Process for producing a composite component comprising a carrier having a specific oh content

Abstract

The present invention relates to a process for producing composite components with improved interlaminar bonding, the components comprising a carrier, which comprises polycarbonate and a further thermoplastic polymer, and at least one polyurethane layer in direct contact with this carrier. The invention also relates to composite components with improved interlaminar bonding, and to the use of a thermoplastic composition having a defined OH content as a carrier material or film material in the production of composite parts with improved interlaminar bonding.

Description

[0001] METHOD FOR PRODUCING A COMPOSITE COMPONENT COMPRISING A CARRIER WITH A SPECIFIC OH CONTENT

[0002] The present invention relates to a process for producing composite components with improved bond strength, comprising a carrier comprising polycarbonate and another thermoplastic polymer, and at least one polyurethane layer in direct contact with this carrier. The invention also relates to composite components with improved bond strength and to the use of a composition with a defined OH content as a carrier material in the production of composite parts with improved bond strength.

[0003] Composite components comprising a carrier made of at least one thermoplastic and at least one polyurethane layer in direct contact with this carrier are known in the art. Solid coated molded parts, for example, can be produced using processes such as the RIM (Reaction Injection Molding) process. So-called in-mold coating (IMC) or direct coating (DC) is particularly advantageous for the production of composite components with thick coatings. Here, the coating components are applied to the corresponding carrier in a mold and cured in the mold cavity. In addition to the requirements mentioned above, the major advantages of IMC technology are fast processing times, low to minimal loss of raw materials, and the production of a coated injection-molded part (composite component) including coating in a single operation.Both the composite components obtained using the RIM and IMC processes possess the mechanical properties of the substrate, whose weathering stability and scratch resistance are improved by the polyurethane layer. It is clear that the overall performance and stability of the composite component are also determined by the adhesion of the polyurethane layer to the substrate. Common composite components that use polycarbonate as a substrate often experience a loss of adhesion after exposure to stress such as climate change testing or storage. This also reduces the overall performance of the composite component. A further advantage of the RIM and IMC processes is that they enable special designs that cannot be achieved using other methods.This is particularly due to the fact that the coating of the composite components can be made relatively thick while simultaneously reacting quickly. DE 196 50 854 C1 discloses such an IMC process for producing a multi-layer plastic part, in which a plastic injection-molded part is coated with at least one layer of a two-component thermosetting resin, preferably polyurethane. In this process, the plastic part and the layer of two-component thermosetting resin are injection-molded sequentially in the same mold in a synchronous cycle. DE 196 50 854 C1 provides no information on the influence of the nature of the carrier material and the process parameters on the adhesion between the carrier material and the layer of the composite component bonded to it.

[0004] WO 2006 / 072366 A1 describes a method for molding and coating a substrate in a mold having at least two cavities. The method comprises the steps: a) molding a substrate in a first cavity of the mold, b) introducing the substrate produced in the previous step into a second cavity of the mold, and c) coating the substrate in the second cavity with a lacquer, wherein the coating takes place under increased pressure.

[0005] In this document, too, the adhesion between the substrate material and the coating layer is not the main focus.

[0006] EP28990008A1 describes how a special surface structuring of the carrier can improve adhesion to the polyurethane layer. It is also known that the use of primers or a special activation of the carrier material can lead to improved adhesion.

[0007] WO2011 / 015286 A1 relates to the provision of an improved bond between the carrier material and the polyurethane layer, with the proviso that no modification of the surface (in particular, priming or surface activation) of the carrier is required. It was found that the use of a foamed carrier material has a positive effect on adhesion to the polyurethane layer. WO2011 / 070044 A4 investigates the influence of the rubber content of a composition containing polycarbonate and a rubber-modified vinyl (co)polymer as carrier material on bond adhesion. In these documents, the improvement in bond adhesion is achieved either through additional steps such as applying a primer, surface activation, surface structuring, or foaming the carrier material, or through the addition of additives to the composition of the carrier material.This means that either an additional step is required in the production of a composite part, which entails corresponding costs and effort. Or a specially additived composition of the carrier material is required, which influences the mechanical properties of the resulting composite component and also entails additional costs for the additive.

[0008] Based on this prior art, the present invention was based on the object of overcoming at least one disadvantage of the prior art. In particular, the present invention was based on the object of providing a composite component with an improved bond between the carrier material, comprising polycarbonate and at least one further thermoplastic polymer, and the at least one polyurethane layer in direct contact with the carrier material. An improved bond should also be characterized in particular by better adhesion resistance. This preferably means that the deterioration in adhesion after hydrolysis storage should be as minimal as possible. Preferably, no additional steps such as modification of the surface, for example by primer or surface activation, should be necessary.Likewise, the use of additional additives for the purpose of improving / increasing bond strength in the carrier material should preferably be avoided. In particular, the polyurethane raw material mixture used to produce the composite component should be highly reactive (i.e., preferably have a mold life of less than 150 s, preferably 100 s). Furthermore, the polyurethane raw material mixture used should preferably have a pot life of at most 30 s, preferably at most 10 s. Most preferably, the composite component should be produced using a RIM or IMC process, in particular an IMC process.

[0009] At least one, and preferably all, of the above-mentioned objects have been achieved by the present invention. Surprisingly, it has been found that the use of a composition or a film comprising polycarbonate and another thermoplastic polymer, with a minimum content of OH groups, as a carrier material leads to an improved bond between the carrier material and the at least one polyurethane layer in direct contact with the carrier material. The resulting bond adheres force-fittingly. This can be assessed in particular by testing using the POSI test (in accordance with DIN EN ISO 4624:2016-08, using method B (8.4.2), if necessary specifying the most defective defect). In deviation from the DIN standard, preferably 8 measurements are carried out per component, with a total of 3 components being measured. The median of these measurements yields the adhesion value.The initial adhesion of the composite component according to the invention is preferably at least 5 MPa, particularly preferably at least 6.5 MPa, measured by the above-mentioned POSI test. Improved adhesion resistance was also observed. This means, in particular, that the adhesion of the composite component according to the invention remains high after the hydrolysis test (i.e., after 72 hours of storage at 90 ± 2 °C and 95 ± 3% relative humidity in a climate-controlled cabinet (the formation of water droplets on the component is to be avoided by suitable positioning in the climate-controlled cabinet)), i.e., preferably above 3 MPa, particularly preferably above 4 MPa, measured by the POSI test. The percentage reduction in adhesion is therefore small.The bond strength between the substrate and the polyurethane coating in the composite components according to the invention can also be measured using 20 mm wide strip samples taken from the component in a roller peel test according to DIN 53357:1982-10 at a test speed of 100 mm / min. Improved adhesion resistance would also be observed here.

[0010] The composite shows an improvement, in particular compared to a comparable system, wherein the carrier or film has an OH number which is below the OH number according to the invention. At the same time, it is preferred that the OH number of the composition of the carrier or film should be kept as low as possible, since an excessively high OH content can negatively influence the thermal stability of the carrier or film. As a rule, a high OH content of the composition of the carrier or film correlates with a high content of free bisphenol. This is undesirable for regulatory reasons alone. Therefore, it is simultaneously desirable to keep the OH content of the composition as low as possible while still achieving the effect according to the invention. According to the invention, it has been found that the lower limit found according to the invention or the range of OH groups of the carrier or film defined as preferredthe film on the one hand effectively improves the bond adhesion, but on the other hand is still low enough that the resulting composite component has good thermal stability and / or in particular also an acceptably low bisphenol A content. Without wishing to be bound by any theory, it is assumed that in particular the OH groups present on the surface of the formed carrier or film are available for reaction with the components of the polyurethane raw material mixture. This leads to the formation of bonds, preferably covalent bonds, between the surface of the carrier or film and the forming polyurethane layer. This leads to a good bond in the resulting composite component. This effect is particularly pronounced in RIM and / or IMC processes, since polyurethane raw material mixtures are used there, which generally have a high isocyanate content.This allows the described reaction to proceed particularly effectively. The formation of covalent bonds also results in particularly good adhesion.

[0011] According to the invention, therefore, in one aspect, a method for producing a composite component is provided, comprising a) a carrier made of a thermoplastic composition and b) at least one polyurethane layer in direct contact with the carrier, comprising the steps

[0012] (i) (ia) injecting a melt of a thermoplastic composition (Z) into a tool cavity and subsequent cooling to form the carrier or (ib) inserting a film comprising an outer layer consisting of a thermoplastic composition (Z) into a tool cavity, back-injecting this film with a melt of a further thermoplastic composition (Z2) on the side facing away from the outer layer of the film and subsequent cooling to form the carrier, wherein the thermoplastic composition (Z)

[0013] A) at least 50% by weight of a polycarbonate and

[0014] B) contains more than 0 wt.% to 50 wt.% of at least one thermoplastic polymer which is different from A), and the OH content in the case of (ia) the carrier or in the case of (ib) the film is at least 230 ppm, wherein the further thermoplastic composition (Z2) may be the same as or different from the thermoplastic composition (Z), (ii) enlarging the cavity of the tool and thereby creating a gap or introducing the carrier into a second cavity of the tool which is larger in terms of its hollow mold dimensions than the first cavity, thereby creating a gap, and wherein in case (ib) the carrier is oriented such that the outer layer of the film, which consists of the thermoplastic composition (Z), faces the gap,

[0015] (iii) Injecting a reactive polyurethane raw material mixture containing

[0016] - at least one polyisocyanate component,

[0017] - at least one polyfunctional H-active compound, and

[0018] - optionally at least one polyurethane additive and / or processing aid into the gap between the carrier and the tool surface, whereby the polyurethane raw material mixture polymerises in contact with the surface of the carrier to form a compact polyurethane layer or a polyurethane foam layer,

[0019] (iv) Demoulding the composite component from the mould cavity.

[0020] It will be apparent to those skilled in the art that step (i) is divided into two alternative sub-steps (ia) or (ib). All statements refer either to step (i) without division and / or to step (i) with division into steps (ia) and (ib). According to the invention, the term "thermoplastic composition" and / or the term "thermoplastic composition (Z)" is occasionally used. Unless the context suggests otherwise, these terms are synonymous. However, the terms must be distinguished in the case where step (i) comprises step (ib), because in this case a further thermoplastic composition is used, which is occasionally also referred to as "thermoplastic composition (Z2)". According to the invention, this can be the same as or different from the thermoplastic composition (Z).

[0021] According to the invention, it is preferred that process steps (i) to (iv) follow one another directly. In this case, however, process steps (i), (ii) and / or (iii), preferably (ii) and (iii), can be carried out multiple times (but do not have to be). If process step (i) is carried out multiple times, it is preferred that the thermoplastic composition used in the second and optionally also each further process step (i) differs from the thermoplastic composition (Z) of the first process step (i). However, it is necessary that the carrier material resulting from step (i) and which is in direct contact with the polymethane raw material mixture in process step (iii) is the thermoplastic composition (Z) according to the invention from which the carrier or film results, which has the OH content according to the invention.The immediate sequence of process steps (i) to (iv) prevents the workpiece temperature from cooling to room temperature during the process. This reduces production times and increases the energy efficiency of the overall process.

[0022] Process steps (ii) and (iii) can be repeated at least once, varying the polyurethane system, whereby one or more polyurethane layers are applied to only one or both sides of the carrier, resulting in a composite component comprising a thermoplastic carrier and at least two identical or different PU components, optionally with more than two layers. If process steps (ii) and (iii) are repeated, it will be apparent to the person skilled in the art that at least the second polyurethane layer is no longer in direct contact with the carrier.

[0023] In process step (ii), a gap is created. The term "gap" is understandable to those skilled in the art. It preferably refers to a cavity that is sealed against the environment so that no material can escape. To create the gap in process step (ii), either the injection molding tool can be opened and one half of the injection molding tool cavity can be replaced with a new half with larger hollow dimensions, or the component can be transferred from the first tool cavity into a second cavity of the same or a second tool that has larger hollow dimensions, or the first cavity can be opened by a gap. Process step (ii) thus comprises enlarging the cavity of the tool and thereby creating a gap, or introducing the carrier into a second cavity of the tool that has larger hollow dimensions than the first cavity, thereby creating a gap.Process step (ii) preferably comprises introducing the carrier into a second cavity of the tool, which is larger than the first cavity in terms of its hollow mold dimensions, thereby creating a gap. If process step (ib) is carried out according to the invention, it is obvious to a person skilled in the art that the carrier from process step (i) is oriented in process step (ii) such that the outer layer of the film, which consists of the thermoplastic composition (Z), faces the gap. This is obvious because this is how the improved bond adhesion found according to the invention can occur. For this, direct contact between the thermoplastic composition (Z) and the polyurethane layer is required. The person skilled in the art thus understands how the carrier from process step (ib) in process step must be oriented in relation to the gap into which the reactive polyurethane raw material mixture is injected.

[0024] The transfer of the substrate in process step (ii) can be carried out using known methods, such as those used in multi-color injection molding. Typical methods include transfer using a turntable, indexing plate, sliding cavity or index plate or similar methods in which the substrate remains on a core. If the substrate remains on the core for transfer, this has the advantage that the position is precisely defined even after transfer. On the other hand, methods for transferring a substrate are known from the prior art in which the substrate is removed from one cavity and placed in another cavity, e.g. with the aid of a handling system. Transferring with removal of the substrate offers greater design freedom in the coating, e.g. when generating a fold or masked areas.Structured lacquer surfaces can also be created, which also offers greater design freedom.

[0025] The process according to the invention also encompasses the possibility of providing the carrier by film insert molding known to those skilled in the art. For this purpose, in process step (i) according to (ib), a film comprising an outer layer consisting of the thermoplastic composition (Z) is inserted into a mold cavity. This film is back-injected with a melt of another thermoplastic composition (Z2) on the side facing away from the outer layer of the film and then cooled to form the carrier. This process step thus provides a carrier in a comparable manner to when, in process step (i) according to (ia), a melt of a thermoplastic composition (Z) is injected into a mold cavity and then cooled. In both cases, a carrier is produced which has the thermoplastic composition on at least one side.According to the invention, this is subsequently brought into contact with the reactive polyurethane raw material mixture. However, since the carrier according to (ib) can also be formed by a layered structure of another thermoplastic composition (Z2) and the film, the cross-section of the carrier according to (ia) and (ib) may differ.

[0026] According to the invention, it is clear that the term "carrier" occasionally includes both a conventional substrate and a multilayer structure comprising a substrate and a film. A substrate differs from a multilayer structure comprising a substrate and a film in that the substrate is generally first formed in the mold cavity by injecting a melt (also referred to as an injection-molded component). In contrast, in a multilayer structure comprising a substrate and a film, the film is first inserted into the mold cavity in its essentially solidified form. To prevent it from slipping, it can be fixed in the mold cavity, preferably by vacuum, static charge, or mechanical anchoring. It cannot be ruled out that the film will at least partially deform during the process according to the invention (for example, due to an increase in temperature).This film is then back-injected with another thermoplastic composition, which forms the actual substrate of the multi-layer structure comprising a substrate and a film upon cooling. However, according to the invention, a distinction is preferably made between substrate and multi-layer structure comprising substrate and film at the time of first introduction into the mold cavity. In the first case, a melt is added, in the latter case a solid, which is subsequently back-injected with a melt. According to the invention, however, an explicit distinction is sometimes made between the carrier and the film in order to make the invention easier to understand. This does not exclude the possibility that occasionally, when reference is made to a "carrier", this also refers to the multi-layer structure comprising substrate and film described above.

[0027] The film used has an outer layer consisting of the thermoplastic composition (Z). The film can be single-layer or multi-layered. If it is multi-layered, at least one of the outer layers is a layer made of the thermoplastic composition (Z). If it is only single-layered, the outer layer is the actual film, and orientation or which side of the film is back-injected is unnecessary, as will be apparent to a person skilled in the art who has understood the invention in particular with regard to achieving better composite adhesion, particularly preferably better adhesion resistance. The film can also consist of the layer containing the thermoplastic composition (Z). According to the invention, a layer is preferably understood to mean a molded body whose extension in the plane is many times greater than its thickness. The surface of the film can be uniform or structured.A textured surface is also referred to as a layer unless otherwise specified. The film may comprise at least one layer.

[0028] The film used can preferably be at least partially coated on at least one side. However, it will be understood by those skilled in the art that this coating, as long as it does not contain the thermoplastic composition (Z) used according to the invention, is brought into direct contact with the further thermoplastic composition (Z2) in step (ib). As a rule, such a coating of the film represents the side referred to in process step (ib) as the "side facing away from the outer layer of the film". The film can be coated by screen printing, by vacuum, or by other known coating techniques. Paints, metals, or the like can be used as coating materials. Likewise, a film composite can also be used according to the invention.The simplest embodiment is a three-layer structure consisting of a plastic film, for example, a metal layer, followed by another plastic film. The advantage of such a structure is that the coating is protected. At least one of the outer layers of the film consists of the thermoplastic composition (Z) used according to the invention.

[0029] The method according to the invention is preferably characterized in that the carrier has a wall thickness of 0.5 mm to 10 mm, preferably 1 mm to 9 mm, particularly preferably 1.5 mm to 6.5 mm and very particularly preferably 2 mm to 5 mm at least at one point.

[0030] The polyurethane layer can be, for example, a PU coating, a PU foam, or a compact PU skin. According to the invention, all of these embodiments are subsumed under the term "polyurethane layer." The polyurethane layers produced using this process can, for example, have thicknesses of 1 μm to 20 cm, preferably 5 μm to 15 cm, particularly preferably 10 μm to 10 cm. The process according to the invention is preferably characterized in that the polyurethane layer has a layer thickness of 1 - 1500 μm, preferably greater than 1.5 mm - 10 mm, particularly preferably greater than 1 cm - 20 cm, and likewise preferably 500 μm to 1 mm. In all of these embodiments, the polyurethane layer can also be foamed.

[0031] The reactive polyurethane raw material mixture preferably has an index of > 90 to < 140, preferably > 100 to < 120, and particularly preferably from 105 to 115. The index is defined as the percentage ratio of the amount of isocyanate actually used to the calculated stoichiometric amount for complete polyol conversion (ie the amount of isocyanate groups calculated for the conversion of the OH equivalents), ie index = ((functionality of the isocyanates * amount of total isocyanates) / (functionality of the alcohols * amount of total hydroxyl groups)) * 100. Preferably, the surface of the injection molding tool in contact with the thermoplastic composition is heated in process step (iii) to a temperature in the range from 50 to 140 °C, preferably 60 to 100 °C and particularly preferably 70 to 105 °C, preferably 80 to 105 °C, and particularly preferably 80 to 100 °C.Alternatively, the surface of the injection molding tool in contact with the thermoplastic composition is particularly preferably heated in process step (iii) to a temperature in the range from 50 to 150 °C, preferably 60 to 140 °C and particularly preferably 70 to 130 °C, preferably 80 to 120 °C, and particularly preferably 90 to 100 °C. These values ​​apply in particular if the carrier material comprises a polycarbonate based on bisphenol A as component A). Should a different (co)polycarbonate be used, the person skilled in the art will be able to adapt preferred temperatures based on the glass transition temperature of this other (co)polycarbonate. Likewise preferably, the surface of the injection molding tool in contact with the reactive polyurethane mixture is heated in process step (iii) to a temperature in the range from 50 to 160 °C, preferably 70 to 130 °C, further preferably 80 to 110 °C, and particularly preferably 90 to 100 °C.Furthermore, in process step (iii), the temperature of the polyurethane-side mold cavity is preferably at least 10 °C, preferably at least 15 °C, and particularly preferably at least 20 °C higher than the temperature of the carrier-side (thermoplastic-side) mold cavity. However, it is also possible to carry out process step (iii) without a temperature delta between the polyurethane-side and the carrier-side mold cavities.

[0032] It is also preferred if polymerization in process step (iii) takes place under elevated pressure. In particular, it is preferred if the pressure in process step (iii) is in the range from 10 to 150 bar, preferably 10 to 90 bar (10,000 to 90,000 hPa). It is also preferred that in process step (iii), the reactive polyurethane raw material mixture is introduced using high-pressure or low-pressure machines. Before demolding the workpiece in steps (ii) and (iv), the workpiece is cooled until dimensional stability is achieved.

[0033] The composite components produced according to the invention are preferably suitable for use as interior or exterior components of a rail, aircraft or motor vehicle.

[0034] Component A

[0035] Polycarbonates according to component A that are suitable for the invention are preferably aromatic. Such aromatic polycarbonates are known from the literature or can be prepared by processes known from the literature (for the preparation of aromatic polycarbonates, see, for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964, as well as DE-AS 1 495 626, DE-A 2 232 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3 000 610, DE-A 3 832 396; for the preparation of aromatic polyestercarbonates, e.g., DE-A 3 077 934). Polycarbonates of component A) within the meaning of the present invention are both homopolycarbonates and copolycarbonates and / or polyestercarbonates; the polycarbonates can be linear or branched in a known manner. According to the invention, mixtures of polycarbonates can also be used.

[0036] A polycarbonate or a material “based on” polycarbonate according to the present invention is a thermoplastic material which preferably comprises at least 50% by weight, particularly preferably at least 60% by weight and particularly preferably at least 70% by weight of polycarbonate.

[0037] A portion, 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. Such polycarbonates, which contain both carbonic acid residues and acid residues of aromatic dicarboxylic acids incorporated into the molecular chain, are referred to as aromatic polyester carbonates. For the purposes of the present invention, they are subsumed under the generic term "polycarbonates."

[0038] The replacement of the carbonate groups by the aromatic dicarboxylic acid ester groups proceeds essentially stoichiometrically and quantitatively, and the molar ratio of the reactants is therefore also reflected in the finished polyester carbonate. The aromatic dicarboxylic acid ester groups can be incorporated both randomly and blockwise. Polyester carbonates are encompassed by the term "polycarbonates" within the meaning of the present invention.

[0039] In the context of the present invention, the term "alkyl" or "alkyl group" preferably refers, unless otherwise stated, to an alkane structure from which a hydrogen atom has been removed. The alkyl group according to the present invention can be linear or branched. It is saturated and therefore comprises nm single bonds between the adjacent carbon atoms. The alkyl group preferably includes methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1,2-Dimethylpropyl, 1-Methylpentyl, 2-Methylpentyl, 3-Methylpentyl, 4-Methylpentyl, 1,1-Dimethylbutyl, 1,2-Dimethylbutyl, 1,3-Dimethylbutyl, 2,2-Dimethylbutyl, 2,3-Dimethylbutyl, 3, 3-Dimethylbutyl, 1-Ethylbutyl, 2-Ethylbutyl, 1,1,2-Trimethylpropyl, 1,2,2-Trimethylpropyl, 1-Ethyl-1-methylpropyl, l-Ethyl-2-methylpropyl, l-Ethyl-2-methylpropyl and the like.The selection of these structures may be limited if the number of carbon atoms is defined differently in the present invention.

[0040] In the context of the present invention, the term "alkylene" or "alkylene group" preferably refers, unless otherwise stated, to a bridging alkane structure from which two hydrogen atoms have been removed from different carbon atoms. In this context, the two hydrogen atoms removed from the two carbon atoms can be removed from any carbon atoms in the alkane structure. This means that the two carbon atoms can be adjacent, but do not necessarily have to be adjacent. An alkylene group can be linear or branched. It is saturated. If the alkylene group comprises only one carbon atom, it is a methylene group (-CH2-), which is linked to the rest of the molecule via two single bonds.The alkylene group preferably comprises methylene, ethylene, n-propylene, isopropylene, n-butylene, sec-butylene, tert-butylene, n-pentylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, neopentylene, 1-ethylpropylene, n-hexylene, 1,1-dimethylpropylene, 1,2-dimethylpropylene, 1,2-dimethylpropylene, 1-methylpentylene, 2-methylpentylene, 3-methylpentylene, 4-methylpentylene, 1,1-dimethylbutylene, 1,2-dimethylbutylene, 1,3-dimethylbutylene, 2,2-dimethylbutylene, 2,3-dimethylbutylene, 3,3-dimethylbutylene, 1-ethylbutylene, 2-ethylbutylene, 1,1,2-trimethylpropylene, 1,2,2-trimethylpropylene, 1-ethyl-1-methylpropylene, l-ethyl-2-methylpropylene, l-ethyl-2-methylpropylene, and the like. The selection of these structures may be limited if the number of carbon atoms is defined differently within the scope of the present invention.

[0041] In the context of the present invention, the term "alkylidene" or "alkylidene group" preferably refers, unless otherwise stated, to a bridging alkane structure in which two hydrogen atoms have been removed from the same carbon atom. The alkylidene group preferably includes isopropylidene, n-propylidene, isoheptylidene, and the like.

[0042] Preferred polyester carbonates are represented by formula (w) in the

[0043] A of each repeating unit independently represents an aliphatic or aromatic divalent group, e.g. an aromatic divalent group having 6 to 30 carbon atoms, which may contain one or more aromatic rings, may be substituted and may contain aliphatic or cycloaliphatic radicals or alkylaryls or heteroatoms as bridging structures, such as a structure of the formula (wi) in the

[0044] R 6 and R 7independently of one another represent H, Ci- to Cis-alkyl-, Ci- to Cis-alkoxy,

[0045] Halogen such as Cl or Br or each optionally substituted aryl or aralkyl, preferably H or Ci- to Ci2-alkyl, particularly preferably H or Ci- to Cs-alkyl and very particularly preferably H or methyl, and

[0046] X represents a single bond, -SO2-, -CO-, -O-, -S-, C1- to C12-alkylene, C2- to C5-alkylidene or C5- to C12-cycloalkylidene, which may be substituted by C1- to C12-alkyl, preferably methyl or ethyl, and also C1- to C12-arylene, which may optionally be condensed with further aromatic rings containing heteroatoms, or - based on A - an aliphatic divalent group which may be cyclic, linear or branched and has 2 to 30 carbon atoms, which may be interrupted by at least one heteroatom and may comprise more than one cycle, such as, for example, structure (wii) or - based on A - a linear alkylene group having 2 to 22 carbon atoms, preferably 2 to 4 carbon atoms, which may be interrupted by at least one heteroatom, or a branched alkylene group having 4 to 20 carbon atoms, preferably 5 to 15 carbon atoms, which may be interrupted by at least one heteroatom or a cycloalkylene group having 4 to 20 carbon atoms, preferably 5 to 15 carbon atoms, which may be interrupted by at least one heteroatom and which may contain more than one cycle;

[0047] D in each repeating unit independently represents A or an aromatic or cycloaliphatic divalent group, preferably an optionally substituted phenylene or an optionally substituted cyclohexylene;y in each repeating unit independently represents an aliphatic divalent group which may be cyclic, linear or branched and has 2 to 30 carbon atoms, which may be interrupted by at least one heteroatom and more than one cycle or an aromatic divalent group, preferably a linear aliphatic divalent group having 2 to 30 carbon atoms, a branched aliphatic divalent group having 2 to 30 carbon atoms, a cycloaliphatic divalent group having 6 to 30 carbon atoms, which may have more than one cycle or an aromatic divalent group having 6 to 30 carbon atoms, particularly preferably an optionally substituted cyclohexylene, an aliphatic linear group having 2 to 18 carbon atoms or an optionally substituted phenylene;

[0048] 0 < x < 1.

[0049] Particularly preferred polyester carbonates are those based on the combination of the following diols and diacids: bisphenol A and sebacic acid; bisphenol A and isophthalic acid, terephthalic acid and / or phthalic acid and optionally resorcinol; isosorbide and cyclohexanedicarboxylic acid and optionally further diols or diacids.

[0050] Dihydroxyaryl compounds 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, a-a'-bis-(hydroxyphenyl)-diisopropylbenzenes, phthalimidines derived from isatin or phenolphthalein derivatives as well as their core-alkylated, core-arylated and core-halogenated compounds or 9,9-bis(4-hydroxyphenyl)fluorene.Preferred dihydroxyaryl compounds 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-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfone, 2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methy ibutane, 1, 1 -bis-(3 ,5-dimethy1-4-hydroxyphenyl)-p- diisopropylbenzene, 9,9-bis(4-hydroxyphenyl)fluorene and l,l-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, as well as the bisphenols (I) to (III). in which R' is each Ci-C4-alkyl, aralkyl or aryl, preferably methyl or phenyl, most preferably methyl.

[0051] Particularly preferred dihydroxyaryl compounds are 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A), 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, l,l-bis-(4-hydroxyphenyl)-cyclohexane, l,l-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and dimethyl-bisphenol A as well as the dihydroxyaryl compounds of the formulas (I), (II) and (III).

[0052] These and other suitable dihydroxyaryl compounds are described, for example, in US-A 3 028 635, US-A

[0053] 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 2,063,050, DE-A 2 036 052, DE-A 2 211 956 and DE-A

[0054] 3 832 396, in FR-A 1 561 518, in the monograph H. Schnell, “Chemistry and Physics of Polycarbonates”, Interscience Publishers, New York 1964".

[0055] Also preferred are polycarbonates for the preparation of which a dihydroxyaryl compound of the following formula (Ia) was used: in the

[0056] R 5 represents hydrogen or CI - to C4-alkyl, CI - to C4-alkoxy, preferably hydrogen or methyl or methoxy, particularly preferably hydrogen,

[0057] R 6 , R 7 , R 8 and R 9 independently of one another represent C6- to C12-aryl or CI- to C4-alkyl, preferably phenyl or methyl, in particular methyl,

[0058] Y represents a single bond, SO2-, -S-, -CO-, -O-, CI- to C6-alkylene, C2- to C5-alkylidene, C6- to C12-arylene, which may optionally be condensed with further aromatic rings containing heteroatoms, or a C5- to C6-cycloalkylidene radical which may be substituted one or more times by CI- to C4-alkyl, preferably a single bond, -O-, isopropylidene or a C5- to C6-cycloalkylidene radical which may be substituted one or more times by CI to C4-alkyl,

[0059] V represents oxygen, C2- to C6-alkylene or C3- to C6-alkylidene, preferably oxygen or C3-alkylene, p, q and r independently of one another each represent 0 or 1, where, when q = 0, W is a single bond, when q = 1 and r = 0, W represents -O-, C2- to C6-alkylene or C3- to C6-alkylidene, preferably -O- or C3-alkylene, when q = 1 and r = 1, W and V independently of one another represent C2- to C6-alkylene or C3- to C6-alkylidene, preferably C3-alkylene,

[0060] Z represents C1-C6-alkylene, preferably C2-alkylene, o represents an average number of repeating units from 10 to 500, preferably 10 to 100, and m represents an average number of repeating units from 1 to 10, preferably 1 to 6, particularly preferably 1.5 to 5. It is also possible to use dihydroxyaryl compounds in which two or more siloxane blocks of the general formula (Ia) are linked via terephthalic acid and / or isophthalic acid to form ester groups.

[0061] Copolycarbonates with monomer units of the general formula (Ia), in particular with bisphenol A, and in particular the preparation of these copolycarbonates are described, for example, in WO 2015 / 052106 A2.

[0062] Dihydroxyaryl compounds can also be used in which two or more siloxane blocks of the general formula (Ia) are linked via terephthalic acid and / or isophthalic acid to form ester groups.

[0063] The polycarbonates are produced in a known manner from diphenols, carbonic acid derivatives, optionally chain terminators and optionally branching agents, whereby to produce the polyester carbonates, some of the carbonic acid derivatives are replaced by aromatic dicarboxylic acids or derivatives of dicarboxylic acids, depending on the carbonate structural units to be replaced in the aromatic polycarbonates by aromatic dicarboxylic acid ester structural units.

[0064] In the case of homopolycarbonates, only one diphenol is used; in the case of copolycarbonates, two or more diphenols are used. The diphenols used, as well as all other chemicals and auxiliaries added to the synthesis, may be contaminated with impurities arising from their own synthesis, handling, and storage. However, it is desirable to work with the purest raw materials possible.

[0065] The monofunctional chain terminators required to regulate the molecular weight, such as phenols or alkylphenols, in particular phenol, p-tert-butylphenol, isooctylphenol, cumylphenol, their chlorocarbonic acid esters or acid chlorides of monocarboxylic acids or mixtures of these chain terminators, are either fed into the reaction with the bisphenolate(s) or added at any time during the synthesis as long as phosgene or chlorocarbonic acid end groups are still present in the reaction mixture, or in the case of acid chlorides and chlorocarbonic acid esters as chain terminators, as long as sufficient phenolic end groups of the forming polymer are available. However, the chain terminator(s) are preferably added after phosgenation at a location or at a time when no more phosgene is present but the catalyst has not yet been added, or they are added before the catalyst, together with the catalyst, or in parallel.Any branching agents or branching agent mixtures that may be used are added to the synthesis in the same way, but usually before the ketene terminators. Typically, trisphenols, quarterphenols, or acid chlorides of tri- or tetracarboxylic acids, or mixtures of polyphenols or acid chlorides, are used. Some of the compounds which can be used as branching agents and which have three or more than three phenolic hydroxyl groups are, for example, phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-2-heptene, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane, l,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.

[0066] Some of the other trifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride, and 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole. Preferred branching agents are 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole and 1,1,1-tri(4-hydroxyphenyl)ethane. The amount of branching agents to be used, if desired, is 0.05 mol% to 2 mol%, again based on the moles of diphenols used. All of these methods for producing polycarbonates are familiar to those skilled in the art. Preferred methods of producing the polycarbonates to be used according to the invention, including the polyestercarbonates, 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 5,340,905 A, US 5,097,002 A, US-A 5,717,057 A). The polycarbonate is preferably produced via the

[0067] produced using a melt transesterification process.

[0068] In the first case, the acid derivatives used are preferably phosgene and optionally dicarboxylic acid dichlorides; in the latter case, diphenyl carbonate and optionally dicarboxylic acid diesters are preferred. Catalysts, solvents, workup, reaction conditions, etc., for polycarbonate or polyester carbonate production are sufficiently described and known in both cases. The relative solution viscosity (r| rei) of the aromatic polycarbonates is preferably in the range from 1.18 to 1.4, particularly preferably in the range from 1.20 to 1.32, very particularly preferably in the range from 1.22 to 1.29 (measured on solutions of 0.5 g of polycarbonate in 100 ml of methylene chloride solution at 25°C). The weight-average molecular weight Mw of the aromatic polycarbonates and polyestercarbonates is preferably in the range from 15,000 to 35,000, more preferably in the range from 20,000 to 33,000, particularly preferably 23,000 to 30,000, determined by. The Mw values ​​are determined by gel permeation chromatography, calibrated against bisphenol A polycarbonate standards using dichloromethane as the eluent. Calibration is performed with linear polycarbonates (made from bisphenol A and phosgene) of known molecular weight distribution from PSS Polymer Standards Service GmbH, Germany; calibration is performed according to method 2301-0257502-09D (2009 Edition) from Currenta GmbH & Co. OHG, Leverkusen. The eluent is dichloromethane.Column combination of cross-linked styrene-divinylbenzene resins. Analytical column diameter: 7.5 mm; length: 300 mm. Column material particle size: 3 μm to 20 μm. Solution concentration: 0.2 wt.%. Flow rate: 1.0 ml / min. Solution temperature: 30°C. Detection with a refractive index detector (RI).

[0069] According to the invention, the carrier or film has a defined OH content. The OH groups can also originate at least partially from the polycarbonate of component A). Preferably, at least some of the OH groups originate from the polycarbonate of component A).

[0070] The skilled person is generally aware of how to adjust / influence the OH content, in particular the aromatic OH content, such as the phenolic OH content of a polycarbonate. If the interfacial process is used, the skilled person can adjust the concentration of phenolic OH desired according to the invention, for example, by adjusting the concentration of the chain terminator or by using special chain terminators, which may also contain phenolic OH groups, or by subsequently reacting the end groups with compounds containing phenolic OH groups. If the melt transesterification process is used to produce the polycarbonate, the skilled person knows that the catalyst used or the ratio of diaryl carbonate to the bisphenol used can influence the phenolic OH content.Here, too, it is possible that, in a subsequent step, the existing polycarbonate can be modified at the end groups in such a way that phenolic OH groups are specifically introduced or reacted.

[0071] In particular, the process according to the invention is characterized in that the polycarbonate of component A) comprises one, particularly preferably several of the following structures (4) to (7): in which the phenyl rings can independently of one another be mono- or disubstituted by C1 to C5 alkyl, halogen, preferably C1 to C4 alkyl, particularly preferably by methyl, and X represents a single bond, a linear or branched C1 to C8 alkylene group, a C2 to C10 alkylidene group, or a C5 to C10 cycloalkylidene group, preferably a single bond or C1 to C4 alkylene, and particularly preferably isopropylidene, and the "-" represents the bonding of the structures (4) to (7) into the aromatic polycarbonate. It is particularly preferred that the amount of structural units (4) to (7) in total is 10 ppm to 1000 ppm, preferably 50 to 950 ppm, particularly preferably 80 ppm to 850 ppm.

[0072] To determine the amount of structural units (4) to (7), the respective polycarbonate is subjected to total saponification, and the amount of degradation products is determined using quantitative HPLC. The degradation products can have the structures (4a) to (7a). Structures (4a) to (7a) are given as examples for the use of a polycarbonate comprising bisphenol A. (This can be done, for example, as follows: The polycarbonate sample is saponified using sodium methylate under reflux. The corresponding solution is acidified and evaporated to dryness. The drying residue is dissolved in acetonitrile, and the phenolic compounds of formulas (4a) to (7a) are determined using HPLC with UV detection.)

[0073] The amount of the compound of formula (4a) released is preferably 10 to 800 ppm, preferably 20 to 75,000 ppm, particularly preferably 25 to 700 ppm and especially preferably 30 to 500 ppm.

[0074] Preferably, the amount of the compound of formula (5a) released is 0 (ie below the detection limit of 10 ppm) to 100 ppm, particularly preferably 0 to 80 ppm and especially preferably 0 to 50 ppm.

[0075] Preferably, the amount of the compound of formula (6a) released is 0 (ie below the detection limit of 10 ppm) to 800 ppm, more preferably 10 to 700 ppm and particularly preferably 20 to 600 ppm and very particularly preferably 30 to 350 ppm.

[0076] Preferably, the amount of the compound of formula (7a) released is 0 (ie below the detection limit of 10 ppm) to 300 ppm, preferably 5 to 250 ppm and particularly preferably 10 to 200 ppm.

[0077] Component B

[0078] The thermoplastic composition (Z) further comprises a thermoplastic polymer which is different from component A). The thermoplastic polymer is preferably a blend partner. The thermoplastic composition (Z) may also comprise more than one thermoplastic polymer of component B). Component B) particularly preferably does not refer to a polycarbonate. Component B) is most preferably not a polycarbonate with a melt volume flow rate (MVR) of 30 cm 3 / (10 min) at a test temperature of 250 °C and 1.2 kg load). The thermoplastic polymer of component B) preferably comprises a rubber-modified and / or rubber-free vinyl (co)polymer and / or a polyester.

[0079] The rubber-free vinyl (co)polymer can preferably be a copolymer of at least one monomer from the group of vinyl aromatics, vinyl cyanides (unsaturated nitriles), (meth)- ,Acrylic acid (Cl to C8) alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and imides) of unsaturated carboxylic acids. Particularly suitable as component B) are (co)polymers of

[0080] B.1 50 to 99 wt.%, preferably 65 to 85 wt.%, particularly preferably 70 to 80 wt.%

[0081] % based on the (co)polymer of at least one monomer selected from the group of vinylaromatics (such as styrene, a-methylstyrene), core-substituted vinylaromatics (such as p-methylstyrene, p-chlorostyrene) and (meth)acrylic acid (C1-C8) alkyl esters (such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate) and

[0082] B.2 1 to 50 wt.%, preferably 15 to 35 wt.%, particularly preferably 20 to 30 wt.%

[0083] % based on the (co)polymer of at least one monomer selected from the group of vinyl cyanides (such as unsaturated nitriles such as acrylonitrile and methacrylonitrile), (meth)acrylic acid (Cl-C8) 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).

[0084] These (co)polymers are resinous, thermoplastic, and rubber-free. The copolymer of B1 styrene and B2 acrylonitrile is particularly preferred.

[0085] Such (co)polymers are known and can be prepared by radical polymerization, in particular by emulsion, suspension, solution, or bulk polymerization. The (co)polymers have a weight-average molecular weight (Mw), determined by gel permeation chromatography with GPC in tetrahydrofuran with polystyrene as standard, of preferably 50,000 to 250,000 g / mol, more preferably 70,000 to 200,000 g / mol, particularly preferably 80,000 to 160,000 g / mol. This weight-average molecular weight (M w) determined by gel permeation chromatography in tetrahydrofuran using a polystyrene as standard (preferably based on DIN 55672-1:2007-08 using a polystyrene calibration). Calibration can be performed using narrowly distributed polystyrene standards (e.g., ReadyCal Kit Polystyrene low, nominal Mp 266 66,000 Da). The general method is defined by Currenta GmbH & Co. OHG under AM 2011-0623701-09D, which can be requested from Currenta at any time. Tetrahydrofuran (THF) was used as the eluent. GPC can comprise one or more commercially available GPC columns (e.g., SDV columns) connected in series for size exclusion chromatography. Detection can be performed using ultraviolet radiation (UV) and / or refractive index.

[0086] The component may also comprise a rubber-modified vinyl (co)polymer. Those skilled in the art will appreciate that, when a rubber-modified vinyl (co)polymer is used, a rubber-free vinyl (co)polymer, as described above, may also be present at the same time. The rubber-modified vinyl (co)polymers thus contain rubber-based graft polymers and, optionally, rubber-free vinyl (co)polymers.

[0087] Such rubber-based graft polymers can

[0088] B.la 5 to 95 wt.%, preferably 20 to 92 wt.%, in particular 30 to 91 wt.%, based on the graft polymer, of at least one vinyl monomer

[0089] B.2a 95 to 5 wt.%, preferably 80 to 8 wt.%, in particular 70 to 9 wt.%, based on the graft polymer, of one or more rubber-elastic graft bases with glass transition temperatures < -50°C, more preferably < -60°C, particularly preferably < -70°C.

[0090] Unless expressly described otherwise in the present invention, the glass transition temperature is determined for all components by means of differential scanning calorimetry (DSC) according to DIN EN 61006 (version of 1994) at a heating rate of 10 K / min with determination of the Tg as the midpoint temperature (tangent method).

[0091] The graft base B.2a generally has an average particle size (D50 value) of 0.05 to 10.00 pm, preferably of 0.1 to 5.0 pm and particularly preferably of 0.2 to 1.5 pm.

[0092] The average particle size D50 is the diameter above and below which 50% by weight of the particles lie. Unless expressly stated otherwise in the present invention, it is determined for all components by ultracentrifuge measurement (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972), 782-1796).

[0093] The monomers B.la are preferably mixtures of

[0094] B.1.1 65 to 85% by weight, particularly preferably 70 to 80% by weight, further preferably 74 to 78% by weight, in each case based on the sum of B.1.1 and B.1.2, of vinylaromatics and / or core-substituted vinylaromatics (such as styrene, a-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or (meth)acrylic acid (C1-C8)-alkyl esters, such as methyl methacrylate, ethyl methacrylate), and

[0095] B.1.2 15 to 35 wt. %, particularly preferably 20 to 30 wt. %, further preferably 22 to 26 wt. %, based in each case on the sum of B.1.1 and B.1.2, of vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth)acrylic acid (C1-C8) alkyl esters, such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids, for example maleic anhydride. Preferred monomers B.1.1 are selected from at least one of the monomers styrene, α-methylstyrene, and methyl methacrylate; preferred monomers B.1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride, and methyl methacrylate. Particularly preferred monomers are B.1.1 styrene and B.1.2 acrylonitrile. Alternatively, preferred monomers are B.1.1 methyl methacrylate and B.1.2 methyl methacrylate.

[0096] Suitable graft bases B.2a of the graft polymers include, for example, diene rubbers, EP(D)M rubbers, i.e. those based on ethylene / propylene and optionally diene, acrylate, polyurethane, silicone, chloroprene, ethylene / vinyl acetate and acrylate-silicone composite rubbers.

[0097] Preferred grafting bases B.1.2 are diene rubbers, preferably containing butadiene or copolymers of dienes, preferably containing butadiene, and further copolymerizable vinyl monomers (e.g. according to B.1.1 and B.1.2) or mixtures of one or more of the aforementioned components.

[0098] Particularly preferred as the graft base B.2a is pure polybutadiene rubber. In another preferred embodiment, B.2a is styrene-butadiene rubber, particularly preferably styrene-butadiene block copolymer rubber.

[0099] The gel content of the graft base B.2a is at least 30 wt. %, preferably at least 40 wt. %, in particular at least 60 wt. %, in each case based on B.2a and measured as the insoluble content in toluene.

[0100] The gel content of the graft base B.2a or of the rubber-modified graft polymers used according to the invention is determined at 25 °C in a suitable solvent as the fraction insoluble in these solvents (M. Hoffmann, H. Krömer, R. Kuhn, Polymeranalytik I and II, Georg Thieme -Verlag, Stuttgart 1977).

[0101] Suitable polymers are, for example, ABS or MBS polymers, as described, for example, in DE-OS 2 035 390 (=US PS 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), p. 280 ff.

[0102] The rubber-modified graft copolymers are produced by radical polymerization, e.g., by emulsion, suspension, solution, or bulk polymerization. Mixtures of graft polymers produced by different processes can also be used.

[0103] If the rubber-modified graft polymers are produced in emulsion polymerization, they include

[0104] B.1a 5 to 75% by weight, preferably 20 to 60% by weight, particularly preferably 25 to 50% by weight, based on the graft polymer, of at least one vinyl monomer on B.2a 95 to 25% by weight, preferably 80 to 40% by weight, particularly preferably 75 to 50% by weight, based on the graft polymer, of one or more rubber-elastic graft bases with glass transition temperatures < -50°C, more preferably < -60°C, particularly preferably < -70°C.

[0105] The graft base B.2a of rubber-modified graft polymers produced by emulsion polymerization have an average particle size (D50 value) of 0.05 to 2.00 pm, preferably of 0.1 to 1.0 pm, particularly preferably of 0.2 to 0.5 pm. Rubber-modified graft polymers produced by emulsion polymerization have a gel content, measured in acetone as solvent, of preferably at least 30 wt. %, particularly preferably at least 60 wt. %, further preferably at least 80 wt. %.

[0106] If the rubber-modified graft polymers are produced by suspension, solution or bulk polymerization, they include

[0107] B. la 80 to 95 wt. %, preferably 84 to 92 wt. %, particularly preferably 87 to 91 wt. %, based on the graft polymer, of at least one vinyl monomer

[0108] B.2a 20 to 5 wt.%, preferably 16 to 8 wt.%, particularly preferably 13 to 9 wt.%, based on the graft polymer, of one or more rubber-elastic graft bases with glass transition temperatures < -50°C, more preferably < -60°C, particularly preferably < -70°C.

[0109] The graft base B.2a of graft polymers prepared in suspension, solution or bulk polymerization have an average particle size (D50 value) of 0.3 to 10.00 pm, preferably of 0.4 to 5.0 pm, particularly preferably of 0.5 to 1.5 pm.

[0110] Graft polymers produced in suspension, solution or bulk polymerization have a gel content, measured in acetone as solvent, of preferably 10 to 50 wt.%, particularly preferably 15 to 40 wt.%, further preferably 18 to 30 wt.%.

[0111] Particularly suitable graft polymers produced by the emulsion polymerization process are, for example, ABS polymers which are produced by the emulsion polymerization process by redox initiation with an initiator system of organic hydroperoxide and ascorbic acid according to US-P 4 937285.

[0112] Other particularly suitable graft polymers produced by the emulsion polymerization process are MBS modifiers with a core-shell structure.

[0113] As already described above, component B) may contain, in addition to the rubber-modified vinyl (co)polymers, free vinyl (co)polymer consisting of the monomers according to B.1a, i.e., vinyl (co)polymer not chemically bonded to the rubber base and not enclosed in the rubber particles. This may arise during the polymerization of the graft polymers (grafting onto the graft base is not always complete) or may be polymerized separately and added. It is also possible that part of the free vinyl (co)polymer originates from the graft polymers themselves, while another part is polymerized separately and added to component B.The proportion of free vinyl (co)polymer (regardless of its origin), measured as the acetone-soluble fraction, in a possible mixture of rubber-modified and rubber-free vinyl (co)polymers of component B), based on this mixture, is preferably at least 5% by weight, particularly preferably at least 30% by weight, further preferably at least 50% by weight.

[0114] Component B) may also comprise polyester. Suitable polyesters are preferably aromatic; more preferably, they are polyalkylene terephthalates.

[0115] 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, as well as mixtures of these reaction products.

[0116] 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 1,4-butanediol residues.

[0117] The preferred aromatic polyalkylene terephthalates can contain, in addition to terephthalic acid residues, up to 20 mol%, preferably up to 10 mol%, residues of other aromatic or cycloaliphatic dicarboxylic acids having 8 to 14 C atoms or aliphatic dicarboxylic acids having 4 to 12 C atoms, such as residues of phthalic acid, isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid, succinic acid, adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid.

[0118] The preferred aromatic polyalkylene terephthalates can contain, in addition to ethylene glycol or butanediol-1,4-residues, up to 20 mol%, preferably up to 10 mol%, other aliphatic diols having 3 to 12 C atoms or cycloaliphatic diols having 6 to 21 C atoms, e.g. residues of 1,3-propanediol, 2-ethyl-1,3-propanediol, neopentyl glycol, 1,5-pentanediol, 1,6-hexanediol, cyclo _, hexane-dimethanol-1,4, 3-ethyl~ , pentanediol-2,4, 2-methylpentanediol- 2,4, 2,2,4-trimethylpentanediol-l,3, 2-ethylpentanediol-l .3. 2,2-diethylpropanediol-1,3, hexanediol-2,5, l,4-di-(ß-hydroxyethoxy)-benzene, 2,2-bis-(4-hydroxycyclohexyl)-propane, 2,4-dihydroxy-l,l,3,3-tetramethyl-cyclobutane, 2,2-bis-(4-ß-hydroxyethoxy-phenyl)-propane and 2,2-Bis-(4-hydroxypropoxyphenyl)-propane (DE-A 2 407 674, 2 407 776, 2 715 932).

[0119] The aromatic polyalkylene terephthalates can be branched by incorporating relatively small amounts of tri- or tetrahydric alcohols or tri- or tetrabasic carboxylic acids, e.g., according to 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.

[0120] Particularly preferred are aromatic polyalkylene terephthalates which have been prepared solely from terephthalic acid and its reactive derivatives (e.g. its dialkyl esters) and ethylene glycol and / or 1,4-butanediol, and mixtures of these polyalkylene terephthalates.

[0121] 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.

[0122] The preferably used aromatic polyalkylene terephthalates have a viscosity number of 0.4 to 1.5 dl / g, preferably 0.5 to 1.2 dl / g, measured in phenol / o-dichlorobenzene (1:1 parts by weight) in a concentration of 0.05 g / ml according to ISO 307 at 25°C in an Ubbelohde viscometer.

[0123] The aromatic polyalkylene terephthalates can be produced by known methods (see, for example, Kunststoff-Handbuch, Volume VIII, p. 695 ff., Carl-Hanser-Verlag, Munich 1973).

[0124] According to the invention, the thermoplastic composition (Z) may further comprise a component C), where C) is one or more additives. Component C) is thus optional.

[0125] Preferably, component C) is selected from the group consisting of flame retardants (e.g. organic phosphorus or halogen compounds, in particular bisphenol A-based oligophosphate), anti-drip agents (e.g. compounds of the substance classes of fluorinated polyolefins, silicones and aramid fibers), flame retardant synergists (e.g. nanoscale metal oxides), smoke inhibitors (e.g. zinc borate), lubricants and mold release agents (e.g. pentaerythritol tetrastearate), nucleating agents, antistatic agents, conductivity additives, stabilizers (e.g.Hydrolysis, heat ageing and UV stabilizers as well as transesterification inhibitors and acid / base quenchers), flow promoters, compatibilizers, impact modifiers (both with and without core-shell structure) provided that they are different from component B), fillers and reinforcing materials (e.g. glass or carbon fibers, talc, mica, kaolin, CaCO,) as well as dyes and pigments (e.g. titanium dioxide or iron oxide).

[0126] In a preferred embodiment, component C) is free of flame retardants, anti-drip agents, flame retardant synergists, and smoke inhibitors, and the composition is therefore free of them. In a likewise preferred embodiment, component C) is free of them, and the composition is therefore free of fillers and reinforcing materials. In a particularly preferred embodiment, component C) is free of them, and the composition is therefore free of them, flame retardants, anti-drip agents, flame retardant synergists, smoke inhibitors, and fillers and reinforcing materials.

[0127] In a preferred embodiment, component C) is at least one additive selected from the group consisting of lubricants and mold-release agents, stabilizers, flow promoters, compatibilizers, impact modifiers, provided that they are different from component B), fillers and reinforcing materials, dyes and pigments.

[0128] In a preferred embodiment, component C) is at least one additive selected from the group consisting of lubricants / molding agents, fillers and reinforcing materials and stabilizers.

[0129] In a particularly preferred embodiment, component C) is at least one additive selected from the group consisting of lubricants / molding agents, fillers and reinforcing agents, stabilizers, dyes and pigments and is free from further polymer additives.

[0130] In a preferred embodiment, component C) comprises the mold release agent pentaerythritol tetrastearate.

[0131] In a preferred embodiment, component C) comprises as stabilizer at least one representative selected from the group consisting of sterically hindered phenols, organic phosphites, sulfur-based co-stabilizers and organic and inorganic Brönsted acids.

[0132] In a particularly preferred embodiment, component C) comprises as stabilizer at least one representative selected from the group consisting of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and tris(2,4-di-tert-butylphenyl)phosphite.

[0133] In a particularly preferred embodiment, component C) comprises as stabilizer a combination of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and tris(2,4-di-tert-butylphenyl)phosphite.

[0134] Particularly preferably, component C) comprises pentaerythritol tetrastearate as mold release agent, 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 as stabilizer and optionally a Brönsted acid and no further polymer additives.

[0135] Component C) further preferably comprises pentaerythritol tetrastearate as mold release agent, a combination of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and tris(2,4-di-tert-butylphenyl)phosphite as stabilizer, optionally a Brönsted acid and is free from further polymer additives.

[0136] Component C) further preferably comprises at least one filler and / or reinforcing material. It is preferred that the at least one filler and / or reinforcing material is selected from the group consisting of aluminum hydroxide, aluminum oxide, aluminum silicates, barium oxide, barium sulfate, boehmite, calcium carbonate, diaspore, dolomite, glass beads, graphite, expanded graphite, kaolin, chalk, magnesium aluminate, magnesium hydroxide, magnesium oxide, montmorillonite, quartz powder, silicates, silicon dioxide, talc, titanium dioxide, vermiculite, wollastonite, zeolites, zirconium oxide, glass fibers, carbon fibers, basalt fibers, aramid fibers, liquid crystal polymer fibers, polyphenylene sulfide fibers, polyether ketone fibers, polyetheretherketone fibers, polyetherimide fibers, and any mixtures thereof.

[0137] Preferred fillers are inorganic fillers such as aluminum hydroxide (gibbsite), aluminum oxide, aluminum silicates such as mica or clay layers, barium oxide, barium sulfate, boehmite, calcium carbonate, diaspore, dolomite, glass beads, graphite, expanded graphite, kaolin, chalk, magnesium aluminate, magnesium hydroxide, magnesium oxide, montmorillonite, especially in an organophilic form modified by ion exchange, quartz powder, silicates, silicon dioxide (unfired), talc, titanium dioxide, vermiculite, wollastonite, zeolites, and / or zirconium oxide. Furthermore, the fillers can be particulate, flaky, or fibrous. Mixtures of various inorganic materials can also be used.

[0138] In a preferred embodiment, talc is used as component C). Preferred amounts of talc are between greater than 5% by weight and 40% by weight, based on the thermoplastics used. Further preferred amounts of talc are between 5.5% by weight and 35% by weight, particularly preferably between 6% by weight and 30% by weight, based on the thermoplastics used. Very particular preference is given to using 10% by weight to 25% by weight of talc, based on the thermoplastics used in the compositions.

[0139] Furthermore, fibers can be used as component C). Examples of fibers suitable for the invention are glass fibers, carbon fibers, basalt fibers, aramid fibers, liquid crystal polymer fibers, polyphenylene sulfide fibers, polyether ketone fibers, polyetheretherketone fibers, polyetherimide fibers, and mixtures thereof. The use of glass fibers or carbon fibers has proven particularly practical.

[0140] In a preferred embodiment, glass fibers are used as component C). Preferred amounts of glass fibers used are between greater than 5% by weight and 40% by weight of glass fibers, based on the thermoplastics used. Further preferred amounts of glass fibers are between 5.5% by weight and 35% by weight, particularly preferably between 6% by weight and 30% by weight, based on the thermoplastics used. Very particular preference is given to using 10% by weight and 25% by weight, and equally preferably between 15% by weight and 25% by weight, of glass fibers, based on the thermoplastics used in the compositions.

[0141] The thermoplastic composition (Z) thus preferably comprises component A), component B) and optionally component C). More preferably, the thermoplastic composition consists essentially of component A), component B) and optionally component C). Very particularly preferably, the thermoplastic composition consists of component A), component B) and optionally component C). In a further preferred embodiment, the thermoplastic composition (Z) consists of 90% by weight, even more preferably 95% by weight and particularly preferably 100% by weight of components A) to C).

[0142] It is preferred that the thermoplastic composition (Z) comprises at least 50% by weight, preferably at least 60% by weight, particularly preferably at least 65% by weight of component A), more than 0% by weight and up to 50% by weight, preferably 0.1% by weight to 40% by weight, particularly preferably 1% by weight to 35% by weight of component B) and optionally component C), preferably 0 to 30% by weight, particularly preferably 0.1% by weight to 25% by weight.

[0143] It is particularly preferred that the thermoplastic composition (Z) comprises 0.1 wt.% to 10 wt.%, particularly preferably 0.3 wt.% to 5 wt.% and very particularly preferably 0.5 to 1.5 wt.% of component C) if C) does not comprise any fillers and reinforcing materials.

[0144] It is also particularly preferred that the thermoplastic composition (Z) comprises 0.1 wt.% to 10 wt.%, particularly preferably 0.3 wt.% to 5 wt.% and very particularly preferably 0.5 to 1.5 wt.% of component C) with the exception of fillers and reinforcing materials and additionally 5.5 wt.% to 35 wt.%, particularly preferably 6 wt.% to 30 wt.%, very particularly preferably 10 wt.% to 25 wt.% of talc or 10 wt.% to 25 wt.%, preferably 15 wt.% to 25 wt.% of a glass fiber.

[0145] It is also preferred that the thermoplastic composition Z) comprises at most 90 wt. %, particularly preferably at most 85 wt. %, further preferably at most 80 wt. %, further preferably at most 75 wt. % of component A). The skilled person can select these upper limits with the above-mentioned lower limits in relation to the other components.

[0146] Unless otherwise stated, all wt% values ​​refer to the total composition.

[0147] According to the invention, the carrier or film has an OH content of at least 230 ppm. Particularly preferably, the carrier or film has an OH content of 230 ppm to 4000 ppm, very particularly preferably of 300 ppm to 3500 ppm, equally preferably of 500 ppm to 3000 ppm, particularly preferably of 350 ppm to 2500 ppm, further preferably of 400 ppm to 2000 ppm, further preferably of 450 ppm to 1500 ppm, and very particularly preferably of 500 ppm to 1000 ppm.

[0148] Unless otherwise stated, ppm values ​​refer to weight.

[0149] The OH content of the carrier or film is preferably at least partially an aromatic OH content. This means that the OH group is directly bonded to an aromatic group. Likewise preferably, the OH content of the carrier or film is at least partially a phenolic OH content. Very particularly preferably, the OH content of the carrier or film is a phenolic OH content. It is also possible for the OH content of the carrier or film to be at least partially an aliphatic OH content. This means that the OH group is directly bonded to an aliphatic group. Very particularly preferably, the OH content of the carrier or film is an aliphatic OH content. It is also possible for the OH content of the carrier or film to be an aromatic, preferably phenolic and / or aliphatic OH content.

[0150] If at least part of the OH content is generated by aliphatic groups, it is preferred that these are end groups of at least one polycarbonate.

[0151] In particular, it is preferred that the part of the OH groups which is bonded to the polycarbonate via an aliphatic group (if present at all) is bonded to the polycarbonate via a structure of formula (X), where

[0152] (X), in which each Z independently represents an ether bond, a carbonyl group, an ester group or a single bond, each R A independently represent a linear or branched alkylene group having 1 to 20 carbon atoms or an alkenylene group having 2 to 20 carbon atoms, each R Bindependently of one another represents a linear or branched alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, an aryl group having 6 to 12 carbon atoms or a halogen, m represents a number from 1 to 3, o represents a number from 0 to 3, with the proviso that the sum of m and o can never be greater than 5 and * represents the bond of formula (X) to the main chain of the polycarbonate.

[0153] It will be clear to the person skilled in the art that the term “single bond” in the definition of Z is to be understood in such a way that “Z” is not present at all. This means that R A is directly bound to the phenyl ring.

[0154] Particularly preferably, in formula (X), each Z independently represents an ether bond or a single bond, each R Aindependently of one another represent a linear or branched alkylene group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, most preferably 1 to 4 carbon atoms, each R B independently of one another represent a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 1 to 8 carbon atoms, very particularly preferably 1 to 4 carbon atoms, or an alkoxy group having 1 to 10 carbon atoms, preferably 1 to 8 carbon atoms, very particularly preferably 1 to 4 carbon atoms, m represents a number from 1 to 3, o represents a number from 0 to 3, preferably 0 to 2, with the proviso that the sum of m and o can never be greater than 5.

[0155] Most preferably, in formula (X) each Z represents a single bond, each R A independently of one another represents a linear alkylene group having 1 to 4 carbon atoms, preferably an ethylene group, each R Bindependently of one another represent a linear alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an alkoxy group having 1 to 4 carbon atoms, preferably a methoxy group, m represents a number from 1 to 3, preferably 1, o represents a number from 0 to 3, preferably 0. Such polycarbonates with aliphatic end groups can be obtained as described, for example, in EP4026871 A1, EP3981822 A1, JP2008-101191A or JP2008-095046A.

[0156] If at least part of the OH content is generated by aromatic, preferably phenolic, groups, it is preferred that these be end groups of at least one polycarbonate. The skilled person is familiar with methods for maintaining and controlling the aromatic OH group content (see also the polycarbonate production processes above).

[0157] The skilled person can adjust the OH content if necessary by using special mixtures of polycarbonates.

[0158] The person skilled in the art knows how to determine OH contents in thermoplastic compositions. For this purpose, the methods of 1 H-NMR spectroscopy or infrared techniques are also available. This is primarily a volumetric analysis method. The choice of method also depends on component B), since bands or signals may overlap within a method. Component C) could also influence the selection of the appropriate method. It is also possible that component C) (for example, if it is a filler or reinforcing material) is insoluble in the solvent required for analysis and can therefore be easily separated. Such a separation can also be performed specifically prior to analysis.

[0159] For example, the skilled person knows how to determine the phenolic OH content of aromatic polycarbonates. This can be done using IR spectroscopy, for example, as described in Horbach, A.; Veiel, U.; Wunderlich, H., Makromolekulare Chemie 1965, Volume 88, pp. 215-231. This is preferred. This method can also be modified by dissolving the sample in dichloromethane as a solvent, scanning it in an infrared spectrometer, and measuring the band height at a wavenumber of 3583 cm'. 1 Calibration can be performed using bisphenol A of known composition. The phenolic OH content can also be determined using '-H NMR spectroscopy. If, for example, the polycarbonate is a polycarbonate based on bisphenol A, the content of OH end groups can be determined using ]H NMR spectroscopy with dichloromethane as solvent at room temperature, evaluating the ratio of the integrals of the signals at 6.68 ppm (two aromatic protons ortho to phenolic OH groups) and at 1.68 ppm (six methyl protons of the bisphenol A unit). If a (co)polycarbonate based on a different bisphenol or with other comonomers other than bisphenol A is used, the skilled person is able to determine the phenolic OH content.

[0160] Further thermoplastic composition (Z2) according to process step (ib)

[0161] In process step (ib), the film is back-injected with a further thermoplastic composition (Z2), wherein the further thermoplastic composition (Z2) can be the same as or different from the thermoplastic composition (Z). Thus, the further thermoplastic composition (Z2) can comprise the above-described components A) and B) in all preferred forms and / or combinations. However, the material of the thermoplastic composition (Z2) is not limited and can be adapted and selected to the properties required by the intended application, as long as this composition is thermoplastic. It is apparent to those skilled in the art that the adhesion between this further thermoplastic composition (Z2) and the film also plays a major role and can be optimized. This lies within the knowledge and skill of the skilled person.

[0162] Polyurethanes

[0163] A polyurethane foam or a compact polyurethane layer is preferably used as a coating.

[0164] 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" also includes polyurethaneureas, in which compounds with NH functionality, optionally in admixture with polyols, are used as H-active polyfunctional compounds.

[0165] Suitable polyisocyanates are the aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates with an NCO functionality of preferably > 2 which are known to those skilled in the art and which may also have iminooxadiazinedione, isocyanurate, uretdione, urethane, allophanate, biuret, urea, oxadiazinetrione, oxazolidinone, acylurea and / or carbodiimide structures. These can be used individually or in any desired mixtures with one another. The aforementioned polyisocyanates are based on di- or triisocyanates with aliphatically, cycloaliphatically, araliphatically and / or aromatically bound isocyanate groups which are known to those skilled in the art, it being irrelevant whether these were prepared using phosgene or by phosgene-free processes. Examples of such di- or triisocyanatesTriisocyanates are 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (HDI), 2-methyl-l,5-diisocyanatopentane, l,5-diisocyanato-2,2-dimethylpentane, 2,2,4- and2,4,4-Trimethyl-l,6-diisocyanatohexane, 1,10-Diisocyanatodecane, 1,3- and 1,4-Diisocyanatocyclohexane, 1,3- and l,4-Bis-(isocyanatomethyl)-cyclohexane, 1-Isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (Isophorone diisocyanate, IPDI), 4,4'-Diisocyanatodicyclohexylmethane (Desmodur® W, Covestro AG, Leverkusen, DE), 4-Isocyanatomethyl-l,8-octane diisocyanate (Triisocyanatononane, TIN), CD, CD -Diisocyanato-1,3-dimethylcyclohexane (H6XDI), l-Isocyanato-l-methyl-3-isocyanato-methylcyclohexane, 1-Isocy anato- 1 -methyl 1-4-isocyanato-methylcyclohexane, Bis-(isocyanatomethyl)-norbornane, 1,5-naphthalene diisocyanate, 1,3- and l,4-bis-(2-isocyanato-prop-2-yl)-benzene (TMXDI), 2,4- and 2,6-diisocyanatotoluene (TDI), in particular the 2,4 and 2,6 isomers and technical mixtures of the two isomers, 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI), polymeric MDI (pMDI), 1,5-diisocyanatonaphthalene, 1,3-bis(isocyanatomethyl)benzene (XDI) and any mixtures of the compounds mentioned.

[0166] The polyisocyanates preferably have an average NCO functionality of 2.0 to 5.0, preferably of 2.2 to 4.5, particularly preferably of 2.2 to 2.7 and a content of isocyanate groups of 5.0 to 37.0 wt.%, preferably of 14.0 to 34.0 wt.%.

[0167] In a preferred embodiment, polyisocyanates or polyisocyanate mixtures of the above-mentioned type with exclusively aliphatically and / or cycloaliphatically bound isocyanate groups are used.

[0168] The polyisocyanates of the type mentioned above are most preferably based on hexamethylene diisocyanate, isophorone diisocyanate, the isomeric bis-(4,4'-isocyanatocyclohexyl)methanes and mixtures thereof.

[0169] Among the higher molecular weight, modified polyisocyanates, the prepolymers known from polyurethane chemistry with terminal isocyanate groups in the molecular weight range of 400 to 15,000, preferably 600 to 12,000, are of particular 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 groups reactive toward isocyanate groups, in particular organic polyhydroxyl compounds. Suitable polyhydroxyl compounds of this type include simple polyhydric alcohols in the molecular weight range of 82 to 599, preferably 62 to 200, such as 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 from polyurethane chemistry with molecular weights of 600 to 12.000, preferably 800 to 4000, which have at least two, generally 2 to 8, but preferably 2 to 6 primary and / or secondary hydroxyl groups. It is of course also possible to use NCO prepolymers obtained, for example, from low-molecular-weight polyisocyanates of the type exemplified and less preferred compounds having groups reactive toward isocyanate groups, such as polythioether polyols, hydroxyl-containing polyacetals, polyhydroxypolycarbonates, hydroxyl-containing polyesteramides, or hydroxyl-containing copolymers of olefinically unsaturated compounds.

[0170] Suitable compounds for producing NCO prepolymers containing isocyanate-reactive groups, particularly hydroxyl groups, are, for example, the compounds disclosed in US Pat. No. 4,218,543. In producing the NCO prepolymers, these compounds containing isocyanate-reactive groups are reacted with simple polyisocyanates of the type exemplified above, while maintaining an NCO excess. The NCO prepolymers generally have an NCO content of 10 to 26, preferably 15 to 26, wt.%. This already makes clear that, for the purposes of the present invention, "NCO prepolymers" or "prepolymers with terminal isocyanate groups" are understood to mean both the reaction products as such and the mixtures with excess amounts of unreacted starting polyisocyanates, which are often also referred to as "semiprepolymers."

[0171] Suitable aliphatic diols with an OH number of >500 mg KOH / g include the chain extenders commonly used in polyurethane chemistry, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, and 1,3-propanediol. Diols such as 2-1,4-butanediol, 1,3-butenediol, 2,3-butanediol, and / or 2-methyl1,3-propanediol are preferred. Of course, it is also possible to use the aliphatic diols in mixtures with one another.

[0172] Suitable H-active components are polyols with an average OH number of 5 to 600 mg KOH / g and an average functionality of 2 to 6. Polyols with an average OH number of 10 to 50 mg KOH / g are preferred. Polyols suitable according to the invention are, for example, polyhydroxypolyethers, which are obtainable by alkoxylation of suitable starter molecules such as ethylene glycol, diethylene glycol, 1,4-dihydroxybutane, 1,6-dihydroxyhexane, dimethylolpropane, glycerol, pentaerythritol, sorbitol, or sucrose. Ammonia or amines such as ethylenediamine, hexamethylenediamine, 2,4-diaminotoluene, aniline, or amino alcohols or phenols such as bisphenol A can also act as starters. The alkoxylation is carried out using propylene oxide and / or ethylene oxide in any desired order or as a mixture.

[0173] In addition to polyols, at least one further crosslinker and / or chain extender may additionally be present, selected from the group comprising amines and amino alcohols, for example ethanolamine, diethanolamine, diisopropanolamine, ethylenediamine, triethanolamine, isophrondiamine, N,N'-dimethyl(diethyl)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 of these compounds.

[0174] Also suitable are polyester polyols, such as those obtainable by reacting low-molecular-weight alcohols with polybasic carboxylic acids such as adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid, or the anhydrides of these acids in a conventional manner, provided the viscosity of the H-active component is not excessive. A preferred polyol containing ester groups is castor oil. In addition, preparations containing castor oil, such as those obtained by dissolving resins, e.g., aldehyde-ketone resins, as well as modifications of castor oil and polyols based on other natural oils, are also suitable.

[0175] Also suitable are those higher-molecular-weight polyhydroxypolyethers in which high-molecular-weight polyadducts, polycondensates, or polymers are present in finely dispersed, dissolved, or grafted form. Such modified polyhydroxy compounds are obtained in a conventional manner, for example, by allowing polyaddition reactions (e.g., reactions between polyisocyanates and amino-functional compounds) or polycondensation reactions (e.g., between formaldehyde and phenols and / or amines) to proceed in situ in the hydroxyl-containing compounds. However, it is also possible to mix a ready-made aqueous polymer dispersion with a polyhydroxy compound and then remove the water from the mixture.

[0176] Polyhydroxyl compounds modified with vinyl polymers, such as those obtained by polymerizing styrene and acrylonitrile in the presence of polyethers or polycarbonate polyols, are also suitable for the production of polyurethanes. When using polyether polyols modified according to DE-A 2 442 101, DE-A 2 844 922, and DE-A 2 646 141 by graft polymerization with vinylphosphonic acid esters and, optionally, (meth)acrylonitrile, (meth)acrylamide, or OH-functional (meth)acrylic acid esters, plastics with exceptional flame resistance are obtained.

[0177] Representatives of the compounds mentioned to be used as H-active compounds are described, for example, in High Polymers, Vol. XVI, "Polyurethanes Chemistry and Technology", Saunders-Frisch (ed.) Interscience Publishers, New York, London, Vol. 1, pp. 32-42, 44, 54 and Vol. II, 1984, pp. 5-6 and pp. 198-199.

[0178] Mixtures of the listed compounds can also be used.

[0179] The limitation of the average OH number and average functionality of the H-active component results primarily from the increasing embrittlement of the resulting polyurethane. However, the skilled person is generally aware of the possibilities for influencing the polymer-physical properties of the polyurethane, so that the NCO component, aliphatic diol, and polyol can be favorably matched.

[0180] The polyurethane layer (b) can be foamed or solid, such as a varnish or coating.

[0181] All known auxiliaries and additives such as release agents, blowing agents, fillers, catalysts and flame retardants can be used in their production.

[0182] If necessary, the following auxiliary and additive materials may be used: a) Water and / or volatile inorganic or organic substances as propellants

[0183] Suitable organic blowing agents include acetone, ethyl acetate, halogen-substituted alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane, and also butane, hexane, heptane, or diethyl ether. Suitable inorganic blowing agents include air, CO2, or N2O. A blowing effect can also be achieved by adding compounds that decompose at temperatures above room temperature, releasing gases such as nitrogen, such as azo compounds such as azodicarbonamide or azoisobutyronitrile. b) Catalysts

[0184] The catalysts are, for example, tertiary amines (such as triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N,N,N',N'-tetramethylethylenediamine, pentamethyldiethylenetriamine and higher homologues, l,4-diazabicyclo-(2,2,2)octane, N-methyl-N'-dimethylaminoethylpiperazine, bis-(dimethylaminoalkyl)piperazines, N,N-dimethylbenzylamine, N,N-

[0185] Dimethylcyclohexylamine, N,N-Diethylbenzylamine, Bis-(N,N-diethylamino-ethyl)adipate, N,N,N',N'-Tetramethyl-1,3-butanediamine, N,N-Dimethyl-ß-phenylethylamine, 1,2-

[0186] Dimethylimidazole, 2-methylimidazole), monocyclic and bicyclic amides, bis-(dialkylamino)alkyl ethers,

[0187] Tertiary amines containing amide groups (preferably formamide groups),

[0188] Mannich bases from 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), tertiary amines containing hydrogen atoms active towards isocyanate groups (e.g. triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine), as well as their reaction products with alkylene oxides such as propylene oxide and / or ethylene oxide, secondary tertiary amines,

[0189] Silaamines with carbon-silicon bonds (2,2,4-trimethyl-2-silamorpholine and 1,3-diethylaminomethyltetramethyldisiloxane), nitrogen-containing bases (such as tetraalkylammonium hydroxides),

[0190] Alkali hydroxides (such as sodium hydroxide, alkali phenolates such as sodium phenolate), alkali alcoholates (such as sodium methylate), and / or hexahydrotriazines.

[0191] The reaction between NCO groups and Zerewitinoff-active hydrogen atoms is also strongly accelerated by lactams and azalactams in a known manner, whereby an association is initially formed between the lactam and the compound with acidic hydrogen.

[0192] Organic metal compounds, particularly organic tin and / or bismuth compounds, can also be used as catalysts. Suitable organic tin compounds include, in addition to sulfur-containing compounds such as di-n-octyltin mercaptide, tin(II) salts of carboxylic acids such as tin(II) acetate, tin(II) octoate, tin(II) ethylhexoate, and tin(II) laurate, as well as tin(IV) compounds, e.g., 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.

[0193] Of course, all of the above-mentioned catalysts can be used as mixtures. Of particular interest are combinations of organic metal compounds and amidines, aminopyridines, or hydrazinopyridines.

[0194] The catalysts are generally used in an amount of approximately 0.001 to 10 wt.%, based on the total amount of compounds containing at least two isocyanate-reactive hydrogen atoms. c) Surface-active additives such as emulsifiers and foam stabilizers.

[0195] Suitable emulsifiers include sodium salts of castor oil sulfonates or salts of fatty acids with amines such as diethylamine oleate or diethanolamine stearate. Alkali or ammonium salts of sulfonic acids such as dodecylbenzenesulfonic acid or dinaphthylmethanedisulfonic acid, or of fatty acids such as ricinoleic acid, or of polymeric fatty acids can also be used as surface-active additives.

[0196] Polyethersiloxanes, especially water-soluble ones, are particularly suitable as foam stabilizers. These compounds are generally structured in such a way that a copolymer of ethylene oxide and propylene oxide is bonded to a polydimethylsiloxane residue. Of particular interest are polysiloxane-polyoxyalkylene copolymers, often branched via allophanate groups. d) Reaction retarders

[0197] Acidic substances (such as hydrochloric acid or organic acid halides) can be used as reaction retarders. e) Additives

[0198] Examples of PU additives that can be considered are cell regulators of a known type (such as paraffins or fatty alcohols) or dimethylpolysiloxanes as well as pigments or dyes and flame retardants of a known type (e.g. tris-chloroethyl phosphate, tricresyl phosphate or ammonium phosphate and polyphosphate), as well as stabilizers against aging and weathering influences, plasticizers and fungistatic and bacteriostatic substances as well as fillers (such as barium sulfate, diatomaceous earth, carbon black or whiting).

[0199] Further examples of surface-active additives and foam stabilizers, as well as cell regulators, reaction retarders, stabilizers, flame-retardant substances, plasticizers, dyes and fillers, as well as fungistatic and bacteriostatic substances, which may optionally be used according to the invention are known to the person skilled in the art and are described in the literature.

[0200] According to the invention, it is preferred that a low-solvent reactive polyurethane raw material mixture with a solvent content of at most 10 wt. %, preferably at most 2 wt. %, particularly preferably at most 1 wt. %, based on the paint content is used. It is also preferred that a solvent-free reactive polyurethane raw material mixture is used. The presence of a solvent can cause blistering. Likewise, the VOC (Volatile Organic Compounds) content is increased during production. Particularly for use in the IMC process and / or RIM process, it is advantageous to use low-solvent to solvent-free polyurethane raw material mixtures, since in these processes the solvent cannot evaporate during the short reaction time, or the tool is sealed.

[0201] Typically, coating systems with a short pot life are used. Systems with a maximum pot life of 1 minute are preferred, particularly with a maximum pot life of 30 seconds, and even more preferably with a maximum pot life of 10 seconds. The cycle time for the reaction of the coating system is preferably adapted to the injection molding cycle time. This is particularly economical. For short pot lives, a high-pressure countercurrent mixing head is preferably used to mix the two components. Compared to other processes, this allows for the highest productivity. Furthermore, no residues of mixed coating raw materials remain in the mold at the end of the process.

[0202] In a further aspect of the present invention, a composite component is provided, comprising a) a (ia) carrier or (ib) a film applied to a carrier, wherein in case (ia) the carrier and in case (ib) the film consists of a thermoplastic composition (Z) which

[0203] A) at least 50% by weight of a polycarbonate and

[0204] B) more than 0 wt.% to 50 wt.% of at least one thermoplastic polymer which is different from A), and wherein the OH content in case (ia) of the carrier or in case (ib) of the film is at least 230 ppm, and b) at least one polyurethane layer in direct contact with the carrier, produced by the process according to the invention, preferably also in all preferences and combinations of preferences.

[0205] These are preferably the components A), B) described above as well as the polyurethane layer described above in all preferences and combinations of preferences.

[0206] The OH content of the composite component refers to the carrier or film. It is possible that the OH content decreases, at least at the surface of the carrier, due to reaction with the reactive polyurethane raw material mixture. However, this is likely limited to the immediate surface and therefore not detectable using conventional volume analysis. This is primarily due to the fact that the reaction essentially only takes place at the interface and the polyurethane raw material mixture barely penetrates the carrier material. The OH content of the carrier or film is determined using volume analysis on the composite component. For this purpose, the polyurethane layer is first removed. Subsequently, the volume analysis of the carrier or film is performed. This preferably involves the preparation and analysis of a representative volume of the carrier or film (not just the surface facing the polyurethane layer).In particular, the methods described above can be used for this purpose, preferably IR spectroscopy. If a film is used, IR microscopy, thin sections, or even micrographs can also be used. Since the coating process generally does not lead to any significant change in the OH content in the volume of the carrier or film, the OH content in the carrier or film corresponds, to a first approximation, to the OH content in the uncoated carrier or film.

[0207] It is particularly preferred if the composite component according to the invention is produced in a 2-component reactive injection molding process with a reactive polyurethane raw material mixture containing

[0208] - at least one polyisocyanate component,

[0209] - at least one polyfunctional H-active compound, and

[0210] - optionally at least one polyurethane additive and / or process aid, wherein the reactive polyurethane raw material mixture has a characteristic number of > 90 to < 140.

[0211] Likewise preferably, the composite component according to the invention is an interior or exterior component of a rail, aircraft or motor vehicle.

[0212] In a further aspect of the present invention, there is provided a use of a composition, wherein the composition

[0213] A) at least 50% by weight of a polycarbonate and

[0214] B) more than 0 wt.% to 50 wt.% of at least one thermoplastic polymer, which differs from A), wherein the OH content of the thermoplastic composition is at least 230 ppm, as a carrier material or as a film material in the production of the composite component according to the invention. These are preferably the components A), B) described above and the polyurethane layer described above in all preferred forms and combinations of preferred forms.

[0215] Examples

[0216] Materials used:

[0217] For Examples 1 and 2, blends consisting of 60 wt.% polycarbonate, 39 wt.% of an acrylonitrile-butadiene-styrene (ABS) copolymer composition, and 1 wt.% of commercially available polymer additives were used. These blends differed only in the concentration of phenolic OH groups. The different OH group contents of the blends were adjusted by the different contents of phenolic OH groups in the polycarbonate components used to produce the blends.

[0218] Linear polycarbonates based on bisphenol A with a weight-average molecular weight M w of 28,000 g / mol (determined at room temperature by GPC in methylene chloride against a BPA-PC standard, see method above) and different OH contents were used. This resulted in OH contents of 450 ppm (Example 1) and 840 ppm (Example 2) in the support of the composite component.

[0219] The acrylonitrile-butadiene-styrene (ABS) copolymer used was a composition consisting of an acrylonitrile-butadiene-styrene (AB S) copolymer produced by the emulsion polymerization process, an acrylonitrile-butadiene-styrene (ABS) graft polymer produced by the emulsion polymerization process, an acrylonitrile-butadiene-styrene (ABS) copolymer produced by the bulk polymerization process and a styrene-acrylonitrile copolymer produced by the bulk polymerization process, wherein the acrylonitrile-butadiene-styrene (AB S) copolymer produced by the emulsion polymerization process contains the monomers acrylonitrile (A), butadiene (B) and styrene (S) in an A:B:S wt.% ratio of 17:25:58, the acrylonitrile-butadiene-styrene (ABS) graft polymer produced by the emulsion polymerization process in a A:B:S wt. % ratio of 12:56:32, the acrylonitrile-butadiene-styrene (AB S) copolymer prepared by the bulk polymerization process in an A:B:S wt.% ratio of 21:10:69 and the styrene-acrylonitrile copolymer produced by the bulk polymerization process in an A:B:S wt. % ratio of 23:0:77. These four components of the acrylonitrile-butadiene-styrene (ABS) composition were used in such a ratio that an A:B:S wt. % ratio of 19:18:63 resulted for the acrylonitrile-butadiene-styrene (ABS) copolymer composition itself. The free styrene-acrylonitrile copolymer, i.e., not covalently bonded to the butadiene rubber or included in the rubber phase in a non-extractable manner, in the acrylonitrile-butadiene-styrene (ABS) copolymer composition used to produce the PC / ABS blend had a weight-average molecular weight M. w of 135,000 g / mol (determined at room temperature by GPC in tetrahydrofuran against a polystyrene standard; method see above).

[0220] An additive mixture consisting of pentaerythritol tetrastearate as a mold release agent, Irganox™ B900 and Irganox™1076 as thermal stabilizers (both BASF, Ludwigshafen, Germany) and a Brönsted acid to buffer any process-related basic impurities in the emulsion ABS components was used.

[0221] Component Al:

[0222] Linear polycarbonate based on bisphenol A with a weight-average molecular weight Mw of 28,000 g / mol (determined by GPC at room temperature in methylene chloride against a BPA-PC standard) with a content of phenolic OH groups (determined by ' H NMR at room temperature in methylene chloride) of about 400 ppm.

[0223] Component A-2:

[0224] Linear polycarbonate based on bisphenol A with a weight-average molecular weight M wof 28,000 g / mol (determined by GPC at room temperature in methylene chloride against a BPA-PC standard) with a content of phenolic OH groups (determined via 1 H NMR at room temperature in methylene chloride) of < 100 ppm.

[0225] Component A-3:

[0226] Linear polycarbonate based on bisphenol A with a weight-average molecular weight M w of 13,000 g / mol (determined by GPC at room temperature in methylene chloride against a BPA-PC standard) with a content of phenolic OH groups (determined via 1 H NMR at room temperature in methylene chloride) of 2800 ppm.

[0227] Component Bl:

[0228] Acrylonitrile(A)-butadiene(B)-styrene(S) polymer, produced by a bulk polymerization process, which contains a disperse phase of rubber particles grafted with styrene-acrylonitrile copolymer based on a polybutadiene rubber as the graft base, containing styrene-acrylonitrile copolymer enclosed as a separate disperse phase, and a styrene-acrylonitrile copolymer matrix that is not chemically bonded to the rubber particles and not enclosed within the rubber particles. Component B1 has an A:B:S ratio of 23:10:67 wt.% and a gel content, determined as the acetone-insoluble portion, of 20 wt.%. The acetone-soluble portion of component B1 has a weight-average molecular weight M w(measured by GPC in tetrahydrofuran as solvent with polystyrene as standard) of 165 kg / mol. The mean particle size of the dispersed phase D50, measured by ultracentrifugation, is 0.85 pm. The melt flow rate (MVR) of component B1, measured according to ISO 1133 (2012 version) at 220°C with a ram load of 10 kg, is 6.7 ml / 10 min.

[0229] Component CI:

[0230] Pentaerythritol tetrastearate

[0231] Reactive polyurethane raw material mixture for all examples: The polyurethane coating system used was a mixture of puroclear 3351 IT (polyol component) and puronat 960 / 1 (diisocyanate component), both from RÜHL PUROMER GmbH, Friedrichsdorf, Germany, with a mixing ratio of 100 to 229. Puroclear 3351 IT is a polyol formulation that can be processed with puronate 960 / 1 (HDI isocyanate component) to form a lightfast cast elastomer system with a density of 1.09 g / cm 3at 20 °C and a viscosity of approximately 1000 mPas at 25 °C. puronate 960 / 1 is a liquid, colorless aliphatic polyisocyanate with a density of approximately 1.13 g / cm 3 at 20 °C and a viscosity of approx. 2500 mPas at 25 °C.

[0232] Test methods used

[0233] Adhesion: Adhesion was determined using the "POSI" test according to DIN EN ISO 4624:2016-08. Method B (8.4.2) was used, specifying the most severe defect pattern. Deviating from the standard, the median of three samples, each with eight measurements, was calculated. The most common defect pattern was determined and listed in the table. In Table 1, A: Cohesive failure of the substrate, A / B: Adhesion failure of the substrate and coating, B: Cohesive failure of the coating, and Y: Cohesive failure of the adhesive.

[0234] Hydrolysis storage: The composite components were stored for 72 hours in a climate chamber at (90 ± 2) °C and (95 ± 3)% relative humidity. The formation of water droplets on the components was prevented by appropriate positioning in the climate chamber. Subsequently, the components were subjected to another adhesion test using the "POSI" test (see above). For examples 1 and 2, a percentage decrease in adhesion of the result obtained using the "POSI" test was calculated in relation to the value before and after hydrolysis storage. For examples 3 to 5, the absolute values ​​of adhesion after hydrolysis storage were determined using the "POSI" test.

[0235] OH content:

[0236] The content of OH end groups of the polycarbonate was determined by ' H-NMR spectroscopy (600 MHz) with methylene chloride as solvent at room temperature.

[0237] The content of OH end groups, in this case phenolic OH end groups, was measured in the compounds and in uncoated areas of the composite components. It was determined in solution using IR spectroscopy in dichloromethane at room temperature. Calibration was performed with bisphenol A. The band at 3583 cm' was measured. 1 evaluated.

[0238] The molecular weights of the polycarbonates used were determined by the methods described as preferred in the general description section.

[0239] Production and characterization of the compounds:

[0240] For Examples 1 and 2: The compounds were produced on a ZSK25. The melt temperature was 260°C and the speed was 225 rpm. The throughputs were between 17.5 and 20 kg / h.

[0241] For examples 3 to 5: The compounds were manufactured on a ZSK25 twin-screw extruder from Coperion, Werner & Pfleiderer (Stuttgart, Germany) at a melt temperature of 260°C and under a vacuum of 100 mbar (absolute).

[0242] Production of composite components:

[0243] Partially surface coated molded parts with a projected area of ​​286.4 cm 2 Manufactured on an injection molding machine in a two-cavity injection mold (a substrate-side cavity and a polyurethane-side coating cavity linked to a RIM system). The composite component was a plate-shaped component made of thermoplastic material (carrier), the surface of which was partially coated with a polyurethane skin. The coated area of ​​the component was 225.5 cm 2 . Of this area, 150 cm 2as a test surface for adhesion tests. Eight measurements were performed on the test surface. The wall thickness of the test surface was either 3 mm (Example 2) or 4 mm (Example 1) or 3.2 mm (Examples 3, 4, and 5) for the injection-molded component, and 0.5 mm for the polyurethane layer. Three composite components were used for the initial adhesion measurement and three composite components for the adhesion measurement after hydrolysis storage.

[0244] In the first process step, the carrier was produced. For this purpose, thermoplastic granules with the compositions described above or in Table 2 were melted in an injection molding cylinder and injected into the first mold cavity of the closed mold at a temperature of 285 °C (Examples 1 and 2) or 290 °C (Examples 3 to 5). This mold cavity was heated to a temperature of 90 °C (Example 1) or 100 °C (Examples 2 to 5). After the holding pressure and cooling times, which led to the solidification of the carrier, the mold was opened in the second process step. The manufactured carrier component was held on the ejector side of the injection mold. The sliding table on the nozzle side of the injection mold was moved to position two. The mold was closed again in the third process step, and the carrier formed a cavity with the mold for the polyurethane coating.

[0245] In the fourth process step, the two reactive components of the polyurethane coating system were conveyed from the RIM system into a high-pressure countercurrent mixing head and mixed there prior to injection. The PU-side cavity was heated to temperatures of 90 °C (Example 1), 105 °C (Example 2), or 100 °C (Examples 3 to 5). After the reaction and cooling time, the mold was opened once more in the fifth process step, and the coated part was demolded.

[0246] The molded parts were then subjected to the adhesion test (initial adhesion). The molded parts were also subjected to the hydrolysis storage described above, and the adhesion was measured again (adhesion after hydrolysis). The same defect pattern was observed in all measurements.

[0247] Table 1:

[0248] As the results in Table 1 show, a reduced percentage loss of adhesion was achieved with increasing OH content of the composition. Thus, compositions with higher OH group content exhibit greater adhesion resistance. Table 2:

[0249] The results in Table 2 show that the absolute value of adhesion after hydrolysis storage is higher for composite components with a higher OH content.

Claims

Patent claims:

1. A method for producing a composite component comprising a) a carrier made of a thermoplastic composition and b) at least one polyurethane layer in direct contact with the carrier, comprising the steps (i) (ia) injecting a melt of a thermoplastic composition (Z) into a tool cavity and subsequent cooling to form the carrier or (ib) inserting a film comprising an outer layer consisting of a thermoplastic composition (Z) into a tool cavity, back-injecting this film with a melt of a further thermoplastic composition (Z2) on the side facing away from the outer layer of the film and subsequent cooling to form the carrier, wherein the thermoplastic composition (Z) A) at least 50% by weight of a polycarbonate and B) contains more than 0 wt.% to 50 wt.% of at least one thermoplastic polymer which is different from A), and the OH content in the case of (ia) the carrier or in the case of (ib) the film is at least 230 ppm, wherein the further thermoplastic composition (Z2) may be the same as or different from the thermoplastic composition (Z), (ii) enlarging the cavity of the tool and thereby creating a gap or introducing the carrier into a second cavity of the tool, which is larger in terms of its hollow mold dimensions than the first cavity, thereby creating a gap, and wherein in case (ib) the carrier is oriented such that the outer layer of the film consisting of the thermoplastic composition (Z) faces the gap, (iii) Injecting a reactive polyurethane raw material mixture containing - at least one polyisocyanate component, - at least one polyfunctional H-active compound, and - optionally at least one polymethane additive and / or processing aid into the gap between the carrier and the tool surface, whereby the polyurethane raw material mixture polymerises in contact with the surface of the carrier to form a compact polyurethane layer or a polyurethane foam layer, (iv) Demoulding the composite component from the mould cavity.

2. Process according to claim 1, characterized in that the OH content in case (ia) of the carrier or in case (ib) of the film is in the range from 230 ppm to 4000 ppm.

3. Process according to claim 2, characterized in that the OH content in case (ia) of the carrier or in case (ib) of the film is in the range from 500 ppm to 3500 ppm.

4. Process according to one of claims 1 to 3, characterized in that a part of the OH groups which contribute to the OH content of the carrier or the film is bonded to the polycarbonate via an aromatic group.

5. Method according to one of claims 1 to 4, characterized in that the carrier has a wall thickness of 0.5 mm to 10 mm at least at one point.

6. Method according to one of claims 1 to 5, characterized in that the polyurethane layer has a layer thickness of 1 pm to 20 cm.

7. The method according to any one of claims 1 to 6, characterized in that the thermoplastic composition (Z) further comprises a component C), wherein C) one or more additives.

8. Process according to one of claims 1 to 7, characterized in that the thermoplastic polymer of component B) comprises a rubber-modified and / or rubber-free vinyl (co)polymer and / or a polyester.

9. Process according to one of claims 1 to 8, characterized in that a low-solvent reactive polyurethane raw material mixture with a solvent content of at most 10 wt.%, preferably at most 2 wt.%, particularly preferably at most 1 wt.%, based on the paint content is used.

10. Process according to one of claims 1 to 8, characterized in that a solvent-free reactive polyurethane raw material mixture is used.

11. Process according to one of claims 1 to 10, characterized in that the reactive polyurethane raw material mixture has a pot life of at most 1 minute, preferably at most 30 seconds, particularly preferably at most 10 seconds.

12. Process according to one of claims 1 to 11, characterized in that the polymerization in process step (iii) takes place under elevated pressure.

13. Composite component comprising a) a (ia) carrier or (ib) a film applied to a carrier, wherein in case (ia) the carrier and in case (ib) the film consists of a thermoplastic composition (Z) which A) at least 50% by weight of a polycarbonate and B) more than 0 wt.% to 50 wt.% of at least one thermoplastic polymer which is different from A), and wherein the OH content in case (ia) of the carrier or in case (ib) of the film is at least 230 ppm, and b) at least one polyurethane layer in direct contact in case (ia) with the carrier or in case (ib) with the film, produced by the process according to any one of claims 1 to 12.

14. Composite component according to claim 13, characterized in that it is an interior or exterior component of a rail, aircraft or motor vehicle.

15. Use of a thermoplastic composition containing A) at least 50% by weight of a polycarbonate and B) more than 0 wt.% to 50 wt.% of at least one thermoplastic polymer which is different from A), wherein the OH content of the thermoplastic composition is at least 230 ppm, as a carrier material or as a film material in the production of a composite component according to one of claims 13 or 14.

Images