JP2014240139A - Laminate tube - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a laminated tube excellent in low-temperature impact resistance, chemical liquid impermeability and interlaminar adhesiveness.SOLUTION: There is provided a laminated tube which comprises: a layer composed of at least one polyamide polymer selected from the group consisting of a polyamide 11, a polyamide 12 and a polyamide 11/12 copolymer; a layer composed of at least one polyamide polymer selected from the group consisting of a polyamide 6/12, a polyamide 610 and a polyamide 612; and a layer composed of a semi-aromatic polyamide polymer having a specific structure.

Description

  The present invention includes a layer made of at least one polyamide polymer selected from the group consisting of polyamide 11, polyamide 12, and polyamide 11/12 copolymer, a group consisting of polyamide 6/12, polyamide 610, and polyamide 612. A laminated tube comprising a layer made of at least one selected polyamide polymer and a layer made of a semi-aromatic polyamide polymer having a specific structure, which has low-temperature impact resistance, chemical permeation prevention, and interlayer adhesion It is related with the laminated tube which is excellent in.

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

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

  As a method for solving this problem, resins having good chemical permeation preventive properties such as saponified ethylene / vinyl acetate copolymer (EVOH), polymetaxylylene adipamide (polyamide MXD6), poly (hexamethylene terephthalamide) / Hexamethylene adipamide) copolymer (polyamide 6T / 66), poly (hexamethylene terephthalamide / hexamethylene isophthalamide / hexamethylene adipamide) copolymer (polyamide 6T / 6I / 66), poly Butylene terephthalate (PBT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyphenylene sulfide (PPS), polyvinylidene fluoride (PVDF), ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / chlorotri Fluoroethylene Polymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (TFE / HFP / VDF, THV), tetrafluoro Ethylene / hexafluoropropylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer (TFE / HFP / VDF / PAVE), tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (TFE / PAVE, PFA), Tetrafluoroethylene / hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer (TFE / HFP / PAVE), chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) / te La fluoroethylene copolymer (CTFE / PAVE / TFE, CPT) have been proposed numerous arranged stacked tubes (e.g., see Patent Document 1).

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

  Furthermore, a fuel transfer tube in which polymetaxylylene adipamide (polyamide MXD6) is disposed in the intermediate layer has been proposed (see Patent Document 3). This polyamide MXD6 is known to have good adhesive strength with polyamide 6. However, since the interlayer adhesion is insufficient for the polyamide 11 or the polyamide 12 conventionally used as a constituent material of the single-layer tube, it is necessary to provide an adhesive layer between the layers. Furthermore, the hose in which the polyamide MXD6 is disposed has a disadvantage that it is inferior in low-temperature impact resistance. As a laminated tube that achieves both chemical penetration prevention and low-temperature impact resistance, a laminated tube in which a polyamide resin having compatibility with polyamide MXD6 and the polyamide MXD6 and softer than polyamide MXD6 is arranged in an intermediate layer has been proposed. (See Patent Document 4). However, further improvement is desired in terms of low-temperature impact, and when modified olefins or polyamide 6/12 copolymers are used as the adhesive layer shown in the examples of the same document, disclosure of data on interlayer adhesion is disclosed. There is no technical suggestion, and the adhesive layer is not an essential component in the laminated tube. Further, with respect to polyamide MXD6 and polyamide 11 and / or polyamide 12, a layer comprising a polyamide resin composition containing a carbodiimide compound having two or more carbodiimide groups in the molecule as a compatibilizing agent, and polyamide 11 and / or Or the laminated body characterized by having the layer which consists of polyamide 12, and the fuel tube using this laminated body are proposed (refer patent document 5). In the fuel tube, although the interlayer adhesion with the polyamide 11 or the polyamide 12 is improved to some extent, the interlayer adhesion is influenced by the morphology of the resin composition comprising the polyamide MXD6 and the polyamide 11 and / or the polyamide 12, and the extrusion. There is a drawback that the interlayer adhesiveness varies greatly and decreases depending on the conditions and use environment conditions. Further, in the case of a fuel tube in which a layer made of a polyamide resin composition containing polyamide MXD6 and polyamide 11 and / or polyamide 12 and a carbodiimide compound is used as a barrier layer (innermost layer), in order to improve interlayer adhesion, polyamide 11 In addition, a considerable amount of polyamide 12 must be added, and the excellent chemical liquid permeation-preventing property of polyamide MXD6 cannot be exhibited.

US Pat. No. 5,554,425 Special table 2007-502726 JP-A-4-272592 JP 2008-18702 A JP 2009-279927 A

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

  As a result of intensive studies to solve the above problems, the present inventors have found that the layer is composed of at least one polyamide polymer selected from the group consisting of polyamide 11, polyamide 12, and polyamide 11/12 copolymer. A laminated tube comprising a layer made of at least one polyamide polymer selected from the group consisting of polyamide 6/12, polyamide 610, and polyamide 612, and a layer made of a semi-aromatic polyamide polymer having a specific structure; It has been found that it is excellent in low temperature impact resistance, chemical solution permeation prevention properties, and interlayer adhesion.

  That is, the present invention provides at least one selected from the group consisting of polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), and poly (undecanamide / dodecanamide) copolymer (polyamide 11/12). (A) layer composed of polyamide polymer (A), poly (caproamide / dodecanamide) copolymer (polyamide 6/12), polyhexamethylene sebacamide (polyamide 610), and polyhexamethylene dodecamide (polyamide 612) (B) layer composed of at least one polyamide polymer (B) selected from the group consisting of) and a semi-aromatic polyamide polymer (C1) of 50% by mass to 95% by mass and conforming to ISO 178 The olefin polymer (C2) having a measured flexural modulus of 500 MPa or less is 5 mass% or more and 5 A laminated tube composed of at least three layers including a layer (c) composed of a semi-aromatic polyamide polymer composition (C) contained in an amount of mass% or less, wherein the semi-aromatic polyamide polymer (C1) is a total diamine A diamine unit containing 60 mol% or more of an aliphatic diamine unit having 4 to 6 carbon atoms having a straight chain and / or a side chain, a terephthalic acid unit of 30 mol% to 100 mol%, terephthalic acid A semi-aromatic comprising a dicarboxylic acid unit composed of 0 to 70 mol% of an aromatic dicarboxylic acid unit other than the above and / or 0 to 70 mol% of an aliphatic dicarboxylic acid unit having 4 to 20 carbon atoms Group polyamide polymer (C3) or m-xylylenediamine unit 30 mol% or more and 100 mol% or less, p-xylylenediamine unit 0 mol% or more and 70 mol% % Or less, an aliphatic dicarboxylic acid unit having 4 to 6 carbon atoms having a straight chain and / or a side chain, 30 mol% to 100 mol%, terephthalic acid unit and / or isophthalic acid unit 0 mol% to 70 mol The laminated tube is characterized by being a semi-aromatic polyamide polymer (C4) comprising at most%.

The preferable aspect of the laminated tube of this invention is shown below. A plurality of preferred embodiments can be combined.
[1] In the semi-aromatic polyamide polymer (C3), an aliphatic diamine unit having a straight chain and / or a side chain and having 4 to 6 carbon atoms is 1,6-hexanediamine and / or 2-methyl-1 In the semiaromatic polyamide polymer (C4), an aliphatic dicarboxylic acid unit having 4 to 6 carbon atoms and having a straight chain and / or a side chain is derived from adipic acid. A laminated tube which is a unit to be induced.
[2] A laminated tube, wherein the (b) layer is in direct contact with the (a) layer and is disposed between the (a) and (c) layers.
[3] A laminated tube, wherein the (a) layer is disposed as the outermost layer, and the (c) layer is disposed inside the (a) layer.
[4] The laminated tube further comprises polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), and a poly (caproamide / hexamethylene adipamide) copolymer (polyamide 6/66). A laminated tube comprising a layer (d) comprising at least one polyamide polymer (D) selected from the group, wherein the layer (d) is disposed in direct contact with the layer (c).
[5] A laminated tube, wherein the (c) layer is disposed in the innermost layer.
[6] The laminated tube further includes an (e) layer composed of a fluorine-containing polymer (E) in which a functional group having reactivity to an amino group is introduced into the molecular chain, the (e) layer Is disposed in the innermost layer.
[7] A laminated tube, wherein a conductive layer made of a thermoplastic resin composition containing a conductive filler is disposed in the innermost layer of the laminated tube.
[8] A laminated tube manufactured by coextrusion molding.
[9] A laminated tube used as a chemical solution transport tube.

  The laminated tube of the present invention achieves both interlayer adhesion and chemical solution permeation prevention properties, and is excellent in various properties such as low-temperature impact resistance, heat resistance, and chemical resistance. Particularly, it is suitable as a chemical solution transport tube, and it is possible to suppress a chemical solution that permeates and evaporates from the tube partition wall.

The polyamide polymer (A) used in the present invention comprises polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), and poly (undecanamide / dodecanamide) copolymer (polyamide 11/12). It is at least one polyamide polymer selected from the group (hereinafter, sometimes referred to as polyamide polymer (A)).
The polyundecanamide (polyamide 11) is composed of undecanamide units represented by the following formula (—CO— (CH ₂ ) ₁₀ —NH—) _n having an amide bond (—CONH—) in the main chain, It can be obtained by polymerizing aminoundecanoic acid or undecane lactam.
The polydodecanamide (polyamide 12) comprises a dodecanamide unit represented by the following formula (—CO— (CH ₂ ) ₁₁ —NH—) _n having an amide bond (—CONH—) in the main chain, It can be obtained by polymerizing aminododecanoic acid or dodecane lactam.
The poly (undecanamide / dodecanamide) copolymer (polyamide 11/12) is a polyamide copolymer having an amide bond (—CONH—) in the main chain and having an undecanamide unit and a dodecanamide unit, It can be obtained by copolymerizing 11-aminoundecanoic acid or undecane lactam and 12-aminododecanoic acid or dodecane lactam. In the poly (undecanamide / dodecanamide) copolymer, the molar ratio of the undecanamide unit to the dodecanamide unit is from 2:98 mol% to 98: 2 in consideration of the heat resistance and mechanical strength of the resulting laminated tube. It is preferably not more than mol%, more preferably not less than 5:95 mol% and not more than 95: 5 mol%.

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

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

  In the polyamide polymer (A), when the terminal amino group concentration per 1 g of the polyamide is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), [A]> [B ] +5 (hereinafter also referred to as terminal-modified polyamide) is preferable in view of interlayer adhesion of the laminated tube, and more preferably [A]> [B] +10, and [A]> [ B] +15 is more preferable. Furthermore, from the viewpoint of the melt stability of the polyamide and the suppression of the generation of gel-like material, [A]> 20 is preferable, and 30 <[A] <120 is more preferable.

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

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

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

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

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

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

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

Examples of the polyalkyleneimine include one or two alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, 1,1-dimethylethyleneimine Examples include homopolymers and copolymers obtained by polymerizing more than one species by a conventional method. Among these, polyethyleneimine is more preferable. Polyalkyleneimine is polymerized from alkyleneimine as a raw material, branched polyalkyleneimine obtained by ring-opening polymerization of alkyleneimine, secondary polyamineimine containing secondary amine and tertiary amine, or alkyloxazoline as a raw material. Either a linear polyalkyleneimine containing only a primary amine and a secondary amine, or a three-dimensionally crosslinked structure may be used. Furthermore, ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine, bisaminopropylethylenediamine, and the like may be included. A polyalkyleneimine is usually derived from the reactivity of an active hydrogen atom on a nitrogen atom contained therein, and in addition to a tertiary amino group, a primary amino group having an active hydrogen atom or a secondary amino group (imino Group).
The number of nitrogen atoms in the polyalkyleneimine is not particularly limited, but is preferably 4 or more and 3,000 or less, more preferably 8 or more and 1,500, and even more preferably 11 or more and 500 or less. . The number average molecular weight of the polyalkyleneimine is preferably 100 or more and 20,000 or less, more preferably 200 or more and 10,000 or less, and further preferably 500 or more and 8,000 or less.

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

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

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

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

  The polyamide polymer (A) may be a mixture with other polyamide-based resins or other thermoplastic resins. The content of the polyamide polymer (A) in the mixture is preferably 50% by mass or more, and more preferably 60% by mass or more.

Other polyamide resins include polyethylene adipamide (polyamide 26), polytetramethylene succinamide (polyamide 44), polytetramethylene glutamide (polyamide 45), polytetramethylene adipamide (polyamide 46), poly Tetramethylene suberamide (polyamide 48), polytetramethylene azelamide (polyamide 49), polytetramethylene sebamide (polyamide 410), polytetramethylene dodecamide (polyamide 412), polypentamethylene succinamide (polyamide 54) , Polypentamethyleneglutamide (polyamide 55), polypentamethylene adipamide (polyamide 56), polypentamethylene suberamide (polyamide 58), polypentamethylene azelamide (polyamide 59), polypenta Tylene sebamide (polyamide 510), polypentamethylene dodecamide (polyamide 512), polyhexamethylene succinamide (polyamide 64), polyhexamethylene glutamide (polyamide 65), polyhexamethylene suberamide (polyamide 68), polyhexamethylene Azelamide (polyamide 69), polyhexamethylenetetradecanide (polyamide 614), polyhexamethylene hexadecanamide (polyamide 616), polyhexamethylene octadecanamide (polyamide 618), polynonamethylene adipamide (polyamide 96) Polynonamethylene suberamide (Polyamide 98), Polynonamethylene azelamide (Polyamide 99), Polynonamethylene sebacamide (Polyamide 910), Polynonamethylene dodecamide (Polyamide) 912), polydecamethylene adipamide (polyamide 106), polydecamethylene suberamide (polyamide 108), polydecamethylene azelamide (polyamide 109), polydecamethylene sebamide (polyamide 1010), polydecamethylene dodeca Mido (polyamide 1012), polydodecamethylene adipamide (polyamide 126), polydodecamethylene suberamide (polyamide 128), polydodecamethylene azelamide (polyamide 129), polydodecamethylene sebacamide (polyamide 1210), polydodeca Methylene dodecamide (polyamide 1212),
Polymetaxylylene beramide (polyamide MXD8), polymetaxylylene azelamide (polyamide MXD9), polymetaxylylene sebamide (polyamide MXD10), polymetaxylylene decanamide (polyamide MXD12), polymetaxylylene hexahydroterephthalamide (Polyamide MXDT (H)), polymetaxylylene naphthalamide (polyamide MXDN), polyparaxylylene beramide (polyamide PXD8), polyparaxylylene azeamide (polyamide PXD9), polyparaxylylene sebacamide (polyamide PXD10) ), Polyparaxylylene decanamide (polyamide PXD12), polyparaxylylene hexahydroterephthalamide (polyamide PXDT (H)), polyparaxylylene naphthalamide (polyamide) PXDN), polyparaphenylene terephthalamide (PPTA), polyparaphenylene isophthalamide (PPIA), polymetaphenylene terephthalamide (PMTA), polymetaphenylene isophthalamide (PMIA), poly (2,6-naphthalene) Dimethylene adipamide) (polyamide 2,6-BAN6), poly (2,6-naphthalene dimethylene suberamide) (polyamide 2,6-BAN8), poly (2,6-naphthalene dimethylene azelamide) (polyamide) 2,6-BAN9), poly (2,6-naphthalene dimethylene sebacamide) (polyamide 2,6-BAN10), poly (2,6-naphthalene dimethylene dodecamide) (polyamide 2,6-BAN12), Poly (2,6-naphthalene dimethylene terephthalamide) (Polyamide 2,6-BA T), poly (2,6-naphthalene dimethylene isophthalamide) (polyamide 2,6-BANI), poly (2,6-naphthalene dimethylene hexahydroterephthalamide) (polyamide 2,6-BANT (H)) ), Poly (2,6-naphthalene dimethylene naphthalamide) (polyamide 2,6-BANN), poly (1,3-cyclohexanedimethylene adipamide) (polyamide 1,3-BAC6), poly (1,3 -Cyclohexane dimethylene suberamide (polyamide 1,3-BAC8), poly (1,3-cyclohexane dimethylene azelamide) (polyamide 1,3-BAC9), poly (1,3-cyclohexane dimethylene sebacamide) ( Polyamide 1,3-BAC10), poly (1,3-cyclohexanedimethylene dodecamide) (polyamide 1,3- BAC12), poly (1,3-cyclohexanedimethylene terephthalamide) (polyamide 1,3-BACT), poly (1,3-cyclohexanedimethylene isophthalamide) (polyamide 1,3-BACI), poly (1 , 3-cyclohexanedimethylenehexahydroterephthalamide) (polyamide 1,3-BACT (H)), poly (1,3-cyclohexanedimethylene naphthalamide) (polyamide 1,3-BACN), poly (1,4 -Cyclohexane dimethylene adipamide) (polyamide 1,4-BAC6), poly (1,4-cyclohexanedimethylene suberamide) (polyamide 1,4-BAC8), poly (1,4-cyclohexanedimethylene azelamide) (Polyamide 1,4-BAC9), poly (1,4-cyclohexanedimethylene sebacami) ) (Polyamide 1,4-BAC10), poly (1,4-cyclohexanedimethylene dodecamide) (polyamide 1,4-BAC12), poly (1,4-cyclohexanedimethylene terephthalamide) (polyamide 1,4- BACT), poly (1,4-cyclohexanedimethylene isophthalamide) (polyamide 1,4-BACI), poly (1,4-cyclohexanedimethylene hexahydroterephthalamide) (polyamide 1,4-BACT (H) ), Poly (1,4-cyclohexanedimethylenenaphthalamide) (polyamide 1,4-BACN), poly (4,4′-methylenebiscyclohexylene adipamide) (polyamide PACM6), poly (4,4′- Methylenebiscyclohexylenesuberamide) (polyamide PACM8), poly (4,4'-methylene) Sucyclohexylene azelamide) (polyamide PACM9), poly (4,4′-methylenebiscyclohexylene sebamide) (polyamide PACM10), poly (4,4′-methylenebiscyclohexylene dodecamide) (polyamide PACM12), Poly (4,4′-methylenebiscyclohexylenetetradecamide) (polyamide PACM14), poly (4,4′-methylenebiscyclohexylenehexadecamide) (polyamide PACM16), poly (4,4′-methylenebiscyclohexylene) Silene octadecamide) (polyamide PACM18), poly (4,4′-methylenebiscyclohexylene terephthalamide) (polyamide PACMT), poly (4,4′-methylenebiscyclohexylene isophthalamide) (polyamide PACMI), Poly (4,4'- Tylene biscyclohexylene hexahydroterephthalamide) (polyamide PACMT (H)), poly (4,4′-methylenebiscyclohexylene naphthalamide) (polyamide PACMN), poly (4,4′-methylene bis (2-methyl-) (Cyclohexylene) adipamide) (polyamide MACM6), poly (4,4′-methylenebis (2-methyl-cyclohexylene) suberamide) (polyamide MACM8), poly (4,4′-methylenebis (2-methyl-cyclohexylene) azeramide ) (Polyamide MACM9), poly (4,4′-methylenebis (2-methyl-cyclohexylene) sebacamide) (polyamide MACM10), poly (4,4′-methylenebis (2-methyl-cyclohexylene) dodecamide) (polyamide MACM12) ), Poly (4 4′-methylenebis (2-methyl-cyclohexylene) tetradecanamide) (polyamide MACM14), poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexadecamide) (polyamide MACM16), poly (4,4′-methylenebis) (2-methyl-cyclohexylene) octadecamide) (polyamide MACM18), poly (4,4′-methylenebis (2-methyl-cyclohexylene) terephthalamide) (polyamide MACMT), poly (4,4′-methylenebis (2-methyl) -Cyclohexylene) isophthalamide) (polyamide MACMI), poly (4,4'-methylenebis (2-methyl-cyclohexylene) hexahydroterephthalamide) (polyamide MACMT (H)), poly (4,4'-methylenebis ( 2-methyl-cyclo Xylene) naphthalamide) (polyamide MACMN), poly (4,4′-propylene biscyclohexylene adipamide) (polyamide PACP6), poly (4,4′-propylene biscyclohexylene suberamide) (polyamide PACP8), poly ( 4,4′-propylene biscyclohexylene azelamide) (polyamide PACP9), poly (4,4′-propylene biscyclohexylene sebacamide) (polyamide PACP10), poly (4,4′-propylene biscyclohexylene dodecamide) ) (Polyamide PACP12), poly (4,4′-propylene biscyclohexylene tetradecanamide) (polyamide PACP14), poly (4,4′-propylene biscyclohexylene hexadecanamide) (polyamide PACP16), poly (4 4'-propi Biscyclohexylene octadecanamide) (polyamide PACP18), poly (4,4′-propylene biscyclohexylene terephthalamide) (polyamide PAPPT), poly (4,4′-propylene biscyclohexylene isophthalamide) (polyamide) PACPI), poly (4,4′-propylene biscyclohexylene hexahydroterephthalamide) (polyamide PACPT (H)), poly (4,4′-propylene biscyclohexylene naphthalamide) (polyamide PACPN), polyisophorone azide Pamide (Polyamide IPD6), Polyisophorone Veramide (Polyamide IPD8), Polyisophorone Azelamide (Polyamide IPD9), Polyisophorone Sebamide (Polyamide IPD10), Polyisoholonand Decamide (Polyamide IPD) 2), polyisophorone terephthalamide (polyamide IPDT), polyisophorone isophthalamide (polyamide IPDI), polyisophorone hexahydroterephthalamide (polyamide IPDT (H)), polyisophorone naphthalamide (polyamide IPDN), polytetramethylene Hexahydroterephthalamide (polyamide 4T (H)), polypentamethylene hexahydroterephthalamide (polyamide 5T (H)), polyhexamethylene hexahydroterephthalamide (polyamide 6T (H)), poly (2-methyl Pentamethylene hexahydroterephthalamide) (polyamide M5T (H)), polynonamethylene terephthalamide (polyamide 9T), polynonamethylene isophthalamide (polyamide 9I), polynonamethylene hexahydroterephthala (Polyamide 9T (H)), polynonamethylene naphthalamide (polyamide 9N), poly (2-methyloctamethylene terephthalamide) (polyamide M8T), poly (2-methyloctamethylene isophthalamide) (polyamide M8I) , Poly (2-methyloctamethylenehexahydroterephthalamide) (polyamide M8T (H)), poly (2-methyloctamethylenenaphthalamide) (polyamide M8N), polytrimethylhexamethylene terephthalamide (polyamide TMHT), poly Trimethylhexamethyleneisophthalamide (polyamide TMHI), polytrimethylhexamethylenehexahydroterephthalamide (polyamide TMHT (H)), polytrimethylhexamethylenenaphthalamide (polyamide TMHN), polydecamethylenetereph Taramide (polyamide 10T), polydecamethylene isophthalamide (polyamide 10I), polydecamemethylene hexahydroterephthalamide (polyamide 10T (H)), polydecamethylene naphthalamide (polyamide 10N), polyundecamethylene terephthalamide (Polyamide 11T), Polyundecamethylene isophthalamide (Polyamide 11I), Polyundecamethylene hexahydroterephthalamide (Polyamide 11T (H)), Polyundecamethylene naphthalamide (Polyamide 11N), Polydodecamethylene terephthalate Lamid (polyamide 12T), polydodecamethylene isophthalamide (polyamide 12I), polydodecamethylene hexahydroterephthalamide (polyamide 12T (H)), polydodecamethylene naphthalamide (polyamide 1) N) and a copolymer using several kinds of raw material monomers of these polyamides. These can use 1 type (s) or 2 or more types.

  Other thermoplastic resins to be mixed include high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and ultra high molecular weight polyethylene (UHMWPE). , Polypropylene (PP), polybutene (PB), polymethylpentene (TPX), ethylene / propylene copolymer (EPR), ethylene / butene copolymer (EBR), ethylene / vinyl acetate copolymer (EVA), ethylene / Saponified vinyl acetate copolymer (EVOH), ethylene / acrylic acid copolymer (EAA), ethylene / methacrylic acid copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methacrylic acid Methyl copolymer (EMMA), ethylene / ethyl acrylate Polyolefin resins such as polymer (EEA), polystyrene (PS), syndiotactic polystyrene (SPS), methyl methacrylate / styrene copolymer (MS), methyl methacrylate / styrene / butadiene copolymer (MBS), Styrene / butadiene copolymer (SBR), styrene / isoprene copolymer (SIR), styrene / isoprene / butadiene copolymer (SIBR), styrene / butadiene / styrene copolymer (SBS), styrene / isoprene / styrene copolymer Polymer (SIS), styrene / ethylene / butylene / styrene copolymer (SEBS), polystyrene resins such as styrene / ethylene / propylene / styrene copolymer (SEPS), carboxyl groups and salts thereof, acid anhydride groups, The above containing functional groups such as epoxy groups Reolefin resin, polystyrene resin, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), poly (ethylene terephthalate / ethylene isophthalate) copolymer (PET / PEI), polytrimethylene Terephthalate (PTT), polycyclohexanedimethylene terephthalate (PCT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyarylate (PAR), liquid crystal polyester (LCP), polylactic acid (PLA), polyglycolic acid Polyester resins such as (PGA), polyether resins such as polyacetal (POM) and polyphenylene ether (PPO), polysulfone (PSU), polyethersulfone (PESU) , Polysulfone resins such as polyphenylsulfone (PPSU), polythioether resins such as polyphenylene sulfide (PPS) and polythioethersulfone (PTES), polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketone ketone (PEKK), polyetheretherketoneketone (PEEKK), polyetherketoneetherketoneketone (PEKEKK) and other polyketone resins, polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene Polynitriles such as copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), acrylonitrile / butadiene copolymer (NBR) Resins, polymethacrylate resins such as polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA), polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride Copolymers, polyvinyl resins such as vinylidene chloride / methyl methacrylate copolymer, cellulose resins such as cellulose acetate and cellulose butyrate, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorofluoroethylene (PCTFE) ), Tetrafluoroethylene / ethylene copolymer (ETFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / hex Fluoropropylene / vinylidene fluoride copolymer (THV), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (PFA) ), Fluororesin such as tetrafluoroethylene / hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer, chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer (CPT), polycarbonate (PC ) And other polycarbonate resins, thermoplastic polyimide (TPI), polyetherimide, polyesterimide, polyamideimide (PAI), polyesteramideimide and other poly Examples thereof include imide resins, thermoplastic polyurethane resins, polyamide elastomers, polyurethane elastomers, and polyester elastomers. These can use 1 type (s) or 2 or more types.

  Moreover, it is preferable to add a plasticizer to the polyamide polymer (A). Examples of the plasticizer include benzenesulfonic acid alkylamides, toluenesulfonic acid alkylamides, and hydroxybenzoic acid alkyl esters.

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

  The content of the plasticizer may be 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the polyamide polymer (A) from the viewpoint of sufficiently ensuring the flexibility and low temperature impact resistance of the laminated tube. Preferably, it is 2 parts by mass or more and 20 parts by mass or less.

Further, in order to improve the low temperature impact resistance of the polyamide polymer (A), it is preferable to add an impact resistance improving material, and particularly, the ISO described in the semi-aromatic polyamide polymer composition (C) described later. It is more preferable to add an olefin polymer having a flexural modulus measured according to 178 of 500 MPa or less. If the flexural modulus exceeds this value, the impact improvement effect may be insufficient.
The content of the impact resistance improving material is 1 part by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the polyamide polymer (A) from the viewpoint of sufficiently ensuring the mechanical strength and low temperature impact resistance of the laminated tube. It is preferable that it is 3 parts by mass or more and 25 parts by mass or less.

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

The polyamide polymer (B) used in the present invention comprises a poly (caproamide / dodecanamide) copolymer (polyamide 6/12), polyhexamethylene sebacamide (polyamide 610), and polyhexamethylene dodecamide (polyamide). 612) is at least one polyamide polymer selected from the group consisting of 612) (hereinafter sometimes referred to as polyamide polymer (B)).
The poly (caproamide / dodecanamide) copolymer (polyamide 6/12) is represented by the following formula (—CO— (CH ₂ ) ₆ —NH—) _n having an amide bond (—CONH—) in the main chain. A polyamide copolymer having a dodecanamide unit represented by the formula: (—CO— (CH ₂ ) ₁₁ —NH—) _n , 6-aminocaproic acid or caprolactam and 12-aminododecanoic acid or dodecane It can be obtained by copolymerizing lactam. The molar ratio of caproamide unit to dodecanamide unit is preferably 50:50 mol% or more and 95: 5 mol% or less from the viewpoint of interlayer adhesion of the laminated tube, and is 60:40 mol% or more and 90:10 mol%. The following is more preferable.
Polyhexamethylene sebacamide (polyamide 610) has an amide bond (—CONH—) in the main chain: (—NH— (CH ₂ ) ₆ —NH—CO— (CH ₂ ) ₈ —CO—) It consists of a hexamethylene sebacamide unit represented by _n and can be obtained by polymerizing 1,6-hexanediamine and sebacic acid.
Polyhexamethylene dodecamide (polyamide 612) has an amide bond (—CONH—) in the main chain: (—NH— (CH ₂ ) ₆ —NH—CO— (CH ₂ ) ₁₀ —CO—) _n It can be obtained by polymerizing 1,6-hexanediamine and dodecanedioic acid.

  As a manufacturing apparatus of a polyamide polymer (B), the well-known polyamide manufacturing apparatus described by description of the polyamide polymer (A) is mentioned. As a manufacturing method of a polyamide polymer (B), the well-known method described by description of the polyamide polymer (A) is mentioned.

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

  In the polyamide polymer (B), when the terminal amino group concentration per 1 g of the polyamide is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), [A]> [B ] +5 is preferable in consideration of interlayer adhesion of the laminated tube, more preferably [A]> [B] +10, and still more preferably [A]> [B] +15. Furthermore, from the viewpoint of the melt stability of the polyamide and the suppression of the generation of gel-like material, [A]> 20 is preferable, and 30 <[A] <120 is more preferable.

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

  The polyamide polymer (B) may contain other polyamide-based resins or other thermoplastic resins. Examples of other polyamide-based resins or other thermoplastic resins include the same resins as in the case of the polyamide polymer (A). Furthermore, it may be a mixture with the polyamide polymer (A). The content of the polyamide polymer (B) in the mixture is preferably 60% by mass or more, and more preferably 80% by mass or more.

In order to improve the low-temperature impact resistance of the polyamide polymer (B), it is preferable to add an impact resistance improver, and particularly in ISO 178 described in the semi-aromatic polyamide polymer composition (C) described later. It is more preferable to add an olefin polymer having a flexural modulus measured in accordance with 500 MPa or less. If the flexural modulus exceeds this value, the impact improvement effect may be insufficient.
The content of the impact resistance improving material is 1 part by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the polyamide polymer (B) from the viewpoint of sufficiently ensuring the mechanical strength and low temperature impact resistance of the laminated tube. It is preferable that it is 3 parts by mass or more and 25 parts by mass or less.
Moreover, in order to improve the softness | flexibility of a polyamide polymer (B), it is preferable to add a plasticizer, and it is more preferable to add the plasticizer described in the said polyamide polymer (A) especially.
The content of the plasticizer may be 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the polyamide polymer (B) from the viewpoint of sufficiently ensuring the flexibility and low temperature impact resistance of the laminated tube. Preferably, it is 2 parts by mass or more and 20 parts by mass or less.

  Furthermore, for the polyamide polymer (B), if necessary, an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, an inorganic filler, an antistatic agent, a flame retardant, a crystallization accelerator. Colorants, lubricants and the like may be added.

The semi-aromatic polyamide polymer composition (C) used in the present invention is a semi-aromatic polyamide polymer (C1) and an olefin polymer (C2) having a flexural modulus of 500 MPa or less measured according to ISO 178. (Hereafter, it may be called a semi-aromatic polyamide polymer composition (C).).
The semi-aromatic polyamide polymer (C1) comprises a diamine unit containing 60 mol% or more of an aliphatic diamine unit having 4 to 6 carbon atoms having a straight chain and / or a side chain with respect to all diamine units; 30 to 100 mol% of acid units, 0 to 70 mol% of aromatic dicarboxylic acid units other than terephthalic acid, and / or 0 to 70 mol of aliphatic dicarboxylic acid units having 4 to 20 carbon atoms Semi-aromatic polyamide polymer (C3) comprising dicarboxylic acid units consisting of mol% or less, or m-xylylenediamine units 30 mol% to 100 mol%, p-xylylenediamine units 0 mol% to 70 mol% Or less, an aliphatic dicarboxylic acid unit having 4 to 6 carbon atoms and having a straight chain and / or a side chain, 30 mol% to 100 mol%, terephthalic acid A position and / or isophthalic acid unit 0 mol% or more consisting of 70 mol% or less semi-aromatic polyamide polymer (C4) (hereinafter sometimes referred to as semi-aromatic polyamide polymer (C1).).

  The semi-aromatic polyamide polymer (C3) includes a diamine unit containing 60 mol% or more of an aliphatic diamine unit having 4 to 6 carbon atoms having a straight chain and / or a side chain with respect to all diamine units; 30 to 100 mol% of acid units, 0 to 70 mol% of aromatic dicarboxylic acid units other than terephthalic acid, and / or 0 to 70 mol of aliphatic dicarboxylic acid units having 4 to 20 carbon atoms It consists of dicarboxylic acid units consisting of less than or equal to mol% (hereinafter sometimes referred to as semi-aromatic polyamide polymer (C3)).

  The content of the aliphatic diamine unit having 4 to 6 carbon atoms having a straight chain and / or a side chain in the semi-aromatic polyamide polymer (C3) depends on the heat resistance, chemical resistance, From the viewpoint of sufficiently ensuring various physical properties such as impact properties and chemical liquid permeation prevention properties, it is 60 mol% or more, preferably 70 mol% or more, and preferably 80 mol% or more based on the total diamine units. Is more preferable.

  Examples of the aliphatic diamine unit having 4 to 6 carbon atoms having a straight chain and / or a side chain include 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1-butyl-1 , 2-ethanediamine, 1,1-dimethyl-1,4-butanediamine, 1-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butanediamine, 1,3-dimethyl-1 , 4-butanediamine, 1,4-dimethyl-1,4-butanediamine, 2,3-dimethyl-1,4-butanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5 -Units derived from pentanediamine and the like. These can use 1 type (s) or 2 or more types. Among these, units derived from 1,6-hexanediamine and 2-methyl-1,5-pentanediamine are preferable from the viewpoint of availability. When 1,6-hexanediamine and 2-methyl-1,5-pentanediamine are used in combination, the molar ratio of the 1,6-hexanediamine unit to the 2-methyl-1,5-pentanediamine unit depends on the moldability and resistance. From the standpoint of impact balance, it is preferably 30:70 mol% or more and 98: 2 mol% or less, and more preferably 40:60 mol% or more and 95: 5 mol% or less.

  The diamine unit in the semi-aromatic polyamide polymer (C3) has 4 to 6 carbon atoms having a straight chain and / or a side chain as long as the excellent properties of the laminated tube of the present invention are not impaired. Other diamine units other than the aliphatic diamine unit may be included. As other diamine units, 1,2-ethanediamine, 1,3-propanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2-methyl-1,8-octane Diamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 1,10-decanediamine, 5-methyl-1,9-nonanediamine, 1 , 11-undecanediamine, 1,12-dodecanediamine, units derived from aliphatic diamines such as 1,13-tridecanediamine, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis (Aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane 2,2-bis (4-aminocyclohexyl) propane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (3-methyl-4-aminocyclohexyl) propane, 5-amino-2,2 , 4-Trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine, bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, 2,5-bis (aminomethyl) Units derived from cycloaliphatic diamines such as norbornane, 2,6-bis (aminomethyl) norbornane, 3,8-bis (aminomethyl) tricyclodecane, 4,9-bis (aminomethyl) tricyclodecane, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, p-xylylenediamine 1,4-bis (aminomethyl) naphthalene, 1,5-bis (aminomethyl) naphthalene, 2,6-bis (aminomethyl) naphthalene, 2,7-bis (aminomethyl) naphthalene, 4,4′- Examples include units derived from aromatic diamines such as diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 4,4′-diaminodiphenylsulfone, and 4,4′-diaminodiphenyl ether. Or 2 or more types can be used. The content of these other diamine units is 40 mol% or less, preferably 30 mol% or less, more preferably 20 mol% or less, based on all diamine units.

  The dicarboxylic acid units in the semi-aromatic polyamide polymer (C3) are terephthalic acid units of 30 mol% to 100 mol%, aromatic dicarboxylic acid units other than terephthalic acid units of 0 mol% to 70 mol%, and / or carbon. It consists of 0 to 70 mol% of aliphatic dicarboxylic acid units having 4 to 20 atoms.

  The content of the terephthalic acid unit is 30 mol% or more and 100 mol% or less, preferably 40% or more and 100 mol% or less, and 50 mol% or more and 100 mol% or less with respect to all the dicarboxylic acid units. More preferably, the content of aromatic dicarboxylic acid units other than terephthalic acid is 0 mol% or more and 70 mol% or less, and 0 mol% or more and 60 mol% or less with respect to all dicarboxylic acid units. Preferably, it is 0 mol% or more and 50 mol% or less, and the content of the aliphatic dicarboxylic acid unit having 4 to 20 carbon atoms is 0 mol% or more and 70 mol% with respect to the total dicarboxylic acid unit. Or less, preferably 0 mol% or more and 60 mol% or less, and more preferably 0 mol% or more and 50 mol% or less.

  As aromatic dicarboxylic acid units other than terephthalic acid, isophthalic acid, 2-methylterephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalene Examples thereof include units derived from dicarboxylic acids and the like. These can use 1 type (s) or 2 or more types.

Examples of the aliphatic dicarboxylic acid unit having 4 to 20 carbon atoms include dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, 2,2- Diethylsuccinic acid, suberic acid, azelaic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecane Examples thereof include units derived from diacid, hexadecanedioic acid, octadecanedioic acid, eicosanedioic acid and the like. These can use 1 type (s) or 2 or more types. Among these, adipic acid, suberic acid, azelaic acid, sebacic acid, undecane diene are used from the viewpoint of sufficiently securing various physical properties such as heat resistance, chemical resistance, impact resistance, and chemical liquid permeation resistance of the obtained laminated tube. A unit derived from an acid, dodecanedioic acid or tridecanedioic acid is preferred, and a unit derived from adipic acid, sebacic acid or dodecanedioic acid is more preferred.
Furthermore, polycarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used within a range where melt molding is possible.

  The semi-aromatic polyamide polymer (C3) may contain other units other than the dicarboxylic acid unit and the diamine unit as long as the excellent properties of the laminated tube of the present invention are not impaired. Other units include units derived from lactams such as caprolactam, enantolactam, undecane lactam, dodecane lactam, α-pyrrolidone, α-piperidone, 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11 -Units derived from aminocarboxylic acids of aliphatic aminocarboxylic acids such as aminoundecanoic acid and 12-aminododecanoic acid, and aromatic aminocarboxylic acids such as p-aminomethylbenzoic acid. These can use 1 type (s) or 2 or more types. The content of other units is preferably 40 mol% or less, more preferably 35 mol% or less, and further preferably 30 mol% or less based on the total dicarboxylic acid unit.

Specific examples of the semi-aromatic polyamide polymer (C3) include poly (tetramethylene terephthalamide / tetramethylene isophthalamide) copolymer (polyamide 4T / 4I), poly (tetramethylene terephthalamide / tetramethylene naphtha). Copolymer (polyamide 4T / 4N), poly (tetramethylene terephthalamide / tetramethylene adipamide) copolymer (polyamide 4T / 46), poly (tetramethylene terephthalamide / tetramethylene azelamide) Polymer (polyamide 4T / 49), poly (tetramethylene terephthalamide / tetramethylene sebacamide) copolymer (polyamide 4T / 410), poly (tetramethylene terephthalamide / tetramethylene dodecamide) copolymer (polyamide 4T) / 412), poly (tetramethylene terf Lamide / tetramethylene isophthalamide / tetramethylene adipamide) copolymer (polyamide 4T / 4I / 46), poly (tetramethylene terephthalamide / tetramethylene isophthalamide / tetramethylene azelamide) copolymer (polyamide) 4T / 4I / 49), poly (tetramethylene terephthalamide / tetramethylene isophthalamide / tetramethylene sebacamide) copolymer (polyamide 4T / 4I / 410), poly (tetramethylene terephthalamide / tetramethylene iso Phthalamide / tetramethylene dodecamide) copolymer (polyamide 4T / 4I / 412), poly (tetramethylene terephthalamide / tetramethylene naphthalamide / tetramethylene adipamide) copolymer (polyamide 4T / 4N / 46) , Poly (tetramethylene terephthala / Pentamethylene terephthalamide) copolymer (polyamide 4T / 5T), poly (tetramethylene terephthalamide / tetramethylene isophthalamide / pentamethylene terephthalamide / pentamethylene isophthalamide) copolymer (polyamide 4T) / 4I / 5T / 5I), poly (tetramethylene terephthalamide / tetramethylene naphthalamide / pentamethylene terephthalamide / pentamethylene naphthalamide) copolymer (polyamide 4T / 4N / 5T / 5N), poly (tetramethylene Terephthalamide / pentamethylene terephthalamide / tetramethylene adipamide / pentamethylene adipamide) copolymer (polyamide 4T / 5T / 46/56), poly (tetramethylene terephthalamide / tetramethylene isophthalamide / Pentamethylene terephthalamide / Pentamethylene isophthalamide / tetramethylene adipamide / pentamethylene adipamide) copolymer (polyamide 4T / 4I / 5T / 5I / 46/56), poly (tetramethylene terephthalamide / tetramethylene naphthalamide / Pentamethylene terephthalamide / pentamethylene naphthalamide / tetramethylene adipamide / pentamethylene adipamide copolymer (polyamide 4T / 4N / 5T / 5N / 46/56), poly (tetramethylene terephthalamide / hexa Methylene terephthalamide) copolymer (polyamide 4T / 6T), poly (tetramethylene terephthalamide / tetramethylene isophthalamide / hexamethylene terephthalamide / hexamethylene isophthalamide) copolymer (polyamide 4T / 4I / 6T / 6I), poly (tetramethylene) Rephthalamide / tetramethylene naphthalamide / hexamethylene terephthalamide / hexamethylene naphthalamide) copolymer (polyamide 4T / 4N / 6T / 6N), poly (tetramethylene terephthalamide / hexamethylene terephthalamide / tetramethylene adipa) Imide / hexamethylene adipamide) copolymer (polyamide 4T / 6T / 46/66), poly (tetramethylene terephthalamide / tetramethylene isophthalamide / hexamethylene terephthalamide / hexamethylene isophthalamide / tetramethylene Adipamide / hexamethylene adipamide) copolymer (polyamide 4T / 4I / 6T / 6I / 46/66), poly (tetramethylene terephthalamide / tetramethylene naphthalamide / hexamethylene terephthalamide / hexamethylene naphtha Lami / Tetramethylene adipamide / pentamethylene adipamide copolymer (polyamide 4T / 4N / 6T / 6N / 46/56), poly (tetramethylene terephthalamide / pentamethylene terephthalamide / hexamethylene terephthalamide) ) Copolymer (polyamide 4T / 5T / 6T), poly (tetramethylene terephthalamide / tetramethylene isophthalamide / pentamethylene terephthalamide / pentamethylene isophthalamide / hexamethylene terephthalamide / hexamethylene isophthalamide ) Copolymer (polyamide 4T / 4I / 5T / 5I / 6T / 6I), poly (tetramethylene terephthalamide / tetramethylene naphthalamide / pentamethylene terephthalamide / pentamethylene naphthalamide / hexamethylene terephthalamide / hexa Methylene naphthala ) Copolymer (polyamide 4T / 4N / 5T / 5N / 6T / 6N), poly (tetramethylene terephthalamide / pentamethylene terephthalamide / hexamethylene terephthalamide / tetramethylene adipamide / pentamethylene adipa Amide / hexamethylene adipamide) copolymer (polyamide 4T / 5T / 6T / 46/56/66), poly (tetramethylene terephthalamide / tetramethylene isophthalamide / pentamethylene terephthalamide / pentamethylene isophthalate) Lamide / hexamethylene terephthalamide / hexamethylene isophthalamide / tetramethylene adipamide / pentamethylene adipamide / hexamethylene adipamide) copolymer (polyamide 4T / 4I / 5T / 5I / 6T / 6I / 46) / 56/66), poly (tetramethylene terephthala) / Tetramethylenenaphthalamide / pentamethyleneterephthalamide / pentamethylenenaphthalamide / hexamethyleneterephthalamide / hexamethylenenaphthalamide / tetramethyleneadipamide / pentamethyleneadipamide / hexamethyleneadipamide) copolymer (Polyamide 4T / 4N / 5T / 5N / 6T / 6N / 46/56/66), poly (tetramethylene terephthalamide / caproamide) copolymer (polyamide 4T / 6), poly (tetramethylene terephthalamide / undecane) Amide) copolymer (polyamide 4T / 11), poly (tetramethylene terephthalamide / dodecanamide) copolymer (polyamide 4T / 12), poly (tetramethylene terephthalamide / tetramethylene isophthalamide / caproamide) Polymer (Polyamide 4T / I / 6), poly (tetramethylene terephthalamide / tetramethylene isophthalamide / undecanamide) copolymer (polyamide 4T / 4I / 11), poly (tetramethylene terephthalamide / tetramethylene isophthalamide / dodecanamide) ) Copolymer (polyamide 4T / 4I / 12), poly (tetramethylene terephthalamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 4T / 9T / M8T), poly ( Tetramethylene terephthalamide / trimethylhexamethylene terephthalamide) copolymer (polyamide 4T / TMHT), poly (tetramethylene terephthalamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / trimethylhexamethylene telee Phthalamide) copolymerization (Polyamide 4T / 9T / M8T / TMHT), poly (tetramethylene terephthalamide / decamethylene terephthalamide) copolymer (polyamide 4T / 10T), poly (tetramethylene terephthalamide / dodecamethylene terephthalamide) Copolymer (polyamide 4T / 12T), poly (tetramethylene terephthalamide / tetramethylene isophthalamide / nonamethylene terephthalamide / nonamethylene isophthalamide / 2-methyloctamethylene terephthalamide / 2-methyloctamethylene Isophthalamide) copolymer (polyamide 4T / 4I / 9T / 9I / M8T / M8I), poly (tetramethylene terephthalamide / tetramethylene isophthalamide / trimethylhexamethylene terephthalamide / trimethylhexamethylene isophthalamide) Copolymer Polyamide 4T / 4I / TMHT / TMHI), poly (tetramethylene terephthalamide / tetramethylene isophthalamide / nonamethylene terephthalamide / nonamethylene isophthalamide / 2-methyloctamethylene terephthalamide / 2-methyloctamethylene Isophthalamide / trimethylhexamethylene terephthalamide / trimethylhexamethylene isophthalamide) copolymer (polyamide 4T / 4I / 9T / 9I / M8T / M8I / TMHT / TMHI), poly (tetramethylene terephthalamide / tetramethylene) Isophthalamide / Decamethylene terephthalamide / Decamethylene isophthalamide) copolymer (polyamide 4T / 4I / 10T / 10I), poly (tetramethylene terephthalamide / tetramethylene isophthalamide / dodecamethylene tele) Taramido / dodecamethylene isophthalamide) copolymer (polyamide 4T / 4I / 12T / 12I),
Poly (pentamethylene terephthalamide / pentamethylene isophthalamide) copolymer (polyamide 5T / 5I), poly (pentamethylene terephthalamide / pentamethylene naphthalamide) copolymer (polyamide 5T / 5N), poly (penta Methylene terephthalamide / pentamethylene adipamide) copolymer (polyamide 5T / 56), poly (pentamethylene terephthalamide / pentamethylene azelamide) copolymer (polyamide 5T / 59), poly (pentamethylene terephthalamide) / Pentamethylene sebacamide) copolymer (polyamide 5T / 510), poly (pentamethylene terephthalamide / pentamethylene dodecamide) copolymer (polyamide 5T / 512), poly (pentamethylene terephthalamide / pentamethylene iso) Phthalamide / pentamethy Adipamide) copolymer (polyamide 5T / 5I / 56), poly (pentamethylene terephthalamide / pentamethylene naphthalamide / pentamethylene adipamide) copolymer (polyamide 5T / 5N / 56), poly (pentamethylene tele Phthalamide / hexamethylene terephthalamide) copolymer (polyamide 5T / 6T), poly (pentamethylene terephthalamide / pentamethylene isophthalamide / hexamethylene terephthalamide / hexamethylene isophthalamide) copolymer (polyamide) 5T / 5I / 6T / 6I), poly (pentamethylene terephthalamide / pentamethylene naphthalamide / hexamethylene terephthalamide / hexamethylene naphthalamide) copolymer (polyamide 5T / 5N / 6T / 6N), poly (penta Methylene terephthalamide / hex Methylene terephthalamide / pentamethylene adipamide / hexamethylene adipamide) copolymer (polyamide 5T / 6T / 56/66), poly (pentamethylene terephthalamide / pentamethylene isophthalamide / hexamethylene terephthalamide) / Hexamethylene isophthalamide / pentamethylene adipamide / hexamethylene adipamide) copolymer (polyamide 5T / 5I / 6T / 6I / 56/66), poly (pentamethylene terephthalamide / pentamethylene naphthalamide / Hexamethylene terephthalamide / hexamethylene naphthalamide / pentamethylene adipamide / hexamethylene adipamide copolymer (polyamide 5T / 5N / 6T / 6N / 56/66), poly (pentamethylene terephthalamide / caproamide) ) Copolymer (Polyamide 5T / 6), poly (pentamethylene terephthalamide / undecanamide) copolymer (polyamide 5T / 11), poly (pentamethylene terephthalamide / dodecanamide) copolymer (polyamide 5T / 12), poly (pentamethylene tele) Phthalamide / pentamethyleneisophthalamide / caproamide) copolymer (polyamide 5T / 5I / 6), poly (pentamethylene terephthalamide / pentamethyleneisophthalamide / undecanamide) copolymer (polyamide 5T / 5I / 11) ), Poly (pentamethylene terephthalamide / pentamethylene isophthalamide / dodecanamide) copolymer (polyamide 5T / 5I / 12), poly (pentamethylene terephthalamide / nonamethylene terephthalamide / 2-methyloctamethylene) Terephthalamide) copolymer (polyamide) 5T / 9T / M8T), poly (pentamethylene terephthalamide / trimethylhexamethylene terephthalamide) copolymer (polyamide 5T / TMHT), poly (pentamethylene terephthalamide / nonamethylene terephthalamide / 2-methylocta Methylene terephthalamide / trimethylhexamethylene terephthalamide) copolymer (polyamide 5T / 9T / M8T / TMHT), poly (pentamethylene terephthalamide / decamemethylene terephthalamide) copolymer (polyamide 5T / 10T), Poly (pentamethylene terephthalamide / dodecamethylene terephthalamide) copolymer (polyamide 5T / 12T), poly (pentamethylene terephthalamide / pentamethylene isophthalamide / nonamethylene terephthalamide / nonamethylene isophthalamide / 2-methyl Octamethylene terephthalamide / 2-methyloctamethylene isophthalamide copolymer (polyamide 5T / 5I / 9T / 9I / M8T / M8I), poly (pentamethylene terephthalamide / pentamethylene isophthalamide / trimethylhexamethylene) Terephthalamide / trimethylhexamethylene isophthalamide) copolymer (polyamide 5T / 5I / TMHT / TMHI), poly (pentamethylene terephthalamide / pentamethylene isophthalamide / nonamethylene terephthalamide / nonamethylene isophthalamide) / 2-methyloctamethylene terephthalamide / 2-methyloctamethylene isophthalamide / trimethylhexamethylene terephthalamide / trimethylhexamethylene isophthalamide) copolymer (polyamide 5T / 5I / 9T / 9I / M8T / M8I / TMHT / TMHI), poly (pentamethylene terephthalamide / pentamethylene isophthalamide / decamethylene terephthalamide / decamethylene isophthalamide) copolymer (polyamide 5T / 5I / 10T / 10I), poly (penta Methylene terephthalamide / pentamethylene isophthalamide / dodecamethylene terephthalamide / dodecamethylene isophthalamide) copolymer (polyamide 5T / 5I / 12T / 12I),
Poly (hexamethylene terephthalamide / hexamethylene isophthalamide) copolymer (polyamide 6T / 6I), poly (hexamethylene terephthalamide / hexamethylene naphthalamide) copolymer (polyamide 6T / 6N), poly (hexa Methylene terephthalamide / hexamethylene adipamide) copolymer (polyamide 6T / 66), poly (hexamethylene terephthalamide / hexamethylene azelamide) copolymer (polyamide 6T / 69), poly (hexamethylene terephthalate) Lamide / hexamethylene sebacamide) copolymer (polyamide 6T / 610), poly (hexamethylene terephthalamide / hexamethylene dodecamide) copolymer (polyamide 6T / 612), poly (hexamethylene terephthalamide / hexa) Methylene isophthalamide / hexamethylene Dipamide) copolymer (polyamide 6T / 6I / 66), poly (hexamethylene terephthalamide / hexamethylene isophthalamide / hexamethylene azelamide) copolymer (polyamide 6T / 6I / 69), poly (hexamethylene tele) Phthalamide / hexamethylene isophthalamide / hexamethylene sebacamide) copolymer (polyamide 6T / 6I / 610), poly (hexamethylene terephthalamide / hexamethylene isophthalamide / hexamethylene dodecamide) copolymer ( Polyamide 6T / 6I / 612), poly (hexamethylene terephthalamide / hexamethylene naphthalamide / hexamethylene adipamide) copolymer (polyamide 6T / 6N / 66), poly (hexamethylene terephthalamide / 2-methyl) Pentamethylene terephthalamide) copolymer Polyamide 6T / M5T), poly (hexamethylene terephthalamide / hexamethylene isophthalamide / 2-methylpentamethylene terephthalamide / 2-methylpentamethylene isophthalamide) copolymer (polyamide 6T / 6I / M5T / M5I) ), Poly (hexamethylene terephthalamide / hexamethylene naphthalamide / 2-methylpentamethylene terephthalamide / 2-methylpentamethylene naphthalamide) copolymer (polyamide 6T / 6N / M5T / M5N), poly (hexamethylene Terephthalamide / 2-methylpentamethylene terephthalamide / hexamethylene adipamide / 2-methylpentamethylene adipamide) copolymer (polyamide 6T / M5T / 66 / M56), poly (hexamethylene terephthalamide / Hexamethylene isophthalamide / 2-methylpentamethylene terephthalamide / 2-methylpentamethylene isophthalamide / hexamethylene adipamide / 2-methylpentamethylene adipamide) (polyamide 6T / 6I / M5T / M5I / 66 / M56) ), Poly (hexamethylene terephthalamide / hexamethylene naphthalamide / 2-methylpentamethylene terephthalamide / 2-methylpentamethylene naphthalamide / hexamethylene adipamide / 2-methylpentamethylene adipamide) copolymer (Polyamide 6T / 6N / M5T / M5N / 66 / M56), poly (hexamethylene terephthalamide / caproamide) copolymer (polyamide 6T / 6), poly (hexamethylene terephthalamide / undecanamide) copolymer ( Polyamide 6T / 11), poly (hexamethylene) Rephthalamide / dodecanamide) copolymer (polyamide 6T / 12), poly (hexamethylene terephthalamide / 2-methylpentamethylene terephthalamide / caproamide) copolymer (polyamide 6T / M5T / 6), poly (hexamethylene) Terephthalamide / 2-methylpentamethylene terephthalamide / undecanamide) copolymer (polyamide 6T / M5T / 11), poly (hexamethylene terephthalamide / 2-methylpentamethylene terephthalamide / dodecanamide) copolymer Polymer (polyamide 6T / M5T / 12), poly (hexamethylene terephthalamide / hexamethylene isophthalamide / caproamide) copolymer (polyamide 6T / 6I / 6), poly (hexamethylene terephthalamide / hexamethylene isophthalate) Lamid / Undecanamide Copolymer (polyamide 6T / 6I / 11), poly (hexamethylene terephthalamide / hexamethylene isophthalamide / dodecanamide) copolymer (polyamide 6T / 6I / 12), poly (hexamethylene terephthalamide / nona) Methylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 6T / 9T / M8T), poly (hexamethylene terephthalamide / trimethylhexamethylene terephthalamide) copolymer (polyamide 6T / TMHT) , Poly (hexamethylene terephthalamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / trimethylhexamethylene terephthalamide) copolymer (polyamide 6T / 9T / M8T / TMHT), poly (hexamethylene terephthalamide) Phthalamide / Decamethylene Terephthalamide) copolymer (polyamide 6T / 10T), poly (hexamethylene terephthalamide / dodecamethylene terephthalamide) copolymer (polyamide 6T / 12T), poly (hexamethylene terephthalamide / 2-methylpentamethylene tele) Phthalamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 6T / M5T / 9T / M8T), poly (hexamethylene terephthalamide / 2-methylpentamethylene terephthalamide / trimethyl) Hexamethylene terephthalamide) copolymer (polyamide 6T / M5T / TMHT), poly (hexamethylene terephthalamide / 2-methylpentamethylene terephthalamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide / Trimethylhe Samethylene terephthalamide) copolymer (polyamide 6T / M5T / 9T / M8T / TMHT), poly (hexamethylene terephthalamide / 2-methylpentamethylene terephthalamide / decamethylene terephthalamide) copolymer (polyamide) 6T / M5T / 10T), poly (hexamethylene terephthalamide / 2-methylpentamethylene terephthalamide / dodecamethylene terephthalamide) copolymer (polyamide 6T / M5T / 12T), poly (hexamethylene terephthalamide / Hexamethylene isophthalamide / nonamethylene terephthalamide / nonamethylene isophthalamide / 2-methyloctamethylene terephthalamide / 2-methyloctamethylene isophthalamide) copolymer (polyamide 6T / 6I / 9T / 9I / M8T / M8I), poly (hexamethy Terephthalamide / hexamethylene isophthalamide / trimethyl hexamethylene terephthalamide / trimethyl hexamethylene isophthalamide) copolymer (polyamide 6T / 6I / TMHT / TMHI), poly (hexamethylene terephthalamide / hexamethylene isophthalamide / Nonamethylene terephthalamide / nonamethylene isophthalamide / 2-methyloctamethylene terephthalamide / 2-methyloctamethylene isophthalamide / trimethylhexamethylene terephthalamide / trimethylhexamethylene isophthalamide) copolymer (polyamide 6T) / 6I / 9T / 9I / M8T / M8I / TMHT / TMHI), poly (hexamethylene terephthalamide / hexamethylene isophthalamide / decamemethylene terephthalamide / decamethylene isophthalamide) ) Copolymer (polyamide 6T / 6I / 10T / 10I), poly (hexamethylene terephthalamide / hexamethylene isophthalamide / dodecamethylene terephthalamide / dodecamethylene isophthalamide) copolymer (polyamide 6T / 6I / 12T / 12I), poly (hexamethylene terephthalamide / hexamethylene isophthalamide / 2-methylpentamethylene terephthalamide / 2-methylpentamethylene isophthalamide / nonamethylene terephthalamide / nonamethylene isophthalamide / 2 -Methyloctamethylene terephthalamide / 2-methyloctamethylene isophthalamide) copolymer (polyamide 6T / 6I / M5T / M5I / 9T / 9I / M8T / M8I), poly (hexamethylene terephthalamide / hexamethylene iso) Phthalamide / 2-methylpe Tamethylene terephthalamide / 2-methylpentamethylene isophthalamide / trimethyl hexamethylene terephthalamide / trimethyl hexamethylene isophthalamide) copolymer (polyamide 6T / 6I / M5T / M5I / TMHT / TMHI), poly (hexa Methylene terephthalamide / hexamethylene isophthalamide / 2-methylpentamethylene terephthalamide / 2-methylpentamethylene isophthalamide / nonamethylene terephthalamide / nonamethylene isophthalamide / 2-methyloctamethylene terephthalamide / 2-methyloctamethyleneisophthalamide / trimethylhexamethyleneterephthalamide / trimethylhexamethyleneisophthalamide) copolymer (polyamide 6T / 6I / M5T / M5I / 9T / 9I / M8T / M8I / TMHT / MHI), poly (hexamethylene terephthalamide / hexamethylene isophthalamide / 2-methylpentamethylene terephthalamide / 2-methylpentamethylene isophthalamide / decamethylene terephthalamide / decamethylene isophthalamide) copolymer (Polyamide 6T / 6I / M5T / M5I / 10T / 10I), poly (hexamethylene terephthalamide / hexamethylene isophthalamide / 2-methylpentamethylene terephthalamide / 2-methylpentamethylene isophthalamide / dodecamethylene tele Phthalamide / dodecamethylene isophthalamide) copolymer (polyamide 6T / 6I / M5T / M5I / 12T / 12I) and the like.

  Among these, poly (hexamethylene terephthalamide / hexahexaterene) from the viewpoint of easy availability and sufficient physical properties such as heat resistance, chemical resistance, impact resistance and chemical liquid permeation resistance of the obtained laminated tube. Methylene isophthalamide) copolymer (polyamide 6T / 6I), poly (hexamethylene terephthalamide / hexamethylene adipamide) copolymer (polyamide 6T / 66), poly (hexamethylene terephthalamide / hexamethylene iso) Phthalamide / hexamethylene adipamide) copolymer (polyamide 6T / 6I / 66), poly (hexamethylene terephthalamide / 2-methylpentamethylene terephthalamide) copolymer (polyamide 6T / M5T), poly ( Hexamethylene terephthalamide / hexamethylene isophthalamide / 2-methylpentamethylene tele Taramide / 2-methylpentamethylene isophthalamide) copolymer (polyamide 6T / 6I / M5T / M5I), poly (hexamethylene terephthalamide / 2-methylpentamethylene terephthalamide / hexamethylene adipamide / 2- Methyl pentamethylene adipamide) copolymer (polyamide 6T / M5T / 66 / M56), poly (hexamethylene terephthalamide / hexamethylene isophthalamide / 2-methylpentamethylene terephthalamide / 2-methylpentamethylene iso) Phthalamide / hexamethylene adipamide / 2-methylpentamethylene adipamide) copolymer (polyamide 6T / 6I / M5T / M5I / 66 / M56), poly (hexamethylene terephthalamide / caproamide) copolymer ( Polyamide 6T / 6), poly (hexamethylene) Phthalamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 6T / 9T / M8T), poly (hexamethylene terephthalamide / decamethylene terephthalamide) copolymer (polyamide 6T / 10T), poly (hexamethylene terephthalamide / dodecamethylene terephthalamide) copolymer (polyamide 6T / 12T), poly (hexamethylene terephthalamide / hexamethylene isophthalamide / nonamethylene terephthalamide / nonamethylene iso Phthalamide / 2-methyloctamethylene terephthalamide / 2-methyloctamethylene isophthalamide) copolymer (polyamide 6T / 6I / 9T / 9I / M8T / M8I), poly (hexamethylene terephthalamide / hexamethylene iso) Phthalamide / Decamethylene Terephthalamide / decamethylene isophthalamide) copolymer (polyamide 6T / 6I / 10T / 10I), poly (hexamethylene terephthalamide / hexamethylene isophthalamide / dodecamethylene terephthalamide / dodecamethylene isophthalamide) copolymer Polymer (polyamide 6T / 6I / 12T / 12I) is preferred, poly (hexamethylene terephthalamide / hexamethylene isophthalamide) copolymer (polyamide 6T / 6I), poly (hexamethylene terephthalamide / hexamethylene isophthalate) A ramid / hexamethylene adipamide) copolymer (polyamide 6T / 6I / 66) and a poly (hexamethylene terephthalamide / 2-methylpentamethylene terephthalamide) copolymer (polyamide 6T / M5T) are more preferable.

  The semi-aromatic polyamide polymer (C4) comprises 30 to 100 mol% of m-xylylenediamine units, 0 to 70 mol% of p-xylylenediamine units, and linear and / or side chains. The aliphatic dicarboxylic acid unit having 4 to 6 carbon atoms and having 30 to 100 mol%, terephthalic acid units and / or isophthalic acid units having 0 to 70 mol% (hereinafter referred to as semi-aromatic polyamide heavy). May be referred to as coalescence (C4)).

The diamine unit in the semi-aromatic polyamide polymer (C4) consists of m-xylylenediamine unit 30 mol% to 100 mol% and p-xylylenediamine unit 0 mol% to 70 mol%.
The content of m-xylylenediamine units is 30 mol% or more and 100 mol% or less, preferably 40 mol% or more and 100 mol% or less, and preferably 50 mol% or more and 100 mol% with respect to all diamine units. The content of p-xylylenediamine units is more preferably 0 mol% or more and 70 mol% or less, and preferably 0 mol% or more and 60 mol% or less, based on all diamine units. More preferably, it is 0 mol% or more and 50 mol% or less.

The dicarboxylic acid unit in the semi-aromatic polyamide polymer (C4) is an aliphatic dicarboxylic acid unit having 4 to 6 carbon atoms and having a straight chain and / or a side chain, 30 mol% to 100 mol%, terephthalic acid unit And / or isophthalic acid unit is 0 mol% or more and 70 mol% or less.
The content of the aliphatic dicarboxylic acid unit having 4 to 6 carbon atoms having a straight chain and / or a side chain is from 30 mol% to 100 mol%, and from 50 mol% to 100 mol, based on all dicarboxylic units. The content of terephthalic acid units and / or isophthalic acid units is preferably 0 mol% or more and 70 mol% or less based on the total dicarboxylic units. The mol% or less, preferably 0 mol% or more and 50 mol% or less, and more preferably 0 mol% or more and 30 mol% or less.

  Examples of the aliphatic dicarboxylic acid unit having 4 to 6 carbon atoms having a straight chain and / or a side chain include succinic acid, methylmalonic acid, ethylmalonic acid, dimethylmalonic acid, methylsuccinic acid, glutaric acid, adipic acid, methyl Examples include units derived from ethylmalonic acid, 2,2-dimethylsuccinic acid, 2,3-dimethylsuccinic acid, 2-methylglutaric acid, 3-methylglutaric acid and the like. These can use 1 type (s) or 2 or more types. Among these, a unit derived from adipic acid is preferable from the viewpoint of availability.

  The semi-aromatic polyamide polymer (C4) may contain other units other than the dicarboxylic acid unit and the diamine unit as long as they do not impair the excellent characteristics of the laminated tube of the present invention. Examples of other units include units derived from lactam and units derived from aminocarboxylic acid described in the description of the semi-aromatic polyamide polymer (C3), and these units should be used alone or in combination of two or more. Can do.

The semi-aromatic polyamide polymer (C4) contains other units derived from α-amino acids and units derived from β-amino acids as other units from the viewpoint of the chemical permeation preventing properties of the laminated tube. Is preferred. As α-amino acid units, alanine, 2-aminobutyric acid (butyrin), valine, norvaline, leucine, norleucine, t-leucine, isoleucine, serine, threonine, cysteine, methionine, 2-phenylglycine, phenylalanine, tyrosine, histidine, Examples thereof include units derived from tryptophan, proline and the like. Examples of the β-amino acid unit include units derived from 3-aminobutyric acid and the like. These may be any of D-form, L-form and racemate, or allo-form. These can use 1 type (s) or 2 or more types.
Among these, from the viewpoints of availability of raw materials, chemical solution permeation prevention properties, and the like, α-amino acid units having tertiary hydrogen in the α carbon are more preferable. Ease of availability, economy, polymerization rate, semi-aromatic polyamide weight From the viewpoint of the yellowness (YI) of the combined (C4), a unit derived from alanine is more preferable. In addition, the purity of the compound that can constitute the unit is 95% or more from the viewpoint of the influence on the polymerization such as the delay of the polymerization rate and the influence on the quality such as the yellowness of the semiaromatic polyamide polymer (C4). Preferably, it is 98.5% or more, and more preferably 99% or more. Further, the sulfate ion or ammonium ion contained as impurities is preferably 0.05% by mass or less, more preferably 0.02% by mass or less, and further preferably 0.005% by mass or less. .

  The content of units derived from lactam, units derived from amino carboxylic acids, units derived from α-amino acids and units derived from β-amino acids is the content of all dicarboxylic acid units. Based on this, it is preferably 40 mol% or less, more preferably 30 mol% or less, and even more preferably 20 mol% or less.

Specific examples of the semi-aromatic polyamide polymer (C4) include polymetaxylylene succinamide (polyamide MXD4), poly (metaxylylene succinamide / paraxylylene succinamide) copolymer (polyamide MXD4 / PXD4), Poly (metaxylylene succinamide / metaxylylene terephthalamide) copolymer (polyamide MXD4 / MXDT), poly (metaxylylene adipamide / metaxylylene isophthalamide) copolymer (polyamide MXD4 / MXDI) , Poly (metaxylylene succinamide / metaxylylene terephthalamide / metaxylylene isophthalamide) copolymer (polyamide MXD4 / MXDT / MXDI), poly (metaxylylene succinamide / paraxylylene succinamide / meta Xylylene terephthalamide / paraxili Terephthalamide) copolymer (polyamide MXD4 / PXD4 / MXDT / PXDT), poly (metaxylylene succinamide / paraxylylene succinamide / metaxylylene isophthalamide / paraxylylene isophthalamide) copolymer (polyamide MXD4) / PXD4 / MXDI / PXDI), poly (metaxylylene succinamide / paraxylylene succinamide / metaxylylene terephthalamide / paraxylylene terephthalamide / metaxylylene isophthalamide / paraxylylene isophthalamide) Copolymer (polyamide MXD4 / PXD4 / MXDT / PXDT / MXDI / PXDI), polymetaxylyleneglutamide (polyamide MXD5), poly (metaxylyleneglutamide / paraxylyleneglutamide) copolymer (polyamide MX) 5 / PXD5), poly (metaxylyleneglutamide / metaxylyleneterephthalamide) copolymer (polyamide MXD5 / MXDT), poly (metaxylyleneglutamide / metaxylyleneisophthalamide) copolymer (polyamide) MXD5 / MXDI), poly (metaxylyleneglutamide / metaxylylene terephthalamide / metaxylylene isophthalamide) copolymer (polyamide MXD5 / MXDT / MXDI), poly (metaxylyleneglutamide / paraxylylene) Glutamide / metaxylylene terephthalamide / paraxylylene terephthalamide) copolymer (polyamide MXD5 / PXD5 / MXDT / PXDT), poly (metaxylylene glutamide / paraxylylene glutamide / metaxylylene isophthalate) Ramide / paraxylylene isophthalamide) Copolymer (polyamide MXD5 / PXD5 / MXDI / PXDI), poly (metaxylyleneglutamide / paraxylyleneglutamide / metaxylyleneterephthalamide / paraxylyleneterephthalamide / metaxylyleneisophthalamide / para Xylylene isophthalamide) copolymer (polyamide MXD5 / PXD5 / MXDT / PXDT / MXDI / PXDI), polymetaxylylene adipamide (polyamide MXD6), poly (metaxylylene adipamide / paraxylylene adipamide) ) Copolymer (polyamide MXD6 / PXD6), poly (metaxylylene adipamide / metaxylylene terephthalamide) copolymer (polyamide MXD6 / MXDT), poly (metaxylylene adipamide / metaxylylene iso) Phthalamide) copolymer (polyamide MXD) / MXDI), poly (metaxylylene adipamide / metaxylylene terephthalamide / metaxylylene isophthalamide) copolymer (polyamide MXD6 / MXDT / MXDI), poly (metaxylylene adipamide / paraxili) Len adipamide / metaxylylene terephthalamide / paraxylylene terephthalamide) copolymer (polyamide MXD6 / PXD6 / MXDT / PXDT), poly (metaxylylene adipamide / paraxylylene adipamide / meta Xylylene isophthalamide / paraxylylene isophthalamide) copolymer (polyamide MXD6 / PXD6 / MXDI / PXDI), poly (metaxylylene adipamide / paraxylylene adipamide / metaxylylene terephthalamide / Paraxylylene terephthalamide / metaxylylene isophthalamide Para-xylylene isophthalamide) copolymer (polyamide MXD6 / PXD6 / MXDT / PXDT / MXDI / PXDI),
Poly (metaxylylene succinamide / alanine) copolymer (polyamide MXD4 / ALA), poly (metaxylylene succinamide / butyrin) copolymer (polyamide MXD4 / BUT), poly (metaxylylene succinamide / valine) Copolymer (polyamide MXD4 / VAL), poly (metaxylylene succinamide / leucine) copolymer (polyamide MXD4 / LEU), poly (metaxylylene succinamide / caproamide) copolymer (polyamide MXD4 / 6), Poly (metaxylylene succinamide / undecanamide) copolymer (polyamide MXD4 / 11), poly (metaxylylene succinamide / dodecanamide) copolymer (polyamide MXD4 / 12), poly (metaxylylene succinamide / Paraxylylene succinamide / alanine Copolymer (polyamide MXD4 / PXD4 / ALA), poly (metaxylylene succinamide / paraxylylene succinamide / butyrin) copolymer (polyamide MXD4 / PXD4 / BUT), poly (metaxylylene succinamide / paraxili) Rensuccinamide / valine) copolymer (polyamide MXD4 / PXD4 / VAL), poly (metaxylylene succinamide / paraxylylene succinamide / leucine) copolymer (polyamide MXD4 / PXD4 / LEU), poly (metaxylil) Rensuccinamide / paraxylylene succinamide / caproamide) copolymer (polyamide MXD4 / PXD4 / 6), poly (metaxylylene succinamide / paraxylylene succinamide / undecanamide) copolymer (polyamide MXD4 / PXD4 / 11), Li (metaxylylene succinamide / paraxylylene succinamide / dodecanamide) copolymer (polyamide MXD4 / PXD4 / 12), poly (metaxylylene succinamide / metaxylylene terephthalamide / alanine) copolymer ( Polyamide MXD4 / MXDT / ALA), poly (metaxylylene succinamide / metaxylylene terephthalamide / butyrin) copolymer (polyamide MXD4 / MXDT / BUT), poly (metaxylylene succinamide / metaxylylene terephthalate) Lamide / valine) copolymer (polyamide MXD4 / MXDT / VAL), poly (metaxylylene succinamide / metaxylylene terephthalamide / leucine) copolymer (polyamide MXD4 / MXDT / LEU), poly (metaxylylene) Xinamide / Metaxylylene Terephthalamide / caproamide) copolymer (polyamide MXD4 / MXDT / 6), poly (metaxylylene succinamide / metaxylylene terephthalamide / undecanamide) copolymer (polyamide MXD4 / MXDT / 11), poly (metaxylil) Rensuccinamide / metaxylylene terephthalamide / dodecanamide) copolymer (polyamide MXD4 / MXDT / 12), poly (metaxylylene succinamide / metaxylylene isophthalamide / alanine) copolymer (polyamide MXD4 / MXDI / 3), poly (metaxylylene succinamide / metaxylylene isophthalamide / caproamide) copolymer (polyamide MXD4 / MXDI / 6), poly (metaxylylene succinamide / metaxylylene isophthalamide / undecane) Amide) copolymerization (Polyamide MXD4 / MXDI / 11), poly (metaxylylenesuccinamide / metaxylyleneisophthalamide / dodecanamide) copolymer (polyamide MXD4 / MXDI / 12), poly (metaxylyleneglutamide / alanine) Polymer (polyamide MXD5 / ALA), poly (metaxylyleneglutamide / butyrin) copolymer (polyamide MXD5 / BUT), poly (metaxylyleneglutamide / valine) copolymer (polyamide MXD5 / VAL), poly (Metaxylyleneglutamide / leucine) copolymer (polyamide MXD5 / LEU), poly (metaxylyleneglutamide / caproamide) copolymer (polyamide MXD5 / 6), poly (metaxylyleneglutamide / undecanamide) Copolymer (polyamide MXD5 / 11), Li (metaxylyleneglutamide / dodecanamide) copolymer (polyamide MXD5 / 12), poly (metaxylyleneglutamide / paraxylyleneglutamide / alanine) copolymer (polyamide MXD5 / PXD5 / ALA), poly (Metaxylyleneglutamide / paraxylyleneglutamide / butyrin) copolymer (polyamide MXD5 / PXD5 / BUT), poly (metaxylyleneglutamide / paraxylyleneglutamide / valine) copolymer (polyamide MXD5 / PXD5 / VAL), poly (metaxylyleneglutamide / paraxylyleneglutamide / leucine) copolymer (polyamide MXD5 / PXD5 / LEU), poly (metaxylyleneglutamide / paraxylyleneglutamide / caproamide) Polymer (Polyamide MXD5 / PXD5 / 6) Copolymer of poly (metaxylyleneglutamide / paraxylyleneglutamide / undecanamide) (polyamide MXD5 / PXD5 / 11), poly (metaxylyleneglutamide / paraxylyleneglutamide / dodecanamide) Polymer (polyamide MXD5 / PXD5 / 12), poly (metaxylyleneglutamide / metaxylylene terephthalamide / alanine) copolymer (polyamide MXD5 / MXDT / ALA), poly (metaxylyleneglutamide / metaxili) Rentelephthalamide / butyrin) copolymer (polyamide MXD5 / MXDT / BUT), poly (metaxylyleneglutamide / metaxylylene terephthalamide / valine) copolymer (polyamide MXD5 / MXDT / VAL), poly ( Metaxylylene Glutamide / Metaxylylene Tele Taramide / leucine copolymer (polyamide MXD5 / MXDT / LEU), poly (metaxylyleneglutamide / metaxylylene terephthalamide / caproamide) copolymer (polyamide MXD5 / MXDT / 6), poly (metaxylylene) Glutamide / metaxylylene terephthalamide / undecanamide) copolymer (polyamide MXD5 / MXDT / 11), poly (metaxylylene glutamide / metaxylylene terephthalamide / dodecanamide) copolymer (polyamide MXD5 / MXDT / 12), poly (metaxylyleneglutamide / metaxylyleneisophthalamide / alanine) copolymer (polyamide MXD5 / MXDI / ALA), poly (metaxylyleneglutamide / metaxylyleneisophthalamide / butyrin) ) Copolymer (Polyamide MX 5 / MXDI / BUT), poly (metaxylyleneglutamide / metaxylyleneisophthalamide / valine) copolymer (polyamide MXD5 / MXDI / VAL), poly (metaxylyleneglutamide / metaxylyleneisophthalamide) / Leucine) copolymer (polyamide MXD5 / MXDI / LEU), poly (metaxylyleneglutamide / metaxylyleneisophthalamide / caproamide) copolymer (polyamide MXD5 / MXDI / 6), poly (metaxylyleneglutami) / Metaxylyleneisophthalamide / undecanamide) copolymer (polyamide MXD5 / MXDI / 11), poly (metaxylyleneglutamide / metaxylyleneisophthalamide / dodecanamide) copolymer (polyamide MXD5 / MXDI) / 12), poly (metaxylylene azimuth Pamide / alanine) copolymer (polyamide MXD6 / ALA), poly (metaxylylene adipamide / butyrin) copolymer (polyamide MXD6 / BUT), poly (metaxylylene adipamide / valine) copolymer ( Polyamide MXD6 / VAL), poly (metaxylylene adipamide / leucine) copolymer (polyamide MXD6 / LEU), poly (metaxylylene adipamide / caproamide) copolymer (polyamide MXD6 / 6), poly ( Metaxylylene adipamide / undecanamide) copolymer (polyamide MXD6 / 11), poly (metaxylylene adipamide / dodecanamide) copolymer (polyamide MXD6 / 12), poly (metaxylylene adipamide) / Paraxylylene adipamide / alanine) copolymer (polyamide MXD6 / PXD6 / LA), poly (metaxylylene adipamide / paraxylylene adipamide / butyrin) copolymer (polyamide MXD6 / PXD6 / BUT), poly (metaxylylene adipamide / paraxylylene adipamide / valine) ) Copolymer (polyamide MXD6 / PXD6 / VAL), poly (metaxylylene adipamide / paraxylylene adipamide / leucine) copolymer (polyamide MXD6 / PXD6 / LEU), poly (metaxylylene adipa) Amide / paraxylylene adipamide / caproamide) copolymer (polyamide MXD6 / PXD6 / 6), poly (metaxylylene adipamide / paraxylylene adipamide / undecanamide) copolymer (polyamide MXD6 / PXD6) / 11), poly (metaxylylene adipamide / paraxylylene adipamide / dode Amide) copolymer (polyamide MXD6 / PXD6 / 12), poly (metaxylylene adipamide / metaxylylene terephthalamide / alanine) copolymer (polyamide MXD6 / MXDT / ALA), poly (metaxylylene azimuth) Pamide / metaxylylene terephthalamide / butyrin) copolymer (polyamide MXD6 / MXDT / BUT), poly (metaxylylene adipamide / metaxylylene terephthalamide / valine) copolymer (polyamide MXD6 / MXDT) / VAL), poly (metaxylylene adipamide / metaxylylene terephthalamide / leucine) copolymer (polyamide MXD6 / MXDT / LEU), poly (metaxylylene adipamide / metaxylylene terephthalamide / Caproamide) copolymer (polyamide MXD6 / MXDT / 6), Poly (metaxylylene adipamide / metaxylylene terephthalamide / undecanamide) copolymer (polyamide MXD6 / MXDT / 11), poly (metaxylylene adipamide / metaxylylene terephthalamide / dodecanamide) Copolymer (polyamide MXD6 / MXDT / 12), poly (metaxylylene adipamide / metaxylylene isophthalamide / alanine) copolymer (polyamide MXD6 / MXDI / ALA), poly (metaxylylene adipamide) / Metaxylylene isophthalamide / butyrin) copolymer (polyamide MXD6 / MXDI / BUT), poly (metaxylylene adipamide / metaxylylene isophthalamide / valine) copolymer (polyamide MXD6 / MXDI / VAL) ), Poly (metaxylylene adipamide / metaxylylene) Phthalamide / leucine) copolymer (polyamide MXD6 / MXDI / LEU), poly (metaxylylene adipamide / metaxylylene isophthalamide / caproamide) copolymer (polyamide MXD6 / MXDI / 6), poly (metaxylyl) Ren adipamide / metaxylylene isophthalamide / undecanamide) copolymer (polyamide MXD6 / MXDI / 11), poly (metaxylylene adipamide / metaxylylene isophthalamide / dodecanamide) copolymer ( And polyamide MXD6 / MXDI / 12).

  Among these, polymetaxylylene adipamide (polyamide MXD6) from the viewpoints of availability and sufficient physical properties such as heat resistance, chemical resistance, impact resistance, and chemical permeation prevention properties of the obtained laminated tube. ), Poly (metaxylylene adipamide / paraxylylene adipamide) copolymer (polyamide MXD6 / PXD6), poly (metaxylylene adipamide / metaxylylene terephthalamide) copolymer (polyamide MXD6) / MXDT), poly (metaxylylene adipamide / metaxylylene isophthalamide) copolymer (polyamide MXD6 / MXDI), poly (metaxylylene adipamide / metaxylylene terephthalamide / metaxylylene iso Phthalamide) copolymer (polyamide MXD6 / MXDT / MXDI), poly (metaxylylene adipamide) Alanine) copolymer (polyamide MXD6 / A), poly (metaxylylene adipamide / leucine) copolymer (polyamide MXD6 / LEU), poly (metaxylylene adipamide / metaxylylene isophthalamide / alanine) ) Copolymer (polyamide MXD6 / MXDI / ALA) and poly (metaxylylene adipamide / metaxylylene isophthalamide / leucine) copolymer (polyamide MXD6 / MXDI / LEU).

  According to JIS K-6920, the relative viscosity of the semi-aromatic polyamide polymer (C1) measured under the conditions of 96% sulfuric acid, 1% polymer concentration and 25 ° C. is the mechanical property of the resulting laminated tube. From the viewpoint of ensuring and ensuring the desirable formability of the laminated tube by setting the viscosity at the time of melting to an appropriate range, it is preferably 1.5 or more and 3.5 or less, and is 1.8 or more and 3.0 or less. More preferably, it is 1.9 or more and 3.0 or less.

  In addition, there is no special restriction | limiting in the kind of the terminal group of semi-aromatic polyamide polymer (C1), its density | concentration, and molecular weight distribution. One or more of monoamine, diamine, polyamine, monocarboxylic acid, and dicarboxylic acid can be added in appropriate combination for molecular weight adjustment and melt stabilization during molding. For example, alicyclic such as aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dicyclohexylamine Aromatic monoamines such as monoamine, aniline, toluidine, diphenylamine, naphthylamine, 1,2-ethanediamine, 1,3-propanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 2 -Methyl-1,8-octanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 1,10-decanediamine, 5-methyl -1,9 Alicyclic diamine such as nonanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, cyclohexanediamine, bis (aminomethyl) cyclohexane, 5-amino-1,3,3-trimethylcyclohexanemethylamine Aromatic amines such as diamine, m-phenylenediamine, p-phenylenediamine, polyalkyleneimines, polyalkylenepolyamines, polyamines such as polyvinylamine, polyallylamine, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, Aliphatic monocarboxylic acids such as lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid, cycloaliphatic carboxylic acid, benzoic acid, toluic acid, α-naphthalenecarboxylic acid acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, aromatic monocarboxylic acid such as phenylacetic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, pimelic acid, suberic acid, azelaic acid, Aliphatic dicarboxylic acids such as sebacic acid, undecanedioic acid, dodecanedioic acid, alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, phthalates Aromatic dicarboxylic acids such as acids can be mentioned. These can use 1 type (s) or 2 or more types. The amount of these molecular weight regulators used varies depending on the reactivity of the molecular weight regulator and the polymerization conditions, but is appropriately determined so that the relative viscosity of the polyamide to be finally obtained falls within the above range.

Considering the melt stability, it is preferable that the end of the molecular chain of the semi-aromatic polyamide polymer (C1) is sealed with an end-capping agent, and that 10% or more of the end groups are sealed. More preferably, 20% or more of the end groups are more preferably sealed. The end capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the end of the polyamide, but from the viewpoint of reactivity, stability of the capped end, etc. An acid or a monoamine is preferable, and a monocarboxylic acid is more preferable from the viewpoint of easy handling. In addition, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, monoalcohols, and the like can be used.
The monocarboxylic acid used as the end-capping agent is not particularly limited as long as it has reactivity with an amino group, but the above-mentioned aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, aromatic monocarboxylic acid is not limited. A carboxylic acid etc. are mentioned. Among these, from the viewpoint of reactivity, stability of the sealing end, price, etc., acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid Benzoic acid is preferred. The monoamine used as the end-capping agent is not particularly limited as long as it has reactivity with a carboxyl group, and examples thereof include the aliphatic monoamines, alicyclic monoamines, and aromatic monoamines. Among these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are preferable from the viewpoints of reactivity, boiling point, sealing end stability, price, and the like.
The amount of the terminal blocking agent used can be appropriately selected in consideration of the reactivity, boiling point, reaction apparatus, reaction conditions, etc. of the terminal blocking agent used. From the viewpoint of adjusting the degree of polymerization, it is preferably 0.1 mol% or more and 15 mol% or less with respect to the total number of moles of the dicarboxylic acid and diamine which are raw material components.

  A phosphorus compound can be added to the semi-aromatic polyamide polymer (C1) in order to increase the processing stability during melt molding or to prevent coloring. As phosphorus compounds, hypophosphorous acid, hypophosphorous acid compounds such as hypophosphite, phosphorous acid compounds such as phosphorous acid, phosphite, phosphite, phosphoric acid, phosphate, Examples thereof include phosphoric acid compounds such as phosphate esters. Examples of hypophosphites include potassium hypophosphite, sodium hypophosphite, calcium hypophosphite, magnesium hypophosphite, vanadium hypophosphite, manganese hypophosphite, nickel hypophosphite, Examples thereof include cobalt hypophosphite and lithium hypophosphite. Examples of the phosphite include potassium phosphite, sodium phosphite, calcium phosphite, magnesium phosphite, manganese phosphite, nickel phosphite, cobalt phosphite and the like. Examples of phosphites include phosphite methyl ester, phosphite ethyl ester, phosphite isopropyl ester, phosphite butyl ester, phosphite hexyl ester, phosphite isodecyl ester, decyl phosphite Examples include esters, stearyl phosphite esters, phenyl phosphite esters, triethyl phosphite, triphenyl phosphite, and the like. Examples of the phosphate include potassium phosphate, sodium phosphate, calcium phosphate, magnesium phosphate, manganese phosphate, nickel phosphate, and cobalt phosphate. Examples of phosphate esters include monomethyl phosphate ester, dimethyl phosphate ester, trimethyl phosphate, monoethyl phosphate ester, diethyl phosphate ester, triethyl phosphate, propyl phosphate ester, dipropyl phosphate ester, tripropyl phosphate, isopropyl Phosphate ester, diisopropyl phosphate ester, triisopropyl phosphate, butyl phosphate ester, dibutyl phosphate ester, tributyl phosphate, isobutyl phosphate ester, diisobutyl phosphate ester, triisobutyl phosphate, hexyl phosphate ester, dihexyl phosphate ester, Trihexyl phosphate, octyl phosphate, dioctyl phosphate, trioctyl phosphate, 2-ethylhexyl phosphate, di (2-ethylhexyl) phosphate Ter, tri (2-ethylhexyl) phosphate decyl phosphate, didecyl phosphate, tridecyl phosphate, isodecyl phosphate, diisodecyl phosphate, triisodecyl phosphate, stearyl phosphate, distearyl phosphate, tristearyl phosphate Examples include acids, monophenyl phosphates, diphenyl phosphates, and triphenyl phosphates. These can use 1 type (s) or 2 or more types. Among these, a hypophosphite metal salt such as sodium hypophosphite, potassium hypophosphite, lithium hypophosphite and the like is preferable from the viewpoint of high effect of promoting amidation reaction and anti-coloring effect, Sodium hypophosphite is more preferred.

The compounding amount of the phosphorus compound is 0.03 mass in terms of phosphorus atom concentration with respect to 100 mass parts of the semi-aromatic polyamide polymer (C1) from the viewpoint of sufficiently ensuring the anti-coloring effect and suppressing the generation of gel. It is preferably no less than 0.35 parts by mass, more preferably no less than 0.05 parts by mass and no greater than 0.30 parts by mass, and even more preferably no less than 0.07 parts by mass and no greater than 0.25 parts by mass. preferable.
The addition method of these phosphorus compounds is the method of adding to the aqueous solution of nylon salt, diamine or dicarboxylic acid which is the raw material of the semi-aromatic polyamide polymer (C1), the method of adding to the dicarboxylic acid in the molten state, Any method may be used as long as it can be uniformly dispersed in the semi-aromatic polyamide polymer (C1), but the method is not limited thereto.

An alkali metal compound can be added to the semi-aromatic polyamide polymer (C1) in combination with the phosphorus compound. In order to prevent coloring of the polyamide during polycondensation, a sufficient amount of phosphorus compound needs to be present, but in some cases there is a risk of causing gelation of the polyamide. It is preferable to coexist an alkali metal compound. As the alkali metal compound, an alkali metal hydroxide or an alkali metal carboxylate is preferable.
Specific examples of the alkali metal compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, lithium formate, sodium formate, potassium formate, rubidium formate, cesium formate, lithium acetate, and acetic acid. Examples include sodium, potassium acetate, rubidium acetate, cesium acetate, lithium propionate, sodium propionate, potassium propionate, rubidium propionate, cesium propionate, lithium butyrate, sodium butyrate, potassium butyrate, rubidium butyrate, cesium butyrate, and the like. These can use 1 type (s) or 2 or more types. Among these, sodium hydroxide or sodium acetate is preferable from the viewpoint of economy.

When an alkali metal compound is added to the polycondensation system of the semi-aromatic polyamide polymer (C1), the value obtained by dividing the number of moles of the compound by the number of moles of the phosphorus compound is the effect of promoting the amidation reaction or the polycondensation. Is preferably 0.5 or more and 1 or less, more preferably 0.55 or more and 0.95 or less, and more preferably 0.6 or more and 0.0. More preferably, it is 9 or less.
The method for adding these alkali metal compounds includes a method for adding to a nylon salt aqueous solution, a diamine or dicarboxylic acid that is a raw material of the semi-aromatic polyamide polymer (C1), a method for adding to a dicarboxylic acid in a molten state, Any method may be used as long as it can be uniformly dispersed in the semi-aromatic polyamide polymer (C1), but is not limited thereto.

  Semi-aromatic polyamide polymer (C1) 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 method for producing the semi-aromatic polyamide polymer (C1), there are known methods such as melt polymerization, solution polymerization and solid phase polymerization, and these methods are used to repeat normal pressure, reduced pressure, and pressurization operations. An aromatic polyamide polymer (C1) can be produced. These production methods can be used alone or in appropriate combination.

  Olefin polymer (C2) having a flexural modulus measured in accordance with ISO 178 in the semi-aromatic polyamide polymer composition (C) of 500 MPa or less (hereinafter, referred to as olefin polymer (C2)). ) Is added to improve the low temperature impact resistance of the semi-aromatic polyamide polymer (C1). When the flexural modulus measured in accordance with ISO 178 of the olefin polymer (C2) exceeds this value, the impact improving effect may be insufficient.

  As the olefin polymer (C2), (ethylene and / or propylene) / α-olefin copolymer, (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid) Ester) -based copolymer, ionomer polymer, aromatic vinyl compound / conjugated diene compound-based block copolymer, and one or more of them can be used.

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

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

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

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

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

  Further, (ethylene and / or propylene) / α-olefin copolymer, (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated) used as the olefin polymer (C2). As the carboxylic acid ester) copolymer, ionomer polymer, and aromatic vinyl compound / conjugated diene compound block copolymer, a polymer modified with a carboxylic acid and / or a derivative thereof is preferably used. By modifying with such a component, a functional group having affinity for the semi-aromatic polyamide polymer (C1) is included in the molecule.

  Functional groups having affinity for the semi-aromatic polyamide polymer (C1) 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 and the like. Examples of compounds containing these functional groups include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid Endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid and metal salts of these carboxylic acids, monomethyl maleate, monomethyl itaconate, methyl acrylate, ethyl acrylate, butyl acrylate 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, itaconic anhydride, citracone anhydride Acid, endobicyclo- 2.2.1] -5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, acrylamide, methacrylamide, glycidyl acrylate, glycidyl methacrylate, Examples include glycidyl ethacrylate, glycidyl itaconate, and glycidyl citraconic acid. These can use 1 type (s) or 2 or more types.

  The mixing ratio of both the semi-aromatic polyamide polymer (C1) and the olefin polymer (C2) in the semi-aromatic polyamide polymer composition (C) maintains the mechanical properties of the resulting tube, and the low-temperature impact resistance From the viewpoint of sufficiently ensuring the property, fluidity and chemical liquid permeation prevention, the content of the semi-aromatic polyamide polymer (C1) is 50% by mass to 95% by mass, and 55% by mass to 93% by mass. The content of the olefin polymer (C2) is preferably 5% by mass or more and 50% by mass or less, and more preferably 7% by mass or more and 45% by mass or less. It is preferably 10% by mass or more and 40% by mass or less.

  There are no particular restrictions on the method of mixing the aromatic polyamide polymer (C1) and the olefin polymer (C2), and various additives that have been conventionally known are employed as required. Can do. For example, using both a tumbler and a mixer, a method of uniformly dry blending the pellets of the aliphatic aromatic polyamide polymer (C1) and the olefin polymer (C2) so as to have the above mixing ratio, both are required. Along with other components added accordingly, it can be produced by a method of dry blending in advance at a concentration used at the time of molding and melt kneading. The melt kneading can be performed using a kneader such as a single screw extruder, a twin screw extruder, a kneader, or a Banbury mixer.

  The semi-aromatic polyamide polymer composition (C) may contain other polyamide-based resins or other thermoplastic resins in addition to the semi-aromatic polyamide polymer (C1) and the olefin polymer (C2). Good. Examples of other polyamide-based resins or other thermoplastic resins include the same resins as in the case of the polyamide polymer (A). Further, it may be a mixture with the polyamide polymer (A) or the polyamide polymer (B). The content of the semi-aromatic polyamide polymer (C1) in the semi-aromatic polyamide polymer composition (C) in the mixture is preferably 50% by mass or more.

  Furthermore, the semi-aromatic polyamide polymer composition (C) includes an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, an inorganic filler, an antistatic agent, and a flame retardant as necessary. Further, a crystallization accelerator, a plasticizer, a colorant, a lubricant and the like may be added.

In addition, a carbodiimide compound can be added to the semi-aromatic polyamide polymer composition (C) in order to improve hydrolysis resistance. The carbodiimide compound has a carbodiimide group (—N═C═N—) of the following general formula, a monocarbodiimide having one carbodiimide group in the molecule, or a poly having two or more carbodiimide groups in the molecule. Examples thereof include carbodiimide, and those synthesized by a generally well-known method can be used.
For example, a compound synthesized by subjecting a diisocyanate compound corresponding to carbodiimide to a decarboxylation condensation reaction in a solvent-free or inert solvent at a temperature of about 70 ° C. or higher in the presence of a carbodiimidization catalyst can be used.

Among the carbodiimide compounds, the mono- or dicarbodiimide compounds include N, N′-dimethylcarbodiimide, N, N′-diisopropylcarbodiimide, N, N′-diisobutylcarbodiimide, N, N′-di-t-butylcarbodiimide, N , N′-dioctylcarbodiimide, N, N′-dioctyldecylcarbodiimide, N, N′-dicyclohexylcarbodiimide, N, N′-diphenylcarbodiimide, N, N′-di-o-tolylcarbodiimide, N, N′-di -P-tolylcarbodiimide, N, N'-di-2,3-xylylphenylcarbodiimide, N, N'-di-2,6-xylylphenylcarbodiimide, N, N'-di-3,4-key Silylphenylcarbodiimide, N, N′-dibenzylcarbodiimide, N, N′-bis (p-aminophen ) Carbodiimide, N, N′-bis (o-chlorophenyl) carbodiimide, N, N′-bis (p-chlorophenyl) carbodiimide, N, N′-bis (p-nitrophenyl) carbodiimide, N, N′-bis (P-hydroxyphenyl) carbodiimide, N, N′-bis (o-ethylphenyl) carbodiimide, N, N′-bis (p-ethylphenyl) carbodiimide, N, N′-bis (o-isopropylphenyl) carbodiimide, N, N′-bis (p-isopropylphenyl) carbodiimide, N, N′-bis (o-isobutylphenyl) carbodiimide, N, N′-bis (p-isobutylphenyl) carbodiimide, N, N′-bis (2 , 5-dichlorophenyl) carbodiimide, N, N′-bis (3,4-dichlorophenyl) carbodiimide, N , N′-bis (2,6-dimethylphenyl) carbodiimide, N, N′-bis (2,6-diethylphenyl) carbodiimide, N, N′-bis (2-ethyl-6-isopropylphenyl) carbodiimide, N , N′-bis (2-butyl-6-isopropylphenyl) carbodiimide, N, N′-bis (2,6-diisopropylphenyl) carbodiimide, N, N′-bis (2,6-di-t-butylphenyl) ) Carbodiimide, N, N′-bis (2,4,6-trimethylphenyl) carbodiimide, N, N′-bis (2,4,6-triisopropylphenyl) carbodiimide, N, N′-bis (2,4 , 6-Tributylphenyl) carbodiimide, N, N′-di-β-naphthylcarbosiimide, Nt-butyl-N′-isopropylcarbodiimide, N-octa Decyl-N'-phenylcarbodiimide, N-benzyl-N'-phenylcarbodiimide, N-benzyl-N'-tolylcarbodiimide, N-octadecyl-N'-tolylcarbodiimide, N-cyclohexyl-N'-tolylcarbodiimide, N- Tolyl-N′-phenylcarbosiimide, p-phenylenebis (o-toluylcarbodiimide), p-phenylenebis (cyclohexylcarbodiimide), p-phenylenebis (p-chlorophenylcarbodiimide), 2,6,2 ′, 6 Examples include '-tetraisopropyldiphenylcarbodiimide, hexamethylenebis (cyclohexylcarbodiimide), ethylenebis (phenylcarbodiimide), and ethylenebis (cyclohexylcarbodiimide). As polycarbodiimide, poly (1,6-hexamethylenecarbodiimide), poly (4,4′-methylenebiscyclohexylcarbodiimide), poly (1,3-cyclohexylenecarbodiimide), poly (1,4-cyclohexylenecarbodiimide) , Poly (4,4′-diphenylmethanecarbodiimide), poly (3,3′-dimethyl-4,4′-diphenylmethanecarbodiimide), poly (naphthylenecarbodiimide), poly (p-phenylenecarbodiimide), poly (m-phenylene) Carbodiimide), poly (tolylcarbodiimide), poly (diisopropylcarbodiimide), poly (methyl-diisopropylphenylenecarbodiimide), poly (triethylphenylenecarbodiimide), poly (triisopropylphenylenecarbodiimi D) and the like.
Among these, from the viewpoint of industrial availability, dicyclohexylcarbodiimide, bis (2,6-diisopropylphenyl) carbodiimide, poly (4,4′-dicyclohexylmethanecarbodiimide) and poly (1,3,5-trimethyl). (Isopropylphenylenecarbodiimide) and poly (1,3,5-triisopropylphenylene and 1,5-diisopropylphenylene) carbodiimide are preferable, and commercially available products include Nisshinbo Carbodilite, Rhein Chemy's Starbazole.

  As the carbodiimide compound, those produced by various methods can be used, but basically, a conventional method for producing polycarbodiimide (US Pat. Chem. 28, 2069-2075 (1963), Chemal Review 1981, Vo1.81 No. 4 p.619-621) can be used. In general, a carbodiimide having an isocyanate terminal is produced by a condensation reaction involving decarboxylation of an organic diisocyanate.

Examples of the diisocyanate that can be used as a synthesis raw material when producing a carbodiimide compound include aliphatic diisocyanates, alicyclic diisocyanates, aromatic diisocyanates, and the like. Specifically, 1,6-hexamen Diisocyanate, cyclohexane-1,4-diisocyanate, isophorone diisocyanate, dicyclohexylmethane-4,4′-diisocyanate, methylcyclohexane diisocyanate, 1,5-naphthalene diisocyanate, 4,4′-diphenylmethane diisocyanate, 4,4′-diphenyldimethylmethane Diisocyanate, 1,3-phenylene diisocyanate, 1,4-phenylene diisocyanate, 2,4-tolylene diisocyanate, 2,6-tolylene diisocyanate, 2,4- Li diisocyanate, xylylene diisocyanate, tetramethylxylylene diisocyanate, 2,6-diisopropylphenyl isocyanate, 1,3,5-triisopropenyl Hill-2,4-diisocyanate. These can use 1 type (s) or 2 or more types.
Among the diisocyanates, carbodiimide compounds using aromatic isocyanates are generally thermosetting resins. Therefore, when melt kneading with a polyamide resin, self-crosslinking occurs and the carbodiimide compound is solidified inside the polyamide resin. Remains, which is not preferable because kneading is insufficient. Therefore, the carbodiimide compound is preferably an aliphatic and / or alicyclic isocyanate-derived carbodiimide compound.

  In the method for producing a carbodiimide compound, the degree of polymerization of polycarbodiimide is appropriately controlled by using a compound that reacts with a terminal isocyanate of carbodiimide and seals, for example, monoisocyanate, in the decarboxylation condensation reaction. can do. Specific examples of monoisocyanate for sealing the end of polycarbodiimide and controlling the degree of polymerization include phenyl isocyanate, tolyl isocyanate, dimethylphenyl isocyanate, naphthyl isocyanate, cyclohexyl isocyanate, butyl isocyanate and the like. These can use 1 type (s) or 2 or more types.

  The end-capping agent for sealing the end of polycarbodiimide and controlling the degree of polymerization is not limited to the above-mentioned monoisocyanate, and active hydrogen having active hydrogen capable of reacting with an isocyanate group. Compounds can be used. As such an active hydrogen compound, a wide range of aliphatic, aromatic and alicyclic compounds having active hydrogen can be used. Specifically, methanol, ethanol, phenol, cyclohexanol, N-methylethanolamine, Compounds having a hydroxyl group such as polyethylene glycol monomethyl ether and polypropylene glycol monomethyl ether, secondary amines such as diethylamine and dicyclohexylamine, primary amines such as butylamine and cyclohexylamine, carboxylic acids such as succinic acid, benzoic acid and cyclohexanecarboxylic acid, Examples include thiols such as ethyl mercaptan, allyl mercaptan, and thiophenol, and compounds having an epoxy group. These can use 1 type (s) or 2 or more types.

  Examples of the carbodiimidization catalyst used when producing a carbodiimide compound by a decarboxylation condensation reaction of a diisocyanate compound include, for example, 1-phenyl-2-phospholene-1-oxide, 3-methyl-1-phenyl-2-phospholene-1 Metal catalysts such as phospholene oxides such as 1-oxide, 1-ethyl-2-phospholene-1-oxide, 3-methyl-2-phospholene-1-oxide, and their 3-phospholene isomers, and tetrabutyl titanate. 1 type or 2 types or more can be used for these. Among these, 3-methyl-1-phenyl-2-phospholene-1-oxide is preferable from the viewpoint of reactivity.

  The content of the carbodiimide compound is sufficient to ensure hydrolysis resistance of the obtained laminated tube, and from the viewpoint of preventing thickening by self-crosslinking or reaction with polyamide during melt molding of the laminated tube. The amount is preferably 0.05 parts by mass or more and 5.0 parts by mass or less, more preferably 0.1 parts by mass or more and 4.0 parts by mass or less, with respect to 100 parts by mass of the combined (C1). More preferably, it is 2 parts by mass or more and 3.0 parts by mass or less.

The laminated tube according to the present invention comprises a (a) layer comprising a polyamide polymer (A), a (b) layer comprising a polyamide polymer (B), and a semi-aromatic polyamide polymer composition (C) (c) ) Including at least three layers. By including (c) layer which consists of a semi-aromatic polyamide polymer composition (C), the chemical | medical solution permeation-proof property of a laminated tube can be improved.
As a preferred embodiment, the (b) layer comprising the polyamide polymer (B) is in direct contact with the (a) layer comprising the polyamide polymer (A), and the (a) layer comprising the polyamide polymer (A) It arrange | positions between the (c) layers which consist of a semi-aromatic polyamide polymer composition (C). The (b) layer made of the polyamide polymer (B) is in direct contact with the (a) layer made of the polyamide polymer (A), and the (a) layer made of the polyamide polymer (A) and the semi-aromatic polyamide weight By disposing between the layers (c) made of the combined composition (C), a laminated tube having good interlayer adhesion can be obtained.
In a more preferred embodiment, the (a) layer made of the polyamide polymer (A) is arranged in the outermost layer of the laminated tube, and the (c) layer made of the semi-aromatic polyamide polymer composition (C) is made of polyamide. It arrange | positions inside with respect to the (a) layer which consists of a polymer (A). By disposing the (a) layer made of the polyamide polymer (A) in the outermost layer, a laminated tube excellent in chemical resistance and flexibility can be obtained.

  In the laminated tube of the present invention, the thickness of each layer is not particularly limited, and can be adjusted according to the type of polymer constituting each layer, the total number of layers in the laminated tube, the use, etc. It is determined in consideration of the properties of the laminated tube, such as chemical penetration prevention, low temperature impact resistance, flexibility, etc. Generally, the thickness of the (a) layer, (b) layer, (c) layer is the thickness of the entire laminated tube. The thickness is preferably 3% or more and 90% or less, respectively. In consideration of the balance between the low temperature impact resistance and the chemical liquid permeation preventing property, the thickness of the layer (c) is more preferably 5% or more and 80% or less, and more preferably 10% or more and 50% with respect to the total thickness of the laminated tube. More preferably, it is% or less.

The total number of layers in the laminated tube of the present invention is as follows: (a) layer composed of polyamide polymer (A), (b) layer composed of polyamide polymer (B), and semi-aromatic polyamide polymer composition ( The layer is not particularly limited as long as it includes at least three layers including the layer (c) composed of C). Furthermore, the laminated tube of the present invention has other functions in addition to the three layers (a), (b), and (c) to provide additional functions or to obtain an economically advantageous laminated tube. The layer made of the plastic resin may have one layer or two or more layers. The number of layers of the laminated tube of the present invention is three or more, but it is eight or less as judged from the mechanism of the structure manufacturing apparatus. It is preferably 3 or more and 7 or less.

  In the laminated tube of the present invention, polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), and poly (caproamide / hexamethylene adipamide) copolymer (polyamide 6 / 66), and the (d) layer is disposed in direct contact with the (c) layer made of the semi-aromatic polyamide polymer composition (C). (D) layer consisting of polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), and poly (caproamide / hexamethylene adipamide) copolymer (polyamide 6/66) is disposed. Thus, a laminated tube having an excellent balance between mechanical properties and economy can be obtained. The layer (d) made of polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), and poly (caproamide / hexamethylene adipamide) copolymer (polyamide 6/66) is semi-aromatic. By directly contacting the layer (c) made of the group polyamide polymer composition (C), a laminated tube having good interlayer adhesion can be obtained.

Polyamide polymer (D) used in the present invention includes polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), and poly (caproamide / hexamethylene adipamide) copolymer (polyamide 6). / 66) is at least one polyamide polymer selected from the group consisting of (66) (hereinafter sometimes referred to as polyamide polymer (D)).
Polycaproamide (polyamide 6) is composed of a caproamide unit represented by the following formula: (—CO— (CH ₂ ) ₆ —NH—) _n having an amide bond (—CONH—) in the main chain, and is composed of 6-aminocaprone. It can be obtained by polymerizing acid or caprolactam.
Polyhexamethylene adipamide (polyamide 66) has an amide bond (—CONH—) in the main chain: (—NH— (CH ₂ ) ₆ —NH—CO— (CH ₂ ) ₄ —CO—) It consists of a hexamethylene adipamide unit represented by _n and can be obtained by polymerizing 1,6-hexanediamine and adipic acid.
The poly (caproamide / hexamethylene adipamide) copolymer (polyamide 6/66) has the following formula having an amide bond (—CONH—) in the main chain: (—CO— (CH ₂ ) ₆ —NH—) A polyamide copolymer having a caproamide unit represented by _n and the following formula: (—NH— (CH ₂ ) ₆ —NH—CO— (CH ₂ ) ₄ —CO—) a hexamethylene adipamide unit represented by _n Yes, it can be obtained by copolymerizing 6-aminocaproic acid or caprolactam, 1,6-hexanediamine and adipic acid. The molar ratio of the caproamide unit to the hexamethylene adipamide unit is preferably 3:97 mol% or more and 97: 3 mol% or less in consideration of the heat resistance and mechanical strength of the obtained laminated tube. More preferably, it is 95 mol% or more and 95: 5 mol% or less.

  As a manufacturing apparatus of a polyamide polymer (D), the well-known polyamide manufacturing apparatus described by description of the polyamide polymer (A) is mentioned. As a manufacturing method of a polyamide polymer (D), the well-known method described by description of the polyamide polymer (A) is mentioned.

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

  In the polyamide polymer (D), when the terminal amino group concentration per 1 g of the polyamide is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), [A]> [B ] +5 (hereinafter sometimes referred to as terminal-modified polyamide) is preferable in view of interlayer adhesion with the polyamide polymer (B) and the semi-aromatic polyamide polymer composition (C), [ A]> [B] +10 is more preferable, and [A]> [B] +15 is more preferable. Furthermore, from the viewpoint of the melt stability of the polyamide and the suppression of the generation of gel-like material, [A]> 20 is preferable, and 30 <[A] <120 is more preferable.

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

  The polyamide polymer (D) may contain other polyamide-based resins or other thermoplastic resins. Examples of other polyamide-based resins or other thermoplastic resins include the same resins as in the case of the polyamide polymer (A). Furthermore, it may be a mixture with a polyamide polymer (A), a polyamide polymer (B), or a semi-aromatic polyamide polymer (C1). The content of the polyamide polymer (D) in the mixture is preferably 50% by mass or more, and more preferably 60% by mass or more.

In order to improve the low temperature impact resistance of the polyamide polymer (D), it is preferable to add an impact resistance improver, and particularly in ISO 178 described in the semi-aromatic polyamide polymer composition (C). It is more preferable to add an olefin polymer having a flexural modulus measured in accordance with 500 MPa or less. If the flexural modulus exceeds this value, the impact improvement effect may be insufficient.
The content of the impact resistance improving material is 1 part by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the polyamide polymer (D) from the viewpoint of sufficiently ensuring the mechanical strength and low temperature impact resistance of the laminated tube. It is preferable that it is 3 parts by mass or more and 25 parts by mass or less.
Moreover, in order to improve the softness | flexibility of a polyamide polymer (D), it is preferable to add a plasticizer, and it is more preferable to add the plasticizer described in the said polyamide polymer (A) especially.
The content of the plasticizer may be 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the polyamide polymer (D) from the viewpoint of sufficiently ensuring the flexibility and low temperature impact resistance of the laminated tube. Preferably, it is 2 parts by mass or more and 20 parts by mass or less.

  Furthermore, for the polyamide polymer (D), 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. Colorants, lubricants and the like may be added.

  In the laminated tube of the present invention, as a further preferred embodiment, the (c) layer made of the semi-aromatic polyamide polymer composition (C) is disposed in the innermost layer of the laminated tube. By arranging the (c) layer made of the semi-aromatic polyamide polymer composition (C) in the innermost layer, a laminated tube having excellent chemical resistance can be obtained.

  In the laminated tube according to the present invention, the (c) layer made of the semi-aromatic polyamide polymer composition (C) is arranged on the inner side with respect to the (a) layer made of the polyamide polymer (A). And further comprising (e) a layer comprising a fluorine-containing polymer (E) in which a functional group having reactivity with an amino group is introduced into the molecular chain, and the (e) layer is disposed in the innermost layer. A laminated tube having a layered structure is a more preferred embodiment.

The fluorine-containing polymer (E) used in the present invention is a fluorine-containing polymer in which a functional group having reactivity with an amino group is introduced into a molecular chain (hereinafter referred to as a fluorine-containing polymer). (E) may be referred to.)
The fluorine-containing polymer (E) is a polymer (homopolymer or copolymer) having a repeating unit derived from at least one fluorine-containing monomer. It is not particularly limited as long as it is a fluorine-containing polymer that can be heat-melted.

Here, as the fluorine-containing monomer, tetrafluoroethylene (TFE), trifluoroethylene, vinylidene fluoride (VDF), vinyl fluoride (VF), chlorotrifluoroethylene (CTFE), trichlorofluoroethylene, hexafluoropropylene (HFP), CF ₂ = CFOR ^f1 (where R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms), CF ₂ = CF—OCH ₂ —R. ^f2 (wherein R ^f2 represents a perfluoroalkylene group which may contain an etheric oxygen atom having 1 to 10 carbon atoms), CF ₂ = CF (CF ₂ ) _p OCF = CF ₂ (where , p is 1 or ^{_{2.), CH 2 = CX}} 1 (CF 2) n X 2 ( wherein, ^{X 1} and ^{X 2} are each other Independently represent a hydrogen atom or a fluorine atom, n is an integer from 2 to 10.), And the like. These can use 1 type (s) or 2 or more types.

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

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

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

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

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

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

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

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

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

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

The copolymer consisting of at least chlorotrifluoroethylene units (CTFE units) has CTFE units [—CFCl—CF ₂ —] and is composed of ethylene units (E units) and / or fluorine-containing monomer units. Chlorotrifluoroethylene copolymer (E4) (hereinafter sometimes referred to as CTFE copolymer (E4)).

The fluorine-containing monomer in the CTFE copolymer (E4) is not particularly limited as long as it is other than CTFE, but vinylidene fluoride (VDF), hexafluoropropylene (HFP), the above general formula CF ₂ = CFOR ^{P1 represented by f1} (wherein R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms), the above general formula CH ₂ = CX ¹ (CF ₂ ) and fluoroolefins represented by _n X ² (wherein X ¹ and X ² each independently represent a hydrogen atom or a fluorine atom, and n is an integer of 2 or more and 10 or less). These can use 1 type (s) or 2 or more types.

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

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

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

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

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

  The total content of CTFE units and TFE units in the CTFE / TFE copolymer (E5) is from the viewpoint of ensuring good moldability, environmental stress crack resistance, chemical penetration resistance, heat resistance, and mechanical properties. It is preferably 90 mol% or more and 99.9 mol% or less with respect to the whole monomer excluding the functional group-containing monomer described later, and the content of the monomer unit copolymerizable with the CTFE and TFE. Is preferably 0.1 mol% or more and 10 mol% or less.

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

  In the CTFE / TFE copolymer (E5), when the monomer copolymerizable with the CTFE and TFE is PAVE, the content of the PAVE unit is the entire monomer excluding the functional group-containing monomer described later. However, it is preferably 0.5 mol% or more and 7.0 mol% or less, and more preferably 1.0 mol% or more and 5.0 mol% or less.

  In the CTFE / TFE copolymer (E5), when the monomers copolymerizable with the CTFE and TFE are HFP and PAVE, the total content of the HFP unit and the PAVE unit is a functional group-containing monomer described later. It is preferably 0.5 mol% or more and 7.0 mol% or less, and more preferably 1.0 mol% or more and 5.0 mol% or less with respect to the whole monomer excluding.

The TFE copolymer (E3), the CTFE copolymer (E4), and the CTFE / TFE copolymer (E5) are excellent in chemical liquid permeation prevention properties, particularly barrier properties against alcohol-containing gasoline. For the alcohol-containing gasoline permeability coefficient, put the sheet obtained from the resin to be measured into a permeability coefficient measuring cup filled with isooctane / toluene / ethanol mixed solvent in which isooctane, toluene, and ethanol are mixed at a volume ratio of 45:45:10. , A value calculated from a change in mass measured at 60 ° C. The alcohol-containing gasoline permeability coefficient of the TFE copolymer (E3), the CTFE copolymer (E4), and the CTFE / TFE copolymer (E5) is 1.5 g · mm / (m ² · day) or less. It is preferably 0.01 g · mm / (m ² · day) or more and 1.0 g · mm / (m ² · day) or less, more preferably 0.02 g · mm / (m ² · day). More preferably, it is 0.8 g · mm / (m ² · day) or less.

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

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

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

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

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

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

  When coextruding the fluorine-containing polymer (E) with the polyamide polymer (A), the polyamide polymer (B), the semi-aromatic polyamide polymer composition (C), the polyamide polymer (D), etc. In order to ensure sufficient melt fluidity in the kneading temperature and molding temperature range without significant deterioration, the melt flow rate at a temperature higher by 50 ° C. than the melting point of the fluorine-containing polymer (E) and at a load of 5 kg. Is preferably 0.5 g / 10 min or more and 200 g / 10 min or less, more preferably 1 g / 10 min or more and 100 g / 10 min or less.

Further, in the fluorinated polymer (E), the melting point and glass transition point of the polymer can be adjusted by selecting the type and composition ratio of the fluorinated monomer and other monomers. The melting point of the fluorine-containing polymer (E) is appropriately selected depending on the purpose, application, and method of use. The polyamide polymer (A), polyamide polymer (B), semi-aromatic polyamide polymer composition (C ), Polyamide polymer (D) and the like, it is preferable that the temperature be close to the molding temperature of the resin. Therefore, it is preferable to optimize the melting point of the fluorine-containing polymer (E) by appropriately adjusting the ratio of the fluorine-containing monomer, the non-fluorine-containing monomer, and the functional group-containing monomer described later. The melting point of the fluorine-containing polymer (E) is determined at the time of co-extrusion with the polyamide polymer (A), the polyamide polymer (B), the semi-aromatic polyamide polymer composition (C) and the polyamide polymer (D). From the viewpoint of sufficiently ensuring the heat melting stability, continuous moldability, heat resistance, chemical resistance and chemical liquid permeation prevention property of the fluorine-containing polymer (E), it is preferably 150 ° C. or higher and 320 ° C. or lower. 170 ° C. or more and 310 ° C. or less is more preferable, and 180 ° C. or more and 300 ° C. or less is more preferable.
Here, the melting point means that the sample is heated to a temperature higher than the expected melting point using a differential scanning calorimeter, and then the sample is cooled at a rate of 10 ° C. per minute and cooled to 30 ° C. The melting point is defined as the temperature of the peak value of the melting curve measured by leaving the sample as it is for about 1 minute and then increasing the temperature at a rate of 10 ° C. per minute.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

Examples of the thermoplastic resin other than the polyamide polymer (D) and the fluorine-containing polymer (E) include the polyamide polymer (A), the polyamide polymer (B), and the semi-aromatic polyamide heavy as defined in the present invention. Other than coalescence (C1), polyethylene adipamide (polyamide 26), polytetramethylene succinamide (polyamide 44), polytetramethylene glutamide (polyamide 45), polytetramethylene adipamide (polyamide 46), polytetramethylene Methylene suberamide (polyamide 48), polytetramethylene azelamide (polyamide 49), polytetramethylene sebamide (polyamide 410), polytetramethylene dodecamide (polyamide 412), polypentamethylene succinamide (polyamide 54), Polypentamethyleneglutamide (Polyamide 5 ), Polypentamethylene adipamide (polyamide 56), polypentamethylene suberamide (polyamide 58), polypentamethylene azelamide (polyamide 59), polypentamethylene sebamide (polyamide 510), polypentamethylene dodecamide ( Polyamide 512), polyhexamethylene succinamide (polyamide 64), polyhexamethylene glutamide (polyamide 65), polyhexamethylene suberamide (polyamide 68), polyhexamethylene azelamide (polyamide 69), polyhexamethylene tetradeca Polyamide (polyamide 614), polyhexamethylene hexadecanamide (polyamide 616), polyhexamethylene octadecanamide (polyamide 618), polynonamethylene adipamide (polyamide 96), polynonamethyle Suberamide (polyamide 98), polynonamethylene azelamide (polyamide 99), polynonamethylene sebamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), polydecamethylene adipamide (polyamide 106), polydeca Methylene suberamide (polyamide 108), polydecamethylene azelamide (polyamide 109), polydecamethylene sebamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), polydodecamethylene adipamide (polyamide 126), Polydodecamethylene suberamide (Polyamide 128), Polydodecamethylene azelamide (Polyamide 129), Polydodecamethylene sebamide (Polyamide 1210), Polydodecamethylene dodecamide (Polyamide 1212) ),
Polymetaxylylene beramide (polyamide MXD8), polymetaxylylene azelamide (polyamide MXD9), polymetaxylylene sebamide (polyamide MXD10), polymetaxylylene decanamide (polyamide MXD12), polymetaxylylene hexahydroterephthalamide (Polyamide MXDT (H)), polymetaxylylene naphthalamide (polyamide MXDN), polyparaxylylene beramide (polyamide PXD8), polyparaxylylene azeamide (polyamide PXD9), polyparaxylylene sebacamide (polyamide PXD10) ), Polyparaxylylene decanamide (polyamide PXD12), polyparaxylylene hexahydroterephthalamide (polyamide PXDT (H)), polyparaxylylene naphthalamide (polyamide) PXDN), polyparaphenylene terephthalamide (PPTA), polyparaphenylene isophthalamide (PPIA), polymetaphenylene terephthalamide (PMTA), polymetaphenylene isophthalamide (PMIA), poly (2,6-naphthalene) Dimethylene adipamide) (polyamide 2,6-BAN6), poly (2,6-naphthalene dimethylene suberamide) (polyamide 2,6-BAN8), poly (2,6-naphthalene dimethylene azelamide) (polyamide) 2,6-BAN9), poly (2,6-naphthalene dimethylene sebacamide) (polyamide 2,6-BAN10), poly (2,6-naphthalene dimethylene dodecamide) (polyamide 2,6-BAN12), Poly (2,6-naphthalene dimethylene terephthalamide) (Polyamide 2,6-BA T), poly (2,6-naphthalene dimethylene isophthalamide) (polyamide 2,6-BANI), poly (2,6-naphthalene dimethylene hexahydroterephthalamide) (polyamide 2,6-BANT (H)) ), Poly (2,6-naphthalene dimethylene naphthalamide) (polyamide 2,6-BANN), poly (1,3-cyclohexanedimethylene adipamide) (polyamide 1,3-BAC6), poly (1,3 -Cyclohexane dimethylene suberamide (polyamide 1,3-BAC8), poly (1,3-cyclohexane dimethylene azelamide) (polyamide 1,3-BAC9), poly (1,3-cyclohexane dimethylene sebacamide) ( Polyamide 1,3-BAC10), poly (1,3-cyclohexanedimethylene dodecamide) (polyamide 1,3- BAC12), poly (1,3-cyclohexanedimethylene terephthalamide) (polyamide 1,3-BACT), poly (1,3-cyclohexanedimethylene isophthalamide) (polyamide 1,3-BACI), poly (1 , 3-cyclohexanedimethylenehexahydroterephthalamide) (polyamide 1,3-BACT (H)), poly (1,3-cyclohexanedimethylene naphthalamide) (polyamide 1,3-BACN), poly (1,4 -Cyclohexane dimethylene adipamide) (polyamide 1,4-BAC6), poly (1,4-cyclohexanedimethylene suberamide) (polyamide 1,4-BAC8), poly (1,4-cyclohexanedimethylene azelamide) (Polyamide 1,4-BAC9), poly (1,4-cyclohexanedimethylene sebacami) ) (Polyamide 1,4-BAC10), poly (1,4-cyclohexanedimethylene dodecamide) (polyamide 1,4-BAC12), poly (1,4-cyclohexanedimethylene terephthalamide) (polyamide 1,4- BACT), poly (1,4-cyclohexanedimethylene isophthalamide) (polyamide 1,4-BACI), poly (1,4-cyclohexanedimethylene hexahydroterephthalamide) (polyamide 1,4-BACT (H) ), Poly (1,4-cyclohexanedimethylenenaphthalamide) (polyamide 1,4-BACN), poly (4,4′-methylenebiscyclohexylene adipamide) (polyamide PACM6), poly (4,4′- Methylenebiscyclohexylenesuberamide) (polyamide PACM8), poly (4,4'-methylene) Sucyclohexylene azelamide) (polyamide PACM9), poly (4,4′-methylenebiscyclohexylene sebamide) (polyamide PACM10), poly (4,4′-methylenebiscyclohexylene dodecamide) (polyamide PACM12), Poly (4,4′-methylenebiscyclohexylenetetradecamide) (polyamide PACM14), poly (4,4′-methylenebiscyclohexylenehexadecamide) (polyamide PACM16), poly (4,4′-methylenebiscyclohexylene) Silene octadecamide) (polyamide PACM18), poly (4,4′-methylenebiscyclohexylene terephthalamide) (polyamide PACMT), poly (4,4′-methylenebiscyclohexylene isophthalamide) (polyamide PACMI), Poly (4,4'- Tylene biscyclohexylene hexahydroterephthalamide) (polyamide PACMT (H)), poly (4,4′-methylenebiscyclohexylene naphthalamide) (polyamide PACMN), poly (4,4′-methylene bis (2-methyl-) (Cyclohexylene) adipamide) (polyamide MACM6), poly (4,4′-methylenebis (2-methyl-cyclohexylene) suberamide) (polyamide MACM8), poly (4,4′-methylenebis (2-methyl-cyclohexylene) azeramide ) (Polyamide MACM9), poly (4,4′-methylenebis (2-methyl-cyclohexylene) sebacamide) (polyamide MACM10), poly (4,4′-methylenebis (2-methyl-cyclohexylene) dodecamide) (polyamide MACM12) ), Poly (4 4′-methylenebis (2-methyl-cyclohexylene) tetradecanamide) (polyamide MACM14), poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexadecamide) (polyamide MACM16), poly (4,4′-methylenebis) (2-methyl-cyclohexylene) octadecamide) (polyamide MACM18), poly (4,4′-methylenebis (2-methyl-cyclohexylene) terephthalamide) (polyamide MACMT), poly (4,4′-methylenebis (2-methyl) -Cyclohexylene) isophthalamide) (polyamide MACMI), poly (4,4'-methylenebis (2-methyl-cyclohexylene) hexahydroterephthalamide) (polyamide MACMT (H)), poly (4,4'-methylenebis ( 2-methyl-cyclo Xylene) naphthalamide) (polyamide MACMN), poly (4,4′-propylene biscyclohexylene adipamide) (polyamide PACP6), poly (4,4′-propylene biscyclohexylene suberamide) (polyamide PACP8), poly ( 4,4′-propylene biscyclohexylene azelamide) (polyamide PACP9), poly (4,4′-propylene biscyclohexylene sebacamide) (polyamide PACP10), poly (4,4′-propylene biscyclohexylene dodecamide) ) (Polyamide PACP12), poly (4,4′-propylene biscyclohexylene tetradecanamide) (polyamide PACP14), poly (4,4′-propylene biscyclohexylene hexadecanamide) (polyamide PACP16), poly (4 4'-propi Biscyclohexylene octadecanamide) (polyamide PACP18), poly (4,4′-propylene biscyclohexylene terephthalamide) (polyamide PAPPT), poly (4,4′-propylene biscyclohexylene isophthalamide) (polyamide) PACPI), poly (4,4′-propylene biscyclohexylene hexahydroterephthalamide) (polyamide PACPT (H)), poly (4,4′-propylene biscyclohexylene naphthalamide) (polyamide PACPN), polyisophorone azide Pamide (Polyamide IPD6), Polyisophorone Veramide (Polyamide IPD8), Polyisophorone Azelamide (Polyamide IPD9), Polyisophorone Sebamide (Polyamide IPD10), Polyisoholonand Decamide (Polyamide IPD) 2), polyisophorone terephthalamide (polyamide IPDT), polyisophorone isophthalamide (polyamide IPDI), polyisophorone hexahydroterephthalamide (polyamide IPDT (H)), polyisophorone naphthalamide (polyamide IPDN), polytetramethylene Hexahydroterephthalamide (polyamide 4T (H)), polypentamethylene hexahydroterephthalamide (polyamide 5T (H)), polyhexamethylene hexahydroterephthalamide (polyamide 6T (H)), poly (2-methyl Pentamethylene hexahydroterephthalamide) (polyamide M5T (H)), polynonamethylene terephthalamide (polyamide 9T), polynonamethylene isophthalamide (polyamide 9I), polynonamethylene hexahydroterephthala (Polyamide 9T (H)), polynonamethylene naphthalamide (polyamide 9N), poly (2-methyloctamethylene terephthalamide) (polyamide M8T), poly (2-methyloctamethylene isophthalamide) (polyamide M8I) , Poly (2-methyloctamethylenehexahydroterephthalamide) (polyamide M8T (H)), poly (2-methyloctamethylenenaphthalamide) (polyamide M8N), polytrimethylhexamethylene terephthalamide (polyamide TMHT), poly Trimethylhexamethyleneisophthalamide (polyamide TMHI), polytrimethylhexamethylenehexahydroterephthalamide (polyamide TMHT (H)), polytrimethylhexamethylenenaphthalamide (polyamide TMHN), polydecamethylenetereph Taramide (polyamide 10T), polydecamethylene isophthalamide (polyamide 10I), polydecamemethylene hexahydroterephthalamide (polyamide 10T (H)), polydecamethylene naphthalamide (polyamide 10N), polyundecamethylene terephthalamide (Polyamide 11T), Polyundecamethylene isophthalamide (Polyamide 11I), Polyundecamethylene hexahydroterephthalamide (Polyamide 11T (H)), Polyundecamethylene naphthalamide (Polyamide 11N), Polydodecamethylene terephthalate Lamid (polyamide 12T), polydodecamethylene isophthalamide (polyamide 12I), polydodecamethylene hexahydroterephthalamide (polyamide 12T (H)), polydodecamethylene naphthalamide (polyamide 1) N) and polyamide resins such as a copolymer using several kinds of raw material monomers of these polyamides.

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

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

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

  Further, in the laminated tube of the present invention, when the conductive layer made of the thermoplastic resin composition containing the conductive filler is disposed in the innermost layer of the laminated tube, the laminated tube is used as a chemical solution conveying tube or the like. It is possible to prevent the spark generated by the internal friction of the chemical liquid circulating in the pipe or the friction with the pipe wall from igniting the chemical liquid. At that time, a layer made of a thermoplastic resin having no conductivity is disposed outside the conductive layer, so that both low temperature impact resistance and conductivity can be achieved, and economically. Is also advantageous.

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

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

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

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

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

Since the content of the conductive filler varies depending on the type of the conductive filler to be used, it cannot be specified unconditionally, but from the viewpoint of balance of conductivity, fluidity, mechanical strength, etc., relative to 100 parts by mass of the thermoplastic resin. In general, the content is preferably 1 part by mass or more and 30 parts by mass or less.
In addition, from the viewpoint of obtaining sufficient antistatic performance, the conductive filler preferably has a surface resistivity of the melt-extruded product of 10 ⁸ Ω / square or less, more preferably 10 ⁶ Ω / square or less. preferable. However, the addition of the conductive filler tends to cause deterioration of strength and fluidity. Therefore, it is desirable that the content of the conductive filler is as small as possible if the target conductivity level is obtained.

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

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

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

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

  The outer diameter of the laminated tube takes into consideration the flow rate of the chemical solution (for example, fuel such as alcohol-containing gasoline). And although it is designed by the thickness which can maintain the softness | flexibility of the grade with the favorable assembly | attachment work of a tube and the vibration resistance at the time of use, it is not limited. Preferably, the outer diameter is 4 mm to 300 mm, the inner diameter is 3 mm to 250 mm, and the wall thickness is 0.5 mm to 25 mm.

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

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

  Furthermore, the laminated tube of the present invention is composed of hydrocarbon refrigerants such as n-butane, isobutane, 2-methylbutane, and n-pentane, and CFC-11, CFC-12, CFC-21, CFC-22, Freon-114, Freon-115, Freon-134A, Freon-32, Freon-123, Freon-124, Freon-125, Freon-143A, Freon-141b, Freon-142b, Freon-225, Freon-C318, Freon- It is excellent in permeation-preventing properties of chlorofluorocarbons such as 502, and can also be used for cooler refrigerant tubes, air conditioner refrigerant tubes, refrigerator refrigerant tubes, and the like.

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

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

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

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

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

Moreover, each physical property of the laminated tube was measured by the following method.
[Low temperature impact resistance]
A low temperature impact test was conducted at −40 ° C. and a weight mass of 500 g by the method described in VOLKSWAGEN AG PV 3905, and the required value of VOLKSWAGEN AG TL-52435 4.2 (the number of fractures was 0 with respect to the number of tests). It was confirmed that it was satisfied.

[Permeability of chemical solution (alcohol-containing gasoline) permeation]
One end of a tube cut to 200 mm was sealed, and alcohol-containing gasoline mixed with Fuel C (isooctane / toluene = 50/50 volume ratio) and ethanol in a 90/10 volume ratio was put inside, and the remaining end was also sealed. Thereafter, the entire mass was measured, and then the test tube was placed in an oven at 60 ° C., and the mass change was measured every day. The change in mass per day was divided by the surface area of the inner layer of the tube to calculate the permeation amount of alcohol-containing gasoline (g / m ² · day).

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

[Materials Used in Examples and Comparative Examples]
Polyamide polymer (A)
Manufacture of Polyamide 12 Resin Composition (A-1) Polyamide 12 (a-1) (Ube Industries, UBESTA3030UX1, relative viscosity 2.21) was coated with maleic anhydride-modified ethylene / propylene as an impact resistance improver. A polymer (manufactured by JSR Co., Ltd., JSR T7761P) is mixed in advance and supplied to a twin-screw melt kneader (manufactured by Nippon Steel Works Co., Ltd., model: TEX44), while the cylinder of the biaxial melt kneader is in the middle Then, benzenesulfonic acid butyramide as a plasticizer is injected by a metering pump, melt kneaded at a cylinder temperature of 180 ° C. to 260 ° C., and the molten resin is extruded into a strand shape, which is then introduced into a water bath, cooled, cut, and vacuumed After drying, a pellet of a polyamide 12 resin composition comprising 85% by mass of polyamide 12, 10% by mass of an impact resistance improving material, and 5% by mass of a plasticizer. To give the door (hereinafter, this polyamide 12 resin composition of (A-1).).

Production of polyamide 12 (a-2) In a pressure-resistant reaction vessel with an internal volume of 70 liters and a stirrer, 20.0 kg of dodecane lactam, 0.5 kg of water and polyethyleneimine (Epomin SP-12, manufactured by Nippon Shokubai Co., Ltd.) After charging 0 g and purging the inside of the polymerization tank with nitrogen, it was heated to 180 ° C. and stirred at this temperature so that the reaction system was in a uniform state. Subsequently, the temperature in the polymerization tank was raised to 270 ° C., and polymerization was performed with stirring for 2 hours while adjusting the pressure in the tank to 3.5 MPa. Thereafter, the pressure was released to normal pressure over about 2 hours, and then the pressure was reduced to 53 kPa, and polymerization was performed for 4 hours under reduced pressure. Next, nitrogen was introduced into the autoclave, and after returning to normal pressure, the strand was extracted from the lower nozzle of the reaction vessel and cut to obtain pellets. This pellet was dried under reduced pressure to obtain a polyamide 12 having a relative viscosity of 2.15, a terminal amino group concentration of 122 μeq / g, and a terminal carboxyl group concentration of 17 μeq / g (hereinafter, this polyamide 12 is referred to as (a-2)).

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

Manufacture of conductive polyamide 12 resin composition (A-3) In manufacture of polyamide 12 resin composition (A-1), polyamide 12 (a-1) was converted to (a-2) (Ube Industries, UBESTA3020U). , Production of polyamide 12 resin composition (A-1) except that carbon black (Cabot Co., Vulcan XC-72) was used as the conductive filler and no plasticizer was used. In the same manner, pellets of conductive polyamide 12 resin composition comprising 60% by mass of polyamide 12, 20% by mass of impact modifier, and 20% by mass of conductive filler were obtained (hereinafter referred to as this conductive polyamide 12 resin composition). A thing is called (A-3).).

Polyamide polymer (B)
Polyamide 6/12 (poly (caproamide / dodecanamide) copolymer) resin composition (B-1)
UBE Kosan Co., Ltd., UBE Nylon 7034U, caproamide unit: dodecanamide unit molar ratio = 87.5: 12.5 (mol%)

Manufacture of polyamide 610 (b-1) In a pressure-resistant reaction vessel with an internal volume of 70 liters equipped with a stirrer, 17.6 kg of 1,6-hexanediamine and 1-hexanediamine, a 50% by weight aqueous solution of an equimolar salt of 1,6-hexanediamine and sebacic acid After charging 63.8 g and replacing the inside of the polymerization tank with nitrogen, it was heated to 220 ° C. and stirred at this temperature so that the reaction system was in a uniform state. Next, the temperature in the polymerization tank was raised to 270 ° C., and polymerization was performed with stirring for 2 hours while adjusting the pressure in the tank to 1.7 MPa. Thereafter, the pressure was released to normal pressure over about 2 hours, and then the pressure was reduced to 53 kPa, and polymerization was performed for 4 hours under reduced pressure. Next, nitrogen was introduced into the autoclave, and after returning to normal pressure, the strand was extracted from the lower nozzle of the reaction vessel and cut to obtain pellets. This pellet was dried under reduced pressure to obtain a polyamide 610 having a relative viscosity of 2.48, a terminal amino group concentration of 73 μeq / g, and a terminal carboxyl group concentration of 14 μeq / g (hereinafter, this polyamide 610 is referred to as (b-1)).

Manufacture of polyamide 610 resin composition (B-2) Polyamide 610 (b-1), maleic anhydride modified ethylene / propylene copolymer (manufactured by JSR Corporation, JSR T7761P) as an impact resistance improver, antioxidant As triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan, IRGANOX 245), and tris (2,4-di -T-Butylphenyl) phosphite (BASF Japan, IRGAFOS168) is mixed in advance and supplied to a twin-screw melt kneader (manufactured by Nippon Steel, Ltd., model: TEX44), with a cylinder temperature of 200 ° C. to 270 ° C. After melt-kneading and extruding the molten resin into strands, it is introduced into a water bath, cooled, and cooled. Polyamide consisting of 0.8 parts by weight of antioxidant and 0.2 parts by weight of phosphorus processing stabilizer for 100 parts by weight in total of 90 parts by weight of polyamide 610 and 10 parts by weight of impact resistance improving material after vacuum drying A pellet of 610 resin composition was obtained (hereinafter, this polyamide 610 resin composition is referred to as (B-2)).

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

Production of polyamide 612 resin composition (B-3) Polyamide 610 resin except that polyamide 610 (b-1) was changed to polyamide 612 (b-2) in the production of polyamide 610 resin composition (B-2). In the same manner as in the production of the composition (B-2), 0.8 parts by mass of an antioxidant and phosphorus-based processing are performed for 100 parts by mass of 90% by mass of polyamide 612 and 10% by mass of an impact resistance improving material. Pellets of polyamide 612 resin composition comprising 0.2 parts by mass of stabilizer were obtained (hereinafter, this polyamide 612 resin composition is referred to as (B-3)).

Semi-aromatic polyamide polymer composition (C)
Production of semi-aromatic polyamide polymer (C1-1) or (C3-1) Terephthalic acid 2.741 kg (16.5 mol), isophthalic acid 0.997 kg (6.0 mol), adipic acid 1.096 kg (7 0.5 mol), 1,602 hexanediamine (3.602 kg, 31.0 mol), benzoic acid 65.9 g (0.54 mol), sodium hypophosphite monohydrate 8.5 g (based on the raw material) 0.1 mass%) and 6.0 L of distilled water were charged into an autoclave, the inside of the polymerization tank was purged with nitrogen, heated to 190 ° 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 250 ° C. At this time, the autoclave was pressurized to 3.1 MPa. The reaction was continued for 1 hour as it was, and then the reaction was carried out while gradually removing water vapor and keeping the pressure at 3.1 MPa. Next, the pressure was reduced to 1.0 MPa over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer. This was dried at 100 ° C. under reduced pressure for 12 hours, pulverized to a size of 2 mm or less, solid-phase polymerized at 230 ° C. and 0.013 kPa for 8 hours, melting point 302 ° C., half viscosity of 2.38. An aromatic polyamide polymer (polyamide 6T / 6I / 66 = 55/20/25 mol%) was obtained (hereinafter, this semi-aromatic polyamide polymer is referred to as (C1-1) or (C3-1)).

Production of Semi-Aromatic Polyamide Polymer Composition (C-1) Maleic anhydride-modified ethylene / propylene copolymer (C2-1) (JSR) Co., Ltd., JSR T7761P, flexural modulus 12 MPa), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] as an antioxidant (manufactured by BASF Japan, IRGANOX245) and tris (2,4-di-t-butylphenyl) phosphite (manufactured by BASF Japan, IRGAFOS168) as a phosphorus processing stabilizer are mixed in advance, and a twin-screw melt kneader (Japan Steel Works, Ltd.) Manufactured and model: TEX44), melt kneaded at a cylinder temperature of 260 ° C to 330 ° C, and the molten resin is After extrusion into a water tank, this was introduced into a water tank, cooled, cut and vacuum dried to prevent oxidation with respect to a total of 100 parts by mass of 80% by mass of semi-aromatic polyamide polymer and 20% by mass of impact resistance improving material. Pellets of a semi-aromatic polyamide polymer composition comprising 0.8 parts by mass of an agent and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained (hereinafter, this semi-aromatic polyamide polymer composition was referred to as (C-1) That said.)

Production of Semi-Aromatic Polyamide Polymer (C1-2) or (C3-2) In the production of semi-aromatic polyamide polymer (C3-1), 2.741 kg (16.5 mol) of terephthalic acid, 0. 997 kg (6.0 mol), adipic acid 1.096 kg (7.5 mol), 1,6-hexanediamine 3.602 kg (31.0 mol), terephthalic acid 4.983 kg (30.0 mol), 1, Semi-aromatic polyamide polymer (C3-1) except that it was changed to 1.801 kg (15.5 mol) of 6-hexanediamine and 1.801 kg (15.5 mol) of 2-methyl-1,5-pentanediamine. A semi-aromatic polyamide polymer (polyamide 6T / M5T = 50/50 mol%) having a melting point of 301 ° C. and a relative viscosity of 2.35 was obtained in the same manner as in the production of The amide polymer is referred to as (C1-2) or (C3-2).)

Production of semi-aromatic polyamide polymer composition (C-2) In production of semi-aromatic polyamide polymer composition (C-1), semi-aromatic polyamide polymer (C3-1) was changed to (C3-2). Except for the change, in the same manner as in the production of the semi-aromatic polyamide polymer composition (C-1), a total of 100 parts by mass of 80% by mass of the semi-aromatic polyamide polymer and 20% by mass of the impact resistance improving material was obtained. On the other hand, a semi-aromatic polyamide polymer composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer was obtained (hereinafter, this semi-aromatic polyamide polymer composition was (C-2).)

Production of Semi-Aromatic Polyamide Polymer (C1-3) or (C3-3) In the production of semi-aromatic polyamide polymer (C3-1), 2.741 kg (16.5 mol) of terephthalic acid, 0. 997 kg (6.0 mol), adipic acid 1.096 kg (7.5 mol), 1,6-hexanediamine 3.602 kg (31.0 mol), terephthalic acid 3.489 kg (21.0 mol), 1, Except for changing to 6-hexanediamine 2.522 kg (21.7 mol) and caprolactam 1.018 kg (9.0 mol), the same method as the production of the semi-aromatic polyamide polymer (C3-1), A semi-aromatic polyamide polymer (polyamide 6T / 6 = 70/30 mol%) having a melting point of 295 ° C. and a relative viscosity of 2.34 was obtained (hereinafter, this semi-aromatic polyamide polymer was referred to as (C1-3) or (Referred to as (C3-3)).

Production of semi-aromatic polyamide polymer composition (C-3) In production of semi-aromatic polyamide polymer composition (C-1), semi-aromatic polyamide polymer (C3-1) was changed to (C3-3). Except for the change, in the same manner as in the production of the semi-aromatic polyamide polymer composition (C-1), a total of 100 parts by mass of 80% by mass of the semi-aromatic polyamide polymer and 20% by mass of the impact resistance improving material was obtained. On the other hand, a semi-aromatic polyamide polymer composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer was obtained (hereinafter, this semi-aromatic polyamide polymer composition was (C-3).)

Production of Semi-Aromatic Polyamide Polymer (C1-4) or (C3-4) In production of semi-aromatic polyamide polymer (C3-1), 2.741 kg (16.5 mol) of terephthalic acid, 0. 997 kg (6.0 mol), adipic acid 1.096 kg (7.5 mol), 1,6-hexanediamine 3.602 kg (31.0 mol), terephthalic acid 4.135 kg (24.0 mol), isophthalic acid Semi-aromatic, except for 1.034 kg (6.0 mol), 1,6-hexanediamine 2.522 kg (21.7 mol), 1,10-decanediamine 1.602 kg (9.3 mol) In the same manner as in the production of the polyamide polymer (C3-1), a semi-aromatic polyamide polymer having a melting point of 302 ° C. and a relative viscosity of 2.32 (polyamide 6T / 6I / 10T / 10I = 56 / 24/14/6 mol%) (hereinafter, this semi-aromatic polyamide polymer is referred to as (C1-4) or (C3-4)).

Production of semi-aromatic polyamide polymer composition (C-4) In production of semi-aromatic polyamide polymer composition (C-1), semi-aromatic polyamide polymer (C3-1) was changed to (C3-4). Except for the change, in the same manner as in the production of the semi-aromatic polyamide polymer composition (C-1), a total of 100 parts by mass of 80% by mass of the semi-aromatic polyamide polymer and 20% by mass of the impact resistance improving material was obtained. On the other hand, a semi-aromatic polyamide polymer composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer was obtained (hereinafter, this semi-aromatic polyamide polymer composition was (Referred to as (C-4)).

Production of semi-aromatic polyamide polymer (C1-5) or (C4-1) Stirrer, thermometer, torque meter, pressure gauge, raw material inlet directly connected to diaphragm pump, nitrogen gas inlet, pressure relief outlet, pressure adjustment A pressure vessel equipped with a device and a polymer outlet has a capacity of 40 liters, and 4.384 kg (30.0 mol) of adipic acid, 8.50 g (0.049 mol) of calcium hypophosphite, and 4.37 g of sodium acetate ( 0.049 mol), pressurizing to 0.3 MPa with nitrogen gas with 99.9999% purity inside the pressure vessel, and then releasing nitrogen gas to normal pressure five times, replacing nitrogen Then, the system was heated while stirring under a sealing pressure. Furthermore, after heating up to 160 degreeC under a small nitrogen stream, 4.086 kg (30.0 mol) of m-xylylenediamine was dripped over 160 minutes under stirring. During this time, the internal pressure of the reaction system was controlled to 0.5 MPa, and the internal temperature was continuously raised to 275 ° C. Further, water distilled with the dropwise addition of m-xylylenediamine was removed from the system through a condenser and a cooler. After completion of the dropwise addition of m-xylylenediamine, the pressure was reduced to normal pressure over 60 minutes, and the reaction was continued for 10 minutes while maintaining the temperature in the container at 275 ° C. Thereafter, the internal pressure of the reaction system was reduced to 79 kPa, and the melt polymerization reaction was continued for 40 minutes. Thereafter, stirring was stopped and the inside of the system was pressurized to 0.2 MPa with nitrogen, and the polycondensate was extracted from the lower outlet of the pressure vessel into a string shape. The string-like polycondensate is immediately cooled, and the water-cooled string-like resin is pelletized by a pelletizer, and then dried under reduced pressure. (Hereinafter, this semi-aromatic polyamide polymer is referred to as (C1-5) or (C4-1)).

Production of semi-aromatic polyamide polymer composition (C-5) In production of semi-aromatic polyamide polymer composition (C-1), semi-aromatic polyamide polymer (C3-1) was changed to (C4-1). In the same manner as the production of the semiaromatic polyamide polymer composition (C-1) except that the cylinder temperature was changed from 330 ° C. to 280 ° C., 80% by mass of semiaromatic polyamide polymer, impact resistance A semi-aromatic polyamide polymer composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer was obtained with respect to a total of 100 parts by weight of 20% by weight of the improving material (hereinafter referred to as “the pellets”). The semi-aromatic polyamide polymer composition is referred to as (C-5)).

Production of semi-aromatic polyamide polymer (C1-6) or (C4-2) In the production of semi-aromatic polyamide polymer (C4-1), 4.384 kg (30.0 mol) of adipic acid was added to 4. Except for changing to 121 kg (28.2 mol) and isophthalic acid 0.299 kg (1.8 mol), the melting point was 230 ° C. in the same manner as in the production of the semi-aromatic polyamide polymer (C4-1). A semi-aromatic polyamide polymer (polyamide MXD6 / MXDI = 94/6 mol%) having a relative viscosity of 2.38 was obtained (hereinafter, this semi-aromatic polyamide polymer was referred to as (C1-6) or (C4-2)). That said.)

Production of semi-aromatic polyamide polymer composition (C-6) In production of semi-aromatic polyamide polymer composition (C-5), semi-aromatic polyamide polymer (C4-1) was changed to (C4-2). Except that the cylinder temperature was changed from 280 ° C. to 270 ° C., in the same manner as in the production of the semi-aromatic polyamide polymer composition (C-5), 80% by mass of semi-aromatic polyamide polymer, impact resistance A semi-aromatic polyamide polymer composition pellet comprising 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer was obtained with respect to a total of 100 parts by weight of 20% by weight of the improving material (hereinafter referred to as “the pellets”). The semi-aromatic polyamide polymer composition is referred to as (C-6)).

Production of conductive semi-aromatic polyamide polymer composition (C-7) Semi-aromatic polyamide, except that in the production of semi-aromatic polyamide polymer (C4-2), the melt polymerization time was changed from 40 minutes to 20 minutes. A semi-aromatic polyamide polymer having a melting point of 230 ° C. and a relative viscosity of 2.12 was obtained in the same manner as in the production of the polymer (C4-2). To the semi-aromatic polyamide polymer, maleic anhydride-modified ethylene / 1-butene copolymer (C2-2) (manufactured by Mitsui Chemicals, Tuffmer MH5010, flexural modulus 7 MPa) and ethylene / 1-butene copolymer (C2-3) (manufactured by Mitsui Chemicals, Inc., Toughmer A-0550, flexural modulus 6 MPa), carbon black as a conductive filler (manufactured by Lion Corporation, Ketjen Black EC600JD), oxidation Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan, IRGANOX 245) as an inhibitor, and tris (2,4 as a phosphorus processing stabilizer) -Di-t-butylphenyl) phosphite (BASF Japan, IRGAFOS168) This is kneaded and mixed, supplied to a twin-screw melt kneader (manufactured by Nippon Steel Works, model: TEX44), melt kneaded at a cylinder temperature of 250 ° C. to 290 ° C., and the molten resin is extruded into a strand shape. Is cooled, cut and vacuum dried to prevent oxidation with respect to a total of 100 parts by mass of a semi-aromatic polyamide polymer 58% by mass, an impact resistance improving material 35% by mass and a conductive filler 7% by mass. Conductive semi-aromatic polyamide polymer composition pellets comprising 0.8 part by weight of an agent and 0.2 part by weight of a phosphorus processing stabilizer were obtained (hereinafter, this semi-aromatic polyamide polymer composition (C- 7).)

Production of semi-aromatic polyamide polymer (C1-7) or (C4-3) In the production of semi-aromatic polyamide polymer (C4-1), 4.086 kg (30.0 mol) of m-xylylenediamine, adipine 4.384 kg (30.0 mol) of acid was transferred to 3.637 kg (26.7 mol) of m-xylylenediamine, 3.902 kg (26.7 mol) of adipic acid, 0.588 kg of alanine (DL-alanine) (6. 6 mol), except that the polymerization temperature was changed from 275 ° C. to 240 ° C., in the same manner as in the production of the semi-aromatic polyamide polymer (C4-1), the melting point was 209 ° C. and the relative viscosity was 2. 35 semi-aromatic polyamide polymers (polyamide MXD6 / ALA = 89/11 mol%) were obtained (hereinafter, this semi-aromatic polyamide polymer is referred to as (C1-7) or (C4-3)).

Production of semi-aromatic polyamide polymer composition (C-8) In production of semi-aromatic polyamide polymer composition (C-5), semi-aromatic polyamide polymer (C4-1) was changed to (C4-3). The semi-aromatic polyamide polymer was 80% by mass and the impact resistance was improved in the same manner as in the production of the semi-aromatic polyamide polymer composition (C-5) except that the cylinder temperature was changed from 280 ° C. to 240 ° C. A pellet of a semi-aromatic polyamide polymer composition comprising 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus processing stabilizer was obtained with respect to 100 parts by mass in total of 20% by mass of the material (hereinafter, This semi-aromatic polyamide polymer composition is referred to as (C-8)).

Production of semi-aromatic polyamide polymer composition (C-9) In the production of semi-aromatic polyamide polymer composition (C-5), maleic anhydride-modified ethylene / propylene copolymer (C2-1) was converted to polyamide 6 (D-1) In the same manner as the production of the semi-aromatic polyamide polymer composition (C-5), except that it was changed to (Ube Industries, Ltd., UBE Nylon 1024B, relative viscosity 3.50), A semi-aromatic polyamide weight composed of 0.8 parts by weight of an antioxidant and 0.2 parts by weight of a phosphorus processing stabilizer with respect to a total of 100 parts by weight of 70% by weight of a semi-aromatic polyamide polymer and 30% by weight of polyamide 6. A pellet of the coalescence composition was obtained (hereinafter, this semi-aromatic polyamide polymer composition is referred to as (C-9)).

Polyamide polymer (D)
Manufacture of a polyamide 6 resin composition (D-1) Polyamide 6 (d-1) (Ube Industries, UBE Nylon 1024B, relative viscosity 3.50), maleic anhydride modified ethylene / propylene as an impact resistance improver Copolymer (manufactured by JSR Co., Ltd., JSR T7761P), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] as an antioxidant (manufactured by BASF Japan, IRGANOX245) and tris (2,4-di-t-butylphenyl) phosphite (manufactured by BASF Japan, IRGAFOS168) as a phosphorus processing stabilizer are mixed in advance, and a twin-screw melt kneader (Japan Steel Works, Ltd.) Manufactured, model: TEX44), while a plasticizer is formed in the middle of the cylinder of the biaxial melt kneader. Benzenesulfonic acid butyramide was injected by a metering pump, melt kneaded at a cylinder temperature of 230 ° C. to 270 ° C., and the molten resin was extruded into a strand shape. Then, this was introduced into a water tank, cooled, cut, and vacuum dried. 6 Polyamide 6 comprising 0.8 parts by weight of antioxidant and 0.2 parts by weight of phosphorus processing stabilizer with respect to a total of 100 parts by weight of 85% by weight, impact resistance 10% by weight, and plasticizer 5% by weight A pellet of the resin composition was obtained (hereinafter, this polyamide 6 resin composition is referred to as (D-1)).

Manufacture of polyamide 6 (d-2) 20.0 kg of caprolactam, 1 kg of water, 70.2 g of polyethyleneimine (manufactured by Nippon Shokubai Co., Ltd., Epomin SP-12) were placed in a pressure-resistant reaction vessel with an internal volume of 70 liters equipped with a stirrer. It heated at 100 degreeC and stirred so that the inside of a reaction system might become a uniform state at this temperature. Subsequently, the temperature was further raised to 260 ° C., and the mixture was stirred for 1 hour under a pressure of 2.5 MPa. Thereafter, the polymerization reaction was performed at 260 ° C. for 2 hours under atmospheric pressure while releasing the pressure to evaporate water from the reaction vessel, and further for 4 hours under reduced pressure at 260 ° C. and 53 kPa. After completion of the reaction, the reaction product taken out in a strand form from the lower nozzle of the reaction vessel was introduced into a water bath, cooled, and cut to obtain pellets. This pellet was immersed in hot water to extract and remove unreacted monomers, and then dried under reduced pressure to obtain polyamide 6 having a relative viscosity of 3.36, a terminal amino group concentration of 55 μeq / g, and a terminal carboxyl group concentration of 35 μeq / g. Obtained (hereinafter, this polyamide 6 is referred to as (d-2)).

Production of polyamide 6 resin composition (D-2) Polyamide 6 resin composition except that polyamide 6 (d-1) was changed to (d-2) in the production of polyamide 6 resin composition (D-1). In the same manner as in the production of (D-1), 0.8 parts by mass of the antioxidant with respect to 100 parts by mass in total of 85% by mass of polyamide 6, 10% by mass of the impact resistance improving material, and 5% by mass of the plasticizer. A pellet of polyamide 6 resin composition comprising 0.2 parts by mass of a phosphorus processing stabilizer was obtained (hereinafter, this polyamide 6 resin composition is referred to as (D-2)).

Manufacture of polyamide 66 resin composition (D-3) In the manufacture of polyamide 6 resin composition (D-1), polyamide 6 (d-1) was converted to polyamide 66 (d-3) (UBE Industries, UBE). Nylon 2026B, relative viscosity 3.36), except that the cylinder temperature was changed from 270 ° C. to 290 ° C., in the same manner as in the production of the polyamide 6 resin composition (D-1), 85% by mass of polyamide 66, Pellets of polyamide 66 resin composition comprising 0.8 parts by weight of antioxidant and 0.2 parts by weight of phosphorus processing stabilizer for 100 parts by weight in total of 10% by weight of impact modifier and 5% by weight of plasticizer (Hereinafter, this polyamide 66 resin composition is referred to as (D-3)).

Production of Conductive Polyamide 6 Resin Composition (D-4) Polyamide 6 (d-4) (manufactured by Ube Industries, UBE Nylon SF1018A, relative viscosity 2.98), maleic anhydride-modified ethylene as an impact resistance improver / 1-butene copolymer (Mitsui Chemicals, Tuffmer MH5010) and ethylene / 1-butene copolymer (Mitsui Chemicals, Tuffmer A-0550), carbon black (Cabot Corporation) as a conductive filler Manufactured by Vulcan XC-72), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan, IRGANOX245) as an antioxidant, and phosphorus-based Tris (2,4-di-t-butylphenyl) phosphite (BASF Japan) as processing stabilizer IRGAFOS 168) is mixed in advance, supplied to a twin-screw melt kneader (manufactured by Nippon Steel Works, model: TEX44), melt-kneaded at a cylinder temperature of 220 ° C. to 280 ° C., and the molten resin is extruded into a strand shape This was introduced into a water tank, cooled, cut, and vacuum dried, and the antioxidant 0 was added to 100 parts by mass of 55% by mass of polyamide 6, 25% by mass of impact resistance improving agent, and 20% by mass of conductive filler. The pellet of the conductive polyamide 6 resin composition which consists of 0.8 mass part and 0.2 mass part of phosphorus processing stabilizers was obtained (henceforth this conductive polyamide 6 resin composition is called (D-4)).

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

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

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

Production of fluorinated polymer (E-4) In the production of fluorinated polymer (E-3), 5-norbornene-2,3-dicarboxylic acid anhydride (NAH) 0.3 mass% 1,3- 7.6 kg of fluorinated polymer in the same manner as the production of the fluorinated polymer (E-3), except that no dichloro-1,1,2,2,3-pentafluoropropane solution was charged. Got.
The composition of the fluorine-containing polymer is TFE-based polymer units / PPVE-based polymer units / HFP-based polymer units = 91.5 / 1.5 / 7.0 (mol%), and the melting point is 257 ° C. Met. This granulated product was melted using an extruder at 300 ° C. for a residence time of 2 minutes to obtain a fluorine-containing polymer pellet (hereinafter, this fluorine-containing polymer is referred to as (E-4)). ).

Example 1
Using the polyamide 12 resin composition (A-1), polyamide 6/12 resin composition (B-1), and semi-aromatic polyamide polymer composition (C-1) shown above, (A) Co., Ltd.) (A-1) at an extrusion temperature of 260 ° C, (B-1) at an extrusion temperature of 230 ° C, and (C-1) at an extrusion temperature of 330 ° C separately. The melted and discharged molten resin was merged with an adapter and formed into a laminated tubular body. Subsequently, cooling is performed by a sizing die for dimension control, and the sheet is taken up. The (a) layer (outermost layer) made of (A-1), the (b) layer (intermediate layer) made of (B-1), (C- 1) (c) layer (innermost layer), the layer configuration is (a) / (b) / (c) = 0.60 / 0.15 / 0.25 mm, the inner diameter is 6 mm, and the outer diameter is 8 mm. A laminated tube was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 2
In Example 1, except that the semi-aromatic polyamide polymer composition (C-1) was changed to (C-2), a laminated tube having a layer structure shown in Table 1 was prepared in the same manner as in Example 1. Obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 3
In Example 1, except that the semi-aromatic polyamide polymer composition (C-1) was changed to (C-3), a laminated tube having a layer structure shown in Table 1 was prepared in the same manner as in Example 1. Obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 4
In Example 1, except that the semi-aromatic polyamide polymer composition (C-1) was changed to (C-4), a laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 1. Obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 5
In Example 1, the semi-aromatic polyamide polymer composition (C-1) was changed to (C-5), and the extrusion temperature of (C-5) was changed to 280 ° C. By the method, the laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 6
In Example 1, the semi-aromatic polyamide polymer composition (C-1) was changed to (C-6), and the extrusion temperature of (C-6) was changed to 270 ° C. The same as in Example 1. By the method, the laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 7
In Example 1, the semi-aromatic polyamide polymer composition (C-1) was changed to the conductive semi-aromatic polyamide polymer composition (C-7), and the extrusion temperature of (C-7) was changed to 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. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 8
In Example 1, the semi-aromatic polyamide polymer composition (C-1) was changed to (C-8), and the extrusion temperature of (C-8) was changed to 240 ° C. By the method, the laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 9
In Example 1, except that the polyamide 6/12 resin composition (B-1) was changed to the polyamide 610 resin composition (B-2) and the extrusion temperature of (B-2) was changed to 270 ° C. 1 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1.

Example 10
In Example 1, except that the polyamide 6/12 resin composition (B-1) was changed to the polyamide 612 resin composition (B-3) and the extrusion temperature of (B-3) was changed to 270 ° C. 1 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1.

Example 11
In Example 1, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 1 except having changed the polyamide 12 resin composition (A-1) into (A-2). The physical property measurement results of the laminated tube are shown in Table 1.

Example 12
Polyamide 12 resin composition (A-1), polyamide 6/12 resin composition (B-1), semi-aromatic polyamide polymer composition (C-6), conductive semi-aromatic polyamide polymer composition shown above (A-1) was extruded at 260 ° C., and (B-1) was extruded at 230 ° C. using a product (C-7) in a 4-layer tube molding machine (Plastic Engineering Laboratory Co., Ltd.). Sizing that melts separately at an extrusion temperature of 270 ° C. and (C-7) at an extrusion temperature of 280 ° C., and the discharged molten resin is joined by an adapter, formed into a tube, and dimension controlled Cooled by a die and picked up, (A) layer (outermost layer) layer (A-1), (B-1) layer (b) layer (intermediate layer), (C-6) The layer consisting of (c) layer (inner layer) and the layer consisting of (C-7) as layer (c ′) ( The innermost layer), the layer structure is (a) / (b) / (c) / (c ′) = 0.60 / 0.15 / 0.15 / 0.10 mm, inner diameter 6 mm, outer diameter 8 mm. A laminated tube was obtained. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 13
In Example 12, the semi-aromatic polyamide polymer composition (C-6) was used as the polyamide 6 resin composition (D-1), and the conductive semi-aromatic polyamide polymer composition (C-7) was used as the semi-aromatic polyamide. In the same manner as in Example 12, except that the polymer composition (C-6) was changed and the extrusion temperature of (D-1) was changed to 260 ° C and the extrusion temperature of (C-6) was changed to 270 ° C. 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 14
In Example 13, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 13 except having changed the polyamide 6 resin composition (D-1) into (D-2). The physical property measurement results of the laminated tube are shown in Table 1.

Example 15
Example 13 is the same as Example 13 except that the polyamide 6 resin composition (D-1) was changed to the polyamide 66 resin composition (D-3) and the extrusion temperature of (D-3) was changed to 290 ° C. A laminated tube having the layer configuration shown in Table 1 was obtained in the same manner. The physical property measurement results of the laminated tube are shown in Table 1.

Example 16
In Example 13, the semi-aromatic polyamide polymer composition (C-6) was changed to (C-8), and the extrusion temperature of (C-8) was changed to 240 ° C. By the method, the laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 17
Polyamide 12 resin composition (A-1), polyamide 6/12 resin composition (B-1), semi-aromatic polyamide polymer composition (C-6), polyamide 6 resin composition (D-1) shown above ) Using a 5-layer tube molding machine (Plastics Engineering Laboratory Co., Ltd.), (A-1) extrusion temperature 260 ° C., (B-1) extrusion temperature 230 ° C., (C- 6) is melted separately at an extrusion temperature of 270 ° C., and (D-1) is melted separately at an extrusion temperature of 260 ° C., and the discharged molten resin is joined by an adapter, formed into a tubular shape, and cooled by a sizing die that controls dimensions, The layer consisting of (A-1) is taken as (a) layer (outermost layer), the layer consisting of (B-1) as (b) layer (outer layer), and the layer consisting of (D-1) as (d). ) Layer (intermediate layer, innermost layer), (C-6) layer consisting of (C) layer (inner layer) Layer structure is (a) / (b) / (d) / (c) / (d) = 0.20 / 0.15 / 0.20 / 0.25 / 0.20 mm, inner diameter 6 mm, outer A laminated tube having a diameter of 8 mm was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 18
Using the polyamide 12 resin composition (A-1), polyamide 6/12 resin composition (B-1), and semi-aromatic polyamide polymer composition (C-6) shown above, (A) Co., Ltd.) (A-1) at an extrusion temperature of 260 ° C, (B-1) at an extrusion temperature of 230 ° C, and (C-6) at an extrusion temperature of 270 ° C separately. The molten resin that has been melted and merged is joined by an adapter, formed into a tubular shape, cooled by a sizing die that controls the dimensions, taken up, and the layer made of (A-1) is changed to layer (a) (outermost layer, outermost layer). When the layer consisting of (inner layer) and (B-1) is (b) layer (outer layer, inner layer), and the layer consisting of (C-6) is (c) layer (intermediate layer), the layer configuration is (a) / (B) / (c) / (b) / (a) = 0.25 / 0.15 / 0.25 / 0.15 0.20 mm, an inner diameter of 6 mm, to obtain a laminated tube having an outer diameter of 8 mm. The physical property measurement results of the laminated tube are shown in Table 1.

Example 19
In Example 18, the polyamide 12 resin composition (A-1) used as the innermost layer material was changed to the conductive polyamide 12 resin composition (A-3), and the extrusion temperature of (A-3) was changed to 270 ° C. A laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 18 except that. 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 20
In Example 19, the semi-aromatic polyamide polymer composition (C-6) was changed to (C-8), and the extrusion temperature of (C-8) was changed to 240 ° C. By the method, the laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 21
In Example 18, the polyamide 6/12 resin composition (B-1) used as the inner layer material was polyamide 6 resin composition (D-1), and the polyamide 12 resin composition (A-1) used as the innermost layer material Was changed to conductive polyamide 6 resin composition (D-4), the extrusion temperature of (D-1) was changed to 260 ° C., and the extrusion temperature of (D-4) was changed to 270 ° C. The laminated tube of the layer structure shown in Table 1 was obtained by this method. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 22
In Example 21, the semi-aromatic polyamide polymer composition (C-6) was changed to (C-8), and the extrusion temperature of (C-8) was changed to 240 ° C. By the method, the laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 23
Polyamide 12 resin composition (A-1), polyamide 612 resin composition (B-3), semi-aromatic polyamide polymer composition (C-1) and fluorine-containing polymer (E-1) shown above are used. Using a Plabor (Plastics Engineering Laboratory Co., Ltd.) 4-layer tube molding machine, (A-1) is an extrusion temperature of 260 ° C., (B-3) is an extrusion temperature of 270 ° C., (C-1) Are melted separately at an extrusion temperature of 330 ° C. and (E-1) at an extrusion temperature of 280 ° C., the discharged molten resin is joined by an adapter, formed into a tubular shape, cooled by a sizing die that controls dimensions, and taken off. The layer made of (A-1) is the layer (a) (outermost layer), the layer made of (B-3) is the layer (b) (outer layer), and the layer made of (C-1) is the layer (c) When the layer consisting of (intermediate layer) and (E-1) is the (e) layer (innermost layer), Formed is (a) / (b) / (c) / (e) = 0.50 / 0.20 / 0.15 / 0.15mm, an inner diameter of 6 mm, to obtain a laminated tube having an outer diameter of 8 mm. The physical property measurement results of the laminated tube are shown in Table 1.

Example 24
In Example 23, the polyamide 612 resin composition (B-3) was changed to the polyamide 6/12 resin composition (B-1), and the semiaromatic polyamide polymer composition (C-1) was changed to (C-6). In the same manner as in Example 23, except that the extrusion temperature of (B-1) was changed to 230 ° C. and the extrusion temperature of (C-6) was changed to 270 ° C., the laminated tube having the layer configuration shown in Table 1 was prepared. Obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 25
In Example 23, except that the fluorine-containing polymer (E-1) was changed to the conductive fluorine-containing polymer (E-2) and the extrusion temperature of (E-2) was changed to 300 ° C. In the same manner as in No. 23, a laminated tube having the layer configuration shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 26
In Example 24, except that the fluorine-containing polymer (E-1) was changed to the conductive fluorine-containing polymer (E-2) and the extrusion temperature of (E-2) was changed to 300 ° C. In the same manner as in No. 24, a laminated tube having the layer configuration shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. 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 27
Polyamide 12 resin composition (A-1), polyamide 612 resin composition (B-3), semi-aromatic polyamide polymer composition (C-1), fluorine-containing polymer (E-1) shown above, Using a conductive fluorine-containing polymer (E-2), Plabor (manufactured by Plastics Engineering Laboratory Co., Ltd.) 5-layer tube molding machine, (A-1) was extruded at 260 ° C., (B- 3) was extruded at an extrusion temperature of 270 ° C., (C-1) was melted at an extrusion temperature of 330 ° C., (E-1) was melted at an extrusion temperature of 280 ° C., and (E-2) was melted separately at an extrusion temperature of 300 ° C. Molten resin is merged with an adapter, formed into a tubular shape, cooled with a sizing die that controls dimensions, taken up, and the layer consisting of (A-1) is changed from (a) layer (outermost layer), (B-3) (B) layer (outer layer) and (C-1) layer (c) layer ( When the layer composed of (interlayer) and (E-1) is the (e) layer (inner layer) and the layer composed of (E-2) is the (e ′) layer (innermost layer), the layer configuration is (a) / (B) / (c) / (e) / (e ′) = 0.45 / 0.20 / 0.15 / 0.10 / 0.10 mm, 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. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 28
In Example 27, the polyamide 612 resin composition (B-3) was changed to the polyamide 6/12 resin composition (B-1), and the semiaromatic polyamide polymer composition (C-1) was changed to (C-6). In the same manner as in Example 27, except that the extrusion temperature of (B-1) was changed to 230 ° C. and the extrusion temperature of (C-6) was changed to 270 ° C., the laminated tube having the layer configuration shown in Table 1 was prepared. 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 29
In Example 27, except that the conductive fluorine-containing polymer (E-2) was changed to the fluorine-containing polymer (E-4), the layer structure shown in Table 1 was used in the same manner as in Example 27. A laminated tube was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 30
In Example 29, except that the fluorine-containing polymer (E-1) was changed to (E-3) and the extrusion temperature of (E-3) was changed to 300 ° C., the same method as in Example 29 was used. The laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 31
In Example 17, the polyamide 6 resin composition (D-1) used as the innermost layer material was changed to the fluorine-containing polymer (E-1), and the extrusion temperature of (E-1) was changed to 280 ° C. Obtained the laminated tube of the layer structure shown in Table 1 by the method similar to Example 17. FIG. The physical property measurement results of the laminated tube are shown in Table 1.

Example 32
In Example 27, the fluorine-containing polymer (E-1) is the polyamide 6 resin composition (D-1), and the conductive fluorine-containing polymer (E-2) is the fluorine-containing polymer (E-1). In the same manner as in Example 27, except that the extrusion temperature of (D-1) was changed to 260 ° C. and the extrusion temperature of (E-1) was changed to 280 ° C., lamination of the layer constitution shown in Table 1 A tube was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 33
In Example 28, the fluorinated polymer (E-1) was the polyamide 6 resin composition (D-1), and the conductive fluorinated polymer (E-2) was the fluorinated polymer (E-1). In the same manner as in Example 28 except that the extrusion temperature of (D-1) was changed to 260 ° C. and the extrusion temperature of (E-1) was changed to 280 ° C., lamination of the layer constitution shown in Table 1 A tube was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 1
In Example 1, the single layer tube shown in Table 1 was obtained by the method similar to Example 1 except not using a polyamide 12 resin composition (A-1). Table 1 shows the physical property measurement results of the single-layer tube.

Comparative Example 2
In Example 1, the single layer tube shown in Table 1 was obtained by the same method as Example 1 except not using polyamide 6/12 resin composition (B-1). Table 1 shows the physical property measurement results of the single-layer tube.

Comparative Example 3
In Example 1, the single layer tube shown in Table 1 was obtained by the same method as Example 1 except not using a semi-aromatic polyamide polymer composition (C-1). Table 1 shows the physical property measurement results of the single-layer tube.

Comparative Example 4
In Example 2, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 2 except not using a polyamide 6/12 resin composition (B-1). The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 5
In Example 3, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 3 except not using a polyamide 6/12 resin composition (B-1). The physical property measurement results of the laminated tube are shown in Table 1.

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

Comparative Example 7
In Example 5, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 5 except not using a polyamide 6/12 resin composition (B-1). The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 8
In Example 6, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 6 except not using a polyamide 6/12 resin composition (B-1). The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 9
In Example 7, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 7 except not using a polyamide 6/12 resin composition (B-1). The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Comparative Example 10
In Example 8, a laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 8 except that the polyamide 6/12 resin composition (B-1) was not used. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 11
In Example 5, except that the semiaromatic polyamide polymer composition (C-5) was changed to (C-9), a laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 5. Obtained. The physical property measurement results of the laminated tube are shown in Table 1.

As is clear from Table 1, the laminated tube of Comparative Example 1 which does not have a layer made of the polyamide polymer (A) defined in the present invention is inferior in low-temperature impact resistance, and the polyamide polymer defined in the present invention ( The laminated tube of Comparative Example 2 having no layer consisting of B) was inferior in interlayer adhesion. The laminated tube of Comparative Example 3 which does not have a layer made of the semi-aromatic polyamide polymer composition (C) defined in the present invention was inferior in chemical solution permeation prevention. The laminated tubes of Comparative Examples 4 to 10 having no layer made of the polyamide polymer (B) defined in the present invention were inferior in interlayer adhesion. The laminated tube of Comparative Example 11 having a layer made of the semi-aromatic polyamide polymer composition (C) not containing the olefin polymer (C2) defined in the present invention was inferior in low-temperature impact resistance.
On the other hand, it is clear that the laminated tubes of Examples 1 to 33 defined in the present invention have good properties such as low-temperature impact resistance, chemical solution permeation prevention properties, and interlayer adhesion properties.

Claims (10)

At least one polyamide polymer (A) selected from the group consisting of polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), and poly (undecanamide / dodecanamide) copolymer (polyamide 11/12). (A) selected from the group consisting of a layer, a poly (caproamide / dodecanamide) copolymer (polyamide 6/12), polyhexamethylene sebacamide (polyamide 610), and polyhexamethylene dodecanamide (polyamide 612) The bending elastic modulus of the layer (b) comprising at least one polyamide polymer (B) and the semi-aromatic polyamide polymer (C1) measured in accordance with ISO 178 is 50% by mass to 95% by mass. Contains 5% by mass or more and 50% by mass or less of an olefin polymer (C2) of 500 MPa or less A laminated tube comprising at least three layers including the (c) layer comprising the semi-aromatic polyamide polymer composition (C), wherein the semi-aromatic polyamide polymer (C1) is based on the total diamine units. , A diamine unit having an aliphatic diamine unit having 4 to 6 carbon atoms having a straight chain and / or a side chain, and 60 mol% or more, a terephthalic acid unit of 30 mol% to 100 mol%, and an aromatic other than terephthalic acid Semiaromatic polyamide polymer comprising dicarboxylic acid units comprising 0 to 70 mol% of dicarboxylic acid units and / or 0 to 70 mol% of aliphatic dicarboxylic acid units having 4 to 20 carbon atoms (C3), or m-xylylenediamine unit 30 mol% or more and 100 mol% or less, p-xylylenediamine unit 0 mol% or more and 70 mol% or less, And / or a semi-fragrance comprising an aliphatic dicarboxylic acid unit having 4 to 6 carbon atoms and having a side chain of 30 mol% to 100 mol%, a terephthalic acid unit and / or an isophthalic acid unit of 0 mol% to 70 mol%. A laminated tube, which is an aromatic polyamide polymer (C4). In the semi-aromatic polyamide polymer (C3), the aliphatic diamine unit having a straight chain and / or a side chain and having 4 to 6 carbon atoms is 1,6-hexanediamine and / or 2-methyl-1,5. A unit derived from pentanediamine, and in the semi-aromatic polyamide polymer (C4), an aliphatic dicarboxylic acid unit having 4 to 6 carbon atoms and having a straight chain and / or a side chain is derived from adipic acid The laminated tube according to claim 1, wherein the laminated tube is a unit. The laminated tube according to claim 1 or 2, wherein the (b) layer is in direct contact with the (a) layer and is disposed between the (a) layer and the (c) layer. The laminated tube according to any one of claims 1 to 3, wherein the (a) layer is disposed as an outermost layer, and the (c) layer is disposed inside the (a) layer. The laminated tube further comprises a group consisting of polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), and a poly (caproamide / hexamethylene adipamide) copolymer (polyamide 6/66). The layer (d) comprising at least one selected polyamide polymer (D), wherein the layer (d) is disposed in direct contact with the layer (c). The laminated tube in any one. The laminated tube according to any one of claims 1 to 5, wherein the (c) layer is disposed in an innermost layer. 6. The laminated tube according to claim 4, further comprising a fluorine-containing polymer (E) in which a functional group having reactivity with an amino group is introduced into a molecular chain. And the layer (e) is disposed in the innermost layer. The laminated tube according to any one of claims 1 to 7, wherein a conductive layer made of a thermoplastic resin composition containing a conductive filler is disposed in the innermost layer of the laminated tube. The laminated tube according to any one of claims 1 to 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 chemical solution transport tube.