JP6255823B2 - Laminated tube - Google Patents

Description

  The present invention is a laminated tube comprising a layer made of an aliphatic polyamide, a layer made of a semi-aromatic polyamide having a specific structure, and a layer made of a fluoropolymer having specific flow characteristics and specific functional groups. The present invention relates to a laminated tube excellent in low temperature impact resistance, chemical solution permeation prevention properties, interlayer adhesion properties, degradation fuel resistance properties, and environmental stress crack resistance properties.

  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.

  In addition, from the viewpoint of saving gasoline consumption and improving performance, alcohols having a low boiling point such as methanol and ethanol, or oxygen-containing gasoline blended with ethers such as ethyl t-butyl ether (ETBE) 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 / chlorotrifluoroethylene copolymer ( ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (TFE / HFP / VDF, THV), tetrafur Ethylene / hexafluoropropylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer (TFE / HFP / VDF / PAVE), tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (TFE / PAVE, PFA), Tetrafluoroethylene / hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer (TFE / HFP / PAVE), chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer (CTFE / PAVE / TFE, Many laminated tubes with CPT) have been proposed (see, for example, Patent Document 1).

  Among these, polyphenylene sulfide (PPS) is extremely excellent in chemical solution permeation prevention properties, particularly in gasoline permeation prevention properties and alcohol permeability. For example, a layer made of polyamide resin, a polyamide resin at a specific ratio, polyphenylene sulfide (PPS), a thermoplastic resin having a functional group, and a layer made of a resin composition containing a thermoplastic resin having no functional group, and polyphenylene sulfide ( Laminated tube composed of a layer composed of a polyphenylene sulfide resin composition containing PPS) and an epoxy-modified thermoplastic resin composition, a layer composed of a polyamide resin, a polyamide resin, polyphenylene sulfide (PPS), and a functional group at a specific ratio There has been proposed a laminated tube composed of a layer composed of a thermoplastic resin and a resin composition containing a thermoplastic resin having no functional group, and a layer composed of a polyphenylene sulfide resin composition not containing an epoxy-modified thermoplastic resin. (See Patent Documents 2 and 3). The above-mentioned technology is applied to polyamide, polyphenylene sulfide (PPS) as an adhesive resin interposed between a layer made of polyamide 11 or polyamide 12 and a layer made of polyphenylene sulfide (PPS), which has been conventionally used as a constituent material of a single-layer tube. ), An adhesive resin mixture containing a thermoplastic resin having a functional group as a compatibilizing agent has been proposed. However, in the laminated tube, the interlayer adhesiveness is affected by the morphology of the adhesive resin composition, and there is a problem that the interlayer adhesiveness varies greatly and decreases depending on the extrusion conditions and the use environment conditions. In particular, it has the disadvantage that the durability of the interlaminar adhesion strength is poor after contacting and immersing in fuel for a long time, and there has been a problem in actual use. Furthermore, when the layer made of polyphenylene sulfide is used as the innermost layer, in the state where a certain stress load is applied during fuel immersion, minute cracks called crazes are generated in the polyphenylene sulfide layer, and the chemical liquid permeation preventing property is greatly impaired. Therefore, development of a laminated tube having resistance to environmental stress load (environmental stress crack resistance) is demanded. In order to solve this problem, a low fuel permeation layer is formed using polyphenylene sulfide (PPS), and a sandwich structure in which the fuel low permeation layer is sandwiched between an inner layer and an outer layer is formed. A laminated tube formed of at least one of a polyolefin-based resin having a functional group has been proposed (see Patent Document 4). In the example of this document, a laminated tube including a layer made of polyamide 12, a layer made of polyphenylene sulfide (PPS), a layer made of polyamide 12, and a layer made of a functional group-containing fluororesin is disclosed, and the fuel immersion is disclosed. Sometimes, when a certain stress load is applied, the problem that microcracks called crazes occur in the polyphenylene sulfide layer and the chemical permeation prevention property is greatly impaired is still solved. When it is used after being immersed or in a state where a certain stress load is applied at the time of fuel contact, there is room for improvement in durability of interlayer adhesion.

  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 a laminated tube comprising at least two layers including a layer made of a semi-aromatic polyamide composed of a dicarboxylic acid unit containing at least 60 mol% of an aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms. (See Patent Document 5). In the example of this document, a laminate comprising a layer made of an aliphatic polyamide, a layer made of a semi-aromatic polyamide made of xylylenediamine units and / or bis (aminomethyl) naphthalene units, and a layer made of a fluorine-containing polymer Although the tube is disclosed, there is no disclosure of technical data or technical suggestion regarding environmental stress crack resistance.

US Pat. No. 5,554,425 JP 2008-213458 A JP 2008-213459 A JP 2005-127503 A JP 2006-044201 A

  An object of the present invention is to solve the above-mentioned problems and to provide a laminated tube excellent in low temperature impact resistance, chemical solution permeation prevention property, interlayer adhesion property, degradation fuel resistance property, and environmental stress crack resistance.

  As a result of intensive investigations to solve the above problems, the present inventors have found that a layer made of an aliphatic polyamide, a semi-aromatic polyamide having a specific structure, and a fluorine having a specific fluidity and a specific functional group. It has been found that a laminated tube including a layer made of a polymer is excellent in low-temperature impact resistance, chemical solution permeation prevention properties, interlayer adhesion properties, deterioration fuel resistance properties, and environmental stress crack resistance properties.

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 based on all dicarboxylic acid units, and ASTM D- MFR (temperature higher by 50 ° C. than melting point of fluorine-containing polymer (C), 49 N load) measured by the method defined in 3159 is 1 g / 10 min to 6 g / 10 min, from the functional groups having reactivity are introduced into the molecular chain, and a conductive filler fluorine-containing polymer which contains a consist (C) including the (c) layer, at least three or more layers It is to provide a laminate tube according to claim Rukoto.

The preferable aspect of the laminated tube of this invention is shown below. A plurality of preferred embodiments can be combined.
[1] The 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 laminated tube comprising at least one selected homopolymer or a copolymer using several kinds of raw material monomers forming these.
[2] The aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms in the semi-aromatic polyamide (B) is selected from the group consisting of units derived from azelaic acid, sebacic acid, and dodecanedioic acid, or at least And xylylenediamine units and / or bis (aminomethyl) naphthalene units are m-xylylenediamine, p-xylylenediamine, 1,5-bis (aminomethyl) naphthalene, and 2,6-bis ( A laminated tube characterized by being at least one selected from the group consisting of units derived from (aminomethyl) naphthalene.
[3] The functional group having reactivity with the amino group in the fluorine-containing polymer (C) is a carboxyl group, an acid anhydride group or a carboxylate, a hydroxyl group, a sulfo group or a sulfonate, an epoxy group. , A cyano group, a carbonate group, and at least one selected from the group consisting of a haloformyl group.
[4] The (a) layer composed of the aliphatic polyamide (A) is disposed in the outermost layer, and the (b) layer composed of the semi-aromatic polyamide (B) is composed of the (a) layer composed of the aliphatic polyamide (A); A laminated tube, which is disposed between layers (c) made of a fluorine-containing polymer (C).
[5] A laminated tube, wherein the (b) layer made of a semi-aromatic polyamide (B) and the (c) layer made of a fluorine-containing polymer (C) are in direct contact.
[6] A laminated tube, wherein a conductive layer made of a fluorine-containing polymer composition containing a conductive filler is disposed in the innermost layer of the laminated tube.
[7] A laminated tube manufactured by coextrusion molding.
[8] A laminated tube having at least a corrugated region.
[9] A laminated tube used as a chemical solution transport tube.

  The 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 layer made of a fluoropolymer having a specific flow characteristic and a specific functional group. Both impact resistance and chemical permeation preventive properties are achieved, and various properties such as interlayer adhesion, degradation fuel resistance, and environmental stress crack resistance are excellent. In particular, alcohol mixed hydrocarbons that permeate and evaporate from the tube partition wall can be suppressed to the limit, and compliance with strict environmental regulations becomes possible. Furthermore, it is excellent in resistance (deterioration fuel resistance) and environmental stress crack resistance to sour gasoline generated by oxidation of gasoline, which is a problem in actual use of the laminated tube. Therefore, the laminated tube of the present invention can be used in any environment, has high reliability, and its utility value is extremely large.

Tube used for evaluation of environmental stress crack resistance

  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.

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

  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. As described above, amines can be added at any stage during polymerization or at any stage after melt kneading after polymerization. However, when the interlayer adhesion of the laminated tube is taken into consideration, the amines are added at the stage during polymerization. It is preferable.
Examples of the amines include monoamines, diamines, triamines, and polyamines. In addition to amines, carboxylic acids such as monocarboxylic 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.

  The terminal-modified aliphatic polyamide may be a mixture of two or more types 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-mentioned homopolymer, a mixture of the above-mentioned copolymer, a mixture of a homopolymer and a copolymer, or another polyamide-based resin, a semi-aromatic as described later. It may be a mixture with an aromatic polyamide (B), a fluorine-containing polymer (C) in which a functional group reactive to an amino group is introduced into the molecular chain, or other thermoplastic 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), polyether ketone ketone (PEKK), polyether ether ether ketone (PEEEK), polyether ether ketone ketone (PEEKK), polyether ketone ketone ketone (PEKKK), polyether ketone ether ketone ketone (PEKEKK), etc. Polyketone resin, polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butane Polynitrile resins such as ene / styrene copolymer (ABS) and acrylonitrile / butadiene copolymer (NBR), polymethacrylate resins such as polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA), polyvinyl alcohol ( PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), polyvinyl chloride resins such as vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer, and cellulose type such as cellulose acetate and cellulose butyrate Resin, polycarbonate resin such as polycarbonate (PC), thermoplastic polyimide (TPI), polyetherimide, polyesterimide, polyamideimide (PAI), polyimide resin such as polyesteramideimide, thermoplastic polyurethane resin , Polyamide elastomer, polyurethane elastomer, polyester elastomer or the like. 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 may be 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the aliphatic polyamide (A) from the viewpoint of sufficiently ensuring the flexibility and low temperature impact resistance of the laminated tube. Preferably, it is 2 parts by mass or more and 20 parts by mass or less.

  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 such as Li, Na, K, Mg, Ca, Sr, Ba, alkaline earth metals, Al, Sn, Sb, Ti, Mn, Fe, Ni, Cu, Zn, Cd, etc. Is mentioned. These can use 1 type (s) or 2 or more types.

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

The aromatic vinyl compound polymer block is a polymer block mainly composed of units derived from an aromatic vinyl compound. In this case, the aromatic vinyl compound includes styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,5-dimethylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene, 4-propyl. Styrene, 4-cyclohexyl styrene, 4-dodecyl styrene, 2-ethyl-4-benzyl styrene, 4- (phenylbutyl) styrene and the like can be mentioned, and one or more of these can be used. In addition, the aromatic vinyl compound-based polymer block may optionally have a unit composed of a small amount of another unsaturated monomer.
Conjugated diene compound-based polymer blocks are 1,3-butadiene, chloroprene, isoprene, 2,3-dimethyl-1,3-butadiene, 1,3-pentadiene, 4-methyl-1,3-pentadiene, 1,3 -A polymer block formed from one or more conjugated diene compounds such as hexadiene, and a hydrogenated aromatic vinyl compound / conjugated diene compound block copolymer, the conjugated diene compound polymer Part or all of the unsaturated bond portions in the block are saturated bonds by hydrogenation.

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

  Further, (ethylene and / or propylene) / α-olefin copolymer, (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) used as an impact resistance improving material ) Type copolymer, ionomer polymer, and aromatic vinyl compound / conjugated diene compound type block copolymer are preferably polymers modified with carboxylic acid and / or derivatives thereof. By modifying with such a component, a functional group having 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 or less with respect to 100 parts by mass of the aliphatic polyamide (A) from the viewpoint of sufficiently ensuring the mechanical strength and low temperature impact resistance of the laminated tube. It is preferable that it is 3 parts by mass or more and 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 the xylylenediamine unit and / or bis (aminomethyl) naphthalene unit in the semi-aromatic polyamide (B) is such as heat resistance, chemical resistance, impact resistance, chemical liquid permeation prevention property of the obtained laminated tube. From the viewpoint of sufficiently securing various physical properties, it is at least 60 mol%, preferably at least 75 mol%, more preferably at least 90 mol%, based on all diamine units.

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 laminated tube of the present invention, other than the xylylenediamine unit and / or the bis (aminomethyl) naphthalene unit. It may contain a diamine unit. Other diamine units include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, , 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) has various physical properties such as heat resistance, chemical resistance and chemical solution permeation prevention property of the obtained laminated tube. From the viewpoint of ensuring sufficiently, 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 laminated tube of the present invention, the dicarboxylic acid unit other than the aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms. 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 excellent properties of the 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. ensures the mechanical properties of the resulting laminated tube. From the viewpoint of securing the desirable formability of the laminated tube by setting the viscosity at the time of melting to an appropriate range, it is preferably 1.5 or more and 4.0 or less, and is 1.8 or more and 3.5 or less More preferably, it is 2.0 or more and 3.0 or less.

  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) or a fluorine-containing polymer (C) in which a functional group having reactivity with the amino group described below is introduced into the molecular chain. 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 fluorine-containing polymer (C) used in the present invention has an MFR (temperature higher by 50 ° C. than the melting point of the fluorine-containing polymer (C), 49 N load) measured by the method defined in ASTM D-3159. 1 g / 10 min to 35 g / 10 min and is a fluorine-containing polymer in which a functional group reactive to an amino group is introduced into the molecular chain (hereinafter referred to as fluorine-containing polymer (C)) May be called).

  When the MFR (melt flow rate) of the fluorine-containing polymer (C) is coextruded with the aliphatic polyamide (A), the semi-aromatic polyamide (B), etc., the kneading temperature and molding without significant deterioration of these In order to ensure sufficient melt fluidity in the temperature range, prevent the occurrence of melt fracture, have good surface characteristics and appearance of the inner surface of the laminated tube, and obtain a laminated tube having excellent environmental stress crack resistance, It is 1 g / 10 min or more and 35 g / 10 min or less, preferably 2 g / 10 min or more and 30 g / 10 min or less, more preferably 2.5 g / 10 min or more and 25 g / 10 min or less. The MFR (melt flow rate) of the fluorinated polymer (C) is 50 ° C. higher than the melting point of the fluorinated polymer (C) by a method prescribed in ASTM D-3159 at a load of 49 N for 10 minutes. It is a value obtained by measuring the amount of resin (g / 10 minutes) passing through a nozzle having a diameter of 2 mm and a length of 10 mm.

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

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

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

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

Among the fluorine-containing polymers (C), from the viewpoint of heat resistance, chemical resistance, and chemical permeation prevention, at least a copolymer (C1) composed of a vinylidene fluoride unit (VDF unit), at least tetrafluoro Copolymer (C2) composed of ethylene units (TFE units) and ethylene units (E units), at least tetrafluoroethylene units (TFE units) and hexafluoropropylene units (HFP units) and / or the above general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group that may contain an etheric oxygen atom having 1 to 10 carbon atoms), and a copolymer (C3 ), At least a copolymer (C4) composed of chlorotrifluoroethylene units (CTFE units), at least It is preferably a chlorotrifluoroethylene unit (CTFE units) and consisting of tetrafluoroethylene units (TFE units) copolymer (C5).

As a copolymer (C1) comprising at least a vinylidene fluoride unit (VDF unit) (hereinafter sometimes referred to as a VDF copolymer (C1)), for example,
Vinylidene fluoride homopolymer (polyvinylidene fluoride (PVDF)) (C1-1),
A copolymer comprising VDF units and TFE units, wherein the content of VDF units is 30 mol% or more and 99 mol% or less with respect to the whole monomer excluding the functional group-containing monomers described later, and TFE units A copolymer (C1-2) having a content of 1 mol% to 70 mol%,
A copolymer comprising a VDF unit, a TFE unit, and a trichlorofluoroethylene unit, wherein the content of the VDF unit is 10 mol% or more and 90 mol with respect to the whole monomer excluding the functional group-containing monomer described later. % Or less, a copolymer (C1-3) having a TFE unit content of 0 mol% to 90 mol%, and a trichlorofluoroethylene unit content of 0 mol% to 30 mol%,
A copolymer comprising a VDF unit, a TFE unit, and an HFP unit, wherein the content of the VDF unit is 10 mol% or more and 90 mol% or less with respect to the whole monomer excluding the functional group-containing monomer described later. And a copolymer (C1-4) in which the content of TFE units is 0 mol% or more and 90 mol% or less, and the content of HFP units is 0 mol% or more and 30 mol% or less.

  In the copolymer (C1-4), the content of VDF units is 15 mol% or more and 84 mol% or less, and the content of TFE units is based on the whole monomer excluding the functional group-containing monomers described later. It is preferable that 15 mol% or more and 84 mol% or less and the content of the HFP unit is 0 mol% or more and 30 mol% or less.

  As a copolymer (C2) comprising at least a tetrafluoroethylene unit (TFE unit) and an ethylene unit (E unit) (hereinafter sometimes referred to as a TFE copolymer (C2)), for example, the functionalities described below Examples include a polymer having a TFE unit content of 20 mol% or more based on the entire monomer excluding the group-containing monomer, and further, the entire monomer excluding the functional group-containing monomer described later. On the other hand, the content of TFE units is 20 mol% or more and 80 mol% or less, the content of E units is 20 mol% or more and 80 mol% or less, and the content of units derived from monomers copolymerizable therewith Examples thereof include a copolymer having an amount of 0 mol% to 60 mol%.

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

As the TFE copolymer (C2), for example,
TFE unit and E unit, and the above general formula CH ₂ = CX ¹ (CF ₂ ) _n X ² (where X ¹ and X ² independently represent a hydrogen atom or a fluorine atom, and n is 2 or more and 10 or less) It is a copolymer composed of fluoroolefin units derived from the fluoroolefin represented by the formula (1), and the content of TFE units is based on the whole monomer excluding the functional group-containing monomers described later. 30 mol% or more and 70 mol% or less, the content of E unit is 20 mol% or more and 55 mol% or less, and the above general formula CH ₂ = CX ³ (CF ₂ ) _n X ⁴ (where X ³ and X ⁴ are Each independently represents a hydrogen atom or a fluorine atom, and n is an integer of 2 or more and 10 or less.) The content of the fluoroolefin unit derived from the fluoroolefin represented by Polymer ( 2-1),
A copolymer composed of TFE units, E units, HFP units, and units derived from monomers copolymerizable therewith, with respect to the entire monomer excluding the functional group-containing monomers described below, TFE unit content of 30 mol% to 70 mol%, E unit content of 20 mol% to 55 mol%, HFP unit content of 1 mol% to 30 mol%, and copolymerization with these A copolymer (C2-2) having a content of units derived from possible monomers of 0 mol% or more and 10 mol% or less,
TFE units and E units, and the general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). A copolymer comprising PAVE units derived from PAVE, wherein the content of TFE units is 30 mol% or more and 70 mol% or less, based on the whole monomer excluding the functional group-containing monomers described later, E units In the general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). The copolymer (C2-3) etc. whose content of the PAVE unit derived from PAVE represented by this is 0 mol% or more and 10 mol% or less are mentioned.

At least a tetrafluoroethylene unit (TFE unit) and a hexafluoropropylene unit (HFP unit) and / or the above general formula CF ₂ = CFOR ^f1 (where R ^f1 represents an etheric oxygen atom having 1 to 10 carbon atoms) As a copolymer (C3) (hereinafter sometimes referred to as a TFE copolymer (C3)) composed of PAVE units derived from PAVE represented by PAVE represented by: ,
It is a copolymer composed of TFE units and HFP units, and the content of TFE units is preferably 70 mol% or more and 95 mol% or less with respect to the whole monomer excluding the functional group-containing monomer described later, Is a copolymer (C3-1) having a HFP unit content of 5 mol% or more and 30 mol% or less, preferably 7 mol% or more and 15 mol% or less,
It is derived from PAVE represented by a TFE unit and the general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). It is a copolymer comprising one or more PAVE units, and the content of TFE units is 70 mol% or more and 95 mol% or less with respect to the whole monomer excluding the functional group-containing monomer described later. And 1 derived from PAVE represented by the general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). A copolymer (C3-2) in which the content of the seed or two or more kinds of PAVE units is 5 mol% or more and 30 mol% or less,
TFE units and HFP units, and the above general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). A copolymer consisting of one or more PAVE units derived from PAVE, wherein the content of TFE units is 70 mol% or more with respect to the whole monomer excluding the functional group-containing monomers described later 95 mol% or less, represented by HFP units and the above general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). A copolymer (C3-3) in which the total content of one or more PAVE units derived from PAVE is 5 mol% to 30 mol%.

The copolymer consisting of at least chlorotrifluoroethylene units (CTFE units) has CTFE units [—CFCl—CF ₂ —] and is composed of ethylene units (E units) and / or fluorine-containing monomer units. Chlorotrifluoroethylene copolymer (C4) (hereinafter sometimes referred to as CTFE copolymer (C4)).
The fluorine-containing monomer in the CTFE copolymer (C4) is not particularly limited as long as it is other than CTFE, but vinylidene fluoride (VDF), hexafluoropropylene (HFP), the above general formula CF ₂ = CFOR ^{P1 represented by f1} (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms), the above general formula CH ₂ = CX ¹ (CF ₂ ) and fluoroolefins represented by _n X ² (wherein X ¹ and X ² each independently represent a hydrogen atom or a fluorine atom, and n is an integer of 2 or more and 10 or less). These can use 1 type (s) or 2 or more types.

  The CTFE copolymer (C4) is not particularly limited. For example, the CTFE / PAVE copolymer, the CTFE / VDF copolymer, the CTFE / HFP copolymer, the CTFE / E copolymer, and the CTFE / PAVE / E copolymer. Examples thereof include a polymer, a CTFE / VDF / E copolymer, and a CTFE / HFP / E copolymer.

  The content of CTFE units in the CTFE copolymer (C4) is preferably 15 mol% or more and 70 mol% or less with respect to the whole monomer excluding the functional group-containing monomer described later, and is 18 mol%. More preferably, it is 65 mol% or less. On the other hand, the content of the E unit and / or the fluorine-containing monomer unit is preferably 30 mol% or more and 85 mol% or less, and more preferably 35 mol% or more and 82 mol% or less.

At least the copolymer (C5) composed of chlorotrifluoroethylene units (CTFE units) and tetrafluoroethylene units (TFE units) has CTFE units [—CFCl—CF ₂ —] and TFE units [—CF ₂ —CF _2. -], And a chlorotrifluoroethylene copolymer composed of monomer units copolymerizable with CTFE and TFE (hereinafter, sometimes referred to as CTFE / TFE copolymer (C5)).

The copolymerizable monomer in the CTFE / TFE copolymer (C5) is not particularly limited as long as it is other than CTFE and TFE, but vinylidene fluoride (VDF), hexafluoropropylene (HFP), the above PAVE represented by the general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms), the general formula CH ₂ = Such as a fluoroolefin represented by CX ¹ (CF ₂ ) _n X ² (wherein X ¹ and X ² independently represent a hydrogen atom or a fluorine atom, and n is an integer of 2 or more and 10 or less). Fluorinated monomers, ethylene, propylene, isobutene and other olefins having 2 to 4 carbon atoms, vinyl acetate, methyl (meth) acrylate, (meth Vinyl esters such as ethyl acrylate, methyl vinyl ether (MVE), ethyl vinyl ether (EVE), non-fluorine-containing monomers of vinyl ether and butyl vinyl ether (BVE), and the like. These can use 1 type (s) or 2 or more types. Among these, PAVE is represented by the above general formula CF ₂ = CFOR ^f1 (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms). Of these, perfluoro (methyl vinyl ether) (PMVE) and perfluoro (propyl vinyl ether) (PPVE) are more preferable, and PPVE is more preferable from the viewpoint of ensuring sufficient heat resistance.

  The CTFE / TFE copolymer (C5) is not particularly limited, and examples thereof include a CTFE / TFE copolymer, a CTFE / TFE / HFP copolymer, a CTFE / TFE / VDF copolymer, and a CTFE / TFE / PAVE copolymer. For example, CTFE / TFE / PFE copolymer, CTFE / TFE / HFP / PAVE copolymer, and CTFE / TFE / VDF / PAVE copolymer. Among these, CTFE / TFE / PAVE copolymer, A CTFE / TFE / HFP / PAVE copolymer is preferred.

  The total content of CTFE units and TFE units in the CTFE / TFE copolymer (C5) is from the viewpoint of ensuring good moldability, environmental stress crack resistance, chemical liquid permeation resistance, heat resistance, and mechanical properties. It is preferably 90 mol% or more and 99.9 mol% or less with respect to the whole monomer excluding the functional group-containing monomer described later, and the content of the monomer unit copolymerizable with the CTFE and TFE. Is preferably 0.1 mol% or more and 10 mol% or less.

  The content of CTFE units in the CTFE / TFE copolymer (C5) is the total amount of the above CTFE units and TFE units from the viewpoint of ensuring good moldability, environmental stress crack resistance, and chemical penetration prevention properties. It is preferably 15 mol% or more and 80 mol% or less, more preferably 17 mol% or more and 70 mol% or less, and further preferably 19 mol% or more and 65 mol% or less with respect to 100 mol%. .

  In the CTFE / TFE copolymer (C5), when the monomer copolymerizable with CTFE and TFE is PAVE, the content of the PAVE unit is the entire monomer excluding the functional group-containing monomer described later. On the other hand, it is preferably 0.5 mol% or more and 7.0 mol% or less, and more preferably 1.0 mol% or more and 5.0 mol% or less.

  In the CTFE / TFE copolymer (C5), when the monomers copolymerizable with CTFE and TFE are HFP and PAVE, the total content of the HFP unit and the PAVE unit is the functional group-containing monomer described later. It is preferably 0.5 mol% or more and 7.0 mol% or less, and more preferably 1.0 mol% or more and 5.0 mol% or less with respect to the whole monomer excluding.

The TFE copolymer (C3), the CTFE copolymer (C4), and the CTFE / TFE copolymer (C5) are excellent in chemical liquid permeation prevention properties, particularly barrier properties against alcohol-containing gasoline. For the alcohol-containing gasoline permeability coefficient, put the sheet obtained from the resin to be measured into a permeability coefficient measuring cup filled with isooctane / toluene / ethanol mixed solvent in which isooctane, toluene, and ethanol are mixed at a volume ratio of 45:45:10. , A value calculated from a change in mass measured at 60 ° C. The alcohol-containing gasoline permeability coefficient of the TFE copolymer (C3), CTFE copolymer (C4) and CTFE / TFE copolymer (C5) is 1.5 g · mm / (m ² · day) or less. It is preferably 0.01 g · mm / (m ² · day) or more and 1.0 g · mm / (m ² · day) or less, more preferably 0.02 g · mm / (m ² · day). More preferably, it is 0.8 g · mm / (m ² · day) or less.

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

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

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

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

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

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

Further, in the fluorinated polymer (C), the melting point and glass transition point of the polymer can be adjusted by selecting the type and composition ratio of the fluorinated monomer and other monomers. The melting point of the fluorine-containing polymer (C) is appropriately selected according to the purpose, application, and method of use. When coextruding with the aliphatic polyamide (A), the semi-aromatic polyamide (B), etc., It is preferable to be close to the molding temperature. Therefore, it is preferable to optimize the melting point of the fluorine-containing polymer (C) by appropriately adjusting the ratio of the fluorine-containing monomer, the non-fluorine-containing monomer, and the functional group-containing monomer described later. The melting point of the fluorine-containing polymer (C) is the heat melting stability, continuous moldability, co-extrusion with the aliphatic polyamide (A) and the semi-aromatic polyamide (B), and the fluorine-containing polymer (C). From the viewpoint of sufficiently ensuring the heat resistance, chemical resistance, and chemical liquid permeation prevention property, it is preferably 150 ° C. or higher and 320 ° C. or lower, more preferably 170 ° C. or higher and 310 ° C. or lower, and 180 ° C. or higher and 300 ° C. or lower. More preferably, it is not higher than ° C.
Here, the melting point means that the sample is heated to a temperature higher than the expected melting point using a differential scanning calorimeter, and then the sample is cooled at a rate of 10 ° C. per minute and cooled to 30 ° C. The melting point is defined as the temperature of the peak value of the melting curve measured by leaving the sample as it is for about 1 minute and then increasing the temperature at a rate of 10 ° C. per minute.

  The fluorine-containing polymer (C) used in the present invention has a functional group having reactivity with an amino group in the molecular structure, and the functional group is the same as that of the fluorine-containing polymer (C). It may be contained at either the molecular end, the side chain or the main chain. Moreover, the functional group may be used alone or in combination of two or more kinds in the fluorine-containing polymer (C). The type and content of the functional group are appropriately determined depending on the type, shape, application, required interlayer adhesion, adhesion method, functional group introduction method, etc. of the counterpart material laminated on the fluorine-containing polymer (C). The

  Functional groups having reactivity with amino groups include carboxyl groups, acid anhydride groups or carboxylates, hydroxyl groups, sulfo groups or sulfonates, epoxy groups, cyano groups, carbonate groups, and haloformyl groups. There may be mentioned at least one selected from the group. In particular, at least one selected from the group consisting of a carboxyl group, an acid anhydride group or carboxylate, an epoxy group, a carbonate group, and a haloformyl group is preferable.

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

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

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

As the functional group-containing fluorine-containing monomer, the general formula CX ³ = CX ⁴ — (R ¹ ) _n —Y (where Y is —OH, —CH ₂ OH, —COOM (M is a hydrogen atom or A functional group selected from the group consisting of a carboxyl group-derived group, —SO ₃ M (M represents a hydrogen atom or an alkali metal), a sulfonic acid-derived group, an epoxy group, and —CN. And X ³ and X ⁴ are the same or different and each represents a hydrogen atom or a fluorine atom (provided that when X ³ and X ⁴ are the same hydrogen atom, n = 1, and R ^{1 represents} a fluorine atom) R ¹ is an alkylene group having 1 to 40 carbon atoms, a fluorine-containing oxyalkylene group having 1 to 40 carbon atoms, a fluorine-containing alkylene group having 1 to 40 carbon atoms having an ether bond, Or etherification It represents a fluorine-containing oxyalkylene group having 1 or more and 40 or less carbon atoms having, n is 0 or 1.) In unsaturated compounds and the like represented.
Examples of the carboxyl group-derived group as Y in the above general formula include a general formula —C (═O) Q ¹ (wherein Q ¹ represents —OR ² , —NH ₂ , F, Cl, Br, or I). R ² represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 22 carbon atoms.) And the like.
Examples of the sulfonic acid-derived group that is Y in the general formula include a general formula —SO ₂ Q ² (wherein Q ² represents —OR ³ , —NH ₂ , F, Cl, Br, or I, and R ³ Represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 22 carbon atoms).
Y is preferably —COOH, —CH ₂ OH, —SO ₃ H, —SO ₃ Na, —SO ₂ F, or —CN.

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

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

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

The carbonate group introduced as a terminal group of the fluorine-containing polymer (C) is generally a group having a bond of —OC (═O) O—, specifically, —OC (═O) O—R. ⁴ groups [R ⁴ is a hydrogen atom, an organic group (for example, an alkyl group having 1 to 20 carbon atoms, an alkyl group having 2 to 20 carbon atoms having an ether bond), or a group I, II, or VII element. . ] Those _{structures, -OC (= O) OCH 3} , -OC (= O) OC 3 H 7, -OC (= O) OC 8 H 17, -OC (= O) OCH 2 CH 2 OCH 2 CH ₃ etc. may be mentioned. The haloformyl group is specifically —COZ [Z is a halogen element. ] And -COF, -COCl, etc. are mentioned. These can use 1 type (s) or 2 or more types.

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

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

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

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

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

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

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

  The laminated tube according to the present invention is a diamine unit comprising 60 mol% or more of a xylylenediamine unit and / or a bis (aminomethyl) naphthalene unit with respect to the (a) layer comprising the aliphatic polyamide (A) and all diamine units. And a (b) layer comprising 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 all dicarboxylic acid units, and amino It is composed of at least three layers including the (c) layer made of the fluorine-containing polymer (C) in which a functional group having reactivity with the group is introduced into the molecular chain. By including the (b) layer which consists of a semi-aromatic polyamide (B), the chemical | medical solution permeation prevention property of a laminated tube, especially a hydrocarbon permeation prevention property can be improved. Moreover, the alcohol permeation | blocking prevention property of a laminated tube becomes favorable by including the (c) layer which consists of a fluorine-containing polymer (C).

In a preferred embodiment, the (a) layer made of the aliphatic polyamide (A) is disposed in the outermost layer of the laminated tube. By disposing the (a) layer made of the aliphatic polyamide (A) as the outermost layer, a laminated tube excellent in chemical resistance and flexibility can be obtained.
Further, 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 fluorine-containing polymer (C). .

  In a more preferred embodiment, the (b) layer made of the semi-aromatic polyamide (B) and the (c) layer made of the fluorine-containing polymer (C) are arranged in direct contact. By using the fluorine-containing polymer (C) defined in the present invention, it is not necessary to provide an adhesive layer, and excellent interlayer adhesion with the (b) layer made of the semi-aromatic polyamide (B) is obtained. It becomes possible.

  Further, in the laminated tube of the present invention, when the conductive layer made of the fluorine-containing polymer composition containing the conductive filler is disposed in the innermost layer of the laminated tube, the chemical liquid permeation preventing property, the deterioration fuel resistance, In addition to being excellent in elution resistance of the monomer oligomer, when used as a fuel piping tube, it is possible to prevent the spark generated by the internal friction of the fuel circulating in the piping or the friction with the tube wall from igniting the fuel. It becomes possible. In that case, it is possible to achieve both low temperature impact resistance and conductivity by arranging a layer made of a fluorine-containing polymer having no conductivity outside the conductive layer, It is also economically advantageous. Furthermore, the fluorine-containing polymer referred to herein also includes a fluorine-containing polymer (C) defined in the present invention in which a functional group having reactivity with an amino group is introduced into a molecular chain, The fluorine-containing polymer which does not have a functional group mentioned later is also indicated.

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

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

  Carbon nanotubes are what are called hollow carbon fibrils, which have an outer region consisting of an essentially continuous multi-layer of regularly arranged carbon atoms and an inner hollow region, each layer And the hollow region are essentially cylindrical fibrils arranged substantially concentrically around the cylindrical axis of the fibrils. 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 or less, preferably 4 nm or more and 60 nm or less, from the viewpoint of imparting sufficient dispersibility in the resin and good conductivity of the obtained resin molding. More preferably. The aspect ratio (referring to the ratio of length / outer diameter) of the carbon 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 may be surface-treated with a surface treatment agent such as titanate, aluminum or 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 varies depending on the type of the conductive filler used, it cannot be specified unconditionally, but from the viewpoint of balance of conductivity, fluidity, mechanical strength, etc., 100 parts by mass of the fluorine-containing polymer On the other hand, generally 3 to 30 parts by mass is preferably selected.
In addition, the conductive filler preferably has a surface specific resistance value of 10 ⁸ Ω / square or less and 10 ⁶ Ω / square or less in order to obtain sufficient antistatic performance. However, the addition of the conductive filler tends to cause deterioration of strength and fluidity. Therefore, it is desirable that the content of the conductive filler is as small as possible if the target conductivity level is obtained.

  In the 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 laminated tube, the use, etc. It is determined in consideration of the properties of the laminated tube, such as chemical penetration prevention, low temperature impact resistance and flexibility. In general, the thicknesses of the (a) layer, (b) layer, and (c) layer are preferably 3% or more and 90% or less, respectively, with respect to the thickness of the entire laminated tube. In consideration of the balance between the low temperature impact resistance and the chemical liquid permeation prevention property, the thicknesses of the layers (b) and (c) are more preferably 5% or more and 80% or less, respectively, with respect to the total thickness of the laminated tube. And more preferably 7% or more and 50% or less.

  The total number of layers in the 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 fluorine-containing polymer (C). As long as there are at least three layers including the layer (c) consisting of: Furthermore, the laminated tube of the present invention has other functions in addition to the three layers (a), (b), and (c) to provide additional functions or to obtain an economically advantageous laminated tube. You may have the layer which consists of a plastic resin 1 layer or 2 layers or more. Although the number of layers of the laminated tube of the present invention is 3 or more, it is preferably 8 or less, more preferably 3 or more and 7 or less, judging from the mechanism of the tube production apparatus.

  Other thermoplastic resins include polymetaxylylene adipamide (polyamide MXD6), polymetaxylylene terephthalamide (polyamide) other than the aliphatic polyamide (A) and semi-aromatic polyamide (B) defined in the present invention. 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), polyparaphenylene isophthalamide (PPIA), polymetaphenylene terephthalamide (PMTA), polymetaphenylene isophthalamide (PMIA), poly (2,6- Naphthalene dimethylene adipamide) (polyamide 2,6-BAN6), poly (2,6-naphthalene dimethylene terephthalamide) (polyamide 2,6-BANT), poly (2,6-naphthalene dimethylene isophthalamide) ) (Polyamide 2,6-BANI), poly (2,6-naphthalenediethylenehexahydroterephthalamide) (polyamide 2,6-BANT (H)), poly (2,6-naphthalenediethylene naphthalamide) ( Polyamide 2,6-BANN), poly (1,3-cyclohexanedimethylene) Adipamide) (polyamide 1,3-BAC6), poly (1,3-cyclohexanedimethylenesveramide (polyamide 1,3-BAC8), poly (1,3-cyclohexanedimethylene azelamide) (polyamide 1,3-BAC9) ), Poly (1,3-cyclohexanedimethylene sebacamide) (polyamide 1,3-BAC10), poly (1,3-cyclohexanedimethylene dodecamide) (polyamide 1,3-BAC12), poly (1,3 -Cyclohexanedimethylene terephthalamide) (polyamide 1,3-BACT), poly (1,3-cyclohexanedimethylene isophthalamide) (polyamide 1,3-BACI), poly (1,3-cyclohexanedimethylene hexahydro Terephthalamide) (polyamide 1,3-BACT (H)), poly (1,3-silane) Chlohexanedimethylenenaphthalamide) (polyamide 1,3-BACN), poly (1,4-cyclohexanedimethylene adipamide) (polyamide 1,4-BAC6), poly (1,4-cyclohexanedimethylene suberamide) (Polyamide 1,4-BAC8), poly (1,4-cyclohexanedimethylene azelamide) (polyamide 1,4-BAC9), poly (1,4-cyclohexanedimethylene sebacamide) (polyamide 1,4-BAC10) ), Poly (1,4-cyclohexanedimethylene dodecamide) (polyamide 1,4-BAC12), poly (1,4-cyclohexanedimethylene terephthalamide) (polyamide 1,4-BACT), poly (1,4 -Cyclohexanedimethyleneisophthalamide) (polyamide 1,4-BACI), poly (1,4 Cyclohexane dimethylene hexahydroterephthalamide) (polyamide 1,4-BACT (H)), poly (1,4-cyclohexane dimethylene naphthalamide) (polyamide 1,4-BACN), poly (4,4′-methylene) Biscyclohexylene adipamide) (polyamide PACM6), poly (4,4′-methylenebiscyclohexylene suberamide) (polyamide PACM8), poly (4,4′-methylenebiscyclohexylene azelamide) (polyamide PACM9), Poly (4,4'-methylenebiscyclohexylene sebacamide) (polyamide PACM10), poly (4,4'-methylenebiscyclohexylene dodecamide) (polyamide PACM12), poly (4,4'-methylenebiscyclohexylene) Tetradecamide) (Polyamide PA) M14), poly (4,4′-methylenebiscyclohexylenehexadecamide) (polyamide PACM16), poly (4,4′-methylenebiscyclohexyleneoctadecamide) (polyamide PACM18), poly (4,4′- Methylenebiscyclohexylene terephthalamide) (polyamide PACMT), poly (4,4′-methylenebiscyclohexylene isophthalamide) (polyamide PACMI), poly (4,4′-methylenebiscyclohexylene hexahydroterephthalamide) (Polyamide PACMT (H)), poly (4,4′-methylenebiscyclohexylenenaphthalamide) (polyamide PACMN), poly (4,4′-methylenebis (2-methyl-cyclohexylene) adipamide) (polyamide MACM6), Poly (4,4'-methyle Bis (2-methyl-cyclohexylene) suberamide) (polyamide MACM8), poly (4,4'-methylenebis (2-methyl-cyclohexylene) azeramide) (polyamide MACM9), poly (4,4'-methylenebis (2- Methyl-cyclohexylene) sebacamide) (polyamide MACM10), poly (4,4′-methylenebis (2-methyl-cyclohexylene) dodecamide) (polyamide MACM12), poly (4,4′-methylenebis (2-methyl-cyclohexylene) ) Tetradecamide) (polyamide MACM14), poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexadecamide) (polyamide MACM16), poly (4,4′-methylenebis (2-methyl-cyclohexylene) octadecamide) ( Polya MACM18), poly (4,4′-methylenebis (2-methyl-cyclohexylene) terephthalamide) (polyamide MACMT), poly (4,4′-methylenebis (2-methyl-cyclohexylene) isophthalamide) (polyamide MACMI), Poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexahydroterephthalamide) (polyamide MACMT (H)), poly (4,4′-methylenebis (2-methyl-cyclohexylene) naphthalamide) (polyamide) MACMN), poly (4,4′-propylene biscyclohexylene adipamide) (polyamide PACP6), poly (4,4′-propylene biscyclohexylene suberamide) (polyamide PACP8), poly (4,4′-propylene) Biscyclohexylene azelami ) (Polyamide PACP9), poly (4,4′-propylene biscyclohexylene sebacamide) (polyamide PACP10), poly (4,4′-propylene biscyclohexylene dodecamide) (polyamide PACP12), poly (4,4 '-Propylene biscyclohexylene tetradecanamide) (polyamide PACP14), poly (4,4'-propylene biscyclohexylene hexadecanamide) (polyamide PACP16), poly (4,4'-propylene biscyclohexylene octadecanamide) (Polyamide PACP18), poly (4,4′-propylene biscyclohexylene terephthalamide) (polyamide PAPPT), poly (4,4′-propylene biscyclohexylene isophthalamide) (polyamide PACPI), poly (4,4 '-Pro Pyrenebiscyclohexylenehexahydroterephthalamide) (polyamide PACPT (H)), poly (4,4′-propylenebiscyclohexylenenaphthalamide) (polyamide PACPN), polyisophorone adipamide (polyamide IPD6), polyisophorones Ramide (polyamide IPD8), polyisophorone azeamide (polyamide IPD9), polyisophorone sebamide (polyamide IPD10), polyisoholondecamide (polyamide IPD12), polyisophorone terephthalamide (polyamide IPDT), polyisophorone isophthalamide ( Polyamide IPDI), polyisophorone hexahydroterephthalamide (polyamide IPDT (H)), polyisophorone naphthalamide (polyamide IPDN), polytetramethylene terephthalate Mido (polyamide 4T), polytetramethylene isophthalamide (polyamide 4I), polytetramethylene hexahydroterephthalamide (polyamide 4T (H)), polytetramethylene naphthalamide (polyamide 4N), polypentamethylene terephthalamide ( Polyamide 5T), polypentamethylene isophthalamide (polyamide 5I), polypentamethylene hexahydroterephthalamide (polyamide 5T (H)), polypentamethylene naphthalamide (polyamide 5N), polyhexamethylene terephthalamide (polyamide 6T) ), Polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene hexahydroterephthalamide (polyamide 6T (H)), polyhexamethylene naphthalamide (polyamide 6N), poly (2-methyl pen) Methylene 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 hexahydroterephthalamide (polyamide 9T (H)), Polynonamethylene naphthalamide (polyamide 9N), poly (2-methyloctamethylene terephthalamide) (polyamide M8T), poly (2-methyloctamethylene isophthalamide) (polyamide M8I), poly (2-methyloctamethylenehexa) Hydroteref Taramide) (polyamide M8T (H)), poly (2-methyloctamethylene naphthalamide) (polyamide M8N), polytrimethylhexamethylene terephthalamide (polyamide TMHT), polytrimethylhexamethylene isophthalamide (polyamide TMHI), poly Trimethylhexamethylene hexahydroterephthalamide (polyamide TMHT (H)), polytrimethylhexamethylene naphthalamide (polyamide TMHN), polydecamethylene terephthalamide (polyamide 10T), polydecamethylene isophthalamide (polyamide 10I), poly Decamethylene hexahydroterephthalamide (polyamide 10T (H)), polydecamethylene naphthalamide (polyamide 10N), polyundecamethylene terephthalamide (polyamide 11T), poly Undecamethylene isophthalamide (polyamide 11I), polyundecamethylene hexahydroterephthalamide (polyamide 11T (H)), polyundecamethylene naphthalamide (polyamide 11N), polydodecamethylene terephthalamide (polyamide 12T), Polydodecamethylene isophthalamide (Polyamide 12I), Polydodecamethylene hexahydroterephthalamide (Polyamide 12T (H)), Polydodecamethylene naphthalamide (Polyamide 12N), raw material monomers of these polyamides and / or the aliphatic Examples thereof include polyamide resins such as copolymers using several kinds of polyamide (A) raw material monomers.

  Fluorine-containing polymer other than those specified in the present invention (Here, other than those specified in the present invention refers to a fluorine-containing polymer that does not contain a functional group having reactivity with an amino group.) 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 / Hexafull Polypropylene copolymer (EFEP), vinylidene fluoride / tetrafluoroethylene copolymer, vinylidene fluoride / hexafluoropropylene copolymer, vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer, tetrafluoroethylene / hexa Fluoropropylene / vinylidene fluoride copolymer (THV), vinylidene fluoride / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer, tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) Polymer, ethylene / chlorotrifluoroethylene copolymer (ECTFE), chlorotrifluoroethylene / tetrafluoroethylene copolymer, vinylidene fluoride / chlorotrifluoroethylene copolymer , Chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) copolymer, chlorotrifluoroethylene / hexafluoropropylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene / hexafluoropropylene copolymer, chlorotrifluoroethylene / tetra Fluoroethylene / 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 / hexafluoropropylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene / fluoride And fluorine-containing polymers such as vinylidene fluoride / perfluoro (alkyl vinyl ether) / hexafluoropropylene copolymer. A layer made of a fluorine-containing polymer not containing a functional group is disposed on the inside of the layer (c) made of the fluorine-containing polymer (C) containing a functional group having reactivity with the amino group. By doing so, it is possible to achieve both low temperature impact resistance, chemical solution permeation prevention properties, and environmental stress crack resistance, and it is economically advantageous.

  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), Polyetheretheretherketone (PEEEK), Polyetheretherketoneketone (PEEKK), Polyetherketoneketoneketone (PEKKK), Polyether Polyketone resins such as ketone ether ketone ketone (PEKEKK), polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer Polynitrile resins such as coalescence (ABS), acrylonitrile / butadiene copolymer (NBR), polymethacrylate such as polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA) Resin, polyvinyl ester resin such as polyvinyl acetate (PVAc), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer Polyvinyl chloride resin such as cellulose acetate, cellulose resin such as cellulose butyrate, polycarbonate resin such as polycarbonate (PC), thermoplastic polyimide (TPI), polyetherimide, polyesterimide, polyamideimide (PAI), polyester Examples thereof include polyimide resins such as amideimide, thermoplastic polyurethane resins, polyamide elastomers, polyurethane elastomers, and polyester elastomers.

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

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

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

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

  The outer diameter of the laminated tube takes into consideration the flow rate of the chemical solution (for example, fuel such as alcohol-containing gasoline), and the thickness is such that the permeation amount of the chemical solution does not increase, and the normal tube breaking pressure can be maintained. And although it is designed by the thickness which can maintain the softness | flexibility of the grade with the favorable assembly | attachment work of a tube and the vibration resistance at the time of use, it is not limited. 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 laminated tube of the present invention includes machine parts such as automobile parts, internal combustion engines, electric tool housings, industrial materials, industrial materials, electrical / electronic parts, medical care, food, household / office supplies, building materials related parts, furniture. It can be used for various applications such as industrial parts.

  Moreover, since the laminated tube of this invention is excellent in chemical-solution permeation prevention property, it is suitable as a chemical-solution transport 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 laminated tube of the present invention is suitable as a tube for conveying the above chemical solution, specifically, a feed tube, a return tube, an evaporation tube, a fuel filler tube, an ORVR tube, a reserve tube, a fuel tube such as a vent tube, an oil Tube, oil drilling tube, underground buried tube for gas station, brake tube, window washer fluid tube, engine coolant (LLC) tube, reservoir tank tube, urea solution transfer tube, cooler tube for cooling water, refrigerant, etc., air conditioner refrigerant Tube, heater tube, load heating tube, floor heating tube, infrastructure supply tube, fire extinguisher and fire extinguishing equipment tube, medical cooling equipment tube, ink, paint spray tube, other medicine 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.

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

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

[Melt flow rate (MFR) of fluorine-containing polymer]
Using a melt flow rate measuring device (manufactured by Toyo Seiki Seisakusho Co., Ltd., model: melt indexer) at a temperature 50 ° C. higher than the melting point of the fluorine-containing polymer (C), the inner diameter is 2 mm and the length is 10 mm under a load of 49N. The mass (g) of the polymer flowing out per unit time (10 minutes) from the nozzle was measured.

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

[Environmental stress crack resistance]
As shown in FIG. 1, both ends of the tube 11 (length: 250 mm) are fixed to the joint 22 of the vibration tester, and isooctane / toluene / methanol = 42.5 / into the tube 11 at an atmospheric temperature of 80 ° C. A methanol-containing gasoline (CM15) mixed at 42.5 / 15% by volume was circulated, and a vibration endurance test was conducted for 500 hours under the conditions that the one end 11a of the tube had an amplitude of ± 10 mm in the arrow direction and a frequency of 1000 cpm. Thereafter, the tube was removed, and the presence or absence of cracks or cracks on the innermost layer surface of the tube was confirmed. When no cracks or cracks occurred, it was judged that the environmental stress crack resistance was excellent. Moreover, the interlayer adhesiveness of the taken out tube was evaluated according to the method described above.

[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 12 (a-2) In a pressure-resistant reaction vessel with an internal volume of 70 liters and a stirrer, 20.0 kg of dodecane lactam, 0.5 kg of water and polyethyleneimine (Epomin SP-12, manufactured by Nippon Shokubai Co., Ltd.) After charging 0 g and substituting the inside of the polymerization tank with nitrogen, it was heated to 180 ° C. and stirred at this temperature so that the reaction system was in a uniform state. Subsequently, the temperature in the polymerization tank was raised to 270 ° C., and polymerization was performed with stirring for 2 hours while adjusting the pressure in the tank to 3.5 MPa. Thereafter, the pressure was released to normal pressure over about 2 hours, and then the pressure was reduced to 53 kPa, and polymerization was performed for 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 12 having a relative viscosity of 2.15, a terminal amino group concentration of 122 μeq / g, and a terminal carboxyl group concentration of 17 μeq / g (hereinafter, this polyamide 12 is referred to as (a-2)).

Manufacture of polyamide 12 resin composition (A-2) In manufacture of polyamide 12 resin composition (A-1), polyamide 12 (a-1) was changed to (a-2), and triethylene glycol was used as an antioxidant. -Bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan, IRGANOX 245), and tris (2,4-di-t-butyl as a phosphorus processing stabilizer Phenyl) phosphite (manufactured by BASF Japan, IRGAFOS168) was used in the same manner as in the production of the polyamide 12 resin composition (A-1) except that the polyamide 12 was 85% by mass and the impact resistance improving material 10 mass. %, And a total of 100 parts by mass of the plasticizer 5% by mass, an antioxidant 0.8 parts by mass and a phosphorus processing stabilizer 0.2 parts by mass. To obtain pellets of polyamide 12 resin composition (hereinafter, this polyamide 12 resin composition of (A-2).).

Manufacture of polyamide 610 (a-3) 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 an equimolar salt of 1,6-hexanediamine and sebacic acid, 1,6-hexanediamine After charging 63.8 g and replacing the inside of the polymerization tank with nitrogen, it was heated to 220 ° C. and stirred at this temperature so that the reaction system was in a uniform state. Next, the temperature in the polymerization tank was raised to 270 ° C., and polymerization was performed with stirring for 2 hours while adjusting the pressure in the tank to 1.7 MPa. Thereafter, the pressure was released to normal pressure over about 2 hours, and then the pressure was reduced to 53 kPa, and polymerization was performed for 4 hours under reduced pressure. Next, nitrogen was introduced into the autoclave, and after returning to normal pressure, the strand was extracted from the lower nozzle of the reaction vessel and cut to obtain pellets. This pellet was dried under reduced pressure to obtain a polyamide 610 having a relative viscosity of 2.48, a terminal amino group concentration of 73 μeq / g, and a terminal carboxyl group concentration of 14 μeq / g (hereinafter, this polyamide 610 is referred to as (a-3)).

Manufacture of polyamide 610 resin composition (A-3) Polyamide 610 (a-3), 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-3).)

Production of polyamide 612 (a-4) In the production of polyamide 610 (a-3), 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. The same as the production of polyamide 610 (a-3), except that 20.0 kg of 50% by weight aqueous solution of equimolar salt of diacid and the amount of 1,6-hexanediamine added were 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-4)).

Manufacture of polyamide 612 resin composition (A-4) Polyamide 610 resin except that polyamide 610 (a-3) was changed to polyamide 612 (a-4) in the manufacture of polyamide 610 resin composition (A-3). In the same manner as in the production of the composition (A-3), 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 polyamide 612 resin composition comprising parts by mass and 0.2 parts by mass of phosphorus processing stabilizer were obtained (hereinafter, this polyamide 612 resin composition is referred to as (A-4)).

Semi-aromatic polyamide (B)
Manufacture of semi-aromatic polyamide (b-1) Equipped with a stirrer, thermometer, torque meter, pressure gauge, raw material inlet directly connected with diaphragm pump, nitrogen gas inlet, pressure outlet, pressure regulator, and polymer outlet A pressure vessel with an internal volume of 40 liters was charged with 6.068 kg (30.0 mol) of sebacic acid, 8.50 g (0.049 mol) of calcium hypophosphite, and 2.19 g (0.025 mol) of sodium acetate. After the pressure inside the pressure vessel was pressurized to 0.3 MPa with 99.9999% nitrogen gas, the operation of releasing the nitrogen gas to normal pressure was repeated 5 times to perform nitrogen substitution, and then the pressure was reduced. The system was heated while stirring. Furthermore, after heating up to 190 degreeC under a small nitrogen stream, 4.086 kg (30.0 mol) of p-xylylenediamine was dripped over 160 minutes under stirring. During this time, the internal pressure of the reaction system was controlled to 0.5 MPa, and the internal temperature was continuously raised to 295 ° C. Further, water distilled with dropping of p-xylylenediamine was removed out of the system through a condenser and a cooler. After completion of the dropwise addition of p-xylylenediamine, the pressure was reduced to normal pressure over 60 minutes, and during this time, the temperature in the container was maintained at 300 ° C. and the reaction was continued for 10 minutes. 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 to have a melting point of 281, 291 ° C. (having two melting points) and a relative viscosity of 2.47. An aromatic polyamide (polyamide PXD10 = 100 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (b-1)).

Manufacture of a semi-aromatic polyamide resin composition (B-1) A maleic anhydride-modified ethylene / propylene copolymer (manufactured by JSR Corporation, JSR T7761P) was used as an impact resistance improver for the semi-aromatic polyamide (b-1). , 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 (IRGAFOS168, manufactured by BASF Japan Ltd.) is mixed in advance and supplied to a twin-screw melt kneader (manufactured by Nippon Steel, Co., Ltd., model: TEX44). After melt-kneading at a temperature of 320 ° C. to 320 ° C. and extruding the molten resin into a strand shape, this is introduced into a water bath, cooled, And 100% by mass of 100% by mass of semi-aromatic polyamide and 10% by mass of impact resistance improving agent, 0.8 parts by mass of antioxidant and 0.2% by mass of phosphorus processing stabilizer. The pellet of the semi-aromatic polyamide resin composition which consists of a part was obtained (henceforth this semi-aromatic polyamide resin composition is called (B-1)).

Production of semi-aromatic polyamide (b-2) In the production of semi-aromatic polyamide (b-1), 6.068 kg (30.0 mol) of sebacic acid was changed to 5.647 kg (30.0 mol) of azelaic acid. Except that a semi-aromatic polyamide (polyamide PXD9 = 100 mol%) having a melting point of 270 ° C. and a relative viscosity of 2.45 was obtained in the same manner as in the production of the semi-aromatic polyamide (b-1) (hereinafter referred to as “this”). (Semi-aromatic polyamide is referred to as (b-2).)

Production of semi-aromatic polyamide resin composition (B-2) In production of semi-aromatic polyamide resin composition (B-1), semi-aromatic polyamide (b-1) was changed to (b-2), and the cylinder temperature was changed. Except that the temperature was changed from 320 ° C. to 310 ° C., in the same manner as in the production of the semi-aromatic polyamide resin composition (B-1), the total of 90% by mass of the semi-aromatic polyamide and 10% by mass of the impact resistance improving material A pellet of a semi-aromatic polyamide resin composition comprising 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus processing stabilizer was obtained with respect to 100 parts by mass (hereinafter, this semi-aromatic polyamide resin composition). A thing is called (B-2).).

Production of semi-aromatic polyamide (b-3) In the production of semi-aromatic polyamide (b-1), 4.086 kg (30.0 mol) of p-xylylenediamine was converted to 4.086 kg (30. Except that the polymerization temperature was changed from 300 ° C. to 250 ° C., in the same manner as in the production of the semi-aromatic polyamide (b-1), a semi-fragrance having a melting point of 191 ° C. and a relative viscosity of 2.46 Group polyamide (polyamide MXD10 = 100 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (b-3)).

Production of semi-aromatic polyamide resin composition (B-3) In production of semi-aromatic polyamide resin composition (B-1), semi-aromatic polyamide (b-1) was changed to (b-3), and the cylinder temperature was changed. The total of 90% by mass of the semi-aromatic polyamide and 10% by mass of the impact resistance improving material was the same as the production of the semi-aromatic polyamide resin composition (B-1) except that the temperature was changed from 320 ° C. to 240 ° C. A pellet of a semi-aromatic polyamide resin composition comprising 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus processing stabilizer was obtained with respect to 100 parts by mass (hereinafter, this semi-aromatic polyamide resin composition). A thing is called (B-3).).

Production of semi-aromatic polyamide (b-4) In the production of semi-aromatic polyamide (b-3), 6.068 kg (30.0 mol) of sebacic acid was changed to 6.488 kg (30.0 mol) of dodecanedioic acid. A semi-aromatic polyamide having a melting point of 175 ° C. and a relative viscosity of 2.40 (polyamide MXD12) was the same as the production of the semi-aromatic polyamide (b-3) except that the polymerization temperature was changed from 250 ° C. to 240 ° C. = 100 mol%) (hereinafter, this semi-aromatic polyamide is referred to as (b-4)).

Production of semi-aromatic polyamide resin composition (B-4) In production of semi-aromatic polyamide resin composition (B-1), semi-aromatic polyamide (b-1) was changed to (b-4), and the cylinder temperature was changed. Except that the temperature was changed from 320 ° C. to 230 ° C., in the same manner as in the production of the semi-aromatic polyamide resin composition (B-1), the total of 90% by mass of the semi-aromatic polyamide and 10% by mass of the impact modifier A pellet of a semi-aromatic polyamide resin composition comprising 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus processing stabilizer was obtained with respect to 100 parts by mass (hereinafter, this semi-aromatic polyamide resin composition). A thing is called (B-4).).

Production of semi-aromatic polyamide (b-5) In the production of semi-aromatic polyamide (b-1), 4.086 kg (30.0 mol) of p-xylylenediamine and m-xylylenediamine and p-xylylenediamine are used. 7: 3 mixed diamine was changed to 4.086 kg (30.0 mol) and the polymerization temperature was changed from 300 ° C. to 260 ° C. in the same manner as in the production of the semi-aromatic polyamide (b-1). 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 (hereinafter, this semi-aromatic polyamide is referred to as (b-5)).

Production of semi-aromatic polyamide resin composition (B-5) In production of semi-aromatic polyamide resin composition (B-1), semi-aromatic polyamide (b-1) was changed to (b-5), and the cylinder temperature was changed. In the same manner as in the production of the semi-aromatic polyamide resin composition (B-1), except that the temperature was changed from 320 ° C. to 250 ° C., the total of 90% by mass of the semi-aromatic polyamide and 10% by mass of the impact resistance improving material A pellet of a semi-aromatic polyamide resin composition comprising 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus processing stabilizer was obtained with respect to 100 parts by mass (hereinafter, this semi-aromatic polyamide resin composition). A thing is called (B-5).).

Production of semi-aromatic polyamide (b-6) In production of semi-aromatic polyamide (b-4), 4.086 kg (30.0 mol) of m-xylylenediamine was converted to 2,6-bis (aminomethyl) naphthalene 5 The melting point was 272 ° C. and the relative viscosity was 2 except that the polymerization temperature was changed from 240 ° C. to 300 ° C. in the same manner as in the production of the semiaromatic polyamide (b-4). .33 semi-aromatic polyamide (polyamide 2,6-BAN12 = 100 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (b-6)).

Production of semi-aromatic polyamide resin composition (B-6) In production of semi-aromatic polyamide resin composition (B-1), semi-aromatic polyamide (b-1) was changed to (b-6), and the cylinder temperature was changed. Except that the temperature was changed from 320 ° C. to 310 ° C., in the same manner as in the production of the semi-aromatic polyamide resin composition (B-1), the total of 90% by mass of the semi-aromatic polyamide and 10% by mass of the impact resistance improving material A pellet of a semi-aromatic polyamide resin composition comprising 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus processing stabilizer was obtained with respect to 100 parts by mass (hereinafter, this semi-aromatic polyamide resin composition). A thing is called (B-6).).

Production of semi-aromatic polyamide (b-7) In the production of semi-aromatic polyamide (b-1), 4.086 kg (30.0 mol) of p-xylylenediamine was converted to 4.086 kg (30. Semi-aromatic polyamide (except that the polymerization temperature was changed from 300 ° C. to 275 ° C.) and 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 (polyamide MXD6 = 100 mol%) having a melting point of 243 ° C. and a relative viscosity of 2.45 was obtained in the same manner as in the production of b-7) (hereinafter, this semi-aromatic polyamide was converted to (b- 7).)

Production of semi-aromatic polyamide resin composition (B-7) In production of semi-aromatic polyamide resin composition (B-1), semi-aromatic polyamide (b-1) was changed to (b-7), and the cylinder temperature was changed. In the same manner as in the production of the semi-aromatic polyamide resin composition (B-1) except that the temperature was changed from 320 ° C. to 280 ° C., the total of 90% by mass of the semi-aromatic polyamide and 10% by mass of the impact modifier A pellet of a semi-aromatic polyamide resin composition comprising 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus processing stabilizer was obtained with respect to 100 parts by mass (hereinafter, this semi-aromatic polyamide resin composition). A thing is called (B-7).).

Production of semi-aromatic polyamide (b-8) 3.240 kg (19.5 mol) of terephthalic acid, 1.246 kg (7.5 mol) of isophthalic acid, 0.438 kg (3.0 mol) of adipic acid, 1,6 -Hexanediamine 3.718 kg (32.0 mol), acetic acid 50.4 g (0.84 mol), sodium hypophosphite monohydrate 7.77 g and distilled water 2.5 liters with an internal volume of 40 liters In a pressure vessel and purged with nitrogen.
The mixture was stirred at 100 ° C. for 30 minutes, and the internal temperature was raised to 220 ° C. over 2 hours. At this time, the autoclave was pressurized to 2.0 MPa. The reaction was continued for 2 hours, and then the temperature was raised to 230 ° C., and then the temperature was maintained at 230 ° C. for 2 hours. The reaction was carried out while gradually removing water vapor and keeping the pressure at 2.0 MPa. Next, the pressure was reduced to 1.0 MPa over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer. This was dried at 100 ° C. under reduced pressure for 12 hours, pulverized to a size of 2 mm or less, solid-phase polymerized at 250 ° C. and 0.013 kPa for 8 hours, a melting point of 315 ° C. and a relative viscosity of 2.38 half. An aromatic polyamide (polyamide 6T / 6I / 66 = 65/25/10 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (b-8)).

Production of semi-aromatic polyamide resin composition (B-8) In production of semi-aromatic polyamide resin composition (B-1), semi-aromatic polyamide (b-1) was changed to (b-8), and the cylinder temperature was changed. In the same manner as the production of the semi-aromatic polyamide resin composition (B-1) except that the temperature was changed from 320 ° C. to 350 ° C., the total of 90% by mass of the semi-aromatic polyamide and 10% by mass of the impact resistance improving material A pellet of a semi-aromatic polyamide resin composition comprising 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus processing stabilizer was obtained with respect to 100 parts by mass (hereinafter, this semi-aromatic polyamide resin composition). A thing is called (B-8).).

Fluorinated polymer (C)
Production of fluorinated polymer (C-1) A polymerization tank with a stirrer having an internal volume of 100 L was degassed, and 92.1 kg of 1-hydrotridecafluorohexane, 1,3-dichloro-1,1,2, , 2,3-pentafluoropropane 16.3 kg, (perfluoroethyl) ethylene _{CH 2 = CH (CF 2)} 2 F73g, charged itaconic anhydride (IAH) 10.1 g, tetrafluoroethylene (TFE) 9.6 kg Then, 0.7 kg of ethylene (E) was injected, the inside of the polymerization tank was heated to 66 ° C., and 1% by mass of t-butyl peroxypivalate as a polymerization initiator 1,3-dichloro-1,1,2,2, A 433 cm ³ of 3-pentafluoropropane solution was charged to initiate the polymerization.
A monomer mixed gas of TFE / E: 60/40 (molar ratio) was continuously charged so that the pressure was constant during the polymerization. In addition, (perfluoroethyl) ethylene corresponding to 2.0 mol% and IAH corresponding to 0.5 mol% were continuously charged with respect to the total number of moles of TFE and E charged during the polymerization. . 5.5 hours after the start of the polymerization, when the monomer mixed gas of 8.0 kg and IAH of 63 g were charged, the temperature inside the polymerization tank was lowered to room temperature and purged to normal pressure.
The obtained slurry-like fluorine-containing polymer was put into a 200 L granulation tank charged with 75.0 kg of water, and then heated to 105 ° C. while stirring and granulated while distilling and removing the solvent. The obtained granulated product was dried at 150 ° C. for 5 hours to obtain 8.3 kg of a fluorine-containing polymer.
The composition of the fluorine-containing polymer is as follows: polymerized units based on TFE / polymerized units based on E / polymerized units based on CH ₂ ═CH (CF ₂ ) ₂ F / polymerized units based on IAH = 58.5 / 39.0 /2.0/0.5 (mol%), and the melting point was 240 ° C. This granulated product was melted at 280 ° C. and a residence time of 2 minutes using an extruder to obtain pellets of a fluorine-containing polymer (hereinafter, this fluorine-containing polymer is referred to as (C-1)). ). The MFR of the fluorine-containing polymer (C-1) was 25 g / 10 min (290 ° C., under a load of 49 N).

Production of conductive fluorine-containing polymer (C-2) 100 parts by mass of fluorine-containing polymer (C-1) and 13 parts by mass of carbon black (manufactured by Electrochemical Co., Ltd.) are mixed in advance and biaxially melted. Supply to a kneading machine (Toshiba Machine Co., Ltd., model: TEM-48S), melt knead at a cylinder temperature of 240 ° C to 300 ° C, extrude the molten resin into a strand, introduce it into a water tank, and discharge The strand was cooled with water, the strand was cut with a pelletizer, and dried for 10 hours with a drier at 120 ° C. to remove moisture to obtain a conductive fluorine-containing polymer pellet (hereinafter referred to as this conductive fluorine-containing polymer). The polymer is referred to as (C-2).) The MFR of the conductive fluorine-containing polymer (C-2) was 6 g / 10 minutes (290 ° C., under a load of 49 N).

Production of fluorinated polymer (C-3) Production of fluorinated polymer (C-1) except that itaconic anhydride (IAH) is not charged in the production of fluorinated polymer (C-1). In the same manner as above, 7.6 kg of a fluorine-containing polymer was obtained.
The composition of the fluorine-containing polymer is as follows: polymerized units based on TFE / polymerized units based on E / polymerized units based on CH ₂ ═CH (CF ₂ ) ₂ F / polymerized units based on IAH = 58.8 / 39.2 /2.0 (mol%), and the melting point was 242 ° C. This granulated material was melted at 280 ° C. and a residence time of 2 minutes using an extruder to obtain pellets of a fluorine-containing polymer (hereinafter, this fluorine-containing polymer is referred to as (C-3). ). The MFR of the fluorine-containing polymer (C-3) was 23 g / 10 min (292 ° C., under a load of 49 N).

Production of conductive fluorine-containing polymer (C-4) In production of conductive fluorine-containing polymer (C-2), fluorine-containing polymer (C-1) was changed to (C-3). Obtained the conductive fluorine-containing polymer pellets in the same manner as in the production of the conductive fluorine-containing polymer (C-2) (hereinafter, this conductive fluorine-containing polymer (C- 4).) The MFR of the conductive fluorine-containing polymer (C-4) was 5 g / 10 minutes (292 ° C., under a load of 49 N).

Production of fluorinated polymer (C-5) A polymerization tank with a stirrer having an internal volume of 100 L was degassed, 42.5 kg of 1,3-dichloro-1,1,2,2,3-pentafluoropropane, _{CF 2 = CFOCF 2 CF 2 CF} 3 ( perfluoro (propyl vinyl ether): PPVE), 1,1,2,4,4,5,5,6,6,6- decafluoro-3-oxa hex-1- Ene) 2.13 kg and hexafluoropropylene (HFP) 51.0 kg were charged. Next, the temperature in the polymerization tank was raised to 50 ° C., 4.25 kg of tetrafluoroethylene (TFE) was charged, and the pressure was increased to 1.0 MPa / G. As a polymerization initiator solution, 340 cm ³ of (perfluorobutyryl) peroxide 0.3 mass% 1,3-dichloro-1,1,2,2,3-pentafluoropropane solution was charged to initiate polymerization, and thereafter 10 minutes Every time, 340 cm ³ of the polymerization initiator solution was charged.
During the polymerization, TFE was continuously charged so that the pressure was maintained at 1.0 MPa / G. Further, the amount of 5-norbornene-2,3-dicarboxylic acid anhydride (NAH) 0.3 mass% 1,3-dichloro-1 in an amount corresponding to 0.1 mol% with respect to the number of moles of TFE charged during the polymerization. 1,2,2,3-pentafluoropropane solution was continuously charged.
After 5 hours from the start of polymerization, when 8.5 kg of TFE was charged, the polymerization tank internal temperature was lowered to room temperature and purged to normal pressure.
The obtained slurry-like fluorine-containing polymer was put into a 200 L granulation tank charged with 75.0 kg of water, and then heated to 105 ° C. while stirring and granulated while distilling and removing the solvent. The obtained granulated product was dried at 150 ° C. for 5 hours to obtain 7.5 kg of a fluoropolymer granulated product.
The composition of the fluorine-containing polymer is as follows: polymerized units based on TFE / polymerized units based on PPVE / polymerized units based on HFP / polymerized units based on NAH = 91.2 / 1.5 / 7.2 / 0.1 ( Mol%) and the melting point was 262 ° C. This granulated product was melted using an extruder at 300 ° C. for a residence time of 2 minutes to obtain a fluorine-containing polymer pellet (hereinafter, this fluorine-containing polymer is referred to as (C-5)). ). The MFR of the fluorine-containing polymer (C-5) was 24 g / 10 min (312 ° C., under a load of 49 N).

Production of conductive fluorine-containing polymer (C-6) In the production of conductive fluorine-containing polymer (C-2), carbon black was prepared by replacing fluorine-containing polymer (C-1) with (C-5). In the same manner as in the production of the conductive fluorine-containing polymer (C-2), except that the addition amount was changed from 13 parts by weight to 11 parts by weight and the cylinder temperature was changed from 300 ° C. to 320 ° C. A conductive fluorine-containing polymer pellet was obtained (hereinafter, this conductive fluorine-containing polymer is referred to as (C-6)). The MFR of the conductive fluorine-containing polymer (C-6) was 4 g / 10 minutes (312 ° C., under a load of 49 N).

Production of fluorinated polymer (C-7) In production of fluorinated polymer (C-5), 5-norbornene-2,3-dicarboxylic anhydride (NAH) 0.3 mass% 1,3- 7.6 kg of fluorinated polymer in the same manner as the production of the fluorinated polymer (C-5) except that no dichloro-1,1,2,2,3-pentafluoropropane solution was charged. Got.
The composition of the fluorine-containing polymer is TFE-based polymer units / PPVE-based polymer units / HFP-based polymer units = 91.5 / 1.5 / 7.0 (mol%), and the melting point is 257 ° C. Met. This granulated material was melted using an extruder at 300 ° C. for a residence time of 2 minutes to obtain a fluorine-containing polymer pellet (hereinafter, this fluorine-containing polymer is referred to as (C-7)). ). The MFR of the fluorine-containing polymer (C-7) was 22 g / 10 min (307 ° C., under a load of 49 N).

Production of conductive fluorine-containing polymer (C-8) In production of conductive fluorine-containing polymer (C-6), fluorine-containing polymer (C-5) was changed to (C-7). Obtained the conductive fluorine-containing polymer pellets in the same manner as in the production of the conductive fluorine-containing polymer (C-6) (hereinafter, this conductive fluorine-containing polymer (C- 8).) The MFR of the conductive fluorine-containing polymer (C-8) was 3 g / 10 minutes (307 ° C., 49 N load).

Production of fluorinated polymer (C-9) 51.5 kg of demineralized pure water was charged in a jacketed stirring polymerization tank capable of holding 174 kg of water, the interior space was sufficiently replaced with pure nitrogen gas, and nitrogen gas was then added. Was eliminated in vacuo. Next, 40.6 kg of octafluorocyclobutane, 1.6 kg of chlorotrifluoroethylene (CTFE), 4.5 kg of tetrafluoroethylene (TFE), and 2.8 kg of perfluoro (propyl vinyl ether) (PPVE) were injected. 0.090 kg of n-propyl alcohol was added as a chain transfer agent, the temperature was adjusted to 35 ° C., and stirring was started. To this, 0.44 kg of 50% by weight methanol solution of di-n-propyl peroxydicarbonate was added as a polymerization initiator to initiate polymerization. During the polymerization, a mixed monomer prepared to have the same composition as the desired copolymer composition is polymerized while being additionally charged so that the pressure in the tank is maintained at 0.66 MPa, and then the residual gas in the tank is exhausted. The produced polymer was taken out, washed with demineralized pure water, and dried to obtain 30.5 kg of a granular powder fluorine-containing polymer.
The composition of the fluoropolymer is 24.4 / 73.1 / 2.5 in terms of the molar ratio of polymerized units based on CTFE / polymerized units based on TFE / polymerized units based on PPVE. The number of carbonate end groups derived from the initiator was 170. The melting point was 241 ° C.
This granulated product was melted at 290 ° C. and a residence time of 2 minutes using an extruder to obtain pellets of a fluorine-containing polymer (hereinafter, this fluorine-containing polymer is referred to as (C-9)). ). The MFR of the fluorine-containing polymer (C-9) was 25 g / 10 min (291 ° C., under a load of 49 N).

Production of conductive fluorine-containing polymer (C-10) In production of conductive fluorine-containing polymer (C-6), the fluorine-containing polymer (C-5) is changed to (C-9), and a cylinder is produced. Except for changing the temperature from 320 ° C. to 310 ° C., conductive fluorine-containing polymer pellets were obtained in the same manner as in the production of the conductive fluorine-containing polymer (C-6) (hereinafter referred to as “this”). A conductive fluorine-containing polymer is referred to as (C-10)). The MFR of the conductive fluorine-containing polymer (C-10) was 6 g / 10 min (291 ° C., 49 N load).

Production of fluorinated polymer (C-11) In production of fluorinated polymer (C-9), fluorinated heavy polymer was used except that 50% by weight di-n-propyl peroxydicarbonate methanol solution was not charged. 29.8 kg of a fluorinated polymer was obtained in the same manner as in the production of the coalescence (C-9).
The composition of the fluorine-containing polymer is 24.4 / 73.1 / 2.5 in terms of the molar ratio of polymerized units based on CTFE / polymerized units based on TFE / polymerized units based on PPVE, and the melting point is 241 ° C. there were.
This granulated product was melted at 290 ° C. and a residence time of 2 minutes using an extruder to obtain pellets of a fluorine-containing polymer (hereinafter, this fluorine-containing polymer is referred to as (C-11). ). The MFR of the fluorine-containing polymer (C-11) was 23 g / 10 min (291 ° C., under a load of 49 N).

Production of conductive fluorine-containing polymer (C-12) In production of conductive fluorine-containing polymer (C-6), the fluorine-containing polymer (C-5) was changed to (C-11), and a cylinder was produced. Except for changing the temperature from 320 ° C. to 310 ° C., conductive fluorine-containing polymer pellets were obtained in the same manner as in the production of the conductive fluorine-containing polymer (C-6) (hereinafter referred to as “this”). A conductive fluorine-containing polymer is referred to as (C-12)). The MFR of the conductive fluorine-containing polymer (C-12) was 5 g / 10 min (291 ° C., 49 N load).

Production of fluorinated polymer (C-13) Preparation of chain transfer agent 1,3-dichloro-1,1,2,2,3-pentafluoropropane in production of fluorinated polymer (C-1) Except for changing the amount, 7.9 kg of a fluorine-containing polymer was obtained in the same manner as in the production of the fluorine-containing polymer (C-1).
The composition of the fluorine-containing polymer is as follows: polymerized units based on TFE / polymerized units based on E / polymerized units based on CH ₂ ═CH (CF ₂ ) ₂ F / polymerized units based on IAH = 58.8 / 39.2 /2.0 (mol%), and the melting point was 242 ° C. This granulated material was melted at 280 ° C. and a residence time of 2 minutes using an extruder to obtain pellets of a fluorine-containing polymer (hereinafter, this fluorine-containing polymer is referred to as (C-13)). ). The MFR of the fluorine-containing polymer (C-13) was 150 g / 10 min (292 ° C., under a load of 49 N).

Production of conductive fluorine-containing polymer (C-14) In production of conductive fluorine-containing polymer (C-2), except that fluorine-containing polymer (C-1) was changed to (C-13) Obtained the conductive fluorine-containing polymer pellets in the same manner as in the production of the conductive fluorine-containing polymer (C-2) (hereinafter, this conductive fluorine-containing polymer (C- 14).) The MFR of the conductive fluorine-containing polymer (C-14) was 38 g / 10 min (292 ° C., under a load of 49 N).

Polyphenylene sulfide (PPS) (D)
Manufacture of polyphenylene sulfide resin composition (D-1) Polyphenylene sulfide (d-1) (Toray Rina A670X01 manufactured by Toray Industries, Inc.), ethylene / glycidyl methacrylate / vinyl acetate copolymer (Sumitomo Chemical Co., Ltd.) as an impact resistance improver Manufactured by Co., Ltd., Bond First 2B), 3,9-bis [2- (3- (3-t-butyl-4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethyl as an antioxidant Ethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane (manufactured by Sumitomo Chemical Co., Ltd., Sumilizer GA-80), and bis (2,6-di-t as a phosphorus processing stabilizer -Butyl-4-methylphenyl) pentaerythritol di-phosphite (manufactured by ADEKA, Adeka Stub PEP-36) Mix and feed to a twin-screw melt kneader (Nippon Steel Works, Model: TEX44), melt knead at a cylinder temperature of 240 ° C. to 310 ° C., and extrude the molten resin into a strand shape. , Cooled, cut, and vacuum-dried, and 0.7 parts by weight of antioxidant and 0 parts of phosphorus processing stabilizer for 100 parts by weight in total of 80% by weight of polyphenylene sulfide and 20% by weight of impact modifier. A pellet of a polyphenylene sulfide resin composition comprising 5 parts by mass was obtained (hereinafter, this polyphenylene sulfide resin composition is referred to as (D-1)).

Production of conductive polyphenylene sulfide resin composition (D-2) In production of polyphenylene sulfide resin composition (D-1), ethylene / glycidyl methacrylate / vinyl acetate copolymer (Sumitomo Chemical Co., Ltd., Bond First 2B) ) Is changed to maleic anhydride modified ethylene / 1-butene copolymer (Mitsui Chemicals, Tuffmer MH5010) and ethylene / 1-butene copolymer (Mitsui Chemicals, Tuffmer A-0550), Similar to the production of the polyphenylene sulfide resin composition (D-1) except that carbon black (manufactured by Lion Corporation, Ketjen Black EC600JD) was added as the conductive filler, and the cylinder temperature was changed from 310 ° C to 330 ° C. In this method, polyphenylene sulfide 68% by mass, impact resistance improving material 25% by mass, Conductive polyphenylene sulfide resin composition pellets comprising 0.7 parts by weight of an antioxidant and 0.5 parts by weight of a phosphorus processing stabilizer with respect to a total of 100 parts by weight of 7% by weight of a conductive filler were obtained (hereinafter referred to as “below”). The conductive polyphenylene sulfide resin composition is referred to as (D-2)).

Production of Adhesive Resin Composition (D-3) Polyamide 12 (a-1) (manufactured by Ube Industries, UBESTA3030UX1, relative viscosity 2.21) and polyphenylene sulfide (d-1) (manufactured by Toray Industries, Inc.) Torelina A670X01), ethylene / glycidyl methacrylate / vinyl acetate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Bond First 2B), 3,9-bis [2- (3- (3-t-butyl-) as an antioxidant 4-hydroxy-5-methylphenyl) propionyloxy) -1,1-dimethylethyl] -2,4,8,10-tetraoxaspiro [5,5] undecane (manufactured by Sumitomo Chemical Co., Ltd., Smither GA-80) ), And bis (2,6-di-t-butyl-4-methylphenyl) pentaerythritol-di-phosphite (( ) ADEKA, ADK STAB PEP-36) is mixed in advance and supplied to a twin-screw melt kneader (manufactured by Nippon Steel Co., Ltd., model: TEX44), melt-kneaded at a cylinder temperature of 180 to 310 ° C. After extruding into a strand, this is introduced into a water bath, cooled, cut, and vacuum dried, and 100 parts by mass in total of polyamide 12 / polyphenylene sulfide / modified polyolefin = 50/30/20 (mass%), The pellet of the adhesive resin composition which consists of 0.7 mass part of antioxidant, and 0.5 mass part of phosphorus processing stabilizers was obtained (henceforth this adhesive resin composition is called (D-3)).

Example 1
Using the polyamide 12 resin composition (A-1), the semi-aromatic polyamide resin composition (B-1) and the fluorine-containing polymer (C-1) shown above, Plabor (Plastic Engineering Laboratory 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 320 ° C, and (C-1) at an extrusion temperature of 280 ° C, 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), (B- When the layer consisting of 1) is the (b) layer (intermediate layer) and the layer consisting of (C-1) is the (c) layer (innermost layer), the layer structure is (a) / (b) / (c) = 0.70 / 0.15 / 0.15 mm, an inner diameter of 6 mm, and an outer diameter of 8 mm were obtained. The physical property measurement results of the laminated tube are shown in Table 1.

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

Example 3
In Example 1, the same method as in Example 1 except that the semi-aromatic polyamide resin composition (B-1) was changed to (B-3) and the extrusion temperature of (B-3) was changed to 240 ° C. Thus, a laminated tube having a layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 4
In Example 1, the same method as in Example 1 except that the semiaromatic polyamide resin composition (B-1) was changed to (B-4) and the extrusion temperature of (B-4) was changed to 230 ° C. Thus, a laminated tube having a layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 5
In Example 1, the same method as in Example 1 except that the semiaromatic polyamide resin composition (B-1) was changed to (B-5) and the extrusion temperature of (B-5) was changed to 250 ° C. Thus, a laminated tube having a layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 6
In Example 1, the same method as in Example 1 except that the semiaromatic polyamide resin composition (B-1) was changed to (B-6) and the extrusion temperature of (B-6) was changed to 310 ° C. Thus, a laminated tube having a layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 7
In Example 1, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 1 except having changed the polyamide 12 resin composition (A-1) into (A-2). The physical property measurement results of the laminated tube are shown in Table 1.

Example 8
Example 1 is the same as Example 1 except that the polyamide 12 resin composition (A-1) is changed to the polyamide 610 resin composition (A-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.

Example 9
Example 1 is the same as Example 1 except that the polyamide 12 resin composition (A-1) is changed to the polyamide 612 resin composition (A-4) and the extrusion temperature of (A-4) 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.

Example 10
In Example 1, except that the fluorine-containing polymer (C-1) was changed to the conductive fluorine-containing polymer (C-2) and the extrusion temperature of (C-2) was changed to 300 ° C. 1 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1. 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 fluorine-containing polymer (C-1) was changed to (C-5) and the extrusion temperature of (C-5) was changed to 300 ° C., the same method as in Example 1 was used. 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. The physical property measurement results of the laminated tube are shown in Table 1.

Example 12
In Example 1, except that the fluorine-containing polymer (C-1) was changed to the conductive fluorine-containing polymer (C-6) and the extrusion temperature of (C-6) was changed to 320 ° C. 1 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1. 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, except that the fluorine-containing polymer (C-1) was changed to (C-9) and the extrusion temperature of (C-9) was changed to 290 ° C., the same method as in Example 1 was used. 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. The physical property measurement results of the laminated tube are shown in Table 1.

Example 14
In Example 1, except that the fluorine-containing polymer (C-1) was changed to the conductive fluorine-containing polymer (C-10) and the extrusion temperature of (C-10) was changed to 310 ° C. 1 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1. 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
Polyamide 12 resin composition (A-1), semi-aromatic polyamide resin composition (B-1), fluorine-containing polymer (C-1), conductive fluorine-containing polymer (C-2) shown above Using a 4-layer tube forming machine (Plastics Engineering Laboratory Co., Ltd.), (A-1) was extruded at 260 ° C., (B-1) was extruded at 310 ° C., (C-1 ) Is melted separately at an extrusion temperature of 280 ° C. and (C-2) is melted at an extrusion temperature of 300 ° C., and the discharged molten resin is joined by an adapter, formed into a tubular shape, cooled by a sizing die that controls dimensions, and taken up The layer made of (A-1) is the layer (a) (outermost layer), the layer made of (B-1) is the layer (b) (intermediate layer), and the layer made of (C-1) is (c) ) Layer (inner layer), (C-2) layer (c ') layer (innermost layer) (A) / (b) / (c) / (c ′) = 0.65 / 0.15 / 0.10 / 0.10 mm, an inner diameter of 6 mm, and an outer diameter of 8 mm were 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 15, except that the conductive fluorine-containing polymer (C-2) was changed to the fluorine-containing polymer (C-3) and the extrusion temperature of (C-3) was changed to 280 ° C. 15 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1.

Example 17
In Example 15, a laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 15 except that the conductive fluorine-containing polymer (C-2) was changed to (C-4). It was. 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 18
In Example 15, the fluorine-containing polymer (C-1) was changed to (C-5), the conductive fluorine-containing polymer (C-2) was changed to (C-6), and (C-5) was extruded. A laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 15 except that the temperature was changed to 300 ° C and the extrusion temperature of (C-6) was changed to 320 ° C. 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 19
In Example 18, except that the conductive fluorine-containing polymer (C-6) was changed to the fluorine-containing polymer (C-7) and the extrusion temperature of (C-7) was changed to 300 ° C. In the same manner as in No. 18, a laminated tube having the layer configuration shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 20
In Example 18, a laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 18 except that the conductive fluorine-containing polymer (C-6) was changed to (C-8). It was. 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 21
In Example 15, the fluorine-containing polymer (C-1) was changed to (C-9), the conductive fluorine-containing polymer (C-2) was changed to (C-10), and (C-9) was extruded. A laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 15 except that the temperature was changed to 290 ° C and the extrusion temperature of (C-10) was changed to 310 ° C. 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 22
In Example 21, except that the conductive fluorine-containing polymer (C-10) was changed to the fluorine-containing polymer (C-11) and the extrusion temperature of (C-11) was changed to 290 ° C. A laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in No. The physical property measurement results of the laminated tube are shown in Table 1.

Example 23
A laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 21 except that the conductive fluorine-containing polymer (C-10) was changed to (C-12) in Example 21. It was. 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
A single layer shown in Table 1 in the same manner as in Example 1 except that the semi-aromatic polyamide resin composition (B-1) and the fluorine-containing polymer (C-1) are not used in Example 1. A 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.

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 resin composition (B-1). The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 4
In Example 1, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 1 except not using a fluorine-containing polymer (C-1). The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 5
In Example 1, the same method as in Example 1 except that the semi-aromatic polyamide resin 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 a layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 6
In Example 1, the same method as in Example 1 except that the semi-aromatic polyamide resin composition (B-1) was changed to (B-8) and the extrusion temperature of (B-8) was changed to 350 ° C. Thus, a laminated tube having a layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 7
In Example 17, the same method as Example 17 except that the semi-aromatic polyamide resin 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 a layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Comparative Example 8
In Example 17, the same method as in Example 17 except that the semi-aromatic polyamide resin composition (B-1) was changed to (B-8) and the extrusion temperature of (B-8) was changed to 350 ° C. Thus, a laminated tube having a 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 9
In Example 20, the same method as in Example 20 except that the semiaromatic polyamide resin 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 a 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 10
In Example 20, the same method as in Example 20 except that the semiaromatic polyamide resin composition (B-1) was changed to (B-8) and the extrusion temperature of (B-8) was changed to 350 ° C. Thus, a laminated tube having a 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 11
In Example 23, the same method as in Example 23, except that the semi-aromatic polyamide resin 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 a 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 12
In Example 23, the same method as in Example 23, except that the semiaromatic polyamide resin composition (B-1) was changed to (B-8) and the extrusion temperature of (B-8) was changed to 350 ° C. Thus, a laminated tube having a 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 13
In Example 1, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 1 except having changed the fluorine-containing polymer (C-1) into (C-3). The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 14
In Example 1, except that the fluorine-containing polymer (C-1) was changed to the conductive fluorine-containing polymer (C-4) and the extrusion temperature of (C-4) was changed to 300 ° C. 1 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Comparative Example 15
In Example 1, except that the fluorine-containing polymer (C-1) was changed to (C-7) and the extrusion temperature of (C-7) was changed to 300 ° C., the same method as in Example 1 was used. 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. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 16
In Example 1, except that the fluorine-containing polymer (C-1) was changed to the conductive fluorine-containing polymer (C-8) and the extrusion temperature of (C-8) was changed to 320 ° C. 1 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1. 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 17
In Example 1, except that the fluorine-containing polymer (C-1) was changed to (C-11) and the extrusion temperature of (C-11) was changed to 290 ° C., the same method as in Example 1 was used. 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. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 18
In Example 1, except that the fluorine-containing polymer (C-1) was changed to the conductive fluorine-containing polymer (C-12) and the extrusion temperature of (C-12) was changed to 310 ° C. 1 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1. 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 19
In Example 1, except that the fluorine-containing polymer (C-1) was changed to the conductive fluorine-containing polymer (C-14) and the extrusion temperature of (C-14) was changed to 300 ° C. 1 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Comparative Example 20
Using the polyamide 12 resin composition (A-1), the polyphenylene sulfide resin composition (D-1), and the adhesive resin composition (D-3) shown above, the product manufactured by Plabor (Plastic Engineering Laboratory Co., Ltd.) ) In a three-layer tube forming machine, (A-1) is melted separately at an extrusion temperature of 260 ° C., (D-1) and (D-3) are melted separately at an extrusion temperature of 310 ° C., and the discharged molten resin is an adapter. Are formed into a tubular shape, cooled by a sizing die that controls dimensions, and taken up, and the layer made of (A-1) is changed to the layer (a) (outermost layer) and the layer made of (D-3) ( d) When the layer (intermediate layer) and (D-1) are the layers (d ′) (innermost layer), the layer structure is (a) / (d) / (d ′) = 0.75 / A laminated tube having a diameter of 0.10 / 0.15 mm, an inner diameter of 6 mm, and an outer diameter of 8 mm was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 21
Comparative Example 20 except that the polyphenylene sulfide resin composition (D-1) was changed to the conductive polyphenylene sulfide resin composition (D-2) and the extrusion temperature of (D-2) was changed to 330 ° C. in Comparative Example 20. 20 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Comparative Example 22
Using the polyamide 12 resin composition (A-1), fluorine-containing polymer (C-1), polyphenylene sulfide resin composition (D-1), and adhesive resin composition (D-3) shown above. , Plabor (Plastics Engineering Laboratory Co., Ltd.) 5-layer tube forming machine, (A-1) extrusion temperature 260 ° C, (C-1) extrusion temperature 280 ° C, (D-1), (D -3) is melted separately at an extrusion temperature of 301 ° C., and the discharged molten resin is merged by an adapter, formed into a tube, cooled by a sizing die that controls dimensions, and taken up, from (A-1) (A) layer (outermost layer), (D) layer (d) layer (outer layer, inner layer), (D-1) layer (d ') layer (intermediate layer), When the layer made of (C-1) is the (c) layer (innermost layer), the layer structure is (a) / (d ) / (D ′) / (d) / (c) = 0.50 / 0.10 / 0.15 / 0.10 / 0.15 mm, an inner diameter of 6 mm, and an outer diameter of 8 mm were obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 23
In Comparative Example 22, Comparative Example 22 except that the fluorine-containing polymer (C-1) was changed to the conductive fluorine-containing polymer (C-2) and the extrusion temperature of (C-2) was changed to 300 ° C. The laminated tube of the layer structure shown in Table 1 was obtained by the same method. The physical property measurement results of the laminated tube are shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

As is clear from Table 1, the single-layer tube of Comparative Example 1 that does not have the layer made of the semi-aromatic polyamide and the layer made of the fluorine-containing polymer defined in the present invention is inferior in chemical solution permeation preventive property. The laminated tube of Comparative Example 2 which did not have a layer made of the aliphatic polyamide specified in the invention was inferior in low temperature impact resistance. The laminated tube of Comparative Example 3 that does not have a layer made of a semi-aromatic polyamide defined in the present invention or the laminated tube of Comparative Example 4 that does not have a layer made of a fluorine-containing polymer specified in the present invention is a chemical solution. It was inferior in permeation prevention. The laminated tubes of Comparative Examples 5 to 12 having a layer made of a semi-aromatic polyamide other than those specified in the present invention were inferior in interlayer adhesion. The laminated tubes of Comparative Examples 13 to 18 having a layer made of a fluorine-containing polymer other than those specified in the present invention were inferior in interlayer adhesion. The laminated tube of Comparative Example 19 having a layer made of a fluorine-containing polymer outside the MFR range defined in the present invention was inferior in environmental stress crack resistance. The laminated tubes of Comparative Examples 20 and 21 in which the polyphenylene sulfide layer is arranged in the innermost layer are inferior in interlayer adhesion and environmental stress crack resistance, have a layer made of polyphenylene sulfide, and contain fluorine as the innermost layer. The laminated tubes of Comparative Examples 22 and 23 having a layer made of a polymer are used for interlaminar adhesion, particularly when used in a state where a constant stress load is applied after being in contact with or immersed in fuel for a long time. In, it was inferior to durability of interlayer adhesiveness.
On the other hand, the laminated tubes of Examples 1 to 23 defined in the present invention have good properties such as low temperature impact resistance, chemical solution permeation prevention properties, interlayer adhesion properties, degradation fuel resistance properties, and environmental stress crack resistance properties. Obviously.

Claims (10)

(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 A layer (b) comprising 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 a method defined in ASTM D-3159 MFR (temperature higher by 50 ° C. than melting point of fluorine-containing polymer (C), 49 N load) measured by 1 is 1 g / 10 min or more and 6 g / 10 min or less, and is a functional group reactive to amino groups and features but is introduced in the molecular chain, and a conductive filler fluorine-containing polymer which contains a consist (C) including the (c) layer, in that it consists of at least three or more layers Laminate tube that.   The aliphatic polyamide (A) is polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene decanamide ( Polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecane methylene decanamide (polyamide 1010), polydecamethylene dodecane (polyamide 1012), and polydodecamethylene dodecane (polyamide 1212). The laminated tube according to claim 1, wherein the laminated tube is at least one homopolymer or a copolymer using several kinds of raw material monomers forming them.   The aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms in the semi-aromatic polyamide (B) is at least one selected from the group consisting of units derived from azelaic acid, sebacic acid, and dodecanedioic acid. Yes, xylylenediamine units and / or bis (aminomethyl) naphthalene units are m-xylylenediamine, p-xylylenediamine, 1,5-bis (aminomethyl) naphthalene, and 2,6-bis (aminomethyl) The laminated tube according to claim 1 or 2, wherein the laminated tube is at least one selected from the group consisting of units derived from naphthalene.   The functional group having reactivity with the amino group in the fluorine-containing polymer (C) is a carboxyl group, an acid anhydride group or a carboxylate salt, a hydroxyl group, a sulfo group or a sulfonate salt, an epoxy group, a cyano group. The laminated tube according to any one of claims 1 to 3, which is at least one selected from the group consisting of a group, a carbonate group, and a haloformyl group.   The (a) layer made of the aliphatic polyamide (A) is arranged in the outermost layer, and the (b) layer made of the semi-aromatic polyamide (B) is a layer (a) made of the aliphatic polyamide (A). It arrange | positions between the (c) layers which consist of the said fluorine-containing polymer (C), The laminated tube in any one of Claim 1 to 4 characterized by the above-mentioned.   The layer (b) made of the semiaromatic polyamide (B) and the layer (c) made of the fluorine-containing polymer (C) are in direct contact with each other. The laminated tube as described.   The laminated tube according to any one of claims 1 to 6, wherein a conductive layer made of a fluorine-containing polymer composition containing a conductive filler is disposed in the innermost layer of the laminated tube.   The laminated tube according to any one of claims 1 to 7, wherein the laminated tube is manufactured by coextrusion molding.   The laminated tube according to any one of claims 1 to 8, wherein the laminated tube has at least a corrugated region.   The laminated tube according to any one of claims 1 to 9, wherein the laminated tube is used as a chemical solution transport tube.

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