JP2016034711A - Laminate tube - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate tube that is excellent in chemical solution impermeability, particularly low-to-high-concentration-alcohol-containing gasoline impermeability, interlayer adhesion and its durability, low-temperature impact resistance, degraded fuel resistance, and monomer/oligomer elution resistance.SOLUTION: A laminate tube comprises a layer comprising an aliphatic polyamide (polyamide 11, 12 or the like), a layer comprising polyamide 6/66/12 composition, a layer comprising an ethylene/vinyl acetate copolymer saponified product, and a layer comprising a fluorine-containing polymer with a specific functional group.SELECTED DRAWING: None

Description

  The present invention relates to a laminated tube.

  In the past, automotive piping tubes were made of metal and made of lightweight resin with excellent rust prevention properties in response to the problem of rusting caused by anti-freezing agents on roads and the need to prevent global warming and save energy. The alternative to is progressing. Usually, resins used as piping tubes include polyamide-based resins, saturated polyester-based resins, polyolefin-based resins, thermoplastic polyurethane-based resins, etc. In the case of single-layer tubes using these, heat resistance, Due to insufficient chemical properties, the applicable range was limited.

  In addition, automobile piping tubes are oxygen-containing gasoline blended with low boiling point alcohols such as methanol and ethanol, or ethers such as ethyl-t-butyl ether (ETBE) from the viewpoint of saving gasoline consumption and improving performance. Etc. are transferred. Furthermore, from the viewpoint of preventing environmental pollution, strict exhaust gas regulations including prevention of leakage into the atmosphere due to diffusion of volatile hydrocarbons and the like through piping tube partition walls are being implemented. In response to such strict regulations, a single-layer tube using a polyamide-based resin, particularly polyamide 11 or polyamide 12 that is excellent in strength, toughness, chemical resistance, flexibility, etc., is used as described above. The permeation-preventing property with respect to a chemical solution is not sufficient, and in particular, an improvement with respect to the permeation-preventing property of alcohol-containing gasoline is required.

  As a method for solving this problem, a resin having good chemical solution permeation prevention properties, for example, saponified ethylene / vinyl acetate copolymer (EVOH), polymetaxylylene adipamide (polyamide MXD6), polybutylene terephthalate (PBT), Polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyphenylene sulfide (PPS), polyvinylidene fluoride (PVDF), ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / tetrafluoroethylene / hexafluoropropylene copolymer Polymer (EFEP), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene Pyrene / vinylidene fluoride copolymer (TFE / HFP / VDF, THV), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer (TFE / HFP / VDF / PAVE), tetra Fluoroethylene / perfluoro (alkyl vinyl ether) copolymer (TFE / PAVE, PFA), tetrafluoroethylene / hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer (TFE / HFP / PAVE), chlorotrifluoroethylene / A laminated tube in which a perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer (CTFE / PAVE / TFE, CPT) is arranged has been proposed (see, for example, Patent Document 1).

  Among these, the saponified ethylene / vinyl acetate copolymer (EVOH) is extremely excellent in chemical solution permeation prevention properties, particularly permeation prevention properties for gasoline. For example, a fuel composed of an outermost layer made of polyamide 12, an adhesive layer made of modified polyolefin, an outer layer made of polyamide 6, an intermediate layer made of saponified ethylene / vinyl acetate copolymer (EVOH), and an innermost layer made of polyamide 6 Piping has been proposed (see Patent Document 2). However, when polyamide 6 is used as the innermost layer in the pipe, the resistance to sour gasoline produced by oxidation of gasoline (deterioration fuel resistance) and the resistance to calcium chloride (chemical resistance) are poor. Further, at least one selected from the group consisting of an outermost layer made of polyamide 12, a polyamide 6/12 copolymer, a polyamide 12/6 copolymer, polyamide 612, polyamide 610, a mixture of polyamide 12, polyamide 6, and a compatibilizer. A laminated composite composed of an adhesive layer made of seed, an intermediate layer made of saponified ethylene / vinyl acetate copolymer (EVOH), and an innermost layer made of polyamide 6 or polyamide 12 has been proposed (Patent Documents 3 and 4). reference). Similarly, an outermost layer made of polyamide 12, an adhesive layer made of a mixture of polyamide 6, polyamide 12 and polyamine / polyamide copolymer, an intermediate layer made of saponified ethylene / vinyl acetate copolymer (EVOH), polyamide 6 or polyamide A laminated composite composed of 12 innermost layers has been proposed (see Patent Document 5). This technique is good for a polyamide copolymer having a specific composition ratio or a mixture of polyamide 6 and polyamide 12 and a compatibilizer as an adhesive layer interposing both polyamide 12 and saponified ethylene / vinyl acetate copolymer. Have been proposed as having a good interlayer adhesion strength.

US Pat. No. 5,554,425 JP-A-3-177683 Japanese translation of PCT publication No. 2003-535717 JP 2003-021276 A JP 2002-210904 A Japanese Patent Laid-Open No. 5-247478 Special table 2008-515658

  However, when polyamide 6 is used as the innermost layer, no solution has been made to the problem of inferior degradation fuel resistance, zinc chloride resistance and calcium chloride resistance. Furthermore, when polyamide 12 is used in the innermost layer of the fuel pipe, low molecular weight components such as monomers and oligomers, additives, and plasticizers are eluted into the alcohol-containing gasoline by contact with fuel such as alcohol-containing gasoline. Precipitate. Therefore, there is a concern about blockage in fuel piping such as automobile piping tubes, filters, nozzles and the like.

  The laminated tube includes a polyamide 6/12 copolymer, a polyamide 12/6 copolymer, and a polyamide between an aliphatic polyamide layer and an ethylene / vinyl acetate copolymer saponified product (EVOH). 612, polyamide 610, an adhesive layer made of a mixture of polyamide 12, polyamide 6, and a compatibilizer, and the initial interlayer adhesion is sufficient. On the other hand, these laminated tubes are generally processed into tubes having a desired shape in a state where bending stress is applied due to restrictions on layout and absorption of displacement at the time of collision. At that time, in order to facilitate thermal processing, the tube is heated in the range from the glass transition temperature of the constituent material to the melting point or less, but after heat treatment, if it does not have sufficient interlayer adhesion, When the innermost layer is peeled off and the piping is blocked, the outermost layer is peeled off, resulting in a problem that the tube does not have the original performance such as pressure resistance and yield strength. Therefore, there is room for improvement in interlayer adhesion after heat treatment (durability of interlayer adhesion).

  Furthermore, the laminated tube containing the saponified ethylene / vinyl acetate copolymer (EVOH) is excellent in permeation resistance for gasoline containing low concentration alcohol, but is insufficient in permeation resistance for gasoline containing high concentration alcohol. Improvement is desired. In order to solve these problems, as a means for overcoming this, for fuel transfer, a fluorine resin is disposed on the inner layer and an ethylene / vinyl acetate copolymer saponified material is disposed on the outer layer. A tube has been proposed (see Patent Documents 6 and 7). The fuel transfer tube according to the present technology is very excellent in chemical solution permeation prevention. However, in the fuel transfer tube, a modified polyolefin resin or polyamide / polyamide / polyamine graft copolymer is used as an adhesive resin interposed between a layer made of a fluorine resin and a layer made of a saponified ethylene / vinyl acetate copolymer. Although it has been proposed that a mixture of a modified fluororesin or a modified polyolefin resin be disposed, there is no disclosure of technical data or technical suggestion regarding durability of interlayer adhesion.

  The object of the present invention is to solve the above-mentioned problems, and prevent chemical liquid permeation, particularly permeation to low-concentration alcohol-containing gasoline, interlayer adhesion and durability, low-temperature impact resistance, deterioration fuel resistance, Another object of the present invention is to provide a laminated tube excellent in the elution resistance of monomers and oligomers.

  As a result of intensive studies to solve the above problems, the present inventors have found that a layer containing an aliphatic polyamide (polyamide 11, 12, etc.), a layer containing a polyamide 6/66/12 composition, ethylene / vinyl acetate. A laminated tube containing a layer containing a copolymer saponified product and a layer containing a fluorine-containing polymer having a specific functional group has a chemical solution permeation prevention property, particularly a permeation prevention property for gasoline containing a low concentration to a high concentration alcohol. It has been found that it is excellent in various properties such as adhesion and durability, low temperature impact resistance, degradation fuel resistance, monomer and oligomer elution resistance.

That is, the present invention is a laminated tube comprising at least four layers including (a) layer, (b) layer, (c) layer, and (d) layer,
The layer (a) contains an aliphatic polyamide (A),
The layer (b) includes a polyamide 6/66/12 composition (B),
The layer (c) includes a saponified ethylene / vinyl acetate copolymer (C),
The layer (d) includes a fluorine-containing polymer (D) in which a functional group having reactivity with an amino group is introduced into a molecular chain,
The aliphatic polyamide (A) does not include poly (caproamide / hexamethylene adipamide / dodecanamide) (polyamide 6/66/12),
The polyamide 6/66/12 composition (B) comprises polyhexamethylene sebamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene decanamide (polyamide 910), polynonamethylene dodecamide. (Polyamide 912), polydecamethylene decanamide (polyamide 1010), polydecane methylene dodecane (polyamide 1012), and at least one polyamide selected from the group consisting of polydocamethylene dodecamide (polyamide 1212), and polyamide 6 / 66/12 polyamide mixture (B1) 50 mass% or more and 98 mass% or less, plasticizer (B2) 1 mass% or more and 20 mass% or less, and the flexural modulus measured according to ISO 178 is 500 MPa or less. 1 mass of olefin polymer (B3) % To 30% by mass or less.

The preferable aspect of the laminated tube of this invention is shown below. A plurality of preferred embodiments can be combined.
[1] The aliphatic polyamide (A) is polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene deca From the group consisting of amide (polyamide 610), polyhexamethylene dodecane (polyamide 612), polydecane methylene decanamide (polyamide 1010), polydecamethylene dodecane (polyamide 1012), and polydodecamethylene dodecane (polyamide 1212). A laminated tube comprising at least one selected homopolymer or a copolymer using several kinds of raw material monomers forming these.
[2] Polyamide 6/66/12 In the polyamide 6/66/12 in the composition (B), the mass ratio of the total units of caproamide units and hexamethylene adipamide units to dodecanamide units is caproamide units, hexamethylenes. A laminated tube comprising 81: 19% by mass or more and 95: 5% by mass or less with respect to a total of 100% by mass of adipamide units and dodecanamide units.
[3] A laminated tube, wherein the saponified ethylene / vinyl acetate copolymer (C) has an ethylene content of 15 mol% to 60 mol% and a saponification degree of 90 mol% or more.
[4] The (a) layer containing the aliphatic polyamide (A) is disposed in the outermost layer, and the (c) layer containing the saponified ethylene / vinyl acetate copolymer (C) contains the aliphatic polyamide (A). A laminated tube, which is disposed between the (a) layer and the (d) layer containing the fluorine-containing polymer (D).
[5] The (b) layer containing the polyamide 6/66/12 composition (B) contains the (a) layer containing the aliphatic polyamide (A) and the saponified ethylene / vinyl acetate copolymer (C) ( c) A laminated tube which is arranged between layers.
[6] A laminated tube, wherein a conductive layer containing a fluorine-containing polymer composition containing a conductive filler is disposed in the innermost layer of the laminated tube.
[7] A laminated tube manufactured by coextrusion molding.
[8] A laminated tube used as a fuel tube.

  The laminated tube of the present invention includes a layer containing an aliphatic polyamide, a layer containing a polyamide 6/66/12 composition, a layer containing a saponified ethylene / vinyl acetate copolymer, and a fluorine-containing heavy polymer having a specific functional group. By including a layer containing coalescence, both interlayer adhesion and chemical permeation prevention properties are achieved, and various properties such as low-temperature impact resistance, degradation fuel resistance, monomer and oligomer elution resistance are excellent. In particular, it is suitable as a fuel tube because alcohol mixed hydrocarbons that permeate and evaporate from the tube partition wall can be suppressed and compliance with strict environmental regulations becomes possible. In addition, the interlayer adhesion strength is less decreased after contact / immersing in fuel for a long time or after heat treatment, and the durability of interlayer adhesion is excellent. Therefore, the laminated tube of the present invention can be used in any environment, has high reliability, and its utility value is extremely large.

(1) Aliphatic polyamide (A)
The aliphatic polyamide (A) used in the present invention has an amide bond (—CONH—) in the main chain and is an aliphatic polyamide structural unit lactam, aminocarboxylic acid, or aliphatic diamine and aliphatic. It can be obtained by polymerization or copolymerization using dicarboxylic acid as a raw material by a known method such as melt polymerization, solution polymerization or solid phase polymerization. However, the aliphatic polyamide (A) does not contain poly (caproamide / hexamethylene adipamide / dodecanamide) (polyamide 6/66/12).

  Examples of lactams include caprolactam, enantolactam, undecane lactam, dodecane lactam, α-pyrrolidone, α-piperidone, and aminocarboxylic acids include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, and 11-aminoundecane. Examples include acid and 12-aminododecanoic acid. These can use 1 type (s) or 2 or more types.

  Examples of the aliphatic diamine include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1, 8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15 -Pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, 1,19-nonadecanediamine, 1,20-eicosanediamine, 2-methyl-1,5- Pentanediamine, 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octane Min, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine or the like. These can use 1 type (s) or 2 or more types.

  Aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, Examples include pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eicosanedioic acid. These can use 1 type (s) or 2 or more types.

  Examples of the aliphatic polyamide (A) include polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyethylene adipamide (polyamide 26), polytetramethylene succinamide (polyamide) 44), polytetramethylene glutamide (polyamide 45), polytetramethylene adipamide (polyamide 46), polytetramethylene suberamide (polyamide 48), polytetramethylene azelamide (polyamide 49), polytetramethylene sebacamide (Polyamide 410), polytetramethylene dodecamide (polyamide 412), polypentamethylene succinamide (polyamide 54), polypentamethylene glutamide (polyamide 55), polypentamethylene adipamide (polyamide) 6), polypentamethylene suberamide (polyamide 58), polypentamethylene azelamide (polyamide 59), polypentamethylene sebamide (polyamide 510), polypentamethylene dodecamide (polyamide 512), polyhexamethylene succinamide (Polyamide 64), polyhexamethylene glutamide (polyamide 65), polyhexamethylene adipamide (polyamide 66), polyhexamethylene suberamide (polyamide 68), polyhexamethylene azelamide (polyamide 69), polyhexamethylene Bacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polyhexamethylene tetradecanamide (polyamide 614), polyhexamethylene hexadecanamide (polyamide 616), polyhexame Lenoctadecamide (Polyamide 618), Polynonamethylene adipamide (Polyamide 96), Polynonamethylene suberamide (Polyamide 98), Polynonamethylene azelamide (Polyamide 99), Polynonamethylene sebacamide (Polyamide 910) , Polynonamethylene dodecamide (polyamide 912), polydecamethylene adipamide (polyamide 106), polydecamethylene suberamide (polyamide 108), polydecamethylene azelamide (polyamide 109), polydecamethylene sebacamide (polyamide) 1010), polydecamethylene dodecamide (polyamide 1012), polydodecamethylene adipamide (polyamide 126), polydodecamethylene suberamide (polyamide 128), polydodecamethylene azelamide (polyamide 129) And homopolymers such as polydodecamethylene sebacamide (polyamide 1210) and polydodecamethylene dodecamide (polyamide 1212), and copolymers using several raw material monomers forming these. From the viewpoints of ensuring sufficient physical properties such as mechanical properties and heat resistance of the obtained laminated tube, and from the viewpoint of economy and availability, aliphatic polyamide (A) is polycaproamide (polyamide 6), polyundecane. Amide (polyamide 11), polydodecanamido 6 (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene decanamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecamethylene At least one homopolymer selected from the group consisting of decamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), and polydodecamethylene dodecamide (polyamide 1212), or a raw material monomer forming these It is preferable that it is a copolymer using several types.

  The production apparatus of the aliphatic polyamide (A) includes kneading reactions such as a batch reaction kettle, a single tank type or multi tank type continuous reaction apparatus, a tubular continuous reaction apparatus, a uniaxial kneading extruder, a biaxial kneading extruder, etc. A known polyamide production apparatus such as an extruder may be used. As a polymerization method, a known method such as melt polymerization, solution polymerization, or solid phase polymerization can be used, and polymerization can be performed by repeating normal pressure, reduced pressure, and pressure operations. These polymerization methods can be used alone or in appropriate combination.

  In addition, the relative viscosity of the aliphatic polyamide (A) measured under the conditions of 96% sulfuric acid, 1% polymer concentration and 25 ° C. in accordance with JIS K-6920 ensures the mechanical properties of the resulting laminated tube. From the viewpoint of securing the desirable formability of the laminated tube by setting the viscosity at the time of melting to an appropriate range, it is preferably 1.5 or more and 5.0 or less, and 2.0 or more and 4.5 or less. Is more preferable.

  In the aliphatic polyamide (A), when the terminal amino group concentration per 1 g of the polyamide is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), [A]> [B ] +5 is preferable from the viewpoint of sufficiently securing the interlayer adhesion of the laminated tube and its durability, and it is more preferable that [A]> [B] +10, and [A]> [B] +15. More preferably (hereinafter sometimes referred to as terminal-modified aliphatic polyamide). Furthermore, [A]> 20 is preferable from the viewpoint of the melt stability of the polyamide and the generation of gel-like substances is suppressed, and 30 <[A] <120 is more preferable.

  The terminal amino group concentration [A] (μeq / g) can be measured by dissolving the polyamide in a phenol / methanol mixed solution and titrating with 0.05N hydrochloric acid. The terminal carboxyl group concentration [B] (μeq / g) can be measured by dissolving the polyamide in benzyl alcohol and titrating with 0.05N sodium hydroxide solution.

The terminal-modified aliphatic polyamide is produced by polymerizing or copolymerizing the polyamide raw material in the presence of amines by a known method such as melt polymerization, solution polymerization or solid phase polymerization. Alternatively, it is produced by melt-kneading in the presence of amines after polymerization. As described above, amines can be added at any stage during polymerization or at any stage after melt kneading after polymerization. However, when the interlayer adhesion of the laminated tube is taken into consideration, the amines are added at the stage during polymerization. It is preferable.
Examples of the amines include monoamines, diamines, triamines, and polyamines. In addition to amines, carboxylic acids such as monocarboxylic acids, dicarboxylic acids, and tricarboxylic acids may be added as necessary as long as they do not deviate from the range of the above-mentioned end group concentration conditions. These amines and carboxylic acids may be added simultaneously or separately. Moreover, 1 type (s) or 2 or more types can be used for the amines and carboxylic acids illustrated below.

  Specific examples of the monoamine to be added include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine , Aliphatic monoamines such as tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, octadecyleneamine, eicosylamine, docosylamine, alicyclic monoamines such as cyclohexylamine, methylcyclohexylamine, benzylamine, β- Aromatic monoamines such as phenylmethylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, N, N-dihexyl Symmetrical secondary amines such as amine, N, N-dioctylamine, N-methyl-N-ethylamine, N-methyl-N-butylamine, N-methyl-N-dodecylamine, N-methyl-N-octadecylamine, N -Hybrid secondary amines such as -ethyl-N-hexadecylamine, N-ethyl-N-octadecylamine, N-propyl-N-hexadecylamine, N-propyl-N-benzylamine and the like. These can use 1 type (s) or 2 or more types.

  Specific examples of the diamine to be added include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, and 1,7-heptanediamine. 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine 2-methyl-1,8-octanediamine, 2,2,4-trimethyl-1,6-hexanedi Amine, aliphatic diamine such as 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (amino) Methyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (3-methyl-4) -Aminocyclohexyl) propane, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine, bis (aminopropyl) piperazine, bis (amino Ethyl) piperazine, 2,5-bis (aminomethyl) norbornane, 2,6-bis (aminomethyl) ) Arocyclic diamine such as norbornane, 3,8-bis (aminomethyl) tricyclodecane, 4,9-bis (aminomethyl) tricyclodecane, aromatic such as m-xylylenediamine, p-xylylenediamine Examples include diamines. These can use 1 type (s) or 2 or more types.

  Specific examples of the triamine to be added include 1,2,3-triaminopropane, 1,2,3-triamino-2-methylpropane, 1,2,4-triaminobutane, 1,2,3,4- Tetraminobutane, 1,3,5-triaminocyclohexane, 1,2,4-triaminocyclohexane, 1,2,3-triaminocyclohexane, 1,2,4,5-tetraminocyclohexane, 1,3,5- Triaminobenzene, 1,2,4-triaminobenzene, 1,2,3-triaminobenzene, 1,2,4,5-tetraminobenzene, 1,2,4-triaminonaphthalene, 2,5,7 -1,4,5,8-tetraminonaphthalene such as -triaminonaphthalene, 2,4,6-triaminopyridine, 1,2,7,8-tetraminonaphthalene and the like. These can use 1 type (s) or 2 or more types.

The polyamine to be added may be a compound having a plurality of primary amino groups (—NH ₂ ) and / or secondary amino groups (—NH—). For example, polyalkyleneimine, polyalkylenepolyamine, polyvinylamine, polyallylamine, etc. Is mentioned. The amino group with active hydrogen is the reaction point of the polyamine.

  The polyalkyleneimine is produced by a method of ionic polymerization of an alkyleneimine such as ethyleneimine or propyleneimine, or a method of polymerizing an alkyloxazoline and then partially hydrolyzing or completely hydrolyzing the polymer. Examples of the polyalkylene polyamine include diethylenetriamine, triethylenetetramine, pentaethylenehexamine, or a reaction product of ethylenediamine and a polyfunctional compound. Polyvinylamine can be obtained, for example, by polymerizing N-vinylformamide to poly (N-vinylformamide), and then partially or completely hydrolyzing the polymer with an acid such as hydrochloric acid. Polyallylamine is generally obtained by polymerizing a hydrochloride of an allylamine monomer and then removing hydrochloric acid. These can use 1 type (s) or 2 or more types. Among these, polyalkyleneimine is preferable.

  Examples of the polyalkyleneimine include one or two alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, 1,1-dimethylethyleneimine Examples include homopolymers and copolymers obtained by polymerizing more than one species by a conventional method. Among these, polyethyleneimine is more preferable. Polyalkyleneimine is polymerized from alkyleneimine as a raw material, branched polyalkyleneimine obtained by ring-opening polymerization of alkyleneimine, secondary polyamineimine containing secondary amine and tertiary amine, or alkyloxazoline as a raw material. Either a linear polyalkyleneimine containing only a primary amine and a secondary amine, or a three-dimensionally crosslinked structure may be used. Furthermore, ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine, bisaminopropylethylenediamine, and the like may be included. A polyalkyleneimine is usually derived from the reactivity of an active hydrogen atom on a nitrogen atom contained therein, and in addition to a tertiary amino group, a primary amino group having an active hydrogen atom or a secondary amino group (imino Group).

  The number of nitrogen atoms in the polyalkyleneimine is not particularly limited, but is preferably 4 or more and 3,000, more preferably 8 or more and 1,500 or less, and even more preferably 11 or more and 500 or less. . The number average molecular weight of the polyalkyleneimine is preferably 100 or more and 20,000 or less, more preferably 200 or more and 10,000 or less, and further preferably 500 or more and 8,000 or less.

  On the other hand, as carboxylic acids to be added, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, capric acid, pelargonic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, myristic acid, Aliphatic monocarboxylic acids such as palmitic acid, stearic acid, oleic acid, linoleic acid, arachidic acid, behenic acid, erucic acid, alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid, methylcyclohexanecarboxylic acid, benzoic acid, toluic acid , Aromatic monocarboxylic acids such as ethylbenzoic acid, phenylacetic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, hexadecanedioic acid , Hexadecenedioic acid, octadecanedioic acid, octadecenedioic acid, Icosandioic acid, eicosenedioic acid, docosandioic acid, diglycolic acid, 2,2,4-trimethyladipic acid, aliphatic dicarboxylic acids such as 2,4,4-trimethyladipic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, cycloaliphatic dicarboxylic acid such as norbornane dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, m-xylylene dicarboxylic acid, p-xylylene dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, Aromatic dicarboxylic acids such as 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, 1,2,6-hexanetricarboxylic acid Acid, 1,3,6-hexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid Tricarboxylic acids such as trimesic acid. These can use 1 type (s) or 2 or more types.

  The amount of amines to be added is appropriately determined by a known method in consideration of the terminal amino group concentration, terminal carboxyl group concentration, and relative viscosity of the terminal-modified aliphatic polyamide to be produced. Usually, the addition amount of amines is sufficient to obtain sufficient reactivity with respect to 1 mol of the polyamide raw material (monomer constituting the repeating unit or 1 mol of the monomer unit) and a polyamide having a desired viscosity. From the viewpoint of facilitating production, it is preferably 0.5 meq / mol or more and 20 meq / mol or less, more preferably 1.0 meq / mol or more and 10 meq / mol or less (equivalent (eq) of amino group is The amount of amino group that reacts 1: 1 with a carboxyl group to form an amide group is 1 equivalent).

  In the terminal-modified aliphatic polyamide, it is preferable to add a diamine and / or a polyamine during polymerization in order to satisfy the condition of the terminal group concentration among the above-exemplified amines. More preferably, it is at least one selected from the group consisting of alicyclic diamine and polyamine.

  Further, the terminal-modified aliphatic polyamide may be a mixture of two or more kinds of polyamides having different terminal group concentrations as long as the terminal group concentration is satisfied. In this case, the terminal amino group concentration and the terminal carboxyl group concentration of the polyamide mixture are determined by the terminal amino group concentration, the terminal carboxyl group concentration, and the blending ratio of the polyamide constituting the mixture.

In order to improve the flexibility of the aliphatic polyamide (A), it is preferable to add a plasticizer described in the polyamide 6/66/12 composition (B) described later.
The content of the plasticizer may be 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the aliphatic polyamide (A) from the viewpoint of sufficiently ensuring the flexibility and low temperature impact resistance of the laminated tube. Preferably, it is 2 parts by mass or more and 20 parts by mass or less.

Further, in order to improve the low temperature impact resistance of the aliphatic polyamide (A), it is preferable to add an impact resistance improving material, and in particular, an ISO described in the polyamide 6/66/12 composition (B) described later. It is more preferable to add an olefin polymer having a flexural modulus measured according to 178 of 500 MPa or less. If the flexural modulus exceeds this value, the impact improvement effect may be insufficient.
The content of the impact resistance improving material is 1 part by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the aliphatic polyamide (A) from the viewpoint of sufficiently ensuring the mechanical strength and low temperature impact resistance of the laminated tube. It is preferable that it is 3 parts by mass or more and 25 parts by mass or less.

  The aliphatic polyamide (A) may be a mixture of the above homopolymers, a mixture of the above copolymers, a mixture of a homopolymer and a copolymer, or another polyamide resin or other heat. It may be a mixture with a plastic resin. The content of the aliphatic polyamide (A) in the mixture is preferably 60% by mass or more, and more preferably 80% by mass or more.

  Other polyamide resins include polymetaxylylene adipamide (polyamide MXD6), polymetaxylylene veramide (polyamide MXD8), polymetaxylylene azelamide (polyamide MXD9), polymetaxylylene sebacamide (polyamide MXD10). , Polymetaxylylene decamide (polyamide MXD12), polymetaxylylene terephthalamide (polyamide MXDT), polymetaxylylene isophthalamide (polyamide MXDI), polymetaxylylene hexahydroterephthalamide (polyamide MXDT (H)), polymer Taxylylene naphthalamide (polyamide MXDN), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylene beramide (polyamide PXD8), polyparaxylylene azelamide Polyamide PXD9), polyparaxylylene sebacamide (polyamide PXD10), polyparaxylylene dodecamide (polyamide PXD12), polyparaxylylene terephthalamide (polyamide PXDT), polyparaxylylene isophthalamide (polyamide PXDI) , Polyparaxylylene hexahydroterephthalamide (polyamide PXDT (H)), polyparaxylylene naphthalamide (polyamide PXDN), polyparaphenylene terephthalamide (PPTA), polyparaphenylene isophthalamide (PPIA), poly Metaphenylene terephthalamide (PMTA), polymetaphenylene isophthalamide (PMIA), poly (2,6-naphthalenediethylene adipamide) (polyamide 2,6-BAN6), poly (2,6-naphthalenedimethyle Suberamide) (polyamide 2,6-BAN8), poly (2,6-naphthalene dimethylene azelamide) (polyamide 2,6-BAN9), poly (2,6-naphthalene dimethylene sebacamide) (polyamide 2,6 -BAN10), poly (2,6-naphthalene dimethylene dodecamide) (polyamide 2,6-BAN12), poly (2,6-naphthalene dimethylene terephthalamide) (polyamide 2,6-BANT), poly (2 , 6-Naphthalenedylene methylene isophthalamide) (polyamide 2,6-BANI), poly (2,6-naphthalenediethylene hexahydroterephthalamide) (polyamide 2,6-BANT (H)), poly (2, 6-naphthalene dimethylene naphthalamide) (polyamide 2,6-BANN), poly (1,3-cyclohexanedimethylene) Dipamide) (polyamide 1,3-BAC6), poly (1,3-cyclohexanedimethylenesberamide (polyamide 1,3-BAC8), poly (1,3-cyclohexanedimethylene azelamide) (polyamide 1,3-BAC9) ), Poly (1,3-cyclohexanedimethylene sebacamide) (polyamide 1,3-BAC10), poly (1,3-cyclohexanedimethylene dodecamide) (polyamide 1,3-BAC12), poly (1,3 -Cyclohexanedimethylene terephthalamide) (polyamide 1,3-BACT), poly (1,3-cyclohexanedimethylene isophthalamide) (polyamide 1,3-BACI), poly (1,3-cyclohexanedimethylene hexahydro Terephthalamide) (polyamide 1,3-BACT (H)), poly (1,3-sic Hexane dimethylene naphthalamide) (polyamide 1,3-BACN), poly (1,4-cyclohexanedimethylene adipamide) (polyamide 1,4-BAC6), poly (1,4-cyclohexanedimethylene suberamide) ( Polyamide 1,4-BAC8), poly (1,4-cyclohexanedimethylene azelamide) (polyamide 1,4-BAC9), poly (1,4-cyclohexanedimethylene sebacamide) (polyamide 1,4-BAC10) , Poly (1,4-cyclohexanedimethylene dodecamide) (polyamide 1,4-BAC12), poly (1,4-cyclohexanedimethylene terephthalamide) (polyamide 1,4-BACT), poly (1,4- Cyclohexanedimethylene isophthalamide) (polyamide 1,4-BACI), poly (1,4- Chlorohexane dimethylene hexahydroterephthalamide) (polyamide 1,4-BACT (H)), poly (1,4-cyclohexanedimethylene naphthalamide) (polyamide 1,4-BACN), poly (4,4′- Methylenebiscyclohexylene adipamide) (polyamide PACM6), poly (4,4′-methylenebiscyclohexylene suberamide) (polyamide PACM8), poly (4,4′-methylenebiscyclohexylene azelamide) (polyamide PACM9) , Poly (4,4′-methylenebiscyclohexylene sebacamide) (polyamide PACM10), poly (4,4′-methylenebiscyclohexylene dodecamide) (polyamide PACM12), poly (4,4′-methylenebiscyclohexyl) Silenetetradecamide) (Polyamide PACM) 14), poly (4,4′-methylenebiscyclohexylenehexadecamide) (polyamide PACM16), poly (4,4′-methylenebiscyclohexyleneoctadecamide) (polyamide PACM18), poly (4,4′- Methylenebiscyclohexylene terephthalamide) (polyamide PACMT), poly (4,4′-methylenebiscyclohexylene isophthalamide) (polyamide PACMI), poly (4,4′-methylenebiscyclohexylene hexahydroterephthalamide) (Polyamide PACMT (H)), poly (4,4′-methylenebiscyclohexylenenaphthalamide) (polyamide PACMN), poly (4,4′-methylenebis (2-methyl-cyclohexylene) adipamide) (polyamide MACM6), Poly (4,4'-methylene (2-methyl-cyclohexylene) suberamide) (polyamide MACM8), poly (4,4′-methylenebis (2-methyl-cyclohexylene) azeramide) (polyamide MACM9), poly (4,4′-methylenebis (2- Methyl-cyclohexylene) sebacamide) (polyamide MACM10), poly (4,4′-methylenebis (2-methyl-cyclohexylene) dodecamide) (polyamide MACM12), poly (4,4′-methylenebis (2-methyl-cyclohexylene) ) Tetradecamide) (polyamide MACM14), poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexadecamide) (polyamide MACM16), poly (4,4′-methylenebis (2-methyl-cyclohexylene) octadecamide) ( Polyami MACM18), poly (4,4′-methylenebis (2-methyl-cyclohexylene) terephthalamide) (polyamide MACMT), poly (4,4′-methylenebis (2-methyl-cyclohexylene) isophthalamide) (polyamide MACMI), poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexahydroterephthalamide) (polyamide MACMT (H)), poly (4,4′-methylenebis (2-methyl-cyclohexylene) naphthalamide) (polyamide MACMN ), Poly (4,4′-propylene biscyclohexylene adipamide) (polyamide PACP6), poly (4,4′-propylene biscyclohexylene suberamide) (polyamide PACP8), poly (4,4′-propylene bis) Cyclohexylene azeamide) (Polyamide PACP9), poly (4,4′-propylene biscyclohexylene sebacamide) (polyamide PACP10), poly (4,4′-propylene biscyclohexylene dodecamide) (polyamide PACP12), poly (4,4 ′ -Propylene biscyclohexylene tetradecanamide (polyamide PACP14), poly (4,4'-propylene biscyclohexylene hexadecanamide) (polyamide PACP16), poly (4,4'-propylene biscyclohexylene octadecanamide) ( Polyamide PACP18), poly (4,4′-propylene biscyclohexylene terephthalamide) (polyamide PACPT), poly (4,4′-propylene biscyclohexylene isophthalamide) (polyamide PACPI), poly (4,4 ′ -Propi Biscyclohexylene hexahydroterephthalamide) (polyamide PACPT (H)), poly (4,4′-propylene biscyclohexylene naphthalamide) (polyamide PACPN), polyisophorone adipamide (polyamide IPD6), polyisophorones Lamide (polyamide IPD8), polyisophorone azeramide (polyamide IPD9), polyisophorone sebamide (polyamide IPD10), polyisoholondecamide (polyamide IPD12), polyisophorone terephthalamide (polyamide IPDT), polyisophorone isophthalamide ( Polyamide IPDI), polyisophorone hexahydroterephthalamide (polyamide IPDT (H)), polyisophorone naphthalamide (polyamide IPDN), polytetramethylene terephthala (Polyamide 4T), polytetramethylene isophthalamide (polyamide 4I), polytetramethylene hexahydroterephthalamide (polyamide 4T (H)), polytetramethylene naphthalamide (polyamide 4N), polypentamethylene terephthalamide ( Polyamide 5T), polypentamethylene isophthalamide (polyamide 5I), polypentamethylene hexahydroterephthalamide (polyamide 5T (H)), polypentamethylene naphthalamide (polyamide 5N), polyhexamethylene terephthalamide (polyamide 6T) ), Polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene hexahydroterephthalamide (polyamide 6T (H)), polyhexamethylene naphthalamide (polyamide 6N), poly (2-methylpentameth) Tylene terephthalamide) (polyamide M5T), poly (2-methylpentamethylene isophthalamide) (polyamide M5I), poly (2-methylpentamethylene hexahydroterephthalamide) (polyamide M5T (H)), poly (2 -Methyl pentamethylene naphthalamide (polyamide M5N), polynonamethylene terephthalamide (polyamide 9T), polynonamethylene isophthalamide (polyamide 9I), polynonamethylene hexahydroterephthalamide (polyamide 9T (H)), poly Nonamethylene naphthalamide (polyamide 9N), poly (2-methyloctamethylene terephthalamide) (polyamide M8T), poly (2-methyloctamethylene isophthalamide) (polyamide M81), poly (2-methyloctamethylene hexahydro) Terephthala (Polyamide M8T (H)), poly (2-methyloctamethylene naphthalamide) (polyamide M8N), polytrimethylhexamethylene terephthalamide (polyamide TMHT), polytrimethylhexamethylene isophthalamide (polyamide TMHI), poly Trimethylhexamethylene hexahydroterephthalamide (polyamide TMHT (H)), polytrimethylhexamethylene naphthalamide (polyamide TMHN), polydecamethylene terephthalamide (polyamide 10T), polydecamethylene isophthalamide (polyamide 10I), poly Decamethylene hexahydroterephthalamide (polyamide 10T (H)), polydecamethylene naphthalamide (polyamide 10N), polyundecamethylene terephthalamide (polyamide 11T), poly Decamethylene isophthalamide (polyamide 11I), polyundecamethylene hexahydroterephthalamide (polyamide 11T (H)), polyundecamethylene naphthalamide (polyamide 11N), polydodecamethylene terephthalamide (polyamide 12T), poly Co-polymerization using dodecamethylene isophthalamide (polyamide 12I), polydodecamethylene hexahydroterephthalamide (polyamide 12T (H)), polydodecamethylene naphthalamide (polyamide 12N) and several raw materials of these polyamides Examples include coalescence. These can use 1 type (s) or 2 or more types.

  Other thermoplastic resins to be mixed include high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and ultra high molecular weight polyethylene (UHMWPE). , Polypropylene (PP), polybutene (PB), polymethylpentene (TPX), ethylene / propylene copolymer (EPR), ethylene / butene copolymer (EBR), ethylene / vinyl acetate copolymer (EVA), ethylene / Acrylic acid copolymer (EAA), ethylene / methacrylic acid copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), ethylene / ethyl acrylate Polyolefin resin such as copolymer (EEA), police Len (PS), syndiotactic polystyrene (SPS), methyl methacrylate / styrene copolymer (MS), methyl methacrylate / styrene / butadiene copolymer (MBS), styrene / butadiene copolymer (SBR), styrene / Isoprene copolymer (SIR), styrene / isoprene / butadiene copolymer (SIBR), styrene / butadiene / styrene copolymer (SBS), styrene / isoprene / styrene copolymer (SIS), styrene / ethylene / butylene / Styrene copolymer (SEBS), polystyrene resins such as styrene / ethylene / propylene / styrene copolymer (SEPS), functional groups such as carboxyl groups and salts thereof, acid anhydride groups, and epoxy groups Polyolefin resin, polystyrene resin, polybuty Terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), poly (ethylene terephthalate / ethylene isophthalate) copolymer (PET / PEI), polytrimethylene terephthalate (PTT), polycyclohexanedimethylene terephthalate Polyester resins such as (PCT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyarylate (PAR), liquid crystal polyester (LCP), polylactic acid (PLA), polyglycolic acid (PGA), and polyacetal Polysulfone such as (POM), polyether resins such as polyphenylene ether (PPO), polysulfone (PSU), polyethersulfone (PESU), polyphenylsulfone (PPSU) Resin, polythioether resin such as polyphenylene sulfide (PPS), polythioether sulfone (PTES), polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK) , Polyether ether ether ketone (PEEEK), polyether ether ketone ketone (PEEKK), polyether ketone ketone ketone (PEKKK), polyether ketone ether ketone ketone (PEKEKK) and other polyketone resins, polyacrylonitrile (PAN), poly Methacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), acrylonitrile / Polynitrile resins such as butadiene copolymer (NBR), polymethacrylate resins such as polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA), polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), poly Polyvinyl resins such as vinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer, cellulose resins such as cellulose acetate and cellulose butyrate, polycarbonate resins such as polycarbonate (PC) , Polyimide resins such as thermoplastic polyimide (TPI), polyetherimide, polyesterimide, polyamideimide (PAI), polyesteramideimide, thermoplastic polyurethane resin, polyamide elastomer, polyurethane elastomer , A polyester elastomer. These can use 1 type (s) or 2 or more types.

  Furthermore, for the aliphatic polyamide (A), an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, an inorganic filler, an antistatic agent, a flame retardant, a crystallization accelerator, if necessary. A colorant or the like may be added.

(2) Polyamide 6/66/12 composition (B)
Polyamide 6/66/12 composition (B) used in the present invention includes polyhexamethylene sebamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene decamide (polyamide 910), At least one selected from the group consisting of polynonamethylene dodecamide (polyamide 912), polydecane methylene decanamide (polyamide 1010), polydecane methylene dodecane (polyamide 1012), and polydocamethylene dodecamide (polyamide 1212). Polyamide mixture (B1) composed of polyamide and poly (caproamide / hexamethylene adipamide / dodecanamide) (polyamide 6/66/12) 50% by mass to 98% by mass, plasticizer (B2) 1% by mass to 20% % By mass and IS The olefin polymer (B3) having a flexural modulus measured in accordance with 178 of 500 MPa or less contains 1% by mass or more and 30% by mass or less (hereinafter sometimes referred to as polyamide 6/66/12 composition (B)). .)

Poly (caproamide / hexamethylene adipamide / dodecanamide) (polyamide 6/66/12) has an amide bond (—CONH—) in the main chain: (—CO— (CH ₂ ) ₆ —NH _-) caproamide units and the following equation represented by _{n: (- NH- (CH 2} ) 6 -NH-CO- (CH 2) 4 -CO-) following equation and hexamethylene adipamide units :( represented by _n —CO— (CH ₂ ) ₁₁ —NH—) A polyamide copolymer having a dodecanamide unit represented by _n (hereinafter sometimes referred to as polyamide 6/66/12). Polyamide 6/66/12 can be obtained by copolymerizing 6-aminocaproic acid or caprolactam, hexamethylenediamine and adipic acid salt, and 12-aminododecanoic acid or dodecane lactam.
In polyamide 6/66/12, the mass ratio of the total unit of caproamide unit and hexamethylene adipamide unit to dodecanamide unit is determined from the viewpoint of sufficiently ensuring the interlayer adhesion of the laminated tube and its durability. , Preferably from 81: 19% by mass to 95: 5% by mass, and from 83: 17% by mass to 92: 8% by mass, based on a total of 100% by mass of hexamethylene adipamide units and dodecanamide units. The following is more preferable.
In polyamide 6/66/12, the mass ratio of caproamide unit to hexamethylene adipamide unit ensures sufficient heat resistance of the laminated tube, and during coextrusion with ethylene / vinyl acetate copolymer saponified product (C) From the viewpoint of molding stability, it is preferably 80: 20% by mass or more and 95: 5% by mass or less, and 82: 18% by mass or more, with respect to 100% by mass in total of caproamide units and hexamethylene adipamide units. It is more preferable that it is 93: 7 mass% or less.

Polyamide 6/66/12 composition (B) comprises polyamide 6/66/12 and polyhexamethylene sebamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene decanamide (polyamide 910). , Polynonamethylene dodecamide (polyamide 912), polydecane methylene decanamide (polyamide 1010), polydecane methylene dodecane (polyamide 1012), and polydodecane methylene dodecamide (polyamide 1212). A polyamide mixture (B1) made of the above polyamide (hereinafter sometimes referred to as a polyamide mixture (B1)).
Polyhexamethylene sebamide (Polyamide 610), Polyhexamethylene dodecane (Polyamide 612), Polynonamethylene decanamide (Polyamide 910), Polynonamethylene dodecamide (Polyamide 912), Polydecamethylene decamide (Polyamide 1010) Polydecamethylene dodecamide (polyamide 1012) and polydocamethylene dodecamide (polyamide 1212) are long-chain aliphatic polyamides (hereinafter sometimes referred to as long-chain aliphatic polyamides), and interlayer adhesion of laminated tubes. From the viewpoint of obtaining sufficient properties and durability, polyhexamethylene sebacamide (polyamide 610) and polyhexamethylene dodecamide (polyamide 612) are preferable.

  The mixing ratio of both polyamide 6/66/12 and long-chain aliphatic polyamide is sufficient to obtain a laminated tube with excellent mechanical properties, chemical resistance, and flexibility, and interlayer adhesion and durability. From the viewpoint of obtaining the above, the polyamide 6/66/12 content is 50% by mass or more and 80% by mass or less with respect to 100% by mass of the polyamide mixture (B1) of polyamide 6/66/12 and long-chain aliphatic polyamide. Preferably, it is 55 to 75% by mass, more preferably 60 to 70% by mass, and the long chain aliphatic polyamide content is 20 to 50% by mass. It is preferably no greater than mass%, more preferably no less than 25 mass% and no greater than 45 mass%, and even more preferably no less than 30 mass% and no greater than 40 mass%.

  As an apparatus for producing polyamide 6/66/12 or a long-chain aliphatic polyamide, known polyamide producing apparatuses described in the explanation of aliphatic polyamide (A) can be mentioned. As a method for producing polyamide 6/66/12 or long-chain aliphatic polyamide, known methods described in the explanation of aliphatic polyamide (A) can be mentioned.

  The relative viscosity of polyamide 6/66/12 or long-chain aliphatic polyamide measured under the conditions of 96% sulfuric acid, polymer concentration of 1% and 25 ° C. according to JIS K-6920 is the laminated tube obtained. From the viewpoints of securing the mechanical properties and ensuring the desirable formability of the laminated tube by setting the viscosity at the time of melting to an appropriate range, it is preferably 1.5 or more and 5.0 or less, and 2.0 or more and 4 or less. More preferably, it is 5 or less.

  Polyamide 6/66/12 and long chain aliphatic polyamide, when the terminal amino group concentration per 1 g of the polyamide is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), Satisfying [A]> [B] +5 is preferable from the viewpoint of sufficiently securing the interlayer adhesiveness and durability of the laminated tube, and more preferably [A]> [B] +10, [A] > [B] +15 is more preferable (hereinafter sometimes referred to as terminal-modified polyamide). Furthermore, [A]> 20 is preferable from the viewpoint of the melt stability of the polyamide and the generation of gel-like substances is suppressed, and 30 <[A] <120 is more preferable.

  The terminal-modified polyamide is produced by polymerizing or copolymerizing the polyamide raw material in the presence of amines by a known method such as melt polymerization, solution polymerization or solid phase polymerization. Alternatively, it is produced by melt-kneading in the presence of amines after polymerization. As described above, amines can be added at any stage during polymerization or at any stage after melt kneading after polymerization. However, when the interlayer adhesion of the laminated tube is taken into consideration, the amines are added at the stage during polymerization. It is preferable. Examples of the amines include monoamines, diamines, triamines, and polyamines. In addition to amines, carboxylic acids such as monocarboxylic acids, dicarboxylic acids, and tricarboxylic acids may be added as necessary as long as they do not deviate from the range of the above-mentioned end group concentration conditions. These amines and carboxylic acids may be added simultaneously or separately. Examples of the amines and carboxylic acids exemplified below include those described in the description of the aliphatic polyamide (A), and these can be used alone or in combination of two or more.

  Examples of the plasticizer (B2) in the polyamide 6/66/12 composition (B) include benzenesulfonic acid alkylamides, toluenesulfonic acid alkylamides, and hydroxybenzoic acid alkyl esters.

  Examples of benzenesulfonic acid alkylamides include benzenesulfonic acid propylamide, benzenesulfonic acid butyramide, and benzenesulfonic acid 2-ethylhexylamide. Examples of toluenesulfonic acid alkylamides include N-ethyl-o-toluenesulfonic acid butyramide, N-ethyl-p-toluenesulfonic acid butyramide, N-ethyl-o-toluenesulfonic acid 2-ethylhexylamide, and N-ethyl-p. -Toluenesulfonic acid 2-ethylhexylamide etc. are mentioned. Examples of hydroxybenzoic acid alkyl esters include ethyl hexyl o-hydroxybenzoate, ethyl hexyl p-hydroxybenzoate, hexyl decyl o-hydroxybenzoate, hexyl decyl p-hydroxybenzoate, ethyl decyl o-hydroxybenzoate, p-hydroxybenzoate Ethyl decyl, octyl octyl o-hydroxybenzoate, octyl octyl p-hydroxybenzoate, decyldodecyl o-hydroxybenzoate, decyldodecyl p-hydroxybenzoate, methyl o-hydroxybenzoate, methyl p-hydroxybenzoate, o -Butyl hydroxybenzoate, butyl p-hydroxybenzoate, hexyl o-hydroxybenzoate, hexyl p-hydroxybenzoate, n-octyl o-hydroxybenzoate, p-hydroxybenzoate n- octyl, o- hydroxybenzoic acid decyl, p- hydroxybenzoic acid decyl, o- hydroxybenzoic acid dodecyl, p- hydroxybenzoic acid dodecyl, and the like. These can use 1 type (s) or 2 or more types.

  Among these, benzenesulfonic acid alkylamides such as benzenesulfonic acid butyramide and benzenesulfonic acid 2-ethylhexylamide, N-ethyl-p-toluenesulfonic acid butyramide, N-ethyl-p-toluenesulfonic acid 2-ethylhexylamide and the like Preferred are hydroxybenzoic acid alkyl esters such as toluenesulfonic acid alkylamides, p-hydroxybenzoic acid ethylhexyl, p-hydroxybenzoic acid hexyldecyl, p-hydroxybenzoic acid ethyldecyl, benzenesulfonic acid butyramide, p-hydroxybenzoic acid More preferred are ethylhexyl and hexyldecyl p-hydroxybenzoate.

  Olefin polymer (B3) having a flexural modulus measured according to ISO 178 in the polyamide 6/66/12 composition (B) of 500 MPa or less (hereinafter sometimes referred to as olefin polymer (B3)). Is added to improve the low temperature impact resistance of polyamide 6/66/12 or long chain aliphatic polyamide. When the flexural modulus measured in accordance with ISO 178 of the olefin polymer (B3) exceeds this value, the impact improving effect may be insufficient.

  As the olefin polymer (B3), (ethylene and / or propylene) / α-olefin copolymer, (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) ) Type copolymer, ionomer polymer, aromatic vinyl compound / conjugated diene compound type block copolymer, and these may be used alone or in combination of two or more.

  The (ethylene and / or propylene) / α-olefin copolymer is a polymer obtained by copolymerizing ethylene and / or propylene and an α-olefin having 3 or more carbon atoms, and α- having 3 or more carbon atoms. Examples of olefins include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4- Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl 1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene, and the like. These can use 1 type (s) or 2 or more types. In addition, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-methyl-1, 5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1,4,8- Decatriene (DMDT), dicyclopentadiene, cyclohexadiene, cyclooctadiene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl -5-Isopropenyl-2-norbornene, 2,3-Diisopropylidene-5-norbornene, 2-E Isopropylidene-3-isopropylidene-5-norbornene may be copolymerized non-conjugated diene polyene such as 2-propenyl-2,5-norbornadiene. These can use 1 type (s) or 2 or more types.

  The (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) copolymer is composed of ethylene and / or propylene and α, β-unsaturated carboxylic acid and / or This is a polymer obtained by copolymerizing an unsaturated carboxylic acid ester monomer, and examples of the α, β-unsaturated carboxylic acid monomer include acrylic acid and methacrylic acid. Examples of the monomer include methyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, heptyl ester, octyl ester, nonyl ester, and decyl ester of these unsaturated carboxylic acids. These can use 1 type (s) or 2 or more types.

  In the ionomer polymer, at least a part of the carboxyl group of the olefin and the α, β-unsaturated carboxylic acid copolymer is ionized by neutralization of metal ions. Ethylene is preferably used as the olefin, and acrylic acid and methacrylic acid are preferably used as the α, β-unsaturated carboxylic acid, but are not limited to those exemplified here, The body may be copolymerized. Metal ions include alkali metals such as Li, Na, K, Mg, Ca, Sr, Ba, alkaline earth metals, Al, Sn, Sb, Ti, Mn, Fe, Ni, Cu, Zn, Cd, etc. Is mentioned. These can use 1 type (s) or 2 or more types.

The aromatic vinyl compound / conjugated diene compound block copolymer is a block copolymer comprising an aromatic vinyl compound polymer block and a conjugated diene compound polymer block, and the aromatic vinyl compound polymer. A block copolymer having at least one block and at least one conjugated diene compound-based polymer block is used. In the block copolymer, the unsaturated bond in the conjugated diene compound-based polymer block may be hydrogenated.
The aromatic vinyl compound polymer block is a polymer block mainly composed of units derived from an aromatic vinyl compound. In this case, the aromatic vinyl compound includes styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,5-dimethylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene, 4-propyl. Styrene, 4-cyclohexyl styrene, 4-dodecyl styrene, 2-ethyl-4-benzyl styrene, 4- (phenylbutyl) styrene and the like can be mentioned, and one or more of these can be used. In addition, the aromatic vinyl compound-based polymer block may optionally have a unit composed of a small amount of another unsaturated monomer.
Conjugated diene compound-based polymer blocks are 1,3-butadiene, chloroprene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3 -A polymer block formed from one or more conjugated diene compounds such as hexadiene, and a hydrogenated aromatic vinyl compound / conjugated diene compound block copolymer, the conjugated diene compound polymer Part or all of the unsaturated bond portions in the block are saturated bonds by hydrogenation.

  The molecular structure of the aromatic vinyl compound / conjugated diene compound block copolymer and the hydrogenated product thereof may be linear, branched, radial, or any combination thereof. Among these, as an aromatic vinyl compound / conjugated diene compound block copolymer and / or a hydrogenated product thereof, one aromatic vinyl compound polymer block and one conjugated diene compound polymer block are linear. The three polymer blocks are bonded in a straight chain in the order of diblock copolymer, aromatic vinyl compound polymer block, conjugated diene compound polymer block, and aromatic vinyl compound polymer block. One or more of these triblock copolymers and hydrogenated products thereof are preferably used. Unhydrogenated or hydrogenated styrene / butadiene block copolymers, unhydrogenated or hydrogenated styrene / isoprene block copolymers Polymer, unhydrogenated or hydrogenated styrene / butadiene / styrene block copolymer, unhydrogenated or hydrogenated styrene / isoprene / styrene block Click copolymer, non-hydrogenated or hydrogenated styrene / (ethylene / butadiene) / styrene block copolymer, non-hydrogenated or include hydrogenated styrene / (isoprene / butadiene) / styrene block copolymer.

  Further, (ethylene and / or propylene) / α-olefin copolymer, (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid) used as the olefin polymer (B3). As the acid ester) copolymer, ionomer polymer, and aromatic vinyl compound / conjugated diene compound block copolymer, a polymer modified with a carboxylic acid and / or a derivative thereof is preferably used. By modifying with such components, functional groups having affinity for polyamide 6/66/12 or long-chain aliphatic polyamide are included in the molecule.

  Functional groups having affinity for polyamide 6/66/12 and long-chain aliphatic polyamides include carboxyl groups, acid anhydride groups, carboxylic acid ester groups, carboxylic acid metal salts, carboxylic acid imide groups, and carboxylic acid amides. Group, epoxy group and the like. Examples of compounds containing these functional groups include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid Endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid and metal salts of these carboxylic acids, monomethyl maleate, monomethyl itaconate, methyl acrylate, ethyl acrylate, butyl acrylate 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, itaconic anhydride, citracone anhydride Acid, endobicyclo- 2.2.1] -5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, acrylamide, methacrylamide, glycidyl acrylate, glycidyl methacrylate, Examples include glycidyl ethacrylate, glycidyl itaconate, and glycidyl citraconic acid. These can use 1 type (s) or 2 or more types.

The content of the polyamide mixture (B1) in the polyamide 6/66/12 composition (B) is 50% by mass to 98% by mass, preferably 60% by mass to 95% by mass, and 70% by mass. % To 92% by mass is more preferable. When the content of the polyamide mixture (B1) is less than the above value, the mechanical properties of the obtained laminated tube may be inferior. On the other hand, when the content exceeds the above value, the interlayer adhesion of the obtained laminated tube and its Durability may be inferior.
The content of the plasticizer (B2) is 1% by mass to 20% by mass, preferably 2% by mass to 15% by mass, and more preferably 3% by mass to 10% by mass. When the content of the plasticizer (B2) is less than the above value, the flexibility of the obtained laminated tube may be inferior. On the other hand, when the content exceeds the above value, the low temperature impact resistance of the obtained laminated tube is inferior. Sometimes.
The content of the olefin polymer (B3) is 1% by mass or more and 30% by mass or less, preferably 3% by mass or more and 25% by mass or less, and more preferably 5% by mass or more and 20% by mass or less. When the content of the olefin polymer (B3) is less than the above value, the resulting laminated tube may be inferior in low-temperature impact resistance and interlayer adhesion and durability thereof, whereas when exceeding the above value, The resulting laminated tube may have inferior mechanical properties.

  The production method of the polyamide 6/66/12 composition (B) is not particularly limited, and various additives that have been conventionally known can be employed by blending various additives as necessary. For example, together with other components to which polyamide 6/66/12 and long-chain aliphatic polyamide and olefin polymer (B3) are added as necessary, pellets are mixed at the above mixing ratio using a tumbler or a mixer. Thus, it can be manufactured by a method of injecting the plasticizer (B2) with a metering pump from the middle of the cylinder of the melt-kneader and melt-kneading it while dry blending uniformly and supplying it to the melt-kneader. The melt kneading can be performed using a kneader such as a single screw extruder, a twin screw extruder, a kneader, or a Banbury mixer.

  The polyamide 6/66/12 composition (B) may contain other polyamide-based resins or other thermoplastic resins. Examples of other polyamide resins or other thermoplastic resins include the same resins as those of the aliphatic polyamide (A). The content of the polyamide 6/66/12 composition (B) in the mixture is preferably 60% by mass or more, and more preferably 70% by mass or more.

  Furthermore, for the polyamide 6/66/12 composition (B), if necessary, an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, an inorganic filler, an antistatic agent, a flame retardant Further, a crystallization accelerator, a colorant, a lubricant and the like may be added.

(3) Saponified ethylene / vinyl acetate copolymer (C)
The saponified ethylene / vinyl acetate copolymer (C) used in the present invention is obtained by saponifying a copolymer composed of ethylene and vinyl acetate by a known method using an alkali catalyst or the like (hereinafter, EVOH (C) may be referred to.)
Furthermore, the ethylene content of EVOH (C) is preferably 15 mol% or more and 60 mol% or less from the viewpoint of sufficiently ensuring melt moldability, flexibility, impact resistance, and chemical penetration prevention properties, It is more preferably 20 mol% or more and 55 mol% or less, and further preferably 25 mol% or more and 45 mol% or less. Here, when EVOH (C) consists of a mixture of two or more types of EVOH having different ethylene contents, the value calculated from the respective ethylene contents and the mixing mass ratio is taken as the ethylene content.

  Further, the saponification degree of the vinyl ester component of EVOH (C) is preferably 90 mol% or more, more preferably 95 mol% or more, and 98% from the viewpoint of obtaining good chemical solution permeation prevention properties. It is more preferably at least mol, and particularly preferably at least 99 mol%. Here, when EVOH (C) consists of a mixture of two or more types of EVOH having different saponification degrees, the value calculated from each saponification degree and the mixing mass ratio is defined as the saponification degree. In addition, the ethylene content and the saponification degree of EVOH can be obtained by a nuclear magnetic resonance (NMR) method.

  EVOH (C) melt flow rate (MFR) (210 ° C, under 2160 g load) ensures a desirable moldability by setting the viscosity at the time of melting to an appropriate range, does not excessively lower the melt tension, and draws down at the time of molding. From the viewpoint of preventing the occurrence of such problems, it is preferably 0.1 g / 10 min or more and 100 g / 10 min or less, more preferably 0.3 g / 10 min or more and 50 g / 10 min or less. More preferably, it is 5 g / 10 min or more and 20 g / 10 min or less.

  Further, other monomers can be copolymerized as long as the object of the present invention is not impaired. Other monomers include vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, Vinyl esters such as vinyl palmitate, vinyl stearate, isopropenyl acetate, 1-butenyl acetate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl cyclohexanecarboxylate, vinyl benzoate, vinyl cinnamate, propylene, 1- Α-olefins such as butene, isobutene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-dodecene, acrylic acid, methacrylic acid, crotonic acid, phthalic acid, (anhydrous) maleic acid, (anhydrous) ) Unsaturated acids such as itaconic acid or salts thereof, or the number of carbon atoms 18 or less mono- or dialkyl esters, acrylamide, N-alkyl acrylamide having 1 to 18 carbon atoms, N, N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or its salt, acrylamidopropyldimethylamine or its acid salt Or an acrylamide such as a quaternary salt thereof, methacrylamide, N-alkyl methacrylamide having 1 to 18 carbon atoms, N, N-dimethylmethacrylamide, 2-methacrylamide propanesulfonic acid or a salt thereof, methacrylamidepropyldimethyl Methacrylamide such as amine or its acid salt or quaternary salt thereof, N-vinylamide such as N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide, vinyl cyanide such as acrylonitrile, methacrylonitrile, etc. Nyls, vinyl ethers such as alkyl vinyl ethers having 1 to 18 carbon atoms, hydroxyalkyl vinyl ethers, alkoxyalkyl vinyl ethers, vinyl halides such as vinyl chloride, vinylidene chloride, vinyl fluoride, vinylidene fluoride, vinyl bromide, Vinylsilanes such as vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, vinylmethyldiethoxysilane, vinyldimethylethoxysilane γ-methacryloxypropylmethoxysilane, allyl acetate, allyl chloride, allyl alcohol Dimethylallyl alcohol, trimethyl- (3-acrylamido-3-dimethylpropyl) -ammonium chloride, acrylamido-2-methylpropanesulfonic acid, Nil ethylene carbonate. These can use 1 type (s) or 2 or more types.

  EVOH (C) can also contain various additives as required. Examples of such additives include antioxidants, plasticizers, heat stabilizers, UV absorbers, antistatic agents, lubricants, colorants, fillers, or other thermoplastic resins, It can contain in the range which does not inhibit the effect of this invention. Specifically, 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4,4′-thiobis (6-t-butyl-m-cresol), 4, 4'-thiobis (6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t-butyphenol), 2,2'-methylene-bis (4-methyl-6-t-butylphenol) 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), n-octadecyl-β- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate, N, N ′ Hexamethylene bis (3,5-di-t-butyl-4-hydroxyhydrocinnamide), 1,1,3-tris (2-methyl-4-hydroxy-5-t-butylphenyl) butane, 1, 3,5-trimethyl- , 4,6-Tris (3,5-di-t-butyl-4-hydroxybenzyl) benzene, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate ], Benzeneerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], tris (2,4-di-t-butylphenyl), di (2,4-di Antioxidants such as -t-butylphenyl) -pentaerythritol-diphosphite, ethylene-2-cyano-3,3'-diphenyl acrylate, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2 -(2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2-hydroxy-4-methoxybenzofe UV absorbers such as non, 2,2′-dihydroxy-4-methoxybenzophenone and 2-hydroxy-4-octoxybenzophenone, plasticizers such as dimethyl phthalate, diethyl phthalate, dioctyl phthalate and phosphate esters, penta Erythlit monostearate, sorbitan monopalmitate, sulfated polyolefins, antistatic agents such as aliphatic polyhydric alcohols such as ethylene glycol, glycerin and hexanediol, saturated fatty acid amides such as stearic acid amide, oleic acid amide, etc. Unsaturated fatty acid amides, bis fatty acid amides such as ethylene bis-stearic acid amide, fatty acid metal salts such as calcium stearate, magnesium stearate, zinc stearate, aluminum stearate, wax, liquid paraffin, low molecular weight polyolefin Lubricants such as acetic acid, organic acids such as acetic acid, propionic acid and stearic acid, inorganic acid compounds such as boric acid compounds and phosphoric acid compounds, stabilizers such as metal salts of hydrotalcite, reduced iron powders, potassium sulfite , Oxygen absorbers such as ascorbic acid, hydroquinone, gallic acid, colorants such as carbon black, phthalocyanine, quinacridone, indoline, azo pigments, bengara, glass fiber, asbestos, ballastite, mica, sericite, talc, silica, Examples include fillers such as kaolin, calcium silicate, and montmorillonite.

  Furthermore, EVOH (C) preferably contains a boron compound. By containing a boron compound, the melt stability is improved, which is effective from the viewpoint of obtaining a laminated tube having a uniform wall thickness. Examples of the boron compound include boric acids, boric acid esters, borates, and borohydrides. Examples of the boric acid include orthoboric acid, metaboric acid, and tetraboric acid. Examples of the boric acid ester include triethyl borate and trimethyl borate. Examples of the boric acid salt include alkali metals of the above various boric acids. Examples thereof include salts, alkaline earth metal salts, and borax. These can use 1 type (s) or 2 or more types. Among these, orthoboric acid is preferable.

  The content of the boron compound in EVOH (C) is 0.002 mass in terms of boron element with respect to 100 mass parts of EVOH (C) from the viewpoint of sufficiently securing the content effect and obtaining a tube having a good appearance. Part to 0.5 parts by mass, more preferably 0.005 parts to 0.2 parts by mass.

  EVOH (C) may contain a phosphoric acid compound. By containing a phosphoric acid compound, it is possible to achieve both long run properties, color resistance, and interlayer adhesion during melt molding. It does not specifically limit as a phosphoric acid compound, Various acids, such as phosphoric acid and phosphorous acid, its salt, etc. can be used. Examples of the phosphate include primary phosphate, secondary phosphate, and tertiary phosphate. These can use 1 type (s) or 2 or more types. The cationic species of phosphate is not particularly limited, but alkali metal salts are preferable. Among these, sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, dipotassium hydrogen phosphate are preferred. preferable.

  The content of the phosphoric acid compound in EVOH (C) is 0.02 in terms of phosphate radical with respect to 100 parts by mass of EVOH (C) from the viewpoint of sufficiently securing the content and obtaining a tube having a good appearance. It is preferably no greater than mass parts, more preferably no less than 0.0005 mass parts and no greater than 0.01 mass parts, and even more preferably no less than 0.001 mass parts and no greater than 0.007 mass parts.

  Moreover, it is also preferable to contain alkali and / or alkaline-earth metal salt with respect to EVOH (C) from a viewpoint of melt stability or long run property. There is no limitation as an anion seed | species of the salt of an alkali metal or alkaline-earth metal, A carboxylate, a hydroxide, carbonate, hydrogencarbonate etc. are mentioned. There is no limitation on the cation species of the alkali metal salt, such as lithium salt, sodium salt, potassium salt, etc. There is no limitation on the cation species of the alkaline earth metal salt, magnesium salt, calcium salt, barium salt, beryllium salt, strontium Examples include salts. Specifically, sodium acetate, lithium acetate, potassium acetate, calcium palmitate, magnesium palmitate, calcium myristate, magnesium myristate, calcium stearate, magnesium stearate, calcium oleate, magnesium oleate, calcium linoleate, linole Examples thereof include magnesium acid, calcium linolenate, magnesium linolenate, sodium phosphate, lithium phosphate and the like. These can use 1 type (s) or 2 or more types.

  The content of the alkali and / or alkaline earth metal salt in the EVOH (C) is sufficient to ensure the content effect, and from the viewpoint of obtaining a tube having a good appearance, the metal is used with respect to 100 parts by mass of the EVOH (C). It is preferably 0.0005 parts by mass or more and 0.2 parts by mass or less in terms of element, more preferably 0.001 parts by mass or more and 0.1 parts by mass or less, and 0.002 parts by mass or more and 0.05 parts by mass or less. More preferably, it is at most parts.

  In addition, EVOH (C) includes one or two antioxidants such as hydrotalcite categorization and hindered phenols within a range not impairing the object of the present invention in order to improve melt stability and the like. It is preferable to add 0.01 parts by mass or more and 1 part by mass or less with respect to 100 parts by mass of EVOH (C).

(4) Fluorinated polymer (D)
The fluorine-containing polymer (D) used in the present invention is a fluorine-containing polymer in which a functional group having reactivity with an amino group is introduced into a molecular chain (hereinafter referred to as a fluorine-containing polymer). (It may be referred to as (D).)
The fluorine-containing polymer (D) is a polymer (homopolymer or copolymer) having a repeating unit derived from at least one fluorine-containing monomer. It is not particularly limited as long as it is a fluorine-containing polymer that can be heat-melted.
Here, as the fluorine-containing monomer, tetrafluoroethylene (TFE), trifluoroethylene, vinylidene fluoride (VDF), vinyl fluoride (VF), chlorotrifluoroethylene (CTFE), trichlorofluoroethylene, hexafluoropropylene (HFP), CF ₂ = CFOR ^f1 (where R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms), CF ₂ = CF—OCH ₂ —R. ^f2 (wherein R ^f2 represents a perfluoroalkylene group which may contain an etheric oxygen atom having 1 to 10 carbon atoms), CF ₂ = CF (CF ₂ ) _p OCF = CF ₂ (where , p is 1 or ^{_{2.), CH 2 = CX}} 1 (CF 2) n X 2 ( wherein, ^{X 1} and ^{X 2} are each other Independently represent a hydrogen atom or a fluorine atom, n is an integer from 2 to 10.), And the like. These can use 1 type (s) or 2 or more types.

Specific examples of the general formula CF ₂ = CFOR ^f1 include CF ₂ = CFOCF ₂ (perfluoro (methyl vinyl ether): PMVE), CF ₂ = CFOCF ₂ CF ₃ (perfluoro (ethyl vinyl ether): PEVE), CF ₂ = CFOCF ₂ CF ₂ CF ₃ (perfluoro (propyl vinyl ether): PPVE), CF ₂ = CFOCF ₂ CF ₂ CF ₂ CF ₃ (perfluoro (butyl vinyl ether): PBVE) and CF ₂ = CFO (CF ₂ ) ₈ F (Perfluoro (octyl vinyl ether): POVE) and other perfluoro (alkyl vinyl ethers) (hereinafter sometimes referred to as PAVE). Among these, CF ₂ = CFOCF ₂ and CF ₂ = CFOCF ₂ CF ₂ CF ₃ are preferable.

Similarly, the general formula ^{_{CH 2 = CX 1 (CF 2}} ) n X 2 ( wherein, ^{X 1} and ^{X 2} represents a hydrogen atom or a fluorine atom independently of one another, n is an integer from 2 to 10.) From the viewpoint of ensuring sufficient polymerization reactivity, n in the compound represented by the formula (1) ensures the effect of modifying the fluorine-containing polymer (for example, suppressing the occurrence of cracks in the molded product or molded product). It is an integer of 2 or more and 10 or less. Specifically, CH ₂ = CF (CF ₂ ) ₂ F, CH ₂ = CF (CF ₂ ) ₃ F, CH ₂ = CF (CF ₂ ) ₄ F, CH ₂ = CF (CF ₂ ) ₅ F, CH _{2 = CF (CF 2) 8} F, CH 2 = CF (CF 2) 2 H, CH 2 = CF (CF 2) 3 H, CH 2 = CF (CF 2) 4 H, CH 2 = CF (CF 2 _{) 5 H, CH 2 = CF} (CF 2) 8 H, CH 2 = CH (CF 2) 2 F, CH 2 = CH (CF 2) 3 F, CH 2 = CH (CF 2) 4 F, CH 2 _{= CH (CF 2) 5 F} , CH 2 = CH (CF 2) 8 F, CH 2 = CH (CF 2) 2 H, CH 2 = CH (CF 2) 3 H, CH 2 = CH (CF 2) ₄ H, CH ₂ ═CH (CF ₂ ) ₅ H, CH ₂ ═CH (CF ₂ ) ₈ H, and the like. These can use 1 type (s) or 2 or more types.
Among these, a compound represented by CH ₂ ═CH (CF ₂ ) _n F or CH ₂ ═CF (CF ₂ ) _n H is preferable, and n in the formula is 2 or more and 4 or less. It is more preferable from the viewpoint of the balance between the chemical solution permeation preventive property and the environmental stress crack resistance of the polymer (D).

  The fluorine-containing polymer (D) may further contain a polymer unit based on a non-fluorine-containing monomer in addition to the fluorine-containing monomer. Non-fluorine-containing monomers include olefins having 2 to 4 carbon atoms such as ethylene, propylene, isobutene, vinyl chloride, vinylidene chloride, vinyl acetate, vinyl chloroacetate, vinyl lactate, vinyl butyrate, vinyl pivalate, benzoic acid Vinyl esters such as vinyl acid, vinyl crotonate, methyl (meth) acrylate, ethyl (meth) acrylate, n-butyl (meth) acrylate and methyl crotonate, methyl vinyl ether (MVE), ethyl vinyl ether (EVE), Examples thereof include vinyl ethers such as butyl vinyl ether (BVE), isobutyl vinyl ether (IBVE), cyclohexyl vinyl ether (CHVE), and glycidyl vinyl ether. These can use 1 type (s) or 2 or more types. Among these, ethylene, propylene, and vinyl acetate are preferable, and ethylene is more preferable.

Among the fluorine-containing polymers (D), from the viewpoint of heat resistance, chemical resistance, and chemical liquid permeation prevention, at least a copolymer (D1) composed of vinylidene fluoride units (VDF units), at least tetrafluoro Copolymer (D2) comprising ethylene units (TFE units) and ethylene units (E units), at least tetrafluoroethylene units (TFE units) and hexafluoropropylene units (HFP units) and / or the above general formula CF ₂ = A copolymer (P3) composed of PAVE units derived from PAVE represented by CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). ), At least a copolymer (D4) comprising chlorotrifluoroethylene units (CTFE units), at least It is preferably a chlorotrifluoroethylene unit (CTFE units) and consisting of tetrafluoroethylene units (TFE units) copolymer (D5).

As a copolymer (D1) (hereinafter sometimes referred to as a VDF copolymer (D1)) comprising at least a vinylidene fluoride unit (VDF unit), for example,
Vinylidene fluoride homopolymer (polyvinylidene fluoride (PVDF)) (D1-1),
A copolymer comprising VDF units and TFE units, wherein the content of VDF units is 30 mol% or more and 99 mol% or less with respect to the whole monomer excluding the functional group-containing monomers described later, and TFE units A copolymer (D1-2) having a content of 1 mol% or more and 70 mol% or less,
A copolymer comprising a VDF unit, a TFE unit, and a trichlorofluoroethylene unit, wherein the content of the VDF unit is 10 mol% or more and 90 mol with respect to the whole monomer excluding the functional group-containing monomer described later. % Or less, a copolymer having a TFE unit content of 0 mol% or more and 90 mol% or less, and a trichlorofluoroethylene unit content of 0 mol% or more and 30 mol% or less (D1-3),
A copolymer comprising a VDF unit, a TFE unit, and an HFP unit, wherein the content of the VDF unit is 10 mol% or more and 90 mol% or less with respect to the whole monomer excluding the functional group-containing monomer described later. And a copolymer (D1-4) in which the content of TFE units is 0 mol% or more and 90 mol% or less, and the content of HFP units is 0 mol% or more and 30 mol% or less.

  In the copolymer (D1-4), the content of the VDF unit is 15 mol% or more and 84 mol% or less, and the content of the TFE unit is based on the whole monomer excluding the functional group-containing monomer described later. It is preferable that 15 mol% or more and 84 mol% or less and the content of the HFP unit is 0 mol% or more and 30 mol% or less.

  As a copolymer (D2) comprising at least a tetrafluoroethylene unit (TFE unit) and an ethylene unit (E unit) (hereinafter sometimes referred to as a TFE copolymer (D2)), for example, a functional group described later Examples include a polymer having a TFE unit content of 20 mol% or more based on the entire monomer excluding the group-containing monomer, and further, the entire monomer excluding the functional group-containing monomer described later. On the other hand, the content of TFE units is 20 mol% or more and 80 mol% or less, the content of E units is 20 mol% or more and 80 mol% or less, and the content of units derived from monomers copolymerizable therewith Examples thereof include a copolymer having an amount of 0 mol% to 60 mol%.

Examples of the copolymerizable monomer include hexafluoropropylene (HFP), and the above general formula CF ₂ = CFOR ^f1 (wherein R ^f1 may contain an etheric oxygen atom having 1 to 10 carbon atoms). Represents a fluoroalkyl group), the above general formula CH ₂ = CX ¹ (CF ₂ ) _n X ² (where X ¹ and X ² independently represent a hydrogen atom or a fluorine atom, and n is 2 or more and 10 or less). And the like.) And the like. These can use 1 type (s) or 2 or more types.

As the TFE copolymer (D2), for example,
TFE unit and E unit, and the above general formula CH ₂ = CX ¹ (CF ₂ ) _n X ² (where X ¹ and X ² independently represent a hydrogen atom or a fluorine atom, and n is 2 or more and 10 or less) It is a copolymer composed of fluoroolefin units derived from the fluoroolefin represented by the formula (1), and the content of TFE units is based on the whole monomer excluding the functional group-containing monomers described later. 30 mol% or more and 70 mol% or less, the content of E unit is 20 mol% or more and 55 mol% or less, and the above general formula CH ₂ = CX ³ (CF ₂ ) _n X ⁴ (where X ³ and X ⁴ are Each independently represents a hydrogen atom or a fluorine atom, and n is an integer of 2 or more and 10 or less.) The content of the fluoroolefin unit derived from the fluoroolefin represented by Polymer ( 2-1),
A copolymer composed of TFE units, E units, HFP units, and units derived from monomers copolymerizable therewith, with respect to the entire monomer excluding the functional group-containing monomers described below, TFE unit content of 30 mol% to 70 mol%, E unit content of 20 mol% to 55 mol%, HFP unit content of 1 mol% to 30 mol%, and copolymerization with these A copolymer (D2-2) in which the content of units derived from possible monomers is 0 mol% or more and 10 mol% or less,
TFE units and E units, and the general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). A copolymer comprising PAVE units derived from PAVE, wherein the content of TFE units is 30 mol% or more and 70 mol% or less, based on the whole monomer excluding the functional group-containing monomers described later, E units In the general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). The copolymer (D2-3) etc. whose content of the PAVE unit derived from PAVE represented by this is 0 mol% or more and 10 mol% or less are mentioned.

At least a tetrafluoroethylene unit (TFE unit) and a hexafluoropropylene unit (HFP unit) and / or the above general formula CF ₂ = CFOR ^f1 (where R ^f1 represents an etheric oxygen atom having 1 to 10 carbon atoms) As a copolymer (D3) (hereinafter sometimes referred to as a TFE copolymer (D3)) composed of PAVE units derived from PAVE represented by PAVE represented by: ,
It is a copolymer composed of TFE units and HFP units, and the content of TFE units is preferably 70 mol% or more and 95 mol% or less with respect to the whole monomer excluding the functional group-containing monomer described later, Is a copolymer (D3-1) having a content of HFP units of 5 mol% to 30 mol%, preferably 7 mol% to 15 mol%,
It is derived from PAVE represented by a TFE unit and the general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). It is a copolymer comprising one or more PAVE units, and the content of TFE units is 70 mol% or more and 95 mol% or less with respect to the whole monomer excluding the functional group-containing monomer described later. And 1 derived from PAVE represented by the general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). A copolymer (D3-2) in which the content of the seed or two or more kinds of PAVE units is 5 mol% or more and 30 mol% or less,
TFE units and HFP units, and the above general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). A copolymer consisting of one or more PAVE units derived from PAVE, wherein the content of TFE units is 70 mol% or more with respect to the whole monomer excluding the functional group-containing monomers described later 95 mol% or less, represented by HFP units and the above general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). And a copolymer (D3-3) in which the total content of one or more PAVE units derived from PAVE is 5 mol% or more and 30 mol% or less.

The copolymer consisting of at least chlorotrifluoroethylene units (CTFE units) has CTFE units [—CFCl—CF ₂ —] and is composed of ethylene units (E units) and / or fluorine-containing monomer units. Chlorotrifluoroethylene copolymer (D4) (hereinafter sometimes referred to as CTFE copolymer (D4)).
Examples of the fluorine-containing monomer in the CTFE copolymer (D4), is not particularly limited as long as it is other than CTFE, vinylidene fluoride (VDF), hexafluoropropylene (HFP), the general formula _CF 2 = CFOR ^{P1 represented by f1} (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms), the above general formula CH ₂ = CX ¹ (CF ₂ ) and fluoroolefins represented by _n X ² (wherein X ¹ and X ² each independently represent a hydrogen atom or a fluorine atom, and n is an integer of 2 or more and 10 or less). These can use 1 type (s) or 2 or more types.

  The CTFE copolymer (D4) is not particularly limited, and examples thereof include a CTFE / PAVE copolymer, a CTFE / VDF copolymer, a CTFE / HFP copolymer, a CTFE / E copolymer, and a CTFE / PAVE / E copolymer. Examples thereof include a polymer, a CTFE / VDF / E copolymer, and a CTFE / HFP / E copolymer.

  The content of CTFE units in the CTFE copolymer (D4) is preferably 15 mol% or more and 70 mol% or less with respect to the whole monomer excluding the functional group-containing monomer described later, and is 18 mol%. More preferably, it is 65 mol% or less. On the other hand, the content of the E unit and / or the fluorine-containing monomer unit is preferably 30 mol% or more and 85 mol% or less, and more preferably 35 mol% or more and 82 mol% or less.

The copolymer (D5) consisting of at least a chlorotrifluoroethylene unit (CTFE unit) and a tetrafluoroethylene unit (TFE unit) has a CTFE unit [—CFCl—CF ₂ —] and a TFE unit [—CF ₂ —CF _2. -], And a chlorotrifluoroethylene copolymer composed of monomer units copolymerizable with CTFE and TFE (hereinafter, sometimes referred to as CTFE / TFE copolymer (D5)).

The copolymerizable monomer in the CTFE / TFE copolymer (D5) is not particularly limited as long as it is other than CTFE and TFE, but vinylidene fluoride (VDF), hexafluoropropylene (HFP), the above PAVE represented by the general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms), the general formula CH ₂ = Such as a fluoroolefin represented by CX ¹ (CF ₂ ) _n X ² (wherein X ¹ and X ² independently represent a hydrogen atom or a fluorine atom, and n is an integer of 2 or more and 10 or less). Fluorinated monomers, ethylene, propylene, isobutene and other olefins having 2 to 4 carbon atoms, vinyl acetate, methyl (meth) acrylate, (meth Vinyl esters such as ethyl acrylate, methyl vinyl ether (MVE), ethyl vinyl ether (EVE), non-fluorine-containing monomers of vinyl ether and butyl vinyl ether (BVE), and the like. These can use 1 type (s) or 2 or more types. Among these, PAVE is represented by the above general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). Of these, perfluoro (methyl vinyl ether) (PMVE) and perfluoro (propyl vinyl ether) (PPVE) are more preferable, and PPVE is more preferable from the viewpoint of heat resistance.

  The CTFE / TFE copolymer (D5) is not particularly limited, and examples thereof include a CTFE / TFE copolymer, a CTFE / TFE / HFP copolymer, a CTFE / TFE / VDF copolymer, and a CTFE / TFE / PAVE copolymer. For example, CTFE / TFE / PFE copolymer, CTFE / TFE / HFP / PAVE copolymer, and CTFE / TFE / VDF / PAVE copolymer. Among these, CTFE / TFE / PAVE copolymer, A CTFE / TFE / HFP / PAVE copolymer is preferred.

  The total content of CTFE units and TFE units in the CTFE / TFE copolymer (D5) is from the viewpoint of ensuring good moldability, environmental stress crack resistance, chemical permeation prevention, heat resistance, and mechanical properties. It is preferably 90 mol% or more and 99.9 mol% or less with respect to the whole monomer excluding the functional group-containing monomer described later, and the content of the monomer unit copolymerizable with the CTFE and TFE. Is preferably 0.1 mol% or more and 10 mol% or less.

  The content of the CTFE unit in the CTFE / TFE copolymer (D5) is the total amount of the CTFE unit and the TFE unit from the viewpoint of ensuring good moldability, environmental stress crack resistance, and chemical penetration prevention. It is preferably 15 mol% or more and 80 mol% or less, more preferably 17 mol% or more and 70 mol% or less, and further preferably 19 mol% or more and 65 mol% or less with respect to 100 mol%. .

  In the CTFE / TFE copolymer (D5), when the monomer copolymerizable with CTFE and TFE is PAVE, the content of the PAVE unit is the entire monomer excluding the functional group-containing monomer described later. However, it is preferably 0.5 mol% or more and 7.0 mol% or less, and more preferably 1.0 mol% or more and 5.0 mol% or less.

  In the CTFE / TFE copolymer (D5), when the monomers copolymerizable with CTFE and TFE are HFP and PAVE, the total content of the HFP unit and the PAVE unit is the functional group-containing monomer described later. It is preferably 0.5 mol% or more and 7.0 mol% or less, and more preferably 1.0 mol% or more and 5.0 mol% or less with respect to the whole monomer excluding.

The TFE copolymer (D3), the CTFE copolymer (D4), and the CTFE / TFE copolymer (D5) are excellent in chemical solution permeation prevention properties, particularly barrier properties against alcohol-containing gasoline. For the alcohol-containing gasoline permeability coefficient, put the sheet obtained from the resin to be measured into a permeability coefficient measuring cup filled with isooctane / toluene / ethanol mixed solvent in which isooctane, toluene, and ethanol are mixed at a volume ratio of 45:45:10. , A value calculated from a change in mass measured at 60 ° C. The alcohol-containing gasoline permeability coefficient of the TFE copolymer (D3), CTFE copolymer (D4), and CTFE / TFE copolymer (D5) is 1.5 g · mm / (m ² · day) or less. It is preferably 0.01 g · mm / (m ² · day) or more and 1.0 g · mm / (m ² · day) or less, more preferably 0.02 g · mm / (m ² · day). More preferably, it is 0.8 g · mm / (m ² · day) or less.

  The fluorine-containing polymer (D) used in the present invention can be obtained by (co) polymerizing monomers constituting the polymer by a conventional polymerization method. Among them, a method by radical polymerization is mainly used. That is, the means for starting the polymerization is not limited as long as it proceeds radically, but for example, it is initiated by organic or inorganic radical polymerization initiator, heat, light, ionizing radiation or the like.

There is no restriction | limiting in particular in the manufacturing method of a fluorine-containing polymer (D), The polymerization method using the radical polymerization initiator generally used is used. Polymerization methods include bulk polymerization, solution polymerization using organic solvents such as fluorinated hydrocarbons, chlorinated hydrocarbons, fluorinated chlorohydrocarbons, alcohols, hydrocarbons, aqueous media, and appropriate organic solvents as required. Known methods such as suspension polymerization, emulsion polymerization using an aqueous medium and an emulsifier can be employed.
Moreover, superposition | polymerization can be implemented as a batch type or a continuous operation using a 1 tank thru | or multi tank type stirring type polymerization apparatus and a pipe | tube type polymerization apparatus.

As a radical polymerization initiator, the decomposition temperature with a half-life of 10 hours is preferably 0 ° C. or higher and 100 ° C. or lower, and more preferably 20 ° C. or higher and 90 ° C. or lower. Specific examples include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2,4-dimethylvaleronitrile), 2,2′-azobis (2-methylvaleronitrile), 2,2 '-Azobis (2-cyclopropylpropionitrile), 2,2'-azobisisobutyric acid dimethyl, 2,2'-azobis [2- (hydroxymethyl) propionitrile], 4,4'-azobis (4-cyano Pentoxides), hydroperoxides such as hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide, dialkyl peroxides such as di-t-butyl peroxide, dicumyl peroxide, acetyl peroxide , Isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide, lauroyl peroxide Non-fluorine type diacyl peroxide such as oxide, ketone peroxide such as methyl ethyl ketone peroxide, cyclohexanone peroxide, peroxydicarbonate such as diisopropylperoxydicarbonate, t-butylperoxypivalate, t-butylperoxyisobuty Rate, peroxyester such as t-butyl peroxyacetate, (Z (CF ₂ ) _p COO) ₂ (where Z is a hydrogen atom, a fluorine atom or a chlorine atom, and p is an integer of 1-10) And inorganic peroxides such as potassium persulfate, potassium persulfate, sodium persulfate, and ammonium persulfate. These can use 1 type (s) or 2 or more types.

  In the production of the fluorine-containing polymer (D), it is also preferable to use an ordinary chain transfer agent for adjusting the molecular weight. Examples of chain transfer agents include alcohols such as methanol and ethanol, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1,1-dichloro-1-fluoroethane, and 1,2-dichloro- Chlorofluorohydrocarbons such as 1,1,2,2-tetrafluoroethane, 1,1-dichloro-1-fluoroethane, 1,1,2-trichloro-1,2,2-trifluoroethane, pentane, hexane , Hydrocarbons such as cyclohexane, and chlorohydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, and methyl chloride. These can use 1 type (s) or 2 or more types.

  The polymerization conditions are not particularly limited, and the polymerization temperature is preferably 0 ° C. or higher and 100 ° C. or lower, and more preferably 20 ° C. or higher and 90 ° C. or lower. In order to avoid a decrease in heat resistance due to ethylene-ethylene chain formation in the polymer, a low temperature is generally preferred. The polymerization pressure is appropriately determined according to other polymerization conditions such as the type, amount, vapor pressure, polymerization temperature and the like of the solvent used, but is preferably 0.1 MPa or more and 10 MPa or less, and is 0.5 MPa or more and 3 MPa or less. It is more preferable. The polymerization time is preferably 1 hour or more and 30 hours or less.

  The molecular weight of the fluorine-containing polymer (D) is not particularly limited, but is preferably a polymer that is a solid at room temperature and can itself be used as a thermoplastic resin, an elastomer, or the like. The molecular weight is controlled by the concentration of the monomer used for the polymerization, the concentration of the polymerization initiator, the concentration of the chain transfer agent, and the temperature.

  When the fluoropolymer (D) is coextruded with the aliphatic polyamide (A), polyamide 6/66/12 composition (B), EVOH (C)), etc., kneading without significant deterioration of these In order to ensure sufficient melt fluidity in the temperature and molding temperature range, the melt flow rate at a temperature 50 ° C. higher than the melting point of the fluorine-containing polymer (D) and a load of 5 kg is 0.5 g / 10 min. It is preferably 200 g / 10 min or less, more preferably 1 g / 10 min or more and 100 g / 10 min or less.

Further, in the fluorinated polymer (D), the melting point and glass transition point of the polymer can be adjusted by selecting the type and composition ratio of the fluorinated monomer and other monomers.
The melting point of the fluorine-containing polymer (D) is appropriately selected depending on the purpose, application, and method of use. The aliphatic polyamide (A), the polyamide 6/66/12 composition (B), EVOH (C), etc. When it is coextruded with the resin, it is preferably close to the molding temperature of the resin. Therefore, it is preferable to optimize the melting point of the fluorine-containing polymer (D) by appropriately adjusting the ratio of the fluorine-containing monomer and other monomers to the functional group-containing monomer described later. In particular, from the viewpoint of sufficiently ensuring the heat melting stability during continuous extrusion with EVOH (C), continuous moldability, heat resistance of the fluorine-containing polymer (D), chemical resistance, and chemical penetration prevention, The melting point of the fluorine-containing polymer is preferably 150 ° C. or higher and 280 ° C. or lower.
Here, the melting point means that the sample is heated to a temperature higher than the expected melting point using a differential scanning calorimeter, and then the sample is cooled at a rate of 10 ° C. per minute and cooled to 30 ° C. The melting point is defined as the temperature of the peak value of the melting curve measured by leaving the sample as it is for about 1 minute and then increasing the temperature at a rate of 10 ° C. per minute.

  The fluorine-containing polymer (D) used in the present invention has a functional group having reactivity with an amino group in the molecular structure, and the functional group is the same as that of the fluorine-containing polymer (D). It may be contained at either the molecular end, the side chain or the main chain. The functional group may be used alone or in combination of two or more in the fluorine-containing polymer (D). The type and content of the functional group are appropriately determined depending on the type, shape, application, required interlayer adhesion, adhesion method, functional group introduction method, etc. of the other material laminated on the fluorine-containing polymer (D). The

  The functional group having reactivity with the amino group is selected from the group consisting of a carboxyl group, an acid anhydride group or carboxylate, a sulfo or sulfonate, an epoxy group, a cyano group, a carbonate group, and a haloformyl group. There is at least one kind. In particular, at least one selected from the group consisting of a carboxyl group, an acid anhydride group or carboxylate, an epoxy group, a carbonate group, and a haloformyl group is preferable.

  As a method for introducing a functional group having reactivity into the fluorine-containing polymer (D), (i) when the fluorine-containing polymer (D) is polymerized, a copolymerizable monomer having a functional group is copolymerized. A method of polymerization, (ii) a method of introducing a functional group to the molecular terminal of the fluorine-containing polymer (D) during polymerization by a polymerization initiator, a chain transfer agent, etc., and (iii) grafting of a functional group having reactivity. And a method of grafting a compound (graft compound) having a functional group capable of forming on a fluorine-containing polymer. These introduction methods can be used alone or in appropriate combination. In view of interlayer adhesion in the laminated tube, the fluorine-containing polymer (D) produced from the above (i) and (ii) is preferable. Regarding (iii), JP-A-7-18035, JP-A-7-259592, JP-A-7-25594, JP-A-7-173230, JP-A-7-173446, JP-A-7- See the production method according to JP-A-173447 and JP-T-10-503236. Hereinafter, (i) a method of copolymerizing a copolymerizable monomer having a functional group at the time of polymerization of the fluorinated polymer, (ii) a functional group at the molecular end of the fluorinated polymer by a polymerization initiator or the like. A method of introducing the will be described.

  (I) In the method of copolymerizing a copolymerizable monomer having a functional group (hereinafter sometimes abbreviated as a functional group-containing monomer) during the production of the fluorine-containing polymer (D), Polymerized monomer containing at least one functional group-containing monomer selected from the group consisting of carboxyl group, acid anhydride group or carboxylate, hydroxyl group, sulfo group or sulfonate, epoxy group, and cyano group And use. Examples of the functional group-containing monomer include a functional group-containing non-fluorine monomer and a functional group-containing fluorine-containing monomer.

  Functional group-containing non-fluorine monomers include acrylic acid, halogenated acrylic acid (excluding fluorine), methacrylic acid, halogenated methacrylic acid (excluding fluorine), maleic acid, halogenated maleic acid (excluding ), Fumaric acid, halogenated fumaric acid (excluding fluorine), itaconic acid, citraconic acid, crotonic acid, endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid Unsaturated carboxylic acids such as acids and derivatives thereof, maleic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid Carboxyl group-containing monomers such as anhydrides, epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, glycidyl ether, etc. And the like. These can use 1 type (s) or 2 or more types. The functional group-containing non-fluorine monomer is determined in consideration of copolymerization reactivity with the fluorine-containing monomer to be used. By selecting an appropriate functional group-containing non-fluorine monomer, the polymerization proceeds well, and it can be easily introduced into the main chain of the functional group-containing non-fluorine monomer, resulting in less unreacted monomer. There is an advantage that impurities can be reduced.

The functional group-containing fluorine monomers, the general formula ^{CX 3 = CX 4 -. (} R 7) n -Y ( where, Y is -COOM (M is, represents a hydrogen atom or an alkali metal), carboxyl Represents a functional group selected from the group consisting of a group-derived group, —SO ₃ M (M represents a hydrogen atom or an alkali metal), a sulfonic acid-derived group, an epoxy group, and —CN, and X ³ and X ⁴ They are the same or different and each represents a hydrogen atom or a fluorine atom (provided that when ^{X 3} and ^{X 4} are identical to the hydrogen atom, a n = 1,. including a fluorine atom in ^{R 7), R 7} is An alkylene group having 1 to 40 carbon atoms, a fluorinated oxyalkylene group having 1 to 40 carbon atoms, a fluorinated alkylene group having 1 to 40 carbon atoms having an ether bond, or a carbon atom having an ether bond Number 1 or more And 40 or less fluorine-containing oxyalkylene groups, and n is 0 or 1.).
Examples of the group derived from a carboxyl group as Y in the above general formula include, for example, a general formula —C (═O) Q ¹ (wherein Q ¹ represents —OR ⁸ , —NH ₂ , F, Cl, Br, or I). R ⁸ represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 22 carbon atoms.) And the like.
Examples of the sulfonic acid-derived group that is Y in the above general formula include a general formula —SO ₂ Q ² (wherein Q ² represents —OR ⁹ , —NH ₂ , F, Cl, Br, or I, and R ⁹ Represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 22 carbon atoms).
Y is preferably —COOH, —SO ₃ H, —SO ₃ Na, —SO ₂ F, or —CN.

  Examples of the functional group-containing fluorine-containing monomer include perfluoroacrylic acid fluoride, 1-fluoroacrylic acid fluoride, acrylic acid fluoride, 1-trifluoromethacrylic acid fluoride, and perfluoro when the functional group has a carbonyl group. Examples include butenoic acid. These can use 1 type (s) or 2 or more types.

The content of the functional group-containing monomer in the fluorine-containing polymer (D) ensures sufficient interlayer adhesion, and ensures sufficient heat resistance without causing a decrease in interlayer adhesion depending on the use environment conditions. From the viewpoint of preventing occurrence of poor adhesion, coloring, foaming, use at high temperatures, peeling, coloring, foaming, elution, etc. due to decomposition during processing at high temperatures, % To 20 mol%, more preferably 0.05 mol% to 10 mol%, and still more preferably 0.1 mol% to 5 mol%. When the content of the functional group-containing monomer is in the above range, the polymerization rate during production does not decrease, and the fluorine-containing polymer (D) has excellent adhesion to the laminated counterpart material. Become. The addition method of the functional group-containing monomer is not particularly limited, and may be added all at once at the start of polymerization or continuously during the polymerization. The addition method is appropriately selected depending on the decomposition reactivity of the polymerization initiator and the polymerization temperature. During the polymerization, the amount consumed is continuously or intermittently as the functional group-containing monomer is consumed in the polymerization. It is preferable to supply in the polymerization tank and maintain the concentration of the functional group-containing monomer in this range.
Moreover, as long as the said content is satisfy | filled, you may be a mixture of the fluorine-containing polymer into which the functional group was introduce | transduced, and the fluorine-containing polymer into which the functional group was not introduce | transduced.

  (Ii) In a method in which a functional group is introduced into the molecular terminal of a fluorine-containing polymer with a polymerization initiator or the like, the functional group is introduced into one or both ends of the molecular chain of the fluorine-containing polymer. The functional group introduced at the terminal is preferably a carbonate group or a haloformyl group.

The carbonate group introduced as a terminal group of the fluorine-containing polymer (D) is generally a group having a —OC (═O) O— bond, and specifically, —OC (═O) O—R. ¹⁰ groups [R ¹⁰ is a hydrogen atom, an organic group (for example, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms having an ether bond, etc.), or an I, II, or VII group element. . ] Those _{structures, -OC (= O) OCH 3} , -OC (= O) OC 3 H 7, -OC (= O) OC 8 H 17, -OC (= O) OCH 2 CH 2 OCH 2 CH ₃ etc. may be mentioned. The haloformyl group is specifically —COZ [Z is a halogen element. ] And -COF, -COCl, etc. are mentioned. These can use 1 type (s) or 2 or more types.

  In order to introduce a carbonate group at the molecular terminal of the polymer, various methods using a polymerization initiator or a chain transfer agent can be employed. However, peroxides, particularly peroxycarbonates and peroxyesters, can be used as polymerization initiators. Can be preferably employed from the viewpoint of performance such as economy, heat resistance and chemical resistance. According to this method, a carbonyl group derived from peroxide, for example, a carbonate group derived from peroxycarbonate, an ester group derived from peroxyester, or a polymer such as a haloformyl group obtained by converting these functional groups It can be introduced at the end. Among these polymerization initiators, it is more preferable to use peroxycarbonate because the polymerization temperature can be lowered and no side reaction is involved in the initiation reaction.

  Various methods can be used to introduce a haloformyl group at the molecular end of the polymer. For example, the carbonate group of the above-mentioned fluorine-containing polymer having a carbonate group at the end is heated to cause thermal decomposition (decarboxylation). Can be obtained.

  As peroxycarbonate, diisopropyl peroxycarbonate, di-n-propyl peroxycarbonate, t-butyl peroxyisopropyl carbonate, t-butyl peroxymethacryloyloxyethyl carbonate, bis (4-t-butylcyclohexyl) peroxy Examples include dicarbonate and di-2-ethylhexyl peroxydicarbonate. These can use 1 type (s) or 2 or more types.

  The amount of peroxycarbonate used varies depending on the type of polymer (composition, etc.), the molecular weight, the polymerization conditions, and the type of initiator used, but the polymerization rate is properly controlled to ensure a sufficient polymerization rate. From a viewpoint, it is preferable that it is 0.05 to 20 mass parts with respect to 100 mass parts of all the polymers obtained by superposition | polymerization, and it is more preferable that it is 0.1 to 10 mass parts. The carbonate group content at the molecular end of the polymer can be controlled by adjusting the polymerization conditions. The method for adding the polymerization initiator is not particularly limited, and may be added all at once at the start of polymerization or may be continuously added during the polymerization. The addition method is appropriately selected depending on the decomposition reactivity of the polymerization initiator and the polymerization temperature.

Terminal functional groups is for several 10 ⁶ main chain carbon atoms in the fluorine-containing polymer (D), ensuring sufficient interlayer adhesion, the operating environment, without causing a reduction in the interlaminar adhesion, the heat resistance 150 or more and 3,000 or less from the standpoint of ensuring sufficient, high-temperature processing, adhesion failure, coloring, foaming, use at high temperatures, and preventing occurrence of peeling, coloring, foaming, elution, etc. due to decomposition Preferably, the number is 200 or more and 2,000 or less, and more preferably 300 or more and 1,000 or less. Further, as long as the number of functional groups is satisfied, it may be a mixture of a fluorine-containing polymer into which a functional group has been introduced and a fluorine-containing polymer into which no functional group has been introduced.

As described above, the fluorine-containing polymer (D) used in the present invention is a fluorine-containing polymer into which a functional group having reactivity with an amino group is introduced. As described above, the fluorine-containing polymer (D) into which the functional group is introduced is itself a heat resistance, water resistance, low friction, chemical resistance, weather resistance, antifouling property peculiar to the fluorine-containing polymer. It is possible to maintain excellent characteristics such as chemical solution permeation prevention, which is advantageous in terms of productivity and cost.
Furthermore, the functional group having reactivity with amino groups is contained in the molecular chain, so that various materials that have insufficient or impossible interlayer adhesion in laminated tubes can be specially treated with surface treatment. It is possible to impart excellent interlayer adhesion with other substrates directly without performing any treatment or coating with an adhesive resin.

  The fluorine-containing polymer (D) used in the present invention is variously filled with inorganic powder, glass fiber, carbon fiber, metal oxide, carbon, etc. within a range that does not impair the performance depending on the purpose and application. An agent can be added. In addition to the filler, a pigment, an ultraviolet absorber, and other optional additives can be mixed. In addition to additives, resins such as other fluororesins and thermoplastic resins, synthetic rubber, etc. can also be added, improving mechanical properties, improving weather resistance, imparting design properties, preventing static electricity, improving moldability Etc. are possible.

[Laminated tube]
The laminated tube according to the present invention includes an (a) layer containing an aliphatic polyamide (A), a (b) layer containing a polyamide 6/66/12 composition (B), a (c) layer containing EVOH (C), And at least four layers including the (d) layer containing the fluorine-containing polymer (D).

  In the laminated tube of the present invention, it is essential to include the (c) layer containing EVOH (C), and the chemical penetration prevention property, particularly hydrocarbon penetration prevention property of the laminated tube becomes good. Moreover, it is essential to include the (d) layer containing the fluorine-containing polymer (D), and the alcohol permeation preventive property of the laminated tube becomes good.

  In a preferred embodiment, the (a) layer containing the aliphatic polyamide (A) is disposed in the outermost layer of the laminated tube. By arranging the (a) layer containing the aliphatic polyamide (A) in the outermost layer, it becomes possible to obtain a laminated tube excellent in chemical resistance and flexibility. The (c) layer containing EVOH (C) is disposed between the (a) layer containing the aliphatic polyamide (A) and the (d) layer containing the fluorine-containing polymer (D). By arranging the (d) layer containing the fluorine-containing polymer (D) in the innermost layer, a laminated tube having excellent resistance to deterioration fuel can be obtained, and a low molecular weight such as a monomer or oligomer by contact with alcohol-containing gasoline. It becomes possible to suppress elution of components.

  In a more preferred embodiment, the (b) layer containing the polyamide 6/66/12 composition (B) is between the (a) layer containing the aliphatic polyamide (A) and the (c) layer containing EVOH (C). Placed in. The (b) layer containing the polyamide 6/66/12 composition (B) is disposed between the (a) layer containing the aliphatic polyamide (A) and the (c) layer containing EVOH (C). It is possible to obtain a laminated tube having excellent interlayer adhesion and durability.

  Further, in the laminated tube of the present invention, when the conductive layer containing the fluorine-containing polymer composition containing the conductive filler is disposed in the innermost layer of the laminated tube, the chemical liquid permeation preventing property, the deterioration fuel resistance, In addition to excellent elution resistance of monomers and oligomers, when used as a fuel piping tube, prevent sparks generated by internal friction of fuel circulating in the piping or friction with the tube wall from igniting the fuel. Is possible. In that case, it is possible to achieve both low temperature impact resistance and conductivity by arranging a layer containing a fluorine-containing polymer having no conductivity outside the conductive layer, and It is also economically advantageous. Furthermore, the fluorine-containing polymer referred to herein includes the fluorine-containing polymer (D) having a functional group in the molecular chain as defined in the present invention, and has no functional group described later. Also refers to polymer.

Conductivity means that, for example, when a flammable fluid such as gasoline is continuously in contact with an insulator such as resin, static electricity may accumulate and ignite, but this static electricity will not accumulate. Says having electrical properties. This makes it possible to prevent an explosion due to static electricity generated when a fluid such as fuel is conveyed.
The conductive filler includes all fillers added to impart conductive performance to the resin, and examples thereof include granular, flaky, and fibrous fillers.

  Examples of the particulate filler include carbon black and graphite. Examples of the flaky filler include aluminum flakes, nickel flakes and nickel-coated mica. Examples of the fibrous filler include carbon fibers, carbon-coated ceramic fibers, carbon whiskers, carbon nanotubes, aluminum fibers, copper fibers, brass fibers, and stainless steel fibers. These can use 1 type (s) or 2 or more types. Among these, carbon nanotubes and carbon black are preferable.

  Carbon nanotubes are what are called hollow carbon fibrils, which have an outer region consisting of an essentially continuous multi-layer of regularly arranged carbon atoms, and an inner hollow region, each layer And the hollow region are essentially cylindrical fibrils arranged substantially concentrically around the cylindrical axis of the fibrils. Further, the regularly arranged carbon atoms in the outer region are preferably graphite-like, and the diameter of the hollow region is preferably 2 nm or more and 20 nm or less. The outer diameter of the carbon nanotube is preferably 3.5 nm or more and 70 nm or less, preferably 4 nm or more and 60 nm or less, from the viewpoint of imparting sufficient dispersibility in the resin and good conductivity of the obtained resin molding. More preferably. The aspect ratio (referring to the ratio of length / outer diameter) of the carbon nanotube is preferably 5 or more, more preferably 100 or more, and further preferably 500 or more. By satisfying the aspect ratio, it is easy to form a conductive network, and excellent conductivity can be exhibited by addition of a small amount.

  Carbon black includes all carbon blacks that are commonly used to impart conductivity. Preferred carbon blacks include acetylene black obtained by incomplete combustion of acetylene gas, and furnace-type incompleteness using crude oil as a raw material. Examples include, but are not limited to, furnace black such as ketjen black produced by combustion, oil black, naphthalene black, thermal black, lamp black, channel black, roll black, and disk black. Among these, acetylene black and furnace black are more preferable.

Carbon black is produced in various carbon powders having different characteristics such as particle diameter, surface area, DBP oil absorption, ash content and the like. Although there is no restriction | limiting in the characteristic of this carbon black, What has a favorable chain structure and a large aggregation density is preferable. A large amount of carbon black is not preferable from the viewpoint of impact resistance, and from the viewpoint of obtaining excellent electrical conductivity with a smaller amount, the average particle size is preferably 500 nm or less, more preferably 5 nm or more and 100 nm or less. More preferably, it is 10 nm or more and 70 nm or less, and the surface area (BET method) is preferably 10 m ² / g or more, more preferably 30 m ² / g or more, and 50 m ² / g or more. Further, the DBP (dibutyl phthalate) oil absorption is preferably 50 ml / 100 g or more, more preferably 100 ml / 100 g, and further preferably 150 ml / 100 g or more. Moreover, it is preferable that an ash content is 0.5 mass% or less, and it is more preferable that it is 0.3 mass% or less. The DBP oil absorption here is a value measured by a method defined in ASTM D-2414. The volatile content of carbon black is preferably less than 1.0% by mass. These conductive fillers may be surface-treated with a surface treatment agent such as titanate, aluminum, or silane. It is also possible to use a granulated product to improve melt kneading workability.

Since the content of the conductive filler varies depending on the type of the conductive filler used, it cannot be defined unconditionally, but from the viewpoint of balance with conductivity, fluidity, mechanical strength, etc., 100 parts by mass of the fluorinated polymer On the other hand, it is generally preferably 3 parts by mass or more and 30 parts by mass or less.
In addition, from the viewpoint of obtaining sufficient antistatic performance, the conductive filler preferably has a surface resistivity of the melt-extruded product of 10 ⁸ Ω / square or less, more preferably 10 ⁶ Ω / square or less. preferable. However, the addition of the conductive filler tends to cause deterioration of strength and fluidity. Therefore, it is desirable that the content of the conductive filler is as small as possible if the target conductivity level is obtained.

  In the laminated tube of the present invention, the thickness of each layer is not particularly limited, and can be adjusted according to the type of polymer constituting each layer, the total number of layers in the laminated tube, the use, etc. It is determined in consideration of the chemical permeation preventive properties, low temperature impact resistance, flexibility and the like of the laminated tube. In general, the thicknesses of the (a) layer, (b) layer, (c) layer, and (d) layer are each preferably 3% or more and 90% or less with respect to the thickness of the entire laminated tube. Considering the balance between low temperature impact resistance and chemical solution permeation prevention, the thicknesses of the (c) layer and (d) layer should be 5% or more and 50% or less, respectively, with respect to the total thickness of the laminated tube. Preferably, it is 7% or more and 30% or less.

  The total number of layers in the laminated tube of the present invention is (a) layer containing aliphatic polyamide (A), (b) layer containing polyamide 6/66/12 composition (B), and EVOH (C). The layer is not particularly limited as long as it is at least 4 layers including the (c) layer and the (d) layer including the fluorine-containing polymer (D). Furthermore, the laminated tube according to the present invention provides a laminated tube which is provided with further functions or is economically advantageous in addition to the four layers (a), (b), (c) and (d). Therefore, you may have one layer or two or more layers containing another thermoplastic resin. The number of layers of the laminated tube of the present invention is 4 or more, but it is preferably 8 or less, more preferably 5 or more and 7 or less, judging from the mechanism of the tube production apparatus.

  Other thermoplastic resins include polymetaxylylene adipamide (polyamide MXD6), polymetaxylylene veramide (polyamide MXD8), polymetaxylylene azelamide other than the aliphatic polyamide (A) defined in the present invention. (Polyamide MXD9), polymetaxylylene sebacamide (polyamide MXD10), polymetaxylylene dodecamide (polyamide MXD12), polymetaxylylene terephthalamide (polyamide MXDT), polymetaxylylene isophthalamide (polyamide MXDI), polymetaxyl Silylene hexahydroterephthalamide (polyamide MXDT (H)), polymetaxylylene naphthalamide (polyamide MXDN), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylene veramide ( Lyamide PXD8), polyparaxylylene azeamide (polyamide PXD9), polyparaxylylene sebacamide (polyamide PXD10), polyparaxylylene decanamide (polyamide PXD12), polyparaxylylene terephthalamide (polyamide PXDT), Polyparaxylylene isophthalamide (polyamide PXDI), polyparaxylylene hexahydroterephthalamide (polyamide PXDT (H)), polyparaxylylene naphthalamide (polyamide PXDN), polyparaphenylene terephthalamide (PPTA), Polyparaphenylene isophthalamide (PPIA), polymetaphenylene terephthalamide (PMTA), polymetaphenylene isophthalamide (PMIA), poly (2,6-naphthalenediethylene adipamide) (polyamide 2) 6-BAN6), poly (2,6-naphthalene dimethylene suberamide) (polyamide 2,6-BAN8), poly (2,6-naphthalene dimethylene azelamide) (polyamide 2,6-BAN9), poly (2 , 6-Naphthalenedimethylene sebacamide) (Polyamide 2,6-BAN10), Poly (2,6-naphthalenedimethylene dodecamide) (Polyamide 2,6-BAN12), Poly (2,6-Naphthalenedylene methylene tele Phthalamide) (polyamide 2,6-BANT), poly (2,6-naphthalene dimethylene isophthalamide) (polyamide 2,6-BANI), poly (2,6-naphthalene dimethylene hexahydroterephthalamide) ( Polyamide 2,6-BANT (H)), poly (2,6-naphthalene dimethylene naphthalamide) (polyamide 2,6-B ANN), poly (1,3-cyclohexanedimethylene adipamide) (polyamide 1,3-BAC6), poly (1,3-cyclohexanedimethylene suberamide (polyamide 1,3-BAC8), poly (1,3 -Cyclohexane dimethylene azelamide) (polyamide 1,3-BAC9), poly (1,3-cyclohexane dimethylene sebacamide) (polyamide 1,3-BAC10), poly (1,3-cyclohexane dimethylene dodecamide) (Polyamide 1,3-BAC12), poly (1,3-cyclohexanedimethylene terephthalamide) (polyamide 1,3-BACT), poly (1,3-cyclohexanedimethylene isophthalamide) (polyamide 1,3- BACI), poly (1,3-cyclohexanedimethylene hexahydroterephthalamide) (poly Amide 1,3-BACT (H)), poly (1,3-cyclohexanedimethylenenaphthalamide) (polyamide 1,3-BACN), poly (1,4-cyclohexanedimethylene adipamide) (polyamide 1,4 -BAC6), poly (1,4-cyclohexanedimethylenesberamide) (polyamide 1,4-BAC8), poly (1,4-cyclohexanedimethyleneazeramide) (polyamide 1,4-BAC9), poly (1, 4-cyclohexanedimethylene sebacamide) (polyamide 1,4-BAD10), poly (1,4-cyclohexanedimethylene dodecamide) (polyamide 1,4-BAD12), poly (1,4-cyclohexanedimethylene terephthalate) Ramide) (polyamide 1,4-BACT), poly (1,4-cyclohexanedimethylene isophthalami) ) (Polyamide 1,4-BACI), poly (1,4-cyclohexanedimethylene hexahydroterephthalamide) (polyamide 1,4-BACT (H)), poly (1,4-cyclohexanedimethylene naphthalamide) ( Polyamide 1,4-BACN), poly (4,4′-methylenebiscyclohexylene adipamide) (polyamide PACM6), poly (4,4′-methylenebiscyclohexylene suberamide) (polyamide PACM8), poly (4 , 4′-methylenebiscyclohexylene azelamide) (polyamide PACM9), poly (4,4′-methylenebiscyclohexylene sebamide) (polyamide PACM10), poly (4,4′-methylenebiscyclohexylene dodecamide) (Polyamide PACM12), poly (4,4′-methylenebissi Chlorhexylenetetradecamide) (polyamide PACM14), poly (4,4′-methylenebiscyclohexylenehexadecamide) (polyamide PACM16), poly (4,4′-methylenebiscyclohexyleneoctadecamide) (polyamide PACM18) ), Poly (4,4′-methylenebiscyclohexylene terephthalamide) (polyamide PACMT), poly (4,4′-methylenebiscyclohexylene isophthalamide) (polyamide PACMI), poly (4,4′-methylene) Biscyclohexylenehexahydroterephthalamide) (polyamide PACMT (H)), poly (4,4′-methylenebiscyclohexylenenaphthalamide) (polyamide PACMN), poly (4,4′-methylenebis (2-methyl-cyclohexene) Silene) Adipamide Polyamide MACM6), poly (4,4′-methylenebis (2-methyl-cyclohexylene) suberamide) (polyamide MACM8), poly (4,4′-methylenebis (2-methyl-cyclohexylene) azeramide) (polyamide MACM9), Poly (4,4′-methylenebis (2-methyl-cyclohexylene) sebacamide) (polyamide MACM10), poly (4,4′-methylenebis (2-methyl-cyclohexylene) dodecamide) (polyamide MACM12), poly (4 4′-methylenebis (2-methyl-cyclohexylene) tetradecanamide) (polyamide MACM14), poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexadecamide) (polyamide MACM16), poly (4,4′-methylenebis) (2-me Ru-cyclohexylene) octadecamide) (polyamide MACM18), poly (4,4′-methylenebis (2-methyl-cyclohexylene) terephthalamide) (polyamide MACMT), poly (4,4′-methylenebis (2-methyl-cyclohexylene) ) Isophthalamide) (polyamide MACMI), poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexahydroterephthalamide) (polyamide MACMT (H)), poly (4,4′-methylenebis (2-methyl) -Cyclohexylene) naphthalamide) (polyamide MACMN), poly (4,4'-propylene biscyclohexylene adipamide) (polyamide PACP6), poly (4,4'-propylene biscyclohexylene suberamide) (polyamide PACP8), Poly (4 , 4′-propylene biscyclohexylene azelamide) (polyamide PACP9), poly (4,4′-propylene biscyclohexylene sebacamide) (polyamide PACP10), poly (4,4′-propylene biscyclohexylene dodecamide) (Polyamide PACP12), poly (4,4′-propylene biscyclohexylene tetradecanamide) (polyamide PACP14), poly (4,4′-propylene biscyclohexylene hexadecanamide) (polyamide PACP16), poly (4,4 '-Propylene biscyclohexylene octadecanamide) (polyamide PACP18), poly (4,4'-propylene biscyclohexylene terephthalamide) (polyamide PAPPT), poly (4,4'-propylene biscyclohexylene isophthalamide) (Polyamide PACPI), poly (4,4′-propylene biscyclohexylene hexahydroterephthalamide) (polyamide PACPT (H)), poly (4,4′-propylene biscyclohexylene naphthalamide) (polyamide PACPN), poly Isophorone adipamide (polyamide IPD6), polyisophorone beramide (polyamide IPD8), polyisophorone azeamide (polyamide IPD9), polyisophorone sebamide (polyamide IPD10), polyisophorondecamide (polyamide IPD12), polyisophorone terephthalate Ramide (polyamide IPDT), polyisophorone isophthalamide (polyamide IPDI), polyisophorone hexahydroterephthalamide (polyamide IPDT (H)), polyisophorone naphthalamide ( Reamide IPDN), polytetramethylene terephthalamide (polyamide 4T), polytetramethylene isophthalamide (polyamide 4I), polytetramethylene hexahydroterephthalamide (polyamide 4T (H)), polytetramethylene naphthalamide (polyamide 4N) ), Polypentamethylene terephthalamide (polyamide 5T), polypentamethylene isophthalamide (polyamide 5I), polypentamethylene hexahydroterephthalamide (polyamide 5T (H)), polypentamethylene naphthalamide (polyamide 5N), Polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene hexahydroterephthalamide (polyamide 6T (H)), polyhexamethylene naphtha Lamid (polyamide 6N), poly (2-methylpentamethylene terephthalamide) (polyamide M5T), poly (2-methylpentamethylene isophthalamide) (polyamide M5I), poly (2-methylpentamethylene hexahydroterephthalamide) ) (Polyamide M5T (H)), poly (2-methylpentamethylene naphthalamide (polyamide M5N), polynonamethylene terephthalamide (polyamide 9T), polynonamethylene isophthalamide (polyamide 9I), polynonamethylene hexahydro Terephthalamide (polyamide 9T (H)), polynonamethylene naphthalamide (polyamide 9N), poly (2-methyloctamethylene terephthalamide) (polyamide M8T), poly (2-methyloctamethylene isophthalamide) (polyamide) M8I), Po (2-methyloctamethylenehexahydroterephthalamide) (polyamide M8T (H)), poly (2-methyloctamethylenenaphthalamide) (polyamide M8N), polytrimethylhexamethylene terephthalamide (polyamide TMHT), polytrimethylhexa Methylene isophthalamide (polyamide TMHI), polytrimethylhexamethylene hexahydroterephthalamide (polyamide TMHT (H)), polytrimethylhexamethylene naphthalamide (polyamide TMHN), polydecamethylene terephthalamide (polyamide 10T), polydeca Methyleneisophthalamide (Polyamide 10I), Polydecamethylenehexahydroterephthalamide (Polyamide 10T (H)), Polydecamethylenenaphthalamide (Polyamide 10N), Polyundeca Tylene terephthalamide (polyamide 11T), polyundecamethylene isophthalamide (polyamide 11I), polyundecamethylene hexahydroterephthalamide (polyamide 11T (H)), polyundecamethylene naphthalamide (polyamide 11N), poly Dodecamethylene terephthalamide (polyamide 12T), polydodecamethylene isophthalamide (polyamide 12I), polydodecamethylene hexahydroterephthalamide (polyamide 12T (H)), polydodecamethylene naphthalamide (polyamide 12N) and these polyamides Examples thereof include polyamide resins such as copolymers using several kinds of raw material monomers and / or raw material monomers of the aliphatic polyamide (A).

  In addition, fluorine-containing polymers other than those specified in the present invention (here, other than those specified in the present invention refers to fluorine-containing polymers that do not contain a functional group having reactivity with amino groups). .) As polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (PFA) ), Tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoro (alkyl vinyl ether) / hexafluoropropylene copolymer, ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / tetrafluoro Ethylene / hex Fluoropropylene copolymer (EFEP), vinylidene fluoride / tetrafluoroethylene copolymer, vinylidene fluoride / hexafluoropropylene copolymer, vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer, tetrafluoroethylene / hexa Fluoropropylene / vinylidene fluoride copolymer (THV), vinylidene fluoride / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer, tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) Polymer, ethylene / chlorotrifluoroethylene copolymer (ECTFE), chlorotrifluoroethylene / tetrafluoroethylene copolymer, vinylidene fluoride / chlorotrifluoroethylene Polymer, chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) copolymer, chlorotrifluoroethylene / hexafluoropropylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene / hexafluoropropylene copolymer, chlorotrifluoroethylene / Tetrafluoroethylene / vinylidene fluoride copolymer, chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer (CPT), chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) / hexafluoropropylene Polymer, chlorotrifluoroethylene / tetrafluoroethylene / hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer, chlorotrifluoro Ethylene / tetrafluoroethylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer, chlorotrifluoroethylene / tetrafluoroethylene / vinylidene fluoride / hexafluoropropylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene / fluoride And vinylidene chloride / perfluoro (alkyl vinyl ether) / hexafluoropropylene copolymer. A layer containing a fluorine-containing polymer not containing a functional group is disposed on the inner side of the layer (d) containing the fluorine-containing polymer (D) containing a functional group having reactivity with the amino group. By doing so, it is possible to achieve both low temperature impact resistance, chemical solution permeation prevention properties, and environmental stress crack resistance, and it is economically advantageous.

  Further, high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra high molecular weight polyethylene (UHMWPE), polypropylene (PP), polybutene (PB) , Polymethylpentene (TPX), ethylene / propylene copolymer (EPR), ethylene / butene copolymer (EBR), ethylene / vinyl acetate copolymer (EVA), ethylene / acrylic acid copolymer (EAA), Polyolefins such as ethylene / methacrylic acid copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), ethylene / ethyl acrylate copolymer (EEA) Resin, polystyrene (PS), syndiotactic plastic Styrene (SPS), methyl methacrylate / styrene copolymer (MS), methyl methacrylate / styrene / butadiene copolymer (MBS), styrene / butadiene copolymer (SBR), styrene / isoprene copolymer (SIR) Styrene / isoprene / butadiene copolymer (SIBR), styrene / butadiene / styrene copolymer (SBS), styrene / isoprene / styrene copolymer (SIS), styrene / ethylene / butylene / styrene copolymer (SEBS) , Polystyrene resins such as styrene / ethylene / propylene / styrene copolymer (SEPS), acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4 -Cyclohexene-1,2-dicarboxylic acid, Carboxyl groups such as endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid, and metal salts thereof (Na, Zn, K, Ca, Mg), maleic anhydride, itaconic anhydride, anhydrous Acid anhydride groups such as citraconic acid and endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid anhydride, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, citracone Polyolefin resins and polystyrene resins containing functional groups such as epoxy groups such as glycidyl acid, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), poly (ethylene terephthalate / ethylene iso Phthalate) copolymer (PET / PEI), polyto Limethylene terephthalate (PTT), polycyclohexanedimethylene terephthalate (PCT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyarylate (PAR), liquid crystal polyester (LCP), polylactic acid (PLA), poly Polyester resins such as glycolic acid (PGA), polyether resins such as polyacetal (POM) and polyphenylene ether (PPO), polysulfones such as polysulfone (PSU), polyethersulfone (PESU), and polyphenylsulfone (PPSU) Resin, polythioether resin such as polyphenylene sulfide (PPS), polythioethersulfone (PTES), polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEE) ), Polyether ketone ketone (PEKK), polyether ether ether ketone (PEEEK), polyether ether ketone ketone (PEEKK), polyether ketone ketone ketone (PEKKK), polyether ketone ether ketone ketone (PEKEKK), etc. Resin, polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), acrylonitrile / butadiene copolymer Polynitrile resins such as (NBR), polymethacrylate resins such as polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA), and polyvinyl chloride such as polyvinyl acetate (PVAc) Polyester resins, polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), polyvinyl chloride / vinylidene chloride copolymers, polyvinyl chloride resins such as vinylidene chloride / methyl acrylate copolymers, cellulose acetate, cellulose butyrate, etc. Cellulose resins, polycarbonate resins such as polycarbonate (PC), thermoplastic polyimide (TPI), polyetherimide, polyesterimide, polyamideimide (PAI), polyesteramideimide, and other polyimide resins, thermoplastic polyurethane resins, Polyamide elastomer, polyurethane elastomer, polyester elastomer and the like can be mentioned.

  In the laminated tube of the present invention, from the viewpoint of melt stability of EVOH (C), among the thermoplastic resins exemplified above, a polyester resin having a melting point of 290 ° C. or lower, a polyamide resin, a polythioether resin, It is preferable to use a polyolefin-based resin and a fluorine-containing polymer that does not contain a functional group.

  It is also possible to laminate any substrate other than thermoplastic resin, such as paper, metal-based material, non-stretched, uniaxially or biaxially stretched plastic film or sheet, woven fabric, non-woven fabric, metal cotton, wood, etc. is there. Metallic materials include metals, metal compounds such as aluminum, iron, copper, nickel, gold, silver, titanium, molybdenum, magnesium, manganese, lead, tin, chromium, beryllium, tungsten, cobalt, and two or more of these. Alloy steels such as stainless steel, aluminum alloys, copper alloys such as brass and bronze, and alloys such as nickel alloys.

  As a laminated tube manufacturing method, using an extruder corresponding to the number of layers or the number of materials, melt extrusion, a method of simultaneously laminating inside or outside the die (coextrusion method), or a single layer tube or There is a method (coating method) in which a laminated tube produced by the above method is produced in advance, and an adhesive is used on the outside sequentially, if necessary, and the resin is integrated and laminated. The laminated tube of the present invention is preferably produced by a co-extrusion method in which various materials are co-extruded in a molten state, and both are thermally fused (melt-bonded) to produce a laminated structure tube in one step.

  In addition, when the obtained laminated tube has a complicated shape, or when it is subjected to heat bending after molding to form a molded product, in order to remove the residual distortion of the molded product, after forming the above laminated tube, It is also possible to obtain a desired molded article by heat treatment at a temperature lower than the lowest melting point of the resin constituting the tube at a temperature of 0.01 hours to 10 hours.

  The laminated tube may have a corrugated region. The waveform region is a region formed in a waveform shape, a bellows shape, an accordion shape, a corrugated shape, or the like. The corrugated region is not limited to having the entire length of the laminated tube, but may be partially provided in an appropriate region on the way. The corrugated region can be easily formed by first forming a straight tube and then molding it to obtain a predetermined corrugated shape or the like. By having such a corrugated region, it has shock absorption and attachment is easy. Furthermore, for example, it is possible to add necessary parts such as a connector, or to form an L shape or a U shape by bending.

  All or part of the outer periphery of the laminated tube formed in this way is made of natural rubber (NR), butadiene rubber (BR), isoprene rubber (IR) in consideration of stone shaving, abrasion with other parts, and flame resistance. ), Butyl rubber (IIR), chloroprene rubber (CR), carboxylated butadiene rubber (XBR), carboxylated chloroprene rubber (XCR), epichlorohydrin rubber (ECO), acrylonitrile butadiene rubber (NBR), hydrogenated acrylonitrile butadiene rubber (HNBR) Carboxylated acrylonitrile butadiene rubber (XNBR), mixture of NBR and polyvinyl chloride, acrylonitrile isoprene rubber (NIR), chlorinated polyethylene rubber (CM), chlorosulfonated polyethylene rubber (CSM), ethylene propylene rubber (EPR), Tylene propylene diene rubber (EPDM), ethylene vinyl acetate rubber (EVM), rubber mixture of NBR and EPDM, acrylic rubber (ACM), ethylene acrylic rubber (AEM), acrylate butadiene rubber (ABR), styrene butadiene rubber (SBR), carboxyl Styrene butadiene rubber (XSBR), styrene isoprene rubber (SIR), styrene isoprene butadiene rubber (SIBR), urethane rubber, silicone rubber (MQ, VMQ), fluoro rubber (FKM, FFKM), fluorosilicone rubber (FVMQ), chloride A solid or sponge-like protective member (protector) composed of a thermoplastic elastomer such as vinyl, olefin, ester, urethane, or amide can be disposed. The protective member may be a sponge-like porous body by a known method. By using a porous body, a protective part that is lightweight and excellent in heat insulation can be formed. Moreover, material cost can also be reduced. Alternatively, the strength may be improved by adding glass fiber or the like. Although the shape of a protection member is not specifically limited, Usually, it is a block-shaped member which has a recessed part which receives a cylindrical member or a laminated tube. In the case of a cylindrical member, the laminated tube can be inserted later into a previously produced cylindrical member, or the cylindrical member can be coated and extruded onto the laminated tube to adhere both together. In order to bond the two, the adhesive is applied to the inner surface of the protective member or the concave surface as necessary, and the laminated tube is inserted or fitted into this, and the two are brought into close contact with each other, thereby integrating the laminated tube and the protective member. Forming a structure. It can also be reinforced with metal or the like.

  The outer diameter of the laminated tube considers the flow rate of chemicals (for example, fuel such as alcohol-containing gasoline), and the thickness is such that the permeability of chemicals does not increase, and the normal tube breaking pressure can be maintained. And although it is designed by the thickness which can maintain the softness | flexibility of the grade with the favorable assembly | attachment work of a tube and the vibration resistance at the time of use, it is not limited. The outer diameter is preferably 4 mm to 300 mm, the inner diameter is preferably 3 mm to 250 mm, and the wall thickness is preferably 0.5 mm to 25 mm.

  The laminated tube of the present invention includes machine parts such as automobile parts, internal combustion engines, electric tool housings, industrial materials, industrial materials, electrical / electronic parts, medical care, food, household / office supplies, building materials related parts, furniture. It can be used for various applications such as industrial parts.

  Moreover, since the laminated tube of this invention is excellent in chemical-solution permeation prevention property, it is suitable as a chemical-solution transport tube. Examples of the chemical solution include aromatic hydrocarbon solvents such as benzene, toluene, xylene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, diethylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol, and the like. Alcohol, phenol solvents, dimethyl ether, dipropyl ether, methyl-t-butyl ether, ethyl t-butyl ether, dioxane, tetrahydrofuran and other ether solvents, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane , Halogen solvents such as dichloroethane, tetrachloroethane, perchlorethane, chlorobenzene, acetone, methylethyl Ton, diethyl ketone, ketone solvents such as acetophenone, gasoline, kerosene, diesel gasoline, alcohol-containing gasoline, ethyl-t-butyl ether blend, oxygen-containing gasoline, amine-containing gasoline, sour gasoline, castor oil base brake fluid, glycol ether brake fluid , Borate ester brake fluid, brake fluid for extremely cold regions, silicone oil brake fluid, mineral oil brake fluid, power steering oil, hydrogen sulfide oil, window washer fluid, engine coolant, urea solution, pharmaceutical agent, ink, A paint etc. are mentioned. The laminated tube of the present invention is suitable as a tube for conveying the above chemical solution, specifically, a feed tube, a return tube, an evaporation tube, a fuel filler tube, an ORVR tube, a reserve tube, a fuel tube such as a vent tube, an oil Tube, oil drilling tube, brake tube, tube for window washer fluid, engine coolant (LLC) tube, reservoir tank tube, urea solution transfer tube, cooler tube for cooling water, refrigerant, etc., air conditioner refrigerant tube, heater tube, load Heating tubes, floor heating tubes, infrastructure supply tubes, fire extinguishers and fire extinguishing equipment tubes, medical cooling equipment tubes, inks, paint spray tubes, and other chemical solution tubes. In particular, it is suitable as a fuel tube.

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited thereto.
In addition, the analysis used in an Example and a comparative example, the measuring method of a physical property, and the material used for the Example and the comparative example are shown.

The properties of the polyamide resin were measured by the following method.
[Relative viscosity]
According to JIS K-6920, the measurement was performed in 96% sulfuric acid under the conditions of a polymer concentration of 1% and a temperature of 25 ° C.

[Terminal amino group concentration]
Put a predetermined amount of polyamide sample in a conical flask with stopcock, add 40 mL of a pre-adjusted solvent phenol / methanol (volume ratio 9/1), dissolve with stirring with a magnetic stirrer, and use thymol blue as an indicator Then, titration with 0.05N hydrochloric acid was performed to determine the terminal amino group concentration.

[Terminal carboxyl group concentration]
A predetermined amount of polyamide sample is placed in a three-neck pear-shaped flask, 40 mL of benzyl alcohol is added, and then immersed in an oil bath set at 180 ° C. under a nitrogen stream. The mixture was stirred and dissolved by a stirring motor attached to the upper portion, and titrated with 0.05N sodium hydroxide solution using phenolphthalein as an indicator to determine the terminal carboxyl group concentration.

The characteristics of the fluorine-containing polymer were measured by the following method.
[Composition of fluorinated polymer]
It was measured by melt NMR analysis, fluorine content analysis, and infrared absorption spectrum.

[Number of terminal carbonate groups in fluorine-containing polymer]
As for the number of terminal carbonate groups in the fluorine-containing polymer, the peak to which the carbonyl group of the carbonate group (—OC (═O) O—) belongs appears at an absorption wavelength of 1817 cm ⁻¹ by infrared absorption spectrum analysis, and the absorption peak The number of carbonate groups relative to 10 ⁶ main chain carbon atoms in the fluorine-containing polymer was calculated according to the following formula.
[Number of carbonate groups with respect to 10 ⁶ main chain carbon atoms in the fluorine-containing polymer] = 500 AW / εdf
A: Absorbance at peak of carbonate group (—OC (═O) O—) ε: Molar absorbance coefficient [cm ⁻¹ · mol ⁻¹ ] of carbonate group (—OC (═O) O—). Ε = 170 from the model compound.
W: Composition average molecular weight calculated from the monomer composition d: Film density [g / cm ³ ]
f: Film thickness [mm]

Moreover, each physical property of the laminated tube was measured by the following method.
[Low temperature impact resistance]
The impact test was performed at −40 ° C. by the method described in VW TL52435 4.2.

[Deterioration fuel resistance]
A deterioration resistant fuel test was carried out by the method described in SAE J-2260 7.8. The tube after the test was subjected to an impact test at −40 ° C. by the method described in SAE J-2260 7.5. Judged to be excellent.

[Permeability of chemical solution (alcohol-containing gasoline) permeation]
One end of a tube cut to 200 mm is sealed, and alcohol-containing gasoline (CE10) mixed in isooctane / toluene / ethanol = 45/45/10 vol%, or isooctane / toluene / ethanol 7.5 / 7.5 / Alcohol-containing gasoline (CE85) mixed in 85% by volume was added, and the remaining ends were sealed. Thereafter, the entire mass was measured, and then the test tube was placed in an oven at 60 ° C., and the mass change was measured every day. The mass change per day was divided by the surface area of the tube to calculate the permeation amount of alcohol-containing gasoline (g / m ² · day).

[Interlayer adhesion]
The tube cut to 200 mm was further cut in half in the vertical direction to create a test piece. Using a universal material testing machine (Orientec Co., Ltd., Tensilon UTM III-200), a 180 ° peel test was performed at a tensile speed of 50 mm / min. The peel strength was read from the maximum point of the SS curve, and the interlayer adhesion was evaluated.

[Interlayer adhesion after heat treatment]
The tube cut to 200 mm was placed in an oven at 160 ° C. and treated for 12 minutes. The interlayer adhesion of the removed tube was evaluated according to the method described above. When the peel strength after heat treatment was 20 N / cm or more, it was judged that the durability of interlayer adhesion was excellent.

[Elution resistance of monomers and oligomers]
Seal one end of the tube cut to 0.5 m, and put alcohol-containing gasoline (CE10) in which Fuel C (isooctane / toluene = 50/50 volume ratio) and ethanol in a 90/10 volume ratio were mixed, and the other end The part was also sealed. Thereafter, the test tube was placed in an oven at 60 ° C. and treated for 48 hours. After completion of the treatment, the alcohol-containing gasoline in the taken out tube was cooled at 0 ° C. for 24 hours, and then filtered through a filter (material: polyethersulfone) having a pore diameter of 0.45 μm, and the mass of the collected material was measured. The mass of the collected material was divided by the number of treatment days and the inner surface area of the tube to calculate the monomer and oligomer elution amounts (g / m ² · day). After the treatment, the color tone of the alcohol-containing gasoline extracted from the tube was also visually observed.

[Materials Used in Examples and Comparative Examples]
Aliphatic polyamide (A)
Manufacture of Polyamide 12 Composition (A-1) Polyamide 12 (a-1) (Ube Industries, UBESTA 3030UX1, relative viscosity 2.21) and maleic anhydride modified ethylene / propylene copolymer as impact modifier Combined (manufactured by JSR Corporation, JSR T7761P), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] as an antioxidant (manufactured by BASF Japan, IRGANOX245) And tris (2,4-di-t-butylphenyl) phosphite (manufactured by BASF Japan, IRGAFOS168) as a phosphorus processing stabilizer are mixed in advance, and a twin-screw melt kneader (manufactured by Nippon Steel Works, Ltd.) As a plasticizer from the middle of the cylinder of the biaxial melt kneader. Insene sulfonic acid butyramide is injected with a metering pump, melt-kneaded at a cylinder temperature of 180 to 260 ° C., and the molten resin is extruded into a strand shape, which is then introduced into a water bath, cooled, cut, and vacuum-dried. 12 Polyamide 12 composition comprising 0.8 parts by weight of antioxidant and 0.2 parts by weight of phosphorus-based processing stabilizer for 100 parts by weight of 85% by weight, 10% by weight of impact modifier, and 5% by weight of plasticizer A pellet of the product was obtained (hereinafter, this polyamide 12 composition is referred to as (A-1)).

Manufacture of polyamide 12 composition (A-2) In the manufacture of polyamide 12 composition (A-1), a polyamide 12 composition (A-) was used except that a plasticizer was not used and the amount of impact modifier added was changed. In the same manner as in the production of 1), 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus-based processing stabilizer with respect to a total of 100 parts by mass of polyamide 12 of 85% by mass and impact modifier 15% by mass. Part of a polyamide 12 composition pellet was obtained (hereinafter, this polyamide 12 composition is referred to as (A-2)).

Production of Conductive Polyamide 12 Composition (A-3) In production of the polyamide 12 composition (A-1), polyamide 12 (a-1) was converted to (a-2) (Ube Industries, UBESTA 3020U, Relative viscosity was changed to 1.86), polyamide was used except that carbon black (Cabot Co., Vulcan XD-72) was used as the conductive filler, the plasticizer was not used, and the cylinder temperature was changed from 260 ° C to 270 ° C. 12 In the same manner as in the production of the composition (A-1), an antioxidant of 0.1% was added to 100 parts by mass in total of 60% by mass of polyamide 12, 20% by mass of impact modifier, and 20% by mass of conductive filler. The pellet of the conductive polyamide 12 composition which consists of 8 mass parts and 0.2 mass parts of phosphorus processing stabilizers was obtained (henceforth this conductive polyamide 12 composition is called (A-3)).

Production of polyamide 610 (a-3) or (b-2) In a pressure-resistant reaction vessel with an internal volume of 70 liters equipped with a stirrer, 17.6 kg of a 50% by weight aqueous solution of an equimolar salt of 1,6-hexanediamine and sebacic acid, After charging 40.0 g of 1,6-hexanediamine and replacing the inside of the polymerization tank with nitrogen, the mixture was heated to 220 ° C. and stirred at this temperature so that the reaction system was in a uniform state. Next, the temperature in the polymerization tank was raised to 270 ° C., and polymerization was performed with stirring for 2 hours while adjusting the pressure in the tank to 1.7 MPa. Thereafter, the pressure was released to normal pressure over about 2 hours, and then the pressure was reduced to 53 kPa, and polymerization was performed for 4 hours under reduced pressure. Next, nitrogen was introduced into the autoclave, and after returning to normal pressure, the strand was extracted from the lower nozzle of the reaction vessel and cut to obtain pellets. This pellet was dried under reduced pressure to obtain a polyamide 610 having a relative viscosity of 3.05, a terminal amino group concentration of 50 μeq / g, and a terminal carboxyl group concentration of 14 μeq / g (hereinafter, this polyamide 610 was converted to (a-3) or (b- 2).)

Production of polyamide 610 composition (A-4) In production of polyamide 12 composition (A-1), polyamide 12 (a-1) was changed to polyamide 610 (a-3), and the cylinder temperature was changed from 260 ° C to 270 ° C. In the same manner as in the production of the polyamide 12 composition (A-1), except that the polyamide 610 is 80% by mass, the impact resistance improving material 10% by mass, and the plasticizer 10% by mass in total 100 parts by mass. Thus, pellets of a polyamide 610 composition comprising 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained (hereinafter, this polyamide 610 composition is referred to as (A-4)).

Production of polyamide 612 (a-4) or (b-3) In the production of polyamide 610 (a-3), 17.6 kg of a 50% by mass aqueous solution of an equimolar salt of 1,6-hexanediamine and sebacic acid was Polyamide 610 (a-3) except that 19.2 kg of a 50% by weight aqueous solution of an equimolar salt of 6-hexanediamine and dodecanedioic acid and the amount of 1,6-hexanediamine added were changed from 40.0 g to 43.5 g. ) To obtain a polyamide 612 having a relative viscosity of 2.78, a terminal amino group concentration of 51 μeq / g, and a terminal carboxyl group concentration of 14 μeq / g (hereinafter, this polyamide 612 is converted to (a-4) or (Referred to as (b-3)).

Production of polyamide 612 composition (A-5) In production of polyamide 12 composition (A-1), polyamide 12 (a-1) was changed to polyamide 612 (a-4), and the cylinder temperature was changed from 260 ° C to 270 ° C. In the same manner as in the production of the polyamide 12 composition (A-1), except that the polyamide 612 is 80% by mass, the impact resistance improving material 10% by mass, and the plasticizer 10% by mass in total 100 parts by mass. Thus, pellets of a polyamide 612 composition comprising 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus processing stabilizer were obtained (hereinafter, this polyamide 612 composition is referred to as (A-5)).

Manufacture of polyamide 6 composition (A-6) In manufacture of polyamide 12 composition (A-1), polyamide 12 (a-1) was converted to polyamide 6 (a-5) (Ube Industries, UBE NYLON 1030B). The relative viscosity was 3.89), and the cylinder temperature was changed from 260 ° C. to 270 ° C., in the same manner as in the production of the polyamide 12 composition (A-1). Polyamide 6 composition pellets comprising 0.8 parts by weight of antioxidant and 0.2 parts by weight of phosphorus processing stabilizer were obtained with respect to 100 parts by weight in total of 10 parts by weight of material and 10 parts by weight of plasticizer ( Hereinafter, this polyamide 6 composition is referred to as (A-6)).

Polyamide 6/66/12 composition (B)
Manufacture of polyamide 6/66/12 (b-1) Caprolactam 16.2 kg, 50 mass% aqueous solution of equimolar salt of 1,6-hexanediamine and sebacic acid 5 0.0 kg and 2.5 kg of 12-aminododecanoic acid were added, heated to 100 ° C., and stirred at this temperature so that the reaction system was in a uniform state. Subsequently, the temperature was further raised to 260 ° C., and the mixture was stirred for 1 hour under a pressure of 2.5 MPa. Then, the polymerization reaction was performed at 260 ° C. for 2 hours under normal pressure while releasing the pressure to evaporate water from the reaction vessel, and further for 7 hours under reduced pressure of 260 ° C. and 53 kPa. After completion of the reaction, the reaction product taken out in a strand form from the lower nozzle of the reaction vessel was introduced into a water bath, cooled, and cut to obtain pellets. This pellet was immersed in hot water to remove unreacted monomers and then dried under reduced pressure to give polyamide 6/66/12 (caproamide unit / hexamethylene adipamide unit / dodecanamide) having a relative viscosity of 4.01. (Unit = 78/11/11% by mass) was obtained (hereinafter, this polyamide 6/66/12 is referred to as (b-1)).

Manufacture of polyamide 6/66/12 composition (B-1) In the manufacture of polyamide 12 composition (A-1), polyamide 12 (a-1) was replaced with polyamide 6/66/12 (b-1) and polyamide 610. Except for changing to (b-2), polyamide 6/66/12 50% by mass, polyamide 610 30% by mass, impact resistance improving material 15 by the same method as in the production of the polyamide 12 composition (A-1) A pellet of polyamide 6/66/12 composition comprising 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus processing stabilizer is obtained with respect to 100 parts by mass in total of 5% by mass and 5% by mass of plasticizer. (Hereinafter, this polyamide 6/66/12 composition is referred to as (B-1)).

Production of polyamide 6/66/12 composition (B-2) Polyamide 610 (b-2) was changed to polyamide 612 (b-3) in the production of polyamide 6/66/12 composition (B-1). Except for the above, in the same manner as in the production of the polyamide 6/66/12 composition (B-1), polyamide 6/66/12 50% by mass, polyamide 612 30% by mass, impact resistance improving material 15% by mass, plasticity A pellet of polyamide 6/66/12 composition comprising 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer was obtained with respect to 100 parts by mass in total of 5% by mass of the agent (hereinafter, This polyamide 6/66/12 composition is referred to as (B-2)).

Manufacture of a polyamide 6/66/12 composition (B-3) In the manufacture of the polyamide 6/66/12 composition (B-1), the polyamide 6/66 / is used except that the polyamide 610 (b-2) is not used. 12 In the same manner as in the production of composition (B-1), oxidation was performed on 100 parts by mass of polyamide 6/66/12 80% by mass, impact resistance improver 15% by mass, and plasticizer 5% by mass. Pellets of a polyamide 6/66/12 composition comprising 0.8 parts by weight of an inhibitor and 0.2 parts by weight of a phosphorus-based processing stabilizer were obtained (hereinafter, this polyamide 6/66/12 composition (B-3 ).)

Production of polyamide 6/66/12 composition (B-4) Polyamide 610 (b-2), impact modifier and plasticizer are not used in the production of polyamide 6/66/12 composition (B-1). Except for polyamide 6/66/12 composition (B-1) in the same manner as in the production of polyamide 6/66/12, 100 parts by mass of polyamide 6/66/12, 0.8 parts by mass of antioxidant, phosphorus-based processing Polyamide 6/66/12 composition pellets comprising 0.2 parts by weight of stabilizer were obtained (hereinafter, this polyamide 6/66/12 composition is referred to as (B-4)).

Production of polyamide 6/12 (b-4) In production of polyamide 6/66/12 (b-1), caprolactam 16.2 kg, 50% by mass aqueous solution of equimolar salt of 1,6-hexanediamine and sebacic acid 5 0.06 kg and 12-aminododecanoic acid 2.5 kg were changed to caprolactam 16.2 kg, 12-aminododecanoic acid 4.4 kg, and 2 kg of water was added, and polyamide 6/66/12 (b-1) A polyamide 6/12 having a relative viscosity of 3.86 (caproamide unit / dodecanamide unit = 80/20% by mass) was obtained in the same manner as in the production (hereinafter, this polyamide 6/12 is referred to as (b-4). .)

Polyamide 6/12 composition (B-5)
In the production of the polyamide 6/66/12 composition (B-1), the polyamide 6/66/12 (b-1) is changed to the polyamide 6/12 (b-4), and the polyamide 610 (b-2) is changed. Except not using, in the same manner as in the production of the polyamide 6/66/12 composition (B-1), a total of 80% by mass of polyamide 6/12, 15% by mass of impact resistance improving agent, and 5% by mass of plasticizer A polyamide 6/12 composition pellet comprising 0.8 part by weight of an antioxidant and 0.2 part by weight of a phosphorus processing stabilizer was obtained with respect to 100 parts by weight (hereinafter, this polyamide 6/12 composition was (B-5).)

Saponified ethylene / vinyl acetate copolymer (C)
EVOH (C-1): manufactured by Nippon Synthetic Chemical Co., Ltd., Soarnol DC3203, ethylene content 32 mol%, saponification degree 99 mol% or more

Fluorinated polymer (D)
Production of fluorinated polymer (D-1) A polymerization tank equipped with a stirrer having an internal volume of 100 L was degassed, and 92.1 kg of 1-hydrotridecafluorohexane, 1,3-dichloro-1,1,2, , 2,3-pentafluoropropane 16.3 kg, (perfluoroethyl) ethylene _{CH 2 = CH (CF 2)} 2 F73g, charged itaconic anhydride (IAH) 10.1 g, tetrafluoroethylene (TFE) 9.6 kg Then, 0.7 kg of ethylene (E) was injected, the inside of the polymerization tank was heated to 66 ° C., and 1% by mass of t-butyl peroxypivalate as a polymerization initiator 1,3-dichloro-1,1,2,2, A 433 cm ³ of 3-pentafluoropropane solution was charged to initiate the polymerization.
A monomer mixed gas of TFE / E: 60/40 (molar ratio) was continuously charged so that the pressure was constant during the polymerization. In addition, (perfluoroethyl) ethylene corresponding to 2.0 mol% and IAH corresponding to 0.5 mol% were continuously charged with respect to the total number of moles of TFE and E charged during the polymerization. . 5.5 hours after the start of the polymerization, when the monomer mixed gas of 8.0 kg and IAH of 63 g were charged, the temperature inside the polymerization tank was lowered to room temperature and purged to normal pressure. The obtained slurry-like fluorine-containing polymer was put into a 200 L granulation tank charged with 75.0 kg of water, and then heated to 105 ° C. while stirring and granulated while distilling and removing the solvent. The obtained granulated product was dried at 150 ° C. for 5 hours to obtain 8.3 kg of a fluorine-containing polymer.
The composition of the fluorine-containing polymer is as follows: polymerized units based on TFE / polymerized units based on E / polymerized units based on CH ₂ = CH (CF ₂ ) ₂ F / polymerized units based on IAH = 58.5 / 39.0 /2.0/0.5 (mol%), and the melting point was 240 ° C. This granulated product was melted at 280 ° C. and a residence time of 2 minutes using an extruder to obtain pellets of a fluorine-containing polymer (hereinafter, this fluorine-containing polymer is referred to as (D-1). ).

Production of conductive fluorine-containing polymer (D-2) 100 parts by mass of fluorine-containing polymer (D-1) and 13 parts by mass of carbon black (manufactured by Electrochemical Co., Ltd.) are mixed in advance and biaxially melted. Supply to a kneading machine (Toshiba Machine Co., Ltd., model: TEM-48S), melt knead at a cylinder temperature of 240 ° C to 300 ° C, extrude the molten resin into a strand, introduce it into a water tank, and discharge The strand was cooled with water, the strand was cut with a pelletizer, and dried for 10 hours with a drier at 120 ° C. to remove moisture to obtain a conductive fluorine-containing polymer pellet (hereinafter referred to as this conductive fluorine-containing polymer). The polymer is referred to as (D-2).)

Production of fluorinated polymer (D-3) Production of fluorinated polymer (D-1) except that itaconic anhydride (IAH) is not charged in the production of fluorinated polymer (D-1). In the same manner as above, 7.6 kg of a fluorine-containing polymer was obtained.
The composition of the fluorine-containing polymer is as follows: polymerized units based on TFE / polymerized units based on E / polymerized units based on CH ₂ ═CH (CF ₂ ) ₂ F / polymerized units based on IAH = 58.8 / 39.2 /2.0 (mol%), and the melting point was 242 ° C. This granulated product was melted at 280 ° C. and a residence time of 2 minutes using an extruder to obtain pellets of a fluorine-containing polymer (hereinafter, this fluorine-containing polymer is referred to as (D-3)). ).

Production of conductive fluorine-containing polymer (D-4) In production of conductive fluorine-containing polymer (D-2), fluorine-containing polymer (D-1) was changed to (D-3). Obtained the conductive fluorine-containing polymer pellets in the same manner as in the production of the conductive fluorine-containing polymer (D-2) (hereinafter this conductive fluorine-containing polymer (D- 4).)

Production of fluorinated polymer (D-5) A polymerization tank equipped with a stirrer having an internal volume of 100 L was degassed, 42.5 kg of 1,3-dichloro-1,1,2,2,3-pentafluoropropane, _{CF 2 = CFOCF 2 CF 2 CF} 3 ( perfluoro (propyl vinyl ether): PPVE), 1,1,2,4,4,5,5,6,6,6- decafluoro-3-oxa hex-1- Ene) 2.13 kg and hexafluoropropylene (HFP) 51.0 kg were charged. Next, the temperature in the polymerization tank was raised to 50 ° C., 4.25 kg of tetrafluoroethylene (TFE) was charged, and the pressure was increased to 1.0 MPa / G. As a polymerization initiator solution, 340 cm ³ of (perfluorobutyryl) peroxide 0.3 mass% 1,3-dichloro-1,1,2,2,3-pentafluoropropane solution was charged to initiate polymerization, and thereafter 10 minutes Every time, 340 cm ³ of the polymerization initiator solution was charged.
During the polymerization, TFE was continuously charged so that the pressure was maintained at 1.0 MPa / G. Further, the amount of 5-norbornene-2,3-dicarboxylic acid anhydride (NAH) 0.3 mass% 1,3-dichloro-1 in an amount corresponding to 0.1 mol% with respect to the number of moles of TFE charged during the polymerization. 1,2,2,3-pentafluoropropane solution was continuously charged. After 5 hours from the start of polymerization, when 8.5 kg of TFE was charged, the polymerization tank internal temperature was lowered to room temperature and purged to normal pressure. The obtained slurry-like fluorine-containing polymer was put into a 200 L granulation tank charged with 75.0 kg of water, and then heated to 105 ° C. while stirring and granulated while distilling and removing the solvent. The obtained granulated product was dried at 150 ° C. for 5 hours to obtain 7.5 kg of a fluoropolymer granulated product.
The composition of the fluorine-containing polymer is as follows: polymerized units based on TFE / polymerized units based on PPVE / polymerized units based on HFP / polymerized units based on NAH = 91.2 / 1.5 / 7.2 / 0.1 ( Mol%) and the melting point was 262 ° C. This granulated product was melted using an extruder at 300 ° C. for a residence time of 2 minutes to obtain a fluorine-containing polymer pellet (hereinafter, this fluorine-containing polymer is referred to as (D-5). ).

Production of conductive fluorine-containing polymer (D-6) In production of conductive fluorine-containing polymer (D-2), fluorine-containing polymer (D-1) was converted to (D-5), carbon black 13 Except for changing the mass part to 11 parts by mass and changing the cylinder temperature from 300 ° C. to 320 ° C., in the same manner as the production of the conductive fluorine-containing polymer (D-2), A coalescence pellet was obtained (hereinafter, this conductive fluorine-containing polymer is referred to as (D-6)).

Production of fluorinated polymer (D-7) In the production of fluorinated polymer (D-5), 5-norbornene-2,3-dicarboxylic acid anhydride (NAH) 0.3 mass% 1,3- 7.6 kg of fluorinated polymer in the same manner as the production of the fluorinated polymer (D-5), except that no dichloro-1,1,2,2,3-pentafluoropropane solution was charged. Got.
The composition of the fluorine-containing polymer is TFE-based polymer units / PPVE-based polymer units / HFP-based polymer units = 91.5 / 1.5 / 7.0 (mol%), and the melting point is 257 ° C. Met. This granulated product was melted using an extruder at 300 ° C. for a residence time of 2 minutes to obtain a fluorine-containing polymer pellet (hereinafter, this fluorine-containing polymer is referred to as (D-7)). ).

Production of conductive fluorine-containing polymer (D-8) In production of conductive fluorine-containing polymer (D-6), except that fluorine-containing polymer (D-5) was changed to (D-7) Obtained the conductive fluorine-containing polymer pellets in the same manner as in the production of the conductive fluorine-containing polymer (D-6) (hereinafter, this conductive fluorine-containing polymer (D- 8).)

Production of fluorinated polymer (D-9) 51.5 kg of demineralized pure water was placed in a jacketed stirring polymerization tank capable of containing 174 kg of water, and the interior space was sufficiently replaced with pure nitrogen gas. Was eliminated in vacuo. Next, 40.6 kg of octafluorocyclobutane, 1.6 kg of chlorotrifluoroethylene (CTFE), 4.5 kg of tetrafluoroethylene (TFE), and 2.8 kg of perfluoro (propyl vinyl ether) (PPVE) were injected. 0.090 kg of n-propyl alcohol was added as a chain transfer agent, the temperature was adjusted to 35 ° C., and stirring was started. To this, 0.44 kg of 50% by weight methanol solution of di-n-propyl peroxydicarbonate was added as a polymerization initiator to initiate polymerization. During the polymerization, a mixed monomer prepared to have the same composition as the desired copolymer composition is polymerized while being additionally charged so that the pressure in the tank is maintained at 0.66 MPa, and then the residual gas in the tank is exhausted. The produced polymer was taken out, washed with demineralized pure water, and dried to obtain 30.5 kg of a granular powder fluorine-containing polymer.
The composition of the fluoropolymer is 24.4 / 73.1 / 2.5 in terms of the molar ratio of polymerized units based on CTFE / polymerized units based on TFE / polymerized units based on PPVE. The number of carbonate end groups derived from the initiator was 170. The melting point was 241 ° C. This granulated product was melted at 290 ° C. and a residence time of 2 minutes using an extruder to obtain pellets of a fluorine-containing polymer (hereinafter, this fluorine-containing polymer is referred to as (D-9)). ).

Production of conductive fluorine-containing polymer (D-10) In production of conductive fluorine-containing polymer (D-6), fluorine-containing polymer (D-5) was changed to (D-9). Obtained the conductive fluorine-containing polymer pellets in the same manner as in the production of the conductive fluorine-containing polymer (D-6) (hereinafter, this conductive fluorine-containing polymer (D- 10).)

Production of fluorinated polymer (D-11) In the production of fluorinated polymer (D-9), fluorinated heavy polymer was used except that 50% by weight di-n-propylperoxydicarbonate methanol solution was not charged. 29.8 kg of a fluorine-containing polymer was obtained in the same manner as in the production of the coalescence (D-9).
The composition of the fluorine-containing polymer is 24.4 / 73.1 / 2.5 in terms of the molar ratio of polymerized units based on CTFE / polymerized units based on TFE / polymerized units based on PPVE, and the melting point is 241 ° C. there were. This granulated material was melted at 290 ° C. and a residence time of 2 minutes using an extruder to obtain a fluorine-containing polymer pellet (hereinafter, this fluorine-containing polymer is referred to as (D-11). ).

Production of conductive fluorine-containing polymer (D-12) In production of conductive fluorine-containing polymer (D-6), except that fluorine-containing polymer (D-5) was changed to (D-11) Obtained the conductive fluorine-containing polymer pellets in the same manner as in the production of the conductive fluorine-containing polymer (D-6) (hereinafter, this conductive fluorine-containing polymer (D- 12)).

(E) Semi-aromatic polyamide (E-1) Polymetaxylylene adipamide: Mitsubishi Gas Chemical Co., Ltd., MX-nylon 6007

Example 1
Polyamide 12 composition (A-1), polyamide 6 composition (A-6), polyamide 6/66/12 composition (B-1), EVOH (C-1), and fluorine-containing polymer shown above (D-1) was used in a Plabor (Plastic Engineering Laboratory Co., Ltd.) 5-layer tube molding machine, (A-1) was extruded at 250 ° C, and (A-6) was extruded at 260 ° C. , (B-1) is melted separately at an extrusion temperature of 260 ° C., (C-1) is extruded at 220 ° C., and (D-1) is melted at an extrusion temperature of 300 ° C., and the discharged molten resin is joined by an adapter. And formed into a laminated tubular body. Subsequently, it is cooled by a sizing die for dimension control and taken up, and the (a) layer (outermost layer) composed of (A-1), the (b) layer (outer layer) composed of (B-1), (C-1 (C) layer (intermediate layer) consisting of (A), (a ') layer (inner layer 1) consisting of (A-6), and (d) layer (innermost layer) consisting of (D-1). (A) / (b) / (c) / (a ′) / (d) = 0.35 / 0.15 / 0.10 / 0.25 / 0.15 mm with an inner diameter of 6 mm and an outer diameter of 8 mm A tube was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 2
In Example 1, except that the polyamide 6 composition (A-6) was changed to a polyamide 6/66/12 composition (B-1), the same procedure as in Example 1 was carried out from (A-1). (A) layer (outermost layer), (B-1) (b) layer (outer layer, inner layer 1), (C-1) (c) layer (intermediate layer), (D-1) (D) layer (innermost layer), the layer structure is (a) / (b) / (c) / (b) / (d) = 0.35 / 0.15 / 0.10 / 0. A laminated tube having an inner diameter of 6 mm and an outer diameter of 8 mm at 25 / 0.15 mm was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 3
Polyamide 12 composition (A-1), polyamide 6 composition (A-6), polyamide 6/66/12 composition (B-1), EVOH (C-1), and fluorine-containing polymer shown above Using (D-1), a 6-layer tube molding machine (manufactured by Plastics Engineering Laboratory Co., Ltd.), (A-1) was extruded at 250 ° C, and (A-6) was extruded at 260 ° C. , (B-1) is melted separately at an extrusion temperature of 260 ° C., (C-1) is extruded at 220 ° C., and (D-1) is melted at an extrusion temperature of 300 ° C., and the discharged molten resin is joined by an adapter. And formed into a laminated tubular body. Subsequently, it is cooled by a sizing die for dimension control and taken up, and (a) layer (outermost layer) made of (A-1), (b) layer (outer layer) made of (B-1), (A-6) (A ′) layer (intermediate layer, inner layer 2), (c-1) layer (inner layer 1), (d) layer (d) layer (innermost layer) The layer structure is (a) / (b) / (a ′) / (c) / (a ′) / (d) = 0.30 / 0.10 / 0.10 / 0.10 / 0.25 / A laminated tube having an inner diameter of 6 mm and an outer diameter of 8 mm at 0.15 mm was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 4
In Example 1, except that the polyamide 12 composition (A-1) was changed to the polyamide 610 composition (A-4) and the extrusion temperature of (A-4) was changed to 260 ° C., the same as in Example 1. By the method, the laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 5
In Example 1, the polyamide 12 composition (A-1) was changed to the polyamide 612 composition (A-5), and the extrusion temperature of (A-5) was changed to 260 ° C. By the method, the laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 6
In Example 1, except that the polyamide 6/66/12 composition (B-1) was changed to (B-2), a laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 1. Obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 7
In Example 1, except that the fluorine-containing polymer (D-1) was changed to the conductive fluorine-containing polymer (D-2) and the extrusion temperature of (D-2) was changed to 310 ° C. 1 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 8
In Example 1, except that the fluorine-containing polymer (D-1) was changed to (D-5) and the extrusion temperature of (D-5) was changed to 310 ° C., the same method as in Example 1 was used. The laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 9
In Example 1, except that the fluorine-containing polymer (D-1) was changed to the conductive fluorine-containing polymer (D-6) and the extrusion temperature of (D-6) was changed to 320 ° C. 1 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 10
In Example 1, except that the fluorine-containing polymer (D-1) was changed to (D-9) and the extrusion temperature of (D-9) was changed to 290 ° C., the same method as in Example 1 was used. The laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 11
In Example 1, except that the fluorine-containing polymer (D-1) was changed to the conductive fluorine-containing polymer (D-10) and the extrusion temperature of (D-10) was changed to 310 ° C. 1 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 12
Polyamide 12 composition (A-1), polyamide 6 composition (A-6), polyamide 6/66/12 composition (B-1), EVOH (C-1), fluorine-containing polymer (shown above) D-1) and a conductive fluorine-containing polymer (D-2), and (A-1) extrusion temperature in a Plabor (Plastics Engineering Laboratory Co., Ltd.) 6-layer tube molding machine 250C, (A-6) extrusion temperature 260C, (B-1) extrusion temperature 260C, (C-1) extrusion temperature 220C, (D-1) extrusion temperature 300C, (D- 2) was melted separately at an extrusion temperature of 310 ° C., and the discharged molten resin was joined by an adapter to form a laminated tubular body. Subsequently, it is cooled by a sizing die for dimension control and taken up, and the (a) layer (outermost layer) composed of (A-1), the (b) layer (outer layer) composed of (B-1), (C-1 (C) layer (intermediate layer) consisting of (A)) (a ') layer (inner layer 1) consisting of (A-6), (d) layer (inner layer 2) consisting of (D-1), (D-2) (D ′) layer (innermost layer) composed of (a) / (b) / (c) / (a ′) / (d) / (d ′) = 0.30 / 0. A laminated tube having an inner diameter of 6 mm and an outer diameter of 8 mm at 15 / 0.10 / 0.25 / 0.10 / 0.10 mm was obtained. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 13
In Example 12, a laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 12 except that the conductive fluorine-containing polymer (D-2) was changed to (D-4). It was. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 14
In Example 12, the same method as in Example 12 except that the conductive fluorine-containing polymer (D-2) was changed to (D-6) and the extrusion temperature of (D-6) was changed to 320 ° C. Thus, a laminated tube having a layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 15
In Example 12, the same method as in Example 12 except that the conductive fluorine-containing polymer (D-2) was changed to (D-8) and the extrusion temperature of (D-8) was changed to 320 ° C. Thus, a laminated tube having a layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 16
In Example 12, a laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 12 except that the conductive fluorine-containing polymer (D-2) was changed to (D-10). It was. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 17
In Example 12, a laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 12 except that the conductive fluorine-containing polymer (D-2) was changed to (D-12). It was. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Comparative Example 1
In Example 1, the laminated tube of the layer structure shown in Table 1 was obtained by the same method as Example 1 except not using EVOH (C-1) and a fluorine-containing polymer (D-1). . The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 2
In Example 1, the laminated tube of the layer structure shown in Table 1 was obtained by the same method as Example 1 except not using EVOH (C-1). The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 3
In Example 1, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 1 except not using a fluorine-containing polymer (D-1). The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 4
In Example 1, it is the same as Example 1 except not using a polyamide 12 composition (A-1), a polyamide 6 composition (A-6), and a polyamide 6/66/12 composition (B-1). By the method, the laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 5
In Example 1, the polyamide 12 composition (A-1) was changed to a semi-aromatic polyamide (E-1), and the extrusion temperature of (E-1) was changed to 280 ° C. By the method, the laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 6
In Example 1, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 1 except not using a polyamide 6/66/12 composition (B-1). The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 7
In Example 1, except that the polyamide 6/66/12 composition (B-1) was changed to (B-3), a laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 1. Obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 8
In Example 1, except that the polyamide 6/66/12 composition (B-1) was changed to (B-4), a laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 1. Obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 9
In Example 1, it shows in Table 1 by the method similar to Example 1 except having changed the polyamide 6/66/12 composition (B-1) into the polyamide 6/12 composition (B-5). A laminated tube having a layer structure was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 10
In Example 1, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 1 except having changed the fluorine-containing polymer (D-1) into (D-3). The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 11
In Example 1, except that the fluorine-containing polymer (D-1) was changed to the conductive fluorine-containing polymer (D-4) and the extrusion temperature of (D-4) was changed to 310 ° C. 1 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Comparative Example 12
In Example 1, except that the fluorine-containing polymer (D-1) was changed to (D-7) and the extrusion temperature of (D-7) was changed to 310 ° C., the same method as in Example 1 was used. The laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 13
In Example 1, except that the fluorine-containing polymer (D-1) was changed to the conductive fluorine-containing polymer (D-8) and the extrusion temperature of (D-8) was changed to 320 ° C. 1 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Comparative Example 14
In Example 1, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 1 except having changed the fluorine-containing polymer (D-1) into (D-11). The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 15
In Example 1, except that the fluorine-containing polymer (D-1) was changed to the conductive fluorine-containing polymer (D-12) and the extrusion temperature of (D-12) was changed to 310 ° C. 1 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Comparative Example 16
Example 2 is the same as Example 2 except that the fluorine-containing polymer (D-1) is changed to the polyamide 12 composition (A-2) and the extrusion temperature of (A-2) is changed to 250 ° C. The laminated tube of the layer structure shown in Table 1 was obtained by this method. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 17
Example 2 except that the fluorine-containing polymer (D-1) was changed to the conductive polyamide 12 composition (A-3) and the extrusion temperature of (A-3) was changed to 260 ° C. in Example 2. The laminated tube of the layer structure shown in Table 1 was obtained by the same method. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

As is clear from Table 1, the laminated tube of Comparative Example 1 that does not have a layer containing the saponified ethylene / vinyl acetate copolymer defined in the present invention or a layer containing a fluorine-containing polymer is a deteriorated fuel. The laminated tube of Comparative Example 2 that does not have a layer containing the saponified ethylene / vinyl acetate copolymer defined in the present invention is inferior in permeation resistance to low-concentration alcohol-containing gasoline. It was. The laminated tube of Comparative Example 3, which does not have a layer containing a fluorine-containing polymer as defined in the present invention and has a layer containing polyamide 6 as the innermost layer, is resistant to deterioration fuel resistance and high-concentration alcohol-containing gasoline. It was inferior in prevention. The laminated tube of Comparative Example 4 which does not have a layer containing an aliphatic polyamide defined in the present invention or a layer containing a polyamide 6/66/12 composition was inferior in low temperature impact resistance and deterioration fuel resistance. The laminated tube of Comparative Example 5 which does not have a layer containing the aliphatic polyamide specified in the present invention was inferior in low-temperature impact resistance and resistance to deterioration fuel. The laminated tube of Comparative Example 6 that did not have a layer containing the polyamide 6/66/12 composition defined in the present invention was inferior in interlayer adhesion. The laminated tubes of Comparative Examples 7 to 9 having a layer containing a polyamide 6/66/12 composition other than those specified in the present invention were inferior in interlayer adhesion after heat treatment. The laminated tubes of Comparative Examples 10 to 15 having a layer containing a fluorine-containing polymer other than those specified in the present invention were inferior in interlayer adhesion. The laminated tube of Comparative Examples 16 and 17 which does not have a layer containing a fluorine-containing polymer defined in the present invention and has a layer containing polyamide 12 as the innermost layer is used to prevent permeation to gasoline containing high concentration alcohol. The elution resistance of the monomer and oligomer was inferior.
On the other hand, the laminated tubes of Examples 1 to 17 defined in the present invention have low temperature impact resistance, deteriorated fuel resistance, chemical liquid permeation prevention property, particularly permeation prevention property for gasoline containing low to high concentration alcohol, interlayer adhesion. It is clear that various properties such as property and durability, and elution resistance of monomers and oligomers are good.

Claims (9)

A laminated tube comprising at least four layers, including (a) layer, (b) layer, (c) layer, and (d) layer,
The layer (a) contains an aliphatic polyamide (A),
The layer (b) includes a polyamide 6/66/12 composition (B),
The layer (c) includes a saponified ethylene / vinyl acetate copolymer (C),
The layer (d) includes a fluorine-containing polymer (D) in which a functional group having reactivity with an amino group is introduced into a molecular chain,
The aliphatic polyamide (A) does not include poly (caproamide / hexamethylene adipamide / dodecanamide) (polyamide 6/66/12),
The polyamide 6/66/12 composition (B) comprises polyhexamethylene sebamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene decanamide (polyamide 910), polynonamethylene dodecamide. (Polyamide 912), polydecamethylene decanamide (polyamide 1010), polydecane methylene dodecane (polyamide 1012), and at least one polyamide selected from the group consisting of polydocamethylene dodecamide (polyamide 1212), and polyamide 6 / 66/12 polyamide mixture (B1) 50 mass% or more and 98 mass% or less, plasticizer (B2) 1 mass% or more and 20 mass% or less, and the flexural modulus measured according to ISO 178 is 500 MPa or less. 1 mass of olefin polymer (B3) % To 30% by mass or less.   The aliphatic polyamide (A) is polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene decanamide ( Polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecane methylene decanamide (polyamide 1010), polydecamethylene dodecane (polyamide 1012), and polydodecamethylene dodecane (polyamide 1212). The laminated tube according to claim 1, wherein the laminated tube is at least one homopolymer or a copolymer using several kinds of raw material monomers forming them.   In the polyamide 6/66/12 in the polyamide 6/66/12 composition (B), the mass ratio of the total units of caproamide units and hexamethylene adipamide units to dodecanamide units is caproamide units, hexamethylene adipa. The laminated tube according to claim 1 or 2, wherein the ratio is 81: 19% by mass or more and 95: 5% by mass or less with respect to 100% by mass in total of the amide unit and the dodecanamide unit.   The ethylene content of the saponified ethylene / vinyl acetate copolymer (C) is 15 mol% or more and 60 mol% or less, and the saponification degree is 90 mol% or more. A laminated tube as described in 1.   The (a) layer containing the aliphatic polyamide (A) is disposed in the outermost layer, and the (c) layer containing the saponified ethylene / vinyl acetate copolymer (C) contains the aliphatic polyamide (A). The laminated tube according to any one of claims 1 to 4, wherein the laminated tube is disposed between the (a) layer and the (d) layer containing the fluorine-containing polymer (D).   The (b) layer containing the polyamide 6/66/12 composition (B) contains the (a) layer containing the aliphatic polyamide (A) and the saponified ethylene / vinyl acetate copolymer (C) ( c) The laminated tube according to any one of claims 1 to 5, which is disposed between the layers.   The laminated tube according to any one of claims 1 to 6, wherein a conductive layer containing a fluorine-containing polymer composition containing a conductive filler is disposed in the innermost layer of the laminated tube.   The laminated tube according to any one of claims 1 to 7, wherein the laminated tube is manufactured by coextrusion molding.   The laminated tube according to any one of claims 1 to 8, wherein the laminated tube is used as a fuel tube.