TW201236867A - Laminate - Google Patents

Abstract

Provided is a laminate in which a layer composed of a fluororesin containing an adhesive functional group and a layer composed of a modified polyolefin resin can be adhered to each other directly and strongly even when a molding method such as a multilayer blow molding method or a multicolor injection molding method is employed, and which has excellent initial adhesion properties, excellent uniformity of initial adhesion properties and excellent retained adhesion properties. The laminate comprises a layer (B-1) composed of a modified polyolefin resin and a layer (C) formed on the layer (B-1) and composed of a fluororesin containing an adhesive functional group, and is characterized in that the modified polyolefin resin which constitutes the layer (B-1) is a modified polyolefin having an imino group or a carbodiimide group and the fluororesin containing an adhesive functional group which constitutes the layer (C) has an adhesive functional group having reactivity with the functional group contained in the modified polyolefin resin that constitutes the layer (B-1) at the terminal of the main chain thereof and/or the terminal of a side chain thereof.

Description

201236867 VI. Description of the Invention: [Technical Field to Which the Invention Is Ascribed] The present invention relates to a laminate. [Prior Art] Conventionally, fluoropolymers have been used in various applications because of their excellent heat resistance, chemical resistance, weather resistance, surface properties (such as low friction properties), and electrical insulation properties. On the other hand, fluoropolymers generally have insufficient mechanical strength or dimensional stability and are expensive. Therefore, in order to maximize the advantages of the active fluoropolymer and to minimize the disadvantages, the adhesion of the sealed fluoropolymer to other organic materials, lamination, adhesion to an inorganic material, lamination, and the like are discussed. For example, Patent Document 1 proposes a laminate of a functional group-containing fluoropolymer and a non-fluorine-based thermoplastic resin such as a polyimide resin. In Patent Document 2, a hollow molded body is described. It has a layer formed of a polyolefin resin (A) a layer (B) formed of a modified polyolefin resin, and a layer (C) formed of a fluororesin, and the layer (C) formed of the fluororesin is the innermost layer a layer of at least either side of the layer or outermost layer. [Prior Art Document] [Patent Document 1] International Publication No. 9 8/5 5 5 5 7 [Patent Document 2] International Publication No. 2008-04 1 643 No. 201236867 [Summary of the Invention] [Problems to be Solved by the Invention] However, in the case of the multi-layer blow molding which is generally used for producing a large groove shape, the hollow molded body described in Patent Document 2 has a short period of time in which the two types of resin constituting the two layers are in contact with each other in a molten state. In the case of color injection molding, since the temperature of the resin which is first ejected is lowered, the adhesion between the layer (B) and the layer (C) is insufficient, and there is still room for improvement. It is an object of the present invention to provide a layer formed of a fluororesin containing an adhesive functional group and a layer formed of a modified polyolefin resin, even when a molding method such as multi-layer blow molding or multi-color injection molding is used. It is a laminate which is strongly adhered and has excellent initial adhesion and initial adhesion, and is excellent in adhesion after fuel impregnation (maintaining adhesion). [Means for Solving the Problem] The inventors of the present invention have found that the modified polyolefin having a specific functional group and the fluororesin having an adhesive functional group can be strongly adhered, and thus the present invention has been completed. That is, the present invention is a laminate (sometimes referred to as a first laminate in the present specification) characterized by having a layer (B-1) formed of a modified polyolefin resin and the above layer (B) -1) a layer (C) formed of a fluororesin containing an adhesive functional group formed thereon, and a modified polyolefin resin constituting the layer (B-1) having an imine group or a carbodiimide group The polyolefin having the adhesive functional group constituting the layer (C) has a functional group for the modified polyolefin resin of the above-mentioned constituent layer (B-1) at the end of the main chain and/or at the side of the side chain. _ 201236867 The base exhibits a reactive adhesive functional group. The modified polyolefin having an imine group is preferably in the presence of a radical generating agent to polymerize the polyolefin with a polyimine compound containing a plurality of imine groups. An imine modified polyolefin obtained by treatment of a branch, a modified polyolefin having a carbodiimide group, which has a polyolefin which can react with a carbodiimide group in the presence of an unmodified polyolefin A carbodiimide modified polyolefin obtained by reacting a compound of a carbodiimide group. Preferably, the layer (A) having a polyolefin resin formed on the layer (B-1) is also a laminate (in the present specification, sometimes referred to as a second laminate), It is characterized by having a layer (A) formed of a polyolefin resin, a layer (B-2) formed of a modified polyolefin resin, and a layer (C) formed of a fluororesin containing an adhesive functional group, and the above-mentioned adhesiveness The layer (C) formed of the functional group fluororesin is a layer of at least one of the innermost layer or the outermost layer, and the fluororesin of the layer (C) containing the adhesive functional group is at the end of the main chain and/or The side chain end has an adhesive functional group which exhibits reactivity with respect to a functional group of the modified polyolefin resin of the above-mentioned constituent layer (B-2), and the above-mentioned adhesive functional group is fluororesin which constitutes an adhesive functional group. The total polymerization unit is 1 0 0 mol%, which is 〇· 2 ~ 1 0 mol%. The above-mentioned adhesive functional group is preferably 100 mol%, preferably 0.2 to 5 mol%, based on the total polymerization unit of the fluororesin constituting the adhesive functional group. The above-mentioned adhesive functional group is preferably 100 mol%, preferably 0.2 to 2 mol%, based on the total polymerization unit of the fluororesin constituting the adhesive functional group. The above adhesive functional group is preferably an amine group, a decylamino group, an amine carbenyl group 201236867, a hydroxyl group, a carboxyl group, a carboxylic acid halide group, an ester group, an acid anhydride group, a carbonate group, an epoxy group, a nitrile group and an isocyanate. The melting point of at least one of the above-mentioned fluororesins containing the adhesive functional group is preferably 120 to 240 〇 C °. The melting point of the fluororesin containing the adhesive functional group is preferably the adhesion of the fluororesin containing the adhesive functional group. The decomposition temperature of the functional group is below. The functionalized polyolefin of the modified polyolefin resin constituting the above layer (B-2) preferably has an amine group, a mercaptoamine group, an amine mercapto group, a hydroxyl group, a carboxyl group, a carboxylic acid halide group, an ester group, an acid anhydride group, At least one selected from the group consisting of a carbonate group, an epoxy group, a nitrile group, and an isocyanate group. The laminate of the present invention is preferably a container for a liquid medicine. The laminate of the present invention is preferably a container for urea water. The laminate of the present invention is preferably a tank for fuel. The laminate of the present invention is preferably a beverage or food tank. The laminate of the present invention is preferably a pipe or hose for embedding underground. The laminate of the present invention is preferably a filler neck hose, a fuel hose, or a fuel line. The invention is described in detail below. The first laminate of the present invention is formed of a layer (B-1) formed of a modified polyolefin resin, and a fluororesin formed of an adhesive functional group formed on the layer (B-1). Layer (C). The modified polyolefin resin constituting the layer (B-1) is an imine group having an imine group or carbon II 201236867 having an imine group, preferably in the presence of a radical generating agent, to make the polyolefin and a plurality of imines The imine-modified polyolefin obtained by grafting the polyimine compound. The above-mentioned imine-modified polyolefin is selected by graft-treating a polyolefin with a polyimine compound containing a plurality of imine groups in the presence of a radical generating agent. The polyolefin is preferably polyethylene. The polyimine compound is preferably, for example, a compound represented by the following formula: R1 R2 R3 [wherein R1, R2 and R3 may be the same or different, and represent a non-reactive atom or an organic group, R1 and R2. They may also be bonded to each other to form a ring, and η represents an integer of 20 to 2000]. R1, R2 and R3 in the formula are the same or different and are preferably a hydrogen atom, an alkyl group, an alkenyl group, an alkynyl group, a cycloalkyl group, an aryl group, a heterocyclic group or an alkoxy group. In this case, the alkyl group is preferably an alkyl group having a carbon number of 1 to 10, preferably a carbon number of 1 to 10, such as a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group, an isopropyl group or an isobutyl group. The alkyl group of 8 is more preferably an alkyl group having 1 to 5 carbon atoms, more preferably an alkyl group having 1 to 3 carbon atoms. The alkenyl group is preferably an alkenyl group having 2 to 10 carbon atoms, more preferably an alkenyl group having 2 to 8 carbon atoms, more preferably an alkenyl group having 2 to 5 carbon atoms, and most preferably an alkene having 2 to 4 carbon atoms. -9- 201236867 The alkynyl group is preferably an alkynyl group having a carbon number of 2 to 18, such as an ethynyl group, a 1-propynyl group or a fluorenyl-heptynyl group, more preferably an alkynyl group having a carbon number of 2 to 10, more preferably The alkynyl group having 2 to 6 carbon atoms is preferably an alkynyl group having 2 to 4 carbon atoms. The cycloalkyl group is preferably a cycloalkyl group having a carbon number of 3 to 10, such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group or a cyclooctyl group, more preferably a cycloalkyl group having a carbon number of 3 to 6 Good for the carbon number 5 ~ 6 ring yard base. The aryl group is preferably an aryl group having 6 to 10 carbon atoms such as a phenyl group, a tolyl group or a naphthyl group. The above heterocyclic group is, for example, a five-membered ring such as a furan ring, an oxazole ring, an isoindole ring or a tetrahydrofuran ring, a six-membered ring such as a pyran ring, a benzofuran ring, an isobenzofuran ring or a dibenzofuran ring. a heterocyclic ring containing an oxygen atom as a hetero atom represented by a condensed ring such as a xanthone ring, a xanthene ring, a color full ring, a heterochromatic ring, or a dilute ring, or, for example, a thiophene ring, a thiazole ring, or an isothiazide ring. a thiadiazole ring, a benzothiazole ring or the like, which is a heterocyclic ring containing a sulfur atom as a hetero atom, and is exemplified by five members such as a pyrrole ring, a pyrazole ring, an imidazole ring, a triterpene ring, and a pyrrolidine ring. Ring, pyridine ring, acridine ring, pyrimidine ring, piperazine ring, piperazine ring, morpholine ring and other six-membered ring, anthracene ring, pseudo-fluorene ring, isoindole ring, indazole ring, carbazole Ring, isoindoline ring, quinoline ring, isoquine ring, quinoline quinoline ring, salin ring, quinazoin, anthraquinone ring, anthracene ring, indazole ring, acridine ring, naphthalene The quinoline ring, the phenanthrene ring, the phenanthroline ring, the naphthalene steep ring, the benzoporphyrin ring, the phthalocyanine ring, the phthalocyanine ring, the phthalocyanine and the like are represented by a shrink ring. Examples of the heterocyclic nitrogen atom and other hetero atoms. The alkoxy group is exemplified by a methoxy group having a carbon number of from 1 to 10, preferably from 1 to 6, such as a methoxy group, an ethoxy group, a propoxy group or an isopropoxy group. -10- 201236867 As a preferred specific example of the polyimine compound, for example, a polyethylenimine is exemplified. The molecular weight of the polyimine compound is preferably 1,000 or more, but from the viewpoint of reactivity with an olefin after activation treatment, etc., a higher molecular weight is preferred. Specifically, the preferred molecular weight is from 1,000 to 200,000, more preferably from 3,000 to 200,000, and most preferably from 5,000 to 200,000. The radical generating agent used in the grafting treatment is exemplified by an organic peroxide or an organic peroxyester. For example, the use of benzammonium peroxide, dichlorobenzhydryl peroxide, dicumyl peroxide, ditributyl peroxide, 2.5-dimethyl-2,5-di (over Oxide benzoate) hexyne-3, 1,4-bis(t-butylperoxyisopropyl)benzene, lauryl peroxide, tert-butyl peroxyacetate, 2,5 -Dimethyl-2,5-di(t-butylperoxy)hexyne-3, 2.5-dimethyl-2,5-di(t-butylperoxy)hexane, third Peroxybenzoic acid ester, tert-butylperoxyphenyl acetate, t-butyl peroxyisobutyrate, t-butyl peroxydioctanoate, tert-butylperoxy Valerate, cumylperoxypivalate and tert-butylperoxydiethylacetate, and azo compounds such as azobisisobutyronitrile, dimethylazoisobutyronitrile. Preferred among these are dicumyl peroxide, ditributyl peroxide, 2,5-dimethyl-2,5.di(t-butylperoxide)hexyne-3,2 a dialkyl peroxide such as 5-dimethyl-2.5-bis(t-butylperoxy)hexane or i,4-bis(t-butylperoxyisopropyl)benzene. Among them, the radical generating agent is preferably an organic peroxide. As for the organic peroxide, it is preferred that the decomposition temperature of the half life is above the loot. Further, the organic peroxide is specifically preferably dicumyl peroxide, benzamidine 201236867-based peroxide, di-tert-butyl peroxide, 2,5-dimethyl-di (third Butylperoxy)hexyne, 2,5-dimethyl-2,5-(t-butylperoxy)hexyne-3, lauryl peroxide, and tert-butylperoxy At least one selected from the group consisting of benzoic acid esters and the like. The use ratio of the radical generator is usually 0.001 to 1 part by weight based on 100 parts by weight of the polyolefin. The above-mentioned imine-modified olefin can be produced by uniformly mixing a polyolefin, a polyimide compound, and a radical generator. Specifically, it is exemplified by a melt kneading method using an extruder or a Banbury kneading machine 'kneader, a solution method dissolved in a suitable solvent, a slurry method suspended in a suitable solvent, or a so-called vapor phase grafting method. The above treatment temperature is appropriately selected in consideration of deterioration of polyolefin, decomposition of a polyimide compound, decomposition temperature of a radical generator used, and the like. For example, in the case of the above melt-kneading method, it is usually carried out at a temperature of 60 to 350 °C. The above treatment temperature is preferably from 190 to 3 50 ° C, more preferably from 200 to 30 (TC. The modified polyolefin having carbodiimide is preferably in the presence of unmodified polyolefin to have carbon and carbon A carbodiimide-modified polyolefin obtained by reacting a polyolefin of a diimine-imine group with a compound containing a carbodiimide group. The method of the reaction is exemplified by melt-kneading at a temperature of 230 ° C or higher. The polyolefin having a group reactive with a carbodiimide group can be obtained by introducing a compound having a group reactive with a carbodiimide group into a polyolefin, and the polyolefin is exemplified as ethylene, propylene, and 1 a homopolymer of butene, 4-methyl-1-penta 201236867 olefin, 3·methyl-1-butene, 1-hexene, 1-octene, tetracyclododecene, norbornene or Copolymers. Compounds having a group reactive with a carbodiimide group are exemplified by acrylic acid, methacrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, and isoforms. An unsaturated carboxylic acid such as crotonic acid, norbornene dicarboxylic acid or bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic acid, or the anhydride or And other derivatives (such as 'halogen halide, decylamine, quinone imine, ester, etc.). Among these, 'maleic anhydride, (meth)acrylic acid, itaconic anhydride, citraconic anhydride, tetrahydrobenzene Formic anhydride, bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic anhydride, hydroxyethyl (meth)acrylate, glycidyl methacrylate, aminopropyl methacrylate. The method of introducing a compound having a group reactive with a carbodiimide group into a polyolefin may be carried out by a conventional method, and is exemplified by, for example, graft copolymerizing a compound having a group reactive with a carbodiimide group to a polyolefin. The method in the main chain is a method of radically copolymerizing a polyolefin with a compound having a group reactive with a carbodiimide group, etc. The polyolefin having a group reactive with a carbodiimide group is preferably a maleic anhydride graft copolymer of a crystalline polyolefin such as polyethylene, polypropylene, polybutene-1, poly-4-methylpentene-1 or the like α-olefin copolymer, preferably polycondensed a maleic anhydride graft copolymer of ethylene. In particular, a maleic acid of polyethylene having a density of 0 to 915 g/cm 3 or more is preferred. The graft copolymer. The compound containing a carbodiimide group is a polycarbodiimide having a repeating unit represented by the following formula: £ -13 - 201236867 -N = C=N-R1- (wherein R1 represents A divalent organic polycarbocarbene having a carbon number of 2 to 4 Å can be made into an aliphatic diisocyanate 'aromatic diisocyanate vinegar, fat in the absence of a solvent or in an inert solvent in the presence of a condensation catalyst. An organic monoisocyanate such as a cyclohexanic acid vinegar is produced by a decarbonation condensation reaction. For example, 'hexamethylene diisocyanate, 4,4-diphenylylene monoisocyanate' 1,4-phenylene group can be used. Isocyanic acid vinegar, 2,4_tolyl diisocyanate, tolyl diisocyanate, cyclohexyl-diisocyanate, dicyclohexylmethyl-4,4'diisocyanate, isophorone Diisocyanate such as diisocyanate. Unmodified polyalkylene hydrocarbons are exemplified by, for example, low density polyethylene, high density polyethylene, linear low density polyethylene, polypropylene, ethylene-propylene copolymer, ethylene-alpha olefin copolymer, ethylene-propylene copolymerization. , ethylene-butene copolymer, ethylene-hexene copolymer, ethylene-octene copolymer, polybutene oxime, poly-4-methyl-1-pentene, poly-3-methyl-1-butene A cyclic polyolefin such as an olefin or an ethylene-tetracyclododecene copolymer. The first laminate of the present invention preferably has a layer (Α) formed of a polyolefin resin formed on the layer (Β-1). The first laminate of the present invention has the advantage of improving mechanical strength when it has a layer. The second laminate of the present invention has a layer formed of a polyolefin resin, a layer formed of a modified polyolefin resin (Β_2), and a layer formed of a fluororesin containing an adhesive functional group ( C). The second laminate of the present invention has a layer (A) formed of a polyolefin resin-formed layer-14-201236867 and a layer (c) formed of a fluororesin containing an adhesive functional group, as compared with the past A widely used plastic or elastomer is excellent in chemical resistance, flame resistance, and low fuel permeability. For example, it can exhibit chemical resistance, fuel resistance, and low fuel for alcohols such as ethanol or methanol or urea water. Transmissive. The second laminate of the present invention further has a layer (B-2) formed of a modified polyolefin resin, and the fluororesin containing the adhesive functional group constituting the layer (C) is at the end of the main chain. The end of the side chain has an adhesive functional group which exhibits reactivity with a functional group which is a modified polyolefin resin constituting the layer (B-2). The above-mentioned adhesive functional group is 0.2 to 10 mol% based on 100 mol% of the total polymerization unit of the fluororesin constituting the adhesive functional group. Therefore, the adhesion between the layer (A) formed of the polyolefin resin and the layer (C) formed of the fluororesin containing the adhesive functional group can be improved, and the laminate having excellent impact resistance and mechanical strength can be obtained. Things. The fluororesin containing the adhesive functional group constituting the layer (C) has a modified polyolefin resin constituting the layer (B-1) and the layer (B-2) at the end of the main chain and/or at the side of the side chain. The functional group shows a reactive adhesive functional group. That is, the fluororesin having an adhesive functional group may be a polymer having an adhesive functional group at either a main chain end or a side chain end, or may be a main chain end and a side chain end. A polymer composed of an adhesive functional group. When the fluororesin having an adhesive functional group has an adhesive functional group at the terminal of the main chain, it may be present at both ends of the main chain or may be present at only one end. The adhesive functional group can also be introduced using a polymerization initiator. -15- 201236867 The fluororesin containing an adhesive functional group is a polymer having an adhesive functional group only at the end of the main chain, and is based on the reason that the mechanical properties and chemical resistance are not significantly lowered, or the productivity and cost are It is advantageous, but the number of adhesive functional groups is affected by the molecular weight, and there is a disadvantage that the maximum content of the content has an upper limit. When the fluororesin having an adhesive functional group has an adhesive functional group at the side of the side chain, it is preferable to increase the amount of the adhesive functional group to some extent to improve the adhesion. The method of introducing the above-mentioned adhesive functional group at the end of the side chain may be carried out by copolymerizing a monomer having an adhesive functional group as described above, or may be introduced by a graft reaction after polymerization. When an adhesive functional group is introduced by a graft reaction, a radical such as an organic peroxide which reacts with a substance having an unsaturated bond and an adhesive functional group in the molecule can be reacted with respect to a resin which is completely free of a functional group. Further, introduction or "copolymerization of a monomer having a relatively stable functional group, reaction of a functional group after polymerization to form a functional group having high reactivity, and introduction of an adhesive functional group therein. In the first layer of the present invention, the fluororesin containing the adhesive functional group has an adhesive functional group '100 mol% relative to the total polymerization unit of the fluororesin constituting the adhesive functional group, preferably 005~1() Moer% 'better 0.05~5 mol%' and better for 02~2 Moer 0/〇. In the second laminate of the present invention, the adhesive functional group of the fluororesin containing the adhesive functional group has a molar % of the total polymerizable monomer relative to the fluororesin constituting the adhesive functional group. 〇 2~1〇% of the ear. By making the adhesive functional group of 201236867 in the above range, the adhesion of the layer (B-2) and the layer (C) is extremely excellent, and accordingly, the initial high adhesion strength of the bonding surface as a whole without unevenness can be maintained. High adhesion strength after long-term use. With this, the laminate is excellent in impact resistance and mechanical strength as a whole. In the second laminate of the present invention, the adhesive functional group is appropriately selected depending on the type, shape, adhesion purpose, use, and the required adhesive force of the laminated material, the type of the fluororesin and the adhesion method. However, it is preferably from 0.2 to 5 mol%, more preferably from 0.2 to 2 mol%, based on 1% by mole of the total polymerization unit of the fluororesin constituting the adhesive functional group. The ratio of the above adhesive functional groups can be determined by the method of N M R or IR. The above-mentioned adhesive functional group is exemplified by a functional group having an amino group, a hydroxyl group, an epoxy group, a nitrile group or a carbonyl group. The above carbonyl group is a divalent group of carbon composed of a carbon-oxygen double bond, and is represented by -c(= 〇)-. The above functional group having a carbonyl group is exemplified by, for example, a carbonate group, a carboxylic acid halide group (halocarbenyl group), a decyl group, a carboxyl group, an ester group [-C(=0)0-], an acid anhydride group [-c ( = 0)0-c( = 0)_], isocyanate, guanamine, fluorenylene [-C(=0)-NH-C(= 0)_], urethane group [ -NH-C(=0)0-], aminomethyl hydrazino [NH2-C(= 0)_], amine methyl methoxy [NH2-C(= 〇) 〇-], urea-based [NH2-C ( = 〇)-NH-], oxalylamine [nh2-c(=o)_c(<0)-] and other chemical structures. a hydrogen atom bonded to a nitrogen atom such as a guanamine group, a guanidino group, a urethane group, an amine carbaryl group, an amine mercapto group, a ureido group or a sulfhydryl group, for example, Substituted by a hydrocarbon group such as an alkyl group. -17- 201236867 The above-mentioned adhesive functional group is preferably an amine group, a decylamine, an amine carbenyl group, a hydroxyl group, a carboxyl group, a carboxylic acid halide group, an ester group, an acid anhydride, a carbonate group, an epoxy group, At least one selected from the group consisting of a nitrile group and an isocyanate group. The above-mentioned adhesive functional group is more preferably at least one selected from the group consisting of an epoxy group, a group, and a carboxyl group, and more preferably a carboxyl group. In the present invention, the fluorine-containing functional group constituting the above layer (C) The fat is a polymer or copolymer having at least one repeating unit derived from a fluorine-containing ethylenic monomer. The fluororesin may be one obtained by polymerizing only a fluorine-containing ethylenic monomer, and may be a mixture of a fluorine-containing ethylenic monomer and an ethylenic monomer having no fluorine atom. In the present invention, the fluororesin layer may be one containing the above-mentioned fluororesin or two or more. The fluororesin containing an adhesive functional group preferably has tetrafluoroethylene [TFE], vinylidene fluoride [VdF], chlorotrifluoroethylene [CTFE], fluorinated ethylene [VF], hexafluoropropylene [HFP], Hexafluoroisobutane [HFIB], CHfCX^CFJnX, where X1 is Η or F, X2 is H, F is 11 and 11 is an integer from 1 to 10), and CFfCF-ORf1 (wherein Rf1) a perfluoroalkyl group having a carbon number of 1 to 8 and a perfluoro(alkyl vinyl group) [PAVE], and a CF2 = CF-OCH2-Rf2 (wherein, Rf2 is a perfluoroalkyl group having a carbon number of 1) a group consisting of an alkyl perfluorovinyl ether derivative, trifluoroethylene, trifluoropropene, tetrafluoropropene, pentafluoropropene, trifluorobutene, tetrafluoroisoene, fluorinated vinyl ether containing iodine At least one monomer unit mainly comprising a monomer is selected. The fluororesin may also have an ethylene [Et], a propyl group, a hydroxy eucalyptus, an olefin, an alkylene, a C1 7 ether, a pentene fluorocarbon, a long chain olefin, and an alkyl ethene. The polymerization unit in which at least one monomer selected from the group consisting of ethers is a fluorine-free monomer.

The fluororesin is more preferably a copolymer containing a polymerization unit mainly composed of at least one monomer selected from the group consisting of TFE, HFP 'PAVE, CTFE and VF. The fluororesin is also preferably a copolymer having a polymerization unit mainly composed of Et as a monomer containing no fluorine. The above PAVE is listed as perfluoro(methyl vinyl ether) [PMVE], perfluoro(ethyl vinyl acid) [PEVE], perfluoro(propyl vinyl ether) [PPVE], perfluoro(butyl vinyl) Ether, etc. Among them, more preferably PMVE, PEVE or PPVE. The above alkyl perfluorovinyl ether derivative is preferably a fluoroalkyl group having a carbon number of 1 to 3, and more preferably CF2 = CF-OCH2- CF2CF3. In the present specification, the above "polymerization unit" means a part of the molecular structure of the fluororesin and is based on a part of the corresponding monomer. The main chain of the above-mentioned fluororesin containing an adhesive functional group is preferably copolymerized by TFE/HFP. [FEP], TFE/PAVE copolymer [PFA], Et/TFE copolymer, Et/TFE/HFP copolymer, polychlorotrifluoroethylene [pcTFE], CTFE/TFE copolymer, Et/CTFE copolymer, TFE At least one selected from the group consisting of: VdF copolymer, ^VdF/HFP/TFE copolymer, VdF/HFP copolymer, and polyfluorinated ethylene [PVF]. The above copolymer may also have a copolymerizable composition. The other polymerization unit in which the monomer is copolymerized is preferably, for example, a polymerization unit having a monomer derived from an adhesive functional group. In the above description, as described above, "TFE/HFP copolymer-19-201236867" means copolymerization of a polymerization unit (TFE unit) mainly composed of TFE and a polymerization unit (HFP unit) mainly composed of HFP. The same is true for the other copolymers. The fluororesin having an adhesive functional group is preferably one having a polymerization unit derived from the monomer [α] containing an adhesive functional group. The monomer of the monomer [α] can easily adjust the content of the adhesive functional group. The above monomer [α] is a monomer having the above-mentioned adhesive functional group, and as long as it is compatible with the composition. The other monomer copolymer of the functional group fluororesin is not particularly limited. The above monomer [α] is exemplified by the following monomers. The monomer having an amine group is exemplified by, for example, allylamine, methacrylic acid. 2-aminomethyl ester, methylaminoethyl methacrylate, tert-butylaminoethyl methacrylate, aminostyrene, etc. Among them, allylamine and aminobenzene are preferred. At least one monomer selected from the group consisting of ethylene. The monomer of the amine group is exemplified by, for example, hydrazine, hydrazine-dimethyl decylamine, hydrazine, tert-butyl acrylamide, hydrazine-(butoxymethyl) acrylamide, decyl-ethenylamine, Ν-vinyl formamide, etc. Among them, at least one monomer selected from the group consisting of ruthenium, osmium-dimethyl decylamine, and fluorene-vinyl acetamide is preferred. The monomer is preferably at least one monomer selected from the group consisting of acrylamide and allyl urea. The monomer having a hydroxyl group is exemplified by allyl alcohol, 4-penten-1-ol, 4- Hydroxybutyl vinyl ether, hydrazine-hydroxymethyl acrylamide, hydrazine-hydroxymethyl methacryl-20 - 201236867 decylamine, and the like. Among them, at least one monomer selected from the group consisting of allyl alcohol and 4-penten-1-ol is preferred. Further, the monomer having a hydroxyl group is preferably one obtained by copolymerizing vinyl acetate and then converting it into a hydroxyl group by a saponification reaction. The monomer having a carboxyl group is exemplified by 3-butenoic acid, 4-pentenoic acid '5-hexenoic acid, acrylic acid, methacrylic acid, monomethyl maleate, crotonic acid and the like having one carboxyl group'. Maleic acid, fumaric acid, itaconic acid, citraconic acid and the like have two sulfhydryl groups. Among them, at least one monomer selected from the group consisting of 3-butyric acid, 4-pentenoic acid, 5-hexenoic acid, acrylic acid, methacrylic acid, maleic acid, and crotonic acid is preferred. The monomer having a carboxyl group is more preferably an unsaturated carboxylic acid represented by the following formula (1): CH2 = CH-(CH2)n-COOH (1) (wherein η is an integer of from 1 to 15). Wherein, η in the formula (1) is preferably an integer of from 2 to 10, more preferably from pentenoic acid, undecylenic acid, crotonic acid, hexenoic acid, decenoic acid, heptenoic acid, octene The at least one unsaturated carboxylic acid selected from the group consisting of acid and decenoic acid is more preferably at least one unsaturated carboxylic acid selected from the group consisting of pentenoic acid and undecylenic acid. The monomer having an acid anhydride group is exemplified by maleic anhydride, itaconic anhydride, citraconic anhydride, bicyclo[2,2,1]hept-2-ene-5,6-dicarboxylic anhydride, and the like. Among them, at least one monomer selected from the group consisting of maleic anhydride, itaconic anhydride, and citraconic anhydride is preferred. -21 - 201236867 The monomer having an ester group is exemplified by vinyl acetate, methyl acrylate, ethyl acrylate, n-butyl acrylate, methyl methacrylate or the like. Among them, at least one monomer selected from the group consisting of vinyl acetate, methyl acrylate, and methyl methacrylate is preferred. The monomer having a carbonate group is exemplified by allyl carbonate, propylene carbonate ethyl carbonate, ethylene carbonate, ethyl acetate, and the like. Among them, at least one monomer selected from the group consisting of methyl allyl carbonate and ethyl allyl carbonate is preferred. The monomers having an epoxy group are exemplified by allyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, 2-vinyloxirane, 2-methyl-2-vinyl epoxy B. Alkyl, 1,2-epoxy-5-hexene, 1,2-epoxy-9-decene, and the like. Among them, at least one selected from the group consisting of allyl glycidyl ether, glycidyl methacrylate, glycidyl acrylate, and 2-vinyloxirane is preferred. The monomer having a nitrile group is exemplified by acrylonitrile, allyl cyanide, cyanoacrylate, cyanomethacrylate or the like. Among them, at least one monomer selected from the group consisting of acrylonitrile and allyl cyanide is preferred. The monomer having an isocyanato group is preferably at least one monomer selected from the group consisting of ethylene isocyanate and propyl isocyanate. The carboxylic acid halide group is preferably introduced by reacting a fluororesin containing a carboxyl group with a halogenating agent such as sulfinium chloride or hydrazine chloride to convert a carboxyl group. The polymerization unit having a carboxylic acid halide group is preferably one obtained by converting a carboxyl group having a polymerization unit of a carboxyl group into a carboxylic acid halide group. The monomer [a] having an adhesive functional group is preferably a single one having an amine group

-22- SS 201236867 A monomer having a mercapto group, a monomer having an amine methyl group, a monomer having a hydroxyl group, a monomer having a carboxyl group, a monomer having an acid anhydride group, a monomer having an ester group, At least one selected from the group consisting of a monomer having a carbonate group, a monomer having an epoxy group, a monomer having a nitrile group, and a monomer having a carboxylic acid halide group, more preferably having an epoxy group At least one selected from the group consisting of a monomer, a monomer having a hydroxyl group, and a monomer having a carboxyl group, and more preferably a monomer having a carboxyl group, preferably an unsaturated carboxylic acid represented by the formula (1) The above fluororesin containing an adhesive functional group is preferably a TFE/HFP/monomer [α] copolymer, a TFE/PAVE/monomer [α] copolymer, an Et/TFE/monomer [α] copolymer, and an Et /TFE/HFP/monomer [α] copolymer, CTFE/monomer [α] copolymer, CTFE/TFE/monomer [α] copolymer, Et/CTFE/monomer [α] copolymer, partial fluorination Ethylene/monomer [α] copolymer, TFE/VdF/monomer [α] copolymer, VdF/HFP/TFE/monomer [α] copolymer, VdF/HFP/monomer [α] copolymer, and fluorine Group of ethylene [PVF] / monomer [α] copolymer Groups of at least one selected. More preferably, at least one selected from the group consisting of Et/TFE/monomer [α] copolymer and Et/TFE/HFP/monomer [α] copolymer, more preferably Et/TFE/HFP/monomer [α] copolymer. In the first laminate of the present invention, the fluororesin having an adhesive functional group derived from the polymerization unit of the above monomer [α] is 100 mol% with respect to the total polymerization unit of the fluororesin constituting the adhesive functional group. Preferably, it is 〇.〇5~10 mol%, more preferably 〇.〇5~5 mol%, and more preferably 0.2~2 mol%. In the second laminate of the present invention, the fluororesin having an adhesive functional group derived from the polymerization unit of the above monomer [α] is derived from the poly-23-201236867 unit of the monomer [α] relative to The total polymerization unit constituting the fluororesin having an adhesive functional group is 100 mol%, preferably 0.2 to 10 mol%. More preferably 0.2 to 5 mol%, and even more preferably 0.2 to 2 mol%. By setting the polymerization unit derived from the monomer [α] to the above range, the adhesive functional group can be adjusted to obtain an extremely excellent adhesion between the layer (Β-1) or the layer (Β-2) and the layer (C). Therefore, as a whole, the laminate has excellent impact resistance and mechanical strength. In the present invention, the melting point of the above-mentioned fluororesin containing an adhesive functional group is preferably from 120 to 240 °C. More preferably, it is 150 to 230 t: and more preferably 150 to 220 ° C, preferably 140 to 20 (TC. By making the melting point within the above range, the adhesion to the modified polyolefin is more excellent. The melting point of the fluororesin containing the adhesive functional group is preferably at least the decomposition temperature of the adhesive functional group contained therein, more preferably 5 ° C or more lower than the decomposition temperature of the adhesive functional group contained. The melting point is in the above range, and the stability during molding processing is further improved. The decomposition temperature of the adhesive functional group can be determined by thermogravimetric measurement (TG) or differential thermal-thermal weight simultaneous measurement (TG-DTA). The molecular weight of the above-mentioned fluororesin containing an adhesive functional group is preferably in a range which exhibits mechanical properties, chemical barrier properties, etc. of the obtained laminate. For example, a melt flow rate [MFR] is used as an index of molecular weight, and a fluororesin is generally used. The MFR at any temperature in the range of the forming temperature range of about 23 to 300 ° C is preferably 0.5 to 1 〇〇 g / l 〇 minutes. In the present specification, the melting point of each resin is a DSC device (manufactured by Seiko Corporation). When heating at a rate of 1 ° C / min In the melting heat curve, the temperature is determined by the temperature corresponding to the maximum 値 - - , , , , , , , , , , , , 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融 熔融The weight (g) of the polymer flowing out of the nozzle per unit time (10 minutes). The fluororesin containing the adhesive functional group may be a conventional polymerization method such as suspension polymerization, solution polymerization, emulsion polymerization, or bulk polymerization. In the above polymerization, various conditions such as temperature, pressure, polymerization initiator or other additives may be appropriately set depending on the composition or amount of the desired fluororesin. Layer (C) formed of the above-mentioned fluororesin containing an adhesive functional group In terms of improving the adhesion between the layers and improving the impact resistance or strength of the obtained laminate, the surface thereof may also be subjected to an adhesive surface treatment. The adhesive surface treatment in the present invention is not particularly limited and is exemplified by etching treatment, for example. , conventional techniques such as plasma treatment, corona treatment, and photochemical treatment. The above adhesive surface treatment can be based on the composition of the fluororesin used. The polyolefin resin constituting the layer (A) is exemplified by, for example, a homopolymer of ethylene or ethylene and one or more other α-olefins, specifically propylene, 1-butene, 4-methyl-1- a copolymer of pentene, 1-hexene, 1-octene, 1-decene, etc. The polyolefin resin is exemplified by a propylene homopolymer, a propylene-ethylene block copolymer, a low density polyethylene, a medium density polyethylene. , high-density polyethylene, ultra-high-density polyethylene, etc. The polyolefin resin preferably has a melt flow rate (MFR) of 0.01 to 100 g/10 min and a density of 0.850 to 0.980 g/cm 3 , wherein the polyolefin resin is preferably a high density. Polyethylene. -25- 201236867 The second laminate of the present invention is a one-side laminate layer (B-2) of layer (C), that is, the layer (C) is in direct contact with the layer (B-2). Floor. The modified polyolefin resin constituting the above layer (B-2) is exemplified by a homopolymer such as ethylene or ethylene and one or more other α-olefins specifically propylene '1-butene, 4-methyl-1- A copolymer of pentene, 1-hexene, 1-octene, 1-decene or the like is modified. The modified polyolefin resin preferably has a melt flow rate (MFR) of 〇.〇1 to l〇〇g/10 minutes and a density of 850.850 to 0.980 g/cm3. The modified polyolefin resin is preferably selected from the group consisting of propylene homopolymer, propylene/ethylene block copolymer, low density polyethylene, medium density polyethylene, high density polyethylene, and ultra high density polyethylene. At least one of those who have been upgraded is better at upgrading high-density polyethylene. The modified polyolefin resin constituting the upper layer (B-2) has a functional group. The functional group of the modified polyolefin resin constituting the layer (B-2) is a functional group which exhibits reactivity with respect to the adhesive functional group of the fluororesin of the adhesive functional group constituting the layer (C). It is not particularly limited, and is preferably, for example, an amine group, a mercaptoamine group, an amine mercapto group, a hydroxyl group, a carboxyl group, a carboxylic acid halide group, an ester group, an acid anhydride group, a carbonate group, an epoxy group, a nitrile group, and an isocyanate group. At least one of the selected groups is selected. More preferably, it is at least one selected from the group consisting of an epoxy group, an amine group, and an isocyanate group. The modified polyolefin resin constituting the above layer (B-2) is preferably a self-propylene homopolymer, a propylene-ethylene block copolymer, a low density polyethylene, a medium density polyethylene, a high density polyethylene, and a super At least one selected from the group consisting of high density polyethylene is modified to have an amine group, a mercaptoamine group, an amine mercapto group, a hydroxyl group, a carboxyl group, a carboxylic acid halide group, an ester group, and an acid anhydride group 'carbonate group.

-26-S 201236867, at least one selected from the group consisting of epoxy, nitrile and isocyanate groups. Among the above modified polyolefin resins, polyethylene modified with an unsaturated carboxylic acid, epoxy modified polyethylene, amine (nh2) modified polyethylene, and isocyanate modified polyethylene are preferred. The at least one modified polyethylene selected from the group is preferably selected from the group consisting of epoxy modified polyethylene, amine (NH2) modified polyethylene, and cyanate modified polyethylene. A modified polyethylene. The above unsaturated carboxylic acid modified polyethylene can be obtained by grafting a polyethylene with an unsaturated carboxylic acid and/or a derivative thereof in the presence of a radical generating agent. The graft amount of the polyethylene is preferably from 0 to 01% by weight to 10% by weight, more preferably from 0.1 to 5% by weight. If the graft amount is in the above range, the adhesion becomes better. The above unsaturated carboxylic acid modified polyethylene preferably has a density of 0.85 0 to 0'980 g/cm3, more preferably 0.870 to 0.970 g/cm3». When the density is 0.85 0g/cm3 or more, the product particles are not easily blocked, so that it is preferred. ^ The above unsaturated carboxylic acid and its derivatives are listed as acrylic acid, maleic acid, fumaric acid, tetrahydrophthalic acid, itaconic acid, citraconic acid, crotonic acid, isocrotonic acid, nadic acid (trade name) Unsaturated carboxylic acids such as (hang-cis-bicyclo[2,2,1]hept-5-ene-2,3-dicarboxylic acid), and derivatives thereof (for example, samarium, decylamine, hydrazine) Imine, anhydride, ester, etc.). Also listed are, for example, propylene dichloride, maleimide, maleic anhydride, citraconic anhydride, monomethyl maleate, dimethyl maleate, glycidyl maleate, and the like.

S -27- 201236867 The above unsaturated carboxylic acid and its derivative are preferably a monounsaturated carboxylic acid, a dibasic unsaturated carboxylic acid, and a metal salt, a guanamine, a quinone imine, an ester or an acid anhydride. At least one of the selected groups is selected. The above monounsaturated carboxylic acid generally has a carbon number of 20 or less, preferably 15 or less. Further, the above-mentioned monounsaturated carboxylic acid derivative is usually 20 or less carbon atoms, preferably 15 or less. The above-mentioned diunsaturated carboxylic acid generally has 30 or less carbon atoms, preferably 25 or less. Further, the derivative of the above-mentioned dibasic unsaturated carboxylic acid usually has a carbon number of 30 or less, preferably 25 or less. The above unsaturated carboxylic acid and its derivative, wherein acrylic acid, methacrylic acid, nadic acid, maleic acid and its anhydride, 5-norbornene-2,3-dicarboxylic acid and its anhydride, and methyl group At least one selected from the group consisting of glycidyl acrylate is preferably at least one selected from the group consisting of maleic anhydride and 5 · norbornene anhydride. The radical generating agent used in the grafting treatment is exemplified by an organic peroxide or an organic peroxyester. For example, the use of benzammonium peroxide, dichlorobenzhydryl peroxide, dicumyl peroxide, ditributyl peroxide, 2.5-dimethyl-2,5-di (over Oxide benzoate) hexyne-3, 1,4-bis(t-butylperoxyisopropyl)benzene, lauryl peroxide, tert-butyl peroxyacetate, 2,5 -Dimethyl-2,5-di(t-butylperoxy)hexyne-3, 2.5-dimethyl-2,5-di(t-butylperoxy)hexane, third Peroxybenzoic acid ester, tert-butylperoxyphenyl acetate, t-butyl peroxyisobutyrate, t-butyl peroxydioctanoate, tert-butylperoxy Valerate, cumylperoxypivalate and tert-butylperoxydiethylacetate, and 28-201236867 azo compounds, such as azobisisobutyronitrile, dimethylazoisobutyronitrile . Preferred among these are dicumyl peroxide, di-tert-butyl peroxide, 2,5-dimethyl-2,5-di(t-butylperoxide)hexyne-3,2 a dialkyl peroxide such as 5-dimethyl-2,5-di(t-butylperoxy)hexane or 1,4-bis(t-butylperoxyisopropyl)benzene. Among them, as the radical generating agent, an organic peroxide is preferred. It is preferred that the organic peroxide has a decomposition temperature of 100 ° C or more in half life. Further, the organic peroxide is preferably preferably dicumyl peroxide, benzamyl peroxide, ditributyl peroxide, 2,5-dimethyl-di (t-butyl) Oxy)hexane, 2,5-dimethyl-2,5-(t-butylperoxy)hexane-3' lauryl peroxide, and tert-butyl peroxybenzoate At least one of the selected groups. The use ratio of the radical generator is usually 0.001 to 1 part by weight based on 1 part by weight of the modified polyolefin. The above unsaturated carboxylic acid-modified polyolefin can be produced by uniformly mixing a polyethylene resin, an unsaturated carboxylic acid and/or a derivative thereof, and a radical generator. Specifically, it is exemplified by a melt kneading method using an extruder or a Banbury kneader or a kneader, a solution method dissolved in a suitable solvent, a slurry method suspended in a suitable solvent, or a so-called vapor phase grafting method. Wait. The treatment temperature is appropriately selected in consideration of deterioration of the polyethylene resin, decomposition of the unsaturated carboxylic acid and/or its derivative, decomposition temperature of the radical generator used, and the like. For example, the above melt-kneading method is usually carried out at a temperature of 60 to 350 °C. The above treatment temperature is preferably from 190 to 3 50 ° C, more preferably from 200 to 300 ° C. -29- 201236867 Whenever the above-mentioned unsaturated carboxylic acid-modified polyethylene is produced, in order to improve its performance, a method known in the art described in JP-A-62-01-01 can be used, for example, in grafting. After the quality or modification, the unreacted monomer (unsaturated carboxylic acid or its derivative) is removed by heating, washing or the like by treating with an epoxy compound, an amine group or a hydroxyl group-containing polyfunctional compound. Or a method of producing components such as by-products. The epoxy modified polyethylene may be copolymerized with an epoxy group-containing unsaturated compound by copolymerization of ethylene and an epoxy group-containing unsaturated compound, or by an epoxy group-containing unsaturated compound in the presence of a radical generating agent. Branch processing. The copolymerization of ethylene and an epoxy group-containing unsaturated compound can be carried out by a radical polymerization method at a pressure of from 200 to 2,500 bar. The grafting treatment can be carried out for the molten phase in the solvent phase or in the presence of a peroxide. This graft treatment method is known per se. The epoxy group-containing unsaturated compound is exemplified by, for example, the following. (1) Aliphatic glycidyl esters and aliphatic glycidyl ethers: for example, allyl glycidyl ether, vinyl glycidyl ether, glycidyl maleate, and itaconate, glycidyl (meth)acrylate (2) alicyclic glycidyl esters and ethers: for example 2-cyclohexene-1-glycidyl hydrazide, 4,5-diglycidylcyclohexene-carboxylate, 4-glycidylcyclohexene carboxylate Acid ester, 5-norbornene-2-methyl-2-glycidyl carboxylate, 2,3-diglycidyl-hang-cis-bicyclic (2.2.1)-5-heptene-carboxylate When the ester polyethylene is grafted, a homopolymer or copolymer of polyethylene can be grafted. The above epoxy-modified polyethylene is also preferably an ethylene/(meth)acrylic acid alkyl-30-201236867 ester/epoxy-containing unsaturated compound copolymer. In this case, it is preferred to contain 40% by weight or less, preferably 5 to 40% by weight, of the alkyl (meth)acrylate, and 10% by weight or less, preferably 0.1 to 8% by weight, based on the epoxy group-containing group. Saturated compound. The epoxy group-containing unsaturated compound is more preferably glycidyl (meth)acrylate. The alkyl (meth)acrylate is preferably at least one selected from the group consisting of methyl (meth)acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylate and 2-ethylhexyl acrylate. Among the above epoxy-modified polyethylenes, the alkyl (meth)acrylate is preferably from 20 to 35 % by weight. Preferably, the MFI is 5 to 1 00 (1 90 ° C / 2.16 kg g / l 〇 minutes), and the melting point is 60 to 110 ° C. The above epoxy-modified polyethylene can be obtained by subjecting a monomer to radical polymerization. The above polyethylene can be purchased from a commercially available product which is generally produced in the form of pellets and which is produced by radical polymerization at a pressure of from 200 to 250 bar. For example, the above-described amine-modified polyethylene can be powdered in the presence of a radical generator by using a water cutting method of GARVA (Gala, Virginia, USA) or a microgranulation method of freeze-grinding. It is obtained by grafting a polyethylene with a polyamine compound containing a majority of an amidino group or an amine group. The above polyamine compound has a primary amine (R-NH2), a secondary amine (RyNH), a tertiary amine (R3-N), or a derivative thereof (for example, decylamine (R-CONH2)) in its molecule. Polymer or copolymer. In the formula, r is a hydrocarbon group, preferably a group consisting of an alkyl group, an aryl group, an aralkyl group, an alkenyl group and an alkynyl group, and at least one hydrocarbon group is selected from -31 to 201236867. More preferably, the number of carbon atoms of methyl, ethyl, propyl, butyl, pentyl, isopropyl, isobutyl or the like is from 1 to 10, preferably from 1 to 8, more preferably from 1 to 5'. The alkyl group of 1 to 3: a vinyl group, an allyl group or the like having 2 to 10 carbon atoms, preferably 2 to 8, more preferably 2 to 5, most preferably 2 to 4 alkenyl groups; or a phenyl group, a naphthyl group or the like. At least one hydrocarbon group selected from the group consisting of aryl groups having 6 to 10 carbon atoms. Preferred specific examples of the above polyamine compound are exemplified by vinylamine, polyallylamine and aromatic amine. The molecular weight of the above polyamine compound is preferably 1,000 or more, but it is preferably a higher molecular weight from the viewpoint of reactivity with an olefin after activation treatment or the like. Specifically, the molecular weight is preferably from 1,000 to 200,000, more preferably from 3,000 to 200,000, and most preferably from 15,000 to 200,000. The above-mentioned radical generating agent can be used as a radical generating agent exemplified by a user when the polyethylene which is an unsaturated carboxylic acid is subjected to graft treatment. The types and proportions of the free radical generators that are suitable are also the same. Further, the method of the graft treatment may be the same as the method of graft-treating the polyethylene in which the unsaturated carboxylic acid is modified. The above-mentioned isocyanate-modified polyethylene is obtained by graft-treating polyethylene and an isocyanate group-containing unsaturated compound in the presence of a radical generating agent. The above isocyanate-modified polyethylene is preferably obtained by grafting 0.001 to 1.5 mol% of an isocyanate group-containing unsaturated compound onto polyethylene. When the amount of the isocyanate group-containing unsaturated compound is too small, there is a lack of adhesion, and when there is too much, there is a lack of adhesion. The above isocyanate group-containing unsaturated compound is a compound having at least one double bond and containing at least one isocyanate group (-NCO). Specifically -32-

S 201236867, listed as (meth) propylene decyl isocyanate, crotonyl isocyanate, barbituric acid isocyanate ethyl ester, crotonic acid isocyanate butyl ester, crotonic acid isocyanate ethyl glycol ester, crotonic acid Isocyanate ethyl diethylene glycol ester, barium acid isocyanate ethyl triethylene glycol ester, (meth)acrylic acid isocyanate ethyl ester '(meth)acrylic acid isocyanate butyl ester '(meth)propanoic acid isocyanate Hexyl hexyl ester, (meth)acrylic acid isocyanate octyl ester, (methyl) acrylic acid isocyanate-based lauryl ester (meth)acrylic acid isocyanate hexadecyl ester, (meth)acrylic acid isocyanate glycolate, (meth)acrylic acid isocyanate ethyl diethylene glycol ester, (meth)acrylic acid isocyanate ethyl triethylene glycol ester, etc., particularly preferably (meth)acrylic acid isocyanate ethyl ester. The radical generating agent is preferably an organic peroxide, more preferably a one-minute half-life of 100 to 280 °C. In particular, it is preferred to have a half-life of one minute of 12 0 to 23 ° C. Representative examples of organic peroxides are exemplified by t-butyl peroxybenzoate, 2,5-dimethyl-2,5-di(t-butylperoxy)hexane, di-tert-butyl peroxide. These organic peroxides may be used singly or in combination of two or more. When the above-mentioned isocyanate-modified polyethylene is subjected to graft treatment, the ratio of the isocyanate group-containing unsaturated compound is preferably 0.01 to 10 parts by weight, more preferably 0.02 to 5 parts by weight, based on 100 parts by weight of the polyethylene. More preferably 0.05 to 5 parts by weight. When the ratio of the isocyanate group-containing unsaturated compound to the 1 part by weight of the polyethylene is too small, the number of functional groups constituting the layer (B-2) decreases, and the layer (B-2) and the layer (C) are lacking. Then the shackles of sex. On the other hand, when there are too many, since the graft reaction efficiency is lowered, the isocyanate group-containing unsaturated compound of the unreacted or by-produced product of 33-201236867 remains in the modified polyethylene resin, so that it does not cause Adhesiveness continues to decline, and it will damage the original physical properties of polyethylene resin. The compounding ratio of the organic peroxide is preferably 0.001 to 0.18 parts by weight, more preferably 0.01 to 0.18 parts by weight, still more preferably 0.02 to 0.15 parts by weight, per 100 parts by weight of the polyethylene. When the compounding amount of the organic peroxide to 100 parts by weight of polyethylene is too small, the layer (B-2) and the layer (C) lack adhesiveness, and when too much, the original physical property of the polyethylene may be impaired. Then, since the graft reaction efficiency is lowered, the isocyanate group-containing unsaturated compound which is unreacted or by-product of the unreacted product remains in the reformed polyethylene, and the adhesiveness is lowered. The above-mentioned modified polyethylene resin can be obtained by upgrading by melt-kneading using an extruder used in the field of general synthetic resin. In this case, the extruder to be used may be either a beltless belt or a belt type, but the viewpoint of removing the isocyanate group-containing unsaturated compound and the decomposition product of the organic peroxide which are unreacted or by-products. In other words, it should be a belt extruder. The above kneading temperature is preferably from 140 to 280 ° C, and although it varies depending on the type of polyethylene or organic peroxide to be used, it is preferably from 1 80 to 23 ° C. When the temperature of the kneading is too low, there is a possibility that the modification cannot be performed well, and when it is too high, there is a possibility that one of the polyethylenes used is deteriorated. Further, the residence time in the extruder is preferably 60 seconds or more, and particularly preferably 90 seconds or more. When the residence time in the extruder is less than 60 seconds, there is a possibility that the satisfactory modification cannot be performed. In the case of melt modification, it is also possible to add a pair of commonly used in the field of polyethylene -34-

S 201236867 Oxygen or heat stabilizers, chelating agents (eg, mica, talc, glass, organic fibers, wood flour), slip agents and flame retardants. The modified polyolefin resin constituting the above layer (B-2) is preferably a modified high-density polyethylene, and among them, a high-density polyethylene modified by an unsaturated carboxylic acid or an epoxy-modified high-density polymer is preferred. At least one modified high-density polyethylene selected from the group consisting of ethylene, amine (NH2) modified high density polyethylene, and isocyanate modified high density polyethylene, and more preferably modified by epoxy At least one modified high density polyethylene selected from the group consisting of density polyethylene, amine (NH2) modified high density polyethylene, and isocyanate modified high density polyethylene. The resin constituting each of the above layers may be one containing only one type of resin, or may be two or more types. The above layers may also be formulated with various kinds of sputum agents such as inorganic powder, glass fiber, metal oxide, etc., depending on the purpose and use, without damaging the performance thereof. , blending thermal stabilizers, reinforcing agents, UV absorbers, pigments and other additives. As for the above additives, for example, montmorillonite, beidellite, saponite, nontronite, hectorite, zinc monoxide may be added from the viewpoint of reducing the permeation of the liquid. A layered mineral with a high aspect ratio such as sauconite, stevenite ore, or a layered viscosity mineral such as mica. As the above additive, for example, a conductive chelating agent may be added to impart conductivity. The conductive chelating agent is not particularly limited, and examples thereof include a metal, a conductive monomer powder such as -35-201236867 carbon, or a conductive monomer fiber; a powder of a conductive compound such as zinc oxide; and a surface conductive powder. The conductive monomer powder or the conductive monomer fiber is not particularly limited, and examples thereof include metal powders such as copper 'nickel; metal fibers such as iron and stainless steel: carbon black, carbon fiber, and JP-A-3-174018. Carbon filaments and the like described. The surface conduction-treated powder is a powder obtained by subjecting a surface of a non-conductive powder such as glass beads or titanium oxide to a conductive treatment. The method of the above-described conductive treatment is not particularly limited, and examples thereof include a printed substrate, metal sputtering, electroless plating, and the like. The carbon black in the above conductive chelating agent is advantageous in terms of economy or prevention of static electricity accumulation. When the above conductive chelating agent is blended, it is preferred to prepare granules by melt-kneading in advance. The volume resistivity of the resin conductive composition obtained by blending the conductive chelating agent is preferably from lxlOG to 1 χ 109 Ω·cm. The lower limit is 1 χ 102 Ω·cm, and the upper limit is 1 χ 1 〇 8 Ω · cm. When conductivity is imparted, conductivity can be imparted only to the fluororesin which is in contact with the chemical solution in the innermost layer. In this case, a conductive fluororesin layer may be provided as the inner layer of the fluororesin layer. The second laminate of the present invention is a layer (A) formed of a polyolefin resin, a layer (B-2) formed of a modified polyolefin resin, and a fluororesin containing an adhesive functional group. The layer (C) formed is formed, and at least one of the innermost layer or the outermost layer is a layer (C). In this case, since the laminate has the layer (B-2) between the layer (A) and the layer (C), the adhesion of the layer (A) to the layer (C) can be improved -36-201236867. The term of the innermost layer or the outermost layer means that when the laminate is a pipe or a hose, it means the innermost layer or the outermost layer according to the meaning of the word, and when the laminate is a sheet or a film, it means the outermost side of the sheet or film. Layer. When the laminate comprises a layer other than the layer (A), the layer (B) and the layer (C), the layer other than the layer (C) may be located inside or outside the layer (C). The preferred layer constitution of the laminated structure of the first and second-layer laminates of the present invention is not particularly limited, and examples thereof include polyethylene resin/modified polyethylene resin/fluororesin, polyethylene resin/modified polyethylene. Resin/fluororesin/fluororesin, fluororesin/modified polyethylene/polyethylene resin/modified polyethylene resin/fluororesin, fluororesin/fluororesin/modified polyethylene/polyethylene resin/modified polyethylene resin/ Fluororesin / fluororesin, etc. The laminated structure of the first and second laminates of the present invention is preferably a polyolefin resin [layer (A)] / modified polyhydrocarbon resin [layer (B-1) or layer (B-2)] / Fluororesin [layer (C)] (outer layer / intermediate layer / inner layer). By providing a modified polyolefin resin [layer (B-1) or layer (B-2)] as an intermediate layer, adhesion of the fluororesin [layer (c)] to the polyolefin resin [layer (A)] can be improved. . In particular, by providing the layer (B-1), an extremely high adhesive strength can be achieved, and a relatively high adhesive strength can be achieved as compared with the case of the layer (B-2). The resin obtained by the multilayer film or the resin waste produced when processed into a bag shape or the resin obtained by recovering the above-mentioned laminate is melt-kneaded by a two-axis extruder or a short-axis extruder as a recovery layer. In the laminate of the present invention, the layer (C) may be 50 to 500 μm, and the layer (C) may be 100 to 50000 μm in total of layers other than -37 to 201236867. The film thickness of the layer (C) is preferably from 100 to 300 μm, and the film thickness of the layer other than the layer (C) is preferably from 30,000 to 20,000 μm, more preferably from 600 to ΙΟΟΟΟμηη. The above laminate may be selected in accordance with its use. In the present specification, the film thickness of each layer is measured by a microscope or the like. The fuel permeability coefficient of the above fluororesin is preferably 10 g·mm/m 2 /day or less, more preferably 7 g·mm/m 2 /day or less, and more preferably 5 g·mm/m 2 /day or less. When the fuel permeability coefficient of the fluororesin is within the above range, the laminate of the present invention can have a higher fuel permeability. In the present specification, the fuel permeability coefficient is obtained by the film obtained from the resin to be measured. An isooctane/toluene/ethanol mixed solvent (hereinafter referred to as CE10) mixed with isooctane, toluene and ethanol in a volume ratio of 45:45:10, and a volume ratio of 7.5:7.5:85 In the fuel permeability coefficient measuring cup of the mixed solvent (hereinafter referred to as CE85), the larger of the two enthalpy calculated from the mass change measured at 6 °C. The lower limit of the fuel permeation rate of the laminate of the present invention may be, for example, 0.05 g/m2/day, and the upper limit may be, for example, 30 g/m2/day. In the present specification, the fuel permeation rate is the mass per unit day of the laminate and the mass per unit area per unit area, and is obtained by measuring the permeation amount at 60° C. using CE10 or CE85. The method for forming the laminate is not particularly limited, and the most appropriate method can be selected depending on the use and shape of the laminate. Examples of the molding method are injection molding, press molding by vacuum or pressurization, blow molding, blow molding, extrusion molding, and the like. -38-

S 201236867 The above injection molding is widely used for the molding of thermoplastic resins, and is suitable for the production of molded bodies of complicated shapes. The formation of the molded body can be carried out, for example, by repeatedly performing a method in which the molten resin is injected into the mold of the molded body member, which is formed by solidification on the resin layer, and the molten other resin is injected and cured. However, when the above injection molding method is used, since it is necessary to remove the mold after molding, the laminate cannot be produced at one time, and it is divided into a plurality of members, and then integrally joined by means of heat fusion, adhesion, or the like, thereby obtaining the desired Laminate. In the laminate of the present invention, since the fluororesin layer must be located at either the innermost layer or the outermost layer, even when the above bonding is performed, since the fluororesin layers are necessarily bonded to each other, the fuel of the entire laminate can be maintained. Low permeability. The order of the forming steps of the above layers may be appropriately selected depending on the desired lamination structure, and the outer layer may be formed as described above, or the inner layer may be formed first. The conditions of the above injection molding can be appropriately selected depending on the kind or amount of the resin to be used. The above press forming is performed by using a sheet or a sheet obtained by a forming method described later (the sheet or sheet is hereinafter referred to as a laminate sheet) as a raw material, which is subjected to vacuum or pressurization under heating, or extruded by a male mold to Formed in the mold. The conditions in the above press forming may be appropriately selected depending on the composition or thickness of the laminate sheet to be used, but in the first step of heating the laminate sheet, the upper heater and the lower heater are preferably heated according to the melting temperature of each layer. The temperature of the device -39 - 201236867 degrees is set to a different temperature. The method of producing a laminate sheet which is the above-mentioned raw material is exemplified by, for example, (1) a method of coextruding a resin in a molten state, thereby thermally melting (melting and adhering) between layers to form a laminate of a multilayer structure. (co-extrusion molding), (2) a method of laminating the separately formed films by an extruder and adhering them by heat fusion, and (3) extruding the molten resin onto the surface of the pre-made film by an extruder a method of forming a laminate thereon, (4) electrostatically coating a polymer constituting a layer adjacent to the film on a surface of a pre-formed film, and heating the entire coated article or the side of the self-coating layer A method of heating and melting a polymer supplied to a coating to form a layer. In the case where the resin constituting each layer can be coextruded, it is generally formed by coextrusion molding of the above (I). The above coextrusion molding is exemplified by a conventional multi-layer coextrusion production method such as a multi-manifold method, a feed sleeve method, a multilayer blowing method, or a multilayer blow molding method. The laminate of the present invention can be formed into a sheet-like or film-like laminate by any of the above methods. The laminate of the present invention can be joined by any means known in the art, and the laminate sheet can be attached to the sheet to form a bag shape and become a hollow such as a groove. Shaped body. In the method of bonding, when a heat fusion bonding method such as a heat sealing method is used, specifically, two sheets of the above-mentioned laminate sheets are preferably superposed such that the fluororesins are adjacent to each other and heat-sealed. The heat-sealing temperature is preferably equal to or higher than the thermal decomposition temperature of the adhesive resin and the laminated thermoplastic resin from the viewpoint of the sealing strength between the sheets. The heat sealing method is not preferred in terms of the influence of deterioration of the adhesive. The above thermal fusion bonding method is exemplified by the method of using a heating plate, using -40-

S 201236867 The method of hot air, the method of using frictional heat (mechanical, ultrasonic) or the method of using high frequency. The laminated sheet is formed by vacuum molding, pressure forming, male mold molding, injection molding, or the like, and then immediately cooled, and may be in the form of a bag by these thermal fusion bonding methods. Vacuum forming, pressure forming, and male mold forming are performed because the laminated sheets are heated at the time of forming, and then heat fusion bonding can be performed immediately, and the production efficiency is better. Further, the above-described heat fusion bonding may be carried out in combination. Further, it is also possible to use a fusion portion of the heating wire for electric fusion (electrofusion bonding) as a method of heat fusion. When the laminate of the present invention is joined to form a bag, it is preferred that the fluororesins are fused to each other from the viewpoint of fuel permeability and chemical resistance, and that the other layers, particularly the outer layer of the polyolefin, are formed. It is preferable from the viewpoint of mechanical strength that the layers are fused to each other. Since the layers are easily melted with each other, at least a portion of the edges of the molten sheet can be processed in advance as shown in Fig. 1. Hereinafter, the processing state of the sheet end of the fusion will be described using Fig. 1 . Fig. 1 is an example of a state in which the end of the above-mentioned laminate sheet joined is preliminarily processed. 3 denotes a layer (A) formed of a polyolefin resin, 4 denotes a layer (B-1) or a layer (B-2) formed of a modified polyolefin resin, and 5 denotes a fluororesin containing an adhesive functional group. The formed layer (C) can be easily melted and adhered by processing the end of the sheet 1 before processing into the processed sheet 2. It is also possible to temporarily melt the sheet 1 before processing, and apply the same processing to the end portion to apply heat and pressure to the fusion portion again. Further, other bonding means may use an adhesive. In this case -41 - 201236867, for example, the seam is coated with an adhesive, pressed against each other, and then the adhesive is hardened at least partially. Next, after being placed in an environment of 135 to 150 ° C, the joint was cooled under pressure. The seam is completely hardened at room temperature for 5 to 8 days. In the case where the laminate of the present invention is in the form of a bag, the thickness thereof may be appropriately set according to the use, and may be 50 μm or more, preferably 1 μm or more. Further, it may be 500 μm or less, preferably 300 μm or less. When the thickness is too thin, there is a problem that the fuel has low permeability or the mechanical strength is insufficient, and when the thickness is too thick, the flexibility is insufficient. The laminate of the present invention can also be obtained by multilayer blow molding. The above-mentioned multi-layer blow molding can use an extruder according to the number of layers required to extrude the molten resin through a multi-layer blow molding die, and clamp the prototype with a mosaic mold to clamp the upper and lower sides. Air or the like is blown into the bag-shaped blank, and is expanded and adhered to the inner wall of the mold having a desired shape, and after cooling and solidifying, the molded article is taken out. Further, injection blow molding or stretch blow molding can also be used. The above multilayer blow molding is a series of successive steps, so that it is preferable in terms of ease of formation. The laminate of the present invention may also be formed by coating a fluororesin layer constituting the inner surface layer. By the above-described coating of the fluororesin layer, for example, the above-described injection molding or vacuum forming can be carried out to obtain a molded body member formed of a layer other than the fluororesin layer having a desired shape, which will be contained in a conventional method. A fluororesin coating is applied onto the formed body member and dried. In order to further improve the liquid barrier property by using the above-mentioned coated fluororesin layer, it is preferred to fluorinate by a conventional method. That is, PVdF copolymer can also be used -42-

S 201236867 A fluororesin layer having a high barrier property is formed by fluorination after forming a coating film of a material or a fluorinated ethylene or the like or a fluorine-containing resin coating material having a low fluorine content. For the use of the laminate of the present invention, a fuel tank such as a printing substrate, a gasoline tank such as a car, a fuel tank such as a light oil tank, a radiator tank, a solvent tank, a coating tank, and a semiconductor liquid can be preferably used. A container for a corrosive or aggressive chemical liquid such as an acid or an alkali, a slurry container for a honing material, a food or a food tank, a liquid bottle, a container, a tank, a bag, and a fuel supply. Underground pipes or hoses used in the station. Further, the laminate of the present invention can also be used as a urea water container in a system for reducing the N 〇 x by spraying urea water to a diesel engine exhaust, and can be preferably used because of its excellent chemical resistance. The present invention is also a container for a liquid medicine formed from the above laminate. Further, it may be a container for urea water formed from the above laminate. It is also a fuel tank formed of the above laminate. It is also a tank for beverages or foods formed from the above laminate. It is also a pipe or hose buried underground by the above laminate. The underground pipeline or hose is preferably used by, for example, a fuel supply station. Also a funnel neck hose, fuel hose or fuel line formed from the above laminate. The funnel neck hose, fuel hose or fuel line is usually used for an internal combustion engine such as an automobile.

[Effect of the Invention] The laminate of the present invention is formed by the above-described constitution, so that the layer formed of the fluororesin containing the adhesive functional group and the layer formed of the modified polyolefin resin can be directly strengthened by the layer of -43-201236867. The bonding is excellent in initial adhesion and initial adhesion, and further maintains adhesion. [Embodiment] The present invention will be described in more detail below by way of examples, but the invention is not limited to the embodiments. In the examples and comparative examples, various measurement systems were carried out by the following methods. [Monomer composition of fluororesin] It was measured in a molten state using an NMR analyzer (manufactured by Bruker BioSpin Co., Ltd., AC3 00, high temperature probe). [Functional group content ratio] [Epoxy group of epoxy group-containing fluororesin] The composition ratio of TFE, Et, and HFP 3 was calculated from the obtained chart by using the following formula using l9F-NMR at 300 MHz. The molar content of TFE = {3B + 3C-2A} / {4A + 6B + 3C}

Mo content ratio of Et = {2A + 3B}/{4A + 6B + 3C} HFP contains Moh ratio = 4A/{4A + 6B + 3C} Further, A = -82~- 61ppm range of integral 値6 = -117~-94?1> The integral of the range of 値0 = -147~-117?? The integral of the range of 111. On the other hand, the fluorine-containing resin ions are used as a solvent at a high temperature, -44-

S 201236867 In the state of full swelling, the composition ratio of Et and the epoxy group-containing monomer was calculated from the obtained chart using 1 H-NMR of 300 MHz.

Et contains molar ratio = {2F-2D-3E}/{2F-2D-E} Mohs ratio of monomer containing epoxy group = 2E/{2F-2D-E} Again, D = 4.04~ The integral of 4.84ppm 箪 値 = E = 3.43~4.04ppm 値F = 1.39~3.43ppm integral 値 From the above results, TFE, Et, HFP, epoxy-containing single The composition ratio of the epoxy group-containing monomer (% by mole) was calculated as the content ratio of the quaternary epoxy group. [Carbide group at the end of the main chain of the carbonate-containing fluororesin] The cut piece of the white powder of the copolymer was compression-molded at room temperature to prepare a film having a thickness of 50 to 200 μm. The film was analyzed by infrared absorption spectroscopy, and the peak of the carbonyl group derived from the carbonate group [-〇C(=0)0-] appeared at the absorption wavelength of 1810~1815 cmlvCCsO)], so the peak of v(C=0) was determined. The absorbance was measured, and the composition of the carbonate group was calculated by the following formula (a). Carbonate group content (% by mole) = AW / (10 · sdf) (a) A : Absorbance of v (C = 0) peak derived from carbonate group [-0C( = 0)0-]: Mohr absorbance coefficient derived from the v (C = 0) peak of the carbonate group [-0<:( = 0)0-]. ε = 170 (1 . cm".moP1 from the model compound W: average molecular weight of the monomer calculated from the composition of the copolymer

C -45- 201236867 [Carboxyl group content of carboxyl group-containing fluororesin] The composition of the carboxyl group-containing fluororesin is melted, and 19F-NMR of 300 MHz is used, and TFE, Et, and HFP 3 are calculated from the obtained chart using the following formula. The composition ratio of the yuan. The molar content of TFE = {3B + 3C-2A} / {4A + 6B + 3C}

Mo content ratio of Et = {2A + 3B}/{4A + 6B + 3C} HFP contains Moh ratio = 4A/{4A + 6B + 3C} Further, A = -82~- 61ppm of the range 値B = -l 17~-9 The integral of the range of 4PPm 値C = integral of the range of -147~-117ppm 压缩 The cut piece of the white powder of the copolymer is compression-molded at room temperature to prepare a film having a thickness of 50 to 200 μm . The film was analyzed by infrared absorption spectroscopy, and the peak of the carbonyl group derived from the carboxyl group [_(C = 0)0H] appeared at the absorption wavelength of 1 630~1 783 CHT1 [v (C = 0)], so the v (C = 0) The absorbance of the peak, and the composition of the carboxyl group is calculated by the following formula (a). The content of the carboxyl group (% by mole) = AW / (10 · edf) (a) A : The absorbance of the peak of v (C = 0) derived from the carboxyl group [_(C = 0)0H] ε: derived from the carboxyl group [- (C = 0) 0H] The v-absorbance coefficient of the v (C = 0) peak. From the model compound ε = 5 00 (1 . cm·1 . mol·1) W: the average molecular weight of the monomer calculated from the composition of the copolymer. From the above results, TFE, Et, HFP, carboxyl group-containing monomer were obtained. The composition ratio of 4 yuan was calculated, and the composition (monogen%) of the monomer having a carboxyl group was calculated as the content ratio of the carboxyl group. -46 -

S 201236867 [Melting Point of Resin] Using a DSC apparatus (manufactured by Mettler Co., Ltd.), the temperature at a temperature of 10 t/min is required to correspond to the maximum temperature in the heat of fusion curve. [MFR] Using a melt coefficient meter (manufactured by Toyo Seiki Seisakusho Co., Ltd.), the weight (g) 接着 [adequate strength] from a nozzle of 2 mm in diameter and 8 mm in length per unit time (10 minutes) at each temperature and 5 kg load was measured. A sample having a length of 5 cm and a width of 1 cm was cut out from the molded body, and the weakest part of the molded body was peeled off, and a peel test of 180 ° was performed using a universal tensile tester (manufactured by Orientec), and the adhesive strength was measured in units of N/cm. . [Tensile Strength and Tensile Elongation] Using a universal tensile tester (manufactured by Orientec), a micro-ring sheet was stretched at a stretching speed of 100 mm/min at room temperature, and the maximum point strength and elongation were measured. The following resins were used in the examples and comparative examples. Fluororesin A (TFE/Et/HFP copolymer containing epoxy resin) Synthetic method Pure water lkg was placed in an autoclave with an internal volume of 4 L, and after fully replacing with nitrogen-47-201236867, octadecacyclobutane was fed. 884 g and 316 g of hexafluoropropylene maintained the internal temperature of the system at 35 ° C and a stirring speed of 580 rpm. Subsequently, 147 g of tetrafluoroethylene, 4.5 g of ethylene, and 1.5 g of allyl glycidyl ether were fed, followed by the addition of 15 g of a 50% by mass methanol solution of di-n-propylperoxydicarboxylate to start polymerization. At the same time as the polymerization was carried out, the pressure in the system was lowered, so that a mixed gas of tetrafluoroethylene/ethylene/hexafluoropropylene = 50.5/42.3/7.2 mol% was continuously supplied, and the pressure in the system was maintained at 1.0 MPaG. Next, a total amount of 5.9 g was continuously fed to the allyl glycidyl ether, and stirring was continued for 24.3 hours. Then, after the pressure was released to atmospheric pressure, the reaction product was washed with water and washed with methanol, and dried to obtain 22 Og of a fluororesin powder. The polymerization rate is almost fixed at 9.1 g/hr» during the whole reaction. The obtained powder has the following composition and physical properties. TFE/Et/HFP/allyl glycidyl ether (epoxy group-containing monomer) = 49.9/ 41 · 1/7.5/1.4 (% by mole).

Melting point: 190 ° C MFR : 22 g/10 min (210 ° C, 5 kg) Functional group content: epoxy group 1.4 mol % Fluoro Resin B (CTFE/TFE/PPVE copolymer having a carbonate group at the end of the main chain) Synthetic method 50 kg of pure water was fed into a stirred polymerization tank containing 175 kg of water, and the internal space was sufficiently replaced with pure nitrogen, and nitrogen was removed by vacuum. Then pressed into the octafluorocyclobutanin 40.5kg, chlorotrioxyethylene -48-

S 201236867 [CTFE] 2.4kg, tetrafluoroethylene [TFE] 6.5kg, perfluoro(propyl vinyl ether) [PPVE] 4.5 kg, adjust the temperature to 35 °C, start stirring. The polymerization was started by adding 2. 2 kg of a 50% by mass methanol solution of di-n-propylperoxydicarboxylate [NPP] as a polymerization initiator. In the polymerization, the mixed monomer which has the same composition as the desired copolymer composition is additionally fed while maintaining the pressure in the tank at 〇8 MPa, and then the gas remaining in the tank is exhausted and taken out. The polymer was demineralized and washed with pure water and dried to obtain 19 kg of a pelletized CTFE copolymer. Next, using a φ50ιηιη short-axis extruder, melt-kneading was carried out at a cylinder temperature of 28 (TC) to obtain pellets, and then the obtained pelletized CTFE copolymer was heated at 180 ° C for 24 hours. The obtained pellets had the following composition and physical properties. CTFE/TFE/PPVE = 3 4.5/63.4/2.1 (mole%) 〇

Melting point: 230 ° C MFR : 18 g/10 min (297 〇 C-5 kg) Functional group content: carboxylate group 0.02 mol % Fluoro Resin C (TFE/Et/HFP copolymer containing carboxyl group) Synthetic method Pure water 1.83 kg was placed in an autoclave having an internal volume of 6 L, and after sufficiently replacing with nitrogen, 848 g of octafluorocyclobutane and 414 g of hexafluoropropylene were fed, and the inside of the system was maintained at 35 ° C, and the stirring speed was 600 rpm. Subsequently, 143 g of tetrafluoroethylene, 4.5 g of ethylene, 50% by mass of methanol solution of hydrazine-carbenoic acid, g.3 g, cyclohexane O.lg, and then 21.5 g of di-n-propylperoxy-49 were added. - 201236867 A 50% by mass methanol solution of a carboxylate starts polymerization. At the same time as the polymerization was carried out, the pressure in the system was lowered, so that a mixed gas of tetrafluoroethylene/ethylene/hexafluoropropylene = 51.2/42.1/6.7 mol% was continuously supplied, and the pressure in the system was maintained at 0.9 2 MPaGf. Next, a 50 mass% methanol solution of undecylenic acid was continuously fed into a total amount of 3.6 g, and stirring was continued for 4.2 hours. Then, after the pressure was released to atmospheric pressure, the reaction product was washed with water and methanol, and dried to obtain 191 g of a white powder. The obtained powder has the following composition and physical properties. Ding? £心/町卩/undecenoic acid=47.6/4 2.5/9.6/0.3 (mole/〇).

Melting point: 1 9 5 ° C MFR : 3.0 g/10 min (230 〇 C, 5 kg) Functional group content: carboxyl group 0.3 mol % Thermoplastic resin modified polyethylene A [PE]: manufactured by Mitsui Chemicals, trade name ADMER HB030 modified polyethylene C[PE]: International Publication No. 2007/04026 No. 1 by the reaction of a polyolefin with a carbon-containing diimine-based compound to obtain an imine-based modified polyethylene HDPE: Japanese poly Manufactured by Olefin Co., Ltd., trade name HJ451 Experimental Example 1 A fluororesin A (thickness 200 μm)/modified polyethylene crucible (thickness 100 pm)/HDPE film (600 μηι) prepared by a multilayer blow molding method was used to form a tube of 20 mm. After sealing the seal on one side, add CE10 (different

-50- S 201236867 Octane/toluene/ethanol = 45/45/1 0 (% by volume)) and sealed on the other side of the heat seal, and placed in an explosion-proof furnace at 60 ° C for 168 hr. After the fuel was discharged, the micro-bells described in ASTM were punched and compared with the tensile strength and elongation of the micro-rings described in ASTM from the film impregnation before fuel impregnation. Further, the tensile strength and elongation were maintained at 75 % or more. Experimental Example 2 A fluororesin C (thickness 250 μm)/modified polyethylene C (thickness 150 pm)/HDPE film (600 μm) prepared by a multilayer blow molding method was used, and a 10 mm-shaped tube was sealed by a heat-sealing method. CE 10 (isooctane / toluene / ethanol = 4.5 / 45 / 10 (% by volume)) was added and sealed on the other side by heat sealing, and placed in an explosion-proof furnace at 60 ° C for 168 hr. After the fuel is discharged, the micro-ring sheet described in ASTM is punched and compared with the tensile strength and elongation of the micro-ring sheet described in ASTM before the fuel impregnation. Tensile strength and elongation are maintained above 75%. The initial adhesive strength of the layer of the fluororesin C of the molded body and the modified polyethylene C layer was 35 N/cm, and the fuel was immersed to 3 lN/cm. Experimental Example 3 A fluororesin B (thickness 200 μm)/modified polyethylene C (thickness 100 pm)/HDPE film (600 μηι) prepared by a multilayer blow molding method was used to form a 20 mm-shaped pipe, which was hermetically sealed by heat sealing. Thereafter, CE 10 (isooctane / toluene / ethanol = 4 5 / 45 / 10 (volume / 〇)) was added and sealed on the other side by heat sealing ' into an explosion-proof furnace at 60 ° C for 168 hr. After the fuel was discharged, the micro-bells described in ASTM were punched in 201236867 and compared with the tensile strength and elongation of the micro-bells described in the ASTM film before the fuel impregnation. Further, the tensile strength and elongation were maintained at 75% or more. The initial adhesive strength of the layer of the fluororesin B of the molded body and the modified polyethylene C layer was i 7 N/cm, and became 1 ON/cm after the immersion of the fuel. [Industrial Applicability] The laminate of the present invention can be preferably used as a container for accommodating a liquid, a bottle, a tank, a bag, a pipe, a hose, a pipe, and the like. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is an example of a processing state of a sheet end which is fused. [Explanation of main component symbols] 1 : Pre-processed sheet 2 : Processed thick sheet 3 : Layer formed of polyolefin resin (A) 4 : Layer (B-1) or layer (B-2) formed by modified polyolefin resin 5 : Layer formed by fluororesin containing an adhesive functional group (C) -52-

Claims (1)

201236867 VII. Patent Application Range: 1. A laminate characterized by having a layer formed of a modified polyolefin resin (B-1) and a fluorine containing an adhesive functional group formed on B-1) Resin (C). The modified polyolefin resin of the second constituent layer (B-1) is a modified polyolefin having a carbodiimide group, and constitutes a main chain end of the layer (C) containing an adhesive functional group. And/or the end of the side chain has an adhesive which exhibits reactivity with the functional group which the above-mentioned layer (E polypoly hydrocarbon resin has). 2. The laminate of the first aspect of the patent application, wherein the modified polycondensation of the imine group The olefin is a modified polyolefin having a carbodiimide group and a modified polyolefin having a polyimination of a polyolefin and a polyimine group. a base-based polyolefin, which is obtained by reacting a carbodiimide based on an unmodified polyolefin. 3. A laminate according to claim 1 or 2, a layer formed of a polyolefin resin formed on the layer (B-1) (4 a laminate, The layer (A) having a polyolefin resin, the layer (B-2) modified with a polyolefin, and the layer (C) containing fluorine of an adhesive functional group, and the layer formed The layer has an imino group or a fluororesin, and a modifying functional group at 5-1). The presence of the biocide is grafted to the compound of the carbohydrazide, and the quinone imine is modified to have a ruthenium. A resin formed of a hydrocarbon resin-53-201236867 The layer (c) formed of the fluororesin containing an adhesive functional group is a layer of at least either side of the innermost layer or the outermost layer, and constitutes the layer (C). The fluororesin having an adhesive functional group has an adhesive functional group exhibiting reactivity with respect to a functional group of the modified polyolefin resin constituting the layer (B-2) at the end of the main chain and/or at the side of the side chain, The adhesive functional group is 0.2 to 10 mol% with respect to 100% by mole of the total polymerization unit constituting the fluororesin having an adhesive functional group. 5. The laminate according to claim 4, wherein the composition The functional group of the modified polyolefin resin of the above layer (B-2) has an amine group , at least 1 selected from the group consisting of amidoxime, an aminecarbamyl group, a hydroxyl group, a carboxyl group, a carboxylic acid halide group 'ester group, an acid anhydride group, a carbonate group, an epoxy group, a nitrile group, and an isocyanate group. 6. The laminate of claim 1, 2, 3, 4 or 5, wherein the adhesive functional group is 100% by mole relative to the total polymerization unit constituting the fluororesin containing the adhesive functional group. , which is 0.2 to 5 mol%. 7. The laminate of claim 1, 2, 3, 4, 5 or 6 wherein 'the aforementioned adhesive functional group is relative to the composition containing an adhesive functional group. The total polymerization unit of the fluororesin is 100 mol%, and is 0.2 to 2 mol%. 8. The laminate of claim 1, 2, 3, 4, 5, 6 or 7 wherein the aforementioned adhesive functional group is an amino group, an amino group, an amine group, a hydroxyl group, At least one selected from the group consisting of a carboxyl group, a carboxylic acid halide group, an ester group 'anhydride group, a carbonate group, an epoxy group, a nitrile group', and an isocyanate group. 9. The composition of claim 1, 2, 3, 4, 5, 6, 7, or 8 -54 - 201236867, wherein the aforementioned adhesive functional group is a carboxyl group. 1. A laminate of the first, second, third, fourth, fifth, sixth, seventh, eighth or ninth aspect of the patent application, wherein the fluororesin containing the adhesive functional group has a melting point of 120 to 240° C. 1 1 . The laminate of claim 1, 2, 3, 4, 5, 6, 7, 8, 9 or 1 wherein the melting point of the fluororesin containing the adhesive functional group It is below the decomposition temperature of the adhesive functional group contained. 12. A laminate according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, or 1 of the patent, which is a container for a chemical liquid or a container for a urea water. 1 3. A laminate according to claim 1, 2, 3, 4, 5, 6, 7, 8, 9, or 10, which is a container for fuel, a material for food, or a container for food. 14. A laminate of claim 1, 2, 3, 4' 5, 6, 7, 8, 9 or 10 which is a buried pipeline or hose. 15. For a laminate of patents 1' 2, 3, 4, 5, 6' 7' 8, 9 or 10, which is a funnel neck (Filler Neck) hose, fuel hose, or fuel Pipeline. S-55-