WO2025132585A1 - Process for producing a composite component having a carrier comprising polycarbonate and an additive, the carrier having a specific oh content - Google Patents

Abstract

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

Description

Method for producing a composite component with a carrier comprising polycarbonate and an additive, the carrier having a specific OH content

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

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

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

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

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

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

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

At least one, preferably all, of the above-mentioned objects have been achieved by the present invention. Surprisingly, it has been found that the use of a composition containing polycarbonate and at least one additive with a defined OH number as a carrier material leads to an improved bond between the carrier material and the at least one polyurethane layer in direct contact with the carrier material. The resulting bond adheres force-fittingly. This can be verified in particular by testing using the POSI test (according to DIN EN ISO 4624:2016-08, Using method B (8.4.2) if necessary, specifying the most defective defect pattern). In deviation from the DIN standard, 8 measurements are preferably carried out per component and a total of 3 components are measured. The median of these measurements gives the adhesion value. The initial adhesion of the composite component according to the invention is preferably at least 5 MPa, measured using the above-mentioned POSI test. Likewise, the adhesion of the composite component according to the invention after the hydrolysis test (i.e. after 72 h storage at 90 ± 2 °C and 95 ± 3% relative humidity in a climatic chamber (formation of water droplets on the component must be avoided by suitable positioning in the climatic chamber)) is preferably at least 2 MPa, measured using the above-mentioned POSI test. An improved adhesion resistance was also observed. This means in particular that the adhesion of the composite component according to the invention remains high after the hydrolysis test (i.e. after 72 h of storage at 90 ± 2 °C and 95 ± 3% relative humidity in a climatic chamber (formation of water droplets on the component must be avoided by suitable positioning in the climatic chamber)), i.e. preferably above 2 MPa as measured by the POSI test. The bond adhesion between the carrier, comprising polycarbonate and at least one additive, and the polyurethane coating in the composite components according to the invention can also be measured on strip samples taken from the component with a width of 20 mm in a roller peel test according to DIN 53357:1982-10 at a test speed of 100 mm/min. Here, too, an improved adhesion resistance would be observed.

The composite shows an improvement, particularly compared to a comparable system, although the composition has an OH number that is below the OH number according to the invention. At the same time, it is preferred that the OH number of the carrier composition be kept as low as possible, since an excessively high OH content can negatively influence the thermal stability of the carrier. In particular, the polycarbonate contained in the carrier is prone to losses of mechanical properties and/or yellowing under heating. According to the invention, it has been found that the lower limit or the range of OH groups of the carrier defined according to the invention, on the one hand, effectively improves the composite adhesion, but on the other hand, is still low enough that the resulting composite component has good thermal stability. Without wishing to be bound to any theory, it is assumed that, in particular, the OH groups present on the surface of the formed carrier are available for a reaction with the components of the polyurethane raw material mixture. This results in to form bonds, preferably covalent bonds, between the surface of the substrate and the developing polyurethane layer. This leads to a strong bond in the resulting composite component. This effect is particularly pronounced in RIM and/or IMC processes, since polyurethane raw material mixtures are used there, which generally have a high isocyanate content. This allows the described reaction to proceed particularly effectively. The formation of covalent bonds also results in particularly good adhesion.

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

(i) injecting a melt of a thermoplastic composition (Z) into a tool cavity and subsequent cooling to form the carrier, wherein the thermoplastic composition (Z)

A) 60 wt% to less than 95 wt% of a polycarbonate and

B) contains 40 wt.% to more than 5 wt.% of at least one polymer additive, and the OH content of the carrier is at least 230 ppm,

(ii) Enlarging the cavity of the tool and thereby creating a gap or introducing the carrier into a second cavity of the tool which is larger in terms of its hollow shape dimensions than the first cavity, thereby creating a gap,

(iii) Injecting a reactive polyurethane raw material mixture containing

- at least one polyisocyanate component,

- at least one polyfunctional H-active compound, and

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

(iv) Demoulding the composite component from the mould cavity.

It is apparent to those skilled in the art that step (i) is divided into two alternative substeps (ia) or (ib). All statements refer either to step (i) without division and/or to step (i) with division into steps (ia) and (ib). Likewise, it is apparent to those skilled in the art that the thermoplastic composition having the OH content according to the invention is generally referred to as a "thermoplastic composition" and/or "thermoplastic composition (Z)". There is no difference here.

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

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

In process step (ii), a gap is created. The term "gap" is understandable to those skilled in the art. It preferably refers to a cavity that is sealed against the environment so that no material can escape. To create the gap in process step (ii), either the injection molding tool can be opened and one half of the injection molding tool cavity can be replaced with a new half with larger hollow dimensions, or the component can be transferred from the first tool cavity into a second cavity of the same or a second tool that has larger hollow dimensions, or the first cavity can be opened by a gap. Process step (ii) thus comprises enlarging the cavity of the tool and thereby creating a gap, or introducing the carrier into a second cavity of the tool that has larger hollow dimensions than the first cavity, thereby creating a gap. Preferably, process step (ii) comprises introducing the carrier into a second cavity of the tool, which is larger than the first cavity in terms of its hollow shape dimensions, thereby creating a gap.

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

According to the invention, it is clear that the term “carrier” includes both a classic substrate and a multi-layer structure.

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

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

The reactive polyurethane raw material mixture preferably has an index of > 90 to < 140, preferably > 100 to < 120, and particularly preferably from 105 to 115. The index is defined as the percentage ratio of the amount of isocyanate actually used to the calculated stoichiometric amount for complete polyol conversion (i.e. the amount of isocyanate groups calculated for the conversion of the OH equivalents), i.e. index = ((functionality of the isocyanates * amount of total isocyanates) / (functionality of the alcohols * amount of total hydroxyl groups)) * 100.

Preferably, the surface of the injection molding tool in contact with the thermoplastic composition is heated in process step (iii) to a temperature in the range from 50 to 140 °C, preferably 60 to 100 °C and particularly preferably 65 to 95 °C, preferably 60 to 85 °C, and particularly preferably 60 to 80 °C. Alternatively, the surface of the injection molding tool in contact with the thermoplastic composition is particularly preferably heated in process step (iii) to a temperature in the range from 50 to 150 °C, preferably 60 to 140 °C and particularly preferably 70 to 130 °C, preferably 80 to 120 °C, and particularly preferably 90 to 100 °C. These values apply in particular when the carrier material comprises a polycarbonate based on bisphenol A as component A). Should a different (co)polycarbonate be used, the person skilled in the art will be able to adjust preferred temperatures based on the glass transition temperature of this other (co)polycarbonate. Likewise, the surface of the injection mold in contact with the reactive polyurethane mixture in process step (iii) is preferably heated to a temperature in the range of 50 to 160°C, preferably 70 to 120°C, more preferably 80 to 110°C, and particularly preferably 90°C. to 100 °C. Furthermore, in process step (iii), the temperature of the polyurethane-side mold cavity is preferably at least 10 °C, preferably at least 15 °C, and particularly preferably at least 20 °C higher than the temperature of the carrier-side (thermoplastic-side) mold cavity. However, it is also possible to carry out process step (iii) without a temperature delta between the polyurethane-side and the carrier-side mold cavities.

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

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

Component A

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

A polycarbonate or a material “based on” polycarbonate according to the present invention is a thermoplastic material which preferably comprises at least 50% by weight, more preferably at least 60% by weight and most preferably at least 70% by weight of polycarbonate. A portion, up to 80 mol%, preferably from 20 mol% to 50 mol%, of the carbonate groups in the polycarbonates used according to the invention can be replaced by aromatic dicarboxylic acid ester groups. Such polycarbonates, which contain both carbonic acid residues and acid residues of aromatic dicarboxylic acids incorporated into the molecular chain, are referred to as aromatic polyester carbonates. For the purposes of the present invention, they are subsumed under the generic term "polycarbonates."

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

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

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

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

Preferred polyester carbonates are represented by formula (w)

(f), in the

in der R⁶ und R⁷ unabhängig voneinander für H, Ci- bis Cis-Alkyl-, Ci- bis Cis-Alkoxy,A of each repeating unit independently represents an aliphatic or aromatic divalent group, e.g. an aromatic divalent group having 6 to 30 carbon atoms, which may contain one or more aromatic rings, may be substituted and may contain aliphatic or cycloaliphatic radicals or alkylaryls or heteroatoms as bridging structures, such as a structure of the formula (wi)

in the R ⁶ and R ⁷ independently of one another represent H, Ci- to Cis-alkyl, Ci- to Cis-alkoxy,

Halogen such as CI or Br or each optionally substituted aryl or aralkyl, preferably H or Ci- to C-alkyl, particularly preferably H or Ci- to Cs-alkyl and very particularly preferably H or methyl, and

oder - bezogen auf A - eine lineare Alkylengruppe mit 2 bis 22 Kohlenstoffatomen, vorzugsweise 2 bis 4 Kohlenstoffatomen, die durch mindestens ein Heteroatom unterbrochen sein kann, oder eine verzweigte Alkylengruppe mit 4 bis 20 Kohlenstoffatomen, vorzugsweise 5 bis 15 Kohlenstoffatomen, die durch mindestens ein Heteroatom oder eine Cycloalkylengruppe mit 4 bis 20 Kohlenstoffatomen, vorzugsweise 5 bis 15 Kohlenstoffatomen, unterbrochen sein kann, die durch mindestens ein Heteroatom unterbrochen sein kann und die mehr als einen Zyklus enthalten kann, X represents a single bond, -SO2-, -CO-, -O-, -S-, C1- to C12-alkylene, C2- to C5-alkylidene or C5- to C12-cycloalkylidene, which may be substituted by C1- to C12-alkyl, preferably methyl or ethyl, and also C1- to C12-arylene, which may optionally be condensed with further aromatic rings containing heteroatoms, or - based on A - an aliphatic divalent group which may be cyclic, linear or branched and has 2 to 30 carbon atoms, which may be interrupted by at least one heteroatom and may comprise more than one cycle, such as, for example, structure (wii)

or - based on A - a linear alkylene group having 2 to 22 carbon atoms, preferably 2 to 4 carbon atoms, which may be interrupted by at least one heteroatom, or a branched alkylene group having 4 to 20 carbon atoms, preferably 5 to 15 carbon atoms, which may be interrupted by at least one heteroatom or a cycloalkylene group having 4 to 20 carbon atoms, preferably 5 to 15 carbon atoms, which may be interrupted by at least one heteroatom and which may contain more than one cycle,

D in each repeating unit independently represents A or an aromatic or cycloaliphatic divalent group, preferably an optionally substituted phenylene or an optionally substituted cyclohexylene; y in each repeating unit independently represents an aliphatic divalent group, which may be cyclic, linear or branched and has 2 to 30 carbon atoms, which may be interrupted by at least one heteroatom and more than one cycle, or an aromatic divalent group, preferably a linear aliphatic divalent group having 2 to 30 carbon atoms, a branched aliphatic divalent group having 2 to 30 carbon atoms, a cycloaliphatic divalent group having 6 to 30 carbon atoms, which more than one cycle or an aromatic divalent group having 6 to 30 carbon atoms, particularly preferably an optionally substituted cyclohexylene, an aliphatic linear group having 2 to 18 carbon atoms or an optionally substituted phenylene and 0 < x < 1.

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

Dihydroxyaryl compounds suitable for the production of polycarbonates are, for example, hydroquinone, resorcinol, dihydroxydiphenyls, bis-(hydroxyphenyl)-alkanes, bis-(hydroxyphenyl)-cycloalkanes, bis-(hydroxyphenyl)-sulfides, bis-(hydroxyphenyl)-ethers, bis-(hydroxyphenyl)-ketones, bis-(hydroxyphenyl)-sulfones, bis-(hydroxyphenyl)-sulfoxides, a-a'-bis-(hydroxyphenyl)-diisopropylbenzenes, phthalimidines derived from isatin or phenolphthalein derivatives as well as their core-alkylated, core-arylated and core-halogenated compounds or 9,9-bis(4-hydroxyphenyl)fluorene.

in denen R‘ jeweils für Ci-C4-Alkyl, Aralkyl oder Aryl, bevorzugt für Methyl oder Phenyl, ganz besonders bevorzugt für Methyl, steht. Besonders bevorzugte Dihydroxyarylverbindungen sind 2,2-Bis-(4-hydroxyphenyl)-propan (Bisphenol A), 2,2-Bis-(3,5-dimethyl-4-hydroxyphenyl)-propan, l,l-Bis-(4-hydroxyphenyl)- cyclohexan, l,l-Bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexan und Dimethyl-Bisphenol A sowie die Dihydroxyarylverbindungen der Formeln (I), (II) und (III). Preferred dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl, 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A), 2,4-bis-(4-hydroxyphenyl)-2-methylbutane, 1,1-bis-(4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis-(3-methyl-4-hydroxyphenyl)-propane, Dimethyl bisphenol A, bis-(3,5-dimethyl-4-hydroxyphenyl)-methane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfone, 2,4-bis-(3,5-dimethyl-4-hydroxyphenyl)-2-methy ibutane, 1, 1 -bis-(3 ,5-dimethy1-4-hydroxyphenyl)-p- diisopropylbenzene, 9,9-bis(4-hydroxyphenyl)fluorene and l,l-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, as well as the bisphenols (I) to (III)

in which R' is each Ci-C4-alkyl, aralkyl or aryl, preferably methyl or phenyl, most preferably methyl. Particularly preferred dihydroxyaryl compounds are 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol A), 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane, l,l-bis-(4-hydroxyphenyl)-cyclohexane, l,l-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and dimethyl-bisphenol A as well as the dihydroxyaryl compounds of the formulas (I), (II) and (III).

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

2,999,825, US-A 3,148,172, US-A 2,991,273, US-A 3,271,367, US-A 4,982,014 and US-A 2,999,846, in DE-A 1,570,703, DE-A 2,063,050, DE-A 2 036 052, DE-A 2 211 956 and DE-A

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

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

in the

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

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

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

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

Z represents C1-C6-alkylene, preferably C2-alkylene, o represents an average number of repeating units of 10 to 500, preferably 10 to 100, and m represents an average number of repeating units of 1 to 10, preferably 1 to 6, particularly preferably 1.5 to 5.

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

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

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

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

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

The monofunctional chain terminators required to regulate the molecular weight, such as phenols or alkylphenols, in particular phenol, p-tert. butylphenol, iso-octylphenol, Cumylphenol, their chlorocarbonic acid esters or acid chlorides of monocarboxylic acids or mixtures of these chain terminators are either fed to the reaction with the bisphenolate(s) or added at any time during the synthesis as long as phosgene or chlorocarbonic acid end groups are still present in the reaction mixture, or in the case of acid chlorides and chlorocarbonic acid esters as chain terminators, as long as sufficient phenolic end groups of the forming polymer are available. However, the chain terminator(s) are preferably added after phosgenation at a time or place when no more phosgene is present but the catalyst has not yet been added, or they are added before the catalyst, together with the catalyst, or in parallel. Any branching agents or branching agent mixtures to be used are added to the synthesis in the same way, but usually before the chain terminators. Trisphenols, quarterphenols, or acid chlorides of tri- or tetracarboxylic acids, or mixtures of polyphenols or acid chlorides, are commonly used. Some of the compounds with three or more phenolic hydroxyl groups that can be used as branching agents include phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-2-heptene, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-heptane, 1,3,5-tris-(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-hydroxyphenyl-isopropyl)-phenol, and tetra-(4-hydroxyphenyl)-methane.

Some of the other trifunctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride, and 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole. Preferred branching agents are 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole and 1,1,1-tri(4-hydroxyphenyl)ethane. The amount of branching agents to be used, if desired, is 0.05 mol% to 2 mol%, again based on the moles of diphenols used. All of these measures for producing the polycarbonates are familiar to the person skilled in the art. Preferred methods of producing the polycarbonates to be used according to the invention, including the polyestercarbonates, are the known interfacial process and the known melt transesterification process (cf., for example, WO 2004/063249 A1, WO 2001/05866 A1, WO 2000/105867, US 5,340,905 A, US 5,097,002 A, US-A 5,717,057 A). The polycarbonate is preferably produced via the

produced using a melt transesterification process. In the first case, the acid derivatives used are preferably phosgene and optionally dicarboxylic acid dichlorides; in the latter case, preferably diphenyl carbonate and optionally dicarboxylic acid diesters. Catalysts, solvents, workup, reaction conditions, etc., for polycarbonate or polyester carbonate production are sufficiently described and known in both cases. The relative solution viscosity (r| _re i) of the aromatic polycarbonates is preferably in the range from 1.18 to 1.4, particularly preferably in the range from 1.20 to 1.32, and most preferably in the range from 1.22 to 1.29 (measured on solutions of 0.5 g of polycarbonate in 100 ml of methylene chloride solution at 25 °C). The weight-average molecular weight Mw of the aromatic polycarbonates and polyestercarbonates is preferably in the range from 15,000 to 35,000, more preferably in the range from 20,000 to 33,000, and particularly preferably 23,000 to 30,000, determined by [the formula: 1]. The values for Mw are determined by gel permeation chromatography, calibrated against bisphenol A polycarbonate standards using dichloromethane as the eluent, calibration with linear polycarbonates (from bisphenol A and phosgene) of known molar mass distribution from PSS Polymer Standards Service GmbH, Germany; calibration according to method 2301-0257502-09D (2009 Edition) from Currenta GmbH & Co. OHG, Leverkusen. The eluent is dichloromethane. Column combination of crosslinked styrene-divinylbenzene resins. Diameter of the analytical columns: 7.5 mm; Length: 300 mm. Particle size of the column material: 3 pm to 20 pm. Solution concentration: 0.2 wt.%. Flow rate: 1.0 ml/min. Solution temperature: 30°C. Detection with a refractive index detector (RI).

According to the invention, the support has a defined OH content. The OH groups can also originate at least partially from the polycarbonate of component A). Preferably, at least some of the OH groups originate from the polycarbonate of component A).

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

in denen die Phenylringe unabhängig voneinander ein- oder zweifach mit Ci bis Cs Alkyl, Halogen, bevorzugt Ci bis C4 Alkyl, besonders bevorzugt mit Methyl substituiert sein können und X für eine Einfachbindung, eine lineare oder verzweigte Ci bis Ce Alkylen-Gruppe, eine C2 bis C10 Alkylidengruppe, oder eine C5 bis C10 Cycloalkylidengruppe, bevorzugt für eine Einfachbindung oder Ci bis C4 Alkylen und insbesondere bevorzugt für Isopropyliden stehen und die „ - „ für die Anbindung der Strukturen (4) bis (7) ins aromatische Poly carbonat stehen. Dabei ist es insbesondere bevorzugt, dass die Menge der Struktureinheiten (4) bis (7) in Summe 10 ppm bis 1000 ppm, bevorzugt 50 bis 950 ppm, besonders bevorzugt 80 ppm bis 850 ppm beträgt. In particular, the process according to the invention is characterized in that the polycarbonate of component A) comprises one, particularly preferably several of the following structures (4) to (7):

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

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

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

The amount of the compound of formula (5a) released is preferably 0 (i.e. below the detection limit of 10 ppm) to 100 ppm, particularly preferably 0 to 80 ppm and especially preferably 0 to 50 ppm.

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

The amount of the compound of formula (7a) released is preferably 0 (i.e. below the detection limit of 10 ppm) to 300 ppm, preferably 5 to 250 ppm and particularly preferably 10 to 200 ppm.

Component B

The composition may contain polymer additives as component B. Commercially available polymer additives are particularly suitable as polymer additives. Preferred polymer additives according to component B are flame retardants, flame retardant synergists, smoke-inhibiting additives, anti-drip agents, internal and external lubricants and mold release agents, flow aids, antistatic agents, conductivity additives, nucleating agents, stabilizers, antibacterial additives, scratch resistance additives, IR absorbers, optical brighteners, fluorescent additives, fillers and reinforcing agents, dyes and pigments and Brønsted acid compounds. Particularly preferred are polymer additives such as flame retardants (for example phosphorus compounds such as phosphoric or phosphonic acid esters, phosphonate amines and phosphazenes or halogen compounds), flame retardant synergists (for example nanoscale metal oxides), smoke-inhibiting additives (for example boric acid or borates), anti-drip agents (for example compounds from the substance classes of fluorinated polyolefins, silicones and aramid fibers), internal and external lubricants and mold release agents (for example pentaerythritol tetrastearate, stearyl stearate, montan wax or polyethylene wax), flow aids (for example low molecular weight vinyl (co)polymers), antistatic agents (for example block copolymers of ethylene oxide and propylene oxide, other polyethers or polyhydroxyethers, polyether amides, polyester amides or sulfonic acid salts), conductivity additives (for example conductive carbon black or carbon nanotubes), nucleating agents, stabilizers (for example UV/light stabilizers, thermal stabilizers, Antioxidants, transesterification inhibitors, hydrolysis protection agents), antibacterial additives (for example silver or silver salts), scratch resistance improving additives (for example silicone oils or hard fillers such as ceramic (hollow) spheres), IR absorbents, optical brighteners, fluorescent additives, fillers and reinforcing materials (for example talc, possibly ground glass or carbon fibers, glass or ceramic (hollow) spheres, mica, kaolin, CaCO3, and glass flakes) as well as dyes and pigments (for example carbon black, titanium dioxide or iron oxide), impact modifiers, and Brönsted acid compounds as base scavengers, or mixtures of several of the additives mentioned.

According to the invention, it is preferred that component B) comprises at least one filler and/or reinforcing material. This is to be understood in particular to mean that further additives, in particular those mentioned above, can be included, but at least at least one filler and/or reinforcing material. It is particularly preferred that the at least one filler and/or reinforcing material is selected from the group consisting of aluminum hydroxide, aluminum oxide, aluminum silicates, barium oxide, barium sulfate, boehmite, calcium carbonate, diaspore, dolomite, glass beads, graphite, expanded graphite, Kaolin, chalk, magnesium aluminate, magnesium hydroxide, magnesium oxide, montmorillonite, quartz powder, silicates, silicon dioxide, talc, titanium dioxide, vermiculite, wollastonite, zeolites, zirconium oxide, glass fibers, carbon fibers, basalt fibers, aramid fibers, liquid crystal polymer fibers, polyphenylene sulfide fibers, polyether ketone fibers, polyetheretherketone fibers, polyetherimide fibers and any mixtures thereof.

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

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

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

In a preferred embodiment, glass fibers are used. Preferred amounts of glass fibers are between greater than 5 wt.% and 40 wt.% glass fibers based on the thermoplastics used. Further preferred is an amount of glass fibers of 5.5 wt.% to 35 wt.%, particularly preferably 6 wt.% to 30 wt.% based on the thermoplastics used. 10 wt.% is most preferred. to 25 wt.%, likewise preferably 15 wt.% to 25 wt.% glass fibers based on the thermoplastics used in the compositions.

Unless otherwise stated, the weight percentages stated with respect to the thermoplastic composition are to be understood as relating to the total weight of the thermoplastic composition. The thermoplastic composition preferably comprises 60 wt.% to less than 95 wt.% of component A) and 40 wt.% 0 wt.% to more than 5 wt.% of component B), with the exception of 95 wt.% of component A) and 5 wt.% of component B). More preferably, the thermoplastic composition (Z) comprises 60 wt.% to 94 wt.% of component A) and 40 wt.% to 6 wt.% of component B), very preferably 70 wt.% to 90 wt.% of component A) and 30 wt.% to 10 wt.% of component B), likewise preferably 75 wt.% to 87 wt.% of component A) and 25 wt.% to 13 wt.% of component B). The thermoplastic composition preferably consists essentially of components A) and B). Most preferably, the thermoplastic composition consists of components A) and B).

Furthermore, it is preferred that component B) comprises at least one thermal stabilizer in addition to the fillers and/or reinforcing materials described above or in addition to the correspondingly preferred fillers and/or reinforcing materials. Particularly suitable thermal stabilizers are phosphorus-based stabilizers selected from the group of phosphates, phosphites, phosphonites, phosphines, and mixtures thereof. Examples are trisisooctyl phosphate, triphenyl phosphite, diphenyl alkyl phosphite, phenyldialkyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearylpentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite (Irgafos 168), Diisodecylpentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,4-di-cumylphenyl)pentaerythritol diphosphite (Doverphos S-9228), bis(2,6-di-tert-butyl-4-methylphenyl)penta-erythritol diphosphite, diisodecyloxypentaerythritol diphosphite, Bis(2,4-di-tert-butyl-6-methylphenyl)-pentaerythritol diphosphite, bis(2,4,6-tris(tert-butylphenyl)pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, 6-Isooctyloxy-2,4,8,10-tetra-tert-butyl-12H-dibenz[d,g]-l,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl)methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl)ethyl phosphite, 6-fluoro-2,4,8, 1 O-tetra-tert-butyl-12- methyl-dibenz[d,g]-l,3,2-dioxaphosphocin, 2,2',2"-nitrilo-[triethyltris(3,3',5,5'-tetra-tert-butyl-l,l'-biphenyl-2,2'-diyl)phosphite], 2-Ethylhexyl(3,3',5,5'-tetra-tert-butyl-l,l'-biphenyl-2,2'-diyl)phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-l,3,2-dioxaphosphiran, Bis(2,6-di-ter-butyl-4-methylphenyl)pentaerythritol diphosphite, triphenylphosphine (TPP), trialkylphenylphosphine, bisdiphenylphosphinoethane, or trinaphthylphosphine. They are used alone or in a mixture, e.g., Irganox B900 (a 4:1 mixture of Irgafos 168 and Irganox 1076) or Doverphos S-9228 with Irganox B900 or Irganox 1076. Particular preference is given to using triphenylphosphine (TPP), trisisooctylphosphate, Irgafos 168, or tris(nonylphenyl)phosphite, or mixtures thereof. The thermal stabilizers are preferably used in amounts of up to 1.0 wt. %, more preferably 0.003 wt. % to 1.0 wt. %, even more preferably 0.005 wt. % to 0.5 wt. %, particularly preferably 0.01 wt. % to 0.2 wt. %. In particular, it is preferred if TPP is used in amounts of 0 to 0.1 wt. %, particularly preferably 0.05 to 0.08 wt. % and very particularly preferably 0.01 to 0.05 wt. %. It is likewise preferred if stabilizers from the group of phosphites are used in amounts of 0.01 to 0.1 wt. %, particularly preferably 0.015 to 0.09 wt. % and particularly preferably 0.02 to 0.08 wt. %. The skilled person is generally able to relate the amounts of the entirety of component B) (e.g., if component B) comprises a filler and/or reinforcing material and additionally another additive) to the thermoplastic composition if component B) comprises more than one additive. This can be done either via the total amount of B), as stated above, or by adding the individual preferred amounts of the different additives, all of which can be component B).

Furthermore, phenolic antioxidants such as alkylated monophenols, alkylated thioalkylphenols, hydroquinones, and alkylated hydroquinones can preferably be used as component B) in addition to the fillers and/or reinforcing agents described above or in addition to the correspondingly preferred fillers and/or reinforcing agents. 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 wt.%, particularly preferably 0.0025 to 0.1 wt.%, and most preferably 0.005 to 0.04 wt.%.

Particularly suitable ultraviolet absorbers as component B), in particular in addition to the fillers and/or reinforcing materials described above or in addition to the correspondingly preferred fillers and/or reinforcing materials, are hydroxybenzotriazoles, such as 2-(3',5'-bis-(l,l-dimethylbenzyl)-2'-hydroxyphenyl)-benzotriazole (Tinuvin® 234, BASF SE, Ludwigshafen), 2-(2'-Hydroxy-5'-(tert.-octyl)-phenyl)-benzotriazole (Tinuvin® 329, BASF SE, Ludwigshafen), Bis-(3-(2H-benzotriazolyl)-2-hydroxy-5-tert.-octyl)methane (Tinuvin® 360, BASF SE, Ludwigshafen), 2-(4,6-Diphenyl-l,3,5-triazin-2-yl)-5-(hexyloxy)-phenol (Tinuvin® 1577, BASF SE, Ludwigshafen), 2-(5chloro-2H-benzotriazol-2-yl)-6-(l,l-dimethylethyl)-4-methyl-phenol (Tinuvin® 326, BASF SE, Ludwigshafen), as well as benzophenones such as 2,4-Dihydroxybenzophenone (Chimasorb® 22, BASF SE, Ludwigshafen) and 2-Hydroxy-4-(octyloxy)-benzophenone (Chimassorb® 81, BASF SE, Ludwigshafen), 2,2-bis[[(2-cyano-l-oxo-3,3-diphenyl-2-propenyl)oxy]-methyl]-l,3-propanediyl ester (9CI) (Uvinul 3030, BASF SE, Ludwigshafen), 2-[2-Hydroxy-4-(2-ethylhexyl)oxy]phenyl-4,6-di(4-phenyl)phenyl-l,3,5-triazine (Tinuvin® 1600, BASF SE, Ludwigshafen), tetraethyl-2,2'-(l,4-phenylene-dimethylidene)bismalonate (Hostavin B-Cap, Clariant AG) or N-(2- Ethoxyphenyl)-N'-(2-ethylphenyl)-ethanediamide (Tinuvin® 312, CAS no. 23949-66-8, BASF SE, Ludwigshafen).

If UV absorbers are included, the composition preferably contains ultraviolet absorbers in an amount of up to 0.8 wt.%, preferably 0.05 wt.% to 0.5 wt.%, more preferably 0.08 wt.% to 0.4 wt.%, most preferably 0.1 wt.% to 0.35 wt.%, based on the total composition.

Component B) may preferably contain a mold release agent in addition to the fillers and/or reinforcing materials described above or in addition to the correspondingly preferred fillers and/or reinforcing materials. Pentaerythritol tetrastearate (PETS) or glycerol monostearate (GMS) are particularly suitable as mold release agents. If mold release agents are present, the composition preferably contains up to 0.8 wt. %, preferably 0.05 wt. % to 0.5 wt. %, more preferably 0.08 wt. % to 0.4 wt. %, most preferably 0.1 wt. % to 0.35 wt. %, based on the total composition.

It has proven particularly advantageous if the thermoplastic composition as component B) further comprises, in addition to the fillers and/or reinforcing materials described above or in addition to the correspondingly preferred fillers and/or reinforcing materials, at least one hydroxyl component (I) comprising at least three carbon atoms and at least three hydroxyl groups, wherein at least one of these at least three hydroxyl groups is esterified with an aliphatic saturated or unsaturated, linear, cyclic or branched Ci-C32 carboxylic acid or benzoic acid and at least one of these at least three hydroxyl groups as free hydroxyl group is present. Of course, other components B) may also be present in this case.

Surprisingly, it was found that the additional use of special hydroxyl components in the carrier material leads to an even further improvement in the improved composite adhesion. However, the special hydroxyl component accumulates predominantly on the surface of the carrier. As a result, the bulk properties of the carrier are hardly affected by the use of the additional additive. The composite shows a further improvement, particularly compared to a comparable system, whereby the polycarbonate of component A) does not have an additive with at least one hydroxyl group, preferably no special hydroxyl component (I). Without wishing to be bound by any theory, it is assumed that the special hydroxyl component (I) can act as an adhesion promoter due to its chemical nature. The hydrophilic OH groups and, if present, also the hydrophobic hydrocarbon chains (particularly if they are long-chain) lead to these accumulating on the surface of the carrier during and/or after the formation of the carrier. At the same time, the hydrophobic hydrocarbon groups lead to a firm anchoring in and on the carrier material (long-chain hydrocarbons in particular can interlock with the carrier material in a manner known to those skilled in the art, thus forming a resilient bond even without the formation of a covalent bond). The mobility and thus the tendency for surface enrichment towards the carrier can be influenced, for example, by the cooling process. The warmer the melt, the more mobile the molecules are. The temperature of the melt can be influenced, for example, by increasing the overall melt temperature during the process or the mold temperature. At the same time, this surface enrichment leads to a depletion of the specific hydroxyl component in the bulk of the carrier material. This means that the hydroxyl component has hardly any influence on the bulk properties of the carrier. On the other hand, it also means that the amount of hydroxyl component can be kept low, since it is effectively used only where it is needed. This further reduces costs.

Without wishing to be bound by theory, it is assumed that, in particular, the additional OH groups present on the surface of the formed support are available for reaction with the components of the polyurethane raw material mixture. The combination of covalent bonds between polycarbonate and polyurethane and the bonds firmly anchored in the carrier material, but still more flexible, between the reacted hydroxyl compound and the polyurethane lead overall to a good bond.

Preferably, the hydroxy I component (I) is represented by the structural formula (I)

(R4-C(=O)O)O-( _R5 )X-(OH) _P (I), wherein each R4 is independently an aliphatic saturated or unsaturated, linear, cyclic or branched C1-C31 alkyl radical or phenyl,

R ₅ is a linear, cyclic or branched alkylene group having x carbon atoms, where 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 R ₅ can each have the substituents (R ₄ - C(=O)O) _o -, -(OH)p and/or hydrogen or an alkyl radical and o is a number from 1 to 12 and p is a number from 1 to 12, with the proviso that o + p is 2 to 12 and the maximum of o + p is determined by the maximum number x of carbon atoms in R5.

It is obvious to the person skilled in the art that only as many substituents are present in formula (I) as there are valences of the carbon atom available. If, for example, a branched _R5 alkylene group has at least one tertiary carbon atom, this tertiary carbon atom thus has at most one valence available for one of the substituents _R4 -C(=O)O) _o- , -(OH) _P and/or hydrogen. Likewise, a branched R5 alkylene group can have a quaternary carbon atom that has no valence for any other substituent.

worin jedes R4 unabhängig voneinander für Wasserstoff, einen aliphatischen gesättigten oder ungesättigten, linearen, cyclischen oder verzweigten C1-C31 -Alkylrest oder Phenyl steht, unter der Bedingungen, dass mindestens ein R₄ Wasserstoff ist und mindestens ein R₄ ein aliphatischer gesättigter oder ungesättigter, linearer, cyclischer oder verzweigter C1 -C31- Alkylrest oder Phenyl ist, jedes Y unabhängig voneinander für Wasserstoff, einen Alkyl- oder Arylrest steht undIt is also preferred that the hydroxyl component (I) is represented by the structural formula (Ia) or (Ib)

wherein each R4 independently represents hydrogen, an aliphatic saturated or unsaturated, linear, cyclic or branched C1-C31 alkyl radical or phenyl, under the conditions that at least one _R4 is hydrogen and at least one _R4 is an aliphatic saturated or unsaturated, linear, cyclic or branched C1-C31 alkyl radical or phenyl, each Y independently represents hydrogen, an alkyl or aryl radical and

Z represents hydrogen, an alkyl radical or OR4,

(Ib), wherein each R4 independently represents hydrogen, an aliphatic saturated or unsaturated, linear, cyclic or branched C1-C31 alkyl radical or phenyl, under the conditions that at least one _R4 is hydrogen and at least one _R4 is an aliphatic saturated or unsaturated, linear, cyclic or branched C1-C31 alkyl radical or phenyl, each Y independently represents hydrogen, an alkyl or aryl radical,

Z represents hydrogen or an alkyl radical and x represents a number between 3 and 12, preferably 3 to 8, particularly preferably 3 to 7, most particularly preferably 3 to 5.

In particular, it is preferred that x in structural formula (I) or (Ib) is 3 to 5.

It is particularly preferred that each R ₄ in structural formula (I), (Ia) or (Ib) independently of one another represents methyl, ethyl, n-propyl, iso-propyl, n-butyl, see. -Butyl, tert-Butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neo-pentyl, 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, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, l-ethyl-2-methylpropyl, l-Ethyl-2-methylpropyl, n-heptyl, n-octyl, pinakyl, adamantyl, the isomeric menthyls, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, or n-octadecyl. Particularly preferably, each R4 in structural formula (I), (Ia), or (Ib) independently represents n-nonyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl, or n-octadecyl.

Likewise preferred, particularly preferred in combination with the above-described meanings for R4, is that each Y in structural formula (I), (Ia) or (Ib) independently represents hydrogen, methyl, ethyl, propyl, butyl or phenyl. Component B) is particularly preferred to be glycerol monostearate.

The thermoplastic composition preferably comprises 0.0001 to 5 wt.%, more preferably 0.001 to 1 wt.%, most preferably 0.01 to 0.8 wt.%, and most preferably 0.02 to 0.06 wt.% of the hydroxyl component (I). These amounts provide the additional advantage of further improving bond strength, but at the same time, the amount is so small that the bulk properties of the carrier are barely altered.

Particularly preferably, component B) preferably comprises, in addition to the fillers and/or reinforcing materials described above or in addition to the correspondingly preferred fillers and/or reinforcing materials, at least one stabilizer, preferably from the group of phosphites and/or phosphates, particularly preferably one of the above-mentioned compounds, at least one mold release agent, at least one UV absorber, at least one phenolic antioxidant and optionally colorants (organic) and/or pigments (organic and inorganic).

Very particularly preferably, component B) preferably comprises, in addition to the above-mentioned amounts of fillers and/or reinforcing materials, TPP in amounts of 0 to 0.1 wt.%, particularly preferably 0.05 to 0.08 wt.% and very particularly preferably 0.01 to 0.05 wt.%, at least one stabilizer from the group of phosphites and/or phosphates in amounts of 0.01 to 0.1 wt.%, particularly preferably 0.015 to 0.09 wt.% and particularly preferably 0.02 to 0.08 wt.%, at least one ultraviolet absorber in an amount of up to

0.8 wt.%, preferably 0.05 wt.% to 0.5 wt.%, more preferably 0.08 wt.% to 0.4 wt.%, most preferably 0.1 wt.% to 0.35 wt.%, at least one mold release agent up to 0.8 wt.%, preferably 0.05 wt.% to 0.5 wt.%, more preferably 0.08 wt.% to 0.4 wt.%, most preferably 0.1 wt.% to 0.35 wt.% Unless otherwise stated, all wt% values refer to the total composition.

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

Unless otherwise stated, ppm values refer to weight.

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

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

in der jedes Z unabhängig voneinander für eine Ether-Bindung, eine Carbonyl-Gruppe, eine Ester- Gruppe oder eine Einfachbindung steht, jedes R^A unabhängig voneinander für eine lineare oder verzweigte Alkylen-Gruppe mit 1 bis 20 Kohlenstoffatomen oder eine Alkenylen-Gruppe mit 2 bis 20 Kohlenstoffatomen steht, jedes R^B unabhängig voneinander für eine lineare oder verzweigte Alkylgruppe mit 1 bis 20 Kohlenstoffatomen, eine Alkoxy-Gruppe mit 1 bis 10 Kohlenstoffatomen, eine Aryl-Gruppe mit 6 bis 12 Kohlenstoffatomen oder ein Halogen steht, m für eine Zahl von 1 bis 3 steht, o für eine Zahl von 0 bis 3 steht, mit der Maßgabe, dass die Summe von m und o nie größer 5 sein kann und der * die Anbindung der Formel (X) an die Hauptkette des Poly carbonats darstellt. In particular, it is preferred that the part of the OH groups which is bonded to the polycarbonate via an aliphatic group (if present at all) is bonded to the polycarbonate via a structure of formula (X), where

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

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

It will be apparent to those skilled in the art that the term "single bond" in the definition of Z is to be understood as meaning that "Z" is not present at all. This means that ^RA is directly bonded to the phenyl ring.

Most preferably, in formula (X), each Z represents a single bond, each ^RA independently represents a linear alkylene group having 1 to 4 carbon atoms, preferably an ethylene group, each R ^B independently represents a linear alkyl group having 1 to 4 carbon atoms, preferably a methyl group or an alkoxy group having 1 to 4 carbon atoms, preferably a methoxy group, m represents a number from 1 to 3, preferably 1, o represents a number from 0 to 3, preferably 0.

Such polycarbonates with aliphatic end groups can be obtained as described, for example, in EP4026871 Al, EP3981822 Al, JP2008-101191A or JP2008-095046A.

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

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

Those skilled in the art know how to determine OH contents in thermoplastic compositions. This is particularly a volume analysis method. ¹ H NMR spectroscopy or infrared techniques are particularly suitable for this purpose. The choice of method also depends on component B), since bands or signals may overlap within one method. It may also be necessary to first remove component B) from the thermoplastic composition in order to carry out the corresponding determination. It may also be possible that component B) (for example, if it is a filler or reinforcing material) is insoluble in the solvent required for the analysis and can therefore be easily separated. Such separation can also be carried out specifically before the analysis.

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

Polyurethanes

A polymethane foam or a compact polyurethane layer is preferably used as a coating.

The polyurethanes used according to the invention are obtained by reacting polyisocyanates with H-active polyfunctional compounds, preferably polyols. In the context of this invention, the term "polyurethane" also includes polyurethaneureas, in which compounds with N-H functionality, optionally in admixture with polyols, are used as H-active polyfunctional compounds.

Suitable polyisocyanates are the aromatic, araliphatic, aliphatic, or cycloaliphatic polyisocyanates known to those skilled in the art with an NCO functionality of preferably > 2, which may also have iminooxadiazinedione, isocyanurate, uretdione, urethane, allophanate, biuret, urea, oxadiazinetrione, oxazolidinone, acylurea, and/or carbodiimide structures. These can be used individually or in any desired mixtures with one another.

The above-mentioned polyisocyanates are based on di- or triisocyanates known per se to those skilled in the art with aliphatically, cycloaliphatically, araliphatically and/or aromatically bound isocyanate groups, it being irrelevant whether these were prepared using phosgene or by phosgene-free processes. Examples of such di- 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- or 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3- and 1,4-diisocyanatocyclohexane, 1,3- and l,4-bis-(isocyanatomethyl)-cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 4,4'-diisocyanatodicyclohexylmethane (Desmodur W, Covestro AG, Leverkusen, DE), 4-isocyanatomethyl-l,8-octane diisocyanate (triisocyanatononane, TIN), CD, CD -diisocyanato-1,3-dimethylcyclohexane (H ₆ XDI), l-isocyanato-l-methyl-3-isocyanato-methylcyclohexane, 1-isocyanato-1-methyl-1-4-isocyanato-methylcyclohexane, bis-(isocyanatomethyl)-norbornane, 1,5-naphthalene diisocyanate, 1,3- and l,4-bis-(2-isocyanato-prop-2-yl)-benzene (TMXDI), 2,4- and 2,6-diisocyanatotoluene (TDI), in particular the 2,4 and 2,6 isomers and technical mixtures of the two isomers, 2,4'- and 4,4'-diisocyanatodiphenylmethane (MDI), polymeric MDI (pMDI), 1,5-diisocyanatonaphthalene, l,3-bis(isocyanatomethyl)benzene (XDI) and any mixtures of the compounds mentioned.

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

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

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

Among the higher molecular weight, modified polyisocyanates, the prepolymers known from polyurethane chemistry with terminal isocyanate groups in the molecular weight range 400 to 15,000, preferably 600 to 12,000, are of particular interest. These compounds are prepared in a conventional manner by reacting excess amounts of simple polyisocyanates of the type exemplified with organic compounds having at least two groups reactive towards isocyanate groups, in particular organic polyhydroxyl compounds. Suitable polyhydroxyl compounds of this type are both simple polyhydric alcohols in the molecular weight range 82 to 599, preferably 62 to 200, such as ethylene glycol, trimethylolpropane, 1,2-propanediol or 1,4-butanediol or 2,3-butanediol, but in particular higher molecular weight polyether polyols and/or polyester polyols from the polyurethane chemistry, having molecular weights of 600 to 12,000, preferably 800 to 4,000, which have at least two, generally 2 to 8, but preferably 2 to 6, primary and/or secondary hydroxyl groups. It is of course also possible to use NCO prepolymers which have been obtained, for example, from low molecular weight polyisocyanates of the type exemplified and less preferred compounds having groups reactive toward isocyanate groups, such as polythioether polyols, hydroxyl-containing polyacetals, polyhydroxypolycarbonates, hydroxyl-containing polyesteramides, or hydroxyl-containing copolymers of olefinically unsaturated compounds.

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

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

Suitable H-active components are polyols with an average OH number of 5 to 600 mg KOH/g and an average functionality of 2 to 6. Polyols with an average OH number of 10 to 50 mg KOH/g are preferred. Polyols suitable according to the invention are, for example, polyhydroxypolyethers, which are 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. are accessible. Ammonia or amines such as ethylenediamine, hexamethylenediamine, 2,4-diaminotoluene, aniline, or amino alcohols or phenols such as bisphenol A can also act as initiators. The alkoxylation is carried out using propylene oxide and/or ethylene oxide in any order or as a mixture.

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

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

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

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

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

Mixtures of the listed compounds can also be used.

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

The polyurethane layer (b) can be foamed or solid, e.g. as a varnish or coating.

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

If necessary, the following auxiliary agents and additives may be used: a) Water and/or volatile inorganic or organic substances as propellants

Suitable organic blowing agents are acetone, ethyl acetate, halogen-substituted alkanes such as methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane, as well as butane, hexane, heptane or diethyl ether, and inorganic blowing agents are air, CO2 or _N2O . A blowing effect can also be achieved by adding at temperatures above room temperature with the release of gases, for example, of nitrogen, decomposing compounds, e.g. azo compounds such as azodicarbonamide or azoisobutyronitrile. b) Catalysts

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

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

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

Tertiary amines containing amide groups (preferably formamide groups),

Mannich bases from secondary amines (such as dimethylamine) and aldehydes (preferably formaldehyde or ketones such as acetone, methyl ethyl ketone or cyclohexanone) and phenols (such as phenol, nonylphenol or bisphenol), tertiary amines containing hydrogen atoms active towards isocyanate groups (e.g. triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine), as well as their reaction products with alkylene oxides such as propylene oxide and/or ethylene oxide, secondary tertiary amines,

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

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

The reaction between NCO groups and Zerewitinoff-active hydrogen atoms is also strongly accelerated by lactams and azalactams in a known manner, whereby an associate is initially formed between the lactam and the compound with acidic hydrogen. Organic metal compounds, in particular organic tin and/or bismuth compounds, can also be used as catalysts. In addition to sulfur-containing compounds such as di-n-octyltin mercaptide, suitable organic tin compounds are preferably tin(II) salts of carboxylic acids such as tin(II) acetate, tin(II) octoate, tin(II) ethylhexoate, and tin(II) laurate, as well as tin(IV) compounds, e.g., dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, or dioctyltin diacetate. Organic bismuth catalysts are described, for example, in patent application WO 2004/000905.

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

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

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

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

Acidic substances (such as hydrochloric acid or organic acid halides) can be used as reaction retarders. e) Additive

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

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

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

Typically, coating systems with a short pot life are used. Systems with a maximum pot life of 1 minute are preferred, with a maximum pot life of 30 seconds being particularly preferred, and a maximum pot life of 10 seconds being even more preferred. The cycle time for the reaction of the coating system is preferably adapted to the injection molding cycle time. This is particularly economical. For short pot lives, a high-pressure countercurrent mixing head is preferably used to mix the two components. Compared to other processes, this allows for the highest productivity. Furthermore, no residues of mixed coating raw materials remain in the mold at the end of the process. In a further aspect of the present invention, a composite component is provided, comprising a) a carrier made of a thermoplastic composition containing

A) 60 wt% to less than 95 wt% of a polycarbonate and

B) 40 wt.% to more than 5 wt.% of at least one polymer additive, and wherein the OH content of the carrier is at least 230 ppm, b) at least one polyurethane layer in direct contact with the carrier, produced by the process according to the invention, preferably also in all preferences and combinations of preferences.

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

The OH content of the composite component refers to the carrier. It is possible that the OH content decreases due to reaction with the reactive polyurethane raw material mixture, at least on the surface of the carrier. However, this is probably limited to the immediate surface and therefore not detectable by conventional volume analysis. This is due in particular to the fact that the reaction essentially only takes place at the interface and the polyurethane raw material mixture hardly penetrates the carrier material. The OH content of the carrier is determined by volume analysis on the composite component. For this purpose, the polyurethane layer is first removed. Subsequently, the volume analysis of the carrier is carried out. This preferably means the preparation and analysis of a representative volume of the carrier (not just the surface facing the polyurethane layer). In particular, the methods described above can be used for this purpose, preferably ' H NMR or IR spectroscopy. Since the coating process usually does not lead to any significant change in the OH content in the volume of the carrier or film, the OH content in the carrier or film corresponds to the OH content in the uncoated carrier or film to a first approximation. It is particularly preferred if the composite component according to the invention is produced in a 2-component reactive injection molding process with a reactive polyurethane raw material mixture containing

- at least one polyisocyanate component,

- at least one polyfunctional H-active compound, and

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

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

In a further aspect of the present invention, a use of a thermoplastic composition is provided, wherein the thermoplastic composition

A) 60 wt% to less than 95 wt% of a polycarbonate and

B) contains 40 wt.% to more than 5 wt.% of at least one polymer additive, wherein the OH content of the thermoplastic composition is at least 230 ppm, as a carrier material in the production of the composite component according to the invention. These are preferably the components A), B) described above and the polyurethane layer described above in all preferred forms and combinations of preferred forms.

Examples

Materials used:

Compound 1: 94 wt.% polycarbonate based on BP A with a melt volume flow rate MVR of 12 cm ³ /(10 min) (according to ISO 1133:2012-03, at a test temperature of 300 °C and 1.2 kg load) and 6 wt.% glass fiber CS7942 (Lanxess Deutschland GmbH; E-glass (DIN 1259) with a diameter of approximately 14 pm and an average length of 4.5 mm); OH content of 610 ppm

Compound 2: 94 wt.% polycarbonate based on BP A with a melt volume flow rate MVR of 12 cm ³ /(10 min) (according to ISO 1133:2012-03, at a test temperature of 300°C and 1.2 kg load) and 6 wt.% glass fiber CS7942 (Lanxess Deutschland GmbH; E-glass (DIN 1259) with a diameter of approximately 14 pm and an average length of 4.5 mm); OH content of 100 ppm

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

Test methods used

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

Hydrolysis storage: The composite components were stored for 72 h at (90 ± 2) °C and (95 ± 3) % relative humidity in a climate chamber. The formation of water droplets on the The component was prevented by appropriate positioning in the climatic chamber. Subsequently, the components were subjected to another adhesion test using the "POSI" test (see above). A percentage decrease in adhesion of the result obtained by the "POSI" test was calculated in relation to the value before and after hydrolysis storage.

OH content:

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

The OH content of the compound used was determined in the same way.

Production and characterization of the compounds:

The components of Compounds 1 and 2 were mixed on a ZSK25 twin-screw extruder from Coperion, Werner & Pfleiderer (Stuttgart, Germany) at a melt temperature of 280 °C and under a vacuum of 50–100 mbar (absolute). The speed was 225 rpm and the throughput was 15 kg/h.

Production of composite components:

Partially surface-coated molded parts with a projected area of 286.4 ^cm² were manufactured on an injection molding machine in a two-cavity injection mold (one substrate-side cavity and one polyurethane-side coating cavity linked to a RIM system). The composite component was a plate-shaped component made of thermoplastic material (carrier), the surface of which was partially coated with a polyurethane skin. The coated area of the component was 225.5 ^cm² . Of this area, 150 ^cm² served as the test area for adhesion tests. Eight measurements were performed on the test area. The wall thickness of the test area was approximately 3.2 mm for the injection-molded component and 0.5 mm for the polyurethane layer. Three composite components were used for the initial adhesion measurement and three composite components for the adhesion measurement after hydrolysis storage.

In the first step, the carrier was produced. For this purpose, thermoplastic granules of the compositions described above were mixed in a The material was melted in the injection molding cylinder and injected into the first mold cavity of the closed mold at a temperature of 290 °C. This mold cavity was then heated to a temperature of 100 °C. After the holding pressure and cooling times, which led to the solidification of the carrier, the mold was opened in the second process step. The manufactured carrier component was held on the ejector side of the injection mold. The sliding table on the nozzle side of the injection mold was moved to position two. The mold was closed again in the third process step, and the carrier formed a cavity with the mold for the polyurethane coating.

In the fourth process step, the two reactive components of the polyurethane coating system were conveyed from the RIM system into a high-pressure countercurrent mixing head and mixed there before injection. The PU-side cavity was heated to 100 °C. After the reaction and cooling time, the mold was opened again in the fifth process step, and the coated part was demolded.

The molded parts were then subjected to the adhesion test (initial adhesion). The molded parts were also subjected to the hydrolysis storage described above, and the adhesion was measured again (adhesion after hydrolysis). The same defect pattern was observed in all measurements. The percentage loss of adhesion was calculated from these values.

Table 1:

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

Claims

Patent claims: 1. A method for producing a composite component comprising a) a carrier made of a thermoplastic composition and b) at least one polyurethane layer in direct contact with the carrier, comprising the steps (i) injecting a melt of a thermoplastic composition (Z) into a tool cavity and subsequent cooling to form the carrier, wherein the thermoplastic composition (Z) A) 60 wt% to less than 95 wt% of a polycarbonate and B) contains 40 wt.% to more than 5 wt.% of at least one polymer additive, and the OH content of the carrier is at least 230 ppm, (ii) Enlarging the cavity of the tool and thereby creating a gap or introducing the carrier into a second cavity of the tool which is larger in terms of its hollow shape dimensions than the first cavity, thereby creating a gap, (iii) Injecting a reactive polyurethane raw material mixture containing - at least one polyisocyanate component, - at least one polyfunctional H-active compound, and - optionally at least one polyurethane additive and/or processing aid into the gap between the carrier and the tool surface, whereby the polyurethane raw material mixture polymerises in contact with the surface of the carrier to form a compact polyurethane layer or a polyurethane foam layer, (iv) Demoulding the composite component from the mould cavity. 2. Process according to claim 1, characterized in that the OH content of the carrier is in the range of 230 ppm to 4000 ppm. 3. Process according to one of claims 1 or 2, characterized in that component B) is selected from the group consisting of at least one representative of the group consisting of flame retardants, flame retardant synergists, smoke-inhibiting additives, anti-drip agents, internal and external lubricants and mold release agents, flow aids, antistatic agents, conductivity additives, nucleating agents, stabilizers, antibacterial additives, scratch-resistance-improving additives, IR absorbents, optical brighteners, fluorescent additives, fillers and reinforcing materials, dyes and pigments and Brönsted acid compounds. 4. Process according to claim 3, characterized in that component B) comprises at least one filler and/or reinforcing material. 5. The method according to claim 4, characterized in that the at least one filler and/or reinforcing material is selected from the group consisting of aluminum hydroxide, aluminum oxide, aluminum silicates, barium oxide, barium sulfate, boehmite, calcium carbonate, diaspore, dolomite, glass beads, graphite, expanded graphite, kaolin, chalk, magnesium aluminate, magnesium hydroxide, magnesium oxide, montmorillonite, quartz powder, silicates, silicon dioxide, talc, titanium dioxide, vermiculite, wollastonite, zeolites, zirconium oxide, glass fibers, carbon fibers, basalt fibers, aramid fibers, liquid crystal polymer fibers, polyphenylene sulfide fibers, polyether ketone fibers, polyetheretherketone fibers, polyetherimide fibers and any mixtures thereof. 6. Method according to one of claims 1 to 5, characterized in that the carrier has a wall thickness of 0.5 mm to 10 mm at least at one point. 7. Method according to one of claims 1 to 6, characterized in that the polyurethane layer has a layer thickness of 1 pm to 20 cm. 8. Process according to one of claims 1 to 7, characterized in that the thermoplastic composition (Z) consists of components A) and B). 9. Process according to one of claims 1 to 8, characterized in that a low-solvent reactive polyurethane raw material mixture with a solvent content of at most 10 wt.%, preferably at most 2 wt.%, particularly preferably at most 1 wt.%, based on the paint content is used. 10. Process according to one of claims 1 to 8, characterized in that a solvent-free reactive polyurethane raw material mixture is used. 11. Process according to one of claims 1 to 10, characterized in that the reactive polyurethane raw material mixture has a pot life of at most 1 minute, preferably at most 30 seconds, particularly preferably at most 10 seconds. 12. Process according to one of claims 1 to 11, characterized in that the polymerization in process step (iii) takes place under elevated pressure. 13. Composite component comprising a) a carrier made of a thermoplastic composition (Z) containing A) 60 wt% to less than 95 wt% of a polycarbonate and B) 40 wt.% to more than 5 wt.% of at least one polymer additive, and wherein the OH content of the carrier is at least 230 ppm, b) at least one polyurethane layer in direct contact with the carrier, produced by the process according to any one of claims 1 to 12. 14. Composite component according to claim 13, characterized in that it is an interior or exterior component of a rail, aircraft or motor vehicle. 15. Use of a thermoplastic composition containing A) 60 wt% to less than 95 wt% of a polycarbonate and B) contains 40 wt.% to more than 5 wt.% of at least one polymer additive, wherein the OH content of the thermoplastic composition is at least 230 ppm, as a carrier material in the production of a composite component according to one of claims 13 or 14.