Laminate in contact with fuel

Abstract

Provided is a laminate which is in contact with a fuel containing at least a compound (1) that is composed only of a carbon atom, a hydrogen atom, and an oxygen atom and has a carbonyl group or an ether bond. The laminate is provided with at least a non-fluorinated polymer layer containing at least one non-fluorinated polymer selected from the group consisting of ethylene / vinyl alcohol copolymers and aromatic polyamides.

Description

Technical Field

[0001] This invention relates to laminates in contact with fuel. Background Technology

[0002] Patent Document 1 describes a laminated structure consisting of two or more layers, comprising at least (A) a (a) layer composed of an aliphatic polyamide and (B) a (b) layer composed of a semi-aromatic polyamide, wherein the (b) layer is disposed as the innermost layer, and the semi-aromatic polyamide is composed of diamine units having aliphatic diamine units containing 60 mol% or more of carbon atoms (9 to 13) relative to all diamine units and dicarboxylic acid units containing 50 mol% or more of terephthalic acid and / or naphthalenedicarboxylic acid units relative to all dicarboxylic acid units.

[0003] Existing technical documents

[0004] Patent documents

[0005] Patent Document 1: International Publication No. 2005 / 102694 Summary of the Invention

[0006] The problem that the invention aims to solve

[0007] The object of the present invention is to provide a laminate that exhibits excellent fuel low permeability for fuels containing compounds consisting only of carbon atoms, hydrogen atoms and oxygen atoms and having carbonyl or ether bonds.

[0008] Methods for solving problems

[0009] According to the present invention, a laminate is provided that is in contact with a fuel, wherein the fuel contains at least a compound (1), the compound (1) being composed only of carbon atoms, hydrogen atoms and oxygen atoms and having a carbonyl or ether bond, and the laminate has at least a non-fluorinated polymer layer containing at least one non-fluorinated polymer selected from the group consisting of ethylene / vinyl alcohol copolymers and aromatic polyamides.

[0010] Invention Effects

[0011] According to the present invention, a laminate can be provided that exhibits excellent fuel low permeability for fuels containing compounds consisting only of carbon atoms, hydrogen atoms, and oxygen atoms and having carbonyl or ether bonds. Detailed Implementation

[0012] The specific embodiments of the present invention will be described in detail below, but the present invention is not limited to the following embodiments.

[0013] Previously, laminates exhibiting low fuel permeability to gasoline or to alcohol-containing gasoline were known.

[0014] For example, Patent Document 1 describes the determination of the fuel permeability coefficient of a laminated structure having the above configuration for an alcohol-containing gasoline containing FuelC (isooctane / toluene = 50 / 50 volume ratio) and ethanol mixed in a volume ratio of 90 / 10.

[0015] However, the type of laminated structure required to suppress the permeation of fuels containing only carbon, hydrogen, and oxygen atoms and having carbonyl or ether bonds has not been adequately studied to date.

[0016] It has been found that by introducing a non-fluorinated polymer layer containing at least one non-fluorinated polymer selected from the group consisting of ethylene / vinyl alcohol copolymers and aromatic polyamides into the laminate, the laminate exhibits surprisingly low fuel permeability for fuels containing compounds consisting only of carbon atoms, hydrogen atoms, and oxygen atoms and having carbonyl or ether bonds.

[0017] That is, the laminate of the present invention is a laminate in contact with a fuel containing at least a compound (1) consisting only of carbon atoms, hydrogen atoms and oxygen atoms and having carbonyl or ether bonds, and having at least a non-fluorinated polymer layer containing at least one non-fluorinated polymer selected from the group consisting of ethylene / vinyl alcohol copolymer and aromatic polyamide.

[0018] The structure of the laminate of the present invention will be described in detail below.

[0019] (fuel)

[0020] The laminate of the present invention is used in contact with fuel containing at least a compound (1) consisting only of carbon atoms, hydrogen atoms, and oxygen atoms and having a carbonyl group or ether bond. In one embodiment, the laminate of the present invention is used to suppress the permeation of fuel containing at least a compound (1) consisting only of carbon atoms, hydrogen atoms, and oxygen atoms and having a carbonyl group or ether bond. In one embodiment, the laminate of the present invention is a pipe or hose for allowing the flow of fuel containing at least a compound (1) consisting only of carbon atoms, hydrogen atoms, and oxygen atoms and having a carbonyl group or ether bond and / or for suppressing the permeation of the fuel.

[0021] That is, the present invention includes the use of a laminate (piping or hose) for the flow of fuel containing at least a compound (1) consisting only of carbon atoms, hydrogen atoms and oxygen atoms and having a carbonyl or ether bond and / or for inhibiting the permeation of the fuel.

[0022] Additionally, the present invention includes a method for circulating a fuel containing at least a compound (1) consisting only of carbon atoms, hydrogen atoms and oxygen atoms and having a carbonyl or ether bond, wherein a laminate (piping or hose) is used while in contact with the fuel.

[0023] Compound (1) can be a compound synthesized from hydrogen and carbon dioxide. Compounds synthesized from hydrogen and carbon dioxide are also known as synthetic fuels and are expected to contribute to the reduction of carbon dioxide emissions. According to the inventors' research, even if conventional fuels such as gasoline, diesel, and alcohol fuels can be suppressed, the permeation of such synthetic fuels cannot be sufficiently suppressed. That is, compound (1) exhibits permeability different from conventional fuels such as gasoline, diesel, and alcohol fuels. Therefore, conventional insights cannot be effectively utilized when selecting the layer composition of a laminate for use with fuels containing compound (1). Thus, the present invention conducted in-depth research and discovered a laminate that also exhibits low fuel permeability for compound (1).

[0024] As compound (1), it is preferably selected from at least one of the group consisting of carbonates, chain ethers and cyclic ethers, more preferably from at least one of the group consisting of carbonates and cyclic ethers, and even more preferably from carbonates.

[0025] Examples of compound (1) include dimethyl carbonate, diethyl carbonate, dimethyl ether, methyl tert-butyl ether (MTBE), oxymethylene dimethyl ether, 1,3-dioxolane, etc. The fuel contains one or more of these compounds. As compound (1), preferably at least one is selected from the group consisting of dimethyl carbonate and diethyl carbonate.

[0026] The fuel may contain only compound (1) or it may contain compound (1) and other fuels.

[0027] Examples of fuels include: fuels containing only compound (1); fuels containing compound (1) and alcohol; fuels containing compound (1) and gasoline; fuels containing compound (1), alcohol and gasoline; fuels containing compound (1) and diesel fuel (light oil); and so on.

[0028] The content of compound (1) in the fuel can be from 0.1 vol% to 100 vol%. The content of compound (1) in the fuel can be more than 1 vol%, more than 5 vol%, or more than 10 vol%. The content of compound (1) in the fuel can be less than 90 vol%, less than 80 vol%, less than 60 vol%, less than 40 vol%, or less than 20 vol%.

[0029] In one embodiment, the fuel contains compound (1) and an alcohol. The laminate of the present invention also exhibits excellent low permeability for fuels containing compound (1) and an alcohol.

[0030] As an alcohol, an alcohol having 1 to 5 carbon atoms is preferred, more preferably at least one of the group consisting of methanol, ethanol, propanol and butanol, and even more preferably at least one of the group consisting of methanol and ethanol.

[0031] The alcohol content in fuel can range from 10% to 99.9% by volume. The alcohol content in fuel can be 20% or more by volume, 40% or more by volume, or 80% or more by volume. The alcohol content in fuel can be less than 99% by volume, less than 95% by volume, or less than 90% by volume.

[0032] When the alcohol in the fuel is methanol, its content can be from 10% to 99.9% by volume. The methanol content in the fuel can be less than 80% by volume, less than 50% by volume, less than 30% by volume, or less than 20% by volume.

[0033] In one embodiment, the fuel contains compound (1) and gasoline. The laminate of the present invention also exhibits excellent low permeability to fuels containing compound (1) and gasoline.

[0034] Gasoline can be obtained by refining crude oil. The boiling point of gasoline is usually between 30°C and 220°C.

[0035] The gasoline content in the fuel can be from 10% to 99.9% by volume. The gasoline content in the fuel can be 20% or more by volume, 40% or more by volume, or 80% or more by volume. The gasoline content in the fuel can be less than 99% by volume, less than 95% by volume, or less than 90% by volume.

[0036] In one embodiment, the fuel does not contain diesel fuel (light oil). The diesel fuel may be refined from crude oil. The boiling point of diesel fuel is typically greater than 220°C and below 350°C.

[0037] In one embodiment, the fuel contains compound (1) and diesel fuel (light oil).

[0038] Previously, aliphatic polyamides, which possess excellent acid resistance, alkali resistance, hydrolysis resistance, and physical properties, were used as forming materials for piping or hoses used for diesel fuel. Unlike gasoline and alcohol-containing fuels, diesel fuel (light oil) is difficult to pipe through aliphatic polyamides. Therefore, research has not yet been conducted on selecting materials from the perspective of inhibiting diesel fuel permeation.

[0039] Compound (1) can be a compound synthesized from hydrogen and carbon dioxide. Compounds synthesized from hydrogen and carbon dioxide are also known as synthetic fuels and are expected to contribute to the reduction of carbon dioxide emissions. Diesel fuel (light oil) is difficult to pass through aliphatic polyamide piping, unlike gasoline and alcohol-containing fuels. However, it has been found that if such synthetic fuels are blended into diesel fuel, the fuel will pass through the piping and diffuse to the outside. Therefore, the present invention has conducted in-depth research and found that a laminate also exhibits low fuel permeability for fuels containing diesel fuel and compound (1).

[0040] That is, it has been found that by introducing a non-fluorinated polymer layer containing at least one non-fluorinated polymer selected from the group consisting of ethylene / vinyl alcohol copolymers and aromatic polyamides into the laminate, the laminate exhibits surprisingly low fuel permeability for diesel fuels and fuels containing compounds consisting only of carbon atoms, hydrogen atoms and oxygen atoms and having carbonyl or ether bonds.

[0041] Diesel fuel can be obtained by refining crude oil. The boiling point of diesel fuel is typically greater than 220°C and below 350°C.

[0042] The diesel fuel content in the fuel can be from 10% to 99.9% by volume. The diesel fuel content in the fuel can be 20% or more by volume, 40% or more by volume, or 80% or more by volume. The diesel fuel content in the fuel can be less than 99% by volume, less than 95% by volume, or less than 90% by volume.

[0043] In one embodiment, the fuel does not contain gasoline. The gasoline may be refined from crude oil. Gasoline typically has a boiling point of 30°C to 220°C.

[0044] In one embodiment, the fuel does not contain alcohol. Examples of alcohols include those with 1 to 5 carbon atoms.

[0045] (Non-fluorinated polymer layer (A))

[0046] The laminate of the present invention comprises at least a non-fluorinated polymer layer (A), said non-fluorinated polymer layer (A) containing at least one non-fluorinated polymer (A) selected from the group consisting of ethylene / vinyl alcohol copolymers and aromatic polyamides.

[0047] Thus, the laminate of the present invention comprises at least a non-fluorinated polymer layer (A) containing at least one non-fluorinated polymer (A) selected from the group consisting of ethylene / vinyl alcohol copolymers and aromatic polyamides. Therefore, it exhibits excellent low fuel permeability for fuels containing compounds consisting only of carbon, hydrogen, and oxygen atoms and having carbonyl or ether bonds. Surprisingly, sufficient low fuel permeability cannot be obtained if non-fluorinated polymers other than ethylene / vinyl alcohol copolymers and aromatic polyamides, such as aliphatic polyamides like PA12, are used.

[0048] The ethylene / vinyl alcohol copolymer used in the laminates of this invention can be a thermoplastic resin. The ethylene / vinyl alcohol copolymer is obtained by saponifying an ethylene / vinyl acetate copolymer derived from ethylene and vinyl acetate. The mixing ratio of the copolymerized ethylene and vinyl acetate is appropriately determined based on the molar ratio of vinyl acetate units specified by the following formula.

[0049] For ethylene / vinyl alcohol copolymers, the preferred vinyl acetate unit molar percentage (X) and saponification degree (Y%) satisfy X×Y / 100 ≥ 7. If X×Y / 100 < 7, the interlayer adhesion may be insufficient. More preferably, X×Y / 100 ≥ 10. The value of X×Y / 100 is an indicator of the hydroxyl content of the ethylene / vinyl alcohol copolymer; a larger X×Y / 100 value means a higher hydroxyl content in the ethylene / vinyl alcohol copolymer.

[0050] Hydroxyl groups are functional groups that can participate in the adhesion between the EVOH layer and the laminated target material. A high hydroxyl content in the ethylene / vinyl alcohol copolymer enhances the interlayer adhesion in the laminate. In this invention, the "laminated target material" refers to the material that is in contact with and laminated with the other materials.

[0051] In this invention, "vinyl acetate unit X moles %" refers to the proportion of the number of moles of vinyl acetate [Ni] from the vinyl acetate unit in the total number of moles of ethylene and vinyl acetate added to the ethylene / vinyl alcohol copolymer molecule [N], which is determined by the following formula

[0052] Xi(%)=(Ni / N)×100

[0053] The molar content Xi represents the average value. The vinyl acetate unit X mol% is a value obtained by infrared absorption spectroscopy [IR].

[0054] In this invention, the "vinyl acetate unit" is a part of the molecular structure of the ethylene / vinyl alcohol copolymer, referring to the portion derived from vinyl acetate. The vinyl acetate unit can be saponified to have hydroxyl groups, or it can remain unsaponified to have acetoxy groups.

[0055] "Saponification degree" is a percentage representing the number of saponified vinyl acetate units relative to the total number of saponified vinyl acetate units and the number of unsaponified vinyl acetate units. The saponification degree is determined using infrared absorption spectrometry (IR).

[0056] Examples of commercially available products that are ethylene / vinyl alcohol copolymers with X and Y satisfying the above formula include EVAL F101 (manufactured by KURARAY, vinyl acetate unit X = 68.0 mol; saponification degree Y = 95%; X×Y / 100 = 64.6), Melthene H6051 (manufactured by Tosoh, vinyl acetate unit X = 11.2 mol; saponification degree Y = 100%; X×Y / 100 = 11.2), and TECHNOLINK K200 (manufactured by Taoka Chemicals, vinyl acetate unit X = 11.2 mol; saponification degree Y = 85%; X×Y / 100 = 9.52).

[0057] The ethylene / vinyl alcohol copolymer preferably has a melt flow rate (MFR) of 0.5 g / 10 min or higher at 200°C, and more preferably 100 g / 10 min or lower. 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 and the melt viscosity of the target material tends to increase, and uneven thickness of each layer may occur, which is therefore not preferred. The preferred lower limit is 1 g / 10 min, and the preferred upper limit is 50 g / 10 min.

[0058] The aromatic polyamide used in the laminates of this invention can be a thermoplastic resin. In this invention, the aromatic polyamides include semi-aromatic polyamides and fully aromatic polyamides. In one embodiment, the aromatic polyamide is a semi-aromatic polyamide containing an aliphatic diamine unit and an aromatic dicarboxylic acid unit.

[0059] Examples of aliphatic diamines include 1,2-ethylenediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,11-undecanediamine, and 1,12-dodecanediamine, among which 1,6-hexanediamine and 1,9-nonanediamine are preferred.

[0060] Examples of aromatic dicarboxylic acids include terephthalic acid, phthalic acid, isophthalic acid, and naphthalic acid, with terephthalic acid being preferred.

[0061] The melting point of the semi-aromatic polyamide is preferably above 200°C, more preferably above 250°C, and most preferably below 350°C.

[0062] As aromatic polyamides, polyamide 6T and polyamide 9T are preferred, with polyamide 9T being more preferred.

[0063] Without prejudice to the purpose of this invention, various additives such as heat stabilizers, reinforcing agents, fillers, ultraviolet absorbers, and pigments may be added to the non-fluorinated polymer layer (A). By using such additives, the properties of the non-fluorinated polymer, such as thermal stability, surface hardness, wear resistance, electrical conductivity, and weather resistance, can be improved.

[0064] In one embodiment, the non-fluorinated polymer layer (A) is not conductive. In another embodiment, the non-fluorinated polymer layer (A) does not contain conductive fillers.

[0065] (Conductive layer (N1))

[0066] The laminate of the present invention may further include a conductive layer (N1), which is conductive and contains a non-fluorinated polymer (N1). By including the conductive layer (N1), the laminate can be prevented from becoming charged even when static electricity is generated due to friction between the laminate and the fuel.

[0067] Non-fluorinated polymers (N1) are polymers that do not have fluorine atoms. Polymers known as thermoplastic resins can be widely used as non-fluorinated polymers (N1). Examples of non-fluorinated polymers (N1) include polyamide resins, polyolefin resins, vinyl chloride resins, polyurethane resins, polyester resins, polyaramid resins, polyimide resins, polyamide-imide resins, polyphenylene ether resins, polyacetal resins, polycarbonate resins, acrylic resins, styrene resins, acrylonitrile / butadiene / styrene resins [ABS], cellulose resins, polyetheretherketone resins [PEEK], polysulfone resins, polyethersulfone resins [PES], polyetherimide resins, ethylene / vinyl alcohol copolymer resins, polyphenylene sulfide resins, polybutylene naphthalate resins, polybutylene terephthalate resins, and polyphthalamide [PPA].

[0068] The melting point of the non-fluorinated polymer (N1) is preferably 50°C or higher, more preferably 100°C or higher, even more preferably 150°C or higher, even more preferably 200°C or higher, particularly preferably 250°C or higher, preferably 400°C or lower, more preferably 350°C or lower, even more preferably 300°C or lower, and even more preferably 250°C or lower.

[0069] As the non-fluorinated polymer (N1) constituting the conductive layer (N1), an aromatic polyamide is preferred. The same material as the aromatic polyamide constituting the non-fluorinated polymer layer (A) can be used as the aromatic polyamide, and preferably the same material.

[0070] In one embodiment, the aromatic polyamide constituting the conductive layer (N1) is an aromatic polyamide containing aliphatic diamine units and aromatic dicarboxylic acid units.

[0071] As an aromatic polyamide constituting the conductive layer (N1), polyamide 6T and polyamide 9T are preferred, and polyamide 9T is more preferred.

[0072] The conductive layer (N1) preferably contains conductive filler. By containing conductive filler, the conductive layer (N1) can be easily made conductive, and even in the event of static electricity generated due to friction between the laminate and the fuel, the charge on the laminate can be further prevented.

[0073] There are no particular limitations on conductive fillers; examples include: conductive single powders or conductive single fibers such as metals and carbon; powders of conductive compounds such as zinc oxide; powders with surface conductive treatment; etc.

[0074] There are no particular limitations on whether it is a conductive single powder or a conductive single fiber. Examples include: metal powders such as copper and nickel; metal fibers such as iron and stainless steel; carbon black, carbon fiber, carbon nanotubes, carbon nanotubes, etc. as described in Japanese Patent Application Publication No. 3-174018.

[0075] Surface-conductive powder is obtained by applying a conductive treatment to the surface of non-conductive powders such as glass beads and titanium dioxide. The method of conductive treatment is not particularly limited, and examples include metal sputtering and electroless plating. Among the conductive fillers mentioned above, carbon black is advantageous from an economic perspective and is therefore preferred.

[0076] The amount of conductive filler used is appropriately determined based on the type of non-fluorinated polymer (N1), the required conductivity of the laminate, molding conditions, etc., and is preferably 1 part by mass or more, and preferably 30 parts by mass or less, relative to 100 parts by mass of non-fluorinated polymer (N1). More preferably, the lower limit is 5 parts by mass, and more preferably, the upper limit is 20 parts by mass.

[0077] In addition to conductive fillers, the conductive layer (N1) can also contain various additives such as reinforcing agents, fillers, ultraviolet absorbers, and pigments, without compromising the purpose of this invention. By using such additives, the properties of the conductive layer (N1), such as surface hardness, wear resistance, electrical conductivity, and weather resistance, can be improved.

[0078] When the laminate of the present invention includes a conductive layer (N1), it is preferable to form a structure in which the conductive layer (N1) is in contact with the fuel. By forming the contact surface between the laminate and the fuel with the conductive layer (N1), even if static electricity is generated due to friction between the laminate and the fuel, it is possible to further prevent the laminate from becoming charged.

[0079] (Fluoropolymer layer (F))

[0080] The laminate of the present invention may further include a fluoropolymer layer (F) containing a fluoropolymer. The fluoropolymer is a partially crystalline fluoropolymer, not a fluororubber, but a fluoroplastic. The fluoropolymer has a melting point and is thermoplastic. The fluoropolymer can be melt-processable or non-melt-processable; from the perspective of enabling high-productivity tube production via melt extrusion molding, a melt-processable fluoropolymer is preferred.

[0081] In this invention, melt processability refers to the ability to melt and process the polymer using existing processing equipment such as extruders and injection molding machines. Therefore, the melt flow rate of melt-processable fluoropolymers is typically between 0.01 g / 10 min and 500 g / 10 min.

[0082] Examples of melt-processable fluoropolymers include tetrafluoroethylene (TFE) / perfluoro(alkyl vinyl ether) (PAVE) copolymer, tetrafluoroethylene (TFE) / hexafluoropropylene (HFP) copolymer, TFE / ethylene copolymer [ETFE], TFE / ethylene / HFP copolymer, polymers containing trifluorochloroethylene (CTFE) units, polyvinylidene fluoride [PVdF], TFE / vinylidene fluoride (VdF) copolymer [VT], polyvinylidene fluoride [PVF], TFE / HFP / VdF copolymer, etc.

[0083] Examples of perfluoro(methyl vinyl ether) (PMVE), perfluoro(ethyl vinyl ether) (PEVE), and perfluoro(propyl vinyl ether) (PPVE) are perfluoro(methyl vinyl ether). PPVE is preferred. One or more of these can be used.

[0084] Fluoropolymers can have polymerization units based on other monomers in amounts that do not impair the inherent properties of each fluoropolymer. These other monomers can be appropriately selected from, for example, TFE, HFP, ethylene, propylene, perfluoro(alkyl vinyl ether), perfluoroalkyl ethylene, hydrofluoroolefin, fluoroalkyl ethylene, and perfluoro(alkyl allyl ether).

[0085] The melting point of the fluoropolymer is preferably above 160°C, more preferably above 190°C, even more preferably above 230°C, particularly preferably above 240°C, more preferably below 324°C, more preferably below 320°C, even more preferably below 300°C, particularly preferably below 280°C, and most preferably below 260°C.

[0086] The melt flow rate (MFR) of the fluoropolymer at an optional temperature (e.g., 265°C or 297°C) within the typical molding temperature range of 230°C to 350°C is preferably 0.5 g / 10 min or more, more preferably 2.0 g / 10 min or more, further preferably 5.0 g / 10 min or more, particularly preferably 10 g / 10 min or more, most preferably 15 g / 10 min or more, preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less, further preferably 40 g / 10 min or less, and particularly preferably 35 g / 10 min or less. The melt flow rate can be determined, for example, by measuring the mass (g) of fluoropolymer flowing out per unit time (10 min) from a nozzle with an inner diameter of 2 mm and a length of 8 mm at an optional load (e.g., 2.16 kg or 5 kg) at an optional temperature (e.g., 265°C or 297°C) using a melt flow index meter.

[0087] As a fluoropolymer, it is preferably at least one selected from the group consisting of TFE / perfluoro(alkyl vinyl ether) (PAVE) copolymer, tetrafluoroethylene (TFE) / hexafluoropropylene (HFP) copolymer, TFE / ethylene copolymer [ETFE], TFE / ethylene / HFP copolymer, polymers containing CTFE units, and tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer [THV], more preferably at least one selected from the group consisting of TFE / ethylene copolymer [ETFE], TFE / ethylene / HFP copolymer, and polymers containing CTFE units, and more preferably at least one selected from the group consisting of TFE / ethylene copolymer [ETFE] and TFE / ethylene / HFP copolymer.

[0088] In this invention, the composition of the fluoropolymer can be calculated by appropriately combining the types of monomers using NMR, FT-IR, elemental analysis, and fluorescence X-ray analysis.

[0089] In the TFE / HFP copolymer, the TFE / HFP ratio is preferably 80-97 / 3-20 by mass, and more preferably 84-92 / 8-16.

[0090] TFE / HFP copolymers can be binary copolymers composed of TFE and HFP, or terpolymers containing monomers capable of copolymerizing with TFE and HFP (e.g., TFE / HFP / PAVE copolymers).

[0091] TFE / HFP copolymers are also preferably TFE / HFP / PAVE copolymers containing PAVE-based polymerization units.

[0092] In the TFE / HFP / PAVE copolymer, the TFE / HFP / PAVE ratio by mass is preferably 70-97 / 2.9-20 / 0.1-10, more preferably 81-92 / 5-16 / 0.3-5.

[0093] In the TFE / PAVE copolymer, the TFE / PAVE ratio is preferably 90-99 / 1-10 by mass, and more preferably 92-97 / 3-8.

[0094] ETFE is a copolymer containing ethylene units and TFE units. Preferably, the molar ratio of TFE units to ethylene units (TFE units / ethylene units) of ETFE is 20 / 80 or more and 90 / 10 or less. More preferably, the molar ratio is 37 / 63 or more and 85 / 15 or less, and even more preferably, the molar ratio is 38 / 62 or more and 80 / 20 or less. The aforementioned ETFE can be a copolymer composed of TFE, ethylene, and monomers capable of copolymerizing with TFE and ethylene. Examples of monomers capable of copolymerization include those shown in the following formula: CH2=CX 5 Rf 3 CF2=CFRf 3 CF2=CFORf 3 CH2=C(Rf 3 )2 (where X) 5 Represents H or F, Rf 3 This indicates that fluoroalkyl groups may contain ether bonds. Among them, the preferred choice is CF2=CFRf 3 CF2=CFORf 3 and CH2=CX 5 Rf 3 At least one of the fluorinated vinyl monomers shown, more preferably HFP, CF2=CF-ORf 4 (where Rf) 4 Perfluoroalkyl groups (representing alkyl groups with 1 to 5 carbon atoms) are shown as perfluoro(alkyl vinyl ethers) and Rf 3 CH2=CX of fluoroalkyl groups having 1 to 8 carbon atoms 5 Rf 3 At least one of the fluorinated vinyl monomers shown is preferred, especially HFP. Additionally, monomers capable of copolymerizing with TFE and ethylene can be aliphatic unsaturated carboxylic acids such as itaconic acid and itaconic anhydride. In ETFE, the monomer units capable of copolymerizing with TFE and ethylene are preferably 0.1 mol% or more, preferably 0.2 mol% or more, preferably 10 mol% or less, more preferably 5 mol% or less, and particularly preferably 4 mol% or less.

[0095] The TFE / ethylene copolymer [ETFE] is also preferably a TFE / ethylene / HFP copolymer containing HFP-based polymerization units (HFP units). In the TFE / ethylene / HFP copolymer, the molar ratio of TFE / ethylene / HFP is preferably 40-65 / 30-59.5 / 0.5-20, more preferably 40-65 / 30-59.5 / 0.5-10.

[0096] The melting point of ETFE is preferably above 160°C, more preferably above 170°C, even more preferably above 180°C, particularly preferably above 190°C, preferably below 324°C, more preferably below 320°C, even more preferably below 300°C, particularly preferably below 280°C, and most preferably below 260°C.

[0097] The MFR (at 265°C) of ETFE is preferably 0.5 g / 10 min or more, more preferably 2.0 g / 10 min or more, further preferably 5.0 g / 10 min or more, particularly preferably 8 g / 10 min or more, most preferably 10 g / 10 min or more, preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less, further preferably 40 g / 10 min or less, particularly preferably 30 g / 10 min or less, and most preferably 25 g / 10 min or less. The MFR of ETFE is determined at a temperature of 297°C or 265°C and a load of 5 kg.

[0098] As for ETFE, the ethylene / tetrafluoroethylene copolymer described in Japanese Patent Application Publication No. 2019-90013 is also preferred.

[0099] As a polymer containing CTFE units, it is preferably selected from at least one of the groups consisting of polychlorotrifluoroethylene [PCTFE] and CTFE copolymers.

[0100] From the perspective of further improving fuel permeability, the content of CTFE units in the polymer containing CTFE units is 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, preferably 100 mol% or less, more preferably 75.0 mol% or less, even more preferably 50.0 mol% or less, and particularly preferably 30.0 mol% or less, relative to all monomer units.

[0101] Examples of polymers containing CTFE units include ethylene / chlorotrifluoroethylene (CTFE) copolymer [ECTFE], polychlorotrifluoroethylene [PCTFE], CTFE / tetrafluoroethylene (TFE) copolymer, TFE / vinylidene fluoride (VdF) / CTFE copolymer [VTC], etc., preferably at least one of the group consisting of PCTFE, ethylene / CTFE copolymer and CTFE / TFE copolymer, and more preferably CTFE / TFE copolymer from the viewpoint of low fuel permeability.

[0102] Examples of PCTFE include CTFE homopolymers and polymers containing CTFE units and a small number of comonomer units.

[0103] The melting point of PCTFE is preferably 150°C or higher, more preferably 190°C or higher, more preferably 230°C or lower, and more preferably 217°C or lower. The melting point is the temperature corresponding to the maximum value in the heat of fusion curve when heated at a rate of 10°C / min using a differential scanning calorimeter [DSC].

[0104] The preferred flow value for PCTFE is 1×10⁻⁶. -4 (cm 3 ( / second) or higher, preferably 5×10 -1 (cm 3 The flow rate was below (per second). The flow value was determined using a high-performance flow tester CFT-500D (manufactured by Shimadzu Corporation), which melted PCTFE at 230°C and applied a 100kg load from a nozzle with a diameter of 1mm. The volume of resin extruded per second during extrusion.

[0105] The content of CTFE units in PCTFE is preferably 95 mol% or more, more preferably 98 mol% or more, even more preferably 99 mol% or more, and preferably 100 mol% or less.

[0106] As a comonomer that can constitute PCTFE, there are no particular limitations on any monomer that can copolymerize with CTFE. Examples include TFE, ethylene, vinylidene fluoride, perfluoroalkyl vinyl ether, hexafluoroethylene, etc.

[0107] Ethylene / CTFE copolymer (ECTFE) is a copolymer comprising ethylene units and CTFE units, preferably with ethylene units comprising 46 mol% to 52 mol% and CTFE units comprising 54 mol% to 48 mol% relative to the total number of ethylene units and CTFE units. ECTFE can be a binary copolymer consisting only of ethylene units and CTFE units, and can further comprise polymeric units based on monomers capable of copolymerizing with ethylene and CTFE (e.g., fluoroalkyl vinyl ether (PAVE) derivatives).

[0108] The content of polymerization units based on monomers capable of copolymerizing with ethylene and CTFE is preferably 0.01 mol% or more, and preferably 5 mol% or less, relative to the total of ethylene units, CTFE units, and the above-mentioned polymerization units based on copolymerizable monomers.

[0109] The MFR (at 230°C) of ECTFE is preferably 0.5 g / 10 min or more, and more preferably 100 g / 10 min or less. The MFR of ECTFE is determined at a temperature of 230°C and a load of 2.16 kg.

[0110] The CTFE / TFE copolymer contains CTFE units and TFE units. As a CTFE / TFE copolymer, it is particularly preferred to contain CTFE units, TFE units and monomer (α) units from monomers (α) that can copolymerize with them.

[0111] As a monomer (α), there are no particular limitations as long as it can copolymerize with CTFE and TFE; examples include ethylene (Et), VdF, and CF2=CF-ORf. 1 (where Rf) 1 Perfluoro(alkyl vinyl ether) [PAVE], CX (represented by perfluoroalkyl groups having 1 to 8 carbon atoms) 3 X 4 =CX 5 (CF2) n X 6 (where X) 3 X 4 and X 5 They may be the same or different, consisting of hydrogen or fluorine atoms; X 6 Vinyl monomers represented by (where n is an integer from 1 to 10, consisting of hydrogen, fluorine, or chlorine atoms) and CF2=CF-OCH2-Rf 2 (where Rf) 2 Alkyl perfluorovinyl ether derivatives, etc., represented by perfluoroalkyl groups having 1 to 5 carbon atoms, preferably at least one selected from the group consisting of PAVE, the above-mentioned vinyl monomers and alkyl perfluorovinyl ether derivatives, more preferably at least one selected from the group consisting of PAVE and HFP.

[0112] As for PAVE, the preferred value is CF2 = CF - ORf. 3 (where Rf) 3The perfluoro(alkyl vinyl ether) represented by a perfluoroalkyl group having 1 to 5 carbon atoms can be exemplified by perfluoro(methyl vinyl ether) [PMVE], perfluoro(ethyl vinyl ether) [PEVE], perfluoro(propyl vinyl ether) [PPVE], perfluoro(butyl vinyl ether], etc., wherein at least one of the group consisting of PMVE, PEVE and PPVE is more preferred, and PPVE is even more preferred.

[0113] Rf is preferred as an alkyl perfluorovinyl ether derivative. 2 It is a perfluoroalkyl group having 1 to 3 carbon atoms, more preferably CF2=CF-OCH2-CF2CF3.

[0114] The preferred ratio of CTFE units to TFE units in the CTFE / TFE copolymer is 15.0 mol% to 90.0 mol% of CTFE units and 85.0 mol% to 10.0 mol% of TFE units, more preferably 15.0 mol% to 50.0 mol% of CTFE units and 85.0 mol% to 50.0 mol% of TFE units, and even more preferably 15.0 mol% to 30.0 mol% of CTFE units and 85.0 mol% to 70.0 mol% of TFE units.

[0115] The preferred CTFE / TFE copolymer has a total CTFE and TFE unit content of 90.0 mol% to 99.9 mol% and a monomer (α) unit content of 0.1 mol% to 10.0 mol%. If the monomer (α) unit content is less than 0.1 mol%, the moldability, environmental stress cracking resistance, and fuel cracking resistance tend to deteriorate. If it exceeds 10.0 mol%, it tends to have poor fuel barrier properties, heat resistance, and mechanical properties.

[0116] As a CTFE / TFE copolymer, a CTFE / TFE / PAVE copolymer is particularly preferred.

[0117] In the CTFE / TFE / PAVE copolymer, the PAVE mentioned above can be perfluoro(methyl vinyl ether) [PMVE], perfluoro(ethyl vinyl ether) [PEVE], perfluoro(propyl vinyl ether) [PPVE], perfluoro(butyl vinyl ether], etc., wherein at least one of the group consisting of PMVE, PEVE and PPVE is preferred, and PPVE is more preferred.

[0118] In the CTFE / TFE / PAVE copolymer, the PAVE unit is preferably 0.5 mol% or more, and more preferably 5 mol% or less, of all monomer units.

[0119] The melting point of the CTFE / TFE copolymer is preferably above 190°C, more preferably above 210°C, further preferably above 220°C, particularly preferably above 230°C, most preferably above 240°C, preferably below 324°C, more preferably below 320°C, further preferably below 270°C, and most preferably below 260°C.

[0120] The MFR (at 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, further preferably 5.0 g / 10 min or more, particularly preferably 7 g / 10 min or more, most preferably 10 g / 10 min or more, preferably 100 g / 10 min or less, more preferably 50 g / 10 min or less, further preferably 40 g / 10 min or less, and particularly preferably 35 g / 10 min or less. The MFR of the CTFE / TFE copolymer is determined at a temperature of 297°C and a load of 5 kg.

[0121] The fluoropolymer layer (F) is preferably conductive, and the conductivity of the fluoropolymer layer (F) prevents the laminate from becoming charged even when static electricity is generated due to friction between the laminate and the fuel.

[0122] The fluoropolymer layer (F) preferably contains a conductive filler. By containing a conductive filler, the fluoropolymer layer (F) is easily made conductive, and the laminate can be prevented from becoming charged even when static electricity is generated due to friction between the laminate and the fuel.

[0123] As a conductive filler, the same material as that which may be contained in the conductive layer (N1) can be used, preferably the same material.

[0124] The amount of conductive filler used is appropriately determined based on the type of fluororesin, the required conductivity of the laminate, molding conditions, etc., and is preferably 1 part by mass or more, and more preferably 30 parts by mass or less, relative to 100 parts by mass of fluororesin. A more preferred lower limit is 5 parts by mass, and a more preferred upper limit is 20 parts by mass.

[0125] In addition to conductive fillers, various additives such as reinforcing agents, fillers, ultraviolet absorbers, and pigments can be added to the fluoropolymer layer (F) without compromising the purpose of this invention. By using such additives, the properties of the fluoropolymer layer (F), such as surface hardness, wear resistance, electrical conductivity, and weather resistance, can be improved.

[0126] When the laminate of the present invention includes a fluoropolymer layer (F), it is preferable to construct it in such a way that the fluoropolymer layer (F) is in contact with the fuel. By forming the contact surface between the laminate and the fuel with the fluoropolymer layer (F), the laminate is endowed with excellent fuel resistance, and the durability of the laminate is improved. In addition, when the fluoropolymer layer (F) is conductive, by forming the contact surface between the laminate and the fuel with the fluoropolymer layer (F), even if static electricity is generated due to friction between the laminate and the fuel, it is possible to further prevent the laminate from becoming charged.

[0127] (Non-fluorinated polymer (N2))

[0128] The laminate of the present invention may further comprise a non-fluorinated polymer layer (N2), which is non-conductive and contains a non-fluorinated polymer (N2) (excluding non-fluorinated polymer (A)). The non-fluorinated polymer (N2) is a non-fluorinated polymer other than ethylene / vinyl alcohol copolymers and aromatic polyamides.

[0129] As a non-fluorinated polymer (N2), polymers known as thermoplastic resins other than ethylene / vinyl alcohol copolymers and aromatic polyamides can be widely used. Examples of non-fluorinated polymers (N2) include aliphatic polyamide resins, polyolefin resins, vinyl chloride resins, polyurethane resins, polyester resins, polyaromatic polyamide resins, polyimide resins, polyamide-imide resins, polyphenylene ether resins, polyacetal resins, polycarbonate resins, acrylic resins, styrene resins, acrylonitrile / butadiene / styrene resins [ABS], cellulose resins, polyetheretherketone resins [PEEK], polysulfone resins, polyethersulfone resins [PES], polyetherimide resins, polyphenylene sulfide resins, polybutylene naphthalate resins, polybutylene terephthalate resins, polyphthalamide [PPA], etc.

[0130] The melting point of the non-fluorinated polymer (N2) is preferably above 50°C, more preferably above 100°C, even more preferably above 150°C, preferably below 400°C, more preferably below 300°C, and even more preferably below 250°C.

[0131] As a non-fluorinated polymer (N2), it is preferably selected from at least one of the group consisting of aliphatic polyamide resins and polyolefin resins, and more preferably aliphatic polyamide resins.

[0132] Aliphatic polyamide resins are so-called nylon resins composed of polymers in which amide bonds within the molecule are bonded to aliphatic or alicyclic structures.

[0133] There are no particular limitations on aliphatic polyamide resins (nylon resins), and examples include polyamide 6, polyamide 66, polyamide 11, polyamide 12, polyamide 610, polyamide 1010, polyamide 612, polyamide 6 / 66, polyamide 66 / 12, polyamide 46, m-phenylenediamine / adipic acid copolymer, polyamide 62, polyamide 92, polyamide 122, polyamide 142, etc.

[0134] Aliphatic polyamide resins can also be resins composed of polymers that are block copolymers or graft copolymers on a portion of the molecules without amide bonds as repeating units. Examples of such aliphatic polyamide resins include resins composed of polyamide-based elastomers such as polyamide 6 / polyester copolymers, polyamide 6 / polyether copolymers, polyamide 12 / polyester copolymers, and polyamide 12 / polyether copolymers. These polyamide-based elastomers are obtained by ester block copolymerization of polyamide oligomers and polyester oligomers, or by ether block copolymerization of polyamide oligomers and polyether oligomers. Examples of the aforementioned polyester oligomers include polycaprolactone and polyethylene adipate, and examples of the aforementioned polyether oligomers include polyethylene glycol, polypropylene glycol, and polytetramethylene glycol. Polyamide 6 / polytetramethylene glycol copolymers and polyamide 12 / polytetramethylene glycol copolymers are preferred as the aforementioned polyamide-based elastomers.

[0135] As an aliphatic polyamide resin, sufficient mechanical strength can be obtained even if the layer composed of aliphatic polyamide resin is thin. Therefore, it is preferred to select at least one of the following: 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, and polyamide 12 / polyether copolymer. More preferably, it is preferred to select at least one of the following: polyamide 11, polyamide 12, and polyamide 612.

[0136] Polyolefin resins are resins containing monomer units derived from vinyl monomers that do not have fluorine atoms.

[0137] There are no particular limitations on polyolefin resins. For example, in addition to polyolefins such as polyethylene, polypropylene, high-density polyolefins, and low-density polyolefins, modified polyolefins, epoxy-modified polyolefins, and amine-modified polyolefins, which are made by modifying the above polyolefins with maleic anhydride, are also examples. High-density polyolefins are preferred.

[0138] Without prejudice to the purpose of this invention, the non-fluorinated polymer layer (N2) can be formed by adding various additives other than conductive fillers, such as reinforcing agents, fillers, ultraviolet absorbers, pigments, etc. By using such additives, the properties of the non-fluorinated polymer layer (N2), such as surface hardness, wear resistance, electrical conductivity, and weather resistance, can be improved.

[0139] The non-fluorinated polymer layer (N2) is not conductive. The non-fluorinated polymer layer (N2) does not contain conductive fillers.

[0140] (The composition of laminates)

[0141] The laminate of the present invention comprises at least a non-fluorinated polymer layer (A), said non-fluorinated polymer layer (A) containing at least one non-fluorinated polymer (A) selected from the group consisting of ethylene / vinyl alcohol copolymers and aromatic polyamides. The number of layers in the laminate of the present invention is not particularly limited as long as it is two or more. The number of layers in the laminate of the present invention can be 2 to 5.

[0142] In addition to the non-fluorinated polymer layer (A), the laminate of the present invention may also include a polymer layer (B) containing a polymer (excluding the non-fluorinated polymer layer (A)). Examples of polymer layers (B) include conductive layers (N1), fluoropolymer layers (F), and non-fluorinated polymer layers (N2).

[0143] In the laminate of the present invention, the non-fluorinated polymer layer (A) and the polymer layer (B) can be directly bonded or bonded via other layers such as an adhesive layer, but direct bonding is preferred.

[0144] Examples of laminates according to the present invention include laminates having at least a conductive layer (N1) and a non-fluorinated polymer layer (A) and laminates having at least a fluoropolymer layer (F) and a non-fluorinated polymer layer (A).

[0145] Examples of the laminates of the present invention include: A laminate having a conductive layer (N1) / a non-fluorinated polymer layer (A) as the innermost / outermost layer, and a laminate having a fluoropolymer layer (F) / a non-fluorinated polymer layer (A) as the innermost / outermost layer; A laminate having a conductive layer (N1) / a non-fluorinated polymer layer (A) / a non-fluorinated polymer layer (N2) as the innermost / middle / outermost layer, and a laminate having a fluoropolymer layer (F) / a non-fluorinated polymer layer (A) / a non-fluorinated polymer layer (N2) as the innermost / middle / outermost layer; A laminate having a conductive layer (N1) / a non-fluorinated polymer layer (N2) / a non-fluorinated polymer layer (A) / a non-fluorinated polymer layer (N2) as the innermost / inner / middle / outermost layer, and a laminate having a fluoropolymer layer (F) / a non-fluorinated polymer layer (N2) / a non-fluorinated polymer layer (A) / a non-fluorinated polymer layer (N2) as the innermost / inner / middle / outermost layer; A laminate having a conductive layer (N1) / a non-fluorinated polymer layer (N2) / a non-fluorinated polymer layer (A) / a non-fluorinated polymer layer (N2) / a non-fluorinated polymer layer (N2) as the innermost / inner / middle / outer / outermost layer, and a laminate having a fluoropolymer layer (F) / a non-fluorinated polymer layer (N2) / a non-fluorinated polymer layer (A) / a non-fluorinated polymer layer (N2) / a non-fluorinated polymer layer (N2) as the innermost / inner / middle / outer / outermost layer; etc.

[0146] When the laminate of the present invention comprises two or more non-fluorinated polymer layers (A), the types of non-fluorinated polymers (A) contained in each layer may be the same or different. When the laminate of the present invention comprises two or more conductive layers (N1), the types of non-fluorinated polymers (N1) contained in each layer may be the same or different. When the laminate of the present invention comprises two or more fluoropolymer layers (F), the types of fluoropolymers contained in each layer may be the same or different. When the laminate of the present invention comprises two or more non-fluorinated polymer layers (N2), the types of non-fluorinated polymers (N2) contained in each layer may be the same or different. In the laminate of the present invention, the boundaries between adjacent layers are not necessarily defined; a layer structure with a concentration gradient can exist where the molecular chains of the polymers constituting each layer interpenetrate from each other.

[0147] The laminate of the present invention may also have other layers. The thickness, shape, etc. of each layer of the laminate of the present invention can be appropriately selected according to the purpose and method of use.

[0148] The fuel permeation rate of the laminate of the present invention is preferably 15 g / m. 2 less than / day, preferably 10g / m 2 Less than / day, further preferably 5.0g / m 2 Less than / day, preferably 3.0g / m 2 / day or less.

[0149] When the fuel contains alcohol, the fuel permeation rate of the laminate of the present invention is preferably 15 g / m. 2 less than / day, preferably 10g / m 2 Less than / day, further preferably 5.0g / m 2Less than / day, preferably 3.0g / m 2 / day or less.

[0150] When the fuel contains gasoline, the fuel permeation rate of the laminate of the present invention is preferably 15 g / m. 2 less than / day, preferably 10g / m 2 Less than / day, further preferably 5.0g / m 2 Less than / day, preferably 3.0g / m 2 / day or less.

[0151] When the fuel contains diesel fuel (light oil), the fuel permeation rate of the laminate of the present invention is preferably 8.0 g / m. 2 less than / day, preferably 5.0g / m 2 Less than / day, further preferably 3.0g / m 2 / day or less.

[0152] The fuel permeation rate of a laminate is the rate at which fuel containing at least a compound (1) consisting only of carbon, hydrogen, and oxygen atoms and having a carbonyl or ether bond permeates through the laminate. The fuel permeation rate of a laminate can be determined as follows: a tubular laminate is prepared, fuel containing compound (1) is prepared at a specified concentration, the fuel is sealed inside the tubular laminate, and the laminate is placed at 60°C or 80°C. The mass change per unit time is measured, and the fuel permeation rate is calculated from the mass change and the inner surface area of ​​the tubular laminate. In the case where the fuel contains alcohol or gasoline, the fuel can be sealed inside the tubular laminate, and the mass change per unit time can be measured after placing it at 60°C. Additionally, in the case where the fuel contains diesel fuel (light oil), the fuel can be sealed inside the tubular laminate, and the mass change per unit time can be measured after placing it at 80°C.

[0153] The laminates of this invention can be manufactured into various shapes, such as membrane shapes, sheet shapes, piping (hose) shapes, bottle shapes, and can shapes. The membrane, sheet, piping, and hose shapes can be corrugated, swirled, or convoluted shapes. The laminates of this invention can be, for example, membranes, sheets, piping, hoses, bottles, containers, and cans. The laminates of this invention are suitable for applications such as automotive fuel piping or hoses, underground piping or hoses for fuel supply facilities, automotive fuel cans, O-rings for fuel pumps, and various automotive seals.

[0154] In one embodiment, the laminate of the present invention is used as a component of a system for circulating fuel containing at least a compound (1) consisting only of carbon atoms, hydrogen atoms, and oxygen atoms and having a carbonyl group or ether bond. The system for circulating fuel is, for example, a system for storing or supplying fuel. Components used in such systems include tanks, piping, hoses, caps, valves, diaphragms, sealing materials (O-rings), etc. Systems for circulating fuel are used not only in automobiles but also in facilities for supplying fuel to fuel tanks in automobiles. Typical examples of components constituting a system for circulating fuel are fuel piping or fuel hoses.

[0155] (Pipes and hoses)

[0156] The laminates of this invention can be suitable for use as piping or hoses. In this invention, "piping or hose" includes articles commonly referred to as piping or hoses, typically articles having a shape capable of conveying fluid. In this invention, the term "piping or hose" does not mean that piping and hoses are different articles.

[0157] The piping or hose of the present invention may have the same structure as the laminate described above.

[0158] The fuel permeation rate of the piping or hose of the present invention is preferably 15 g / m. 2 less than / day, preferably 10g / m 2 Less than / day, further preferably 5.0g / m 2 Less than / day, preferably 3.0g / m 2 / day or less.

[0159] When the fuel contains alcohol, the fuel permeation rate of the piping or hose of the present invention is preferably 15 g / m. 2 less than / day, preferably 10g / m 2 Less than / day, further preferably 5.0g / m 2 Less than / day, preferably 3.0g / m 2 / day or less.

[0160] When the fuel contains gasoline, the fuel permeation rate of the piping or hose of the present invention is preferably 15 g / m. 2 less than / day, preferably 10g / m 2 Less than / day, further preferably 5.0g / m 2 Less than / day, preferably 3.0g / m 2 / day or less.

[0161] When the fuel contains diesel fuel (light oil), the fuel permeation rate of the piping or hose of the present invention is preferably 8.0 g / m. 2less than / day, preferably 5.0g / m 2 Less than / day, further preferably 3.0g / m 2 / day or less.

[0162] The fuel permeation rate of a pipe or hose is the rate at which fuel containing at least a compound (1) consisting only of carbon, hydrogen, and oxygen atoms and having a carbonyl or ether bond permeates through the pipe or hose. The fuel permeation rate of a pipe or hose can be determined as follows: fuel containing compound (1) at a specified concentration is prepared, the fuel is sealed in the pipe or hose, placed at 60°C or 80°C, and the mass change per unit time is measured. The fuel permeation rate is calculated from the mass change and the inner surface area of ​​the pipe or hose, thereby determining the fuel permeation rate of the pipe or hose. In the case where the fuel contains alcohol or gasoline, the fuel can be sealed in the pipe or hose, placed at 60°C, and the mass change per unit time can be measured. Additionally, in the case where the fuel contains diesel fuel (light oil), the fuel can be sealed in the pipe or hose, placed at 80°C, and the mass change per unit time can be measured.

[0163] The outer diameter of the piping or hose is preferably 2 mm or more, more preferably 3 mm or more, further preferably 4 mm or more, most preferably 6 mm or more, preferably 20 mm or less, more preferably 18 mm or less, further preferably 16 mm or less, and most preferably 14 mm or less.

[0164] The inner diameter of the piping or hose is preferably 1 mm or more, more preferably 2 mm or more, further preferably 3 mm or more, most preferably 4 mm or more, preferably 15 mm or less, more preferably 13 mm or less, further preferably 11 mm or less, and most preferably 10 mm or less.

[0165] The thickness of the piping 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, 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.

[0166] The thickness of the non-fluorinated polymer layer (A) in the laminate and piping or hose is preferably 0.05 mm or more, more preferably 0.10 mm or more, even more preferably 0.15 mm or more, preferably 0.40 mm or less, more preferably 0.30 mm or less, and even more preferably 0.20 mm or less. The thickness of the non-fluorinated polymer layer (A) is the total thickness of each layer when the laminate and piping or hose have two or more non-fluorinated polymer layers (A).

[0167] The thickness of the polymer layer (B) in the laminate and the piping or hose is preferably 0.10 mm or more, more preferably 0.20 mm or more, even more preferably 0.30 mm or more, preferably 0.90 mm or less, more preferably 0.80 mm or less, and even more preferably 0.70 mm or less. When the laminate and the piping or hose have two or more polymer layers (B), the thickness of the polymer layer (B) is the total thickness of each layer.

[0168] The thickness of the conductive layer (N1) in the laminate and the piping or hose is preferably 0.05 mm or more, more preferably 0.10 mm or more, 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 piping or hose have two or more conductive layers (N1), the thickness of the conductive layer (N1) is the total thickness of each layer.

[0169] The thickness of the fluoropolymer layer (F) in the laminate and piping or hose is preferably 0.05 mm or more, more preferably 0.10 mm or more, 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 piping or hose have two or more fluoropolymer layers (F), the thickness of the fluoropolymer layer (F) is the total thickness of each layer.

[0170] The thickness of the non-fluorinated polymer layer (N2) in the laminate and piping or hose is preferably 0.10 mm or more, more preferably 0.20 mm or more, even more preferably 0.30 mm or more, preferably 0.90 mm or less, more preferably 0.80 mm or less, and even more preferably 0.70 mm or less. The thickness of the non-fluorinated polymer layer (N2) is the total thickness of each layer when the laminate and piping or hose have two or more non-fluorinated polymer layers (N2).

[0171] Piping or hoses can be corrugated, serpentine, convoluted, or similar shapes. When piping (hose) is corrugated, multiple annular areas are formed by wavy creases. One side of the annulus can be compressed and the other side expanded outward within these areas, allowing it to be easily bent at any angle without stress fatigue or interlayer delamination.

[0172] There is no limitation on the method of forming the waveform area. Straight tubular pipes or hoses can be formed, and then molding can be performed to form a specified waveform shape, which can be easily achieved.

[0173] As a method for manufacturing the laminate of the present invention, examples include: (1) A method of forming a multilayered laminate by hot-melting (melt bonding) between layers through co-extrusion molding of polymers forming each layer, thereby forming a multilayered laminate in one step (co-extrusion molding); (2) The layers are overlapped by heat fusion to bond them together; (3) A method of forming a laminate by extruding a polymer that forms a layer adjacent to the layer onto the surface of a pre-made layer using an extruder; (4) After electrostatically coating a polymer that forms an adjacent layer onto the surface of a pre-made layer, the resulting coating is heated as a whole or from the coating side, thereby heating and melting the polymer to be coated to form the layer; etc.

[0174] When the laminate of the present invention is a pipe or hose, for example, as a method equivalent to (2) above, (2a) can be described as forming each cylindrical layer separately using an extruder, and forming a coating of the layer in contact with the inner layer in the form of a heat-shrinkable pipe on the inner layer; as a method equivalent to (3) above, (3a) can be described as forming the inner layer first using an inner layer extruder, and forming the layer in contact with the inner layer on its outer circumference using an outer layer extruder; as a method equivalent to (4) above, (4a) electrostatically coating the polymer constituting the inner layer onto the inner side of the layer in contact with the inner layer, and then placing the resulting coating in a heating oven for overall heating, or inserting a rod-shaped heating device into the inner side of the cylindrical coating and heating from the inside, thereby heating and melting the polymer constituting the inner layer to form a mold; and so on.

[0175] If the layers constituting the laminate and piping or hose of the present invention can be co-extruded, they are typically formed by the co-extrusion molding described in (1) above. Examples of the co-extrusion molding described above include existing multilayer co-extrusion manufacturing methods such as multi-channel method and feed block method.

[0176] In the forming methods described in (2) and (3) above, after each layer is formed, the contact surfaces between each layer and other layers can be surface-treated to improve interlayer adhesion. Examples of such surface treatments include etching treatments such as sodium etching, corona treatment, and plasma treatments such as low-temperature plasma treatment.

[0177] As a molding method for the laminated body of the present invention, it can also be a molding method in which two or more materials are laminated in multiple stages by rotational molding. In this case, the melting point of the outer layer material does not need to be higher than the melting point of the inner layer material, and the melting point of the inner layer material can be 100°C or more higher than the melting point of the outer layer material. In this case, it is preferable to also have a heating element inside.

[0178] The piping or hose of the present invention can be used for fuel piping or hoses such as automotive fuel piping or automotive fuel hoses, underground buried piping or hoses for fuel supply facilities, etc.

[0179] The embodiments have been described above, but it is understood that various changes in form and detail can be made without departing from the spirit and scope of the claims.

[0180] <1> According to a first aspect of the invention, a laminated body is provided that is in contact with fuel, wherein, The fuel contains at least compound (1), which consists only of carbon atoms, hydrogen atoms, and oxygen atoms and has a carbonyl or ether bond. The laminate has at least one non-fluorinated polymer layer, which contains at least one non-fluorinated polymer selected from the group consisting of ethylene / vinyl alcohol copolymers and aromatic polyamides.

[0181] <2> According to a second aspect of the invention, a laminate based on the first aspect is provided, wherein the compound (1) is at least one selected from the group consisting of carbonates, chain ethers and cyclic ethers.

[0182] <3> According to a third aspect of the invention, a laminate based on the first or second aspect is provided, wherein the 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.

[0183] <4> According to a fourth aspect of the invention, a laminate based on any one of the first to third aspects is provided, wherein the fuel further contains an alcohol.

[0184] <5> According to a fifth aspect of the invention, a laminate based on any one of the first to fourth aspects is provided, wherein the fuel further comprises gasoline.

[0185] <6> According to a sixth aspect of the invention, a laminate based on any one of the first to fifth aspects is provided, wherein the fuel further comprises diesel fuel.

[0186] <7> According to a seventh aspect of the present invention, a laminate based on any one of the first to sixth aspects is provided, wherein the content of compound (1) in the fuel is 0.1 vol% to 20 vol%.

[0187] <8> According to an eighth aspect of the present invention, a laminate based on any one of the first to seventh aspects is provided, wherein the thickness of the non-fluorinated polymer layer is 0.05 mm to 0.40 mm.

[0188] <9> According to a ninth aspect of the present invention, a laminate based on any one of the first to eighth aspects is provided, which further comprises a conductive layer having conductivity and containing a non-fluorinated polymer.

[0189] <10> According to a tenth aspect of the invention, a laminate based on a ninth aspect is provided, wherein the non-fluorinated polymer is an aromatic polyamide.

[0190] <11> According to the 11th aspect of the invention, a laminate based on the 9th or 10th aspect is provided, wherein the conductive layer is in contact with the fuel.

[0191] <12> According to a 12th aspect of the present invention, a laminate based on any one of the 1st to 11th aspects is provided, which further comprises a fluoropolymer layer containing a fluoropolymer.

[0192] <13> According to a 13th aspect of the invention, a laminate based on a 12th aspect is provided, wherein the fluororesin is at least one selected from the group consisting of fluororesins containing ethylene units and tetrafluoroethylene units and fluororesins containing trifluorochloroethylene units and tetrafluoroethylene units.

[0193] <14> According to a 14th aspect of the invention, a laminate based on a 12th or 13th aspect is provided, wherein the fluoropolymer layer is conductive.

[0194] <15> According to a 15th aspect of the invention, a laminate based on any one of the 12th to 14th aspects is provided, wherein the fluoropolymer layer is in contact with the fuel.

[0195] <16> According to a 16th aspect of the present invention, a laminate based on any one of the 1st to 15th aspects is provided, wherein the fuel permeation rate is 15 g / m. 2 / day or less.

[0196] <17> According to a 17th aspect of the invention, a piping or hose is provided, which is formed of a laminate based on any one of the 1st to 16th aspects.

[0197] <18> According to an 18th aspect of the present invention, a piping or hose is provided, which is formed of a laminate based on any one of the 1st to 11th aspects, wherein, The laminate sequentially comprises: A conductive layer (N1) containing conductive fillers and aromatic polyamides; A non-fluorinated polymer layer (A) containing aromatic polyamide; and A non-fluorinated polymer layer (N2) containing aliphatic polyamide resin. The conductive layer (N1) is the innermost layer and is in contact with the fuel.

[0198] <19> According to a 19th aspect of the present invention, a piping or hose is provided, which is formed of a laminate based on any one of the first to eighth and twelfth to fifteenth aspects, wherein, The laminate sequentially comprises: A fluoropolymer layer (F) containing conductive fillers and a fluoropolymer, wherein the fluoropolymer contains ethylene units and tetrafluoroethylene units; A non-fluorinated polymer layer (N2) containing aliphatic polyamide resin; A non-fluorinated polymer layer (A) containing an ethylene / vinyl alcohol copolymer; A non-fluorinated polymer layer (N2) containing aliphatic polyamide resin; and A non-fluorinated polymer layer (N2) containing aliphatic polyamide resin. The fluoropolymer layer (F) is the innermost layer and is in contact with the fuel.

[0199] Example

[0200] Next, embodiments will be given to illustrate the implementation of the present invention, but the present invention is not limited to the embodiments described herein.

[0201] The values ​​in the examples were measured using the following methods.

[0202] <Polymer Composition (Monomer Composition of Fluoropolymer)>

[0203] The procedure was performed using an AC300 nuclear magnetic resonance (NMR) device (manufactured by Bruker-Biospin). 19 F-NMR determination is used to determine the monomer composition of the fluoropolymer (the content of each monomer unit in the polymer) from the integrated values ​​of each peak. The monomer composition of the fluoropolymer is determined by appropriately combining the results of elemental analysis based on the types of monomers.

[0204] Melting point

[0205] The melting point of the fluoropolymer was determined by using a differential scanning calorimeter RDC220 (manufactured by Seiko Instruments) at a heating rate of 10 °C / min according to ASTM D 4591, and the peak of the resulting endothermic curve was used.

[0206] Melt Flow Rate (MFR)

[0207] The mass (g / 10 min) of fluoropolymer flowing out of a nozzle with an inner diameter of 2 mm and a length of 8 mm was determined every 10 minutes using a melt flow index tester (manufactured by Yasuda Seiki Co., Ltd.) at 265°C or 297°C and a load of 5 kg, according to ASTM D 1238. This mass was used as the MFR.

[0208] <Fuel permeation speed>

[0209] The pipes obtained in the experimental and comparative experiments were cut, and their inner diameter and length were measured. Swagelok fittings were installed at both ends of the pipes, and the pipes were filled with the following fuel and capped. The mass of the fuel-filled pipes was measured. The pipes were then maintained at 60°C or 80°C for 1000 hours, and the mass was measured again. The mass reduction was calculated from the measured masses, and then the fuel permeation rate (g / m²) was calculated from the mass reduction and the inner surface area of ​​the pipes. 2 / sky).

[0210] In the determination of fuel permeation rate, the following fuels were used, containing CE10 (toluene / isooctane / ethanol = 45 / 45 / 10 vol%), CM15 (toluene / isooctane / methanol = 42.5 / 42.5 / 15 vol%), FuelC (toluene / isooctane = 50 / 50 vol%), E (ethanol), M (methanol), and DMC (dimethyl carbonate) in optional proportions. With these fuels, the piping was maintained at 60°C for 1000 hours, and the mass was measured to calculate the fuel permeation rate.

[0211] Fuel (1): CE10 100% by volume

[0212] Fuel (2): FuelC / E / DMC = 85 / 10 / 5 (volume %)

[0213] Fuel (3): FuelC / E / DMC = 80 / 10 / 10 (volume %)

[0214] Fuel (4): FuelC / E / DMC = 70 / 10 / 20 (volume %)

[0215] Fuel (5): E / DMC = 10 / 90 (volume %)

[0216] Fuel (6): DMC 100% by volume

[0217] Fuel (7): CM15 100% by volume

[0218] Fuel (8): FuelC / M / DMC = 65 / 15 / 20 (volume %)

[0219] In addition, the following fuels containing diesel fuel and DMC (dimethyl carbonate) in optional proportions were used in the determination of fuel permeability. With these fuels, the piping was maintained at 80°C for 1000 hours, and the mass was measured to calculate the fuel permeability.

[0220] Fuel (1): diesel 100% by volume

[0221] Fuel (2): diesel / DMC = 95 / 5 (volume %)

[0222] Fuel (3): diesel / DMC = 90 / 10 (volume %)

[0223] Fuel (4): diesel / DMC = 80 / 20 (volume %)

[0224] The following materials were used in the experimental and comparative experimental cases.

[0225] Conductive polyamide 9T (PA9T cond.)

[0226] Genestar TS341 manufactured by KURARAY

[0227] Polyamide 9T (PA9T)

[0228] Genestar N1001D manufactured by KURARAY

[0229] Fluororesin A

[0230] Polymer composition (molar percentage): TFE / Et / HFP / 2,3,3,4,4,5,5-heptafluoro-1-pentene = 45.5 / 44.4 / 9.5 / 0.6

[0231] Melting point: 197℃

[0232] Melt flow rate (265℃): 5.0 g / 10 minutes

[0233] Carbon black content: 12% by mass

[0234] Ethylene / vinyl alcohol copolymer (EVOH)

[0235] F101B manufactured by KURARAY

[0236] Polyamide 12 (PA12)

[0237] Daiamid X7297 manufactured by Polyplastics Ebonic

[0238] Polyamide 612 (PA612)

[0239] Ebonic manufactures the Vestamid SX8002.

[0240] Experimental Examples 1-2 and Comparative Experiment 1

[0241] Using a five-layer piping extrusion unit with multiple flow channels (manufactured by PLABOR Research Laboratory of Plastics Technology Co., Ltd), each material is fed into the extruder according to the material composition of each layer as shown in Table 1, to form a multi-layered pipe with an outer diameter of 8 mm and an inner diameter of 6 mm.

[0242] Using the obtained multilayer piping, various physical properties were determined using the methods described above. The results are shown in Table 2.

[0243] [Table 1]

[0244] [Table 2]

[0245] Experimental Examples 3-4 and Comparative Experimental Examples 2-3

[0246] Using a five-layer piping extrusion unit with multiple flow channels (manufactured by PLABOR Research Laboratory of Plastics Technology Co., Ltd), each material is fed into the extruder according to the material composition of each layer as shown in Table 1, to form a multi-layered pipe with an outer diameter of 8 mm and an inner diameter of 6 mm.

[0247] Using the obtained multilayer piping, various physical properties were determined using the methods described above. The results are shown in Table 2.

[0248] [Table 3]

[0249] [Table 4]

Claims

1. A laminate which is in contact with a fuel, wherein the fuel contains at least a compound (1) which consists only of carbon atoms, hydrogen atoms and oxygen atoms and has a carbonyl group or an ether bond, the laminate has at least a non-fluorinated polymer layer which contains at least one non-fluorinated polymer selected from the group consisting of an ethylene / vinyl alcohol copolymer and an aromatic polyamide.

2. The laminate according to claim 1, wherein the compound (1) is at least one selected from the group consisting of a carbonate, a chain ether and a cyclic ether.

3. The laminate according to claim 1 or 2, wherein the 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. The laminate according to any one of claims 1 to 3, wherein the fuel further contains an alcohol.

5. The laminate according to any one of claims 1 to 4, wherein the fuel further contains gasoline.

6. The laminate according to any one of claims 1 to 5, wherein the fuel further contains a diesel fuel.

7. The laminate according to any one of claims 1 to 6, wherein the content of the compound (1) in the fuel is 0.1 to 20% by volume.

8. The laminate according to any one of claims 1 to 7, wherein the thickness of the non-fluorinated polymer layer is 0.05 to 0.40 mm.

9. The laminate according to any one of claims 1 to 8, further comprising an electrically conductive layer which has electrical conductivity and contains a non-fluorinated polymer.

10. The laminate according to claim 9, wherein the non-fluorinated polymer is an aromatic polyamide.

11. The laminate according to claim 9 or 10, wherein the electrically conductive layer is in contact with the fuel.

12. The laminate according to any one of claims 1 to 11, further comprising a fluororesin layer which contains a fluororesin.

13. The laminate according to claim 12, wherein the fluororesin is at least one selected from the group consisting of a fluororesin containing an ethylene unit and a tetrafluoroethylene unit and a fluororesin containing a trifluorochloroethylene unit and a tetrafluoroethylene unit.

14. The laminate according to claim 12 or 13, wherein the fluororesin layer has electrical conductivity.

15. The laminate according to any one of claims 12 to 14, wherein the fluororesin layer is in contact with the fuel.

16. The laminate according to any one of claims 1 to 15, wherein The fuel permeation rate is 15 g / m 2 / day or less.

17. A pipe or hose formed from the laminate according to any one of claims 1 to 16.

18. A pipe or hose formed from the laminate according to any one of claims 1 to 11, wherein the laminate has, in this order, an electrically conductive layer (N1) containing an electrically conductive filler and an aromatic polyamide; a non-fluorinated polymer layer (A) containing an aromatic polyamide; and a non-fluorinated polymer layer (N2) containing an aliphatic polyamide resin, the electrically conductive layer (N1) is the innermost layer and is in contact with the fuel.

19. A pipe or hose formed from the laminate according to any one of claims 1 to 8 and 12 to 15, wherein the laminate has, in this order, a fluororesin layer (F) containing an electrically conductive filler and a fluororesin containing an ethylene unit and a tetrafluoroethylene unit; a non-fluorinated polymer layer (N2) containing an aliphatic polyamide resin; a non-fluorinated polymer layer (A) containing an ethylene / vinyl alcohol copolymer; a non-fluorinated polymer layer (N2) containing an aliphatic polyamide resin; and a non-fluorinated polymer layer (N2) containing an aliphatic polyamide resin, the fluororesin layer (F) is the innermost layer and is in contact with the fuel.

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