EP4051497A1 - Composite stratifié comprenant du polycarbonate et un mélange de polycarbonate pour une meilleure peignabilité - Google Patents

Composite stratifié comprenant du polycarbonate et un mélange de polycarbonate pour une meilleure peignabilité

Info

Publication number
EP4051497A1
EP4051497A1 EP20793725.1A EP20793725A EP4051497A1 EP 4051497 A1 EP4051497 A1 EP 4051497A1 EP 20793725 A EP20793725 A EP 20793725A EP 4051497 A1 EP4051497 A1 EP 4051497A1
Authority
EP
European Patent Office
Prior art keywords
layer
weight
polyester component
thermoplastic polymer
particularly preferably
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP20793725.1A
Other languages
German (de)
English (en)
Inventor
Christopher Schirwitz
Matthias KNAUPP
Marius Nolte
Ralf Hufen
Dirk Hinzmann
Sven SIEGEMUND
Uwe Klippert
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 Intellectual Property GmbH and Co KG
Original Assignee
Covestro Intellectual Property GmbH and Co KG
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 Covestro Intellectual Property GmbH and Co KG filed Critical Covestro Intellectual Property GmbH and Co KG
Publication of EP4051497A1 publication Critical patent/EP4051497A1/fr
Withdrawn legal-status Critical Current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
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/12—Layered products comprising a layer of synthetic resin next to a fibrous or filamentary layer
    • 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
    • B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • 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
    • B32B33/00—Layered products characterised by particular properties or particular surface features, e.g. particular surface coatings; Layered products designed for particular purposes not covered by another single class
    • 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
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • 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
    • B32B5/02—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 structural features of a fibrous or filamentary layer
    • B32B5/12—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 structural features of a fibrous or filamentary layer characterised by the relative arrangement of fibres or filaments of different layers, e.g. the fibres or filaments being parallel or perpendicular to each other
    • 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
    • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
    • 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
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B37/00—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding
    • B32B37/14—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers
    • B32B37/24—Methods or apparatus for laminating, e.g. by curing or by ultrasonic bonding characterised by the properties of the layers with at least one layer not being coherent before laminating, e.g. made up from granular material sprinkled onto a substrate
    • B32B2037/243—Coating
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/10—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer
    • B32B2255/102—Coating on the layer surface on synthetic resin layer or on natural or synthetic rubber layer synthetic resin or rubber layer being a foamed layer
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/26—Polymeric coating
    • 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
    • B32B2255/00—Coating on the layer surface
    • B32B2255/28—Multiple coating on one surface
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/02—Composition of the impregnated, bonded or embedded layer
    • B32B2260/021—Fibrous or filamentary layer
    • 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
    • B32B2260/00—Layered product comprising an impregnated, embedded, or bonded layer wherein the layer comprises an impregnation, embedding, or binder material
    • B32B2260/04—Impregnation, embedding, or binder material
    • B32B2260/046—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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • 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
    • B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
    • 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
    • B32B2305/00—Condition, form or state of the layers or laminate
    • B32B2305/08—Reinforcements
    • 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
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/558—Impact strength, toughness
    • 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
    • B32B2307/732—Dimensional properties
    • 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
    • B32B2313/00—Elements other than metals
    • B32B2313/04—Carbon
    • 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
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • 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
    • B32B2369/00—Polycarbonates
    • 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

Definitions

  • the present invention relates to a layer composite of a polycarbonate-based matrix, optionally containing fibers, and a top layer of special polycarbonate-polyester blends, and a layer composite as described above, the top layer of which is provided with a coating on the side facing away from the matrix Production of these composites, as well as their use for the production of, for example, automobile add-on parts.
  • Polycarbonates polycarbonate blends, for example based on PC and ASA or ABS, and polycarbonate composites, i.e. fiber-reinforced polycarbonates, have long been established in the automotive industry. They are used, for example, in the manufacture of automotive add-on parts. Due to their low weight, the weight of the vehicle components produced in this way is significantly reduced in comparison to corresponding vehicle components which were produced using conventional materials, and this while maintaining the same strength and safety. This can significantly reduce fuel consumption.
  • the plastic parts are coated with primer layers, so-called primers, to protect against environmental influences, and layers of lacquer to achieve optical or effect properties.
  • primers to protect against environmental influences
  • layers of lacquer to achieve optical or effect properties.
  • bubbles, blisters, sink marks and cracks can form in the coating, as shown in the experimental section of this document. This is undesirable for aesthetic reasons and can also impair the protective effect of the coating.
  • the object of the present invention was to provide a polycarbonate-based system which can be provided with a coating, in particular a coating for automotive add-on parts, without the disadvantages of the prior art shown.
  • the problem was solved by a multi-layer structure made of a polycarbonate-based matrix and a top layer made of special polycarbonate-polyester blends.
  • the present invention relates to a layer composite comprising a substrate layer S and a cover layer D at least partially connected to the substrate layer S, wherein the material of the substrate layer S comprises a first thermoplastic polymer and the material of the cover layer D also comprises the first thermoplastic polymer, characterized in that the first thermoplastic polymer is an aromatic polycarbonate and in the material of the cover layer D the first thermoplastic polymer as a blend a polyester component P is present, i) the proportion of this polyester component P> 2% by weight, preferably> 5
  • the total weight of the material of the outer layer D is, and the polyester component P comprises or consists of at least one polycycloalkylene terephthalate, ii) the proportion of this polyester component P> 10% by weight, preferably> 15
  • the total weight of the material of the outer layer D is, and the polyester component P comprises or consists of at least one polyalkylene terephthalate, iii) the proportion of this polyester component P> 20% by weight, preferably> 30
  • the total weight of the material of the outer layer D is, and the polyester component P comprises or consists of at least one polyalkylene naphthalate, iv) the proportion of this polyester component P> 2% by weight, preferably> 5
  • the polyester component P comprises a mixture or consists of a mixture of at least 2 of the following components: at least one polycycloalkylene terephthalate, at least one polyalkylene terephthalate, at least one polyalkylene naphthalate.
  • a mixture which comprises or consists of at least one polycycloalkylene terephthalate and at least one polyalkylene terephthalate, or - At least one polycycloalkylene terephthalate and at least one polyalkylene naphthalate, or
  • At least one polyalkylene terephthalate and at least one polyalkylene naphthalate At least one polyalkylene terephthalate and at least one polyalkylene naphthalate.
  • a mixture which comprises or consists of at least one polycycloalkylene terephthalate and at least one polyalkylene terephthalate.
  • DE 202017004083 U1 discloses a multilayer structure made of a core based on a fiber-containing thermoplastic, which is preferably polypropylene or polyamide, and a cover layer made of a thermoplastic film, which is also preferably made of polypropylene or polyamide (claim 1, [0014], [0041]). Polycarbonate-based systems are not mentioned. The document also does not deal with the paintability of thermoplastics.
  • component P comprises or consists of certain polyester components (see i) to iv)).
  • the corresponding polyester component can contain, for example, impurities or other plastics, such as further polyesters, the latter not being those mentioned in the other polyester components.
  • embodiment i) describes a polyester component P which comprises one or more polycycloalkylene terephthalate (s).
  • polyalkylene terephthalates for example, cannot additionally be contained in the polyester component. If polyalkylene terephthalates are also contained, this is to be treated as embodiment iv).
  • polycarbonates are both homopolycarbonates and copolycarbonates and / or polyester carbonates; the polycarbonates can be linear or branched in a known manner. Mixtures of polycarbonates can also be used according to the invention.
  • the weight-average molecular weight M w of the aromatic polycarbonates and polyester carbonates is in the range from 15,000 to 35,000, preferably in the range from 20,000 to 33,000, more preferably 23,000 to 31,000, determined by GPC (gel permeation chromatography in methylene chloride with polycarbonate as standard).
  • aromatic polyester carbonates Some, up to 80 mol%, preferably from 20 mol% to 50 mol%, of the carbonate groups in the polycarbonates used according to the invention can 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 built into the molecular chain, are referred to as aromatic polyester carbonates. In the context of the present invention, they are subsumed under the generic term of thermoplastic, aromatic polycarbonates.
  • the polycarbonates are produced in a known manner from diphenols, carbonic acid derivatives, optionally chain terminators and optionally branching agents, some of the carbonic acid derivatives being replaced by aromatic dicarboxylic acids or derivatives of dicarboxylic acids, depending on the amount to be replaced in the aromatic polycarbonates, to produce the polyester carbonates
  • Dihydroxyaryl compounds suitable for the production of polycarbonates are those of the formula (1)
  • HO-Z-OH (1) in which Z is an aromatic radical with 6 to 30 carbon atoms, which can contain one or more aromatic nuclei, can be substituted and can contain aliphatic or cycloaliphatic radicals or alkylaryls or heteroatoms as bridge members .
  • Z in formula (1) is preferably a radical of the formula (2) in the
  • R 6 and R 7 independently of one another for H, Ci- to Cis-alkyl, Ci- to Cis-alkoxy, halogen such as Cl or Br or for each optionally substituted aryl or aralkyl, preferably for H or Ci- to Ci2-alkyl, particularly preferred for H or C1 to Cs-alkyl and very particularly preferably for H or methyl, and
  • X represents a single bond, -SO2-, -CO-, -O-, -S-, Ci- to C ö alkylene, C2- to C5-alkylidene or C 5 to CVCycloalkylidcn which, with Ci- to Ce- alkyl preferably methyl or ethyl, can also be substituted for Ce- to C12-
  • Arylene which can optionally be fused with further aromatic rings containing heteroatoms.
  • X is preferably a single bond, C j to C 5 alkylene, C 2 to C 5 alkylidene, C 5 to C 8 cycloalkylidene, -O-, -SO-, -CO-, -S-, -S0 2 - or for a radical of the formula (3a)
  • dihydroxyaryl compounds diphenols
  • dihydroxybenzenes dihydroxydiphenyls
  • Diphenols suitable for producing the polycarbonates to be used according to the invention 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, a, a'-bis (hydroxyphenyl) diisopropylbenzenes and their alkylated, ring alkylated and ring halogenated compounds.
  • Preferred diphenols are 4,4'-dihydroxydiphenyl, 2,2-bis- (4-hydroxyphenyl) -l-phenylpropane, 1,1-bis- (4-hydroxyphenyl) -phenylethane, 2,2-bis- (4-hydroxyphenyl) ) propane, 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 1,3-bis- [2- (4-hydroxyphenyl) -2-propyl] benzene
  • 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 I, I -bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (Bisphenol TMC).
  • the monofunctional chain terminators required to regulate the molecular weight such as phenols or alkylphenols, in particular phenol, p-tert. Butylphenol, iso-octylphenol, cumylphenol, their chlorocarbonic acid esters or acid chlorides of monocarboxylic acids or mixtures of these chain terminators are either added to the reaction with the bisphenolate or bisphenolates or added at any point in the synthesis as long as phosgene or chlorocarbonic acid end groups are still in the reaction mixture are present, or in the case of the acid chlorides and chlorocarbonic acid esters as chain terminators, as long as sufficient phenolic end groups of the polymer being formed are available.
  • the chain terminator or terminators are added after the phosgenation at one point or at a time when no more phosgene is present but the catalyst has not yet been metered in, or they are metered in before the catalyst, together with the catalyst or in parallel.
  • Any branching agents or branching mixtures to be used are added to the synthesis in the same way, but usually before the chain terminators.
  • trisphenols, quarter phenols or acid chlorides of tri- or tetracarboxylic acids or mixtures of the polyphenols or the acid chlorides are used.
  • Some of the compounds with three or more than three phenolic hydroxyl groups that can be used as branching agents are, for example, phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2, 4,6-dimethyl-2, 4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tris- (4-hydroxyphenyl) -benzene, l, l, l-tri- (4-hydroxyphenyl) -ethane, tris- (4 -hydroxyphenyl) - phenylmethane, 2,2-bis- [4,4-bis- (4-hydroxyphenyl) -cyclohexyl] -propane, 2,4-bis- (4-hydroxyphenyl-isopropyl) -phenol, tetra- (4 hydroxyphenyl) methane.
  • 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-tri (4-hydroxyphenyl) ethane.
  • the amount of branching agents to be used is 0.05 mol% to 2 mol%, again based on the moles of diphenols used in each case.
  • the branching agents can either be initially introduced with the diphenols and the chain terminators in the aqueous alkaline phase or dissolved in an organic solvent and added before the phosgenation.
  • Aromatic dicarboxylic acids suitable for preparing the polyester carbonates are, for example, orthophthalic acid, terephthalic acid, isophthalic acid, tert-butyl isophthalic acid, 3,3'-diphenyldicarboxylic acid, 4,4'-diphenyldicarboxylic acid, 4,4'-benzophenonedicarboxylic acid, 3,4'-benzophenonedicarboxylic acid, 4,4 '-Diphenyletherdicarboxylic acid, 4,4'-
  • Diphenylsulfonedicarboxylic acid 2,2-bis- (4-carboxyphenyl) -propane, trimethyl-3-phenylindan-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 dicarboxylic acid dimethyl esters.
  • the replacement of the carbonate groups by the aromatic dicarboxylic acid ester groups takes place essentially stoichiometrically and also quantitatively, 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 take place either randomly or in blocks.
  • Preferred methods of production of the polycarbonates to be used according to the invention, including the polyester carbonates, are the known interfacial process and the known melt transesterification process (cf., for example, WO 2004/063249 A1, WO 2001/05866 A1, WO 2000/105867, US Pat 5,097,002 A, US-A 5,717,057 A).
  • the acid derivatives used are preferably phosgene and optionally dicarboxylic acid dichlorides, in the latter case preferably diphenyl carbonate and optionally dicarboxylic acid diesters.
  • Catalysts, solvents, work-up, reaction conditions, etc. for the production of polycarbonate or polyester carbonate are adequately described and known in both fields.
  • the material of the substrate layer S can also contain plastics other than polycarbonate as blend partners.
  • the blend partners are used in amounts of preferably a maximum of 70% by weight, particularly preferably a maximum of 50% by weight, very particularly preferably a maximum of 35% by weight based on the total weight
  • additives up to 10.0% by weight, preferably 0.10 to 8.0% by weight, particularly preferably 0.2 to 3.0% by weight, based on the total weight of the material of the substrate layer, are other customary ones Contains additives.
  • This group includes flame retardants, anti-dripping agents, thermal stabilizers, mold release agents, antioxidants, UV absorbers, IR absorbers, antistatic agents, optical brighteners, light scattering agents, colorants such as pigments, including inorganic pigments, carbon black and / or dyes, and inorganic fillers in the usual polycarbonate materials Amounts.
  • additives can be added individually or as a mixture.
  • the substrate layer can contain one or more reinforcement fiber layers made of a fiber material. This creates fiber-containing composite materials, hereinafter referred to as fiber composite materials.
  • the substrate layer S can also consist of several layers of fiber composite material and is then referred to as a multilayer composite material.
  • the chemical structure of the fibers of the fiber material can be of the most varied of types.
  • the fiber materials have a higher softening or melting point than the thermoplastic matrix material present in each case.
  • the fiber material used is preferably coated with suitable sizes.
  • the fiber layer is designed as a unidirectional fiber layer, as a woven or gauze layer, as a knitted fabric, knitted fabric or braid, as random fiber mats or fleeces or as a combination thereof.
  • the best properties of fiber composite materials were achieved with unidirectional fiber layers, fabrics and scrims.
  • Unidirectional in the context of the invention means that the fibers are aligned essentially unidirectionally, that is to say point lengthwise in one direction and thus have the same running direction.
  • essentially unidirectional it is meant here that a deviation of the grain direction of up to 5% is possible.
  • the deviation in the grain direction is preferably well below 3%, particularly preferably well below 1%.
  • the fiber material can be present as short fibers (length ⁇ 1mm), as long fibers (1 to 50 mm) or as continuous fibers (> 50 mm). It is preferably in the form of long fibers or continuous fibers in front. According to the invention, the fiber material is preferably ground fibers or chopped glass fibers. “Available” means that it can also be a mixture with other fiber materials. However, the respective fiber material is preferably the only fiber material.
  • continuous fiber is to be understood in the sense of the invention as a delimitation from the short or long fibers likewise known to the person skilled in the art.
  • Continuous fibers usually extend over the entire length of the layer of fiber composite material.
  • the term continuous fiber is derived from the fact that these fibers are wound up on a roll and are unwound and impregnated with plastic during the production of the individual fiber composite material layers, so that, with the exception of occasional breakage or roll changes, their length is usually essentially the same as the length of the manufactured fiber composite material layer matches.
  • fiber materials are inorganic materials such as silicate and non-silicate glasses of various types, carbon, basalt, boron, silicon carbide, metals, metal alloys, metal oxides, metal nitrides, metal carbides and silicates, as well as organic materials such as natural and synthetic polymers, for example polyacrylonitriles, polyesters, ultra-vertically oriented ones Polyamides, polyimides, aramids, liquid crystalline polymers, polyphenylene sulfides, polyether ketones, polyether ether ketones, polyether imides.
  • High-melting materials for example glasses, carbon, aramids, basalt, liquid crystal polymers, polyphenylene sulfides, polyether ketones, polyether ether ketones and polyether imides are preferred.
  • Particularly preferred fiber materials are glass fibers or carbon fibers.
  • a layer of fiber material also referred to as a fiber layer, is understood to be a flat layer which is formed by fibers arranged essentially in a surface.
  • the fibers can be connected to one another by their position to one another, for example by a fabric-like arrangement of the fibers.
  • the fiber layer can also have a proportion of resin or another adhesive in order to connect the fibers to one another.
  • the fibers can also be unconnected. This is understood to mean that the fibers can be detached from one another without the application of any significant force.
  • the fiber layer can also have a combination of connected and unconnected fibers. At least one side of the fiber layer is embedded in the polycarbonate-based compositions used according to the invention as a matrix material.
  • the fiber layer is surrounded at least on one side, preferably on both sides, by the polycarbonate-based composition.
  • the outer edge of the fiber composite material is preferably formed by the matrix made of a polycarbonate-based composition.
  • the number of fiber layers in a layer of fiber composite material is basically not restricted. Two or more fiber layers can therefore also be arranged one above the other. Two fiber layers lying one above the other can each be embedded individually in the matrix material so that they are each surrounded on both sides by the matrix material. Furthermore, two or more fiber layers can also lie directly on top of one another, so that their entirety is surrounded by the matrix material. In this case, these two or more fiber layers can also be viewed as one thick fiber layer.
  • Multilayer composites and materials have at least two, preferably at least three superimposed layers of fiber composite material, whereby in the case of three composite material layers these are defined relative to one another as two outer layers of fiber composite material and at least one inner layer of fiber composite material.
  • the preferred fiber material in the layers of fiber composite material are continuous fibers, which are preferably aligned unidirectionally.
  • the inner layers of fiber composite material can be oriented essentially identically and their orientation relative to the outer layers of fiber composite material can be rotated by 30 ° to 90 °, the orientation of a layer of fiber composite material being determined by the orientation of the unidirectional fibers contained therein becomes.
  • the layers are arranged alternately.
  • the outer layers are in a 0 ° orientation. It has proven to be particularly practical if the inner layers of fiber composite material are oriented in the same way and their orientation is rotated by 90 ° relative to the outer layers of fiber composite material. “Alternating” means that the inner layers are arranged alternately at an angle of 90 ° or an angle of 30 ° to 90 °.
  • the outer layers are each in a 0 ° orientation. The angles can be varied from 30 ° to 90 ° for each position.
  • Another preferred embodiment is that at least some of the layers have the same orientation and at least one other part of the layers is rotated by 30 ° to 90 °.
  • the outer layers are in a 0 ° orientation.
  • Another preferred embodiment is that the inner layers have the same orientation and their orientation relative to the outer layers of laser composite material is rotated by 30 ° to 90 ° and the outer layers are in a 0 ° orientation for this purpose.
  • the layers of laser composite materials are stacked alternately in the warp direction (0 °) and weft direction (90 °) or at the angles indicated above in the Lalle of fabrics.
  • the laser or multilayer composite materials can have a metallic sound. They also have the advantage that they can be manufactured inexpensively and are extremely lightweight due to the plastic used therein. Another advantage of the laser or multilayer composite materials is that the design, for example of a housing part, can be particularly simple and flexible due to the thermoformability of the composite materials.
  • the multilayer composite material according to the invention can also contain one or more further layers in addition to the layers of laser composite material.
  • Additional layers made of plastic which can be identical to or different from the plastic matrix used in the layers of laser composite material, may be mentioned here by way of example.
  • These plastic layers can in particular also contain fillers that are different from the laser materials provided according to the invention.
  • Learner can also be included in the multilayer composite material according to the invention, adhesive, fabric, fleece or surface coating layers, for example lacquer layers.
  • These further layers can be contained between inner and outer layers of laser composite material, between several inner layers of laser composite material and / or on the outer layer of laser composite material, which is on the side facing away from cover layer D.
  • the outer layer and the at least one inner layer of laser composite material are preferably connected to one another in such a way that no further layers lie between them.
  • the individual layers of laser composite material can be constructed and / or oriented essentially identically or differently.
  • an essentially identical structure of the layers of laser composite material is understood to mean that at least one feature from the group of chemical composition, laser volume content and layer thickness is the same.
  • Chemical composition is understood to mean the chemical composition of the plastic matrix of the fiber composite material and / or the chemical composition of the fiber material such as continuous fibers.
  • the outer layers of fiber composite material have essentially the same structure with regard to their composition, their fiber volume content and their layer thickness.
  • the multilayer composite material preferably has a total thickness of 0.4 to 2.5 mm, preferably 0.7 to 1.8 mm, in particular 0.9 to 1.2 mm. Practical tests have shown that it is possible with the multilayer composite material according to the invention to achieve extremely good mechanical properties even with these small thicknesses.
  • the sum of all inner layers of fiber composite material has a total thickness of 200 ⁇ m to 1200 ⁇ m, preferably 400 ⁇ m to 1000 ⁇ m, particularly preferably 500 ⁇ m to 750 ⁇ m.
  • each of the two outer layers of fiber composite material is 100 to 250 ⁇ m, preferably 120 ⁇ m to 230 ⁇ m, particularly preferably 130 ⁇ m to 180 ⁇ m.
  • Fiber composite layers preferred according to the invention have a fiber volume content of> 30% by volume and ⁇ 60% by volume, preferably> 35% by volume and ⁇ 55% by volume, particularly preferably> 37% by volume and ⁇ 52% by volume. -% on.
  • a fiber volume content of over 60% by volume leads to a deterioration in the mechanical properties of the fiber composite material. Without wishing to be bound by scientific theories, this seems to be due to the fact that the fibers can no longer be adequately wetted during impregnation with such high fiber volume contents, which leads to an increase in air inclusions and an increased occurrence of surface defects in the fiber composite material, and more significantly Reduction of the mechanical load capacity leads.
  • the volume content of the fiber material in the total volume of the multilayer composite material is in the range from 30 to 60% by volume, preferably in the range from 40 to 55% by volume.
  • the outer layers of fiber composite material have a fiber volume content of at most 50% by volume, preferably at most 45% by volume, in particular at most 42% by volume. According to a particular embodiment of the invention, the outer layers of fiber composite material have a fiber volume content of at least 30% by volume, preferably at least 35% by volume, in particular at least 37% by volume.
  • the outer layers of fiber composite material have a lower volume content of fibers, based on the total volume of the layer of fiber composite material, than the at least one inner layer of fiber composite material.
  • the inner layers of fiber composite material can have a fiber volume content of 40 to 60% by volume, preferably 45 to 55% by volume, particularly preferably 48 to 52% by volume, based on the total volume of the fiber composite material layer.
  • Vol .-% is understood here to mean the volume fraction (% v / v) based on the total volume of the layer of fiber composite material.
  • the material of the cover layer D comprises the aromatic polycarbonate, which is also contained in the substrate layer S as a blend with a polyester component P which comprises poly (cyclo) alkylene terephthalates and polyalkylene naphthalates or mixtures of these polyesters according to the statements of claim 1.
  • polyesters are reaction products of terephthalic acid or
  • Naphthalene-2,6-dicarboxylic acid or its reactive derivatives such as, for example, the dimethyl esters of these two acids, and aliphatic or cycloaliphatic diols.
  • (ar) aliphatic diols with 3 to 12 carbon atoms such as, for example: Ethylene glycol, 1,4-butanediol, 1,3-propanediol, 2-ethylpropanediol-1,3, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-ethylpentanediol-2,4, 2-methylpentanediol-2, 4, 2,2,4-trimethylpentanediol-1,3, 2-ethylhexanediol-1,3, 2,2-diethylpropanediol-1,3, hexanediol-2,5, 1,4-di- (ß-hydroxyethoxy) - benzene, 2,2-bis- (4-ß-hydroxyethoxyphenyl
  • cycloaliphatic diols with 6 to 21 carbon atoms, such as, for example: cyclohexane-1,4-dimethanol,
  • Particularly preferred polyalkylene terephthalates or naphthalates contain at least 80% by weight, preferably at least 90% by weight, based on the dicarboxylic acid component, terephthalic acid residues or naphthalene-2,6-dicarboxylic acid residues and at least 80% by weight, preferably at least 90 mol- %, based on the diol component, ethylene glycol and / or 1,4-butanediol residues.
  • Particularly preferred polycycloalkylene terephthalates contain at least 80% by weight, preferably at least 90% by weight, based on the dicarboxylic acid component tere phthalic acid residues and at least 80% by weight, preferably at least 90 mol%, based on the diol component cyclohexane-dimethanol-1, 4- and / or 2,2,4,4-tetramethyl-1,3cyclobutanediol residues.
  • the preferred poly (cyclo) alkylene terephthalates or polyalkylene naphthalates can contain, in addition to terephthalic acid residues or naphthalene-2,6-dicarboxylic acid residues, up to 20 mol%, preferably up to 10 mol%, residues of other aromatic or cycloaliphatic dicarboxylic acids having 8 to 14 carbon atoms or aliphatic dicarboxylic acids with 4 to 12 carbon atoms, such as residues of phthalic acid, isophthalic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.
  • the preferred polyalkylene terephthalates or naphthalates can contain, in addition to ethylene glycol or butanediol 1,4 radicals, up to 20 mol%, preferably up to 10 mol%, of other (ar) aliphatic diols with 3 to 12 carbon atoms, For example, residues of 1,3-propanediol, 2-ethylpropanediol-1,3, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, 3-ethylpentanediol-2,4, 2-methylpentanediol-2,4,2 , 2,4-trimethylpentanediol-1,3,2-ethylhexanediol 1,3, 2,2-Diethylpropanediol-1,3, hexanediol-2,5, 1,4-di- (ß-hydroxyethoxy) -benzene,
  • the preferred polycycloalkylene terephthalates can contain up to 20 mol%, preferably up to 10 mol%, of other cyclo aliphatic diols Contain 6 to 21 carbon atoms, for example residues of 2,2-bis (4-hydroxycyclohexyl) propane.
  • polyesters can be branched by incorporating relatively small amounts of 3- or 4-valent alcohols or 3- or 4-basic carboxylic acids, e.g. according to DE-A 1 900270 and US Pat. No. 3,692,744.
  • preferred branching agents are trimesic acid, trimellitic acid, trimethylol ethane and propane and pentaerythritol.
  • Very particularly preferred polyalkylene terephthalates are based solely on terephthalic acid or its reactive derivatives (e.g. its dialkyl esters) and ethylene glycol or 1,4-butanediol.
  • Very particularly preferred polycycloalkylene terephthalates are based solely on terephthalic acid or its reactive derivatives (e.g. its dialkyl esters) and cyclohexanedimethanol-1,4 and / or 2,2,4,4-tetramethyl-1,3cyclobutanediol.
  • Very particularly preferred polyalkylene naphthalates are based solely on naphthalene-2,6-dicarboxylic acid or its reactive derivatives (e.g. their dialkyl esters) and ethylene glycol or 1,4-butanediol.
  • poly (cyclo) alkylene terephthalates and polyalkylene naphthalates can be produced by known methods (see e.g. Kunststoff-Handbuch, Volume VIII, pp. 695 ff., Carl-Hanser-Verlag, Kunststoff 1973).
  • the proportion of polyester component P is very particularly preferably> 30% by weight, even more preferably> 35% by weight, based on the total weight of the material of the outer layer D, provided that polyester component P according to variant i) comprises or consists of at least one polycycloalkylene terephthalate.
  • the proportion of the polyester component P is very particularly preferably> 30% by weight, even more preferably> 35% by weight, based on the total weight of the material Cover layer D, provided that polyester component P according to variant ii) comprises or consists of at least one polyalkylene terephthalate.
  • polyester component P is moreover preferably> 45% by weight, most preferably> 50% by weight, based on the total weight of the material of the outer layer D, provided that polyester component P according to variant ii) comprises or consists of polyethylene terephthalate.
  • the proportion of the polyester component P for all embodiments is preferably ⁇ 60, particularly preferably ⁇ 55% by weight, based on the total weight of the material of the cover layer D.
  • the material of the cover layer can contain further blend partners.
  • blend partners polyamides, polyesters different from the polyesters described above, polylactide, polyether, thermoplastic polyurethane, polyacetal, fluoropolymer, in particular polyvinylidene fluoride, polyether sulfones, polyolefin, in particular polyethylene and polypropylene, polyimide, polyacrylate, in particular poly (methyl) methacrylate, polyphenylene oxide,
  • the cover layer D has a thickness ⁇ 500 mih, preferably ⁇ 300 mih, particularly preferably ⁇ 200 mih, very particularly preferably ⁇ 100 mih.
  • the cover layer D has a thickness> 5 mhi, preferably> 10 mhi.
  • Lacquer is the name for a liquid or powdery coating material that is applied thinly to objects and by chemical or physical means Processes (for example evaporation of the solvent) is built up into a continuous, solid film.
  • lacquer layer L All lacquers known to the person skilled in the art for use on polycarbonate-containing substrates are suitable as lacquer layer L.
  • the lacquer layer L preferably comprising one or more of the following layers:
  • a primer layer is understood to mean coatings that optimize the adhesive strength of paints on plastic parts, for example even after weathering.
  • the plastic parts are usually coated with a primer, also called a primer, before the color and effect paint layer or layers are applied.
  • the primer should also help protect against falling rocks.
  • a primer can be made conductive by adding appropriate additives such as conductive carbon black, so that the subsequently applied layers can be applied by means of electrostatic spray application and thus with particularly high transfer efficiency.
  • Basecoat is a name for a color-imparting intermediate coating material customary in automotive painting.
  • a clear coat protects the base coat from the effects of the weather, as well as mechanical and chemical attacks.
  • the number of basecoat layers and clearcoat layers to be applied is in each case not limited to one layer. It is also possible to apply two, three, four or more layers of basecoat or alternating layers of basecoat and clearcoat. The individual layers can each be dried completely or only partially dried before the next layer is applied. The latter is also known as the “wet-on-wet” application. Even when overcoating with a clear lacquer, the number of layers is not limited to one.
  • primers, basecoats and topcoats known to the person skilled in the art, aqueous or based on organic solvents, can be used to produce the lacquer layer L.
  • primer layers G that can be used according to the invention can be found, for example, in EP-B 1226218 or the European patent application with the application number 18213389.2, which was still unpublished at the time the present invention was applied for.
  • basecoat films B which can be used according to the invention can be found, for example, in US-A-3,639,147, DE-A-33 33 072, DE-A-38 14 853, GB-A-2012 191, US-A-3,953,644, EP-A -260 447, DE-A-39 03 804, EP-A-320 552, DE-A-36 28 124, US-A-4,719,132, EP-A-297 576, EP-A-69 936, EP-A -89 497, EP-A-195 931, EP-A-228 003, EP-A-38 127, DE-A-28 18 100 and WO-A 2017/202692.
  • Another object of the present invention is a method for producing a layer composite, comprising the step:
  • step II Application of at least one lacquer layer to the side of the top layer D facing away from the substrate layer S in the layer composite obtained after step I).
  • the layer composites according to the invention are used for the production of, for example, automobile add-on parts.
  • composite plates of a composite material made of polycarbonate and carbon fiber (hereinafter referred to as composite) with the dimensions 350 ⁇ 350 mm 2 were used as the substrate layer.
  • the composites were produced by Covestro Thermplast Composite GmbH (CTC) from 8 layers of UD tape, whereby the UD tapes themselves are made from 40-45% by volume of unidirectional carbon fiber of the Mitsubishi TRH-50 60M type and 60-55% by volume.
  • Polycarbonate matrix type Makroion® 3107 in color 901510
  • the layer structure in the individual UD tape layers was chosen so that there was a quasi-isotropic reinforcement of the composite (0745 ° / -45 ° / 90 ° / 90 ° / -45 ° / 45 ° / 0 °).
  • Thermoplastic molding compositions containing components A to E with the formulations given in Table 1 were produced on a ZSK25 twin-screw extruder from Coperion, Werner and Pfleiderer (Germany) at melt temperatures of 250.degree. C. to 300.degree. Films with a thickness of about 100 ⁇ m were then extruded from the granules obtained.
  • the corresponding material was pre-dried (4 h, 85-90 ° C) on the extruder (speed approx. 50 / min, melt temperature 265 ° C (entries 1-16 in table 1) and 300 ° C (entry 17 in table 1)) melted and extruded onto a rolling mill through a 450 mm wide slot nozzle.
  • Component A linear bisphenol A polycarbonate with an average molecular weight Mw of approx. 31,000 g / mol and a softening temperature (VST / B 120 according to ISO 306: 2014-3) of 150 ° C, which does not contain any UV absorber.
  • VST / B 120 a softening temperature
  • the melt Volume flow rate (MVR) according to ISO 1133: 2012-03 was 6.0 cm 3 / (10 min) at 300 ° C and 1.2 kg load.
  • Component B1 Polybutylene terephthalate (PBT) with a melt-mass flow rate (MFR) of 9.0g / 10min to 14.5g / 10min measured according to DIN EN ISO 1133 at a temperature of 250 ° C and with a load of 2.16 kg.
  • PBT Polybutylene terephthalate
  • MFR melt-mass flow rate
  • Component B2 polyethylene terephthalate (PET) with an intrinsic viscosity of 0.623 dl / g.
  • the specific viscosity is measured in dichloroacetic acid in a concentration of 1% by weight at 25 ° C.
  • Component B3 Polyester based on terephthalic acid, cyclohexanedimethanol and 2,2,4,4-tetramethyl-1,3-cyclobutanediol with an inherent viscosity of 0.69-0.75 dl / g measured in a 60/40 mixture (% by weight /% By weight) of phenol / tetrachloroethane at 25 ° C in a concentration of 0.5 g / 100 ml.
  • Component B4 polyethylene naphthalate (PEN).
  • Component C impact modifier with core-shell morphology, a styrene-butadiene-rubber core and a grafted-on shell made of methyl methacrylate-styrene copolymer, a butadiene content of 68% - 72% and a rubber
  • Component Dl Talc with an average particle diameter dso of 1.2 ⁇ m, measured by means of Sedigraph and with an APO content of 0.5% by weight.
  • Component D2 Irganox 1076, thermal stabilizer, BASF SE
  • Component D3 Phosphorous acid H 3 PO 3 as a solid.
  • Component E Pentaerythrityl tetrastearate as a lubricant / mold release agent.
  • the composites (substrate) were then laminated on both sides of a static laboratory press (type Joos LAP 100) with the films to be examined (cover layer D).
  • a polished insert (“high-gloss stamp”) and an external release agent (Frekote®, Henckel) were used.
  • Aerosil® R 972 Evonik Resource Efficiency GmbH, DE, fumed silica matting agent
  • Bayhydrol® U 2757, Covestro AG, DE aliphatic, anionic, hydroxy-functional polyurethane dispersion based on a mixture of aromatic polyester diol and a polycarbonate diol, co-solvent-free.
  • Bayhydrol® UH 2606, Covestro AG, DE aliphatic, polycarbonate-containing anionic polyurethane dispersion, co-solvent-free. Binder for the production of water-thinnable coatings for plastic substrates and wood-based materials, approx. 35% in water, neutralized with N-ethyldiisopropylamine (bound as salt) in the ratio: approx. 35: 64: 1, information according to data sheet edition 2016-09-13.
  • Bayhydrol® UA 2856 XP, Covestro AG, DE Aliphatic, acrylate-modified polyurethane dispersion Binder for aqueous, air- and oven-drying basecoats for 2-layer vehicle painting, plastic painting, automotive refinishing, industrial painting and for low-temperature-drying stone chip functional layers.
  • Viscosity ⁇ 100 mPa s at 23 ° C (ISO 3219 / A.3), information according to data sheet edition 2016-03-03
  • Bayhydur® XP 2655 Covestro AG, DE, hydrophilic polyisocyanate based on trimers of hexamethylene diisocyanate, NCO content 20.8% (ISO 11909), viscosity 3500 mPa s at 23 ° C (ISO 3219 / A.3), information in accordance with Data sheet edition 2017-06-01.
  • Desmodur® ultra N 3390, Covestro AG, DE aliphatic polyisocyanate (trimer of hexamethylene diisocyanate).
  • aliphatic polyisocyanate trimer of hexamethylene diisocyanate.
  • NCO content 19.6% (ISO 11909), viscosity 500 mPa s at 23 ° C (ISO 3219 / A.3), information according to data sheet edition 2018-11-14.
  • Desmodur® ultra N 3600, Covestro AG, DE polyisocyanate based on trimers of hexamethylene diisocyanate, NCO content 23.0% (ISO 11909), viscosity 1200 mPa s at 23 ° C (ISO 3219 / A.3), information in accordance with Data sheet edition 2017-06-01.
  • Desmophen® 670 BA, Covestro AG, DE slightly branched polyester containing hydroxyl groups for the production of weatherproof, elastic coatings.
  • Viscosity 3000 mPa s at 23 ° C (ISO 3219 / A.3), information according to data sheet edition 2018-03-01
  • DAA Diacetone Alcohol
  • Acros Organics Solvent
  • component 1 To produce component 1, the binder was initially introduced and then the other ingredients were weighed in in the order shown, glass beads (2.85 - 3.45 mm) were added 1: 1 (by volume) and then shaken with a Skandex BA laboratory shaker for 30 minutes. S20 from Lau rubbed. The glass beads were then sieved off. While stirring with a dissolver (dissolver disk 5 cm, at 800 rpm), the thickener was then slowly metered in and stirred in for a further 5 minutes. Component 1 was then adjusted with demineralized water to a flow time in the 4 mm DIN cup of 25 to 30 s.
  • a dissolver dissolver disk 5 cm, at 800 rpm
  • component 2 was incorporated while stirring with a paddle stirrer (5 min, 700 rpm) and the ready-to-use primer was applied within 30 minutes.
  • Water-based metallic basecoat (one-component hydro-basecoat HEBE 4134/1 according to the starting formulation published by Covestro GmbH AG (Edition 2016-08-23): First, the metallic paste (Table 2, Part 3) was prepared in a separate container all ingredients in table 2, part 3, mixed in the specified order while stirring with a propeller stirrer. The pH value was then tested (target: pH 8.0-8.5) and, if necessary, adjusted with DMEA. After stirring again for 30 minutes at approx. 10.5 m / s (maximum heating to 50 ° C) the paste was ready for use. For the metallic basecoat, part 1 and part 2 from Table 2 were mixed with a propeller stirrer at approx. 5.2 m / s.
  • Part 3 was then added and stirred in for 30 minutes at about 10.5 m / s. Finally, part 4 was added and stirred in again for 5 minutes at 5.2 m / s. Before application, the pH of the paint was adjusted to 8.0-8.5 with DMEA. The outflow time was set to 40 seconds in accordance with DIN cup 4 mm with demineralized water and the paint was filtered off through a 56 ⁇ m sieve.
  • binders were initially introduced. While stirring with a dissolver (dissolver disk 5 cm, at 800 rpm), all the other components in Table 3, Part 1, are metered in in the order given and stirred in for a further 5-10 minutes.
  • dissolver dissolver disk 5 cm, at 800 rpm
  • component 2 was incorporated while stirring with a paddle stirrer (5 min, 700 rpm) and the ready-to-use clearcoat was applied within 30 minutes.
  • the procedure for the production of the paint formulations and subsequent painting of the substrate-top layer laminates is described, inter alia, in the European patent application with the application number 18213389.2, which was still unpublished at the time of the application of the present invention.
  • the aqueous, two-component plastic primer was prepared as described above and applied over the entire surface with a Satajet RP gravity gun, 1.3 mm, air pressure 2.1 bar in 1 cross-pass to create a layer thickness (dry) of 20-25 ⁇ m. After application, the primer was dried for 10 min at room temperature, 30 min at 80 ° C. in a convection oven and stored for 16 h at room temperature.
  • the one-component hydro-base paint was then prepared as described above and also applied over the entire surface with a Satajet HVLP gravity gun, 1.2 mm, air pressure 2.1 bar in 1 cross-pass to produce a layer thickness (dry) of 9-12 ⁇ m.
  • the basecoat was dried for 10 min at room temperature, 30 min at 80 ° C. in a convection oven and stored for 3 h at room temperature.
  • the solvent-based clearcoat was prepared as described above and immediately after mixing the base paint and hardener with a Satajet HVLP gravity gun, 1.2 mm, air pressure 2.1 bar, applied in 1 cross-pass to achieve a layer thickness (dry) of 25-32 ⁇ m produce.
  • the clearcoat was dried for 10 minutes at room temperature and 45 minutes at 80 ° C. in a circulating air oven.
  • the grade “1” was awarded if the coated substrate layer-top layer laminate was free of bubbles, collapses, blisters or cracks and if fibers from the substrate underneath the film were at most minimally visible on the surface.
  • the grade “2” was awarded if the coated substrate layer-top layer laminate was free of bubbles, sink marks, blisters or cracks, but if fibers from the substrate underneath the film were visible on the surface.
  • the grade “3” was awarded if the if the coated substrate layer-top layer laminates had bubbles, sink marks, blisters and / or cracks.
  • grades 1 and 2 could only be achieved with a certain concentration of the polyester components B1 to B4 in the top layer, whereas always without admixing a polyester component (when using the pure component A) Bubbles, sink marks, blisters and / or cracks occurred after painting (Example 17, grade 3).

Abstract

La présente invention concerne un composite stratifié comprenant une matrice à base de polycarbonate, contenant éventuellement des fibres, et une couche externe de mélanges spéciaux de polycarbonate-polyester, ainsi qu'un composite stratifié tel que celui décrit ci-dessus et présentant une peinture sur le côté de sa couche externe qui est orientée à l'opposé de la matrice, un procédé de production de ces composites ainsi que leur utilisation pour la production, par exemple, de pièces automobiles rapportées.
EP20793725.1A 2019-10-28 2020-10-28 Composite stratifié comprenant du polycarbonate et un mélange de polycarbonate pour une meilleure peignabilité Withdrawn EP4051497A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP19205537.4A EP3815898A1 (fr) 2019-10-28 2019-10-28 Composite stratifié de polycarbonate et d'un mélange de polycarbonate destiné à l'aptitude à la mise en peinture améliorée
PCT/EP2020/080223 WO2021083925A1 (fr) 2019-10-28 2020-10-28 Composite stratifié comprenant du polycarbonate et un mélange de polycarbonate pour une meilleure peignabilité

Publications (1)

Publication Number Publication Date
EP4051497A1 true EP4051497A1 (fr) 2022-09-07

Family

ID=68382243

Family Applications (2)

Application Number Title Priority Date Filing Date
EP19205537.4A Ceased EP3815898A1 (fr) 2019-10-28 2019-10-28 Composite stratifié de polycarbonate et d'un mélange de polycarbonate destiné à l'aptitude à la mise en peinture améliorée
EP20793725.1A Withdrawn EP4051497A1 (fr) 2019-10-28 2020-10-28 Composite stratifié comprenant du polycarbonate et un mélange de polycarbonate pour une meilleure peignabilité

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP19205537.4A Ceased EP3815898A1 (fr) 2019-10-28 2019-10-28 Composite stratifié de polycarbonate et d'un mélange de polycarbonate destiné à l'aptitude à la mise en peinture améliorée

Country Status (6)

Country Link
US (1) US20220371309A1 (fr)
EP (2) EP3815898A1 (fr)
JP (1) JP2022554102A (fr)
KR (1) KR20220095187A (fr)
CN (1) CN114599518A (fr)
WO (1) WO2021083925A1 (fr)

Family Cites Families (48)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1007996B (de) 1955-03-26 1957-05-09 Bayer Ag Verfahren zur Herstellung thermoplastischer Kunststoffe
US2991273A (en) 1956-07-07 1961-07-04 Bayer Ag Process for manufacture of vacuum moulded parts of high molecular weight thermoplastic polycarbonates
US3148172A (en) 1956-07-19 1964-09-08 Gen Electric Polycarbonates of dihydroxyaryl ethers
US2999846A (en) 1956-11-30 1961-09-12 Schnell Hermann High molecular weight thermoplastic aromatic sulfoxy polycarbonates
US2999835A (en) 1959-01-02 1961-09-12 Gen Electric Resinous mixture comprising organo-polysiloxane and polymer of a carbonate of a dihydric phenol, and products containing same
GB1122003A (en) 1964-10-07 1968-07-31 Gen Electric Improvements in aromatic polycarbonates
NL152889B (nl) 1967-03-10 1977-04-15 Gen Electric Werkwijze ter bereiding van een lineair polycarbonaatcopolymeer, alsmede orienteerbare textielvezel van dit copolymeer.
FR1580834A (fr) 1968-01-04 1969-09-12
GB1284755A (en) 1968-09-30 1972-08-09 Celanese Coatings Co Process for coating surfaces and compositions for use therein
DE2036052A1 (en) 1970-07-21 1972-01-27 Milchwirtschafthche Forschungs und Untersuchungs Gesellschaft mbH, 2100 Hamburg Working up of additives in fat and protein - contng foodstuffs
DE2063050C3 (de) 1970-12-22 1983-12-15 Bayer Ag, 5090 Leverkusen Verseifungsbeständige Polycarbonate, Verfahren zu deren Herstellung und deren Verwendung
DE2211956A1 (de) 1972-03-11 1973-10-25 Bayer Ag Verfahren zur herstellung verseifungsstabiler blockcopolycarbonate
US3953644A (en) 1974-12-20 1976-04-27 Ford Motor Company Powa--method for coating and product
NZ186925A (en) 1977-04-25 1979-12-11 Ici Ltd Top-coating based on a basecoat and top-coat compositions not requiring an intermediate baking operation
GB2012191B (en) 1977-09-29 1982-03-03 Kodak Ltd Coating process utilising cellulose esters such as cellulose acetate butyrate
EP0038127B1 (fr) 1980-04-14 1984-10-17 Imperial Chemical Industries Plc Procédé pour enduire en plusieurs couches, comprenant l'utilisation d'une composition aqueuse à caractère thixotropique d'enduit de fond contenant des particules d'un polymère réticulé
DE3126549A1 (de) 1981-07-04 1983-01-20 Bollig & Kemper, 5000 Köln Verfahren zur herstellung von stabilen waessrigen dispersionen und deren verwendung als bindemittel zur herstellung von lacken, insbesondere zweischicht-metalleffektlacksystemen
DE3210051A1 (de) 1982-03-19 1983-09-29 Basf Farben + Fasern Ag, 2000 Hamburg Wasserverduennbares ueberzugsmittel zur herstellung der basisschicht eines mehrschichtueberzuges
DE3333072A1 (de) 1983-09-14 1985-03-21 Basf Farben + Fasern Ag, 2000 Hamburg Ueberzugsmasse, verfahren zur herstellung von ueberzuegen und beschichtetes substrat
US4719132A (en) 1984-09-21 1988-01-12 Ppg Industries, Inc. Process for the preparation of multi-layered coatings and coated articles derived therefrom
AT381499B (de) 1985-02-27 1986-10-27 Vianova Kunstharz Ag Wasserverduennbare ueberzugsmittel, verfahren zur herstellung und ihre verwendung fuer basisschichtenbei zweischicht-decklackierung
DE3545618A1 (de) 1985-12-21 1987-06-25 Basf Lacke & Farben Wasserverduennbares ueberzugsmittel zur herstellung der basisschicht eines mehrschichtueberzuges
US4804566A (en) * 1986-06-25 1989-02-14 General Electric Company Multilayer polyester structures and containers thereof
DE3628124A1 (de) 1986-08-19 1988-03-03 Herberts Gmbh Waessriges ueberzugsmittel, verfahren zu seiner herstellung und dessen verwendung
EP0320552A1 (fr) 1987-12-18 1989-06-21 E.I. Du Pont De Nemours And Company Procédé d'amélioration de l'apparence d'un revêtement multicouche
US4981759A (en) 1987-05-02 1991-01-01 Kansa Paint Co., Ltd. Coating method
DE3722005A1 (de) 1987-07-03 1989-01-12 Herberts Gmbh Verfahren zur herstellung eines mehrschichtueberzuges und hierfuer geeignetes waessriges ueberzugsmittel
BR8903379A (pt) 1988-07-11 1990-03-13 Ge Plastics Japan Ltd Processo para preparacao de policarbonatos
DE3832396A1 (de) 1988-08-12 1990-02-15 Bayer Ag Dihydroxydiphenylcycloalkane, ihre herstellung und ihre verwendung zur herstellung von hochmolekularen polycarbonaten
NO170326C (no) 1988-08-12 1992-10-07 Bayer Ag Dihydroksydifenylcykloalkaner
DE3903804C2 (de) 1989-02-09 2001-12-13 Bollig & Kemper Wäßrige Lackdispersionen und deren Verwendung
TW222292B (fr) 1991-02-21 1994-04-11 Ciba Geigy Ag
DE4238123C2 (de) 1992-11-12 2000-03-09 Bayer Ag Verfahren zur Herstellung von thermoplastischen Polycarbonaten
AU3980395A (en) 1994-11-10 1996-06-06 Basf Aktiengesellschaft 2-cyanoacrylic acid esters
US5717057A (en) 1994-12-28 1998-02-10 General Electric Company Method of manufacturing polycarbonate
EP0839623B1 (fr) 1996-10-30 2001-01-31 Ciba SC Holding AG Combinaison de stabilisateurs pour le procédé rotomolding
DE19933128A1 (de) 1999-07-19 2001-01-25 Bayer Ag Polycarbonat und dessen Formkörper
DE19933132A1 (de) 1999-07-19 2001-01-25 Bayer Ag Verfahren zur Herstellung von modifizierten Polycarbonaten
DE19948821A1 (de) 1999-10-09 2001-05-23 Basf Coatings Ag Elektrisch leitfähiger Hydroprimer für Kunststoffe
DE10300598A1 (de) 2003-01-10 2004-07-22 Bayer Ag Verfahren zur Herstellung von Polycarbonaten
DE102007050192A1 (de) * 2007-10-20 2009-04-23 Bayer Materialscience Ag Zusammensetzung mit UV-Schutz
TWI576389B (zh) * 2012-07-24 2017-04-01 三菱瓦斯化學股份有限公司 熱可塑性樹脂組成物及利用此組成物之片材
JP6567508B2 (ja) 2013-10-08 2019-08-28 コベストロ、ドイチュラント、アクチエンゲゼルシャフトＣｏｖｅｓｔｒｏ Ｄｅｕｔｓｃｈｌａｎｄ Ａｇ 繊維複合体、その使用およびその生産方法
US10815330B2 (en) 2016-04-22 2020-10-27 Covestro Deutschland Ag Thermolatently catalysed two-component system
KR20190010876A (ko) 2016-05-24 2019-01-31 바스프 코팅스 게엠베하 개선된 내오염성 및 (자기)세정 특성을 갖는 코팅제 및 그로부터 제조된 코팅 및 그의 용도
EP3464471B1 (fr) 2016-06-03 2021-10-06 Covestro Intellectual Property GmbH & Co. KG Matiere composite multicouches contenant des copolymères blocs de polydiorganosiloxane-polycarbonate en tant que materiau matriciel
TWI764909B (zh) 2016-07-04 2022-05-21 德商科思創德意志股份有限公司 含特定聚碳酸酯組成物作為基質材料之多層複合材料
DE202017004083U1 (de) 2017-07-29 2017-08-11 Bond-Laminates Gmbh Faser-Matrix-Halbzeuge mit abdichtenden Decklagen

Also Published As

Publication number Publication date
JP2022554102A (ja) 2022-12-28
US20220371309A1 (en) 2022-11-24
EP3815898A1 (fr) 2021-05-05
KR20220095187A (ko) 2022-07-06
CN114599518A (zh) 2022-06-07
WO2021083925A1 (fr) 2021-05-06

Similar Documents

Publication Publication Date Title
EP2046906B1 (fr) Laques à base aqueuse renfermant des polycarbonates hautement ou hyper-ramifiés hautement fonctionnels
EP2459625B1 (fr) Adhérence améliorée entre des matières thermoplastiques et des polyuréthanes
EP0691201A2 (fr) Stratifiés revêtus par projection comprenant une couche de couleur
EP3116926B1 (fr) Masses de revêtement à séchage rapide, élastiques dures, résistances aux rayures et robustes
WO2019046062A1 (fr) Stratifié composite comprenant une couche de film de polyuréthane thermoplastique
WO2002074860A2 (fr) Compositions de polycarbonate pour une meilleure adherence de la mousse
EP3058016A1 (fr) Compositions de polycarbonate à adhérence améliorée à des couches de polyuréthane
EP3727851B1 (fr) Feuilles en matière plastique pour document d'id à luminosité des hologrammes estampés améliorée
EP0398060B1 (fr) Utilisation de mélanges à base de polyuréthanes comme agent liant d'adhésifs pour coller des blocpolymères du type SBS.
WO2018122137A1 (fr) Élément composite
EP4051497A1 (fr) Composite stratifié comprenant du polycarbonate et un mélange de polycarbonate pour une meilleure peignabilité
WO2018122143A1 (fr) Procédé de fabrication par couches d'un objet présentant différents matériaux de couche et objet présentant différents matériaux de couche
WO2008092558A1 (fr) Matériau composite multicouche comprenant une couche de polycarbonate
DE112013001482B4 (de) Tiefschwarzer Mehrschichtbeschichtungsfilm und Bildungsverfahren davon
WO2010089042A1 (fr) Composite en feuille multicouches, comportant une couche en polycarbonate
DE4446333A1 (de) Verfahren zur kontinuierlichen Kratzfestausrüstung von Polycarbonaten
TW201815961A (zh) 包括覆蓋層及pc/abs層之多層複合製品及其方法
EP2168783A1 (fr) Utilisation d'un film plastique dans l'impression laser couleur
WO2001044121A1 (fr) Installation de dessalement solaire contenant des corps moules transparents revetus
EP0337206A2 (fr) Mélanges de poly(ester)carbonates thermoplastiques avec polyuréthanes thermoplastiques
WO2008107133A1 (fr) Produit avec adhérence améliorée de la peinture
EP2808354A1 (fr) Masses de revêtement à séchage rapide, élastiques dures, résistances aux rayures et robustes
EP3794073B1 (fr) Compositions de polycarbonate chargées présentant une bonne résistance aux rayures et un jaunissement réduit
WO2018007436A1 (fr) Système de revêtement
WO2014122149A1 (fr) Température de traitement maximale améliorée de substrats en plastique obtenue à l'aide de revêtements durs

Legal Events

Date Code Title Description
STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: UNKNOWN

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE INTERNATIONAL PUBLICATION HAS BEEN MADE

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

Free format text: ORIGINAL CODE: 0009012

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: REQUEST FOR EXAMINATION WAS MADE

17P Request for examination filed

Effective date: 20220530

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

17Q First examination report despatched

Effective date: 20230331

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE APPLICATION IS DEEMED TO BE WITHDRAWN

18D Application deemed to be withdrawn

Effective date: 20230811