WO2011070043A1 - Verfahren zur herstellung von polyurethan-verbundbauteilen sowie diese verbundbauteile - Google Patents

Verfahren zur herstellung von polyurethan-verbundbauteilen sowie diese verbundbauteile Download PDF

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Publication number
WO2011070043A1
WO2011070043A1 PCT/EP2010/069117 EP2010069117W WO2011070043A1 WO 2011070043 A1 WO2011070043 A1 WO 2011070043A1 EP 2010069117 W EP2010069117 W EP 2010069117W WO 2011070043 A1 WO2011070043 A1 WO 2011070043A1
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WIPO (PCT)
Prior art keywords
component
polyurethane
weight
components
carrier
Prior art date
Application number
PCT/EP2010/069117
Other languages
German (de)
English (en)
French (fr)
Inventor
Andreas Seidel
Rainer Protte
Eckhard Wenz
Uli Franz
Philipp MÖLLER
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.)
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Publication date
Family has litigation
First worldwide family litigation filed litigation Critical https://patents.darts-ip.com/?family=43447182&utm_source=google_patent&utm_medium=platform_link&utm_campaign=public_patent_search&patent=WO2011070043(A1) "Global patent litigation dataset” by Darts-ip is licensed under a Creative Commons Attribution 4.0 International License.
Priority claimed from DE102009058180A external-priority patent/DE102009058180A1/de
Priority to JP2012542528A priority Critical patent/JP5840618B2/ja
Priority to PL10785452T priority patent/PL2509764T3/pl
Priority to CN201080063363XA priority patent/CN102762354A/zh
Priority to BR112012013919A priority patent/BR112012013919A2/pt
Application filed by Bayer Materialscience Ag filed Critical Bayer Materialscience Ag
Priority to EP20100785452 priority patent/EP2509764B1/de
Priority to CA 2783167 priority patent/CA2783167A1/en
Priority to IN5073DEN2012 priority patent/IN2012DN05073A/en
Priority to MX2012006521A priority patent/MX2012006521A/es
Priority to ES10785452.3T priority patent/ES2468834T3/es
Priority to KR1020127017614A priority patent/KR101823167B1/ko
Publication of WO2011070043A1 publication Critical patent/WO2011070043A1/de

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Classifications

    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/16—Making multilayered or multicoloured articles
    • B29C45/1635—Making multilayered or multicoloured articles using displaceable mould parts, e.g. retractable partition between adjacent mould cavities
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
    • B29C37/0025—Applying surface layers, e.g. coatings, decorative layers, printed layers, to articles during shaping, e.g. in-mould printing
    • B29C37/0028—In-mould coating, e.g. by introducing the coating material into the mould after forming the article
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/16—Making multilayered or multicoloured articles
    • B29C45/1615—The materials being injected at different moulding stations
    • B29C45/162—The materials being injected at different moulding stations using means, e.g. mould parts, for transferring an injected part between moulding stations
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/16—Making multilayered or multicoloured articles
    • B29C45/1676—Making multilayered or multicoloured articles using a soft material and a rigid material, e.g. making articles with a sealing part
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/16—Making multilayered or multicoloured articles
    • B29C45/1679—Making multilayered or multicoloured articles applying surface layers onto injection-moulded substrates inside the mould cavity, e.g. in-mould coating [IMC]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/72—Heating or cooling
    • B29C45/73—Heating or cooling of the mould
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/17—Component parts, details or accessories; Auxiliary operations
    • B29C45/76—Measuring, controlling or regulating
    • B29C45/78—Measuring, controlling or regulating of temperature
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C67/00—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00
    • B29C67/24—Shaping techniques not covered by groups B29C39/00 - B29C65/00, B29C70/00 or B29C73/00 characterised by the choice of material
    • B29C67/246—Moulding high reactive monomers or prepolymers, e.g. by reaction injection moulding [RIM], liquid injection moulding [LIM]
    • 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
    • B32B27/08—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 synthetic resin
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B27/40—Layered products comprising a layer of synthetic resin comprising polyurethanes
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
    • 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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C37/00—Component parts, details, accessories or auxiliary operations, not covered by group B29C33/00 or B29C35/00
    • B29C37/0025—Applying surface layers, e.g. coatings, decorative layers, printed layers, to articles during shaping, e.g. in-mould printing
    • B29C37/0028—In-mould coating, e.g. by introducing the coating material into the mould after forming the article
    • B29C2037/0035—In-mould coating, e.g. by introducing the coating material into the mould after forming the article the coating being applied as liquid, gel, paste or the like
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2075/00—Use of PU, i.e. polyureas or polyurethanes or derivatives thereof, as moulding material
    • 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
    • B32B2250/03—3 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
    • 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
    • B32B2605/00—Vehicles
    • B32B2605/003—Interior finishings
    • 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
    • B32B2605/08—Cars
    • 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
    • B32B2605/18—Aircraft
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31507—Of polycarbonate
    • 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
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31565—Next to polyester [polyethylene terephthalate, etc.]

Definitions

  • the present invention relates to a method for the production of composite components with stable composite adhesion, wherein these comprise a structuring support of a thermoplastic material and at least one standing in direct contact with this support polyurethane layer.
  • the present invention relates to the use of particular high melt flow polycarbonate compositions and toughness in a 2-component injection or 2-component reactive injection molding process [2K- (R) IM] to produce a polyurethane coated with at least one polyurethane (PU) - or multi-component component, which is characterized by good adhesion of the PU coating (s) on the substrate.
  • 2-component injection or 2-component reactive injection molding process [2K- (R) IM]
  • Another object of the present invention relates to composite components with high toughness and stable adhesion, which comprise a structuring support made of a thermoplastic material and at least one standing in direct contact with this support polyurethane layer, and their use.
  • DE 196 50 854 C1 discloses a method for producing a multilayer plastic part in which a plastic injection molded part is coated with at least one layer of a 2-component thermoset, preferably polyurethane. In this process, the plastic part and the layer of 2-component thermosetting plastic are successively injected synchronously in the same mold. About the influence of the nature of the carrier material and the process parameters on the adhesion between the carrier material and with this related layer of the composite component are given in DE 196 50 854 Cl no evidence.
  • No. 6,558,599 B1 describes a method for producing a painted part from a molded thermoplastic material.
  • the method comprises the steps of a) injection molding the thermoplastic material into a first cavity of a tool for forming the part, b) opening the tool to cool at least the surface of the part, causing shrinkage of the part, and c) injecting a paint into a second cavity of the tool with the part, the second cavity having the same dimensions as the first cavity.
  • WO 2006/072366 A1 describes a method for forming and coating a substrate in a mold having at least two cavities. The method comprises the steps of: a) forming a substrate in a first cavity of the molding tool, b) introducing the substrate produced in the previous step into a second cavity of the molding tool, and c) coating the substrate in the second cavity with a paint, wherein the Coating is done under increased pressure.
  • a) forming a substrate in a first cavity of the molding tool b) introducing the substrate produced in the previous step into a second cavity of the molding tool, and c) coating the substrate in the second cavity with a paint, wherein the Coating is done under increased pressure.
  • PC + ABS substrates polycarbonate + acrylonitrile-butadiene-styrene substrates
  • DE 10 2006 048 252 B3 discloses a method for producing a composite component, in particular comprising an injection molded part and a polyurethane element, comprising the steps of a) producing a carrier component, b) moving or transferring the carrier component into an opened cavity of a tool, c) closing d) creating a negative pressure in the enlarged first size cavity, e) filling a flooding material into the enlarged cavity, and f) performing an embossing step simultaneously with the filling and / or subsequently to the filling of the flooding material, wherein the cavity is at least slightly reduced.
  • DE 10 2006 033 059 A1 discloses a method for producing plastic interior parts.
  • the carrier in a first step, is formed in a first tool, wherein the first tool is at least partially replaced by a second tool and then in a second step, the cover layer is formed on the support.
  • the carrier material is a hard component, for example PA + ABS blends (polyamide + acrylonitrile-butadiene-styrene) or PC + ABS blends (polycarbonate + acrylonitrile-butadiene-styrene), and a soft component, preferably polyurethane foam, is used as cover layer.
  • the technical object of the present invention was therefore to provide a process for the production of composite components with stable composite adhesion comprising (a) a structuring support of a thermoplastic material and (b) at least one polyurethane layer in direct contact with this support.
  • Another technical objective has been to provide polycarbonate compositions having high melt flowability and toughness that achieve good adhesion of the coating to the substrate when coated with a polyurethane system in a 2-component injection molding or 2-component (reactive) injection molding process.
  • the object of the present invention was also to provide composite components with high toughness and stable composite adhesion, which comprise a structuring support of a thermoplastic material and at least one standing in direct contact with this support polyurethane layer and in a 2-component injection molding process or 2-component (reactive) injection molding process.
  • the polyurethane layer can serve, for example, for improving the surface properties, the feel, the appearance, the noise and heat insulation of the composite components.
  • the object of the present invention is achieved by a process for the production of a composite component comprising a) a carrier of a thermoplastic composition and b) at least one polyurethane layer in direct contact with the carrier, in which (i) in a first process step the melt of the thermoplastic composition injected into a first mold cavity and subsequently cooled, the thermoplastic composition
  • the polyurethane raw material mixture polymerizing in contact with the surface of the thermoplastic carrier to form a compact polyurethane layer or to a polyurethane foam layer,
  • the composite component is removed from the mold cavity, wherein the method steps follow one another directly.
  • the immediate sequence of process steps prevents the temperature of the workpiece from cooling to room temperature during the process. This achieves a reduction of the production times and a higher energy efficiency of the overall process.
  • steps (ii) and (iii) can be repeated at least once, with variation of the polyurethane system, wherein one or more polyurethane layers are applied to only one or both sides of the support so that a composite component of thermoplastic support and at least two identical or different polyurethane layers. Components with possibly also more than two-layer structure results.
  • the workpiece is cooled to dimensional stability.
  • To produce the gap in process step (ii) can either open the injection mold and then replaced a half of the Spritzgusstechnikmaschine Wegvmaschine by a new half with larger cavity dimensions, or the component from the first mold cavity in a second, with respect to its mold cavity larger cavity or a second Tool implemented, or the first cavity to be opened by a gap.
  • the reaction of the substrate in process step (ii) can be carried out by known processes, as used for example in multicolor injection molding. Typical methods are on the one hand the turntable, insert, Schiebekavmaschine or index plate or similar methods in which the substrate remains on a core. If the substrate remains to be transferred on the core, this has the advantage that the position is defined accurately even after transfer. On the other hand, known in the art are methods of reacting a substrate in which the substrate, e.g. with the help of a handling system, removed from a cavity and placed in another cavity. The transfer with removal of the substrate offers greater latitude in the coating, e.g. when generating a wrap around or masked areas.
  • the polyurethane layer can represent, for example, a PU varnish, a PU foam or a compact PU skin.
  • the polyurethane layers produced by this process can have, for example, thicknesses of 1 ⁇ m to 20 cm.
  • the polyurethane layer is a paint having a layer thickness of 1 to 1000 ⁇ m.
  • the polyurethane layer is a compact skin with a layer thickness of 1 mm - 10 mm.
  • the polyurethane layer is a foam having a layer thickness of 1 cm to 20 cm.
  • the thermoplastic compositions of the carrier a) contain: A) 65.0 to 80.0 parts by weight, in particular 70.0 to 80.0 parts by weight, based on the sum of components A and B, at least one polymer selected from the group of aromatic polycarbonates, aromatic polyester and aromatic polyesters and B) 20.0 to 35.0 parts by weight, in particular 20.0 to 30.0 parts by wt., Based on the sum of components A and B, of an optionally rubber-modified vinyl (co) polymer.
  • Component C is preferably used in a proportion of 0.1 to 15.0 parts by weight, in particular 0.2 to 5.0 parts by weight, based on the sum of components A to C, is used.
  • the form of component A used is a mixture of at least one aromatic polycarbonate and / or polyester carbonate and at least one aromatic polyester.
  • the reactive polyurethane raw material mixture preferably has an index of> 90 to ⁇ 125, preferably> 100 to ⁇ 120, and particularly preferably from 105 to 115.
  • thermoplastic polyurethane may also be used instead of the reactive polyurethane raw material mixture.
  • the surface of the injection molding tool which is in contact with the thermoplastic polymer composition in process step (iii) is heated to a temperature in the range from 50 to 95.degree. C., preferably from 60 to 85.degree. C., and particularly preferably from 60 to 80.degree.
  • the temperature of the polyurethane-side mold cavity is at least 10 ° C., preferably at least 15 ° C., especially preferably at least 20 ° C higher than the temperature of the carrier side (thermoplastic side) horrkavtician.
  • thermoplastic composition carrier a thermoplastic composition carrier
  • polyurethane layer in direct contact with the carrier
  • thermoplastic composition in a first method step, the melt of the thermoplastic composition is injected into a first mold cavity and subsequently cooled, (ii) in a second method step, the cavity of the injection molding tool is enlarged, thereby creating a gap space,
  • polyurethane raw material mixture polymerises in contact with the surface of the thermoplastic carrier to form a compact polyurethane layer or to a polyurethane foam layer,
  • the composite component is removed from the mold cavity, wherein the process steps (ii) and (iii) can be repeated several times, the process steps immediately follow each other, and in process step (iii) the temperature of the polyurethane mold cavity at least 10 ° C. , preferably at least 15 ° C, more preferably at least 20 ° C higher than the temperature of the carrier side (thermoplastic side) horrkavtician.
  • a thermoplastic polymer composition is used in the first process step, which at room temperature and more preferably also at -30 ° C a tough fracture behavior in the notch impact test according to ISO 180-lA, characterized by a notched impact strength value of greater than 25 kJ / m 2 , and / or a tough (not splintering) fracture pattern in the penetration test according to ISO 6603 shows.
  • the present invention furthermore relates to the use of compositions comprising A) 65.0 to 90.0 parts by weight, based on the sum of components A and B, of at least one polymer selected from the group of aromatic polycarbonates, aromatic polyester carbonates and aromatic polyesters .
  • component A is preferably a mixture of at least one aromatic polycarbonate and / or polyester carbonate and at least one aromatic polyester.
  • the present invention relates to composite components comprising a) containing a carrier of a composition
  • component A is preferably a mixture of at least one aromatic polycarbonate and / or polyester carbonate and at least one aromatic polyester.
  • the composite components are preferably produced by a 2-component reactive injection molding process with a reactive polyurethane raw material mixture containing - at least one polyisocyanate component,
  • the reactive polyurethane raw material mixture has a ratio of> 90 to ⁇ 125, preferably> 100 to ⁇ 120, and particularly preferably from 105 to 115.
  • the composite component at -30 ° C a tough (not splintering) fracture behavior under multiaxial impact load measured on the fracture pattern in the penetration test according to ISO 6603.
  • the composite adhesion between the polycarbonate composition carrier and the polyurethane coating in the composite components according to the invention is in a preferred embodiment at least 1 N / mm, measured on strip samples taken from the component with a width of 20 mm in a roller peel test according to DIN 53357 A with a test speed of 100 mm / min.
  • the composite components according to the invention are preferably suitable for use as inner or outer component of a rail, aviation or motor vehicle.
  • the polymer compositions used in the process according to the invention contain:
  • Aromatic polycarbonates and polyestercarbonates according to component A which are suitable according to the invention are known from the literature or can be prepared by processes known from the literature (for example, see Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, 1964, and DE-A-1 495 626, DE-A 2 for the preparation of aromatic polycarbonates 232 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3 000 610, DE-A 3 832 396, for the preparation of aromatic polyester carbonates, eg DE-A 3 077 934).
  • aromatic polycarbonates and polyester carbonates takes place for. B. by reaction of diphenols with carbonic acid halides, preferably phosgene, and / or with aromatic Dicarbonklaredihalogeniden, preferably Benzoldicarbonklaihalogeniden, by the interfacial process, optionally using chain terminators, for example monophenols and optionally using trifunctional or more than trifunctional branching agents, for example, triphenols or tetraphenols.
  • chain terminators for example monophenols and optionally using trifunctional or more than trifunctional branching agents, for example, triphenols or tetraphenols.
  • preparation via a melt polymerization process by reaction of diphenols with, for example, diphenyl carbonate is possible.
  • Diphenols for the preparation of the aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (I)
  • A is a single bond, C 5 to C 5 alkylene, C 2 to C 5 alkylidene, C 5 to C 6 cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO 2 -, C fi to C [2 -aryl, to which further aromatic rings containing optionally heteroatoms may be condensed, or a radical of the formula (II) or (III)
  • C 1 to C 4 -alkyl preferably methyl, halogen, preferably chlorine and / or bromine, each independently of one another 0, 1 or 2, P is 1 or 0, and
  • R 5 and R 6 are individually selectable for each X 1 , independently of one another hydrogen or C 1 -C 4 -alkyl, preferably hydrogen, methyl or ethyl,
  • X 1 is carbon and m is an integer from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom X 1 , R 5 and R 6 are simultaneously alkyl.
  • Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis (hydroxyphenyl) -C 1 -C 5 -alkanes, bis (hydroxyphenyl) -C 5 -C 6 -cycloalkanes, bis (hydroxyphenyl) ethers, bis (hydroxy-) phenyl) sulfoxides, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) -sulfones and a, a-bis (hydroxyphenyl) -diisopropyl-benzenes and their nuclear-brominated and / or ring-chlorinated derivatives.
  • diphenols are 4,4'-dihydroxydiphenyl, bisphenol A, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 1, 1 - Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenylsulfone and their di- and tetrabrominated or chlorinated derivatives such as 2,2-bis (3-chloro-4-) hydroxyphenyl) -propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) -propane or 2,2-bis (3,5-dibromo-4-hydroxyphenyl) -propane.
  • 2,2-bis (4-hydroxyphenyl) propane bisphenol-A
  • bisphenol-A 2,2-bis (4-hydroxyphenyl) propane
  • the diphenols can be used individually or as any mixtures.
  • the diphenols are known from the literature or obtainable by literature methods.
  • Chain terminators suitable for the preparation of the thermoplastic, aromatic polycarbonates are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4- [2- (2,4,4 -Trimethylpentyl)] - phenol, 4- (l, 3-tetramethyl-butyl) -phenol according to DE-A 2,842,005 or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents such as 3,5-di-tert.
  • alkylphenols such as 4- [2- (2,4,4 -Trimethylpentyl)] - phenol, 4- (l, 3-tetramethyl-butyl) -phenol according to DE-A 2,842,005 or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents such as 3,5-d
  • the amount of chain terminators to be used is generally between 0.5 mol%, and 10 mol%, based on the molar sum of the diphenols used in each case.
  • thermoplastic, aromatic polycarbonates may be branched in a known manner, preferably by the incorporation of 0.05 to 2.0 mol%, based on the sum of the diphenols used, of trifunctional or more than trifunctional compounds, for example those with three and more phenolic groups. Both homopolycarbonates and copolycarbonates are suitable.
  • inventive copolycarbonates according to component A it is also possible to use from 1 to 25% by weight, preferably from 2.5 to 25% by weight, based on the total amount of diphenols to be used, of hydroxyaryloxy endblocked polydiorganosiloxanes. These are known (US 3 419 634) and can be prepared by literature methods. The preparation of polydiorganosiloxane-containing copolycarbonates is described in DE-A 3 334 782.
  • Preferred polycarbonates in addition to the bisphenol A homopolycarbonates, are the copolycarbonates of bisphenol A with up to 15 mol%, based on the molar sums of diphenols, of other than preferred or particularly preferred diphenols, in particular 2,2-bis (3,5-bis). dibromo-4-hydroxyphenyl) -propane.
  • Aromatic dicarboxylic acid dihalides for the preparation of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.
  • a carbonyl halide preferably phosgene, is additionally used as the bifunctional acid derivative.
  • the amount of chain terminators is in each case 0.1 to 10 mol%, based on moles of diphenol in the case of the phenolic chain terminators and on moles of dicarboxylic acid dichloride in the case of monocarboxylic acid chloride chain terminators.
  • the aromatic polyester carbonates may also contain incorporated aromatic hydroxycarboxylic acids.
  • the aromatic polyester carbonates can be branched both linearly and in a known manner (see DE-A 2 940 024 and DE-A 3 007 934).
  • suitable branching agents are trifunctional or polyfunctional carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric trichloride, 3,3 ', 4,4'-benzophenone tetracarboxylic acid tetrachloride, 1,1,5,8-naphthalene tetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride Amounts of from 0.01 to 1.0 mol% (based on the dicarboxylic acid di chlorides used) or difunctional or polyfunctional phenols, such as phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hept- 2-ene, 4,6-dimethyl-2,4,6-tris (4-hydroxyphenyl) hept
  • the proportion of carbonate structural units can vary as desired.
  • the proportion of carbonate groups is preferably up to 100 mol%, in particular up to 80 mol%, particularly preferably up to 50 mol%, based on the sum of ester groups and carbonate groups.
  • Both the ester and the carbonate portion of the aromatic polyester carbonates may be present in the form of blocks or randomly distributed in the polycondensate.
  • the relative solution viscosity ( ⁇ ⁇ ⁇ ) of the aromatic polycarbonates and polyester carbonates is preferably in the range of 1.18 to 1.4, particularly preferably in the range 1.20 to 1.32 (measured on solutions of 0.5 g of polycarbonate or polyester carbonate in 100 ml of methylene chloride solution at 25 ° C).
  • the weight-average molecular weight Mw of the aromatic polycarbonates and polyestercarbonates is preferably in the range of 15,000 to 35,000, more preferably in the range of 20,000 to 33,000, particularly preferably 23,000 to 30,000, determined by GPC (gel permeation chromatography in methylene chloride with polycarbonate as a standard).
  • component A eligible aromatic polyesters are in a preferred embodiment, polyalkylene terephthalates.
  • these are reaction products of aromatic dicarboxylic acids or their reactive derivatives, such as dimethyl esters or anhydrides, and aliphatic, cycloaliphatic or araliphatic diols and mixtures of these reaction products.
  • Particularly preferred polyalkylene terephthalates comprise at least 80% by weight, preferably at least 90% by weight, based on the dicarboxylic acid component, of terephthalic acid residues and at least 80% by weight, preferably at least 90% by mol, based on the diol component of ethylene glycol and / or butanediol l, 4-residues.
  • the preferred polyalkylene terephthalates may contain up to 20 mol%, preferably up to 10 mol%, of other aromatic or cycloaliphatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids having 4 to 12 carbon atoms, such as.
  • the preferred polyalkylene terephthalates may contain up to 20 mol%, preferably up to 10 mol%, of other aliphatic diols having 3 to 12 carbon atoms or cycloaliphatic diols having 6 to 21 carbon atoms.
  • Contain atoms eg Residues of propanediol 1, 3, 2-ethylpropanediol-1,3, neopentyl glycol, pentanediol-1,5, 1,6-hexanediol, cyclohexane-dimethanol-1,4, 3-ethylpentanediol-2,4, 2-methylpentanediol 2,4,2,2,4-trimethylpentanediol-1,3,2-ethylhexanediol-1,3,3,2-diethylpropanediol-1,3-hexanediol 2,5,1,4-di- ( ⁇ -hydroxyethoxy ) benzene, 2,2-bis (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis (4-.beta.-hydroxyethoxy) phenyl) -propan
  • the polyalkylene terephthalates can be prepared by incorporation of relatively small amounts of trihydric or trihydric alcohols or 3- or 4-basic carboxylic acids, e.g. according to DE-A 1 900 270 and US-PS
  • branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.
  • polyalkylene terephthalates prepared from terephthalic acid alone and their reactive derivatives (e.g., their dialkyl esters) and ethylene glycol and / or butane-1,4-diol, and mixtures of these polyalkylene terephthalates.
  • Polyalkylene terephthalates contain from 1 to 50% by weight, preferably from 1 to 30% by weight, of polyethylene terephthalate and from 50 to 99% by weight, preferably from 70 to 99% by weight, of polybutylene terephthalate.
  • the polyalkylene terephthalates which are preferably used generally have an intrinsic viscosity of 0.4 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, measured in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C in the Ubbelohde viscometer.
  • polyalkylene terephthalates can be prepared by known methods (see, for example, Kunststoff-Handbuch, Volume VIII, pp. 695 et seq., Carl Hanser Verlag, Kunststoff 1973).
  • Component B
  • Component B is rubber-based graft polymers or rubber-free vinyl (co) polymers or a mixture of several such polymers.
  • B.1.2 from 95 to 5, preferably 85 to 8, in particular 75 to 40 wt .-%, based on component Bl, one or more graft bases with glass transition temperatures ⁇ 10 ° C, preferably ⁇ 0 ° C, particularly preferably ⁇ -20 ° C. ,
  • the glass transition temperature was determined by means of differential scanning calorimetry (DSC) according to the standard DIN EN 61006 at a heating rate of 10 K / min with definition of T g as the center temperature (tangent method).
  • the graft B.1.2 generally has an average particle size (d 50 value) of 0.05 to 10 ⁇ , preferably 0.1 to 5 ⁇ , more preferably 0.2 to 1 ⁇ .
  • the average particle size dso is the diameter, above and below which each 50 wt .-% of the particles are. It can be determined by ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymere 250 (1972), 782-1796).
  • Monomers B.1.1 are preferably mixtures of
  • B.l .1.1 50 to 99, preferably 65 to 85, in particular 75 to 80 parts by weight, based on B.1.1,
  • Vinylaromatics and / or ring-substituted vinylaromatics such as styrene, ⁇ -methylstyrene, p-methylstyrene, p-chlorostyrene
  • CC 8 methacrylic acid alkyl esters, such as methyl methacrylate, ethyl methacrylate
  • Bl .1.2 1 to 50, preferably 15 to 35, in particular 20 to 25 parts by weight, based on B.1.1,
  • Vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth) acrylic acid (C C8) alkyl esters, such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids, for example maleic anhydride and N-phenyl-maleimide.
  • C C8 alkyl esters such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids, for example maleic anhydride and N-phenyl-maleimide.
  • Preferred monomers B.I.1.1 are selected from at least one of the monomers styrene, ⁇ -methylstyrene and methyl methacrylate
  • preferred monomers B.I.1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate.
  • Particularly preferred monomers are B.l.1.1 styrene and B.l.1.2 acrylonitrile.
  • diene rubbers EP (D) M rubbers, ie those based on ethylene / propylene and, if appropriate, are suitable for the graft polymers B1 suitable grafting bases B.1.2 Diene, acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers, and silicone / acrylate composite rubbers.
  • Preferred grafting bases B.1.2 are diene rubbers, for example based on butadiene and isoprene, or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with other copolymerizable monomers (for example according to B.1.1.1 and B.1.1.2), with the proviso that the glass transition temperature of component B.1.2 is below ⁇ 10 ° C., preferably ⁇ 0 ° C., particularly preferably ⁇ -20 ° C.
  • graft base B.1.2 is pure polybutadiene rubber.
  • the graft copolymers B.l are obtained by free-radical polymerization, e.g. by emulsion, suspension, solution or bulk polymerization, preferably by emulsion or bulk polymerization, in particular by emulsion polymerization.
  • the content of graft base B.1.2 is preferably 20 to 95% by weight, particularly preferably 40 to 85% by weight, in particular 50 to 75% by weight, in each case based on B.I.
  • the content of graft base B.1.2 is preferably 5 to 50% by weight, more preferably 8 to 25% by weight, in particular 10 to 20% by weight, in each case on B. l.
  • the gel content of the graft base B.1.2 is at least 30% by weight, preferably at least 40% by weight, in particular at least 60% by weight, in each case based on B.1.2 and measured as the insoluble fraction in toluene.
  • Particularly suitable graft rubbers are also ABS polymers which are prepared by redox initiation with an initiator system of organic hydroperoxide and ascorbic acid according to US Pat. No. 4,937,285.
  • graft polymers B 1 according to the invention are also those products which are obtained by (co) polymerization of the grafting monomers in the presence of the grafting base and are obtained during the workup. These products Accordingly, they may also contain free (ie not chemically bound to the rubber (co) polymer of the graft monomers.
  • Suitable Acrylatkauts chuke according to B .1.2 are preferably polymers of alkyl acrylates, optionally with up to 40 wt .-%, based on B.1.2 other polymerizable, ethylenically unsaturated monomers.
  • Preferred polymerizable acrylic esters include C 1 to C 6 alkyl esters, for example, methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl esters, preferably halo-C 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 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 three ethylenically unsaturated groups.
  • Particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, 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 B.1.2.
  • Preferred "other" polymerizable, ethylenically unsaturated monomers which may optionally be used for preparing the graft B.1.2 addition to the acrylic esters are, for example acrylonitrile, styrene, ⁇ -methyl styrene, acrylamides, vinyl-Ci-C ö -alkyl ethers, methyl methacrylate, butadiene.
  • Preferred acrylate rubbers as the graft base B.1.2 are emulsion polymers which have a gel content of at least 60% by weight.
  • Suitable graft bases according to B .1.2 are silicone rubbers with graft-active sites, as described in DE-OS 3,704,657, DE-OS 3,704,655, DE-OS 3 631 540 and DE-OS 3 631 539.
  • the gel content of the graft base B.1.2 or of the graft polymers B.l is determined at 25 ° C. in a suitable solvent as insoluble in these solvents (M. Hoffmann, H. Krömer, R. Kuhn, Polymer Analytics I and II, Georg Thieme-Verlag, Stuttgart 1977).
  • the rubber-free vinyl (co) polymers according to component B.2 are preferably rubber-free homopolymers and / or copolymers of at least one monomer from the group of vinylaromatics, vinyl cyanides (unsaturated nitriles), (meth) acrylic acid (C 1 to C 4) 8 ) -alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids.
  • (Meth) acrylic acid (C C8) -alkyl ester for example, methyl methacrylate, n-butyl acrylate, tert-butyl acrylate, and
  • B.2.2 1 to 50 wt .-%, preferably 20 to 40 wt .-%, in particular 20 to 30 wt .-%, each based on the total weight of the (co) polymer B.2, at least one monomer selected from the group the vinyl cyanides, such as unsaturated nitriles such as Acrylonitrile and methacrylonitrile, (meth) acrylic acid (C C8) alkyl esters, such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate, unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids, such as maleic anhydride and N-phenyl-maleimide.
  • These (co) polymers B.2 are resinous, thermoplastic and rubber-free.
  • the copolymer of B.2.1 styrene and B.2.2 acrylonitrile is particularly preferred.
  • Such (co) polymers B.2 are known and can be prepared by free-radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization.
  • the (co) polymers preferably have average molecular weights M w (weight average, determined by GPC) between 15,000 and 250,000 g / mol, preferably in the range 80,000 to 150,000 g mol
  • the composition may contain as component C commercial polymer additives.
  • Commercially available polymer additives according to component C are additives such as flame retardants (for example phosphorus compounds such as phosphoric or phosphonic acid esters, phosphonatamines and phosphazenes or halogen compounds), flame retardant synergists (for example nanoscale metal oxides), smoke-inhibiting additives (for example boric acid or borates), antidripping agents (for example compounds of the Classes of fluorinated polyolefins, silicones and aramid fibers), internal and external Lubricants and mold release agents (for example, pentaerythritol tetrastearate, stearyl stearate, montan wax or polyethylene wax), flowability improvers (for example low molecular weight vinyl (co) polymers), antistatics (for example block copolymers of ethylene oxide and propylene oxide, other polyethers or polyhydroxyethers, polyetheramides, polyesteramides or sulfonic
  • the coating used is preferably a polyurethane foam or a compact polyurethane layer.
  • the polyurethanes used according to the invention are obtained by reacting polyisocyanates with H-active polyfunctional compounds, preferably polyols.
  • polyurethane is also understood as meaning polyurethaneureas in which H-active polyfunctional compounds such compounds having N-H functionality, if appropriate in admixture with polyols, are used.
  • Suitable polyisocyanates are the aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates known per se with an NCO functionality of preferably> 2, which also include iminooxadiazinedione, isocyanurate, uretdione, urethane, allophanate, biuret, urea, oxadiazinetrione , Oxazolidinone, acylurea and / or carbodiimide structures. These can be used individually or in any mixtures with each other.
  • polyisocyanates are based on diisocyanates or triisocyanates known per se with aliphatic, cycloaliphatic, araliphatic and / or aromatically bound isocyanate groups, it being immaterial whether these are using phosgene or produced by phosgene-free processes.
  • di- or triisocyanates examples include 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (HDI), 2-methyl-1-1,5-diisocyanato-pentane, 1,5-diisocyanato-2,2 -dimethylpentane, 2,2,4- and 2,4,4-trimethyl-l, 6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1, 4-diisocyanatocyclohexane, 1,3- and 1,4 - bis (isocyanatomethyl) cyclohexane, l-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl cyclohexane (isophorone diisocyanate, IPDI), 4,4'-diisocyanatodicyclohexylmethane (Desmod)
  • the polyisocyanates preferably have an average NCO functionality of from 2.0 to 5.0, preferably from 2.2 to 4.5, particularly preferably from 2.2 to 2.7, and a content of isocyanate groups of from 5.0 to 37 , 0 wt .-%, preferably from 14.0 to 34.0 wt .-% to.
  • polyisocyanates or polyisocyanate mixtures of the abovementioned type with exclusively aliphatically and / or cycloaliphatically bonded isocyanate groups are used.
  • modified polyisocyanates are in particular the known from polyurethane chemistry prepolymers having terminal isocyanate groups in the molecular weight range 400 to 15,000, preferably 600 to 12,000 of interest. These compounds are prepared in a conventional manner by reacting excess amounts of simple polyisocyanates of the type exemplified with organic compounds having at least two isocyanate-reactive groups, in particular organic polyhydroxyl compounds.
  • Suitable such polyhydroxy compounds are both simple polyhydric alcohols in the molecular weight range 82 to 599, preferably 62 to 200, such as ethylene glycol, trimethylolpropane, 1,2-propanediol or 1,4-butanediol or 2,3-butanediol, but especially higher molecular weight polyether polyols and / or polyester polyols the type known per se from polyurethane chemistry having molecular weights of from 600 to 12,000, preferably from 800 to 4,000, which have at least two, as a rule from 2 to 8, but preferably from 2 to 6, primary and / or secondary hydroxyl groups.
  • NCO prepolymers which have been obtained, for example, from low molecular weight polyisocyanates of the type mentioned by way of example and less preferred compounds having isocyanate-reactive groups such as polythioether polyols, hydroxyl-containing polyacetals, polyhydroxypolycarbonates, polyesteramides containing hydroxyl groups or copolymers of olefinically unsaturated compounds having hydroxyl groups are.
  • Suitable compounds for preparing the NCO prepolymers with isocyanate-reactive groups, in particular hydroxyl groups are, for example, the compounds disclosed in US Pat. No. 4,218,543. In the preparation of the NCO prepolymers, these compounds are reacted with isocyanate-reactive groups with simple polyisocyanates of the type exemplified above while maintaining an NCO excess.
  • the NCO prepolymers generally have an NCO content of from 10 to 26, preferably from 15 to 26,% by weight.
  • the chain extenders usually crosslinking in polyurethane chemistry come in terms of ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-propanediol. Preference is given to diols such as 2-butanediol-1,4-butanediol-1,3, butanediol-2,3 and / or 2-methylpropanediol-1,3. Of course, it is also possible to use the aliphatic diols in a mixture with each other.
  • Polyols having an average OH number of from 5 to 600 mg KOH / g and an average functionality of from 2 to 6 are suitable as the H-active component. Polyols having an average OH number of from 10 to 50 mg KOH / g are preferred.
  • suitable polyols according to the invention are polyhydroxypolyethers obtainable by alkoxylation of suitable starter molecules, such as ethylene glycol, diethylene glycol, 1,4-dihydroxybutane, 1,6-dihydroxyhexane, dimethylolpropane, glycerol, pentaerythritol, sorbitol or sucrose.
  • ammonia or amines such as ethylenediamine, hexamethylenediamine, 2,4-diaminotoluene, aniline or amino alcohols or phenols such as bisphenol-A.
  • the alkoxylation is carried out using propylene oxide and / or ethylene oxide in any order or as a mixture.
  • At least one further crosslinker and / or chain extender may additionally be selected from the group comprising amines and amino alcohols, for example ethanolamine, diethanolamine, diisopropanolamine, ethylenediamine, triethanolamine, isophronediamine, N, N'-dimethyl (diethyl) -ethylenediamine, 2 amino-2-methyl (or ethyl) -l-propanol, 2-amino-1-butanol, 3-amino-1,2-propanediol, 2-amino-2-methyl (ethyl) -l, 3-propanediol, and alcohols, for example ethylene glycol, diethylene glycol, 1, 4-dihydroxybutane, 1, 6-dihydroxyhexane, dimethylolpropane, glycerol and pentaerythritol, and sorbitol and sucrose, or mixtures of these compounds.
  • amines and amino alcohols for example ethanolamine, di
  • polyester polyols as are obtainable by reacting low molecular weight alcohols with polybasic carboxylic acids, such as adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid or the anhydrides of these acids, in a manner known per se, unless the viscosity of the H-active component becomes too great.
  • a preferred polyol having ester groups is castor oil.
  • polyhydroxypolyethers in which high molecular weight polyadducts or polycondensates or polymers in finely dispersed, dissolved or grafted form are present.
  • modified polyhydroxy compounds are prepared in a manner known per se, for example. when polyaddition reactions (e.g., reactions between polyisocyanates and aminofunctional compounds) and polycondensation reactions (e.g., between formaldehyde and phenols and / or amines) occur in situ in the hydroxyl group-containing compounds.
  • polyaddition reactions e.g., reactions between polyisocyanates and aminofunctional compounds
  • polycondensation reactions e.g., between formaldehyde and phenols and / or amines
  • Vinyl polymer-modified polyhydroxyl compounds as obtained, for example, by polymerization of styrene and acrylonitrile in the presence of polyethers or polycarbonate polyols, are also suitable for the preparation of polyurethanes.
  • polyether polyols which according to DE-A 2 442 101, DE-A 2 844 922 and DE-A 2 646 141 by graft polymerization with vinylphosphonic and optionally (meth) acrylonitrile, (meth) acrylamide or OH-functional (meth) acrylic acid esters were modified, we obtain plastics of particular flame retardancy.
  • Representatives of said compounds to be used as H-active compounds are described, for example, in High Polymers, Vol.
  • the limitation of the average OH number and average functionality of the H-active component results in particular from the increasing embrittlement of the resulting polyurethane.
  • the person skilled in the Eml. Eml. on the polymer-physical properties of the polyurethane are known, so that NCO component, aliphatic diol and polyol can be matched to one another in a favorable manner.
  • the polyurethane layer (b) may be foamed or solid, e.g. present as a paint or coating.
  • auxiliaries and additives are to be used: a) water and / or volatile inorganic or organic substances as blowing agents
  • organic blowing agents are, for example, acetone, ethyl acetate, halogen-substituted alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane Butane, hexane, heptane or diethyl ether, as inorganic blowing agents air, C0 2 or N 2 0 in question.
  • a blowing effect can also be achieved by adding compounds which decompose at temperatures above room temperature with elimination of gases, for example nitrogen, for example azo compounds, such as azodicarbonamide or azoisobutyronitrile.
  • catalysts for example, acetone, ethyl acetate, halogen-substitute
  • the catalysts are, for example, to
  • tertiary amines such as triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, ⁇ , ⁇ , ⁇ ', ⁇ '-tetramethylethylenediamine, pentamethyldiethylenetriamine and higher homologs, 1,4-diazabicyclo- (2,2,2) octane, N- Methyl-N'-dimethylaminoethylpiperazine, bis (dimethylaminoalkyl) piperazine, N, N-dimethylbenzylamine, ⁇ , ⁇ -dimethylcyclohexylamine, N, N-diethylbenzene cylamine, bis- (N, N-diethylamino-ethyl) adipate, N, N, N ', N'-tetramethyl-1,3-butanediamine, N, N-
  • Amide groups (preferably formamide groups) having tertiary amines
  • Mannich bases of secondary amines such as dimethylamine
  • aldehydes preferably
  • tertiary amines containing isocyanate-active hydrogen atoms for example triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldietanolamine, N, N-dimethylethanolamine
  • alkylene oxides such as propylene oxide and / or
  • nitrogenous bases such as tetraalkylammonium hydroxides
  • Alkali hydroxides such as sodium hydroxide, alkali phenolates such as sodium phenolate
  • Alkali alcoholates such as sodium methylate
  • Alkali alcoholates such as sodium methylate
  • organic metal compounds in particular organic tin and / or bismuth compounds
  • Suitable tin compounds in addition to sulfur-containing compounds such as di-n-octyl-tin-mercaptide are preferably tin (II) salts of carboxylic acids such as tin (II) acetate, tin (II) octoate, tin (II) ethylhexoate and tin ( II) laurate and the tin (IV) compounds, eg Dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate or dioctyltin diacetate.
  • Organic bismuth catalysts are described, for example, in the patent application WO 2004/000905.
  • catalysts mentioned above can be used as mixtures.
  • combinations of organic metal compounds and amides, aminopyridines or hydrazinopyridines are generally used in an amount of about 0.001 to 10 wt.%, Based on the total amount of compounds having at least two isocyanate-reactive hydrogen atoms.
  • Surface-active additives such as emulsifiers and foam stabilizers.
  • emulsifiers are e.g. the sodium salts of castor oil sulfonates or salts of fatty acids with amines such as diethylamine or diethanolamine stearic acid.
  • alkali metal ammonium salts of sulfonic acids such as dodecylbenzenesulfonic acid or dinaphthylmethanedisulfonic acid or of fatty acids such as ricinoleic acid or of polymeric fatty acids can also be used as surface-active additives.
  • Suitable foam stabilizers are in particular polyethersiloxanes, especially water-soluble representatives. These compounds are generally designed so that a copolymer of ethylene oxide and propylene oxide is connected to a Polydimethylsiloxanrest. Of particular interest are branched polysiloxane-polyoxyalkylene copolymers in many cases via allophanate groups. d) reaction retarder
  • reaction retarder e.g. acidic substances (such as hydrochloric acid or organic acid halides) in question.
  • additives e.g. acidic substances (such as hydrochloric acid or organic acid halides) in question.
  • Suitable PU additives are, for example, cell regulators of the type known per se (such as paraffins or fatty alcohols) or dimethylpolysiloxanes and also pigments or dyes and flame retardants of the type known per se (for example tris-chloroethyl phosphate, tricresyl phosphate or ammonium phosphate and polyphosphate), and stabilizers against aging. and weathering agents, plasticizers and fungistatic and bacteriostatic substances and fillers (such as barium sulfate, diatomaceous earth, carbon black or whiting) into account.
  • cell regulators of the type known per se such as paraffins or fatty alcohols
  • dimethylpolysiloxanes also pigments or dyes and flame retardants of the type known per se (for example tris-chloroethyl phosphate, tricresyl phosphate or ammonium phosphate and polyphosphate)
  • stabilizers against aging for example tris-ch
  • Component Al Linear polycarbonate based on bisphenol A having a weight-average molecular weight M w of 17,000 g / mol.
  • MVR melt volume flow rate
  • Component B-1 Precompound of an ABS graft polymer prepared in emulsion and a bulk polymerized SAN polymer.
  • the precompound has an acrymitrile: butadiene: styrene weight ratio of 20:28:52 wt%.
  • Precompound of an AB S graft polymer prepared in emulsion and a bulk polymerized SAN polymer.
  • the precompound has an acrymitrile: butadiene: styrene weight ratio of 16:27:57 wt%.
  • Component B-3
  • ABS graft polymer with core-shell structure prepared in emulsion polymerization consisting of 42 wt .-% styrene-acrylonitrile copolymer with a ratio of styrene to acrylonitrile of 72: 28 wt .-% as a shell to 58 wt .-% of a particulate graft with a average particle size d 50 of 0.3 ⁇ core, wherein the graft base consists of pure polybutadiene rubber.
  • ABS polymer prepared by bulk polymerization of 88 wt .-% based on the ABS polymer of a mixture of 24 wt .-% acrylonitrile and 76 wt .-% of styrene in the presence of 12 wt .-% based on the ABS polymer a linear polybutadiene rubber.
  • Clearstrength® E920 Methyl methacrylate / butadiene / styrene polymer (MBS) with core-shell structure, prepared in emulsion polymerization, with a polybutadiene content of about 75% by weight (Arkema, France).
  • MMS Methyl methacrylate / butadiene / styrene polymer
  • Paraloid® EXL 2650 Methyl methacrylate / butadiene polymer (MB) with core-shell structure, prepared in emulsion polymerization, with a polybutadiene content of about 80% by weight (Rohm & Haas, France).
  • PETS pentaerythritol tetrastearate
  • Irganox® B900 Mixture of 80% by weight of Irgafos® 168 (tris (2,4-di-tert-butyl) phenyl-phosphite) and 20% by weight of Irganox® 1076 (octadecyl-3 ( 3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (BASF, Germany)
  • C3 Irganox® 1076 (octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate) (BASF, Germany)
  • C4 carbon black as pigment
  • Bayflex® VP.PU 47IF01A is a polyol based on a long-chain polyether containing ethanediol, diethanolamine, isophoronediamine, with a viscosity according to DIN 53019 of 1,600 mPa.s at 20 ° C, a density according to DIN 51757 of 1.04 g / cm 3 at 20 ° C and a hydroxyl number of 166 mg KOH / g.
  • Desmodur® VP.PU 48IF30 is an aliphatic isocyanate based on isophorone diisocyanate (IPDI) with an NCO content according to DIN EN ISO 11909 of 30.5 wt.%, A viscosity at 23 ° C. according to DIN EN ISO 3219 / A. 3 of 200 mPa-s and a density at 20 ° C according to DIN EN ISO 2811 of 1.1 g / cm 3 .
  • the granules resulting from the respective compounding are processed on an injection molding machine (Arburg) at a melt temperature of 260 ° C. and a mold temperature of 80 ° C. to form test specimens measuring 80 mm ⁇ 10 mm ⁇ 4 mm.
  • the sizes mentioned in the present application are determined by the following methods: The ductility of the molding compositions is assessed on the basis of the impact value a k measured on these test specimens according to ISO 180-1A at 23 ° C. and -30 ° C.
  • the heat resistance is assessed using the Vicat B 120 or Vicat B50 values measured on these test specimens in accordance with ISO 306.
  • the melt flowability is assessed on the basis of the melt viscosity measured at 260 ° C. and a shear rate of 1000 s -1 on the basis of ISO 11443.
  • the composite adhesion between the polycarbonate composition substrate and the polyurethane skin is measured on strip samples having a width of 20 mm, which have been sawn from the partially PU-coated 2-component composite panels thus produced by a roller peel test according to DIN 53357 A determined at a test speed of 100 mm / min.
  • Partially surface coated moldings having a 412 cm 2 projected area were produced on an injection molding machine in a two cavity injection mold (a substrate side cavity and a polyurethane side coating cavity associated with a RIM unit).
  • the composite component is a plate-shaped component made of thermoplastic material (carrier) whose surface has been partially coated with a polyurethane skin.
  • the wall thickness of the carrier molding b was approx. 4 mm.
  • the polyurethane layer thickness was also 4 mm.
  • FIG. 1 The inventive method for producing the composite components described in the examples according to the invention is shown in FIG. 1 for better illustration.
  • the carrier molding was produced.
  • thermoplastic granules of the compositions as described in Tables 1 to 3 was melted in an injection cylinder and injected at a temperature of 270 ° C in the first mold cavity of the closed tool (steps 1 and 2 in Figure 1).
  • This mold cavity was tempered to temperatures of 80 or 100 ° C.
  • the tool was opened in the second step (step 3 in Figure 1).
  • the support member produced was held on the off weref erseite the injection mold and from the carrier position (step 3 in Figure 1) completely with the tool core via a slider in the coating position (step 4 in Figure 1).
  • the injection mold was closed again (step 5 in FIG. 1), a closing force for a maximum pressure of 200 bar was established, and in the third process step the solvent-free reactive polyurethane system (see above) was injected under a pressure of about 30 bar into the coating cavity (step 6 in Figure 1).
  • the two reactive components of the polyurethane coating system were thereby conveyed by the RIM system in a high-pressure countercurrent mixing head and mixed there before injection.
  • the PU-side cavity was tempered to temperatures of 80 or 100 ° C.
  • the injection nozzle of the polyurethane mixing head was sealed by means of a hydraulic cylinder under a pressure of initially 50 bar to prevent backflow of the coating material.
  • the tool was opened a further time (step 7 in Figure 1) and the coated molded part removed from the mold (step 8 in Figure 1).
  • Table 1 shows the influence of the carrier compositions (polyurethane system in all cases: mixture of Bayflex VP.PU 47IF01 A and Desmodur VP.PU 48IF30 with a ratio of 95. Temperature of the substrate-side mold cavity in all cases: 80 ° C, temperature of the PU side Tool cavity in all cases: 80 ° C) on the adhesion between the layers of the composite component.
  • Table 2 shows the influence of a polyester-containing system on the adhesion of the composite component (PU system: mixture of Bayflex VP.PU 47IF01A and Desmodur VP.PU 48IF30 with a ratio of 95. Temperature of the substrate-side tool cavity: 80 ° C, temperature of PU-side mold cavity: 80 ° C). Table 2:
  • Table 3 shows influences of the polyurethane composition and the mold temperatures (composition of the substrate material in all cases of Example 9 in Table 1)
  • the composite adhesion between the carrier composition and the polyurethane layer proves largely independent of the type of graft polymer / vinyl (co) polymer (component B) present in the carrier composition and of the molecular weight of the polycarbonate used (components A) ( compare Example 4 with Examples 7-10).
  • Example 11 in Table 2 shows that a particularly good composite adhesion is then achieved if instead of aromatic polycarbonate as component A a mixture of aromatic polycarbonate and aromatic polyester is used.

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  • Mechanical Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Medicinal Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Polyurethanes Or Polyureas (AREA)
PCT/EP2010/069117 2009-12-08 2010-12-08 Verfahren zur herstellung von polyurethan-verbundbauteilen sowie diese verbundbauteile WO2011070043A1 (de)

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KR1020127017614A KR101823167B1 (ko) 2009-12-08 2010-12-08 폴리우레탄 복합 부품의 제조 방법, 및 상기 복합 부품
ES10785452.3T ES2468834T3 (es) 2009-12-08 2010-12-08 Procedimiento para la fabricación de piezas de construcción de material compuesto de poliuretano as� como el uso de estas piezas de construcción de material compuesto
PL10785452T PL2509764T3 (pl) 2009-12-08 2010-12-08 Sposób wytwarzania poliuretanowych konstrukcyjnych elementów kompozytowych jak i zastosowanie tych konstrukcyjnych elementów kompozytowych
CN201080063363XA CN102762354A (zh) 2009-12-08 2010-12-08 聚氨酯复合构件的制造方法和这些复合构件
BR112012013919A BR112012013919A2 (pt) 2009-12-08 2010-12-08 método para a produção de componentes de compósito de poliuretano assim como estes componentes de compósito
JP2012542528A JP5840618B2 (ja) 2009-12-08 2010-12-08 ポリウレタン複合材料部材の製造方法および複合材料部材
EP20100785452 EP2509764B1 (de) 2009-12-08 2010-12-08 Verfahren zur herstellung von polyurethan-verbundbauteilen sowie die verwendung dieser verbundbauteile
CA 2783167 CA2783167A1 (en) 2009-12-08 2010-12-08 Method for producing polyurethane composite components, and said composite components
IN5073DEN2012 IN2012DN05073A (zh) 2009-12-08 2010-12-08
MX2012006521A MX2012006521A (es) 2009-12-08 2010-12-08 Procedimiento para la fabricacion de piezas de construccion combinadas de poliuretano asi como estas piezas de construccion combinadas.

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JP2015510524A (ja) * 2011-12-29 2015-04-09 バイエル・インテレクチュアル・プロパティ・ゲゼルシャフト・ミット・ベシュレンクテル・ハフツングＢａｙｅｒ Ｉｎｔｅｌｌｅｃｔｕａｌ Ｐｒｏｐｅｒｔｙ ＧｍｂＨ 改良された接着性を有するポリマー組成物
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US11559951B2 (en) 2016-12-28 2023-01-24 Covestro Deutschland Ag Composite component

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