EP1713639A1 - Corps moule comportant une plaque ou une pellicule a couche composite et une couche support presentant un meilleur pouvoir de brillance - Google Patents

Corps moule comportant une plaque ou une pellicule a couche composite et une couche support presentant un meilleur pouvoir de brillance

Info

Publication number
EP1713639A1
EP1713639A1 EP05701207A EP05701207A EP1713639A1 EP 1713639 A1 EP1713639 A1 EP 1713639A1 EP 05701207 A EP05701207 A EP 05701207A EP 05701207 A EP05701207 A EP 05701207A EP 1713639 A1 EP1713639 A1 EP 1713639A1
Authority
EP
European Patent Office
Prior art keywords
weight
component
layer
graft
film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP05701207A
Other languages
German (de)
English (en)
Inventor
Achim Grefenstein
Steffen Funkhauser
Herbert Fisch
Norbert Effen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1713639A1 publication Critical patent/EP1713639A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
    • C08L25/02—Homopolymers or copolymers of hydrocarbons
    • C08L25/04—Homopolymers or copolymers of styrene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249924—Noninterengaged fiber-containing paper-free web or sheet which is not of specified porosity
    • Y10T428/24994—Fiber embedded in or on the surface of a polymeric matrix
    • Y10T428/24995—Two or more layers
    • Y10T428/249952—At least one thermosetting synthetic polymeric material layer

Definitions

  • Shaped part comprising a composite layer plate or film and a carrier layer with improved gloss behavior
  • the invention relates to molded parts comprising a composite layer plate or film and a back-molded, back-foamed, back-molded or back-pressed carrier layer made of plastic, the composite layer plate or film comprising
  • a substrate layer containing, based on the sum of the amounts of components A and B, and possibly C and / or D, which gives a total of 100% by weight, a 1-99% by weight of a rubber-elastic graft copolymer as Component A, b 1-99% by weight of one or more hard copolymers containing units which are derived from vinylaromatic monomers as component B, c 0-80% by weight polycarbonates as component C, and d 0-50% by weight .-% fibrous or particulate fillers or mixtures thereof as component D, and
  • the invention further relates to methods for producing these molded parts, their use in the exterior of motor vehicles, and outer parts for motor vehicles.
  • DE 10228376.1 (file number) describes molded parts comprising a composite layer plate or film and a back-molded, back-foamed or back-molded carrier layer made of plastic, which have a good surface quality, in particular a low waviness, even at high temperatures.
  • the composite layered plate or film of these molded parts has a substrate layer which contains polymers with a high ⁇ -methylstyrene content as a hard copolymer component.
  • Weather-resistant, transparent and scratch-resistant polymers in particular polymethyl methacrylate, polycarbonate or styrene-acrylonitrile copolymers, are disclosed as suitable cover layer materials for this composite layer plate or film.
  • Aliphatic thermoplastic polyurethane is known as a polymer that can be used in the automotive field.
  • Kunststoffe 92 (2002) 6, pages 93 - 95 the special properties of this material, for example light stability, low-temperature flexibility, good mechanics, aging stability and the scratch resistance which is better than that of conventionally used materials, which limit the use enables automatic car washes, disclosed. No statements are made about the change in surface gloss over the course of the service life, for example due to frequent soiling and the need for cleaning in automatic washing systems.
  • EP-B 567 883 discloses composite molded articles made of at least one layer made of an ABS plastic and at least one layer made of a thermoplastic polyurethane with a Shore D hardness> 50.
  • the composite molded articles are characterized by chemical resistance and deformability in the deep-drawing process. Their application for the production of inner refrigerator containers is described. Use in outdoor or motor vehicle areas is not described.
  • the object of the present invention is to provide molded parts, comprising a composite layer plate or film and a back-injected, back-foamed, back-molded or back-pressed carrier layer made of plastic with an improved surface gloss over the period of use, in particular in connection with frequent soiling and thereby required cleaning in automatic washing systems.
  • molded parts comprising a composite layer plate or film and a back-injected, back-foamed, back-molded or back-pressed carrier layer made of plastic, the composite layer plate or film comprising
  • a substrate layer containing, based on the sum of the amounts of components A and B, and possibly C and / or D, which gives a total of 100% by weight, a 1-99% by weight of a rubber-elastic graft copolymer as Component A, b 1-99% by weight of one or more hard copolymers containing units which are derived from vinylaromatic monomers as component B, c 0-80% by weight polycarbonates as component C, and d 0-50% by weight .-% fibrous or particulate fillers or mixtures thereof as component D, and
  • the molded parts according to the invention have an improved surface gloss over the period of use, in particular in connection with frequent soiling and consequently necessary cleaning in automatic washing systems. They are therefore particularly suitable for outdoors, in which they are exposed to environmental influences such as weather, temperature fluctuations or contamination, for example as motor vehicle exterior parts.
  • Layer (1) is composed of the following components A and B and, if appropriate, C and / or D, which give a total of 100% by weight.
  • the substrate layer (1) contains impact-modified copolymers of vinyl aromatic monomers and vinyl cyanides (SAN), and moreover optionally further components, preferably polycarbonate.
  • SAN vinyl cyanides
  • ASA polymers are generally understood to be impact-modified SAN polymers in which graft copolymers of vinylaromatic compounds, in particular styrene, and vinylcyanides, in particular acrylonitrile, on polyalkylacrylate rubbers are present in a copolymer matrix of, in particular, styrene and / or ⁇ -methylstyrene and acrylonitrile ,
  • component A is a rubber-elastic graft copolymer made of
  • the graft pad A2 consists of at least one graft shell, the graft copolymer A overall having an average particle size of 50
  • Component A1 consists of the monomers
  • the average particle size of component A is 50-800 nm, preferably 50-600 nm.
  • the particle size distribution of component A is bimodal, 60-90% by weight having an average particle size of 50-200 nm and 10-40% by weight having an average particle size of 50-400 nm on the total weight of component A.
  • the sizes determined from the integral mass distribution are given as the average particle size or particle size distribution.
  • the mean particle sizes according to the invention are in all cases the weight average of the particle sizes, as determined by means of an analytical ultracentrifuge according to the method of W. Scholtan and H. Lange, Kolloid-Z. and Z.-Polymer 250 (1972), pages 782-796.
  • the ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this it can be seen what percentage by weight of the particles have a diameter equal to or smaller than a certain size.
  • the mean particle diameter which is also referred to as the d 50 value of the integral mass distribution, is defined here as the particle diameter at which 50% by weight of the particles have a smaller diameter than the diameter which corresponds to the d 50 value. Likewise, 50% by weight of the particles then have a larger diameter than the d 50 value.
  • the dio and dgo values resulting from the integral mass distribution are used to characterize the width of the particle size distribution of the rubber particles.
  • the d 10 or d 90 value of the integral mass distribution is defined in accordance with the d 50 value with the difference that they are based on 10 or 90% by weight of the particles. The quotient
  • Emulsion polymers A which can be used according to the invention as component A preferably have Q values less than 0.5, in particular less than 0.35.
  • the acrylate rubbers A1 are preferably alkyl acrylate rubbers composed of one or more preferably C 1 - alkyl acrylates, butyl, hexyl, octyl or 2-ethylhexyl acrylate, in particular n-butyl and 2-ethylhexyl acrylate, preferably being used at least in part.
  • These alkyl acrylate rubbers can contain up to 30% by weight of monomers forming hard polymers, such as vinyl acetate, (meth) acrylonitrile, styrene, substituted styrene, methyl methacrylate, vinyl ether, in copolymerized form.
  • the acrylate rubbers further contain 0.01-20% by weight, preferably 0.1-5% by weight, of crosslinking, polyfunctional monomers (crosslinking monomers).
  • crosslinking monomers polyfunctional monomers
  • examples of these are monomers which contain 2 or more double bonds capable of copolymerization, which are preferably not conjugated in the 1,3 positions.
  • Suitable crosslinking monomers are, for example, divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate, diethyl phthalate, triallyl cyanurate, triallyl isocyanurate, tricyclodecenyl acrylate, dihydrodicyclopentadienyl acrylate, triallyl phosphate, allyl methacrylate and allyl methacrylate.
  • Dicyclopentadienyl acrylate (DCPA) has proven to be a particularly favorable crosslinking monomer (cf. DE-PC 1260 135).
  • Component A is a graft copolymer.
  • the graft copolymers A have a mean particle size d 50 of 50-1000 nm, preferably 50-800 nm and particularly preferably 50-600 nm. These particle sizes can be achieved if particle size is used as the graft base A1 of this component A. from 50 to 350 nm, preferably from 50 to 300 nm and particularly preferably from 50 to 250 nm.
  • the graft copolymer A is generally one or more stages, i.e. a polymer composed of a core and one or more shells.
  • the polymer consists of a basic stage (graft core) A1 and one or - preferably - several stages A2 (grafted pad) grafted thereon, the so-called grafting stages or graft shells.
  • One or more graft shells can be applied to the rubber particles by simple grafting or multiple stepwise grafting, each
  • Graft shell can have a different composition.
  • polyfunctional crosslinking or reactive groups can be included Monomers are also grafted on (see, for example, EP-A 230282, DE-AS 36 01 419, EP-A 269 861).
  • component A consists of a multi-stage graft copolymer, the graft stages being generally made from resin-forming monomers and having a glass transition temperature T g above 30 ° C., preferably above 50 ° C.
  • the multi-stage structure serves, among other things, to achieve (partial) compatibility of the rubber particles A with the thermoplastic B.
  • Graft copolymers A are prepared, for example, by grafting at least one of the monomers A2 listed below onto at least one of the graft bases or graft core materials A1 listed above.
  • the graft base A1 is composed of 15-99% by weight of acrylate rubber, 0.1-5% by weight of crosslinking agent and 0-49.9% by weight of one of the further monomers or rubbers indicated.
  • Suitable monomers for forming the graft A2 are styrene, a-methylstyrene, (meth) acrylic acid ester, acrylonitrile and methacrylonitrile, in particular acrylonitrile.
  • crosslinked acrylic acid ester polymers with a glass transition temperature below 0 ° C. serve as the graft base A1.
  • the crosslinked acrylic ester polymers should preferably have a glass transition temperature below -20 ° C., in particular below -30 ° C.
  • the graft A2 consists of at least one graft shell and the outermost graft shell thereof has a glass transition temperature of more than 30 ° C., a polymer formed from the monomers of the graft A2 would have a glass transition temperature of more than 80 ° C.
  • Suitable preparation processes for graft copolymers A are emulsion, solution, bulk or suspension polymerization.
  • the graft copolymers A are preferably prepared by free-radical emulsion polymerization in the presence of latices of component A1 at temperatures from 20 ° C. to 90 ° C. using water-soluble or oil-soluble initiators such as peroxodisulfate or benzyl peroxide, or with the aid of redox initiators. Redox initiators are also suitable for polymerization below 20 ° C.
  • Suitable emulsion polymerization processes are described in DE-A 2826 925, 31 49 358 and in DE-C 1260 135.
  • the graft casings are preferably built up in the emulsion polymerization process as described in DE-A 3227555, 31 49 357, 31 49 358, 34 14 118.
  • the defined particle sizes of 50-1000 nm according to the invention are preferably carried out by the process, which are described in DE-C 12 60 135 and DE-A 2826 925, or Applied Polymer Science, Volume 9 (1965), page 2929.
  • the use of polymers with different particle sizes is known, for example, from DE-A 2826 925 and US-A 5 196480.
  • the graft base A1 is first prepared by adding the acrylic acid ester (s) used according to one embodiment of the invention and the multi-functional crosslinking monomers, optionally together with the other comonomers, in an aqueous emulsion in a known manner at temperatures between 20 and 100 ° C, preferably between 50 and 80 ° C, polymerized.
  • the usual emulsifiers such as, for example, alkali metal salts of alkyl or alkylarylsulfonic acids, alkyl sulfates, fatty alcohol sulfonates, salts of higher fatty acids with 10 to 30 carbon atoms or resin soaps can be used.
  • the sodium salts of alkyl sulfonates or fatty acids having 10 to 18 carbon atoms are preferably used.
  • the emulsifiers are used in amounts of 0.5-5% by weight, in particular 1-2% by weight, based on the monomers used in the preparation of the graft base A1.
  • the weight ratio of water to monomers is from 2: 1 to 0.7: 1.
  • the usual persulfates, such as, for example, potassium persulfate, are used in particular as polymerization initiators. However, redox systems can also be used.
  • the initiators are generally used in amounts of 0.1-1% by weight, based on the monomers used in the preparation of the graft base A1.
  • the usual buffer substances by means of which pH values of preferably 6-9, such as sodium bicarbonate and sodium pyrophosphate, and 0-3% by weight of a molecular weight regulator, such as mercaptans, terpinols or dimeric a-methylstyrene, can be added as further polymerization auxiliaries the polymerization can be used.
  • a molecular weight regulator such as mercaptans, terpinols or dimeric a-methylstyrene
  • the exact polymerization conditions in particular the type, dosage and amount of the emulsifier, are determined in detail within the ranges given above such that the latex of the crosslinked acrylic acid ester polymer obtained has ad 50 value in the range from about 50-1000 nm, preferably 50-600 nm , particularly preferably in the range of 80-500 nm.
  • the particle size distribution of the latex should preferably be narrow.
  • a monomer mixture of styrene and acrylonitrile is then polymerized in a next step in the presence of the latex of the crosslinked acrylic ester polymer thus obtained, the weight ratio of styrene to acrylonitrile in the monomer mixture according to one embodiment of the invention in the range of 100: 0 to 40:60, preferably in the range from 65: 35 to 85: 15. It is advantageous to carry out this graft copolymerization of styrene and acrylonitrile on the crosslinked polyacrylic acid ester polymer used as the graft base again in aqueous emulsion under the customary conditions described above.
  • the graft copolymerization can expediently take place in the same system as the emulsion polymerization for the preparation of the graft base A1, it being possible, if necessary, to add further emulsifier and initiator.
  • the monomer mixture of styrene and acrylonitrile to be grafted on according to one embodiment of the invention can be added to the reaction mixture all at once, batchwise in several stages or preferably continuously during the polymerization.
  • the graft copolymerization of the mixture of styrene and acrylonitrile in the presence of the crosslinking acrylic ester polymer is carried out in such a way that a degree of grafting of 1-99% by weight, preferably 20-45% by weight, in particular 35-45% by weight, based on the Total weight of component A, resulting in graft copolymer A. Since the graft yield in the graft copolymerization is not 100%, a somewhat larger amount of the monomer mixture of styrene and acrylonitrile must be used in the graft copolymerization than corresponds to the desired degree of grafting.
  • the control of the graft yield in the graft copolymerization and thus the degree of grafting of the finished graft copolymer A is known to the person skilled in the art and can be carried out, for example, by the metering rate of the monomers or by adding a regulator (Chauvel, Daniel, ACS Polymer Preprints 15 (1974), page 329 ff .).
  • the emulsion graft copolymerization generally gives rise to about 5-15% by weight, based on the graft copolymer, of free, non-grafted styrene / acrylonitrile copolymer.
  • the proportion of the graft copolymer A in the polymerization product obtained in the graft copolymerization is determined by the method given above.
  • graft copolymers A In the production of the graft copolymers A by the emulsion process, in addition to the process advantages, reproducible changes in particle size are also possible, for example by at least partially agglomerating the particles into larger particles. This means that polymers with different particle sizes can also be present in the graft copolymers A.
  • Component A in particular, consisting of the graft base and graft shell (s) can be optimally adapted for the particular application, in particular with regard to the particle size.
  • the graft copolymers A generally contain 1-99% by weight, preferably 55-80 and particularly preferably 55-65% by weight of graft base A1 and 1-99% by weight, preferably 20-45, particularly preferably 35-45% by weight .-% of the graft A2, each based on the entire graft copolymer.
  • ABS polymers are generally understood to be impact-modified SAN polymers in which diene polymers, in particular 1,3-polybutadiene, are present in a copolymer matrix composed in particular of styrene and / or ⁇ -methylstyrene and acrylonitrile.
  • component A is a rubber-elastic graft copolymer
  • a1 V 60 to 100 preferably 70 to 100% by weight of at least one conjugated diene and / or C to C 1 -alkyl acrylate, in particular butadiene, isoprene, n-butyl acrylate and / or 2-ethylhexyl acrylate,
  • crosslinking monomer preferably divinylbenzene, diallyl maleate, allyl ester of (meth) acrylic acid, di-hydrodicyclopentadienyl acrylate, dinvinyl ester of dicarboxylic acids such as succinic and adipic acid, and diallyl and divinyl ethers of bifunctional alcohols such as ethylene glycol or butane-1,4-diol,
  • a2 '10 to 60 preferably 15 to 55% by weight of a graft A2', based on A2 ',
  • a21 '50 to 100 preferably 55 to 90 wt .-% of at least one vinyl aromatic monomer, preferably styrene and / or ⁇ -methylstyrene,
  • a22 '5 to 35 preferably 10 to 30% by weight of acrylonitrile and / or methacrylonitrile, preferably acrylonitrile,
  • component A is a graft rubber with a bimodal particle size distribution, based on A,
  • component B is at least one hard copolymer which contains units which are derived from vinylaromatic monomers and, based on the total weight of units which are derived from vinylaromatic monomers, 0-100% by weight, preferably 40-100% by weight, particularly preferably 60-100% by weight, of ⁇ -methylstyrene and 0-100% by weight, preferably 0-60% by weight, particularly preferably 0-40% by weight of units derived from styrene are present
  • component B is at least one hard copolymer which contains units which are derived from vinylaromatic monomers and, based on the total weight of units which are derived from vinylaromatic monomers, 0-100% by weight, preferably 40-100% by weight, particularly preferably 60-100% by weight, of ⁇ -methylstyrene and 0-100% by weight, preferably 0-60% by weight, particularly preferably 0-40% by weight of units deriving from styrene are present, based on B,
  • b1 '50 to 100 preferably 55 to 90% by weight of vinyl aromatic monomers, b2' 0 to 50% by weight of acrylonitrile or methacrylonitrile or mixtures thereof, b3 "0 to 50% by weight of at least one further monoethylenically unsaturated monomer, for example Methyl methacrylate and N-alkyl or N-aryl maleimides such as N-phenyl maleimide.
  • component B is at least one hard copolymer with a viscosity number VZ (determined according to DIN 53726 at 25 ° C. in 0.5% strength by weight solution in dimethylformamide) of 50 up to 120 ml / g “which contains units which are derived from vinylaromatic monomers and, based on the total weight of units which are derived from vinylaromatic monomers, 0-100% by weight, preferably 40-100% by weight, particularly preferably 60 to 100% by weight of ⁇ -methylstyrene and 0 to 100% by weight, preferably 0 to 60% by weight, particularly preferably 0 to 40% by weight of units derived from styrene are contained , related to B
  • components B are present side by side in the ABS polymers, which differ from one another in their viscosity numbers VZ by at least five units (ml / g) and / or in their acrylonitrile contents by five units (% by weight).
  • copolymers of ( ⁇ -methyl) styrene and maleic anhydride or maleimides of ( ⁇ -methyl) styrene, maleimides and methyl methacrylate or acrylonitrile, or of ( ⁇ -methyl) stryol, maleimides , Methyl methacrylate and acrylonitrile.
  • the graft polymers A are preferably obtained by means of emulsion polymerization.
  • the graft polymers A are mixed with the components B and, if appropriate, further additives in a mixing device, an essentially molten polymer mixture being formed. It is advantageous to cool the molten polymer mixture as quickly as possible.
  • ABS polymers mentioned can have other customary auxiliaries and fillers.
  • Such substances are, for example, lubricants or mold release agents, waxes, pigments, dyes, flame retardants, antioxidants, light stabilizers or antistatic agents.
  • the viscosity number of component B is 50-90, preferably 60-80.
  • Component B is preferably an amorphous polymer. According to one embodiment of the invention, a mixture of a copolymer of styrene with acrylonitrile and a copolymer of ⁇ -methylstyrene with acrylonitrile is used as component B.
  • the acrylonitrile content in these copolymers of component B is 0-60% by weight, preferably 15-40% by weight, based on the total weight of component B.
  • Component B also includes those formed in the graft copolymerization to produce component A. free, non-grafted ( ⁇ -methyl) - styrene / acrylonitrile copolymers.
  • component B may be a sufficient proportion of component B has already been formed in the graft copolymerization. In general, however, it will be necessary to mix the products obtained in the graft copolymerization with additional, separately produced component B.
  • This additional, separately produced component B can preferably be a mixture of styrene / acrylonitrile copolymer with ⁇ -methylstyrene / acrylonitrile copolymer or an ⁇ -methylstyrene / styrene / acrylonitrile terpolymer.
  • These copolymers can be used individually or as a mixture for component B, so that the additional, separately prepared component B can be, for example, a mixture of a styrene / acrylonitrile copolymer and an ⁇ -methylstyrene / acrylonitrile copolymer.
  • component B consists of a mixture of a styrene / acrylonitrile copolymer and an ⁇ -methylstyrene / acrylonitrile copolymer
  • the acrylonitrile content of the two copolymers should preferably not be more than 10% by weight, preferably not differ from one another by more than 5% by weight, based on the total weight of the copolymer.
  • the additional, separately manufactured component B can be obtained by the conventional methods.
  • the copolymerization of the styrene and / or ⁇ -methylstyrene with the acrylonitrile can be carried out in bulk, solution, suspension or aqueous emulsion.
  • Component B preferably has a viscosity number of 40 to 100, preferably 50 to 90, in particular 60 to 80. The viscosity number is determined in accordance with DIN 53 726, 0.5 g of material being dissolved in 100 ml of dimethylformamide.
  • Components A and B and, if appropriate, C, D can be mixed in any desired manner by all known methods. If components A and B have been prepared, for example, by emulsion polymerization, it is possible to mix the polymer dispersions obtained with one another, to precipitate the polymers together and to work up the polymer mixture. However, components A and B are preferably mixed by extruding, kneading or rolling the components together, the components having, if necessary, been isolated beforehand from the solution or aqueous dispersion obtained in the polymerization.
  • the products of the graft copolymerization (component A) obtained in aqueous dispersion can also only be partially dewatered and mixed as a moist crumb with component B, the complete drying of the graft copolymers then taking place during the mixing.
  • layer (1) contains, in addition to components A and B, additional components C and / or D, and, if appropriate, further additives, as described below.
  • polycarbonates suitable as component C preferably have a molecular weight (weight average M w , determined by means of gel permeation chromatography in tetrahydrofuran against polystyrene standards) in the range from 10,000 to 60,000 g / mol. They can be obtained, for example, in accordance with the processes of DE-B-1 300266 by interfacial polycondensation or in accordance with the process of DE-A-1 495730 by reacting diphenyl carbonate with bisphenols.
  • Preferred bisphenol is 2,2-di (4-hydroxyphenyl) propane, generally - as also hereinafter - referred to as bisphenol A.
  • aromatic dihydroxy compounds can also be used, in particular 2,2-di (4-hydroxyphenyl) pentane, 2,6-dihydroxynaphthalene, 4,4'-dihydroxydiphenylsulfane, 4,4'-dihydroxydiphenyl ether, 4,4 '-Dihydroxy-diphenylsulfite, 4,4'-dihydroxydiphenylmethane, 1,1-di- (4-hydroxyphenyl) ethane, 4,4-di-hydroxydiphenyl or dihydroxydiphenylcycloalkanes, preferably dihydroxydiphenylcyclohexanes or dihydroxylcyclopentanes, especially 1,1-bis ( 4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and mixtures of the aforementioned dihydroxy compounds.
  • 2,2-di (4-hydroxyphenyl) pentane 2,6-dihydroxynaphthalene
  • 4,4'-dihydroxydiphenylsulfane 4,4
  • Particularly preferred polycarbonates are those based on bisphenol A or bisphenol A together with up to 80 mol% of the aromatic dihydroxy compounds mentioned above.
  • Polycarbonates which are particularly suitable as component C are those which contain units which are derived from resorcinol or alkylresorcinol esters, as are described, for example, in WO 00/61664, WO 00/15718 or WO 00/26274; These polycarbonates are, for example, sold by General Electric Company under the trademark SollX ®.
  • Copolycarbonates according to US Pat. No. 3,737,409 can also be used; Of particular interest are copolycarbonates based on bisphenol A and di (3,5-dimethyl-dihydroxyphenyl) sulfone, which are characterized by high heat resistance. It is also possible to use mixtures of different polycarbonates.
  • the average molecular weights (weight average M w , determined by means of gel permeation chromatography in tetrahydrofuran against polystyrene standards) of the polycarbonates C are in the range from 10,000 to 64,000 g / mol. They are preferably in the range from 15,000 to 63,000, in particular in the range from 15,000 to 60,000 g / mol. This means that the polycarbonates C have relative solution viscosities in the range from 1.1 to 1.3, measured in 0.5% strength by weight solution in dichloromethane at 25 ° C., preferably from 1.15 to 1.33. The relative solution viscosities of the polycarbonates used preferably differ by no more than 0.05, in particular no more than 0.04.
  • the polycarbonates C can be used both as regrind and in granular form. They are present as component C in amounts of 0-80% by weight, preferably 20-70% by weight, particularly preferably 40-70% by weight, in each case based on the sum of components A, B, C and possibly D, before.
  • Layer (1) contains, as component D, 0-50% by weight, preferably 0-40% by weight, in particular 0-30% by weight, of fibrous or particulate fillers or mixtures thereof, in each case based on the entire layer 1. These are preferably commercially available products.
  • Reinforcing agents such as carbon fibers and glass fibers are usually used in amounts of 5-50% by weight, based on the entire layer (1).
  • the glass fibers used can be made of E, A or C glass and are preferably equipped with a size and an adhesion promoter. Their diameter is generally between 6 and 20 ⁇ m. Both continuous fibers (rovings) and chopped glass fibers (staples) with a length of 1 - 10 mm, preferably 3 - 6 mm, can be used.
  • fillers or reinforcing materials such as glass balls, mineral fibers, whiskers, aluminum oxide fibers, mica, quartz powder and wollastonite can be added.
  • metal flakes e.g. aluminum flakes from Transmet Corp.
  • metal powder e.g. aluminum powder
  • metal fibers e.g. nickel-coated glass fibers
  • metal-coated fillers e.g. nickel-coated glass fibers
  • other additives that shield electromagnetic waves
  • Aluminum flakes K 102 from Transmet
  • EMI purposes electro-magnetic] interference
  • the masses can be mixed with additional carbon fibers, carbon black, in particular conductivity carbon black, or nickel-coated carbon fibers.
  • the layer (1) used according to the invention can also contain further additives which are typical and customary for polycarbonates, SAN polymers and graft copolymers or their mixtures.
  • additives are: dyes, pigments, colorants, antistatic agents, antioxidants, stabilizers for improving the thermostability, for increasing the light stability, for increasing the resistance to hydrolysis and the resistance to chemicals, agents against heat decomposition and in particular the lubricants for the production of moldings or moldings are expedient.
  • These additional additives can be metered in at any stage of the production process, but preferably at an early point in time, in order to take advantage of the stabilizing effects (or other special effects) of the additive at an early stage.
  • Heat stabilizers or oxidation retardants are usually metal halides (chlorides, bromides, iodides) which are derived from metals of group I of the periodic table of the elements (such as Li, Na, K, Cu).
  • Suitable stabilizers are the usual hindered phenols, but also vitamin E or compounds with an analog structure.
  • HALS stabilizers hindered amine light stabilizers
  • benzophenones hindered amine light stabilizers
  • resorcinols resorcinols
  • salicylates e.g., benzotriazoles
  • TinuvinRP UV absorber 2 - (2H-benzotriazol-2-yl) -4-methylphenol from CIBA
  • Suitable lubricants and mold release agents are stearic acids, stearyl alcohol, stearic acid esters or generally higher fatty acids, their derivatives and corresponding fatty acid mixtures with 12-30 carbon atoms.
  • the amounts of these additives are in the range of 0.05-1% by weight.
  • Silicone oils, oligomeric isobutylene or similar substances are also suitable as additives, the usual amounts being 0.05-5% by weight.
  • Pigments, dyes, color brighteners such as ultramarine blue, phthalocyanines, titanium dioxide, cadmium sulfides, derivatives of perylene tetracarboxylic acid can also be used.
  • Processing aids and stabilizers such as UV stabilizers, lubricants and antistatic agents are usually used in amounts of 0.01-5% by weight.
  • Layer (1) can be produced by methods known per se by mixing the components. It can be advantageous to premix individual components. Mixing the components in solution and removing the solvents is also possible.
  • Suitable organic solvents are, for example, chlorobenzene, mixtures of chlorobenzene and methylene chloride or mixtures of chlorobenzene or aromatic hydrocarbons, e.g. Toluene.
  • the solvent mixtures can be evaporated, for example, in evaporation extruders.
  • Mixing e.g. dry components can be made by all known methods. However, the mixing is preferably carried out by extruding, kneading or rolling the components together, preferably at temperatures of 180-400 ° C., the components having, if necessary, been isolated beforehand from the solution obtained in the polymerization or from the aqueous dispersion.
  • the components can be metered in together or separately / one after the other.
  • the substrate layer (1) preferably has an elastic modulus E t (measured according to ISO 527-2 / 1 B at 5 mm / min at a temperature of 100 ° C.) of at least 1000 MPa.
  • Layer (2) is a colored intermediate layer, which can preferably contain effect pigments, such as metal flakes or mica. Layer (2) is different from layers (1) and (3), for example due to a different polymer composition and / or different additive contents such as colorants or effect pigments.
  • One embodiment of the invention relates to a molded part comprising a composite layer plate or film composed of a substrate layer (1), top layer (3) and an intermediate layer (2) as described above, which is made of aliphatic thermoplastic polyurethane, impact-resistant PMMA, polycarbonate or styrene (co ) polymers such as SAN, which can be impact modified, for example ASA or ABS, or mixtures of these polymers, with the proviso that layer (2) is neither constructed nor composed in the same way as layer (1) on the one hand, and layer (3) on the other hand. If aliphatic thermoplastic polyurethane is used as the material of the intermediate layer (2), the aliphatic thermoplastic polyurethane described under layer (3) can be used.
  • the polycarbonate described under layer (1), component C can be used.
  • Impact-resistant PMMA high impact PMMA: HI-PMMA
  • HI-PMMA is a polymethyl methacrylate that is impact-resistant with suitable additives. Suitable impact-modified PMMAs are described, for example, by M. Stickler, T. Rhein in Ullmann's encyclopedia of industrial chemistry Vol. A21, pages 473-486, VCH Publishers Weinheim, 1992, and H. Domininghaus, The Plastics and Their Properties, VDI- Verlag Düsseldorf, 1992.
  • the intermediate layer (2) contains coloring substances known to the person skilled in the art. These are, for example, dyes or pigments.
  • the dyes or pigments can be organic or inorganic compounds.
  • any aliphatic thermoplastic polyurethane is suitable for forming the top layer (3) of the molded parts according to the invention; amorphous aliphatic thermoplastic polyurethanes which are transparent are preferred.
  • Aliphatic thermoplastic polyurethanes and their preparation are known in the art, for example from EP-B1 567 883 or DE 10321081.4 (application number), and com- shoutally available, for example under the trade marks Texin ® and Desmopan ® Bayer Aktiengesellschaft.
  • Preferred aliphatic thermoplastic polyurethanes have a Shore hardness D of 45 to 70.
  • the surface gloss of the cover layer (3) measured in accordance with DIN 67530 at viewing angles of both 20 ° and 60 ° is preferably above 80 units.
  • the layer thickness of the above composite layer plates or films is preferably 110 ⁇ m to 2.8 mm.
  • the composite layer plates or films consist of a substrate layer (1) and a cover layer (3) with the following layer thicknesses: substrate layer (1) 50 ⁇ m to 1.5 mm; Cover layer (3) 10 - 500 ⁇ m.
  • the composite layer plates or films consist of a substrate layer (1), an intermediate layer (2) and a cover layer (3).
  • Composite layer plates or films composed of a substrate layer (1), an intermediate layer (2) and a cover layer (3) preferably have the following layer thicknesses: substrate layer (1) 50 ⁇ m to 1.5 mm; Intermediate layer (2) 50 to 500 ⁇ m; Cover layer (3) 10 - 500 ⁇ m.
  • the material forming the substrate layer (1) of the composite layer plates or foils, which are encompassed by the moldings according to the invention has a Vicat softening temperature (Vicat B measured according to DIN 53460 with a temperature increase of 50 K / h) of at least 105 ° C, preferably at least 108 ° C.
  • Vicat B measured according to DIN 53460 with a temperature increase of 50 K / h
  • the composite layered sheets or films which are encompassed by the moldings according to the invention have an elastic modulus E t (measured according to ISO 527-2 / 1 B at 5 mm / min at a temperature of 90 ° C.) of at least 1300 MPa , preferably at least 1400 MPa, an elastic modulus E t (measured according to ISO 527-2 / 1 B at 5 mm / min at a temperature of 100 ° C.) of at least 900 Mpa, preferably at least
  • a Shore C hardness (measured according to DIN 53505 at a temperature of 90 ° C) of at least 70, preferably at least 80, particularly preferably at least 90, very particularly preferably at least 100, and a Shore C hardness (measured according to DIN 53505 at a temperature of 100 ° C.) of at least 60, preferably at least 70, particularly preferably at least 80, very particularly preferably at least 90.
  • Three-layer plates or films can be produced, for example, from a composite layer film with two layers (2) and (3) by providing them with a substrate layer (1).
  • the production can be carried out according to methods known to the person skilled in the art, in particular according to the so-called adapter coextrusion method described below.
  • the size ratio of the MFI values (meld flow index: melt flow index) of the individual layers of the composite layer plates or foils is at most 3: 1, particularly preferably at most 2: 1.
  • the greatest MFI value of one of the layers (1), (2), (3), provided that they are present in the respective composite layer plates or films is a maximum of three times, particularly preferably a maximum of twice the lowest MFI value. This ensures a uniform flow behavior of all components used in the composite layer plates or films. This coordinated flow behavior is particularly advantageous in the adapter coextrusion manufacturing processes described below.
  • the molded parts according to the invention can have, for example, an adhesion promoter layer on the side of the substrate layer (1) facing away from the cover layer (3).
  • adhesion promoter layers are preferably produced from a material compatible with polyolefins, such as, for example, SEBS (styrene-ethylene-butadiene-styrene copolymer, sold, for example, under the brand Kraton® ). If such an adhesion promoter layer is present, it preferably has a thickness of 10 to 300 ⁇ m.
  • the composite layer plates or films of the moldings according to the invention can be produced by known processes, for example by adapter or coextrusion or by laminating the layers together.
  • the individual components are made flowable in extruders and brought into contact with one another by means of special devices in such a way that the composite layer plates or films result with the layer sequence described above.
  • the components can be co-extruded through a slot die or a multi-layer die tool. This method is explained in EP-A2-0225500.
  • the composite layer plates and foils according to the invention can be produced by laminating foils or plates of the components together in a heatable gap. First of all, foils or plates of the individual components are produced. This can be done by known methods. Then the desired layer sequence is achieved by superimposing the foils or Plates produced, whereupon they are passed through a heatable nip and are connected to a composite layer plate or film under the action of pressure and heat.
  • the composite layer plates or films can be used for the production of molded parts. Any molded parts are accessible.
  • the composite layer plates or foils are particularly preferably used for the production of molded parts in which very good surface properties, in particular gloss properties, are important.
  • the surfaces are also very scratch-resistant and adhesive, so that destruction of the surfaces by scratching or detaching the surfaces is minimized. Shaped bodies for use outdoors, for example outside of buildings, are therefore a preferred area of application.
  • the composite layer plates or foils are used for the production of motor vehicle parts, especially motor vehicle parts for exterior applications in the vehicle sector.
  • the manufacture of roof modules, bonnets, fenders, door leaves, bumpers, rear panels, as well as other large-scale external parts come into consideration.
  • the molded parts according to the invention can be produced from the composite layered sheets or films by known processes.
  • the composite laminated sheets or films can be back-injected, back-foamed, back-cast or back-pressed without any further processing stage.
  • the use of the composite layered sheets or films described enables, owing to the significantly improved elongation at break (compared to films coextruded with PMMA or SAN as the top layer), to produce even slightly three-dimensional components without prior thermoforming.
  • the composite layer plates or foils can also be subjected to a previous thermoforming process.
  • composite layer plates or foils with the three-layer structure consisting of substrate layer, intermediate layer and cover layer or the two-layer structure consisting of substrate layer and cover layer can be thermoformed to produce more complex components.
  • thermoforming processes can be used. Appropriate methods are known to the person skilled in the art.
  • the composite layer plates or foils are stretched in the thermoforming process. Since the gloss or surface quality of the composite layer plates or foils does not decrease with the stretching at high stretching ratios, for example up to 1: 5, the thermoforming processes are subject to almost no restrictions with regard to the possible stretching.
  • the molded parts according to the invention can be produced from the composite layer plates or foils, if necessary after a thermoforming process, by back injection, back foaming, back casting or back pressing. These methods are known to the person skilled in the art and are described, for example, in DE-A1 100 55 190 or DE-A1 199 39 111.
  • the molded parts according to the invention are obtained by back-molding, back-foaming, back-casting or back-pressing the composite layer films with a plastic material.
  • Thermoplastic molding compounds based on ASA or ABS are preferred plastic materials for back injection molding, back pressing or back casting.
  • Polymers Polymers, SAN polymers, poly (meth) acrylates, polyether sulfones, polybutylene terephthalate, polycarbonates, polypropylene (PP) or polyethylene (PE) as well as blends from ASA or ABS polymers and polycarbonates or polybutylene terephthalate and blends from polycarbonates and polybutylene terephthalate used, it being advisable when using PE and / or PP to provide the substrate layer beforehand with an adhesion promoter layer.
  • Amorphous thermoplastics and their blends are particularly suitable.
  • ABS or SAN polymers are preferably used as the plastic material for the back injection.
  • thermosetting molding compositions known to those skilled in the art are used for back-foaming and back-pressing.
  • these plastic materials are glass fiber reinforced, suitable variants are described in particular in DE-A1 10055 190.
  • Polyurethane foams such as are described, for example, in DE-A1 199 39 111, are preferably used for back-foaming.
  • the composite layer plate or film is deformed by hot forming, then placed in a rear molding tool and back-molded, back-molded or back-pressed with thermoplastic molding compositions, or back-foamed or back-pressed with thermosetting molding compositions.
  • the composite layer plate or film can undergo a contour cut after hot forming and before insertion into the rear mold.
  • the contour cut can also only be made after removal from the rear mold.
  • Multi-layer films produced by adapter coextrusion with the following structure were examined: 1. Transparent covering film 80 .mu.m (layer thickness) of Plexiglas ® 7M (PMMA) Rohm GmbH to 920 microns (thickness) black colored Luran ® S 778TE (ASA) BASF Aktiengesellschaft
  • Transparent cover layer made of Lexan ® SLX (modified PC) from GE Plastics on a black colored carrier made from Lexan ® (PC) from GE Plastics, total thickness 1.3 mm
  • ASA polymer with a SAN hard phase consisting of Luran ® KR2556 from BASF Aktiengesellschaft and a rubber component (acrylic ester rubber with a particle diameter of 500 nm) of 50% is used as the substrate layer.
  • ASA polymers such as Luran ® S 778TE from BASF Aktiengesellschaft
  • this product has improved heat resistance.
  • a black-colored monofilm with a thickness of 1.0 mm was produced from the ASA polymer.
  • the TPU was applied to the substrate layer using the so-called extrusion coating process.
  • the TPU was pre-dried at 60 ° C to less than 0.05% residual moisture, melted at an extruder temperature of 150 to 180 ° C and discharged via a slot die.
  • the substrate layer made of ASA was fed to the subsequent smoothing unit, so that the TPU melt emerging from the slot die was extruded onto the ASA film and smoothed on the cooled rollers and solidified.
  • the composite layer film for the molded parts according to the invention had the following structure:
  • the depth of penetration increased with decreasing hardness of the cover layer material (from PMMA to SAN to PC).
  • the film for the moldings according to the invention has an average depth of penetration immediately after scratching, but this almost completely disappeared after one day or storage at 60 ° C. Results for 2.
  • the film for the moldings according to the invention hardly lost any gloss or, surprisingly, in particular even had higher gloss values after reflow (1 h at 60 ° C.).
  • the comparative examples showed no influence of the storage on the gloss after scratching.
  • the examples demonstrate that the molded parts according to the invention have an improved surface gloss over known molded parts over the period of use, in particular in connection with frequent soiling and consequently required cleaning in automatic washing systems.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)

Abstract

L'invention concerne des corps moulés comportant une plaque ou une pellicule à couche composite et une couche support en plastique rétro-pulvérisée, rétro-expansée, rétro-coulée ou rétro-compressée. Ladite plaque ou pellicule à couche composite comporte (1) une couche de substrat contenant, par rapport à la somme des quantités des composants A, B et éventuellement C et/ou D, formant un total de 100 %, (a) 1 à 99 % d'un copolymérisat greffé viscoélastique en tant que composant A; (b) 1 à 99 % d'un ou plusieurs copolymérisats durs contenant des unités dérivées de monomères vinylaromatiques en tant que composant B; (c) 0 à 80 % de polycarbonates en tant que composant C; et (d) 0 à 50 % de charges fibreuses ou particulaires ou leurs mélanges en tant que composant (D); et (3) une couche de couverture en polyuréthane thermoplastique aliphatique. L'invention concerne également des procédés de fabrication de ces corps moulés, leur utilisation sur la partie extérieure d'un véhicule, et des parties extérieures de véhicule.
EP05701207A 2004-01-29 2005-01-27 Corps moule comportant une plaque ou une pellicule a couche composite et une couche support presentant un meilleur pouvoir de brillance Withdrawn EP1713639A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE102004004694 2004-01-29
PCT/EP2005/000783 WO2005072955A1 (fr) 2004-01-29 2005-01-27 Corps moule comportant une plaque ou une pellicule a couche composite et une couche support presentant un meilleur pouvoir de brillance

Publications (1)

Publication Number Publication Date
EP1713639A1 true EP1713639A1 (fr) 2006-10-25

Family

ID=34813049

Family Applications (1)

Application Number Title Priority Date Filing Date
EP05701207A Withdrawn EP1713639A1 (fr) 2004-01-29 2005-01-27 Corps moule comportant une plaque ou une pellicule a couche composite et une couche support presentant un meilleur pouvoir de brillance

Country Status (3)

Country Link
US (1) US20080230938A1 (fr)
EP (1) EP1713639A1 (fr)
WO (1) WO2005072955A1 (fr)

Families Citing this family (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8852744B2 (en) * 2009-12-08 2014-10-07 Bayer Materialscience Ag Composite components with improved adhesion of polycarbonate/polyester compositions and polyurethane
DE102011114362A1 (de) * 2011-09-27 2013-03-28 Gummiwerk Kraiburg Gmbh & Co. Kg Verbundbauteil aus thermoplastischem Kunststoff und Elastomeren sowie Verfahren zur Herstellung eines solchen Verbundbauteils
US9655691B2 (en) 2012-05-14 2017-05-23 Align Technology, Inc. Multilayer dental appliances and related methods and systems
WO2013172812A1 (fr) 2012-05-14 2013-11-21 Bayer Materialscience Ag Film multicouche ayant des propriétés de modules améliorées
US10286635B2 (en) 2012-05-14 2019-05-14 Covestro Deutschland Aktiengesellschaft Multi-layer film with improved modulus properties
US9138943B2 (en) 2012-09-06 2015-09-22 Xamax Industries, Inc. Composite sheet material and method for forming the same
US9205635B2 (en) 2012-09-06 2015-12-08 Xamax Industries, Inc. Composite sheet material and method for forming the same
WO2015034877A1 (fr) * 2013-09-06 2015-03-12 Xamax Industries, Inc. Matériau en feuille composite et procédé de formation
CN112677588A (zh) * 2020-11-17 2021-04-20 苏州洛瑞卡新材料科技有限公司 一种asa双层复合覆膜

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19531586A1 (de) * 1995-08-28 1997-03-06 Basf Lacke & Farben Schichtstoff
EP0847852A3 (fr) * 1996-12-10 2004-03-03 Basf Aktiengesellschaft Feuilles ou panneaux laminés et articles formés à partir de ceux-ci
DE10228376A1 (de) * 2002-06-25 2004-01-15 Basf Ag Formteil umfassend eine Verbundschichtplatte oder -folie und eine Trägerschicht

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
None *
See also references of WO2005072955A1 *

Also Published As

Publication number Publication date
WO2005072955A1 (fr) 2005-08-11
US20080230938A1 (en) 2008-09-25

Similar Documents

Publication Publication Date Title
EP0847852A2 (fr) Feuilles ou panneaux laminés et articles formés à partir de ceux-ci
EP1713639A1 (fr) Corps moule comportant une plaque ou une pellicule a couche composite et une couche support presentant un meilleur pouvoir de brillance
EP1352013A1 (fr) Preparations de pigments
EP1352012A1 (fr) Preparations de pigments
EP1192033B1 (fr) Pieces moulees en plastique pourvues sur leur partie arriere d'un revetement moule par injection
DE19651350A1 (de) Verbundschichtplatten oder -folien und Formkörper daraus
WO2004000935A1 (fr) Piece moulee qui comporte une plaque ou feuille composite et une couche de support
DE10055190A1 (de) Verfahren zur Herstellung folienhinterspritzter Kunststoffformteile sowie folienhinterspritzte Kunststoffformteile
WO2006114430A1 (fr) Objets en plastique à haptique et à aspect similaires à un métal ou à un minéral et à excellentes propriétés de façonnage
DE69907002T2 (de) Verbundwerkstoff
DE102005050930A1 (de) Formteil umfassend eine Verbundschichtplatte oder -folie und eine Trägerschicht mit verbesserter Kratzfestigkeit
DE19725560A1 (de) Verbundschichtplatten oder -folien und Formkörper daraus
EP1123353B1 (fr) Corps moules pour le secteur du batiment, utilises a l'exterieur
WO2000020505A1 (fr) Corps moules pour le secteur du batiment, utilises a l'interieur
WO1998004422A1 (fr) Enjoliveurs
WO2000020509A1 (fr) Article de sport realise a partir de melanges de polycarbonates
WO1998004625A1 (fr) Boitiers pour dispositifs de securite
DE19630103A1 (de) Wärmeisolierte Transportbehältnisse
DE10308506A1 (de) Acrylatkautschuke und Verfahren zu ihrer Herstellung
WO2005103153A1 (fr) Film ou plaque extrude(e) a tenacite amelioree
WO1998004329A1 (fr) Voitures miniatures pour enfants
DE102005027547A1 (de) Verbundschichtplatten mit hoher Kratzfestigkeit
EP0912389A1 (fr) Becquets arriere
DE19846246A1 (de) Karosserieteile für Kraftfahrzeuge
WO2000020507A1 (fr) Carters et elements de recouvrement pour filtres, pompes et moteurs

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20060829

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HU IE IS IT LI LT LU MC NL PL PT RO SE SI SK TR

17Q First examination report despatched

Effective date: 20061218

DAX Request for extension of the european patent (deleted)
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION HAS BEEN WITHDRAWN

18W Application withdrawn

Effective date: 20070426