[go: up one dir, main page]

WO2015086562A1 - Élément composite à toucher amélioré ainsi sa fabrication et son application - Google Patents

Élément composite à toucher amélioré ainsi sa fabrication et son application Download PDF

Info

Publication number
WO2015086562A1
WO2015086562A1 PCT/EP2014/076980 EP2014076980W WO2015086562A1 WO 2015086562 A1 WO2015086562 A1 WO 2015086562A1 EP 2014076980 W EP2014076980 W EP 2014076980W WO 2015086562 A1 WO2015086562 A1 WO 2015086562A1
Authority
WO
WIPO (PCT)
Prior art keywords
acid
hydroxyphenyl
bis
meth
mol
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.)
Ceased
Application number
PCT/EP2014/076980
Other languages
German (de)
English (en)
Inventor
Birgit Meyer Zu Berstenhorst
Uwe Pfeuffer
Gregor MURLOWSKI
Sebastian SCHLECHT
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.)
Covestro Deutschland AG
Original Assignee
Bayer MaterialScience AG
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 Bayer MaterialScience AG filed Critical Bayer MaterialScience AG
Publication of WO2015086562A1 publication Critical patent/WO2015086562A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B5/00—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts
    • B32B5/18—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material
    • B32B5/20—Layered products characterised by the non- homogeneity or physical structure, i.e. comprising a fibrous, filamentary, particulate or foam layer; Layered products characterised by having a layer differing constitutionally or physically in different parts characterised by features of a layer of foamed material foamed in situ
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/065—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of foam
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0023—Use of organic additives containing oxygen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0014—Use of organic additives
    • C08J9/0042—Use of organic additives containing silicon
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/0061—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof characterized by the use of several polymeric components
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
    • C08J9/04—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent
    • C08J9/12—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent
    • C08J9/14—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof using blowing gases generated by a previously added blowing agent by a physical blowing agent organic
    • C08J9/143—Halogen containing compounds
    • C08J9/144—Halogen containing compounds containing carbon, halogen and hydrogen only
    • C08J9/146—Halogen containing compounds containing carbon, halogen and hydrogen only only fluorine as halogen atoms
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2250/00—Layers arrangement
    • B32B2250/02—2 layers
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2266/00—Composition of foam
    • B32B2266/02—Organic
    • B32B2266/0214—Materials belonging to B32B27/00
    • B32B2266/0278—Polyurethane
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/71—Resistive to light or to UV
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/746—Slipping, anti-blocking, low friction
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2605/00—Vehicles
    • B32B2605/003—Interior finishings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2201/00—Foams characterised by the foaming process
    • C08J2201/02—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments
    • C08J2201/022—Foams characterised by the foaming process characterised by mechanical pre- or post-treatments premixing or pre-blending a part of the components of a foamable composition, e.g. premixing the polyol with the blowing agent, surfactant and catalyst and only adding the isocyanate at the time of foaming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/14—Saturated hydrocarbons, e.g. butane; Unspecified hydrocarbons
    • C08J2203/142—Halogenated saturated hydrocarbons, e.g. H3C-CF3
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2203/00—Foams characterized by the expanding agent
    • C08J2203/18—Binary blends of expanding agents
    • C08J2203/182—Binary blends of expanding agents of physical blowing agents, e.g. acetone and butane
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2375/00—Characterised by the use of polyureas or polyurethanes; Derivatives of such polymers
    • C08J2375/04—Polyurethanes
    • C08J2375/08—Polyurethanes from polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2483/00—Characterised by the use of macromolecular compounds obtained by reactions forming in the main chain of the macromolecule a linkage containing silicon with or without sulfur, nitrogen, oxygen, or carbon only; Derivatives of such polymers
    • C08J2483/10—Block- or graft-copolymers containing polysiloxane sequences
    • C08J2483/12—Block- or graft-copolymers containing polysiloxane sequences containing polyether sequences

Definitions

  • the invention relates to a composite component of a foamed, lightfast polyurethane layer and a plastic carrier, its preparation and use.
  • PUR Polyurethanes based on isocyanates with aromatic-bonded NCO groups are known to discolor under the action of light. This is a problem in outdoor or under light exposed interior parts. For the production of light-resistant moldings therefore a surface with appropriate properties is required.
  • PVC sheets are first contoured into an instrument panel of a car, then a carrier component, e.g. made of polypropylene. Both components are placed in a tool and then foamed with polyurethane foam, wherein the same also the bonding of the layer structure takes place.
  • the so-called "direct skinning" method has the advantage that it is possible to work with a turning tool or a sliding table, whereby the two-layer component can be produced on a machine and removed directly as a finished component (WO2010 / 083959)
  • One mold half is removed, leaving the carrier in the other mold half and replaced with a new, larger mold half, and then the resulting cavity is filled with polyurethane, at the same time adhering to the carrier
  • This procedure represents a cost-effective alternative, although the materials used are slightly more expensive than the standard materials currently used.
  • silicone-containing and / or siloxane-containing reagents can be used as surface additives in polyurethanes.
  • Such substances are described for example in “auxiliaries and additives” in “Kunststoffhandbuch 7 -Polyurethanes", Becker / Braun, Carl Hanser Verlag, Müchen / Vienna, 1993, pages 104ff.
  • properties such as e.g. Demoulding or sliding feel (friction coefficient) can be influenced. It is advantageous if as much reagent accumulates on the surface, since then either less substance used or a higher effect can be achieved.
  • the substances used are described for example in US 20120101175 AI.
  • siloxane-polyalkylene oxide copolymers in contrast to organofunctional polydimethylsiloxanes. It is shown that siloxane-polyalkylene oxide copolymers, in contrast to organofunctional polydimethylsiloxanes, lead to more stable, more emulsified mixtures. This means that the siloxane-polyalkylene oxide copolymers used are more emulsifiable than the organofunctional polydimethylsiloxanes.
  • this object could be achieved by a composite component made of a polyurethane cover layer I) and a plastic support II), wherein the plastic of the support of I) is different, which is preferably produced in the direct-skinning process, wherein for the layer A) used lightfast polyurethane containing a siloxane-polyalkylene oxide copolymer.
  • the present invention relates to composite components made of a lightfast polyurethane top layer I) and a plastic backing II) different from I), characterized in that the polyurethane cover layer I) is obtainable from
  • polystyrene resin having an average molecular weight of from 1,000 to 15,000 g / mol and a functionality of from 2 to 8, preferably from 2 to 6,
  • a further subject of the present invention is a process for the production of the composite components according to the invention from a light-fast polyurethane cover layer I) and a plastic backing II) different from I) by the DirectSkinning method by application of the lightfast polyurethane cover layer I) to the plastic support II), characterized the polyurethane cover layer I) is obtainable from
  • polystyrene resin having an average molecular weight of from 1,000 to 15,000 g / mol and a functionality of from 2 to 8, preferably from 2 to 6,
  • the outer skin of the composite component is defined for the measurement of the density as the outer layer of the composite component with a thickness of 1.5 mm on the side of the polyurethane cover layer I).
  • (cyclo) aliphatic polyisocyanates are used as starting compounds.
  • Suitable (cyclo) aliphatic polyisocyanates are preferably any by phosgenation or by phosgene-free processes, for example by thermal urethane cleavage, accessible diisocyanates of the molecular weight range 140 to 400 with aliphatically or cycloaliphatically bound isocyanate groups.
  • (cyclo) aliphatic compounds are suitable for. B.
  • modified compounds A) prepared from the monomeric (cyclo) aliphatic polyisocyanates are prepared by customary known processes. They contain as modification, for example, uretdione, isocyanurate, allophanate, biuret, iminooxadiazinedione and / or oxadiazinetrione structures, as described, for example, in J. Prakt. Chem. 336 (1994), pages 185-200, in DE-A 1670666 and EP-A 0798299 are described by way of example.
  • modified polyisocyanates A) it is also possible to use reaction products containing urethane and isocyanate groups, so-called isocyanate prepolymers and carbodiimide-modified polyisocyanates.
  • the polyisocyanates A) preferably have an isocyanate content of 10 to 30 wt .-%.
  • Preferred modified polyisocyanates A) are low-viscosity products based on HDI with a monomer content of ⁇ 0.5% by weight. Particular preference is given to using polyisocyanates based on HDI, which contain uretdione groups, and / or prepolymers based on HDI.
  • Component B) has an average hydroxyl functionality of 2 to 8 and preferably consists of at least one polyhydroxy polyether having an average molecular weight of from 1,000 to 15,000 g / mol, preferably from 2,000 to 13,000 g / mol and / or at least one polyhydroxy polyester having an average molecular weight Molecular weight of 2,000 to 10,000 g / mol, preferably 2,000 to 8,000 g / mol and / or at least one oligocarbonate polyol having an average molecular weight of 1,000 - 5,000 g / mol.
  • Suitable polyhydroxypolyethers are the alkoxylation products known per se from polyurethane chemistry of preferably di- or trifunctional starter molecules or mixtures of such starter molecules.
  • starter molecules examples include water, ethylene glycol, diethylene glycol, propylene glycol, trimethylolpropane, glycerol and sorbitol.
  • Alkylene oxides used for the alkoxylation are in particular propylene oxide and ethylene oxide, these alkylene oxides being able to be used in any order and / or as a mixture.
  • component B) it is also possible to use aliphatic oligocarbonate polyols having an average molecular weight of from 1,000 to 5,000 g / mol, preferably from 1,000 to 2,000 g / mol.
  • Suitable aliphatic oligocarbonate polyols are the per se known transesterification products of monomeric dialkyl carbonates such as dimethyl carbonate, diethyl carbonate etc. with polyols or mixtures of polyols having an OH functionality> 2.0 such as 1, 4-butanediol, 1,3-butanediol, 1, 5- pentanediol, 1,6-hexanediol, 3-methyl-l, 5-pentanediol, 1,12-dodecanediol, cyclohexanedimethanol, trimethylolpropane and / or mixtures of said polyols with lactones, as described by way of example in EP-A 1 404 740 and EP-A 1 518 879 A2.
  • Suitable polyester polyols are the esterification products of preferably dihydric alcohols which are known per se, such as, for example, ethylene glycol, propylene glycol, neopentyl glycol, 1,4-butanediol, 1,6-hexanediol, with lower amounts of preferably difunctional carboxylic acids, for example succinic acid, adipic acid, Phthalic acid, tetrahydrophthalic acid, hexahydrophthalic acid or mixtures of such acids.
  • Component C) is a chain extender having a functionality of 2 to 8 and a molecular weight of 62 to 500 g / mol, preferably 62 to 400 g / mol.
  • Preferred chain extenders C) include dihydric alcohols such as ethylene glycol, diethylene glycol, 1,4-butanediol, 1,6-hexanediol, or mixtures of such diols. Also suitable as component C) or as part of component C) are diols containing ether groups with molecular weights of less than 400 g / mol, as obtainable by propoxylation and / or ethoxylation of divalent starter molecules of the type already mentioned above by way of example. Also suitable as chain extenders C) are diamines having arylalkyl-containing amino groups, for example 1,3-xylyenediamine.
  • chain extenders C) are used in amounts of 2 to 15, preferably 4 to 12 wt .-%, based on the weight of the sum of components B), C), D) and E).
  • the blowing agents D) which are essential to the invention are physical blowing agents from the group of (cyclo) aliphatic hydrocarbons having up to 5 carbon atoms, partially halogenated hydrocarbons having up to 5 carbon atoms or partially halogenated olefins having up to 5 carbon atoms or ethers, ketones or acetates each having up to 5 carbon atoms or nitrogen-containing hydrocarbons having up to 5 carbon atoms.
  • Examples of cyclic hydrocarbons are cyclopropane and cyclopentane.
  • Non-cyclic hydrocarbons include butane, n-pentane and isopentane.
  • Halogen-containing hydrocarbons include hydrogen-containing fluorochlorohydrocarbons or fluorohydrocarbons or perfluoro compounds, for. As perfluoroalkanes understood. As chlorofluorocarbons z. For example, chlorodifluoromethane (R22), 1,1-dichloro-1-fluoroethane (R141b), 1-chloro-1, 1 -difluoroethane (R142b) or l, 3-dichloro-l, l, 2,3,3, hexafluoropropane (R216a) can be used.
  • fluorohydrocarbons examples include pentafluoroethane (R125), 1,1,1-trifluoroethane (R143a), 1,1,1,2-tetrafluoroethane (R134a), 1,1,2-trifluoroethane (R143), 1,1-difluoroethane ( R152a), 1,1,1,3,3-pentafluoropropane (R245fa), octafluoropropane (R218) or 1,1,1,3,3-pentafluorobutane (R365 mfc).
  • Halogen-containing ethers include hydrogen-containing fluorochloro or fluoro ethers, such as. B.
  • difluoro-methoxy-2,2,2-trifluoroethane (E245) understood.
  • usable ethers are dimethyl ether or diethyl ether.
  • Preferred nitrogen-containing hydrocarbon is nitromethane.
  • examples of partially halogenated olefins are trans-1,3,3,3-tetrafluoroprop-1-ene (HFO-1234ze), 2,3,3,3-tetrafluoroprop-1-ene (HFO-1234yf), FEA 1100 (1, 1 , l, 4,4,4-hexafluoro-2-butene) and FEA 1200 understood.
  • HFO-1234ze trans-1,3,3,3-tetrafluoroprop-1-ene
  • HFO-1234yf 2,3,3,3-tetrafluoroprop-1-ene
  • FEA 1100 (1, 1 , l, 4,4,4-hexafluoro-2-butene
  • FEA 1200 understood.
  • the physical blowing agent D) in an amount of 0.1 to 15 wt .-%, preferably 1 to 10 wt .-%, particularly preferably 2 to 8 wt .-% based on the weight of Sum of components B), C), D) E) and F).
  • Preferred siloxane-polyalkylene oxide copolymers used are compounds having the following formula:
  • R 1 , R 3 and R 5 are each independently selected from the group consisting of hydrogen, monovalent hydrocarbon groups of 1 to 12 carbon atoms, (R 7 ) 3Si and R 7 C (0) groups, wherein R 7 is a monovalent hydrogen group with 1 to 18 carbon atoms, R 2 , R 4 and R 6 are each independently a divalent hydrocarbon group of 1 to 12
  • Carbon atoms; a, m, n, o, p, q, x, y and z are each independently and a is 0 to 1; m is 0 to 200; n is 0 to 200; o is 1 to 200; p is 1 to 200; q is 1 to 200; x is 1 to 100; y is 1 to 50 and z is 1 to 50; at least one of R 3 or R 5 is preferably hydrogen and most preferably both R 3 and R 5 are hydrogen.
  • the siloxane-polyalkylene oxide copolymers are preferably in an amount of 0.1 to 5 wt .-%, particularly preferably from 0.2 to 4% by weight, most preferably from> 0.2 to 2% by weight, based on the weight of the sum of components B), C), D) E) and F).
  • auxiliary and additive F) to be used are compounds of the type known per se. These are the usual and known in the preparation of polyurethane foams compounds such.
  • Catalysts, stabilizers, pigments, fillers or water which may optionally be used in an amount of up to 0.3 wt .-%, based on the weight of component B).
  • the preparation of the PUR cover layer is preferably carried out without added water.
  • Catalysts which can be used are the known catalysts customary for polyurethanes, which are listed, for example, in WO 2008/034884 or EP-A 0929586. These include salts and chelates of tin, zinc, bismuth, iron, mercury as well as tertiary amine compounds.
  • Organotin compounds such as, for example, dimethyltin (IV) didodecylmercaptide, dimethyltin (IV) bis (2-ethylhexylthioglycolate), dimethyltin (rV) dimethyleneisooctyl ester mercaptide, dimethyltin (IV) didecylmercaptide, dimethyltin (IV) butenyldicarboxylate, dimethyltin dilaurate and Dimethyltin (IV) di (neo-decylcarboxylate) are preferably used.
  • non-fungicidal catalysts should be used.
  • UV absorbers may contain both inorganic compounds, such as, for example, titanium dioxide, zinc oxide or cerium dioxide, and also organic compounds, such as 2-hydroxybenzophenones, 2- (2-hydroxyphenyl) benzotriazoles, 2- (2-hydroxyphenyl) -1,3- tri-azines, 2-cyanoacrylates and oxalanilides.
  • Radical scavengers are known to include HALS systems (Hindered Amine Light Stabilizer), and as hindered phenols and / or secondary aromatic amines can be used as antioxidants.
  • Foam stabilizers usually consist of polyether siloxanes or block copolymers of polyoxyalkylenes.
  • pigments and fillers e.g. Calcium carbonate, graphite, carbon black, titanium dioxide, titanium dioxide, iron oxide, wollastonite, glass fibers, carbon fibers and organic dyes or
  • component E auxiliaries and additives
  • component E "auxiliaries and additives” are listed in "Kunststoffhandbuch 7 -Polyurethanes", Becker / Braun, Carl Hanser Verlag, Kunststoff, 1993, pages 104ff.
  • the starting components are used in amounts such that preferably one
  • Isocyanate index is the ratio of the number of NCO groups divided by the number of NCO-reactive groups multiplied by 100.
  • the components B) to F) are generally combined to form a so-called “polyol component", which is then combined with the polyisocyanate component
  • A) is mixed and reacted in closed molds.
  • an external release agent can be used to avoid adhesion of the polyurethane topcoat to the mold.
  • the temperature of the reaction components is generally within the temperature range from 20 to 60 ° C.
  • the temperature of the molding tools is generally from 20 to 100 ° C, for aliphatic PUR preferably at 50 to 90 ° C.
  • thermoplastic materials include polycarbonate, copolycarbonate, polyestercarbonate, polystyrene, styrene copolymers, aromatic polyesters such as polyethylene terephthalate (PET), PET-cyclohexanedimethanol copolymer (PETG), polyethylene naphthalate (PEN), polybutylene terephthalate (PBT), cyclic polyolefin , Poly- or copolyacrylates and poly- or copolymer methacrylate such as poly- or copolymethyl methacrylates (such as PMMA) and copolymers with styrene such as transparent polystyrene acrylonitrile (PSAN), thermoplastic
  • Polyurethanes polymers based on cyclic olefins (eg TOPAS®, a commercial product of Ticona) and polyamides (PA).
  • Thermoplastic, aromatic polycarbonates suitable as carrier material are both homopolycarbonates and copolycarbonates;
  • the polycarbonates may be linear or branched in a known manner.
  • thermoplastic polycarbonates including the thermoplastic aromatic polyester carbonates have average molecular weights M w (determined by measuring the relative viscosity at 25 ° C in CH 2 Cl 2 and a concentration of 0.5 g per 100 ml of CH 2 Cl 2 ) of 20,000 g / mol to 32,000 g / mol, preferably from 23,000 g / mol to 28,000 g / mol.
  • a portion, up to 80 mole%, preferably from 20 mole% to 50 mole%, of the carbonate groups in the appropriate polycarbonates may be replaced by aromatic dicarboxylic acid ester groups.
  • aromatic polyester carbonates Such polycarbonates, which contain both acid residues of carbonic acid and acid residues of aromatic dicarboxylic acids incorporated into the molecular chain, are referred to as aromatic polyester carbonates. They are subsumed for simplicity in the present application under the generic term of the thermoplastic, aromatic polycarbonates.
  • the preparation of the polycarbonates is carried out in a known manner from diphenols, carbonic acid derivatives, optionally chain terminators and optionally branching agents, wherein for the production of polyester carbonates, a part of the carbonic acid derivatives is replaced by aromatic dicarboxylic acids or derivatives of dicarboxylic acids, depending on the extent to be replaced in the aromatic polycarbonates Carbonate structural units by aromatic dicarboxylic ester structural units.
  • Dihydroxyaryl compounds suitable for the preparation of polycarbonates are those of the formula (2)
  • Z is an aromatic radical having 6 to 30 carbon atoms, which may contain one or more aromatic nuclei, may be substituted and aliphatic or cycloaliphatic radicals or
  • Alkylaryl or heteroatoms may contain as bridge members.
  • Z in formula (2) preferably represents a radical of the formula (3)
  • R 6 and R 7 are each independently H, Ci-Ci8-alkyl, Ci-Ci8-alkoxy, halogen such as Cl or Br or each optionally substituted aryl or aralkyl, preferably H or Ci-Ci2-alkyl, particularly preferably are H or Ci-Cs-alkyl and most preferably H or methyl, and
  • X is a single bond, -SO 2 -, -CO-, -O-, -S-, Ci- to Ce-alkylene, C 2 - to C 5 -alkylidene or C 5 - to C 6 -cycloalkylidene which is substituted by C 1 - to C 6 -cycloalkyl- Alkyl, preferably methyl or ethyl may be substituted, further for Ce to Ci2-arylene, which may optionally be condensed with further heteroatom-containing aromatic rings is.
  • X is preferably a single bond, C 1 to C 5 -alkylene, C 2 to C 5 -alkylidene, C 5 to C 8 -cycloalkylidene, -O-, -SO-, -CO-, -S-, - SO 2 -, or one for a radical of the formula (3a) or (3b)
  • R 8 and R 9 are individually selectable for each X 1 , independently of one another denote hydrogen or C 1 to C 6 -alkyl, preferably hydrogen, methyl or ethyl, and
  • X 1 is carbon and n is an integer from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom X 1 , R 8 and R 9 are simultaneously alkyl.
  • Dihydroxyarylverbmditch diphenols
  • Dihydroxydiphenyle bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) -aryl, bis (hydroxyphenyl) ether, bis (hydroxyphenyl ) ketones, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) - sulfones, bis (hydroxyphenyl) sulfoxides, l, l 'bis- (hydroxyphenyl) -diisopropylbenzenes, and their ring-alkylated and ring-halogenated compounds.
  • Diphenols suitable for the preparation of the polycarbonates to be used are, for example, hydroquinone, resorcinol, dihydroxydiphenyl, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) -cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ethers, Bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, ⁇ , ⁇ '-bis (hydroxyphenyl) diisopropylbenzenes, and their alkylated, nuclear alkylated and nuclear halogenated compounds.
  • Preferred diphenols are 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) -l-phenyl-propane, 1,1-bis (4-hydroxyphenyl) -phenyl-ethane, 2,2-bis- (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene (bisphenol M), 2,2-bis- (3-methyl-4-hydroxyphenyl) -propane, bis (3,5-dimethyl-4-hydroxyphenyl) -methane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl ) -propane, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,3-bis- [2 - (3,5-dimethyl-4-hydroxyphen
  • diphenols are 4,4'-dihydroxydiphenyl, 1, 1-bis (4-hydroxyphenyl) phenyl ethane, 2,2-bis (4-hydroxyphenyl) propane, 2,2-bis (3,5 -dimethyl-4-hydroxyphenyl) -propane, 1,1-bis (4-hydroxyphenyl) -cyclohexane and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC).
  • the chain terminator (s) are added after phosgenation at one point or at a time when phosgene is no longer present but the catalyst has not yet been metered, or before the catalyst, with the catalyst together or in parallel.
  • any branching or debranching compounds to be used are added to the synthesis, but usually before the chain terminators.
  • trisphenols, quarterphenols or acid chlorides of tri- or tetracarboxylic acids are used, or mixtures of polyphenols or acid chlorides.
  • branching compounds having three or more than three phenolic hydroxyl groups include, for example, phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene-2, 4,6-dimethyl-2, 4,6-tri- (4-hydroxyphenyl) -heptane, 1, 3,5-tri- (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4 -hydroxyphenyl) phenylmethane, 2,2-bis (4,4-bis (4-hydroxyphenyl) cyclohexyl] propane, 2,4-bis- (4-hydroxyphenyl-isopropyl) -phenol, tetra- (4-hydroxyphenyl) methane.
  • Some of the other trifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.
  • Preferred branching agents are 3,3-bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole and 1,1,1-
  • the amount of optionally used branching agent is 0.05 mol% to 2 mol%, based in turn on moles of diphenols used in each case.
  • the branching agents may be presented either with the diphenols and the chain terminators in the aqueous alkaline phase, or dissolved in an organic solvent before
  • Phosgenation can be added.
  • Suitable aromatic dicarboxylic acids for the preparation of the polyester carbonates are, for example, orthophthalic acid, terephthalic acid, isophthalic acid, tert-butyl isophthalic acid, 3,3'-diphenyl dicarboxylic acid, 4,4'-diphenyl dicarboxylic acid, 4,4-benzophenone dicarboxylic acid, 3,4'-benzophenone dicarboxylic acid, 4,4'-diphenyl ether dicarboxylic acid, 4,4'-diphenylsulfonedicarboxylic acid, 2,2-bis (4-carboxyphenyl) -propane, trimethyl-3-phenylindane-4,5'-dicarboxylic acid.
  • terephthalic acid and / or isophthalic acid are particularly preferably used.
  • Derivatives of the dicarboxylic acids are the dicarboxylic acid dihalides and the dicarboxylic acid dialkyl esters, in particular the dicarboxylic acid dichlorides and the dimethyl dicarboxylates.
  • Substitution of the carbonate groups by the aromatic dicarboxylic ester groups is essentially stoichiometric and also quantitative, so that the molar ratio of the reactants is also found in the finished polyester carbonate.
  • the incorporation of the aromatic dicarboxylic acid ester groups can be carried out both statistically and in blocks.
  • Preferred methods of preparation of the polycarbonates to be used, including the polyester carbonates are the known interfacial method and the known melt transesterification method (cf., for example, WO 2004/063249 A1, WO 2001/05866 A1, WO 2000/105867, US Pat. No. 5,340,905, US Pat. No. 5,097,002, US-A 5,717,057).
  • acid derivatives are phosgene and optionally dicarboxylic acid dichlorides, in the latter case preferably diphenyl carbonate and optionally dicarboxylic acid diester.
  • Catalysts, solvents, work-up, reaction conditions, etc. for the production of polycarbonate or production of polyester carbonate are adequately described and known in both cases.
  • the polycarbonates, polyester carbonates and polyesters can be worked up in a known manner and processed to form any shaped articles, for example by extrusion or injection molding.
  • the polycarbonate compositions may also contain the customary for the thermoplastics mentioned additives such as fillers, UV stabilizers, heat stabilizers, antistatic agents, dyes and pigments, mold release agents, IR absorbers and flame retardants in the usual amounts of generally up to 5 wt .-%, preferably 0 , 01 to 3 wt .-% based on the total composition can be added.
  • additives such as fillers, UV stabilizers, heat stabilizers, antistatic agents, dyes and pigments, mold release agents, IR absorbers and flame retardants in the usual amounts of generally up to 5 wt .-%, preferably 0 , 01 to 3 wt .-% based on the total composition can be added.
  • thermoplastic polymers which are suitable as carrier material may be homopolymers or copolymers of ethylenically unsaturated monomers or polymers of bifunctional reactive Be connections. Suitable thermoplastic polymers may also be mixtures of different polymers.
  • Suitable thermoplastic polymers include homopolymers or copolymers of one or more ethylenically unsaturated monomers (vinyl monomers) such as vinyl acetate, styrene, ⁇ -methylstyrene, nucleus-substituted styrenes, acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, N-substituted-maleimides, chloroprene, butadiene-1, 3, isoprene and C 1 -C 8 -alkyl acrylates and alkyl methacrylates.
  • vinyl monomers such as vinyl acetate, styrene, ⁇ -methylstyrene, nucleus-substituted styrenes, acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride, N-substituted-maleimides, chloroprene, butadiene-1,
  • Suitable vinyl polymers are:
  • Rubber-free vinyl polymers (hereinafter referred to as VP.1)
  • Rubber-containing vinyl polymers such as graft polymers of vinyl monomers, on a rubber (hereinafter referred to as VP.2)
  • Copolymeriste VP.l are resinous, thermoplastic and rubber-free.
  • Preferred vinyl copolymers VP.l are those from
  • Particularly preferred copolymers VP. l are those of styrene, acrylonitrile and optionally methyl methacrylate, of ⁇ -methyl styrene, acrylonitrile and optionally methyl methacrylate and of styrene, ⁇ -methyl styrene, acrylonitrile and optionally methyl methacrylate.
  • the styrene-acrylonitrile copolymers VP. l are known and can be prepared by free-radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization.
  • the copolymers VP.l preferably have molecular weights Mw (weight average, determined by light scattering or sedimentation) of 15,000 to 200,000.
  • Further particularly preferred copolymers VP. l are random copolymers of styrene and maleic anhydride, which are preferably prepared by a continuous bulk or solution polymerization in incomplete conversions from the corresponding monomer.
  • Their composition can be varied within wide limits. Preferably, they contain 5 to 25 wt .-% maleic anhydride units.
  • the polymers may also contain ring-substituted styrenes such as p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene and other substituted styrenes such as ⁇ -methylstyrene.
  • ring-substituted styrenes such as p-methylstyrene, vinyltoluene, 2,4-dimethylstyrene and other substituted styrenes such as ⁇ -methylstyrene.
  • Their molecular weights are preferably 60,000 to 200,000. They preferably have an intrinsic viscosity of from 0.3 to 0.9 (measured in dimethylformamide at 25 ° C., see Hoffmann, Krömer, Kuhn, Polymeranalytik I, Stuttgart, 1977, page 316 et seq.).
  • the vinyl polymers VP.2 are thermoplastic and rubber-containing.
  • Preferred vinyl polymers VP.2 are graft polymers. These include, e.g. Graft copolymers having rubbery elastic properties which are essentially obtainable from at least two of the following monomers: chloroprene, 1,3-butadiene, isoprene, styrene, acrylonitrile, ethylene, propylene, vinyl acetate and C 1 -C 8 -alkyl acrylates and methacrylates. Such polymers are e.g. in "Methods of Organic Chemistry” (Houben-Weyl), Vol. 14/1, Georg Thieme-Verlag, Stuttgart, 1961, pp. 393-406 and in C.B. Bucknall, "Toughened Plastics", Appl. Science Publishers, London 1977. Preferred polymers VP.2 are partially crosslinked and have gel contents of more than 20% by weight, preferably more than 40% by weight, in particular more than 60% by weight.
  • Preferred vinyl polymers VP.2 are graft polymers of: VP.2.1
  • styrene, ⁇ -methylstyrene, alkylkemsubstitu preferably methylene-substituted styrenes, C 1 -C 8 -alkyl methacrylates, preferably methyl methacrylate, C 1 -C 8 -alkyl acrylates, preferably methacrylate or mixtures of these compounds and VP.2.1.2
  • rubber polymer having a glass transition temperature below -10 ° C preferably a diene, acrylate, silicone or ethylene-propylene-diene rubber, in particular polybutadiene.
  • Particularly preferred graft polymers VP.2 are obtainable by graft polymerization of a. 10 to 70, preferably 15 to 50, in particular 20 to 40 wt .-%, based on graft polymer A.2, of acrylic acid esters or methacrylic acid esters or from 10 to 70, preferably 15 to 50, especially 20 to 40 wt .-% of a mixture from 10 to 50, preferably 20 to 35 wt .-%; based on mixture, acrylonitrile, acrylic ester or methacrylic acid ester and 50 to 90, preferably 65 to 80 wt .-%, based on the mixture, styrene (as grafting VP.2.1) on ß.
  • From 30 to 90 preferably from 50 to 85, in particular from 60 to 80,% by weight, based on graft polymer VP.2, of a butadiene polymer having at least 50% by weight, based on ⁇ , butadiene radicals (as grafting base VP.2.2), wherein preferably the gel content of the graft base ß at least 70 wt .-% (measured in toluene), the graft G 0.15 to 0.55 and the average particle diameter dso of the graft polymer VP.2 0.05 to 2 m, preferably 0.1 to 0.6 m.
  • Acrylic esters or methacrylic esters are esters of acrylic acid or methacrylic acid and monohydric alcohols having 1 to 8 carbon atoms. Particularly preferred are methyl methacrylate, ethyl methacrylate, propyl methacrylate, n-butyl acrylate, t-butyl acrylate and t-butyl methacrylate.
  • the butadiene polymer ⁇ can, in addition to butadiene radicals, contain up to 50% by weight, based on ⁇ , of radicals of other ethylenically unsaturated monomers, such as styrene, acrylonitrile, C 1 -C 4 -alkyl ester or acrylonitrile. or methacrylic acid (such as methyl acrylate, ethyl acrylate, methyl methacrylate, ethyl methacrylate), vinyl esters and / or vinyl ethers. Preference is given to polybutadiene.
  • graft polymers VP.2 include products obtained by polymerization of the graft monomers in the presence of the grafting base.
  • the degree of graft G is the weight ratio of graft grafted gomomers to the graft base (dimensionless number).
  • the mean particle diameter dso is the diameter, above and below which each 50 wt .-% of the particles are. It can be determined by means of ultracentrifuge measurement (for example Scholtan, H. Lange, Kolloid, Z. and Z. Polymere 250 (1972), 782-796).
  • polymers VP.2 are graft polymers of x. 20 to 90 wt .-%, based on VP.2, acrylate rubber having a glass transition temperature below -20 ° C as a grafting base VP.2.2 and ⁇ . From 10 to 80% by weight, based on VP.2, of at least one polymerisable, ethylenically unsaturated monomer, the or thereof in the absence of x. resulting homo- or
  • Copolymers would have a glass transition temperature above 25 ° C, as graft monomers VP.2.1.
  • the acrylate rubbers of the polymers VP.2 are preferably polymers of alkyl acrylates, optionally with up to 40% by weight, based on x, of other polymerizable, ethylenically unsaturated monomers.
  • Preferred polymerizable acrylic acid esters include C 1 -C 8 alkyl esters, for example, methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl esters, preferably halo-C 1 -C 8 -alkyl esters, such as chloroethyl acrylate, and mixtures of these monomers.
  • crosslinking monomers having more than one polymerizable double bond can be copolymerized.
  • Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having 3 to 8 C atoms and unsaturated monohydric alcohols having 3 to 12 C atoms or saturated polyols having 2 to 4 OH groups and 2 to 20 C atoms, such as, for example, ethylene glycol dimethacrylate Allyl methacrylate; polyunsaturated heterocyclic compounds, such as trivinyl and triallyl cyanurate; polyfunctional vinyl compounds such as di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.
  • Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds having at least 3 ethylenically unsaturated groups.
  • crosslinking monomers are the cyclic monomers triallylcyanurate, triallylisocyanurate, trivinylcyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes.
  • the amount of crosslinking monomers is preferably 0.02 to 5, in particular 0.05 to 2 wt .-%, based on the graft base x.
  • Preferred "other" polymerisable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, may optionally be used for the preparation of the graft base are e.g.
  • acrylate rubbers as graft base x are emulsion polymers which have a gel content of at least 60% by weight.
  • Further suitable graft bases according to VP.2.2 are silicone rubbers with graft-active sites, as described in DE-OS 37 04 657, DE-OS 37 04 655, DE-OS 36 31 540 and DE-OS 36 31 539.
  • the gel content of the grafting base VP.2.2 is determined at 25 ° C. in dimethylformamide (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I and II, Georg Thieme Verlag, Stuttgart 1977).
  • the graft polymers VP.2 can be prepared by known processes, such as mass, suspension, emulsion or bulk suspension processes.
  • Preferred polyalkylene terephthalates can be prepared from terephthalic acids (or their reactive derivatives) and aliphatic and cycloaliphatic diols having 2 to 10 carbon atoms by known methods (Kunststoff-Handbuch), Vol. VIII, p. 695 ff, Carl Hanser Verlag, Kunststoff 1973).
  • Preferred polyalkylene terephthalates contain from 80 to 100, preferably from 90 to 100, mol%, based on the dicarboxylic acid component, of terephthalic acid residues and from 80 to 100, preferably from 90 to 100 Mol%, based on the diol component, ethylene glycol and / or butanediol-l, 4 radicals.
  • radicals of other aromatic dicarboxylic acids having 8 to 14 C atoms or aliphatic dicarboxylic acids having 4 to 12 C atoms such as radicals of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4.4 'Diphenyl dicarboxylic acid, succinic, adipic, sebacic, azelaic or cyclohexanediacetic acid.
  • 1,4-radicals are 0 to 20 mole% of other aliphatic diols having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 12 carbon atoms, e.g. Residues of pentanediol-1,5, hexanediol-1,6, cyclohexanedimethanol-1,4, 3-methylpentanediol-1,3,3 and 1,6,2-ethylhexanediol-1,3,2,2-diethylpropanediol-1,3, Hexanediol 2,5, 1-4-di ( ⁇ -hydroxyethoxyphenyl) -propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis (3- ⁇ -hydroxyethoxyphenyl) -propane and 2,2-bis (4-hydroxypropoxyphenyl) propane (DE-OS 2,407,647, 2,407,776, 2,
  • the polyalkylene terephthalates can be branched by incorporation of relatively small amounts of dihydric or trihydric alcohols or of tri- or tetrabasic carboxylic acids, as described in DE-OS 1 900 270 and US Pat. No. 3,692,744.
  • Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and propane, and pentaerythritol. It is advisable not more than 1
  • polyalkylene terephthalates which have been prepared solely from terephthalic acid (or its reactive derivatives, for example their dialkyl esters) and ethanediol and / or butanediol-1,4, and mixtures thereof.
  • Preferred polyalkylene terephthalates are also copolyesters prepared from at least two of the above diols; Particularly preferred copolyesters are poly (ethylene glycol / butanediol-1,4-terephthalates).
  • the various diol residues may be in the form of blocks or randomly distributed.
  • the polyalkylene terephthalates generally have an intrinsic viscosity of 0.4 to 1.4 dl / g, preferably 0.5 to 1.3 dl / g, in particular 0.6 to 1.2 dl / g, each measured in phenol / o-Dichlorobenzene (1: 1 wt. -Tl.) At 25 ° C.
  • thermoplastic polymers suitable as carrier material may be polyolefins
  • Polyethylene can be of high and low density, ie densities from 0.91 g / cm 3 to 0.97 g / cm 3 , which are prepared by known methods, Ullmann (4.), 19, page 167 et seq., Winnacker-Kückler (4th ed.). ), 6, 353-367, Elias et al. Vohwinkel, New Polymeric Materials for Industrial Application, Kunststoff, Hanser 1983, can be used.
  • polypropylenes having molecular weights of from 10,000 g / mol to 1,000,000 g / mol, which are prepared by known processes, Ullmann (5.) A10, page 615 et seq., Houben-Weyl E20 / 2, page 722 et seq., Ullmann (4. ) 19, page 195 ff, Kirk Othmer (3rd) 16, page 357 ff, can be produced.
  • copolymers of said olefins or with other ⁇ -olefins such as polymers of ethylene with butene, hexene and / or octene and EVA (ethylene vinyl acetate copolymers), EEA (ethylene ethyl acrylate), EBA (ethylene-butyl acrylate), EAS (Acrylklareethylenacrylatcopolymerisate ), EVK (ethylene-vinylcarbazole copolymers), EPB (ethylene-propylene block copolymers), EPDM (ethylene-propylene-diene copolymers), PB (polybutylenes), PMP (polymethylpentenes), PIB (polyisobutylenes), NBR (acrylonitrile-butadiene copolymers), polyisoprenes , Methyl butylene copolymers, isoprene isobutylene copolymers.
  • EVA ethylene vinyl a
  • thermoplastic polymers which are suitable as carrier material may be poly (meth) acrylates.
  • (meth) acrylates include methacrylates and acrylates as well as mixtures of both.
  • Poly (meth) acrylates are polymers which are obtainable by polymerization of a monomer mixture which has at least 60% by weight, preferably at least 80% by weight of (meth) acrylates, based on the weight of the monomers. These monomers are well known in the art and commercially available.
  • ⁇ (meth) acrylic acid and (meth) acrylates derived from saturated alcohols such as methyl (meth) acrylate, ethyl (meth) acrylate, propyl (meth) acrylate, butyl (meth) acrylate, pentyl (meth) acrylate, Hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, heptyl (meth) acrylate;
  • ⁇ (meth) acrylates derived from unsaturated alcohols, such as. B. 01eyl (meth) acrylate, 2-
  • cycloalkyl (meth) acrylates such as 3-vinylcyclohexyl (meth) acrylate, bornyl (meth) acrylates;
  • ⁇ hydroxyalkyl (meth) acrylates such as 3-hydroxypropyl (meth) acrylate, 3,4-dihydroxybutyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate;
  • glycol di (meth) acrylates such as l, 4-butanediol (meth) acrylates
  • ⁇ (meth) acrylates of ether alcohols such as tetrahydrofurfuryl (meth) acrylate, vinyloxyethoxyethyl (meth) acrylate; and
  • polyvalent (meth) acrylates such as trimethyloylpropane tri (meth) acrylate.
  • (meth) acrylates set out above, it is also possible to use for the preparation of the poly (meth) acrylates other unsaturated monomers which are copolymerizable with the abovementioned methacrylates. In general, these compounds are used in an amount of 0 to 40 wt .-%, preferably 0 to 20 wt .-%, based on the weight of the monomers, wherein the comonomers can be used individually or as a mixture.
  • 1-alkenes such as hexene-1, heptene-1
  • branched alkenes such as vinylcyclohexane, 3,3-dimethyl-1-propene, 3-methyl-1-diisobutylene, 4-methylpentene-1
  • Vinyl esters such as vinyl acetate
  • Styrene substituted styrenes having an alkyl substituent in the side chain, such as.
  • Preferred poly (meth) acrylates are obtainable by polymerization of mixtures which have at least 20% by weight, in particular at least 60% by weight and particularly preferably at least 80% by weight, based in each case on the total weight of the monomers to be polymerized, of methyl methacrylate , These polymers are called polymethyl methacrylates.
  • Preferred thermoplastics may contain various poly (meth) acrylates, which differ, for example, in molecular weight or in the monomer composition. Further preferred embodiments are mixtures of polymethyl methacrylate copolymers, in particular polymethylmethacrylate-poly (meth) acrylimide copolymers.
  • the preparation of the (meth) acrylate homopolymers and / or copolymers from the monomers set forth above according to the various processes of radical polymerization is known per se.
  • the polymers can be prepared in bulk, solution, suspension or emulsion polymerization.
  • the bulk polymerization is exemplified in Houben-Weyl, Vol. E20, Part 2 (1987), pp. 1145ff. described.
  • Valuable information regarding solution polymerization can be found on p. 1156ff.
  • Explanations of the suspension polymerization technique can be found on p. 1149ff, while the emulsion polymerization can be found on p. 1150ff. is executed and explained.
  • thermoplastic polymers suitable as carrier material may be polyamides.
  • Preferred polyamides include aliphatic polyamides such as PA-6, PA-11, PA-12, PA-4,6, PA-4,8, PA-4,10, PA-4,12, PA-6,6 , PA-6,9, PA-6, 10, PA-6, 12, PA-10, 10, PA-12, 12, PA-6 / 6,6 copolyamide, PA-6/12 copolyamide, PA -6/11 copolyamide, PA-6,6 / 11 copolyamide, PA-6,6 / 12 copolyamide, PA-6/6, 10-copolyamide, PA-6,6 / 6,10-copolyamide, PA -4,6 / 6-copolyamide, PA
  • semi-crystalline polyamides selected from the group comprising PA-6, PA-6,6, PA-6,10, PA-4,6, PA-11, PA-12, PA-12,12, PA- 6.1, PA-6, T, PA-6, T / 6,6-copolyamide, PA-6, T / 6-copolyamide, PA-6 / 6,6-copolyamide, PA-6,6 / 6, T / 6, 1-copolyamide, PA-6, T / 2-MPMDT copolyamide, PA-9, T, PA-4,6 / 6-copolyamide and mixtures of the aforementioned polyamides.
  • the activated anionic polymerization of lactams to polyamides is carried out on an industrial scale by preparing on the one hand a solution of catalyst in lactam, optionally with impact modifier, and on the other hand a solution of activator in lactam, usually both solutions are composed so that a combination in the same ratio gives the desired total formulation. That is not necessary. It is also possible to choose other compositions, for example to meter a concentrated activator and catalyst melt into a lactam melt. Depending on the compatibility, further additives can be added to the activator, catalyst or optionally lactam melt.
  • the polymerization is carried out by mixing the individual solutions to the total formulation at 80 ° C to 200 ° C, preferably 100 ° C to 140 ° C.
  • foaming is usually carried out in closed molds.
  • the components according to the invention are preferably produced by the so-called DirectSkinning technology, which combines the injection molding of thermoplastics with the reaction injection molding (RIM) process of PUR processing. Similar to multi-component injection molding, the composite component can be manufactured directly on an injection molding machine in just one tool (multiple tools are also possible). In this case, the reaction mixture is introduced into a mold in which the plastic support II) is already located. As a molding material is metal, such as aluminum, or plastic, such as epoxy resin, in question. In the mold, the foamable reaction mixture foams and forms the composite component. When using a turntable or insert tool, for example, both manufacturing steps can be performed in parallel, which ensures short cycle times and thus high productivity.
  • the foaming of the mold can be carried out in such a way that the component has cell structure on its surface, but it can also be carried out in such a way that the molded part has a compact skin and a cellular core.
  • the post-processing effort for the composite components thus produced is very low.
  • the thickness of the polyurethane layer can be varied within wide ranges. Since the composite component is produced in just one tool, DirectSkinning does not require a separate coating system, unlike conventional processes.
  • the transport and intermediate storage of the pure injection molded parts (plastic carrier) is eliminated, which simplifies the logistical processes and minimizes the risk of contamination and damage.
  • the composite components according to the invention are used for example for the production of steering wheels, door side panels, instrument panel covers, consoles, protective pads and shelves in the vehicle interior.
  • blowing agent mixture is added in such a way that the blowing agent content is in each case about 7.5% by weight, based on all starting materials.
  • IPDA isophorone diamine
  • Irganox ® 1135 Antioxidant phenolic-based BASF SE
  • Tinuvin ® B75 mixture of Irganox ® 1135 (Antioxidant), Tinuvin ® 765 (HALS), and Tinuvin ® 571 (UV stabilizer), BASF SE.
  • Fomrez ® UL22 dimethyl tin mercaptide (activator), from Momentive.
  • Fomrez ® UL28 dimethyl tin di-neodecanoate (activator), from Momentive.
  • Niax ® Silicone 1160 organo-functional polydimethylsiloxane, company Momentive
  • Niax Silicone ® 1162 Siloxane polyalkylene oxide copolymer, from Momentive.
  • Niax Silicone ® 1166 Siloxane polyalkylene oxide copolymer, from Momentive.
  • PUR sheets were produced in the laboratory.
  • the mold temperature in the experiments was 70 ° C. and the mold size was 100 mm ⁇ 100 mm ⁇ 20 mm.
  • the surface of the samples was made with a KA3A leather grain.
  • "Eckert und Wölk VP 84151" was used as the external release agent.
  • the temperature of the components used was 25 ° C for both the isocyanate and the polyol formulation.
  • the amount that was poured into the mold was sized to give the stated mold density.
  • the friction behavior was determined using the friction slide method according to DIN EN ISO 8295 and a Zwicki 2.5KN tensile testing machine with attached mirror table.
  • the friction slide is 200g heavy and occupied on one side with open needle felt (The felt covering was not changed in the course of the measurements).
  • the sample was fixed once parallel to the longer side of the sample ("longitudinal") and once across it ("across") on the mirror table, and the friction slide was pulled over the surface at a constant speed of 500 mm / min. Traction and friction were measured and graphically displayed.
  • the samples were previously one day in standard atmosphere at 23 ° C and 50% rel. Moisture stored and measured under these conditions.
  • Niax ® Silicone L-1162 and L-1160 the coefficient of friction even in small concentrations (0.5% and 1%) to lower than 0.6, whereas when Niax Silicone L-1166 ® Also significantly higher concentrations (2%), the lubricity (low coefficient of friction) can not lower in this perceived as pleasant area. Haptikverticianer be used for cost reasons only in low concentrations. The use of Niax silicones L ® 1162 and L-1160 is therefore advantageous.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Emergency Medicine (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un élément composite constitué d'une couche de polyuréthane expansé stable à la lumière et d'un support en matière plastique, sa fabrication et son application.
PCT/EP2014/076980 2013-12-13 2014-12-09 Élément composite à toucher amélioré ainsi sa fabrication et son application Ceased WO2015086562A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP13197049.3 2013-12-13
EP13197049 2013-12-13

Publications (1)

Publication Number Publication Date
WO2015086562A1 true WO2015086562A1 (fr) 2015-06-18

Family

ID=49816808

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2014/076980 Ceased WO2015086562A1 (fr) 2013-12-13 2014-12-09 Élément composite à toucher amélioré ainsi sa fabrication et son application

Country Status (1)

Country Link
WO (1) WO2015086562A1 (fr)

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008034884A2 (fr) * 2006-09-22 2008-03-27 Dow Global Technologies Inc. Article en mousse polyuréthane
WO2011070044A1 (fr) * 2009-12-08 2011-06-16 Bayer Materialscience Ag Éléments composites à adhérence améliorée réalisés à partir de compositions de polycarbonate / polyester et de polyuréthane
US20120101175A1 (en) * 2007-08-10 2012-04-26 Kenneth Lloyd Willoughby Silicone Copolymer Surfactants For Use In Polyurethane Foams
WO2013098176A1 (fr) * 2011-12-29 2013-07-04 Bayer Intellectual Property Gmbh Compositions de polymères à adhérence améliorée

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008034884A2 (fr) * 2006-09-22 2008-03-27 Dow Global Technologies Inc. Article en mousse polyuréthane
US20120101175A1 (en) * 2007-08-10 2012-04-26 Kenneth Lloyd Willoughby Silicone Copolymer Surfactants For Use In Polyurethane Foams
WO2011070044A1 (fr) * 2009-12-08 2011-06-16 Bayer Materialscience Ag Éléments composites à adhérence améliorée réalisés à partir de compositions de polycarbonate / polyester et de polyuréthane
WO2013098176A1 (fr) * 2011-12-29 2013-07-04 Bayer Intellectual Property Gmbh Compositions de polymères à adhérence améliorée

Similar Documents

Publication Publication Date Title
EP2459625B1 (fr) Adhérence améliorée entre des matières thermoplastiques et des polyuréthanes
EP2509764B1 (fr) Procédé de fabrication d'éléments composites à base de polyuréthane et utilisation desdits éléments composites
TWI572669B (zh) 具改良之黏著性之聚合物組成物
KR101848940B1 (ko) 개선된 층간 접착력을 갖는, 폴리카르보네이트 / 폴리에스테르 조성물 및 폴리우레탄으로부터의 복합 부품
EP1024955B1 (fr) Composites a base de polyurethane et d'un materiau thermoplastique contenant un additif polaire inorganique
US9896578B2 (en) Thermoplastically processable transparent blends of thermoplastic polyurethane and poly(meth)acrylates
EP1414905B1 (fr) Compositions de polycarbonate pour une meilleure adherence de la mousse
JP7111697B2 (ja) カバー層及びｐｃ／ａｂｓ層を備える多層コンポジット物品ならびにその方法
EP3057754A1 (fr) Compositions de polycarbonate à adhérence améliorée à des couches de polyuréthane
EP3058016B1 (fr) Compositions de polycarbonate ayant une adhérence améliorée aux couches de polyuréthane
EP2899008B1 (fr) Procédé de moulage par injection pour la fabrication d'un élément composite avec structuration de surface dans la zone de contact des couches afin d'améliorer l'adhérence
EP3057755A1 (fr) Compositions de polycarbonate à adhérence améliorée à des couches de polyuréthane
WO2017068045A1 (fr) Procédé pour la préparation de masses de moulage à base de polycarbonate présentant une stabilité de mise en œuvre thermique améliorée
US11559951B2 (en) Composite component
WO2015086562A1 (fr) Élément composite à toucher amélioré ainsi sa fabrication et son application
EP4021977B1 (fr) Composition de polycarbonate ignifuge et pièces moulées et articles fabriqués à partir de cette composition
DE102009058182A1 (de) Verbundbauteile mit verbesserter Haftung aus Polycarbonat- / Polyesterzusammensetzungen und Polyurethan

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 14818905

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 14818905

Country of ref document: EP

Kind code of ref document: A1