Method for producing composite part having support comprising polycarbonate having specific OH content

Abstract

The invention relates to a method for producing a composite part with improved composite adhesion, said composite part comprising a support comprising polycarbonate and at least one polyurethane layer in direct contact with the support. The invention also relates to a composite component having improved composite adhesion, and to the use of a polycarbonate having a specific OH content as a carrier material for producing a composite component having improved composite adhesion.

Description

[0001] The invention relates to a method for producing a composite component with improved composite adhesion, wherein the composite component comprises a carrier comprising polycarbonate and at least one polyurethane layer in direct contact with the carrier. The invention also relates to a composite component with improved composite adhesion and to the use of a polycarbonate with a specific OH content as a carrier material for producing a composite component with improved composite adhesion.

[0002] Composite parts comprising a carrier made of thermoplastic and at least one polyurethane layer in direct contact with the carrier are known in the prior art. For example, coated solid molded parts can be produced by processes such as the RIM process (reaction injection molding). A particularly advantageous method for producing composite parts with a high-layer thickness coating is the so-called in-mold coating (IMC) or direct coating (DC). Here, the coating component is applied to the corresponding carrier in the mold and cured in the mold cavity. In addition to the above requirements, the significant advantages of the IMC technology also include fast processing time, low to lower raw material losses and the production of coated injection molded parts (composite parts) including coatings in one operation. The composite parts obtained by the RIM process and the IMC process all show the mechanical properties of the carrier material, although their weathering stability and scratch resistance are improved by the polyurethane layer. It goes without saying that the overall performance and overall stability of the composite part are also determined by the adhesion of the polyurethane layer to the carrier. Commonly used composite parts containing polycarbonate as a carrier material usually suffer from adhesion loss after being subjected to loads such as environmental change tests or storage. This also reduces the overall performance of the composite part. Another advantage of RIM and IMC processes is that these processes can produce specific designs that are not achievable with other processes. This is primarily because the coating of the composite part can be made relatively thick while reacting quickly.

[0003] DE 19650854 C1 discloses an IMC process for producing multilayer plastic parts, wherein the plastic injection-molded part is coated with at least one layer made of a two-component thermosetting plastic, preferably polyurethane. In this process, the plastic part and the two-component thermosetting plastic layer are injected into the same mold one after the other in a cyclically synchronized manner. DE 19650854 C1 does not describe the influence of the properties of the carrier material and the process parameters on the adhesion between the carrier material of the composite part and the layers in contact therewith.

[0004] WO 2006 / 072366 A1 describes a method for forming and coating a substrate in a mold having at least two cavities. The method comprises the following steps:

[0005] A) forming a substrate in a first cavity of a mold;

[0006] B) introducing the substrate produced in the previous step into the second cavity of the mold,

[0007] C) coating the substrate in the second cavity with a lacquer, wherein the coating is performed under elevated pressure.

[0008] In this document, the adhesion between carrier material and lacquer layer is also not a priority.

[0009] EP28990008A1 describes that special surface structuring of the carrier can improve adhesion to the polyurethane layer. It is also known that the use of primers or special activation of the carrier material can improve adhesion.

[0010] WO2011 / 015286A1 is concerned with providing improved lamination between a carrier material and a polyurethane layer without requiring any modification of the surface of the carrier (particularly a primer or surface activation). It has been found that the use of a foamed carrier material has a positive effect on the adhesion of the polyurethane layer. WO2011 / 070044A4 studies the effect of the rubber content of a composition containing polycarbonate and a rubber-modified vinyl (co)polymer as a carrier material on the lamination adhesion.

[0011] In these documents, the improvement of composite adhesion is achieved by additional steps, such as applying a primer, surface activation, surface structuring or foaming of the carrier material, or by adding additives to the composition of the carrier material. This means that additional steps are required in the production of the composite part, which is accompanied by corresponding costs and complexity. Or a special additive-added composition of the carrier material is required, which affects the mechanical and optical properties of the resulting composite part and is likewise accompanied by additional costs for the additives.

[0012] Based on this prior art, the object of the present invention is to overcome at least one shortcoming of the prior art. The object of the present invention is in particular to provide a composite component, which has an improved composite between a carrier material comprising polycarbonate and at least one polyurethane layer in direct contact with the carrier material. Preferably, no additional steps such as by, for example, primer modified surface or surface activation should be required. It is also preferred to avoid using additional additives to improve / increase the composite adhesion in the carrier material. In particular, the polyurethane raw material mixture used to produce the composite component should have high reactivity (i.e., preferably less than 150 seconds, preferably a mold residence time of 100 seconds). The polyurethane raw material mixture used should also preferably have a pot life of up to 30 seconds, preferably up to 10 seconds. The composite component should be very particularly preferably produced by RIM or IMC process, particularly IMC process.

[0013] The present invention achieves at least one of the above-mentioned purposes, preferably all of them. Surprisingly, it was found that the use of a polycarbonate with a specific OH value as a carrier material can improve the composite between the carrier material and at least one polyurethane layer in direct contact with the carrier material. The resulting composite material adheres in the form of a force fit. This can be evaluated in particular by an experiment using a POSI test (according to DIN EN ISO 4624:2016-08, using method B (8.4.2), optionally illustrating the most damaged defect mode). Unlike the DIN standard, it is preferred that 8 measurements are made for each component and a total of 3 components are analyzed. The median of the measurements gives the adhesion value. The initial adhesion of the composite component according to the present invention measured by the above-mentioned POSI test is preferably at least 5MPa. The adhesion of the composite component of the present invention measured by the above-mentioned POSI test after the hydrolysis test (i.e., after storage for 72 hours in a climate cabinet at 90±2°C and 95±3% relative air humidity (water droplets should be properly positioned in the climate cabinet to avoid the formation of water droplets on the component)) is preferably also at least 2MPa. The composite adhesion between the carrier made of the polycarbonate composition and the polyurethane coating in the composite component of the invention can also be measured in a roller peel test according to DIN 53357:1982-10 on strip specimens with a width of 20 mm removed from the component at a test speed of 100 mm / min.

[0014] The composite material shows an improvement, especially relative to a similar system, but in which the OH value of the polycarbonate is lower than the OH value of the present invention. At the same time, it is known to those skilled in the art that the OH value of the polycarbonate should be kept as low as possible, because too high an OH content will have an adverse effect on the thermal stability of the polycarbonate. Such polycarbonates tend to turn yellow when heated. According to the present invention, it is found that the range of OH groups specifically defined in the polycarbonate used effectively improves composite adhesion on the one hand, but is still low enough on the other hand to ensure that the resulting composite part has good thermal stability. Without wishing to be bound by a particular theory, it is believed that the OH groups present in particular on the surface of the formed carrier can be used to react with the components of the polyurethane raw material mixture. This results in the formation of bonds, preferably covalent bonds, between the carrier surface and the formed polyurethane layer. This results in good adhesion in the resulting composite part. This effect is particularly evident in RIM and / or IMC processes, because polyurethane raw material mixtures that usually have a high isocyanate content are used here. This enables the reaction to be carried out particularly effectively.

[0015] Thus, one aspect of the present invention provides a method of producing a composite component, the composite component comprising

[0016] a) a carrier made of a thermoplastic composition, and

[0017] b) at least one polyurethane layer in direct contact with the carrier,

[0018] The method comprises the following steps

[0019] (i) injecting a melt of the thermoplastic composition into a mold cavity and then cooling to form a carrier,

[0020] The thermoplastic composition comprises

[0021] A) at least 95.0% by weight of an aromatic polycarbonate having a phenolic hydroxyl group content of 230 ppm to 1500 ppm, and

[0022] B) 0 to 5.0% by weight of at least one polymer additive,

[0023] (ii) enlarging the cavity of the mold to create a gap, or introducing the carrier into a second cavity of the mold, the hollow mold size of the second cavity being larger than the first cavity, thereby creating a gap,

[0024] (iii) injecting a reactive polyurethane raw material mixture containing the following components into the gap between the carrier and the mold surface

[0025] - at least one polyisocyanate component,

[0026] - at least one polyfunctional H-active compound, and

[0027] - optionally at least one polyurethane additive and / or processing aid,

[0028] The polyurethane raw material mixture in contact with the carrier surface is polymerized to form a dense polyurethane layer or polyurethane foam layer.

[0029] (iv) demoulding the composite part from the mold cavity.

[0030] Likewise, one aspect of the present invention therefore provides a method for producing a composite component, the composite component comprising

[0031] a) a carrier made of a thermoplastic composition, and

[0032] b) at least one polyurethane layer in direct contact with the carrier,

[0033] The method comprises the following steps

[0034] (i) (ia) injecting a melt of the thermoplastic composition (Z) into a mold cavity and then cooling it to form a carrier, or (ib) introducing a film comprising an outer layer consisting of the thermoplastic composition (Z) into a mold cavity, post-molding the film with a melt of another thermoplastic composition (Z2) on the side facing away from the outer layer of the film, and then cooling it to form a carrier,

[0035] The thermoplastic composition (Z) contains

[0036] A) at least 95.0% by weight of an aromatic polycarbonate having a phenolic hydroxyl group content of 230 ppm to 1500 ppm, and

[0037] B) 0 to 5.0 wt. % of at least one polymer additive, and

[0038] wherein the further thermoplastic composition (Z2) may be the same as or different from the thermoplastic composition (Z),

[0039] (ii) enlarging the cavity of the mold, thereby creating a gap, or introducing the carrier into a second cavity of the mold, the hollow mold size of which is larger than the first cavity, thereby creating a gap, and wherein in case (ib), the carrier is oriented so that the outer layer of the film consisting of the thermoplastic composition (Z) faces the gap,

[0040] (iii) injecting a reactive polyurethane raw material mixture containing the following components into the gap between the carrier and the mold surface

[0041] - at least one polyisocyanate component,

[0042] - at least one polyfunctional H-active compound, and

[0043] - optionally at least one polyurethane additive and / or processing aid,

[0044] The polyurethane raw material mixture in contact with the carrier surface is polymerized to form a dense polyurethane layer or polyurethane foam layer.

[0045] (iv) demoulding the composite part from the mold cavity.

[0046] It is obvious to the person skilled in the art that step (i) is divided into two alternative sub-steps (ia) or (ib). All descriptions relate to step (i) which is not subdivided, and / or to step (i) which is subdivided into steps (ia) and (ib). It is also obvious to the person skilled in the art that a thermoplastic composition comprising a phenolic hydroxyl content in the proportions according to the invention is in principle referred to as a "thermoplastic composition" and / or a "thermoplastic composition (Z)". There is no distinction here. However, in the case where step (i) includes step (ib), a distinction needs to be made, since in this case another thermoplastic composition is used, sometimes also referred to as a "thermoplastic composition (Z2)". According to the invention, it may be identical to or different from the thermoplastic composition (Z).

[0047] According to the present invention, preferably, method steps (i) to (iv) are directly carried out in succession. However, in this case, method steps (i), (ii) and / or (iii), preferably (ii) and (iii) can be performed multiple times (but not necessarily). If method step (i) is performed multiple times, the thermoplastic composition used in the second step and optionally in each further method step (i) is preferably different from the thermoplastic composition (Z) in the first method step (i). However, it is required that the carrier material produced by step (i) and in direct contact with the polyurethane raw material mixture in method step (iii) is a thermoplastic composition (Z) according to the present invention, which contains a defined phenolic hydroxyl content. The direct sequence of method steps (i) to (iv) prevents the workpiece temperature from cooling to room temperature during the process. This achieves a reduction in production time and a higher energy efficiency of the entire process.

[0048] Method steps (ii) and (iii) can be repeated at least once with a change in the polyurethane system, wherein one or more polyurethane layers are applied only on one or both sides of the carrier, thereby providing a composite component made of a thermoplastic carrier and at least two identical or different PU components, which PU components optionally also have a more than two-layer structure. If method steps (ii) and (iii) are repeated, it will be apparent to a person skilled in the art that at least the second polyurethane layer is no longer in direct contact with the carrier.

[0049] In method step (ii), a gap is generated. The term "gap" is understood by a person skilled in the art. It preferably describes a cavity that is sealed relative to the environment so that no material can escape. In order to generate a gap in method step (ii), the injection molding mold can be opened and then the half mold of the injection molding mold cavity can be replaced with a new half mold with a larger hollow mold size, or the part is moved from the first mold cavity to a second cavity with a larger hollow mold size of the same mold or a second mold, or the first cavity is opened to a certain gap size. Therefore, method step (ii) includes expanding the cavity of the mold and thereby generating a gap, or introducing the carrier into the second cavity of the mold, the hollow mold size of the second cavity is larger than the first cavity, thereby generating a gap. Preferably, method step (ii) includes introducing the carrier into the second cavity of the mold, the hollow mold size of the second cavity is larger than the first cavity, thereby generating a gap. If method step (ib) is performed according to the present invention, it is obvious to a person skilled in the art that in method step (ii), the orientation of the carrier from method step (i) is such that the outer layer of the film composed of the thermoplastic composition (Z) faces the gap. This is obvious, since the improved composite adhesion found according to the invention can only be achieved in this way. This requires direct contact between the thermoplastic composition (Z) and the polyurethane layer. Therefore, the person skilled in the art knows how the carrier of method step (ib) must be oriented in the method step relative to the gap into which the reactive polyurethane raw material mixture is injected.

[0050] The transfer of the substrate in method step (ii) can be carried out by known methods, such as those used in multi-color injection molding. A typical method is, on the one hand, to use a turntable, a rotating disk, a sliding cavity or a dividing plate, or a similar method in which the substrate is held on the core for transfer. If the substrate to be transferred is held on the core, the advantage is that the position can be accurately defined even after the transfer. On the other hand, the prior art discloses a method for transferring a substrate, wherein the substrate is removed from a cavity, for example with the aid of a handling system, and placed in another cavity. The transfer of the removed substrate provides greater design freedom in the coating operation, for example when producing hemming or shielding areas. Structured paint surfaces can also be produced, which also produces greater design freedom.

[0051] The method of the present invention also includes the possibility of providing a carrier by film insert molding known to those skilled in the art. For this purpose, in method step (i), a film comprising an outer layer composed of a thermoplastic composition (Z) is introduced into a mold cavity according to (ib), and the film is post-injected on the side away from the outer layer of the film with a melt of another thermoplastic composition (Z2), and then cooled to form a carrier. Therefore, this method step provides a carrier in a manner similar to that in method step (i), the melt of the thermoplastic composition (Z) is injected into the mold cavity and then cooled according to (ia). In both cases, a carrier comprising a thermoplastic composition at least on one side is formed. According to the present invention, it is then contacted with a reactive polyurethane raw material mixture. However, since the carrier can also be formed by the layer structure of another thermoplastic composition (Z2) and the film according to (ib), the cross section of the carrier according to (ia) and (ib) can be different.

[0052] According to the present invention, it is clear that the term "carrier" includes both conventional substrates and multilayer structures consisting of substrates and films. The substrate differs from the multilayer structure consisting of substrates and films in that the substrate is usually formed only by the injection of a melt in a mold cavity (it can also be called an injection molded part). In contrast, in a multilayer structure consisting of a substrate and a film, the film is initially introduced into the mold cavity in a solidified form. In order to prevent slippage, the film is preferably fixed in the mold cavity using a vacuum, an electrostatic charge or by mechanical anchoring. It cannot be ruled out that the film is at least partially deformed (for example by temperature increase) during the method according to the present invention. Subsequently, the film is post-injected with another thermoplastic composition, which forms the actual substrate of the multilayer structure comprising the substrate and the film by cooling. However, according to the present invention, the substrate and the multilayer structure consisting of the substrate and the film are preferably defined when they are first introduced into the mold cavity. In the first case, the melt is introduced; in the latter case, the solid is introduced and then post-injected with the melt.

[0053] The film used has an outer layer consisting of a thermoplastic composition (Z). The film can be a single-layer or multi-layer film. If it is a multi-layer, at least one outer layer is a layer consisting of a thermoplastic composition (Z). If it is only a single layer, the outer layer is the actual film, so that the orientation or which side of the film is post-injected becomes redundant, which is obvious to those skilled in the art who have understood the present invention, especially with regard to achieving better composite adhesion. The film can also be composed of layers comprising a thermoplastic composition (Z). According to the present invention, a layer is preferably understood to be a molded part whose extension in a plane is many times greater than its thickness. The surface of the film can be uniform or structured. Unless otherwise specified, a structured surface is also referred to as a layer. The film can include at least one layer.

[0054] The film used can preferably be at least partially coated on at least one side. However, it is obvious to those skilled in the art that the coating, as long as it does not contain the thermoplastic composition (Z) used according to the present invention, is in direct contact with another thermoplastic composition (Z2) in step (ib). Such a coating of the film usually refers to the side mentioned as "the side facing away from the outer layer of the film" in method step (ib). The film can be coated by screen printing, vacuum or other known coating technologies. Ink, metal, etc. can be used as coating materials. According to the present invention, a film composite can also be used. The simplest embodiment is a three-layer structure, which consists of a plastic film, for example a metal layer and another plastic film connected thereto. The advantage of this 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 present invention.

[0055] The method according to the invention is preferably characterized in that the carrier has a wall thickness at at least one point of 0.5 mm to 10 mm, preferably 1 mm to 9 mm, particularly preferably 1.5 mm to 6.5 mm, very preferably 2 mm to 5 mm.

[0056] The polyurethane can be, for example, a PU paint, a PU foam or a dense PU skin. According to the invention, all of these embodiments are included in the term "polyurethane layer". The thickness of the polyurethane layer prepared by the method can be, for example, 1 μm to 20 cm, preferably 5 μm to 15 cm, particularly preferably 10 μm to 10 cm. The method according to the invention is preferably characterized in that the layer thickness of the polyurethane layer is 1-1500 μm, preferably greater than 1.5 mm to 10 mm, particularly preferably greater than 1 cm to 20 cm, and also preferably 500 μm to 1 mm. In all of these configurations, the polyurethane layer can also be foamed.

[0057] The index of the reactive polyurethane raw material mixture is preferably >90 to <140, preferably >100 to <120, particularly preferably 105 to 115. The index is defined as the percentage of the amount of isocyanate actually used to the stoichiometric amount calculated in the case of complete conversion of the polyol (i.e. the amount of isocyanate groups calculated as OH equivalent reaction), i.e. index=((isocyanate functionality*total molar amount of isocyanates) / (alcohol functionality*total molar amount of hydroxyl groups))*100.

[0058] Preferably, the surface of the injection molding tool that is in contact with the thermoplastic polymer composition is temperature-controlled in process step (iii) to a temperature of 50° C. to 140° C., preferably 60° C. to 100° C., particularly preferably 65° C. to 95° C., preferably 60° C. to 85° C., particularly preferably 60° C. to 80° C. Alternatively, particularly preferably, the surface of the injection molding tool that is in contact with the thermoplastic polymer composition is temperature-controlled in process step (iii) to a temperature of 50° C. to 150° C., preferably 60° C. to 140° C., particularly preferably 70° C. to 130° C., preferably 80° C. to 120° C., particularly preferably 90° C. to 110° C. These values ​​apply in particular to the case where the carrier material comprises a polycarbonate based on bisphenol A as component A). If other (co)polycarbonates are to be used, the person skilled in the art can adjust the preferred temperatures accordingly based on the glass transition temperature of the other (co)polycarbonate. It is also preferred that in method step (iii) the surface of the injection molding tool which is in contact with the reactive polyurethane mixture is temperature-controlled to a temperature of 50° C. to 160° C., preferably 70° C. to 120° C., more preferably 80° C. to 110° C., particularly preferably 90° C. to 100° C. It is further preferred that in method step (iii) the temperature of the mold cavity on the polyurethane side is at least 10° C., preferably at least 15° C., particularly preferably at least 20° C. higher than the temperature of the mold cavity on the carrier side (thermoplastic side). However, method step (iii) can also be carried out without a temperature difference between the polyurethane-side and carrier-side mold cavities.

[0059] It is also preferred that the polymerization is carried out under elevated pressure in method step (iii). Particularly preferably, the pressure in method step (iii) is 10 to 150 bar, preferably 10 to 90 bar (10,000 to 90,000 hPa). It is also preferred that the reactive polyurethane raw material mixture is introduced in method step (iii) using a high-pressure or low-pressure device. Before the workpiece is demoulded in steps (ii) and (iv), the workpiece is cooled until dimensional stability is achieved.

[0060] The composite components produced according to the invention are preferably suitable for use as interior or exterior components for rail vehicles, aircraft or motor vehicles.

[0061] Component A

[0062] Aromatic polycarbonates of component A) suitable according to the invention are known from the literature or can be prepared by methods known from the literature (for the preparation of aromatic polycarbonates, see, for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964 and DE-AS 1495626, DE-A 2232877, DE-A 2703376, DE-A 2714544, DE-A 3000610, DE-A 3832396; for the preparation of aromatic polyester carbonates, see, for example, DE-A 3077934). In the present invention, the aromatic polycarbonates of component A) include not only homopolycarbonates but also copolycarbonates and / or polyester carbonates; the polycarbonates may be linear or branched in a known manner. According to the invention, mixtures of polycarbonates can also be used.

[0063] The polycarbonate or “polycarbonate-based” material according to the invention is a thermoplastic material which preferably comprises at least 50% by weight, particularly preferably at least 60% by weight, particularly preferably at least 70% by weight of polycarbonate.

[0064] A portion of the carbonate groups in the polycarbonates used according to the invention, up to 80 mol %, preferably 20 mol % to 50 mol %, can be replaced by aromatic dicarboxylic acid ester groups. Such polycarbonates which contain not only acid groups from carbonic acid but also acid groups from aromatic dicarboxylic acids embedded in the molecular chain are referred to as aromatic polyester carbonates. In the context of the present invention, they are grouped under the general term "thermoplastic aromatic polycarbonates".

[0065] The replacement of carbonate groups by aromatic dicarboxylic acid ester groups is carried out essentially stoichiometrically and quantitatively, so that the molar ratio of the reaction partners is also reflected in the final polyester carbonate. The aromatic dicarboxylic acid groups can be added both randomly and in blocks. In the context of the present invention, polyester carbonates are included in the term "polycarbonate".

[0066] In the context of the present invention, unless otherwise indicated, the term "alkyl" or "alkyl group" preferably refers to an alkane structure from which one hydrogen atom has been removed. The alkyl group according to the invention may be straight-chain or branched. It is saturated and therefore contains only single bonds between adjacent carbon atoms. Preferably, the alkyl group 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, 1-ethyl-2-methylpropyl, 1-ethyl-2-methylpropyl, and the like. If the number of carbon atoms were defined differently in the context of the present invention, the choice of these structures might be restricted.

[0067] In the context of the present invention, unless otherwise indicated, the term "alkylene" or "alkylene group" preferably refers to a bridged alkane structure in which two hydrogen atoms have been removed from different carbon atoms. In this case, the two hydrogen atoms removed from the two carbon atoms can be removed from any carbon atom in the alkane structure. This means that the two carbon atoms can be adjacent but not necessarily adjacent. The alkylene group can be straight-chain or branched. It is saturated. If the alkylene contains only one carbon atom, it refers to a methylene group (-CH2-) connected to the rest of the molecule by two single bonds. Preferably, the alkylene group 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-methyl Pentylene, 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, 1-ethyl-2-methylpropylene, 1-ethyl-2-methylpropylene, etc. If the definition of the number of carbon atoms is different in the context of the present invention, the selection of these structures may be limited.

[0068] In the context of the present invention, unless otherwise specified, the term "alkylidene" or "alkylidene group" preferably refers to a bridged alkane structure with two hydrogen atoms removed from the same carbon atom. Alkylidene groups preferably include isopropylidene, n-propylidene, isoheptylidene, and the like.

[0069] Preferred polyester carbonates are represented by formula (w)

[0070]

[0071] in

[0072] A in each repeating unit independently represents an aliphatic or aromatic divalent group, for example an aromatic divalent group having 6 to 30 carbon atoms, which may contain one or more aromatic rings, may be substituted and may contain an aliphatic or alicyclic group or an alkyl aromatic group or a heteroatom as a bridging structure, for example a structure of formula (wi)

[0073]

[0074] in

[0075] R 6 and R 7 H, C1 to C 18 Alkyl, C1 to C 18 alkoxy, halogen, for example Cl or Br, or in each case optionally substituted aryl or aralkyl, preferably H or C1 to C 12 alkyl, particularly preferably H or C1 to C8 alkyl, very particularly preferably H or methyl, and

[0076] X represents a single bond, -SO2-, -CO-, -O-, -S-, C1 to C6 alkylene, C2 to C5 alkylidene or C5 to C6 cycloalkylidene which may be substituted by C1 to C6 alkyl, preferably methyl or ethyl, or represents a C6 to C6 alkyl group which may be optionally fused to an aromatic ring containing other heteroatoms. 12 Arylene,

[0077] or - based on A - an aliphatic divalent radical 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 contain more than one ring, for example structure (wii)

[0078]

[0079] or - based on A - a linear alkylene radical 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 radical having 4 to 20 carbon atoms, preferably 5 to 15 carbon atoms, which may be interrupted by at least one heteroatom or a cycloalkylene radical having 4 to 20 carbon atoms, preferably 5 to 15 carbon atoms, which may be interrupted by at least one heteroatom and may contain more than one ring,

[0080] D in each repeating unit independently represents A or an aromatic or alicyclic divalent group, preferably an optionally substituted phenylene or an optionally substituted cyclohexylene;

[0081] y in each repeating unit independently represents an aliphatic divalent group which may be cyclic, linear or branched and contains 2 to 30 carbon atoms, which may be interrupted by at least one heteroatom and contains more than one ring, 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, an alicyclic divalent group having 6 to 30 carbon atoms (which may contain more than one ring) or an aromatic divalent group having 6 to 30 carbon atoms, particularly preferably an optionally substituted cyclohexylene group, an aliphatic linear group having 2 to 18 carbon atoms or an optionally substituted phenylene group, and

[0082] 0 <x<1。

[0083] Particularly preferred polyester carbonates are those based on the following combinations of 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 other diols or diacids.

[0084] Dihydroxy aromatic compounds suitable for producing polycarbonates include, for example, hydroquinone, resorcinol, dihydroxybiphenyl, bis(hydroxyphenyl)alkanes, bis(hydroxyphenyl)cycloalkanes, bis(hydroxyphenyl)sulfides, bis(hydroxyphenyl)ethers, bis(hydroxyphenyl)ketones, bis(hydroxyphenyl)sulfones, bis(hydroxyphenyl)sulfoxides, α,α′-bis(hydroxyphenyl)diisopropylbenzene, benzopyrrolidines derived from isatin derivatives or phenolphthalein derivatives, and ring-alkylated, ring-arylated and ring-halogenated compounds thereof, or 9,9-bis(4-hydroxyphenyl)fluorene.

[0085] Preferred dihydroxyaryl compounds include 4,4'-dihydroxybiphenyl, 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, dimethylbisphenol A, bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5- bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl)sulfone, 2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene, 9,9-bis(4-hydroxyphenyl)fluorene and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane as well as bisphenols (I) to (III)

[0086]

[0087] Therein R' represents in each case C1-C4-alkyl, aralkyl or aryl, preferably methyl or phenyl, very particularly preferably methyl.

[0088] Particularly preferred dihydroxyaryl compounds include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and dimethylbisphenol A as well as dihydroxyaryl compounds of formula (I), (II) and (III).

[0089] These and other suitable dihydroxyaryl compounds are described, for example, in U.S. Pat. Nos. 3,028,635, 2,999,825, 3,148,172, 2,991,273, 3,271,367, 4,982,014 and 2,999,846, DE-A 1,570,703, 2,063,050, 2,036,052, 2,211,956 and 3,832,396, FR-A 1,561,518, in the monograph H. Schnell, “Chemistry and Physics of Polycarbonates”, Interscience Publishers, New York 1964.

[0090] Also preferred are polycarbonates produced using a dihydroxyaryl compound of the following formula (1a):

[0091]

[0092] in

[0093] R 5 represents hydrogen or C1 to C4 alkyl, C1 to C4 alkoxy, preferably hydrogen or methyl or methoxy, particularly preferably hydrogen.

[0094] R 6 , R 7 , R 8 and R 9 independently of one another represent C6 to C12 aryl or C1 to C4 alkyl, preferably phenyl or methyl, in particular methyl,

[0095] Y represents a single bond, SO2, -S-, -CO-, -O-, C1- to C6-alkylene, C2- to C5-alkylidene, C6- to C12-arylene (which may optionally be fused to a further aromatic ring having heteroatoms) or represents a C5- to C6-cycloalkylidene (which may be mono- or polysubstituted by C1- to C4-alkyl), preferably represents a single bond, -O-, isopropylidene or represents a C5- to C6-cycloalkylidene which may be mono- or polysubstituted by C1- to C4-alkyl,

[0096] V represents oxygen, C2- to C6-alkylene or C3- to C6-alkylidene, preferably oxygen or C3-alkylene,

[0097] p, q and r are each independently 0 or 1,

[0098] 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,

[0099] When q=1 and r=1, W and V independently represent C2- to C6-alkylene or C3- to C6-alkylidene, preferably C3-alkylene,

[0100] Z represents a C1 to C6 alkylene group, preferably a C2 alkylene group,

[0101] o is an average number of repeating units of 10 to 500, preferably 10 to 100, and

[0102] m is an average number of repeating units of 1 to 10, preferably 1 to 6, particularly preferably 1.5 to 5.

[0103] It is likewise possible to use dihydroxyaryl compounds in which two or more siloxane blocks of the general formula (1a) are linked via terephthalic acid and / or isophthalic acid to form ester groups.

[0104] Copolycarbonates comprising monomer units of the general formula (1a), in particular copolycarbonates comprising bisphenol A, and in particular processes for the preparation of these copolycarbonates are described, for example, in WO 2015 / 052106 A2.

[0105] It is likewise possible to use dihydroxyaryl compounds in which two or more siloxane blocks of the general formula (1a) are linked via terephthalic acid and / or isophthalic acid to form ester groups.

[0106] Polycarbonates are produced in a known manner from diphenols, carbonic acid derivatives, optionally chain terminators and optionally branching agents, wherein, to produce polyester carbonates, a portion of the carbonic acid derivatives is replaced by aromatic dicarboxylic acids or dicarboxylic acid derivatives, more precisely to the extent to which the carbonate structural units in the aromatic polycarbonate are replaced by aromatic dicarboxylic ester structural units.

[0107] For homopolycarbonates, only one diphenol is used; for copolycarbonates, two or more diphenols are used. The diphenols used and all other chemicals and auxiliaries added in the synthesis may be contaminated with impurities from their own synthesis, handling and storage. However, it is best to work with raw materials that are as pure as possible.

[0108] The monofunctional chain terminators required for molecular weight regulation, for example phenol or alkylphenols, in particular phenol, p-tert-butylphenol, isooctylphenol, cumylphenol, their chlorocarbonates or acid chlorides of monocarboxylic acids or mixtures of these chain terminators, are either added to the reaction together with the bisphenol ester or bisphenol esters or at any time during the synthesis, as long as phosgene or chlorocarbonate end groups are still present in the reaction mixture or, in the case of acid chlorides and chlorocarbonates as chain terminators, as long as the polymer formed has sufficient phenolic end groups. However, it is preferred to add the one or more chain terminators after phosgenation at a point or time at which phosgene is no longer present but the catalyst has not yet been metered in, or to meter the chain terminators before, together with or simultaneously with the catalyst. Branching agents or branching agent mixtures that may be used are added to the synthesis in the same way, but usually before the chain terminators. The compounds usually used are triphenols, tetraphenols or acid chlorides of tricarboxylic acids or tetracarboxylic acids, or mixtures of polyphenols or mixtures of acid chlorides. Some examples of compounds useful as branching agents and having three or more phenolic hydroxyl groups include phloroglucinol, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)hept-2-ene, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)heptane, 1,3,5-tri(4-hydroxyphenyl)benzene, 1,1,1-tri(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)phenylmethane, 2,2-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]propane, 2,4-bis(4-hydroxyphenylisopropyl)phenol, tetrakis(4-hydroxyphenyl)methane.

[0109] Other trifunctional compounds include 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-tris(4-hydroxyphenyl)ethane. The amount of branching agents used optionally is 0.05 mol % to 2 mol %, again based on the molar number of diphenols used in each case. The person skilled in the art is familiar with all these measures for the production of polycarbonates. Preferred production methods for the polycarbonates (including polyester carbonates) used according to the invention are the known interfacial process and the known melt transesterification process (see, 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 polycarbonates are preferably produced by the melt transesterification process.

[0110] In the former case, the acid derivatives used are preferably phosgene and optionally dicarbonyl dichloride, and in the latter case, preferably diphenyl carbonate and optionally dicarboxylic acid diesters. In both cases, the catalysts, solvents, workup, reaction conditions, etc. for the production of polycarbonates or polyester carbonates are well described and known. The relative solution viscosity (η) of the aromatic polycarbonates is rel ) is preferably 1.18 to 1.4, particularly preferably 1.20 to 1.32, very particularly preferably 1.22 to 1.29 (measured on a solution of 0.5 g of polycarbonate in 100 ml of dichloromethane at 25° C.). The weight-average molecular weight Mw of the aromatic polycarbonates and polyester carbonates is preferably 15 000 to 35 000, more preferably 20 000 to 33 000, particularly preferably 23 000 to 30 000. The Mw values ​​are determined by gel permeation chromatography, which is calibrated to bisphenol A polycarbonate standards, using dichloromethane as eluent, using linear polycarbonates (composed of bisphenol A and phosgene) of known molar mass distribution from PSS Polymer Standards Service GmbH, Germany; calibration is carried out according to method 2301-0257502-09D (2009 edition) of Currenta GmbH & Co. OHG, Leverkusen. The eluent is dichloromethane. Column combination of cross-linked styrene-divinylbenzene resin. 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, detected by refractive index detector (RI).

[0111] According to the invention, the aromatic polycarbonate of component A has a phenolic hydroxyl content of 230 ppm to 1500 ppm, preferably 260 ppm to 1300 ppm, particularly preferably 300 ppm to 1000 ppm, likewise preferably 310 ppm to 800 ppm, very particularly preferably 350 ppm to 790 ppm. It is also preferred that the aromatic polycarbonate of component A has a phenolic hydroxyl content of 240 ppm to 1400 ppm, preferably 300 ppm to 1300 ppm, particularly preferably 400 ppm to 1200 ppm, likewise preferably 500 ppm to 1100 ppm, very particularly preferably 350 ppm to 1050 ppm.

[0112] Those skilled in the art know how to determine the phenolic hydroxyl content of aromatic polycarbonates. Suitable methods include 1 H-NMR spectroscopy or infrared techniques. Preferably by 1 The phenolic hydroxyl content is determined by H-NMR spectroscopy. If the aromatic polycarbonate is, for example, a polycarbonate based on bisphenol A, the OH end group content is determined by spectroscopy at room temperature using dichloromethane as solvent. 1 The phenolic hydroxyl content is determined by H-NMR spectroscopy, where the integrated ratio of the signals at 6.68 ppm (two aromatic protons in ortho position relative to the phenolic hydroxyl group) and 1.68 ppm (six methyl protons of the bisphenol A unit) is evaluated. If (co)polycarbonates based on different bisphenols / comprising other comonomers than bisphenol A are used, the person skilled in the art is able to determine the phenolic hydroxyl group content.

[0113] Unless stated otherwise, ppm data are based on weight.

[0114] The person skilled in the art knows in principle how the phenolic hydroxyl group content of the polycarbonate can be adjusted / influenced. If the interphase process is used, the person skilled in the art can adjust the phenolic hydroxyl group concentration required according to the invention, for example via the concentration of the chain terminators or the use of special chain terminators which optionally also contain phenolic hydroxyl groups, or subsequently react the end groups with compounds containing phenolic hydroxyl groups. If the polycarbonate is produced using the melt transesterification process, the person skilled in the art knows that the catalyst used or the ratio of diaryl carbonate to bisphenol used can influence the phenolic hydroxyl group content. Here, it is likewise possible to modify the end groups of the polycarbonate present in a downstream step, so that the phenolic hydroxyl groups are introduced or reacted in a targeted manner.

[0115] The process of the invention is characterized in particular in that the aromatic polycarbonate of component A) comprises one, particularly preferably a plurality, of the following structures (4) to (7):

[0116]

[0117] wherein the benzene rings may be independently mono- or di-substituted by C1 to C8 alkyl, halogen, preferably C1 to C4 alkyl, particularly preferably methyl, and X represents a single bond, a straight-chain or branched C1 to C6 alkylene, a C2 to C 10 Alkylene or C5 to C 10 The cycloalkylidene group preferably represents a single bond or a C1 to C4 alkylene group, particularly preferably an isopropylidene group, and "---" represents a bond of the structures (4) to (7) to the aromatic polycarbonate. It is particularly preferred that the amount of the structural units (4) to (7) is 10 ppm to 1000 ppm in total, preferably 50 to 950 ppm, particularly preferably 80 ppm to 850 ppm.

[0118] To determine the amount of structural units (4) to (7), the respective polycarbonate is subjected to total hydrolysis and the amount of the decomposition products is determined by quantitative HPLC. The decomposition products may include structures (4a) to (7a). Structures (4a) to (7a) are given, for example, for the use of a polycarbonate containing bisphenol A. (This can be achieved, for example, as follows: a polycarbonate sample is hydrolyzed with sodium methoxide under reflux. The corresponding solution is acidified and concentrated to dryness. The dry residue is dissolved in acetonitrile and the phenolic compounds of the formulae (4a) to (7a) are determined by HPLC with UV detection):

[0119]

[0120] The amount of the compound of the formula (4a) thus released is from 10 to 800 ppm, preferably from 20 to 75000 ppm, particularly preferably from 25 to 700 ppm, particularly preferably from 30 to 500 ppm.

[0121] The amount of the compound of the formula (5a) thus released is preferably from 0 (ie below the detection limit of 10 ppm) to 100 ppm, particularly preferably from 0 to 80 ppm, particularly preferably from 0 to 50 ppm.

[0122] The amount of the compound of the formula (6a) thus released is preferably from 0 (ie below the detection limit of 10 ppm) to 800 ppm, more preferably from 10 to 700 ppm, particularly preferably from 20 to 600 ppm and very particularly preferably from 30 to 350 ppm.

[0123] The amount of the compound of the formula (7a) thus released is preferably from 0 (ie below the detection limit of 10 ppm) to 300 ppm, preferably from 5 to 250 ppm, particularly preferably from 10 to 200 ppm.

[0124] Component B

[0125] The composition may comprise polymer additives as component B. Contemplated polymer additives include in particular commercially available polymer additives. Preferred polymer additives according to component B are flame retardants, flame retardant synergists, smoke suppressant additives, drip inhibitors, internal and external lubricants and release agents, flow aids, antistatic agents, conductive additives, nucleating agents, stabilizers, antimicrobial additives, scratch resistance improving additives, infrared absorbers, fluorescent brighteners, fluorescent additives, fillers and reinforcing agents, dyes and pigments and Bronsted acidic compounds. Particularly preferred polymer additives include flame retardants (e.g. phosphorus compounds such as phosphates or phosphonates, phosphonate amines and phosphazenes or halogen compounds), flame retardant synergists (e.g. nano-sized metal oxides), smoke suppressant additives (e.g. boric acid or borates), drip-proofing agents (e.g. compounds from the class of fluorinated polyolefins, silicones and aramid fibers), internal and external lubricants and mold release agents (e.g. pentaerythritol tetrastearate, stearyl stearate, montan wax or polyethylene wax), flow aids (e.g. low molecular weight vinyl (co)polymers), antistatic agents (e.g. block copolymers of ethylene oxide and propylene oxide, other polyethers or polyhydroxy ethers, polyether amides, polyester amides or sulfonates), conductive additives. agents (e.g. conductive carbon black or carbon nanotubes), nucleating agents, stabilizers (e.g. UV / light stabilizers, heat stabilizers, antioxidants, transesterification inhibitors, hydrolysis stabilizers), antimicrobial additives (e.g. silver or silver salts), scratch resistance improving additives (e.g. silicone oils or hard fillers, such as (hollow) ceramic beads), infrared absorbers, fluorescent brighteners, fluorescent additives, fillers and reinforcing agents (e.g. talc, optionally ground glass or carbon fibers, (hollow) glass or ceramic beads, mica, kaolin, CaCO3 and glass flakes) as well as dyes and pigments (e.g. carbon black, titanium dioxide or iron oxide), impact modifiers and Bronsted acidic compounds as alkali scavengers, or mixtures of a plurality of the abovementioned additives.

[0126] According to the invention, the percentages by weight given for the thermoplastic composition are to be understood as being based on the total weight of the thermoplastic composition. The thermoplastic composition preferably comprises at least 95.0% by weight of component A) and >0% by weight to 5.0% by weight of component B), particularly preferably at least 95.0% by weight of component A) and 0.01 to 5.0% by weight of component B), very particularly preferably at least 96.0% by weight of component A) and 0.05% by weight to 4.0% by weight of component B). It is preferred that the thermoplastic composition consists essentially of components A) and B). It is very particularly preferred that the thermoplastic composition consists of components A) and B).

[0127] Preferably, at least one heat stabilizer is used as component B in the thermoplastic composition. Suitable heat stabilizers are in particular phosphorus-based stabilizers selected from the group consisting of phosphates, phosphites, phosphonites, phosphines and mixtures thereof. Examples include triisooctyl phosphate, triphenyl phosphite, diphenyl alkyl phosphites, dialkyl phenyl phosphites, tris(nonylphenyl) phosphite, trilauryl phosphite, tri(octadecyl) phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite (Irgafos 168), diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite (Doverphos S-9228), pentaerythritol diphosphite bis(2,6-di-tert-butyl-4-methylphenyl) ester, pentaerythritol diphosphite diisodecyl ester, pentaerythritol diphosphite bis(2,4-di-tert-butyl-6-methylphenyl) ester, pentaerythritol diphosphite bis(2,4,6-tri(tert-butylphenyl) ester, sorbitol triphosphite tristearyl ester, 4,4'-biphenyl diphosphite tetra(2,4-di-tert-butylphenyl) ester, 6-isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenzo[d,g]-1,3,2-dioxaphosphooctate, phosphite bis(2,4-di-tert-butyl-6-methylphenyl) methyl ester, phosphite bis(2,4-di-tert-butyl-6-methylphenyl) ethyl ester, 6-fluoro-2,4,8,1 0-Tetra-tert-butyl-12-methyldibenzo[d,g]-1,3,2-dioxaphosphocene, 2,2',2"-nitrilo[triethyltris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite], 2-ethylhexyl(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl)phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphocene, pentaerythritol diphosphite bis(2,6-di-tert-butyl-4-methylphenyl) ester, triphenylphosphine (TPP), trialkylphenylphosphine, bisdiphenylphosphine ethane or trinaphthylphosphine. They are used alone or in combination, such as Irganox B900 (Irgafos 168 and Irganox 1076 mixed in a ratio of 4:1) or Doverphos S-9228 with Irganox B900 or Irganox 1076. Particularly preferably, triphenylphosphine (TPP), triisooctyl phosphate, Irgafos 168 or tris (nonylphenyl) phosphite or mixtures thereof are used. The amount of heat stabilizer used is preferably up to 1.0% by weight, more preferably 0.003% by weight to 1.0% by weight, more preferably 0.005% by weight to 0.5% by weight, and particularly preferably 0.01% by weight to 0.2% by weight.Particularly preferably, 0 to 0.1% by weight, particularly preferably 0.05 to 0.08% by weight, very particularly preferably 0.01 to 0.05% by weight of TPP is used. It is likewise preferred to use 0.01 to 0.1% by weight, particularly preferably 0.015 to 0.09% by weight, very particularly preferably 0.02 to 0.08% by weight of a stabilizer selected from the group consisting of phosphites.

[0128] Phenolic antioxidants such as alkylated monophenols, alkylated sulfoalkylphenols, hydroquinone and alkylated hydroquinone can also be used. Particular preference is given to using Irganox 1010 (pentaerythritol-3-(4-hydroxy-3,5-di-tert-butylphenyl) propionate; CAS: 6683-19-8) and Irganox 1076 (octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate). These are preferably used in amounts of 0.001% to 0.5% by weight, particularly preferably 0.0025% to 0.1% by weight, very particularly preferably 0.005% to 0.04% by weight.

[0129] Particularly suitable UV absorbers are hydroxybenzotriazoles, for example 2-(3',5'-bis(1,1-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole ( 234, BASF SE, Ludwigshafen), 2-(2'-hydroxy-5'-(tert-octyl)phenyl)benzotriazole ( 329, BASF SE, Ludwigshafen), bis(3-(2H-benzotriazolyl)-2-hydroxy-5-tert-octyl)methane ( 360, BASF SE, Ludwigshafen), 2-(4,6-diphenyl-1,3,5-triazine-2-yl)-5-(hexyloxy)phenol ( 1577, BASF SE, Ludwigshafen), 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methylphenol ( 326, BASF SE, Ludwigshafen), and benzophenones, such as 2,4-dihydroxybenzophenone ( 22, BASF SE, Ludwigshafen) and 2-hydroxy-4-(octyloxy)benzophenone ( 81, BASF SE, Ludwigshafen), 2,2-bis[[(2-cyano-1-oxo-3,3-diphenyl-2-propenyl)oxy]methyl]-1,3-propanediol (9CI) (Uvinul 3030, BASF SE, Ludwigshafen), 2-[2-hydroxy-4-(2-ethylhexyl)oxy]phenyl-4,6-di(4-phenyl)phenyl-1,3,5-triazine ( 1600, BASF SE, Ludwigshafen), tetraethyl 2,2'-(1,4-phenyldimethylene)bismalonate (Hostavin B-Cap, Clariant AG) or N-(2-ethoxyphenyl)-N'-(2-ethylphenyl)ethanediamide ( 312, CAS No. 23949-66-8, BASF SE, Ludwigshafen).

[0130] If UV absorbers are present, the composition preferably comprises at most 0.8% by weight, preferably 0.05% to 0.5% by weight, more preferably 0.08% to 0.4% by weight and very particularly preferably 0.1% to 0.35% by weight of UV absorbers, based on the entire composition.

[0131] Suitable mold release agents include, in particular, pentaerythritol tetrastearate (PETS) and glycerol monostearate (GMS). If a mold release agent is included, the composition preferably contains up to 0.8% by weight, preferably 0.05% to 0.5% by weight, more preferably 0.08% to 0.4% by weight, very particularly preferably 0.1% to 0.35% by weight, based on the total composition.

[0132] It has proven to be particularly advantageous if the thermoplastic composition comprises at least one hydroxyl component (I) as component B) which comprises at least three carbon atoms and at least three hydroxyl groups, wherein at least one of these at least three hydroxyl groups is replaced by an aliphatically saturated or unsaturated linear, cyclic or branched C1-C 32 The carboxylic acid or benzoic acid is esterified and at least one of these at least three hydroxyl groups is in the form of a free hydroxyl group. It goes without saying that further components B) may also be present in this case.

[0133] Surprisingly, the additional use of a special hydroxyl component in the carrier material can further improve the improved composite adhesion. However, the special hydroxyl component is mainly gathered on the surface of the carrier. This causes the bulk properties of the carrier to be almost unaffected by the use of additional additives. The composite material shows further improvements, especially relative to similar, but wherein the polycarbonate of component A) does not contain an additive with at least one hydroxyl group, preferably does not contain a system of the special hydroxyl component (I). Without wishing to be bound by theory, it is assumed that the special hydroxyl component (I) can act as an adhesion promoter due to its chemical properties. Hydrophilic OH groups and optional hydrophobic hydrocarbon chains (if present) (especially when they are long chains) cause them to gather on the surface of the carrier during and / or after the carrier is formed. At the same time, the hydrophobic hydrocarbon group causes the strong anchoring of the carrier material inside and on the surface (especially the long-chain hydrocarbon can be anchored with the carrier material in a manner known to those skilled in the art, thereby forming a loadable bond, even if a covalent bond is not formed). For example, the mobility toward the carrier and thus the surface aggregation tendency can be affected by the cooling process. The higher the temperature of the melt, the stronger the mobility of the molecule. For example, the temperature of the melt can be influenced by increasing the total melt temperature or the mold temperature in the process. This surface aggregation has the effect that the specific hydroxyl components in the bulk of the carrier material are depleted. This results in the hydroxyl components having little influence on the bulk properties of the carrier. However, this also has the effect that the amount of hydroxyl components can be kept low, since the hydroxyl components are only effectively utilized when needed. This further reduces costs.

[0134] Without being bound by theory, it is assumed that in particular the further additional OH groups present at the surface of the formed support are available for reaction with the components of the polyurethane raw material mixture. The combination of the covalent bonds between polycarbonate and polyurethane and the bonds between the reacted hydroxyl compound and polyurethane, which are firmly anchored in the support material but are overall more flexible, generally results in good compounding.

[0135] The hydroxy component (I) is preferably represented by the structural formula (I)

[0136] (R4-C(=O)O) o -(R5) x -(OH) p (I)

[0137] in

[0138] Each R4 is independently an aliphatic saturated or unsaturated, linear, cyclic or branched C1-C 31 Alkyl or phenyl,

[0139] R5 is a straight-chain, cyclic or branched alkylene group having x carbon atoms, wherein x is 3 to 12, preferably 3 to 8, particularly preferably 3 to 7, very particularly preferably 3 to 5, and each of these carbon atoms contained in R5 may each contain a substituent (R4-C(=O)O) o -、-(OH) p and / or hydrogen or alkyl, and

[0140] o is a number from 1 to 12, and p is a number from 1 to 12, provided that o+p is from 2 to 12, and the maximum value of o+p is determined by the maximum number x of carbon atoms in R5.

[0141] For a person skilled in the art, the number of substituents in formula (I) is the same as the available valences of the carbon atoms. If the branched R5-alkylene contains, for example, at least one tertiary carbon, this tertiary carbon atom therefore has at most only one valence left for the substituent R4-C(=O)O) o -、-(OH) p and / or hydrogen. Branched R5-alkylene groups may likewise contain quaternary carbon atoms which do not have the valences for other substituents.

[0142] It is also preferred that the hydroxy component (I) is represented by the formula (Ia) or (Ib)

[0143]

[0144] wherein each R4 is independently hydrogen, aliphatic saturated or unsaturated, linear, cyclic or branched C1-C 31 -alkyl or phenyl, with the proviso that at least one R4 is hydrogen and at least one R4 is an aliphatic saturated or unsaturated, linear, cyclic or branched C1-C 31 - alkyl or phenyl,

[0145] Each Y independently represents hydrogen, alkyl or aryl, and

[0146] Z represents hydrogen, alkyl or OR4,

[0147]

[0148] wherein each R4 is independently hydrogen, aliphatic saturated or unsaturated, linear, cyclic or branched C1-C 31 -alkyl or phenyl, with the proviso that at least one R4 is hydrogen and at least one R4 is an aliphatic saturated or unsaturated, linear, cyclic or branched C1-C 31 - alkyl or phenyl,

[0149] Each Y independently represents hydrogen, alkyl or aryl,

[0150] Z represents hydrogen or an alkyl group, and

[0151] x is a number from 3 to 12, preferably from 3 to 8, particularly preferably from 3 to 7 and very particularly preferably from 3 to 5.

[0152] It is particularly preferred that x is 3 to 5 in the formula (I) or (Ib).

[0153] Particularly preferred are those in which each R4 in the structural formula (I), (Ia) or (Ib) is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl, cyclohexyl, cyclopentyl, 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, Methylbutyl, 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, 1-ethyl-2-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n-octyl, pinacolyl, adamantyl, isomeric menthyl, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl. Particularly preferred are structural formulas (I), (Ia) or (Ib) wherein each R4 independently represents n-nonyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

[0154] It is also preferred, particularly preferably in combination with the above definition of R4, that each Y in the formula (I), (Ia) or (Ib) independently of one another represents hydrogen, methyl, ethyl, propyl, butyl or phenyl. Component B) is particularly preferably glycerol monostearate.

[0155] The thermoplastic composition preferably comprises 0.0001% to 5% by weight, particularly preferably 0.001% to 1% by weight, very particularly preferably 0.01% to 0.8% by weight, most preferably 0.02% to 0.06% by weight of hydroxyl component (I). These amounts ensure an effect of improving the adhesion of the composite, while being so low that the bulk properties of the carrier are hardly changed.

[0156] It is particularly preferred that component B) comprises at least one stabilizer, preferably selected from phosphites and / or phosphates, particularly preferably one of the abovementioned compounds, at least one mold release agent, at least one UV absorber, at least one phenolic antioxidant, and optionally dyes (organic) and / or pigments (organic and inorganic).

[0157] Very particularly preferably, component B) comprises TPP in an amount of 0% to 0.1% by weight, particularly preferably 0.05% to 0.08% by weight, and very particularly preferably 0.01% to 0.05% by weight; at least one stabilizer selected from the group consisting of phosphites and / or phosphates in an amount of 0.01% to 0.1% by weight, particularly preferably 0.015% to 0.09% by weight, and particularly preferably 0.02% to 0.08% by weight; at least one UV absorber in an amount of up to 0.8% by weight, preferably 0.05% to 0.5% by weight, more preferably 0.08% to 0.4% by weight, and very particularly preferably 0.1% to 0.35% by weight; at least one mold release agent in an amount of up to 0.8% by weight, preferably 0.05% to 0.5% by weight, more preferably 0.08% to 0.4% by weight, and very particularly preferably 0.1% to 0.35% by weight.

[0158] Another thermoplastic composition (Z2) according to method step (ib)

[0159] In method step (ib), the film is post-injected with another thermoplastic composition (Z2), wherein the other thermoplastic composition (Z2) may be identical or different from the thermoplastic composition (Z). The other thermoplastic composition (Z2) may comprise all preferences and / or combinations of the above-mentioned components A) and B). However, the material of the thermoplastic composition (Z2) is not limited and can be adjusted and selected according to the performance required for the purpose of use, provided that the composition is thermoplastic. It is obvious to those skilled in the art that the adhesion between the other thermoplastic composition (Z2) and the film is also very important and can be optimized. This is within the knowledge and ability of those skilled in the art.

[0160] Polyurethane

[0161] The coating used is preferably a polyurethane foam or a dense polyurethane layer.

[0162] The polyurethanes employed according to the invention are obtained by reacting polyisocyanates with H-reactive polyfunctional compounds, preferably polyols. In the context of the present invention, the term "polyurethane" is understood to also mean polyurethane ureas, in which compounds having NH functions, optionally mixed with polyols, are used as H-reactive polyfunctional compounds.

[0163] Suitable polyisocyanates are aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates known per se to the person skilled in the art, whose NCO functionality is preferably ≥ 2 and which may also contain iminooxadiazinedione, isocyanurate, uretdione, carbamate, allophanate, biuret, urea, oxadiazinetriae, oxazolidinone, acylurea and / or carbodiimide structures. These may be used alone or in any desired mixtures.

[0164] The abovementioned polyisocyanates are based on diisocyanates and / or triisocyanates known per se to the person skilled in the art having aliphatically, cycloaliphatically, araliphatically and / or aromatically bonded isocyanate groups, it being immaterial whether they have been prepared using phosgene or by a phosgene-free process. Examples of such diisocyanates or triisocyanates are 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4- and 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and 1,4-bis(isocyanatomethyl)cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 4,4'-diisocyanatodicyclohexylmethane ( W, Covestro AG, Leverkusen, DE), 4-isocyanatomethyl-1,8-octane diisocyanate (triisocyanatononane, TIN), ω,ω'-diisocyanato-1,3-dimethylcyclohexane (H6XDI), 1-isocyanato-1-methyl-3-isocyanatomethylcyclohexane, 1-isocyanato-1-methyl-4-isocyanatomethylcyclohexane, bis(isocyanatomethyl)norbornane, 1,5-naphthalene diisocyanate, 1,3- and 1,4-bis(2-isocyanatoprop-2-yl)benzene (TMXDI), 2,4- and 2,6-diisocyanatotoluene (TDI), in particular the 2,4- and 2,6-isomers and technical mixtures of these two isomers, 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI), polymeric MDI (pMDI), 1,5-diisocyanatonaphthalene, 1,3-bis(isocyanatomethyl)benzene (XDI) and any mixtures thereof.

[0165] Preferably, the polyisocyanates have an average NCO functionality of 2.0 to 5.0, preferably 2.2 to 4.5, particularly preferably 2.2 to 2.7, and a content of isocyanate groups of 5.0 to 37.0% by weight, preferably 14.0 to 34.0% by weight.

[0166] In a preferred embodiment, polyisocyanates or polyisocyanate mixtures of the abovementioned type are employed which have exclusively aliphatically and / or cycloaliphatically bonded isocyanate groups.

[0167] Very particularly preferably, polyisocyanates of the aforementioned type are based on hexamethylene diisocyanate, isophorone diisocyanate, isomeric bis(4,4′-isocyanatocyclohexyl)methane and mixtures thereof.

[0168] Among the high molecular weight modified polyisocyanates, prepolymers with terminal isocyanate groups, which are known in polyurethane chemistry and have a molecular weight range of 400 to 15 000, preferably 600 to 12 000, are of particular interest. These compounds are prepared in a manner known per se by reaction of an excess of simple polyisocyanates, for example of the type described, with organic compounds, in particular organic polyols, which have at least two groups reactive toward isocyanate groups. Suitable polyols of this type include not only simple polyols, such as ethylene glycol, trimethylolpropane, 1,2-propylene glycol or 1,4-butanediol or 2,3-butanediol, which have a molecular weight range of 82 to 599, preferably 62 to 200, but also, in particular, higher molecular weight polyether polyols and / or polyester polyols of the type known per se in polyurethane chemistry, which have a molecular weight of 600 to 12 000, preferably 800 to 4000, and which have at least two, usually 2 to 8, but preferably 2 to 6, primary and / or secondary hydroxyl groups. It will be appreciated that it is also possible to use NCO prepolymers which are prepared, for example, from low molecular weight polyisocyanates of the abovementioned type and less preferred compounds having groups reactive toward isocyanate groups, for example polythioether polyols, hydroxyl-containing polyacetals, polyhydroxy polycarbonates, hydroxyl-containing polyesteramides or hydroxyl-containing copolymers of olefinically unsaturated compounds.

[0169] Compounds having groups reactive toward isocyanate groups, in particular hydroxyl groups, which are suitable for preparing NCO prepolymers are, for example, the compounds disclosed in US Pat. No. 4,218,543. During the preparation of the NCO prepolymers, these compounds having groups reactive toward isocyanate groups are reacted with simple polyisocyanates of the above-described exemplary type, wherein an excess of NCO is observed. The NCO content of the NCO prepolymers is generally 10% to 26% by weight, preferably 15% to 26% by weight. As can be seen from the above, in the context of the present invention, the terms "NCO prepolymer" and "prepolymer with terminal isocyanate groups" are to be understood as meaning both the reaction product itself and a mixture with an excess of unconverted starting polyisocyanates, which is often also referred to as a "semi-prepolymer".

[0170] Aliphatic diols with an OH value of >500 mg KOH / g include chain extenders commonly used for crosslinking in polyurethane chemistry, such as ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-propanediol. Preference is given to using diols such as 2-1,4-butanediol, 1,3-butanediol, 2,3-butanediol and / or 2-methyl-1,3-propanediol. It will be appreciated that the aliphatic diols can also be used in mixtures with one another.

[0171] Suitable H-active components include polyols having an average OH value of 5 to 600 mg KOH / g and an average functionality of 2 to 6. Preference is given to polyols having an average OH value of 10 to 50 mg KOH / g. Suitable polyols according to the invention include, for example, polyhydroxy polyethers obtained by alkoxylation of suitable starter molecules, such as ethylene glycol, diethylene glycol, 1,4-dihydroxybutane, 1,6-dihydroxyhexane, dimethylolpropane, glycerol, pentaerythritol, sorbitol or sucrose. Also suitable as starters are ammonia or amines, such as ethylenediamine, hexamethylenediamine, 2,4-diaminotoluene, aniline or amino alcohols or phenols, such as bisphenol A. The alkoxylation is carried out using propylene oxide and / or ethylene oxide in any order or as a mixture.

[0172] In addition to the polyols, at least one further crosslinker and / or chain extender may be present, selected from amines and amino alcohols, such as ethanolamine, diethanolamine, diisopropanolamine, ethylenediamine, triethanolamine, isophoronediamine, 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, such as 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.

[0173] Also suitable are polyester polyols, such as are obtained, for example, by reacting low molecular weight alcohols with polycarboxylic acids (e.g. adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid or the anhydrides of these acids) in a manner known per se, provided that the viscosity of the H-active component does not become too high. A preferred polyol containing ester groups is ricinoleic acid. Also suitable are preparations containing castor oil, such as can be obtained, for example, by dissolving resins (e.g. aldehyde-ketone resins), and modifications of castor oil and polyols based on other natural oils.

[0174] Likewise suitable are high molecular weight polyhydroxy polyethers in which high molecular weight adducts or polycondensates or polymers are present in finely dispersed, dissolved or grafted form. Such modified polyols are obtained in a manner known per se, for example when a polyaddition reaction (for example between polyisocyanates and amino-functional compounds) or a polycondensation reaction (for example between formaldehyde and phenols and / or amines) takes place in situ in the hydroxyl-containing compounds. However, it is also possible to mix ready-to-use aqueous polymer dispersions with the polyols and then remove the water from the mixture.

[0175] Polyhydroxy compounds modified by vinyl polymers (obtained, for example, by polymerization of styrene and acrylonitrile in the presence of polyether or polycarbonate polyols) are also suitable for the production of polyurethanes. When polyether polyols modified by graft polymerization with vinylphosphonates and optionally (meth)acrylonitrile, (meth)acrylamide or OH-functional (meth)acrylates according to DE-A 2442101, DE-A 2844922 and DE-A 2646141 are used, plastics having particularly flame retardant properties are obtained.

[0176] Representatives of such compounds for use as H-active compounds are described, for example, in High Polymers, Volume XVI, "Polyurethanes Chemistry and Technology", Saunders-Frisch (ed.) Interscience Publishers, New York, London, Volume 1, pages 32-42, 44, 54 and Volume II, 1984, pages 5-6 and 198-199.

[0177] It is also possible to use mixtures of the compounds mentioned.

[0178] The limitation of the average OH number and the average functionality of the H-active components results in an increased brittleness of the resulting polyurethanes. However, the skilled person is aware in principle of the possibilities of influencing the physical properties of the polyurethane polymers so that the NCO component, the aliphatic diols and the polyols can be advantageously adapted to one another.

[0179] The polyurethane layer (b) can be foamed or solid, for example in the form of a lacquer or coating.

[0180] All auxiliaries and additives known per se, such as release agents, blowing agents, fillers, catalysts and flame retardants, can be used for their production.

[0181] Optionally useful as auxiliaries and additives are:

[0182] a) Water and / or volatile inorganic or organic substances as blowing agents

[0183] Suitable organic blowing agents include, for example, acetone, ethyl acetate, halogen-substituted alkanes, such as dichloromethane, chloroform, ethylenedichloride, vinylidene chloride, fluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane, as well as butane, hexane, heptane or diethyl ether, and suitable inorganic blowing agents include air, CO2 or N2 O. The blowing effect can also be achieved by adding compounds that decompose at temperatures above room temperature and eliminate gases (e.g. nitrogen), such as azo compounds, such as azodicarbonamide or azoisobutyronitrile.

[0184] b) Catalyst

[0185] The catalyst is, for example, a tertiary amine (e.g. triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N,N,N',N'-tetramethylethylenediamine, pentamethyldiethylenetriamine and higher homologues, 1,4-diazabicyclo-(2,2,2)octane, N-methyl-N'-dimethylaminoethylpiperazine, bis(dimethylaminoalkyl)piperazine, N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, N,N-diethylbenzylamine, bis(N,N-diethylaminoethyl) adipate, N,N,N',N'-tetramethyl-1,3-butanediamine, N,N-dimethyl-β-phenylethylamine, 1,2-dimethylimidazole, 2-methylimidazole),

[0186] Monocyclic and bicyclic amides, bis(dialkylamino)alkyl ethers,

[0187] a tertiary amine comprising an amide group, preferably a carboxamide group,

[0188] a Mannich base composed of a secondary amine, for example dimethylamine, with an aldehyde, preferably formaldehyde or a ketone, for example acetone, methyl ethyl ketone or cyclohexanone, and a phenol, for example phenol, nonylphenol or bisphenol,

[0189] Tertiary amines containing hydrogen atoms which are reactive toward isocyanate groups (for example triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine) and reaction products thereof with alkylene oxides (for example propylene oxide and / or ethylene oxide),

[0190] Secondary / tertiary amines,

[0191] Silylamines with carbon-silicon bonds (2,2,4-trimethyl-2-silylmorpholine and 1,3-diethylaminomethyltetramethyldisiloxane),

[0192] A nitrogen base (e.g. tetraalkylammonium hydroxide),

[0193] Alkali metal hydroxides (e.g. sodium hydroxide, alkali metal phenates, e.g. sodium phenate),

[0194] Alkali metal alkoxide (such as sodium methoxide) and / or

[0195] Hexahydrotriazine.

[0196] The reaction between NCO groups and Zerewitinoff-active hydrogen atoms is also greatly accelerated in a manner known per se by lactams and azalactams, wherein initially an adduct is formed between the lactam and the compound comprising an acidic hydrogen.

[0197] Also useful as catalysts are organometallic compounds, in particular organotin and / or bismuth compounds. In addition to sulfur-containing compounds (e.g. di-n-octyltin mercaptide), preferred organotin compounds are tin(II) salts of carboxylic acids, such as tin(II) acetate, tin(II) octoate, tin(II) ethylhexanoate and tin(II) laurate, and tin(IV) compounds, such as dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate or dioctyltin diacetate. Organobismuth catalysts are described, for example, in patent application WO 2004 / 000905.

[0198] Of course, all of the above catalysts can be used in combination. Combinations of organometallic compounds with amidines, aminopyridines or hydrazinopyridines are particularly interesting.

[0199] The catalyst is generally used in an amount of about 0.001 to 10 weight percent based on the total amount of compounds having at least two isocyanate-reactive hydrogen atoms.

[0200] c) Surface active additives such as emulsifiers and foam stabilizers.

[0201] Suitable emulsifiers are, for example, the sodium salt of castor oil sulfonate or salts of fatty acids with amines, such as diethylamine oleate or diethanolamine stearate. Alkali metal or ammonium salts of sulfonic acids (e.g. dodecylbenzenesulfonic acid or dinaphthylmethanedisulfonic acid) or fatty acids (e.g. ricinoleic acid) or polymerized fatty acids can also be used as surface-active additives.

[0202] Suitable foam stabilizers include in particular polyether siloxanes, especially water-soluble polyether siloxanes. The structure of these compounds is usually a copolymer of ethylene oxide and propylene oxide connected to a polydimethylsiloxane group. Particularly interesting are polysiloxane-polyoxyalkylene copolymers that are multiply branched through allophanate groups.

[0203] d) Reaction retardants

[0204] Suitable reaction retardants are, for example, acidic reacting substances (eg hydrochloric acid or organic acid halides).

[0205] e) Additives

[0206] The PU additives that come into consideration include, for example, cell regulators of the known type, such as paraffins or fatty alcohols, or dimethylpolysiloxanes, and pigments or dyes and flame retardants of the known type, such as trichloroethyl phosphate, tricresyl phosphate or ammonium phosphate and polyphosphates, and also stabilizers against the effects of aging and weathering, plasticizers, fungistatic and bacteriostatic substances and fillers, such as barium sulfate, diatomaceous earth, carbon black or precipitated chalk.

[0207] Further examples of surface-active additives and foam stabilizers and cell regulators, reaction retarders, stabilizers, flame retardants, plasticizers, dyes and fillers and fungistatic and bacteriostatic substances which are optionally co-used according to the invention are known to the person skilled in the art and are described in the literature.

[0208] According to the present invention, it is preferred to use a low-solvent reactive polyurethane raw material mixture, whose solvent content is based on the paint part and is at most 10% by weight, preferably at most 2% by weight, and particularly preferably at most 1% by weight. It is also preferred to use a solvent-free reactive polyurethane raw material mixture. The presence of solvents can lead to bubble formation. It also increases the VOC (volatile organic compound) content in production. In particular, when used in IMC processes and / or RIM processes, it is advantageous to use a low-solvent to solvent-free polyurethane raw material mixture, because in these processes, the solvent cannot evaporate and / or the mold is closed within a short reaction time.

[0209] Typically, lacquer systems with a short pot life are used. Preference is given to selecting systems with a pot life of up to 1 minute, particularly preferably a pot life of up to 30 seconds, very particularly preferably a pot life of up to 10 seconds. The reaction cycle time of the lacquer system is preferably adjusted to the injection molding cycle time. This is particularly economical. For short pot lives, it is preferred to use a high-pressure countercurrent mixing head for mixing the two components. This allows the highest productivity to be achieved compared to other processes. In addition, no residues of the mixed lacquer raw materials remain in the mold at the end of the process.

[0210] Another aspect of the present invention provides a composite component comprising

[0211] a) a carrier made of a thermoplastic composition, the thermoplastic composition comprising

[0212] A) at least 95.0% by weight of an aromatic polycarbonate having a phenolic hydroxyl group content of 230 ppm to 1500 ppm, and

[0213] B) 0 to 5.0% by weight of at least one commercially available polymer additive,

[0214] b) at least one polyurethane layer in direct contact with the carrier,

[0215] It is produced by a two-component reactive injection molding process, particularly preferably an IMC process or a RIM process, particularly preferably an IMC process.

[0216] Preference is given here to all preferences and combinations of preferences mentioned above for components A), B) and for the polyurethane layer mentioned above. It is likewise preferred that the composite component according to the invention is obtained by the process according to the invention.

[0217] Preferably, the phenolic hydroxyl group content of component A) in the composite part is based on the starting composition. It is possible that the OH content at least at the surface of the carrier is reduced by the reaction with the reactive polyurethane raw material mixture. However, this is probably impossible to verify. This is especially because the reaction occurs essentially only at the interface and the polyurethane raw material mixture hardly penetrates into the carrier material. The OH content of the carrier of the finished composite part can be determined by destroying the carrier, for example scraping it off. This can be done in particular using the above-mentioned method, preferably 1 In the case of thin films, infrared microscopy, thin sections or micrographs may also be used.

[0218] It is particularly preferred that the composite component according to the invention is produced by a two-component reactive injection molding process from a reactive polyurethane raw material mixture containing

[0219] - at least one polyisocyanate component,

[0220] - at least one polyfunctional H-active compound, and

[0221] - optionally at least one polyurethane additive and / or processing aid,

[0222] The index of the reactive polyurethane raw material mixture is ≥90 to ≤140.

[0223] It is likewise preferred that the composite component according to the invention is an interior or exterior component of a rail vehicle, aircraft or motor vehicle.

[0224] Another aspect of the invention provides the use of a composition as a carrier material for producing a composite component comprising a carrier and at least one polyurethane layer in direct contact with the carrier in a two-component reactive injection molding process, wherein the composition contains

[0225] A) at least 95.0% by weight of an aromatic polycarbonate having a phenolic hydroxyl group content of 230 ppm to 1500 ppm, and

[0226] B) 0 to 5.0% by weight of at least one commercially available polymer additive.

[0227] Preference is given here to all preferences and combinations of preferences mentioned above for components A), B) and for the above mentioned polyurethane layer. Example

[0228] Materials used:

[0229] PC1: Linear polycarbonate based on bisphenol A, based on 60 wt% polycarbonate (melt volume flow rate MVR is 12 cm 3 / (10 min) (according to ISO 1133:2012-03, test temperature is 300°C, load is 1.2 kg) and 40 wt% polycarbonate (melt volume flow rate MVR is 30 cm 3 / (10min), test temperature is 250℃, load is 1.2kg)

[0230] PC2: Linear polycarbonate based on bisphenol A, with a melt volume flow rate MVR of 30 cm 3 / (10 minutes)(test temperature is 250℃, load is 1.2kg)

[0231] PC3: Linear polycarbonate based on bisphenol A, with a melt volume flow rate MVR of 12 cm 3 / (10 minutes) (according to ISO 1133:2012-03, test temperature is 300℃, load is 1.2kg)

[0232] PC4: Powdered linear polycarbonate based on bisphenol A with a melt volume flow rate MVR of 6 cm 3 / (10 minutes) (according to ISO 1133:2012-03, the test temperature is 300°C and the load is 1.2 kg).

[0233] GMS: Glyceryl Monostearate (CAS 91052-47-0)

[0234] Reactive polyurethane raw material mixture: The polyurethane coating system used is a mixture of puroclear3351IT (polyol component) and puronat 960 / 1 (diisocyanate component), both of which are from 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 provide a light-resistant casting elastomer system with a density of 1.09 g / cm at 20 °C. 3 Puronate 960 / 1 is a liquid, colorless, aliphatic polyisocyanate with a density of about 1.13 g / cm at 20°C. 3 , the viscosity is about 2500 mPas at 25°C.

[0235] Test methods used

[0236] Adhesion: Adhesion was determined by the "POSI" test according to DIN EN ISO 4624:2016-08. Method B (8.4.2) was used, in which the most damaging defect mode was stated. In contrast to the standard, a median of 3 specimens was taken and 8 measurements were made in each case. The most common defect modes were determined and given in the table. Notes on Table 1: A: cohesive failure of substrate; A / B: adhesion failure of substrate and coating, B: cohesive failure of coating; Y: cohesive failure of adhesive.

[0237] Hydrolysis storage: The composite parts are stored in a climatic cabinet at (90±2)°C and (95±3)% relative air humidity for 72 hours. The formation of water drops on the parts is avoided by suitable positioning in the climatic cabinet. The parts are then retested for adhesion by means of the "POSI" test (see above).

[0238] Phenolic hydroxyl content: measures the OH end group content of the unpainted area of ​​the composite part. 1 H-NMR spectroscopy (600 MHz) was determined at room temperature with CDCl3 as solvent by evaluating the integrated ratio of the signals at 6.68 ppm (two aromatic protons ortho to the phenolic hydroxyl group) and 1.68 ppm (six methyl protons of the bisphenol A unit).

[0239] Production and characterization of molding compounds:

[0240] The compound was produced in a ZSK 25. The material temperature was 260° C. and the speed was 225 rpm. The throughput was 17.5 to 20 kg / h.

[0241] Production of composite parts:

[0242] The projected area of ​​the polyurethane coating was 286.4 cm2 and the coating was produced on an injection molding machine in an injection molding mold with two cavities (a cavity on the substrate side and a coating cavity on the polyurethane side connected to the RIM machine). 2 The composite component is a sheet-like component consisting of a thermoplastic (carrier) whose surface has been partially coated with a polyurethane skin. The coated area of ​​the component is 225.5 cm 2 In this area, 150cm 2 The test area used for the adhesion test was 8 times measured on this test area. The wall thickness of this test area was about 3.2 mm in the case of the injection molded part and about 0.5 mm in the case of the polyurethane layer. In each case, three composite parts were used for the initial adhesion measurement and three composite parts were used for the adhesion measurement after hydrolysis storage.

[0243] In a first method step, the carrier is produced. For this purpose, thermoplastic granules of the composition described in Table 1 are melted in an injection molding barrel and injected at a temperature of 300° C. into a first mold cavity of a closed mold. The mold cavity is temperature-controlled to a temperature of 100° C. After a pressure holding time and a cooling time, which lead to solidification of the carrier, the mold is opened in a second method step. The produced carrier part is held on the ejection side of the injection molding mold. The slide table on the nozzle side of the injection molding mold is moved to position two. In a third method step, the mold is closed again and the carrier forms a cavity for the polyurethane coating together with the mold.

[0244] In the fourth method step, the two reactive components of the polyurethane coating system are conveyed from the RIM plant to a high-pressure countercurrent mixing head and mixed there before injection. The PU-side cavity is tempered to a temperature of 100° C. After the reaction time and cooling time have expired, in the fifth method step, the mold is opened again and the coated molded part is demoulded.

[0245] The molded parts were subsequently subjected to adhesion tests (initial adhesion). In addition, the molded parts were subjected to the above-described hydrolysis storage and the adhesion was measured again (adhesion after hydrolysis). In all measurements, the same defect pattern was observed in each case.

[0246] Table 1:

[0247]

[0248]

[0249] As can be seen from the results in Table 1, the components of the thermoplastic composition of the carrier having the phenolic hydroxyl content of the present invention exhibit improved composite adhesion and at the same time have a good defect mode. The initial composite adhesion of Examples 1, 2 and 5 of the present invention is higher than that of Comparative Examples 3 and 4. At the same time, all the composite components of the present invention exhibit improved composite adhesion after hydrolysis storage.

[0250] It can likewise be seen from Example 5 that the addition of specific hydroxyl components to the thermoplastic composition further improves the composite adhesion in particular after hydrolytic storage.

Claims

1. A method for producing a composite component, the composite component comprising a) a carrier made of a thermoplastic composition, and b) at least one polyurethane layer in direct contact with the carrier, The method comprises the following steps (i) (ia) injecting a melt of the thermoplastic composition (Z) into a mold cavity and then cooling it to form a carrier, or (ib) introducing a film comprising an outer layer consisting of the thermoplastic composition (Z) into a mold cavity, post-molding the film with a melt of another thermoplastic composition (Z2) on the side facing away from the outer layer of the film, and then cooling it to form a carrier, The thermoplastic composition (Z) contains A) at least 95.0% by weight of an aromatic polycarbonate having a phenolic hydroxyl group content of 230 ppm to 1500 ppm, and B) 0 to 5.0 wt. % of at least one polymer additive, and wherein the further thermoplastic composition (Z2) may be the same as or different from the thermoplastic composition (Z), (ii) enlarging the cavity of the mold, thereby creating a gap, or introducing the carrier into a second cavity of the mold, the hollow mold size of which is larger than the first cavity, thereby creating a gap, and wherein in case (ib), the carrier is oriented so 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 the following components into the gap between the carrier and the mold surface - at least one polyisocyanate component, - at least one polyfunctional H-active compound, and - optionally at least one polyurethane additive and / or processing aid, The polyurethane raw material mixture in contact with the carrier surface is polymerized to form a dense polyurethane layer or polyurethane foam layer. (iv) demoulding the composite part from the mold cavity.

2. The method according to claim 1, characterized in that The aromatic polycarbonate of component A) has a phenolic hydroxyl group content of 310 ppm to 1100 ppm.

3. The method according to any one of claims 1 or 2, characterized in that The aromatic polycarbonate of component A) comprises one, particularly preferably more than one, of the following structures (4) to (7): wherein the benzene rings may be independently mono- or di-substituted by C1 to C8 alkyl, halogen, preferably C1 to C4 alkyl, particularly preferably methyl, and X represents a single bond, a straight-chain or branched C1 to C6 alkylene, a C2 to C 10 Alkylene or C5 to C 10 The cycloalkylidene group preferably represents a single bond or a C1 to C4 alkylene group, and isopropylidene group is particularly preferred, and "---" represents a bond of structures (4) to (7) to the aromatic polycarbonate.

4. The method according to claim 3, characterized in that The amount of structural units (4) to (7) is 50 ppm to 1000 ppm in total, preferably 80 ppm to 850 ppm.

5. The method according to any 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. The method according to any one of claims 1 to 5, characterized in that The layer thickness of the polyurethane layer is from 1 μm to 20 cm.

7. The method according to any one of claims 1 to 6, characterized in that The thermoplastic composition (Z) consists of components A) and B).

8. The method according to any one of claims 1 to 7, characterized in that Component B) is selected from at least one representative of flame retardants, flame retardant synergists, smoke suppressant additives, anti-drip agents, internal and external lubricants and release agents, flow aids, antistatic agents, conductive additives, nucleating agents, stabilizers, antimicrobial additives, scratch resistance improving additives, infrared absorbers, fluorescent brighteners, fluorescent additives, fillers and reinforcing agents, dyes and pigments and Bronsted acidic compounds.

9. The method according to any one of claims 1 to 8, characterized in that Low-solvent reactive polyurethane starting material mixtures are used having a solvent content of up to 10% by weight, preferably up to 2% by weight, particularly preferably up to 1% by weight, based on the coating material.

10. The method according to any one of claims 1 to 8, characterized in that Use solvent-free reactive polyurethane raw material mixtures.

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

12. The method according to any one of claims 1 to 11, characterized in that The polymerization in process step (iii) is carried out under elevated pressure.

13. A composite part produced by the method of any one of claims 1 to 12, comprising a) a carrier made of a thermoplastic composition (Z), said thermoplastic composition (Z) comprising A) at least 95.0% by weight of an aromatic polycarbonate having a phenolic hydroxyl group content of 230 ppm to 1500 ppm, and B) 0 to 5.0% by weight of at least one commercially available polymer additive, b) At least one polyurethane layer in direct contact with the carrier.

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

15. A composition comprising the following ingredients A) at least 95.0% by weight of an aromatic polycarbonate having a phenolic hydroxyl group content of 230 ppm to 1500 ppm, and B) 0 to 5.0% by weight of at least one commercially available polymer additive, Use as a carrier material for producing a composite component in a two-component reactive injection molding process, the composite component comprising a carrier and at least one polyurethane layer in direct contact with the carrier.

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