JP2021151785A - 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 laminated tubes.

In automobile piping tubes, in response to the problem of rusting caused by road antifreeze agents, prevention of global warming, and energy saving, the main material is metal, which has excellent rust prevention and is lightweight. Substitution to resin is progressing. Examples of resins usually used as piping tubes include polyamide-based resins, saturated polyester-based resins, polyolefin-based resins, and thermoplastic polyurethane-based resins, but single-layer tubes using these include heat resistance and resistance. The applicable range was limited due to insufficient chemical properties.

Further, in automobile piping tubes, oxygen-containing gasoline blended with alcohols having a low boiling point 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 emission regulations are being implemented, including prevention of leakage into the atmosphere due to diffusion of volatile hydrocarbons and the like through the partition of the pipe tube. In response to such strict regulations, a single-layer tube using a polyamide resin, particularly a polyamide 11 or a polyamide 12 having excellent strength, toughness, chemical resistance, flexibility, etc., which has been conventionally used, is described above. The barrier property to the chemical solution is not sufficient, and improvement in the alcohol-containing gasoline barrier property is particularly required.

As a method for solving this problem, resins having good chemical barrier properties, such as ethylene / vinyl acetate copolymer saponified product (EVOH), polymethoxylylene adipamide (polyamide MXD6), polybutylene terephthalate (PBT), and polyethylene. Naphthalate (PEN), polybutylene naphthalate (PBN), polyphenylene sulfide (PPS), polyvinylidene fluoride (PVDF), ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / tetrafluoroethylene / hexafluoropropylene co-weight Combined (EFEP), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (TFE / HFP / VDF, THV), Tetrafluoroethylene / Hexafluoropropylene / Vinylidene fluoride / Perfluoro (alkyl vinyl ether) copolymer (TFE / HFP / VDF / PAVE), Tetrafluoroethylene / Perfluoro (alkyl vinyl ether) ) Copolymer (TFE / PAVE, PFA), Tetrafluoroethylene / Hexafluoropropylene / Perfluoro (alkyl vinyl ether) copolymer (TFE / HFP / PAVE), Chlorotrifluoroethylene / Perfluoro (alkyl vinyl ether) / Tetra Laminated tubes in which fluoroethylene copolymers (CTFE / PAVE / TFE, CPT) are arranged have been proposed (see, for example, Patent Document 1 and the like).

Further, a molded product using a conventionally used polyamide resin, particularly nylon 11 or nylon 12 having excellent strength, toughness, chemical resistance, and flexibility in the innermost layer, is a monomer, which is brought into contact with the fuel. It has been confirmed that low molecular weight components such as oligomers gradually elute and precipitate in the fuel, and adhesion to the moving parts of the injector and fuel tank valve may cause the engine to become unstartable, or the internal pressure of the fuel tank may be 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 elution resistance of monomers and oligomers, and having a low specific density and low cost. The present inventors have prepared a layer made of an aliphatic polyamide, a diamine unit containing 60 mol% or more of 1,9-nonanediamine unit and / or 2-methyl-1,8-octanediamine unit with respect to all diamine units. Lamination 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 the dicarboxylic acid units. A structure has been proposed (see Patent Documents 2 to 5).

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

Further, a multilayer structure having 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 an aliphatic ketone are directly adjacent to each other, or a layer made of an aliphatic ketone. 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 has been proposed (Patent Documents 6 and 7). reference). Further, a multilayer structure has been proposed 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 are arranged directly adjacent to each other (see Patent Document 8). ).

U.S. Pat. No. 5,554,425 Japanese Unexamined Patent Publication No. 3-177683 Special Table 2003-535717 Japanese Unexamined Patent Publication No. 2003-021276 JP-A-2002-210904 Japanese Unexamined Patent Publication No. 7-266503 JP-A-11-245358 JP-A-11-245340 U.S. Pat. No. 2,495,286 Japanese Unexamined Patent Publication No. 53-128690 JP-A-59-197427 Japanese Unexamined Patent Publication No. 61-91226 Japanese Unexamined Patent Publication No. 62-232434 Japanese Unexamined Patent Publication No. 62-53332 Japanese Unexamined Patent Publication No. 63-3025 Japanese Unexamined Patent Publication No. 63-105031 Japanese Unexamined Patent Publication No. 63-154737 Japanese Unexamined Patent Publication No. 1-148929 Japanese Unexamined Patent Publication No. 1-201333 Japanese Unexamined Patent Publication No. 2-67319

However, although polynonamethylene terephthalamide (PA9T) satisfies the barrier property against hydrocarbons, further improvement in the barrier property against gasoline containing high-concentration alcohol such as ethanol is desired. In order to improve the barrier property against high-concentration alcohol-containing gasoline, there is a method of laminating a fluorine-based polymer such as ethylene / tetrafluoroethylene copolymer (ETFE), but the use of halogen-containing materials is avoided due to environmental friendliness. In addition to the problems of high specific gravity and high cost, halogen-free materials are used, excellent barrier properties against low-concentration to high-concentration alcohol-containing gasoline, and excellent elution resistance of low-molecular-weight components such as monomers and oligomers. There is a need to develop a piping system that can be used for various fuels.

Further, 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, displacement absorption at the time of collision, and the like. 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 lower. There arises a problem that the innermost layer is peeled off, causing blockage of the pipe, or the outermost layer is peeled off, and the original performance as a tube such as pressure resistance and yield strength is lost. Therefore, it is one of the important performances that should be considered not only in the initial stage but also in the interlayer adhesiveness (durability of interlayer adhesiveness) after heat treatment.

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

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

As a result of diligent studies to solve the above problems, the present inventors have conducted a layer containing an aliphatic polyamide (polyamide 11, 12, etc.), a layer containing a semi-aromatic polyamide composition, a polyamide 6 composition and /. Or a layer containing a polyamide 6/66/12 composition and a layer containing an aliphatic polyketone, and at least one set of polyamide 6 composition and / or a layer containing a polyamide 6/66/12 composition and an aliphatic polyketone. The laminated tube in which the layer containing the layer containing the layer is arranged adjacent to the layer contains low-temperature impact resistance, barrier property against low-concentration to high-concentration alcohol-containing gasoline, interlayer adhesion and its durability, and elution resistance of low molecular weight components. It was found that it is excellent in various characteristics such as.

That is, the present invention
A laminated tube having four or more layers including a layer (a), a layer (b), a layer (c), and a layer (d).
At least one set of the layer (c) and the layer (d) are arranged adjacent to each other.
The layer (a) contains an aliphatic polyamide (A) and contains
The layer (b) contains the semi-aromatic polyamide composition (B) and contains.
The layer (c) contains a polyamide 6 composition (C1) and / or a polyamide 6/66/12 composition (C2).
The layer (d) contains an aliphatic polyketone (D) and contains
The aliphatic polyamide (A) does not contain polycaproamide (polyamide 6) and / or poly (caproamide / hexamethylene adipamide / dodecane amide) (polyamide 6/66/12).
The semi-aromatic polyamide composition (B) contains a semi-aromatic polyamide (B1) or a semi-aromatic polyamide (B2).
The semi-aromatic polyamide (B1) contains 50 mol% or more of an aliphatic diamine unit having 9 or 10 carbon atoms with respect to the total diamine units of the semi-aromatic polyamide (B1), and the semi-aromatic polyamide (B1). B1) contains 50 mol% or more of terephthalic acid units and / or naphthalenedicarboxylic acid units with respect to all dicarboxylic acid units.
The semi-aromatic polyamide (B2) contains 50 mol% or more of xylylene diamine units and / or bis (aminomethyl) naphthalene units with respect to the total diamine units of the semi-aromatic polyamide (B2), and the semi-aromatic polyamide (B2). It contains 50 mol% or more of an aliphatic dicarboxylic acid unit having 9 or 10 carbon atoms with respect to all the dicarboxylic acid units of the group polyamide (B2).
The polyamide 6 composition (C1) contains 50% by mass or more and 98% by mass or less of polycaproamide (polyamide 6) (C11), 1% by mass or more and 20% by mass or less of a plasticizer (C3), and an elastomer polymer (C4). Contains 1% by mass or more and 30% by mass or less,
The polyamide 6/66/12 composition (C2) contains 50% by mass or more and 98% by mass or less of the polyamide mixture, 1% by mass or more and 20% by mass or less of the plasticizer (C3), and the elastomer polymer (C4) 1 in the composition. Containing by mass% or more and 30% by mass or less,
The polyamide mixture contains 50% by mass or more and 100% by mass or less of polyamide 6/66/12 (C21) and 0% by mass or more and 50% by mass or less of polyamide (C22) other than polyamide 6/66/12 (C21). 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。 A preferred embodiment of the laminated tube is shown below. A plurality of preferred embodiments can be combined.
[1] The aliphatic polyamide (A) includes polyundecaneamide (polyamide 11), polydodecaneamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylenedecamide (polyamide 610), and poly. At least one single selected from the group consisting of hexamethylene dodecamide (polyamide 612), polydecamethylene decamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), and polydodecamethylene dodecamide (polyamide 1212). A laminated tube which is a copolymer using a polymer and / or 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 the total unit of caproamide unit and hexamethylene adipamide unit and the mass ratio of dodecaneamide unit are 81:19 or more and 95: 5.
[4] The polyamide (C22) is other than polyamide 6/66/12 (C21), and is polycaproamide (polyamide 6), polyundecaneamide (polyamide 11), polydodecaneamide (polyamide 12), polyhexa. Methylene adipamide (polyamide 66), polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene decamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), Forming at least one homopolymer selected from the group consisting of polydecamethylene decamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), and polydodecamethylene dodecamide (polyamide 1212), and / or these. A laminated tube which is a copolymer using several kinds of raw material 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 the 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 positive integers. ]
[6] The layer (a) is arranged on the outermost layer.
A laminated tube in which the layer (c) is arranged between the layer (a) and the layer (d).
[7] A laminated tube in which at least one set of the layer (a) and the layer (c) are arranged adjacent to each other.
[8] The layer (d) is arranged 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.
In addition, the present invention
A laminated tube having four or more layers including a layer (a), a layer (b), a layer (c), and a layer (d).
At least one set of the layer (c) and the layer (d) are arranged adjacent to each other.
The layer (a) contains an aliphatic polyamide (A) and contains
The layer (b) contains the semi-aromatic polyamide composition (B) and contains.
The layer (c) contains a polyamide 6 composition (C1) and / or a polyamide 6/66/12 composition (C2).
The layer (d) contains an aliphatic polyketone (D) and contains
The aliphatic polyamide (A) does not contain polycaproamide (polyamide 6) and / or poly (caproamide / hexamethylene adipamide / dodecane amide) (polyamide 6/66/12).
The semi-aromatic polyamide composition (B) contains a semi-aromatic polyamide (B1) or a semi-aromatic polyamide (B2).
The semi-aromatic polyamide (B1) contains 50 mol% or more of an aliphatic diamine unit 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). On the other hand, it contains 50 mol% or more of aromatic carboxylic acid units.
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). On the other hand, it contains 50 mol% or more of an aliphatic dicarboxylic acid unit.
The polyamide 6 composition (C1) contains a polycarbonate (polyamide 6) (C11), a plasticizer (C3), and an elastomer polymer (C4).
The polyamide 6/66/12 composition (C2) is a laminated tube containing the polyamide 6/66/12 (C21), a plasticizer (C3), and an elastomer polymer (C4).

According to the present invention, it is possible to provide a laminated tube having excellent low temperature impact resistance, barrier property against gasoline containing low to high concentration alcohol, interlayer adhesion and durability thereof, and elution resistance of low molecular weight components. ..

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 otherwise specified, when a plurality of substances corresponding to each component are present in the composition. means.

The laminated tube according to the present embodiment contains 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. Adhesiveness is provided by having a layer containing at least one set of polyamide 6 composition and / or a layer containing a polyamide 6/66/12 composition and a layer containing an aliphatic polyketone arranged adjacent to each other. It has both barrier properties against alcohol-containing gasoline, and is excellent in various 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 contacting / immersing in fuel for a long time, after heat treatment, etc., there is little decrease in interlayer adhesive strength, excellent durability of interlayer adhesiveness, and small elution amount of low molecular weight components such as monomers and oligomers. Therefore, the laminated tube according to the present embodiment can be used in any environment, has high reliability, and has extremely high utility value.

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

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

Examples of the lactam include enantractum, 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 be used alone or in combination of two or more.

As the aliphatic diamine, 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptandiamine, 1, 8-octane diamine, 1,9-nonan diamine, 1,10-decane diamine, 1,11-undecane diamine, 1,12-dodecane diamine, 1,13-tridecane diamine, 1,14-tetradecane diamine, 1,15 -Pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecandiamine, 1,19-nonadecandiamine, 1,20-eicosandiamine, 2-methyl-1,5- Pentandiamine, 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1, Examples thereof include 6-hexanediamine and 5-methyl-1,9-nonanediamine. These can be used alone or in combination of two or more.

Examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, and tetradecanedioic acid. Examples thereof include pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eikosandioic acid. These can be used alone or in combination of two or more.

Examples of the aliphatic polyamide (A) include polyundecaneamide (polyamide 11), polydodecaneamide (polyamide 12), polyethylene adipamide (polyamide 26), polytetramethylene succinamide (polyamide 44), and polytetramethylene glutamide. (Polyamide 45), Polytetramethylene adipamide (Polyamide 46), Polytetramethylene sveramide (Polyamide 48), Polytetramethylene azelamide (Polyamide 49), Polytetramethylene sebacamide (Polyamide 410), Polytetramethylene Dodecamide (polyamide 412), polypentamethylene succinamide (polyamide 54), polypentamethylene glutamide (polyamide 55), polypentamethylene adipamide (polyamide 56), polypentamethylene sveramide (polyamide 58), poly Pentamethylene azelamide (polyamide 59), polypentamethylene sebacamide (polyamide 510), polypentamethylene dodecamide (polyamide 512), polyhexamethylene succinamide (polyamide 64), polyhexamethylene glutamide (polyamide 65) , Polyhexamethylene adipamide (polyamide 66), polyhexamethylene sveramide (polyamide 68), polyhexamethylene azelamide (polyamide 69), polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide) 612), polyhexamethylene tetradecamide (polyamide 614), polyhexamethylene hexadecamide (polyamide 616), polyhexamethylene octadecamide (polyamide 618), polynonamethylene adipamide (polyamide 96), polynonamethylene Suberamide (polyamide 98), polynonamethylene azelamide (polyamide 99), polynonamethylene sebacamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), polydecamethylene adipamide (polyamide 106), poly Decamethylene sveramide (polyamide 108), polydecamethylene azelamide (polyamide 109), polydecamethylene sebacamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), polydodecamethylene adipamide (polyamide 126) , Polydodecamethylene sveramide (polyamide 128), polydodecamethylene azelamide (polyamide 129), polydodecamethylene sebacamide (po) Examples thereof include homopolymers such as rearamide 1210) and polydodecamethylene dodecamide (polyamide 1212), and / or copolymers using several kinds of raw material monomers forming these.

Among these, polyundecaneamide (polyamide 11) and polydodecaneamide (polyamide 12) are available from the viewpoints of economic efficiency and availability, while sufficiently ensuring various physical properties such as mechanical properties and heat resistance of the obtained laminated tube. ), Polyhexamethylene adipamide (polyamide 66), polyhexamethylene decamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecamethylene decamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1010). 1012) and at least one homopolymer selected from the group consisting of polydodecamethylene dodecamide (polyamide 1212), and / or a copolymer using several raw materials monomers forming these are preferable.

Examples of the apparatus for producing the aliphatic polyamide (A) include a batch type reaction kettle, a single-tank or multi-tank continuous reaction device, a tubular continuous reaction device, a uniaxial kneading extruder, a twin-screw kneading extruder, and the like. Known polyamide production equipment such as an extruder can be mentioned. As a polymerization method, known methods such as melt polymerization, solution polymerization, and solid phase polymerization can be used, and polymerization can be carried out by repeating normal pressure, reduced pressure, and pressurizing operations. These polymerization methods can be used alone or in combination as appropriate.

In addition, the relative viscosity of the aliphatic polyamide (A) measured under the conditions of 96% sulfuric acid, polymer concentration 1%, and 25 ° C. in accordance with JIS K-6920 ensures the mechanical properties of the obtained laminated tube. From the viewpoint of ensuring the desirable moldability of the laminated tube by setting the viscosity at the time of melting in 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 the aliphatic polyamide (A) is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), the interlayer adhesiveness of the laminated tube and its durability thereof. From the viewpoint of sufficiently securing, [A]> [B] +5 is preferable, [A]> [B] +10 is more preferable, and [A]> [B] +15 is further preferable. preferable. Further, from the viewpoint of the melt stability of the polyamide and the suppression of the generation of gel-like substances, [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 mixed solution of phenol / methanol and titrating with 0.05 N hydrochloric acid. The terminal carboxyl group concentration [B] (μeq / g) can be measured by dissolving the polyamide in benzyl alcohol and titrating with a 0.05 N 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, or solid phase polymerization. Alternatively, it is produced by melt-kneading in the presence of amines after polymerization. As described above, amines can be added at any stage during polymerization or at any stage during melt-kneading after polymerization, but when the interlayer adhesiveness of the laminated tube is taken into consideration, they are added at the stage during polymerization. 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, if necessary, as long as they do not deviate from the above-mentioned terminal group concentration conditions. These amines and carboxylic acids may be added at the same time or separately. Further, as the amines and carboxylic acids exemplified below, one kind or two or more kinds can be used.

Specific examples of the monoamine to be added include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine and 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-dihexylamine, N, N-dioctyl Symmetrical secondary amines such as amines; N-methyl-N-ethylamine, N-methyl-N-butylamine, N-methyl-N-dodecylamine, N-methyl-N-octadecylamine, N-ethyl-N-hexadecyl Examples thereof include mixed secondary amines such as amines, N-ethyl-N-octadecylamines, N-propyl-N-hexadecylamines and N-propyl-N-benzylamines. These can be used alone or in combination of two or more.

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-nonandiamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-Pentadecanediamine, 1,16-hexadecandiamine, 1,17-heptadecanediamine, 1,18-octadecandiamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine , 2-Methyl-1,8-octanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9- Aliper diamines such as nonandiamine; 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) norbornan, 2,6-bis (aminomethyl) norbornan , 3,8-Bis (aminomethyl) tricyclodecane, 4,9-bis (aminomethyl) tricyclodecane and other alicyclic diamines; Can be mentioned. These can be used alone or in combination of two or more.

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 Examples thereof include 1,4,5,8-tetraminonaphthalene such as −triaminonaphthalene, 2,4,6-triaminopyridine, 1,2,7,8-tetraminonaphthalene and the like. These can be used alone or in combination of two or more.

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 and the like. Can be mentioned. The amino group with active hydrogen is the reaction site for polyamines.

Polyalkyleneimine is produced by a method of ion-polymerizing an alkyleneimine such as ethyleneimine or propyleneimine, or a method of polymerizing an alkyloxazoline and then partially or completely hydrolyzing the polymer. Examples of the polyalkylene polyamine include diethylenetriamine, triethylenetetramine, pentaethylenehexamine, and a reaction product of ethylenediamine and a polyfunctional compound. Polyvinylamine can be obtained, for example, by polymerizing N-vinylformamide to obtain 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 salt of an allylamine monomer and then removing hydrochloric acid. These can be used alone or in combination of two or more. Among these, polyalkyleneimine is preferable.

The polyalkyleneimine is one or 2 of alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, and 1,1-dimethylethyleneimine. Examples thereof include homopolymers and / or copolymers obtained by polymerizing seeds or more by a conventional method. Among these, polyethyleneimine is more preferable. Polyalkyleneimine is obtained by ring-opening polymerization of alkyleneimine as a raw material, and branched polyalkyleneimine containing primary amine, secondary amine, and tertiary amine, or alkyloxazoline as a raw material, which is polymerized. It may be either a linear polyalkyleneimine containing only the primary amine and the secondary amine obtained by the above, or a three-dimensionally crosslinked structure. Further, it may contain ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine, bisaminopropylethylenediamine and the like. Polyalkyleneimines are usually derived from the reactivity of active hydrogen atoms on the contained nitrogen atoms, and in addition to tertiary amino groups, primary amino groups and / or secondary amino groups having active hydrogen atoms. It has (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 further preferably 11 or more and 500 or less. .. The number average molecular weight of 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 the carboxylic acids to be added, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, capric acid, capric acid, pelargonic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, myristoleic acid, Adicyclic monocarboxylic acids such as palmitic acid, stearic acid, oleic acid, linoleic acid, araquinic acid, behenic acid and erucic acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid and methylcyclohexanecarboxylic acid; benzoic acid and toluic acid , Ethylbenzoic acid, aromatic monocarboxylic acids such as phenylacetic acid; malonic acid, succinic acid, glutaric acid, adipic acid, pimelliic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, hexadecanedioic acid , Hexadecenedioic acid, octadecanedioic acid, octadecenedioic acid, eicosandioic acid, eicosendioic acid, docosanedioic acid, diglycolic acid, 2,2,4-trimethyladiponic acid, 2,4,4-trimethyladiponic acid, etc. Aliphatic dicarboxylic acid; alicyclic dicarboxylic acid such as 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, norbornandicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, m-xylylene dicarboxylic acid, p- Aromatic dicarboxylic acids such as xylylene dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid; 1,2,4-butanetricarboxylic acid, 1,3,5 Examples thereof include tricarboxylic acids such as -pentanetricarboxylic acid, 1,2,6-hexanetricarboxylic acid, 1,3,6-hexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid and trimesic acid. These can be used alone or in combination of two or more.

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

In the aliphatic polyamide (A), among the above-exemplified amines, it is preferable to add a diamine and / or a polyamine at the time of polymerization in order to satisfy the condition of the terminal group concentration, and from the viewpoint of suppressing gel generation, the aliphatic polyamide (A) is used. More preferably, it is at least one selected from the group consisting of diamines, alicyclic diamines, and polyalkyleneimines.

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

In order to improve the flexibility of the aliphatic polyamide (A), the plasticizer (C3) described in the polyamide 6 composition (C1) and / or the polyamide 6/66/12 composition (C2) described later is added. You may.
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 preferably 2 parts by mass or more and 20 parts by mass or less.

Further, in order to improve the low temperature impact resistance of the aliphatic polyamide (A), it is preferable to add an impact improving material, and in particular, the polyamide 6 composition (C1) and / or the polyamide 6/66/12 composition described later. It is more preferable to add the elastomer polymer (C4) containing the structural unit derived from the unsaturated compound having a carboxyl group and / or an acid anhydride group described in (C2). If the elastomer polymer (C4), which will be 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 improving material is 1 part by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the aliphatic polyamide (A) from the viewpoint of sufficiently ensuring the mechanical strength and low temperature impact resistance of the laminated tube. It is 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-mentioned homopolymers, a mixture of the above-mentioned copolymers, a mixture of a homopolymer and a copolymer, or another polyamide-based 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-based resins include polymethoxylylene succinamide (polyamide MXD4), polymethoxylylen glutamide (polyamide MXD5), polymethoxylylen adipamide (polyamide MXD6), and polymethoxylylence veramide (polyamide MXD8). , Polymethaxylylene dedecamide (Polyamide MXD12), Polymethoxylylene terephthalamide (Polyamide MXDT), Polymethoxylylene isophthalamide (Polyamide MXDI), Polymethoxylylene hexahydroterephthalamide (Polyamide MXDT (H)), Polyme Taxylylene naphthalamide (polyamide MXDN), polyparaxylylene succinamide (polyamide PXD4), polyparaxylylene glutamide (polyamide PXD5), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylene veramide (polyamide PXD6) Polyamide PXD8), polyparaxylylene dedecamide (polyamide PXD12), polyparaxylylene terephthalamide (polyamide PXDT), polyparaxylylene isophthalamide (polyamide PXDI), polyparaxylylene hexahydroterephthalamide (polyamide) PXDT (H)), polyparaxylylene naphthalamide (polyamide PXDN), polyparaphenylene terephthalamide (PPTA), polyparaphenylene isophthalamide (PPIA), polymetaphenylene terephthalamide (PMTA), polymetaphenylene Isophthalamide (PMIA), poly (2,6-naphthalenedimethylene adipamide) (polyamide 2,6-BAN6), poly (2,6-naphthalenedimethylene sveramide) (polyamide 2,6-BAN8), Poly (2,6-naphthalenedimethylene azelamide) (polyamide 2,6-BAN9), poly (2,6-naphthalenedimethylene sebacamide) (polyamide 2,6-BAN10), poly (2,6-naphthalene) Dimethylene dodecamide) (polyamide 2,6-BAN12), poly (2,6-naphthalenedimethylene terephthalamide) (polyamide 2,6-BANT), poly (2,6-naphthalenedimethylene isophthalamide) ( Polyamide 2,6-BANI), poly (2,6-naphthalenedimethylene hexahydroterephthalamide) (polyamide 2,6-BANT (H)), poly (2,6-naphthalenedimethylene naphthalamide) (polyamide 2) , 6-BANN), Poly (1,3-Cyclohexanedimethylenea) Zipamide) (polyamide 1,3-BAC6), poly (1,3-cyclohexanedimethylene sveramide (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-cyclohexanedimethyleneisophthalamide) (polyamide 1,3-BACI), poly (1,3-cyclohexanedimethylenehexahydro) Tereftalamide) (polyamide 1,3-BACT (H)), poly (1,3-cyclohexanedimethylenenaphthalamide) (polyamide 1,3-BACN), poly (1,4-cyclohexanedimethyleneadipamide) (Polyamide 1,4-BAC6), Poly (1,4-cyclohexanedimethylene sveramide) (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-BAC12), poly (1,4-BAC12) Cyclohexanedimethylene terephthalamide) (polyamide 1,4-BACT), poly (1,4-cyclohexanedimethyleneisophthalamide) (polyamide 1,4-BACI), poly (1,4-cyclohexanedimethylenehexahydroteramide) Phthalamide) (polyamide 1,4-BACT (H)), poly (1,4-cyclohexanedimethylenenaphthalamide) (polyamide 1,4-BACN), poly (4,4'-methylenebiscyclohexylene adipamide) ) (Polyamide PACM6), Poly (4,4'-methylenebiscyclohexylene veramide) (Polyamide PACM8), Poly (4,5'-methylenebiscyclohexylene azelamide) (Polyamide PACM9), Poly (4,4' -Methylenebiscyclohexylene sebacamide) (polyamide PACM10), poly (4,4'-methylenebiscyclohexylenedodecamide) (polyamide PACM12), poly (4,4'-methylenebiscyclohexylenetetradecamide) (polyamide) PACM 14), Poly (4,4'-methylenebiscyclohexylene hexadecamide) (polyamide PACM16), Poly (4,4'-methylenebiscyclohexylene octadecamide) (polyamide PACM18), Poly (4,4'- Methylenebiscyclohexylene terephthalamide) (polyamide PACMT), poly (4,5'-methylenebiscyclohexylene isophthalamide) (polyamide PACMI), poly (4,5'-methylenebiscyclohexylene hexahydroterephthalamide) (Polyamide PACMT (H)), Poly (4,4'-methylenebiscyclohexylene naphthalamide) (Polyamide PACMN), Poly (4,4'-Methylenebis (2-methyl-cyclohexylene) adipamide) (Polyamide MACM6), Poly (4,4'-methylenebis (2-methyl-cyclohexylene) sveramide) (polyamide MACM8), poly (4,4'-methylenebis (2-methyl-cyclohexylene) azelamide) (polyamide MACM9), poly (4, 4'-Methylenebis (2-methyl-cyclohexylene) sebacamide) (polyamide MACM10), poly (4,5'-methylenebis (2-methyl-cyclohexylene) dodecamide) (polyamide MACM12), poly (4,5'-methylenebis) (2-Methyl-cyclohexylene) tetradecamide) (polyamide MACM14), poly (4,5'-methylenebis (2-methyl-cyclohexylene) hexadecamide) (polyamide MACM16), poly (4,4'-methylenebis (2-methyl) -Cyclohexylene) octadecamide) (polyamide MACM18), poly (4,5'-methylenebis (2-methyl-cyclohexylene) terephthalamide) (polyamide MACMT), poly (4,5'-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 (4,5'-propylene biscyclohexylene adipamide) (polyamide PACP6), poly (4,5'-propylene biscyclohexylene veramide) (polyamide PACP8), poly (4,4'-propylene biscyclohexylene azelamide) (Polyamide PACP9), Poly (4,4'-propylene biscyclohexylene sebacamide) (Polyamide PACP10), Poly (4,4'-propylene biscyclohexylenedodecamide) (Polyamide PACP12), Poly (4,4' -Propropylene biscyclohexylene tetradecamide) (polyamide PACP14), poly (4,4'-propylene biscyclohexylene hexadecamide) (polyamide PACP16), poly (4,4'-propylene biscyclohexylene octadecamide) ( Polyamide PACP18), poly (4,5'-propylene biscyclohexylene terephthalamide) (polyamide PACPT), poly (4,5'-propylene biscyclohexylene isophthalamide) (polyamide PACPI), poly (4,4' -Propropylene biscyclohexylene hexahydroterephthalamide) (polyamide PACPT (H)), poly (4,4'-propylene biscyclohexylene naphthalamide) (polyamide PACPN), polyisophorone adipamide (polyamide IPD6), polyisophorone Suberamide (polyamide IPD8), polyisophorone azelamide (polyamide IPD9), polyisophorone sebacamide (polyamide IPD10), polyisophorondodecamide (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)), polytetramethylenenaphthalamide (polyamide 4N), polypentamethylene terephthalamide (polyamide 5T), polypentamethylene isophthalamide (polyamide 5I), poly Pentamethylene hexahydroterephthalamide (polyamide 5T (H)), polypentamethylene naphthalamide (polyamide 5N), polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene Hexahydroterephthalamide (polyamide 6T (H)), polyhexamethylenenaphthalamide (polyamide 6N), poly (2-methylpentame) Tyrene terephthalamide) (polyamide M5T), poly (2-methylpentamethyleneisophthalamide) (polyamide M5I), poly (2-methylpentamethylenehexahydroterephthalamide) (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)), Polytrimethylhexamethyleneisophthalamide (PolyamideTMHI), Polytrimethylhexamethylenehexahydroterephthalamide (PolyamideTMHT (PolyamideTMHT) H)), polydecamethylene isophthalamide (polyamide 10I), polydecamethylene hexahydroterephthalamide (polyamide 10T (H)), polyundecamethylene terephthalamide (polyamide 11T), polyundecamethylene isophthalamide (Polyamide 11I), Polyundecamethylene hexahydroterephthalamide (Polyamide 11T (H)), Polyundecamethylene naphthalamide (Polyamide 11N), Polydodecamethylene terephthalamide (Polyamide 12T), Polydodecamethylene isophthalamide (Polyamide 12I), polydodecamethylene hexahydroterephthalamide (polyamide 12T (H)), homopolymers such as polydodecamethylene naphthalamide (polyamide 12N), and / or several kinds of raw material monomers of these polyamides are used. Examples thereof include the copolymers that were present. These can be used alone or in combination of two or more.

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 ultrahigh-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 Polypropylene-based resins such as copolymers (EEA); polystyrene (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 Polystyrene resins such as copolymers (SIS), styrene / ethylene / butylene / styrene copolymers (SEBS), styrene / ethylene / propylene / styrene copolymers (SEPS); carboxyl groups and salts thereof, acid anhydride groups , The polyolefin-based resin and the polystyrene-based resin containing a functional group such as an epoxy group; all of polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), and poly (ethylene terephthalate / ethylene isophthalate). Polymer (PET / PEI), polytrimethylene terephthalate (PTT), polycyclohexanedimethylene terephthalate (PCT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyarylate (PAR), liquid crystal polyester (LCP) ), Polylactic acid (PLA), polyglycolic acid (PGA) and other polymer resins; polyether resins such as polyacetal (POM) and polyphenylene ether (PPO); polysulfone (PSU), polyether sulfone (PESU), poly Polymers such as phenylsalphon (PPSU) Copolymer-based resin: Polythioether-based resin 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 (PEEEK), polyether ether ketone ketone (PEEKK), polyether ketone ketone ketone (PEKKK), polyether ketone ether ketone ketone (PEKEKK); polyacrylonitrile (PAN), polymethacrylonitrile, Polynitrile resins such as acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), acrylonitrile / butadiene copolymer (NBR); polymethylmethacrylate Polymethacrylate-based resins such as (PMMA), polyethyl methacrylate (PEMA); polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / Polyvinyl resin such as methyl acrylate copolymer; Cellulosic resin such as cellulose acetate and cellulose butyrate; Polycarbonate resin such as polycarbonate (PC); Thermoplastic polyimide (TPI), polyetherimide, polyesterimide, polyamideimide ( PAI), polyimide resins such as polyesteramidoimide; thermoplastic polyurethane resins; polyamide elastomers, polyurethane elastomers, polyester elastomers and the like, and in some cases, polyvinylidene fluoride (PVDF), vinyl fluoride (PVF), polytetra Fluoroethylene (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), tetrafluoroe Fluorine-based resins such as chillene / hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer and chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer (CPT) can be mentioned. These can be used alone or in combination of two or more.

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

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

[Semi-aromatic polyamide composition (B)]
The semi-aromatic polyamide composition (B) contains 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). The unit contains 50 mol% or more of an aliphatic diamine unit having 9 or 10 carbon atoms, and the terephthalic acid unit and / or the naphthalenedicarboxylic acid unit is based on the total dicarboxylic acid unit of the semi-aromatic polyamide (B1). The semi-aromatic polyamide (B2) contains 50 mol% or more of xylylene diamine units and / or bis (aminomethyl) naphthalene units with respect to the total diamine units of the semi-aromatic polyamide (B2). % Or more, and 50 mol% or more of an aliphatic dicarboxylic acid unit having 9 or 10 carbon atoms is contained with respect to the total dicarboxylic acid unit of the semi-aromatic polyamide (B2) (hereinafter, semi-aromatic polyamide composition (B). ).).

[Semi-aromatic polyamide (B1)]
The semi-aromatic polyamide composition (B) may contain a semi-aromatic polyamide (B1) (hereinafter, may be referred to as a semi-aromatic polyamide (B1)), and the semi-aromatic polyamide (B1) is a semi-aromatic polyamide (B1). For all diamine units of semi-aromatic polyamide (B1), for diamine units containing 50 mol% or more of aliphatic diamine units having 9 or 10 carbon atoms, and for all dicarboxylic acid units of semi-aromatic polyamide (B1). It contains 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) sufficiently satisfies various physical properties such as heat resistance, chemical resistance, impact resistance, and chemical barrier property of the obtained laminated tube. From the viewpoint of ensuring the above, the amount is 50 mol% or more, preferably 55 mol% or more, and more preferably 60 mol% or more, 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. 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2,4-diethyl-1,6-hexane as long as the number of carbon atoms satisfies the above. 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 −Diamine-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-1,9-nonanediamine, 4-methyl-1 , 9-Nonandiamine, 5-Methyl-1,9-Nonandiamine and the like may contain units derived from branched chain aliphatic diamines. These can be used alone or in combination of two or more.

Among the aliphatic diamine units having 9 or 10 carbon atoms, from 1,9-nonandiamine, 2-methyl-1,8-octanediamine, and 1,10-decanediamine from the viewpoint of availability and economy. Induced units are preferred. Furthermore, when 1,9-nonandiamine and 2-methyl-1,8-octanediamine are used in combination, the molar ratio of 1,9-nonandiamine unit and 2-methyl-1,8-octanediamine unit is moldability and resistance. From the viewpoint of the balance of impact resistance, 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) contains 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 be. Other diamine units include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptandiamine, 1 , 8-octane diamine, 1,11-undecane diamine, 1,12-dodecane diamine, 1,13-tridecane diamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, etc. Units derived from the aliphatic diamines of: 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- From alicyclic diamines such as bis (aminomethyl) norbornan, 2,6-bis (aminomethyl) norbornan, 3,8-bis (aminomethyl) tricyclodecane, 4,9-bis (aminomethyl) tricyclodecane, etc. Units to be derived; m-phenylenediamine, p-phenylenediamine, m-xylylene diamine, p-xylylene diamine, 1,4-bis (aminomethyl) naphthalene, 1,5-bis (aminomethyl) naphthalene, 2 , 6-bis (aminomethyl) naphthalene, 2,7-bis (aminomethyl) naphthalene, 4,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 4,4'-diaminodiphenylsulfone , 4,4'-Diaminodiphenyl ether and other units derived from aromatic diamines, 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 semi-aromatic polyamide (B1). More preferred.

Further, the content of the terephthalic acid unit and / or the 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, based on the total dicarboxylic acid unit 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 be used alone or in combination of two or more. Among the naphthalene dicarboxylic 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) may be a dicarboxylic acid unit other than the terephthalic acid unit and / or the naphthalenedicarboxylic acid unit as long as it does not impair the excellent properties of the obtained laminated tube. It may be included. Other dicarboxylic acid units include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, pimeric 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, hexadecanedi Units derived from aliphatic dicarboxylic acids such as acids, octadecanedioic acids and eicosandioic acids; alicyclic formulas such as 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. Units derived from dicarboxylic acids; phthalic acid, isophthalic 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, diphenylether-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 4,4' Examples thereof include units derived from aromatic dicarboxylic acids such as −biphenyldicarboxylic acid and 4,4′-triphenyldicarboxylic acid, and these may be used alone or in combination of two or more. Among these, units derived from aromatic dicarboxylic acids are preferable. 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 the total dicarboxylic acid units of the semi-aromatic polyamide (B1). Is more preferable. Further, polyvalent carboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid can be used within a range in which 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, enanthractam, undecanthractam, dodecanlactam, α-pyrrolidone, α-piperidone; 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11 Examples thereof include aliphatic aminocarboxylic acids such as −aminoundecanoic acid and 12-aminododecanoic acid; and units derived from aminocarboxylic acids of aromatic aminocarboxylic acids such as p-aminomethylbenzoic acid. These can be used alone or in combination of two or more. The content of the other units is preferably 45 mol% or less, more preferably 40 mol% or less, and 35 mol% or less, based on all the monomer units of the semi-aromatic polyamide (B1). Is more preferable.

Further, as the equipment for producing the semi-aromatic polyamide (B1), a batch type reaction kettle, a single-tank or multi-tank continuous reaction device, a tubular continuous reaction device, a uniaxial kneading extruder, a twin-screw kneading extruder, etc. Examples thereof include known polyamide production equipment such as a kneading reaction extruder of the above. As a polymerization method, known methods such as melt polymerization, solution polymerization, and solid phase polymerization can be used, and polymerization can be carried out by repeating normal pressure, reduced pressure, and pressurizing operations. These polymerization methods can be used alone or in combination as appropriate.

When producing the semi-aromatic polyamide (B1), phosphoric acid, phosphorous acid, hypophosphoric acid, salts or esters thereof and the like can be added as a catalyst. Examples of salts or esters of phosphoric acid, phosphite, hypophosphoric acid include phosphoric acid, phosphite, or phosphoric acid and potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin. , Tungsten, germanium, titanium, antimony and other metal salts, phosphoric acid, phosphoric acid, or ammonium salt of hypophosphoric acid, phosphoric acid, phosphoric acid, or ethyl ester, isopropyl ester, butyl ester of hypophosphoric acid. , Hexyl ester, isodecyl ester, decyl ester, stearyl ester, phenyl ester and the like. These can be used alone or in combination of two or more.

[Semi-aromatic polyamide (B2)]
The semi-aromatic polyamide composition (B) may contain a semi-aromatic polyamide (B2) (hereinafter, may be referred to as a semi-aromatic polyamide (B2)), and the semi-aromatic polyamide (B2) is a semi-aromatic polyamide (B2). Diamine units containing 50 mol% or more of xylylene diamine units and / or bis (aminomethyl) naphthalene units with respect to the total diamine units of the semi-aromatic polyamide (B2), and the total dicarboxylic acid 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 with respect to the unit.

The content of the xylylenediamine unit and / or the bis (aminomethyl) naphthalene unit in the semi-aromatic polyamide (B2) includes various factors such as heat resistance, chemical resistance, impact resistance, and chemical barrier property of the obtained laminated tube. From the viewpoint of ensuring sufficient physical properties, the content is 50 mol% or more, preferably 55 mol% or more, and more preferably 60 mol% or more, based on the total 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 be used alone or in combination of two or more. Among the xylylenediamine units, units derived from m-xylylenediamine and p-xylylenediamine are preferable.

The bis (aminomethyl) naphthalene unit is 1,4-bis (aminomethyl) naphthalene, 1,5-bis (aminomethyl) naphthalene, 2,6-bis (aminomethyl) naphthalene, and 2,7-bis (amino). Examples thereof include units derived from methyl) naphthalene and the like. These can be used alone or in combination of two or more. 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 it does not impair the excellent properties of the obtained laminated tube. It may include units. Other diamine units include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1 , 8-octane diamine, 1,9-nonan diamine, 1,10-decane diamine, 1,11-undecane diamine, 1,12-dodecane diamine, 1,13-tridecane diamine, 1,14-tetradecane diamine, 1, 15-Pentadecanediamine, 1,16-Hexadecandiamine, 1,17-Heptadecandiamine, 1,18-Octadecanediamine, 1,19-Nonadecanediamine, 1,20-Eicosandiamine, 2-Methyl-1,5 -Pentanediamine, 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1 , 6-Hexanediamine, 5-Methyl-1,9-Nonandiamine and other aliphatic diamines; 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 (3-methyl-4-aminocyclohexyl) Aminopropyl) piperazine, bis (aminoethyl) piperazine, 2,5-bis (aminomethyl) norbornan, 2,6-bis (aminomethyl) norbornan, 3,8-bis (aminomethyl) tricyclodecane, 4,9 Units derived from alicyclic diamines such as -bis (aminomethyl) tricyclodecane; m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) Units derived from aromatic diamines such as propane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl ether can be mentioned, and one or more of these can be used. Among these, units derived from aromatic diamines are preferable. 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 chain aliphatic dicarboxylic acid such as 2,2,4-trimethyladipic acid and 2,4,4-trimethylazipic acid. .. These can be used alone or in combination of two or more. 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.

Further, the content of the aliphatic dicarboxylic acid unit having 9 or 10 carbon atoms in the semi-aromatic polyamide (B2) sufficiently satisfies various physical properties such as heat resistance, chemical resistance, and chemical barrier property of the obtained laminated tube. From the viewpoint of ensuring, the amount is 50 mol% or more, preferably 55 mol% or more, and more preferably 60 mol% or more, based on the total 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 properties of the obtained laminated tube. It may include a unit. Other dicarboxylic acid units include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelli 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, eikosandioic acid, 2-methyladipic acid, 2,2-dimethylglutaric acid, 2,2-diethylsuccinic acid, and 2-butylsveric 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 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, diphenylether-4,4'-dicarboxylic acid, diphenylsulfone- Units derived from aromatic dicarboxylic acids such as 4,4'-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, and 4,4'-triphenyldicarboxylic acid can be mentioned, and these may be one or more. Can be used. 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 the total dicarboxylic acid units of the semi-aromatic polyamide (B2). Is more preferable. Further, polyvalent carboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid can be used within a range in which 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, enanthractam, undecanthractam, dodecanlactam, α-pyrrolidone, α-piperidone; 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11 Examples thereof include aliphatic aminocarboxylic acids such as −aminoundecanoic acid and 12-aminododecanoic acid; and units derived from aminocarboxylic acids of aromatic aminocarboxylic acids such as p-aminomethylbenzoic acid. These can be used alone or in combination of two or more. The content of the other units is preferably 45 mol% or less, more preferably 40 mol% or less, and 35 mol% or less, based on all the monomer units of the semi-aromatic polyamide (B2). Is more preferable.

Examples of the semi-aromatic polyamide (B2) manufacturing apparatus include a batch type reaction kettle, a single-tank or multi-tank continuous reaction device, a tubular continuous reaction device, a uniaxial kneading extruder, a twin-screw kneading extruder, and the like. Known polyamide production equipment such as a reaction extruder can be mentioned. As a method for producing a semi-aromatic polyamide (B2), there are known methods such as melt polymerization, solution polymerization, and solid phase polymerization. Using these methods, normal pressure, reduced pressure, and pressurization are repeated to achieve semi-aromatic polyamide. 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 xylylene diamine and / or bis (aminomethyl) naphthalene and an aliphatic dicarboxylic acid having 9 or 10 carbon atoms is pressurized and heated in the presence of water, and added water and condensed water. It is produced by a method of polymerizing in a molten state while removing the above. It is also produced by a method in which xylylene diamine and / or bis (aminomethyl) naphthalene is directly added to an aliphatic dicarboxylic acid having 9 or 10 carbon atoms in a molten state 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, and during that time, the reaction system is added. Polymerization proceeds while raising the temperature of the reaction system so that the temperature is equal to or higher than the melting points of the oligoamide and polyamide produced. Further, the semi-aromatic polyamide (B2) may be subjected to solid phase polymerization after being produced by the melt polymerization method.

A phosphorus atom-containing compound can be added to the semi-aromatic polyamide (B2) as a catalyst, to enhance processing stability during melt molding, and to prevent coloring. Phosphoric acid-containing compounds include hypophosphoric acid, phosphite, phosphoric acid, pyrophosphoric acid, metaphosphoric acid, phosphonic acid phosphonic acid and derivatives thereof, alkaline earth metal salts of hypophosphoric acid, and phosphite. Alkali metal salt, alkaline earth metal salt of phosphoric 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 Metal salts, alkaline earth metal salts of metaphosphoric acid, alkali metal salts of phosphonic acid, alkaline earth metal salts of phosphonic acid, alkali metal salts of phosphonic acid, alkaline earth metal salts of phosphonic acid, etc. Be done.
Phosphoric acid-containing compounds include phosphinic acid (hypophosphoric acid), ethyl hypophosphate, dimethylphosphoric acid, phenylmethylphosphinic acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, and the following. Calcium phosphite, magnesium hypophosphite, phosphite, 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, pyrophosphoric 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 , Phosphoric acid, sodium phosphite, lithium phosphite, potassium phosphite, magnesium phosphite, calcium phosphite, ethyl phenyl phosphite, sodium phenyl phosphite, potassium phenyl phosphite, phenyl sub Lithium phosphonate, phosphonic acid, sodium phosphonate, potassium phosphonate, lithium phosphonate, potassium phosphonate, magnesium phosphonate, calcium phosphonate, phenylphosphonic acid, ethylphosphonic acid, sodium phenylphosphonate, potassium phenylphosphonate, phenyl Examples thereof include lithium phosphonate, diethyl phenylphosphonate, sodium ethylphosphonate, potassium ethylphosphonate and the like. These can be used alone or in combination of two or more. Among these, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, calcium hypophosphate, magnesium hypophosphite, calcium phosphite, calcium hydrogen phosphite, calcium dihydrogen phosphate, phosphite Sodium, sodium phosphite, sodium hydrogen phosphite, potassium phosphite, potassium hydrogen phosphite, lithium phosphite, lithium hydrogen phosphite, magnesium phosphite, magnesium hydrogen phosphite, calcium phosphite, sub 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 the phosphorus atom concentration with respect to 100 parts by mass of the semi-aromatic polyamide (B2) from the viewpoint of sufficiently ensuring the catalytic effect and the anti-coloring effect at the time of polymerization and suppressing the generation of gel. In terms of conversion, it is preferably 0.030 parts by mass or more and 0.30 parts by mass or less, more preferably 0.050 parts by mass or more and 0.20 parts by mass or less, and 0.070 parts by mass or more and 0.15 parts by mass or less. The following is more preferable.
The method of adding these phosphorus atom-containing compounds is a method of adding to a nylon salt aqueous solution, a diamine or a dicarboxylic acid which is a raw material of a semi-aromatic polyamide (B2), a method of adding to a dicarboxylic acid in a molten state, and a method of adding to a molten dicarboxylic acid. Examples thereof include a method of addition, but any method may be used as long as it can be uniformly dispersed in the semi-aromatic polyamide (B2), and the method is not limited thereto.

An alkali metal compound or an alkaline earth metal compound can be added to the semi-aromatic polyamide (B2) in combination with a phosphorus atom-containing compound. In order to prevent the coloration of the polyamide during polycondensation, it is necessary to have a sufficient amount of the phosphorus atom-containing compound, but in some cases, it may cause gelation of the polyamide, so in order to adjust the amidation reaction rate. It is also preferable that an alkali metal compound or an alkaline earth metal compound coexists. 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. Examples thereof include earth metal alkoxides, and alkali metal hydroxides and / or alkali metal acetates are preferable.

Alkali metal compounds include alkali metals / alkaline earth metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide. Hydroxide; Alkali metal / alkaline earth metal acetates such as lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, magnesium acetate, calcium acetate, strontium acetate, barium acetate; 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 methoxyde, sodium ethoxide, sodium propoxide, sodium butoxide, potassium methoxy Examples thereof include alkali metal / alkaline earth metal alkoxides such as de, lithium methoxyd, magnesium methoxyd, and calcium methoxyd. These can be used alone or in combination of two or more. Among these, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium acetate, and potassium acetate are preferable from the viewpoint of economic efficiency.

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 phosphorus atom-equivalent moles of the phosphorus atom-containing compound is calculated. 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. Is more preferable.
The method of adding these alkali metal compounds or alkaline earth metal compounds is a method of adding to a nylon salt aqueous solution, a diamine or a dicarboxylic acid, which is a raw material of a semi-aromatic polyamide (B2), or a method of adding to a molten dicarboxylic acid. , However, any method may be used as long as it can be uniformly dispersed in the semi-aromatic polyamide (B2), and the method is not limited thereto.

According to JIS K-6920, the relative viscosities of the semi-aromatic polyamide (B1) and the semi-aromatic polyamide (B2) measured under the conditions of 96% sulfuric acid, polymer concentration 1%, and 25 ° C. are the obtained laminated tubes. From the viewpoint of ensuring the mechanical properties of the above and ensuring the desirable moldability of the laminated tube by setting the viscosity at the time of melting in an appropriate range, it is preferably 1.5 or more and 4.0 or less, and 1.8 or more and 3 It is more preferably 5.5 or less, and further preferably 2.0 or more and 3.0 or less.

There are no particular restrictions on the type, concentration, and molecular weight distribution of the terminal groups of the semi-aromatic polyamide (B1) and the semi-aromatic polyamide (B2). For adjusting the molecular weight and stabilizing the melt during molding, one or more of monoamine, diamine, polyamine, monocarboxylic acid, and dicarboxylic acid can be added as appropriate. For example, aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine; alicyclic type such as cyclohexylamine and dicyclohexylamine. Monoamines; aromatic monoamines such as aniline, toluidine, diphenylamine, naphthylamine; 1,4-butanedimine, 1,5-pentanedimine, 1,6-hexanediamine, 1,8-octanediamine, 2-methyl-1,5 -Adioxydiamines such as pentanediamine; alicyclic diamines such as cyclohexanediamine, bis (aminomethyl) cyclohexane, 5-amino-1,3,3-trimethylcyclohexanemethylamine; m-phenylenediamine, p-phenylenediamine and the like. Aromatic diamines; polyamines such as polyalkyleneimines, polyalkylene polyamines, polyvinylamines, polyallylamines; acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, capric acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, Adicyclic monocarboxylic acids such as stearic acid, pivalic acid, and isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid , Aromatic monocarboxylic acids such as phenylacetic acid; aliphatic dicarboxylic acids such as adipic acid and pimelic acid, fats such as 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. Cyclic dicarboxylic acid; Examples thereof include aromatic dicarboxylic acids such as phthalic acid and isophthalic acid. These can be used alone or in combination of two or more. The amount of these molecular weight adjusting agents used varies depending on the reactivity of the molecular weight adjusting agent and the polymerization conditions, but is appropriately determined so that the relative viscosity of the polyamide to be finally obtained is 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 a terminal sealant, and 10% or more of the terminal groups are sealed. It is more preferable that it is stopped, and it is further preferable that 20% or more of the terminal groups are sealed. The terminal encapsulant is not particularly limited as long as it is a monofunctional compound having reactivity with an amino group or a carboxyl group at the polyamide terminal, but from the viewpoint of reactivity, stability of the encapsulating end, etc., it is a monocarboxylic acid. Acids or monoamines are preferable, and monocarboxylic acids are more preferable from the viewpoint of ease of handling and the like. In addition, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, monoalcohols and the like can also be used.

The monocarboxylic acid used as the terminal encapsulant is not particularly limited as long as it has reactivity with an amino group, but the above-mentioned aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, and aromatic monocarboxylic acid are not particularly limited. Examples include carboxylic acid. Among these, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, etc. from the viewpoints of reactivity, stability of the sealing end, price, etc. , Saprosylic acid is preferred. The monoamine used as the terminal encapsulant is not particularly limited as long as it has reactivity with a carboxyl group, and examples thereof include the above-mentioned aliphatic monoamine, alicyclic monoamine, and aromatic monoamine. Among these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are preferable from the viewpoints of reactivity, boiling point, stability of sealing end, price, and the like.
The amount of the end-capping agent used can be appropriately selected in consideration of the reactivity, boiling point, reaction apparatus, reaction conditions, etc. of the end-capping agent to be 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 raw material components dicarboxylic acid and diamine.

In order to improve the low temperature impact resistance of the semi-aromatic polyamide (B1) and the semi-aromatic polyamide (B2), it is preferable to add an impact improving material to the semi-aromatic polyamide composition (B), and particularly described later. Containing a structural unit derived from an unsaturated compound having a carboxyl group and / or an acid anhydride group, which is described in the polyamide 6 composition (C1) and / or the polyamide 6/66/12 composition (C2) of the above. It is more preferable to add the elastomer polymer (C4). If the elastomer polymer (C4), which will be 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 improving material 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. It is preferably 3 parts by mass or more and 30 parts by mass or less, and more preferably 3 parts by mass or more and 25 parts by mass or less.

The semi-aromatic polyamide composition (B) may contain another polyamide-based resin or other thermoplastic resin together with the semi-aromatic polyamide (B1) or the semi-aromatic polyamide (B2). Examples of the other polyamide-based resin or the other thermoplastic resin include the same resin as in the case of the aliphatic polyamide composition (A). Further, it may be a mixture of the aliphatic polyamide (A1) and / or the polyamide 6 (C11) and / or the 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, preferably 70% by mass or more. Is more preferable.

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

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

[Polyamide 6 (C11)]
Polycaproamide (polyamide 6) is a polyamide having an amide bond (-CONH-) in the main chain and having a caproamide unit _{represented by the following formula: (-CO- (CH 2} ) _{5- NH-) n} (-CO- (CH 2) 5-NH-). Hereinafter, it may be referred to as polyamide 6 (C11)).

[Polyamide 6/66/12 composition (C2)]
The polyamide 6/66/12 composition (C2) contains 50% by mass or more and 98% by mass or less of the polyamide mixture, 1% by mass or more and 20% by mass or less of the plasticizer (C3), and the elastomer polymer (C4) 1 in the composition. The polyamide mixture contains 50% by mass or more and 30% by mass or less, and the polyamide mixture contains 50% by mass or more and 100% by mass or less of polyamide 6/66/12 (C21) and polyamide (C22) other than polyamide 6/66/12 (C21). ) 0% by mass or more and 50% by mass, and the elastomer polymer (C4) contains a structural unit derived from an unsaturated compound having a carboxyl group and / or an acid anhydride group (hereinafter, polyamide 6/66). It may be referred to as a / 12 composition (C2)).

[Polyamide 6/66/12 (C21)]
Polyamide 6/66/12 (poly (caproamide / hexamethylene adipamide / dodecaneamide)) has an amide bond (-CONH-) in the main chain: (-CO- (CH ₂ ) _5- NH -) _{Caproamide unit represented by n} and the following formula: ( _{-NH- (CH 2} ) ₆ -NH-CO- (CH ₂ ) ₄ -CO-) _{Hexamethylene adipamide unit represented by n} and the following formula: ( -CO- (CH ₂ ) _11- NH-) A polyamide copolymer having a dodecane amide unit represented by n. Polyamide 6/66/12 can be obtained by copolymerizing 6-aminocaproic acid and / or a salt of caprolactam, hexamethylenediamine and adipic acid, and 12-aminododecanoic acid and / or dodecanlactam (hereinafter, polyamide). It may be referred to as 6/66/12 (C21)).

In polyamide 6/66/12 (C21), the mass ratio of the total unit of caproamide unit and hexamethylene adipamide unit to the mass ratio of dodecaneamide unit is from the viewpoint of sufficiently ensuring the interlayer adhesiveness 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 a total of 100% by mass of the caproamide unit, the hexamethylene adipamide unit, and the dodecaneamide unit. It is more preferably mass% or less.
In polyamide 6/66/12 (C21), the mass ratio of caproamide unit and hexamethylene adipamide unit ensures sufficient heat resistance of the laminated tube and coextrudes with the semi-aromatic 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, preferably 82:18% by mass, based on 100% by mass of the total of the caproamide unit and the hexamethylene adipamide unit. More preferably, it is 93: 7% by mass or less.

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

[Polyamide (C22)]
Polyamide (C22) has an amide bond (-CONH-) in the main chain and uses lactam, aminocarboxylic acid, or diamine and dicarboxylic acid, which are polyamide structural units, as raw materials for melt polymerization, solution polymerization, and solid phase. It is obtained by polymerizing or copolymerizing by a known method such as polymerization (hereinafter, may be referred to as polyamide (C22)). However, the polyamide (C22) does not contain the above-mentioned poly (caproamide / hexamethylene adipamide / dodecane amide) (polyamide 6/66/12) (C21).

The polyamide (C22) is a polycaproamide (polymer 6), a polyundecane amide (polyamide 11), a polydodecane amide (polyamide 12), or a polyhexamethylene from the viewpoint of sufficiently obtaining the interlayer adhesiveness of the laminated tube and its durability. Adipamide (Polymer 66), Polyhexamethylene sebacamide (Polymer 610), Polyhexamethylene dodecamide (Polymer 612), Polynonamethylene decamide (Polymer 910), Polynonamethylene dodecamide (Polymer 912), Poly Form at least one homopolymer selected from the group consisting of decamethylene decamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), and polydodecamethylene dodecamide (polyamide 1212), and / or these. It is preferably a copolymer using several kinds of raw material monomers, and is preferably polycaproamide (polyamide 6), polyundecaneamide (polyamide 11), polydodecaneamide (polyamide 12), polyhexamethylene adipamide (polyamide). 66), polyhexamethylene sebacamide (polymer 610), polyhexamethylene dodecamide (polymer 612), polydecamethylene decamide (polymer 1010), polydecamethylene dodecamide (polymer 1012), and polydecamethylene dodecamide. More preferably, it is a copolymer using at least one homopolymer selected from the group consisting of (polyamide 1212) and / or several kinds of raw material monomers forming these, and polycaproamide (polyamide 6). ), Polyundecane amide (polymer 11), polydodecane amide (polyamide 12), polyhexamethylene adipamide (polymer 66), polyhexamethylene sebacamide (polymer 610), polyhexamethylene dodecamide (polymer 612), And at least one homopolymer selected from the group consisting of polydecamethylene decamide (polyamide 1010), and / or a copolymer using several kinds of raw material monomers forming these are more preferable. Particularly preferred are polyhexamethylene sebacamide (polymer 610) and / or polyhexamethylene dodecamide (polymer 612).

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

Further, according to JIS K-6920, polyamide 6 (C1), polyamide 6/66/12 (C21), and polyamide (C22) measured under the conditions of 96% sulfuric acid, polymer concentration 1%, and 25 ° C. The relative viscosity of 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 moldability of the laminated tube by keeping the viscosity at the time of melting within an appropriate range. It is preferable, and it is more preferable that it is 1.8 or more and 4.5 or less.

The terminal amino group concentration per gram of polyamide 6 (C11), polyamide 6/66/12 (C21), and polyamide (C22) was [A] (μeq / g), and the terminal carboxyl group concentration was [B] ( When μeq / g) is set, it is preferably [A]> [B] +5, and [A]> [B] +10 from the viewpoint of sufficiently ensuring the interlayer adhesiveness of the laminated tube and its durability. It is more preferable, and it is further preferable that [A]> [B] +15. Further, from the viewpoint of the melt stability of the polyamide and the suppression of the generation of gel-like substances, [A]> 20 is preferable, and 30 <[A] <120 is more preferable.

Polyamide 6 (C11), polyamide 6/66/12 (C21), and polyamide (C22) are known methods such as melt polymerization, solution polymerization, and solid phase polymerization of the above-mentioned polyamide raw materials in the presence of amines. It is produced by polymerization or copolymerization in. 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 during melt-kneading after polymerization, but when the interlayer adhesiveness of the laminated tube is taken into consideration, they are added at the stage during polymerization. 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, if necessary, as long as they do not deviate from the above-mentioned terminal group concentration conditions. These amines and carboxylic acids may be added at the same time or separately. In addition, examples of these amines and carboxylic acids include those described in the description of the aliphatic polyamide (A), and one or more of these can be used.

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 of the total of polyamide 6/66/12 (C21) and polyamide (C22). 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 the polyamide (C22) in the polyamide mixture is 0% by mass or more and 50% by mass or less with respect to the total 100% by mass of the polyamide 6/66/12 (C21) and the polyamide (C22). It is preferably 5% by mass or more and 45% by mass or less, and more preferably 15% by mass or more and 40% by mass or less.
If 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. If 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 of the obtained laminated tube and its durability are insufficient. It becomes.

The content of the polyamide mixture in the polyamide 6/66/12 composition (C2) is 50% by mass or more and 98% by mass or less, preferably 60% by mass or more and 95% by mass or less, and 70% by mass or more and 92. It is more preferably mass% or less. If the content of the polyamide mixture is less than the above value, the mechanical properties of the obtained laminated tube are inferior, while if it exceeds the above value, the interlayer adhesiveness of the obtained laminated tube and its durability 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. Kind and the like.

Examples of the benzenesulfonic acid alkylamides include benzenesulfonic acid propylamide, benzenesulfonic acid butyramide, and benzenesulfonic acid 2-ethylhexylamide. Examples of toluenesulfonic acid alkylamides include N-ethyl-o-toluenesulfonic acid butyramide, N-ethyl-p-toluenesulfonic acid butyramide, N-ethyl-o-toluenesulfonic acid 2-ethylhexylamide, and N-ethyl-p. -Toluenesulfonic acid 2-ethylhexylamide and the like can be mentioned. Examples of hydroxybenzoic acid alkyl esters include ethylhexyl o-hydroxybenzoate, ethylhexyl p-hydroxybenzoate, hexyldecyl o-hydroxybenzoate, hexyldecyl p-hydroxybenzoate, ethyldecyl o-hydroxybenzoate, and p-hydroxybenzoic acid. Ethyldecyl acid acid, 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, n-octyl p-hydroxybenzoate, o-hydroxybenzoic acid Examples thereof include decyl, decyl p-hydroxybenzoate, dodecyl o-hydroxybenzoate, and dodecyl p-hydroxybenzoate. These can be used alone or in combination of two or more.

Among these, benzenesulfonic acid alkylamides such as benzenesulfonic acid butylamide and benzenesulfonic acid 2-ethylhexylamide, N-ethyl-p-toluenesulfonic acid butylamide, N-ethyl-p-toluenesulfonic acid 2-ethylhexylamide and the like. Alkylamides of toluenesulfonic acid, ethylhexyl p-hydroxybenzoate, hexyldecyl p-hydroxybenzoate, ethyldecyl p-hydroxybenzoate and other hydroxybenzoic acid alkyl esters are preferable, and benzenesulfonic acid butylamide and p-hydroxybenzoic acid. Ethylhexyl and hexyldecyl p-hydroxybenzoate are more preferred.

The content of the thermoplastic agent (C3) in the polyamide 6 composition (C1) and the polyamide 6/66/12 composition (C2) is 1% by mass or more and 20% by mass or less, and 2% by mass or more and 15% by mass or less. It is preferable that it is 3% by mass or more and 10% by mass or less. If the content of the plasticizer (C3) is less than the above value, the flexibility of the obtained laminated tube is inferior, while if 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 carboxyl groups and / or acid anhydride groups. (Hereinafter, it may be referred to as an elastomer polymer (C4)).

Examples of the elastomer polymer (C4) include (ethylene and / or propylene) / α-olefin-based copolymers, (ethylene and / or propylene) / (α, β-unsaturated carboxylic acids and / or unsaturated carboxylic acid esters). ) -Based copolymers, ionomer polymers, aromatic vinyl compounds / conjugated diene compound-based block copolymers, and one or more of these can be used.

The (ethylene and / or propylene) / α-olefin-based copolymer is a polymer obtained by copolymerizing ethylene and / or propylene with an α-olefin having 3 or more carbon atoms, and is an α-olefin having 3 or more carbon atoms. Examples of the olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-hexene, 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-eicosene, 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, Examples thereof include 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. These can be used alone or in combination of two or more. In addition, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadene, 1,5-octadien, 1,6-octadene, 1,7-octadien, 2-methyl-1, 5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadene, 4-ethylidene-8-methyl-1,7-norbornene, 4,8-dimethyl-1,4,8- Decatrine (DMDT), dicyclopentadiene, cyclohexadiene, cyclooctadiene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl Non-conjugated diene such as -5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornene Polyene may be copolymerized. These can be used alone or in combination of two or more.

The (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) -based copolymer contains ethylene and / or propylene and α, β-unsaturated carboxylic acid and / or It 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, and the α, β-unsaturated carboxylic acid ester simple substance. Examples of the metric include methyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, heptyl ester, octyl ester, nonyl ester, decyl ester and the like of these unsaturated carboxylic acids. These can be used alone or in combination of two or more.

In the ionomer polymer, at least a part of the carboxyl groups 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 the olefin is not limited to those exemplified here, and an unsaturated carboxylic acid ester is used alone. The body may be copolymerized. The metal ions include alkali metals such as Li, Na, K, Mg, Ca, Sr, and Ba and alkaline earth metals, as well as Al, Sn, Sb, Ti, Mn, Fe, Ni, Cu, Zn, and Cd. Can be mentioned. These can be used alone or in combination of two or more.

The aromatic vinyl compound / conjugated diene compound-based block copolymer is a block copolymer composed of an aromatic vinyl compound-based polymer block and a conjugated diene compound-based polymer block, and is an aromatic vinyl compound-based polymer. A block copolymer having at least one block and at least one conjugated diene compound polymer block is used. Further, in the block copolymer described above, the unsaturated bond in the conjugated diene compound-based polymer block may be hydrogenated.
The aromatic vinyl compound-based polymer block is a polymer block mainly composed of units derived from an aromatic vinyl compound. Examples of the aromatic vinyl compound in this case include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,5-dimethylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene, and 4-propyl. Examples thereof include styrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene and the like, 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 other unsaturated monomers.

Conjugated diene compound-based polymer blocks include 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 in the hydrogenated aromatic vinyl compound / conjugated diene compound block copolymer, the conjugated diene compound polymer. Part or all of the unsaturated bond portion in the block is saturated by hydrogenation.

The molecular structure of the aromatic vinyl compound / conjugated diene compound block copolymer and its hydrogenated product may be linear, branched, radial, or any combination thereof. Among these, one aromatic vinyl compound polymer block and one conjugated diene compound polymer block are linear as an aromatic vinyl compound / conjugated diene compound-based block copolymer and / or its hydrogen additive. Three polymer blocks are linearly bonded in the order of a diblock copolymer bonded in a shape, an aromatic vinyl compound-based polymer block-conjugated diene compound-based polymer block-an aromatic vinyl compound-based polymer block. One or more of the triblock copolymers and hydrogenated products thereof are preferably used, and both unhydrogenated or hydrogenated styrene / butadiene block copolymers and unhydrogenated or hydrogenated styrene / isoprene blocks are used. Polymer, unhydrogenated or hydrogenated styrene / butadiene / styrene block copolymer, unhydrogenated or hydrogenated styrene / isoprene / styrene block copolymer, unhydrogenated or hydrogenated styrene / (ethylene / butadiene) / styrene Examples include block copolymers, unhydrogenated or hydrogenated styrene / (isoprene / butadiene) / styrene block copolymers.

Examples of unsaturated compounds having a carboxyl group forming a constituent unit of the elastomeric polymer (C4) include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, and 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. Acid is mentioned. Examples of unsaturated compounds having an acid anhydride group forming a constituent unit of the elastomeric polymer (C4) include maleic anhydride, itaconic anhydride, citraconic anhydride, and endobicyclo- [2.2.1] -5-heptene. Examples thereof include dicarboxylic acid anhydrides having α, β-unsaturated bonds such as −2,3-dicarboxylic acid anhydrides. These can be used alone or in combination of two or more. Among these, a dicarboxylic acid anhydride having an α, β-unsaturated bond is preferable, and maleic anhydride and itaconic anhydride are more preferable.

The concentration of the carboxyl group and / or the acid anhydride group in the elastomer polymer (C4) sufficiently obtains the effect of improving low-temperature impact resistance, interlayer adhesion, and 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 a sample solution prepared by dissolving the elastomer polymer in a toluene solution and further adding ethanol, and using phenolphthalein as an indicator. Then, it can be measured by titrating with a 0.1 N 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 or more and 30% by mass or less, and 3% by mass or more and 25% by mass. It is preferably 5% by mass or more and 20% by mass or less. If the content of the elastomer polymer (C4) is less than the above value, the low temperature impact resistance, interlayer adhesion, and durability of the obtained laminated tube are inferior, while if it exceeds the above value, it is obtained. The mechanical properties of the laminated tube are inferior.

The method for producing the polyamide 6 composition (C1) and the polyamide 6/66/12 composition (C2) is not particularly limited, and various additives are blended as necessary, and various conventionally known methods are adopted. 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 the elastomer polymer (C4) is added as needed. Then, the pellets are uniformly dry-blended so as to have the above-mentioned mixing ratio and supplied to the melt-kneader, while the plasticizer (C3) is injected from the middle of the cylinder of the melt-kneader by a metering pump and melted. It can be manufactured by a kneading method or the like. 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-based resins or other thermoplastic resins include resins similar to those in the case of the aliphatic polyamide (A). The total content of the polyamide 6 (C11), the plasticizer (C3), and the elastomer polymer (C4) in the polyamide 6 composition (C1) as a mixture is preferably 80% by mass or more, preferably 90% by mass. The above is more preferable. Further, the total content of the polyamide 6/66/12 (C21), the polyamide (C22), the plasticizer (C3), and the elastomer polymer (C4) in the polyamide 6/66/12 composition (C2) which is a mixture. Is preferably 80% by mass or more, and more preferably 90% by mass or more.

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

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

[Alphatic 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 having high crystallinity is preferable (hereinafter, it may be referred to as an aliphatic polyketone (D)).
Repeating units (poly (1-oxotrimethylene)) of linear alternating copolymers in which units derived from ethylene and units derived from carbon monoxide are alternately arranged represented by the following formula (1). It is preferable to have a repeating unit of a linear alternating copolymer in which units derived from an unsaturated compound having 3 or more carbon atoms other than ethylene 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 positive integers.

Further, 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 completely alternately, and carbon atoms other than ethylene. The structural unit in which the units derived from the unsaturated compound of several 3 or more and the units derived from carbon monoxide are arranged completely alternately is preferably 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 α-olefins having 3 or more carbon atoms include propylene, 1-butene, isobutene, 1-pentene, 1-hexene, 1-hexene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-undecene. Dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-hexene, 1-octadecene, 1-nonadecene, 1-eicosene, 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 thereof include hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and the like. These can be used alone or in combination of two or more.

The alkenyl aromatic compound is an aryl aliphatic compound containing an aryl substituent on an ethylene unsaturated carbon atom, and examples thereof include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, o-ethylstyrene, and the like. m-Ethylstyrene, p-ethylstyrene, o-propylstyrene, p-propylstyrene, o-isopropylstyrene, m-isopropylstyrene, p-isopropylstyrene, m-butylstyrene, p-butylstyrene, pt-butyl Styrene, 4-propyl styrene, 4-cyclohexyl styrene,
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, mesitylstyrene, vinylnaphthalene and vinylanthracene. These can be used alone or in combination of two or more.

As the conjugated diene, 1,3-butadiene, 1,3-pentadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadene, 1,5-octadene, 1 , 6-octadene, 1,7-octadene, 1,9-decadien, 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-norbornene, 4,8-dimethyl-1,4,8-decatorien (DMDT), dicyclo Pentaziene, cyclohexadiene, cyclopentadiene, cyclooctadiene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropyridene-2-norbornene, 6-chloromethyl-5-iso Examples thereof include propenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornene and the like. These can be used alone or in combination of two or more.

Vinyl esters include vinyl formate, vinyl acetate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, Examples thereof include vinyl palmitate, vinyl stearate, isopropenyl acetate, 1-butenyl acetate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl cyclohexanecarboxylate, vinyl benzoate, vinyl cinnate and the like. These can be used alone or in combination of two or more.

The aliphatic unsaturated carboxylic acid, its salt and its ester include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, methylmaleic acid, methylfumaric acid and cis. -4-Cyclohexene-1,2-dicarboxylic acid, endobicyclo- [2.2.1] -5-hepten-2,3-dicarboxylic acid, maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- [ 2.2.1] -5-heptene-2,3-dicarboxylic acid anhydride, acrylic acid ester, methacrylic acid ester, maleic acid monoester, maleic acid diester, fumaric acid monoester, fumaric acid diester, itaconic acid monoester , Itaconic acid diesters (these esters include methyl esters, ethyl esters, propyl esters, butyl esters, pentyl esters, hexyl esters, heptyl esters, octyl esters, nonyl esters, alkyl esters such as decyl esters, etc.), acrylates, Examples thereof include methacrylate, maleate, andtaconate (these salts include monovalent or divalent metal salts) and the like. These can be used alone or in combination of two or more.

Among the ethylenically unsaturated compounds other than ethylene, α-olefins having 3 to 8 carbon atoms are 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 are alternately arranged, which are represented by the following formula (2). Repeating units of poly (1-oxotrimethylene) and linear alternating copolymers in which units derived from propylene and units derived from carbon monoxide are arranged alternately (poly (1-oxo-2)). -Methyl-trimethylene))) is more preferable.

In equation (2), m and n represent positive integers.

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

The melting point of the aliphatic polyketone (D) can be adjusted by selecting the type, composition ratio, etc. of carbon monoxide, ethylene, and other monomers, and the polymerization composition ratio of carbon monoxide, ethylene, and propylene. It is preferable to adjust the melting point by The melting point of the aliphatic polyketone (D) is preferably 200 ° C. or higher and 250 ° C. or lower, and 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 by using a differential scanning calorimetry device, 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 raising the temperature at a rate of 10 ° C. per minute.

The melt flow rate (MFR) (melting point + 20 ° C., under a load of 2,160 g) of the polyketone (D) ensures desirable moldability by keeping the viscosity at the time of melting within an appropriate range, and does not excessively reduce the melt tension. From the viewpoint of preventing the occurrence of problems such as drawdown during molding, it is preferably 0.01 g / 10 minutes or more and 50 g / 10 minutes or less, and 0.1 g / 10 minutes or more and 10 g / 10 minutes or less. More preferred.

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

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

In addition, various additives can be contained in the aliphatic polyketone (D), if necessary. Examples of such additives include conductive fillers, antioxidants, heat stabilizers, UV absorbers, light stabilizers, lubricants, inorganic fillers, antistatic agents, flame retardants, crystallization accelerators, and plasticizers. Examples include 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 set of the (c) layer and the (d) layer are arranged adjacent to each other. Will be done.

It is essential that the laminated tube contains the layer (b) and the layer (d), and the chemical barrier property of the laminated tube, particularly the hydrocarbon barrier property, is improved. Further, by arranging at least one set of the layer (c) and the layer (d) adjacent to each other, it is possible to obtain a laminated tube having excellent interlayer adhesiveness and durability thereof.

In a preferred embodiment, layer (a) is located on the outermost layer of the laminated tube. By arranging the layer (a) on the outermost layer, it is possible to obtain a laminated tube having excellent chemical resistance and flexibility. Further, the layer (c) is arranged between the layer (a) and the layer (d).

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

In a more preferable embodiment, by arranging the layer (d) in the innermost layer, a laminated tube having excellent deterioration fuel resistance can be obtained, and low molecular weight components such as monomers and oligomers are eluted by contact with alcohol-containing gasoline. When 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 layer (a) is arranged in the outermost layer, the layer (c) and the layer (d) are arranged adjacent to each other, and the layer (d) is arranged in the innermost layer is more preferable.

Further, in the laminated tube, when a conductive layer containing an aliphatic polyketone (D) containing a conductive filler is arranged in the innermost layer of the laminated tube, it has chemical barrier property, deterioration fuel resistance, and resistance to low molecular weight components. In addition to being excellent in elution, when used as a fuel pipe tube, it is possible to prevent sparks generated by internal friction of the fuel circulating in the pipe or friction with the pipe wall from igniting the fuel. At that time, by arranging the layer containing the non-conductive aliphatic polyketone on the outside with respect to the conductive layer, it is possible to achieve both low temperature impact resistance and conductivity, and it is economical. It is also advantageous.

Conductivity means, for example, that when a flammable fluid such as gasoline comes into continuous contact with an insulator such as resin, static electricity may accumulate and ignite, but this static electricity does not accumulate. It means having electrical characteristics. 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 includes granular, flake-shaped, fibrous fillers and the like.

Examples of the granular filler include carbon black and graphite. Examples of the flake-like filler include aluminum flakes, nickel flakes, nickel-coated mica, and the like. Examples of the fibrous filler include carbon fibers, carbon-coated ceramic fibers, carbon whiskers, carbon nanotubes, aluminum fibers, copper fibers, brass fibers, and metal fibers such as stainless fibers. These can be used alone or in combination of two or more. Among these, carbon nanotubes and carbon black are preferable.

Carbon nanotubes are referred to as hollow carbon fibrils, which have an outer region consisting of essentially continuous multiple layers of regularly arranged carbon atoms and an inner hollow region, each layer. And hollow regions are essentially columnar fibrils that are substantially concentrically arranged around the cylindrical axis of the fibril. Further, it is preferable that the regularly arranged carbon atoms in the outer region are graphite-like and the diameter of the hollow region is 2 nm or more and 20 nm or less. The outer diameter of the carbon nanotubes is preferably 3.5 nm or more and 70 nm or less, and 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 product. Is more preferable. The aspect ratio (referring to the length / outer diameter ratio) 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 adding a small amount.

Carbon black includes all carbon blacks generally used for imparting conductivity, and preferred carbon blacks are acetylene black obtained by incomplete combustion of acetylene gas and furnace-type incomplete combustion using crude oil as a raw material. Examples include, but are not limited to, furnace black such as Ketjen black, oil black, naphthalin black, thermal black, lamp black, channel black, roll black, and disc black produced by. Among these, acetylene black and furnace black are more preferable.

Further, as carbon black, various carbon powders having different characteristics such as particle size, surface area, DBP oil absorption amount, ash content and the like are produced. The characteristics of the carbon black are not limited, but those having a good chain structure and a high aggregation density are preferable. A large amount of carbon black is not preferable from the viewpoint of impact resistance, and the average particle size is preferably 500 nm or less, more preferably 5 nm or more and 100 nm or less, from the viewpoint of obtaining excellent electrical conductivity with a smaller amount. It is more preferably 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 amount of DBP (dibutyl phthalate) oil absorbed is preferably 50 ml / 100 g or more, more preferably 100 ml / 100 g, and even more preferably 150 ml / 100 g or more. The ash content is preferably 0.5% by mass or less, and more preferably 0.3% by mass or less. The DBP oil absorption amount referred to here is a value measured by the method specified in ASTM D-2414. Further, the volatile content of carbon black is preferably less than 1% by mass.
These conductive fillers may be surface-treated with a surface treatment agent such as titanate-based, aluminum-based, or silane-based. It is also possible to use granulated products in order to improve the workability of melt-kneading.

Since the content of the conductive filler differs depending on the type of the conductive filler used, it cannot be unconditionally specified, but from the viewpoint of the balance with conductivity, fluidity, mechanical strength, etc., 100 mass of the aliphatic polyketone (D) Generally, it is preferably 3 parts by mass or more and 30 parts by mass or less.
Further, such conductive filler is more that from the viewpoint of obtaining a sufficient antistatic performance, it is preferable that the surface resistivity of the molten extrudate is less than 10 ⁸ Ω / square, is 10 ⁶ Ω / square or less preferable. However, the addition of the conductive filler tends to cause deterioration of strength and fluidity. Therefore, if the target conductive level can be obtained, it is desirable that the content of the conductive filler is as small as possible.

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 application, etc., but the thickness of each layer is the chemical solution of the laminated tube. It is determined in consideration of characteristics such as barrier property, low temperature impact resistance, and flexibility. In general, the thickness of the layer (a), the layer (b), the layer (c), and the layer (d) is preferably 3% or more and 90% or less with respect to the thickness of the entire laminated tube. Considering the balance between low temperature impact resistance and chemical barrier property, the thickness of the layer (b) and the layer (d) is more preferably 5% or more and 50% or less, respectively, with respect to the thickness of the entire laminated tube. , 7% or more and 30% or less is more preferable.

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. Further, the laminated tube of the first aspect is provided with additional functions other than the four layers (a), (b), (c), and (d), or is economically advantageous. In order to obtain the above, the layer containing another thermoplastic resin may have one layer or two or more layers. The number of layers of the laminated tube of the first aspect is 4 or more, but judging from the mechanism of the tube manufacturing apparatus, it is preferably 8 or less, and more preferably 4 or more and 7 or less.

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), and the like. Polyamidexylylene succinamide (polyamide MXD4) other than polyamide (C22) and aliphatic polyketone (D), polymethoxylylen glutamide (polyamide MXD5), polymethoxylylence veramide (polyamide MXD8), polymethoxylylend deca Mido (polyamide MXD12), polymethoxylylene terephthalamide (polyamide MXDT), polymethoxylylene isophthalamide (polyamide MXDI), polymethoxylylene hexahydroterephthalamide (polyamide MXDT (H)), polymethoxylylen naphthalamide (polyamide MXDT (H)) Polyamide MXDN), polyparaxylylene succinamide (polyamide PXD4), polyparaxylylene glutamide (polyamide PXD5), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylene veramide (polyamide PXD8), poly Paraxylylene dedecamide (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 (PMTA) PMIA), poly (2,6-naphthalenedimethylene adipamide) (polyamide 2,6-BAN6), poly (2,6-naphthalenedimethylene terephthalamide) (polyamide 2,6-BANT), poly (2) , 6-Naphthalenedimethylene methyleneisophthalamide) (polyamide 2,6-BANI), poly (2,6-naphthalenedimethylene hexahydroterephthalamide) (polyamide 2,6-BANT (H)), poly (2, 6-Naphthalene methylene naphtha Lamide) (Polyamide 2,6-BANN), Poly (1,3-Cyclohexanedimethylene adipamide) (Polyamide 1,3-BAC6), Poly (1,3-Cyclohexanedimethylenesveramide (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-BAC10) 3-Cyclohexanedimethylene dodecamide) (polyamide 1,3-BAC12), poly (1,3-cyclohexanedimethylene terephthalamide) (polyamide 1,3-BACT), poly (1,3-cyclohexanedimethyleneisophthalate) Lamide) (Polyamide 1,3-BACI), Poly (1,3-Cyclohexanedimethylenehexahydroterephthalamide) (Polyamide 1,3-BACT (H)), Poly (1,3-Cyclohexanedimethylenenaphthalamide) (Polyamide 1,3-BACN), Poly (1,4-cyclohexanedimethylene adipamide) (Polyamide 1,4-BAC6), Poly (1,4-Cyclohexanedimethylene sveramide) (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-cyclohexanedimethylenehexahydroterephthalamide) (Polyamide 1,4-BACT (H)), Poly (1,4-cyclohexanedimethylenenaphthalamide) ( Polyamide 1,4-BACN), poly (4,4'-methylenebiscyclohexylene adipamide) (polyamide PACM6), poly (4,4'-methylenebiscyclohexylene veramide) (polyamide PACM8), poly (4) , 4'-methylenebiscyclohexylene azelamide) (polyamide PACM9), poly (4,5'-methylenebiscyclohexylene sebacamide) (polyamide PACM10), poly (4,5'-methylenebiscyclohexylenedodecamide) (Polyamide PACM12), Poly (4,4'-methylenebiscyclohexylenetetradecamide) (polyamide PACM14), poly (4,4'-methylenebiscyclohexylene hexadecamide) (polyamide PACM16), poly (4,4'-methylenebiscyclohexide) Silen octadecamide) (polyamide PACM18), poly (4,5'-methylenebiscyclohexylene terephthalamide) (polyamide PACMT), poly (4,5'-methylenebiscyclohexylene isophthalamide) (polyamide PACMI), Poly (4,4'-methylenebiscyclohexylene hexahydroterephthalamide) (polyamide PACMT (H)), poly (4,4'-methylenebiscyclohexylene naphthalamide) (polyamide PACMN), poly (4,4' -Methylenebis (2-methyl-cyclohexylene) adipamide) (polyamide MACM6), poly (4,5'-methylenebis (2-methyl-cyclohexylene) sveramide) (polyamide MACM8), poly (4,4'-methylenebis (2) -Methyl-cyclohexylene) azelamide) (polyamide MACM9), poly (4,4'-methylenebis (2-methyl-cyclohexylene) sebacamide) (polyamide MACM10), poly (4,4'-methylenebis (2-methyl-cyclohexyl) Silen) dodecamide) (polyamide MACM12), poly (4,5'-methylenebis (2-methyl-cyclohexylene) tetradecamide) (polyamide MACM14), poly (4,5'-methylenebis (2-methyl-cyclohexylene) hexadecamide) (Polyamide MACM16), Poly (4,4'-methylenebis (2-methyl-cyclohexylene) octadecamide) (Polyamide MACM18), Poly (4,4'-methylenebis (2-methyl-cyclohexylene) terephthalamide) (Polyamide MACMT) , Poly (4,5'-methylenebis (2-methyl-cyclohexylene) isophthalamide) (polyamide MACMI), Poly (4,5'-methylenebis (2-methyl-cyclohexylene) hexahydroterephthalamide) (polyamide MACMT (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 veramide) (Po Riamide PACP8), poly (4,4'-propylene biscyclohexylene azelamide) (polyamide PACP9), poly (4,4'-propylene biscyclohexylene sebacamide) (polyamide PACP10), poly (4,4'- Propropylene biscyclohexylenedodecamide) (polyamide PACP12), poly (4,4'-propylene biscyclohexylene tetradecamide) (polyamide PACP14), poly (4,4'-propylene biscyclohexylene hexadecamide) (polyamide PACP16) ), Poly (4,4'-propylene biscyclohexylene octadecamide) (polyamide PACP18), poly (4,4'-propylene biscyclohexylene terephthalamide) (polyamide PACPT), poly (4,4'-propylene Biscyclohexylene isophthalamide) (polyamide PACPI), poly (4,5'-propylene biscyclohexylene hexahydroterephthalamide) (polyamide PACPT (H)), poly (4,5'-propylene biscyclohexylene naphthalamide) ) (Polyamide PACPN), Polyisophorone adipamide (Polyamide IPD6), Polyisophorone sveramide (Polyamide IPD8), Polyisophorone azelamide (Polyamide IPD9), Polyisophorone sebacamide (Polyamide IPD10), Polyisophorondodecamide (Polyamide IPD10) IPD12), polyisophorone terephthalamide (polyamide IPDT), polyisophorone isophthalamide (polyamide IPDI), polyisophorone hexahydroterephthalamide (polyamide IPDT (H)), polyisophorone naphthalamide (polyamide IPDN), polytetramethylene Telephthalamide (polyamide 4T), polytetramethylene isophthalamide (polyamide 4I), polytetramethylene hexahydroterephthalamide (polyamide 4T (H)), polytetramethylenenaphthalamide (polyamide 4N), polypentamethylene terephthal. Ramide (polyamide 5T), polypentamethylene isophthalamide (polyamide 5I), polypentamethylene hexahydroterephthalamide (polyamide 5T (H)), polypentamethylene naphthalamide (polyamide 5N), polyhexamethylene terephthalamide (polyamide 5N) Polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene hexahydroterephthalamide (polyamide 6T (H) )), Polyhexamethylene naphthalamide (polyamide 6N), poly (2-methylpentamethylene terephthalamide) (polyamide M5T), poly (2-methylpentamethyleneisophthalamide) (polyamide M5I), poly (2-methyl) Pentamethylene hexahydroterephthalamide) (polyamide M5T (H)), poly (2-methylpentamethylenenaphthalamide (polyamide M5N), polynonamethyleneisophthalamide (polyamide 9I), polynonamethylene hexahydroterephthalamide (polyamide 9I) Polyamide 9T (H)), poly (2-methyloctamethyleneisophthalamide) (polyamide M8I), poly (2-methyloctamethylenehexahydroterephthalamide) (polyamide M8T (H)), polytrimethylhexamethyleneisophthal. Ramide (polyamide TMHI), polytrimethylhexamethylene hexahydroterephthalamide (polyamide TMHT (H)), polydecamethylene isophthalamide (polyamide 10I), polydecamethylene hexahydroterephthalamide (polyamide 10T (H)), Polyundecamethylene terephthalamide (polyamide 11T), polyundecamethylene isophthalamide (polyamide 11I), polyundecamethylene hexahydroterephthalamide (polyamide 11T (H)), polyundecamethylene naphthalamide (polyamide 11N) ), Polydodecamethylene terephthalamide (polyamide 12T), polydodecamethylene isophthalamide (polyamide 12I), polydodecamethylene hexahydroterephthalamide (polyamide 12T (H)), polydodecamethylene naphthalamide (polyamide 12N), etc. Examples thereof include polyamide-based resins such as homopolymers of the above, and / or the raw material monomers of these polyamides, and / or the copolymers using several kinds of the raw material monomers of the aliphatic polyamide (A).

In addition, polyvinylidene fluoride (PVDF), vinyl 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 / hexafluoropropylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) Copolymer, ethylene / chlorotrifluoroethylene copolymer (ECTFE), chlorotrifluoroethylene / tetrafluoroethylene copolymer, vinylidene fluoride / chlorotrifluoroethylene copolymer, 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 / He Reactivity to fluorine-containing polymers such as xafluoropropylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) / hexafluoropropylene copolymer and / or amino group Examples thereof include 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), ultrahigh 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), Polyethylene-based products such as ethylene / methyl methacrylate copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), and ethylene / ethyl acrylate copolymer (EEA). Resins; polystyrene (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 Polystyrene resins such as / butylene / styrene copolymer (SEBS), 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, endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid and other carboxyl groups, and metal salts thereof. Acids such as (Na, Zn, K, Ca, Mg), maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid anhydride and the like. Anhydrous group; said polyolefin resin and polystyrene resin containing a functional group such as an epoxy group such as glycidyl acrylate, glycidyl methacrylate, glycidyl etacrilate, glycidyl itacone, glycidyl citracone; polybutylene terephthalate (PBT). , Polyethylene terephthalate (PET), Polyethylene isophthalate (PEI), Poly (ethylene terephthalate / ethylene isophthalate) 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 resin such as glycolic acid (PGA); Polyether resin such as polyacetal (POM) and polyphenylene ether (PPO); Polysalphon such as polysalphon (PSU), polyethersulfone (PESU), polyphenylsalphon (PPSU) Polymer-based resin: Polythioether-based resin such as polyphenylene sulfide (PPS) and polythioethersalphon (PTES); polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK), polyetheretheretherether Polymeric resins such as ketone (PEEEK), polyetheretherketoneketone (PEEKK), polyetherketoneketoneketone (PEKKK), polyetherketoneetherketoneketone (PEKEKK); polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile Polynitrile resins such as / styrene copolymer (AS), methacrylnitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), acrylonitrile / butadiene copolymer (NBR); polymethylmethacrylate ( Polymethacrylate-based resins such as PMMA) and polyethyl methacrylate (PEMA); polyvinyl ester-based resins such as polyvinylacetate (PVAc); polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride Polyvinyl chloride resins such as polymers, vinylidene chloride / methyl acrylate copolymers; cellulose resins such as cellulose acetate and cellulose butyrate; polycarbonate resins such as polycarbonate (PC); thermoplastic polyimide (TPI), polyether Polyetherketone resins such as imide, polyesterimide, polyamideimide (PAI) and polyesteramideimide; thermoplastic polyurethane resins; polyamide elastomers, polyurethane elastomers, polyester elastomers and the like can be mentioned.

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

It is also possible to laminate any base material other than thermoplastic resin, for example, paper, metal-based material, non-stretched, uniaxially stretched or biaxially stretched plastic film or sheet, woven fabric, non-woven fabric, metal cotton, wood and the like. be. Metallic materials include metals such as aluminum, iron, copper, nickel, gold, silver, titanium, molybdenum, magnesium, manganese, lead, tin, chromium, beryllium, tungsten and cobalt, and / or metal compounds thereof, and these. Examples thereof include alloy steels such as stainless steels composed of two or more types, aluminum alloys, copper alloys such as brass and bronze, and alloys such as nickel alloys.

As a laminated tube manufacturing method, a method of melt extrusion using an extruder corresponding to the number of layers or the number of materials and simultaneously laminating inside or outside the die (coextrusion molding method), or once a single-layer tube or An example is a method (coating method) in which a laminated tube manufactured by the above method is manufactured in advance, and the resins are integrated and laminated on the outside in sequence using an adhesive if necessary. The laminated tube is preferably manufactured by a coextrusion molding method in which various materials are coextruded in a molten state and both are heat-sealed (melt-bonded) to produce a tube having a laminated structure in one step. That is, the method for producing a laminated tube preferably includes coextrusion molding.

Further, when the obtained laminated tube has a complicated shape or is subjected to heat bending after molding to obtain a molded product, in order to remove the residual strain of the molded product, after forming the laminated tube, It is also possible to obtain a desired molded product by heat treatment for 0.01 hours or more and 10 hours or less at a temperature lower than the lowest melting point of the resins constituting the tube.

The laminated tube may have a corrugated region. The corrugated region is a region formed in a corrugated shape, a bellows shape, an accordion shape, a corrugated shape, or the like. The corrugated region may be not only provided over the entire length of the laminated tube, but may be partially provided in an appropriate region in the middle. The corrugated region can be easily formed by first molding a straight tubular tube and then molding the tube to obtain a predetermined corrugated shape or the like. By having such a corrugated region, it has shock absorption and is easy to attach. Further, for example, it is possible to form an L-shape, a U-shape, or the like by adding necessary parts such as a connector or bending the connector.

Natural rubber (NR), butadiene rubber (BR), isoprene rubber (IR) are applied to all or part of the outer circumference of the laminated tube thus formed in consideration of wear and flame resistance with stone splashes and other parts. , Butyl rubber (IIR), chloroprene rubber (CR), carboxylated butadiene rubber (XBR), carboxylated chloroprene rubber (XCR), epichlorohydrin rubber (ECO), acrylonitrile butadiene rubber (NBR), hydride acrylonitrile butadiene rubber (HNBR), Carboxylated acrylonitrile butadiene rubber (XNBR), a mixture of NBR and polyvinyl chloride, acrylonitrile isoprene rubber (NIR), chlorinated polyethylene rubber (CM), chlorosulfonated polyethylene rubber (CSM), ethylene propylene rubber (EPR), ethylene propylene Diene rubber (EPDM), ethylene vinyl acetate rubber (EVM), NBR and EPDM mixture rubber, acrylic rubber (ACM), ethylene acrylic rubber (AEM), acrylate butadiene rubber (ABR), styrene butadiene rubber (SBR), carboxylated styrene Butadiene rubber (XSBR), styrene isoprene rubber (SIR), styrene isoprene butadiene rubber (SIBR), urethane rubber, silicone rubber (MQ, VMQ), fluororubber (FKM, FFKM), fluorosilicone rubber (FVMQ), vinyl chloride type , A solid or sponge-like protective member (protector) composed of an olefin-based, ester-based, urethane-based, amide-based or other thermoplastic elastomer can be arranged. The protective member may be a sponge-like porous body by a known method. By making it a porous body, it is possible to form a protective portion that is lightweight and has excellent heat insulating properties. In addition, the material cost can be reduced. Alternatively, glass fiber or the like may be added to improve the strength. The shape of the protective member is not particularly limited, but is usually a block-shaped member having a recess for receiving a cylindrical member or a laminated tube. In the case of a tubular member, the laminated tube can be inserted into the previously prepared tubular member later, or the tubular member can be coated and extruded on the laminated tube to make them in close contact with each other. In order to bond the two, an adhesive is applied to the inner surface of the protective member or the concave surface as necessary, and a laminated tube is inserted or fitted therein, and the laminated tube and the protective member are integrated by bringing them into close contact with each other. Form a structure. It is also possible to reinforce with metal or the like.

The outer diameter of the laminated tube is such that the flow rate of the chemical solution (for example, fuel such as alcohol-containing gasoline) is taken into consideration, and the wall thickness is such that the permeability of the chemical solution does not increase and the breaking pressure of the normal tube can be maintained. In addition, the thickness is designed so that the ease of assembling the tube and the vibration resistance during use can be maintained to a good degree, but the thickness is not limited. The outer diameter is preferably 4 mm or more and 300 mm or less, the inner diameter is preferably 3 mm or more and 250 mm or less, and the wall thickness is preferably 0.5 mm or more and 25 mm or less.

The laminated tube of this embodiment includes mechanical parts such as automobile parts, internal combustion engine applications, power tool housings, industrial materials, industrial materials, electrical / electronic parts, medical care, foods, household / office supplies, building material-related parts, etc. It can be used for various purposes such as furniture parts.

Further, the laminated tube is suitable as a chemical liquid transport tube because it has an excellent chemical liquid barrier property. Examples of the chemical solution 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 glycols; phenolic solvents; ether solvents such as dimethyl ethers, dipropyl ethers, methyl-t-butyl ethers, ethyl-t-butyl ethers, dioxane, tetrahydrofurans, polyol esters, polyvinyl ethers; HFC-23 (trifluoromethane), HFC-32 (difluoromethane), HFC-41 (fluoromethane), HFC-123 (2,2-dichloro-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-hepta) Fluoropropane), HFC-236fa (1,1,1,3,3,3-hexafluoropropane), HFC-236ea (1,1,1,2,3,3-hexafluoropropane), HFC-236cc (1,1,1,2,3,3-hexafluoropropane) 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-245cc (1,1,1,2,2-pentafluoropropane), HFC-254eb (1,1,1,2-tetrafluoropropane), HFC-254cc (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-329mmz (1,1,1,1) 3,3,3-Hexafluoro-2- (trifluoro) propane), HFC-338mf (1,1,1,3,3,4,5,4-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-propen), HFC-1225zc (1,1,3,3,3-pentafluoro-1-propen), 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-propen), HFC-1234ze (1,3,3,3-tetrafluoro-1-propen), HFC-1234yf (2,3,3,3-tetrafluoro) -1-Propen), HFC-1234yc (1,1,2,3-tetrafluoro-1-propen), HFC-1234zc (1,1,3,3-tetrafluoro-1-propen), HFC-1243yf (1,1,2,3-tetrafluoro-1-propen) 2,3,3-trifluoro-1-propen), HFC-1243zc (1,1) , 3-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 (1,2,3,3,4,5,4-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-propen), HFC-1327cz (1,1,3,3,4,5,4-heptafluoro-1-butene), HFC-1327cye (1,1,2,3,4,5,4-hepta) Fluoro-1-butene), HFC-1327cyc (1,1,2,3,3,4,4-heptafluoro-1-butene), HFC-1336yf (2,3,3,4,5,4-hexa) Fluoro-1-butene), HFC-1336ze (1,3,3,4,5,4-hexafluoro-1-butene), HFC-1336eye (1,2,3,4,5,4-hexafluoro-) 1-butene), HFC-1336eyec (1,2,3,3,4,4-hexafluoro-1-butene), HFC-1336py (1,1,2,3,4,4-hexafluoro-2-) Butene), HFC-1336pz (1,1,1,2,4,4-hexafluoro-2-butene), HFC-1336mzy (1,1,1,3,4,5-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 (1,1,2,3,4,5-hexafluoro-1-butene), HFC-1336ft (3,3,3-trifluoro-2- (trifluoromethyl) -1-propen), HFC -1345qz (1,1,1,2,4-pentafluo) Lo-2-butene), HFC-1345mzy (1,1,1,3,4-pentafluoro-2-butene), HFC-1345fz (3,3,4,5,4-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-1345py (1,1,2,3,4-pentafluoro-2-butene), HFC-1345eyec (1,2,3,3,4-pentafluoro-) 1-butene), HFC-1345ctm (1,1,3,3,3-pentafluoro-2-methyl-1-propene), HFC-1345ftp (2- (difluoromethyl) -3,3,3-trifluoro -1-propen), HFC1345fy (2,3,4,5,4-pentafluoro-1-butene), HFC-1345eye (1,2,4,5,4-pentafluoro-1-butene), HFC- 1345 eze (1,3,4,5,4-pentafluoro-1-butene), HFC-1345 ezc (1,3,3,4,5-pentafluoro-1-butene), HFC-1345eye (1,2, 3,4,4-Pentafluoro-1-butene), HFC-1354fzzc (3,3,4,5-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) -Propen), HFC-1354 my (1,1,1,2-tetrafluoro-2-butene), HFC-1354mzy (1,1,1,3-tetrafluoro-2-butene), FC-141-10 myy (1,1,1,3-tetrafluoro-2-butene) 1,1,1,2,3,4,5,5,5-decafluoro-2-pentene), FC-141-10cy (1,1,2,3,3,4,5, 5,5-decafluoro-1-pentene) HFC-1429mzzt (1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene), HFC-1429 myz (1,1,1,2,4,5,5,5-nonafluoro-2-pentene), HFC-1429mzy (1,1,1,3,4,5,5,5-nonafluoro) -2-Pentene), HFC-1429eyec (1,2,3,3,4,5,5,5-nonafluoro-1-pentene), HFC-1429czc (1,1,3,3,4,4) , 5,5,5-Nonafluoro-1-pentene), HFC-1429cycc (1,1,2,3,3,4,5,5-Nonafluoro-1-pentene), HFC-1429py (1,1) , 2,3,4,4,5,5,5-nonafluoro-2-pentene), HFC-1429myyc (1,1,1,2,3,4,5,5-nonafluoro-2-pentene) , HFC-1429myy (1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene), HFC-1429myy (1,2,3,4,5,4-hexafluoro-3) -(Trifluoromethyl) -1-butene), HFC-1429sysm (1,1,2,4,4,4-hexafluoro-3- (trifluoromethyl) -1-butene), HFC-1429mzzt (1,1) 1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene), HFC-1429csym (1,1,3,4,5,4-hexafluoro-3- (trifluoro)) Methyl) -1-butene), HFC-1438fy (2,3,3,4,5,5,5-octafluoro-1-pentene), HFC-1438eycc (1,2,3,3,4) 4,5,5-octafluoro-1-pentene), HFC-1438ftmc (3,3,4,5,4-pentafluoro-2- (trifluoromethyl) -1-butene), HFC-1438czzm (1,1) 1,4,4,4-pentafluoro-3- (trifluoromethyl) -1-butene), HFC-1438ezym (1,3,4,5,4-pentafluoro-3- (trifluoromethyl) -1) -Buten), HFC-1438ctmf (1,1,4,4,4-pentafluoro-2- (trifluoromethyl) -1-butene), HFC-1447fzy (3,4,5,4-tetrafluoro-3) -(Trifluoromethyl) -1-butene), HFC-1447fz (3,3,4,5,5,5-ptafluoro-1-pentene), HFC-1447fycc (2,3,3,4,4) , 5,5-Heptafluoro-1-pentene), HF C-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 (2,4,5,4-tetrafluoro-3- (trifluoromethyl)) ) -1-Butene), HFC-1447ezz (1,4,5,4-tetrafluoro-3- (trifluoromethyl) -1-butene), HFC-1447qzzt (1,4,5,4-tetrafluoro-) 2- (Trifluoromethyl) -2-butene), HFC-1447syst (2,4,5,4-tetrafluoro-2- (trifluoromethyl) -2-butene), HFC-1456szt (3- (trifluoromethyl) szzt) Methyl) -4,4,4-trifluoro-2-butene), HFC-1456szy (3,4,5,5,5,hexafluoro-2-pentene), HFC-1456mstz (1,1,1,1) 4,4,4-Hexafluoro-2-methyl-2-butene), HFC-1456fzce (3,3,4,5,5,5-hexafluoro-1-pentene), HFC-1456ftmf (4,4) 4-Trifluoro-2- (trifluoromethyl) -1-butene), FC-151-12c (1,1,2,3,3,4,5,5,6,6,6-dodeca- 1-Hexene, Perfluoro-1-Hexene), FC-151-12mcy (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-152-11 mmyz (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-1549fzztmm (4,4,4-trifluoro-3,3-bis (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-1549fycz (2,3,3,5) , 5,5-Hexafluoro-4- (trifluoromethyl) -1-pentene), HFC-1549myts (1,1,1,2,4,5,5,5-nonafluoro-3-methyl-2) -Pentene), HFC-1549mzz (1,1,1,5,5,5-hexafluoro-4- (trifluoromethyl) -2-pentene), HFC-1558szy (3,4,5,5,5) 6,6,6-octafluoro-2-hexene), HFC-1558fzccc (3,3,4,4,5,5,6,6-octafluoro-2-hexene), HFC-1558mmtzc (1,1,1) 1,4,4-Pentafluoro-2- (trifluoromethyl) -2-pentene), HFC-1558ftmf (4,4,5,5,5-pentafluoro-2- (trifluoromethyl) -1-pentene) ), HFC-1567fts (3,3,4,5,5,5,5-heptenefluoro-2-methyl-1-pentene), HFC-1567szz (4,4,5,5,6,6-6-) Heptenefluoro-2-hexene), HFC-1567fzfc (4,5,5,6,6,6-heptenefluoro-1-hexene), HFC-1567sfy (1,1,1,2,2,3) 4-Heptafluoro-3-hexene), HFC-1567fzfy (4,5,5,5-tetrafluoro-4- (trifluoromethyl) -1-pentene), HFC-1567myzzm (1,1,1,2, 5,5,5-Heptenefluoro-4-methyl-2-pentene), HFC-1567mmtyf (1,1,1,3-tetrafluoro-2- (trifluoromethyl) -2-pentene), FC-161- 14myy (1,1,1,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene), FC-161-14mcyy (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 (1,1,1,2,2,2) 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), HCFC-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-pentafluoro) Propane), HCFC-225cc (1,3-dichloro-1,1,2,2,3-pentafluoropropane), HCFC-240db (1,1,1,2,3-pentachloropropane), HCFC-243db (1,3-dichloro-1,1,2,3-pentachloropropane) 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-trifluoro-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) Fluoroolefins such as fluoro-2-chloropropene), HCFC-1233zd (3,3,3-trifluoro-1-chloropropene), and mixtures thereof; ketone solvents such as acetone, methylethylketone, diethylketone, and 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 Liquid: GTL), coal liquefaction oil (Coal To Liquid: CTL), biomass liquefied oil (Biomass To Liquid: BTL), alcohol-containing gasoline, ethyl-t-butyl ether blend oxygen-containing gasoline , Amin-containing gasoline, sour gasoline, compressed natural gas (CNG), liquefied petroleum gas (LPG), liquefied hydrocarbon gas (LHG), liquefied natural gas (LNG), dimethyl ether for fuel (DME), castor oil base brake liquid, glycol Ether-based brake fluid, borate ester-based brake fluid, frigid region brake fluid, silicone oil-based brake fluid, mineral oil-based brake fluid, power steering oil, hydrogen sulfide oil, window washer fluid, engine coolant, urea solution, medicine Examples include chemicals, inks, paints and the like. The laminated tube is suitable as a tube for transporting the chemical solution, and specifically, a fuel tube such as a feed tube, a return tube, an evaporator tube, a fuel filler tube, an ORVR tube, a reserve tube, and a vent tube, and hydrogen for a fuel cell. Transport 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 tube, engine coolant (LLC) tube, reservoir tank tube, urea solution transport tube, cooling water, cooler tube for refrigerant, air conditioner refrigerant tube, heater tube, radiator tube, road heating tube, floor Examples include heating tubes, infrastructure supply tubes, fire extinguishing and fire extinguishing equipment tubes, medical cooling equipment tubes, inks, paint spray tubes, and other chemical tubes. 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.

Examples and comparative examples are shown below, and the present invention will be specifically described, but the present invention is not limited thereto. The analysis and physical property measurement methods in Examples and Comparative Examples, and the materials used in Examples and Comparative Examples are shown.

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

In addition, each physical property of the laminated tube was measured by the following method.
[Low temperature impact resistance]
An 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 with isooctane / toluene / ethanol = 45/45/10 by volume inside, or isooctane / toluene / ethanol 7.5 / 7.5 / Alcohol-containing gasoline (CE85) mixed in 85% by volume was put in, and the remaining end was also sealed. The total mass was then measured, then the test tube was placed in an oven at 60 ° C. and the mass change was measured daily. The daily mass change was divided by the inner layer surface area per 1 m of the tube ^{to calculate the alcohol-containing gasoline permeation amount (g / m 2} · day).

[Interlayer adhesiveness]
A tube cut to 200 mm was further cut in half in the vertical direction to prepare a test piece. Universal Material Testing Machine (Orientec, Tensilon UTM)
Using III-200), a 180 ° peeling test was carried out at a tensile speed of 50 mm / min. The peel strength was read from the maximum point of the SS curve, and the interlayer adhesiveness 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 adhesiveness of the removed tube was evaluated according to the above method. When the peel strength after the heat treatment was 2.0 N / mm or more, it was judged that the interlayer adhesive durability was excellent.

[Elution resistance of low molecular weight components]
A mixture of 42.25% toluene, 25.35% isooctane, 12.68% diisobutylene, 4.23% ethanol, 15% methanol, and 0.5% water, with one end of a tube cut to 0.5 m sealed. FAM compliant with DIN51604B
B was put inside and the remaining end was also sealed. Then, the test tube was placed in an oven at 60 ° C. and treated for 96 hours. Then, after cooling the alcohol-containing gasoline in the taken-out tube at room temperature, the test solution was evaporated to dry the residue, 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 was completed, 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) 19.7 kg (100.0 mol) of dodecane lactam, 5-amino-1,3,3-trimethylcyclohexanemethylamine 45. In a pressure-resistant reaction vessel with a stirrer with an internal volume of 70 liters. 0 g (0.26 mol) and 2.0 L of distilled water were charged, the inside of the polymerization tank was replaced with nitrogen, and then heated to 180 ° C., and the inside of the reaction system was stirred at this temperature so as to be in a uniform state. Next, the temperature inside the polymerization tank was raised to 270 ° C., and the pressure inside the tank was adjusted to 3.5 MPa, and the polymerization was carried out under stirring for 2 hours. Then, the pressure was released to normal pressure over about 2 hours, then the pressure was reduced to 53 kPa, and the polymerization was carried out under reduced pressure for 5 hours. Next, nitrogen was introduced into the autoclave, the pressure was restored to normal pressure, and then the strands were extracted from the lower nozzle of the reaction vessel and cut to obtain pellets. The pellet was dried under reduced pressure to obtain a 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 the 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 stearate (159.0 g of stearate). Polyamide 12 having a relative viscosity of 1.86 was prepared in the same manner as in the production of polyamide 12 (A1-1) except that the polyamide 12 (0.56 mol) was changed and the post-polymerization time was changed from 5 hours to 2.5 hours. Obtained (hereinafter, this polyamide 12 is referred to as (A1-2)).

Production of Polyamide 610 (A1-3) or (C22-1) 3.66 kg (31.5 mol) of 1,6-hexanediamine and 6.07 kg of sebacic acid (31.5 mol) in a pressure-resistant reaction vessel with a stirrer with an internal volume of 70 liters. 30.0 mol), 11.5 g of sodium hypophosphate monohydrate (0.1% by mass based on the raw material), and 5.0 L of distilled water were charged, and the inside of the polymerization tank was replaced with nitrogen, and then 220 ° C. The mixture was heated to the above temperature and stirred so that the inside of the reaction system became uniform at this temperature. Next, the temperature inside the polymerization tank was raised to 270 ° C., and the pressure inside the tank was adjusted to 1.7 MPa, and the polymerization was carried out under stirring for 2 hours. Then, the pressure was released to normal pressure over about 2 hours, then the pressure was reduced to 53 kPa, and the polymerization was carried out under reduced pressure for 4 hours. Next, nitrogen was introduced into the autoclave, the pressure was restored to normal pressure, and then the strands were extracted from the lower nozzle of the reaction vessel and cut to obtain pellets. The pellet was dried under reduced pressure to obtain a polyamide 610 having a relative viscosity of 2.58 (hereinafter, the 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 added to 6.91 kg (30.0 mol) of dodecanedioic acid. Polyamide 612 having a relative viscosity of 2.48 was obtained in the same manner as in the production of polyamide 610 (A1-3) except that the polyamide 612 was changed to (A1-4) or (C22-2). ).).

Aliphatic polyamide composition (A)
Production of Polyamide 12 Composition (A-1) On polyamide 12 (A1-1), maleic anhydride-modified ethylene / 1-butene copolymer (C4-1) described later as an impact improver, and triethylene as an antioxidant. Glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (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 Japan Steel Works, Ltd., model: TEX44), and melt-kneaded at a cylinder temperature of 180 ° C to 260 ° C. Then, after extruding the molten resin into a strand shape, this is introduced into a water tank, cooled, cut, and vacuum dried to make a total of 100 parts by mass of polyamide 12 (A1-1) 80% by mass and impact improving material 20% by mass. On the other hand, pellets of a polyamide 12 composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained (hereinafter, this polyamide 12 composition is referred to as (A-1). ).

Production of Polyamide 12 Composition (A-2) The production of the Polyamide 12 Composition (A-1) is the same as the production of the Polyamide 12 Composition (A-1) except that the amount of the impact improving material added is changed. By the method, from a total of 100 parts by mass of the polyamide 12 (A1-1) 85% by mass and the impact improving material 15% by mass, 0.8 parts by mass of the antioxidant and 0.2 parts by mass of the phosphorus-based processing stabilizer. A pellet of the polyamide 12 composition was obtained (hereinafter, this polyamide 12 composition is referred to as (A-2)).

Production of Conductive Polyamide 12 Composition (A-3) In the production of the polyamide 12 composition (A-1), the polyamide 12 (A1-1) was changed to (A1-2), and carbon black (Cabot) was used as a conductive filler. Polyamide 12 (A1-2) was produced in the same manner as in the production of the polyamide 12 composition (A-1), except that the cylinder temperature was changed from 260 ° C. to 270 ° C. using Vulcan XD-72) manufactured by the same company. Conductive polyamide composed of 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus-based processing stabilizer with respect to a total of 100 parts by mass of 60% by mass, 20% by mass of impact improving material, and 20% by mass of conductive filler. Pellets of 12 compositions were obtained (hereinafter, this conductive polyamide 12 composition is referred to as (A-3)).

Production of Polyamide 610 Composition (A-4) In the production of the polyamide 12 composition (A-1), the polyamide 12 (A1-1) was changed to the polyamide 610 (A1-3), and the cylinder of the biaxial melt kneader was used. Production of polyamide 12 composition (A-1) except that the benzenesulfonic acid butylamide (C3-1) described later was injected as a plasticizer from the middle of the above with 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 80% by mass of polyamide 610 (A1-3), 10% by mass of impact improving material, and 10% by mass of thermoplastic agent, 0.8 parts by mass of antioxidant and phosphorus-based Pellets of a polyamide 610 composition composed of 0.2 parts by mass of a processing stabilizer were obtained (hereinafter, this polyamide 610 composition is referred to as (A-4)).

Production of Polyamide 612 Composition (A-5) In the production of the polyamide 12 composition (A-1), the polyamide 12 (A1-1) was changed to the polyamide 612 (A1-4), and the cylinder of the biaxial melt kneader was used. Production of polyamide 12 composition (A-1) except that the benzenesulfonic acid butylamide (C3-1) described later was injected as a plasticizer from the middle of the above with 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 80% by mass of polyamide 612 (A1-4), 10% by mass of impact improving material, and 10% by mass of thermoplastic agent, 0.8 parts by mass of antioxidant and phosphorus-based Pellets of a polyamide 612 composition composed of 0.2 parts by mass of a processing stabilizer were obtained (hereinafter, this polyamide 612 composition is referred to as (A-5)).

Semi-aromatic polyamide (B1)
Production of Semi-Aromatic Polyamide (B1-1) 1,9-Nonandiamine 2.37 kg (15.0 mol), 2-Methyl-1,8-octanediamine 2.37 kg (15.0 mol), Terephthalic Acid 4. 94 kg (29.7 mol), 65.9 g (0.54 mol) of benzoic acid, 9.8 g of sodium hypophosphate monohydrate (0.1% by mass based on the raw material), and 6.0 L of distilled water. Was placed in an autoclave and replaced 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 boosted to 2.0 MPa. After continuing the reaction for 1 hour as it was, the temperature was raised to 230 ° C., and then the temperature was maintained at 230 ° C. for 2 hours, water vapor was gradually removed, and the reaction was carried out while maintaining the pressure at 2.0 MPa. Next, the pressure was lowered to 1.0 MPa over 30 minutes, and the reaction was carried out for another 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, subjected to solid phase polymerization at 210 ° C. and 0.013 kPa for 8 hours, having 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 the production of Semi-Aromatic Polyamide (B1-1), 2.37 kg (15.0 mol) of 1,9-nonanediamine and 2-methyl-1,8-octanediamine 2 Change .37 kg (15.0 mol) to 4.04 kg (25.5 mol) of 1,9-nonanediamine and 0.712 kg (4.5 mol) of 2-methyl-1,8-octanediamine, and solid-phase polymerization temperature. Semi-aromatic polyamide (polyamide 9T / M8T = 85) having a melting point of 305 ° C. and a relative viscosity of 2.34, in the same manner as in the production of the semi-aromatic polyamide (B1-1), except that the temperature was changed from 210 to 240 ° C. / 15 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B1-2)).

Production of Semi-Aromatic Polyamide (B1-3) In the production of semi-aromatic polyamide (B1-1), 4.94 kg (29.7 mol) of terephthalic acid was added to 6.43 kg (29.7 mol) of 2,6-naphthalenedicarboxylic acid. Semi-aromatic polyamide (polyamide 9N / M8N = 50/50 mol) having a melting point of 275 ° C. and a relative viscosity of 2.37 by the same method as for producing the semi-aromatic polyamide (B1-1) except that it was changed to (molar). %) Was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B1-3)).

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

Production of Semi-Aromatic Polyamide (B1-5) In the 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 ) 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 (polyamide 10T / 11 = 60/40 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B1-5)).

Production of Semi-Aromatic Polyamide (B1-6) In the production of Semi-Aromatic Polyamide (B1-4), 4.98 kg (30.0 mol) of terephthalic acid was combined with 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 semi-aromatic polyamide (B1-4), except that the solid phase polymerization temperature was changed from 260 ° C. to 220 ° C. by changing to 2.02 kg (10.0 mol). A semi-aromatic polyamide having a relative viscosity of 2.37 (polyamide 10T / 1010 = 67/33 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B1-6)).

Production of Semi-Aromatic Polyamide (B1-7) In the 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 an isomolar salt of 1,10-decanediamine and terephthalic acid, and 1.863 kg (6.0 mol) of an 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 (in the same manner as in the production of the semi-aromatic polyamide (B1-4), except that the solid phase 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 the production of Semi-Aromatic Polyamide (B1-1), 4.94 kg (29.7 mol) of terephthalic acid and 2.37 kg (15.0 mol) of 1,9-nonanediamine. , 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. Adipic acid. Semi-aromatic polyamide except that the weight was changed to 10 kg (7.5 mol) and 1,6-hexanediamine 3.60 kg (31.0 mol), the polymerization temperature was changed to 250 ° C, and the solid phase polymerization temperature was changed 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 by the same method as in the production of (B1-1) (hereinafter, This 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 to diaphragm pump, nitrogen gas inlet, pressure discharge port, pressure regulator, and polymer discharge port. In a pressure vessel with an internal volume of 70 liters, 6.07 kg (30.0 mol) of sebacic acid, 8.5 g (0.049 mol) of calcium hypophosphate, and 2.2 g (0.025 mol) of sodium acetate were charged. After pressurizing the inside of the pressure vessel with nitrogen gas having a purity of 99.9999% to 0.3 MPa, the operation of releasing the nitrogen gas to normal pressure was repeated 5 times, and after nitrogen substitution, the pressure was reduced. The temperature inside the system was raised while stirring. After raising the temperature to 190 ° C. under a further small amount of nitrogen stream, 4.09 kg (30.0 mol) of m-xylylenediamine was added dropwise over 160 minutes under stirring. During this period, the internal pressure of the reaction system was controlled to 0.5 MPa, and the internal temperature was continuously raised to 295 ° C. In addition, the water distilled out with the dropping of m-xylylenediamine was removed from the system through a condenser and a cooler. After the addition of m-xylylenediamine was completed, the pressure was lowered to normal pressure over 60 minutes, and during this period, the temperature inside the container was maintained at 250 ° C. and the reaction was continued for 10 minutes. Then, the internal pressure of the reaction system was reduced to 79 kPa, and the melt polymerization reaction was continued for 40 minutes. Then, the stirring was stopped and the inside of the system was pressurized to 0.2 MPa with nitrogen, and the polycondensate was extracted in a string shape from the outlet at the bottom of the pressure vessel. The string-shaped polycondensate is immediately cooled, the water-cooled string-shaped resin is pelletized with a pelletizer, and then dried under reduced pressure to achieve a semi-aromatic polyamide (polyamide MXD10 = 100 mol%) having a melting point of 191 ° C. and a relative viscosity of 2.46. ) (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 was added to m-xylylenediamine and p-xylylenediamine. In the same manner as for the production of semi-aromatic polyamide (B2-1), except that the mixture was changed to 4.09 kg (30.0 mol) of the 7: 3 mixed amine and the polymerization temperature was changed from 250 ° C. to 260 ° C. , 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 was added to m-xylylenediamine and p-xylylenediamine. The same method as for the production of semi-aromatic polyamide (B2-1) except that the ratio was changed to 4.09 kg (30.0 mol) of the 6: 4 mixed amine 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 added to 4.09 kg (30. The melting point is 281 and 291 ° C. (having two melting points) in the same manner as in the production of the semi-aromatic polyamide (B2-1) except that the polymerization temperature is changed from 250 ° C. to 300 ° C. (0 mol). , 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 the 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. A semi-aromatic polyamide (polyamide MXD9 = 100 mol%) having a melting point of 194 ° C. and a relative viscosity of 2.45 was obtained by the same method as for producing the semi-aromatic polyamide (B2-1) except for the above. The 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-xylylene diamine 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 weight was changed to .59 kg (30.0 mol) and the polymerization temperature was changed from 240 ° C. to 300 ° C. A semi-aromatic polyamide of .33 (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 the 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. Semi-aromatic polyamide (polyamide MXD6 =) having a melting point of 243 ° C and a relative viscosity of 2.42 in the same manner as in the production of semi-aromatic polyamide (B2-1) except that the polymerization temperature was changed from 250 ° C to 275 ° C. 100 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B2-7)).

Semi-aromatic polyamide composition (B)
Production of Semi-Aromatic Polyamide Composition (B-1) Anti-oxidation of semi-aromatic polyamide (B1-1) with maleic anhydride-modified ethylene / 1-butene copolymer (C4-1) described later as an impact improver. Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (BASF Japan, Inc., IRGANOX245) as an agent, and Tris (2,4-) as a phosphorus-based processing stabilizer. 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 Co., Ltd., model: TEX44), and the cylinder temperature is 220 ° C. to 300 ° C. After melt-kneading at ° C and extruding the molten resin into strands, this is introduced into a water tank, cooled, cut, and vacuum-dried to 90% by mass of semi-aromatic polyamide (B1-1) and 10 mass of impact improver. A pellet of a semi-aromatic polyamide composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer was obtained with respect to 100 parts by mass of the total of% (hereinafter, this semi-aromatic polyamide). The composition is referred to as (B-1)).

Production of Semi-Aromatic Polyamide Composition (B-2) In the production of the semi-aromatic polyamide composition (B-1), the semi-aromatic polyamide (B1-1) was changed to (B1-2) and the cylinder temperature was set to 300. 90% by mass of the semi-aromatic polyamide (B1-2) and 10% by mass of the impact improver by the same method as in the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from 340 ° C to 340 ° C. Pellets of a semi-aromatic polyamide composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained with respect to 100 parts by mass in total (hereinafter, this semi-aromatic polyamide composition). Is called (B-2).

Production of Semi-Aromatic Polyamide Composition (B-3) In the production of the semi-aromatic polyamide composition (B-1), the semi-aromatic polyamide (B1-1) was changed to (B1-3) and the cylinder temperature was set to 300. 90% by mass of the semi-aromatic polyamide (B1-3) and 10% by mass of the impact improving material were prepared in the same manner as in the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from ° C to 310 ° C. Pellets of a semi-aromatic polyamide composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained with respect to 100 parts by mass in total (hereinafter, this semi-aromatic polyamide composition). Is called (B-3).

Production of Semi-Aromatic Polyamide Composition (B-4) In the production of the 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. 90% by mass of semi-aromatic polyamide (B1-4) and 10% by mass of impact improving material by the same method as in the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from ℃ to 340 ° C. Pellets of a semi-aromatic polyamide composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained with respect to 100 parts by mass in total (hereinafter, this semi-aromatic polyamide composition). Is called (B-4).).

Production of Semi-Aromatic Polyamide Composition (B-5) In the production of the semi-aromatic polyamide composition (B-1), the semi-aromatic polyamide (B1-1) was changed to (B1-5) and the cylinder temperature was set to 300. 90% by mass of the semi-aromatic polyamide (B1-5) and 10% by mass of the impact improver by the same method as in the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from ℃ to 290 ° C. Pellets of a semi-aromatic polyamide composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained with respect to 100 parts by mass in total (hereinafter, this semi-aromatic polyamide composition). Is called (B-5)).

Production of Semi-Aromatic Polyamide Composition (B-6) In the production of the semi-aromatic polyamide composition (B-1), the semi-aromatic polyamide (B1-1) was changed to (B1-6) and the cylinder temperature was set to 300. 90% by mass of semi-aromatic polyamide (B1-6) and 10% by mass of impact improver by the same method as in the production of semi-aromatic polyamide composition (B-1) except that the temperature was changed from ° C to 310 ° C. Pellets of a semi-aromatic polyamide composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained with respect to 100 parts by mass in total (hereinafter, this semi-aromatic polyamide composition). Is called (B-6).

Production of Semi-Aromatic Polyamide Composition (B-7) In the production of semi-aromatic polyamide composition (B-1), except that the semi-aromatic polyamide (B1-1) was changed to (B1-7). By the same method as in the production of the aromatic polyamide composition (B-1), an antioxidant is applied to a total of 100 parts by mass of 90% by mass of the semi-aromatic polyamide (B1-7) and 10% by mass of the impact improving material. Pellets of a semi-aromatic polyamide composition consisting of 0.8 parts by mass and 0.2 parts by mass of a phosphorus-based processing stabilizer were 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 the semi-aromatic polyamide composition (B-1), the semi-aromatic polyamide (B1-1) was changed to (B1-8) and the cylinder temperature was set to 300. 90% by mass of the semi-aromatic polyamide (B1-8) and 10% by mass of the impact improver by the same method as in the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from 340 ° C to 340 ° C. Pellets of a semi-aromatic polyamide composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained with respect to 100 parts by mass in total (hereinafter, this semi-aromatic polyamide composition). Is called (B-8)).

Production of Semi-Aromatic Polyamide Composition (B-9) In the production of the semi-aromatic polyamide composition (B-1), the semi-aromatic polyamide (B1-1) was changed to (B2-1) and the cylinder temperature was set to 300. 90% by mass of the semi-aromatic polyamide (B2-1) and 10% by mass of the impact improving material were prepared in the same manner as in the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from ° C to 240 ° C. Pellets of a semi-aromatic polyamide composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained with respect to 100 parts by mass in total (hereinafter, this semi-aromatic polyamide composition). Is called (B-9)).

Production of Semi-Aromatic Polyamide Composition (B-10) In the production of the semi-aromatic polyamide composition (B-9), the semi-aromatic polyamide (B2-1) was changed to (B2-2) and the cylinder temperature was changed to 240. 90% by mass of semi-aromatic polyamide (B2-2) and 10% by mass of impact improver by the same method as in the production of semi-aromatic polyamide composition (B-9) except that the temperature was changed from ° C to 250 ° C. Pellets of a semi-aromatic polyamide composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained with respect to 100 parts by mass in total (hereinafter, this semi-aromatic polyamide composition). Is called (B-10)).

Production of Semi-Aromatic Polyamide Composition (B-11) In the production of the semi-aromatic polyamide composition (B-9), the semi-aromatic polyamide (B2-1) was changed to (B2-3) and the cylinder temperature was changed to 240. 90% by mass of semi-aromatic polyamide (B2-3) and 10% by mass of impact improver by the same method as in the production of semi-aromatic polyamide composition (B-9) except that the temperature was changed from ° C to 260 ° C. Pellets of a semi-aromatic polyamide composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained with respect to 100 parts by mass in total (hereinafter, this semi-aromatic polyamide composition). Is referred to as (B-11)).

Production of Semi-Aromatic Polyamide Composition (B-12) In the production of the semi-aromatic polyamide composition (B-9), the semi-aromatic polyamide (B2-1) was changed to (B2-4) and the cylinder temperature was changed to 240. 90% by mass of semi-aromatic polyamide (B2-4) and 10% by mass of impact improver by the same method as in the production of semi-aromatic polyamide composition (B-9) except that the temperature was changed from ° C to 320 ° C. Pellets of a semi-aromatic polyamide composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained with respect to 100 parts by mass in total (hereinafter, this semi-aromatic polyamide composition). Is called (B-12)).

Production of Semi-Aromatic Polyamide Composition (B-13) In the production of semi-aromatic polyamide composition (B-9), except that the semi-aromatic polyamide (B2-1) was changed to (B2-5). By the same method as in the production of the aromatic polyamide composition (B-9), an antioxidant is applied to a total of 100 parts by mass of 90% by mass of the semi-aromatic polyamide (B2-5) and 10% by mass of the impact improving material. Pellets of a semi-aromatic polyamide composition consisting of 0.8 parts by mass and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained (hereinafter, this semi-aromatic polyamide composition is referred to as (B-13)).

Production of Semi-Aromatic Polyamide Composition (B-14) In the production of the semi-aromatic polyamide composition (B-9), the semi-aromatic polyamide (B2-1) was changed to (B2-6) and the cylinder temperature was changed to 240. 90% by mass of semi-aromatic polyamide (B2-6) and 10% by mass of impact improver by the same method as in the production of semi-aromatic polyamide composition (B-9) except that the temperature was changed from ° C to 320 ° C. Pellets of a semi-aromatic polyamide composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained with respect to 100 parts by mass in total (hereinafter, this semi-aromatic polyamide composition). Is called (B-14)).

Production of Semi-Aromatic Polyamide Composition (B-15) In the production of the semi-aromatic polyamide composition (B-9), the semi-aromatic polyamide (B2-1) was changed to (B2-7) and the cylinder temperature was changed to 240. 90% by mass of the semi-aromatic polyamide (B2-7) and 10% by mass of the impact improver by the same method as in the production of the semi-aromatic polyamide composition (B-9) except that the temperature was changed from ℃ to 280 ° C. Pellets of a semi-aromatic polyamide composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained with respect to 100 parts by mass in total (hereinafter, this semi-aromatic polyamide composition). Is called (B-15)).

Polyamide 6 (C11)
Production of Polyamide 6 (C11-1) 11.32 kg (100.0 mol) of caprolactam and 2.0 L of distilled water were placed in a pressure-resistant reaction vessel with an internal volume of 70 liters and heated to 100 ° C. at this temperature. The mixture was stirred so that the inside of the reaction system became uniform. Subsequently, the temperature was further raised to 260 ° C., and the mixture was stirred under a pressure of 2.5 MPa for 1 hour. Then, the pressure was released to volatilize the water from the reaction vessel, and the polymerization reaction was carried out at 260 ° C. for 2 hours under normal pressure, and further the polymerization reaction was carried out at 260 ° C. under a reduced pressure of 53 kPa for 6 hours. After completion of the reaction, the reaction product taken out in a strand shape from the lower nozzle of the reaction vessel was introduced into a water tank, cooled, and cut to obtain pellets. The pellets were immersed in hot water to extract and remove unreacted monomers, and then dried under reduced pressure to obtain a 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 added to 9.93 kg (87.7 mol) of caprolactam, 1,6-. Production of Polyamide 6 (C11-1), except that the equimolar salt of hexanediamine and adipic acid was changed to 1.40 kg (5.7 mol) and 12-aminododecanoic acid 1.40 kg (6.5 mol). In the same manner, a polyamide 6/66/12 (caprolactam unit / hexamethylene adipamide unit / dodecaneamide unit = 78/11/11 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 the production of Polyamide 6/66/12 (C21-1), caprolactam 9.93 kg (87.7 mol), an 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, 9.90 kg (87.5 mol) of caprolactam and 2.69 kg (12.5 mol) of 12-aminododecanoic acid. ), The same method as for the production of polyamide 6/66/12 (C21-1), with a relative viscosity of 3.86 polyamide 6/12 (caprolactam unit / dodecaneamide unit = 80/20 mass%). ) (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) (manufactured by Mitsui Chemicals, Inc., Toughmer MH5010)

Polyamide 6 Composition Production of Polyamide 6 Composition (C1-1) In the production of the polyamide 12 composition (A-1), the polyamide 12 (A1-1) was changed to the polyamide 6 (C11-3) and the biaxial melting was performed. Production of polyamide 12 composition (A-1) except that benzenesulfonic acid butylamide (C3-1) was injected from the middle of the cylinder of the kneader by a metering pump and the cylinder temperature was changed from 260 ° C to 270 ° C. Antioxidation is applied to a total of 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 in the same manner. Pellets of a polyamide 6 composition composed of 0.8 parts by mass of an agent and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained (hereinafter, this polyamide 6 composition is referred to as (C1-1)).

Polyamide 6/66/12 composition (C2)
Production 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), as an antioxidant, triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (BASF Japan, Inc., IRGANOX245), and as a phosphorus-based processing stabilizer. 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 Co., Ltd., model: TEX44). After injecting benzenesulfonic acid butylamide (C3-1) from the middle of the cylinder of the twin-screw melt-kneader by a metering pump, melt-kneading at a cylinder temperature of 180 ° C. to 260 ° C., and extruding the molten resin into a strand shape. , This was introduced into a water tank, cooled, cut, and vacuum dried to obtain 50% by mass of polyamide 6/66/12 (C21-1), 30% by mass of polyamide 610 (C22-1), and a plastic agent (C3-1). Polyamide 6/66 / consisting of 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 and 15% by mass of elastomer polymer (C4-1). Pellets of 12 compositions were obtained (hereinafter, this polyamide 6/66/12 composition is referred to as (C2-1)).

Production of Polyamide 6/66/12 Composition (C2-2) In the production of Polyamide 6/66/12 Composition (C2-1), polyamide 610 (C22-1) was changed to polyamide 612 (C22-2). Except for the above, the same method as for the production of the polyamide 6/66/12 composition (C2-1) was used, with 60% by mass of the polyamide 6/66/12 (C21-1) and 20% by mass of the polyamide 612 (C22-2). , 5% by mass of plasticizer (C3-1) and 15% by mass of elastomer polymer (C4-1), 0.8 parts by mass of antioxidant and 0.2% by mass of phosphorus-based processing stabilizer. Pellets of a polyamide 6/66/12 composition composed of parts were 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 / in the production of Polyamide 6/66/12 Composition (C2-1), except that Polyamide 610 (C22-1) is not used. 12 Polyamide 6/66/12 (C21-1) 80% by mass, thermoplastic (C3-1) 5% by mass, elastomer polymer (C4-1) in the same manner as in the production of the composition (C2-1). ) A pellet of a polyamide 6/66/12 composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer was obtained with respect to 100 parts by mass in total of 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) In the production of polyamide 6/66/12 composition (C2-1), polyamide 610 (C22-1), plasticizer (C3-1), and elastomer 100% by mass of polyamide 6/66/12 (C21-1) by the same method as for producing the polyamide 6/66/12 composition (C2-1) except that the polymer (C4-1) is not used. On the other hand, pellets of a polyamide 6/66/12 composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained (hereinafter, this polyamide 6/66/12 composition is used. (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 used as Polyamide 6/12 (C21-2). ), In the same manner as in the production of the polyamide 6/12 (C2-4) composition, the antioxidant 0. Pellets of a polyamide 6/12 composition consisting of 8 parts by mass and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained (hereinafter, this polyamide 6/12 composition is referred to as (C2-5)).

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

Production of Polyketone Polyketone Composition (D-2) In addition to polyketone (D-1), carbon black (Vulcan XD-72 manufactured by Cabot) as a conductive filler and triethylene glycol-bis as an antioxidant. [3- (3-t-Butyl-5-methyl-4-hydroxyphenyl) propionate] (BASF Japan, Inc., IRGANOX245), and tris (2,4-di-t-butylphenyl) as a phosphorus-based processing stabilizer. Phosphite (manufactured by BASF Japan, IRGAFOS168) is mixed in advance and supplied to a twin-screw melt-kneader (manufactured by Nippon Steel Co., Ltd., model: TEX44), while from the middle of the cylinder of the twin-screw melt-kneader. Benzenesulfonic acid butylamide as a plasticizer is injected by a metering pump, melt-kneaded at a cylinder temperature of 180 ° C. to 260 ° C., the molten resin is extruded into a strand shape, introduced into a water tank, cooled, cut, and vacuum-dried. It is composed of 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus-based processing stabilizer with respect to a total of 100 parts by mass of 85% by mass of the aliphatic polyketone (D-1) and 15% by mass of the conductive filler. Pellets of the conductive polyketone composition were obtained (hereinafter, this conductive aliphatic polyketone composition is referred to as (D-2)).

Example 1
Using the above-mentioned polyamide 12 composition (A-1), semi-aromatic polyamide composition (B-1), polyamide 6 composition (C1-1), and aliphatic polyketone (D-1), a plastic (A-1) is an extrusion temperature of 250 ° C., (B-1) is an extrusion temperature of 300 ° C., and (C-1) is an extrusion temperature of 260 ° C. in a 4-layer tube molding machine (manufactured by Plastic Engineering Laboratory Co., Ltd.). , (D-1) were separately melted at an extrusion temperature of 250 ° C., and the discharged molten resins were merged by an adapter to form a laminated tubular body. Subsequently, it is cooled by a sizing die whose dimensions are controlled and taken over, and the (a) layer (outermost layer) composed of (A-1), the (b) layer (intermediate layer) composed of (B-1), and (C-) When the (c) layer (inner layer) consisting of 1) and the (d) layer (innermost layer) consisting of (D-1) are used, the layer structure 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. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 2
In Example 1, the same as 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. By the method, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 3
In Example 1, the same as in Example 1 except that 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, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 4
In Example 1, the method was the same as 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. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 5
In Example 1, the method was the same as 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. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 6
In Example 1, the method was the same as in Example 1 except that the semi-aromatic polyamide composition (B-1) was changed to (B-4) and the extrusion temperature of (B-4) was changed to 340 ° C. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 7
In Example 1, the method was the same as in Example 1 except that the semi-aromatic polyamide composition (B-1) was changed to (B-5) and the extrusion temperature of (B-5) was changed to 290 ° C. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 8
In Example 1, the method was the same as in Example 1 except that the semi-aromatic polyamide composition (B-1) was changed to (B-6) and the extrusion temperature of (B-6) was changed to 310 ° C. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 9
In Example 1, a laminated tube having a layer structure shown in Table 1 was obtained in the same manner as in Example 1 except that the semi-aromatic polyamide composition (B-1) was changed to (B-7). .. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 10
In Example 1, the method was the same as in Example 1 except that the semi-aromatic polyamide composition (B-1) was changed to (B-9) and the extrusion temperature of (B-9) was changed to 240 ° C. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 11
In Example 1, the method was the same as in Example 1 except that the semi-aromatic polyamide composition (B-1) was changed to (B-10) and the extrusion temperature of (B-10) was changed to 250 ° C. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 12
In Example 1, the method was the same as in Example 1 except that the semi-aromatic polyamide composition (B-1) was changed to (B-11) and the extrusion temperature of (B-11) was changed to 260 ° C. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 13
In Example 1, the method was the same as in Example 1 except that the semi-aromatic polyamide composition (B-1) was changed to (B-12) and the extrusion temperature of (B-12) was changed to 320 ° C. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 14
In Example 1, the method was the same as 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. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 15
In Example 1, the method was the same as in Example 1 except that the semi-aromatic polyamide composition (B-1) was changed to (B-14) and the extrusion temperature of (B-14) was changed to 320 ° C. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 16
In Example 1, the layer configuration shown in Table 1 was carried out in the same manner as in Example 1 except that the polyamide 6 composition (C1-1) was changed to the polyamide 6/66/12 composition (C2-1). Obtained a laminated tube. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 17
In Example 1, the layer configuration shown in Table 1 was carried out in the same manner as in Example 1 except that the polyamide 6 composition (C1-1) was changed to the polyamide 6/66/12 composition (C2-2). Obtained a laminated tube. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 18
In Example 1, the layer configuration shown in Table 1 was carried out in the same manner as in Example 1 except that the polyamide 6 composition (C1-1) was changed to the polyamide 6/66/12 composition (C2-3). Obtained a laminated tube. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 19
In Example 1, the same as 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. In the same manner, laminated tubes having the layer structure shown in Table 1 were obtained. Table 1 shows the results of measuring the physical properties of the laminated tube. Further, the electrical conductivity of the laminate tube was measured according to SAE J-2260, and at 10 ⁶ Ω / square or less, it was confirmed that an excellent destaticizing 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 Polybor (manufactured by Plastic Engineering Laboratory Co., Ltd.) 5-layer tube molding machine, (A-1) was extruded at an extrusion temperature of 250 ° C., (B-). 1) was separately melted at an extrusion temperature of 300 ° C., (C1-1) at an extrusion temperature of 260 ° C., (D-1) at an extrusion temperature of 250 ° C., and (D-2) at an extrusion temperature of 270 ° C. The molten resin was merged by an adapter and molded into a laminated tubular body. Subsequently, it is cooled by a sizing die whose dimensions are controlled and taken over, and the (a) layer (outermost layer) composed of (A-1), the (b) layer (outer layer) composed of (B-1), and (C1-1). ) (C) layer (intermediate layer), (D-1) (d) layer (inner layer), and (D-2) (d') layer (innermost layer). (A) / (b) / (c) / (d) / (d') = 0.35 / 0.15 / 0.30 / 0.10 / 0.10 mm, laminated tube with inner diameter 6 mm and outer diameter 8 mm Got Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 21
The above-mentioned 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 an aliphatic polyketone (D-1), (A-1) is extruded at an extrusion temperature of 250 ° C. and (B-1) is extruded using a Polybor (manufactured by Plastic Engineering Laboratory Co., Ltd.) 5-layer tube forming machine. The temperature is 300 ° C., (C1-1) and (C2-1) are separately melted at an extrusion temperature of 260 ° C., and (D-1) is melted separately at an extrusion temperature of 250 ° C., and the discharged molten resins are merged by an adapter and laminated. It was molded into a tubular body. Subsequently, it is cooled by a sizing die whose dimensions are controlled and taken over, and the (a) layer (outermost layer) composed of (A-1), the (c) layer (outer layer) composed of (C2-1), and (B-1) ), The layer (c') consists of (C1-1), and the layer (d) consists of (D-1). (A) / (c) / (b) / (c') / (d) = 0.30 / 0.10 / 0.15 / 0.30 / 0.15 mm, laminated tube with an inner diameter of 6 mm and an outer diameter of 8 mm Got Table 1 shows the results of measuring the physical properties of the laminated tube. , The electrical conductivity of the laminate tube was measured according to SAE J-2260, and at 10 ⁶ Ω / square or less, it was confirmed that an excellent destaticizing performance.

Example 22
In Example 21, the polyamide 6 composition (C1-1) used for the inner layer was changed to the polyamide 6/66/12 composition (C2-1), except that the same method as in Example 21 was used in Table 1. A laminated tube having the layer structure shown in the above was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

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

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

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) in a Polybor (manufactured by Plastic Engineering Laboratory Co., Ltd.) 6-layer tube molding machine (A-1). Is an extrusion temperature of 250 ° C., (B-1) is an extrusion temperature of 300 ° C., (C1-1) and (C2-1) are extrusion temperatures of 260 ° C., (D-1) is an extrusion temperature of 250 ° C., (D-2). Was separately melted at an extrusion temperature of 270 ° C., and the discharged molten resins were merged by an adapter to form a laminated tubular body. Subsequently, it is cooled by a sizing die whose dimensions are controlled and taken over, and the (a) layer (outermost layer) composed of (A-1), the (c) layer (outer layer) composed of (C2-1), and (B-1) ) (B) (intermediate layer), (C1-1) (c') (inner layer), (D-1) (d) (inner layer 2), (D-2) (D') (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. Table 1 shows the results of measuring the physical properties of the laminated tube. Further, the electrical conductivity of the laminate tube was measured according to SAE J-2260, and at 10 ⁶ Ω / square or less, it was confirmed that an excellent destaticizing performance.

Example 26
In Example 25, Table 1 was carried out in the same manner as in Example 25, except that the polyamide 6 composition (C1-1) used for the inner layer was changed to the polyamide 6/66/12 composition (C2-1). A laminated tube having the layer structure shown in the above was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

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

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

Comparative Example 1
In Example 1, a laminated tube having a layer structure shown in Table 1 was obtained in the same manner as in Example 1 except that the polyamide 12 composition (A-1) was not used. Table 1 shows the results of measuring the physical properties of the laminated tube.

Comparative Example 2
In Example 1, a laminated tube having a layer structure shown in Table 1 was obtained by the same method as in Example 1 except that the semi-aromatic polyamide composition (B-1) was not used. Table 1 shows the results of measuring the physical properties of the laminated tube.

Comparative Example 3
In Example 1, the method was the same as in Example 1 except that the semi-aromatic polyamide composition (B-1) was changed to (B-8) and the extrusion temperature of (B-8) was changed to 350 ° C. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Comparative Example 4
In Example 1, the method was the same as in Example 1 except that the semi-aromatic polyamide composition (B-1) was changed to (B-15) and the extrusion temperature of (B-15) was changed to 280 ° C. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Comparative Example 5
In Example 1, a laminated tube having a layer structure shown in Table 1 was obtained in the same manner as in Example 1 except that the polyamide 6 composition (C1-1) was not used. Table 1 shows the results of measuring the physical properties of the laminated tube.

Comparative Example 6
In Example 1, a laminated tube having a layer structure shown in Table 1 was obtained in the same manner as in Example 1 except that the aliphatic polyketone (D-1) was not used. Table 1 shows the results of measuring the physical properties of the laminated tube.

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

Comparative Example 8
In Example 17, the same as in Example 1 except that 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. A laminated tube having a layered structure shown in Table 1 was obtained by the method of. Table 1 shows the results of measuring the physical properties of the laminated tube. Further, the electrical conductivity of the laminate tube was measured according to SAE J-2260, and at 10 ⁶ Ω / square or less, it was confirmed that an excellent destaticizing performance.

Comparative Example 9
In Example 22, the laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 22 except that the polyamide 6/66/12 composition (C2-1) was changed to (C2-4). Obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Comparative Example 10
In Example 22, the method shown in Table 1 is the same as in Example 22 except that the polyamide 6/66/12 composition (C2-1) is changed to the polyamide 6/12 composition (C2-5). A layered laminated tube was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

As is clear from Table 1, the laminated tube of Comparative Example 1 which does not have the layer containing the aliphatic polyamide specified in the present invention is inferior in low temperature impact resistance, and the layer containing the semi-aromatic polyamide composition of the present invention is used. The laminated tube of Comparative Example 2 which did not have was inferior in chemical barrier property. The laminated tubes of Comparative Examples 3 and 4 having a layer containing a semi-aromatic polyamide composition other than those specified 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 specified in the present invention was inferior in the durability of interlayer adhesion. The laminated tube of Comparative Example 6 which does not have the aliphatic polyketone specified in the present invention was inferior in elution resistance of low molecular weight components. The laminated tubes of Comparative Examples 7 and 8 having no layer containing the aliphatic polyketone specified in the present invention and having a layer containing a polyamide 12 composition as the innermost layer are inferior in elution resistance of low molecular weight components. rice field. board. The laminated tubes of Comparative Examples 9 and 10 having a polyamide 6/66/12 composition or a layer containing a polyamide 6/12 composition other than those specified in the present invention were inferior in the durability of interlayer adhesion.
On the other hand, the laminated tubes of Examples 1 to 28 specified in the present invention have low-temperature impact resistance, interlayer adhesion and durability to low-concentration to high-concentration alcohol-containing gasoline, elution resistance of low molecular weight components, and the like. It is clear that the properties of are good.

Claims (12)

A laminated tube having four or more layers including a layer (a), a layer (b), a layer (c), and a layer (d).
At least one set of the layer (c) and the layer (d) are arranged adjacent to each other.
The layer (a) contains an aliphatic polyamide (A) and contains
The layer (b) contains the semi-aromatic polyamide composition (B) and contains.
The layer (c) contains the polyamide 6 composition (C1).
The layer (d) contains an aliphatic polyketone (D) and contains
The aliphatic polyamide (A) does not contain polycaproamide (polyamide 6) and / or poly (caproamide / hexamethylene adipamide / dodecane amide) (polyamide 6/66/12).
The semi-aromatic polyamide composition (B) contains a semi-aromatic polyamide (B1) or a semi-aromatic polyamide (B2).
The semi-aromatic polyamide (B1) contains 50 mol% or more of an aliphatic diamine unit having 9 or 10 carbon atoms with respect to the total diamine units of the semi-aromatic polyamide (B1), and the semi-aromatic polyamide (B1). B1) contains 50 mol% or more of terephthalic acid units and / or naphthalenedicarboxylic acid units with respect to all dicarboxylic acid units.
The semi-aromatic polyamide (B2) contains 50 mol% or more of xylylene diamine units and / or bis (aminomethyl) naphthalene units with respect to the total diamine units of the semi-aromatic polyamide (B2), and the semi-aromatic polyamide (B2). It contains 50 mol% or more of an aliphatic dicarboxylic acid unit having 9 or 10 carbon atoms with respect to all the dicarboxylic acid units of the group polyamide (B2).
The polyamide 6 composition (C1) contains 50% by mass or more and 98% by mass or less of polycaproamide (polyamide 6) (C11), 1% by mass or more and 20% by mass or less of a plasticizer (C3), and an elastomer polymer (C4). Contains 1% by mass or more and 30% by mass or less,
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. The aliphatic polyamide (A) includes polyundecaneamide (polyamide 11), polydodecaneamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylenedecamide (polyamide 610), and polyhexamethylenedodeca. At least one homopolymer selected from the group consisting of mid (polyamide 612), polydecamethylene decamide (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 and / or these. The laminated tube according to claim 1 or 2, wherein the semi-aromatic polyamide composition (B) contains the elastomer polymer (C4). 13. The laminated tube according to item 1. The polyamide (C22) is other than polyamide 6/66/12 (C21), and is polycaproamide (polyamide 6), polyundecaneamide (polyamide 11), polydodecaneamide (polyamide 12), polyhexamethylene adipa. Mido (polyamide 66), polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene decamide (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 unit for forming these. The laminated tube according to any one of claims 1 to 4, which is a copolymer using several kinds of weights. 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 the 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 positive integers. ] The layer (a) is arranged on the outermost layer,
The laminated tube according to any one of claims 1 to 6, wherein the layer (c) is arranged between the layer (a) and the layer (d). The laminated tube according to any one of claims 1 to 7, wherein at least one set of the layer (a) and the layer (c) are arranged adjacent to each other. The layer (d) is arranged 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 manufactured 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 having four or more layers including a layer (a), a layer (b), a layer (c), and a layer (d).
At least one set of the layer (c) and the layer (d) are arranged adjacent to each other.
The layer (a) contains an aliphatic polyamide (A) and contains
The layer (b) contains the semi-aromatic polyamide composition (B) and contains.
The layer (c) contains the polyamide 6 composition (C1).
The layer (d) contains an aliphatic polyketone (D) and contains
The aliphatic polyamide (A) does not contain polycaproamide (polyamide 6) and / or poly (caproamide / hexamethylene adipamide / dodecane amide) (polyamide 6/66/12).
The semi-aromatic polyamide composition (B) contains a semi-aromatic polyamide (B1) or a semi-aromatic polyamide (B2).
The semi-aromatic polyamide (B1) contains 50 mol% or more of an aliphatic diamine unit 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). On the other hand, it contains 50 mol% or more of aromatic carboxylic acid units.
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). On the other hand, it contains 50 mol% or more of an aliphatic dicarboxylic acid unit.
The polyamide 6 composition (C1) is a laminated tube containing a polycarbonate (polyamide 6) (C11), a plasticizer (C3), and an elastomer polymer (C4).