by friction between the laminate and fuel.

[0060] The conductive filler is not particularly limited, and examples thereof include conductive simple substance powders or conductive simple substance fibers of metals, carbon, etc.; powders of conductive compounds such as zinc oxide; and powders that have been surface-treated to be conductive.

[0061] The conductive elemental powder or conductive elemental fiber is not particularly limited, and examples thereof include metal powders such as copper and nickel; metal fibers such as iron and stainless steel; carbon black, carbon fibers, carbon fibrils, carbon nanotubes, and carbon nanohorns, as described in JP-A-3-174018, etc.

[0062] The surface-conductively treated powder is a powder obtained by subjecting the surface of a non-conductive powder such as glass beads or titanium oxide to a conductive treatment. The method of the conductive treatment is not particularly limited, and examples thereof include metal sputtering and electroless plating. Among the above-mentioned conductive fillers, carbon black is preferably used because it is advantageous from the viewpoint of economy.

[0063] The amount of the conductive filler is appropriately determined based on the type of fluororesin, the conductive performance required for the laminate, molding conditions, etc., but is preferably 1 part by mass or more and 30 parts by mass or less per 100 parts by mass of fluororesin. The more preferred lower limit is 5 parts by mass, and the more preferred upper limit is 20 parts by mass.

[0064] In addition to the conductive filler, the fluororesin layer may contain various additives such as reinforcing agents, bulking agents, ultraviolet absorbers, pigments, etc., within the scope of the present disclosure. By using such additives, the properties of the fluororesin layer, such as surface hardness, abrasion resistance, electrostatic property, weather resistance, etc., can be improved.

[0065] In the laminate of the present disclosure, it is preferable that the fluororesin layer is configured to come into contact with the fuel. By forming the contact surface between the laminate and the fuel with a fluororesin layer, the laminate is endowed with excellent fuel resistance and the durability of the laminate is improved. In addition, when the fluororesin layer has electrical conductivity, by forming the contact surface between the laminate and the fuel with a fluororesin layer, the laminate can be further prevented from being charged even if static electricity is generated due to friction between the laminate and the fuel.

[0066] (Non-fluorinated polymer layer) The laminate of the present disclosure may include a non-fluorinated polymer layer containing a non-fluorinated polymer in addition to the fluororesin layer. The non-fluorinated polymer is a polymer that does not contain fluorine atoms. As the non-fluorinated polymer, a wide range of polymers known as thermoplastic resins can be used.

[0067] Examples of non-fluorinated polymers include resins that have excellent mechanical strength and whose main role is to maintain pressure resistance and the shape of molded products (hereinafter referred to as structural material resins), such as aliphatic polyamide resins, aromatic polyamide resins, polyolefin resins, modified polyolefin resins, vinyl chloride resins, polyurethane resins, polyester resins, polyaramid resins, polyimide resins, polyamideimide resins, polyphenylene oxide resins, polyacetal resins, polycarbonate resins, acrylic resins, styrene resins, acrylonitrile / butadiene / styrene resins (ABS), cellulose resins, polyether ether ketone resins (PEEK), polysulfone resins, polyethersulfone resins (PES), and polyetherimide resins, and resins that have high permeation resistance to fuels and gases (hereinafter referred to as permeation-resistant resins), such as ethylene / vinyl alcohol copolymer resins, polyphenylene sulfide resins, polybutylene naphthalate resins, polybutylene terephthalate resins, and polyphthalamide (PPA).

[0068] As the non-fluorinated polymer, among others, at least one selected from the group consisting of an aliphatic polyamide resin, an aromatic polyamide resin, a polyolefin resin, a modified polyolefin resin, and an ethylene / vinyl alcohol copolymer resin is preferable, at least one selected from the group consisting of an aliphatic polyamide resin, an aromatic polyamide resin, and an ethylene / vinyl alcohol copolymer resin is more preferable, and at least one selected from the group consisting of an aliphatic polyamide resin and an aromatic polyamide resin is even more preferable.

[0069] The laminate of the present disclosure has excellent mechanical strength when the non-fluorinated polymer layer contains the structural member resin, and has excellent permeation resistance to fuel when the non-fluorinated polymer layer contains the permeation-resistant resin.

[0070] Aliphatic polyamide resins and aromatic polyamide resins (collectively sometimes simply referred to as "polyamide resins") are polymers that contain amide bonds [-NH-C(=O)-] as repeating units within the molecule.

[0071] The polyamide resin may be either a so-called nylon resin made of a polymer in which an amide bond in the molecule is bonded to an aliphatic structure or an alicyclic structure, or a so-called aramid resin made of a polymer in which an amide bond in the molecule is bonded to an aromatic structure.

[0072] The polyamide resin (nylon resin) is not particularly limited, and examples thereof include polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyamide 1010, polyamide 612, polyamide 6 / 66, polyamide 66 / 12, polyamide 46, metaxylylenediamine / adipic acid copolymer, polyamide 62, polyamide 92, polyamide 122, polyamide 142, and aromatic polyamides such as polyamide 6T and polyamide 9T. Two or more of these may be used in combination.

[0073] The aramid resin is not particularly limited, and examples thereof include polyparaphenylene terephthalamide, polymetaphenylene isophthalamide, and the like.

[0074] The polyamide resin may also be a polymer in which a structure having no amide bond as a repeating unit is block-copolymerized or graft-copolymerized in a part of the molecule. Examples of such polyamide resins include polyamide-based elastomers such as polyamide 6 / polyester copolymer, polyamide 6 / polyether copolymer, polyamide 12 / polyester copolymer, and polyamide 12 / polyether copolymer. These polyamide-based elastomers are obtained by block-copolymerizing a polyamide oligomer and a polyester oligomer via an ester bond, or by block-copolymerizing a polyamide oligomer and a polyether oligomer via an ether bond. Examples of the polyester oligomer include polycaprolactone and polyethylene adipate, and examples of the polyether oligomer include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Examples of the polyamide-based elastomers include polyamide 6 / polytetramethylene glycol copolymer and polyamide 12 / polytetramethylene glycol copolymer.

[0075] As the polyamide resin, since a layer made of the polyamide resin can have sufficient mechanical strength even in a thin layer, among others, polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyamide 1010, polyamide 612, polyamide 62, polyamide 6 / 66, polyamide 66 / 12, polyamide 6 / polyester copolymer, polyamide 6 / polyether copolymer, polyamide 12 / polyester copolymer, polyamide 12 / polyether copolymer, polyamide 9T, etc. are preferred, and two or more of these may be used in combination.

[0076] The amine value of polyamide resin is 10 (equivalent / 10 6g) or more is preferable, and 80 (equivalent / 10 6 When the amine value is within the above range, excellent interlayer adhesive strength can be obtained even in the case of coextrusion at a relatively low temperature. 6 If the thickness is less than 80 (equivalent weight / 10 6 If the ratio exceeds 15 (equivalent weight / 10 g), the mechanical strength of the laminate is insufficient, and the laminate may be easily discolored during storage, resulting in poor handling properties. 6 g), and a more preferable lower limit is 23 (equivalent / 10 6 g), and a more preferred upper limit is 60 (equivalent / 10 6 g), and a more preferable upper limit is 50 (equivalent / 10 6 g).

[0077] In the present disclosure, the amine value is a value obtained by dissolving 1 g of polyamide resin in 50 ml of m-cresol under heating, and titrating the solution with a 1 / 10 N aqueous solution of p-toluenesulfonic acid using thymol blue as an indicator, and unless otherwise specified, means the amine value of the polyamide resin before lamination. It is considered that a part of the number of amino groups possessed by the polyamide resin before lamination is consumed for adhesion with the adjacent layer, but the number is very small relative to the entire layer, so that the amine value of the polyamide resin before lamination described above and the amine value of the laminate of the present disclosure are substantially the same.

[0078] The polyolefin resin is a resin having a monomer unit derived from a vinyl group-containing monomer having no fluorine atom. The vinyl group-containing monomer having no fluorine atom is not particularly limited, but in applications requiring interlayer adhesion, it is preferable to use one having the polar functional group described above.

[0079] The polyolefin resin is not particularly limited, and examples thereof include polyolefins such as polyethylene, polypropylene, high-density polyolefins, and low-density polyolefins, as well as modified polyolefins obtained by modifying the above-mentioned polyolefins with maleic anhydride or the like, epoxy-modified polyolefins, and amine-modified polyolefins, among which high-density polyolefins are preferred.

[0080] The ethylene / vinyl alcohol copolymer resin is obtained by saponifying an ethylene / vinyl acetate copolymer obtained from ethylene and vinyl acetate. The blending ratio of the ethylene and vinyl acetate to be copolymerized is appropriately determined according to the ratio of the moles of the vinyl acetate unit defined by the formula described below.

[0081] The ethylene / vinyl alcohol copolymer resin preferably has a vinyl acetate unit content of X mole % and a saponification degree of Y percent that satisfy X×Y / 100≧7. If X×Y / 100<7, the interlayer adhesive strength may be insufficient. X×Y / 100≧10 is more preferable. The value of X×Y / 100 is an index of the hydroxyl group content of the ethylene / vinyl alcohol copolymer resin, and a large value of X×Y / 100 means that the hydroxyl group content of the ethylene / vinyl alcohol copolymer resin is high.

[0082] Hydroxyl groups are groups that can participate in adhesion between the EVOH layer and the other material to be laminated, and when the ethylene / vinyl alcohol copolymer resin has a high content of hydroxyl groups, the interlayer adhesion in the laminate is improved. In this disclosure, the above-mentioned "other material to be laminated" refers to a material that is in contact with the material to be laminated.

[0083] In the present disclosure, the term "X mol % of vinyl acetate units" refers to the ratio of the number of moles [Ni] of vinyl acetate derived from vinyl acetate units to the total number of moles [N] of ethylene and vinyl acetate added in the molecule of an ethylene / vinyl alcohol copolymer resin, and is expressed by the following formula: Xi(%)=(Ni / N)×100 The vinyl acetate unit X mol % is a value obtained by measurement using infrared absorption spectroscopy (IR).

[0084] In the present disclosure, the term "vinyl acetate unit" refers to a portion of the molecular structure of an ethylene / vinyl alcohol copolymer resin that is derived from vinyl acetate. The vinyl acetate unit may be saponified and have a hydroxyl group, or may be unsaponified and have an acetoxyl group.

[0085] The "saponification degree" is a percentage that represents the ratio of the number of saponified vinyl acetate units to the total number of saponified vinyl acetate units and the number of unsaponified vinyl acetate units. The saponification degree is a value obtained by measurement using infrared absorption spectroscopy (IR).

[0086] Examples of ethylene / vinyl alcohol copolymer resins in which X and Y satisfy the above formula include commercially available products such as EVAL F101 (manufactured by Kuraray Co., Ltd., vinyl acetate unit X=68.0 mol %; saponification degree Y=95%; X×Y / 100=64.6), MERSEN H6051 (manufactured by Tosoh Corporation, vinyl acetate unit X=11.2 mol %; saponification degree Y=100%; X×Y / 100=11.2), and Technolink K200 (manufactured by Taoka Chemical Co., Ltd., vinyl acetate unit X=11.2 mol %; saponification degree Y=85%; X×Y / 100=9.52).

[0087] The ethylene / vinyl alcohol copolymer resin preferably has an MFR of 0.5 g / 10 min or more at 200 ° C., and preferably has an MFR of 100 g / 10 min or less. If the MFR is less than 0.5 g / 10 min or more than 100 g / 10 min, the difference between the melt viscosity of the ethylene / vinyl alcohol copolymer resin and the melt viscosity of the mating material tends to become large, and there is a possibility that unevenness may occur in the thickness of each layer, which is not preferable. The preferred lower limit is 1 g / 10 min, and the preferred upper limit is 50 g / 10 min.

[0088] The non-fluorinated polymer has a melting point of preferably 50° C. or higher and 400° C. or lower. The lower limit is more preferably 100° C., and further preferably 150° C. The upper limit is more preferably 350° C., and further preferably 300° C.

[0089] The melting point is determined as the temperature corresponding to the maximum value on the heat of fusion curve when the temperature is increased at a rate of 10° C. / min using a differential scanning calorimeter (DSC) (manufactured by Seiko Corporation).

[0090] The non-fluorinated polymer layer may contain various additives, such as stabilizers such as heat stabilizers, reinforcing agents, fillers, ultraviolet absorbers, pigments, etc., within the scope of the present disclosure. By using such additives, the properties of the non-fluorinated polymer, such as heat stability, surface hardness, abrasion resistance, electrostatic properties, weather resistance, etc., can be improved.

[0091] (Structure of Laminate) The laminate of the present disclosure includes at least a fluororesin layer. The number of layers of the laminate of the present disclosure is not particularly limited as long as it is 2 or more. The number of layers of the laminate of the present disclosure may be 2 to 5, and is preferably 2.

[0092] In the laminate of the present disclosure, the fluororesin layer and the non-fluorinated polymer layer may be directly bonded to each other or may be bonded to each other via another layer such as an adhesive layer, but it is preferable that they are directly bonded to each other.

[0093] The laminate of the present disclosure preferably has a fuel permeation rate of 15 g / m 2 / day or less, and more preferably 10 g / m 2 / day or less, and more preferably 5.0 g / m 2 / day or less, and particularly preferably 3.0 g / m 2 / day or less.

[0094] The fuel permeation rate of the laminate is the rate at which a fuel containing at least compound (1) consisting only of carbon, hydrogen and oxygen atoms and having a carbonyl group or an ether bond permeates the laminate. The fuel permeation rate of the laminate can be determined by producing a tubular laminate, preparing a fuel containing compound (1) at a predetermined concentration, sealing the fuel in the tubular laminate, leaving it at 60°C or 80°C, measuring the mass change per unit time, and calculating the fuel permeation rate from the mass change and the internal area of ​​the tubular laminate.

[0095] The laminate of the present disclosure can be in various shapes such as a film shape, a sheet shape, a tube (hose) shape, a bottle shape, a tank shape, etc. The film shape, sheet shape, tube shape, and hose shape may be a corrugated shape, a corrugated shape, a convoluted shape, etc. The laminate of the present disclosure may be, for example, a film, a sheet, a tube, a hose, a bottle, a container, a tank, etc. The laminate of the present disclosure can be suitably used for, for example, a fuel tube or a fuel hose such as an automobile fuel tube or an automobile fuel hose, an underground buried tube or hose for a fuel supply facility, an automobile fuel tank, various automobile seals such as an O-ring for a fuel pump, etc.

[0096] In one embodiment, the laminate of the present disclosure is used as a member constituting a system for distributing fuel that is composed of only carbon atoms, hydrogen atoms, and oxygen atoms and contains at least a compound (1) having a carbonyl group or an ether bond. The system for distributing fuel is, for example, a system used for storing or supplying fuel. Members used in such a system include tanks, tubes, hoses, caps, valves, diaphragms, seals (O-rings), and the like. The system for distributing fuel is, for example, not only used in automobiles, but also in facilities for supplying fuel to automobile fuel tanks. A typical example of a member constituting a system for distributing fuel is a fuel tube or a fuel hose.

[0097] (Tubes and Hoses) The laminate of the present disclosure can be suitably used as a tube or a hose. In the present disclosure, the term "tube or hose" includes an article generally called a tube or a hose, and is usually an article having a shape capable of transporting a fluid. In the present disclosure, the term "tube or hose" does not mean that a tube and a hose are different articles.

[0098] The tube or hose of the present disclosure may, for example, comprise a fluororesin layer / a non-fluorinated polymer layer as the innermost layer / outermost layer.

[0099] The fuel permeation rate of the tube or hose of the present disclosure is preferably 15 g / m 2 / day or less, and more preferably 10 g / m 2 / day or less, and more preferably 5.0 g / m 2 / day or less, and particularly preferably 3.0 g / m 2 / day or less.

[0100] The fuel permeation rate of a tube or hose is the rate at which a fuel containing at least compound (1) consisting only of carbon, hydrogen and oxygen atoms and having a carbonyl group or an ether bond permeates the laminate. The fuel permeation rate of a tube or hose can be determined by preparing a fuel containing compound (1) at a specified concentration, sealing the fuel in the tube or hose, leaving it at 60°C or 80°C, measuring the mass change per unit time, and calculating the fuel permeation rate from the mass change and the inner area of ​​the tube or hose.

[0101] The outer diameter of the tube or hose is preferably 2 mm or more, more preferably 3 mm or more, even more preferably 4 mm or more, and most preferably 6 mm or more, and is preferably 20 mm or less, more preferably 18 mm or less, even more preferably 16 mm or less, and most preferably 14 mm or less.

[0102] The inner diameter of the tube or hose is preferably 1 mm or more, more preferably 2 mm or more, even more preferably 3 mm or more, and most preferably 4 mm or more, and is preferably 15 mm or less, more preferably 13 mm or less, even more preferably 11 mm or less, and most preferably 10 mm or less.

[0103] The thickness of the tube or hose (the difference between the outer diameter and the inner diameter) is preferably 0.5 mm or more, more preferably 0.6 mm or more, even more preferably 0.7 mm or more, and preferably 8 mm or less, more preferably 6 mm or less, even more preferably 4 mm or less, and particularly preferably 2 mm or less.

[0104] The thickness of the fluororesin layer in the laminate and the tube or hose is preferably 0.05 mm or more, more preferably 0.10 mm or more, even more preferably 0.15 mm or more, and preferably 0.40 mm or less, more preferably 0.30 mm or less, and even more preferably 0.20 mm or less. When the laminate and the tube or hose have two or more fluororesin layers, the thickness of the fluororesin layer is the total thickness of the layers.

[0105] The thickness of the non-fluorinated polymer layer in the laminate and the tube or hose is preferably 0.60 mm or more, more preferably 0.70 mm or more, even more preferably 0.80 mm or more, and preferably 0.95 mm or less, more preferably 0.90 mm or less, even more preferably 0.80 mm or less. When the laminate and the tube or hose have two or more non-fluorinated polymer layers, the thickness of the non-fluorinated polymer layer is the total thickness of the layers.

[0106] When the laminate and the tube or hose have a two-layer structure of an innermost layer / outermost layer, the thickness of the innermost layer is preferably 0.05 mm or more, more preferably 0.10 mm or more, even more preferably 0.15 mm or more, and preferably 0.40 mm or less, more preferably 0.30 mm or less, even more preferably 0.20 mm or less.

[0107] When the laminate and the tube or hose have a two-layer structure of an innermost layer / outermost layer, the thickness of the outermost layer is preferably 0.60 mm or more, more preferably 0.70 mm or more, even more preferably 0.80 mm or more, and preferably 0.95 mm or less, more preferably 0.90 mm or less, even more preferably 0.80 mm or less.

[0108] The tube or hose may be corrugated, corrugated, convoluted, etc. When the tube or hose has a corrugated shape, it has an area with a plurality of corrugated folds arranged in an annular shape, which allows one side of the annular shape to be compressed and the other side to be stretched outward, allowing it to be easily bent to any angle without stress fatigue or delamination.

[0109] There is no particular limitation on the method for forming the corrugated region, but it can be easily formed by forming a straight tube or hose, and then subsequently molding the tube or hose to give it a predetermined corrugated shape.

[0110] The method for producing the laminate of the present disclosure includes, for example, (1) A method of forming a multi-layered laminate in one step by co-extrusion molding the polymers that form each layer and heat-sealing (melting and bonding) the layers together (co-extrusion molding); (2) A method in which each layer is produced separately using an extruder, and then the layers are laminated together and bonded by heat fusion. (3) A method of forming a laminate by extruding a polymer for forming a layer adjacent to a previously prepared layer onto the surface of the previously prepared layer using an extruder; (4) A method in which a polymer that will form a layer adjacent to a previously prepared layer is electrostatically coated on the surface of the layer, and the resulting coated product is heated overall or from the coated side to heat and melt the coated polymer and form a layer. etc.

[0111] When the laminate of the present disclosure is a tube or a hose, examples of the method corresponding to the above (2) include (2a) a method in which each cylindrical layer is separately formed by an extruder, and a layer that comes into contact with the layer that will become the inner layer is coated with a heat-shrinkable tube; a method corresponding to the above (3) includes (3a) a method in which a layer that will become the inner layer is first formed by an inner layer extruder, and a layer that comes into contact with the inner layer is formed on the outer surface of the inner layer by an outer layer extruder; and a method corresponding to the above (4) includes (4a) a method in which a polymer that constitutes the inner layer is electrostatically coated on the inside of a layer that will come into contact with the inner layer, and the resulting coated article is placed in a heating oven and heated overall, or a rod-shaped heating device is inserted inside a cylindrical coated article and heated from the inside, thereby heating and melting the polymer that constitutes the inner layer to form the article.

[0112] If the layers constituting the laminate and tube or hose of the present disclosure are coextrudable, they are generally formed by the coextrusion molding method (1) above. Examples of the coextrusion molding include conventionally known multilayer coextrusion manufacturing methods such as the multi-manifold method and the feed block method.

[0113] In the above molding methods (2) and (3), after each layer is formed, the contact surface of each layer with other layers may be surface-treated in order to enhance interlayer adhesion. Examples of such surface treatments include etching treatments such as sodium etching treatment, corona treatments, and plasma treatments such as low-temperature plasma treatments.

[0114] The laminate of the present disclosure may also be formed by laminating multiple materials in multiple stages by rotational molding. In this case, the melting point of the outer layer material does not necessarily have to be higher than that of the inner layer material, and the melting point of the inner layer material may be 100° C. or more higher than that of the outer layer material. In this case, it is preferable to have a heating section inside as well.

[0115] The tube or hose of the present disclosure can be suitably used, for example, as a fuel tube or fuel hose, such as an automobile fuel tube or automobile fuel hose, or an underground buried tube or hose for a fuel supply facility.

[0116] Although the embodiments have been described above, it will be understood that various changes in form and details are possible without departing from the spirit and scope of the claims.

[0117] <1> According to a first aspect of the present disclosure, A laminate in contact with a fuel, comprising: The fuel contains at least a compound (1) consisting of only carbon atoms, hydrogen atoms, and oxygen atoms and having a carbonyl group or an ether bond; The laminate includes at least a fluororesin layer containing a fluororesin containing chlorotrifluoroethylene units. <2> According to a second aspect of the present disclosure, There is provided a laminate according to a first aspect, wherein the compound (1) is at least one selected from the group consisting of a carbonate ester, a chain ether, and a cyclic ether. <3> According to a third aspect of the present disclosure, There is provided a laminate according to the first or second aspect, wherein compound (1) is at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, dimethyl ether, methyl tert-butyl ether, oxymethylene dimethyl ether and 1-3 dioxolane. <4> According to a fourth aspect of the present disclosure, There is provided a laminate according to any one of the first to third aspects, wherein the fuel further contains alcohol. <5> According to a fifth aspect of the present disclosure, There is provided a laminate according to any one of the first to fourth aspects, wherein the fuel further contains at least one selected from the group consisting of gasoline and diesel fuel. <6> According to a sixth aspect of the present disclosure, There is provided a laminate according to any one of the first to fifth aspects, wherein the content of compound (1) in the fuel is 0.1 to 20% by volume. <7> According to a seventh aspect of the present disclosure, The laminate according to any one of the first to sixth aspects is provided, wherein the content of chlorotrifluoroethylene units in the fluororesin is 15.0 to 30.0 mol % based on the total monomer units constituting the fluororesin. <8> According to an eighth aspect of the present disclosure, According to any one of the first to seventh aspects, there is provided a laminate, wherein the fluororesin contains chlorotrifluoroethylene units and tetrafluoroethylene units. <9> According to a ninth aspect of the present disclosure, According to any one of the first to eighth aspects, there is provided a laminate, wherein the fluororesin contains chlorotrifluoroethylene units, tetrafluoroethylene units and perfluoro(alkyl vinyl ether) units. <10> According to a tenth aspect of the present disclosure, According to an eighth or ninth aspect, there is provided a laminate, wherein the content of tetrafluoroethylene units in the fluororesin is 85.0 to 70.0 mol % based on the total monomer units constituting the fluororesin. <11> According to an eleventh aspect of the present disclosure, According to any one of the first to tenth aspects, there is provided a laminate, wherein the fluororesin layer has electrical conductivity. <12> According to a twelfth aspect of the present disclosure, According to any one of the first to eleventh aspects, there is provided a laminate, wherein the fluororesin layer is in contact with the fuel. <13> According to a thirteenth aspect of the present disclosure, There is provided a laminate according to any one of the first to twelfth aspects, further comprising a non-fluorinated polymer layer containing a non-fluorinated polymer. <14> According to a fourteenth aspect of the present disclosure, There is provided a laminate according to a thirteenth aspect, wherein the non-fluorinated polymer is at least one selected from the group consisting of an aliphatic polyamide resin, an aromatic polyamide resin, a polyolefin resin, a modified polyolefin resin and an ethylene / vinyl alcohol copolymer resin. <15> According to a fifteenth aspect of the present disclosure, The fuel permeation rate is 15 g / m 2 / day or less according to any one of the first to fourteenth aspects. <16> According to a sixteenth aspect of the present disclosure, There is provided a tube or hose formed from the laminate according to any one of the first to fifteenth aspects. <17> According to a seventeenth aspect of the present disclosure, A tube or hose formed from the laminate according to any one of the first to fifteenth aspects, The laminate comprises: A conductive filler and a fluororesin layer containing a fluororesin containing a chlorotrifluoroethylene unit and a tetrafluoroethylene unit; and a non-fluorinated polymer layer containing an aliphatic polyamide resin; In this order, The fluororesin layer is the innermost layer and contacts the fuel. A tube or hose is provided. EXAMPLES

[0118] Next, embodiments of the present disclosure will be described with reference to examples, but the present disclosure is not limited to these examples.

[0119] The values ​​in the examples were measured by the following methods.

[0120] <Polymer composition (monomer composition of fluororesin)> Using a nuclear magnetic resonance spectrometer AC300 (manufactured by Bruker-Biospin), 19 F-NMR measurements were performed, and the monomer composition of the fluororesin (content of each monomer unit in the polymer) was calculated from the integral value of each peak. Depending on the type of monomer, the results of elemental analysis were appropriately combined to determine the monomer composition of the fluororesin.

[0121] <Melting point> Using a differential scanning calorimeter RDC220 (Seiko Instruments), heat measurement was carried out at a temperature increase rate of 10° C. / min in accordance with ASTM D 4591, and the melting point of the fluororesin was determined from the peak of the obtained endothermic curve.

[0122] <Melt flow rate (MFR)> Using a melt indexer (manufactured by Yasuda Seiki Seisakusho), the mass (g / 10 min) of the fluororesin flowing out per 10 min from a nozzle with an inner diameter of 2 mm and a length of 8 mm at 265°C or 297°C under a load of 5 kg was determined as the MFR in accordance with ASTM D 1238.

[0123] <Fuel permeation rate> The tubes obtained in the experimental and comparative experimental examples were cut and the inside diameter and length were measured. Swagelok fittings were attached to both ends of the tube, the tube was filled with the following fuel, the lid was tightened, and the mass of the tube with the fuel sealed inside was measured. Next, the tube was kept at 60°C for the measurement of the fuel permeation rate shown in Table 2, and at 80°C for the measurement of the fuel permeation rate shown in Table 3, and the mass was measured after 1000 hours had passed. The amount of mass loss was calculated from each measured mass, and the fuel permeation rate (g / m2) was calculated from the amount of mass loss and the inner area of ​​the tube. 2 / day) was calculated.

[0124] The fuel permeation rates shown in Table 2 were measured using the following fuels, which contained any ratio of CE10 (toluene / isooctane / ethanol = 45 / 45 / 10 volume%), CM15 (toluene / isooctane / methanol = 42.5 / 42.5 / 15 volume%), Fuel C (toluene / isooctane = 50 / 50 volume%), E (ethanol), M (methanol) and DMC (dimethyl carbonate). Fuel (1-1): CE10 100% by volume Fuel (1-2): Fuel C / E / DMC = 85 / 10 / 5 (volume%) Fuel (1-3): Fuel C / E / DMC = 80 / 10 / 10 (volume%) Fuel (1-4): Fuel C / E / DMC = 70 / 10 / 20 (volume%) Fuel (1-5): E / DMC=10 / 90 (volume%) Fuel (1-6): DMC 100% by volume Fuel (1-7): CM15 100% by volume Fuel (1-8): Fuel C / M / DMC = 65 / 15 / 20 (volume%)

[0125] For the measurement of the fuel permeation rate shown in Table 3, the following fuels containing diesel and DMC (dimethyl carbonate) in arbitrary ratios were used. Fuel (2-1): diesel 100% by volume Fuel (2-2): diesel / DMC=95 / 5 (volume%) Fuel (2-3): diesel / DMC=90 / 10 (volume%) Fuel (2-4): diesel / DMC=80 / 20 (volume%)

[0126] The following materials were used in the experimental and comparative examples.

[0127] Fluorine Resin (1) Polymer composition (mol%): CTFE / TFE / PPVE=21.0 / 76.5 / 2.5 Melting point: 248℃ Melt flow rate (297℃): 7.0g / 10min Carbon black content: 10% by mass

[0128] Fluorine resin (2) Polymer composition (mol%): TFE / Et / HFP / 2,3,3,4,4,5,5-heptafluoro-1-pentene) = 45.5 / 44.4 / 9.5 / 0.6 Melting point: 197℃ Melt flow rate (265℃): 5.0g / 10min Carbon black content: 12% by mass

[0129] Polyamide 12 (PA12) Polypla-Evonik, Daiamid X7297

[0130] Experimental Example 1 and Comparative Experimental Example 1 Using a five-type, five-layer tube extrusion device equipped with a multi-manifold (manufactured by Plastics Engineering Research Institute), each material was supplied to the extruder so that each layer was composed of the material listed in Table 1, and a two-layer tube with an outer diameter of 8 mm and an inner diameter of 6 mm was molded.

[0131] The physical properties of the obtained two-layer tube were measured by the methods described above. The results are shown in Tables 2 and 3.

[0132] Comparative Experiment Example 2 Using a 5-type, 5-layer tube extrusion device (manufactured by Plastics Engineering Research Institute) equipped with a multi-manifold, polyamide 12 (PA12) was fed into the extruder to form a single-layer tube with an outer diameter of 8 mm and an inner diameter of 6 mm.

[0133] The obtained single-layer tube was used to measure various physical properties by the methods described above. The results are shown in Table 3.

[0134] [Table 1]

[0135] [Table 2]

[0136]

Table 3

Claims

1. A laminate in contact with a fuel, comprising: The fuel contains at least a compound (1) consisting of only carbon atoms, hydrogen atoms, and oxygen atoms and having a carbonyl group or an ether bond; Compound (1) is at least one selected from the group consisting of dimethyl carbonate and diethyl carbonate, The laminate comprises at least a fluororesin layer containing a fluororesin containing chlorotrifluoroethylene units.

2. 10. The laminate of claim 1, wherein the fuel further comprises an alcohol.

3. 3. The laminate according to claim 1, wherein the fuel further comprises at least one selected from the group consisting of gasoline and diesel fuel.

4. 3. The laminate according to claim 1, wherein the content of the compound (1) in the fuel is 0.1 to 20% by volume.

5. 3. The laminate according to claim 1, wherein the content of chlorotrifluoroethylene units in the fluororesin is 15.0 to 30.0 mol % based on the total monomer units constituting the fluororesin.

6. 3. The laminate according to claim 1, wherein the fluororesin contains chlorotrifluoroethylene units and tetrafluoroethylene units.

7. 3. The laminate according to claim 1, wherein the fluororesin contains chlorotrifluoroethylene units, tetrafluoroethylene units and perfluoro(alkyl vinyl ether) units.

8. 7. The laminate according to claim 6, wherein the content of tetrafluoroethylene units in the fluororesin is 85.0 to 70.0 mol % based on the total monomer units constituting the fluororesin.

9. The laminate according to claim 1 or 2, wherein the fluororesin layer has electrical conductivity.

10. The laminate according to claim 1 or 2, wherein the fluororesin layer is in contact with the fuel.

11. The laminate of claim 1 or 2, further comprising a non-fluorinated polymer layer containing a non-fluorinated polymer.

12. 12. The laminate according to claim 11, wherein the non-fluorinated polymer is at least one selected from the group consisting of an aliphatic polyamide resin, an aromatic polyamide resin, a polyolefin resin, a modified polyolefin resin, and an ethylene / vinyl alcohol copolymer resin.

13. The fuel permeation rate is 15 g / m ２ 3. The laminate according to claim 1 or 2, wherein the average molecular weight is 10 ...

14. A tube or hose formed from the laminate of claim 1 or 2.

15. A tube or hose formed from the laminate of claim 1 or 2, The laminate comprises: A conductive filler and a fluororesin layer containing a fluororesin containing a chlorotrifluoroethylene unit and a tetrafluoroethylene unit; and a non-fluorinated polymer layer containing an aliphatic polyamide resin; In this order, The fluororesin layer is the innermost layer and contacts the fuel. Tube or hose.

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