JP2006029574A - Layered hose - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a layered hose superior in chemical permeation preventing property, layer-to-layer adhesiveness, low temperature impact resistance, chemical resistance, and environmental stress loading resistance. <P>SOLUTION: The layered hose comprises at least three layers, (A) a (a) layer formed of aliphatic polyamide, (B) a (b) layer formed of a 5-55 mol%-ethylene content modified ethylene/vinyl acetate copolymer saponified material containing a 0.3-40 mol% structural unit (I), and (C) a (c) layer formed of a fluorine containing polymer having functional groups reactive on amino groups or hydroxyl groups and introduced into molecular chains. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to a layer comprising an aliphatic polyamide (polyamide 11, 12, etc.), a layer comprising a saponified modified ethylene / vinyl acetate copolymer having a specific polymerization unit, and a fluorine-containing polymer having a specific functional group. More particularly, the present invention relates to a laminated hose having excellent interlayer adhesion, chemical solution permeation prevention, low-temperature impact resistance, chemical resistance, and environmental stress load resistance.

  In the hose for automobile piping, in response to the problem of rusting due to antifreezing agents on roads and the request for global warming prevention and energy saving, the main material is metal, excellent in rust prevention and lightweight, Replacement with resin is progressing. Usually, resins used as piping hoses include polyamide-based resins, saturated polyester-based resins, polyolefin-based resins, thermoplastic polyurethane-based resins, etc. In the case of single-layer hoses using these, heat resistance, Since the chemical properties are insufficient, the applicable range is limited.

  Also, automotive piping hoses are oxygen-containing gasoline blended with low boiling point alcohols such as methanol and ethanol or ethers such as methyl-t-butyl ether (MTBE) from the viewpoint of saving gasoline consumption and improving performance. Etc. are transferred. Furthermore, from the viewpoint of preventing environmental pollution, strict exhaust gas regulations including prevention of leakage into the atmosphere due to diffusion of volatile hydrocarbons and the like through piping hose partition walls are being implemented. In response to such strict regulations, a single-layer hose using a polyamide-based resin, particularly polyamide 11 or polyamide 12 excellent in strength, toughness, chemical resistance and flexibility, which has been used conventionally, is the above chemical solution. The permeation-preventing property against water is not sufficient, and in particular, improvement of the permeation-preventing property of alcohol-containing gasoline is required.

  As a method for solving this problem, a resin having good chemical liquid permeation preventive properties such as saponified ethylene / vinyl acetate copolymer (EVOH), polymetaxylylene adipamide (polyamide MXD6), polybutylene terephthalate (PBT), polyethylene Naphthalate (PEN), polybutylene naphthalate (PBN), polyphenylene sulfide (PPS), polyvinylidene fluoride (PVDF), ethylene / tetrafluoroethylene copolymer (ETFE), ethylene / chlorotrifluoroethylene copolymer (ECTFE) ), Tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (TFE / HFP / VDF, THV) Hoses have been proposed (e.g., refer to Jpn.).

  In particular, the saponified ethylene / vinyl acetate copolymer (EVOH) is extremely excellent in chemical solution permeation prevention properties, particularly permeation prevention properties for ethanol-containing gasoline. For example, a fuel composed of an outermost layer made of polyamide 12, an adhesive layer made of modified polyolefin, an outer layer made of polyamide 6, an intermediate layer made of saponified ethylene / vinyl acetate copolymer (EVOH), and an innermost layer made of polyamide 6 Piping has been proposed (see Patent Document 2). However, also in this piping, when polyamide 6 is used as the innermost layer, the resistance (chemical resistance) to sour gasoline produced by oxidation of gasoline is poor. Further, in the fuel pipe, static electricity generated by internal friction of the fuel circulating in the pipe or friction with the pipe wall accumulates and may ignite the chemical solution, and measures to prevent this are required. As a method for solving this, an outermost layer made of polyamide 12, an adhesive layer made of modified polyolefin, an outer layer made of polyamide 6, an intermediate layer made of saponified ethylene / vinyl acetate copolymer (EVOH), a conductive polyamide 6 resin composition An innermost layer made of a product, or an outermost layer made of polyamide 12, an adhesive layer made of modified polyolefin, an intermediate layer made of saponified ethylene / vinyl acetate copolymer (EVOH), an adhesive layer made of modified polyolefin, conductive polyamide 12 A fuel pipe composed of an innermost layer made of a resin composition has been proposed (see Patent Document 3). Also in this pipe, when the conductive polyamide 6 resin composition is used as the innermost layer, the resistance to sour gasoline is inferior to the non-conductive fuel pipe, and the conductive polyamide 12 resin composition is used as the innermost layer. Is used, the resistance improvement effect to sour gasoline is recognized as compared with the conductive polyamide 6 resin composition, but the resistance is not satisfactory.

  On the other hand, in automotive piping hoses, as inner layer materials that are in direct contact with the fuel, it is required to use a resin that is resistant to corrosive chemicals such as ethanol and methanol present in the fuel and has excellent permeation-preventing properties. ing. In this regard, as the inner layer material, it is considered that one of the most preferable ones is a fluororesin excellent in heat resistance, chemical resistance, and chemical liquid permeation prevention.

In particular, in order to make the best use of the advantages of the fluororesin and to minimize the disadvantages, various studies have been made on adhesion, lamination, etc. between the fluororesin and other dissimilar materials. However, the fluororesin inherently has poor adhesion, and it is difficult to directly bond with other different materials, and sufficient adhesive strength cannot be obtained. Even when a certain degree of adhesive strength is obtained, the adhesive strength tends to vary depending on the type of different materials, and the adhesive strength is often insufficient practically.
Such a laminated hose needs to have a strong interlayer adhesion strength so that delamination does not occur during processing or use. Examples of means for increasing the adhesive strength include a method in which a fluororesin hose is molded in advance and a surface treatment is performed, and then a different material is coated, a coextrusion molding method using an adhesive resin, and the like. In particular, the coextrusion molding method using an adhesive resin can be said to be a low-cost method because it does not require a surface treatment step. Furthermore, a method of directly bonding a fluororesin and a different material without using an adhesive resin is a more advantageous method in terms of cost and management.

  In the future, more stringent laws and regulations will be imposed from the viewpoint of preventing environmental pollution, and it is desirable to limit the amount of fuel that permeates and evaporates from the piping hose bulkhead. Even in the hose, it is difficult to suppress the fuel that permeates from the partition wall and evaporates to the limit. As a means for overcoming this, a fuel transfer hose has been proposed that has a fluorine-based resin disposed on the inner layer and a layer disposed on the outside with a saponified ethylene / vinyl acetate copolymer (patent) Reference 4). The fuel transfer hose according to the present technology is very excellent in chemical solution permeation prevention. However, in the fuel transfer hose, it has been proposed that a modified polyolefin resin is disposed as an adhesive resin interposed between a layer made of a fluorine-based resin and a layer made of a saponified ethylene / vinyl acetate copolymer. However, the interlayer adhesion is not sufficient, and further improvement is desired. In addition, these fuel transfer hoses are generally piped in a state where bending stress is applied due to layout restrictions and displacement absorption at the time of a collision. In such fuel transfer hoses, both ethylene / vinyl acetate are used. Development of a laminated hose that has resistance to environmental stress load due to the problem that minute cracks called crazes occur in the layer made of saponified polymer, and the chemical permeation prevention property is greatly impaired. Is the place that is required.

US Pat. No. 5,554,425 JP-A-3-177683 JP 2002-160314 A Japanese Patent Laid-Open No. 5-247478

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

  As a result of intensive studies to solve the above problems, the present inventor has found that a layer composed of an aliphatic polyamide (polyamide 11, 12, etc.), a modified ethylene / vinyl acetate copolymer saponified product having specific polymer units. Layered hose consisting of a layer made of a fluorine-containing polymer having a specific functional group achieves both interlaminar adhesion and chemical liquid permeation prevention properties, and also has low-temperature impact resistance, chemical resistance, and environmental stress load resistance It has been found that they are excellent in various properties.

  That is, the present invention provides (A) a layer made of an aliphatic polyamide (a), (B) a modified ethylene having an ethylene content of 5 to 55 mol%, containing 0.3 to 40 mol% of the following structural unit (I). (B) layer made of saponified vinyl acetate copolymer, and (C) a fluorine-containing polymer in which a functional group having reactivity to amino group or hydroxyl group is introduced into the molecular chain (c A laminated hose comprising at least three layers)

（式中、Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は、水素原子、炭素数１〜１０の脂肪族炭化水素基、炭素数３〜１０の脂環式炭化水素基、炭素数６〜１０の芳香族炭化水素基を表す。Ｒ^１、Ｒ^２、Ｒ^３及びＲ^４は同じ基でもよいし、異なっていてもよい。また、Ｒ^３とＲ^４は結合していてもよい。また上記のＲ^１、Ｒ^２、Ｒ^３及びＲ^４は他の基、例えば、水酸基、カルボキシル基、ハロゲン原子等を有していてもよい。）
を提供することにある。

(Wherein R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or 6 to 10 carbon atoms. R ¹ , R ² , R ³ and R ⁴ may be the same group or different from each other, and R ³ and R ⁴ may be bonded to each other. R ¹ , R ² , R ³ and R ⁴ may have other groups such as a hydroxyl group, a carboxyl group, and a halogen atom.)
Is to provide.

  The laminated hose of the present invention achieves both interlayer adhesion and chemical solution permeation prevention properties and is excellent in various properties such as low-temperature impact resistance, chemical resistance, and environmental stress load resistance. In particular, alcohol-mixed hydrocarbons that permeate and evaporate from the hose partition wall can be suppressed to the limit, making it possible to comply with strict environmental regulations. Furthermore, it is excellent in resistance (chemical resistance) to sour gasoline produced by oxidation of gasoline and environmental stress load resistance such as bending stress, which are problems in actual use of the laminated hose. Therefore, the laminated hose of the present invention can be used in any environment, has high reliability, and its utility value is extremely high.

The present invention is described in detail below.
The (A) aliphatic polyamide used in the present invention has an amide bond (—CONH—) in the main chain, and is an aliphatic polyamide structural unit lactam, aminocarboxylic acid, or aliphatic diamine and aliphatic. It can be obtained by polymerization or copolymerization using a nylon salt comprising dicarboxylic acid as a raw material by a known method such as melt polymerization, solution polymerization or solid phase polymerization.

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

  Examples of the aliphatic diamine 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 or the like. These can use 1 type (s) or 2 or more types.

  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. An acid, octadecanedicarboxylic acid, eicosane dicarboxylic acid, etc. are mentioned. These can use 1 type (s) or 2 or more types.

  (A) As the aliphatic polyamide, polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyethylene adipamide (polyamide 26), polytetramethylene adipamide (polyamide) 46), polyhexamethylene adipamide (polyamide 66), polyhexamethylene azelamide (polyamide 69), polyhexamethylene sebamide (polyamide 610), polyhexamethylene undecamide (polyamide 611), polyhexamethylene dodeca Polyamide (polyamide 612), polynonamethylene adipamide (polyamide 96), polynonamethylene azelamide (polyamide 99), polynonamethylene sebamide (polyamide 910), polynonamethylene undecamide (polyamide 91) ), Polynonamethylene dodecamide (polyamide 912), polydecamethylene dodecamide (polyamide 1012), polydodecamethylene dodecamide (polyamide 1212) and other homopolymers, and co-polymerization using several raw material monomers forming them Examples include coalescence.

  Among these, polycaproamide (polyamide 6), polyundecanamide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene adipamide (polyamide 66), polyhexamethylene azelamide (polyamide 69), poly Hexamethylene sebacamide (polyamide 610), polyhexamethylene undecamide (polyamide 611), polyhexamethylene dodecamide (polyamide 612), polynonamethylene dodecamide (polyamide 912) and several kinds of raw material monomers The copolymers used are preferred, and polycaproamide (polyamide 6), polyhexamethylene dodecane (polyamide 612), polyundecanamide (polyamide 11), and polydodecanamide (polyamide 12) are most preferred.

  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 It may be a mixture with other polyamide-based resins or other thermoplastic resins. The content of the (A) aliphatic polyamide in the mixture is preferably 60% by weight or more.

  Other polyamide resins include polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polymetaxylylene adipamide (polyamide MXD6), polymetaxylylene beramide (polyamide MXD8). ), Polymetaxylylene azelamide (polyamide MXD9), polymetaxylylene sebamide (polyamide MXD10), polymetaxylylene decanamide (polyamide MXD12), polymetaxylylene terephthalamide (polyamide MXDT), polymetaxylylene isophthalamide (Polyamide MXDI), polymetaxylylene naphthalamide (polyamide MXDN), polybis (4-aminocyclohexyl) methane dodecamide (polyamide PACM12), polybis (4-aminosilane) Rohexyl) methane terephthalamide (polyamide PACMT), polybis (4-aminocyclohexyl) methane isophthalamide (polyamide PACMI), polybis (3-methyl-4-aminocyclohexyl) methane dodecamide (polyamide dimethyl PACM12), polyisophorone azimuth Pamide (polyamide IPD6), polyisophorone terephthalamide (polyamide IPDT), polytrimethylhexamethylene terephthalamide (polyamide TMHT), polynonamethylene terephthalamide (polyamide 9T), polynonamethylene isophthalamide (polyamide 9I) ), Polynonamethylene hexahydroterephthalamide (polyamide 9T (H)), polynonamethylene naphthalamide (polyamide 9N), polydecamethylene terephthalamide (polyamide) 0T), polydecamethylene isophthalamide (polyamide 10I), polydecamethylene hexahydroterephthalamide (polyamide 10T (H)), polydecamethylene naphthalamide (polyamide 10N), polyundecamethylene terephthalamide (polyamide 11T) ), Polyundecamethylene isophthalamide (polyamide 11I), polyundecamethylene hexahydroterephthalamide (polyamide 11T (H)), polyundecamethylene naphthalamide (polyamide 11N), polydodecamethylene terephthalamide (polyamide) 12T), polydodecamethylene isophthalamide (polyamide 12I), polydodecamethylene hexahydroterephthalamide (polyamide 12T (H)), polydodecamethylene naphthalamide (polyamide 12N) and these polyamidos. And a copolymer using several kinds of raw material monomers and / or raw material monomers of the above aliphatic polyamide. These can use 1 type (s) or 2 or more types.

  Other thermoplastic resins to be mixed include high density polyethylene (HDPE), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), and ultra high molecular weight polyethylene (UHMWPE). , Polypropylene (PP), ethylene / propylene copolymer (EPR), ethylene / butene copolymer (EBR), ethylene / vinyl acetate copolymer (EVA), ethylene / acrylic acid copolymer (EAA), ethylene / Polyolefin resins such as methacrylic acid copolymer (EMAA), ethylene / methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), and ethylene / ethyl acrylate copolymer (EEA); , Carboxyl groups and their salts, acid anhydride groups, epoxy groups, etc. Polyolefin resin containing functional groups, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), PET / PEI copolymer, polyarylate (PAR), polyethylene naphthalate (PEN) Polyester resins such as polybutylene naphthalate (PBN) and liquid crystal polyester (LCP), polyether resins such as polyacetal (POM) and polyphenylene oxide (PPO), polysulfone (PSF), polyethersulfone (PES), etc. Polysulfone resin, polyphenylene sulfide (PPS), polythioether resin such as polythioethersulfone (PTES), polyetheretherketone (PEEK), polyallyletherketone (PAEK), etc. Polyketone resin, polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / butadiene / styrene copolymer (ABS), methacrylonitrile / Polynitrile resins such as styrene / butadiene copolymer (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 resins such as cellulose acetate and cellulose butyrate, polycarbonate (PC), etc. Polycarbonate resins, thermoplastic polyimide (PI), polyamideimide (PAI), polyimide-based resins such as polyether imide, thermoplastic polyurethane resins, polyurethane elastomers, polyester elastomers, and the like. These can use 1 type (s) or 2 or more types. However, from the viewpoint of coextrusion with the (B) modified ethylene / vinyl acetate copolymer saponified product described later, from the viewpoint of melt stability, among the other polyamide resins or thermoplastic resins exemplified above, preferably, It is preferable to mix a resin having a melting point of 240 ° C. or lower.

  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. It is done. 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, o- or p-hydroxybenzoic acid dodecyl. These can use 1 type (s) or 2 or more types.

  Among these, benzenesulfonic acid alkylamides such as benzenesulfonic acid butyramide and benzenesulfonic acid 2-ethylhexylamide, N-ethyl-p-toluenesulfonic acid butyramide, N-ethyl-p-toluenesulfonic acid 2-ethylhexylamide and the like Preferred are hydroxybenzoic acid alkyl esters such as toluenesulfonic acid alkylamides, p-hydroxybenzoic acid ethylhexyl, p-hydroxybenzoic acid hexyldecyl, p-hydroxybenzoic acid ethyldecyl, benzenesulfonic acid butyramide, p-hydroxybenzoic acid More preferred are ethylhexyl and hexyldecyl p-hydroxybenzoate.

  The compounding amount of the plasticizer is preferably 1 to 30 parts by weight and more preferably 1 to 15 parts by weight with respect to 100 parts by weight of the (A) aliphatic polyamide component. When the blending amount of the plasticizer exceeds 30 parts by weight, the low temperature impact resistance of the laminated hose 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 the flexural modulus measured according to ASTM D-790 is preferably 500 MPa or less. If the flexural modulus exceeds this value, the impact improvement 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) A polymer, an ionomer polymer, an aromatic vinyl compound / conjugated diene compound block copolymer can be mentioned, and these can be used alone or in combination of two or more.

The above (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 an α-olefin having 3 or more carbon atoms. As propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1 -Pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicocene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl -1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1 -Hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and the like. These can use 1 type (s) or 2 or more types.
In addition, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-methyl-1, 5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl-1,4,8- Decatriene (DMDT), dicyclopentadiene, cyclohexadiene, cyclooctadiene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloromethyl -5-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. These can use 1 type (s) or 2 or more types.

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

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

  The aromatic vinyl compound / conjugated diene compound block copolymer is a block copolymer comprising an aromatic vinyl compound polymer block and a conjugated diene compound polymer block, and the aromatic vinyl compound polymer block. And a block copolymer having at least one conjugated diene compound-based polymer block. 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 may be mentioned, and these may be used alone or in combination of two or more. it can. 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 these, one aromatic vinyl compound polymer block and one conjugated diene compound polymer block are directly used as an aromatic vinyl compound / conjugated diene compound block copolymer and / or a hydrogenated product thereof. Three polymer blocks are linearly bonded in the order of chain-bonded diblock copolymer, aromatic vinyl compound polymer block-conjugated diene compound polymer block-aromatic vinyl compound polymer block. One or more of the triblock copolymers and hydrogenated products thereof are preferably used, and the unhydrogenated or hydrogenated styrene / butadiene block copolymer, the unhydrogenated or hydrogenated styrene / isoprene block Copolymer, 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 carboxylic acid groups, acid anhydride groups, carboxylic acid ester groups, carboxylic acid metal salts, carboxylic acid imide groups, carboxylic acid amide groups, and epoxy groups. Is 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. These can use 1 type (s) or 2 or more types.

  The blending amount of the impact modifier is preferably 1 to 35 parts by weight and more preferably 5 to 25 parts by weight with respect to 100 parts by weight of the (A) aliphatic polyamide component. If the blending amount of the impact modifier exceeds 35 parts by weight, the original mechanical properties of the laminated hose may be impaired.

  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) Aliphatic polyamide production equipment includes batch-type reaction kettles, one-tank or multi-tank continuous reaction equipment, tubular continuous reaction equipment, uniaxial kneading extruder, biaxial kneading extruder, etc. A known polyamide production apparatus such as an extruder may be used. As a polymerization method, a known method such as melt polymerization, solution polymerization, or solid phase polymerization can be used, and polymerization can be performed by repeating normal pressure, reduced pressure, and pressure operations. These polymerization methods can be used alone or in appropriate combination.

  Moreover, it is preferable that the relative viscosity measured based on JIS K-6920 of (A) aliphatic polyamide is 1.5-5.0, and it is more preferable that it is 2.0-4.5. If the relative viscosity is less than the above value, the mechanical properties of the resulting laminated hose may be insufficient, and if it exceeds the above value, the extrusion pressure and torque will be too high, Manufacturing can be difficult.

  The (B) saponified ethylene / vinyl acetate copolymer used in the present invention contains 0.3 to 40 mol% of the following structural unit (I), and ethylene / acetic acid having an ethylene content of 5 to 55 mol%. This is a saponified product of a vinyl copolymer (hereinafter referred to as (B) modified EVOH).

(Wherein R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or 6 to 10 carbon atoms. R ¹ , R ² , R ³ and R ⁴ may be the same group or different from each other, and R ³ and R ⁴ may be bonded to each other. R ¹ , R ² , R ³ and R ⁴ may have other groups such as a hydroxyl group, a carboxyl group, and a halogen atom.)

In a more preferred embodiment, both R ¹ and R ² are hydrogen atoms. In a more preferred embodiment, R ¹ and R ² are both hydrogen atoms, one of R ³ and R ⁴ is an aliphatic hydrocarbon group having 1 to 10 carbon atoms, and the other is a hydrogen atom. It is. The aliphatic hydrocarbon group is preferably an alkyl group or an alkenyl group. (B) From the viewpoint of placing particular emphasis on the chemical EV permeation preventive property of the modified EVOH, it is more preferable that one of the R ³ and R ⁴ is a methyl group or an ethyl group and the other is a hydrogen atom.

In addition, from the viewpoint of the chemical permeation preventing property of (B) modified EVOH, one of R ³ and R ⁴ is a substituent represented by (CH ₂ ) _i OH (where i is an integer of 1 to 8) It is also preferable that the other is a hydrogen atom. (B) In the case where emphasis is placed on the chemical EV permeation preventive property of the modified EVOH, in the substituent represented by the above (CH ₂ ) _i OH, i is preferably an integer of 1 to 4, and 1 or 2 More preferably, it is more preferably 1.

  The amount of the structural unit (I) contained in the (B) modified EVOH used in the present invention needs to be in the range of 0.3 to 40 mol%. The lower limit of the amount of the structural unit (I) is preferably 0.5 mol% or more, more preferably 1 mol% or more, and further preferably 2 mol% or more. On the other hand, the upper limit of the amount of the structural unit (I) is preferably 35 mol% or less, more preferably 30 mol% or less, and further preferably 25 mol% or less. (B) When the amount of the structural unit (I) contained in the modified EVOH is within the above range, a laminated hose having both chemical permeation preventing property, low temperature impact resistance, and environmental stress load resistance can be obtained.

  Furthermore, it is preferable that the ethylene content of (B) modified EVOH is 5 to 55 mol%. From the viewpoint of (B) the modified EVOH obtaining good flexibility and impact resistance, the lower limit of the ethylene content of the (B) modified EVOH is more preferably 10 mol% or more, and 20 mol% or more. More preferably, it is more preferably 25 mol% or more, and most preferably 31 mol% or more. On the other hand, from the viewpoint of the chemical permeation preventing property of (B) modified EVOH, the upper limit of the ethylene content of (B) modified EVOH is more preferably 50 mol% or less, and further preferably 45 mol% or less. . If the ethylene content is less than 5 mol%, melt moldability may be deteriorated, and if it exceeds 55 mol%, chemical liquid permeation preventive properties may be insufficient.

  The structural unit other than the structural unit (I) and the ethylene unit constituting the (B) modified EVOH used in the present invention is mainly a vinyl alcohol unit. This vinyl alcohol unit is a vinyl alcohol unit which did not react with the below-mentioned (b2) monohydric epoxy compound among the vinyl alcohol units contained in the raw material (b1) EVOH. Further, (b1) unsaponified vinyl acetate units that may be contained in EVOH are usually contained in (B) modified EVOH as they are. (B) Modified EVOH is a random copolymer containing these structural units. Furthermore, other structural units can be included as long as the object of the present invention is not impaired.

  (B) The melt flow rate (MFR) (under 190 ° C. and 2160 g load) of the modified EVOH is preferably 0.1 to 30 g / 10 minutes, and more preferably 0.3 to 25 g / 10 minutes. More preferably, it is 0.5 to 20 g / 10 min. However, those having a melting point near 190 ° C. or exceeding 190 ° C. were measured under a load of 2160 g and at a plurality of temperatures higher than the melting point. The value is extrapolated to 190 ° C.

  The method for producing the (B) modified EVOH is not particularly limited. (B1) Saponified ethylene / vinyl acetate copolymer having ethylene content of 5 to 55 mol% (hereinafter sometimes referred to as (b1) EVOH) and (b2) monovalent epoxy compound having molecular weight of 500 or less (hereinafter referred to as “b1”). (B2) The method of obtaining (B) modified EVOH by making it react with (it may be called a monovalent | monohydric epoxy compound.) Is preferable.

  (B1) EVOH is preferably obtained by saponifying an ethylene / vinyl ester copolymer. A typical vinyl ester used in the production of EVOH is vinyl acetate, but other fatty acid vinyl esters (such as vinyl propionate and vinyl pivalate) can also be used. In addition, as long as the object of the present invention is not inhibited, α-olefin such as propylene, butylene, isobutene, 4-methyl-1-pentene, 1-hexene, 1-octene, (Meth) acrylic acid, methyl (meth) acrylate, unsaturated carboxylic acid or ester thereof such as ethyl (meth) acrylate, vinylsilane compound such as vinyltrimethoxysilane, unsaturated sulfonic acid or salt thereof, alkylthiols, Vinyl pyrrolidone such as N-vinyl pyrrolidone can also be copolymerized. These can use 1 type (s) or 2 or more types.

  (B1) When using EVOH obtained by copolymerizing a vinylsilane compound as a copolymerization component as EVOH, it is preferable to contain 0.0002 to 0.2 mol% as a copolymerization amount. By having a vinylsilane compound as a copolymer component within such a range, the consistency of the melt viscosity between the base resin and (B) the modified EVOH during coextrusion molding is improved, and the coextrusion moldability is improved. There is a case. In particular, when a base resin having a high melt viscosity is used, it is easy to obtain a homogeneous laminated hose. Examples of the vinylsilane compound include vinyltrimethoxysilane, vinyltriethoxysilane, vinyltri (β-methoxy-ethoxy) silane, and γ-methacryloxypropylmethoxysilane. These can use 1 type (s) or 2 or more types. Among these, vinyltrimethoxysilane and vinyltriethoxysilane are preferable.

  Furthermore, the ethylene content of (b1) EVOH is preferably 5 to 55 mol%. From the viewpoint that the (B) modified EVOH used in the present invention obtains good impact resistance, the lower limit of the ethylene content of (b1) EVOH is more preferably 10 mol% or more, and 20 mol% or more. Is more preferably 25 mol% or more, and most preferably 31 mol% or more. On the other hand, from the viewpoint of the chemical permeation preventing property of (B) modified EVOH, the upper limit of the ethylene content of (b1) EVOH is more preferably 50 mol% or less, and further preferably 45 mol% or less. . If the ethylene content is less than 5 mol%, melt moldability may be deteriorated, and if it exceeds 55 mol%, chemical liquid permeation preventive properties may be insufficient.

  Here, when EVOH consists of a blend of two or more types of EVOH having different ethylene contents, the average value calculated from the blending weight ratio is taken as the ethylene content.

  Moreover, (b1) The saponification degree of the vinyl ester component of EVOH is preferably 90% or more. The saponification degree of the vinyl ester component is more preferably 95% or more, further preferably 98% or more, and particularly preferably 99% or more. If the degree of saponification is less than 90%, the chemical solution permeation preventive property may decrease.

  Here, when EVOH consists of a blend of two or more types of EVOH having different saponification degrees, the average value calculated from the blending weight ratio is taken as the saponification degree. In addition, the ethylene content and the saponification degree of EVOH can be obtained by a nuclear magnetic resonance (NMR) method.

  Further, (b1) EVOH may contain a boron compound within a range that does not interfere with the object of the present invention. Examples of the boron compound include boric acids, boric acid esters, borates, and borohydrides. Specifically, examples of boric acids include orthoboric acid, metaboric acid, and tetraboric acid. Examples of boric acid esters include triethyl borate and trimethyl borate. Examples include alkali metal salts of acids, alkaline earth metal salts, and borax. These can use 1 type (s) or 2 or more types. Of these compounds, orthoboric acid is preferred.

  (B1) The content of the boron compound in EVOH is preferably 20 to 2000 ppm, more preferably 50 to 1000 ppm in terms of boron element. When the content of the boron compound is within this range, EVOH in which torque fluctuation during heating and melting is suppressed can be obtained. If the boron element concentration is less than 20 ppm, such an effect may be reduced, and if it exceeds 2000 ppm, gelation tends to occur and moldability may be deteriorated.

  Moreover, (b1) EVOH may contain a phosphoric acid compound. Thereby, the quality (coloring, etc.) of the resin can be stabilized. It does not specifically limit as a phosphoric acid compound, Various acids, such as phosphoric acid and phosphorous acid, its salt, etc. can be used. The phosphate may be contained in any form of a first phosphate, a second phosphate, and a third phosphate, but the first phosphate is preferable. The cationic species is not particularly limited, but is preferably an alkali metal salt. Among these, sodium dihydrogen phosphate and potassium dihydrogen phosphate are preferable.

  (B1) The content of the phosphate compound in EVOH is preferably 200 ppm or less, more preferably 5 to 100 ppm, and even more preferably 5 to 50 ppm in terms of phosphate radical.

  Further, as described later, the (B) modified EVOH used in the present invention is preferably obtained by allowing the reaction between (b1) EVOH and (b2) a monovalent epoxy compound having a molecular weight of 500 or less to be carried out in an extruder. In that case, (b1) EVOH is exposed to heating conditions. At this time, if (b1) EVOH contains an excessive amount of an alkali metal salt and / or an alkaline earth metal salt, the resulting (B) modified EVOH may be colored. In addition, problems such as (B) a decrease in viscosity of the modified EVOH may occur, and the moldability may decrease.

  In order to avoid the above problem, the alkali metal salt contained in (b1) EVOH is preferably 50 ppm or less in terms of metal element, more preferably 30 ppm or less, and further preferably 20 ppm or less. preferable. From the same viewpoint, (b1) the alkaline earth metal salt contained in EVOH is preferably 20 ppm or less, more preferably 10 ppm or less, and further preferably 5 ppm or less in terms of metal element. (B1) It is particularly preferred that the EVOH is substantially free of alkaline earth metal salt.

  Moreover, if it is in the range which does not obstruct the objective of this invention, a heat stabilizer and antioxidant can also be mix | blended with (b1) EVOH.

  (B1) The intrinsic viscosity of EVOH is preferably 0.06 L / g or more. More preferably in the range of 0.07 to 0.2 L / g, still more preferably in the range of 0.075 to 0.15 L / g, and 0.080 to 0.12 L / g. Is particularly preferred. (B1) When the intrinsic viscosity of EVOH is less than 0.06 L / g, stretchability, flexibility, and bending resistance may decrease. On the other hand, when the intrinsic viscosity of (b1) EVOH exceeds 0.2 L / g, gels and blisters are likely to occur in a molded product made of (B) modified EVOH.

  In addition, (b1) EVOH melt flow rate (MFR) (190 ° C. under 2160 g load) is preferably 0.1 to 30 g / 10 min, more preferably 0.3 to 25 g / 10 min. Preferably, it is 0.5-20 g / 10min. However, those having a melting point near 190 ° C. or exceeding 190 ° C. were measured under a load of 2160 g and at a plurality of temperatures higher than the melting point. The value is extrapolated to 190 ° C.

  It is essential that the (b2) monovalent epoxy compound having a molecular weight of 500 or less used in the present invention is a monovalent epoxy compound. That is, it must be an epoxy compound having only one epoxy group in the molecule. When a divalent or higher polyvalent epoxy compound is used, the effects of the present invention cannot be achieved. However, in the production process of the monovalent epoxy compound, a very small amount of the polyvalent epoxy compound may be contained. However, a monovalent epoxy compound containing a very small amount of a polyvalent epoxy compound may be used as the (b2) monovalent epoxy compound having a molecular weight of 500 or less in the present invention as long as the effects of the present invention are not impaired. Is possible.

  The (b2) monovalent epoxy compound having a molecular weight of 500 or less is not particularly limited. Specifically, compounds represented by the following formulas (III) to (IX) are preferably used.

(In the formula, R ⁵ , R ⁶ , R ⁷ , R ⁸ and R ⁹ are each a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms (such as an alkyl group or an alkenyl group), or an oil having 3 to 10 carbon atoms. Represents a cyclic hydrocarbon group (cycloalkyl group, cycloalkenyl group, etc.) and an aromatic hydrocarbon group (phenyl group etc.) having 6 to 10 carbon atoms, and i, j, k, l and m are 1 to Represents an integer of 8.)

  As the (b2) monovalent epoxy compound having a molecular weight of 500 or less represented by the above formula (III), epoxy ethane (ethylene oxide), epoxy propane, 1,2-epoxybutane, 2,3-epoxybutane, 3-methyl -1,2-epoxybutane, 1,2-epoxypentane, 2,3-epoxypentane, 3-methyl-1,2-epoxypentane, 4-methyl-1,2-epoxypentane, 4-methyl-2, 3-epoxypentane, 3-ethyl-1,2-epoxypentane, 1,2-epoxyhexane, 2,3-epoxyhexane, 3,4-epoxyhexane, 3-methyl-1,2-epoxyhexane, 4- Methyl-1,2-epoxyhexane, 5-methyl-1,2-epoxyhexane, 3-ethyl-1,2-epoxyhexane, 3-propyl 1,2-epoxyhexane, 4-ethyl-1,2-epoxyhexane, 5-methyl-1,2-epoxyhexane, 4-methyl-2,3-epoxyhexane, 4-ethyl-2,3-epoxyhexane 2-methyl-3,4-epoxyhexane, 2,5-dimethyl-3,4-epoxyhexane, 3-methyl-1,2-epoxyheptane, 4-methyl-1,2-epoxyheptane, 5, -Methyl-1,2-epoxyheptane, 6-methyl-1,2-epoxyheptane, 3-ethyl-1,2-epoxyheptane, 3-propyl-1,2-epoxyheptane, 3-butyl -1,2-epoxyheptane, 4-ethyl-1,2-epoxyheptane, 4-propyl-1,2-epoxyheptane, 5-ethyl-1,2-epoxyheptane, 4-methyl-2 , 3- To poxyheptane, 4-ethyl-2,3-epoxyheptane, 4-propyl-2,3-epoxyheptane, 2-methyl-3,4-epoxyheptane, 5-methyl-3,4-epoxy Butane, 5-ethyl-3,4-epoxyheptane, 2,5-dimethyl-3,4-epoxyheptane, 2-methyl-5-ethyl-3,4-epoxyheptane, 1,2-epoxyheptane 2,3-epoxyheptane, 3,4-epoxyheptane, 1,2-epoxyoctane, 2,3-epoxyoctane, 3,4-epoxyoctane, 4,5-epoxyoctane, 1,2-epoxynonane, 2,3-epoxynonane, 3,4-epoxynonane, 4,5-epoxynonane, 1,2-epoxydecane, 2,3-epoxydecane, 3,4-epoxydecane, 4,5-epoxy Sidecan, 5,6-epoxydecane, 1,2-epoxyundecane, 2,3-epoxyundecane, 3,4-epoxyundecane, 4,5-epoxyundecane, 5,6-epoxyundecane, 1,2-epoxydodecane 2,3-epoxydodecane, 3,4-epoxydodecane, 4,5-epoxydodecane, 5,6-epoxydodecane, 6,7-epoxydodecane, epoxyethylbenzene, 1-phenyl-1,2-epoxypropane, 3-phenyl-1,2-epoxypropane, 1-phenyl-1,2-epoxybutane, 3-phenyl-1,2-epoxybutane, 4-phenyl-1,2-epoxybutane, 1-phenyl-1, 2-epoxypentane, 3-phenyl-1,2-epoxypentane, 4-phenyl-1,2-epoxypentane 5-phenyl-1,2-epoxypentane, 1-phenyl-1,2-epoxyhexane, 3-phenyl-1,2-epoxyhexane, 4-phenyl-1,2-epoxyhexane, 5-phenyl-1, Examples include 2-epoxyhexane and 6-phenyl-1,2-epoxyhexane. These can use 1 type (s) or 2 or more types.

  Examples of the (b2) monovalent epoxy compound having a molecular weight of 500 or less represented by the above formula (IV) include methyl glycidyl ether, ethyl glycidyl ether, n-propyl glycidyl ether, isopropyl glycidyl ether, n-butyl glycidyl ether, isobutyl glycidyl ether. Tert-butyl glycidyl ether, 1,2-epoxy-3-pentyloxypropane, 1,2-epoxy-3-hexyloxypropane, 1,2-epoxy-3-heptyloxypropane, 1,2-epoxy-3 -Octyloxypropane, 1,2-epoxy-3-phenoxypropane, 1,2-epoxy-3-benzyloxypropane, 1,2-epoxy-4-methoxybutane, 1,2-epoxy-4-ethoxybutane, 1,2-epoxy-4-propo Sibutane, 1,2-epoxy-4-butoxybutane, 1,2-epoxy-4-pentyloxybutane, 1,2-epoxy-4-hexyloxybutane, 1,2-epoxy-4-heptyloxybutane, 1 , 2-epoxy-4-phenoxybutane, 1,2-epoxy-4-benzyloxybutane, 1,2-epoxy-5-methoxypentane, 1,2-epoxy-5-ethoxypentane, 1,2-epoxy- 5-propoxypentane, 1,2-epoxy-5-butoxypentane, 1,2-epoxy-5-pentyloxypentane, 1,2-epoxy-5-hexyloxypentane, 1,2-epoxy-5-phenoxypentane 1,2-epoxy-6-methoxyhexane, 1,2-epoxy-6-ethoxyhexane, 1,2-epoxy-6-propyl Poxyhexane, 1,2-epoxy-6-butoxyhexane, 1,2-epoxy-6-heptyloxyhexane, 1,2-epoxy-7-methoxyheptane, 1,2-epoxy-7-ethoxyheptane, 1,2-epoxy-7-propoxyheptane, 1,2-epoxy-7-butyloxyheptane, 1,2-epoxy-8-methoxyheptane, 1,2-epoxy-8-ethoxyheptane, 1, 2-epoxy-8-butoxyheptane, glycidol, 3,4-epoxy-1-butanol, 4,5-epoxy-1-pentanol, 5,6-epoxy-1-hexanol, 6,7-epoxy-1 -Heptanol, 7,8-epoxy-1-octanol, 8,9-epoxy-1-nonanol, 9,10-epoxy-1-decanol, 10,11-epoxy And xyl-1-undecanol. These can use 1 type (s) or 2 or more types.

  As the (b2) monovalent epoxy compound having a molecular weight of 500 or less represented by the above formula (V), ethylene glycol monoglycidyl ether, propanediol monoglycidyl ether, butanediol monoglycidyl ether, heptanediol monoglycidyl ether, hexanediol Examples thereof include monoglycidyl ether, heptanediol monoglycidyl ether, and octanediol monoglycidyl ether. These can use 1 type (s) or 2 or more types.

  As the (b2) monovalent epoxy compound having a molecular weight of 500 or less represented by the above formula (VI), 3- (2,3-epoxy) propoxy-1-propene, 4- (2,3-epoxy) propoxy-1 -Butene, 5- (2,3-epoxy) propoxy-1-pentene, 6- (2,3-epoxy) propoxy-1-hexene, 7- (2,3-epoxy) propoxy-1-heptene, 8- (2,3-epoxy) propoxy-1-octene and the like. These can use 1 type (s) or 2 or more types.

  As the (b2) monovalent epoxy compound having a molecular weight of 500 or less represented by the above formula (VII), 3,4-epoxy-2-butanol, 2,3-epoxy-1-butanol, 3,4-epoxy-2 -Pentanol, 2,3-epoxy-1-pentanol, 1,2-epoxy-3-pentanol, 2,3-epoxy-4-methyl-1-pentanol, 2,3-epoxy-4,4 -Dimethyl-1-pentanol, 2,3-epoxy-1-hexanol, 3,4-epoxy-2-hexanol, 4,5-epoxy-3-hexanol, 1,2-epoxy-3-hexanol, 2, 3-epoxy-4-methyl-1-hexanol, 2,3-epoxy-4-ethyl-1-hexanol, 2,3-epoxy-4,4-dimethyl-1-hexanol, 2,3-epoxy -4,4-diethyl-1-hexanol, 2,3-epoxy-4-methyl-4-ethyl-1-hexanol, 3,4-epoxy-5-methyl-2-hexanol, 3,4-epoxy-5 , 5-dimethyl-2-hexanol, 3,4-epoxy-2-heptanol, 2,3-epoxy-1-heptanol, 4,5-epoxy-3-heptanol, 2,3-epoxy-4-heptanol, 1 , 2-epoxy-3-heptanol, 2,3-epoxy-1-octanol, 3,4-epoxy-2-octanol, 4,5-epoxy-3-octanol, 5,6-epoxy-4-octanol, 2 , 3-epoxy-4-octanol, 1,2-epoxy-3-octanol, 2,3-epoxy-1-nonanol, 3,4-epoxy-2-nonanol, , 5-epoxy-3-nonanol, 5,6-epoxy-4-nonanol, 3,4-epoxy-5-nonanol, 2,3-epoxy-4-nonanol, 1,2-epoxy-3-nonanol, 2, , 3-epoxy-1-decanol, 3,4-epoxy-2-decanol, 4,5-epoxy-3-decanol, 5,6-epoxy-4-decanol, 6,7-epoxy-5-decanol, 3, , 4-epoxy-5-decanol, 2,3-epoxy-4-decanol, 1,2-epoxy-3-decanol, and the like. These can use 1 type (s) or 2 or more types.

  Examples of the (b2) monovalent epoxy compound having a molecular weight of 500 or less represented by the above formula (VIII) include 1,2-epoxycyclopentane, 1,2-epoxycyclohexane, 1,2-epoxycycloheptane, 1,2- Examples thereof include epoxycyclooctane, 1,2-epoxycyclononane, 1,2-epoxycyclodecane, 1,2-epoxycycloundecane, 1,2-epoxycyclododecane and the like. These can use 1 type (s) or 2 or more types.

  Examples of the (b2) monovalent epoxy compound having a molecular weight of 500 or less represented by the above formula (IX) include 3,4-epoxycyclopentene, 3,4-epoxycyclohexene, 3,4-epoxycycloheptene, 3,4- Examples thereof include epoxycyclooctene, 3,4-epoxycyclononene, 1,2-epoxycyclodecene, 1,2-epoxycycloundecene, 1,2-epoxycyclododecene and the like. These can use 1 type (s) or 2 or more types.

  The (b2) monovalent epoxy compound having a molecular weight of 500 or less is more preferably an epoxy compound having 2 to 8 carbon atoms. The (b2) monovalent epoxy compound is more preferably a compound represented by the above formula (III) or (IV). From the viewpoint of (b1) reactivity with EVOH and prevention of chemical permeation of the obtained (B) modified EVOH, 1,2-epoxybutane, 2,3-epoxybutane, epoxypropane, epoxyethane and glycidol are further included. Of these, epoxypropane and glycidol are particularly preferable.

  (B) Modified EVOH is obtained by reacting the (b1) EVOH with the (b2) monovalent epoxy compound. At this time, the blending amount of the ((b2) monovalent epoxy compound is preferably 1 to 50 parts by weight, more preferably 2 to 40 parts by weight with respect to 100 parts by weight of (b1) EVOH, More preferably, it is 5-35 weight part.

  The method for producing (B) modified EVOH by reacting (b1) EVOH with (b2) monovalent epoxy compound having a molecular weight of 500 or less is not particularly limited, but (b1) EVOH and (b2) monovalent epoxy compound And a production method in which (b1) EVOH and (b2) a monovalent epoxy compound are reacted in an extruder, and the like.

  In the production method by solution reaction, (B1) modified EVOH is obtained by reacting (b2) a monovalent epoxy compound with (b1) EVOH solution in the presence of an acid catalyst or an alkali catalyst. Alternatively, (B) modified EVOH can be produced by dissolving (b1) EVOH and (b2) a monovalent epoxy compound in a reaction solvent and performing a heat treatment. The reaction solvent is preferably a polar aprotic solvent that is a good solvent for (b1) EVOH, such as dimethyl sulfoxide, dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.

  Reaction catalysts include acid catalysts such as p-toluenesulfonic acid, methanesulfonic acid, trifluoromethanesulfonic acid, sulfuric acid, and boron trifluoride, and alkali catalysts such as sodium hydroxide, potassium hydroxide, lithium hydroxide, and sodium methoxide. Is mentioned. Among these, it is preferable to use an acid catalyst. The amount of the catalyst is suitably about 0.0001 to 10 parts by weight per 100 parts by weight of (b1) EVOH. The reaction temperature is suitably from room temperature to 150 ° C.

  In the production method in which (b1) EVOH and (b2) a monovalent epoxy compound are reacted in an extruder, the extruder to be used is not particularly limited, but a single screw extruder, a twin screw extruder, or a multi-screw having two or more screws. It is preferable to react (b1) EVOH with (b2) the monovalent epoxy compound at a temperature of about 200 ° C. to 300 ° C. using an extruder. When a twin screw extruder or a multi-screw extruder having two or more screws is used, it is easy to increase the pressure in the reaction part by changing the screw configuration, and (b1) EVOH and (b2) a monovalent epoxy compound The reaction can be performed efficiently. In the single screw extruder, it is possible to increase the pressure in the reaction section by connecting two or more extruders and arranging a valve in the resin flow path therebetween. Similarly, two or more twin-screw extruders or two or more multi-screw extruders may be connected and manufactured.

  When the production method that reacts in the extruder and the production method by solution reaction are compared, in the case of solution reaction, (b1) a solvent that dissolves EVOH is required, and the solvent is recovered and removed from the reaction system after completion of the reaction. The process is complicated. In order to increase the reactivity between (b1) EVOH and (b2) the monovalent epoxy compound, it is preferable to maintain the reaction system under heating and / or pressure conditions, but compared with the case of solution reaction. In the reaction in the extruder, it is easy to heat and / or maintain the pressure condition of the reaction system, and the merit of the reaction in the extruder is great from that viewpoint.

  Furthermore, when a reaction between (b1) EVOH and (b2) a monovalent epoxy compound is performed by a solution reaction, the reaction control is not always easy and the reaction may proceed excessively. That is, as a result of the reaction between (b1) EVOH and (b2) a monovalent epoxy compound, (B) modified EVOH having the above structural unit (I) is obtained, but the hydroxyl group contained in the structural unit (I) In addition, (b2) a monovalent epoxy compound may react to obtain a compound different from the structural unit specified in the present invention.

  Specifically, when the (b2) monovalent epoxy compound is ethylene oxide, EVOH containing the structural unit (II) shown below is generated by the above-described excessive reaction.

（式中、ｎは１以上の自然数を表す。）

(In the formula, n represents a natural number of 1 or more.)

  When the proportion of the structural unit (II) shown above, which is different from the structural unit (I) specified in the present invention, increases, the chemical solution permeation preventive property of the obtained (B) modified EVOH may decrease. is there. Furthermore, when the reaction between (b1) EVOH and (b2) the monovalent epoxy compound is carried out in the extruder, the occurrence of such a side reaction can be effectively suppressed. Also from this viewpoint, a method of producing (B) modified EVOH by reacting (b1) EVOH with (b2) a monovalent epoxy compound in an extruder is preferable.

  In addition, since the (b2) monovalent epoxy compound having a molecular weight of 500 or less used in the present invention is not necessarily high in boiling point, in the production method by solution reaction, when the reaction system is heated, (b2) Monovalent epoxy compounds may volatilize. However, it is possible to suppress volatilization of the (b2) monovalent epoxy compound outside the system by reacting (b1) EVOH with (b2) the monovalent epoxy compound in the extruder. In particular, when (b2) the monovalent epoxy compound is added to the extruder, the reactivity between (b1) EVOH and (b2) the monovalent epoxy compound is increased by press-fitting under pressure, and (b2) one It is possible to remarkably suppress volatilization of the valent epoxy compound out of the system.

  The method for mixing (b1) EVOH and (b2) monovalent epoxy compound during the reaction in the extruder is not particularly limited, and (b2) monovalent epoxy compound is added to (b1) EVOH before feeding to the extruder. Examples thereof include a method of spraying, a method of feeding (b1) EVOH to an extruder, and a method of contacting (b2) a monovalent epoxy compound in the extruder. Among these, from the viewpoint of suppressing volatilization of the (b2) monovalent epoxy compound to the outside of the system, a method of feeding (b1) EVOH to the extruder and then contacting the (b2) monovalent epoxy compound in the extruder is preferable. . Moreover, although the addition position of the (b2) monovalent epoxy compound in the extruder is also arbitrary, from the viewpoint of the reactivity between (b1) EVOH and (b2) the monovalent epoxy compound, with respect to the molten (b1) EVOH (B2) It is preferable to add a monovalent epoxy compound.

  Preferably, the production method of (b1) EVOH and (b2) monovalent epoxy compound by reaction in the extruder is (1) (b1) EVOH melting step, (2) (b2) monovalent epoxy compound It comprises an addition step and (3) a step of removing unreacted (b2) monovalent epoxy compound by venting or the like. From the viewpoint of smoothly performing the reaction, it is more preferable to remove moisture and oxygen from the system. For this reason, moisture and oxygen may be removed using a vent or the like before the (b2) monovalent epoxy compound is added into the extruder.

  In addition, as described above, in the step (b2) of adding the monovalent epoxy compound, it is preferable to press-fit the (b2) monovalent epoxy compound under pressure. At this time, if this pressure is insufficient, problems such as a decrease in the reaction rate and fluctuation in the discharge amount occur. The required pressure varies greatly depending on the boiling point of the (b2) monovalent epoxy compound and the extrusion temperature, but is usually preferably in the range of 0.5 to 30 MPa, more preferably in the range of 1 to 20 MPa.

  The (B) modified EVOH used in the present invention includes at least one selected from the group consisting of alkali metal salts, alkaline earth metal salts, carboxylic acids and phosphoric acid compounds, (b1) EVOH and (b2) It can also be added after (B) modified EVOH is obtained by reaction with a monovalent epoxy compound. Generally, at least one selected from the group consisting of alkali metal salts, alkaline earth metal salts, carboxylic acids, and phosphoric acid compounds as necessary in order to improve various physical properties of EVOH such as improvement of adhesion and suppression of coloring. Often seeds are added. However, as described above, the addition of the various compounds described above may cause coloring or a decrease in viscosity during the reaction between (b1) EVOH and (b2) monovalent epoxy compound by an extruder. . For this reason, after the reaction between (b1) EVOH and (b2) the monovalent epoxy compound, the remaining (b2) monovalent epoxy compound is removed by a vent, and then an alkali metal salt, alkaline earth metal salt, carboxylic acid and phosphorus are removed. It is preferable to add at least one selected from the group consisting of acid compounds to the obtained (B) modified EVOH. By adopting this addition method, (B) modified EVOH can be obtained without causing problems such as coloring and viscosity reduction.

  Various additives may be added to the (B) modified EVOH used in the present invention, if necessary. Examples of such additives include antioxidants, plasticizers, heat stabilizers, UV absorbers, antistatic agents, lubricants, colorants, fillers, or other thermoplastic resins, It can mix | blend in the range which does not inhibit the effect of this invention.

  Specifically, 2,5-di-t-butylhydroquinone, 2,6-di-t-butyl-p-cresol, 4,4′-thiobis- (6-t-butylphenol), 2,2′- Methylene-bis- (4-methyl-6-tert-butylphenol), octadecyl-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate, 4,4′-thiobis- (6 -T-butylphenol) and other antioxidants, ethylene-2-cyano-3,3'-diphenyl acrylate, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-) 5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-5′-methylphenyl) benzotriazole, 2- (2′-hydroxy-3′-t-butyl-5′-me Ruphenyl) UV absorbers such as 5-chlorobenzotriazole, 2-hydroxy-4-methoxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, dimethyl phthalate, diethyl phthalate, dioctyl phthalate, wax, liquid paraffin , Plasticizers such as phosphate esters, pentaerythritol monostearate, sorbitan monopalmitate, sulfated polyolefins, antistatic agents such as polyethylene oxide and carbowax, lubricants such as ethylene bisstearamide and butyl stearate, Examples thereof include colorants such as carbon black, phthalocyanine, quinacridone, indoline, azo pigments, bengara, fillers such as glass fiber, asbestos, ballastite, calcium silicate, and the like.

  In addition, the modified EVOH (B) used in the present invention has a hydrotalcite compound, a hindered phenol-based heat, a hindered amine-based heat to such an extent that the effects of the present invention are not hindered in order to improve the melt stability and the like. One or two or more kinds of stabilizers and metal salts of higher aliphatic carboxylic acids (for example, calcium stearate, magnesium stearate, etc.) are used to such an extent that the effect of the present invention is not inhibited against (B) modified EVOH (0.01 ˜1 wt%) can also be added.

The (C) fluorine-containing polymer used in the present invention is a fluorine-containing polymer in which a functional group having reactivity to an amino group or a hydroxyl group is introduced into a molecular chain (hereinafter referred to as ( C) Sometimes referred to as a 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 Nylidene / pentafluoropropylene / tetrafluoroethylene copolymer, vinylidene fluoride / perfluoroalkyl vinyl ether / tetrafluoroethylene copolymer, ethylene / chlorotrifluoroethylene copolymer (ECTFE), vinylidene fluoride / chlorotrifluoroethylene A copolymer is mentioned. These can use 1 type (s) or 2 or more types.

  Among the fluorine-containing polymers exemplified above (C), in terms of heat resistance and chemical resistance, fluorine-containing polymers having tetrafluoroethylene units as essential components, 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 preferable. .

  An ethylene / tetrafluoroethylene copolymer (hereinafter sometimes referred to as ETFE) includes 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 60/40 to 40 / More preferably, it is 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), cyclohex Vinyl ethers such as xyl 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 can be mentioned. These can use 1 type (s) or 2 or more types.

In (C) fluorine-containing polymer, wherein the general formula _{CH 2 = CX (CF 2)} n compounds represented by Y is preferably used (hereinafter, referred to. FAE). The content of polymerized units based on FAE is preferably 0.01 to 20 mol%, more preferably 0.1 to 15 mol%, and more preferably 1 to 10 mol% in all polymerized units. More preferably. If the content of FAE is less than the above value, crack resistance may be reduced, or a fracture phenomenon may occur under stress, and if it exceeds the above value, mechanical strength may be reduced. .

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 crack generation in the molded product or molded product) may be insufficient, while When 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 . These can use 1 type (s) or 2 or more types.

Among these, a compound represented by CH ₂ ═CH (CF ₂ ) _n Y is more preferable, and in that case, n in the formula is n = 2 to 4 (C) fluorinated polymer. It is further preferable because both the chemical solution permeation preventive property and the crack resistance property 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 copolymerizable with the 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 can be mentioned. These can use 1 type (s) or 2 or more types. The amount of polymerized units based on vinylidene fluoride is preferably at least 30 mol% in 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), dimethyl 2,2'-azobisisobutyrate, 2,2'-azobis [2- (hydroxymethyl) propionitrile], 4,4'-azobis (4-cyano Pentenoic 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, acetyl peroxide , Isobutyryl peroxide, octanoyl peroxide, benzoyl peroxide , Non-fluorinated diacyl peroxides such as lauroyl peroxide, methyl ethyl ketone peroxide, ketone peroxides such as cyclohexanone peroxide, peroxydicarbonates 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 a chlorine atom, and p is an integer of 1 to 10.) Fluorine-containing diacyl peroxide such as a compound represented by the following formula, inorganic peroxides such as potassium persulfate, sodium persulfate, and ammonium persulfate. The These can use 1 type (s) or 2 or more types.

  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. These can use 1 type (s) or 2 or more types.

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

  When (C) a fluorine-containing polymer is coextruded with the above (A) aliphatic polyamide, (B) modified EVOH, etc., sufficient melt fluidity can be obtained at a kneading temperature and a molding temperature range without significant deterioration. In order to ensure the above, it is preferable that 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, and 1 to 100 g / More preferably, it is 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, but when coextruded with the (A) aliphatic polyamide, (B) modified EVOH, etc., the molding temperature of the resin It is preferable that it is close to. 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. In particular, the melting point of the fluorine-containing polymer is preferably 180 to 230 ° C. in view of the heat melting stability during coextrusion with (B) the modified EVOH. If the melting point is out of the above range, the continuous productivity of the laminated hose may be inferior, and (B) in order to ensure the heat melting stability during co-extrusion with the modified EVOH, the (C) fluorine-containing system When the molding temperature of the polymer is lowered, pulsation of the layer made of the fluorinated polymer is induced, and (B) good interlayer adhesion with the modified EVOH may be inferior. Here, the melting point means that the sample is heated to a temperature higher than the expected melting point using a differential scanning calorimeter, and then the sample is cooled at a rate of 10 ° C. per minute and cooled to 30 ° C. The temperature of the peak value of the melting curve measured by standing for about 1 minute and then increasing the temperature at a rate of 10 ° C. per minute is defined as the melting point.

  The (C) fluorine-containing polymer used in the present invention has a functional group having reactivity with an amino group or hydroxyl group in the molecular structure, and the functional group is (C) a fluorine-containing polymer. It may be contained either at the molecular end of the polymer or at the side chain or 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 polyamide resins include carboxyl groups, acid anhydride groups or carboxylates, hydroxyl groups, sulfo groups or sulfonates, epoxy groups, cyano groups, carbonate groups, and carboxylic acid halides. There may be mentioned at least one selected from the group. 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 hose, (C) a 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, hydroxypropyl acrylate, hydroxypropyl methacrylate, hydroxyl group-containing monomers such as hydroxyalkyl vinyl ether. These can use 1 type (s) or 2 or more types.

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 CH2COOH
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. These can use 1 type (s) or 2 or more types.

  (C) The content of the functional group-containing monomer in the fluorine-containing polymer is preferably 0.05 to 20 mol%, and 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. On the other hand, if it exceeds 20 mol%, the heat resistance is lowered, and when processing at high temperature, adhesion failure, coloring or foaming, use at high temperature, peeling, coloring, foaming, elution, etc. may occur due to decomposition. 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 the terminal group of the fluorine-containing polymer is generally a group having a bond of —OC (═O) O—, 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. ] Those _{structures, -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. The carboxylic acid halide group specifically has a structure of —COY [Y is a halogen element], and examples thereof include —COF and —COCl. These can use 1 type (s) or 2 or more types.

  In order to introduce a carbonate group at the molecular terminal of the polymer, various methods using a polymerization initiator or a chain transfer agent can be employed. However, a method using peroxide, particularly peroxycarbonate, as a polymerization initiator is available. It can be preferably used in terms of quality such as economical efficiency, heat resistance, chemical resistance and the like. Further, it is preferable to use peroxycarbonate because the polymerization temperature can be lowered and the side reaction does not accompany 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 Examples thereof include dicarbonate and di-2-ethylhexyl peroxydicarbonate. These can use 1 type (s) or 2 or more types.

  The amount of peroxycarbonate used varies depending on the type of polymer (composition, etc.), the molecular weight, the polymerization conditions, and the type of initiator used, but is 0 for 100 parts by weight of the total polymer obtained by polymerization. The amount is preferably 0.05 to 20 parts by weight, more preferably 0.1 to 10 parts by weight. 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 exceeds the above value, it may be difficult to control the polymerization rate. When the amount used is less than the above value, 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 300 to 1000. More preferably. 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. When the number exceeds 3000, the heat resistance is lowered, and when processing at a high temperature, poor adhesion, coloring, foaming, peeling at the time of use, coloring / foaming, elution, etc. may occur during use at a high temperature. 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 or a hydroxyl 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, the functional group having reactivity with amino groups or hydroxyl groups is contained in the molecular chain, so that the surface of various materials whose interlayer adhesion is insufficient or impossible in the laminated hose Excellent interlaminar adhesion with other substrates can be imparted directly without performing special treatment such as treatment or coating with an adhesive resin.

  The (C) fluorine-containing polymer used in the present invention has various fillings such as inorganic powder, glass fiber, carbon fiber, metal oxide, or carbon as long as the performance is not impaired 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 blended, improving mechanical properties, improving weather resistance, imparting design properties, preventing static electricity, improving moldability Etc. are possible.

  The laminated hose according to the present invention comprises (A) an (a) layer composed of an aliphatic polyamide, (B) a (b) layer composed of a saponified ethylene / vinyl acetate copolymer ((B) modified EVOH), (C) ) At least three layers having (c) layer composed of a fluorine-containing polymer ((C) fluorine-containing polymer) in which a functional group having reactivity to an amino group or hydroxyl group is introduced into the molecular chain Consists of the above.

  In the laminated hose 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 hose. (A) By arranging the (a) layer made of aliphatic polyamide in the outermost layer, a laminated hose excellent in chemical resistance and flexibility can be obtained.

  In the laminated hose of the present invention, it is essential to include (B) a layer consisting of (B) a saponified ethylene / vinyl acetate copolymer, (A) a layer consisting of (A) an aliphatic polyamide, and (C (B) a layer (b) made of a saponified product of (B) a modified ethylene / vinyl acetate copolymer and (C) a fluorine-containing polymer (c) More preferably, the layer is directly bonded. (B) If the (b) layer made of modified EVOH is not included, the chemical solution permeation-preventing property, particularly hydrocarbon permeation-preventing property, of the laminated hose is lowered. Furthermore, when normal (b1) EVOH, which is not (B) modified EVOH, is used, the chemical solution permeation prevention property is excellent, but the low-temperature impact resistance and environmental stress load resistance of the laminated hose are inferior. Moreover, when the (c) layer which consists of (C) a fluorine-containing polymer is not included, it will be inferior to the chemical resistance of a laminated hose. Further, by using the (C) fluorine-containing polymer defined in the present invention, it is not necessary to provide an adhesive layer, and (B) an excellent interlayer adhesion with the (b) layer made of modified EVOH is obtained. It becomes possible.

  In the laminated hose of the present invention, when the conductive layer made of the fluorine-containing polymer composition containing a conductive filler is disposed in the innermost layer of the laminated hose, the chemical resistance and the chemical liquid permeation preventive property are excellent. At the same time, when used as a fuel pipe hose, it is possible to prevent the spark generated by the internal friction of the fuel circulating in the pipe or the friction with the pipe wall from igniting the fuel. At that time, by arranging the layer made of a fluorine-containing polymer having no conductivity outside the conductive layer, it is possible to achieve both low temperature impact resistance and conductivity, and economical. This is also advantageous. Furthermore, the fluorine-containing polymer referred to here includes the (C) fluorine-containing polymer having a functional group in the molecular chain as defined in the present invention, and includes a fluorine-containing polymer having no functional group described later. Also refers to polymer.

  Conductivity means that, for example, when a flammable fluid such as gasoline is continuously in contact with an insulator such as resin, static electricity may accumulate and ignite, but this static electricity will not accumulate. Says having electrical properties. This makes it possible to prevent explosion due to static electricity generated when a fluid such as fuel is conveyed.

  The conductive filler includes all fillers added to impart conductive performance to the resin, and examples thereof include granular, flaky and fibrous fillers.

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

  Carbon nanotubes are what are called hollow carbon fibrils, which have an outer region consisting of an essentially continuous multi-layer of regularly arranged carbon atoms, and an inner hollow region, each layer And the hollow region are essentially cylindrical fibrils arranged substantially concentrically around the cylindrical axis of the fibrils. 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, and 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 the outer diameter 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 that are commonly used to impart conductivity. Preferred carbon blacks include acetylene black obtained by incomplete combustion of acetylene gas, and furnace-type incompleteness using crude oil as a raw material. Examples include, but are not limited to, ketjen black, oil black, naphthalene black, thermal black, lamp black, channel black, roll black, and disk black produced by 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.

Since the blending amount of the conductive filler varies depending on the type of the conductive filler to be used, it cannot be specified unconditionally. However, from the viewpoint of balance between conductivity, fluidity, mechanical strength, etc., 100 wt. In general, 3 to 30 parts by weight are preferably selected with respect to parts.
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.

  In the laminated hose 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 hose, the use, etc., but the thickness of each layer is It is determined in consideration of the properties of the laminated hose, such as chemical solution permeation prevention, low temperature impact resistance, and flexibility. In general, the thicknesses of the (a) layer, (b) layer, and (c) layer are each preferably 3 to 90% with respect to the total thickness of the laminated hose. In consideration of the chemical solution permeation prevention property, the thickness of the layers (b) and (c) is more preferably 5 to 80%, and further preferably 10 to 50% with respect to the thickness of the entire laminated hose.

  Further, the total number of layers in the laminated hose of the present invention is (A) a layer (a) made of aliphatic polyamide, (B) a layer (b) made of modified EVOH, and (C) a fluorine-containing polymer ( As long as there are at least three layers including c) layers, there is no particular limitation. Furthermore, the laminated hose of the present invention has other functions in addition to the three layers (a), (b), and (c) to provide additional functions or to obtain an economically advantageous laminated hose. You may have the layer which consists of a plastic resin 1 layer or 2 layers or more.

  Other thermoplastic resins include polymetaxylylene adipamide (polyamide MXD6), polymetaxylylene veramide (polyamide MXD8), polymetaxylylene azelamide other than (A) aliphatic polyamide defined in the present invention. (Polyamide MXD9), polymetaxylylene sebacamide (polyamide MXD10), polymetaxylylene dodecamide (polyamide MXD12), polymetaxylylene terephthalamide (polyamide MXDT), polymetaxylylene isophthalamide (polyamide MXDI), polymetaxyl Silylene naphthalamide (polyamide MXDN), polybis (4-aminocyclohexyl) methane dodecamide (polyamide PACM12), polybis (4-aminocyclohexyl) methane terephthalamide (polyamide PACM) ), Polybis (4-aminocyclohexyl) methane isophthalamide (polyamide PACMI), polybis (3-methyl-4-aminocyclohexyl) methane dodecamide (polyamide dimethyl PACM12), polyisophorone adipamide (polyamide IPD6), polyisophorone Terephthalamide (polyamide IPDT), polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide 6I), polytrimethylhexamethylene terephthalamide (polyamide TMHT), polynonamethylene terephthalamide (polyamide) 9T), polynonamethylene isophthalamide (polyamide 9I), polynonamethylene hexahydroterephthalamide (polyamide 9T (H)), polynonamethylene naphthalamide (polyamide) N), polydecamethylene terephthalamide (polyamide 10T), polydecamethylene isophthalamide (polyamide 10I), polydecamethylene hexahydroterephthalamide (polyamide 10T (H)), polydecamethylene naphthalamide (polyamide 10N) Polyundecamethylene terephthalamide (Polyamide 11T), Polyundecamethylene isophthalamide (Polyamide 11I), Polyundecamethylene hexahydroterephthalamide (Polyamide 11T (H)), Polyundecamethylene naphthalamide (Polyamide) 11N), polydodecamethylene terephthalamide (polyamide 12T), polydodecamethylene isophthalamide (polyamide 12I), polydodecamethylene hexahydroterephthalamide (polyamide 12T (H)), polydodecamethylene Examples thereof include nnaphthalamide (polyamide 12N) and copolymers using several kinds of these polyamide raw material monomers.

  In addition, fluorine-containing polymers other than those specified in the present invention (here, other than those specified in the present invention are fluorine-containing polymers that do not contain functional groups having reactivity with amino groups or hydroxyl groups) (Polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), ethylene / tetrafluoroethylene copolymer (ETFE), polychlorotrifluoroethylene (PCTFE), ethylene / chlorotrifluoroethylene copolymer) Polymer (ECTFE), tetrafluoroethylene / hexafluoropropylene copolymer (TFE / HFP, FEP), tetrafluoroethylene / hexafluoropropylene / vinylidene fluoride copolymer (TFE / HFP / VDF, THV), tetrafluoro Ethylene / fluoro (alkyl vinyl ether) Polymer (PFA), 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), ethylene / acrylic acid copolymer (EAA), ethylene / methacrylic acid copolymer (EMAA), ethylene / Polyolefin resins such as methyl acrylate copolymer (EMA), ethylene / methyl methacrylate copolymer (EMMA), ethylene / ethyl acrylate copolymer (EEA), and acrylic acid, methacrylic acid, maleic acid, Fumaric acid, itaconic acid, crotonic acid, mesaconic acid, cytosine Carboxylic acid, glutaconic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic acid and other carboxyl groups and metal salts thereof (Na , Zn, K, Ca, Mg), maleic anhydride, itaconic anhydride, citraconic anhydride, acid anhydrides such as endobicyclo- [2.2.1] -5-heptene-2,3-dicarboxylic anhydride Group polyolefin resin, polybutylene terephthalate (PBT), polyethylene terephthalate (PET) containing functional groups such as epoxy groups such as glycidyl acrylate, glycidyl methacrylate, glycidyl ethacrylate, glycidyl itaconate, glycidyl itaconate ), Polyethylene isophthalate (PEI), PET / PEI copolymer, polyaryle (PAR), polybutylene naphthalate (PBN), polyethylene naphthalate (PEN), polyester resins such as liquid crystal polyester (LCP), polyether resins such as polyacetal (POM) and polyphenylene oxide (PPO), polysulfone ( PSF), polysulfone resins such as polyethersulfone (PES), polythioether resins such as polyphenylene sulfide (PPS) and polythioethersulfone (PTES), polyetheretherketone (PEEK), polyallyletherketone (PAEK) Such as polyketone resins, polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile / styrene copolymer (AS), methacrylonitrile / styrene copolymer, acrylonitrile / budadiene / styrene Polynitrile resins such as len copolymer (ABS), methacrylonitrile / styrene / butadiene copolymer (MBS), polymethacrylate resins such as polymethyl methacrylate (PMMA), polyethyl methacrylate (PEMA), poly Polyvinyl chloride resins such as polyvinyl ester resins such as vinyl acetate (PVAc), polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride / vinylidene chloride copolymers, vinylidene chloride / methyl acrylate copolymers, etc. Cellulose resins such as cellulose acetate and cellulose butyrate, polycarbonate resins such as polycarbonate (PC), polyimide resins such as thermoplastic polyimide (PI), polyamideimide (PAI), and polyetherimide, thermoplastic polyurethane resins, Polyamide ela Tomah, polyurethane elastomers, polyester elastomers.

  In the laminated hose of the present invention, (B) From the viewpoint of the melt stability of the modified EVOH, among the above-exemplified thermoplastic resins, the polyester resin, polyamide resin, polythioethylene having a melting point of 240 ° C. or lower is preferable. -Tellurium resins and fluorine-containing polymers are used.

  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.

  The number of layers of the laminated hose of the present invention is 3 layers or more, but it is 8 layers or less, preferably 3 to 7 layers as judged from the mechanism of the hose production apparatus.

  As a laminated hose manufacturing method, using an extruder corresponding to the number of layers or the number of materials, melt extrusion, a method of simultaneously laminating inside or outside the die (coextrusion method), or once a single layer hose, There is a method (coating method) in which a laminated hose produced by the above method is produced in advance, and an adhesive is used on the outside in order to integrate the resins and laminate them. The laminated hose of the present invention is preferably produced by a co-extrusion method in which various materials are co-extruded in a molten state and both are heat-sealed (melt-bonded) to produce a laminated structure hose in one step.

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

  The laminated 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 having the entire length of the laminated hose, but may be partially provided in an appropriate region on the way. The corrugated region can be easily formed by first molding a straight tubular hose and then molding it to obtain a predetermined corrugated shape. 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.

  In all or part of the outer periphery of the laminated hose thus formed, epichlorohydrin rubber (ECO), acrylonitrile / butadiene rubber (NBR), NBR, and poly are considered in consideration of wear with stones, other parts, and flame resistance. Mixture of vinyl chloride, chlorosulfonated polyethylene rubber, chlorinated polyethylene rubber, acrylic rubber (ACM), chloroprene rubber (CR), ethylene / propylene rubber (EPR), ethylene / propylene / diene rubber (EPDM), mixture of NBR and EPDM A solid or sponge-like protective member (protector) made of a thermoplastic elastomer such as rubber, vinyl chloride, olefin, ester or amide can be disposed. The protective member may be a sponge-like porous body by a known method. By using a porous body, a protective part that is lightweight and excellent in heat insulation can be formed. Moreover, material cost can also be reduced. Alternatively, the strength may be improved by adding glass fiber or the like. Although the shape of a protection member is not specifically limited, Usually, it is a block-shaped member which has a recessed part which receives a cylindrical member or a laminated hose. In the case of a cylindrical member, the laminated hose can be inserted later into a cylindrical member prepared in advance, or the cylindrical member can be coated and extruded onto the laminated hose to adhere both together. In order to bond them together, an adhesive is applied to the inner surface of the protective member or the concave surface as necessary, and the laminated hose and the protective member are integrated by inserting or fitting the laminated hose thereto and bringing them into close contact. Forming a structure. It can also be reinforced with metal or the like.

  The outer diameter of the laminated hose is determined so that the flow rate of chemicals (for example, fuel such as alcohol-containing gasoline) is taken into consideration, and the wall thickness is such that the permeation amount of fuel does not increase and the normal hose breaking pressure can be maintained. The hose is designed to have a thickness that can maintain flexibility with a satisfactory degree of ease of assembly work and vibration resistance during use, but is not limited thereto. Preferably, the outer diameter is 4 to 300 mm, the inner diameter is 3 to 250 mm, and the wall thickness is 0.5 to 25 mm.

  The laminated hose of the present invention includes machine parts such as automobile parts, internal combustion engines, electric tool housings, industrial materials, industrial materials, electrical / electronic parts, medical care, food, household / office supplies, building materials-related parts, furniture. There are various uses such as parts.

  Moreover, since the laminated hose of the present invention is excellent in chemical solution permeation prevention properties, it is suitable for a chemical solution transport 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. Alcohols, 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. . The laminated hose of the present invention is suitable as a hose for conveying the above chemical solution, specifically, a fuel hose such as a feed hose, a return hose, an evaporative hose, a fuel filler hose, an ORVR hose, a reserve hose, a vent hose, an oil hose, etc. , Oil drilling hose, brake hose, window washer fluid hose, radiator hose, cooling water, refrigerant cooler hose, air conditioner refrigerant hose, heater hose, road heating hose, floor heating hose, infrastructure supply hose, fire extinguisher And fire extinguishing equipment hoses, medical cooling equipment hoses, ink, paint spraying hoses, and other chemical hose. In particular, it is suitable as a fuel hose.

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 characteristics of EVOH were measured by the following method.
<(B1) EVOH characteristic value>
[Ethylene content and saponification degree]
It calculated from the spectrum obtained by the 1H-NMR (nuclear magnetic resonance) measurement (The JEOL Co., Ltd. make, JNM-GX-500 type | mold) which used deuterated dimethyl sulfoxide as a solvent.

[Intrinsic viscosity]
0.20 g of dry pellets as a sample is precisely weighed and dissolved in 40 ml of hydrous phenol (water / phenol = 15/85: weight ratio) at 60 ° C. for 3 to 4 hours. The viscosity was measured with a type viscometer (t ₀ = 90 seconds), and the intrinsic viscosity [η] was determined by the following equation.
[Η] = (2 × (ηsp−lnηrel)) 1/2 / C (L / g)
ηsp = t / t ₀ −1
ηrel = _t / t ₀
C: EVOH concentration (g / L)
t ₀ : Time for blank (hydrous phenol) to pass through viscometer t: Time for hydrous phenol solution in which sample is dissolved to pass through viscometer

[Quantification of content of alkali metal salt and alkaline earth metal salt]
10 g of dried pellets as a sample was put into 50 ml of 0.01 N hydrochloric acid aqueous solution and stirred at 95 ° C. for 6 hours. The aqueous solution after stirring was quantitatively analyzed using ion chromatography to obtain an alkali metal ion or alkaline earth metal ion content. The column used was ICS-C25 manufactured by Yokogawa Electric Corporation, and the eluent was a mixed solution of 5.0 mM tartaric acid aqueous solution and 1.0 mM 2,6-pyridinedicarboxylic acid aqueous solution. For quantitative determination, calibration curves prepared with various metal hydrochloride aqueous solutions (for example, sodium chloride aqueous solution, potassium chloride aqueous solution, magnesium chloride aqueous solution and calcium chloride aqueous solution) were used. From the amount of alkali metal ions and alkaline earth metal ions thus obtained, the amount of alkali metal salt and alkaline earth metal salt in the dried pellets was obtained in terms of metal element.

[Quantification of acetic acid content]
20 g of dried pellets as a sample were put into 100 ml of ion-exchanged water and extracted by heating at 95 ° C. for 6 hours. The extract was neutralized and titrated with 1/50 N NaOH using phenolphthalein as an indicator, and the acetic acid content was quantified.

[Quantification of phosphate compounds]
10 g of dried pellets as a sample were put into 50 ml of 0.01 N hydrochloric acid aqueous solution and stirred at 95 ° C. for 6 hours. The aqueous solution after stirring was quantitatively analyzed using ion chromatography to determine the amount of phosphate ions. The column used was ICS-A23 manufactured by Yokogawa Electric Corporation, and the eluent was an aqueous solution containing 2.5 mM sodium carbonate and 1.0 mM sodium bicarbonate. A calibration curve prepared with an aqueous sodium dihydrogen phosphate solution was used for the determination. From the amount of phosphate ions thus obtained, the content of the phosphate compound was obtained in terms of phosphate radical.

<(B) Structural unit content of modified EVOH>
[Trifluoroacetylation of modified EVOH and NMR measurement]
After the manufactured (B) modified EVOH was pulverized to a particle size of 0.2 mm or less, 1 g of this powder was put into a 100 ml eggplant flask, 20 g of methylene chloride and 10 g of trifluoroacetic anhydride were added, and the mixture was stirred at room temperature. One hour after the start of stirring, the polymer was completely dissolved. After the polymer was completely dissolved, the mixture was further stirred for 1 hour, and then the solvent was removed by a rotary evaporator. The obtained trifluoroacetylated (B) modified EVOH was dissolved in a mixed solvent of deuterated chloroform and trifluoroacetic anhydride (deuterated chloroform / trifluoroacetic anhydride = 2/1 (weight ratio)) at a concentration of 2 g / L. Then, 500 MHz 1H-NMR was measured using tetramethylsilane as an internal standard. By assigning the peak in the obtained NMR measurement chart, the ethylene content contained in (B) the modified EVOH and the content of the structural unit (I) were calculated.

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.

[Chemical resistance, sour gasoline resistance]
A sour resistant gasoline test was carried out by the method described in SAE J-2260 7.8. The low-temperature impact resistance of the hose after the test is evaluated according to SAE J-2260 7.5, and when the number of breaks is 0 with respect to 10 test pieces, it is excellent in sour gasoline resistance (chemical resistance). It was judged.

[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 chemical permeation coefficient (g / m ² · day) was calculated by dividing the weight change per day by the surface area of the inner layer of the hose.

[Interlayer adhesion]
The hose cut to 200 mm was further cut in half in the longitudinal 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.

[Environmental stress load resistance]
The hose cut to 200 mm was bent into an R50 state. The hose was placed in an oven at 120 ° C. and 80% relative humidity and treated for 200 hours. The cross section in the hose after taking out was observed to check for cracks.

[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.) (U-1STA3020U, relative viscosity 1.86), except that carbon black (manufactured by Akzo Nobel Co., Ltd., Ketjen Black EC600JD) is used as the conductive filler, and no plasticizer is used (A-1) polyamide 12 resin In the same manner as in the production of the 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 polyamide). The 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) Modified EVOH
(B-1) Production of Modified EVOH Water-containing pellets (water-containing pellets) comprising an ethylene / vinyl acetate copolymer saponified product (EVOH) having an ethylene content of 32 mol%, a saponification degree of 99.6%, and an intrinsic viscosity of 0.0882 L / g (Rate: 130% (dry base)) 100 parts by weight were immersed in 370 parts by weight of an aqueous solution containing 0.1 g / L of acetic acid and 0.044 g / L of potassium dihydrogen phosphate at 25 ° C. for 6 hours and stirred. The obtained pellets were dried at 105 ° C. for 20 hours to obtain dry EVOH pellets (hereinafter, this EVOH is referred to as (b1) EVOH). (B1) The potassium content of EVOH pellets was 8 ppm (converted to metal elements), the acetic acid content was 53 ppm, the phosphate compound content was 20 ppm (phosphate group converted value), and the alkaline earth metal salt content was 0 ppm. It was. Moreover, MFR was 8 g / 10min (under 190 degreeC and 2160g load).

  A biaxial melt kneader (manufactured by Toshiba Machine Co., Ltd., model: TEM-35BS) was used, the cylinder temperature was set to 200 to 240 ° C., and the screw was rotated at 400 rpm. (B1) EVOH is fed from the feed port at a rate of 11 kg / h, melted, water and oxygen are removed from the vent, and (b2) monovalent epoxy having a molecular weight of 500 or less from the hydraulic inlet in the middle of the cylinder. As a compound, (b2-1) 1,2-epoxybutane was fed at a rate of 2.5 kg / h (pressure during feeding: 6 MPa). Thereafter, unreacted 1,2-epoxybutane was removed from the vent to obtain pellets of modified EVOH (hereinafter, this modified EVOH is referred to as (B-1)). The MFR of the obtained (B-1) modified EVOH was 2.5 g / 10 minutes (under 190 ° C. and 2160 g load), and the melting point was 141 ° C. Moreover, according to said trifluoroacetylation and NMR measurement, the ethylene content in (B-1) modified EVOH was 32 mol%, and content of structural unit (I) was 4.8 mol%.

(B-2) Production of Modified EVOH (B-1) In the production of modified EVOH, (b1) EVOH feed amount is 16 kg / h, (b2-1) 1,2-epoxybutane feed amount is 1. Except for using 2 kg / h, (B-1) modified EVOH pellets were obtained in the same manner as in the production of modified EVOH (hereinafter, this modified EVOH is referred to as (B-2)). The MFR of the obtained (B-2) modified EVOH was 3.0 g / 10 min (under 190 ° C. and 2160 g load), and the melting point was 155 ° C. Moreover, according to said trifluoroacetylation and NMR measurement, ethylene content in (B-2) modified EVOH was 32 mol%, and content of structural unit (I) was 3.0 mol%.

(B-3) Production of modified EVOH (B-1) In the production of modified EVOH, (b1) EVOH feed amount was 16 kg / h, and (b2-1) 1,2-epoxybutane was (b2-2) Except for changing to epoxypropane and changing the feed rate to 2.4 kg / h, (B-1) modified EVOH pellets were obtained in the same manner as in the production of modified EVOH (hereinafter, this modified EVOH was changed to (B -3)). The MFR of the obtained (B-3) modified EVOH was 2.8 g / 10 minutes (under a load of 190 ° C. and 2160 g), and the melting point was 135 ° C. Moreover, according to said trifluoroacetylation and NMR measurement, ethylene content in (B-3) modified EVOH was 32 mol%, and content of structural unit (I) was 5.0 mol%.

(B-4) Production of modified EVOH (B-1) In the production of modified EVOH, (b1) EVOH feed amount is 15 kg / h, and (b2-1) 1,2-epoxybutane is (b2-3) Except for changing to glycidol and changing the feed rate to 2.5 kg / h, (B-1) modified EVOH pellets were obtained in the same manner as in the production of modified EVOH (hereinafter, this modified EVOH was converted to (B- 4)). The MFR of the obtained (B-4) modified EVOH was 1.8 g / 10 min (under 190 ° C. and 2160 g load), and the melting point was 135 ° C. Moreover, according to said trifluoroacetylation and NMR measurement, ethylene content in (B-4) modified EVOH was 32 mol%, and content of structural unit (I) was 5.0 mol%.

(B-5) Production of modified EVOH (B-1) In production of modified EVOH, (b1) EVOH feed amount was 15 kg / h, and (b2-1) 1,2-epoxybutane was (b2-4) Except for changing to bisphenol A glycidyl ether and changing the feed rate to 0.12 kg / h, pellets of modified EVOH were obtained in the same manner as in the production of (B-1) modified EVOH (hereinafter referred to as this modified EVOH). (Referred to as (B-5)). The MFR of the obtained (B-5) modified EVOH was 2.5 g / 10 minutes (under 190 ° C. and 2160 g load), and the melting point was 182 ° C.

(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), tetrafluoroethylene (TFE) (3.36 kg), and ethylene (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 using an extruder at 250 ° C. for a residence time of 2 minutes to obtain a fluorine-containing polymer pellet (hereinafter, this fluorine-containing polymer is referred to as (C-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.) are mixed in advance and biaxially melted. Supplied to a kneading machine (Toshiba Machine Co., Ltd., model: TEM-48S), melted and kneaded at a cylinder temperature of 240 to 270 ° C., extruded the molten resin into a strand shape, introduced into a water tank, and then 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. in order to remove moisture, to obtain conductive fluorine-containing polymer pellets. (Hereinafter, this conductive fluorine-containing polymer is referred to as (C-2).)

(C-3) Production of fluorinated polymer A polymerization tank equipped with a stirrer having an internal volume of 94 liters was degassed, and 71.3 kg of 1-hydrotridecafluorohexane and 1,3-dichloro-1 as a chain transfer agent , 1,2,2,3-pentafluoropropane 20.4 kg and CH ₂ ═CH (CF ₂ ) ₂ F562 g, the temperature inside the polymerization tank was raised to 66 ° C., and tetrafluoroethylene (TFE) / ethylene ( E) The pressure was increased to 1.5 MPa / G with a gas (molar ratio: 89/11). As a polymerization initiator, 1 L of a 0.7% -hydrotridecafluorohexane solution of tert-butyl peroxypivalate was charged to initiate polymerization.
A monomer mixed gas of TFE / E (molar ratio: 59.5 / 40.5) was continuously charged so as to keep the pressure constant during the polymerization. Further, CH ₂ ═CH (CF ₂ ) ₂ F in an amount corresponding to 3.3 mol% with respect to the total number of moles of TFE and E charged during the polymerization is 1,3-dichloro-1,1,2,2 , 3-pentafluoropropane was continuously charged with a 1% solution. 9.9 hours after the start of polymerization, when 7.28 kg of the monomer mixed gas was charged, the temperature in the polymerization tank was lowered to room temperature and purged to normal pressure. The obtained slurry-like fluorine-containing polymer was put into a 200 L granulation tank charged with 77 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 150 ° C. for 15 hours to obtain 7.0 kg of a fluoropolymer granulated product.
The composition of the fluorine-containing polymer was 57.6 / 38.7 / 3.7 in a molar ratio of polymerized units based on TFE / polymerized units based on E / CH ₂ ═CH (CF ₂ ) ₂ F. . The melting point was 232 ° 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-3)). .

(C-4) Production of conductive fluorine-containing polymer (C-3) 100 parts by weight of fluorine-containing polymer and 13 parts by weight of carbon black (manufactured by Electrochemical Co., Ltd.) are mixed in advance and biaxially melted. Supplied to a kneader (Toshiba Machine Co., Ltd., model: TEM-48SS), melted and kneaded at a cylinder temperature of 240 to 300 ° C., extruded the molten resin into a strand, and 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-4).)

(D) Adhesive resin (D-1) Maleic acid-modified polypropylene Admer QF500 manufactured by Mitsui Chemicals, Inc.
(D-2) Polyamide 6/12 copolymer UBE Nylon 7034U manufactured by Ube Industries, Ltd.
(D-3) Ethylene / glycidyl methacrylate copolymer Rexper RA3150 manufactured by Nippon Polyolefin Co., Ltd.

Example 1
(A) polyamide 12 resin composition (A-1), (B) modified EVOH (B-1), (C) fluorine-containing polymer (C-1), (D) adhesive resin (D) shown above -1) using a 4-layer hose molding machine manufactured by Plastic (Plastic Engineering Laboratory Co., Ltd.), (A) extrusion temperature 240 ° C, (B) extrusion temperature 200 ° C, (C) The extrusion temperature was 240 ° C. and (D) was melted separately at an extrusion temperature of 200 ° C., and the discharged molten resin was merged with an adapter to form a laminated tubular body. Subsequently, it is cooled by a sizing die for dimension control, and taken up. (A) Layer (outermost layer) made of polyamide 12 resin composition (A-1), (D) Adhesive resin (D-1) (D) layer (outer layer) consisting of (B) layer (intermediate layer) consisting of (B) modified EVOH (B-1), (C) layer (c) consisting of (C) fluorine-containing polymer (C-1) (A) / (d) / (b) / (c) = 0.60 / 0.10 / 0.15 / 0.15 mm with an inner diameter of 6 mm and an outer diameter of 8 mm. A laminated hose was obtained. The physical property measurement results of the laminated hose are shown in Table 1.

Example 2
In Example 1, except that (B) modified EVOH (B-1) was changed to (B-2), a laminated hose having the layer structure shown in Table 1 was obtained in the same manner as in Example 1. The physical property measurement results of the laminated hose are shown in Table 1.

Example 3
A laminated hose having the layer structure shown in Table 1 was obtained in the same manner as in Example 1 except that (B) modified EVOH (B-1) was changed to (B-3) in Example 1. The physical property measurement results of the laminated hose are shown in Table 1.

Example 4
A laminated hose having the layer structure shown in Table 1 was obtained in the same manner as in Example 1 except that (B) modified EVOH (B-1) was changed to (B-4) in Example 1. The physical property measurement results of the laminated hose are shown in Table 1.

Example 5
In Example 1, except that (C) the fluorine-containing polymer (C-1) was changed to the conductive fluorine-containing polymer (C-2) and (C) was melted at an extrusion temperature of 250 ° C., In the same manner as in Example 1, a laminated hose having the layer structure shown in Table 1 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
In Example 1, except that (D) adhesive resin (D-1) was changed to (D-2) and (D) was melted at an extrusion temperature of 220 ° C., the same method as in Example 1 was used. The laminated hose having the layer structure shown in Table 1 was obtained. The physical property measurement results of the laminated hose are shown in Table 1.

Example 7
(A) Polyamide 12 resin composition (A-1), (B) modified EVOH (B-1), (C) fluorine-containing polymer (C-1), (C-3), (D ) Using an adhesive resin (D-1) and a Plabor (Plastic Engineering Laboratory Co., Ltd.) 5-layer hose molding machine, (A) has an extrusion temperature of 240 ° C. and (B) has an extrusion temperature of 220. C., (C) was melted separately at an extrusion temperature of 250.degree. C., and (D) was melted separately at an extrusion temperature of 200.degree. C., and the discharged molten resin was merged with an adapter to form a laminated tubular body. Subsequently, it is cooled by a sizing die for dimension control, and taken up. (A) Layer (outermost layer) made of polyamide 12 resin composition (A-1), (D) Adhesive resin (D-1) (D) layer (outer layer), (B) layer (intermediate layer) made of modified EVOH (B-1), (C) fluorine-containing polymer (C-1) (c) Layer structure (a) / (d) / (b) / (layer (inner layer), (C) (c ') layer (innermost layer) made of fluorine-containing polymer (C-3) c) / (c ′) = 0.60 / 0.10 / 0.15 / 0.05 / 0.10 mm to obtain a laminated hose having an inner diameter of 6 mm and an outer diameter of 8 mm. The physical property measurement results of the laminated hose are shown in Table 1.

Example 8
In Example 7, the (C) fluorine-containing polymer (C-3) disposed in the innermost layer was changed to a conductive fluorine-containing polymer (C-4), and (C) was extruded at 260 ° C. A laminated hose having the layer structure shown in Table 1 was obtained in the same manner as in Example 7 except that the molten hose was melted. 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
Using (A) polyamide 6 resin composition (A-3), (B) modified EVOH (B-1) and (C) fluorine-containing polymer (C-1) shown above, Engineering Laboratory Co., Ltd.) 3 layer hose molding machine, (A) is melted separately at an extrusion temperature of 240 ° C, (B) is melted at an extrusion temperature of 200 ° C, and (C) is melted separately at an extrusion temperature of 240 ° C. The molten resin thus formed was merged with an adapter and formed into a laminated tubular body. Subsequently, it is cooled by a sizing die that controls the size and taken up, and (A) layer (outermost layer) made of polyamide 6 resin composition (A-3), (B) from modified EVOH (B-1) (B) layer (intermediate layer), (C) layer configuration when (c) layer (innermost layer) made of a fluorine-containing polymer (C-1) is (a) / (b) / ( c) A laminated hose having an inner diameter of 6 mm and an outer diameter of 8 mm at 0.70 / 0.15 / 0.15 mm was obtained. The physical property measurement results of the laminated hose are shown in Table 1.

Comparative Example 1
In Example 1, Example 1 except that (B) modified EVOH (B-1), (C) fluorine-containing polymer (C-1), and (D) adhesive resin (D-1) were not used. The hose having the layer structure shown in Table 1 was obtained in the same manner as described above. Table 1 shows the physical property measurement results of the hose.

Comparative Example 2
In Example 1, the hose of the layer structure shown in Table 1 was obtained by the same method as Example 1 except not using (C) fluorine-containing polymer (C-1). Table 1 shows the physical property measurement results of the hose.

Comparative Example 3
In Example 1, except that (B) modified EVOH (B-1) and (D) adhesive resin (D-1) were not used, the layer structure shown in Table 1 was used in the same manner as in Example 1. I got a hose. Table 1 shows the physical property measurement results of the hose.

Comparative Example 4
A hose having a layer structure shown in Table 1 was obtained in the same manner as in Example 1 except that (B) modified EVOH (B-1) was changed to (b1) EVOH in Example 1. Table 1 shows the physical property measurement results of the hose.

Comparative Example 5
A hose having a layer structure shown in Table 1 was obtained in the same manner as in Example 1 except that (B) modified EVOH (B-1) was changed to (B-5) in Example 1. Table 1 shows the physical property measurement results of the hose.

Comparative Example 6
In Example 1, except that (C) the fluorine-containing polymer (C-1) was changed to (C-3), the laminated hose having the layer structure shown in Table 1 was prepared in the same manner as in Example 1. Obtained. The physical property measurement results of the laminated hose are shown in Table 1.

Comparative Example 7
In Example 1, the same method as in Example 1 except that (C) the fluorine-containing polymer (C-1) was changed to (C-4) and (C) was melted at an extrusion temperature of 260 ° C. Thus, a laminated hose having a layer structure shown in Table 1 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.

Comparative Example 8
(A) Polyamide 12 resin composition (A-1), (b1) EVOH, (C) fluorinated polymer (C-3), (D) adhesive resin (D-1), (D -3) using a 5-layer hose molding machine manufactured by Plastic (Plastic Engineering Laboratory Co., Ltd.), (A) at an extrusion temperature of 250 ° C, (B) at an extrusion temperature of 220 ° C, and (C). The extrusion temperature was 250 ° C. and (D) was melted separately at an extrusion temperature of 200 ° C., and the discharged molten resin was merged with an adapter to form a laminated tubular body. Subsequently, it is cooled by a sizing die for dimension control, and taken up. (A) Layer (outermost layer) made of polyamide 12 resin composition (A-1), (D) Adhesive resin (D-1) (D) layer (outer layer) composed of (b1) EVOH (b) layer (intermediate layer), (D) adhesive resin (D-3) (d ') layer (inner layer), (C) When the (c) layer (innermost layer) made of the fluorine-containing polymer (C-3) is used, the layer structure is (a) / (d) / (b) / (d ′) / (c) = 0. A laminated hose having an inner diameter of 6 mm and an outer diameter of 8 mm at 50 / 0.10 / 0.15 / 0.10 / 0.15 mm was obtained. The physical property measurement results of the laminated hose are shown in Table 1.

Comparative Example 9
Using (A) polyamide 12 resin composition (A-1), polyamide 6 resin composition (A-3), (b1) EVOH, (D) adhesive resin (D-2) shown above, Using a 4-layer hose molding machine (made by Plastic Engineering Laboratory Co., Ltd.), (A) was melted separately at an extrusion temperature of 250 ° C, (B) at an extrusion temperature of 220 ° C, and (D) at an extrusion temperature of 230 ° C. Then, the discharged molten resin was joined by an adapter and formed into a laminated tubular body. Subsequently, it is cooled by a sizing die for dimension control, and taken up. (A) Layer (outermost layer) made of polyamide 12 resin composition (A-1), (D) Adhesive resin (D-2) (D) layer (outer layer) made of (b1) (b) layer (intermediate layer) made of EVOH, (A) (a ′) layer (innermost layer) made of polyamide 6 resin composition (A-3) A laminated hose having a layer configuration of (a) / (d) / (b) / (a ′) = 0.40 / 0.10 / 0.15 / 0.35 mm and an inner diameter of 6 mm and an outer diameter of 8 mm. Obtained. The physical property measurement results of the laminated hose are shown in Table 1.

Comparative Example 10
In Comparative Example 9, a laminated hose having the layer structure shown in Table 1 was obtained in the same manner as in Comparative Example 9, except that (b1) EVOH was changed to (B) modified EVOH (B-1). The physical property measurement results of the laminated hose are shown in Table 1.

Comparative Example 11
(A) polyamide 12 resin composition (A-1), conductive polyamide 12 resin composition (A-2), (B) modified EVOH (B-1), (D) adhesive resin (D-) shown above 2) using a 5-layer hose molding machine (made by Plastic Engineering Laboratory Co., Ltd.), (A) is extruded at 250 ° C., (B) is extruded at 220 ° C., and (D) is extruded. The molten resin was melted separately at a temperature of 230 ° 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 for dimension control, and taken up. (A) Layer (outermost layer) made of polyamide 12 resin composition (A-1), (D) Adhesive resin (D-2) (D) layer (outer layer, inner layer), (B) layer (intermediate layer) composed of modified EVOH (B-1), (A) conductive polyamide 12 resin composition (A-2) When the layer (a ′) (the innermost layer) is used, the layer structure is (a) / (d) / (b) / (d) / (a ′) = 0.50 / 0.10 / 0.15 / A laminated hose having an inner diameter of 6 mm and an outer diameter of 8 mm at 0.10 / 0.15 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.

Claims (10)

(A) Layer (a) made of aliphatic polyamide, (B) Modified ethylene / vinyl acetate copolymer having an ethylene content of 5 to 55 mol%, containing 0.3 to 40 mol% of the following structural unit (I) (B) a layer formed of a saponified product, and (C) a layer (c) formed of a fluorine-containing polymer in which a functional group having reactivity to an amino group or a hydroxyl group is introduced into a molecular chain, A laminated hose comprising three or more layers.

(Wherein R ¹ , R ² , R ³ and R ⁴ are a hydrogen atom, an aliphatic hydrocarbon group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 3 to 10 carbon atoms, or 6 to 10 carbon atoms. R ¹ , R ² , R ³ and R ⁴ may be the same group or different from each other, and R ³ and R ⁴ may be bonded to each other. R ¹ , R ² , R ³ and R ⁴ may have other groups such as a hydroxyl group, a carboxyl group, and a halogen atom.) The (A) aliphatic polyamide is polycaproamide (polyamide 6), polyhexamethylene adipamide (polyamide 66), polyhexamethylene dodecanamide (polyamide 612), polyundecanamide (polyamide 11), polydodecanamide ( The laminated hose according to claim 1, wherein the laminated hose is at least one selected from the group consisting of polyamide 12). The (B) modified ethylene / vinyl acetate copolymer saponified product has an ethylene content of 20 to 45 mol% and a saponification degree of 90 mol% or more (b1) an ethylene / vinyl acetate copolymer saponified product and (b2) The laminated hose according to claim 1, wherein the laminated hose is produced by melt-mixing a valence epoxy compound. (C) In the fluorine-containing polymer in which a functional group having reactivity to an amino group or a hydroxyl group is introduced into a molecular chain, the melting point of the fluorine-containing polymer is 180 to 230 ° C. The laminated hose according to any one of claims 1 to 3, characterized in that: The laminated hose according to any one of claims 1 to 4, wherein the (a) layer made of the (A) aliphatic polyamide is disposed in an outermost layer. The (b) layer made of the saponified product of the (B) modified ethylene / vinyl acetate copolymer is reactive with the (a) layer made of the (A) aliphatic polyamide and (C) an amino group or a hydroxyl group. 2. The functional group having a fluorine-containing polymer introduced in the molecule is disposed between the (c) layers, and the (b) layer and the (c) layer are directly bonded to each other. To the laminated hose according to any one of 5 to 5. The laminated hose according to any one of claims 1 to 6, wherein a conductive layer made of a fluorine-containing polymer composition containing a conductive filler is disposed in the innermost layer of the laminated hose. The laminated hose according to claim 1, wherein the laminated hose is manufactured by coextrusion molding. The laminated hose according to any one of claims 1 to 8, wherein the laminated hose is used as a fuel hose. The laminated hose according to any one of claims 1 to 9, wherein the laminated hose has at least a corrugated region.