JP6202254B2 - Conductive laminated tube - Google Patents

Description

  The present invention includes a layer comprising an aliphatic polyamide, a layer comprising a semi-aromatic polyamide having a specific structure, and a conductive semi-aromatic polyamide composition comprising a semi-aromatic polyamide having a specific structure and a conductive filler. The present invention relates to a conductive laminated tube, which is excellent in heat stability during molding, low temperature impact resistance, deterioration fuel resistance, chemical permeation prevention, and interlayer adhesion, and has conductivity.

  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, but when single-layer molded products using these are used, heat resistance, chemical resistance, etc. are insufficient. 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 property for chemical liquids such as these fuels is not sufficient, and in particular, an improvement for the permeation-preventing property of alcohol-containing gasoline is required.

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

  Among these, a fuel transfer tube in which polymetaxylylene adipamide (polyamide MXD6) is arranged in an intermediate layer has been proposed (see Patent Document 2). Polyamide MXD6 is known to have good adhesive strength with polyamide 6, but the interlayer adhesion is insufficient for polyamide 11 or polyamide 12 conventionally used as the constituent material of single-layer tube It is. For this reason, it is necessary to provide an adhesive layer between the layers, resulting in complexity in terms of cost and management. Moreover, the tube which has arrange | positioned polyamide MXD6 has the fault that it is inferior to low temperature impact resistance. As a laminated tube that achieves both chemical permeation prevention and low-temperature impact resistance, a laminated composition in which a polyamide MXD6 and a resin composition containing a polyamide resin that is compatible with the polyamide MXD6 and softer than the polyamide MXD6 is disposed in the intermediate layer A tube has been proposed (see Patent Document 3). However, further improvement is desired in terms of low-temperature impact properties, and the interlayer adhesion is still insufficient for polyamide 11 or polyamide 12, and it is necessary to provide an adhesive layer between the layers as in the above-described technique.

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, a method of melt-mixing a soft polymer such as an olefin polymer has been proposed. 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 has a higher molding processing temperature than the aliphatic polyamide such as polyamide 11 or polyamide 12 generally used at the time of co-extrusion, and the material has a conductive filler. In order to ensure fluidity, the tube is manufactured at extremely severe molding processing temperatures in the resin composition containing the. When a laminated tube is manufactured under such conditions, the soft polymer such as an olefin polymer added to the material used for the innermost layer has a problem that decomposition, foaming and deterioration occur. In the case where the amount of the soft polymer such as the olefin polymer added is large, this phenomenon is particularly noticeable. Therefore, there is a demand for the development of a laminated tube having electrical conductivity that balances thermal stability during molding, low-temperature impact resistance, and chemical solution permeation prevention at a high level.
Furthermore, the inventors of the present invention have a layer composed of an aliphatic polyamide, all diamine units, diamine units containing 60 mol% or more of xylylenediamine and / or naphthalenedimethylamine units, and all dicarboxylic acid units. Proposed laminated structure comprising at least two layers including a layer made of a semi-aromatic polyamide composed of dicarboxylic acid units containing 60 mol% or more of aliphatic dicarboxylic acid units having 8 to 13 carbon atoms (See Patent Document 4). In this document, there is no disclosure of specific technical data regarding the resistance (deterioration fuel resistance) to sour gasoline produced by oxidation of gasoline in a conductive laminated tube and the thermal stability during molding.

US Pat. No. 5,554,425 JP-A-4-272592 JP 2008-18702 A JP 2006-044201 A

  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. And a laminated tube having conductivity comprising a layer made of a conductive semi-aromatic polyamide composition comprising a conductive filler, and heat stability during molding, low temperature impact resistance, deteriorated fuel resistance, chemical liquid permeation prevention, and It was found that the interlayer adhesion was excellent.

  That is, the present invention comprises (a) layer composed of aliphatic polyamide (A), diamine units containing 60 mol% or more of xylylenediamine units and / or bis (aminomethyl) naphthalene units, based on all diamine units; (B) layer composed of a semi-aromatic polyamide (B) comprising a dicarboxylic acid unit containing 60 mol% or more of an aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms with respect to the total dicarboxylic acid unit, and a total diamine unit And (c1) m-xylylenediamine units and (c2) p-xylylenediamine units, or (c1) xylylenediamine units composed of m-xylylenediamine units containing 60 mol% or more, (c1) And (c2) in a molar ratio of 50:50 mol% or more and 100: 0 mol% or less with respect to all dicarboxylic acid units and carbon atoms A layer (c) comprising a semi-aromatic polyamide composed of a dicarboxylic acid unit containing 60 mol% or more of an aliphatic dicarboxylic acid unit of 8 to 13 inclusive and a conductive semi-aromatic polyamide composition (C) composed of a conductive filler. The present invention provides a conductive laminated tube 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] The aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms in the semiaromatic polyamide (B) and the conductive semiaromatic polyamide composition (C) is composed of azelaic acid, sebacic acid, and dodecanedioic acid. It is at least 1 sort (s) chosen from the group which consists of the unit induced | guided | derived, The electroconductive laminated tube characterized by the above-mentioned.
[2] Aliphatic polyamide (A) is polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene deca From the group consisting of amide (polyamide 610), polyhexamethylene dodecane (polyamide 612), polydecane methylene decanamide (polyamide 1010), polydecamethylene dodecane (polyamide 1012), and polydodecamethylene dodecane (polyamide 1212). A conductive laminated tube, which is at least one homopolymer selected, or a copolymer using several kinds of raw material monomers forming these.
[3] 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 composition (C) is disposed in the innermost layer. Conductive laminated tube.
[4] 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 composition (C). An electrically conductive laminated tube characterized by being arranged in
[5] A conductive laminated tube manufactured by coextrusion molding.

  The conductive laminated tube of the present invention includes a layer made of an aliphatic polyamide, a layer made of a semi-aromatic polyamide having a specific structure, and a conductive semi-aromatic made of a semi-aromatic polyamide having a specific structure and a conductive filler It includes a layer made of a polyamide composition, has excellent heat stability during molding, low-temperature impact resistance, anti-degradation fuel resistance, chemical solution permeation-preventing property, 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 sebacamide (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 a multi tank type continuous reaction apparatus, a tubular continuous reaction apparatus, a uniaxial kneading extruder, a biaxial kneading extruder, etc. A known polyamide production apparatus such as an extruder may be used. As a polymerization method, a known method such as melt polymerization, solution polymerization, or solid phase polymerization can be used, and polymerization can be performed by repeating normal pressure, reduced pressure, and pressure operations. These polymerization methods can be used alone or in appropriate combination.

  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, [A]> 20 is preferable from the viewpoint of the melt stability of the polyamide and the generation of gel-like substances is suppressed, and 30 <[A] <120 is more preferable.

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

The terminal-modified aliphatic polyamide is produced by polymerizing or copolymerizing the polyamide raw material in the presence of amines by a known method such as melt polymerization, solution polymerization or solid phase polymerization. Alternatively, it is produced by melt-kneading in the presence of amines after polymerization. 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 a conventional method. Among these, polyethyleneimine is more preferable. Polyalkyleneimine is polymerized from alkyleneimine as a raw material, branched polyalkyleneimine obtained by ring-opening polymerization of alkyleneimine, secondary polyamineimine containing secondary amine and tertiary amine, or alkyloxazoline as a raw material. Either a linear polyalkyleneimine containing only a primary amine and a secondary amine, or a three-dimensionally crosslinked structure may be used. Furthermore, ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine, bisaminopropylethylenediamine and the like may be included. A polyalkyleneimine is usually derived from the reactivity of an active hydrogen atom on a nitrogen atom contained therein, and in addition to a tertiary amino group, a primary amino group having an active hydrogen atom or a secondary amino group (imino Group).

  The number of nitrogen atoms in the polyalkyleneimine is not particularly limited, but is preferably 4 or more and 3,000 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 the amino group that reacts 1: 1 with the 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 terephthalamide (polyamide MXDT), polymetaxylylene isophthalamide (polyamide MXDI), polymetaxylylene hexahydroterephthalamide ( Polyamide MXDT (H)), polymetaxylylene naphthalamide (polyamide MXDN), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylene terephthalamide (polyamide PXDT), polyparaxylylene isophthalamide (polyamide) PXDI), polyparaxylylene hexahydroterephthalamide (polyamide PXDT (H)), polyparaxylylene naphthalamide (polyamide PXDN), polyparaphenylene terephthalamide (PPTA), polypara Phenylene isophthalamide (PPIA), polymetaphenylene terephthalamide (PMTA), polymetaphenylene isophthalamide (PMIA), poly (2,6-naphthalenediethylene adipamide) (polyamide 2,6-BAN6), Poly (2,6-naphthalene dimethylene terephthalamide) (polyamide 2,6-BANT), poly (2,6-naphthalene dimethylene isophthalamide) (polyamide 2,6-BANI), poly (2,6- Naphthalene dimethylene hexahydroterephthalamide) (polyamide 2,6-BANT (H)), poly (2,6-naphthalene dimethylene naphthalamide) (polyamide 2,6-BANN), poly (1,3-cyclohexanedi) Methylene adipamide) (polyamide 1,3-BAC6), poly (1,3-cyclohexanedi) Tyrensberamide (polyamide 1,3-BAC8), poly (1,3-cyclohexanedimethylene azelamide) (polyamide 1,3-BAC9), poly (1,3-cyclohexanedimethylene sebacamide) (polyamide 1,3- BAC10), poly (1,3-cyclohexanedimethylene dodecamide) (polyamide 1,3-BAC12), poly (1,3-cyclohexanedimethylene terephthalamide) (polyamide 1,3-BACT), poly (1, 3-cyclohexanedimethyleneisophthalamide) (polyamide 1,3-BACI), poly (1,3-cyclohexanedimethylene hexahydroterephthalamide) (polyamide 1,3-BACT (H)), poly (1,3 -Cyclohexanedimethylenenaphthalamide) (polyamide 1,3-BACN), poly (1 , 4-cyclohexanedimethyleneadipamide) (polyamide 1,4-BAC6), poly (1,4-cyclohexanedimethylenesuberamide) (polyamide 1,4-BAC8), poly (1,4-cyclohexanedimethylene ase) Lamid) (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-cyclohexanedimethylene hexahydroterephthalamide) (polyamide 1,4-B CT (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 dodecamide) (polyamide PACM12), poly (4,4′-methylenebiscyclohexylenetetradecanamide) (polyamide PACM14), poly (4,4 ′ -Methylenebiscyclohexylene hexadecamide) Amide 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'-methylenebiscyclohexylene) Naphthalamide) (polyamide PACMN), poly (4,4′-methylenebis (2-methyl-cyclohexylene) adipamide) (polyamide MACM6), poly (4,4′-methylenebis (2-methyl-cyclohexylene) suberamide) ( Polyamide MACM8), Poly (4,4′-methylenebis (2-methyl-cyclohexylene) azeramide) (polyamide MACM9), poly (4,4′-methylenebis (2-methyl-cyclohexylene) sebacamide) (polyamide MACM10), poly (4 4′-methylenebis (2-methyl-cyclohexylene) dodecamide) (polyamide MACM12), poly (4,4′-methylenebis (2-methyl-cyclohexylene) tetradecanamide) (polyamide MACM14), poly (4,4′-methylenebis) (2-methyl-cyclohexylene) hexadecamide) (polyamide MACM16), poly (4,4′-methylenebis (2-methyl-cyclohexylene) octadecamide) (polyamide MACM18), poly (4,4′-methylenebis (2-methyl) -Cyclohexyl ) Terephthalamide) (polyamide MACMT), poly (4,4′-methylenebis (2-methyl-cyclohexylene) isophthalamide) (polyamide MACMI), poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexahydrotere Phthalamide) (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 Bacamide) (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 PACPT), 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), polyisophorone veramide (polyamide IPD8), polyisophorone azeamide (polyamide IPD9) ), Polyisophorone sebacamide (polyamide IPD10), polyisophorodecamide (polyamide IPD12), polyisophorone terephthalamide (polyamide IPDT), polyisophorone isophthalamide (polyamide IPDI), polyisophorone hexahydroterephthalamide (polyamide) IPDT (H)), polyisophorone naphthalamide (polyamide IPDN), polytetramethylene terephthalamide (polyamide 4T), polytetramethylene isophthalamide (polyamide 4I) Polytetramethylene hexahydroterephthalamide (polyamide 4T (H)), polytetramethylene naphthalamide (polyamide 4N), polypentamethylene terephthalamide (polyamide 5T), polypentamethylene isophthalamide (polyamide 5I), polypenta Methylenehexahydroterephthalamide (polyamide 5T (H)), polypentamethylene naphthalamide (polyamide 5N), polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene hexa Hydroterephthalamide (polyamide 6T (H)), polyhexamethylene naphthalamide (polyamide 6N), poly (2-methylpentamethylene terephthalamide) (polyamide M5T), poly (2-methylpentamethyle Isophthalamide) (polyamide M5I), poly (2-methylpentamethylene hexahydroterephthalamide) (polyamide M5T (H)), poly (2-methylpentamethylene naphthalamide) (polyamide M5N), polynonamethylene terephthalamide ( Polyamide 9T), Polynonamethylene isophthalamide (Polyamide 9I), Polynonamethylene hexahydroterephthalamide (Polyamide 9T (H)), Polynonamethylene naphthalamide (Polyamide 9N), Poly (2-methyloctamethylene terephthalate) Lamid) (Polyamide M8T), Poly (2-methyloctamethyleneisophthalamide) (Polyamide M8I), Poly (2-methyloctamethylenehexahydroterephthalamide) (Polyamide M8T (H)), Poly (2-methylocta Methylene naphthala Mido) (polyamide M8N), polytrimethylhexamethylene terephthalamide (polyamide TMHT), polytrimethylhexamethylene isophthalamide (polyamide TMHI), polytrimethylhexamethylene hexahydroterephthalamide (polyamide TMHT (H)), polytrimethyl Hexamethylene naphthalamide (polyamide TMHN), polydecamethylene terephthalamide (polyamide 10T), polydecamethylene isophthalamide (polyamide 10I), polydecamethylene hexahydroterephthalamide (polyamide 10T (H)), polydecamethylene Naphthalamide (Polyamide 10N), Polyundecamethylene terephthalamide (Polyamide 11T), Polyundecamethylene isophthalamide (Polyamide 11I), Polyundecamethylene Sahydroterephthalamide (polyamide 11T (H)), polyundecamethylene naphthalamide (polyamide 11N), polydodecamethylene terephthalamide (polyamide 12T), polydodecamethylene isophthalamide (polyamide 12I), polydodecamethylene hexa Examples thereof include hydroterephthalamide (polyamide 12T (H)), polydodecamethylene naphthalamide (polyamide 12N), and copolymers using several raw material monomers of these polyamides. 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 in accordance with 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 and alkaline earth metals such as Li, Na, K, Mg, Ca, Sr, Ba, Al, Sn, Sb, Ti, Mn, Fe, Ni, Cu, Zn, Cd, etc. Is mentioned. These can use 1 type (s) or 2 or more types.

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

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

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

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

  Further, (ethylene and / or propylene) / α-olefin copolymer, (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid 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 an affinity for the aliphatic polyamide (A) is contained 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 comprises a diamine unit containing 60 mol% or more of a xylylenediamine unit and / or a bis (aminomethyl) naphthalene unit with respect to all diamine units, and all dicarboxylic acid units. On the other hand, it consists of a dicarboxylic acid unit containing 60 mol% or more of an aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms (hereinafter sometimes referred to as semi-aromatic polyamide (B)).

  The content of xylylenediamine units and / or bis (aminomethyl) naphthalene units in the semi-aromatic polyamide (B) is determined by the heat resistance, chemical resistance, impact resistance, and chemical liquid permeation resistance of the resulting conductive laminated tube. From the viewpoint of sufficiently securing various physical properties such as, the total diamine unit is 60 mol% or more, preferably 75 mol% or more, and more preferably 90 mol% or more.

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

  As long as the diamine 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, it is not a xylylenediamine unit and / or a bis (aminomethyl) naphthalene unit. Other diamine units may be included. Other diamine units include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, , 8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1, 15-pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, 1,19-nonadecanediamine, 1,20-eicosanediamine, 2-methyl-1,5 -Pentanediamine, 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octane Derived from aliphatic diamines such as amines, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine Unit, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,2 -Bis (4-aminocyclohexyl) propane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (3-methyl-4-aminocyclohexyl) propane, 5-amino-2,2,4- Trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine Bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, 2,5-bis (aminomethyl) norbornane, 2,6-bis (aminomethyl) norbornane, 3,8-bis (aminomethyl) tricyclodecane, 4 , 9-bis (aminomethyl) tricyclodecane and other units derived from alicyclic diamines, m-phenylenediamine, p-phenylenediamine, 4,4′-diaminodiphenylmethane, 2,2-bis (4-amino) Examples include units derived from aromatic diamines such as phenyl) propane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl ether, and these may be used alone or in combination of two or more. 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.

  In addition, the content of the aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms in the semi-aromatic polyamide (B) depends on various factors such as heat resistance, chemical resistance, and chemical liquid permeation prevention properties of the obtained conductive laminated tube. From the viewpoint of sufficiently securing physical properties, 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 aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms include units derived from suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and the like. As long as the number of carbon atoms satisfies the above, branched aliphatic dicarboxylic such as 2,2-diethylsuccinic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, 2-butylsuberic acid You may contain the unit induced | guided | derived from an acid. These can use 1 type (s) or 2 or more types.
Among the aliphatic dicarboxylic acid units having 8 or more and 13 or less carbon atoms, units derived from azelaic acid and sebacic acid are preferable from the viewpoint of the balance between coextrusion moldability and chemical liquid permeation prevention property, and low temperature impact resistance is achieved. From the viewpoint of ensuring sufficiently, units derived from dodecanedioic acid are preferred.

  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 than the aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms. Other dicarboxylic acid units may be included. Other dicarboxylic acid units include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, tetradecanedioic acid, pentadecanedioic acid, hexadecane Units derived from aliphatic dicarboxylic acids such as diacid, octadecanedioic acid and eicosane diacid, alicyclic rings such as 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid Units derived from the formula dicarboxylic acid, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,3 -Phenylenedioxydiacetic acid, 1,4-phenylenedioxydiacetic acid, 4,4'-o Sidibenzoic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylethane-4,4′-dicarboxylic acid, diphenylpropane-4,4′-dicarboxylic acid, diphenylether-4,4′-dicarboxylic acid, diphenylsulfone-4 , 4′-dicarboxylic acid, 4,4′-biphenyldicarboxylic acid, units derived from aromatic dicarboxylic acid such as 4,4′-triphenyldicarboxylic acid, and the like, and one or more of these are used. be able to. Among the above units, units derived from aromatic dicarboxylic acids are preferred. The content of these 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. 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 30 mol% or less, more preferably 10 mol% or less, based on the total dicarboxylic acid units.

  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, 1,9-nonanediamine, 1,10-decanediamine, 1 Aliphatic diamines such as aliphatic diamines such as 1,12-dodecanediamine, cyclohexanediamine, bis (aminomethyl) cyclohexane, 5-amino-1,3,3-trimethylcyclohexanemethylamine , Aromatic diamines such as m-phenylenediamine and p-phenylenediamine, polyalkyleneimines, polyalkylenepolyamines, polyamines such as polyvinylamine and polyallylamine, acetic acid, propionic acid, butyric acid, butyric acid, caproic acid, caprylic acid, lauric acid Acids, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid and other aliphatic monocarboxylic acids, cyclohexanecarboxylic acid and other alicyclic monocarboxylic acids, benzoic acid, toluic acid, α-naphthalenecarboxylic acid , Β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, aromatic monocarboxylic acid such as phenylacetic acid, aliphatic dicarboxylic acid such as adipic acid and pimelic acid, 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid 1,4-cyclohexa Alicyclic dicarboxylic acids such as dicarboxylic acids, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalene dicarboxylic acid, aromatic dicarboxylic acids such as 2,7-naphthalene dicarboxylic acid. These can use 1 type (s) or 2 or more types. The amount of these molecular weight regulators to be used varies depending on the reactivity of the molecular weight regulator and the polymerization conditions, but is appropriately determined so that the relative viscosity of the finally obtained polyamide falls within the following 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.

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

The content of the phosphorus compound is 0.03 parts by mass or more in terms of phosphorus atom concentration with respect to 100 parts by mass of the semi-aromatic polyamide (B) from the viewpoint of sufficiently ensuring the anti-coloring effect and suppressing the generation of gel. It is preferably 0.30 parts by mass or less, more preferably 0.05 parts by mass or more and 0.20 parts by mass or less, and further preferably 0.07 parts by mass or more and 0.15 parts by mass or less.
The addition method of these phosphorus compounds is a method of adding to a nylon salt aqueous solution, a diamine or dicarboxylic acid which is a raw material of the semi-aromatic polyamide (B), a method of adding to a dicarboxylic acid in a molten state, and adding during melt polymerization. Any method may be used as long as it can be uniformly dispersed in the semi-aromatic polyamide (B), but the method is not limited to these.

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

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

When an alkali metal compound is added to the polycondensation system of the semi-aromatic polyamide (B), the value obtained by dividing the number of moles of the compound by the number of moles of the phosphorus compound converted to phosphorus atoms is the acceleration and suppression of the amidation reaction. From the viewpoint of balance, it is preferably 0.3 or more and 1.0 or less, more preferably 0.40 or more and 0.95 or less, and further preferably 0.5 or more and 0.9 or less.
The methods for adding these alkali metal compounds are the method of adding to the aqueous solution of nylon salt, diamine or dicarboxylic acid, which is the raw material of the semi-aromatic polyamide (B), the method of adding to the dicarboxylic acid in the molten state, and the addition during melt polymerization Any method may be used as long as it can be uniformly dispersed in the semi-aromatic polyamide (B), but is not limited thereto.

  Semi-aromatic polyamide (B) production equipment includes batch-type reaction kettles, single- or multi-tank continuous reaction equipment, tubular continuous reaction equipment, uniaxial kneading extruder, biaxial kneading extruder, etc. A known polyamide production apparatus such as a reaction extruder may be used. As a method for producing the semi-aromatic polyamide (B), there are known methods such as melt polymerization, solution polymerization, and solid-phase polymerization, and these methods are used to repeat normal pressure, reduced pressure, and pressurizing operations to make the semi-aromatic polyamide. Polyamide (B) can be produced. These production methods can be used alone or in combination as appropriate, and among these, the melt polymerization method is preferable. For example, a nylon salt composed of xylylenediamine and / or bis (aminomethyl) naphthalene and an aliphatic dicarboxylic acid having 8 to 13 carbon atoms is pressurized, heated in the presence of water, added water and condensation. It is produced by a method of polymerizing in a molten state while removing water. It can also be produced by a method in which xylylenediamine and / or bis (aminomethyl) naphthalene is directly added to an aliphatic dicarboxylic acid having 8 to 13 carbon atoms in a molten state and polycondensed under normal pressure. In this case, in order to keep the reaction system in a uniform liquid state, xylylenediamine and / or bis (aminomethyl) naphthalene is continuously added to the aliphatic dicarboxylic acid having 8 to 13 carbon atoms, Polymerization proceeds while the temperature of the reaction system is raised so that the temperature of the reaction is higher than the melting point of the generated oligoamide and polyamide. Further, the semi-aromatic polyamide (B) may be subjected to solid phase polymerization after being produced by a melt polymerization method.

  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.

  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 improving material. It is more preferable to add a rubbery polymer having an elastic modulus of 500 MPa or less.

  The conductive semi-aromatic polyamide composition (C) used in the present invention has (c1) m-xylylenediamine units and (c2) p-xylylenediamine units, or (c1) with respect to all diamine units. A diamine unit containing 60 mol% or more of xylylenediamine units composed of m-xylylenediamine units, and having a molar ratio of (c1) to (c2) of 50:50 mol% or more and 100: 0 mol% or less, and all dicarboxylic acids Semi-aromatic polyamide (C1) comprising a dicarboxylic acid unit containing 60 mol% or more of an aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms based on the acid unit (hereinafter referred to as semi-aromatic polyamide (C1)) And a conductive filler (C2). The semi-aromatic polyamide (C1) is a polymer included in the semi-aromatic polyamide (B).

  The content of xylylenediamine units consisting of (c1) m-xylylenediamine units and (c2) p-xylylenediamine units or (c1) m-xylylenediamine units in the semi-aromatic polyamide (C1) From the viewpoint of sufficiently ensuring various physical properties such as heat resistance, chemical resistance and chemical solution permeation prevention properties of the obtained conductive laminated tube, it is 60 mol% or more and 75 mol% or more with respect to all diamine units. Preferably, it is 90 mol% or more.

  The molar ratio of the (c1) m-xylylenediamine unit to the (c2) p-xylylenediamine unit is (c1) :( c2 ) = 50: 50 mol% to 100: 0 mol%, preferably 55:45 mol% to 100: 0 mol%, preferably 60:40 mol to 100: 0 mol% Is more preferably 65:35 mol% or more and 100: 0 mol or less.

  If the diamine unit in the semi-aromatic polyamide (C1) is within a range that does not impair the excellent characteristics of the conductive laminated tube of the present invention, (c1) m-xylylenediamine unit and (c2) p-xylyl Other diamine units other than the range amine unit may be included. Examples of other diamine units include the diamine units described in the description of the semi-aromatic polyamide (B). The content of other diamine units is 40 mol% or less, preferably 25 mol% or less, more preferably 10 mol% or less, based on all diamine units.

In addition, the content of the aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms in the semi-aromatic polyamide (C1) depends on various factors such as heat resistance, chemical resistance, and chemical solution permeation prevention properties of the obtained conductive laminated tube. From the viewpoint of sufficiently securing physical properties, it is at least 60 mol%, preferably at least 75 mol%, more preferably at least 90 mol%, based on all dicarboxylic acid units.
The aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms in the semi-aromatic polyamide (C1) is derived from suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, etc. Units are listed. As long as the number of carbon atoms satisfies the above, branched aliphatic dicarboxylic such as 2,2-diethylsuccinic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, 2-butylsuberic acid You may contain the unit induced | guided | derived from an acid. These can use 1 type (s) or 2 or more types.
Among the aliphatic dicarboxylic acid units having 8 or more and 13 or less carbon atoms, units derived from azelaic acid and sebacic acid are preferable from the viewpoint of the balance between coextrusion moldability and chemical liquid permeation prevention property, and low temperature impact resistance is achieved. From the viewpoint of ensuring sufficiently, units derived from dodecanedioic acid are preferred.

  As long as the dicarboxylic acid unit in the semi-aromatic polyamide (C1) is within a range that does not impair the excellent characteristics of the conductive laminated tube of the present invention, it is other than the aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms. 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 (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. 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 units.

  In addition, there is no special restriction | limiting in the kind of terminal group of semi-aromatic polyamide (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 fall within the range described later.

  Considering the melt stability, it is preferable that the end of the molecular chain of the semi-aromatic polyamide (C1) is preferably 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. 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.

A phosphorus compound can be added to the semi-aromatic polyamide (C1) in order to increase the processing stability during melt molding or to prevent coloring. For example, the phosphorus compound described by description of semi-aromatic polyamide (B) is mentioned.
The content of the phosphorus compound is 0.03 parts by mass or more in terms of phosphorus atom concentration with respect to 100 parts by mass of the semi-aromatic polyamide (C1) from the viewpoint of sufficiently securing the coloring prevention effect and suppressing the generation of gel. It is preferably 0.30 parts by mass or less, more preferably 0.05 parts by mass or more and 0.20 parts by mass or less, and further preferably 0.07 parts by mass or more and 0.15 parts by mass or less.

An alkali metal compound can be added to the semiaromatic polyamide (C1) in combination with the phosphorus compound. In order to prevent coloring of the polyamide during polycondensation, a sufficient amount of phosphorus compound needs to be present, but in some cases there is a risk of causing gelation of the polyamide. It is preferable to coexist an alkali metal compound. For example, the alkali metal compound described in the description of the semi-aromatic polyamide (B) can be given.
When an alkali metal compound is added to the polycondensation system of the semi-aromatic polyamide (C1), the value obtained by dividing the number of moles of the compound by the number of moles of the phosphorus compound converted to phosphorus atoms is the acceleration and suppression of the amidation reaction. From the viewpoint of balance, it is preferably 0.3 or more and 1.0 or less, more preferably 0.40 or more and 0.95 or less, and further preferably 0.5 or more and 0.9 or less.

  Examples of the production apparatus for the semi-aromatic polyamide (C1) include known polyamide production apparatuses described in the description of the semi-aromatic polyamide (B). As a manufacturing method of semi-aromatic polyamide (C1), the well-known manufacturing method described in description of semi-aromatic polyamide (B) is mentioned.

  According to JIS K-6920, the relative viscosity of the semi-aromatic polyamide (C1) 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 3.0 or less, and 1.7 or more and 2.5 or less. More preferably, it is 1.8 or more and 2.3 or less.

The conductive filler (C2) in the conductive semi-aromatic polyamide composition (C) includes all fillers added to impart conductive performance to the resin, and is in the form of granular, flaky, and fibrous fillers. Etc.
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 balance of conductivity, fluidity, mechanical strength, etc., semi-aromatic polyamide (C1 ) Generally, it is preferably 1 to 30 parts by mass, more preferably 2 to 25 parts by mass with respect to 100 parts by mass.
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 composition (C) may contain other polyamide-based resin or other thermoplastic resin in addition to the semi-aromatic polyamide (C1) and the conductive filler (C2). 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 (C1) in the conductive semi-aromatic polyamide composition (C) is preferably 50% by mass or more.

  Further, the conductive semi-aromatic polyamide composition (C) includes an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, an inorganic filler, an antistatic agent, a flame retardant as necessary. Further, a crystallization accelerator, a plasticizer, a colorant, a lubricant, an impact resistance improving material, and the like may be added. In order to improve the low temperature impact resistance of the conductive semi-aromatic polyamide composition (C), it is preferable to add an impact resistance improver, and in particular according to ISO 178 described in the aliphatic polyamide (A). It is more preferable to add a rubber-like polymer having a bending elastic modulus of 500 MPa or less.

  The production of the conductive semi-aromatic polyamide composition (C) used in the present invention is made of raw materials such as semi-aromatic polyamide (C1), conductive filler (C2), and additives that are added as necessary. It is manufactured using components, and a known method can be used as the method, but it is generally manufactured by melt mixing. As a specific method for melt mixing, the raw material components are uniformly mixed using a Henschel mixer, a ribbon blender, a V-type blender, etc. at a predetermined blending ratio, and then a 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 the above or the like may be used.

  The conductive laminated tube according to the present invention contains 60 mol% or more of xylylenediamine units and / or bis (aminomethyl) naphthalene units with respect to the (a) layer composed of the aliphatic polyamide (A) and all diamine units. (B) layer comprising a diamine unit and a semi-aromatic polyamide (B) comprising a dicarboxylic acid unit containing 60 mol% or more of an aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms based on all dicarboxylic acid units; And (c1) m-xylylenediamine units and (c2) p-xylylenediamine units, or (c1) xylylenediamine units composed of m-xylylenediamine units A diamine unit having a molar ratio of (c1) to (c2) of 50:50 mol% or more and 100: 0 mol% or less, and all dicarboxylic acid units On the other hand, from a semi-aromatic polyamide comprising a dicarboxylic acid unit containing 60 mol% or more of an aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms and a conductive semi-aromatic polyamide composition (C) comprising a conductive filler. (C) It is comprised from at least 3 layers including a layer. By including the (b) layer made of the semi-aromatic polyamide (B) and the (c) layer made of the conductive semi-aromatic polyamide composition (C), the chemical liquid permeation preventive property of the conductive laminated tube can be improved.

  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. Moreover, the (c) layer which consists of an electroconductive semi-aromatic polyamide composition (C) is arrange | positioned at the innermost layer of an electroconductive laminated tube. By arranging the (c) layer made of the conductive semi-aromatic polyamide composition (C) in the innermost layer, the heat stability at the time of molding processing, low temperature impact resistance, degradation fuel resistance, chemical solution permeation prevention, etc. A laminated tube having excellent balance and conductivity can be obtained.

  In a more preferred embodiment, the layer (b) made of the semi-aromatic polyamide (B) includes the layer (a) made of the aliphatic polyamide (A) of the conductive laminated tube and the conductive semi-aromatic polyamide composition (C (C) between the layers. The (b) layer made of the semi-aromatic polyamide (B) is disposed between the (a) layer made of the aliphatic polyamide (A) and the (c) layer made of the conductive semi-aromatic polyamide composition (C). Thus, 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 As long as it is at least 3 layers including the (c) layer which consists of a composition (C), it does not restrict | limit. 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 (polyamide MXD6) other than the aliphatic polyamide (A), semi-aromatic polyamide (B), and semi-aromatic polyamide (C1) defined in the present invention. , Polymetaxylylene terephthalamide (polyamide MXDT), polymetaxylylene isophthalamide (polyamide MXDI), polymetaxylylene hexahydroterephthalamide (polyamide MXDT (H)), polymetaxylylene naphthalamide (polyamide MXDN), poly Paraxylylene adipamide (polyamide PXD6), polyparaxylylene terephthalamide (polyamide PXDT), polyparaxylylene isophthalamide (polyamide PXDI), polyparaxylylene hexahydroterephthalamide (polyamide PXDT (H)) ) Polyparaxylylene naphthalamide (polyamide PXDN), polyparaphenylene terephthalamide (PPTA), polyparaphenylene isophthalamide (PPIA), polymetaphenylene terephthalamide (PMTA), polymetaphenylene isophthalamide (PMIA) , Poly (2,6-naphthalene dimethylene adipamide) (polyamide 2,6-BAN6), poly (2,6-naphthalene dimethylene terephthalamide) (polyamide 2,6-BANT), poly (2,6 -Naphthalenedylene methylene isophthalamide) (polyamide 2,6-BANI), poly (2,6-naphthalenediethylene hexahydroterephthalamide) (polyamide 2,6-BANT (H)), poly (2,6- Naphthalene dimethylene naphthalamide) (polyamide 2,6-BANN), poly 1,3-cyclohexanedimethylene adipamide) (polyamide 1,3-BAC6), poly (1,3-cyclohexanedimethylene suberamide (polyamide 1,3-BAC8), poly (1,3-cyclohexanedimethylene ase) Lamid) (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 hexahydroterephthalamide) (polyamide 1,3-B ACT (H)), poly (1,3-cyclohexanedimethylenenaphthalamide) (polyamide 1,3-BACN), poly (1,4-cyclohexanedimethylene adipamide) (polyamide 1,4-BAC6), poly (1,4-cyclohexanedimethylenesuberamide) (polyamide 1,4-BAC8), poly (1,4-cyclohexanedimethylene azelamide) (polyamide 1,4-BAC9), poly (1,4-cyclohexanedimethylene) Sebacamide) (polyamide 1,4-BAC10), poly (1,4-cyclohexanedimethylene dodecamide) (polyamide 1,4-BAC12), poly (1,4-cyclohexanedimethylene terephthalamide) (polyamide 1) , 4-BACT), poly (1,4-cyclohexanedimethyleneisophthalamide) (polyamide) , 4-BACI), poly (1,4-cyclohexanedimethylene hexahydroterephthalamide) (polyamide 1,4-BACT (H)), poly (1,4-cyclohexanedimethylene naphthalamide) (polyamide 1,4) -BACN), poly (4,4'-methylenebiscyclohexylene adipamide) (polyamide PACM6), poly (4,4'-methylenebiscyclohexylene suberamide) (polyamide PACM8), poly (4,4'- Methylenebiscyclohexylene azelamide) (polyamide PACM9), poly (4,4′-methylenebiscyclohexylene sebamide) (polyamide PACM10), poly (4,4′-methylenebiscyclohexylene dodecamide) (polyamide PACM12) Poly (4,4'-methylenebiscyclohexylene Tradecamide) (polyamide PACM14), poly (4,4′-methylenebiscyclohexylenehexadecamide) (polyamide PACM16), poly (4,4′-methylenebiscyclohexyleneoctadecamide) (polyamide PACM18), poly (4 , 4'-methylenebiscyclohexylene terephthalamide) (polyamide PACMT), poly (4,4'-methylenebiscyclohexylene isophthalamide) (polyamide PACMI), poly (4,4'-methylenebiscyclohexylene hexahydro Terephthalamide) (polyamide PACMT (H)), poly (4,4′-methylenebiscyclohexylenenaphthalamide) (polyamide PACMN), poly (4,4′-methylenebis (2-methyl-cyclohexylene) adipamide) ( Polyamide MA CM6), 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-cyclohex Len) octadecamide) (polyamide MACM18), poly (4,4′-methylenebis (2-methyl-cyclohexylene) terephthalamide) (polyamide MACMT), poly (4,4′-methylenebis (2-methyl-cyclohexylene) isophthalamide) (Polyamide MACMI), poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexahydroterephthalamide) (polyamide MACMT (H)), poly (4,4′-methylenebis (2-methyl-cyclohexylene) ) Naphthalamide) (polyamide MACMN), poly (4,4′-propylene biscyclohexylene adipamide) (polyamide PACP6), poly (4,4′-propylene biscyclohexylene suberamide) (polyamide PACP8), poly (4 , 4'-propi Biscyclohexylene azelamide) (polyamide PACP9), poly (4,4′-propylene biscyclohexylene sebacamide) (polyamide PACP10), poly (4,4′-propylene biscyclohexylene dodecamide) (polyamide PACP12) , Poly (4,4′-propylene biscyclohexylene tetradecanamide) (polyamide PACP14), poly (4,4′-propylene biscyclohexylene hexadecanamide) (polyamide PACP16), poly (4,4′-propylene bis (Cyclohexylene octadecanamide) (polyamide PACP18), poly (4,4′-propylene biscyclohexylene terephthalamide) (polyamide PAPPT), poly (4,4′-propylene biscyclohexylene isophthalamide) (polyamide P) ACPI), poly (4,4′-propylene biscyclohexylene hexahydroterephthalamide) (polyamide PACPT (H)), poly (4,4′-propylene biscyclohexylene naphthalamide) (polyamide PACPN), polyisophorone azide Pamide (Polyamide IPD6), Polyisophorone Veramide (Polyamide IPD8), Polyisophorone Azelamide (Polyamide IPD9), Polyisophorone Sebamide (Polyamide IPD10), Polyisophoron Decamide (Polyamide IPD12), Polyisophorone Terephthalamide ( Polyamide IPDT), polyisophorone isophthalamide (polyamide IPDI), polyisophorone hexahydroterephthalamide (polyamide IPDT (H)), polyisophorone naphthalamide (polyamide IPD) ), Polytetramethylene terephthalamide (polyamide 4T), polytetramethylene isophthalamide (polyamide 4I), polytetramethylene hexahydroterephthalamide (polyamide 4T (H)), polytetramethylene naphthalamide (polyamide 4N), Polypentamethylene terephthalamide (polyamide 5T), polypentamethylene isophthalamide (polyamide 5I), polypentamethylene hexahydroterephthalamide (polyamide 5T (H)), polypentamethylene naphthalamide (polyamide 5N), polyhexa Methylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene hexahydroterephthalamide (polyamide 6T (H)), polyhexamethylene naphthalamide (polyamide) 6N), poly (2-methylpentamethylene terephthalamide) (polyamide M5T), poly (2-methylpentamethylene isophthalamide) (polyamide M5I), poly (2-methylpentamethylene hexahydroterephthalamide) ( Polyamide M5T (H)), poly (2-methylpentamethylene naphthalamide) (polyamide M5N), polynonamethylene terephthalamide (polyamide 9T), polynonamethylene isophthalamide (polyamide 9I), polynonamethylene hexahydrotere Phthalamide (polyamide 9T (H)), polynonamethylene naphthalamide (polyamide 9N), poly (2-methyloctamethylene terephthalamide) (polyamide M8T), poly (2-methyloctamethylene isophthalamide) (polyamide M81) ), Poly (2-methyl) Octamethylene hexahydroterephthalamide) (polyamide M8T (H)), poly (2-methyloctamethylene naphthalamide) (polyamide M8N), polytrimethylhexamethylene terephthalamide (polyamide TMHT), polytrimethylhexamethylene isophthalamide (Polyamide TMHI), polytrimethylhexamethylene hexahydroterephthalamide (polyamide TMHT (H)), polytrimethylhexamethylene naphthalamide (polyamide TMHN), polydecamethylene terephthalamide (polyamide 10T), polydecamethylene isophthalamide (Polyamide 10I), polydecamethylene hexahydroterephthalamide (polyamide 10T (H)), polydecamethylene naphthalamide (polyamide 10N), polyundecamethylene terephthale Lamidamide (polyamide 11T), polyundecamethylene isophthalamide (polyamide 11I), polyundecamethylene hexahydroterephthalamide (polyamide 11T (H)), polyundecamethylene naphthalamide (polyamide 11N), polydodecamethylene tele Phthalamide (polyamide 12T), polydodecamethylene isophthalamide (polyamide 12I), polydodecamethylenehexahydroterephthalamide (polyamide 12T (H)), polydodecamethylene naphthalamide (polyamide 12N) and raw materials of these polyamides And / or a polyamide-based resin such as a copolymer using several kinds of raw material monomers of the aliphatic polyamide (A).

  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 resins such as vinylidene chloride / methyl acrylate copolymer, cellulose resins 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. Further, for example, necessary parts such as a connector can be added, or L-shaped or U-shaped can be formed 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). 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.

[Deterioration fuel 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 in which Fuel C (isooctane / toluene = 50/50 volume ratio) and ethanol were mixed in a 90/10 volume ratio was placed inside, and the remaining ends were 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, 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 in the middle of the cylinder of the twin-screw melt kneader. 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).).

Production 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 50 mass% aqueous solution of a salt of 1,6-hexanediamine and sebacic acid, 1,6-hexanediamine 63 .8 g was charged and the inside of the polymerization tank was purged with nitrogen, then 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) or (C1-1) Stirrer, thermometer, torque meter, pressure gauge, raw material inlet directly connected to diaphragm pump, nitrogen gas inlet, pressure relief outlet, pressure regulator, And a pressure vessel equipped with a polymer outlet and having an internal volume of 40 liters, sebacic acid 6.068 kg (30.0 mol), calcium hypophosphite 8.50 g (0.049 mol), and sodium acetate 2.19 g (0 0.025 mol), and pressurizing to 0.3 MPa with nitrogen gas having a purity of 99.9999% inside the pressure vessel, and then releasing nitrogen gas to normal pressure five times to replace nitrogen. Then, the system was heated while stirring under a sealing pressure. Furthermore, after heating up to 190 degreeC under a small nitrogen stream, 4.086 kg (30.0 mol) of (c1) m-xylylenediamine was dripped over 160 minutes under stirring. During this time, the internal pressure of the reaction system was controlled to 0.5 MPa, and the internal temperature was continuously raised to 245 ° C. In addition, (c1) water distilled with the dropwise addition of m-xylylenediamine was removed from the system through a condenser and a cooler. (C1) After completion of the dropwise addition of m-xylylenediamine, the pressure was reduced to normal pressure over 60 minutes, and the reaction was continued for 10 minutes while maintaining the temperature in the container at 250 ° C. Thereafter, the internal pressure of the reaction system was reduced to 79 kPa, and the melt polymerization reaction was continued for 40 minutes. Thereafter, stirring was stopped and the inside of the system was pressurized to 0.2 MPa with nitrogen, and the polycondensate was extracted from the lower outlet of the pressure vessel into a string shape. The string-like polycondensate is immediately cooled, and the water-cooled string-like resin is pelletized by a pelletizer, and then dried under reduced pressure. A semi-aromatic polyamide having a melting point of 191 ° C. and a relative viscosity of 2.48 (polyamide MXD10 = 100 mol). %) (Hereinafter, this semi-aromatic polyamide is referred to as (B1-1) or (C1-1)).

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, IRGAFOS 168) is mixed in advance and supplied to a biaxial melt kneader (manufactured by Nippon Steel, Ltd., model: TEX44), with a cylinder temperature of 200 ° C. From 240 to 240 ° C., and the molten resin is extruded in 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) or (C1-2) In production of semi-aromatic polyamide (B1-1), 4.086 kg (30.0 mol) of (c1) m-xylylenediamine (c1) Semi-aromatic except that the polymerization temperature was changed from 250 ° C. to 260 ° C. except that it was changed to 4.086 kg (30.0 mol) of a 7: 3 mixed diamine of m) -xylylenediamine and (c2) p-xylylenediamine. A semi-aromatic polyamide (polyamide MXD10 / PXD10 = 70/30 mol%) having a melting point of 215 ° C. and a relative viscosity of 2.45 was obtained in the same manner as in the production of the aromatic polyamide (B1-1) (hereinafter, this half (Aromatic polyamide is referred to as (B1-2) or (C1-2).)

Production of semi-aromatic polyamide composition (B-2) In production of semi-aromatic polyamide composition (B-1), semi-aromatic polyamide (B1-1) was changed to (B1-2), and the cylinder temperature was adjusted to 240. 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 250 ° C. to 250 ° 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) or (C1-3) In the production of semi-aromatic polyamide (B1-1), 4.086 kg (30.0 mol) of (c1) m-xylylenediamine (c1) Semi-fragrance except that the polymerization temperature was changed from 250 ° C. to 270 ° C., except that the polymerization temperature was changed from 250 ° C. to 270 ° C. and changed to 4.086 kg (30.0 mol) of 6: 4 mixed diamine of m-xylylenediamine and (c2) A semi-aromatic polyamide (polyamide MXD10 / PXD10 = 60/40 mol%) having a melting point of 224 ° C. and a relative viscosity of 2.44 was obtained in the same manner as in the production of the aromatic polyamide (B1-1) (hereinafter, this half Aromatic polyamide is referred to as (B1-3) or (C1-3)).

Production of semi-aromatic polyamide composition (B-3) In production of semi-aromatic polyamide composition (B-1), semi-aromatic polyamide (B1-1) was changed to (B1-3), and the cylinder temperature was 240. A total of 100 parts by mass of 90% by mass of a semi-aromatic polyamide and 10% by mass of an impact resistance improver, in the same manner as in the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from 260 ° C. to 260 ° 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- 3).)

Production of semi-aromatic polyamide (B1-4) or (C1-4) In the production of semi-aromatic polyamide (B1-1), 6.068 kg (30.0 mol) of sebacic acid was converted to 6.488 kg (30 mol of dodecanedioic acid). 0.0 mol), and the polymerization temperature was changed from 250 ° C. to 240 ° C., in the same manner as in the production of the semi-aromatic polyamide (B1-1), with a melting point of 175 ° C. and a relative viscosity of 2.40 half. An aromatic polyamide (polyamide MXD12 = 100 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B1-4) or (C1-4)).

Production of semi-aromatic polyamide composition (B-4) In production of semi-aromatic polyamide composition (B-1), semi-aromatic polyamide (B1-1) was changed to (B1-4), and the cylinder temperature was 240. 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 230 ° C. to 230 ° 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- 4).)

Production of Semi-Aromatic Polyamide (B1-5) In the production of semi-aromatic polyamide (B1-1), 4.086 kg (30.0 mol) of (c1) m-xylylenediamine was (c2) p-xylylenediamine. Except for changing to 4.086 kg (30.0 mol) and changing the polymerization temperature from 250 ° C. to 300 ° C., in the same manner as the production of the semi-aromatic polyamide (B1-1), A semi-aromatic polyamide having 2 melting points and a relative viscosity of 2.42 (polyamide PXD10 = 100 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B1-5)).

Production of semi-aromatic polyamide composition (B-5) In production of semi-aromatic polyamide composition (B-1), semi-aromatic polyamide (B1-1) was changed to (B1-5), and the cylinder temperature was adjusted to 240. 100 parts by mass in total of 90% by mass of semi-aromatic polyamide and 10% by mass of impact resistance improving material, in the same manner as the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from 320 ° C. to 320 ° 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 (B1-6) In the production of semi-aromatic polyamide (B1-4), 4.086 kg (30.0 mol) of (c1) m-xylylenediamine was added to 2,6-bis (aminomethyl). ) The melting point was 272 ° C. in the same manner as in the production of the semi-aromatic polyamide (B1-4), except that it was changed to naphthalene 5.588 kg (30.0 mol) and the polymerization temperature was changed from 240 ° C. to 300 ° C. A semi-aromatic polyamide having a relative viscosity of 2.33 (polyamide 2,6-BAN12 = 100 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B1-6)).

Production of semi-aromatic polyamide composition (B-6) In production of semi-aromatic polyamide composition (B-1), semi-aromatic polyamide (B1-1) was changed to (B1-6), and the cylinder temperature was adjusted to 240. A total of 100 parts by mass of 90% by mass of a semi-aromatic polyamide and 10% by mass of an impact resistance improver, in the same manner as in the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from 300 ° C. to 300 ° 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- 6).)

Production of semi-aromatic polyamide (B1-7) In the production of semi-aromatic polyamide (B1-1), 6.068 kg (30.0 mol) of sebacic acid was changed to 4.384 kg (30.0 mol) of adipic acid, A semi-aromatic polyamide having a melting point of 243 ° C. and a relative viscosity of 2.42 (polyamide MXD6 = polyamide) was prepared in the same manner as in the production of the semi-aromatic polyamide (B1-1) except that the polymerization temperature was changed from 250 ° C. to 275 ° C. 100 mol%) (hereinafter, this semi-aromatic polyamide is referred to as (B1-7)).

Production of semi-aromatic polyamide composition (B-7) In the production of semi-aromatic polyamide composition (B-1), semi-aromatic polyamide (B1-1) was changed to (B1-7), and the cylinder temperature was adjusted to 240. 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 ℃ to 280 ° 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- 7).)

Conductive semi-aromatic polyamide composition (C)
Production of semi-aromatic polyamide (C1-5) Production of semi-aromatic polyamide (C1-1) except that the melt polymerization time was changed from 40 minutes to 20 minutes in the production of semi-aromatic polyamide (C1-1). In the same manner, a semi-aromatic polyamide (polyamide MXD10 = 100 mol%) having a melting point of 191 ° C. and a relative viscosity of 2.16 was obtained (hereinafter, this semi-aromatic polyamide is referred to as (C1-5)).

Production of Conductive Semi-Aromatic Polyamide Composition (C-1) Maleic anhydride-modified ethylene / 1-butene copolymer (manufactured by Mitsui Chemicals, Inc.) as a semi-aromatic polyamide (C1-5) as an impact resistance improver , Tuffmer MH5010) and ethylene / 1-butene copolymer (manufactured by Mitsui Chemicals, Inc., Tuffmer A-0550), carbon black as a conductive filler (manufactured by Lion Corporation, Ketjen Black EC600JD), as an antioxidant Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan, IRGANOX245), and tris (2,4-di-) as a phosphorus processing stabilizer t-Butylphenyl) phosphite (BASF Japan, IRGAFOS168) is mixed in advance, Supply to a shaft melt kneader (manufactured by Nippon Steel Works, model: TEX44), melt knead at a cylinder temperature of 200 ° C. to 250 ° C., extrude the molten resin into a strand, and then introduce it into a water tank. Cooled, cut and vacuum dried, with a total of 100 parts by mass of 68% by mass of semi-aromatic polyamide, 25% by mass of impact resistance improving agent, and 7% by mass of conductive filler, 0.8 parts by mass of antioxidant, phosphorus A pellet of conductive semi-aromatic polyamide composition comprising 0.2 parts by mass of a system processing stabilizer was obtained (hereinafter, this conductive semi-aromatic polyamide composition is referred to as (C-1)).

Production of Conductive Semi-Aromatic Polyamide Composition (C-2) In production of the conductive semi-aromatic polyamide composition (C-1), carbon black (manufactured by Lion Corporation, Ketjen Black EC600JD) is converted to carbon nanotube ( Except for the change to Nanosil Corporation, NC7000), in the same manner as in the production of the conductive semiaromatic polyamide composition (C-1), 70% by mass of semiaromatic polyamide, 25% by mass of impact resistance improver, Conductive semi-aromatic polyamide composition pellets comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer with respect to a total of 100 parts by weight of 5% by weight of a conductive filler were obtained ( Hereinafter, this conductive semi-aromatic polyamide composition is referred to as (C-2)).

Production of semi-aromatic polyamide (C1-6) Production of semi-aromatic polyamide (C1-2) except that the melt polymerization time was changed from 40 minutes to 20 minutes in the production of semi-aromatic polyamide (C1-2). In the same manner, a semi-aromatic polyamide (polyamide MXD10 / PXD10 = 70/30 mol%) having a melting point of 215 ° C. and a relative viscosity of 2.15 was obtained (hereinafter, this semi-aromatic polyamide is referred to as (C1-6)). .)

Production of conductive semi-aromatic polyamide composition (C-3) In production of conductive semi-aromatic polyamide composition (C-1), semi-aromatic polyamide (C1-5) was changed to (C1-6), Except for changing the cylinder temperature from 250 ° C. to 270 ° C., in the same manner as in the production of the conductive semi-aromatic polyamide composition (C-1), 68% by mass of semi-aromatic polyamide and 25% by mass of impact resistance improver %, A conductive semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer is obtained with respect to 100 parts by weight in total of 7% by weight of a conductive filler. (Hereinafter, this conductive semi-aromatic polyamide composition is referred to as (C-3)).

Production of conductive semi-aromatic polyamide composition (C-4) In production of conductive semi-aromatic polyamide composition (C-2), semi-aromatic polyamide (C1-5) was changed to (C1-6), Except for changing the cylinder temperature from 250 ° C. to 270 ° C., the same method as the production of the conductive semi-aromatic polyamide composition (C-2) was performed. %, A conductive semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer is obtained with respect to 100 parts by weight in total of 5% by weight of a conductive filler. (Hereinafter, this conductive semi-aromatic polyamide composition is referred to as (C-4)).

Production of semi-aromatic polyamide (C1-7) Production of semi-aromatic polyamide (C1-3), except that the melt polymerization time was changed from 40 minutes to 20 minutes in the production of semi-aromatic polyamide (C1-3) In the same manner, a semiaromatic polyamide (polyamide MXD10 / PXD10 = 60/40 mol%) having a melting point of 224 ° C. and a relative viscosity of 2.13 was obtained (hereinafter, this semiaromatic polyamide is referred to as (C1-7)). .)

Production of conductive semi-aromatic polyamide composition (C-5) In production of conductive semi-aromatic polyamide composition (C-1), semi-aromatic polyamide (C1-5) was changed to (C1-7), Except for changing the cylinder temperature from 250 ° C. to 280 ° C., in the same manner as in the production of the conductive semi-aromatic polyamide composition (C-1), 68% by mass of semi-aromatic polyamide and 25% by mass of impact resistance improver %, A conductive semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer is obtained with respect to 100 parts by weight in total of 7% by weight of a conductive filler. (Hereinafter, this conductive semi-aromatic polyamide composition is referred to as (C-5)).

Production of semi-aromatic polyamide (C1-8) Production of semi-aromatic polyamide (C1-4), except that the melt polymerization time was changed from 40 minutes to 20 minutes in the production of semi-aromatic polyamide (C1-4) In the same manner, a semi-aromatic polyamide (polyamide MXD12 = 100 mol%) having a melting point of 175 ° C. and a relative viscosity of 2.16 was obtained (hereinafter, this semi-aromatic polyamide is referred to as (C1-8)).

Production of conductive semi-aromatic polyamide composition (C-6) In production of conductive semi-aromatic polyamide composition (C-1), semi-aromatic polyamide (C1-5) was changed to (C1-8), Except for changing the cylinder temperature from 250 ° C. to 240 ° C., in the same manner as in the production of the conductive semi-aromatic polyamide composition (C-1), 68% by mass of semi-aromatic polyamide and 25% by mass of impact resistance improver %, A conductive semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer is obtained with respect to 100 parts by weight in total of 7% by weight of a conductive filler. (Hereinafter, this conductive semi-aromatic polyamide composition is referred to as (C-6)).

Production of conductive semi-aromatic polyamide composition (C-7) In production of conductive semi-aromatic polyamide composition (C-1), semi-aromatic polyamide (C1-5) was changed to (B1-5), Except for changing the cylinder temperature from 250 ° C. to 350 ° C., in the same manner as in the production of the conductive semi-aromatic polyamide composition (C-1), 68% by mass of semi-aromatic polyamide and 25% by mass of impact resistance improver %, A conductive semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer is obtained with respect to 100 parts by weight in total of 7% by weight of a conductive filler. (Hereinafter, this conductive semi-aromatic polyamide composition is referred to as (C-7)).

Production of conductive semi-aromatic polyamide composition (C-8) In production of conductive semi-aromatic polyamide composition (C-1), semi-aromatic polyamide (C1-5) was changed to (B1-6), Except for changing the cylinder temperature from 250 ° C. to 330 ° C., in the same manner as in the production of the conductive semi-aromatic polyamide composition (C-1), 68% by mass of semi-aromatic polyamide and 25% by mass of impact resistance improver %, A conductive semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer is obtained with respect to 100 parts by weight in total of 7% by weight of a conductive filler. (Hereinafter, this conductive semi-aromatic polyamide composition is referred to as (C-8)).

Production of conductive semi-aromatic polyamide composition (C-9) In production of conductive semi-aromatic polyamide composition (C-1), semi-aromatic polyamide (C1-5) was changed to (B1-7), Except for changing the cylinder temperature from 250 ° C. to 290 ° C., in the same manner as in the production of the conductive semi-aromatic polyamide composition (C-1), 68% by mass of semi-aromatic polyamide and 25% by mass of impact resistance improver %, A conductive semi-aromatic polyamide composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer is obtained with respect to 100 parts by weight in total of 7% by weight of a conductive filler. (Hereinafter, this conductive semi-aromatic polyamide composition is referred to as (C-9)).

Example 1
Using the polyamide 12 resin composition (A-1), semi-aromatic polyamide composition (B-1), and conductive semi-aromatic polyamide composition (C-1) shown above, (Made by Co., Ltd.) In a three-layer tube molding machine, (A-1) was melted separately at an extrusion temperature of 260 ° C, (B-1) at an extrusion temperature of 240 ° C, and (C-1) at an extrusion temperature of 250 ° C. And the discharged molten resin is merged by an adapter, formed into a tubular shape, cooled by a sizing die that controls dimensions, taken up, and the layer made of (A-1) is changed to (a) layer (outermost layer), ( When the layer consisting of B-1) is (b) layer (intermediate layer) and the layer consisting of (C-1) is (c) layer (innermost layer), the layer configuration is (a) / (b) / ( c) = 0.75 / 0.15 / 0.10 mm, laminated tube having an inner diameter of 6 mm and an outer diameter of 8 mm 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 2
In Example 1, except that the conductive semi-aromatic polyamide composition (C-1) was changed to (C-2), the laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 1. Obtained. The physical property measurement results of the laminated tube are shown in Table 1. 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 composition (C-1) was changed to (C-3) and the extrusion temperature of (C-3) was changed to 270 ° C, the same as in Example 1. By the method, the laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. 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, the same as Example 1 except that the conductive semi-aromatic polyamide composition (C-1) was changed to (C-4) and the extrusion temperature of (C-4) was changed to 270 ° C. By the method, the laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. 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 conductive semi-aromatic polyamide composition (C-1) was changed to (C-5) and the extrusion temperature of (C-5) was changed to 280 ° C, the same as in Example 1. By the method, the laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. 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 conductive semi-aromatic polyamide composition (C-1) was changed to (C-6) and the extrusion temperature of (C-6) was changed to 240 ° C, it was the same as Example 1. By the method, the laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. 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
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 8
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.

Example 9
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 250 ° 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 10
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 260 ° 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 11
In Example 1, except that the semi-aromatic polyamide composition (B-1) was changed to (B-4) and the extrusion temperature of (B-4) was changed to 230 ° 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 12
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 320 ° C. Thus, a laminated tube having the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 13
In Example 1, the semiaromatic polyamide composition (B-1) was changed to (B-6), and the extrusion temperature of (B-6) was changed to 300 ° 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 14
In Example 9, except that the conductive semi-aromatic polyamide composition (C-1) was changed to (C-3) and the extrusion temperature of (C-3) was changed to 270 ° C. A laminated tube having the layer configuration shown in Table 1 was obtained in the same manner. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 15
In Example 10, the conductive semi-aromatic polyamide composition (C-1) was changed to (C-5), and the extrusion temperature of (C-5) was changed to 280 ° C. By the method, the laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 16
In Example 11, the conductive semi-aromatic polyamide composition (C-1) was changed to (C-6), and the extrusion temperature of (C-6) was changed to 240 ° C. By the method, the laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. 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, it shows in Table 1 by the method similar to Example 1 except not using a semi-aromatic polyamide composition (B-1) and a conductive semi-aromatic polyamide composition (C-1). A single layer tube 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, except that the conductive semi-aromatic polyamide composition (C-1) was changed to (C-7) and the extrusion temperature of (C-7) was changed to 350 ° C., the same as in Example 1. By the method, the laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. 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, except that the conductive semi-aromatic polyamide composition (C-1) was changed to (C-8) and the extrusion temperature of (C-8) was changed to 330 ° C., the same as in Example 1. By the method, the laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. 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 semi-aromatic polyamide composition (B-1) was changed to (B-7), and the extrusion temperature of (B-7) was changed to 280 ° C. Thus, a laminated tube having the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. 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 6, except that the conductive semi-aromatic polyamide composition (C-1) was changed to (C-9) and the extrusion temperature of (C-9) was changed to 290 ° C, the same as in Example 1. By the method, the laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. 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 composed of the semi-aromatic polyamide and the conductive semi-aromatic polyamide composition defined in the present invention is inferior in chemical solution permeation prevention, Does not have sex. The laminated tube of Comparative Example 2 that does not have a layer made of the aliphatic polyamide defined in the present invention was inferior in low-temperature impact resistance and degradation fuel resistance. The laminated tube of Comparative Example 3 which does not have a layer made of the aliphatic polyamide specified in the present invention was inferior in chemical permeation prevention. The laminated tubes of Comparative Examples 4 and 5 having a layer made of a conductive semi-aromatic polyamide composition other than those specified in the present invention were inferior in thermal stability and resistance to deterioration fuel during molding. The laminated tube of Comparative Example 6 having a layer made of a semi-aromatic polyamide other than specified in the present invention was inferior in deterioration fuel resistance and interlayer adhesion. The laminated tube of Comparative Example 7 having a layer made of a semi-aromatic polyamide other than those defined in the present invention and a layer made of a conductive semi-aromatic polyamide composition was inferior in deterioration fuel resistance and interlayer adhesion.
On the other hand, the laminated tubes of Examples 1 to 16 defined in the present invention have electrical conductivity, thermal stability at the time of molding, low temperature impact resistance, degradation fuel resistance, chemical liquid permeation prevention, and It is clear that various properties such as interlayer adhesion are good.

Claims (6)

(A) layer composed of aliphatic polyamide (A), diamine units containing 60 mol% or more of xylylenediamine units and / or bis (aminomethyl) naphthalene units with respect to all diamine units, and with respect to all dicarboxylic acid units And (b) layer (b) made of a semi-aromatic polyamide (B) comprising a dicarboxylic acid unit containing 60 mol% or more of an aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms, and (c1 60 mol% or more of xylylenediamine units consisting of m) -xylylenediamine units and (c2) p-xylylenediamine units or (c1) m-xylylenediamine units, and the moles of (c1) and (c2) The number of carbon atoms is 8 or more and 13 or less with respect to the diamine unit having a ratio of 50:50 mol% or more and 100: 0 mol% or less and all dicarboxylic acid units. At least three or more layers including (c) layer composed of a semi-aromatic polyamide comprising a dicarboxylic acid unit containing 60 mol% or more of an aliphatic dicarboxylic acid unit and a conductive semi-aromatic polyamide composition (C) comprising a conductive filler. An electrically conductive laminated tube comprising: Aliphatic dicarboxylic acid units having 8 to 13 carbon atoms in the semiaromatic polyamide (B) and the conductive semiaromatic polyamide composition (C) are derived from azelaic acid, sebacic acid, and dodecanedioic acid. The conductive laminated tube according to claim 1, wherein the conductive laminated tube is at least one selected from the group consisting of: 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). 3. The conductive laminated tube according to claim 1, 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 composed of the aliphatic polyamide (A) is disposed in the outermost layer, and the (c) layer composed of the conductive semi-aromatic polyamide composition (C) is disposed in the innermost layer. The electroconductive laminated tube in any one of Claim 1 to 3. 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 composition (C). The conductive laminated tube according to any one of claims 1 to 4, wherein the conductive laminated tube is disposed in the middle. The conductive laminated tube according to any one of claims 1 to 5, wherein the conductive laminated tube is manufactured by coextrusion molding.