Title of invention: Laminated tube
Technical field
[0001]
　The present invention relates to a laminated tube.
Background technology
[0002]
　Various pressure tubes such as hydraulic tubes and water pressure tubes, vacuum tubes, fuel piping tubes used in automobiles, brake tubes, cooling liquid hoses, air conditioning piping tubes, SCR (diesel engine exhaust gas removal device) tubes, control cable liners, etc. Many hoses and tubes are used in. In these hoses and tubes, liquid chemicals such as cooling liquid (alcohol and water), refrigerant, oil, and urea solution are conveyed. Various hoses and tubes used in the automobile industry are required to have extremely high performance such as high breaking pressure strength at high temperature, long-term heat resistance, chemical resistance, water vapor and chemical liquid barrier properties, and flexibility. .
[0003]
　In particular, the circulating fluid is used as a coolant (LLC) mainly composed of ethylene glycol to prevent freezing in winter, a urea solution enclosed as a catalyst for removing NOx emitted from a diesel engine, an air conditioner/radiator, etc. In the case of carbon dioxide, chlorofluorocarbon, chlorofluorocarbon, chlorofluorocarbon, propane, water and the like, unless the barrier property against these chemicals is sufficient, the cooling effect and the catalytic effect cannot be sufficiently exerted during actual use. Further, as the regulation of evaporation of ozone-depleting gas is strengthened, the demand for the refrigerant barrier property of the refrigerant-conveying tubes used in automobiles and the like has become strict.
[0004]
　On the other hand, the quality of refrigerants used in automobiles and the like has been improved in recent years with the stricter regulation of evaporation of ozone depleting gas. For example, the R-1234yf refrigerant was developed as an alternative refrigerant to the HFC-134a refrigerant, has a lower ozone depletion potential and global warming potential than the HFC-134a refrigerant, and is a very environmentally friendly refrigerant. However, the R-1234yf refrigerant is particularly prone to generate an acid (formic acid, etc.) by being hydrolyzed by contact with water under a high temperature environment, and the acid causes the hydrolysis depending on the material that comes into contact with the chemical solution. There is a problem in that, in the worst case, a crack is generated, and the fluid leaks and cannot serve the purpose of transporting the fluid. Alternatively, it may adversely affect the parts which come into contact with the tube body by permeation of the liquid medicine or water.
[0005]
　Conventionally used single-layer tubes using polyamide-based resins, particularly polyamide 11 or polyamide 12 having excellent strength, toughness, chemical resistance, flexibility, etc., have long-term durability and barrier against the above-mentioned chemicals. The sex is not enough.
[0006]
　Fluorine-based resins such as ethylene/tetrafluoroethylene copolymer (ETFE) have excellent resistance to various chemicals and are considered to be one of the material members having a barrier property against water vapor. In recent years, development of fluororesins having adhesiveness with polyamides has become active (see Patent Documents 1 to 3). However, due to environmental concerns, the use of halogen-containing materials is being shunned, and there are problems of high specific gravity and high cost. Using halogen-free materials, they have excellent barrier properties against chemicals and have resistance to various chemicals. Development of piping system is required.
[0007]
　On the other hand, polyolefin is inexpensive and has excellent chemical solution permeation resistance and chemical solution long-term resistance. For example, there has been proposed a cooling pipe composed of an outer layer made of polyamide and an inner layer made of crosslinked polyethylene (see Patent Document 4). Further, there has been proposed a cooling pipe which is composed of an outer layer made of polyamide and an inner layer made of polypropylene having a certain thickness and containing a specific additive (see Patent Document 5). Similarly, it is inert to the coolant and non-swellable, and the outer and inner layers made of polyamide are composed of halogenated or non-halogenated homopolyolefins or copolyolefins, and are manufactured by extrusion blow molding. Over the years, there has been proposed a cooling pipe characterized in that the wall thicknesses of the layers are different, and the polymers of the inner layer and the outer layer are distinctly different in flexibility (see Patent Document 6). Further, from the inner side to the outer side, an inner layer of polyolefin, a first intermediate layer based on an adhesive, a second intermediate layer of ethylene/vinyl alcohol copolymer, a third intermediate layer of polyamide, and an outer layer of A multilayer tube including a protective layer has been proposed (see Patent Document 7). Further, a fuel having an outer layer material containing polyamide resin and styrene/isobutylene block copolymer as essential components as an outer layer, and a polyolefin resin and inner layer material containing styrene/isobutylene block copolymer as essential components Battery piping has also been proposed (see Patent Document 8).
Prior art documents
Patent literature
[0008]
Patent Document 1: International Publication No. 2001-058686
Patent Document 2: International Publication No. 2001-060606
Patent Document 3: Japanese Patent Laid-Open No. 2004-301247
Patent Document 4: Japanese Patent Laid-Open No. 9-29869
Patent Document 5: Special Table 2008- 507436 JP
Patent Document 6: JP-A 7-214647 Patent Publication
Patent Document 7: JP 2006-116966 JP
Patent Document 8: JP 2005-216725 JP
Disclosure of the invention
Problems to be Solved by the Invention
[0009]
　However, in the pipe disclosed in Patent Document 4, when polyethylene is used as the inner layer, long-term resistance at high temperatures and tube properties are poor.
　Further, there is a concern that the chemical solution transport tube and the like may be clogged in the tube due to catalyst contamination due to contamination of the sulfur component into the chemical solution flowing inside and elution of low molecular weight materials. No data or technical suggestions.
　In Patent Document 8, the styrene/isobutylene block copolymer contained in the outer layer material does not have a sufficient flexibility improving effect, and further improvement is required. On the other hand, the space in which piping can be installed is becoming smaller, and in electric vehicles and the like, the piping layout is becoming more complicated in order to improve cooling efficiency. Under such circumstances, the flexibility of the laminated tube is required from the viewpoints of workability of parts and flexibility of layout, and further, it is required to have both high pressure resistance capable of withstanding the internal pressure of the chemical liquid in a high temperature atmosphere. ing.
[0010]
　An object of the present invention is to solve the above problems and provide a laminated tube excellent in low temperature impact resistance, breaking pressure strength at high temperature, flexibility, dimensional stability, and elution resistance of low molecular weight substances and ionic components. To do.
Means for solving the problems
[0011]
　In order to solve the above-mentioned problems, the inventors of the present invention have made extensive studies and found that the ratio of the number of methylene groups to the number of amide groups is from an aliphatic polyamide having a predetermined range and an unsaturated compound having a carboxyl group and/or an acid anhydride group. A layer containing an aliphatic polyamide composition having a flexural modulus in a specific range, which contains an elastomeric polymer containing a constitutional unit to be derived, and contains a plasticizer having a specific structure as necessary. A laminated tube having a layer containing a modified polyolefin having a specific melting point or more, wherein the thickness of the layer containing an aliphatic polyamide composition has a specific proportion or more of the total wall thickness of the tube, thereby providing low temperature resistance. They have found that they are excellent in impact resistance, breaking pressure strength at high temperature, flexibility, dimensional stability, and elution resistance of low molecular weight substances and ionic components.
[0012]
　That is, the present invention is a laminated tube of two or more layers including a layer (a) and a layer (b),
　wherein the layer (a) contains the aliphatic polyamide composition (A) and the
　layer (b). Contains a modified polyolefin (B), the
　aliphatic polyamide composition (A) contains a polyamide (A1) and an elastomer polymer (A2), and the
　polyamide (A1) has a ratio of the number of methylene groups to the number of amide groups. It is 7.0 or more aliphatic polyamide, 55 mass% or more and 95 mass% or less is contained in the
　said aliphatic polyamide composition (A), and the said elastomer polymer (A2) is a carboxyl group and/or acid anhydride. Containing a structural unit derived from an unsaturated compound having a physical group, the aliphatic polyamide composition (A) is contained in an amount of 5% by mass or more and 30% by mass or less,
　and the aliphatic polyamide composition (A ) May contain a plasticizer (A3), and the plasticizer (A3)
　does not contain a sulfur atom, and contains p- and/or o-hydroxybenzoic acid and a linear chain having 12 to 24 carbon atoms and / or contain branched alkyl fatty alcohol, an ester structure, the content of the plasticizer (A3) in the aliphatic polyamide composition (a) is 15 mass% or less 0% by mass or more,
　the The aliphatic polyamide composition (A) has a flexural modulus of 400 MPa or more and 1,000 MPa or less measured according to ISO 178, and the
　modified polyolefin (B) is an α-olefin having 2 to 10 carbon atoms. Has a unit derived from a monomer based on, and has a melting point of 130° C. or higher measured according to ISO 11357-3,
　In the laminated tube, the layer (a) and the layer (b) are arranged in this order from the outside to the inside, and
　the thickness of the layer (a) accounts for 60% or more of the total thickness of the tube.
[0013]
　A preferred embodiment of the laminated tube is shown below. Plural preferable modes can be combined.
[0014]
　[1] The polyamide (A1) is polyundecane amide (polyamide 11), polydodecane amide (polyamide 12), polyhexamethylene decamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecamethylene deca At least one homopolymer selected from the group consisting of amide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), and polydodecamethylene dodecamide (polyamide 1212), and/or a raw material monomer forming these A laminated tube which is a copolymer using several kinds.
[0015]
　[2] When the terminal amino group concentration per 1 g of the polyamide (A1) is [A] (μeq/g) and the terminal carboxyl group concentration is [B] (μeq/g), [A]>[B] +5 laminated tube.
[0016]
　[3] The modified polyolefin (B) is at least selected from the group consisting of a carboxyl group or a derivative thereof, a hydroxyl group, an epoxy group, an amino group, an amide group, an imide group, a nitrile group, a thiol group, and an isocyanate group. Laminated tubes containing units derived from unsaturated compounds having one functional group.
[0017]
　[4] The modified polyolefin (B) is a laminated tube produced by a method in which a polyolefin before modification is melted, the unsaturated compound having a functional group is added, and graft copolymerization is performed.
[0018]
　[5] A laminated tube in which the modified polyolefin (B) has an MFR value measured according to ISO 1133 of not less than 1.0 g/10 min and not more than 10.0 g/10 min under the condition of 230° C./2160 g.
[0019]
　[6] A laminated tube in which the modified polyolefin (B) has a density of 0.85 g/cm 3 or more measured according to ISO 1183-3 .
[0020]
　[7] A laminated tube in which the modified polyolefin (B) is maleic anhydride modified polypropylene, and the content of polypropylene is 50% by mass or more.
[0021]
　[8] Further includes a layer (c), the layer (c) contains a polyolefin (C), and the polyolefin (C) is derived from an α-olefin-based monomer having 2 to 10 carbon atoms. Has a melting point of 120° C. or higher measured according to ISO 11357-3, a tensile yield stress of 20 MPa or higher measured according to ISO 527, measured according to ISO 179/1eA. A laminated tube having a Charpy impact strength (notched) at 23° C. of 40 kJ/m 2 or more.
[0022]
　[9] A laminated tube in which the layer (c) is arranged inside the layer (b).
[0023]
　[10] A laminated tube produced by a coextrusion molding method.
[0024]
　[11] A laminated tube which is any one of a cooling liquid (LLC) cooler tube, a urea solution transport tube, a battery cooling and heating tube, and an air conditioner tube.
Effect of the invention
[0025]
　According to the present invention, it is possible to provide a laminated tube excellent in low-temperature impact resistance, breaking pressure strength at high temperature, flexibility, dimensional stability, and elution resistance of low molecular weight substances and ionic components.
MODE FOR CARRYING OUT THE INVENTION
[0026]
　The laminated tube of the present invention is a laminated tube of two or more layers including a layer (a) and a layer (b), wherein the layer (a) contains an aliphatic polyamide composition (A) and the layer (b). The layer contains a modified polyolefin (B), the aliphatic polyamide composition (A) contains a polyamide (A1) and an elastomer polymer (A2), and the polyamide (A1) has a ratio of the number of methylene groups to the number of amide groups. Is 7.0 or more aliphatic polyamide, 55 mass% or more and 95 mass% or less is contained in the aliphatic polyamide composition (A), and the elastomer polymer (A2) has a carboxyl group and/or an acid. The aliphatic polyamide composition (A) contains a structural unit derived from an unsaturated compound having an anhydride group, and the aliphatic polyamide composition (A) contains 5% by mass or more and 30% by mass or less of the aliphatic polyamide composition ( A) may contain a plasticizer (A3), and the plasticizer (A3) does not contain a sulfur atom, and is p- and/or o-hydroxybenzoic acid and a linear chain having 12 to 24 carbon atoms. And/or an ester structure with a branched chain alkyl aliphatic alcohol, and the content of the plasticizer (A3) in the aliphatic polyamide composition (A) is 0% by mass or more and 15% by mass or less. The aliphatic polyamide composition (A) has a flexural modulus of 400 MPa or more and 1,000 MPa or less measured according to ISO 178, and the modified polyolefin (B) has an α of 2 to 10 carbon atoms. A layer (a) having units derived from an olefin-based monomer, having a melting point of 130° C. or higher measured according to ISO 11357-3, and from the outside to the inside in the laminated tube , (B) layers are arranged in this order, and the thickness of the (a) layer accounts for 60% or more of the total thickness of the tube.
[0027]
1. (A) Layer
　The (a) layer of the laminated tube of the present invention contains the aliphatic polyamide composition (A).
[0028]
　 The
　aliphatic polyamide composition (A) contains a polyamide (A1) and an elastomer polymer (A2), and the polyamide (A1) has a ratio of the number of methylene groups to the number of amide groups of 7. It is 0 or more aliphatic polyamide, 55 mass% or more and 95 mass% or less are contained in aliphatic polyamide composition (A), and elastomer polymer (A2) has a carboxyl group and/or an acid anhydride group. The aliphatic polyamide composition (A) contains a structural unit derived from an unsaturated compound, is contained in an amount of 5% by mass or more and 30% by mass or less, and may optionally contain a plasticizer (A3). The agent (A3) does not contain a sulfur atom, and contains an ester structure of p- and/or o-hydroxybenzoic acid and a linear and/or branched alkyl aliphatic alcohol having 12 to 24 carbon atoms. The content of the plasticizer (A3) in the aliphatic polyamide composition (A) is 0% by mass or more and 15% by mass or less, and the aliphatic polyamide composition (A) is in accordance with ISO 178. The measured flexural modulus is 400 MPa or more and 1,000 MPa or less (hereinafter, may be referred to as an aliphatic polyamide composition (A)).
[0029]
　[Polyamide (A1)] The
　polyamide (A1) is an aliphatic polyamide having a ratio of the number of methylene groups to the number of amide groups (hereinafter sometimes referred to as [CH 2 ]/[NHCO]) of 7.0 or more (hereinafter, referred to as "polyamide (A1)" ) . , Sometimes referred to as polyamide (A1)). By using an aliphatic polyamide having a [CH 2 ]/[NHCO] of 7.0 or more, various properties such as mechanical properties of the obtained laminated tube can be made excellent.
[0030]
　The polyamide (A1) has an amide bond (—CONH—) in the main chain, and is made from an aliphatic lactam, an aliphatic aminocarboxylic acid, or an aliphatic diamine and an aliphatic dicarboxylic acid as raw materials, melt polymerization, solution polymerization or It can be obtained by polymerization or copolymerization by a known method such as solid phase polymerization.
[0031]
　Examples of the aliphatic lactam include caprolactam, enanthlactam, undecane lactam, dodecane lactam, α-pyrrolidone and α-piperidone, and aliphatic aminocarboxylic acids include 6-aminocaproic acid, 7-aminoheptanoic acid, 9-aminononanoic acid, Examples thereof include 11-aminoundecanoic acid and 12-aminododecanoic acid. These can use 1 type(s) or 2 or more types.
[0032]
　As the aliphatic diamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine, 1,8-octanediamine, 1,9-nonanediamine, 1,10 -Decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine, 1,16-hexadecanediamine, 1,17 -Heptadecanediamine, 1,18-octadecanediamine, 1,19-nonadecanediamine, 1,20-eicosanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine, 2-methyl-1,8-octanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9-nonanediamine Etc. These can use 1 type(s) or 2 or more types.
[0033]
　Examples of the aliphatic dicarboxylic acid include glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, tridecanedioic acid, tetradecanedioic acid, pentadecanedioic acid, hexadecanedioic acid, octadecane. Diacid, eicosane diacid, etc. are mentioned. These can use 1 type(s) or 2 or more types.
[0034]
　Examples of the polyamide (A1) include polyundecane amide (polyamide 11), polydodecane amide (polyamide 12), polytetramethylene dodecamide (polyamide 412), polypentamethylene dodecamide (polyamide 512), polyhexamethylene dodecamide. (Polyamide 612), polyhexamethylene tetradecamide (polyamide 614), polyhexamethylene hexadecamide (polyamide 616), polyhexamethylene octadecamide (polyamide 618), polynonamethylene adipamide (polyamide 96), poly Nonamethylene sveramide (polyamide 98), polynonamethylene azeramide (polyamide 99), polynonamethylene sebacamide (polyamide 910), polynonamethylene dodecamide (polyamide 912), polydecamethylene adipamide (polyamide 106) , Polydecamethylene sveramide (polyamide 108), polydecamethylene azeramide (polyamide 109), polydecamethylene sebacamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012), polydodecamethylene adipamide (polyamide) 126), polydodecamethylenesveramide (polyamide 128), polydodecamethylene azamide (polyamide 129), polydodecamethylene sebacamide (polyamide 1210), polydodecamethylene dodecamide (polyamide 1212) and the like, and homopolymers thereof. Examples thereof include copolymers using several kinds of raw material monomers for forming.
[0035]
　Among them, as the polyamide (A1), polyundecane amide (polyamide) is used as the polyamide (A1) from the viewpoints of sufficiently securing various physical properties such as mechanical properties and heat resistance of the resulting laminated tube, economical efficiency and availability. 11), polydodecanamide (polyamide 12), polyhexamethylene decamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecamethylene decamide (polyamide 1010), polydecamethylene dodecamide (polyamide 1012) , And at least one homopolymer selected from the group consisting of polydodecamethylene dodecamide (polyamide 1212), and/or a copolymer using several raw material monomers forming them.
[0036]
　For example, in the case of polyundecane amide (polyamide 11), [CH 2 ]/[NHCO]=10.0, in the case of polydodecane amide (polyamide 12), [CH 2 ]/[NHCO]=11.0, polyhexamethylene In the case of decamide (polyamide 610), [CH 2 ]/[NHCO]=7.0, in the case of polyhexamethylene dodecamide (polyamide 612), [CH 2 ]/[NHCO]=8.0, polydecamethylene In the case of sebacamide (polyamide 1010), [CH 2 ]/[NHCO]=9.0, in the case of polydecamethylene dodecamide (polyamide 1012), [CH 2 ]/[NHCO]=10.0, polydodeca In the case of methylenedodecamide (polyamide 1212), [CH 2 ]/[NHCO]=11.0, and the ratio of the number of methylene groups to the number of amide groups is 7.0 or more.
[0037]
　The polyamide (A1) production apparatus includes a kneading reaction extruder such as a batch reaction kettle, a one-tank or multi-tank continuous reaction apparatus, a tubular continuous reaction apparatus, a single-screw kneading extruder, and a twin-screw kneading extruder. Etc., a known polyamide manufacturing apparatus can be used. As the polymerization method, known methods such as melt polymerization, solution polymerization and solid phase polymerization can be used, and polymerization can be carried out by repeating normal pressure, reduced pressure and pressure operations. These polymerization methods can be used alone or in an appropriate combination.
[0038]
　Further, the relative viscosity of the polyamide (A1) measured under the conditions of 96% sulfuric acid, polymer concentration 1% and 25° C. according to JIS K-6920 should ensure the mechanical properties of the obtained laminated tube. From the viewpoint of ensuring the desired moldability of the laminated tube by adjusting the viscosity of the molten tube to an appropriate range, it is preferably 1.5 or more and 5.0 or less, and more preferably 2.0 or more and 4.5 or less. preferable.
[0039]
　When the terminal amino group concentration per gram of polyamide (A1) is [A] (μeq/g) and the terminal carboxyl group concentration is [B] (μeq/g), sufficient interlayer adhesion of the laminated tube is ensured. From the viewpoint, [A]>[B]+5 is preferable, [A]>[B]+10 is more preferable, and [A]>[B]+15 is further preferable). Further, from the viewpoint of the melt stability of the polyamide and the suppression of gelled substance generation, [A]>20 is preferable, and 30<[A]<120 is more preferable.
[0040]
　The terminal amino group concentration [A] (μeq/g) can be measured by dissolving the polyamide in a phenol/methanol mixed solution and titrating with 0.05N hydrochloric acid. The terminal carboxyl group concentration [B] (μeq/g) can be measured by dissolving the polyamide in benzyl alcohol and titrating with a 0.05N sodium hydroxide solution.
[0041]
　The polyamide (A1) is produced by polymerizing or copolymerizing the polyamide raw material in the presence of amines by a known method such as melt polymerization, solution polymerization or solid phase polymerization. Alternatively, it is produced by melt-kneading in the presence of amines after polymerization. As described above, amines can be added at any stage during polymerization, or at any stage after melt-kneading after polymerization, but in consideration of the interlayer adhesion of the laminated tube, amines are added at the stage during polymerization. It is preferable.
[0042]
　Examples of the amines include monoamine, diamine, triamine, tetramine, and polyamine. In addition to amines, carboxylic acids such as monocarboxylic acids, dicarboxylic acids, and tricarboxylic acids may be added, if necessary, as long as they do not fall outside the range of the terminal group concentration conditions described above. These amines and carboxylic acids may be added simultaneously or separately. The amines and carboxylic acids exemplified below may be used either individually or in combination of two or more.
[0043]
　Specific examples of the monoamine added include methylamine, ethylamine, propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, 2-ethylhexylamine, nonylamine, decylamine, undecylamine, dodecylamine, tridecylamine. , Aliphatic monoamines such as tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, octadecyleneamine, eicosylamine and docosylamine; cycloaliphatic monoamines such as cyclohexylamine and methylcyclohexylamine; benzylamine, β- Aromatic monoamines such as phenylmethylamine; N,N-dimethylamine, N,N-diethylamine, N,N-dipropylamine, N,N-dibutylamine, N,N-dihexylamine, N,N-dioctyl Symmetrical secondary amines such as amines; N-methyl-N-ethylamine, N-methyl-N-butylamine, N-methyl-N-dodecylamine, N-methyl-N-octadecylamine, N-ethyl-N-hexadecyl Examples include mixed secondary amines such as amines, N-ethyl-N-octadecylamine, N-propyl-N-hexadecylamine, and N-propyl-N-benzylamine. These can use 1 type(s) or 2 or more types.
[0044]
　Specific examples of the diamine to be added include 1,2-ethanediamine, 1,3-propanediamine, 1,4-butanediamine, 1,5-pentanediamine, 1,6-hexanediamine, 1,7-heptanediamine. , 1,8-octanediamine, 1,9-nonanediamine, 1,10-decanediamine, 1,11-undecanediamine, 1,12-dodecanediamine, 1,13-tridecanediamine, 1,14-tetradecanediamine, 1,15-pentadecanediamine, 1,16-hexadecanediamine, 1,17-heptadecanediamine, 1,18-octadecanediamine, 2-methyl-1,5-pentanediamine, 3-methyl-1,5-pentanediamine , 2-methyl-1,8-octanediamine, 2,2,4-trimethyl-1,6-hexanediamine, 2,4,4-trimethyl-1,6-hexanediamine, 5-methyl-1,9- Aliphatic diamines such as nonanediamine; 1,3-bis(aminomethyl)cyclohexane, 1,4-bis(aminomethyl)cyclohexane, bis(4-aminocyclohexyl)methane, 2,2-bis(4-aminocyclohexyl)propane , Bis(3-methyl-4-aminocyclohexyl)methane, 2,2-bis(3-methyl-4-aminocyclohexyl)propane, 5-amino-2,2,4-trimethyl-1-cyclopentanemethylamine, 5-amino-1,3,3-trimethylcyclohexanemethylamine, bis(aminopropyl)piperazine, bis(aminoethyl)piperazine, 2,5-bis(aminomethyl)norbornane, 2,6-bis(aminomethyl)norbornane Alicyclic diamines such as 3,8-bis(aminomethyl)tricyclodecane and 4,9-bis(aminomethyl)tricyclodecane; aromatic diamines such as m-xylylenediamine and p-xylylenediamine Can be mentioned. These can use 1 type(s) or 2 or more types.
[0045]
　Specific examples of triamine and tetramine to be added include 1,2,3-triaminopropane, 1,2,3-triamino-2-methylpropane, 1,2,4-triaminobutane, 1,2,3. 4-tetraminobutane, 1,3,5-triaminocyclohexane, 1,2,4-triaminocyclohexane, 1,2,3-triaminocyclohexane, 1,2,4,5-tetraminocyclohexane, 1,3 5-triaminobenzene, 1,2,4-triaminobenzene, 1,2,3-triaminobenzene, 1,2,4,5-tetraminobenzene, 1,2,4-triaminonaphthalene, 2,5 , 7,-triaminonaphthalene, 2,4,6-triaminopyridine, 1,2,7,8-tetraminonaphthalene and 1,4,5,8-tetraminonaphthalene. These can use 1 type(s) or 2 or more types.
[0046]
　The polyamine to be added may be a compound having a plurality of primary amino groups (—NH 2 ) and/or secondary amino groups (—NH—), and examples thereof include polyalkyleneimine, polyalkylenepolyamine, polyvinylamine, Examples include polyallylamine and the like. Amino groups with active hydrogen are the reactive sites for polyamines.
[0047]
　The polyalkyleneimine is produced by a method of ionically polymerizing an alkyleneimine such as ethyleneimine or propyleneimine, or a method of polymerizing an alkyloxazoline and then partially or completely hydrolyzing the polymer. Examples of the polyalkylene polyamine include diethylene triamine, triethylene tetramine, pentaethylene hexamine, or a reaction product of ethylene diamine and a polyfunctional compound. Polyvinylamine can be obtained, for example, by polymerizing N-vinylformamide to form poly(N-vinylformamide) and then partially or completely hydrolyzing the polymer with an acid such as hydrochloric acid. Polyallylamine is generally obtained by polymerizing a hydrochloride salt of an allylamine monomer and then removing hydrochloric acid. These can use 1 type(s) or 2 or more types. Among these, polyalkyleneimine is preferable.
[0048]
　As the polyalkyleneimine, one or two of alkyleneimines having 2 to 8 carbon atoms, such as ethyleneimine, propyleneimine, 1,2-butyleneimine, 2,3-butyleneimine, and 1,1-dimethylethyleneimine. Examples thereof include homopolymers and copolymers obtained by polymerizing one or more species by a conventional method. Among these, polyethyleneimine is more preferable. The polyalkyleneimine is obtained by polymerizing a branched polyalkyleneimine containing a primary amine, a secondary amine, and a tertiary amine obtained by ring-opening polymerization of the alkyleneimine as a raw material, or an alkyloxazoline as a raw material. Any of a linear polyalkyleneimine containing only the primary amine and the secondary amine obtained in this way, or a three-dimensionally crosslinked structure may be used. In addition, ethylenediamine, propylenediamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dipropylenetriamine, tripropylenetetramine, dihexamethylenetriamine, aminopropylethylenediamine, bisaminopropylethylenediamine monomers are copolymerized. It may be. A polyalkyleneimine is usually derived from the reactivity of an active hydrogen atom on a nitrogen atom contained therein, and in addition to a tertiary amino group, a primary amino group having an active hydrogen atom or a secondary amino group (imino). Group).
[0049]
　The number of nitrogen atoms in the polyalkyleneimine is not particularly limited and is preferably 4 or more and 3,000, more preferably 8 or more and 1,500 or less, and further preferably 11 or more and 500 or less. The number average molecular weight of the polyalkyleneimine is preferably 100 or more and 20,000 or less, more preferably 200 or more and 10,000 or less, and further preferably 500 or more and 8,000 or less.
[0050]
　On the other hand, as carboxylic acids to be added, acetic acid, propionic acid, butyric acid, valeric acid, caproic acid, enanthic acid, caprylic acid, capric acid, pelargonic acid, undecanoic acid, lauric acid, tridecanoic acid, myristic acid, myristoleic acid, Aliphatic monocarboxylic acids such as palmitic acid, stearic acid, oleic acid, linoleic acid, arachidic acid, behenic acid and erucic acid; alicyclic monocarboxylic acids such as cyclohexanecarboxylic acid and methylcyclohexanecarboxylic acid; benzoic acid and toluic acid , Aromatic monocarboxylic acids such as ethylbenzoic acid and phenylacetic acid; malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecanedioic acid, dodecanedioic acid, hexadecanedioic acid , Hexadecenedioic acid, octadecanedioic acid, octadecenedioic acid, eicosanedioic acid, eicosenedioic acid, docosanedioic acid, diglycolic acid, 2,2,4-trimethyladipic acid, 2,4,4-trimethyladipic acid, etc. Aliphatic dicarboxylic acids; alicyclic dicarboxylic acids such as 1,3-cyclohexanedicarboxylic acid, 1,4-cyclohexanedicarboxylic acid, norbornanedicarboxylic acid; terephthalic acid, isophthalic acid, phthalic acid, m-xylylenedicarboxylic acid, p- Aromatic dicarboxylic acids such as xylylenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid and 2,7-naphthalenedicarboxylic acid; 1,2,4-butanetricarboxylic acid, 1,3,5 Examples include tricarboxylic acids such as pentanetricarboxylic acid, 1,2,6-hexanetricarboxylic acid, 1,3,6-hexanetricarboxylic acid, 1,3,5-cyclohexanetricarboxylic acid and trimesic acid. These can use 1 type(s) or 2 or more types.
[0051]
　The amount of amines to be added is appropriately determined by a known method in consideration of the terminal amino group concentration, terminal carboxyl group concentration, and relative viscosity of the polyamide (A1) to be produced. Usually, the amount of amines added to 1 mol of the polyamide raw material (1 mol of the monomer constituting the repeating unit or 1 mol of the monomer unit) is sufficient to obtain sufficient reactivity and to obtain a polyamide having a desired viscosity. From the viewpoint of facilitating the production, it is preferably 0.5 meq/mol or more and 20 meq/mol or less, and more preferably 1.0 meq/mol or more and 10 meq/mol or less (the equivalent of the amino group (eq) is The amount of an amino group which reacts with a carboxyl group in a ratio of 1:1 to form an amide group is 1 equivalent.).
[0052]
　In the polyamide (A1), it is preferable to add a diamine and/or polyamine during the polymerization in order to satisfy the condition of the terminal group concentration among the above-exemplified amines. From the viewpoint of suppressing gel generation, an aliphatic diamine, It is more preferable to add at least one selected from the group consisting of alicyclic diamine and polyalkyleneimine during polymerization.
[0053]
　The polyamide (A1) is also preferably an aliphatic polyamide mixture composed of two or more kinds of aliphatic polyamides having different end group concentrations as long as the above end group concentration is satisfied. In this case, the terminal amino group concentration and terminal carboxyl group concentration of the aliphatic polyamide mixture are determined by the terminal amino group concentration and terminal carboxyl group concentration of the aliphatic polyamide constituting the mixture, and the mixing ratio thereof.
[0054]
　[Elastomer polymer (A2)] The
　aliphatic polyamide composition (A) contains an elastomer polymer (A2) having a structural unit derived from an unsaturated compound having a carboxyl group and/or an acid anhydride group ( Hereinafter, it may be referred to as an elastomer polymer (A2).
[0055]
　Examples of the elastomeric polymer (A2) include (ethylene and/or propylene)/α-olefin copolymers, (ethylene and/or propylene)/(α,β-unsaturated carboxylic acid ester) copolymers, and the like. These may be used alone or in combination of two or more.
[0056]
　The (ethylene and/or propylene)/α-olefin copolymer is a copolymer of ethylene and/or propylene and α-olefin having 3 or more carbon atoms, and α-olefin having 3 or more carbon atoms. Examples of the olefin include propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-pentadecene, 1-hexadecene, 1-heptadecene, 1-octadecene, 1-nonadecene, 1-eicosene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4- Methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 9-methyl-1-decene, 11-methyl-1-dodecene, 12-ethyl-1-tetradecene and the like can be mentioned. These can use 1 type(s) or 2 or more types. Further, 1,3-butadiene, 1,4-pentadiene, 1,4-hexadiene, 1,5-hexadiene, 1,4-octadiene, 1,5-octadiene, 1,6-octadiene, 1,7-octadiene, 2-methyl-1,5-hexadiene, 6-methyl-1,5-heptadiene, 7-methyl-1,6-octadiene, 4-ethylidene-8-methyl-1,7-nonadiene, 4,8-dimethyl- 1,4,8-decatriene (DMDT), dicyclopentadiene, cyclohexadiene, cyclooctadiene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2- Norbornene, 6-chloromethyl-5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene Polyenes of non-conjugated dienes such as These may be used alone or in combination of two or more.
[0057]
　The (ethylene and/or propylene)/(α,β-unsaturated carboxylic acid ester)-based copolymer is a polymer obtained by copolymerizing ethylene and/or propylene with an α,β-unsaturated carboxylic acid ester monomer. And the α,β-unsaturated carboxylic acid ester monomers include methyl acrylate, methyl methacrylate, ethyl acrylate, ethyl methacrylate, propyl acrylate, propyl methacrylate, butyl acrylate, butyl methacrylate, Pentyl acrylate, Pentyl methacrylate, Hexyl acrylate, Hexyl methacrylate, Heptyl acrylate, Heptyl methacrylate, Octyl acrylate, Octyl methacrylate, Nonyl acrylate, Nonyl methacrylate, Decyl acrylate, Decyl methacrylate, Acrylic acid Examples thereof include 2-ethylhexyl, 2-ethylhexyl methacrylate, hydroxyethyl acrylate, hydroxyethyl methacrylate, monomethyl maleate, monomethyl itaconate, dimethyl maleate, dimethyl itaconate and the like. These can use 1 type(s) or 2 or more types.
[0058]
　Examples of the unsaturated compound having a carboxyl group in the elastomer polymer (A2) include acrylic acid, methacrylic acid, maleic acid, fumaric acid, itaconic acid, crotonic acid, mesaconic acid, citraconic acid, glutaconic acid, cis-4-cyclohexene- Examples thereof include 1,2-dicarboxylic acid, endobicyclo-[2.2.1]-5-heptene-2,3-dicarboxylic acid, and α,β-unsaturated carboxylic acids such as metal salts of these carboxylic acids. Examples of the unsaturated compound having an acid anhydride group include maleic anhydride, itaconic anhydride, citraconic anhydride, and abicyclo-[2.2.1]-5-heptene-2,3-dicarboxylic anhydride. , A dicarboxylic acid anhydride having a β-unsaturated bond. These can use 1 type(s) or 2 or more types. Among these, dicarboxylic acid anhydrides having an α,β-unsaturated bond are preferable, and maleic anhydride and itaconic anhydride are more preferable.
[0059]
　The carboxyl group and/or acid anhydride group concentration in the elastomer polymer (A2) expresses good compatibility with the polyamide (A1), and also the viewpoint of fluidity of the obtained aliphatic polyamide composition (A). Therefore, it is preferably 25 μeq/g or more and 200 μeq/g or less, and more preferably 50 μeq/g or more and 150 μeq/g or less.
[0060]
　The concentration of the carboxyl group and/or the acid anhydride group in the elastomer polymer (A2) was measured by dissolving the elastomer polymer in a toluene solution and adding ethanol to the sample solution to prepare phenolphthalein as an indicator. And can be measured by titrating with 0.1N KOH ethanol solution.
[0061]
　[Plasticizer (A3)] The
　aliphatic polyamide composition (A) also preferably contains a plasticizer (A3) from the viewpoint of imparting flexibility to the obtained laminated tube.
　The plasticizer (A3) does not contain a sulfur atom, and has an ester structure of p- and/or o-hydroxybenzoic acid and a linear and/or branched alkyl aliphatic alcohol having 12 to 24 carbon atoms. Contains (hereinafter, may be referred to as a plasticizer (A3)).
[0062]
　The plasticizer (A3) comprises an ester of p- and/or o-hydroxybenzoic acid and a linear or branched aliphatic alcohol having 12 to 24 carbon atoms. The aliphatic alcohol that is a raw material of the ester may have either a straight chain or a branched chain. The number of carbon atoms in the aliphatic alcohol is preferably 12 or more and 22 or less. If the number of carbon atoms is 12 or more and 22 or less, both saturated alcohols and unsaturated alcohols can be used. Such an ester of alcohol and hydroxybenzoic acid has a good compatibility with a polyamide resin, gives little stickiness on the surface, has a low volatility, and has a sufficient plasticizing effect.
[0063]
　Examples of the plasticizer (A3) include dodecyl o-hydroxybenzoate, dodecyl p-hydroxybenzoate, tridecyl o-hydroxybenzoate, tridecyl p-hydroxybenzoate, tetradecyl o-hydroxybenzoate, p-hydroxybenzoic acid. Tetradecyl, pentadecyl o-hydroxybenzoate, pentadecyl p-hydroxybenzoate, hexadecyl o-hydroxybenzoate, hexadecyl p-hydroxybenzoate, heptadecyl o-hydroxybenzoate, heptadecyl p-hydroxybenzoate, octadecyl o-hydroxybenzoate , Octadecyl p-hydroxybenzoate, nonadecyl o-hydroxybenzoate, nonadecyl p-hydroxybenzoate, icosyl o-hydroxybenzoate, icosyl p-hydroxybenzoate, henicosyl o-hydroxybenzoate, henicosyl p-hydroxybenzoate, Docosyl o-hydroxybenzoate, docosyl p-hydroxybenzoate, tricosyl o-hydroxybenzoate, tricosyl p-hydroxybenzoate, tetracosyl o-hydroxybenzoate, tetracosyl p-hydroxybenzoate, hexyldecyl o-hydroxybenzoate, Hexyldecyl p-hydroxybenzoate, ethyldecyl o-hydroxybenzoate, ethyldecyl p-hydroxybenzoate, ethyldodecyl o-hydroxybenzoate, ethyldodecyl p-hydroxybenzoate, octyloctyl o-hydroxybenzoate, p-hydroxybenzoic acid Octyl octyl acid, octyldodecyl o-hydroxybenzoate, octyldodecyl p-hydroxybenzoate, decyldecyl o-hydroxybenzoate, decyldecyl p-hydroxybenzoate, decyldodecyl p-hydroxybenzoate, decyldodecyl p-hydroxybenzoate, etc. Is mentioned. These can use 1 type(s) or 2 or more types. Among these, p-hydroxybenzoic acid 2-hexyldecyl ester (HDPB) and p-hydroxybenzoic acid hexadecyl ester (CEPB) are preferable.
[0064]
　The content of the polyamide (A1) in the aliphatic polyamide composition (A) is 55% by mass or more and 95% by mass or less, and 60% by mass or more 95% with respect to 100% by mass of the aliphatic polyamide composition (A). It is preferably not more than 70% by mass, more preferably not less than 70% by mass and not more than 89% by mass. When the content of the polyamide (A1) is within the above range, the resulting laminated tube can have sufficiently excellent properties such as breaking pressure strength at high temperature. On the other hand, when the content of the polyamide (A1) is less than the lower limit value, the breaking pressure strength of the laminated tube at high temperature cannot be sufficiently obtained. On the other hand, when the content of the polyamide (A1) exceeds the above upper limit, the flexibility and low temperature impact resistance of the laminated tube cannot be sufficiently obtained.
[0065]
　Content of elastomer polymer (A2) in aliphatic polyamide composition (A) is 5 mass% or more and 30 mass% or less with respect to 100 mass% of aliphatic polyamide composition (A), and is 7 mass%. It is preferably 25% by mass or more and more preferably 10% by mass or more and 20% by mass or less. When the content of the elastomer polymer (A2) is within the above range, the flexibility and the low temperature impact resistance can be excellent while maintaining the mechanical properties of the obtained laminated tube. On the other hand, when the content of the elastomer polymer (A2) is less than the lower limit value described above, the flexibility and the low temperature impact resistance of the laminated tube cannot be sufficiently obtained. On the other hand, when the content of the elastomer polymer (A2) exceeds the upper limit value, the breaking pressure strength of the laminated tube at high temperature and other mechanical properties cannot be sufficiently obtained.
[0066]
　The content of the plasticizer (A3) in the aliphatic polyamide composition (A) is 0% by mass or more and 15% by mass or less, and 1% by mass or more based on 100% by mass of the aliphatic polyamide composition (A). It is preferably 10% by mass or less. When the content of the plasticizer (A3) is within the appropriate range, the flexibility of the laminated tube can be made excellent while maintaining the high temperature breaking pressure strength of the obtained laminated tube. On the other hand, when the content of the plasticizer (A3) exceeds the upper limit value, the breaking pressure strength of the laminated tube at high temperature may not be sufficiently obtained.
[0067]
　The flexural modulus of the aliphatic polyamide composition (A) measured according to ISO 178 is 400 MPa or more and 1,000 MPa or less, preferably 450 MPa or more and 950 MPa or less, and more preferably 500 MPa or more and 900 MPa or less. preferable. When the flexural modulus of the aliphatic polyamide composition (A) is within the above range, the flexibility of the laminated tube can be made excellent while maintaining the high temperature breaking pressure strength of the obtained laminated tube. The flexural modulus of the aliphatic polyamide composition (A) can be adjusted by appropriately changing the addition amount of the elastomer polymer (A2) and, if necessary, the plasticizer (A3).
[0068]
　There are no particular restrictions on the method for producing the aliphatic polyamide composition (A), and various conventionally known methods can be employed by incorporating various additives as necessary. For example, a polyamide (A1), an elastomeric polymer (A2), and a plasticizer (A3) together with other components to be added as necessary are used so that the pellets have the above mixing ratio by using a tumbler or a mixer. Uniformly dry blending method, polyamide (A1), elastomer polymer (A2), and plasticizer (A3) together with other components optionally added, a method of dry blending in advance and melt kneading, polyamide ( A1), the elastomeric polymer (A2), and the plasticizer (A3) are previously dry-blended together with other components to be added as required, and each of them is separately fed and melt-kneaded. be able to. The melt-kneading can be performed using a kneader such as a single-screw extruder, a twin-screw extruder, a kneader, a Banbury mixer.
[0069]
　Furthermore, if necessary, the aliphatic polyamide composition (A) contains an antioxidant, a heat stabilizer, an ultraviolet absorber, a light stabilizer, a lubricant, an inorganic filler, an antistatic agent, a flame retardant, and crystallization. Accelerators, colorants and the like may be added.
[0070]
2. (B) Layer
　The (b) layer of the laminated tube of the present invention contains the modified polyolefin (B).
[0071]
　The modified polyolefin (B) has a unit derived from a monomer based on an α-olefin having 2 to 10 carbon atoms, and has a melting point of 130° C. or higher measured according to ISO 11357-3 ( Hereinafter, it may be referred to as modified polyolefin (B).).
[0072]
　The polyolefin (B1) constituting the modified polyolefin (B) is a polymer having a unit derived from a monomer based on an α-olefin having 2 to 10 carbon atoms as a main component, and having 2 or more carbon atoms. It is preferably a polymer having as a main component a unit derived from a monomer based on α-olefin of 8 or less. When the number of carbon atoms of the unit derived from the α-polyolefin-based monomer in the modified polyolefin (B) is within the above range, the elution resistance of low molecular weight substances and ionic components of the resulting laminated tube is particularly improved. It can be excellent.
　In the case of a copolymer, the content of units derived from an α-polyolefin-based monomer having 2 to 10 carbon atoms as a main component is 60 mol% or more based on 100 mol% of all polymerized units. Is preferable, 70 mol% or more is more preferable, and 90 mol% or more is further preferable. When the content of the unit derived from the α-polyolefin-based monomer having 2 to 10 carbon atoms is at least the above value, the obtained laminated tube has a sufficient flexibility and a low molecular weight. The elution resistance of substances and ionic components is further improved.
[0073]
　Examples of the α-olefin-based monomer having 2 to 10 carbon atoms include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1-nonene and 1-decene. , 2-butene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4,4-dimethyl-1-pentene, 4-methyl- 1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene and the like can be mentioned. These can use 1 type(s) or 2 or more types. Among these, a monomer based on an α-olefin having 2 to 8 carbon atoms is preferable.
[0074]
　Within the range that does not impair the excellent properties of the obtained laminated tube, for example, styrenes, non-conjugated dienes, cyclic olefins other than the α-olefin-based monomer having 2 to 10 carbon atoms. Other monomers such as oxygen atom-containing olefins may be included. Examples of styrenes include styrene, o-methylstyrene, m-methylstyrene, p-methylstyrene, 1,5-dimethylstyrene, 2,4-dimethylstyrene, vinylnaphthalene, vinylanthracene, 4-propylstyrene, 4-cyclohexyl. Examples thereof include styrene, 4-dodecylstyrene, 2-ethyl-4-benzylstyrene, 4-(phenylbutyl)styrene and the like. Non-conjugated dienes include 1,3-butadiene 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) and the like can be mentioned. Examples of cyclic olefins include dicyclopentadiene, cyclohexadiene, cyclooctadiene, 5-vinylnorbornene, 5-ethylidene-2-norbornene, 5-methylene-2-norbornene, 5-isopropylidene-2-norbornene, 6-chloro. Examples thereof include methyl-5-isopropenyl-2-norbornene, 2,3-diisopropylidene-5-norbornene, 2-ethylidene-3-isopropylidene-5-norbornene, 2-propenyl-2,5-norbornadiene and the like. Examples of the oxygen atom-containing olefins include hexenol, hexenoic acid, and methyl octenoate. The content of units derived from other monomers is preferably less than 40 mol%, more preferably less than 30 mol%, and less than 10 mol% based on 100 mol% of all polymerized units. Is more preferable.
[0075]
　As these polyolefins (B1), α with a monomer copolymerizable with polyethylene, polypropylene, polybutene-1, poly(4-methylpentene-1), ethylene, propylene, 1-butene, or 4-methylpentene-1. -Crystalline polyolefin such as olefin copolymer is preferred. These can use 1 type(s) or 2 or more types. Among these, a polypropylene homopolymer, a random copolymer of propylene and 20% by mole or less of other α-olefins, and a block copolymer of propylene and 30% by mole or less of other α-olefins are more preferable.
[0076]
　The polyolefin (B1) can be produced by any conventionally known method, for example, polymerization can be performed using a titanium-based catalyst, a vanadium-based catalyst, a metallocene catalyst, or the like. Further, the polyolefin (B1) may be in the form of either a resin or an elastomer, and can have both an isotactic structure and a syndiotactic structure, and there is no particular restriction on stereoregularity. When the polyolefin (B1) is a copolymer, it may be any of alternating copolymerization, random copolymerization and block copolymerization.
[0077]
　The modified polyolefin (B) has a melting point of 130° C. or higher, preferably 145° C. or higher, measured according to ISO 11357-3. When the melting point of the modified polyolefin (B) is at least the above value, the resulting laminated tube will have excellent breaking pressure strength at high temperatures and long-term resistance to chemicals.
[0078]
　The modified polyolefin (B) is at least one functional group selected from the group consisting of a carboxyl group or a derivative thereof, a hydroxyl group, an epoxy group, an amino group, an amide group, an imide group, a nitrile group, a thiol group and an isocyanate group. It is preferred to contain units derived from unsaturated compounds having The modified polyolefin (B) contains a unit derived from an unsaturated compound having the above functional group, whereby the interlayer adhesion between the (a) layer and the (b) layer in the obtained laminated tube is made high. You can
[0079]
　Examples of the unsaturated compound having a carboxyl group include acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, norbornene dicarboxylic acid, bicyclo[2,2,2]. 1] Unsaturated carboxylic acids such as hept-2-ene-5,6-dicarboxylic acid and their derivatives (eg, acid anhydrides, acid halides, amides, imides, esters, etc.). These can use 1 type(s) or 2 or more types.
[0080]
　Examples of the unsaturated compound derivative having a carboxyl group include maleenyl chloride, maleenyl imide, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, bicyclo[2,2,1]hept-2-ene- 5,6-dicarboxylic acid anhydride, dimethyl maleate, monomethyl maleate, diethyl maleate, diethyl fumarate, dimethyl itaconate, diethyl citracone, dimethyl tetrahydrophthalate, bicyclo[2,2,1]hept-2- Examples thereof include dimethyl ene-5,6-dicarboxylate and the like. These can use 1 type(s) or 2 or more types.
[0081]
　Examples of the unsaturated compound having a hydroxyl group include hydroxyl group-containing (meth)acryl such as hydroxyethyl acrylate, hydroxyethyl methacrylate, hydroxypropyl acrylate, hydroxypropyl methacrylate, glycerin mono(meth)acrylate, and pentaerythritol mono(meth)acrylate. Examples thereof include acid esters, 10-undecen-1-ol, 1-octen-3-ol, glycerin monoallyl ether, allyl alcohol, 2-butene-1,4-diol, and glycerin monoalcohol. These can use 1 type(s) or 2 or more types.
[0082]
　As the unsaturated compound having an epoxy group, for example, glycidyl acrylate, glycidyl ester of unsaturated carboxylic acid such as glycidyl methacrylate, or maleic acid, monoglycidyl ester of unsaturated dicarboxylic acid such as fumaric acid (in the case of monoglycidyl ester An alkyl group having 1 to 12 carbon atoms), alkyl glycidyl ester of p-styrenecarboxylic acid, 2-methylallyl glycidyl ether, 3,4-epoxy-1-butene, 3,4-epoxy-3-methyl-1 -Butene, 3,4-epoxy-1-pentene, 3,4-epoxy-3-methyl-1-pentene, 5,6-epoxy-1-hexene, vinylcyclohexene monoxide and the like can be mentioned. These can use 1 type(s) or 2 or more types.
[0083]
　Examples of the unsaturated compound having an amino group include acrylic acid or methacrylic acid such as aminomethyl acrylate, aminomethyl methacrylate, dimethylaminoethyl methacrylate, aminopropyl acrylate, aminopropyl methacrylate, and cyclohexylaminoethyl methacrylate. And aminoamine ester derivatives of N-vinyldiethylamine, N-acetylvinylamine and other vinylamine derivatives. These can use 1 type(s) or 2 or more types.
[0084]
　Examples of the unsaturated compound having an amide group include acrylamide derivatives such as acrylamide, methacrylamide, N-methylacrylamide, N,N-dimethylacrylamide, and N,N-dimethylaminopropylacrylamide. These can use 1 type(s) or 2 or more types.
[0085]
　Examples of the unsaturated compound having an imide group include N-acryloyloxyethyl-1,2,3,6-tetrahydrophthalimide (manufactured by Toagosei Co., Ltd., trade name: Aronix TO-1428), N-acryloyloxyethyl. Hexahydrophthalimide (Toagosei Co., Ltd., trade name: Aronix TO-1429), N-acryloyloxyethyl-3,4,5,6-tetrahydrophthalimide (Toagosei Co., Ltd., trade name: Aronix TO- 1534) and the like. These can use 1 type(s) or 2 or more types.
[0086]
　Examples of the unsaturated compound having a nitrile group include acrylonitrile, methacrylonitrile, 5-hexenenitrile, 5-methyl-5-hexenenitrile, methyl-2-cyanoacrylate, ethyl-2-cyanoacrylate, butyl-2- Examples thereof include cyanoacrylate, cyclohexyl-2-cyanoacrylate, 2-ethylhexyl-2-cyanoacrylate, ethoxyethyl-2-cyanoacrylate and the like. These can use 1 type(s) or 2 or more types.
[0087]
　Examples of unsaturated compounds having a thiol group include 2-mercaptoethanol, ethanedithiol, 1,2-propanedithiol, 1,3-propanedithiol, parahydroxythiophenol, 3-mercapto-1,2-propanedithiol, Compounds containing thiol group-containing compounds such as aliphatic or aromatic mercapto alcohols or dithiols such as 1,4-butanedithiol, 2-mercaptoethyl ether, and 2-mercaptoethyl sulfide, and esters with acrylic acid or methacrylic acid Can be mentioned. These can use 1 type(s) or 2 or more types.
[0088]
　Examples of the unsaturated compound having an isocyanate group include 2-methacryloyloxyethyl isocyanate (manufactured by Showa Denko KK, trade name: Karenz MOI), 2-acryloyloxyethyl isocyanate (manufactured by Showa Denko KK, Product name: Karens AOI) and the like. These can use 1 type(s) or 2 or more types.
[0089]
　Among these, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, endobicyclo-[2.2.1]-5-heptene-2,3-dicarboxylic anhydride, acrylic acid, methacrylic acid , Hydroxyethyl acrylate, hydroxyethyl methacrylate, glycidyl methacrylate, aminopropyl methacrylate are preferable, maleic anhydride, itaconic anhydride, citraconic anhydride, tetrahydrophthalic anhydride, endobicyclo-[2.2.1]-5-heptene- A dicarboxylic acid anhydride of 2,3-dicarboxylic acid anhydride is more preferable, and maleic anhydride is still more preferable.
[0090]
　As a method for introducing the unit derived from the unsaturated compound having a functional group into the polyolefin, a well-known method can be adopted. For example, a method of graft-copolymerizing an unsaturated compound having the functional group on the polyolefin (B1), a method of radical copolymerizing an olefin monomer and an unsaturated compound having the functional group, and the like can be exemplified. A method of graft-copolymerizing an unsaturated compound having the functional group with the polyolefin (B1) is preferable.
[0091]
　For such a modified polyolefin (B), various known methods can be adopted for graft-modifying the polyolefin (B1) with the unsaturated compound having the functional group. For example, there is a method of melting the unmodified polyolefin and adding the unsaturated compound having a functional group for graft copolymerization, or a method of dissolving the polyolefin in a solvent and adding a graft monomer for graft copolymerization. In any case, in order to efficiently graft-polymerize the unsaturated compound having the functional group, it is preferable to carry out the reaction in the presence of a radical polymerization initiator.
[0092]
　The radical polymerization initiator used is not particularly limited as long as it accelerates the reaction between the polyolefin main chain and the unsaturated compound having the functional group, but organic peroxides and organic peresters are preferable. Specifically, benzoyl peroxide, dichlorobenzoyl peroxide, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(peroxybenzoate) hexyne-3,1,4-bis(t -Butylperoxyisopropyl)benzene, lauroyl peroxide, t-butylperacetate, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,2,5-dimethyl-2,5-di(t -Butyl peroxide) hexane, t-butyl benzoate, t-butyl perphenyl acetate, t-butyl perisobutyrate, t-butyl per-sec-octoate, t-butyl perpivalate, cumyl perpivalate, t-butyl Examples thereof include perdiethyl acetate, and other azo compounds such as azobis-isobutylnitrile and dimethylazoisobutylnitrile. These can use 1 type(s) or 2 or more types. Among these, dicumyl peroxide, di-t-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxy)hexyne-3,2,5-dimethyl-2,5-di(t- Dialkyl peroxides such as butylperoxy)hexane and 1,4-bis(t-butylperoxyisopropyl)benzene are more preferable.
[0093]
　The radical polymerization initiator is preferably used in an amount of about 0.001 to 10 parts by mass with respect to 100 parts by mass of the polyolefin (B1).
　The graft amount of the unsaturated compound having a functional group is preferably 0.05% by mass or more and 20% by mass or less, and 0.05% by mass or more and 10% by mass, with respect to 100% by mass of the polyolefin (B1). The content is more preferably the following or less, still more preferably 0.05% by mass or more and 5% by mass or less, and particularly preferably 0.05% by mass or more and 3% by mass or less. The graft amount of the polyolefin (B1) is the net graft amount measured after removing the unsaturated compound having the functional group from the polyolefin (B1). The grafting amount can be determined by a known means such as 13 C-NMR and 1 H-NMR measurement. When a monomer having an acidic functional group such as unsaturated carboxylic acid and its acid anhydride is used as the unsaturated compound having a functional group, an amount serving as a guide for the amount of the functional group introduced into the polyolefin (B1). For example, the acid value can also be used. In addition, when maleic anhydride is used as the unsaturated compound having the functional group, it is based on the absorption spectrum of the carbonyl group of maleic anhydride, which is usually detected around 1780 to 1790 cm -1 by using an infrared spectrophotometer. Then, the graft amount can be obtained.
[0094]
　The modified polyolefin (B) is preferably a maleic anhydride modified polypropylene from the viewpoint of obtaining a laminated tube having good mechanical properties, long-term resistance to chemicals, and interlayer adhesion. The content of polypropylene in the maleic anhydride-modified polypropylene is preferably 50% by mass or more and 99.5% by mass or less, and 60% by mass or more and 97% by mass or less, based on 100% by mass of the maleic anhydride modified polypropylene. It is more preferable that the amount is 70% by mass or more and 95% by mass or less. When the content of polypropylene in the maleic anhydride-modified polypropylene is the above value or more, the flexibility of the obtained laminated tube is sufficient, and the elution resistance of low molecular weight substances and ionic components is further excellent. Can be
[0095]
　The modified polyolefin (B) has an MFR value measured according to ISO 1133 under the conditions of 230° C./2160 g, which is preferably 1.0 g/10 min or more and 10.0 g/10 min or less. It is more preferably 0.5 g/10 min or more and 7.0 g/10 min or less. When the MFR value of the modified polyolefin (B) is within the above range, it is possible to further improve the molding stability of the obtained laminated tube.
[0096]
　Also, the modified polyolefin (B) has a density, as measured in accordance with ISO 1183-3 is 0.85 g / cm 3 is preferably at least, 0.85 m 3 or more 0.95 m 3 and more not more than preferable. When the density of the modified polyolefin (B) is within the above range, the resulting laminated tube has sufficiently excellent flexibility and breaking pressure strength.
[0097]
　The modified polyolefin (B) may contain various additives as required. Examples of such additives include conductive fillers, antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, lubricants, inorganic fillers, antistatic agents, flame retardants, crystallization accelerators, plasticizers. Agents, colorants, lubricants, and other thermoplastic resins.
[0098]
3. The (c) layer
　laminated tube preferably further has a (c) layer.
　Layer (c) of the laminated tube contains polyolefin (C).
[0099]
　The polyolefin (C) has a unit derived from a monomer based on an α-olefin having 2 to 10 carbon atoms and has a melting point of 120° C. or higher measured according to ISO 11357-3. The tensile yield stress measured according to 527 is 20 MPa or more, and the Charpy impact strength (notched) at 23° C. measured according to ISO 179/1eA is 40 kJ/m 2 or more (hereinafter, polyolefin (C)). Sometimes called).
[0100]
　The polyolefin (C) is a polymer whose main component is a unit derived from a monomer based on an α-olefin having 2 to 10 carbon atoms, and is based on an α-olefin having 2 to 8 carbon atoms. It is preferably a polymer containing a unit derived from a monomer as a main component. When the number of carbon atoms of the unit derived from the α-polyolefin-based monomer in the polyolefin (C) falls within the above range, the resulting laminated tube has sufficient flexibility while preventing chemical liquid permeation. In addition, the long-term resistance of the drug solution can be further improved.
[0101]
　Examples of the polyolefin (C) include the polyolefin (B1) described in the description of the modified polyolefin (B). Among these, from the viewpoint of obtaining a laminated tube having good mechanical properties and long-term resistance to chemicals, (1) ethylene homopolymer (manufacturing method may be either low pressure method or high pressure method), (2) ethylene 99 Ethylene/propylene copolymer of 1 mol% or more and 20 mol% or less of propylene, preferably 95 mol% or less and 85 mol% or more of ethylene, and ethylene of 5 mol% or more and 15 mol% or less of propylene /Propylene copolymer, (3) 99 mol% or less and 80 mol% or less of ethylene, and 1 mol% to 20 mol% of 1/butene ethylene/1-butene copolymer, preferably 95 mol% or less and 85 mol% of ethylene %, 1-butene 5 mol% or more and 15 mol% or less ethylene/1-butene copolymer, (4) ethylene 99 mol% or less 80 mol% or more, 1-octene 1 mol% or more and 20 mol% or less Ethylene/1-octene copolymer, preferably ethylene 97 mol% or less and 85 mol% or more, 1-octene 3 mol% or more and 15 mol% or less ethylene/1-octene copolymer, (5) ethylene, An ethylene-based copolymer such as a copolymer of 10 mol% or less of other α-olefin (excluding propylene, 1-butene and 1-octene) or a vinyl monomer (for example, vinyl acetate, ethyl acrylate), (6 ) Propylene homopolymer, (7) Random copolymer of propylene and 30 mol% or less of other α-olefin, preferably random copolymer of propylene and 20 mol% or less of other α-olefin, (8) Block copolymer of propylene and 40 mol% or less of other α-olefins, (9) 1-butene homopolymer, (10) 1-butene and random copolymer of 10 mol% or less of other α-olefins , (11) 4-methyl-1-pentene homopolymer, (12) 4-methyl-1-pentene homopolymer or copolymer such as random copolymer of 20 mol% or less of other α-olefins Are preferred, (6) propylene homopolymer, (7) propolymer
[0102]
　The melting point of the polyolefin (C) measured according to ISO 11357-3 is 120° C. or higher, and preferably 125° C. or higher. When the melting point of the polyolefin (C) is at least the above value, the breaking pressure strength of the obtained laminated tube at high temperature and the long-term resistance to a chemical solution can be further improved.
[0103]
　Further, the polyolefin (C) has a tensile yield stress measured according to ISO 527 of 20 MPa or more, and preferably 25 MPa or more.
　Further, the polyolefin (C) has a Charpy impact strength (notched) at 23° C. measured according to ISO 179/1eA of 40 kJ/m 2 or more, and preferably 45 kJ/m 2 or more. When the tensile yield stress and the Charpy impact strength (with notch) at 23° C. of the polyolefin (C) are the above values ​​or more, the resulting laminated tube is further excellent in low temperature impact resistance and fracture pressure strength at high temperature. Can be one.
[0104]
　The polyolefin (C) can be produced by any conventionally known method, for example, polymerization can be performed using a titanium-based catalyst, a vanadium-based catalyst, a metallocene catalyst, or the like. Further, the polyolefin (C) may be in the form of either a resin or an elastomer, and can have both an isotactic structure and a syndiotactic structure, and there is no particular restriction on stereoregularity. When the polyolefin (C) is a copolymer, it may be any of alternating copolymerization, random copolymerization and block copolymerization.
[0105]
　The polyolefin (C) may contain various additives as required. Examples of such additives include conductive fillers, antioxidants, heat stabilizers, ultraviolet absorbers, light stabilizers, lubricants, inorganic fillers, antistatic agents, flame retardants, crystallization accelerators, plasticizers. Agents, colorants, lubricants, and other thermoplastic resins.
[0106]
　[Laminated tube] A
　first aspect of the laminated tube includes two or more layers of a layer (a) and a layer (b), and the layers (a) and (b) are arranged in this order from the outer side to the inner side. The thickness of the (a) layer accounts for 60% or more of the total wall thickness of the tube.
[0107]
　In the laminated tube of the first aspect, it is essential to include the layer (a), and it becomes possible to obtain a laminated tube having excellent mechanical properties, chemical resistance and flexibility. It is also essential to include the (b) layer, and the chemical barrier property of the laminated tube, particularly the barrier property against water vapor, cooling liquid (LLC), and urea solution, and long-term chemical solution resistance are improved.
　The thickness of the layer (a) in the laminated tube accounts for 60% or more and 95% or less of the total wall thickness of the tube, preferably 65% ​​or more and 90% or less, and 70% or more and 85% or less. More preferable. When the layer thickness of the (a) layer falls within the above range, each of the above characteristics can be effectively exhibited.
　The thickness of the layer (b) in the laminated tube accounts for more than 5% and less than 40% of the total wall thickness of the tube, preferably more than 10% and less than 35%, and more than 15% and less than 30%. More preferable. When the layer thickness of the layer (b) is within the above range, each of the above characteristics can be effectively exhibited.
[0108]
　In a preferred embodiment, the (a) layer and the (b) layer are arranged adjacent to each other. This makes it possible to obtain a laminated tube having excellent interlayer adhesion.
[0109]
　In a more preferred embodiment, the layer (a) is arranged in the outermost layer of the laminated tube. By arranging the layer (a) as the outermost layer, it is possible to obtain a laminated tube having excellent breaking pressure strength at high temperature. The layer (b) is arranged in the innermost layer of the laminated tube. By disposing the layer (b) as the innermost layer, it becomes possible to suppress the elution of the low molecular weight substance due to contact with the chemical liquid.
[0110]
　The total number of layers in the laminated tube of the first aspect is not particularly limited as long as it is at least two layers including the (a) layer and the (b) layer. Further, in the laminated tube of the first aspect, in addition to the two layers of (a) layer and (b) layer, other thermoplastic resin is added in order to impart a further function or to obtain an economically advantageous laminated tube. You may have 1 layer or 2 or more layers containing. The number of layers of the laminated tube of the first aspect is 2 or more, but it is preferably 8 or less, more preferably 2 or more and 7 or less as judged from the mechanism of the tube manufacturing apparatus.
[0111]
　The second aspect of the laminated tube includes three or more layers having the layer (c) in addition to the first aspect.
[0112]
　In the laminated tube of the second aspect, it is essential to include the layer (a), and it becomes possible to obtain a laminated tube having excellent mechanical properties, chemical resistance and flexibility. It is also essential to include the layer (b), and the chemical barrier property of the laminated tube, particularly the barrier property against water vapor, cooling liquid (LLC), and urea solution is improved. It is also essential to include the layer (c), and it becomes possible to obtain a laminated tube which is excellent in low temperature impact resistance of the obtained laminated tube, breaking pressure strength at high temperature, and long-term chemical solution resistance.
　The thickness of the layer (a) in the laminated tube accounts for 60% or more and 95% or less of the total wall thickness of the tube, preferably 65% ​​or more and 90% or less, and 70% or more and 85% or less. More preferable. When the layer thickness of the (a) layer falls within the above range, each of the above characteristics can be effectively exhibited.
　The total thickness of layers (b) and (c) in the laminated tube accounts for more than 5% and less than 40% of the total wall thickness of the tube, preferably more than 10% and less than 35%, and more than 15% 30. % Is more preferable. When the total thickness of the (b) layer and the (c) layer is within the above range, each of the above properties can be effectively exhibited.
[0113]
　In a preferred embodiment, the layer (c) is arranged inside the layer (b). That is, it is preferable that the layers (a), (b), and (c) are arranged in this order from the outside to the inside. By arranging the layers in such an order, it is possible to further improve the chemical liquid permeation-preventing property and the chemical liquid long-term resistance of the obtained laminated tube.
[0114]
　In a more preferred embodiment, the (b) layer and the (c) layer are arranged adjacent to each other. That is, in the laminated tube, the layer (a) is arranged as the outermost layer, the layer (b) is arranged as the intermediate layer, and the layer (c) is arranged as the innermost layer. By arranging the layer (a) as the outermost layer, it is possible to obtain a laminated tube having excellent breaking pressure strength at high temperature. By arranging the layer (b) as the intermediate layer, it is possible to obtain a laminated tube having excellent interlayer adhesion. By disposing the layer (c) as the innermost layer, it is possible to suppress the elution of the low molecular weight substance due to contact with the chemical liquid.
[0115]
　The total number of layers in the laminated tube of the second aspect is not particularly limited as long as it is at least 3 layers having (a) layer, (b) layer, and (c) layer. Furthermore, the laminated tube of the second aspect, in addition to the three layers of the (a) layer, the (b) layer, and the (c) layer, is provided with a further function, or in order to obtain an economically advantageous laminated tube, You may have one layer or two or more layers containing another thermoplastic resin. The number of layers of the laminated tube of the second aspect is 3 or more, but it is preferably 8 or less, more preferably 3 or more and 7 or less as judged from the mechanism of the tube manufacturing apparatus.
[0116]
　As the other thermoplastic resin in the laminated tube of the first aspect and the second aspect, polyamide (A1), modified polyolefin (B), polycaproamide (polyamide 6) other than polyolefin (C), polyethylene adipamide (polyamide) 26), polytetramethylene succinamide (polyamide 44), polytetramethylene glutamide (polyamide 45), polytetramethylene adipamide (polyamide 46), polytetramethylene sveramide (polyamide 48), polytetramethylene azeramide (Polyamide 49), polytetramethylene sebacamide (polyamide 410), polypentamethylene succinamide (polyamide 54), polypentamethylene glutamide (polyamide 55), polypentamethylene adipamide (polyamide 56), polypenta Methylene suberamide (polyamide 58), polypentamethylene azeramide (polyamide 59), polypentamethylene sebacamide (polyamide 510), polyhexamethylene succinamide (polyamide 64), polyhexamethylene glutamide (polyamide 65), Polyhexamethylene adipamide (polyamide 66), polyhexamethylene suberamide (polyamide 68), polyhexamethylene azeramide (polyamide 69), polynonamethylene adipamide (polyamide 96), polymetaxylylene succinamide (polyamide) MXD4), polymeta-xylylene glutamide (polyamide MXD5), ​​poly-meta-xylylene adipamide (polyamide MXD6), poly-meta-xylylene ceramide (polyamide MXD8), poly-meta-xylylene azeramide (polyamide MXD9), poly-meta-xylylene sebaca. Mido (polyamide MXD10), polymetaxylylene dodecamide (polyamide MXD12), polymetaxylylene terephthalamide (polyamide MXDT), polymetaxylylene isophthalamide (polyamide MXDI), polymetaxylylene hexahydroterephthalamide (polyamide MXDT (polyamide MXDT). H)), polymethaxylylene naphthalamide (polyamide MXDN), polyparaxylyleneCucinamide (polyamide PXD4), polyparaxylylene glutamide (polyamide PXD5), ​​polyparaxylylene adipamide (polyamide PXD6), polyparaxylylene ceramide (polyamide PXD8), polyparaxylylene azeramide (polyamide PXD9) , Polyparaxylylene sebacamide (polyamide PXD10), polyparaxylylene dodecamide (polyamide PXD12), polyparaxylylene terephthalamide (polyamide PXDT), polyparaxylylene isophthalamide (polyamide PXDI), polypara Xylylene hexahydroterephthalamide (polyamide PXDT(H)), polyparaxylylenenaphthalamide (polyamide PXDN), polyparaphenylene terephthalamide (PPTA), polyparaphenylene isophthalamide (PPIA), polymetaphenylene tere Phthalamide (PMTA), polymetaphenylene isophthalamide (PMIA), poly(2,6-naphthalene dimethylene succinamide) (polyamide 2,6-BAN4), poly(2,6-naphthalene dimethylene glutamide) ( Polyamide 2,6-BAN5), poly(2,6-naphthalene methylene adipamide) (polyamide 2,6-BAN6), poly(2,6-naphthalene dimethylene sveramide) (polyamide 2,6-BAN8) , Poly(2,6-naphthalene dimethylene azamide) (polyamide 2,6-BAN9), poly(2,6-naphthalene dimethylene sebacamide) (polyamide 2,6-BAN10), poly(2,6- Naphthalene dimethylene dodecamide) (polyamide 2,6-BAN12), poly(2,6-naphthalene dimethylene terephthalamide) (polyamide 2,6-BANT), poly(2,6-naphthalene dimethylene isophthalamide) (Polyamide 2,6-BANI), poly(2,6-naphthalene dimethylene hexahydroterephthalamide) (polyamide 2,6-BANT(H)), poly(2,6-naphthalene dimethylene naphthalamide) (polyamide 2,6-BANN), poly(1,3-cyclohexanedimethylene succinamide)) (Polyamide 1,3-BAC4), poly(1,3-cyclohexanedimethylene glutamide) (polyamide 1,3-BAC5), poly(1,3-cyclohexanedimethylene adipamide) (polyamide 1,3- BAC6), poly(1,3-cyclohexanedimethylenesveramide (polyamide 1,3-BAC8), poly(1,3-cyclohexanedimethyleneazeramide) (polyamide1,3-BAC9), poly(1,3- Cyclohexane dimethylene sebacamide) (polyamide 1,3-BAC10), poly(1,3-cyclohexane dimethylene dodecamide) (polyamide 1,3-BAC12), poly(1,3-cyclohexane dimethylene terephthalamide) (Polyamide 1,3-BACT), poly(1,3-cyclohexanedimethylene isophthalamide) (polyamide 1,3-BACI), poly(1,3-cyclohexanedimethylene hexahydroterephthalamide) (polyamide 1, 3-BACT(H)), poly(1,3-cyclohexanedimethylenenaphthalamide) (polyamide 1,3-BACN), poly(1,4-cyclohexanedimethylenesuccinamide) (polyamide 1,4-BAC4), Poly(1,4-cyclohexane dimethylene glutamide) (polyamide 1,4-BAC5), poly(1,4-cyclohexane dimethylene adipamide) (polyamide 1,4-BAC6), poly(1,4-cyclohexane Dimethylene suberamide) (polyamide 1,4-BAC8), poly(1,4-cyclohexane dimethylene azeramide) (polyamide 1,4-BAC9), poly(1,4-cyclohexane dimethylene sebacamide) (polyamide 1,4-BAC10), poly(1,4-cyclohexanedimethylene dodecamide) (polyamide 1,4-BAC12), poly(1,4-cyclohexanedimethylene terephthalamide) (polyamide 1,4-BACT), Poly(1,4-cyclohexanedimethylene isophthalamide) (polyamide 1,4-BACI), Poly(1,4-cyclohexanedimethylene hexahydroterephthalamide) (polyamide 1, 4-BACT(H)), poly(1,4-cyclohexanedimethylenenaphthalamide) (polyamide 1,4-BACN), poly(4,4′-methylenebiscyclohexylene succinamide) (polyamide PACM4), Poly(4,4'-methylenebiscyclohexylene glutamide) (polyamide PACM5), poly(4,4'-methylenebiscyclohexylene adipamide) (polyamide PACM6), poly(4,4'-methylenebiscyclohexylene) Suberamide) (polyamide PACM8), poly(4,4′-methylenebiscyclohexyleneazeramide) (polyamide PACM9), poly(4,4′-methylenebiscyclohexylene sebacamide) (polyamide PACM10), poly(4 ,4'-methylenebiscyclohexylene dodecamide) (polyamide PACM12), poly(4,4'-methylenebiscyclohexylene tetradecamide) (polyamide PACM14), poly(4,4'-methylenebiscyclohexylene hexadecamide) ) (Polyamide PACM16), poly(4,4′-methylenebiscyclohexylene octadecamide) (polyamide PACM18), poly(4,4′-methylenebiscyclohexylene terephthalamide) (polyamide PACMT), poly(4,4) 4'-methylenebiscyclohexylene isophthalamide) (polyamide PACMI), poly(4,4'-methylenebiscyclohexylene hexahydroterephthalamide) (polyamide PACMT(H)), poly(4,4'-methylenebis Cyclohexylene naphthalamide) (polyamide PACMN), poly(4,4′-methylenebis(2-methyl-cyclohexylene)succinamide) (polyamide MACM4), poly(4,4′-methylenebis(2-methyl-cyclohexylene)glutamide ) (Polyamide MACM5), poly(4,4′-methylenebis(2-methyl-cyclohexylene)adipamide) (polyamide MACM6), poly(4,4′-methylenebis(2-methyl-cyclohexylene)suberamide) (polyamide MACM8) ), poly(4,4'-Methylenebis(2-methyl-cyclohexylene)azeramide) (polyamide MACM9), poly(4,4'-methylenebis(2-methyl-cyclohexylene)sebacamide) (polyamide MACM10), poly(4,4'-methylenebis(2 -Methyl-cyclohexylene)dodecamide) (polyamide MACM12), poly(4,4'-methylenebis(2-methyl-cyclohexylene)tetradecamide) (polyamide MACM14), poly(4,4'-methylenebis(2-methyl-cyclohexyl) Silen) hexadecamide) (polyamide MACM16), poly(4,4'-methylenebis(2-methyl-cyclohexylene) octadecamide) (polyamide MACM18), poly(4,4'-methylenebis(2-methyl-cyclohexylene) terephthalamide) (Polyamide MACMT), poly(4,4′-methylenebis(2-methyl-cyclohexylene)isophthalamide) (polyamide MACMI), poly(4,4′-methylenebis(2-methyl-cyclohexylene)hexahydroterephthalamide) (Polyamide MACMT(H)), poly(4,4'-methylenebis(2-methyl-cyclohexylene)naphthalamide) (polyamide MACMN), poly(4,4'-propylenebiscyclohexylene succinamide) (polyamide PACP4) , Poly(4,4'-propylenebiscyclohexylene glutamide) (polyamide PACP5), poly(4,4'-propylenebiscyclohexylene adipamide) (polyamide PACP6), poly(4,4'-propylenebiscyclohexyl) Silence beramide) (polyamide PACP8), poly(4,4′-propylenebiscyclohexylene azamide) (polyamide PACP9), poly(4,4′-propylenebiscyclohexylene sebacamide) (polyamide PACP10), poly( 4,4'-Propylenebiscyclohexylene dodecamide) (polyamide PACP12), poly(4,4'-propylenebiscyclohexylene tetradecamide) (polyamide PACP14), poly(4,4'-Propylene biscyclohexylene hexadecamide) (polyamide PACP16), poly(4,4′-propylenebiscyclohexylene octadecamide) (polyamide PACP18), poly(4,4′-propylenebiscyclohexylene terephthalamide) (polyamide PACPT), poly(4,4′-propylenebiscyclohexylene isophthalamide) (polyamide PACPI), poly(4,4′-propylenebiscyclohexylene hexahydroterephthalamide) (polyamide PACPT(H)), poly( 4,4'-Propylenebiscyclohexylenenaphthalamide) (polyamide PACPN), polyisophorone succinamide (polyamide IPD4), polyisophorone lutamide (polyamide IPD5), polyisophorone adipamide (polyamide IPD6), polyisophorone sveramide (Polyamide IPD8), polyisophorone azeramide (polyamide IPD9), polyisophorone sebacamide (polyamide IPD10), polyisophorone dodecamide (polyamide IPD12), polyisophorone terephthalamide (polyamide IPDT), polyisophorone isophthalamide (polyamide) IPDI), polyisophorone hexahydroterephthalamide (polyamide IPDT(H)), polyisophorone naphthalamide (polyamide IPDN), polytetramethylene terephthalamide (polyamide 4T), polytetramethylene isophthalamide (polyamide 4I), poly Tetramethylene hexahydroterephthalamide (polyamide 4T(H)), polytetramethylene naphthalamide (polyamide 4N), polypentamethylene terephthalamide (polyamide 5T), polypentamethylene isophthalamide (polyamide 5I), polypentamethylene Hexahydroterephthalamide (polyamide 5T(H)), polypentamethylene naphthalamide (polyamide 5N), polyhexamethylene terephthalamide (polyamide 6T), polyhexamethylene isophthalamide (polyamide)
6I), polyhexamethylene hexahydroterephthalamide (polyamide 6T(H)), polyhexamethylene naphthalamide (polyamide 6N), poly(2-methylpentamethylene terephthalamide) (polyamide M5T), poly(2-methyl) Pentamethylene isophthalamide) (polyamide M5I), poly(2-methylpentamethylene hexahydroterephthalamide) (polyamide M5T(H)), poly(2-methylpentamethylenenaphthalamide (polyamide M5N), polynonamethylene tere Phthalamide (polyamide 9T), polynonamethylene isophthalamide (polyamide 9I), polynonamethylene hexahydroterephthalamide (polyamide 9T(H)), polynonamethylene naphthalamide (polyamide 9N), poly(2-methylocta) Methylene terephthalamide) (polyamide M8T), poly(2-methyloctamethylene isophthalamide) (polyamide M8I), poly(2-methyloctamethylene hexahydroterephthalamide) (polyamide M8T(H)), poly(2 -Methyl octamethylene naphthalamide) (polyamide M8N), polytrimethylhexamethylene terephthalamide (polyamide TMHT), polytrimethylhexamethylene isophthalamide (polyamide TMHI), polytrimethylhexamethylene hexahydroterephthalamide (polyamide TMHT(H )), polytrimethylhexamethylene naphthalamide (polyamide TMHN), polydecamethylene terephthalamide (polyamide 10T), polydecamethylene isophthalamide (polyamide 10I), polydecamethylene hexahydroterephthalamide (polyamide 10T(H)). ), polydecamethylene naphthalamide (polyamide 10N), polyundecamethylene terephthalamide (polyamide 11T), polyundecamethylene isophthalamide (polyamide 11I), polyundecamethylene hexahydroterephthalamide (polyamide 11T(H )), polyundecamethylene naphthalamide (polyamide 11N), polydodecamethylene terephthalamide (polyamide 12T), polyHomopolymers such as dodecamethylene isophthalamide (polyamide 12I), polydodecamethylene hexahydroterephthalamide (polyamide 12T(H)), polydodecamethylene naphthalamide (polyamide 12N), and/or the raw material unit amount of these polyamides Examples thereof include polyamide-based resins such as copolymers using several kinds of raw material monomers for the body and/or the polyamide (A1).
[0117]
　Further, polyvinylidene fluoride (PVDF), polyvinyl fluoride (PVF), polytetrafluoroethylene (PTFE), polychlorotrifluoroethylene (PCTFE), tetrafluoroethylene/perfluoro(alkyl vinyl ether) copolymer (PFA), Tetrafluoroethylene/hexafluoropropylene copolymer (FEP), tetrafluoroethylene/perfluoro(alkyl vinyl ether)/hexafluoropropylene copolymer, ethylene/tetrafluoroethylene copolymer (ETFE), ethylene/tetrafluoroethylene/ Hexafluoropropylene copolymer (EFEP), vinylidene fluoride/tetrafluoroethylene copolymer, vinylidene fluoride/hexafluoropropylene copolymer, vinylidene fluoride/perfluoro(alkyl vinyl ether) copolymer, tetrafluoroethylene/ Hexafluoropropylene/vinylidene fluoride copolymer (THV), vinylidene fluoride/perfluoro(alkyl vinyl ether)/tetrafluoroethylene copolymer, tetrafluoroethylene/hexafluoropropylene/vinylidene fluoride/perfluoro(alkyl vinyl ether) Copolymer, ethylene/chlorotrifluoroethylene copolymer (ECTFE), chlorotrifluoroethylene/tetrafluoroethylene copolymer, vinylidene fluoride/chlorotrifluoroethylene copolymer, chlorotrifluoroethylene/perfluoro(alkyl Vinyl ether) copolymer, chlorotrifluoroethylene/hexafluoropropylene copolymer, chlorotrifluoroethylene/tetrafluoroethylene/hexafluoropropylene copolymer, chlorotrifluoroethylene/tetrafluoroethylene/vinylidene fluoride copolymer, Chlorotrifluoroethylene/perfluoro(alkyl vinyl ether)/tetrafluoroethylene copolymer (CPT), chlorotrifluoroethylene/perfluoro(alkyl vinyl ether)/hexafluoropropylene copolymer, chlorotrifluoroethylene/tetraFluoroethylene/hexafluoropropylene/perfluoro(alkyl vinyl ether) copolymer, chlorotrifluoroethylene/tetrafluoroethylene/vinylidene fluoride/perfluoro(alkyl vinyl ether) copolymer, chlorotrifluoroethylene/tetrafluoroethylene/fluorine For fluorine-containing polymers such as vinylidene fluoride/hexafluoropropylene copolymer, chlorotrifluoroethylene/tetrafluoroethylene/vinylidene fluoride/perfluoro(alkyl vinyl ether)/hexafluoropropylene copolymer and/or amino groups And the above-mentioned fluorine-containing polymer having a reactive functional group.
[0118]
　Furthermore, polybutylene terephthalate (PBT), polyethylene terephthalate (PET), polyethylene isophthalate (PEI), poly(ethylene terephthalate/ethylene isophthalate) copolymer (PET/PEI), polytrimethylene terephthalate (PTT), polycyclohexane Polyester system such as dimethylene terephthalate (PCT), polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyarylate (PAR), liquid crystal polyester (LCP), polylactic acid (PLA), polyglycolic acid (PGA) Resin; Polyether resin such as polyacetal (POM) and polyphenylene ether (PPO); Polysulfone resin such as polysulfone (PSU), polyethersulfone (PESU) and polyphenylsulfone (PPSU); Polyphenylene sulfide (PPS), Polythioether resins such as polythioether sulfone (PTES); aliphatic polyketone, polyether ketone (PEK), polyether ether ketone (PEEK), polyether ketone ketone (PEKK), polyether ether ether ketone (PEEEK), Polyketone-based resins such as polyetheretherketoneketone (PEEKK), polyetherketoneketoneketone (PEKKK), and polyetherketoneetherketoneketone (PEKEKK); polyacrylonitrile (PAN), polymethacrylonitrile, acrylonitrile/styrene copolymer (AS), methacrylonitrile/styrene copolymer, acrylonitrile/butadiene/styrene copolymer (ABS), acrylonitrile/butadiene copolymer (NBR), and other polynitrile resins; polymethylmethacrylate (PMMA), polymethacryl Polymethacrylate resin such as ethyl acidate (PEMA); polyvinyl ester resin such as polyvinyl acetate (PVAc); polyvinylidene chloride (PVDC), polyvinyl chloride (PVC), vinyl chloride/vinylidene chloride copolymer, vinylidene chloride /Polyvinyl chloride resin such as methyl acrylate copolymer;Cellulose resins such as cellulose acetate and cellulose butyrate; polycarbonate resins such as polycarbonate (PC); polyimide resins such as thermoplastic polyimide (TPI), polyetherimide, polyesterimide, polyamideimide (PAI), polyesteramideimide; Thermoplastic polyurethane-based resin; saponified ethylene/vinyl acetate copolymer (EVOH), polyamide elastomer, polyurethane elastomer, polyester elastomer and the like.
[0119]
　It is also possible to laminate any substrate other than the thermoplastic resin, for example, paper, metallic material, unstretched, uniaxially or biaxially stretched plastic film or sheet, woven cloth, nonwoven cloth, metallic cotton, wood, etc. is there. Examples of the metal-based material include metals such as aluminum, iron, copper, nickel, gold, silver, titanium, molybdenum, magnesium, manganese, lead, tin, chromium, beryllium, tungsten, and cobalt, and/or their metal compounds, and these 2 Examples include alloy steels made of more than one kind, such as stainless steel, aluminum alloys, copper alloys such as brass and bronze, and alloys such as nickel alloys.
[0120]
　As a method for producing a laminated tube, a method of melt extrusion using an extruder corresponding to the number of layers or the number of materials and laminating at the same time inside or outside a die (coextrusion molding method), or once a single layer tube or A method (coating method) in which the laminated tube manufactured by the above method is manufactured in advance and the resin is integrated and laminated on the outside sequentially by using an adhesive if necessary, may be mentioned. The laminated tube of the present invention is preferably manufactured by a coextrusion method in which various materials are coextruded in a molten state, and both are heat-sealed (melt-bonded) to manufacture a tube having a laminated structure in one step.
[0121]
　Further, in the case where the obtained laminated tube has a complicated shape, or when the molded product is subjected to heat bending after molding, in order to remove the residual strain of the molded product, after forming the above laminated tube, It is also possible to obtain the target molded article by heat-treating for 0.01 hours or more and 10 hours or less at a temperature lower than the lowest melting point of the melting points of the resin forming the tube.
[0122]
　The laminated tube may have a corrugated region. The corrugated region is a region formed in a corrugated shape, a bellows shape, an accordion shape, a corrugated shape, or the like. The corrugated region is not limited to one having the entire length of the laminated tube, and may be one having a part in an appropriate region on the way. The corrugated region can be easily formed by first molding a straight tube and then molding it into a predetermined corrugated shape. By having such a corrugated region, it has a shock absorbing property and the mountability becomes easy. Further, for example, it is possible to add necessary parts such as a connector, or to form an L-shape or a U-shape by bending.
[0123]
　The whole or part of the outer periphery of the laminated tube molded in this manner has natural rubber (NR), butadiene rubber (BR), isoprene rubber (IR) in consideration of stone splash, abrasion with other parts, and flame resistance. ), butyl rubber (IIR), chloroprene rubber (CR), carboxylated butadiene rubber (XBR), carboxylated chloroprene rubber (XCR), epichlorohydrin rubber (ECO), acrylonitrile butadiene rubber (NBR), hydrogenated acrylonitrile butadiene rubber (HNBR) , Carboxylated acrylonitrile butadiene rubber (XNBR), mixture of NBR and polyvinyl chloride, acrylonitrile isoprene rubber (NIR), chlorinated polyethylene rubber (CM), chlorosulfonated polyethylene rubber (CSM), ethylene propylene rubber (EPR), ethylene Propylene diene rubber (EPDM), ethylene vinyl acetate rubber (EVM), rubber mixture of NBR and EPDM, acrylic rubber (ACM), ethylene acrylic rubber (AEM), acrylate butadiene rubber (ABR), styrene butadiene rubber (SBR), carboxylated Styrene butadiene rubber (XSBR), styrene isoprene rubber (SIR), styrene isoprene butadiene rubber (SIBR), urethane rubber, silicone rubber (MQ, VMQ), fluororubber (FKM, FFKM), fluorosilicone rubber (FVMQ), vinyl chloride A solid or sponge-like protective member (protector) made of a thermoplastic elastomer such as a olefin-based, olefin-based, ester-based, urethane-based, or amide-based resin can be provided. The protective member may be a sponge-like porous body by a known method. By using a porous body, it is possible to form a lightweight and highly heat-insulating protective portion. Also, the material cost can be reduced. Alternatively, glass fiber or the like may be added to improve its strength. The shape of the protective member is not particularly limited, but it is usually a tubular member or a block-shaped member having a recess for receiving the laminated tube. In the case of a tubular member, insert the laminated tube into the tubular member that was made in advance, or The tubular member can be coated and extruded on the tube to closely adhere the two. To bond the two, an adhesive is applied to the inner surface of the protective member or the concave surface as required, and the laminated tube is inserted or fitted into the adhesive, and the both are adhered to each other, whereby the laminated tube and the protective member are integrated. To form a damaged structure. It is also possible to reinforce with metal or the like.
[0124]
　The outer diameter of the laminated tube considers the flow rate of the circulating chemical liquid and/or gas (for example , engine cooling liquid), and the wall thickness does not increase the permeability of the chemical liquid, and can maintain the normal tube breaking pressure. The thickness is designed so that the tube can be easily assembled and the vibration resistance at the time of use can maintain a sufficient degree of flexibility, but the thickness is not limited. It is preferable that the outer diameter is 4 mm or more and 300 mm or less, the inner diameter is 3 mm or more and 250 mm or less, and the wall thickness is 0.5 mm or more and 25 mm or less.
[0125]
　The laminated tube of the present invention includes automobile parts, internal combustion engine applications, mechanical parts such as electric tool housings, industrial materials, industrial materials, electric/electronic parts, medical care, food, household/office supplies, building material-related parts, and furniture. It can be used for various purposes such as parts for use.
[0126]
　Further, the laminated tube of the present invention is excellent in the resistance to permeation of a chemical solution, and thus is suitably used as a chemical solution transfer tube. Examples of the chemical liquid include aromatic hydrocarbon solvents such as benzene, toluene, xylene, and alkylbenzenes; methanol, ethanol, propanol, butanol, pentanol, ethylene glycol, propylene glycol, diethylene glycol, phenol, cresol, polyethylene glycol, polypropylene glycol. , Alcohols such as polyalkylene glycol; phenol solvents; ether solvents such as dimethyl ether, dipropyl ether, methyl-t-butyl ether, ethyl-t-butyl ether, dioxane, tetrahydrofuran, polyol esters, polyvinyl ethers; HFC-23 (trifluoromethane), HFC-32 (difluoromethane), HFC-41 (fluoromethane), HFC-123 (2,2-dichloro-1,1,1-trifluoroethane), HFC-125 (1 , 1,1,2,2-pentafluoroethane), HFC-134 (1,1,2,2-tetrafluoroethane), HFC-134a (1,1,1,2-tetrafluoroethane), HFC- 143 (1,1,2-trifluoroethane), HFC-143a (1,1,1-trifluoroethane), HFC-152 (1,2-difluoroethane), HFC-152a (1,1-difluoroethane), HFC-161 (fluoroethane), HFC-227ea (1,1,1,2,3,3,3-heptafluoropropane), HFC-227ca (1,1,2,2,3,3,3-hepta) Fluoropropane), HFC-236fa (1,1,1,3,3,3-hexafluoropropane), HFC-236ea (1,1,1,2,3,3-hexafluoropropane), HFC-236cb( 1,1,1,2,2,3-hexafluoropropane), HFC-236ca (1,1,2,2,3,3-hexafluoropropane), HFC-245ca (1,1,2,2,2) 3-pentafluoropropane), HFC-245ea
Ro-3-methyl-2-butene), HFC-1447fyz (2,4,4,4-tetrafluoro-3-(trifluoromethyl)-1-butene), HFC-1447ezz (1,4,4,4) -Tetrafluoro-3-(trifluoromethyl)-1-butene), HFC-1447qzt (1,4,4,4-tetrafluoro-2-(trifluoromethyl)-2-butene), HFC-1447syt (2 , 4,4,4-Tetrafluoro-2-(trifluoromethyl)-2-butene), HFC-1456szt (3-(trifluoromethyl)-4,4,4-trifluoro-2-butene), HFC -1456szy (3,4,4,5,5,5 hexafluoro-2-pentene), HFC-1456mstz (1,1,1,4,4,4-hexafluoro-2-methyl-2-butene), HFC-1456fzce (3,3,4,5,5,5-hexafluoro-1-pentene), HFC-1456ftmf (4,4,4-trifluoro-2-(trifluoromethyl)-1-butene), FC-151-12c (1,1,2,3,3,4,4,5,5,6,6,6-dodeca-1-hexene, perfluoro-1-hexene), FC-151-12mcy (1 , 1,1,2,2,3,4,5,5,6,6,6-dodeca-3-hexene, perfluoro-3-hexene), FC-151-12mmtt (1,1,1,4, 4,4-hexafluoro-2,3-bis(trifluoromethyl)-2-butene), FC-151-12mmzz (1,1,1,2,3,4,5,5,5-nonafluoro-4 -(Trifluoromethyl)-2-pentene), HFC-152-11mmtz (1,1,1,4,4,5,5,5-octafluoro-2-(trifluoromethyl)-2-pentene), HFC-152-11mmyyz (1,1,1,3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene), HFC-152-11mmyyz (1,1,1, 3,4,5,5,5-octafluoro-4-(trifluoromethyl)-2-pentene), HFC-1549fz(PFBE) (3,3,4,4,5,5,6,6,6-nonafluoro-1-hexene, perfluorobutyl), HFC-1549fztmm(4,4,4-trifluoro- 3,3-bis(trifluoromethyl)-1-butene), HFC-1549mmtts (1,1,1,4,4,4-hexafluoro-3-methyl-2-(trifluoromethyl)-2-butene ), HFC-1549fycz (2,3,3,5,5,5-hexafluoro-4-(trifluoromethyl)-1-pentene), HFC-1549myts (1,1,1,2,4,4,4) 5,5,5-Nonafluoro-3-methyl-2-pentene), HFC-1549mzzzz (1,1,1,5,5,5-hexafluoro-4-(trifluoromethyl)-2-pentene), HFC -1558szy (3,4,4,5,5,6,6,6-octafluoro-2-hexene), HFC-1558fzccc (3,3,4,4,5,5,6,6-octafluoro- 2-hexene), HFC-1558mmtzc (1,1,1,4,4-pentafluoro-2-(trifluoromethyl)-2-pentene), HFC-1558ftmf (4,4,5,5,5-penta) Fluoro-2-(trifluoromethyl)-1-pentene), HFC-1567fts (3,3,4,4,5,5,5-heptafluoro-2-methyl-1-pentene), HFC-1567szz (4 , 4,5,5,6,6,6-heptafluoro-2-hexene), HFC-1567fzfc (4,4,5,5,6,6,6-heptafluoro-1-hexene), HFC-1567sfyy (1,1,1,2,2,3,4-heptafluoro-3-hexene), HFC-1567fzfy (4,5,5,5-tetrafluoro-4-(trifluoromethyl)-1-pentene) , HFC-1567myzzm (1,1,1,2,5,5,5-heptafluoro-4-methyl-2-pentene), HFC-1567mmtyf (1,1,1,3-tetrafluoro-2-(tri Fluoromethyl)-2-pentene),FC-161-14myy (1,1,1,2,3,4,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene), FC-161-14mcyy(1 , 1,1,2,2,3,4,5,5,6,6,7,7,7-tetradecafluoro-2-heptene), HFC-162-13mzy (1,1,1,3,3) 4,4,5,5,6,6,7,7,7-tridecafluoro-2-heptene), HFC162-13myz (1,1,1,2,4,4,5,5,6,6) , 7,7,7-Tridecafluoro-2-heptene), HFC-162-13mczy (1,1,1,2,2,4,5,5,6,6,7,7,7-trideca) Fluoro-3-heptene), HFC-162-13mcyz (1,1,1,2,2,3,5,6,6,7,7,7-tridecafluoro-3-heptene), CFC- 11 (fluorotrichloromethane), CFC-12 (dichlorodifluoromethane), CFC-114 (1,1,2,2-tetrafluoro-1,2-dichloroethane), CFC-114a (1,1,1,2- Tetrafluoro-2,2-dichloroethane), CFC-115 (1,1,1,2,2-pentafluoro-2-dichloroethane), HCFC-21 (dichlorofluoromethane), HCFC-22 (chlorodifluoromethane), HCFC-122 (1,1,2-trichloro-2,2-difluoroethane), HCFC-123 (1,1,1-trifluoro-2,2-dichloroethane), HCFC-124 (1,1,1,2) -Tetrafluoro-2-chloroethane), HCFC-124a (1,1,2,2-tetrafluoro-2-chloroethane), HCFC-132 (dichlorodifluoroethane), HCFC-133a (1,1,1-trifluoro-) 2-chloroethane), HCFC-141b (1,1-dichloro-1-fluoroethane), HCFC-142 (1,1-difluoro-2-chloroethane), HCFC-142b (1,1-difluoro-1-chloroethane) , HCFC-225ca (3,3-dichloro-1,1,1,2,2-Pentafluoropropane), HCFC-225cb (1,3-dichloro-1,1,2,2,3-pentafluoropropane), HCFC-240db (1,1,1,2,3-pentachloropropane), HCFC- 243db (1,1,1-trifluoro-2,3-dichloropropane), HCFC-243ab (1,1,1-trifluoro-2,2-dichloropropane), HCFC-244eb (1,1,1, 2-tetrafluoro-3-chloropropane), HCFC-244bb (1,1,1,2-tetrafluoro-2-chloropropane), HCFC-244db (1,1,1,3-tetrafluoro-2-chloropropane), HCFC-1111 (1,1,2-trichloro-2-fluoroethylene), HCFC-1113 (1,1,2-trifluoro-2-chloroethylene), HCFC-1223xd (3,3,3-trifluoro-) 1,2-dichloropropene), HCFC-1224xe (1,3,3,3-tetrafluoro-2-chloropropene), HCFC-1232xf (3,3-difluoro-1,3-dichloropropene), HCFC-1233xf (3,3,3-trifluoro-2-chloropropene), HCFC-1233zd (3,3,3-trifluoro-1-chloropropene), and haloolefins such as mixtures thereof; acetone, methyl ethyl ketone, diethyl Ketones, ketone solvents such as acetophenone; mineral oils, silicone oils, natural paraffins, naphthenes, synthetic paraffins, polyalphaolefins, gasoline, kerosene, diesel gasoline, rapeseed oil methyl ester, soybean oil methyl ester, Palm oil methyl ester, coconut oil methyl ester, gas liquefied oil (Gas To Liquid: GTL), coal liquefied oil (Coal To Liquid: CTL), biomass liquefied oil (Biomass To Liquid: BTL), alcohol-containing gasoline, ethyl ester -T-butyl ether blend oxygenated gasoline, amine-containing gasoline, sour gasoline, compressed natural gas (CNG), liquefied petroleum gasGas (LPG), liquefied hydrocarbon gas (LHG), liquefied natural gas (LNG), dimethyl ether (DME) for fuel, castor oil-based brake fluid, glycol ether brake fluid, borate ester brake fluid, brake fluid for extremely cold regions , Silicone oil-based brake fluid, mineral oil-based brake fluid, power steering oil, hydrogen sulfide-containing oil, window washer fluid, engine cooling fluid, urea solution, pharmaceutical agent, ink, paint and the like.
[0127]
　The laminated tube is suitable as a tube for conveying the chemical liquid, and specifically, a feed tube, a return tube, an evaporation tube, a fuel filler tube, an ORVR tube, a reserve tube, a fuel tube such as a vent tube, an oil tube, and a petroleum oil. Drilling tube, air pressure, hydraulic tube, clutch tube, brake tube, brake negative pressure tube, suspension tube, air tube, turbo air tube, air duct tube, blow-by tube, EGR valve control tube, window washer fluid tube, cooling fluid (LLC) cooler tube, reservoir tank tube, urea solution transfer tube, battery cooling and heating tube, fuel cell tube, air conditioner tube, heater tube, radiator tube, load heating tube, floor heating tube, infrastructure supply It is preferably used as a tube, a fire extinguisher and a tube for fire extinguishing equipment, a tube for medical cooling equipment, an ink, a paint spray tube, and other chemical solution tubes. Coolant (LLC) cooler tube, urea solution transfer tube, battery cooling heating More preferably, it is used as an air conditioner tube and an air conditioner tube.
Example
[0128]
　The present invention will be specifically described below with reference to Examples and Comparative Examples, but the present invention is not limited thereto.
　First, analysis and measurement methods of physical properties in Examples and Comparative Examples, and materials used in Examples and Comparative Examples will be shown.
[0129]
　1. The properties of polyamide were measured by the following methods.
　[Relative Viscosity] The relative viscosity
　was measured according to JIS K-6920 in 96% sulfuric acid under the conditions of a polymer concentration of 1% and a temperature of 25° C.
[0130]
　[Flexural Modulus] The
　flexural modulus was measured according to ISO 178.
[0131]
　[Terminal amino group concentration] A
　predetermined amount of polyamide sample was placed in an Erlenmeyer flask with a stopcock, 40 mL of a solvent phenol/methanol (volume ratio 9/1) adjusted in advance was added, and then dissolved by stirring with a magnetic stirrer. Using thymol blue as an indicator, titration was performed with 0.05 N hydrochloric acid to determine the terminal amino group concentration.
[0132]
　[Terminal Carboxyl Group Concentration] A
　predetermined amount of a polyamide sample is placed in a three-necked pear-shaped flask, 40 mL of benzyl alcohol is added, and then immersed in an oil bath set at 180° C. under a nitrogen stream. The solution was stirred and dissolved by a stirring motor attached to the upper portion, and titrated with a 0.05N sodium hydroxide solution using phenolphthalein as an indicator to determine the terminal carboxyl group concentration.
[0133]
　2. The properties of the polyolefin were measured by the following methods.
[0134]
　[Melting point] The
　melting point was measured according to ISO11357-3.
[0135]
　[MFR] According
　to ISO1133, MFR was measured under the conditions of 230° C. and 2,160 g.
[0136]
　[Density] The
　density was measured according to ISO 1183-3.
[0137]
　3. Each physical property of the laminated tube was measured by the following methods.
　[Low temperature impact resistance] An
　impact test was carried out at -40°C by the method described in SAE J 2260 7.5.
[0138]
　[High Temperature Breaking Strength] A
　breaking strength test was conducted at 115° C. by the method described in SAE J 2260 7.2.
[0139]
　[Bending Stiffness (Flexibility)]
　A tube cut to 280 mm was treated with a hot air circulation oven at 110° C. for 72 hours, and then, using the specified tester by the method described in SAE J 844 9.8, 23 The load was measured at 50° C. when the tip of the test piece moved 50 mm. When the measured load was 30 N or less, it was judged that the flexibility was excellent.
[0140]
　[Weight reduction amount (dimensional stability)] The
　tube cut to 0.3 m was treated with a hot air circulation oven at 100°C for 72 hours, and then the weight change was evaluated.
[0141]
　[Elution resistance of low molecular weight material (plasticizer)]
　One end of a tube cut to 0.5 m was tightly sealed, LLC of a mixture of 50% water and 50% ethylene glycol was put inside, and the remaining end was also tightly plugged. .. Then, the test tube was placed in an oven at 135° C. and treated for 96 hours. Then, the solution in the taken out tube was subjected to quantitative analysis of the plasticizer by gas chromatography, and the content of the plasticizer eluted in the LLC was measured. The content of the plasticizer eluted in the LLC was divided by the inner surface area of ​​the tube to calculate the amount of plasticizer eluted (g/m 2 ). When the elution amount was 2.0 g/m 2 or less, it was judged that the elution resistance was excellent.
[0142]
　[Sulfur atom detection presence/absence] The presence or absence of sulfur atom detection
　was confirmed by performing elemental analysis of the solution in the tube obtained in the above-mentioned "elution resistance of low molecular weight substance (plasticizer)".
[0143]
　4. Materials Used in Examples and Comparative Examples
　(1) Aliphatic Polyamide (A1)
　[Production of Polyamide 12 (A1-1)] In
　a pressure-resistant reaction vessel with an internal volume of 70 liters equipped with a stirrer, dodecane lactam 19.73 kg (100. 0 mol), 5-amino-1,3,3-trimethylcyclohexanemethylamine 45.0 g (0.264 mol), and 0.5 L of distilled water were charged, the inside of the polymerization tank was replaced with nitrogen, and then heated to 180°C. Then, the mixture was stirred at this temperature so that the inside of the reaction system became uniform. Then, the temperature in the polymerization tank was raised to 270° C., and the polymerization was carried out under stirring for 2 hours while adjusting the pressure in the tank to 3.5 MPa. Then, the pressure was released to normal pressure over about 2 hours, then the pressure was reduced to 53 kPa, and the polymerization was performed for 5 hours under reduced pressure. Then, nitrogen was introduced into the autoclave, and after returning to normal pressure, it was extracted as a strand from the lower nozzle of the reaction vessel and cut to obtain pellets. The pellets were dried under reduced pressure to obtain a polyamide 12 having a relative viscosity of 2.20, a terminal amino group concentration of 48 μeq/g, and a terminal carboxyl group concentration of 24 μeq/g (hereinafter, this polyamide 12 is referred to as (A1-1)). The ratio [CH 2 ]/[NHCO] of the number of methylene groups of polyamide 12 (A1-1) to the number of amide groups is 11.0, which satisfies 7.0 or more. The terminal amino group concentration [A] (μeq/g) and the terminal carboxyl group concentration [B] (μeq/g) of polyamide 12 (A1-1) satisfy [A]>[B]+5.
[0144]
　[Production of Polyamide 612 (A1-2)] In
　a pressure-resistant reaction vessel equipped with a stirrer and having an internal volume of 70 liters, 16.42 kg (50.0 mol) of equimolar salt of 1,6-hexanediamine and dodecanedioic acid, 1, After charging 16.3 g (0.14 mol) of 6-hexanediamine and 5.0 L of distilled water and replacing the inside of the polymerization tank with nitrogen, the temperature is raised to 220° C., and the reaction system becomes uniform at this temperature. So that it was stirred. Then, the temperature inside the polymerization tank was raised to 270° C., and while controlling the pressure inside the tank to 1.7 MPa, polymerization was carried out under stirring for 2 hours. Then, the pressure was released to normal pressure over about 2 hours, then the pressure was reduced to 53 kPa, and the polymerization was performed for 4 hours under reduced pressure. Then, nitrogen was introduced into the autoclave, and after returning to normal pressure, it was extracted as a strand from the lower nozzle of the reaction vessel and cut to obtain pellets. The pellets were dried under reduced pressure to obtain a polyamide 612 having a relative viscosity of 2.48, a terminal amino group concentration of 50 μeq/g, and a terminal carboxyl group concentration of 35 μeq/g (hereinafter, this polyamide 612 is referred to as (A1-2)). The ratio [CH 2 ]/[NHCO] of the number of methylene groups of polyamide 612 (A1-2) to the number of amide groups is 8.0, which satisfies 7.0 or more. The terminal amino group concentration [A] (μeq/g) and the terminal carboxyl group concentration [B] (μeq/g) of polyamide 612 (A1-2) satisfy [A]>[B]+5.
[0145]
　(2) Elastomer polymer (A2)
　Maleic anhydride-modified ethylene/1-butene copolymer (A2-1) (manufactured by Mitsui Chemicals, Inc., Tuffmer MH5010, acid anhydride group concentration: 50 μeq/g)
[0146]
　Maleic anhydride modified ethylene/1-butene copolymer (A2-2) (manufactured by Mitsui Chemicals, Inc., Tufmer MH5020, acid anhydride group concentration: 100 μeq/g)
[0147]
　(3) Plasticizer (A3)
　p-Hydroxybenzoic acid 2-hexyldecyl ester (A3-1) (Exepar HDPB manufactured by Kao Corporation)
[0148]
　p-Hydroxybenzoic acid hexadecyl ester (A3-2) (manufactured by Ueno Pharmaceutical Co., Ltd., CEPB)
[0149]
　N-Butylbenzenesulfonamide (A3-3) (Provilast 024, Provilast 024)
[0150]
　p-Hydroxybenzoic acid 2-ethylhexyl ester (A3-4) (manufactured by Ueno Pharmaceutical Co., Ltd., EHPB)

the scope of the claims
[Claim 1]
　A laminated tube of two or more layers including a layer (a) and a layer (b),
　wherein the layer (a) contains an aliphatic polyamide composition (A) and the
　layer (b) is a modified polyolefin (B). ), the
　aliphatic polyamide composition (A) includes a polyamide (A1) and an elastomer polymer (A2), and the
　polyamide (A1) is a fat having a ratio of the number of methylene groups to the number of amide groups of 7.0 or more. Which is a group polyamide and is contained in the aliphatic polyamide composition (A) in an amount of 70% by mass or more and 90% by mass or less, and the
　elastomer polymer (A2) is unsaturated having a carboxyl group and/or an acid anhydride group. The aliphatic polyamide composition (A) contains a structural unit derived from a compound and is contained in an amount of 5% by mass or more and 30% by mass or less,
　and the aliphatic polyamide composition (A) is a plasticizer ( A3), and the
　plasticizer (A3) does not contain a sulfur atom, and contains p- and/or o-hydroxybenzoic acid and a linear and/or branched alkyl group having 12 to 24 carbon atoms. The aliphatic polyamide composition contains an ester structure with an aliphatic alcohol, and the content of the plasticizer (A3) in the aliphatic polyamide composition (A) is 0% by mass or more and 15% by mass or less
　. (A) has a flexural modulus of 400 MPa or more and 1,000 MPa or less measured according to ISO 178, and the
　modified polyolefin (B) is a monomer based on an α-olefin having 2 to 10 carbon atoms. And has a melting point of 130° C. or higher measured according to ISO 11357-3,
　In the laminated tube, a laminated tube in which layers (a) and (b) are arranged in this order from the outside to the inside, and
　the thickness of the (a) layer accounts for 60% or more of the total thickness of the tube.
[Claim 2]
　The polyamide (A1) is polyundecane amide (polyamide 11), polydodecanamide (polyamide 12), polyhexamethylene decamide (polyamide 610), polyhexamethylene dodecamide (polyamide 612), polydecamethylene decamide (polyamide). 1010), polydecamethylene dodecamide (polyamide 1012), and at least one homopolymer selected from the group consisting of polydodecamethylene dodecamide (polyamide 1212), and/or several raw material monomers forming these. The laminated tube according to claim 1, which is the copolymer used.
[Claim 3]
　When the terminal amino group concentration per 1 g of the polyamide (A1) is [A] (μeq/g) and the terminal carboxyl group concentration is [B] (μeq/g), [A]>[B]+5. The laminated tube according to claim 1.
[Claim 4]
　The modified polyolefin (B) is at least one functional group selected from the group consisting of a carboxyl group or a derivative thereof, a hydroxyl group, an epoxy group, an amino group, an amide group, an imide group, a nitrile group, a thiol group, and an isocyanate group. The laminated tube according to any one of claims 1 to 3, which contains a unit derived from an unsaturated compound having a group.
[Claim 5]
　The modified polyolefin (B) is produced by a method in which a polyolefin before modification is melted, an unsaturated compound having the functional group is added, and graft copolymerization is performed. The described laminated tube.
[Claim 6]
　The modified polyolefin (B) has an MFR value of 1.0 g/10 min or more and 10.0 g/10 min or less measured according to ISO 1133 under the conditions of 230° C./2,160 g. The laminated tube according to any one of items.
[Claim 7]
The laminated tube according to any one of claims 1 to 6, 　wherein the modified polyolefin (B) has a density measured according to ISO 1183-3 of 0.85 g/cm 3 or more.
[Claim 8]
　The laminated tube according to any one of claims 1 to 7, wherein the modified polyolefin (B) is maleic anhydride modified polypropylene, and the content of polypropylene is 50% by mass or more.
[Claim 9]
　The layer further includes a layer (c), the layer (c) contains a
　polyolefin (C), and the
　polyolefin (C) is a unit derived from an α-olefin-based monomer having 2 to 10 carbon atoms. Has a melting point of 120° C. or higher measured according to ISO 11357-3, a tensile yield stress of 20 MPa or higher measured according to ISO 527, and a 23° C. measured according to ISO 179/1eA. The laminated tube according to any one of claims 1 to 8, which has a Charpy impact strength (notched) of 40 kJ/m 2 or more.
[Claim 10]
　The laminated tube according to claim 9, wherein the (c) layer is disposed inside the (b) layer.
[Claim 11]
　The laminated tube according to any one of claims 1 to 10, which is manufactured by a coextrusion molding method.
[Claim 12]
　The laminated tube according to any one of claims 1 to 11, which is one of a cooling liquid (LLC) cooler tube, a urea solution transfer tube, a battery cooling and heating tube, and an air conditioner tube.