JP6299943B2 - Laminated tube - Google Patents

Description

  The present invention comprises a layer made of an aliphatic polyamide (polyamide 11, 12, etc.), a layer made of a modified vinyl alcohol polymer having a specific structural unit, and a layer made of a fluorine polymer having a specific functional group. The present invention relates to a laminated tube, which is excellent in interlayer adhesion, chemical solution permeation prevention, low temperature impact resistance, degradation fuel resistance, environmental stress load resistance, and monomer and oligomer elution resistance.

  In the past, automotive piping tubes were made of metal and made of lightweight resin with excellent rust prevention properties in response to the problem of rusting caused by anti-freezing agents on roads and the need to prevent global warming and save energy. The alternative to is progressing. Usually, resins used as piping tubes include polyamide-based resins, saturated polyester-based resins, polyolefin-based resins, thermoplastic polyurethane-based resins, etc. In the case of single-layer tubes using these, heat resistance, Due to insufficient chemical properties, the applicable range was limited.

  In addition, automobile piping tubes are oxygen-containing gasoline blended with alcohols with low boiling points such as methanol and ethanol or ethers such as methyl-t-butyl ether (MTBE) from the viewpoint of saving gasoline consumption and improving performance. Etc. are transferred. Furthermore, from the viewpoint of preventing environmental pollution, strict exhaust gas regulations including prevention of leakage into the atmosphere due to diffusion of volatile hydrocarbons and the like through piping tube partition walls are being implemented. In response to such strict regulations, a single-layer tube using a polyamide-based resin, particularly polyamide 11 or polyamide 12 excellent in strength, toughness, chemical resistance, flexibility, etc., which has been used conventionally, The permeation-preventing property with respect to a chemical solution is not sufficient, and in particular, an improvement for the permeation-preventing property of alcohol-containing gasoline is required.

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

  In particular, the saponified ethylene / vinyl acetate copolymer (EVOH) is very excellent in chemical liquid permeation prevention properties, particularly permeation prevention properties for gasoline. For example, a fuel composed of an outermost layer made of polyamide 12, an adhesive layer made of modified polyolefin, an outer layer made of polyamide 6, an intermediate layer made of saponified ethylene / vinyl acetate copolymer (EVOH), and an innermost layer made of polyamide 6 Piping has been proposed (see Patent Document 2). However, when polyamide 6 is used as the innermost layer in the pipe, the resistance to sour gasoline produced by oxidation of gasoline (deterioration fuel resistance) and the resistance to calcium chloride (chemical resistance) are poor. Further, at least one selected from the group consisting of an outermost layer made of polyamide 12, a polyamide 6/12 copolymer, a polyamide 12/6 copolymer, polyamide 612, polyamide 610, a mixture of polyamide 12, polyamide 6, and a compatibilizer. A laminated composite composed of an adhesive layer made of seed, an intermediate layer made of saponified ethylene / vinyl acetate copolymer (EVOH), and an innermost layer made of polyamide 6 or polyamide 12 has been proposed (Patent Documents 3 and 4). reference). Similarly, an outermost layer made of polyamide 12, an adhesive layer made of a mixture of polyamide 6, polyamide 12 and polyamine / polyamide copolymer, an intermediate layer made of saponified ethylene / vinyl acetate copolymer (EVOH), polyamide 6 or polyamide A laminated composite composed of 12 innermost layers has been proposed (see Patent Document 5). This technique is good for a polyamide copolymer having a specific composition ratio or a mixture of polyamide 6 and polyamide 12 and a compatibilizer as an adhesive layer interposing both polyamide 12 and saponified ethylene / vinyl acetate copolymer. Have been proposed as having a good interlayer adhesion strength. However, when polyamide 6 is used as the innermost layer, no solution has been made to the problem of inferior degradation fuel resistance, zinc chloride resistance, and calcium chloride resistance. Furthermore, when polyamide 12 is used in the innermost layer of the fuel pipe, low molecular weight components such as monomers and oligomers, additives, and plasticizers are eluted into the alcohol-containing gasoline by contact with fuel such as alcohol-containing gasoline. Precipitate. Therefore, there is a concern about blockage in the fuel piping such as the automobile piping tube, the filter, and the nozzle.

  On the other hand, in automotive piping tubes, as inner layer materials that are in direct contact with fuel, it is required to use a resin that is resistant to corrosive chemicals such as ethanol and methanol present in the fuel and has excellent permeation resistance to these. It has been. In this regard, as the inner layer material, it is considered that one of the most preferable materials is a fluorine-based resin that is excellent in heat resistance, chemical resistance, and chemical solution permeation prevention.

  In particular, in order to make the best use of the advantages of the fluororesin and to minimize the disadvantages, various studies have been made on adhesion, lamination, etc. between the fluororesin and other dissimilar materials. However, the fluororesin inherently has poor adhesion, and it is difficult to directly bond with other different materials, and sufficient adhesive strength cannot be obtained. Even when a certain degree of adhesive strength is obtained, the adhesive strength tends to vary depending on the type of different materials, and the adhesive strength is often insufficient practically. Examples of means for increasing the adhesive strength include a method in which a fluororesin tube is formed in advance and a surface treatment is performed, and then a different material is coated, a co-extrusion method using an adhesive resin, and the like. In particular, the coextrusion molding method using an adhesive resin can be said to be a low-cost method because it does not require a surface treatment step. Furthermore, a method of directly bonding a fluororesin and a different material without using an adhesive resin is a more advantageous method in terms of cost and management.

  In the future, more stringent laws and regulations will be imposed from the viewpoint of preventing environmental pollution, and it is desirable to limit the amount of fuel that permeates and evaporates from the tube partition walls for piping. Even in the tube, it is difficult to suppress the fuel that permeates and evaporates from the partition wall to the limit. As a means for overcoming this, a fuel transfer tube having a layer in which a fluorine-based resin is arranged on the inner layer and an ethylene / vinyl acetate copolymer saponified product is arranged on the outer side has been proposed (patent) References 6 and 7). The fuel transfer tube according to the present technology is very excellent in chemical solution permeation prevention. However, in the fuel transfer tube, a modified polyolefin resin or polyamide / polyamide / polyamine graft copolymer is used as an adhesive resin interposed between a layer made of a fluorine resin and a layer made of a saponified ethylene / vinyl acetate copolymer. It is proposed that a mixture of a modified fluororesin or a modified polyolefin resin is disposed, but the interlayer adhesion is not sufficient, and further improvement is desired. In addition, these fuel transfer tubes are generally piped in a state where bending stress is applied due to layout restrictions and displacement absorption at the time of collision. When using the fuel transfer tubes, ethylene / vinyl acetate is often used. There is a problem that microcracks called craze are generated in the layer made of the copolymer saponified product, and the chemical liquid permeation preventing property is greatly impaired, and the laminated tube having resistance to such environmental stress load Development is required.

US Pat. No. 5,554,425 JP-A-3-177683 Special table 2003-535717 JP2003-021276 JP 2002-210904 A JP-A-5-247478 Special table 2008-515658

  The object of the present invention is to solve the above-mentioned problems, and is a laminated tube excellent in interlayer adhesion, chemical solution permeation prevention, low temperature impact resistance, degradation fuel resistance, environmental stress load resistance, and monomer and oligomer elution resistance. Is to provide.

  As a result of intensive studies to solve the above problems, the present inventors have found that a layer made of an aliphatic polyamide (polyamide 11, 12, etc.), a layer made of a modified vinyl alcohol polymer having a specific structural unit, And a laminated tube composed of a layer made of a fluoropolymer having a specific functional group achieves both interlaminar adhesion and chemical solution permeation prevention properties, and further has low temperature impact resistance, deteriorated fuel resistance, environmental stress load resistance, monomer, It has been found that the oligomer has excellent properties such as elution resistance.

  That is, the present invention comprises a (a) layer comprising an aliphatic polyamide (A) and a vinyl alcohol polymer (B) containing a side chain 1,2-diol unit represented by the following formula (1) (b) And (c) a layer composed of a fluorine-based polymer (C) in which a functional group having reactivity to an amino group or a hydroxyl group is introduced into the molecular chain. A laminated tube having the characteristics is provided.

[In General Formula (1), R ¹ , R ² , and R ³ each independently represent a hydrogen atom or an organic group, X represents a single bond or a bonded chain, and R ⁴ , R ⁵ , and R ⁶ represent Each independently represents a hydrogen atom or an organic group. ]

The preferable aspect of the laminated tube of this invention is shown below. A plurality of preferred embodiments can be combined.
[1] The aliphatic polyamide (A) is polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene deca From the group consisting of amide (polyamide 610), polyhexamethylene dodecane (polyamide 612), polydecane methylene decanamide (polyamide 1010), polydecamethylene dodecane (polyamide 1012), and polydodecamethylene dodecane (polyamide 1212). A laminated tube comprising at least one selected homopolymer or a copolymer using several kinds of raw material monomers forming these.
[2] A laminated tube, wherein the content of the side chain 1,2-diol unit in the vinyl alcohol polymer (B) is 0.1 mol% or more and 30 mol% or less.
[3] The laminated tube, wherein the vinyl alcohol polymer (B) is a saponified product of a polyvinyl alcohol polymer or an ethylene / vinyl ester copolymer.
[4] The laminated tube, wherein the vinyl alcohol polymer (B) is a saponified ethylene / vinyl acetate copolymer containing 20 mol% to 60 mol% of ethylene units.
[5] A laminated tube, wherein the melting point of the fluoropolymer (C) is 150 ° C. or higher and 230 ° C. or lower.
[6] A laminated tube, wherein the (a) layer made of the aliphatic polyamide (A) is disposed in the outermost layer.
[7] The (b) layer composed of the vinyl alcohol polymer (B) is disposed between the (a) layer composed of the aliphatic polyamide (A) and the (c) layer composed of the fluoropolymer (C). , (B) layer and (c) layer are directly bonded to each other.
[8] A laminated tube, wherein a conductive layer made of a fluoropolymer composition containing a conductive filler is disposed in the innermost layer of the laminated tube.
[9] A laminated tube, wherein the laminated tube is manufactured by coextrusion molding.
[10] A laminated tube used as a fuel tube.
[11] The laminated tube according to any one of claims 1 to 11, wherein the laminated tube has at least a corrugated region.

  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, resistance to deterioration fuel, resistance to environmental stress load, and elution resistance of monomers and oligomers. In particular, alcohol mixed hydrocarbons that permeate and evaporate from the tube partition wall can be suppressed to the limit, and compliance with strict environmental regulations becomes possible. Furthermore, it is excellent in resistance to sour gasoline produced by oxidation of gasoline (deterioration fuel resistance) and environmental stress load resistance such as bending stress, which are problems in actual use of the laminated tube. Therefore, the laminated tube of the present invention can be used in any environment, has high reliability, and its utility value is extremely large.

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

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

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

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

Examples of the aliphatic polyamide (A) include polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyethylene adipamide (polyamide 26), polytetramethylene succinamide (polyamide) 44), polytetramethylene glutamide (polyamide 45), polytetramethylene adipamide (polyamide 46), polytetramethylene suberamide (polyamide 48), polytetramethylene azelamide (polyamide 49), polytetramethylene sebacamide (Polyamide 410), polytetramethylene dodecamide (polyamide 412), polypentamethylene succinamide (polyamide 54), polypentamethylene glutamide (polyamide 55), polypentamethylene adipamide (polyamide) 6), polypentamethylene suberamide (polyamide 58), polypentamethylene azelamide (polyamide 59), polypentamethylene sebamide (polyamide 510), polypentamethylene dodecamide (polyamide 512), polyhexamethylene succinamide (Polyamide 64), polyhexamethylene glutamide (polyamide 65), polyhexamethylene adipamide (polyamide 66), polyhexamethylene suberamide (polyamide 68), polyhexamethylene azelamide (polyamide 69), polyhexamethylene Bacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polyhexamethylene tetradecanamide (polyamide 614), polyhexamethylene hexadecanamide (polyamide 616), polyhexame Lenoctadecamide (Polyamide 618), Polynonamethylene adipamide (Polyamide 96), Polynonamethylene suberamide (Polyamide 98), Polynonamethylene azelamide (Polyamide 99), Polynonamethylene sebacamide (Polyamide 910) , Polynonamethylene dodecamide (polyamide 912), polydecamethylene adipamide (polyamide 106), polydecamethylene suberamide (polyamide 108), polydecamethylene azelamide (polyamide 109), polydecamethylene sebacamide (polyamide) 1010), polydecamethylene dodecamide (polyamide 1012), polydodecamethylene adipamide (polyamide 126), polydodecamethylene suberamide (polyamide 128), polydodecamethylene azelamide (polyamide 129) And homopolymers such as polydodecamethylene sebacamide (polyamide 1210) and polydodecamethylene dodecamide (polyamide 1212), and copolymers using several raw material monomers forming these.
Among these, polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene azelamide (polyamide 69), poly Hexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene dodecamide (polyamide 912), polydecamethylene sebacamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012) Polydodecamethylene dodecamide (polyamide 1212) and a copolymer using several kinds of raw material monomers forming these are preferable, such as polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydode Amide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene decanamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecamethylene decanamide (polyamide 1010), polydecamethylene There are at least one homopolymer selected from the group consisting of dodecamide (polyamide 1012) and polydodecamethylene dodecamide (polyamide 1212), or a copolymer using several raw material monomers forming these. preferable.

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

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

  In the aliphatic polyamide (A), when the terminal amino group concentration per 1 g of the polyamide is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), [A]> [B ] To the vinyl alcohol polymer (B) containing a side chain 1,2-diol unit, an amino group or a hydroxyl group. In view of interlayer adhesion with the fluoropolymer (C) in which a functional group having reactivity is introduced into the molecular chain, [A]> [B] +10 is more preferable, and [A]> More preferably, [B] +15. Furthermore, [A]> 20 is preferable from the viewpoint of the melt stability of the polyamide and the generation of gel-like substances is suppressed, and 30 <[A] <120 is more preferable.

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

  The terminal-modified aliphatic polyamide is produced by polymerizing or copolymerizing the polyamide raw material in the presence of amines by a known method such as melt polymerization, solution polymerization or solid phase polymerization. Alternatively, it is produced by melt-kneading in the presence of amines after polymerization. As described above, amines can be added at any stage during polymerization or at any stage after melt kneading after polymerization. However, when the interlayer adhesion of the laminated tube is taken into consideration, the amines are added at the stage during polymerization. It is preferable.

  Examples of the amines include monoamines, diamines, triamines, and polyamines. In addition to amines, carboxylic acids such as monocarboxylic acids, dicarboxylic acids, and tricarboxylic acids may be added as necessary as long as they do not deviate from the range of the above-mentioned end group concentration conditions. These amines and carboxylic acids may be added simultaneously or separately. Moreover, 1 type (s) or 2 or more types can be used for the amines and carboxylic acids illustrated below.

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

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

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

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

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

  Examples of the polyalkyleneimine include one or two alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, 1,1-dimethylethyleneimine Examples include homopolymers and copolymers obtained by polymerizing more than one species by a conventional method. Among these, polyethyleneimine is more preferable. Polyalkyleneimine is polymerized from alkyleneimine as a raw material, branched polyalkyleneimine obtained by ring-opening polymerization of alkyleneimine, secondary polyamineimine containing secondary amine and tertiary amine, or alkyloxazoline as a raw material. Either a linear polyalkyleneimine containing only a primary amine and a secondary amine, or a three-dimensionally crosslinked structure may be used. Furthermore, ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine, bisaminopropylethylenediamine and the like may be included. A polyalkyleneimine is usually derived from the reactivity of an active hydrogen atom on a nitrogen atom contained therein, and in addition to a tertiary amino group, a primary amino group having an active hydrogen atom or a secondary amino group (imino Group).

  The number of nitrogen atoms in the polyalkyleneimine is not particularly limited, but is preferably 4 or more and 3,000 or less, more preferably 8 or more and 1,500 or less, and further preferably 11 or more and 500 or less. preferable. The number average molecular weight of the polyalkyleneimine is preferably 100 or more and 20,000 or less, more preferably 200 or more and 10,000 or less, and further preferably 500 or more and 8,000 or less.

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

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

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

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

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

  Other polyamide resins include polymetaxylylene adipamide (polyamide MXD6), polymetaxylylene veramide (polyamide MXD8), polymetaxylylene azelamide (polyamide MXD9), polymetaxylylene sebacamide (polyamide MXD10). , Polymetaxylylene decanamide (polyamide MXD12), polymetaxylylene terephthalamide (polyamide MXDT), polymetaxylylene isophthalamide (polyamide MXDI), polymetaxylylene hexahydroterephthalamide (polyamide MXDT (H)), polymer Taxylylene naphthalamide (polyamide MXDN), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylene beramide (polyamide PXD8), polyparaxylylene azelamide Polyamide PXD9), polyparaxylylene sebacamide (polyamide PXD10), polyparaxylylene dodecamide (polyamide PXD12), polyparaxylylene terephthalamide (polyamide PXDT), polyparaxylylene isophthalamide (polyamide PXDI) , Polyparaxylylene hexahydroterephthalamide (polyamide PXDT (H)), polyparaxylylene naphthalamide (polyamide PXDN), polyparaphenylene terephthalamide (PPTA), polyparaphenylene isophthalamide (PPIA), poly Metaphenylene terephthalamide (PMTA), polymetaphenylene isophthalamide (PMIA), poly (2,6-naphthalenediethylene adipamide) (polyamide 2,6-BAN6), poly (2,6-naphthalenedimethyle Suberamide) (polyamide 2,6-BAN8), poly (2,6-naphthalene dimethylene azelamide) (polyamide 2,6-BAN9), poly (2,6-naphthalene dimethylene sebacamide) (polyamide 2,6 -BAN10), poly (2,6-naphthalene dimethylene dodecamide) (polyamide 2,6-BAN12), poly (2,6-naphthalene dimethylene terephthalamide) (polyamide 2,6-BANT), poly (2 , 6-Naphthalenedylene methylene isophthalamide) (polyamide 2,6-BANI), poly (2,6-naphthalenediethylene hexahydroterephthalamide) (polyamide 2,6-BANT (H)), poly (2, 6-naphthalene dimethylene naphthalamide) (polyamide 2,6-BANN), poly (1,3-cyclohexanedimethylene) Dipamide) (polyamide 1,3-BAC6), poly (1,3-cyclohexanedimethylenesberamide (polyamide 1,3-BAC8), poly (1,3-cyclohexanedimethylene azelamide) (polyamide 1,3-BAC9) ), Poly (1,3-cyclohexanedimethylene sebacamide) (polyamide 1,3-BAC10), poly (1,3-cyclohexanedimethylene dodecamide) (polyamide 1,3-BAC12), poly (1,3 -Cyclohexanedimethylene terephthalamide) (polyamide 1,3-BACT), poly (1,3-cyclohexanedimethylene isophthalamide) (polyamide 1,3-BACI), poly (1,3-cyclohexanedimethylene hexahydro Terephthalamide) (polyamide 1,3-BACT (H)), poly (1,3-sic Hexane dimethylene naphthalamide) (polyamide 1,3-BACN), poly (1,4-cyclohexanedimethylene adipamide) (polyamide 1,4-BAC6), poly (1,4-cyclohexanedimethylene suberamide) ( Polyamide 1,4-BAC8), poly (1,4-cyclohexanedimethylene azelamide) (polyamide 1,4-BAC9), poly (1,4-cyclohexanedimethylene sebacamide) (polyamide 1,4-BAC10) , Poly (1,4-cyclohexanedimethylene dodecamide) (polyamide 1,4-BAC12), poly (1,4-cyclohexanedimethylene terephthalamide) (polyamide 1,4-BACT), poly (1,4- Cyclohexanedimethylene isophthalamide) (polyamide 1,4-BACI), poly (1,4- Chlorohexane dimethylene hexahydroterephthalamide) (polyamide 1,4-BACT (H)), poly (1,4-cyclohexanedimethylene naphthalamide) (polyamide 1,4-BACN), poly (4,4′- Methylenebiscyclohexylene adipamide) (polyamide PACM6), poly (4,4′-methylenebiscyclohexylene suberamide) (polyamide PACM8), poly (4,4′-methylenebiscyclohexylene azelamide) (polyamide PACM9) , Poly (4,4′-methylenebiscyclohexylene sebacamide) (polyamide PACM10), poly (4,4′-methylenebiscyclohexylene dodecamide) (polyamide PACM12), poly (4,4′-methylenebiscyclohexyl) Silenetetradecamide) (Polyamide PACM) 14), poly (4,4′-methylenebiscyclohexylenehexadecamide) (polyamide PACM16), poly (4,4′-methylenebiscyclohexyleneoctadecamide) (polyamide PACM18), poly (4,4′- Methylenebiscyclohexylene terephthalamide) (polyamide PACMT), poly (4,4′-methylenebiscyclohexylene isophthalamide) (polyamide PACMI), poly (4,4′-methylenebiscyclohexylene hexahydroterephthalamide) (Polyamide PACMT (H)), poly (4,4′-methylenebiscyclohexylenenaphthalamide) (polyamide PACMN), poly (4,4′-methylenebis (2-methyl-cyclohexylene) adipamide) (polyamide MACM6), Poly (4,4'-methylene (2-methyl-cyclohexylene) suberamide) (polyamide MACM8), poly (4,4′-methylenebis (2-methyl-cyclohexylene) azeramide) (polyamide MACM9), poly (4,4′-methylenebis (2- Methyl-cyclohexylene) sebacamide) (polyamide MACM10), poly (4,4′-methylenebis (2-methyl-cyclohexylene) dodecamide) (polyamide MACM12), poly (4,4′-methylenebis (2-methyl-cyclohexylene) ) Tetradecamide) (polyamide MACM14), poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexadecamide) (polyamide MACM16), poly (4,4′-methylenebis (2-methyl-cyclohexylene) octadecamide) ( Polyami MACM18), poly (4,4′-methylenebis (2-methyl-cyclohexylene) terephthalamide) (polyamide MACMT), poly (4,4′-methylenebis (2-methyl-cyclohexylene) isophthalamide) (polyamide MACMI), poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexahydroterephthalamide) (polyamide MACMT (H)), poly (4,4′-methylenebis (2-methyl-cyclohexylene) naphthalamide) (polyamide MACMN ), Poly (4,4′-propylene biscyclohexylene adipamide) (polyamide PACP6), poly (4,4′-propylene biscyclohexylene suberamide) (polyamide PACP8), poly (4,4′-propylene bis) Cyclohexylene azeamide) (Polyamide PACP9), poly (4,4′-propylene biscyclohexylene sebacamide) (polyamide PACP10), poly (4,4′-propylene biscyclohexylene dodecamide) (polyamide PACP12), poly (4,4 ′ -Propylene biscyclohexylene tetradecanamide (polyamide PACP14), poly (4,4'-propylene biscyclohexylene hexadecanamide) (polyamide PACP16), poly (4,4'-propylene biscyclohexylene octadecanamide) ( Polyamide PACP18), poly (4,4′-propylene biscyclohexylene terephthalamide) (polyamide PACPT), poly (4,4′-propylene biscyclohexylene isophthalamide) (polyamide PACPI), poly (4,4 ′ -Propi Biscyclohexylene hexahydroterephthalamide) (polyamide PACPT (H)), poly (4,4′-propylene biscyclohexylene naphthalamide) (polyamide PACPN), polyisophorone adipamide (polyamide IPD6), polyisophorones Lamide (polyamide IPD8), polyisophorone azeramide (polyamide IPD9), polyisophorone sebamide (polyamide IPD10), polyisoholondecamide (polyamide IPD12), polyisophorone terephthalamide (polyamide IPDT), polyisophorone isophthalamide Polyamide IPDI), polyisophorone hexahydroterephthalamide (polyamide IPDT (H)), polyisophorone naphthalamide (polyamide IPDN), polytetramethylene terephthala (Polyamide 4T), polytetramethylene isophthalamide (polyamide 4I), polytetramethylene hexahydroterephthalamide (polyamide 4T (H)), polytetramethylene naphthalamide (polyamide 4N), polypentamethylene terephthalamide ( Polyamide 5T), polypentamethylene isophthalamide (polyamide 5I), polypentamethylene hexahydroterephthalamide (polyamide 5T (H)), polypentamethylene naphthalamide (polyamide 5N), polyhexamethylene terephthalamide (polyamide 6T) ), Polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene hexahydroterephthalamide (polyamide 6T (H)), polyhexamethylene naphthalamide (polyamide 6N), poly (2-methylpentameth) Tylene terephthalamide) (polyamide M5T), poly (2-methylpentamethylene isophthalamide) (polyamide M5I), poly (2-methylpentamethylene hexahydroterephthalamide) (polyamide M5T (H)), poly (2 -Methylpentamethylene naphthalamide) (polyamide M5N), polynonamethylene terephthalamide (polyamide 9T), polynonamethylene isophthalamide (polyamide 9I), polynonamethylene hexahydroterephthalamide (polyamide 9T (H)), Polynonamethylene naphthalamide (polyamide 9N), poly (2-methyloctamethylene terephthalamide) (polyamide M8T), poly (2-methyloctamethylene isophthalamide) (polyamide M8I), poly (2-methyloctamethylenehexa) Hydroterephthala (Polyamide M8T (H)), poly (2-methyloctamethylene naphthalamide) (polyamide M8N), polytrimethylhexamethylene terephthalamide (polyamide TMHT), polytrimethylhexamethylene isophthalamide (polyamide TMHI), poly Trimethylhexamethylene hexahydroterephthalamide (polyamide TMHT (H)), polytrimethylhexamethylene naphthalamide (polyamide TMHN), polydecamethylene terephthalamide (polyamide 10T), polydecamethylene isophthalamide (polyamide 10I), poly Decamethylene hexahydroterephthalamide (polyamide 10T (H)), polydecamethylene naphthalamide (polyamide 10N), polyundecamethylene terephthalamide (polyamide 11T), poly Ndecamethylene isophthalamide (polyamide 11I), polyundecamethylene hexahydroterephthalamide (polyamide 11T (H)), polyundecamethylene naphthalamide (polyamide 11N), polydodecamethylene terephthalamide (polyamide 12T), Polydodecamethylene isophthalamide (polyamide 12I), polydodecamethylene hexahydroterephthalamide (polyamide 12T (H)), polydodecamethylene naphthalamide (polyamide 12N), A polymer etc. are mentioned. 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 Polymers (SIS), polystyrene resins such as styrene / ethylene / butylene / styrene copolymer (SEBS), styrene / ethylene / propylene / styrene copolymer (SEPS), carboxyl groups, and salts thereof, acid anhydride groups Containing functional groups such as epoxy groups Polyolefin resins and polystyrene resins, 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), polyetherether Polyketone resins such as ketone (PEEK), polyetherketoneketone (PEKK), polyetheretherketoneketone (PEEKK), polyetherketoneetherketoneketone (PEKEKK), polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / Polynitriles such as styrene 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 / chloride Polyvinyl resins such as vinylidene copolymers, vinylidene chloride / methyl acrylate copolymers, 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 aliphatic polyamide (A). Examples of the plasticizer include benzenesulfonic acid alkylamides, toluenesulfonic acid alkylamides, and hydroxybenzoic acid alkyl esters.

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

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

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

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

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

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

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

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

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

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

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

Further, (ethylene and / or propylene) / α-olefin copolymer, (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) used as an impact resistance improving material ) Type copolymer, ionomer polymer, and aromatic vinyl compound / conjugated diene compound type block copolymer are preferably polymers modified with carboxylic acid and / or derivatives thereof. By modifying with such a component, a functional group having affinity for the aliphatic polyamide (A) is included in the molecule.
Examples of the functional group having affinity for the aliphatic polyamide (A) include a carboxyl group, an acid anhydride group, a carboxylic acid ester group, a carboxylic acid metal salt, a carboxylic acid imide group, a carboxylic acid amide group, and an epoxy group. Can be mentioned. Examples of compounds containing these functional groups include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid Endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid and metal salts of these carboxylic acids, monomethyl maleate, monomethyl itaconate, methyl acrylate, ethyl acrylate, butyl acrylate 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, itaconic anhydride, citracone anhydride Acid, endobicyclo- 2.2.1] -5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, acrylamide, methacrylamide, glycidyl acrylate, glycidyl methacrylate, Examples include glycidyl ethacrylate, glycidyl itaconate, and glycidyl citraconic acid. These can use 1 type (s) or 2 or more types.

  The content of the impact resistance improving material is 1 part by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the aliphatic polyamide (A) from the viewpoint of sufficiently ensuring the mechanical strength and low temperature impact resistance of the laminated tube. It is preferable that it is 3 parts by mass or more and 25 parts by mass or less.

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

  The vinyl alcohol polymer (B) used in the present invention is a vinyl alcohol polymer containing a side chain 1,2-diol unit represented by the following formula (1) (hereinafter referred to as side chain 1, 2). -A diol unit containing vinyl alcohol polymer (B) may be called.).

In the formula (1), R ¹ to R ⁶ each independently represents a hydrogen atom or an organic group. The organic group is not particularly limited, but examples thereof include saturated hydrocarbon groups such as methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, phenyl And aromatic hydrocarbon groups such as a benzyl group, and optionally have a substituent such as a halogen group, a hydroxyl group, an acyloxy group, an alkoxycarbonyl group, a carboxyl group, or a sulfonic acid group. Among these, a saturated hydrocarbon group or hydrogen atom having 1 to 30 carbon atoms is preferable, a saturated hydrocarbon group or hydrogen atom having 1 to 15 carbon atoms is more preferable, and a saturated hydrocarbon group having 1 to 4 carbon atoms is more preferable. A hydrocarbon group or a hydrogen atom is more preferable, and a hydrogen atom is particularly preferable. Most preferably, all of R ¹ to R ⁶ are hydrogen atoms.

In the formula (1), X is a single bond or a bond chain, and is preferably a single bond from the viewpoint of suitably maintaining chemical solution permeation prevention properties. The bonding chain is not particularly limited, but is a hydrocarbon chain such as alkylene, alkenylene, alkynylene, phenylene, or naphthylene (these hydrocarbons may be substituted with halogen such as fluorine, chlorine, or bromine). _{other, -O -, - (CH 2} O) m -, - (OCH 2) m -, - (CH 2 O) n CH 2 - units containing an ether binding site, such as, -CO -, - COCO-, A unit containing a carbonyl group such as —CO (CH ₂ ) _m CO— or —CO (C ₆ H ₄ ) CO—, or a sulfur atom such as —S—, —CS—, —SO— or —SO ₂ —. units, -NR -, - CONR -, - NRCO -, - CSNR -, - NRCS -, - NRNR- like unit containing a nitrogen atom, -HPO ₄ - including the hetero atoms in the unit and the like including a phosphorus atom, such as units, -Si _(OR) 2 -, _{OSi (OR) 2 -, -} OSi (OR) 2 O- such unit containing a silicon _{atom, -Ti (OR) 2 -,} - OTi (OR) 2 -, - OTi (OR) 2 O- and the like titanium Units containing atoms, units containing metal atoms such as aluminum atoms such as -Al (OR)-, -OAl (OR)-, and -OAl (OR) O- It is independently an arbitrary substituent, preferably a hydrogen atom or an alkyl group, and m is a natural number, usually 1 or more and 30 or less, preferably 1 or more and 15 or less, and preferably 1 or more and 10 or less. More preferred). Among these, from the viewpoint of stability during production or use, a hydrocarbon chain having 1 to 10 carbon atoms is more preferable, a hydrocarbon chain having 1 to 6 carbon atoms is more preferable, and the number of carbon atoms is 1 The hydrocarbon chain is particularly preferred.

The most preferable structure in the side chain 1,2-diol unit represented by the above formula (1) is a structural unit in which all of R ¹ to R ⁶ are hydrogen atoms and X is a single bond. That is, the structural unit represented by the following formula (1a) is most preferable.

  The side chain 1,2-diol unit-containing vinyl alcohol polymer (B) has a lower melting point than those of the vinyl alcohol polymer having no side chain 1,2-diol unit, and melt moldability. Excellent.

The content of the side chain 1,2-diol unit in the side chain 1,2-diol unit-containing vinyl alcohol polymer (B) ensures good low-temperature impact resistance, environmental stress load resistance and melt moldability. From the viewpoint of suitably maintaining the chemical solution permeation prevention property, it is preferably 0.1 mol% or more and 30 mol% or less, and 0.5 mol% or more and 25 mol% or less with respect to all monomer units. Is more preferable, and it is further more preferable that they are 1 mol% or more and 20 mol% or less. Here, the content of the side chain 1,2-diol unit can be calculated from the measurement result of ¹ H-NMR.

  The vinyl alcohol polymer constituting the side chain 1,2-diol unit-containing vinyl alcohol polymer (B) is a polyvinyl alcohol polymer (PVA polymer) or ethylene as a saponified vinyl ester polymer. / Concept including saponified vinyl ester copolymer (EVOH polymer). That is, as the side chain 1,2-diol unit-containing vinyl alcohol polymer (B) used in the present invention, the side chain 1,2-diol unit containing the side chain 1,2-diol unit represented by the above formula (1) is used. In addition to the 2-diol-containing PVA polymer, EVOH polymers containing side chain 1,2-diol units may be mentioned.

  The side chain 1,2-diol-containing PVA polymer is included within a range that does not impair the characteristics as a vinyl ester monomer, a monomer that becomes a side chain 1,2-diol unit, and a PVA polymer. A saponified product of a copolymer of a vinyl ester and a copolymerizable monomer, which is a vinyl alcohol unit, a side chain 1,2-diol unit, a unit derived from a copolymerizable monomer, and a residual Has vinyl ester units. The total content of vinyl alcohol units and side chain 1,2-diol units in the side chain 1,2-diol-containing PVA polymer is 80 mol% or more and 100 mol% or less with respect to all monomer units. It is preferable.

  The side chain 1,2-diol-containing EVOH polymer is an ethylene, vinyl ester monomer, a monomer that becomes a side chain 1,2-diol unit, and a range that does not impair the characteristics of the EVOH polymer. A saponified product of a copolymer of a vinyl ester and / or a monomer copolymerizable with ethylene, which is an ethylene unit, a vinyl alcohol unit, a side chain 1,2-diol unit, a copolymerizable monomer It has a unit derived from a monomer and a remaining vinyl ester unit. The content of the ethylene unit is preferably 20 mol% or more and 60 mol% or less, and preferably 20 mol% or more and 50 mol% or less, based on the total monomer units, from the viewpoint of suitably maintaining the chemical solution permeation preventing property. More preferably, it is 25 mol% or more and 48 mol% or less. The total content of the vinyl alcohol unit and the side chain 1,2-diol unit in the side chain 1,2-diol-containing EVOH polymer is 40 mol% or more and 80 mol% or less with respect to the total monomer units. It is preferable that

  Examples of the vinyl ester monomers include vinyl formate, vinyl acetate, vinyl propionate, vinyl valelate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl caprate, and laurin. Vinyl acid, vinyl myristate, vinyl palmitate, vinyl stearate, vinyl stearate, isopropenyl acetate, 1-butenyl acetate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl cyclohexanecarboxylate, vinyl benzoate, versatic acid Vinyl etc. are mentioned. Among these, vinyl acetate is preferable from the economical aspect.

  The side chain 1,2-diol unit-containing vinyl alcohol polymer (B) can be copolymerized with other monomers as long as the object of the present invention is not inhibited. Other monomers include, for example, propylene, 1-butene, isobutene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-dodecene and other α-olefins, acrylic acid, methacrylic acid, Unsaturated acids such as crotonic acid, phthalic acid, (anhydrous) maleic acid, (anhydrous) itaconic acid, or unsaturated acids or salts thereof, mono- or dialkyl esters having 1 to 18 carbon atoms, acrylamide, N-alkyl acrylamide having 1 to 18 carbon atoms, N, N-dimethylacrylamide, 2-acrylamidopropanesulfonic acid or its salt, acrylamide such as acrylamidopropyldimethylamine or its acid salt or its quaternary salt, methacrylamide N-alkyl methacrylamide having 1 to 18 carbon atoms, N, -Methacrylamide such as dimethylmethacrylamide, 2-methacrylamidepropanesulfonic acid or its salt, methacrylamideamidopropylamine or its acid salt or its quaternary salt, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide N-vinylamides such as acrylonitrile, methacrylonitrile, vinyl cyanides such as alkyl vinyl ethers having 1 to 18 carbon atoms, vinyl ethers such as hydroxyalkyl vinyl ether and alkoxyalkyl vinyl ether, vinyl chloride, vinylidene chloride, fluoride Vinyl, vinylidene fluoride, vinyl halides such as vinyl bromide, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyldimethylmethoxysilane, vinyltriethoxysilane, vinyl Vinylsilanes such as methyldiethoxysilane, vinyldimethylethoxysilane γ-methacryloxypropylmethoxysilane, allyl acetate, allyl chloride, allyl alcohol, dimethylallyl alcohol, trimethyl- (3-acrylamido-3-dimethylpropyl) -ammonium chloride, Examples include acrylamide-2-methylpropanesulfonic acid. These can use 1 type (s) or 2 or more types.

  When the side chain 1,2-diol unit-containing vinyl alcohol polymer (B) is exemplified by a vinyl alcohol polymer containing the structural unit (1a) which is the most preferable structure, [1] side chain 1,2 -3,4-diol-1-butene, 3,4-diasiloxy-1-butene, 3-acyloxy-4-ol-1-butene, 4-acyloxy-3-ol as monomers capable of supplying diol units Using 1-butene, 3,4-diacyloxy-2-methyl-1-butene, etc., these are copolymerized with a vinyl ester monomer (or ethylene in the case of EVOH polymer) to obtain a copolymer. And then saponifying this, [2] using vinyl ethylene carbonate or the like as a monomer capable of supplying side chain 1,2-diol units, and these and vinyl ester monomers (EVOH polymer) In some cases, the copolymer is further copolymerized with ethylene) to obtain a copolymer, which is then saponified and decarboxylated, [3] 2,2- Dialkyl-4-vinyl-1,3-dioxolane and the like are copolymerized with a vinyl ester monomer (in the case of EVOH polymer, further ethylene) to obtain a copolymer, then saponified, It can be produced by a method of deacetalization or the like.

  Of the above production methods, the method [1] is preferably employed. In consideration of copolymerization reactivity, 3,4-diacyloxy-1-butene and a vinyl ester monomer (and ethylene) are copolymerized. A method of saponifying the copolymer obtained in this manner is preferred. More preferably, 3,4-diacetoxy-1-butene is used as 3,4-diasiloxy-1-butene. According to such a production method, the polymerization proceeds well, and side chain 1,2-diol units are easily introduced uniformly into the main chain of the vinyl alcohol polymer, resulting in fewer unreacted monomers and impurities. There is an advantage that it can be reduced.

Specifically, the reactivity ratio of each monomer when vinyl acetate and 3,4-diacetoxy-1-butene are copolymerized is r (vinyl acetate) = 0.710, r (3,4). -Diacetoxy-1-butene) = 0.701. Compared with the reactivity ratio of each monomer when using vinyl ethylene carbonate of [2], r (vinyl acetate) = 0.85, r (vinyl ethylene carbonate) = 5.4, -Diacetoxy-1-butene has better copolymerization reactivity with vinyl acetate.
The chain transfer constant of 3,4-diacetoxy-1-butene is Cx (3,4-diacetoxy-1-butene) = 0.003 (65 ° C.). Cx (vinyl ethylene carbonate) = 0.005 (65 ° C.) of vinyl ethylene carbonate used in the method [2] and 2,2-dimethyl-4-vinyl-1,3-dioxolane used in the method [3] Compared with Cx (2,2-dimethyl-4-vinyl-1,3-dioxolane) = 0.023 (65 ° C), the chain transfer constant of 3,4-diacetoxy-1-butene is small, and the degree of polymerization is increased. It is easy to cause a decrease in polymerization rate.

  Furthermore, when 3,4-diacetoxy-1-butene is used, the by-product produced when the obtained copolymer is saponified is the same as the by-product derived from the vinyl acetate unit. Therefore, the method [1] using 3,4-diacetoxy-1-butene also has an industrial advantage that it is not necessary to provide a special apparatus or process for the post-treatment.

  On the other hand, a vinyl alcohol polymer having a side chain 1,2-diol unit produced by the production method [2] has a carbonate ring in the side chain when the degree of saponification is low or when decarboxylation is insufficient. Remains, tends to be decarboxylated during melt molding and cause the resin to foam. Further, the vinyl alcohol polymer having a side chain 1,2-diol unit produced by [3] is also a functional group derived from a monomer remaining in the side chain (as in the production method [2] ( Since the acetal ring) tends to be detached during melt molding to generate an odor, it should be used with this in mind.

  In addition, 3,4-diol-1-butene used as a raw material in the method of [1] is from Eastman Chemical Company, and 3,4-diacetoxy-1-butene is from Eastman Chemical Company for industrial production, and at reagent level. Acros products can be obtained from the market. 3,4-diacetoxy-1-butene obtained as a by-product during the production process of 1,4-butanediol can also be used. 3,4-diacetoxy-1-butene used as a raw material includes 3,4-diacetoxy-1-butane, 1,4-diacetoxy-1-butene, 1,4-diacetoxy-1-butane, etc. as a small amount of impurities. May be included.

  The degree of saponification of the side chain 1,2-diol unit-containing vinyl alcohol polymer (B) (content of vinyl ester units in the vinyl alcohol polymer that are converted to vinyl alcohol units by saponification) is Although not particularly limited, from the viewpoint of suitably maintaining the chemical solution permeation preventing property, it is preferably 90 mol% or more and 100 mol% or less, more preferably 95 mol% or more and 100 mol% or less, and 99 mol% or more. More preferably, it is 100 mol% or less.

  The melting point of the side chain 1,2-diol unit-containing vinyl alcohol polymer (B) having the above structure is preferably 100 ° C. or higher and 220 ° C. or lower, and 130 ° C. or higher and 200 ° C. or lower. More preferably, it is 150 degreeC or more and 190 degrees C or less.

  The melt flow rate (MFR) at 210 ° C. and a load of 2160 g of the side chain 1,2-diol unit-containing vinyl alcohol polymer (B) ensures a desirable moldability by setting the viscosity at the time of melting within an appropriate range, and melt tension. From the viewpoint of preventing the occurrence of problems such as drawdown during molding without excessively reducing the thickness, it is preferably 0.1 g / 10 min to 200 g / 10 min, and preferably 1 g / 10 min to 100 g / 10 min. It is more preferable that it is 2 g / 10 min or more and 50 g / 10 min or less.

  The side chain 1,2-diol unit-containing vinyl alcohol polymer (B) is not only one type, but the side chain 1,2-diol unit-containing vinyl alcohol polymer (B) having a different saponification degree, the molecular weight is Different side chain 1,2-diol unit-containing vinyl alcohol polymer (B), PVA polymer, or side copolymer 1,2 having different types of comonomer constituting EVOH polymer Two or more kinds of side chain 1,2-diol unit-containing vinyl alcohol polymers (B) such as a diol unit-containing vinyl alcohol polymer (B) may be used in combination.

  When the side chain 1,2-diol unit-containing vinyl alcohol polymer (B) is a side chain 1,2-diol-containing EVOH polymer, those having different ethylene unit contents may be used in combination. . When those having different ethylene unit contents are used together, the other units may be the same or different, but the ethylene content difference is preferably 1 mol% or more, preferably 2 mol% or more. More preferably, it is 2 mol% or more and 20 mol% or less.

  Furthermore, a PVA polymer not containing a side chain 1,2-diol unit or an EVOH polymer not containing a side chain 1,2-diol unit may be mixed. In the case of a mixture of a side chain 1,2-diol unit-containing vinyl alcohol polymer and another vinyl alcohol polymer, the content of the side chain 1,2-diol unit in the mixture is calculated from the mixing mass ratio. The value is preferably 0.1 mol% or more and 30 mol% or less, more preferably 0.5 mol% or more and 25 mol% or less, and more preferably 0.75 mol based on the total polymerization units of the mixture. % To 20 mol% is more preferable.

  When blending and using two or more different types of side-chain 1,2-diol unit-containing vinyl alcohol polymers (B), the method for producing the blend is not particularly limited. For example, a method of saponifying each paste of vinyl ester copolymer before saponification, and a method of mixing a solution obtained by dissolving a saponified vinyl alcohol polymer in alcohol or a mixed solvent of water and alcohol And a method of melt-kneading after mixing the pellets or powders of each vinyl alcohol polymer.

  The side chain 1,2-diol unit-containing vinyl alcohol polymer (B) alone may be constituted, or other thermoplastic resins other than the vinyl alcohol polymer as long as the effects of the present invention are not impaired. In addition, various additives, inevitably contained monomer residues for the production of vinyl alcohol polymers, saponified monomers, and so-called impurities may be contained.

  Specific examples of inevitable impurities include 3,4-diacetoxy-1-butene, 3,4-diol-1-butene, 3,4-diacetoxy-1-butene, and 3-acetoxy-4-ol-1. -Butene, 4-acetoxy-3-ol-1-butene and the like.

  Examples of additives include plasticizers such as dimethyl phthalate, diethyl phthalate, dioctyl phthalate, and phosphate esters, pentaerythritol monostearate, sorbitan monopalmitate, sulfated polyolefins, ethylene glycol, glycerin, and hexane. Antistatic agent such as aliphatic polyhydric alcohols such as diol, saturated fatty acid amide such as stearic acid amide, unsaturated fatty acid amide such as oleic acid amide, bis fatty acid amide such as ethylene bis stearic acid amide, calcium stearate, stearic acid Lubricants such as fatty acid metal salts such as magnesium, zinc stearate, aluminum stearate, wax, liquid paraffin, low molecular weight polyethylene having a molecular weight of about 500 to 10,000, low molecular weight polyolefin such as low molecular weight polypropylene, etc. Stabilizers such as organic acids such as acetic acid, propionic acid, stearic acid, inorganic acid compounds such as boric acid compounds and phosphoric acid compounds, metal salts of hydrotalcite, reduced iron powders, potassium sulfite, ascorbic acid, hydroquinone , Oxygen absorbers such as gallic acid, colorants such as carbon black, phthalocyanine, quinacridone, indoline, azo pigments, bengara, glass fiber, asbestos, ballastite, mica, sericite, talc, silica, kaolin, calcium silicate , Fillers such as montmorillonite, 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4,4′-thiobis (6-t-butyl-m-cresol), 4,4'-thiobis (6-t-butylphenol), 4,4'-thiobis (3-methyl-6-t- Thiphenol), 2,2′-methylene-bis (4-methyl-6-tert-butylphenol), 2,2′-methylenebis (4-ethyl-6-tert-butylphenol), n-octadecyl-β- (3 ', 5'-di-t-butyl-4'-hydroxyphenyl) propionate, N, N'-hexamethylenebis (3,5-di-t-butyl-4-hydroxyhydrocinnamide), 1,1, 3-tris (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di-tert-butyl-4-hydroxy Benzyl) benzene, tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl) propionate], benzeneerythrityl-tetrakis [3- (3,5-di-t-butyl) Ru-4-hydroxyphenyl) propionate], tris (2,4-di-t-butylphenyl), di (2,4-di-t-butylphenyl) -pentaerythritol-diphosphite, etc., ethylene 2-cyano-3,3′-diphenyl acrylate, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-methylphenyl) ) -5-chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone, 2,2′-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and other ultraviolet absorbers.

  In addition to the above additives, hydrotalcite compounds, hindered phenol-based antioxidants, etc., within the range that does not obstruct the object of the present invention in order to improve various physical properties such as thermal stability during melt molding It is preferable to add 0.01 part by mass or more and 1 part by mass or less of 1 type or 2 types to 100 parts by mass of the side chain 1,2-diol unit-containing vinyl alcohol polymer (B).

  Further, in addition to the above additives, in order to improve various physical properties such as thermal stability during melt molding, organic acids such as acid, propionic acid, butyric acid, lauric acid, stearic acid, oleic acid, behenic acid, or the like Salts such as alkali metal salts (sodium, potassium, etc.), alkaline earth metal salts (calcium, magnesium, etc.), inorganic acids such as sulfuric acid, sulfurous acid, carbonic acid, phosphoric acid, boric acid, or alkali metal salts thereof ( Additives such as salts such as sodium and potassium) and alkaline earth metal salts (calcium, magnesium, etc.) may be added. Among these, it is preferable to add a boron compound, acetate, and phosphate containing acetic acid, boric acid, and a salt thereof.

  The content of acetic acid is sufficient to ensure its content effect, and from the viewpoint of obtaining a tube having a uniform thickness, with respect to 100 parts by mass of the side chain 1,2-diol unit-containing vinyl alcohol polymer (B). 0.001 to 1 part by mass, preferably 0.005 to 0.2 part by mass, and more preferably 0.01 to 0.1 part by mass More preferably.

  The boron compound content is 100 parts by mass of the side chain 1,2-diol unit-containing vinyl alcohol polymer (B) from the viewpoint of sufficiently securing the content and obtaining a tube having a uniform thickness. In terms of boron element (after ashing, analysis by ICP emission analysis) is preferably 0.001 part by mass or more and 1 part by mass or less, and 0.002 part by mass or more and 0.2 part by mass or less. More preferably, it is 0.005 parts by mass or more and 0.1 parts by mass or less.

  In addition, the content of acetate and phosphate (including hydrogen phosphate) is sufficient to ensure the content, and from the viewpoint of obtaining a tube having a uniform thickness, the side chain 1,2-diol unit It is 0.0005 parts by mass or more and 0.1 parts by mass or less in terms of metal element (analyzed by ICP emission analysis after ashing) with respect to 100 parts by mass of the vinyl alcohol polymer (B). Preferably, it is 0.001 part by mass or more and 0.05 part by mass or less, and more preferably 0.002 part by mass or more and 0.03 part by mass or less. In addition, when adding 2 or more types of salt to a side chain 1, 2- diol unit containing vinyl alcohol polymer (B), it is preferable that the total is the range of said content.

  The method for adding a boron compound, acetate, and phosphate to the side chain 1,2-diol unit-containing vinyl alcohol polymer (B) is not particularly limited, and i) a water content of 20% by mass to 80% by mass. A method in which a porous precipitate of the following side chain 1,2-diol unit-containing vinyl alcohol polymer (B) is brought into contact with an aqueous solution of the additive to contain the additive and then dried; ii) the side chain After adding an additive to a uniform solution (water / alcohol solution, etc.) of 1,2-diol unit-containing vinyl alcohol polymer (B), it is extruded into a coagulating liquid and then the resulting strand is cut. And iii) a method in which the side chain 1,2-diol unit-containing vinyl alcohol polymer (B) and the additive are mixed together and then melt-kneaded with an extruder or the like. Iv) During production of the side chain 1,2-diol unit-containing vinyl alcohol polymer (B), the alkali (sodium hydroxide, potassium hydroxide, etc.) used in the saponification step is replaced with organic acids such as acetic acid. For example, there may be mentioned a method of adjusting the amount of remaining organic acids such as acetic acid and by-product salts by washing with water. In order to obtain the effects of the present invention more remarkably, the method i) and ii), which are excellent in the dispersibility of the additive, and the method iv) are preferred when an organic acid and a salt thereof are contained.

  As described above, it can be prepared by adding the side chain 1,2-diol unit-containing vinyl alcohol polymer (B), other polymers added as necessary, additives, etc., and melt-kneading. From the viewpoint of sufficiently securing the properties of the side-chain 1,2-diol unit-containing vinyl alcohol polymer (B), the side in the side-chain 1,2-diol unit-containing vinyl alcohol polymer (B) -containing composition The content of the chain 1,2-diol unit-containing vinyl alcohol polymer (B) is preferably 70% by mass or more, more preferably 80% by mass or more, based on the total composition, 90% More preferably, it is at least mass%. Accordingly, the total content of the additives is preferably less than 30% by mass, more preferably less than 20% by mass, and even more preferably less than 10% by mass.

The fluoropolymer (C) used in the present invention is a fluoropolymer in which a functional group having reactivity to an amino group or a hydroxyl group is introduced into a molecular chain (hereinafter referred to as a fluoropolymer). (C) may be referred to.)
The fluoropolymer (C) is a polymer (homopolymer or copolymer) having a repeating unit derived from at least one fluorine-containing monomer. It is not particularly limited as long as it is a fluorine-based polymer that can be melt-processed.
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.) N in the compound represented by the formula is ensured for the effect of modifying the fluorine-based polymer (for example, suppressing the occurrence of cracks in the molded product or molded product), and from the viewpoint of obtaining sufficient polymerization reactivity, 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 combined body (C).

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  The fluorine-based polymer (C) used in the present invention can be obtained by (co) polymerizing monomers constituting the polymer by a conventional polymerization method. Among them, a method by radical polymerization is mainly used. That is, 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-type polymer (C), The polymerization method using the radical polymerization initiator generally used is used. Polymerization methods include bulk polymerization, solution polymerization using organic solvents such as fluorinated hydrocarbons, chlorinated hydrocarbons, fluorinated chlorohydrocarbons, alcohols, hydrocarbons, aqueous media, and appropriate organic solvents as required. Known methods such as suspension polymerization, emulsion polymerization using an aqueous medium and an emulsifier can be employed.
Moreover, superposition | polymerization can be implemented as a batch type or a continuous operation using a 1 tank thru | or multi tank type stirring type polymerization apparatus and a pipe | tube type polymerization apparatus.

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

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

  When the fluoropolymer (C) is coextruded with the aliphatic polyamide (A), the side chain 1,2-diol unit-containing vinyl alcohol polymer (B), etc., the kneading temperature without significant deterioration of these In order to ensure sufficient melt fluidity in the molding temperature range, the melt flow rate at a temperature 50 ° C. higher than the melting point of the fluoropolymer (C) and a load of 5 kg is 0.5 g / 10 min or more and 200 g. / 10 minutes or less is preferable, and 1 g / 10 minutes or more and 100 g / 10 minutes or less is more preferable.

Further, in the fluoropolymer (C), the melting point and glass transition point of the polymer can be adjusted by selecting the type and composition ratio of the fluorine-containing monomer and other monomers.
The melting point of the fluorine-based polymer (C) is appropriately selected depending on the purpose, application, and method of use. The aliphatic polyamide (A), the side chain 1,2-diol unit-containing vinyl alcohol polymer (B), etc. When it is coextruded with the resin, it is preferably close to the molding temperature of the resin. Therefore, it is preferable to optimize the melting point of the fluoropolymer (C) by appropriately adjusting the ratio of the fluorine-containing monomer, other monomers and the functional group-containing monomer described later. In particular, hot melt stability during coextrusion with the side chain 1,2-diol unit-containing vinyl alcohol polymer (B), continuous moldability, heat resistance of the fluoropolymer (C), chemical resistance, and From the viewpoint of sufficiently ensuring the chemical solution permeation prevention property, the melting point of the fluoropolymer is preferably 150 ° C. or higher and 230 ° C. or lower.
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-based polymer (C) used in the present invention has a functional group having reactivity with an amino group or a hydroxyl group in the molecular structure, and the functional group is a fluorine-based polymer (C). It may be contained at any of the molecular ends, side chains or main chains. Moreover, the functional group may be used alone or in combination of two or more in the fluoropolymer (C). The type and content of the functional group are appropriately determined depending on the type, shape, application, required interlayer adhesion, adhesion method, functional group introduction method, and the like of the counterpart material laminated on the fluoropolymer (C). .

  Functional groups having reactivity with amino groups or hydroxyl groups include carboxyl groups, acid anhydride groups or carboxylates, sulfo groups or sulfonates, epoxy groups, cyano groups, carbonate groups, and haloformyl groups. The at least 1 sort chosen from more is mentioned. 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-based polymer (C), (i) at the time of polymerization of the fluorine-based polymer (C), a copolymerizable monomer having a functional group is copolymerized. A method, (ii) a method of introducing a functional group to the molecular terminal of the fluoropolymer (C) at the time of polymerization by a polymerization initiator, a chain transfer agent, etc., and (iii) a reactive functional group can be grafted. Examples thereof include a method of grafting a compound having a functional group (graft compound) onto a fluoropolymer. These introduction methods can be used alone or in appropriate combination. In consideration of interlayer adhesion in the laminated tube, the fluoropolymer (C) produced from the above (i) and (ii) is preferable. Regarding (iii), JP-A-7-18035, JP-A-7-259592, JP-A-7-25594, JP-A-7-173230, JP-A-7-173446, JP-A-7- See the production method according to JP-A-173447 and JP-T-10-503236. In the following, (i) a method of copolymerizing a copolymerizable monomer having a functional group at the time of polymerization of the fluoropolymer, (ii) introduction of a functional group at the molecular end of the fluoropolymer by a polymerization initiator or the like How to do 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 fluoropolymer (C), A monomer comprising at least one functional group-containing monomer selected from the group consisting of a group, an acid anhydride group or carboxylate, a hydroxyl group, a sulfo or sulfonate, an epoxy group, and a cyano group. 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, epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, glycidyl ether, etc. And the like. 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.

The functional group-containing fluorine monomers, the general formula ^{CX 3 = CX 4 -. (} R 7) n -Y ( where, Y is -COOM (M is, represents a hydrogen atom or an alkali metal), carboxyl Represents a functional group selected from the group consisting of a 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 They are the same or different and each represents a hydrogen atom or a fluorine atom (provided that when ^{X 3} and ^{X 4} are identical to the hydrogen atom, a n = 1,. including a fluorine atom in ^{R 7), R 7} is An alkylene group having 1 to 40 carbon atoms, a fluorinated oxyalkylene group having 1 to 40 carbon atoms, a fluorinated alkylene group having 1 to 40 carbon atoms having an ether bond, or a carbon atom having an ether bond Number 1 or more And 40 or less fluorine-containing oxyalkylene groups, and n is 0 or 1.).
Examples of the group derived from a carboxyl group as Y in the above general formula include, for example, a general formula —C (═O) Q ¹ (wherein Q ¹ represents —OR ⁸ , —NH ₂ , F, Cl, Br, or I). R ⁸ 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 above general formula include a general formula —SO ₂ Q ² (wherein Q ² represents —OR ⁹ , —NH ₂ , F, Cl, Br, or I, and R ⁹ Represents an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 22 carbon atoms).
Y is preferably —COOH, —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 fluoropolymer (C) ensures sufficient interlayer adhesion, and ensures sufficient heat resistance without causing a decrease in interlayer adhesion depending on the use environment conditions. 0.05 mol% with respect to all polymerized units from the viewpoint of preventing the occurrence of poor adhesion, coloration and foaming during processing at high temperature, occurrence of peeling, coloring, foaming and elution due to decomposition during use at high temperatures. It is preferably 20 mol% or less, more preferably 0.05 mol% or more and 10 mol% or less, and further preferably 0.1 mol% or more and 5 mol% or less. When the content of the functional group-containing monomer is in the above range, the polymerization rate during production does not decrease, and the fluorine-based polymer (C) has excellent adhesion with the laminated counterpart material. . 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 fluoropolymer in which the functional group was introduce | transduced, and the fluoropolymer in which the functional group was not introduce | transduced.

  (Ii) In the method of introducing a functional group into the molecular terminal of a fluoropolymer with a polymerization initiator or the like, the functional group is introduced into one or both ends of the molecular chain of the fluoropolymer. 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 fluoropolymer (C) is generally a group having a —OC (═O) O— bond, specifically, —OC (═O) O—R ^10. The group [R ¹⁰ 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 polymer such as a haloformyl group obtained by converting these functional groups It can be introduced at the end. Of these polymerization initiators, it is more preferable to use peroxycarbonate because the polymerization temperature can be lowered and no side reaction is involved in the initiation reaction.

  Various methods can be used to introduce a haloformyl group at the molecular end of the polymer. For example, the carbonate group of the above-mentioned fluoropolymer 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 fluoropolymer (C) ensures sufficient interlayer adhesion, and does not cause deterioration of interlayer adhesion depending on the use environment conditions, and has sufficient heat resistance From the viewpoint of preventing the occurrence of peeling, coloring, foaming, elution, etc. due to decomposition, adhesion failure, coloring, foaming, use at high temperatures, decomposition at the time of processing at high temperatures, Preferably, it 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 polymer into which a functional group has been introduced and a fluorine polymer into which no functional group has been introduced.

As described above, the fluoropolymer (C) used in the present invention is a fluoropolymer into which a functional group having reactivity with an amino group or a hydroxyl group is introduced. As described above, the fluoropolymer (C) having a functional group introduced is itself a heat-resistant, water-resistant, low-friction, chemical-resistant, weather-resistant, antifouling, chemical solution specific to the fluoropolymer. It is possible to maintain excellent characteristics such as permeation prevention, which is advantageous in terms of productivity and cost.
Furthermore, by containing functional groups having reactivity with amino groups or hydroxyl groups in the molecular chain, the surface of various materials whose interlayer adhesion is insufficient or impossible in the laminated tube can be reduced. Excellent interlaminar adhesion with other substrates can be imparted directly without performing special treatment such as treatment or coating with an adhesive resin.

  The fluoropolymer (C) used in the present invention has various fillers such as inorganic powder, glass fiber, carbon fiber, metal oxide, or carbon, as long as the performance is not impaired depending on the purpose and application. Can be added. In addition to the filler, a pigment, an ultraviolet absorber, and other optional additives can be mixed. In addition to additives, resins such as other fluororesins and thermoplastic resins, synthetic rubber, etc. can also be added, improving mechanical properties, improving weather resistance, imparting design properties, preventing static electricity, improving moldability Etc. are possible.

  The laminated tube according to the present invention comprises an (a) layer comprising an aliphatic polyamide (A), a (b) layer comprising a side chain 1,2-diol unit-containing vinyl alcohol polymer (B), and an amino group or hydroxyl group. It is composed of at least three layers including the (c) layer composed of the fluoropolymer (C) in which a functional group having reactivity with the group is introduced into the molecular chain. By including the (b) layer comprising the side chain 1,2-diol unit-containing vinyl alcohol polymer (B), the chemical permeation prevention property of the laminated tube, particularly the hydrocarbon permeation prevention property is improved, and the low temperature resistance It becomes possible to obtain a laminated tube having both impact properties and environmental stress load resistance. Moreover, the alcohol permeation | blocking prevention property of a laminated tube becomes favorable by including the (c) layer which consists of a fluoropolymer (C).

In a preferred embodiment, the (a) layer made of the aliphatic polyamide (A) is disposed in the outermost layer of the laminated tube. By arranging the (a) layer made of the aliphatic polyamide (A) in the outermost layer, it is possible to obtain a laminated tube excellent in chemical resistance and flexibility.
As a more preferred embodiment, the (b) layer comprising the side chain 1,2-diol unit-containing vinyl alcohol polymer (B), the (a) layer comprising the aliphatic polyamide (A), and the fluoropolymer (C) It is arrange | positioned between (c) layers which consist of (C), As a more preferable embodiment, (b) layer which consists of a side chain 1, 2-diol unit containing vinyl alcohol polymer (B), and a fluorine-type polymer The (c) layer made of (C) is placed in direct contact. By using the fluorine-based polymer (C) defined in the present invention, it is not necessary to provide an adhesive layer, and the layer (b) comprising the side chain 1,2-diol unit-containing vinyl alcohol polymer (B) It is possible to obtain excellent interlayer adhesion.

  Further, in the laminated tube of the present invention, when a conductive layer made of a fluoropolymer composition containing a conductive filler is disposed in the innermost layer of the laminated tube, the chemical solution permeation prevention property, the deterioration fuel resistance, and Excellent elution resistance of monomers and oligomers, and when used as a fuel piping tube, prevents sparks generated by internal friction of fuel circulating in the piping or friction with the tube wall from igniting the fuel. It becomes possible. At that time, by arranging the layer made of a fluoropolymer having no conductivity outside the conductive layer, it is possible to achieve both low temperature impact resistance and conductivity, and economically. It is also advantageous. Furthermore, the fluorine polymer referred to here includes the fluorine polymer (C) having a functional group in the molecular chain as defined in the present invention, and also includes a fluorine polymer having no functional group described later. Point to.

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

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

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

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

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

Since the content of the conductive filler varies depending on the type of conductive filler used, it cannot be specified unconditionally, but from the viewpoint of the balance of conductivity, fluidity, mechanical strength, etc. In general, 3 parts by mass or more and 30 parts by mass or less is preferably selected.
In addition, the conductive filler preferably has a surface specific resistance value of 10 ⁸ Ω / square or less and 10 ⁶ Ω / square or less in order to obtain sufficient antistatic performance. However, the addition of the conductive filler tends to cause deterioration of strength and fluidity. Therefore, it is desirable that the content of the conductive filler is as small as possible if the target conductivity level is obtained.

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

  The total number of layers in the laminated tube of the present invention is as follows: (a) layer made of aliphatic polyamide (A), (b) layer made of side chain 1,2-diol unit-containing vinyl alcohol polymer (B) And at least three layers including the (c) layer composed of the fluoropolymer (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. You may have the layer which consists of a plastic resin 1 layer or 2 layers or more. Although the number of layers of the laminated tube of the present invention is 3 or more, it is preferably 8 or less, more preferably 3 or more and 7 or less, judging from the mechanism of the tube production apparatus.

  Other thermoplastic resins include polymetaxylylene adipamide (polyamide MXD6), polymetaxylylene veramide (polyamide MXD8), polymetaxylylene azelamide other than the aliphatic polyamide (A) defined in the present invention. (Polyamide MXD9), polymetaxylylene sebacamide (polyamide MXD10), polymetaxylylene dodecamide (polyamide MXD12), polymetaxylylene terephthalamide (polyamide MXDT), polymetaxylylene isophthalamide (polyamide MXDI), polymetaxyl Silylene hexahydroterephthalamide (polyamide MXDT (H)), polymetaxylylene naphthalamide (polyamide MXDN), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylene veramide ( Lyamide PXD8), polyparaxylylene azeamide (polyamide PXD9), polyparaxylylene sebacamide (polyamide PXD10), polyparaxylylene decanamide (polyamide PXD12), polyparaxylylene terephthalamide (polyamide PXDT), Polyparaxylylene isophthalamide (polyamide PXDI), polyparaxylylene hexahydroterephthalamide (polyamide PXDT (H)), polyparaxylylene naphthalamide (polyamide PXDN), polyparaphenylene terephthalamide (PPTA), Polyparaphenylene isophthalamide (PPIA), polymetaphenylene terephthalamide (PMTA), polymetaphenylene isophthalamide (PMIA), poly (2,6-naphthalenediethylene 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-Naphthalenedimethylene sebacamide) (Polyamide 2,6-BAN10), Poly (2,6-naphthalenedimethylene dodecamide) (Polyamide 2,6-BAN12), Poly (2,6-Naphthalenedylene methylene tele Phthalamide) (polyamide 2,6-BANT), poly (2,6-naphthalene dimethylene isophthalamide) (polyamide 2,6-BANI), poly (2,6-naphthalene dimethylene hexahydroterephthalamide) ( Polyamide 2,6-BANT (H)), poly (2,6-naphthalene dimethylene naphthalamide) (polyamide 2,6-B ANN), poly (1,3-cyclohexanedimethylene adipamide) (polyamide 1,3-BAC6), poly (1,3-cyclohexanedimethylene 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-cyclohexane dimethylene dodecamide) (Polyamide 1,3-BAC12), poly (1,3-cyclohexanedimethylene terephthalamide) (polyamide 1,3-BACT), poly (1,3-cyclohexanedimethylene isophthalamide) (polyamide 1,3- BACI), poly (1,3-cyclohexanedimethylene hexahydroterephthalamide) (poly Amide 1,3-BACT (H)), poly (1,3-cyclohexanedimethylenenaphthalamide) (polyamide 1,3-BACN), poly (1,4-cyclohexanedimethylene adipamide) (polyamide 1,4 -BAC6), poly (1,4-cyclohexanedimethylenesberamide) (polyamide 1,4-BAC8), poly (1,4-cyclohexanedimethyleneazeramide) (polyamide 1,4-BAC9), poly (1, 4-cyclohexanedimethylene sebacamide) (polyamide 1,4-BAC10), poly (1,4-cyclohexanedimethylene dodecamide) (polyamide 1,4-BAC12), poly (1,4-cyclohexanedimethylene terephthalate) Ramide) (polyamide 1,4-BACT), poly (1,4-cyclohexanedimethylene isophthalami) ) (Polyamide 1,4-BACI), poly (1,4-cyclohexanedimethylene hexahydroterephthalamide) (polyamide 1,4-BACT (H)), poly (1,4-cyclohexanedimethylene naphthalamide) ( Polyamide 1,4-BACN), poly (4,4′-methylenebiscyclohexylene adipamide) (polyamide PACM6), poly (4,4′-methylenebiscyclohexylene suberamide) (polyamide PACM8), poly (4 , 4′-methylenebiscyclohexylene azelamide) (polyamide PACM9), poly (4,4′-methylenebiscyclohexylene sebamide) (polyamide PACM10), poly (4,4′-methylenebiscyclohexylene dodecamide) (Polyamide PACM12), poly (4,4′-methylenebissi Chlorhexylenetetradecamide) (polyamide PACM14), poly (4,4′-methylenebiscyclohexylenehexadecamide) (polyamide PACM16), poly (4,4′-methylenebiscyclohexyleneoctadecamide) (polyamide PACM18) ), Poly (4,4′-methylenebiscyclohexylene terephthalamide) (polyamide PACMT), poly (4,4′-methylenebiscyclohexylene isophthalamide) (polyamide PACMI), poly (4,4′-methylene) Biscyclohexylenehexahydroterephthalamide) (polyamide PACMT (H)), poly (4,4′-methylenebiscyclohexylenenaphthalamide) (polyamide PACMN), poly (4,4′-methylenebis (2-methyl-cyclohexene) Silene) 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-me Ru-cyclohexylene) octadecamide) (polyamide MACM18), poly (4,4′-methylenebis (2-methyl-cyclohexylene) terephthalamide) (polyamide MACMT), poly (4,4′-methylenebis (2-methyl-cyclohexylene) ) Isophthalamide) (polyamide MACMI), poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexahydroterephthalamide) (polyamide MACMT (H)), poly (4,4′-methylenebis (2-methyl) -Cyclohexylene) naphthalamide) (polyamide MACMN), poly (4,4'-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 '-Propylene 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), poly Isophorone adipamide (polyamide IPD6), polyisophorone beramide (polyamide IPD8), polyisophorone azeamide (polyamide IPD9), polyisophorone sebamide (polyamide IPD10), polyisophorondecamide (polyamide IPD12), polyisophorone terephthalate Ramide (polyamide IPDT), polyisophorone isophthalamide (polyamide IPDI), polyisophorone hexahydroterephthalamide (polyamide IPDT (H)), polyisophorone naphthalamide ( Reamide IPDN), polytetramethylene terephthalamide (polyamide 4T), polytetramethylene isophthalamide (polyamide 4I), polytetramethylene hexahydroterephthalamide (polyamide 4T (H)), polytetramethylene naphthalamide (polyamide 4N) ), Polypentamethylene terephthalamide (polyamide 5T), polypentamethylene isophthalamide (polyamide 5I), polypentamethylene hexahydroterephthalamide (polyamide 5T (H)), polypentamethylene naphthalamide (polyamide 5N), Polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene hexahydroterephthalamide (polyamide 6T (H)), polyhexamethylene naphtha Lamid (polyamide 6N), poly (2-methylpentamethylene terephthalamide) (polyamide M5T), poly (2-methylpentamethylene isophthalamide) (polyamide M5I), poly (2-methylpentamethylene hexahydroterephthalamide) ) (Polyamide M5T (H)), Poly (2-methylpentamethylene naphthalamide) (Polyamide M5N), Polynonamethylene terephthalamide (Polyamide 9T), Polynonamethylene isophthalamide (Polyamide 9I), Polynonamethylene hexa Hydroterephthalamide (polyamide 9T (H)), polynonamethylene naphthalamide (polyamide 9N), poly (2-methyloctamethylene terephthalamide) (polyamide M8T), poly (2-methyloctamethylene isophthalamide) ( Polyamide M8I), Li (2-methyloctamethylenehexahydroterephthalamide) (polyamide M8T (H)), poly (2-methyloctamethylenenaphthalamide) (polyamide M8N), polytrimethylhexamethylene terephthalamide (polyamide TMHT), polytrimethyl Hexamethylene isophthalamide (polyamide TMHI), polytrimethylhexamethylene hexahydroterephthalamide (polyamide TMHT (H)), polytrimethylhexamethylene naphthalamide (polyamide TMHN), polydecamethylene terephthalamide (polyamide 10T), poly Decamethylene isophthalamide (polyamide 10I), polydecamethylene hexahydroterephthalamide (polyamide 10T (H)), polydecamethylene naphthalamide (polyamide 10N), polyunde Methylene terephthalamide (polyamide 11T), polyundecamethylene isophthalamide (polyamide 11I), polyundecamethylene hexahydroterephthalamide (polyamide 11T (H)), polyundecamethylene naphthalamide (polyamide 11N), poly Dodecamethylene terephthalamide (polyamide 12T), polydodecamethylene isophthalamide (polyamide 12I), polydodecamethylene hexahydroterephthalamide (polyamide 12T (H)), polydodecamethylene naphthalamide (polyamide 12N) and these polyamides Examples thereof include copolymers using several kinds of raw material monomers and / or raw material monomers of the aliphatic polyamide (A).

  Further, a fluorine-based polymer other than those specified in the present invention (here, other than those specified in the present invention, a fluorine-based polymer that does not contain a functional group having reactivity with an amino group or a hydroxyl group) As 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 / tetra Fluoroe Rene / hexafluoropropylene copolymer (EFEP), vinylidene fluoride / tetrafluoroethylene copolymer, vinylidene fluoride / hexafluoropropylene copolymer, vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer, tetrafluoro Ethylene / hexafluoropropylene / vinylidene fluoride copolymer (THV), vinylidene fluoride / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer, tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride / perfluoro (alkyl) Vinyl ether) copolymer, ethylene / chlorotrifluoroethylene copolymer (ECTFE), chlorotrifluoroethylene / tetrafluoroethylene copolymer, vinylidene fluoride / chlorotrifluoro Low ethylene copolymer, chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) copolymer, chlorotrifluoroethylene / hexafluoropropylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene / hexafluoropropylene copolymer, chlorotri Fluoroethylene / tetrafluoroethylene / vinylidene fluoride copolymer, chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer (CPT), chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) / hexafluoro Propylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene / hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer, chloro Trifluoroethylene / tetrafluoroethylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer, chlorotrifluoroethylene / tetrafluoroethylene / vinylidene fluoride / hexafluoropropylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene / Vinylidene fluoride / perfluoro (alkyl vinyl ether) / hexafluoropropylene copolymer. In contrast to the layer (c) made of the fluorine-containing polymer (C) containing a functional group having reactivity with the amino group or hydroxyl group, the layer made of the fluorine-containing polymer containing no functional group is on the inside. By being arranged, 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), ethylene / acrylic acid copolymer (EAA), Polyolefins such as ethylene / methacrylic acid copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), ethylene / ethyl acrylate copolymer (EEA) Resin, polystyrene (PS), syndiotactic plastic Styrene (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, cis-4 -Cyclohexene-1,2-dicarboxylic acid, Carboxyl groups such as endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid, and metal salts thereof (Na, Zn, K, Ca, Mg), maleic anhydride, itaconic anhydride, anhydrous Acid anhydride groups such as citraconic acid and endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid anhydride, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, citracone Polyolefin resins and polystyrene resins containing functional groups such as epoxy groups such as glycidyl acid, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), poly (ethylene terephthalate / ethylene iso Phthalate) copolymer (PET / PEI), polyto Limethylene terephthalate (PTT), polycyclohexanedimethylene terephthalate (PCT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyarylate (PAR), liquid crystal polyester (LCP), polylactic acid (PLA), poly Polyester resins such as glycolic acid (PGA), polyether resins such as polyacetal (POM) and polyphenylene ether (PPO), polysulfones such as polysulfone (PSU), polyethersulfone (PESU), and polyphenylsulfone (PPSU) Resin, polythioether resin such as polyphenylene sulfide (PPS), polythioethersulfone (PTES), polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEE) ), Polyetherketoneketone (PEKK), polyetheretherketoneketone (PEEKK), polyetherketoneetherketoneketone (PEKEKK) and other polyketone resins, polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer Polynitrile resins such as coalescence (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), acrylonitrile / butadiene copolymer (NBR), polymethyl methacrylate (PMMA), poly Polymethacrylate resins such as ethyl methacrylate (PEMA), polyvinyl ester resins such as polyvinyl acetate (PVAc), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinyl chloride Riden copolymers, polyvinyl chloride resins such as vinylidene chloride / methyl acrylate copolymer, cellulose resins such as cellulose acetate and cellulose butyrate, polycarbonate resins such as polycarbonate (PC), thermoplastic polyimide (TPI), Polyimide resins such as polyether imide, polyester imide, polyamide imide (PAI), and polyester amide imide, thermoplastic polyurethane resins, polyamide elastomers, polyurethane elastomers, polyester elastomers, and the like.

  In the laminated tube of the present invention, from the viewpoint of the melt stability of the side chain 1,2-diol unit-containing vinyl alcohol polymer (B), among the thermoplastic resins exemplified above, the melting point is 240 ° C. or lower. It is preferable to use a polyester-based resin, a polyamide-based resin, a polythioether-based resin, a polyolefin-based resin, and a fluorine-based polymer that does not contain a functional group having reactivity with an amino group or a hydroxyl group.

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

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

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

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

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

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

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

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

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

The characteristics of the aliphatic polyamide (A) 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 side chain 1,2-diol unit-containing vinyl alcohol polymer (B) were measured by the following method.
[Ethylene content and saponification degree]
It was calculated from the spectrum obtained by ¹ H-NMR (nuclear magnetic resonance) measurement (AVANCE500 manufactured by Bruker BioSpin) using deuterated dimethyl sulfoxide as a solvent.

[Introduction amount of 1,2-glycol bond]
¹ H-NMR (nuclear magnetic resonance) measurement using a vinyl alcohol polymer containing a side chain 1,2-diol unit before saponification using tetramethylsilane as an internal standard substance and deuterated dimethyl sulfoxide as a solvent The amount of 1,2-glycol bond introduced was calculated from the spectrum obtained by (AVANCE500 manufactured by Bruker BioSpin).

Moreover, the characteristic of the fluoropolymer (C) was measured by the following method.
[Composition of fluoropolymer]
It was measured by melt NMR analysis, fluorine content analysis, and infrared absorption spectrum.

[Number of terminal carbonate groups in fluoropolymer]
As for the number of terminal carbonate groups in the fluoropolymer, the peak to which the carbonyl group of the carbonate group (—OC (═O) O—) belongs appears at an absorption wavelength of 1809 cm ⁻¹ by infrared absorption spectrum analysis. Absorbance was measured, and the number of carbonate groups with respect to 10 ⁶ main chain carbon atoms in the fluoropolymer was calculated according to the following formula.
[Number of carbonate groups with respect to 10 ⁶ main chain carbon atoms in the fluoropolymer] = 500 AW / εdf
A: Absorbance at peak of carbonate group (—OC (═O) O—) ε: Molar absorbance coefficient [cm ⁻¹ · mol ⁻¹ ] of carbonate group (—OC (═O) O—). Ε = 170 from the model compound.
W: Composition average molecular weight calculated from the monomer composition d: Film density [g / cm ³ ]
f: Film thickness [mm]

Moreover, each physical property of the laminated tube was measured by the following method.
[Low temperature impact resistance]
The impact test was performed at -40 ° C by the method described in SAE J-2260 7.5.

[Deterioration fuel resistance]
A deterioration resistant fuel test was carried out by the method described in SAE J-2260 7.8. The tube after the test was subjected to an impact test at −40 ° C. by the method described in SAE J-2260 7.5. Judged to be excellent.

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

[Interlayer adhesion]
The tube cut to 200 mm was further cut in half in the vertical direction to create a test piece. Using a universal material testing machine (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.

[Environmental stress load resistance]
A tube cut to 500 mm was bent into a state of R50, and the tube was placed in an oven at 120 ° C. and a relative humidity of 80% and treated for 200 hours. The cross section in the tube after taking out was observed to confirm the presence or absence of cracks.

[Elution resistance of monomers and oligomers]
One end of the tube cut to 1 m was sealed, and alcohol-containing gasoline in which Fuel C (isooctane / toluene = 50/50 volume ratio) and ethanol were mixed in a 90/10 volume ratio was placed inside, and the remaining end was sealed. Thereafter, the test tube was placed in an oven at 60 ° C. and treated for 7 days. After completion of the treatment, the alcohol-containing gasoline in the tube taken out was filtered with a filter having a passing particle diameter of 8 μm, and the mass of the collected material was measured. The mass of the collected matter was divided by the number of treatment days and the inner surface area of the tube to calculate the monomer and oligomer elution amounts (g / m ² · day). After the treatment, the color tone of the alcohol-containing gasoline extracted from the tube was also visually observed.

[Materials Used in Examples and Comparative Examples]
Aliphatic polyamide (A)
Manufacture of polyamide 12 resin composition (A-1) Polyamide 12 (a-1) (manufactured by Ube Industries, UBESTA3030U, relative viscosity 2.27) and maleic anhydride modified ethylene / propylene copolymer as impact modifier The coalesced product (manufactured by JSR Co., Ltd., JSR T7761P) is mixed in advance and supplied to a twin-screw melt kneader (manufactured by Nippon Steel Co., Ltd., model: TEX44). Benzenesulfonic acid butyramide as a plasticizer is injected with a metering pump, melt-kneaded at a cylinder temperature of 200 ° C. to 270 ° C., and the molten resin is extruded into a strand shape, which is then introduced into a water bath, cooled, cut, and vacuum dried To obtain pellets of polyamide 12 resin composition comprising 85% by mass of polyamide 12, 10% by mass of impact modifier, and 5% by mass of plasticizer. (Hereinafter, this polyamide 12 resin composition of (A-1).).

Production of Conductive Polyamide 12 Resin Composition (A-2) In production of polyamide 12 resin composition (A-1), polyamide 12 (a-1) was changed 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-2).).

Manufacture of polyamide 12 (a-3) A 70 liter autoclave was charged with 20.0 kg of dodecane lactam, 0.5 kg of water and 49.3 g of 5-amino-1,3,3-trimethylcyclohexanemethylamine, and the inside of the polymerization tank was After substituting with nitrogen, it was heated to 180 ° C. and stirred at this temperature so that the inside of the reaction system became uniform. Next, the temperature in the polymerization tank was raised to 260 ° C., and polymerization was performed with stirring for 2 hours while adjusting the pressure in the tank to 3.5 MPa. Thereafter, the pressure was released to normal pressure over about 2 hours, and then the pressure was reduced to 53 kPa, and polymerization was performed for 4 hours under reduced pressure. Next, nitrogen was introduced into the autoclave, and after returning to normal pressure, the strand was extracted from the lower nozzle of the reaction vessel and cut to obtain pellets. This pellet was dried under reduced pressure to obtain a polyamide 12 having a relative viscosity of 2.26, a terminal amino group concentration of 45 μeq / g, and a terminal carboxyl group concentration of 20 μeq / g (hereinafter, this polyamide 12 is referred to as (a-3)).

Manufacture of polyamide 12 resin composition (A-3) In manufacture of polyamide 12 resin composition (A-1), polyamide 12 (a-1) was changed to (a-3), and triethylene glycol- was used as an antioxidant. Bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan, IRGANOX245), and tris (2,4-di-t-butylphenyl) as a phosphorus processing stabilizer ) Except for adding phosphite (manufactured by BASF Japan, IRGAFOS168) in advance, in the same manner as in the production of the polyamide 12 resin composition (A-1), 85 mass% of polyamide 12, 10 mass% of impact modifier, A total of 100 parts by mass of 5% by mass of plasticizer is composed of 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus processing stabilizer. To obtain pellets of the amide 12 resin composition (hereinafter, this polyamide 12 resin composition of (A-3).).

Manufacture of a polyamide 612 resin composition (A-4) In manufacture of the polyamide 12 resin composition (A-3), polyamide 12 (a-3) is made from polyamide 612 (made by DoPont Co., Ltd., ZYTEL 158, relative viscosity 2. 45) In the same manner as in the production of the polyamide 12 resin composition (A-3), the total amount of polyamide 612 80% by mass, impact modifier 10% by mass, and plasticizer 10% by mass is 100 parts by mass. In contrast, 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained to obtain a pellet of a polyamide 612 resin composition (hereinafter, this polyamide 612 resin composition is referred to as (A-4)). That said.)

Manufacture of polyamide 6 resin composition (A-5) In manufacture of polyamide 12 resin composition (A-3), polyamide 12 (a-3) is polyamide 6 (made by Ube Industries, UBE Nylon 1024B, relative viscosity) Except for changing to 3.50), in the same manner as in the production of the polyamide 12 resin composition (A-3), a total of 100 of polyamide 6 85 mass%, impact modifier 10 mass%, plasticizer 5 mass% is 100. Pellets of polyamide 6 resin composition comprising 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus processing stabilizer were obtained with respect to parts by mass (hereinafter, this polyamide 6 resin composition (A- 5).)

Polyamide 6/12 resin composition (A-6)
Polyamide 6/12 (poly (caproamide / dodecanamide) copolymer) resin composition (A-6): UBE Industries, UBE Nylon 7034U

Side chain 1,2-diol unit-containing vinyl alcohol polymer (B)
Production of side chain 1,2-diol unit-containing vinyl alcohol polymer composition (modified EVOH composition) (B-1) 500.0 kg of vinyl acetate and 100.0 kg of methanol in a 1 m ³ polymerization can having a cooling coil , 1 ppm of acetyl peroxide 500 ppm (vs. vinyl acetate), citric acid 20 ppm, and 3,4-diacetoxy-1-butene were charged, and the system was temporarily replaced with nitrogen gas, and then replaced with ethylene. The mixture was injected until the pressure became 3.5 MPa, stirred, and then heated to 67 ° C. to polymerize 3,4-diacetoxy-1-butene at 15.0 g / min while adding a total amount of 4.5 kg, Polymerization was conducted for 6 hours until the polymerization rate reached 50%. Thereafter, the polymerization reaction was stopped to obtain an ethylene / vinyl acetate copolymer having an ethylene content of 29 mol%.

A methanol solution of the ethylene / vinyl acetate copolymer was supplied at a rate of 10.0 kg / hour from the top of the plate tower (saponification tower), and at the same time, 0% of the remaining acetic acid groups in the copolymer were 0. A methanol solution containing 0.012 equivalent of sodium hydroxide was fed from the top of the tower. On the other hand, methanol was supplied from the bottom of the tower at 15.0 kg / hour. The temperature inside the tower was 100 ° C. to 110 ° C., and the tower pressure was 0.3 MPaG. From 30 minutes after the start of charging, a methanol solution of EVOH containing side chain 1,2-diol units (modified EVOH 30%, methanol 70%) was taken out. The saponification degree of the vinyl acetate component of the modified EVOH was 99.5 mol%.
Next, a methanol solution of the obtained modified EVOH was supplied from the top of the methanol / water solution adjusting tower at 10.0 kg / hour, methanol vapor at 120 ° C. was 4.0 kg / hour, and water vapor was 2.5 kg / hour. At the same time, methanol was distilled from the top of the column at 8.0 kg / hr. At the same time, 6 equivalents of methyl acetate with respect to the amount of sodium hydroxide used in the saponification was 95 ° C to 110 ° C. A water / alcohol solution of modified EVOH (resin concentration: 35%) was obtained from the center of the tower and from the bottom of the tower.
The obtained modified EVOH water / alcohol solution was extruded in a strand form from a nozzle having a pore diameter of 4 mm into a coagulation liquid tank maintained at 5 ° C. composed of 5% methanol and 95% water. Was cut with a cutter to obtain porous pellets of modified EVOH having a diameter of 3.8 mm and a length of 4 mm and a moisture content of 45%.
After washing with 100 parts of water with respect to 100 parts of the porous pellets, the mixture was put into a mixed solution containing 0.032% boric acid and 0.007% calcium dihydrogen phosphate, and at 30 ° C. for 5 hours. Stir. Further, the porous pellets were dried for 12 hours by passing nitrogen gas having a temperature of 70 ° C. and a moisture content of 0.6% in a batch-type ventilated box dryer, and the moisture content was adjusted to 30%. Using a batch tower type fluidized bed dryer, drying was performed with nitrogen gas having a temperature of 120 ° C. and a water content of 0.5% for 12 hours to obtain pellets of the desired modified EVOH composition (hereinafter, this modified EVOH composition). EVOH composition is referred to as (B-1)). Such pellets contained 0.015 parts by mass (in terms of boron element) and 0.005 parts by mass (in terms of phosphate group) of boric acid and calcium dihydrogen phosphate with respect to 100 parts by mass of the modified EVOH. The MFR of the modified EVOH composition (B-1) was 4.0 g / 10 min (210 ° C., 2160 g load), and the content of side chain 1,2-diol units was 2.5 mol%. It was.

Production of side chain 1,2-diol unit-containing vinyl alcohol polymer composition (modified EVOH composition) (B-2) Production of side chain 1,2-diol unit-containing vinyl alcohol polymer (B-1) 3,4-diacetoxy-1-butene is 70:20:10 of 3,4-diacetoxy-1-butene, 3-acetoxy-4-ol-1-butene and 1,4-diacetoxy-1-butene. A modified EVOH composition pellet was obtained in the same manner as in the production of the side chain 1,2-diol unit-containing vinyl alcohol polymer (B-1) except that the mixture was changed to a mixture (hereinafter referred to as this modified EVOH). The composition is referred to as (B-2).) Such pellets contained 0.015 parts by mass (in terms of boron element) and 0.005 parts by mass (in terms of phosphate group) of boric acid and calcium dihydrogen phosphate with respect to 100 parts by mass of the modified EVOH. The MFR of the modified EVOH composition (B-2) is 3.7 g / 10 min (210 ° C., 2160 g under load), the content of ethylene units is 29 mol%, and the side chain 1,2-diol units are The content was 2.5 mol% and the degree of saponification was 99.5 mol%.

Production of side chain 1,2-diol unit-containing vinyl alcohol polymer (modified PVA) (B-3) In a reaction can (1 m ³ ) equipped with a reflux condenser, a dropping funnel and a stirrer, 250.0 kg of vinyl acetate , 250.0 kg of methanol, 23.8 kg of 3,4-diacetoxy-1-butene were charged, 0.09 mol% of azobisisobutyronitrile (vs. vinyl acetate) was added, and the temperature was maintained under a nitrogen stream while stirring. The polymerization was started. Thereafter, 33.1 kg of a 20% methanol solution of 3,4-diacetoxy-1-butene was added dropwise over 10 hours according to the HANNA method, and when the polymerization rate of vinyl acetate reached 95%, m- Dinitrobenzene 10 ppm (vs. vinyl acetate) was added to complete the polymerization. Subsequently, unreacted vinyl acetate monomer was removed out of the system by a method of blowing methanol vapor to obtain a methanol solution of the copolymer.
The solution was then diluted with methanol to a concentration of 40% and charged into a kneader. While maintaining the solution temperature at 40 ° C., a 2% methanol solution of sodium hydroxide was added to vinyl acetate and 3,4 in the copolymer. -Saponification was carried out for 4 hours by adding 10.5 mmol to 1.0 mol of the total amount of diacetoxy-1-butene. As saponification progressed, when saponified substances were precipitated and became particulate, they were separated by filtration, washed well with methanol, and dried in a hot air dryer at 70 ° C. for 12 hours to obtain modified PVA.
This granulated material was melted at 200 ° C. for 2 minutes using a biaxial melt kneader to obtain modified PVA pellets (hereinafter, this modified PVA is referred to as (B-3)). The obtained modified PVA (B-3) had an MFR of 3.0 g / 10 min (210 ° C., under a load of 2160 g), a side chain 1,2-diol unit content of 6.0 mol%, and saponification. The degree was 98.9 mol%.

EVOH composition (B-4)
Ethylene content 32 mol%, saponification degree 99.5 mol%, boric acid content 0.015 parts by mass (in terms of boron element), calcium dihydrogen phosphate content 0.005 parts by mass (in terms of phosphate radical), MFR 3.2 g / 10 min (at 210 ° C. under 2160 g load), content of side chain 1,2-diol units 0 mol%.

Fluoropolymer (C)
Production of Fluoropolymer (C-1) A polymerization tank equipped with a stirrer having an internal volume of 94 liters was degassed, 48.53 kg of 1-hydrotridecafluorohexane, 1,3-dichloro-1,1,2,2 , 3-pentafluoropropane 12.13 kg, CH ₂ ═CH (CF ₂ ) ₄ F 0.24 kg, hexafluoropropylene (HFP) 25.40 kg, tetrafluoroethylene (TFE) 7.9 kg, ethylene (E ) 0.25 kg was injected, the temperature in the polymerization vessel was raised to 66 ° C., and 484 mL of a 5 mass% 1-hydrotridecafluorohexane solution of t-butylperoxypivalate was charged as a polymerization initiator to initiate polymerization. I let you. A monomer mixed gas having a composition of TFE / E = 54/46 (molar ratio) is continuously charged so that the pressure is constant during the polymerization so that the pressure becomes 1.0 mol% with respect to the monomer mixed gas of TFE / E. Itaconic anhydride was continuously charged so that CH ₂ ═CH (CF ₂ ) ₄ F was 0.25 mol%. 3.6 hours after the start of polymerization, when 5.06 kg of the monomer mixed gas was charged, the temperature in the polymerization tank was lowered to room temperature and purged to normal pressure. The obtained slurry-like fluoropolymer was suction filtered with a glass filter, and the separated fluoropolymer was dried at 120 ° C. for 15 hours to obtain 5.6 kg of a granulated product of the fluoropolymer. It was.
The composition of the fluoropolymer is as follows: polymerized units based on TFE / polymerized units based on E / polymerized units based on HFP / polymerized units based on CH ₂ ═CH (CF ₂ ) ₄ F / polymerized units based on itaconic anhydride. The molar ratio was 48.1 / 42.7 / 8.2 / 0.8 / 0.2. The melting point was 175 ° C.
This granulated material was melted at 230 ° C. and a residence time of 2 minutes using an extruder to obtain a fluorine polymer pellet (hereinafter, this fluorine polymer is referred to as (C-1)).

Production of Conductive Fluoropolymer (C-2) 100 parts by mass of fluoropolymer (C-1) and 13 parts by mass of carbon black (manufactured by Electrochemical Co., Ltd.) are mixed in advance, and a biaxial melt kneader. (Toshiba Machine Co., Ltd., model: TEM-48S), melt kneaded at a cylinder temperature of 220 ° C to 250 ° C, extrude the molten resin into a strand shape, introduce this 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 conductive fluoropolymer pellets (hereinafter, this conductive fluoropolymer was ( C-2).).

Production of Fluoropolymer (C-3) An autoclave with a stirrer having an internal volume of 94 liters was degassed, 19.7 kg of ion-exchanged water, 77.1 kg of perfluoropentyldifluoromethane, CH ₂ = CH (CF ₂ ) ₂ 0.427 kg of F, 3.36 kg of tetrafluoroethylene (TFE), and 0.127 kg of ethylene (E) were injected, and the temperature inside the autoclave was raised to 66 ° C. At this time, the pressure was 0.65 MPa. As a polymerization initiator, 72 g of diisopropyl peroxydicarbonate was charged to initiate polymerization. A monomer mixed gas having a molar ratio of TFE / E = 60/40 was continuously charged so that the pressure was kept constant during the polymerization. Further, CH ₂ ═CH (CF ₂ ) ₂ F in an amount corresponding to 6.0 mol% with respect to the total number of moles of TFE and E charged during the polymerization was continuously charged. 5.6 hours after the start of polymerization, when 11.5 kg of the monomer mixed gas was charged, the autoclave internal temperature was cooled to room temperature and the pressure in the polymerization layer was purged to normal pressure. The obtained slurry-like fluoropolymer was put into a 300 L granulation tank charged with 100.0 kg of water, and the temperature was raised to 105 ° C. while stirring to granulate while removing the solvent by distillation. The obtained granulated product was dried at 135 ° C. for 3 hours to obtain 12.1 kg of a fluoropolymer granulated product.
The composition of the fluoropolymer is 57.2 / 37.0 / 5.8 in terms of a molar ratio of polymerized units based on TFE / polymerized units based on E / polymerized units based on CH ₂ ═CH (CF ₂ ) ₂ F. The number of carbonate end groups derived from the polymerization initiator of the fluoropolymer was 359. The melting point was 205 ° C.
This granulated material was melted at 250 ° C. and a residence time of 2 minutes using an extruder to obtain a fluorine polymer pellet (hereinafter, this fluorine polymer is referred to as (C-3)).

Production of conductive fluoropolymer (C-4) In production of conductive fluoropolymer (C-2), the fluoropolymer (C-1) was changed to (C-3) and the cylinder temperature was 250. Except for changing from 260 ° C. to 260 ° C., conductive fluorine-based polymer pellets were obtained in the same manner as in the production of the conductive fluorine-based polymer (C-2) (hereinafter referred to as “conductive fluorine-based heavy polymer”). The coalescence is referred to as (C-4).)

Production of fluorinated polymer (C-5) In the production of fluorinated polymer (C-1), the same method as in the production example of fluorinated polymer (C-1) except that itaconic anhydride is not charged. Thus, a granulated product of 5.7 kg of a fluoropolymer was obtained.
The composition of the fluoropolymer is 48 in terms of a molar ratio of polymerized units based on TFE / polymerized units based on E / polymerized units based on HFP / polymerized units based on polymerized units based on CH ₂ ═CH (CF ₂ ) ₄ F. It was 0.2 / 42.8 / 8.2 / 0.8. The melting point was 176 ° C. This granulated product was melted at 230 ° C. and a residence time of 2 minutes using an extruder to obtain fluorine polymer pellets (hereinafter, this fluorine polymer is referred to as (C-5)).

Adhesive resin (D)
Maleic anhydride-modified polypropylene (D-1): manufactured by Mitsui Chemicals, Admer QF500
Ethylene / glycidyl methacrylate copolymer (D-2): manufactured by Nippon Polyolefin Co., Ltd., Lexper RA3150

Example 1
Using the polyamide 12 resin composition (A-1), polyamide 6/12 resin composition (A-6), modified EVOH composition (B-1), and fluoropolymer (C-1) shown above (A-1) is extrusion temperature 250 ° C., (A-6) is extrusion temperature 230 ° C., and (B-1) is extrusion temperature in a 4-layer tube molding machine manufactured by Plastic (Plastics Engineering Laboratory Co., Ltd.). 220 ° C. and (C-1) were melted separately at an extrusion temperature of 230 ° C., and the discharged molten resin was merged with an adapter to form a laminated tubular body. Subsequently, it is cooled by a sizing die for dimension control and taken up, and (a) layer (outermost layer) composed of (A-1), (a ') layer (outer layer) composed of (A-6), (B- (B) layer (intermediate layer) composed of 1) and (c) layer (innermost layer) composed of (C-1), the layer configuration is (a) / (a ′) / (b) / (c ) = 0.65 / 0.10 / 0.10 / 0.15 mm, and a laminated tube having an inner diameter of 6 mm and an outer diameter of 8 mm was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

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

Example 3
In Example 1, the modified EVOH composition (B-1) was changed to the modified PVA (B-3), and the extrusion temperature of (B-3) was changed to 210 ° C. Thus, a laminated tube having the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 4
In Example 1, except that the fluoropolymer (C-1) was changed to the conductive fluoropolymer (C-2) and the extrusion temperature of (C-2) was changed to 250 ° C. By the same method, the laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 5
In Example 1, except that the fluoropolymer (C-1) was changed to (C-3) and the extrusion temperature of (C-3) was changed to 250 ° C., the same method as in Example 1, A laminated tube having the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 6
In Example 1, except that the fluoropolymer (C-1) was changed to the conductive fluoropolymer (C-4) and the extrusion temperature of (C-4) was changed to 260 ° C. A laminated tube having the layer configuration shown in Table 1 was obtained in the same manner. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 7
In Example 1, except that the polyamide 6/12 resin composition (A-6) was changed to maleic anhydride-modified polypropylene (D-1) and the extrusion temperature of (D-1) was changed to 200 ° 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 8
In Example 1, the polyamide 12 resin composition (A-1) is changed to (A-3), the polyamide 6/12 resin composition (A-6) is changed to a fluoropolymer (C-1), and (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 extrusion temperature of 1) was changed to 230 ° C. The physical property measurement results of the laminated tube are shown in Table 1.

Example 9
Polyamide 12 resin composition (A-1), polyamide 6/12 resin composition (A-6), modified EVOH composition (B-1), fluoropolymer (C-1), (C- 5) is used in a Plabor (Plastics Engineering Laboratory Co., Ltd.) 5-layer tube forming machine, (A-1) is extrusion temperature 250 ° C., (A-6) is extrusion temperature 230 ° C., (B -1) is extruded at 220 ° C., (C-1) and (C-5) are melted separately at an extrusion temperature of 230 ° C., and the discharged molten resin is merged by an adapter to form a laminated tubular body. did. 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 layer (a ′) made of (A-6) (outer layer), -1) (b) layer (intermediate layer), (C-1) (c) layer (inner layer), (C ') (c') layer (innermost layer) The configuration is (a) / (a ′) / (b) / (c) / (c ′) = 0.60 / 0.10 / 0.10 / 0.10 / 0.10 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 10
In Example 9, except that the fluoropolymer (C-5) used for the innermost layer was changed to a conductive fluoropolymer (C-2) and the extrusion temperature of (C-2) was changed to 250 ° C. In the same manner as in Example 9, a laminated tube having the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 11
Using the polyamide 612 resin composition (A-4), the modified EVOH composition (B-1), and the fluoropolymer (C-1) shown above, Plabor (Plastics Engineering Laboratory Co., Ltd.) 3 In a layer tube forming machine, (A-4) was melted separately at an extrusion temperature of 260 ° C., (B-1) was melted at an extrusion temperature of 220 ° C., and (C-1) was melted separately at an extrusion temperature of 230 ° C. Resins were joined by an adapter and formed into a laminated tubular body. Subsequently, it is cooled by a sizing die for dimension control and taken up, and the (a) layer (outermost layer) composed of (A-4), the (b) layer (intermediate layer) composed of (B-1), (C- 1) (c) layer (innermost layer), the layer structure is (a) / (b) / (c) = 0.75 / 0.10 / 0.15 mm, an inner diameter of 6 mm, and an outer diameter of 8 mm. A laminated tube was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 1
In Example 1, except that the modified EVOH composition (B-1) and the fluorine-based polymer (C-1) were not used, the laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 1. Obtained. The physical property measurement results of the laminated tube are shown in Table 1.

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

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

Comparative Example 4
A tube having a layer configuration shown in Table 1 was obtained in the same manner as in Example 1, except that the modified EVOH composition (B-1) was changed to the EVOH composition (B-4) in Example 1. . Table 1 shows the physical property measurement results of the tube.

Comparative Example 5
In Example 1, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 1 except having changed the fluorine-type polymer (C-1) into (C-5). The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 6
Polyamide 12 resin composition (A-1), EVOH composition (B-4), fluorine-based polymer (C-5), maleic anhydride-modified polypropylene (D-1), ethylene / glycidyl methacrylate copolymer shown above Using the union (D-2), (A-1) at an extrusion temperature of 250 ° C. and (B-4) at an extrusion temperature of 220 in a Plabor (Plastic Engineering Laboratory Co., Ltd.) 5-layer tube molding machine. C., (C-5) is extruded at 230.degree. C., (D-1) and (D-2) are melted separately at an extrusion temperature of 200.degree. C., and the discharged molten resin is merged by an adapter. Molded into. Subsequently, it is cooled by a sizing die for dimension control and taken up, and the (a) layer (outermost layer) consisting of (A-1), the (d) layer (outer layer) consisting of (D-1), (B-4) ) (B) layer (intermediate layer), (D-2) (d ′) layer (inner layer), and (c) layer (c) layer (innermost layer). (A) / (d) / (b) / (d ′) / (c) = 0.55 / 0.10 / 0.10 / 0.10 / 0.15 mm, laminated tube having an inner diameter of 6 mm and an outer diameter of 8 mm Got. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 7
Using the polyamide 12 resin composition (A-1), polyamide 6 resin composition (A-5), polyamide 6/12 resin composition (A-6) and EVOH composition (B-4) shown above (A-1) and (A-5) are extruded at 250 ° C., (A-6) is extruded at 230 ° C., (B -4) was melted separately at an extrusion temperature of 220 ° C., and the discharged molten resin was merged with an adapter to form a laminated tubular body. Subsequently, it is cooled by a sizing die for dimension control and taken up, and (a) layer (outermost layer) composed of (A-1), (a ') layer (outer layer) composed of (A-6), (B- 4) (b) layer (intermediate layer) and (A ″) layer (innermost layer) (A-5), the layer structure is (a) / (a ′) / (b) / (A ″) = 0.45 / 0.10 / 0.10 / 0.35 mm, and a laminated tube having an inner diameter of 6 mm and an outer diameter of 8 mm was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 8
In Comparative Example 7, a laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Comparative Example 7, except that the EVOH composition (B-4) was changed to the modified EVOH composition (B-1). It was. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 9
Using the polyamide 12 resin composition (A-1), polyamide 6/12 resin composition (A-6), and modified EVOH composition (B-1) shown above, Plabor (Plastic Engineering Laboratory Co., Ltd.) (Manufactured) In a five-layer tube forming machine, (A-1) is melted separately at an extrusion temperature of 250 ° C, (A-6) at an extrusion temperature of 230 ° C, and (B-1) at an extrusion temperature of 220 ° C. The molten resin thus formed was merged with an adapter and formed into a laminated tubular body. Subsequently, it is cooled by a sizing die for dimension control and taken up, and (a) layer (outermost layer, innermost layer) composed of (A-1), (a ′) layer (outer layer, inner layer composed of (A-6)) ), (B-1) (b) layer (intermediate layer), the layer structure is (a) / (a ′) / (b) / (a ′) / (a) = 0.45 / A laminated tube having an inner diameter of 6 mm and an outer diameter of 8 mm at 0.10 / 0.10 / 0.10 / 0.25 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.

Comparative Example 10
In Comparative Example 9, except that the polyamide 12 resin composition (A-1) used for the innermost layer was changed to the conductive polyamide 12 resin composition (A-2), and the extrusion temperature of (A-2) was changed to 270 ° C. Obtained the laminated tube of the layer structure shown in Table 1 by the method similar to the comparative example 9. 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 having no side chain 1,2-diol unit-containing vinyl alcohol polymer and a layer made of a fluoropolymer as defined in the present invention The laminated tube of Comparative Example 2 which is inferior in chemical solution permeation prevention and does not have a layer made of the fluoropolymer specified in the present invention is inferior in low temperature impact resistance, deteriorated fuel resistance and environmental stress load resistance. . The laminated tube of Comparative Example 3 which does not have a layer made of the vinyl alcohol polymer containing the side chain 1,2-diol unit defined in the present invention was inferior in chemical solution permeation prevention. The laminated tube of Comparative Example 4 having a layer made of a vinyl alcohol polymer other than those specified in the present invention was inferior in environmental stress load resistance. The laminated tubes of Comparative Examples 5 and 6 having a layer made of a fluoropolymer other than those specified in the present invention were inferior in interlayer adhesion. The laminated tubes of Comparative Examples 7 and 8 that do not have a layer made of the fluoropolymer specified in the present invention and have a layer made of polyamide 6 as the innermost layer are inferior in deterioration fuel resistance, and are the innermost layer. As a result, the laminated tubes of Comparative Examples 9 and 10 having a layer made of polyamide 12 were inferior in the elution resistance of monomers and oligomers.
On the other hand, the laminated tubes of Examples 1 to 11 defined in the present invention have low temperature impact resistance, deteriorated fuel resistance, chemical solution permeation preventive property, interlayer adhesion, environmental stress load resistance, and monomer and oligomer dissolution resistance. It is clear that various properties such as properties are good.

Claims (10)

(A) layer composed of aliphatic polyamide (A), (b) composed of a polyvinyl alcohol polymer (B) not containing an ethylene unit containing a side chain 1,2-diol unit represented by the following formula (1) Comprising at least three layers, including a layer, and a layer (c) comprising a fluoropolymer (C) in which a functional group having reactivity to an amino group or a hydroxyl group is introduced into a molecular chain,
The (b) layer made of the vinyl alcohol polymer (B) is disposed between the (a) layer made of the aliphatic polyamide (A) and the (c) layer made of the fluorine polymer (C). A laminated tube characterized by
[In General Formula (1), R ¹ , R ² , and R ³ each independently represent a hydrogen atom or an organic group, X represents a single bond or a bonded chain, and R ⁴ , R ⁵ , and R ⁶ represent Each independently represents a hydrogen atom or an organic group. ] The aliphatic polyamide (A) is polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene decanamide ( Polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecane methylene decanamide (polyamide 1010), polydecamethylene dodecane (polyamide 1012), and polydodecamethylene dodecane (polyamide 1212). The laminated tube according to claim 1, wherein the laminated tube is at least one homopolymer or a copolymer using several kinds of raw material monomers forming them. The laminated tube according to claim 1 or 2, wherein the content of the side chain 1,2-diol unit in the polyvinyl alcohol polymer (B) is 0.1 mol% or more and 30 mol% or less. The laminated tube according to any one of claims 1 to 3 , wherein a melting point of the fluoropolymer (C) is 150 ° C or higher and 230 ° C or lower. The laminated tube according to any one of claims 1 to 4 , wherein the (a) layer made of the aliphatic polyamide (A) is disposed in an outermost layer. To any one of claims 1-5, wherein the polyvinyl alcohol polymer consisting (B) (b) layer and the fluorine-based polymer consisting of (C) (c) layer is directly adhered The laminated tube as described. The laminated tube according to any one of claims 1 to 6 , wherein a conductive layer made of a fluoropolymer composition containing a conductive filler is disposed in the innermost layer of the laminated tube. The laminated tube according to any one of claims 1 to 7 , wherein the laminated tube is manufactured by coextrusion molding. The laminated tube according to any one of claims 1 to 8 , wherein the laminated tube is used as a fuel tube. The laminated tube according to any one of claims 1 to 9 , wherein the laminated tube has at least a corrugated region.