Method for manufacturing a composite member having a support including a polycarbonate with a specific OH content

Abstract

The present invention relates to a method for manufacturing a composite member with improved interlayer bonding, the composite member comprising a carrier containing polycarbonate and at least one polyurethane layer in direct contact with the carrier. The present invention also relates to a composite member with improved interlayer bonding and to the use of a polycarbonate having a defined OH content as a carrier material in the manufacture of a composite member with improved interlayer bonding.

Description

Technical Field

[0001] The present invention relates to a method for manufacturing a composite member with improved composite adhesiveness, the composite member comprising a carrier containing polycarbonate and at least one polyurethane layer in direct contact with the carrier. The present invention also relates to a composite member with improved composite adhesiveness and the use of a polycarbonate carrier material having a defined OH content in the manufacture of a composite member with improved composite adhesiveness.

Background Art

[0002] A composite member comprising a carrier made of a thermoplastic material and at least one polyurethane layer in direct contact with the carrier is known in the prior art. Solid coated molded articles can be manufactured, for example, by methods such as the RIM method (reaction injection molding). A particularly advantageous manufacturing method for composite members having a thick coating is the so-called in-mold coating (IMC) or direct coating (DC). This involves applying the coating components to the corresponding carrier in the mold and curing them in the mold cavity. In addition to the above requirements, the major advantages of the IMC technology include short processing time, less or reduced loss of raw materials, and the manufacture of the coated injection molded article (composite member) including the coating being carried out in one operation. Both the composite member obtained by the RIM method and the composite member obtained by the IMC method exhibit the mechanical properties of the carrier material, but their weather stability and scratch resistance are improved by the polyurethane layer. Needless to say, the overall performance and overall stability of the composite member are also determined by the adhesion of the polyurethane layer to the carrier. Commonly used composite members having a polycarbonate as the carrier material often exhibit a decrease in adhesion after being subjected to stresses such as environmental cycle tests or storage. As a result, the overall performance of the composite member also decreases. Another advantage of the RIM method and the IMC method is that when these methods are used, it is possible to produce unique designs that cannot be obtained by other methods. This is particularly due to the fact that the coating of the composite member can be made relatively thick while the reaction is rapid.

[0003] Patent Document 1 discloses an IMC method for manufacturing a multi-layer plastic part in which at least one layer of a two-component duromer, preferably polyurethane, is coated on a plastic injection molded article. In this method, the plastic part and the layer of the two-component duromer are continuously injected into the same mold in a cycle-synchronized manner. Patent Document 1 does not show anything regarding the influence of the properties of the carrier material and method parameters on the adhesion between the carrier material and the layer of the composite member in contact with the carrier material.

[0004] Patent Document 2 describes a method for forming and coating a substrate in a mold having at least two cavities. The method includes A) a step of forming a substrate in a first cavity of the mold, and B) a step of introducing the substrate produced in the previous step into a second cavity of the mold, and C) a step of coating the substrate with a paint in the second cavity, the coating being carried out under high pressure. It includes.

[0005] Also in Patent Document 2, the focus is not on the adhesion between the carrier material and the paint layer.

[0006] Patent Document 3 describes that the adhesion to a polyurethane layer can be improved by a special surface structuring of the carrier. It is also known that the use of a primer or a special activation of the carrier material can lead to an improvement in adhesion.

[0007] Patent Document 4 relates to providing an improvement in the bonding of a carrier material and a polyurethane layer under the condition that surface modification of the carrier (especially primer or surface activation) is not required. The use of a foamed carrier material has been found to have a positive effect on the adhesion to the polyurethane layer. In Patent Document 5, the influence of the rubber content of a composition containing polycarbonate and a rubber-modified vinyl (co)polymer as a carrier material on the composite adhesion has been investigated.

[0008] In these documents, the improvement of the bonding adhesion is achieved either by additional steps such as the application of a primer, the surface activation of the carrier material, surface structuring or foaming, or by adding an additive to the composition of the carrier material. This all means that in the manufacture of composite parts, additional steps with corresponding costs and complexity are required. Alternatively, a specially added composition of the carrier material that affects the mechanical and optical properties of the resulting composite member is required, which also involves additional costs for the additive.

Prior Art Documents

Patent Documents

[0009]

Patent Document 1

Patent Document 2

Patent Document 3

Patent Document 4

Patent Document 5

Summary of the Invention

Problems to be Solved by the Invention

[0010] Starting from this prior art, it is an object of the present invention to overcome at least one disadvantage of the prior art. In particular, the object of the present invention was to provide a composite member in which the bond between a carrier material containing polycarbonate and at least one polyurethane layer in direct contact with the carrier material was improved. It is preferred that no additional steps such as surface modification by primer or surfactant are required. Similarly, the use of additional additives to improve / increase the composite adhesiveness of the carrier material should also be avoided. In particular, the polyurethane raw material mixture used in the production of the composite member should be highly reactive (i.e., preferably the mold holding time is less than 150 seconds, preferably less than 100 seconds). More preferably, the polyurethane raw material mixture used should have a pot life of at most 30 seconds, preferably at most 10 seconds. It is particularly highly preferred that the composite member is produced by the RIM method or the IMC method, particularly the IMC method.

[0011] At least one, preferably all, of the above objects have been achieved by the present invention. Surprisingly, it has been found that by using a polycarbonate having a defined OH number as a carrier material, an improvement in the bond between the carrier material and at least one polyurethane layer in direct contact with the carrier material is brought about. The resulting composite is bonded in a frictionally connecting manner. This can be evaluated, in particular, by using the POSI test (using method B (8.4.2) which shows the most damaged defect pattern optionally according to DIN EN ISO 4624:2016-08). Away from the DIN standard, it is preferred to carry out 8 measurements per component and analyze a total of 3 components. The adhesiveness value is obtained from the median of the measurements. The initial adhesiveness of the composite member according to the present invention is preferably at least 5 MPa as measured by the above POSI test. The adhesiveness of the composite member according to the present invention after the hydrolysis test (i.e., after storage in a conditioning cabinet at 90 ± 2 °C and 95 ± 3% relative humidity for 72 hours (avoiding the formation of water droplets on the component by positioning it appropriately in the conditioning chamber)) is also preferably at least 2 MPa as measured by the above POSI test. The composite adhesiveness between the carrier composed of the polycarbonate composition and the polyurethane coating in the composite member according to the present invention can also be tested at a test speed of 100 mm / min in a wheel peel test according to DIN 53357:1982-10 using a strip-shaped test piece with a width of 20 mm obtained from the component.

[0012] The composite shows an improvement, in particular, compared to an equivalent system which is a polycarbonate but has a lower OH number than the OH number according to the invention. At the same time, since an excessive OH content has a harmful effect on the thermal stability of the polycarbonate, it is known to those skilled in the art that the OH number of the polycarbonate should be kept as low as possible. Such polycarbonates tend to turn yellow when heated. The specifically defined range of OH groups in the polycarbonate used, while effectively improving the composite adhesion on the one hand, has been found according to the invention to still be sufficiently low on the other hand to ensure that the resulting composite member exhibits good thermal stability. Without wishing to be bound by a particular theory, it is considered that, in particular, the OH groups present on the surface of the formed carrier are available for reaction with the components of the polyurethane raw material mixture. This results in the formation of a bond, preferably a covalent bond, between the surface of the carrier and the polyurethane layer formed. As a result, good bonding in the resulting composite member is achieved. This effect is particularly pronounced in the RIM process and / or the IMC process, because the polyurethane raw material mixtures used in the RIM process and / or the IMC process generally have a high isocyanate content. This makes it possible to particularly effectively carry out the described reaction.

Means for Solving the Problems

[0013] Therefore, in one aspect, the present invention provides a) a carrier composed of a thermoplastic composition, and b) at least one polyurethane layer in direct contact with the carrier, and provides a method for manufacturing a composite member comprising: (i) injecting a melt of the thermoplastic composition into a mold cavity and then cooling to form the carrier, wherein the thermoplastic composition comprises A) at least 95.0% by weight of an aromatic polycarbonate having a phenolic OH content of 230 ppm to 1500 ppm, and B) 0% to 5.0% by weight of at least one polymer additive, A step comprising, (ii) creating a gap by expanding the cavity of the mold, or introducing the carrier into a second cavity of the mold having a hollow mold dimension larger than that of the first cavity to create a gap; (iii) at least one polyisocyanate component, at least one polyfunctional active hydrogen compound, optionally, at least one polyurethane additive and / or processing aid, injecting a reactive polyurethane raw material mixture containing the same into the gap between the carrier and the mold surface, wherein the polyurethane raw material mixture polymerizes to provide a dense polyurethane layer or a polyurethane foam layer in contact with the surface of the carrier; (iv) demolding the composite member from the mold cavity; and comprising.

[0014] Thus, in one aspect, the present invention also provides a) a carrier composed of a thermoplastic composition, b) at least one polyurethane layer in direct contact with the carrier, and provides a method for manufacturing a composite member comprising the same, the method comprising (i) (ia) injecting a melt of a thermoplastic composition (Z) into a mold cavity and then cooling to form the carrier, or (ib) introducing a film comprising an outer ply composed of a thermoplastic composition (Z) into the mold cavity and overmolding the opposite side of the outer ply of the film with a melt of a further thermoplastic composition (Z2), and then cooling to form the carrier, wherein the thermoplastic composition (Z) A) at least 95.0% by weight of an aromatic polycarbonate having a phenol OH content of 230 ppm to 1500 ppm, B) 0% to 5.0% by weight of at least one polymer additive, and contains, The further thermoplastic composition (Z2) may be the same as or different from the thermoplastic composition (Z). process, and (ii) creating a gap by expanding the cavity of the mold, or introducing the carrier into a second cavity of the mold having a hollow mold dimension larger than the first cavity to create a gap, wherein in case (ib), the carrier is oriented such that the outer ply of the film composed of the thermoplastic composition (Z) faces the gap; (iii) injecting a reactive polyurethane raw material mixture containing at least one polyisocyanate component, at least one polyfunctional active hydrogen compound, optionally at least one polyurethane additive and / or processing aid, into the gap between the carrier and the mold surface, such that the polyurethane raw material mixture polymerizes to provide a dense polyurethane layer or a polyurethane foam layer in contact with the surface of the carrier; (iv) demolding the composite member from the mold cavity; and comprising.

[0015] It is obvious to a person skilled in the art that step (i) is divided into two alternative sub-steps (ia) or (ib). All descriptions relate to either step (i) without sub-division or step (i) with sub-division into steps (ia) and (ib). It is also obvious to a person skilled in the art that the thermoplastic composition containing the phenolic OH content in the proportion of the present invention is generally referred to as "thermoplastic composition" and / or also as "thermoplastic composition (Z)". There is no difference in this regard in this specification. However, when step (i) includes step (ib), a further thermoplastic composition, also referred to as "thermoplastic composition (Z2)", may be used and thus should be distinguished. According to the present invention, the thermoplastic composition (Z2) may be the same as or different from the thermoplastic composition (Z).

[0016] According to the present invention, it is preferable that steps (i) to (iv) of the method are continuous without interruption. However, in this case, steps (i), (ii) and / or (iii) of the method, preferably steps (ii) and (iii), may be carried out several times (not necessarily). When step (i) of the method is carried out two or more times, in the second step and optionally in each further step (i) of the method, the thermoplastic composition used is preferably different from the thermoplastic composition (Z) of the first step (i) of the method. However, the carrier material obtained from step (i) and coming into direct contact with the polyurethane raw material mixture in step (iii) of the method must be the thermoplastic composition (Z) according to the invention having a defined phenolic OH content. By the continuous steps (i) to (iv) of the method without interruption, the temperature of the workpiece is prevented from cooling down to room temperature during the method. Thereby, a shortening of the production time and a higher energy efficiency of the whole method are achieved.

[0017] Steps (ii) and (iii) of the method may be repeated at least once with variation of the polyurethane system to apply one or more polyurethane layers on only one side or both sides of the carrier, optionally resulting in a composite member composed of a thermoplastic carrier and at least two identical or different PU components having a configuration of three or more layers. It will be apparent to those skilled in the art that when steps (ii) and (iii) of the method are repeated, at least the second polyurethane layer is no longer in direct contact with the support at that time.

[0018] A gap is created in step (ii) of the method. The term "gap" is understood by those skilled in the art. This term preferably describes a cavity that is sealed off from the environment and thus does not allow material leakage. To create a gap in step (ii) of the method, the injection mold is opened and then one half of the injection mold cavity is replaced with a new half having a larger hollow mold dimension, or the component is moved from the first mold cavity to a second cavity in the same mold or a second mold having a larger hollow mold dimension, or the first cavity can be opened by the gap width. Thus, step (ii) of the method includes creating a gap by expanding the mold cavity or introducing the carrier into a second cavity of the mold having a hollow mold dimension larger than the first cavity to create a gap. Step (ii) of the method preferably includes creating a gap by introducing the carrier into a second cavity of the mold having a hollow mold dimension larger than the first cavity. When performing step (ib) of the method according to the present invention, it is obvious to those skilled in the art that in step (ii) of the method, the carrier from step (i) is oriented such that the outer ply of the film composed of the thermoplastic composition (Z) faces the gap. This is obvious because the improvement in composite adhesion found according to the present invention is only achievable in this way. For this, the thermoplastic composition (Z) and the polyurethane layer need to be in direct contact. Thus, those skilled in the art recognize how the carrier of step (ib) of the method must be oriented with respect to the gap into which the reactive polyurethane raw material mixture is injected.

[0019] The movement of the substrate in step (ii) of the method can be carried out by known methods used, for example, in multi-color injection molding. Typical methods are movement using a turntable, turning plate, sliding cavity or index plate, or equivalent methods where the substrate remains on the core. When the substrate to be moved remains on the core, there is the advantage that its position is precisely defined even after replacement. On the other hand, in the prior art, methods of moving the substrate have been disclosed, for example, using a handling system to remove the substrate from a cavity and place it in another cavity. Using a movement involving removing the substrate provides greater freedom in the configuration in the coating operation, for example, in the folding of edges or the generation of mask areas. It is also possible to produce structured lacquer surfaces, and likewise, the degree of freedom in design is increased.

[0020] The method according to the invention also encompasses the possibility of providing the carrier by film insert molding known to those skilled in the art. For this purpose, in step (i) of the method, according to (ib), a film comprising an outer ply composed of the thermoplastic composition (Z) is introduced into the mold cavity, and the melt of a further thermoplastic composition (Z2) is overmolded on the side of the film opposite the outer ply of the film, and then cooled to form the carrier. Thus, using this method, a carrier is provided in a similar manner as when the melt of the thermoplastic composition (Z) is injected into the mold cavity according to (ia) in step (i) of the method and then cooled. In both cases, a carrier comprising a thermoplastic composition on at least one side is formed. According to the invention, the composition is then brought into contact with a reactive polyurethane raw material mixture. However, the carrier according to (ib) can also be formed by the layer structure of a further thermoplastic composition (Z2) and the film, so the cross-sections of the carrier according to (ia) and the carrier according to (ib) can be different.

[0021] According to the present invention, it is clear that the term "carrier" includes both classical substrates and multi-layered structures composed of a substrate and a film. The substrate differs from the multi-layered structure of the substrate and the film in that the substrate is generally formed only by injecting a melt into a mold cavity (which can also be referred to as an injection-molded component). In contrast, for the multi-layered structure of the substrate and the film, the film is first introduced into the mold cavity in an essentially solid state. To prevent slippage, it is preferably possible to fix the film by using a vacuum, an electrostatic charge, or mechanically anchoring it within the mold cavity. It is not excluded that the film undergoes at least partial deformation during the process of the method according to the invention (for example due to a temperature increase). Subsequently, a further thermoplastic composition is overmolded onto this film and cooled, whereby the thermoplastic composition forms the actual substrate of the multi-layered structure comprising the substrate and the film. However, according to the present invention, the substrate and the multi-layered structure composed of the substrate and the film are preferably defined at the boundary upon introduction into the initial mold cavity. In the first case, a melt is introduced, while in the latter case, a solid is introduced, and subsequently, a melt is overmolded onto the solid.

[0022] The film used has an outer ply composed of a thermoplastic composition (Z). The film may be a single-ply film or a multi-ply film. In the case of a multi-ply film, at least one of the outer layers is a ply composed of the thermoplastic composition (Z). In the case of a film with only a single ply, the outer ply is the actual film, and thus, as is apparent to those skilled in the art, particularly in relation to achieving better composite adhesion, orientation, i.e., which side of the film to overmold, becomes unnecessary. The film may also be composed of plies containing the thermoplastic composition (Z). According to the present invention, it is preferable that the ply be understood as a molded article whose planar extent is many times its thickness. The surface of the film may be further structured. Unless otherwise specified, the structured surface is also referred to as a ply. The film may include at least one ply.

[0023] The film used may preferably be at least partially coated on at least one side. However, it is apparent to those skilled in the art that this coating is in direct contact with / directly contacts a further thermoplastic composition (Z2) on the condition that it does not contain the thermoplastic composition (Z) used according to the present invention. Such a coating of the film generally represents the side opposite to the outer ply of the film in step (ib) of the method. The coating of the film can be carried out by screen printing, by vacuum, or by other known coating techniques. Paints, metals, etc. can be used as coating materials. According to the present invention, it is equally possible to use a film composite. The simplest embodiment is a three-layer structure composed of a plastic film, for example a metal film, and then another plastic film. The advantage of such a structure is that the coating is protected. At least one of the outer plies of the film is composed of the thermoplastic composition (Z) used according to the present invention.

[0024] The method according to the invention is preferably characterized in that, at least at one point, the wall thickness of the carrier is from 0.5 mm to 10 mm, preferably from 1 mm to 9 mm, particularly preferably from 1.5 mm to 6.5 mm, very preferably from 2 mm to 5 mm.

[0025] The polyurethane can thereupon be, for example, a PU paint, a PU foam or a dense PU skin. According to the invention, all these embodiments are subsumed under the term "polyurethane layer". The thickness of the polyurethane layer produced by the method can be, for example, from 1 μm to 20 cm, preferably from 5 μm to 15 cm, particularly preferably from 10 μm to 10 cm. The method according to the invention is preferably characterized in that the layer thickness of the polyurethane layer is from 1 μm to 1500 μm, preferably greater than 1.5 mm to 10 mm, particularly preferably greater than 1 cm to 20 cm, equally preferably from 500 μm to (bis) 1 mm. In all of these configurations, the polyurethane layer may be foamed.

[0026] The reactive polyurethane raw material mixture preferably has an index of greater than 90 to less than 140, preferably greater than 100 to less than 120, particularly preferably 105 to 115. This index is the percentage ratio of the amount of isocyanate actually used to the stoichiometric amount calculated in the case of complete polyol conversion (i.e., conversion of the OH equivalent amount of the calculated amount of isocyanate groups), i.e., index = ((functionality of isocyanate × total molar amount of isocyanate) / (functionality of alcohol × total molar amount of hydroxy groups)) × 100.

[0027] In step (iii) of the method, it is preferred to heat the surface of the injection mold in contact with the thermoplastic polymer composition to a temperature in the range of 50°C to 140°C, preferably 60°C to 100°C, particularly preferably 65°C to 95°C, preferably 60°C to 85°C, particularly preferably 60°C to 80°C. Alternatively, in step (iii) of the method, it is particularly preferred to heat the surface of the injection mold in contact with the thermoplastic polymer composition to a temperature in the range of 50°C to 150°C, preferably 60°C to 140°C, particularly preferably 70°C to 130°C, preferably 80°C to 120°C, particularly preferably 90°C to 110°C. These values are particularly applicable when the carrier material contains a polycarbonate based on bisphenol A as component A). When using different copolycarbonates, those skilled in the art can correspondingly adapt the preferred temperature based on the glass transition temperature of this other (co)polycarbonate. Similarly, it is preferred to heat the surface of the injection mold in contact with the reactive polyurethane mixture in step (iii) of the method to a temperature in the range of 50°C to 160°C, preferably 70°C to 120°C, more preferably 80°C to 110°C, particularly preferably 90°C to 100°C. It is further preferred that the temperature of the mold cavity on the polyurethane side in step (iii) of the method is at least 10°C, preferably at least 15°C, particularly preferably at least 20°C higher than the temperature of the mold cavity on the carrier side (thermoplastic side). However, it is also possible to carry out step (iii) of the method without providing a temperature difference between the polyurethane side mold cavity and the carrier side mold cavity.

[0028] Similarly, it is preferred to carry out the polymerization in step (iii) of the method under high pressure. The pressure in step (iii) of the method is particularly preferably in the range of 10 bar to (bis) 150 bar, preferably 10 bar to (bis) 90 bar (10000 hPa to 90000 hPa). In step (iii) of the method, it is also preferred to introduce the reactive polyurethane of the raw material mixture using a high-pressure device or a low-pressure device. Before demolding the workpiece in steps (ii) and (iv), the workpiece is cooled until dimensional stability is achieved.

[0029] The composite member produced according to the present invention is preferably suitable for use as an interior or exterior component of a railway vehicle, an aircraft or an automobile.

[0030] Component A An aromatic polycarbonate with a suitable Component A according to the present invention can be produced from what is known in the literature or by methods known from the literature (for the production of aromatic polycarbonates, see, for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964 and German Patent Application Publication No. 1495626, German Patent Application Publication No. 2232877, German Patent Invention No. 2703376, German Patent Invention No. 2714544, German Patent Invention No. 3000610, German Patent Application Publication No. 3832396. For the production of aromatic polyester carbonates, see, for example, German Patent No. 3077934). The aromatic polycarbonate of Component A) includes not only homopolycarbonates but also copolycarbonates and / or polyester carbonates in the context of the present invention. The polycarbonate may be linear or branched in a known manner. According to the present invention, it is also possible to use a mixture of polycarbonates.

[0031] The polycarbonate or a material "based on" polycarbonate according to the present invention is a thermoplastic material preferably containing at least 50% by weight, particularly preferably at least 60% by weight, particularly preferably at least 70% by weight of polycarbonate.

[0032] Up to 80 mol%, preferably 20 mol% to 50 mol% of the carbonate groups of the polycarbonate used according to the present invention may be replaced by aromatic dicarboxylic acid ester groups. This type of polycarbonate containing not only acid radicals derived from carbonic acid but also acid radicals derived from aromatic dicarboxylic acids incorporated into the molecular chain is referred to as an aromatic polyester carbonate. In the context of the present invention, aromatic polyester carbonates are encompassed by the broader term "thermoplastic aromatic polycarbonates".

[0033] The replacement of carbonate groups by aromatic dicarboxylic acid ester groups proceeds substantially stoichiometrically and quantitatively, and thus the molar ratio of the reactants is also reflected in the final polyester carbonate. The aromatic dicarboxylic acid groups may be incorporated in either a random or a block pattern. In the context of the present invention, polyester carbonates are encompassed by the term "polycarbonates".

[0034] In the context of the present invention, the term "alkyl" or "alkyl group" preferably refers to an alkane structure from which a hydrogen atom has been removed, unless otherwise specified. The alkyl groups according to the present invention may be linear or branched. The alkyl group is of the saturated type and thus contains only single bonds between 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, 1-ethyl-2-methylpropyl, 1-ethyl-2-methylpropyl, etc. The selection of these structures may be limited when defined with different numbers of carbon atoms in the context of the present invention.

[0035] In the context of the present invention, the term "alkylene" or "alkylene group" preferably refers to a crosslinked alkane structure in which two hydrogen atoms have been removed from different carbon atoms, unless otherwise specified. In this context, the two hydrogen atoms removed from the two carbon atoms may be removed from any carbon atom within the alkane structure. This means that the two carbon atoms may or may not be adjacent. The alkylene group may be linear or branched. The alkylene group is of a saturated type. When the alkylene group contains only one carbon atom, a methylene group (-CH2-) connected to the rest of the molecule by two single bonds corresponds thereto. The alkylene group preferably includes methylene, ethylene, n-propylene, iso-propylene, 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, 1-ethyl-2-methylpropylene, 1-ethyl-2-methylpropylene, etc. The selection of these structures may be limited when the number of carbon atoms is defined differently in the context of the present invention.

[0036] In the context of the present invention, the term "alkylidene" or "alkylidene group" preferably refers to a crosslinked alkane structure in which two hydrogen atoms have been removed from the same carbon atom, unless otherwise specified. The alkylidene group preferably includes isopropylidene, n-propylidene, isoheptylidene, etc.

[0037] Preferred polyester carbonates are of formula (w): TIFF2025523890000001.tif30170(wherein A in each repeating unit is independently an aliphatic or aromatic divalent group, for example, an aromatic divalent group having 6 to 30 carbon atoms, which may contain one or more aromatic rings, may be substituted, and an aliphatic radical or alicyclic radical or alkylaryl or heteroatom having a crosslinked structure, for example, formula (wi): TIFF2025523890000002.tif30170(wherein R 6 and R 7 are independently H, C1-C 18 alkyl, C1-C 18 alkoxy, a halogen such as Cl or Br, or in each case an aryl or aralkyl which may be substituted, preferably H or C1-C 12 alkyl, particularly preferably H or C1-C8 alkyl, very particularly preferably H or methyl, and X is a single bond, -SO2-, -CO-, -O-, -S-, C1-C6 alkylene, C2-C5 alkylidene, or C5-C6-cycloalkylidene which may be substituted with C1-C6 alkyl, preferably methyl or ethyl, or C6-C 12 arylene which may optionally be fused with another heteroatom-containing aromatic ring), a group which may be contained as a structure of or, as A, an aliphatic divalent group which may be cyclic, straight-chain or branched and may have 2 to 30 carbon atoms with at least one heteroatom present therein and may contain two or more rings, for example, structure (wii): TIFF2025523890000003.tif32170 or, as A, a linear alkylene group having 2 to 22 carbon atoms, preferably 2 to 4 carbon atoms, in which at least one heteroatom may be present in between, or a branched alkylene group having 4 to 20 carbon atoms, preferably 5 to 15 carbon atoms, in which at least one heteroatom may be present in between, or a cycloalkylene group having 4 to 20 carbon atoms, preferably 5 to 15 carbon atoms, in which at least one heteroatom may be present in between and which may contain more than one ring, In each repeating unit, D independently represents A or an aromatic or alicyclic divalent group, preferably optionally substituted phenylene or optionally substituted cyclohexylene, In each repeating unit, Y may independently be cyclic, linear or branched and contains 2 to 30 carbon atoms in which at least one heteroatom may be present in between, and represents a divalent group having two or more cyclic or aromatic groups, preferably a linear aliphatic divalent group having 2 to 30 carbon atoms, a branched aliphatic divalent group having 2 to 30 carbon atoms, an alicyclic divalent group having 6 to 30 carbon atoms and containing two or more rings, or an aromatic divalent group having 6 to 30 carbon atoms, particularly preferably optionally substituted cyclohexylene, an aliphatic linear group having 2 to 18 carbon atoms or an aliphatic divalent group containing optionally substituted phenylene. It is represented by 0 < x < 1).

[0038] Particularly preferred polyester carbonates are based on the following combinations of diols and diacids: bisphenol A and sebacic acid; bisphenol A and isophthalic acid, terephthalic acid and / or phthalic acid and optionally resorcinol; isosorbide and cyclohexanedicarboxylic acid and optionally another diol or diacid.

[0039] Examples of dihydroxyaryl compounds suitable for the production of polycarbonates include, for example, hydroquinone, resorcinol, dihydroxydiphenyl, bis(hydroxyphenyl)alkane, bis(hydroxyphenyl)cycloalkane, bis(hydroxyphenyl)sulfide, bis(hydroxyphenyl)ether, bis(hydroxyphenyl)ketone, bis(hydroxyphenyl)sulfone, bis(hydroxyphenyl)sulfoxide, α,α'-bis(hydroxyphenyl)diisopropylbenzene, phthalimidine derived from an isatin derivative or a phenolphthalein derivative, and their cyclic alkylated compounds, cyclic arylated compounds and cyclic halogenated compounds or 9,9-bis(4-hydroxyphenyl)fluorene.

[0040] Preferred dihydroxyaryl compounds include 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-methylbutane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene, 9,9-bis(4-hydroxyphenyl)fluorene and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and bisphenols (I) to (III): TIFF2025523890000004.tif51170(wherein, in each case, R'represents C1-C4 alkyl, aralkyl or aryl, preferably methyl or phenyl, particularly very preferably methyl).

[0041] Particularly preferred dihydroxyaryl compounds include 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and dimethyl bisphenol A, and dihydroxyaryl compounds of formula (I), formula (II), and formula (III).

[0042] These and other suitable dihydroxyaryl compounds are described, for example, in U.S. Patent No. 3,028,635, U.S. Patent No. 2,999,825, U.S. Patent No. 3,148,172, U.S. Patent No. 2,991,273, U.S. Patent No. 3,271,367, U.S. Patent No. 4,982,014, and U.S. Patent No. 2,999,846, German Patent Application Publication No. 1,570,703, German Patent Invention No. 2,063,050, German Patent Application Publication No. 2,036,052, German Patent Application Publication No. 2,211,956, and German Patent Application Publication No. 3,832,396, French Patent Application Publication No. 1,561,518, monograph H. Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, New York 1964.

[0043] The following formula (1a): TIFF2025523890000005.tif37170 (wherein, R 5 represents hydrogen or C1-C4 alkyl, C1-C4 alkoxy, preferably hydrogen or methyl or methoxy, particularly preferably hydrogen, R 6 , R 7 , R 8 and R 9 each independently represents C6-C 12 aryl or C1-C4 alkyl, preferably phenyl or methyl, particularly methyl, Y represents a single bond, SO2, -S-, -CO-, -O-, C1-C6 alkylene, C2-C5 alkylidene, or a C6-C which may be condensed with another aromatic ring having a hetero atom12 An arylene, or a C5-C6 cycloalkylidene radical which may be mono- or polysubstituted by C1-C4 alkyl, preferably a single bond, -O-, isopropylidene, or a C5-C6 cycloalkylidene radical which may be mono- or polysubstituted by C1-C4 alkyl, represents, V represents oxygen, C2-C6 alkylene or C3-C6 alkylidene, preferably oxygen or C3 alkylene, p, q and r are each independently 0 or 1, Here, when q = 0, W is a single bond, and when q = 1 and r = 0, W represents -O-, C2-C6 alkylene or C3-C6 alkylidene, preferably -O- or C3 alkylene, When q = 1 and r = 1, W and V each independently represent C2-C6 alkylene or C3-C6 alkylidene, preferably C3 alkylene, Z represents C1-C6 alkylene, preferably C2 alkylene, o is an average number of repeating units of 10 to 500, preferably 10 to 100, m is an average number of repeating units of 1 to 10, preferably 1 to 6, particularly preferably 1.5 to 5) of dihydroxyaryl compounds used in the production of polycarbonates are also preferred.

[0044] It is likewise possible to use dihydroxyaryl compounds in which two or more siloxane blocks of the general formula (1a) are linked via terephthalic acid and / or isophthalic acid to form an ester group.

[0045] The production of copolycarbonates containing monomer units of the general formula (1a), in particular containing bisphenol A, in particular these copolycarbonates is described, for example, in WO 2015 / 052106.

[0046] It is likewise possible to use dihydroxyaryl compounds in which two or more siloxane blocks of the general formula (1a) are linked via terephthalic acid and / or isophthalic acid to form an ester group.

[0047] Polycarbonates are manufactured in a known manner from diphenols, carbonic acid derivatives, optionally chain terminators, and optionally branching agents. Polyester carbonates are manufactured by replacing part of the carbonic acid derivatives to an extent depending on the degree to which the carbonate structural units in the aromatic polycarbonate are replaced by aromatic dicarboxylic acid ester structural units with aromatic dicarboxylic acids or derivatives of dicarboxylic acids.

[0048] In the case of homopolycarbonates, only one diphenol is used, and in the case of copolycarbonates, two or more diphenols are used. The diphenols used, like all other chemicals and auxiliaries added to the synthesis, may be contaminated with impurities due to their own synthesis, handling, and storage. However, it is desirable to use raw materials of the highest possible purity.

[0049] The monofunctional chain terminators necessary for molecular weight regulation, such as phenol or alkylphenols, especially phenol, p-tert-butylphenol, isooctylphenol, cumylphenol, their chloro carbonates, or the acid chlorides of monocarboxylic acids, or mixtures of these chain terminators, are supplied to the reaction together with bisphenoxide(s), or, provided that phosgene or chloro carbonate end groups are still present in the reaction mixture, or in the case of acid chloride and chloro carbonate chain terminators, as long as the phenol end groups of the starting polymer are sufficiently available, they are added at any desired point in the synthesis. However, the chain terminator(s) are preferably added after phosgenation at a position or point in time where phosgene is no longer present but the catalyst has not yet been added, or before or in parallel with the catalyst. Any of the branching agents or mixtures of branching agents used can be added to the synthesis in the same manner, but generally they are added before the chain terminator. Typically, the compounds used are the acid chlorides of trisphenol, quaterphenol or tricarboxylic acid or tetracarboxylic acid, or mixtures of polyphenols or mixtures of acid chlorides. Some examples of compounds that can be used as branching agents and have three or more phenol hydroxyl groups include phloroglucinol, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)hepta-2-ene, 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-hydroxyphenylisopropyl)phenol, tetra(4-hydroxyphenyl)methane.

[0050] 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 any branching agent used is from 0.05 mol% to 2 mol% based on the number of moles of diphenol used in each case. All of these measures regarding the production of polycarbonate are well known to those skilled in the art. Preferred production methods for the polycarbonates used according to the present invention, including polyester carbonate, are the known interfacial method and the known melt transesterification reaction method (see, for example, WO 2004 / 063249, WO 2001 / 05866, WO 2000 / 105867, US Patent No. 5,340,905, US Patent No. 5,097,002, US Patent No. 5,717,057). The polycarbonate is preferably produced by the melt transesterification reaction method.

[0051] The acid derivatives used are preferably phosgene and optionally dicarbonyl dichloride in the former case, and diphenyl carbonate and optionally diester of dicarboxylic acid in the latter case. Catalysts, solvents, post-treatments, reaction conditions, etc. for polycarbonate production or polyester carbonate production are well described and known in both cases. The relative solution viscosity (η rel) is preferably in the range of 1.18 to 1.4, particularly preferably in the range of 1.20 to 1.32, and particularly very preferably in the range of 1.22 to 1.29 (measured with respect to a solution 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 polycarbonate and the polyester carbonate is preferably in the range of 15,000 to 35,000, more preferably in the range of 20,000 to 33,000, and particularly preferably in the range of 23,000 to 30,000. The value of Mw is determined by gel permeation chromatography calibrated against bisphenol A polycarbonate standard substances, using dichloromethane as the eluent and calibration using linear polycarbonates (composed of bisphenol A and phosgene) with known molar mass distributions from PSS Polymer Standards Service GmbH (Germany). The calibration is carried out according to the 2301-0257502-09D method (2009 edition) from Currenta GmbH & Co. OHG (Leverkusen). The eluent is dichloromethane. The column combination is a cross-linked styrene-divinylbenzene resin. Diameter of the analytical column: 7.5 mm; length: 300 mm. Particle size of the column material: 3 μm to 20 μm. Concentration of the solution: 0.2 wt%. Flow rate: 1.0 ml per minute, temperature of the solution: 30 °C, detection using a refractive index detector (RI). According to the present invention, the phenol OH content of the aromatic polycarbonate of component A is 230 ppm to 1500 ppm, preferably 260 ppm to 1300 ppm, particularly preferably 300 ppm to 1000 ppm, equally preferably 310 ppm to 800 ppm, and particularly very preferably 350 ppm to 790 ppm. It is equally preferable that the phenol OH content of the aromatic polycarbonate of component A is 240 ppm to 1400 ppm, preferably 300 ppm to 1300 ppm, particularly preferably 400 ppm to 1200 ppm, equally preferably 500 ppm to 1100 ppm, and particularly very preferably 350 ppm to 1050 ppm.

[0052] The method for determining the phenol OH content of the aromatic polycarbonate is known to those skilled in the art. As an appropriate method, 1Examples include H-NMR spectroscopy or infrared techniques. The phenol OH content is 1 preferably determined by H-NMR spectroscopy. When the aromatic polycarbonate is, for example, a polycarbonate based on bisphenol A, the content of OH end groups is determined at room temperature using a dichloromethane solvent 1 by evaluating the integral ratio of the signals determined by H-NMR spectroscopy at 6.68 ppm (two aromatic protons ortho to the phenol OH group) and 1.68 ppm (six methyl protons of the bisphenol A unit). When using (co)polycarbonates based on different bisphenols / further comonomers separate from bisphenol A, those skilled in the art are able to determine the phenol OH content.

[0053] Unless otherwise specified, the ppm values reported are based on weight.

[0054] Those skilled in the art recognize the principle by which it is possible to adjust / affect the phenol OH content of the polycarbonate. When using the interfacial method, those skilled in the art can adjust the desired concentration of phenol OH according to the present invention, for example, by the concentration of a chain terminator, or by using a special chain terminator that also contains a phenol OH group, or by reacting the terminal groups with a compound containing a phenol OH group later. When using the melt transesterification reaction method to produce polycarbonate, it is known to those skilled in the art that the catalyst used or the ratio of diaryl carbonate to bisphenol used can affect the phenol OH content. Here too, in downstream processes, it is possible to modify the polycarbonate present in the terminal groups so that a phenol OH group is specifically introduced or reacts.

[0055] The method according to the present invention is particularly characterized in that the aromatic polycarbonate as component A) has the following structures (4) to (7): TIFF2025523890000006.tif75170(wherein the phenyl ring is independently mono- or disubstituted, which may be substituted with C1-C8 alkyl, halogen, preferably C1-C4 alkyl, particularly preferably methyl, and X is a single bond, a linear or branched C1-C6 alkylene group, a C2-C 10 alkylidene group or a C5-C 10 cycloalkylidene group, preferably represents a single bond or C1-C4 alkylene, particularly preferably isopropylidene, and "---" represents the bond of structure (4) to structure (7) to the aromatic polycarbonate), and particularly preferably contains two or more. It is particularly preferred that the total amount of structural units (4) to structural units (7) is 10 ppm to 1000 ppm, preferably 50 ppm to 950 ppm, particularly preferably 80 ppm to 850 ppm.

[0056] To determine the amounts of structural units (4) to structural units (7), each polycarbonate is subjected to total hydrolysis, and the amount of the decomposition product is determined by quantitative HPLC. The decomposition product may contain structures (4a) to (7a). Structures (4a) to (7a) have been reported as examples of the use of polycarbonates containing bisphenol A (this can be achieved, for example, as follows: The polycarbonate sample is hydrolyzed under reflux using sodium methoxide. The corresponding solution is acidified and concentrated until dry. The dry residue is dissolved in acetonitrile, and the phenolic compounds of formula (4a) to formula (7a) are determined by HPLC and UV detection): TIFF2025523890000007.tif101170

[0057] As a result, the amount of the compound of formula (4a) released is 10 ppm to 800 ppm, preferably 20 ppm to 75000 ppm, particularly preferably 25 ppm to 700 ppm, and particularly preferably 30 ppm to 500 ppm.

[0058] The amount of the compound of formula (5a) released as a result is preferably 0 ppm (i.e., less than the detection limit of 10 ppm) to 100 ppm, particularly preferably 0 ppm to 80 ppm, and particularly preferably 0 ppm to 50 ppm.

[0059] The amount of the compound of formula (6a) released as a result is preferably 0 ppm (i.e., less than the detection limit of 10 ppm) to 800 ppm, more preferably 10 ppm to 700 ppm, particularly preferably 20 ppm to 600 ppm, and particularly very preferably 30 ppm to 350 ppm.

[0060] The amount of the compound of formula (7a) released as a result is preferably 0 ppm (i.e., less than the detection limit of 10 ppm) to 300 ppm, preferably 5 ppm to 250 ppm, and particularly preferably 10 ppm to 200 ppm.

[0061] Component B The composition may contain a polymer additive as component B. Intended polymer additives include, in particular, commercially available polymer additives. Preferred polymer additives for component B are flame retardants, flame retardant synergists, smoke suppression additives, dripping inhibitors, internal lubricants and external lubricants and mold release agents, flowability aids, antistatic agents, conductive additives, nucleating agents, stabilizers, antibacterial additives, abrasion resistance improving additives, IR absorbers, fluorescent brighteners, fluorescent additives, fillers and reinforcing agents, dyes and pigments, and Bronsted acidic compounds. Particularly preferred intended polymer additives are flame retardants (e.g., phosphate esters or phosphonate esters, phosphorus compounds such as phosphonatamine and phosphazenes or halogen compounds), flame retardant synergists (e.g., nanoscale metal oxides), smoke suppression additives (e.g., boric acid or borate salts), dripping inhibitors (e.g., compounds of the substance class of fluorinated polyolefins, silicones and aramid fibers), internal lubricants and external lubricants and mold release agents (e.g., pentaerythritol tetrastearate, stearyl stearate, montan wax or polyethylene wax), flowability aids (e.g., low molecular weight vinyl (co)polymers), antistatic agents (e.g., block copolymers of ethylene oxide and propylene oxide, other polyethers or polyhydroxyethers, polyetheramides, polyesteramides or sulfonates), conductive additives (e.g., conductive carbon black or carbon nanotubes), nucleating agents, stabilizers (e.g., UV / light stabilizers, thermal stabilizers, antioxidants, transesterification inhibitors, hydrolysis stabilizers), antibacterial additives (e.g., silver or silver salts), abrasion resistance improving additives (e.g., silicone oil or hard fillers, e.g., (hollow) ceramic beads), IR absorbers, fluorescent brighteners, fluorescent additives, fillers and reinforcing agents (e.g., talc, optionally powdered glass or carbon fibers, (hollow) glass or ceramic beads, mica, kaolin, CaCO3 and glass flakes), and dyes and pigments (e.g., carbon black, titanium dioxide or iron oxide), impact resistance improvers, and Bronsted acidic compounds as base scavengers, or mixtures of a plurality of the above additives.

[0062] According to the present invention, the weight percentages specified for the thermoplastic composition should be understood as being relative to the total weight of the thermoplastic composition. The thermoplastic composition preferably contains at least 95.0% by weight of component A) and more than 0% to 5.0% by weight of component B), particularly preferably at least 95.0% by weight of component A) and 0.01% to 5.0% by weight of component B), and very particularly preferably at least 96.0% by weight of component A) and 0.05% to 4.0% by weight of component B). The thermoplastic composition is preferably substantially composed of component A) and component B). It is particularly preferred that the thermoplastic composition is composed of component A) and component B).

[0063] It is preferable to use at least one heat stabilizer as component B) in the thermoplastic composition. Suitable heat stabilizers are, in particular, phosphorus-based stabilizers selected from the group of phosphates, phosphites, phosphonites, phosphines and mixtures thereof. Examples include tris(isooctyl) phosphate, triphenyl phosphite, diphenylalkyl phosphite, phenyldialkyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite (Irgafos 168), diisodecyl pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis(2,4-dicumylphenyl) pentaerythritol diphosphite (Doverphos S-9228), bis(2,6-di-tert-butyl-4-methylphenyl) pentaerythritol 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-dibenzo[d,g]-1,3,2-dioxaphosphocin, bis(2,4-di-tert-butyl-6-methylphenyl) methyl phosphite, bis(2,4-di-tert-butyl-6-methylphenyl) ethyl phosphite, 6-fluoro-2,4,8,10-tetra-tert-butyl-12-methyl dibenzo[d,g]-1,3,2-dioxaphosphocin, 2,2',2''-nitrilo[triethyl tris(3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,2'-diyl) phosphite], 2-ethylhexyl (3,3',5,5'-tetra-tert-butyl-1,1'-biphenyl-2,Examples of the heat stabilizer include 2'-diyl phosphite, 5-butyl-5-ethyl-2-(2,4,6-tri-tert-butylphenoxy)-1,3,2-dioxaphosphirene, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, triphenylphosphine (TPP), trialkylphenylphosphine, bisdiphenylphosphinoethane, or trinaphthylphosphine. The heat stabilizer is used alone or as a mixture, for example, Irganox B900 (a mixture of Irgafos 168 and Irganox 1076 in a ratio of 4:1) or a mixture of Doverphos S-9228 and Irganox B900 or Irganox 1076. It is particularly preferred to use triphenylphosphine (TPP), tris(isooctyl) phosphate, Irgafos 168, or tris(nonylphenyl) phosphite, or a mixture thereof. The heat stabilizer is preferably used in an amount of up to 1.0% by weight, more preferably 0.003% to 1.0% by weight, even more preferably 0.005% to 0.5% by weight, and particularly preferably 0.01% to 0.2% by weight. TPP is particularly preferably used in an amount of 0% to 0.1% by weight, particularly preferably 0.05% to 0.08% by weight, and very particularly preferably 0.01% to 0.05% by weight. The phosphite-based stabilizer is also preferably used in an amount of 0.01% to 0.1% by weight, particularly preferably 0.015% to 0.09% by weight, and particularly preferably 0.02% to 0.08% by weight.,

[0064] Phenolic antioxidants such as alkylated monophenols, alkylated thioalkylphenols, hydroquinones and alkylated hydroquinones can also be used. It is particularly preferred to use Irganox 1010 (pentaerythritol-3-(4-hydroxy-3,5-di-tert-butylphenyl)propionate; CAS: 6683-19-8) and Irganox 1076 (octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate). These are preferably used in amounts of 0.001% to 0.5% by weight, particularly preferably 0.0025% to 0.1% by weight, and very particularly preferably 0.005% to 0.04% by weight.

[0065] Particularly suitable UV absorbers are hydroxybenzotriazoles, for example, 2-(3’,5’-bis(1,1-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-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol (Tinuvin™ 1577, BASF SE, Ludwigshafen), 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methylphenol (Tinuvin™ 326, BASF SE, Ludwigshafen), and benzophenones, for example, 2,4-dihydroxybenzophenone (Chimassorb™ 22, BASF SE, Ludwigshafen) and 2-hydroxy-4-(octyloxy)benzophenone (Chimassorb™ 81, BASF SE, Ludwigshafen), 2,2-bis[[(2-cyano-1-oxo-3,3-diphenyl-2-propenyl)oxy]methyl]-1,3-propanediyl ester (9CI) (Uvinul 3030, BASF SE, Ludwigshafen), 2-[2-hydroxy-4-(2-ethylhexyl)oxy]phenyl-4,6-di(4-phenyl)phenyl-1,3,5-triazine (Tinuvin™ 1600, BASF SE, Ludwigshafen), tetraethyl 2,2’-(1,4-phenylenedimethylene)bis malonate (Hostavin B-Cap, Clariant AG) or N-(2-ethoxyphenyl)-N’-(2-ethylphenyl)ethanediamide (Tinuvin™ 312, CAS No. 23949-66-8, BASF SE, Ludwigshafen).

[0066] When a UV absorber is present, the composition preferably contains the UV absorber in an amount of at most 0.8% by weight, preferably 0.05% to 0.5% by weight, more preferably 0.08% to 0.4% by weight, and particularly very preferably 0.1% to 0.35% by weight, based on the total composition.

[0067] Suitable release agents include, in particular, pentaerythritol tetrastearate (PETS) and glycerol monostearate (GMS). When a release agent is present, the composition preferably contains it in an amount of at most 0.8% by weight, preferably 0.05% to 0.5% by weight, more preferably 0.08% to 0.4% by weight, and particularly very preferably 0.1% to 0.35% by weight, based on the total amount of the composition.

[0068] The thermoplastic composition contains at least one hydroxyl component (I) as component B) in any ratio, and the hydroxyl component (I) contains at least 3 carbon atoms and at least 3 hydroxyl groups, and at least one of these at least 3 hydroxyl groups is, in each case, an aliphatic saturated or unsaturated straight-chain, cyclic or branched C1-C 32 It has been particularly proven to be advantageous that it is esterified with a carboxylic acid or benzoic acid and at least one of these at least 3 hydroxyl groups is in the form of a free hydroxyl group. Needless to say, in this case, other component B) may be present.

[0069] Surprisingly, as a result of the additional use of a special hydroxyl component on the carrier material, it has been found that the improved composite adhesion is further improved. However, the special hydroxyl component accumulates mainly on the surface of the carrier. Therefore, the bulk properties of the carrier are hardly affected by the use of additional additives. The composite shows further improvement, in particular, compared to a system which is equivalent but does not contain an additive in which the polycarbonate of component A) has at least one hydroxyl group, preferably does not contain the special hydroxyl component (I). Without wishing to be bound by theory, the special hydroxyl component (I) is assumed to be able to act as an adhesion promoter due to its chemical nature. The hydrophilic OH groups, and optionally, if present, also the hydrophobic hydrocarbon chains (especially in the case of long chains) accumulate on the surface of the carrier during and / or after the formation of the carrier. At the same time, the hydrophobic hydrocarbon groups provide a firm anchoring within and on the carrier material (especially long-chain hydrocarbons entangle in a manner known to those skilled in the art with the carrier material, and thus a bond that can withstand stress is formed even without the formation of a covalent bond). The mobility, and thus the tendency for surface accumulation, can in this case be affected with respect to the carrier, for example by the cooling method. The higher the temperature of the melt remains, the greater the molecular mobility. The temperature of the melt can be affected, for example, by the influence of an increase in the overall melt temperature or the mold temperature in the process. This surface accumulation also has the effect that the special hydroxyl component is depleted in the bulk of the carrier material at the same time. Therefore, the hydroxyl component hardly affects the bulk properties of the carrier. This also has the effect, secondly, that the amount of the hydroxyl component can be minimized since the hydroxyl component is only efficiently utilized if necessary. This further reduces costs.

[0070] Without wishing to be bound by theory, it is assumed in particular that other additional OH groups present on the surface of the formed carrier are available for reaction with the components of the polyurethane raw material mixture. A good bond is provided by combining the covalent bond between the polycarbonate and the polyurethane and the more flexible bond which is firmly anchored to the carrier material between the reacted hydroxyl compound and the polyurethane.

[0071] The hydroxyl component (I) has the structural formula (I): (R4-C(=O)O) o -(R5) x -(OH) p (I) (wherein each R4 is independently an aliphatic saturated or unsaturated, straight-chain, cyclic or branched C1-C 31 alkyl radical or phenyl, R5 is a straight-chain, cyclic or branched alkylene group having x carbon atoms, x is from 3 to 12, preferably from 3 to 8, particularly preferably from 3 to 7, and very particularly preferably from 3 to 5, and each of these carbon atoms present in R5 may contain the substituent (R4-C(=O)O) o -, -(OH) p and / or hydrogen or an alkyl radical), o is a number from 1 to 12, p is a number from 1 to 12, provided that o + p is from 2 to 12, and the maximum o + p is determined by the maximum number x of carbon atoms in R5) is preferably represented by

[0072] It is clear to the person skilled in the art that formula (I) has only as many substituents as the valency of carbon has. If the branched-chain R5-alkylene group contains, for example, at least one tertiary carbon, this tertiary carbon atom thus leaves at most only one valency for one of the substituents R4-C(=O)O) o -, -(OH) p and / or hydrogen. The branched-chain R5-alkylene group may likewise have a quaternary carbon atom which has no valency for further substituents.

[0073] The hydroxyl component (I) has the structural formula (Ia) or (Ib): TIFF2025523890000008.tif34170(wherein each R4 is independently hydrogen, aliphatic saturated or unsaturated, straight-chain, cyclic or branched C1-C 31is an alkyl radical or phenyl, where at least one R4 is hydrogen and at least one R4 is aliphatic saturated or unsaturated, straight-chain, cyclic or branched C1-C 31 is an alkyl radical or phenyl, provided that each Y independently represents hydrogen, an alkyl radical or an aryl radical, Z represents hydrogen, an alkyl radical or OR4) TIFF2025523890000009.tif32170(wherein each R4 independently represents hydrogen, aliphatic saturated or unsaturated, straight-chain, cyclic or branched C1-C 31 is an alkyl radical or phenyl, where at least one R4 is hydrogen and at least one R4 is aliphatic saturated or unsaturated, straight-chain, cyclic or branched C1-C 31 is an alkyl radical or phenyl, provided that each Y independently represents hydrogen, an alkyl radical or an aryl radical, Z represents hydrogen or an alkyl radical, x is a number from 3 to 12, preferably from 3 to 8, particularly preferably from 3 to 7, and very particularly preferably from 3 to 5) is likewise preferred.

[0074] In structural formula (I) or structural formula (Ib), x particularly preferably represents from 3 to 5.

[0075] Each R4 in Structural Formula (I), Structural Formula (Ia) or Structural Formula (Ib) is independently methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, n-pentyl, 1-methylbutyl, 2-methylbutyl, 3-methylbutyl, neopentyl, 1-ethylpropyl, cyclohexyl, cyclopentyl, n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl, 2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, 1-ethyl-2-methylpropyl, 1-ethyl-2-methylpropyl, n-heptyl, n-octyl, pinacyl, adamantyl, menthyl isomers, n-nonyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl, and it is particularly preferred that each R4 in Structural Formula (I), Structural Formula (Ia) or Structural Formula (Ib) independently represents n-nonyl, n-decyl, n-dodecyl, n-tridecyl, n-tetradecyl, n-hexadecyl or n-octadecyl.

[0076] Particularly preferably in combination with the above definitions for R4, it is also equally preferred that each Y in Structural Formula (I), Structural Formula (Ia) or Structural Formula (Ib) independently represents hydrogen, methyl, ethyl, propyl, butyl or phenyl. Component B) is particularly preferably glycerol monostearate.

[0077] The thermoplastic composition preferably contains 0.0001% to 5% by weight, particularly preferably 0.001% to 1% by weight, particularly very preferably 0.01% to 0.8% by weight, and most preferably 0.02% to 0.06% by weight of the hydroxyl component (I). These amounts are small enough to ensure the effect of improving the composite adhesiveness while hardly changing the bulk properties of the carrier.

[0078] Component B) preferably contains a phosphite and / or phosphate, particularly preferably at least one stabilizer from one of the groups of the above-mentioned compounds, at least one release agent, at least one UV absorber, at least one phenolic antioxidant and optionally a dye (organic) and / or a pigment (organic and inorganic).

[0079] Component B) contains TPP in an amount of 0 wt% to 0.1 wt%, particularly preferably 0.05 wt% to 0.08 wt%, very particularly preferably 0.01 wt% to 0.05 wt%, and contains at least one stabilizer from the group of phosphites and / or phosphates in an amount of 0.01 wt% to 0.1 wt%, particularly preferably 0.015 wt% to 0.09 wt%, particularly preferably 0.02 wt% to 0.08 wt%, contains at least one UV absorber in an amount of at most 0.8 wt%, preferably 0.05 wt% to 0.5 wt%, more preferably 0.08 wt% to 0.4 wt%, very particularly preferably 0.1 wt% to 0.35 wt%, and contains at least one release agent in an amount of at most 0.8 wt%, preferably 0.05 wt% to 0.5 wt%, more preferably 0.08 wt% to 0.4 wt%, very particularly preferably 0.1 wt% to 0.35 wt%.

[0080] Further thermoplastic composition (Z2) by step (ib) of the method In step (ib) of the method, the film is overmolded with a further thermoplastic composition (Z2), where the further thermoplastic composition (Z2) may be the same as or different from the thermoplastic composition (Z). The further thermoplastic composition (Z2) may contain the above components A) and B) in all preferred forms and / or combinations. However, the material of the thermoplastic composition (Z2) is not limited, and it can be adapted and selected based on the properties required for the intended use, provided that the composition is thermoplastic. The adhesiveness between this further thermoplastic composition (Z2) and the film is also very important, and it is obvious to those skilled in the art that it can be optimized. This is within the scope of the knowledge and capabilities of those skilled in the art.

[0081] Polyurethane The coating used is preferably a foamed polyurethane or a dense polyurethane layer.

[0082] The polyurethane used according to the present invention is obtained by reacting a polyisocyanate with a polyfunctional compound having active hydrogen (H-active), preferably a polyol. In the context of the present invention, the term "polyurethane" should be understood to also mean polyurethane urea in which a compound having an NH functionality is used as a polyfunctional compound having active hydrogen, optionally in a mixture with a polyol.

[0083] Suitable polyisocyanates are aromatic, araliphatic, aliphatic or cycloaliphatic polyisocyanates having an NCO functionality preferably of two or more, which are known per se to those skilled in the art and may also contain iminooxadiazinedione, isocyanurate, uretdione, urethane, allophanate, biuret, urea, oxadiazinetrione, oxazolidinone, acylurea and / or carbodiimide structures. These can be used individually or as any desired mixture with each other.

[0084] The above polyisocyanate is based on diisocyanates and / or triisocyanates having isocyanate groups bonded aliphatically, cycloaliphatically, araliphatically and / or aromatically, which are known per se to those skilled in the art, and it is not important whether it is produced using phosgene or by a phosgene-free method.Examples of such diisocyanates or triisocyanates are 1,4-diisocyanatobutane, 1,5-diisocyanatopentane, 1,6-diisocyanatohexane (HDI), 2-methyl-1,5-diisocyanatopentane, 1,5-diisocyanato-2,2-dimethylpentane, 2,2,4-trimethyl-1,6-diisocyanatohexane and 2,4,4-trimethyl-1,6-diisocyanatohexane, 1,10-diisocyanatodecane, 1,3-diisocyanatocyclohexane and 1,4-diisocyanatocyclohexane, 1,3-bis(isocyanatomethyl)cyclohexane and 1,4-bis(isocyanatomethyl)cyclohexane, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethylcyclohexane (isophorone diisocyanate, IPDI), 4,4'-diisocyanatodicyclohexylmethane (Desmodur® W, Covestro AG, Leverkusen, Germany), 4-isocyanatomethyl-1,8-octanediisocyanate (triisocyanatononane, TIN), ω,ω'-diisocyanato-1,3-dimethylcyclohexane (H6XDI), 1-isocyanato-1-methyl-3-isocyanatomethylcyclohexane, 1-isocyanato-1-methyl-4-isocyanatomethylcyclohexane, bis(isocyanatomethyl)norbornane, 1,5-naphthalenediisocyanate, 1,3-bis(2-isocyanatoprop-2-yl)benzene and 1,4-bis(2-isocyanatoprop-2-yl)benzene (TMXDI), 2,4-diisocyanatotoluene and 2,6-diisocyanatotoluene (TDI), in particular the 2,4 isomer and the 2,6 isomer, and technical mixtures of these two isomers, 2,4'-diisocyanatodiphenylmethane and 4,4'-diisocyanatodiphenylmethane (MDI), polymeric MDI (pMDI), 1,5-diisocyanatonaphthalene, 1,3-bis(isocyanatomethyl)benzene (XDI), and any desired mixture of the listed compounds.

[0085] The polyisocyanate has an average NCO functionality of 2.0 to 5.0, preferably 2.2 to 4.5, particularly preferably 2.2 to 2.7, and the isocyanate group content is preferably 5.0% by weight to 37.0% by weight, preferably 14.0% by weight to 34.0% by weight.

[0086] In a preferred embodiment, the above-described type of polyisocyanate or polyisocyanate mixture having only aliphatically and / or cycloaliphatically bonded isocyanate groups is used.

[0087] The above-described type of polyisocyanate is particularly preferably based on hexamethylene diisocyanate, isophorone diisocyanate, isomer bis(4,4'-isocyanatocyclohexyl)methane, and mixtures thereof.

[0088] Higher molecular weight modified polyisocyanates, in particular terminal isocyanate-containing prepolymers in the molecular weight range from 400 to 15,000, preferably from 600 to 12,000, known from polyurethane chemistry, are of interest. These compounds are prepared in a manner known per se by reaction of an excess of simple polyisocyanates of the type described by way of example with organic compounds having at least two isocyanate-reactive groups, in particular organic polyhydroxyl compounds. Suitable polyhydroxyl compounds of this type include not only simple polyhydric alcohols in the molecular weight range from 82 to 599, preferably from 62 to 200, such as ethylene glycol, trimethylolpropane, 1,2-propanediol or 1,4-butanediol or 2,3-butanediol, but in particular polyether polyols and / or polyester polyols of high molecular weight of a type known per se from polyurethane chemistry having a molecular weight of 600 to 12,000, preferably 800 to 4000, and having at least two, generally from 2 to 8, preferably from 2 to 6 primary hydroxyl groups and / or secondary hydroxyl groups. It will be understood that it is also possible to use, for example, NCO prepolymers prepared from low molecular weight polyisocyanates of the type described by way of example, and compounds having less preferred isocyanate-reactive groups, such as polythioether polyols, hydroxyl-containing polyacetals, polyhydroxy polycarbonates, hydroxyl-containing polyester amides or hydroxyl-containing copolymers of olefinically unsaturated compounds.

[0089] Compounds having isocyanate-reactive groups, especially hydroxyl groups, suitable for the production of NCO prepolymers are, for example, the compounds disclosed in U.S. Patent No. 4,218,543. During the production of the NCO prepolymer, these compounds having isocyanate-reactive groups are reacted with simple polyisocyanates of the type exemplified above while maintaining an NCO excess. The NCO content of the NCO prepolymer is generally from 10% to 26% by weight, preferably from 15% to 26% by weight. In the context of the present invention, the terms "NCO prepolymer" and "prepolymer having terminal isocyanate groups" are understood to mean both such reaction products and mixtures with an excess of unconverted starting polyisocyanate, often also known as "semi-prepolymers", as is clear from the above.

[0090] Intended aliphatic diols having an OH number of more than 500 mg KOH per gram are chain extenders customarily used in crosslinking in polyurethane chemistry, for example, ethylene glycol, diethylene glycol, propylene glycol, dipropylene glycol, 1,4-butanediol, 1,3-propanediol. Diols such as 2-1,4-butanediol, 1,3-butanediol, 2,3-butanediol and / or 2-methyl-1,3-propanediol are preferred. It will be understood that it is also possible to use aliphatic diols as mixtures with one another.

[0091] Examples of components having appropriate active hydrogen include polyols having an average OH number of 5 mg to 600 mg of KOH per gram and an average functionality of 2 to 6. Polyols having an average OH number of 10 mg to 50 mg of KOH per gram are preferred. Examples of suitable polyols according to the present invention include polyhydroxy polyethers obtainable by alkoxylation of suitable starter molecules such as ethylene glycol, diethylene glycol, 1,4-dihydroxybutane, 1,6-dihydroxyhexane, dimethylolpropane, glycerol, pentaerythritol, sorbitol or sucrose. Ammonia or amines such as ethylenediamine, hexamethylenediamine, 2,4-diaminotoluene, aniline or amino alcohols or phenols such as bisphenol A are likewise suitable as starters. The alkoxylation is carried out using propylene oxide and / or ethylene oxide or as a mixture in any desired order. In addition to the polyol, at least one further crosslinking agent and / or chain extender selected from the group consisting of amines and amino alcohols such as ethanolamine, diethanolamine, diisopropanolamine, ethylenediamine, triethanolamine, isophoronediamine, N,N'-dimethyl(diethyl)ethylenediamine, 2-amino-2-methyl(or ethyl)-1-propanol, 2-amino-1-butanol, 3-amino-1,2-propanediol, 2-amino-2-methyl(ethyl)-1,3-propanediol, and alcohols such as ethylene glycol, diethylene glycol, 1,4-dihydroxybutane, 1,6-dihydroxyhexane, dimethylolpropane, glycerol and pentaerythritol, and sorbitol and sucrose or mixtures of these compounds can be further used.

[0092] Polyester polyols such as those obtainable by reaction of a low molecular weight alcohol with a polybasic carboxylic acid, for example adipic acid, phthalic acid, hexahydrophthalic acid, tetrahydrophthalic acid or the anhydrides of these acids, in a manner known per se, are also suitable, provided that the viscosity of the component having active hydrogen does not become excessively high. A preferred polyol containing an ester group is ricinoleic acid. Also suitable are preparations containing castor oil, such as those obtainable by dissolving a resin, for example an aldehyde-ketone resin, and also by modifying castor oil, and polyols based on other natural oils.

[0093] Also suitable are higher molecular weight polyhydroxy polyethers in which a higher molecular weight adduct or polycondensate or polymer is present in finely dispersed form, dissolved form or grafted form. Such modified hydroxyl compounds can be obtained in a manner known per se, for example when an addition reaction (for example the reaction of a polyisocyanate with an amino-functional compound) or a polycondensation reaction (for example the reaction of formaldehyde with phenol and / or an amine) can occur in situ in the hydroxyl-containing compound. However, it is also possible to mix an immediately usable aqueous polymer dispersion with the polyhydroxyl compound and then remove the water from the mixture.

[0094] Also suitable for the production of polyurethanes are hydroxyl compounds modified with vinyl polymers, such as those obtainable by polymerization of styrene and acrylonitrile in the presence of, for example, a polyether or a polycarbonate polyol. Plastics having specific flame retardancy are obtained by using polyether polyols modified by graft polymerization according to German Patent Application Publication Nos. 2442101, 2844922 and 2646141 using vinyl phosphonic acid esters and optionally (meth)acrylonitrile, (meth)acrylamide or OH-functional (meth)acrylic acid esters.

[0095] Typical compounds described as being used as compounds having active hydrogen are, for example, described 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.

[0096] It is also possible to use a mixture of the described compounds.

[0097] The limitation on the average OH number and average functionality of the components having active hydrogen is particularly due to an increase in the embrittlement of the resulting polyurethane. However, those skilled in the art generally recognize the possibility of affecting the polymer physical properties of the polyurethane, and thus, the NCO component, aliphatic diol, and polyol can be favorably adapted to each other.

[0098] The polyurethane layer (b) may be in the form of a foam or a solid, for example, in the form of a paint or a coating.

[0099] All auxiliaries and additives known per se, such as release agents, blowing agents, fillers, catalysts, and flame retardants, can be used in its production.

[0100] Examples of those optionally usable as auxiliaries and additives include: a) Water and / or volatile inorganic or organic substances as blowing agents Suitable organic blowing agents include, for example, halogenated alkanes such as acetone, ethyl acetate, methylene chloride, chloroform, ethylidene chloride, vinylidene chloride, monofluorotrichloromethane, chlorodifluoromethane, dichlorodifluoromethane, and in addition butane, hexane, heptane or diethyl ether. Suitable inorganic blowing agents include air, CO2 or N2O. The foaming effect can also be achieved by adding compounds that decompose upon discharging a gas, such as nitrogen, at a temperature exceeding room temperature, for example, azo compounds such as azodicarbonamide or azoisobutyronitrile.

[0101] b) Catalyst The catalyst is, for example, tertiary amines (e.g., triethylamine, tributylamine, N-methylmorpholine, N-ethylmorpholine, N,N,N’,N’-tetramethylethylenediamine, pentamethyldiethylenetriamine and higher homologs, 1,4-diazabicyclo-(2,2,2)octane, N-methyl-N’-dimethylaminoethylpiperazine, bis(dimethylaminoalkyl)piperazine, N,N-dimethylbenzylamine, N,N-dimethylcyclohexylamine, N,N-diethylbenzylamine, bis(N,N-diethylaminoethyl)adipate, N,N,N’,N’-tetramethyl-1,3-butanediamine, N,N-dimethyl-β-phenylethylamine, 1,2-dimethylimidazole, 2-methylimidazole), monocyclic and bicyclic amides, bis(dialkylamino)alkyl ethers, tertiary amines containing an amide group (preferably a formamide group), Mannich bases composed of secondary amines (such as dimethylamine) and aldehydes (preferably formaldehyde or ketones such as acetone, methyl ethyl ketone or cyclohexanone) and phenols (such as phenol, nonylphenol or bisphenol), Tertiary amines containing isocyanate-active hydrogen atoms (e.g., triethanolamine, triisopropanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N,N-dimethylethanolamine) and reaction products thereof with alkylene oxides, such as propylene oxide and / or ethylene oxide, Secondary / tertiary amines, Silaamines having a carbon-silicon bond (2,2,4-trimethyl-2-silamorpholine and 1,3-diethylaminomethyltetramethyldisiloxane), Nitrogen-containing bases (such as tetraalkylammonium hydroxide, etc.), Alkali metal hydroxides (e.g., alkali metal phenoxides such as sodium hydroxide, sodium phenoxide, etc.), Alkali metal alkoxides (such as sodium methoxide, etc.), and / or, Hexahydrotriazine.

[0102] The reaction of the NCO group with the Zerewitinoff active hydrogen atom is also significantly accelerated in a known manner by lactams and azalactams, first by forming an adduct between the lactam and a compound containing acidic hydrogen.

[0103] Organometallic compounds, especially organotin and / or bismuth compounds, can also be used as catalysts. As organotin compounds, in addition to sulfur-containing compounds such as di-n-octyltin mercaptide, tin(II) salts of carboxylic acids, such as tin(II) acetate, tin(II) octylate, tin(II) ethylhexanoate, and tin(II) laurate, and tin(IV) compounds, such as dibutyltin oxide, dibutyltin dichloride, dibutyltin diacetate, dibutyltin dilaurate, dibutyltin maleate, or dioctyltin diacetate are preferably also contemplated. Organobismuth catalysts are described, for example, in International Publication No. WO 2004 / 000905.

[0104] It will be understood that all of the above catalysts may be used as a mixture. Combinations of organometallic compounds with amidines, aminopyridines or hydrazinopyridines are of particular interest.

[0105] The catalyst is generally used in an amount of about 0.001% to 10% by weight based on the total amount of the compound having at least two isocyanate-reactive hydrogen atoms.

[0106] c) Surface-active additives, such as emulsifiers and foam stabilizers Suitable emulsifiers are, for example, the sodium salts of castor oil sulfonic acid or salts of fatty acids and amines, such as diethylamine oleate or diethanolamine stearate. Alkali metal salts or ammonium salts of sulfonic acids, such as dodecylbenzene sulfonic acid or dinaphthylmethane disulfonic acid, or alkali metal salts or ammonium salts of fatty acids, such as ricinoleic acid, or alkali metal salts or ammonium salts of polymeric fatty acids can also be used as surface-active additives.

[0107] Suitable foam stabilizers include, in particular, polyether siloxanes, especially typical water-soluble ones. The constitution of these compounds generally involves copolymers of ethylene oxide and propylene oxide bonded to polydimethylsiloxane radicals. Particularly interesting are polysiloxane-polyoxyalkylene copolymers multiply branched via allophanate groups.

[0108] d) Reaction inhibitors Suitable reaction inhibitors are, for example, acidic substances (such as hydrochloric acid or organic acid halides, etc.).

[0109] e) Additives The intended PU additives are, for example, cell regulators of a type known per se (such as paraffin or fatty alcohol), or dimethylpolysiloxanes of a type known per se, and pigments or dyes and flame retardants (such as tris(2-chloroethyl) phosphate, tricresyl phosphate or ammonium phosphate and polyphosphates), in addition to stabilizers, plasticizers and antifungal and antibacterial substances and fillers (such as barium sulfate, diatomaceous earth, carbon black or precipitated calcium carbonate) against the effects of change over time and weathering.

[0110] Further examples of surface-active additives, foam stabilizers and cell regulators, reaction inhibitors, stabilizers, flame retardants, plasticizers, dyes and fillers and antifungal and antibacterial substances optionally used in combination according to the invention are known to the person skilled in the art and are described in the literature.

[0111] According to the invention, it is preferred to use a low-solvent reactive polyurethane raw material mixture in which the solvent content is at most 10% by weight, preferably at most 2% by weight and particularly preferably at most 1% by weight, based on the amount of the paint. It is likewise preferred to use a solvent-free reactive polyurethane raw material mixture. The presence of a solvent may cause the formation of bubbles. The solvent also increases the VOC (volatile organic compound) content in the production. Especially with regard to use in the IMC process and / or the RIM process, in these processes it is advantageous to use a low-solvent or solvent-free polyurethane raw material mixture since in these processes the reaction time is short and / or the solvent does not evaporate while the mold is closed.

[0112] It is common practice to use a paint system with a short pot life. It is preferable to select a system with a pot life of up to 1 minute, particularly preferably up to 30 seconds, and very particularly preferably up to 10 seconds. It is preferable to adapt the cycle time of the reaction of the paint system to the cycle time of injection molding. This is particularly economical. To obtain a short pot life, it is preferable to use a high-pressure countercurrent mixing head for mixing the two components. Thereby, higher productivity becomes possible compared to other methods. Furthermore, at the end of the method, no residue of the mixed paint raw material remains in the mold.

[0113] Another aspect of the present invention is produced by a two-component reaction injection molding method, a) A) at least 95.0% by weight of an aromatic polycarbonate having a phenol OH content of 230 ppm to 1500 ppm, and B) 0% to 5.0% by weight of at least one commercially available polymer additive, and a carrier composed of a thermoplastic composition containing b) at least one polyurethane layer in direct contact with the carrier, A composite member is provided. The two-component reaction injection molding method is particularly preferably the IMC method or the RIM method. It is very particularly preferably the IMC method.

[0114] It is preferable that the above components A), component B) and the above polyurethane layer in all preferred forms and combinations of preferred forms are considered herein. It is equally preferable that the composite member according to the present invention is obtained by the method according to the present invention.

[0115] The phenolic OH content of component A) with respect to the composite member is preferably based on the starting composition. It is possible that the OH content at least on the surface of the carrier may decrease due to reaction with the reactive polyurethane raw material mixture. However, it is very likely that this cannot be confirmed. This is particularly due to the fact that the reaction occurs substantially only at the interface and the polyurethane raw material mixture hardly penetrates into the carrier material. The OH content of the carrier of the finished composite member can be determined by destroying the carrier, for example, by shaving it off. This can be carried out, in particular, by the above method, preferably 1 using 1H-NMR. When using a film, it is also possible to use IR microscopy, thin sections, or polished sections.

[0116] The composite member according to the invention is in a two-component reaction injection molding process with at least one polyisocyanate component, at least one polyfunctional active hydrogen compound, optionally at least one polyurethane additive and / or processing aid, and is particularly preferably produced using a reactive polyurethane raw material mixture containing, where the index of the reactive polyurethane raw material mixture is greater than 90 and less than 140.

[0117] The composite member according to the invention is likewise preferably an interior or exterior component of a railway vehicle, aircraft or motor vehicle.

[0118] Another aspect of the invention is A) at least 95.0% by weight of an aromatic polycarbonate having a phenolic OH content of 230 ppm to 1500 ppm, B) 0% to 5.0% by weight of at least one commercially available polymer additive, Provided is the use of a composition containing [component] as a carrier material in the production of a composite member comprising a carrier by a two-component reaction injection molding method and at least one polyurethane layer in direct contact with the carrier. It is preferred that all preferred forms and combinations of preferred forms of the above component A), component B) and the above polyurethane layer are contemplated herein.

Mode for Carrying Out the Invention

Examples

[0119] Materials Used: PC1: A linear bisphenol A-based polycarbonate based on a mixture of 60% by weight of a polycarbonate having a melt volume flow rate MVR of 12 cm 3 / (10 min) (in accordance with ISO 1133:2012-03, test temperature 300 °C and load 1.2 kg) and 40% by weight of a polycarbonate having a melt volume flow rate MVR of 30 cm 3 / (10 min) (test temperature 250 °C and load 1.2 kg).

[0120] PC2: A linear bisphenol A-based polycarbonate having a melt volume flow rate MVR of 30 cm 3 / (10 min) (test temperature 250 °C and load 1.2 kg).

[0121] PC3: A linear bisphenol A-based polycarbonate having a melt volume flow rate MVR of 12 cm 3 / (10 min) (in accordance with ISO 1133:2012-03, test temperature 300 °C and load 1.2 kg).

[0122] PC4: A linear bisphenol A-based polycarbonate in powder form having a melt volume flow rate MVR of 6 cm 3 / (10 min) (in accordance with ISO 1133:2012-03, test temperature 300 °C and load 1.2 kg).

[0123] GMS: Glycerol monostearate (CAS 91052-47-0)

[0124] Reactive polyurethane raw material mixture: The polyurethane coating systems used were both mixtures of puroclear 3351 IT (polyol component) and puronat 960 / 1 (diisocyanate component) from RUEHL PUROMER GmbH, Friedrichsdorf, Germany, and the mixing ratio was 100 - 229. Puroclear 3351 IT is a polyol formulation, which, when treated with puronate 960 / 1 (HDI isocyanate component), can result in an elastomer system for light-resistant pouring 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.

[0125] Test methods used Adhesion: Adhesion was determined by the "POSI" test in accordance with DIN EN ISO 4624:2016 - 08. Method B (8.4.2), which shows the most damaged defect pattern, was used. Away from the reference, the median values of three test specimens were formed and measured 8 times in each case. The most common defect patterns were determined and reported as a table. The following are shown in Table 1: A: Poor adhesion to the substrate, A / B: Poor adhesion between the substrate and the coating, B: Poor adhesion to the coating, and Y: Poor adhesion of the adhesive.

[0126] Hydrolytic storage: The composite members were stored in a conditioning cabinet at (90 ± 2)°C and (95 ± 3)% relative humidity for 72 hours. The formation of water droplets on the component parts was avoided by properly positioning them in the conditioning cabinet. The component parts were then subjected again to the adhesion test by the "POSI" test (see above).

[0127] Phenol OH content: The content of OH end groups was measured in the area of the composite member where the paint was not applied. 1Measured by 1H-NMR spectroscopy (600 MHz) using CDCl3 as a solvent at room temperature by evaluating the integration ratio of the signal at 6.68 ppm (two aromatic protons ortho to the phenolic OH group) and the signal at 1.68 ppm (six methyl protons of the bisphenol A unit).

[0128] Production and characterization of the molding compound: The compound was produced on a ZSK25. The melt temperature was 260 °C and the rotational speed was 225 rpm. The throughput was between 17.5 kg / hour and 20 kg / hour.

[0129] Fabrication of the composite member: 286.4 cm 2 A partially surface-coated injection molded product having a protruding region of was produced in an injection molding machine using an injection mold having two cavities (a cavity on the substrate side and a coating cavity on the polyurethane side connected to the RIM system). The composite member was a sheet-like component member composed of a thermoplastic substance (carrier) whose surface was partially coated with a polyurethane skin. The coated area of the component member was 225.5 cm 2 It was. 150 cm of this area 2 served as the test area for the adhesion test. Eight measurements were performed on this test area. The wall thickness of the test area was approximately 3.2 mm for the injection molded component member and 0.5 mm for the polyurethane layer. In each case, three composite members were used for the first adhesion measurement and three composite members were used for the adhesion measurement of hydrolysis storage.

[0130] In the steps of the first method, a carrier was produced. For this purpose, as described in Table 1, the thermoplastic particles of the composition were melted in an injection molding barrel and injected into the first mold cavity of a closed mold at a temperature of 300°C. The temperature of this mold cavity was adjusted to 100°C. After the holding time and the cooling time resulting in the solidification of the carrier had elapsed, the mold was opened in the steps of the second method. The produced carrier component was held on the ejector side surface of the injection molding mold. The sliding table on the die side of the injection molding mold was shifted to position 2. In the steps of the third method, the mold was closed again, and a cavity for polyurethane coating was formed together with the carrier and the mold.

[0131] In the steps of the fourth method, two reactive components of a polyurethane coating system from a RIM system were carried into a high-pressure countercurrent mixing head, mixed therein, and then injected. The temperature of the PU side cavity was adjusted to 100°C. After the reaction time and the cooling time had elapsed, the mold was opened again in the steps of the fifth method, and the coated molded product was demolded.

[0132] Thereafter, the molded product was subjected to an adhesion test (initial adhesion). The molded product was further subjected to the above hydrolysis storage, and the adhesion was measured again (adhesion after hydrolysis). For all measurements, the same defect pattern was always observed in each case.

[0133] TIFF2025523890000010.tif82170

[0134] As is apparent from the results in Table 1, the component having a phenol OH group content according to the present invention of the thermoplastic composition of the carrier showed a good defect pattern together with high composite adhesion. The initial composite adhesion was higher for Examples 1, 2, and 5 according to the present invention, for example, than for Comparative Examples 3 and 4. At the same time, all composite members according to the present invention showed high composite adhesion after hydrolysis storage.

[0135] From Example 5, it is similarly clear that by adding a special hydroxyl component to the thermoplastic composition, the composite adhesiveness after hydrolysis storage is particularly further improved.

Claims

1. a) A carrier composed of a thermoplastic composition, b) At least one polyurethane layer in direct contact with the carrier, A method for manufacturing a composite member comprising: (i) (ia) injecting a molten thermoplastic composition (Z) into a mold cavity and then cooling to form the carrier, or (ib) introducing a film including an outer ply made of thermoplastic composition (Z) into a mold cavity, overmolding the film on the opposite side of the outer ply with a further molten thermoplastic composition (Z2), and then cooling to form the carrier, The thermoplastic composition (Z) A) Aromatic polycarbonate having a phenol OH content of 230 ppm to 1500 ppm, at least 95.0% by weight, B) At least one polymer additive in an amount of 0% to 5.0% by weight, It contains, The further thermoplastic composition (Z2) may be the same as or different from the thermoplastic composition (Z). The process, (ii) A step of creating a gap by widening the cavity of the mold, or by introducing the carrier into a second cavity of the mold, the hollow mold dimensions of which are larger than those of the first cavity, wherein in the case of (ib), the carrier is oriented such that the outer ply of the film, which is composed of the thermoplastic composition (Z), faces the gap. (iii) At least one polyisocyanate component, At least one polyfunctional active hydrogen compound, Optionally, at least one polyurethane additive and / or processing aid, A step of injecting a reactive polyurethane raw material mixture containing into the gap between the carrier and the mold surface, wherein the polyurethane raw material mixture polymerizes to provide a dense polyurethane layer or a polyurethane foam layer in contact with the surface of the carrier, (iv) A step of releasing the composite member from the mold cavity, Methods that include...

2. The method according to claim 1, characterized in that the phenol OH content of the aromatic polycarbonate, which is component A), is 310 ppm to 1100 ppm.

3. The aromatic polycarbonate, which is component A, has the following structures (4) to (7): 【Chemistry 1】 (In the formula, the phenyl ring is independently C １ ~C ８ X may be monosubstituted or disubstituted with alkyl or halogen, and X may be a single bond, a linear chain or a branched C １ ~C ６ Alkylene group, C ２ ~C １０ Alkylidene group or C ５ ~C １０ The method according to claim 1, characterized in that it includes one of the structures (4) to (7) (where "---" represents a cycloalkylidene group and "---" represents the bonding of structures (4) to (7) to the aromatic polycarbonate).

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

5. The method according to claim 1, characterized in that the wall thickness of the carrier at at least one point is 0.5 mm to 10 mm.

6. The method according to claim 1, characterized in that the thickness of the polyurethane layer is 1 μm to 20 cm.

7. The method according to claim 1, characterized in that the thermoplastic composition (Z) is composed of component A) and component B).

8. The method according to claim 1, characterized in that component B) is selected from the group consisting of at least one of the following: flame retardants, flame retardant synergists, smoke suppression additives, anti-dripping agents, internal and external lubricants and release agents, flow enhancers, antistatic agents, conductive additives, nucleating agents, stabilizers, antibacterial additives, scratch resistance improving additives, IR absorbers, fluorescent whitening agents, fluorescent additives, fillers and reinforcing agents, dyes and pigments, and Brønsted acid compounds.

9. The method according to claim 1, characterized in that a low-solvent reactive polyurethane raw material mixture is used, wherein the solvent content is up to 2% by weight relative to the amount of paint used.

10. The method according to claim 1, characterized in that a solvent-free reactive polyurethane raw material mixture is used.

11. The method according to claim 1, characterized in that the pot life of the reactive polyurethane raw material mixture is a maximum of 1 minute.

12. The method according to claim 1, characterized in that polymerization in step (iii) of the method is carried out under high pressure.

13. A product manufactured by the method described in claim 1, a) A) Aromatic polycarbonate having a phenol OH content of 230 ppm to 1500 ppm, at least 95.0% by weight, B) At least one commercially available polymer additive in an amount of 0% to 5.0% by weight, A carrier comprising a thermoplastic composition (Z) containing, b) At least one polyurethane layer in direct contact with the carrier, A composite member comprising the same components.

14. The composite member according to claim 13, characterized in that it is an interior component or exterior component of a railway vehicle, aircraft, or automobile.

15. A) Aromatic polycarbonate having a phenol OH content of 230 ppm to 1500 ppm, at least 95.0% by weight, B) At least one commercially available polymer additive in an amount of 0% to 5.0% by weight, Use of a composition containing as a carrier material in the manufacture of a composite member comprising a carrier and at least one polyurethane layer in direct contact with the carrier by a two-component reaction injection molding method.

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