EP3562869A1

EP3562869A1 - Composite component

Info

Publication number: EP3562869A1
Application number: EP17821921.8A
Authority: EP
Inventors: Andreas Seidel; Sven Hobeika; Ralf Hufen
Original assignee: Covestro Deutschland AG
Current assignee: Covestro Deutschland AG
Priority date: 2016-12-28
Filing date: 2017-12-22
Publication date: 2019-11-06
Also published as: WO2018122137A1; US20190352500A1; US11559951B2; CN110088178B; CN110088178A

Abstract

The invention relates to a composite component that has improved bonding properties and includes a substrate (i) made of a thermoplastic polymer blend composition, and a coating (ii); in a layer located 5 to 10 μm below the boundary surface between the substrate (i) and the coating (ii), the substrate (i) has a dispersed, non-lamellar phase structure. The invention also relates to a method for manufacturing the composite component.

Description

Verhundhautcü

The present invention relates to a composite member containing a carrier of a polycarbonate composition and a surface coating, and a method for producing the composite member.

Composite components are used for numerous applications in the areas of rail, aviation or motor vehicles as well as electrical / electronics. Such components are produced, for example, by first producing a carrier in an injection molding process and providing this carrier in a second step on at least one side with a decorative and / or functional coating. The coating can serve to improve the aesthetic appearance or surface properties, such as scratch resistance, haptics, surface conductivity or light resistance of the component. The coating can be applied by various methods such as spray painting, electroplating, foaming, curtain coating or 2K-RiM-Direct-Coating-V experienced.

An essential requirement for composite components is a stable two-component structure and the preservation of this structure even under mechanical loads or under the influence of aging influences. For example, scratches that penetrate the surface coating down to the substrate should not lead to a detachment of the coating from the substrate

Surface defect drove. The quality of structure conservation is often referred to as compound adhesion. She is in the

Generally indicated as the force required to peel off the coating. In the context of this application, this designation is used regardless of whether only the surface coating and the carrier layer separate (adhesive fracture behavior) or if there is a near-surface fracture failure within the carrier material or in the coating (cohesive failure in the carrier or in the coating) comes. Such a distinction is phenomenologically visually non-differentiable, i. it requires more specific, for example, microscopic and / or chemical-physical-analytical techniques to distinguish the mechanism and location of the fracture.

Numerous publications describe how good bond adhesion can be achieved. DE 10 2006 033 059 A1 discloses composite components consisting of polycarbonate (PC) / ABS or polyamide / ABS molding compositions as a carrier and a polyurethane-based coating produced in a two-component reactive injection molding process in which the carrier surface is pretreated with a primer to improve the bond adhesion or a laser, corona or plasma treatment has been subjected.

The Journal of Applied Polymer Science, Vol. 104, 479-488 (2007) discloses studies on the adhesion of polyurethane foams to polycarbonate / ABS blends. The maximum disclosed bond strengths are all limited by the tear strength of the polyurethane foam at 0.30 +/- 0.05 N / mm.

WO 2011/070043 Al and WO 2011/070044 Al describe composite components with improved

Bond strength and a two-component reactive injection molding process for the production of polyurethane-coated components of PC ABS molding compositions with improved bond strength, in which injected in a first step in a first cavity, a carrier of a thermoplastic PC / ABS composition, subsequently cooled and thereby solidified in a second method, the cavity of the injection molding tool is enlarged and thereby a gap is created and finally in a third process step a reactive polyurethane raw material mixture comprising a polyisocyanate and a polyfunctional I I active compound is sprayed into the gap thus created, the mixture polymerized in contact with the surface of the thermoplastic carrier to a compact polyurethane layer or to a polyurethane foam layer. The applications disclose that improved bond strength of polyurethane skin to the PC / ABS carrier results if PC / ABS compositions having a high polycarbonate content or a high rubber content are used in the first process step. However, such compositions have a high melt viscosity and thus often poor processability in the injection molding process. WO 2015055577 AI describes poly carbonate / AB S compositions with improved paint adhesion and composite components of a support of such compositions and a polyurethane-based coating, wherein the PC / ABS composition based on the sum of polycarbonate and ABS content 10 bis Contains 20 parts by weight of polybutadiene rubber and 12 to 23 parts by weight of free, rubber-free SAN.

WO 2015055719 Al describes polycarbonate compositions with improved adhesion to polyurethane systems and composite components of a support of such Compositions and a polyurethane-based coating, wherein the PC composition contains polycarbonate, polyalkylene terephthalate and a mixture of polybutadiene rubber-containing graft polymer and butadiene-free vinyl (co) polymer and based on the sum of the above polymeric constituents of the composition 8 to 18 parts by weight Polybutadiene and 3 to 12 parts by weight of butadiene-free vinyl (co) polymer.

WO 2015055561 A1 discloses flame-retardant polycarbonate / AB S compositions with improved adhesion to polyurethane systems and composite components comprising a support of such compositions and a polyurethane-based coating, wherein the

PC / ABS composition polycarbonate, a mixture of polybutadiene rubber-containing graft polymer and butadiene-free vinyl (co) polymer and a phosphorus-containing flame retardant and based on the sum of o.g. Ingredients of the composition contains 0.5 to 5.5 parts by weight of polybutadiene and 0.5 to 5.0 parts by weight of butadiene-free vinyl (co) polymer.

WO 99/20464 discloses composite components with improved composite adhesion after climate change test consisting of a support of a finely divided metal oxides containing PC / ABS composition and a polyurethane foam coating.

WO 201 1015286 AI discloses composite components with improved composite adhesion consisting of a carrier of a foamed by means of a chemical or physical process by injection molding polycarbonate / ABS composition and one in a

Reactive injection molding process applied thereto polyurethane coating.

The disclosed composite components obtain their good adhesion properties via particular compositions of the carrier material or a pretreatment of the carrier surface. This is associated with a limited performance property profile or a more complex manufacturing process.

It was thus desirable to provide components with good composite adhesion which can be readily manufactured and in which the substrate can be made from a wide range of compositions. In a preferred embodiment, the composite adhesion in the composite components according to the invention should be at least 0.8 N / mm, more preferably at least 1.0 N / mm, measured on stripped samples taken from the component with a width of 20 mm in a roll chase according to DI EN 1464 (version of 2010) with a Test speed of 100 mm / min, amount. This means that both the strength of the substrate, as well as the strength of the coating material and also the

Adhesive strength in the boundary layer between support and coating exceeds this value.

It has now surprisingly been found that composite components containing

(i) a thermoplastic composition carrier containing at least the following ingredients

A) 45 to 90 wt .-%, preferably 50 to 80 wt .-%, particularly preferably 55 to 75 wt .-%, each based on the sum of all components of the composition, at least one representative selected from the group consisting of polycarbonate, Polyester, polyester and polyamide, preferably selected from the group consisting of polycarbonate, polyester and polyester, more preferably

Polycarbonate, in particular aromatic polycarbonate,

B) 10 to 55 wt .-%, preferably 19.9 to 49.9 wt .-%, particularly preferably 24.8 to 44.8 wt .-%, each based on the sum of all components of the composition, rubber-modified vinyl ( co) containing polymer

B.l) one or more graft polymers of

B.l .l) 10 to 80 wt .-% of at least one vinyl monomer

B.l .2) 20 to 90 wt .-% of one or more rubbery

Graft bases, the polymer chains formed from the monomers B.I.1) being chemically bound to the graft base B.I.2) or being enclosed in the graft base in such a way that they do not escape from this graft base in the production and processing of the compositions according to the invention and

B.2) one or more rubber-free (co) polymers of at least one vinyl monomer and C) 0 to 30 wt .-%, preferably 0.1 to 20 wt .-%, particularly preferably 0.2 to 10 wt .-%, each based on the sum of all components of the composition, one or more polymer additives, wherein the Content of rubber B.1.2) based on component B), at 10 to 40

Wt .-%, preferably 15 to 35 wt .-%, particularly preferably 20 to 30 wt .-%, and wherein the component B) at least 20 wt .-%, preferably at least 30 wt .-%, particularly preferably at least 40 wt .-%, each based on the

Component B), non-chemically bonded to the graft or included in this graft base vinyl (co) polymer B.2) contains and

(ii) at least one single or multi-layer coating in direct contact with this support selected from at least one member of the group consisting of polymer and metal coating, preferably polymer coating, more preferably polyurethane coating, wherein the support (i) in a layer, the 5 to 10 μιη below the interface of the support (i) to the coating (ii), has a phase structure, which is characterized in that the kauts chukmodi fizi erte vinyl (co) polymer according to component B) in the component A) dispersed in Phases having a respective ratio of the geometric extension parallel to the melt flow direction in the thermoplastic preparation of the support to the geometrical extent perpendicular to the support surface, determined by transmission electron microscopy after Os04 / Ru04 double contrasting, of <10, preferably <7, in particular <5,

have the desired properties.

The support is a shaped body which, in a preferred embodiment, is produced by an injection molding process.

In a preferred embodiment, the carrier used for the two-component component already has the above-described phase structure before the coating process.

A component of the invention is also a process for producing the composite components, in which a support is coated from a composition as described above. In a In a preferred embodiment, a support having the above-described phase structure is used in this process.

The phase structure described above can be achieved in various ways, it being immaterial to the invention, which approach is chosen.

Possible approaches include the use of compositions

Phase compatibility agent as a component of component C), use of suitable process parameters in the preparation of the carrier such as low ScheiTaten and / or high mold temperatures, heat treatment of the carrier, preferably above the glass transition temperatures of components A) and B) before coating and quenching of the carrier surface in suitable Solvents before coating.

Components of the carrier material (i)

Component A

As component A) is a thermoplastic or a mixture of different thermoplastics selected from at least one polymer P from the group consisting of polycarbonate, polyester, polyester and polyamide used. In a preferred embodiment, component A) is selected from at least one polymer selected from the group consisting of polycarbonate, polyester carbonate and polyester.

According to the invention, "polycarbonate" is understood as meaning both homopolycarbonates and copolycarbonates, in which case the polycarbonates can be linear or branched in a known manner .Mic mixtures of polycarbonates can also be used according to the invention.

A part, up to 80 mol%, preferably from 20 mol% up to 50 mol%, of the carbonate sipes in the polycarbonates used according to the invention may be replaced by aromatic dicarboxylic acid ester groups. Such Poiycarbonate containing both acid residues of carbonic acid and acid residues of aromatic dicarboxylic acids incorporated in the molecular chain are referred to as aromatic polyester.

Substitution of the carbonate groups by the aromatic dicarboxylic ester groups is essentially stoichiometric and also quantitative, so that the molar ratio of the reactants is also found in the finished polyester carbonate. The incorporation of the aromatic dicarboxylic acid ester groups can be carried out both statistically and in blocks. The thermoplastic polycarbonates including the thermoplastic aromatic polyester carbonates have average molecular weights Mw determined by GPC (Geipermeationschromatographie in methylene chloride with polycarbonate as standard) of 15,000 g / mol to 50,000 g / mol, preferably from 20,000 g / mol to 35,000 g mol, more preferably from 23,000 g mol to 33,000 g / mol.

The preparation of the polycarbonates and polyester carbonates in a known manner from diphenols, carbonic acid derivatives, optionally chain terminators and branching agents. Details of the production of polycarbonates have been laid down in many patents for about 40 years. For example, see Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, Interscience Publishers, New York, London, Sydney 1964, D. Freitag, U. Grigo, P.R. Müller, I i. Nouvertne, BAYER AG, "Polycarbonates" in Encyclopedia of Polymer Science and Engineering, Volume 11, Second Edition, 1988, pages 648-718, and finally U. Grigo, K. Kirchner and P.R. Müller "Polycarbonates" in Becker Braun. Plastics Handbook, Volume 3/1, polycarbonates, polyacetals, polyesters, cellulose esters, Carl Hanser Verlag Munich, Vienna, 1992, pages 117-299 referenced. The preparation of aromatic polycarbonates is e.g. by reaction of diphenols with carbonyl halides, preferably phosgene, and / or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, after the phase deterioration, optionally break off using chains! and optionally using tri-functional or more than tri-functional branching agents, wherein for the preparation of the polyester carbonates, a part of the carbonic acid derivatives is replaced by aromatic dicarboxylic acids or derivatives of dicarboxylic acids, depending on the extent to be replaced in the aromatic polycarbonates carbonate structural units by aromatic Dicarbonsäureesterstruktureinheiten. Likewise, preparation via a melt polymerization process by reaction of diphenols with, for example, diphenyl carbonate is possible.

Dihydroxyaryl compounds suitable for the preparation of polycarbonates are those of the formula (1)

HO-Z-OH (1),

in which

Z is an aromatic radical having 6 to 30 C atoms, which may contain one or more aromatic nuclei, may be substituted and may contain aliphatic or cycloaliphatic radicals or alkylaryls or heteroatoms as bridge members. Z in formula (1) preferably represents a radical of the formula (2)

in the

R ⁶ and R ⁷ independently of one another are H, C i - to C is -alkyl, C i - to C is -alkoxy,

Halogen such as Ci or Br or for each optionally substituted aryl or aralkyl, preferably for H or C i - to C n-alkyl, particularly preferably for H or C i - to Cx-Alkvl and very particularly preferably for H or methyl, and

X for a single bond, -SO.- -, -CO-, -0-. -S-, C i - to C-alkylene, C ₂ - to C ₅ -

Alkylidene or C to Ce-cycloalkylidene which may be substituted by C i - to C, -Alk l, preferably methyl or ethyl, further for Ce to C n-arylene, which may be optionally fused with further heteroatom-containing aromatic rings , stands.

Preferably, X is a single bond, C - to C. Alkylene, C ₂ to C ₅ alkylidene, C ₅ C ₆ cycloalkylidene, -0-. -SO-, -CO-, -S-, -SO _; or for a radical of the formula (2a)

Diphenols suitable for the production of polycarbonates are, for example, hydroquinone, resorcinol, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ethers, bis ( hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, α-α'-bis (hydroxyphenyl) -diisopropylbenzenes, phthalimidines derived from isatin or phenolphthalein derivatives, and their alkylened, nuclear-arylated, and kenehalogenated compounds. Preferred diphenols are 4,4'-dihydroxydiphenyl, 2.2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis (3-methyl-4-hydroxyphenyl) -propane, dimethyl-bisphenol A, bis (3,5-dimethyl-4-hydroxyphenyl) -methane, 2.2-Bi sl 3. -tlimethyl -4-h ydroxyphenyl) -propane. Bis- (3,5-dimethyl-4-hydroxyphenyl) sulfone, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane, 1,1'-bis (3,5-dimethyl 4-hydroxyphenyl) -p-diisopropylbenzene and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

Particularly preferred diphenols are 2,2-bis- (4-hydroxyphenyl) -propane (bisphenol A), 2,2-bis- (3,5-dimethyl-4-hydroxyphenyl) -propane, 1,1-bis- (4 -hydroxyphenyl) -cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and dimethyl-bisphenol A.

These and other suitable diphenols are e.g. in US-A 3,028,635, US-A 2,999,825, US-A 3,148,172, US-A 2,991,273, US-A 3,271,367, US-A 4,982,014 and US-A 2,999,846, in DE-A 1 570 703, DE-A 2063 050, DE-A 2 036 052, DE-A 2 21 1 956 and DE-A 3 832 396, in FR-A

1 61518, in the monograph "H. Schnell. Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964", as well as JP-A 62039/1986, JP-A 62040/1986 and JP-A 105550/1986. In the case of homopolycarbonates, only one diphenol is used, in the case of

Copolycarbonates are used several diphenols. The diphenols used, as well as all other chemicals and auxiliaries added to the synthesis, may be contaminated with the impurities derived from their synthesis, handling and storage. However, it is desirable to work with as pure as possible raw materials.

Suitable carbonic acid derivatives are, for example, phosgene or diphenyl carbonate.

(Suitable chain terminators that can be used in the preparation of the polycarbonates are monophenols. (Suitable monophenols are, for example, phenol itself, alkylphenols such as cresols, p-tert-butylphenol, cumylphenol and mixtures thereof.

Preferred Kettenabbre rather are the phenols which are mono- or polysubstituted with C i - to C30- alkyl radicals, linear or branched, preferably unsubstituted, or substituted with tert-butyl. Particularly preferred chain terminators are phenol, cumylphenol and / or p-tert-butylphenol. The amount of chain terminator to be used is preferably 0.1 to 5 mol%, based on moles of diphenols used in each case. The addition of the chain terminators can be carried out before, during or after the reaction with a carbonic acid derivative. Suitable branching agents are the tri- or more than tri-functional compounds known in polycarbonate chemistry, especially those having three or more than three phenolic OH groups.

Suitable branching agents are, for example, 1,3,5-tri (4-hydroxyphenyl) benzoi, 1,1,1-tri (4-hydroxyphenyl) ethane, tri- (4-hydroxyphenyl) -phenyl methane, 2,4- Bis (4-hydroxyphenylisopropyl) phenol, 2,6-bis (2-hydroxy-5'-methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4- dihydroxyphenyl) propane, tetra (4-hydroxyphenyl) methane, tetra-

(4- (4-hydroxyphenylisopropyl) phenoxy) methane and 1,4-bis - ((4 ', 4 "-dihydroxytriphenyl) methyl) benzene and 3,3-bis (3-methyl-4-hydroxyphenyl ) -2-oxo-2,3-dihydroindole.

The amount of optionally used branching agent is preferably 0.05 mol% to 2.00 mol%, based on moles of diphenols used in each case.

The branching agents may either be initially charged with the diphenols and the chain terminators in the aqueous alkaline phase or may be added dissolved in an organic solvent prior to phosgenation. In the case of the transesterification process, the

Branching agent used together with the diphenols.

Particularly preferred polycarbonates are the homopolycarbonate based on bisphenol A, the homopolycarbonate based on 1,3-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and the copolycarbonates based on the two monomers bisphenol A and I, l Bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

Preferred production positions of the polycarbonates to be used according to the invention, including the polyester carbonates, are the known interfacial process and the known process

Melt transesterification processes (see, for example, WO 2004/063249 A1, WO 2001/05866 A1, WO 2000/105867, US Pat. No. 5,340,905 A, US Pat. No. 5,097,002 A, US Pat. No. 5,717,057 A).

For incorporation of additives into the composition, component A) or a part of component A) can be used in the form of powders.

Eligible polyesters in a preferred embodiment are aromatic, more preferably polyalkylene terephthalates. In a particularly preferred embodiment, 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 aromatic polyalkylene terephthalates contain 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 weight, based on the diol component of ethylene glycol and / or butanediol -l, 4-residues.

The preferred aromatic polyalkylene terephthalates may contain, in addition to terephthalic acid residues, up to 20 mole%, preferably up to 10 mole%, of other aromatic or cycloaliphatic dicarboxylic acids having 8 to 14 C atoms or aliphatic dicarboxylic acids having 4 to 12 C atoms, e.g. Residues of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldi-carboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.

The preferred aromatic polyalkylene terephthalates, in addition to ethylene glycol or

4-radicals up to 20 mol%, preferably up to 10 mol%, of other aliphatic diols having 3 to 12 C atoms or cycloaliphatic diols having 6 to 21 C atoms, e.g. Remains of Propamliole-1.3. 2-Ethylpropanediol-1,3-neopentylglycol, pentanediol-1,5, 1,6-hexanediol, cyclohexanedimethanol-1,4,3-ethyipentanediol-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 (β-hydroxyethoxy) benzene, 2,2-bis (4-hydroxycyclohexyl) propane, 2,4-dihydroxy-1,1,3,3-tetramethylcyclobutane, 2,2-bis (4-.beta.-hydroxyethoxy-phenyl) -propane and 2,2-bis (4-hydroxypropoxyphenyl) -propane (DE-A 2 407 674, 2 407 776, 2 715 932).

The aromatic polyalkylene terephthalates may be prepared by incorporation of relatively small amounts of trihydric or trihydric alcohols or 3- or 4-basic carboxylic acids, e.g. in accordance with DE-A 1 900 270 and US Pat. No. 3,692,744. Examples of preferred branching agents are trimesic acid, trimellitic acid, trimethylolethane and -propane and pentaerythritol.

Particularly preferred are aromatic polyalkylene terephthalates which have been prepared solely from terephthalic acid and their reactive derivatives (for example their dialkyl esters) and ethylene glycol and / or 1,4-butanediol, and mixtures of these polyalkyl enterephthalates. Preferred mixtures of aromatic polyalkylene terephthalates contain 1 to 50% by weight, preferably 1 to 30% by weight, of polyethylene terephthalate and 50 to 99% by weight, preferably 70 to 99% by weight, of polybutylene terephthalate. The aromatic poly (ethylene terephthalates) which are preferably used have a viscosity number of 0.4 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, measured in phenol / o-dichlorobenzoi (1: 1 parts by weight) in a concentration of 0 , 05g / ml according to ISO 307 at 25 ° C in Ubbelohde viscometer. The aromatic poly (ethylene terephthalates) can be prepared by known methods (see, for example, Kunststoff-Handbuch, Vol. VIII. P. 695 et seq., Carl-Hanser-Verlag, Munich 1973).

In a further embodiment of the present invention are as thermoplastic

Polymer according to component A) used amorphous and / or semi-crystalline polyamides.

If polyamides are used as component A), the compositions in a preferred embodiment are free of polycarbonates, polyester carbonates and polyesters.

Suitable polyamides are aliphatic polyamides, for example P-6. PA-11, PA-12. PA-4,6, PA-4,8, PA-4,10, PA-4.12. PA-6,6, PA -6.9. PA-6,10, PA-6,12, PA-10, 10, PA-12.12. PA-6 / 6,6-copolyamide, PA-6/12-copolyamide, PA-6/11-copolyamide, PA-6,6 / 11-copolyamide, PA-6,6 / 12-copolyamide, PA-6 / 6, 10-copolyamide, PA-6,6 / 6, 10-copolyamide, PA-4,6-copolyamide, PA-6 / 6,6 / 6, 10-Teφolyamid, and Copolyamide of 1, 4-Cyclohexandi carboxylic acid and 2,2,4- and 2,4,4-trimethyihexamethylenediamine, aromatic polyamides, / for example PA-6.1. PA-6, l / 6,6-Copolyamide, PA-6.T. PA-6, T / 6 copolyamide, PA-6, T / 6,6 copolyamide,

PA-6, l / 6, T-Copolyamide, PA-6,6 / 6, T / 6, 1 -Copolyamide, P A-6 .T 2-M PM DT Copolyami (2-MPMDT = 2-methylpentamethylenediamine) , PA-9.T. Copolyamide of terephthalic acid, 2,2,4- and 2,4,4-trimethylhexamethylenediamine, copolyamide of isophthalic acid, laurolactam and 3,5-dimethyl-4,4-diaminodicyclohexyimethane, copolyamide of isophthalic acid, azelaic acid and / or sebacic acid and 4,4 Diaminodicyclohexylmethane, copolyamide of caprolactam, isophthalic acid and / or terephthalic acid and 4,4-diaminodicyclohexylmethane, copolyamide of caprolactam, isophthalic acid and / or terephthalic acid and isophoronediamine, copolyamide of isophthalic acid and / or terephthalic acid and / or other aromatic or aliphatic dicarboxylic acids, optionally alkyl-substituted hexamethylenediamine and alkyl-substituted 4,4-diaminodicyclohexylamine or their copolyamides and mixtures of the aforementioned polyamides. When polyamides are used as component A) preferably semi-crystalline polyamides are used, which have advantageous thermal properties. In this case, semi-crystalline polyamides are used which have a melting point of at least 200 ° C., preferably of at least 220 ° C., more preferably of at least 240 ° C. and even more preferably of at least 260 ° C. The higher the melting point of the semi-crystalline polyamides, the more advantageous the thermal behavior of the carrier material. The melting point is determined by DSC.

Preferred semi-crystalline polyamides are selected from the group containing PA-6, PA-6,6, PA-6,10. PA 4.6. PA-11, PA-12. PA-12, 12, PA-6.1. PA 6.T. PA-6, T / 6,6-copolyamide

PA-6, T / 6-co-polyamide, PA-6 / 6,6-copolyamide, PA-6,6 / 6, T / 6, 1-copolyamide, PA-6T 2-MPMDT copolyamide, ΡΛ-. Τ. PA-4,6 / 6-Copoiyamid and mixtures thereof or

Copoiyamide. In a preferred embodiment, the component A is either polyamide or at least one polymer selected from the group consisting of polycarbonate, polyester and polyester carbonate. in a further preferred embodiment, as component A, exactly one polymer selected from the group consisting of polycarbonate, polyester and polyester carbonate is used

Commitment.

Aromatic polycarbonate based on bisphenol A is most preferably used as component A.

Component ß

Component B) is rubber-modified vinyl (co) polymer.

Component B) comprises one or more graft polymers as component B.l) and rubber-free vinyl (co) polymer which is not chemically bonded to a rubber or enclosed in this rubber as component B.2).

Component B.l)

Component B.l) comprises one or more graft polymers of

Bl .l 10 to 80 wt .-%, preferably 20 to 70 wt .-%, particularly preferably 25 to 55 wt .-% of at least one vinyl monomer on B.1.2 from 20 to 90% by weight, preferably from 30 to 80% by weight, particularly preferably from 45 to 75% by weight, of one or more rubbery, preferably in the form of particulate graft bases, preferably with glass transition temperatures <10 ° C., more preferably <0 ° C, particularly preferably <-20 ° C, wherein the polymer chains formed from the monomers B.1.1) are chemically bonded to the graft B.1.2) or are included in the graft base so that they in the preparation and Processing of the compositions of the invention do not escape from this graft.

The glass transition temperature is determined by means of differential scanning calorimetry (DSC) according to the standard DIN EN 61006 (2004 version) at a heating rate of 10 K / min with definition of the Tg as the center temperature (tangent method).

The preferred particulate Pfropfgrundiagen B.1.2) generally have an average particle size (d50 value) of 0.05 to 10 μιη, preferably 0.1 to 5 μιη, more preferably 0.2 to 1, 5 μπι. The mean particle size d50 is the diameter, above and below which each 50 wt .-% of the particles are. It can be determined by ultracentrifuge measurement (W. Scholtan, I.I. Lange, Kolloid, Z. and Z. Polymere 250 (1972), 782-1796).

Monomers B.1.1 are preferably mixtures of

Bl .1.1 50 to 99 wt .-%, preferably 65 to 85 wt .-%, preferably 70 to 80 wt .-%, each based on the totality of the monomers of the graft shell B.1.1, vinyl aromatics and / or ring-substituted vinyl aromatic (such Styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or (meth) acrylic acid (C 1 -C 8) alkyl esters, such as methyl methacrylate, ethyl methacrylate and butyl acrylate, and

B.1 .1 .2 1 to 50 wt .-%, preferably 15 to 35 wt .-%, particularly preferably 20 to 30 wt .-%, each based on the totality of the monomers of Pfropfhülie B.1.1, Vinyi Cyanide ( unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth) acrylic acid (C 1 -C 8) -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 Bl .1.1 are selected from at least one of the monomers styrene, α-methylstyrene and methyl methacrylate. Preferred monomers B.1 .1 .2 are selected from at least one of the monomers acrylonitrile, n-butyl acrylate, maleic anhydride and methyl methacrylate. Particularly preferred monomers are B. 1 .1. 1 styrene and B. 1. 1 .2 acrylonitrile.

For the graft polymers Bl) suitable grafting B. 1 .2) are for example diene rubbers, EP (D) M rubbers, ie those based on ethylene / propylene and optionally diene, acrylate, polyurethane, silicone, chloroprene and ethyl ene / Vinylac etat-Kauts chuke and silicone / acrylate composite rubbers.

Preferred graft bases B.1.2) are diene rubbers, for example based on butadiene and isoprene, or mixtures of diene rubbers or copolymer grades of diene rubbers or mixtures thereof with other copolymerizable monomers (for example according to B.l.1.1 and B.l.1.2). Particularly preferred as the graft B.1.2) is pure polybutadiene rubber.

Particularly preferred graft polymers B.I) are, for example, ABS polymers, as described, for example, in US Pat. in DE-OS 2 035 390 (= US Pat. No. 3,644,574) or in DE-OS 2 248 242 (= GB-PS 1 409 275) or in Ullmanns, Enzyklopädie der Technischen Chemie, Vol. 19 (1980) , Pp. 280 et seq. The graft copolymers B.l) are prepared by free-radical polymerization, e.g. produced by emulsion, suspension, solution or bulk polymerization.

The gel content of the graft base B.1.2) is determined at 25 ° C. in a suitable solvent as a fraction which is insoluble in these solvents (M. Hoffmann, H. Kramer, R. Kuhn, Polymeranalytik I and I. Georg Thieme-Verlag, Stuttgart 1977 ). In the grafting, it is known that the graft monomers B.1.1) are not necessarily completely grafted onto the grafting base. To this extent, products of grafting reactions often still contain significant proportions of free (i.e., not chemically bound to the grafting base and irreversibly entrapped in the grafting base) copolymer having a composition analogous to that of the grafted shell. For the purposes of the present invention, component B.1) is understood to mean exclusively the graft polymer as defined above, whereas the copolymer of component B.2) which is not bound chemically to the graft base and is not included in this graft base is associated with the preparation.

The proportion of this free copolymer in products of grafting reactions can be determined from their gel contents (proportion of free copolymer = 100 wt .-% - gel content of the product in wt .-%), wherein the gel content at 25 ° C in a suitable Solvents (such as acetone, M. Hoffmann, H. Krämer, R. Kuhn, Polymeranalytik I and I, Georg Thieme Verlag, Stuttgart 1977) are determined to be insoluble in these solvents. Preferably, the graft polymer of the components B. I. I and B. 1 .2 a core-shell structure, wherein the component B. 1 .1 forms the shell (also referred to as shell) and the component B.1.2) forms the core (see, for example, Ulimann's Encyclopedia of Industrial Chemistry, VCH-Veriag, Vol. A21, 1992, page 635 and page 656. Component B.2)

The composition contains as further component B.2) one or more rubber-free (co) polymers of at least one vinyl monomer, preferably selected from the group of vinyl aromatics, vinyl cyanides (unsaturated nitriles), (meth) acrylic acid (C 1 to C 8) alkyl esters , unsaturated carboxylic acids and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids.

Particularly suitable as component B.2) are (co) polymers

B.2.1) 50 to 99 wt .-%, preferably 65 to 85 wt .-%, particularly preferably 70 to 80 wt .-% based on the (co) polymer B.2) at least one monomer selected from the group of vinyl aromatics (such as, for example, styrene, α-methylstyrene), ring-substituted vinylaromatics (such as, for example, p-methylstyrene, p-chlorostyrene) and (meth) acrylic acid (C 1 -C 8) -alkyl esters (such as, for example, methyl methacrylate, n-butyl acrylate, tert-butyl). Butyl acrylate) and

B.2.2) 1 to 50 wt .-%, preferably 15 to 35 wt .-%, particularly preferably 20 to 30 wt .-% based on the (co) polymer B.2) of at least one monomer selected from the group of vinyl cyanides (Such as unsaturated nitriles such as acrylonitrile and methacrylonitrile), (meth) acrylic acid (C 1 -C 8) alkyl esters (such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate), unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids (for example, maleic anhydride and N phenyl-maleimide).

These (co) polymers B.2) are resinous, thermoplastic and rubber-free. The copolymer of B2.1) styrene and B2.2) 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 B.2) have a weight-average molecular weight (Mw), determined by gel permeation chromatography with polystyrene as standard, of preferably 50,000 to 200,000 g / mol, more preferably from 70,000 to 170000 g / mol, most preferably from 80,000 to 130000 g / mol. Component C

The carrier may optionally contain as component C) one or more polymer additives, preferably selected from the group consisting of flame retardants, Antidrippingmitteln, Flamms chutzsynergi costs, smoke inhibitors, lubricants and defoliants, nucleating agents, antistatic agents, conductivity additives, stabilizers (eg hydrolysis, heat aging and UV stabilizers and transesterification inhibitors), flowability promoters, phase compatibility agents, other impact modifiers (both with and without core-shell structure) which differ from component B), other polymeric constituents (for example functional blend partners) other than components A) and B), filler and reinforcing materials and dyes and pigments.

In a preferred embodiment, the composition comprises at least one polymer additive selected from the group consisting of lubricants and mold release agents, stabilizers, flowability promoters, phase compatibility agents, others

Impact modifiers, other polymeric constituents, dyes and

Pigments.

In a preferred embodiment, the composition contains pentaerythritol tetrastearate as the mold release agent.

In a preferred embodiment, the composition contains at least one phase compatibilizer. Preferred phase compatibilizers are graft or block copolymers comprising blocks of polymers according to component A and blocks of polymers according to component B.2), optionally containing further vinyl monomers having reactive groups such as anhydride groups or epoxide groups, preferably glycidyl methacrylate.

In a preferred embodiment, the composition contains as stabilizer at least one member selected from the group consisting of sterically hindered phenols, organic phosphites and sulfur-based co-stabilizers.

In a particularly preferred embodiment, the composition contains as stabilizer at least one member selected from the group consisting of octadecyl 3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionate and tris (2,4-di-tert-butylphenyl) phosphite. Structure of the surface coating (ii)

As Besmchtung (ii) in the context of the present invention, a one or more layers in contact with the carrier selected from at least one member of the group consisting of polymer layers and metal layers used.

In a preferred embodiment, the coating used is a polymer film, more preferably a polyurethane foam or a compact polyurethane film, in a particularly preferred embodiment a compact polyurethane layer. The polyurethane chi cht is polymerized in a preferred embodiment in direct contact with the carrier.

In a particularly preferred embodiment, the polyurethane layer is applied to the support by a 2K RIM direct coating process, that is

(i) in a first method, the melt of the thermoplastic composition is injected into a first mold cavity and subsequently cooled,

(ii) in a second method, the cavity of the injection molding tool is enlarged and thereby a gap is created,

(Iii) in the third step in the resulting gap between the thermoplastic component and the tool surface of the enlarged cavity containing a reactive polyurethane raw material mixture

at least one polyisocyanate component,

at least one polyfunctional H-active compound, and

optionally at least one polyurethane additive and / or processing aid

the polyurethane raw material mixture is polymerized in contact with the surface of the thermoplastic carrier to form a compact polyurethane layer or a polyurethane foam layer,

(iv) in the fourth method step, the composite component is removed from the mold cavity,

wherein the process steps (ii) and (iii) can be repeated several times and wherein the process steps follow one another directly. An alternative embodiment, which is particularly suitable for thermoplastic polyurethanes, is the polymerization of the polyurethane in a first process step followed by a second process step in which the polyurethane layer is applied to the carrier in a two-component injection molding process. Another alternative In an embodiment, the production of a polyurethane film is carried out in a first process step followed by a second process step in which this film is back-injected with the polycarbonate composition of the carrier (i). The polyurethanes used according to the invention are obtained by reacting polyisocyanates with H-active polyfunctional compounds, preferably polyols.

In the context of this invention, the term "polyurethane" is also understood as meaning polyurethaneureas in which H-active polyfunctional compounds such compounds having N-H functionality are optionally used in admixture with polyols.

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, oxazoiidinone, Acylurea and / or carbodiimide structures may have. These can be used individually or in any mixtures with each other. The abovementioned 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 were prepared by using phosgene or by phosgene-free processes. Examples of such di- or triisocyanates are 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (HDD, 2-methyl-1,5-diisocyanatopentane, 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-diiso-xyanatocyclohexan, 1,3- and 1,4 Bis- (isocyanatomethyl) -cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 4,4'-dinocyanatodicyclohexylmethane (Desmodur ™ W, Bayer AG, Leverkusen, DE), 4 Isocyanatomethyl-l, 8-octane diisocyanate (triisocyanatononane, TIN), co, co'-diisocyanato-1,3-dimethylcyclohexane (H6XDI), 1-isocyanato-1-methyl-3-isocyanato-methylcyclohexane, 1-isocyanato-1 - methyl-4-isocyanato-methylcyclohexane, bis (isocyanatomethyl) -norbornane, 1,5-naphthalene diisocyanate, 1,3- and 1,4-bis- (2-isocyanato-prop-2-yl) -benzoi (TMXDI ), 2,4- and 2,6-diisocyanatotoluene (TDI), in particular the 2,4 and the 2,6-isomeric and technical mixtures de r two isomers, 2,4'- and 4,4'-diisocyanato-diphenylmethane (MDI), polymeric MDI (pMDI), 1, 5-diisocyanatonaphthalene, 1, 3 -Bis (isocyanato-methyl) benzene (XDI) and any Mixtures of said compounds. 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. In a preferred embodiment, polyisocyanates or polyiso cyanatgemi s che of the type mentioned above are used with exclusively aliphatic and / or cycloaliphatic bound isocyanate groups.

The polyisocyanates of the abovementioned type are very particularly preferably based on hexamethylene diisocyanate, isophorone diisocyanate, the isomeric bis (4,4'-isocyanatocyclohexyl) methanes and mixtures thereof.

Among the higher molecular eyepiece, 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 polyhydroxyl compounds are both simple polyhydric alcohols of molecular weight range 62-599, preferably 62-200, e.g. Ethylene glycol, trimethylolpropane, 1,2-propanediol or 1,4-butanediol or 2,3-butanediol, but in particular higher molecular weight polyether polyols and / or polyester polyols of the type known per se from polyurethane chemistry with molecular weights of 600 to 12,000, preferably 800 to 4,000 having at least two, usually 2 to 8, but preferably 2 to 6 primary and / or secondary hydroxyl groups. Of course, those NCO prepolymers can be used, for example, of low molecular weight polyisocyanates of the type exemplified and less preferred compounds with isocyanate-reactive groups such. Polythioether. Hydroxyl-containing polyacetals, polyhydroxypolycarbonates, hydroxyl-containing polyesteramides or hydroxyl-containing copolymers of olefinically unsaturated compounds have been obtained.

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 NCO prepolymers, these compounds with isocyanate-reactive groups with simple polyisocyanates of the type exemplified above with an NCO excess / ur conversion brought. The NCO prepolymers generally have an NCO content of 10 to 26, preferably 1 5 to 26 wt .-%. From this it is already apparent that in the context of the present invention under "NCO prepolymers" or "prepolymers with terminal isocyanate groups" both the Umsetzungsprodulcte as such and the mixtures with excess amounts of unreacted starting polyisocyanates, often as,, emiprepolymer e "are to be understood.

Suitable aliphatic diols having an OH number of> 500 mg KOH / g are the chain extenders customarily used in polyurethane chemistry, such as 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-Methyipropandiol- 1.3. Of course, it is also possible to use the aliphatic diols in a mixture with each other.

Polyols having a mean 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 suitable according to the invention are, for example, polyhydroxypolyethers which are obtained by alkoxylation of suitable starter molecules such as ethylene glycol, diethylene glycol, 1 , 4-dihydroxybutane, 1,6-dihydroxyhexane, dimethylolpropane, glycerol, pentaerythritol, sorbitol or sucrose. Also suitable as initiators are ammonia or amines such as ethylenediamine, hexamethylenediamine, 2,4-diaminotoluene, aniline or aminoalkohoie 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.

In addition to polyols, at least one further crosslinker and / or chain extender may be additionally selected from the group consisting of amines and amino alcohols, for example ethanolamine, diethanolamine, diisopropanolamine, ethylenediamine, triethanolamine, isophoronediamine, N, N'-dimethyl (diethyi) -ethylenediamine, 2 -amino-2-methyl (or ethyl) -1-propanol, 2-amino-1-butanol, 3-amino-1,2-propanediol. 2-amino-2-methyl (ethyl) -1,3-propanediol, and alcohols, for example ethylene glycol, diethylene glycol, 1,4-dihydroxybutane, 1,6-dihydroxyhexane, dimethylolpropane, glycerol and pentaerythritol, as well as sorbitol and sucrose, or mixtures contains these compounds.

Also suitable are polyester polyols, as they are accessible 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 conventional manner, unless the viscosity of the H-active component is too large. A preferred polyol having ester groups is castor oil. In addition, preparations with castor oil, such as those obtained by dissolving resins, for example aldehyde-ketone Resins that can be obtained as well as modifications of castor oil and polyols based on other natural oils are suitable.

Also suitable are those relatively high molecular weight polyhydroxypolyethers in which high molecular weight polyadducts or polycondensates or polymers in finely dispersed, dissolved or grafted form are present. Such modified polyhydroxy compounds are prepared in a manner known per se, e.g. when polyaddition reactions (for example reactions between polyisocyanates and amino-functional compounds) or polycondensation reactions (for example between formaldehyde and phenols and / or amines) take place in situ in the hydroxyl-containing compounds. However, it is also possible to mix a finished aqueous polymer dispersion with a polyhydroxyl compound and then remove the water from the mixture. Also, vinyl polymer-modified polyhydroxyl compounds such as those described in U.S. Pat. obtained by polymerization of styrene and acrylonitrile in the presence of polyethers or polycarbonate polyols are suitable for the preparation of polyurethanes. When using Polyetherpoiyolen, soft 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 e.g. in High Polymers, Vol. XVI, "Polyurethanes Chemistry and Technology", Saunders-Frisch (ed.) Interscience Pubishers, New York, London, Vol. 1, pp. 32-42, 44, 54 and Vol. II. 1984, 5-6 and pages 198-199.

It is also possible to use mixtures of the compounds listed.

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. In principle, however, the person skilled in the influence on the polymer-physical properties of the polyurethane are known, so that NCO component, aliphatic diol and Po Kol can be matched in a favorable manner to each other.

The polyurethane layer (b) can be foamed or solid, such as present as a paint or coating. For their preparation, all known auxiliaries and additives such as release agents, blowing agents, fillers, catalysts and flame retardants can be used.

If necessary as auxiliaries and admixtures are to be used: a) water and / or volatile inorganic or organic substances as propellant As organic propellants are e.g. Acetone, ethyl acetate, halogen-substituted alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, Chlordi fluoromethane, dichlorodifluoromethane, butane, hexane, heptane or diethyl ether, as inorganic blowing agents air, C02 or N20 in question. A blowing effect can also be achieved by the addition of compounds decomposing at temperatures above room temperature with elimination of gases, for example nitrogen, e.g. Azo compounds such as azodicarbonamide or Azoisobuttersäurenitril be achieved. b) catalysts

The catalysts are, for example, tertiary amines (such as triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, Ν, Ν, Ν ', Ν'-tetramethylethylenediamine, pentamethyldiethylenetriamine and higher homologs, 1, 4-diazabicyclo- (2,2 , 2) octane, - methyl-N'-dimethylaminoethylpiperazine, bis (dimethylaminoalkyl) piperazines, N, N-dimethylbenzylamine, N, N-dimethylcyclohexylamine, Ν, Ν-diethylbenzylamine, bis (N, N-diethylamino-ethyl) adipate , N, N, N ', N'-tetramethyl-1,3-butanediamine, N, N-dimethyl-.beta.-phenyl-ethylamine, 1, 2-dimethylimidazole, 2-methylimidazole), monocyclic and bicyclic amides, bis ( dialkylamino) alkyl ethers, amide groups (preferably Fonnamidgruppen) having tertiary amines, Mannich bases of secondary amines (such as dimethylamine) and aldehydes, (preferably formaldehyde or ketones such as acetone, methyl ethyl ketone or cyclohexanone) and phenols (such as phenol, nonylphenol or bisphenol), towards isocyanate groups Hydrogen atoms containing tertiary amines (eg triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldietanolamine, Ν, Ν-dimethylethanolamine), and their reaction products with alkylene oxides such as propylene oxide and / or ethylene oxide, secondary / tertiary amines, silaamines with carbon-silicon bonds (2, 2,4-trimethyl-2-silamorpholine and 1,3-diethylaminomethyltetramethyldisiloxane), nitrogenous bases (such as tetraalkylammonium hydroxides), alkali hydroxides (such as sodium hydroxide, alkali phenolates such as sodium phenolate), alkali metal alcoholates (such as sodium methylate), and / or hexahydrotriazines. The reaction between NCO groups and Zerewitinoff-active hydrogen atoms is also greatly accelerated in a manner known per se by lactams and azalactams, initially forming an associate between the lactam and the compound with acidic hydrogen. It is also possible to use organic metal compounds, in particular organic tin and / or bismuth compounds, as catalysts. 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, for example dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate or dioctyltin diacetate. Organic bismuth catalysts are described, for example, in patent application WO 2004/000905. Of course, all the catalysts mentioned above can be used as mixtures.

Of particular interest are combinations of organic metal compounds and amidines, aminopyridines or hydrazinopyridines.

The catalysts 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. c) Surface-active additives such as emulsifiers and foam stabilizers.

As 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.

Also, alkali metal or ammonium salts of sulfonic acids such as dodecylbenzenesulfonic acid or dinaphthylmethanedisulfonic acid or of fatty acids such as ricinic 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, often via allophanate groups. d) reaction retarder

As a reaction retarder, e.g. acidic substances (such as hydrochloric acid or organic acid halides) in question. e) additives

As PU additives are, for example, cell rule of the known type (such as paraffins or fatty alcohols) or dimethylpolysiloxane e and pigments or dyes and Flame retardants of the type known per se (for example tri-chloroethyl phosphate, tricresyl phosphate or ammonium phosphate and polyphosphate), furthermore stabilizers against aging and weathering influences, plasticizers and fungistatic and bacteriostatic substances and fillers (such as barium sulfate, kieselguhr, carbon black or whiting) into consideration.

Further examples of optionally used according to the invention surface-active additives and foam stabilizers and cell regulators, reaction retarders, stabilizers, flame retardants, plasticizers, dyes and fillers and fungistatic and bacteriostatic substances are known in the art and described in the literature.

Production of the molding compounds for the carrier and the carrier itself

From the carrier compositions of the invention thermoplastic molding compositions can be prepared.

The thermoplastic molding compositions according to the invention can for example be prepared by mixing the respective constituents of the compositions in a known manner and at temperatures of preferably 200 ° C to 320 ° C, more preferably at 240 to 300 ° C in conventional units such as internal kneaders, extruders and twin-screw screws are melt-compounded and melt-extruded.

The mixing of the individual constituents of the compositions can be carried out in a known manner both successively and simultaneously, both at about 20 ° C (room temperature) and at a higher temperature. This means that, for example, some of the components can be metered via the main intake of an extruder and the remaining components can be fed later via a side extruder in the compounding process.

The molding compositions of the invention can be used for the preparation of carriers of any kind. These can be produced for example by injection molding, extrusion and blow molding. Another form of processing is the production of carriers by deep drawing from previously prepared plates or films.

It is also possible to meter the components of the compositions directly into an injection molding machine or into an extrusion unit and to process them into carriers. Examples of composite components according to the invention are coated films, profiles, housing parts of any kind, eg for household appliances such as juice presses, coffee machines, mixers; for office machines such as monitors, flat screens, notebooks, printers, copiers; Panels, pipes, electrical installation ducts, windows, doors and other profiles for the construction sector (interior fittings and outdoor applications) and electrical and electronic parts such as switches, plugs and sockets and components for commercial vehicles, especially for the automotive sector, interior fittings for rail vehicles, ships, aircraft, buses and other motor vehicles, body parts for motor vehicles, housings of Kl eintrans formators containing electrical appliances, housing for information processing equipment and

Transmission, housing and cladding of medical devices, massagers and housings therefor, toy vehicles for children, flat wall elements, housings for safety devices, heat-insulated transport containers, coated moldings for sanitary and bath equipment, grille for ventilation openings and housings for garden tools.

Hereinafter, further embodiments 1 to 27 of the present invention will be described: 1. Containing composite component

(i) a carrier of a thermoplastic composition containing at least the following constituents A) from 45 to 90% by weight, based on the sum of all constituents of the composition, of at least one polymer selected from the group consisting of polycarbonate, polyester, polyestercarbonate and polyamide,

B) 10 to 55 wt .-%, based on the sum of all components of the composition, containing rubber-modified vinyl (co) polymer

B.l) one or more graft polymers of

B.l .l) 10 to 80 wt .-% of at least one vinyl monomer

B.l .2) 20 to 90 wt .-% of one or more chewing chukartiger

Graft bases, wherein the polymer chains formed from the monomers Bl. I) are chemically bonded to the graft base Bl .2) or enclosed in the graft base in such a way that they do not escape from this graft base during the production and processing of the compositions according to the invention and B.2) one or more rubber-free (co) polymers of at least one vinyl monomer and C) 0 to 30 wt .-%, based on the sum of all components of the composition, one or more polymer additives, wherein the rubber content B.1.2) related to component B), at 10 to 40

% By weight, and wherein component B) contains at least 20% by weight of vinyl (co) polymer B.2) not chemically bonded to the graft base or enclosed in this gypsum base;

(ii) at least one monolayer or multilayer coating in direct contact with this support selected from at least one member of the group consisting of polymer and metal coating, wherein the support (i) in a layer, the 5 to 10 μηι below the interface of Support (i) for coating (ii), has a phase structure, which is characterized in that the rubber-modified vinyl (co) polymer according to component B) in the component A) dispersed in phases with a respective ratio of the geometric extension parallel to Melt flow direction in the thermoplastic preparation of the support to the geometric extent perpendicular to the support surface, determined by transmission electron microscopy after Os04 / Ru04 double contrast, of <10, is present. 2. Composite component according to embodiment 1, wherein the coating is a polyurethane coating.

3. Composite component according to one of the embodiments 1 or 2, wherein component A) is aromatic polycarbonate.

4. Composite component according to one of the preceding embodiments, wherein the content of rubber B.1.2) based on the component B), at 15 to 35 wt .-%, is located. 5. composite component according to one of the previous embodiments, wherein the content of rubber B.! .2) based on the component B), at 20 to 30 wt .-%, is located. 6. Composite component according to one of the preceding embodiments, wherein component B) is at least 30% by weight, based on component B), of vinyl (co) polymer B 2 not bound chemically to the graft base or enclosed in this graft base. contains. 7. Composite component according to one of the preceding embodiments, wherein component B) is at least 40% by weight, based on component B), of vinyl (co) polymer B 2 not bound chemically to the graft base or enclosed in this graft base. contains. 8. Composite component according to one of the previous embodiments, the content of the

Component B.2) based on the sum of components A), B) and C) in the range of 5 to 40 wt .-% is.

9. Composite component according to one of the preceding embodiments, wherein the content of component B.2) based on the sum of components A), B) and C) is in the range from 10 to 30% by weight.

10. Composite component according to one of the preceding embodiments, wherein the component B) as a rubber at least one rubber selected from the group consisting of diene rubbers, mixtures of diene rubbers and copolymers of

Diene rubbers or mixtures thereof with other copolymerizable monomers.

11. Composite component according to one of the preceding embodiments, wherein the carrier contains 50 to 80% by weight of component A)

19.9 to 49.9 wt .-% of component B) and

0.1 to 20 wt .-% of the component C.

contains. 12. Composite component according to one of the previous embodiments from the guide, wherein the carrier

55 to 75% by weight of component A)

24.8 to 44.8 wt .-% of component B) and

0.2 to 10 wt .-% of component C. contains.

13. Composite component according to one of the preceding embodiments, in which the carrier (i) has a phase structure in a layer which is 5 to 10 μm below the boundary surface of the carrier (i) for coating (ii), characterized in that the rubber-modified vinyl (co) polymer according to component B) in component A) is dispersed in phases with a respective ratio of the geometric extension parallel to the melt orientation in the thermoplastic preparation of the support to the geometric extension perpendicular to the support surface, determined by transmission electron microscopy Os04 / u04 double-peak trastring of <7.

14. Composite component according to one of the preceding embodiments, in which the support (i) has a phase structure in a layer which is 5 to 10 μm below the boundary surface of the support (i) for the coating (ii), characterized in that the rubber-modified vinyl (co) polymer according to component B) in component A) is dispersed in phases with a respective ratio of the geometric extension parallel to the melt orientation in the thermoplastic production of the carrier to the geometric extension perpendicular to the TrägeroberAäche, determined by transmission electron microscopy after Os04 / Ru04 double contrast, <5.

15. Composite component according to one of the preceding embodiments, wherein the coating is a compact lacquer layer.

16. Composite component according to the embodiment 15, wherein the compact lacquer layer has a thickness of at most 500 μιη.

17. Composite component according to one of the preceding embodiments, wherein component C is selected from the group consisting of flame retardants, anti-dripping agents,

Flame retardant synergists, smoke inhibitors, lubricants and mold release agents, nucleating agents, antistatic agents, conductivity additives, stabilizers, flowability promoters, phase compatibility agents, other impact modifiers different from component B.I), other polymeric constituents, fillers and reinforcing materials as well as dyes and pigments other than components A) and B).

18. Composite component according to one of the preceding embodiments, wherein component C contains a phase compatibility agent. 19. Composite component according to embodiment 18, wherein the phase compatibilizer is a graft or block copolymer comprising blocks of polymers according to component A and blocks of polymers according to component B.2), optionally containing further vinyl monomers with reactive groups selected from anhydride groups and epoxide groups ,

20. Composite component according to embodiment 19, wherein the phase compatibility agent comprises styrene, acrylonitrile and glycidyl methacrylate.

21. Composite component according to one of the preceding embodiments, wherein the carrier was produced by an injection molding process.

22. Composite component according to one of the preceding embodiments, wherein the carrier consists of at least 90 wt .-%, of the components A), B) and C).

23. Composite component according to one of the preceding embodiments, wherein the carrier consists of at least 95 wt .-%, of the components A), B) and C). 24. Composite component according to one of the preceding embodiments, wherein the carrier consists of the components A), B) and C).

25. A method for producing a composite component according to one of the previous embodiments, wherein in a first method step, the carrier produced by an injection molding process and in a second process step the

Surface coating is applied.

26. A method for producing a composite component according to one of embodiments 2 to 24, wherein in a first method step, the carrier produced by an injection molding process and in the second process step, a polyurethane layer is applied by a 2K-RIM direct coating method.

27. Method according to one of the embodiments 25 or 26, wherein before the second method step, the carrier has a phase structure which lies in a layer which is 5 to 10 μm below the boundary surface of the carrier (i) for coating (ii) characterized in that the rubber-modified vinyl (co) polymer according to component B) in component A) is dispersed in phases having a respective ratio of geometric expansion parallel to the melt flow in the thermoplastic Production of the support to the geometric extent perpendicular to the support surface, determined by transmission electron microscopy after Os04 / Ru04 double contrast, of <5, is present.

Examples

Used components in the carrier material

Component A:

Bisphenol A-based linear polycarbonate having a weight-average molecular weight Mw of 32,000 g / mol (determined by GPC in methylene chloride against a bisphenol A-PC standard).

Component B-1:

ABS type graft polymer precipitated in an acidic medium with magnesium sulfate prepared by grafting in the emulsion polymerization method using

Potassium peroxodisulfate as a polymerization initiator of 52 parts by weight of a mixture of styrene and acrylonitrile in a weight% ratio of 72:28 to 48 parts by weight of a particulate particulate cross-linked polybutadiene chewing with a particle diameter determined by ultracentrifugation of d50 = 0, 3 μτη. The gel content of the component Bl, measured as acetone-insoluble fraction, is 78 wt .-%, that is, component Bl contains 22 wt .-% not chemically bonded to the rubber base or included in the rubber base vinyl (co) polymer component B-2 :

Styrene-acrylonitrile copolymer having an acrylonitrile content of 24% by weight and having a weight-average molecular weight Mw of 102,000 g / mol (determined by G C against a polystyrene standard). Component Cl:

Modiper ™ CL430-G (NOF Corporation, Japan): Phase Compatibilizer

(Graft polymer of polycarbonate and a styrene-acrylonitrile-glycidyl methacrylate copolymer) Component C2:

Irganox ™ B900 (BASF, Germany): stabilizer Production of the molding compounds

The components were mixed on a twin-screw extruder ZSK 26 MCC from Coperion at a melt temperature of 275 ° C. Reactive polyurethane coating system

The polyurethane coating system used was a mixture of Desmophen ™ XP 2488 (polyol component) and Desmodur ™ N3600 (polyisocyanate component), both from Covestro, Leverkusen, Germany, in a mixing ratio of 1: 1, 7 parts by weight.

Desmophen ™ P 2488 is a branched polyester polyol with a viscosity according to DI 53019 (version of 2008) of 13250 mPa.s at 20 ° C, a density according to DIN 51757 (version of 201 1) of 1, 12 g / cm ³ at 20 ° C and an OH content of 16.0%. Desmodur ™ N3600 is an aliphatic isocyanate based on hexamethylene diisocyanate with an NCO content according to DIN EN ISO 1 1909 (version of 2007) of 23.5 wt .-%, a viscosity at 23 ° C according to DIN EN ISO 3219 / A. 3 (version from 1994) of 1,200 mPa s and a density at 20 ° C according to DIN EN ISO 281 1 (version of 2014) of 1, 16 g / cm ³ . The crosslinking of the polyurethane coating system was carried out with a dibutylmindilaurate

(DBTL) commercially available catalyzed by OMG Borchers GmbH, Langenfeld. The amount added was 0.5 parts by weight based on the sum of Poiyol component and polyisocyanate component. Production of composite components

Partially surface coated moldings having an area of 412 cm ^{2 were produced} on an injection molding machine in an injection mold having two cavities (a substrate-side cavity and a polyurethane-side cavitation cavity which was linked to a RIM installation). The composite component is a plate-shaped component made of thermoplastic material with a composition according to Table 1 (carrier) whose surface has been partially coated with a polyurethane layer. The wall thickness of the carrier molding was about 4 mm. The polyurethane layer thickness was about 200 μιη. The inventive method for producing the composite components according to the invention described in the examples is shown in Figure 1 for better illustration. In the first process step, the carrier molding was produced. For this purpose, thermoplastic granules of the compositions as described in Table 1 was melted in an injection cylinder and injected at a temperature of 270 ° C in the first mold cavity of the closed mold (steps I and 2 in Figure 1). This mold cavity was heated to a temperature of 80 ° C. After expiration of the holding pressure time and cooling time, which led to solidification of the carrier, the tool was opened in the second process step (step 3 in Figure 1). The produced carrier component was held on the ejector side of the injection mold and moved 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). Thereafter, the injection mold was closed again (step 5 in Figure 1), a closing force for a maximum pressure of 200 bar was constructed and in the third process, the solvent-free reactive polyurethane system (see above) injected under a pressure of about 30 bar into the coating cavity (Step 6 in Figure I). The two reactive components of the polyurethane coating system were conveyed by the RIM system into a high-pressure countercurrent mixing head and mixed there before being injected. The polyurethane-side cavity was tempered to a temperature of 80 ° C. After the end of the injection, 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. At the end of the reaction and cooling time, the tool was opened a second time in the fourth process step (step 7 in FIG. 1) and the coated molded part removed (step 8 in FIG. 1).

Determination of liability properties

The composite adhesion was tested on 20 mm wide strip samples sawn from the partially polyurethane-coated 2-component composite panels prepared as described above by a roll peel test according to DI EN 1464 (version of 2010) a test speed of 100 mm / min determined. Characterization of the component morphology according to Roilensehälversuch

From the components samples were prepared and using an ultramicrotome (Leica EM UC7 type) low-temperature thin sections with a thickness of about 50 nm of the areas to be examined (near the surface, that is directly on the surface of the support after removal of the polyurethane coating in the roller peel test, and remote from the surface, that is, 2 mm below the surface, that is centered in the volume of the carrier) with a cutting direction parallel to the injection molding. These samples were first contrasted in vacuum with OsO for 30 seconds (polybutadiene rubber contrasting) and then contrasted in RuOs for 15 minutes (Constrast of polycarbonate). Subsequently, the thus doubly contrasted thin sections were examined with a Leo 922 A EFTEM transmission electron microscope (TEM) (Carl Zeiss, Germany). Figure 2 shows a near-surface TEM image of a non-inventive composite component (containing a support of the composition according to Comparative Example 1 in Table 1) after roller peel test, that is, after removal of the polyurethane coating. At the substrate-side surface of the peeled lacquer layer adhered a 0.5-4 μιτι thick layer of the PC / AB S-substrate composition, which shows that the "delamination" on a cohesive failure in the carrier material in a layer 0.5-4 μιη below The TEM image shows a lamellar phase morphology of strongly stretched rubber-modified styrene-acrylonitrile copolymer domains dispersed in a polycarbonate matrix to a depth of approximately 10 μm (ie in the entire image). Ratio of the geometric extension parallel to the melt flow direction in the thermoplastic preparation of the carrier to the geometric extension perpendicular to the carrier surface) of all rubber-modified styrene-acrylonitrile copolymer domains is> 20. The surface of the composite component after roller peeling test has a comparatively low roughness

FIG. 3 shows a near-surface TEM action of a composite component according to the invention (containing a support from the composition according to Example 2 in Table 1) after roller peel test, that is to say after removal of the polyurethane coating. At the substrate-side surface of the peeled lacquer layer adhered a 0.5-4 μιη thick layer of the PC / ABS substrate composition, which shows that the "delamination" on a cohesive failure in the carrier material in a layer 0.5-4 μιη below the The TEM image shows a disperse phase morphology largely isotropic to a depth of about 10 μm (that is to say in the entire image), that is to say it reverses rubber-modified styrene-acrylonitrile copolymer domains dispersed in a continuous polycarbonate -

Matrix. The aspect ratio (ratio of the geometric extension parallel to the melt flow direction in the thermoplastic preparation of the carrier to the geometric extension perpendicular to the carrier surface) of the rubber-modified styrene-acrylonitrile copolymer domains is <5 in all cases. The surface of the composite component after Rollenschälversuch has a comparatively high roughness.

FIG. 4 shows a surface-distant TEM image of a composite component not according to the invention comprising a support of the composition according to FIG Comparative Example I in Table 1. The TEM uptake shows a coarse-disperse phase morphology of largely isotropic, that is, undrawn, rubber-modified styrene-acrylonitrile copolymer domains dispersed in a continuous polycarbonate.

Matrix.

FIG. 5 shows a surface-distant TEM image of a composite component according to the invention comprising a support of the composition according to Example 2 in Table 1. The TEM image shows a finely dispersed phase morphology of largely isotropic, that is undrawn, rubber-modified styrene-acrylonitrile copolymer domains dispersed in a continuous polycarbonate matrix.

A comparison of Figures 3 (near the surface) and 5 (maximum surface removal because 2 mm distance from the surface for a 4 mm thick sample) reveals that in the composite components of the invention the phase morphology over the entire carrier thickness is substantially constant, i. in that the rubber-modified vinyl (co) polymer according to component B) in component A) is dispersed in phases with a respective ratio of the geometric extension parallel to the melt flow direction in the thermoplastic preparation of the support to the geometric extension perpendicular to the support surface, determined by Os04 transmission electron microscopy Rii (34) opperation, <5, is present.

Table 1 Compositions of the carrier materials and the component properties

The data in Table 1 show that a significantly improved bond strength measured in the roller peel test is achieved when the interfacial phase morphology in the carrier the composite component is such that in a layer 5 to 10 μιη below the interface from coating to support the ABS phase is only slightly stretched out ver, that is, a low aspect ratio of the geometric extension parallel to the melt flow direction in the thermoplastic production of the carrier to the geometric Has expansion perpendicular to the carrier surface and thus present in this layer, a non-lamellar disperse phase structure.

Claims

claims

1.Verbundbauteil containing a carrier of a thermoplastic composition containing at least the following components

A) 45 to 90% by weight, based on the sum of all constituents of the composition, of at least one polymer selected from the group consisting of polycarbonate, polyester, polyester carbonate and polyamide,

B. l) one or more graft polymers of

B.l. l) 10 to 80 wt .-% of at least one vinyl monomer

B.l .2) 20 to 90 wt .-% of one or more chewing chukartiger

Grafting, wherein the monomers from the B. l. l) formed polymer chains are chemically bonded to the graft B. 1 .2) or are included in the graft base so that they do not escape from this graft base in the preparation and processing of the compositions of the invention and

B.2) one or more rubber-free (co) polymers of at least one vinyl monomer and

C) 0 to 30 wt .-%, based on the sum of all components of the composition, one or more polymer additives, wherein the rubber content B. l .2), based on the component B), at 10 to 40

% By weight, and wherein component B) contains at least 20% by weight of vinyl (co) polymer B.2) not chemically bonded to the graft base or enclosed in this graft base, and

(ii) at least one monolayer or multilayer coating in direct contact with this support selected from at least one member of the group consisting of polymer and metal coating, wherein the support (i) in a layer, the 5 to 10 μιη below the interface of Support (i) for coating (ii), has a phase structure, which is characterized in that the rubber-modified vinyl (co) polymer according to component B) in the component A) dispersed in phases with a respective ratio of the geometric extension parallel to Melt flow direction in the thermoplastic production of the carrier to the geometric extent perpendicular to the carrier surface, determined by

Transmission electron microscopy after Os04 / Ru04 double contrast, of <10, is present.

2. Composite component according to claim 1, wherein the coating is a polyurethane coating.

3. Composite component according to one of claims 1 or 2, wherein the component A) is aromatic polycarbonate.

4. Composite component according to one of the preceding claims, wherein the content of component B.2) based on the sum of components A), B) and C) in the range of 10 to 30 wt .-% is.

5. Composite component according to one of the preceding claims, wherein the carrier

55 to 75% by weight of component A)

24.8 to 44.8 wt .-% of component B) and

0.2 to 10 wt .-% of component C.

contains.

6. Composite component according to one of the preceding claims, wherein the coating is a compact lacquer layer.

7. Composite component according to claim 7, wherein the compact lacquer layer has a thickness of at most 500 μιη.

8. Composite component according to one of the preceding claims, wherein component C is selected from the group consisting of flame retardants, Antidrippingmitteln, flame retardant synergists, smoke inhibitors, lubricants and mold release agents, nucleating agents, antistatic agents, conductivity additives, stabilizers, flowability promoters, phase compatibility agents, further of component Bl) different impact modi ficators. other of components A) and B) different polymeric constituents, fillers and reinforcing agents and dyes and pigments.

9. Composite component according to one of the preceding claims, wherein the component C is a

Phase compatibilizer contains.

10. The composite component according to claim 9, wherein the phase compatibilizer is a graft or block copolymer containing blocks of polymers according to component A and blocks of polymers according to component B.2), optionally containing further vinyl monomers having reactive groups selected from anhydride groups and epoxide groups.

11. The composite component of claim 9, wherein the phase compatibilizer is a graft or block copolymer comprising blocks of polymers of component A and blocks of a styrene-acrylonitrile-glycidyl methacrylate copolymer and wherein the backing is made by an injection molding process and wherein the coating is a polyurethane coating.

12. Composite component according to one of the preceding claims, wherein the carrier consists of the components A), B) and C).

13. A method for producing a composite component according to one of the preceding claims, wherein in a first method step, the carrier produced by an injection molding process and in a second method step, the surface coating is applied.

14. A method for producing a composite component according to one of claims 2 to 12, wherein in a first method step, the carrier is produced by an injection molding process and in the second method step a polyurethane chi cht by a 2K-RIM direct coating method is applied.

15. The method according to claim 13 or 14, wherein the carrier before the second process s chritt in a layer which 5 to 10 μιη below the interface of the carrier (i) to the coating (ii), has a phase structure, which is characterized in that the rubber-modified vinyl (co) polymer according to component B) in the component A) dispersed in phases with a respective ratio of the geometric extension parallel to the melt flow direction in the thermoplastic Production of the support to the geometric extent perpendicular to the support surface, determined by transmission electron microscopy after Os04 / Ru04 double contrasting, of <5, is present.