JP2012020571A - Laminated tube - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated tube excellent in chemical liquid impermeability, interlayer adhesion, and particularly, durability of interlayer adhesion under the high-temperature atmosphere.SOLUTION: The laminated tube includes at least the following four layers: a layer consisting of aliphatic polyamide; a layer comprising polyester polymer composition made of specific amount polyglycolic acid polymer and aromatic polyester polymer; a layer comprising modified polyester elastomer graft-modified with α, β-ethylene nature unsaturated carboxylic acid, diamine unit containing C9-13 aliphatic diamine unit by a specific amount, diamine unit containing C9-13 aliphatic diamine unit by a specific amount, semi-aromatic polyamide which consists of dicarboxylic acid unit containing terephthalic acid and/or naphthalenedicarboxylic acid unit of specific amount; and a layer comprising polyoxamide which comprises dicarboxylic acid unit containing a specific amount of oxalic acid.

Description

  The present invention relates to a laminated tube, and more specifically, relates to a laminated tube excellent in chemical solution permeation preventing properties and interlayer adhesion, particularly durability of interlayer adhesion in a high temperature atmosphere.

  In the past, automobile piping tubes were rusting due to antifreezing agents on roads, and in recent years, in response to requests for global warming prevention and energy saving, the main material is excellent in rust prevention. Substitution with lightweight resin is progressing. Resin used as a tube for piping usually includes polyamide-based resin, saturated polyester-based resin, polyolefin-based resin, thermoplastic polyurethane-based resin, etc., but in the case of a single-layer tube using these, heat resistance The applicable range is limited due to insufficient chemical resistance and the like.

  From the viewpoint of saving gasoline consumption and improving performance, automobile piping tubes include low-boiling alcohols such as methanol and ethanol, or oxygen-containing gasoline blended with ethers such as methyl-t-butyl ether (MTBE). Be transported. Furthermore, in recent years, strict exhaust gas regulations including prevention of leakage into the atmosphere due to diffusion of volatile hydrocarbons and the like through piping tube partition walls have been implemented from the viewpoint of preventing environmental pollution. In the future, since stricter regulations are imposed, it is desirable to suppress the fuel that permeates and evaporates from the piping tube partition wall to the limit. For such strict regulations, conventionally used single-layer tubes using polyamide-based resins, particularly polyamide 11 or polyamide 12 excellent in strength, toughness, chemical resistance and flexibility, The permeation-preventing property with respect to a chemical solution 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, resins having good chemical permeation preventive properties such as saponified ethylene / vinyl acetate copolymer (EVOH), polymetaxylylene adipamide (polyamide MXD6), polybutylene terephthalate (PBT), poly Butylene naphthalate (PBN), polyphenylene sulfide (PPS), polyvinylidene fluoride (PVDF), ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexa Fluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (TFE / HFP / VDF, THV), tetrafluoroethylene / perfluoro (alkylbiphenyl) Laminated tubes ether) copolymer (PFA) are arranged has been proposed (e.g., see Patent Document 1).

  On the other hand, since polyglycolic acid has better chemical solution permeation-prevention properties than polyamide and saponified ethylene / vinyl acetate copolymer (EVOH), a high-density polyethylene layer is disposed on the inner and outer layers, and polyglycol is disposed on the core layer. A multilayer plastic fuel container having a layer structure in which an acid layer is arranged has been proposed (see Patent Document 2). In this technology, there is no suggestion regarding a laminated tube with polyglycolic acid having a polyamide-based resin as a constituent material. In addition, the laminated tube needs to have strong interlayer adhesive strength so that delamination does not occur during processing or use. In the multilayer plastic fuel container, a glycidyl group-containing polyolefin copolymer or the like has been proposed as an adhesive resin interposed between the layers of high-density polyethylene and polyglycolic acid. There is no disclosure of data on peel strength, and even when a glycidyl group-containing polyolefin copolymer is used as an adhesive resin interposed between the polyamide resin and the polyglycolic acid, the interlaminar adhesion may be reduced depending on the use environment conditions. There is a problem in actual use because there is a drawback that the dispersion and reduction are large, and particularly the durability of the interlaminar adhesive strength is inferior in a high temperature atmosphere. Furthermore, in advanced countries such as North America, Europe, and Japan, regulations on the total amount of exhaust gas and fuel are being further strengthened, and more advanced chemical permeation prevention performance has been demanded for automobile piping tubes.

US Pat. No. 5,554,425 JP 2003-261168 A

  An object of the present invention is to solve the above problems and to provide a laminated tube excellent in chemical solution permeation preventive property, interlayer adhesiveness, particularly durability of interlayer adhesive strength in a high temperature atmosphere.

  As a result of intensive studies to solve the above problems, the present inventor has found that a layer made of an aliphatic polyamide, a layer made of a polyester-based polymer composition made of a polyglycolic acid polymer and an aromatic polyester polymer, α , Β-ethylenically unsaturated carboxylic acid grafted modified polyester elastomer layer, laminated tube composed of a semi-aromatic polyamide or polyoxamide layer with a specific structure, prevents chemical permeation, and interlayer adhesion In particular, the present inventors have found that the interlaminar adhesion durability under a high temperature atmosphere is excellent, and the properties such as low temperature impact resistance, heat resistance and chemical resistance are good.

That is, the present invention comprises (A) (a) layer made of aliphatic polyamide, (B) (b) layer made of polyester polymer composition, (C) (c) layer made of modified polyester elastomer, and (D1) It is a laminated tube consisting of at least four layers, including a (d) layer made of semi-aromatic polyamide or (D2) polyoxamide,
(B) The polyester polymer composition is a polyester polymer composition comprising (B1) 60 to 90% by mass of a polyglycolic acid polymer and (B2) 40 to 10% by mass of an aromatic polyester polymer,
(C) The modified polyester elastomer is a modified polyester elastomer graft-modified with an α, β-ethylenically unsaturated carboxylic acid,
(D1) The semi-aromatic polyamide is a diamine unit containing 60 mol% or more of an aliphatic diamine unit having 9 to 13 carbon atoms with respect to all diamine units, and terephthalic acid and / or naphthalene with respect to all dicarboxylic acid units. A semi-aromatic polyamide comprising a dicarboxylic acid unit containing at least 50 mol% of a dicarboxylic acid unit,
(D2) The dioxan in which the polyoxamide contains 60 mol% or more of aliphatic diamine units having 9 to 13 carbon atoms with respect to all diamine units and 60 mol% or more of oxalic acid units with respect to all dicarboxylic acid units. The present invention provides a laminated tube which is a polyoxamide comprising acid units.

  The laminated tube of the present invention has good chemical solution permeation preventive properties and excellent interlayer adhesion, and in particular, does not have the disadvantage of a significant decrease in interlayer adhesive strength in a high-temperature atmosphere, and is excellent in durability of interlayer adhesive strength. Therefore, the laminated tube of the present invention can be used in any environment, and its utility value is extremely large.

The present invention is described in detail below.
[(A) Aliphatic polyamide]
The (A) aliphatic polyamide used in the present invention has an amide bond (—CONH—) in the main chain, and is a nylon salt comprising a lactam, an aminocarboxylic acid, or an aliphatic diamine and an aliphatic dicarboxylic acid. Is obtained by polymerization or copolymerization by a known method such as melt polymerization, solution polymerization or solid phase polymerization.

  Examples of lactams include caprolactam, enantolactam, undecane lactam, dodecane lactam, α-pyrrolidone, α-piperidone, and aminocarboxylic acids 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 constituting the nylon salt 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-tetradecane Diamine, 1,15-pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, 1,19-nonadecanediamine, 1,20-eicosanediamine, 2- / 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, 2, , 4 / 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.

  Examples of aliphatic dicarboxylic acids constituting the nylon salt include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, and tridecanedicarboxylic acid. Examples include acid, tetradecanedicarboxylic acid, pentadecanedicarboxylic acid, hexadecanedicarboxylic acid, octadecanedicarboxylic acid, and eicosanedicarboxylic acid. These can use 1 type (s) or 2 or more types.

  (A) As the aliphatic polyamide, 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 azelamide (polyamide 49), polytetramethylene sebacamide (polyamide 410), polytetramethylene dodecamide (Polyamide 412), polypentamethylene succinamide (polyamide 54), polypentamethylene glutamide (polyamide 55), polypentamethylene adipamide (polyamide 56), polypentamethylene azelamide (polyamide) 9), polypentamethylene sebamide (polyamide 510), polypentamethylene dodecamide (polyamide 512), polyhexamethylene succinamide (polyamide 64), polyhexamethylene glutamide (polyamide 65), polyhexamethylene adipa Amide (polyamide 66), polyhexamethylene azelamide (polyamide 69), polyhexamethylene sebamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene adipamide (polyamide 96), polynona Methylene azeramide (polyamide 99), polynonamethylene sebamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), polydecamethylene adipamide (polyamide 106), polydecamethylene azelamide ( Reamide 109), polydecamethylene sebamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), polydodecamethylene adipamide (polyamide 126), polydodecamethylene azelamide (polyamide 129), polydodecamethylene se Examples thereof include homopolymers such as bacamide (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 copolymers using several kinds of raw material monomers forming these are preferable, such as polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66). Polyhexamethylene decanamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecamethylene decanamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), polydodecamethylene dodecamide (polyamide 1212), At least one selected from the group consisting of polyundecanamide (polyamide 11) and polydodecanamide (polyamide 12) is more preferable.

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

  Other polyamide resins include polymetaxylylene adipamide (polyamide MXD6), polymetaxylylene veramide (polyamide MXD8), polymetaxylylene azelamide (polyamide MXD9), polymetaxylylene sebacamide (polyamide MXD10). , Polymetaxylylene decanamide (polyamide MXD12), polymetaxylylene terephthalamide (polyamide MXDT), polymetaxylylene isophthalamide (polyamide MXDI), polymetaxylylene naphthalamide (polyamide MXDN), polybis (4-aminocyclohexyl) Methanedecamide (Polyamide PACM12), Polybis (4-aminocyclohexyl) methane terephthalamide (Polyamide PACMT), Polybis (4-aminocyclohexyl) methane Phthalamide (polyamide PACMI), polyisophorone adipamide (polyamide IPD6), polyisophoron decanamide (polyamide IPD12), polyisophorone terephthalamide (polyamide IPDT), polyisophorone isophthalamide (polyamide IPDI), 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 Taramide (polyamide 6N), poly-2-methylpentamethylene terephthalamide (polyamide M5T), poly-2-methylpentamethylene isophthalamide (polyamide M5I), poly-2-methylpentamethylene hexahydroterephthalamide (polyamide M5T (H)) , Poly-2-methylpentamethylene naphthalamide (polyamide M5N), polynonamethylene isophthalamide (polyamide 9I), polynonamethylene hexahydroterephthalamide (polyamide 9T (H)), poly-2-methyloctamethylene isophthalamide ( Polyamide M8I), poly 2-methyloctamethylene hexahydroterephthalamide (polyamide M8T (H)), polytrimethylhexamethylene isophthalamide (polyamide TMHI), polytrimethylhexamethylene Hexahydroterephthalamide (polyamide TMHT (H)), polydecamethylene isophthalamide (polyamide 10I), polydecamethylene hexahydroterephthalamide (polyamide 10T (H)), polyundecamethylene isophthalamide (polyamide 11I) ), Polyundecamethylene hexahydroterephthalamide (polyamide 11T (H)), polydodecamethylene isophthalamide (polyamide 12I), polydodecamethylene hexahydroterephthalamide (polyamide 12T (H)) and these polyamide raw materials monomers And / or a copolymer using several kinds of raw material monomers of the aliphatic polyamide. 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), 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 / acrylic acid Polyolefin resins such as ethyl copolymer (EEA) and Polyolefin resin containing a functional group such as a boxyl group and a salt thereof, an acid anhydride group, an epoxy group, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI Polymer, Polytrimethylene terephthalate (PTT), Polyarylate (PAR), Polyethylene naphthalate (PEN), Polybutylene naphthalate (PBN), Polyester resins such as liquid crystal polyester (LCP), Polyacetal (POM), Polyphenylene oxide Polyether resins such as (PPO), polysulfone resins such as polysulfone (PSF) and polyethersulfone (PES), polythiones such as polyphenylene sulfide (PPS) and polythioethersulfone (PTES) Ether resins, polyether ether ketone (PEEK), polyketone resins such as polyallyl ether ketone (PAEK), polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / Polystyrene resins such as styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), methacrylonitrile / styrene / butadiene copolymer (MBS), polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA) ) And other polymethacrylate resins, polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymers, vinylidene chloride / methyl acrylate copolymers, etc. Cellulosic resins such as vinyl resins, cellulose acetate, cellulose butyrate, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorofluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE), ethylene / Chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (TFE / HFP / VDF) , THV), fluororesin such as tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (PFA), polycarbonate resin such as polycarbonate (PC), thermoplastic polyimide (PI), poly Midoimido (PAI), polyimide-based resins such as polyether imide, thermoplastic polyurethane resins, polyurethane elastomers, polyester elastomers, and the like. These can use 1 type (s) or 2 or more types.

  (A) Aliphatic polyamide production equipment includes batch reaction kettles, one-tank or multi-tank continuous reaction equipment, tubular continuous reaction equipment, uniaxial kneading extruder, 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, from the viewpoint of ensuring the mechanical properties of the obtained laminated tube and ensuring the desirable formability of the laminated tube by setting the viscosity at the time of melting to an appropriate range, 96% sulfuric acid in accordance with JIS K-6920, The relative viscosity of the (A) aliphatic polyamide measured under the conditions of a polyamide concentration of 1% and 25 ° C. is preferably 1.5 to 5.0, more preferably 2.0 to 4.5. preferable.

  (A) When the aliphatic polyamide has a terminal amino group concentration per gram of the polyamide [A] (μeq / g) and a terminal carboxyl group concentration [B] (μeq / g), [A]> [B ] Satisfying +5 (hereinafter sometimes referred to as terminally adjusted aliphatic polyamide) is preferable in consideration of interlayer adhesion with (C) modified polyester elastomer, particularly durability of interlayer adhesion strength in a high temperature atmosphere, [ A]> [B] +10 is more preferable, and [A]> [B] +15 is more preferable. Furthermore, [A]> 20 is preferable, and 30 <[A] <120 is more preferable from the viewpoint of the melt stability of the polyamide and the suppression of the generation of the gel-like material.

  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-adjusted aliphatic polyamide is produced by polymerizing or copolymerizing the raw material of the (A) aliphatic polyamide in the presence of amines by a known method such as melt polymerization, solution polymerization or solid phase polymerization. The Alternatively, it is produced by melt-kneading in the presence of amines after polymerization. Thus, amines can be added at any stage during polymerization, or after polymerization, at any stage during melt-kneading, but considering the durability of interlayer adhesion strength in a high-temperature atmosphere of the laminated tube, It is preferable to add at the stage of polymerization.

  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. In addition, the following exemplified amines and carboxylic acids can be used alone or in combination of two or more.

  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 and docosylamine, alicyclic monoamines such as cyclohexylamine and 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- / 3-methyl-1,5-pentanediamine, 2-methyl-1,8 -Octanediamine, 2,2,4- / 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl Aliphatic diamines such as 1,9-nonanediamine, 1,3- / 1,4-cyclohexanedimethylamine, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, bis (3-methyl-4- Aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) propane, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexanemethyl Examples thereof include alicyclic diamines such as amine, bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, norbornane dimethylamine, and tricyclodecanedimethylamine, and aromatic diamines such as m- / p-xylylenediamine. 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- / 1,2,4- / 1,2,3-triaminocyclohexane, 1,2,4,5-tetraminocyclohexane, 1,3,5- / 1,2,4 -/ 1,2,3-triaminobenzene, 1,2,4,5-tetraminobenzene, 1,2,4- / 2,5,7-triaminonaphthalene, 2,4,6-triaminopyridine, 1,2,7,8- / 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 more kinds of alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, and 1,1-dimethylethyleneimine. The homopolymer and copolymer obtained by superposing | polymerizing by a conventional method are mentioned. Among these, polyethyleneimine is more preferable. A polyalkyleneimine is obtained by polymerizing an alkyleneimine as a raw material and using a branched polyalkyleneimine containing a primary amine, a secondary amine or a tertiary amine obtained by ring-opening polymerization of the alkyleneimine or an 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 to 3,000, more preferably 8 to 1,500, and still more preferably 11 to 500. The number average molecular weight of the polyalkyleneimine is preferably from 100 to 20,000, more preferably from 200 to 10,000, and further preferably from 500 to 8,000.

  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, octadecadioic acid, octadecenedioic acid, ray Sandioic acid, eicosenedioic acid, docosandioic acid, diglycolic acid, aliphatic dicarboxylic acids such as 2,2,4- / 2,4,4-trimethyladipic acid, 1,3- / 1,4-cyclohexanedicarboxylic acid Acids, cycloaliphatic dicarboxylic acids such as norbornane dicarboxylic acid, terephthalic acid, isophthalic acid, phthalic acid, m- / p-xylylene dicarboxylic acid, 1,4- / 2,6- / 2,7-naphthalenedicarboxylic acid, etc. Aromatic dicarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,3,5-pentanetricarboxylic acid, 1,2,6- / 1,3,6-hexanetricarboxylic acid, 1,3,5-cyclohexane And tricarboxylic acids such as tricarboxylic acid and 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 terminally adjusted aliphatic polyamide to be produced. From the viewpoint of obtaining sufficient reactivity and facilitating the production of a polyamide having a desired viscosity, the amount of amines is usually based on 1 mol of polyamide raw material (monomer or monomer unit 1 mol constituting a repeating unit). The addition amount is preferably 0.5 to 20 meq / mol, and more preferably 1.0 to 10 meq / mol (the equivalent (eq) of amino group reacts 1: 1 with the carboxyl group). The amount of the amino group forming the amide group is 1 equivalent).

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

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

  Moreover, it is preferable to add a plasticizer to (A) aliphatic polyamide. 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- / N-ethyl-p-toluenesulfonic acid butyramide, N-ethyl-o- / N-ethyl-p-toluenesulfonic acid 2-ethylhexylamide, and the like. It is done. Examples of hydroxybenzoic acid alkyl esters include ethylhexyl o- / p-hydroxybenzoate, hexyldecyl o- / p-hydroxybenzoate, ethyldecyl o- / p-hydroxybenzoate, octyloctyl o- / p-hydroxybenzoate Decyldodecyl o- / p-hydroxybenzoate, methyl o- / p-hydroxybenzoate, butyl o- / p-hydroxybenzoate, hexyl o- / p-hydroxybenzoate, o- / p-hydroxybenzoic acid n-octyl, o- / p-hydroxybenzoic acid decyl, o- / 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 is ethylhexyl and / or hexyldecyl p-hydroxybenzoate.

  The blending amount of the plasticizer is preferably 1 to 30 parts by mass, and 1 to 15 parts by mass with respect to 100 parts by mass of the (A) aliphatic polyamide, from the viewpoint of sufficiently ensuring the low temperature impact resistance of the laminated tube. More preferably, it is a part.

  Moreover, it is preferable to add an impact resistance improving material to (A) aliphatic polyamide. Examples of the impact resistance improving material include rubbery polymers, and the flexural modulus measured according to ASTM D-790 is preferably 500 MPa or less from the viewpoint of sufficiently imparting the impact improving effect.

  Examples of the impact resistance improver include a copolymer containing an α-olefin and ethylene and / or propylene, a copolymer containing ethylene and / or propylene and an α, β-unsaturated carboxylic acid and / or an unsaturated carboxylic acid ester, The block copolymer containing an ionomer polymer, an aromatic vinyl compound, and a conjugated diene compound is mentioned, These can use 1 type (s) or 2 or more types.

  The copolymer containing the α-olefin and ethylene and / or propylene is a polymer obtained by copolymerizing ethylene and / or propylene and an α-olefin having 3 or more carbon atoms, and as an α-olefin having 3 or more carbon atoms. Are 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-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl- 1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1 Hexene, 3-ethyl-1-hexene, 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- / 1,5-hexadiene, 1,4- / 1,5- / 1,6- / 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-iso Propenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene The non-conjugated diene polyene such as 2-propenyl-2,5-norbornadiene may be copolymerized. These can use 1 type (s) or 2 or more types.

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

  The ionomer polymer is obtained by ionizing at least part of the carboxyl group of a copolymer containing an olefin and an α, β-unsaturated carboxylic acid 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 block copolymer containing an aromatic vinyl compound and a conjugated diene compound 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- / m- / p-methylstyrene, 1,5- / 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene, 4-propylstyrene, 4-cyclohexylstyrene. , 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene, and the like, and one or more of them 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 copolymer containing a hydrogenated aromatic vinyl compound and a conjugated diene compound, part of the unsaturated bond Or all are saturated bonds.

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

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

  (A) Examples of functional groups having affinity for aliphatic polyamides include carboxyl groups, acid anhydride groups, carboxylic acid ester groups, carboxylic acid metal salts, carboxylic acid imide groups, carboxylic acid amide groups, and epoxy groups. 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 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 blending amount of the impact resistance improving material is preferably 1 to 35 parts by mass with respect to 100 parts by mass of the (A) aliphatic polyamide, from the viewpoint of sufficiently securing the mechanical strength of the laminated tube, and 5 to 25 More preferably, it is part by mass.

  Further, (A) the aliphatic polyamide may contain 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.

[(B) Polyester polymer composition]
The (B) polyester polymer composition used in the present invention comprises (B1) 60 to 90% by mass of a polyglycolic acid polymer and (B2) 40 to 10% by mass of an aromatic polyester polymer.

[(B1) polyglycolic acid polymer]
(B1) The polyglycolic acid polymer has the following general formula (1)

It is a homopolymer or a copolymer containing the repeating unit represented by these. (B1) The content ratio of the repeating unit represented by the formula (1) in the polyglycolic acid polymer does not impair the crystallinity originally possessed by the (B1) polyglycolic acid polymer, and prevents the chemical penetration of the laminated tube. From the viewpoint of suitably maintaining the properties, heat resistance, etc., it is preferably 60% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and 100% by mass. It is particularly preferred.

  (B1) In addition to the repeating unit represented by the general formula (1), the polyglycolic acid polymer contains, for example, at least one repeating unit selected from the group consisting of the following formulas (2) to (6) Can be made.

In the said General formula (2), n represents the integer of 1-10 and m represents the integer of 0-10. Moreover, in the said General formula (3), j represents the integer of 1-10. Furthermore, the general formula (4), _{R 1} and _{R 2} may be the same or different, represent a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, k is an integer of 2 to 10. By introducing these other repeating units at a ratio of 1% by mass or more, the melting point of the polyglycolic acid homopolymer can be lowered. If the melting point of the (B1) polyglycolic acid polymer is lowered, the processing temperature can be lowered, and the thermal decomposition during the melt processing can be reduced. Also, the processability can be improved by controlling the crystallization rate of the polyglycolic acid polymer by copolymerization.

  Examples of the method for synthesizing the (B1) polyglycolic acid polymer include a method of dehydrating polycondensation of glycolic acid, a method of dealcoholating polycondensation of glycolic acid alkyl ester, a method of ring-opening polymerization of glycolide, and the like. Among these, glycolide is subjected to ring-opening polymerization by heating to a temperature of about 120 to 250 ° C. in the presence of a small amount of a catalyst (for example, a cation catalyst such as organic carboxylate tin, tin halide, antimony halide, etc.). A method of synthesizing polyglycolic acid (ie, polyglycolide) by a method is preferred. Such ring-opening polymerization is preferably performed by a bulk polymerization method or a solution polymerization method.

  On the other hand, the (B1) polyglycolic acid polymer is obtained by copolymerizing at least one repeating unit selected from the group consisting of units derived from glycolic acid, glycolic acid alkyl ester and glycolide with other repeating units. Can do. Other repeating units include, for example, ethylene oxalate, lactide, β-propiolactone, β-butyrolactone, pivalolactone, γ-butyrolactone, δ-valerolactone, β-methyl-δ-valerolactone, ε-caprolactone, etc. Units derived from lactones, units derived from cyclic monomers such as trimethylene carbonate, 1,3-dioxane, lactic acid, 3-hydroxypropanoic acid, 3-hydroxybutanoic acid, 4-hydroxybutanoic acid, 6-hydroxy Units derived from hydroxycarboxylic acids such as caproic acid or their alkyl esters, units derived from aliphatic diols such as 1,2-ethanediol and 1,4-butanediol, fats such as succinic acid and adipic acid Derived from aliphatic dicarboxylic acids or their alkyl esters Unit, and the like. These can use 1 type (s) or 2 or more types.

  Among these, a unit derived from a cyclic compound such as lactide, caprolactone, trimethylene carbonate, or a hydroxycarboxylic acid such as lactic acid is preferable because it is easy to copolymerize and a copolymer having excellent physical properties is easily obtained. (B1) The content ratio of other repeating units in the polyglycolic acid polymer does not impair the crystallinity of the polymer to be produced, and suitably maintains the heat resistance, chemical permeation prevention, mechanical strength, etc. of the laminated tube. From a viewpoint, it is preferable that it is 40 mass% or less with respect to 100 mass parts of all the monomer units, It is more preferable that it is 30 mass% or less, It is further more preferable that it is 20 mass% or less.

(B1) The polyglycolic acid polymer is excellent in chemical solution permeation prevention properties, particularly barrier properties against alcohol-containing gasoline. Alcohol-containing gasoline permeability coefficient, put the sheet obtained from the resin to be measured into a permeability coefficient measuring cup charged with isooctane / toluene / ethanol mixed solvent mixed with isooctane, toluene and ethanol in a volume ratio of 45:45:10, It is a value calculated from the mass change measured at 60 ° C. By selecting a (B1) polyglycolic acid polymer in which the content of the repeating units described above is in a suitable range, the alcohol-containing gasoline permeability coefficient of the polymer is 1.0 g · mm / (m ² · Day) or less, preferably 0.01 to 0.5 g · mm / (m ² · day), more preferably 0.02 to 0.4 g · mm / (m ² · day). More preferably,

From the viewpoint of setting the viscosity at the time of melting to an appropriate range and ensuring the preferable moldability of the laminated tube of the present invention, the viscosity was measured under conditions of a temperature 20 ° C. higher than the melting point Tm (Tm + 20 ° C.) and a shear rate of 120 sec ⁻¹ (B1 ) The melt viscosity of the polyglycolic acid polymer is preferably 300 to 10,000 Pa · s, more preferably 400 to 8,000 Pa · s, and 500 to 5,000 Pa · s. Is more preferable. (B1) From the viewpoint of suppressing the degradation of the polyglycolic acid polymer and the accompanying decrease in molecular weight and foaming, the melt processing temperature of the (B1) polyglycolic acid polymer is around 260 ° C. (for example, in the range of 250 to 270 ° C. It is desirable to set the temperature at (in).

(B1) The melting point (Tm) of the polyglycolic acid polymer is preferably 200 ° C. or higher, preferably 210 ° C. or higher, from the viewpoint of suitably maintaining the chemical solution permeation preventing property, heat resistance, etc. of the laminated tube of the present invention. More preferably. The polyglycolic acid homopolymer has a melting point of about 220 ° C., a glass transition temperature of about 38 ° C., and a crystallization temperature of about 91 ° C. However, these thermal properties vary depending on the molecular weight of the (B1) polyglycolic acid polymer, the copolymer component, and the like. The crystal density (ρ) of the polyglycolic acid homopolymer is about 1.7 g / cm ³ .

  In the present invention, the (B1) polyglycolic acid polymer includes inorganic fillers, other thermoplastic resins, plasticizers, catalyst deactivators, heat stabilizers, ultraviolet absorptions, as long as the object of the present invention is not impaired. Various additives such as an agent, a light stabilizer, a moisture proofing agent, a waterproofing agent, a water repellent, a lubricant, a mold release agent, a coupling agent, a pigment, and a dye can be contained.

  (B1) The polyglycolic acid polymer has a hydroxyl group and / or a carboxyl group at its end during synthesis. (B1) The polyglycolic acid polymer can be modified with a non-acid-forming OH group blocking agent and / or a carboxyl group blocking agent. (B1) The polyglycolic acid polymer is hydrolyzable and easily colored during melt processing, and by blending a non-acid-forming OH group sealing agent and / or a carboxyl group sealing agent. Water resistance and hydrolyzability can be improved and coloring can be suppressed.

“Non-acid-forming” in a non-acid-forming OH group-capping agent means that (B1) OH groups remaining in the polyglycolic acid polymer are bonded and sealed to form no carboxyl group. It means that. Examples of the non-acid-forming OH group blocking agent include diketene compounds and isocyanates. These can use 1 type (s) or 2 or more types. Among these OH group blocking agents, diketene compounds are preferable from the viewpoint of reactivity.
The blending amount of the OH group terminal blocking agent is preferably 0.01 to 20 parts by mass, and 0.1 to 10 parts by mass with respect to 100 parts by mass of the (B1) polyglycolic acid polymer. More preferred.

As the carboxyl group blocking agent, a compound having a carboxyl group end blocking action and known as a water resistance improver for aliphatic polyesters can be used. Specific examples of the carboxyl group-capping agent include, for example, carbodiimide compounds such as N, N-2,6-diisopropylphenylcarbodiimide, 2,2′-m-phenylenebis (2-oxazoline), 2,2′-p. -Oxazoline compounds such as phenylenebis (2-oxazoline), 2-phenyl-2-oxazoline, styrene isopropenyl-2-oxazoline, and oxazines such as 2-methoxy-5,6-dihydro-4H-1,3-oxazine Examples thereof include epoxy compounds such as compounds, N-glycidylphthalimide, cyclohexene oxide, and tris (2,3-epoxypropyl) isocyanurate. These can use 1 type (s) or 2 or more types.
Among these carboxyl group-capping agents, carbodiimide compounds are more preferable, and aromatic, alicyclic, and aliphatic carbodiimide compounds are also used, but aromatic carbodiimide compounds are more preferable, and those with particularly high purity are used. Gives water resistance stabilization effect. It is preferable that the compounding quantity of a carboxyl group sealing agent is 0.01-10 mass parts with respect to 100 mass parts of (B1) polyglycolic acid polymers, and it is 0.05-2.5 mass parts. Is more preferable.

  (B1) A poly (glycolic acid) polymer can be blended with a heat stabilizer in order to increase melt stability. As the heat stabilizer, a heavy metal deactivator, a phosphate ester having a pentaerythritol skeleton structure, a phosphorus compound having at least one hydroxyl group and at least one long-chain alkyl ester group, a metal carbonate, and the like are preferable. These can use 1 type (s) or 2 or more types.

Many phosphorous compounds such as phosphite antioxidants exhibit the action of inhibiting the melt stability of the (B1) polyglycolic acid polymer, and are therefore not preferred for use as heat stabilizers. On the other hand, the phosphate ester having a pentaerythritol skeleton structure exhibits an action of specifically improving the melt stability of the polyglycolic acid polymer. Specific examples of the phosphate ester having a pentaerythritol skeleton structure include cyclic neopentanetetrayl bis (2,6-di-t-butyl-4-methylphenyl) phosphite, cyclic neopentanetetrayl bis (2 , 4-di-t-butylphenyl) phosphite, bis (monononylphenyl) pentaerythritol diphosphite, bis (4-octadecylphenyl) pentaerythritol diphosphite, and the like. These can use 1 type (s) or 2 or more types.
Among the phosphorus compounds, phosphorus compounds having at least one hydroxyl group and at least one long-chain alkyl ester group are preferable. The long-chain alkyl preferably has 8 to 24 carbon atoms. Specific examples of such phosphorus compounds include mono- or di-stearyl acid phosphate.

  Examples of heavy metal deactivators include 2-hydroxy-N-1H-1,2,4-triazol-3-yl-benzamide, bis [2- (2-hydroxybenzoyl) hydrazine] dodecanedicarboxylic acid, and the like. . Examples of the metal carbonate include calcium carbonate and strontium carbonate.

  The blending ratio of the heat stabilizer is 0.001 to 5 parts by mass with respect to 100 parts by mass of the (B1) polyglycolic acid polymer from the viewpoint of securing the melt stability and the processing stability at the time of forming the laminated tube. It is preferable that it is 0.003 to 3 parts by mass, and more preferably 0.005 to 1 part by mass.

[(B2) aromatic polyester polymer]
The (B2) aromatic polyester polymer used in the present invention is a polymer having a structural unit of an aromatic ring and an ester bond in the main chain, and an aromatic dicarboxylic acid or an ester-forming derivative thereof and a diol Alternatively, it is a polymer or copolymer composed of units derived from ester-forming derivatives thereof.

  Units derived from aromatic dicarboxylic acids include terephthalic acid, isophthalic acid, phthalic acid, 1,4- / 1,5- / 2,6- / 2,7-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, 4, 4′-diphenyldicarboxylic acid, diphenylmethane-4,4′-dicarboxylic acid, diphenylethane-4,4′-dicarboxylic acid, diphenylpropane-4,4′-dicarboxylic acid, 4,4′-diphenylethercarboxylic acid, 4, 4'-diphenyl sulfide dicarboxylic acid, 4,4'-diphenyl sulfone dicarboxylic acid, 4,4'-diphenyl ketone dicarboxylic acid, sodium 3-sulfoisophthalate, potassium 3-sulfoisophthalate, etc., or ester-forming derivatives thereof Units derived from are exemplified. These can use 1 type (s) or 2 or more types. Among these, units derived from terephthalic acid, 2,6-naphthalenedicarboxylic acid, dimethyl terephthalate, and / or dimethyl 2,6-naphthalene are preferred.

  It is also possible to copolymerize other dicarboxylic acid units. Examples of other dicarboxylic acid units include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and the like, 1 , 3- / 1,4-cyclohexanedicarboxylic acid, alicyclic dicarboxylic acids such as dicyclohexyl-4,4-dicarboxylic acid, or units derived from these ester-forming derivatives. These can use 1 type (s) or 2 or more types.

  Moreover, as a unit derived from diol, a C2-C12 aliphatic diol unit is preferable. Examples of the aliphatic diol having 2 to 12 carbon atoms include 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methyl-1,5-pentanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol, 1,10-decanediol, 1,12-dodecanediol, etc. Units derived from. These can use 1 type (s) or 2 or more types. Among these, units derived from 1,2-ethanediol and / or 1,4-butanediol are preferable.

  It is also possible to copolymerize units derived from other diols. Examples of units derived from other diols include alicyclic diols such as 1,3- / 1,4-cyclohexanediol, xylylene glycol, 1,2- / 1,3- / 1,4-dihydroxybenzene, 4,4′-dihydroxydiphenyl, 4,4′-dihydroxydiphenyl ether, 1,1-bis (4-hydroxyphenyl) methane, 4,4′-dihydroxydiphenylethane, 2,2-bis (4-hydroxyphenyl) propane , Units derived from aromatic diols such as 4,4′-dihydroxydiphenyl ketone, 4,4′-dihydroxydiphenyl sulfide, and 4,4′-dihydroxydiphenyl sulfone. These can use 1 type (s) or 2 or more types.

  The (B2) aromatic polyester polymer is a copolymer of trifunctional or higher functional compounds such as glycerin, trimethylpropane, pentaerythritol, trimellitic acid, pyromellitic acid, etc., as long as the molding performance is not substantially lost. It is also possible.

  (B2) Specific examples of the aromatic polyester polymer include polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyhexamethylene terephthalate, polycyclohexylene dimethylene terephthalate, polyethylene naphthalate, polybutylene naphthalate, ethylene terephthalate / isophthalate. Examples thereof include a copolymer, a butylene terephthalate / isophthalate copolymer, a butylene terephthalate / sebacate copolymer, and an ethylene terephthalate / cyclohexylene dimethylene terephthalate copolymer. Among these, at least one selected from the group consisting of polyethylene terephthalate, polybutylene terephthalate, polyethylene naphthalate, and polybutylene naphthalate is preferable, and polybutylene is excellent because of its economical efficiency, molding temperature, and chemical penetration prevention properties. Terephthalate and / or polybutylene naphthalate are more preferred.

  (B2) The aromatic polyester polymer is obtained by polycondensing the raw material components using a conventionally known polyester production method. The monomer component is charged into the reaction vessel at a predetermined ratio, and the reaction is started in the presence of a catalyst while blowing an inert gas such as nitrogen. By-product low molecular weight compounds are continuously removed from the reaction system. The reaction can be carried out under normal pressure, reduced pressure, or increased pressure, but the reaction is preferably performed under reduced pressure. Then, if desired, the polymer is used in the form of chips or pellets or in the form of blocks. If necessary, solid phase polymerization may be performed according to a conventional method.

Examples of the catalyst used include tin, antimony, cobalt, manganese, calcium, germanium, nickel, zinc, lead, iron, magnesium, and / or a titanium compound. The addition amount of the catalyst is preferably 5 to 100 mmol%, more preferably 10 to 50 mmol%, based on the raw material components. Furthermore, an alkali metal may be added to control the quality such as the number of carboxyl terminal groups. As an alkali metal, lithium, sodium, and potassium are preferable, and potassium is preferable among these. It is preferable that the addition amount of an alkali metal is 0.1-20 mmol% based on a raw material component.
For the purpose of adjusting the molecular weight and controlling the reaction, monocarboxylic acid, monoalcohol and the like may be used as necessary. Examples of the monocarboxylic acid include benzoic acid, p-oxybenzoic acid, toluene carboxylic acid, salicylic acid, acetic acid, propionic acid, stearic acid and the like. Examples of the monoalcohol include benzyl alcohol, toluene-4-methanol, and cyclohexanemethanol.

  The intrinsic viscosity of the (B2) aromatic polyester polymer measured at 25 ° C. using a 1: 1 mixed solvent of phenol / tetrachloroethane is from the viewpoint of ensuring the productivity during polymerization and the mechanical strength of the laminated tube. It is preferable that it is 0.25-3.0, and it is more preferable that it is 0.40-2.5.

  (B2) Aromatic polyester polymer, if necessary, various additives, for example, reinforcing agents having various shapes such as fibrous, plate-like, and granular, antioxidants, as long as the physical properties are not significantly impaired. Agent, heat stabilizer, colorant, ultraviolet absorber, mold release agent, antistatic agent, antibacterial agent, fluorescent whitening agent, crystallization accelerator, crystal nucleating agent, filler, lubricant, antifogging agent, antiblocking An agent, a slip agent, a plasticizer, a bending fatigue resistance improving material, a flame retardant, a flame retardant aid and the like can be added.

  The (B) polyester polymer composition used in the present invention comprises (B1) a polyglycolic acid polymer and (B2) an aromatic polyester polymer, and the mixing ratio of both is the chemical liquid permeation preventing property of the laminated tube. And (B1) the amount of the polyglycolic acid polymer with respect to 100% by mass of the (B) polyester polymer composition, from the viewpoint of ensuring the durability of the interlayer adhesion, particularly the interlayer adhesion under a high temperature atmosphere. Is 60 to 90% by mass, preferably 62 to 87% by mass, more preferably 65 to 85% by mass, and the blending amount of (B2) aromatic polyester polymer is 40 to 10% by mass. Yes, it is preferably 38 to 13% by mass, and more preferably 35 to 15% by mass.

  (B) Polyester polymer composition, if necessary, various additives, for example, reinforcing agents having various shapes such as fibrous, plate-like, and granular, oxidation within a range that does not significantly impair the physical properties Inhibitors, heat stabilizers, colorants, UV absorbers, mold release agents, antistatic agents, antibacterial agents, fluorescent whitening agents, crystallization accelerators, crystal nucleating agents, fillers, lubricants, antifogging agents, anti A blocking agent, a slip agent, a plasticizer, a bending fatigue resistance improving material, a flame retardant, a flame retardant aid and the like can be added. (B) In order to improve the low temperature impact resistance of the polyester-based polymer composition, it is preferable to add an impact resistance improver, and (A) according to ASTM D-790 described in the description of the aliphatic polyamide. It is more preferable to add a rubber-like polymer having a flexural modulus measured by measuring 500 MPa or less.

  In the (B) polyester polymer composition, there are no particular limitations on the method of blending and mixing the (B1) polyglycolic acid polymer and the (B2) aromatic polyester polymer, and various conventionally known methods. Can be adopted. Along with other additives blended as necessary, it can be produced by, for example, a dry blending method of both, a melt kneading method of both, or the like. The melt kneading can be performed using a kneader such as a single screw extruder, a twin screw extruder, a kneader, or a Banbury mixer.

[(C) Modified polyester-based elastomer]
The (C) modified polyester elastomer used in the present invention is a polyester elastomer graft-modified with an α, β-ethylenically unsaturated carboxylic acid, and an α, β-ethylenically unsaturated carboxylic acid (an anhydride thereof). Is also a polymer obtained by graft-modifying a polyester-based elastomer.

(C) The polyester elastomer that is a constituent of the modified polyester elastomer is preferably a saturated polyester elastomer, and more preferably a saturated polyester elastomer containing a soft segment made of polyalkylene ether glycol. For example, it is more preferable to use an aromatic polyester as the hard segment and a polyalkylene ether glycol or an aliphatic polyester as the soft segment. Polyester polyether block copolymers using polyalkylene ether glycol as the soft segment are particularly preferred. From the viewpoint of exhibiting sufficient adhesion to (A) aliphatic polyamide and (B) polyester polymer composition and imparting sufficient strength and low-temperature impact resistance to the laminated tube, the polyalkylene ether glycol component It is preferable that content is 5-90 mass% with respect to the block copolymer to produce | generate, It is more preferable that it is 30-80 mass%, It is further more preferable that it is 55-80 mass%.
The content of the polyalkylene ether glycol component can be calculated based on the chemical shift of the hydrogen atom and its content using ¹ H-NMR.

  Polyester polyether block copolymers include aliphatic and / or alicyclic diols having 2 to 12 carbon atoms, aromatic dicarboxylic acids and / or alicyclic dicarboxylic acids or ester-forming derivatives thereof, and poly A product obtained by polycondensing an oligomer obtained by esterification or transesterification using alkylene ether glycol as a raw material is preferable.

  As the aliphatic and / or alicyclic diol having 2 to 12 carbon atoms, those usually used as raw materials for polyesters, particularly polyester thermoplastic elastomers, can be used. For example, 1,2-ethanediol, 1, 3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1,8-octanediol, 1,9-nonanediol, 2-methyl-1,8-octanediol 1,10-decanediol, 1,12-dodecanediol, 1,3- / 1,4-cyclohexanediol, 1,4-cyclohexanedimethanol, and the like, and these should be used alone or in combination. Can do. Among these, 1,2-ethanediol and 1,4-butanediol are preferable, and 1,4-butanediol is more preferable.

  As the aromatic dicarboxylic acid and / or alicyclic dicarboxylic acid, those generally used as raw materials for polyesters, particularly polyester thermoplastic elastomers can be used. For example, terephthalic acid, isophthalic acid, phthalic acid 1,4- / 2,6- / 2,7-naphthalenedicarboxylic acid, 1,3- / 1,4-cyclohexanedicarboxylic acid, and the like. These can use 1 type (s) or 2 or more types. Among these, terephthalic acid and 2,6-naphthalenedicarboxylic acid are preferable, and terephthalic acid is more preferable. Examples of the ester-forming derivative of aromatic dicarboxylic acid and / or alicyclic dicarboxylic acid include alkyl esters such as dimethyl ester and diethyl ester of the dicarboxylic acid. These can use 1 type (s) or 2 or more types. Among these, dimethyl terephthalate and dimethyl 2,6-naphthalene are preferable.

  In addition to the above components, trifunctional triols, tricarboxylic acids, or esters thereof may be copolymerized in small amounts, and aliphatic dicarboxylic acids such as adipic acid or dialkyl esters thereof may also be copolymerized.

  As said polyalkylene ether glycol, the number average molecular weight is 400-6 from a viewpoint of ensuring the block property of a copolymer, suppressing generation | occurrence | production of phase separation in a system, and ensuring the physical property of a polymer sufficiently. 000, preferably 500 to 4,000, more preferably 600 to 3,000. Here, the number average molecular weight refers to that measured by gel permeation chromatography (GPC). For calibration of GPC, a POLYTETRAHYDROFURAN calibration kit manufactured by POLYMERLABORATORIES, UK may be used.

  Specific examples of the polyalkylene ether glycol include polyethylene glycol, poly (propylene ether) glycol, poly (tetramethylene ether) glycol, poly (hexamethylene ether) glycol and the like. These can use 1 type (s) or 2 or more types. Among these, poly (tetramethylene ether) glycol is preferable.

  (C) Examples of the α, β-ethylenically unsaturated carboxylic acid that is a constituent of the modified polyester elastomer include acrylic acid, maleic acid, fumaric acid, tetrahydrofumaric acid, itaconic acid, citraconic acid, crotonic acid, and isocrotone. Unsaturated carboxylic acids such as acids, succinic acid 2-octen-1-yl anhydride, succinic acid 2-dodecen-1-yl anhydride, succinic acid 2-octadecene-1-yl anhydride, maleic acid anhydride, 2 , 3-dimethylmaleic anhydride, bromomaleic anhydride, dichloromaleic anhydride, citraconic anhydride, itaconic anhydride, 1-butene-3,4-dicarboxylic anhydride, 1-cyclopentene-1, 2-dicarboxylic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, exo-3,6-epoxy-1,2,3,6-tetrahydrophthalic anhydride, 5-norbornene-2,3-dicarboxylic anhydride, methyl-5-norbornene-2,3-dicarboxylic anhydride, endo-bicyclo [2.2.2] oct-5-ene-2,3-dicarboxylic anhydride, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid Examples thereof include unsaturated carboxylic acid anhydrides such as anhydrides. The above α, β-ethylenically unsaturated carboxylic acid can be appropriately selected according to the polyester elastomer to be modified and the modification conditions, and one or more can be used. The α, β-ethylenically unsaturated carboxylic acid can be used by dissolving in an organic solvent or the like.

  The modification reaction of the polyester elastomer is preferably performed by reacting the polyester elastomer with an α, β-ethylenically unsaturated carboxylic acid. And this modification | denaturation reaction can also be performed simultaneously with high molecular weight reaction by performing in presence of an active hydrogen compound. In the modification, a radical generator is preferably used. In this modification reaction, a graft reaction in which an α, β-ethylenically unsaturated carboxylic acid or a derivative thereof is added to a polyester elastomer mainly occurs, but a decomposition reaction also occurs. As a result, the modified polyester elastomer has a lower molecular weight and a lower melt viscosity. Further, in the above modification reaction, it is generally considered that a transesterification reaction or the like occurs as another reaction, and the obtained reaction product is generally a composition containing unreacted raw materials, The modified polyester elastomer may be used alone. When the reaction product is a composition, the content of the modified polyester elastomer is preferably 10% by mass or more, and more preferably 30% by mass or more.

  As radical generators, t-butyl hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, 2,5-dimethyl-2,5-bis (tertiary butyl) Oxy) hexane, 3,5,5-trimethylhexanoyl peroxide, t-butyl peroxybenzoate, benzoyl peroxide, dicumyl peroxide, 1,3-bis (t-butylperoxyisopropyl) benzene, dibutyl peroxy Organic and inorganic peroxides such as oxide, methyl ethyl ketone peroxide, potassium peroxide, hydrogen peroxide, 2,2′-azobisisobutyronitrile, 2,2′-azobis (isobutylamide) dihalide, 2,2 '-Azobis [2-methyl-N- (2-hydroxyethyl Propionamide], azo compounds such as azodi -t- butane, carbon radical generating agents such as dicumyl like. The radical generator can be appropriately selected according to the type of polyester elastomer used for the modification reaction, the type of α, β-ethylenically unsaturated carboxylic acid, and the modification conditions, and one or more of them can be selected. Can be used. The radical generator can be used by dissolving in an organic solvent or the like.

(C) As a modification reaction for obtaining a modified polyester elastomer, a known reaction method such as a melt-kneading reaction method, a solution reaction method, a suspension-dispersion reaction or the like can be used, but a melt-kneading reaction method is usually preferable. .
In the case of the melt-kneading reaction method, the components described above and other additives as necessary may be uniformly mixed at a predetermined blending ratio and then melt-kneaded. For mixing, after mixing uniformly using a Henschel mixer, ribbon blender, V-type blender, etc., a Banbury mixer, kneader, roll, uniaxial or biaxial multi-screw kneading extruder, etc. are used for melt-kneading. The Further, an active hydrogen compound described later and other optional components may be supplied from the middle and melt kneaded. The melt-kneading temperature is preferably 100 to 300 ° C., more preferably 120 to 280 ° C., and further preferably 150 to 250 ° C. so that the resin is not thermally deteriorated.

  The blending amount of the α, β-ethylenically unsaturated carboxylic acid is sufficiently modified, ensures adhesion, and does not excessively reduce the melt viscosity of the (C) modified polyester elastomer to be produced. From the viewpoint of securing the above, it is preferably 0.01 to 30 parts by mass, more preferably 0.05 to 5 parts by mass, and 0.1 to 1 part by mass with respect to 100 parts by mass of the polyester elastomer. More preferably it is. ,

  From the standpoint of ensuring the strength of the resulting laminated tube, the blending amount of the radical generator is sufficiently modified, ensuring adhesion, suppressing low molecular weight (decrease in viscosity) during modification of the polyester elastomer, The amount is preferably 0.001 to 3 parts by mass, more preferably 0.005 to 0.5 parts by mass, and 0.01 to 0.2 parts by mass with respect to 100 parts by mass of the polyester elastomer. Is more preferable, and it is especially preferable that it is 0.01-0.1 mass part.

  About the (C) modified polyester elastomer obtained as described above, from the viewpoint of ensuring the mechanical strength of the obtained laminated tube and the rubber elasticity and interlayer adhesion, the hardness according to durometer type D measured according to JIS K-6253 (JIS-D hardness) is preferably 10 to 80, more preferably 15 to 70, and still more preferably 20 to 60. Furthermore, (C) MFR of modified polyester elastomer (230 ° C, 2.16 kg load) does not excessively lower the melt tension of (C) modified polyester elastomer, preventing problems such as drawdown during molding. From the viewpoint of securing moldability without excessively shorting the fluidity, it is preferably 1 to 300 g / 10 minutes, more preferably 3 to 150 g / 10 minutes, and 5 to 100 g / 10 minutes. More preferably it is.

The modification rate (graft amount) of the (C) modified polyester elastomer can be determined from the spectrum obtained by ¹ H-NMR measurement according to the following formula. Graft amount (mass%) = 100 × (C ÷ 3 × 98) / {(A × 148 ÷ 4) + (B × 72 ÷ 4) + (C ÷ 3 × 98)}
(However, A is an integral value of 7.8 to 8.4 ppm, B is an integral value of 1.2 to 2.2 ppm, and C is an integral value of 2.4 to 2.9 ppm.)

  The modification rate (graft amount) of the (C) modified polyester elastomer determined as described above is such that the functional group in the (C) modified polyester elastomer is not too small, and the interlayer adhesion is appropriately ensured. From the viewpoint of suppressing the molecular deterioration in the process and securing the strength of the obtained laminated tube, it is preferably 0.01 to 10% by mass, more preferably 0.03 to 7% by mass, and More preferably, it is 05-5 mass%.

  Further, in order to improve adhesiveness, vinyl aroma such as styrene, methyl styrene, ethyl styrene, isopropyl styrene, phenyl styrene, o-methyl styrene, 2,4-dimethyl styrene, o-chloro styrene, o-chloromethyl styrene, etc. A group monomer or the like can also be blended as a modification aid.

  (C) Arbitrary components can be mix | blended with a modified polyester elastomer according to the objective. Specifically, resin component, rubber component, talc, calcium carbonate, mica, glass fiber filler, plasticizer such as paraffin oil, antioxidant, heat stabilizer, light stabilizer, ultraviolet absorber, neutralizer Add various additives such as lubricants, anti-fogging agents, anti-blocking agents, slip agents, cross-linking agents, cross-linking aids, colorants, flame retardants, dispersants, antistatic agents, antibacterial agents, fluorescent whitening agents, etc. be able to.

  As described above, the (C) modified polyester elastomer is a polyester elastomer graft-modified with an α, β-ethylenically unsaturated carboxylic acid. That is, since the (C) modified polyester elastomer is a saturated polyester thermoplastic elastomer containing a polyalkylene ether glycol segment, it has excellent interlayer adhesion with the (B) polyester polymer composition, and α, β- Since it is graft-modified with an ethylenically unsaturated carboxylic acid, it has excellent interlayer adhesion with (A) aliphatic polyamide and (D) semi-aromatic polyamide or polyoxamide, and in particular, interlayer adhesion in the laminated tube is: Even in a high temperature atmosphere of 80 ° C. or higher, the decrease is small and the durability is good.

[(D1) Semi-aromatic polyamide or (D2) polyoxamide] The (D1) semi-aromatic polyamide used in the present invention contains 60 mol% of aliphatic diamine units having 9 to 13 carbon atoms with respect to the total diamine units. It consists of the diamine unit containing above and the dicarboxylic acid unit containing 50 mol% or more of terephthalic acid and / or naphthalenedicarboxylic acid units with respect to all dicarboxylic acid units. On the other hand, the polyoxamide is a dicarboxylic acid containing 60 mol% or more of oxalic acid units relative to all dicarboxylic acid units, and a diamine unit containing 60 mol% or more of aliphatic diamine units having 9 to 13 carbon atoms based on all diamine units. Units (hereinafter,

  (D1) The content of the terephthalic acid and / or naphthalenedicarboxylic acid unit in the semi-aromatic polyamide is from the viewpoint of sufficiently ensuring various physical properties such as heat resistance, chemical resistance and chemical solution permeation prevention properties of the obtained laminated tube. , 50 mol% or more, preferably 60 mol% or more, more preferably 75 mol% or more, and still more preferably 90 mol% or more with respect to all dicarboxylic acid units. Examples of the naphthalenedicarboxylic acid unit include units derived from 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, and 1,5-naphthalenedicarboxylic acid. These can use 1 type (s) or 2 or more types. Among the naphthalenedicarboxylic acid units, units derived from 2,6-naphthalenedicarboxylic acid are preferred.

  (D1) The dicarboxylic acid unit in the semi-aromatic polyamide may be other than units derived from terephthalic acid and / or naphthalenedicarboxylic acid as long as the excellent properties of the laminated tube of the present invention are not impaired. Dicarboxylic acid units may be included. Other dicarboxylic acid units include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, 2,2,4- / 2,4,4-trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 2,2-diethylsuccinic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and other aliphatic dicarboxylic acids, 1,3-cyclopentanedicarboxylic acid, 1, Alicyclic dicarboxylic acids such as 3- / 1,4-cyclohexanedicarboxylic acid, isophthalic acid, 1,3- / 1,4-phenylenedioxydiacetic acid, 4,4′-oxydibenzoic acid, diphenylmethane-4,4 '-Dicarboxylic acid, diphenylethane-4,4'-dicarboxylic acid, diphenylpropane-4,4'-dicarboxylic acid, diphenyl ether-4,4'- Examples include units derived from aromatic dicarboxylic acids such as carboxylic acid, diphenylsulfone-4,4′-dicarboxylic acid, 4,4′-biphenyldicarboxylic acid, and 4,4′-triphenyldicarboxylic acid. Species or two or more can be used. Among these, units derived from aromatic dicarboxylic acids are preferred. The content of other dicarboxylic acid units is 50 mol% or less, preferably 40 mol%, more preferably 25 mol% or less, and even more preferably 10 mol% or less. Furthermore, polycarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used within a range where melt molding is possible.

  In addition, the content of the aliphatic diamine unit having 9 to 13 carbon atoms in the (D1) semi-aromatic polyamide is from the viewpoint of sufficiently ensuring the heat resistance, chemical resistance, impact resistance, etc. of the obtained laminated tube. It is 60 mol% or more with respect to all the diamine units, it is preferable that it is 75 mol% or more, and it is more preferable that it is 90 mol% or more.

  The aliphatic diamine unit having 9 to 13 carbon atoms is derived from 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, and 1,13-tridecanediamine. Units. As long as the carbon number satisfies the above, 2,2,4- / 2,4,4-trimethyl-1,6-hexanediamine, 2,4-diethyl-1,6-hexanediamine, 2,2- / 2, 3- / 2,4- / 2,5-dimethyl-heptanediamine, 2- / 3- / 4-methyl-1,8-octanediamine, 1,3- / 1,4- / 2,2- / 2 , 4- / 3,3- / 3,4- / 4,4- / 4,5-dimethyl-1,8-octanediamine, 5-methyl-1,9-nonanediamine, 2- / 3-butyl-1 , Units derived from branched aliphatic diamines such as 8-octanediamine may be contained. These can use 1 type (s) or 2 or more types.

  Among the above aliphatic diamine units having 9 to 13 carbon atoms, (A) 1,9-nonanediamine and / or 2-methyl-1 from the viewpoint of coextrusion moldability with an aliphatic polyamide and the like, and prevention of chemical liquid permeation. , 8-octanediamine is preferred, and units derived from 1,10-decanediamine and 1,12-dodecanediamine are preferred from the viewpoint of low-temperature impact resistance. Furthermore, the molar ratio of the 1,9-nonanediamine unit to the 2-methyl-1,8-octanediamine unit is 30:70 to 98: 2 mol% from the viewpoint of the balance between moldability and impact resistance. Preferably, it is 40: 60-95: 5 mol%.

  (D1) If the diamine unit in the semi-aromatic polyamide is within a range that does not impair the excellent properties of the laminated tube of the present invention, other units other than units derived from aliphatic diamines having 9 to 13 carbon atoms It may contain a diamine unit. Other diamine units include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,14-tetradecanediamine, , 15-pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, aliphatic diamine such as 2- / 3-methyl-1,5-pentanediamine, 1,3 -/ 1,4-cyclohexanediamine, 1,3- / 1,4-cyclohexanedimethylamine, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, bis (3-methyl-4-aminocyclohexyl) ) Methane, 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, norbornanedimethylamine, tricyclodecanedimethyl Alicyclic diamines such as amines, m- / p-phenylenediamine, m- / p-xylylenediamine, 1,4- / 1,5- / 2,6- / 2,7-naphthalenedimethylamine, 4, Examples include units derived from aromatic diamines such as 4′-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl ether. Can use 1 type (s) or 2 or more types. The content of these other diamine units is 40 mol% or less, preferably 25 mol% or less, and more preferably 10 mol% or less.

  (D1) The semi-aromatic polyamide may contain 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 caprolactam, enantolactam, undecane lactam, dodecane lactam, α-pyrrolidone, α-piperidone, 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-amino Examples include units derived from dodecanoic acid. These can use 1 type (s) or 2 or more types. The content of units other than dicarboxylic acid units and diamine units is preferably 30 mol% or less, and more preferably 10 mol% or less.

  Based on JIS K-6920, the relative viscosity of the semi-aromatic polyamide measured under the conditions of 96% sulfuric acid, polyamide concentration of 1% and 25 ° C. is sufficient for the productivity and mechanical strength of the laminated tube. From the viewpoint of ensuring the thickness, it is preferably 1.5 to 4.0, more preferably 1.8 to 3.5, and still more preferably 2.0 to 3.0.

  Furthermore, (D1) semi-aromatic polyamide production equipment includes batch-type reaction kettles, one-tank or multi-tank continuous reaction equipment, tubular continuous reaction equipment, single-screw kneading extruder, twin-screw kneading extruder, etc. A known polyamide production apparatus such as a kneading reaction extruder may be used. As a polymerization method, a known method such as melt polymerization, solution polymerization, or solid phase polymerization can be used, and polymerization can be performed by repeating normal pressure, reduced pressure, and pressure operations. These polymerization methods can be used alone or in appropriate combination.

  (D2) The polyoxamide is a dicarboxylic acid containing 60 mol% or more of an aliphatic diamine unit having 9 to 13 carbon atoms with respect to all diamine units, and a dicarboxylic acid containing 60 mol% or more of oxalic acid units with respect to all dicarboxylic acid units. Polyamide composed of acid units.

  (D2) The content of the oxalic acid unit in the polyoxamide is 60% with respect to all the dicarboxylic acid units from the viewpoint of sufficiently securing various physical properties such as heat resistance, chemical resistance, and chemical solution permeation prevention properties of the obtained laminated tube. It is preferably at least 70 mol%, more preferably at least 80 mol%, still more preferably at least 90 mol%.

  Examples of oxalic acid units include units derived from oxalic acid or its ester-forming derivatives. Units derived from ester-forming derivatives include aliphatic monohydric alcohols such as dimethyl oxalate, diethyl oxalate, di-n- (or i-) propyl oxalate, di-n- (or i-, or t-) butyl oxalate And units derived from aromatic alcohols such as oxalic acid diesters of alicyclic alcohols such as dicyclohexyl oxalate and diphenyl oxalate. These can use 1 type (s) or 2 or more types. Among these, a unit derived from an oxalic acid diester of an aliphatic monohydric alcohol having 3 or more carbon atoms, an oxalic acid diester of an alicyclic alcohol, or an oxalic acid diester of an aromatic alcohol, and preferably dibutyl oxalate and / or More preferred are units derived from diphenyl oxalate.

  (D2) The dicarboxylic acid unit in the polyoxamide may contain other dicarboxylic acid units other than the unit derived from oxalic acid as long as the excellent properties of the laminated tube of the present invention are not impaired. Other dicarboxylic acid units include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, 2,2,4- / 2,4,4-trimethyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 2,2-diethylsuccinic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid and other aliphatic dicarboxylic acids, 1,3-cyclopentanedicarboxylic acid, 1, Alicyclic dicarboxylic acids such as 3- / 1,4-cyclohexanedicarboxylic acid, phthalic acid, terephthalic acid, isophthalic acid, 1,3- / 1,4-phenylenedioxydiacetic acid, 2,6- / 2,7 -/ 1,4- / 1,5-naphthalenedicarboxylic acid, anthracene dicarboxylic acid, 4,4'-oxydibenzoic acid, 4,4'-diphenyldicarboxylic acid, diphenylmeth 4,4′-dicarboxylic acid, diphenylethane-4,4′-dicarboxylic acid, diphenylpropane-4,4′-dicarboxylic acid, diphenyl ether-4,4′-dicarboxylic acid, diphenylsulfone-4,4′- Examples thereof include units derived from aromatic dicarboxylic acids such as dicarboxylic acids and 4,4′-triphenyldicarboxylic acids, and these may be used alone or in combination of two or more. The content of other dicarboxylic acid units is 40 mol% or less, preferably 30 mol%, more preferably 20 mol% or less, and even more preferably 10 mol% or less. Furthermore, polycarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used within a range where melt molding is possible.

  The content of the aliphatic diamine unit having 9 to 13 carbon atoms in (D2) polyoxamide is all diamine units from the viewpoint of sufficiently ensuring the heat resistance, chemical resistance, impact resistance, etc. of the obtained laminated tube. On the other hand, it is 60 mol% or more, preferably 75 mol% or more, and more preferably 90 mol% or more.

  The aliphatic diamine unit having 9 to 13 carbon atoms is derived from 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, and 1,13-tridecanediamine. Units. As long as the carbon number satisfies the above, 2,2,4- / 2,4,4-trimethyl-1,6-hexanediamine, 2,4-diethyl-1,6-hexanediamine, 2,2- / 2, 3- / 2,4- / 2,5-dimethyl-heptanediamine, 2- / 3- / 4-methyl-1,8-octanediamine, 1,3- / 1,4- / 2,2- / 2 , 4- / 3,3- / 3,4- / 4,4- / 4,5-dimethyl-1,8-octanediamine, 5-methyl-1,9-nonanediamine, 2- / 3-butyl-1 , Units derived from branched aliphatic diamines such as 8-octanediamine may be contained. These can use 1 type (s) or 2 or more types.

  Among the above aliphatic diamine units having 9 to 13 carbon atoms, 1,9-nonanediamine and / or 2-methyl- are excellent from the viewpoint of melt moldability and low water absorption, chemical resistance and hydrolysis resistance. Units derived from 1,8-octanediamine, 1,10-decanediamine and 1,12-dodecanediamine are preferred. Furthermore, the molar ratio of the 1,9-nonanediamine unit to the 2-methyl-1,8-octanediamine unit is 30:70 to 98: 2 mol% from the viewpoint of the balance between moldability and impact resistance. Preferably, it is 40: 60-95: 5 mol%.

  (D2) The diamine unit in the polyoxamide is a diamine unit other than a unit derived from an aliphatic diamine having 9 to 13 carbon atoms, as long as the excellent properties of the laminated tube of the present invention are not impaired. May be included. Other diamine units include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,14-tetradecanediamine, , 15-pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, aliphatic diamine such as 2- / 3-methyl-1,5-pentanediamine, 1,3 -/ 1,4-cyclohexanediamine, 1,3- / 1,4-cyclohexanedimethylamine, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, bis (3-methyl-4-aminocyclohexyl) ) Methane, 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, norbornanedimethylamine, tricyclodecanedimethyl Alicyclic diamines such as amines, m- / p-phenylenediamine, m- / p-xylylenediamine, 1,4- / 1,5- / 2,6- / 2,7-naphthalenedimethylamine, 4, Examples include units derived from aromatic diamines such as 4′-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl ether. Can use 1 type (s) or 2 or more types. The content of other diamine units is 40 mol% or less, preferably 25 mol% or less, and more preferably 10 mol% or less.

  (D2) The polyoxamide 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 caprolactam, enantolactam, undecane lactam, dodecane lactam, α-pyrrolidone, α-piperidone, 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11-aminoundecanoic acid, 12-amino Examples include units derived from dodecanoic acid. These can use 1 type (s) or 2 or more types. The content of units other than dicarboxylic acid units and diamine units is preferably 30 mol% or less, and more preferably 10 mol% or less.

  According to JIS K-6920, the relative viscosity of the polyoxamide measured under the conditions of 96% sulfuric acid, polyamide concentration of 1% and 25 ° C. ensures sufficient productivity and mechanical strength of the laminated tube. From the viewpoint, it is preferably 1.8 to 6.0, more preferably 2.0 to 5.5, and still more preferably 2.5 to 4.5.

  (D2) As a polyoxamide production apparatus, a kneading reaction extruder 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. For example, a known polyamide production apparatus can 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. Specifically, it is preferable to carry out in the order of (i) pre-polycondensation step and (ii) post-polycondensation step as shown by the following operations.

(I) Pre-polycondensation step: First, the inside of the reactor is purged with nitrogen, and then the diamine and, for example, oxalic acid diester are mixed. When mixing, a solvent in which both the diamine and the oxalic acid diester are soluble may be used. The solvent in which both the diamine component and the oxalic acid diester are soluble is not particularly limited, and examples thereof include toluene, xylene, trichlorobenzene, phenol, trifluoroethanol and the like. Of these, toluene is preferred. For example, after heating the toluene solution which melt | dissolved diamine to 50 degreeC, oxalic acid diester is added with respect to this. At this time, the charging ratio of the oxalic acid diester and the diamine is oxalic acid diester / the diamine, and is usually 0.8 to 1.5 (molar ratio) and 0.91 to 1.1 (molar ratio). Preferably, it is 0.99 to 1.01 (molar ratio).
The temperature in the reactor charged in this way is increased under normal pressure while stirring and / or nitrogen bubbling. The final temperature reached in the prepolycondensation step is preferably 80 to 150 ° C, and more preferably 100 to 140 ° C. The reaction time at the final temperature is preferably 3 to 6 hours.

  (Ii) Post-polycondensation step: In order to further increase the molecular weight, the polymer produced in the pre-polycondensation step is gradually heated in the reactor under normal pressure. From the final reached temperature of the pre-polycondensation step, that is, from 80 to 150 ° C. in the temperature raising process, the final reached temperature of the post-polycondensation step is preferably 220 to 300 ° C., more preferably 230 to 280 ° C. It is more preferable that it is 240-270 degreeC. The post-polymerization reaction time including the temperature raising time is preferably 1 to 8 hours, and more preferably 2 to 6 hours. Furthermore, in the post-polymerization step, polymerization can be performed under reduced pressure as necessary. When carrying out vacuum polymerization, the final ultimate pressure is preferably 13.3 Pa to 0.1 MPa.

  Hereinafter, the manufacturing method of (D2) polyoxamide is demonstrated concretely. First, the raw material oxalic acid diester is charged into a container and purged with nitrogen. The container is not particularly limited as long as it can withstand the temperature and pressure of the polycondensation reaction to be performed later. Thereafter, the container is heated to a temperature at which it is mixed with the raw material diamine, and then the diamine is injected to start the polycondensation reaction. The temperature at which the raw materials are mixed is not particularly limited as long as it is a temperature not lower than the melting point and lower than the boiling point of the oxalic acid diester and diamine, and the polyoxamide generated by the polycondensation reaction of the oxalic acid diester and diamine is not thermally decomposed. When the mixing temperature is equal to or higher than the boiling point of the alcohol produced by the condensation reaction, it is desirable to use a container equipped with a device for distilling and condensing the alcohol. In addition, when pressure polymerization is performed in the presence of an alcohol generated by a condensation reaction, a pressure vessel is used. The charging ratio of oxalic acid diester and diamine is oxalic acid diester / diamine, and is usually 0.8 to 1.2 (molar ratio), preferably 0.91 to 1.09 (molar ratio). It is more preferable that it is .98 to 1.02 (molar ratio).

  Next, the inside of the container is heated to a temperature not lower than the melting point of the polyoxamide resin and not higher than the temperature at which it is not thermally decomposed. For example, a diamine and oxalic acid composed of 1,9-nonanediamine and 2-methyl-1,8-octanediamine and having a molar ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine of 85:15 In the case of a polyoxamide resin using dibutyl as a raw material, since the melting point is 235 ° C., it is preferable to raise the temperature to 240 to 280 ° C. (pressure is 2 to 4 MPa). While distilling off the produced alcohol, the polycondensation reaction is continued under an atmospheric pressure of nitrogen or reduced pressure as necessary. When raw materials are mixed in a pressure-resistant vessel and subjected to pressure polymerization in the presence of an alcohol produced by a condensation reaction, the pressure is first released while the produced alcohol is distilled off. Thereafter, the polycondensation reaction is continued under an atmospheric pressure of nitrogen or reduced pressure as necessary. In the case of performing the polymerization under reduced pressure, the final ultimate pressure is preferably 0.1 to 760 Torr (13.3 Pa to 0.1 MPa). It is preferable that temperature is 240-280 degreeC. The alcohol is cooled and liquefied by a water-cooled condenser and recovered.

  (D1) Semi-aromatic polyamide or (D2) polyoxamide has a terminal amino group concentration per gram of the polyamide [A] (μeqg), a terminal carboxyl group concentration or a terminal formamide group concentration [B] (μeq / g). (A)> [B] +5 (hereinafter sometimes referred to as (D1) terminal-adjusted semi-aromatic polyamide or (D2) terminal-adjusted polyoxamide). In view of the interlaminar adhesiveness, particularly the durability of the interlaminar adhesive strength in a high temperature atmosphere, it is more preferable that [A]> [B] +10, and further that [A]> [B] +15. preferable. Furthermore, [A]> 20 is preferable, and 30 <[A] <120 is more preferable from the viewpoints of melt stability and suppression of gelled material generation.

  Polyamide is a mixture of a large number of polymer chains of different lengths, and one polymer chain of a polyamide has two end groups unless it is branched, and usually has amino groups derived from polyamide raw materials and It is a carboxyl group. However, the type of terminal group varies depending on the type of raw material, the ratio of the raw material, the manufacturing method, the modifier, the end-capping agent, and the like during polyamide production. (D2) In the polyoxamide, when the diamine and oxalic acid diester are used as raw materials, the terminal group is any one of an amino group, an alkoxy group, and a formamide group. The formation of the formamide group is generated by decarboxylation of the terminal alkoxy group during the polycondensation reaction, and is affected by moisture in the raw material (the diamine and oxalic acid diester) and moisture in the reaction system.

The terminal amino group concentration [A] (μeq / 1 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 / 1 g) can be measured by dissolving the polyamide in benzyl alcohol and titrating with 0.05N sodium hydroxide solution. The terminal formamide group concentration [B] (μeq / 1 g) can be calculated from the signal intensity obtained from the ¹ H-NMR spectrum, as described in Examples below.

  (D1) terminal-adjusted semi-aromatic polyamide or (D2) terminal-adjusted polyoxamide is polymerized or copolymerized in the presence of amines by a known method such as melt polymerization, solution polymerization or solid phase polymerization. It is manufactured by the thing. Alternatively, it is produced by melt-kneading in the presence of amines after polymerization. Thus, amines can be added at any stage during polymerization, or after polymerization, at any stage during melt-kneading, but it is preferable to add them at the stage during polymerization.

  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. One or more amines and carboxylic acids can be used. (A) Monoamines, diamines, triamines, polyamines, monocarboxylic acids, dicarboxylic acids, tricarboxylic acids, etc. described in the description of the aliphatic polyamide As well.

  The amount of amines to be added takes into account the terminal amino group concentration, terminal carboxyl group concentration or terminal formamide group concentration and relative viscosity of the (D1) terminal-adjusted semi-aromatic polyamide or (D2) terminal-adjusted polyoxamide to be produced. Thus, it is determined appropriately by a known method. From the viewpoint of obtaining sufficient reactivity and facilitating the production of polyamide having a desired viscosity, (), amines are usually used with respect to 1 mol of the monomer constituting the polyamide repeating unit or 1 mol of the polyamide raw material of the monomer unit. Is preferably 0.5 to 200 meq / mol, more preferably 1.0 to 100 meq / mol (the equivalent of the amino group reacts 1: 1 with a carboxyl group or an alkoxy group). The amount of the amino group forming the amide group or oxamide group is 1 equivalent).

  In (D1) terminal-adjusted semi-aromatic polyamide or (D2) terminal-adjusted polyoxamide, it is preferable to add diamine and / or polyamine during polymerization in order to satisfy the condition of terminal group concentration among the amines exemplified above. From the viewpoint of suppression of gel generation, at least one selected from the group consisting of aliphatic diamines, alicyclic diamines, and polyamines is more preferable. (D1) The semi-aromatic polyamide is a diamine unit containing 60 mol% or more of an aliphatic diamine unit having 9 to 13 carbon atoms with respect to all diamine units, and terephthalic acid and / or naphthalene with respect to all dicarboxylic acid units. A dicarboxylic acid unit containing 50 mol% or more of a dicarboxylic acid unit, and (D2) polyoxamide is a diamine unit containing 60 mol% or more of an aliphatic diamine unit having 9 to 13 carbon atoms with respect to the diamine unit; Since it consists of a dicarboxylic acid unit containing 60 mol% or more of oxalic acid units with respect to the unit, in order to satisfy the condition of the terminal group concentration, the raw material diamine component at the time of polymerization is compared with the raw material dicarboxylic acid or its ester-forming derivative component It is a simple and preferable method to charge excessively.

  Further, (D1) terminal-adjusted semi-aromatic polyamide or (D2) terminal-adjusted polyoxamide may be a mixture of two or more kinds of polyamides having different terminal group concentrations as long as the terminal group concentration is satisfied. In this case, the terminal amino group concentration, terminal group carboxyl or formamide group concentration of the polyamide mixture is determined by the terminal amino group concentration, terminal carboxyl group or formamide group concentration of the polyamide constituting the mixture and the blending ratio thereof.

  Furthermore, (D1) semi-aromatic polyamide or (D2) polyoxamide may contain an antioxidant, heat stabilizer, ultraviolet absorber, light stabilizer, lubricant, inorganic filler, antistatic agent, A flame retardant, a crystallization accelerator, a plasticizer, a colorant, a lubricant, an impact resistance improving material, another thermoplastic resin, and the like may be added. In order to improve the low temperature impact resistance of (D1) semi-aromatic polyamide or (D2) polyoxamide, it is preferable to add an impact resistance improver. (A) ASTM D- described in the explanation of aliphatic polyamide It is more preferable to add a polymer having a flexural modulus measured according to 790 of 500 MPa or less.

  (D1) Semi-aromatic polyamide or (D2) polyoxamide may contain other polyamide-based resins or other thermoplastic resins. Examples of the other polyamide-based resin or other thermoplastic resin include the same resins as those in the case of the (A) aliphatic polyamide. Furthermore, it may be a mixture with (A) an aliphatic polyamide. The content of other polyamide resins or other thermoplastic resins in the mixture is preferably 20% by mass or less.

  The laminated tube according to the present invention comprises (A) a layer made of an aliphatic polyamide (a), (B1) a polyglycolic acid polymer and (B2) an aromatic polyester polymer, and (B) a polyester polymer composition. (B) layer, (C) (c) layer made of a modified polyester elastomer, and (D1) a semi-aromatic polyamide or (D2) a (d) layer made of polyoxamide. The

  As a preferable embodiment, the (c) layer is disposed between the (a) layer and the (b) layer and between the (b) layer and ((d) layer. It is possible to obtain a laminated tube having excellent durability and strength, and it is essential to include the layer (b), thereby obtaining a laminated tube having excellent chemical liquid permeation preventive properties. As a preferred embodiment, the (a) layer is arranged in the innermost layer of the laminated tube (d), and the (a) layer is arranged in the outermost layer, so that the laminated layer has excellent chemical resistance and flexibility. In addition, since the layer (d) is disposed in the innermost layer, a laminated tube excellent in chemical resistance and chemical solution permeation prevention property can be obtained.

  Moreover, the layer which consists of a polyoxamide composition which contains (D1) a semi-aromatic polyamide composition or conductive filler which contains a conductive filler in the innermost layer of the laminated tube of this invention is arrange | positioned in the innermost layer of a laminated tube. If it is used, it is excellent in chemical resistance and chemical permeation prevention, and when used as a fuel piping tube, the spark generated by the internal friction of the fuel circulating in the piping or friction with the tube wall ignites the fuel. Can be prevented. At that time, a layer made of (D1) semi-aromatic polyamide that does not contain conductive filler or (D2) polyoxamide that does not contain conductive filler is disposed outside the conductive layer, thereby providing low temperature impact resistance. It is possible to achieve both electrical conductivity and economically advantageous.

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

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

  Carbon nanotubes are referred to as hollow carbon fibrils, which have an outer region consisting of an essentially continuous multi-layer of regularly arranged carbon atoms, an inner hollow region, A hollow region is an essentially cylindrical fibril that is disposed substantially concentrically around the cylindrical axis of the fibril. Furthermore, the regularly arranged carbon atoms in the outer region are preferably graphite-like, and the diameter of the hollow region is preferably 2 to 20 nm. The outer diameter of the carbon nanotube is preferably 3.5 to 70 nm, preferably 4 to 60 nm, from the viewpoint of ensuring good dispersibility in the resin and imparting good conductivity to the resin molded body. More preferred. 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 / or 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 in terms 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 to 100 nm, The surface area (BET method) is preferably 10 m ² / g or more, more preferably 30 m ² / g or more, and more preferably 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. Carbon black preferably has a volatile content of less than 1.0% by mass.
These conductive fillers may be surface-treated with a titanate-based, aluminum-based or silane-based surface treatment agent. It is also possible to use a granulated product to improve melt kneading workability.

Since the blending amount of the conductive filler varies depending on the type of the conductive filler to be used, it cannot be specified unconditionally. However, from the viewpoint of balance between conductivity, fluidity, mechanical strength, etc., (D1) semi-aromatic polyamide or (D2) Generally, it is preferable that it is 3-30 mass parts with respect to 100 mass parts of polyoxamide.
In addition, from the viewpoint of obtaining sufficient antistatic performance, the conductive filler preferably has a surface resistivity of the melt-extruded product of 10 ⁸ Ω / square or less, more preferably 10 ⁶ Ω / square or less. preferable. However, the blending of the conductive filler tends to cause deterioration of strength and fluidity. Therefore, if the target conductivity level is obtained, it is desirable that the amount of the conductive filler is as small as possible.

[Laminated tube]
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 properties such as alcohol gasoline permeation prevention property, low temperature impact resistance, flexibility, etc. of the laminated tube. Generally, the thickness of the (a) layer, (b) layer, (c) layer, (d) layer Is preferably 3 to 90% of the total thickness of the laminated tube. In consideration of the chemical solution permeation prevention property, the thickness of the (b) layer and the (d) layer is more preferably 5 to 50% and further preferably 7 to 30% with respect to the thickness of the entire laminated tube. .

The total number of layers in the laminated tube of the present invention is not particularly limited as long as it is at least four layers including the (a) layer, the (b) layer, the (c) layer, and the (d) layer. Although the number of layers of the laminated tube of the present invention is 4 or more, it is preferably 8 or less, more preferably 5 to 7 layers, judging from the mechanism of the tube production apparatus.
In addition, the laminated tube of the present invention provides a laminated tube that has additional functions or is economically advantageous in addition to the four layers (a), (b), (c), and (d). Therefore, it may have one layer or two or more layers made of other thermoplastic resins.

Specific examples of the layer structure of the laminated tube of the present invention are shown below.
Here, it is set as the (d ') layer which consists of (D1) semi-aromatic polyamide composition containing a conductive filler, or (D2) polyoxamide composition containing a conductive filler.
4-layer structure: (a) / (c) / (b) / (d)
5-layer structure: (a) / (c) / (b) / (c) / (d), (a) / (c) / (b) / (c) / (d ′)
6-layer structure: (a) / (c) / (b) / (c) / (d) / (d ′), (a) / (c) / (b) / (c) / (a) / ( d), (a) / (c) / (b) / (c) / (a) / (d ′)
7-layer structure: (a) / (c) / (b) / (c) / (a) / (d) / (d ′)
However, it is not limited to this.
Preferred layer configurations are (a) / (c) / (b) / (c) / (d), (a) / (c) / (b) / (c) / (d) / (d ′), (A) / (c) / (b) / (c) / (a) / (d), (a) / (c) / (b) / (c) / (a) / (d) / (d ').

  Other thermoplastic resins include polymetaxylylene adipamide (polyamide MXD6) other than (A) aliphatic polyamide, (D1) semi-aromatic polyamide or (D2) polyoxamide defined in the present invention, polymetaxylyl Lensberamide (polyamide MXD8), polymetaxylylene azeamide (polyamide MXD9), polymetaxylylene sebamide (polyamide MXD10), polymetaxylylene decanamide (polyamide MXD12), polymetaxylylene terephthalamide (polyamide MXDT), Polymetaxylylene isophthalamide (polyamide MXDI), polymetaxylylene naphthalamide (polyamide MXDN), polybis (4-aminocyclohexyl) methane dodecamide (polyamide PACM12), polybis (4-aminosilane) Rohexyl) methane terephthalamide (polyamide PACMT), polybis (4-aminocyclohexyl) methane isophthalamide (polyamide PACMI), polyisophorone adipamide (polyamide IPD6), polyisophorondodecanide (polyamide IPD12), polyisophorone terephthalate Ramide (polyamide IPDT), polyisophorone isophthalamide (polyamide IPDI), polypentamethylene terephthalamide (polyamide 5T), polypentamethylene isophthalamide (polyamide 5I), polypentamethylene hexahydroterephthalamide (polyamide 5T (H) ), Polypentamethylene naphthalamide (polyamide 5N), polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (poly) Imide 6I), polyhexamethylene hexahydroterephthalamide (polyamide 6T (H)), polyhexamethylene naphthalamide (polyamide 6N), poly-2-methylpentamethylene terephthalamide (polyamide M5T), poly-2-methylpentamethylene isophthal Amide (polyamide M5I), poly 2-methylpentamethylene hexahydroterephthalamide (polyamide M5T (H)), poly 2-methylpentamethylene naphthalamide (polyamide M5N), polynonamethylene isophthalamide (polyamide 9I), poly Nonamethylene hexahydroterephthalamide (polyamide 9T (H)), poly 2-methyloctamethylene isophthalamide (polyamide M81), poly 2-methyloctamethylene hexahydroterephthalamide (polyamide M8T ( H)), polytrimethylhexamethylene isophthalamide (polyamide TMHI), polytrimethylhexamethylene hexahydroterephthalamide (polyamide TMHT (H)), polydecamethylene isophthalamide (polyamide 10I), polydecamethylenehexahydroterephthalate Lamide (polyamide 10T (H)), polyundecamethylene isophthalamide (polyamide 11I), polyundecamethylene hexahydroterephthalamide (polyamide 11T (H)), polydodecamethylene isophthalamide (polyamide 12I), poly Examples thereof include polyamide resins such as dodecamemethylene hexahydroterephthalamide (polyamide 12T (H)) and copolymers using several kinds of these polyamide raw material monomers.

  Polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer (PFA), tetrafluoro Ethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoroalkyl vinyl ether / hexafluoropropylene copolymer, ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / tetrafluoroethylene / hexafluoropropylene copolymer Polymer (EFEP), vinylidene fluoride / tetrafluoroethylene copolymer, vinylidene fluoride / hexafluoropropylene copolymer, vinylidene fluoride / perfluoroalkyl Vinyl ether copolymer, tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (THV), vinylidene fluoride / perfluoroalkyl vinyl ether / tetrafluoroethylene copolymer, ethylene / chlorotrifluoroethylene copolymer (ECTFE) ), Chlorotrifluoroethylene / tetrafluoroethylene copolymer, vinylidene fluoride / chlorotrifluoroethylene copolymer, chlorotrifluoroethylene / perfluoroalkyl vinyl ether copolymer, chlorotrifluoroethylene / hexafluoropropylene copolymer , Chlorotrifluoroethylene / tetrafluoroethylene / hexafluoropropylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene / vinylidene fluoride copolymer , Chlorotrifluoroethylene / tetrafluoroethylene / perfluoroalkyl vinyl ether copolymer, chlorotrifluoroethylene / perfluoroalkyl vinyl ether / hexafluoropropylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene / hexafluoropropylene / perfluoro Fluorine-based resins such as alkyl vinyl ether copolymers and chlorotrifluoroethylene / tetrafluoroethylene / vinylidene fluoride / perfluoroalkyl vinyl ether copolymers may be mentioned.

  Furthermore, high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultra high molecular weight polyethylene (UHMWPE), polypropylene (PP), ethylene / propylene Polymer (EPR), ethylene / butene copolymer (EBR), ethylene / vinyl acetate copolymer (EVA), saponified ethylene / vinyl acetate copolymer (EVOH), ethylene / acrylic acid copolymer (EAA) Polyolefins such as ethylene / methacrylic acid copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), ethylene / ethyl acrylate copolymer (EEA) Resin and acrylic acid, methacrylic acid, maleic acid, Malic 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- Carboxyl groups such as dicarboxylic acids and their metal salts (Na, Zn, K, Ca, Mg), maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- [2.2.1] -5-heptene-2 The above polyolefin resin containing functional groups such as epoxy groups such as acid anhydride groups such as 1,3-dicarboxylic acid anhydride, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid, etc. , Polyether resins such as polyacetal (POM) and polyphenylene oxide (PPO), polysulfone (P F), polysulfone resins such as polyethersulfone (PES), polyphenylene sulfide (PPS), polythioether resins such as polythioethersulfone (PTES), polyetheretherketone (PEEK), polyallyletherketone (PAEK) Such as polyketone resins, polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), methacrylo Polynitrile resins such as nitrile / styrene / butadiene copolymer (MBS), polymethacrylate resins such as polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA), polyvinyl acetate (PVAc), etc. Polyvinyl ester resins, polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), polyvinyl chloride / vinylidene chloride copolymers, polyvinyl chloride resins such as vinylidene chloride / methyl acrylate copolymers, cellulose acetate, cellulose butyrate, etc. Cellulose resin, polycarbonate resin such as polycarbonate (PC), polyimide resin such as thermoplastic polyimide (PI), polyamideimide (PAI), polyetherimide, thermoplastic polyurethane resin, polyamide elastomer, polyurethane elastomer, etc. Can be mentioned.

  It is also possible to laminate any substrate other than thermoplastic resin, such as paper, metal-based material, non-stretched, uniaxially or biaxially stretched plastic film or sheet, woven fabric, non-woven fabric, metal cotton, wood, etc. is there. Examples of the metal-based material include aluminum, iron, copper, nickel, gold, silver, titanium, molybdenum, magnesium, manganese, lead, tin, chromium, beryllium, tungsten, cobalt, and other metals and metal compounds, and two or more of these. Examples include 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 the laminated tube produced by the above method is produced in advance and laminated on the outside sequentially using an adhesive if necessary. The laminated tube of the present invention is preferably manufactured by coextrusion molding in which various materials are coextruded in a molten state, and both are heat-fused (melt-bonded) to produce a tube having a laminated structure in one stage.

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

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

  In all or part of the outer periphery of the laminated tube thus formed, epichlorohydrin rubber (ECO), acrylonitrile / butadiene rubber (NBR), NBR, and poly, considering stone wear, wear with other parts, and flame resistance Mixture of vinyl chloride, chlorosulfonated polyethylene rubber, chlorinated polyethylene rubber, acrylic rubber (ACM), chloroprene rubber (CR), ethylene / propylene rubber (EPR), ethylene / propylene / diene rubber (EPDM), mixture of NBR and EPDM A solid or sponge-like protective member (protector) made of a thermoplastic elastomer such as rubber, vinyl chloride, olefin, ester 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 account the flow rate of fuel (eg gasoline), and the wall thickness does not increase the permeability of the fuel, and the thickness that can maintain the normal breaking pressure of the tube. The thickness is designed so as to maintain flexibility with a satisfactory degree of workability and vibration resistance during use, but is not limited thereto. The outer diameter is preferably 4 to 300 mm, the inner diameter is 3 to 250 mm, and the wall thickness is preferably 0.5 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 the present invention is excellent in chemical solution permeation prevention properties, it is suitable for 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, brake tube, tube for window washer fluid, engine coolant (LLC) tube, reservoir tank tube, urea solution transport tube, cooler tube for cooling water, refrigerant, etc., air conditioner refrigerant tube, heater tube, Examples include load heating tubes, floor heating tubes, infrastructure supply tubes, fire extinguishers and fire extinguishing equipment tubes, medical cooling equipment tubes, ink, paint spray tubes, and other chemical solution tubes. In particular, it is suitable as a fuel tube.

Hereinafter, the present invention will be specifically described with reference to examples and comparative examples, but the present invention is not limited thereto.
In addition, the analysis and measurement of physical properties in Examples and Comparative Examples were performed as follows.

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 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 part, and titrated with 0.05N sodium hydroxide solution using phenolphthalein as an indicator to determine the terminal carboxyl group concentration.

[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. Titration with 0.05N hydrochloric acid was performed to determine the terminal amino group concentration.

[Terminal formamide group concentration]
When dibutyl oxalate was used, the terminal amino group concentration [NH ₂ ], the terminal butoxy group concentration [OBu], and the terminal formamide group concentration [NHCHO] were determined according to the following equations.
Terminal amino group concentration [NH ₂ ] = n (NH ₂ ) / Mn
Terminal butoxy group concentration [OBu] = n (OBu) / Mn
Terminal formamide group concentration [NHCHO] = n (NHCHO) / Mn
The number average molecular weight (Mn) is based on the signal intensity obtained from the ¹ H-NMR spectrum, for example, polyoxamide produced using dibutyl oxalate as the oxalic acid source and diamine having carbon number X as the diamine component [hereinafter referred to as PAX2 and Abbreviated. ] Was calculated by the following formula.
Mn = np × (14.02 × (carbon number X) +86.06) + n (NH 2) × (14.02 × (carbon number X) +31.044) + n (OBu) × 129.13 + n (NHCHO) × 29 .02
In addition, the measurement conditions of ¹ H-NMR are as follows.
・ Model used: Bruker Biospin, AVANCE500
・ Solvent: Bisulfuric acid ・ Accumulated times: 1,024 times

Moreover, each term in the said formula is prescribed | regulated as follows.
Np = Np / [(N (NH2) + N (NHCHO) + N (OBu)) / 2]
N (NH ₂ ) = N (NH ₂ ) / [(N (NH ₂ ) + N (NHCHO) + N (OBu)) / 2]
N (NHCHO) = N (NHCHO) / [(N (NH ₂ ) + N (NHCHO) + N (OBu)) / 2]
N (OBu) = N (OBu) / [(N (NH ₂ ) + N (NHCHO) + N (OBu)) / 2]
Np = Sp / sp-N (NHCHO)
N (NH ₂ ) = S (NH ₂ ) / s (NH ₂ )
N (NHCHO) = S (NHCHO) / s (NHCHO)
N (OBu) = S (OBu) / s (OBu)
However, each term has the following meaning.
Np: total number of repeating units in the molecular chain excluding the terminal unit of PAX2.
Np: the number of repeating units in the molecular chain per molecule.
Sp: The integral value of the signal (around 3.1 ppm) based on the proton of the methylene group adjacent to the oxamide group in the repeating unit in the molecular chain excluding the end of PAX2.
Sp: The number of hydrogens (4) counted in the integral value Sp.
N (NH ₂ ): Total number of terminal amino groups of PAX2.
N (NH ₂ ): number of terminal amino groups per molecule.
S (NH ₂ ): an integral value of a signal (around 2.6 ppm) based on the proton of the methylene group adjacent to the terminal amino group of PAX2.
S (NH ₂ ): Number of hydrogens (2) counted in the integral value S (NH ₂ ).
N (NHCHO): total number of terminal formamide groups of PAX2.

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.

[Permeability of chemical solution (alcohol-containing gasoline) permeation]
One end of a tube cut to 200 mm was sealed, and alcohol-containing gasoline mixed with Fuel C (isooctane / toluene = 50/50 volume ratio) and ethanol in a 90/10 volume ratio was put inside, and the remaining end was also sealed. Thereafter, the entire mass was measured, and then the test tube was placed in an oven at 60 ° C., and the mass change was measured every day. The change in mass per day was divided by the surface area of the inner layer per 1 m of the tube to calculate the alcohol-containing gasoline permeation amount (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 (Tensilon UTM III-200, manufactured by Orientec Co., Ltd.), 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.

[Durability of interlayer adhesion strength in high temperature atmosphere]
A sample obtained by cutting a laminated tube into a length of 20 cm was used as a sample. This sample was set in a constant temperature bath at 100 ° C. and held for 250 hours. Thereafter, the tube was taken out, the adhesive strength was measured by the above method, and the durability of the interlayer adhesive strength in a high temperature atmosphere was evaluated.

[Monomer and oligomer elution resistance]
One end of the tube cut to 1 m 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 test tube was placed in an oven at 60 ° C. and treated for 7 days. After completion of the treatment, the alcohol-containing gasoline in the taken-out tube was filtered with a filter having a passing particle diameter of 8 μm, and the mass of the collected material was measured. The mass of the collected matter was divided by the number of treatment days and the inner surface area of the tube to calculate the monomer and oligomer elution amounts (g / m ² · day). After the treatment, the color tone of the alcohol-containing gasoline extracted from the tube was also visually observed.

[Materials Used in Examples and Comparative Examples]
(A) Production of Aliphatic Polyamide (a-1) Polyamide 12 In a 70 liter autoclave, 20 kg of dodecane lactam, 0.5 kg of water and 49.3 g of 5-amino-1,3,3-trimethylcyclohexanemethylamine (1 / 175 eq / mol dodecane lactam) and the inside of the polymerization tank was purged with nitrogen, and then heated to 180 ° 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 260 ° 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 2.26, a terminal amino group concentration of 45 μeq / g, and a terminal carboxyl group concentration of 24 μeq / g (hereinafter, this polyamide 12 is referred to as (a-1)). . When the terminal amino group concentration of the polyamide 12 is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), [A]> [B] +5 is satisfied.

(A-1) Manufacture of polyamide 12 resin composition In (a-1), maleic anhydride-modified ethylene / propylene copolymer (manufactured by JSR Corporation, JSR T7712SP) is mixed in advance as an impact resistance improver. Benzenesulfonic acid butyramide was injected as a plasticizer with a metering pump from the middle of the cylinder of the biaxial melt kneader while supplying to the axial melt kneader (Nippon Steel Works, Model: TEX44). After melt-kneading at a temperature of 180 to 260 ° 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 12 resin 85 mass%, impact resistance improving material 10 mass%. Then, a pellet of polyamide 12 resin composition comprising 5% by mass of a plasticizer was obtained (hereinafter, this polyamide 12 resin composition is referred to as (A-1)).

(A-2) Production of polyamide 12 In the production of (a-1), 49.3 g of 5-amino-1,3,3-trimethylcyclohexanemethylamine was converted to polyethyleneimine (Nippon Shokubai Co., Ltd., Epomin SP-12). (A-1) A polyamide having a relative viscosity of 1.90, a terminal amino group concentration of 122 μeq / g, and a terminal carboxyl group concentration of 17 μeq / g, in the same manner as in the production of polyamide 12, except for changing to 92.0 g (Hereinafter, this polyamide 12 is referred to as (a-2)). When the terminal amino group concentration of the polyamide 12 is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), [A]> [B] +5 is satisfied.

(A-2) Production of polyamide 12 resin composition In the production of (A-1), except that (a-1) was changed to (a-2), the same method as in the production of (A-1) was applied. Thus, pellets of polyamide 12 resin composition comprising 85% by mass of polyamide 12 resin, 10% by mass of impact resistance improving material, and 5% by mass of plasticizer were obtained (hereinafter, this polyamide 12 resin composition is referred to as (A-2)). .)

(A-3) Manufacture of polyamide 12 resin composition In the manufacture of (A-1), except that no plasticizer is used, 90% by mass of polyamide 12 resin in the same manner as in the manufacture of (A-1), A pellet of polyamide 12 resin composition comprising 10% by mass of the impact resistance improving material was obtained (hereinafter, this polyamide 12 resin composition is referred to as (A-3)).

(B1) Polyglycolic acid polymer (B1-1) Polyglycolic acid polymer composition Polypropylene having a melt viscosity of 1,600 Pa · s measured at a temperature 20 ° C. higher than the melting point Tm (Tm + 20 ° C.) and a shear rate of 120 sec ^−1. 0.03 parts by mass of Adekastab AX-71 (monostearyl phosphate 50 mol% and distearyl phosphate 50 mol%) manufactured by Asahi Denka Co., Ltd. as a heat stabilizer with respect to 100 parts by mass of glycolic acid homopolymer (Hereinafter, this polyglycolic acid polymer composition is referred to as (B1-1)).

(B1-2) At the time of synthesizing the polyglycolic acid polymer composition, 100 parts by mass of the polyglycolic acid polymer is reacted with 0.5 parts by mass of N, N-2,6-diisopropylphenylcarbodiimide to produce polyglycolic acid. The carboxyl group terminal of the polymer was sealed. The melt viscosity measured at a temperature 20 ° C. higher than the melting point Tm of the polymer composition (Tm + 20 ° C.) and a shear rate of 120 sec ⁻¹ is 1,200 Pa · s, and 100 parts by mass of the polyglycolic acid polymer is Asahi Denka. ADK STAB AX-71 manufactured by Co., Ltd. was further added at a ratio of 0.03 parts by mass (hereinafter, this polyglycolic acid polymer composition is referred to as (B1-2)).

(B2) Aromatic polyester polymer (B2-1) Polybutylene terephthalate: Mitsubishi Engineering Plastics, Nova Duran 5020
(B2-2) Polybutylene naphthalate: Teijin Limited, TQB-0T

(C) Modified polyester elastomer (C-1) Modified polyester elastomer A polyester polyether block copolymer comprising polybutylene terephthalate as a hard segment and polytetramethylene ether glycol having a number average molecular weight of 2,000 as a soft segment. 100 parts by mass of a polyester elastomer having a polytetramethylene ether glycol segment content of 65% by mass in the copolymer, 0.5 parts by mass of maleic anhydride (manufactured by Wako Pure Chemical Industries, Ltd.), and , 0.05 parts by mass of 2,5-dimethyl-2,5-bis (t-butylperoxy) hexane (manufactured by NOF Corporation, Perhexa 25B) as a radical generator is mixed in advance, and a biaxial melt kneader (Nippon Steel Works Model: TEX44) -After melt-kneading at a temperature of 190-230 ° C and extruding the molten resin into a strand shape, this was introduced into a water bath, cooled, cut and vacuum dried to obtain pellets of a modified polyester elastomer (hereinafter referred to as this modified polyester). (The polyester elastomer is referred to as (C-1).) In the modified polyester elastomer, the amount of modification measured by infrared absorption spectrum was 0.34.
(C-2) Unmodified polyester elastomer: manufactured by Toray DuPont, Hytrel 4275

(D) Production of semi-aromatic polyamide or polyoxamide (D1) semi-aromatic polyamide (d1-1) semi-aromatic polyamide 10,178 g (61.3 mol) of terephthalic acid, 4,995 g of 1,9-nonanediamine (31. 6 mol), 2,995 g (31.6 mol) of 2-methyl-1,8-octanediamine, 75.2 g (0.62 mol) of benzoic acid, 20 g of sodium hypophosphite monohydrate (total amount of raw materials) 0.1 mass% with respect to the mass) and 5 liters of distilled water were placed in an autoclave with an internal volume of 40 liters 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 and pulverized to a size of 2 mm or less. This was solid-phase polymerized at 230 ° C. and 0.013 kPa for 10 hours, and then dried under reduced pressure. The melting point was 265 ° C., the relative viscosity was 2.38, the terminal amino group concentration was 79 μeq / g, and the terminal carboxyl group concentration was 5 μeq. / G semi-aromatic polyamide was obtained (hereinafter, this semi-aromatic polyamide is referred to as (d1-1)). When the terminal amino group concentration of the semi-aromatic polyamide is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), [A]> [B] +5 is satisfied.

(D1-1) Manufacture of a semi-aromatic polyamide resin composition A semi-aromatic polyamide (d1-1) and a maleic anhydride-modified ethylene / propylene copolymer (manufactured by JSR Corporation, JSR T7761P) as an impact resistance improver. Mix in advance, supply to a twin-screw melt kneader (manufactured by Nippon Steel Works, Model: TEX44), melt knead at a cylinder temperature of 240-330 ° C., extrude the molten resin into a strand shape, And cooled, cut, and vacuum dried to obtain a semi-aromatic polyamide resin composition pellet comprising 85% by mass of a semi-aromatic polyamide and 15% by mass of an impact resistance improving material (hereinafter referred to as this semi-aromatic polyamide). The resin composition is referred to as (D1-1).)

(D1-2) Production of semi-aromatic polyamide In the production of (d1-1), 1,9-nonanediamine 4,995 g (31.6 mol), 2-methyl-1,8-octanediamine 4,995 g (31 .6 mol) was changed to 1,12-dodecanediamine 12,645.7 g (63.1 mol) in the same manner as in the production of (d1-1), with a melting point of 301 ° C. and a relative viscosity. Was a semi-aromatic polyamide having a terminal amino group concentration of 76 μeq / g and a terminal carboxyl group concentration of 7 μeq / g (hereinafter, this semi-aromatic polyamide is referred to as (d1-2)). When the terminal amino group concentration of the semi-aromatic polyamide is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), [A]> [B] +5 is satisfied.

(D1-2) Manufacture of a semi-aromatic polyamide resin composition In the manufacture of (D1-1), except that (d1-1) was changed to (d1-2), the same as the manufacture of (D1-1) By the method, pellets of a semi-aromatic polyamide resin composition comprising 85% by mass of a semi-aromatic polyamide and 15% by mass of an impact resistance improving material were obtained (hereinafter, this semi-aromatic polyamide resin composition is referred to as (D1-2) That said.)

(D1-3) Production of semi-aromatic polyamide In production of (d1-1), 10,178 g (61.3 mol) of terephthalic acid was converted to 13,244.7 g (61.3 mol) of 2,6-naphthalenedicarboxylic acid. The melting point is 275 ° C., the relative viscosity is 2.32, the terminal amino group concentration is 74 μeq / g, and the terminal carboxyl group concentration is 8 μeq / g, in the same manner as in the production of (d1-1). An aromatic polyamide was obtained (hereinafter, this semi-aromatic polyamide is referred to as (d1-3)). When the terminal amino group concentration of the semi-aromatic polyamide is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), [A]> [B] +5 is satisfied.

(D1-3) Production of semi-aromatic polyamide resin composition In the production of (D1-1), except that (d1-1) was changed to (d1-3), the same as the production of (D1-1) By the method, pellets of a semi-aromatic polyamide resin composition comprising 85% by mass of a semi-aromatic polyamide and 15% by mass of an impact resistance improving material were obtained (hereinafter, this semi-aromatic polyamide resin composition (D1-3) That said.)

(D1-4) Production of semi-aromatic polyamide In production of (d1-2), 10,178 g (61.3 mol) of terephthalic acid was converted to 13,244.7 g (61.3 mol) of 2,6-naphthalenedicarboxylic acid. Except that the melting point is 310 ° C., the relative viscosity is 2.36, the terminal amino group concentration is 73 μeq / g, and the terminal carboxyl group concentration is 8 μeq / g, in the same manner as in the production of (d1-2). An aromatic polyamide was obtained (hereinafter, this semi-aromatic polyamide is referred to as (d1-4)). When the terminal amino group concentration of the semi-aromatic polyamide is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), [A]> [B] +5 is satisfied.

(D1-4) Manufacture of a semi-aromatic polyamide resin composition In the manufacture of (D1-1), except that (d1-1) was changed to (d1-4), the same as the manufacture of (D1-1) By the method, pellets of a semi-aromatic polyamide resin composition comprising 85% by mass of a semi-aromatic polyamide and 15% by mass of an impact resistance improving material were obtained (hereinafter, this semi-aromatic polyamide resin composition is referred to as (D1-4) That said.)

(D1-5) Production of Conductive Semi-Aromatic Polyamide Resin Composition In the production of (D1-2), maleic anhydride-modified ethylene / propylene copolymer (JSR Corporation, JSR T7761P) is modified with maleic anhydride. The production of (D1-2) except that the ethylene / propylene copolymer (manufactured by JSR Co., Ltd., JSR T7761P) and the conductive filler were changed to carbon black (manufactured by Akzo Nobel Co., Ltd., Ketjen Black EC600JD) In the same manner, a pellet of conductive semi-aromatic polyamide resin composition comprising 79% by mass of semi-aromatic polyamide, 15% by mass of impact resistance improving material, and 6% by mass of conductive filler was obtained (hereinafter referred to as this conductive property). The semi-aromatic polyamide resin composition is referred to as (D1-5)).

(D1-5) Production of semi-aromatic polyamide 7720.4 g (46.5 mol) of terephthalic acid, 2,262 g (15.5 mol) of adipic acid, 5,750.7 g (49.5) of 1,6-hexanediamine Mol), 1,717.7 g (14.8 mol) of 2-methyl-1,5-pentanediamine, 113.2 g (1.89 mol) of acetic acid, 17.4 g of sodium hypophosphite monohydrate and distillation 5 liters of water was placed in a 40 liter autoclave 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 and pulverized to a size of 2 mm or less. This was solid-phase polymerized at 230 ° C. and 0.013 kPa for 10 hours, and then dried under reduced pressure. A semi-fragrance having a relative viscosity of 2.13, a terminal amino group concentration of 91 μeq / g, and a terminal carboxyl group concentration of 14 μeq / g. (Hereinafter, this semi-aromatic polyamide is referred to as (d1-5)). When the terminal amino group concentration of the semi-aromatic polyamide is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), [A]> [B] +5 is satisfied.

(D1-6) Production of semi-aromatic polyamide resin composition The production of (D1-1) was the same as the production of (D1-1) except that (d1-1) was changed to (d1-5). By the method, pellets of a semi-aromatic polyamide resin composition comprising 85% by mass of a semi-aromatic polyamide and 15% by mass of an impact resistance improving material were obtained (hereinafter, this semi-aromatic polyamide resin composition was referred to as (D1-6) That said.)

(D2) Production of polyoxamide (d2-1) polyoxamide A stirrer, thermometer, torque meter, pressure gauge, raw material inlet directly connected with a diaphragm pump, nitrogen gas inlet, pressure outlet, pressure regulator, and polymer outlet After charging 28.40 kg (140.4 mol) of dibutyl oxalate into a pressure vessel having an internal volume of 150 liters and pressurizing to 0.5 MPa with nitrogen gas having an internal purity of 99.9999%, The operation of releasing nitrogen gas to normal pressure was repeated 5 times to perform nitrogen substitution, and then the system was heated while stirring under a sealing pressure. After adjusting the temperature of dibutyl oxalate to 100 ° C. over about 30 minutes, 18.89 kg (119.3 mol) of 1,9-nonanediamine and 3.34 kg (21.1 mol) of 2-methyl-1,8-octanediamine (Mole ratio of 1,9-nonanediamine and 2-methyl-1,8-octanediamine is 85:15) is fed into the reaction vessel by a diaphragm pump at a flow rate of 1.49 liter / min for about 17 minutes. The temperature rose simultaneously. The internal pressure in the pressure vessel immediately after the supply increased to 0.35 MPa by butanol generated by the polycondensation reaction, and the temperature of the polycondensate increased to about 170 ° C. Thereafter, the temperature was raised to 235 ° C. over 1 hour. Meanwhile, the internal pressure was adjusted to 0.5 MPa while extracting the generated butanol from the pressure relief port. Immediately after the temperature of the polycondensate reached 235 ° C., butanol was extracted from the pressure release port over about 20 minutes, and the internal pressure was brought to normal pressure. From the normal pressure, the temperature was raised while flowing nitrogen gas at 1.5 liters / minute, the temperature of the polycondensate was raised to 260 ° C. over about 1 hour, and the reaction was carried out at 260 ° C. for 4.5 hours. . Thereafter, stirring was stopped, the inside of the system was pressurized to 1 MPa with nitrogen and allowed to stand for about 10 minutes, then released to an internal pressure of 0.5 MPa, and the polycondensate was extracted in a string form from the lower outlet of the pressure vessel. The string-like polycondensate is immediately cooled, and the water-cooled string-like resin is pelletized by a pelletizer. The melting point is 235 ° C., the relative viscosity is 3.36, the terminal amino group concentration is 46 μeq / g, and the terminal formamide group concentration is 34 μeq / g. A polyoxamide was obtained (hereinafter, this polyoxamide is referred to as (d2-1)). When the terminal amino group concentration of polyoxamide is [A] (μeq / g) and the terminal formamide group concentration is [B] (μeq / g), [A]> [B] +5 is satisfied.

(D2-1) Manufacture of polyoxamide resin composition (d2-1) and maleic anhydride-modified ethylene / propylene copolymer (manufactured by JSR Corporation, JSR T7761P) as an impact resistance improver are mixed in advance and biaxially melted Supply to a kneading machine (Nippon Steel Works, Model: TEX44), melt knead at a cylinder temperature of 240-330 ° C, extrude the molten resin into a strand, introduce it into a water bath, cool, cut Then, vacuum drying was performed to obtain a pellet of a polyoxamide resin composition comprising 85% by mass of polyoxamide and 15% by mass of an impact resistance improving material (hereinafter, this polyoxamide resin composition is referred to as (D2-1)).

(D2-2) Production of polyoxamide In the production of (d2-1), 18.89 kg (119.3 mol) of 1,9-nonanediamine and 3.34 kg (21.1 mol) of 2-methyl-1,8-octanediamine ) Is changed to 28.08 kg (140.4 mol) of 1,12-dodecanediamine, and the melting point is 235 ° C. and the relative viscosity is 3.02, in the same manner as in the production of (d2-1). A polyoxamide having a terminal amino group concentration of 45 μeq / g and a terminal formamide group concentration of 22 μeq / g was obtained (hereinafter, this polyoxamide is referred to as (d2-2)). When the terminal amino group concentration of polyoxamide is [A] (μeq / g) and the terminal formamide group concentration is [B] (μeq / g), [A]> [B] +5 is satisfied.

(D2-2) Production of polyoxamide resin composition Except that (d2-1) was changed to (d2-2) in the production of (D2-1), the same method as the production of (D2-1), A pellet of a polyoxamide resin composition comprising 85% by mass of polyoxamide and 15% by mass of an impact resistance improving material was obtained (hereinafter, this polyoxamide resin composition is referred to as (D2-2)).

(D2-3) Production of polyoxamide In production of (d2-1), 18.89 kg (119.3 mol) of 1,9-nonanediamine and 3.34 kg (21.1 mol) of 2-methyl-1,8-octanediamine ) Was changed to 24.15 kg (140.4 mol) of 1,10-dodecanediamine, (d2-1) in the same manner as in the production of polyoxamide, the melting point was 251 ° C., and the relative viscosity was 3.09. Thus, a polyoxamide having a terminal amino group concentration of 41 μeq / g and a terminal formamide group concentration of 29 μeq / g was obtained (hereinafter, this polyoxamide is referred to as (d2-3)). When the terminal amino group concentration of polyoxamide is [A] (μeq / g) and the terminal formamide group concentration is [B] (μeq / g), [A]> [B] +5 is satisfied.

(D2-3) Production of polyoxamide resin composition Except that (d2-1) was changed to (d2-3) in the production of (D2-1), the same method as in the production of (D2-1), A pellet of a polyoxamide resin composition comprising 85% by mass of polyoxamide and 15% by mass of an impact resistance improving material was obtained (hereinafter, this polyoxamide resin composition is referred to as (D2-3)).

(D2-4) Production of conductive polyoxamide resin composition In the production of (D2-1), maleic anhydride-modified ethylene / propylene copolymer (manufactured by JSR Corporation, JSR T7761P) was converted to maleic anhydride-modified ethylene / propylene. A method similar to the production of (D2-1) except that the copolymer (manufactured by JSR Co., Ltd., JSR T7761P) and the conductive filler is changed to carbon black (manufactured by Akzo Nobel Co., Ltd., Ketjen Black EC600JD). Thus, pellets of a conductive polyoxamide resin composition comprising 79% by mass of polyoxamide, 15% by mass of impact resistance improving material, and 6% by mass of conductive filler were obtained (hereinafter, this conductive polyoxamide resin composition (D2-4) was obtained. ).)

(E) Adhesive resin (E-1) Production of adhesive resin composition (a-1), (B1-1), ethylene / glycidyl methacrylate / vinyl acetate copolymer (manufactured by Sumitomo Chemical Co., Ltd., Bond First 2B) (hereinafter sometimes referred to as a modified polyolefin) is mixed in advance and supplied to a twin-screw melt kneader (manufactured by Nippon Steel Works, Model: TEX44) at a cylinder temperature of 180 to 250 ° C. After melt-kneading and extruding the molten resin into a strand shape, this is introduced into a water tank, cooled, cut, and vacuum-dried to obtain (a-1) / (B1-1) / modified polyolefin = 40/55/5. The pellet of the adhesive resin composition which consists of (mass ratio) was obtained (henceforth this adhesive resin composition is called (E-1)).

(E-2) Production of Adhesive Resin Composition In the production of (E-1), (B-2) is converted to (C-2) an unmodified polyester elastomer and an ethylene / glycidyl methacrylate / vinyl acetate copolymer ( Similar to the production of (E-1) except that Sumitomo Chemical Co., Ltd., Bond First 2B) was changed to polyurethane elastomer (Kuraray Co., Ltd., Kuramylon U1180) and the cylinder temperature was changed to 200-230 ° C. By the method, pellets of an adhesive resin composition comprising (a-1) / unmodified polyester elastomer / polyurethane elastomer = 45/45/10 (mass ratio) were obtained (hereinafter, this adhesive resin composition is referred to as “adhesive resin composition”). (E-2).)

(E-3) Production of adhesive resin composition In the production of (E-1), (a-1) was changed to (d1-1), and the cylinder temperature was changed to 230 to 300 ° C. In the same manner as in the production of 1), pellets of an adhesive resin composition consisting of (d1-1) / (B1-1) / modified polyolefin = 55/40/5 (mass ratio) were obtained (hereinafter, This adhesive resin composition is referred to as (E-3)).

(E-4) Production of Adhesive Resin Composition (E-1) Except that (a-1) was changed to (d2-1) and the cylinder temperature was changed to 230 to 270 ° C. in (E-1) The pellets of the adhesive resin composition consisting of (d2-1) / (B1-1) / modified polyolefin = 55/40/5 (mass ratio) were obtained in the same manner as in the production of (hereinafter referred to as this adhesion). The functional resin composition is referred to as (E-4).)

  (E-5) Ethylene / glycidyl methacrylate / vinyl acetate copolymer: manufactured by Sumitomo Chemical Co., Ltd., Bond First 2B, MFR 3.0 g / 10 min (under 190 ° C. and 2160 g load), melting point 95 ° C.

Example 1
(B-1) a polyester polymer composition (hereinafter referred to as this polyester polymer) comprising (A-1), (B1-1) 75% by mass and (B2-1) 25% by mass of polybutylene terephthalate shown above. The composition may be referred to as (B-1).), (C-1), (D1-1), using a Plabor (Plastic Engineering Laboratory Co., Ltd.) 5-layer tube molding machine, (A-1) was melted separately at an extrusion temperature of 260 ° C., (B-1) at an extrusion temperature of 280 ° C., (C-1) at an extrusion temperature of 220 ° C., and (D1-1) at an extrusion temperature of 300 ° C. separately. The discharged molten resin was merged with an adapter and formed into a laminated tubular body. Subsequently, it is cooled by a sizing die for dimension control and taken up, and (a) layer (outermost layer) made of (A-1), (b) layer (intermediate layer) made of (B-1), (C- (C) layer (outer layer, inner layer 1) consisting of 1), and (d) layer (innermost layer) consisting of (D1-1), the layer configuration is (a) / (c) / (b) / (C) / (d) = 0.55 / 0.10 / 0.10 / 0.10 / 0.15 mm, and a laminated tube having 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.

Example 2
In Example 1, except that (B1-1) port in (B-1) was changed to (B1-2), the laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 1. Obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 3
Table 1 shows the same method as in Example 1 except that (B2-1) polybutylene terephthalate in (B-1) was changed to (B2-2) polybutylene naphthalate in Example 1. A laminated tube having a layer structure was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Examples 4-5
In Example 1, the same method as in Example 1 except that the blending ratio of (B1-1) and (B2-1) polybutylene terephthalate in (B-1) was changed to the amounts shown in Table 1. The laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 6
A laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 1 except that (D1-1) was changed to (D1-2) in Example 1. The physical property measurement results of the laminated tube are shown in Table 1.

Example 7
In Example 1, except that (D1-1) was changed to (D1-3) and the extrusion temperature of (D1-3) was 310 ° C., the layers shown in Table 1 were used in the same manner as in Example 1. A laminated tube with a configuration was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 8
In Example 1, it is shown in Table 1 by the same method as Example 1 except having changed ((D1-1) to (D1-4) and having made the extrusion temperature of (D1-4) 330 degreeC. Table 1 shows the measurement results of physical properties of the laminated tube.

Example 9
In Example 1, except that (D1-1) was changed to (D1-5) and the extrusion temperature of (D1-5) was changed to 330 ° C., the layers shown in Table 1 were used in the same manner as in Example 1. A laminated tube with a configuration was obtained. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 10
In Example 1, except that (D1-1) was changed to (D2-1) and the extrusion temperature of (D2-1) was changed to 270 ° C., the layers shown in Table 1 were used in the same manner as in Example 1. A laminated tube with a configuration was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 11
In Example 10, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 10 except having changed (D2-1) to (D2-2). The physical property measurement results of the laminated tube are shown in Table 1.

Example 12
A laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 10 except that (D2-1) was changed to (D2-3) in Example 10. The physical property measurement results of the laminated tube are shown in Table 1.

Example 13
(B-1), (C-1), and (D1-4) comprising 75% by mass of (A-1) and (B1-1) and 25% by mass of (B2-1) polybutylene terephthalate shown above. Using a Plabor (Plastics Engineering Laboratory Co., Ltd.) 6-layer tube molding machine, (A-1) is an extrusion temperature of 260 ° C, (B1-1 is an extrusion temperature of 280 ° C, and (C-1) is The extrusion temperature was 220 ° C., and (D1-4) was melted separately at an extrusion temperature of 300 ° C., and the discharged molten resin was merged with an adapter and formed into a laminated tubular body. (A-1) (a) layer (outermost layer, inner layer 2), (B-1) (b) layer (intermediate layer), (C-1) (c) (D) layer (innermost layer) consisting of layers (outer layer, inner layer 1), (D1-4) and The layer structure is (a) / (c) / (b) / (c) / (a) / (d) = 0.35 / 0.10 / 0.10 / 0.10 / 0.20. A laminated tube having an inner diameter of 6 mm and an outer diameter of 8 mm was obtained at 0.15 mm, and the physical property measurement results of the laminated tube are shown in Table 1.

Example 14
In Example 13, except that (D1-4) was changed to (D1-5) and the extrusion temperature of (D1-5) was changed to 330 ° C., the layers shown in Table 1 were prepared in the same manner as in Example 13. A laminated tube with a configuration was obtained. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 15
(B-1), (C-1), ((D1-4), (D1-) comprising (A-1), (B1-1) 75% by mass and (B2-1) 25% by mass of polybutylene terephthalate. 5) using a 6-layer tube molding machine (Plastic Engineering Laboratory Co., Ltd.), (A-1) is extrusion temperature 260 ° C., (B1-1) is extrusion temperature 280 ° C., (C -1) was melted separately at an extrusion temperature of 220 ° C., and (D1-4) was melted separately at an extrusion temperature of 330 ° C., and the discharged molten resin was joined by an adapter to form a laminated tubular body. (A) layer (outermost layer) made of A-1), (b) layer (intermediate layer) made of (B-1), (c-1) made (c-1) Layer (outer layer, inner layer 1), (D1) consisting of (D1) layer (inner layer 2), (D −5) (d ′) layer (innermost layer), the layer configuration is (a) / (c) / (b) / (c) / (d) / (d ′) = 0.50 A laminated tube having an inner diameter of 6 mm and an outer diameter of 8 mm was obtained at /0.10/0.10/0.10/0.10/0.10 mm. 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, (D1-4) is changed to (D2-1), (D1-5) is changed to (D2-4), the extrusion temperature of (D2-1) is 270 ° C., and the extrusion of (D2-4) 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 280 ° 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 17
A laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 1 except that (A-1) was changed to (A-2) in Example 1. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 1
In Example 1, the layer structure shown in Table 1 is the same as in Example 1 except that (B-1) the polyester-based polymer composition, (C-1), and (D1-1) are not used. A laminated tube was obtained. Table 1 shows the physical property measurement results of the single-layer tube.

Comparative Example 2
In Example 1, the tube of the layer structure shown in Table 1 was obtained by the same method as Example 1 except not using (C-1). The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 3
In Example 9, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 9 except not using (C-1). The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 4
In Example 1, (C-1)) is changed to (E-1) and (E-3), the extrusion temperature of (E-1) is 280 ° C., and the extrusion temperature of (E-3) is 280 ° C. A laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 1 except that. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 5
In Comparative Example 4, the layers shown in Table 1 were prepared in the same manner as in Comparative Example 4 except that (E-1) was changed to (E-2) and the extrusion temperature of (E-2) was changed to 230 ° C. A laminated tube with a configuration was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 6
In Example 10, Example 10 except that (C-1) was changed to (E-1) and (E-4) and the extrusion temperature of (E-1) and (E-4) was 280 ° 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.

Comparative Example 7
A laminated tube having a layer structure shown in Table 1 was obtained in the same manner as in Example 1, except that (C-1) was changed to (C-2) unmodified polyester elastomer in Example 1. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 8
In Example 1, except that (C-1) was changed to (E-5) ethylene / glycidyl methacrylate / vinyl acetate copolymer, lamination of the layer constitutions shown in Table 1 was performed in the same manner as in Example 1. A tube was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 9
In Example 1, the laminated tube of the layer structure shown in Table 1 was obtained by the same method as Example 1 except not using (B2-1) polybutylene terephthalate in (B-1). The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 10
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 (B1-1) in (B-1). The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Examples 11-12
In Example 1, the same method as in Example 1 except that the blending ratio of (B1-1)) and (B2-1) polybutylene terephthalate in (B-1) was changed to the amounts shown in Table 1. Thus, a laminated tube having the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 13
In Example 1, (D1-1) was changed to (D1-6) and (D1-6) was changed to an extrusion temperature of 330 ° C., in the same manner as in Example 1, and the layer structure shown in Table 1 A laminated tube was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 14
In Example 1, except that (D1-1) was changed to (A-3) and (A-3) was changed to an extrusion temperature of 270 ° C., the layer structure shown in Table 1 was used in the same manner as in Example 1. A laminated tube was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Claims (10)

(A) (a) layer made of aliphatic polyamide, (B) (b) layer made of polyester polymer composition, (C) (c) layer made of modified polyester elastomer, and (D1) semi-aromatic A laminated tube consisting of at least four layers, including a (d) layer made of polyamide or (D2) polyoxamide;
(B) The polyester polymer composition is a polyester polymer composition comprising (B1) 60 to 90% by mass of a polyglycolic acid polymer and (B2) 40 to 10% by mass of an aromatic polyester polymer,
(C) The modified polyester elastomer is a modified polyester elastomer graft-modified with an α, β-ethylenically unsaturated carboxylic acid,
(D1) The semi-aromatic polyamide is a diamine unit containing 60 mol% or more of an aliphatic diamine unit having 9 to 13 carbon atoms with respect to all diamine units, and terephthalic acid and / or naphthalene with respect to all dicarboxylic acid units. A semi-aromatic polyamide comprising a dicarboxylic acid unit containing at least 50 mol% of a dicarboxylic acid unit,
(D2) The dioxan in which the polyoxamide contains 60 mol% or more of aliphatic diamine units having 9 to 13 carbon atoms with respect to all diamine units and 60 mol% or more of oxalic acid units with respect to all dicarboxylic acid units. A laminated tube which is a polyoxamide composed of acid units. The laminated tube according to claim 1, wherein the (c) layer is disposed between the (a) layer and the (b) layer and between the (b) layer and the (d) layer. (A) Aliphatic polyamide is polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polyhexamethylene decamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecamethylene At least selected from the group consisting of decamide (polyamide 1010), polydecane methylene dodecane (polyamide 1012), poly dodecane methylene dodecane (polyamide 1212), polyundecanamide (polyamide 11), and polydodecanamide (polyamide 12). It is 1 type, The laminated tube of Claim 1 or 2 characterized by the above-mentioned. The terminal amino group concentration of (A) aliphatic polyamide, (D1) semi-aromatic polyamide or (D2) polyoxamide is [A] (μeq / g), and the terminal carboxyl group concentration or terminal formamide group concentration is [B] (μeq / The laminated tube according to any one of claims 1 to 3, wherein [A]> [B] +5 is satisfied when g) is satisfied. 0057, 0058
(B1) The polyglycolic acid polymer has the following formula (1)

The laminated tube according to any one of claims 1 to 4, which contains 60% by mass or more of a repeating unit represented by: The laminated tube according to any one of claims 1 to 5, wherein (a) the layer is disposed on the outermost layer and (d) the layer is disposed on the innermost layer. The layer structure of the laminated tube is (a) / (c) / (b) / (c) / (d), or (a) / (c) / (b) / (c) / (a) / (d The laminated tube according to any one of claims 1 to 6, wherein 8. A layer made of (D1) a semi-aromatic polyamide composition containing a conductive filler or a (D2) polyoxamide composition containing a conductive filler is disposed in the innermost layer of the laminated tube. A laminated tube according to any one of the above. The laminated tube according to any one of claims 1 to 8, wherein the laminated tube is manufactured by coextrusion molding. The laminated tube according to any one of claims 1 to 9, wherein the laminated tube is used as a fuel tube.