MXPA00006394A - Multilayer composite - Google Patents

Abstract

A thermoplastic multilayer composite, and articles made therefrom, which has at least one layer I of a thermoplastic molding composition, at least one layer II of a further thermoplastic molding composition, bonded together with at least one layer of an adhesion promoter disposed between at least one layer I and at least one layer II. The adhesion promoter is at least 5%by weight of a graft copolymer prepared from 0.5 to 25%by weight, based on the total amount of graft copolymer, of a polyamine having at least 4 nitrogen atoms and having a number average molecular weight Mn of at least 146 g/mol, and polyamide-forming monomersselected from lactams, omega-aminocarboxylic acids, equimolar mixtures of diamines and dicarboxylic acids, and their mixtures

Description

UNION OF MULTIPLE LAYERS The object of the present invention is an adhesive agent for establishing a multilayer bond, and it also relates to the multilayer bond itself containing the aforementioned adhesive agent. Certain polymers, such as polyamides or polyesters, are not very useful, as such, for a wide range of applications. Thus, for example, polyamides do not have resistance to inclemencies since under an illumination they get older, absorbing moisture from the air. This leads to discolouration, • worsening of the mechanical properties and also causes certain distortion phenomena. Although the polyamides have good mechanical properties, and in particular good toughness, they possess a defective blocking action and particularly the polar substances can migrate easily through the polyamides. This is a very important disadvantage, for example, in the lines that drive fuel, in which the presence of some alcohol-based fuel is required. In general terms, it can be said that polyesters have a good resistance to inclemency and they show an outstanding blocking action both before polar and non-polar means. But as rules are sensitive to shocks, and particularly the tenacity under impact with notching is often not enough in the case of polyesters. Consequently, polyesters alone can not be used in many cases in which it would be desirable to have other properties such as their outstanding blocking action, high resistance to high temperatures and an outstanding degree of rigidity. Also other polymers generally show a picture of unbalanced properties and therefore are not suitable for many applications. It would therefore be desirable to achieve the fabrication of a firm bond between different polymers, for example between polyamide and polyester. This would create the possibility of protecting certain molded bodies made of polyamide by a coating with polyester, to protect these materials against light and moisture. A molded polyester body could also be protected by a coating with polyamide to withstand chemical and mechanical influences. This would also generate the possibility of providing the fuel lines, which usually consist of a polyamide (PA) as PA 6, PA 11 or PA 12, with a protective layer for fuel, and in particular against a fuel containing alcohol . On the other hand it can be said that the laminates that consist of different layers, which show different functions, are more suitable for food packages than the layers that consist of a single material, also called mono-strata. In principle, the connections between polyamide and polyester are already known. European Patent EP-A-0 336 806 describes the combined extrusion of PA 12 and polybutylene terephthalate (PBT) to form a tube based on two layers. In the German specification DE-PS 38 27 092 a multi-layer tube is described, which seen from the inside to the outside have layers of polyamide, polyvinyl alcohol, polyamide and polyester. In any case, the expert is aware that the vast majority of polymers, also polyamides and polyesters, are incompatible with each other, so that in the manufacture of polymer laminates no adhesion is achieved between the layers of the laminates . However, it is highly desirable to have a fixed connection between the different layers of polymers, especially in modern technical applications. German specification DE-OS 196 33 133 describes a multilayer tube consisting of at least two perfectly interconnectable layers, in which one layer is a protective layer while the thermoplastic material of the second layer has been treated with polyethyleneimine as adhesive agent. However, when putting into practice the details indicated in the German Report DE-OS 196 33 133, the desired effect could not be achieved. As it would seem obvious to join for example, layers of polyester and polyamide by an adhesive agent consisting of a mixture of polyamide and polyester. In any case, these mixtures are very fragile and, as a rule, they are made by mixing melts inside an extruder. The corresponding tests on a combined extrusion, using polyamide and polyester, show an adhesion either to the polyamide or to the polyester, but the two polymers are simultaneously charged. EP-A-0 509 211 discloses multilayer thermoplastic joints, in which a layer of a molded mass of polyamide and a layer of a molded mass of polyester is joined by an adhesive agent, which contains a mixture of polyamide and polyester. Since in this case the above-mentioned problems arise, in a preferred embodiment, as regards the adhesive agent, at least a part of the polyamide and a part of the polyester are present in the form of a block copolymer based on of polyamide and polyester. The preparation of these block copolymers on the other hand is not entirely simple and requires the addition of auxiliaries or catalysts. Furthermore, precise inspection or control of the end groups is necessary since the block copolymers are manufactured by interlacing suitable end groups and therefore must be sure that the appropriate terminal groups are present in a sufficient concentration. In view of the fact that commercial products are not adapted to these requirements, it is necessary to manufacture specific types, which will then be converted into a block copolymer. The production of such adhesive agents is therefore linked with a high degree of investment expense. This is applicable to an even greater extent for the block copolyester amides, which are used as adhesive agents in multilayer joints based on polyamides and polyesters in the process according to EP-A-0 37 088. Also the unions of other materials correspond to the current state of the art. However, as a result of the incompatibility of most polymeric working materials, in the majority of cases there are certain special solutions that have their own adhesive agent, individually adapted. The task of the present invention was to offer an adhesive agent for a multilayer bond having a favorable price, which was easy to manufacture and which nevertheless had a good effectiveness. With regard to such multilayer bonding, the adhesion between the layers must also be conserved for a long time, even when the materials are in contact with certain reagents such as, for example, a fuel, solvents, oils or fats. higher temperatures. This problem has been solved by a thermoplastic-type multilayer union containing a layer I of a thermoplastic molded mass, a layer II consisting of an additional thermoplastic molded mass and between both a layer consisting of an adhesive agent consisting of less than 5% by weight and preferably at least 10% by weight and very particularly at least 20% by weight, of a graft copolymer, which is prepared using the following monomers: a) 0.5% at 25% by weight, preferably between 1% and 20% by weight and very particularly from 1.5% to 16% by weight, relative to the graft copolymer, of a polyamine containing at least 4 carbon atoms, preferably at at least 8 carbon atoms and very particularly at least 11 carbon atoms, and having a number average molecular weight Mn of at least 146 g / mol, preferably of at least 500 g / mol and very special preference of 800 g / mol, and also b) d-forming monomers and polyamides, selected from lactams,? -aminocarboxylic acids and / or equimolar combinations of diamine and dicarboxylic acid. In a preferred embodiment, the concentration of amino groups of the graft copolymer in a range of 100 to 2500 mmol / kg is present. As polyamine, for example, they can be used, the following classes of substances: - Polyvinylamines (Rummp Chemie Lexikon, 9th Edition, Volume 6, Page 4921, Editorial: Georg Thieme Verlag Stuttgart 1992), Polyamines which are made from alternating polyketones (German Memory DE-OS 196 54 058 ), - The dendrimers as for example, ((H2N- (CHa) 3) 2N- (CH2) 3) 2-N (CH2) 2-N ((CH2) 2-N ((CH2) 3-NH2) 2 ) 2 (German report DE-A 196 54 179), or Tris (2-aminoethyl) amine, t N, N-Bis (2-aminoethyl) -N ', N' -bis [2- [bis (2 - amino-ethyl) amino] ethyl] -1,2-ethanediamine, 3, 15-Bis (2-aminoethyl) -6,12-bis [2- [bis (2-aminoethyl) amino] ethyl] -9- [2 - [bis [2-bis (2-aminoethyl) amino] ethyl] 3, 6, 9, 12, 15-pentaazaheptadecan-1,17-diamine (JM Warakomski, Chem. Mat. 1992, 4, 1000-1004); The linear polyethyleneimines, which can be obtained by polymerization of 4, 5-dihydro-l, 3 -oxazoles and subsequent hydrolysis (Houben-Weyl, Methoden der Organischen Chemie, Volume E20, Pages 1482 1487, Editorial: Georg Thieme Verlag Stuttgart, 1987); The branched polyethylene imines obtainable by the polymerization of aziridines (Houben-Weyl, Methoden der Organischen Chemie, Volume E20, Pages 1482 - 1487, Editorial: Georg Thieme Verlag Stuttgart, 1987) and which as a rule have the following distribution of the amino groups : 25% to 46% of primary amino groups, 30% to 45% of secondary amino groups and 16% to 40% of tertiary amino groups. In the case of preference, the polyamine has a molecular weight of numerical average Mn of 20,000 g / mol, at most and with particular preference in a maximum of 10,000 g / mol and very particularly preferably of 5000 g / mol. The lactams or the α-aminocarboxylic acids, which are used as polyamide-forming monomers, contain from 4 to 19 and in particular from 6 to 12 carbon atoms. They prefer in particular e-caprolactam, e-aminocaproic acid, caprylic lactam, acid? -aminocaprylic acid, lactic lactam,? -aminododecanic acid and / or? -aminoundecanic acid. The combinations of diamine and dicarboxylic acid are, for example, hexamethylenediamine and dodecanediic acid, octamethylenediamine and cebasic acid, decamethylenediamine and cebasic acid, decamethylenediamine and dodecanediic acid, dodecamethylenediamine and dodecanediic acid, as well as dodecamethylene diamine and 2,6-naphthalenedicarboxylic acid. In addition, all kinds of different combinations can also be used, such as decarnet iledenediamine / dodecandiazide / terephthalic acid, hexamethylenediamine / adipic acid / terephthalic acid, hexamethylenediamine / adipic acid / caprolactam, decamethylenediamine / dodecandiazide /? -aminoundecanic acid, decamethylenediamine / dodecandiazide / laurinlactam, deca-methylenediamine / terephthalic acid / laurinlactam or dodecamethylenediamine / 2,6-naphthalenedicarboxylic acid / laurinlactam. In a further preferred embodiment, the graft copolymer is prepared using an oligocarboxylic acid, which is selected from 0.015 mol% to approximately 3 mol% dicarboxylic acid and 0.1% to approximately 1.2 mol% tricarboxylic acid, in each case. This case is related to the sum of the other polyamide-forming monomers In this reference, as regards the equivalent combination of diamine and dicarboxylic acid, each one of these monomers is individually, in this way the polyamide-forming monomers have a total slight excess of carboxylic groups If a dicarboxylic acid is used, 0.03% up to 2.2 mol%, in particular 0.05% to 1.5 mol% and preferably very particular from 0.1% to 1 mol% and especially 0.15% are preferably used. 0.65 mol%, when a tricarboxylic acid is used, then an amount of 0.02% to 0.09 mol%, with particular preference of 0.02, is preferably taken. 5% to 0.6% molar and with a very special preference from 0.03% to 0.4 molar% and particularly from 0.04% to 0.25 molar%. By using the oligocarboxylic acid comitant, the resistance to solvents and fuels, especially the resistance through hydrolysis and alcoholysis and the resistance to cracks created by stresses, but also the behavior during swelling and the dimensional resistance attached to the previous one, is clearly improved. even blocking action against diffusion. As the oligocarboxylic acid, any dicarboxylic or tricarboxylic acid having 6 to 24 carbon atoms can be used, for example, adipic acid, suberic acid, azelaic acid, cebasic acid, dodecanediic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, acid cyclohexane-1,4-dicarboxylic acid, trimesic acid and / or trimellitic acid. In addition and if desired, the aliphatic, alicyclic monocarboxylic acids can be used, aromatic, aralkyl 'and / or substituted by alkylaryl with 3- to 50 carbon atoms such as, for example, lauric acid, unsaturated fatty acids, acrylic acid or benzoic acid, as regulators. With these regulators, the concentration of amino groups can be decreased, without modifying the molecular configuration. In addition and in this way it is possible to introduce certain functional groups such as double or triple bonds, etc. But it is convenient that the graft copolymer, ie a substantial portion of amino groups. Preferably, the concentration of the amino groups of the graft copolymer is in the range of 150 to 1500 mmol / kg, most preferably in the range of 250 to 1300 mmol / kg and very particularly preferably in the range of 300 to 1100 mmol / kg. By amino groups, here and hereinafter, not only the amino end groups but also the secondary or tertiary amino functions, optionally present, of the polyamine are understood. The graft copolymers according to the invention can be made according to different methods. One possibility is to load together the lactam or? -aminocarboxylic acid as well as the polyamine as a whole and then carry out the polymerization or polycondensation. The oligocarboxylic acid can be added either at the beginning or in the course of the reaction. On the other hand, there is a preferred method in which, in the two-step process, lactam dissociation and prepolymerization are carried out in the presence of water (as an alternative, the corresponding amino-aminocarboxylic acids are directly used and prepolymerized, or its case diamines and dicarboxylic acids); in the second step, the polyamine is added, whereas the oligocarboxylic acid, which is commonly used with the present invention, is introduced before, during or after the prepolymerization. The pressure is then relieved at temperatures between 200 and 290 ° C and polycondensed in the nitrogen stream or under vacuum. Another preferred method consists in the hydrolytic cleavage of a polyamide to obtain a prepolymer to make the reaction with the polyamine simultaneously or later. Preferably, polyamides are used in which the difference between the final groups is practically zero or in which the oligocarboxylic acid optionally used at the same time is already incorporated by polycondensation. However, oligocarboxylic acid can also be added at the beginning or in the course of the splitting reaction. With this process, the ultra-high-grade branched polyamides can be prepared with acid levels of less than 40 mmol / kg, preferably less than 20 mmol / kg and particularly preferably less than 10 mmol / kg. Already after a reaction time of 1 hour to 5 hours, at temperatures between 200 ° C and 290 ° C an approximately complete conversion is achieved. If desired, in another step of the process, a phase can be combined under vacuum for several hours. This step lasts at least 4 hours, preferably at least 6 hours and with particular preference at least 8 hours, at a temperature of 200 ° C to 290 ° C. After an induction period of several hours an increase in the viscosity of the melt is then observed, which undoubtedly derives from the circumstance that a reaction of amino end groups takes place between them under dissociation of ammonia and entanglement of the chains. This further increases the molecular weight, which is particularly advantageous for the extrusion-molded masses. In case the reaction in the melt is not carried out, a subsequent condition of the branched polyamide can also be made ultra-high according to the current state of the art, also in the solid phase. A plurality of molded polymers or masses based thereon can be interconnected with this adhesive. In general terms all polymers are suitable due to their structural similarity to be physically compatible with the graft copolymer used according to the invention, such as, for example, polyamides. Also suitable are all polymers which enter the amino groups of the graft copolymer in a chemical crosslinking reaction or which at least form hydrogen bonds, for example polyester. Embodiments according to the invention are for example: a multilayer bond containing layers of different polyamide molded masses, less compatible with each other or incompatible, which are bonded by the adhesive agent according to the present invention; a multi-layered union, containing layers of different, incompatible, molded polyester masses, which are joined by the adhesive agent according to the present invention; a multilayer bond containing a layer of a molded mass of polyamide, which is bonded by the adhesive agent according to the invention to a layer consisting of another molded mass, and which is based on a polymer not containing a polyamide; a multilayer joint, containing a layer of a molded mass of polyester, which is bonded by the adhesive agent according to the invention to a layer of another molded mass, which is based on a polymer that is not a polyester; a multilayer union., containing the following layers: I. A layer I of a molded polyamide mass; II. A layer II of a molded mass of polyester; and a layer of the adhesive agent according to the present invention is interspersed. invention. As polyamides, the homocondensates and copolycondensates of the aliphatic type come into consideration here in the first instance., for example, PA 46, PA 66, PA 68, PA 612, PA 88, PA 810, PA 1010, PA 1012, PA 1212, PA 6, PA 7, PA 8, PA 9, PA 10, PA 11 and PÁ 12. (The characterization of the polyamides corresponds to the International Standard in which the first number or the first numbers indicate the number of carbon atoms of the starting diamine and the last number or the last numbers represent the number of carbon atoms of the dicarboxylic acid When no more than a single number or digit is mentioned, this means that it is based on an acid, α-aminocarboxylic acid or, where appropriate, lactama derived from it; for the rest, reference is made to H. Domininghaus, Die Kunststoffe und ihre Eigenschaften, Page 272 etc., Editorial VDI-Verlag, 1976). In the mean in which copolyamides are used, they may contain, for example, adipic acid, cebasic acid, suberic acid, isophthalic acid, terephthalic acid, naphthalene-2,6-dicarboxylic acid, etc., as co-acid or bis respectively. (4-aminocyclohexyl) methane, trimethylhexamethylenediamine, hexamethylenediamine or a similar substance such as co-diamine. The lactams can also be incorporated as caprolactam or laurinlactam or, if appropriate, aminocarboxylic acids such as? -aminoundecanic acid as co-component. The production of these polyamides is known (see, for example, B. D. 'Jacobs, J. Zimmermann, Polymerization Processes, Pages 424-467, Interscience Publishers, New York, 1977, German Report DE-AS 21 52 194). Above it can be said that mixed aliphatic / aromatic polycondensates are also suitable as polyamides, as described, for example, in US Pat. Nos. 2 071 250, 2 071 251, 2 130 523, 2 130 948, 2 241 322, 2 312 966, 2 512 606 and 3 393 210 as well as Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Edition, Volume 18, Pages 328 et seq. And 435 et seq., Editorial Wiley & Sons, 1982. Other suitable polyamides are poly (ether esters) or (ether); such products are described, for example, in German Memoirs DE-OSS 25 23 991, 27 12 987 and 30 06 961. The molded polyamide mass can contain some of these polyamides or several of them in the form of a mixture. In addition, other thermoplastics may be present in a percentage up to 40% by weight, insofar as they do not affect the adhesion capacity, particularly the rubbers that create a resistance to shocks (toughness under impact) as for example, the copolymers of ethylene / propylene or ethylene / propylene / diene (European Memory EP-A-0 295 076), polypentenylene, polyoctenylene, the copolymers structured in a static form or as blocks from alkenylaromatic compounds with olefins or aliphatic-type dienes (Memory EP-A-0 261 748) or the core-type rubbers or sheath with a tenacious elastic core from the rubber of (meth) acrylate, butadiene or styrene / butadiene with glass transition temperatures Tg < -10 ° C, in which case the core may be cross-linked and the shell may be structured on the basis of styrene and / or methyl methacrylate and / or other unsaturated monomers (German Memoirs DE-OSS 21 44 528, 37 28 685).

The customary auxiliaries and additives for polyamides can be added to the polyamide molding composition, such as, for example, flame retardants, stabilizers, auxiliary softeners for processing, fillers, especially for improving electrical conductance, reinforcing fibers, pigments or Similar. The quantity of the mentioned agents must be dosed in such a way that the desired properties are not seriously affected. Suitable polyesters are linearly structured thermoplastic polyesters. They are prepared by the polycondensation of diols with the dicarboxylic acid or, where appropriate, the polyester-forming derivatives such as dimethyl esters. Suitable diols have the formula HO-R-OH, in which R is a bivalent, straight-chain or branched aliphatic and / or cycloaliphatic radical with 2 to 40 atoms and preferably 2 to 12 carbon atoms. Suitable dicarboxylic acids have the formula HOOC-R '-COOH, where R' is a bivalent aromatic radical with 6 to 20 and preferably 6 to 12 carbon atoms. As an example of the diols, we mention ethylene glycol, trimethylene glycol, tetramethylene glycol, hexamethylene glycol, neopentyl glycol, cyclohexanedimethanol, as well as dimerdiol which is a diol with 36 carbon atoms. The diols can be used alone or as mixtures of diols. A portion of up to 25 mol% of said diol may be substituted by a polyalkylene glycol having the following general formula: wherein R "is a bivalent radical with 2 to 4 carbon atoms and x denotes a value of 2 to 50. Suitable aromatic dicarboxylic acids include, for example, terephthalic acid, isophthalic acid, 1,4-, 1,5-acid. -, 2,6- or, where appropriate, 2, 7-naphthalindicarboxylic acid, diphenic acid and diphenyl-4,4'-dicarboxylic acid Up to 30 mol% of these dicarboxylic acids can be substituted by aliphatic or cycloaliphatic dicarboxylic acids Examples of suitable polyesters are polyethylene terephthalate, polypropylene terephthalate, polybutylene terephthalate, polyethylene-2,6-naphthalate, polypropylene, polyethylene terephthalate, polyethylene terephthalate, polyethylene terephthalate. 2, 6-naphthalate and polybutylene-2,6-naphthalate The preparation of these polyesters belongs to the state of the art (German Memoirs DE-OSS24 07 155, 24 07 156, the Encyclopedia: Ullmanns Encyc lopádie der technischen Chemie, 4th Edition, Volume 19, Pages 65 et seq., Editorial Verlag, Chemie, Weinheim, 1980). The polyester molding compound can contain any of these polyesters or several of them in the form of a mixture. In addition, up to 40% by weight of other thermoplastics can be contained therein insofar as they do not affect the adhesion capacity, particularly those rubbers that create a toughness under impact, as already indicated above for polyamide. In addition, the polyester molding composition can contain those auxiliaries and additives customary for polyesters, such as, for example, fireproofing agents, stabilizers, processing aids, fillers, especially for improving electrical conductance, reinforcing fibers, pigments or the like. . The quantity of the mentioned agents must be dosed in such a way that the desired properties are not seriously affected. Generally, the polyamide molding compound has a continuous polyamide phase and the polyester molding compound has a continuous polyester phase. When the joint contains a layer of a polyamide molding compound, then the adhesion promoter in a preferred embodiment in addition to the graft copolymer contains a polyamide, and especially preferably from 10 to 90% by weight with respect to the sum of the graft copolymer and polyamide. When the joint contains a layer of a polyester molding mass, then the adhesion promoter, "in a further preferred embodiment, in addition to the graft copolymer, it also contains a polyester, particularly preferably from 10% to 90% by weight, based on the sum of the graft copolymer and polyester, when the bond contains a layer I from a polyamide molding compound and a layer II of a polyester molding compound, which are interconnected by the adhesion promoter according to the invention, it is preferred that this adhesion promoter in addition to the graft copolymer contains both a polyamide and a polyester The corresponding molding compositions are also an object of the invention In this embodiment, the adhesion promoter preferably contains the following composition: I. from 5 to 60 parts by weight of a graft copolymer which is prepared by using the following monomers: a) from 5% to 25% by weight with respect to the graft copolymer, of a polyamine containing at least 4 and preferably at least 8 and very particularly a minimum of 11 nitrogen atoms and a molecular weight of numerical average Mn of at least 146 g / mol, preferably a minimum of 500 g / mol and particularly preferably a minimum of 800 g / mol as well as b) polyamide-forming monomers selected from lactams,? -aminocarboxylic acids and / or equimolar combinations of diamine and dicarboxylic acid; II. from 10 to 85 parts by weight of a polyamide; III. from 10 to 85 parts by weight of a polyester; the sum of the parts by weight of I, II and III: 100 being; IV. a maximum of 40 parts by weight of additives, selected from rubber that causes tenacity under impacts and / or auxiliary 'and usual additives. The polyamide of the adhesion promoter must be perfectly compatible with the polyamide of layer I and must therefore allow good adhesion. Suitable combinations of polyamides are known to the person skilled in the art or can also be determined without difficulty by simple routine tests, for example by means of press plates. It is often sufficient when both polyamides have at least one monomeric module in common or when both have a corresponding monomeric module with an equal number of carbon atoms or with an equal length. The best thing is when the polyamide corresponds in a maximum to the polyamide in layer I. The same can be said for the polyester of the promoter agent which must be perfectly compatible with the polyester of layer II. In this case, too, suitable combinations of the polyesters are known to the person skilled in the art, or they can be determined easily by simple routine tests, for example using press plates. It is often sufficient when both polyesters have a monomer module in common or when the corresponding monomer modules are at least similar. The best thing is that when the polyester corresponds in a maximum to the polyester of layer II. The adhesion promoter can contain not only the graft copolymer and the polyamide and / or the polyester as possible additives but also supplementary components such as, for example, a rubber that creates the toughness under impact and / or certain auxiliaries or additives, such as they are explained in greater detail in the foregoing as possible components of layers I and II. The total amount of all the additives amounts to a maximum of 40 parts by weight, preferably a maximum of 30 parts by weight and particularly preferably a maximum of 20 parts by weight. As regards the joining of multiple layers, according to the present invention, it is, in one embodiment, a tube of an inlet channel or of a container, particularly for the conduction or supply of liquids or gases . Such a tube may be configured in a straight or wavy shape or be welded only in partial sections. The welded pipes correspond to the current state of the art (see for example, the North American Memory US 5 460 771), reason for which there are more explanations here on this subject. Important purposes of use are the use as a fuel conductor line, as a channel for the introduction of materials in tanks, such as a steam line (ie a line in which the fuels are conducted in the form of steam, such as air ducts). exhaust), as well as lines to tank assemblies, such as a line for driving cooling liquids, such as a line used in air conditioning equipment or also in the form of a fuel container. The multilayer bonding according to the present invention may also be present as a flat bond, for example, as a film such as a packaging film for food, as a body combined with its coating layer to improve the resistance to ultraviolet light or as a multi-layer extruded plate. In the use of the multilayer joint according to the present invention which serves to become a line or to supply combustible liquids, gases or powders such as fuels or fuels in the form of vapors, it is advisable to equip with qualities of electrical conductance to the layers belonging to the joint or a supplementary inner layer. This operation can be carried out by means of a compound formation with electrically conductive additive according to all kinds of methods corresponding to the current state of the art. As a conductive additive, for example, conductive soot can be used, metal shavings, powdered metal, metallized glass pellets, metallized glass fibers, metallic fibers (for example, made of stainless steel), so-called "Whiskers" (fine threads), metallized, carbon fibers (also metallized), polymers or the graphite fibrils, intrinsically conductive. It is also possible to use mixtures of different conductive additives. In the preferred case, the electrically conductive layer is in direct contact with the medium to be transported or supplied and said layer has a surface resistance of 109 ohms / cm. In the embodiment of the multilayer connection according to the invention, in the form of a tube, the latter can also be coated with an additional elastomer layer. Both rubber masses that are subject to crosslinking and thermoplastic elastomers are useful for this coating. This coating or wrapping can be applied to the tube with some additional adhesion promoter or also without the use thereof, for example, by extrusion through a transverse injection head or by the system in which a prefabricated elastomer hose is pushed around a multi-layer tube, already extruded in finished condition. The manufacture of the multilayer connection can be carried out in a single operation or in several stages, for example, by means of a single-phase process, with injection molded material composed of different components, it can also be carried out in the form of a co-extrusion or a blow molding and coextrusion and also through methods based on different stages as described, for example, in the North American Memory US 5 554 425. The union of multiple layers, in its simplest form of execution, can consist of the layer I, the adhesion promoter or layer II; with the use of additional layers on the other hand, for example, the following layer configurations may be present: Rubber / layer 1 / adhesion agent / layer II; Layer I / adhesion agent / layer II / electrically conductive layer II; Layer I / adhesion agent / layer II / adhesion agent / layer I; Layer I / adhesion agent / layer II / adhesion agent / electrically conductive layer I; Rubber / Layer 1 / adhesion agent / layer II / adhesion agent / layer I / electrically conductive layer I; Layer 11 / adhesion agent / layer i / electrically conductive layer I. The results indicated in the examples were determined with the help of the following measurement procedures. To determine the carboxyl terminal groups, 1 gram of graft copolymer was dissolved in 50 ml of benzyl alcohol under nitrogen coating at a temperature of 165 ° C. The dissolution time was 20 minutes maximum. The solution was titrated with a solution of KOH in ethylene glycol (0.05 KOH / 1) against phenolphthalein until a color change was achieved. To determine the amino groups, 1 gram of the graft copolymer was dissolved in 50 ml of m-Kresol at 25 ° C. The solution was titrated with perchloric acid by the potentiometric route. The determination of the viscosity of the solution (relative viscosity) was carried out using a 0.5% by weight solution of m-Kresol at 25 ° C according to the German Standard DIN 53727 / ISO 307. Ex emplos: In The following components were used for the tests: Graft copolymer 1: An amount of 29.7 laurinlactam was melted in a heating boiler at a temperature between 180 ° C and 210 ° C and transferred to a high-resistant polycondensation boiler. pressures. Then 1.5 kg of water and 1.71 g of hypophosphorous acid were added. The dissociation of laurinlactam was carried out at 280 ° C under the proper pressure that was adjusted and then within 3 hours the pressure was relieved at a remaining pressure of water vapor of 3 bar and 300 grams of polyethyleneimine were added (LUPASOL G 100 of the Company BASF AG, Ludwigshafen). The polyethyleneimine was incorporated at the proper pressure that was adjusted; then it was relieved at atmospheric pressure and then for 2 hours and at 280 ° C nitrogen was conducted above the melt. The transparent melt was extracted as a cord, by using a melt pump, the product was cooled in a water bath and then granulated. ? rel: 1.68 Melt temperature Tm: 175 ° C Concentration of amino groups: 225 mmol / kg. Concentration of the carboxyl end groups: < 10 mmo1 / kg. Graft copolymer 2: 9.5 kg of laurinlactam was melted in a heating boiler at a temperature of 180 ° C to 210 ° C and the material was transferred to a high pressure resistant polycondensation tank. Then 475 grams of water and 0.54 grams of hypophosphorous acid were added. The dissociation of the lactam was carried out at 280 ° C under the proper pressure that was adjusted. Then, within 3 hours, the tension was relieved to a level of the remaining water vapor of 5 bar and 500 grams of polyethyleneimine (LUPASOL G 100 from BASF AG, Ludwigshafen) were dosed into the material, as well as 15 grams of dodecandiazide. Both components were incorporated under the proper pressure that was adjusted and then relieved at atmospheric pressure. Then nitrogen was conducted over the melt at a temperature of 280 ° C, for a period of 2 hours. The transparent melt was extracted as through a melt pump, in the form of a cord, which was cooled in a water bath and then converted into granules. ? reí: 1-52 Melt temperature Tm: 169 ° C Concentration of amino groups: 810 mmol / kg. Concentration of the carboxyl end groups: < 10 mmol / kg. PA 1: PA 12 molding compound, extrudable, with? Re? = 2.1 and with an excess of carboxyl end groups. PA 2: PA 12 molding compound, extrudable, with? rei = 2.1 and with an excess of amino terminal groups. PES 1: VESTODUR 1000, a homopolybutylene terephthalate from the company Degussa-Hüls AG with a solution viscosity J, measured in phenol / o-dichlorobenzene (1: 1), of 107 cm3 / g. PES 2: VESTODUR 1000, a homopolybutylene terephthalate from the company Degussa-Hüls AG which has a solution viscosity J of 164 cm3 / g. EXXELOR VA 1803: A functionalized EPM rubber with approximately 1% maleic acid anhydride from Exxon Chemical, Cologne. Polyamide of Layer I: PA 3: A PA 12 molding compound, extrudable, softened and modified in terms of its low impact toughness with a? Re value? equivalent to 2.1 and an excess of carboxyl end groups. Layer II polyester: PES 3: VESTODUR 2000, a homopolybutylene terephthalate from Degussa-Hüls AG which has a solution viscosity J of 145 cm3 / g. Example 1 : At a temperature of 250 ° C and a pressing time of 30 seconds, a 3-layer connection was made in a plate pressed from PA 3, the graft copolymer 1 as adhesive agent and the PES 3. In this case an inseparable union with respect to both the polyester layer and the polyamide layer. Example 2: As in Example 1, but now with graft copolymer 2 as an adhesion agent. Also in this case an inseparable adhesion was obtained both with respect to the polyester layer and polyamide layer. Comparative Example 1: As in Example 1 a pressed plate joint was made from PA 3 and PS 3. Instead of the graft copolymer 1, LUPASOL G 100 was applied in its very anhydrous form in an anhydrous form on the side top of the plate composed of PA 3, which had to be joined to PS 3. After pressing and cooling, the plate was removed and the adhesion of the layers was verified. Here it turned out that he did not find any adhesion present. Comparative Example 2: In a laboratory mixer, Haake type, according to Table 1, 4 different mixtures of PA 2 and polyethyleneimine (LUPASOL G 100 in anhydrous form from BASF AG, Ludwigshafen) abla 1; Mixtures of Polyamide and Polyethyleneimine The mixing was carried out within 8 minutes at 180 ° C and at 64 revolutions per minute. The mixtures were then comminuted and the material was applied on an injection-molded plate based on PES 1, which was in a press mold. The pressing was then carried out as indicated in Example 1. In all four cases, when checking the adhesion of the layers, it turned out that the joint, in its bordering areas, could be separated by hand. Adhesive Agents Mixtures; HV 1 (not according to the present invention): An amount of 12.6 kg of PA 1 and 22.82 kg of PES 1 was mixed to form a melt, in a double screw auger ZE 25 33D of the Berstorff house at a temperature of 270 ° C and with 200 revolutions per minute and with a flow rate of 10 kg / h, then pressed the material to form beads that were granulated. HV 2 (according to the invention): An amount of 12.6 kg of PA 2, 22.82 kg of PES 1 and 5.0 kg of the graft copolymer 2 were melt-mixed in a ZE 25 33D twin-screw kneader from the Berstorff house. a temperature of 270 ° C and with 150 revolutions per minute and with a flow rate of 10 kg / h, then the material was pressed to form a cord and granulated. HV 3 (according to the invention): An amount of 12.6 kg of PA 2, 22.82 kg of PES 2 and 5.0 kg of the graft copolymer 2 were mixed in a melt in a ZE 25 33D twin screw kneader from the Berstorff house at 270 ° C and a 150 revolutions per minute, with a flow rate of 10 kg / h, the material was pressed to form beads that were granulated. HV 4 (according to the invention): It was treated as HV 3 but with the additional use of 4.0 kg EXXELOR VA 803. Comparative Example 3 and Examples 3 to 5; To make the multilayer joints, a coextrusion mold of small bands with an output width of 30 mm was used, in which the union of the different layers in the mold was made shortly before the melt left the mold. The mold was fed from three Storck 25 extruders. After the exit of the mold, the three-layer joint was deposited on a roll mill with cooling and was removed from the equipment ("Chill-Roll" procedure). The results have been consigned to the following Table; the adhesion ratings presented here mean the following: 0 There is no accession. 1 Slight adhesion. 2 A little adhesion; It can be separated with little effort. 3 Good adhesion; It can only be separated with great effort and eventually with the help of tools. 4 Union not separable.

Table 2: Elaboration of Small Bands based on Three Layers Examples 4 and 5 according to the invention were further repeated in a modified form, three-layer tubes are elaborated with the corresponding configuration of the layers (with PA 3 as outer layer). The results have the same coating value (in all cases with an adhesion rating of 4). In all the investigated cases, the long-term resistance of the multilayer joints in contact with the fuel containing alcohol at 40 ° C as well as at 60 ° C was highlighted.

Claims (22)

1. CLAIMS; 1. A multilayer thermoplastic bond containing the following layers: I. a layer I consisting of a thermoplastic molding compound; II. a layer II consisting of another thermoplastic molding mass with an interlayer layer consisting of an adhesion agent comprising at least 5% by weight of a graft copolymer which is produced using the following monomers: a) 0.5% to 25% by weight, with respect to the graft copolymer, of a polyamine containing at least 4 nitrogen atoms and with a molecular weight with numerical average Mn of at least 146 grams per mole, as well as b) monomers forming polyamides, selected from lactams,? -aminocarboxylic acids and / or equimolar combinations of diamine and dicarboxylic acid.
2. 2. A multilayer connection of thermoplastic material according to claim 1, characterized in that at least one of the caps I and II consists of a polyamide molding compound or a polyester molding compound.
3. 3. The joining of multiple layers of thermoplastic material according to any one of the preceding claims, characterized in that layer I consists of a polyamide molding compound and layer II of a polyester molding compound.
4. 4. The multilayer joining of thermoplastic material according to any of the preceding claims, characterized in that the polyamine contains at least 8 nitrogen atoms.
5. 5. The joining of multiple layers of thermoplastic material according to any of the preceding claims, characterized in that the polyamine contains at least 11 nitrogen atoms.
6. 6. The joining of multiple layers of thermoplastic material according to any of the preceding claims, characterized in that the polyamine has a molecular weight of numerical average Mn of at least 500 grams per mole.
7. 7. The multilayer joining of thermoplastic material according to any of the preceding claims, characterized in that the polyamine has a molecular weight of numerical average Mn of at least 800 grams per ton.
8. 8. The joining of multiple layers of thermoplastic material according to any of the preceding claims, characterized in that the concentration of the amino groups of the graft copolymer is in the range of 100 to 2500 mmol per kg.
9. 9. The multiple layer joining of thermoplastic material according to any of the preceding claims, characterized in that the graft copolymer is made with the use of the following additional monomers: c) the oligocarboxylic acid selected from 0.015% up to about 3 mol% acid dicarboxylic acid and 0.1% to approximately 1.2 mol% tricarboxylic acid, in each case based on the sum of the other polyamide-forming monomers.
10. 10. The multilayer joining of thermoplastic material according to any of claims 2 and 3, characterized in that the adhesion agent also contains a polyamide and / or a polyester in addition to the graft copolymer. The multilayer joining of thermoplastic material according to any of the preceding claims, characterized in that it contains more than a single layer I and / or more than a single layer
11. II. The joining of multiple layers of thermoplastic material according to any of the preceding claims, characterized in that one of the layers has been adjusted with electrical conductance. The joining of multiple layers of thermoplastic material according to any of claims 1 to 11, characterized in that after the inner end layer follows another additional layer, which has electrical conductance. 14. The multiple layer bonding according to any of the preceding claims, characterized in that it constitutes a tube. 15. The multiple layer bonding according to claim 14, characterized in that it is corrugated in total or in partial areas. 16. The multiple layer bonding according to any of claims 14 and 15, characterized in that after the outer outer layer another rubber layer follows. 17. The multilayer connection according to any of claims 14 to 16, characterized in that it constitutes a fuel line, a liquid brake line, a line for cooling liquid, a line for hydraulic fluid, a line that leads to equipment of tanks, a climate conditioning line or a line of vapors ("Vapor Line"). 18. The multiple layer bonding according to any of claims 1 to 13, characterized in that it constitutes a hollow body. The multilayer connection according to any of claims 1 to 13 and 18, characterized in that it is a container, especially a container for containing fuel or an inlet channel, especially a tube for filling a tank. 20. A multi-layer joint according to any of claims 1 to 13, characterized in that it is a film or a multilayer film. 21. The multilayer bonding according to any of the preceding claims, characterized in that it has been made with injected casting material based on multiple components, through a coextrusion or in blow molds with coextrus ion. 22. The molding composition containing the following components: I. From 5 to 60 parts by weight of a graft copolymer which has been prepared using the following monomers: a) 0.5 to 25% by weight with respect to the graft copolymer, of a polyamine containing at least 4 nitrogen atoms and a number average molecular weight Mn of at least 146 grams per mole, as well as b) Polyamide-forming monomers selected from lactams,? -aminocarboxylic acids and / or equimolar combinations of diamine and dicarboxylic acid; II. From 10 to 85 parts by weight of a polyamide; III. From 10 to 85 parts by weight of a polyester; in which the sum of the parts by weight of I, II and III reaches 100; IV. A maximum of 40 parts by weight of additives selected from rubber that forms the toughness under impact and / or the usual auxiliaries and additives.