JP2014240148A - Electroconductive laminate tube - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminate tube not only excellent in terms of thermal stability at the time of a molding work, low-temperature impact resistance, degraded fuel resistance, chemical liquid transmission prevention, and interlayer adhesiveness but also electroconductive.SOLUTION: The provided electroconductive laminate tube consists of at least three layers including: a layer consisting of an aliphatic polyamide; a layer consisting of a semi-aromatic polyamide having a specified structure consisting of diamine units including at least 80% of C9-13 aliphatic diamine units and dicarboxylic acid units including at least 80% of terephthalic acid units and/or naphthalenedicarboxylic acid units; and a layer consisting of an electroconductive semi-aromatic polyamide copolymer composition consisting of: a semi-aromatic polyamide copolymer having a specified structure; and an electroconductive filler.

Description

  The present invention relates to a layer comprising an aliphatic polyamide, a layer comprising a semi-aromatic polyamide having a specific structure, and a conductive semi-aromatic polyamide copolymer comprising a semi-aromatic polyamide copolymer having a specific structure and a conductive filler. A conductive laminated tube comprising a polymer composition, wherein the laminated tube has excellent heat stability during molding, low temperature impact resistance, deteriorated fuel resistance, chemical liquid permeation prevention and interlayer adhesion, and has conductivity. About.

  In the old days of automobile-related fuel tubes, hoses, tanks, etc., in response to the problem of rusting caused by antifreezing agents on roads, prevention of global warming, and energy saving, the main material is rust prevention from metal Substitution with lightweight resin with excellent properties is progressing. For example, saturated polyester resins, polyolefin resins, polyamide resins, thermoplastic polyurethane resins, etc. may be mentioned. Therefore, the applicable range was limited.

  Further, from the viewpoint of saving gasoline consumption and improving performance, alcohols having a low boiling point such as methanol and ethanol or oxygenated gasoline blended with ethers such as methyl-t-butyl ether (MTBE) are used. . Furthermore, from the viewpoint of preventing environmental pollution, strict exhaust gas regulations are implemented including prevention of leakage into the atmosphere due to diffusion of volatile hydrocarbons through partition walls such as fuel tubes, hoses, and tanks. For such strict regulations, a single-layer molded product using a polyamide-based resin, particularly polyamide 11 or polyamide 12 that is excellent in strength, toughness, chemical resistance, flexibility, etc. The permeation-preventing properties for chemical liquids such as these fuels are not sufficient, and in particular, improvements to the permeation-preventing properties of alcohol-containing gasoline are required.

  As a method for solving this problem, resins having good chemical permeation preventive properties such as saponified ethylene / vinyl acetate copolymer (EVOH), polymetaxylylene adipamide (polyamide MXD6), poly (hexamethylene terephthalamide) / Hexamethylene adipamide) copolymer (polyamide 6T / 66), poly (hexamethylene terephthalamide / hexamethylene isophthalamide / hexamethylene adipamide) copolymer (polyamide 6T / 6I / 66), poly Butylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyphenylene sulfide (PPS), polyvinylidene fluoride (PVDF), ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / tetrafluoro Ethylene / f Safluoropropylene copolymer (EFEP), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / fluoride Vinylidene fluoride copolymer (TFE / HFP / VDF, THV), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer (TFE / HFP / VDF / PAVE), tetrafluoroethylene / Perfluoro (alkyl vinyl ether) copolymer (TFE / PAVE, PFA), tetrafluoroethylene / hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer (TFE / HFP / P) VE), many laminated tubes in which chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer (CTFE / PAVE / TFE, CPT) is arranged have been proposed (see, for example, Patent Document 1) ).

  Among these, a layer made of an aliphatic polyamide and a poly (hexamethylene terephthalamide / hexamethylene adipamide) copolymer (polyamide 6T / 66), poly (hexamethylene terephthalamide / hexamethylene isophthalamide / hexa). A hollow molded body including a layer made of polyterephthalamide (PPA) such as a methylene adipamide) copolymer (polyamide 6T / 6I / 66) and an impact resistance improving material has been proposed (see Patent Document 2). Polyamide 6T / 6I / 66 shown in Examples in the specification is known to have good adhesive strength with polyamide 6, but has been conventionally used as a constituent material of a single-layer tube. For polyamide 11 or polyamide 12, the interlayer adhesion is insufficient and it is difficult to withstand actual use. For this reason, it is necessary to provide an adhesive layer between the layers, resulting in complexity in terms of cost and management.

  On the other hand, when used as a chemical pipe transport tube, etc., static electricity generated by internal friction of the chemical circulating in the pipe or friction with the pipe wall accumulates, and there is a risk of ignition and explosion of the chemical, preventing this It is requested to do. Therefore, a laminated tube in which a layer made of a resin composition containing a conductive filler is disposed in the innermost layer is preferable. However, the material used for the innermost layer of the laminated tube is often a resin that is excellent in resistance to chemicals circulating in the piping and has good chemical solution permeation prevention properties, and contains a conductive filler in the material. The resin composition has a drawback that it is inferior in fluidity and mechanical strength, particularly low temperature impact resistance. In order to improve these, the method of melt-mixing soft polymers including an olefin polymer is proposed (for example, refer patent document 3). However, if the amount of the soft polymer added to the material used for the innermost layer of the laminated tube is large, a decrease in fluidity and chemical liquid permeation prevention is unavoidable. The effect of improving the property is not seen so much. Furthermore, the material used for the innermost layer of the laminated tube is generally higher in molding temperature than aliphatic polyamides such as polyamide 11 or polyamide 12 used during coextrusion, and a conductive filler is added to the material. In the resin composition to be contained, the tube is manufactured at an extremely severe molding temperature in order to ensure fluidity. However, the productivity of the resin composition is reduced due to the inappropriate melt viscosity range. Mechanical strength such as problems, elongation of molded products such as tubes, and low-temperature impact resistance may be insufficient. Also, when tubes are manufactured at extremely severe molding temperatures, soft polymers such as olefin polymers added to the material used for the innermost layer will decompose, foam, and deteriorate. This phenomenon is particularly noticeable when the amount of soft polymer such as olefin polymer added is large. In order to optimize the melt viscosity in a resin composition containing a conductive filler, a semi-aromatic polyamide having a specific terminal amino group concentration, an olefin polymer having a carboxyl group and an acid anhydride group, and a conductive filler In the polyamide resin composition to be contained, a resin composition in which the number of moles of terminal amino groups of the semi-aromatic polyamide and the number of moles of carboxyl groups and acid anhydride groups of the olefin polymer are in a specific range has been proposed ( (See Patent Document 4). However, even in this resin composition, low-temperature impact resistance and resistance to sour gasoline produced by oxidation of gasoline (deterioration fuel resistance) are not yet satisfactory, thermal stability during molding, low-temperature impact resistance, There is a need for the development of a laminated tube having conductivity that balances deterioration resistance fuel resistance and chemical solution permeation prevention at a high level.

US Pat. No. 5,554,425 Special table 2007-502726 JP-A-10-230556 International Patent Publication No. 2012-98840

  The object of the present invention is to solve the above-mentioned problems, and is a laminated tube having excellent electrical stability during molding, low temperature impact resistance, fuel resistance against deterioration, chemical liquid permeation prevention, interlayer adhesion, and conductivity. Is to provide.

  As a result of intensive studies to solve the above problems, the present inventors have found that a layer composed of an aliphatic polyamide, a layer composed of a semi-aromatic polyamide having a specific structure, and a semi-aromatic polyamide having a specific structure. A laminated tube having conductivity comprising a layer made of a conductive semi-aromatic polyamide copolymer composition comprising a copolymer and a conductive filler has thermal stability during molding, low temperature impact resistance, resistance to deterioration fuel, It has been found that the chemical solution permeation preventing property and the interlayer adhesion are excellent.

  That is, the present invention relates to a layer (a) comprising an aliphatic polyamide (A), a diamine unit containing 80 mol% or more of an aliphatic diamine unit having 9 to 13 carbon atoms, (B) layer composed of a semi-aromatic polyamide (B) composed of a dicarboxylic acid unit containing 80 mol% or more of a terephthalic acid unit and / or a naphthalene dicarboxylic acid unit with respect to the acid unit, and the total diamine unit ( c1) 1,9-nonanediamine unit and 2-methyl-1,8-octanediamine unit and (c2) an aliphatic diamine unit having 4 to 6 carbon atoms in an amount of 60 mol% or more, (c1) and (c2) Terephthalic acid unit and / or naphthalene dicarboxyl with respect to the diamine unit having a molar ratio of 40:60 mol% to 80:20 mol% and all dicarboxylic acid units A layer (c) comprising a conductive semi-aromatic polyamide copolymer composition (C) comprising a semi-aromatic polyamide copolymer (C1) containing 60 mol% or more of acid units and a conductive filler (C2); The present invention provides a conductive laminated tube characterized by comprising at least three layers.

The preferable aspect of the electroconductive laminated tube of this invention is shown below. A plurality of preferred embodiments can be combined.
[1] In the semi-aromatic polyamide (B), the aliphatic diamine unit having 9 to 13 carbon atoms is 1,9-nonanediamine and / or 2-methyl-1,8-octanediamine, 1,10-decane. A conductive laminated tube, which is at least one selected from the group consisting of diamines and units derived from 1,12-dodecanediamine.
[2] In the semi-aromatic polyamide copolymer (C1), (c2) an aliphatic diamine unit having 4 to 6 carbon atoms is 1,6-hexanediamine and / or 2-methyl-1,5- A conductive laminated tube characterized by being a unit derived from pentanediamine.
[3] The aliphatic polyamide (A) is polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene decane. From the group consisting of amide (polyamide 610), polyhexamethylene dodecane (polyamide 612), polydecane methylene decanamide (polyamide 1010), polydecamethylene dodecane (polyamide 1012), and polydodecamethylene dodecane (polyamide 1212). A conductive laminated tube, which is at least one homopolymer selected, or a copolymer using several kinds of raw material monomers forming these.
[4] The (a) layer composed of the aliphatic polyamide (A) is disposed in the outermost layer, and the (c) layer composed of the conductive semi-aromatic polyamide copolymer composition (C) is disposed in the innermost layer. Conductive laminated tube characterized by
[5] A conductive laminated tube manufactured by coextrusion molding.

  The conductive laminated tube of the present invention has a layer made of an aliphatic polyamide, a layer made of a semi-aromatic polyamide having a specific structure, and a conductive material made of a semi-aromatic polyamide copolymer having a specific structure and a conductive filler. It includes a layer made of a semi-aromatic polyamide copolymer composition, and is excellent in thermal stability during molding, low temperature impact resistance, degradation fuel resistance, chemical liquid permeation resistance, and interlayer adhesion, and has electrical conductivity. Therefore, starting with machine parts such as automobile parts, internal combustion engines, power tool housings, etc., industrial materials, industrial materials, electrical / electronic parts, medical care, food, household / office supplies, building materials related parts, furniture parts, household goods It is useful for various uses. Particularly suitable as a chemical solution transport tube, suppresses alcohol-mixed hydrocarbons that permeate and evaporate from the tube partition, accumulates static electricity generated by internal friction of the chemical solution circulating in the piping or friction with the tube wall, and chemical solution It is possible to prevent ignition and explosion.

  The aliphatic polyamide (A) used in the present invention has an amide bond (—CONH—) in the main chain and is melted using lactam, aminocarboxylic acid, or aliphatic diamine and aliphatic dicarboxylic acid as raw materials. It can be obtained by polymerization or copolymerization by a known method such as polymerization, solution polymerization or solid phase polymerization.

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

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

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

  Examples of the aliphatic polyamide (A) include polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyethylene adipamide (polyamide 26), polytetramethylene succinamide (polyamide) 44), polytetramethylene glutamide (polyamide 45), polytetramethylene adipamide (polyamide 46), polytetramethylene suberamide (polyamide 48), polytetramethylene azelamide (polyamide 49), polytetramethylene sebacamide (Polyamide 410), polytetramethylene dodecamide (polyamide 412), polypentamethylene succinamide (polyamide 54), polypentamethylene glutamide (polyamide 55), polypentamethylene adipamide (polyamide) 6), polypentamethylene suberamide (polyamide 58), polypentamethylene azelamide (polyamide 59), polypentamethylene sebamide (polyamide 510), polypentamethylene dodecamide (polyamide 512), polyhexamethylene succinamide (Polyamide 64), polyhexamethylene glutamide (polyamide 65), polyhexamethylene adipamide (polyamide 66), polyhexamethylene suberamide (polyamide 68), polyhexamethylene azelamide (polyamide 69), polyhexamethylene Bacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polyhexamethylene tetradecanamide (polyamide 614), polyhexamethylene hexadecanamide (polyamide 616), polyhexame Lenoctadecamide (Polyamide 618), Polynonamethylene adipamide (Polyamide 96), Polynonamethylene suberamide (Polyamide 98), Polynonamethylene azelamide (Polyamide 99), Polynonamethylene sebacamide (Polyamide 910) , Polynonamethylene dodecamide (polyamide 912), polydecamethylene adipamide (polyamide 106), polydecamethylene suberamide (polyamide 108), polydecamethylene azelamide (polyamide 109), polydecamethylene sebacamide (polyamide) 1010), polydecamethylene dodecamide (polyamide 1012), polydodecamethylene adipamide (polyamide 126), polydodecamethylene suberamide (polyamide 128), polydodecamethylene azelamide (polyamide 129) And homopolymers such as polydodecamethylene sebacamide (polyamide 1210) and polydodecamethylene dodecamide (polyamide 1212), and copolymers using several raw material monomers forming these.

  Among these, polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene azelamide (polyamide 69), poly Hexamethylene sebamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene dodecamide (polyamide 912), polydecamethylene sebacamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012) Polydodecamethylene dodecamide (polyamide 1212) and a copolymer using several kinds of raw material monomers forming these are preferable, such as polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydode Amide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene decanamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecamethylene decanamide (polyamide 1010), polydecamethylene There are at least one homopolymer selected from the group consisting of dodecamide (polyamide 1012) and polydodecamethylene dodecamide (polyamide 1212), or a copolymer using several raw material monomers forming these. preferable.

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

  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 is the mechanical property of the resulting conductive laminated tube. And from the viewpoint of securing the desirable moldability of the conductive 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. The following is more preferable.

  In the aliphatic polyamide (A), when the terminal amino group concentration per 1 g of the polyamide is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), [A]> [B ] +5 (hereinafter sometimes referred to as terminal-modified aliphatic polyamide) is preferable in view of interlayer adhesion with the semi-aromatic polyamide (B) described later, and [A]> [B] +10. It is more preferable that [A]> [B] +15. Furthermore, from the viewpoint of the melt stability of the polyamide and the suppression of the generation of gel-like 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. Thus, amines can be added at any stage during polymerization, or at any stage after melt kneading after polymerization, but when considering the interlayer adhesion of the conductive laminated tube, at the stage during polymerization. It is preferable to add.
Examples of the amines include monoamines, diamines, triamines, and polyamines. In addition to amines, carboxylic acids such as monocarboxylic acids, dicarboxylic acids, and tricarboxylic acids may be added as necessary as long as they do not deviate from the range of the above-mentioned end group concentration conditions. These amines and carboxylic acids may be added simultaneously or separately. Moreover, 1 type (s) or 2 or more types can be used for the amines and carboxylic acids illustrated below.

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

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

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

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

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

  Examples of the polyalkyleneimine include one or two alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, 1,1-dimethylethyleneimine Examples include homopolymers and copolymers obtained by polymerizing more than one species by conventional methods. 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 or less, more preferably 8 or more and 1,500 or less, and further preferably 11 or more and 500 or less. preferable. The number average molecular weight of the polyalkyleneimine is preferably 100 or more and 20,000 or less, more preferably 200 or more and 10,000 or less, and further preferably 500 or more and 8,000 or less.

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

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

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

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

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

  Other polyamide resins include polymetaxylylene adipamide (polyamide MXD6), polymetaxylylene veramide (polyamide MXD8), polymetaxylylene azelamide (polyamide MXD9), polymetaxylylene sebacamide (polyamide MXD10). , Polymetaxylylene decamide (polyamide MXD12), polymetaxylylene terephthalamide (polyamide MXDT), polymetaxylylene isophthalamide (polyamide MXDI), polymetaxylylene hexahydroterephthalamide (polyamide MXDT (H)), polymer Taxylylene naphthalamide (polyamide MXDN), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylene beramide (polyamide PXD8), polyparaxylylene azelamide Polyamide PXD9), polyparaxylylene sebacamide (polyamide PXD10), polyparaxylylene dodecamide (polyamide PXD12), polyparaxylylene terephthalamide (polyamide PXDT), polyparaxylylene isophthalamide (polyamide PXDI) , Polyparaxylylene hexahydroterephthalamide (polyamide PXDT (H)), polyparaxylylene naphthalamide (polyamide PXDN), polyparaphenylene terephthalamide (PPTA), polyparaphenylene isophthalamide (PPIA), poly Metaphenylene terephthalamide (PMTA), polymetaphenylene isophthalamide (PMIA), poly (2,6-naphthalenediethylene adipamide) (polyamide 2,6-BAN6), poly (2,6-naphthalenedimethyle Suberamide) (polyamide 2,6-BAN8), poly (2,6-naphthalene dimethylene azelamide) (polyamide 2,6-BAN9), poly (2,6-naphthalene dimethylene sebacamide) (polyamide 2,6 -BAN10), poly (2,6-naphthalene dimethylene dodecamide) (polyamide 2,6-BAN12), poly (2,6-naphthalene dimethylene terephthalamide) (polyamide 2,6-BANT), poly (2 , 6-Naphthalenedylene methylene isophthalamide) (polyamide 2,6-BANI), poly (2,6-naphthalenediethylene hexahydroterephthalamide) (polyamide 2,6-BANT (H)), poly (2, 6-naphthalene dimethylene naphthalamide) (polyamide 2,6-BANN), poly (1,3-cyclohexanedimethylene) Dipamide) (polyamide 1,3-BAC6), poly (1,3-cyclohexanedimethylenesberamide (polyamide 1,3-BAC8), poly (1,3-cyclohexanedimethylene azelamide) (polyamide 1,3-BAC9) ), Poly (1,3-cyclohexanedimethylene sebacamide) (polyamide 1,3-BAC10), poly (1,3-cyclohexanedimethylene dodecamide) (polyamide 1,3-BAC12), poly (1,3 -Cyclohexanedimethylene terephthalamide) (polyamide 1,3-BACT), poly (1,3-cyclohexanedimethylene isophthalamide) (polyamide 1,3-BACI), poly (1,3-cyclohexanedimethylene hexahydro Terephthalamide) (polyamide 1,3-BACT (H)), poly (1,3-sic Hexane dimethylene naphthalamide) (polyamide 1,3-BACN), poly (1,4-cyclohexanedimethylene adipamide) (polyamide 1,4-BAC6), poly (1,4-cyclohexanedimethylene suberamide) ( Polyamide 1,4-BAC8), poly (1,4-cyclohexanedimethylene azelamide) (polyamide 1,4-BAC9), poly (1,4-cyclohexanedimethylene sebacamide) (polyamide 1,4-BAC10) , Poly (1,4-cyclohexanedimethylene dodecamide) (polyamide 1,4-BAC12), poly (1,4-cyclohexanedimethylene terephthalamide) (polyamide 1,4-BACT), poly (1,4- Cyclohexanedimethylene isophthalamide) (polyamide 1,4-BACI), poly (1,4- Chlorohexane dimethylene hexahydroterephthalamide) (polyamide 1,4-BACT (H)), poly (1,4-cyclohexanedimethylene naphthalamide) (polyamide 1,4-BACN), poly (4,4′- Methylenebiscyclohexylene adipamide) (polyamide PACM6), poly (4,4′-methylenebiscyclohexylene suberamide) (polyamide PACM8), poly (4,4′-methylenebiscyclohexylene azelamide) (polyamide PACM9) , Poly (4,4′-methylenebiscyclohexylene sebacamide) (polyamide PACM10), poly (4,4′-methylenebiscyclohexylene dodecamide) (polyamide PACM12), poly (4,4′-methylenebiscyclohexyl) Silenetetradecamide) (Polyamide PACM) 14), poly (4,4′-methylenebiscyclohexylenehexadecamide) (polyamide PACM16), poly (4,4′-methylenebiscyclohexyleneoctadecamide) (polyamide PACM18), poly (4,4′- Methylenebiscyclohexylene terephthalamide) (polyamide PACMT), poly (4,4′-methylenebiscyclohexylene isophthalamide) (polyamide PACMI), poly (4,4′-methylenebiscyclohexylene hexahydroterephthalamide) (Polyamide PACMT (H)), poly (4,4′-methylenebiscyclohexylenenaphthalamide) (polyamide PACMN), poly (4,4′-methylenebis (2-methyl-cyclohexylene) adipamide) (polyamide MACM6), Poly (4,4'-methylene (2-methyl-cyclohexylene) suberamide) (polyamide MACM8), poly (4,4′-methylenebis (2-methyl-cyclohexylene) azeramide) (polyamide MACM9), poly (4,4′-methylenebis (2- Methyl-cyclohexylene) sebacamide) (polyamide MACM10), poly (4,4′-methylenebis (2-methyl-cyclohexylene) dodecamide) (polyamide MACM12), poly (4,4′-methylenebis (2-methyl-cyclohexylene) ) Tetradecamide) (polyamide MACM14), poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexadecamide) (polyamide MACM16), poly (4,4′-methylenebis (2-methyl-cyclohexylene) octadecamide) ( Polyami MACM18), poly (4,4′-methylenebis (2-methyl-cyclohexylene) terephthalamide) (polyamide MACMT), poly (4,4′-methylenebis (2-methyl-cyclohexylene) isophthalamide) (polyamide MACMI), poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexahydroterephthalamide) (polyamide MACMT (H)), poly (4,4′-methylenebis (2-methyl-cyclohexylene) naphthalamide) (polyamide MACMN ), Poly (4,4′-propylene biscyclohexylene adipamide) (polyamide PACP6), poly (4,4′-propylene biscyclohexylene suberamide) (polyamide PACP8), poly (4,4′-propylene bis) Cyclohexylene azeamide) (Polyamide PACP9), poly (4,4′-propylene biscyclohexylene sebacamide) (polyamide PACP10), poly (4,4′-propylene biscyclohexylene dodecamide) (polyamide PACP12), poly (4,4 ′ -Propylene biscyclohexylene tetradecanamide (polyamide PACP14), poly (4,4'-propylene biscyclohexylene hexadecanamide) (polyamide PACP16), poly (4,4'-propylene biscyclohexylene octadecanamide) ( Polyamide PACP18), poly (4,4′-propylene biscyclohexylene terephthalamide) (polyamide PACPT), poly (4,4′-propylene biscyclohexylene isophthalamide) (polyamide PACPI), poly (4,4 ′ -Propi Biscyclohexylene hexahydroterephthalamide) (polyamide PACPT (H)), poly (4,4′-propylene biscyclohexylene naphthalamide) (polyamide PACPN), polyisophorone adipamide (polyamide IPD6), polyisophorones Ramide (polyamide IPD8), polyisophorone azeamide (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 isophthala (Polyamide 4I), polytetramethylene hexahydroterephthalamide (polyamide 4T (H)), polypentamethylene isophthalamide (polyamide 5I), polypentamethylene hexahydroterephthalamide (polyamide 5T (H)), poly Hexamethylene isophthalamide (polyamide 6I), polyhexamethylene hexahydroterephthalamide (polyamide 6T (H)), poly (2-methylpentamethylene isophthalamide) (polyamide M5I), poly (2-methylpentamethylene hexa) Hydroterephthalamide) (polyamide M5T (H)), polynonamethylene isophthalamide (polyamide 9I), polynonamethylene hexahydroterephthalamide (polyamide 9T (H)), poly (2-methyloctamethylene isophthalamide) )(polyamide M8I), poly (2-methyloctamethylenehexahydroterephthalamide) (polyamide M8T (H)), polytrimethylhexamethyleneisophthalamide (polyamide TMHI), polytrimethylhexamethylenehexahydroterephthalamide (polyamide TMHT (H )), Polydecamethylene isophthalamide (polyamide 10I), polydecamethylene hexahydroterephthalamide (polyamide 10T (H)), polyundecamethylene isophthalamide (polyamide 11I), polyundecamethylene hexahydroterephthalate Copolymers using ramid (polyamide 11T (H)), polydodecamethylene isophthalamide (polyamide 12I), polydodecamethylene hexahydroterephthalamide (polyamide 12T (H)) and several raw material monomers of these polyamides. Coalescence, and the like. 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 / Saponified vinyl acetate copolymer (EVOH), ethylene / acrylic acid copolymer (EAA), ethylene / methacrylic acid copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methacrylic acid Methyl copolymer (EMMA), ethylene / ethyl acrylate Polyolefin resins such as polymer (EEA), polystyrene (PS), syndiotactic polystyrene (SPS), methyl methacrylate / styrene copolymer (MS), methyl methacrylate / styrene / butadiene copolymer (MBS), Styrene / butadiene copolymer (SBR), styrene / isoprene copolymer (SIR), styrene / isoprene / butadiene copolymer (SIBR), styrene / butadiene / styrene copolymer (SBS), styrene / isoprene / styrene copolymer Polymer (SIS), styrene / ethylene / butylene / styrene copolymer (SEBS), polystyrene resins such as styrene / ethylene / propylene / styrene copolymer (SEPS), carboxyl groups and salts thereof, acid anhydride groups, The above containing functional groups such as epoxy groups Reolefin resin, polystyrene resin, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), poly (ethylene terephthalate / ethylene isophthalate) copolymer (PET / PEI), polytrimethylene Terephthalate (PTT), polycyclohexanedimethylene terephthalate (PCT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyarylate (PAR), liquid crystal polyester (LCP), polylactic acid (PLA), polyglycolic acid Polyester resins such as (PGA), polyether resins such as polyacetal (POM) and polyphenylene ether (PPO), polysulfone (PSU), polyethersulfone (PESU) , Polysulfone resins such as polyphenylsulfone (PPSU), polythioether resins such as polyphenylene sulfide (PPS) and polythioethersulfone (PTES), polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketone ketone (PEKK), polyetheretherketoneketone (PEEKK), polyetherketoneetherketoneketone (PEKEKK) and other polyketone resins, polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene Polynitriles such as copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), acrylonitrile / butadiene copolymer (NBR) Resins, polymethacrylate resins such as polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA), polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride Copolymers, polyvinyl resins such as vinylidene chloride / methyl acrylate copolymer, cellulose resins such as cellulose acetate and cellulose butyrate, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorofluoroethylene (PCTFE) ), Tetrafluoroethylene / ethylene copolymer (ETFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / hexa Fluoropropylene / vinylidene fluoride copolymer (THV), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer ( PFA), fluororesin such as tetrafluoroethylene / hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer, chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer (CPT), polycarbonate ( Polycarbonate resins such as PC), thermoplastic polyimide (TPI), polyetherimide, polyesterimide, polyamideimide (PAI), polyesteramideimide, etc. Examples thereof include amide resins, thermoplastic polyurethane resins, polyamide elastomers, polyurethane elastomers, and polyester elastomers. These can use 1 type (s) or 2 or more types.

  Moreover, it is preferable to add a plasticizer to the aliphatic polyamide (A). Examples of the plasticizer 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 is 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the aliphatic polyamide (A) from the viewpoint of sufficiently ensuring the flexibility and low temperature impact resistance of the conductive laminated tube. It is preferably 2 parts by mass or more and 20 parts by mass or less.

  Moreover, it is preferable to add an impact resistance improving material to the aliphatic polyamide (A). Examples of the impact resistance improving material include rubbery polymers, and the flexural modulus measured according to ISO 178 is preferably 500 MPa or less. If the flexural modulus exceeds this value, the impact improvement effect may be insufficient.

  As the impact resistance improver, (ethylene and / or propylene) / α-olefin copolymer, (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) system A copolymer, an ionomer polymer, an aromatic vinyl compound / conjugated diene compound block copolymer may be mentioned, and these may be used alone or in combination of two or more.

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

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

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

  The aromatic vinyl compound / conjugated diene compound block copolymer is a block copolymer comprising an aromatic vinyl compound polymer block and a conjugated diene compound polymer block, and the aromatic vinyl compound polymer. A block copolymer having at least one block and at least one conjugated diene compound-based polymer block is used. In the block copolymer, the unsaturated bond in the conjugated diene compound-based polymer block may be hydrogenated.

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

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

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

  Further, (ethylene and / or propylene) / α-olefin copolymer, (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) used as an impact resistance improving material ) Type copolymer, ionomer polymer, and aromatic vinyl compound / conjugated diene compound type block copolymer are preferably polymers modified with carboxylic acid and / or derivatives thereof. By modifying with such a component, a functional group having affinity for the aliphatic polyamide (A) is included in the molecule.

  Examples of the functional group having affinity for the aliphatic polyamide (A) include a carboxyl group, an acid anhydride group, a carboxylic acid ester group, a carboxylic acid metal salt, a carboxylic acid imide group, a carboxylic acid amide group, and an epoxy group. Can be mentioned. 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 impact resistance improving material is 1 part by mass or more and 35 parts by mass 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 conductive laminated tube. The content is preferably 3 parts by mass or more and more preferably 25 parts by mass or less.

  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.

The semi-aromatic polyamide (B) used in the present invention is a diamine unit containing 80 mol% or more of an aliphatic diamine unit having 9 to 13 carbon atoms with respect to all diamine units, and all dicarboxylic acid units. And a dicarboxylic acid unit containing 80 mol% or more of terephthalic acid units and / or naphthalenedicarboxylic acid units (hereinafter sometimes referred to as semi-aromatic polyamide (B)).
The content of the aliphatic diamine unit having 9 to 13 carbon atoms in the semi-aromatic polyamide (B) is such as heat resistance, chemical resistance, impact resistance, chemical liquid permeation prevention property of the obtained conductive laminated tube. From the viewpoint of sufficiently ensuring various physical properties, it is at least 80 mol%, preferably at least 85 mol%, more preferably at least 90 mol%, based on all diamine units.

  Examples of aliphatic diamine units having 9 to 13 carbon atoms include 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, and 1,13-tridecanediamine. Units derived from. As long as the number of carbon atoms satisfies the above, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2,4-diethyl-1,6-hexane Diamine, 2,2-dimethyl-heptanediamine, 2,3-dimethyl-heptanediamine, 2,4-dimethyl-heptanediamine, 2,5-dimethyl-heptanediamine, 2-methyl-1,8-octanediamine, 3 -Methyl-1,8-octanediamine, 4-methyl-1,8-octanediamine, 1,3-dimethyl-1,8-octanediamine, 1,4-dimethyl-1,8-octanediamine, 2,2 -Dimethyl-1,8-octanediamine, 2,4-dimethyl-1,8-octanediamine, 3,3-dimethyl-1,8-octanediamine, 3,4-dimethyl -1,8-octanediamine, 4,4-dimethyl-1,8-octanediamine, 4,5-dimethyl-1,8-octanediamine, 5-methyl-1,9-nonanediamine, 2-butyl-1, You may contain the unit induced | guided | derived from branched aliphatic diamines, such as 8-octane diamine and 3-butyl-1, 8-octane diamine. These can use 1 type (s) or 2 or more types.

  Among the aliphatic diamine units having 9 to 13 carbon atoms, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, 1, from the viewpoint of the balance between coextrusion moldability and chemical solution permeation prevention Units derived from 10-decanediamine are preferred, and units derived from 1,12-dodecanediamine are preferred from the viewpoint of sufficiently ensuring low temperature impact resistance. Furthermore, when 1,9-nonanediamine and 2-methyl-1,8-octanediamine are used in combination, the molar ratio of 1,9-nonanediamine unit to 2-methyl-1,8-octanediamine unit is determined by the moldability and resistance. From the standpoint of impact balance, it is preferably 30:70 mol% or more and 98: 2 mol% or less, and more preferably 40:60 mol% or more and 95: 5 mol% or less.

  As long as the diamine unit in the semi-aromatic polyamide (B) is within the range that does not impair the excellent characteristics of the conductive laminated tube of the present invention, other than the aliphatic diamine unit having 9 to 13 carbon atoms. It may contain a diamine unit. Other diamine units include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, Units derived from aliphatic diamines such as 1,8-octanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexane Diamine, 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) pro 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine, bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, Fats such as 2,5-bis (aminomethyl) norbornane, 2,6-bis (aminomethyl) norbornane, 3,8-bis (aminomethyl) tricyclodecane, 4,9-bis (aminomethyl) tricyclodecane Units derived from cyclic diamines, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, 1,4-bis (aminomethyl) naphthalene, 1,5-bis (aminomethyl) ) Naphthalene, 2,6-bis (aminomethyl) naphthalene, 2,7-bis (aminomethyl) naphthalene , Units derived from aromatic diamines such as 4,4′-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl ether. These may be used alone or in combination of two or more. The content of these other diamine units is 20 mol% or less, preferably 15 mol% or less, more preferably 10 mol% or less, based on all diamine units.

  In addition, the content of the terephthalic acid unit and / or naphthalenedicarboxylic acid unit in the semi-aromatic polyamide (B) is sufficient for various physical properties such as heat resistance, chemical resistance and chemical solution permeation prevention of the obtained conductive laminated tube From the viewpoint of ensuring the above, it is at least 80 mol%, preferably at least 85 mol%, more preferably at least 90 mol%, based on all dicarboxylic acid units.

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

  As long as the dicarboxylic acid unit in the semi-aromatic polyamide (B) is within a range that does not impair the excellent characteristics of the conductive laminated tube of the present invention, other dicarboxylic acid other than the terephthalic acid unit and / or naphthalenedicarboxylic acid unit. It may contain an acid unit. Examples of other dicarboxylic acid units include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 2,2-diethylsuccinic acid, and suberin. Acid, azelaic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanediate Unit derived from aliphatic dicarboxylic acid such as acid, octadecanedioic acid, eicosanedioic acid, alicyclic such as 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid Units derived from dicarboxylic acids, phthalic acid, isophthalic acid, 1,3-phenylenedioxydiacetic acid, , 4-phenylenedioxydiacetic acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylethane-4,4′-dicarboxylic acid, diphenylpropane-4,4′-dicarboxylic acid, Units derived from aromatic dicarboxylic acids such as diphenyl ether-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-triphenyldicarboxylic acid These may be used alone or in combination of two or more. Among the above units, units derived from aromatic dicarboxylic acids are preferred. The content of these other dicarboxylic acid units is 20 mol% or less, preferably 15 mol% or less, more preferably 10 mol% or less, based on all dicarboxylic acid units. Furthermore, polycarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used within a range where melt molding is possible.

  The semi-aromatic polyamide (B) may contain other units other than the dicarboxylic acid unit and the diamine unit as long as the various excellent properties of the conductive laminated tube of the present invention are not impaired. Other units include units derived from lactams such as caprolactam, enantolactam, undecane lactam, dodecane lactam, α-pyrrolidone, α-piperidone, 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11 -Units derived from aminocarboxylic acids of aliphatic aminocarboxylic acids such as aminoundecanoic acid and 12-aminododecanoic acid, and aromatic aminocarboxylic acids such as p-aminomethylbenzoic acid. These can use 1 type (s) or 2 or more types. The content of other units is preferably 20 mol% or less, more preferably 10 mol% or less, and even more preferably 5 mol% or less, based on all dicarboxylic acid units.

  According to JIS K-6920, the relative viscosity of the semi-aromatic polyamide (B) measured under the conditions of 96% sulfuric acid, 1% polymer concentration and 25 ° C. is the mechanical property of the resulting conductive laminated tube. From the viewpoint of ensuring and ensuring the desirable moldability of the conductive laminated tube by setting the viscosity at the time of melting to an appropriate range, it is preferably 1.5 or more and 4.0 or less, and 1.8 or more and 3.5 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 (B), 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, alicyclic such as aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dicyclohexylamine Aromatic monoamines such as monoamine, aniline, toluidine, diphenylamine, naphthylamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, Aliphatic diamines such as 2-methyl-1,5-pentanediamine, cyclohexanediamine, bis (aminomethyl) cyclohexane, 5-amino-1,3,3-trimethylcyclohexanemethylamine, etc. Aromatic diamines such as cyclic diamine, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine, polyalkyleneimine, polyalkylenepolyamine, polyamine such as polyamine, polyallylamine, acetic acid, Aliphatic monocarboxylic acids such as propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid, cyclohexanecarboxylic acid, etc. Aromatic monocarboxylic acids such as monocarboxylic acid, benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, phenylacetic acid, adipic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid Pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and other aliphatic dicarboxylic acids, 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid And aromatic dicarboxylic acids such as alicyclic dicarboxylic acids such as phthalic acid and isophthalic acid. These can use 1 type (s) or 2 or more types. The amount of these molecular weight regulators used varies depending on the reactivity of the molecular weight regulator and the polymerization conditions, but is appropriately determined so that the relative viscosity of the polyamide to be finally obtained falls within the above range.

Considering the melt stability, it is preferable that the end of the molecular chain of the semi-aromatic polyamide (B) 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.

  Furthermore, as a semi-aromatic polyamide (B) production apparatus, a batch type reaction kettle, a single tank type or multi tank type continuous reaction apparatus, a tubular continuous reaction apparatus, a uniaxial kneading extruder, a biaxial kneading extruder, etc. A known polyamide production apparatus such as a kneading reaction extruder may be used. As 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.

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

  The semi-aromatic polyamide (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). Further, it may be a mixture with the aliphatic polyamide (A). The content of the semi-aromatic polyamide (B) in the mixture is preferably 60% by mass or more.

  Furthermore, for the semi-aromatic polyamide (B), an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, an inorganic filler, an antistatic agent, a flame retardant, and crystallization promotion, if necessary. Agents, plasticizers, colorants, lubricants, impact resistance improvers and the like may be added. In order to improve the low temperature impact resistance of the semi-aromatic polyamide (B), it is preferable to add an impact resistance improver, and in particular, bending measured according to ISO 178 described in the aliphatic polyamide (A). It is more preferable to add a rubbery polymer having an elastic modulus of 500 MPa or less.

  The conductive semi-aromatic polyamide copolymer composition (C) used in the present invention comprises (c1) 1,9-nonanediamine unit and 2-methyl-1,8-octanediamine unit with respect to all diamine units. And (c2) a diamine unit comprising an aliphatic diamine unit having 4 to 6 carbon atoms in an amount of 60 mol% or more and a molar ratio of (c1) to (c2) of 40:60 mol% to 80:20 mol% And a semi-aromatic polyamide copolymer (C1) (hereinafter referred to as semi-aromatic polyamide copolymer (C1)) containing 60 mol% or more of terephthalic acid units and / or naphthalenedicarboxylic acid units with respect to all dicarboxylic acid units And a conductive filler (C2).

(C1) 1,9-nonanediamine unit and 2-methyl-1,8-octanediamine unit in the semiaromatic polyamide copolymer (C1) and (c2) an aliphatic diamine unit having 4 to 6 carbon atoms. The total content is 60 mol% or more based on the total diamine units from the viewpoint of sufficiently ensuring various physical properties such as heat resistance, chemical resistance, impact resistance, and chemical liquid permeation resistance of the obtained conductive laminated tube. It is preferable that it is 75 mol% or more, and it is more preferable that it is 90 mol% or more.
(C1) In the 1,9-nonanediamine unit and the 2-methyl-1,8-octanediamine unit, the molar ratio of the 1,9-nonanediamine unit to the 2-methyl-1,8-octanediamine unit depends on the moldability and resistance. From the standpoint of impact balance, it is preferably 30:70 mol% or more and 98: 2 mol% or less, and more preferably 40:60 mol% or more and 95: 5 mol% or less.

  (C2) As the aliphatic diamine unit having 4 to 6 carbon atoms, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1,4-butanediamine, 1-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1,4-butanediamine, Derived from 1,4-dimethyl-1,4-butanediamine, 2,3-dimethyl-1,4-butanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, etc. Units. These can use 1 type (s) or 2 or more types. Among these, a unit derived from 1,6-hexanediamine and / or 2-methyl-1,5-pentanediamine is preferable from the viewpoint of availability.

  When 1,6-hexanediamine and 2-methyl-1,5-pentanediamine are used in combination, the molar ratio of the 1,6-hexanediamine unit to the 2-methyl-1,5-pentanediamine unit depends on the moldability and resistance. From the standpoint of impact balance, it is preferably 30:70 mol% or more and 98: 2 mol% or less, and more preferably 40:60 mol% or more and 95: 5 mol% or less.

  The molar ratio of the (c1) 1,9-nonanediamine unit and 2-methyl-1,8-octanediamine unit to the (c2) aliphatic diamine unit having 4 to 6 carbon atoms depends on moldability and low-temperature impact resistance. And (c1) :( c2) = 40: 60 mol% or more and 80:20 mol% or less, and 50:50 mol% or more and 78:22 mol% or less from the viewpoint of the balance of chemical solution permeation prevention properties. Is more preferably 55:45 mol% or more and 75:25 mol% or less.

  If the diamine unit in the semi-aromatic polyamide copolymer (C1) is within a range that does not impair the excellent properties of the conductive laminated tube of the present invention, (c1) 1,9-nonanediamine unit and 2-methyl -1,8-octanediamine units and (c2) diamine units other than aliphatic diamine units having 4 to 6 carbon atoms may be included. Other diamine units include 1,2-ethanediamine, 1,3-propanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,10-decanediamine, 1,11-undecanediamine, , 12-dodecanediamine, 1,13-tridecanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,4-dimethyl-1,6-hexanediamine, 3,3-dimethyl-1,6- Hexanediamine, 2,2-dimethyl-1,6-hexanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2,4- Diethyl-1,6-hexanediamine, 2,2-dimethyl-1,7-heptanediamine, 2,3-dimethyl-1,7-heptanediamine, 2,4-dimethyl 1,7-heptanediamine, 2,5-dimethyl-1,7-heptanediamine, 3-methyl-1,8-octanediamine, 4-methyl-1,8-octanediamine, 1,3-dimethyl-1, 8-octanediamine, 1,4-dimethyl-1,8-octanediamine, 2,4-dimethyl-1,8-octanediamine, 3,4-dimethyl-1,8-octanediamine, 4,5-dimethyl- 1,8-octanediamine, 2,2-dimethyl-1,8-octanediamine, 3,3-dimethyl-1,8-octanediamine, 4,4-dimethyl-1,8-octanediamine, 5-methyl- Units derived from aliphatic diamines such as 1,9-nonanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis (aminomethyl) silane Hexane, 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, m-xylylenediamine, 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-aminophenyl) propane, 4,4′-diaminodiphenylsulfone, 4,4 Examples include units derived from aromatic diamines such as' -diaminodiphenyl ether, and these may be used alone or in combination of two or more. The content of these other diamine units is 40 mol% or less, preferably 25 mol% or less, more preferably 10 mol% or less, based on all diamine units.

  Moreover, the content of the terephthalic acid unit and / or naphthalenedicarboxylic acid unit in the semi-aromatic polyamide copolymer (C1) is sufficient for the heat resistance, chemical resistance, chemical solution permeation prevention property, etc. of the obtained conductive laminated tube. From the viewpoint of ensuring the above, it is at least 60 mol%, preferably at least 75 mol%, more preferably at least 90 mol%, based on all dicarboxylic acid units.

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

  As long as the dicarboxylic acid unit in the semi-aromatic polyamide copolymer (C1) is within a range that does not impair the excellent characteristics of the conductive laminated tube of the present invention, other than the terephthalic acid unit and / or the naphthalene dicarboxylic acid unit. Other dicarboxylic acid units may be included. Examples of other dicarboxylic acid units include the dicarboxylic acid units described in the description of the semi-aromatic polyamide (B). The content of other dicarboxylic acid units is 40 mol% or less, preferably 25 mol% or less, more preferably 10 mol% or less, based on all dicarboxylic acid units.

  The semi-aromatic polyamide copolymer (C1) may contain other units other than the dicarboxylic acid unit and the diamine unit as long as the excellent properties of the conductive laminated tube of the present invention are not impaired. Good. Examples of the other units include units derived from lactam and units derived from aminocarboxylic acid described in the description of the semi-aromatic polyamide (B). The content of other units is preferably 30 mol% or less, more preferably 10 mol% or less, based on the total dicarboxylic acid unit.

Specific examples of the semi-aromatic polyamide copolymer (C1) include a poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / tetramethylene terephthalamide) copolymer (polyamide 9T / M8T / 4T). , Poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / tetramethylene terephthalamide / nonamethylene adipamide / 2-methyloctamethylene adipamide / tetramethylene adipamide) copolymer (polyamide) 9T / M8T / 4T / 96 / M86 / 46), poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / tetramethylene terephthalamide / trimethylhexamethylene terephthalamide) copolymer (polyamide 9T / M8T / 4T / TMHT), poly (nonamethylenete) Phthalamide / 2-methyloctamethylene terephthalamide / tetramethylene terephthalamide / decamethylene terephthalamide) copolymer (polyamide 9T / M8T / 4T / 10T), poly (nonamethylene terephthalamide / 2-methyloctamethylene) Terephthalamide / tetramethylene terephthalamide / dodecamethylene terephthalamide) copolymer (polyamide 9T / M8T / 4T / 12T), poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / pentamethylene tele Phthalamide) copolymer (polyamide 9T / M8T / 5T), poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / pentamethylene terephthalamide / nonamethylene adipamide / 2-methyloctamethylene azide Pamide / Pentamethi Adipamide) copolymer (polyamide 9T / M8T / 5T / 96 / M86 / 56), poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / pentamethylene terephthalamide / trimethylhexamethylene terephthalamide) Copolymer (polyamide 9T / M8T / 5T / TMHT), poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / pentamethylene terephthalamide / decamethylene terephthalamide) copolymer (polyamide 9T / M8T / 5T / 10T), poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / pentamethylene terephthalamide / dodecamethylene terephthalamide) copolymer (polyamide 9T / M8T / 5T / 12T), Poly (nonamethylene terephthala Imide / 2-methyloctamethylene terephthalamide / hexamethylene terephthalamide) copolymer (polyamide 9T / M8T / 6T), poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / hexamethylene terephthalate) Lamid / nonamethylene adipamide / 2-methyloctamethylene adipamide / hexamethylene adipamide) copolymer (polyamide 9T / M8T / 6T / 96 / M86 / 66), poly (nonamethylene terephthalamide / 2 -Methyloctamethylene terephthalamide / hexamethylene terephthalamide / nonamethylene azeramide / 2-methyloctamethylene azeramide / hexamethylene azelamide) copolymer (polyamide 9T / M8T / 6T / 99 / M89 / 69), Poly (nonamethylene terephthalamide / 2-methyl Cotamethylene terephthalamide / hexamethylene terephthalamide / nonamethyle sebacamide / 2-methyloctamethylene sebacamide / hexamethylene sebacamide) copolymer (polyamide 9T / M8T / 6T / 910 / M810 / 610) Poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / hexamethylene terephthalamide / nonamethylene dodecamide / 2-methyloctamethylene dodecamide / hexamethylene dodecamide) copolymer (polyamide 9T / M8T / 6T / 912 / M812 / 612), poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / hexamethylene terephthalamide / trimethylhexamethylene terephthalamide) copolymer (polyamide 9T / M8T / 6T / TMHT), Po (Nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / hexamethylene terephthalamide / decamethylene terephthalamide) copolymer (polyamide 9T / M8T / 6T / 10T), poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / hexamethylene terephthalamide / dodecamethylene terephthalamide) copolymer (polyamide 9T / M8T / 6T / 12T), poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalate) Lamide / 2-methylpentamethylene terephthalamide) copolymer (polyamide 9T / M8T / M5T), poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / 2-methylpentamethylene terephthalamide / nona Methylene adipamide / 2-methyl Leoctamethylene adipamide / 2-methylpentamethylene adipamide copolymer (polyamide 9T / M8T / M5T / 96 / M86 / M56), poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) / 2-methylpentamethylene terephthalamide / trimethylhexamethylene terephthalamide) copolymer (polyamide 9T / M8T / M5T / TMHT), poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / 2- Methylpentamethylene terephthalamide / decamethylene terephthalamide) copolymer (polyamide 9T / M8T / M5T / 10T), poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / 2-methylpentamethylene terephthalate) Phthalamide / dodecamethylene teref (Ramide) copolymer (polyamide 9T / M8T / M5T / 12T), poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / hexamethylene terephthalamide / 2-methylpentamethylene terephthalamide) copolymer Polymer (polyamide 9T / M8T / 6T / M5T), poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / hexamethylene terephthalamide / 2-methylpentamethylene terephthalamide / nonamethylene adipamide / 2-methyloctamethyleneadipamide / hexamethyleneadipamide / 2-methylpentamethyleneadipamide) copolymer (polyamide 9T / M8T / 6T / M5T / 96 / M86 / 66 / M56), poly (nonamethylene Terephthalamide / 2-methyloctamethylene terephthalate Imide / hexamethylene terephthalamide / 2-methylpentamethylene terephthalamide / trimethylhexamethylene terephthalamide) copolymer (polyamide 9T / M8T / 6T / M5T / TMHT), poly (nonamethylene terephthalamide / 2- Methyloctamethylene terephthalamide / hexamethylene terephthalamide / 2-methylpentamethylene terephthalamide / decamethylene terephthalamide) copolymer (polyamide 9T / M8T / 6T / M5T / 10T), poly (nonamethylene terephthalate) Ramid / 2-methyloctamethylene terephthalamide / hexamethylene terephthalamide / 2-methylpentamethylene terephthalamide / dodecamethylene terephthalamide) copolymer (polyamide 9T / M8T / 6T / M5T / 12T),
Poly (nonamethylenenaphthalamide / 2-methyloctamethylenenaphthalamide / tetramethylenenaphthalamide) copolymer (polyamide 9N / M8N / 4N), poly (nonamethylenenaphthalamide / 2-methyloctamethylenenaphthalamide / tetramethylenenaphthalene) Lamid / nonamethylene adipamide / 2-methyloctamethylene adipamide / tetramethylene adipamide) copolymer (polyamide 9N / M8N / 4N / 96 / M86 / 46), poly (nonamethylene naphthalamide / 2- Methyloctamethylenenaphthalamide / tetramethylenenaphthalamide / trimethylhexamethylenenaphthalamide) copolymer (polyamide 9N / M8N / 4N / TMHN), poly (nonamethylenenaphthalamide / 2-methyloctamethylenenaphthalamide / tetramethylenenaphthalamide) De / methylene naphthalamide) copolymer (polyamide 9N / M8N / 4N / 10N), poly (nonamethylene naphthalamide / 2-methyloctamethylene naphthalamide / tetramethylene naphthalamide / dodecamethylene terephthalamide) copolymer (Polyamide 9N / M8N / 4N / 12N), poly (nonamethylene naphthalamide / 2-methyloctamethylene naphthalamide / pentamethylene naphthalamide) copolymer (polyamide 9N / M8N / 5N), poly (nonamethylene naphthalamide / 2-methyloctamethylenenaphthalamide / pentamethylenenaphthalamide / nonamethyleneadipamide / 2-methyloctamethyleneadipamide / pentamethyleneadipamide) copolymer (polyamide 9N / M8N / 5N / 96 / M86 / 56) ), Poly (nonamethylenena) Taramide / 2-methyloctamethylenenaphthalamide / pentamethylenenaphthalamide / trimethylhexamethylenenaphthalamide) copolymer (polyamide 9N / M8N / 5N / TMHN), poly (nonamethylenenaphthalamide / 2-methyloctamethylenenaphthalamide / Pentamethylenenaphthalamide / Decamethylenenaphthalamide) copolymer (polyamide 9N / M8N / 5N / 10N), poly (nonamethylenenaphthalamide / 2-methyloctamethylenenaphthalamide / pentamethylenenaphthalamide / dodecamethyleneterephthalamide) Copolymer (polyamide 9N / M8N / 5N / 12N), poly (nonamethylene naphthalamide / 2-methyloctamethylene naphthalamide / hexamethylene naphthalamide) copolymer (polyamide 9N / M8N / 6N), poly (no Namethylene naphthalamide / 2-methyloctamethylene naphthalamide / nonamethylene adipamide / 2-methyloctamethylene adipamide / hexamethylene naphthalamide / hexamethylene adipamide) copolymer (polyamide 9N / M8N / 6N / 96 / M86 / 66), poly (nonamethylenenaphthalamide / 2-methyloctamethylenenaphthalamide / hexamethylenenaphthalamide / trimethylhexamethylenenaphthalamide) copolymer (polyamide 9N / M8N / 6N / TMHN), poly (nona Methylenenaphthalamide / 2-methyloctamethylenenaphthalamide / hexamethylenenaphthalamide / decamethylenenaphthalamide) copolymer (polyamide 9N / M8N / 6N / 10N), poly (nonamethylenenaphthalamide / 2-methyloctamethylenenaphthalamide) / Hexamethylene naphthalamide / dodecamethylene terephthalamide) copolymer (polyamide 9N / M8N / 6N / 12N), poly (nonamethylene naphthalamide / 2-methyloctamethylene naphthalamide / 2-methylpentamethylene naphthalamide) Polymer (polyamide 9N / M8N / M5N), poly (nonamethylenenaphthalamide / 2-methyloctamethylenenaphthalamide / 2-methylpentamethylenenaphthalamide / nonamethyleneadipamide / 2-methyloctamethyleneadipamide / 2 -Methylpentamethylene adipamide) copolymer (polyamide 9N / M8N / M5N / 96 / M86 / M56), poly (nonamethylenenaphthalamide / 2-methyloctamethylenenaphthalamide / 2-methylpentamethylenenaphthalamide / trimethyl Hexamethylene (Phthalamide) copolymer (polyamide 9N / M8N / M5N / TMHN), poly (nonamethylene naphthalamide / 2-methyloctamethylene naphthalamide / 2-methylpentamethylene naphthalamide / decamethylene naphthalamide) copolymer (polyamide 9N) / M8N / M5N / 10N), poly (nonamethylenenaphthalamide / 2-methyloctamethylenenaphthalamide / 2-methylpentamethylenenaphthalamide / dodecamethyleneterephthalamide) copolymer (polyamide 9N / M8N / M5N / 12N) , Poly (nonamethylenenaphthalamide / 2-methyloctamethylenenaphthalamide / hexamethylenenaphthalamide / 2-methylpentamethylenenaphthalamide) copolymer (polyamide 9N / M8N / 6N / M5N), poly (nonamethylenenaphthalamide / 2-me Tiloctamethylene naphthalamide / hexamethylene naphthalamide / 2-methylpentamethylene naphthalamide / nonamethylene adipamide / 2-methyloctamethylene adipamide / hexamethylene adipamide / 2-methylpentamethylene adipamide) Polymer (polyamide 9N / M8N / 6N / M5N / 96 / M86 / 66 / M56), poly (nonamethylenenaphthalamide / 2-methyloctamethylenenaphthalamide / hexamethylenenaphthalamide / 2-methylpentamethylenenaphthalamide / trimethyl Hexamethylenenaphthalamide) copolymer (polyamide 9N / M8N / 6N / M5N / TMHN), poly (nonamethylenenaphthalamide / 2-methyloctamethylenenaphthalamide / hexamethylenenaphthalamide / 2-methylpentamethylenenaphthalamide) Decamethylenenaphthalamide) copolymer (polyamide 9N / M8N / 6N / M5N / 10N), poly (nonamethylenenaphthalamide / 2-methyloctamethylenenaphthalamide / hexamethylenenaphthalamide / 2-methylpentamethylenenaphthalamide / dodeca Methylene terephthalamide) copolymer (polyamide 9N / M8N / 6N / M5N / 12N),
Poly (nonamethylene terephthalamide / nonamethylene naphthalamide / 2-methyloctamethylene terephthalamide / 2-methyloctamethylene naphthalamide / tetramethylene terephthalamide / tetramethylene naphthalamide) copolymer (polyamide 9T / 9N / M8T / M8N / 4T / 4N), poly (nonamethylene terephthalamide / nonamethylene naphthalamide / 2-methyloctamethylene terephthalamide / 2-methyloctamethylene naphthalamide / tetramethylene terephthalamide / nonamethylene adipamide / 2-methyloctamethylene adipamide / tetramethylene naphthalamide / tetramethylene adipamide) copolymer (polyamide 9T / 9N / M8T / M8N / 4T / 4N / 96 / M86 / 46), poly (nonamethylene tele Phthalamide / Nonamethyle Naphthalamide / 2-methyloctamethylene terephthalamide / 2-methyloctamethylene naphthalamide / pentamethylene terephthalamide / pentamethylene naphthalamide copolymer (polyamide 9T / 9N / M8T / M8N / 5T / 5N), poly ( Nonamethylene terephthalamide / Nonamethylene naphthalamide / 2-Methyloctamethylene terephthalamide / 2-Methyloctamethylene naphthalamide / Pentamethylene terephthalamide / Pentamethylene naphthalamide / Nonamethylene adipamide / 2-Methyloctamethylene Adipamide / pentamethylene adipamide) copolymer (polyamide 9T / 9N / M8T / M8N / 5T / 5N / 96 / M86 / 56), poly (nonamethylene terephthalamide / nonamethylenenaphthalamide / 2-methyl Octamethylene tele Taramide / 2-methyloctamethylene naphthalamide / hexamethylene terephthalamide / hexamethylene naphthalamide copolymer (polyamide 9T / 9N / M8T / M8N / 6T / 6N), poly (nonamethylene terephthalamide / nonamethylene naphtha) Lamide / 2-methyloctamethylene terephthalamide / 2-methyloctamethylene naphthalamide / hexamethylene terephthalamide / hexamethylene naphthalamide / nonamethylene adipamide / 2-methyloctamethylene adipamide / hexamethylene adipamide ) Copolymer (polyamide 9T / 9N / M8T / M8N / 6T / 6N / 96 / M86 / 66), poly (nonamethylene terephthalamide / nonamethylene naphthalamide / 2-methyloctamethylene terephthalamide / 2-methyl Octamethylene naphthalami / 2-methylpentamethylene terephthalamide / 2-methylpentamethylene naphthalamide) copolymer (polyamide 9T / 9N / M8T / M8N / M5T / M5N), poly (nonamethylene terephthalamide / nonamethylene naphthalamide / 2-methyloctamethyleneterephthalamide / 2-methyloctamethylenenaphthalamide / 2-methylpentamethyleneterephthalamide / 2-methylpentamethylenenaphthalamide / nonamethyleneadipamide / 2-methyloctamethyleneadipamide / 2 -Methylpentamethylene adipamide) copolymer (polyamide 9T / 9N / M8T / M8N / M5T / M5N / 96 / M86 / M56), poly (nonamethyleneterephthalamide / nonamethylenenaphthalamide / 2-methyloctamethylene) Terephthalamide / 2-methyloctame Lennaphthalamide / hexamethylene terephthalamide / hexamethylene naphthalamide / 2-methylpentamethylene terephthalamide / 2-methylpentamethylene naphthalamide copolymer (polyamide 9T / 9N / M8T / M8N / 6T / 6N / M5T / M5N) ), Poly (nonamethyleneterephthalamide / nonamethylenenaphthalamide / 2-methyloctamethyleneterephthalamide / 2-methyloctamethylenenaphthalamide / hexamethyleneterephthalamide / hexamethylenenaphthalamide / 2-methylpentamethyleneterephthalate Lamide / 2-methylpentamethylene naphthalamide / nonamethylene adipamide / 2-methyloctamethylene adipamide / hexamethylene adipamide / 2-methylpentamethylene adipamide) copolymer (polyamide 9T / 9N / M8 / M8N / 6T / 6N / M5T / M5N / 96 / M86 / 66 / M56),
Poly (nonamethylene terephthalamide / nonamethylene isophthalamide / 2-methyloctamethylene terephthalamide / 2-methyloctamethylene isophthalamide / tetramethylene terephthalamide / tetramethylene isophthalamide) copolymer (polyamide 9T / 9I / M8T / M8I / 4T / 4I), poly (nonamethylene terephthalamide / nonamethylene isophthalamide / 2-methyloctamethylene terephthalamide / 2-methyloctamethylene isophthalamide / tetramethylene terephthalamide / Tetramethylene isophthalamide / nonamethylene adipamide / 2-methyloctamethylene adipamide / tetramethylene adipamide) copolymer (polyamide 9T / 9I / M8T / M8I / 4T / 4I / 96 / M86 / 46) , Poly (nonamethylene terephthalamide Nonamethylene isophthalamide / 2-methyloctamethylene terephthalamide / 2-methyloctamethylene isophthalamide / pentamethylene terephthalamide / pentamethylene isophthalamide) copolymer (polyamide 9T / 9I / M8T / M8I / 5T / 5I), poly (nonamethylene terephthalamide / nonamethylene isophthalamide / 2-methyloctamethylene terephthalamide / 2-methyloctamethylene isophthalamide / pentamethylene terephthalamide / pentamethylene isophthalamide / nonamethylene Adipamide / 2-methyloctamethylene adipamide / pentamethylene adipamide) copolymer (polyamide 9T / 9I / M8T / M8I / 5T / 5I / 96 / M86 / 56), poly (nonamethylene terephthalamide) / Nonamethylene isophthalamide / 2 Methyl octamethylene terephthalamide / 2-methyloctamethylene isophthalamide / hexamethylene terephthalamide / hexamethylene isophthalamide copolymer (polyamide 9T / 9I / M8T / M8I / 6T / 6I), poly (nonamethylene Terephthalamide / nonamethylene isophthalamide / 2-methyloctamethylene terephthalamide / 2-methyloctamethylene isophthalamide / hexamethylene terephthalamide / hexamethylene isophthalamide / nonamethylene adipamide / 2-methylocta Methylene adipamide / hexamethylene adipamide) copolymer (polyamide 9T / 9I / M8T / M8I / 6T / 6I / 96 / M86 / 66), poly (nonamethylene terephthalamide / nonamethylene isophthalamide / 2) -Methyloctamethylene terephthalami / 2-methyloctamethyleneisophthalamide / 2-methylpentamethyleneterephthalamide / 2-methylpentamethyleneisophthalamide) copolymer (polyamide 9T / 9I / M8T / M8I / M5T / M5I), poly (nona) Methylene terephthalamide / nonamethylene isophthalamide / 2-methyloctamethylene terephthalamide / 2-methyloctamethylene isophthalamide / 2-methylpentamethylene terephthalamide / 2-methylpentamethylene isophthalamide / nonamethylene azide Pamide / 2-methyloctamethylene adipamide / 2-methylpentamethylene adipamide) copolymer (polyamide 9T / 9I / M8T / M8I / M5T / M5I / 96 / M86 / M56), poly (nonamethylene tele Phthalamide / nonamethylene isophthalamide / 2-methyl Octamethylene terephthalamide / 2-methyloctamethylene isophthalamide / hexamethylene terephthalamide / hexamethylene isophthalamide / 2-methylpentamethylene terephthalamide / 2-methylpentamethylene isophthalamide) copolymer (polyamide) 9T / 9I / M8T / M8I / 6T / 6I / M5T / M5I), poly (nonamethylene terephthalamide / nonamethylene isophthalamide / 2-methyloctamethylene terephthalamide / 2-methyloctamethylene isophthalamide / hexa Methylene terephthalamide / hexamethylene isophthalamide / 2-methylpentamethylene terephthalamide / 2-methylpentamethylene isophthalamide / nonamethylene adipamide / 2-methyloctamethylene adipamide / hexamethylene adipamide / 2-methyl Pentamethylene adipamide) copolymer (polyamide 9T / 9I / M8T / M8I / 6T / 6I / M5T / M5I / 96 / M86 / 66 / M56),
Poly (nonamethylenenaphthalamide / nonamethyleneisophthalamide / 2-methyloctamethylenenaphthalamide / 2-methyloctamethyleneisophthalamide / tetramethylenenaphthalamide / tetramethyleneisophthalamide) copolymer (polyamide 9N / 9I / M8N / M8I / 4N / 4I), poly (nonamethylenenaphthalamide / nonamethyleneisophthalamide / 2-methyloctamethylenenaphthalamide / 2-methyloctamethyleneisophthalamide / tetramethylenenaphthalamide / tetramethyleneisophthalamide / Nonamethylene adipamide / 2-methyloctamethylene adipamide / tetramethylene adipamide copolymer (polyamide 9N / 9I / M8N / M8I / 4N / 4I / 96 / M86 / 46), poly (nonamethylene naphtha Lamid / Nonamethylene Sophthalamide / 2-methyloctamethylenenaphthalamide / 2-methyloctamethyleneisophthalamide / pentamethylenenaphthalamide / pentamethyleneisophthalamide) copolymer (polyamide 9N / 9I / M8N / M8I / 5N / 5I), poly ( Nonamethylene naphthalamide / nonamethylene isophthalamide / 2-methyloctamethylene naphthalamide / 2-methyloctamethylene isophthalamide / pentamethylenenaphthalamide / pentamethyleneisophthalamide / nonamethylene adipamide / 2-methyloctamethylene Adipamide / pentamethylene adipamide) copolymer (polyamide 9N / 9I / M8N / M8I / 5N / 5I / 96 / M86 / 56), poly (nonamethylenenaphthalamide / nonamethyleneisophthalamide / 2-methyl Octamethylene naphth Lamide / 2-methyloctamethyleneisophthalamide / hexamethylenenaphthalamide / hexamethyleneisophthalamide) copolymer (polyamide 9N / 9I / M8N / M8I / 6N / 6I), poly (nonamethylenenaphthalamide / nonamethyleneiso) Phthalamide / 2-methyloctamethylenenaphthalamide / 2-methyloctamethyleneisophthalamide / hexamethylenenaphthalamide / hexamethyleneisophthalamide / nonamethyleneadipamide / 2-methyloctamethyleneadipamide / hexamethyleneadipa (Midamide) copolymer (polyamide 9N / 9I / M8N / M8I / 6N / 6I / 96 / M86 / 66), poly (nonamethylenenaphthalamide / nonamethyleneisophthalamide / 2-methyloctamethylenenaphthalamide / 2-methyl Octamethylene isophthalami / 2-methylpentamethylenenaphthalamide / 2-methylpentamethyleneisophthalamide) copolymer (polyamide 9N / 9I / M8N / M8I / M5N / M5I), poly (nonamethylenenaphthalamide / nonamethyleneisophthalamide / 2-methyloctamethylenenaphthalamide / 2-methyloctamethyleneisophthalamide / 2-methylpentamethylenenaphthalamide / 2-methylpentamethyleneisophthalamide / nonamethyleneadipamide / 2-methyloctamethyleneadipamide / 2 -Methylpentamethylene adipamide) copolymer (polyamide 9N / 9I / M8N / M8I / M5N / M5I / 96 / M86 / M56), poly (nonamethylenenaphthalamide / nonamethyleneisophthalamide / 2-methyloctamethylene) Naphthalamide / 2-methyloctamethy Isophthalamide / hexamethylenenaphthalamide / hexamethyleneisophthalamide / 2-methylpentamethylenenaphthalamide / 2-methylpentamethyleneisophthalamide) (polyamide 9N / 9I / M8N / M8I / 6N / 6I / 6M / M5N / M5I) ), Poly (nonamethylenenaphthalamide / nonamethyleneisophthalamide / 2-methyloctamethylenenaphthalamide / 2-methyloctamethyleneisophthalamide / hexamethylenenaphthalamide / hexamethyleneisophthalamide / 2-methylpentamethylenenaphthalamide / 2-methylpentamethyleneisophthalamide / nonamethyleneadipamide / 2-methyloctamethyleneadipamide / hexamethyleneadipamide / 2-methylpentamethyleneadipamide) copolymer (polyamide 9N / 9I / M8 / M8I / 6N / 6I / M5N / M5I / 96 / M86 / 66 / M56), and the like.

  Among these, poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / hexamethylene terephthalamide) copolymer (polyamide) from the viewpoint of easy availability and balance between chemical solution permeation prevention and low temperature impact resistance 9T / M8T / 6T), poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / hexamethylene terephthalamide / nonamethylene adipamide / 2-methyloctamethylene adipamide / hexamethylene adipamide ) Copolymer (polyamide 9T / M8T / 6T / 96 / M86 / 66), poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / hexamethylene terephthalamide / 2-methylpentamethylene terephthalamide) ) Copolymer (Polyamide 9T / M8T / 6T / M5T Poly (nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / hexamethylene terephthalamide / 2-methylpentamethylene terephthalamide / nonamethylene adipamide / 2-methyloctamethylene adipamide / hexamethylene Adipamide / 2-methylpentamethylene adipamide) copolymer (polyamide 9T / M8T / 6T / M5T / 96 / M86 / 66 / M56), poly (nonamethylenenaphthalamide / 2-methyloctamethylenenaphthalamide / Hexamethylenenaphthalamide) copolymer (polyamide 9N / M8N / 6N), poly (nonamethylenenaphthalamide / 2-methyloctamethylenenaphthalamide / hexamethylenenaphthalamide / nonamethyleneadipamide / 2-methyloctamethyleneadipa Mid / Hexamethylene Adipa D) Copolymer (polyamide 9N / M8N / 6N / 96 / M86 / 66), poly (nonamethylenenaphthalamide / 2-methyloctamethylenenaphthalamide / hexamethylenenaphthalamide / 2-methylpentamethylenenaphthalamide) copolymer Combined (polyamide 9N / M8N / 6N / M5N), poly (nonamethylenenaphthalamide / 2-methyloctamethylenenaphthalamide / hexamethylenenaphthalamide / 2-methylpentamethylenenaphthalamide / nonamethyleneadipamide / 2-methylocta Methylene adipamide / hexamethylene adipamide / 2-methylpentamethylene adipamide) copolymer (polyamide 9N / M8N / 6N / M5N / 96 / M86 / 66 / M56), poly (nonamethylene terephthalamide / Nonamethylene naphthalamide / 2-methyloctame Tylene terephthalamide / 2-methyloctamethylene naphthalamide / hexamethylene terephthalamide / hexamethylene naphthalamide copolymer (polyamide 9T / 9N / M8T / M8N / 6T / 6N), poly (nonamethylene terephthalamide / Nonamethylene naphthalamide / 2-methyloctamethylene terephthalamide / 2-methyloctamethylene naphthalamide / hexamethylene terephthalamide / hexamethylene naphthalamide / nonamethylene adipamide / 2-methyloctamethylene adipamide / hexamethylene Adipamide) copolymer (polyamide 9T / 9N / M8T / M8N / 6T / 6N / 96 / M86 / 66), poly (nonamethylene terephthalamide / nonamethylene naphthalamide / 2-methyloctamethylene terephthalamide / 2-methyloctamethyle Naphthalamide / hexamethylene terephthalamide / hexamethylene naphthalamide / 2-methylpentamethylene terephthalamide / 2-methylpentamethylene naphthalamide copolymer (polyamide 9T / 9N / M8T / M8N / 6T / 6N / M5T / M5N) ), Poly (nonamethyleneterephthalamide / nonamethylenenaphthalamide / 2-methyloctamethyleneterephthalamide / 2-methyloctamethylenenaphthalamide / hexamethyleneterephthalamide / hexamethylenenaphthalamide / 2-methylpentamethyleneterephthalate Lamide / 2-methylpentamethylene naphthalamide / nonamethylene adipamide / 2-methyloctamethylene adipamide / hexamethylene adipamide / 2-methylpentamethylene adipamide) copolymer (polyamide 9T / 9N / M8T / 8N / 6T / 6N / M5T / M5N / 96 / M86 / 66 / M56), poly (nonamethylene terephthalamide / nonamethylene isophthalamide / 2-methyloctamethylene terephthalamide / 2-methyloctamethylene isophthalamide / Hexamethylene terephthalamide / hexamethylene isophthalamide) copolymer (polyamide 9T / 9I / M8T / M8I / 6T / 6I), poly (nonamethylene terephthalamide / nonamethylene isophthalamide) / 2-methyloctamethylene Terephthalamide / 2-methyloctamethylene isophthalamide / hexamethylene terephthalamide / hexamethylene isophthalamide / nonamethylene adipamide / 2-methyloctamethylene adipamide / hexamethylene adipamide) copolymer ( Polyamide 9T / 9I / M8T / M8I / 6 T / 6I / 96 / M86 / 66), poly (nonamethylene terephthalamide / nonamethylene isophthalamide / 2-methyloctamethylene terephthalamide / 2-methyloctamethylene isophthalamide / hexamethylene terephthalamide / hexa Methyleneisophthalamide / 2-methylpentamethyleneterephthalamide / 2-methylpentamethyleneisophthalamide copolymer (polyamide 9T / 9I / M8T / M8I / 6T / 6I / M5T / M5I), poly (nonamethylenetere) Phthalamide / nonamethylene isophthalamide / 2-methyloctamethylene terephthalamide / 2-methyloctamethylene isophthalamide / hexamethylene terephthalamide / hexamethylene isophthalamide / 2-methylpentamethylene terephthalamide / 2 Methyl pentamethylene isophthal Mido / nonamethylene adipamide / 2-methyloctamethylene adipamide / hexamethylene adipamide / 2-methylpentamethylene adipamide) (polyamide 9T / 9I / M8T / M8I / 6T / 6I / M5T) / M5I / 96 / M86 / 66 / M56).

  The relative viscosity of the semi-aromatic polyamide copolymer (C1) measured under the conditions of 96% sulfuric acid, 1% polymer concentration and 25 ° C. according to JIS K-6920 is the machine of the conductive laminated tube obtained. Is preferably 1.5 or more and 3.0 or less, from the viewpoint of securing the desired properties and ensuring the desirable formability of the conductive laminated tube by setting the viscosity at the time of melting to an appropriate range. It is more preferably 0.5 or less, and further preferably 1.8 or more and 2.3 or less.

  In addition, there is no special restriction | limiting in the kind of terminal group of the semi-aromatic polyamide copolymer (C1), 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, monoamine, diamine, polyamine, monocarboxylic acid and dicarboxylic acid described in the description of the semi-aromatic polyamide (B) can be mentioned, and the amount of the molecular weight regulator used varies depending on the reactivity of the molecular weight regulator and the polymerization conditions. The relative viscosity of the polyamide to be finally obtained is appropriately determined so as to be in the above range.

  In consideration of melt stability, it is preferable that the end of the molecular chain of the semi-aromatic polyamide copolymer (C1) is sealed with a terminal blocking agent, and that 10% or more of the terminal group is sealed. It is more preferable that 20% or more of the end groups are sealed. The end capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the end of the polyamide, but from the viewpoint of reactivity, stability of the capped end, etc. An acid or a monoamine is preferable, and a monocarboxylic acid is more preferable from the viewpoint of easy handling. In addition, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, monoalcohols, and the like can be used. For example, monocarboxylic acids and monoamines described in the description of the semi-aromatic polyamide (B) are used as the end-capping agent. 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.

  As a manufacturing apparatus of a semi-aromatic polyamide copolymer (C1), the well-known polyamide manufacturing apparatus described by description of a semi-aromatic polyamide (B) is mentioned. As a manufacturing method of a semi-aromatic polyamide copolymer (C1), the well-known method described by description of a semi-aromatic polyamide (B) is mentioned.

  In producing the semi-aromatic polyamide copolymer (C1), phosphoric acid, phosphorous acid, hypophosphorous acid, a salt or ester thereof or the like can be added as a catalyst or to prevent coloring. Can be added. Examples thereof include phosphoric acid, phosphorous acid, hypophosphorous acid, salts or esters thereof described in the description of the semi-aromatic polyamide (B).

The conductive filler (C2) in the conductive semi-aromatic polyamide copolymer composition (C) includes all fillers added to impart conductive performance to the resin, and is granular, flaky, and A fibrous filler etc. are mentioned.
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.

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

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

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

Carbon black is produced in various carbon powders having different characteristics such as particle diameter, surface area, DBP oil absorption, ash content and the like. Although there is no restriction | limiting in the characteristic of this carbon black, What has a favorable chain structure and a large aggregation density is preferable. A large amount of carbon black is not preferable from the viewpoint of impact resistance, and from the viewpoint of obtaining excellent electrical conductivity with a smaller amount, the average particle size is preferably 500 nm or less, more preferably 5 nm or more and 100 nm or less. More preferably, it is 10 nm or more and 70 nm or less, and the surface area (BET method) is preferably 10 m ² / g or more, more preferably 30 m ² / g or more, and 50 m ² / g or more. Further, the DBP (dibutyl phthalate) oil absorption is preferably 50 ml / 100 g or more, more preferably 100 ml / 100 g, and further preferably 150 ml / 100 g or more. Moreover, it is preferable that an ash content is 0.5 mass% or less, and it is more preferable that it is 0.3 mass% or less. The DBP oil absorption here is a value measured by a method defined in ASTM D-2414. Moreover, it is preferable that the volatile content of carbon black is less than 1.0 mass%.
These conductive fillers (C2) may be surface-treated with a surface treatment agent such as titanate, aluminum, and silane. Moreover, it is also possible to use what was granulated in order to improve melt-kneading workability.

Since the content of the conductive filler (C2) varies depending on the type of conductive filler used, it cannot be specified unconditionally. However, from the viewpoint of the balance of conductivity, fluidity, mechanical strength, etc., semi-aromatic polyamide copolymer Generally, it is preferably 1 part by mass or more and 30 parts by mass or less, and more preferably 2 parts by mass or more and 25 parts by mass or less with respect to 100 parts by mass of the combined (C1).
In addition, the conductive filler (C2) preferably has a surface resistivity value of 10 ⁸ Ω / square or less, preferably 10 ⁶ Ω / square or less, from the viewpoint of obtaining sufficient antistatic performance. It is more preferable. However, the addition of the conductive filler tends to deteriorate strength and fluidity. Therefore, if the target conductivity level is obtained, it is desirable that the content of the conductive filler is as small as possible.

  The conductive semi-aromatic polyamide copolymer composition (C) contains other polyamide-based resin or other thermoplastic resin in addition to the semi-aromatic polyamide copolymer (C1) and the conductive filler (C2). You may do it. 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 copolymer (C1) in the conductive semi-aromatic polyamide copolymer composition (C) is preferably 50% by mass or more.

  Furthermore, the conductive semi-aromatic polyamide copolymer composition (C) includes an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, an inorganic filler, and an antistatic agent as necessary. In addition, flame retardants, crystallization accelerators, plasticizers, colorants, lubricants, impact resistance improvers and the like may be added. In order to improve the low temperature impact resistance of the conductive semi-aromatic polyamide copolymer composition (C), it is preferable to add an impact resistance improver, particularly ISO 178 described in the aliphatic polyamide (A). It is more preferable to add a rubber-like polymer having a flexural modulus of 500 MPa or less measured according to the above.

  In the production of the conductive semi-aromatic polyamide copolymer composition (C) used in the present invention, the semi-aromatic polyamide copolymer (C1), the conductive filler (C2), and, if necessary, are added. It is manufactured using raw material components such as additives, and the method can be a known method, but is generally manufactured by melt mixing. As a specific method for melt mixing, the raw material components are uniformly mixed using a Henschel mixer, ribbon blender, V-type blender, etc. at a predetermined blending ratio, and then Banbury mixer, kneader, roll, uniaxial Or the method of kneading | mixing using kneading machines, such as multi-screw kneading extruders, such as a biaxial, is mentioned. Furthermore, the kneading order and method of each component are not particularly limited, and (C1), (C2), and a method of kneading additional compounding materials at once, (C1) and (C2) A method of blending a part and melt-kneading by the above method and then blending the remaining raw materials and melt-kneading, or blending a part of (C1) and (C2) A method of mixing the remaining raw materials using a side feeder or the like during melt kneading in (1), (C1) and a part of the additional compounding materials are blended, and during the melt kneading by the above method, the side feeder Any of the methods of mixing (C2) and the remaining raw materials using a method such as

  The conductive laminated tube according to the present invention is a diamine unit comprising 80 mol% or more of an aliphatic diamine unit having 9 to 13 carbon atoms based on (a) layer composed of aliphatic polyamide (A) and all diamine units. And a (b) layer comprising a semi-aromatic polyamide (B) comprising a dicarboxylic acid unit containing 80 mol% or more of a terephthalic acid unit and / or a naphthalene dicarboxylic acid unit with respect to all dicarboxylic acid units, and (c1) carbon A dicarboxylic acid unit comprising at least one selected from the group consisting of a diamine unit containing an aliphatic diamine unit having 9 to 13 atoms, a terephthalic acid unit, an isophthalic acid unit, and a naphthalenedicarboxylic acid unit, and (c2) a lactam A diester containing a unit and / or an aminocarboxylic acid unit, or (c3) an aliphatic diamine unit having 9 to 13 carbon atoms And a dicarboxylic acid unit containing an aliphatic dicarboxylic acid unit having 9 to 13 carbon atoms, and the molar ratio of (c1) and (c2) or (c3) is 50:50 mol% or more and 80:20 mol % Including at least three layers including (c) layer made of conductive semi-aromatic polyamide copolymer composition (C) made of semi-aromatic polyamide copolymer (C1) and conductive filler (C2) Consists of Improvement of chemical liquid permeation prevention of conductive laminated tube by including (b) layer made of semi-aromatic polyamide (B) and (c) layer made of conductive semi-aromatic polyamide copolymer composition (C) Can be planned.

In a preferred embodiment, the (a) layer made of the aliphatic polyamide (A) is disposed in the outermost layer of the conductive laminated tube. By disposing the (a) layer made of the aliphatic polyamide (A) in the outermost layer, it is possible to obtain a conductive laminated tube excellent in chemical resistance and flexibility.
As a more preferred embodiment, the (c) layer comprising the conductive semi-aromatic polyamide copolymer composition (C) is disposed in the innermost layer of the conductive laminated tube. The (c) layer made of the conductive semi-aromatic polyamide copolymer composition (C) is arranged in the innermost layer, so that thermal stability during molding, low-temperature impact resistance, deteriorated fuel resistance, chemical liquid permeation prevention It is possible to obtain a laminated tube having an excellent balance of properties and the like and having conductivity.

  In a more preferred embodiment, the (b) layer comprising the semi-aromatic polyamide (B) comprises the (a) layer comprising the aliphatic polyamide (A) and the conductive semi-aromatic polyamide copolymer composition (C). (C) between the layers. The layer (b) made of the semi-aromatic polyamide (B) is between the layer (a) made of the aliphatic polyamide (A) and the layer (c) made of the conductive semi-aromatic polyamide copolymer composition (C). By being disposed in, it is possible to achieve both low temperature impact resistance and chemical solution permeation prevention properties, and an economically advantageous conductive laminated tube can be obtained.

  In the conductive laminated tube of the present invention, the thickness of each layer is not particularly limited, and can be adjusted according to the type of polymer constituting each layer, the total number of layers in the conductive laminated tube, the use, etc. The thickness of is determined in consideration of the properties of the conductive laminated tube, such as chemical solution permeation prevention, low-temperature impact resistance, and flexibility. Generally, the thickness of the (a) layer, (b) layer, (c) layer Are preferably 3% or more and 90% or less, respectively, with respect to the thickness of the entire conductive laminated tube. In consideration of the balance between low temperature impact resistance and chemical solution permeation prevention, the thickness of the (b) layer and (c) layer should be 5% or more and 80% or less, respectively, with respect to the total thickness of the conductive laminated tube. Is more preferably 7% or more and 50% or less.

The total number of layers in the conductive laminated tube of the present invention is as follows: (a) layer made of aliphatic polyamide (A), (b) layer made of semi-aromatic polyamide (B), and conductive semi-aromatic polyamide The layer is not particularly limited as long as it is at least 3 layers including the (c) layer composed of the copolymer composition (C). Further, the conductive laminated tube of the present invention is to provide a further function or to obtain an economically advantageous conductive laminated tube in addition to the three layers (a), (b) and (c). In addition, the number of layers of the conductive laminated tube of the present invention may be three or more, but may be determined from the mechanism of the tube manufacturing apparatus. It is preferably 8 layers or less, more preferably 3 layers or more and 7 layers or less.

  Other thermoplastic resins include polymetaxylylene adipamide (other than the aliphatic polyamide (A), semi-aromatic polyamide (B), and semi-aromatic polyamide copolymer (C1) defined in the present invention. Polyamide MXD6), polymetaxylylene veramide (polyamide MXD8), polymetaxylylene azelamide (polyamide MXD9), polymetaxylylene sebacamide (polyamide MXD10), polymetaxylylene decanamide (polyamide MXD12), polymetaxylylene tele Phthalamide (polyamide MXDT), polymetaxylylene isophthalamide (polyamide MXDI), polymetaxylylene hexahydroterephthalamide (polyamide MXDT (H)), polymetaxylylene naphthalamide (polyamide MXDN), polyparaxylile Adipamide (polyamide PXD6), polyparaxylylene beramide (polyamide PXD8), polyparaxylylene azeamide (polyamide PXD9), polyparaxylylene sebacamide (polyamide PXD10), polyparaxylylene decanamide (polyamide PXD12) , Polyparaxylylene terephthalamide (polyamide PXDT), polyparaxylylene isophthalamide (polyamide PXDI), polyparaxylylene hexahydroterephthalamide (polyamide PXDT (H)), polyparaxylylene naphthalamide (polyamide) PXDN), polyparaphenylene terephthalamide (PPTA), polyparaphenylene isophthalamide (PPIA), polymetaphenylene terephthalamide (PMTA), polymetaphenylene isophthalamide (PMI) ), 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-naphthalene dimethylene dodecamide) (Polyamide 2,6-BAN12), poly (2,6-naphthalene dimethylene terephthalamide) (polyamide 2,6-BANT), poly (2,6-naphthalene dimethylene isophthalamide) (polyamide 2,6- BANI), poly (2,6-naphthalene dimethylene hexahydroterephthalamide) (polyamide 2,6-BANT (H)), poly (2,6-naphthalene dimethylene naphthalamide) (polyamide 2,6-BANN), poly (1,3-cyclohexanedimethylene adipamide) (polyamide 1,3-BAC6), poly (1,3-cyclohexanedimethyl) Lensberamide (polyamide 1,3-BAC8), poly (1,3-cyclohexanedimethylene azelamide) (polyamide 1,3-BAC9), poly (1,3-cyclohexanedimethylene sebacamide) (polyamide 1, 3-BAC10), poly (1,3-cyclohexanedimethylene dodecamide) (polyamide 1,3-BAC12), poly (1,3-cyclohexanedimethylene terephthalamide) (polyamide 1,3-BACT), poly ( 1,3-cyclohexanedimethyleneisophthalamide) (polyamide 1,3-BACI), poly ( , 3-cyclohexanedimethylenehexahydroterephthalamide) (polyamide 1,3-BACT (H)), poly (1,3-cyclohexanedimethylene naphthalamide) (polyamide 1,3-BACN), poly (1,4 -Cyclohexane dimethylene adipamide) (polyamide 1,4-BAC6), poly (1,4-cyclohexanedimethylene suberamide) (polyamide 1,4-BAC8), poly (1,4-cyclohexanedimethylene azelamide) (Polyamide 1,4-BAC9), poly (1,4-cyclohexanedimethylene sebacamide) (polyamide 1,4-BAC10), poly (1,4-cyclohexanedimethylene dodecamide) (polyamide 1,4-BAC12) ), Poly (1,4-cyclohexanedimethylene terephthalamide) (polyamide 1, -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'-methylenebiscyclohexylene dode Camide) (polyamide PACM12), poly (4,4′-methylenebiscyclohexylenetetradecanamide) (polyamide PACM14), poly (4,4′-methylenebiscyclohexylenehexadecamide) (polyamide PACM16), poly (4 , 4′-methylenebiscyclohexyleneoctadecamide) (polyamide PACM18), poly (4,4′-methylenebiscyclohexylene terephthalamide) (polyamide PACMT), poly (4,4′-methylenebiscyclohexylene isophthalate) Lamid) (polyamide PACMI), poly (4,4′-methylenebiscyclohexylene hexahydroterephthalamide) (polyamide PACMT (H)), poly (4,4′-methylenebiscyclohexylene naphthalamide) (polyamide PACMN) , Poly ( , 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) tetradecamide) (polyamide MACM14), poly (4,4′-methylenebis (2-methyl-cyclohexylene) ) Hexadecamide (Polyamide MACM16), poly (4,4′-methylenebis (2-methyl-cyclohexylene) octadecamide) (polyamide MACM18), poly (4,4′-methylenebis (2-methyl-cyclohexylene) terephthalamide) (polyamide MACMT) , Poly (4,4′-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 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) Hexadecamide) (polyamide PACP16), poly (4,4′-propylene biscyclohexylene octadecanamide) (polyamide PACP18), poly (4,4′-propylene biscyclohexylene terephthalamide) (polyamide PACP) ), Poly (4,4′-propylene biscyclohexylene isophthalamide) (polyamide PACPI), poly (4,4′-propylene biscyclohexylene hexahydroterephthalamide) (polyamide PACPT (H)), poly (4 , 4′-propylenebiscyclohexylenenaphthalamide) (polyamide PACPN), polyisophorone adipamide (polyamide IPD6), polyisophoron beramide (polyamide IPD8), polyisophorone azeamide (polyamide IPD9), polyisophorone sebacamide ( Polyamide IPD10), Polyisophoron decamide (Polyamide IPD12), Polyisophorone terephthalamide (Polyamide IPDT), Polyisophorone isophthalamide (Polyamide IPDI), Polyisophorone hexahydrotereph Ramide (polyamide IPDT (H)), polyisophorone naphthalamide (polyamide IPDN), polytetramethylene isophthalamide (polyamide 4I), polytetramethylene hexahydroterephthalamide (polyamide 4T (H)), polypentamethylene isophthal Ramide (polyamide 5I), polypentamethylene hexahydroterephthalamide (polyamide 5T (H)), polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene hexahydroterephthalamide (polyamide 6T (H)), poly (2-methylpentamethyleneisophthalamide) (polyamide M5I), poly (2-methylpentamethylenehexahydroterephthalamide) (polyamide M5T (H)), polynonamethyleneisophthalamide (polyamide 9I), polynoname Tylene hexahydroterephthalamide (polyamide 9T (H)), poly (2-methyloctamethyleneisophthalamide) (polyamide M8I), poly (2-methyloctamethylenehexahydroterephthalamide) (polyamide M8T (H)) , Polytrimethylhexamethylene isophthalamide (polyamide TMHI), polytrimethylhexamethylene hexahydroterephthalamide (polyamide TMHT (H)), polydecamethylene isophthalamide (polyamide 10I), polydecamethylene hexahydroterephthalamide ( Polyamide 10T (H)), polyundecamethylene isophthalamide (polyamide 11I), polyundecamethylene hexahydroterephthalamide (polyamide 11T (H)), polydodecamethylene isophthalamide (polyamide 12I) Polydodecamethylenehexahydroterephthalamide (polyamide 12T (H)), a raw material monomer of these polyamides and / or a copolymer using several raw material monomers of the aliphatic polyamide (A), and the like. .

  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 Functional groups having reactivity with fluororesins such as oxafluoropropylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) / hexafluoropropylene copolymer, and amino groups The said fluororesin containing is mentioned.

  Further, high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra high molecular weight polyethylene (UHMWPE), polypropylene (PP), polybutene (PB) , Polymethylpentene (TPX), ethylene / propylene copolymer (EPR), ethylene / butene copolymer (EBR), ethylene / vinyl acetate copolymer (EVA), saponified ethylene / vinyl acetate copolymer (EVOH) ), Ethylene / acrylic acid copolymer (EAA), ethylene / methacrylic acid copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), ethylene / Polyolefins such as ethyl acrylate copolymer (EEA) Resin, polystyrene (PS), syndiotactic polystyrene (SPS), methyl methacrylate / styrene copolymer (MS), methyl methacrylate / styrene / butadiene copolymer (MBS), styrene / butadiene copolymer (SBR) Styrene / isoprene copolymer (SIR), styrene / isoprene / butadiene copolymer (SIBR), styrene / butadiene / styrene copolymer (SBS), styrene / isoprene / styrene copolymer (SIS), styrene / ethylene / 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 Carboxyl groups such as cis-4-cyclohexene-1,2-dicarboxylic acid, endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid, and metal salts thereof (Na, Zn, K, Ca, Mg), maleic anhydride, itaconic anhydride, citraconic anhydride, acid anhydride groups such as endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic anhydride, glycidyl acrylate , Polyolefin resins and polystyrene resins containing a functional group such as an epoxy group such as glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl itaconate, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), Polyethylene isophthalate (PEI), poly (ethylene terephthalate / ethylene) Isophthalate) copolymer (PET / PEI), polytrimethylene terephthalate (PTT), polycyclohexanedimethylene terephthalate (PCT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyarylate (PAR), Polyester resins such as liquid crystal polyester (LCP), polylactic acid (PLA) and polyglycolic acid (PGA), polyether resins such as polyacetal (POM) and polyphenylene ether (PPO), polysulfone (PSU), polyethersulfone ( Polysulfone resins such as PESU) and polyphenylsulfone (PPSU), polythioether resins such as polyphenylene sulfide (PPS) and polythioethersulfone (PTES), polyketone (PK), and polyether ketone (PEK), Polyetheretherketone (PEEK), Polyetherketoneketone (PEKK), Polyetheretherketoneketone (PEEKK), Polyetherketoneetherketoneketone (PEKEKK) and other polyketone resins, Polyacrylonitrile (PAN) Polynitriles such as polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), and acrylonitrile / butadiene copolymer (NBR) Resin, polymethacrylate resins such as polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA), polyvinyl ester resins such as polyvinyl acetate (PVAc), polyvinylidene chloride (PVD) ), Polyvinyl chloride (PVC), polyvinyl chloride / vinylidene chloride copolymer, polyvinyl chloride resin such as vinylidene chloride / methyl acrylate copolymer, cellulose resin such as cellulose acetate and cellulose butyrate, polycarbonate (PC) Polycarbonate resins such as thermoplastic polyimide (TPI), polyetherimide, polyesterimide, polyamideimide (PAI), polyesteramideimide, and other polyimide resins, thermoplastic polyurethane resins, polyamide elastomers, polyurethane elastomers, polyester elastomers, etc. Is mentioned.

  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 method for producing a conductive laminated tube, a method of melt extrusion using an extruder corresponding to the number of layers or the number of materials, a method of simultaneously laminating inside or outside a die (coextrusion method), or a single-layer tube once. Alternatively, there is a method (coating method) in which a conductive laminated tube produced by the above method is produced in advance, and an adhesive is used on the outside in order to integrate the resins and laminate them. . The conductive laminated tube of the present invention is preferably produced by a co-extrusion method in which various materials are coextruded in a molten state, and both are heat-fused (melt-bonded) to produce a laminated structure tube in one step. .

  In addition, when the obtained conductive laminated tube has a complicated shape or when it is subjected to heat bending after molding to form a molded product, the above-mentioned conductive laminated tube is used to remove residual distortion of the molded product. After forming, the target molded product can be obtained 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 conductive 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 conductive laminated tube, but may be partially provided in an appropriate region in the middle. The corrugated region can be easily formed by first forming a straight tube and then molding it to obtain a predetermined corrugated shape or the like. By having such a corrugated region, it has shock absorption and attachment is easy. Furthermore, for example, it is possible to add necessary parts such as a connector, or to form an L shape or a U shape by bending.

  All or part of the outer periphery of the conductive laminated tube formed in this way is made of natural rubber (NR), butadiene rubber (BR), isoprene rubber, taking into account stones, abrasion with other parts, and flame resistance. (IR), 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 (EP) ), Ethylene propylene diene rubber (EPDM), ethylene vinyl acetate rubber (EVM), mixed rubber of NBR and EPDM, acrylic rubber (ACM), ethylene acrylic rubber (AEM), acrylate butadiene rubber (ABR), styrene butadiene rubber (SBR) , Carboxylated styrene butadiene rubber (XSBR), styrene isoprene rubber (SIR), styrene isoprene butadiene rubber (SIBR), urethane rubber, silicone rubber (MQ, VMQ), fluoro rubber (FKM, FFKM), fluorosilicone rubber (FVMQ) Further, a solid or sponge-like protective member (protector) made of a thermoplastic elastomer such as vinyl chloride, 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 conductive laminated tube. In the case of a cylindrical member, the conductive laminated tube can be inserted later into a previously produced cylindrical member, or the cylindrical member can be coated and extruded onto the conductive laminated tube to adhere both together. . In order to bond them together, an adhesive is applied to the inner surface of the protective member or the concave surface as necessary, and the conductive laminated tube is inserted or fitted into this, and the two are brought into close contact with each other. To form an integrated structure. It can also be reinforced with metal or the like.

  The outer diameter of the conductive laminated tube takes into account the flow rate of chemicals (for example, fuel such as alcohol-containing gasoline), and the wall thickness is such that the permeation rate of chemicals does not increase and the normal tube breaking pressure can be maintained. In addition, the thickness is designed so as to maintain flexibility with a satisfactory degree of ease of assembling the tube and vibration resistance during use, but is not limited thereto. Preferably, the outer diameter is 4 mm to 300 mm, the inner diameter is 3 mm to 250 mm, and the wall thickness is 0.5 mm to 25 mm.

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

  Moreover, since the electroconductive laminated tube of this invention is excellent in chemical | medical solution permeation prevention property, it is suitable as a chemical | medical solution conveyance tube. Examples of the chemical solution include aromatic hydrocarbon solvents such as benzene, toluene, xylene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, diethylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol, and the like. Alcohol, phenol solvents, dimethyl ether, dipropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran and other ether solvents, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, tetrachloroethane Halogen solvents such as perchloroethane, chlorobenzene, acetone, methyl ethyl ketone, diethyl ketone, acetone Ketone solvents such as phenone, gasoline, kerosene, diesel gasoline, alcohol-containing gasoline, methyl-t-butyl ether, oxygen-containing gasoline, amine-containing gasoline, sour gasoline, castor oil base brake fluid, glycol ether brake fluid, borate ester Examples include brake fluid, brake fluid for extremely cold regions, silicone fluid brake fluid, mineral oil brake fluid, power steering oil, hydrogen sulfide oil, window washer fluid, engine coolant, urea solution, pharmaceutical agent, ink, paint, etc. . The conductive laminated tube of the present invention is suitable as a tube for conveying the above chemical solution, and specifically, a fuel tube such as a feed tube, a return tube, an evaporation tube, a fuel filler tube, an ORVR tube, a reserve tube, a vent tube, etc. , Oil tube, oil drilling tube, underground buried tube for gas station, brake tube, window washer fluid tube, engine coolant (LLC) tube, reservoir tank tube, urea solution transport tube, cooler tube for cooling water, refrigerant, etc. Air conditioner refrigerant tube, heater tube, load heating tube, floor heating tube, infrastructure supply tube, fire extinguisher and fire extinguishing equipment tube, medical cooling equipment tube, ink, paint spray tube, etc. Other chemical liquid tube and the like. 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 polyamide 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.

Moreover, each physical property of the conductive laminated tube was measured by the following methods.
[Thermal stability during molding]
By observing the cross section of 10 places in the molded tube, it was confirmed whether foaming caused by the added olefin polymer or the occurrence of a deteriorated product called “eye” was generated. When foaming or a deteriorated product was not observed, it was judged that the thermal stability during molding was good.

[Low temperature impact resistance]
The impact test was performed at -40 ° C by the method described in SAE J-2260 7.5.

[Degradation resistance]
A solution containing 18.1 ml of 80% cumene hydroperoxide having a purity of 18.1 ml per liter of the fuel in methanol-containing gasoline (CM15) mixed in isooctane / toluene / methanol = 42.5 / 42.5 / 15% by volume; 0.73 g of copper stearate and 3 ml of acetic acid were added, and the fuel was adjusted so that the number of peroxides (PON) was 200 (mg equivalent / L). One end of the tube cut to 200 mm was sealed, the deteriorated fuel was sealed inside, and the remaining end was sealed. The test tube was then held in an 80 ° C. oven for 336 hours. Thereafter, the tube was taken out and subjected to an impact test at −40 ° C. by the method described in SAE J-2260 7.5. Judged to be excellent.

[Permeability of chemical solution (alcohol-containing gasoline) permeation]
One end of a tube cut to 200 mm was sealed, and alcohol-containing gasoline mixed with Fuel C (isooctane / toluene = 50/50 volume ratio) and ethanol in a 90/10 volume ratio was put inside, and the remaining end was 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 change in mass per day was divided by the surface area of the inner layer of the tube to calculate the permeation amount of alcohol-containing gasoline (g / m ² · day).

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

[Materials Used in Examples and Comparative Examples]
Aliphatic polyamide (A)
Manufacture of Polyamide 12 Resin Composition (A-1) Polyamide 12 (a-1) (Ube Industries, UBESTA3030UX1, relative viscosity 2.21) was coated with maleic anhydride-modified ethylene / propylene as an impact resistance improver. A polymer (manufactured by JSR Co., Ltd., JSR T7761P) is mixed in advance and supplied to a twin-screw melt kneader (manufactured by Nippon Steel Works Co., Ltd., model: TEX44), while the cylinder of the biaxial melt kneader is in the middle Then, benzenesulfonic acid butyramide as a plasticizer is injected by 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 bath, cooled, cut, and vacuumed After drying, a pellet of a polyamide 12 resin composition comprising 85% by mass of polyamide 12, 10% by mass of an impact resistance improving material, and 5% by mass of a plasticizer. To give the door (hereinafter, this polyamide 12 resin composition of (A-1).).

Manufacture of polyamide 610 (a-2) In a pressure-resistant reaction vessel with an internal volume of 70 liters equipped with a stirrer, 17.6 kg of a 1,6 hexanediamine and sebacic acid equimolar salt 1 wt. After charging 63.8 g and replacing the inside of the polymerization tank with nitrogen, it was heated to 220 ° C. and stirred at this temperature so that the reaction system was in a uniform state. Next, the temperature in the polymerization tank was raised to 270 ° C., and polymerization was performed with stirring for 2 hours while adjusting the pressure in the tank to 1.7 MPa. Thereafter, the pressure was released to normal pressure over about 2 hours, and then the pressure was reduced to 53 kPa, and polymerization was performed for 4 hours under reduced pressure. Next, nitrogen was introduced into the autoclave, and after returning to normal pressure, the strand was extracted from the lower nozzle of the reaction vessel and cut to obtain pellets. This pellet was dried under reduced pressure to obtain a polyamide 610 having a relative viscosity of 2.48, a terminal amino group concentration of 73 μeq / g, and a terminal carboxyl group concentration of 14 μeq / g (hereinafter, this polyamide 610 is referred to as (a-2)).

Manufacture of polyamide 610 resin composition (A-2) Polyamide 610 (a-2) was modified with maleic anhydride-modified ethylene / propylene copolymer (manufactured by JSR Corporation, JSR T7761P) as an impact resistance improver, antioxidant. As triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan, IRGANOX 245), and tris (2,4-di -T-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 biaxial melt kneader Benzenesulfonic acid butyramide as a plasticizer is injected from the middle of the cylinder with a metering pump, After melting and kneading at a binder temperature of 200 ° C. to 270 ° C. and extruding the molten resin into a strand shape, this is introduced into a water tank, cooled, cut, and vacuum dried to give polyamide 610 80 mass%, impact resistance improving material 10 mass. %, A pellet of polyamide 610 resin composition 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 of 10% by weight of a plasticizer (hereinafter referred to as This polyamide 610 resin composition is referred to as (A-2)).

Production of polyamide 612 (a-3) In the production of polyamide 610 (a-2), 17.6 kg of a 50 mass% aqueous solution of an equimolar salt of 1,6-hexanediamine and sebacic acid was added to 1,6-hexanediamine and dodecane. 20.0 kg of 50% by weight aqueous solution of equimolar salt of diacid, except that the amount of 1,6-hexanediamine added was changed from 63.8 g to 70.0 g. By the method, a polyamide 612 having a relative viscosity of 2.52, a terminal amino group concentration of 65 μeq / g, and a terminal carboxyl group concentration of 19 μeq / g was obtained (hereinafter, this polyamide 612 is referred to as (a-3)).

Manufacture of polyamide 612 resin composition (A-3) Polyamide 610 resin except that polyamide 610 (a-2) was changed to polyamide 612 (a-3) in the manufacture of polyamide 610 resin composition (A-2). In the same manner as in the production of the composition (A-2), an antioxidant of 0.8% is added to 100 parts by mass of 80% by mass of polyamide 612, 10% by mass of an impact resistance improving material, and 10% by mass of a plasticizer. Pellets of a polyamide 612 resin composition comprising parts by mass and 0.2 parts by mass of a phosphorus processing stabilizer were obtained (hereinafter, this polyamide 612 resin composition is referred to as (A-3)).

Semi-aromatic polyamide (B)
Production of semi-aromatic polyamide (B1-1): 4.984 kg (30.0 mol) of terephthalic acid, 2.374 kg (15.0 mol) of 1,9-nonanediamine, 2.methyl-1,8-octanediamine 374 kg (15.0 mol), 65.9 g (0.54 mol) of benzoic acid, 9.8 g of sodium hypophosphite monohydrate (0.1% by mass with respect to the raw material), and 6.0 L of distilled water Was placed in an autoclave and purged with nitrogen. The mixture was stirred at 100 ° C. for 30 minutes, and the internal temperature was raised to 190 ° C. over 2 hours. At this time, the autoclave was pressurized to 2.0 MPa. The reaction was continued as it was for 1 hour, then the temperature was raised to 230 ° C., and then the temperature was maintained at 230 ° C. for 2 hours, and the reaction was carried out while gradually removing water vapor and keeping the pressure at 2.0 MPa. Next, the pressure was reduced to 1.0 MPa over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer. This was dried at 100 ° C. under reduced pressure for 12 hours, pulverized to a size of 2 mm or less, and solid-phase polymerized at 210 ° C. and 0.013 kPa for 8 hours, with a melting point of 265 ° C. and a relative viscosity of 2.38. An aromatic polyamide (polyamide 9T / M8T = 50/50 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B1-1)).

Manufacture of a semi-aromatic polyamide composition (B-1) To a semi-aromatic polyamide (B1-1), a maleic anhydride-modified ethylene / propylene copolymer (manufactured by JSR Corporation, JSR T7761P) as an impact resistance improver, Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan, IRGANOX 245) as an antioxidant, and tris (2, 4-di-t-butylphenyl) phosphite (manufactured by BASF Japan, IRGAFOS168) is mixed in advance and supplied to a twin-screw melt kneader (manufactured by Nippon Steel Works, model: TEX44), and the cylinder temperature is 240 ° C. From 300 to 300 ° C., and the molten resin is extruded into a strand shape. G, vacuum-dried, 100 parts by mass of semi-aromatic polyamide 90% by mass and 10% by mass of impact resistance improving material, 0.8 parts by mass of antioxidant, 0.2 parts by mass of phosphorus processing stabilizer A pellet of a semi-aromatic polyamide composition was obtained (hereinafter, this semi-aromatic polyamide composition is referred to as (B-1)).

Production of semi-aromatic polyamide (B1-2) In production of semi-aromatic polyamide (B1-1), 2,374 kg (15.0 mol) of 1,9-nonanediamine, 2-methyl-1,8-octanediamine 2 374 kg (15.0 mol) was changed to 4.09 kg (25.5 mol) of 1,9-nonanediamine and 0.712 kg (4.5 mol) of 2-methyl-1,8-octanediamine, and the solid-state polymerization temperature Is a semi-aromatic polyamide having a melting point of 305 ° C. and a relative viscosity of 2.34 (polyamide 9T / M8T = 85) in the same manner as in the production of the semi-aromatic polyamide (B1-1) except that the temperature is changed from 210 to 240 ° C. / 15 mol%) (hereinafter, this semi-aromatic polyamide is referred to as (B1-2)).

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

Production of semi-aromatic polyamide (B1-3) Production of semi-aromatic polyamide (B1-3) In production of semi-aromatic polyamide (B1-1), 2.374 kg (15.0 mol) of 1,9-nonanediamine, 2.374 kg (15.0 mol) of 2-methyl-1,8-octanediamine was changed to 5.169 kg (30.0 mol) of 1,10-decanediamine, and the solid-state polymerization temperature was changed from 210 to 260 ° C. Except that a semi-aromatic polyamide (polyamide 10T = 100 mol%) having a melting point of 315 ° C. and a relative viscosity of 2.33 was obtained in the same manner as in the production of the semi-aromatic polyamide (B1-1) (hereinafter referred to as “this”). Semi-aromatic polyamide is referred to as (B1-3)).

Production of semi-aromatic polyamide composition (B-3) In the production of semi-aromatic polyamide composition (B-1), the semi-aromatic polyamide (B1-1) is changed to (B1-3) and the cylinder temperature is set to 300. 100 parts by mass in total of 90% by mass of semi-aromatic polyamide and 10% by mass of impact modifier, in the same manner as the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from 350C to 350C. In contrast, a pellet of a semi-aromatic polyamide composition comprising 0.8 part by mass of an antioxidant and 0.2 part by mass of a phosphorus processing stabilizer was obtained (hereinafter, this semi-aromatic polyamide composition (B- 3).)

Production of conductive semi-aromatic polyamide composition (B-4) Maleic anhydride-modified ethylene / 1-butene copolymer (manufactured by Mitsui Chemicals, Inc.) as a semi-aromatic polyamide (B1-3) as an impact resistance improver , Tuffmer MH5010) and ethylene / 1-butene copolymer (Mitsui Chemicals, Tafmer A-0550), carbon black (C2-1) as conductive filler (Lion, Ketjen Black EC600JD) , Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan, IRGANOX 245) as an antioxidant, and tris (2 , 4-di-t-butylphenyl) phosphite (BASF Japan, IRGAFOS168) Mixed and fed to a twin-screw melt kneader (manufactured by Nippon Steel Works, model: TEX44), melt kneaded at a cylinder temperature of 260 ° C. to 360 ° C., and the molten resin is extruded into a strand shape. The mixture was introduced into a water tank, cooled, cut and vacuum dried, and the antioxidant was added to 100 parts by mass of the total amount of semi-aromatic polyamide 68% by mass, impact resistance improving material 25% by mass, and conductive filler 7% by mass. A conductive semi-aromatic polyamide composition pellet comprising 8 parts by mass and phosphorus-based processing stabilizer 0.2 part by mass was obtained (hereinafter, this conductive semi-aromatic polyamide composition is referred to as (B-4)). .

Production of semi-aromatic polyamide (B1-4) In the production of semi-aromatic polyamide (B1-1), 4.984 kg (30.0 mol) of terephthalic acid was added to 6.486 kg (30.0 mol) of 2,6-naphthalenedicarboxylic acid. The semi-aromatic polyamide having a melting point of 275 ° C. and a relative viscosity of 2.37 (polyamide 9N / M8N = 50/50 mol), in the same manner as in the production of the semi-aromatic polyamide (B1-1) %) (Hereinafter, this semi-aromatic polyamide is referred to as (B1-4)).

Production of semi-aromatic polyamide composition (B-5) In the production of semi-aromatic polyamide composition (B-1), the semi-aromatic polyamide (B1-1) is changed to (B1-4), and the cylinder temperature is set to 300. 100 parts by mass in total of 90% by mass of semi-aromatic polyamide and 10% by mass of impact modifier, in the same manner as in the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from 310 ° C. to 310 ° C. In contrast, a pellet of a semi-aromatic polyamide composition comprising 0.8 part by mass of an antioxidant and 0.2 part by mass of a phosphorus processing stabilizer was obtained (hereinafter, this semi-aromatic polyamide composition (B- 5).)

Production of semi-aromatic polyamide (B1-5) In production of semi-aromatic polyamide (B1-1), 2,374 kg (15.0 mol) of 1,9-nonanediamine, 2-methyl-1,8-octanediamine 2 374 kg (15.0 mol) was changed to 1,326-decanediamine (1,326 mol) (13.5 mol) and 1,6-hexanediamine (1.917 kg (16.5 mol)), and the solid-state polymerization temperature was changed from 210. A semi-aromatic polyamide having a melting point of 307 ° C. and a relative viscosity of 2.32 (polyamide 10T / 6T = 45/55 mol) in the same manner as in the production of the semi-aromatic polyamide (B1-1) except that the temperature was changed to 260 ° C. %) (Hereinafter, this semi-aromatic polyamide is referred to as (B1-5)).

Production of semi-aromatic polyamide composition (B-6) In production of semi-aromatic polyamide composition (B-1), semi-aromatic polyamide (B1-1) was changed to (B1-5), and the cylinder temperature was set to 300. 100 parts by mass in total of 90% by mass of semi-aromatic polyamide and 10% by mass of impact modifier, in the same manner as the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from 350C to 350C. In contrast, a pellet of a semi-aromatic polyamide composition comprising 0.8 part by mass of an antioxidant and 0.2 part by mass of a phosphorus processing stabilizer was obtained (hereinafter, this semi-aromatic polyamide composition (B- 6).)

Production of conductive semi-aromatic polyamide composition (B-7) In production of conductive semi-aromatic polyamide composition (B-4), semi-aromatic polyamide (B1-3) was changed to (B1-5). Except for the above, in the same manner as in the production of the conductive semi-aromatic polyamide composition (B-4), a total of 100% of the semi-aromatic polyamide 68% by mass, the impact resistance improving material 25% by mass, and the conductive filler 7% by mass. A conductive semi-aromatic polyamide composition pellet comprising 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus processing stabilizer was obtained with respect to parts by mass (hereinafter referred to as this conductive semi-aromatic polyamide). The composition is referred to as (B-7).)

Production of semi-aromatic polyamide (B1-6) In production of semi-aromatic polyamide (B1-1), terephthalic acid 4.984 kg (30.0 mol), 1,9-nonanediamine 2.374 kg (15.0 mol) 2-methyl-1,8-octanediamine 2.374 kg (15.0 mol), terephthalic acid 3.240 kg (19.5 mol), isophthalic acid 1.246 kg (7.5 mol), adipic acid 0.438 kg (3.0 moles), 1,6-hexanediamine 3.718 kg (32.0 moles), except that the solid-state polymerization temperature was changed from 210 to 260 ° C. of the semi-aromatic polyamide (B1-1). A semi-aromatic polyamide (polyamide 6T / 6I / 66 = 65/25/10 mol%) having a melting point of 315 ° C. and a relative viscosity of 2.38 was obtained in the same manner as in the production (hereinafter, this semi-fine An aromatic polyamide is referred to as (B1-6).)

Production of semi-aromatic polyamide composition (B-8) In the production of semi-aromatic polyamide composition (B-1), semi-aromatic polyamide (B1-1) was changed to (B1-6), and the cylinder temperature was set to 300. 100 parts by mass in total of 90% by mass of semi-aromatic polyamide and 10% by mass of impact modifier, in the same manner as the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from 350C to 350C. In contrast, a pellet of a semi-aromatic polyamide composition comprising 0.8 part by mass of an antioxidant and 0.2 part by mass of a phosphorus processing stabilizer was obtained (hereinafter, this semi-aromatic polyamide composition (B- 8).)

Production of conductive semi-aromatic polyamide composition (B-9) In production of conductive semi-aromatic polyamide composition (B-4), semi-aromatic polyamide (B1-3) was changed to (B1-6). Except for the above, in the same manner as in the production of the conductive semi-aromatic polyamide composition (B-4), a total of 100% of the semi-aromatic polyamide 68% by mass, the impact resistance improving material 25% by mass, and the conductive filler 7% by mass. A conductive semi-aromatic polyamide composition pellet comprising 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus processing stabilizer was obtained with respect to parts by mass (hereinafter referred to as this conductive semi-aromatic polyamide). The composition is referred to as (B-9).)

Conductive semi-aromatic polyamide copolymer composition (C)
Production of semi-aromatic polyamide copolymer (C1-1) terephthalic acid 4.943 kg (29.7 mol), (c1) 1.425 kg (9.0 mol) 1,9-nonanediamine and 2-methyl-1, 8-octanediamine 1.425 kg (9.0 mol), (c2) 1,6-hexanediamine 1.394 kg (12.0 mol), benzoic acid 65.9 g (0.54 mol), sodium hypophosphite 9.3 g of monohydrate (0.1% by mass with respect to the raw material) and 6.0 L of distilled water were placed in an autoclave and purged with nitrogen. The mixture was stirred at 100 ° C. for 30 minutes, and the internal temperature was raised to 190 ° C. over 2 hours. At this time, the autoclave was pressurized to 1.8 MPa. The reaction was continued as it was for 1 hour, then the temperature was raised to 200 ° C., and then the temperature was maintained at 200 ° C. for 2 hours, and the reaction was carried out while gradually removing water vapor and keeping the pressure at 2.0 MPa. Next, the pressure was reduced to 1.0 MPa over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer. This was dried at 100 ° C. under reduced pressure for 12 hours, pulverized to a size of 2 mm or less, solid-phase polymerized at 190 ° C. and 0.013 kPa for 8 hours, a melting point of 226 ° C. and a relative viscosity of 2.15 half. An aromatic polyamide copolymer (polyamide 9T / M8T / 6T = 30/30/40 mol%) was obtained (hereinafter, this semi-aromatic polyamide copolymer is referred to as (C1-1)).

Production of conductive semi-aromatic polyamide copolymer composition (C-1) In production of conductive semi-aromatic polyamide composition (B-4), semi-aromatic polyamide (B1-1) is mixed with semi-aromatic polyamide copolymer. A semi-aromatic polyamide was prepared in the same manner as in the production of the conductive semi-aromatic polyamide composition (B-4) except that the temperature of the cylinder was changed from 360 ° C. to 280 ° C. instead of the polymer (C1-1). From a total of 100 parts by mass of 68% by mass of the copolymer, 25% by mass of the impact resistance improving material, and 7% by mass of the conductive filler, from 0.8 parts by mass of the antioxidant and 0.2 parts by mass of the phosphorus processing stabilizer. Thus obtained conductive semi-aromatic polyamide copolymer composition pellets (hereinafter, this conductive semi-aromatic polyamide copolymer composition is referred to as (C-1)).

Production of conductive semi-aromatic polyamide copolymer composition (C-2) In production of conductive semi-aromatic polyamide copolymer composition (C-1), carbon black (C2-1) was converted to carbon nanotube (C2). -2) A semi-aromatic polyamide copolymer of 70 mass by the same method as the production of the conductive semi-aromatic polyamide copolymer composition (C-1) except that it was changed to (Nanosil Co., Ltd., NC7000). %, Impact resistance improver 25% by mass, conductive filler 5% by mass, 100 parts by mass of conductive semi-fragrance comprising 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus processing stabilizer A pellet of an aromatic polyamide copolymer composition was obtained (hereinafter, this conductive semi-aromatic polyamide copolymer composition is referred to as (C-2)).

Production of semi-aromatic polyamide copolymer (C1-2) In production of semi-aromatic polyamide copolymer (C1-1), (c1) 1.425 kg (9.0 mol) of 1,9-nonanediamine and 2- 1.45 kg (9.0 mol) of methyl-1,8-octanediamine, 1.394 kg (12.0 mol) of (c2) 1,6-hexanediamine and 1.543 kg of (c1) 1,9-nonanediamine (9 mol) .75 mol) and 2-methyl-1,8-octanediamine 1.543 kg (9.75 mol), (c2) 1,6-hexanediamine 1.220 kg (10.5 mol) A semi-aromatic polyamide copolymer having a melting point of 230 ° C. and a relative viscosity of 2.16 (polyamide 9T / M8T / 6T = 32.5 / 3) in the same manner as in the production of the aromatic polyamide copolymer (C1-1). 2.5 / 35 mol%) (hereinafter, this semi-aromatic polyamide copolymer is referred to as (C1-2)).

Production of conductive semi-aromatic polyamide copolymer composition (C-3) In production of conductive semi-aromatic polyamide copolymer composition (C-1), semi-aromatic polyamide copolymer (C1-1) In the same manner as in the production of the conductive semi-aromatic polyamide copolymer composition (C-1), except that is changed to (C1-2), the semi-aromatic polyamide copolymer 68% by mass, impact resistance Conductive semi-aromatic polyamide copolymer consisting of 0.8 parts by weight of antioxidant and 0.2 parts by weight of phosphorus-based processing stabilizer for 100 parts by weight in total of 25% by weight of improving material and 7% by weight of conductive filler A pellet of the coalescence composition was obtained (hereinafter, this conductive semi-aromatic polyamide copolymer composition is referred to as (C-3)).

Production of semi-aromatic polyamide copolymer (C1-3) In the production of semi-aromatic polyamide copolymer (C1-1), 1.394 kg (12.0 mol) of (c2) 1,6-hexanediamine was ( c2) Semi-aromatic polyamide copolymer, except that it was changed to 0.697 kg (6.0 mol) of 1,6-hexanediamine and 0.697 kg (6.0 mol) of 2-methyl-1,5-pentanediamine A semi-aromatic polyamide copolymer having a melting point of 217 ° C. and a relative viscosity of 2.14 (polyamide 9T / M8T / 6T / M5T = 30/30/20/20 mol%) in the same manner as in the production of (C1-1). (Hereinafter, this semi-aromatic polyamide copolymer is referred to as (C1-3)).

Production of conductive semi-aromatic polyamide copolymer composition (C-4) In production of conductive semi-aromatic polyamide copolymer composition (C-1), semi-aromatic polyamide copolymer (C1-1) In the same manner as in the production of the conductive semi-aromatic polyamide copolymer composition (C-1), except that is changed to (C1-3), the semi-aromatic polyamide copolymer 68% by mass, impact resistance Conductive semi-aromatic polyamide copolymer consisting of 0.8 parts by weight of antioxidant and 0.2 parts by weight of phosphorus-based processing stabilizer for 100 parts by weight in total of 25% by weight of improving material and 7% by weight of conductive filler A pellet of the coalescence composition was obtained (hereinafter, this conductive semi-aromatic polyamide copolymer composition is referred to as (C-4)).

Example 1
Using the polyamide 12 resin composition (A-1), semi-aromatic polyamide composition (B-1), and conductive semi-aromatic polyamide copolymer composition (C-1) shown above, (A-1) at a extrusion temperature of 260 ° C, (B-1) at an extrusion temperature of 300 ° C, and (C-1) at an extrusion temperature of 280 ° C. Separately melted, the molten resin discharged is merged by an adapter, formed into a tube, cooled by a sizing die that controls dimensions, taken up, and the layer made of (A-1) is the layer (a) (outermost layer) ), (B-1) is the layer (b) (intermediate layer), and (C-1) is the layer (c) (innermost layer), the layer structure is (a) / (b ) / (C) = 0.70 / 0.15 / 0.15 mm, inner diameter 6 mm, outer diameter 8 mm To obtain a cube. 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 2
In Example 1, except that the conductive semi-aromatic polyamide copolymer composition (C-1) was changed to (C-2), the layer structure shown in Table 1 was used in the same manner as in Example 1. A laminated tube was obtained. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 3
In Example 1, except that the conductive semi-aromatic polyamide copolymer composition (C-1) was changed to (C-3), the layer structure shown in Table 1 was used in the same manner as in Example 1. A laminated tube was obtained. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 4
In Example 1, except that the conductive semi-aromatic polyamide copolymer composition (C-1) was changed to (C-4), the layer structure shown in Table 1 was used in the same manner as in Example 1. A laminated tube was obtained. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 5
In Example 1, except that the semi-aromatic polyamide composition (B-1) was changed to (B-2) and the extrusion temperature of (B-2) was changed to 340 ° C., the same method as in Example 1 was used. Thus, a laminated tube having the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. 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 6
In Example 1, except that the semi-aromatic polyamide composition (B-1) was changed to (B-3) and the extrusion temperature of (B-3) was changed to 350 ° C., the same method as in Example 1 was used. Thus, a laminated tube having the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. 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 7
In Example 1, the semi-aromatic polyamide composition (B-1) was changed to (B-5), and the extrusion temperature of (B-5) was changed to 310 ° C. Thus, a laminated tube having the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 8
Example 1 is the same as Example 1 except that the polyamide 12 resin composition (A-1) is changed to the polyamide 610 resin composition (A-2) and the extrusion temperature of (A-2) is changed to 270 ° C. A laminated tube having the layer configuration shown in Table 1 was obtained in the same manner. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 9
Example 1 is the same as Example 1 except that the polyamide 12 resin composition (A-1) is changed to the polyamide 612 resin composition (A-3) and the extrusion temperature of (A-3) is changed to 270 ° C. A laminated tube having the layer configuration shown in Table 1 was obtained in the same manner. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Comparative Example 1
In Example 1, except that the semiaromatic polyamide composition (B-1) and the conductive semiaromatic polyamide copolymer composition (C-1) were not used, 1 was obtained. Table 1 shows the physical property measurement results of the single-layer tube.

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 polyamide 12 resin composition (A-1). The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Comparative Example 3
In Example 1, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 1 except not using a semi-aromatic polyamide composition (B-1). The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Comparative Example 4
In Example 1, the conductive semi-aromatic polyamide copolymer composition (C-1) is changed to the conductive semi-aromatic polyamide composition (B-4), and the extrusion temperature of (B-4) is 360 ° C. A laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 1 except that the change was made. 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 5
In Example 1, the semi-aromatic polyamide composition (B-1) was changed to (B-6) and the extrusion temperature of (B-6) was changed to 350 ° C. Thus, a laminated tube having the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. 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 6
In Example 1, the conductive semi-aromatic polyamide copolymer composition (C-1) is changed to the conductive semi-aromatic polyamide composition (B-7), and the extrusion temperature of (B-7) is set to 360 ° C. A laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 1 except that the change was made. 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 7
In Example 1, the semi-aromatic polyamide composition (B-1) was changed to (B-8), and the extrusion temperature of (B-8) was changed to 350 ° C. Thus, a laminated tube having the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. 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 8
In Example 1, the conductive semi-aromatic polyamide copolymer composition (C-1) is changed to the conductive semi-aromatic polyamide composition (B-9), and the extrusion temperature of (B-9) is 360 ° C. A laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 1 except that the change was made. 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 single-layer tube of Comparative Example 1 that does not have a layer made of the semi-aromatic polyamide and the conductive semi-aromatic polyamide copolymer composition defined in the present invention has chemical liquid permeation preventive properties. It is inferior and has no electrical conductivity. The laminated tube of Comparative Example 2 which does not have a layer made of the aliphatic polyamide specified in the present invention was inferior in low temperature impact resistance and deterioration fuel resistance. The laminated tube of Comparative Example 3 that did not have a layer made of the semi-aromatic polyamide composition defined in the present invention was inferior in chemical solution permeation prevention. The laminated tubes of Comparative Example 4, Comparative Example 6 and Comparative Example 8 having a layer made of a conductive semi-aromatic polyamide composition other than those specified in the present invention were inferior in molding heat stability and resistance to deterioration fuel. The laminated tubes of Comparative Example 5 and Comparative Example 7 having a layer made of a semi-aromatic polyamide composition other than those specified in the present invention were inferior in interlayer adhesion.
On the other hand, the laminated tubes of Examples 1 to 9 defined in the present invention have conductivity, and have molding heat stability, low temperature impact resistance, deterioration fuel resistance, chemical permeation prevention, and interlayer adhesion. It is clear that various properties such as properties are good.

Claims (6)

(A) layer composed of aliphatic polyamide (A), based on all diamine units, diamine units containing 80 mol% or more of aliphatic diamine units having 9 to 13 carbon atoms, and all dicarboxylic acid units, (C1) 1,9- with respect to the (b) layer composed of a semi-aromatic polyamide (B) composed of a dicarboxylic acid unit containing 80 mol% or more of terephthalic acid units and / or naphthalenedicarboxylic acid units, and all diamine units Nonanediamine unit and 2-methyl-1,8-octanediamine unit and (c2) an aliphatic diamine unit having 4 to 6 carbon atoms in an amount of 60 mol% or more, and a molar ratio of (c1) to (c2) is 40: 60 mol% or more and 80:20 mol% or less of diamine units and all dicarboxylic acid units, terephthalic acid units and / or naphthalene dicarboxylic acid units % Including at least three layers including (c) layer composed of conductive semi-aromatic polyamide copolymer composition (C) composed of semi-aromatic polyamide copolymer (C1) and conductive filler (C2). A conductive laminated tube characterized by comprising: In the semiaromatic polyamide (B), the aliphatic diamine unit having 9 to 13 carbon atoms is 1,9-nonanediamine and / or 2-methyl-1,8-octanediamine, 1,10-decanediamine, And at least one member selected from the group consisting of units derived from 1,12-dodecanediamine. In the semiaromatic polyamide copolymer (C1), (c2) an aliphatic diamine unit having 4 to 6 carbon atoms is composed of 1,6-hexanediamine and / or 2-methyl-1,5-pentanediamine. The conductive laminated tube according to claim 1 or 2, wherein the conductive laminated tube is an induced unit. The aliphatic polyamide (A) is polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene decanamide ( Polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecane methylene decanamide (polyamide 1010), polydecamethylene dodecane (polyamide 1012), and polydodecamethylene dodecane (polyamide 1212). The conductive laminated tube according to any one of claims 1 to 3, wherein the conductive laminated tube is at least one homopolymer or a copolymer using several kinds of raw material monomers forming them. The (a) layer made of the aliphatic polyamide (A) is arranged in the outermost layer, and the (c) layer made of the conductive semi-aromatic polyamide copolymer composition (C) is arranged in the innermost layer. The electroconductive laminated tube in any one of Claim 1 to 4 characterized by the above-mentioned. The conductive laminated tube according to any one of claims 1 to 5, wherein the conductive laminated tube is manufactured by coextrusion molding.