JP2018196933A - Laminated tube - Google Patents

Abstract

To provide a laminated tube excellent in low-temperature impact resistance, barrier property against gasoline with high-content or low-content alcohol, interlayer adhesive property and durability thereof, and resistance to elution of low-molecular weight components.SOLUTION: A laminated tube has a layer comprising an aliphatic polyamide (polyamide 11, 12, etc.), a layer comprising a semi-aromatic polyamide composition, a layer comprising a polyamide-6 composition and/or a polyamide-6/66/12 composition, and a layer comprising an aliphatic polyketone. The layer comprising the polyamide-6 composition and/or the polyamide-6/66/12 composition and the layer comprising the aliphatic polyketone are disposed adjacent to each other to make at least one pair.SELECTED DRAWING: None

Description

  The present invention relates to a laminated tube.

  In the past, automotive piping tubes were made of metal, with excellent rust prevention and light weight, in response to the problem of rusting caused by antifreezing agents on roads and the need to prevent global warming and save energy. Replacement with resin 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.

  For automobile piping tubes, 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 barrier property against the chemical solution is not sufficient, and in particular, an improvement to the alcohol-containing gasoline barrier property is required.

  As a method for solving this problem, resins having good chemical barrier properties such as 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 / hexafluoropro Rene / 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).

  Furthermore, a molded product using a polyamide-based resin, particularly nylon 11 or nylon 12 that is excellent in strength, toughness, chemical resistance, and flexibility in the innermost layer, is used as a monomer by contact with the fuel, It has been confirmed that low molecular weight components such as oligomers gradually elute and precipitate in the fuel, and the engine cannot be started due to adhesion to the moving parts of the injector and fuel tank valve, and the internal pressure of the fuel tank is controlled. It has been pointed out that it may be a problem. Polynonamethylene terephthalamide (PA9T) is attracting attention as a tube component having excellent chemical barrier properties and monomer / oligomer elution resistance and low specific gravity and low cost. The present inventors have a layer composed of an aliphatic polyamide, a diamine unit containing 60 mol% or more of a 1,9-nonanediamine unit and / or 2-methyl-1,8-octanediamine unit with respect to all diamine units, A laminate comprising at least two layers having a layer made of a semi-aromatic polyamide composed of a dicarboxylic acid unit containing 60 mol% or more of a terephthalic acid unit and / or a naphthalenedicarboxylic acid unit with respect to all dicarboxylic acid units. A structure is proposed (see Patent Documents 2 to 5).

  In recent years, from the viewpoint of exhaustion of gasoline resources and environmental conservation, use of alcohol-containing gasoline (biofuel) obtained by adding alcohol such as ethanol derived from biomass (bioethanol) to gasoline is being promoted. For example, as biofuel, gasoline containing bioethanol, bioethanol 10% mixed gasoline (E10), bioethanol 85% mixed gasoline (E85), bioethanol 100% (E100) are in Brazil, North America, China, etc. There is an urgent need to develop a piping system for flex-fuel vehicles that can be used for both bioethanol-mixed gasoline and gasoline.

  Also, a multilayer structure of two or more layers in which a layer made of polyamide obtained by polycondensation containing hexamethylenediamine and adipic acid as main components and a layer made of aliphatic ketone are directly adjacent to each other, or a layer made of aliphatic ketone And a multilayer structure including an adhesive layer composed of a polyamide 6/66/12 copolymer having a specific polymerization composition ratio and a residual monomer, and a layer composed of a long-chain aliphatic polyamide (Patent Documents 6 and 7). reference). Furthermore, a multilayer structure in which a layer made of polyamide and a layer made of an aliphatic ketone in which the ratio of the terminal carboxyl group concentration to the terminal amino group concentration is in a specific range and the layer made of an aliphatic ketone are arranged directly adjacent to each other has been proposed (see Patent Document 8). ).

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 JP 7-266503 A Japanese Patent Laid-Open No. 11-245358 Japanese Patent Laid-Open No. 11-245340 US Pat. No. 2,495,286 JP-A-53-128690 JP 59-197427 A JP 61-91226 A JP 62-232434 A JP-A-62-53332 JP-A-63-3025 JP-A 63-105031 JP-A 63-154737 Japanese Patent Laid-Open No. 1-149829 JP-A-1-201333 JP-A-2-67319

  However, although polynonamethylene terephthalamide (PA9T) satisfies the barrier property against hydrocarbons, further improvement of the barrier property against high-concentration alcohol-containing gasoline such as ethanol is desired. In order to improve the barrier property against gasoline containing high concentration alcohol, there is a method of laminating fluoropolymers such as ethylene / tetrafluoroethylene copolymer (ETFE). However, for environmental reasons, the use of halogen-containing materials is avoided. At the same time, there is a problem of high specific gravity and high cost, using halogen-free materials, excellent barrier properties against low to high concentration alcohol-containing gasoline, and excellent elution resistance of low molecular weight components such as monomers and oligomers, Development of piping systems that can be used for various fuels is in demand.

  In addition, the laminated tube for fuel piping is generally processed into a tube having a desired shape in a state where bending stress is applied due to layout restrictions 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, it is one of important performances that should be considered not only in the initial stage but also in interlayer adhesion after heat treatment (durability of interlayer adhesion).

  Furthermore, although the laminated tube containing the aliphatic ketone has some excellent barrier properties against low-concentration alcohol-containing gasoline, further improvement is desired. In addition, in the above-mentioned document relating to a multilayer structure including an aliphatic ketone layer, the basic performance of the tube such as the amount of alcohol-containing gasoline permeated, the interlayer adhesion after heat treatment (durability of interlayer adhesion), and the elution amount of low molecular weight components, There is no specific technical data disclosure or technical suggestion. Further, in the comparative example of Document 6, it is disclosed that the interlayer adhesion strength between the polyamide 6 and the polyketone after bending is low and easily peeled off, but as shown in the examples described later, both the initial stage and after the heat treatment are sufficient. It was found to have a good peel strength.

  The object of the present invention is to solve the above-mentioned problems, and is a laminate excellent in low temperature impact resistance, barrier properties against gasoline containing low to high concentration alcohol, interlayer adhesion and durability, and elution resistance of low molecular weight components. To provide a tube.

  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 semi-aromatic polyamide composition, a polyamide 6 composition and / or Or a layer comprising a polyamide 6/66/12 composition, and a layer comprising an aliphatic polyketone, and at least one layer comprising a polyamide 6 composition and / or a polyamide 6/66/12 composition and an aliphatic polyketone Laminate tube that is placed adjacent to the layer containing the layer is low temperature impact resistance, barrier property against gasoline containing low to high concentration alcohol, interlayer adhesion and durability, elution resistance of low molecular weight components It has been found that they are excellent in various properties.

That is, the present invention
A laminated tube of four or more layers including (a) layer, (b) layer, (c) layer, and (d) layer,
At least one set of the (c) layer and the (d) layer are disposed adjacent to each other;
The layer (a) contains an aliphatic polyamide (A),
The layer (b) includes a semi-aromatic polyamide composition (B),
The layer (c) includes a polyamide 6 composition (C1) and / or a polyamide 6/66/12 composition (C2),
The layer (d) includes an aliphatic polyketone (D),
The aliphatic polyamide (A) does not include polycaproamide (polyamide 6) and / or poly (caproamide / hexamethylene adipamide / dodecanamide) (polyamide 6/66/12),
The semi-aromatic polyamide composition (B) includes a semi-aromatic polyamide (B1) or a semi-aromatic polyamide (B2),
The semi-aromatic polyamide (B1) contains 50 mol% or more of aliphatic diamine units having 9 or 10 carbon atoms with respect to the total diamine units of the semi-aromatic polyamide (B1). Containing 50 mol% or more of terephthalic acid units and / or naphthalenedicarboxylic acid units with respect to all dicarboxylic acid units of B1),
The semiaromatic polyamide (B2) contains 50 mol% or more of xylylenediamine units and / or bis (aminomethyl) naphthalene units with respect to all diamine units of the semiaromatic polyamide (B2), Containing 50 mol% or more of aliphatic dicarboxylic acid units having 9 or 10 carbon atoms, based on all dicarboxylic acid units of the aromatic polyamide (B2),
The polyamide 6 composition (C1) comprises polycaproamide (polyamide 6) (C11) 50% by mass to 98% by mass, plasticizer (C3) 1% by mass to 20% by mass, and an elastomer polymer (C4). Containing 1% by mass or more and 30% by mass or less,
The polyamide 6/66/12 composition (C2) is composed of 50% by mass to 98% by mass of a polyamide mixture, 1% by mass to 20% by mass of a plasticizer (C3), and an elastomer polymer (C4) 1 Containing from 30% to 30% by weight,
The polyamide mixture contains polyamide 6/66/12 (C21) 50 mass% to 100 mass% and polyamide (C22) other than polyamide 6/66/12 (C21) 0 mass% to 50 mass%. Including
The elastomer polymer (C4) is a laminated tube containing a structural unit derived from an unsaturated compound having a carboxyl group and / or an acid anhydride group.

［一般式（１）において、Ｘはエチレン性不飽和化合物に由来する、炭素原子数３以上を有する有機基を表し、ｍ及びｎは正の整数を表す。］
［６］前記（ａ）層が、最外層に配置され、
前記（ｃ）層が、前記（ａ）層と前記（ｄ）層との間に配置される積層チューブ。
［７］少なくとも１組の前記（ａ）層と前記（ｃ）層とが隣接して配置される積層チューブ。
［８］前記（ｄ）層が、最内層に配置され、
前記脂肪族ポリケトン（Ｄ）は、更に導電性フィラーを含む積層チューブ。
［９］共押出成形法により製造される積層チューブ。
［１０］燃料チューブとして使用される積層チューブ。
また、本発明は、
（ａ）層、（ｂ）層、（ｃ）層、及び（ｄ）層を含む４層以上の積層チューブであって、
少なくとも１組の前記（ｃ）層と前記（ｄ）層とが隣接して配置され、
前記（ａ）層は、脂肪族ポリアミド（Ａ）を含み、
前記（ｂ）層は、半芳香族ポリアミド組成物（Ｂ）を含み、
前記（ｃ）層は、ポリアミド６組成物（Ｃ１）及び／又はポリアミド６／６６／１２組成物（Ｃ２）を含み、
前記（ｄ）層は、脂肪族ポリケトン（Ｄ）を含み、
前記脂肪族ポリアミド（Ａ）は、ポリカプロアミド（ポリアミド６）及び／又はポリ（カプロアミド／ヘキサメチレンアジパミド／ドデカンアミド）（ポリアミド６／６６／１２）を含まず、
前記半芳香族ポリアミド組成物（Ｂ）は、半芳香族ポリアミド（Ｂ１）又は半芳香族ポリアミド（Ｂ２）を含み、
前記半芳香族ポリアミド（Ｂ１）は、前記半芳香族ポリアミド（Ｂ１）の全ジアミン単位に対して、脂肪族ジアミン単位を５０モル％以上含み、前記半芳香族ポリアミド（Ｂ１）の全ジカルボン酸単位に対して、芳香族カルボン酸単位を５０モル％以上含み、
前記半芳香族ポリアミド（Ｂ２）は、前記半芳香族ポリアミド（Ｂ２）の全ジアミン単位に対して、芳香族ジアミン単位を５０モル％以上含み、前記半芳香族ポリアミド（Ｂ２）の全ジカルボン酸単位に対して、脂肪族ジカルボン酸単位を５０モル％以上含み、
前記ポリアミド６組成物（Ｃ１）は、ポリカプロアミド（ポリアミド６）（Ｃ１１）、可塑剤（Ｃ３）、及びエラストマー重合体（Ｃ４）を含有し、
前記ポリアミド６／６６／１２組成物（Ｃ２）は、ポリアミド６／６６／１２（Ｃ２１）、可塑剤（Ｃ３）、及びエラストマー重合体（Ｃ４）を含有する積層チューブである。 The preferable aspect of a laminated tube is shown below. A plurality of preferred embodiments can be combined.
[1] The aliphatic polyamide (A) includes polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene decanamide (polyamide 610), poly At least one single selected from the group consisting of hexamethylene dodecamide (polyamide 612), polydecane methylene decanamide (polyamide 1010), polydecamethylene dodecane (polyamide 1012), and polydodecamethylene dodecane (polyamide 1212). A laminated tube which is a polymer and / or a copolymer using several kinds of raw material monomers forming these.
[2] A laminated tube in which the semi-aromatic polyamide composition (B) contains the elastomer polymer (C4).
[3] The polyamide 6/66/12 (C21) is a laminated tube in which a mass ratio of a total unit of caproamide units and hexamethylene adipamide units to a dodecanamide unit is 81:19 or more and 95: 5.
[4] The polyamide (C22) is other than polyamide 6/66/12 (C21), and is polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexa Methylene adipamide (polyamide 66), polyhexamethylene sebamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene decanamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), At least one homopolymer selected from the group consisting of polydecane methylene decanamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), and polydocamethylene dodecamide (polyamide 1212), and / or forming these To do Laminate tube is a copolymer using several kinds of monomers.
[5] The laminated tube according to any one of claims 1 to 4, wherein the aliphatic polyketone (D) is a polymer having a repeating unit represented by the following formula (1).

[In General Formula (1), X represents an organic group having 3 or more carbon atoms derived from an ethylenically unsaturated compound, and m and n represent a positive integer. ]
[6] The layer (a) is disposed on the outermost layer,
A laminated tube in which the (c) layer is disposed between the (a) layer and the (d) layer.
[7] A laminated tube in which at least one pair of the (a) layer and the (c) layer is disposed adjacent to each other.
[8] The layer (d) is disposed in the innermost layer,
The aliphatic polyketone (D) is a laminated tube further containing a conductive filler.
[9] A laminated tube manufactured by a coextrusion molding method.
[10] A laminated tube used as a fuel tube.
The present invention also provides:
A laminated tube of four or more layers including (a) layer, (b) layer, (c) layer, and (d) layer,
At least one set of the (c) layer and the (d) layer are disposed adjacent to each other;
The layer (a) contains an aliphatic polyamide (A),
The layer (b) includes a semi-aromatic polyamide composition (B),
The layer (c) includes a polyamide 6 composition (C1) and / or a polyamide 6/66/12 composition (C2),
The layer (d) includes an aliphatic polyketone (D),
The aliphatic polyamide (A) does not include polycaproamide (polyamide 6) and / or poly (caproamide / hexamethylene adipamide / dodecanamide) (polyamide 6/66/12),
The semi-aromatic polyamide composition (B) includes a semi-aromatic polyamide (B1) or a semi-aromatic polyamide (B2),
The semi-aromatic polyamide (B1) contains 50 mol% or more of aliphatic diamine units with respect to the total diamine units of the semi-aromatic polyamide (B1), and the total dicarboxylic acid units of the semi-aromatic polyamide (B1). With respect to the aromatic carboxylic acid unit 50 mol% or more,
The semi-aromatic polyamide (B2) contains 50 mol% or more of aromatic diamine units with respect to the total diamine units of the semi-aromatic polyamide (B2), and the total dicarboxylic acid units of the semi-aromatic polyamide (B2). In contrast, the aliphatic dicarboxylic acid unit contains 50 mol% or more,
The polyamide 6 composition (C1) contains polycaproamide (polyamide 6) (C11), a plasticizer (C3), and an elastomer polymer (C4).
The polyamide 6/66/12 composition (C2) is a laminated tube containing polyamide 6/66/12 (C21), a plasticizer (C3), and an elastomer polymer (C4).

  ADVANTAGE OF THE INVENTION According to this invention, the laminated tube excellent in low temperature impact resistance, the barrier property with respect to gasoline containing a low concentration to a high concentration alcohol, interlayer adhesiveness and its durability, and the elution resistance of a low molecular weight component can be provided. .

  In the present specification, the amount of each component in the composition is the total amount of the plurality of substances present in the composition unless there is a specific indication when there are a plurality of substances corresponding to each component in the composition. means.

  The laminated tube according to this embodiment includes a layer containing an aliphatic polyamide, a layer containing a semi-aromatic polyamide composition, a layer containing a polyamide 6 composition and / or a polyamide 6/66/12 composition, and an aliphatic polyketone. A layer comprising at least one polyamide 6 composition and / or a polyamide 6/66/12 composition and a layer comprising an aliphatic polyketone are disposed adjacent to each other, Excellent barrier properties against alcohol-containing gasoline and excellent properties such as low temperature impact resistance and elution resistance of low molecular weight components. In particular, it is suitable as a fuel tube because it has excellent barrier properties against gasoline containing low to high concentration alcohol. Further, after contact / immersing in fuel for a long time, after heat treatment, etc., the decrease in interlayer adhesion is small, the durability of interlayer adhesion is excellent, and the amount of elution of low molecular weight components such as monomers and oligomers is small. Therefore, the laminated tube according to the present embodiment can be used in any environment, has high reliability, and has a very high utility value.

1. (A) Layer The (a) layer of the laminated tube contains an aliphatic polyamide (A).

[Aliphatic polyamide (A)]
Aliphatic polyamide (A) has an amide bond (—CONH—) in the main chain, and is melted using as raw materials lactam, aminocarboxylic acid, or aliphatic diamine and aliphatic dicarboxylic acid, which are aliphatic polyamide structural units. It can be obtained by polymerization or copolymerization by a known method such as polymerization, solution polymerization, and solid phase polymerization (hereinafter sometimes referred to as aliphatic polyamide (A)). However, the aliphatic polyamide (A) does not contain polycaproamide (polyamide 6) and / or poly (caproamide / hexamethylene adipamide / dodecanamide) (polyamide 6/66/12).

  Examples of the lactam include enantolactam, undecane lactam, dodecane lactam, α-pyrrolidone, α-piperidone and the like. Examples of the aminocarboxylic acid include 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. 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 polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyethylene adipamide (polyamide 26), polytetramethylene succinamide (polyamide 44), and polytetramethylene glutamide. (Polyamide 45), polytetramethylene adipamide (polyamide 46), polytetramethylene suberamide (polyamide 48), polytetramethylene azelamide (polyamide 49), polytetramethylene sebamide (polyamide 410), polytetramethylene Dodecamide (polyamide 412), polypentamethylene succinamide (polyamide 54), polypentamethylene glutamide (polyamide 55), polypentamethylene adipamide (polyamide 56), polypentamethylene suberami (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 sebacamide (polyamide 610), poly Hexamethylene dodecamide (polyamide 612), polyhexamethylene tetradecanamide (polyamide 614), polyhexamethylene hexadecanamide (polyamide 616), polyhexamethylene octadecanamide (polyamide 6) 8) Polynonamethylene adipamide (Polyamide 96), Polynonamethylene suberamide (Polyamide 98), Polynonamethylene azelamide (Polyamide 99), Polynonamethylene sebamide (Polyamide 910), Polynonamethylene dodecamide (Polyamide 912), polydecamethylene adipamide (polyamide 106), polydecamethylene suberamide (polyamide 108), polydecamethylene azelamide (polyamide 109), polydecamethylene sebamide (polyamide 1010), polydecamethylene Dodecamide (polyamide 1012), polydodecamethylene adipamide (polyamide 126), polydodecamethylene suberamide (polyamide 128), polydodecamethylene azelamide (polyamide 129), polydodecamethylene sebacamide (polyamide) Examples thereof include homopolymers such as lyamide 1210) and polydodecamethylene dodecamide (polyamide 1212), and / or copolymers using several kinds of raw material monomers forming these.

  Among these, the physical properties such as mechanical properties and heat resistance of the obtained laminated tube are sufficiently secured, and from the viewpoint of economy and availability, polyundecanamide (polyamide 11), polydodecanamide (polyamide 12). ), Polyhexamethylene adipamide (polyamide 66), polyhexamethylene decanamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecamethylene decanamide (polyamide 1010), polydecamethylene dodecamide (polyamide) 1012) and at least one homopolymer selected from the group consisting of polydodecamethylene dodecamide (polyamide 1212), and / or a copolymer using several kinds of raw material monomers forming these.

  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 the polymerization method, known methods such as melt polymerization, solution polymerization, and 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.

  When the terminal amino group concentration per 1 g of aliphatic polyamide (A) is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), the interlayer adhesion of the laminated tube and its durability Is preferably [A]> [B] +5, more preferably [A]> [B] +10, and further preferably [A]> [B] +15. preferable. Furthermore, from the viewpoint of the melt stability of the polyamide and the suppression of the generation of gelled material, [A]> 20 is preferable, 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 aliphatic polyamide (A) 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, and 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 acid, dicarboxylic acid, and tricarboxylic acid 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 , Tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, octadecyleneamine, eicosylamine, docosylamine and other aliphatic monoamines; cyclohexylamine, methylcyclohexylamine and other alicyclic monoamines; 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 Aliphatic diamines such as amine, 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) ) Cycloaliphatic diamines such as norbornane, 3,8-bis (aminomethyl) tricyclodecane, 4,9-bis (aminomethyl) tricyclodecane; aromatics such as m-xylylenediamine and 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 in which an alkyleneimine such as ethyleneimine or propyleneimine is ionically polymerized, or a method in which an alkyloxazoline is polymerized and then the polymer is partially or completely hydrolyzed. 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 The homopolymer and / or copolymer obtained by superposing | polymerizing a seed | species or more by a conventional method are mentioned. 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. The polyalkyleneimine is usually derived from the reactivity of the active hydrogen atom on the nitrogen atom contained therein, and in addition to the tertiary amino group, the primary amino group and / or the secondary amino group having an active hydrogen atom. (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 and 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, Aliphatic dicarboxylic acids such as icosanedioic acid, eicosenedioic acid, docosanedioic acid, diglycolic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid; 1,3-cyclohexanedicarboxylic acid, Alicyclic dicarboxylic acids such as 1,4-cyclohexanedicarboxylic acid and norbornane dicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, m-xylylenedicarboxylic acid, p-xylylenedicarboxylic 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 aliphatic polyamide (A) 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 to 20 meq / mol, more preferably 1 meq / mol to 10 meq / mol (the amino group equivalent (eq) is a carboxyl group). The amount of the amino group that reacts 1: 1 with the amide group is 1 equivalent).

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

  The aliphatic polyamide (A) may be a mixture of two or more types of polyamides having different end group concentrations as long as the end 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), a plasticizer (C3) described in the following polyamide 6 composition (C1) and / or polyamide 6/66/12 composition (C2) is added. May be.
The content of the plasticizer (C3) is 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. It is preferable that it is 2 parts by mass or more and 20 parts by mass or less.

In order to improve the low temperature impact resistance of the aliphatic polyamide (A), it is preferable to add an impact modifier, and in particular, the polyamide 6 composition (C1) and / or the polyamide 6/66/12 composition described later. It is more preferable to add an elastomer polymer (C4) containing a structural unit derived from an unsaturated compound having a carboxyl group and / or an acid anhydride group described in (C2). If the elastomer polymer (C4) described later does not have a carboxyl group and / or an acid anhydride group, the impact improving effect may be insufficient.
The content of the impact modifier 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 preferably 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 70% by mass or more.

  Other polyamide resins include polymetaxylylene succinamide (polyamide MXD4), polymetaxylylene glutaamide (polyamide MXD5), polymetaxylylene adipamide (polyamide MXD6), polymetaxylylene veramide (polyamide MXD8). , Polymetaxylylene decamide (polyamide MXD12), polymetaxylylene terephthalamide (polyamide MXDT), polymetaxylylene isophthalamide (polyamide MXDI), polymetaxylylene hexahydroterephthalamide (polyamide MXDT (H)), polymer Taxylylene naphthalamide (polyamide MXDN), polyparaxylylene succinamide (polyamide PXD4), polyparaxylylene glutamide (polyamide PXD5), polyparaxylylene adipami (Polyamide PXD6), polyparaxylylene beramide (polyamide PXD8), 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), 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 isophthalamide (polyamide 9I), polynonamethylene hexahydroterephthalamide (polyamide 9T (H)), poly (2-methyloctamethylene isophthalamide) ( Polyamide M8I), poly (2-methyloctamethylenehexahydroterephthalamide) (polyamide M8T (H)), polytrimethylhexamethyleneisophthalamide (polyamide TMHI), polytrimethylhexamethylenehexahydroterephthalamide (polyamide) MHT (H)), polydecamethylene isophthalamide (polyamide 10I), polydecamethylene hexahydroterephthalamide (polyamide 10T (H)), polyundecamethylene terephthalamide (polyamide 11T), polyundecamethylene iso Phthalamide (Polyamide 11I), Polyundecamethylene hexahydroterephthalamide (Polyamide 11T (H)), Polyundecamethylene naphthalamide (Polyamide 11N), Polydodecamethylene terephthalamide (Polyamide 12T), Polydodecamethylene iso Homopolymers such as phthalamide (polyamide 12I), polydodecamethylene hexahydroterephthalamide (polyamide 12T (H)), polydodecamethylene naphthalamide (polyamide 12N), and / or raw material monomers of these polyamides It includes a copolymer using seeds. 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); 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 / Polystyrene resins such as styrene copolymer (SEBS) and styrene / ethylene / propylene / styrene copolymer (SEPS); functional groups such as carboxyl groups and salts thereof, acid anhydride groups, and epoxy groups Polyolefin resin and polystyrene resin; Polyb Renterephthalate (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); Polyether resins such as (POM) and polyphenylene ether (PPO); polysulfones such as polysulfone (PSU), polyethersulfone (PESU), and polyphenylsulfone (PPSU) Polythiol resins such as polyphenylene sulfide (PPS) and polythioether sulfone (PTES); polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether ether Polyketone resins such as ether ketone (PEEEEK), polyether ether ketone ketone (PEEKK), polyether ketone ketone ketone (PEKKK), polyether ketone ether ketone ketone (PEKEKK); polyacrylonitrile (PAN), polymethacrylonitrile, Acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), acrylonitrile / butadiene copolymer (NBR) and other polynitrile resins; polymethyl methacrylate (PMMA) and polymethacrylate resins such as polyethyl methacrylate (PEMA); polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC) ), Polyvinyl chloride such as vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer; cellulose resin such as cellulose acetate and cellulose butyrate; polycarbonate resin such as polycarbonate (PC); thermoplastic polyimide (TPI), polyetherimide, polyesterimide, polyamideimide (PAI), polyesteramideimide and other polyimide resins; thermoplastic polyurethane resins; polyamide elastomers, polyurethane elastomers, polyester resins In some cases, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE), polychlorofluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE). , Ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (THV), tetrafluoroethylene / Hexafluoropropylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (PFA), tetrafluoroethylene Examples thereof include fluororesins such as a tylene / hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer and a chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer (CPT). 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. , And a coloring agent may be added.

2. (B) Layer The (b) layer of the laminated tube contains the semi-aromatic polyamide composition (B).

[Semi-aromatic polyamide composition (B)]
The semi-aromatic polyamide composition (B) includes a semi-aromatic polyamide (B1) or a semi-aromatic polyamide (B2), and the semi-aromatic polyamide (B1) is a total diamine of the semi-aromatic polyamide (B1). 50 mol% or more of aliphatic diamine units having 9 or 10 carbon atoms with respect to the units, and terephthalic acid units and / or naphthalenedicarboxylic acid units with respect to all dicarboxylic acid units of the semiaromatic polyamide (B1) The semi-aromatic polyamide (B2) contains 50 mol% of xylylenediamine units and / or bis (aminomethyl) naphthalene units with respect to the total diamine units of the semi-aromatic polyamide (B2). % Of the aliphatic dicarboxylic acid unit having 9 or 10 carbon atoms with respect to the total dicarboxylic acid unit of the semi-aromatic polyamide (B2). Including more than 50 mol% (hereinafter sometimes referred to as semi-aromatic polyamide composition (B).).

[Semi-aromatic polyamide (B1)]
The semi-aromatic polyamide composition (B) has an embodiment containing the semi-aromatic polyamide (B1) (hereinafter sometimes referred to as semi-aromatic polyamide (B1)), and the semi-aromatic polyamide (B1) is With respect to all diamine units of the semi-aromatic polyamide (B1), diamine units containing 50 mol% or more of aliphatic diamine units having 9 or 10 carbon atoms, and all dicarboxylic acid units of the semi-aromatic polyamide (B1) And a dicarboxylic acid unit containing 50 mol% or more of a terephthalic acid unit and / or a naphthalenedicarboxylic acid unit.

  The content of the aliphatic diamine unit having 9 or 10 carbon atoms in the semi-aromatic polyamide (B1) has sufficient physical properties such as heat resistance, chemical resistance, impact resistance and chemical barrier properties of the obtained laminated tube. From the viewpoint of ensuring the above, it is at least 50 mol%, preferably at least 55 mol%, more preferably at least 60 mol%, based on the total diamine units of the semi-aromatic polyamide (B1).

  Examples of the aliphatic diamine unit having 9 or 10 carbon atoms include units derived from 1,9-nonanediamine, 1,10-decanediamine and the like. As long as the number of carbon atoms satisfies the above, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2,4-diethyl-1,6-hexane Diamine, 2,2-dimethyl-heptanediamine, 2,3-dimethyl-heptanediamine, 2,4-dimethyl-heptanediamine, 2,5-dimethyl-heptanediamine, 2-methyl-1,8-octanediamine, 3 -Methyl-1,8-octanediamine, 4-methyl-1,8-octanediamine, 1,3-dimethyl-1,8-octanediamine, 1,4-dimethyl-1,8-octanediamine, 2,2 -Dimethyl-1,8-octanediamine, 2,4-dimethyl-1,8-octanediamine, 3,3-dimethyl-1,8-octanediamine, 3,4-dimethyl -1,8-octanediamine, 4,4-dimethyl-1,8-octanediamine, 4,5-dimethyl-1,8-octanediamine, 2-methyl-1,9-nonanediamine, 3-methyl-1, A unit derived from a branched aliphatic diamine such as 9-nonanediamine, 4-methyl-1,9-nonanediamine, and 5-methyl-1,9-nonanediamine may be contained. These can use 1 type (s) or 2 or more types.

  Among the aliphatic diamine units having 9 or 10 carbon atoms, from the viewpoint of availability and economic efficiency, from 1,9-nonanediamine, 2-methyl-1,8-octanediamine, and 1,10-decanediamine. Derived units are preferred. Further, when 1,9-nonanediamine and 2-methyl-1,8-octanediamine are used in combination, the molar ratio of 1,9-nonanediamine unit to 2-methyl-1,8-octanediamine unit is determined by the moldability and resistance to resistance. From the viewpoint of balance of impact properties, it is preferably 30:70 mol% or more and 98: 2 mol% or less, and more preferably 40:60 mol% or more and 95: 5 mol% or less.

  The diamine unit in the semi-aromatic polyamide (B1) includes other diamine units other than the aliphatic diamine unit having 9 or 10 carbon atoms as long as the excellent properties of the obtained laminated tube are not impaired. You may go out. Other diamine units include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, , 8-octanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, etc. 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) 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 (aminoethyl) piperazine, 2,5-bis (aminomethyl) norbornane, 2,6-bis (aminomethyl) norbornane, 3,8-bis (aminomethyl) ) Units derived from alicyclic diamines such as tricyclodecane and 4,9-bis (aminomethyl) tricyclodecane; m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine 1,4-bis (aminomethyl) naphthalene, 1,5-bis (aminomethyl) Phthalene, 2,6-bis (aminomethyl) naphthalene, 2,7-bis (aminomethyl) naphthalene, 4,4′-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 4,4′- Examples include units derived from aromatic diamines such as diaminodiphenyl sulfone and 4,4′-diaminodiphenyl ether, and these may be used alone or in combination of two or more. The content of these other diamine units is less than 50 mol%, preferably 45 mol% or less, and preferably 40 mol% or less, based on the total diamine units of the semiaromatic polyamide (B1). More preferred.

  Further, the content of the terephthalic acid unit and / or naphthalenedicarboxylic acid unit in the semi-aromatic polyamide (B1) sufficiently secures various physical properties such as heat resistance, chemical resistance and chemical barrier property of the obtained laminated tube. From the viewpoint, it is 50 mol% or more, preferably 55 mol% or more, and more preferably 60 mol% or more with respect to all dicarboxylic acid units of the semi-aromatic polyamide (B1).

  Examples of the naphthalenedicarboxylic acid unit include units derived from 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, and the like. These can use 1 type (s) or 2 or more types. Among the naphthalenedicarboxylic acid units, units derived from 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid are preferable in consideration of economy and availability.

  The dicarboxylic acid unit in the semi-aromatic polyamide (B1) is a dicarboxylic acid unit other than the terephthalic acid unit and / or the naphthalene dicarboxylic acid unit as long as the excellent properties of the obtained laminated tube are not impaired. May be included. Examples of other dicarboxylic acid units include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 2,2-diethylsuccinic acid, and suberin. Acid, azelaic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanediate Units derived from aliphatic dicarboxylic acids such as acid, octadecanedioic acid, eicosanedioic acid; alicyclic such as 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid Units derived from dicarboxylic acids; phthalic acid, isophthalic acid, 1,3-phenylenedioxydiacetic acid, , 4-phenylenedioxydiacetic acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylethane-4,4′-dicarboxylic acid, diphenylpropane-4,4′-dicarboxylic acid, Units derived from aromatic dicarboxylic acids such as diphenyl ether-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-triphenyldicarboxylic acid These may be used alone or in combination of two or more. Among these, units derived from aromatic dicarboxylic acids are preferred. The content of these other dicarboxylic acid units is less than 50 mol%, preferably 45 mol% or less, and preferably 40 mol% or less, based on all dicarboxylic acid units of the semi-aromatic polyamide (B1). It is more preferable. Furthermore, polycarboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid can be used as long as melt molding is possible.

  The semi-aromatic polyamide (B1) may contain other units other than the dicarboxylic acid unit and the diamine unit as long as the excellent properties of the obtained laminated tube are not impaired. Other units include units derived from lactams such as caprolactam, enantolactam, undecane lactam, dodecane lactam, α-pyrrolidone, α-piperidone; 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11 -Units derived from aminocarboxylic acids of aliphatic aminocarboxylic acids such as aminoundecanoic acid and 12-aminododecanoic acid; and aromatic aminocarboxylic acids such as p-aminomethylbenzoic acid. These can use 1 type (s) or 2 or more types. The content of other units is preferably 45 mol% or less, more preferably 40 mol% or less, and more preferably 35 mol% or less, based on the total monomer units of the semi-aromatic polyamide (B1). More preferably.

  Furthermore, as a semi-aromatic polyamide (B1) production apparatus, a batch-type 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 a kneading reaction extruder may be used. As the polymerization method, known methods such as melt polymerization, solution polymerization, and 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.

  When producing the semi-aromatic polyamide (B1), phosphoric acid, phosphorous acid, hypophosphorous acid, a salt or ester thereof, or the like can be added as a catalyst. Examples of phosphoric acid, phosphorous acid, hypophosphorous acid salts or esters include phosphoric acid, phosphorous acid, or hypophosphorous acid and potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin Metal salts such as tungsten, germanium, titanium, antimony, phosphoric acid, phosphorous acid, or ammonium salt of hypophosphorous acid, phosphoric acid, phosphorous acid, or hypophosphorous acid ethyl ester, isopropyl ester, butyl ester Hexyl ester, isodecyl ester, decyl ester, stearyl ester, phenyl ester and the like. These can use 1 type (s) or 2 or more types.

[Semi-aromatic polyamide (B2)]
The semi-aromatic polyamide composition (B) has an embodiment containing the semi-aromatic polyamide (B2) (hereinafter sometimes referred to as semi-aromatic polyamide (B2)), and the semi-aromatic polyamide (B2) is A diamine unit containing 50 mol% or more of xylylenediamine units and / or bis (aminomethyl) naphthalene units with respect to all diamine units of the semi-aromatic polyamide (B2), and all dicarboxylic acids of the semi-aromatic polyamide (B2) It contains a dicarboxylic acid unit containing 50 mol% or more of an aliphatic dicarboxylic acid unit having 9 or 10 carbon atoms based on the unit.

  The content of xylylenediamine units and / or bis (aminomethyl) naphthalene units in the semi-aromatic polyamide (B2) depends on the heat resistance, chemical resistance, impact resistance, chemical barrier properties, etc. of the resulting laminated tube. From the viewpoint of sufficiently securing the physical properties, it is 50 mol% or more, preferably 55 mol% or more, more preferably 60 mol% or more, based on all diamine units of the semi-aromatic polyamide (B2). preferable.

  Examples of the xylylenediamine unit include units derived from o-xylylenediamine, m-xylylenediamine, and p-xylylenediamine. These can use 1 type (s) or 2 or more types. Among the xylylenediamine units, units derived from m-xylylenediamine and p-xylylenediamine are preferable.

  As the bis (aminomethyl) naphthalene unit, 1,4-bis (aminomethyl) naphthalene, 1,5-bis (aminomethyl) naphthalene, 2,6-bis (aminomethyl) naphthalene, 2,7-bis (amino) And units derived from methyl) naphthalene. These can use 1 type (s) or 2 or more types. Among the bis (aminomethyl) naphthalene units, units derived from 1,5-bis (aminomethyl) naphthalene and 2,6-bis (aminomethyl) naphthalene are preferable.

  The diamine unit in the semi-aromatic polyamide (B2) is a diamine other than the xylylenediamine unit and / or the bis (aminomethyl) naphthalene unit as long as the excellent properties of the obtained laminated tube are not impaired. Units may be included. Other diamine units include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, , 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 Derived from aliphatic diamines such as amines, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine Unit: 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) 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 (aminoethyl) piperazine, 2,5-bis (aminomethyl) norbornane, 2,6-bis (aminomethyl) norbornane, 3,8-bis (aminomethyl) tricyclodecane, 4 , 9-bis (aminomethyl) tricyclodecane and other units derived from alicyclic diamines; m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 2,2-bis (4-amino) Examples include units derived from aromatic diamines such as phenyl) propane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl ether, and these may be used alone or in combination of two or more. Among these, units derived from aromatic diamines are preferred. The content of these other diamine units is less than 50 mol%, preferably 45 mol% or less, and preferably 40 mol% or less, based on the total diamine units of the semi-aromatic polyamide (B2). More preferred.

  Examples of the aliphatic dicarboxylic acid unit having 9 or 10 carbon atoms include units derived from azelaic acid, sebacic acid and the like. As long as the number of carbon atoms satisfies the above, it may contain a unit derived from a branched aliphatic dicarboxylic acid such as 2,2,4-trimethyladipic acid and 2,4,4-trimethyladipic acid. . These can use 1 type (s) or 2 or more types. Among the aliphatic dicarboxylic acid units having 9 or 10 carbon atoms, a unit derived from sebacic acid is preferable from the viewpoint of availability and economy.

  In addition, the content of the aliphatic dicarboxylic acid unit having 9 or 10 carbon atoms in the semi-aromatic polyamide (B2) has sufficient physical properties such as heat resistance, chemical resistance and chemical barrier properties of the obtained laminated tube. From the viewpoint of ensuring, it is 50 mol% or more, preferably 55 mol% or more, and more preferably 60 mol% or more with respect to all dicarboxylic acid units of the semi-aromatic polyamide (B2).

  The dicarboxylic acid unit in the semi-aromatic polyamide (B2) is a dicarboxylic acid other than the aliphatic dicarboxylic acid unit having 9 or 10 elementary atoms as long as it does not impair the excellent characteristics of the obtained laminated tube. Units may be included. Other dicarboxylic acid units include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, Units derived from aliphatic dicarboxylic acids such as hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid, 2-methyladipic acid, 2,2-dimethylglutaric acid, 2,2-diethylsuccinic acid, 2-butylsuberic acid Units derived from alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid; terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic Acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7 Naphthalenedicarboxylic acid, 1,3-phenylenedioxydiacetic acid, 1,4-phenylenedioxydiacetic acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylethane-4,4 ′ -Dicarboxylic acid, diphenylpropane-4,4'-dicarboxylic acid, diphenyl ether-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'- Examples thereof include units derived from aromatic dicarboxylic acids such as triphenyldicarboxylic acid, and these may be used alone or in combination of two or more. The content of these other dicarboxylic acid units is less than 50 mol%, preferably 45 mol% or less, and preferably 40 mol% or less, based on all dicarboxylic acid units of the semi-aromatic polyamide (B2). It is more preferable. Furthermore, polycarboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid can be used as long as melt molding is possible.

  The semi-aromatic polyamide (B2) may contain other units other than the dicarboxylic acid unit and the diamine unit as long as the excellent properties of the obtained laminated tube are not impaired. Other units include units derived from lactams such as caprolactam, enantolactam, undecane lactam, dodecane lactam, α-pyrrolidone, α-piperidone; 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11 -Units derived from aminocarboxylic acids of aliphatic aminocarboxylic acids such as aminoundecanoic acid and 12-aminododecanoic acid; and aromatic aminocarboxylic acids such as p-aminomethylbenzoic acid. These can use 1 type (s) or 2 or more types. The content of other units is preferably 45 mol% or less, more preferably 40 mol% or less, and more preferably 35 mol% or less, based on the total monomer units of the semi-aromatic polyamide (B2). More preferably.

  Semi-aromatic polyamide (B2) production equipment includes kneading in batch-type reaction kettles, single- or multi-tank continuous reaction equipment, tubular continuous reaction equipment, uniaxial kneading extruder, biaxial kneading extruder, etc. A known polyamide production apparatus such as a reaction extruder may be used. As a method for producing the semi-aromatic polyamide (B2), there are known methods such as melt polymerization, solution polymerization, and solid-phase polymerization. Group polyamide (B2) can be produced. These production methods can be used alone or in combination as appropriate, and among these, the melt polymerization method is preferable. For example, a nylon salt composed of xylylenediamine and / or bis (aminomethyl) naphthalene and an aliphatic dicarboxylic acid having 9 or 10 carbon atoms is pressurized, heated in the presence of water, added water and condensed water. It is produced by a method of polymerizing in a molten state while removing. It can also be produced by a method in which xylylenediamine and / or bis (aminomethyl) naphthalene is directly added to a molten aliphatic dicarboxylic acid having 9 or 10 carbon atoms and polycondensed under normal pressure. In this case, in order to keep the reaction system in a uniform liquid state, xylylenediamine and / or bis (aminomethyl) naphthalene is continuously added to the aliphatic dicarboxylic acid having 9 or 10 carbon atoms, Polymerization proceeds while raising the temperature of the reaction system so that the temperature is equal to or higher than the melting point of the generated oligoamide and polyamide. Further, the semi-aromatic polyamide (B2) may be subjected to solid phase polymerization after being produced by a melt polymerization method.

To the semi-aromatic polyamide (B2), a phosphorus atom-containing compound can be added as a catalyst or to improve processing stability during melt molding and to prevent coloring. Phosphorus atom-containing compounds include hypophosphorous acid, phosphorous acid, phosphoric acid, pyrophosphoric acid, metaphosphoric acid, phosphonous phosphonic acid and their derivatives, alkaline earth metal salts of hypophosphorous acid, phosphorous acid Alkali metal salt, alkaline earth metal salt of phosphorous acid, alkali metal salt of phosphoric acid, alkaline earth metal salt of phosphoric acid, alkali metal salt of pyrophosphoric acid, alkaline earth metal salt of pyrophosphoric acid, alkali of metaphosphoric acid Examples include metal salts, alkaline earth metal salts of metaphosphoric acid, alkali metal salts of phosphonous acid, alkaline earth metal salts of phosphonous acid, alkali metal salts of phosphonic acid, and alkaline earth metal salts of phosphonic acid It is done.
Examples of phosphorus atom-containing compounds include phosphinic acid (hypophosphorous acid), ethyl hypophosphite, dimethylphosphinic acid, phenylmethylphosphinic acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, Calcium phosphite, magnesium hypophosphite, phosphorous acid, triethyl phosphite, triphenyl phosphite, sodium phosphite, sodium hydrogen phosphite, potassium phosphite, potassium hydrogen phosphite, lithium phosphite , Lithium hydrogen phosphite, magnesium phosphite, magnesium hydrogen phosphite, calcium phosphite, calcium hydrogen phosphite, pyrophosphorous acid, phosphoric acid, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate , Potassium phosphate, dipotassium hydrogen phosphate, potassium dihydrogen phosphate, magnesium phosphate , Dimagnesium hydrogen phosphate, magnesium dihydrogen phosphate, calcium phosphate, dicalcium hydrogen phosphate, calcium dihydrogen phosphate, lithium phosphate, dilithium hydrogen phosphate, lithium dihydrogen phosphate, sodium pyrophosphate, potassium pyrophosphate , Magnesium pyrophosphate, calcium pyrophosphate, lithium pyrophosphate, sodium metaphosphate, potassium metaphosphate, magnesium metaphosphate, calcium metaphosphate, lithium metaphosphate, phosphonite, sodium phosphonite, lithium phosphonite, potassium phosphonite, Magnesium phosphonite, calcium phosphite, ethyl phenylphosphonite, sodium phenylphosphonite, potassium phenylphosphonite, lithium phenylphosphonite, phosphonic acid, phospho Sodium phosphate, potassium phosphonate, lithium phosphonate, potassium phosphonate, magnesium phosphonate, calcium phosphonate, phenylphosphonic acid, ethylphosphonic acid, sodium phenylphosphonate, potassium phenylphosphonate, lithium phenylphosphonate, diethyl phenylphosphonate , Sodium ethylphosphonate, potassium ethylphosphonate and the like. These can use 1 type (s) or 2 or more types. Among these, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, calcium hypophosphite, magnesium hypophosphite, calcium phosphite, calcium hydrogen phosphite, calcium dihydrogen phosphate, phosphorous acid Sodium, sodium phosphite, sodium hydrogen phosphite, potassium phosphite, potassium hydrogen phosphite, lithium phosphite, lithium hydrogen phosphite, magnesium phosphite, magnesium hydrogen phosphite, calcium phosphite, Calcium hydrogen phosphate is preferable, and sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, calcium hypophosphite, and magnesium hypophosphite are more preferable. These phosphorus atom-containing compounds may be hydrates.

The content of the phosphorus atom-containing compound is sufficient to ensure a catalytic effect and an anti-coloring effect during polymerization, and from the viewpoint of suppressing the generation of gel, the phosphorus atom concentration with respect to 100 parts by mass of the semi-aromatic polyamide (B2). It is preferably 0.030 to 0.30 parts by mass, more preferably 0.050 to 0.20 parts by mass, and 0.070 to 0.15 parts by mass. More preferably, it is as follows.
The addition method of these phosphorus atom-containing compounds is a method of adding to a nylon salt aqueous solution, a diamine or dicarboxylic acid, which is a raw material of the semi-aromatic polyamide (B2), a method of adding to a dicarboxylic acid in a molten state, Although the method of adding etc. is mentioned, as long as it can disperse | distribute uniformly in a semi-aromatic polyamide (B2), what kind of method may be sufficient and it is not limited to these.

  An alkali metal compound or an alkaline earth metal compound can be added to the semiaromatic polyamide (B2) in combination with the phosphorus atom-containing compound. In order to prevent coloring of the polyamide during polycondensation, it is necessary that a sufficient amount of the phosphorus atom-containing compound is present, but in some cases, the gelation of the polyamide may be caused, so that the amidation reaction rate is adjusted. In addition, it is preferable to coexist an alkali metal compound or an alkaline earth metal compound. Examples of alkali metal compounds include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal acetates, alkaline earth metal acetates, alkali metal carbonates, alkaline earth metal carbonates, alkali metal alkoxides, and alkalis. An earth metal alkoxide etc. are mentioned, An alkali metal hydroxide and / or an alkali metal acetate are preferable.

  Examples of the alkali metal compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, and other alkali metals / alkaline earth metals. Lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, magnesium acetate, calcium acetate, strontium acetate, barium acetate, and other alkali metal / alkaline earth metal acetates; lithium carbonate, sodium carbonate, Alkali metal / alkaline earth metal carbonates such as potassium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate; sodium methoxide, sodium ethoxide, sodium propoxide, Thorium butoxide, potassium methoxide, lithium methoxide, magnesium methoxide, alkoxides of an alkali metal / alkaline earth metal such as calcium methoxide and the like. These can use 1 type (s) or 2 or more types. Among these, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium acetate, and potassium acetate are preferable from the economical viewpoint.

When an alkali metal compound or an alkaline earth metal compound is added into the polycondensation system of the semi-aromatic polyamide (B2), the value obtained by dividing the number of moles of the compound by the number of moles of phosphorus atoms in the phosphorus atom-containing compound is: From the viewpoint of the balance between promotion and suppression of the amidation reaction, it is preferably 0.30 or more and 2.0 or less, more preferably 0.40 or more and 1.9 or less, and 0.50 or more and 1.8 or less. More preferably.
The addition method of these alkali metal compounds or alkaline earth metal compounds is a method of adding to a nylon salt aqueous solution, diamine or dicarboxylic acid which is a raw material of the semi-aromatic polyamide (B2), a method of adding to a dicarboxylic acid in a molten state Any method may be used as long as it can be uniformly dispersed in the semi-aromatic polyamide (B2), but the method is not limited to these.

  Based on JISK-6920, the relative viscosity of the semi-aromatic polyamide (B1) and the semi-aromatic polyamide (B2) measured under the conditions of 96% sulfuric acid, polymer concentration of 1% and 25 ° C. is obtained as a laminated tube. From the viewpoints of securing the mechanical properties of the above 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 4.0 or less, and 1.8 or more and 3 Is more preferably 0.5 or less, and further preferably 2.0 or more and 3.0 or less.

  In addition, there is no special restriction | limiting in the kind of terminal group of a semi-aromatic polyamide (B1) and a semi-aromatic polyamide (B2), its density | concentration, and molecular weight distribution. One or more of monoamine, diamine, polyamine, monocarboxylic acid and dicarboxylic acid can be added in combination as appropriate for molecular weight adjustment and melt stabilization during molding. For example, aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine; alicyclic such as cyclohexylamine, dicyclohexylamine Monoamines; aromatic monoamines such as aniline, toluidine, diphenylamine, naphthylamine; 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine, 2-methyl-1,5 -Aliphatic diamines such as pentanediamine; cycloaliphatic diamines such as cyclohexanediamine, bis (aminomethyl) cyclohexane, 5-amino-1,3,3-trimethylcyclohexanemethylamine; m-pheny Aromatic diamines such as polydiamine and p-phenylenediamine; polyamines such as polyalkyleneimine, polyalkylenepolyamine, polyvinylamine and polyallylamine; acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecyl acid Aliphatic monocarboxylic acids such as myristic acid, palmitic acid, stearic acid, pivalic acid and isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalene Aromatic monocarboxylic acids such as carboxylic acid, methylnaphthalene carboxylic acid and phenylacetic acid; aliphatic dicarboxylic acids such as adipic acid and pimelic acid, 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4 -Cyclohexanedicarboxylic acid Alicyclic dicarboxylic acids phthalic acid, aromatic dicarboxylic acids such as isophthalic acid. These can use 1 type (s) or 2 or more types. The amount of these molecular weight regulators used varies depending on the reactivity of the molecular weight regulator and the polymerization conditions, but is appropriately determined so that the relative viscosity of the finally obtained polyamide falls within the above range.

  Considering the melt stability, it is preferable that the ends of the molecular chains of the semi-aromatic polyamide (B1) and the semi-aromatic polyamide (B2) are sealed with an end-capping agent, and 10% or more of the end groups are sealed. It is more preferable that it is stopped, and it is still more preferable that 20% or more of the end groups are sealed. The end capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the end of the polyamide, but from the viewpoint of reactivity, stability of the capped end, etc. An acid or a monoamine is preferable, and a monocarboxylic acid is more preferable from the viewpoint of easy handling. In addition, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, monoalcohols, and the like can be used.

The monocarboxylic acid used as the end-capping agent is not particularly limited as long as it has reactivity with an amino group, but the above-mentioned aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid is not limited. A carboxylic acid etc. are mentioned. Among these, from the viewpoint of reactivity, stability of the sealing end, price, etc., acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid Benzoic acid is preferred. The monoamine used as the end-capping agent is not particularly limited as long as it has reactivity with a carboxyl group, and examples thereof include the aliphatic monoamines, alicyclic monoamines, and aromatic monoamines. Among these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are preferable from the viewpoints of reactivity, boiling point, sealing end stability, price, and the like.
The amount of the terminal blocking agent used can be appropriately selected in consideration of the reactivity, boiling point, reaction apparatus, reaction conditions, etc. of the terminal blocking agent used. From the viewpoint of adjusting the degree of polymerization, it is preferably 0.1 mol% or more and 15 mol% or less with respect to the total number of moles of the dicarboxylic acid and diamine which are raw material components.

In order to improve the low temperature impact resistance of the semiaromatic polyamide (B1) and the semiaromatic polyamide (B2), it is preferable to add an impact modifier to the semiaromatic polyamide composition (B). Containing a structural unit derived from an unsaturated compound having a carboxyl group and / or an acid anhydride group described in the polyamide 6 composition (C1) and / or the polyamide 6/66/12 composition (C2) It is more preferable to add an elastomer polymer (C4). If the elastomer polymer (C4) described later does not have a carboxyl group and / or an acid anhydride group, the impact improving effect may be insufficient.
The content of the impact modifier is 1 with respect to 100 parts by mass of the semi-aromatic polyamide (B1) or the semi-aromatic polyamide (B2) from the viewpoint of sufficiently ensuring the mechanical strength and low-temperature impact resistance of the laminated tube. The mass is preferably 30 parts by mass or more and more preferably 3 parts by mass or more and 25 parts by mass or less.

  The semi-aromatic polyamide composition (B) may contain other polyamide-based resin or other thermoplastic resin together with the semi-aromatic polyamide (B1) or the semi-aromatic polyamide (B2). Examples of other polyamide-based resins or other thermoplastic resins include the same resins as in the case of the aliphatic polyamide composition (A). Furthermore, it may be a mixture of the aliphatic polyamide (A1) and / or polyamide 6 (C11) and / or polyamide 6/66/12 (C22) described later. The content of the semi-aromatic polyamide (B1) or the semi-aromatic polyamide (B2) in the semi-aromatic polyamide composition (B) which is a mixture is preferably 60% by mass or more, and 70% by mass or more. It is more preferable.

  Further, the semi-aromatic polyamide composition (B) may be added to an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, an inorganic filler, an antistatic agent, a flame retardant, a crystal as necessary. Accelerators, plasticizers, colorants, lubricants, and the like may be added.

3. (C) Layer The (c) layer of the laminated tube comprises a polyamide 6 composition (C1) and / or a polyamide 6/66/12 composition (C2).
[Polyamide 6 composition (C1)]
The polyamide 6 composition (C1) has a polycaproamide (polyamide 6) of 50% by mass to 98% by mass, a plasticizer (C3) of 1% by mass to 20% by mass, and a carboxyl group and / or an acid anhydride group. The elastomer polymer (C4) containing a structural unit derived from an unsaturated compound having 1% by mass to 30% by mass (hereinafter sometimes referred to as a polyamide 6 composition (C1)).

[Polyamide 6 (C11)]
The polycaproamide (polyamide 6) is a polyamide having a caproamide unit represented by the following formula (—CO— (CH ₂ ) ₅ —NH—) _n having an amide bond (—CONH—) in the main chain ( Hereinafter, it may be referred to as polyamide 6 (C11).

[Polyamide 6/66/12 composition (C2)]
The polyamide 6/66/12 composition (C2) comprises a polyamide mixture in an amount of 50% by mass to 98% by mass, a plasticizer (C3) of 1% by mass to 20% by mass, and an elastomer polymer (C4) 1 The polyamide mixture contains polyamide 6/66/12 (C21) 50 mass% to 100 mass% and polyamides other than polyamide 6/66/12 (C21) (C22). The elastomer polymer (C4) contains 0 to 50% by mass, and the elastomer polymer (C4) contains structural units derived from an unsaturated compound having a carboxyl group and / or an acid anhydride group (hereinafter referred to as polyamide 6/66). / 12 composition (C2)).

[Polyamide 6/66/12 (C21)]
Polyamide 6/66/12 (poly (caproamide / hexamethylene adipamide / dodecanamide)) has the following formula having an amide bond (—CONH—) in the main chain: (—CO— (CH ₂ ) ₅ —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 A polyamide copolymer having a dodecanamide unit represented by —CO— (CH ₂ ) ₁₁ —NH—) n. Polyamide 6/66/12 can be obtained by copolymerizing 6-aminocaproic acid and / or caprolactam, hexamethylenediamine and adipic acid salt, and 12-aminododecanoic acid and / or dodecanactam (hereinafter referred to as polyamide). 6/66/12 (C21)).

In the polyamide 6/66/12 (C21), the mass ratio of the total unit of the caproamide unit and the hexamethylene adipamide unit and the dodecanamide unit is from the viewpoint of sufficiently ensuring the interlayer adhesion of the laminated tube and its durability. It is preferably 81: 19% by mass or more and 95: 5% by mass or less, and 83: 17% by mass or more and 92: 8 with respect to 100% by mass in total of caproamide unit, hexamethylene adipamide unit and dodecanamide unit. It is more preferable that the amount is not more than mass%.
In polyamide 6/66/12 (C21), the mass ratio of caproamide units to hexamethylene adipamide units ensures sufficient heat resistance of the laminated tube, and coextrusion with the semiaromatic polyamide composition (B) From the viewpoint of molding stability at the time, it is preferably 80: 20% by mass or more and 95: 5% by mass or less, and 82: 18% by mass with respect to 100% by mass in total of caproamide unit and hexamethylene adipamide unit. More preferably, it is 93: 7 mass% or less.

  The polyamide 6/66/12 composition (C2) contains a polyamide mixture containing polyamide 6/66/12 (C21) and polyamide (C22) (hereinafter sometimes referred to as a polyamide mixture).

[Polyamide (C22)]
Polyamide (C22) has an amide bond (—CONH—) in the main chain, and is made from melt structural polymerization, solution polymerization, and solid phase using polyamide structural units lactam, aminocarboxylic acid, or diamine and dicarboxylic acid as raw materials. It can be obtained by polymerization or copolymerization by a known method such as polymerization (hereinafter sometimes referred to as polyamide (C22)). However, the polyamide (C22) does not include the above-mentioned poly (caproamide / hexamethylene adipamide / dodecanamide) (polyamide 6/66/12) (C21).

  Polyamide (C22) is a polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene from the viewpoint of obtaining sufficient interlayer adhesion and durability of laminated tubes. Adipamide (polyamide 66), polyhexamethylene sebamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene decanamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), poly At least one homopolymer selected from the group consisting of decamethylene decanamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), and polydodecamethylene dodecamide (polyamide 1212), and / or these. It is preferably a copolymer using several kinds of monomer, such as polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene adipamide (polyamide) 66), polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecamethylene decanamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), and polydodecamethylene dodecamide. It is more preferable to use at least one homopolymer selected from the group consisting of (polyamide 1212) and / or a copolymer using several kinds of raw material monomers forming these, and polycaproamide (polyamide 6). ), Polyundecanamide (polyamide 11) , Polydodecanamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene sebamide (polyamide 610), polyhexamethylene dodecane (polyamide 612), and polydecane methylenedecanamide (polyamide 1010). It is more preferable to use at least one homopolymer selected from the group consisting of) and / or a copolymer using several kinds of raw material monomers forming these, and polyhexamethylene sebacamide (polyamide 610). And / or polyhexamethylene dodecamide (polyamide 612).

  Examples of the production apparatus for polyamide 6 (C11), polyamide 6/66/12 (C21), and polyamide (C22) include known polyamide production apparatuses described in the explanation of the aliphatic polyamide (A). Examples of the method for producing polyamide 6 (C11), polyamide 6/66/12 (C21), and polyamide (C22) include known methods described in the description of the aliphatic polyamide (A).

  Further, polyamide 6 (C1), polyamide 6/66/12 (C21), and polyamide (C22) measured under the conditions of 96% sulfuric acid, polymer concentration 1%, 25 ° C. in accordance with JIS K-6920 The relative viscosity is 1.5 or more and 5.0 or less from the viewpoint of ensuring the mechanical properties of the obtained laminated tube and ensuring the desirable formability of the laminated tube by setting the viscosity at the time of melting to an appropriate range. Preferably, it is 1.8 or more and 4.5 or less.

  In each of polyamide 6 (C11), polyamide 6/66/12 (C21), and polyamide (C22), the terminal amino group concentration per gram is [A] (μeq / g), and the terminal carboxyl group concentration is [B] ( [mu] eq / g), it is preferable that [A]> [B] +5, and [A]> [B] +10 from the viewpoint of sufficiently securing the interlayer adhesion and durability of the laminated tube. It is more preferable that [A]> [B] +15. Furthermore, from the viewpoint of the melt stability of the polyamide and the suppression of the generation of gelled material, [A]> 20 is preferable, and 30 <[A] <120 is more preferable.

  Polyamide 6 (C11), polyamide 6/66/12 (C21), and polyamide (C22) are prepared by known methods such as melt polymerization, solution polymerization, and solid phase polymerization in the presence of amines. It is manufactured by polymerizing or copolymerizing. 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, but are added at the stage during polymerization in consideration of the interlayer adhesion of the laminated tube. It is preferable. Examples of the amines include monoamines, diamines, triamines, and polyamines. In addition to amines, carboxylic acids such as monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid 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 these amines and carboxylic acids include those described in the description of the aliphatic polyamide (A), and these can be used alone or in combination of two or more.

The content of polyamide 6/66/12 (C21) in the polyamide mixture is 50% by mass or more and 100% by mass or less with respect to 100% by mass in total of polyamide 6/66/12 (C21) and polyamide (C22). Yes, it is preferably 55% by mass or more and 90% by mass or less, and more preferably 60% by mass or more and 85% by mass or less. On the other hand, the content of polyamide (C22) in the polyamide mixture is 0% by mass or more and 50% by mass or less with respect to 100% by mass in total of polyamide 6/66/12 (C21) and polyamide (C22). It is preferable that they are mass% or more and 45 mass% or less, and it is more preferable that they are 15 mass% or more and 40 mass% or less.
When the content of polyamide 6/66/12 (C21) is less than the above value and the content of polyamide (C22) exceeds the above value, the mechanical properties and flexibility of the obtained laminated tube are inferior. When the content of polyamide 6/66/12 (C21) exceeds the above value and the content of polyamide (C22) is less than the above value, the interlayer adhesiveness and durability of the obtained laminated tube are insufficient. It becomes.

  The content of the polyamide mixture in the polyamide 6/66/12 composition (C2) is 50% by mass to 98% by mass, preferably 60% by mass to 95% by mass, and more preferably 70% by mass to 92%. It is more preferable that the amount is not more than mass%. When the content of the polyamide mixture is less than the above value, the mechanical properties of the obtained laminated tube are inferior. On the other hand, when the content exceeds the above value, the interlayer adhesion and the durability of the obtained laminated tube are inferior.

[Plasticizer (C3)]
Examples of the plasticizer (C3) in the polyamide 6 composition (C1) and / or the polyamide 6/66/12 composition (C2) include benzenesulfonic acid alkylamides, toluenesulfonic acid alkylamides, and hydroxybenzoic acid alkyl esters. And the like.

  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, 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.

  The content of the plasticizer (C3) in the polyamide 6 composition (C1) and the polyamide 6/66/12 composition (C2) is 1% by mass to 20% by mass, and 2% by mass to 15% by mass. It is preferable that it is 3 mass% or more and 10 mass% or less. When the content of the plasticizer (C3) is less than the above value, the flexibility of the obtained laminated tube is inferior, whereas when it exceeds the above value, the low temperature impact resistance of the obtained laminated tube is inferior.

[Elastomer polymer (C4)]
The polyamide 6 composition (C1) and the polyamide 6/66/12 composition (C2) are elastomer polymers (C4) containing structural units derived from unsaturated compounds having a carboxyl group and / or an acid anhydride group. (Hereinafter, it may be referred to as an elastomer polymer (C4)).

  The elastomer polymer (C4) includes (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 and alkaline earth metals such as Li, Na, K, Mg, Ca, Sr, Ba, 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.

  Examples of the unsaturated compound having a carboxyl group forming the structural unit of the elastomer polymer (C4) include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, cis Α, β-unsaturated carboxylic acids such as -4-cyclohexene-1,2-dicarboxylic acid, endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid, and metal salts of these carboxylic acids Examples include acids. Examples of the unsaturated compound having an acid anhydride group forming the structural unit of the elastomer polymer (C4) include maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- [2.2.1] -5-heptene. Examples include dicarboxylic anhydrides having an α, β-unsaturated bond such as -2,3-dicarboxylic anhydride. These can use 1 type (s) or 2 or more types. Among these, a dicarboxylic anhydride having an α, β-unsaturated bond is preferable, and maleic anhydride and itaconic anhydride are more preferable.

  The carboxyl group and / or acid anhydride group concentration in the elastomer polymer (C4) sufficiently obtains the effect of improving the low-temperature impact resistance, the interlaminar adhesion, and the durability thereof, and the obtained polyamide 6 composition (C1) From the viewpoint of the fluidity of the polyamide 6/66/12 composition (C2), it is preferably 25 μeq / g or more and 200 μeq / g or less, and more preferably 50 μeq / g or more and 150 μeq / g or less.

  The concentration of carboxyl group and / or acid anhydride group in the elastomer polymer (C4) is determined by using phenolphthalein as an indicator using a sample solution prepared by dissolving the elastomer polymer in a toluene solution and further adding ethanol. And titration with a 0.1N KOH ethanol solution.

  The content of the elastomer polymer (C4) in the polyamide 6 composition (C1) and the polyamide 6/66/12 composition (C2) is 1% by mass to 30% by mass, and 3% by mass to 25% by mass. The content is preferably 5% by mass or more and more preferably 20% by mass or less. When the content of the elastomer polymer (C4) is less than the above value, the obtained laminated tube is inferior in low-temperature impact resistance, interlayer adhesion, and durability, while when it exceeds the above value, it is obtained. The mechanical properties of the laminated tube are inferior.

  The production method of the polyamide 6 composition (C1) and the polyamide 6/66/12 composition (C2) is not particularly limited, and various conventionally known methods are adopted by adding various additives as necessary. can do. For example, using a tumbler and / or mixer with polyamide 6 (C11) or polyamide 6/66/12 (C21) and polyamide (C22), and other components to which an elastomer polymer (C4) is added as necessary. Then, the pellets are uniformly dry blended so as to have the above mixing ratio and supplied to the melt kneader, while the plasticizer (C3) is injected from the middle of the cylinder of the melt kneader with a metering pump to melt. It can be produced by a kneading method or the like. 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 composition (C1) and the polyamide 6/66/12 composition (C2) 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 total content of polyamide 6 (C11), plasticizer (C3), and elastomer polymer (C4) in the polyamide 6 composition (C1) as a mixture is preferably 80% by mass or more, and 90% by mass More preferably. The total content of polyamide 6/66/12 (C21), polyamide (C22), plasticizer (C3), and elastomer polymer (C4) in the polyamide 6/66/12 composition (C2) as a mixture Is preferably 80% by mass or more, and more preferably 90% by mass or more.

  Furthermore, for the polyamide 6 composition (C1) and the polyamide 6/66/12 composition (C2), an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, and an inorganic filler are added as necessary. Materials, antistatic agents, flame retardants, crystallization accelerators, colorants, lubricants, and the like may be added.

4). (D) Layer The (d) layer of the laminated tube contains an aliphatic polyketone (D).

[Aliphatic polyketone (D)]
The aliphatic polyketone (D) is a copolymer in which units derived from carbon monoxide and units derived from at least one ethylenically unsaturated compound are alternately arranged, and has barrier properties and moldability. From the viewpoint, a linear alternating copolymer with high crystallinity is preferable (hereinafter sometimes referred to as aliphatic polyketone (D)).
A repeating unit (poly (1-oxotrimethylene)) of a linear alternating copolymer in which units derived from ethylene and units derived from carbon monoxide represented by the following formula (1) are alternately arranged: It is preferable to have a repeating unit of a linear alternating copolymer in which units derived from an unsaturated compound other than ethylene having 3 or more carbon atoms and units derived from carbon monoxide are alternately arranged.

  In the formula (1), X represents an organic group having 3 or more carbon atoms derived from an ethylenically unsaturated compound, and m and n represent a positive integer.

  In addition, a structural unit (poly (1-oxotrimethylene)) in which units derived from ethylene and units derived from carbon monoxide represented by the formula (1) are arranged alternately and carbon atoms other than ethylene It is preferable that the structural unit in which the unit derived from the unsaturated compound of several formulas or more and the unit derived from carbon monoxide are completely alternately arranged is a random copolymer.

  Examples of the ethylenically unsaturated compound other than ethylene include α-olefins having 3 or more carbon atoms, alkenyl aromatic compounds, conjugated dienes, vinyl esters, aliphatic unsaturated carboxylic acids, salts thereof and esters thereof.

  Examples of the α-olefin having 3 or more carbon atoms include propylene, 1-butene, isobutene, 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- Examples include hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene.These can use 1 type (s) or 2 or more types.

Alkenyl aromatic compounds are aryl aliphatics containing an aryl substituent on an ethylenically unsaturated carbon atom such as styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, m-ethylstyrene, p-ethylstyrene, o-propylstyrene, p-propylstyrene, o-isopropylstyrene, m-isopropylstyrene, p-isopropylstyrene, m-butylstyrene, p-butylstyrene, pt-butyl Styrene, 4-propylstyrene, 4-cyclohexylstyrene,
4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, 1,5-dimethylstyrene, 2,4-dimethylstyrene, 2,5-dimethylstyrene, 3,5-dimethylstyrene, Examples thereof include p-phenylstyrene, mesityl styrene, vinyl naphthalene, vinyl anthracene and the like. These can use 1 type (s) or 2 or more types.

  The conjugated dienes include 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, , 6-octadiene, 1,7-octadiene, 1,9-decadiene, 2-methyl-1,3-butadiene, 4-methyl-1,3-pentadiene, 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), dicyclo Pentadiene, cyclohexadiene, cyclopentadiene, 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-ethylidene-3-isopropylidene-5 Examples include norbornene and 2-propenyl-2,5-norbornadiene. These can use 1 type (s) or 2 or more types.

  Vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl valelate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, Examples include vinyl palmitate, vinyl stearate, isopropenyl acetate, 1-butenyl acetate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl cyclohexanecarboxylate, vinyl benzoate, and vinyl cinnamate. These can use 1 type (s) or 2 or more types.

  Aliphatic unsaturated carboxylic acids, salts and esters thereof include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, methyl maleic acid, methyl fumaric acid, cis -4-cyclohexene-1,2-dicarboxylic acid, endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- [ 2.2.1] -5-heptene-2,3-dicarboxylic anhydride, acrylic acid ester, methacrylic acid ester, maleic acid monoester, maleic acid diester, fumaric acid monoester, fumaric acid diester, itaconic acid monoester Itaconic acid diester (these esters include methyl ester, ethyl ester Tellurium, propyl ester, butyl ester, pentyl ester, hexyl ester, heptyl ester, octyl ester, nonyl ester, alkyl ester such as decyl ester, etc.), acrylate, methacrylate, maleate, itaconate (these Examples of the salt include monovalent or divalent metal salts. These can use 1 type (s) or 2 or more types.

  Among the ethylenically unsaturated compounds other than ethylene, an α-olefin having 3 to 8 carbon atoms is preferable and propylene is more preferable from the viewpoint of easy availability and sufficient polymerization reactivity.

  That is, the aliphatic polyketone (D) is a repeating unit of a linear alternating copolymer in which units derived from ethylene and units derived from carbon monoxide represented by the following formula (2) are alternately arranged ( Poly (1-oxotrimethylene)) and a repeating unit of a linear alternating copolymer in which units derived from propylene and units derived from carbon monoxide are alternately arranged (poly (1-oxo-2) It is more preferred to have -methyl-trimethylene)).

In the formula (2), m and n represent a positive integer.

In the formulas (1) and (2), m / (m + n) is preferably 0.5 or more, and from 0.01 to 0.09 from the viewpoint of ensuring appropriate crystallinity and melt stability. It is more preferable.

The aliphatic polyketone (D) can adjust the melting point by selecting the types and composition ratios of carbon monoxide and ethylene and other monomers, and the polymerization composition ratio of carbon monoxide, ethylene and propylene. It is preferable to adjust the melting point. The melting point of the aliphatic polyketone (D) is preferably 200 ° C. or higher and 250 ° C. or lower, more preferably 210 ° C. or higher and 240 ° C. or lower, from the viewpoint of sufficiently ensuring heat resistance and melt processing stability.
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 melt flow rate (MFR) of the aliphatic polyketone (D) (melting point + 20 ° C. under 2,160 g load) ensures a desirable moldability by setting the viscosity at the time of melting within an appropriate range, and does not excessively lower the melt tension. From the viewpoint of preventing the occurrence of problems such as drawdown during molding, it is preferably from 0.01 g / 10 min to 50 g / 10 min, and preferably from 0.1 g / 10 min to 10 g / 10 min. More preferred.

  The limiting viscosity number (LVN) of the aliphatic polyketone (D) measured at 60 ° C. in m-cresol with a standard capillary viscosity measurement device ensures the mechanical properties of the resulting laminated tube and the viscosity at the time of melting. From the viewpoint of securing the desirable formability of the laminated tube with an appropriate range, it is preferably 0.5 dl / g or more and 10.0 dl / g or less, and preferably 0.75 dl / g or more and 5.0 dl / g or less. Is more preferably 0.8 dl / g or more and 4.0 dl / g or less.

  Examples of the method for producing the aliphatic polyketone (D) include known methods, for example, methods described in Patent Documents 9 to 20, but are not particularly limited thereto.

  The aliphatic polyketone (D) can also contain various additives as required. Examples of such additives include conductive fillers, antioxidants, thermal stabilizers, UV absorbers, light stabilizers, lubricants, inorganic fillers, antistatic agents, flame retardants, crystallization accelerators, plasticizers. Agents, colorants, lubricants, and other thermoplastic resins.

[Laminated tube]
The laminated tube has four or more layers including the (a) layer, the (b) layer, the (c) layer, and the (d) layer, and at least one pair of the (c) layer and the (d) layer are arranged adjacent to each other. Is done.

  In the laminated tube, it is essential to include the (b) layer and the (d) layer, and the chemical barrier property, particularly the hydrocarbon barrier property, of the laminated tube is improved. Furthermore, by arranging at least one pair of the (c) layer and the (d) layer adjacent to each other, it becomes possible to obtain a laminated tube excellent in interlayer adhesion and durability.

  In a preferred embodiment, the layer (a) is disposed in the outermost layer of the laminated tube. (A) By arrange | positioning a layer in the outermost layer, it becomes possible to obtain the laminated tube excellent in chemical resistance and a softness | flexibility. The (c) layer is disposed between the (a) layer and the (d) layer.

  In a more preferred embodiment, at least one pair of the (a) layer and the (c) layer are arranged adjacent to each other. By arranging the (c) layer between the (a) layer and the (b) layer, it becomes possible to obtain better interlayer adhesion and its durability. In this case, the (a) layer and The (c) layer disposed between the (b) layer is more preferably a layer containing the polyamide 6/66/12 composition (C2). That is, a laminated tube in which the (a) layer, (c) layer, (b) layer, (c) layer, and (d) layer are arranged adjacent to each other from the outside to the inside is more preferable.

  As a more preferred embodiment, the (d) layer is arranged in the innermost layer, whereby a laminated tube having excellent resistance to deterioration fuel can be obtained, and elution of low molecular weight components such as monomers and oligomers by contact with alcohol-containing gasoline. In the case where the semi-aromatic polyamide composition (B) and the aliphatic polyketone (D) are coextruded, sufficient melt stability and molding stability can be ensured. That is, a laminated tube in which the (a) layer is disposed as the outermost layer, the (c) layer and the (d) layer are disposed adjacent to each other, and the (d) layer is disposed as the innermost layer is more preferable.

  Moreover, in the laminated tube, when the conductive layer containing the aliphatic polyketone (D) containing the conductive filler is disposed in the innermost layer of the laminated tube, the chemical barrier property, the deterioration fuel resistance, and the low molecular weight component resistance In addition to being excellent in elution, when used as a fuel piping tube, it is possible to prevent the spark generated by the internal friction of the fuel circulating in the piping or the friction with the tube wall from igniting the fuel. At that time, the layer containing the aliphatic polyketone having no conductivity is disposed outside the conductive layer, so that both low temperature impact resistance and conductivity can be achieved, and economical. It is also advantageous.

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. Furthermore, 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 molded body. It is more preferable. The aspect ratio (referring to the ratio of length / outer diameter) of the carbon nanotubes 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 electrical conductivity. Preferred carbon blacks include acetylene black obtained by incomplete combustion of acetylene gas, and furnace-type incomplete combustion using crude oil as a raw material. Furnace black such as ketjen black, oil black, naphthalene black, thermal black, lamp black, channel black, roll black, disk black, etc., manufactured by: 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. More preferably, the DBP (dibutyl phthalate) oil absorption is preferably 50 ml / 100 g or more, more preferably 100 ml / 100 g, and even more 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% by mass.
These conductive fillers may be subjected to surface treatment 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 specified unconditionally, but from the viewpoint of balance with conductivity, fluidity, mechanical strength, etc., aliphatic polyketone (D) 100 mass Generally, it is preferably 3 parts by mass or more and 30 parts by mass or less with respect to parts.
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 deteriorate strength and fluidity. Therefore, it is desirable that the content of the conductive filler is as small as possible if a target conductivity level is obtained.

  The thickness of each layer in the laminated tube 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. The thickness of each layer is a chemical solution for the laminated tube. It is determined in consideration of characteristics such as barrier properties, low-temperature impact resistance, and flexibility. 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. In consideration of the balance between low-temperature impact resistance and chemical barrier properties, the thickness of the (b) layer and (d) layer is more preferably 5% or more and 50% or less, respectively, with respect to the total thickness of the laminated tube. More preferably, it is 7% or more and 30% or less.

  Further, the total number of layers in the laminated tube is not particularly limited as long as it is four or more layers including the (a) layer, the (b) layer, the (c) layer, and the (d) layer. Furthermore, the laminated tube according to the first aspect is a laminated tube that provides a further function or is economically advantageous in addition to the four layers (a), (b), (c), and (d). In order to obtain, it may have one layer or two or more layers containing other thermoplastic resins. The number of layers of the laminated tube of the first aspect is 4 or more, but it is preferably 8 or less, more preferably 4 or more and 7 or less, judging from the mechanism of the tube production apparatus.

  Other thermoplastic resins in the laminated tube include aliphatic polyamide (A), semi-aromatic polyamide (B1), semi-aromatic polyamide (B2), polyamide 6 (C11), polyamide 6/66/12 (C21), Polymetaxylylene succinamide (polyamide MXD4), polymetaxylylene glutamide (polyamide MXD5), polymetaxylylene veramide (polyamide MXD8), polymetaxylylene deca other than polyamide (C22) and aliphatic polyketone (D) Mido (polyamide MXD12), polymetaxylylene terephthalamide (polyamide MXDT), polymetaxylylene isophthalamide (polyamide MXDI), polymetaxylylene hexahydroterephthalamide (polyamide MXDT (H)), polymetaxylylene naphthalami (Polyamide MXDN), polyparaxylylene succinamide (polyamide PXD4), polyparaxylylene glutamide (polyamide PXD5), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylene veramide (polyamide PXD8), 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), polyparaxylylene naphthalamide (polyamide PXDN), polyparaphenylene terephthalamide (PPTA), polyparaphenylene isophthalamide (PPIA), polymetaphenylene terephthalamide (PMTA) , Polymetaphenylene isophthalamide (PMIA), poly (2,6-naphthalene dimethylene adipamide) (polyamide 2,6-BAN6), poly (2,6-naphthalene dimethylene terephthalamide) (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 naphthalate) Ramide) (polyamide 2,6-BANN), poly (1,3-cyclohexanedimethylene adipamide) (polyamide 1,3-BAC6), poly (1,3-cyclohexanedimethylene suberamide (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 isophthalate) Ramide) (polyamide 1,3-BACI), poly (1,3-cyclohexanedimethylene hex) Hydroterephthalamide) (polyamide 1,3-BACT (H)), poly (1,3-cyclohexanedimethylene naphthalamide) (polyamide 1,3-BACN), poly (1,4-cyclohexanedimethylene adipamide) ) (Polyamide 1,4-BAC6), Poly (1,4-cyclohexanedimethylenesberamide) (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-cyclo Xanthodimethyleneisophthalamide) (polyamide 1,4-BACI), poly (1,4-cyclohexanedimethylene hexahydroterephthalamide) (polyamide 1,4-BACT (H)), poly (1,4-cyclohexane) Dimethylene 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′-methylene) Biscyclohexylene dodecamide) (polyamide PACM12), Poly (4,4′-methylenebiscyclohexylenetetradecamide) (polyamide PACM14), poly (4,4′-methylenebiscyclohexylenehexadecamide) (polyamide PACM16), poly (4,4′-methylenebiscyclohexylene) Silene octadecamide) (polyamide PACM18), poly (4,4′-methylenebiscyclohexylene terephthalamide) (polyamide PACMT), poly (4,4′-methylenebiscyclohexylene isophthalamide) (polyamide PACMI), Poly (4,4′-methylenebiscyclohexylenehexahydroterephthalamide) (polyamide PACMT (H)), poly (4,4′-methylenebiscyclohexylenenaphthalamide) (polyamide PACMN), poly (4,4 ′ -Methylenebis (2-methyl- Chloroxylene) 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) hexadecanamide) (polyamide MACM16), poly ( , 4′-methylenebis (2-methyl-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′-propylenebiscyclohexyladipamide) (polyamide PACP6), poly (4,4′-propylenebiscyclohexylene) Suberamide) (Po Reamide 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 tetradecamide) (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) Screw Chlohexylene isophthalamide) (polyamide PACPI), poly (4,4′-propylene biscyclohexylene hexahydroterephthalamide) (polyamide PACPT (H)), poly (4,4′-propylene biscyclohexylene naphthalamide) ) (Polyamide PACPN), polyisophorone adipamide (polyamide IPD6), polyisophorone beramide (polyamide IPD8), polyisophorone azeramide (polyamide IPD9), polyisophorone sebamide (polyamide IPD10), polyisoholondodecanamide (polyamide) IPD12), polyisophorone terephthalamide (polyamide IPDT), polyisophorone isophthalamide (polyamide IPDI), polyisophorone hexahydroterephthalamide (polyamide IPDT (H)) Polyisophorone naphthalamide (polyamide 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 naphthalamide (polyamide 6N), poly (2-methylpentamethylene terephthalamide) (polyamide M5T), poly (2-methylpentamethylene isophthalamide) (polyamide M5I), poly (2-methyl) Pentamethylenehexahydroterephthalamide) (polyamide M5T (H)), poly (2-methylpentamethylenenaphthalamide (polyamide M5N), polynonamethyleneisophthalamide (polyamide 9I), polynonamethylenehexahydroterephthalamide ( Polyamide 9T (H)), poly (2-methyloctamethyleneisophthalamide) (polyamide M8I), poly (2-methyloctamethylenehexahydroterephthalamide) (polyamide M8T (H)), polytrimethylhexamethyleneisophthalate Lamid (polyamide) TMHI), polytrimethylhexamethylene hexahydroterephthalamide (polyamide TMHT (H)), polydecamethylene isophthalamide (polyamide 10I), polydecamethylenehexahydroterephthalamide (polyamide 10T (H)), polyundeca Methylene 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 naphthala Polyamide resins such as homopolymers such as polyamide (polyamide 12N), and / or raw material monomers of these polyamides, and / or copolymers using several types of raw material monomers of the aliphatic polyamide (A) Is mentioned.

  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 / tetrafluoroethylene / Hexafluoropropylene copolymer (EFEP), vinylidene fluoride / tetrafluoroethylene copolymer, vinylidene fluoride / hexafluoropropylene copolymer, vinylidene fluoride / perfluoro (Alkyl vinyl ether) copolymer, tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (THV), vinylidene fluoride / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer, tetrafluoroethylene / hexafluoro Propylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer, ethylene / chlorotrifluoroethylene copolymer (ECTFE), chlorotrifluoroethylene / tetrafluoroethylene copolymer, vinylidene fluoride / chlorotrifluoroethylene copolymer 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 copolymer, chlorotrifluoroethylene / tetrafluoroethylene / hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer, chlorotrifluoroethylene / tetrafluoroethylene / Vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer, chlorotrifluoroethylene / tetrafluoroethylene / vinylidene fluoride / f Reactive to fluorinated polymers such as oxafluoropropylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) / hexafluoropropylene copolymer and / or amino groups The fluorine-containing polymer containing a functional group having

  Furthermore, 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 Poly Tylene (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 dobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid and their metal salts (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) Resins: polythioether resins such as polyphenylene sulfide (PPS) and polythioether sulfone (PTES); polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone Polyketone resins such as Nketone (PEKK), Polyetheretheretherketone (PEEEK), Polyetheretherketoneketone (PEEEKK), Polyetherketoneketoneketone (PEKKK), Polyetherketoneetherketoneketone (PEKEKK); PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), acrylonitrile / butadiene copolymer (NBR), etc. Polynitrile resins; polymethacrylate resins such as polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA); polyvinyl ester resins such as polyvinyl acetate (PVAc); Polyvinyl chloride resins such as vinylidene chloride (PVDC), polyvinyl 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), and polyesteramideimide; thermoplastic polyurethane resins; polyamide elastomers, polyurethane An elastomer, a polyester elastomer, etc. are mentioned.

  In the laminated tube, from the viewpoint of melt stability of the aliphatic polyketone (D), among the thermoplastic resins exemplified above, a polyester resin having a melting point of 300 ° C. or lower, a polyamide resin, a polythioether resin, It is preferable to use a polyolefin-based resin and a fluorine-containing polymer.

  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. Examples of metallic materials include metals such as aluminum, iron, copper, nickel, gold, silver, titanium, molybdenum, magnesium, manganese, lead, tin, chromium, beryllium, tungsten, cobalt, and / or metal compounds thereof, and these Examples thereof include 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, a melt extrusion, a method of simultaneously laminating inside or outside a die (coextrusion molding 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 is preferably manufactured by a co-extrusion method in which various materials are co-extruded in a molten state and both are heat-fused (melt-bonded) to produce a tube having a laminated structure in one step. That is, it is preferable that the manufacturing method of a laminated tube includes co-extrusion molding.

  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 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 make L-shaped, U-shaped or the like by adding necessary parts such as connectors or bending the connector.

  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 abrasion with stones and 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), Lempylene 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. 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 this embodiment includes machine parts such as automobile parts, internal combustion engine applications, power tool housings, industrial materials, industrial materials, electrical / electronic parts, medical care, food, household / office supplies, building material-related parts, It can be used for various purposes such as furniture parts.

Moreover, since a laminated tube is excellent in a chemical | medical solution barrier property, it is suitable as a chemical | medical solution conveyance tube. Examples of chemical solutions include aromatic hydrocarbon solvents such as benzene, toluene, xylene, and alkylbenzenes; methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, diethylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol Alcohols such as polyalkylene glycol; phenol solvents; ether solvents such as dimethyl ether, dipropyl ether, methyl-t-butyl ether, ethyl-t-butyl ether, dioxane, tetrahydrofuran, polyol esters, polyvinyl ethers; HFC-23 (trifluoromethane), HFC-32 (difluoromethane), HFC-41 (fluoromethane), HFC-123 (2,2-di Loro-1,1,1-trifluoroethane), HFC-125 (1,1,1,2,2-pentafluoroethane), HFC-134 (1,1,2,2-tetrafluoroethane), HFC -134a (1,1,1,2-tetrafluoroethane), HFC-143 (1,1,2-trifluoroethane), HFC-143a (1,1,1-trifluoroethane), HFC-152 ( 1,2-difluoroethane), HFC-152a (1,1-difluoroethane), HFC-161 (fluoroethane), HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane), HFC -227ca (1,1,2,2,3,3,3-heptafluoropropane), HFC-236fa (1,1,1,3,3,3-hexafluoropropane), HFC 236ea (1,1,1,2,3,3-hexafluoropropane), HFC-236cb (1,1,1,2,2,3-hexafluoropropane), HFC-236ca (1,1,2, 2,3,3-hexafluoropropane), HFC-245ca (1,1,2,2,3-pentafluoropropane), HFC-245ea (1,1,2,3,3-pentafluoropropane), HFC -245eb (1,1,1,2,3-pentafluoropropane), HFC-245fa (1,1,1,3,3-pentafluoropropane), HFC-245cb (1,1,1,2,2) -Pentafluoropropane), HFC-254eb (1,1,1,2-tetrafluoropropane), HFC-254cb (1,1,2,2-tetrafluoropropane), HFC-2 54ca (1,2,2,3-tetrafluoropropane), HFC-263fb (1,1,1-trifluoropropane), HFC-263ca (1,2,2-trifluoropropane), HFC-272fb (1 , 1-difluoropropane), HFC-272ea (1,2-difluoropropane), HFC-272fa (1,3-difluoropropane), HFC-272ca (2,2-difluoropropane), HFC-281fa (1-fluoro Propane), HFC-281ea (2-fluoropropane), HFC-329p (1,1,1,2,2,3,3,4,4-nonafluorobutane), HFC-329 mmz (1,1,1, 3,3,3-hexafluoro-2- (trifluoro) propane), HFC-338mf (1,1,1,3,3,4, , 4-octafluorobutane), HFC-338mcc (1,1,1,2,2,3,4,4-octafluorobutane), HFC-338pcc (1,1,2,2,3,3,4) , 4-octafluorobutane), HFC-347s (1,1,1,2,2,3,3-heptafluorobutane), HFC-365mfc (1,1,1,3,3-pentafluorobutane), HFC-4310mee (1,1,1,2,3,4,4,5,5,5-decafluoropentane), HFC-1123 (trifluoroethylene), HFC-1132a (1,2-difluoroethylene), FC-1216 (hexafluoro-1-propene), HFC-1223 (3,3,3-trifluoro-1-propene), HFC-1225zc (1,1,3,3,3-pentafluoro -1-propene), HFC-1225ye (1,2,3,3,3-pentafluoro-1-propene), HFC-1225yc (1,1,2,3,3-pentafluoro-1-propene), HFC-1232xf (3,3-difluoro-1-propene), HFC-1234ye (1,2,3,3-tetrafluoro-1-propene), HFC-1234ze (1,3,3,3-tetrafluoro- 1-propene), HFC-1234yf (2,3,3,3-tetrafluoro-1-propene), HFC-1234yc (1,1,2,3-tetrafluoro-1-propene), HFC-1234zc (1 , 1,3,3-tetrafluoro-1-propene), HFC-1243yf (2,3,3-trifluoro-1-propene), HFC-1243zc (1,1, -Trifluoro-1-propene), HFC-1243ye (1,2,3-trifluoro-1-propene), HFC-1243ze (1,3,3-trifluoro-1-propene), HFC-1243zf (3 , 3,3-trifluoro-1-propene), HFC-1243yc (1,1,2-trifluoro-1-propene), HFC-1261yf (2-fluoropropene), FC-1318my (1,1,1 , 2,3,4,4,4-octafluoro-2-butene), FC-1318cy (1,1,2,3,3,4,4,4-octafluoro-1-butene), HFC-1327my (1,1,1,2,4,4,4-heptafluoro-2-butene), HFC-1327ye (1,2,3,3,4,4,4-heptafluoro-1-butene), HFC 1327py (1,1,1,2,3,4,4-heptafluoro-2-butene), HFC-1327et (1,3,3,3-tetrafluoro-2- (trifluoromethyl) -1-propene ), HFC-1327cz (1,1,3,3,4,4,4-heptafluoro-1-butene), HFC-1327cye (1,1,2,3,4,4,4-heptafluoro-1) -Butene), HFC-1327cyc (1,1,2,3,3,4,4-heptafluoro-1-butene), HFC-1336yf (2,3,3,4,4,4-hexafluoro-1) -Butene), HFC-1336ze (1,3,3,4,4,4-hexafluoro-1-butene), HFC-1336eye (1,2,3,4,4,4-hexafluoro-1-butene) ), HFC-1336eyc (1,2,3,3,4,4-hexafluoro-1-butene), HFC-1336pyy (1,1,2,3,4,4-hexafluoro-2-butene), HFC-1336pz (1 , 1,1,2,4,4-hexafluoro-2-butene), HFC-1336mzy (1,1,1,3,4,4-hexafluoro-2-butene), HFC-1336mzz (1,1 , 1,4,4,4-hexafluoro-2-butene), HFC-1336qc (1,1,2,3,3,4-hexafluoro-1-butene), HFC-1336pe (1,1,2, , 3,4,4-hexafluoro-1-butene), HFC-1336ft (3,3,3-trifluoro-2- (trifluoromethyl) -1-propene), HFC-1345qz (1,1,1 , 2,4-Pentafluoro 2-butene), HFC-1345mzy (1,1,1,3,4-pentafluoro-2-butene), HFC-1345fz (3,3,4,4,4-pentafluoro-1-butene), HFC -1345mzz (1,1,1,4,4-pentafluoro-2-butene), HFC-1345sy (1,1,1,2,3-pentafluoro-2-butene), HFC-1345fyc (2,3 , 3,4,4-pentafluoro-1-butene), HFC-1345pyz (1,1,2,4,4-pentafluoro-2-butene), HFC-1345cyc (1,1,2,3,3) -Pentafluoro-1-butene), HFC-1345pyy (1,1,2,3,4-pentafluoro-2-butene), HFC-1345eyc (1,2,3,4,4-pentafluoro-1 Butene), HFC-1345ctm (1,1,3,3,3-pentafluoro-2-methyl-1-propene), HFC-1345ftp (2- (difluoromethyl) -3,3,3-trifluoro-1) -Propene), HFC1345fye (2,3,4,4,4-pentafluoro-1-butene), HFC-1345eyf (1,2,4,4,4-pentafluoro-1-butene), HFC-1345eze ( 1,3,4,4,4-pentafluoro-1-butene), HFC-1345ezc (1,3,3,4,4-pentafluoro-1-butene), HFC-1345eye (1,2,3, 4,4-pentafluoro-1-butene), HFC-1354fzc (3,3,4,4-tetrafluoro-1-butene), HFC-1354ctp (1,1,3,3) -Tetrafluoro-2-methyl-1-propene), HFC-1354etm (1,3,3,3-tetrafluoro-2-methyl-1-propene), HFC-1354tfp (2- (difluoromethyl) -3, 3-difluoro-1-propene), HFC-1354my (1,1,1,2-tetrafluoro-2-butene), HFC-1354mzy (1,1,1,3-tetrafluoro-2-butene), FC -141-10myy (1,1,1,2,3,4,4,5,5,5-decafluoro-2-pentene), FC-141-10cy (1,1,2,3,3,4) , 4,5,5,5-decafluoro-1-pentene) HFC-1429mzt (1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene), HFC- 1429m z (1,1,1,2,4,4,5,5,5-nonafluoro-2-pentene), HFC-1429mzy (1,1,1,3,4,4,5,5,5-nonafluoro) -2-pentene), HFC-1429eyc (1,2,3,3,4,4,5,5,5-nonafluoro-1-pentene), HFC-1429czc (1,1,3,3,4,4) , 5,5,5-nonafluoro-1-pentene), HFC-1429cycc (1,1,2,3,3,4,4,5,5-nonafluoro-1-pentene), HFC-1429pyy (1,1 , 2,3,4,4,5,5,5-nonafluoro-2-pentene), HFC-1429myc (1,1,1,2,3,4,4,5,5-nonafluoro-2-pentene) , HFC-1429myye (1,1,1,2,3,4, , 5,5-nonafluoro-2-pentene), HFC-1429eyym (1,2,3,4,4,4-hexafluoro-3- (trifluoromethyl) -1-butene), HFC-1429 cyzm (1, 1,2,4,4,4-hexafluoro-3- (trifluoromethyl) -1-butene), HFC-1429mzt (1,1,1,4,4,4-hexafluoro-2- (trifluoro) Methyl) -2-butene), HFC-1429czym (1,1,3,4,4,4-hexafluoro-3- (trifluoromethyl) -1-butene), HFC-1438fy (2,3,3, 4,4,5,5,5-octafluoro-1-pentene), HFC-1438eycc (1,2,3,3,4,4,5,5-octafluoro-1-pentene), HFC-1438ft mc (3,3,4,4,4-pentafluoro-2- (trifluoromethyl) -1-butene), HFC-1438czzm (1,1,4,4,4-pentafluoro-3- (trifluoro) Methyl) -1-butene), HFC-1438ezym (1,3,4,4,4-pentafluoro-3- (trifluoromethyl) -1-butene), HFC-1438ctmf (1,1,4,4, 4-pentafluoro-2- (trifluoromethyl) -1-butene), HFC-1447fzy (3,4,4,4-tetrafluoro-3- (trifluoromethyl) -1-butene), HFC-1447fz ( 3,3,4,4,5,5,5-ptafluoro-1-pentene), HFC-1447 fycc (2,3,3,4,4,5,5-heptafluoro-1-pentene), HFC 1447cz (1,1,3,3,5,5,5- heptafluoro-1-pentene),
HFC-1447mytm (1,1,1,2,4,4,4 heptafluoro-3-methyl-2-butene), HFC-1447fyz (2,4,4,4-tetrafluoro-3- (trifluoromethyl) ) -1-butene), HFC-1447ezzz (1,4,4,4-tetrafluoro-3- (trifluoromethyl) -1-butene), HFC-1447 qzt (1,4,4,4-tetrafluoro- 2- (trifluoromethyl) -2-butene), HFC-1447syt (2,4,4,4-tetrafluoro-2- (trifluoromethyl) -2-butene), HFC-1456szt (3- (trifluoro Methyl) -4,4,4-trifluoro-2-butene), HFC-1456szy (3,4,4,5,5,5 hexafluoro-2-pentene), HFC-1 56 mstz (1,1,1,4,4,4-hexafluoro-2-methyl-2-butene), HFC-1456 fzce (3,3,4,5,5,5-hexafluoro-1-pentene), HFC-1456ftmf (4,4,4-trifluoro-2- (trifluoromethyl) -1-butene), FC-151-12c (1,1,2,3,3,4,4,5,5,5) 6,6,6-dodeca-1-hexene, perfluoro-1-hexene), FC-151-12 mcy (1,1,1,2,2,3,4,5,5,6,6,6-dodeca) -3-hexene, perfluoro-3-hexene), FC-151-12 mmtt (1,1,1,4,4,4-hexafluoro-2,3-bis (trifluoromethyl) -2-butene), FC −151-12 mmzz (1, 1, 1, 2 3,4,5,5,5-nonafluoro-4- (trifluoromethyl) -2-pentene), HFC-152-11 mmtz (1,1,1,4,4,5,5,5-octafluoro- 2- (trifluoromethyl) -2-pentene), HFC-152-11 mmyz (1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-pentene) , HFC-152-11mmyyz (1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-pentene), HFC-1549fz (PFBE) (3, 3, 4,4,5,5,6,6,6-nonafluoro-1-hexene, perfluorobutyl), HFC-1549 fztmm (4,4,4-trifluoro-3,3-bis (trifluoromethyl)- 1-bute ), HFC-1549 mmtts (1,1,1,4,4,4-hexafluoro-3-methyl-2- (trifluoromethyl) -2-butene), HFC-1549phycz (2,3,3,5) , 5,5-hexafluoro-4- (trifluoromethyl) -1-pentene), HFC-1549myts (1,1,1,2,4,4,5,5,5-nonafluoro-3-methyl-2) -Pentene), HFC-1549mzz (1,1,1,5,5,5-hexafluoro-4- (trifluoromethyl) -2-pentene), HFC-1558szy (3,4,4,5,5, 6,6,6-octafluoro-2-hexene), HFC-1558 fzccc (3,3,4,4,5,5,6,6-octafluoro-2-hexene), HFC-1558 mmtzc (1,1 1,4,4-pentafluoro-2- (trifluoromethyl) -2-pentene), HFC-1558ftmf (4,4,5,5,5-pentafluoro-2- (trifluoromethyl) -1-pentene ), HFC-1567fts (3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene), HFC-1567szz (4,4,5,5,6,6,6- Heptafluoro-2-hexene), HFC-1567fzfc (4, 4, 5, 5, 6, 6, 6-heptafluoro-1-hexene), HFC-1567 sfyy (1, 1, 1, 2, 2, 3, 4-heptafluoro-3-hexene), HFC-1567fzfy (4,5,5,5-tetrafluoro-4- (trifluoromethyl) -1-pentene), HFC-1567myzzm (1, , 1,2,5,5,5-heptafluoro-4-methyl-2-pentene), HFC-1567 mmtyf (1,1,1,3-tetrafluoro-2- (trifluoromethyl) -2-pentene) , FC-161-14myy (1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene), FC-161-14mcy ( 1,1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene), HFC-162-13mzy (1,1,1,3 , 4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene), HFC162-13myz (1,1,1,2,4,4,5,5,6, 6,7,7,7-tridecafluoro-2-heptene), HFC-162-13mczy (1 , 1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene), HFC-162-13mcyz (1,1,1,2,2, 3,5,5,6,6,7,7,7-tridecafluoro-3-heptene), CFC-11 (fluorotrichloromethane), CFC-12 (dichlorodifluoromethane), CFC-114 (1,1 , 2,2-tetrafluoro-1,2-dichloroethane), CFC-114a (1,1,1,2-tetrafluoro-2,2-dichloroethane), CFC-115 (1,1,1,2,2) -Pentafluoro-2-dichloroethane), HCFC-21 (dichlorofluoromethane), HCFC-22 (chlorodifluoromethane), HCFC-122 (1,1,2-trichloro-2,2-difluoroethane), HC C-123 (1,1,1-trifluoro-2,2-dichloroethane), HCFC-124 (1,1,1,2-tetrafluoro-2-chloroethane), HCFC-124a (1,1,2, 2-tetrafluoro-2-chloroethane), HCFC-132 (dichlorodifluoroethane), HCFC-133a (1,1,1-trifluoro-2-chloroethane), HCFC-141b (1,1-dichloro-1-fluoroethane) ), HCFC-142 (1,1-difluoro-2-chloroethane), HCFC-142b (1,1-difluoro-1-chloroethane), HCFC-225ca (3,3-dichloro-1,1,1,2, 2-pentafluoropropane), HCFC-225cb (1,3-dichloro-1,1,2,2,3-pentafluoropropane) HCFC-240db (1,1,1,2,3-pentachloropropane), HCFC-243db (1,1,1-trifluoro-2,3-dichloropropane), HCFC-243ab (1,1,1- Trifluoro-2,2-dichloropropane), HCFC-244eb (1,1,1,2-tetrafluoro-3-chloropropane), HCFC-244bb (1,1,1,2-tetrafluoro-2-chloropropane) , HCFC-244db (1,1,1,3-tetrafluoro-2-chloropropane), HCFC-1111 (1,1,2-trichloro-2-fluoroethylene), HCFC-1113 (1,1,2-triphenyl) Fluoro-2-chloroethylene), HCFC-1223xd (3,3,3-trifluoro-1,2-dichloropropene), HC FC-1224xe (1,3,3,3-tetrafluoro-2-chloropropene), HCFC-1232xf (3,3-difluoro-1,3-dichloropropene), HCFC-1233xf (3,3,3-tri Haloolefins such as fluoro-2-chloropropene), HCFC-1233zd (3,3,3-trifluoro-1-chloropropene), and mixtures thereof; ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, acetophenone; Mineral oils, silicone oils, natural paraffins, naphthenes, synthetic paraffins, polyalphaolefins, etc., gasoline, kerosene, diesel gasoline, rapeseed oil methyl ester, soybean oil methyl ester, palm oil methyl ester, coconut Oil methyl ester, gas liquefied oil (Gas To Liq id: GTL), coal liquefied oil (Coal To Liquid: CTL), biomass liquefied oil (Biomass To Liquid: BTL), alcohol-containing gasoline, ethyl-t-butyl ether blend oxygen-containing gasoline, amine-containing gasoline, sour gasoline, compressed natural Gas (CNG), liquefied petroleum gas (LPG), liquefied hydrocarbon gas (LHG), liquefied natural gas (LNG), dimethyl ether (DME) for fuel, castor oil base brake fluid, glycol ether brake fluid, borate ester brake Fluid, brake fluid for extremely cold regions, silicone oil-based brake fluid, mineral oil-based brake fluid, power steering oil, hydrogen sulfide oil, window washer fluid, engine coolant, urea solution, pharmaceutical agent, ink, paint and the like. The laminated tube is suitable as a tube for conveying the chemical solution. Specifically, a feed tube, a return tube, an evaporation tube, a fuel filler tube, an ORVR tube, a reserve tube, a vent tube or other fuel tube, a fuel cell hydrogen Conveying tube, oil tube, oil drilling tube, pneumatic, hydraulic tube, clutch tube, brake tube, brake negative pressure tube, suspension tube, air tube, turbo air tube, air duct tube, blow-by tube, EGR valve control tube , Window washer fluid tubes, engine coolant (LLC) tubes, reservoir tank tubes, urea solution transfer tubes, cooler tubes for cooling water, refrigerant, etc., air conditioner refrigerant tubes Bed, heater tube, radiator tube, road heating tube, floor heating tube, infrastructure supply tube, fire extinguishers and fire extinguishing equipment tube, medical cooling equipment tubes, ink, paint spraying tubes, other chemical tubes and the like. In particular, it is suitable as a fuel tube. That is, the present invention includes the use of the laminated tube 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.

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 TL 52435 6.5.

[Chemical solution (alcohol-containing gasoline barrier property)
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 change in mass per day was divided by the surface area of the inner layer per 1 m of the tube to calculate the alcohol-containing gasoline permeation amount (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. Universal material testing machine (Orientec, Tensilon UTM
III-200), and a 180 ° peel test was conducted 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 2.0 N / mm or more, it was judged that the durability of interlayer adhesion was excellent.

[Elution resistance of low molecular weight components]
One end of a tube cut to 0.5 m was sealed and mixed with 42.25% toluene, 25.35% isooctane, 12.68% diisobutylene, 4.23% ethanol, 15% methanol, and 0.5% water. FAM compliant with DIN 51604B
B was put inside, and the remaining end was sealed. Thereafter, the test tube was placed in an oven at 60 ° C. and treated for 96 hours. Then, after cooling at room temperature with alcohol-containing gasoline in the taken-out tube, the test solution was evaporated, the residue was dried, and the mass of the residue was measured. The mass of the residue was divided by the inner surface area of the tube to calculate the elution amount (g / m ² ) of the low molecular weight component. 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 (A1), polyamide (C22)
Production of polyamide 12 (A1-1) In a pressure-resistant reaction vessel with an internal volume of 70 liters and a stirrer, 19.7 kg (100.0 mol) of dodecane lactam, 5-amino-1,3,3-trimethylcyclohexanemethylamine 45. 0 g (0.26 mol) and 2.0 L of distilled water were charged, and the inside of the polymerization tank was purged with nitrogen, and then heated to 180 ° C., and stirred at this temperature so that the reaction system was in a uniform state. Subsequently, 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 3.5 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 5 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. The pellets were dried under reduced pressure to obtain polyamide 12 having a relative viscosity of 2.20 (hereinafter, this polyamide 12 is referred to as (A1-1)).

Production of polyamide 12 (A1-2) In production of polyamide 12 (A1-1), 45.0 g (0.26 mol) of 5-amino-1,3,3-trimethylcyclohexanemethylamine was added to 159.0 g of stearic acid ( The polyamide 12 having a relative viscosity of 1.86 was prepared in the same manner as in the production of the polyamide 12 (A1-1) except that the post-polymerization time was changed from 5 hours to 2.5 hours. (Hereinafter, this polyamide 12 is referred to as (A1-2)).

Production of polyamide 610 (A1-3) or (C22-1) In a pressure-resistant reaction vessel with an internal volume of 70 liters equipped with a stirrer, 3.66 kg (31.5 mol) 1,6-hexanediamine, 6.07 kg sebacic acid ( 30.0 mol), sodium hypophosphite monohydrate 11.5 g (0.1% by mass with respect to the raw material), and 5.0 L of distilled water were charged, and the inside of the polymerization tank was purged with nitrogen, then 220 ° C. The mixture was 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 2.58 (hereinafter, this polyamide 610 is referred to as (A1-3) or (C22-1)).

Production of polyamide 612 (A1-4) or (C22-2) In the production of polyamide 610 (A1-3), 6.07 kg (30.0 mol) of sebacic acid was 6.91 kg (30.0 mol) of dodecanedioic acid. A polyamide 612 having a relative viscosity of 2.48 was obtained in the same manner as in the production of the polyamide 610 (A1-3) except that the polyamide 612 was converted to (A1-4) or (C22-2). ).)

Aliphatic polyamide composition (A)
Production of Polyamide 12 Composition (A-1) Polyamide 12 (A1-1) was coated with maleic anhydride-modified ethylene / 1-butene copolymer (C4-1) as an impact modifier and triethylene as an antioxidant. Glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan, IRGANOX245), and tris (2,4-di-t- as a phosphorus-based processing stabilizer (Butylphenyl) phosphite (manufactured by BASF Japan, IRGAFOS168) is mixed in advance and supplied to a twin-screw melt kneader (manufactured by Nippon Steel Works, model: TEX44), and melt kneaded at a cylinder temperature of 180 ° C. to 260 ° C. After the molten resin is extruded into a strand shape, this is introduced into a water tank, cooled, cut and vacuum dried to obtain polyamide 1 Polyamide 12 composition comprising 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus processing stabilizer for 100 parts by mass of 2 (A1-1) 80% by mass and 20% by mass of impact modifier. (Hereinafter, this polyamide 12 composition is referred to as (A-1)).

Production of polyamide 12 composition (A-2) Production of polyamide 12 composition (A-1) was the same as the production of polyamide 12 composition (A-1) except that the amount of impact modifier added was changed. In the method, with respect to a total of 100 parts by mass of polyamide 12 (A1-1) 85% by mass and impact modifier 15% by mass, 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus processing stabilizer 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), the polyamide 12 (A1-1) is changed to (A1-2), and carbon black (cabot) is used as the conductive filler. Polyamide 12 (A1-2) was manufactured in the same manner as in the preparation of the polyamide 12 composition (A-1) except that Vulcan XD-72) was used and the cylinder temperature was changed from 260 ° C to 270 ° C. Conductive polyamide composed of 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus processing stabilizer for a total of 100 parts by mass of 60% by mass, impact modifier 20% by mass, and conductive filler 20% by mass. A pellet of 12 composition was obtained (hereinafter, this conductive polyamide 12 composition is referred to as (A-3)).

Production of polyamide 610 composition (A-4) In production of polyamide 12 composition (A-1), polyamide 12 (A1-1) was changed to polyamide 610 (A1-3), and the cylinder of the biaxial melt kneader In the middle of the production of polyamide 12 composition (A-1), except that benzenesulfonic acid butyramide (C3-1) described later as a plasticizer was injected by a metering pump and the cylinder temperature was changed from 260 ° C. to 270 ° C. In the same manner as above, with respect to 100 parts by mass in total of 80% by mass of polyamide 610 (A1-3), 10% by mass of impact modifier, and 10% by mass of plasticizer, 0.8 parts by mass of antioxidant, phosphorus system A pellet of a polyamide 610 composition comprising 0.2 parts by mass of a processing stabilizer was obtained (hereinafter, this polyamide 610 composition is referred to as (A-4)).

Production of polyamide 612 composition (A-5) In production of polyamide 12 composition (A-1), polyamide 12 (A1-1) was changed to polyamide 612 (A1-4), and the cylinder of the biaxial melt kneader In the middle of the production of polyamide 12 composition (A-1), except that benzenesulfonic acid butyramide (C3-1) described later as a plasticizer was injected by a metering pump and the cylinder temperature was changed from 260 ° C. to 270 ° C. In the same manner as above, with respect to a total of 100 parts by mass of polyamide 612 (A1-4) 80% by mass, impact modifier 10% by mass, and plasticizer 10% by mass, 0.8 parts by mass of antioxidant, phosphorus system A pellet of a polyamide 612 composition comprising 0.2 parts by weight of a processing stabilizer was obtained (hereinafter, this polyamide 612 composition is referred to as (A-5)).

Semi-aromatic polyamide (B1)
Production of semi-aromatic polyamide (B1-1) 2.37 kg (15.0 mol) of 1,9-nonanediamine, 2.37 kg (15.0 mol) of 2-methyl-1,8-octanediamine, 4. terephthalic acid 94 kg (29.7 mol), 65.9 g (0.54 mol) of benzoic acid, 9.8 g of sodium hypophosphite monohydrate (0.1% by mass relative to the raw material), and 6.0 L of distilled water Was placed in an autoclave and purged with nitrogen. The mixture was stirred at 100 ° C. for 30 minutes, and the internal temperature was raised to 190 ° C. over 2 hours. At this time, the autoclave was pressurized to 2.0 MPa. The reaction was continued as it was for 1 hour, then the temperature was raised to 230 ° C., and then the temperature was maintained at 230 ° C. for 2 hours, and the reaction was carried out while gradually removing water vapor and keeping the pressure at 2.0 MPa. Next, the pressure was reduced to 1.0 MPa over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer. This was dried at 100 ° C. under reduced pressure for 12 hours, pulverized to a size of 2 mm or less, and solid-phase polymerized at 210 ° C. and 0.013 kPa for 8 hours, with a melting point of 265 ° C. and a relative viscosity of 2.38. An aromatic polyamide (polyamide 9T / M8T = 50/50 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B1-1)).

Production of semi-aromatic polyamide (B1-2) In production of semi-aromatic polyamide (B1-1), 2.37 kg (15.0 mol) of 1,9-nonanediamine and 2-methyl-1,8-octanediamine 2 .37 kg (15.0 mol) is changed to 4.04 kg (25.5 mol) of 1,9-nonanediamine and 0.712 kg (4.5 mol) of 2-methyl-1,8-octanediamine, Is a semi-aromatic polyamide having a melting point of 305 ° C. and a relative viscosity of 2.34 (polyamide 9T / M8T = 85) in the same manner as in the production of the semi-aromatic polyamide (B1-1) except that the temperature is changed from 210 to 240 ° C. / 15 mol%) (hereinafter, this semi-aromatic polyamide is referred to as (B1-2)).

Production of semi-aromatic polyamide (B1-3) In production of semi-aromatic polyamide (B1-1), 4.94 kg (29.7 mol) of terephthalic acid was converted to 6.43 kg (29.7 mol) of 2,6-naphthalenedicarboxylic acid. The semi-aromatic polyamide having a melting point of 275 ° C. and a relative viscosity of 2.37 (polyamide 9N / M8N = 50/50 mol), in the same manner as in the production of the semi-aromatic polyamide (B1-1) %) (Hereinafter, this semi-aromatic polyamide is referred to as (B1-3)).

Production of semi-aromatic polyamide (B1-4) In production of semi-aromatic polyamide (B1-1), 2.37 kg (15.0 mol) of 1,9-nonanediamine and 2-methyl-1,8-octanediamine 2 .37 kg (15.0 mol) was changed to 5.17 kg (30.0 mol) of 1,10-decanediamine and the solid state polymerization temperature was changed from 230 ° C. to 260 ° C. 1) A semi-aromatic polyamide (polyamide 10T = 100 mol%) having a melting point of 315 ° C. and a relative viscosity of 2.33 was obtained in the same manner as in the production of 1) (hereinafter, this semi-aromatic polyamide (B1-4) That said.)

Production of semi-aromatic polyamide (B1-5) In production of semi-aromatic polyamide (B1-4), 5.17 kg (30.0 mol) of 1,10-decanediamine and 4.98 kg (30.0 mol) of terephthalic acid ) Is changed to 3.10 kg (18.0 mol) of 1,10-decanediamine, 2.99 kg (18.0 mol) of terephthalic acid, and 2.42 kg (12.0 mol) of 11-aminoundecanoic acid. A semi-aromatic polyamide having a melting point of 255 ° C. and a relative viscosity of 2.34 (polyamide 10T / polyamide) was produced in the same manner as in the production of the semi-aromatic polyamide (B1-4) except that the polymerization temperature was changed from 260 ° C. to 200 ° C. 11 = 60/40 mol%) (hereinafter, this semi-aromatic polyamide is referred to as (B1-5)).

Production of semi-aromatic polyamide (B1-6) In production of semi-aromatic polyamide (B1-4), 4.98 kg (30.0 mol) of terephthalic acid, 3.32 kg (20.0 mol) of terephthalic acid and sebacic acid The melting point was 279 ° C. in the same manner as in the production of the semi-aromatic polyamide (B1-4) except that the solid-state polymerization temperature was changed from 260 ° C. to 220 ° C. A semi-aromatic polyamide (polyamide 10T / 1010 = 67/33 mol%) having a relative viscosity of 2.37 was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B1-6)).

Production of semi-aromatic polyamide (B1-7) In production of semi-aromatic polyamide (B1-4), 5.17 kg (30.0 mol) of 1,10-decanediamine and 4.98 kg (30.0 mol) of terephthalic acid ) Is changed to 7.26 kg (24.0 mol) of equimolar salt of 1,10-decanediamine and terephthalic acid, and 1.863 kg (6.0 mol) of equimolar salt of 1,6-hexanediamine and dodecanedioic acid. A semi-aromatic polyamide having a melting point of 261 ° C. and a relative viscosity of 2.34 was obtained in the same manner as in the production of the semi-aromatic polyamide (B1-4) except that the solid-state polymerization temperature was changed from 260 ° C. to 210 ° C. Polyamide 10T / 612 = 80/20 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B1-7)).

Production of semi-aromatic polyamide (B1-8) In production of semi-aromatic polyamide (B1-1), terephthalic acid 4.94 kg (29.7 mol), 1,9-nonanediamine 2.37 kg (15.0 mol) , And 2.37 kg (15.0 mol) of 2-methyl-1,8-octanediamine, 2.74 kg (16.5 mol) of terephthalic acid, 0.997 kg (6.0 mol) of isophthalic acid, 1. Semi-aromatic polyamide, except for changing to 10 kg (7.5 mol) and 1,6-hexanediamine 3.60 kg (31.0 mol), changing the polymerization temperature to 250 ° C. and the solid-state polymerization temperature to 230 ° C. A semi-aromatic polyamide (polyamide 6T / 6I / 66 = 55/20/25 mol%) having a melting point of 302 ° C. and a relative viscosity of 2.28 was obtained in the same manner as in the production of (B1-1) (hereinafter, referred to as “B1-1”). This The semi-aromatic polyamide is referred to as (B1-8).

Semi-aromatic polyamide (B2)
Manufacture of semi-aromatic polyamide (B2-1) Equipped with a stirrer, thermometer, torque meter, pressure gauge, raw material inlet directly connected with diaphragm pump, nitrogen gas inlet, pressure outlet, pressure regulator, and polymer outlet A pressure vessel having an internal volume of 70 liters was charged with 6.07 kg (30.0 mol) of sebacic acid, 8.5 g (0.049 mol) of calcium hypophosphite, and 2.2 g (0.025 mol) of sodium acetate. After the pressure inside the pressure vessel was pressurized to 0.3 MPa with 99.9999% nitrogen gas, the operation of releasing the nitrogen gas to normal pressure was repeated 5 times to perform nitrogen substitution, and then the pressure was reduced. The system was heated while stirring. Furthermore, after heating up to 190 degreeC under a small amount of nitrogen stream, 4.09 kg (30.0 mol) of m-xylylenediamine was dripped over 160 minutes under stirring. During this time, the internal pressure of the reaction system was controlled to 0.5 MPa, and the internal temperature was continuously raised to 295 ° C. Moreover, the water distilled with the dropwise addition of m-xylylenediamine was removed out of the system through a condenser and a cooler. After completion of the dropwise addition of m-xylylenediamine, the pressure was reduced to normal pressure over 60 minutes, and the reaction was continued for 10 minutes while maintaining the temperature in the container at 250 ° C. Thereafter, the internal pressure of the reaction system was reduced to 79 kPa, and the melt polymerization reaction was continued for 40 minutes. Thereafter, stirring was stopped and the inside of the system was pressurized to 0.2 MPa with nitrogen, and the polycondensate was extracted from the lower outlet of the pressure vessel into a string shape. The string-like polycondensate is immediately cooled, and the water-cooled string-like resin is pelletized by a pelletizer, and then dried under reduced pressure, a semi-aromatic polyamide having a melting point of 191 ° C. and a relative viscosity of 2.46 (polyamide MXD10 = 100 mol% (Hereinafter, this semi-aromatic polyamide is referred to as (B2-1)).

Production of semi-aromatic polyamide (B2-2) In the production of semi-aromatic polyamide (B2-1), 4.09 kg (30.0 mol) of m-xylylenediamine and m-xylylenediamine and p-xylylenediamine are used. The 7: 3 mixed diamine was changed to 4.09 kg (30.0 mol) and the polymerization temperature was changed from 250 ° C. to 260 ° C. in the same manner as in the production of the semi-aromatic polyamide (B2-1). A semi-aromatic polyamide (polyamide MXD10 / PXD10 = 70/30 mol%) having a melting point of 215 ° C. and a relative viscosity of 2.40 was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B2-2)).

Production of semi-aromatic polyamide (B2-3) In the production of semi-aromatic polyamide (B2-1), 4.09 kg (30.0 mol) of m-xylylenediamine and m-xylylenediamine and p-xylylenediamine are used. In the same manner as the production of the semi-aromatic polyamide (B2-1) except that the 6: 4 mixed diamine was changed to 4.09 kg (30.0 mol) and the polymerization temperature was changed from 250 ° C. to 270 ° C. A semi-aromatic polyamide (polyamide MXD10 / PXD10 = 60/40 mol%) having a melting point of 224 ° C. and a relative viscosity of 2.42 was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B2-3)).

Production of semi-aromatic polyamide (B2-4) In the production of semi-aromatic polyamide (B2-1), 4.09 kg (30.0 mol) of m-xylylenediamine was converted to 4.09 kg (30. The melting point was 281, 291 ° C. (having two melting points) in the same manner as the production of the semi-aromatic polyamide (B2-1) except that the polymerization temperature was changed from 250 ° C. to 300 ° C. A semi-aromatic polyamide having a relative viscosity of 2.41 (polyamide PXD10 = 100 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B2-4)).

Production of semi-aromatic polyamide (B2-5) In production of semi-aromatic polyamide (B2-1), 6.07 kg (30.0 mol) of sebacic acid was changed to 5.65 kg (30.0 mol) of azelaic acid. Except that a semi-aromatic polyamide (polyamide MXD9 = 100 mol%) having a melting point of 194 ° C. and a relative viscosity of 2.45 was obtained in the same manner as in the production of the semi-aromatic polyamide (B2-1) (hereinafter referred to as “this”). Semi-aromatic polyamide is referred to as (B2-5).)

Production of semi-aromatic polyamide (B2-6) In the production of semi-aromatic polyamide (B2-1), 4.09 kg (30.0 mol) of m-xylylenediamine was added to 2,6-bis (aminomethyl) naphthalene 5 The melting point was 286 ° C. and the relative viscosity was 2 in the same manner as in the production of the semi-aromatic polyamide (B2-1) except that the polymerization temperature was changed from 240 ° C. to 300 ° C. by changing to .59 kg (30.0 mol). .33 semi-aromatic polyamide (polyamide 2,6-BAN10 = 100 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B2-6)).

Production of semi-aromatic polyamide (B2-7) In production of semi-aromatic polyamide (B2-1), 6.07 kg (30.0 mol) of sebacic acid was changed to 4.38 kg (30.0 mol) of adipic acid, A semi-aromatic polyamide having a melting point of 243 ° C. and a relative viscosity of 2.42 (polyamide MXD6 = polyamide) was prepared in the same manner as in the production of the semi-aromatic polyamide (B2-1) except that the polymerization temperature was changed from 250 ° C. to 275 ° C. 100 mol%) (hereinafter, this semi-aromatic polyamide is referred to as (B2-7)).

Semi-aromatic polyamide composition (B)
Manufacture of semi-aromatic polyamide composition (B-1) Maleic anhydride-modified ethylene / 1-butene copolymer (C4-1), which will be described later, as an impact-improving material, semi-aromatic polyamide (B1-1), antioxidant Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan, IRGANOX 245) as an agent, and tris (2,4- Di-t-butylphenyl) phosphite (manufactured by BASF Japan, IRGAFOS 168) is mixed in advance and supplied to a twin-screw melt kneader (manufactured by Nippon Steel Works, model: TEX44). After melt-kneading at ℃ and extruding the molten resin into a strand shape, this is introduced into a water tank, cooled, cut, and vacuum-dried. Semi-fragrance comprising 0.8 parts by weight of antioxidant and 0.2 parts by weight of phosphorus processing stabilizer with respect to 90 parts by weight of aromatic polyamide (B1-1) and 10 parts by weight of impact modifier 10 parts in total. Group polyamide composition pellets were obtained (hereinafter, this semi-aromatic polyamide composition is referred to as (B-1)).

Production of semi-aromatic polyamide composition (B-2) In the production of semi-aromatic polyamide composition (B-1), the semi-aromatic polyamide (B1-1) is changed to (B1-2), and the cylinder temperature is set to 300. In the same manner as the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from ℃ to 340 ° C., 90% by mass of the semi-aromatic polyamide (B1-2) and 10% by mass of the impact modifier A semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer was obtained with respect to 100 parts by weight in total (hereinafter, this semi-aromatic polyamide composition). (Referred to as (B-2)).

Production of semi-aromatic polyamide composition (B-3) In the production of semi-aromatic polyamide composition (B-1), the semi-aromatic polyamide (B1-1) is changed to (B1-3) and the cylinder temperature is set to 300. In the same manner as the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from 310C to 310 ° C, 90% by mass of the semi-aromatic polyamide (B1-3) and 10% by mass of the impact modifier A semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer was obtained with respect to 100 parts by weight in total (hereinafter, this semi-aromatic polyamide composition). (B-3)).

Production of semi-aromatic polyamide composition (B-4) In the production of semi-aromatic polyamide composition (B-1), the semi-aromatic polyamide (B1-1) was changed to (B1-4), and the cylinder temperature was set to 300. In the same manner as the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from ℃ to 340 ° C., 90% by mass of the semi-aromatic polyamide (B1-4) and 10% by mass of the impact modifier A semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer was obtained with respect to 100 parts by weight in total (hereinafter, this semi-aromatic polyamide composition). (B-4)).

Production of semi-aromatic polyamide composition (B-5) In production of semi-aromatic polyamide composition (B-1), semi-aromatic polyamide (B1-1) was changed to (B1-5), and the cylinder temperature was set to 300. In the same manner as the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from 290 ° C. to 290 ° C., 90% by mass of the semi-aromatic polyamide (B1-5) and 10% by mass of the impact modifier A semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer was obtained with respect to 100 parts by weight in total (hereinafter, this semi-aromatic polyamide composition). (Referred to as (B-5)).

Production of semi-aromatic polyamide composition (B-6) In production of semi-aromatic polyamide composition (B-1), semi-aromatic polyamide (B1-1) was changed to (B1-6), and the cylinder temperature was set to 300. In the same manner as the production of the semiaromatic polyamide composition (B-1) except that the temperature was changed from 310 ° C to 310 ° C, 90% by mass of the semiaromatic polyamide (B1-6) and 10% by mass of the impact modifier A semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer was obtained with respect to 100 parts by weight in total (hereinafter, this semi-aromatic polyamide composition). (Referred to as (B-6)).

Production of semi-aromatic polyamide composition (B-7) In the production of semi-aromatic polyamide composition (B-1), the semi-aromatic polyamide (B1-1) was changed to (B1-7), In the same manner as in the production of the aromatic polyamide composition (B-1), the antioxidant is added to 100 parts by mass of 90% by mass of the semi-aromatic polyamide (B1-7) and 10% by mass of the impact modifier. A semi-aromatic polyamide composition pellet comprising 0.8 part by mass and phosphorus-based processing stabilizer 0.2 part by mass was obtained (hereinafter, this semi-aromatic polyamide composition is referred to as (B-7)).

Production of semi-aromatic polyamide composition (B-8) In the production of semi-aromatic polyamide composition (B-1), the semi-aromatic polyamide (B1-1) was changed to (B1-8), and the cylinder temperature was changed to 300. In the same manner as the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from ℃ to 340 ° C., 90% by mass of the semi-aromatic polyamide (B1-8) and 10% by mass of the impact modifier A semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer was obtained with respect to 100 parts by weight in total (hereinafter, this semi-aromatic polyamide composition). (Referred to as (B-8)).

Production of semi-aromatic polyamide composition (B-9) In production of semi-aromatic polyamide composition (B-1), semi-aromatic polyamide (B1-1) was changed to (B2-1), and the cylinder temperature was set to 300. In the same manner as the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from 240 ° C. to 240 ° C., 90% by mass of the semi-aromatic polyamide (B2-1) and 10% by mass of the impact modifier A semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer was obtained with respect to 100 parts by weight in total (hereinafter, this semi-aromatic polyamide composition). (Referred to as (B-9)).

Production of semi-aromatic polyamide composition (B-10) In the production of semi-aromatic polyamide composition (B-9), semi-aromatic polyamide (B2-1) was changed to (B2-2), and the cylinder temperature was adjusted to 240. Except for changing from ℃ to 250 ℃, by the same method as the production of the semi-aromatic polyamide composition (B-9), 90% by mass of the semi-aromatic polyamide (B2-2) and 10% by mass of the impact modifier. A semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer was obtained with respect to 100 parts by weight in total (hereinafter, this semi-aromatic polyamide composition). (Referred to as (B-10)).

Production of semi-aromatic polyamide composition (B-11) In production of semi-aromatic polyamide composition (B-9), semi-aromatic polyamide (B2-1) was changed to (B2-3), and the cylinder temperature was adjusted to 240. With the same method as the production of the semi-aromatic polyamide composition (B-9) except that the temperature was changed from 260 ° C. to 260 ° C., 90% by mass of the semi-aromatic polyamide (B2-3) and 10% by mass of the impact modifier A semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer was obtained with respect to 100 parts by weight in total (hereinafter, this semi-aromatic polyamide composition). (Referred to as (B-11)).

Production of semi-aromatic polyamide composition (B-12) In production of semi-aromatic polyamide composition (B-9), semi-aromatic polyamide (B2-1) was changed to (B2-4), and the cylinder temperature was adjusted to 240. Except for changing from ℃ to 320 ℃, in the same manner as the production of the semi-aromatic polyamide composition (B-9), A semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer was obtained with respect to 100 parts by weight in total (hereinafter, this semi-aromatic polyamide composition). (Referred to as (B-12)).

Production of semi-aromatic polyamide composition (B-13) In production of semi-aromatic polyamide composition (B-9), semi-aromatic polyamide (B2-1) was changed to (B2-5), In the same manner as in the production of the aromatic polyamide composition (B-9), an antioxidant is added to 100 parts by mass of 90% by mass of the semi-aromatic polyamide (B2-5) and 10% by mass of the impact modifier. A semi-aromatic polyamide composition pellet comprising 0.8 part by mass and phosphorus-based processing stabilizer 0.2 part by mass was obtained (hereinafter, this semi-aromatic polyamide composition is referred to as (B-13)).

Production of semi-aromatic polyamide composition (B-14) In production of semi-aromatic polyamide composition (B-9), semi-aromatic polyamide (B2-1) was changed to (B2-6) and the cylinder temperature was adjusted to 240. Except for changing from 320 ° C. to 320 ° C., 90% by mass of the semi-aromatic polyamide (B2-6) and 10% by mass of the impact improving material were produced in the same manner as in the production of the semi-aromatic polyamide composition (B-9). A semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer was obtained with respect to 100 parts by weight in total (hereinafter, this semi-aromatic polyamide composition). (Referred to as (B-14)).

Production of semi-aromatic polyamide composition (B-15) In production of semi-aromatic polyamide composition (B-9), semi-aromatic polyamide (B2-1) was changed to (B2-7) and the cylinder temperature was adjusted to 240. Except for changing from ℃ to 280 ℃, in the same manner as the production of the semi-aromatic polyamide composition (B-9), 90% by mass of the semi-aromatic polyamide (B2-7), 10% by mass of the impact modifier A semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer was obtained with respect to 100 parts by weight in total (hereinafter, this semi-aromatic polyamide composition). (Referred to as (B-15)).

Polyamide 6 (C11)
Production of polyamide 6 (C11-1) Caprolactam 11.32 kg (100.0 mol) and distilled water 2.0 L were placed in a pressure-resistant reaction vessel with a stirrer having an internal volume of 70 liters, heated to 100 ° C. and heated at this temperature. The reaction system was stirred so as to be uniform. Subsequently, the temperature was further raised to 260 ° C., and the mixture was stirred for 1 hour under a pressure of 2.5 MPa. Thereafter, 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 6 hours under reduced pressure at 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 extract and remove unreacted monomers, followed by drying under reduced pressure to obtain polyamide 6 having a relative viscosity of 4.06 (hereinafter, this polyamide 6 is referred to as (C11-1)). ).

Polyamide 6/66/12 (C21)
Production of polyamide 6/66/12 (C21-1) In the production of polyamide 6 (C11-1), 11.32 kg (100.0 mol) of caprolactam was converted to 9.93 kg (87.7 mol) of caprolactam, 1,6- Preparation of polyamide 6 (C11-1) except that it was changed to 1.40 kg (5.7 mol) of equimolar salt of hexanediamine and adipic acid and 1.40 kg (6.5 mol) of 12-aminododecanoic acid In the same manner, polyamide 6/66/12 (caproamide unit / hexamethylene adipamide unit / dodecanamide unit = 78/11/11% by mass) having a relative viscosity of 4.01 was obtained (hereinafter, this polyamide 6). / 66/12 is referred to as (C21-1).)

Production of polyamide 6/12 (C21-2) In production of polyamide 6/66/12 (C21-1), 9.93 kg (87.7 mol) of caprolactam, equimolar salt of 1,6-hexanediamine and adipic acid 1.40 kg (5.7 mol) and 1.40 kg (6.5 mol) of 12-aminododecanoic acid were added to 9.90 kg (87.5 mol) of caprolactam and 2.69 kg (12.5 mol) of 12-aminododecanoic acid. The polyamide 6/12 with a relative viscosity of 3.86 (caproamide unit / dodecanamide unit = 80/20% by mass) in the same manner as in the production of polyamide 6/66/12 (C21-1) except that (Hereinafter, this polyamide 6/12 is referred to as (C21-2)).

Plasticizer (C3)
Benzenesulfonic acid butyramide (C3-1) (manufactured by Daihachi Chemical Industry Co., Ltd., BM-4)

Elastomer polymer (C4)
Maleic anhydride modified ethylene / 1-butene copolymer (C4-1) (Mitsui Chemicals, Tuffmer MH5010)

Polyamide 6 composition Manufacture of polyamide 6 composition (C1-1) In the manufacture of polyamide 12 composition (A-1), polyamide 12 (A1-1) is changed to polyamide 6 (C11-3), and the biaxial melting is performed. From the middle of the cylinder of the kneader, benzenesulfonic acid butyramide (C3-1) was injected with a metering pump, and the cylinder temperature was changed from 260 ° C to 270 ° C. By the same method, the antioxidant was added to 100 parts by mass of polyamide 6 (C11-1) 80% by mass, plasticizer (C3-1) 10% by mass, and elastomer polymer (C4-1) 10% by mass. A pellet of polyamide 6 composition comprising 0.8 part by weight of the agent and 0.2 part by weight of the phosphorus processing stabilizer was obtained (hereinafter, this polyamide 6 composition is referred to as (C1-1)).

Polyamide 6/66/12 composition (C2)
Preparation of polyamide 6/66/12 composition (C2-1) Polyamide 6/66/12 (C21-1) and polyamide 610 (C22-1) were mixed with maleic anhydride-modified ethylene / 1-butene copolymer (C4). -1), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan, IRGANOX245) as an antioxidant, and phosphorus-based processing stabilizer While tris (2,4-di-t-butylphenyl) phosphite (manufactured by BASF Japan, IRGAFOS168) is mixed in advance and supplied to a twin-screw melt kneader (manufactured by Nippon Steel, Ltd., model: TEX44) Benzenesulfonic acid butyramide (C3-1) is injected from the middle of the cylinder of the biaxial melt kneader with a metering pump. Then, after melt-kneading at a cylinder temperature of 180 ° C. to 260 ° C. and extruding the molten resin into a strand shape, this is introduced into a water tank, cooled, cut, and vacuum dried to give polyamide 6/66/12 (C21-1 ) 50 mass%, polyamide 610 (C22-1) 30 mass%, plasticizer (C3-1) 5 mass%, elastomer polymer (C4-1) 15 mass% total 100 mass parts antioxidant A pellet of polyamide 6/66/12 composition comprising 0.8 part by mass and 0.2 part by mass of phosphorus-based processing stabilizer was obtained (hereinafter, this polyamide 6/66/12 composition is referred to as (C2-1). .)

Manufacture of polyamide 6/66/12 composition (C2-2) In the manufacture of polyamide 6/66/12 composition (C2-1), polyamide 610 (C22-1) was changed to polyamide 612 (C22-2). Except for the above, in the same manner as in the production of the polyamide 6/66/12 composition (C2-1), 60% by mass of polyamide 6/66/12 (C21-1), 20% by mass of polyamide 612 (C22-2) , 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus-based processing stabilizer with respect to 100 parts by mass in total of 5% by mass of plasticizer (C3-1) and 15% by mass of elastomer polymer (C4-1). Part of a polyamide 6/66/12 composition pellet was obtained (hereinafter, this polyamide 6/66/12 composition is referred to as (C2-2)).

Production of polyamide 6/66/12 composition (C2-3) Polyamide 6/66 /, except that polyamide 610 (C22-1) is not used in the production of polyamide 6/66/12 composition (C2-1). 12 Polyamide 6/66/12 (C21-1) 80% by mass, plasticizer (C3-1) 5% by mass, elastomer polymer (C4-1) in the same manner as in the production of composition (C2-1). ) 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 was obtained with respect to 100 parts by mass in total of 15% by mass (hereinafter, This polyamide 6/66/12 composition is referred to as (C2-3)).

Production of polyamide 6/66/12 composition (C2-4) Polyamide 610 (C22-1), plasticizer (C3-1), and elastomer in the production of polyamide 6/66/12 composition (C2-1) Except not using a polymer (C4-1), it is the same method as manufacture of a polyamide 6/66/12 composition (C2-1), and polyamide 6/66/12 (C21-1) is 100 mass%. In contrast, a pellet of a polyamide 6/66/12 composition comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus-based processing stabilizer was obtained (hereinafter, this polyamide 6/66/12 composition was (Referred to as (C2-4)).

Production of polyamide 6/12 composition (C2-5) In the production of polyamide 6/66/12 composition (C2-4), polyamide 6/66/12 (C21-1) was converted to polyamide 6/12 (C21-2). Except for the change to the polyamide 6/66/12 composition (C2-4), the antioxidant is 0.1% with respect to 100% by mass of the polyamide 6/12 (C21-2). Pellets of a polyamide 6/12 composition comprising 8 parts by mass and 0.2 parts by mass of a phosphorus processing stabilizer were obtained (hereinafter, this polyamide 6/12 composition is referred to as (C2-5)).

Aliphatic polyketone (D)
Aliphatic polyketone (D-1): manufactured by Sosei Co., Ltd., HYOSUNG POKETONE M630A (carbon monoxide / ethylene / propylene copolymer, melting point: 220 ° C., intrinsic viscosity (LVN): 2.1 dl / g, MFR ( 240 ° C. under 2,160 g load): 6 g / 10 min)

Production of Conductive Aliphatic Polyketone Composition (D-2) To the aliphatic polyketone (D-1), carbon black (Vulcan XD-72, manufactured by Cabot Corporation) as a conductive filler and triethylene glycol-bis as an antioxidant [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan, IRGANOX245), and tris (2,4-di-tert-butylphenyl) as a phosphorus processing stabilizer While mixing phosphite (BASF Japan, IRGAFOS168) in advance and supplying it to a twin-screw melt kneader (manufactured by Nippon Steel Works, model: TEX44), from the middle of the cylinder of the twin-screw melt kneader, Benzenesulfonic acid butyramide as a plasticizer was injected by a metering pump, and the cylinder temperature was changed from 180 ° C to 26 ° C. After melt-kneading at 0 ° C. and extruding the molten resin into a strand shape, this is introduced into a water tank, cooled, cut, and vacuum dried to obtain 85% by weight of aliphatic polyketone (D-1) and 15% by weight of conductive filler. % Of a conductive fatty polyketone composition comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus-based processing stabilizer (hereinafter referred to as this conductive aliphatic group). The polyketone composition is referred to as (D-2)).

Example 1
Using the polyamide 12 composition (A-1), semi-aromatic polyamide composition (B-1), polyamide 6 composition (C1-1), and aliphatic polyketone (D-1) shown above, (Plastic Engineering Laboratory Co., Ltd.) 4 layer tube molding machine, (A-1) extrusion temperature 250 ° C, (B-1) extrusion temperature 300 ° C, (C-1) extrusion temperature 260 ° C. , (D-1) were melted separately at an extrusion temperature of 250 ° C., and the discharged molten resin was joined by an adapter to form a laminated tubular body. Subsequently, cooling is performed by a sizing die that controls the size, and the sheet is taken up. (C) layer (inner layer) consisting of 1) and (d) layer (innermost layer) consisting of (D-1), the layer configuration is (a) / (b) / (c) / (d) = A laminated tube having an inner diameter of 6 mm and an outer diameter of 8 mm was obtained at 0.40 / 0.15 / 0.30 / 0.15 mm. The physical property measurement results of the laminated tube are shown in Table 1.

Example 2
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 3
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 4
In Example 1, except that the semi-aromatic polyamide composition (B-1) was changed to (B-2) and the extrusion temperature of (B-2) was changed to 340 ° C., the same method as in Example 1 was used. Thus, a laminated tube having 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, except that the semi-aromatic polyamide composition (B-1) was changed to (B-3) and the extrusion temperature of (B-3) was changed to 310 ° C., the same method as in Example 1 was used. Thus, a laminated tube having 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, the semi-aromatic polyamide composition (B-1) was changed to (B-4), and the extrusion temperature of (B-4) was changed to 340 ° C. Thus, a laminated tube having the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 7
In Example 1, the semi-aromatic polyamide composition (B-1) was changed to (B-5) and the extrusion temperature of (B-5) was changed to 290 ° C. Thus, a laminated tube having the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 8
In Example 1, the semi-aromatic polyamide composition (B-1) was changed to (B-6), and the extrusion temperature of (B-6) was changed to 310 ° C. Thus, a laminated tube having 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, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 1 except having changed the semi-aromatic polyamide composition (B-1) into (B-7). . The physical property measurement results of the laminated tube are shown in Table 1.

Example 10
In Example 1, the semi-aromatic polyamide composition (B-1) was changed to (B-9), and the extrusion temperature of (B-9) was changed to 240 ° C. Thus, a laminated tube having 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, the semi-aromatic polyamide composition (B-1) was changed to (B-10), and the extrusion temperature of (B-10) was changed to 250 ° C. Thus, a laminated tube having the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 12
In Example 1, the semi-aromatic polyamide composition (B-1) was changed to (B-11), and the extrusion temperature of (B-11) was changed to 260 ° C. Thus, a laminated tube having the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 13
In Example 1, the semi-aromatic polyamide composition (B-1) was changed to (B-12) and the extrusion temperature of (B-12) was changed to 320 ° C. Thus, a laminated tube having the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 14
In Example 1, except that the semi-aromatic polyamide composition (B-1) was changed to (B-13) and the extrusion temperature of (B-13) was changed to 240 ° C., the same method as in Example 1 was used. Thus, a laminated tube having the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 15
In Example 1, the semiaromatic polyamide composition (B-1) was changed to (B-14) and the extrusion temperature of (B-14) was changed to 320 ° C. Thus, a laminated tube having the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 16
In Example 1, except that the polyamide 6 composition (C1-1) was changed to a polyamide 6/66/12 composition (C2-1), the layer configuration shown in Table 1 was the same as in Example 1. A laminated tube was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 17
In Example 1, except that the polyamide 6 composition (C1-1) was changed to a polyamide 6/66/12 composition (C2-2), the layer constitution shown in Table 1 was the same as in Example 1. A laminated tube was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 18
In Example 1, except that the polyamide 6 composition (C1-1) was changed to a polyamide 6/66/12 composition (C2-3), the layer configuration shown in Table 1 was the same as in Example 1. A laminated tube was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 19
In Example 1, except that the aliphatic polyketone (D-1) was changed to the conductive aliphatic polyketone composition (D-2) and the extrusion temperature of (D-2) was changed to 270 ° C. A laminated tube having the layer configuration shown in Table 1 was obtained in the same manner. 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 20
Polyamide 12 composition (A-1), semi-aromatic polyamide composition (B-1), polyamide 6 composition (C1-1), aliphatic polyketone (D-1), and conductive aliphatic polyketone shown above Using the composition (D-2), using a Plabor (Plastics Engineering Laboratory Co., Ltd.) 5-layer tube molding machine, (A-1) was extruded at an extrusion temperature of 250 ° C., (B- 1) was extruded at 300 ° C., (C1-1) was extruded at 260 ° C., (D-1) was melted at 250 ° C., and (D-2) was melted separately at 270 ° C. and discharged. The molten resin was 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), (C1-1 ) (C) layer (intermediate layer), (D-1) layer (inner layer), (D-2) layer (d ′) layer (innermost layer) (A) / (b) / (c) / (d) / (d ') = 0.35 / 0.15 / 0.30 / 0.10 / 0.10 mm, laminated tube having an inner diameter of 6 mm and an outer diameter of 8 mm Got. The physical property measurement results of the laminated tube are shown in Table 1.

Example 21
Polyamide 12 composition (A-1), semi-aromatic polyamide composition (B-1), polyamide 6 composition (C1-1), polyamide 6/66/12 composition (C2-1), and Using aliphatic polyketone (D-1), extrusion (A-1) is extruded at 250 ° C. and (B-1) is extruded in a 5-layer tube molding machine (made by Plastic Engineering Laboratory Co., Ltd.). 300 ° C, (C1-1) and (C2-1) are melted separately at an extrusion temperature of 260 ° C, and (D-1) is melted at an extrusion temperature of 250 ° C. Molded into a tubular body. Subsequently, cooling is performed by a sizing die for dimension control, and the sheet is taken up. ) (B) layer (intermediate layer), (C'-1) layer (inner layer), and (D) layer (d) layer (innermost layer). (A) / (c) / (b) / (c ′) / (d) = 0.30 / 0.10 / 0.15 / 0.30 / 0.15 mm, laminated tube having an inner diameter of 6 mm and an outer diameter of 8 mm Got. The physical property measurement results of the laminated tube are shown in Table 1. When the conductivity of the laminated tube was measured according to SAE J-2260, it was 10 ⁶ Ω / square or less, and it was confirmed that the static electricity removal performance was excellent.

Example 22
In Example 21, except that the polyamide 6 composition (C1-1) used for the inner layer was changed to a polyamide 6/66/12 composition (C2-1), Table 1 was prepared in the same manner as in Example 21. A laminated tube having the layer structure shown in FIG. The physical property measurement results of the laminated tube are shown in Table 1.

Example 23
In Example 22, except that the polyamide 6/66/12 composition (C2-1) was changed to (C2-2), a laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 22. Obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 24
In Example 22, except that the polyamide 6/66/12 composition (C2-1) was changed to (C2-3), a laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 22. Obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 25
Polyamide 12 composition (A-1), semi-aromatic polyamide composition (B-1), polyamide 6/66/12 composition (C2-1), polyamide 6 composition (C1-1), fat shown above Using a group polyketone (D-1) and a conductive aliphatic polyketone composition (D-2), a 6-layer tube molding machine (A-1) manufactured by Plabor (Plastics Engineering Laboratory Co., Ltd.) Extrusion temperature 250 ° C., (B-1) extrusion temperature 300 ° C., (C1-1) and (C2-1) extrusion temperature 260 ° C., (D-1) extrusion temperature 250 ° C., (D-2) Were melted separately at an extrusion temperature of 270 ° C., and the discharged molten resin was joined by an adapter to form a laminated tubular body. Subsequently, cooling is performed by a sizing die for dimension control, and the sheet is taken up. (B) layer (intermediate layer) consisting of (), (c ′) layer (inner layer) consisting of (C1-1), (d) layer (inner layer 2) consisting of (D-1), (D-2) (D ′) layer (innermost layer), the layer structure is (a) / (c) / (b) / (c ′) / (d) / (d ′) = 0.30 / 0.10 A laminated tube having an inner diameter of 6 mm and an outer diameter of 8 mm was obtained at /0.10/0.30/0.10/0.10 mm. 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 26
In Example 25, Table 1 was prepared in the same manner as in Example 25 except that the polyamide 6 composition (C1-1) used for the inner layer was changed to a polyamide 6/66/12 composition (C2-1). A laminated tube having the layer structure shown in FIG. The physical property measurement results of the laminated tube are shown in Table 1.

Example 27
In Example 26, except that the polyamide 6/66/12 composition (C2-1) was changed to (C2-2), a laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 26. Obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 28
In Example 26, except that the polyamide 6/66/12 composition (C2-1) was changed to (C2-3), a laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 26. Obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 1
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 12 composition (A-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 method similar to Example 1 except not using a semi-aromatic polyamide composition (B-1). The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 3
In Example 1, the semi-aromatic polyamide composition (B-1) was changed to (B-8), and the extrusion temperature of (B-8) was changed to 350 ° C. Thus, a laminated tube having 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 4
In Example 1, the semi-aromatic polyamide composition (B-1) was changed to (B-15), and the extrusion temperature of (B-15) was changed to 280 ° C. Thus, a laminated tube having 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 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 composition (C1-1). 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 same method as Example 1 except not using aliphatic polyketone (D-1). The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 7
In Example 17, except that the aliphatic polyketone (D-1) was changed to the polyamide 12 composition (A-2), a laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 1. It was. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 8
In Example 17, the aliphatic polyketone (D-1) was changed to the conductive polyamide 12 composition (A-3), and the extrusion temperature of (A-3) was changed to 270 ° C., as in Example 1. 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. 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 9
In Example 22, except that the polyamide 6/66/12 composition (C2-1) was changed to (C2-4), a laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 22. Obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 10
In Example 22, it shows in Table 1 by the method similar to Example 22 except having changed the polyamide 6/66/12 composition (C2-1) into the polyamide 6/12 composition (C2-5). A laminated tube having a layer structure was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

As is apparent from Table 1, the laminated tube of Comparative Example 1 that does not have a layer containing the aliphatic polyamide specified in the present invention is inferior in low-temperature impact resistance, and has a layer containing the semi-aromatic polyamide composition of the present invention. The laminated tube of Comparative Example 2 that did not have was inferior in chemical solution barrier properties. The laminated tubes of Comparative Examples 3 and 4 having a layer containing a semi-aromatic polyamide composition other than those defined in the present invention were inferior in interlayer adhesion. The laminated tube of Comparative Example 5 which did not have a layer containing the polyamide 6 composition and / or the polyamide 6/66/12 composition defined in the present invention was inferior in interlayer adhesion durability. The laminated tube of Comparative Example 6 that did not have the aliphatic polyketone defined in the present invention was inferior in the elution resistance of the low molecular weight component. The laminated tubes of Comparative Examples 7 and 8 that do not have a layer containing an aliphatic polyketone defined in the present invention and have a layer containing a polyamide 12 composition as the innermost layer are inferior in the elution resistance of low molecular weight components. It was. It was. The laminated tubes of Comparative Examples 9 and 10 having a layer containing a polyamide 6/66/12 composition or a polyamide 6/12 composition other than those specified in the present invention were inferior in durability of interlayer adhesion.
On the other hand, the laminated tubes of Examples 1 to 28 defined in the present invention have low temperature impact resistance, interlaminar adhesion and durability against low to high alcohol content gasoline, elution resistance of low molecular weight components, etc. It is clear that these properties are good.

Claims (12)

A laminated tube of four or more layers including (a) layer, (b) layer, (c) layer, and (d) layer,
At least one set of the (c) layer and the (d) layer are disposed adjacent to each other;
The layer (a) contains an aliphatic polyamide (A),
The layer (b) includes a semi-aromatic polyamide composition (B),
The layer (c) includes a polyamide 6 composition (C1) and / or a polyamide 6/66/12 composition (C2),
The layer (d) includes an aliphatic polyketone (D),
The aliphatic polyamide (A) does not include polycaproamide (polyamide 6) and / or poly (caproamide / hexamethylene adipamide / dodecanamide) (polyamide 6/66/12),
The semi-aromatic polyamide composition (B) includes a semi-aromatic polyamide (B1) or a semi-aromatic polyamide (B2),
The semi-aromatic polyamide (B1) contains 50 mol% or more of aliphatic diamine units having 9 or 10 carbon atoms with respect to the total diamine units of the semi-aromatic polyamide (B1). Containing 50 mol% or more of terephthalic acid units and / or naphthalenedicarboxylic acid units with respect to all dicarboxylic acid units of B1),
The semiaromatic polyamide (B2) contains 50 mol% or more of xylylenediamine units and / or bis (aminomethyl) naphthalene units with respect to all diamine units of the semiaromatic polyamide (B2), Containing 50 mol% or more of aliphatic dicarboxylic acid units having 9 or 10 carbon atoms, based on all dicarboxylic acid units of the aromatic polyamide (B2),
The polyamide 6 composition (C1) comprises polycaproamide (polyamide 6) (C11) 50% by mass to 98% by mass, plasticizer (C3) 1% by mass to 20% by mass, and an elastomer polymer (C4). Containing 1% by mass or more and 30% by mass or less,
The polyamide 6/66/12 composition (C2) is composed of 50% by mass to 98% by mass of a polyamide mixture, 1% by mass to 20% by mass of a plasticizer (C3), and an elastomer polymer (C4) 1 Containing from 30% to 30% by weight,
The polyamide mixture contains polyamide 6/66/12 (C21) 50 mass% to 100 mass% and polyamide (C22) other than polyamide 6/66/12 (C21) 0 mass% to 50 mass%. Including
The said elastomer polymer (C4) is a laminated tube containing the structural unit induced | guided | derived from the unsaturated compound which has a carboxyl group and / or an acid anhydride group.   The aliphatic polyamide (A) includes polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene decanamide (polyamide 610), polyhexamethylene dodeca At least one homopolymer selected from the group consisting of amide (polyamide 612), polydecamethylene decanamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), and polydodecamethylene dodecamide (polyamide 1212), The laminated tube according to claim 1, which is a copolymer using several kinds of raw material monomers forming these.   The laminated tube according to claim 1 or 2, wherein the semi-aromatic polyamide composition (B) contains the elastomer polymer (C4).   The polyamide 6/66/12 (C21) has a mass ratio of a total unit of caproamide units and hexamethylene adipamide units to dodecanamide units of from 81:19 to 95: 5. The laminated tube of Claim 1.   The polyamide (C22) is other than polyamide 6/66/12 (C21), and is polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene adipa Amide (polyamide 66), polyhexamethylene sebamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene decanamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), polydecamethylene At least one homopolymer selected from the group consisting of decamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), and polydodecamethylene dodecamide (polyamide 1212), and / or a raw material for forming them. amount Laminated tube according to any one of claims 1 to 4, a copolymer using several kinds of. The laminated tube according to any one of claims 1 to 5, wherein the aliphatic polyketone (D) is a polymer having a repeating unit represented by the following formula (1).

[In General Formula (1), X represents an organic group having 3 or more carbon atoms derived from an ethylenically unsaturated compound, and m and n represent a positive integer. ] The layer (a) is disposed on the outermost layer,
The laminated tube according to any one of claims 1 to 6, wherein the (c) layer is disposed between the (a) layer and the (d) layer.   The laminated tube according to any one of claims 1 to 7, wherein at least one pair of the (a) layer and the (c) layer is disposed adjacent to each other. The (d) layer is disposed in the innermost layer,
The laminated tube according to any one of claims 1 to 8, wherein the aliphatic polyketone (D) further contains a conductive filler.   The laminated tube according to any one of claims 1 to 9, which is produced by a coextrusion molding method.   The laminated tube according to any one of claims 1 to 10, which is used as a fuel tube. A laminated tube of four or more layers including (a) layer, (b) layer, (c) layer, and (d) layer,
At least one set of the (c) layer and the (d) layer are disposed adjacent to each other;
The layer (a) contains an aliphatic polyamide (A),
The layer (b) includes a semi-aromatic polyamide composition (B),
The layer (c) includes a polyamide 6 composition (C1) and / or a polyamide 6/66/12 composition (C2),
The layer (d) includes an aliphatic polyketone (D),
The aliphatic polyamide (A) does not include polycaproamide (polyamide 6) and / or poly (caproamide / hexamethylene adipamide / dodecanamide) (polyamide 6/66/12),
The semi-aromatic polyamide composition (B) includes a semi-aromatic polyamide (B1) or a semi-aromatic polyamide (B2),
The semi-aromatic polyamide (B1) contains 50 mol% or more of aliphatic diamine units with respect to the total diamine units of the semi-aromatic polyamide (B1), and the total dicarboxylic acid units of the semi-aromatic polyamide (B1). With respect to the aromatic carboxylic acid unit 50 mol% or more,
The semi-aromatic polyamide (B2) contains 50 mol% or more of aromatic diamine units with respect to the total diamine units of the semi-aromatic polyamide (B2), and the total dicarboxylic acid units of the semi-aromatic polyamide (B2). In contrast, the aliphatic dicarboxylic acid unit contains 50 mol% or more,
The polyamide 6 composition (C1) contains polycaproamide (polyamide 6) (C11), a plasticizer (C3), and an elastomer polymer (C4).
The polyamide 6/66/12 composition (C2) is a laminated tube containing polyamide 6/66/12 (C21), a plasticizer (C3), and an elastomer polymer (C4).