MXPA00005171A - Adhesion-stable composite material comprising polyurethane and a further thermoplastic material, a method for its manufacture and its use in vehicles - Google Patents

Abstract

Composite material comprising bonded layers of polyurethane with a residual ether group content of at most 400 ppm, preferab below 100 ppm, and of a different thermoplastic. Composite material comprising bonded layers of different polymers comprises a composite layer of polyurethane (PU) with a residual ether group content of at most 400 ppm, preferably below 100 ppm, and a composite layer of different thermoplastic. An Independent claim is included for the production of the composite material by contacting the layers.

Description

Composite material stable to the adhesion of polyurethane v • other thermoplastic material. a procedure for your Fa > tion as well as their use in automobiles Description of the invention: The subject of the present invention are composites composed of at least two distinct layers of plastic material bonded directly to each other, of which one layer is polyurethane and the layer directly bonded to each other. This is another thermoplastic plastic material different from that. It is known that products composed of thermoplastic material and a polyurethane / especially a polyurethane foam material do not have sufficient bonding strength. This bonding bond can be improved by using layers of bonding agents. However, this is not desirable in the use in the automotive industry, where such composite materials are increasingly used, because due to the required processing and recycling possibilities the least possible amount of different materials should be used. The objective has therefore been to improve the bond between a polyurethane layer and a layer of another thermoplastic material bonded directly thereto. The objective is achieved according to the invention by providing a composite material which is constituted by at least two layers bonded directly together, of which A) a layer of the composite material is polyurethane REF .: 120559 obtained by reaction of polyisocyanates with polyfunctional compounds with active H and B) a layer of the composite material bonded directly thereto is of a thermoplastic plastic different from that of A), characterized in that layer A) presents the preparation of the polyurethane a residual content of reaction components containing ether groups that have not reacted with the isocyanate component of 400 ppm maximum, preferably <100 ppm. The polyurethanes or polyurethanes which are used according to the invention in layer A) are obtained by reacting polyisocyanates with polyfunctional compounds with active H, preferably polyols. As the polyisocyanate component, those known from the chemistry of polyurethanes and commonly used therein are preferably considered. This applies in particular to aromatic-based polyisocyanates, for example 2-diisocyanatotoluene, their technical mixtures with 2, 6-diisocyanatotoluene, 4, '-diisocyanatodiphenylmethane, their mixtures with the corresponding 2,4'- isomers and 2,2'-, mixtures of polyisocyanates of the diphenylmethane series, such as those obtained in a known manner by condensation phosgenation of aniline / formaldehyde, the modification products having biuret or isocyanate groups of these technical polyisocyanates and especially prepolymers NCO of the type indicated based on these technical polyisocyanates on the one hand and the polyols and / or polyether polyols and / or polyester polyols * indicated by way of example on component A) described below, on the other, as well as discrete mixtures of such diisocyanates, both are sufficiently stable to storage. Among the modified polyisocyanates of high molecular weight, the known prepolymers of the polyurethane chemistry with terminal isocyanate groups, with a molecular weight in the range of 400 to 10,000 g / mol, preferably of 600 to 8,000 g / mol and of especially from 800 to 5,000 g / mol. These compounds are obtained in a manner known per se by reacting excess amounts of simple polyisocyanates of the type indicated by way of example with organic compounds with at least two groups reactive towards isocyanate groups, especially organic polyhydroxy compounds. Suitable polyhydroxyl compounds of this type are both simple polyvalent alcohols with a molecular weight in the range from 82 to 599 g / mol, preferably from 62 to 200 g / mol, such as, for example, ethylene glycol, trimethylpropane, propanediol-1, 2 or butanediol-1, 4 or > butanediol-23, in particular those polyether polyols and / or high molecular weight polyol esters of the type known per se from the chemistry of polyurethanes with molecular weights of 600 to 8,000 g / mol, preferably 800 to 4,000 g / mol, which have minus 2, as a rule from 2 to 8, but preferably from 2 to 4, primary and / or secondary hydroxyl groups. Naturally, it is also possible to use NCO prepolymers obtained, for example, from low molecular weight polyisocyanates of the type indicated by way of example and less preferred compounds with groups reactive towards isocyanate groups, such as polyol thioethers, polyacetals they have hydroxyl groups, polyhydroxycarbonates, polyesteramides having hydroxyl groups or copolymers of olefinically unsaturated compounds having hydroxyl groups. For the preparation of the NCO prepolymers are compounds with groups reactive towards isocyanate groups, especially suitable hydroxyl groups, for example the compounds described by way of example in US-PS 4 218 543, column 7, line 29 to column 9, line 25. In the preparation of the NCO prepolymers these compounds are reacted with groups reactive towards isocyanate groups with simple polyisocyanates of the type indicated above by way of example maintaining an excess of NCO. The NCO prepolymers generally have an NCO content of 10 to 25, preferably 15 to 22% by weight. From this it already follows that in the context of the present invention "NCO prepolymers" or "prepolymers with terminal isocyanate groups" are to be understood as the reaction products as well as their mixtures with excess amounts of starting polyisocyanates which do not have reacted, which are often also called "se iprepolímeros". The polyisocyanate component has an average functionality of 2 to 3, preferably of 2.3 to 2.7. For the adjustment of a certain NCO content of the isocyanate component it may be convenient to mix proportions of crude MDI with an NCO prepolymer. The proportions of highly functionalized material (functionality > 4) contained in the raw MDI can be tolerated without delay provided the average functionality of 3 is not exceeded until that of the isocyanate component. As aliphatic diols with an index of OH > 200 mg KOH / g, preferably > 500 mg of KOH / g, are considered the cross-linked chain extenders common in the chemistry of polyurethanes, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, butanediol-1,4, propanediol-1,3. Preferred diols are those which have improved compatibility with the polyols (ii) of component B). Mention may be made, for example, of butanediol-1,4-butanediol-1,3-butanediol-2, 3, 2-methyl-propanediol-1, 3. Of course, it is also possible to use the aliphatic diols in admixture with one another.

Polyols with an average OH value of 5 to 500 mg KOH / g and an average functionality of 2 a are suitable as components with active H. Preferred are those with an average OH number of 10 to 50 mg KOH / g and an average functionality of 2.7 to 3. Such polyols are, for example, polyhydroxyethers known from the chemistry of polyurethanes and can be obtained by alkoxylation of suitable starter molecules such as ethylene glycol, diethylene glycol, 1,4-dihydroxybutane, 1,6-dihydroxyhexane, dimethylolpropane, glycerin, pentaerythritol, sorbitol or sucrose. Ammonia or amines, such as ethylenediamine, hexamethylenediamine, 2,4-diaminotoluene, aniline or aminoalcohols or phenols, such as bisphenol A, can be used as the initiators. The alkoxylation is carried out using propylene oxide and / or ethylene oxide in a discrete sequence. Polyester polyols such as those obtainable in a manner known per se by the reaction of low molecular weight alcohols with polyvalent carboxylic acids, such as adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid or the anhydrides of these acids, are also suitable. that the viscosity of the active H component is not too high. A preferred polyol, which has ester groups, is castor oil. Also suitable are castor oil preparations such as those obtained by dissolving resins, eg aldehyde-ketone resins, as well as castor oil and polyol modifications based on other natural oils. High molecular weight polyhydroxyethers in which polyadducts or polycondensates or high molecular weight polymerized polymers are present in finely dispersed, dissolved or grafted form are also suitable. Such modified polyhydroxy compounds are obtained, eg, if polyaddition reactions are developed (eg reactions between polyisocyanates and aminofunctional compounds) or polycondensation reactions (eg between formaldehyde and * phenols and / or amines) in in the compounds that have hydroxyl groups. Such processes are described, for example, in DE-AS 1 168 075 and 1 280 142 as well as in DE-A-2 324 134, 2 423 984, 2 512 385, 2 513 815, 2 550 796, 2 550 797 , 2 550 833, 2 550 882, 2 633 293 and 2 639 254. But it is also possible according to US-A-3 869 413 or DE-A-2 550 860 to mix a prepared aqueous dispersion of polymer with a compound polyhydroxylic and then remove the water from the mixture. Also suitable for the preparation of polyurethanes are polyhydroxy compounds modified with vinyl polymers such as are obtained, for example, by polymerization of styrene and acrylonitrile in the presence of polyethers.

(US-A-3 383 351, 3 304 273, 3 533 093, 3 110 695; DE-A-1 152 536) or polycarbonate polyols (DE-B 1 769 795; US-A-3 637 909). When polyether polyols which have been modified by graft polymerization are used according to DE-A-2 442 101, 2 844 922 and 2 646 141 with vinyl phosphonic acid esters, as the case may be (meth) acrylonitrile, (meth) acrylamide or acid esters (methyl) acrylic, plastics with special non-flammability are obtained. Representatives of the compounds to be used indicated as active H compounds are described, eg, in High Polymers, vol. XVI, "Polyurethanes Chemistry and Technology", by • Saunders-Frisch, Interscience Publishers, New York / 'London, Volume 1, 1982, p. 32-34 and pages 44-54 and Volume II, 1984, pages 5-6 and 198-199, as well as in Kunststoff-Handbuch, Volume VII, Carl Hanser Verlag, Munich, 1983, eg on pages 45- 61 Obviously, mixtures of the mentioned compounds can also be used. The limitation of the average OH index and the average functionality of the component with active H is given in particular by the increasing fragility of the resulting polyurethane, but basically the possibilities for influencing the physical properties of the polymer of the polymer are known to the person skilled in the art. polyurethane so that the NCO component, aliphatic diol and polyol can be coordinated in a suitable manner with each other. The layer A) of the composite material can be foamed or solid, for example as a lacquer or coating. In this respect, all known adjuvants and additives, such as for example mold release agents, blowing agents, fillers, catalysts and flame retardants, can be used. In this respect, the following can be used as adjuvants and additives: a) Water and / or easily volatile inorganic or organic substances as blowing agents. Suitable organic blowing agents are, for example, acetone, ethyl acetate, halogen-substituted alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane, • in addition to butane, hexane , heptane or diethyl ether, as inorganic blowing agents, eg air, C02 or N20. An expansion effect can also be achieved by the addition of compounds which, at temperatures above room temperature, decompose by removing gases, for example nitrogen, for example azo compounds such as azodicarbonamide or azobutyronitrile. Other examples of blowing agents as well as details on the use of blowing agents are described in Kunststoffhandbuch, Volume VII, edited by Vieweg and Hochtlen, Carl-Hanser Verlag, Munich 1966, eg on pages 108 and 109, 453 to 455 and 507 to 510. b) Catalysts of a type known per se, eg tertiary amines, such as triethylamine, tributylamine, N-methylmorpholine, N-ethyl-morpholine, N, N, N ', N' - tetramethylenediamine, pentamethyl-diethylenetriamine and higher homologs (publications for German patent application DE-2 624 257 and 2 624 528), 1,4-diaza-bicyclo- (2, 2, 2) -octane, N- methyl-N '-dimethylaminoethyl-piperazine, bis- (dimethylaminoalkyl) -piperazines (publication for German patent application DE-2 737 787), N, N-dimethylbenzylamine, N, N-dimethylcyclohexylamine, N, N-diethylbenzylamine, bis- (N, N-diethylaminoethyl) -adipate, N, N, N ', N'-tetramethyl-l, 3-butanediamine, N, N-dimethyl-β-phenylethylamine, 1,2-dimethylimidazole, 2- meti limidazole # monocyclic and bicyclic amidines (publication for information of * German patent application DE-1 720 633), bis- (dialkylamino) alkyl ethers (patent publication US-3 330 782, publication for call for oppositions of patent application German DE-1 030 558, publications for German patent application DE-1 804 361 and 2 618 280) as well as tertiary amides having amide groups (preferably formamide groups) according to the publications for German patent application information DE -2,523,633 and 2,732,292. Mannich bases of secondary amines known per se, such as dimethylamine, and aldehydes, preferably formaldehyde, or ketones such as acetone, methyl ethyl ketone or cyclohexanone and phenols, such as phenol, nonylphenol or Bisphenol Tertiary amines having hydrogen atoms active against isocyanate groups as catalyst are, for example, triethanolamine, triisopropylamine, N-methyl-diethanolamine, N-ethyl-diethanolamine, N, N-dimethyl-ethanolamine, their reaction products with alkylene oxides such as propylene oxide and / or ethylene oxide as well as secondary and tertiary amines according to the publication for German patent application DE-2 732 292. As catalysts are further considered silaa inas with carbon-silicon bonds, such as those described, for example, in German patent publication DE-1 229 290 (corresponding to US patent publication US-3 620 984), eg 2,2,4-trimethyl-2-syllamorpholine and 1,3-diethyl-aminomethyl-disiloxane. As catalysts, nitrogenous bases are also considered as tetraalkylammonium hydroxides, furthermore alkali hydroxides such as sodium hydroxide, alkaline phenolates such as sodium phenolate or alkali alcoholates such as sodium methylate. Hexahydrotriazines can also be used as catalysts (publication for German patent application DE-1 769 043). The reaction between NCO groups and active hydrogen atoms is strongly accelerated with lactam and azalactams, first forming an associate between the lactam and the compound with hydrogen-acid. Such partners and their catalytic activity are described in the publications for German patent application DE-2 062 286, 2 062 289, 2 117 576 (US patent publication US-3 758 444), 2 129 198, 2330 175 and 2 330 211. Organometallic compounds, in particular organic tin compounds, can also be used as catalysts. As organic tin compounds, sulfur-containing compounds such as di-n-octyl tin mercaptide are also considered (publication for call to oppositions of German patent application DE-1 769 367, US patent publication US-3 645 927) preferably tin (II) salts of carboxylic acids such as tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and tin (II) laurate, and tin (IV) compounds, e.g. dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dimethyltin dilaurate, dibutyltin maleate or dioctyltin diacetate. Obviously, all the above-mentioned catalysts can be used as mixtures. Of particular interest in this regard are combinations of organometallic compounds and amidines, aminopyridines or hydrazinopyridines (publications for German patent application DE-2 434 185, 2 601 802 and 2 603 834). Other representatives of catalysts to be used according to the invention as well as details on the mode of action of the catalysts are described in the Kunststoff-Handbuch, Volume VII, edited by Vieweg and Hochtlen, Carl-Hanser Verlag, Munich 1966, eg on pages 96 to 102. The catalysts are generally used in an amount between approximately 0.001 and 10% by weight, based on the total amount of compounds with at least two hydrogen atoms reactive with respect to isocyanates. c) Surfactants, such as emulsifiers and foam stabilizers. Suitable emulsifiers are, for example, the sodium salts of castor oil sulfonates or salts of fatty acids with amines such as oleic acid with diethylamine or stearic acid with diethanolamine. Sulphonic acids such as "dodecylbenzenesulfonic acid or dinaphthylmethane-disulfonic acid or fatty acid such as ricinoleic acid or polymeric fatty acids can also be used as the sulphonic acid additives." As foam stabilizers, polyethersiloxanes, in particular water-soluble representatives, are considered. These compounds are generally structured such that a copolymerized ethylene oxide and propylene oxide with a polydimethylsiloxane moiety are attached, such foam stabilizers are described, for example, in US Patent Publication US-2 834 748. 2 917 480 and 3 629 308. Of particular interest are copolymers of polysiloxane-polyoxyalkylene multiply branched via allophanate groups according to the publication for German patent application DE-2 558 523. d) Reaction retarders, e.g. Acid reaction substances such as hydrochloric acid or halides of organic acids, furthermore cellular regulators of a type known per se as paraffins or fatty alcohols or dimethylpolysiloxanes as well as pigments or dyes or flame retardants of known type per se, eg tris-chloroethyl phosphate, phosphate tricresilo or ammonium phosphate and polyphosphate, in addition stabilizers against aging or weathering, plasticizers and. fungistatically and bacteriostatically active substances as well as fillers such as barium sulphate, diatomaceous earth, soot or washed chalk. Other examples of surfactant additives and foam stabilizers as well as cell regulators, reaction retarders, stabilizers, flame retardants, plasticizers, dyes and fillers as well as fungistatically and bacteriostatically active substances to be used according to the invention as well as details on the mode of application and action of these additives are described in the Kunststoff-Handbuch, Volume VII, edited by Vieweg and Höchtlen, Carl-Hanser Verlag, Munich 1966, eg on pages 103 to 113. As thermoplastic plastics of the layer B) are all known thermoplastics, preferably thermoplastic polyolefins, such as, for example, polypropylenes or polyethylenes, polycarbonates, polyester carbonates, copolymers of styrene, graft styrene copolymers containing rubber, such as ABS polymers, polyamides and / or mixtures thereof thermoplastic In particular, the following polymers are suitable as thermoplastic plastic B): Polyolefins such as high and low density polyethylene, that is, densities from 0.91 g / cm3 to 0.97 g / cm3, which can be prepared by known methods, Ullmann ( 4.), JJ, page 167 et seq., Innacker-Kückler (4.), 6, 353 to 367, Elias and Vohwinkel, Neue Polymere Werkstoffe für die industrielle Anwendung, Munich, Hanser 1983.

Further, polypropylenes with molecular weights of 10,000 g / mol to 1,000,000 g / mol which can be prepared by known methods, Ullmann (5.), A10, are suitable. page 615 ff., Houben-Weyl E20 / 2. page 722 ff., Ullmann (4.), 19_, page 195 ff., Kirk-Ohtmer (3.), 1 £, page 357 ff. However, copolymers of the indicated olefins or with other α-olefins are also possible, such as, for example, ethylene polymers with butene, hexene and / or octene EVA (ethylene-vinyl acetate copolymers) EEA (ethylene-ethyl acrylate copolymers) ) EBA (ethylene-acrylate copolymers) butyl) EAS (copolymers of acrylic acid-ethylene acrylate) EVK (ethylene-vinylcarbazole copolymers) EPB (ethylene-propylene block copolymers) EPDM (ethylene-propylene-diene copolymers) PB (Polybutylenes) PMP (Polymethylpentenes) PIB (Polyisobutylenes) NBR (acrylonitrile-butadiene copolymers) Copolymerized polybutylenes of methyl-butylene Copolymers of isoprene-isobutylene Preparation procedure: These polymers are described, for example, in Kunststoff-Handbuch, Volume IV, Hanser Verlag, Ullmann (4.), 19., page 167 ff., Winnacker-Kückler (4.), 6, 353-367, Elias and Vohwinkel, Neue Polymeré Werkstoffe, Munich, Hanser 1983, Franck and Biederbick, Kunststoff Kompendium Würzburg, Vogel 1984. Thermoplastic aromatic polycarbonates, especially those based on diphenols of formula (I), are also suitable thermoplastics according to the invention for layer B) of the composite material. wherein A is a single bond, alkylene Ca-C5, C2-C5 alkylidene, C5-C6 cycloalkylidene, -S-, -S02-, -O-, -CO-, - or a C6-C12 arylene residue, which optionally it may be condensed with other aromatic rings containing heteroatoms, the B moieties, independently of each other, a respective Cx-C8 alkyl, C6-C10 aryl, especially phenyl, C7-C12 aralkyl, preferably benzyl, halogen, preferably chlorine, bromine, x independently of each other, respectively 0, 1 or 2 and p 1 or 0, ~ < ~ -o alkyl substituted dihydroxyphenylcycloalkanes of formula (II), wherein R 1 and R 2, independently of each other, respectively hydrogen, halogen, preferably chlorine or bromine, C 1 -C 6 alkyl, C 5 cycloalkyl, C 6 -C 10 aryl, preferably phenyl, and C 7 -C 12 aralkyl, preferably phenyl-C 1 -C 6 alkyl. C ^ especially benzyl, m an integer from 4 to 7, preferably 4 or 5, R3 and R4 independently selectable for each Z individually, independently from each other, hydrogen or Cx-Cg alkyl, preferably hydrogen, methyl or ethyl, and Z carbon, with the proviso that in at least one Z atom, R3 and R4 simultaneously mean alkyl. Suitable diphenols of formula (I) are, for example, hydroquinone, resorcin, 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -propane, 2,4-bis- (4-hydroxyphenyl) -2 -methylbutane, 1,1-bis- (4-hydroxyphenyl) -cciohexane, 2,2-bis- (3-chloro-4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dibromo-4-) hydroxyphenyl) - • propane. Preferred diphenols of formula (I) are 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3,5-dichloro-4-hydroxyphenyl) -propane and 1,1-bis- ( 4-hydroxyphenyl) -cydohexane. Preferred diphenols of formula (II) are dihydroxydiphenylcycloalkanes having 5 and 6 C atoms in the ring in the cycloaliphatic radical [(m = 4 or 5 in formula (II)], such as, for example, diphenols of the formulas (He), with 1, 1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (Formula I) being especially preferred. Suitable polycarbonates according to the invention can be branched in a known manner, in particular preferably by incorporation of 0.05 to 2.0 mole%, based on the sum of the diphenols used, of trifunctional or more than trifunctional compounds, e.g. eg those with three or more phenolic groups, for example Floroglucin, 4,6-Dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene-2,4,6-dimethyl-2,4,4- tri- (4-hydroxyphenyl) -heptene, 1, 3, 5-Tri- (4-hydroxyphenyl) -benzene, 1,1-tri- (4-hydroxyphenyl) -ethane, Tri- (4-hydroxyphenyl) - Phenylmethane, 2,2-Bis- (4, -bis- (4-hydroxyphenyl) -cyclohexyl-propane, 2,4-Bis- (4-hydroxyphenyl) -isopropyl) -phenol, 2,6-Bis- (2- hydroxy-5'-methyl-benzyl) -4-methylphenol, 2- (4-Hydroxyphenyl) -2- (2,4-dihydroxyphenyl) -propane, ortho-terephthalate of hexa- (4- (4-hydroxyphenyl-isopropyl) phenyl), Tetra- (4-hydroxyphenyl) -methane, Tetra- (4- (4-hydroxyphenyl-isopropyl) -phenoxy) -methane and 1,4-Bis- ((4 ', 4"-dihydroxytriphenyl) -me useful) -benzene. Some of the other trifunctional compounds are 2,4-dihydroxybenzoic acid,. trimesinic acid, cyanuric chloride and 3, 3-bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole. Preferred polycarbonates besides the * bisphenol homopolycarbonate A are bisphenol A copolycarbonates with up to 15 mol%, based on the sum of diphenols, of 2,2-bis- (3, 5-dibromo-4-hydroxyphenyl) -propane . The aromatic polycarbonates which are used for the manufacture of layer B) of the composite material can be partially replaced by aromatic polyester carbonates. The aromatic polycarbonates and / or polyester carbonates of component A are known from the literature or can be prepared by processes known from the literature (for the preparation of aromatic polycarbonates see for example Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964). The preparation of aromatic polycarbonates and / or polyester carbonates can be carried out, for example, by reacting diphenols with carbonic acid halides., preferably phosgene and / or dihalogenides of dicarboxylic acids, preferably dihalogenides of benzenedicarboxylic acids, according to the interface process, optionally using a chain switch and optionally using a trifunctional or more than trifunctional branch. Furthermore, they are suitable as thermoplastic plastics for layer B) copolymerized styrene of one or at least two ethylenically unsaturated monomers (vinyl monomers), such as styrene, α-methylstyrene, substituted styrenes in the nucleus, acrylonitrile, methacrylonitrile, methacrylate of methyl, maleic anhydride, substituted N-maleiimides and esters of (meth) acrylic acid with 1 to 8 carbon atoms in the alcohol component. The copolymers are resin-type and rubber-free. Preferred styrene copolymers are those of at least one monomer from the series of styrene, α-methylstyrene and / or styrene substituted in the core with at least one monomer from the series of acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride and / or N-substituted maleiimide. Especially preferred weight ratios in the thermoplastic copolymer are from 60 to 95% by weight of styrene monomers and from 40 to 5% by weight of the other vinyl monomers. Especially preferred copolymers are those of styrene with acrylonitrile and optionally with methyl methacrylate, of a-methylstyrene with acrylonitrile and optionally with methyl methacrylate, or of styrene with a-methylstyrene with acrylonitrile and optionally with methyl methacrylate. . The copolymers of styrene-acrylonitrile are known and can be prepared by radical polymerization, in particular by emulsion, suspension, solution or block polymerization. The copolymers preferably have molecular weights M "(weight average, determined by light scattering or sedimentation) between 15,000 and 200,000 g / mol. Are too . Especially preferred copolymerized copolymerized, statistically structured copolymers of styrene and maleic anhydride, which can preferably be obtained by continuous block or solution polymerization in incomplete reactions of the corresponding monomers.

The proportions of the two components of the styrene-maleic anhydride copolymers structured statistically suitable according to the invention can vary within wide limits. The preferred content of maleic anhydride is between 5 and 25% by weight. Instead of styrene the polymers can also contain styrenes substituted in the nucleus, such as p-methylstyrene, 2,4-dimethylstyrene and other substituted styrenes, such as α-methylstyrene. The molecular weights (number average Mn) of the styrene-maleic anhydride copolymers can vary over a wide range. The preferred range is between 60. 000 and 200,000 g / mol. For these products, a limit viscosity of 0.3 to 0.9 is preferred (measured in dimethylformamide a • 25 ° C). They are also suitable as thermoplastic plastics for layer B) copolymerized grafts. These comprise graft copolymers with rubber elastic properties, which can be obtained. essentially from at least 2 of the following monomers: chloroprene, butadiene-1,3, isopropene, styrene, acrylonitrile, ethylene, propylene, vinyl acetate and esters of (meth) acrylic acid with 1 to 8 carbon atoms in the alcohol component; that is, polymerized as described, for example, in "Methoden der organischen Chemie" (Houben.Weyl), Volume 14/1, Georg Thieme Verlag Stuttgart 1961, p. 393-406. Preferred graft copolymers are partially crosslinked and have gel contents of greater than 20%, preferably greater than 40%, in particular greater than 60% by weight. Graft copolymers which are preferably used are, for example, copolymers of styrene and / or acrylonitrile and / or esters of (meth) acrylic acid grafted onto polybutadiene, EPDM, copolymerized butadiene / styrene and acrylic rubbers of the type described; polybutadienes, copolymers of butadiene / styrene or butadiene / acrylonitrile, polyisobutenes or polyisoprenes grafted with esters of acrylic or methacrylic acid, vinyl acetate, acrylonitrile, styrene and / or alkylstyrenes. Particularly preferred polymers are, for example, ABS polymerized. Graft copolymers can be prepared by methods known as block, suspension, emulsion, or block-suspension procedures. As thermoplastic polyamides, polyamide 66 (polyhexamethylene adipamide) or cyclic lactam polyamides with 5 to 12 C atoms, preferably laurinlactam and especially e-caprolactam = polyamide 6, can be used as the thermoplastic polyamides. (polycaprolactam) or cspolyamides with main component 6 or 66 or mixtures with main component of the indicated polyamides. The copolyamide with polycaprolactam as the main component prepared by activated anionic polymerization is preferred. Activated anionic polymerization of lactams to polyamides is carried out on an industrial scale by preparing on the one hand a lactam catalyst solution, optionally with a shock resistance modifier, and on the other hand a lactam activator solution, both solutions being composed of so that a combination in the same ratio provides the desired total formulation. This however is not necessary. Other compositions can also be chosen, for example by metering a concentrated melt of activator and catalyst into a lactam melt. Other additives according to the respective compatibilities can be added to the melt of activator, catalyst or in the case of lactam. The polymerization is carried out by mixing the individual solutions to obtain the complete formulation at a temperature of 80 ° C to 200 ° C, preferably 100 ° C to 140 ° C. The catalyst is an alkaline or alkaline earth lactamate, preferably as a lactam solution, with particular preference caprolactamate sodium in e-caprolactam. The activator in the sense according to the invention can be N-alkyl-lactams or acid chlorides or, preferably, aliphatic isocyanates, especially oligomers of hexamethylene diisocyanate. As the activator, both the pure substance and also preferably a solution, preferably in N-methylpyrrolidone, can be used. The composite materials can be manufactured in a known manner. Preferably the layer B) of thermoplastic polymer of the composite material is prepared in advance and on it the reaction system of polyurethane is applied and reacted. Depending on the reactivity of the reaction components of the polyurethane, these may already be premixed or mixed in a known manner during application. The application is preferably carried out by spraying, scratching or calendering. However, it is also possible to manufacture the composite material according to the invention by coextrusion by known methods. In particular, the reaction components of the polyurethane are reacted according to the one-step process known per se, to the prepolymer process or to the semiprepolymer process. In the manufacture of PU foams, foaming according to the invention can also be carried out in closed molds. In this respect, the reaction mixture is introduced into a mold in which layer B) of the composite material is already located. As the material of the mold metals, eg, aluminum, or plastics, eg epoxy resin, are considered. In the foam mold the foaming reaction mixture and the composite molding body is formed. The foaming in the mold can be carried out in this respect so that the molded part has a cellular structure on its surface, but it can also be realized in such a way that the molding part has a compact skin and a cellular core. Here, in this context, one can proceed so that the amount of foaming reaction mixture necessary for the foam formed to fill the mold is exactly introduced into the mold. But it can also be worked by introducing more foaming reaction mixture into the mold than is necessary for filling the inside of the mold with foam. In the latter case, therefore, overloading is carried out ("over-charging"); a procedure of this type is generally known. In the mold foaming, multiple "external mold release agents" known per se are used as silicone oils. However, so-called "internal mold release agents" may also be used, optionally mixed with external mold release agents. Cold hardening foams can also be manufactured according to the invention. Obviously, foams can also be manufactured by block foam or by the double conveyor method known per se, which is preferred for the continuous manufacture of composite materials according to the invention. Also preferred is the manufacture of polyurethane composite bodies in sandwich form. The process can be carried out in this respect as a depositing or wrapping process. Both the deposit method and the shell method are known per se. In the depositing process (filling method) two half-shells are prepared (eg plastic cover layers), inserted into a mold and the hollow space between the covers is filled with foam with the PUR foam. In the wrapping method, a core of PUR foam is placed in a mold and then wrapped with a suitable wrapping material, eg with one of the indicated thermoplastics. In the manufacture of the composite body of the sandwich type, the wrapping method is preferred.

For the manufacture of compact PUR materials the two components of the PU reaction are reacted as indicated above by simple mixing at room temperature. Another subsequent coating of the layer can be carried out by the usual known methods of lacquering, metallizing or other coating with a polymer layer (eg as layer A). The composite materials according to the invention are preferably used in the manufacture of automobiles, in particular in the coating of interiors, eg as covering material for dashboards or column coverings. The invention is illustrated with the following Examples.

EXAMPLES The content of unreacted reaction components containing ether groups in the polyurethane of the A layer of is determined as follows: The polymer layer A) is mechanically separated from the composite material, mechanically comminuted and extracted with solvents as methylene chloride. Then a determination of the polyether components that have not reacted in the extract chromatographically in conjunction with NMR spectroscopy or IR spectroscopy is possible. The bonding adhesion is tested as follows in accordance with DIN 53 357: The polymer layer A) is applied as a thin film according to the corresponding DIN standard on support B). The separation bore is then measured in the separation of the composite material by, for example, a roller delamination test according to DIN 53 357. Example 1 A layer A) of polyurethane of the following composition is applied to a support B) polymer composed of polycarbonate based on bis-phenol A . { molar mass Mn = 12,000 g / mol): "For this purpose, a polyether is mixed thoroughly, prepared from * propylene oxide and ethylene oxide (functionality = 3) with a molar mass of Mn = 7,000 g / mol with 4 , 4'-diisocyanatodiphenylmethane (MDI) and water (1% by weight based on MDI) in stoichiometric ratios (NCO: OH) For the simulation of unreacted free polyether a proportion of 4,000 ppm of a poly (ethylene oxide) is added. ) of the same molar mass (Mn = 7,000 g / mol) with non-reactive end groups (terminal groups: diphenylmethyl and methyl) Then the mixture is poured immediately onto the polycarbonate support B), a pouring frame being arranged around the polycarbonate support to achieve a uniform layer thickness After storage of these composite bodies under the conditions of use of the technical product (0 to 14 days of storage at 80 ° C and 80% relative humidity) the foam layer is removed from the polyurethane by des lamination of 20 mm wide sample strips (90 ° roller delamination test) and the separation force is measured for bond determination. After the separation of the substrate from the polyurethane layer, the proportion of polyether on the surface of the substrate was determined by X-ray photoelectron spectroscopy (XPS) by determining the proportion of C-0 of the Cls line. The increase over time of the proportion of polyether on the separate substrate surface is shown in Figure 1. 'In Figure 2 it can be seen that an increase in the proportion of polyether in the surface area during storage (determined by the ratio of C-0 to XPS in the separate substrate surface) leads to a decrease in binding adhesion. Example 2 is repeated analogously as in Example 1, but an addition of a non-reactive polyether ratio of 400 ppm was made instead of 4000 ppm (polyethylene oxide) Mn = 7,000 g / mol with non-reactive end groups : dimethyl and methyl). The increase over time of the proportion of the polyether on the separated substrate surface increased after 14 days to a CO ratio of 20% in atoms with separation forces of 2.5 N. The lowest proportion of unreacted polyether with respect to Example 1 therefore indicates a clear lower decrease in the separation force. Comparative Example 3 Example 1 was repeated without addition of the proportion of unreacted polyether until storage times of 30 days at 80 ° C and 80% relative humidity. The separation force for the determination of the bonding bond was in all cases >; 6 N. From the 3 examples, it follows, therefore, that the binding adhesion decreases strongly if the unreacted residual content of the ether-containing component exceeds 400 ppm.

It is noted that in relation to this date, the best method known to the applicant to carry. the practice of said invention is that which is clear from the present description of the invention.

Claims (7)

CLAIMS Having described the invention as above, the content of the following claims is claimed as property:

1. Material composed of layers of different plastics joined directly together, of which A) a layer of the composite material is polyurethane and B) a layer of the composite material bonded directly thereto is a thermoplastic plastic different from that of A), characterized in that the layer A) presents, from the polyurethane preparation, a residual content of reaction components containing ether groups of not more than 400 ppm, preferably < 100 ppm.

2. Composite material according to claim 1, characterized in that the layer A) of the composite material is a polyurethane foam or a polyurethane lacquer.

3. Composite material according to claim 1 or 2, characterized in that the layer B) of the composite material consists of polycarbonate, polyester carbonate, copolymerized styrene or a corresponding graft copolymer or mixtures thereof.

4. Composite material according to claim 1 or 2, characterized in that a polyolefin, preferably polyethylene, polypropylene or copolymerized ethylene-propylene, or a polyamide, preferably polyamide 6 or polyamide 6, is used as the thermoplastic plastic of the layer B) of the composite material. , 6.

5. Composite material according to claim 3, characterized in that the residual content of reaction components containing ether groups in the polyurethane foam of the layer A) of the composite material is at most 100 ppm and the layer B) of the composite material is constituted by polycarbonate.

6. Process for the manufacture of a composite material of at least two layers of different plastics bonded directly together, of which A) a layer of the composite material is polyurethane and B) a layer of the composite material bonded directly thereto is of a thermoplastic plastic different from that of A), characterized in that layer A) with a residual content of reaction components containing ether groups of 400 ppm as maximum, preferably < 100 ppm, is applied on layer B).

7. Use of a composite material according to one or more of claims 1 to 5 as working material in the construction of automobiles.