JP6583648B2 - Laminated structure - Google Patents

Description

  The present invention is a laminated structure comprising a layer made of an aliphatic polyamide, a layer made of a semi-aromatic polyamide having a specific structure, low-temperature impact resistance, chemical solution permeation prevention, interlayer adhesion, chemical resistance, And a laminated structure excellent in heat resistance.

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

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

  As a method for solving this problem, a resin having good chemical solution permeation prevention properties, for example, saponified ethylene / vinyl acetate copolymer (EVOH), polymetaxylylene adipamide (polyamide MXD6), polybutylene terephthalate (PBT), 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), tetrafur Ethylene / hexafluoropropylene / vinylidene fluoride / perfluoro (alkyl vinyl ether) copolymer (TFE / HFP / VDF / PAVE), tetrafluoroethylene / perfluoro (alkyl vinyl ether) copolymer (TFE / PAVE, PFA), Tetrafluoroethylene / hexafluoropropylene / perfluoro (alkyl vinyl ether) copolymer (TFE / HFP / PAVE), chlorotrifluoroethylene / perfluoro (alkyl vinyl ether) / tetrafluoroethylene copolymer (CTFE / PAVE / TFE, Many laminated structures in which CPT) are arranged, in particular, laminated tubes have been proposed (see, for example, Patent Document 1).

Among these, a fuel transfer tube in which polymetaxylylene adipamide (polyamide MXD6) is arranged in an intermediate layer has been proposed (see Patent Document 2). Polyamide MXD6 is known to have good adhesive strength with polyamide 6, but the interlayer adhesion is insufficient for polyamide 11 or polyamide 12 conventionally used as the constituent material of single-layer tube It is. For this reason, it is necessary to provide an adhesive layer between the layers, resulting in complexity in terms of cost and management. Moreover, the tube which has arrange | positioned polyamide MXD6 has the fault that it is inferior to low temperature impact resistance. As a laminated tube that achieves both chemical permeation prevention and low-temperature impact resistance, a laminated composition in which a polyamide MXD6 and a resin composition containing a polyamide resin that is compatible with the polyamide MXD6 and softer than the polyamide MXD6 is disposed in the intermediate layer A tube has been proposed (see Patent Document 3). However, further improvement is desired in terms of low-temperature impact properties, and the interlayer adhesion is still insufficient for polyamide 11 or polyamide 12, and it is necessary to provide an adhesive layer between the layers as in the above-described technique.
Furthermore, the inventors of the present invention have a layer composed of an aliphatic polyamide, all diamine units, diamine units containing 60 mol% or more of xylylenediamine and / or naphthalenedimethylamine units, and all dicarboxylic acid units. Proposed laminated structure comprising at least two layers including a layer made of a semi-aromatic polyamide composed of dicarboxylic acid units containing 60 mol% or more of aliphatic dicarboxylic acid units having 8 to 13 carbon atoms (See Patent Document 4). In the same literature, m-xylylenediamine units are mentioned as suitable xylylenediamine units, and in the examples, a laminated structure including a layer made of a semi-aromatic polyamide composed of p-xylylenediamine units. There is no disclosure of specific technical data regarding chemical resistance and heat resistance.

US Pat. No. 5,554,425 JP-A-4-272592 JP 2008-18702 A JP 2006-044201 A

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

  As a result of intensive studies to solve the above problems, the present inventors have found that a laminated structure including a layer made of an aliphatic polyamide and a layer made of a semi-aromatic polyamide having a specific structure has low-temperature impact resistance. The present inventors have found that it is excellent in chemical solution permeation prevention, interlayer adhesion, chemical resistance, and heat resistance.

  That is, the present invention comprises (a) layer composed of aliphatic polyamide (A), diamine units containing 60 mol% or more of p-xylylenediamine units, and all dicarboxylic acid units, based on all diamine units. A laminate structure comprising at least two layers including a layer (b) made of a semi-aromatic polyamide composed of a dicarboxylic acid unit containing at least 60 mol% of an aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms. Provide the body.

Preferred embodiments of the laminated structure of the present invention are shown below. A plurality of preferred embodiments can be combined.
[1] The aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms in the semi-aromatic polyamide (B) is selected from the group consisting of units derived from azelaic acid, sebacic acid, and dodecanedioic acid, or at least A laminated structure characterized by being one type.
[2] Aliphatic polyamide (A) is polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene deca From the group consisting of amide (polyamide 610), polyhexamethylene dodecane (polyamide 612), polydecane methylene decanamide (polyamide 1010), polydecamethylene dodecane (polyamide 1012), and polydodecamethylene dodecane (polyamide 1212). 1. A laminated structure characterized in that it is at least one homopolymer selected, or a copolymer using several kinds of raw material monomers forming these.
[3] The (a) layer made of the aliphatic polyamide (A) is arranged in the outermost layer, and the (b) layer made of the semi-aromatic polyamide (B) is arranged inside the (a) layer. A laminated structure characterized.
[4] A laminated structure in which the (b) layer made of the semi-aromatic polyamide (B) is disposed in the innermost layer.
[5] The layered structure further includes a layer (c) composed of a fluorine-containing polymer (C) in which a functional group having reactivity with an amino group is introduced into the molecular chain, the (c) A layered structure characterized in that the layer is disposed in the innermost layer.
[6] A laminated structure, wherein the laminated structure is produced by coextrusion molding.
[7] A laminated structure characterized by being used as a laminated molded product selected from the group consisting of a film, a tube, a hose, a bottle, and a tank.
[8] A laminated molded product used as a chemical solution transport tube.

  The laminated structure of the present invention includes a layer made of an aliphatic polyamide and a layer made of a semi-aromatic polyamide having a specific structure, and achieves both low temperature impact resistance and chemical liquid permeation prevention properties, interlayer adhesion and chemical resistance. Excellent properties such as heat resistance. Therefore, the film, tube, hose, bottle, and tank are useful for automobile parts, industrial materials, industrial materials, electrical and electronic parts, machine parts, office equipment parts, household goods, and container applications. It is particularly suitable as a chemical solution transport tube, and it is possible to suppress alcohol mixed hydrocarbons that permeate and evaporate from the tube partition.

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

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

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

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

  Examples of the aliphatic polyamide (A) include polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyethylene adipamide (polyamide 26), polytetramethylene succinamide (polyamide) 44), polytetramethylene glutamide (polyamide 45), polytetramethylene adipamide (polyamide 46), polytetramethylene suberamide (polyamide 48), polytetramethylene azelamide (polyamide 49), polytetramethylene sebacamide (Polyamide 410), polytetramethylene dodecamide (polyamide 412), polypentamethylene succinamide (polyamide 54), polypentamethylene glutamide (polyamide 55), polypentamethylene adipamide (polyamide) 6), polypentamethylene suberamide (polyamide 58), polypentamethylene azelamide (polyamide 59), polypentamethylene sebamide (polyamide 510), polypentamethylene dodecamide (polyamide 512), polyhexamethylene succinamide (Polyamide 64), polyhexamethylene glutamide (polyamide 65), polyhexamethylene adipamide (polyamide 66), polyhexamethylene suberamide (polyamide 68), polyhexamethylene azelamide (polyamide 69), polyhexamethylene Bacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polyhexamethylene tetradecanamide (polyamide 614), polyhexamethylene hexadecanamide (polyamide 616), polyhexame Lenoctadecamide (Polyamide 618), Polynonamethylene adipamide (Polyamide 96), Polynonamethylene suberamide (Polyamide 98), Polynonamethylene azelamide (Polyamide 99), Polynonamethylene sebacamide (Polyamide 910) , Polynonamethylene dodecamide (polyamide 912), polydecamethylene adipamide (polyamide 106), polydecamethylene suberamide (polyamide 108), polydecamethylene azelamide (polyamide 109), polydecamethylene sebacamide (polyamide) 1010), polydecamethylene dodecamide (polyamide 1012), polydodecamethylene adipamide (polyamide 126), polydodecamethylene suberamide (polyamide 128), polydodecamethylene azelamide (polyamide 129) And homopolymers such as polydodecamethylene sebacamide (polyamide 1210) and polydodecamethylene dodecamide (polyamide 1212), and copolymers using several raw material monomers forming these.

  Among these, polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene azelamide (polyamide 69), poly Hexamethylene sebacamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polynonamethylene dodecamide (polyamide 912), polydecamethylene sebacamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012) Polydodecamethylene dodecamide (polyamide 1212) and a copolymer using several kinds of raw material monomers forming these are preferable, such as polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydode Amide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene decanamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecamethylene decanamide (polyamide 1010), polydecamethylene There are at least one homopolymer selected from the group consisting of dodecamide (polyamide 1012) and polydodecamethylene dodecamide (polyamide 1212), or a copolymer using several raw material monomers forming these. preferable.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  In the terminal-modified aliphatic polyamide, it is preferable to add a diamine and / or polyamine during polymerization in order to satisfy the condition of the terminal group concentration among the above-exemplified amines, from the viewpoint of suppressing the gel generation. More preferably, it is at least one selected from the group consisting of aliphatic diamines, alicyclic diamines, and polyamines.

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

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

  Other polyamide resins include polymetaxylylene adipamide (polyamide MXD6), polymetaxylylene veramide (polyamide MXD8), polymetaxylylene azelamide (polyamide MXD9), polymetaxylylene sebacamide (polyamide MXD10). , Polymetaxylylene decamide (polyamide MXD12), polymetaxylylene terephthalamide (polyamide MXDT), polymetaxylylene isophthalamide (polyamide MXDI), polymetaxylylene hexahydroterephthalamide (polyamide MXDT (H)), polymer Taxylylene naphthalamide (polyamide MXDN), polyparaxylylene adipamide (polyamide PXD6), polyparaxylylene terephthalamide (polyamide PXDT), polyparaxylylene isofol Ramide (polyamide PXDI), polyparaxylylene hexahydroterephthalamide (polyamide PXDT (H)), polyparaxylylene naphthalamide (polyamide PXDN), polyparaphenylene terephthalamide (PPTA), polyparaphenylene isophthalamide (PPIA), polymetaphenylene terephthalamide (PMTA), polymetaphenylene isophthalamide (PMIA), poly (2,6-naphthalenediethylene adipamide) (polyamide 2,6-BAN6), poly (2, 6-naphthalene dimethylene terephthalamide) (polyamide 2,6-BANT), poly (2,6-naphthalene dimethylene isophthalamide) (polyamide 2,6-BANI), poly (2,6-naphthalene dimethylene hexa) Hydroterephthalamide) (Polyamide 2,6 BANT (H)), poly (2,6-naphthalene dimethylene naphthalamide) (polyamide 2,6-BANN), poly (1,3-cyclohexanedimethylene adipamide) (polyamide 1,3-BAC6), poly (1,3-cyclohexanedimethylenesuberamide (polyamide 1,3-BAC8), poly (1,3-cyclohexanedimethylene azelamide) (polyamide 1,3-BAC9), poly (1,3-cyclohexanedimethylene Bacamide) (polyamide 1,3-BAC10), poly (1,3-cyclohexanedimethylene dodecamide) (polyamide 1,3-BAC12), poly (1,3-cyclohexanedimethylene terephthalamide) (polyamide 1, 3-BACT), poly (1,3-cyclohexanedimethylene isophthalamide) (polyamide 1, 3-BACI), poly (1,3-cyclohexanedimethylene hexahydroterephthalamide) (polyamide 1,3-BACT (H)), poly (1,3-cyclohexanedimethylene naphthalamide) (polyamide 1,3- BACN), poly (1,4-cyclohexanedimethylene adipamide) (polyamide 1,4-BAC6), poly (1,4-cyclohexanedimethylene suberamide) (polyamide 1,4-BAC8), poly (1, 4-cyclohexanedimethylene azelamide) (polyamide 1,4-BAC9), poly (1,4-cyclohexanedimethylene sebacamide) (polyamide 1,4-BAC10), poly (1,4-cyclohexanedimethylene dodecamide) ) (Polyamide 1,4-BAC12), poly (1,4-cyclohexanedimethylene terephthala) Do) (polyamide 1,4-BACT), poly (1,4-cyclohexanedimethylene isophthalamide) (polyamide 1,4-BACI), poly (1,4-cyclohexanedimethylene hexahydroterephthalamide) (polyamide) 1,4-BACT (H)), poly (1,4-cyclohexanedimethylenenaphthalamide) (polyamide 1,4-BACN), poly (4,4′-methylenebiscyclohexylene adipamide) (polyamide PACM6) Poly (4,4′-methylenebiscyclohexylene suberamide) (polyamide PACM8), poly (4,4′-methylenebiscyclohexylene azelamide) (polyamide PACM9), poly (4,4′-methylenebiscyclohexylene) Sebacamide) (polyamide PACM10), poly (4,4'-methylene Sucyclohexylene dodecamide) (polyamide PACM12), poly (4,4′-methylenebiscyclohexylene tetradecanamide) (polyamide PACM14), poly (4,4′-methylenebiscyclohexylene hexadecanamide) (polyamide PACM16) , Poly (4,4′-methylenebiscyclohexylene octadecanamide) (polyamide PACM18), poly (4,4′-methylenebiscyclohexylene terephthalamide) (polyamide PACMT), poly (4,4′-methylenebis) (Cyclohexylene isophthalamide) (polyamide PACMI), poly (4,4′-methylenebiscyclohexylene hexahydroterephthalamide) (polyamide PACMT (H)), poly (4,4′-methylenebiscyclohexylene naphthalamide) (Polyami PACMN), poly (4,4′-methylenebis (2-methyl-cyclohexylene) adipamide) (polyamide MACM6), poly (4,4′-methylenebis (2-methyl-cyclohexylene) suberamide) (polyamide MACM8), Poly (4,4′-methylenebis (2-methyl-cyclohexylene) azeramide) (polyamide MACM9), poly (4,4′-methylenebis (2-methyl-cyclohexylene) sebacamide) (polyamide MACM10), poly (4 4′-methylenebis (2-methyl-cyclohexylene) dodecamide) (polyamide MACM12), poly (4,4′-methylenebis (2-methyl-cyclohexylene) tetradecanamide) (polyamide MACM14), poly (4,4′-methylenebis) (2-methyl-cyclohex Len) hexadecamide) (polyamide MACM16), poly (4,4′-methylenebis (2-methyl-cyclohexylene) octadecamide) (polyamide MACM18), poly (4,4′-methylenebis (2-methyl-cyclohexylene) terephthalamide) (Polyamide MACMT), poly (4,4′-methylenebis (2-methyl-cyclohexylene) isophthalamide) (polyamide MACMI), poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexahydroterephthalamide) (Polyamide MACMT (H)), poly (4,4′-methylenebis (2-methyl-cyclohexylene) naphthalamide) (polyamide MACMN), poly (4,4′-propylenebiscyclohexylene adipamide) (polyamide PACP6) The (4,4′-propylene biscyclohexylene suberamide) (polyamide PACP8), poly (4,4′-propylene biscyclohexylene azelamide) (polyamide PACP9), poly (4,4′-propylene biscyclohexylene sebaca) Amide) (polyamide PACP10), poly (4,4′-propylene biscyclohexylene dodecamide) (polyamide PACP12), poly (4,4′-propylene biscyclohexylene tetradecanamide) (polyamide PACP14), poly (4 4′-propylene biscyclohexylene hexadecamide) (polyamide PACP16), poly (4,4′-propylene biscyclohexylene octadecanamide) (polyamide PACP18), poly (4,4′-propylene biscyclohexylene terephthalamide) ) (Polyamide PACPT), poly (4,4′-propylene biscyclohexylene isophthalamide) (polyamide PACPI), poly (4,4′-propylene biscyclohexylene hexahydroterephthalamide) (polyamide PACPT (H)) , Poly (4,4′-propylenebiscyclohexylenenaphthalamide) (polyamide PACPN), polyisophorone adipamide (polyamide IPD6), polyisophorones veramide (polyamide IPD8), polyisophorone azelamide (polyamide IPD9), polyisophorone Sebacamide (Polyamide IPD10), Polyisohoronde Decamide (Polyamide IPD12), Polyisophorone Terephthalamide (Polyamide IPDT), Polyisophorone Isophthalamide (Polyamide IPDI), Polyisophor Hexahydroterephthalamide (polyamide IPDT (H)), polyisophorone naphthalamide (polyamide IPDN), polytetramethylene terephthalamide (polyamide 4T), polytetramethylene isophthalamide (polyamide 4I), polytetramethylene hexahydro Terephthalamide (polyamide 4T (H)), polytetramethylene naphthalamide (polyamide 4N), polypentamethylene terephthalamide (polyamide 5T), polypentamethylene isophthalamide (polyamide 5I), polypentamethylene hexahydroterephthalate Lamidamide (polyamide 5T (H)), polypentamethylene naphthalamide (polyamide 5N), polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), poly Xamethylenehexahydroterephthalamide (polyamide 6T (H)), polyhexamethylene naphthalamide (polyamide 6N), poly (2-methylpentamethylene terephthalamide) (polyamide M5T), poly (2-methylpentamethylene isophthalate) Lamid) (Polyamide M5I), Poly (2-methylpentamethylene hexahydroterephthalamide) (Polyamide M5T (H)), Poly (2-methylpentamethylene naphthalamide) (Polyamide M5N), Polynonamethylene terephthalamide ( Polyamide 9T), Polynonamethylene isophthalamide (Polyamide 9I), Polynonamethylene hexahydroterephthalamide (Polyamide 9T (H)), Polynonamethylene naphthalamide (Polyamide 9N), Poly (2-methyloctamethylene terephthalate) Ramid) ( Polyamide M8T), poly (2-methyloctamethyleneisophthalamide) (polyamide M8I), poly (2-methyloctamethylenehexahydroterephthalamide) (polyamide M8T (H)), poly (2-methyloctamethylenenaphthalamide) ) (Polyamide M8N), polytrimethylhexamethylene terephthalamide (polyamide TMHT), polytrimethylhexamethylene isophthalamide (polyamide TMHI), polytrimethylhexamethylene hexahydroterephthalamide (polyamide TMHT (H)), polytrimethylhexa Methylene naphthalamide (polyamide TMHN), polydecamethylene terephthalamide (polyamide 10T), polydecamethylene isophthalamide (polyamide 10I), polydecamethylene hexahydroterephthalamide Polyamide 10T (H)), polydecamethylene naphthalamide (polyamide 10N), polyundecamethylene terephthalamide (polyamide 11T), polyundecamethylene isophthalamide (polyamide 11I), polyundecamethylene hexahydroterephthalamide (Polyamide 11T (H)), polyundecamethylene naphthalamide (polyamide 11N), polydodecamethylene terephthalamide (polyamide 12T), polydodecamethylene isophthalamide (polyamide 12I), polydodecamethylene hexahydroterephthalamide ( Polyamide 12T (H)), polydodecamethylene naphthalamide (polyamide 12N), and copolymers using several kinds of raw material monomers of these polyamides. These can use 1 type (s) or 2 or more types.

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

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

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

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

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

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

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

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

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

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

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

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

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

  Further, (ethylene and / or propylene) / α-olefin copolymer, (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) used as an impact resistance improving material ) Type copolymer, ionomer polymer, and aromatic vinyl compound / conjugated diene compound type block copolymer are preferably polymers modified with carboxylic acid and / or derivatives thereof. By modifying with such a component, a functional group having an affinity for the aliphatic polyamide (A) is contained in the molecule.

  Examples of the functional group having affinity for the aliphatic polyamide (A) include a carboxyl group, an acid anhydride group, a carboxylic acid ester group, a carboxylic acid metal salt, a carboxylic acid imide group, a carboxylic acid amide group, and an epoxy group. Can be mentioned. Examples of compounds containing these functional groups include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid Endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid and metal salts of these carboxylic acids, monomethyl maleate, monomethyl itaconate, methyl acrylate, ethyl acrylate, butyl acrylate 2-ethylhexyl acrylate, hydroxyethyl acrylate, methyl methacrylate, 2-ethylhexyl methacrylate, hydroxyethyl methacrylate, aminoethyl methacrylate, dimethyl maleate, dimethyl itaconate, maleic anhydride, itaconic anhydride, citracone anhydride Acid, endobicyclo- 2.2.1] -5-heptene-2,3-dicarboxylic anhydride, maleimide, N-ethylmaleimide, N-butylmaleimide, N-phenylmaleimide, acrylamide, methacrylamide, glycidyl acrylate, glycidyl methacrylate, Examples include glycidyl ethacrylate, glycidyl itaconate, and glycidyl citraconic acid. These can use 1 type (s) or 2 or more types.

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

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

  The semi-aromatic polyamide (B) used in the present invention has diamine units containing 60 mol% or more of p-xylylenediamine units with respect to all diamine units, and 8 carbon atoms with respect to all dicarboxylic acid units. It consists of dicarboxylic acid units containing 60 mol% or more of aliphatic dicarboxylic acid units of 13 or less (hereinafter sometimes referred to as semi-aromatic polyamide (B)).

  The content of the p-xylylenediamine unit in the semi-aromatic polyamide (B) sufficiently secures various physical properties such as heat resistance, chemical resistance, impact resistance, and chemical liquid permeation prevention properties of the resulting laminated structure. From a viewpoint, it is 60 mol% or more with respect to all the diamine units, it is preferable that it is 75 mol% or more, and it is more preferable that it is 90 mol% or more.

  The diamine unit in the semi-aromatic polyamide (B) may contain other diamine units other than the p-xylylenediamine unit as long as the excellent properties of the laminated structure of the present invention are not impaired. Good. Other diamine units include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, , 8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1, 15-pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, 1,19-nonadecanediamine, 1,20-eicosanediamine, 2-methyl-1,5 -Pentanediamine, 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octane Derived from aliphatic diamines such as amines, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine Unit, 1,3-cyclohexanediamine, 1,4-cyclohexanediamine, 1,3-bis (aminomethyl) cyclohexane, 1,4-bis (aminomethyl) cyclohexane, bis (4-aminocyclohexyl) methane, 2,2 -Bis (4-aminocyclohexyl) propane, bis (3-methyl-4-aminocyclohexyl) methane, 2,2-bis (3-methyl-4-aminocyclohexyl) propane, 5-amino-2,2,4- Trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine Bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, 2,5-bis (aminomethyl) norbornane, 2,6-bis (aminomethyl) norbornane, 3,8-bis (aminomethyl) tricyclodecane, 4 , Units derived from alicyclic diamines such as 9-bis (aminomethyl) tricyclodecane, m-phenylenediamine, p-phenylenediamine, m-xylylenediamine, 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-amino) Phenyl) propane, 4,4′-diaminodiphenyl sulfone, 4,4′-diaminodiphenyl ether, etc. The unit derived from the aromatic diamine of these is mentioned, These can use 1 type (s) or 2 or more types. The content of these other diamine units is 40 mol% or less, preferably 25 mol% or less, more preferably 10 mol% or less, based on all diamine units.

  In addition, the content of the aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms in the semi-aromatic polyamide (B) is determined by various physical properties such as heat resistance, chemical resistance, and chemical liquid permeation resistance of the resulting laminated structure. From the viewpoint of sufficiently ensuring the above, it is at least 60 mol%, preferably at least 75 mol%, more preferably at least 90 mol%, based on all dicarboxylic acid units.

Examples of the aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms include units derived from suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid and the like. As long as the number of carbon atoms satisfies the above, branched aliphatic dicarboxylic such as 2,2-diethylsuccinic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, 2-butylsuberic acid You may contain the unit induced | guided | derived from an acid. These can use 1 type (s) or 2 or more types.
Among the aliphatic dicarboxylic acid units having 8 or more and 13 or less carbon atoms, units derived from azelaic acid and sebacic acid are preferable from the viewpoint of the balance between coextrusion moldability and chemical liquid permeation prevention property, and low temperature impact resistance is achieved. From the viewpoint of ensuring sufficient, units derived from dodecanedioic acid are preferred.

  The dicarboxylic acid unit in the semi-aromatic polyamide (B) is other than the aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms as long as it does not impair the excellent characteristics of the laminated structure of the present invention. The dicarboxylic acid unit may be included. Other dicarboxylic acid units include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, tetradecanedioic acid, pentadecanedioic acid, hexadecane Units derived from aliphatic dicarboxylic acids such as diacid, octadecanedioic acid and eicosane diacid, alicyclic rings such as 1,3-cyclopentanedicarboxylic acid, 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid Units derived from the formula dicarboxylic acid, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid, 1,3 -Phenylenedioxydiacetic acid, 1,4-phenylenedioxydiacetic acid, 4,4'-o Sidibenzoic 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′-biphenyldicarboxylic acid, units derived from aromatic dicarboxylic acid such as 4,4′-triphenyldicarboxylic acid, and the like, and one or more of these are used. be able to. Among the above units, units derived from aromatic dicarboxylic acids are preferred. The content of these other dicarboxylic acid units is 40 mol% or less, preferably 25 mol% or less, more preferably 10 mol% or less, based on all dicarboxylic acid units. Furthermore, polycarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used within a range where melt molding is possible.

  The semi-aromatic polyamide (B) may contain other units other than the dicarboxylic acid unit and the diamine unit as long as the excellent properties of the laminated structure of the present invention are not impaired. Other units include units derived from lactams such as caprolactam, enantolactam, undecane lactam, dodecane lactam, α-pyrrolidone, α-piperidone, 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, 11 -Units derived from aminocarboxylic acids of aliphatic aminocarboxylic acids such as aminoundecanoic acid and 12-aminododecanoic acid, and aromatic aminocarboxylic acids such as p-aminomethylbenzoic acid. These can use 1 type (s) or 2 or more types. The content of other units is preferably 30 mol% or less, more preferably 10 mol% or less, based on the total dicarboxylic acid units.

  In addition, there is no special restriction | limiting in the kind of terminal group of semi-aromatic polyamide (B), its density | concentration, and molecular weight distribution. One or more of monoamine, diamine, polyamine, monocarboxylic acid, and dicarboxylic acid can be added in appropriate combination for molecular weight adjustment and melt stabilization during molding. For example, alicyclic such as aliphatic monoamines such as methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, stearylamine, dimethylamine, diethylamine, dipropylamine, dibutylamine, cyclohexylamine, dicyclohexylamine Aromatic monoamines such as monoamine, aniline, toluidine, diphenylamine, naphthylamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1 Aliphatic diamines such as aliphatic diamines such as 1,12-dodecanediamine, cyclohexanediamine, bis (aminomethyl) cyclohexane, 5-amino-1,3,3-trimethylcyclohexanemethylamine , M-phenylenediamine, p-phenylenediamine, aromatic diamine such as m-xylylenediamine, polyalkyleneimine, polyalkylenepolyamine, polyvinylamine, polyallylamine and other polyamines, acetic acid, propionic acid, butyric acid, valeric acid, capron Acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid and other aliphatic monocarboxylic acids, cyclohexanecarboxylic acid and other alicyclic monocarboxylic acids, benzoic acid, toluic acid , Α-naphthalenecarboxylic acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, aromatic monocarboxylic acid such as phenylacetic acid, aliphatic dicarboxylic acid such as adipic acid and pimelic acid, 1,3-cyclopentanedicarboxylic acid, 1 , 3-Cyclohexanedicarboxylic acid 1,4-cyclohexanedicarboxylic acid and other alicyclic dicarboxylic acids, terephthalic acid, isophthalic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 2,7-naphthalenedicarboxylic acid and other aromatic dicarboxylic acids Examples include acids. These can use 1 type (s) or 2 or more types. The amount of these molecular weight regulators to be used varies depending on the reactivity of the molecular weight regulator and the polymerization conditions, but is appropriately determined so that the relative viscosity of the finally obtained polyamide falls within the following range.

  Considering the melt stability, it is preferable that the end of the molecular chain of the semi-aromatic polyamide (B) is sealed with an end-capping agent, and more preferably 10% or more of the end groups are sealed. More preferably, 20% or more of the end groups are sealed. The end capping agent is not particularly limited as long as it is a monofunctional compound having reactivity with the amino group or carboxyl group at the end of the polyamide, but from the viewpoint of reactivity, stability of the capped end, etc. An acid or a monoamine is preferable, and a monocarboxylic acid is more preferable from the viewpoint of easy handling. In addition, acid anhydrides such as phthalic anhydride, monoisocyanates, monoacid halides, monoesters, monoalcohols, and the like can be used.

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

A phosphorus compound can be added to the semi-aromatic polyamide (B) in order to increase the processing stability during melt molding or to prevent coloring. Phosphorus compounds include alkaline earth metal salts of hypophosphorous acid, alkali metal salts of phosphorous acid, alkaline earth metal salts of phosphorous acid, alkali metal salts of phosphoric acid, alkaline earth metal salts of phosphoric acid, Examples include alkali metal salts of pyrophosphoric acid, alkaline earth metal salts of pyrophosphoric acid, alkali metal salts of metaphosphoric acid, and alkaline earth metal salts of metaphosphoric acid.
Specifically, calcium hypophosphite, magnesium hypophosphite, sodium phosphite, sodium hydrogen phosphite, potassium phosphite, potassium hydrogen phosphite, lithium phosphite, lithium hydrogen phosphite, phosphorus phosphite Magnesium phosphate, magnesium hydrogen phosphite, calcium phosphite, calcium hydrogen phosphite, 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 phosphate, lithium pyrophosphate, sodium metaphosphate, potassium metaphosphate, magnesium metaphosphate, calcium metaphosphate, and lithium metaphosphate and the like. These can use 1 type (s) or 2 or more types. Among these, calcium hypophosphite, magnesium hypophosphite, calcium phosphite, calcium hydrogen phosphite, and calcium dihydrogen phosphate are preferable, and calcium hypophosphite is more preferable. These phosphorus compounds may be hydrates.

The content of the phosphorus compound is 0.03 parts by mass or more in terms of phosphorus atom concentration with respect to 100 parts by mass of the semi-aromatic polyamide (B) from the viewpoint of sufficiently ensuring the anti-coloring effect and suppressing the generation of gel. It is preferably 0.30 parts by mass or less, more preferably 0.05 parts by mass or more and 0.20 parts by mass or less, and further preferably 0.07 parts by mass or more and 0.15 parts by mass or less.
The addition method of these phosphorus compounds is a method of adding to a nylon salt aqueous solution, a diamine or dicarboxylic acid which is a raw material of the semi-aromatic polyamide (B), a method of adding to a dicarboxylic acid in a molten state, and adding during melt polymerization. Any method may be used as long as it can be uniformly dispersed in the semi-aromatic polyamide (B), but the method is not limited to these.

  An alkali metal compound can be added to the semiaromatic polyamide (B) in combination with the phosphorus compound. In order to prevent coloring of the polyamide during polycondensation, a sufficient amount of phosphorus compound needs to be present, but in some cases there is a risk of causing gelation of the polyamide. It is preferable to coexist an alkali metal compound. Examples of the alkali metal compound include alkali metal hydroxides, alkaline earth metal hydroxides, alkali metal acetates, and alkaline earth metal acetates, and alkali metal hydroxides and alkali metal acetates are preferable.

  Specific examples of the alkali metal compound include lithium hydroxide, sodium hydroxide, potassium hydroxide, rubidium hydroxide, cesium hydroxide, magnesium hydroxide, calcium hydroxide, strontium hydroxide, barium hydroxide, lithium acetate, Examples thereof include sodium acetate, potassium acetate, rubidium acetate, cesium acetate, magnesium acetate, calcium acetate, strontium acetate, and barium acetate. These can use 1 type (s) or 2 or more types. Among these, sodium hydroxide, potassium hydroxide, magnesium hydroxide, calcium hydroxide, sodium acetate, and potassium acetate are preferable from the economical viewpoint, and sodium hydroxide, sodium acetate, and potassium acetate are preferable.

When an alkali metal compound is added to the polycondensation system of the semi-aromatic polyamide (B), the value obtained by dividing the number of moles of the compound by the number of moles of the phosphorus compound converted to phosphorus atoms is the acceleration and suppression of the amidation reaction. From the viewpoint of balance, it is preferably 0.3 or more and 1.0 or less, more preferably 0.40 or more and 0.95 or less, and further preferably 0.5 or more and 0.9 or less.
The methods for adding these alkali metal compounds are the method of adding to the aqueous solution of nylon salt, diamine or dicarboxylic acid, which is the raw material of the semi-aromatic polyamide (B), the method of adding to the dicarboxylic acid in the molten state, and the addition during melt polymerization Any method may be used as long as it can be uniformly dispersed in the semi-aromatic polyamide (B), but is not limited thereto.

  Semi-aromatic polyamide (B) production equipment includes batch-type reaction kettles, single- or multi-tank continuous reaction equipment, tubular continuous reaction equipment, uniaxial kneading extruder, biaxial kneading extruder, etc. A known polyamide production apparatus such as a reaction extruder may be used. As a method for producing the semi-aromatic polyamide (B), there are known methods such as melt polymerization, solution polymerization, and solid-phase polymerization, and these methods are used to repeat normal pressure, reduced pressure, and pressurizing operations to make the semi-aromatic polyamide. Polyamide (B) 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 p-xylylenediamine and an aliphatic dicarboxylic acid having 8 to 13 carbon atoms is pressurized and heated in the presence of water, and in a molten state while removing added water and condensed water. Manufactured by a polymerization method. It can also be produced by a method in which p-xylylenediamine is directly added to an aliphatic dicarboxylic acid having 8 to 13 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, p-xylylenediamine is continuously added to the aliphatic dicarboxylic acid having 8 to 13 carbon atoms, during which the oligoamide that generates the temperature of the reaction system and Polymerization proceeds while raising the temperature of the reaction system so that the melting point of the polyamide is higher than the melting point. Further, the semi-aromatic polyamide (B) may be subjected to solid phase polymerization after being produced by a melt polymerization method.

  Based on JIS K-6920, the relative viscosity of the semi-aromatic polyamide (B) measured under the conditions of 96% sulfuric acid, 1% polymer concentration and 25 ° C. ensures the mechanical properties of the resulting laminated structure. From the viewpoint of securing the desirable moldability of the laminated structure by setting the viscosity at the time of melting to an appropriate range, it is preferably 1.5 or more and 4.0 or less, and is 1.8 or more and 3.5 or less. More preferably, it is 2.0 or more and 3.0 or less.

  The semi-aromatic polyamide (B) may contain other polyamide-based resins or other thermoplastic resins. Examples of other polyamide resins or other thermoplastic resins include the same resins as those of the aliphatic polyamide (A). Further, it may be a mixture with the aliphatic polyamide (A). The content of the semi-aromatic polyamide (B) in the mixture is preferably 60% by mass or more.

  Furthermore, for the semi-aromatic polyamide (B), an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, an inorganic filler, an antistatic agent, a flame retardant, and crystallization promotion, if necessary. Agents, plasticizers, colorants, lubricants, impact resistance improvers and the like may be added. In order to improve the low temperature impact resistance of the semi-aromatic polyamide (B), it is preferable to add an impact resistance improver, and in particular, bending measured according to ISO 178 described in the aliphatic polyamide (A). It is more preferable to add a rubbery polymer having an elastic modulus of 500 MPa or less.

The laminated structure according to the present invention comprises an aliphatic polyamide (A) layer (a), a diamine unit containing 60 mol% or more of p-xylylenediamine units with respect to all diamine units, and all dicarboxylic acid units. On the other hand, it is composed of at least two or more layers including the (b) layer composed of a semi-aromatic polyamide (B) comprising a dicarboxylic acid unit containing 60 mol% or more of an aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms. The By including the (b) layer which consists of a semi-aromatic polyamide (B), the chemical | medical solution permeation-proof property of a laminated structure can be improved.
In a preferred embodiment, the (a) layer made of the aliphatic polyamide (A) is disposed in the outermost layer of the laminated structure. By disposing the (a) layer made of the aliphatic polyamide (A) as the outermost layer, a laminated structure having excellent chemical resistance and flexibility can be obtained.

  In a more preferred embodiment, the (b) layer made of the semi-aromatic polyamide (B) is arranged inside the (a) layer made of the aliphatic polyamide (A) of the laminated structure. In a more preferred embodiment, the (b) layer made of the semi-aromatic polyamide (B) is disposed in the innermost layer of the laminated structure. By arranging the (b) layer made of the semi-aromatic polyamide (B) in the innermost layer, a laminated structure having excellent chemical resistance can be obtained.

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

Further, the total number of layers in the laminated structure of the present invention is at least two layers including (a) layer made of aliphatic polyamide (A) and (b) layer made of semi-aromatic polyamide (B). There are no particular restrictions. In addition to the two layers (a) and (b), the laminated structure of the present invention can be used from other thermoplastic resins in order to provide additional functions or to obtain an economically advantageous laminated structure. The number of layers of the laminated structure of the present invention may be 2 or more, but may be 8 or less as judged from the mechanism of the structure manufacturing apparatus. Preferably, it is 2 layers or more and 7 layers or less.

  The laminated structure in the present invention is a laminated structure in which the (b) layer made of the semi-aromatic polyamide (B) is disposed inside the (a) layer made of the aliphatic polyamide (A), A layer structure comprising a (c) layer comprising a fluorine-containing polymer (C) in which a functional group having reactivity with an amino group is introduced into a molecular chain, and the (c) layer is disposed in the innermost layer This laminated structure is also a preferred embodiment.

  The fluorine-containing polymer (C) used in the present invention is a fluorine-containing polymer in which a functional group reactive to an amino group is introduced into a molecular chain (hereinafter referred to as a fluorine-containing polymer). (C) may be referred to.)

The fluorine-containing polymer (C) is a polymer (homopolymer or copolymer) having a repeating unit derived from at least one fluorine-containing monomer. It is not particularly limited as long as it is a fluorine-containing polymer that can be heat-melted.
Here, as the fluorine-containing monomer, tetrafluoroethylene (TFE), trifluoroethylene, vinylidene fluoride (VDF), vinyl fluoride (VF), chlorotrifluoroethylene (CTFE), trichlorofluoroethylene, hexafluoropropylene (HFP), CF ₂ = CFOR ^f1 (where R ^f1 represents a perfluoroalkyl group which may contain an etheric oxygen atom having 1 to 10 carbon atoms), CF ₂ = CF—OCH ₂ —R. ^f2 (wherein R ^f2 represents a perfluoroalkylene group which may contain an etheric oxygen atom having 1 to 10 carbon atoms), CF ₂ = CF (CF ₂ ) _p OCF = CF ₂ (where , p is 1 or ^{_{2.), CH 2 = CX}} 1 (CF 2) n X 2 ( wherein, ^{X 1} and ^{X 2} are each other Independently represent a hydrogen atom or a fluorine atom, n is an integer from 2 to 10.), And the like. These can use 1 type (s) or 2 or more types.

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

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

  When the fluorine-containing polymer (C) is coextruded with the aliphatic polyamide (A), semi-aromatic polyamide (B), etc., sufficient melting can be achieved within the kneading temperature and molding temperature range without significant deterioration. In order to ensure fluidity, the melt flow rate at a temperature 50 ° C. higher than the melting point of the fluorine-containing polymer (C) and a load of 5 kg may be 0.5 g / 10 min or more and 200 g / 10 min or less. Preferably, it is 1 g / 10 min or more and 100 g / 10 min or less.

Further, in the fluorinated polymer (C), the melting point and glass transition point of the polymer can be adjusted by selecting the type and composition ratio of the fluorinated monomer and other monomers. The melting point of the fluorine-containing polymer (C) is appropriately selected according to the purpose, application, and method of use. When coextruding with the aliphatic polyamide (A), the semi-aromatic polyamide (B), etc., It is preferable to be close to the molding temperature. 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, the non-fluorine-containing monomer, and the functional group-containing monomer described later. The melting point of the fluorine-containing polymer (C) is the heat melting stability, continuous moldability, co-extrusion with the aliphatic polyamide (A) and the semi-aromatic polyamide (B), and the fluorine-containing polymer (C). From the viewpoint of sufficiently ensuring the heat resistance, chemical resistance, and chemical liquid permeation prevention property, it is preferably 150 ° C. or higher and 320 ° C. or lower, more preferably 170 ° C. or higher and 310 ° C. or lower, and 180 ° C. or higher and 300 ° C. or lower. More preferably, it is not higher than ° C.
Here, the melting point means that the sample is heated to a temperature higher than the expected melting point using a differential scanning calorimeter, and then the sample is cooled at a rate of 10 ° C. per minute and cooled to 30 ° C. The melting point is defined as the temperature of the peak value of the melting curve measured by leaving the sample as it is for about 1 minute and then increasing the temperature at a rate of 10 ° C. per minute.

  The fluorine-containing polymer (C) used in the present invention has a functional group having reactivity with an amino group in the molecular structure, and the functional group is the same as that of the fluorine-containing polymer (C). It may be contained at either the molecular end, the side chain or the main chain. Moreover, 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, application, required interlayer adhesion, adhesion method, functional group introduction method, etc. of the counterpart material laminated on the fluorine-containing polymer (C). The

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

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

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

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

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

  Examples of the functional group-containing fluorine-containing monomer include perfluoroacrylic acid fluoride, 1-fluoroacrylic acid fluoride, acrylic acid fluoride, 1-trifluoromethacrylic acid fluoride, and perfluoro when the functional group has a carbonyl group. Examples include butenoic acid. These can use 1 type (s) or 2 or more types.

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

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

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

  In order to introduce a carbonate group at the molecular terminal of the polymer, various methods using a polymerization initiator or a chain transfer agent can be employed. Can be preferably employed from the viewpoint of performance such as economy, heat resistance and chemical resistance. According to this method, a carbonyl group derived from peroxide, for example, a carbonate group derived from peroxycarbonate, an ester group derived from peroxyester, or a haloformyl group formed by converting these functional groups is overlapped. It can be introduced at the end of the coalescence. Of these polymerization initiators, it is more preferable to use peroxycarbonate because the polymerization temperature can be lowered and no side reaction is involved in the initiation reaction.

  Various methods can be used to introduce a haloformyl group at the molecular end of the polymer. For example, the carbonate group of the above-mentioned fluorine-containing polymer having a carbonate group at the end is heated to cause thermal decomposition (decarboxylation). Can be obtained.

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

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

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

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

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

  Examples of the thermoplastic resin other than the fluorine-containing polymer (C) include polymetaxylylene adipamide (polyamide MXD6) other than the aliphatic polyamide (A) and semi-aromatic polyamide (B) defined in the present invention. ), Polymetaxylylene beramide (polyamide MXD8), polymetaxylylene azelamide (polyamide MXD9), polymetaxylylene sebacamide (polyamide MXD10), polymetaxylylene decamide (polyamide MXD12), polymetaxylylene terephthalamide (Polyamide MXDT), polymetaxylylene isophthalamide (polyamide MXDI), polymetaxylylene hexahydroterephthalamide (polyamide MXDT (H)), polymetaxylylene naphthalamide (polyamide MXDN), polyparaxylylene adipamide Polyamide PXD6), polyparaxylylene terephthalamide (polyamide PXDT), polyparaxylylene isophthalamide (polyamide PXDI), polyparaxylylene hexahydroterephthalamide (polyamide PXDT (H)), polyparaxylylene naphtha Ramide (polyamide PXDN), polyparaphenylene terephthalamide (PPTA), polyparaphenylene isophthalamide (PPIA), polymetaphenylene terephthalamide (PMTA), polymetaphenylene isophthalamide (PMIA), poly (2, 6-naphthalene dimethylene adipamide) (polyamide 2,6-BAN6), poly (2,6-naphthalene dimethylene terephthalamide) (polyamide 2,6-BANT), poly (2,6-naphthalene dimethylene iso) Phthalamide) (Polya 2,6-BANI), poly (2,6-naphthalenediethylenehexahydroterephthalamide) (polyamide 2,6-BANT (H)), poly (2,6-naphthalenedimethylenenaphthalamide) (polyamide 2) , 6-BANN), poly (1,3-cyclohexanedimethylene adipamide) (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-cyclohexanedimethylene isophthalamide) (polyamide 1,3-BACI), poly (1,3-cyclohexanedimethylene hexahydroterephthalamide) (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-cyclohexanedimethylenesberamide) (polyamide 1,4-BAC8), poly (1,4-cyclohexanedimethylene azelamide) (polyamide 1,4-BAC9), poly (1,4- Cyclohexane dimethylene sebacamide) (polyamide 1,4-BAC10), poly (1,4-cyclohexane) Methylene dodecamide) (polyamide 1,4-BAC12), poly (1,4-cyclohexanedimethylene terephthalamide) (polyamide 1,4-BACT), poly (1,4-cyclohexanedimethylene isophthalamide) (polyamide) 1,4-BACI), poly (1,4-cyclohexanedimethylene hexahydroterephthalamide) (polyamide 1,4-BACT (H)), poly (1,4-cyclohexanedimethylene naphthalamide) (polyamide 1, 4-BACN), poly (4,4'-methylenebiscyclohexylene adipamide) (polyamide PACM6), poly (4,4'-methylenebiscyclohexylene suberamide) (polyamide PACM8), poly (4,4 ' -Methylenebiscyclohexylene azelamide) (polyamide PACM9), poly 4,4′-methylenebiscyclohexylene sebacamide) (polyamide PACM10), poly (4,4′-methylenebiscyclohexylene dodecamide) (polyamide PACM12), poly (4,4′-methylenebiscyclohexylene tetradeca) Amide) (polyamide PACM14), poly (4,4′-methylenebiscyclohexylenehexadecamide) (polyamide PACM16), poly (4,4′-methylenebiscyclohexyloctadecanamide) (polyamide PACM18), poly (4 , 4'-methylenebiscyclohexylene terephthalamide) (polyamide PACMT), poly (4,4'-methylenebiscyclohexylene isophthalamide) (polyamide PACMI), poly (4,4'-methylenebiscyclohexylene hexahydro Terephthalami (Polyamide PACMT (H)), poly (4,4′-methylenebiscyclohexylenenaphthalamide) (polyamide PACMN), poly (4,4′-methylenebis (2-methyl-cyclohexylene) adipamide) (polyamide MACM6) ), Poly (4,4′-methylenebis (2-methyl-cyclohexylene) suberamide) (polyamide MACM8), poly (4,4′-methylenebis (2-methyl-cyclohexylene) azeramide) (polyamide MACM9), poly ( 4,4′-methylenebis (2-methyl-cyclohexylene) sebacamide) (polyamide MACM10), poly (4,4′-methylenebis (2-methyl-cyclohexylene) dodecamide) (polyamide MACM12), poly (4,4 ′ -Methylenebis (2-methyl-cyclohex Len) tetradecanamide) (polyamide MACM14), poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexadecanamide) (polyamide MACM16), poly (4,4′-methylenebis (2-methyl-cyclohexylene) octadecamide) (Polyamide MACM18), poly (4,4′-methylenebis (2-methyl-cyclohexylene) terephthalamide) (polyamide MACMT), poly (4,4′-methylenebis (2-methyl-cyclohexylene) isophthalamide) (polyamide MACMI) , Poly (4,4′-methylenebis (2-methyl-cyclohexylene) hexahydroterephthalamide) (polyamide MACMT (H)), poly (4,4′-methylenebis (2-methyl-cyclohexylene) naphthalamide) ( Polya MACMN), poly (4,4′-propylene biscyclohexylene adipamide) (polyamide PACP6), poly (4,4′-propylene biscyclohexylene suberamide) (polyamide PACP8), poly (4,4′- Propylene biscyclohexylene azelamide) (polyamide PACP9), poly (4,4′-propylene biscyclohexylene sebacamide) (polyamide PACP10), poly (4,4′-propylene biscyclohexylene dodecamide) (polyamide PACP12) , Poly (4,4′-propylene biscyclohexylene tetradecanamide) (polyamide PACP14), poly (4,4′-propylene biscyclohexylene hexadecanamide) (polyamide PACP16), poly (4,4′-propylene bis Cyclohexylene Octadecamide) (polyamide PACP18), poly (4,4′-propylene biscyclohexylene terephthalamide) (polyamide PAPPT), poly (4,4′-propylene biscyclohexylene isophthalamide) (polyamide PACPI), poly (4 , 4′-propylene biscyclohexylene hexahydroterephthalamide) (polyamide PACPT (H)), poly (4,4′-propylene biscyclohexylene naphthalamide) (polyamide PACPN), polyisophorone adipamide (polyamide IPD6) , Polyisophoron beramide (polyamide IPD8), polyisophorone azeramide (polyamide IPD9), polyisophorone sebamide (polyamide IPD10), polyisophorondecamide (polyamide IPD12), polyisophor 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)), polytetramethylene naphthalamide (polyamide 4N), polypentamethylene terephthalamide (polyamide 5T), poly Pentamethylene isophthalamide (polyamide 5I), polypentamethylene hexahydroterephthalamide (polyamide 5T (H)), polypentamethylene naphthalamide (polyamide 5N), poly Xamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polyhexamethylene hexahydroterephthalamide (polyamide 6T (H)), polyhexamethylene naphthalamide (polyamide 6N), poly (2 -Methylpentamethylene terephthalamide) (polyamide M5T), poly (2-methylpentamethylene isophthalamide) (polyamide M5I), poly (2-methylpentamethylene hexahydroterephthalamide) (polyamide M5T (H)), Poly (2-methylpentamethylenenaphthalamide) (Polyamide M5N), Polynonamethylene terephthalamide (Polyamide 9T), Polynonamethylene isophthalamide (Polyamide 9I), Polynonamethylene hexahydroterephthalamide (Polyamide 9T ( H)), polynonamethylene naphthalamide (polyamide 9N), poly (2-methyloctamethylene terephthalamide) (polyamide M8T), poly (2-methyloctamethylene isophthalamide) (polyamide M8I), poly (2- Methyloctamethylenehexahydroterephthalamide) (polyamide M8T (H)), poly (2-methyloctamethylenenaphthalamide) (polyamide M8N), polytrimethylhexamethyleneterephthalamide (polyamide TMHT), polytrimethylhexamethyleneisophthalate Ramide (polyamide TMHI), polytrimethylhexamethylene hexahydroterephthalamide (polyamide TMHT (H)), polytrimethylhexamethylene naphthalamide (polyamide TMHN), polydecamethylene terephthalamide (polyamide) 0T), polydecamethylene isophthalamide (polyamide 10I), polydecamethylene hexahydroterephthalamide (polyamide 10T (H)), polydecamethylene naphthalamide (polyamide 10N), polyundecamethylene terephthalamide (polyamide 11T) ), Polyundecamethylene isophthalamide (polyamide 11I), polyundecamethylene hexahydroterephthalamide (polyamide 11T (H)), polyundecamethylene naphthalamide (polyamide 11N), polydodecamethylene terephthalamide (polyamide) 12T), polydodecamethylene isophthalamide (polyamide 12I), polydodecamethylene hexahydroterephthalamide (polyamide 12T (H)), polydodecamethylene naphthalamide (polyamide 12N) and these polyamides They include de of the starting monomer and / or polyamide resin such as a copolymer using several kinds of raw material monomers of the aliphatic polyamide (A).

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

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

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

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

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

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

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

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

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

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

  The laminated structure of the present invention is a film-like, sheet-like, tube-like, or the like, using a thermoplastic resin molding machine that is usually used, such as an extrusion molding machine, blow molding machine, compression molding machine, injection molding machine, etc. It can be manufactured in a hose shape and other various shapes, and adopts any melt molding method including co-extrusion molding method (T-die extrusion, inflation extrusion, blow molding, profile extrusion, extrusion coating, etc.), laminated injection molding method, etc. Is done.

  Laminated molded products comprising the laminated structure of the present invention are automotive parts, internal combustion engine applications, mechanical parts such as electric tool housings, industrial materials, industrial materials, electrical and electronic parts, office equipment parts, household goods, medical care, foods Used in various applications such as building material parts and furniture parts. More specifically, tubes for automobile fuel pipes, automobile radiator tubes, brake tubes, air conditioner tubes and other chemical solution transport tubes, electric wire coating materials, optical fiber coating materials, etc. tubes, hoses, agricultural films, linings, architectural interiors Examples include materials (wallpaper, etc.), films such as laminated steel sheets, sheets, automobile radiator tanks, chemical bottles, chemical tanks, bags, chemical containers, tanks such as gasoline tanks, and the like. Among these, it is useful as a chemical solution transport tube.

  Examples of the chemical solution include aromatic hydrocarbon solvents such as benzene, toluene, xylene, methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, diethylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol, and the like. Alcohol, phenol solvents, dimethyl ether, dipropyl ether, methyl-t-butyl ether, dioxane, tetrahydrofuran and other ether solvents, chloroform, methylene chloride, trichloroethylene, ethylene dichloride, perchlorethylene, monochloroethane, dichloroethane, tetrachloroethane Halogen solvents such as perchloroethane, chlorobenzene, acetone, methyl ethyl ketone, diethyl ketone, acetone Ketone solvents such as phenone, gasoline, kerosene, diesel gasoline, alcohol-containing gasoline, methyl-t-butyl ether, oxygen-containing gasoline, amine-containing gasoline, sour gasoline, castor oil base brake fluid, glycol ether brake fluid, borate ester Examples include brake fluid, brake fluid for extremely cold regions, silicone fluid brake fluid, mineral oil brake fluid, power steering oil, hydrogen sulfide oil, window washer fluid, engine coolant, urea solution, pharmaceutical agent, ink, paint, etc. .

Hereinafter, the chemical solution transport tube which is a preferred embodiment will be described in detail.
Specific examples of chemical transport tubes include feed tubes, return tubes, evaporation tubes, fuel filler tubes, ORVR tubes, reserve tubes, vent tubes and other fuel tubes, oil tubes, oil drilling tubes, underground buried tubes for gas stations, brakes Tube, Window Osher Liquid Tube, Engine Cooling Liquid (LLC) Tube, Reservoir Tank Tube, Urea Solution Transfer Tube, Cooling Tube for Cooling Water, Refrigerant, etc., Air Conditioner Refrigerant Tube, Heater Tube, Load Heating Tube, Floor Heating Tube , Infrastructure supply tubes, fire extinguishers and fire extinguishing equipment tubes, medical cooling equipment tubes, inks, paint spray tubes, and other chemical solution tubes. In particular, it is suitable as a fuel tube.

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

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

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

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

  The outer diameter of the chemical solution transport tube takes into consideration the flow rate of the chemical solution (for example, fuel such as alcohol-containing gasoline). In addition, the thickness is designed so as to maintain flexibility with a satisfactory degree of ease of assembly work of the tube and vibration resistance during use, but is not limited thereto. The outer diameter is preferably 4 mm to 500 mm, the inner diameter is preferably 3 mm to 400 mm, and the wall thickness is preferably 0.5 mm to 50 mm.

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

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

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

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

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

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

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

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

[Chemical resistance, heat resistance]
One end of the tube cut to 200 mm was sealed, engine coolant (LLC, ethylene glycol / water = 50/50 mass ratio) was put inside, and the remaining end was also sealed. The test tube was then placed in an oven at 120 ° C. and treated for 2,000 hours. About the tube after a process, the impact test was implemented at -40 degreeC by the method as described in SAE J-2260 7.5. When the number of fractures was 0 with respect to 10 tests, it was judged that the chemical resistance and heat resistance were excellent.

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

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

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

Production of Conductive Polyamide 12 Resin Composition (A-3) In production of polyamide 12 resin composition (A-1), polyamide 12 (a-1) was changed to (a-3) (UBE Kosan Co., Ltd., UBESTA3020U). , Production of polyamide 12 resin composition (A-1) except that carbon black (Cabot Co., Vulcan XC-72) was used as the conductive filler and no plasticizer was used. In the same manner as above, pellets of conductive polyamide 12 resin composition comprising 60% by mass of polyamide 12, 20% by mass of impact resistance improving material, and 20% by mass of conductive filler were obtained (hereinafter referred to as this conductive polyamide 12 resin). The composition is referred to as (A-3)).

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

Production of Polyamide 610 Resin Composition (A-4) Polyamide 610 (a-4) was coated with maleic anhydride-modified ethylene / propylene copolymer (manufactured by JSR Corporation, JSR) as an impact resistance improver.
T7761P), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (BASF Japan, IRGANOX245) as an antioxidant, and Tris as a phosphorus processing stabilizer While (2,4-di-t-butylphenyl) phosphite (manufactured by BASF Japan, IRGAFOS 168) is mixed in advance and supplied to a biaxial melt kneader (manufactured by Nippon Steel, Ltd., model: TEX44), From the middle of the cylinder of the biaxial melt kneader, benzenesulfonic acid butyramide as a plasticizer is injected by a metering pump, melt kneaded at a cylinder temperature of 200 ° C. to 270 ° C., and the molten resin is extruded into a strand shape. Introduced into water tank, cooled, cut, vacuum dried, polyamide 610 80% by mass, impact resistance Pellets of polyamide 610 resin composition comprising 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus-based processing stabilizer with respect to a total of 100 parts by mass of impact-improving material 10% by mass and plasticizer 10% by mass. (Hereinafter, this polyamide 610 resin composition is referred to as (A-4)).

Manufacture of polyamide 612 (a-5) In manufacture of polyamide 610 (a-4), 17.6 kg of 50 mass% aqueous solution of an equimolar salt of 1,6-hexanediamine and sebacic acid was added to 1,6-hexanediamine and dodecane. The same as the production of polyamide 610 (a-4) except that 20.0 kg of 50% by weight aqueous solution of equimolar salt of diacid and the addition amount of 1,6-hexanediamine were changed from 63.8 g to 70.0 g. By the method, a polyamide 612 having a relative viscosity of 2.52, a terminal amino group concentration of 65 μeq / g, and a terminal carboxyl group concentration of 19 μeq / g was obtained (hereinafter, this polyamide 612 is referred to as (a-5)).

Manufacture of polyamide 612 resin composition (A-5) Polyamide 610 resin except that polyamide 610 (a-4) was changed to polyamide 612 (a-5) in the manufacture of polyamide 610 resin composition (A-4). In the same manner as in the production of the composition (A-4), an antioxidant of 0.8% was added to 100 parts by mass of 80% by mass of polyamide 612, 10% by mass of an impact resistance improving material, and 10% by mass of a plasticizer. Pellets of a polyamide 612 resin composition comprising mass parts and 0.2 parts by mass of a phosphorus processing stabilizer were obtained (hereinafter, this polyamide 612 resin composition is referred to as (A-5)).

Production of polyamide 6 resin composition (A-6) Polyamide 6 (UBE Nylon 1024B, relative viscosity 3.50, manufactured by Ube Industries, Ltd.) and maleic anhydride-modified ethylene / propylene copolymer (JSR) as impact resistance improver JSR manufactured by JSR
T7761P), triethylene glycol-bis [3- (3-tert-butyl-5-methyl-4-hydroxyphenyl) propionate] (BASF Japan, IRGANOX245) as an antioxidant, and Tris as a phosphorus processing stabilizer While (2,4-di-t-butylphenyl) phosphite (manufactured by BASF Japan, IRGAFOS 168) is mixed in advance and supplied to a biaxial melt kneader (manufactured by Nippon Steel, Ltd., model: TEX44), From the middle of the cylinder of the biaxial melt kneader, benzenesulfonic acid butyramide as a plasticizer is injected by a metering pump, melt kneaded at a cylinder temperature of 230 ° C. to 270 ° C., and the molten resin is extruded into a strand shape. Introduced into water tank, cooled, cut, vacuum dried, polyamide 6 85 mass%, improved impact resistance Pellets of polyamide 6 resin composition comprising 0.8 parts by mass of antioxidant and 0.2 parts by mass of phosphorus processing stabilizer were obtained for a total of 100 parts by mass of 10% by mass of good material and 5% by mass of plasticizer. (Hereinafter, this polyamide 6 resin composition is referred to as (A-6).)

Polyamide 6/12 resin composition (A-7)
Polyamide 6/12 (poly (caproamide / dodecanamide) copolymer) resin composition (A-7): UBE Industries, UBE Nylon 7034U

Semi-aromatic polyamide (B)
Manufacture of semi-aromatic polyamide (b-1) Equipped with a stirrer, thermometer, torque meter, pressure gauge, raw material inlet directly connected with diaphragm pump, nitrogen gas inlet, pressure outlet, pressure regulator, and polymer outlet A pressure vessel with an internal volume of 40 liters was charged with 6.068 kg (30.0 mol) of sebacic acid, 8.50 g (0.049 mol) of calcium hypophosphite, and 2.19 g (0.025 mol) of sodium acetate. After the pressure inside the pressure vessel was pressurized to 0.3 MPa with 99.9999% nitrogen gas, the operation of releasing the nitrogen gas to normal pressure was repeated 5 times to perform nitrogen substitution, and then the pressure was reduced. The system was heated while stirring. Furthermore, after heating up to 190 degreeC under a small nitrogen stream, 4.086 kg (30.0 mol) of p-xylylenediamine was dripped over 160 minutes under stirring. During this time, the internal pressure of the reaction system was controlled to 0.5 MPa, and the internal temperature was continuously raised to 295 ° C. Further, water distilled with dropping of p-xylylenediamine was removed out of the system through a condenser and a cooler. After completion of the dropwise addition of p-xylylenediamine, the pressure was reduced to normal pressure over 60 minutes, and during this time, the temperature in the container was maintained at 300 ° C. and the reaction was continued for 10 minutes. Thereafter, the internal pressure of the reaction system was reduced to 79 kPa, and the melt polymerization reaction was continued for 40 minutes. Thereafter, stirring was stopped and the inside of the system was pressurized to 0.2 MPa with nitrogen, and the polycondensate was extracted from the lower outlet of the pressure vessel into a string shape. The string-like polycondensate is immediately cooled, and the water-cooled string-like resin is pelletized by a pelletizer, and then dried under reduced pressure to have a melting point of 281, 291 ° C. (having two melting points) and a relative viscosity of 2.47. An aromatic polyamide (polyamide PXD10 = 100 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (b-1)).

Manufacture of a semi-aromatic polyamide resin composition (B-1) A maleic anhydride-modified ethylene / propylene copolymer (manufactured by JSR Corporation, JSR T7761P) was used as an impact resistance improver for the semi-aromatic polyamide (b-1). , Triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan, IRGANOX 245) as an antioxidant, and tris (2 , 4-di-t-butylphenyl) phosphite (IRGAFOS168, manufactured by BASF Japan Ltd.) is mixed in advance and supplied to a twin-screw melt kneader (manufactured by Nippon Steel, Co., Ltd., model: TEX44). After melt-kneading at a temperature of 310 ° C. to 310 ° C. and extruding the molten resin into a strand shape, this is introduced into a water tank, cooled, And 100% by mass of 100% by mass of semi-aromatic polyamide and 10% by mass of impact resistance improving agent, 0.8 parts by mass of antioxidant and 0.2% by mass of phosphorus processing stabilizer. The pellet of the semi-aromatic polyamide resin composition which consists of a part was obtained (henceforth this semi-aromatic polyamide resin composition is called (B-1)).

Production of semi-aromatic polyamide (b-2) In the production of semi-aromatic polyamide (b-1), 4.086 kg (30.0 mol) of p-xylylenediamine was converted to 3.269 kg (24. 0 mol) and 0.817 kg (6.0 mol) of m-xylylenediamine, and the method similar to the production of the semi-aromatic polyamide (b-1) except that the melt polymerization time was changed from 40 minutes to 20 minutes. Thus, a semi-aromatic polyamide (polyamide PXD10 / MXD10 = 80/20 mol%) having a melting point of 263 ° C. and a relative viscosity of 2.13 was obtained (hereinafter, this semi-aromatic polyamide is referred to as (b-2)).

Production of Conductive Semi-Aromatic Polyamide Resin Composition (B-2) Maleic anhydride-modified ethylene / 1-butene copolymer (Mitsui Chemicals, Inc.) as an impact resistance improver to semi-aromatic polyamide (b-2) Manufactured by Tuffmer MH5010) and ethylene / 1-butene copolymer (manufactured by Mitsui Chemicals, Inc., Tafmer A-0550), carbon black as a conductive filler (manufactured by Lion Corporation, Ketjen Black EC600JD), antioxidant As triethylene glycol-bis [3- (3-t-butyl-5-methyl-4-hydroxyphenyl) propionate] (manufactured by BASF Japan, IRGANOX 245), and tris (2,4-di -T-butylphenyl) phosphite (BASF Japan, IRGAFOS168) is mixed in advance, Supply to a twin-screw melt kneader (Nippon Steel Works, model: TEX44), melt knead at a cylinder temperature of 240 ° C to 310 ° C, extrude the molten resin into a strand, and then introduce it into a water tank , Cooled, cut, and vacuum dried, with respect to a total of 100 parts by mass of 68% by mass of semi-aromatic polyamide, 25% by mass of impact resistance improver, and 7% by mass of conductive filler, 0.8 parts by mass of antioxidant, A pellet of a conductive semi-aromatic polyamide resin composition comprising 0.2 parts by mass of a phosphorus processing stabilizer was obtained (hereinafter, this conductive semi-aromatic polyamide resin composition is referred to as (B-2)).

Production of semi-aromatic polyamide (b-3) In the production of semi-aromatic polyamide (b-1), 6.068 kg (30.0 mol) of sebacic acid was changed to 5.647 kg (30.0 mol) of azelaic acid. Except that a semi-aromatic polyamide (polyamide PXD9 = 100 mol%) having a melting point of 270 ° C. and a relative viscosity of 2.45 was obtained in the same manner as in the production of the semi-aromatic polyamide (b-1) (hereinafter referred to as “this”). Semi-aromatic polyamide is referred to as (b-3).)

Production of semi-aromatic polyamide resin composition (B-3) In production of semi-aromatic polyamide resin composition (B-1), semi-aromatic polyamide (b-1) was changed to (b-3), and the cylinder temperature was changed. In the same manner as in the production of the semi-aromatic polyamide resin composition (B-1) except that the temperature was changed from 310 ° C. to 300 ° C., the total of 90% by mass of the semi-aromatic polyamide and 10% by mass of the impact resistance improving material A pellet of a semi-aromatic polyamide resin composition comprising 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus processing stabilizer was obtained with respect to 100 parts by mass (hereinafter, this semi-aromatic polyamide resin composition). A thing is called (B-3).).

Production of semi-aromatic polyamide (b-4) In the production of semi-aromatic polyamide (b-1), 4.086 kg (30.0 mol) of p-xylylenediamine was converted to 4.086 kg (30. Except that the polymerization temperature was changed from 300 ° C. to 250 ° C., in the same manner as in the production of the semi-aromatic polyamide (b-1), a semi-fragrance having a melting point of 191 ° C. and a relative viscosity of 2.46 Group polyamide (polyamide MXD10 = 100 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (b-4)).

Production of semi-aromatic polyamide resin composition (B-4) In production of semi-aromatic polyamide resin composition (B-1), semi-aromatic polyamide (b-1) was changed to (b-4), and the cylinder temperature was changed. In the same manner as the production of the semi-aromatic polyamide resin composition (B-1) except that the temperature was changed from 310 ° C. to 240 ° C., the total of 90% by mass of the semi-aromatic polyamide and 10% by mass of the impact resistance improving material A pellet of a semi-aromatic polyamide resin composition comprising 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus processing stabilizer was obtained with respect to 100 parts by mass (hereinafter, this semi-aromatic polyamide resin composition). A thing is called (B-4).).

Production of semi-aromatic polyamide (b-5) In the production of semi-aromatic polyamide (b-1), 4.086 kg (30.0 mol) of p-xylylenediamine was converted to 4.086 kg (30. Semi-aromatic polyamide (except that the polymerization temperature was changed from 300 ° C. to 275 ° C.) and 6.068 kg (30.0 mol) of sebacic acid was changed to 4.384 kg (30.0 mol) of adipic acid. A semi-aromatic polyamide (polyamide MXD6 = 100 mol%) having a melting point of 243 ° C. and a relative viscosity of 2.45 was obtained in the same manner as in the production of b-1) (hereinafter, this semi-aromatic polyamide was converted to (b- 5).)

Production of semi-aromatic polyamide resin composition (B-5) In production of semi-aromatic polyamide resin composition (B-1), semi-aromatic polyamide (b-1) was changed to (b-5), and the cylinder temperature was changed. In the same manner as in the production of the semi-aromatic polyamide resin composition (B-1) except that the temperature was changed from 310 ° C. to 280 ° C., a total of 90% by mass of the semi-aromatic polyamide and 10% by mass of the impact resistance improving material. A pellet of a semi-aromatic polyamide resin composition comprising 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus processing stabilizer was obtained with respect to 100 parts by mass (hereinafter, this semi-aromatic polyamide resin composition). A thing is called (B-5).).

Production of semi-aromatic polyamide (b-6) 3.240 kg (19.5 mol) of terephthalic acid, 1.246 kg (7.5 mol) of isophthalic acid, 0.438 kg (3.0 mol) of adipic acid, 1,6 -Hexanediamine 3.718 kg (32.0 mol), acetic acid 50.4 g (0.84 mol), sodium hypophosphite monohydrate 7.77 g and distilled water 2.5 liters with an internal volume of 40 liters In a pressure vessel and purged with nitrogen.
The mixture was stirred at 100 ° C. for 30 minutes, and the internal temperature was raised to 220 ° C. over 2 hours. At this time, the autoclave was pressurized to 2.0 MPa. The reaction was continued for 2 hours, and then the temperature was raised to 230 ° C., and then the temperature was maintained at 230 ° C. for 2 hours. The reaction was carried out while gradually removing water vapor and keeping the pressure at 2.0 MPa. Next, the pressure was reduced to 1.0 MPa over 30 minutes, and the reaction was further continued for 1 hour to obtain a prepolymer. This was dried at 100 ° C. under reduced pressure for 12 hours, pulverized to a size of 2 mm or less, solid-phase polymerized at 250 ° C. and 0.013 kPa for 8 hours, a melting point of 315 ° C. and a relative viscosity of 2.38 half. An aromatic polyamide (polyamide 6T / 6I / 66 = 65/25/10 mol%) was obtained (hereinafter, this semi-aromatic polyamide is referred to as (b-6)).

Production of semi-aromatic polyamide resin composition (B-6) In production of semi-aromatic polyamide resin composition (B-1), semi-aromatic polyamide (b-1) was changed to (b-6), and the cylinder temperature was changed. In the same manner as in the production of the semi-aromatic polyamide resin composition (B-1) except that the temperature was changed from 310 ° C. to 350 ° C. A pellet of a semi-aromatic polyamide resin composition comprising 0.8 parts by mass of an antioxidant and 0.2 parts by mass of a phosphorus processing stabilizer was obtained with respect to 100 parts by mass (hereinafter, this semi-aromatic polyamide resin composition). A thing is called (B-6).).

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

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

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

Production of fluorinated polymer (C-4) In production of fluorinated polymer (C-3), 5-norbornene-2,3-dicarboxylic acid anhydride (NAH) 0.3 mass% 1,3- 7.6 kg of the fluorinated polymer in the same manner as the production of the fluorinated polymer (C-3) except that the dichloro-1,1,2,2,3-pentafluoropropane solution was not charged. Got.
The composition of the fluorine-containing polymer is TFE-based polymer units / PPVE-based polymer units / HFP-based polymer units = 91.5 / 1.5 / 7.0 (mol%), and the melting point is 257 ° C. Met. This granulated product was melted using an extruder at 300 ° C. for a residence time of 2 minutes to obtain a fluorine-containing polymer pellet (hereinafter, this fluorine-containing polymer is referred to as (C-4). ).

Modified polyolefin (D)
Maleic anhydride-modified polypropylene (D-1): manufactured by Mitsui Chemicals, Admer QF500

Example 1
Using the polyamide 12 resin composition (A-1) and the semi-aromatic polyamide resin composition (B-1) shown above, in a Plabor (Plastics Engineering Laboratory Co., Ltd.) two-layer tube molding machine, (A-1) was melted separately at an extrusion temperature of 260 ° C. and (B-1) was melted separately at an extrusion temperature of 310 ° C., and the discharged molten resin was merged with an adapter to form a laminated tubular body. Subsequently, when cooled by a sizing die for dimension control and taken up, the (a) layer (outermost layer) composed of (A-1) and the (b) layer (innermost layer) composed of (B-1) are obtained. A laminated tube having a layer configuration of (a) / (b) = 0.75 / 0.25 mm, an inner diameter of 6 mm, and an outer diameter of 8 mm was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 2
In Example 1, except that the semi-aromatic polyamide resin composition (B-1) was changed to the conductive semi-aromatic polyamide resin composition (B-2), Table 1 A laminated tube having the layer structure shown in FIG. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 3
In Example 1, the same method as in Example 1 except that the semiaromatic polyamide resin composition (B-1) was changed to (B-3) and the extrusion temperature of (B-3) was changed to 300 ° C. Thus, a laminated tube having a layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 4
In Example 1, the laminated tube of the layer structure shown in Table 1 was obtained by the method similar to Example 1 except having changed the polyamide 12 resin composition (A-1) into (A-2). The physical property measurement results of the laminated tube are shown in Table 1.

Example 5
Example 1 is the same as Example 1 except that the polyamide 12 resin composition (A-1) is changed to the polyamide 610 resin composition (A-4) and the extrusion temperature of (A-4) is changed to 270 ° C. A laminated tube having the layer configuration shown in Table 1 was obtained in the same manner. The physical property measurement results of the laminated tube are shown in Table 1.

Example 6
In Example 1, the polyamide 12 resin composition (A-1) was changed to the polyamide 612 resin composition (A-5), and the extrusion temperature of (A-5) was changed to 270 ° C. A laminated tube having the layer configuration shown in Table 1 was obtained in the same manner. The physical property measurement results of the laminated tube are shown in Table 1.

Example 7
Using the polyamide 12 resin composition (A-1), polyamide 6/12 resin composition (A-7), and semi-aromatic polyamide resin composition (B-1) shown above, (Made by Co., Ltd.) In a three-layer tube molding machine, (A-1) was melted separately at an extrusion temperature of 260 ° C, (A-7) at an extrusion temperature of 250 ° C, and (B-1) at an extrusion temperature of 310 ° C. And the discharged molten resin is merged by an adapter, formed into a tubular shape, cooled by a sizing die that controls dimensions, taken up, and the layer made of (A-1) is changed to (a) layer (outermost layer), ( When the layer consisting of A-7) is the layer (a ′) (intermediate layer) and the layer consisting of (B-1) is the layer (b) (innermost layer), the layer configuration is (a) / (a ′). /(B)=0.60/0.15/0.25 mm, inner diameter 6 mm, outer diameter 8 mm laminated tube To obtain a drive. The physical property measurement results of the laminated tube are shown in Table 1.

Example 8
In Example 7, except that the polyamide 6/12 resin composition (A-7) was changed to the polyamide 610 resin composition (A-4) and the extrusion temperature of (A-4) was changed to 270 ° C. 7 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1.

Example 9
In Example 7, except that the polyamide 6/12 resin composition (A-7) was changed to the polyamide 612 resin composition (A-5) and the extrusion temperature of (A-5) was changed to 270 ° C. 7 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1.

Example 10
In Example 7, the polyamide 6/12 resin composition (A-7) is a semi-aromatic polyamide resin composition (B-1), and the semi-aromatic polyamide resin composition (B-1) is a conductive semi-aromatic polyamide. The layer structure shown in Table 1 was changed in the same manner as in Example 7 except that the extrusion temperature of (B-1) and (B-2) was changed to 310 ° C. instead of the resin composition (B-2). A laminated tube was obtained. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 11
In Example 10, except that the conductive semi-aromatic polyamide resin composition (B-2) was changed to the polyamide 6 resin composition (A-6) and the extrusion temperature of (A-6) was changed to 260 ° C, A laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 10. The physical property measurement results of the laminated tube are shown in Table 1.

Example 12
In Example 10, except that the conductive semi-aromatic polyamide resin composition (B-2) was changed to the polyamide 12 resin composition (A-1) and the extrusion temperature of (A-1) was changed to 260 ° C, A laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 10. The physical property measurement results of the laminated tube are shown in Table 1.

Example 13
In Example 10, except that the conductive semi-aromatic polyamide resin composition (B-2) was changed to the conductive polyamide 12 resin composition (A-3) and the extrusion temperature of (A-3) was changed to 270 ° C. Obtained the laminated tube of the layer structure shown in Table 1 by the method similar to Example 10. FIG. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 14
In Example 10, except that the conductive semi-aromatic polyamide resin composition (B-2) was changed to the fluorine-containing polymer (C-1) and the extrusion temperature of (C-1) was changed to 280 ° C, A laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 10. The physical property measurement results of the laminated tube are shown in Table 1.

Example 15
Example 14 is the same as Example 14 except that the polyamide 12 resin composition (A-1) was changed to the polyamide 612 resin composition (A-5) and the extrusion temperature of (A-5) was changed to 270 ° C. A laminated tube having the layer configuration shown in Table 1 was obtained in the same manner. The physical property measurement results of the laminated tube are shown in Table 1.

Example 16
In Example 14, except that the fluorine-containing polymer (C-1) was changed to the conductive fluorine-containing polymer (C-2) and the extrusion temperature of (C-2) was changed to 300 ° C. 14 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 17
Using the polyamide 12 resin composition (A-1), conductive polyamide 12 resin composition (A-3), and semi-aromatic polyamide resin composition (B-1) shown above, (Made by Co., Ltd.) In a four-layer tube molding machine, (A-1) was melted separately at an extrusion temperature of 260 ° C, (A-3) at an extrusion temperature of 270 ° C, and (B-1) at an extrusion temperature of 310 ° C. The molten resin discharged is joined by an adapter, formed into a tubular shape, cooled by a sizing die for dimension control, and taken up. , (B-1) is the layer (b) (intermediate layer), and (A-3) is the layer (a ′) (innermost layer), the layer configuration is (a) / (b ) / (A) / (a ′) = 0.40 / 0.25 / 0.25 / 0.10 mm, inner diameter 6 m, to obtain a laminated tube having an outer diameter of 8 mm. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 18
In Example 17, except that the conductive polyamide 12 resin composition (A-3) was changed to the fluorine-containing polymer (C-1) and the extrusion temperature of (C-1) was changed to 280 ° C. In the same manner as in No. 17, a laminated tube having the layer configuration shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 19
In Example 18, except that the fluorine-containing polymer (C-1) was changed to the conductive fluorine-containing polymer (C-2) and the extrusion temperature of (C-2) was changed to 300 ° C. In the same manner as in No. 18, a laminated tube having the layer configuration shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 20
In Example 19, except that the polyamide 12 resin composition (A-1) used as the inner layer material was changed to the fluorine-containing polymer (C-1), and the extrusion temperature of (C-1) was changed to 280 ° C. A laminated tube having the layer structure shown in Table 1 was obtained in the same manner as in Example 19. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

Example 21
In Example 20, except that the conductive fluorine-containing polymer (C-2) was changed to the fluorine-containing polymer (C-4) and the extrusion temperature of (C-4) was changed to 300 ° C. 20 was used to obtain a laminated tube having the layer structure shown in Table 1. The physical property measurement results of the laminated tube are shown in Table 1.

Example 22
In Example 21, the fluorine-containing polymer (C-1) was changed to (C-3), and the extrusion temperature of (C-3) was changed to 300 ° C., in the same manner as in Example 21. The laminated tube of the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Example 23
Polyamide 12 resin composition (A-1), semi-aromatic polyamide resin composition (B-1), fluorine-containing polymer (C-1), conductive fluorine-containing polymer (C-2) shown above And (A-1) with an extrusion temperature of 260 ° C., (B-1) with an extrusion temperature of 310 ° C., (C-1 ) Is melted separately at an extrusion temperature of 280 ° C. and (C-2) is melted at an extrusion temperature of 300 ° C., and the discharged molten resin is joined by an adapter, formed into a tubular shape, cooled by a sizing die that controls dimensions, and taken up. The layer consisting of (A-1) is changed to (a) layer (outermost layer, intermediate layer), the layer consisting of (B-1) is changed to (b) layer (outer layer), and the layer consisting of (C-1). When (c) layer (inner layer), (C-2) layer is (c ′) layer (innermost layer), layer The configuration is (a) / (b) / (a) / (c) / (c ′) = 0.45 / 0.15 / 0.15 / 0.15 / 0.10 mm, inner diameter 6 mm, outer diameter 8 mm A laminated tube was obtained. The physical property measurement results of the laminated tube are shown in Table 1. Moreover, when the electroconductivity of the said laminated tube was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square and it confirmed that it was excellent in the static electricity removal performance.

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

Comparative Example 2
In Example 1, the single layer tube shown in Table 1 was obtained by the method similar to Example 1 except not using a polyamide 12 resin composition (A-1). Table 1 shows the physical property measurement results of the single-layer tube.

Comparative Example 3
In Example 1, the same method as in Example 1 except that the semiaromatic polyamide resin composition (B-1) was changed to (B-4) and the extrusion temperature of (B-4) was changed to 240 ° C. Thus, a laminated tube having a layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 4
In Example 1, the same method as in Example 1 except that the semiaromatic polyamide resin composition (B-1) was changed to (B-5) and the extrusion temperature of (B-5) was changed to 280 ° C. Thus, a laminated tube having a layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 5
In Example 11, the same method as in Example 11 except that the semi-aromatic polyamide resin composition (B-1) was changed to (B-5) and the extrusion temperature of (B-5) was changed to 280 ° C. Thus, a laminated tube having a layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 6
In Example 12, the same method as in Example 12 except that the semiaromatic polyamide resin composition (B-1) was changed to (B-5) and the extrusion temperature of (B-5) was changed to 280 ° C. Thus, a laminated tube having a layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 7
In Example 1, the same method as in Example 1 except that the semi-aromatic polyamide resin composition (B-1) was changed to (B-6) and the extrusion temperature of (B-6) was changed to 350 ° C. Thus, a laminated tube having a layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 8
In Example 11, the same method as in Example 11 except that the semiaromatic polyamide resin composition (B-1) was changed to (B-6) and the extrusion temperature of (B-6) was changed to 350 ° C. Thus, a laminated tube having a layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 9
In Example 12, the same method as in Example 12 except that the semiaromatic polyamide resin composition (B-1) was changed to (B-6) and the extrusion temperature of (B-6) was changed to 350 ° C. Thus, a laminated tube having a layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 10
In the comparative example 8, the lamination | stacking of the layer structure shown in Table 1 is the same method as the comparative example 8 except having changed the polyamide 12 resin composition (A-1) into the polyamide 6 resin composition (A-6). A tube was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 11
Using the polyamide 12 resin composition (A-1), semi-aromatic polyamide resin composition (B-6), and modified polyolefin (D-1) shown above, Plabor (manufactured by Plastic Engineering Laboratory Co., Ltd.) In a five-layer tube forming machine, (A-1) was melted separately at an extrusion temperature of 260 ° C., (B-6) at an extrusion temperature of 350 ° C., and (D-1) was melted at an extrusion temperature of 200 ° C., and discharged. The molten resin is merged with an adapter, formed into a tubular shape, cooled with a sizing die for dimension control, and taken up. The layer consisting of (A-1) is changed to (a) layer (outermost layer, innermost layer), (B- When the layer consisting of 5) is the (b) layer (intermediate layer) and the layer consisting of (D-1) is the (d) layer (outer layer, inner layer), the layer configuration is (a) / (d) / (b ) / (D) / (a) = 0.30 / 0.10 / 0.25 / 0.10 / 0.25 m , An inner diameter of 6 mm, to obtain a laminated tube having an outer diameter of 8 mm. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 12
In Example 14, the same method as in Example 14 except that the semi-aromatic polyamide resin composition (B-1) was changed to (B-6) and the extrusion temperature of (B-6) was changed to 350 ° C. Thus, a laminated tube having a layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 13
In Example 18, the same method as in Example 18 except that the semiaromatic polyamide resin composition (B-1) was changed to (B-6) and the extrusion temperature of (B-6) was changed to 350 ° C. Thus, a laminated tube having a layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated tube are shown in Table 1.

As is apparent from Table 1, the single-layer tube of Comparative Example 1 that does not have a layer made of the semi-aromatic polyamide defined in the present invention is inferior in chemical solution permeation preventing property and is composed of the aliphatic polyamide defined in the present invention. The single-layer tube of Comparative Example 2 having no layer was inferior in low-temperature impact resistance. The laminated tube of Comparative Example 3 having a layer made of a semi-aromatic polyamide other than those specified in the present invention was inferior in chemical resistance and heat resistance. The laminated tubes of Comparative Examples 4 to 9 having a layer made of a semi-aromatic polyamide other than those specified in the present invention were inferior in chemical resistance, heat resistance and interlayer adhesion. The laminated tubes of Comparative Examples 10 and 11 having a layer made of a semi-aromatic polyamide other than those specified in the present invention were inferior in chemical resistance and heat resistance. The laminated tubes of Comparative Examples 12 and 13 having a layer made of a semi-aromatic polyamide other than those specified in the present invention and having a layer made of a fluorine-containing polymer as the innermost layer were inferior in interlayer adhesion.
On the other hand, the laminated tubes of Examples 1 to 23 defined in the present invention have good properties such as low-temperature impact resistance, chemical solution permeation prevention properties, interlayer adhesion properties, chemical resistance properties, and heat resistance properties. it is obvious.

Claims (7)

Layer (a) composed of aliphatic polyamide (A), diamine units containing 60 mol% or more of p-xylylenediamine units with respect to all diamine units, and 8 to 13 carbon atoms with respect to all dicarboxylic acid units Comprising at least two or more layers, including (b) a layer comprising a semi-aromatic polyamide (B) comprising a dicarboxylic acid unit comprising 60 mol% or more of the following aliphatic dicarboxylic acid units;
A laminated structure characterized by being used as a laminated molded product selected from the group consisting of a chemical solution transport tube, a chemical solution transport hose, a chemical solution storage bottle, and a chemical solution storage tank . The aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms in the semi-aromatic polyamide (B) is at least one selected from the group consisting of units derived from azelaic acid, sebacic acid, and dodecanedioic acid. The laminated structure according to claim 1, wherein there is a laminated structure. The aliphatic polyamide (A) is polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene decanamide ( Polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecane methylene decanamide (polyamide 1010), polydecamethylene dodecane (polyamide 1012), and polydodecamethylene dodecane (polyamide 1212). The laminate structure according to claim 1 or 2, wherein the laminate structure is at least one homopolymer or a copolymer using several kinds of raw material monomers forming them. The (a) layer composed of the aliphatic polyamide (A) is disposed in the outermost layer, and the (b) layer composed of the semi-aromatic polyamide (B) is disposed inside the (a) layer. The laminated structure according to any one of claims 1 to 3. The layered structure according to any one of claims 1 to 4, wherein the (b) layer made of the semi-aromatic polyamide (B) is disposed in an innermost layer. The laminated structure according to claim 4, further comprising a (c) layer comprising a fluorine-containing polymer (C) in which a functional group having reactivity to an amino group is introduced into a molecular chain, c) A laminated structure characterized in that the layer is disposed in the innermost layer. The laminated structure according to any one of claims 1 to 6, wherein the laminated structure is manufactured by coextrusion molding.