JP2017193101A - Laminated tube - Google Patents

Abstract

An object of the present invention is to provide a laminated tube excellent in chemical solution permeation prevention, interlayer adhesion and durability, low temperature impact resistance, monomer and oligomer elution resistance, and melt stability and molding stability. There is to do.
A layer comprising an aliphatic polyamide (polyamide 11, 12, etc.), a layer comprising a polyamide 6/66/12 composition, a layer comprising an ethylene / vinyl acetate copolymer saponified product, and a semi-structure having a specific structure. A layer containing an aromatic polyamide composition, at least one layer containing a saponified ethylene / vinyl acetate copolymer and a layer containing a semi-aromatic polyamide composition having a specific structure arranged adjacent to each other Laminated tube.
[Selection figure] None

Description

  The present invention relates to a laminated tube.

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

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

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

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

  Also, two gas barrier layers comprising a polyamide resin layer obtained by polycondensation of m-xylylenediamine, aliphatic dicarboxylic acid and isophthalic acid as main components, and an ethylene / vinyl acetate copolymer saponified product (EVOH) layer A gas barrier multilayer structure in which at least three layers of a thermoplastic resin layer are laminated has been proposed (see Patent Document 6). Further, there has been proposed a laminated tube in which a fluorine-based resin is disposed on the inner layer, a saponified ethylene / vinyl acetate copolymer is disposed on the outer side, and polyterephthalamide (PPA) is disposed on the outer layer (see Patent Document 7). ).

US Pat. No. 5,554,425 JP-A-3-177683 Special table 2003-535717 JP 2003-021276 A JP 2002-210904 A JP 2004-351769 A US 2010-0035116 Specification

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

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

In addition, it has excellent gas barrier performance in a wide humidity range, and even after hot water sterilization, there is very little reduction in gas barrier performance, and there is little coloration or gel generation due to resin deterioration, which is sufficient as a packaging material. Polyamide resin layer obtained by polycondensation with m-xylylenediamine, aliphatic dicarboxylic acid and isophthalic acid as main components, having strength and good secondary processability such as deep drawing, and ethylene / A gas barrier multilayer structure in which at least three layers of two gas barrier layers composed of a saponified vinyl acetate copolymer (EVOH) layer and a thermoplastic resin layer are laminated has been proposed. However, in the same document, there are disclosures of melt molding stability (thermal deterioration and generation of gel-like materials) and film performance at the time of coextrusion, but tubes such as interlayer adhesion, low temperature impact resistance and monomer and oligomer elution There is no specific technical data disclosure or technical suggestion regarding basic performance.
Furthermore, the laminated tube having the saponified ethylene / vinyl acetate copolymer (EVOH) is excellent in permeation resistance for gasoline containing low concentration alcohol, but is insufficient in permeation resistance for gasoline containing high concentration alcohol. An improvement is desired. In order to solve these problems, a laminated tube is proposed in which a fluorine-based resin is disposed on the inner layer, a saponified ethylene / vinyl acetate copolymer is disposed on the outer side, and polyterephthalamide (PPA) is disposed on the outer layer. Yes. However, in the same document, there is no specific technical data disclosure or technical suggestion regarding the tube basic performance such as interlaminar adhesion, low temperature impact resistance, alcohol-containing gasoline permeability and monomer / oligomer elution.

  The object of the present invention is to solve the above-mentioned problems, and is excellent in chemical solution permeation prevention, interlayer adhesion and durability, low temperature impact resistance, monomer and oligomer elution resistance, and melt stability and molding stability. It is to provide a laminated tube.

  As a result of intensive studies to solve the above problems, the present inventors have found that a layer containing an aliphatic polyamide (polyamide 11, 12, etc.), a layer containing a polyamide 6/66/12 composition, ethylene / vinyl acetate. A layer comprising a saponified copolymer and a layer comprising a semi-aromatic polyamide composition having a specific structure, and having a specific structure with a layer comprising at least one saponified ethylene / vinyl acetate copolymer The laminated tube in which the layers containing the semi-aromatic polyamide composition are arranged adjacent to each other has a chemical solution permeation prevention property, interlayer adhesion and durability, low temperature impact resistance, monomer and oligomer elution resistance, melt stability, It has been found that it has excellent properties such as molding stability.

That is, the present invention
A laminated tube of four or more layers including (a) layer, (b) layer, (c) layer, and (d) layer,
At least one set of the (c) layer and the (d) layer is disposed adjacent to each other;
The layer (a) contains an aliphatic polyamide (A),
The layer (b) includes a polyamide 6/66/12 composition (B),
The layer (c) includes a saponified ethylene / vinyl acetate copolymer (C),
The layer (d) includes a semi-aromatic polyamide composition (D),
The aliphatic polyamide (A) does not include polyamide 6/66/12 (b1),
The polyamide 6/66/12 composition (B) is a polyamide mixture of 50% by mass to 98% by mass, a plasticizer (B1) of 1% by mass to 20% by mass, and an olefin polymer (B2) 1 Containing from 30% to 30% by weight,
The polyamide mixture includes, in the mixture, polyamide 6/66/12 (b1) 50% by mass to 100% by mass and polyamide (b2) 0% by mass to 50% by mass,
The polyamide (b2) includes polyhexamethylene sebamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene decamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), polydecam It is at least one polyamide selected from the group consisting of methylene decanamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), and polydodecamethylene dodecamide (polyamide 1212).
The olefin polymer (B2) has a flexural modulus measured according to ISO 178 of 500 MPa or less,
The semi-aromatic polyamide composition (D) includes a semi-aromatic polyamide (d),
The semi-aromatic polyamide (d) is a diamine unit containing 60 mol% or more of m-xylylenediamine units with respect to all diamine units, and a fat having 6 to 10 carbon atoms with respect to all dicarboxylic acid units. It is a laminated tube which has the dicarboxylic acid unit which contains 60 mol% or more of group dicarboxylic acid units.

The preferable aspect of a laminated tube is shown below. A plurality of preferred embodiments can be combined.
[1] The aliphatic polyamide (A) includes polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene decanamide (polyamide 610), poly At least one single selected from the group consisting of hexamethylene dodecamide (polyamide 612), polydecane methylene decanamide (polyamide 1010), polydecamethylene dodecane (polyamide 1012), and polydodecamethylene dodecane (polyamide 1212). A laminated tube which is a polymer and / or a copolymer using several kinds of raw material monomers forming these.
[2] The polyamide 6/66/12 (b1) is a laminated tube having a mass ratio of a total unit of caproamide units and hexamethylene adipamide units to a dodecanamide unit of 81:19 or more and 95: 5.
[3] A laminated tube in which the ethylene content of the saponified ethylene / vinyl acetate copolymer (C) is 15 mol% or more and 60 mol% or less, and the saponification degree is 90 mol% or more.
[4] A laminated tube in which the aliphatic dicarboxylic acid unit having 6 to 10 carbon atoms in the semi-aromatic polyamide (d) is a unit derived from adipic acid and / or sebacic acid.
[5] The layer (a) is disposed on the outermost layer,
The laminated tube in which the (c) layer is disposed between the (a) layer and the (d) layer.
[6] A laminated tube in which at least one pair of the (b) layer and the (c) layer is disposed adjacent to each other.
[7] The layer (d) is disposed in the innermost layer,
The semi-aromatic polyamide composition (D) is a laminated tube further containing a conductive filler.
[8] It further has (e) layer,
The layer (e) includes a fluorine-containing polymer (E),
In the fluorine-containing polymer (E), a functional group having reactivity with an amino group is introduced into the molecular chain,
A laminated tube in which at least one pair of the (d) layer and the (e) layer is disposed adjacent to each other.
[9] A laminated tube in which a layer containing a fluorine-containing polymer composition containing a conductive filler is disposed in the innermost layer.
[10] A laminated tube manufactured by a coextrusion molding method.
[11] A laminated tube used as a fuel tube.

  According to the present invention, it is possible to provide a laminated tube excellent in chemical solution permeation prevention, interlayer adhesion and durability, low temperature impact resistance, monomer and oligomer elution resistance, and melt stability and molding stability. it can.

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

  The laminated tube according to this embodiment includes a layer containing an aliphatic polyamide, a layer containing a polyamide 6/66/12 composition, a layer containing an ethylene / vinyl acetate copolymer saponified product, and a semi-aromatic having a specific structure. A layer comprising a semi-aromatic polyamide composition comprising a polyamide, wherein at least one layer comprising a saponified ethylene / vinyl acetate copolymer is adjacent to a layer comprising a semi-aromatic polyamide composition having a specific structure. Therefore, both the interlaminar adhesion and the chemical liquid permeation-preventing property are achieved, and the low temperature impact resistance, the elution resistance of monomers and oligomers, the melt stability and the molding stability are excellent. In particular, it is suitable as a fuel tube because alcohol mixed hydrocarbons that permeate and evaporate from the tube partition wall can be suppressed and compliance with strict environmental regulations becomes possible. Furthermore, after contact / immersing in fuel for a long time or after heat treatment, the interlayer adhesion strength is hardly reduced, the durability of interlayer adhesion is excellent, and the melt stability and molding stability during molding are good. Therefore, the laminated tube according to the present embodiment can be used in any environment, has high reliability, and has a very high utility value.

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

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

  Examples of the lactam include enantolactam, undecane lactam, dodecane lactam, α-pyrrolidone, α-piperidone and the like. Examples of the aminocarboxylic acid include 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid and the like. These can use 1 type (s) or 2 or more types.

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

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

  Examples of the aliphatic polyamide (A) include polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyethylene adipamide (polyamide 26), polytetramethylene succinamide (polyamide 44), and polytetramethylene glutamide. (Polyamide 45), polytetramethylene adipamide (polyamide 46), polytetramethylene suberamide (polyamide 48), polytetramethylene azelamide (polyamide 49), polytetramethylene sebamide (polyamide 410), polytetramethylene Dodecamide (polyamide 412), polypentamethylene succinamide (polyamide 54), polypentamethylene glutamide (polyamide 55), polypentamethylene adipamide (polyamide 56), polypentamethylene suberami (Polyamide 58), polypentamethylene azelamide (polyamide 59), polypentamethylene sebamide (polyamide 510), polypentamethylene dodecamide (polyamide 512), polyhexamethylene succinamide (polyamide 64), polyhexamethylene Glutamide (polyamide 65), polyhexamethylene adipamide (polyamide 66), polyhexamethylene suberamide (polyamide 68), polyhexamethylene azelamide (polyamide 69), polyhexamethylene sebacamide (polyamide 610), poly Hexamethylene dodecamide (polyamide 612), polyhexamethylene tetradecanamide (polyamide 614), polyhexamethylene hexadecanamide (polyamide 616), polyhexamethylene octadecanamide (polyamide 6) 8) Polynonamethylene adipamide (Polyamide 96), Polynonamethylene suberamide (Polyamide 98), Polynonamethylene azelamide (Polyamide 99), Polynonamethylene sebamide (Polyamide 910), Polynonamethylene dodecamide (Polyamide 912), polydecamethylene adipamide (polyamide 106), polydecamethylene suberamide (polyamide 108), polydecamethylene azelamide (polyamide 109), polydecamethylene sebamide (polyamide 1010), polydecamethylene Dodecamide (polyamide 1012), polydodecamethylene adipamide (polyamide 126), polydodecamethylene suberamide (polyamide 128), polydodecamethylene azelamide (polyamide 129), polydodecamethylene sebacamide (polyamide) Examples thereof include homopolymers such as lyamide 1210) and polydodecamethylene dodecamide (polyamide 1212), and copolymers using several raw material monomers forming these.

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

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

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

  When the terminal amino group concentration per 1 g of aliphatic polyamide (A) is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), the interlayer adhesion of the laminated tube and its durability Is preferably [A]> [B] +5, more preferably [A]> [B] +10, and further preferably [A]> [B] +15. Preferred (hereinafter sometimes referred to as terminal-modified aliphatic polyamide). Furthermore, from the viewpoint of the melt stability of the polyamide and the suppression of the generation of gelled material, [A]> 20 is preferable, and 30 <[A] <120 is more preferable.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Further, in order to improve the low temperature impact resistance of the aliphatic polyamide (A), it is preferable to add an impact modifier, and in particular, ISO 178 described in the polyamide 6/66/12 composition (B) described later. It is more preferable to add an olefin polymer (B2) having a flexural modulus of 500 MPa or less measured according to the above. If the flexural modulus exceeds this value, the impact improvement effect may be insufficient.
The content of the impact modifier is 1 part by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the aliphatic polyamide (A) from the viewpoint of sufficiently ensuring the mechanical strength and low temperature impact resistance of the laminated tube. It is preferably 3 parts by mass or more and 25 parts by mass or less.

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

  Other polyamide resins include polymetaxylylene succinamide (polyamide MXD4), polymetaxylylene glutamide (polyamide MXD5), polymetaxylylene decanamide (polyamide MXD12), polymetaxylylene terephthalamide (polyamide MXDT), Polymetaxylylene isophthalamide (polyamide MXDI), polymetaxylylene hexahydroterephthalamide (polyamide MXDT (H)), polymetaxylylene naphthalamide (polyamide MXDN), polyparaxylylene succinamide (polyamide PXD4), polypara Xylyleneglutamide (polyamide PXD5), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylene veramide (polyamide PXD8), polyparaxylylene azelami (Polyamide PXD9), polyparaxylylene sebacamide (polyamide PXD10), polyparaxylylene dodecamide (polyamide PXD12), polyparaxylylene terephthalamide (polyamide PXDT), polyparaxylylene isophthalamide (polyamide PXDI) ), Polyparaxylylene hexahydroterephthalamide (polyamide PXDT (H)), polyparaxylylene naphthalamide (polyamide PXDN), polyparaphenylene terephthalamide (PPTA), polyparaphenylene isophthalamide (PPIA), Polymetaphenylene terephthalamide (PMTA), polymetaphenylene isophthalamide (PMIA), poly (2,6-naphthalenediethylene adipamide) (polyamide 2,6-BAN6), poly (2,6-naphthalenedimethyl) Enseveramide) (polyamide 2,6-BAN8), poly (2,6-naphthalene dimethylene azelamide) (polyamide 2,6-BAN9), poly (2,6-naphthalene dimethylene sebacamide) (polyamide 2,6) -BAN10), poly (2,6-naphthalene dimethylene dodecamide) (polyamide 2,6-BAN12), poly (2,6-naphthalene dimethylene terephthalamide) (polyamide 2,6-BANT), poly (2 , 6-Naphthalenedylene methylene isophthalamide) (polyamide 2,6-BANI), poly (2,6-naphthalenediethylene hexahydroterephthalamide) (polyamide 2,6-BANT (H)), poly (2, 6-naphthalene dimethylene naphthalamide) (polyamide 2,6-BANN), poly (1,3-cyclohexanedimethylene) 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-cyclohexanedimethylene dodecamide) (polyamide 1,3-BAC12), poly (1,3 -Cyclohexanedimethylene terephthalamide) (polyamide 1,3-BACT), poly (1,3-cyclohexanedimethylene isophthalamide) (polyamide 1,3-BACI), poly (1,3-cyclohexanedimethylene hexahydro Terephthalamide) (polyamide 1,3-BACT (H)), poly (1,3-silane) Lohexane dimethylene naphthalamide) (polyamide 1,3-BACN), poly (1,4-cyclohexane dimethylene adipamide) (polyamide 1,4-BAC6), poly (1,4-cyclohexane dimethylene suberamide) (Polyamide 1,4-BAC8), poly (1,4-cyclohexanedimethylene azelamide) (polyamide 1,4-BAC9), poly (1,4-cyclohexanedimethylene sebacamide) (polyamide 1,4-BAC10) ), Poly (1,4-cyclohexanedimethylene dodecamide) (polyamide 1,4-BAC12), poly (1,4-cyclohexanedimethylene terephthalamide) (polyamide 1,4-BACT), poly (1,4 -Cyclohexanedimethyleneisophthalamide) (polyamide 1,4-BACI), poly (1,4 Cyclohexane dimethylene hexahydroterephthalamide) (polyamide 1,4-BACT (H)), poly (1,4-cyclohexane dimethylene naphthalamide) (polyamide 1,4-BACN), poly (4,4′-methylene) Biscyclohexylene adipamide) (polyamide PACM6), poly (4,4′-methylenebiscyclohexylene suberamide) (polyamide PACM8), poly (4,4′-methylenebiscyclohexylene azelamide) (polyamide PACM9), Poly (4,4'-methylenebiscyclohexylene sebacamide) (polyamide PACM10), poly (4,4'-methylenebiscyclohexylene dodecamide) (polyamide PACM12), poly (4,4'-methylenebiscyclohexylene) Tetradecamide) (Polyamide PAC M14), poly (4,4′-methylenebiscyclohexylenehexadecamide) (polyamide PACM16), poly (4,4′-methylenebiscyclohexyleneoctadecamide) (polyamide PACM18), poly (4,4′- Methylenebiscyclohexylene terephthalamide) (polyamide PACMT), poly (4,4′-methylenebiscyclohexylene isophthalamide) (polyamide PACMI), poly (4,4′-methylenebiscyclohexylene hexahydroterephthalamide) (Polyamide PACMT (H)), poly (4,4′-methylenebiscyclohexylenenaphthalamide) (polyamide PACMN), poly (4,4′-methylenebis (2-methyl-cyclohexylene) adipamide) (polyamide MACM6), Poly (4,4'-methyle Bis (2-methyl-cyclohexylene) suberamide) (polyamide MACM8), poly (4,4′-methylenebis (2-methyl-cyclohexylene) azeramide) (polyamide MACM9), poly (4,4′-methylenebis (2- Methyl-cyclohexylene) sebacamide) (polyamide MACM10), poly (4,4′-methylenebis (2-methyl-cyclohexylene) dodecamide) (polyamide MACM12), poly (4,4′-methylenebis (2-methyl-cyclohexylene) ) Tetradecamide) (polyamide MACM14), poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexadecamide) (polyamide MACM16), poly (4,4′-methylenebis (2-methyl-cyclohexylene) octadecamide) ( Polya MACM18), poly (4,4′-methylenebis (2-methyl-cyclohexylene) terephthalamide) (polyamide MACMT), poly (4,4′-methylenebis (2-methyl-cyclohexylene) isophthalamide) (polyamide MACMI), Poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexahydroterephthalamide) (polyamide MACMT (H)), poly (4,4′-methylenebis (2-methyl-cyclohexylene) naphthalamide) (polyamide) MACMN), poly (4,4′-propylene biscyclohexylene adipamide) (polyamide PACP6), poly (4,4′-propylene biscyclohexylene suberamide) (polyamide PACP8), poly (4,4′-propylene) Biscyclohexylene azelamide ) (Polyamide PACP9), poly (4,4′-propylene biscyclohexylene sebacamide) (polyamide PACP10), poly (4,4′-propylene biscyclohexylene dodecamide) (polyamide PACP12), poly (4,4 '-Propylene biscyclohexylene tetradecanamide) (polyamide PACP14), poly (4,4'-propylene biscyclohexylene hexadecanamide) (polyamide PACP16), poly (4,4'-propylene biscyclohexylene octadecanamide) (Polyamide PACP18), poly (4,4′-propylene biscyclohexylene terephthalamide) (polyamide PAPPT), poly (4,4′-propylene biscyclohexylene isophthalamide) (polyamide PACPI), poly (4,4 '-Pro Lenbiscyclohexylene hexahydroterephthalamide) (polyamide PACPT (H)), poly (4,4'-propylene biscyclohexylene naphthalamide) (polyamide PACPN), polyisophorone adipamide (polyamide IPD6), polyisophorones Lamide (polyamide IPD8), polyisophorone azeramide (polyamide IPD9), polyisophorone sebamide (polyamide IPD10), polyisoholondecamide (polyamide IPD12), polyisophorone terephthalamide (polyamide IPDT), polyisophorone isophthalamide ( Polyamide IPDI), polyisophorone hexahydroterephthalamide (polyamide IPDT (H)), polyisophorone naphthalamide (polyamide IPDN), polytetramethylene terephthalate Mido (polyamide 4T), polytetramethylene isophthalamide (polyamide 4I), polytetramethylene hexahydroterephthalamide (polyamide 4T (H)), polytetramethylene naphthalamide (polyamide 4N), polypentamethylene terephthalamide ( Polyamide 5T), polypentamethylene isophthalamide (polyamide 5I), polypentamethylene hexahydroterephthalamide (polyamide 5T (H)), polypentamethylene naphthalamide (polyamide 5N), polyhexamethylene terephthalamide (polyamide 6T) ), Polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene hexahydroterephthalamide (polyamide 6T (H)), polyhexamethylene naphthalamide (polyamide 6N), poly (2-methylpenta) Methylene terephthalamide) (polyamide M5T), poly (2-methylpentamethylene isophthalamide) (polyamide M5I), poly (2-methylpentamethylene hexahydroterephthalamide) (polyamide M5T (H)), poly (2 -Methyl pentamethylene naphthalamide (polyamide M5N), polynonamethylene terephthalamide (polyamide 9T), polynonamethylene isophthalamide (polyamide 9I), polynonamethylene hexahydroterephthalamide (polyamide 9T (H)), poly Nonamethylene naphthalamide (polyamide 9N), poly (2-methyloctamethylene terephthalamide) (polyamide M8T), poly (2-methyloctamethylene isophthalamide) (polyamide M81), poly (2-methyloctamethylene hexahydro) Terephthal (Polyamide M8T (H)), poly (2-methyloctamethylene naphthalamide) (polyamide M8N), polytrimethylhexamethylene terephthalamide (polyamide TMHT), polytrimethylhexamethylene isophthalamide (polyamide TMHI), poly Trimethylhexamethylene hexahydroterephthalamide (polyamide TMHT (H)), polytrimethylhexamethylene naphthalamide (polyamide TMHN), polydecamethylene terephthalamide (polyamide 10T), polydecamethylene isophthalamide (polyamide 10I), poly Decamethylene hexahydroterephthalamide (polyamide 10T (H)), polydecamethylene naphthalamide (polyamide 10N), polyundecamethylene terephthalamide (polyamide 11T), poly Ndecamethylene 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), A polymer etc. are mentioned. These can use 1 type (s) or 2 or more types.

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

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

2. (B) Layer The (b) layer of the laminated tube contains a polyamide 6/66/12 composition (B).

[Polyamide 6/66/12 composition (B)]
The polyamide 6/66/12 composition (B) comprises a polyamide mixture in an amount of 50% by mass to 98% by mass, a plasticizer (B1) of 1% by mass to 20% by mass, and an olefin polymer (B2) 1 The polyamide mixture contains 50% by mass or more and 100% by mass or less of polyamide 6/66/12 (b1) and 0% by mass or more and 50% by mass of polyamide (b2) in the mixture. The polyamide (b2) includes polyhexamethylene sebamide (polyamide 610), polyhexamethylene dodecane (polyamide 612), polynonamethylene decanamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), polydeca Methylene decanamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), and At least one polyamide selected from the group consisting of poly dodecamethylene dodecamide (polyamide 1212), wherein the olefin polymer (B2) is flexural modulus was measured according to ISO 178 is less than 500 MPa.

[Polyamide 6/66/12 (b1)]
Polyamide 6/66/12 (poly (caproamide / hexamethyleneadipamide / dodecanamide)) has the following formula having an amide bond (—CONH—) in the main chain: (—CO— (CH ₂ ) ₆ —NH _-) caproamide units and the following equation represented by _{n: (- NH- (CH 2} ) 6 -NH-CO- (CH 2) 4 -CO-) following equation and hexamethylene adipamide units :( represented by _n —CO— (CH ₂ ) ₁₁ —NH—) A polyamide copolymer having a dodecanamide unit represented by _n . Polyamide 6/66/12 can be obtained by copolymerizing 6-aminocaproic acid and / or caprolactam, hexamethylenediamine and adipic acid salt, and 12-aminododecanoic acid and / or dodecanactam.

In the polyamide 6/66/12 (b1), the mass ratio of the total unit of the caproamide unit and the hexamethylene adipamide unit and the dodecanamide unit is from the viewpoint of sufficiently ensuring the interlayer adhesion of the laminated tube and its durability. It is preferably 81: 19% by mass or more and 95: 5% by mass or less, and 83: 17% by mass or more and 92: 8 with respect to 100% by mass in total of caproamide unit, hexamethylene adipamide unit and dodecanamide unit. It is more preferable that the amount is not more than mass%.
In polyamide 6/66/12 (b1), the mass ratio of the caproamide unit and the hexamethylene adipamide unit ensured sufficient heat resistance of the laminated tube, and the saponified ethylene / vinyl acetate copolymer (C) described later From the viewpoint of molding stability at the time of coextrusion, it is preferably 80:20 mass% or more and 95: 5 mass% or less with respect to 100 mass% in total of caproamide units and hexamethylene adipamide units, 82: More preferably, it is 18 mass% or more and 93: 7 mass% or less.

  The polyamide 6/66/12 composition (B) contains a polyamide mixture containing polyamide 6/66/12 (b1) and polyamide (b2) (hereinafter sometimes referred to as a polyamide mixture).

[Polyamide (b2)]
Polyamide (b2) is polyhexamethylene sebamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene decanamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), polydecamethylene. It is at least one polyamide selected from the group consisting of decamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), and polydodecamethylene dodecamide (polyamide 1212), and among these, interlayer adhesion of laminated tubes From the viewpoint of obtaining sufficient properties and durability, polyhexamethylene sebacamide (polyamide 610) and / or polyhexamethylene dodecamide (polyamide 612) is preferable.

  Examples of the production apparatus for polyamide 6/66/12 (b1) and polyamide (b2) include known polyamide production apparatuses described in the explanation of aliphatic polyamide (A). As a manufacturing method of polyamide 6/66/12 (b1) and polyamide (b2), the well-known method described by description of aliphatic polyamide (A) is mentioned.

  In addition, relative viscosity of polyamide 6/66/12 (b1) and polyamide (b2) measured under the conditions of 96% sulfuric acid, polymer concentration 1%, 25 ° C. according to JIS K-6920 can be obtained. From the viewpoint of ensuring the mechanical properties of the laminated tube and ensuring the desirable formability of the laminated tube by setting the viscosity at the time of melting to an appropriate range, it is preferably 1.5 or more and 5.0 or less, 1.8 More preferably, it is 4.5 or less.

  When the terminal amino group concentration per 1 g of polyamide 6/66/12 (b1) and polyamide (b2) is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), a laminated tube [A]> [B] +5 is more preferable, [A]> [B] +10 is more preferable, and [A]> [B] +10 is preferable. B] +15 is more preferable (hereinafter sometimes referred to as terminal-modified polyamide). Furthermore, from the viewpoint of the melt stability of the polyamide and the suppression of the generation of gelled material, [A]> 20 is preferable, and 30 <[A] <120 is more preferable.

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

  The content of polyamide 6/66/12 (b1) in the polyamide mixture is 50% by mass or more and 100% by mass or less with respect to 100% by mass in total of polyamide 6/66/12 (b1) and polyamide (b2). Yes, it is preferably 55% by mass or more and 90% by mass or less, and more preferably 60% by mass or more and 85% by mass or less. On the other hand, the content of the polyamide (b2) in the polyamide mixture is 0% by mass or more and 50% by mass or less with respect to 100% by mass in total of the polyamide 6/66/12 (b1) and the polyamide (b2). It is preferable that they are mass% or more and 45 mass% or less, and it is more preferable that they are 15 mass% or more and 40 mass% or less. If the content of polyamide 6/66/12 (b1) is less than the above value and the content of polyamide (b2) exceeds the above value, the mechanical properties and flexibility of the resulting laminated tube may be inferior. is there. When the content of polyamide 6/66/12 (b1) exceeds the above value and the content of polyamide (b2) is less than the above value, the interlayer adhesiveness and durability of the obtained laminated tube are insufficient. There is something wrong.

  The content of the polyamide mixture in the polyamide 6/66/12 composition (B) is 50% by mass to 98% by mass, preferably 60% by mass to 95% by mass, and more preferably 70% by mass to 92%. It is more preferable that the amount is not more than mass%. If the content of the polyamide mixture is less than the above value, the mechanical properties of the resulting laminated tube may be inferior. On the other hand, if it exceeds the above value, the interlayer adhesion of the obtained laminated tube and its durability may be poor. May be inferior.

[Plasticizer (B1)]
Examples of the plasticizer (B1) in the polyamide 6/66/12 composition (B) include benzenesulfonic acid alkylamides, toluenesulfonic acid alkylamides, and hydroxybenzoic acid alkyl esters.

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

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

  The content of the plasticizer (B1) in the polyamide 6/66/12 composition (B) is 1% by mass or more and 20% by mass or less, and preferably 2% by mass or more and 15% by mass or less. It is more preferable that it is 10% by mass or more. When the content of the plasticizer (B1) is less than the above value, the flexibility of the obtained laminated tube may be inferior. On the other hand, when the content exceeds the above value, the low temperature impact resistance of the obtained laminated tube is inferior. Sometimes.

[Olefin polymer (B2)]
The olefin polymer (B2) in the polyamide 6/66/12 composition (B) has a flexural modulus of 500 MPa or less as measured in accordance with ISO 178, and polyamide 6/66/12 (b1) or polyamide ( It is added to improve the low temperature impact resistance of b2). If the flexural modulus measured according to ISO 178 of the olefin polymer (B2) exceeds this value, the impact improving effect may be insufficient.

  As the olefin polymer (B2), (ethylene and / or propylene) / α-olefin copolymer, (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) ) Type copolymer, ionomer polymer, aromatic vinyl compound / conjugated diene compound type block copolymer, and these may be used alone or in combination of two or more.

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

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

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

The aromatic vinyl compound / conjugated diene compound block copolymer is a block copolymer comprising an aromatic vinyl compound polymer block and a conjugated diene compound polymer block, and the aromatic vinyl compound polymer. A block copolymer having at least one block and at least one conjugated diene compound-based polymer block is used. In the block copolymer, the unsaturated bond in the conjugated diene compound-based polymer block may be hydrogenated.
The aromatic vinyl compound polymer block is a polymer block mainly composed of units derived from an aromatic vinyl compound. In this case, the aromatic vinyl compound includes styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,5-dimethylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene, 4-propyl. Styrene, 4-cyclohexyl styrene, 4-dodecyl styrene, 2-ethyl-4-benzyl styrene, 4- (phenylbutyl) styrene and the like can be mentioned, and one or more of these can be used. In addition, the aromatic vinyl compound-based polymer block may optionally have a unit composed of a small amount of another unsaturated monomer.

  Conjugated diene compound-based polymer blocks are 1,3-butadiene, chloroprene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3 -A polymer block formed from one or more conjugated diene compounds such as hexadiene, and a hydrogenated aromatic vinyl compound / conjugated diene compound block copolymer, the conjugated diene compound polymer Part or all of the unsaturated bond portions in the block are saturated bonds by hydrogenation.

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

  Further, (ethylene and / or propylene) / α-olefin copolymer, (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid) used as the olefin polymer (B2). As the acid ester) copolymer, ionomer polymer, and aromatic vinyl compound / conjugated diene compound block copolymer, a polymer modified with a carboxylic acid and / or a derivative thereof is preferably used. By modifying with such components, functional groups having affinity for polyamide 6/66/12 (b1), polyamide (b2) and the aliphatic polyamide (A) are included in the molecule. .

  Examples of functional groups having affinity for polyamide 6/66/12 (b1), polyamide (b2) and the aliphatic polyamide (A) include a carboxyl group, an acid anhydride group, a carboxylate group, and a carboxylate metal. Examples thereof include a salt, a carboxylic acid imide group, a carboxylic acid amide group, and an epoxy group. Examples of compounds containing these functional groups include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid Endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid and metal salts of these carboxylic acids, monomethyl maleate, monomethyl itaconate, methyl acrylate, ethyl acrylate, butyl acrylate 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, itaconic anhydride, citracone anhydride Acid, endobicyclo- 2.2.1] -5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, acrylamide, methacrylamide, glycidyl acrylate, glycidyl methacrylate, Examples include glycidyl ethacrylate, glycidyl itaconate, and glycidyl citraconic acid. These can use 1 type (s) or 2 or more types.

  The content of the olefin polymer (B2) in the polyamide 6/66/12 composition (B) is 1% by mass to 30% by mass, preferably 3% by mass to 25% by mass. It is more preferable that the content be 20% by mass or more. If the content of the olefin polymer (B2) is less than the above value, the resulting laminated tube may be inferior in low-temperature impact resistance and interlayer adhesion and its durability, whereas when exceeding the above value, The resulting laminated tube may have inferior mechanical properties.

  The production method of the polyamide 6/66/12 composition (B) is not particularly limited, and various additives that have been conventionally known can be employed by blending various additives as necessary. For example, together with other components to which polyamide 6/66/12 (b1), polyamide (b2), and olefin polymer (B2) are added as necessary, the pellets are mixed together using a tumbler or mixer. The mixture is uniformly dry blended to a ratio and supplied to the melt-kneader, while the plasticizer (B1) is injected from the middle of the cylinder of the melt-kneader with a metering pump and melt-kneaded. Can do. The melt kneading can be performed using a kneader such as a single screw extruder, a twin screw extruder, a kneader, or a Banbury mixer.

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

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

3. (C) Layer The (c) layer of the laminated tube contains an ethylene / vinyl acetate copolymer saponified product (C).

[Saponified ethylene / vinyl acetate copolymer (C)]
The saponified ethylene / vinyl acetate copolymer (C) is obtained by saponifying a copolymer comprising ethylene and vinyl acetate by a known method using an alkali catalyst or the like (hereinafter referred to as EVOH (C)). May be.)

  Furthermore, the ethylene content of EVOH (C) is preferably 15 mol% or more and 60 mol% or less from the viewpoint of sufficiently ensuring melt moldability, flexibility, impact resistance, and chemical liquid permeation prevention properties, It is more preferably 20 mol% or more and 55 mol% or less, and further preferably 25 mol% or more and 45 mol% or less. Here, when EVOH (C) consists of a mixture of two or more types of EVOH having different ethylene contents, the value calculated from the respective ethylene contents and the mixing mass ratio is taken as the ethylene content.

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

  EVOH (C) melt flow rate (MFR) (210 ° C., under a load of 2,160 g) ensures a desirable formability by setting the viscosity at the time of melting to an appropriate range, does not excessively lower the melt tension, and at the time of molding. From the viewpoint of preventing the occurrence of problems such as drawdown, it is preferably 0.1 g / 10 min or more and 100 g / 10 min or less, more preferably 0.3 g / 10 min or more and 50 g / 10 min or less, More preferably, it is 0.5 g / 10 min or more and 20 g / 10 min or less.

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

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

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

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

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

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

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

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

  Furthermore, in order to improve the melt stability and the like, EVOH (C) has an antioxidant such as hydrotalcite and hindered phenol as long as the excellent properties of the resulting laminated tube are not impaired. It is preferable to add 0.01 part by mass or more and 1 part by mass or less of 1 type or 2 types or more to 100 parts by mass of EVOH (C).

4). (D) Layer The (d) layer of the laminated tube contains the semiaromatic polyamide composition (D).

[Semi-aromatic polyamide composition (D)]
The semi-aromatic polyamide composition (D) contains a semi-aromatic polyamide (d), and the semi-aromatic polyamide (d) is a diamine containing 60 mol% or more of m-xylylenediamine units with respect to the total diamine units. And a dicarboxylic acid unit containing 60 mol% or more of an aliphatic dicarboxylic acid unit having 6 to 10 carbon atoms with respect to all the dicarboxylic acid units (hereinafter sometimes referred to as semi-aromatic polyamide (d)). is there.).

  The content of the m-xylylenediamine unit in the semi-aromatic polyamide (d) is a viewpoint that sufficiently secures various physical properties such as heat resistance, chemical resistance, impact resistance, and chemical liquid permeation prevention properties of the obtained laminated tube. Therefore, it is 60 mol% or more, preferably 70 mol% or more, and more preferably 80 mol% or more with respect to all diamine units.

  The diamine unit in the semi-aromatic polyamide (d) may contain other diamine units other than the m-xylylenediamine unit as long as the excellent properties of the resulting laminated tube are not impaired. Other diamine units include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, , 8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1, 15-pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, 1,19-nonadecanediamine, 1,20-eicosanediamine, 2-methyl-1,5 -Pentanediamine, 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octane Derived from aliphatic diamines such as amines, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine Unit: 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,2 -Bis (4-aminocyclohexyl) propane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (3-methyl-4-aminocyclohexyl) propane, 5-amino-2,2,4- Trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine Bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, 2,5-bis (aminomethyl) norbornane, 2,6-bis (aminomethyl) norbornane, 3,8-bis (aminomethyl) tricyclodecane, 4 , Units derived from alicyclic diamines such as 9-bis (aminomethyl) tricyclodecane; m-phenylenediamine, p-phenylenediamine, p-xylylenediamine, 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-amino) Phenyl) propane, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ether, etc. These units may be derived from aromatic diamines, and these may be used alone or in combination of two or more. Among these, units derived from aromatic diamines are preferred. The content of these other diamine units is 40 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less, based on all diamine units.

  In addition, the content of the aliphatic dicarboxylic acid unit having 6 to 10 carbon atoms in the semi-aromatic polyamide (d) has various physical properties such as heat resistance, chemical resistance and chemical liquid permeation preventive property of the obtained laminated tube. From the viewpoint of ensuring sufficiently, it is at least 60 mol%, preferably at least 70 mol%, more preferably at least 80 mol%, based on all dicarboxylic acid units.

Examples of the aliphatic dicarboxylic acid unit having 6 to 10 carbon atoms include units derived from adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid and the like. As long as the number of carbon atoms satisfies the above, 2-methyladipic acid, 2,2-dimethylglutaric acid, 2,2-diethylsuccinic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid A unit derived from a branched aliphatic dicarboxylic acid such as the above may be contained. These can use 1 type (s) or 2 or more types.
Among the aliphatic dicarboxylic acid units having 6 to 10 carbon atoms, units derived from adipic acid and sebacic acid are preferred from the viewpoint of the balance between coextrusion moldability and chemical permeation preventive property and economy.

  The dicarboxylic acid unit in the semi-aromatic polyamide (d) is a dicarboxylic acid unit other than the aliphatic dicarboxylic acid unit having 6 to 10 carbon atoms as long as the excellent properties of the obtained laminated tube are not impaired. It may contain an acid unit. Other dicarboxylic acid units include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, undecanedioic acid, 2-butylsuberic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid , Units derived from aliphatic dicarboxylic acids such as octadecanedioic acid and eicosanedioic acid; alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid Units derived from acids; terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,3-pheny Rangeoxydiacetic acid, 1,4-phenylenedioxydiacetic acid, 4,4'-oxydi Benzoic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylethane-4,4′-dicarboxylic acid, diphenylpropane-4,4′-dicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, diphenylsulfone-4 , 4′-dicarboxylic acid, 4,4′-biphenyldicarboxylic acid, units derived from aromatic dicarboxylic acid such as 4,4′-triphenyldicarboxylic acid, and the like, and one or more of these are used. be able to. The content of these other dicarboxylic acid units is 40 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less, based on all dicarboxylic acid units. Furthermore, polycarboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid can be used as long as melt molding is possible.

  The semi-aromatic polyamide (d) may contain other units other than the dicarboxylic acid unit and the diamine unit as long as the excellent properties of the obtained laminated tube are not impaired. Other units include units derived from lactams such as caprolactam, enantolactam, undecane lactam, dodecane lactam, α-pyrrolidone, α-piperidone; 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11 -Units derived from aminocarboxylic acids of aliphatic aminocarboxylic acids such as aminoundecanoic acid and 12-aminododecanoic acid; and aromatic aminocarboxylic acids such as p-aminomethylbenzoic acid. These can use 1 type (s) or 2 or more types. Among these, units derived from caprolactam and / or 6-aminocaproic acid are preferable. The content of other units is preferably 20 mol% or less, more preferably 10 mol% or less, based on all dicarboxylic acid units.

  Semi-aromatic polyamide (d) production equipment includes batch reactors, one- or multi-tank continuous reactors, tubular continuous reactors, single-screw kneading extruders, twin-screw kneading extruders, etc. A known polyamide production apparatus such as a reaction extruder may be used. As a method for producing the semi-aromatic polyamide (d), there are known methods such as melt polymerization, solution polymerization, and solid-phase polymerization, and these methods are used to repeat the normal pressure, reduced pressure, and pressurization operations to make the semi-aromatic polyamide. Polyamide (d) 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 m-xylylenediamine and an aliphatic dicarboxylic acid having 6 to 10 carbon atoms is pressurized and heated in the presence of water in a molten state while removing added water and condensed water. Manufactured by a polymerization method. It can also be produced by a method in which m-xylylenediamine is directly added to an aliphatic dicarboxylic acid having 6 to 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, m-xylylenediamine is continuously added to the aliphatic dicarboxylic acid having 6 to 10 carbon atoms, during which the oligoamide that generates the temperature of the reaction system and Polymerization proceeds while raising the temperature of the reaction system so that the melting point of the polyamide is higher than the melting point. In addition, the semi-aromatic polyamide (d) may be subjected to solid phase polymerization after being produced by a melt polymerization method.

Phosphorus compounds can be added to the semi-aromatic polyamide (d) as a catalyst, in order to improve processing stability during melt molding or to prevent coloring. Phosphorus compounds include alkaline earth metal salts of hypophosphorous acid, alkali metal salts of phosphorous acid, alkaline earth metal salts of phosphorous acid, alkali metal salts of phosphoric acid, alkaline earth metal salts of phosphoric acid, Examples include alkali metal salts of pyrophosphoric acid, alkaline earth metal salts of pyrophosphoric acid, alkali metal salts of metaphosphoric acid, and alkaline earth metal salts of metaphosphoric acid.
Specifically, calcium hypophosphite, magnesium hypophosphite, sodium phosphite, sodium hydrogen phosphite, potassium phosphite, potassium hydrogen phosphite, lithium phosphite, lithium hydrogen phosphite, phosphorus phosphite Magnesium phosphate, magnesium hydrogen phosphite, calcium phosphite, calcium hydrogen phosphite, 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 phosphate, lithium pyrophosphate, sodium metaphosphate, potassium metaphosphate, magnesium metaphosphate, calcium metaphosphate, and lithium metaphosphate and the like. These can use 1 type (s) or 2 or more types. Among these, calcium hypophosphite, magnesium hypophosphite, calcium phosphite, calcium hydrogen phosphite, and calcium dihydrogen phosphate are preferable, and calcium hypophosphite is more preferable. These phosphorus compounds may be hydrates.

The content of the phosphorus compound ensures a catalytic effect and a coloration preventing effect at the time of polymerization, and from the viewpoint of suppressing the generation of gel, in terms of phosphorus atom concentration in terms of 100 parts by mass of the semi-aromatic polyamide (d). 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. More preferably it is.
The addition method of these phosphorus compounds is a method of adding to a nylon salt aqueous solution, a diamine or dicarboxylic acid, which is a raw material of the semiaromatic polyamide (d), a method of adding to a dicarboxylic acid in a molten state, and adding during melt polymerization. Any method may be used as long as it can be uniformly dispersed in the semi-aromatic polyamide (d), and the method is not limited to these.

  An alkali metal compound can be added to the semiaromatic polyamide (d) in combination with the phosphorus compound. In order to prevent coloring of the polyamide during polycondensation, a sufficient amount of phosphorus compound needs to be present, but in some cases there is a risk of causing gelation of the polyamide. It is preferable to coexist an alkali metal compound. Examples of the alkali metal compound include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal acetates, and alkaline earth metal acetates, and alkali metal hydroxides and alkali metal acetates are preferable.

  Specific examples of the alkali metal compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, lithium acetate, Examples thereof include sodium acetate, potassium acetate, rubidium acetate, cesium acetate, magnesium acetate, calcium acetate, strontium acetate, and barium acetate. These can use 1 type (s) or 2 or more types. Among these, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium acetate, and potassium acetate are preferable from the economical viewpoint, and sodium hydroxide, sodium acetate, and potassium acetate are preferable.

When an alkali metal compound is added to the polycondensation system of the semi-aromatic polyamide (d), the value obtained by dividing the number of moles of the compound by the number of moles of the phosphorus compound converted to phosphorus atoms is the acceleration and suppression of the amidation reaction. From the viewpoint of balance, it is preferably 0.30 or more and 1.0 or less, more preferably 0.40 or more and 0.95 or less, and further preferably 0.50 or more and 0.90 or less.
The method for adding these alkali metal compounds includes the method of adding to the aqueous solution of nylon salt, diamine or dicarboxylic acid, the raw material of the semi-aromatic polyamide (d), the method of adding to the dicarboxylic acid in the molten state, and the addition during melt polymerization Any method may be used as long as it can be uniformly dispersed in the semi-aromatic polyamide (d), but is not limited thereto.

  According to JIS K-6920, the relative viscosity of the semi-aromatic polyamide (d) measured under the conditions of 96% sulfuric acid, 1% polymer concentration and 25 ° C. ensures the mechanical properties of the resulting laminated tube. From the viewpoint of securing the desirable formability of the laminated tube by setting the viscosity at the time of melting to an appropriate range, it is preferably 1.5 or more and 4.0 or less, and is 1.8 or more and 3.5 or less. More preferably, it is 2.0 or more and 3.0 or less.

  In addition, there is no special restriction | limiting in the kind of terminal group of semi-aromatic polyamide (d), its density | concentration, and molecular weight distribution. One or more of monoamine, diamine, polyamine, monocarboxylic acid, and dicarboxylic acid can be added in appropriate combination for molecular weight adjustment and melt stabilization during molding. For example, aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine; alicyclic such as cyclohexylamine, dicyclohexylamine Monoamines; aromatic monoamines such as aniline, toluidine, diphenylamine, naphthylamine; 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1 , 10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2-methyl-1,8- Oh Aliphatic diamines such as tandiamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine; Alicyclic diamines such as bis (aminomethyl) cyclohexane and 5-amino-1,3,3-trimethylcyclohexanemethylamine; m-phenylenediamine, p-phenylenediamine, p-xylylenediamine, 1,4-bis ( Aromatic diamines such as aminomethyl) naphthalene, 1,5-bis (aminomethyl) naphthalene, 2,6-bis (aminomethyl) naphthalene, 2,7-bis (aminomethyl) naphthalene; polyalkyleneimine, polyalkylenepolyamine , Polyvinylamine, polyallylamine and other polyamines, acetic acid, Aliphatic monocarboxylic acids such as pionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid; cycloaliphatic carboxylic acid Monocarboxylic acid; benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid and other aromatic monocarboxylic acids; malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, Alicyclic dicarboxylic acids such as aliphatic dicarboxylic acids such as undecanedioic acid, 2-butylsuberic acid and dodecanedioic acid, 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid Acid; phthalic acid, isophthalic acid, terephthalic acid, 1,4-naphthalenedica Bon acid, 1,5-naphthalene dicarboxylic acid, 2,6-naphthalene dicarboxylic acid, aromatic dicarboxylic acids such as 2,7-naphthalene dicarboxylic acid. These can use 1 type (s) or 2 or more types. The amount of these molecular weight regulators used varies depending on the reactivity of the molecular weight regulator and the polymerization conditions, but is appropriately determined so that the relative viscosity of the polyamide to be finally obtained falls within the above range. Moreover, it is also possible to adjust the addition amount of the said m-xylylenediamine which is a raw material of semi-aromatic polyamide (d), or aliphatic dicarboxylic acid having 6 to 10 carbon atoms.

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

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

  The semi-aromatic polyamide composition (D) may contain other polyamide-based resins or other thermoplastic resins together with the semi-aromatic polyamide (d). Examples of other polyamide resins or other thermoplastic resins include the same resins as those of the aliphatic polyamide (A). Further, it may be a mixture with the aliphatic polyamide (A). The content of the semi-aromatic polyamide (d) in the mixture is preferably 60% by mass or more.

  Further, the semi-aromatic polyamide composition (D) may be added to an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, an inorganic filler, an antistatic agent, a flame retardant, a crystal as necessary. Accelerators, plasticizers, colorants, lubricants, impact modifiers and the like may be added. In order to improve the low temperature impact resistance of the semi-aromatic polyamide (d), it is preferable to add an impact modifier, and in particular, the olefin polymer (B2) described in the polyamide 6/66/12 composition (B). ) Is more preferable.

5). (E) Layer The (e) layer of the laminated tube contains a fluorinated polymer (E).

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

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

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

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

Among the fluorine-containing polymers (E), from the viewpoints of heat resistance, chemical resistance, and chemical liquid permeation prevention, at least a copolymer (E1) composed of a vinylidene fluoride unit (VDF unit), at least tetrafluoro Copolymer (E2) comprising an ethylene unit (TFE unit) and an ethylene unit (E unit), at least a tetrafluoroethylene unit (TFE unit) and a hexafluoropropylene unit (HFP unit) and / or the general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). A copolymer (E3) derived from PAVE represented by PAVE ), At least a copolymer (E4) comprising chlorotrifluoroethylene units (CTFE units), at least It is preferably a chlorotrifluoroethylene unit (CTFE units) and consisting of tetrafluoroethylene units (TFE units) copolymer (E5).

As a copolymer (E1) comprising at least a vinylidene fluoride unit (VDF unit) (hereinafter sometimes referred to as a VDF copolymer (E1)), for example,
Vinylidene fluoride homopolymer (polyvinylidene fluoride (PVDF)) (E1-1),
A copolymer comprising VDF units and TFE units, wherein the content of VDF units is 30 mol% or more and 99 mol% or less with respect to the whole monomer excluding the functional group-containing monomers described later, and TFE units A copolymer (E1-2) having a content of 1 mol% or more and 70 mol% or less,
A copolymer comprising a VDF unit, a TFE unit, and a trichlorofluoroethylene unit, wherein the content of the VDF unit is 10 mol% or more and 90 mol with respect to the whole monomer excluding the functional group-containing monomer described later. % Or less, a copolymer (E1-3) having a TFE unit content of 0 mol% or more and 90 mol% or less, and a trichlorofluoroethylene unit content of 0 mol% or more and 30 mol% or less,
A copolymer comprising a VDF unit, a TFE unit, and an HFP unit, wherein the content of the VDF unit is 10 mol% or more and 90 mol% or less with respect to the whole monomer excluding the functional group-containing monomer described later. , A copolymer (E1-4) having a TFE unit content of 0 mol% to 90 mol% and a HFP unit content of 0 mol% to 30 mol%.

  In the copolymer (E1-4), the content of the VDF unit is 15 mol% or more and 84 mol% or less, and the content of the TFE unit is based on the whole monomer excluding the functional group-containing monomer described later. It is preferable that 15 mol% or more and 84 mol% or less and the content of the HFP unit is 0 mol% or more and 30 mol% or less.

  As a copolymer (E2) comprising at least a tetrafluoroethylene unit (TFE unit) and an ethylene unit (E unit) (hereinafter sometimes referred to as a TFE copolymer (E2)), for example, a functional group described below Examples include a polymer having a TFE unit content of 20 mol% or more based on the entire monomer excluding the group-containing monomer, and further, the entire monomer excluding the functional group-containing monomer described later. On the other hand, the content of TFE units is 20 mol% or more and 80 mol% or less, the content of E units is 20 mol% or more and 80 mol% or less, and the content of units derived from monomers copolymerizable therewith Examples thereof include a copolymer having an amount of 0 mol% to 60 mol%.

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

As the TFE copolymer (E2), for example,
TFE unit and E unit, and the general formula CH ₂ = CX ¹ (CF ₂ ) _n X ² (where X ¹ and X ² independently represent a hydrogen atom or a fluorine atom, and n is 2 or more and 10 or less. It is a copolymer composed of fluoroolefin units derived from the fluoroolefin represented by the formula (1), and the content of TFE units is based on the whole monomer excluding the functional group-containing monomers described later. 30 mol% or more and 70 mol% or less, the content of E units is 20 mol% or more and 55 mol% or less, and the general formula CH ₂ = CX ³ (CF ₂ ) _n X ⁴ (where X ³ and X ⁴ are Each independently represents a hydrogen atom or a fluorine atom, and n is an integer of 2 or more and 10 or less.) The content of the fluoroolefin unit derived from the fluoroolefin represented by Polymer ( 2-1),
A copolymer composed of TFE units, E units, HFP units, and units derived from monomers copolymerizable therewith, with respect to the entire monomer excluding the functional group-containing monomers described below, TFE unit content of 30 mol% to 70 mol%, E unit content of 20 mol% to 55 mol%, HFP unit content of 1 mol% to 30 mol%, and copolymerization with these A copolymer (E2-2) in which the content of units derived from possible monomers is 0 mol% or more and 10 mol% or less,
TFE units and E units, and the general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). A copolymer comprising PAVE units derived from PAVE, wherein the content of TFE units is 30 mol% or more and 70 mol% or less, based on the whole monomer excluding the functional group-containing monomers described later, E units In the general formula CF ₂ ═CFOR ^f1 (wherein R ^f1 is a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). The copolymer (E2-3) etc. whose content of the PAVE unit derived from PAVE represented by this is 0 mol% or more and 10 mol% or less are mentioned.

At least a tetrafluoroethylene unit (TFE unit) and a hexafluoropropylene unit (HFP unit) and / or the general formula CF ₂ = CFOR ^f1 (where R ^f1 represents an etheric oxygen atom having 1 to 10 carbon atoms) As a copolymer (E3) (hereinafter sometimes referred to as TFE copolymer (E3)) composed of PAVE units derived from PAVE represented by PAVE represented by: ,
It is a copolymer composed of TFE units and HFP units, and the content of TFE units is preferably 70 mol% or more and 95 mol% or less with respect to the whole monomer excluding the functional group-containing monomer described later, Is a copolymer (E3-1) having a HFP unit content of from 5 mol% to 30 mol%, preferably from 7 mol% to 15 mol%,
It is derived from PAVE represented by a TFE unit and the general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). It is a copolymer comprising one or more PAVE units, and the content of TFE units is 70 mol% or more and 95 mol% or less with respect to the whole monomer excluding the functional group-containing monomer described later. And 1 derived from PAVE represented by the general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). A copolymer (E3-2) in which the content of the seeds or two or more kinds of PAVE units is 5 mol% or more and 30 mol% or less,
TFE units and HFP units, and the general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). A copolymer consisting of one or more PAVE units derived from PAVE, wherein the content of TFE units is 70 mol% or more with respect to the whole monomer excluding the functional group-containing monomers described later 95 mol% or less, represented by an HFP unit and the general formula CF ₂ ═CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). A copolymer (E3-3) in which the total content of one or more PAVE units derived from PAVE is 5 mol% to 30 mol%.

The copolymer consisting of at least chlorotrifluoroethylene units (CTFE units) has CTFE units [—CFCl—CF ₂ —] and is composed of ethylene units (E units) and / or fluorine-containing monomer units. Chlorotrifluoroethylene copolymer (E4) (hereinafter sometimes referred to as CTFE copolymer (E4)).
Examples of the fluorine-containing monomer in the CTFE copolymer (E4), is not particularly limited as long as other than CTFE, vinylidene fluoride (VDF), hexafluoropropylene (HFP), the general formula _CF 2 = CFOR ^{P1 represented by f1} (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms), the general formula CH ₂ = CX ¹ (CF ₂ ) and fluoroolefins represented by _n X ² (wherein X ¹ and X ² independently represent a hydrogen atom or a fluorine atom, and n is an integer of 2 or more and 10 or less). These can use 1 type (s) or 2 or more types.

  The CTFE copolymer (E4) is not particularly limited, and examples thereof include a CTFE / PAVE copolymer, a CTFE / VDF copolymer, a CTFE / HFP copolymer, a CTFE / E copolymer, and a CTFE / PAVE / E copolymer. Examples thereof include a polymer, a CTFE / VDF / E copolymer, and a CTFE / HFP / E copolymer.

  The CTFE unit content in the CTFE copolymer (E4) is preferably 15 mol% or more and 70 mol% or less, based on the whole monomer excluding the functional group-containing monomer described later, and is 18 mol%. More preferably, it is 65 mol% or less. On the other hand, the content of the E unit and / or the fluorine-containing monomer unit is preferably 30 mol% or more and 85 mol% or less, and more preferably 35 mol% or more and 82 mol% or less.

The copolymer (E5) consisting of at least a chlorotrifluoroethylene unit (CTFE unit) and a tetrafluoroethylene unit (TFE unit) has a CTFE unit [—CFCl—CF ₂ —] and a TFE unit [—CF ₂ —CF _2. -], And a chlorotrifluoroethylene copolymer composed of monomer units copolymerizable with CTFE and TFE (hereinafter, sometimes referred to as CTFE / TFE copolymer (E5)).

The copolymerizable monomer in the CTFE / TFE copolymer (E5) is not particularly limited as long as it is other than CTFE and TFE, but vinylidene fluoride (VDF), hexafluoropropylene (HFP), PAVE represented by the general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms), the general formula CH ₂ = Such as a fluoroolefin represented by CX ¹ (CF ₂ ) _n X ² (wherein X ¹ and X ² independently represent a hydrogen atom or a fluorine atom, and n is an integer of 2 or more and 10 or less). Fluorinated monomers and olefins having 2 to 4 carbon atoms such as ethylene, propylene and isobutene; vinyl acetate, methyl (meth) acrylate, (meta Vinyl esters such as ethyl acrylate; methyl vinyl ether (MVE), ethyl vinyl ether (EVE), non-fluorine-containing monomers of vinyl ether and butyl vinyl ether (BVE), and the like. These can use 1 type (s) or 2 or more types. Among these, PAVE is represented by the general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). Of these, perfluoro (methyl vinyl ether) (PMVE) and perfluoro (propyl vinyl ether) (PPVE) are more preferable, and PPVE is more preferable from the viewpoint of heat resistance.

  The CTFE / TFE copolymer (E5) is not particularly limited, and examples thereof include a CTFE / TFE copolymer, a CTFE / TFE / HFP copolymer, a CTFE / TFE / VDF copolymer, and a CTFE / TFE / PAVE copolymer. For example, CTFE / TFE / PFE copolymer, CTFE / TFE / HFP / PAVE copolymer, and CTFE / TFE / VDF / PAVE copolymer. Among these, CTFE / TFE / PAVE copolymer, A CTFE / TFE / HFP / PAVE copolymer is preferred.

  The total content of CTFE units and TFE units in the CTFE / TFE copolymer (E5) is from the viewpoint of ensuring good moldability, environmental stress crack resistance, chemical penetration resistance, heat resistance, and mechanical properties. It is preferable that it is 90.0 mol% or more and 99.9 mol% or less with respect to the whole monomer except the functional group containing monomer of a postscript, The monomer unit copolymerizable with the said CTFE and TFE. The content is preferably 0.10 mol% or more and 10.0 mol% or less.

  The content of the CTFE unit in the CTFE / TFE copolymer (E5) is the total amount of the CTFE unit and the TFE unit from the viewpoint of ensuring good moldability, environmental stress crack resistance, and chemical penetration prevention. It is preferably 15 mol% or more and 80 mol% or less, more preferably 17 mol% or more and 70 mol% or less, and further preferably 19 mol% or more and 65 mol% or less with respect to 100 mol%. .

  In the CTFE / TFE copolymer (E5), when the monomer copolymerizable with CTFE and TFE is PAVE, the content of the PAVE unit is the entire monomer excluding the functional group-containing monomer described later. On the other hand, it is preferably 0.5 mol% or more and 7 mol% or less, more preferably 1 mol% or more and 5 mol% or less.

  In the CTFE / TFE copolymer (E5), when the monomers copolymerizable with CTFE and TFE are HFP and PAVE, the total content of the HFP unit and the PAVE unit is the functional group-containing monomer described later. It is preferably 0.5 mol% or more and 7 mol% or less, and more preferably 1 mol% or more and 5 mol% or less with respect to the whole monomer excluding.

The TFE copolymer (E3), the CTFE copolymer (E4), and the CTFE / TFE copolymer (E5) are excellent in chemical liquid permeation prevention properties, particularly barrier properties against alcohol-containing gasoline. For the alcohol-containing gasoline permeability coefficient, put the sheet obtained from the resin to be measured into a permeability coefficient measuring cup filled with isooctane / toluene / ethanol mixed solvent in which isooctane, toluene, and ethanol are mixed at a volume ratio of 45:45:10. , A value calculated from a change in mass measured at 60 ° C. The alcohol-containing gasoline permeability coefficient of the TFE copolymer (E3), CTFE copolymer (E4) and CTFE / TFE copolymer (E5) is 1.5 g · mm / (m ² · day) or less. ^{preferably, 0.010g · mm / (m 2} · day) or more 1.0 g · mm ^/ more preferably (m 2 · day) or ^{less, 0.020g · mm / (m 2} · day) or more 0 More preferably, it is 80 g · mm / (m ² · day) or less.

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

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

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

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

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

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

  When coextruding the fluorinated polymer (E) with the aliphatic polyamide (A), polyamide 6/66/12 composition (B), EVOH (C), semi-aromatic polyamide composition (D), etc. In order to ensure a sufficient melt fluidity in a molding temperature range not accompanied by such remarkable deterioration, the melt flow rate at a temperature higher by 50 ° C. than the melting point of the fluorine-containing polymer (E) and a load of 5 kg is 0. It is preferably from 5 g / 10 min to 200 g / 10 min, more preferably from 1 g / 10 min to 100 g / 10 min.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

The number of terminal functional groups with respect to 10 ⁶ main chain carbon atoms in the fluorine-containing polymer (E) ensures sufficient interlayer adhesion, and does not cause deterioration of interlayer adhesion depending on the use environment conditions. 150 or more and 3,000 or less from the standpoint of ensuring sufficient, high-temperature processing, adhesion failure, coloring, foaming, use at high temperatures, and preventing occurrence of peeling, coloring, foaming, elution, etc. due to decomposition Preferably, the number is 200 or more and 2,000 or less, and more preferably 300 or more and 1,000 or less. Moreover, as long as the number of functional groups is satisfied, it may be a mixture of a fluorine-containing polymer into which a functional group has been introduced and a fluorine-containing polymer into which no functional group has been introduced.

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

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

[Laminated tube]
The first aspect of the laminated tube is at least four layers including (a) layer, (b) layer, (c) layer, and (d) layer, and at least one pair of (c) layer and (d) layer are adjacent to each other. Arranged.

  In the laminated tube of the first aspect, it is essential to include the (c) layer and the (d) layer, and the chemical solution permeation prevention property, particularly hydrocarbon permeation prevention property, of the laminated tube is improved. Further, by arranging at least one pair of the (c) layer and the (d) layer adjacent to each other, it becomes possible to obtain better interlayer adhesion, and EVOH (C) and a semi-aromatic polyamide composition ( When D) is coextruded, sufficient melt stability and molding stability can be ensured.

  In a preferred embodiment, the layer (a) is disposed in the outermost layer of the laminated tube. (A) By arrange | positioning a layer in the outermost layer, it becomes possible to obtain the laminated tube excellent in chemical resistance and a softness | flexibility. The (c) layer is disposed between the (a) layer and the (d) layer. In addition, by arranging the layer (d) in the innermost layer, a laminated tube having excellent resistance to deterioration fuel can be obtained, and the elution of low molecular weight components such as monomers and oligomers due to contact with alcohol-containing gasoline can be suppressed. It becomes possible. That is, a laminated tube in which the (a) layer is disposed in the outermost layer, the (c) layer and the (d) layer are disposed adjacent to each other, and the (d) layer is disposed in the innermost layer is preferable.

  In a more preferred embodiment, at least one pair of the (b) layer and the (c) layer are arranged adjacent to each other. By arranging the (b) layer on the other side adjacent to the (c) layer, it becomes possible to obtain better interlayer adhesion, and the polyamide 6/66/12 composition (B), EVOH ( When C) and the semi-aromatic polyamide composition (D) are co-extruded, sufficient melt stability and molding stability can be ensured. That is, a laminated tube in which the (a) layer, (b) layer, (c) layer, and (d) layer are arranged adjacent to each other from the outside to the inside is more preferable.

  Further, in the laminated tube of the first aspect, when the conductive layer containing the semi-aromatic polyamide composition (D) containing the conductive filler is disposed in the innermost layer of the laminated tube, the chemical permeation preventive property and the deterioration resistant fuel In addition to excellent elution resistance and monomer / oligomer elution resistance, when used as a fuel piping tube, it prevents the spark generated by the internal friction of the fuel circulating in the piping or friction with the tube wall from igniting the fuel. It becomes possible to do. At that time, a layer containing a semi-aromatic polyamide having no conductivity is disposed on the outside of the conductive layer, so that both low temperature impact resistance and conductivity can be achieved. This is also advantageous.

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

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

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

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

Carbon black is produced in various carbon powders having different characteristics such as particle diameter, surface area, DBP oil absorption, ash content and the like. Although there is no restriction | limiting in the characteristic of this carbon black, What has a favorable chain structure and a large aggregation density is preferable. A large amount of carbon black is not preferable from the viewpoint of impact resistance, and from the viewpoint of obtaining excellent electrical conductivity with a smaller amount, the average particle size is preferably 500 nm or less, more preferably 5 nm or more and 100 nm or less. More preferably, it is 10 nm or more and 70 nm or less, and the surface area (BET method) is preferably 10 m ² / g or more, more preferably 30 m ² / g or more, and 50 m ² / g or more. More preferably, the DBP (dibutyl phthalate) oil absorption is preferably 50 ml / 100 g or more, more preferably 100 ml / 100 g, and even more preferably 150 ml / 100 g or more. Moreover, it is preferable that an ash content is 0.5 mass% or less, and it is more preferable that it is 0.3 mass% or less. The DBP oil absorption here is a value measured by a method defined in ASTM D-2414. The volatile content of carbon black is preferably less than 1% by mass.
These conductive fillers may be subjected to surface treatment with a surface treatment agent such as titanate, aluminum or silane. It is also possible to use a granulated product to improve melt kneading workability.

Since the content of the conductive filler varies depending on the type of conductive filler used, it cannot be specified unconditionally, but from the viewpoint of balance with conductivity, fluidity, mechanical strength, etc., the semi-aromatic polyamide (d) 100 Generally, it is preferably 3 parts by mass or more and 30 parts by mass or less with respect to parts by mass.
In addition, from the viewpoint of obtaining sufficient antistatic performance, the conductive filler preferably has a surface resistivity of the melt-extruded product of 10 ⁸ Ω / square or less, more preferably 10 ⁶ Ω / square or less. preferable. However, the addition of the conductive filler tends to deteriorate strength and fluidity. Therefore, it is desirable that the content of the conductive filler is as small as possible if a target conductivity level is obtained.

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

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

  The second embodiment of the laminated tube is composed of 5 layers or more including (a) layer, (b) layer, (c) layer, (d) layer, and (e) layer, and at least one (c) layer ( d) The layers are disposed adjacent to each other, and at least one pair of the (d) layer and the (e) layer is disposed adjacent to each other.

  In the laminated tube of the second aspect, it is essential to include the (c) layer and the (d) layer, and the chemical solution permeation prevention property, particularly hydrocarbon permeation prevention property, of the laminated tube is improved. In addition, it is essential to include a layer (e), and the chemical permeation preventing property of the laminated tube, in particular, the alcohol permeation preventing property and the permeation preventing property for high-concentration alcohol-containing gasoline are improved. At least one pair of (c) layer and (d) layer are disposed adjacent to each other, and at least one pair of (d) layer (e) layer is disposed adjacent to each other, thereby providing superior interlayer adhesion. When EVOH (C), semi-aromatic polyamide composition (D), and fluorine-containing polymer (E) are coextruded, sufficient melt stability and molding stability should be ensured. Is possible. That is, it is a laminated tube in which the (c) layer and the (e) layer are arranged on both sides adjacent to the (d) layer.

  In a preferred embodiment, the layer (a) is disposed in the outermost layer of the laminated tube. (A) By arrange | positioning a layer in the outermost layer, it becomes possible to obtain the laminated tube excellent in chemical resistance and a softness | flexibility. The (c) layer and the (d) layer are disposed between the (a) layer and the (e) layer. In addition, by arranging the (e) layer as the innermost layer, a laminated tube having excellent resistance to deterioration fuel can be obtained, and the elution of low molecular weight components such as monomers and oligomers due to contact with alcohol-containing gasoline can be suppressed. It becomes possible. That is, a laminated tube in which the (a) layer is disposed in the outermost layer, the (c) layer, the (d) layer, and the (e) layer are disposed adjacent to each other, and the (e) layer is disposed in the innermost layer is preferable. .

  In a more preferred embodiment, at least one pair of the (b) layer and the (c) layer are arranged adjacent to each other. By arranging the (b) layer on the other side adjacent to the (c) layer, it becomes possible to obtain better interlayer adhesion, and the polyamide 6/66/12 composition (B), EVOH ( When C), the semi-aromatic polyamide composition (D), and the fluorine-containing polymer (E) are coextruded, it becomes possible to ensure sufficient melt stability and molding stability. That is, a laminated tube in which the (a) layer, (b) layer, (c) layer, (d) layer, and (e) layer are arranged adjacent to each other from the outside to the inside is more preferable.

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

  The details of the conductive and conductive filler are the same as those of the laminated tube of the first aspect.

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

  In the laminated tube of the second embodiment, the thickness of each layer is not particularly limited and can be adjusted according to the type of polymer constituting each layer, the total number of layers in the laminated tube, the use, etc., but the thickness of each layer is It is determined in consideration of the properties of the laminated tube, such as chemical penetration prevention, low temperature impact resistance, and flexibility. Generally, the thicknesses of the (a) layer, (b) layer, (c) layer, (d) layer, and (e) layer are 3% or more and 90% or less, respectively, with respect to the thickness of the entire laminated tube. It is preferable. In consideration of the balance between low temperature impact resistance and chemical solution permeation prevention, the thickness of the (c) layer, (d) layer, and (e) layer is 5% or more and 50%, respectively, with respect to the total thickness of the laminated tube. More preferably, it is 7% or more and 30% or less.

  Moreover, as long as the total number of layers in the laminated tube of the second embodiment is 5 layers or more including (a) layer, (b) layer, (c) layer, (d) layer, and (e) layer, It is not limited. Furthermore, the laminated tube according to the second aspect provides a further function in addition to the five layers (a), (b), (c), (d), and (e), or is economical. In order to obtain an advantageous laminated tube, one or more layers containing other thermoplastic resins may be included. The number of layers of the laminated tube of the second aspect is 5 layers or more, but it is preferably 8 layers or less, more preferably 5 layers or more and 7 layers or less, judging from the mechanism of the tube manufacturing apparatus.

  Other thermoplastic resins in the laminated tube of the first embodiment and the second embodiment include those other than aliphatic polyamide (A), polyamide 6/66/12 (b1), polyamide (b2) and semi-aromatic polyamide (d). Polymetaxylylene succinamide (polyamide MXD4), polymetaxylylene glutaamide (polyamide MXD5), polymetaxylylene decanamide (polyamide MXD12), polymetaxylylene terephthalamide (polyamide MXDT), polymetaxylylene isophthalamide (polyamide) MXDI), polymetaxylylene hexahydroterephthalamide (polyamide MXDT (H)), polymetaxylylene naphthalamide (polyamide MXDN), polyparaxylylene succinamide (polyamide PXD4), polyparaxylyleneglutamide (polyamide) PXD5), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylene veramide (polyamide PXD8), polyparaxylylene azelamide (polyamide PXD9), polyparaxylylene sebacamide (polyamide PXD10), Polyparaxylylene decanamide (Polyamide PXD12), Polyparaxylylene terephthalamide (Polyamide PXDT), Polyparaxylylene isophthalamide (Polyamide PXDI), Polyparaxylylene hexahydroterephthalamide (Polyamide PXDT (H)) ), Polyparaxylylene naphthalamide (polyamide PXDN), polyparaphenylene terephthalamide (PPTA), polyparaphenylene isophthalamide (PPIA), polymetaphenylene terephthalamide (PMTA), polymeta Enylene isophthalamide (PMIA), poly (2,6-naphthalene dimethylene adipamide) (polyamide 2,6-BAN6), poly (2,6-naphthalene dimethylene suberamide) (polyamide 2,6-BAN8) ), Poly (2,6-naphthalene dimethylene azelamide) (polyamide 2,6-BAN9), poly (2,6-naphthalene dimethylene sebacamide) (polyamide 2,6-BAN10), poly (2,6 -Naphthalenedylene methylene dodecamide) (polyamide 2,6-BAN12), poly (2,6-naphthalenediethylene terephthalamide) (polyamide 2,6-BANT), poly (2,6-naphthalenediethylene methylene isophthalamide) ) (Polyamide 2,6-BANI), poly (2,6-naphthalenediethylenehexahydroterephthalamide) (polyamide) 2,6-BANT (H)), poly (2,6-naphthalene dimethylene naphthalamide) (polyamide 2,6-BANN), poly (1,3-cyclohexanedimethylene adipamide) (polyamide 1,3 -BAC6), poly (1,3-cyclohexanedimethylenesberamide (polyamide 1,3-BAC8), poly (1,3-cyclohexanedimethyleneazeamide) (polyamide 1,3-BAC9), poly (1,3 -Cyclohexanedimethylene sebacamide) (polyamide 1,3-BAC10), poly (1,3-cyclohexanedimethylene dodecamide) (polyamide 1,3-BAC12), poly (1,3-cyclohexanedimethylene terephthalamide) ) (Polyamide 1,3-BACT), poly (1,3-cyclohexanedimethylene isophthalamide) (poly Amide 1,3-BACI), poly (1,3-cyclohexanedimethylene hexahydroterephthalamide) (polyamide 1,3-BACT (H)), poly (1,3-cyclohexanedimethylene naphthalamide) (polyamide 1) , 3-BACN), poly (1,4-cyclohexanedimethylene adipamide) (polyamide 1,4-BAC6), poly (1,4-cyclohexanedimethylene suberamide) (polyamide 1,4-BAC8), poly (1,4-cyclohexanedimethylene azelamide) (polyamide 1,4-BAC9), poly (1,4-cyclohexanedimethylene sebacamide) (polyamide 1,4-BAC10), poly (1,4-cyclohexanedi) Methylene dodecamide) (polyamide 1,4-BAC12), poly (1,4-cyclohexanedimethylene) Reftalamide) (polyamide 1,4-BACT), poly (1,4-cyclohexanedimethylene isophthalamide) (polyamide 1,4-BACI), poly (1,4-cyclohexanedimethylene hexahydroterephthalamide) (polyamide) 1,4-BACT (H)), poly (1,4-cyclohexanedimethylenenaphthalamide) (polyamide 1,4-BACN), poly (4,4′-methylenebiscyclohexylene adipamide) (polyamide PACM6) Poly (4,4′-methylenebiscyclohexylene suberamide) (polyamide PACM8), poly (4,4′-methylenebiscyclohexylene azelamide) (polyamide PACM9), poly (4,4′-methylenebiscyclohexylene) Sebacamide) (polyamide PACM10), poly (4,4'- Methylene biscyclohexylene dodecamide) (polyamide PACM12), poly (4,4′-methylenebiscyclohexylene tetradecamide) (polyamide PACM14), poly (4,4′-methylenebiscyclohexylene hexadecanamide) (polyamide PACM16) ), Poly (4,4′-methylenebiscyclohexyleneoctadecamide) (polyamide PACM18), poly (4,4′-methylenebiscyclohexylene terephthalamide) (polyamide PACMT), poly (4,4′-methylene) Biscyclohexyleneisophthalamide) (polyamide PACMI), poly (4,4′-methylenebiscyclohexylenehexahydroterephthalamide) (polyamide PACMT (H)), poly (4,4′-methylenebiscyclohexylenenaphthalamide) ) Polyamide PACMN), poly (4,4′-methylenebis (2-methyl-cyclohexylene) adipamide) (polyamide MACM6), poly (4,4′-methylenebis (2-methyl-cyclohexylene) suberamide) (polyamide MACM8), Poly (4,4′-methylenebis (2-methyl-cyclohexylene) azeramide) (polyamide MACM9), poly (4,4′-methylenebis (2-methyl-cyclohexylene) sebacamide) (polyamide MACM10), poly (4 4′-methylenebis (2-methyl-cyclohexylene) dodecamide) (polyamide MACM12), poly (4,4′-methylenebis (2-methyl-cyclohexylene) tetradecanamide) (polyamide MACM14), poly (4,4′-methylenebis) (2-methyl- Chloroxylene) hexadecamide) (polyamide MACM16), poly (4,4′-methylenebis (2-methyl-cyclohexylene) octadecamide) (polyamide MACM18), poly (4,4′-methylenebis (2-methyl-cyclohexylene) terephthalamide) (Polyamide MACMT), poly (4,4′-methylenebis (2-methyl-cyclohexylene) isophthalamide) (polyamide MACMI), poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexahydroterephthalamide) (Polyamide MACMT (H)), poly (4,4′-methylenebis (2-methyl-cyclohexylene) naphthalamide) (polyamide MACMN), poly (4,4′-propylenebiscyclohexylene adipamide) (polyamide PACP) 6), poly (4,4′-propylene biscyclohexylene suberamide) (polyamide PACP8), poly (4,4′-propylene biscyclohexylene azelamide) (polyamide PACP9), poly (4,4′-propylene bis) Cyclohexylene sebacamide) (polyamide PACP10), poly (4,4′-propylene biscyclohexylene dodecamide) (polyamide PACP12), poly (4,4′-propylene biscyclohexylene tetradecanamide) (polyamide PACP14), Poly (4,4′-propylene biscyclohexylene hexadecanamide) (polyamide PACP16), poly (4,4′-propylene biscyclohexylene octadecanamide) (polyamide PACP18), poly (4,4′-propylene biscyclohexyl) Silentele Taramide) (polyamide PACPT), poly (4,4′-propylene biscyclohexylene isophthalamide) (polyamide PACPI), poly (4,4′-propylene biscyclohexylene hexahydroterephthalamide) (polyamide PACPT (H) ), Poly (4,4′-propylene biscyclohexylene naphthalamide) (polyamide PACPN), polyisophorone adipamide (polyamide IPD6), polyisophorone veramide (polyamide IPD8), polyisophorone azelamide (polyamide IPD9), poly Isophorone sebacamide (polyamide IPD10), polyisophorodecamide (polyamide IPD12), polyisophorone terephthalamide (polyamide IPDT), polyisophorone isophthalamide (polyamide IPDI), Liisophorone hexahydroterephthalamide (polyamide IPDT (H)), polyisophorone naphthalamide (polyamide IPDN), polytetramethylene terephthalamide (polyamide 4T), polytetramethylene isophthalamide (polyamide 4I), polytetramethylene hexa Hydroterephthalamide (polyamide 4T (H)), polytetramethylene naphthalamide (polyamide 4N), polypentamethylene terephthalamide (polyamide 5T), polypentamethylene isophthalamide (polyamide 5I), polypentamethylene hexahydrotere Phthalamide (polyamide 5T (H)), polypentamethylene naphthalamide (polyamide 5N), polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I) ), Polyhexamethylene hexahydroterephthalamide (polyamide 6T (H)), polyhexamethylene naphthalamide (polyamide 6N), poly (2-methylpentamethylene terephthalamide) (polyamide M5T), poly (2-methylpenta) Methyleneisophthalamide) (polyamide M5I), poly (2-methylpentamethylene hexahydroterephthalamide) (polyamide M5T (H)), poly (2-methylpentamethylenenaphthalamide (polyamide M5N), polynonamethylene terephthalate Lamidamide (polyamide 9T), polynonamethylene isophthalamide (polyamide 9I), polynonamethylene hexahydroterephthalamide (polyamide 9T (H)), polynonamethylenenaphthalamide (polyamide 9N), poly (2-methyloctamethylene) Terephthala (Polyamide M8T), poly (2-methyloctamethyleneisophthalamide) (polyamide M8I), poly (2-methyloctamethylenehexahydroterephthalamide) (polyamide M8T (H)), poly (2-methylocta Methylene naphthalamide) (polyamide M8N), polytrimethylhexamethylene terephthalamide (polyamide TMHT), polytrimethylhexamethylene isophthalamide (polyamide TMHI), polytrimethylhexamethylene hexahydroterephthalamide (polyamide TMHT (H)), Polytrimethylhexamethylene naphthalamide (polyamide TMHN), polydecamethylene terephthalamide (polyamide 10T), polydecamethylene isophthalamide (polyamide 10I), polydecamethylene hexahydroteref Lamidamide (polyamide 10T (H)), polydecamethylene naphthalamide (polyamide 10N), polyundecamethylene terephthalamide (polyamide 11T), polyundecamethylene isophthalamide (polyamide 11I), polyundecamethylene hexahydrotere Phthalamide (polyamide 11T (H)), polyundecamethylene naphthalamide (polyamide 11N), polydodecamethylene terephthalamide (polyamide 12T), polydodecamethylene isophthalamide (polyamide 12I), polydodecamethylene hexahydroterephthalate Lamide (polyamide 12T (H)), polydodecamethylene naphthalamide (polyamide 12N), raw material monomers of these polyamides and / or copolymers using several raw material monomers of the aliphatic polyamide (A), etc. Polyamide Based resins.

Also, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (PFA), Tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoro (alkyl vinyl ether) / hexafluoropropylene copolymer, ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / tetrafluoroethylene / Hexafluoropropylene copolymer (EFEP), vinylidene fluoride / tetrafluoroethylene copolymer, vinylidene fluoride / hexafluoropropylene copolymer, vinylidene fluoride / perfluoro (Alkyl vinyl ether) copolymer, tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (THV), vinylidene fluoride / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer, tetrafluoroethylene / hexafluoro Propylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer, ethylene / chlorotrifluoroethylene copolymer (ECTFE), chlorotrifluoroethylene / tetrafluoroethylene copolymer, vinylidene fluoride / chlorotrifluoroethylene copolymer Polymer, chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) copolymer, chlorotrifluoroethylene / hexafluoropropylene copolymer, chlorotrifluoroethylene / Tetrafluoroethylene / hexafluoropropylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene / vinylidene fluoride copolymer, chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer (CPT), Chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) / hexafluoropropylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene / hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer, chlorotrifluoroethylene / tetrafluoroethylene / Vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer, chlorotrifluoroethylene / tetrafluoroethylene / vinylidene fluoride / f Containing no functional groups reactive with amino groups such as oxafluoropropylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) / hexafluoropropylene copolymer A fluorine-type polymer is mentioned.
When the laminated tube has the (e) layer, the low temperature impact resistance and the chemical liquid permeation preventive property are provided by disposing a layer containing a fluorine-based polymer not containing a functional group with respect to the (e) layer. , And environmental stress crack resistance, and it is economically advantageous. The fluorine-containing polymer (E) is not contained other than the layer (e).

  Furthermore, high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra high molecular weight polyethylene (UHMWPE), polypropylene (PP), polybutene (PB) , Polymethylpentene (TPX), ethylene / propylene copolymer (EPR), ethylene / butene copolymer (EBR), ethylene / vinyl acetate copolymer (EVA), ethylene / acrylic acid copolymer (EAA), Polyolefins such as ethylene / methacrylic acid copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), ethylene / ethyl acrylate copolymer (EEA) Resin; Polystyrene (PS), Syndiotactic Poly Tylene (SPS), methyl methacrylate / styrene copolymer (MS), methyl methacrylate / styrene / butadiene copolymer (MBS), styrene / butadiene copolymer (SBR), styrene / isoprene copolymer (SIR) Styrene / isoprene / butadiene copolymer (SIBR), styrene / butadiene / styrene copolymer (SBS), styrene / isoprene / styrene copolymer (SIS), styrene / ethylene / butylene / styrene copolymer (SEBS) , Polystyrene resins such as styrene / ethylene / propylene / styrene copolymer (SEPS); acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4 -Cyclohexene-1,2-dicarboxylic acid, Carboxyl groups such as dobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid and their metal salts (Na, Zn, K, Ca, Mg), maleic anhydride, itaconic anhydride, anhydrous Acid anhydride groups such as citraconic acid and endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid anhydride; glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, citracone Polyolefin resins and polystyrene resins containing functional groups such as epoxy groups such as glycidyl acid; polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), poly (ethylene terephthalate / ethylene iso Phthalate) copolymer (PET / PEI), polytri Methylene terephthalate (PTT), polycyclohexanedimethylene terephthalate (PCT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyarylate (PAR), liquid crystalline polyester (LCP), polylactic acid (PLA), polyglycol Polyester resins such as acid (PGA); Polyether resins such as polyacetal (POM) and polyphenylene ether (PPO); Polysulfones such as polysulfone (PSU), polyethersulfone (PESU), and polyphenylsulfone (PPSU) Resins; Polythioether resins such as polyphenylene sulfide (PPS) and polythioether sulfone (PTES); Polyketone (PK), Polyetherketone (PEK), Polyetheretherketone (PEEK) , Polyether Ketone Ketone (PEKK), Polyether Ether Ether Ketone (PEEEK), Polyether Ether Ketone Ketone (PEEEKK), Polyether Ketone Ketone Ketone (PEKKK), Polyether Ketone Ether Ketone Ketone (PEKEKK), etc. Polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), acrylonitrile / butadiene copolymer ( Polynitrile resins such as NBR); Polymethacrylate resins such as polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA); Polyvinyl resins such as polyvinyl acetate (PVAc) Ester resin: Polyvinyl chloride resin such as polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer; cellulose acetate, cellulose butyrate, etc. Cellulose-based resins; polycarbonate-based resins such as polycarbonate (PC); Polyimide-based resins such as thermoplastic polyimide (TPI), polyetherimide, polyesterimide, polyamideimide (PAI), and polyesteramideimide; Thermoplastic polyurethane-based resins; Polyamide elastomer, polyurethane elastomer, polyester elastomer and the like can be mentioned.

In the laminated tube of the first aspect, from the viewpoint of the melt stability of EVOH (C), among the thermoplastic resins exemplified above, a polyester resin having a melting point of 280 ° C. or less, a polyamide resin, a polythioether resin It is preferable to use a resin, a polyolefin-based resin, and a fluorine-based polymer.
In the laminated tube of the second embodiment, from the viewpoint of the melt stability of EVOH (C), among the thermoplastic resins exemplified above, a polyester resin having a melting point of 280 ° C. or less, a polyamide resin, a polythioether resin It is preferable to use a resin, a polyolefin-based resin, and a fluoropolymer that does not contain a functional group.

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

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

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

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

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

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

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

  Moreover, since the laminated tube is excellent in chemical solution permeation preventive properties, it is suitable as a chemical solution transport tube. Examples of the chemical solution include aromatic hydrocarbon solvents such as benzene, toluene, and xylene; alcohols such as methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, diethylene glycol, phenol, cresol, polyethylene glycol, and polypropylene glycol Phenol solvent; ether solvents such as dimethyl ether, dipropyl ether, methyl-t-butyl ether, ethyl-t-butyl ether, dioxane, tetrahydrofuran; chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, Halogen solvents such as tetrachloroethane, perchlorethane, chlorobenzene; seton, methyl ethyl ketone, di Ketone solvents such as tilketone and acetophenone; gasoline, kerosene, diesel gasoline, alcohol-containing gasoline, ethyl-t-butyl ether blend, oxygen-containing gasoline, amine-containing gasoline, sour gasoline, castor oil base brake fluid, glycol ether brake fluid, boric acid ester Brake fluids for extremely cold regions, brake fluids for extremely cold regions, brake fluids for silicone oils, brake fluids for mineral oils, power steering oils, hydrogen sulfide oils, window washer fluids, engine coolants, urea solutions, pharmaceutical agents, inks, paints, etc. It is done. The laminated tube is suitable as a tube for conveying the chemical solution. Specifically, a feed tube, a return tube, an evaporation tube, a fuel filler tube, an ORVR tube, a reserve tube, a fuel tube such as a vent tube, an oil tube, an oil tube, etc. Drilling tube, brake tube, window washer fluid tube, engine coolant (LLC) tube, reservoir tank tube, urea solution transfer tube, cooler tube for cooling water, refrigerant, etc., air conditioner refrigerant tube, heater tube, load heating tube , Floor heating tubes, infrastructure supply tubes, fire extinguishers and fire extinguishing equipment tubes, medical cooling equipment tubes, inks, paint spray tubes, and other chemical solution tubes. In particular, it is suitable as a fuel tube.

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

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

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

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

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

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

Moreover, each physical property of the laminated tube was measured by the following method.
[Low temperature impact resistance]
The impact test was performed at −40 ° C. by the method described in VW TL 52435 6.5.

[Medical solution (alcohol-containing gasoline (CE10)) permeation-preventing property]
Seal one end of the tube cut to 200 mm, put alcohol-containing gasoline (CE10) mixed with Fuel C (isooctane / toluene = 50/50 volume ratio) and ethanol in a 90/10 volume ratio inside, and the other end also Sealed. Thereafter, the entire mass was measured, and then the test tube was placed in an oven at 60 ° C., and the mass change was measured every day. The mass change per day was divided by the surface area of the tube to calculate the alcohol-containing gasoline permeation amount (CE10) (g / m ² · day). When the alcohol-containing gasoline permeation amount (CE10) was 3.0 g / m ² · day or less, it was judged that the chemical solution (alcohol-containing gasoline (CE10)) was excellent in permeation prevention.

[Permeability of chemical solution (alcohol-containing gasoline (CE85))]
Seal one end of the tube cut to 200 mm, and put alcohol-containing gasoline (CE85) mixed with Fuel C (isooctane / toluene = 50/50 volume ratio) and ethanol in a 15/85 volume ratio inside, and the other end also Sealed. Thereafter, the entire mass was measured, and then the test tube was placed in an oven at 60 ° C., and the mass change was measured every day. The mass change per day was divided by the surface area of the tube to calculate the alcohol-containing gasoline permeation amount (CE85) (g / m ² · day).

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

[Interlayer adhesion after heat treatment]
The tube cut to 200 mm was placed in an oven at 160 ° C. and treated for 12 minutes. The interlayer adhesion of the removed tube was evaluated according to the method described above. When the peel strength after heat treatment was 2.0 N / mm or more, it was judged that the durability of interlayer adhesion was excellent.

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

[Melting stability, molding stability]
The laminated tube is molded under the conditions shown below, and the cross section in the laminated tube 1 hour after the start of molding is cut and then observed with a microscope, thereby containing a saponified ethylene / vinyl acetate copolymer (C). (C) The thickness of the layer was measured at four locations in the east, west, south, and north. The average value of the (c) layer thickness was calculated, and when the deviation from the target value was within 20%, it was judged that the melt stability and the molding stability were good. On the other hand, when it exceeded 20%, it was judged that the melt stability and the molding stability were poor.

[Materials Used in Examples and Comparative Examples]
Aliphatic polyamide (a), polyamide (b2)
Polyamide 12 (a-1) (manufactured by Ube Industries, UBESTA 3030UX1, relative viscosity 2.21)
Polyamide 12 (a-2) (Ube Industries, UBESTA 3020U, relative viscosity 1.86)

Production of polyamide 610 (a-3) or (b2-1) In a pressure-resistant reaction vessel equipped with a stirrer with an internal volume of 70 liters, equimolar salt of 1,6-hexanediamine and sebacic acid 15.02 kg (50.0 mol) 1,1-hexanediamine (15.1 g, 0.13 mol) and distilled water (5.0 L) were charged, the inside of the polymerization tank was purged with nitrogen, and then heated to 220 ° C., and the reaction system was homogeneous at this temperature. The mixture was stirred so as to be in a state. Next, the temperature in the polymerization tank was raised to 270 ° C., and polymerization was performed with stirring for 2 hours while adjusting the pressure in the tank to 1.7 MPa. Thereafter, the pressure was released to normal pressure over about 2 hours, and then the pressure was reduced to 53 kPa, and polymerization was performed for 4 hours under reduced pressure. Next, nitrogen was introduced into the autoclave, and after returning to normal pressure, the strand was extracted from the lower nozzle of the reaction vessel and cut to obtain pellets. This pellet was dried under reduced pressure to obtain a polyamide 610 having a relative viscosity of 2.58, a terminal amino group concentration of 73 μeq / g, and a terminal carboxyl group concentration of 53 μeq / g (hereinafter, this polyamide 610 was converted to (a-3) or (b2- 1).)

Production of polyamide 612 (a-4) or (b2-2) In the production of polyamide 610 (a-3), 15.02 kg (50.0 mol) of an equimolar salt of 1,6-hexanediamine and sebacic acid was 1 , 6-hexanediamine and dodecanedioic acid equimolar salt 16.43 kg (50.0 mol), except that the relative viscosity 2.48, in the same manner as the production of polyamide 610 (a-3), A polyamide 612 having a terminal amino group concentration of 70 μeq / g and a terminal carboxyl group concentration of 51 μeq / g was obtained (hereinafter, this polyamide 612 is referred to as (a-4) or (b2-2)).

Aliphatic polyamide composition (A)
Manufacture of polyamide 12 composition (A-1) Polyamide 12 (a-1) was coated with maleic anhydride-modified ethylene / propylene copolymer (JSR T7761P, JSR Co., Ltd.) as an impact modifier, and trioxide as an antioxidant. Ethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan, IRGANOX 245), and tris (2,4-di-t as a phosphorus processing stabilizer -Butylphenyl) phosphite (manufactured by BASF Japan, IRGAFOS168) is mixed in advance and supplied to a biaxial melt kneader (manufactured by Nippon Steel Works, model: TEX44), while the cylinder of the biaxial melt kneader Benzenesulfonic acid butyramide as a plasticizer is injected from the middle of After melt-kneading from 180 ° C to 260 ° C and extruding the molten resin into a strand shape, this is introduced into a water bath, cooled, cut, and vacuum dried to give polyamide 12 (a-1) 85 mass%, an impact modifier. Polyamide 12 composition pellets comprising 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus processing stabilizer were obtained with respect to a total of 100 parts by mass of 10% by mass and 5% by mass of plasticizer (hereinafter referred to as “below”). The polyamide 12 composition is referred to as (A-1).

Manufacture of polyamide 12 composition (A-2) In the manufacture of polyamide 12 composition (A-1), a polyamide 12 composition (A- 1) In the same manner as in the production of 1), 0.8 parts by mass of antioxidant and phosphorus-based processing stability with respect to 100 parts by mass in total of 85% by mass of polyamide 12 (a-1) and 15% by mass of impact modifier. The pellet of the polyamide 12 composition which consists of 0.2 mass part of agents was obtained (Hereinafter, this polyamide 12 composition is called (A-2).).

Production of Conductive Polyamide 12 Composition (A-3) In production of the polyamide 12 composition (A-1), the polyamide 12 (a-1) is changed to (a-2), and carbon black (cabot) is used as the conductive filler. Except for changing the cylinder temperature from 260 ° C. to 270 ° C. without using a plasticizer using Vulcan XD-72, manufactured by the company, in the same manner as the production of the polyamide 12 composition (A-1), For 100 parts by mass of polyamide 12 (a-2) 60% by mass, impact modifier 20% by mass, and conductive filler 20% by mass, 0.8 parts by mass of antioxidant and 0.2% of phosphorus processing stabilizer 0.2%. The pellet of the conductive polyamide 12 composition which consists of a mass part was obtained (henceforth this conductive polyamide 12 composition is called (A-3)).

Production of polyamide 610 composition (A-4) In production of polyamide 12 composition (A-1), polyamide 12 (a-1) was changed to polyamide 610 (a-3), and the cylinder temperature was changed from 260 ° C to 270 ° C. In the same manner as in the production of the polyamide 12 composition (A-1), the total amount of polyamide 610 (a-3) 80% by mass, impact modifier 10% by mass, and plasticizer 10% by mass is 100. Pellets of polyamide 610 composition comprising 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus processing stabilizer were obtained with respect to parts by mass (hereinafter, this polyamide 610 composition was referred to as (A-4)). That said.)

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

Polyamide 6/66/12 (b1)
Production of polyamide 6/66/12 (b1-1) Caprolactam 9.93 kg (87.7 mol), equimolar salt of 1,6-hexanediamine and adipic acid in a pressure-resistant reaction vessel equipped with a stirrer with an internal volume of 70 liters 1.40 kg (5.7 mol), 1.40 kg (6.5 mol) of 12-aminododecanoic acid, and 2.0 L of distilled water are added, heated to 100 ° C., and the reaction system is homogeneous at this temperature It stirred so that it might become. Subsequently, the temperature was further raised to 260 ° C., and the mixture was stirred for 1 hour under a pressure of 2.5 MPa. Then, the polymerization reaction was performed at 260 ° C. for 2 hours under atmospheric pressure while releasing the pressure to evaporate water from the reaction vessel, and further for 7 hours under reduced pressure of 260 ° C. and 53 kPa. After completion of the reaction, the reaction product taken out in a strand form from the lower nozzle of the reaction vessel was introduced into a water bath, cooled, and cut to obtain pellets. This pellet was immersed in hot water to remove unreacted monomers and then dried under reduced pressure to give polyamide 6/66/12 (caproamide unit / hexamethylene adipamide unit / dodecanamide) having a relative viscosity of 4.01. (Unit: 78/11/11% by mass) was obtained (hereinafter, this polyamide 6/66/12 is referred to as (b1-1)).

Production of polyamide 6/12 (b1-2) In production of polyamide 6/66/12 (b1-1), 9.93 kg (87.7 mol) of caprolactam, equimolar salt of 1,6-hexanediamine and adipic acid 1.40 kg (5.7 mol) and 1.40 kg (6.5 mol) of 12-aminododecanoic acid were added to 9.90 kg (87.5 mol) of caprolactam and 2.69 kg (12.5 mol) of 12-aminododecanoic acid. The polyamide 6/12 having a relative viscosity of 3.86 (caproamide unit / dodecanamide unit = 80/20% by mass) was produced in the same manner as in the production of polyamide 6/66/12 (b1-1) except that (Hereinafter, this polyamide 6/12 is referred to as (b1-2)).

Polyamide 6/66/12 composition (B)
Production of Polyamide 6/66/12 Composition (B-1) Polyamide 6/66/12 (b1-1) and polyamide 610 (b2-1) were mixed with maleic anhydride-modified ethylene / 1-butene copolymer (B2). -1) (Mitsui Chemicals, Tuffmer MH5020; flexural modulus measured according to ISO 178: 5 MPa), triethylene glycol-bis [3- (3-t-butyl-5-5 as an antioxidant) Methyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan, IRGANOX245), and tris (2,4-di-t-butylphenyl) phosphite (manufactured by BASF Japan, IRGAFOS168) as a phosphorus processing stabilizer. The mixture is mixed and supplied to a twin-screw melt kneader (manufactured by Nippon Steel Co., Ltd., model: TEX44). Benzenesulfonic acid butyramide (B1-1) is injected from the middle of the cylinder of the machine with a metering pump, melt-kneaded at a cylinder temperature of 180 ° C to 260 ° C, and the molten resin is extruded into a strand shape, which is then introduced into a water tank Cooling, cutting, and vacuum drying, polyamide 6/66/12 (b1-1) 50% by mass, polyamide 610 (b2-1) 30% by mass, plasticizer (B1-1) 5% by mass, olefin weight A pellet of a polyamide 6/66/12 composition comprising 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus processing stabilizer with respect to a total of 100 parts by mass of 15% by mass of the combined (B2-1). (Hereinafter, this polyamide 6/66/12 composition is referred to as (B-1)).

Production of polyamide 6/66/12 composition (B-2) In the production of polyamide 6/66/12 composition (B-1), polyamide 610 (b2-1) was changed to polyamide 612 (b2-2). Except for polyamide 6/66/12 (b1-1) 60 mass%, polyamide 612 (b2-2) 20 mass% in the same manner as in the production of the polyamide 6/66/12 composition (B-1). , 5 parts by mass of plasticizer (B1-1) and 15 parts by mass of olefin polymer (B2-1), 100 parts by mass in total, 0.8 parts by mass of antioxidant, 0.2 mass of phosphorus processing stabilizer Part of a polyamide 6/66/12 composition pellet was obtained (hereinafter, this polyamide 6/66/12 composition is referred to as (B-2)).

Manufacture of polyamide 6/66/12 composition (B-3) Polyamide 6/66 / except that polyamide 610 (b2-1) is not used in the manufacture of polyamide 6/66/12 composition (B-1). 12 Polyamide 6/66/12 (b1-1) 80% by mass, plasticizer (B1-1) 5% by mass, olefin polymer (B2-1) in the same manner as in the production of composition (B-1). ) A pellet of polyamide 6/66/12 composition comprising 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus processing stabilizer was obtained with respect to 100 parts by mass in total of 15% by mass (hereinafter, This polyamide 6/66/12 composition is referred to as (B-3)).

Production of polyamide 6/66/12 composition (B-4) Polyamide 610 (b2-1), plasticizer (B1-1), and olefin in the production of polyamide 6/66/12 composition (B-1) Except not using a polymer (B2-1), it is the same method as manufacture of a polyamide 6/66/12 composition (B-1), and polyamide 6/66/12 (b1-1) is 100 mass%. In contrast, a pellet of a polyamide 6/66/12 composition comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus-based processing stabilizer was obtained (hereinafter, this polyamide 6/66/12 composition was (B-4).)

Production of polyamide 6/12 composition (B-5) In the production of polyamide 6/66/12 composition (B-4), polyamide 6/66/12 (b1-1) was converted to polyamide 6/12 (b1-2). Except for the change to the polyamide 6/66/12 composition (B-4), the antioxidant was adjusted to 0.1% with respect to 100% by mass of the polyamide 6/12 (b1-2). A pellet of a polyamide 6/12 composition comprising 8 parts by mass and 0.2 parts by mass of a phosphorus processing stabilizer was obtained (hereinafter, this polyamide 6/12 composition is referred to as (B-5)).

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

Semi-aromatic polyamide (d)
Manufacture of semi-aromatic polyamide (d-1) Equipped with a stirrer, thermometer, torque meter, pressure gauge, raw material inlet directly connected with diaphragm pump, nitrogen gas inlet, pressure outlet, pressure regulator, and polymer outlet In a pressure vessel having an internal volume of 40 liters, 4.121 kg (28.2 mol) of adipic acid, 0.299 kg (1.8 mol) of isophthalic acid, 8.50 g (0.049 mol) of calcium hypophosphite, and sodium acetate After charging 4.37 g (0.049 mol), pressurizing to 0.3 MPa with 99.9999% nitrogen gas inside the pressure vessel, and then releasing nitrogen gas to normal pressure five times After repeatedly performing nitrogen substitution, the system was heated while stirring under a sealing pressure. Furthermore, the temperature was raised to 160 ° C. under a small amount of nitrogen stream, and the mixture was melted with stirring and mixing at the same temperature to form a slurry. To this, 4.086 kg (30.0 mol) of m-xylylenediamine was added dropwise over 160 minutes with stirring. During this time, the internal pressure of the reaction system was controlled to 0.5 MPa, and the internal temperature was continuously raised to 260 ° C. Moreover, the water distilled with the dropwise addition of m-xylylenediamine was removed out of the system through a condenser and a cooler. After completion of the dropwise addition of m-xylylenediamine, the pressure was reduced to normal pressure over 60 minutes, and the reaction was continued for 10 minutes while maintaining the temperature in the container at 260 ° C. Thereafter, the internal pressure of the reaction system was reduced to 79 kPa, and the melt polymerization reaction was continued for 40 minutes. Thereafter, stirring was stopped and the inside of the system was pressurized to 0.2 MPa with nitrogen, and the polycondensate was extracted from the lower outlet of the pressure vessel into a string shape. The string-like polycondensate is immediately cooled, and the water-cooled string-like resin is pelletized by a pelletizer and then dried under reduced pressure, and a semi-aromatic polyamide (polyamide MXD6 / MXDI = 94/6 mol%) (hereinafter, this semi-aromatic polyamide is referred to as (d-1)).

Production of semi-aromatic polyamide (d-2) In the production of semi-aromatic polyamide (d-1), 4.121 kg (28.2 mol) of adipic acid and 0.299 kg (1.8 mol) of isophthalic acid were added to adipic acid. Except for changing to 3.946 kg (27.0 mol) and terephthalic acid 0.498 kg (3.0 mol), the same method as the production of the semi-aromatic polyamide (d-1), melting point 229 ° C., relative A semi-aromatic polyamide having a viscosity of 2.35 (polyamide MXD6 / MXDT = 90/10 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (d-2)).

Production of semi-aromatic polyamide (d-3) In production of semi-aromatic polyamide (d-1), 0.299 kg (1.8 mol) of isophthalic acid was converted to 0.389 kg (1.8 mol) of 2,6-naphthalenedicarboxylic acid. Mol) A semi-aromatic polyamide having a melting point of 230 ° C. and a relative viscosity of 2.36 (polyamide MXD6 / MXDN = 94/6 mol%) in the same manner as in the production of the semi-aromatic polyamide (d-1) except that it was changed. (Hereinafter, this semi-aromatic polyamide is referred to as (d-3)).

Production of semi-aromatic polyamide (d-4) In the production of semi-aromatic polyamide (d-1), 4.112 kg (28.2 mol) of adipic acid and 0.299 kg (1.8 mol) of isophthalic acid were mixed with adipic acid. The production of semi-aromatic polyamide (d-1) except that 3.858 kg (26.4 mol) and 0.598 kg (3.6 mol) of isophthalic acid were changed and the polymerization temperature was changed from 260 ° C to 250 ° C. In the same manner, a semi-aromatic polyamide (polyamide MXD6 / MXDI = 88/12 mol%) having a melting point of 219 ° C. and a relative viscosity of 2.34 was obtained (hereinafter, this semi-aromatic polyamide is referred to as (d-4). .)

Production of semi-aromatic polyamide (d-5) In the production of semi-aromatic polyamide (d-1), 4.121 kg (28.2 mol) of adipic acid and 0.299 kg (1.8 mol) of isophthalic acid were mixed with adipic acid. 3. Preparation of semi-aromatic polyamide (d-1), except that it was changed to 3.507 kg (24.0 mol) and 0.997 kg (6.0 mol) of isophthalic acid, and the polymerization temperature was changed from 260 ° C to 240 ° C. In the same manner, a semi-aromatic polyamide (polyamide MXD6 / MXDI = 80/20 mol%) having a melting point of 207 ° C. and a relative viscosity of 2.39 was obtained (hereinafter, this semi-aromatic polyamide is referred to as (d-5). .)

Production of semi-aromatic polyamide (d-6) In production of semi-aromatic polyamide (d-1), 4.121 kg (28.2 mol) of adipic acid and 0.299 kg (1.8 mol) of isophthalic acid were mixed with adipic acid. The production of the semi-aromatic polyamide (d-1) except that the polymerization temperature was changed from 260 ° C to 230 ° C by changing to 3.069 kg (21.0 mol) and 1.495 kg (9.0 mol) of isophthalic acid. In the same manner, a semi-aromatic polyamide (polyamide MXD6 / MXDI = 70/30 mol%) having a melting point of 186 ° C. and a relative viscosity of 2.45 was obtained (hereinafter, this semi-aromatic polyamide is referred to as (d-6). .)

Production of semi-aromatic polyamide (d-7) In the production of semi-aromatic polyamide (d-1), 4.121 kg (28.2 mol) of adipic acid, 0.299 kg (1.8 mol) of isophthalic acid, and m -4.086 kg (30.0 mol) of xylylenediamine, 3.946 kg (27.0 mol) of adipic acid, 0.598 kg (3.0 mol) of ε-caprolactam, and 3.677 kg of m-xylylenediamine ( A semi-aromatic polyamide having a melting point of 229 ° C. and a relative viscosity of 2.40 (polyamide MXD6 / 6 = 90) was produced in the same manner as in the production of the semi-aromatic polyamide (d-1) except that the amount was changed to 27.0 mol). / 10 mol%) (hereinafter, this semi-aromatic polyamide is referred to as (d-7)).

Production of semi-aromatic polyamide (d-8) Production of semi-aromatic polyamide (d-6) except that the melt polymerization time was changed from 40 minutes to 20 minutes in the production of semi-aromatic polyamide (d-6). In the same manner, a semi-aromatic polyamide (polyamide MXD6 / MXDI = 70/30 mol%) having a melting point of 186 ° C. and a relative viscosity of 2.08 was obtained (hereinafter, this semi-aromatic polyamide is referred to as (d-8). .)

Production of semi-aromatic polyamide (d-9) In the production of semi-aromatic polyamide (d-1), 4.121 kg (28.2 mol) of adipic acid, 0.299 kg (1.8 mol) of isophthalic acid, and m -4.086 kg (30.0 mol) of xylylenediamine, 6.068 kg (30.0 mol) of sebacic acid, and 4.086 kg (30.30) of a mixed diamine of m-xylylenediamine and p-xylylenediamine of 3: 7. Except that the polymerization temperature was changed from 260 ° C. to 320 ° C., in the same manner as in the production of the semi-aromatic polyamide (d-1), a semi-fragrance having a melting point of 299 ° C. and a relative viscosity of 2.30 Group polyamide (polyamide MXD10 / PXD10 = 30/70 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (d-9)).

Semi-aromatic polyamide composition (D)
Manufacture of a semi-aromatic polyamide composition (D-1) A semi-aromatic polyamide (d-1) was coated with a maleic anhydride-modified ethylene / propylene copolymer (manufactured by JSR Corporation, JSR T7761P) as an impact modifier. Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan, IRGANOX 245) as an inhibitor, and tris (2,4 as a phosphorus 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 Works, model: TEX44). After melt-kneading at 280 ° C and extruding the molten resin into strands, this is introduced into a water bath, cooled and cut After vacuum drying, the total amount of 100 parts by mass of 85% by mass of semi-aromatic polyamide (d-1) and 15% by mass of the impact modifier is 0.8 parts by mass of antioxidant and 0.2 phosphorus processing stabilizer. The pellet of the semi-aromatic polyamide composition which consists of a mass part was obtained (henceforth this semi-aromatic polyamide composition is called (D-1)).

Production of semi-aromatic polyamide composition (D-2) In the production of semi-aromatic polyamide composition (D-1), the semi-aromatic polyamide (d-1) was changed to (d-2), In the same manner as in the production of the aromatic polyamide composition (D-1), an antioxidant is added to a total of 100 parts by mass of 85% by mass of the semi-aromatic polyamide (d-2) and 15% by mass of the impact modifier. A pellet of a semi-aromatic polyamide composition comprising 0.8 part by mass and 0.2 part by mass of a phosphorus processing stabilizer was obtained (hereinafter, this semi-aromatic polyamide composition is referred to as (D-2)).

Production of semi-aromatic polyamide composition (D-3) In the production of semi-aromatic polyamide composition (D-1), semi-aromatic polyamide (d-1) was changed to (d-3), In the same manner as in the production of the aromatic polyamide composition (D-1), an antioxidant is added to a total of 100 parts by mass of 85% by mass of the semi-aromatic polyamide (d-3) and 15% by mass of the impact modifier. A semi-aromatic polyamide composition pellet comprising 0.8 part by mass and phosphorus-based processing stabilizer 0.2 part by mass was obtained (hereinafter, this semi-aromatic polyamide composition is referred to as (D-3)).

Production of semi-aromatic polyamide composition (D-4) In production of semi-aromatic polyamide composition (D-1), semi-aromatic polyamide (d-1) was changed to (d-4), and the cylinder temperature was 280. In the same manner as the production of the semi-aromatic polyamide composition (D-1) except that the temperature was changed from 270 ° C. to 270 ° C., 85% by mass of the semi-aromatic polyamide (d-4) and 15% by mass of the impact modifier A semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer was obtained with respect to 100 parts by weight in total (hereinafter, this semi-aromatic polyamide composition). (D-4).)

Production of semi-aromatic polyamide composition (D-5) In production of semi-aromatic polyamide composition (D-1), semi-aromatic polyamide (d-1) was changed to (d-5), and the cylinder temperature was 280. Except for changing from ℃ to 260 ℃, in the same manner as in the production of the semi-aromatic polyamide composition (D-1), the semi-aromatic polyamide (d-5) was 85 mass% and the impact modifier was 15 mass%. A semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer was obtained with respect to 100 parts by weight in total (hereinafter, this semi-aromatic polyamide composition). (Referred to as (D-5)).

Production of semi-aromatic polyamide composition (D-6) In production of semi-aromatic polyamide composition (D-1), semi-aromatic polyamide (d-1) was changed to (d-6), and the cylinder temperature was 280. Except for changing from ℃ to 240 ℃, by the same method as the production of the semi-aromatic polyamide composition (D-1), 85% by mass of the semi-aromatic polyamide (d-6) and 15% by mass of the impact modifier A semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer was obtained with respect to 100 parts by weight in total (hereinafter, this semi-aromatic polyamide composition). (Referred to as (D-6)).

Production of Semi-Aromatic Polyamide Composition (D-7) In the production of the semi-aromatic polyamide composition (D-1), the semi-aromatic polyamide (d-1) was changed to (d-7), In the same manner as in the production of the aromatic polyamide composition (D-1), an antioxidant is added to a total of 100 parts by mass of 85% by mass of the semi-aromatic polyamide (d-7) and 15% by mass of the impact modifier. A pellet of a semi-aromatic polyamide composition comprising 0.8 part by mass and 0.2 part by mass of a phosphorus processing stabilizer was obtained (hereinafter, this semi-aromatic polyamide composition is referred to as (D-7)).

Production of conductive semi-aromatic polyamide composition (D-8) In production of semi-aromatic polyamide composition (D-1), semi-aromatic polyamide (d-1) was used as (d-8) as an impact modifier. Maleic anhydride-modified ethylene / propylene copolymer (manufactured by JSR Corp., JSR T7761P) Instead of a copolymer (Mitsui Chemicals, Tuffmer A-0550), carbon black (Lion Corporation, Ketjen Black EC600JD) was used as the conductive filler, and the cylinder temperature was changed from 280 ° C to 260 ° C. Except for the above, in the same manner as in the production of the semi-aromatic polyamide composition (D-1), 68% by mass of the semi-aromatic polyamide (d-8), impact improvement Pellet of conductive semi-aromatic polyamide composition comprising 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus processing stabilizer with respect to 100 parts by mass of 25% by mass and 7% by mass of conductive filler. (Hereinafter, this conductive semi-aromatic polyamide composition is referred to as (D-8)).

Production of semi-aromatic polyamide composition (D-9) In production of semi-aromatic polyamide composition (D-1), semi-aromatic polyamide (d-1) was changed to (d-9), and the cylinder temperature was 280. Except for changing from ℃ to 330 ℃, in the same manner as the production of the semi-aromatic polyamide composition (D-1), the semi-aromatic polyamide (d-9) was 85% by mass and the impact modifier was 15% by mass. A semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer was obtained with respect to 100 parts by weight in total (hereinafter, this semi-aromatic polyamide composition). (Referred to as (D-9)).

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

Production of conductive fluorine-containing polymer (E-2) 100 parts by mass of fluorine-containing polymer (E-1) and 13 parts by mass of carbon black (manufactured by Electrochemical Co., Ltd.) are mixed in advance and biaxial melt kneading. Machine (manufactured by Toshiba Machine Co., Ltd., model: TEM-48S), melt kneaded at a cylinder temperature of 240 ° C. to 300 ° C., and extruded the molten resin in a strand shape. The strand was cooled with water, the strand was cut with a pelletizer, and dried for 10 hours with a drier at 120 ° C. to remove moisture to obtain conductive fluorine-containing polymer pellets (hereinafter referred to as this conductive fluorine-containing heavy polymer). The coalescence is referred to as (E-2).)

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

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

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

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

Production of fluorinated polymer (E-7) In the production of fluorinated polymer (E-5), 5-norbornene-2,3-dicarboxylic anhydride (NAH) 0.3 mass% 1,3- 7.6 kg of the fluorinated polymer in the same manner as the production of the fluorinated polymer (E-5) except that the dichloro-1,1,2,2,3-pentafluoropropane solution was not charged. Got.
The composition of the fluorine-containing polymer is TFE-based polymer units / PPVE-based polymer units / HFP-based polymer units = 91.5 / 1.5 / 7.0 (mol%), and the melting point is 257 ° C. Met. This granulated product was melted using an extruder at 300 ° C. for a residence time of 2 minutes to obtain a fluorine-containing polymer pellet (hereinafter, this fluorine-containing polymer is referred to as (E-7)). ).

Production of fluorinated polymer (E-8) 51.5 kg of demineralized pure water was charged in a jacketed stirring polymerization tank capable of containing 174 kg of water, the interior space was sufficiently replaced with pure nitrogen gas, and nitrogen gas was then added. Was eliminated in vacuo. Next, 40.6 kg of octafluorocyclobutane, 1.6 kg of chlorotrifluoroethylene (CTFE), 4.5 kg of tetrafluoroethylene (TFE), and 2.8 kg of perfluoro (propyl vinyl ether) (PPVE) were injected. 0.090 kg of n-propyl alcohol was added as a chain transfer agent, the temperature was adjusted to 35 ° C., and stirring was started. To this, 0.44 kg of 50% by weight methanol solution of di-n-propyl peroxydicarbonate was added as a polymerization initiator to initiate polymerization. During the polymerization, a mixed monomer prepared to have the same composition as the desired copolymer composition is polymerized while being additionally charged so that the pressure in the tank is maintained at 0.66 MPa, and then the residual gas in the tank is exhausted. The produced polymer was taken out, washed with demineralized pure water, and dried to obtain 30.5 kg of a granular powder fluorine-containing polymer.
The composition of the fluoropolymer is 24.4 / 73.1 / 2.5 in terms of the molar ratio of polymerized units based on CTFE / polymerized units based on TFE / polymerized units based on PPVE. The number of carbonate end groups derived from the initiator was 170. The melting point was 241 ° C. This granulated product was melted at 290 ° C. and a residence time of 2 minutes using an extruder to obtain pellets of a fluorine-containing polymer (hereinafter, this fluorine-containing polymer is referred to as (E-8)). ).

Production of conductive fluorine-containing polymer (E-9) In production of conductive fluorine-containing polymer (E-6), fluorine-containing polymer (E-5) was changed to (E-8). Obtained the conductive fluorine-containing polymer pellets in the same manner as in the production of the conductive fluorine-containing polymer (E-6) (hereinafter, this conductive fluorine-containing polymer (E- 9).)

Production of fluorinated polymer (E-10) In production of fluorinated polymer (E-8), fluorinated heavy polymer was used except that a 50 mass% di-n-propyl peroxydicarbonate methanol solution was not charged. 29.8 kg of a fluorine-containing polymer was obtained in the same manner as in the production of the combined product (E-8).
The composition of the fluorine-containing polymer is 24.4 / 73.1 / 2.5 in terms of the molar ratio of polymerized units based on CTFE / polymerized units based on TFE / polymerized units based on PPVE, and the melting point is 241 ° C. there were. This granulated material was melted at 290 ° C. and a residence time of 2 minutes using an extruder to obtain a fluorine-containing polymer pellet (hereinafter, this fluorine-containing polymer is referred to as (E-10)). ).

Example 1
Using the polyamide 12 composition (A-1), polyamide 6/66/12 composition (B-1), EVOH (C-1), and semi-aromatic polyamide composition (D-1) shown above (A-1) is extrusion temperature 250 ° C., (B-1) is extrusion temperature 260 ° C., and (C-1) is extrusion temperature in a 4-layer tube molding machine manufactured by Plastic (Plastics Engineering Laboratory Co., Ltd.). 220 ° C. and (D-1) were melted separately at an extrusion temperature of 270 ° C., and the discharged molten resin was joined by an adapter, and formed into a laminated tubular body through a die set at 250 ° C. Subsequently, it is cooled by a sizing die for dimension control and taken up, and the (a) layer (outermost layer) composed of (A-1), the (b) layer (outer layer) composed of (B-1), (C-1 ) (C) layer (intermediate layer) and (D1-1) layer (innermost layer), 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 at 0.65 / 0.10 / 0.10 / 0.15 mm was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 2
In Example 1, except that the polyamide 12 composition (A-1) was changed to the polyamide 610 composition (A-4) and the extrusion temperature of (A-4) was changed to 260 ° C., the same as in Example 1. By the method, the laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 3
In Example 1, the polyamide 12 composition (A-1) was changed to the polyamide 612 composition (A-5), and the extrusion temperature of (A-5) was changed to 260 ° C. By the method, the laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 4
In Example 1, except that the polyamide 6/66/12 composition (B-1) was changed to (B-2), a laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 1. Obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 5
In Example 1, except that the polyamide 6/66/12 composition (B-1) was changed to (B-3), a laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 1. Obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 6
In Example 1, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 1 except having changed the semi-aromatic polyamide composition (D-1) into (D-2). . The physical property measurement results of the laminated tube are shown in Table 1.

Example 7
In Example 1, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 1 except having changed the semi-aromatic polyamide composition (D-1) into (D-3). . The physical property measurement results of the laminated tube are shown in Table 1.

Example 8
In Example 1, except that the semiaromatic polyamide composition (D-1) was changed to (D-4), the extrusion temperature of (D-4) was changed to 260 ° C., and the die temperature was changed to 240 ° C. 1 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1.

Example 9
In Example 1, except that the semi-aromatic polyamide composition (D-1) was changed to (D-5), the extrusion temperature of (D-5) was changed to 250 ° C, and the die temperature was changed to 230 ° C. 1 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1.

Example 10
In Example 1, except that the semi-aromatic polyamide composition (D-1) was changed to (D-6), the extrusion temperature of (D-6) was changed to 230 ° C, and the die temperature was changed to 210 ° C. 1 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1.

Example 11
In Example 1, the laminated tube of the layer structure shown in Table 2 was obtained by the method similar to Example 1 except having changed the semi-aromatic polyamide composition (D-1) into (D-7). . Table 2 shows the physical property measurement results of the laminated tube.

Example 12
In Example 1, except that the semiaromatic polyamide composition (D-1) was changed to the conductive semiaromatic polyamide composition (D-8) and the extrusion temperature of (D-8) was changed to 260 ° C, A laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 1. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 13
Polyamide 12 composition (A-1), polyamide 6/66/12 composition (B-1), EVOH (C-1), semi-aromatic polyamide composition (D-6), and conductive half Using aromatic polyamide composition (D-8), Plabor (manufactured by Plastics Engineering Laboratory Co., Ltd.) 5-layer tube molding machine, (A-1) extrusion temperature 250 ° C., (B-1) Was melted separately at an extrusion temperature of 260 ° C., (C-1) at an extrusion temperature of 220 ° C., (D-5) at an extrusion temperature of 240 ° C., and (D-6) at an extrusion temperature of 260 ° C. Were joined by an adapter, and formed into a laminated tubular body through a die set at 250 ° C. Subsequently, it is cooled by a sizing die for dimension control and taken up, and the (a) layer (outermost layer) composed of (A-1), the (b) layer (outer layer) composed of (B-1), (C-1 (C) layer (intermediate layer) consisting of (D), (d) layer (inner layer) consisting of (D-6), and (d ') layer (innermost layer) consisting of (D-8). (A) / (b) / (c) / (d) / (d ′) = 0.60 / 0.10 / 0.10 / 0.10 / 0.10 mm, laminated tube having an inner diameter of 6 mm and an outer diameter of 8 mm Got. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

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

Comparative Example 2
In Example 1, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 1 except not using a semi-aromatic polyamide composition (D-1). The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 3
In Example 1, the layer structure shown in Table 1 is the same as in Example 1 except that the polyamide 12 composition (A-1) and the polyamide 6/66/12 composition (B-1) are not used. A laminated tube was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 4
In Example 1, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 1 except not using a polyamide 6/66/12 composition (B-1). The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 5
In Example 1, except that the polyamide 6/66/12 composition (B-1) was changed to (B-4), a laminated tube having a layer structure shown in Table 1 was prepared in the same manner as in Example 1. Obtained. The physical property measurement results of the laminated tube are shown in Table 1.

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

Comparative Example 7
In Example 1, except that the semi-aromatic polyamide composition (D-1) was changed to (D-9), the extrusion temperature of (D-9) was changed to 330 ° C, and the die temperature was changed to 330 ° C. 1 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 8
In Example 1, the semi-aromatic polyamide composition (D-1) was changed to the polyamide 12 composition (A-2), and the extrusion temperature of (A-2) was changed to 250 ° C. A laminated tube having the layer configuration shown in Table 1 was obtained in the same manner. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 9
In Example 1, except that the semi-aromatic polyamide composition (D-1) was changed to the conductive polyamide 12 composition (A-3) and the extrusion temperature of (A-3) was changed to 270 ° C. 1 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

As is clear from Table 1, the laminated tube of Comparative Example 1 that does not have a layer containing a saponified ethylene / vinyl acetate copolymer or a semi-aromatic polyamide composition as defined in the present invention is The laminated tube of Comparative Example 2 is inferior in preventing property, does not have a layer containing the semi-aromatic polyamide composition defined in the present invention, and has a layer containing a saponified ethylene / vinyl acetate copolymer as the innermost layer. The chemical solution permeation-preventing property was poor due to absorption of polar molecules. The laminated tube of Comparative Example 3 which did not have a layer containing an aliphatic polyamide as defined in the present invention, a polyamide 6 composition or a layer containing a polyamide 6/66/12 composition was inferior in low-temperature impact resistance. The laminated tube of Comparative Example 4 which does not have a layer containing the polyamide 6/66/12 composition defined in the present invention was inferior in interlayer adhesion. The laminated tubes of Comparative Examples 5 and 6 having a layer containing a polyamide 6/66/12 composition or a polyamide 6/12 composition other than those specified in the present invention were inferior in interlayer adhesion after heat treatment. The laminated tube of Comparative Example 7 having a layer containing a semi-aromatic polyamide composition other than specified in the present invention was inferior in melt stability, molding stability and interlayer adhesion. The laminated tube of Comparative Examples 8 and 9 having no layer containing the semi-aromatic polyamide composition defined in the present invention and having a layer containing the polyamide 12 composition as the innermost layer is resistant to the dissolution of monomers and oligomers. It was inferior to.
On the other hand, the laminated tubes of Examples 1 to 13 defined in the present invention have low-temperature impact resistance, chemical solution permeation prevention properties, particularly permeation resistance properties against low-concentration alcohol-containing gasoline, interlayer adhesion properties and durability, monomers, It is clear that the oligomer has good properties such as dissolution resistance, melt stability and molding stability.

Example 14
Polyamide 12 composition (A-1), polyamide 6/66/12 composition (B-1), EVOH (C-1), semi-aromatic polyamide composition (D-1), and fluorine-containing system shown above Using the polymer (E-1), in a Plabor (Plastics Engineering Laboratory Co., Ltd.) 5-layer tube molding machine, (A-1) is an extrusion temperature of 250 ° C., and (B-1) is an extrusion temperature. 260 ° C, (C-1) is extruded at 220 ° C, (D-1) is extruded at 260 ° C, and (E-1) is melted at 300 ° C separately. They were merged and passed through a die set at 280 ° C. to form a laminated tubular body. Subsequently, it is cooled by a sizing die for dimension control and taken up, and the (a) layer (outermost layer) composed of (A-1), the (b) layer (outer layer) composed of (B-1), (C-1 (C) layer (intermediate layer) consisting of (D), (d) layer (inner layer) consisting of (D-1), and (e) layer (innermost layer) consisting of (E-1). a) / (b) / (c) / (d) / (e) = 0.60 / 0.10 / 0.10 / 0.10 / 0.10 mm and a laminated tube having an inner diameter of 6 mm and an outer diameter of 8 mm is obtained. It was. Table 2 shows the physical property measurement results of the laminated tube.

Example 15
In Example 14, 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, the laminated tube of the layer structure shown in Table 2 was obtained. Table 2 shows the physical property measurement results of the laminated tube.

Example 16
In Example 14, the polyamide 12 composition (A-2) was changed to the polyamide 612 composition (A-5), and the extrusion temperature of (A-5) was changed to 260 ° C. By the method, the laminated tube of the layer structure shown in Table 2 was obtained. Table 2 shows the physical property measurement results of the laminated tube.

Example 17
In Example 14, except that the polyamide 6/66/12 composition (B-1) was changed to (B-2), a laminated tube having the layer structure shown in Table 2 was prepared in the same manner as in Example 14. Obtained. Table 2 shows the physical property measurement results of the laminated tube.

Example 18
In Example 14, except that the polyamide 6/66/12 composition (B-1) was changed to (B-3), a laminated tube having the layer structure shown in Table 2 was prepared in the same manner as in Example 14. Obtained. Table 2 shows the physical property measurement results of the laminated tube.

Example 19
In Example 14, the laminated tube of the layer structure shown in Table 2 was obtained by the same method as Example 14 except having changed the semi-aromatic polyamide composition (D-1) into (D-2). . Table 2 shows the physical property measurement results of the laminated tube.

Example 20
In Example 14, the laminated tube of the layer structure shown in Table 2 was obtained by the same method as Example 14 except having changed the semi-aromatic polyamide composition (D-1) into (D-3). . Table 2 shows the physical property measurement results of the laminated tube.

Example 21
In Example 14, the semi-aromatic polyamide composition (D-1) was changed to (D-4), and the extrusion temperature of (D-4) was changed to 260 ° C. Thus, a laminated tube having a layer structure shown in Table 2 was obtained. Table 2 shows the physical property measurement results of the laminated tube.

Example 22
In Example 14, the semi-aromatic polyamide composition (D-1) was changed to (D-5), and the extrusion temperature of (D-5) was changed to 250 ° C. Thus, a laminated tube having a layer structure shown in Table 2 was obtained. Table 2 shows the physical property measurement results of the laminated tube.

Example 23
In Example 14, the semi-aromatic polyamide composition (D-1) was changed to (D-6), and the extrusion temperature of (D-6) was changed to 230 ° C. Thus, a laminated tube having a layer structure shown in Table 2 was obtained. Table 2 shows the physical property measurement results of the laminated tube.

Example 24
A laminated tube having the layer structure shown in Table 2 was obtained in the same manner as in Example 14 except that the semiaromatic polyamide composition (D-1) was changed to (D-7) in Example 14. . Table 2 shows the physical property measurement results of the laminated tube.

Example 25
In Example 14, the fluorine-containing polymer (E-1) was changed to the conductive fluorine-containing polymer (E-2), the extrusion temperature of (E-2) was changed to 310 ° C, and the die temperature was changed to 300 ° C. A laminated tube having the layer structure shown in Table 2 was obtained in the same manner as in Example 14 except that. Table 2 shows the physical property measurement results of the laminated tube. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 26
In Example 14, the fluorine-containing polymer (E-1) was changed to (E-5), and the extrusion temperature of (E-5) was changed to 310 ° C., in the same manner as in Example 14. The laminated tube of the layer structure shown in Table 2 was obtained. Table 2 shows the physical property measurement results of the laminated tube.

Example 27
In Example 14, the fluorine-containing polymer (E-1) was changed to the conductive fluorine-containing polymer (E-6), the extrusion temperature of (E-6) was changed to 320 ° C, and the die temperature was changed to 300 ° C. A laminated tube having the layer structure shown in Table 2 was obtained in the same manner as in Example 14 except that. Table 2 shows the physical property measurement results of the laminated tube. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 28
In Example 14, the fluoropolymer (E-1) was changed to (E-8), and the extrusion temperature of (E-8) was changed to 290 ° C., in the same manner as in Example 14. The laminated tube of the layer structure shown in Table 2 was obtained. Table 2 shows the physical property measurement results of the laminated tube.

Example 29
In Example 14, the fluorine-containing polymer (E-1) was changed to the conductive fluorine-containing polymer (E-9), and the extrusion temperature of (E-9) was changed to 310 ° C and the die temperature was changed to 300 ° C. A laminated tube having the layer structure shown in Table 2 was obtained in the same manner as in Example 14 except that. Table 2 shows the physical property measurement results of the laminated tube. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Comparative Example 10
In Example 14, except that EVOH (C-1), semi-aromatic polyamide composition (D-1), and fluorine-containing polymer (E-1) were not used, the same method as in Example 14, A laminated tube having the layer structure shown in Table 2 was obtained. Table 2 shows the physical property measurement results of the laminated tube.

Comparative Example 11
In Example 14, the laminated tube of the layer structure shown in Table 2 was obtained by the method similar to Example 14 except not using a semi-aromatic polyamide composition (D-1). Table 2 shows the physical property measurement results of the laminated tube.

Comparative Example 12
In Example 14, the layer structure shown in Table 2 was used in the same manner as in Example 14 except that the polyamide 12 composition (A-1) and the polyamide 6/66/12 composition (B-1) were not used. A laminated tube was obtained. Table 2 shows the physical property measurement results of the laminated tube.

Comparative Example 13
In Example 14, the laminated tube of the layer structure shown in Table 2 was obtained by the method similar to Example 14 except not using a polyamide 6/66/12 composition (B-1). Table 2 shows the physical property measurement results of the laminated tube.

Comparative Example 14
In Example 14, except that the polyamide 6/66/12 composition (B-1) was changed to (B-4), a laminated tube having the layer structure shown in Table 2 was prepared in the same manner as in Example 14. Obtained. Table 2 shows the physical property measurement results of the laminated tube.

Comparative Example 15
In Example 14, it shows in Table 2 by the method similar to Example 14 except having changed the polyamide 6/66/12 composition (B-1) into the polyamide 6/12 composition (B-5). A laminated tube having a layer structure was obtained. Table 2 shows the physical property measurement results of the laminated tube.

Comparative Example 16
In Example 14, the semi-aromatic polyamide composition (D-1) was changed to (D-9), and the extrusion temperature of (D-9) was changed to 330 ° C and the die temperature was changed to 330 ° C. 14 was used to obtain a laminated tube having the layer structure shown in Table 2. Table 2 shows the physical property measurement results of the laminated tube.

Comparative Example 17
In Comparative Example 15, a laminated tube having a layer structure shown in Table 2 was obtained in the same manner as in Comparative Example 15 except that the fluorinated polymer (E-1) was changed to (E-3). Table 2 shows the physical property measurement results of the laminated tube.

Comparative Example 18
In Comparative Example 15, the fluorine-containing polymer (E-1) was changed to the conductive fluorine-containing polymer (E-4), the extrusion temperature of (E-4) was changed to 310 ° C, and the die temperature was changed to 300 ° C. A laminated tube having the layer structure shown in Table 2 was obtained in the same manner as in Comparative Example 15 except that. Table 2 shows the physical property measurement results of the laminated tube. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Comparative Example 19
In Comparative Example 15, the same method as in Comparative Example 15 was used except that the fluorine-containing polymer (E-1) was changed to (E-7) and the extrusion temperature of (E-7) was changed to 310 ° C. The laminated tube of the layer structure shown in Table 2 was obtained. Table 2 shows the physical property measurement results of the laminated tube.

Comparative Example 20
In Comparative Example 15, a laminated tube having the layer structure shown in Table 2 was obtained in the same manner as in Comparative Example 15 except that the fluorinated polymer (E-1) was changed to (E-10). Table 2 shows the physical property measurement results of the laminated tube.

  As is apparent from Table 2, the present invention does not have a layer containing a saponified ethylene / vinyl acetate copolymer, a layer containing a semi-aromatic polyamide composition, and a layer containing a fluorinated polymer. The laminated tube of Comparative Example 10 is inferior in permeation resistance to gasoline containing a high concentration of alcohol, and the laminated tube of Comparative Example 11 having no layer containing the semi-aromatic polyamide composition defined in the present invention is melt stable. And molding stability was poor. The laminated tube of Comparative Example 12 which does not have a layer containing an aliphatic polyamide specified in the present invention or a layer containing a polyamide 6/66/12 composition is inferior in low-temperature impact resistance, and is specified in the present invention. The laminated tube of Comparative Example 13 having no layer containing the polyamide 6/66/12 composition was inferior in interlayer adhesion. The laminated tubes of Comparative Examples 14 and 15 having a layer containing a polyamide 6/66/12 composition or a polyamide 6/12 composition other than those specified in the present invention were inferior in interlayer adhesion after heat treatment. The laminated tube of Comparative Example 16 having a layer containing a semi-aromatic polyamide composition other than those specified in the present invention was inferior in melt stability and molding stability. The laminated tubes of Comparative Examples 17 to 20 having a layer containing a polyamide 6/66/12 composition other than those specified in the present invention and a layer containing a fluorine-containing polymer were inferior in interlayer adhesion.

  On the other hand, the laminated tubes of Examples 14 to 29 defined in the present invention have low temperature impact resistance, chemical solution permeation prevention properties, particularly permeation resistance properties for high-concentration alcohol-containing gasoline, interlayer adhesion properties and durability thereof, monomers, It is clear that the oligomer has good properties such as dissolution resistance, melt stability and molding stability.

Claims (12)

A laminated tube of four or more layers including (a) layer, (b) layer, (c) layer, and (d) layer,
At least one set of the (c) layer and the (d) layer is disposed adjacent to each other;
The layer (a) contains an aliphatic polyamide (A),
The layer (b) includes a polyamide 6/66/12 composition (B),
The layer (c) includes a saponified ethylene / vinyl acetate copolymer (C),
The layer (d) includes a semi-aromatic polyamide composition (D),
The aliphatic polyamide (A) does not include polyamide 6/66/12 (b1),
The polyamide 6/66/12 composition (B) is a polyamide mixture of 50% by mass to 98% by mass, a plasticizer (B1) of 1% by mass to 20% by mass, and an olefin polymer (B2) 1 Containing from 30% to 30% by weight,
The polyamide mixture includes, in the mixture, polyamide 6/66/12 (b1) 50% by mass to 100% by mass and polyamide (b2) 0% by mass to 50% by mass,
The polyamide (b2) includes polyhexamethylene sebamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene decamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), polydecam It is at least one polyamide selected from the group consisting of methylene decanamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), and polydodecamethylene dodecamide (polyamide 1212).
The olefin polymer (B2) has a flexural modulus measured according to ISO 178 of 500 MPa or less,
The semi-aromatic polyamide composition (D) includes a semi-aromatic polyamide (d),
The semi-aromatic polyamide (d) is a diamine unit containing 60 mol% or more of m-xylylenediamine units with respect to all diamine units, and a fat having 6 to 10 carbon atoms with respect to all dicarboxylic acid units. Laminated tube having a dicarboxylic acid unit containing 60 mol% or more of a group dicarboxylic acid unit.   The aliphatic polyamide (A) includes polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene decanamide (polyamide 610), polyhexamethylene dodeca At least one homopolymer selected from the group consisting of amide (polyamide 612), polydecamethylene decanamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), and polydodecamethylene dodecamide (polyamide 1212), The laminated tube according to claim 1, which is a copolymer using several kinds of raw material monomers forming these.   The polyamide 6/66/12 (b1) has a mass ratio of a total unit of caproamide units and hexamethylene adipamide units to a dodecanamide unit of 81:19 or more and 95: 5. Laminated tube.   The ethylene content of the saponified ethylene / vinyl acetate copolymer (C) is 15 mol% or more and 60 mol% or less, and the saponification degree is 90 mol% or more. Laminated tube.   The aliphatic dicarboxylic acid unit having 6 to 10 carbon atoms in the semi-aromatic polyamide (d) is a unit derived from adipic acid and / or sebacic acid. The laminated tube as described. The layer (a) is disposed on the outermost layer,
The laminated tube according to any one of claims 1 to 5, wherein the (c) layer is disposed between the (a) layer and the (d) layer.   The laminated tube according to any one of claims 1 to 6, wherein at least one pair of the (b) layer and the (c) layer is disposed adjacent to each other. The (d) layer is disposed in the innermost layer,
The laminated tube according to any one of claims 1 to 7, wherein the semi-aromatic polyamide composition (D) further contains a conductive filler. (E) further comprising a layer;
The layer (e) includes a fluorine-containing polymer (E),
In the fluorine-containing polymer (E), a functional group having reactivity with an amino group is introduced into the molecular chain,
The laminated tube according to any one of claims 1 to 7, wherein at least one pair of the (d) layer and the (e) layer is disposed adjacent to each other.   The laminated tube according to claim 9, wherein the layer containing the fluorine-containing polymer composition containing the conductive filler is disposed in the innermost layer.   The laminated tube according to any one of claims 1 to 10, which is produced by a coextrusion molding method.   The laminated tube according to any one of claims 1 to 11, which is used as a fuel tube.