JP2006044074A - Laminated structure - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a laminated structure excellent in low temperature impact resistance, chemical liquid impermeability, interlaminar adhesiveness and chemical resistance. <P>SOLUTION: The laminated structure is composed of at least two layers, that is, a layer (a) comprising an aliphatic polyamide (A) and a layer (b) comprising a layered silicate-containing half-aromatic polyamide composition (B) having 0.1-30 pts.wt. of a layered silicate (B2) uniformly dispersed in its molecule with respect to 100 pts.wt. of a half-aromatic polyamide polymer (B1) comprising a diamine unit containing 60 mol% or above of a xylylenediamine and/or a naphthalenedimethylamine with respect to the whole diamine unit and a dicarboxylic acid unit containing 60 mol% or above of a 8-13C aliphatic dicarboxylic acid unit with respect to the whole dicarboxylic acid unit. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention provides a laminated structure including a layer made of an aliphatic polyamide and a layer made of a layered silicate-containing semi-aromatic polyamide composition, particularly for low-temperature impact resistance, chemical resistance, chemical penetration prevention, and interlayer adhesion. The present invention relates to an excellent laminated structure.

  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 resin that is superior in properties and light weight 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.

  Further, 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. In response to 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, and flexibility, is used as described above. The permeation-preventing property for chemical liquids including fuel is not sufficient, and in particular, an improvement for the permeation-preventing property of alcohol-containing gasoline is required.

  As a method for solving this problem, resins having good chemical permeation preventive properties such as saponified ethylene / vinyl acetate copolymer (EVOH), polymetaxylylene adipamide (polyamide MXD6), polybutylene terephthalate (PBT), polyethylene Naphthalate (PEN), polybutylene naphthalate (PBN), polyvinylidene fluoride (PVDF), ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE), tetrafluoroethylene / Laminated structure in which hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (TFE / HFP / VDF, THV) are arranged, particularly laminated tube or hose It has been proposed (e.g., refer to Jpn.).

  Among these, a fuel transfer tube or hose in which polymetaxylylene adipamide (polyamide MXD6) is disposed in an intermediate layer has been proposed (see Patent Document 2 and the like). This polyamide MXD6 is known to have good adhesive strength with polyamide 6. However, since polyamide 11 or polyamide 12 conventionally used as a constituent material of a single-layer tube or hose has insufficient interlayer adhesion, it is necessary to provide an adhesive layer between the layers, which is a cost aspect. , Inconvenience in management. Furthermore, the hose in which the polyamide MXD6 is disposed has a disadvantage that it is inferior in low-temperature impact resistance, and it is desired to develop a laminated structure that achieves both chemical permeation prevention and low-temperature impact resistance.

US Pat. No. 5,554,425 JP-A-4-272592

  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 properties, interlayer adhesion properties, and chemical resistance.

The present inventor has made extensive studies to solve the above problems, and as a result, a layered silicate-containing semi-aromatic polyamide composition in which a layered silicate is uniformly dispersed in a semi-aromatic polyamide polymer having a specific structure. It has been found that a laminated structure including a layer composed of the above and a layer composed of an aliphatic polyamide is excellent in low-temperature impact resistance, chemical resistance, chemical solution permeation prevention properties, and interlayer adhesion.
That is, the present invention comprises (A) a layer composed of an aliphatic polyamide (a), a diamine unit containing 60 mol% or more of xylylenediamine and / or naphthalenedimethylamine units with respect to all diamine units, and all dicarboxylic acid units. On the other hand, (B2) layered silicic acid in the molecule with respect to 100 weight of (B1) semi-aromatic polyamide polymer consisting of dicarboxylic acid units containing 60 mol% or more of aliphatic dicarboxylic acid units having 8 to 13 carbon atoms (B) Layered silicate-containing semi-aromatic polyamide composition in which 0.1 to 30 parts by weight of salt are uniformly dispersed and (b) a layered structure comprising at least two layers Is to provide.

  The laminated structure of the present invention includes a layer made of an aliphatic polyamide and a layer made of a layered silicate-containing semi-aromatic polyamide composition in which a layered silicate is uniformly dispersed in a semi-aromatic polyamide polymer having a specific structure. It has both low temperature impact resistance and chemical solution permeation prevention properties, and is excellent in various properties such as interlayer adhesion, heat resistance, and chemical resistance. Therefore, the film, hose, tube, 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. Particularly suitable as a chemical solution transporting tube or hose, it is possible to suppress alcohol-mixed hydrocarbons that permeate and evaporate from the tube or hose partition wall.

The present invention is described in detail below.
The (A) aliphatic polyamide used in the present invention refers to a polyamide comprising an amide bond (—NHCO—) in the main chain and comprising an aliphatic polyamide forming unit. (A) Aliphatic polyamide is polymerized by a known method such as melt polymerization, solution polymerization or solid phase polymerization using lactam, aminocarboxylic acid, or nylon salt composed of aliphatic diamine and aliphatic dicarboxylic acid, or Obtained by copolymerization.

  Examples of lactams include caprolactam, enantolactam, undecane lactam, dodecane lactam, α-pyrrolidone, α-piperidone, and aminocarboxylic acids include 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, and 9-aminononane. Examples thereof include acid, 10-aminocapric acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid.

  Examples of the aliphatic diamine constituting the nylon salt include ethylenediamine, 1,3-propylenediamine, 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 / 3-methyl-1, 5-pentanediamine, 2-methyl-1,8-octanediamine, 2,2,4 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine, and the like.

  Examples of the aliphatic dicarboxylic acid constituting the nylon salt include adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, tridecanedicarboxylic acid, tetradecanedicarboxylic acid, pentadecanedicarboxylic acid, hexadecanedicarboxylic acid. Examples include acid, octadecanedicarboxylic acid, eicosanedicarboxylic acid and the like.

In the present invention, (A) aliphatic polyamide includes polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyethylene adipamide (polyamide 26), polytetramethylene azide Pamide (polyamide 46), polyhexamethylene adipamide (polyamide 66), polyhexamethylene azelamide (polyamide 69), polyhexamethylene sebamide (polyamide 610), polyhexamethylene undecamide (polyamide 611), Polyhexamethylene dodecamide (Polyamide 612), Polynonamethylene adipamide (Polyamide 96), Polynonamethylene azelamide (Polyamide 99), Polynonamethylene sebacamide (Polyamide 910), Polynonamethylene undecamide Polyamide 911), polynonamethylene dodecamide (polyamide 912), polydecamethylene adipamide (polyamide 106), polydecamethylene azelamide (polyamide 109), polydecamethylene sebamide (polyamide 1010), polydecamethylene dodecamide Amide (polyamide 1012), polydodecamethylene adipamide (polyamide 126), polydodecamethylene azelamide (polyamide 129), polydodecamethylene sebamide (polyamide 1210), polydodecamethylene dodecamide (polyamide 1212), etc. Examples thereof include a polymer and a copolymer using several kinds of raw material monomers forming these.
Among these, polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene dodecanamide (polyamide 612), polynona. Methylene azeamide (polyamide 99), polynonamethylene sebacamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), polydecamethylene sebacamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), At least one homopolymer selected from the group consisting of polydodecamethylene dodecamide (polyamide 1212) or a copolymer using several kinds of raw material monomers forming these is preferable, and further, heat resistance and cost are taken into consideration. if you did this Homopolymers of polycaproamide (polyamide 6) and polyhexamethylene adipamide (polyamide 66) are preferable. When considering hot water resistance, zinc chloride resistance, calcium chloride resistance, etc., polyundecanamide (polyamide 11) A homopolymer of polydodecanamide (polyamide 12) and polyhexamethylene dodecanamide (polyamide 612) is preferable.

  The (A) aliphatic polyamide used in the present invention may be a mixture of the above homopolymers, a mixture of the above copolymers, a mixture of a homopolymer and a copolymer, or other It may also be a mixture with a polyamide-based resin or other thermoplastic resin. The content of (A) aliphatic polyamide in the mixture is preferably 60% by weight or more.

  Other polyamide resins include polymetaxylylene adipamide (polyamide MXD6), polybis (4-aminocyclohexyl) methane dodecamide (polyamide PACM12), polybis (4-aminocyclohexyl) methane terephthalamide (polyamide PACMT), Polybis (4-aminocyclohexyl) methane isophthalamide (polyamide PACMI), polybis (3-methyl-4-aminocyclohexyl) methane dodecamide (polyamide dimethyl PACM12), polyisophorone adipamide (polyamide IPD6), polyisophorone terephthalate Ramide (polyamide IPDT), polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polytrimethylhexamethylene terephthalate Polyamide (polyamide TMHT), polynonamethylene terephthalamide (polyamide 9T), polynonamethylene isophthalamide (polyamide 9I), polynonamethylene naphthalamide (polyamide 9N), polynonamethylene hexahydroterephthalamide (polyamide 9T (polyamide 9T) H)), polydecamethylene terephthalamide (polyamide 10T), polydecamethylene isophthalamide (polyamide 10I), polydecamethylene naphthalamide (polyamide 10N), polydecamethylene hexahydroterephthalamide (polyamide 10T (H )), Polyundecamethylene terephthalamide (polyamide 11T), polyundecamethylene isophthalamide (polyamide 11I), polyundecamethylene naphthalamide (polyamide 11N), polyundecamethylene hexaldehyde Terephthalamide (polyamide 11T (H)), polydodecamethylene terephthalamide (polyamide 12T), polydodecamethylene isophthalamide (polyamide 12I), polydodecamethylene naphthalamide (polyamide 12N), polydodecamethylene hexahydroterephthalamide (Polyamide 12T (H)), a copolymer using these polyamide raw material monomers and / or several kinds of the above polyamide raw material monomers, and the like.

  Other thermoplastic resins include 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), ethylene / propylene copolymer (EPR), ethylene / butene copolymer (EBR), ethylene / vinyl acetate copolymer (EVA), ethylene / vinyl acetate copolymer saponified product (EVOH), ethylene / Acrylic acid copolymer (EAA), ethylene / methacrylic acid copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), ethylene / ethyl acrylate copolymer Polyolefin resins such as polymers (EEA) and carboxy The above-mentioned polyolefin resin containing functional groups such as salts thereof, acid anhydride groups, and epoxy groups, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer weight Polyester resins such as coalesced polyarylate (PAR), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), liquid crystal polyester (LCP), and polyether resins such as polyacetal (POM) and polyphenylene oxide (PPO) Polysulfone resins such as polysulfone (PSF) and polyethersulfone (PES), polythioether resins such as polyphenylene sulfide (PPS) and polythioethersulfone (PTES), polyetheretherketone (PEE) ), Polyketone resins such as polyallyl ether ketone (PAEK), polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene Polynitrile resins such as copolymers (ABS), methacrylonitrile / styrene / butadiene copolymers (MBS), polymethacrylate resins such as polymethyl methacrylate (PMMA) and polyethyl methacrylate (PEMA), polyvinyl alcohol (PVA), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), polyvinyl chloride such as vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate copolymer, cellulose acetate, cellulose butyrate Rulose resin, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polychlorofluoroethylene (PCTFE), tetrafluoroethylene / ethylene copolymer (ETFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE) , Tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (TFE / HFP / VDF, THV), tetrafluoroethylene / fluoro (alkyl) Vinyl ether) copolymer (PFA) and other fluorine resins, polycarbonate (PC) and other polycarbonate resins, thermoplastic polyimide (PI), polyamideimide (PAI), polyetherimide and other polyimide resins System resins, thermoplastic polyurethane resins. These may be used alone or in combination.

  Moreover, it is preferable to add a plasticizer to the (A) aliphatic polyamide used in the present invention. 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- or N-ethyl-p-toluenesulfonic acid butyramide, N-ethyl-o- or N-ethyl-p-toluenesulfonic acid 2-ethylhexylamide, and the like. Is mentioned.
Examples of hydroxybenzoic acid alkyl esters include ethylhexyl o- or p-hydroxybenzoate, hexyldecyl o- or p-hydroxybenzoate, ethyl decyl o- or p-hydroxybenzoate, octyloctyl o- or p-hydroxybenzoate Decyldodecyl o- or p-hydroxybenzoate, methyl o- or p-hydroxybenzoate, butyl o- or p-hydroxybenzoate, hexyl o- or p-hydroxybenzoate, o- or p-hydroxybenzoic acid Examples include n-octyl, o- or p-hydroxybenzoic acid decyl and o- or p-hydroxybenzoic acid dodecyl.

  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 Toluenesulfonic acid alkylamides and hydroxybenzoic acid alkyl esters such as ethylhexyl p-hydroxybenzoate, hexyldecyl p-hydroxybenzoate and ethyldecyl p-hydroxybenzoate are preferably used. Particularly preferably, benzenesulfonic acid butyramide, ethylhexyl p-hydroxybenzoate, hexyldecyl p-hydroxybenzoate, or the like is used.

  The amount of the plasticizer is preferably 1 to 30 parts by weight, more preferably 1 to 15 parts by weight with respect to 100 parts by weight of the (A) aliphatic polyamide component. If the blending amount of the plasticizer exceeds 30 parts by weight, the low temperature impact resistance of the laminated structure may be lowered.

  Moreover, it is preferable to add an impact modifier to the (A) aliphatic polyamide used in the present invention. Examples of the impact modifier include rubbery polymers, and those having a flexural modulus of 500 MPa or less as measured in accordance with ASTM D-790 are preferable. If the flexural modulus is higher than this value, the impact improving effect may be insufficient.

  Impact modifiers include (ethylene and / or propylene) / α-olefin copolymers, (ethylene and / or propylene) / (α, β-unsaturated carboxylic acids and / or unsaturated carboxylic esters) Examples thereof include a polymer, an ionomer polymer, and an aromatic vinyl compound / conjugated diene compound block copolymer, and these can be used alone or in combination.

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 combinations thereof.
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-isopropylene-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.

  The above (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) copolymer is ethylene and / or propylene and α, β-unsaturated carboxylic acid and And / or a polymer obtained by copolymerizing an unsaturated carboxylic acid ester monomer, and examples of the α, β-unsaturated carboxylic acid monomer include acrylic acid and methacrylic acid, and α, β-unsaturated carboxylic acid. Examples of the ester monomer include methyl esters, ethyl esters, propyl esters, butyl esters, pentyl esters, hexyl esters, heptyl esters, octyl esters, nonyl esters, decyl esters, and the like of these unsaturated carboxylic acids, or mixtures thereof. It is done.

  The ionomer polymer is obtained by ionizing at least a part of an olefin and a carboxyl group of an α, β-unsaturated carboxylic acid copolymer by neutralization of a metal ion. 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, and the unsaturated carboxylic acid ester 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. Can be mentioned.

  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 structural units derived from an aromatic vinyl compound. In this case, the aromatic vinyl compound includes styrene, α-methylstyrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,5-dimethylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinyl. Anthracene, 4-propyl styrene, 4-cyclohexyl styrene, 4-dodecyl styrene, 2-ethyl-4-benzyl styrene, 4- (phenylbutyl) styrene and the like can be mentioned, and the aromatic vinyl compound polymer block is the above-mentioned It may have a structural unit consisting of one or more of the monomers. In addition, the aromatic vinyl compound-based polymer block may optionally have a structural unit composed of a small amount of other 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 in a hydrogenated aromatic vinyl compound / conjugated diene compound block copolymer, the conjugated diene compound polymer block A part or the whole of the unsaturated bond part in is a saturated bond 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 them, one aromatic vinyl compound polymer block and one conjugated diene compound polymer block are linear as an aromatic vinyl compound / conjugated diene compound block copolymer and / or a hydrogenated product thereof. 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 / isoprene / styrene block copolymer, unhydrogenated or hydrogenated styrene / butadiene / styrene block Click copolymer, non-hydrogenated or include hydrogenated styrene / (isoprene / butadiene) / styrene block copolymer.

  In addition, (ethylene and / or propylene) / α-olefin copolymers used as impact modifiers, (ethylene and / or propylene) / (α, β-unsaturated carboxylic acid and / or unsaturated carboxylic acid ester) As the copolymer, ionomer polymer, and aromatic vinyl compound / conjugated diene compound block copolymer, a polymer modified with a carboxylic acid and / or a derivative thereof is preferably used. By modifying with such a component, a functional group having an affinity for (A) aliphatic polyamide is included in the molecule.

  (A) Examples of functional groups having affinity for aliphatic polyamides include carboxyl groups, acid anhydride groups, carboxylic acid ester groups, carboxylic acid metal salts, carboxylic acid imide groups, carboxylic acid amide groups, and epoxy groups. 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 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, glycidyl citraconic acid, and the like.

  The blending amount of the impact modifier is preferably 1 to 35 parts by weight, more preferably 5 to 25 parts by weight with respect to 100 parts by weight of the (A) aliphatic polyamide component. When the amount of the impact modifier exceeds 35 parts by weight, the original mechanical properties of the laminated structure are impaired, which is not preferable.

  Furthermore, the (A) aliphatic polyamide used in the present invention includes an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, an inorganic filler, an antistatic agent, if necessary. You may add a flame retardant, a crystallization accelerator, etc.

  (A) Production equipment used in the production of aliphatic polyamides includes batch reaction kettles, single-tank or multi-tank continuous reaction equipment, tubular continuous reaction equipment, single-screw kneading extruder, twin-screw kneading extrusion A known polyamide production apparatus such as a kneading reaction extruder such as a machine can 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 (A) aliphatic polyamide used in the present invention has a relative viscosity measured according to JIS K-6920, preferably 1.5 to 5.0, more preferably 2.0 to 4. 5. If the relative viscosity is less than the above value, the mechanical properties of the resulting laminated structure may be insufficient, and if it exceeds the above value, the extrusion pressure and torque become too high, and the laminated structure. May be difficult to manufacture.

The (B) layered silicate-containing semi-aromatic polyamide composition used in the present invention comprises diamine units containing 60 mol% or more of xylylenediamine and / or naphthalenedimethylamine units with respect to all diamine units, (B1) semi-aromatic polyamide polymer (hereinafter referred to as (B1) semi-aromatic polyamide polymer) comprising a dicarboxylic acid unit containing 60 mol% or more of an aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms to the dicarboxylic acid unit And (B2) layered silicate uniformly dispersed in the molecule.

  (B1) The semi-aromatic polyamide polymer is a diamine unit containing 60 mol% or more of xylylenediamine and / or naphthalenedimethylamine units with respect to all diamine units, and 8 to 8 carbon atoms with respect to all dicarboxylic acid units. 13 dicarboxylic acid units containing 60 mol% or more of aliphatic dicarboxylic acid units.

(B1) The content of xylylenediamine and / or naphthalenedimethylamine units in the semi-aromatic polyamide polymer is 60 mol% or more, preferably 75 mol% or more, based on the total diamine units. Preferably it is 90 mol% or more. When the content of the xylylenediamine and / or naphthalenedimethylamine unit is less than 60 mol%, various physical properties such as heat resistance, chemical resistance, and chemical solution permeation resistance of the resulting laminated structure tend to be lowered.
Examples of the xylylenediamine unit include units derived from orthoxylylenediamine, metaxylylenediamine, and paraxylylenediamine. Among the above xylylenediamine units, units derived from metaxylylenediamine are preferable.
Examples of the naphthalenedimethylamine unit include units derived from 1,4-naphthalenedimethylamine, 1,5-naphthalenedimethylamine, 2,6-naphthalenedimethylamine, and 2,7-naphthalenedimethylamine. Among the naphthalenedimethylamine units, units derived from 1,5-naphthalenedimethylamine and 2,6-naphthalenedimethylamine are preferable.

(B1) The diamine unit in the semi-aromatic polyamide polymer is other than a unit derived from xylylenediamine and / or naphthalenedimethylamine as long as it does not impair the excellent characteristics of the laminated structure of the present invention. Other diamine units may be included. Examples of the other diamine units include ethylenediamine, 1,3-propylenediamine, 1,4-butanediamine, 1,6-hexanediamine, 1,8-octanediamine, 1,9-nonanediamine, and 1,10-decanediamine. 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 2 / 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, 2,2 , 4 / 2,4,4-trimethyl-1,6-hexanediamine, aliphatic diamine such as 5-methyl-1,9-nonanediamine, 1,3 / 1,4-cyclohexanediamine, 1,3 / 1, 4-cyclohexanedimethylamine, bis (4-aminocyclohexyl) methane, bis (4-aminocyclohexyl) propane, bis (3-methyl) -4-aminocyclohexyl) methane, bis (3-methyl-4-aminocyclohexyl) propane, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3- Cycloaliphatic diamines such as trimethylcyclohexanemethylamine, bis (aminopropyl) piperazine, bis (aminoethyl) piperazine, norbornanedimethylamine, tricyclodecanedimethylamine, paraphenylenediamine, metaphenylenediamine, 4,4'-diaminodiphenylmethane , 4,4′-diaminodiphenyl sulfone, units derived from aromatic diamines such as 4,4′-diaminodiphenyl ether, etc., and one or more of these can be used. Among the above units, units derived from aromatic diamine units are preferred. The content of these other diamine units is preferably 40 mol% or less, more preferably 25 mol% or less, and even more preferably 10 mol% or less.

In addition, the content of the aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms in the (B1) semi-aromatic polyamide polymer is 60 mol% or more, preferably 75 mol, based on all dicarboxylic acid units. % Or more, more preferably 90 mol% or more. When the content of the aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms is less than 60 mol%, the heat resistance, chemical resistance and impact resistance of the laminated structure tend to be lowered.

Examples of the aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms include units derived from suberic acid, azelaic acid, sebacic acid, undecanedicarboxylic acid, dodecanedicarboxylic acid, and tridecanedicarboxylic acid. Derived from branched aliphatic dicarboxylic acids such as 2,2,4 / 2,4,4-trimethyladipic acid and 2-butylsuberic acid as long as the carbon number satisfies the above It may contain the unit to be. Among the aliphatic dicarboxylic acid units having 8 to 13 carbon atoms, units derived from suberic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid are preferred.

(B1) The dicarboxylic acid unit in the semi-aromatic polyamide polymer is derived from an aliphatic dicarboxylic acid having 8 to 13 carbon atoms as long as the excellent properties of the laminated structure of the present invention are not impaired. Other dicarboxylic acid units other than the unit may be contained. Examples of the other dicarboxylic acid units include malonic acid, dimethylmalonic acid, succinic acid, glutaric acid, adipic acid, 2-methyladipic acid, pimelic acid, 2,2-dimethylglutaric acid, tetradecanedicarboxylic acid, pentadecanedicarboxylic acid, Hexadecanedicarboxylic acid, octadecanedicarboxylic acid, aliphatic dicarboxylic acid such as eicosanedicarboxylic acid, alicyclic dicarboxylic acid such as 1,3-cyclopentanedicarboxylic acid, 1,3 / 1,4-cyclohexanedicarboxylic acid, terephthalic acid, Isophthalic acid, 1,4 / 2,6 / 2,7-naphthalenedicarboxylic acid, 1,3 / 1,4-phenylenedioxydiacetic acid, diphenic acid, 4,4'-oxydibenzoic acid, diphenylmethane-4,4 '-Dicarboxylic acid, diphenylsulfone-4,4'-dicarboxylic acid, 4,4'-bifu Can be mentioned units derived from aromatic dicarboxylic acids such as Nirujikarubon acid, may be used alone or two or more of these. The content of these other dicarboxylic acid units is preferably 40 mol% or less, more preferably 25 mol% or less, and even more preferably 10 mol% or less. Furthermore, polycarboxylic acids such as trimellitic acid, trimesic acid, and pyromellitic acid can be used within a range where melt molding is possible.

  The (B1) semi-aromatic polyamide polymer preferably has its molecular chain end sealed with an end-capping agent, more preferably 20% or more of the end groups are sealed, More preferably, 40% 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. From the viewpoint of reactivity and stability of the capping end, monocarboxylic acid is used. An acid or a monoamine is preferable, and a monocarboxylic acid is more preferable from the viewpoint of easy handling. In addition, monoisocyanates, monoacid halides, monoesters, monoalcohols, and the like can be used.

  The monocarboxylic acid used as the terminal blocking agent is not particularly limited as long as it has reactivity with an amino group. For example, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, Aliphatic monocarboxylic acid such as lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, pivalic acid, isobutyric acid, cycloaliphatic carboxylic acid, benzoic acid, toluic acid, α-naphthalenecarboxylic acid Examples thereof include aromatic monocarboxylic acids such as acid, β-naphthalenecarboxylic acid, methylnaphthalenecarboxylic acid, and phenylacetic acid, or any mixture thereof. Of these, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, caprylic acid, lauric acid, tridecylic acid, myristic acid, palmitic acid, stearic acid, in terms of reactivity, stability of the sealing end, price, etc. Benzoic acid is particularly preferred.

  The monoamine used as a terminal blocking agent is not particularly limited as long as it has reactivity with a carboxyl group. For example, methylamine, ethylamine, propylamine, butylamine, hexylamine, octylamine, decylamine, Aliphatic monoamines such as stearylamine, dimethylamine, diethylamine, dipropylamine and dibutylamine, alicyclic monoamines such as cyclohexylamine and dicyclohexylamine, aromatic monoamines such as aniline, toluidine, diphenylamine and naphthylamine, or any of these Mention may be made of mixtures. Of these, butylamine, hexylamine, octylamine, decylamine, stearylamine, cyclohexylamine, and aniline are particularly preferable from the viewpoints of reactivity, boiling point, stability of the sealing end, and price.

  (B1) The amount of end-capping agent used when producing the semi-aromatic polyamide polymer is determined from the relative viscosity of the finally obtained polyamide and the end-group capping rate. The specific amount used varies depending on the reactivity, boiling point, reaction apparatus, reaction conditions, etc. of the end-capping agent to be used, but is usually 0.1 to 10 with respect to the total number of moles of dicarboxylic acid and diamine as raw materials. Used in the range of mol%.

Furthermore, the (B1) semi-aromatic polyamide polymer can be produced by using a known polyamide polymerization method known as a method for producing polyamide. Production equipment includes known polyamides such as batch reaction kettles, single tank or multi-tank continuous reaction apparatuses, tubular continuous reaction apparatuses, kneading reaction extruders such as uniaxial kneading extruders and biaxial kneading extruders, etc. Manufacturing equipment can be used. As a polymerization method, a known method such as melt polymerization, solution polymerization, or solid phase polymerization can be used, and polymerization can be performed by repeating normal pressure, reduced pressure, and pressure operations. These polymerization methods can be used alone or in appropriate combination.

  In the present invention, the (B2) layered silicate contained in the (B) layered silicate-containing semi-aromatic polyamide composition is uniformly dispersed at the molecular level without locally agglomerating to form a silicate layer. Need to be. Here, the silicate layer is a basic unit constituting the (B2) layered silicate, and is obtained by cleaving the (B2) layered silicate. Here, the (B2) layered silicate is preferably, for example, one unit indicating one unit of a substance having a thickness of 0.002 to 1 μm and a thickness of 6 to 20 mm.

  Uniformly dispersed at the molecular level here means that when the (B2) layered silicate is dispersed in the (B1) semi-aromatic polyamide polymer, each of the (B2) layered silicates has an average of 20 mm or more. The state where the interlayer distance is maintained. Here, the interlayer distance refers to the distance between the center of gravity of the (B2) layered silicate flat plate, and being dispersed means that (B2) each layered silicate has an average overlap of 5 layers or less. The laminate is in a state where 50% by weight or more, preferably 70% by weight or more of the laminate is dispersed without forming a lump in a state where the laminate is parallel or random, or a mixture of parallel and random. Specifically, (B) wide-angle X-ray diffraction measurement is performed on the specimen of the layered silicate-containing semi-aromatic polyamide composition, and the peak due to the thickness direction of the silicate layer has disappeared, or the transmission type This can be confirmed from the absence of a layered silicate mass by electron microscopic photography observation.

Preferred examples of the (B2) layered silicate used in the present invention include smectite groups such as montmorillonite, beidellite, saponite, hectorite, and saconite, vermiculite groups such as vermiculite, fluorine mica, muscovite, paragonite, phlogopite, black Examples include mica groups such as mica and lepidrite, brittle mica groups such as margarite, clintnite, and anandite, and chlorite groups such as donbasite, sudite, kukuite, clinochlore, chamosite, and nimite.
The above-exemplified (B2) layered silicate may be natural, synthesized or modified, and may be used alone or in combination of several kinds.

(B2) The layered silicate has a structure composed of a negatively charged layer containing silicate as a main component and a positive charge (ion) having ion exchange ability interposed between the layers.
The cation exchange capacity (CEC) of these (B2) layered silicates is preferably in the range of 50 to 200 meq / 100 g. The cation exchange capacity is measured by determining the adsorption amount of methylene blue. When the cation exchange capacity is less than 50 meq / 100 g, (B2) dispersion cleavage of the layered silicate may not proceed sufficiently. On the other hand, when the cation exchange capacity exceeds 200 meq / 100 g, the bonding force between the layers is strong, so that it may be difficult to cleave the (B2) layered silicate.

  In particular, montmorillonite obtained by purifying bentonite is most suitable for the present invention because of its cation exchange capacity and availability.

Montmorillonite is represented by the following formula and can be obtained by purifying a naturally occurring product. M _a Si ₄ (Al _{2 -a} Mg _a ) O ₁₀ (OH) ₂ .nH ₂ O (wherein M represents a cation of sodium, and a is 0.25 to 0.60. (The number of water molecules bonded to the ion-exchangeable cation can vary depending on conditions such as the cation species and humidity, and hence will be represented by nH ₂ O in the formulas hereinafter.)
In addition, montmorillonite also includes the same type of ion substitution products of magnesia montmorillonite, iron montmorillonite, and iron magnesia montmorillonite represented by the following formula group, and these may be used.
M _a Si ₄ (Al _1.67-a Mg _{0.5 + a} ) O ₁₀ (OH) ₂ .nH ₂ O
M _a Si ₄ (Fe _2−a ³⁺ Mg _a ) O ₁₀ (OH) ₂ .nH ₂ O
M _a Si ₄ (Fe _1.67-a ³⁺ Mg _{0.5 + a} ) O ₁₀ (OH) ₂ .nH ₂ O
(In the formula, M represents a cation of sodium, and a is 0.25 to 0.60.)

  Usually, montmorillonite has an ion exchange cation such as sodium or calcium between its layers, but the content ratio varies depending on the production area. In the present invention, it is necessary that the ion exchange cation between layers is replaced with sodium by ion exchange treatment or the like. Moreover, it is preferable to use the montmorillonite refine | purified by the hydrating process.

  In the present invention, for the purpose of further improving dispersibility, a layered silicate in which organic onium ions are inserted (intercalated) between the layers of the (B2) layered silicate is preferably used.

  The organic onium ion has a structure represented by ammonium ion, phosphonium ion, sulfonium ion, onium ion derived from a heteroaromatic ring, and the like. Of these, ammonium ions, phosphonium ions, and onium ions derived from a heteroaromatic ring are preferable from the viewpoint of availability and stability.

  Ammonium ions include alkylammonium such as hexylammonium, octylammonium, decylammonium, dodecylammonium, hexadecylammonium and octadecylammonium, and primary amine ammoniums having hydroxyl groups such as ethanolamine, p-aminophenol and m-aminophenol. Glycine, alanine, valine, leucine, isoleucine, phenylalanine, tyrosine, threonine, serine, proline, tryptophan, thyroxine, methionine, cystine, cysteine, asparagine, aspartic acid, glutamine, glutamic acid, lysine, arginine, histidine, etc. Ammonium, 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononane Primary ammoniums such as ammonium of an aminocarboxylic acid such as 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, dialkylammonium such as methyldodecylammonium, butyldodecylammonium, methyloctadecylammonium, diethanolamine, etc. Secondary ammonium having a hydroxyl group such as ammonium, trimethyl ammonium such as dimethyl octyl ammonium, dimethyl dodecyl ammonium, dimethyl hexadecyl ammonium, dimethyl octadecyl ammonium, dimethylphenyl ammonium, diphenyl dodecyl ammonium, diphenyl octadecyl ammonium, etc. Tertiary ammonium having a hydroxyl group such as tertiary ammonium having a phenyl group or triethanolamine Tertiary ammonium such as ammonium, quaternary ammonium having the same alkyl group such as tetraethylammonium, tetrabutylammonium, tetraoctylammonium, trimethyloctylammonium, trimethyldecylammonium, trimethyldodecylammonium, trimethyltetradecylammonium, trimethyl Hexadecyl ammonium, trimethyl octadecyl ammonium, trimethyl eicosanyl ammonium, trimethyl octadecenyl ammonium, trimethyl alkyl ammonium such as trimethyl octadecadienyl ammonium, triethyl dodecyl ammonium, triethyl tetradecyl ammonium, triethyl hexadecyl ammonium, triethyl octadecyl ammonium Trieti etc. Alkylammonium, tributyldodecylammonium, tributyltetradecylammonium, tributylhexadecylammonium, tributylalkylammonium such as tributyloctadecylammonium, dimethyldioctylammonium, dimethyldidecylammonium, dimethyldidodecylammonium, dimethylditetradecylammonium, dimethyldihexadecyl Ammonium, dimethyldioctadecylammonium, dimethyldioctadecenylammonium, dimethyldialkylammonium such as dimethyldioctadecadienylammonium, diethyldidodecylammonium, diethylditetradecylammonium, diethyldihexadecylammonium, diethyldioctadecylammonium, etc. Diethyldi Dibutyldialkylammonium such as rukylammonium, dibutyldidodecylammonium, dibutylditetradecylammonium, dibutyldihexadecylammonium, dibutyldioctadecylammonium, methylbenzyldialkylammonium such as methylbenzyldihexadecylammonium, dibenzyldihexadecylammonium, etc. Of dibenzyldialkylammonium, trioctylmethylammonium, tridodecylmethylammonium, tritetradecylmethylammonium and the like trialkylmethylammonium, trioctylethylammonium, tridodecylethylammonium and the like trialkylethylammonium, trioctylbutylammonium, tri Trialkylbutyl such as dodecylbutylammonium Examples include ions such as quaternary ammonium having an aromatic ring such as ammonium and trimethylbenzylammonium, and quaternary ammonium derived from an aromatic amine such as trimethylphenylammonium.

  Examples of phosphonium ions include tetrabutylphosphonium, tetraoctylphosphonium, trimethyldecylphosphonium, trimethyldodecylphosphonium, trimethylhexadecylphosphonium, trimethyloctadecylphosphonium, tributyldodecylphosphonium, tributylhexadecylphosphonium, alkyl quaternary phosphonium such as tributyloctadecylphosphonium, phenyl Quaternary phosphoniums such as phenylalkyl quaternary phosphonium such as trimethylphosphonium, phenyltributylphosphonium, diphenyldimethylphosphonium, triphenylmethylphosphonium, and tetraphenylphosphonium are onium ions derived from the heteroaromatic ring. Pyridinium, methylpyridinium, dimethyl Pyridinium, quinori Um, and ion such as isoquinolinium. The organic onium ion may be an ammonium ion or phosphonium ion to which ethylene oxide is added in order to impart hydrophilicity. You may use these in combination of multiple types.

  Among these organic onium ions, those having a relatively low molecular weight, for example, alkylammonium such as hexylammonium, octylammonium, decylammonium, 6-aminocaproic acid, 7-aminoheptanoic acid, 8-aminooctanoic acid, 9-aminononanoic acid Ammonium carboxylic acids such as 10-aminodecanoic acid, 11-aminoundecanoic acid, 12-aminododecanoic acid, valine, leucine, isoleucine, phenylalanine, tyrosine, threonine, serine, proline, hydroxyproline, tryptophan, methionine, cystine, Primary ammoniums such as ammonium of α-amino acids such as cysteine, aspartic acid, glutamic acid, asparagine, glutamine, lysine, arginine, histidine, pyridinium, methylpyri Preferred are oniums derived from heteroaromatic rings such as nium and dimethylpyridinium, more preferably amino such as 8-aminooctanoic acid, 9-aminononanoic acid, 10-aminodecanoic acid, 11-aminoundecanoic acid, and 12-aminododecanoic acid. Ions of carboxylic acids such as ammonium and pyridinium are more preferably ammonium ions of aminocarboxylic acids such as 10-aminodecanoic acid, 11-aminoundecanoic acid and 12-aminododecanoic acid.

  The amount of the organic onium ions is preferably in the range of 0.8 to 2.0 equivalents and in the range of 0.9 to 1.3 equivalents with respect to the cation exchange capacity of the (B2) layered silicate. More preferred. If this amount is less than 0.8 equivalents, the dispersibility in the (B1) semi-aromatic polyamide polymer may be reduced, and if it exceeds 2.0 equivalents, the free compounds derived from the onium ions become prominent. This may cause a decrease in thermal stability at the time of molding, generation of scouring, fuming, mold contamination, odor and the like.

  Insertion of organic onium ions between layers of (B2) layered silicate is easy by adding onium ions or a solution containing this to the suspension of layered silicate (B2) and performing cation exchange. To be achieved. (B2) Introduction of an organic structure between layers of a negatively charged silicate layer by introduction of the onium ion between layers, which is simply performed by contact between the (B2) layered silicate and the organic onium ion in a solvent-containing solution Thus, the penetration of the polyamide raw material into the interlayer and the progress of the polymerization are promoted, and the uniform dispersion of the (B2) layered silicate into the (B1) semi-aromatic polyamide polymer is achieved.

  The dispersion medium used when the organic onium ions are inserted between the layers of the (B2) layered silicate is appropriately determined depending on the types of the (B2) layered silicate, the organic onium ion, and the (B1) semiaromatic polyamide polymer. However, it is preferable that the layered silicate is uniformly dispersed and has good compatibility with the organic onium ion and the semi-aromatic polyamide polymer.

  As a dispersion medium, water, methanol, ethanol, propanol, isopropanol, ethylene glycol, diethylene glycol, 1,4-butanediol, glycerin, dimethyl sulfoxide, dimethylformamide, acetic acid, formic acid, pyridine, aniline, phenol, nitrobenzene, acetonitrile, acetone , Methyl ethyl ketone, chloroform, carbon disulfide, propylene carbonate, 2-methoxyethanol, carbon tetrachloride, n-hexane, caprolactam, dodecane lactam, 6-aminocaproic acid, 12-aminododecanoic acid and the like. One type or two or more types of dispersion media can be used. Among these, it is preferable to use water, methanol, ethanol and / or caprolactam.

  The addition amount of (B2) layered silicate in the present invention is 0.1 to 30 parts by weight and 0.5 to 10 parts by weight with respect to 100 parts by weight of (B1) semiaromatic polyamide polymer. Is preferred. When the amount of (B2) layered silicate added is less than 0.1 parts by weight relative to 100 parts by weight of (B1) semi-aromatic polyamide polymer, the chemical solution permeation-preventing property is insufficient, and (B1) semi-aromatic When the amount exceeds 30 parts by weight with respect to 100 parts by weight of the group polyamide polymer, molding of the laminated structure becomes difficult, and mechanical properties such as low-temperature impact resistance and tensile elongation decrease, which is not preferable.

  (B1) For the method of uniformly dispersing the (B2) layered silicate in the semi-aromatic polyamide polymer, (i) (B2) contacting the layered silicate with the organic onium ion and spreading the layer in advance to form a monomer between the layers After facilitating the incorporation of molecules, (B1) a method of polymerizing by mixing with a polyamide raw material monomer of a semi-aromatic polyamide polymer (see JP-A-62-74957), (ii) (B2) layered in a dispersion medium (B1) A method of mixing or kneading a layered silicate complex in which silicate is uniformly dispersed in a state swollen by organic onium ions with (B1) a semi-aromatic polyamide polymer (see JP-A-2-305828). iii) (B2) a layered silicate-containing semi-aromatic polyamide composition containing the layered silicate at a high concentration is prepared in advance by the above method, and (B2) the layered silicate-containing semi-aromatic polyamide is prepared. Free composition and layered silicate (B1) can be applied a method of mixing the semi-aromatic polyamide polymer.

  The (B) layered silicate-containing semi-aromatic polyamide composition may contain another polyamide-based resin or other thermoplastic resin together with the (B1) semi-aromatic polyamide polymer. Examples of the other polyamide-based resin or other thermoplastic resin include the same resins as those in the case of the (A) aliphatic polyamide. Furthermore, it may be a mixture with the (A) aliphatic polyamide used in the present invention. The content of the (B) layered silicate-containing semi-aromatic polyamide composition in the mixture is preferably 80% by weight or more.

  Furthermore, the (B) layered silicate-containing semi-aromatic polyamide composition used in the present invention is optionally provided with an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, and an inorganic filling. Materials, antistatic agents, flame retardants, crystallization accelerators, plasticizers, colorants, lubricants, impact modifiers, and the like may be added.

The (B) layered silicate-containing semi-aromatic polyamide composition used in the present invention preferably has a relative viscosity measured in accordance with JIS K-6920 of 1.5 to 4.0, more preferably. It is 1.8-3.5, More preferably, it is 2.0-3.0. If it is less than the above value, the mechanical properties of the resulting laminated structure may be insufficient, and if it exceeds the above value, the extrusion pressure and torque become too high, producing a laminated structure. It can be difficult.

  The laminated structure according to the present invention comprises (A) a layer made of an aliphatic polyamide, (a) a diamine unit containing 60 mol% or more of xylylenediamine and / or naphthalenedimethylamine units with respect to all diamine units, The dicarboxylic acid unit is composed of a dicarboxylic acid unit containing 60 mol% or more of an aliphatic dicarboxylic acid unit having 8 to 13 carbon atoms. It comprises at least two layers, including (b) a layer (b) composed of (B) a layered silicate-containing semi-aromatic polyamide composition in which 0.1 to 30 parts by weight of layered silicate is uniformly dispersed.

  In the laminated structure of the present invention, as a preferred embodiment, (A) the layer (a) made of aliphatic polyamide is disposed in the outermost layer of the laminated structure. (A) When the (a) layer made of aliphatic polyamide is disposed in the outermost layer, a laminated structure having excellent chemical resistance and flexibility can be obtained.

  In the laminated structure of the present invention, it is essential to include the (B) layer comprising the (B) layered silicate-containing semi-aromatic polyamide composition, and the (A) comprising the aliphatic polyamide (A) in the laminated structure. More preferably, it is arranged inside the layer. If the (B) layer which consists of (B) layered silicate containing semi-aromatic polyamide composition is not included, the chemical | medical solution permeation-proof property of a laminated structure will fall. As a more preferred embodiment, (B) the layer (B) made of the layered silicate-containing semi-aromatic polyamide composition is disposed in the innermost layer.

  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, applications, etc. The thickness is determined in consideration of properties such as chemical solution permeation prevention, low-temperature impact resistance, and flexibility of the laminated structure. In general, the thickness of the (a) layer and the (b) layer is the entire laminated structure. It is preferable that it is 3-90% with respect to the thickness of each. In consideration of the chemical solution permeation prevention property, the thickness of the layer (b) is more preferably 5 to 80%, and still more preferably 10 to 50% with respect to the thickness of the entire laminated structure.

  Further, the total number of layers in the laminated structure of the present invention includes (A) a layer composed of an aliphatic polyamide (B) and (b) a layer (b) composed of a layered silicate-containing semi-aromatic polyamide composition. As long as it has at least two layers, it is not particularly limited. 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. It may have one layer or two or more layers.

  Although the number of layers of the laminated structure of the present invention is 2 or more, it is 8 layers or less, preferably 2 to 7 layers as judged from the mechanism of the structure production apparatus.

  In the laminated structure in the present invention, (B) the layer (b) made of the layered silicate-containing semi-aromatic polyamide composition is arranged on the inner side with respect to the (a) layer made of (A) the aliphatic polyamide. The laminated structure further includes (C) a layer (c) made of a fluorine-containing polymer in which a functional group having reactivity with an amino group is introduced into the molecular chain, and the layer (c) A laminated structure having a layer structure disposed in the inner layer is also a preferred embodiment.

The fluorine-containing polymer in which a functional group having reactivity to an amino group (C) used in the present invention is introduced into a molecular chain has a functional group having reactivity in the molecular structure. (Referred to below as (C) fluorine-containing polymer).
(C) The fluorine-containing polymer 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. For example, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene / perfluoroalkyl ether copolymer (PFA), tetrafluoro Ethylene / hexafluoropropylene copolymer (FEP), ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / tetrafluoroethylene / hexafluoropropylene copolymer, vinylidene fluoride / tetrafluoroethylene copolymer, fluoride Vinylidene / hexafluoropropylene copolymer, vinylidene fluoride / pentafluoropropylene copolymer, tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (THV), vinyl fluoride Ridene / pentafluoropropylene / tetrafluoroethylene copolymer, vinylidene fluoride / perfluoroalkyl vinyl ether / tetrafluoroethylene copolymer, ethylene / chlorotrifluoroethylene copolymer (ECTFE), vinylidene fluoride / chlorotrifluoroethylene Copolymers and mixtures thereof may be used.

  Among the fluorine-containing polymers exemplified above (C), a fluorine-containing polymer containing tetrafluoroethylene units as essential components in terms of heat resistance and chemical resistance, and in terms of molding, vinylidene fluoride units are used. A fluorine-containing polymer as an essential component is preferable, and ethylene / tetrafluoroethylene copolymer (ETFE), polyvinylidene fluoride (PVDF), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (THV) are more preferred. preferable.

  The ethylene / tetrafluoroethylene copolymer (hereinafter sometimes referred to as ETFE) is a polymerized unit based on ethylene (hereinafter sometimes referred to as E) and a polymerized unit based on tetrafluoroethylene (hereinafter referred to as TFE). The polymerization ratio (molar ratio) is preferably 80/20 to 20/80, more preferably 70/30 to 30/70, and still more preferably 60/40. ~ 40/60.

  When the molar ratio of (polymerized unit based on E) / (polymerized unit based on TFE) is extremely large, the heat resistance, weather resistance, chemical resistance, chemical solution permeation prevention, etc. of the ETFE may be reduced. If the molar ratio is extremely small, the mechanical strength, melt moldability, etc. may decrease. Within this range, the ETFE is excellent in heat resistance, weather resistance, chemical resistance, chemical penetration prevention, mechanical strength, melt moldability, and the like.

(C) In addition to the polymer units based on E and TFE, the fluorine-containing polymer may contain one or more other monomers as long as the essential characteristics are not impaired.
Other monomers include α-olefins such as propylene and butene, CH ₂ ═CX (CF ₂ ) _n Y (where X and Y are independently hydrogen or fluorine atoms, n is an integer of 2 to 8) ), A fluoroolefin having a hydrogen atom in an unsaturated group, such as vinylidene fluoride (VDF), vinyl fluoride (VF), trifluoroethylene, hexafluoroisobutylene (HFIB), and hexafluoropropylene. (HFP), chlorotrifluoroethylene (CTFE), perfluoro (methyl vinyl ether) (PMVE), perfluoro (ethyl vinyl ether) (PEVE), perfluoro (propyl vinyl ether) (PPVE), perfluoro (butyl vinyl ether) (PBVE) ) And other perfluoro (alkyl vinyl ether) (P VE) fluoroolefins having no hydrogen atom in an unsaturated group (excluding TFE), methyl vinyl ether (MVE), ethyl vinyl ether (EVE), butyl vinyl ether (BVE), isobutyl vinyl ether (IBVE), cyclo Vinyl ethers such as hexyl vinyl ether (CHVE), vinyl chloride, vinylidene chloride, vinyl acetate, vinyl chloroacetate, vinyl lactate, vinyl butyrate, vinyl pivalate, vinyl benzoate, vinyl crotonate vinyl esters, alkyl (meth) acrylates , (Fluoroalkyl) acrylate, (fluoroalkyl) methacrylate and the like are preferable. One of these other monomers may be used alone, or two or more thereof may be used in combination.

(C) In the fluorine-containing polymer, it is preferable to use a compound represented by the general formula CH ₂ = CX (CF ₂ ) _n Y (hereinafter referred to as FAE). The content of the polymerization units based on FAE is preferably 0.01 to 20 mol%, more preferably 0.1 to 15 mol% in the (C) fluorine-containing polymer. More preferably, it is 10 mol%. When the content of FAE is less than the above value, crack resistance may be reduced, or a destructive phenomenon may easily occur under stress. When the content exceeds the above value, mechanical strength may be reduced. There is.

FAE, as described above, (wherein, X, Y are each independently a hydrogen atom or a fluorine atom, n is an integer from 2-8.) General formula _{CH 2 = CX (CF 2)} n Y in It is a compound represented. When n in the formula is less than 2, modification of the fluorine-containing polymer (for example, suppression of cracking of the molded product or molded product) may not be sufficiently performed. If n exceeds 8, it may be disadvantageous in terms of polymerization reactivity.

The _{FAE, 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 .
Among these, a compound represented by CH ₂ ═CH (CF ₂ ) _n Y is more preferable. In this case, n in the formula is n = 2 to 4, and (C) the fluorine-containing polymer is It is more preferable since both the chemical solution permeation preventing property and the crack resistance are compatible.

  The vinylidene fluoride copolymer is a copolymer comprising a polymer unit based on vinylidene fluoride and at least one fluorine-containing monomer copolymerizable therewith. Examples of other monomers that can be copolymerized with polymerized units based on vinylidene fluoride include tetrafluoroethylene (TFE), hexafluoropropylene (HFP), chlorotrifluoroethylene (CTFE), hexafluoroisobutylene, and hexafluoro. Acetone, pentafluoropropylene, trifluoroethylene, vinyl fluoride, fluoro (alkyl vinyl ether), chlorotrifluoroethylene and the like are exemplified. In the vinylidene fluoride-based copolymer, the amount of polymerized units based on vinylidene fluoride is at least 30 mol% or more of all polymerized units. Tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (THV) can be mentioned as a preferred vinylidene fluoride copolymer.

  The (C) fluorine-containing polymer 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 it is started by, for example, organic or inorganic radical polymerization initiator, heat, light or ionizing radiation.

(C) There is no restriction | limiting in particular in the manufacturing method of a fluorine-containing polymer, 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.
The polymerization can be carried out batchwise or continuously using a single tank or multi-tank type stirring polymerization apparatus or tube polymerization apparatus.

As a radical polymerization initiator, the decomposition temperature with a half-life of 10 hours is preferably 0 ° C to 100 ° C, and more preferably 20 to 90 ° C. 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 Pentenic acid) and other azo compounds, hydrogen peroxide, tert-butyl hydroperoxide, cumene hydroperoxide and other hydroperoxides, di-tert-butyl peroxide, dicumyl peroxide and other dialkyl peroxides, and acetyl peroxide , Isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide, Non-fluorine type diacyl peroxide such as uroyl peroxide, ketone peroxide such as methyl ethyl ketone peroxide, cyclohexanone peroxide, peroxydicarbonate such as diisopropylperoxydicarbonate, tert-butylperoxypivalate, tert-butylperoxide Peroxyesters such as oxyisobutyrate and tert-butylperoxyacetate, hydroperoxides such as tert-butylhydroperoxide, (Z (CF ₂ ) _p COO) ₂ (where Z is a hydrogen atom, a fluorine atom Or, it is a chlorine atom, and p is an integer of 1 to 10.) Fluorine-containing diacyl peroxide such as a compound represented by formula (1), inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate. .

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

  It does not specifically limit about polymerization conditions, It is preferable that polymerization temperature is 0 degreeC-100 degreeC, and it is more preferable that it is 20-90 degreeC. In order to avoid a decrease in heat resistance due to ethylene-ethylene chain formation in the polymer, it is generally preferable that the temperature is low. The polymerization pressure is appropriately determined according to other polymerization conditions such as the type, amount and vapor pressure of the solvent used, and the polymerization temperature, but is preferably 0.1 to 10 MPa, and preferably 0.5 to 3 MPa. More preferred. The polymerization time is preferably 1 to 30 hours.

  The molecular weight of the (C) fluorine-containing polymer 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.

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

In addition, (C) the fluorine-containing polymer can adjust the melting point and glass transition point of the polymer by selecting the type and composition ratio of the fluorine-containing monomer and other monomers.
The melting point of the (C) fluorine-containing polymer is appropriately selected depending on the purpose, application, and method of use, and is coextruded with the (A) aliphatic polyamide, (B) layered silicate-containing semi-aromatic polyamide composition, etc. When it does, it is preferable that it is close to the molding temperature of the polyamide. Therefore, it is preferable to optimize the melting point of the (C) fluorine-containing polymer by appropriately adjusting the ratio of the fluorine-containing monomer and other monomers and the functional group-containing monomer described later.

  The (C) fluorine-containing polymer of the present invention has a functional group having reactivity with an amino group in the molecular structure, and the functional group is the molecular end of (C) the fluorine-containing polymer or It may be contained in either 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 (C) fluorine-containing polymer. The type and content of the functional group are appropriately determined according to the type, shape, application, required interlayer adhesion, adhesion method, functional group introduction method, etc. of the other material laminated to the (C) fluorine-containing polymer. Is done.

  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 carboxylic acid halide groups. At least one selected from the group consisting of: In particular, at least one selected from a carboxyl group, an acid anhydride group or a carboxylate, a hydroxyl group, an epoxy group, a carbonate group, and a carboxylic acid halide group is preferable.

  (C) As a method of introducing a functional group having reactivity into the fluorine-containing polymer, (i) (C) a copolymerizable monomer having a functional group is used during the polymerization of the fluorine-containing polymer. A method of copolymerization, (ii) a method of introducing a functional group at the molecular terminal of a fluorine-containing polymer during 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 conversion to 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 (C) fluorine-containing polymer 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) (C) 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, At least one functional group-containing monomer selected from a carboxyl group, an acid anhydride group or carboxylate, a hydroxyl group, a sulfo or sulfonate, an epoxy group, and a cyano group is used as a polymerization monomer. 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, glycidyl acrylate, glycidyl methacrylate, epoxy group-containing monomers such as glycidyl ether, Acrylic acid hydroxyethyl, hydroxyethyl methacrylate, acrylic acid hydroxypropyl, hydroxypropyl methacrylate, hydroxyl group-containing monomers such as hydroxyalkyl vinyl ether.

As specific examples of the functional group-containing fluorine-containing monomer,
CF ₂ = CFOCF ₂ CF ₂ COOH
CF ₂ = CFO (CF ₂ ) ₃ COOH
CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOH
CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COOH
CF ₂ = CFCF ₂ COOH
CF ₂ = CFCF ₂ CF ₂ COOH
CF ₂ = CFOCF ₂ CF ₂ COONH ₄
CF ₂ = CFO (CF ₂ ) ₃ COONa
CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COONH ₄
CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ COONa
CF ₂ = CFCF ₂ COONH ₄
CF ₂ = CFCF ₂ CF ₂ COOZn
CF ₂ = CFOCF ₂ CF ₂ CH ₂ OH
_{CF 2 = CFO (CF 2)} 3 CH 2 OH
CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CH ₂ OH
CF ₂ = CFCF ₂ CH ₂ OH
CF ₂ = CFCF ₂ CF ₂ CH ₂ OH
CF ₂ = CFOCF ₂ CF ₂ SO ₃ H
CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ SO ₃ H
CF ₂ = CFOCF ₂ CF (CF ₃ ) OCF ₂ CF ₂ CN
CF ₂ = CFCF ₂ OCF ₂ CF ₂ CF ₂ COOH
CF ₂ = CFCF ₂ OCCFCF (CF ₃ ) COOH
CF ₂ = CFCF ₂ OCF ₂ CF ₂ CF ₂ COONH ₄
CF ₂ = CFCF ₂ OCCFCF (CF ₃ ) COONH ₄
CF ₂ = CFCF ₂ OCF ₂ CF ₂ CF ₂ COONa
CF ₂ = CFCF ₂ OCCFCF (CF ₃ ) COOZn
CF ₂ = CFCF ₂ OCF ₂ CF ₂ CF ₂ CH ₂ OH
CF ₂ = CFCF ₂ OCCFCF (CF ₃ ) CH ₂ OH
CF ₂ = CFCF ₂ OCF ₂ CF ₂ CF ₂ SO ₃ H
CF ₂ = CFCF ₂ OCF ₂ CF ₂ CF ₂ CN
CH ₂ = CFCF ₂ CF ₂ CH ₂ COOH
CH ₂ = CFCF ₂ CF ₂ COOH
_{CH 2 = CF (CF 2)} 8 COOH
_{CH 2 = CF (CF 2)} 4 CH 2 COOH
_{CH 2 = CFCF 2 OCF (CF} 3) COOH
_{CH 2 = CFCF 2 OCF (CF} 3) CF 2 OCF (CF 3) COOH
CH ₂ = CFCF ₂ CF ₂ CH ₂ COONH ₄
CH ₂ = CFCF ₂ CF ₂ COONa
_{CH 2 = CF (CF 2)} 4 CH 2 COOZn
CH ₂ = CFCF ₂ OCF (CF ₃ ) COONH _{4
CH 2 = CFCF 2 OCF (CF} 3) CF 2 OCF (CF 3) COONH 4
_{CH 2 = CFCF 2 OCF (CF} 3) CF 2 OCF (CF 3) COOZn
CH ₂ = CFCF ₂ CF ₂ CH ₂ CH ₂ OH
CH ₂ = CFCF ₂ CF ₂ CH ₂ OH
_{CH 2 = CF (CF 2)} 8 CH 2 CH 2 OH
_{CH 2 = CFCF 2 OCF (CF} 3) CH 2 OH
_{CH 2 = CFCF 2 OCF (CF} 3) CF 2 OCF (CF 3) CH 2 OH
CH ₂ = CHCF ₂ CF ₂ CH ₂ COOH
_{CH 2 = CH (CF 2)} 2 CH 2 CH 2 COOH
_{CH 2 = CH (CF 2)} 4 CH 2 CH 2 COOH
_{CH 2 = CH (CF 2)} 6 CH 2 COOH
CH ₂ = CH (CF ₂ ) ₄ CH ₂ COONH _{4
CH 2 = CH (CF 2)} 4 CH 2 CH 2 COONa
_{CH 2 = CH (CF 2)} 6 CH 2 COOZn
CH ₂ = CHCF ₂ CF ₂ CH ₂ CH ₂ OH
_{CH 2 = CH (CF 2)} 4 CH 2 CH 2 CH 2 OH
_{CH 2 = CH (CF 2)} 6 CH 2 CH 2 OH
Etc. are exemplified.

  (C) The content of the functional group-containing monomer in the fluorine-containing polymer is preferably 0.05 to 20 mol%, more preferably 0.05 to 10 mol%, in all the polymerized units. More preferably, it is 0.1-5 mol%. When the content of the functional group-containing monomer is less than 0.05 mol%, it is difficult to obtain sufficient interlayer adhesion, and the interlayer adhesion may be lowered depending on the use environment conditions. Also, if the content exceeds 20 mol%, the heat resistance is lowered, and peeling, coloring, foaming, elution, etc. occur due to poor adhesion during processing at high temperature, coloring and foaming, and decomposition during use at high temperature. It may be easy to do. Moreover, as long as the said content is satisfy | filled, you may be a mixture of the fluorine-containing polymer in which the functional group was introduce | transduced, and the fluorine-containing polymer in which the functional group was not introduce | transduced.

  (Ii) In the method of introducing a functional group 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. As the functional group introduced at the terminal, a carbonate group or a carboxylic acid halide group is preferable.

(C) The carbonate group introduced as a terminal group of the fluorine-containing polymer is generally a group having a —OC (═O) O— bond, and specifically, —OC (═O) O—. R group [R is a hydrogen atom, an organic group (for example, a C1-C20 alkyl group, a C2-C20 alkyl group having an ether bond, etc.) or a group I, II, or VII element. ]. Examples of carbonate _{groups, -OC (= O) OCH 3} , -OC (= O) OC 3 H-OC (= O) OC 8 H 17, -OC (= O) OCH 2 CH 2 OCH 2 CH 3 , etc. Is preferred. The carboxylic acid halide group specifically has a structure of —COY [Y is a halogen element], and examples thereof include —COF and —COCl.

  In order to introduce a carbonate group at the molecular terminal of the polymer, various methods using a polymerization initiator or a chain transfer agent can be employed. However, a method using peroxide, particularly peroxycarbonate, as a polymerization initiator is available. It can be preferably employed in terms of quality such as economy, heat resistance and chemical resistance. Further, it is preferable to use peroxycarbonate because the polymerization temperature can be lowered and the side reaction is not involved in the initiation reaction.

  Various methods can be employed to introduce a carboxylic acid halide 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 for thermal decomposition (desorption). Carbonic acid).

  As peroxycarbonate, diisopropyl peroxycarbonate, di-n-isopropyl peroxycarbonate, t-butyl peroxyisopropyl carbonate, t-butyl peroxymethacryloyloxyethyl carbonate, bis (4-t-butylcyclohexyl) peroxy Dicarbonate, di-2-ethylhexyl peroxydicarbonate and the like are preferable.

  The amount of peroxycarbonate used varies depending on the type (composition, etc.) of the target polymer, the molecular weight, the polymerization conditions, and the type of initiator used, but is 0.1% relative to 100 parts by weight of the total polymer obtained by polymerization. It is preferable that it is 05-20 weight part, and it is more preferable that it is 0.1-10 weight part. The carbonate group content at the molecular end of the polymer can be controlled by adjusting the polymerization conditions. When the amount of the polymerization initiator used is large, it may be difficult to control the polymerization rate, and when the amount used is small, the polymerization rate may be slow. The addition method of a polymerization initiator is not specifically limited, You may add collectively at the time of superposition | polymerization, and may add continuously during superposition | polymerization. The addition method is appropriately selected depending on the decomposition reactivity of the polymerization initiator and the polymerization temperature.

(C) The number of terminal functional groups with respect to 10 ⁶ main chain carbon atoms in the fluorine-containing polymer is preferably 150 to 3000, more preferably 200 to 2000, and still more preferably 300 to 1000. is there. When the number of functional groups is less than 150, it is difficult to obtain sufficient interlayer adhesion, and the interlayer adhesion may be lowered depending on the use environment conditions. Also, if the number of functional groups exceeds 3000, the heat resistance will be reduced, resulting in poor adhesion, coloring, foaming during processing at high temperatures, peeling, coloring, foaming, elution, etc. due to decomposition during use at high temperatures. It may be easy. 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 (C) fluorine-containing polymer 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 introduced with a functional group (C) is itself a heat-resistant, water-resistant, low-friction, chemical-resistant, weather-resistant, antifouling property specific 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, surface treatment is performed on various materials whose interlayer adhesion with the (A) aliphatic polyamide or the like is insufficient or impossible in the laminated structure by including the functional group in the molecular chain. Excellent interlaminar adhesion with other substrates can be imparted directly without performing special treatment such as coating with an adhesive resin.

  The (C) fluorine-containing polymer 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 blended. 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 designability, preventing static electricity, improving moldability Etc. are possible.

  Other thermoplastic resins include polymetaxylylene adipamide (polyamide MXD6), polybis (4-aminocyclohexyl) other than (A) aliphatic polyamide and (B1) semi-aromatic polyamide polymer defined in the present invention. ) Methane dodecamide (polyamide PACM12), polybis (4-aminocyclohexyl) methane terephthalamide (polyamide PACMT), polybis (4-aminocyclohexyl) methane isophthalamide (polyamide PACMI), polybis (3-methyl-4-amino) (Cyclohexyl) methane dodecamide (polyamide dimethyl PACM12), polyisophorone adipamide (polyamide IPD6), polyisophorone terephthalamide (polyamide IPDT), polyhexamethylene terephthalamide (polyamide 6T), poly Xamethylene isophthalamide (polyamide 6I), polytrimethylhexamethylene terephthalamide (polyamide TMHT), polynonamethylene terephthalamide (polyamide 9T), polynonamethylene isophthalamide (polyamide 9I), polynonamethylene naphthalamide (Polyamide 9N), polynonamethylene hexahydroterephthalamide (polyamide 9T (H)), polydecamethylene terephthalamide (polyamide 10T), polydecamethylene isophthalamide (polyamide 10I), polydecamethylene naphthalamide (polyamide) 10N), polydecamethylenehexahydroterephthalamide (polyamide 10T (H)), polyundecamethylene terephthalamide (polyamide 11T), polyundecamethylene isophthalamide (polyamide 11I), Riundecamethylene Naphthalamide (Polyamide 11N), Polyundecamethylene Hexahydroterephthalamide (Polyamide 11T (H)), Polydodecamethylene terephthalamide (Polyamide 12T), Polydodecamethylene isophthalamide (Polyamide 12I) Polydodecamethylene naphthalamide (polyamide 12N), polydodecamethylene hexahydroterephthalamide (polyamide 12T (H)), copolymers using several kinds of these polyamide raw material monomers, and the like.

  In addition, fluorine-containing polymers other than those specified in the present invention (here, other than those specified in the present invention refers to fluorine-containing polymers that do not contain a functional group having reactivity with amino groups). .) As polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), ethylene / tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE). ), Tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (TFE / HFP / VDF, THV), tetrafluoroethylene / fluoro ( Alkyl vinyl ether) copolymer (PF ), And the like.

  Furthermore, 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), ethylene / propylene Polymer (EPR), ethylene / butene copolymer (EBR), ethylene / vinyl acetate copolymer (EVA), saponified ethylene / vinyl acetate copolymer (EVOH), ethylene / acrylic acid copolymer (EAA) Polyolefins such as ethylene / methacrylic acid copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), ethylene / ethyl acrylate copolymer (EEA) Resin and acrylic acid, methacrylic acid, maleic acid, Malic 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- Carboxyl groups such as dicarboxylic acids and their metal salts (Na, Zn, K, Ca, Mg), maleic anhydride, itaconic anhydride, citraconic anhydride, endobicyclo- [2.2.1] -5-heptene-2 The above polyolefin resin containing functional groups such as epoxy groups such as acid anhydride groups such as 1,3-dicarboxylic acid anhydride, glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl citraconic acid, etc. , Polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polybutylene naphthalate (PBN), polyethylene naphthalate (PEN), polyester resins such as liquid crystal polyester (LCP), polyacetal (POM), polyphenylene Polyether resins such as oxide (PPO), polysulfone resins such as polysulfone (PSF) and polyethersulfone (PES), polythioether resins such as polyphenylene sulfide (PPS) and polythioether sulfone (PTES), polyethers Polyketone resins such as ether ketone (PEEK) and polyallyl ether ketone (PAEK), polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / s Polynitrile resins such as tyrene copolymer, acrylonitrile / budadiene / styrene copolymer (ABS), methacrylonitrile / styrene / butadiene copolymer (MBS), polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA) ), Etc., polyvinyl ester resins such as polyvinyl acetate (PVAc), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymer, vinylidene chloride / methyl acrylate Polyvinyl chloride resins such as polymers, cellulose resins such as cellulose acetate and cellulose butyrate, polycarbonate resins such as polycarbonate (PC), polyimides such as thermoplastic polyimide (PI), polyamideimide (PAI), and polyetherimide Resins, thermoplastic polyurethane resins, polyamide elastomers, polyurethane elastomers, and polyester elastomers.

  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 the metal-based material include aluminum, iron, copper, nickel, gold, silver, titanium, molybdenum, magnesium, manganese, lead, tin, chromium, beryllium, tungsten, cobalt, and other metals and metal compounds, and two or more of these. Examples include alloy steels such as stainless steel, aluminum alloys, copper alloys such as brass and bronze, and alloys such as nickel alloys.

  Further, 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 chemical resistance and the chemical liquid permeation preventive property are excellent. At the same time, when used in a chemical solution transport tube or hose, it is possible to prevent the chemical solution from igniting sparks generated by internal friction of the chemical solution circulating in the pipe or friction with the tube wall. 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. As a result, it is possible to prevent explosion due to static electricity generated when a chemical solution 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.

  As the particulate filler, carbon black, graphite or the like can be preferably used. As the flaky filler, aluminum flakes, nickel flakes, nickel-coated mica and the like can be suitably used. As the fibrous filler, carbon fibers, carbon-coated ceramic fibers, carbon whiskers, carbon nanotubes, aluminum fibers, copper fibers, brass fibers, stainless fibers, and other metal fibers can be preferably used. Among these, carbon nanotubes and carbon black are particularly preferable.

  Carbon nanotubes are what are referred to as 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, An essentially cylindrical fibril in which each layer and the hollow region are arranged substantially concentrically around the cylindrical axis of the fibril. Furthermore, the regularly arranged carbon atoms in the outer region are preferably graphite-like, and the diameter of the hollow region is preferably 2 to 20 nm. The outer diameter of the carbon nanotube is preferably 3.5 to 70 nm, more preferably 4 to 60 nm. When the outer diameter is less than 3.5 nm, the dispersibility in the resin may be inferior, and when it exceeds 70 nm, the resulting resin molded article may have poor conductivity. 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 commonly used for imparting electrical conductivity. Preferred carbon blacks include acetylene black obtained by incomplete combustion of acetylene gas, and furnace type Examples include, but are not limited to, ketjen black, oil black, naphthalene black, thermal black, lamp black, channel black, roll black, and disk black produced by complete combustion. Among these, acetylene black and furnace black (Ketjen black) are particularly preferably used.

Carbon black is produced in various carbon powders having different characteristics such as particle diameter, surface area, DBP oil absorption, ash content and the like. Although there is no restriction | limiting in the characteristic of this carbon black, What has a favorable chain structure and a large aggregation density is preferable. A large amount of carbon black is not preferable in terms of impact resistance, and from the viewpoint of obtaining excellent electrical conductivity with a smaller amount, the average particle size is preferably 500 nm or less, more preferably 5 to 100 nm, more preferably from 10 to 70 nm, also the surface area (BET method) is preferably ^{10 m} 2 / g or more, more preferably 300 meters ² / g or more, to be 500 to 1500 ² / g Further, the DBP (dibutyl phthalate) oil absorption is preferably 50 ml / 100 g or more, more preferably 100 ml / 100 g or more, and further preferably 300 ml / 100 g or more. The ash content is preferably 0.5% by weight or less, and more preferably 0.3% by weight or less. The DBP oil absorption here is a value measured by a method defined in ASTM D-2414. Carbon black preferably has a volatile content of less than 1.0% by weight.
These conductive fillers may be surface-treated with a titanate-based, aluminum-based or silane-based surface treatment agent. It is also possible to use a granulated product to improve melt kneading workability.

The blending amount of the conductive filler varies depending on the type of the conductive filler to be used, and thus cannot be specified unconditionally. However, from the viewpoint of balance between conductivity, fluidity, mechanical strength, etc., the amount of the thermoplastic resin component is 100 parts by weight. On the other hand, generally 1 to 30 parts by weight is preferably selected.
In addition, such a conductive filler preferably has a surface resistivity value of 10 ⁸ Ω / square or less, particularly 10 ⁶ Ω / square or less, in order to obtain sufficient antistatic performance. However, the blending of the conductive filler tends to cause deterioration of strength and fluidity. Therefore, if the target conductivity level is obtained, it is desirable that the amount of the conductive filler is as small as possible.

  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 various shapes such as a hose shape, and any melt molding method is used, including co-extrusion molding methods (T-die extrusion, inflation extrusion, blow molding, profile extrusion, extrusion coating, etc.), laminated injection molding methods, etc. The

  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 or hoses for automobile fuel pipes, automobile radiator tubes or hoses, brake tubes or hoses, tubes or hoses for chemical solutions such as air conditioner tubes or hoses, tubes for electric wire coating materials, optical fiber coating materials, hoses, etc. Films, agricultural films, linings, architectural interior materials (wallpaper, etc.), films such as laminated steel sheets, sheets, automotive radiator tanks, chemical bottles, chemical tanks, bags, chemical containers, tanks such as gasoline tanks, etc. It is done. Among them, it is useful as a chemical solution transport tube or hose.

  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 fluids, brake fluids for extremely cold regions, silicone oil brake fluids, mineral oil brake fluids, power steering oils, hydrogen sulfide oils, window washer fluids, engine coolants, urea solutions, pharmaceutical agents, inks and paints. .

  Hereinafter, the chemical solution transfer tube or hose which is a preferred embodiment will be described in detail.

  Specific examples of the chemical transport tube or hose include fuel such as feed tube or hose, return tube or hose, evaporation tube or hose, fuel filler tube or hose, ORVR tube or hose, reserve tube or hose, vent tube or hose, etc. Tube or hose, oil tube or hose, oil drilling tube or hose, brake tube or hose, tube or hose for window washer fluid, radiator tube or hose, cooler tube or hose for cooling water, refrigerant, etc., air conditioner refrigerant tube or hose Heater tubes or hoses, load heating tubes or hoses, floor heating tubes or hoses, infrastructure supply tubes or hoses, fire extinguishers and fire extinguishing equipment tubes or Hoses, medical cooling equipment tubes or hoses, ink, paint spraying tube or hose, other chemical tube or hose and the like. Particularly, it is suitable as a fuel tube or a hose.

  As a method for manufacturing a chemical solution transporting tube or hose, using an extruder corresponding to the number of layers or the number of materials, melt extrusion, a method of simultaneously laminating inside or outside a die (coextrusion method), or once, A single-layer tube or hose or a laminated tube or hose manufactured by the above method is manufactured in advance, and an adhesive is used on the outside sequentially, if necessary, and the resin is integrated and laminated (coating Law). The chemical solution transport tube or hose of the present invention is manufactured by a coextrusion method in which various materials are coextruded in a molten state, and both are heat-sealed (melt-bonded) to produce a laminated structure tube or hose in one step. It is preferred that

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

  The chemical solution transporting tube or hose may have a corrugated region. The waveform region is a region formed in a waveform shape, a bellows shape, an accordion shape, a corrugated shape, or the like. The corrugated region is not limited to the entire length of the chemical solution conveying tube or hose, but may be partially included in an appropriate region on the way. The corrugated region can be easily formed by first forming a straight tube or hose 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, necessary parts such as a connector can be added, or an L shape or a U shape can be formed by bending.

  Epichlorohydrin rubber (ECO), acrylonitrile / butadiene rubber (NBR) are applied to all or a part of the outer periphery of the chemical delivery tube or hose formed in this way in consideration of abrasion with stones and other parts and flame resistance. , NBR and polyvinyl chloride mixture, chlorosulfonated polyethylene rubber, chlorinated polyethylene rubber, acrylic rubber (ACM), chloroprene rubber (CR), ethylene / propylene rubber (EPR), ethylene / propylene / diene rubber (EPDM), NBR It is possible to dispose a solid or sponge-like protective member (protector) composed of a rubber mixture of EPDM and EPDM, a thermoplastic elastomer such as vinyl chloride, olefin, ester or amide. 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 or a hose. In the case of a cylindrical member, the chemical solution transporting tube or hose is inserted later into the cylindrical member prepared in advance, or the cylindrical member is coated and extruded onto the chemical solution transporting tube or hose, and both are in close contact with each other. Can be made. In order to bond both, an adhesive is applied to the inner surface of the protective member or the concave surface as necessary, and a tube or hose for chemical transport is inserted or fitted into this, and the tube or hose An integrated structure of the protective member is formed. It can also be reinforced with metal or the like.

  The outer diameter of the chemical solution transport tube or hose considers the flow rate of the chemical solution (for example, fuel such as alcohol-containing gasoline), and the wall thickness does not increase the permeation amount of the chemical solution, and the normal tube or hose breaking pressure Designed to a thickness that can maintain the flexibility of the tube and the hose, and to maintain flexibility with a good degree of vibration resistance during use. Absent. Preferably, the outer diameter is 4 to 500 mm, the inner diameter is 3 to 400 mm, and the wall thickness is 0.5 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.

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

[Number of terminal carbonate groups in fluorine-containing polymer]
As for the number of terminal carbonate groups in the fluorine-containing polymer, the peak to which the carbonyl group of the carbonate group (—OC (═O) O—) belongs appears at the absorption wavelength of 1809 cm ⁻¹ by the infrared absorption spectrum analysis. absorbance was measured to calculate the number of main chain carbonate groups to the number ¹⁰⁶ carbons in the fluorine-containing polymer by the following equation.
[Number of carbonate groups relative to 10 ⁶ main chain carbon atoms in the fluorine-containing polymer] = 500 AW / εdf
A: Absorbance at peak of carbonate group (—OC (═O) O—) ε: Molar absorbance coefficient [cm ⁻¹ · mol ⁻¹ ] of carbonate group (—OC (═O) O—). Ε = 170 from the model compound.
W: Composition average molecular weight calculated from the monomer composition d: Film density [g / cm ³ ]
f: Film thickness [mm]

Moreover, each physical property of the laminated hose was measured by the following method.
[Low temperature impact resistance]
Evaluation was performed by the method described in SAE J-2260 7.5.

[Permeability of chemical solution (alcohol-containing gasoline) permeation]
One end of a hose 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 placed inside, and the remaining end was also sealed. Thereafter, the entire weight was measured, and then the test hose was placed in an oven at 60 ° C., and the change in weight was measured every day. The change in weight per day was divided by the surface area of the inner layer of the hose to calculate the chemical solution permeability coefficient (g / m ² · day).

[Interlayer adhesion]
A hose cut to 200 mm is further cut in half in the vertical direction to create a test piece. Using a Tensilon universal testing machine, a 180 ° peel test was performed at a tensile speed of 50 mm / min. The peel strength was read from the maximum point of the SS curve, and the interlayer adhesion was evaluated.

[Materials Used in Examples and Comparative Examples]
(A) Manufacture of aliphatic polyamide (A-1) polyamide 12 resin composition (a-1) Polyamide 12 (manufactured by Ube Industries, UBESTA3030U, relative viscosity 2.27), maleic anhydride as an impact modifier A modified ethylene / propylene copolymer (manufactured by JSR Co., Ltd., JSR T7712SP) is mixed in advance and supplied to a biaxial melt kneader (manufactured by Nippon Steel Works, Ltd., model: TEX44), while the biaxial melt kneader From the middle of the cylinder of the machine, as a plasticizer, benzenesulfonic acid butyramide was injected by a metering pump, melt-kneaded at a cylinder temperature of 180 to 260 ° C., extruded the molten resin in a strand shape, and then introduced it into a water tank, After cooling, cutting and vacuum drying, polyamide 12 consisting of 85% polyamide 12 resin, 10% impact modifier, 5% plasticizer To obtain a pellet of 12 resin composition (hereinafter, referred to as the polyamide resin composition (A-1)).

(A-2) Manufacture of conductive polyamide 12 resin composition (A-1) In manufacture of polyamide 12 resin composition, (a-1) Polyamide 12 is replaced with (a-2) Polyamide 12 (manufactured by Ube Industries, Ltd.) (A-1) Polyamide 12 except that carbon black (manufactured by Akzo Nobel Co., Ltd., Ketjen Black EC600JD) is used as the conductive filler, and no plasticizer is used. In the same manner as in the production of the resin composition, pellets of conductive polyamide 12 resin composition comprising 73% by weight of polyamide 12 resin, 20% by weight of impact modifier, and 7% by weight of conductive filler were obtained (hereinafter referred to as “this”). The polyamide resin composition is referred to as (A-2)).

(A-3) Manufacture of polyamide 6 resin composition Polyamide 6 (manufactured by Ube Industries, UBE Nylon 1024B relative viscosity 3.50), maleic anhydride modified ethylene / propylene copolymer (JSR Co., Ltd.) as an impact modifier. ), JSR T7712SP) is mixed in advance and supplied to a biaxial melt kneader (manufactured by Nippon Steel, Ltd., model: TEX44). Benzenesulfonic acid butyramide was injected with a metering pump, melted and kneaded at a cylinder temperature of 230 to 270 ° C., and the molten resin was extruded into a strand shape. Then, this was introduced into a water tank, cooled, cut, and vacuum dried. Pellets of polyamide 6 resin composition comprising 85% by weight of resin, 10% by weight of impact modifier, and 5% by weight of plasticizer were obtained (hereinafter referred to as the following) The polyamide resin composition is referred to as (A-3)).

(B) Layered silicate-containing semi-aromatic polyamide composition

(B1) Production of semi-aromatic polyamide polymer (B1-1) Production of semi-aromatic polyamide polymer 34524 g (198.2 mol) of suberic acid, 27239 g (200 mol) of metaxylyldiamine, 122.1 g of benzoic acid ( 1.0 mol), 62 g of sodium hypophosphite monohydrate (0.1% by weight based on the raw material) and 40 L of distilled water were placed in an autoclave 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 1.9 MPa. The reaction was continued for 3 hours, and then returned to normal pressure over 1 hour. At the same time, the temperature was raised to 235 ° C. When the internal temperature reached 235 ° C., pressure reduction was started and the reaction was allowed to proceed at 27 kPa for 8 hours. It was. Thereafter, the pressure was restored, the molten polymer was extracted from the bottom of the autoclave, cooled and pelletized to obtain a semi-aromatic polyamide polymer having a melting point of 203 ° C. and a relative viscosity of 2.72 (hereinafter, this semi-aromatic polyamide polymer was (Referred to as (B1-1)).

(B1-2) Production of semi-aromatic polyamide polymer (B1-1) In the production of semi-aromatic polyamide polymer, 34524 g (198.2 mol) of suberic acid was converted to 42864 g (198.2 mol) of undecanedicarboxylic acid. (B1-1) A semi-aromatic polyamide polymer having a melting point of 169 ° C. and a relative viscosity of 2.75 was obtained in the same manner as in the production of the (B1-1) semi-aromatic polyamide polymer, except that this was changed (hereinafter referred to as this A semi-aromatic polyamide polymer is referred to as (B1-2)).

(B1-3) Production of semi-aromatic polyamide polymer 34524 g (198.2 mol) of suberic acid, 37250 g (200 mol) of 1,5-naphthalenedimethylamine, 122.1 g (1.0 mol) of benzoic acid, hypochlorous acid 72 g of sodium phosphate monohydrate (0.1% by weight based on the raw material) and 40 L of distilled water were placed in an autoclave 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 1.9 MPa. The reaction was continued for 1 hour, 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 maintaining the pressure at 1.9 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 and pulverized to a size of 2 mm or less. This was solid-phase polymerized at 240 ° C. and 0.013 kPa for 12 hours to obtain a semi-aromatic polyamide polymer having a melting point of 316 ° C. and a relative viscosity of 2.68 (hereinafter, this semi-aromatic polyamide polymer). (Referred to as (B1-3)).

(B1-4) Production of semi-aromatic polyamide polymer (B1-3) In production of semi-aromatic polyamide polymer, 34524 g (198.2 mol) of suberic acid was converted to 45645 g (198.2 mol) of dodecanedicarboxylic acid, (B1-3) Semi-aromatic polyamide polymer, except that 37,250 g (200 mol) of 1,5-naphthalenedimethylamine was changed to 37250 g (200 mol) of 2,6-naphthalenedimethylamine and solid-phase polymerized at 220 ° C. A semi-aromatic polyamide polymer having a melting point of 272 ° C. and a relative viscosity of 2.72 was obtained in the same manner as in the production of (hereinafter, this semi-aromatic polyamide polymer is referred to as (B1-4)).

(B1-5) Production of semi-aromatic polyamide polymer 28964 g (198.2 mol) of adipic acid, 27239 g (200 mol) of metaxylyldiamine, 122.1 g (1.0 mol) of benzoic acid, sodium hypophosphite 56 g of monohydrate (0.1% by weight with respect to the raw material) and 40 L of distilled water were placed in an autoclave 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 1.9 MPa. The reaction was continued for 3 hours. After returning to normal pressure over 1 hour, the temperature was raised to 265 ° C. When the internal temperature reached 265 ° C, pressure reduction was started and the reaction was allowed to proceed at 27 kPa for 3 hours. It was. Thereafter, the pressure was restored, the molten polymer was extracted from the bottom of the autoclave, cooled and pelletized to obtain a semi-aromatic polyamide polymer having a melting point of 239 ° C. and a relative viscosity of 2.40 (hereinafter, this semi-aromatic polyamide polymer was (Referred to as (B1-5)).

(B1-6) Production of conductive semi-aromatic polyamide polymer composition (B1-4) In the production of semi-aromatic polyamide polymer, except that the solid-phase polymerization time was changed to 8 hours (B1-4) A semi-aromatic polyamide polymer having a melting point of 272 ° C. and a relative viscosity of 2.40 was obtained in the same manner as in the production of the semi-aromatic polyamide polymer (hereinafter, this semi-aromatic polyamide polymer (B1- 4 ')). (B1) Semi-aromatic polyamide polymer (B1-4 ′), as impact modifier, (C) fluorinated polymer (C-1), and carbon black (Akzo Nobel Co., Ltd.) as a conductive filler Manufactured by Ketjen Black EC600JD), supplied in advance to a twin-screw melt kneader (manufactured by Nippon Steel, Ltd., model: TEX44), melt-kneaded at a cylinder temperature of 240-310 ° C., and the molten resin in a strand form After being extruded into a water tank, this is cooled, cut, and vacuum dried to form a conductive semi-fragrance comprising 80% by weight of a semi-aromatic polyamide polymer, 13% by weight of an impact modifier, and 7% by weight of a conductive filler. Group polyamide polymer composition pellets were obtained (hereinafter, this semi-aromatic polyamide polymer composition is referred to as (B1-6)).

(B) Manufacture of layered silicate-containing semi-aromatic polyamide composition (B-1) Manufacture of layered silicate-containing semi-aromatic polyamide composition The average thickness of one unit of layered silicate is 9.5 mm, 100 g of montmorillonite having a length of about 0.1 μm was dispersed in 2.3 liters of water, and 28.1 g of 12-aminododecanoic acid and 12 ml of concentrated hydrochloric acid were added thereto, followed by stirring at 80 ° C. for 60 minutes. Furthermore, what was sufficiently washed was subjected to suction filtration using a Buchner funnel to obtain a water-containing composite (hereinafter abbreviated as 12MMT). A part of this composite was sampled and the water content was determined to be 88%. The interlayer distance of the composite of 12-aminododecanoic acid and montmorillonite (12MMT) was measured by X-ray diffraction and found to be 18 mm.
Next, water and caprolactam were added to this 12MMT so that the ratio might become 1: 9: 9, and it stirred and mixed.
Thereafter, a 12MMT composite obtained by adding water and caprolactam to the composite (12MMT) with montmorillonite 12-aminododecanoate to 100 parts by weight of the semi-aromatic polyamide polymer (B1-1) produced above. After supplying 38.8 parts by weight to a biaxial melt kneader (manufactured by Nippon Steel Works, model: TEX44), melt kneading at a cylinder temperature of 180 to 240 ° C., and extruding the molten resin into a strand shape, This was introduced into a water tank to obtain pellets composed of cooling, cutting, semi-aromatic polyamide polymer and composite. This pellet was immersed in hot water to remove caprolactam, which is one of the dispersion media in the 12MMT, and then vacuum dried to obtain a layered silicate-containing semi-aromatic polyamide composition (layered silicate-containing). 2.0 parts by weight, relative viscosity 2.5, hereinafter, this layered silicate-containing semi-aromatic polyamide composition is referred to as (B-1)). A test piece was prepared using the composition and subjected to wide-angle X-ray diffraction measurement. As a result, it was confirmed that the peak due to the thickness direction of the silicate layer had disappeared.

(B-2) Production of layered silicate-containing semi-aromatic polyamide composition (B-1) In production of layered silicate-containing semi-aromatic polyamide composition, semi-aromatic polyamide polymer (B1-1) is (B1). 2), except that melt kneading is performed at a cylinder temperature of 150 to 200 ° C., (B-1) layered silicate-containing semi-aromatic in the same manner as the production of layered silicate-containing semi-aromatic polyamide composition A polyamide composition was obtained (layered silicate content 2.0 parts by weight, relative viscosity 2.54, hereinafter, this layered silicate-containing semi-aromatic polyamide composition is referred to as (B-2)). A test piece was prepared using the composition and subjected to wide-angle X-ray diffraction measurement. As a result, it was confirmed that the peak due to the thickness direction of the silicate layer had disappeared.

(B-3) Production of layered silicate-containing semi-aromatic polyamide composition (B-1) In production of layered silicate-containing semi-aromatic polyamide composition, semi-aromatic polyamide polymer (B1-1) is (B1). 3), except that the cylinder temperature was changed to 260 to 320 ° C., (B-1) a layered silicate-containing semi-aromatic in the same manner as the production of the layered silicate-containing semi-aromatic polyamide composition A polyamide composition was obtained (layered silicate content 2.0 parts by weight, relative viscosity 2.45, hereinafter, this layered silicate-containing semi-aromatic polyamide composition is referred to as (B-3)). A test piece was prepared using the composition and subjected to wide-angle X-ray diffraction measurement. As a result, it was confirmed that the peak due to the thickness direction of the silicate layer had disappeared.

(B-4) Production of layered silicate-containing semi-aromatic polyamide composition (B-1) In production of layered silicate-containing semi-aromatic polyamide composition, semi-aromatic polyamide polymer (B1-1) is (B1). 4), except that the cylinder temperature was changed to 240 to 285 ° C., (B-1) layered silicate-containing semi-aromatic in the same manner as the production of layered silicate-containing semi-aromatic polyamide composition A polyamide composition was obtained (layered silicate content 2.0 parts by weight, relative viscosity 2.51, hereinafter, this layered silicate-containing semi-aromatic polyamide composition is referred to as (B-4)). A test piece was prepared using the composition and subjected to wide-angle X-ray diffraction measurement. As a result, it was confirmed that the peak due to the thickness direction of the silicate layer had disappeared.

(B-5) Production of layered silicate-containing semi-aromatic polyamide composition (B-1) In production of layered silicate-containing semi-aromatic polyamide composition, semi-aromatic polyamide polymer (B1-1) is (B1). (B-1) In the same manner as the production of the layered silicate-containing semi-aromatic polyamide composition, except that the cylinder temperature was changed to 220 to 270 ° C., the layered silicate-containing semi-aromatic polyamide was changed. A composition was obtained (layered silicate content 2.0 parts by weight, relative viscosity 2.18, hereinafter this layered silicate-containing semi-aromatic polyamide composition is referred to as (B-5)). A test piece was prepared using the composition and subjected to wide-angle X-ray diffraction measurement. As a result, it was confirmed that the peak due to the thickness direction of the silicate layer had disappeared.

(C) Production of fluorinated polymer (C-1) Production of fluorinated polymer An autoclave with a stirrer having an internal volume of 94 liters was degassed, 19.7 kg of ion-exchanged water, 77.1 kg of perfluoropentyldifluoromethane. , CH ₂ = CH (CF ₂ ) ₂ F (427 g), TFE (3.36 kg), and E (127 g) were injected under pressure, and the temperature in the autoclave was raised to 66 ° C. At this time, the pressure was 0.65 MPa. As a polymerization initiator, 72 g of diisopropyl peroxydicarbonate was charged to initiate polymerization. A monomer mixed gas having a molar ratio of TFE / E = 60/40 was continuously charged so that the pressure was kept constant during the polymerization. Further, CH ₂ ═CH (CF ₂ ) ₂ F in an amount corresponding to 6 mol% with respect to the total number of moles of TFE and E charged during the polymerization was continuously charged. 5.6 hours after the start of polymerization, when 11.5 kg of the monomer mixed gas was charged, the autoclave internal temperature was cooled to room temperature and the pressure in the polymerization layer was purged to normal pressure. The obtained slurry-like fluorine-containing polymer was put into a 300 L granulation tank charged with 100 kg of water, and the temperature was raised to 105 ° C. while stirring to granulate while removing the solvent by distillation. The obtained granulated product was dried at 135 ° C. for 3 hours to obtain 12.1 kg of a granulated product of a fluorine-containing polymer.

The composition of the fluorine-containing polymer was 57.2 / 37.0 / 5.8 in terms of a molar ratio of polymerized units based on TFE / polymerized units based on E / polymerized units based on CH ₂ ═CH (CF ₂ ) ₂ F. The number of carbonate end groups derived from the polymerization initiator of the fluorine-containing polymer was 359. The melting point was 205 ° C.
This granulated product was melted at 260 ° 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)). .

(C-2) Production of conductive fluorine-containing polymer (C-1) 100 parts by weight of fluorine-containing polymer and 13 parts by weight of carbon black (manufactured by Electrochemical Co., Ltd.) Supplied to a shaft extruder (Toshiba Machine Co., Ltd. Model: TEM-48S), melt-kneaded at a cylinder temperature of 240-280 ° C., extruded the molten resin into a strand, then introduced it into a water tank and discharged The strand was cooled with water, the strand was cut with a pelletizer, and dried for 10 hours with a drier at 120 ° C. to remove moisture to obtain conductive fluorine-containing polymer pellets (hereinafter referred to as this conductive fluorine-containing heavy polymer). The coalescence is referred to as (C-2).)

(D) Modified polyolefin (D-1) Maleic acid-modified polypropylene Admer QF500 manufactured by Mitsui Chemicals, Inc.

Example 1
Using (A) polyamide 12 resin composition (A-1) and (B) layered silicate-containing semi-aromatic polyamide composition (B-1) shown above, Plabor (Plastic Engineering Laboratory Co., Ltd.) (Manufactured) In a two-layer hose molding machine, (A) is melted separately at an extrusion temperature of 250 ° C and (B) is melted at an extrusion temperature of 240 ° C, and the discharged molten resin is merged by an adapter to form a laminated tubular body did. Subsequently, it is cooled by a sizing die for dimension control, and taken up, and (A) a layer (outermost layer) made of a polyamide 12 resin composition, (B) a layered silicate-containing semi-aromatic polyamide composition ( b) A laminated hose 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 when the layer (innermost layer) was formed was obtained. The physical property measurement results of the laminated hose are shown in Table 1.

Example 2
In Example 1, except that (B) the layered silicate-containing semi-aromatic polyamide composition (B-1) was changed to (B-2) and (B) was melted at an extrusion temperature of 220 ° C. 1 was used to obtain a laminated hose having the layer structure shown in Table 1. The physical property measurement results of the laminated hose are shown in Table 1.

Example 3
In Example 1, except that (B) the layered silicate-containing semi-aromatic polyamide composition (B-1) was changed to (B-3) and (B) was melted at an extrusion temperature of 330 ° C. 1 was used to obtain a laminated hose having the layer structure shown in Table 1. The physical property measurement results of the laminated hose are shown in Table 1.

Example 4
In Example 3, except that (B) the layered silicate-containing semi-aromatic polyamide composition (B-3) was changed to (B-4) and (B) was melted at an extrusion temperature of 300 ° C. 3 was used to obtain a laminated hose having the layer structure shown in Table 1. The physical property measurement results of the laminated hose are shown in Table 1.

Example 5
(A) polyamide 12 resin composition (A-1), (B) layered silicate-containing semi-aromatic polyamide composition (B-4), (B1) conductive semi-aromatic polyamide polymer composition ( B1-6) using a three-layer hose molding machine (made by Plastic Engineering Laboratory Co., Ltd.), (A) is extrusion temperature 250 ° C., (B) is extrusion temperature 300 ° C., (B1) Were melted separately at an extrusion temperature of 320 ° C., and the discharged molten resin was joined by an adapter to form a laminated tubular body. Subsequently, it is cooled by a sizing die that controls dimensions, and taken up. (A) Layer (outermost layer) made of polyamide 12 resin composition, (B) Layered silicate-containing semi-aromatic polyamide composition (B- (B) layer (inner layer) consisting of 4) and (B) layer (innermost layer) consisting of (B) conductive semi-aromatic polyamide polymer composition (B1-6). A laminated hose having a) / (b) / (b ′) = 0.85 / 0.10 / 0.05 mm and an inner diameter of 6 mm and an outer diameter of 8 mm was obtained. The physical property measurement results of the laminated hose are shown in Table 1. Moreover, when the electroconductivity of the said laminated hose was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square, and it confirmed that it was excellent in static electricity removal performance.

Example 6
(A) Polyamide 12 resin composition (A-1), polyamide 6 resin composition (A-3), and (B) layered silicate-containing semi-aromatic polyamide composition (B-3) shown above are used. Using a three-layer hose molding machine (made by Plastic Engineering Laboratory Co., Ltd.), (A) was melted separately at an extrusion temperature of 250 ° C. and (B) was melted at an extrusion temperature of 330 ° C., and the molten resin discharged. Are combined with an adapter, formed into a tubular shape, cooled with a sizing die that controls dimensions, taken up, and (A) a layer composed of the polyamide 12 resin composition (A-1) (a) layer (outermost layer), (B) A layer composed of a layered silicate-containing semi-aromatic polyamide composition is referred to as (b) layer (intermediate layer), and (A) a layer composed of the polyamide 6 resin composition (A-3) is referred to as (a ′) layer (the top layer). (Inner layer), the layer structure is (a) / (b) / (a ′) = 0.45 / 0.15 / 0.40 mm, a laminated hose having an inner diameter of 6 mm and an outer diameter of 8 mm was obtained. The physical property measurement results of the laminated hose are shown in Table 1.

Example 7
In Example 6, (B) layered silicate-containing semi-aromatic polyamide composition (B-3) is changed to (B-4), and (A) polyamide 6 resin composition (A-3) is changed to polyamide 12 resin composition. A laminated hose having the layer structure shown in Table 1 was obtained in the same manner as in Example 6 except that (A-1) was changed and (B) was melted at an extrusion temperature of 300 ° C. The physical property measurement results of the laminated hose are shown in Table 1.

Example 8
In Example 7, (A) polyamide 12 resin composition (A-1) used as the innermost layer material was changed to (A) conductive polyamide 12 resin composition (A-2), and (A) was extruded at temperature 270. A laminated hose having the layer structure shown in Table 1 was obtained in the same manner as in Example 7 except that the hose was melted at 0 ° C. The physical property measurement results of the laminated hose are shown in Table 1. Moreover, when the electroconductivity of the said laminated hose was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square, and it confirmed that it was excellent in static electricity removal performance.

Example 9
(A) Polyamide 12 resin composition (A-1), conductive polyamide 12 resin composition (A-2), polyamide 12 (a-1), (B) layered silicate-containing semi-aromatic polyamide composition shown above Using a product (B-4), a 4-layer hose molding machine (Plastics Engineering Laboratory Co., Ltd.), (A) at an extrusion temperature of 270 ° C., and (B) at an extrusion temperature of 300 ° C. Separately melted, the discharged molten resin is joined by an adapter, formed into a tube, cooled by a sizing die that controls the dimensions, taken up, and (A) a layer comprising a polyamide 12 resin composition (A-1) (A) layer (outermost layer), (B) a layer composed of a layered silicate-containing semi-aromatic polyamide composition, (b) a layer (intermediate layer), and (A) a layer composed of polyamide 12 (a-1). (A ′) layer (inner layer), (A) conductive layer When the layer made of the reamide 12 resin composition (A-2) is the (a ″) layer (innermost layer), the layer structure is (a) / (b) / (a ′) / (a ″) = A laminated hose having a diameter of 0.45 / 0.15 / 0.30 / 0.10 mm, an inner diameter of 6 mm, and an outer diameter of 8 mm was obtained. The physical property measurement results of the laminated hose are shown in Table 1. Moreover, when the electroconductivity of the said laminated hose was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square, and it confirmed that it was excellent in static electricity removal performance.

Example 10
(A) polyamide 12 resin composition (A-1), polyamide 12 (a-1), (B) layered silicate-containing semi-aromatic polyamide composition (B-4), (C) fluorine-containing system shown above Using the polymer (C-1), in a Plabor (Plastics Engineering Laboratory Co., Ltd.) 4-layer hose molding machine, (A) is an extrusion temperature of 260 ° C, (B) is an extrusion temperature of 300 ° C, (C) is melted separately at an extrusion temperature of 260 ° 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. (A) Polyamide 12 resin The layer made of the composition (A-1) is (a) layer (outermost layer), (B) the layer made of layered silicate-containing semi-aromatic polyamide composition is (b) layer (intermediate layer), and (A) polyamide 12 (a-1) layer (a ′) layer (inner layer ), (C) When the layer made of the fluorine-containing polymer (C-1) is the (c) layer (innermost layer), the layer structure is (a) / (b) / (a ′) / (c) = 0.45 / 0.15 / 0.25 / 0.15 mm, an inner diameter of 6 mm, and an outer diameter of 8 mm were obtained. The physical property measurement results of the laminated hose are shown in Table 1.

Example 11
In Example 10, (C) fluorinated polymer (C-1) was changed to (C) conductive fluorinated polymer (C-2), and (C) was melted at an extrusion temperature of 280 ° C. Except for the above, a layered hose 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 hose are shown in Table 1. Moreover, when the electroconductivity of the said laminated hose was measured based on SAE J-2260, it was below 10 < ⁶ > ohm / square, and it confirmed that it was excellent in static electricity removal performance.

Comparative Example 1
In Example 1, the single layer hose of the layer structure shown in Table 1 is obtained by the same method as Example 1 except not using (B) layered silicate containing semi-aromatic polyamide composition (B-1). It was. The physical property measurement results of the single-layer hose are shown in Table 1.

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

Comparative Example 3
Example 1 is the same as Example 1 except that (B) the layered silicate-containing semi-aromatic polyamide composition (B-1) is changed to (B1) the semi-aromatic polyamide polymer (B1-1). A laminated tube having the layer structure shown in Table 1 was obtained by the method. The physical property measurement results of the laminated tube are shown in Table 1.

Comparative Example 4
In Example 1, (B) the layered silicate-containing semi-aromatic polyamide composition (B-1) is changed to (B1) a semi-aromatic polyamide polymer (B1-5), and (B1) is brought to an extrusion temperature of 270 ° C. A laminated hose having the layer structure shown in Table 1 was obtained in the same manner as in Example 1 except that the hose was melted. The physical property measurement results of the laminated hose are shown in Table 1.

Comparative Example 5
In Example 1, except that (B) the layered silicate-containing semi-aromatic polyamide composition (B-1) was changed to (B-5) and (B) was melted at an extrusion temperature of 270 ° C. 1 was used to obtain a laminated hose having the layer structure shown in Table 1. The physical property measurement results of the laminated hose are shown in Table 1.

Comparative Example 6
In Example 6, except that (B) the layered silicate-containing semi-aromatic polyamide composition (B-1) was changed to (B-5) and (B) was melted at an extrusion temperature of 270 ° C. 6 was used to obtain a laminated hose having the layer structure shown in Table 1. The physical property measurement results of the laminated hose are shown in Table 1.

Comparative Example 7
In Comparative Example 6, the layer structure shown in Table 1 is the same as in Comparative Example 6 except that (A) the polyamide 12 resin composition (A-1) is changed to the polyamide 6 resin composition (A-3). A laminated hose was obtained. The physical property measurement results of the laminated hose are shown in Table 1.

Comparative Example 8
(A) Polyamide 12 resin composition (A-1), (B) Layered silicate-containing semi-aromatic polyamide composition (B-5), (D) Modified polyolefin (D-1) shown above are used. Using a 5-layer hose molding machine (made by Plastic Engineering Laboratory Co., Ltd.), (A) was extruded at 260 ° C, (B) was extruded at 270 ° C, and (C) was extruded at 200 ° C. The molten resin discharged is joined by an adapter, formed into a tubular shape, cooled by a sizing die for dimension control, taken up, and (A) a layer made of the polyamide 12 resin composition (A-1) (A) layer (outermost layer, innermost layer), (B) layer made of layered silicate-containing semi-aromatic polyamide composition (b) layer (intermediate layer), (D) layer made of modified polyolefin (d) Layer (outer layer, inner layer), layer Lamination of (a) / (d) / (b) / (d) / (a) = 0.35 / 0.05 / 0.25 / 0.05 / 0.30 mm, inner diameter 6 mm, outer diameter 8 mm I got a hose. The physical property measurement results of the laminated hose are shown in Table 1.

Claims (10)

(A) layer composed of aliphatic polyamide (a), diamine units containing 60 mol% or more of xylylenediamine and / or naphthalenedimethylamine units with respect to all diamine units, and carbon number with respect to all dicarboxylic acid units (B2) layered silicate 0.1-30 in the molecule with respect to 100 weight of (B1) semi-aromatic polyamide polymer consisting of dicarboxylic acid unit containing 60 mol% or more of 8-13 aliphatic dicarboxylic acid units A laminated structure comprising at least two layers including (b) a layer (b) made of a layered silicate-containing semi-aromatic polyamide composition in which parts by weight are uniformly dispersed. The (B) layered silicate-containing semi-aromatic polyamide composition according to claim 1, wherein (B2) the layered silicate has a side of 0.002 to 1 µm with respect to the (B1) semi-aromatic polyamide polymer. The laminated structure according to claim 1, wherein the thickness is 6 to 20 mm, and each layer is uniformly dispersed with an average separation of 20 mm or more. In the laminated structure, the (B1) semi-aromatic polyamide polymer is selected from the group consisting of metaxylylenediamine, 1,5-naphthalenedimethylamine, and 2,6-naphthalenedimethylamine with respect to all diamine units. 60 moles of at least one unit selected from the group consisting of suberic acid, azelaic acid, sebacic acid, and dodecanedicarboxylic acid with respect to the diamine unit containing 60 mol% or more of at least one unit and all dicarboxylic acid units 3. The laminated structure according to claim 1, wherein the laminated structure is a polyamide composed of dicarboxylic acid units containing at least%. In the laminated structure, (A) aliphatic polyamide is polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polyhexamethylene dodecamide (polyamide 612), polyundecanamide (polyamide 11). The at least one homopolymer selected from the group consisting of polydodecanamide (polyamide 12), or a copolymer using several kinds of raw material monomers forming them. The laminated structure according to any one of the above. In the laminated structure, (A) a layer made of an aliphatic polyamide (a) is arranged in the outermost layer, and (B) a layer (b) made of a layered silicate-containing semi-aromatic polyamide composition becomes a layer (a). The laminated structure according to any one of claims 1 to 4, wherein the laminated structure is disposed on the inner side. 6. The laminated structure according to claim 5, wherein the (b) layer comprising the (B) layered silicate-containing semi-aromatic polyamide composition is disposed in the innermost layer. 6. The laminated structure according to claim 5, further comprising (c) a layer (c) made of a fluorine-containing polymer in which a functional group having reactivity with 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 7, wherein the laminated structure is manufactured by coextrusion molding. A laminated molded product selected from the group consisting of a film, a hose, a tube, a bottle, and a tank, comprising the laminated structure according to any one of claims 1 to 8. It is a chemical | medical solution conveyance tube or a hose, The laminated molded product of Claim 9 characterized by the above-mentioned.