JP6856889B2 - Laminated tube - Google Patents

Description

The present invention relates to laminated tubes.

In the old days, in response to the problem of rusting caused by road antifreeze agents, prevention of global warming, and energy saving in automobile piping tubes, the main material is metal, which is a lightweight resin with excellent rust prevention properties. 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 barrier property to the chemical solution is not sufficient, and improvement in the alcohol-containing gasoline barrier property is particularly required.

As a method for solving this problem, resins having good chemical barrier properties, such as ethylene / vinyl acetate copolymer saponified product (EVOH), polymethoxylylene adipamide (polyamide MXD6), polybutylene terephthalate (PBT), and polyethylene. Naphthalate (PEN), polybutylene naphthalate (PBN), polyphenylene sulfide (PPS), polyvinylidene fluoride (PVDF), ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE) ), Tetrafluoroethylene / Hexafluoropropylene copolymer (TFE / HFP, FEP), Tetrafluoroethylene / Hexafluoropropylene / Vinylidene fluoride copolymer (TFE / HFP / VDF, THV), Tetrafluoroethylene / Hexafluoro Propylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer (TFE / HFP / VDF / PAVE), tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (TFE / PAVE, PFA), tetrafluoroethylene / Hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer (TFE / HFP / PAVE), chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer (CTFE / PAVE / TFE, CPT) are arranged. Laminated tubes have been proposed (see, for example, Patent Document 1 and the like).

Further, a molded product using a conventionally used polyamide-based resin, particularly nylon 11 or nylon 12 having excellent strength, toughness, chemical resistance, and flexibility in the innermost layer, becomes a monomer or a molded product due to contact with the fuel. It has been confirmed that low molecular weight components such as oligomers gradually elute and precipitate in the fuel, and adhesion to the moving parts of the injector and fuel tank valve may cause the engine to become unstartable, or the internal pressure of the fuel tank may be controlled. It has been pointed out that it may be a problem. Polynonamethylene terephthalamide (PA9T) is attracting attention as a tube component having excellent chemical barrier properties and elution resistance of monomers and oligomers, and having a low specific gravity and low cost. The present inventors have prepared a layer made of an aliphatic polyamide, a diamine unit containing 60 mol% or more of 1,9-nonanediamine unit and / or 2-methyl-1,8-octanediamine unit with respect to all diamine units. Lamination comprising at least two layers having a layer made of a semi-aromatic polyamide composed of a dicarboxylic acid unit containing 60 mol% or more of a terephthalic acid unit and / or a naphthalenedicarboxylic acid unit with respect to all the dicarboxylic acid units. A structure has been proposed (see Patent Documents 2 to 5).

In order to improve the interlayer adhesion between the layer made of aliphatic polyamide and the layer made of polynonamethylene terephthalamide (PA9T), the layer made of aliphatic polyamide such as polyamide 12 and polynonamethylene terephthal with excellent chemical barrier properties A laminated tube having a layer made of a semi-aromatic polyamide composition containing a specific organic acid salt (organic acid salt having 10 or more and 24 or less carbon atoms) in a semi-aromatic polyamide such as lamin (PA9T) has been proposed. (See Patent Document 6).
Further, a layer composed of a specific polyamide copolymer composed of hexamethylenediamine, terephthalic acid and an aliphatic dicarboxylic acid having 8 or more and less than 19 carbon atoms, m- and / or p-xylylene diamine, and 4 or more carbon atoms 12 It consists of a laminated structure having a layer made of a semi-aromatic polyamide made of less than aliphatic dicarboxylic acid, or a specific polyamide copolymer made of hexamethylenediamine, terephthalic acid and an aliphatic dicarboxylic acid having 8 or more and less than 19 carbon atoms. A laminated structure having a layer and a layer made of a semi-aromatic polyamide composed of an aromatic dicarboxylic acid such as terephthalic acid and an aliphatic diamine has been proposed (see Patent Documents 7 and 8).

U.S. Pat. No. 5,554,425 Japanese Unexamined Patent Publication No. 2004-203012 Publication No. 2005-58600 Publication No. 2005-102681 Publication No. 2005-102964 Japanese Unexamined Patent Publication No. 2011-214592 Japanese Unexamined Patent Publication No. 2016-172445 Japanese Unexamined Patent Publication No. 2016-172449

In the laminated tubes described in Patent Documents 2 to 5, it is not necessary to provide an adhesive layer between the layer made of aliphatic polyamide and the layer made of polynonamethylene terephthalamide (PA9T), and the initial interlayer adhesiveness is sufficient. Is. However, there is still room for improvement in the durability of interlayer adhesion after contacting / immersing in fuel for a long time, after heat treatment, or the like. Further, with respect to the laminated tube described in Patent Document 6, further improvement in the durability of interlayer adhesiveness is desired as in the above technique.
Further, in the examples of Patent Document 7, polymethoxylylen adipamide (polyamide MXD6) is used as a semi-aromatic polyamide composed of m- and / or p-xylylene diamine and an aliphatic dicarboxylic acid having 4 or more and less than 12 carbon atoms. ), And although there is disclosure of data on interlayer adhesion, it consists of a diamine unit containing xylylene diamine and / or naphthalenedimethylamine unit and an aliphatic dicarboxylic acid unit having 9 and / or 10 carbon atoms. There is no disclosure or technical suggestion of specific technical data on interlayer adhesion to semi-aromatic polyamide and its durability, and as will be described later, the tube has long-term resistance (chemical resistance) to calcium chloride and zinc chloride. Inferior to, further improvement is desired. Also in the examples of Patent Document 8, as a semi-aromatic polyamide copolymer composed of an aromatic dicarboxylic acid, a poly (hexamethylene dodecamide / hexamethylene terephthalamide) which is the same as the inner and outer layer materials and does not contain an impact improving material. Although copolymers are mentioned and data on interlayer adhesion are disclosed, a semi-aromatic polyamide composed of an aliphatic diamine having 9 and / or 10 carbon atoms and a terephthalic acid unit and / or a naphthalenedicarboxylic acid unit. There is no disclosure or technical suggestion of specific technical data on the interlayer adhesion with and its durability, and as will be described later, the tube is inferior in long-term resistance (chemical resistance) to calcium chloride and zinc chloride, and further. Improvement is desired.
An object of the present invention is to solve the above problems and maintain various properties such as chemical barrier property, low temperature impact resistance, and elution resistance of monomers and oligomers, while maintaining high temperature fracture pressure, chemical resistance, and interlayer adhesion. , And to provide a laminated tube having excellent durability thereof.

As a result of diligent studies to solve the above problems, the present inventors have made a constituent unit derived from a polyamide copolymer having a specific structure and an unsaturated compound having a carboxyl group and / or an acid anhydride group. It has a layer containing a polyamide copolymer composition containing a specific amount of an elastomer polymer containing the above and a layer containing a semi-aromatic polyamide composition containing a semi-aromatic polyamide having a specific structure, and both layers are adjacent to each other. Laminated tubes have excellent chemical barrier properties, low-temperature impact resistance, monomer and oligomer elution resistance, as well as high-temperature breaking pressure, chemical resistance, interlayer adhesion, and durability. I found that I could get it.

That is, the present invention
A laminated tube having two or more layers including a layer (a) and a layer (b).
At least one set of the layer (a) and the layer (b) are arranged adjacent to each other.
The layer (a) contains the polyamide copolymer composition (A).
The layer (b) contains the semi-aromatic polyamide composition (B) and contains.
The polyamide copolymer composition (A) contains a polyamide copolymer (A1) and an elastomer polymer (A2).
The polyamide copolymer (A1) is a unit derived from (a1) an aliphatic diamine having 6 or more and 12 or less carbon atoms and an aliphatic dicarboxylic acid having 9 or more and 18 or less carbon atoms, or (a2) the number of carbon atoms. Units derived from 10 to 12 lactams and / or aliphatic aminocarboxylic acids, and (a3) units derived from aliphatic diamines and terephthalic acids having 9 or 10 carbon atoms and / or naphthalenedicarboxylic acids, or (A4) Containing units derived from xylylene diamine and / or bis (aminomethyl) naphthalene and an aliphatic dicarboxylic acid having 9 or 10 carbon atoms, (a1) or (a2) and (a3) or (a4). The molar ratio of is 55:45 mol% or more and 90:10 mol% or less, and 70% by mass or more and 95% by mass or less is contained in the polyamide copolymer composition (A).
The elastomer polymer (A2) contains a structural unit derived from an unsaturated compound having a carboxyl group and / or an acid anhydride group, and is contained in the polyamide copolymer composition (A) in an amount of 5% by mass or more of 30. Contains less than% by mass,
The semi-aromatic polyamide composition (B) contains a semi-aromatic polyamide (B1) or a semi-aromatic polyamide (B2).
The semi-aromatic polyamide (B1) contains 50 mol% or more of an aliphatic diamine unit having 9 or 10 carbon atoms with respect to the total diamine units of the semi-aromatic polyamide (B1), and the semi-aromatic polyamide (B1). B1) contains 50 mol% or more of terephthalic acid units and / or naphthalenedicarboxylic acid units with respect to all dicarboxylic acid units.
The semi-aromatic polyamide (B2) contains 50 mol% or more of xylylenediamine units and / or bis (aminomethyl) naphthalene units with respect to the total diamine units of the semi-aromatic polyamide (B2), and the semi-aromatic polyamide (B2). It is a laminated tube containing 50 mol% or more of an aliphatic dicarboxylic acid unit having 9 or 10 carbon atoms with respect to all the dicarboxylic acid units of the group polyamide (B2).

A preferred embodiment of the laminated tube is shown below. A plurality of preferred embodiments can be combined.
[1] In the polyamide copolymer (A1), the unit derived from (a1) an aliphatic diamine having 6 or more and 12 or less carbon atoms and an aliphatic dicarboxylic acid having 9 or more and 18 or less carbon atoms is hexamethylene se. Bacamido, hexamethylene dodecamide, hexamethylene tetradecamide, nonamethylene azelamide, nonamethylene sebacamide, nonamethylene dodecamide, nonamethylene tetradecamide, 2-methyloctamethylene azelamide, 2-methyloctamethylenese Bacamide, 2-methyloctamethylene dodecamide, 2-methyloctamethylenetetradecamide, decamethylene azelamide, decamethylene sebacamide, decamethylene dodecamide, decamethylenetetradecamide, dodecamethylene azelamide, dodecamethylenese A unit derived from (a2) lactam having 10 or more and 12 or less carbon atoms and / or an aliphatic aminocarboxylic acid, which is at least one raw material monomer selected from the group consisting of bacamide and dodecamethylene dodecamide. Is at least one raw material monomer selected from the group consisting of 11-aminoundecanoic acid, 12-aminododecanoic acid, and dodecanthactam, and (a3) an aliphatic diamine having 9 or 10 carbon atoms and a terephthalic acid. And / or the unit derived from the naphthalenedicarboxylic acid is at least one raw material monomer selected from the group consisting of nonamethylene terephthalamide, 2-methyloctamethylene terephthalamide, and decamethylene terephthalamide. , (A4) Xylylene diamine and / or bis (aminomethyl) naphthalene and aliphatic dicarboxylic acids having 9 or 10 carbon atoms are the units derived from metaxylylene azelamide, metaxylylene sebacamide, paraxili. A laminated tube which is at least one raw material monomer selected from the group consisting of lenazelamide and paraxylylene sebacamide.
[2] A laminated tube in which the semi-aromatic polyamide composition (B) contains the elastomer polymer (A2).
[3] A laminated tube in which the layer (b) is arranged adjacent to the inside of the layer (a).
[4] Further including the layer (c), at least one set of the layer (b) and the layer (c) are arranged adjacent to each other, and the layer (c) has reactivity with an amino group. A laminated tube containing a fluorine-containing polymer (C) in which a functional group is introduced into a molecular chain.
[5] A laminated tube in which the layer (c) is arranged inside the layer (b).
[6] A laminated tube in which the innermost layer is a conductive layer containing a thermoplastic resin composition containing a conductive filler.
[7] Laminated tube manufactured by coextrusion molding.
[8] A laminated tube used as a fuel tube.

According to the present invention, a laminated tube having excellent chemical resistance, interlayer adhesion, and durability thereof is provided while maintaining various properties such as chemical barrier property, low temperature impact resistance, and elution resistance of monomers and oligomers. be able to.

1. 1. Layer (a) The layer (a) of the laminated tube contains the polyamide copolymer composition (A).

[Polyamide copolymer composition (A)]
The polyamide copolymer composition (A) contains a polyamide copolymer (A1) and an elastomer polymer (A2), and the polyamide copolymer (A1) is (a1) an aliphatic having 6 or more and 12 or less carbon atoms. A unit derived from a diamine and an aliphatic dicarboxylic acid having 9 or more and 18 or less carbon atoms, or (a2) a unit derived from a lactam having 10 or more and 12 or less carbon atoms and / or an aliphatic aminocarboxylic acid, and (a3). ) A unit derived from an aliphatic diamine having 9 or 10 carbon atoms and terephthalic acid and / or a naphthalenedicarboxylic acid, or (a4) xylylene diamine and / or bis (aminomethyl) naphthalene and 9 or 10 carbon atoms. A polyamide copolymer containing a unit derived from an aliphatic dicarboxylic acid, having a molar ratio of (a1) or (a2) to (a3) or (a4) of 55:45 mol% or more and 90:10 mol% or less. The composition (A) contains 70% by mass or more and 95% by mass or less, and the elastomer polymer (A2) contains a structural unit derived from an unsaturated compound having a carboxyl group and / or an acid anhydride group. , 5% by mass or more and 30% by mass or less is contained in the polyamide copolymer composition (A) (hereinafter, may be referred to as a polyamide copolymer composition (A)).

[Polyamide copolymer (A1)]
The polyamide copolymer (A1) has an amide bond (-CONH-) in the main chain, and (a1) an aliphatic diamine having 6 to 12 carbon atoms and an aliphatic dicarboxylic having 9 to 18 carbon atoms. Units derived from acids, or (a2) units derived from lactams with 10 or more and 12 or less carbon atoms and / or aliphatic aminocarboxylic acids, and (a3) aliphatic diamines and terephthals having 9 or 10 carbon atoms. Contains units derived from acids and / or naphthalenedicarboxylic acids, or (a4) xylylene diamines and / or bis (aminomethyl) naphthalene and units derived from aliphatic dicarboxylic acids having 9 or 10 carbon atoms. The molar ratio of a1) or (a2) to (a3) or (a4) is 55:45 mol% or more and 90:10 mol% or less (hereinafter, may be referred to as a polyamide copolymer (A1)).

A unit derived from (a1) an aliphatic diamine having 6 or more and 12 or less carbon atoms and an aliphatic dicarboxylic acid having 9 or more and 18 or less carbon atoms in the polyamide copolymer (A1), or (a2) 10 carbon atoms. Units derived from 12 or less lactams and / or aliphatic aminocarboxylic acids, and (a3) units derived from aliphatic diamines and terephthalic acids having 9 or 10 carbon atoms and / or naphthalenedicarboxylic acids, or ( a4) The content of the unit derived from xylylene diamine and / or bis (aminomethyl) naphthalene and an aliphatic dicarboxylic acid having 9 or 10 carbon atoms is 100, which is the total monomer unit of the polyamide copolymer (A1). The molar ratio of (a1) or (a2) to (a3) or (a4) is 55:45 mol% or more and 90:10 mol% or less, and 60:40 mol% or more and 85:15 mol. % Or less, preferably 65:35 mol% or more and 80:20 mol% or less.
(A1) A unit derived from an aliphatic diamine having 6 to 12 carbon atoms and an aliphatic dicarboxylic acid having 9 to 18 carbon atoms, or (a2) a lactam having 10 to 12 carbon atoms and / or a fat. If the content of the unit derived from the group aminocarboxylic acid is less than the above value, the mechanical properties and chemical resistance of the obtained laminated tube are inferior, while if it exceeds the above value, the obtained laminated tube The interlayer adhesiveness and its durability are inferior.
(A3) A unit derived from an aliphatic diamine having 9 or 10 carbon atoms and terephthalic acid and / or a naphthalenedicarboxylic acid, or (a4) xylylenediamine and / or bis (aminomethyl) naphthalene and 9 or 9 carbon atoms. If the content of the unit derived from the aliphatic dicarboxylic acid of 10 is less than the above value, the interlayer adhesiveness and durability of the obtained laminated tube are inferior, while if it exceeds the above value, the obtained lamination is obtained. Poor mechanical properties and chemical resistance of the tube.

(A1) As the aliphatic diamine having 6 or more and 12 or less carbon atoms in the unit derived from the aliphatic diamine having 6 or more and 12 or less carbon atoms and the aliphatic dicarboxylic acid having 9 or more and 18 or less carbon atoms, 1, 6-Hexanediamine, 1,7-Heptanediamine, 1,8-octanediamine, 1,9-nonandiamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13- Tridecanediamine, 1-butyl-1,2-ethanediamine, 1,1-dimethyl-1,4-butanediamine, 1-ethyl-1,4-butanediamine, 1,2-dimethyl-1,4-butane Diamine, 1,3-dimethyl-1,4-butanediamine, 1,4-dimethyl-1,4-butanediamine, 2,3-dimethyl-1,4-butanediamine, 2-methyl-1,5-pentane Diamine, 3-methyl-1,5-pentanediamine, 2,5-dimethyl-1,6-hexanediamine, 2,4-dimethyl-1,6-hexanediamine, 3,3-dimethyl-1,6-hexane Diamine, 2,2-dimethyl-1,6-hexanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2,4-diethyl -1,6-hexanediamine, 2,2-dimethyl-1,7-heptanediamine, 2,3-dimethyl-1,7-heptanediamine, 2,4-dimethyl-1,7-heptanediamine, 2,5 −Diamine-1,7-heptanediamine, 2-methyl-1,8-octanediamine, 3-methyl-1,8-octanediamine, 4-methyl-1,8-octanediamine, 1,3-dimethyl-1 , 8-octane diamine, 1,4-dimethyl-1,8-octane diamine, 2,4-dimethyl-1,8-octane diamine, 3,4-dimethyl-1,8-octane diamine, 4,5-dimethyl -1,8-octanediamine, 2,2-dimethyl-1,8-octanediamine, 3,3-dimethyl-1,8-octanediamine, 4,4-dimethyl-1,8-octanediamine, 5-methyl -1,9-nonandiamine and the like can be mentioned. These can be used alone or in combination of two or more.

(A1) Azeline is an aliphatic dicarboxylic acid having 9 or more and 18 or less carbon atoms in a unit derived from an aliphatic diamine having 6 or more and 12 or less carbon atoms and an aliphatic dicarboxylic acid having 9 or more and 18 or less carbon atoms. Acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecanedioic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyl Examples thereof include adipic acid and 2-butylsveric acid. These can be used alone or in combination of two or more.

(A2) Examples of the lactam having 10 or more and 12 or less carbon atoms and / or the lactam having 10 or more and 12 or less carbon atoms in the unit derived from the aliphatic aminocarboxylic acid include decane lactam, undecane lactam, and dodecane lactam. .. Examples of the aliphatic aminocarboxylic acid having 10 or more and 12 or less carbon atoms include 10-aminodecanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. These can be used alone or in combination of two or more.

(A3) As the aliphatic diamine having 9 or 10 carbon atoms in the unit derived from the aliphatic diamine having 9 or 10 carbon atoms and terephthalic acid and / or naphthalenedicarboxylic acid, 1,9-nonanediamine, 1, Examples thereof include 10-decanediamine. 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2,4-diethyl-1,6-hexane as long as the number of carbon atoms satisfies the above. Diamine, 2,2-dimethyl-heptanediamine, 2,3-dimethyl-heptanediamine, 2,4-dimethyl-heptanediamine, 2,5-dimethyl-heptanediamine, 2-methyl-1,8-octanediamine, 3 -Methyl-1,8-octanediamine, 4-methyl-1,8-octanediamine, 1,3-dimethyl-1,8-octanediamine, 1,4-dimethyl-1,8-octanediamine, 2,2 −Diamine-1,8-octanediamine, 2,4-dimethyl-1,8-octanediamine, 3,3-dimethyl-1,8-octanediamine, 3,4-dimethyl-1,8-octanediamine, 4 , 4-Dimethyl-1,8-octanediamine, 4,5-dimethyl-1,8-octanediamine, 2-methyl-1,9-nonanediamine, 3-methyl-1,9-nonanediamine, 4-methyl-1 , 9-Nonandiamine, 5-Methyl-1,9-Nonandiamine and the like may be contained in a branched chain aliphatic diamine. These can be used alone or in combination of two or more.

Among these, 1,9-nonanediamine, 2-methyl-1,8-octanediamine, and 1,10-decanediamine are preferable from the viewpoint of availability and economy. Furthermore, when 1,9-nonandiamine and 2-methyl-1,8-octanediamine are used in combination, the molar ratio of 1,9-nonandiamine unit and 2-methyl-1,8-octanediamine is the moldability and impact resistance. From the viewpoint of sex balance, it is preferably 30:70 mol% or more and 98: 2 mol% or less, and more preferably 40:60 mol% or more and 95: 5 mol% or less.

(A3) The naphthalenedicarboxylic acid unit among the units derived from the aliphatic diamine having 9 or 10 carbon atoms and terephthalic acid and / or naphthalenedicarboxylic acid includes 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid. Examples thereof include acids, 1,4-naphthalenedicarboxylic acids and 1,5-naphthalenedicarboxylic acids. These can be used alone or in combination of two or more. Among these, units derived from 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid are preferable from the viewpoint of availability and economy.

(A4) Examples of the xylylenediamine in the unit derived from xylylenediamine and / or bis (aminomethyl) naphthalene and an aliphatic dicarboxylic acid having 9 or 10 carbon atoms include o-xylylenediamine and m-xylylenedi. Examples include amines and p-xylylenediamines. These can be used alone or in combination of two or more. Among these, m-xylylenediamine and p-xylylenediamine are preferable from the viewpoint of availability and economy.
As bis (aminomethyl) naphthalene, 1,4-bis (aminomethyl) naphthalene, 1,5-bis (aminomethyl) naphthalene, 2,6-bis (aminomethyl) naphthalene, 2,7-bis (aminomethyl) ) Naphthalene and the like can be mentioned. These can be used alone or in combination of two or more. Among these, 1,5-bis (aminomethyl) naphthalene and 2,6-bis (aminomethyl) naphthalene are preferable from the viewpoint of availability and economy.

(A4) Azelaic acid is an aliphatic dicarboxylic acid having 9 or 10 carbon atoms in a unit derived from xylylene diamine and / or bis (aminomethyl) naphthalene and an aliphatic dicarboxylic acid having 9 or 10 carbon atoms. , Sebacic acid and the like. As long as the number of carbon atoms satisfies the above, it may contain a branched chain aliphatic dicarboxylic acid such as 2,2,4-trimethylazipic acid and 2,4,4-trimethylazipic acid. These can be used alone or in combination of two or more. Among these, azelaic acid and sebacic acid are preferable from the viewpoint of availability and economy.

As the polyamide copolymer (A1), it is necessary to sufficiently secure various physical properties such as mechanical properties, heat resistance, and chemical resistance of the obtained laminated tube, and the semi-aromatic polyamide composition (B) described later. From the viewpoint of obtaining sufficient interlayer adhesion and durability thereof, poly (hexamethylene sebacamide / nonamethylene terephthalamide) copolymer (polyamide 610 / 9T), poly (hexamethylene dodecamide / nonamethylene terephthalamide) ) Copolymer (Polyamide 612 / 9T), Poly (Hexamethylenetetradecamide / Nonamethylene terephthalamide) Copolymer (Polyamide 614 / 9T), Poly (Hexamethylene hexadecamide / Nonamethylene terephthalamide) Polymer (polyamide 616 / 9T), poly (hexamethylene octadecamide / nonamethylene terephthalamide) copolymer (polyamide 618 / 9T), poly (nonamethylene azelamide / nonamethylene terephthalamide) copolymer ( Polyamide 99 / 9T), poly (nonamethylene sebacamide / nonamethylene terephthalamide) copolymer (polyamide 910 / 9T), poly (nonamethylene dodecamide / nonamethylene terephthalamide) copolymer (polyamide 912 / 9T), poly (nonamethylenetetradecamide / nonamethylene terephthalamide) copolymer (polyamide 914 / 9T), poly (decamethylene azelamide / nonamethylene terephthalamide) copolymer (polyamide 109 / 9T), Poly (decamethylene sebacamide / nonamethylene terephthalamide) copolymer (polyamide 1010 / 9T), poly (decamethylene dodecamide / nonamethylene terephthalamide) copolymer (polyamide 1012 / 9T), poly (deca) Methylenetetradecamide / nonamethylene terephthalamide) copolymer (polyamide 1014 / 9T), poly (dodecamethylene azelamide / nonamethylene terephthalamide) copolymer (polyamide 129 / 9T), poly (dodecamethylene sebaca) Mid / nonamethylene terephthalamide) copolymer (polyamide 1210 / 9T), poly (dodecamethylene dodecamide / nonamethylene terephthalamide) copolymer (polyamide 1212 / 9T), poly (undecanamide / nonamethylene terephthalamide) Lamid) copolymer (polyamide 11 / 9T), poly (dodecaneamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 12 / 9T),
Poly (hexamethylene sebacamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 610 / 9T / M8T), poly (hexamethylene dodecamide / nonamethylene terephthalamide / 2- Methyloctamethylene terephthalamide) copolymer (polyamide 612 / 9T / M8T), poly (hexamethylenetetradecamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 614 / 9T) / M8T), poly (hexamethylene hexadecamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 616 / 9T / M8T), poly (hexamethylene octadecamide / nonamethylene tele) Phthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 618 / 9T / M8T), poly (nonamethylene azelamide / 2-methyloctamethylene azelamide / nonamethylene terephthalamide / 2-methyloctamethylene Telephthalamide) copolymer (polyamide 99 / M89 / 9T / M8T), poly (nonamethylene sebacamide / 2-methyloctamethylene sebacamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) Copolymer (polyamide 910 / M810 / 9T / M8T), poly (nonamethylene dodecamide / 2-methyloctamethylenedodecamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 912) / M812 / 9T / M8T), poly (nonamethylenetetradecamide / 2-methyloctamethylenetetradecamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 914 / M814 / 9T) / M8T), poly (decamethylene azelamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 109 / 9T / M8T), poly (decamethylene sebacamide / nonamethylene terephthalamide) Lamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 1010 / 9T / M8T), poly (decamethylene dodecamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide) 1012 / 9T / M8T), poly (decamethylenetetradecamide / nonamethylene terephthalamide / 2-methyloctameti) Lentelephthalamide) copolymer (polyamide 1014 / 9T / M8T), poly (dodecamethylene azelamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 129 / 9T / M8T) , Poly (dodecamethylene sebacamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 1210 / 9T / M8T), poly (dodecamethylene dodecamide / nonamethylene terephthalamide / 2) -Methyloctamethylene terephthalamide) copolymer (polyamide 1212 / 9T / M8T), poly (undecaneamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 11 / 9T / M8T) ), Poly (dodecaneamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 12 / 9T / M8T),
Poly (hexamethylene sebacamide / decamethylene terephthalamide) copolymer (polyamide 610 / 10T), poly (hexamethylene dodecamide / decamethylene terephthalamide) copolymer (polyamide 612 / 10T), poly (hexa) Methylenetetradecamide / decamethylene terephthalamide) copolymer (polyamide 614 / 10T), poly (hexamethylene hexadecamide / decamethylene terephthalamide) copolymer (polyamide 616 / 10T), poly (hexamethylene octalamide) Decamide / decamethylene terephthalamide) copolymer (polyamide 618 / 10T), poly (nonamethylene azelamide / decamethylene terephthalamide) copolymer (polyamide 99 / 10T), poly (nonamethylene sebacamide / Decamethylene terephthalamide) copolymer (polyamide 910 / 10T), poly (nonamethylene dodecamide / decamethylene terephthalamide) copolymer (polyamide 912 / 10T), poly (nonamethylenetetradecamide / decamethylene tere) Phtalamide) copolymer (polyamide 914 / 10T), poly (nonamethylene azelamide / 2-methyloctamethylene azelamide / decamethylene terephthalamide) copolymer (polyamide 99 / M89 / 10T), poly (nonamethylene) Sebacamide / 2-methyloctamethylene sebacamide / decamethylene terephthalamide) copolymer (polyamide 910 / M810 / 10T), poly (nonamethylene dodecamide / 2-methyloctamethylene dodecamide / decamethylene terephthalamide) Lamide) copolymer (polyamide 912 / M812 / 10T), poly (nonamethylenetetradecamide / 2-methyloctamethylenetetradecamide / decamethylene terephthalamide) copolymer (polyamide 914 / M814 / 10T), poly (Decamethylene azelamide / decamethylene terephthalamide) copolymer (polyamide 109 / 10T), poly (decamethylene sebacamide / decamethylene terephthalamide) copolymer (polyamide 1010 / 10T), poly (decamethylene 10 / 10T), poly (decamethylene terephthalamide) Dodecamide / decamethylene terephthalamide) copolymer (polyamide 1012 / 10T), poly (decamethylenetetradecamide / decamethylene terephthalamide) copolymer (polyamide 1014 / 10T), poly (dodecamethylene azelamide / Decamethylene terephthalamide) copolymer (polyamide 129 / 10T), poly (dodecamethylene sebacamide / decamethylene tele) Phtalamide) copolymer (polyamide 1210 / 10T), poly (dodecamethylene dodecamide / decamethylene terephthalamide) copolymer (polyamide 1212 / 10T), poly (undecaneamide / decamethylene terephthalamide) copolymer ( Polyamide 11 / 10T), poly (dodecaneamide / decamethylene terephthalamide) copolymer (polyamide 12 / 10T),
Poly (hexamethylene sebacamide / metaxylylene azelamide) copolymer (polyamide 610 / MXD9), poly (hexamethylene dodecamide / metaxylylene azelamide) copolymer (polyamide 612 / MXD9), poly (hexa) Methylenetetradecamide / Metaxylylene Azelamide) Copolymer (Polyamide 614 / MXD9), Poly (Hexamethylene Hexadecamido / Metaxylylene Azelamide) Copolymer (Polyamide 616 / MXD9), Poly (Hexamethylene Octa) Decamide / metaxylylene azelamide) copolymer (polyamide 618 / MXD9), poly (nonamethylene azelamide / metaxylylene azelamide) copolymer (polyamide 99 / MXD9), poly (nonamethylene sebacamide / Metaxylylene azelamide) copolymer (polyamide 910 / MXD9), poly (nonamethylenedodecamide / metaxylylene azelamide) copolymer (polyamide 912 / MXD9), poly (nonamethylenetetradecamide / metaxylylene) Azelamide) copolymer (polyamide 914 / MXD9), poly (nonamethylene azelamide / 2-methyloctamethylene azelamide / metaxylylene azelamide) copolymer (polyamide 99 / M89 / MXD9), poly (nonamethylene) Sebacamide / 2-methyloctamethylene sebacamide / metaxylylene azelamide) copolymer (polyamide 910 / M810 / MXD9), poly (nonamethylene dodecamide / 2-methyloctamethylene dodecamide / metaxylylene aze) Lamid) copolymer (polyamide 912 / M812 / MXD9), poly (nonamethylenetetradecamide / 2-methyloctamethylenetetradecamide / metaxylylene azelamide) copolymer (polyamide 914 / M814 / MXD9), poly (Decamethylene azelamide / metaxylylene azelamide) copolymer (polyamide 109 / MXD9), poly (decamethylene sebacamide / metaxylylene azelamide) copolymer (polyamide 1010 / MXD9), poly (decamethylene) Dodecamide / Metaxylylene Azelamide) Copolymer (Polyamide 1012 / MXD9), Poly (Decamethylenetetradecamide / Metaxylylene Azelamide) Copolymer (Polyamide 1014 / MXD9), Poly (Dodecamethylene Azelamide / Metaxylylene azelamide) copolymer (polyamide 129 / MXD9), poly (dodecamethylene sebacamide / metaxylylene) Zeramide) Copolymer (Polyamide 1210 / MXD9), Poly (Dodecamethylene Dodecamide / Metaxylylene Azelamide) Polymer (Polyamide 1212 / MXD9), Poly (Undecaneamide / Metaxylylene Azelamide) Copolymer ( Polyamide 11 / MXD9), poly (dodecaneamide / metaxylylene azelamide) copolymer (polyamide 12 / MXD9),
Poly (hexamethylene sebacamide / metaxylylene sebacamide) copolymer (polyamide 610 / MXD10), poly (hexamethylene dodecamide / metaxylylene sebacamide) copolymer (polyamide 612 / MXD10), poly (Hexamethylenetetradecamide / Metaxylylene sebacamide) copolymer (Polyamide 614 / MXD10), Poly (Hexamethylene hexadecamide / Metaxylylene sevacamido) copolymer (Polyamide 616 / MXD10), Poly (Hexamethylene octadecamide / metaxylylene sebacamide) copolymer (polyamide 618 / MXD10), poly (nonamethylene azelamide / metaxylylene sebacamide) copolymer (polyamide 99 / MXD10), poly (polyamide 99 / MXD10) Nonamethylene sebacamide / metaxylylene sebacamide) copolymer (polyamide 910 / MXD10), poly (nonamethylene dodecamide / metaxylylene sebacamide) copolymer (polyamide 912 / MXD10), poly (nona) Methylenetetradecamide / metaxylylene sevacamido) copolymer (polyamide 914 / MXD10), poly (nonamethylene azelamide / 2-methyloctamethylene azelamide / metaxylylene sevacamido) copolymer (polyamide 99) / M89 / MXD10), poly (nonamethylene sebacamide / 2-methyloctamethylene sebacamide / metaxylylene sebacamide) copolymer (polyamide 910 / M810 / MXD10), poly (nonamethylene dodecamide / 2) -Methyloctamethylene dodecamide / metaxylylene sebacamide) copolymer (polyamide 912 / M812 / MXD10), poly (nonamethylenetetradecamide / 2-methyloctamethylenetetradecamide / metaxylylene sebacamide) Copolymer (Polyamide 914 / M814 / MXD10), Poly (Decamethylene Azelamide / Metaxylylene sebacamide) Copolymer (Polyamide 109 / MXD10), Poly (Decamethylene sebacamide / Metaxylylene sebacamide) ) Copolymer (Polyamide 1010 / MXD10), Poly (Decamethylenedodecamide / Metaxylylene sebacamide) Copolymer (Polyamide 1012 / MXD10), Poly (Decamethylenetetradecamide / Metaxylylene sebacamide) Copolymer (Polyamide 1014 / MXD10), Poly (Dodecamethylene Azelamide / Metaxylylene sebacamide) Copolymer (Polyamide 129 / MXD10), Poly (Dodeca) Methylene sebacamide / metaxylylene sebacamide) copolymer (polyamide 1210 / MXD10), poly (dodecamethylene dodecamide / metaxylylene sebacamide) copolymer (polyamide 1212 / MXD10), poly (undecaneamide) / Metaxylylene sebacamide) copolymer (polyamide 11 / MXD10), poly (dodecaneamide / metaxylylene sebacamide) copolymer (polyamide 12 / MXD10),
Poly (hexamethylene sebacamide / paraxylylene azelamide) copolymer (polyamide 610 / PXD9), poly (hexamethylene dodecamide / paraxylylene azelamide) copolymer (polyamide 612 / PXD9), poly (hexa) Methylenetetradecamide / paraxylylene azelamide) copolymer (polyamide 614 / PXD9), poly (hexamethylene hexadecamide / paraxylylene azelamide) copolymer (polyamide 616 / PXD9), poly (hexamethylene octa) Decamide / paraxylylene azelamide) copolymer (polyamide 618 / PXD9), poly (nonamethylene azelamide / paraxylylene azelamide) copolymer (polyamide 99 / PXD9), poly (nonamethylene sebacamide / Paraxylylene azelamide) copolymer (polyamide 910 / PXD9), poly (nonamethylene dodecamide / paraxylylene azelamide) copolymer (polyamide 912 / PXD9), poly (nonamethylenetetradecamide / paraxylylene) Azelamide) copolymer (polyamide 914 / PXD9), poly (nonamethylene azelamide / 2-methyloctamethylene azelamide / paraxylylene azelamide) copolymer (polyamide 99 / M89 / PXD9), poly (nonamethylene) Sebacamide / 2-methyloctamethylene sebacamide / paraxylylene azelamide) copolymer (polyamide 910 / M810 / PXD9), poly (nonamethylene dodecamide / 2-methyloctamethylene dodecamide / paraxylylene aze) Lamid) copolymer (polyamide 912 / M812 / PXD9), poly (nonamethylenetetradecamide / 2-methyloctamethylenetetradecamide / paraxylylene azelamide) copolymer (polyamide 914 / M814 / PXD9), poly (Decamethylene azelamide / paraxylylene azelamide) copolymer (polyamide 109 / PXD9), poly (decamethylene sebacamide / paraxylylene azelamide) copolymer (polyamide 1010 / PXD9), poly (decamethylene) Dodecamide / paraxylylene azelamide) copolymer (polyamide 1012 / PXD9), poly (decamethylenetetradecamide / paraxylylene azelamide) copolymer (polyamide 1014 / PXD9), poly (polyamide 1014 / PXD9), poly (dodecamethylene azelamide / Paraxylylene azelamide) copolymer (polyamide 129 / PXD9), poly (dodecamethylene sebacamide / paraxylylene) Zeramide) Copolymer (Polyamide 1210 / PXD9), Poly (Dodecamethylene Dodecamide / Paraxylylene Azelamide) Polymer (Polyamide 1212 / PXD9), Poly (Undecaneamide / Paraxylylene Azelamide) Copolymer ( Polyamide 11 / PXD9), poly (dodecaneamide / paraxylylene azelamide) copolymer (polyamide 12 / PXD9),
Poly (hexamethylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 610 / PXD10), poly (hexamethylene dodecamide / paraxylylene sebacamide) copolymer (polyamide 612 / PXD10), poly (Hexamethylenetetradecamide / paraxylylene sevacamido) copolymer (polyamide 614 / PXD10), poly (hexamethylene hexadecamide / paraxylylene sevacamido) copolymer (polyamide 616 / PXD10), poly (Hexamethylene octadecamide / paraxylylene sebacamide) copolymer (polyamide 618 / PXD10), poly (nonamethylene azelamide / paraxylylene sebacamide) copolymer (polyamide 99 / PXD10), poly (polyamide 99 / PXD10) Nonamethylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 910 / PXD10), poly (nonamethylene dodecamide / paraxylylene sebacamide) copolymer (polyamide 912 / PXD10), poly (nona) Methylenetetradecamide / paraxylylene sebacamide) copolymer (polyamide 914 / PXD10), poly (nonamethylene azelamide / 2-methyloctamethylene azelamide / paraxylylene sebacamide) copolymer (polyamide 99) / M89 / PXD10), poly (nonamethylene sebacamide / 2-methyloctamethylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 910 / M810 / PXD10), poly (nonamethylene dodecamide / 2) -Methyloctamethylene dodecamide / paraxylylene sebacamide) copolymer (polyamide 912 / M812 / PXD10), poly (nonamethylenetetradecamide / 2-methyloctamethylenetetradecamide / paraxylylene sebacamide) Copolymer (Polyamide 914 / M814 / PXD10), Poly (Decamethylene Azelamide / Paraxylylene sebacamide) Copolymer (Polyamide 109 / PXD10), Poly (Decamethylene sebacamide / Paraxylylene sebacamide) ) Copolymer (Polyamide 1010 / PXD10), Poly (Decamethylenedodecamide / Paraxylylene sebacamide) Copolymer (Polyamide 1012 / PXD10), Poly (Decamethylenetetradecamide / Paraxylylene sebacamide) Copolymer (Polyamide 1014 / PXD10), Poly (Dodecamethylene Azelamide / Paraxylylene sebacamide) Copolymer (Polyamide 129 / PXD10), Poly (Dodeca) Methylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 1210 / PXD10), poly (dodecamethylene dodecamide / paraxylylene sebacamide) copolymer (polyamide 1212 / PXD10), poly (undecanamide) / Paraxylylene sebacamide) copolymer (polyamide 11 / PXD10), poly (dodecaneamide / paraxylylene sebacamide) copolymer (polyamide 12 / PXD10),
Poly (hexamethylene sebacamide / metaxylylene azelamide / paraxylylene azelamide) copolymer (polyamide 610 / MXD9 / PXD9), poly (hexamethylene dodecamide / metaxylylene azelamide / paraxylylene azelamide) ) Copolymer (Polyamide 612 / MXD9 / PXD9), Poly (Hexamethylenetetradecamide / Metaxylylene Azelamide / Paraxylylene Azelamide) Copolymer (Polyamide 614 / MXD9 / PXD9), Poly (Hexamethylene Hexa) Decamide / Metaxylylene Azelamide / Paraxylylene Azelamide) Copolymer (Polyamide 616 / MXD9 / PXD9), Poly (Hexamethylene Octadecamide / Metaxylylene Azelamide / Paraxylylene Azelamide) Copolymer (Polyamide 618 / MXD9 / PXD9), Poly (nonamethylene azelamide / metaxylylene azelamide / paraxylylene azelamide) copolymer (polyamide 99 / MXD9 / PXD9), poly (nonamethylene sebacamide / metaxili) Ren Azelamide / Paraxylylene Azelamide) Copolymer (Polyamide 910 / MXD9 / PXD9), Poly (Nonamethylene Dodecamide / Metaxylylene Azelamide / Paraxylylene Azelamide) Copolymer (Polyamide 912 / MXD9 / PXD9), poly (nonamethylenetetradecamide / metaxylylene azelamide / paraxylylene azelamide) copolymer (polyamide 914 / MXD9 / PXD9), poly (nonamethylene azelamide / 2-methyloctamethylene azelamide / Metaxylylene azelamide / paraxylylene azelamide) copolymer (polyamide 99 / M89 / MXD9 / PXD9), poly (nonamethylene sebacamide / 2-methyloctamethylene sebacamide / metaxylylene azelamide / para Xylylene azelamide) copolymer (polyamide 910 / M810 / MXD9 / PXD9), poly (nonamethylene dodecamide / 2-methyloctamethylene dodecamide / metaxylylene azelamide / paraxylylene azelamide) copolymer ( Polyamide 912 / M812 / MXD9 / PXD9), poly (nonamethylenetetradecamide / 2-methyloctamethylenetetradecamide / metaxylylene azelamide / paraxylylene azelamide) copolymer (polyamide 914 / M814 / MXD9 / PXD9), Poly (Decamethylene Azelamide / Metaxylylene Azelamide / Paraxylylene A) Zeramide) copolymer (polyamide 109 / MXD9 / PXD9), poly (decamethylene sebacamide / metaxylylene azelamide / paraxylylene azelamide) copolymer (polyamide 1010 / MXD9 / PXD9), poly (decamethylene) Dodecamide / Metaxylylene Azelamide / Paraxylylene Azelamide) Copolymer (Polyamide 1012 / MXD9 / PXD9), Poly (Decamethylenetetradecamide / Metaxylylene Azelamide / Paraxylylene Azelamide) Copolymer (Polyamide 1014 / MXD9 / PXD9), Poly (dodecamethylene azelamide / metaxylylene azelamide / paraxylylene azelamide) copolymer (polyamide 129 / MXD9 / PXD9), poly (dodecamethylene sebacamide / metaxili) Ren Azelamide / Paraxylylene Azelamide) Copolymer (Polyamide 1210 / MXD9 / PXD9), Poly (Dodecamethylene Dodecamide / Metaxylylene Azelamide / Paraxylylene Azelamide) Copolymer (Polyamide 1212 / MXD9 / PXD9), poly (undecaneamide / metaxylylene azelamide / paraxylylene azelamide) copolymer (polyamide 11 / MXD9 / PXD9), poly (dodecaneamide / metaxylylene azelamide / paraxylylene azelamide) Polymer (polyamide 12 / MXD9 / PXD9),
Poly (hexamethylene sebacamide / metaxylylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 610 / MXD10 / PXD10), poly (hexamethylene dodecamide / metaxylylene sebacamide / paraxili) Lensebacamide) copolymer (polyamide 612 / MXD10 / PXD10), poly (hexamethylenetetradecamide / metaxylylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 614 / MXD10 / PXD10) , Poly (hexamethylene hexadecamide / metaxylylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 616 / MXD10 / PXD10), poly (hexamethylene octadecamide / metaxylylene sebacamide / Paraxylylene sebacamide) copolymer (polyamide 618 / MXD10 / PXD10), poly (nonamethylene azelamide / metaxylylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 99 / MXD10 / PXD10) ), Poly (nonamethylene sebacamide / metaxylylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 910 / MXD10 / PXD10), poly (nonamethylene dodecamide / metaxylylene sebacamide / Paraxylylene sebacamide) copolymer (polyamide 912 / MXD10 / PXD10), poly (nonamethylenetetradecamide / metaxylylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 914 / MXD10 / PXD10), poly (nonamethylene azelamide / 2-methyloctamethylene azelamide / metaxylylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 99 / M89 / MXD10 / PXD10), poly (nonamethylene) Sebacamide / 2-methyloctamethylene sebacamide / metaxylylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 910 / M810 / MXD10 / PXD10), poly (nonamethylene dodecamide / 2- Methyloctamethylene dodecamide / metaxylylene sevacamido / paraxylylene sevacamido) copolymer (polyamide 912 / M812 / MXD10 / PXD10), poly (nonamethylenetetradecamide / 2-methyloctamethylenetetradecamide) / Metaxylylene sebacamide / Paraxylylene sebacamide) copolymer (polyamide 914 / M814 / MXD10 / PXD10), poly (decamethylenea) Zeramide / Metaxylylene sebacamide / Paraxylylene sebacamide) Copolymer (Polyamide 109 / MXD10 / PXD10), Poly (Decamethylene sebacamide / Metaxylylene sebacamide / Paraxylylene sebacamide) Copolymer (Polyamide 1010 / MXD10 / PXD10), Poly (Decamethylenedodecamide / Metaxylylene sebacamide / Paraxylylene sebacamide) Copolymer (Polyamide 1012 / MXD10 / PXD10), Poly (Decamethylenetetra) Decamide / Metaxylylene sebacamide / Paraxylylene sebacamide) Copolymer (Polyamide 1014 / MXD10 / PXD10), Poly (Dodecamethylene azelamide / Metaxylylene sebacamide / Paraxylylene sebacamide) Copolymer (Polyamide 129 / MXD10 / PXD10), Poly (Dodecamethylene sebacamide / Metaxylylene sebacamide / Paraxylylene sebacamide) Copolymer (Polyamide 1210 / MXD10 / PXD10), Poly (Dodecamethylene) Dodecamide / Metaxylylene sebacamide / Paraxylylene sebacamide) Copolymer (Polyamide 1212 / MXD10 / PXD10), Poly (Undecaneamide / Metaxylylene sebacamide / Paraxylylene sebacamide) Combined (polyamide 11 / MXD10 / PXD10) and poly (dodecaneamide / metaxylylene sebacamide / paraxylylene sebacamide) copolymers (polyamide 12 / MXD10 / PXD10) are preferable.

Poly (hexamethylene sebacamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 610 / 9T / M8T), poly (hexamethylene dodecamide / nonamethylene terephthalamide / 2- Methyloctamethylene terephthalamide) copolymer (polyamide 612 / 9T / M8T), poly (hexamethylenetetradecamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 614 / 9T) / M8T), poly (nonamethylene azelamide / 2-methyloctamethylene azelamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 99 / M89 / 9T / M8T), poly (polycarbonate 99 / M89 / 9T / M8T) Nonamethylene sebacamide / 2-methyloctamethylene sebacamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 910 / M810 / 9T / M8T), poly (nonamethylene dodecamide) / 2-Methyloctamethylene dodecamide / Nonamethylene terephthalamide / 2-Methyloctamethylene terephthalamide) copolymer (polyamide 912 / M812 / 9T / M8T), poly (nonamethylenetetradecamide / 2-methylocta) Methylenetetradecamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 914 / M814 / 9T / M8T), poly (decamethylene azelamide / nonamethylene terephthalamide / 2-methyl Octamethylene terephthalamide) copolymer (polyamide 109 / 9T / M8T), poly (decamethylene sebacamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 1010 / 9T / M8T), poly (decamethylene dodecamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 1012 / 9T / M8T), poly (decamethylenetetradecamide / nonamethylene terephthalamide) / 2-Methyloctamethylene terephthalamide) copolymer (polyamide 1014 / 9T / M8T), poly (dodecamethylene azelamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 129) / 9T / M8T), poly (dodecamethylene sebacamide / nonamethylene terephthalamide / 2-methyloctamethylenete Reftalamide) copolymer (polyamide 1210 / 9T / M8T), poly (dodecamethylene dodecamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 1212 / 9T / M8T), poly (polyamide 1212 / 9T / M8T), poly (polyamide 1212 / 9T / M8T) Undecaneamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 11 / 9T / M8T), poly (dodecaneamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) Copolymer (polyamide 12 / 9T / M8T),
Poly (hexamethylene sebacamide / decamethylene terephthalamide) copolymer (polyamide 610 / 10T), poly (hexamethylene dodecamide / decamethylene terephthalamide) copolymer (polyamide 612 / 10T), poly (hexa) Methylenetetradecamide / decamethylene terephthalamide) copolymer (polyamide 614 / 10T), poly (nonamethylene azelamide / 2-methyloctamethylene azelamide / decamethylene terephthalamide) copolymer (polyamide 99 / M89) / 10T), poly (nonamethylene sebacamide / 2-methyloctamethylene sebacamide / decamethylene terephthalamide) copolymer (polyamide 910 / M810 / 10T), poly (nonamethylene dodecamide / 2-methylocta) Methylenedodecamide / decamethylene terephthalamide) copolymer (polyamide 912 / M812 / 10T), poly (nonamethylenetetradecamide / 2-methyloctamethylenetetradecamide / decamethylene terephthalamide) copolymer (polyamide) 914 / M814 / 10T), poly (decamethylene azelamide / decamethylene terephthalamide) copolymer (polyamide 109 / 10T), poly (decamethylene sebacamide / decamethylene terephthalamide) copolymer (polyamide 1010) / 10T), Poly (decamethylene dodecamide / decamethylene terephthalamide) copolymer (polyamide 1012 / 10T), poly (decamethylene tetradecamide / decamethylene terephthalamide) copolymer (polyamide 1014 / 10T) , Poly (dodecamethylene azelamide / decamethylene terephthalamide) copolymer (polyamide 129 / 10T), poly (dodecamethylene sebacamide / decamethylene terephthalamide) copolymer (polyamide 1210 / 10T), poly (polyamide 1210 / 10T), poly (polyamide 1210 / 10T) Dodecamethylene dodecamide / decamethylene terephthalamide) copolymer (polyamide 1212 / 10T), poly (undecaneamide / decamethylene terephthalamide) copolymer (polyamide 11 / 10T), poly (dodecaneamide / decamethylene tere) Phtalamide) copolymer (polyamide 12 / 10T),
Poly (hexamethylene sebacamide / metaxylylene azelamide) copolymer (polyamide 610 / MXD9), poly (hexamethylene dodecamide / metaxylylene azelamide) copolymer (polyamide 612 / MXD9), poly (hexa) Methylenetetradecamide / metaxylylene azelamide) copolymer (polyamide 614 / MXD9), poly (nonamethylene azelamide / 2-methyloctamethylene azelamide / metaxylylene azelamide) copolymer (polyamide 99 / M89) / MXD9), poly (nonamethylene sebacamide / 2-methyloctamethylene sebacamide / metaxylylene azelamide) copolymer (polyamide 910 / M810 / MXD9), poly (nonamethylene dodecamide / 2-methylocta) Methylenedodecamide / Metaxylylene Azelamide) Copolymer (Polyamide 912 / M812 / MXD9), Poly (Nonamethylenetetradecamide / 2-Methyloctamethylenetetradecamide / Metaxylylene Azelamide) Copolymer (Polyamide) 914 / M814 / MXD9), poly (decamethylene azelamide / metaxylylene azelamide) copolymer (polyamide 109 / MXD9), poly (decamethylene sebacamide / metaxylylene azelamide) copolymer (polyamide 1010) / MXD9), poly (decamethylene dodecamide / metaxylylene azelamide) copolymer (polyamide 1012 / MXD9), poly (decamethylenetetradecamide / metaxylylene azelamide) copolymer (polyamide 1014 / MXD9) , Poly (dodecamethylene azelamide / metaxylylene azelamide) copolymer (polyamide 129 / MXD9), poly (dodecamethylene sebacamide / metaxylylene azelamide) copolymer (polyamide 1210 / MXD9), poly (polyamide 1210 / MXD9), poly (polyamide 1210 / MXD9), poly (polyamide 1210 / MXD9), poly (polyamide 1210 / MXD9) Dodecamethylene Dodecamide / Metaxylylene Azelamide) Copolymer (Polyamide 1212 / MXD9), Poly (Undecaneamide / Metaxylylene Azelamide) Copolymer (Polyamide 11 / MXD9), Poly (Polyamide 11 / MXD9), Poly (Dodecaneamide / Metaxylylene) Azelamide) copolymer (polyamide 12 / MXD9),
Poly (hexamethylene sebacamide / metaxylylene sebacamide) copolymer (polyamide 610 / MXD10), poly (hexamethylene dodecamide / metaxylylene sebacamide) copolymer (polyamide 612 / MXD10), poly (Hexamethylenetetradecamide / Metaxylylene sebacamide) copolymer (Polyamide 614 / MXD10), Poly (Nonamethylene azelamide / 2-methyloctamethylene azelamide / Metaxylylene sebacamide) copolymer ( Polyamide 99 / M89 / MXD10), poly (nonamethylene sebacamide / 2-methyloctamethylene sebacamide / metaxylylene sebacamide) copolymer (polyamide 910 / M810 / MXD10), poly (nonamethylene dodecamide) / 2-Methyloctamethylene dodecamide / Metaxylylene sebacamide) Copolymer (Polyamide 912 / M812 / MXD10), Poly (Nonamethylenetetradecamide / 2-Methyloctamethylenetetradecamide / Metaxylylene sevacam) Mid) Copolymer (Polyamide 914 / M814 / MXD10), Poly (Decamethylene Azelamide / Metaxylylene sebacamide) Copolymer (Polyamide 109 / MXD10), Poly (Decamethylene sebacamide / Metaxylylene) Bacamido) Copolymer (Polyamide 1010 / MXD10), Poly (Decamethylenedodecamido / Metaxylylene sebacamide) Copolymer (Polyamide 1012 / MXD10), Poly (Decamethylenetetradecamide / Metaxylylene sebaca) Mid) copolymer (polyamide 1014 / MXD10), poly (dodecamethylene azelamide / metaxylylene sevacamido) copolymer (polyamide 129 / MXD10), poly (dodecamethylene sebacamide / metaxylylene sevacamido) ) Copolymer (Polyamide 1210 / MXD10), Poly (Dodecamethylene dodecamide / Metaxylylene sebacamide) Copolymer (Polyamide 1212 / MXD10), Poly (Undecaneamide / Metaxylylene sebacamide) (Polyamide 11 / MXD10), Poly (dodecaneamide / metaxylylene sebacamide) copolymer (Polyamide 12 / MXD10),
Poly (hexamethylene sebacamide / paraxylylene azelamide) copolymer (polyamide 610 / PXD9), poly (hexamethylene dodecamide / paraxylylene azelamide) copolymer (polyamide 612 / PXD9), poly (hexa) Methylenetetradecamide / paraxylylene azelamide) copolymer (polyamide 614 / PXD9), poly (nonamethylene azelamide / 2-methyloctamethylene azelamide / paraxylylene azelamide) copolymer (polyamide 99 / M89) / PXD9), poly (nonamethylene sebacamide / 2-methyloctamethylene sebacamide / paraxylylene azelamide) copolymer (polyamide 910 / M810 / PXD9), poly (nonamethylene dodecamide / 2-methylocta) Methylenedodecamide / paraxylylene azelamide) copolymer (polyamide 912 / M812 / PXD9), poly (nonamethylenetetradecamide / 2-methyloctamethylenetetradecamide / paraxylylene azelamide) copolymer (polyamide) 914 / M814 / PXD9), poly (decamethylene azelamide / paraxylylene azelamide) copolymer (polyamide 109 / PXD9), poly (decamethylene sebacamide / paraxylylene azelamide) copolymer (polyamide 1010) / PXD9), poly (decamethylene dodecamide / paraxylylene azelamide) copolymer (polyamide 1012 / PXD9), poly (decamethylenetetradecamide / paraxylylene azelamide) copolymer (polyamide 1014 / PXD9) , Poly (dodecamethylene azelamide / paraxylylene azelamide) copolymer (polyamide 129 / PXD9), poly (dodecamethylene sebacamide / paraxylylene azelamide) copolymer (polyamide 1210 / PXD9), poly (polyamide 1210 / PXD9), poly (polyamide 1210 / PXD9), poly (polyamide 1210 / PXD9) Dodecamethylene dodecamide / paraxylylene azelamide) copolymer (polyamide 1212 / PXD9), poly (undecaneamide / paraxylylene azelamide) copolymer (polyamide 11 / PXD9), poly (polyamide 11 / PXD9), poly (dodecaneamide / paraxylylene) Azelamide) copolymer (polyamide 12 / PXD9),
Poly (hexamethylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 610 / PXD10), poly (hexamethylene dodecamide / paraxylylene sebacamide) copolymer (polyamide 612 / PXD10), poly (Hexamethylenetetradecamide / paraxylylene sebacamide) copolymer (polyamide 614 / PXD10), poly (nonamethylene azelamide / 2-methyloctamethylene azelamide / paraxylylene sebacamide) copolymer ( Polyamide 99 / M89 / PXD10), poly (nonamethylene sebacamide / 2-methyloctamethylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 910 / M810 / PXD10), poly (nonamethylene dodecamide) / 2-Methyloctamethylenedodecamide / Paraxylylene sebacamide) Copolymer (Polyamide 912 / M812 / PXD10), Poly (Nonamethylenetetradecamide / 2-Methyloctamethylenetetradecamide / Paraxylylene sevacam) Mid) copolymer (polyamide 914 / M814 / PXD10), poly (decamethylene azelamide / paraxylylene sebacamide) copolymer (polyamide 109 / PXD10), poly (decamethylene sebacamide / paraxylylene) Bacamide) copolymer (polyamide 1010 / PXD10), poly (decamethylene dodecamide / paraxylylene sebacamide) copolymer (polyamide 1012 / PXD10), poly (decamethylenetetradecamide / paraxylylene sebaca) Mid) copolymer (polyamide 1014 / PXD10), poly (dodecamethylene azelamide / paraxylylene sebacamide) copolymer (polyamide 129 / PXD10), poly (dodecamethylene sebacamide / paraxylylene sebacamide) ) Copolymer (Polyamide 1210 / PXD10), Poly (Dodecamethylene dodecamide / Paraxylylene sebacamide) Copolymer (Polyamide 1212 / PXD10), Poly (Undecaneamide / Paraxylylene sebacamide) (Polyamide 11 / PXD10), Poly (dodecaneamide / paraxylylene sebacamide) copolymer (Polyamide 12 / PXD10),
Poly (hexamethylene sebacamide / metaxylylene azelamide / paraxylylene azelamide) copolymer (polyamide 610 / MXD9 / PXD9), poly (hexamethylene dodecamide / metaxylylene azelamide / paraxylylene azelamide) ) Copolymer (Polyamide 612 / MXD9 / PXD9), Poly (Hexamethylenetetradecamide / Metaxylylene Azelamide / Paraxylylene Azelamide) Copolymer (Polyamide 614 / MXD9 / PXD9), Poly (Nona Methylene Aze) Ramide / 2-methyloctamethylene azelamide / metaxylylene azelamide / paraxylylene azelamide) copolymer (polyamide 99 / M89 / MXD9 / PXD9), poly (nonamethylene sebacamide / 2-methyloctamethylenese) Bacamido / Metaxylylene Azelamide / Paraxylylene Azelamide) Copolymer (Polyamide 910 / M810 / MXD9 / PXD9), Poly (Nonamethylene Dodecamide / 2-Methyloctamethylene Dodecamide / Metaxylylene Azelamide / Paraxylylene Azelamide) Copolymer (Polyamide 912 / M812 / MXD9 / PXD9), Poly (Nonamethylenetetradecamide / 2-Methyloctamethylenetetradecamide / Metaxylylene Azelamide / Paraxylylene Azelamide) Polymer (Polyamide 914 / M814 / MXD9 / PXD9), Poly (Decamethylene Azelamide / Metaxylylene Azelamide / Paraxylylene Azelamide) Copolymer (Polyamide 109 / MXD9 / PXD9), Poly (Decamethylene Sevaca) Mid / Metaxylylene Azelamide / Paraxylylene Azelamide) Copolymer (Polyamide 1010 / MXD9 / PXD9), Poly (Decamethylenedodecamido / Metaxylylene Azelamide / Paraxylylene Azelamide) Copolymer (Polyamide) 1012 / MXD9 / PXD9), poly (decamethylenetetradecamide / metaxylylene azelamide / paraxylylene azelamide) copolymer (polyamide 1014 / MXD9 / PXD9), poly (dodecamethylene azelamide / metaxylylene aze) Lamid / paraxylylene azelamide) copolymer (polyamide 129 / MXD9 / PXD9), poly (dodecamethylene sebacamide / metaxylylene azelamide / paraxylylene azelamide) copolymer (polyamide 1210 / MXD9 / PXD9) ), Poly (dodecamethylene dodecamide / metaxylylene azelamide / paraxylile) N-Azelamide) Copolymer (Polyamide 1212 / MXD9 / PXD9), Poly (Undecaneamide / Metaxylylene Azelamide / Paraxylylene Azelamide) Copolymer (Polyamide11 / MXD9 / PXD9), Poly (Dodecaneamide / Metaxili) Ren Azelamide / Paraxylylene Azelamide) Copolymer (Polyamide 12 / MXD9 / PXD9),
Poly (hexamethylene sebacamide / metaxylylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 610 / MXD10 / PXD10), poly (hexamethylene dodecamide / metaxylylene sebacamide / paraxili) Lensebacamide) copolymer (polyamide 612 / MXD10 / PXD10), poly (hexamethylenetetradecamide / metaxylylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 614 / MXD10 / PXD10) , Poly (polyamide 99 / M89 / MXD10 / PXD10), poly (nonamethylene sebaca / 2-methyloctamethylene azelamide / metaxylylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 99 / M89 / MXD10 / PXD10) Mid / 2-methyloctamethylene sebacamide / metaxylylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 910 / M810 / MXD10 / PXD10), poly (nonamethylene dodecamide / 2-methylocta) Methylenedodecamide / Metaxylylene sebacamide / Paraxylylene sebacamide) Copolymer (Polyamide 912 / M812 / MXD10 / PXD10), Poly (Nonamethylenetetradecamide / 2-Methyloctamethylenetetradecamide / Meta Xylylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 914 / M814 / MXD10 / PXD10), poly (decamethylene azelamide / metaxylylene sebacamide / paraxylylene sebacamide) co-weight Combined (Polyamide 109 / MXD10 / PXD10), Poly (Decamethylene sebacamide / Metaxylylene sebacamide / Paraxylylene sebacamide) copolymer (Polyamide 1010 / MXD10 / PXD10), Poly (Decamethylene dodecamide) / Metaxylylene sebacamide / Paraxylylene sebacamide) Copolymer (Polyamide 1012 / MXD10 / PXD10), Poly (Decamethylenetetradecamide / Metaxylylene sebacamide / Paraxylylene sebacamide) Polymer (Polyamide 1014 / MXD10 / PXD10), Poly (Dodecamethylene azelamide / Metaxylylene sebacamide / Paraxylylene sebacamide) Copolymer (Polyamide 129 / MXD10 / PXD10), Poly (Dodecamethylene sebaca) Mid / Metaxylylene sebacamide / Paraxylylene sebacamide) copolymer (polyamide 1210 / MXD10 / PXD10), poly (dodecametile) Ndodecamide / Metaxylylene sebacamide / Paraxylylene sebacamide) Copolymer (Polyamide 1212 / MXD10 / PXD10), Poly (Undecaneamide / Metaxylylene sebacamide / Paraxylylene sebacamide) copolymer (Polyamide 11 / MXD10 / PXD10), poly (dodecaneamide / metaxylylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 12 / MXD10 / PXD10) is more preferable.

Poly (polyamide 99 / M89 / 9T / M8T) copolymer (polyamide 99 / M89 / 9T / M8T), poly (nonamethylene sebaca) Mid / 2-methyloctamethylene sebacamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 910 / M810 / 9T / M8T), poly (nonamethylene dodecamide / 2-methyl) Octamethylene dodecamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 912 / M812 / 9T / M8T), poly (nonamethylene tetradecamide / 2-methyl octamethylene tetradecamide) / Nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) copolymer (polyamide 914 / M814 / 9T / M8T), poly (undecaneamide / nonamethylene terephthalamide / 2-methyloctamethylene terephthalamide) Copolymer (Polyamide 11 / 9T / M8T), Poly (Dodecaneamide / Nonamethylene terephthalamide / 2-Methyloctamethylene terephthalamide) Copolymer (Polyamide 12 / 9T / M8T), Poly (Decamethylene azeramide) / Decamethylene terephthalamide) copolymer (polyamide 109 / 10T), poly (decamethylene sebacamide / decamethylene terephthalamide) copolymer (polyamide 1010 / 10T), poly (decamethylene dodecamide / decamethylene) Co-polymer (polyamide 1012 / 10T), poly (decamethylenetetradecamide / decamethylene terephthalamide) copolymer (polyamide 1014 / 10T), poly (undecaneamide / decamethylene terephthalamide) Polymer (polyamide 11 / 10T), poly (dodecaneamide / decamethylene terephthalamide) copolymer (polyamide 12 / 10T), poly (nonamethylene azelamide / 2-methyloctamethylene azelamide / metaxylylene azelamide) ) Copolymer (Polyamide 99 / M89 / MXD9), Poly (Decamethylene Azelamide / Metaxylylene Azelamide) Copolymer (Polyamide 109 / MXD9), Poly (Dodecamethylene Azelamide / Metaxylylene Azelamide) Polymer (polyamide 129 / MXD9), poly (undecaneamide / metaxylylene azelamide) copolymer (polyamide 11 / M) XD9), poly (dodecaneamide / metaxylylene azelamide) copolymer (polyamide 12 / MXD9), poly (hexamethylene sebacamide / metaxylylene sebacamide) copolymer (polyamide 610 / MXD10), poly (Nonamethylene sebacamide / 2-methyloctamethylene sebacamide / metaxylylene sebacamide) Copolymer (polyamide 910 / M810 / MXD10), poly (decamethylene sebacamide / metaxylylene sebacamide) Copolymer (Polyamide 1010 / MXD10), Poly (Dodecamethylene sebacamide / Metaxylylene sebacamide copolymer (Polyamide 1210 / MXD10), Poly (Undecaneamide / Metaxylylene sebacamide) copolymer ( Polyamide 11 / MXD10), poly (dodecaneamide / metaxylylene sebacamide) copolymer (polyamide 12 / MXD10), poly (nonamethylene azelamide / 2-methyloctamethylene azelamide / paraxylylene azelamide) Polymer (Polyamide 99 / M89 / PXD9), Poly (Decamethylene Azelamide / Paraxylylene Azelamide) Copolymer (Polyamide 109 / PXD9), Poly (Dodecamethylene Azelamide / Paraxylylene Azelamide) Copolymer (Polyamide 129 / PXD9), Poly (Undecaneamide / Paraxylylene Azelamide) Copolymer (Polyamide 11 / PXD9), Poly (Dodecaneamide / Paraxylylene Azelamide) Copolymer (Polyamide 12 / PXD9), Poly (Hexamethylene sebacamide / paraxylylene sebacamide) Copolymer (polyamide 610 / PXD10), poly (nonamethylene sebacamide / 2-methyloctamethylene sebacamide / paraxylylene sebacamide) Combined (Polyamide 910 / M810 / PXD10), Poly (Decamethylene sebacamide / Paraxylylene sebacamide) copolymer (Polyamide 1010 / PXD10), Poly (Dodecamethylene sebacamide / Paraxylylene sebacamide) Copolymer (Polyamide 1210 / PXD10), Poly (Undecaneamide / Paraxylylene sebacamide) Copolymer (Polyamide 11 / PXD10), Poly (Dodecaneamide / Paraxylylene sebacamide) Copolymer (Polyamide 12) / PXD10), poly (nonamethylene azelamide / 2-methyloctamethylene azelamide / metaxylylene azelamide / paraxylylene azelamide) copolymer (polyamide 99 / M89 / MXD9 / PXD9), poly (decamethylene azelamide / metaxylylene azelamide / paraxylylene azelamide) copolymer (polyamide 109 / MXD9 / PXD9), poly (dodecamethylene azelamide / metaxylylene azelamide / para) Xylylene azelamide) copolymer (polyamide 129 / MXD9 / PXD9), poly (undecaneamide / metaxylylene azelamide / paraxylylene azelamide) copolymer (polyamide 11 / MXD9 / PXD9), poly (dodecaneamide) / Metaxylylene azelamide / Paraxylylene azelamide) Copolymer (Polyamide 12 / MXD9 / PXD9), Poly (Hexamethylene sebacamide / Metaxylylene sebacamide / Paraxylylene sebacamide) (Polyamide 610 / MXD10 / PXD10), Poly (Nonamethylene sebacamide / 2-methyloctamethylene sebacamide / Metaxylylene sebacamide / Paraxylylene sebacamide) copolymer (Polyamide 910 / M810 / MXD10) / PXD10), poly (decamethylene sebacamide / metaxylylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 1010 / MXD10 / PXD10), poly (dodecamethylene sebacamide / metaxylylene) Bacamido / paraxylylene sebacamide) copolymer (polyamide 1210 / MXD10 / PXD10), poly (undecaneamide / metaxylylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 11 / MXD10 / PXD10), poly (dodecaneamide / metaxylylene sebacamide / paraxylylene sebacamide) copolymer (polyamide 12 / MXD10 / PXD10) is more preferable.

Examples of the equipment for producing the polyamide copolymer (A1) 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 a reaction extruder can be mentioned. As a polymerization method, known methods such as melt polymerization, solution polymerization, and solid phase polymerization can be used, and polymerization can be carried out by repeating normal pressure, reduced pressure, and pressurizing operations. These polymerization methods can be used alone or in combination as appropriate.

The relative viscosity of the polyamide copolymer (A1) measured under the conditions of 96% sulfuric acid, polymer concentration 1% and 25 ° C. according to 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 1.8 or more and 4.5 or less. More preferable.

When the terminal amino group concentration per 1 g of the polyamide copolymer (A1) is [A] (μeq / g) and the terminal carboxyl group concentration is [B] (μeq / g), the semi-aromatic polyamide composition described later ( From the viewpoint of sufficiently obtaining interlayer adhesion with B) and its durability, it is preferably [A]> [B] +5, more preferably [A]> [B] +15, and [A]. > [B] +20 is more preferable. Further, from the viewpoint of the melt stability of the polyamide and the suppression of the generation of gel-like substances, [A]> 30 is preferable, and 30 <[A] <140 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 polyamide copolymer (A1) 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-hexadecandiamine, 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; 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 -Triaminonaphthalene, 2,4,6-triaminopyridine, 1,2,7,8-tetraminonaphthalene, 1,4,5,8-tetraminonaphthalene and the like can be mentioned. 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, etc. Examples thereof include polyallylamine. 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 or 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 / or secondary amino groups having active hydrogen atoms. It has (imino group).

The number of nitrogen atoms in the polyalkyleneimine is not particularly limited, and 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, Adicyclic monocarboxylic acids such as palmitic acid, stearic acid, oleic acid, linoleic acid, araquinic acid, behenic 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, octadecenedioic acid, eicosandioic acid, eicosendioic acid, docosanedioic acid, diglycolic acid, 2,2,4-trimethyladiponic acid, 2,4,4-trimethyladiponic acid, etc. Aliphatic dicarboxylic acid; alicyclic dicarboxylic acid such as 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, norbornandicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, m-xylylene dicarboxylic acid, 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 polyamide copolymer (A1) 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 having a desired viscosity is obtained. 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 meq / mol or more and 10 meq / mol or less (the equivalent of amino groups (eq) is a carboxyl group. The amount of amino groups that form an amide group by reacting with 1: 1 is defined as 1 equivalent).

In the polyamide copolymer (A1), among the above-exemplified amines, it is preferable to add diamine and / or 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, fat It is more preferable to add at least one selected from the group consisting of group diamines, alicyclic diamines, and polyalkyleneimines at the time of polymerization.

[Elastomer polymer (A2)]
The polyamide copolymer composition (A) contains an elastomer polymer (A2) containing a structural unit derived from an unsaturated compound having a carboxyl group and / or an acid anhydride group (elastomer polymer (A2)). It may be called.).

Examples of the elastomer polymer (A2) include (ethylene and / or propylene) / α-olefin copolymer, (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid ester) copolymer, and fragrance. Examples thereof include group vinyl compounds / conjugated diene compound-based block copolymers, and these may be used alone or in combination of two or more.

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-hexene, 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-hexadien, 1,5-hexadien, 1,4-octadien, 1,5-octadien, 1,6-octadien, 1,7-octadien, 2-methyl-1, 5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadien, 4-ethylidene-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 ester) -based copolymer is a copolymer of ethylene and / or propylene and an α, β-unsaturated carboxylic acid ester monomer. The α, β-unsaturated carboxylic acid ester monomer includes methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, and the like. Pentyl acrylate, pentyl methacrylate, hexyl acrylate, hexyl methacrylate, heptyl acrylate, heptyl methacrylate, octyl acrylate, octyl methacrylate, nonyl acrylate, nonyl methacrylate, decyl acrylate, decyl methacrylate, acrylic acid Examples thereof include 2-ethylhexyl, 2-ethylhexyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, monomethyl maleate, monomethyl itacone, dimethyl maleate, and dimethyl itacone. These can be used alone or in combination of two or more.

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 block copolymer described above, 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 an 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. In addition, the aromatic vinyl compound-based polymer block may optionally have a unit composed of a small amount of other unsaturated monomers.

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, one aromatic vinyl compound polymer block and one conjugated diene compound polymer block are linear as an aromatic vinyl compound / conjugated diene compound-based block copolymer and / or its hydrogenated material. Three polymer blocks are linearly bonded in the order of a diblock copolymer bonded in a shape, an aromatic vinyl compound-based polymer block-conjugated diene compound-based polymer block-an aromatic vinyl compound-based polymer block. One or more of the above triblock copolymers and their hydrogenated products are preferably used, and both unhydrogenated or hydrogenated styrene / butadiene block copolymers and unhydrogenated 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.

Examples of unsaturated compounds having a carboxyl group forming a constituent unit of the elastomeric polymer (A2) include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, and cis. Α, β-unsaturated carboxylic acids such as -4-cyclohexene-1,2-dicarboxylic acid, endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid, and metal salts of these carboxylic acids. Acid is mentioned. Examples of unsaturated compounds having an acid anhydride group forming a constituent unit of the elastomeric polymer (A2) include maleic anhydride, itaconic anhydride, citraconic anhydride, and endobicyclo- [2.2.1] -5-heptene. Examples thereof include dicarboxylic acid anhydrides having α, β-unsaturated bonds such as −2,3-dicarboxylic acid anhydrides. These can be used alone or in combination of two or more. Among these, a dicarboxylic acid anhydride having an α, β-unsaturated bond is preferable, and maleic anhydride and itaconic anhydride are more preferable.

The concentration of the carboxyl group and / or acid anhydride group in the elastomer polymer (A2) sufficiently improves the low-temperature impact resistance, the interlayer adhesiveness with the semi-aromatic polyamide composition (B) described later, and its durability. From the viewpoint of the fluidity of the obtained polyamide copolymer composition (A), it is preferably 25 μeq / g or more and 200 μeq / g or less, and more preferably 50 μeq / g or more and 150 μeq / g or less.

The concentration of carboxyl group and / or acid anhydride group in the elastomer polymer (A2) is determined by using a sample solution prepared by dissolving the elastomer polymer in a toluene solution and further adding ethanol, and using phenolphthalein as an indicator. Then, it can be measured by titrating with a 0.1 N KOH ethanol solution.

The content of the polyamide copolymer (A1) in the polyamide copolymer composition (A) is 70% by mass or more and 95% by mass or less with respect to 100% by mass of the polyamide copolymer composition (A). It is preferably 72% by mass or more and 92% by mass or less, and more preferably 75% by mass or more and 90% by mass or less. If the content of the polyamide copolymer (A1) is less than the above value, the mechanical properties of the obtained laminated tube are inferior, while if it exceeds the above value, the interlayer adhesiveness of the obtained laminated tube and its durability thereof. Inferior in sex.

The content of the elastomer polymer (A2) in the polyamide copolymer composition (A) is 5% by mass or more and 30% by mass or less with respect to 100% by mass of the polyamide copolymer composition (A), which is 8 It is preferably mass% or more and 28 mass% or less, and more preferably 10 mass% or more and 25 mass% or less. If the content of the elastomer polymer (A2) is less than the above value, the low temperature impact resistance, interlayer adhesion, and durability of the obtained laminated tube are inferior, while if it exceeds the above value, it is obtained. The mechanical properties of the laminated tube and the fluidity of the obtained polyamide copolymer composition (A) are inferior.

The method of mixing the polyamide copolymer (A1) and the elastomer polymer (A2) is not particularly limited, and various additives can be blended as needed, and various conventionally known methods can be adopted. .. For example, a method of uniformly dry-blending the pellets of the polyamide copolymer (A1) and the elastomer polymer (A2) so as to have the above-mentioned mixing ratio using a tumbler and / or a mixer is required. It can be produced by a method such as dry blending in advance at a concentration used at the time of molding together with other components added accordingly, and melt-kneading. Melt kneading can be performed using a kneader such as a single-screw extruder, a twin-screw extruder, a kneader, or a Banbury mixer.

Further, the polyamide copolymer composition (A) preferably does not contain a plasticizer from the viewpoint of durability of interlayer adhesiveness after contact / immersion with fuel for a long time and after heat treatment.

The polyamide copolymer composition (A) may be a mixture with another polyamide resin or other thermoplastic resin. The total content of the polyamide (A1) and the elastomer polymer (A2) in the polyamide copolymer composition (A) which is a mixture is preferably 60% by mass or more, and more preferably 70% by mass or more. preferable.

Other polyamide-based resins include polymethoxylylene succinamide (polyamide MXD4), polymethoxylylen glutamide (polyamide MXD5), polymethoxylylen adipamide (polyamide MXD6), and polymethoxylylence veramide (polyamide MXD8). , Polymethaxylylene dedecamide (Polyamide MXD12), Polymethoxylylene terephthalamide (Polyamide MXDT), Polymethoxylylene isophthalamide (Polyamide MXDI), Polymethoxylylene hexahydroterephthalamide (Polyamide MXDT (H)), Polyme Taxylylene naphthalamide (polyamide MXDN), polyparaxylylene succinamide (polyamide PXD4), polyparaxylylene glutamide (polyamide PXD5), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylene veramide (polyamide PXD6) Polyamide PXD8), 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 (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-naphthalene) Dimethylene 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-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) Telephthalamide) (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 (4,54'-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 (4,4'-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 (4,5'-propylene biscyclohexylene terephthalamide) (polyamide PACPT), poly (4,5'-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), polynonamethyleneisophthalamide (polyamide 9I), polynonamethylenehexahydroterephthalamide (polyamide 9T (H)), poly (2-methyloctamethyleneisophthalamide) ( Polyamide M8I), Poly (2-methyloctamethylenehexahydroterephthalamide) (Polyamide M8T (H)), Polytrimethylhexamethyleneisophthalamide (PolyamideTMHI), Polytrimethylhexamethylenehexahydroterephthalamide (PolyamideTMHT (PolyamideTMHT) H)), polydecamethylene isophthalamide (polyamide 10I), polydecamethylene hexahydroterephthalamide (polyamide 10T (H)), 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)), homopolymers such as polydodecamethylene naphthalamide (polyamide 12N), and / or several kinds of raw material monomers of these polyamides are used. Examples thereof include the copolymers used. 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 Polyethylene-based resins such as copolymers (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 , The polyolefin-based resin and the polystyrene-based resin containing a functional group such as an epoxy group; polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), poly (ethylene terephthalate / ethylene isophthalate) Copolymer (PET / PEI), Polytrimethylene terephthalate (PTT), Polycyclohexanedimethylene terephthalate (PCT), Polyethylene naphthalate (PEN), Polybutylene naphthalate (PBN), Polyallylate (PAR), Liquid crystal polyester (LCP) ), Polylactic acid (PLA), polyglycolic acid (PGA) and other polyester-based resins; polyacetal (POM), polyphenylene ether (PPO) and other polyether-based resins; Polysalho such as phenylsalphon (PPSU) Copolymer resin: Polyetherene sulfide (PPS), polythioether sulphon (PTES) and other polythioether resins; polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK) ), Polyetheretheretherketone (PEEEK), Polyetheretherketoneketone (PEEKK), Polyetherketoneketoneketone (PEKKK), Polyetherketoneetherketoneketone (PEKEKK) and other copolymer-based resins; polyacrylonitrile (PAN), Polynitrile resins such as polymethacrylonitrile, 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 coalescence, vinylidene chloride / methyl acrylate copolymer; cellulose resin such as cellulose acetate and cellulose butyrate; polycarbonate resin such as polycarbonate (PC); thermoplastic polyimide (TPI), polyetherimide, polyester Polygonic resins such as imide, polyamideimide (PAI), polyesteramideimide; thermoplastic polyurethane resins; polyamide elastomers, polyurethane elastomers, polyester elastomers and the like, and in some cases, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVDF) PVF), polytetrafluoroethylene (PTFE), polychlorofluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / hexafluoro Propylene copolymer (FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (THV), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer, tetrafluoro Ethylene / perfluoro (alkyl vinyl ether) copolymer (PFA) ), Tetrafluoroethylene / hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer, chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer (CPT) and other fluororesins. These can be used alone or in combination of two or more.

Further, the polyamide copolymer composition (A) contains, if necessary, an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, an inorganic filler, an antioxidant, a flame retardant, and crystals. A crystallization accelerator, a colorant and the like may be added.

2. Layer (b) The layer (b) of the laminated tube contains the semi-aromatic polyamide composition (B).

[Semi-aromatic polyamide composition (B)]
The semi-aromatic polyamide composition (B) contains a semi-aromatic polyamide (B1) or a semi-aromatic polyamide (B2), and the semi-aromatic polyamide (B1) is a total diamine of the semi-aromatic polyamide (B1). The unit contains 50 mol% or more of an aliphatic diamine unit having 9 or 10 carbon atoms, and the terephthalic acid unit and / or the naphthalenedicarboxylic acid unit is based on the total dicarboxylic acid unit of the semi-aromatic polyamide (B1). The semi-aromatic polyamide (B2) contains 50 mol% or more of xylylene diamine units and / or bis (aminomethyl) naphthalene units with respect to the total diamine units of the semi-aromatic polyamide (B2). % Or more, and 50 mol% or more of the aliphatic dicarboxylic acid unit having 9 or 10 carbon atoms is contained with respect to the total dicarboxylic acid unit of the semi-aromatic polyamide (B2) (hereinafter, the semi-aromatic polyamide composition (B). ).).

[Semi-aromatic polyamide (B1)]
The semi-aromatic polyamide composition (B) may include a semi-aromatic polyamide (B1) (hereinafter, may be referred to as a semi-aromatic polyamide composition (B1)), and the semi-aromatic polyamide (B1). Is a diamine unit containing 50 mol% or more of an aliphatic diamine unit having 9 or 10 carbon atoms with respect to the total diamine unit of the semi-aromatic polyamide (B1) and a total dicarboxylic acid unit of the semi-aromatic polyamide (B1). On the other hand, it contains a dicarboxylic acid unit containing 50 mol% or more of a terephthalic acid unit and / or a naphthalenedicarboxylic acid unit.

The content of the aliphatic diamine unit having 9 or 10 carbon atoms in the semi-aromatic polyamide (B1) sufficiently satisfies various physical properties such as heat resistance, chemical resistance, impact resistance, and chemical barrier property of the obtained laminated tube. From the viewpoint of ensuring the above, the amount is 50 mol% or more, preferably 55 mol% or more, and more preferably 60 mol% or more, based on the total diamine units of the semi-aromatic polyamide (B1).

Examples of the aliphatic diamine unit having 9 or 10 carbon atoms include units derived from 1,9-nonanediamine, 1,10-decanediamine and the like. 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 2,4-diethyl-1,6-hexane as long as the number of carbon atoms satisfies the above. Diamine, 2,2-dimethyl-heptanediamine, 2,3-dimethyl-heptanediamine, 2,4-dimethyl-heptanediamine, 2,5-dimethyl-heptanediamine, 2-methyl-1,8-octanediamine, 3 -Methyl-1,8-octanediamine, 4-methyl-1,8-octanediamine, 1,3-dimethyl-1,8-octanediamine, 1,4-dimethyl-1,8-octanediamine, 2,2 −Diamine-1,8-octanediamine, 2,4-dimethyl-1,8-octanediamine, 3,3-dimethyl-1,8-octanediamine, 3,4-dimethyl-1,8-octanediamine, 4 , 4-Dimethyl-1,8-octanediamine, 4,5-dimethyl-1,8-octanediamine, 2-methyl-1,9-nonanediamine, 3-methyl-1,9-nonanediamine, 4-methyl-1 , 9-Nonandiamine, 5-Methyl-1,9-Nonandiamine and the like may contain units derived from branched chain aliphatic diamines. These can be used alone or in combination of two or more.

Among the aliphatic diamine units having 9 or 10 carbon atoms, from 1,9-nonandiamine, 2-methyl-1,8-octanediamine, and 1,10-decanediamine from the viewpoint of availability and economy. Induced units are preferred. Furthermore, when 1,9-nonandiamine and 2-methyl-1,8-octanediamine are used in combination, the molar ratio of 1,9-nonandiamine unit and 2-methyl-1,8-octanediamine unit is moldability and resistance. From the viewpoint of the balance of impact resistance, it is preferably 30:70 mol% or more and 98: 2 mol% or less, and more preferably 40:60 mol% or more and 95: 5 mol% or less.

The diamine unit in the semi-aromatic polyamide (B1) contains other diamine units other than the aliphatic diamine unit having 9 or 10 carbon atoms as long as the excellent properties of the obtained laminated tube are not impaired. You may be. Other diamine units include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptandiamine, 1 , 8-octane diamine, 1,11-undecane diamine, 1,12-dodecane diamine, 1,13-tridecane diamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, etc. Units derived from the aliphatic diamines of: 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, bis (4- Aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (3-methyl-4-aminocyclohexyl) propane, 5- Amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine, bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, 2,5- From alicyclic diamines such as bis (aminomethyl) norbornan, 2,6-bis (aminomethyl) norbornan, 3,8-bis (aminomethyl) tricyclodecane, 4,9-bis (aminomethyl) tricyclodecane, etc. Units to be derived; m-phenylenediamine, p-phenylenediamine, m-xylylene diamine, p-xylylene diamine, 1,4-bis (aminomethyl) naphthalene, 1,5-bis (aminomethyl) naphthalene, 2 , 6-bis (aminomethyl) naphthalene, 2,7-bis (aminomethyl) naphthalene, 4,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) propane, 4,4'-diaminodiphenylsulfone , 4,4'-Diaminodiphenyl ether and other units derived from aromatic diamines, and these may be used alone or in combination of two or more. The content of these other diamine units is less than 50 mol%, preferably 45 mol% or less, and preferably 40 mol% or less, based on the total diamine units of the semi-aromatic polyamide (B1). More preferred.

Further, the content of the terephthalic acid unit and / or the naphthalene dicarboxylic acid unit in the semi-aromatic polyamide (B1) sufficiently secures various physical properties such as heat resistance, chemical resistance, and chemical barrier property of the obtained laminated tube. From the viewpoint, it is 50 mol% or more, preferably 55 mol% or more, and more preferably 60 mol% or more, based on the total dicarboxylic acid units of the semi-aromatic polyamide (B1).

Examples of the naphthalene dicarboxylic acid unit include units derived from 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid and the like. These can be used alone or in combination of two or more. Among the naphthalene dicarboxylic acid units, units derived from 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid are preferable in consideration of economy and availability.

The dicarboxylic acid unit in the semi-aromatic polyamide (B1) may be a dicarboxylic acid unit other than the terephthalic acid unit and / or the naphthalenedicarboxylic acid unit as long as it does not impair the excellent properties of the obtained laminated tube. It may be included. Other dicarboxylic acid units include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, pimeric acid, 2,2-dimethylglutaric acid, 2,2-diethylsuccinic acid, and suberin. Acid, azelaic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedi Units derived from aliphatic dicarboxylic acids such as acids, octadecanedioic acids and eicosandioic acids; alicyclic formulas such as 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. Units derived from dicarboxylic acids; phthalic acid, isophthalic acid, 1,3-phenylenedioxydiacetic acid, 1,4-phenylenedioxydiacetic acid, 4,4'-oxydibenzoic acid, diphenylmethane-4,4'- Dicarboxylic acid, diphenylethane-4,4'-dicarboxylic acid, diphenylpropane-4,4'-dicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 4,4' Examples thereof include units derived from aromatic dicarboxylic acids such as −biphenyldicarboxylic acid and 4,4′-triphenyldicarboxylic acid, and these may be used alone or in combination of two or more. Among these, units derived from aromatic dicarboxylic acids are preferable. The content of these other dicarboxylic acid units is less than 50 mol%, preferably 45 mol% or less, and preferably 40 mol% or less, based on the total dicarboxylic acid units of the semi-aromatic polyamide (B1). Is more preferable. Further, polyvalent carboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid can be used within a range in which melt molding is possible.

The semi-aromatic polyamide (B1) may contain other units other than the dicarboxylic acid unit and the diamine unit as long as the excellent properties of the obtained laminated tube are not impaired. Other units include units derived from lactams such as caprolactam, enanthractam, undecanthractam, dodecanlactam, α-pyrrolidone, α-piperidone; 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11 Aliphatic aminocarboxylic acids such as −aminoundecanoic acid and 12-aminododecanoic acid; units derived from aminocarboxylic acids of aromatic aminocarboxylic acids such as p-aminomethylbenzoic acid can be mentioned. These can be used alone or in combination of two or more. The content of the other units is preferably 45 mol% or less, more preferably 40 mol% or less, and 35 mol% or less, based on all the monomer units of the semi-aromatic polyamide (B1). Is more preferable.

Further, as the equipment for producing the semi-aromatic polyamide (B1), 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, etc. Examples thereof include known polyamide production equipment such as a kneading reaction extruder of the above. As a polymerization method, known methods such as melt polymerization, solution polymerization, and solid phase polymerization can be used, and polymerization can be carried out by repeating normal pressure, reduced pressure, and pressurizing operations. These polymerization methods can be used alone or in combination as appropriate.

When producing the semi-aromatic polyamide (B1), phosphoric acid, phosphorous acid, hypophosphorous acid, salts or esters thereof and the like can be added as a catalyst. Examples of salts or esters of phosphoric acid, phosphite, hypophosphoric acid include phosphoric acid, phosphite, or phosphoric acid and potassium, sodium, magnesium, vanadium, calcium, zinc, cobalt, manganese, tin. , Tungsten, germanium, titanium, antimony and other metal salts, phosphoric acid, phosphoric acid, or ammonium salt of hypophosphoric acid, phosphoric acid, phosphoric acid, or ethyl ester, isopropyl ester, butyl ester of hypophosphoric acid. , Hexyl ester, isodecyl ester, decyl ester, stearyl ester, phenyl ester and the like. These can be used alone or in combination of two or more.

[Semi-aromatic polyamide (B2)]
The semi-aromatic polyamide composition (B) may contain a semi-aromatic polyamide (B2) (hereinafter, may be referred to as a semi-aromatic polyamide (B2)), and the semi-aromatic polyamide (B2) is a semi-aromatic polyamide (B2). Diamine units containing 50 mol% or more of xylylene diamine units and / or bis (aminomethyl) naphthalene units with respect to the total diamine units of the semi-aromatic polyamide (B2), and the total dicarboxylic acid of the semi-aromatic polyamide (B2). It contains a dicarboxylic acid unit containing 50 mol% or more of an aliphatic dicarboxylic acid unit having 9 or 10 carbon atoms with respect to the unit.

The content of the xylylenediamine unit and / or the bis (aminomethyl) naphthalene unit in the semi-aromatic polyamide (B2) includes various factors such as heat resistance, chemical resistance, impact resistance, and chemical barrier property of the obtained laminated tube. From the viewpoint of ensuring sufficient physical properties, the content is 50 mol% or more, preferably 55 mol% or more, and more preferably 60 mol% or more, based on the total diamine units of the semi-aromatic polyamide (B2). preferable.

Examples of the xylylenediamine unit include units derived from o-xylylenediamine, m-xylylenediamine, and p-xylylenediamine. These can be used alone or in combination of two or more. Among the xylylenediamine units, units derived from m-xylylenediamine and p-xylylenediamine are preferable.

The bis (aminomethyl) naphthalene unit is 1,4-bis (aminomethyl) naphthalene, 1,5-bis (aminomethyl) naphthalene, 2,6-bis (aminomethyl) naphthalene, and 2,7-bis (amino). Examples thereof include units derived from methyl) naphthalene and the like. These can be used alone or in combination of two or more. Among the bis (aminomethyl) naphthalene units, units derived from 1,5-bis (aminomethyl) naphthalene and 2,6-bis (aminomethyl) naphthalene are preferable.

The diamine unit in the semi-aromatic polyamide (B2) is a diamine other than the xylylenediamine unit and / or the bis (aminomethyl) naphthalene unit as long as it does not impair the excellent properties of the obtained laminated tube. It may include units. Other diamine units include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 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-Heptadecandiamine, 1,18-Octadecanediamine, 1,19-Nonadecanediamine, 1,20-Eicosandiamine, 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-Nonandiamine and other aliphatic diamines; 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane , 1,4-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,2-bis (4-aminocyclohexyl) propane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2 -Bis (3-methyl-4-aminocyclohexyl) propane, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine, bis (3-methyl-4-aminocyclohexyl) Aminopropyl) piperazine, bis (aminoethyl) piperazine, 2,5-bis (aminomethyl) norbornan, 2,6-bis (aminomethyl) norbornan, 3,8-bis (aminomethyl) tricyclodecane, 4,9 Units derived from alicyclic diamines such as -bis (aminomethyl) tricyclodecane; m-phenylenediamine, p-phenylenediamine, 4,4'-diaminodiphenylmethane, 2,2-bis (4-aminophenyl) Units derived from aromatic diamines such as propane, 4,4'-diaminodiphenyl sulfone, and 4,4'-diaminodiphenyl ether can be mentioned, and one or more of these can be used. Among these, units derived from aromatic diamines are preferable. The content of these other diamine units is less than 50 mol%, preferably 45 mol% or less, and preferably 40 mol% or less, based on the total diamine units of the semi-aromatic polyamide (B2). More preferred.

Examples of the aliphatic dicarboxylic acid unit having 9 or 10 carbon atoms include units derived from azelaic acid, sebacic acid and the like. As long as the number of carbon atoms satisfies the above, it may contain a unit derived from a branched chain aliphatic dicarboxylic acid such as 2,2,4-trimethyladipic acid and 2,4,4-trimethyladipic acid. .. These can be used alone or in combination of two or more. Among the aliphatic dicarboxylic acid units having 9 or 10 carbon atoms, a unit derived from sebacic acid is preferable from the viewpoint of availability and economy.

Further, the content of the aliphatic dicarboxylic acid unit having 9 or 10 carbon atoms in the semi-aromatic polyamide (B2) sufficiently satisfies various physical properties such as heat resistance, chemical resistance, and chemical barrier property of the obtained laminated tube. From the viewpoint of ensuring, the amount is 50 mol% or more, preferably 55 mol% or more, and more preferably 60 mol% or more, based on the total dicarboxylic acid units of the semi-aromatic polyamide (B2).

The dicarboxylic acid unit in the semi-aromatic polyamide (B2) is a dicarboxylic acid other than the aliphatic dicarboxylic acid unit having 9 or 10 elementary atoms as long as it does not impair the excellent properties of the obtained laminated tube. It may include a unit. Other dicarboxylic acid units include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, pimelli acid, suberic acid, undecanoic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, Units derived from aliphatic dicarboxylic acids such as hexadecanedioic acid, octadecanedioic acid, eikosandioic acid, 2-methyladipic acid, 2,2-dimethylglutaric acid, 2,2-diethylsuccinic acid, and 2-butylsveric acid. Units derived from alicyclic dicarboxylic acids such as 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid; terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid Acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,3-phenylenedioxydiacetic acid, 1,4-phenylenedioxydiacetic acid, 4,4' -Oxydibenzoic acid, diphenylmethane-4,4'-dicarboxylic acid, diphenylethane-4,4'-dicarboxylic acid, diphenylpropane-4,4'-dicarboxylic acid, diphenylether-4,4'-dicarboxylic acid, diphenylsulfone- Units derived from aromatic dicarboxylic acids such as 4,4'-dicarboxylic acid, 4,4'-biphenyldicarboxylic acid, and 4,4'-triphenyldicarboxylic acid can be mentioned, and these may be one or more. Can be used. The content of these other dicarboxylic acid units is less than 50 mol%, preferably 45 mol% or less, and preferably 40 mol% or less, based on the total dicarboxylic acid units of the semi-aromatic polyamide (B2). Is more preferable. Further, polyvalent carboxylic acids such as trimellitic acid, trimesic acid and pyromellitic acid can be used within a range in which melt molding is possible.

The semi-aromatic polyamide (B2) may contain other units other than the dicarboxylic acid unit and the diamine unit as long as the excellent properties of the obtained laminated tube are not impaired. Other units include units derived from lactams such as caprolactam, enanthractam, undecanthractam, dodecanlactam, α-pyrrolidone, α-piperidone; 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11 Aliphatic aminocarboxylic acids such as −aminoundecanoic acid and 12-aminododecanoic acid; units derived from aminocarboxylic acids of aromatic aminocarboxylic acids such as p-aminomethylbenzoic acid can be mentioned. These can be used alone or in combination of two or more. The content of the other units is preferably 45 mol% or less, more preferably 40 mol% or less, and 35 mol% or less, based on all the monomer units of the semi-aromatic polyamide (B2). Is more preferable.

Examples of the semi-aromatic polyamide (B2) manufacturing apparatus 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 a reaction extruder can be mentioned. As a method for producing the semi-aromatic polyamide (B2), there are known methods such as melt polymerization, solution polymerization, and solid phase polymerization. Using these methods, normal pressure, reduced pressure, and pressurization are repeated to achieve semi-aromaticity. Group polyamide (B2) can be produced. These production methods can be used alone or in combination as appropriate, and among these, the melt polymerization method is preferable. For example, a nylon salt composed of xylylene diamine and / or bis (aminomethyl) naphthalene and an aliphatic dicarboxylic acid having 9 or 10 carbon atoms is pressurized and heated in the presence of water, and added water and condensed water. It is produced by a method of polymerizing in a molten state while removing the above. It is also produced by a method in which xylylenediamine and / or bis (aminomethyl)naphthalene is directly added to an aliphatic dicarboxylic acid having 9 or 10 carbon atoms in a molten state and polycondensed under normal pressure. In this case, in order to keep the reaction system in a uniform liquid state, xylylenediamine and / or bis (aminomethyl) naphthalene is continuously added to the aliphatic dicarboxylic acid having 9 or 10 carbon atoms, and during that time, the reaction system is added. Polymerization proceeds while raising the temperature of the reaction system so that the temperature is equal to or higher than the melting points of the oligoamide and polyamide produced. Further, the semi-aromatic polyamide (B2) may be subjected to solid phase polymerization after being produced by the melt polymerization method.

A phosphorus atom-containing compound can be added to the semi-aromatic polyamide (B2) as a catalyst, to enhance processing stability during melt molding, and to prevent coloring. Phosphoric acid-containing compounds include hypophosphoric acid, phosphite, phosphoric acid, pyrophosphoric acid, metaphosphoric acid, phosphonic acid phosphonic acid and derivatives thereof, alkaline earth metal salts of hypophosphoric acid, and phosphite. Alkali metal salt, alkaline earth metal salt of phosphoric acid, alkali metal salt of phosphoric acid, alkaline earth metal salt of phosphoric acid, alkali metal salt of pyrophosphoric acid, alkaline earth metal salt of pyrophosphoric acid, alkali of metaphosphoric acid Metal salts, alkaline earth metal salts of metaphosphoric acid, alkali metal salts of phosphonic acid, alkaline earth metal salts of phosphonic acid, alkali metal salts of phosphonic acid, alkaline earth metal salts of phosphonic acid, etc. Be done.
Phosphoric acid-containing compounds include phosphinic acid (hypophosphoric acid), ethyl hypophosphate, dimethylphosphoric acid, phenylmethylphosphinic acid, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, and the following. Calcium phosphite, magnesium hypophosphite, phosphite, triethyl phosphite, triphenyl phosphite, sodium phosphite, sodium hydrogen phosphite, potassium phosphite, potassium hydrogen phosphite, lithium phosphite , Lithium hydrogen phosphite, magnesium phosphite, magnesium hydrogen phosphite, calcium phosphite, calcium hydrogen phosphite, pyrophosphoric acid, phosphoric acid, sodium phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate , Potassium phosphate, Dipotassium hydrogen phosphate, Potassium dihydrogen phosphate, Magnesium phosphate, Dimagnesium hydrogen phosphate, Magnesium dihydrogen phosphate, Calcium phosphate, Dicalcium hydrogen phosphate, Calcium dihydrogen phosphate, Lithium phosphate , Dilithium hydrogen phosphate, Lithium dihydrogen phosphate, Sodium pyrophosphate, Potassium pyrophosphate, Magnesium pyrophosphate, Calcium pyrophosphate, Lithium pyrophosphate, Sodium metaphosphate, Potassium metaphosphate, Magnesium metaphosphate, Calcium metaphosphate, Lithium metaphosphate , Phosphoric acid, sodium phosphite, lithium phosphite, potassium phosphite, magnesium phosphite, calcium phosphite, ethyl phenyl phosphite, sodium phenyl phosphite, potassium phenyl phosphite, phenyl sub Lithium phosphonate, phosphonic acid, sodium phosphonate, potassium phosphonate, lithium phosphonate, potassium phosphonate, magnesium phosphonate, calcium phosphonate, phenylphosphonic acid, ethylphosphonic acid, sodium phenylphosphonate, potassium phenylphosphonate, phenyl Examples thereof include lithium phosphonate, diethyl phenylphosphonate, sodium ethylphosphonate, potassium ethylphosphonate and the like. These can be used alone or in combination of two or more. Among these, sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, calcium hypophosphate, magnesium hypophosphite, calcium phosphite, calcium hydrogen phosphite, calcium dihydrogen phosphate, phosphite Sodium, sodium phosphite, sodium hydrogen phosphite, potassium phosphite, potassium hydrogen phosphite, lithium phosphite, lithium hydrogen phosphite, magnesium phosphite, magnesium hydrogen phosphite, calcium phosphite, sub Calcium hydrogen phosphate is preferable, and sodium hypophosphite, potassium hypophosphite, lithium hypophosphite, calcium hypophosphite, and magnesium hypophosphite are more preferable. In addition, these phosphorus atom-containing compounds may be hydrates.

The content of the phosphorus atom-containing compound is the phosphorus atom concentration with respect to 100 parts by mass of the semi-aromatic polyamide (B2) from the viewpoint of sufficiently ensuring the catalytic effect and the anti-coloring effect at the time of polymerization and suppressing the generation of gel. In terms of conversion, it is preferably 0.030 parts by mass or more and 0.30 parts by mass or less, more preferably 0.050 parts by mass or more and 0.20 parts by mass or less, and 0.070 parts by mass or more and 0.15 parts by mass or less. The following is more preferable.
The methods for adding these phosphorus atom-containing compounds include a method of adding to a nylon salt aqueous solution, a diamine or a dicarboxylic acid, which is a raw material of a semi-aromatic polyamide (B2), a method of adding to a dicarboxylic acid in a molten state, and a method of adding them during melt polymerization. Examples thereof include a method of addition, but any method may be used as long as it can be uniformly dispersed in the semi-aromatic polyamide (B2), and the method is not limited thereto.

An alkali metal compound or an alkaline earth metal compound can be added to the metalloid polyamide (B2) in combination with a phosphorus atom-containing compound. In order to prevent the coloration of the polyamide during polycondensation, it is necessary to have a sufficient amount of the phosphorus atom-containing compound, but in some cases, it may cause gelation of the polyamide. It is also preferable that an alkali metal compound or an alkaline earth metal compound coexists. Alkali metal compounds include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal acetates, alkaline earth metal acetates, alkali metal carbonates, alkaline earth metal carbonates, alkali metal alkoxides, and alkalis. Examples thereof include earth metal alkoxides, and alkali metal hydroxides and / or alkali metal acetates are preferable.

Alkali metal compounds include alkali metals / alkaline earth metals such as lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, and barium hydroxide. Hydroxide; Alkali metal / alkaline earth metal acetates such as lithium acetate, sodium acetate, potassium acetate, rubidium acetate, cesium acetate, magnesium acetate, calcium acetate, strontium acetate, barium acetate; lithium carbonate, sodium carbonate, Alkali metal / alkaline earth metal carbonates such as potassium carbonate, rubidium carbonate, cesium carbonate, magnesium carbonate, calcium carbonate, strontium carbonate, barium carbonate; sodium methoxyde, sodium ethoxide, sodium propoxide, sodium butoxide, potassium methoxy Examples thereof include alkali metal / alkaline earth metal alkoxides such as de, lithium methoxyd, magnesium methoxyd, and calcium methoxyd. These can be used alone or in combination of two or more. Among these, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium acetate, and potassium acetate are preferable from the viewpoint of economic efficiency.

When an alkali metal compound or an alkaline earth metal compound is added into the polycondensation system of the semi-aromatic polyamide (B2), the value obtained by dividing the number of moles of the compound by the number of phosphorus atom-equivalent moles of the phosphorus atom-containing compound is calculated. From the viewpoint of the balance between promotion and suppression of the amidation reaction, it is preferably 0.30 or more and 2.0 or less, more preferably 0.40 or more and 1.9 or less, and 0.50 or more and 1.8 or less. Is more preferable.
The method of adding these alkali metal compounds or alkaline earth metal compounds is a method of adding to a nylon salt aqueous solution, a diamine or a dicarboxylic acid, which is a raw material of a semi-aromatic polyamide (B2), or a method of adding to a molten dicarboxylic acid. , However, any method may be used as long as it can be uniformly dispersed in the semi-aromatic polyamide (B2), and the method is not limited thereto.

The relative viscosities of the semi-aromatic polyamide (B1) and semi-aromatic polyamide (B2) measured under the conditions of 96% sulfuric acid, polymer concentration 1%, and 25 ° C. according to JIS K-6920 are obtained laminated tubes. 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 4.0 or less, and 1.8 or more and 3 It is more preferably 5.5 or less, and further preferably 2.0 or more and 3.0 or less.

There are no particular restrictions on the type, concentration, and molecular weight distribution of the terminal groups of the semi-aromatic polyamide (B1) and the semi-aromatic polyamide (B2). One or a combination of two or more of monoamine, diamine, polyamine, monocarboxylic acid, and dicarboxylic acid can be added as appropriate for adjusting the molecular weight and stabilizing the melt during molding. For example, aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine; alicyclic type such as cyclohexylamine and dicyclohexylamine. Monoamines; aromatic monoamines such as aniline, toluidine, diphenylamine, naphthylamine; 1,4-butanedimine, 1,5-pentanedimine, 1,6-hexanediamine, 1,8-octanediamine, 2-methyl-1,5 -Adioxydiamine such as pentanediamine; alicyclic diamine such as cyclohexanediamine, bis (aminomethyl) cyclohexane, 5-amino-1,3,3-trimethylcyclohexanemethylamine; m-phenylenediamine, p-phenylenediamine and the like. Aromatic diamines; polyamines such as polyalkyleneimines, polyalkylene polyamines, polyvinylamines, polyallylamines; acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, capric acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, Adicyclic monocarboxylic acids such as stearic acid, pivalic acid, and isobutyric acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid; benzoic acid, toluic acid, α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid , Aromatic monocarboxylic acids such as phenylacetic acid; aliphatic dicarboxylic acids such as adipic acid and pimelic acid, fats such as 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid and 1,4-cyclohexanedicarboxylic acid. Cyclic dicarboxylic acid; Examples thereof include aromatic dicarboxylic acids such as phthalic acid and isophthalic acid. These can be used alone or in combination of two or more. The amount of these molecular weight adjusting agents used varies depending on the reactivity of the molecular weight adjusting agent and the polymerization conditions, but is appropriately determined so that the relative viscosity of the polyamide to be finally obtained is within the above range.

Considering the melt stability, it is preferable that the ends of the molecular chains of the semi-aromatic polyamide (B1) and the semi-aromatic polyamide (B2) are sealed with a terminal sealant, and 10% or more of the terminal groups are sealed. It is more preferable that it is stopped, and it is further preferable that 20% or more of the terminal groups are sealed. The terminal encapsulant is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the polyamide terminal, but from the viewpoint of reactivity, stability of the encapsulating end, etc. Acids or monoamines are preferable, and monocarboxylic acids are more preferable from the viewpoint of ease of handling and the like. In addition, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, monoalcohols and the like can also be used.

The monocarboxylic acid used as the terminal encapsulant is not particularly limited as long as it has reactivity with an amino group, but the above-mentioned aliphatic monocarboxylic acid, alicyclic monocarboxylic acid, and aromatic monocarboxylic acid. Carboxylic acid and the like can be mentioned. Among these, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, etc. from the viewpoints of reactivity, stability of the sealing end, price, etc. , Saprosylic acid is preferred. The monoamine used as the terminal encapsulant is not particularly limited as long as it has reactivity with a carboxyl group, and examples thereof include the above-mentioned aliphatic monoamine, alicyclic monoamine, and aromatic monoamine. Among these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are preferable from the viewpoints of reactivity, boiling point, stability of sealing end, price, and the like.
The amount of the end-capping agent used can be appropriately selected in consideration of the reactivity, boiling point, reaction apparatus, reaction conditions, etc. of the end-capping agent to be used. From the viewpoint of adjusting the degree of polymerization, it is preferably 0.1 mol% or more and 15 mol% or less with respect to the total number of moles of the raw material components dicarboxylic acid and diamine.

In order to improve the low temperature impact resistance of the semi-aromatic polyamide (B1) and the semi-aromatic polyamide (B2), it is preferable to add an impact improving material to the semi-aromatic polyamide composition (B), and in particular, the above-mentioned It is more preferable to add the elastomer polymer (A2) containing the structural unit derived from the unsaturated compound having a carboxyl group and / or an acid anhydride group described in the polyamide copolymer composition (A). .. If the elastomer polymer (A2) does not have a carboxyl group and / or an acid anhydride group, the impact improving effect may be insufficient.
The content of the impact improving material is 1 with respect to 100 parts by mass of the semi-aromatic polyamide (B1) or the semi-aromatic polyamide (B2) 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 30 parts by mass or less, and more preferably 3 parts by mass or more and 25 parts by mass or less.

The semi-aromatic polyamide composition (B) may contain another polyamide-based resin or other thermoplastic resin together with the semi-aromatic polyamide (B1) or the semi-aromatic polyamide (B2). Examples of the other polyamide-based resin or the other thermoplastic resin include the same resins as in the case of the polyamide copolymer composition (A). Further, it may be a mixture with the polyamide copolymer (A1). The content of the semi-aromatic polyamide (B1) or the semi-aromatic polyamide (B2) in the semi-aromatic polyamide composition (B) which is a mixture is preferably 60% by mass or more, preferably 70% by mass or more. Is more preferable.

Further, the semi-aromatic polyamide composition (B) contains, 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 the like. Flame retardants, crystallization accelerators, plasticizers, colorants, lubricants and the like may be added.

3. 3. (C) layer The laminated tube preferably further has a (c) layer.
The layer (c) of the laminated tube contains a fluorine-containing polymer (C) in which a functional group reactive with an amino group is introduced into the molecular chain (hereinafter referred to as a fluorine-containing polymer (C)). It may be called.).

[Fluorine-containing polymer (C)]
The fluorine-containing polymer (C) is a fluorine-containing polymer in which a functional group having reactivity with an amino group is introduced into the molecular chain.
The fluorine-containing polymer (C) is a polymer (homogeneous polymer or copolymer) having a repeating unit derived from at least one fluorine-containing monomer. It is not particularly limited as long as it is a fluorine-containing polymer that can be hot-melt processed.
Here, as the fluorine-containing monomer, tetrafluoroethylene (TFE), trifluoroethylene, vinylidene fluoride (VDF), vinyl fluoride (VF), chlorotrifluoroethylene (CTFE), trichlorofluoroethylene, hexafluoropropylene. (HFP), CF ₂ = CFOR ^f1 (where R ^f1 represents a perfluoroalkyl group which may contain etheric oxygen atoms having 1 or more and 10 or less carbon atoms), CF ₂ = CF-OCH _2- R. ^f2 (here, R ^f2 represents a perfluoroalkylene group which may contain an ethereal oxygen atom having 1 or more and 10 or less carbon atoms), CF ₂ = CF (CF ₂ ) _p OCF = CF ₂ (here, R f2). , P is 1 or 2), CH ₂ = CX ¹ (CF ₂ ) _n X ² (where X ¹ and X ² represent hydrogen or fluorine atoms independently of each other, and n is 2 or more and 10 or less. ), Etc. can be mentioned. These can be used alone or in combination of two or more.

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

Further, the general formula CH ₂ = CX ¹ (CF ₂ ) _n X ² (where X ¹ and X ² represent hydrogen atoms or fluorine atoms independently of each other, and n is an integer of 2 or more and 10 or less). From the viewpoint of ensuring the effect of modifying the fluorine-containing polymer (for example, during molding of the copolymer and suppressing the occurrence of cracks in the molded product) and obtaining sufficient polymerization reactivity, n in the compound represented by It is an integer of 2 or more and 10 or less. Specifically, CH ₂ = CF (CF ₂ ) ₂ F, CH ₂ = CF (CF ₂ ) ₃ F, CH ₂ = CF (CF ₂ ) ₄ F, CH ₂ = CF (CF ₂ ) ₅ F, CH ₂ = CF (CF ₂ ) ₈ F, CH ₂ = CF (CF ₂ ) ₂ H, CH ₂ = CF (CF ₂ ) ₃ H, CH ₂ = CF (CF ₂ ) ₄ H, CH ₂ = CF (CF ₂₎ ) ₅ H, CH ₂ = CF (CF ₂ ) ₈ H, CH ₂ = CH (CF ₂ ) ₂ F, CH ₂ = CH (CF ₂ ) ₃ F, CH ₂ = CH (CF ₂ ) ₄ F, CH ₂ = CH (CF ₂ ) ₅ F, CH ₂ = CH (CF ₂ ) ₈ F, CH ₂ = CH (CF ₂ ) ₂ H, CH ₂ = CH (CF ₂ ) ₃ H, CH ₂ = CH (CF ₂ ) ₄ H, CH ₂ = CH (CF ₂ ) ₅ H, CH ₂ = CH (CF ₂ ) ₈ H and the like. These can be used alone or in combination of two or more.
Among these, from the viewpoint of the balance between the chemical barrier property and the environmental stress crack resistance of the fluorine-containing polymer (C), CH ₂ = CH (CF ₂ ) _n F or CH ₂ = CF (CF ₂ ) _n H. The represented compound is preferable, and n in the formula is more preferably 2 or more and 4 or less.

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

Among the fluorine-containing polymers (C), at least a copolymer (C1) composed of vinylidene fluoride units (VDF units), at least tetrafluoroethylene, from the viewpoint of heat resistance, chemical resistance, and chemical barrier property. Copolymer (C2) consisting of units (TFE units) and ethylene units (E units), at least tetrafluoroethylene units (TFE units) and hexafluoropropylene units (HFP units) and / or the general formula CF ₂ = CFOR. ^A copolymer (C3) composed of PAVE units derived from PAVE represented by f1 (where R ^f1 represents a perfluoroalkyl group which may contain etheric oxygen atoms having 1 or more and 10 or less carbon atoms). , At least a copolymer consisting of chlorotrifluoroethylene units (CTFE units) (C4), and at least a copolymer consisting of chlorotrifluoroethylene units (CTFE units) and tetrafluoroethylene units (TFE units) (C5). It is preferable to have.

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

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

At least, the copolymer (C2) composed of tetrafluoroethylene units (TFE units) and ethylene units (E units) (hereinafter, may be referred to as TFE copolymer (C2)), for example, the functionality described below. Examples thereof include polymers having a TFE unit content of 20 mol% or more with respect to the entire monomer excluding the group-containing monomer, and further, the entire monomer excluding the functional group-containing monomer described later. On the other hand, the content of TFE units is 20 mol% or more and 80 mol% or less, the content of E units is 20 mol% or more and 80 mol% or less, and the content of units derived from a monomer copolymerizable with these is contained. Examples thereof include copolymers having an amount of 0 mol% or more and 60 mol% or less.

Examples of the copolymerizable monomer include hexafluoropropylene (HFP) and the general formula CF ₂ = CFOR ^{f1 (where R f1} may contain ether oxygen atoms having 1 to 10 carbon atoms). ), The general formula CH ₂ = CX ¹ (CF ₂ ) _n X ² (where X ¹ and X ² represent hydrogen or fluorine atoms independently of each other, and n is 2 or more and 10 or less. It is an integer of.) And the like. These can be used alone or in combination of two or more.

Examples of the TFE copolymer (C2) include, for example.
The TFE unit and the E unit, and the general formula CH ₂ = CX ¹ (CF ₂ ) _n X ² (where X ¹ and X ² represent hydrogen atoms or fluorine atoms independently of each other, and n is 2 or more and 10 or less. It is a copolymer composed of fluoroolefin units derived from fluoroolefin represented by an integer.), And the content of TFE units is the total amount of the monomer excluding the functional group-containing monomer described later. 30 mol% or more and 70 mol% or less, the content of E unit is 20 mol% or more and 55 mol% or less, and the general formula CH ₂ = CX ³ (CF ₂ ) _n X ⁴ (where X ³ and X ⁴ are It represents a hydrogen atom or a fluorine atom independently of each other, and n is an integer of 2 or more and 10 or less.) The content of the fluoroolefin unit derived from the fluoroolefin is 0 mol% or more and 10 mol% or less. Polymer (C2-1),
A copolymer consisting of a TFE unit, an E unit, an HFP unit, and a unit derived from a monomer copolymerizable with these, with respect to the entire monomer excluding the functional group-containing monomer described later. The content of TFE units is 30 mol% or more and 70 mol% or less, the content of E units is 20 mol% or more and 55 mol% or less, the content of HFP units is 1 mol% or more and 30 mol% or less, and copolymerization with these. A copolymer (C2-2) in which the content of a unit derived from a possible monomer is 0 mol% or more and 10 mol% or less,
It is represented by a TFE unit and an E unit, and the general formula CF ₂ = CFOR ^f1 (where R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 or more and 10 or less carbon atoms). A copolymer composed of PAVE units derived from PAVE, wherein the content of TFE units is 30 mol% or more and 70 mol% or less, E units, with respect to the entire monomer excluding the functional group-containing monomer described later. The content of is 20 mol% or more and 55 mol% or less, and the general formula CF ₂ = CFOR ^f1 (where R ^f1 is a perfluoroalkyl group which may contain an etheric oxygen atom having 1 or more and 10 or less carbon atoms. Examples thereof include a copolymer (C2-3) in which the content of PAVE units derived from PAVE represented by (represented) is 0 mol% or more and 10 mol% or less.

At least a tetrafluoroethylene unit (TFE unit) and a hexafluoropropylene unit (HFP unit) and / or the general formula CF ₂ = CFOR ^f1 (where R ^f1 is an ether oxygen atom having 1 or more carbon atoms and 10 or less carbon atoms. As a copolymer (C3) composed of PAVE units derived from PAVE represented by (representing a perfluoroalkyl group that may be contained) (hereinafter, may be referred to as a TFE copolymer (C3)), for example. ,
It is a copolymer composed of TFE units and HFP units, and the content of TFE units is preferably 70 mol% or more and 95 mol% or less with respect to the entire monomer excluding the functional group-containing monomer described later. Is 85 mol% or more and 93 mol% or less, and the content of HFP units is 5 mol% or more and 30 mol% or less, preferably 7 mol% or more and 15 mol% or less of the copolymer (C3-1).
It is derived from the TFE unit and _{PAVE represented by the general formula CF 2} = CFOR ^f1 (where R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 or more and 10 or less carbon atoms). A copolymer composed of one or more PAVE units, wherein the content of TFE units is 70 mol% or more and 95 mol% or less with respect to the entire monomer excluding the functional group-containing monomer described later. , And the above general formula CF ₂ = CFOR ^f1 (where R ^f1 represents a perfluoroalkyl group which may contain an ethereal oxygen atom having 1 or more and 10 or less carbon atoms). A copolymer (C3-2) in which the content of the seed or two or more PAVE units is 5 mol% or more and 30 mol% or less.
It is represented by a TFE unit, an HFP unit, and the general formula CF ₂ = CFOR ^f1 (where R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 or more carbon atoms and 10 or less carbon atoms). A copolymer composed of one or more PAVE units derived from PAVE, wherein the content of TFE units is 70 mol% or more with respect to the entire monomer excluding the functional group-containing monomer described later. It is represented by 95 mol% or less, HFP unit and the general formula CF ₂ = CFOR ^f1 (where R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 or more and 10 or less carbon atoms). Examples thereof include a copolymer (C3-3) in which the total content of one or more PAVE units derived from PAVE is 5 mol% or more and 30 mol% or less.

At least, the copolymer composed of chlorotrifluoroethylene units (CTFE units) has CTFE units [-CFCl-CF _2- ] and is composed of ethylene units (E units) and / or fluorine-containing monomer units. The chlorotrifluoroethylene copolymer (C4) to be used (hereinafter, may be referred to as CTFE copolymer (C4)).
The fluorine-containing monomer in the CTFE copolymer (C4) is not particularly limited as long as it is other than CTFE, but vinylidene fluoride (VDF), hexafluoropropylene (HFP), and the general formula CF ₂ = CFOR. ^{PAVE represented by f1} (where R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 or more and 10 or less carbon atoms), the general formula CH ₂ = CX ¹ (CF ₂ ). Examples thereof include _{fluoroolefins represented by n} X ^{2 (where X 1} and X ² represent hydrogen atoms or fluorine atoms independently of each other, and n is an integer of 2 or more and 10 or less). These can be used alone or in combination of two or more.

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

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

At least, a copolymer consisting of chlorotrifluoroethylene units (CTFE units) and tetrafluoroethylene units (TFE units) (C5) is, CTFE unit [-CFCl-CF ₂ -] and TFE units _[-CF 2 -CF ₂ -], And a chlorotrifluoroethylene copolymer composed of CTFE and a monomer unit copolymerizable with TFE (hereinafter, may be referred to as CTFE / TFE copolymer (C5)).

The copolymerizable monomer in the CTFE / TFE copolymer (C5) is not particularly limited as long as it is other than CTFE and TFE, but vinylidene fluoride (VDF), hexafluoropropylene (HFP), the above. PAVE represented by the general formula CF ₂ = CFOR ^f1 (where R ^f1 represents a perfluoroalkyl group which may contain an ethereal oxygen atom having 1 or more and 10 or less carbon atoms), the general formula CH ₂ =. CX ¹ (CF ₂ ) _n X ² (where X ¹ and X ² represent hydrogen atoms or fluorine atoms independently of each other, and n is an integer of 2 or more and 10 or less), or the like. Fluorine-containing monomer; olefins having 2 to 4 carbon atoms such as ethylene, propylene and isobutene; vinyl esters such as vinyl acetate, methyl (meth) acrylate, ethyl (meth) acrylate; methyl vinyl ether (MVE) , Non-fluorine-containing monomers such as vinyl ethers such as ethyl vinyl ether (EVE) and butyl vinyl ether (BVE). These can be used alone or in combination of two or more. Among these, _{PAVE represented by the general formula CF 2} = CFOR ^f1 (here, R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 or more and 10 or less carbon atoms). It is preferable, perfluoro (methyl vinyl ether) (PMVE) and perfluoro (provir vinyl ether) (PPVE) are more preferable, and PPVE is further preferable from the viewpoint of heat resistance.

The CTFE / TFE copolymer (C5) is not particularly limited, and for example, a CTFE / TFE copolymer, a CTFE / TFE / HFP copolymer, a CTFE / TFE / VDF copolymer, and a CTFE / TFE / PAVE copolymer. Examples thereof include coalescence, CTFE / TFE / E copolymer, CTFE / TFE / HFP / PAVE copolymer, CTFE / TFE / VDF / PAVE copolymer, etc. Among these, CTFE / TFE / PAVE copolymer, CTFE / TFE / HFP / PAVE copolymers are preferred.

The total content of CTFE units and TFE units in the CTFE / TFE copolymer (C5) will be described later from the viewpoint of ensuring good moldability, environmental stress crack resistance, chemical barrier property, heat resistance, and mechanical properties. 90.0 mol% or more and 99.9 mol% or less are preferable with respect to the whole monomer excluding the functional group-containing monomer, and the content of the monomer unit copolymerizable with the CTFE and TFE The amount is preferably 0.10 mol% or more and 10.0 mol% or less.

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

In the CTFE / TFE copolymer (C5), when the monomer copolymerizable with CTFE and TFE is PAVE, the content of the PAVE unit is the entire monomer excluding the functional group-containing monomer described later. On the other hand, it is preferably 0.5 mol% or more and 7 mol% or less, and more preferably 1 mol% or more and 5 mol% or less.

In the CTFE / TFE copolymer (C5), when the monomers copolymerizable with CTFE and TFE are HFP and PAVE, the total content of the HFP unit and the PAVE unit is the functional group-containing monomer described later. It is preferably 0.5 mol% or more and 7 mol% or less, and more preferably 1 mol% or more and 5 mol% or less with respect to the whole monomer excluding.

The TFE copolymer (C3), CTFE copolymer (C4), and CTFE / TFE copolymer (C5) are excellent in chemical barrier properties, particularly barrier properties against alcohol-containing gasoline. For the alcohol-containing gasoline permeation coefficient, a sheet obtained from the resin to be measured is placed in a permeation coefficient measurement cup containing an isooctane / toluene / ethanol mixed solvent in which isooctane, toluene, and ethanol are mixed at a volume ratio of 45:45:10. , A value calculated from the mass change measured at 60 ° C. The alcohol-containing gasoline permeation coefficient of the TFE copolymer (C3), CTFE copolymer (C4), and CTFE / TFE copolymer (C5) is 1.5 g · mm / (m ² · day) or less. it is preferred, more preferably not more than ^{0.010g · mm / (m 2 ·} day) or more ^{1.0g · mm / (m 2 ·} day), 0.020g · mm / (m 2 · day) or more It is more preferably 0.80 g · mm / (m ² · day) or less.

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

The method for producing the fluorine-containing polymer (C) is not particularly limited, and a commonly used polymerization method using a radical polymerization initiator is used. As the polymerization method, bulk polymerization, solution polymerization using an organic solvent such as fluorinated hydrocarbon, chlorinated hydrocarbon, fluorinated hydrocarbon, alcohol, hydrocarbon, aqueous medium and suitable organic solvent if necessary are used. Known methods such as suspension polymerization, emulsion polymerization using an aqueous medium and an emulsifier, etc. can be adopted.
Further, the polymerization can be carried out as a batch type or a continuous type operation using a one-tank or multi-tank type stirring type polymerization device or tube type polymerization device.

As the radical polymerization initiator, the decomposition temperature having a half-life of 10 hours is preferably 0 ° C. or higher and 100 ° C. or lower, and more preferably 20 ° C. or higher and 90 ° C. or lower. Specific examples include 2,2'-azobisisobutyronitrile, 2,2'-azobis (2,4-dimethylvaleronitrile), 2,2'-azobis (2-methylvaleronitrile), 2,2. '-Azobis (2-cyclopropylpropionitrile), 2,2'-azobisisobutyrate dimethyl, 2,2'-azobis [2- (hydroxymethyl) propionitrile], 4,4'-azobis (4-cyano) Azo compounds such as pentenoic acid); hydroperoxides such as hydrogen peroxide, t-butyl hydroperoxide, cumene hydroperoxide; dialkyl peroxides such as di-t-butyl peroxide and dicumyl peroxide; acetyl peroxide , Isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide, lauroyl peroxide and other non-fluorine diacyl peroxides; methyl ethyl ketone peroxide, cyclohexanone peroxide and other ketone peroxides; diisopropyl peroxydicarbonate and other peroxydi Carbonate; peroxyesters such as t-butylperoxypivalate, t-butylperoxyisobutyrate, t-butylperoxyacetate; (Z (CF ₂ ) _p COO) ₂ (where Z is a hydrogen atom, It is a fluorine atom or a chlorine atom, and p is an integer of 1 or more and 10 or less.) A fluorine-containing diacyl peroxide such as a compound; an inorganic peroxide such as potassium persulfate, sodium persulfate, ammonium persulfate, etc. Can be mentioned. These can be used alone or in combination of two or more.

Further, in the production of the fluorine-containing polymer (C), it is also preferable to use an ordinary chain transfer agent for adjusting the molecular weight. Examples of the chain transfer agent include alcohols such as methanol and ethanol, 1,3-dichloro-1,1,2,2,3-pentafluoropropane, 1,1-dichloro-1-fluoroethane, and 1,2-dichloro-. Chlorofluorohydrocarbons such as 1,1,2,2-tetrafluoroethane, 1,1-dichloro-1-fluoroethane, 1,1,2-trichloro-1,2,2-trifluoroethane; pentane, hexane , Hydrocarbons such as cyclohexane; chlorohydrocarbons such as carbon tetrachloride, chloroform, methylene chloride, methyl chloride and the like. These can be used alone or in combination of two or more.

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

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

When the fluorine-containing polymer (C) is co-extruded with the polyamide copolymer composition (A), semi-aromatic polyamide composition (B), etc., the kneading temperature and molding temperature range without significant deterioration thereof. In order to ensure sufficient melt fluidity, the melt flow rate at a temperature 50 ° C. higher than the melting point of the fluoropolymer (C) and a load of 5 kg is 0.5 g / 10 minutes or more and 200 g / 10 minutes. It is preferably 1 g / 10 minutes or more and 100 g / 10 minutes or less.

Further, in the fluorine-containing polymer (C), the melting point and the glass transition point of the polymer can be adjusted by selecting the type, composition ratio, etc. of the fluorine-containing monomer and other monomers. The melting point of the fluorine-containing polymer (C) is appropriately selected depending on the purpose, use, and method of use, and is coextruded with the polyamide copolymer composition (A), the semi-aromatic polyamide composition (B), and the like. In this case, it is preferable that the temperature is close to the molding temperature of the resin. Therefore, it is preferable to optimize the melting point of the fluorine-containing polymer (C) by appropriately adjusting the ratio of the fluorine-containing monomer and other monomers to the functional group-containing monomer described later.
Here, the melting point means that the sample is heated to a temperature higher than the expected melting point by using a differential scanning calorimetry device, and then the sample is cooled at a rate of 10 ° C. per minute and cooled to 30 ° C. The melting point is defined as the temperature of the peak value of the melting curve measured by leaving the sample as it is for about 1 minute and then raising the temperature at a rate of 10 ° C. per minute.

The fluorine-containing polymer (C) has a functional group reactive with an amino group in the molecular structure, and the functional group is the molecular terminal or side chain of the fluorine-containing polymer (C) or the side chain. It may be contained in any of the main chains. Further, the functional group may be used alone or in combination of two or more kinds in the fluorine-containing polymer (C). The type and content of the functional group are appropriately determined depending on the type, shape, use, required interlayer adhesiveness, adhesion method, functional group introduction method, etc. of the mating material laminated on the fluorine-containing polymer (C). To.

The functional group having a reactivity with an amino group is selected from the group from a carboxyl group, an acid anhydride group or a carboxylate, a sulfo group or a sulfonate group, an epoxy group, a cyano group, a carbonate group, and a haloformyl group. At least one type is mentioned. Among these, at least one selected from the group consisting of a carboxyl group, an acid anhydride group or a carboxylate, an epoxy group, a carbonate group, and a haloformyl group is preferable.

As a method for introducing a functional group having a reactivity into the fluorine-containing polymer (C), (i) a copolymerizable monomer having a functional group is used together with the fluorine-containing polymer (C) at the time of polymerization. A method of polymerizing, (ii) a method of introducing a functional group into the molecular terminal of the fluoropolymer (C) at the time of polymerization by a polymerization initiator, a chain transfer agent, etc., (iii) grafting a reactive functional group. Examples thereof include a method of grafting a compound (graft compound) having a functional group capable of using a fluorine-containing polymer to a fluoropolymer. These introduction methods can be used alone or in combination as appropriate. Considering the interlayer adhesiveness in the laminated tube, the fluorine-containing polymer (C) produced from the above (i) and (ii) is preferable. Regarding (iii), JP-A-7-18835, JP-A-7-25952, JP-A-7-25954, JP-A-7-173230, JP-A-7-173446, JP-A-7- Please refer to the manufacturing method according to Japanese Patent Publication No. 173447 and Japanese Square Root 10-503236. Hereinafter, (i) a method of copolymerizing a copolymerizable monomer having a functional group at the time of polymerization of the fluoropolymer, (ii) a functional group at the molecular terminal of the fluoropolymer by a polymerization initiator or the like. Explains how to introduce.

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

The functional group-containing non-fluorine monomer includes acrylic acid, halogenated acrylic acid (excluding fluorine), methacrylic acid, halogenated methacrylic acid (excluding fluorine), maleic acid, and maleic anhydride (excluding fluorine). , Fluorine excluded), fumaric acid, halogenated fumaric acid (excluding fluorine), esteric acid, citraconic acid, crotonic acid, endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic Unsaturated carboxylic acids such as acids and derivatives such as esters thereof; maleic anhydride, itaconic anhydride, succinic anhydride, citraconic anhydride, endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic Carboxyl group-containing monomers such as acid anhydride; and epoxy group-containing monomers such as glycidyl acrylate, glycidyl methacrylate, and glycidyl ether can be mentioned. These can be used alone or in combination of two or more. The functional group-containing non-fluorine monomer is determined in consideration of the copolymerization reactivity with the fluorine-containing monomer used. By selecting an appropriate functional group-containing non-fluorine monomer, polymerization proceeds well, and it is easy to uniformly introduce the functional group-containing non-fluorine monomer into the main chain, resulting in less unreacted monomers. , There is an advantage that impurities can be reduced.

As the functional group-containing fluorine-containing monomer, the general formula CX ³ X ⁴ = CX ^5- (R ⁷ ) _n- Y (where Y is -COMM (M represents a hydrogen atom or an alkali metal)). , carboxyl group derived base, (the M,. represents a hydrogen atom or an alkali metal) _-SO 3 M, represents a sulfonic acid-derived group, an epoxy group, and a functional group selected from the group consisting of ^{-CN, X} 3, X ⁴ and X ⁵ represent the same or different hydrogen atom or fluorine atom (provided that if X ³ , X ⁴ and X ⁵ are the same hydrogen atom, n = 1 and R ⁷ is fluorine. Includes atoms.), R ⁷ is an alkylene group having 1 to 40 carbon atoms, a fluorine-containing oxyalkylene group having 1 to 40 carbon atoms, and a fluorine-containing alkylene having an ether bond and having 1 to 40 carbon atoms. Examples thereof include an unsaturated compound represented by a group or a fluorine-containing oxyalkylene group having an ether bond having 1 or more and 40 or less carbon atoms, and n being 0 or 1).
As the carboxyl group-derived group that is Y in the general formula, for example, the general formula −C (= O) Q ¹ (in the formula, Q ¹ is −OR ⁸ , −NH ₂ , F, Cl, Br or I. In addition, R ⁸ represents an alkyl group having 1 or more and 20 or less carbon atoms or an aryl group having 6 or more and 22 or less carbon atoms).
The Y is preferably -COOH, -SO ₃ H, -SO ₃ Na, -SO ₂ F or -CN.

Examples of the functional group-containing fluorine-containing monomer include perfluoroacrylic acid fluoride, 1-fluoroacrylic acid fluoride, acrylic acid fluoride, 1-trifluoromethacrylic acid fluoride, and perfluoro when the functional group has a carbonyl group. Butenoic acid and the like can be mentioned. These can be used alone or in combination of two or more.

The content of the functional group-containing monomer in the fluorine-containing polymer (C) ensures sufficient interlayer adhesiveness, does not cause a decrease in interlayer adhesiveness depending on the operating environment conditions, and sufficiently secures heat resistance. However, from the viewpoint of preventing the occurrence of peeling, coloring, foaming, elution, etc. due to decomposition during processing at high temperature, poor adhesion, coloring, foaming, and use at high temperature, 0. It is preferably 01 mol% or more and 5.0 mol% or less, more preferably 0.015 mol% or more and 4.0 mol% or less, and 0.02 mol% or more and 3.0 mol% or less. Is more preferable. When the content of the functional group-containing monomer is within the above range, the polymerization rate during production does not decrease, and the fluorine-containing polymer (C) has excellent adhesiveness to the mating material to be laminated. Become. The method of adding the functional group-containing monomer is not particularly limited, and the functional group-containing monomer may be added all at once at the start of polymerization or continuously during the polymerization. The method of addition is appropriately selected depending on the decomposition reactivity of the polymerization initiator and the polymerization temperature, and the amount consumed is continuously or intermittently as the functional group-containing monomer is consumed in the polymerization during the polymerization. It is preferable to supply the polymer in a polymerization tank and maintain the concentration of the functional group-containing monomer in this range.
The content of the functional group-containing monomer in the fluorine-containing copolymer (C) is 0.01 mol% with respect to the total polymerization unit, which is the functionality in the fluorine-containing copolymer (C). The content of the group residue corresponds to 100 for the main chain carbon number of 1 × 10 ^{6 of the fluorine-containing copolymer (C).} Further, 5.0 mol% with respect to the total polymerization units in the fluorine-containing copolymer (C) means that the content of the functional group residue in the fluorine-containing copolymer (C) is the fluorine-containing copolymer. This corresponds to 50,000 for ^{every 1 × 10 6} main chain carbons in (C).
Further, as long as the above content is satisfied, it may be a mixture of a fluorine-containing polymer having a functional group introduced therein and a fluorine-containing polymer having no functional group introduced therein.

(Ii) In the method of introducing a functional group into the molecular end of a fluorine-containing polymer using a polymerization initiator or the like, the functional group is introduced into one end or both ends of the molecular chain of the fluorine-containing polymer. As the functional group introduced at the terminal, a carbonate group and a haloformyl group are preferable.

The carbonate group introduced as the terminal group of the fluorine-containing polymer (C) is generally a group having an −OC (= O) O− bond, and specifically, −OC (= O) OR. ¹⁰ groups [R ¹⁰ is a hydrogen atom, an organic group (for example, an alkyl group having 1 or more and 20 or less carbon atoms, an alkyl group having 2 or more and 20 or less carbon atoms having an ether bond, etc.), or an I, II, or VII group element. .. ] Structure, -OC (= O) OCH ₃ , -OC (= O) OC ₃ H ₇ , -OC (= O) OC ₈ H ₁₇ , -OC (= O) OCH ₂ CH ₂ OCH ₂ CH _{3 and the} like can be mentioned. Specifically, the haloformyl group is -COZ [Z is a halogen element. ], Examples thereof include -COF and -COCl. These can be used alone or in combination of two or more.

Further, in order to introduce a carbonate group into the molecular terminal of the polymer, various methods using a polymerization initiator and / or a chain transfer agent can be adopted, but peroxides, particularly peroxycarbonates and / or peroxyesters, can be adopted. Can be preferably adopted from the viewpoint of performance such as economy, heat resistance, and chemical resistance. According to this method, a carbonyl group derived from peroxide, for example, a carbonate group derived from peroxycarbonate, an ester group derived from peroxyester, or a polymer such as a haloformyl group obtained by converting these functional groups. It can be introduced at the end. Of these polymerization initiators, it is more preferable to use peroxycarbonate because the polymerization temperature can be lowered and the initiation reaction does not involve a side reaction.

Various methods can be adopted for introducing a haloformyl group into the molecular terminal of the polymer. For example, the carbonate group of the fluorine-containing polymer having the above-mentioned carbonate group at the terminal is heated and thermally decomposed (decarboxylation). It can be obtained by letting it.

Examples of the peroxy carbonate include diisopropyl peroxy carbonate, di-n-propyl peroxy carbonate, t-butyl peroxyisopropyl carbonate, t-butylperoxymethacryloyloxyethyl carbonate, and bis (4-t-butylcyclohexyl) peroxy. Examples thereof include dicarbonate and di-2-ethylhexyl peroxydicarbonate. These can be used alone or in combination of two or more.

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

Terminal functional groups is for several 10 ⁶ main chain carbon atoms in the fluorine-containing polymer (C), ensuring sufficient interlayer adhesion, the operating environment, without causing a reduction in the interlaminar adhesion, the heat resistance From the viewpoint of ensuring sufficient and preventing the occurrence of peeling, coloring, foaming, elution, etc. due to decomposition when processing at high temperature, poor adhesion, coloring, and foaming, and when using at high temperature, 150 or more 3,000 The number is preferably less than, more preferably 200 or more and 2,000 or less, and further preferably 300 or more and 1,000 or less. Further, as long as the number of functional groups is satisfied, it may be a mixture of a fluorine-containing polymer into which a functional group has been introduced and a fluorine-containing polymer into which no functional group has been introduced.

As described above, the fluorine-containing polymer (C) is a fluorine-containing polymer into which a functional group having reactivity with an amino group has been introduced. As described above, the fluorine-containing polymer (C) into which a functional group has been introduced has its own heat resistance, water resistance, low friction resistance, chemical resistance, weather resistance, and stain resistance peculiar to the fluorine-containing polymer. , It is possible to maintain excellent properties such as chemical barrier properties, which is advantageous in terms of productivity and cost.

Further, since a functional group having a reactivity with an amino group is contained in the molecular chain, various materials having insufficient or impossible interlayer adhesiveness in the laminated tube are specially treated such as surface treatment. It is possible to directly impart excellent interlayer adhesiveness to other base materials without performing any treatment and / or coating with an adhesive resin.

The fluorine-containing polymer (C) can be added with various fillers such as inorganic powder, glass fiber, carbon fiber, metal oxide, and carbon as long as its performance is not impaired depending on the purpose and application. In addition to the filler, pigments, ultraviolet absorbers, and any other additives can be mixed. In addition to the additives, other fluororesins, resins such as thermoplastic resins, synthetic rubber, etc. can be added to improve mechanical properties, improve weather resistance, impart design, antistatic, and moldability. Improvements can be made.

[Laminated tube]
The first aspect of the laminated tube includes at least two layers (a) and (b), and at least one set of layers (a) and (b) are arranged adjacent to each other.

In the laminated tube of the first aspect, it is essential to include the layer (b), and the chemical barrier property of the laminated tube, particularly the hydrocarbon barrier property, becomes good. Further, by arranging the layer (a) and the layer (b) adjacent to each other, it is possible to obtain a laminated tube having excellent interlayer adhesiveness and durability thereof.

In a preferred embodiment, the layer (b) is arranged inside the layer (a). In a more preferred embodiment, layer (a) is located on the outermost layer of the laminated tube. By arranging the layer (a) on the outermost layer, it is possible to obtain a laminated tube having excellent chemical resistance and flexibility.

In a more preferred embodiment, the layer (b) is arranged in the innermost layer of the laminated tube. By arranging the layer (b) in the innermost layer, a laminated tube having excellent deterioration fuel resistance can be obtained, and elution of low molecular weight components such as monomers and oligomers due to contact with alcohol-containing gasoline can be suppressed. Become. That is, a laminated tube in which the layer (a) is arranged in the outermost layer and the layer (b) is arranged in the innermost layer is more preferable.

Further, in the laminated tube of the first aspect, when the conductive layer containing the semi-aromatic polyamide composition (B) containing the conductive filler is arranged in the innermost layer of the laminated tube, it has chemical barrier properties and deterioration resistance fuel. It has excellent properties and elution resistance of monomers and oligomers, and when used as a fuel pipe tube, it prevents sparks generated by internal friction of the fuel circulating in the pipe or friction with the pipe wall from igniting the fuel. It becomes possible to do. At that time, by arranging the layer containing the semi-aromatic polyamide having no conductivity on the outside with respect to the conductive layer, it is possible to achieve both low temperature impact resistance and conductivity, and it is economical. It is also 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 transported.
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 carbon fibers, carbon-coated ceramic fibers, carbon whiskers, carbon nanotubes, aluminum fibers, copper fibers, brass fibers, and metal fibers such as 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, and 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. Is more preferable. 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.

Carbon black includes all carbon blacks generally used for imparting conductivity, and preferred carbon blacks are acetylene black obtained by incomplete combustion of acetylene gas and furnace-type incomplete combustion using crude oil as a raw material. Examples include, but are not limited to, furnace black such as Ketjen black, oil black, naphthalin black, thermal black, lamp black, channel black, roll black, and disc black produced by. 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, ash content and the like 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% 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 balance with conductivity, fluidity, mechanical strength, etc., semi-aromatic polyamide (B1) or Generally, it is preferably 3 parts by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the semi-aromatic polyamide (B2).
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 first aspect, 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 in consideration of characteristics such as chemical barrier property, low temperature impact resistance, and flexibility of the laminated tube. In general, the thickness of the layer (a) and the layer (b) is preferably 3% or more and 90% or less, respectively, with respect to the thickness of the entire laminated tube. Considering the balance between low temperature impact resistance and chemical barrier property, the thickness of the layer (b) is more preferably 5% or more and 50% or less, and 7% or more and 30% with respect to the total thickness of the laminated tube. The following is more preferable.

Further, the total number of layers in the laminated tube of the first aspect is not particularly limited as long as it has at least two layers having a layer (a) and a layer (b). Further, in the laminated tube of the first aspect, in addition to the two layers of the layer (a) and the layer (b), another thermoplastic resin may be used in order to impart further functions or obtain an economically advantageous laminated tube. The containing layer may have one layer or two or more layers. The number of layers of the laminated tube of the first aspect is two or more, but judging from the mechanism of the tube manufacturing apparatus, it is preferably 8 or less, and more preferably 2 or more and 7 or less.

The second aspect of the laminated tube includes at least three layers having the (c) layer in the first aspect, and at least one set of the (b) layer and the (c) layer are arranged adjacent to each other.

In the laminated tube of the second aspect, it is essential to include the layer (b), and the chemical barrier property of the laminated tube, particularly the hydrocarbon barrier property, becomes good. Further, it is also essential to include the layer (c), and the chemical barrier property of the laminated tube, particularly the alcohol barrier property and the barrier property against high-concentration alcohol-containing gasoline, becomes good. Further, by arranging the layer (b) and the layer (c) adjacent to each other, it is possible to obtain a laminated tube having excellent interlayer adhesiveness and durability thereof.

In a preferred embodiment, the layer (c) is arranged inside the layer (b). Further, the layer (b) is arranged between the layer (a) and the layer (c). In a more preferred embodiment, layer (a) is located on the outermost layer of the laminated tube. By arranging the layer (a) on the outermost layer, it is possible to obtain a laminated tube having excellent chemical resistance and flexibility. In a more preferred embodiment, the layer (c) is arranged in the innermost layer. By arranging the layer (c) in the innermost layer, a laminated tube having excellent deterioration fuel resistance can be obtained, and elution of low molecular weight components such as monomers and oligomers due to contact with alcohol-containing gasoline can be suppressed. Become. That is, a laminated tube in which the layer (a) is arranged in the outermost layer, the layer (b) is arranged in the intermediate layer, and the layer (c) is arranged in the innermost layer is more preferable.

Further, in the laminated tube of the second aspect, when the conductive layer containing the fluorine-containing polymer composition containing the conductive filler is arranged in the innermost layer of the laminated tube, the chemical barrier property and the deterioration fuel resistance are improved. In addition to having excellent elution resistance of monomers and oligomers, when used as a fuel pipe tube, prevent sparks generated by internal friction of the fuel circulating in the pipe or friction with the pipe wall from igniting the fuel. Is possible. At that time, by arranging the layer containing the fluorine-containing polymer having no conductivity on the outside with respect to the conductive layer, it is possible to achieve both low temperature impact resistance and conductivity, and also. It is also economically advantageous. Further, the fluorine-containing polymer referred to here also includes the fluorine-containing polymer (C) having a functional group in the molecular chain, and also refers to the fluorine-containing polymer having no functional group described later.

The details of the conductive and the conductive filler are the same as those of the laminated tube of the first aspect.

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 balance with conductivity, fluidity, mechanical strength, etc., 100 parts by mass of the fluorine-containing polymer On the other hand, it is generally preferable that the amount is 3 parts by mass or more and 30 parts by mass or less.
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 second aspect, 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 in consideration of characteristics such as chemical barrier property, low temperature impact resistance, and flexibility of the laminated tube. In general, the thickness of the layer (a), the layer (b), and the layer (c) is preferably 3% or more and 90% or less, respectively, with respect to the thickness of the entire laminated tube. Considering the balance between low temperature impact resistance and chemical barrier property, the thickness of the layer (b) and the layer (c) is more preferably 5% or more and 50% or less, respectively, with respect to the thickness of the entire laminated tube. , 7% or more and 30% or less is more preferable.

Further, the total number of layers in the laminated tube of the second aspect is not particularly limited as long as it has at least three layers having a layer (a), a layer (b), and a layer (c). Further, the laminated tube of the second aspect is provided with additional functions other than the three layers (a), (b), and (c), or in order to obtain an economically advantageous laminated tube. It may have one layer or two or more layers containing another thermoplastic resin. The number of layers of the laminated tube of the second aspect is 3 or more, but judging from the mechanism of the tube manufacturing apparatus, it is preferably 8 or less, and more preferably 3 or more and 7 or less.

Examples of the thermoplastic resin in the laminated tubes of the first aspect and the second aspect include polymethaxylylene succina other than the polyamide copolymer (A1), the semi-aromatic polyamide (B1) and the semi-aromatic polyamide (B2). Mido (Polyamide MXD4), Polymethoxylylen Glutamide (Polyamide MXD5), Polymethoxylylence Veramide (Polyamide MXD8), Polymethoxylylend Decamide (Polyamide MXD12), Polymethaxylylene terephthalamide (Polyamide MXDT), Polymetaki Syrylene isophthalamide (polyamide MXDI), polymethoxylylene hexahydroterephthalamide (polyamide MXDT (H)), polymethoxylylen naphthalamide (polyamide MXDN), polyparaxylylene succinamide (polyamide PXD4), polyparaxylylene Glutamide (polyamide PXD5), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylene veramide (polyamide PXD8), polyparaxylylene dedecamide (polyamide PXD12), polyparaxylylene terephthalamide (polyamide PXD12) PXDT), polyparaxylylene isophthalamide (polyamide PXDI), polyparaxylylene hexahydroterephthalamide (polyamide PXDT (H)), polyparaxylylene naphthalamide (polyamide PXDN), polyparaphenylene terephthalamide (polyamide PXDN) PPTA), polyparaphenylene isophthalamide (PPIA), polymetaphenylene terephthalamide (PMTA), polymetaphenylene isophthalamide (PMIA), polyparaxylylene naphthalamide (polyamide PXDN), polyparaphenylene terephthalamide. (PPTA), polyparaphenylene isophthalamide (PPIA), polymetaphenylene terephthalamide (PMTA), polymetaphenylene isophthalamide (PMIA), poly (2,6-naphthalenedimethylene adipamide) (polyamide 2) , 6-BAN6), Poly (2,6-naphthalenedimethylene terephthalamide) (Polyamide 2,6-BANT), Poly (2,6-naphthalenedimethyleneisophthalamide) (Polyamide 2,6-BANI), Poly (2,6-naphthalenedimethylene hexahydroterephthalamide) (polyamide 2,6-BANT (H)), poly (2,6-naphthalenedimethylene naphthalamide) (polyamide 2,6-BANN), poly (polyamide 2,6-BANN) 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) Telephthalamide) (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 (4,54'-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 (4,4'-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 (4,5'-propylene biscyclohexylene terephthalamide) (polyamide PACPT), poly (4,5'-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), polynonamethyleneisophthalamide (polyamide 9I), polynonamethylenehexahydroterephthalamide (polyamide 9T (H)), poly (2-methyloctamethyleneisophthalamide) ( Polyamide M8I), poly (2-methyloctamethylenehexahydroterephthalamide) (polyamide M8T (H)), polytrimethylhexamethylene isophthalamide (polyamide TMHI), polytrimethylhexamethylene hexahydroterephthalamide (polyamide TMHT (polyamide TMHT) H)), polydecamethylene isophthalamide (polyamide 10I), polydecamethylene hexahydroterephthalamide (polyamide 10T (H)), 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)), homopolymers such as polydodecamethylene naphthalamide (polyamide 12N), raw material monomers of these polyamides, and / or the above-mentioned polyamide. Examples thereof include polyamide-based resins such as copolymers using several kinds of raw material monomers of the copolymer (A1).

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 Contains no functional groups reactive with amino groups such as xafluoropropylene copolymer, chlorotrifluoroethylene / tetrafluoroethylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) / hexafluoropropylene copolymer Fluoropolymers can be mentioned.
When the laminated tube has the layer (c), the layer containing the fluorine-based polymer containing no functional group is arranged inside the layer (c), so that the low temperature impact resistance and the chemical barrier property can be improved. It is possible to achieve both environmental stress crack resistance and environmental stress crack resistance, and it is also economically advantageous.

Furthermore, 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). Resins; 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 Polystyrene resins such as / butylene / styrene copolymer (SEBS), 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. Anhydrous group; said polyolefin resin and polystyrene resin containing a functional group such as an epoxy group such as glycidyl acrylate, glycidyl methacrylate, glycidyl etacrilate, glycidyl itacone, glycidyl citracone; polybutylene terephthalate (PBT). , 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); polysalphon such as polysalphon (PSU), polyethersulfone (PESU), polyphenylsalphon (PPSU) Based resin; Polythioether based resin such as polyphenylene sulfide (PPS) and polythioetheralphon (PTES); Polyketone (PK), polyetherketone (PEK), polyetheretherketone (PEEK), polyetherketoneketone (PEKK) , Polyetheretheretherketone (PEEEK), polyetheretherketoneketone (PEEKK), polyetherketoneketoneketone (PEKKK), polyetherketoneetherketoneketone (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 vinylacetate (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 ( Polyetherketone resins such as TPI), polyetherimide, polyesterimide, polyamideimide (PAI), and polyesteramideimide; thermoplastic polyurethane resins; polyamide elastomers, polyurethane elastomers, polyester elastomers, and the like can be mentioned.

In the laminated tube of the first aspect, from the viewpoint of melt stability and molding stability, among the above-exemplified thermoplastic resins, polyester resins having a melting point of 290 ° C. or lower, polyamide resins, polythioether resins, etc. It is preferable to use a polyolefin resin and a fluorine-containing polymer containing no functional group.
Further, in the laminated tube of the second aspect, from the viewpoint of melt stability and molding stability, among the above-exemplified thermoplastic resins, polyester resins having a melting point of 290 ° C. or lower, polyamide resins, polythioether resins, etc. It is preferable to use a polyolefin resin and a fluorine-containing polymer containing no functional group.

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 and the like. is there. Metallic materials include metals such as aluminum, iron, copper, nickel, gold, silver, titanium, molybdenum, magnesium, manganese, lead, tin, chromium, beryllium, tungsten and cobalt, and / or metal compounds thereof, and 2 thereof. Examples thereof include alloy steels such as stainless steels, 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 using an extruder corresponding to the number of layers or the number of materials and simultaneously laminating inside or outside the die (coextrusion molding method), 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 is preferably manufactured by a coextrusion molding 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. That is, the method for producing a laminated tube preferably includes coextrusion molding.

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 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 is not limited to the one 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 form an L-shape, a U-shape, or the like by adding necessary parts such as a connector or bending the connector.

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), NBR and EPDM mixture rubber, 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 this embodiment 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, etc. It can be used for various purposes such as furniture parts.

Further, the laminated tube is suitable as a chemical solution transport tube because it has an excellent chemical solution barrier property. Examples of the chemical solution include aromatic hydrocarbon solvents such as benzene, toluene, xylene, and alkylbenzene; methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, diethylene glycol, phenol, cresol, polyethylene glycol, and polypropylene glycol. , Alcohol such as polyalkylene glycol; phenol solvent; ether solvent such as dimethyl ether, dipropyl ether, methyl-t-butyl ether, ethyl-t-butyl ether, dioxane, tetrahydrofuran, polyol esters, polyvinyl ethers, etc.; HFC-23 (trifluoromethane), HFC-32 (difluoromethane), HFC-41 (fluoromethane), HFC-123 (2,2-dichloro-1,1,1-trifluoroethane), HFC-125 (1) , 1,1,2,2-pentafluoroethane), HFC-134 (1,1,2,2-tetrafluoroethane), HFC-134a (1,1,1,2-tetrafluoroethane), HFC- 143 (1,1,2-trifluoroethane), HFC-143a (1,1,1-trifluoroethane), HFC-152 (1,2-difluoroethane), HFC-152a (1,1-difluoroethane), HFC-161 (fluoroethane), HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane), HFC-227ca (1,1,2,2,3,3,3-hepta) Fluoropropane), HFC-236fa (1,1,1,3,3,3-hexafluoropropane), HFC-236ea (1,1,1,2,3,3-hexafluoropropane), HFC-236cc (1,1,1,2,3,3-hexafluoropropane) 1,1,1,2,2,3-hexafluoropropane), HFC-236ca (1,1,2,2,3,3-hexafluoropropane), HFC-245ca (1,1,2,2) 3-Pentafluoropropane), HFC-245ea (1,1,2,3,3-pentafluoropropane), HFC-245eb (1,1,1,2,3-pentafluoropropane), HFC-245fa (1) , 1,1,3,3-pentafluoropropane), HFC-245cc (1,1,1,2,2-pentafluoropropane), HFC-254eb (1,1,1,2-tetrafluoropropane), HFC-254cc (1,1,2,2-tetrafluoropropane), HFC-2 54ca (1,2,2,3-tetrafluoropropane), HFC-263fb (1,1,1-trifluoropropane), HFC-263ca (1,2,2-trifluoropropane), HFC-272fb (1) , 1-difluoropropane), HFC-272ea (1,2-difluoropropane), HFC-272fa (1,3-difluoropropane), HFC-272ca (2,2-difluoropropane), HFC-281fa (1-fluoro) (Propane), HFC-281ea (2-fluoropropane), HFC-329p (1,1,1,2,2,3,3,4,4-nonafluorobutane), HFC-329mmz (1,1,1,1) 3,3,3-Hexafluoro-2- (trifluoro) propane), HFC-338mf (1,1,1,3,3,4,5,4-octafluorobutane), HFC-338mcc (1,1) , 1,2,2,3,4,4-octafluorobutane), HFC-338pcc (1,1,2,2,3,3,4,4-octafluorobutane), HFC-347s (1,1) , 1,2,2,3,3-heptafluorobutane), HFC-365mfc (1,1,1,3,3-pentafluorobutane), HFC-4310mee (1,1,1,2,3,4) , 4,5,5,5-decafluoropentane), HFC-1123 (trifluoroethylene), HFC-1132a (1,2-difluoroethylene), FC-1216 (hexafluoro-1-propene), HFC-1223 (3,3,3-trifluoro-1-propen), HFC-1225zc (1,1,3,3,3-pentafluoro-1-propen), HFC-1225ye (1,2,3,3,3) −Pentafluoro-1-propene), HFC-1225yc (1,1,2,3,3-pentafluoro-1-propene), HFC-1232xf (3,3-difluoro-1-propene), HFC-1234ye ( 1,2,3,3-tetrafluoro-1-propen), HFC-1234ze (1,3,3,3-tetrafluoro-1-propen), HFC-1234yf (2,3,3,3-tetrafluoro) -1-Propen), HFC-1234yc (1,1,2,3-tetrafluoro-1-propen), HFC-1234zc (1,1,3,3-tetrafluoro-1-propen), HFC-1243yf (1,1,2,3-tetrafluoro-1-propen) 2,3,3-trifluoro-1-propen), HFC-1243zc (1,1) , 3-Trifluoro-1-propene), HFC-1243ye (1,2,3-trifluoro-1-propene), HFC-1243ze (1,3,3-trifluoro-1-propene), HFC-1243zf (3,3,3-trifluoro-1-propene), HFC-1243yc (1,1,2-trifluoro-1-propene), HFC-1261yf (2-fluoropropene), FC-1318my (1,1) , 1,2,3,4,4,4-octafluoro-2-butene), FC-1318cy (1,1,2,3,3,4,5,4-octafluoro-1-butene), HFC -1327my (1,1,1,2,4,4,4-heptafluoro-2-butene), HFC-1327ye (1,2,3,3,4,5,4-heptafluoro-1-butene) , HFC-1327py (1,1,1,2,3,4,4-heptafluoro-2-butene), HFC-1327et (1,3,3,3-tetrafluoro-2- (trifluoromethyl)- 1-propen), HFC-1327cz (1,1,3,3,4,5,4-heptafluoro-1-butene), HFC-1327cye (1,1,2,3,4,5,4-hepta) Fluoro-1-butene), HFC-1327cyc (1,1,2,3,3,4,4-heptafluoro-1-butene), HFC-1336yf (2,3,3,4,5,4-hexa) Fluoro-1-butene), HFC-1336ze (1,3,3,4,5,4-hexafluoro-1-butene), HFC-1336eye (1,2,3,4,5,4-hexafluoro-) 1-butene), HFC-1336eyec (1,2,3,3,4,4-hexafluoro-1-butene), HFC-1336py (1,1,2,3,4,4-hexafluoro-2-) Butene), HFC-1336pz (1,1,1,2,4,4-hexafluoro-2-butene), HFC-1336mzy (1,1,1,3,4,5-hexafluoro-2-butene) , HFC-1336mzz (1,1,1,4,4,4-hexafluoro-2-butene), HFC-1336qc (1,1,2,3,3,4-hexafluoro-1-butene), HFC -1336pe (1,1,2,3,4,5-hexafluoro-1-butene), HFC-1336ft (3,3,3-trifluoro-2- (trifluoromethyl) -1-propen), HFC -1345qz (1,1,1,2,4-pentafluo) Lo-2-butene), HFC-1345mzy (1,1,1,3,4-pentafluoro-2-butene), HFC-1345fz (3,3,4,5,4-pentafluoro-1-butene) , HFC-1345mzz (1,1,1,4,4-pentafluoro-2-butene), HFC-1345sy (1,1,1,2,3-pentafluoro-2-butene), HFC-1345fyc (2) , 3,3,4,4-pentafluoro-1-butene), HFC-1345pyz (1,1,2,4,4-pentafluoro-2-butene), HFC-1345cyc (1,1,2,3) , 3-Pentafluoro-1-butene), HFC-1345py (1,1,2,3,4-pentafluoro-2-butene), HFC-1345eyec (1,2,3,3,4-pentafluoro-) 1-butene), HFC-1345ctm (1,1,3,3,3-pentafluoro-2-methyl-1-propene), HFC-1345ftp (2- (difluoromethyl) -3,3,3-trifluoro -1-propen), HFC1345fy (2,3,4,5,4-pentafluoro-1-butene), HFC-1345eye (1,2,4,5,4-pentafluoro-1-butene), HFC- 1345 eze (1,3,4,5,4-pentafluoro-1-butene), HFC-1345 ezc (1,3,3,4,5-pentafluoro-1-butene), HFC-1345eye (1,2, 3,4,4-Pentafluoro-1-butene), HFC-1354fzzc (3,3,4,5-tetrafluoro-1-butene), HFC-1354ctp (1,1,3,3-tetrafluoro-2) -Methyl-1-propene), HFC-1354etm (1,3,3,3-tetrafluoro-2-methyl-1-propene), HFC-1354tfp (2- (difluoromethyl) -3,3-difluoro-1) -Propen), HFC-1354 my (1,1,1,2-tetrafluoro-2-butene), HFC-1354mzy (1,1,1,3-tetrafluoro-2-butene), FC-141-10 myy (1,1,1,3-tetrafluoro-2-butene) 1,1,1,2,3,4,5,5,5-decafluoro-2-pentene), FC-141-10cy (1,1,2,3,3,4,5, 5,5-decafluoro-1-pentene) HFC-1429mzzt (1,1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene), HFC-1429 myz (1,1,1,2,4,5,5,5-nonafluoro-2-pentene), HFC-1429mzy (1,1,1,3,4,5,5,5-nonafluoro) -2-Pentene), HFC-1429eyc (1,2,3,3,4,5,5,5-Nonafluoro-1-pentene), HFC-1429czc (1,1,3,3,4,4) , 5,5,5-Nonafluoro-1-pentene), HFC-1429cycc (1,1,2,3,3,4,5,5-Nonafluoro-1-pentene), HFC-1429py (1,1) , 2,3,4,4,5,5,5-nonafluoro-2-pentene), HFC-1429myyc (1,1,1,2,3,4,5,5-nonafluoro-2-pentene) , HFC-1429myy (1,1,1,2,3,4,5,5,5-nonafluoro-2-pentene), HFC-1429myy (1,2,3,4,5,4-hexafluoro-3) -(Trifluoromethyl) -1-butene), HFC-1429yzm (1,1,2,4,4,4-hexafluoro-3- (trifluoromethyl) -1-butene), HFC-1429mzzt (1, 1,1,4,4,4-hexafluoro-2- (trifluoromethyl) -2-butene), HFC-1429csym (1,1,3,4,5,4-hexafluoro-3- (trifluoro)) Methyl) -1-butene), HFC-1438fy (2,3,3,4,5,5,5-octafluoro-1-pentene), HFC-1438eycc (1,2,3,3,4) 4,5,5-octafluoro-1-pentene), HFC-1438ftmc (3,3,4,5,4-pentafluoro-2- (trifluoromethyl) -1-butene), HFC-1438czzm (1,1) 1,4,4,4-pentafluoro-3- (trifluoromethyl) -1-butene), HFC-1438ezym (1,3,4,5,4-pentafluoro-3- (trifluoromethyl) -1) -Butene), HFC-1438ctmf (1,1,4,4,4-pentafluoro-2- (trifluoromethyl) -1-butene), HFC-1447fzy (3,4,5,4-tetrafluoro-3) -(Trifluoromethyl) -1-butene), HFC-1447fz (3,3,4,5,5,5-ptafluoro-1-pentene), HFC-1447fycc (2,3,3,4,4) , 5,5-Heptafluoro-1-pentene), HF C-1447cz (1,1,3,3,5,5,5-heptafluoro-1-pentene),
HFC-1447mytm (1,1,1,2,4,4,4 heptafluoro-3-methyl-2-butene), HFC-1447fyz (2,4,5,4-tetrafluoro-3- (trifluoromethyl)) ) -1-Butene), HFC-1447ezz (1,4,4,4-tetrafluoro-3- (trifluoromethyl) -1-butene), HFC-1447qzzt (1,4,5,4-tetrafluoro-) 2- (Trifluoromethyl) -2-butene), HFC-1447syst (2,4,5,4-tetrafluoro-2- (trifluoromethyl) -2-butene), HFC-1456szt (3- (trifluoromethyl) szt) Methyl) -4,4,4-trifluoro-2-butene), HFC-1456szy (3,4,5,5,5,hexafluoro-2-pentene), HFC-1456mstz (1,1,1,1) 4,4,4-Hexafluoro-2-methyl-2-butene), HFC-1456fzce (3,3,4,5,5,5-hexafluoro-1-pentene), HFC-1456ftmf (4,4) 4-Trifluoro-2- (trifluoromethyl) -1-butene), FC-151-12c (1,1,2,3,3,4,5,5,6,6,6-dodeca- 1-hexene, perfluoro-1-hexene), FC-151-12mcy (1,1,1,2,2,3,4,5,5,6,6,6-dodeca-3-hexene, perfluoro-3) -Hexen), FC-151-12 mmtt (1,1,1,4,4,4-hexafluoro-2,3-bis (trifluoromethyl) -2-butene), FC-151-12 mmzz (1,1) , 1,2,3,4,5,5,5-nonafluoro-4- (trifluoromethyl) -2-pentene), HFC-152-11 mmtz (1,1,1,4,4,5,5) 5-Octafluoro-2- (trifluoromethyl) -2-pentene), HFC-152-11 mmyz (1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl)) -2-Pentene), HFC-152-11 mmyz (1,1,1,3,4,5,5,5-octafluoro-4- (trifluoromethyl) -2-pentene), HFC-1549fz (PFBE) (3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene, perfluorobutyl), HFC-1549fzztmm (4,4,4-trifluoro-3,3-bis Trifluoromethyl) -1-bute , HFC-1549 mmtts (1,1,1,4,4,4-hexafluoro-3-methyl-2- (trifluoromethyl) -2-butene), HFC-1549fycz (2,3,3,5) , 5,5-Hexafluoro-4- (trifluoromethyl) -1-pentene), HFC-1549myts (1,1,1,2,4,5,5,5-nonafluoro-3-methyl-2) -Pentene), HFC-1549mzz (1,1,1,5,5,5-hexafluoro-4- (trifluoromethyl) -2-pentene), HFC-1558szy (3,4,5,5,5) 6,6,6-octafluoro-2-heptene), HFC-1558fzccc (3,3,4,4,5,5,6,6-octafluoro-2-heptene), HFC-1558mmtzc (1,1,1, 1,4,4-Pentafluoro-2- (trifluoromethyl) -2-pentene), HFC-1558ftmf (4,4,5,5,5-pentafluoro-2- (trifluoromethyl) -1-pentene) ), HFC-1567fts (3,3,4,5,5,5,5-heptafluoro-2-methyl-1-pentene), HFC-1567szz (4,4,5,5,6,6-6-) Heptafluoro-2-hexene), HFC-1567fzfc (4,4,5,5,6,6,6-heptafluoro-1-hexene), HFC-1567sfy (1,1,1,2,2,3) 4-Heptafluoro-3-hexene), HFC-1567fzfy (4,5,5,5-tetrafluoro-4- (trifluoromethyl) -1-pentene), HFC-1567myzm (1,1,1,2, 5,5,5-Heptafluoro-4-methyl-2-pentene), HFC-1567mmtyf (1,1,1,3-tetrafluoro-2- (trifluoromethyl) -2-pentene), FC-161- 14myy (1,1,1,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene), FC-161-14mcyy (1,1,1) , 2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene), HFC-162-13mzy (1,1,1,3,4,4) 5,5,6,6,7,7,7-tridecafluoro-2-heptene), HFC162-13myz (1,1,1,2,4,4,5,5,6,6,7,7) , 7-Tridecafluoro-2-heptene), HFC-162-13mczy (1) , 1,1,2,2,4,5,5,6,6,7,7,7-tridecafluoro-3-heptene), HFC-162-13mcyz (1,1,1,2,2,2) 3,5,5,6,6,7,7,7-tridecafluoro-3-heptene), CFC-11 (fluorotrichloromethane), CFC-12 (dichlorodifluoromethane), CFC-114 (1,1) , 2,2-Tetrafluoro-1,2-dichloroethane), CFC-114a (1,1,1,2-tetrafluoro-2,2-dichloroethane), CFC-115 (1,1,1,2,2) -Pentafluoro-2-dichloroethane), HCFC-21 (dichlorofluoromethane), HCFC-22 (chlorodifluoromethane), HCFC-122 (1,1,2-trichloro-2,2-difluoroethane), HCFC-123 ( 1,1,1-trifluoro-2,2-dichloroethane), HCFC-124 (1,1,1,2-tetrafluoro-2-chloroethane), HCFC-124a (1,1,2,2-tetrafluoro) -2-chloroethane), HCFC-132 (dichlorodifluoroethane), HCFC-133a (1,1,1-trifluoro-2-chloroethane), HCFC-141b (1,1-dichloro-1-fluoroethane), HCFC- 142 (1,1-difluoro-2-chloroethane), HCFC-142b (1,1-difluoro-1-chloroethane), HCFC-225ca (3,3-dichloro-1,1,1,2,2-pentafluoro) Propane), HCFC-225cc (1,3-dichloro-1,1,2,2,3-pentafluoropropane), HCFC-240db (1,1,1,2,3-pentachloropropane), HCFC-243db (1,3-dichloro-1,1,2,3-pentachloropropane) 1,1,1-trifluoro-2,3-dichloropropane), HCFC-243ab (1,1,1-trifluoro-2,2-dichloropropane), HCFC-244eb (1,1,1,2- Tetrafluoro-3-chloropropane), HCFC-244bb (1,1,1,2-tetrafluoro-2-chloropropane), HCFC-244db (1,1,1,3-tetrafluoro-2-chloropropane), HCFC- 1111 (1,1,2-trichloro-2-fluoroethylene), HCFC-1113 (1,1,2-trifluoro-2-chloroethylene), HCFC-1223xd (3,3,3-trifluoro-1, 2-dichloropropene), HC FC-1224xe (1,3,3,3-tetrafluoro-2-chloropropene), HCFC-1232xf (3,3-difluoro-1,3-dichloropropene), HCFC-1233xf (3,3,3-tri) Fluoroolefins such as fluoro-2-chloropropene), HCFC-1233zd (3,3,3-trifluoro-1-chloropropene), and mixtures thereof; ketone solvents such as acetone, methyl ethyl ketone, diethyl ketone, and acetophenone; Mineral oils, silicone oils, natural paraffins, naphthenes, synthetic paraffins, polyalphaolefins, etc., gasoline, kerosene, diesel gasoline, rapeseed oil methyl ester, soybean oil methyl ester, palm oil methyl ester, coconut Oil methyl ester, gas liquefied oil (Gas To Liquid: GTL), coal liquefaction oil (Coal To Liquid: CTL), biomass liquefied oil (Biomass To Liquid: BTL), alcohol-containing gasoline, ethyl-t-butyl ether blend oxygen-containing gasoline , Amine-containing gasoline, sour gasoline, compressed natural gas (CNG), liquefied petroleum gas (LPG), liquefied hydrocarbon gas (LHG), liquefied natural gas (LNG), dimethyl ether for fuel (DME), mineral oil base brake liquid, glycol Ether-based brake fluid, borate ester-based brake fluid, frigid region brake fluid, silicone oil-based brake fluid, mineral oil-based brake fluid, power steering oil, hydrogen sulfide oil, window washer fluid, engine coolant, urea solution, medicine Examples include chemicals, inks, paints and the like. The laminated tube is suitable as a tube for transporting the chemical solution, and specifically, a fuel tube such as a feed tube, a return tube, an evaporator tube, a fuel filler tube, an ORVR tube, a reserve tube, and a vent tube, and hydrogen for a fuel cell. Transport tube, oil tube, oil drilling tube, pneumatic, hydraulic tube, clutch tube, brake tube, brake negative pressure tube, suspension tube, air tube, turbo air tube, air duct tube, blow-by tube, EGR valve control tube , Window washer fluid tube, engine coolant (LLC) tube, reservoir tank tube, urea solution transport tube, cooling water, cooler tube for refrigerant, air conditioner refrigerant tube, heater tube, radiator tube, road heating tube, floor Examples include heating tubes, infrastructure supply tubes, fire extinguishing and fire extinguishing equipment tubes, medical cooling equipment tubes, ink, paint spray tubes, and other chemical tube. In particular, it is suitable as a fuel tube. That is, the present invention includes the use of the laminated tube 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 polyamide concentration of 1%, and a temperature of 25 ° C.

The characteristics of the fluorine-containing polymer were measured by the following method.
[Content of each structural unit of fluorine-containing polymer]
The ratio (mol%) of each constituent unit was determined by molten NMR (nuclear magnetic resonance) analysis and fluorine content analysis.

[Content of constituent units based on itaconic anhydride (IAH)]
The fluorine-containing polymer was press-molded to obtain a 200 μm film. In the infrared absorption spectrum, the absorption peak derived from the NAH-based structural unit in the fluorine-containing polymer appears at ^{1870 cm -1.} The absorbance of the absorption peak was measured, and the molar extinction coefficient of IAH 237 L / (mol · cm) determined from the model compound was used to determine the proportion (mol%) of the structural units based on IAH.

[Content of constituent units based on 5-norbornene-2,3-dicarboxylic acid anhydride (NAH)]
The fluorine-containing polymer was press-molded to obtain a 200 μm film. In the infrared absorption spectrum, the absorption peak derived from the NAH-based structural unit in the fluorine-containing polymer appears at ^{1778 cm -1.} The absorbance of the absorption peak was measured, and the molar extinction coefficient of NAH of 20810 L / (mol · cm) obtained from the model compound was used to determine the ratio (mol%) of the structural units based on NAH.

[Number of terminal carbonate groups in fluorine-containing polymer]
As for the number of terminal carbonate groups in the fluorine-containing polymer, the peak to which the carbonyl group of the carbonate group (-OC (= O) O-) belongs appears at the absorption wavelength of ^{181 to 18 cm -1 by infrared absorption spectrum analysis.} the absorbance of the absorption peak was measured to calculate the number of carbonate groups to the number ¹⁰⁶ main chain carbon atoms in the fluorine-containing polymer by the following equation.
[The number of fluorine-containing main chain carbonate groups to carbon atoms 10 ⁶ polymer] = 500AW / εdf
A: Absorbance of the peak of the carbonate group (-OC (= O) O-) ε: Molar extinction coefficient of the carbonate group (-OC (= O) O-) [cm- ¹ · mol ^-1 ]. From the model compound, ε = 170.
W: Composition average molecular weight calculated from monomer composition d: Film density [g / cm ³ ]
f: Film thickness [mm]

In addition, each physical property of the laminated tube was measured by the following method.
[Destruction pressure at high temperature]
The fracture pressure was evaluated at 115 ° C. by the method described in SAE J-2260 7.1. When the breaking pressure at the same temperature was 2.0 MPa or more, it was judged that the breaking pressure at high temperature was excellent.

[Low temperature impact resistance]
An impact test was performed at −40 ° C. by the method described in SAE J-2260 7.5. After observing the appearance of the sample after the test and confirming the presence or absence of cracks, the fracture pressure was evaluated at 23 ° C. by the method described in SAE J-2260 7.1, and the presence or absence of microcracks was confirmed.

[Chemical resistance (zinc chloride resistance)]
A polyamide 12 joint is press-fitted into the end of the tube, and a tube pre-curved with a bending radius of 40 mm is used in a 50% zinc chloride aqueous solution at 23 ° C. for 200 hours by the method described in SAE J-2260 7.12. Soaked. After that, the sample was taken out and the presence or absence of cracks was confirmed. Then, an impact test was carried out at −40 ° C. by the method described in SAE J-2260 7.5.

[Interlayer adhesiveness]
A tube cut to 200 mm was further cut in half in the vertical direction to prepare a test piece. A 90 ° peeling test was carried out at a tensile speed of 50 mm / min using a universal material testing machine (Tencilon UTMIII-200 manufactured by Orientec). The peel strength was read from the maximum point of the SS curve, and the interlayer adhesiveness was evaluated.

[Durability of interlayer adhesion]
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.

[Chemical solution (alcohol-containing gasoline) barrier property]
One end of a tube cut to 200 mm was sealed, and alcohol-containing gasoline in which FuelC (isooctane / toluene = 50/50 volume ratio) and ethanol were mixed in a 90/10 volume ratio was put therein, and the other end was also 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 daily mass change was divided by the surface area of the inner layer of the tube ^{to calculate the alcohol-containing gasoline permeation amount (g / m 2} · day).

[Materials used in Examples and Comparative Examples]
Polyamide copolymer (A1)
Aliphatic polyamide (A1)
Production of Polyamide 12 / 9T (A1-1) 4.52 kg (21.0 mol) of aminododecanoic acid and 1.27 kg (8.0 mol) of 1,9-nonanediamine in a pressure-resistant reaction vessel with a stirrer with an internal volume of 70 liters. ), 2-Methyl-1,8-octanediamine 0.224 kg (1.4 mol), terephthalic acid 1.50 kg (9.0 mol), benzoic acid 19.5 g (0.16 mol), hypophosphite 7.5 g of sodium monohydrate (0.1% by mass based on the raw material) and 5.0 L of distilled water were charged, the inside of the polymerization tank was replaced with nitrogen, and then heated to 220 ° C., and the inside of the reaction system was heated at this temperature. Was stirred so that the mixture became uniform. 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 12 / 9T having a relative viscosity of 2.12 = 70/30 mol% (hereinafter, this polyamide 12 / 9T is referred to as (A1-1)).

Production of Polyamide 11 / 10T (A1-2) In the production of Polyamide 12 / 9T (A1-1), 4.52 kg (21.0 mol) of aminododecanoic acid and 1.27 kg (8.0 mol) of 1,9-nonanediamine. ), 2-Methyl-1,8-octanediamine 0.224 kg (1.4 mol), terephthalic acid 1.50 kg (9.0 mol), aminoundecanoic acid 4.23 kg (21.0 mol), 1,10 -Relative viscosity by the same method as for the production of polyamide 12 / 9T (A1-1), except that it was changed to 1.91 kg (9.45 mol) of decanediamine and 1.50 kg (9.0 mol) of terephthalic acid. 2.18 Polyamide 11 / 10T = 70/30 mol% was obtained (hereinafter, this polyamide 11 / 10T is referred to as (A1-2)).

Production of Polyamide 1010 / 10T (A1-3) In the production of Polyamide 12 / 9T (A1-1), 4.52 kg (21.0 mol) of aminododecanoic acid and 1.27 kg (8.0 mol) of 1,9-nonanediamine. ), 0.224 kg (1.4 mol) of 2-methyl-1,8-octanediamine, 1.50 kg (9.0 mol) of terephthalic acid and 5.43 kg (31.5 mol) of 1,10-decanediamine. Relative viscosity 2 by the same method as for the production of polyamide 12 / 9T (A1-1), except that sebacic acid was changed to 4.25 kg (21.0 mol) and terephthalic acid was changed to 1.50 kg (9.0 mol). .20 Polyamide 1010 / 10T = 70/30 mol% was obtained (hereinafter, this polyamide 1010 / 10T is referred to as (A1-3)).

Production of Polyamide 12 / MXD10 (A1-4) In the production of Polyamide 12 / 9T (A1-1), 1.27 kg (8.0 mol) of 1,9-nonanediamine, 2-methyl-1,8-octanediamine 0 .224 kg (1.4 mol) and 1.50 kg (9.0 mol) of terephthalic acid were changed to 1.29 kg (9.45 mol) of m-xylylenediamine and 1.82 kg (9.0 mol) of sebacic acid. Polyamide 12/1 MXD10 = 70/30 mol% having a relative viscosity of 2.12 was obtained by the same method as in the production of polyamide 12 / 9T (A1-1) (hereinafter, this polyamide 12 / MXD10 was used. (A1-4).

Production of Polyamide 1010 / MXD10 (A1-5) In the production of Polyamide 12 / 9T (A1-1), 4.52 kg (21.0 mol) of aminododecanoic acid and 1.27 kg (8.0 mol) of 1,9-nonanediamine. ), 2-Methyl-1,8-octanediamine 0.224 kg (1.4 mol), terephthalic acid 1.50 kg (9.0 mol) 1,10-decanediamine 3.80 kg (22.05 mol), In the same manner as for the production of polyamide 12 / 9T (A1-1), except that the amount was changed to 1.29 kg (9.45 mol) of m-xylylenediamine and 6.07 kg (30.0 mol) of sebacic acid. Polyamide 1010 / MXD10 with a relative viscosity of 2.12 = 70/30 mol% was obtained (hereinafter, this polyamide 1010 / MXD10 is referred to as (A1-5)).

Production of Polyamide 612 / 6T (A1-6) In the production of Polyamide 12 / 9T (A1-1), 4.52 kg (21.0 mol) of aminododecanoic acid and 1.27 kg (8.0 mol) of 1,9-nonanediamine. ), 0.224 kg (1.4 mol) of 2-methyl-1,8-octanediamine, 3.66 kg (31.5 mol) of 1,6-hexanediamine, 4.84 kg (21.0 mol) of dodecanedioic acid. 612 / 6T = 70/30 mol% of polyamide having a relative viscosity of 2.12 was obtained by the same method as in the production of polyamide 12 / 9T (A1-1) except that it was changed to (hereinafter, this polyamide 612 / 6T is referred to as (A1-6)).

Production of Polyamide 612 / 6T (A1-7) 3.66 kg (31.5 mol) of 1,6-hexanediamine and 3.45 kg (15.0) of dodecanedioic acid in a pressure-resistant reaction vessel with a stirrer with an internal volume of 70 liters. Mol), 2.49 kg (15.0 mol) of terephthalic acid, 19.5 g (0.16 mol) of benzoic acid, 9.6 g of sodium hypophosphate monohydrate (0.1% by mass based on the raw material) , And 5.0 L of distilled water were charged and replaced with nitrogen. The mixture was stirred at 100 ° C. for 30 minutes, and the internal temperature was raised to 190 ° C. over 2 hours. At this time, the autoclave was boosted to 2.0 MPa. After continuing the reaction for 1 hour as it was, the temperature was raised to 250 ° C., and then the temperature was maintained at 250 ° C. for 2 hours, water vapor was gradually removed, and the reaction was carried out while maintaining the pressure at 2.0 MPa. Next, the pressure was lowered to 1.0 MPa over 30 minutes, and the reaction was carried out for another 1 hour to obtain a prepolymer. This was dried at 100 ° C. under reduced pressure for 12 hours, pulverized to a size of 2 mm or less, solid-phase polymerized at 230 ° C. under 0.013 kPa for 8 hours, and a polyamide 612 / 6T having a relative viscosity of 2.15 = 50/50 mol% was obtained (hereinafter, this polyamide 612 / 6T is referred to as (A1-7)).

Production of Polyamide 11 (A1-8) In the production of Polyamide 11 / 10T (A1-2), 1.91 kg (9.45 mol) of 1,10-decanediamine and 1.50 kg (9.0 mol) of terephthalic acid were added. Polyamide 11 having a relative viscosity of 2.30 was obtained in the same manner as in the production of polyamide 11 / 10T (A1-2) except that it was not used (hereinafter, this polyamide 11 is referred to as (A1-8)).

Elastomer polymer (A2)
Maleic anhydride-modified ethylene / 1-butene copolymer (A2-1) (manufactured by Mitsui Chemicals, Inc., Toughmer MH5010)

Polyamide copolymer composition (A)
Production of Polyamide 12 / 9T Composition (A-1) Polyamide 12 / 9T (A1-1) with maleic anhydride-modified ethylene / 1-butene copolymer (A2-1), triethylene glycol-bis as an antioxidant [3- (3-t-Butyl-5-methyl-4-hydroxyphenyl) propionate] (BASF Japan, Inc., IRGANOX245), and Tris (2,4-di-t-butylphenyl) as a phosphorus-based processing stabilizer. Phosphite (made by BASF Japan, IRGAFOS168) is mixed in advance, supplied to a twin-screw melt kneader (manufactured by Nippon Steel Co., Ltd., model: TEX44), melt-kneaded at a cylinder temperature of 180 ° C to 270 ° C, and melted. After extruding the resin into strands, it was introduced into a water tank, cooled, cut, and vacuum dried to obtain 85.0% by mass of polyamide 12 / 9T (A1-1) and an elastomer polymer (A2-1). Pellets of a polyamide 12 / 9T 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 0% by mass (hereinafter, this polyamide 12). The / 9T composition is referred to as (A-1)).

Production of Polyamide 11 / 10T Composition (A-2) In the production of Polyamide 12 / 9T Composition (A-1), Polyamide 12 / 9T (A1-1) was changed to Polyamide 11 / 10T (A1-2). Except for the above, the same method as for the production of the polyamide 12 / 9T composition (A-1) was used, in which the polyamide 111 / 10T (A1-2) was 85.0% by mass and the elastomer polymer (A2-1) was 15.0% by mass. Pellets of a polyamide 11 / 10T 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 a total of 100 parts by mass of the ratio% (hereinafter, this polyamide 11 / The 10T composition is referred to as (A-2)).

Production of Polyamide 1010 / 10T Composition (A-3) In the production of Polyamide 12 / 9T Composition (A-1), Polyamide 12 / 9T (A1-1) was changed to Polyamide 1010 / 10T (A1-3). Except for the above, the same method as for the production of the polyamide 12 / 9T composition (A-1) was used, with 85.0% by mass of the polyamide 1010 / 10T (A1-3) and 15.0% by mass of the elastomer polymer (A2-1). A pellet of a polyamide 1010 / 10T 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 the total of% (hereinafter, this polyamide 1010 / 10T). The composition is referred to as (A-3)).

Production of Polyamide 12 / MXD10 Composition (A-4) In the production of Polyamide 12 / 9T Composition (A-1), Polyamide 12 / 9T (A1-1) was changed to Polyamide 12 / MXD10 (A1-4). Except for the above, the same method as for the production of the polyamide 12 / 9T composition (A-1) was used, with 85.0% by mass of the polyamide 12 / MXD10 (A1-4) and 15.0% by mass of the elastomer polymer (A2-1). A pellet of a polyamide 12 / MXD10 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 the total of% (hereinafter, this polyamide 12 / MXD10). The composition is referred to as (A-4)).

Production of Polyamide 1010 / MXD10 Composition (A-5) In the production of Polyamide 12 / 9T Composition (A-1), Polyamide 12 / 9T (A1-1) was changed to Polyamide 1010 / MXD10 (A1-5). Except for the above, the same method as for the production of the polyamide 12 / 9T composition (A-1) was used, in which the polyamide 1010 / MXD10 (A1-5) was 85.0% by mass and the elastomer polymer (A2-1) was 15.0% by mass. A pellet of a polyamide 1010 / MXD10 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 the total of% (hereinafter, this polyamide 1010 / MXD10). The composition is referred to as (A-5)).

Production of Polyamide 612 / 6T Composition (A-6) In the production of Polyamide 12 / 9T Composition (A-1), Polyamide 12 / 9T (A1-1) was changed to Polyamide 612 / 6T (A1-6). Except for the above, the same method as for the production of the polyamide 12 / 9T composition (A-1) was used, with 85.0% by mass of the polyamide 612 / 6T (A1-6) and 15.0% by mass of the elastomer polymer (A2-1). A pellet of a polyamide 612 / 6T 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 the total of% (hereinafter, this polyamide 612 / 6T). The composition is referred to as (A-6)).

Production of Polyamide 612 / 6T Composition (A-7) In the production of Polyamide 12 / 9T Composition (A-1), polyamide 12 / 9T (A1-1) was changed to polyamide 612 / 6T (A1-7). Polyamide 612 / 6T (A1-7) 85.0% by mass, elastomer in the same manner as in the production of the polyamide 12 / 9T composition (A-1), except that the cylinder temperature was changed from 270 ° C to 310 ° C. Pellets of polyamide 612 / 6T composition composed of 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus-based processing stabilizer with respect to 100 parts by mass of 15.0% by mass of polymer (A2-1) in total. (Hereinafter, this polyamide 612 / 6T composition is referred to as (A-7)).

Production of Polyamide 11 Composition (A-8) In the production of the polyamide 12 / 9T composition (A-1), the polyamide 12 / 9T (A1-1) was changed to the polyamide 11 (A1-8) and the biaxial melting was performed. From the middle of the cylinder of the kneader, benzenesulfonic acid butylamide was injected as a plasticizing agent by a metering pump, and the polyamide 11 (A-1) was produced in the same manner as in the production of the polyamide 12 / 9T composition (A-1), except that the polyamide 11 ( A1-8) 85.0% by mass, elastomer polymer (A2-1) 5.0% by mass, plasticizer) 10.0% by mass, for a total of 100 parts by mass, 0.8 parts by mass of antioxidant. Pellets of a polyamide 11 composition composed of 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained (hereinafter, this polyamide 11 composition is referred to as (A-8)).

Production of Polyamide 12 / 9T Composition (A-9) Polyamide 12 / 9T Composition (A-1), except that the elastomer polymer (A2-1) is not used in the production of the Polyamide 12 / 9T Composition (A-1). It is composed of 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus-based processing stabilizer with respect to 100 parts by mass of polyamide 12 / 9T (A1-1) by the same method as in the production of A-1). Pellets of the polyamide 12 / 9T composition were obtained (hereinafter, this polyamide 12 / 9T composition is referred to as (A-9)).

Production of Polyamide 12 / 9T Composition (A-10) Polyamide 12 / 9T Composition in the production of Polyamide 12 / 9T Composition (A-1), except that the amount of elastomer polymer (A2-1) added was changed. By the same method as the production of the product (A-1), with respect to a total of 100 parts by mass of the polyamide 12 / 9T (A1-1) 51.0 mass% elastomer polymer (B2-2) 49.0 mass%. , 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus-based processing stabilizer obtained pellets of a polyamide 612 / 6T composition (hereinafter, this polyamide 12 / 9T composition is referred to as (A-10)). .).

Semi-aromatic polyamide (B1)
Production of semi-aromatic polyamide (B1-1) 1,9-nonanediamine 2.37 kg (15.0 mol), 2-methyl-1,8-octanediamine 2.37 kg (15.0 mol), terephthalic acid 4. 94 kg (29.7 mol), 65.9 g (0.54 mol) of benzoic acid, 9.8 g of sodium hypophosphate monohydrate (0.1% by mass based on the raw material), and 6.0 L of distilled water. Was placed in an autoclave and replaced with nitrogen. The mixture was stirred at 100 ° C. for 30 minutes, and the internal temperature was raised to 190 ° C. over 2 hours. At this time, the autoclave was boosted to 2.0 MPa. After continuing the reaction for 1 hour as it was, the temperature was raised to 230 ° C., and then the temperature was maintained at 230 ° C. for 2 hours, water vapor was gradually removed, and the reaction was carried out while maintaining the pressure at 2.0 MPa. Next, the pressure was lowered to 1.0 MPa over 30 minutes, and the reaction was carried out for another 1 hour to obtain a prepolymer. This was dried at 100 ° C. under reduced pressure for 12 hours, pulverized to a size of 2 mm or less, and solid-phase polymerized at 210 ° C. under 0.013 kPa for 8 hours to have a melting point of 265 ° C. and a relative viscosity of 2.38. An aromatic polyamide (polyamide 9T / M8T = 50/50 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B1-1)).

Production of Semi-Aromatic Polyamide (B1-2) In the production of Semi-Aromatic Polyamide (B1-1), 2.37 kg (15.0 mol) of 1,9-nonanediamine and 2-methyl-1,8-octanediamine 2 Change .37 kg (15.0 mol) to 4.04 kg (25.5 mol) of 1,9-nonanediamine and 0.712 kg (4.5 mol) of 2-methyl-1,8-octanediamine, and solid-phase polymerization temperature. Semi-aromatic polyamide (polyamide 9T / M8T = 85) having a melting point of 305 ° C. and a relative viscosity of 2.34 by the same method as for producing the semi-aromatic polyamide (B1-1) except that the temperature was changed from 210 to 240 ° C. / 15 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B1-2)).

Production of Semi-Aromatic Polyamide (B1-3) In the production of Semi-Aromatic Polyamide (B1-1), 4.94 kg (29.7 mol) of terephthalic acid was added to 6.43 kg (29.7 mol) of 2,6-naphthalenedicarboxylic acid. Semi-aromatic polyamide (polyamide 9N / M8N = 50/50 mol) having a melting point of 275 ° C. and a relative viscosity of 2.37 by the same method as for the production of semi-aromatic polyamide (B1-1) except that it was changed to (molar). %) Was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B1-3)).

Production of Semi-Aromatic Polyamide (B1-4) In the production of Semi-Aromatic Polyamide (B1-1), 2.37 kg (15.0 mol) of 1,9-nonanediamine and 2-methyl-1,8-octanediamine 2 Semi-aromatic polyamide (B1-) except that .37 kg (15.0 mol) was changed to 1,10-decanediamine 5.17 kg (30.0 mol) and the solid phase polymerization temperature was changed from 230 ° C to 260 ° C. A semi-aromatic polyamide (polyamide 10T = 100 mol%) having a melting point of 315 ° C. and a relative viscosity of 2.33 was obtained by the same method as in the production of 1) (hereinafter, this semi-aromatic polyamide is (B1-4). That.).

Production of Semi-Aromatic Polyamide (B1-5) In the production of Semi-Aromatic Polyamide (B1-4), 5.17 kg (30.0 mol) of 1,10-decanediamine and 4.98 kg (30.0 mol) of terephthalic acid ) To 3.10 kg (18.0 mol) of 1,10-decanediamine, 2.99 kg (18.0 mol) of terephthalic acid, and 2.42 kg (12.0 mol) of 11-aminoundecanoic acid. A semi-aromatic polyamide (polyamide 10T /) having a melting point of 255 ° C. and a relative viscosity of 2.34 was carried out in the same manner as in the production of the semi-aromatic polyamide (B1-4) except that the polymerization temperature was changed from 260 ° C. to 200 ° C. 11 = 60/40 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B1-5)).

Production of Semi-Aromatic Polyamide (B1-6) In the production of Semi-Aromatic Polyamide (B1-4), 4.98 kg (30.0 mol) of terephthalic acid was combined with 3.32 kg (20.0 mol) of terephthalic acid and sebacic acid. The melting point was 279 ° C. in the same manner as in the production of semi-aromatic polyamide (B1-4), except that the solid phase polymerization temperature was changed from 260 ° C. to 220 ° C. by changing to 2.02 kg (10.0 mol). A semi-aromatic polyamide having a relative viscosity of 2.37 (polyamide 10T / 1010 = 67/33 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B1-6)).

Production of Semi-Aromatic Polyamide (B1-7) In the production of Semi-Aromatic Polyamide (B1-4), 5.17 kg (30.0 mol) of 1,10-decanediamine and 4.98 kg (30.0 mol) of terephthalic acid. ) Is changed to 7.26 kg (24.0 mol) of an isomolar salt of 1,10-decanediamine and terephthalic acid, and 1.863 kg (6.0 mol) of an equimolar salt of 1,6-hexanediamine and dodecanedioic acid. A semi-aromatic polyamide having a melting point of 261 ° C and a relative viscosity of 2.34 (in the same manner as in the production of the semi-aromatic polyamide (B1-4), except that the solid phase polymerization temperature was changed from 260 ° C. to 210 ° C. Polyamide 10T / 612 = 80/20 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B1-7)).

Production of Semi-Aromatic Polyamide (B1-8) In the production of Semi-Aromatic Polyamide (B1-1), except that the solid phase polymerization time was changed from 8 hours to 4 hours, the semi-aromatic polyamide (B1-1) A semi-aromatic polyamide (polyamide 9T / M8T = 50/50 mol%) having a melting point of 265 ° C. and a relative viscosity of 2.08 was obtained by the same method as in the production (hereinafter, this semi-aromatic polyamide is (B1-8). ).).

Production of Semi-Aromatic Polyamide (B1-9) In the production of Semi-Aromatic Polyamide (B1-1), 4.94 kg (29.7 mol) of terephthalic acid and 2.37 kg (15.0 mol) of 1,9-nonanediamine. , And 2-methyl-1,8-octanediamine 2.37 kg (15.0 mol), terephthalic acid 2.74 kg (16.5 mol), isophthalic acid 0.997 kg (6.0 mol), adipic acid 1. Semi-aromatic polyamide except that the weight was changed to 10 kg (7.5 mol) and 1,6-hexanediamine 3.60 kg (31.0 mol), the polymerization temperature was changed to 250 ° C, and the solid phase polymerization temperature was changed to 230 ° C. A semi-aromatic polyamide (polyamide 6T / 6I / 66 = 55/20/25 mol%) having a melting point of 302 ° C. and a relative viscosity of 2.28 was obtained by the same method as in the production of (B1-1) (hereinafter, This semi-aromatic polyamide is referred to as (B1-9)).

Semi-aromatic polyamide (B2)
Manufacture of semi-aromatic polyamide (B2-1) Equipped with a stirrer, thermometer, torque meter, pressure gauge, raw material inlet directly connected to diaphragm pump, nitrogen gas inlet, pressure discharge port, pressure regulator, and polymer discharge port. In a pressure vessel with an internal volume of 70 liters, 6.07 kg (30.0 mol) of sebacic acid, 8.5 g (0.049 mol) of calcium hypophosphate, and 2.2 g (0.025 mol) of sodium acetate were charged. After pressurizing the inside of the pressure vessel with nitrogen gas having a purity of 99.9999% to 0.3 MPa, the operation of releasing the nitrogen gas to normal pressure was repeated 5 times, and after nitrogen substitution, the pressure was reduced. The temperature inside the system was raised while stirring. After raising the temperature to 190 ° C. under a further small amount of nitrogen stream, 4.09 kg (30.0 mol) of m-xylylenediamine was added dropwise over 160 minutes with stirring. During this period, the internal pressure of the reaction system was controlled to 0.5 MPa, and the internal temperature was continuously raised to 295 ° C. In addition, the water distilled out with the dropping of m-xylylenediamine was removed from the system through a condenser and a cooler. After the addition of m-xylylenediamine was completed, the pressure was lowered to normal pressure over 60 minutes, and during this period, the temperature inside the container was maintained at 250 ° C. and the reaction was continued for 10 minutes. Then, the internal pressure of the reaction system was reduced to 79 kPa, and the melt polymerization reaction was continued for 40 minutes. Then, the stirring was stopped and the inside of the system was pressurized to 0.2 MPa with nitrogen, and the polycondensate was extracted in a string shape from the outlet at the bottom of the pressure vessel. The string-shaped polycondensate is immediately cooled, the water-cooled string-shaped resin is pelletized with a pelletizer, and then dried under reduced pressure to have a melting point of 191 ° C. and a relative viscosity of 2.46. Semi-aromatic polyamide (polyamide MXD10 = 100 mol%). ) (Hereinafter, this semi-aromatic polyamide is referred to as (B2-1)).

Production of Semi-Aromatic Polyamide (B2-2) In the production of semi-aromatic polyamide (B2-1), 4.09 kg (30.0 mol) of m-xylylenediamine was added to m-xylylenediamine and p-xylylenediamine. 7: 3 mixed diamine (30.0 mol) was changed to 4.09 kg (30.0 mol), and the polymerization temperature was changed from 250 ° C. to 260 ° C. in the same manner as in the production of semi-aromatic polyamide (B2-1). , A semi-aromatic polyamide (polyamide MXD10 / PXD10 = 70/30 mol%) having a melting point of 215 ° C. and a relative viscosity of 2.40 was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B2-2)).

Production of Semi-Aromatic Polyamide (B2-3) In the production of semi-aromatic polyamide (B2-1), 4.09 kg (30.0 mol) of m-xylylenediamine was added to m-xylylenediamine and p-xylylenediamine. The same method as for the production of semi-aromatic polyamide (B2-1) except that the ratio was changed to 4.09 kg (30.0 mol) of the 6: 4 mixed diamine and the polymerization temperature was changed from 250 ° C. to 270 ° C. , A semi-aromatic polyamide (polyamide MXD10 / PXD10 = 60/40 mol%) having a melting point of 224 ° C. and a relative viscosity of 2.42 was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B2-3)).

Production of Semi-Aromatic Polyamide (B2-4) In the production of semi-aromatic polyamide (B2-1), 4.09 kg (30.0 mol) of m-xylylenediamine was added to 4.09 kg (30. The melting point is 281 and 291 ° C. (having two melting points) in the same manner as in the production of the semi-aromatic polyamide (B2-1) except that the polymerization temperature is changed from 250 ° C. to 300 ° C. (0 mol). , A semi-aromatic polyamide having a relative viscosity of 2.42 (polyamide PXD10 = 100 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B2-4)).

Production of Semi-Aromatic Polyamide (B2-5) In the production of Semi-Aromatic Polyamide (B2-1), 6.07 kg (30.0 mol) of sebacic acid was changed to 5.65 kg (30.0 mol) of azelaic acid. A semi-aromatic polyamide (polyamide MXD9 = 100 mol%) having a melting point of 194 ° C. and a relative viscosity of 2.45 was obtained by the same method as for producing the semi-aromatic polyamide (B2-1) except for the above. The semi-aromatic polyamide is referred to as (B2-5)).

Production of Semi-Aromatic Polyamide (B2-6) In the production of Semi-Aromatic Polyamide (B2-1), 4.09 kg (30.0 mol) of m-xylylenediamine was added to 2,6-bis (aminomethyl) naphthalene 5 The melting point was 286 ° C. and the relative viscosity was 2 in the same manner as in the production of the semi-aromatic polyamide (B2-1), except that the weight was changed to .59 kg (30.0 mol) and the polymerization temperature was changed from 240 ° C. to 300 ° C. A semi-aromatic polyamide of .33 (polyamide 2,6-BAN10 = 100 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B2-6)).

Production of semi-aromatic polyamide (B2-7) In the production of semi-aromatic polyamide (B2-1), except that the melt polymerization time was changed from 40 minutes to 20 minutes, the production of semi-aromatic polyamide (B2-1) and By the same method, a semi-aromatic polyamide (polyamide MXD10 = 100 mol%) having a melting point of 191 ° C. and a relative viscosity of 2.15 was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B2-7)).

Production of Semi-Aromatic Polyamide (B2-8) In the production of semi-aromatic polyamide (B2-1), 6.07 kg (30.0 mol) of sebacic acid was changed to 4.38 kg (30.0 mol) of adipic acid. Semi-aromatic polyamide (polyamide MXD6 =) having a melting point of 243 ° C and a relative viscosity of 2.42 in the same manner as in the production of semi-aromatic polyamide (B2-1) except that the polymerization temperature was changed from 250 ° C to 275 ° C. 100 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (B2-8)).

Semi-aromatic polyamide composition (B)
Production of Semi-Aromatic Polyamide Composition (B-1) In addition to semi-aromatic polyamide (B1-1), maleic anhydride-modified ethylene / 1-butene copolymer (A2-1) as an impact improver, as an antioxidant. Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (made by BASF Japan, IRGANOX245), and tris (2,4-di-) as a phosphorus-based processing stabilizer. t-Butylphenyl) phosphite (manufactured by BASF Japan, IRGAFOS168) is mixed in advance and supplied to a twin-screw melt-kneader (manufactured by Japan Steel Works, Ltd., model: TEX44) at a cylinder temperature of 220 ° C to 300 ° C. After melt-kneading and extruding the molten resin into strands, this is introduced into a water tank, cooled, cut, and vacuum-dried to contain 90% by mass of semi-aromatic polyamide (B1-1) and 10% by mass of impact improving material. Pellets of a semi-aromatic polyamide 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 semi-aromatic polyamide composition). Is called (B-1).

Production of Semi-Aromatic Polyamide Composition (B-2) In the production of semi-aromatic polyamide composition (B-1), the semi-aromatic polyamide (B1-1) was changed to (B1-2) and the cylinder temperature was set to 300. 90% by mass of the semi-aromatic polyamide (B1-2) and 10% by mass of the impact improving material were prepared in the same manner as in the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from ℃ to 340 ° C. Pellets of a semi-aromatic polyamide 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 semi-aromatic polyamide composition). Is called (B-2).

Production of Semi-Aromatic Polyamide Composition (B-3) In the production of the semi-aromatic polyamide composition (B-1), the semi-aromatic polyamide (B1-1) was changed to (B1-3) and the cylinder temperature was set to 300. 90% by mass of the semi-aromatic polyamide (B1-3) and 10% by mass of the impact improver by the same method as in the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from ° C to 310 ° C. Pellets of a semi-aromatic polyamide 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 semi-aromatic polyamide composition). Is called (B-3).

Production of Semi-Aromatic Polyamide Composition (B-4) In the production of the semi-aromatic polyamide composition (B-1), the semi-aromatic polyamide (B1-1) was changed to (B1-4) and the cylinder temperature was set to 300. 90% by mass of the semi-aromatic polyamide (B1-4) and 10% by mass of the impact improving material were prepared in the same manner as in the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from ℃ to 340 ° C. Pellets of a semi-aromatic polyamide 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 semi-aromatic polyamide composition). Is called (B-4).

Production of Semi-Aromatic Polyamide Composition (B-5) In the production of the semi-aromatic polyamide composition (B-1), the semi-aromatic polyamide (B1-1) was changed to (B1-5) and the cylinder temperature was set to 300. 90% by mass of the semi-aromatic polyamide (B1-5) and 10% by mass of the impact improving material were prepared in the same manner as in the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from ℃ to 290 ° C. Pellets of a semi-aromatic polyamide 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 semi-aromatic polyamide composition). Is called (B-5)).

Production of Semi-Aromatic Polyamide Composition (B-6) In the production of the semi-aromatic polyamide composition (B-1), the semi-aromatic polyamide (B1-1) was changed to (B1-6) and the cylinder temperature was set to 300. 90% by mass of semi-aromatic polyamide (B1-6) and 10% by mass of impact improving material by the same method as in the production of semi-aromatic polyamide composition (B-1) except that the temperature was changed from ° C to 310 ° C. Pellets of a semi-aromatic polyamide 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 semi-aromatic polyamide composition). Is called (B-6).

Production of Semi-Aromatic Polyamide Composition (B-7) In the production of semi-aromatic polyamide composition (B-1), except that the semi-aromatic polyamide (B1-1) was changed to (B1-7). By the same method as for the production of the aromatic polyamide composition (B-1), the antioxidant is applied to 100 parts by mass of 90% by mass of the semi-aromatic polyamide (B1-7) and 10% by mass of the impact improving material. Pellets of a semi-aromatic polyamide composition consisting of 0.8 parts by mass and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained (hereinafter, this semi-aromatic polyamide composition is referred to as (B-7)).

Production of Semi-Aromatic Polyamide Composition (B-8) In the production of the semi-aromatic polyamide composition (B-1), the semi-aromatic polyamide (B1-1) was changed to (B1-9) and the cylinder temperature was set to 300. 90% by mass of the semi-aromatic polyamide (B1-9) and 10% by mass of the impact improving material were prepared in the same manner as in the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from ℃ to 340 ° C. Pellets of a semi-aromatic polyamide 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 semi-aromatic polyamide composition). Is called (B-8)).

Production of Semi-Aromatic Polyamide Composition (B-9) In the production of the semi-aromatic polyamide composition (B-1), the semi-aromatic polyamide (B1-1) was changed to (B2-1) and the cylinder temperature was set to 300. 90% by mass of the semi-aromatic polyamide (B2-1) and 10% by mass of the impact improving material were prepared in the same manner as in the production of the semi-aromatic polyamide composition (B-1) except that the temperature was changed from ° C to 240 ° C. Pellets of a semi-aromatic polyamide 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 semi-aromatic polyamide composition). Is called (B-9)).

Production of Semi-Aromatic Polyamide Composition (B-10) In the production of the semi-aromatic polyamide composition (B-9), the semi-aromatic polyamide (B2-1) was changed to (B2-2) and the cylinder temperature was changed to 240. 90% by mass of semi-aromatic polyamide (B2-2) and 10% by mass of impact improver by the same method as in the production of semi-aromatic polyamide composition (B-9) except that the temperature was changed from ° C to 250 ° C. Pellets of a semi-aromatic polyamide 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 semi-aromatic polyamide composition). Is called (B-10)).

Production of Semi-Aromatic Polyamide Composition (B-11) In the production of the semi-aromatic polyamide composition (B-9), the semi-aromatic polyamide (B2-1) was changed to (B2-3) and the cylinder temperature was changed to 240. 90% by mass of the semi-aromatic polyamide (B2-3) and 10% by mass of the impact improving material were prepared in the same manner as in the production of the semi-aromatic polyamide composition (B-9) except that the temperature was changed from ° C to 260 ° C. Pellets of a semi-aromatic polyamide 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 semi-aromatic polyamide composition). Is referred to as (B-11)).

Production of Semi-Aromatic Polyamide Composition (B-12) In the production of the semi-aromatic polyamide composition (B-9), the semi-aromatic polyamide (B2-1) was changed to (B2-4) and the cylinder temperature was changed to 240. 90% by mass of semi-aromatic polyamide (B2-4) and 10% by mass of impact improver by the same method as in the production of semi-aromatic polyamide composition (B-9) except that the temperature was changed from ° C to 320 ° C. Pellets of a semi-aromatic polyamide 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 semi-aromatic polyamide composition). Is called (B-12)).

Production of Semi-Aromatic Polyamide Composition (B-13) In the production of semi-aromatic polyamide composition (B-9), except that the semi-aromatic polyamide (B2-1) was changed to (B2-5). The antioxidant was applied to 100 parts by mass of 90% by mass of the semi-aromatic polyamide (B2-5) and 10% by mass of the impact improving material by the same method as in the production of the aromatic polyamide composition (B-9). Pellets of a semi-aromatic polyamide composition consisting of 0.8 parts by mass and 0.2 parts by mass of a phosphorus-based processing stabilizer were obtained (hereinafter, this semi-aromatic polyamide composition is referred to as (B-13)).

Production of Semi-Aromatic Polyamide Composition (B-14) In the production of the semi-aromatic polyamide composition (B-9), the semi-aromatic polyamide (B2-1) was changed to (B2-6) and the cylinder temperature was changed to 240. 90% by mass of semi-aromatic polyamide (B2-6) and 10% by mass of impact improver by the same method as in the production of semi-aromatic polyamide composition (B-9) except that the temperature was changed from ° C to 320 ° C. Pellets of a semi-aromatic polyamide 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 semi-aromatic polyamide composition). Is called (B-14)).

Production of Semi-Aromatic Polyamide Composition (B-15) In the production of the semi-aromatic polyamide composition (B-9), the semi-aromatic polyamide (B2-1) was changed to (B2-8) and the cylinder temperature was changed to 240. 90% by mass of the semi-aromatic polyamide (B2-8) and 10% by mass of the impact improver by the same method as in the production of the semi-aromatic polyamide composition (B-9) except that the temperature was changed from ℃ to 280 ° C. Pellets of a semi-aromatic polyamide 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 semi-aromatic polyamide composition). Is called (B-15)).

Production of Conductive Semi-Aromatic Polyamide Composition (B-16) In addition to semi-aromatic polyamide (B1-8), maleic anhydride-modified ethylene / 1-butene copolymer (A2-1) and ethylene / 1-Butene copolymer (Mitsui Kagaku Co., Ltd., Toughmer A-0550), carbon black (Lion Co., Ltd., Ketjen Black EC600JD) as a conductive filler, triethylene glycol-bis [3] as an antioxidant -(3-t-Butyl-5-methyl-4-hydroxyphenyl) propionate] (BASF Japan, Inc., IRGANOX245), and tris (2,4-di-t-butylphenyl) phosphite as a phosphorus-based processing stabilizer. (BASF Japan, IRGAFOS168) is mixed in advance, supplied to a twin-screw melt-kneader (manufactured by Nippon Steel Co., Ltd., model: TEX44), melt-kneaded at a cylinder temperature of 240 ° C to 320 ° 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 obtain 68% by mass of semi-aromatic polyamide (B1-8), 25% by mass of impact modifier, and 7% by mass of conductive filler. Pellets of a conductive semi-aromatic polyamide 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 semi-aromatic). The group polyamide composition is referred to as (B-16)).

Production of Conductive Semi-Aromatic Polyamide Composition (B-17) In the production of the conductive semi-aromatic polyamide composition (B-16), the semi-aromatic polyamide (B1-8) was changed to (B2-7). Semi-aromatic polyamide (B2-7) 68% by mass, impact in the same manner as in the production of the conductive semi-aromatic polyamide composition (B-16), except that the cylinder temperature was changed from 320 ° C to 270 ° C. A conductive semi-aromatic polyamide 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 25% by mass of the improving material and 7% by mass of the conductive filler. (Hereinafter, this conductive semi-aromatic polyamide composition is referred to as (B-17)).

Fluorine-containing polymer (C)
Production of Fluorine-Containing Polymer (C-1) 92.1 kg of 1-hydrotridecafluorohexane, 1,3-dichloro-1,1,2 by degassing a polymerization tank with a stirrer having an internal volume of 100 L. , 2,3-Pentafluoropropane 16.3 kg, (perfluoroethyl) ethylene CH ₂ = CH (CF ₂ ) ₂ F 73 g, itaconic anhydride (IAH) 10.1 g, tetrafluoroethylene (TFE) 9.6 kg , 0.7 kg of ethylene (E) was press-fitted, the temperature inside the polymerization tank was raised to 66 ° C., and t-butylperoxypivalate 1% by mass 1,3-dichloro-1,1,2,2 as a polymerization initiator. ^{433 cm 3} of a 3-pentafluoropropane solution was charged and polymerization was started. A monomer mixed gas having a TFE / E: 60/40 (molar ratio) was continuously charged so that the pressure during the polymerization became constant. In addition, 2.0 mol% of (perfluoroethyl) ethylene and 0.5 mol% of IAH were continuously charged with respect to the total number of moles of TFE and E charged during the polymerization. .. 5.5 hours after the start of polymerization, when 8.0 kg of the monomer mixed gas and 63 g of IAH were charged, the temperature inside the polymerization tank was lowered to room temperature and purged to bring the pressure to normal pressure. The obtained slurry-like fluorine-containing polymer was put into a 200 L granulation tank charged with 75.0 kg of water, and then the temperature was raised to 105 ° C. with stirring to granulate while distilling off the solvent. The obtained granulated product was dried at 150 ° C. for 5 hours to obtain 8.3 kg of a fluorine-containing polymer.
The composition of those fluorinated polymers, polymerized units _/ CH based on polymerized units / E based on TFE 2 = CH _{(CF 2)} based on polymerized units / IAH based on ₂ F polymerized units = 58.5 / 39.0 It was /2.0/0.5 (mol%) and had a melting point of 240 ° C. This granulated product was melted at 280 ° C. for a residence time of 2 minutes using an extruder to obtain pellets of a fluorine-containing polymer (hereinafter, this fluorine-containing polymer is referred to as (C-1). )

Production of conductive fluorinated polymer (C-2) 100 parts by mass of fluorinated polymer (C-1) and 13 parts by mass of carbon black (manufactured by Electrochemical Co., Ltd.) are mixed in advance and biaxially melted. It is supplied to a kneader (manufactured by Toshiba Machine Co., Ltd., model: TEM-48S), melt-kneaded at a cylinder temperature of 240 ° C to 300 ° C, extruded into a strand of molten resin, introduced into a water tank, and discharged. The strands were cooled with water, the strands were cut with a pelletizer, and dried in a dryer at 120 ° C. for 10 hours to remove water, to obtain pellets of a conductive fluorine-containing polymer (hereinafter, this conductive fluorine-containing polymer). The polymer is referred to as (C-2)).

Production of Fluorine-Containing Polymer (C-3) In the production of Fluorine-Containing Polymer (C-1), except that itaconic anhydride (IAH) is not charged, production of Fluorine-Containing Polymer (C-1) In the same manner as in the above, 7.6 kg of a fluorine-containing polymer was obtained.
The composition of the fluorine-containing polymer is as follows: TFE-based polymerization unit / E-based polymerization unit / CH ₂ = CH (CF ₂ ) ₂ F-based polymerization unit / IAH-based polymerization unit = 58.8 / 39.2. It was /2.0 (mol%) and had a melting point of 242 ° C. This granulated product was melted at 280 ° C. for a residence time of 2 minutes using an extruder to obtain pellets of a fluorine-containing polymer (hereinafter, this fluorine-containing polymer is referred to as (C-3). ).

Production of conductive fluorinated polymer (C-4) In the production of conductive fluorinated polymer (C-2), except that the fluorinated polymer (C-1) was changed to (C-3). Obtained pellets of the conductive fluorinated polymer by the same method as in the production of the conductive fluorinated polymer (C-2) (hereinafter, this conductive fluorinated polymer is referred to as (C-). 4).

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

Production of Fluorine-Containing Polymer (C-6) In the production of Fluorine-Containing Polymer (C-5), 5-norbornene-2,3-dicarboxylic acid anhydride (NAH) 0.3% by mass 1,3- A 7.6 kg fluorinated polymer was produced in the same manner as in the production of the fluorinated polymer (C-5), except that a dichloro-1,1,2,2,3-pentafluoropropane solution was not charged. Got
The composition of the fluorine-containing polymer is TFE-based polymerization unit / PPVE-based polymerization unit / HFP-based polymerization unit = 91.5 / 1.5 / 7.0 (mol%), and the melting point is 257 ° C. Met. This granulated product was melted at 300 ° C. for a residence time of 2 minutes using an extruder to obtain pellets of a fluorine-containing polymer (hereinafter, this fluorine-containing polymer is referred to as (C-6). ).

Production of Conductive Fluorine-Containing Polymer (C-7) In the production of the conductive fluorine-containing polymer (C-2), the fluorine-containing polymer (C-1) was used as (C-6), and carbon black 13 was used. Conductive fluorine-containing weight in the same manner as in the production of the conductive fluorine-containing polymer (C-2), except that the mass part was changed to 11 parts by mass and the cylinder temperature was changed from 300 ° C to 320 ° C. Combined pellets were obtained (hereinafter, this conductive fluorine-containing polymer is referred to as (C-7)).

Production of fluoropolymer (C-8) In a stirring polymer tank with a jacket that can accommodate 174 kg of water, 51.5 kg of demineralized pure water is charged, the internal space is sufficiently replaced with pure nitrogen gas, and then nitrogen gas is used. Was eliminated by vacuum. Next, 40.6 kg of octafluorocyclobutane, 1.6 kg of chlorotrifluoroethylene (CTFE), 4.5 kg of tetrafluoroethylene (TFE), and 2.8 kg of perfluoro (propyl vinyl ether) (PPVE) were press-fitted. 0.090 kg of n-propyl alcohol was added as a chain transfer agent, the temperature was adjusted to 35 ° C., and stirring was started. 0.44 kg of a 50% by mass methanol solution of di-n-propylperoxydicarbonate was added thereto as a polymerization initiator to initiate polymerization. During the polymerization, a mixed monomer prepared to have the same composition as the desired copolymer composition is polymerized while being additionally charged so as to maintain the pressure in the tank at 0.66 MPa, and then the residual gas in the tank is exhausted. The produced polymer was taken out, washed with demineralized pure water, and dried to obtain a fluorine-containing polymer of 30.5 kg of granular powder.
The composition of the fluorine-based polymer is 24.4 / 73.1 / 2.5 in terms of the molar ratio of the polymerization unit based on CTFE / the polymerization unit based on TFE / the polymerization unit based on PPVE, and is contained in the fluorine-based polymer. The number of carbonate terminal groups derived from the polymerization initiator of the fluorine-based polymer was 170 with respect to the number of carbon atoms in the main chain of 1 × 10 ^6. The melting point was 241 ° C. This granulated product was melted at 290 ° C. for a residence time of 2 minutes using an extruder to obtain pellets of a fluorine-containing polymer (hereinafter, this fluorine-containing polymer is referred to as (C-8)). ).

Production of Fluorine-Containing Polymer (C-9) In the production of Fluorine-Containing Polymer (C-8), Fluorine-containing weight except that a 50% by mass methanol solution of di-n-propylperoxydicarbonate is not charged. 29.8 kg of a fluorine-containing polymer was obtained by the same method as in the production of the coalescence (C-9).
The composition of the fluorine-containing polymer is 24.4 / 73.1 / 2.5 in terms of the molar ratio of the polymerization unit based on CTFE / the polymerization unit based on TFE / the polymerization unit based on PPVE, and the melting point is 241 ° C. there were. This granulated product was melted at 290 ° C. for a residence time of 2 minutes using an extruder to obtain pellets of a fluorine-containing polymer (hereinafter, this fluorine-containing polymer is referred to as (C-9). ).

Production of conductive fluorinated polymer (C-10) In the production of conductive fluorinated polymer (C-7), the fluorinated polymer (C-6) was changed to (C-9) to form a cylinder. Pellets of the conductive fluorinated polymer were obtained by the same method as in the production of the conductive fluorinated polymer (C-7) except that the temperature was changed from 320 ° C. to 300 ° C. (hereinafter, this). The conductive fluorine-containing polymer is referred to as (C-10)).

Example 1
Using the polyamide 12 / 9T composition (A-1) and semi-aromatic polyamide composition (B-1) shown above, in a two-layer tube molding machine manufactured by Plabor (manufactured by Plastic Engineering Laboratory Co., Ltd.). (A-1) was separately melted at an extrusion temperature of 270 ° C. and (B-1) at an extrusion temperature of 300 ° C., and the discharged molten resins were merged by an adapter to form a laminated tubular body. Subsequently, when it is cooled by a sizing die whose size is controlled and taken over to form a (a) layer (outermost layer) composed of (A-1) and a (b) layer (innermost layer) composed of (B-1). A laminated tube having a layer structure of (a) / (b) = 0.80 / 0.20 mm and an inner diameter of 6 mm and an outer diameter of 8 mm was obtained. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

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 / 9T composition (A-1) was changed to the polyamide 11 / 10T composition (A-2). Obtained a laminated tube of. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 3
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 / 9T composition (A-1) was changed to the polyamide 1010 / 10T composition (A-3). Obtained a laminated tube of. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 4
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 / 9T composition (A-1) was changed to the polyamide 12 / MXD10 composition (A-4). Obtained a laminated tube of. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 5
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 / 9T composition (A-1) was changed to the polyamide 1010 / MXD10 composition (A-5). Obtained a laminated tube of. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 6
In Example 1, the method was the same as in Example 1 except that the semi-aromatic polyamide composition (B-1) was changed to (B-2) and the extrusion temperature of (B-2) was changed to 340 ° C. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 7
In Example 1, the method was the same as in Example 1 except that the semi-aromatic polyamide composition (B-1) was changed to (B-3) and the extrusion temperature of (B-3) was changed to 310 ° C. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 8
In Example 2, the method was the same as in Example 2 except that the semi-aromatic polyamide composition (B-1) was changed to (B-4) and the extrusion temperature of (B-4) was changed to 340 ° C. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 9
In Example 2, the method was the same as in Example 2 except that the semi-aromatic polyamide composition (B-1) was changed to (B-5) and the extrusion temperature of (B-5) was changed to 290 ° C. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 10
In Example 2, the method was the same as in Example 2 except that the semi-aromatic polyamide composition (B-1) was changed to (B-6) and the extrusion temperature of (B-6) was changed to 310 ° C. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 11
In Example 2, a laminated tube having a layer structure shown in Table 1 was obtained in the same manner as in Example 2 except that the semi-aromatic polyamide composition (B-1) was changed to (B-7). .. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 12
In Example 4, the method was the same as in Example 4 except that the semi-aromatic polyamide composition (B-1) was changed to (B-9) and the extrusion temperature of (B-9) was changed to 240 ° C. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 13
In Example 4, the method was the same as in Example 4 except that the semi-aromatic polyamide composition (B-1) was changed to (B-10) and the extrusion temperature of (B-10) was changed to 250 ° C. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 14
In Example 4, the method was the same as in Example 4 except that the semi-aromatic polyamide composition (B-1) was changed to (B-11) and the extrusion temperature of (B-11) was changed to 260 ° C. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 15
In Example 4, the method was the same as in Example 4 except that the semi-aromatic polyamide composition (B-1) was changed to (B-12) and the extrusion temperature of (B-12) was changed to 320 ° C. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 16
In Example 4, the method was the same as in Example 4 except that the semi-aromatic polyamide composition (B-1) was changed to (B-13) and the extrusion temperature of (B-13) was changed to 240 ° C. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 17
In Example 4, the method was the same as in Example 4 except that the semi-aromatic polyamide composition (B-1) was changed to (B-14) and the extrusion temperature of (B-14) was changed to 320 ° C. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 18
Except that in Example 1, the semi-aromatic polyamide composition (B-1) was changed to the conductive semi-aromatic polyamide composition (B-16) and the extrusion temperature of (B-16) was changed to 320 ° C. A laminated tube having a layer structure shown in Table 1 was obtained by the same method as in Example 1. Table 1 shows the results of measuring the physical characteristics 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
Except that in Example 4, the semi-aromatic polyamide composition (B-1) was changed to the conductive semi-aromatic polyamide composition (B-17) and the extrusion temperature of (B-17) was changed to 270 ° C. A laminated tube having a layer structure shown in Table 1 was obtained by the same method as in Example 4. Table 1 shows the results of measuring the physical characteristics 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 20
Using the above-mentioned polyamide 12 / 9T composition (A-1), semi-aromatic polyamide composition (B-1), and conductive semi-aromatic polyamide composition (B-16), Prabor (Plastic Engineering Research). (A-1) at an extrusion temperature of 260 ° C., (B-1) at an extrusion temperature of 300 ° C., and (B-16) at an extrusion temperature of 320 ° C. separately using a three-layer tube molding machine manufactured by Tokoro Co., Ltd. By melting, the discharged molten resin was merged by an adapter and molded into 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 (intermediate layer) composed of (B-1), and (B-) are obtained. When the (b') layer (innermost layer) composed of 16) is used, the layer structure is (a) / (b) / (b') = 0.80 / 0.10 / 0.10 mm, the inner diameter is 6 mm, and the outer diameter is outer diameter. An 8 mm laminated tube was obtained. Table 1 shows the results of measuring the physical characteristics 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 21
In Example 20, the polyamide 12 / 9T composition (A-1) was the polyamide 12 / MXD10 composition (A-4), the semi-aromatic polyamide composition (B-1) was (B-9), and the conductive semi. Examples except that the aromatic polyamide composition (B-16) was changed to (B-17), the extrusion temperature of (B-9) was changed to 240 ° C., and the extrusion temperature of (B-17) was changed to 270 ° C. A laminated tube having a layer structure shown in Table 1 was obtained by the same method as in No. 20. Table 1 shows the results of measuring the physical characteristics 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 22
Using the above-mentioned polyamide 12 / 9T composition (A-1), semi-aromatic polyamide composition (B-1), and fluorine-containing polymer (C-1), Plover (Plastic Engineering Laboratory Co., Ltd.) ), (A-1) is melted separately at an extrusion temperature of 260 ° C., (B-1) at an extrusion temperature of 300 ° C., and (C-1) at an extrusion temperature of 290 ° C. in a three-layer tube molding machine. The discharged molten resin is merged by an adapter, molded into a tubular shape, cooled by a sizing die that controls dimensions, and taken over, and the layer composed of (A-1) is formed into the layer (a) (outermost layer) and (B-). When the layer composed of 1) is the layer (b) (intermediate layer) and the layer composed of (C-1) is the layer (c) (innermost layer), the layer structure is (a) / (b) / (c). = 0.80 / 0.10 / 0.10 mm, 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 characteristics of the laminated tube.

Example 23
In Example 22, the polyamide 12 / 9T composition (A-1) was changed to the polyamide 12 / MXD10 composition (A-4), and the semi-aromatic polyamide composition (B-1) was changed to (B-9). A laminated tube having a layer structure shown in Table 1 was obtained in the same manner as in Example 22 except that the extrusion temperature of B-9) was changed to 240 ° C. Table 1 shows the results of measuring the physical characteristics of the laminated tube. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 24
Example 22 except that the fluorinated polymer (C-1) was changed to the conductive fluorinated polymer (C-2) and the extrusion temperature of (C-2) was changed to 310 ° C. A laminated tube having a layer structure shown in Table 1 was obtained by the same method as in No. 22. Table 1 shows the results of measuring the physical characteristics of the laminated tube. Table 1 shows the results of measuring the physical characteristics 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 25
In Example 22, the same method as in Example 22 was used except that the fluorine-containing polymer (C-1) was changed to (C-5) and the extrusion temperature of (C-5) was changed to 310 ° C. , A laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical characteristics of the laminated tube. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 26
In Example 22, the same method as in Example 22 was used except that the fluorine-containing polymer (C-1) was changed to (C-8) and the extrusion temperature of (C-8) was changed to 300 ° C. , A laminated tube having a layer structure shown in Table 1 was obtained. Table 1 shows the results of measuring the physical characteristics of the laminated tube. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 27
Polyamide 12 / 9T composition (A-1), semi-aromatic polyamide composition (B-1), fluoropolymer (C-1), conductive fluoropolymer (C-2) shown above. In a 4-layer tube forming machine manufactured by Polymer (manufactured by Plastic Engineering Laboratory Co., Ltd.), (A-1) has an extrusion temperature of 260 ° C., (B-1) has an extrusion temperature of 300 ° C., and (C-1). ) Is melted separately at an extrusion temperature of 290 ° C. and (C-2) is melted separately at an extrusion temperature of 310 ° C. The layer composed of (A-1) is the layer (a) (outermost layer), the layer composed of (B-1) is the layer (b) (intermediate layer), and the layer composed of (C-1) is (c). ) Layer (inner layer), when the layer composed of (C-2) is the (c') layer (innermost layer), the layer structure is (a) / (b) / (c) / (c') = 0. A laminated tube having a diameter of 70 / 0.10 / 0.10 / 0.10 mm, an inner diameter of 6 mm, and an outer diameter of 8 mm was obtained. Table 1 shows the results of measuring the physical characteristics 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 28
In Example 27, the polyamide 12 / 9T composition (A-1) was changed to the polyamide 12 / MXD10 composition (A-4), and the semi-aromatic polyamide composition (B-1) was changed to (B-9). A laminated tube having a layer structure shown in Table 1 was obtained in the same manner as in Example 27 except that the extrusion temperature of B-9) was changed to 240 ° C. Table 1 shows the results of measuring the physical characteristics of the laminated tube. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 29
In Example 27, except that the conductive fluorinated polymer (C-2) was changed to the fluorinated polymer (C-3) and the extrusion temperature of (C-3) was changed to 290 ° C. In the same manner as in 27, laminated tubes having the layer structure shown in Table 1 were obtained. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 30
In Example 27, a laminated tube having a layer structure shown in Table 1 was obtained in the same manner as in Example 27 except that the conductive fluorine-containing polymer (C-2) was changed to (C-4). It was. Table 1 shows the results of measuring the physical characteristics 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 31
In Example 27, the fluorinated polymer (C-1) was changed to (C-5), the conductive fluorinated polymer (C-2) was changed to the fluorinated polymer (C-6), and (C. A laminated tube having a layer structure shown in Table 1 was obtained in the same manner as in Example 27 except that the extrusion temperature in −5) was changed to 310 ° C. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 32
In Example 27, the fluorinated polymer (C-1) was changed to (C-5), the conductive fluorinated polymer (C-2) was changed to (C-7), and the extrusion of (C-5) was performed. A laminated tube having a layer structure shown in Table 1 was obtained in the same manner as in Example 27 except that the temperature was changed to 310 ° C. and the extrusion temperature of (C-7) was changed to 330 ° C. Table 1 shows the results of measuring the physical characteristics 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 33
In Example 27, except that the fluorinated polymer (C-1) was changed to (C-8) and the conductive fluorinated polymer (C-2) was changed to the fluorinated polymer (C-9). , A laminated tube having a layer structure shown in Table 1 was obtained in the same manner as in Example 27. Table 1 shows the results of measuring the physical characteristics of the laminated tube.

Example 34
Example 27, except that the fluorinated polymer (C-1) was changed to (C-8) and the conductive fluorinated polymer (C-2) was changed to (C-10) in Example 27. A laminated tube having a layer structure shown in Table 1 was obtained in the same manner as in Table 1. Table 1 shows the results of measuring the physical characteristics 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 2 was obtained in the same manner as in Example 1 except that the polyamide 12 / 9T composition (A-1) was not used. Table 2 shows the measurement results of the physical properties of the laminated tube.

Comparative Example 2
In Example 1, the layer configuration shown in Table 2 was carried out in the same manner as in Example 1 except that the polyamide 12 / 9T composition (A-1) was changed to the polyamide 612 / 6T composition (A-6). Obtained a laminated tube of. Table 2 shows the measurement results of the physical properties of the laminated tube.

Comparative Example 3
In Example 1, the layer configuration shown in Table 2 was carried out in the same manner as in Example 1 except that the polyamide 12 / 9T composition (A-1) was changed to the polyamide 612 / 6T composition (A-7). Obtained a laminated tube of. Table 2 shows the measurement results of the physical properties of the laminated tube.

Comparative Example 4
Lamination of the layer structure shown in Table 2 in the same manner as in Example 1 except that the polyamide 12 / 9T composition (A-1) was changed to the polyamide 11 composition (A-8) in Example 1. I got a tube. Table 2 shows the measurement results of the physical properties of the laminated tube.

Comparative Example 5
In Example 1, the layer configuration shown in Table 2 was carried out in the same manner as in Example 1 except that the polyamide 12 / 9T composition (A-1) was changed to the polyamide 12 / 9T composition (A-9). Obtained a laminated tube of. Table 2 shows the measurement results of the physical properties of the laminated tube.

Comparative Example 6
In Example 1, the layer configuration shown in Table 2 was carried out in the same manner as in Example 1 except that the polyamide 12 / 9T composition (A-1) was changed to the polyamide 12 / 9T composition (A-10). Obtained a laminated tube. Table 2 shows the measurement results of the physical properties of the laminated tube.

Comparative Example 7
In Example 1, a laminated tube having a layer structure shown in Table 2 was obtained by the same method as in Example 1 except that the semi-aromatic polyamide composition (B-1) was not used. Table 2 shows the measurement results of the physical properties of the laminated tube.

Comparative Example 8
In Example 1, the method was the same as in Example 2 except that the semi-aromatic polyamide composition (B-1) was changed to (B-8) and the extrusion temperature of (B-8) was changed to 350 ° C. Then, a laminated tube having a layer structure shown in Table 1 was obtained. Table 2 shows the measurement results of the physical properties of the laminated tube.

Comparative Example 9
In Example 4, the method was the same as in Example 4 except that the semi-aromatic polyamide composition (B-1) was changed to (B-15) and the extrusion temperature of (B-15) was changed to 280 ° C. Then, a laminated tube having a layer structure shown in Table 2 was obtained. Table 2 shows the measurement results of the physical properties of the laminated tube.

Comparative Example 10
In Example 22, a laminated tube having a layer structure shown in Table 2 was obtained in the same manner as in Example 22 except that the polyamide 12 / 9T composition (A-1) was not used. Table 2 shows the measurement results of the physical properties of the laminated tube.

Comparative Example 11
In Example 22, the layer configuration shown in Table 2 was carried out in the same manner as in Example 22 except that the polyamide 12 / 9T composition (A-1) was changed to the polyamide 612 / 6T composition (A-6). Obtained a laminated tube of. Table 2 shows the measurement results of the physical properties of the laminated tube.

Comparative Example 12
In Example 22, the layer configuration shown in Table 2 was carried out in the same manner as in Example 22 except that the polyamide 12 / 9T composition (A-1) was changed to the polyamide 612 / 6T composition (A-7). Obtained a laminated tube of. Table 2 shows the measurement results of the physical properties of the laminated tube.

Comparative Example 13
In Example 22, the layer structure shown in Table 2 was laminated in the same manner as in Example 22 except that the polyamide 12 / 9T composition (A-1) was changed to the polyamide 11 composition (A-8). I got a tube. Table 2 shows the measurement results of the physical properties of the laminated tube.

Comparative Example 14
In Example 22, the method was the same as in Example 22 except that the semi-aromatic polyamide composition (B-1) was changed to (B-8) and the extrusion temperature of (B-8) was changed to 350 ° C. Then, a laminated tube having a layer structure shown in Table 2 was obtained. Table 2 shows the measurement results of the physical properties of the laminated tube.

Comparative Example 15
In Example 23, the method was the same as in Example 23, except that the semi-aromatic polyamide composition (B-1) was changed to (B-15) and the extrusion temperature of (B-15) was changed to 280 ° C. Then, a laminated tube having a layer structure shown in Table 2 was obtained. Table 2 shows the measurement results of the physical properties of the laminated tube.

Comparative Example 16
In Example 27, a laminated tube having a layer structure shown in Table 2 was obtained in the same manner as in Example 27 except that the polyamide 12 / 9T composition (A-1) was not used. Table 2 shows the measurement results of the physical properties of the laminated tube.

Comparative Example 17
In Example 27, the layer configuration shown in Table 2 was carried out in the same manner as in Example 27, except that the polyamide 12 / 9T composition (A-1) was changed to the polyamide 612 / 6T composition (A-6). Obtained a laminated tube of. Table 2 shows the measurement results of the physical properties of the laminated tube.

Comparative Example 18
In Example 27, the layer configuration shown in Table 2 was carried out in the same manner as in Example 27, except that the polyamide 12 / 9T composition (A-1) was changed to the polyamide 612 / 6T composition (A-7). Obtained a laminated tube of. Table 2 shows the measurement results of the physical properties of the laminated tube.

Comparative Example 19
In Example 27, the layer structure shown in Table 2 was laminated in the same manner as in Example 27, except that the polyamide 12 / 9T composition (A-1) was changed to the polyamide 11 composition (A-8). I got a tube. Table 2 shows the measurement results of the physical properties of the laminated tube.

Comparative Example 20
In Example 27, the method was the same as in Example 27, except that the semi-aromatic polyamide composition (B-1) was changed to (B-8) and the extrusion temperature of (B-8) was changed to 350 ° C. Then, a laminated tube having a layer structure shown in Table 2 was obtained. Table 2 shows the measurement results of the physical properties of the laminated tube.

Comparative Example 21
In Example 28, the method was the same as in Example 28, except that the semi-aromatic polyamide composition (B-1) was changed to (B-15) and the extrusion temperature of (B-15) was changed to 280 ° C. Then, a laminated tube having a layer structure shown in Table 2 was obtained. Table 2 shows the measurement results of the physical properties of the laminated tube.

As is clear from the comparison with Tables 1 and 2, the laminated tubes of Comparative Examples 1, 10 and 16 having no layer containing the polyamide copolymer composition (A) specified in the present invention have a low temperature. It was inferior in impact resistance. The laminated tubes of Comparative Examples 2 and 3, 11, 12, 17 and 18 having a layer containing the polyamide copolymer composition (A) other than those specified in the present invention were inferior in chemical resistance. The laminated tubes of Comparative Examples 4, 13 and 19 having a layer containing the polyamide copolymer composition (A) other than those specified in the present invention were inferior in the durability of interlayer adhesion. The laminated tube of Comparative Example 5 having a layer containing the polyamide copolymer composition (A) in which the content of the elastomer polymer (A2) was less than the specified range of the present invention was inferior in low temperature impact resistance. The laminated tube of Comparative Example 6 having a layer containing the polyamide copolymer composition (A) in which the content of the elastomer polymer (A2) exceeded the specified range of the present invention was inferior in breaking pressure at high temperature. The laminated tube of Comparative Example 7 having no layer containing the semi-aromatic polyamide composition (B) specified in the present invention was inferior in alcohol-containing gasoline barrier property. The laminated tubes of Comparative Examples 8 and 9, 14, 15, 20 and 21 having a layer containing the semi-aromatic polyamide composition (B) other than those specified in the present invention were inferior in the durability of interlayer adhesion.
On the other hand, the laminated tubes of Examples 1 to 34 specified in the present invention have various features such as breaking pressure at high temperature, low temperature impact resistance, chemical resistance, alcohol-containing gasoline barrier property, interlayer adhesiveness and durability thereof. It is clear that the properties are good.

Claims (9)

A laminated tube having two or more layers including a layer (a) and a layer (b).
At least one set of the layer (a) and the layer (b) are arranged adjacent to each other.
The layer (a) contains the polyamide copolymer composition (A).
The layer (b) contains the semi-aromatic polyamide composition (B) and contains.
The polyamide copolymer composition (A) contains a polyamide copolymer (A1) and an elastomer polymer (A2).
The polyamide copolymer (A1) is a unit derived from (a1) an aliphatic diamine having 6 or more and 12 or less carbon atoms and an aliphatic dicarboxylic acid having 9 or more and 18 or less carbon atoms, or (a2) the number of carbon atoms. Units derived from 10 to 12 lactams and / or aliphatic aminocarboxylic acids, and (a3) units derived from aliphatic diamines and terephthalic acids having 9 or 10 carbon atoms and / or naphthalenedicarboxylic acids, or (A4) Containing units derived from xylylene diamine and / or bis (aminomethyl) naphthalene and an aliphatic dicarboxylic acid having 9 or 10 carbon atoms, (a1) or (a2) and (a3) or (a4). The molar ratio of is 55:45 mol% or more and 90:10 mol% or less, and 70% by mass or more and 95% by mass or less is contained in the polyamide copolymer composition (A).
The elastomer polymer (A2) contains a structural unit derived from an unsaturated compound having a carboxyl group and / or an acid anhydride group, and is contained in the polyamide copolymer composition (A) in an amount of 5% by mass or more of 30. Contains less than% by mass,
The semi-aromatic polyamide composition (B) contains a semi-aromatic polyamide (B1) or a semi-aromatic polyamide (B2).
The semi-aromatic polyamide (B1) contains 50 mol% or more of an aliphatic diamine unit having 9 or 10 carbon atoms with respect to the total diamine units of the semi-aromatic polyamide (B1), and the semi-aromatic polyamide (B1). B1) contains 50 mol% or more of terephthalic acid units and / or naphthalenedicarboxylic acid units with respect to all dicarboxylic acid units.
The semi-aromatic polyamide (B2) contains 50 mol% or more of xylylenediamine units and / or bis (aminomethyl) naphthalene units with respect to the total diamine units of the semi-aromatic polyamide (B2), and the semi-aromatic polyamide (B2). A laminated tube containing 50 mol% or more of an aliphatic dicarboxylic acid unit having 9 or 10 carbon atoms with respect to all the dicarboxylic acid units of the group polyamide (B2). In the polyamide copolymer (A1), the unit derived from (a1) an aliphatic diamine having 6 to 12 carbon atoms and an aliphatic dicarboxylic acid having 9 to 18 carbon atoms is hexamethylene sebacamide. Hexamethylene dodecamide, hexamethylene tetradecamide, nonamethylene azelamide, nonamethylene sebacamide, nonamethylene dodecamide, nonamethylene tetradecamide, 2-methyloctamethylene azelamide, 2-methyloctamethylene sebacamide, 2-Methyloctamethylene dodecamide, 2-methyloctamethylenetetradecamide, decamethylene azelamide, decamethylene sebacamide, decamethylene dodecamide, decamethylenetetradecamide, dodecamethylene azelamide, dodecamethylene sebacamide, And dodecamethylene Dodecamide is at least one raw material monomer selected from the group consisting of dodecamide, and (a2) a unit derived from lactam having 10 or more and 12 or less carbon atoms and / or an aliphatic aminocarboxylic acid is 11 It is at least one raw material monomer selected from the group consisting of −aminoundecanoic acid, 12-aminododecanoic acid, and dodecanthactam. The unit derived from naphthalenedicarboxylic acid is at least one raw material monomer selected from the group consisting of nonamethylene terephthalamide, 2-methyloctamethylene terephthalamide, and decamethylene terephthalamide (a4). The units derived from xylylene diamine and / or bis (aminomethyl) naphthalene and aliphatic dicarboxylic acids having 9 or 10 carbon atoms are metaxylylene azelamide, metaxylylene sebacamide, paraxylylene azelamide. The laminated tube according to claim 1, which is at least one raw material monomer selected from the group consisting of paraxylylene sebacamide. The laminated tube according to any one of claims 1 or 2, wherein the semi-aromatic polyamide composition (B) contains the elastomer polymer (A2). The laminated tube according to any one of claims 1 to 3, wherein the layer (b) is arranged adjacent to the inside of the layer (a). Further including layer (c)
At least one set of the layer (b) and the layer (c) are arranged adjacent to each other.
The laminate according to any one of claims 1 to 4, wherein the layer (c) contains a fluorine-containing polymer (C) in which a functional group reactive with an amino group is introduced into the molecular chain. tube. The laminated tube according to claim 5, wherein the layer (c) is arranged inside the layer (b). The laminated tube according to any one of claims 1 to 6, wherein the innermost layer is a conductive layer containing a thermoplastic resin composition containing a conductive filler. The laminated tube according to any one of claims 1 to 7, which is manufactured by coextrusion molding. The laminated tube according to any one of claims 1 to 8, which is used as a fuel tube.