JP6791236B2 - Laminated tube - Google Patents

Description

The present invention relates to laminated tubes.

In automobile piping tubes, in response to the problem of rusting caused by road antifreeze agents, prevention of global warming, and energy saving, the main material is metal, which is a lightweight resin with excellent rust prevention. The alternative to is progressing. Examples of resins usually used as piping tubes include polyamide-based resins, saturated polyester-based resins, polyolefin-based resins, and thermoplastic polyurethane-based resins, but single-layer tubes using these include heat resistance and resistance. The applicable range was limited due to insufficient chemical properties.

In addition, the tube for automobile piping is an oxygen-containing gasoline blended with alcohols having a low boiling point such as methanol and ethanol, or ethers such as ethyl-t-butyl ether (ETBE) 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 are being implemented, including prevention of leakage into the atmosphere due to diffusion of volatile hydrocarbons and the like through the partition walls of pipe tubes. In response to such strict regulations, a single-layer tube using a polyamide resin, particularly a polyamide 11 or a polyamide 12 having excellent strength, toughness, chemical resistance, flexibility, etc., which has been conventionally used, is described above. The permeation prevention property for chemicals is not sufficient, and improvement is required.

As a method for solving this problem, resins having good chemical permeation prevention properties, for example, ethylene / vinyl acetate copolymer saponified product (EVOH), polymethoxylylene adipamide (polyamide MXD6), polybutylene terephthalate (PBT), Polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyphenylene sulfide (PPS), polyvinylidene fluoride (PVDF), ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / tetrafluoroethylene / hexafluoropropylene Polymer (EFEP), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride co-weight Combined (TFE / 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) / Laminated tubes in which a tetrafluoroethylene copolymer (CTFE / PAVE / TFE, CPT) is arranged have been proposed (see, for example, Patent Document 1 and the like).

Among these, ethylene / vinyl acetate copolymer saponified product (EVOH) is extremely excellent in chemical permeation prevention property, particularly permeation prevention property for hydrocarbons. For example, a fuel composed of an outermost layer made of polyamide 12, an adhesive layer made of modified polyolefin 6, an outer layer made of polyamide 6, an intermediate layer made of ethylene / vinyl acetate copolymer saponified product (EVOH), and an innermost layer made of polyamide 6. Piping has been proposed (see Patent Document 2). Further, at least one selected from the group consisting of the outermost layer made of polyamide 12, polyamide 6/12 copolymer, polyamide 12/6 copolymer, polyamide 612, polyamide 610, and a mixture of polyamide 12 and polyamide 6 and a compatibilizer. Laminated composites composed of an adhesive layer made of seeds, an intermediate layer made of a saponified ethylene / vinyl acetate copolymer (EVOH), and an innermost layer made of polyamide 6 or polyamide 12 have 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 and polyamide 12 and a polyamine / polyamide copolymer, an intermediate layer made of ethylene / vinyl acetate copolymer saponified product (EVOH), polyamide 6 or polyamide. A laminated composite composed of the innermost layer composed of 12 has been proposed (see Patent Document 5). In this technique, a polyamide copolymer having a specific composition ratio or a mixture of polyamide 6 and polyamide 12 and a compatibilizer is preferable as an adhesive layer in which both polyamide 12 and ethylene / vinyl acetate copolymer saponified product are interposed. It has been proposed as having a high interlayer adhesion strength.

U.S. Pat. No. 5,554,425 Japanese Unexamined Patent Publication No. 3-177683 Special Table 2003-535717 Japanese Unexamined Patent Publication No. 2003-021276 JP-A-2002-210904

On the other hand, these laminated tubes are generally processed into tubes having a desired shape in a state where bending stress is applied due to layout restrictions, displacement absorption at the time of collision, and the like. At that time, in order to facilitate thermal processing, the tube is heated in the range from the glass transition temperature of the constituent material to the melting point or lower, but if it does not have sufficient interlayer adhesiveness after the heat treatment, when the joint is inserted, There arises a problem that the innermost layer is peeled off, causing blockage of the pipe, or the outermost layer is peeled off, and the original performance as a tube such as pressure resistance and yield strength is lost. Therefore, there is room for improvement in the interlayer adhesiveness (durability of interlayer adhesiveness) after the heat treatment.
Further, in the examples in the above document, a polyamide composition containing a plasticizer in the innermost layer of the laminated tube is used, but the plasticizer is a monomer, an oligomer, or the like due to contact with a fuel such as alcohol-containing gasoline. It is eluted with alcohol-containing gasoline together with low molecular weight components and additives, and precipitates at room temperature. Therefore, there is a concern that the fuel pipes such as automobile pipe tubes, filters, and nozzles may be blocked.

An object of the present invention is to solve the above-mentioned problems and to provide a laminated tube having excellent chemical permeation prevention property, interlayer adhesion and durability thereof, low temperature impact resistance, and resistance to elution.

As a result of diligent studies in order to solve the above problems, the present inventors have conducted a layer containing an aliphatic polyamide (polyamide 11, 12, etc.), a layer containing a polyamide composition, and an ethylene / vinyl acetate copolymer saponified product. Laminated tubes having a layer containing a layer and a layer containing an aliphatic polyamide composition containing no plasticizer have various properties such as chemical permeation prevention property, interlayer adhesiveness and durability thereof, low temperature impact resistance, and resistance to elution. Found to be excellent.

That is, the present invention is a laminated tube composed of at least four layers having a layer (a), a layer (b), a layer (c), and a layer (d).
The layer (a) contains an aliphatic polyamide (A) and contains
The layer (b) contains the polyamide 6/66/12 composition (B).
The layer (c) contains an ethylene / vinyl acetate copolymer saponified product (C).
The layer (d) contains the aliphatic polyamide composition (D).
The aliphatic polyamide (A) does not contain poly (caproamide / hexamethylene adipamide / dodecane amide) (polyamide 6/66/12).
The polyamide 6/66/12 composition (B) includes polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene decamide (polyamide 910), and polynonamethylene dodecamide. At least one polyamide and polyamide 6 / selected from the group consisting of (polyamide 912), polydecamethylene decamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), and polydodecamethylene dodecamide (polyamide 1212). Polyamide mixture (B1) consisting of 66/12 50% by mass or more and 98% by mass or less, plastic agent (B2) 1% by mass or more and 20% by mass or less, and an olefin having a bending elasticity of 500 MPa or less measured in accordance with ISO 178. Contains 1% by mass or more and 30% by mass or less of the polymer (B3),
The aliphatic polyamide composition (D) does not contain a plasticizer, and has an olefin weight of 70% by mass or more and 99% by mass or less of the aliphatic polyamide (A) and a flexural modulus of 500 MPa or less measured in accordance with ISO 178. Combined (B3) is a laminated tube characterized by containing 1% by mass or more and 30% by mass or less.

A preferred embodiment of the laminated tube of the present invention is shown below. A plurality of preferred embodiments can be combined.
[1] The aliphatic polyamide (A) is polycaproamide (polyamide 6), polyundecaneamide (polyamide 11), polydodecaneamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylenedeca. From the group consisting of mid (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecamethylene decamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), and polydodecamethylene dodecamide (polyamide 1212). A laminated tube characterized by being a copolymer using at least one selected homopolymer and / or several kinds of raw material monomers forming them.
[2] In the polyamide 6/66/12 in the polyamide 6/66/12 composition (B), the mass ratio of the total unit of the caproamide unit and the hexamethylene adipamide unit to the dodecaneamide unit is the caproamide unit or hexamethylene. A laminated tube characterized in that it is 81: 19% by mass or more and 95: 5% by mass or less with respect to a total of 100% by mass of adipamide units and dodecaneamide units.
[3] A laminated tube characterized in that the ethylene content of the ethylene / vinyl acetate copolymer saponified product (C) is 15 mol% or more and 60 mol% or less, and the degree of saponification is 90 mol% or more.
[4] The layer (a) is arranged in the outermost layer, the layer (d) is arranged in the innermost layer, and the layer (c) is arranged between the layers (a) and (d). Laminated tube.
[5] A laminated tube in which the layer (b) is arranged between the layers (a) and (c).
[6] A laminated tube characterized in that a conductive layer containing an aliphatic polyamide composition (D) further containing a conductive filler is arranged on the innermost layer of the laminated tube.
[7] A laminated tube produced by a coextrusion molding method.
[8] A laminated tube characterized by being used as a fuel tube.

The laminated tube of the present invention includes a layer containing an aliphatic polyamide, a layer containing a polyamide 6/66/12 composition, a layer containing an ethylene / vinyl acetate copolymer saponified product, and an aliphatic polyamide composition containing no plasticizer. By having a layer containing the above, both interlayer adhesion and chemical permeation prevention property are achieved, and various properties such as low temperature impact resistance and resistance to elution are excellent. In particular, it is suitable as a fuel tube because it suppresses hydrocarbons that permeate and evaporate from the tube partition wall and can comply with strict environmental regulations. Further, after contacting / immersing in fuel for a long time, after heat treatment, etc., there is little decrease in interlayer adhesive strength, and the durability of interlayer adhesiveness is excellent. Therefore, the laminated tube of the present invention can be used in any environment, has high reliability, and has extremely high utility value.

1. 1. (A) Layer The (a) layer of the laminated tube of the present invention contains an aliphatic polyamide (A).

[Aliphatic polyamide (A)]
The aliphatic polyamide (A) used in the present invention has an amide bond (-CONH-) in the main chain and is an aliphatic polyamide structural unit such as lactam, aminocarboxylic acid, or an aliphatic diamine and an aliphatic. It is obtained by polymerizing or copolymerizing a dicarboxylic acid as a raw material by a known method such as melt polymerization, solution polymerization or solid phase polymerization. However, the aliphatic polyamide (A) does not contain poly (caproamide / hexamethylene adipamide / dodecane amide) (polyamide 6/66/12).

Lactams include caprolactam, enanthractum, undecanelactam, dodecanelactam, α-pyrrolidone, α-piperidone, etc., and aminocarboxylic acids include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, and 11-aminoundecane. Acids, 12-aminododecanoic acid and the like can be mentioned. These can be used alone or in combination of two or more.

As the aliphatic diamine, 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptandiamine, 1, 8-octane diamine, 1,9-nonan diamine, 1,10-decane diamine, 1,11-undecane diamine, 1,12-dodecane diamine, 1,13-tridecane diamine, 1,14-tetradecane diamine, 1,15 -Pentadecanediamine, 1,16-hexadecandiamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, 1,19-nonadecandiamine, 1,20-eicosandiamine, 2-methyl-1,5- Pentandiamine, 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1, Examples thereof include 6-hexanediamine and 5-methyl-1,9-nonanediamine. These can be used alone or in combination of two or more.

Examples of aliphatic dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimeric acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, and tetradecanedioic acid. Examples thereof include pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, and eikosandioic acid. These can be used alone or in combination of two or more.

Examples of the aliphatic polyamide (A) include polycaproamide (polyamide 6), polyundecaneamide (polyamide 11), polydodecaneamide (polyamide 12), polyethylene adipamide (polyamide 26), and polytetramethylene succinamide (polyamide 26). 44), Polytetramethylene glutamide (polyamide 45), polytetramethylene adipamide (polyamide 46), polytetramethylene sveramide (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 56), Polypentamethylene Suberamide (polyamide 58), polypentamethylene azelamide (polyamide 59), polypentamethylene sebacamide (polyamide 510), polypentamethylene dodecamide (polyamide 512), polyhexamethylene succinamide (polyamide 64), poly Hexamethylene glutamide (polyamide 65), polyhexamethylene adipamide (polyamide 66), polyhexamethylene sveramide (polyamide 68), polyhexamethylene azelamide (polyamide 69), polyhexamethylene sebacamide (polyamide 610) , Polyhexamethylene dodecamide (polyamide 612), polyhexamethylenetetradecamide (polyamide 614), polyhexamethylene hexadecamide (polyamide 616), polyhexamethylene octadecamide (polyamide 618), polynonamethylene adipamide (Polyamide 96), polynonamethylene sveramide (polyamide 98), polynonamethylene azelamide (polyamide 99), polynonamethylene sebacamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), polydecamethylene hydrangea Pamide (polyamide 106), polydecamethylene sveramide (polyamide 108), polydecamethylene azelamide (polyamide 109), polydecamethylene sebacamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), polydodeca Methylene adipamide (polyamide 126), polydodecamethylene sveramide (polyamide 128), polydodecamethylene azelamide (polyamide 129) , Polydodecamethylene sebacamide (polyamide 1210), polydodecamethylene dodecamide (polyamide 1212) and other homopolymers, and copolymers using several kinds of raw material monomers forming these.
Among these, polycaproamide (polyamide 6) and polyundecaneamide (polyamide 11) are available from the viewpoints of economic efficiency and availability, while sufficiently ensuring various physical properties such as mechanical properties and heat resistance of the obtained laminated tube. ), Polydodecaneamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene decamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecamethylene decamide (polyamide 1010). , Polydecamethylene dodecamide (polyamide 1012), and at least one homopolymer selected from the group consisting of polydecamethylene dodecamide (polyamide 1212), and / or several raw materials monomers forming these. The copolymer that was used is preferable.

Examples of the apparatus for producing the aliphatic polyamide (A) include a batch type reaction kettle, a single-tank or multi-tank continuous reaction device, a tubular continuous reaction device, a uniaxial kneading extruder, a twin-screw kneading extruder, and the like. Known polyamide production equipment such as an extruder can be mentioned. As a polymerization method, a known method such as melt polymerization, solution polymerization or solid phase polymerization can be used, and polymerization can be carried out by repeating normal pressure, reduced pressure and pressurization operations. These polymerization methods can be used alone or in combination as appropriate.

In addition, the relative viscosity of the aliphatic polyamide (A) measured under the conditions of 96% sulfuric acid, polymer concentration 1%, and 25 ° C. in accordance with JIS K-6920 ensures the mechanical properties of the obtained laminated tube. From the viewpoint of ensuring the desirable moldability of the laminated tube by setting the viscosity at the time of melting in 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.

The aliphatic polyamide (A) has interlayer adhesion of the laminated tube 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). From the viewpoint of sufficiently ensuring the durability thereof, [A]> [B] +5 is preferable, [A]> [B] +10 is more preferable, and [A]> [B] +15. It is more preferable to have (hereinafter, it may be referred to as a terminally modified aliphatic polyamide). Further, from the viewpoint of the melt stability of the polyamide and the suppression of the generation of gel-like substances, [A]> 20 is preferable, and 30 <[A] <120 is more preferable.

The terminal amino group concentration [A] (μeq / g) can be measured by dissolving the polyamide in a mixed solution of phenol / methanol and titrating with 0.05 N hydrochloric acid. The terminal carboxyl group concentration [B] (μeq / g) can be measured by dissolving the polyamide in benzyl alcohol and titrating with a 0.05 N 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 during melt-kneading after polymerization, but when the interlayer adhesiveness of the laminated tube is taken into consideration, they are added at the stage during polymerization. Is preferable.
Examples of the amines include monoamines, diamines, triamines and polyamines. In addition to amines, carboxylic acids such as monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid may be added, if necessary, as long as they do not deviate from the above-mentioned terminal group concentration conditions. These amines and carboxylic acids may be added at the same time or separately. Further, as the amines and carboxylic acids exemplified below, one kind or two or more kinds can be used.

Specific examples of the monoamine to be added include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine and tridecylamine. , Tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, octadecyleneamine, eicosylamine, docosylamine and other aliphatic monoamines, cyclohexylamine, methylcyclohexylamine and other alicyclic monoamines, benzylamine, β- Aromatic monoamines such as phenylmethylamine, N, N-dimethylamine, N, N-diethylamine, N, N-dipropylamine, N, N-dibutylamine, N, N-dihexylamine, N, N-dioctyl Symmetrical secondary amines such as amines, N-methyl-N-ethylamine, N-methyl-N-butylamine, N-methyl-N-dodecylamine, N-methyl-N-octadecylamine, N-ethyl-N-hexadecyl Examples thereof include mixed secondary amines such as amines, N-ethyl-N-octadecylamines, N-propyl-N-hexadecylamines and N-propyl-N-benzylamines. These can be used alone or in combination of two or more.

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-nonandiamine, 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-octadecandiamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine , 2-Methyl-1,8-octanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9- Aliper diamines such as nonandiamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane , Bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (3-methyl-4-aminocyclohexyl) propane, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-Amino-1,3,3-trimethylcyclohexanemethylamine, bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, 2,5-bis (aminomethyl) norbornan, 2,6-bis (aminomethyl) norbornan , 3,8-bis (aminomethyl) tricyclodecane, 4,9-bis (aminomethyl) tricyclodecane and other alicyclic diamines, m-xylylene diamine, p-xylylene diamine and other aromatic diamines Can be mentioned. These can be used alone or in combination of two or more.

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 Examples thereof include 1,4,5,8-tetraminonaphthalene such as −triaminonaphthalene, 2,4,6-triaminopyridine, 1,2,7,8-tetraminonaphthalene and the like. These can be used alone or in combination of two or more.

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, polyalkylene polyamine, polyvinylamine, polyallylamine and the like. Can be mentioned. The amino group with active hydrogen is the reaction site for polyamines.

Polyalkyleneimine is produced by a method of ion-polymerizing an alkyleneimine such as ethyleneimine or propyleneimine, or a method of polymerizing an alkyloxazoline and then partially or completely hydrolyzing the polymer. Examples of the polyalkylene polyamine include diethylenetriamine, triethylenetetramine, pentaethylenehexamine, and a reaction product of ethylenediamine and a polyfunctional compound. Polyvinylamine can be obtained, for example, by polymerizing N-vinylformamide to obtain 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 salt of an allylamine monomer and then removing hydrochloric acid. These can be used alone or in combination of two or more. Among these, polyalkyleneimine is preferable.

The polyalkyleneimine is one or 2 of alkyleneimines having 2 to 8 carbon atoms such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, and 1,1-dimethylethyleneimine. Examples thereof include homopolymers and copolymers obtained by polymerizing seeds or more by a conventional method. Among these, polyethyleneimine is more preferable. Polyalkyleneimine is obtained by ring-opening polymerization of alkyleneimine as a raw material, and branched polyalkyleneimine containing primary amine, secondary amine, and tertiary amine, or alkyloxazoline as a raw material, which is polymerized. It may be either a linear polyalkyleneimine containing only the primary amine and the secondary amine obtained by the above, or a three-dimensionally crosslinked structure. Further, it may contain ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine, bisaminopropylethylenediamine and the like. Polyalkyleneimines are usually derived from the reactivity of active hydrogen atoms on the contained nitrogen atoms, and in addition to tertiary amino groups, primary amino groups and secondary amino groups (imino) having active hydrogen atoms. Group).

The number of nitrogen atoms in the polyalkyleneimine is not particularly limited, but is preferably 4 or more and 3,000, more preferably 8 or more and 1,500 or less, and further preferably 11 or more and 500 or less. .. The number average molecular weight of 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 the carboxylic acids to be added, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, capric acid, capric acid, pelargonic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, myristoleic acid, Alipid monocarboxylic acids such as palmitic acid, stearic acid, oleic acid, linoleic acid, araquinic acid, bechenic acid and erucic acid, alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid and methylcyclohexanecarboxylic acid, benzoic acid and toluic acid. , Ethylbenzoic acid, aromatic monocarboxylic acids such as phenylacetic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelliic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, hexadecanedioic acid , Hexadecenedioic acid, octadecanedioic acid, octadecenoic acid, eicosandioic acid, eicosendioic acid, docosanedioic acid, diglycolic acid, 2,2,4-trimethyladiponic acid, 2,4,4-trimethyladipic acid, etc. Alicyclic dicarboxylic acids such as aliphatic dicarboxylic acids, 1,3-cyclohexanedicarboxylic acids, 1,4-cyclohexanedicarboxylic acids, norbornandicarboxylic acids, terephthalic acids, isophthalic acids, phthalic acids, m-xylylene dicarboxylic acids, p- Aromatic dicarboxylic acids such as xylylene dicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,2,4-butanetricarboxylic acid, 1,3,5 Examples thereof include tricarboxylic acids such as -pentanetricarboxylic acid, 1,2,6-hexanetricarboxylic acid, 1,3,6-hexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid and trimesic acid. These can be used alone or in combination of two or more.

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

In the terminal-modified aliphatic polyamide, among the above-exemplified amines, it is preferable to add a diamine and / or a polyamine at the time of polymerization in order to satisfy the condition of the terminal group concentration, and from the viewpoint of suppressing gel generation, the aliphatic diamine , Alicyclic diamine, and polyalkyleneimine are more preferably at least one selected from the group.

Further, 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 thereof of the polyamide constituting the mixture.

In order to improve the flexibility of the aliphatic polyamide (A), it is preferable to add the plasticizer described in the polyamide 6/66/12 composition (B) described later.
The content of the plasticizer should 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. It is preferably 2 parts by mass or more and 20 parts by mass or less.

Further, in order to improve the low temperature impact resistance of the aliphatic polyamide (A), it is preferable to add an impact resistance improving material, and in particular, the ISO described in the polyamide 6/66/12 composition (B) described later. It is more preferable to add an olefin polymer having a flexural modulus of 500 MPa or less measured according to 178. If the flexural modulus exceeds this value, the impact improvement effect may be insufficient.
The content of the impact resistance improving material is 1 part by mass or more and 35 parts by mass or less with respect to 100 parts by mass of the aliphatic polyamide (A) from the viewpoint of sufficiently ensuring the mechanical strength and low temperature impact resistance of the laminated tube. It is preferably 3 parts by mass or more and 25 parts by mass or less.

The aliphatic polyamide (A) may be a mixture of the above-mentioned homopolymers, a mixture of the above-mentioned copolymers, a mixture of a homopolymer and a copolymer, or another polyamide-based 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-based resins include polymethoxylylene adipamide (polyamide MXD6), polymethoxylylence veramide (polyamide MXD8), polymethoxylylene azelamide (polyamide MXD9), and polymethoxylylene sebacamide (polyamide MXD10). , Polymethaxylylene dedecamide (Polyamide MXD12), Polymethoxylylene terephthalamide (Polyamide MXDT), Polymethoxylylene isophthalamide (Polyamide MXDI), Polymethoxylylene hexahydroterephthalamide (Polyamide MXDT (H)), Polyme Taxylylene naphthalamide (polyamide MXDN), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylene veramide (polyamide PXD8), polyparaxylylene azelamide (polyamide PXD9), polyparaxylylene sebacamide (Polyamide PXD10), Polyparaxylylene dedecamide (Polyamide PXD12), Polyparaxylylene terephthalamide (Polyamide PXDT), Polyparaxylylene isophthalamide (Polyamide PXDI), Polyparaxylylene hexahydroterephthalamide (Polyamide PXDI) Polyamide PXDT (H)), polyparaxylylene naphthalamide (polyamide PXDN), polyparaphenylene terephthalamide (PPTA), polyparaphenylene isophthalamide (PPIA), polymetaphenylene terephthalamide (PMTA), polymeta Phenylene isophthalamide (PMIA), poly (2,6-naphthalenedimethylene adipamide) (polyamide 2,6-BAN6), poly (2,6-naphthalenedimethylene sveramide) (polyamide 2,6-BAN8) , Poly (2,6-naphthalenedimethylene azelamide) (polyamide 2,6-BAN9), Poly (2,6-naphthalenedimethylene sebacamide) (polyamide 2,6-BAN10), Poly (2,6-BAN10) Naphthalenediene methylenedodecamide) (polyamide 2,6-BAN12), poly (2,6-naphthalenedimethylene terephthalamide) (polyamide 2,6-BANT), poly (2,6-naphthalenedimethylene isoftalamide) (Polyamide 2,6-BANI), Poly (2,6-naphthalenedimethylene hexahydroterephthalamide) (Polyamide 2,6-BANT (H)), Poly (2,6-naphthalenedimethylene naphthalamide) (Polyamide) 2,6-BANN), poly (1,3-cyclohexanedimethylenea) Zipamide) (Polyamide 1,3-BAC6), Poly (1,3-Cyclohexanedimethylene Suberamide (Polyamide 1,3-BAC8), Poly (1,3-Cyclohexanedimethylene Azelamide) (Polyamide 1,3-BAC9) ), Poly (1,3-cyclohexanedimethylene sebacamide) (polyamide 1,3-BAC10), poly (1,3-cyclohexanedimethylene dodecamide) (polyamide 1,3-BAC12), poly (1,3) -Cyclohexanedimethylene terephthalamide) (polyamide 1,3-BACT), poly (1,3-cyclohexanedimethyleneisophthalamide) (polyamide 1,3-BACI), poly (1,3-cyclohexanedimethylenehexahydro) Tereftalamide) (polyamide 1,3-BACT (H)), poly (1,3-cyclohexanedimethylenenaphthalamide) (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-BAC12) Cyclohexanedimethylene terephthalamide) (polyamide 1,4-BACT), poly (1,4-cyclohexanedimethyleneisophthalamide) (polyamide 1,4-BACI), poly (1,4-cyclohexanedimethylenehexahydroteramide) Phtalamide) (Polyamide 1,4-BACT (H)), Poly (1,4-Cyclohexanedimethylenenaphthalamide) (Polyamide 1,4-BACN), Poly (4,4'-Methylenebiscyclohexylene adipamide) ) (Polyamide PACM6), Poly (4,4'-methylenebiscyclohexylene veramide) (Polyamide PACM8), Poly (4,4'-Methylenebiscyclohexylene azelamide) (Polyamide PACM9), Poly (4,4' -Methylenebiscyclohexylene sebacamide) (polyamide PACM10), poly (4,4'-methylenebiscyclohexylenedodecamide) (polyamide PACM12), poly (4,4'-methylenebiscyclohexylenetetradecamide) (polyamide) PACM 14), Poly (4,4'-methylenebiscyclohexylene hexadecamide) (polyamide PACM16), Poly (4,4'-methylenebiscyclohexylene octadecamide) (polyamide PACM18), Poly (4,4'- Methylenebiscyclohexylene terephthalamide) (polyamide PACMT), poly (4,5'-methylenebiscyclohexylene isophthalamide) (polyamide PACMI), poly (4,5'-methylenebiscyclohexylene hexahydroterephthalamide) (Polyamide PACMT (H)), Poly (4,4'-methylenebiscyclohexylene naphthalamide) (Polyamide PACMN), Poly (4,4'-Methylenebis (2-methyl-cyclohexylene) adipamide) (Polyamide MACM6), Poly (4,4'-methylenebis (2-methyl-cyclohexylene) sveramide) (polyamide MACM8), poly (4,4'-methylenebis (2-methyl-cyclohexylene) azelamide) (polyamide MACM9), poly (4, 4'-Methylenebis (2-methyl-cyclohexylene) sebacamide) (polyamide MACM10), poly (4,5'-methylenebis (2-methyl-cyclohexylene) dodecamide) (polyamide MACM12), poly (4,5'-methylenebis) (2-Methyl-cyclohexylene) tetradecamide) (polyamide MACM14), poly (4,5'-methylenebis (2-methyl-cyclohexylene) hexadecamide) (polyamide MACM16), poly (4,4'-methylenebis (2-methyl) -Cyclohexylene) octadecamide) (polyamide MACM18), poly (4,5'-methylenebis (2-methyl-cyclohexylene) terephthalamide) (polyamide MACMT), poly (4,5'-methylenebis (2-methyl-cyclohexylene) Isophthalamide) (polyamide MACMI), poly (4,4'-methylenebis (2-methyl-cyclohexylene) hexahydroterephthalamide) (polyamide MACMT (H)), poly (4,5'-methylenebis (2-methyl-) Cyclohexylene) naphthalamide) (polyamide MACMN), poly (4,4'-propylene biscyclohexylene adipamide) (polyamide PACP6), poly (4,5'-propylene biscyclohexylene veramide) (polyamide PACP8), poly (4,4'-propylene biscyclohexylene azelamide) (Polyamide PACP9), Poly (4,4'-propylene biscyclohexylene sebacamide) (Polyamide PACP10), Poly (4,4'-propylene biscyclohexylenedodecamide) (Polyamide PACP12), Poly (4,4' -Propropylene biscyclohexylene tetradecamide) (polyamide PACP14), poly (4,4'-propylene biscyclohexylene hexadecamide) (polyamide PACP16), poly (4,4'-propylene biscyclohexylene octadecamide) ( Polyamide PACP18), poly (4,4'-propylene biscyclohexylene terephthalamide) (polyamide PACPT), poly (4,4'-propylene biscyclohexylene isophthalamide) (polyamide PACPI), poly (4,4' -Propropylene biscyclohexylene hexahydroterephthalamide) (polyamide PACPT (H)), poly (4,4'-propylene biscyclohexylene naphthalamide) (polyamide PACPN), polyisophorone adipamide (polyamide IPD6), polyisophorone Suberamide (polyamide IPD8), polyisophorone azelamide (polyamide IPD9), polyisophorone sebacamide (polyamide IPD10), polyisophorondodecamide (polyamide IPD12), polyisophorone terephthalamide (polyamide IPDT), polyisophorone isophthalamide (Polyamide IPDI), Polyisophorone hexahydroterephthalamide (Polyamide IPDT (H)), Polyisophorone naphthalamide (Polyamide IPDN), Polytetramethylene terephthalamide (Polyamide 4T), Polytetramethylene isophthalamide (Polyamide 4I) , Polytetramethylene hexahydroterephthalamide (polyamide 4T (H)), polytetramethylenenaphthalamide (polyamide 4N), polypentamethylene terephthalamide (polyamide 5T), polypentamethylene isophthalamide (polyamide 5I), poly Pentamethylene hexahydroterephthalamide (polyamide 5T (H)), polypentamethylene naphthalamide (polyamide 5N), polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene Hexahydroterephthalamide (polyamide 6T (H)), polyhexamethylenenaphthalamide (polyamide 6N), poly (2-methylpentame) Tyrene terephthalamide) (polyamide M5T), poly (2-methylpentamethyleneisophthalamide) (polyamide M5I), poly (2-methylpentamethylenehexahydroterephthalamide) (polyamide M5T (H)), poly (2) -Methylpentamethylenenaphthalamide (polyamide M5N), polynonamethylene terephthalamide (polyamide 9T), polynonamethylene isophthalamide (polyamide 9I), polynonamethylene hexahydroterephthalamide (polyamide 9T (H)), poly Nonamethylene naphthalamide (polyamide 9N), poly (2-methyloctamethylene terephthalamide) (polyamide M8T), poly (2-methyloctamethyleneisophthalamide) (polyamide M8I), poly (2-methyloctamethylenehexahydro) Telephthalamide) (Polyamide M8T (H)), Poly (2-Methyloctamethylenenaphthalamide) (Polyamide M8N), Polytrimethylhexamethylene terephthalamide (PolyamideTMHT), Polytrimethylhexamethyleneisophthalamide (PolyamideTMHI) , Polytrimethylhexamethylene hexahydroterephthalamide (polyamide TMHT (H)), polytrimethylhexamethylenenaphthalamide (polyamide TMHN), polydecamethylene terephthalamide (polyamide 10T), polydecamethylene isophthalamide (polyamide 10I) , Polydecamethylene hexahydroterephthalamide (polyamide 10T (H)), polydecamethylene naphthalamide (polyamide 10N), polyundecamethylene terephthalamide (polyamide 11T), polyundecamethylene isophthalamide (polyamide 11I) , Polyundecamethylene 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), and copolymers using several kinds of raw material monomers of these polyamides. These can be used alone or in combination of two or more.

Examples of 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 / Acrylic acid copolymer (EAA), ethylene / methacrylic acid copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), ethylene / ethyl acrylate Polyolefin-based resin such as copolymer (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 Polystyrene-based resins such as copolymers (SIS), styrene / ethylene / butylene / styrene copolymers (SEBS), styrene / ethylene / propylene / styrene copolymers (SEPS), carboxyl groups and salts thereof, acid anhydride groups , Polyethylene-based resin, polystyrene-based resin, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), poly (ethylene terephthalate / ethylene isophthalate) containing functional groups such as epoxy groups. Copolymer (PET / PEI), Polytrimethylene terephthalate (PTT), Polycyclohexanedimethylene terephthalate (PCT), Polyethylene naphthalate (PEN), Polybutylene naphthalate (PBN), Polyallylate (PAR), Liquid crystal polyester (LCP) ), Polylactic acid (PLA), polyglycolic acid (PGA) and other polyester resins, polyacetal (POM), polyphenylene ether (PPO) and other polyether resins, polysalphon (PSU), polyether sulfone (PESU), poly Polysalphon such as phenylsalphon (PPSU) Co-resin, polythioether-based resin such as polyphenylene sulfide (PPS), polythioetheralphon (PTES), polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK) , Polyetheretheretherketone (PEEEK), Polyetheretherketoneketone (PEEKK), Polyetherketoneketoneketone (PEKKKK), Polyetherketone etherketoneketone (PEKEKK) and other copolymer-based resins, polyacrylonitrile (PAN), poly Polynitrile resins such as methacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylnitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), acrylonitrile / butadiene copolymer (NBR), Polymethacrylate resins such as polymethyl methacrylate (PMMA) and ethyl polymethacrylate (PEMA), polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer , Polyvinyl resin such as vinylidene chloride / methyl acrylate copolymer, cellulose resin such as cellulose acetate and cellulose butyrate, polyvinylidene fluoride (PVDF), vinyl fluoride (PVF), polytetrafluoroethylene (PTFE), poly Chlorfluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / Hexafluoropropylene / vinylidene fluoride copolymer (THV), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer, tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer ( PFA), tetrafluoroethylene / hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer, chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer (CPT) and other fluororesins, polycarbonate (PFA) Polyetherketone resin such as PC), thermoplastic polyimide (TPI), polyether imitation Do, polyesterimide, polyamideimide (PAI), polyimide resins such as polyesteramideimide, thermoplastic polyurethane resins, polyamide elastomers, polyurethane elastomers, polyester elastomers and the like. These can be used alone or in combination of two or more.

Further, the aliphatic polyamide (A) may contain an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, an inorganic filler, an antistatic agent, a flame retardant, and a crystallization accelerator, if necessary. , Colorants and the like may be added.

2. 2. (B) Layer The (b) layer of the laminated tube of the present invention contains the polyamide 6/66/12 composition (B).

[Polyamide 6/66/12 composition (B)]
The polyamide 6/66/12 composition (B) used in the present invention includes polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene decamide (polyamide 910), and the like. At least one selected from the group consisting of polynonamethylene dodecamide (polyamide 912), polydecamethylene decamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), and polydodecamethylene dodecamide (polyamide 1212). Polyamide mixture (B1) consisting of polyamide and poly (caproamide / hexamethylene adipamide / dodecaneamide) (polyamide 6/66/12) 50% by mass or more and 98% by mass or less, plasticizer (B2) 1% by mass or more and 20% by mass % Or less, and 1% by mass or more and 30% by mass or less of the olefin polymer (B3) having a bending elasticity of 500 MPa or less measured in accordance with ISO 178 (hereinafter, polyamide 6/66/12 composition (B)). It may be called.).

Poly (caproamide / hexamethyleneadipamide / dodecaneamide) (polyamide 6/66/12) has an amide bond (-CONH-) in the main chain: (-CO- (CH ₂ ) _6- NH -) Caproamide unit represented by _n and the following formula: (-NH- (CH ₂ ) ₆ -NH-CO- (CH ₂ ) ₄ -CO-) Hexamethylene adipamide unit represented by _n and the following formula: ( -CO- (CH ₂ ) _11- NH-) A polyamide copolymer having a dodecaneamide unit represented by _n (hereinafter, may be referred to as polyamide 6/66/12). Polyamide 6/66/12 can be obtained by copolymerizing 6-aminocaproic acid or caprolactam, a salt of hexamethylenediamine and adipic acid, and 12-aminododecanoic acid or dodecanlactam.

In polyamide 6/66/12, the mass ratio of the total unit of caproamide unit and hexamethylene adipamide unit to the mass ratio of dodecaneamide unit is the caproamide unit, from the viewpoint of sufficiently ensuring the interlayer adhesiveness of the laminated tube and its durability. It is preferably 81: 19% by mass or more and 95: 5% by mass or less, and 83: 17% by mass or more and 92: 8% by mass or less, based on 100% by mass of the total of hexamethylene adipamide units and dodecaneamide units. Is more preferable.
In polyamide 6/66/12, the mass ratio of caproamide unit and hexamethylene adipamide unit ensures sufficient heat resistance of the laminated tube and during coextrusion with ethylene / vinyl acetate copolymer saponified product (C). From the viewpoint of molding stability, it is preferably 80:20% by mass or more and 95: 5% by mass or less, preferably 82:18% by mass or more, with respect to 100% by mass of the total of the caproamide unit and the hexamethylene adipamide unit. It is more preferably 93: 7% by mass or less.

The polyamide 6/66/12 composition (B) includes polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene decamide (polyamide 910), and polynonamethylene dodecamide (polyamide 910). Polyamide 912), polydecamethylene decamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), and polydodecamethylene dodecamide (polyamide 1212) at least one polyamide and polyamide 6/66 selected from the group. It contains a polyamide mixture (B1) composed of / 12 (hereinafter, may be referred to as a polyamide mixture (B1)).
Polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene decamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), polydecamethylene decamide (polyamide 1010) , Polydecamethylene dodecamide (polyamide 1012), and polydodecamethylene dodecamide (polyamide 1212) are long-chain aliphatic polyamides (hereinafter, may be referred to as long-chain aliphatic polyamides), and interlayer adhesion of laminated tubes. From the viewpoint of obtaining sufficient properties and durability thereof, polyhexamethylene sebacamide (polyamide 610) and polyhexamethylene dodecamide (polyamide 612) are preferable.

The mixing ratio of both polyamide 6/66/12 and long-chain aliphatic polyamide obtains a laminated tube having excellent mechanical properties, chemical resistance and flexibility, and sufficiently interlayer adhesion and durability thereof. From the viewpoint, the content of polyamide 6/66/12 is 50% by mass or more and 90% by mass or less with respect to 100% by mass of the polyamide mixture (B1) of polyamide 6/66/12 and long-chain aliphatic polyamide. Is more preferable, 55% by mass or more and 85% by mass or less, more preferably 60% by mass or more and 80% by mass or less, and the content of the long-chain aliphatic polyamide is 10% by mass or more and 50% by mass or less. It is preferably 15% by mass or more, more preferably 45% by mass or less, and further preferably 20% by mass or more and 40% by mass or less.

Examples of the polyamide 6/66/12 and long-chain aliphatic polyamide production apparatus include the known polyamide production apparatus described in the description of the aliphatic polyamide (A). Examples of the method for producing the polyamide 6, the polyamide 6/66/12, and the long-chain aliphatic polyamide include the known methods described in the description of the aliphatic polyamide (A).

Further, the relative viscosities of the polyamide 6/66/12 and the long-chain aliphatic polyamide measured under the conditions of 96% sulfuric acid, 1% polymer concentration and 25 ° C. according to JIS K-6920 can be obtained from the laminated tube. From the viewpoint of ensuring the mechanical properties of the above and ensuring the desirable moldability of the laminated tube by setting the viscosity at the time of melting in an appropriate range, it is preferably 1.5 or more and 5.0 or less, and 2.0 or more and 4 More preferably, it is 5.5 or less.

For polyamide 6/66/12 and long-chain aliphatic polyamide, 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), From the viewpoint of sufficiently ensuring the interlayer adhesiveness of the laminated tube and its durability, it is preferably [A]> [B] +5, more preferably [A]> [B] +10, and [A]. > [B] +15 is more preferable (hereinafter, it may be referred to as terminal-modified polyamide). Further, from the viewpoint of the melt stability of the polyamide and the suppression of the generation of gel-like substances, [A]> 20 is preferable, and 30 <[A] <120 is more preferable.

The terminal-modified polyamide is produced by polymerizing or copolymerizing the above-mentioned 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 during melt-kneading after polymerization, but when the interlayer adhesiveness of the laminated tube is taken into consideration, they are added at the stage during polymerization. Is preferable. Examples of the amines include monoamines, diamines, triamines and polyamines. In addition to amines, carboxylic acids such as monocarboxylic acid, dicarboxylic acid, and tricarboxylic acid may be added, if necessary, as long as they do not deviate from the above-mentioned terminal group concentration conditions. These amines and carboxylic acids may be added at the same time or separately. Further, as these amines and carboxylic acids, those described in the description of the aliphatic polyamide (A) can be mentioned, and one or more of these can be used.

Examples of the plasticizer (B2) in the polyamide 6/66/12 composition (B) include benzenesulfonic acid alkylamides, toluenesulfonic acid alkylamides, hydroxybenzoic acid alkylesters and the like.

Examples of the benzenesulfonic acid alkylamides include benzenesulfonic acid propylamide, benzenesulfonic acid butyramide, and benzenesulfonic acid 2-ethylhexylamide. Examples of the toluenesulfonic acid alkylamides include N-ethyl-o-toluenesulfonic acid butyramide, N-ethyl-p-toluenesulfonic acid butyramide, N-ethyl-o-toluenesulfonic acid 2-ethylhexylamide, and N-ethyl-p. -Toluenesulfonic acid 2-ethylhexylamide and the like can be mentioned. Examples of hydroxybenzoic acid alkyl esters include ethylhexyl o-hydroxybenzoate, ethylhexyl p-hydroxybenzoate, hexyldecyl o-hydroxybenzoate, hexyldecyl p-hydroxybenzoate, ethyldecyl o-hydroxybenzoate, and p-hydroxybenzoate. Ethyldecyl acid acid, octyloctyl o-hydroxybenzoate, octyloctyl 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, n-octyl p-hydroxybenzoate, o-hydroxybenzoic acid Examples thereof include decyl, decyl p-hydroxybenzoate, dodecyl o-hydroxybenzoate, dodecyl p-hydroxybenzoate and the like. These can be used alone or in combination of two or more.

Among these, benzenesulfonic acid alkylamides such as benzenesulfonic acid butylamide and benzenesulfonic acid 2-ethylhexylamide, N-ethyl-p-toluenesulfonic acid butylamide, N-ethyl-p-toluenesulfonic acid 2-ethylhexylamide and the like. Alkylamides of toluenesulfonic acid, ethylhexyl p-hydroxybenzoate, hexyldecyl p-hydroxybenzoate, ethyldecyl p-hydroxybenzoate and other hydroxybenzoic acid alkyl esters are preferable, and benzenesulfonic acid butylamide and p-hydroxybenzoic acid. Ethylhexyl and hexyldecyl p-hydroxybenzoate are more preferred.

An olefin polymer (B3) having a flexural modulus of 500 MPa or less measured in accordance with ISO 178 in the polyamide 6/66/12 composition (B) (hereinafter, may be referred to as an olefin polymer (B3)). Is added to improve the low temperature impact resistance of polyamide 6/66/12 and long-chain aliphatic polyamides. If the flexural modulus of the olefin polymer (B3) measured in accordance with ISO 178 exceeds this value, the impact improving effect may be insufficient.

Examples of the olefin polymer (B3) include (ethylene and / or propylene) / α-olefin polymer, (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester). ) -Based copolymers, ionomer polymers, aromatic vinyl compounds / conjugated diene compounds-based block copolymers, and one or more of these can be used.

The (ethylene and / or propylene) / α-olefin-based copolymer is a polymer obtained by copolymerizing ethylene and / or propylene with an α-olefin having 3 or more carbon atoms, and is an α-olefin having 3 or more carbon atoms. Examples of the olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonen, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4- Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, Examples thereof include 9-methyl-1-decene, 11-methyl-1-dodecene, and 12-ethyl-1-tetradecene. These can be used alone or in combination of two or more. In addition, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadien, 1,5-octadien, 1,6-octadien, 1,7-octadien, 2-methyl-1, 5-Hexadien, 6-Methyl-1,5-Heptadien, 7-Methyl-1,6-octadien, 4-Etylidene-8-Methyl-1,7-Norbornene, 4,8-Dimethyl-1,4,8- Decatrine (DMDT), dicyclopentadiene, cyclohexadiene, cyclooctadien, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl Of non-conjugated diene such as -5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornene Polyene may be copolymerized. These can be used alone or in combination of two or more.

The (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) -based copolymer contains ethylene and / or propylene and α, β-unsaturated carboxylic acid and / or It 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, and α, β-unsaturated carboxylic acid ester simple. Examples of the metric include methyl ester, ethyl ester, propyl ester, butyl ester, pentyl ester, hexyl ester, heptyl ester, octyl ester, nonyl ester, decyl ester and the like of these unsaturated carboxylic acids. These can be used alone or in combination of two or more.

In the ionomer polymer, at least a part of the carboxyl groups of the olefin and the α, β-unsaturated carboxylic acid copolymer is ionized by neutralizing 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 the olefin is not limited to those exemplified here, and an unsaturated carboxylic acid ester is used alone. The body may be copolymerized. The metal ions include alkali metals such as Li, Na, K, Mg, Ca, Sr, and Ba, alkaline earth metals, Al, Sn, Sb, Ti, Mn, Fe, Ni, Cu, Zn, and Cd. Can be mentioned. These can be used alone or in combination of two or more.

Further, the aromatic vinyl compound / conjugated diene compound-based block copolymer is a block copolymer composed of an aromatic vinyl compound-based polymer block and a conjugated diene compound-based polymer block, and is an aromatic vinyl compound-based polymer. A block copolymer having at least one block and at least one conjugated diene compound polymer block is used. Further, in the above-mentioned block copolymer, the unsaturated bond in the conjugated diene compound-based polymer block may be hydrogenated.

The aromatic vinyl compound-based polymer block is a polymer block mainly composed of units derived from the aromatic vinyl compound. In that case, the aromatic vinyl compounds include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,5-dimethylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene, and 4-propyl. Examples thereof include styrene, 4-cyclohexylstyrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4- (phenylbutyl) styrene and the like, and one or more of these can be used. Further, the aromatic vinyl compound-based polymer block may have a unit composed of a small amount of other unsaturated monomers, as the case may be.

Conjugated diene compound-based polymer blocks include 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 in the hydrogenated aromatic vinyl compound / conjugated diene compound block copolymer, the conjugated diene compound polymer. Part or all of the unsaturated bond portion in the block is saturated by hydrogenation.

The molecular structure of the aromatic vinyl compound / conjugated diene compound block copolymer and its hydrogenated product may be linear, branched, radial, or any combination thereof. Among these, as an aromatic vinyl compound / conjugated diene compound-based block copolymer and / or its hydrogen additive, one aromatic vinyl compound polymer block and one conjugated diene compound-based polymer block are linear. Three polymer blocks are linearly bonded in the order of diblock copolymer, aromatic vinyl compound-based polymer block-conjugated diene compound-based polymer block-aromatic vinyl compound-based polymer block. One or more of the triblock copolymers and hydrogenated products thereof are preferably used, and both unhydrated or hydrogenated styrene / butadiene block copolymers and unhydrated or hydrogenated styrene / isoprene blocks are used. Polymer, unhydrogenated or hydrogenated styrene / butadiene / styrene block copolymer, unhydrogenated or hydrogenated styrene / isoprene / styrene block copolymer, unhydrogenated or hydrogenated styrene / (ethylene / butadiene) / styrene Examples include block copolymers, unhydrogenated or hydrogenated styrene / (isoprene / butadiene) / styrene block copolymers.

Further, (ethylene and / or propylene) / α-olefin-based copolymer used as the olefin polymer (B3), (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid). As the acid ester) -based copolymer, the ionomer polymer, and the aromatic vinyl compound / conjugated diene compound-based block copolymer, a polymer modified with a carboxylic acid and / or a derivative thereof is preferably used. By modifying with such a component, the molecule contains a functional group having an affinity for polyamide 6/66/12 and long-chain aliphatic polyamide.

Functional groups having an affinity for polyamide 6/66/12 and long-chain aliphatic polyamides include carboxyl groups, acid anhydride groups, carboxylic acid ester groups, carboxylic acid metal salts, carboxylic acid imide groups, and carboxylic acid amides. Groups, epoxy groups and the like can be mentioned. Examples of compounds containing these functional groups are 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 itaconic acid, methyl acrylate, ethyl acrylate, butyl acrylate. , 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconic acid, maleic anhydride, itaconic anhydride, citracon anhydride Acid, Endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, acrylamide, methacrylic acid, acrylic acid Examples thereof include glycidyl, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconic acid, and glycidyl citraconic acid. These can be used alone or in combination of two or more.

The content of the polyamide mixture (B1) in the polyamide 6/66/12 composition (B) is 50% by mass or more and 98% by mass or less, preferably 60% by mass or more and 95% by mass or less, preferably 70% by mass. More preferably, it is% or more and 92% by mass or less. If the content of the polyamide mixture (B1) is less than the above value, the mechanical properties of the obtained laminated tube may be inferior, while if it exceeds the above value, the interlayer adhesiveness of the obtained laminated tube and its interlayer adhesion thereof. May be inferior in durability.
The content of the plasticizer (B2) is 1% by mass or more and 20% by mass or less, preferably 2% by mass or more and 15% by mass or less, and more preferably 3% by mass or more and 10% by mass or less. If the content of the plasticizer (B2) is less than the above value, the flexibility of the obtained laminated tube may be inferior, while if it exceeds the above value, the low temperature impact resistance of the obtained laminated tube is inferior. Sometimes.
The content of the olefin polymer (B3) is 1% by mass or more and 30% by mass or less, preferably 3% by mass or more and 25% by mass or less, and more preferably 5% by mass or more and 20% by mass or less. If the content of the olefin polymer (B3) is less than the above value, the low temperature impact resistance, interlayer adhesion and durability of the obtained laminated tube may be inferior, while if it exceeds the above value, The mechanical properties of the resulting laminated tube may be inferior.

The method for producing the polyamide 6/66/12 composition (B) is not particularly limited, and various additives can be blended as needed, and various conventionally known methods can be adopted. For example, the pellets are mixed in the above-mentioned mixing ratio using a tumbler or a mixer together with the polyamide 6/66/12 and the long-chain aliphatic polyamide and other components to which the olefin polymer (B3) is added as needed. While the polymer is uniformly dry-blended and supplied to the melt-kneader, the plasticizer (B2) can be injected from the middle of the cylinder of the melt-kneader by a metering pump and melt-kneaded. Melt kneading can be performed using a kneader such as a single-screw extruder, a twin-screw extruder, a kneader, or a Banbury mixer.

The polyamide 6/66/12 composition (B) may contain other polyamide-based resins or other thermoplastic resins. Examples of the other polyamide-based resin or other thermoplastic resin include the same resin as in the case of the aliphatic polyamide (A). The content of the polyamide 6/66/12 composition (B) in the mixture is preferably 60% by mass or more, and more preferably 70% by mass or more.

Further, the polyamide 6/66/12 composition (B) contains, if necessary, an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, an inorganic filler, an antistatic agent, and a flame retardant. , Crystallization accelerator, colorant, lubricant and the like may be added.

3. 3. (C) Layer The (c) layer of the laminated tube of the present invention contains an ethylene / vinyl acetate copolymer saponified product (C).

[Ethylene / vinyl acetate copolymer saponified product (C)]
The ethylene / vinyl acetate copolymer saponified product (C) used in the present invention is obtained by saponifying a copolymer composed of ethylene and vinyl acetate by a known method using an alkali catalyst or the like (hereinafter, It may be referred to as EVOH (C)).
Further, the ethylene content of EVOH (C) is preferably 15 mol% or more and 60 mol% or less from the viewpoint of sufficiently ensuring melt moldability, flexibility, impact resistance, and chemical permeation prevention property. It is more preferably 20 mol% or more and 55 mol% or less, and further preferably 25 mol% or more and 45 mol% or less. Here, when EVOH (C) is composed of a mixture of two or more types of EVOH having different ethylene contents, the value calculated from each ethylene content and mixed mass ratio is defined as the ethylene content.

Further, the degree of saponification of the vinyl ester component of EVOH (C) is preferably 90 mol% or more, more preferably 95 mol% or more, and 98% from the viewpoint of obtaining good chemical permeation prevention property. It is more preferably mol or more, and particularly preferably 99 mol% or more. Here, when EVOH (C) is composed of a mixture of two or more types of EVOH having different degrees of saponification, the value calculated from each degree of saponification and the mixed mass ratio is defined as the degree of saponification. The ethylene content and the degree of saponification of EVOH can be determined by a nuclear magnetic resonance (NMR) method.

The melt flow rate (MFR) of EVOH (C) (210 ° C., under a load of 2160 g) ensures desirable moldability by keeping the viscosity at the time of melting within an appropriate range, does not excessively reduce the melt tension, and draws down at the time of molding. From the viewpoint of preventing the occurrence of problems such as 0.1 g / 10 minutes or more and 100 g / 10 minutes or less, 0.3 g / 10 minutes or more and 50 g / 10 minutes or less is more preferable. It is more preferably 5 g / 10 minutes or more and 20 g / 10 minutes or less.

Further, other monomers can be copolymerized as long as the object of the present invention is not impaired. Other monomers include vinyl formate, vinyl propionate, vinyl valerate, vinyl butyrate, vinyl isobutyrate, vinyl pivalate, vinyl caproate, vinyl caprylate, vinyl caprate, vinyl laurate, vinyl myristate, etc. Vinyl esters such as vinyl palmitate, vinyl stearate, isopropenyl acetate, 1-butenyl acetate, vinyl pivalate, vinyl 2-ethylhexanoate, vinyl cyclohexanecarboxylate, vinyl benzoate, vinyl laurate, propylene, 1- Α-olefins such as butene, isobutene, 4-methyl-1-pentene, 1-hexene, 1-octene, 1-dodecene, allyl, methacrylic acid, clonic acid, phthalic acid, (anhydrous) maleic acid, (anhydrous) ) Unsaturated acids such as itaconic acid or salts thereof, mono or dialkyl esters having 1 to 18 carbon atoms, acrylamide, N-alkylacrylamide with 1 to 18 carbon atoms, N, N-dimethylacrylamide, 2 -Acrylamides such as acrylamide propanesulfonic acid or a salt thereof, acrylamidepropyldimethylamine or an ester thereof or a quaternary salt thereof, methallylamide, N-alkylmetharylamide having 1 to 18 carbon atoms, N, N-dimethylmethacryl Methylamides such as amide, 2-methacrylamide propanesulfonic acid or a salt thereof, methacrylicamidepropyldimethylamine or an ester thereof or a quaternary salt thereof, N-vinylpyrrolidone, N-vinylformamide, N-vinylacetamide and the like -Vinyl amides, vinyl cyanide such as acrylic nitrile and methacryl nitrile, vinyl ethers such as alkyl vinyl ethers having 1 to 18 carbon atoms, hydroxyalkyl vinyl ethers and alkoxyalkyl vinyl ethers, vinyl chloride, vinylidene chloride, vinyl fluoride, and foot. Vinyl halides such as vinylidene bromide and vinyl bromide, vinyl trimethoxysilane, vinyl methyl dimethoxysilane, vinyl dimethylmethoxylan, vinyl triethoxysilane, vinyl methyl diethoxysilane, vinyl dimethyl ethoxysilane γ-methacryloxypropyl methoxysilane Vinyl silanes such as allyl acetate, allyl chloride, allyl alcohol, dimethyl allyl alcohol, trimethyl- (3-acrylamide-3-dimethylpropyl) -ammonium chloride, acrylamide-2-methylpropanesulfonic acid, etc. Examples include vinyl ethylene carbonate. These can be used alone or in combination of two or more.

In addition, EVOH (C) can also contain various additives, if necessary. Examples of such additives include antioxidants, plasticizers, heat stabilizers, UV absorbers, antistatic agents, lubricants, colorants, fillers, or other thermoplastic resins. It can be contained within a range in which the action and effect of the present invention are not impaired. Specifically, 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-butyphenol), 2,2'-methylene-bis (4-methyl-6-t-butylphenol) , 2,2'-Methylenebis (4-ethyl-6-t-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-t-butylphenyl) butane, 1, 3,5-trimethyl-2,4,6-tris (3,5-di-t-butyl-4-hydrokibenzyl) benzene, tetrakis [methylene-3- (3', 5'-di-t-butyl-) 4'-Hydroxyphenyl) propionate], benzeneerythrityl-tetrakis [3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate], tris (2,4-di-t-butylphenyl), Antioxidants such as di (2,4-di-t-butylphenyl) -pentaesterol-diphosphite, ethylene-2-cyano-3,3'-diphenylacrylate, 2- (2'-hydroxy-5'- Methylphenyl) benzotriazole, 2- (2'-hydroxy-3'-t-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy- Ultraviolet absorbers such as 4-methoxybenzophenone and 2-hydroxy-4-octoxybenzophenone, plasticizers such as dimethyl phthalate, diethyl phthalate, dioctyl phthalate, phosphate ester, pentaerythlit monostearate, sorbitan monopalmi Antistatic agents such as tate, sulfated polyolefins, ethylene glycol, glycerin, hexanediol and other aliphatic polyhydric alcohols, saturated fatty acid amides such as stearic acid amide, unsaturated fatty acid amides such as oleic acid amide, and ethylene bisstea. Butyl fatty acid amide such as acid amide, calcium stearate, magnesium stearate, zinc stearate, fatty acid metal salt such as aluminum stearate, wax, liquid paraffin, low molecular weight polyolef Lubricants such as inn, organic acids such as acetic acid, propionic acid, stearic acid, inorganic acid compounds such as boric acid compounds and phosphoric acid compounds, stabilizers such as metal salts of hydrotalcites, reduced iron powders, sulfites. Oxygen absorbers such as potassium, ascorbic acid, hydroquinone, and gallic acid, colorants such as carbon black, phthalocyanine, quinacridone, indolin, azo pigments, and red iron oxide, glass fiber, asbestos, ballastonite, mica, sericite, talc, silica. , Kaolin, calcium silicate, fillers such as montmorillonite and the like.

Further, EVOH (C) preferably contains a boron compound. The inclusion of the boron compound is effective from the viewpoint of improving the melt stability and obtaining a laminated tube having a uniform wall thickness. Examples of the boron compound include boric acids, borate esters, borates, and boron hydrides. Examples of boric acid include orthoboric acid, metaboric acid, tetraboric acid and the like, examples of boric acid ester include triethyl borate, trimethyl borate and the like, and examples of borate are alkali metals of the above-mentioned various boric acids. Examples include salt, alkaline earth metal salt, boric acid and the like. These can be used alone or in combination of two or more. Among these, orthoboric acid is preferable.

The content of the boron compound in EVOH (C) is 0.002 mass by mass in terms of boron element with respect to 100 parts by mass of EVOH (C) from the viewpoint of sufficiently ensuring the content effect and obtaining a tube having a good appearance. It is preferably parts or more and 0.5 parts by mass or less, and more preferably 0.005 parts by mass or more and 0.2 parts by mass or less.

EVOH (C) may contain a phosphoric acid compound. By containing the phosphoric acid compound, it is possible to achieve both long-run property, color resistance, and interlayer adhesion during melt molding. The phosphoric acid compound is not particularly limited, and various acids such as phosphoric acid and phosphorous acid and salts thereof can be used. Examples of the phosphate include a first phosphate, a second phosphate and a third phosphate. These can be used alone or in combination of two or more. The cation species of the phosphate is not particularly limited, but an alkali metal salt is preferable, and among these, sodium dihydrogen phosphate, potassium dihydrogen phosphate, disodium hydrogen phosphate, and dipotassium hydrogen phosphate are selected. preferable.

The content of the phosphoric acid compound in EVOH (C) is 0.02 in terms of phosphoric acid root with respect to 100 parts by mass of EVOH (C) from the viewpoint of sufficiently ensuring the content effect and obtaining a tube having a good appearance. It is preferably 0.0005 parts by mass or more, more preferably 0.01 parts by mass or less, and further preferably 0.001 parts by mass or more and 0.007 parts by mass or less.

Further, it is also preferable to add alkali and / or alkaline earth metal salt to EVOH (C) from the viewpoint of melt stability and long-running property. The anion species of the salt of the alkali metal or alkaline earth metal is not limited, and examples thereof include carboxylates, hydroxides, carbonates, and hydrogen carbonates. The cationic species of the alkali metal salt is not limited, and examples thereof include lithium salt, sodium salt, potassium salt, etc., and the cationic species of the alkaline earth metal salt is not limited, and magnesium salt, calcium salt, barium salt, beryllium salt, strontium, etc. Examples include salt. Specifically, sodium acetate, lithium acetate, potassium acetate, calcium palmitate, magnesium palmitate, calcium myristate, magnesium myristate, calcium stearate, magnesium stearate, calcium oleate, magnesium oleate, calcium linoleate, linole Examples thereof include magnesium acid, calcium linolenate, magnesium linolenate, sodium phosphate, lithium phosphate and the like. These can be used alone or in combination of two or more.

The content of the alkali and / or alkaline earth metal salt in EVOH (C) is a metal with respect to 100 parts by mass of EVOH (C) from the viewpoint of sufficiently ensuring the content effect and obtaining a tube having a good appearance. In terms of element, it is preferably 0.0005 parts by mass or more and 0.2 parts by mass or less, more preferably 0.001 parts by mass or more and 0.1 parts by mass or less, and 0.002 parts by mass or more and 0.05 parts by mass. More preferably, it is less than or equal to a portion.

Further, EVOH (C) is one or 2 of antioxidants such as hydrotalcites, hindered phenols, etc., in order to improve melt stability and the like, as long as the object of the present invention is not impaired. It is preferable to add 0.01 parts by mass or more and 1 part by mass or less of seeds or more with respect to 100 parts by mass of EVOH (C).

4. Layer (d) The layer (d) of the laminated tube of the present invention contains the aliphatic polyamide composition (D).

[Alphatic Polyamide Composition (D)]
The aliphatic polyamide composition (D) used in the present invention does not contain a plasticizer and has a flexural modulus of 70% by mass or more and 99% by mass or less of the aliphatic polyamide (A) measured in accordance with ISO 178. It contains 1% by mass or more and 30% by mass or less of the olefin polymer (B3) of 500 MPa or less (hereinafter, may be referred to as an aliphatic polyamide composition (D)).
The aliphatic polyamide composition (D) does not contain the plasticizer described in the polyamide 6/66/12 composition (B). By not containing the plasticizer, the amount of low molecular weight components eluted into alcohol-containing gasoline can be reduced when it comes into contact with fuel such as alcohol-containing gasoline, and can be used in fuel pipes such as automobile piping tubes, filters, and nozzles. It is possible to prevent blockage.

Further, in order to improve the low temperature impact resistance of the aliphatic polyamide composition (D) and impart flexibility, in accordance with ISO 178 described in the polyamide 6/66/12 composition (B). It contains an olefin polymer (B3) having a measured flexural modulus of 500 MPa or less. If the flexural modulus of the olefin polymer (B3) measured in accordance with ISO 178 exceeds this value, the impact improving effect may be insufficient.
The content of the aliphatic polyamide (A) in the aliphatic polyamide composition (D) is 70% by mass or more and 99% by mass or less, preferably 75% by mass or more and 97% by mass or less, preferably 80% by mass or more. More preferably, it is 95% by mass or less. If the content of the aliphatic polyamide (A) is less than the above value, the mechanical properties of the obtained laminated tube may be inferior, while if it exceeds the above value, the low temperature impact resistance of the obtained laminated tube may be deteriorated. May be inferior.
The content of the olefin polymer (B3) is 1% by mass or more and 30% by mass or less, preferably 3% by mass or more and 25% by mass or less, and more preferably 5% by mass or more and 20% by mass or less. If the content of the olefin polymer (B3) is less than the above value, the low temperature impact resistance of the obtained laminated tube may be inferior, while if it exceeds the above value, the mechanical properties of the obtained laminated tube may be inferior. May be inferior.

The method for producing the aliphatic polyamide composition (D) is not particularly limited, and various conventionally known methods can be adopted by blending various additives as needed. For example, it can be produced in the same manner by the known production method described in the description of the polyamide 6/66/12 composition (B) except that a plasticizer is not used.

The aliphatic polyamide composition (D) may contain another polyamide-based resin or other thermoplastic resin. Examples of the other polyamide-based resin or other thermoplastic resin include the same resin as in the case of the aliphatic polyamide (A). The content of the aliphatic polyamide composition (D) in the mixture is preferably 60% by mass or more, and more preferably 70% by mass or more.

Further, in the aliphatic polyamide composition (D), if necessary, a conductive filler, an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, an inorganic filler, an antistatic agent, and a difficulty A flame retardant, a crystallization accelerator, a colorant, a lubricant and the like may be added.

[Laminated tube]
The laminated tube according to the present invention includes a layer (a) containing an aliphatic polyamide (A), a layer (b) containing a polyamide 6/66/12 composition (B), and a layer (c) containing EVOH (C). And at least 4 layers having a layer (d) containing the aliphatic polyamide composition (D).

In the laminated tube of the present invention, it is essential to include the layer (c) containing EVOH (C), and the chemical solution permeation prevention property of the laminated tube, particularly the hydrocarbon permeation prevention property is good.

In a preferred embodiment, the layer (a) containing the aliphatic polyamide (A) is arranged on the outermost layer of the laminated tube. By arranging the layer (a) containing the aliphatic polyamide (A) in the outermost layer, it is possible to obtain a laminated tube having excellent chemical resistance and flexibility. The layer (d) containing the aliphatic polyamide composition (D) is arranged in the innermost layer of the laminated tube. By arranging the layer (d) containing the aliphatic polyamide composition (D) in the innermost layer, it is possible to suppress the elution of low molecular weight components due to contact with alcohol-containing gasoline. Further, the layer (c) containing EVOH (C) is arranged between the layer (a) containing the aliphatic polyamide (A) and the layer (d) containing the aliphatic polyamide composition (D).

In a more preferred embodiment, the layer (b) containing the polyamide 6/66/12 composition (B) is a layer (a) containing an aliphatic polyamide (A) and a layer (c) containing EVOH (C). Placed in between. By arranging the layer (b) containing the polyamide 6/66/12 composition (B) between the layer (a) containing the aliphatic polyamide (A) and the layer (c) containing EVOH (C). It is possible to obtain a laminated tube having excellent interlayer adhesiveness and durability thereof.

Further, in the laminated tube of the present invention, when the conductive layer containing the aliphatic polyamide composition (D) further containing the conductive filler is arranged in the innermost layer of the laminated tube, the elution resistance of the low molecular weight component is improved. In addition to being excellent, when used as a fuel pipe tube, it is possible to prevent sparks generated by internal friction of the fuel circulating in the pipe or friction with the pipe wall from igniting the fuel. At that time, the layer containing the non-conductive aliphatic polyamide (A) and the aliphatic polyamide composition (D) is arranged on the outside with respect to the conductive layer, thereby providing low temperature impact resistance and conductivity. It is possible to achieve both, and it is also economically advantageous.

Conductivity means, for example, that when a flammable fluid such as gasoline comes into continuous contact with an insulator such as resin, static electricity may accumulate and ignite, but this static electricity does not accumulate. It means having electrical characteristics. 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 includes granular, flake-shaped, fibrous fillers and the like.

Examples of the granular filler include carbon black and graphite. Examples of the flake-like filler include aluminum flakes, nickel flakes, nickel-coated mica, and the like. Examples of the fibrous filler include metal fibers such as carbon fibers, carbon-coated ceramic fibers, carbon whiskers, carbon nanotubes, aluminum fibers, copper fibers, brass fibers, and stainless fibers. These can be used alone or in combination of two or more. Among these, carbon nanotubes and carbon black are preferable.

Carbon nanotubes are referred to as hollow carbon fibrils, which have an outer region consisting of essentially continuous multiple layers of regularly arranged carbon atoms and an inner hollow region, each layer. And hollow regions are essentially columnar fibrils that are substantially concentrically arranged around the cylindrical axis of the fibril. Further, it is preferable that the regularly arranged carbon atoms in the outer region are graphite-like and the diameter of the hollow region is 2 nm or more and 20 nm or less. The outer diameter of the carbon nanotubes 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 molded product. More preferably. The aspect ratio (referring to the length / outer diameter ratio) of the carbon nanotubes 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 adding a small amount.

The carbon black includes all carbon blacks generally used for imparting conductivity, and preferred carbon blacks include acetylene black obtained by incomplete combustion of acetylene gas and incomplete furnace type using crude oil as a raw material. Furnace black such as Ketjen black produced by combustion, oil black, naphthalin black, thermal black, lamp black, channel black, roll black, disc black and the like can be mentioned, but are not limited thereto. Among these, acetylene black and furnace black are more preferable.

Further, as carbon black, various carbon powders having different characteristics such as particle size, surface area, DBP oil absorption amount, and ash content are produced. The characteristics of the carbon black are not limited, but those having a good chain structure and a high aggregation density are preferable. A large amount of carbon black is not preferable from the viewpoint of impact resistance, and the average particle size is preferably 500 nm or less, more preferably 5 nm or more and 100 nm or less, from the viewpoint of obtaining excellent electrical conductivity with a smaller amount. It is more preferably 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. More preferably, the amount of DBP (dibutyl phthalate) oil absorbed is preferably 50 ml / 100 g or more, more preferably 100 ml / 100 g, and even more preferably 150 ml / 100 g or more. The ash content is preferably 0.5% by mass or less, and more preferably 0.3% by mass or less. The DBP oil absorption amount referred to here is a value measured by the method specified in ASTM D-2414. Further, the volatile content of carbon black is preferably less than 1.0% by mass.
These conductive fillers may be surface-treated with a surface treatment agent such as titanate-based, aluminum-based, or silane-based. It is also possible to use granulated products in order to improve the workability of melt-kneading.

Since the content of the conductive filler differs depending on the type of the conductive filler used, it cannot be unconditionally specified, but from the viewpoint of the balance with conductivity, fluidity, mechanical strength, etc., the aliphatic polyamide composition (D) Generally, it is preferably 3 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass.
Further, such conductive filler is more that from the viewpoint of obtaining a sufficient antistatic performance, it is preferable that the surface resistivity of the molten extrudate is less than 10 ⁸ Ω / square, is 10 ⁶ Ω / square or less preferable. However, the addition of the conductive filler tends to cause deterioration of strength and fluidity. Therefore, if the target conductive level can be obtained, it is desirable that the content of the conductive filler is as small as possible.

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 application, etc., but the thickness of each layer is determined. It is determined in consideration of characteristics such as chemical permeation prevention property, low temperature impact resistance, and flexibility of the laminated tube. In general, the thickness of the layer (a), the layer (b), the layer (c), and the layer (d) is preferably 3% or more and 90% or less with respect to the thickness of the entire laminated tube. Considering the balance between low-temperature impact resistance and chemical permeation prevention, the thickness of the layer (c) is more preferably 5% or more and 50% or less, and 7% or more, respectively, with respect to the thickness of the entire laminated tube. It is more preferably 30% or less.

The total number of layers in the laminated tube of the present invention includes the layer (a) containing the aliphatic polyamide (A), the layer (b) containing the polyamide 6/66/12 composition (B), and EVOH (C). The number of layers is not particularly limited as long as it has at least four layers having a layer (c) containing the layer (c) and a layer (d) containing the aliphatic polyamide composition (D). Further, the laminated tube of the present invention imparts further functions or obtains an economically advantageous laminated tube in addition to the four layers (a), (b), (c), and (d). Therefore, it may have one layer or two or more layers containing other thermoplastic resins. The number of layers of the laminated tube of the present invention is 4 or more, but judging from the mechanism of the tube manufacturing apparatus, it is preferably 8 or less, and more preferably 4 or more and 6 or less.

Examples of other thermoplastic resins include polymethoxylylene adipamide (polyamide MXD6), polymethoxylylence veramide (polyamide MXD8), and polymethoxylylene azeramide other than the aliphatic polyamide (A) specified in the present invention. (Polyamide MXD9), Polymethaxylylene sebacamide (Polyamide MXD10), Polymethoxylylend Decamide (Polyamide MXD12), Polymethoxylylene terephthalamide (Polyamide MXDT), Polymethoxylylene isophthalamide (Polyamide MXDI), Polymetaki Sirilenhexahydroterephthalamide (polyamide MXDT (H)), polymetaxylylene naphthalamide (polyamide MXDN), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylene veramide (polyamide PXD8), polyparaxili Lene azelamide (polyamide PXD9), polyparaxylylene sebacamide (polyamide PXD10), polyparaxylylene dedecamide (polyamide PXD12), polyparaxylylene terephthalamide (polyamide PXDT), polyparaxylylene isophthalamide (Polyamide PXDI), polyparaxylylene hexahydroterephthalamide (polyamide PXDT (H)), polyparaxylylene naphthalamide (polyamide PXDN), polyparaphenylene terephthalamide (PPTA), polyparaphenylene isophthalamide (polyamide PXDN) PPIA), polymetaphenylene terephthalamide (PMTA), polymetaphenylene isophthalamide (PMIA), poly (2,6-naphthalenedimethylene adipamide) (polyamide 2,6-BAN6), poly (2,6) -Naphthalenedimethylene sveramide) (polyamide 2,6-BAN8), poly (2,6-naphthalenedimethylene 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-naphthalenedimethylene terephthalamide) (Polyamide 2,6-BANT) ), Poly (2,6-naphthalenedimethylene isophthalamide) (Polyamide 2,6-BANI), Poly (2,6-naphthalenedimethylene hexahydroterephthalamide) (Polyamide 2,6-BANT (H)) , Poly (2,6-naphthalenedimethylene naphthalamide) (Polyamide 2,6-B) ANN), poly (1,3-cyclohexanedimethylene adipamide) (polyamide 1,3-BAC6), poly (1,3-cyclohexanedimethylenes veramide (polyamide 1,3-BAC8), poly (1,3) -Cyclohexanedimethylene azelamide) (polyamide 1,3-BAC9), poly (1,3-cyclohexanedimethylene sebacamide) (polyamide 1,3-BAC10), poly (1,3-cyclohexanedimethylene dodecamide) (Polyamide 1,3-BAC12), Poly (1,3-Cyclohexanedimethylene terephthalamide) (Polyamide 1,3-BACT), Poly (1,3-Cyclohexanedimethyleneisophthalamide) (Polyamide 1,3- BACI), poly (1,3-cyclohexanedimethylenehexahydroterephthalamide) (polyamide 1,3-BACT (H)), poly (1,3-cyclohexanedimethylenenaphthalamide) (polyamide 1,3-BACN) , Poly (1,4-cyclohexanedimethylene adipamide) (polyamide 1,4-BAC6), poly (1,4-cyclohexanedimethylenes veramide) (polyamide 1,4-BAC8), poly (1,4-BAC8) Cyclohexanedimethylene azelamide) (polyamide 1,4-BAC9), poly (1,4-cyclohexanedimethylene sebacamide) (polyamide 1,4-BAD10), poly (1,4-cyclohexanedimethylene dodecamide) ( Polyamide 1,4-BAD12), Poly (1,4-Cyclohexanedimethylene terephthalamide) (Polyamide 1,4-BACT), Poly (1,4-Cyclohexanedimethyleneisophthalamide) (Polyamide 1,4-BACI) ), Poly (1,4-cyclohexanedimethylenehexahydroterephthalamide) (polyamide 1,4-BACT (H)), poly (1,4-cyclohexanedimethylenenaphthalamide) (polyamide 1,4-BACN), Poly (4,4'-methylenebiscyclohexylene adipamide) (polyamide PACM6), poly (4,4'-methylenebiscyclohexylene veramide) (polyamide PACM8), poly (4,4'-methylenebiscyclohexylene Azelamide) (Polyamide PACM9), Poly (4,4'-Methylenebiscyclohexylene sebacamide) (Polyamide PACM10), Poly (4,4'-Methylenebiscyclohexylenedodecamide) (Polyamide PACM12), Poly (4) , 4'-Methylenebissi Clohexylene tetradecamide) (polyamide PACM14), poly (4,5'-methylenebiscyclohexylene hexadecamide) (polyamide PACM16), poly (4,5'-methylenebiscyclohexylene octadecamide) (polyamide PACM18) ), Poly (4,4'-methylenebiscyclohexylene terephthalamide) (polyamide PACMT), Poly (4,4'-methylenebiscyclohexylene isophthalamide) (polyamide PACMI), Poly (4,4'-methylene Biscyclohexylene hexahydroterephthalamide) (polyamide PACMT (H)), poly (4,4'-methylenebiscyclohexylene naphthalamide) (polyamide PACMN), poly (4,4'-methylenebis (2-methyl-cyclohexyl) Silen) adipamide) (polyamide MACM6), poly (4,5'-methylenebis (2-methyl-cyclohexylene) sveramide) (polyamide MACM8), poly (4,5'-methylenebis (2-methyl-cyclohexylene) azelamide) (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) (polyamide MACM18), poly (4,5'-methylenebis (2-methyl-cyclohexylene) terephthalamide) (polyamide MACMT), poly (4,4'- Methylenebis (2-methyl-cyclohexylene) isophthalamide) (polyamide MACMI), poly (4,5'-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 (4,5'-propylene biscyclohexylene sebacamide) (polyamide PACP10), poly (4,4'-propylene biscyclohexylenedodecamide) (Polyamide PACP12), Poly (4,4'-propylene biscyclohexylene tetradecamide) (Polyamide PACP14), Poly (4,4'-propylene biscyclohexylene hexadecamide) (Polyamide PACP16), Poly (4,4) '-Propylene biscyclohexylene octadecamide) (polyamide PACP18), poly (4,5'-propylene biscyclohexylene terephthalamide) (polyamide PACPT), poly (4,4'-propylene biscyclohexylene isophthalamide) (Polyamide PACPI), Poly (4,4'-propylene biscyclohexylene hexahydroterephthalamide) (Polyamide PACPT (H)), Poly (4,4'-propylene biscyclohexylene naphthalamide) (Polyamide PACPN), Poly Isophorone adipamide (polyamide IPD6), polyisophorone sveramide (polyamide IPD8), polyisophorone azelamide (polyamide IPD9), polyisophorone sebacamide (polyamide IPD10), polyisophorondodecamide (polyamide IPD12), polyisophorone terephthal Ramide (polyamide IPDT), polyisophorone isophthalamide (polyamide IPDI), polyisophorone hexahydroterephthalamide (polyamide IPDT (H)), polyisophoron naphthalamide (polyamide IPDN), polytetramethylene terephthalamide (polyamide 4T) , Polytetramethylene isophthalamide (polyamide 4I), polytetramethylene hexahydroterephthalamide (polyamide 4T (H)), polytetramethylene naphthalamide (polyamide 4N), polypentamethylene terephthalamide (polyamide 5T), poly Pentamethylene 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)), polyhexamethylenenaphthalide Ramide (Polyamide 6N), Poly (2-Methylpentamethylene terephthalamide) (Polyamide M5T), Poly (2-Methylpentamethyleneisophthalamide) (Polyamide M5I), Poly (2-Methylpentamethylene hexahydroterephthalamide) ) (Polyamide M5T (H)), poly (2-methylpentamethylenenaphthalamide (polyamide M5N), polynonamethylene terephthalamide (polyamide 9T), polynonamethylene isophthalamide (polyamide 9I), polynonamethylene hexahydro Telephthalamide (polyamide 9T (H)), polynonamethylene naphthalamide (polyamide 9N), poly (2-methyloctamethylene terephthalamide) (polyamide M8T), poly (2-methyloctamethyleneisophthalamide) (polyamide) M8I), Poly (2-methyloctamethylenehexahydroterephthalamide) (Polyamide M8T (H)), Poly (2-Methyloctamethylenenaphthalamide) (Polyamide M8N), Polytrimethylhexamethyleneterephthalamide (PolyamideTMHT) , Polytrimethylhexamethylene isophthalamide (polyamide TMHI), polytrimethylhexamethylene hexahydroterephthalamide (polyamide TMHT (H)), polytrimethylhexamethylenenaphthalamide (polyamide TMHN), polydecamethylene terephthalamide (polyamide 10T) ), Polydecamethylene isophthalamide (polyamide 10I), polydecamethylene hexahydroterephthalamide (polyamide 10T (H)), polydecamethylene naphthalamide (polyamide 10N), polyundecamethylene terephthalamide (polyamide 11T) , Polyundecamethylene isophthalamide (polyamide 11I), polyundecamethylene hexahydroterephthalamide (polyamide 11T (H)), polyundecamethylene naphthalamide (polyamide 11N), polydodecamethylene terephthalamide (polyamide 12T) ), Polydodecamethylene isophthalamide (polyamide 12I), polydodecamethylene hexahydroterephthalamide (polyamide 12T (H)), polydodecamethylene naphthalamide (polyamide 12N), raw material monomers of these polyamides and / or the above. Examples thereof include polyamide-based resins such as copolymers using several kinds of raw material monomers of the aliphatic polyamide (A).

In addition, polyvinylidene fluoride (PVDF), vinyl fluoride (PVF), polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (PFA), Tetrafluoroethylene / hexafluoropropylene copolymer (FEP), tetrafluoroethylene / perfluoro (alkyl vinyl ether) / hexafluoropropylene copolymer, ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / tetrafluoroethylene / Hexafluoropropylene copolymer (EFEP), vinylidene fluoride / tetrafluoroethylene copolymer, vinylidene fluoride / hexafluoropropylene copolymer, vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer, tetrafluoroethylene / Hexafluoropropylene / vinylidene fluoride copolymer (THV), vinylidene fluoride / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer, tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) Copolymer, ethylene / chlorotrifluoroethylene copolymer (ECTFE), chlorotrifluoroethylene / tetrafluoroethylene copolymer, vinylidene fluoride / chlorotrifluoroethylene copolymer, chlorotrifluoroethylene / perfluoro (alkyl) Vinyl ether) copolymer, chlorotrifluoroethylene / hexafluoropropylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene / hexafluoropropylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene / vinylidene fluoride copolymer, Chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer (CPT), chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) / hexafluoropropylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene / Hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer, chlorotrifluoroethylene / tetrafluoroethylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer, chlorotrifluoroethylene / tetrafluoroethylene / vinylidene fluoride / He Functional groups that are reactive with fluorine-based resins such as xafluoropropylene copolymers, chlorotrifluoroethylene / tetrafluoroethylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) / hexafluoropropylene copolymers, and amino groups. The fluororesin containing the above can be mentioned.

In addition, high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), ultrahigh 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), Polyethylene-based products such as ethylene / methyl methacrylate copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), and ethylene / ethyl acrylate copolymer (EEA). Resin, polystyrene (PS), syndiotactic polystyrene (SPS), methyl methacrylate / styrene copolymer (MS), methyl methacrylate / styrene / butadiene copolymer (MBS), styrene / butadiene copolymer (SBR) , Styrene / isoprene copolymer (SIR), styrene / isoprene / butadiene copolymer (SIBR), styrene / butadiene / styrene copolymer (SBS), styrene / isoprene / styrene copolymer (SIS), styrene / ethylene / Butylene / styrene copolymer (SEBS), polystyrene resin 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, endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid and other carboxyl groups, and metal salts thereof. Acids such as (Na, Zn, K, Ca, Mg), maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid anhydride and the like. The above-mentioned polyolefin-based resin, polystyrene-based resin, and polybutylene terephthalate (PBT) containing a functional group such as an anhydride group, glycidyl acrylate, glycidyl methacrylate, glycidyl etacrilate, glycidyl itacone, and glycidyl citracone. , Polyethylene terephthalate (PET), Polyethylene isophthalate (PEI), Poly (ethylene terephthalate / ethylene isophthalate) 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 resin such as glycolic acid (PGA), polyether resin such as polyacetal (POM) and polyphenylene ether (PPO), polysulfone such as polysulfone (PSU), polyethersulfone (PESU) and polyphenylsulfone (PPSU). Polyetherether-based resin, poly-thioether-based resin such as polyphenylene sulfide (PPS) and polythioethersulfone (PTES), polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK) , Polyetheretheretherketone (PEEEK), Polyetheretherketoneketone (PEEKK), Polyetherketoneketoneketone (PEKKKK), Polyetherketone etherketoneketone (PEKEKK) and other polyketone resins, polyacrylonitrile (PAN), poly Polynitrile resins such as methacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylnitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), acrylonitrile / butadiene copolymer (NBR), Polymethacrylate-based resins such as polymethylmethacrylate (PMMA) and ethylpolymethacrylate (PEMA), polyvinyl ester-based resins such as polyvinylacetate (PVAc), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), chloride. Polyvinyl chloride resin such as vinyl / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer, cellulose resin such as cellulose acetate and cellulose butyrate, polycarbonate resin such as polycarbonate (PC), thermoplastic polyimide ( Examples thereof include polyimide resins such as TPI), polyetherimide, polyesterimide, polyamideimide (PAI) and polyesteramideimide, thermoplastic polyurethane resins, polyamide elastomers, polyurethane elastomers and polyester elastomers.

In the laminated tube of the present invention, from the viewpoint of melt stability of EVOH (C), among the above-exemplified thermoplastic resins, polyester resins, polyamide resins, polythioether resins having a melting point of 290 ° C. or lower, It is preferable to use a polyolefin-based resin and a fluorine-based resin.

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

As a laminated tube manufacturing method, a method of melt extrusion and simultaneous lamination inside or outside the die (coextrusion molding method) using an extruder corresponding to the number of layers or the number of materials, or once a single-layer tube or An example is a method (coating method) in which a laminated tube manufactured by the above method is manufactured in advance, and the resins are integrated and laminated on the outside in order by using an adhesive if necessary. The laminated tube of the present invention is preferably manufactured by a coextrusion method in which various materials are coextruded in a molten state and both are heat-sealed (melt-bonded) to produce a tube having a laminated structure in one step.

Further, when the obtained laminated tube has a complicated shape or is subjected to heat bending after molding to obtain a molded product, in order to remove the residual strain of the molded product, after forming the above-mentioned laminated tube, It is also possible to obtain a desired molded product by heat treatment for 0.01 hours or more and 10 hours or less at a temperature lower than the lowest melting point of the resins constituting the tube.

The laminated tube may have a corrugated region. The corrugated region is a region formed in a corrugated shape, a bellows shape, an accordion shape, a corrugated shape, or the like. The corrugated region may be not only provided over the entire length of the laminated tube, but may be partially provided in an appropriate region in the middle. The corrugated region can be easily formed by first molding a straight tubular tube and then molding the tube to obtain a predetermined corrugated shape or the like. By having such a corrugated region, it has shock absorption and is easy to attach. Further, for example, it is possible to add necessary parts such as a connector, or to make an L-shape, a U-shape, or the like by bending.

Natural rubber (NR), butadiene rubber (BR), and isoprene rubber (IR) are applied to all or part of the outer circumference of the laminated tube thus formed in consideration of stone splash, wear 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), hydride 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), ethylene Propropylene diene rubber (EPDM), ethylene vinyl acetate rubber (EVM), mixture rubber of NBR and EPDM, acrylic rubber (ACM), ethylene acrylic rubber (AEM), acrylate butadiene rubber (ABR), styrene butadiene rubber (SBR), carboxylation Styrene butadiene rubber (XSBR), styrene isoprene rubber (SIR), styrene isoprene butadiene rubber (SIBR), urethane rubber, silicone rubber (MQ, VMQ), fluororubber (FKM, FFKM), fluorosilicone rubber (FVMQ), vinyl chloride A solid or sponge-like protective member (protector) composed of a thermoplastic elastomer such as a system, an olefin system, an ester system, a urethane system, or an amide system can be arranged. The protective member may be a sponge-like porous body by a known method. By making it a porous body, it is possible to form a protective portion that is lightweight and has excellent heat insulating properties. In addition, the material cost can be reduced. Alternatively, glass fiber or the like may be added to improve the strength. The shape of the protective member is not particularly limited, but is usually a block-shaped member having a recess for receiving a tubular member or a laminated tube. In the case of a tubular member, the laminated tube can be inserted into the previously prepared tubular member later, or the tubular member can be coated and extruded on the laminated tube to make them in close contact with each other. In order to bond the two, an adhesive is applied to the inner surface of the protective member or the concave surface as necessary, and a laminated tube is inserted or fitted therein, and the laminated tube and the protective member are integrated by bringing them into close contact with each other. Form a structure. It is also possible to reinforce with metal or the like.

The outer diameter of the laminated tube is such that the flow rate of the chemical solution (for example, fuel such as alcohol-containing gasoline) is taken into consideration, and the wall thickness is such that the permeability of the chemical solution does not increase and the breaking pressure of the normal tube can be maintained. In addition, the thickness is designed so that the ease of assembling the tube and the vibration resistance during use can be maintained to a good degree, but the thickness is not limited. The outer diameter is preferably 4 mm or more and 300 mm or less, the inner diameter is preferably 3 mm or more and 250 mm or less, and the wall thickness is preferably 0.5 mm or more and 25 mm or less.

The laminated tube of the present invention includes mechanical parts such as automobile parts, internal combustion engine applications, power tool housings, industrial materials, industrial materials, electrical / electronic parts, medical care, foods, household / office supplies, building material-related parts, and furniture. It can be used for various purposes such as parts for parts.

In addition, the laminated tube of the present invention is preferably used as a chemical transfer tube because it has excellent chemical permeation prevention properties. Examples of the chemical solution include aromatic hydrocarbon solvents such as benzene, toluene and xylene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, diethylene glycol, phenol, cresol, polyethylene glycol and polypropylene glycol. Alcohol, phenolic solvent, dimethyl ether, dipropyl ether, methyl-t-butyl ether, ethyl-t-butyl ether, dioxane, tetrahydrofuran and other ether solvents, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane , Dichloroethane, tetrachloroethane, perchlorethane, halogen-based solvents such as chlorobenzene, ketone solvents such as acetone, methylethylketone, diethylketone, acetophenone, gasoline, kerosene, diesel gasoline, alcohol-containing gasoline, ethyl-t-butyl ether blend Oxygen-containing gasoline, amine-containing gasoline, sour gasoline, castor oil-based brake liquid, glycol ether-based brake liquid, borate ester-based brake liquid, frigid region brake liquid, silicone oil-based brake liquid, mineral oil-based brake liquid, power steering oil, Examples thereof include hydrogen sulfide oil, window washer fluid, engine coolant, urea solution, pharmaceutical agents, ink, paint and the like. The laminated tube of the present invention is preferably used as a tube for transporting the above-mentioned chemical solution, and specifically, a feed tube, a return tube, an air conditioner tube, a fuel filler tube, an ORVR tube, a reserve tube, a vent tube and the like. Fuel tube, oil tube, oil drilling tube, brake tube, window washer fluid tube, engine coolant (LLC) tube, reservoir tank tube, urea solution transport tube, cooling water, cooler tube for refrigerant, etc., tube for air conditioner refrigerant , 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, and other chemical solution tubes. More preferably it is used as a fuel tube.

Examples and comparative examples are shown below, and the present invention will be specifically described, but the present invention is not limited thereto.
The analysis and physical property measurement methods in Examples and Comparative Examples, and the materials used in Examples and Comparative Examples are shown.

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

[Terminal amino group concentration]
Put a predetermined amount of polyamide sample in an Erlenmeyer flask with a stopper, add 40 mL of the solvent phenol / methanol (volume ratio 9/1) prepared in advance, dissolve by stirring with a magnet stirrer, and use thymol blue as an indicator. The titration was carried out with 0.05N of hydrochloric acid to determine the terminal amino group concentration.

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

In addition, each physical property of the laminated tube was measured by the following method.
[Low temperature impact resistance]
An impact test was performed at −40 ° C. by the method described in VW TL52435 4.2.

[Chemical solution (alcohol-containing gasoline) permeation prevention]
One end of the tube cut to 200 mm is sealed, and alcohol-containing gasoline (CE10), which is a mixture of FuelC (isooctane / toluene = 50/50 volume ratio) and ethanol in a 90/10 volume ratio, is put inside, and the other end is also It was sealed. The total mass was then measured, then the test tube was placed in an oven at 60 ° C. and the mass change was measured daily. The amount of alcohol-containing gasoline permeated (g / m ² · day) was calculated by dividing the daily mass change by the surface area inside the tube.

[Interlayer adhesiveness]
A tube cut to 200 mm was further cut in half in the vertical direction to prepare a test piece. A 180 ° peeling test was carried out at a tensile speed of 50 mm / min using a universal material testing machine (Tencilon UTM III-200, manufactured by Orientec). The peel strength was read from the maximum point of the SS curve, and the interlayer adhesiveness was evaluated.

[Interlayer adhesion after heat treatment]
The tube cut to 200 mm was placed in an oven at 160 ° C. and treated for 12 minutes. The interlayer adhesiveness of the removed tube was evaluated according to the above method. When the peel strength after the heat treatment was 2.0 N / mm or more, it was judged that the interlayer adhesive durability was excellent.

[Elution resistance of low molecular weight components]
A mixture of 42.25% toluene, 25.35% isooctane, 12.68% diisobutylene, 4.23% ethanol, 15% methanol, and 0.5% water, with one end of a tube cut to 0.5 m sealed. FAM B conforming to DIN 511604B was put inside, and the remaining end was also sealed. Then, the test tube was placed in an oven at 60 ° C. and treated for 96 hours. Then, after cooling the alcohol-containing gasoline in the taken-out tube at room temperature, the test solution was evaporated to dry the residue, and the mass of the residue was measured. The elution amount (g / m ² ) was calculated by dividing the mass of the residue by the inner surface area of the tube. When the elution amount was 15.0 g / m ² or less, it was judged that the resistance to elution was excellent.

[Materials used in Examples and Comparative Examples]
Aliphatic polyamide (A)
Production of Polyamide 12 Composition (A-1) Polyamide 12 (a-1) (manufactured by Ube Kosan Co., Ltd., UBESTA 3030UX1, relative viscosity 2.21) and maleic anhydride-modified ethylene / propylene co-weight as an impact improver Combined (JSR Co., Ltd., JSR T7761P), triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] as an antioxidant (BASF Japan, IRGANOX245) , And tris (2,4-di-t-butylphenyl) phosphite (manufactured by BASF Japan, IRGAFOS168) as a phosphorus-based processing stabilizer were mixed in advance, and a twin-screw melt-kneader (manufactured by Japan Steel Works, Ltd.) While supplying to model: TEX44), benzenesulfonic acid butylamide as a plasticizer is injected from the middle of the cylinder of the twin-screw melt-kneader by a metering pump, melt-kneaded at a cylinder temperature of 180 ° C to 260 ° C, and the molten resin is prepared. After extruding into a strand shape, this is introduced into a water tank, cooled, cut, and vacuum dried to make a total of 100 parts by mass of polyamide 12 85% by mass, impact improver 10% by mass, and plasticizer 5% by mass. Pellets of a polyamide 12 composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained (hereinafter, this polyamide 12 composition is referred to as (A-1)).

Production of Polyamide 610 (a-2) or (b-2) In a pressure-resistant reaction vessel with a stirrer with an internal volume of 70 liters, 17.6 kg of a 50 mass% aqueous solution of an equimolar salt of 1,6-hexanediamine and sebacic acid, After charging 40.0 g of 1,6-hexanediamine and replacing the inside of the polymerization tank with nitrogen, the mixture was heated to 220 ° C. and stirred so that the inside of the reaction system became uniform at this temperature. Next, the temperature inside the polymerization tank was raised to 270 ° C., and the pressure inside the tank was adjusted to 1.7 MPa, and the polymerization was carried out under stirring for 2 hours. Then, the pressure was released to normal pressure over about 2 hours, then the pressure was reduced to 53 kPa, and the polymerization was carried out under reduced pressure for 4 hours. Next, nitrogen was introduced into the autoclave, the pressure was restored to normal pressure, and then the strands were extracted from the lower nozzle of the reaction vessel and cut to obtain pellets. The pellet was dried under reduced pressure to obtain a polyamide 610 having a relative viscosity of 3.05, a terminal amino group concentration of 50 μeq / g, and a terminal carboxyl group concentration of 14 μeq / g (hereinafter, this polyamide 610 is referred to as (a-2) or (b-). 2).

Production of Polyamide 610 Composition (A-2) In the production of the polyamide 12 composition (A-1), the polyamide 12 (a-1) was changed to the polyamide 610 (a-2), and the cylinder temperature was changed from 260 ° C. to 270 ° C. In the same manner as in the production of the polyamide 12 composition (A-1), 80% by mass of the polyamide 610, 10% by mass of the impact-resistant improving material, and 10% by mass of the plasticizing agent were added to 100 parts by mass in total, except that the value was changed to Then, pellets of a polyamide 610 composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained (hereinafter, this polyamide 610 composition is referred to as (A-2)).

Production of Polyamide 612 (a-3) or (b-3) In the production of Polyamide 610 (a-2), 17.6 kg of a 50 mass% aqueous solution of an equimolar salt of 1,6-hexanediamine and sebacic acid was added as 1, Polyamide 610 (a-2), except that 19.2 kg of a 50 mass% aqueous solution of an equimolar salt of 6-hexanediamine and dodecanedic acid and the amount of 1,6-hexanediamine added were changed from 40.0 g to 43.5 g. ), A polyamide 612 having a relative viscosity of 2.78, a terminal amino group concentration of 51 μeq / g, and a terminal carboxyl group concentration of 14 μeq / g was obtained (hereinafter, this polyamide 612 is obtained from (a-3) or (B-3).

Production of Polyamide 612 Composition (A-3) In the production of the polyamide 12 composition (A-1), the polyamide 12 (a-1) was changed to the polyamide 612 (a-3), and the cylinder temperature was changed from 260 ° C. to 270 ° C. In the same manner as in the production of the polyamide 12 composition (A-1), 80% by mass of the polyamide 612, 10% by mass of the impact-resistant improving material, and 10% by mass of the plasticizing agent were added to 100 parts by mass in total, except that the value was changed to Then, pellets of a polyamide 612 composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained (hereinafter, this polyamide 612 composition is referred to as (A-3)).

Production of Polyamide 6 Composition (A-4) In the production of the polyamide 12 composition (A-1), the polyamide 12 (a-1) was used as a polyamide 6 (a-4) (manufactured by Ube Industries, Ltd., UBE NYLON 1030B). , Relative viscosity 3.89), and the cylinder temperature was changed from 260 ° C. to 270 ° C., except that the polyamide 12 composition (A-1) was produced in the same manner as in the production of the polyamide 12 composition (A-1). A pellet of a polyamide 6 composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer was obtained with respect to a total of 100 parts by mass of 10% by mass of the material and 15% by mass of the plasticizer ( Hereinafter, this polyamide 6 composition is referred to as (A-4)).

Polyamide 6/66/12 composition (B)
Production of Polyamide 6/66/12 (b-1) In a pressure-resistant reaction vessel with a stirrer with an internal volume of 70 liters, 16.2 kg of caprolactam, a 50 mass% aqueous solution of an equimolar salt of 1,6-hexanediamine and adipic acid 5 .0 kg and 2.5 kg of 12-aminododecanoic acid were added, heated to 100 ° C., and stirred so that the inside of the reaction system became uniform at this temperature. Subsequently, the temperature was further raised to 260 ° C., and the mixture was stirred under a pressure of 2.5 MPa for 1 hour. Then, the pressure was released to volatilize the water from the reaction vessel, and the polymerization reaction was carried out at 260 ° C. for 2 hours under normal pressure, and further carried out under a reduced pressure of 260 ° C. and 53 kPa for 7 hours. After completion of the reaction, the reaction product taken out in a strand shape from the lower nozzle of the reaction vessel was introduced into a water tank, cooled, and cut to obtain pellets. The pellets are immersed in hot water to extract and remove unreacted monomers, then dried under reduced pressure, and the polyamide 6/66/12 (caproamide unit / hexamethylene adipamide unit / dodecane amide) having a relative viscosity of 4.01 is used. Unit = 78/11/11 mass%) was obtained (hereinafter, this polyamide 6/66/12 is referred to as (b-1)).

Production of Polyamide 6/66/12 Composition (B-1) In the production of Polyamide 12 Composition (A-1), polyamide 12 (a-1) was used as Polyamide 6/66/12 (b-1) and Polyamide 610. Polyamide 6/66/12 50% by mass, polyamide 610 30% by mass, impact-resistant improving material 15 by the same method as in the production of the polyamide 12 composition (A-1) except that it was changed to (b-2). A pellet of a polyamide 6/66/12 composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer was obtained with respect to 100 parts by mass of a total of 5% by mass of a plasticizer. (Hereinafter, this polyamide 6/66/12 composition is referred to as (B-1)).

Production of Polyamide 6/66/12 Composition (B-2) In the production of polyamide 6/66/12 composition (B-1), polyamide 610 (b-2) was changed to polyamide 612 (b-3). Except for the above, the same method as for the production of the polyamide 6/66/12 composition (B-1) was used, with polyamide 6/66/12 50% by mass, polyamide 612 30% by mass, impact resistant improving material 15% by mass, and plastic. Pellets of a polyamide 6/66/12 composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained with respect to 100 parts by mass in total of 5% by mass of the agent (hereinafter, This polyamide 6/66/12 composition is referred to as (B-2)).

Production of Polyamide 6/66/12 Composition (B-3) Polyamide 6/66 / in the production of Polyamide 6/66/12 Composition (B-1), except that Polyamide 610 (b-2) is not used. 12 Oxidation with respect to 100 parts by mass in total of polyamide 6/66/12 80% by mass, impact resistant improving material 15% by mass, and plasticizer 5% by mass by the same method as in the production of the composition (B-1). Pellets of a polyamide 6/66/12 composition composed of 0.8 parts by mass of an inhibitor and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained (hereinafter, this polyamide 6/66/12 composition is (B-3). ).).

Production of Polyamide 6/66/12 Composition (B-4) Polyamide 610 (b-2), impact improver, and plasticizer are not used in the production of polyamide 6/66/12 composition (B-1). Except for the above, 0.8 parts by mass of the antioxidant and phosphorus-based processing with respect to 100% by mass of the polyamide 6/66/12 by the same method as in the production of the polyamide 6/66/12 composition (B-1). Pellets of a polyamide 6/66/12 composition composed of 0.2 parts by mass of a stabilizer were obtained (hereinafter, this polyamide 6/66/12 composition is referred to as (B-4)).

Production of Polyamide 6/12 (b-4) In the production of Polyamide 6/66/12 (b-1), 16.2 kg of caprolactam, a 50 mass% aqueous solution of an equimolar salt of 1,6-hexanediamine and adipic acid 5 Polyamide 6/66/12 (b-1) except that 0.0 kg and 2.5 kg of 12-aminododecanoic acid were changed to 16.2 kg of caprolactam and 4.4 kg of 12-aminododecanoic acid and 2 kg of water was added. Polyamide 6/12 (caprolactam unit / dodecaneamide unit = 80/20% by mass) having a relative viscosity of 3.86 was obtained by the same method as in the production (hereinafter, this polyamide 6/12 is referred to as (b-4). .).

Production of Polyamide 6/12 Composition (B-5) In the production of Polyamide 6/66/12 Composition (B-1), Polyamide 6/66/12 (b-1) was used as Polyamide 6/12 (b-4). ), And the same method as for the production of the polyamide 6/66/12 composition (B-1), except that the polyamide 610 (b-2) is not used, the polyamide 6/12 80% by mass, impact resistance. Pellets of a polyamide 6/12 composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer with respect to a total of 100 parts by mass of 15% by mass of the improving material and 5% by mass of the plasticizing agent. Obtained (hereinafter, this polyamide 6/12 composition is referred to as (B-5)).

Ethylene / vinyl acetate copolymer saponified product (C)
EVOH (C-1): manufactured by Nippon Synthetic Chemistry Co., Ltd., Soanol DC3203, ethylene content 32 mol%, saponification degree 99 mol% or more

Aliphatic polyamide composition containing no plasticizer (D)
Production of Polyamide 12 Composition (D-1) In the production of the polyamide 12 composition (A-1), the polyamide 12 composition (A-) was produced except that the amount of the impact improving material added was changed without using a plasticizer. By the same method as in the production of 1), 0.8 parts by mass of the antioxidant and 0.2% by mass of the phosphorus-based processing stabilizer are used for a total of 100 parts by mass of the polyamide 12 85% by mass and the impact improving material 15% by mass. Pellets of a polyamide 12 composition composed of parts were obtained (hereinafter, this polyamide 12 composition is referred to as (D-1)).

Production of Conductive Polyamide 12 Composition (D-2) In the production of the polyamide 12 composition (A-1), polyamide 12 (a-1) was used as (a-5) (manufactured by Ube Industries, Ltd., UBESTA 3020U, Polyamide, except that the relative viscosity was changed to 1.86), carbon black (Vulcan XD-72 manufactured by Cabot) was used as the conductive filler, no plasticizer was used, and the cylinder temperature was changed from 260 ° C to 270 ° C. In the same manner as in the production of the 12 composition (A-1), 70% by mass of the polyamide 12, 10% by mass of the impact improving material, and 20% by mass of the conductive filler were added to 100 parts by mass of the antioxidant. Pellets of a conductive polyamide 12 composition consisting of 8 parts by mass and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained (hereinafter, this conductive polyamide 12 composition is referred to as (D-2)).

Production of Polyamide 610 Composition (D-3) In the production of the polyamide 610 composition (A-2), the polyamide 610 composition (A-) was produced except that the amount of the impact improving material added was changed without using a plasticizer. By the same method as in the production of 2), 0.8 parts by mass of the antioxidant and 0.2 parts of the phosphorus-based processing stabilizer are used for a total of 100 parts by mass of the polyamide 610 85% by mass and the impact resistance improving material 15% by mass. Pellets of a polyamide 610 composition composed of parts by mass were obtained (hereinafter, this polyamide 610 composition is referred to as (D-3)).

Production of Polyamide 610 (a-6) In the production of polyamide 610 (a-2), the same method as the production of polyamide 610 (a-2) was used except that the post-polymerization time was changed from 4 hours to 2 hours. , A polyamide 610 having a relative viscosity of 2.28, a terminal amino group concentration of 72 μeq / g, and a terminal carboxyl group concentration of 34 μeq / g was obtained (hereinafter, this polyamide 610 is referred to as (a-6)).

Production of Conductive Polyamide 610 Composition (D-4) In the production of the conductive polyamide 12 composition (D-2), the polyamide 12 (a-5) was changed to the polyamide 610 (a-6) and the cylinder temperature was changed to 270. Polyamide 610 65% by mass, impact improver 15% by mass, and conductive filler 20% by mass were prepared in the same manner as in the production of the conductive polyamide 12 composition (D-2) except that the temperature was changed from ° C to 280 ° C. Pellets of a conductive polyamide 610 composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained with respect to 100 parts by mass in total (hereinafter, this conductive polyamide 610). The composition is referred to as (D-4)).

Production of Polyamide 612 Composition (D-5) In the production of the polyamide 612 composition (A-3), the polyamide 612 composition (A-) was produced except that the amount of the impact improving material added was changed without using a plasticizer. By the same method as in the production of 3), 0.8 parts by mass of the antioxidant and 0.2 parts of the phosphorus-based processing stabilizer are used for a total of 100 parts by mass of the polyamide 612 85% by mass and the impact resistance improving material 15% by mass. Pellets of a polyamide 612 composition composed of parts by mass were obtained (hereinafter, this polyamide 612 composition is referred to as (D-5)).

Production of Polyamide 612 (a-7) In the production of polyamide 612 (a-3), the same method as in the production of polyamide 612 (a-3) was used except that the post-polymerization time was changed from 4 hours to 2 hours. , Polyamide 612 having a relative viscosity of 2.06, a terminal amino group concentration of 73 μeq / g, and a terminal carboxyl group concentration of 35 μeq / g was obtained (hereinafter, this polyamide 612 is referred to as (a-7)).

Production of Conductive Polyamide 612 Composition (D-6) In the production of the conductive polyamide 12 composition (D-2), the polyamide 12 (a-5) was changed to the polyamide 612 (a-7) and the cylinder temperature was changed to 270. Polyamide 612 65% by mass, impact improving material 15% by mass, and conductive filler 20% by mass by the same method as in the production of the conductive polyamide 12 composition (D-2) except that the temperature was changed from ℃ to 280 ° C. Pellets of a conductive polyamide 612 composition composed of 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained with respect to 100 parts by mass in total (hereinafter, this conductive polyamide 612 composition). Is called (D-6).

Production of Polyamide 1010 (a-8) In the production of Polyamide 610 (a-2), 17.6 kg of a 50 mass% aqueous solution of an equimolar salt of 1,6-hexanediamine and sebacic acid was added to 1,10-decanediamine and sebacic acid. Except for changing the addition amount of 10.4 kg of the polyamethylene salt of acid, 3.4 kg of water, and 1,6-hexanediamine from 40.0 g to 47.0 g, and changing the temperature in the polymerization tank from 270 ° C to 240 ° C. By the same method as in the production of the polyamide 610 (a-2), a polyamide 1010 having a relative viscosity of 2.55, a terminal amino group concentration of 50 μeq / g, and a terminal carboxyl group concentration of 14 μeq / g was obtained (hereinafter, this polyamide 1010 is used. (A-8).

Production of Polyamide 1010 Composition (D-7) In the production of the polyamide 12 composition (A-1), the polyamide 12 (a-1) was changed to the polyamide 1010 (a-8), and no plasticizer was used. By the same method as in the production of the polyamide 12 composition (A-1) except that the amount of the improving material added was changed, with respect to a total of 100 parts by mass of the polyamide 1010 85% by mass and the impact resistant improving material 15% by mass. , 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus-based processing stabilizer were obtained as pellets of the polyamide 1010 composition (hereinafter, this polyamide 1010 composition is referred to as (D-7)).

Production of Polyamide 1010 (a-9) In the production of polyamide 1010 (a-8), the same method as in the production of polyamide 1010 (a-8) was used except that the post-polymerization time was changed from 4 hours to 2 hours. , A polyamide 1010 having a relative viscosity of 1.96, a terminal amino group concentration of 70 μeq / g, and a terminal carboxyl group concentration of 32 μeq / g was obtained (hereinafter, this polyamide 1010 is referred to as (a-9)).

Production of Conductive Polyamide 1010 Composition (D-8) Conductive in the production of the conductive polyamide 12 composition (D-2), except that the polyamide 12 (a-5) was changed to the polyamide 1010 (a-9). Antioxidant based on 100 parts by mass of polyamide 1010 70% by mass, impact improving material 10% by mass, and conductive filler 20% by mass by the same method as in the production of the sexual polyamide 12 composition (D-2). Pellets of a conductive polyamide 1010 composition composed of 0.8 parts by mass and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained (hereinafter, this conductive polyamide 1010 composition is referred to as (D-8)).

Production of Polyamide 1012 (a-10) In the production of Polyamide 610 (a-2), 17.6 kg of a 50 mass% aqueous solution of an equimolar salt of 1,6-hexanediamine and sebacic acid was added to 1,10-decanediamine and dodecane. Except for changing the addition amount of 11.1 kg of isomorphic salt of diacid, 3.7 kg of water, and 1,6-hexanediamine from 40.0 g to 50.6 g, and changing the temperature in the polymerization tank from 270 ° C to 230 ° C. , Polyamide 1012 having a relative viscosity of 2.36, a terminal amino group concentration of 51 μeq / g, and a terminal carboxyl group concentration of 15 μeq / g was obtained in the same manner as in the production of the polyamide 610 (a-2) (hereinafter, this polyamide 1012). Is called (a-10)).

Production of Polyamide 1012 Composition (D-9) In the production of the polyamide 12 composition (A-1), the polyamide 12 (a-1) was changed to the polyamide 1012 (a-10), and no plasticizer was used. By the same method as in the production of the polyamide 12 composition (A-1) except that the amount of the improving material added was changed, with respect to a total of 100 parts by mass of the polyamide 1012 85% by mass and the impact resistant improving material 15% by mass. , 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus-based processing stabilizer were obtained as pellets of the polyamide 1012 composition (hereinafter, this polyamide 1012 composition is referred to as (D-9)).

Production of Polyamide 1012 (a-11) In the production of polyamide 1012 (a-10), the same method as in the production of polyamide 1012 (a-10) was used except that the post-polymerization time was changed from 4 hours to 2 hours. , A polyamide 1012 having a relative viscosity of 1.80, a terminal amino group concentration of 70 μeq / g, and a terminal carboxyl group concentration of 31 μeq / g was obtained (hereinafter, this polyamide 1012 is referred to as (a-11)).

Production of Conductive Polyamide 1012 Composition (D-10) Conductive in the production of the conductive polyamide 12 composition (D-2), except that the polyamide 12 (a-5) was changed to the polyamide 1012 (a-11). Antioxidant with respect to 100 parts by mass in total of 70% by mass of polyamide 1012, 10% by mass of impact improving material, and 20% by mass of conductive filler by the same method as in the production of the sexual polyamide 12 composition (D-2). Pellets of a conductive polyamide 1012 composition consisting of 0.8 parts by mass and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained (hereinafter, this conductive polyamide 1012 composition is referred to as (D-10)).

Production of Polyamide 6 Composition (D-11) In the production of the polyamide 6 composition (A-4), the polyamide 6 composition (A-) was produced except that the amount of the impact improving material added was changed without using a plasticizer. By the same method as in the production of 4), 0.8 parts by mass of the antioxidant and 0.2 parts of the phosphorus-based processing stabilizer are used for a total of 100 parts by mass of the polyamide 6 85% by mass and the impact resistance improving material 15% by mass. Pellets of a polyamide 6 composition composed of parts by mass were obtained (hereinafter, this polyamide 6 composition is referred to as (D-11)).

Production of Conductive Polyamide 6 Composition (D-12) In the production of the conductive polyamide 12 composition (D-2), polyamide 12 (a-5) was used as polyamide 6 (a-12) (manufactured by Ube Industries, Ltd.). , UBE NYLON 1015B, relative viscosity 2.63) and the cylinder temperature was changed from 270 ° C to 280 ° C, except that the polyamide 6 was produced in the same manner as in the production of the conductive polyamide 12 composition (D-2). Conductive polyamide composed of 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus-based processing stabilizer with respect to a total of 100 parts by mass of 60% by mass, 20% by mass of impact improving material, and 20% by mass of conductive filler. Pellets of 6 compositions were obtained (hereinafter, this conductive polyamide 6 composition is referred to as (D-12)).

Example 1
Using the above-mentioned polyamide 12 composition (A-1), polyamide 6/66/12 composition (B-1), EVOH (C-1), and polyamide 12 composition (D-1), a plastic In a 5-layer tube forming machine (manufactured by Plastic Engineering Laboratory Co., Ltd.), (A-1) has an extrusion temperature of 250 ° C., (B-1) has an extrusion temperature of 260 ° C., and (C-1) has an extrusion temperature of 220 ° C. , (D-1) were separately melted at an extrusion temperature of 250 ° C., and the discharged molten resins were merged by an adapter to form a laminated tubular body. Subsequently, it is cooled by a sizing die whose size is controlled and taken over, and the (a) layer (outermost layer) composed of (A-1), the (b) layer (outer layer, inner layer) composed of (B-1), and (C). When the (c) layer (intermediate layer) composed of (-1) and the (d) layer (innermost layer) composed of (D-1) are used, the layer structure is (a) / (b) / (c) / (b). ) / (D) = 0.35 / 0.10 / 0.15 / 0.10 / 0.30 mm, and a laminated tube having an inner diameter of 6 mm and an outer diameter of 8 mm was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 2
In Example 1, the same as in Example 1 except that the polyamide 12 composition (A-1) was changed to the polyamide 610 composition (A-2) and the extrusion temperature of (A-2) was changed to 260 ° C. By the method, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 3
In Example 1, the same as in Example 1 except that the polyamide 12 composition (A-1) was changed to the polyamide 612 composition (A-3) and the extrusion temperature of (A-3) was changed to 260 ° C. By the method, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 4
In Example 1, the laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 1 except that the polyamide 6/66/12 composition (B-1) was changed to (B-2). Obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 5
In Example 1, the polyamide 12 composition (D-1) was changed to the conductive polyamide 12 composition (D-2), and the extrusion temperature of (D-2) was changed to 260 ° C. By the same method, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube. Further, the electrical conductivity of the laminate tube was measured according to SAE J-2260, and at 10 ⁶ Ω / square or less, it was confirmed that an excellent destaticizing performance.

Example 6
In Example 1, the same as in Example 1 except that the polyamide 12 composition (D-1) was changed to the polyamide 610 composition (D-3) and the extrusion temperature of (D-3) was changed to 260 ° C. By the method, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 7
In Example 1, the polyamide 12 composition (D-1) was changed to the conductive polyamide 610 composition (D-4), and the extrusion temperature of (D-4) was changed to 270 ° C. By the same method, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube. Further, the electrical conductivity of the laminate tube was measured according to SAE J-2260, and at 10 ⁶ Ω / square or less, it was confirmed that an excellent destaticizing performance.

Example 8
In Example 1, the same as in Example 1 except that the polyamide 12 composition (D-1) was changed to the polyamide 612 composition (D-5) and the extrusion temperature of (D-5) was changed to 260 ° C. By the method, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 9
In Example 1, the polyamide 12 composition (D-1) was changed to the conductive polyamide 612 composition (D-6), and the extrusion temperature of (D-6) was changed to 270 ° C. By the same method, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube. Further, the electrical conductivity of the laminate tube was measured according to SAE J-2260, and at 10 ⁶ Ω / square or less, it was confirmed that an excellent destaticizing performance.

Example 10
In Example 1, the same as in Example 1 except that the polyamide 12 composition (D-1) was changed to the polyamide 1010 composition (D-7) and the extrusion temperature of (D-7) was changed to 260 ° C. By the method, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 11
In Example 1, the polyamide 12 composition (D-1) was changed to the conductive polyamide 1010 composition (D-8), and the extrusion temperature of (D-8) was changed to 270 ° C. By the same method, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube. Further, the electrical conductivity of the laminate tube was measured according to SAE J-2260, and at 10 ⁶ Ω / square or less, it was confirmed that an excellent destaticizing performance.

Example 12
In Example 1, the laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 1 except that the polyamide 12 composition (D-1) was changed to the polyamide 1012 composition (D-9). Obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 13
In Example 1, the polyamide 12 composition (D-1) was changed to the conductive polyamide 1012 composition (D-10), and the extrusion temperature of (D-10) was changed to 260 ° C. By the same method, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube. Further, the electrical conductivity of the laminate tube was measured according to SAE J-2260, and at 10 ⁶ Ω / square or less, it was confirmed that an excellent destaticizing performance.

Example 14
Using the above-mentioned polyamide 12 composition (A-1), polyamide 6/66/12 composition (B-1), EVOH (C-1), and polyamide 6 composition (D-11), a plastic In a 4-layer tube forming machine (manufactured by Plastic Engineering Laboratory Co., Ltd.), (A-1) has an extrusion temperature of 250 ° C., (B-1) has an extrusion temperature of 260 ° C., and (C-1) has an extrusion temperature of 220 ° C. , (D-11) were separately melted at an extrusion temperature of 260 ° C., and the discharged molten resins were merged by an adapter to form a laminated tubular body. Subsequently, it is cooled by a sizing die whose size is controlled, and is taken over. The (a) layer (outermost layer) composed of (A-1), the (b) layer (outer layer) composed of (B-1), and (C-1) ) (C) layer (intermediate layer) and (D-11) (d) layer (innermost layer), the layer structure is (a) / (b) / (c) / (d) = A laminated tube having an inner diameter of 6 mm and an outer diameter of 8 mm was obtained at 0.35 / 0.10 / 0.15 / 0.40 mm. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 15
In Example 14, the laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 14 except that the polyamide 6 composition (D-11) was changed to the polyamide 610 composition (D-3). Obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Example 16
In Example 14, the polyamide 6 composition (D-11) was changed to the conductive polyamide 610 composition (D-4), and the extrusion temperature of (D-4) was changed to 270 ° C. By the same method, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube. Further, the electrical conductivity of the laminate tube was measured according to SAE J-2260, and at 10 ⁶ Ω / square or less, it was confirmed that an excellent destaticizing performance.

Example 17
Polyamide 12 composition (A-1), polyamide 610 composition (A-2), polyamide 6/66/12 composition (B-1), EVOH (C-1), and conductive polyamide 610 composition shown above. Using the object (D-4), (A-1) is extruded at 250 ° C. and (A-2) is extruded at 260 ° C. using a Polybor (manufactured by Plastic Engineering Laboratory Co., Ltd.) 5-layer tube molding machine. ° C., (B-1) is separately melted at an extrusion temperature of 260 ° C., (C-1) is melted separately at an extrusion temperature of 220 ° C., and (D-4) is melted separately at an extrusion temperature of 270 ° C. It was formed into a laminated tubular body. Subsequently, it is cooled by a sizing die whose size is controlled, and is taken over. The (a) layer (outermost layer) composed of (A-1), the (b) layer (outer layer) composed of (B-1), and (C-1) ) (C) layer (intermediate layer), (A-2) (a') layer (inner layer), and (D-4) (d) layer (innermost layer). (A) / (b) / (c) / (a') / (d) = 0.35 / 0.10 / 0.15 / 0.30 / 0.10 mm, laminated tube with inner diameter 6 mm and outer diameter 8 mm Got Table 1 shows the results of measuring the physical properties of the laminated tube. Further, the electrical conductivity of the laminate tube was measured according to SAE J-2260, and at 10 ⁶ Ω / square or less, it was confirmed that an excellent destaticizing performance.

Example 18
In Example 17, the layer configuration shown in Table 1 was carried out in the same manner as in Example 17 except that the conductive polyamide 610 composition (D-4) was changed to the conductive polyamide 612 composition (D-6). Obtained a laminated tube of. Table 1 shows the results of measuring the physical properties of the laminated tube. Further, the electrical conductivity of the laminate tube was measured according to SAE J-2260, and at 10 ⁶ Ω / square or less, it was confirmed that an excellent destaticizing performance.

Example 19
In Example 17, the polyamide 610 composition (A-2) was changed to the polyamide 6 composition (A-4), and the conductive polyamide 610 composition (D-4) was changed to the conductive polyamide 6 composition (D-12). A laminated tube having a layer structure shown in Table 1 was obtained in the same manner as in Example 17. Table 1 shows the results of measuring the physical properties of the laminated tube. Further, the electrical conductivity of the laminate tube was measured according to SAE J-2260, and at 10 ⁶ Ω / square or less, it was confirmed that an excellent destaticizing performance.

Comparative Example 1
In Example 1, a laminated tube having a layer structure shown in Table 1 was obtained in the same manner as in Example 1 except that EVOH (C-1) was not used. Table 1 shows the results of measuring the physical properties of the laminated tube.

Comparative Example 2
In Example 1, the layer configuration shown in Table 1 was carried out in the same manner as in Example 1 except that the polyamide 12 composition (A-1) and the polyamide 6/66/12 composition (B-1) were not used. Obtained a laminated tube of. Table 1 shows the results of measuring the physical properties of the laminated tube.

Comparative Example 3
A laminated tube having a layer structure shown in Table 1 was obtained in the same manner as in Example 1 except that the polyamide 6/66/12 composition (B-1) was not used in Example 1. Table 1 shows the results of measuring the physical properties of the laminated tube.

Comparative Example 4
In Example 1, the laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 1 except that the polyamide 6/66/12 composition (B-1) was changed to (B-3). Obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Comparative Example 5
In Example 1, the laminated tube having the layer structure shown in Table 1 was prepared in the same manner as in Example 1 except that the polyamide 6/66/12 composition (B-1) was changed to (B-4). Obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Comparative Example 6
Table 1 shows in the same manner as in Example 1 except that the polyamide 6/66/12 composition (B-1) was changed to the polyamide 6/12 composition (B-5) in Example 1. A layered laminated tube was obtained. Table 1 shows the results of measuring the physical properties of the laminated tube.

Comparative Example 7
A laminated tube having a layer structure shown in Table 1 was obtained in the same manner as in Example 1 except that the polyamide 12 composition (D-1) was changed to (A-1) in Example 1. Table 1 shows the results of measuring the physical properties of the laminated tube.

Comparative Example 8
In Example 6, a laminated tube having a layer structure shown in Table 1 was obtained in the same manner as in Example 6 except that the polyamide 610 composition (D-3) was changed to (A-2). Table 1 shows the results of measuring the physical properties of the laminated tube.

Comparative Example 9
In Example 8, a laminated tube having a layer structure shown in Table 1 was obtained in the same manner as in Example 8 except that the polyamide 612 composition (D-5) was changed to (A-3). Table 1 shows the results of measuring the physical properties of the laminated tube.

Comparative Example 10
A laminated tube having a layer structure shown in Table 1 was obtained in the same manner as in Example 14 except that the polyamide 6 composition (D-11) was changed to (A-4) in Example 14. Table 1 shows the results of measuring the physical properties of the laminated tube.

As is clear from Table 1, the laminated tube of Comparative Example 1 having no layer containing the ethylene / vinyl acetate copolymer saponified product specified in the present invention was inferior in chemical permeation prevention property. The laminated tube of Comparative Example 2 which does not have the layer containing the aliphatic polyamide specified in the present invention or the layer containing the polyamide 6/66/12 composition is inferior in low temperature impact resistance and interlayer adhesiveness, and is specified in the present invention. The laminated tube of Comparative Example 3 which did not have a layer containing the polyamide 6/66/12 composition of the above was inferior in interlayer adhesion. The laminated tubes of Comparative Examples 4 to 6 having a polyamide 6/66/12 composition or a layer containing a polyamide 6/12 composition other than those specified in the present invention have interlayer adhesiveness (durability of interlayer adhesiveness) after heat treatment. Was inferior to. The laminated tubes of Comparative Examples 7 to 10 having a layer containing an aliphatic polyamide composition containing a plasticizer other than those specified in the present invention as the innermost layer have a large amount of low molecular weight components eluted by contact with alcohol-containing gasoline. It was inferior in resistance to elution.
On the other hand, the laminated tubes of Examples 1 to 19 specified in the present invention have good properties such as chemical permeation prevention property, interlayer adhesiveness and durability thereof, low temperature impact resistance, and resistance to elution. it is obvious.

Claims (9)

A laminated tube consisting of at least four layers having a layer (a), a layer (b), a layer (c), and a layer (d).
The layer (a) contains an aliphatic polyamide (A) and contains
The layer (b) contains the polyamide 6/66/12 composition (B).
The layer (c) contains an ethylene / vinyl acetate copolymer saponified product (C).
The layer (d) contains the aliphatic polyamide composition (D).
The aliphatic polyamide (A) does not contain poly (caproamide / hexamethylene adipamide / dodecane amide) (polyamide 6/66/12).
The polyamide 6/66/12 composition (B) includes polyhexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene decamide (polyamide 910), and polynonamethylene dodecamide. At least one polyamide and polyamide 6 / selected from the group consisting of (polyamide 912), polydecamethylene decamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), and polydodecamethylene dodecamide (polyamide 1212). Polyamide mixture (B1) consisting of 66/12 50% by mass or more and 98% by mass or less, plastic agent (B2) 1% by mass or more and 20% by mass or less, and an olefin having a bending elasticity of 500 MPa or less measured in accordance with ISO 178. Contains 1% by mass or more and 30% by mass or less of the polymer (B3),
The aliphatic polyamide composition (D) does not contain a plasticizer, and has an olefin weight of 70% by mass or more and 99% by mass or less of the aliphatic polyamide (A) and a bending elasticity of 500 MPa or less measured in accordance with ISO 178. Combined (B3) containing 1% by mass or more and 30% by mass or less,
From the outside, the (a) layer, the (b) layer, the (c) layer, the (d) layer , and the (d) layer are arranged in the innermost layer, and the (b) layer and (c) are arranged. ) Laminated tubes characterized by adjacent layers. The aliphatic polyamide (A) is polycaproamide (polyamide 6), polyundecaneamide (polyamide 11), polydodecaneamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylenedecamide (polyamide 66). Selected from the group consisting of polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecamethylene decamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), and polydodecamethylene dodecamide (polyamide 1212). The laminated tube according to claim 1, wherein the polyamide tube is a copolymer using at least one homopolymer and / or several kinds of raw material monomers forming them. In the polyamide 6/66/12 in the polyamide 6/66/12 composition (B), the mass ratio of the total unit of the caproamide unit and the hexamethylene adipamide unit to the dodecaneamide unit is the caproamide unit and the hexamethylene adipa. The laminated tube according to claim 1 or 2, wherein the amount is 81: 19% by mass or more and 95: 5% by mass or less with respect to a total of 100% by mass of the amide unit and the dodecaneamide unit. Any of claims 1 to 3, wherein the ethylene / vinyl acetate copolymer saponified product (C) has an ethylene content of 15 mol% or more and 60 mol% or less, and a saponification degree of 90 mol% or more. The laminated tube described in. The laminated tube according to any one of claims 1 to 4, wherein the layer (a) is arranged on the outermost layer. It is characterized in that it contains at least two layers (b) and is arranged in the order of the layer (a), the layer (b), the layer (c), the layer (b), and the layer (d) from the outside. The laminated tube according to any one of claims 1 to 5. The laminated tube according to any one of claims 1 to 6, wherein a conductive layer containing an aliphatic polyamide composition (D) further containing a conductive filler is arranged on 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 a coextrusion molding method. The laminated tube according to any one of claims 1 to 8, wherein the laminated tube is used as a fuel tube.