Multilayer tube
View Patent ↗A multilayer tube including at least three layers including a layer (a) formed of (A) polyamide 11 and/or polyamide 12, a layer (b) formed of (B) a polyamide (semi-aromatic polyamide) including a dicarboxylic acid unit containing a terephthalic acid and/or naphthalenedicarboxylic acid unit in a proportion of 50 mol % or more based on all dicarboxylic acid units, and a diamine unit containing an aliphatic diamine unit having a carbon number of 9 to 13 in a proportion of 60 mol % or more based on all diamine units, and a layer (c) formed of (C) a fluorine-containing polymer having introduced into the molecular chain thereof a functional group having reactivity with a polyamide-based resin, is provided as a multilayer tube excellent in an alcohol gasoline permeation-preventing property, interlayer adhesion, low-temperature impact resistance, heat resistance and chemical resistance.
1. A multilayer tube comprising at least three layers including:
a layer (a) comprising (A) polyamide 11 and/or polyamide 12,
a layer (b) consisting of (B) a semi-aromatic polyamide or a combination of a
semi-aromatic polyamide and an additive selected from the group consisting of an antioxidant, a heat stabilizer, an ultraviolet absorbent, a light stabilizer, a lubricant, an inorganic filler, an antistatic agent, a flame retardant, a crystallization accelerator, a plasticizer, a colorant, a lubricating agent and an impact resistance improver, said semi-aromatic polyamide (B) consisting of a dicarboxylic acid unit containing a terephthalic acid and/or naphthalenedicarboxylic acid unit in a proportion of about 50 mol % or more based on all dicarboxylic acid units, and a diamine unit containing a 1,9-nonane-diamine and/or 2-methyl-1,8-octanediamine unit in a proportion of about 60 mol % or more based on all diamine units and
a layer (c) comprising (C) a fluorine-containing polymer having introduced into the molecular chain thereof at least one functional group selected from the group consisting of a carboxy group, an acid anhydride group, a carboxylate group, an alkoxycarbonyl group, a hydroxyl group, a sulfo group, a sulfonate group, an epoxy group, a cyano group, a carbonate group and a carboxylic acid halide group, as said functional group having reactivity with the polyamide-based resin, and
wherein said layer (b) comprising (B) the semi-aromatic polyamide is disposed between said layer (a) comprising (A) polyamide 11 and/or polyamide 12 and said layer (c) comprising (C) a fluorine-containing polymer.
2. The multilayer tube as claimed in claim 1 , wherein said layer (a) comprising (A) polyamide 11 and/or polyamide 12 is disposed as an outermost layer.
3. The multilayer tube as claimed in claim 1 , wherein said (C) fluorine-containing polymer having introduced into the molecular chain thereof a functional group having reactivity with a polyamide-based resin is based on at least one fluorine-containing polymer selected from the group consisting of an ethylene/tetrafluoroethylene copolymer, a polyvinyl idene fluoride, and a tetrafluoroethylene/hexafluoropropylene/vinylidene fluoride copolymer.
4. The multilayer tube as claimed in claim 1 , wherein an electrically conducting layer comprising a fluorine-containing polymer composition having incorporated thereinto an electrically conducting filler is disposed as an innermost layer in the multilayer tube.
5. The multilayer tube as claimed in claim 1 , which is a fuel tube.
6. The multilayer tube according to claim 1 , wherein said fluorine-containing polymer has an acid anhydride group as said functional group having reactivity with a polyamide-based resin.
7. The multilayer tube according to claim 1 , wherein said functional group of said layer (c) is itaconic acid anhydride.
8. A multilayer tube comprising at least four layers including:
a layer (a) comprising (A) polyamide 11 and/or polyamide 12,
a layer (b) comprising (B) a semi-aromatic polyamide consisting of a dicarboxylic acid unit containing a terephthalic acid and/or naphthalene-dicarboxylic acid unit in a proportion of about 50 mol % or more based on all dicarboxylic acid units, and a diamine unit containing a 1,9-nonanediamine and/or 2-methyl-1,8-octanediamine unit in a proportion of about 60 mol % or more based on all diamine units,
a layer (c) comprising (C) a fluorine-containing polymer having introduced into the molecular chain thereof a functional group having reactivity with a polyamide-based resin, and
a layer (d) consisting of (D) a terminal modified polyamide and optionally an additive selected from the group consisting of an antioxidant, a heat stabilizer, an ultraviolet absorbent, a light stabilizer, a lubricant, an inorganic filler, an antistatic agent, a flame retardant, a crystallization accelerator and an impact resistance improver, said terminal modified polyamide satisfying [A]>[B]+5, wherein [A] is the terminal amino group concentration (μeq/g-polymer) of the polyamide and [B] is the terminal carboxyl group concentration (μeq/g-polymer) of the polyamide,
wherein said layer (b) comprising (B) the semi-aromatic polyamide is disposed between said layer (a) comprising (A) polyamide 11 and/or polyamide 12 and said layer (c) comprising (C) the fluorine-containing polymer, and said layer (d) comprising (D) the terminal modified polyamide is disposed between said layer (b) comprising (B) the semi-aromatic polyamide and said layer (c) comprising (C) the fluorine-containing polymer, and
wherein each of said layers (a), (b), (c) and (d) is a coextrusion molded article.
9. The multilayer tube as claimed in claim 8 , wherein said layer (a) comprising (A) polyamide 11 and/or polyamide 12 is disposed as an outermost layer.
10. The multilayer tube as claimed in claim 8 , wherein said (C) fluorine-containing polymer having introduced into the molecular chain thereof a functional group having reactivity with a polyamide-based resin is based on at least one fluorine-containing polymer selected from the group consisting of an ethylene/tetrafluoroethylene copolymer, a polyvinylidene fluoride, and a tetrafluoroethylene/hexafluoropropylene/vinylidene fluoride copolymer.
11. The multilayer tube as claimed in claim 8 , wherein said (D) terminal modified polyamide is a polyamide produced by adding a diamine at the polymerization.
12. The multilayer tube as claimed in claim 8 , wherein an electrically conducting layer comprising a fluorine-containing polymer composition having incorporated thereinto an electrically conducting filler is disposed as an innermost layer in the multilayer tube.
13. The multilayer tube as claimed in claim 8 , which is a fuel tube.
14. The multilayer tube according to claim 8 , wherein said fluorine-containing polymer has at least one functional group selected from the group consisting of a carboxyl group, an acid anhydride group, a carboxylate group, an alkoxycarbonyl group, a hydroxyl group, a sulfo group, a sulfonate group, an epoxy group, a cyano group, a carbonate group and a carboxylic acid halide group, as said functional group having reactivity with the polyamide-based resin.
15. The multilayer tube according to claim 8 , wherein said fluorine-containing polymer has an acid anhydride group as said functional group having reactivity with a polyamide-based resin.
16. The multilayer tube according to claim 8 , wherein said functional group of layer (c) is itaconic acid anhydride.