Composition and method for producing a transparent thermoplastic polycarbonate / polymethyl methacrylate molding compound

Description

[0001] The present invention relates to a polycarbonate / polymethyl methacrylate composition for producing a thermoplastic polycarbonate / polymethyl methacrylate molding compound, a process for producing the molding compound, the molding compound itself, the use of the molding compound for producing molded articles, the molded articles containing such a molding compound and a process for producing molded articles.

[0002] Not least driven by the development of LED light source technology and the resulting new lighting and functional integration concepts, transparent and translucent thermoplastic molding compounds, which are suitable for the production of molded bodies that can be illuminated by visible light, have become increasingly important in many application areas, for example in the automotive sector, the construction sector and the electronics sector, in recent years.

[0003] The property profile of traditional transparent thermoplastic polymer materials such as polycarbonate (PC) and polymethyl methacrylate (PMMA) is increasingly encountering technical limitations in many of these new applications. For example, translucent components in automotive interiors, such as instrument panel supports or decorative panels, or in automotive bodywork applications intended for ambient lighting or on-demand function displays, often require improved material ductility compared to PMMA, as well as improved scratch or chemical resistance compared to PC. For the expert, it is therefore logical to use polymer blend technology to combine the individual advantages of these two materials (high scratch resistance and good chemical resistance of PMMA on the one hand, and high ductility of PC on the other).

[0004] The properties of such PC / PMMA blend molding compounds and the molded articles produced from them can be varied widely and adapted to the requirements of the respective application by appropriately selecting their composition and manufacturing conditions. This allows molding compounds with a wide range of property profiles to be realized, which often lie essentially between those of pure PC and those of pure PMMA.

[0005] However, this generally does not apply to light transmission (transparency). Since PC and PMMA melts are not completely miscible, two-phase morphologies generally form during compounding of PC / PMMA blends. In this case, the polymer used in excess forms the matrix phase, within which the other polymer is relatively finely dispersed and thus exists with a multitude of microscopic phase interfaces. At these PC-PMMA phase interfaces, incident light is scattered due to the different refractive indices of the two polymers. The result is a high opacity (i.e., very low light transmission) of the PC / PMMA blends compared to the two polymer blend partners.

[0006] Furthermore, the phase boundaries can represent weak points with regard to mechanical stresses. These phase boundaries can lead to brittle fracture failure under (multiaxial) impact and / or fracture failure due to external stresses acting on the molded body, particularly when the molded body is in contact with certain chemicals / media such as fats or oils, which are components of food, lubricants, or cosmetic products (such as hand or sunscreen).

[0007] A technical challenge in materials development that has so far been inadequately solved has been the provision of PC / PMMA blends that are suitable for the production of transparent or translucent (i.e., translucent) molded bodies using a thermoplastic forming process and that exhibit an advantageous combination of scratch resistance, ductility, and stress crack resistance under the influence of chemicals.

[0008] Various scientific publications and patent documents reveal that transparent PC / PMMA blends can be produced using block copolymers that can be formed in-situ in a reactive extrusion.

[0009] WO 2020 / 212229 A1 discloses a reactive compounding process for producing a thermoplastic molding compound using aromatic polycarbonate and another polymer containing at least one type of functional group selected from ester, epoxy, hydroxy, carboxy, and carboxylic anhydride groups, with a specific phosphonium salt being used as the catalyst. The application also discloses, in particular, the production of transparent thermoplastic PC / PMMA molding compounds using such a process.

[0010] WO 2016 / 138246 A1 discloses transparent PC / PMMA blends containing 9.9 to 40 wt.% polycarbonate and 59.9 to 90 wt.% PMMA, which are produced in a melt extrusion using 0.0025 to 0.1 wt.% of a tin catalyst.

[0011] WO 2016 / 189494 A1 discloses transparent PC / PMMA blends containing 80 to 95 wt.% of a specifically specified branched polycarbonate with an end-cap content of 45% to 80% and 4.9 to 20 wt.% PMMA, which are produced in a melt extrusion by transesterification using 0.1 to 1.5 wt.% of a catalyst, preferably selected from Zn, Sn and Ag compounds.

[0012] AK Singh, et al. "Reactive Compatibilization of Polycarbonate and Poly(methyl)methacrylate in the Presence of a Novel Transesterification Catalyst SnCl2·2H2O", J. Phys. Chem. B 2011, 115, 1601-1607 discloses transparent PC / PMMA molding compounds prepared in a reactive extrusion process using SnCl2·2H2O as catalyst.

[0013] AK Singh, et al. "Evidence for in situ graft copolymer formation and compatibilization of PC and PMMA during reactive extrusion processing in the presence of the novel organometallic transesterification catalyst tin(II) 2-ethylhexanoate", RSC Advances, 2012, 2, 10316-10323 discloses translucent PC / PMMA molding compounds prepared in a reactive extrusion process using tin(II) 2-ethylhexanoate as a catalyst.

[0014] T. Bubmann et al., "Transparent PC / PMMA Blends Via Reactive Compatibilization in a Twin-Screw Extruder," Polymers 2019, 11, 2070, discloses that such PC+PMMA molding compounds produced in reactive extrusion processes according to the previously cited prior art are transparent due to an interpolymer transesterification reaction and thus the formation of PC-g-PMMA graft polymers during reactive extrusion, but exhibit insufficient material ductility for any industrial application. The reason for this is the molecular weight reduction of the polycarbonate associated with the transesterification, which also contributes significantly to the development of transparency in the blends produced in this way, since the miscibility of PC and PMMA improves with decreasing PC molecular weight, resulting in single-phase morphologies in the reactive-extruded blends.

[0015] The PC / PMMA blends of the state of the art still have insufficient light transmission for some application areas and / or a light transmission that is not sufficiently constant over the entire wavelength range of visible light.

[0016] US 4,959,411 discloses a process for producing a block copolymer by reacting an epoxy-functionalized olefin polymer with a carboxy-functionalized polycarbonate in organic solution or by melt compounding, as well as the use of such a copolymer for compatibilizing polymer blends of polycarbonate and polyolefin with the aim of reducing their tendency to delaminate. The production of copolymers of polycarbonate and polymethyl methacrylate, as well as transparent PC / PMMA molding compounds with the desired profile of mechanical properties, is not disclosed.

[0017] It was therefore desirable to provide a composition for producing a transparent or translucent (i.e. translucent with light in the visible wavelength range), thermoplastic polymethyl methacrylate-containing polycarbonate molding compound with improved light transmission, preferably with a light transmission that is largely constant over the entire wavelength range of visible light, wherein translucent moldings with improved scratch resistance compared to polycarbonate can be produced from the molding compound, which moldings are suitable for the production of components for use in particular in fiber optic technology and lighting applications.

[0018] It was further desirable that these compositions exhibit improved stress cracking resistance under the influence of chemicals compared to state-of-the-art PC / PMMA molding compounds, ideally also compared to pure polycarbonate.

[0019] Furthermore, it was desirable that these compositions have good ductility, preferably improved ductility compared to translucent PC / PMMA molding compounds of the prior art.

[0020] Furthermore, it was desirable to provide a process which is suitable for the production of such molding compounds and can preferably be carried out in commercially available and industrially established compounding units such as single-screw extruders, co-rotating or counter-rotating twin-screw extruders, planetary roller extruders, internal kneaders or co-kneaders.

[0021] Furthermore, it was desirable to provide a simple process for the production of PC / PMMA molded bodies with the described property profile.

[0022] In the context of the present application, a translucent shaped body is understood to mean a shaped body which has a transmission Y(D65, 10°) measured and calculated in accordance with DIN 5033-7 in version 2014-10 or in accordance with DIN EN ISO 11664-3 in version 2013-08 of at least 35%, preferably at least 50%, more preferably at least 65%, most preferably at least 75% at least at least one point.

[0023] In the context of the present application, a preferred transilluminable shaped body with a transmission that is largely constant over the entire wavelength range of visible light is understood to mean a shaped body for which, at at least one point, the amount of the difference between the local wavelength-specific total transmittances measured at wavelengths of 700 nm (T 700 ) and 400 nm (T 400 ) is a maximum of 70%, preferably a maximum of 50%, particularly preferably a maximum of 30% of the value of the local transmission Y(D65, 10°).

[0024] The corresponding wavelength-dependent total transmittances are determined according to DIN 5033-7, version 2014-10. From this, the value Y(D65, 10°) is calculated according to DIN EN ISO 11664-3, version 2013-08, using illuminant D65 and a 10° observer. In the following, this value Y(D65, 10°) is referred to as "transmission."

[0025] The translucent moldings produced from the molding compound are said to exhibit improved scratch resistance compared to pure polycarbonate, as assessed by pencil hardness, which is determined based on the Wolff-Wilborn method. Pure polycarbonate exhibits a pencil hardness of F in this test method, meaning that the moldings according to the invention should exhibit a pencil hardness of at least H, preferably at least 2H, particularly preferably at least 3H.

[0026] The molded articles produced should preferably have improved scratch resistance compared to pure polycarbonate and improved resistance to fats and oils and / or compositions containing fats and / or oils, such as cosmetics, hand creams and sun lotion, compared to pure polycarbonate and / or PC / PMMA compositions according to the prior art.

[0027] Surprisingly, it has now been found that thermoplastic molding compositions obtained by melt compounding a composition containing A) an aromatic polycarbonate and / or aromatic polyestercarbonate containing carboxy groups, wherein the polycarbonate has an acid number in the range of 0.5 to 10 mg potassium hydroxide (KOH) / g, determined in dichloromethane (DCM) / ethanol as solvent by potentiometric titration according to DIN EN ISO 2114, Method A in version 2002-6 with ethanolic KOH solution at room temperature, and a weight-average molecular weight M w , determined by gel permeation chromatography at room temperature in dichloromethane as solvent using a BPA polycarbonate standard, in the range of 10,000 to 40,000 g / mol and B) a polymethyl methacrylate copolymer containing structural units derived from glycidyl methacrylate, wherein the copolymer has an epoxy equivalent, determined in dichloromethane as solvent at room temperature according to DIN EN 1877-1 in version 2000-12, of 0.05 to 3 wt.-% and a weight-average molecular weight M w , determined by gel permeation chromatography at room temperature in tetrahydrofuran as solvent with a polystyrene standard, of 20,000 to 200,000 g / mol. wherein the weight ratio of components A and component B is in the range of 95:5 to 35:65, exhibiting the desired properties.

[0028] In this application, the terms "carboxy" and "carboxyl" are used synonymously and stand for COOH groups.

[0029] In a preferred embodiment, the nature and amounts of components A and B are selected such that the ratio of (i) the product of the acid number of component A (in mg KOH / g) and the weight fraction of component A, based on a total of 100 parts by weight of components A and B, and (ii) the product of the epoxy equivalent of component B (in wt. %) and the weight fraction of component B, based on a total of 100 parts by weight of components A and B, is at least 15, more preferably at least 20, particularly preferably at least 25 and most preferably at least 30.

[0030] The ratio of (i) the product of the acid number of component A (in mg KOH / g) and the weight fraction of component A, based on a total of 100 parts by weight of components A and B, and (ii) the product of the epoxy equivalent of component B (in wt. %) and the weight fraction of component B, based on a total of 100 parts by weight of components A and B, is preferably at most 200, particularly preferably at most 100 and most preferably at most 50.

[0031] The ratio of (i) the product of the acid number of component A (in mg KOH / g) and the weight fraction of component A, based on a total of 100 parts by weight of components A and B, and (ii) the product of the epoxy equivalent of component B (in wt. %) and the weight fraction of component B, based on a total of 100 parts by weight of components A and B, is preferably in the range from 15 to 200, particularly preferably in the range from 20 to 100, further preferably in the range from 25 to 100 and most preferably in the range from 25 to 50.

[0032] In melt compounding, at least a portion of component A is covalently coupled to at least a portion of component B in a chemical reaction to form a copolymer containing blocks of components A and B.

[0033] In a preferred embodiment, the weight ratio of components A and B is in the range from 90:10 to 60:40, particularly preferably in the range from 85:15 to 75:25.

[0034] In a preferred embodiment, the compositions contain components A and B in total in an amount of at least 75% by weight, more preferably at least 90% by weight, particularly preferably at least 95% by weight and most preferably at least 99% by weight.

[0035] Preference is also given to compositions which consist of components A and B. In a further preferred embodiment, such compositions consist of 35 to 95 wt%, more preferably 60 to 90 wt%, most preferably 75 to 85 wt% of component A and 5 to 65 wt%, more preferably 10 to 40 wt%, most preferably 25 to 30 wt% of component B.

[0036] In addition to components A and B, the composition may contain as component C one or more polymer additives, processing aids and / or polymers different from components A and B, provided that these do not conflict with the solution of the problem with regard to their type and amount used.

[0037] This component C is used in an amount of preferably up to 25% by weight, more preferably up to 10% by weight, particularly preferably up to 5% by weight and most preferably up to 1% by weight in the compositions.

[0038] Such compositions containing component C preferably consist of 35 to 95% by weight, particularly preferably 60 to 90% by weight, most preferably 75 to 85% by weight of component A, 4.99 to 64.99% by weight, particularly preferably 9.98 to 39.98% by weight, most preferably 14.9 to 24.9% by weight of component B, 0.01 to 10% by weight, particularly preferably 0.02 to 5% by weight, most preferably 0.1 to 1% by weight of component C, the % by weight of components A to C being selected so that they add up to 100% by weight. Component A

[0039] An aromatic polycarbonate and / or an aromatic polyestercarbonate is used as component A. Mixtures of several aromatic polycarbonates and / or polyestercarbonates can also be used.

[0040] The polycarbonate and / or polyestercarbonate according to component A contains carboxy (COOH) groups, in a preferred embodiment terminal COOH groups. In a particularly preferred embodiment, the COOH groups in component A are exclusively terminal in nature.

[0041] The polycarbonate and / or polyestercarbonate according to component A has an acid number in the range of 0.5 to 10 mg potassium hydroxide (KOH) / g. In a preferred embodiment, the acid number of component A is 1 to 7 mg KOH / g, particularly preferably 1.3 to 5.0 mg KOH / g, most preferably 1.5 to 3.5 mg KOH / g.

[0042] The acid number is determined in dichloromethane (DCM) / ethanol as solvent according to DIN EN ISO 2114, Method A, version 2002-6, using potentiometric titration with ethanolic KOH solution at room temperature. The polymer to be tested is dissolved in 50 ml of dichloromethane at a concentration of 10 g / L at room temperature. Before the potentiometric titration with 0.1 N ethanolic KOH, 5 ml of ethanol is added to the sample solution.

[0043] The polycarbonate and / or polyestercarbonate according to component A has a weight-average molecular weight M w , measured by GPC (gel permeation chromatography) at room temperature in methylene chloride with BPA polycarbonate standard), of 10,000 to 40,000 g / mol, preferably of 15,000 to 35,000 g / mol, particularly preferably of 20,000 to 30,000 g / mol.

[0044] If a mixture of several polycarbonates with different individual acid numbers and / or different individual weight-average molecular weights M w is used as component A, this mixture has an acid number or a weight-average molecular weight M w in one of the above-mentioned ranges.

[0045] Aromatic polycarbonates according to component A which are suitable according to the invention are known from the literature or can be prepared by processes known from the literature (for the preparation of aromatic polycarbonates see, for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964 and DE-AS 1 495 626, DE-A 2 232 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3 000 610, DE-A 3 832 396).

[0046] Aromatic polycarbonates are produced according to the component, for example, by reacting diphenols with carbonic acid halides, preferably phosgene, and / or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, by the interfacial process, preferably using chain terminators, for example monophenols, and optionally using trifunctional or more than trifunctional branching agents, for example triphenols or tetraphenols. Likewise, production via a melt polymerization process is also possible by reacting diphenols with, for example, diphenyl carbonate in the presence of a transesterification catalyst.

[0047] The interfacial polymerization process is particularly suitable for producing the COOH-group-containing polycarbonates according to component A of the invention.

[0048] A preferred process for producing polycarbonates containing terminal COOH groups according to component A is described in US 4,853,458 B. In this process, carboxylic acid groups or carboxylic acid group derivatives, such as monophenols containing ester, anhydride, or amide groups, are used as chain terminators in an interfacial polymerization process. After polymerization, the COOH groups are released as described below. The molecular weight of the polycarbonates produced in this way can be precisely adjusted within a wide range by varying the ratio of monophenolic chain terminators to diphenols. Alkyl, aryl, or alkylaryl esters of 4-hydroxybenzoic acid are preferably used as chain terminators containing carboxylic acid groups or carboxylic acid group derivatives.Alkyl esters of 4-hydroxybenzoic acid, more preferably the tert-butyl ester of 4-hydroxybenzoic acid, i.e., tert-butyl 4-hydroxybenzoate, are particularly preferably used as chain terminators. The chain terminators containing carboxylic acid groups or carboxylic acid group derivatives can also be used as a mixture with other monophenolic chain terminators that do not contain carboxylic acid groups or carboxylic acid group derivatives, i.e., as a chain terminator mixture. The ratio of the chain terminator molecules containing carboxylic acid groups or carboxylic acid group derivatives to those not containing carboxylic acid groups or carboxylic acid group derivatives, as well as the conditions during the subsequent release of the COOH groups, allows the content of COOH groups in component A to be adjusted in a targeted manner over a wide range.

[0049] Suitable chain terminators for the production of aromatic polycarbonates in the interfacial process which do not contain any carboxylic acid groups or carboxylic acid group derivatives are, for example, phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols such as 4-[2-(2,4,4-trimethylpentyl)]phenol, 4-(1,3-tetramethylbutyl)phenol according to DE-A 2 842 005 or monoalkylphenol or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-iso-octylphenol, p-tert-octylphenol, p-dodecylphenol and 2-(3,5-dimethylheptyl)phenol and 4-(3,5-dimethylheptyl)phenol. Preferred chain terminators are phenol or p-tert-butylphenol, most preferred is p-tert-butylphenol.

[0050] More preferably, in the production of the polycarbonates, these chain terminators, which do not contain any carboxylic acid groups or carboxylic acid group derivatives, are used in a molar proportion, based on a total of 100 mol% of all chain terminators, of 20 to 90 mol%, particularly preferably 40 to 85 mol%, further preferably 45 to 80 mol%, particularly preferably 50 to 75 mol%.

[0051] The terminal COOH groups (i.e. 4-hydroxybenzoic acid end groups) can be obtained from polycarbonates with 4-hydroxybenzoic acid ester end groups, for example, by end group pyrolysis or by acid-catalyzed ester cleavage. With the preferred use of tert-butyl 4-hydroxybenzoate as a chain terminator, the COOH end groups can be released from the tert-butyl 4-hydroxybenzoate end groups in the polycarbonate particularly easily by thermal elimination of isobutylene at temperatures above 200°C, preferably in the range from 230 to 275°C, more preferably in the range from 230 to 260°C, particularly preferably in the range from 230 to 255°C, without significantly degenerating the polycarbonate backbone. By varying the temperature in particular during this end group pyrolysis, the proportion of COOH end groups and also the ratio to undesired by-products can be controlled.

[0052] Diphenols for the preparation of the aromatic polycarbonates and / or aromatic polyester carbonates are preferably those of the formula (1) where A is a single bond, C 1 to C 5 alkylene, C 2 to C 5 alkylidene, C 5 to C 6 cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO 2 -, C 6 to C 12 arylene, to which further aromatic rings optionally containing heteroatoms may be condensed, or a radical of the formula (2) or (3) B is each C 1 to C 12 alkyl, preferably methyl, halogen, preferably chlorine and / or bromine, x is each independently 0, 1 or 2, p is 1 or 0, and R 5< and R 6< for each X 1< can be selected individually, independently of one another are hydrogen or C 1 to C 6 alkyl, preferably hydrogen, methyl or ethyl, X1 is carbon and m is an integer from 4 to 7, preferably 4 or 5, with the proviso that on at least one atom X 1<, R 5< and R 6< are simultaneously alkyl.

[0053] Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis-(hydroxyphenyl)-C 1 -C 5 -alkanes, bis-(hydroxyphenyl)-C 5 -C 6 -cycloalkanes, bis-(hydroxyphenyl) ethers, bis-(hydroxyphenyl) sulfoxides, bis-(hydroxyphenyl) ketones, bis-(hydroxyphenyl) sulfones and α,α-bis-(hydroxyphenyl)-diisopropylbenzenes and their nuclear-brominated and / or nuclear-chlorinated derivatives.

[0054] Particularly preferred diphenols are 4,4'-dihydroxydiphenyl, bisphenol A, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone, and their di- and tetrabrominated or chlorinated derivatives, such as 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, or 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane. 2,2-bis(4-hydroxyphenyl)propane (bisphenol A) is particularly preferred.

[0055] The diphenols can be used individually or as any mixture. The diphenols are known from the literature or are available by known methods.

[0056] In a preferred embodiment, the proportion of bisphenol A, based on the sum of all diphenols used to produce component A, is at least 50 mol%, particularly preferably at least 75 mol%, and most preferably at least 95 mol%. Most preferably, bisphenol A is used exclusively as the diphenol in the production of component A.

[0057] The aromatic polycarbonates can be branched in a known manner, preferably by incorporating 0.01 to 2.0 mol%, based on the sum of the diphenols used, of trifunctional or more than trifunctional compounds, for example those with three or more phenolic groups.

[0058] Preference is given to using linear aromatic polycarbonates, more preferably linear aromatic polycarbonates based on bisphenol A, particularly preferably exclusively based on bisphenol A.

[0059] Aromatic dicarboxylic acid dihalides for the production of aromatic polyester carbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, diphenyl ether-4,4'-dicarboxylic acid and naphthalene-2,6-dicarboxylic acid.

[0060] Particularly preferred are mixtures of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio between 1:20 and 20:1.

[0061] In the production of polyester carbonates, a carbonic acid halide, preferably phosgene, is also used as a bifunctional acid derivative.

[0062] In addition to the monophenols already mentioned, the chlorocarbonic acid esters thereof and the acid chlorides of aromatic monocarboxylic acids, which may optionally be substituted by C1 to C22 alkyl groups or by halogen atoms, as well as aliphatic C2 to C22 monocarboxylic acid chlorides can be considered as chain terminators for the production of aromatic polyester carbonates.

[0063] In the production of aromatic polyester carbonates, one or more aromatic hydroxycarboxylic acids can additionally be used.

[0064] The aromatic polyester carbonates can be either linear or branched in a known manner (see DE-A 2 940 024 and DE-A 3 007 934), with linear polyester carbonates being preferred.

[0065] Branching agents which can be used are, for example, trifunctional or polyfunctional carboxylic acid chlorides, such as trimesic acid trichloride, cyanuric acid trichloride, 3,3'-,4,4'-benzophenonetetracarboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in amounts of 0.01 to 2.0 mol% based on the dicarboxylic acid dichlorides used, or trifunctional or polyfunctional phenols, such as phloroglucinol, 4,6-dimethyl-2,4,6-tri-(4-hydroxyphenyl)-hept-2-ene, 4,6-dimethyl-2,4-6-tri-(4-hydroxyphenyl)-heptane, 1,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1,1-tri-(4-hydroxyphenyl)-ethane, tri-(4-hydroxyphenyl)-phenylmethane, 2,2-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]propane, 2,4-bis(4-hydroxyphenylisopropyl)phenol, tetra(4-hydroxyphenyl)methane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 2-(4-Hydroxyphenyl)-2-(2,4-dihy-droxyphenyl)-propane, tetra-(4-[4-hydroxyphenyl-isopropyl]-phenoxy)-methane, 1,4-bis[4,4'-dihydroxytri-phenyl)-methyl]-benzene, in amounts of 0.01 to 2,0 mol% based on the diphenols used. Phenolic branching agents can be added with the diphenols; acid chloride branching agents can be added together with the acid dichlorides.

[0066] The proportion of carbonate structural units in the thermoplastic aromatic polyester carbonates can vary as desired. The proportion of carbonate groups is preferably up to 100 mol%, in particular up to 80 mol%, and particularly preferably up to 50 mol%, based on the sum of ester groups and carbonate groups. Both the ester and carbonate portions of the aromatic polyester carbonates can be present in the form of blocks or randomly distributed in the polycondensate.

[0067] Most preferably, exclusively linear aromatic polycarbonates, preferably based on bisphenol A, particularly preferably based exclusively on bisphenol A, are used as component A. Component B

[0068] Component B is a polymethyl methacrylate copolymer containing structural units derived from glycidyl methacrylate.

[0069] Component B can also be a mixture of several polymethyl methacrylate copolymers. These polymethyl methacrylate copolymers can also contain portions of polymethyl methacrylate polymer molecules that do not themselves contain structural units derived from glycidyl methacrylate. This is generally unavoidable due to manufacturing processes, especially with low glycidyl methacrylate contents in the polymethyl methacrylate copolymer.

[0070] The polymethyl methacrylate copolymers according to component B have epoxy equivalents, determined in dichloromethane as solvent at room temperature according to DIN EN 1877-1 in version 2000-12, of 0.05 to 3 wt.%, preferably of 0.1 to 1.5 wt.%, particularly preferably of 0.13 to 0.60 wt.%, most preferably of 0.15 to 0.45 wt.%.

[0071] The polymethyl methacrylate copolymers according to component B have a weight-average molecular weight M w , determined by gel permeation chromatography at room temperature in tetrahydrofuran as solvent using a polystyrene standard, of 20,000 to 200,000 g / mol, preferably of 30,000 to 150,000 g / mol, particularly preferably 50,000 to 100,000 g / mol.

[0072] If component B is a mixture of several polymethyl methacrylate copolymers, the previously mentioned (preferred) ranges for the epoxy content and the weight-average molecular weights M w as well as all (preferred) ranges described below apply to the corresponding mixture of the polymethyl methacrylate copolymers according to component B.

[0073] The term "copolymer containing structural units derived from" means that the copolymer is prepared from the said monomers by copolymerization.

[0074] Component B preferably contains 0.2 to 10 wt.%, more preferably 0.3 to 5 wt.%, particularly preferably 0.4 to 2 wt.%, most preferably 0.5 to 1.5 wt.% of structural units derived from glycidyl methacrylate.

[0075] These copolymers are preferably prepared by polymerizing methyl methacrylate in the presence of 0.2 to 10 wt.%, more preferably 0.3 to 5 wt.%, particularly preferably 0.4 to 2 wt.%, most preferably 0.5 to 1.5 wt.% of glycidyl methacrylate.

[0076] The copolymers according to component B can contain up to 50% by weight, preferably up to 25% by weight, particularly preferably up to 10% by weight, of structural units derived from further copolymerizable vinylic, preferably acrylic (i.e., containing acrylic groups) monomers. Examples of suitable copolymerizable acrylic monomers include methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, hexyl acrylate, 2-ethylhexyl acrylate, butyl methacrylate, and other compounds structurally related to these acrylates.

[0077] The wt% given in this section for component B refers to component B.

[0078] In a most preferred embodiment, component B does not contain any structural units derived from other copolymerizable vinylic monomers.

[0079] The copolymers according to component B are thermoplastic.

[0080] The preparation of the copolymers according to component B containing structural units derived from methyl methacrylate and glycidyl methacrylate is known to the person skilled in the art and is preferably carried out by radically initiated polymerization of the corresponding monomers, in particular by emulsion, suspension, solution or bulk polymerization.

[0081] In solution polymerization, which is preferably carried out in aprotic solvents, for example optionally halogen-substituted aliphatic or aromatic hydrocarbons as solvents, conditions should preferably be maintained that at least largely avoid hydrolysis of the epoxy groups. Suitable and preferred conditions for this include, for example, low contents of protic solvents such as water, alcohols, acids, or bases and working in solvents from the group of organic hydrocarbons that are inert toward epoxy groups, such as toluene, ethylbenzene, xylene, high-boiling aliphatics, chlorinated aromatic hydrocarbons such as mono-, di-, tri-, or tetrachlorobenzenes, chlorinated aliphatic hydrocarbons such as dichloromethane or chloroform, ketones such as methyl ethyl ketone, esters, or ethers.

[0082] By adding regulators, especially sulfur regulators, in particular mercaptans, the molecular weights of component B can be adjusted during the radical polymerization so that the weight-average molecular weight M w according to the invention results. Component C

[0083] As component C, one or more polymer additives, processing aids and / or further polymeric components different from components A and B can be included in the composition, preferably selected from the group consisting of flame retardants, anti-drip agents, flame retardant synergists, smoke inhibitors, lubricants and mold release agents, nucleating agents, polymeric and non-polymeric antistatic agents, conductivity additives, stabilizers (e.g. hydrolysis, heat aging and UV stabilizers as well as transesterification inhibitors), flow promoters, phase compatibilizers, impact modifiers (both with and without core-shell structure), polymeric blend partners, catalysts, fillers and reinforcing materials as well as dyes and pigments.

[0084] The type and amount of component C is selected in such a way that influences on the mechanical properties and transparency of the molded articles produced from the molding compositions are as small as possible, i.e. in such a way that the addition of component C does not conflict with the solution of the problem according to the invention.

[0085] If component C is used, it is used in a maximum proportion of 25 wt.%, based on the composition. This proportion is then the sum of all polymer additives, processing aids, and polymer components other than components A and B used as component C.

[0086] Anti-drip agents, flame retardant synergists, smoke inhibitors, lubricants and mold release agents, nucleating agents, non-polymeric antistatic agents, conductivity additives and stabilizers are preferably used in a proportion of up to 1 wt.% each, particularly preferably in a proportion of 0.05 to 1 wt.% and in total preferably in a proportion of 0.05 to 3 wt.%, based on the composition.

[0087] If flame retardants are used, they are preferably used in an amount of up to 15% by weight, particularly preferably 0.05 to 15% by weight, based on the composition.

[0088] If flow promoters, polymeric antistatic agents and phase compatibilizers are used, the proportion used is in each case preferably up to 10 wt.%, particularly preferably 0.05 to 10 wt.% and in total preferably 0.05 to 15 wt.%, based on the composition.

[0089] If impact modifiers or polymeric blend parts are used, the total amount used is preferably up to 18% by weight, particularly preferably 0.05 to 18% by weight, based on the composition.

[0090] If dyes or pigments are used, the proportion used in total of all dyes and pigments used is preferably up to 10 wt.%, particularly preferably 0.1 to 10 wt.%, based on the composition.

[0091] In a preferred embodiment, inorganic pigments are used in a proportion of not more than 3% by weight in total, particularly preferably not more than 1.5% by weight in total, further preferably not more than 0.5% by weight, in each case based on the composition. In In the most preferred embodiment, no inorganic pigments are used as part of component C.

[0092] If fillers and reinforcing materials are used, the proportion used is preferably 3 to 10 wt.%, based on the composition.

[0093] In a preferred embodiment, no fillers or reinforcing materials are used.

[0094] In a preferred embodiment, at least one polymer additive selected from the group consisting of lubricants and mold release agents, stabilizers, flow promoters, phase compatibilizers, impact modifiers, other polymeric blend partners and dyes is used.

[0095] In a preferred embodiment, pentaerythritol tetrastearate is used as a mold release agent.

[0096] In a preferred embodiment, at least one member selected from the group consisting of sterically hindered phenols, organic phosphites and sulfur-based co-stabilizers is used as the stabilizer.

[0097] In a particularly preferred embodiment, at least one representative selected from the group consisting of octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate and tris(2,4-di-tert-butylphenyl)phosphite is used as stabilizer. Production of molding compounds and moldings from the compositions according to the invention

[0098] Thermoplastic molding compounds can be produced from the compositions according to the invention.

[0099] The thermoplastic molding compositions according to the invention can be prepared, for example, by melt-mixing the respective components of the compositions at temperatures of 220°C to 320°C, preferably 230 to 300°C, particularly preferably 240 to 280°C, most preferably 250 to 270°C.

[0100] The invention also relates to a corresponding process for producing the molding compositions according to the invention.

[0101] The procedure includes the steps (i) melting the components of the composition by introducing thermal energy and / or mechanical shear, (ii) mixing and dispersing the various components of the composition with or into each other, (iii) solidifying the melt by cooling, (iv) granulating the solidified polymer blend resulting from steps (i) - (iii).

[0102] The residence time of the components at the above-mentioned temperatures is preferably in the range of 15 seconds to 30 minutes, more preferably 30 seconds to 20 minutes. When using extruders or continuous co-kneaders as the compounding unit, the residence time is preferably 15 seconds to 5 minutes, particularly preferably 30 seconds to 2 minutes.

[0103] After step ii), the present composition can also be degassed by applying a negative pressure. The absolute pressure is preferably set to a maximum of 400 mbar, more preferably to a maximum of 200 mbar, and particularly preferably to a maximum of 100 mbar.

[0104] Mixing can take place in conventional equipment, such as single-screw extruders, co-rotating or counter-rotating twin-screw extruders, planetary roller extruders, internal kneaders, or continuous or discontinuous co-kneaders. In these, the compositions are melt compounded or melt extruded to form molding compounds. This process is generally referred to as compounding or melt compounding in the context of this application. A molding compound is therefore understood to be the product obtained when the components of the composition are melt compounded and melt extruded. Such a molding compound is a further subject matter of the present invention.

[0105] The mixing of the individual components of the compositions can be carried out in a known manner, both successively and simultaneously, at approximately 20°C (room temperature) and at higher temperatures. This means, for example, that some of the components can be metered entirely or partially via the main feed of an extruder, and the remaining components can be added entirely or partially via a side extruder later in the compounding process.

[0106] During the process described above, the epoxy groups in the structural units derived from glycidyl methacrylate in component B are partially or completely chemically converted. This conversion can be detected and quantitatively monitored via the decrease in the epoxy equivalent, determined in dichloromethane as a solvent at room temperature according to DIN EN 1877-1 (version 12-2000). Alternatively, the conversion can be quantitatively monitored and detected using 1< H NMR spectroscopy. The characteristic 1< H NMR multiplet signals of the protons in the unopened epoxy ring at 2.58–2.64 ppm, 2.80–2.84 ppm, and 3.15–3.22 ppm (measured in deuterated chloroform CD 2 Cl 2 as solvent using a 600 MHz instrument from Bruker, Karlsruhe, Germany) are used. Their intensity decreases with increasing conversion of the epoxy groups. The chemical shifts are given relative to tetramethylsilane.When carrying out the process described above, component A or a portion of component A is preferably chemically coupled to component B or a portion of component B to form a PC-PMMA copolymer. In general, the COOH groups in component A react with the epoxy groups of component B. In general, the copolymer resulting from the reaction of polymers A and B is a block copolymer or graft copolymer containing blocks of components A and B.

[0107] The chemical reaction of the epoxy groups in the glycidyl methacrylate-derived structural units in component B with the carboxyl groups in component A to form a copolymer containing blocks of components A and B can be monitored by the simultaneous decrease in the acid number, determined in DCM / ethanol as solvent by potentiometric titration with ethanolic KOH solution at room temperature. Detection of the reaction product is possible via 1< H NMR spectroscopy. As an alternative to the previously mentioned titration methods, NMR spectroscopy also allows quantitative monitoring of the chemical reaction.When coupling products containing blocks from components A and B are formed, several new, often very broad and poorly resolved multiplet signals appear in the 1< H NMR spectrum in the range between 4.18 and 4.55 ppm due to the addition linkage of the carboxy group of component A to the epoxy group of component B. However, due to their breadth and the generally very low concentration of the linking groups, NMR spectroscopic detection is not always (easily) possible and regularly requires a strong magnification of the corresponding spectrum range and the acquisition of a spectrum with an excellent signal-to-noise ratio.

[0108] Another way to detect the formation of copolymers containing blocks of components A and B is to conduct 2D DOSY 1H NMR studies. The formation of copolymers is reflected in a reduction in the diffusion coefficient of the reaction product compared to the components in the corresponding physical polymer mixture of components A and B.

[0109] It is further preferred that the mixture used in step i) comprising components A, B, and optionally C has a residual moisture content determined by Karl Fischer titration of 0.01 to 0.50 wt.%, more preferably 0.07 to 0.20 wt.%, in each case based on the sum of A, B, and C. If the moisture content is too high, there is a risk of undesirably high molecular weight degradation.

[0110] The molding compositions of the invention can be used to produce molded articles of any type. These can be produced, for example, by injection molding, extrusion, and blow molding. Another processing method is the production of molded articles by deep drawing from previously produced sheets or films. The molding compositions of the invention are particularly suitable for processing by extrusion, blow molding, and deep drawing processes.

[0111] It is also possible to dose the components of the compositions directly into the conveyor extruder of an injection molding machine, to produce the molding compound according to the invention in the conveyor extruder and to process it directly into molded articles by appropriately discharging the molding compound into an injection mold (compounding or reactive compounding injection molding).

[0112] Such a method is a further subject of the present invention and comprises the following steps: (i) Dosing the components of the composition according to the invention into the conveyor extruder of an injection molding machine, (ii) Melting the components of the composition according to the invention by introducing thermal energy and / or mechanical shear, (iii) Conveying the melt to the discharge point of the extruder, (iv) Discharge of the melt from the conveyor extruder into an injection mold, (v) Cooling and solidifying the melt in the injection mold to form a molded article, (vi) Removing the molded article from the injection mold.

[0113] In In a preferred embodiment of this process, the residence time of the melt in the conveyor extruder is at least two, more preferably at least five, particularly preferably at least seven minutes.

[0114] In a preferred embodiment of this process, the residence time of the melt in the conveyor extruder is 2 to 30 minutes, more preferably 5 to 20 minutes, particularly preferably 7 to 15 minutes.

[0115] In a preferred embodiment, process steps (iii) and (iv) are carried out under shearing. This can be achieved, for example, by a high screw speed during melt conveyance in step (iii) and / or by a suitable screw configuration of the conveying screw, for example, by the use of kneading elements, as well as by a suitably narrow geometry of the melt outlet nozzle in step (iv).

[0116] A further subject matter of the present invention thus relates to the use of a composition according to the invention or a molding composition according to the invention for producing molded articles, and also to a molded article which is obtainable from a composition according to the invention or from a molding composition according to the invention or which contains such a molding composition.

[0117] Examples of such molded bodies are films, profiles, housing parts of all kinds, e.g. for household appliances such as juicers, coffee machines, mixers; for office machines such as monitors, flat screens, notebooks, printers, copiers; panels, pipes, electrical installation ducts, windows, doors and other profiles for the construction sector (interior and exterior applications) as well as electrical and electronic parts such as switches, plugs and sockets and components for commercial vehicles, in particular for the automotive sector.The compositions and molding compounds according to the invention are also suitable for producing the following molded bodies or molded parts: interior fittings for rail vehicles, ships, aircraft, buses and other motor vehicles, body parts for motor vehicles, housings of electrical devices containing small transformers, housings for information processing and transmission devices, housings and cladding of medical devices, massage devices and housings therefor, toy vehicles for children, flat wall elements, housings for safety devices, heat-insulated transport containers, molded parts for sanitary and bathroom equipment, cover grilles for ventilation openings and housings for gardening tools.

[0118] Due to their particular technical properties, the compositions and molding compounds according to the invention are particularly suitable for the production of molded articles transilluminable with light in the visible wavelength range, for example, an LED light source, for lighting and light guide applications in the automotive sector, the construction sector, and the electronics sector. They are particularly suitable for the production of transilluminable molded parts for use in automotive interiors, such as instrument panel supports or decorative panels, or in automotive body applications intended, for example, for ambient lighting or a need-based function display (for example, day / night differentiation). Examples Compositions Component A1

[0119] Bisphenol A-based polycarbonate with terminal carboxyl groups and a weight-average molecular weight Mw of 26,000 g / mol and a number-average molecular weight Mn of 15,000 g / mol, measured at room temperature in methylene chloride as solvent against a BPA polycarbonate calibration standard. The acid number of component A1 was determined to be 1.7 mg KOH / g. For the acid number determination, the polymer to be investigated was dissolved in 50 ml of methylene chloride at room temperature at a concentration of 10 g / L. Before potentiometric titration with 0.1 N ethanolic KOH, 2.5 ml of ethanol was added to the sample solution.

[0120] Component A1 was prepared in two steps. In step a), a precursor containing structural units derived from tert-butyl 4-hydroxybenzoate as end groups was prepared, and in step b), terminal carboxy groups were released by thermal end-group pyrolysis. a) Production of the polycarbonate precursor (PC-1)

[0121] In a continuously operated laboratory reactor, bisphenol A was subjected to a polycondensation reaction with phosgene in an interfacial process in a mixture of methylene chloride and chlorobenzene as solvent in the presence of a chain terminator mixture consisting of p-tert-butylphenol and tert-butyl 4-hydroxybenzoate.

[0122] In this synthesis, 72.2 g / h of gaseous phosgene were dissolved in 959 g / h of an organic solvent mixture of 50 wt.% methylene chloride and 50 wt.% chlorobenzene at -7°C. The phosgene solution thus prepared was brought into contact with 907 g / h of a 15 wt.% aqueous alkaline bisphenol A solution maintained at 30°C. The alkaline bisphenol A solution was pressed through a stainless steel filter with a pore size of 90 µm in the phosgene solution, thereby dispersing it. 2 mol of NaOH were used per mol of bisphenol A in the bisphenol A solution. The reaction mixture was reacted in a Fink HMR040 mixing pump maintained at 25°C until the phosgene was completely converted. Thereafter, 4.11 g / h of a mixture of 50 mol% p-tert-butylphenol and 50 mol% tert-butyl 4-hydroxybenzoate were added as a chain terminator in the form of a 3 wt% solution in the solvent mixture of 50 wt% methylene chloride and 50 wt% chlorobenzene.The resulting reaction mixture was further reacted in a second Fink HMR040 mixing pump maintained at 25°C with 66.52 g / h of 32 wt. % aqueous sodium hydroxide solution. This was followed by two flooded stirred tanks equipped with baffles, each with a residence time of 600 s, each followed by a gear pump, which served both to convey the reaction mixture and to further disperse it. Downstream of the first pump, i.e. upstream of the second stirred tank, 0.679 g / h of a 10 wt. % solution of N-ethylpiperidine in chlorobenzene was metered in as catalyst. At the end of the reaction, the pH was approximately 11.5. The organic phase of the two-phase reaction mixture was separated from the aqueous phase in a phase separation vessel, and the organic phase was washed with a 0.1 wt. % aqueous HCl solution to remove the catalyst. Subsequently, washing was continued with demineralized water to remove the salt residues.The thus washed polymer solution was precipitated in organic solvent and dried overnight in a vacuum oven at 120 °C. b) End-group pyrolysis of the polycarbonate precursor PC-1

[0123] The release of the COOH end groups by thermal end-group pyrolysis of the polycarbonate precursor PC-1, produced according to the previously described process, with cleavage of the protecting group in the form of isobutylene gas, was carried out in a continuous twin-screw extruder of the Process 11 type (Thermofischer Scientific, Karlsruhe, Germany) with a screw configuration with three mixing zones and a length-to-diameter (L / D) ratio of 40. The melt temperature was 250°C, measured using a thermocouple installed near the nozzle outlet in the last barrel element of the extruder. The melt temperature resulted from the input of mechanical energy by the kneading elements and the input of thermal energy by heating the extruder barrel. The extruder barrel is divided into eight separately and differently heated zones. The three kneading zones were located at the transition between heating zones 3 and 4, in heating zone 5, and at the transition between heating zones 6 and 7.The raw material feed is located in heating zone 1. In addition, the outlet nozzle can be heated separately. To adjust the melt temperature, the barrel temperatures in the barrel zones and the outlet nozzle were controlled as follows: The first barrel (raw material feed zone) was not heated, zone 2 was heated to a target temperature of 70°C, zone 3 was heated to a target temperature of 160°C, and zones 4 to 8 were heated to the same target temperature of 260°C. The nozzle was also heated to 260°C. The extruder was operated at a throughput of approximately 300 g / h and a speed of 175 min-1. By applying a negative pressure of approximately 100 mbar (absolute), the isobutylene gas released in the extruder under these process conditions was continuously removed from the extruder via a vent dome in the penultimate (seventh) heating zone. Under these process conditions, the polycarbonate's residence time in the extruder was approximately 70 seconds. Component A2

[0124] Component A2 differs from component A1 only in the temperature control in process step b), i.e., in the end-group pyrolysis of the polycarbonate precursor PC-1. The first barrel (raw material feed zone) was not heated; zone 2 was heated to a target temperature of 70°C, zone 3 was heated to a target temperature of 190°C, and zones 4 to 8 were heated to the same target temperature of 240°C. The die was also heated to 240°C. The other process parameters were unchanged from the production of component A1. This resulted in a melt temperature of 231°C, measured using the thermocouple installed near the die outlet in the last barrel element of the extruder. Component A2 has an acid number of 3.0 mg KOH / g and the same molecular weight as component A1. Component A3

[0125] Bisphenol A-based polycarbonate, produced by the interfacial process, with a weight-average molecular weight Mw of 26,000 g / mol, measured at room temperature in methylene chloride as solvent against a BPA polycarbonate calibration standard. Only 4-tert-butylphenol was used as a chain terminator in the production of component A3. The polycarbonate contains no carboxyl groups. Component B1

[0126] Random polymethyl methacrylate-glycidyl methacrylate copolymer with a content of 1.0 wt.% of structural units derived from glycidyl methacrylate, produced by radical polymerization. Component B1 has a weight-average molecular weight M w of 60,000 g / mol, measured by gel permeation chromatography at room temperature in tetrahydrofuran as solvent against a polystyrene calibration standard. The epoxy equivalent of component B1 was determined to be 0.32 wt.% in dichloromethane at room temperature according to DIN EN 1877-1 (version 12-2000). Component B2

[0127] Polymethyl methacrylate with a weight-average molecular weight Mw of 58,000 g / mol, measured by gel permeation chromatography at room temperature in tetrahydrofuran as solvent against a polystyrene calibration standard. Component B2 contains no structural units derived from glycidyl methacrylate.

[0128] Component C1: Tetrabutylphosphonium acetate acetic acid complex (Sachem Inc., Austin, USA) Production of thermoplastic molding compounds

[0129] The raw materials used for the production of the thermoplastic molding compounds were used in compounding as powders, which were produced from granules by cryogenic grinding.

[0130] The thermoplastic PC / PMMA molding compounds with the compositions shown in Table 1 were compounded on a continuous twin-screw extruder of the Process 11 type (Thermofischer Scientific, Karlsruhe, Germany) with a dispersing screw configuration with two mixing zones at a melt temperature of 260°C, a throughput of approximately 300 g / h, a rotational speed of 125 min -1<, and an absolute pressure of 100 mbar. Under these conditions, a residence time of approximately 90 s was achieved. After exiting through a die plate, the melt strand was cooled, thereby solidifying, and then granulated. For the compounding, powder mixtures of components A and B were first prepared and uniformly metered into the inlet zone of the twin-screw extruder via a volumetric metering device. Production of the test specimens

[0131] Round plates with a diameter of 25 mm and a thickness of 1 mm were produced from the thermoplastic molding compounds, which were prepared from the compositions according to Table 1, using a laboratory thermopress of the type Polystat 200 from Servitec Maschinenservice GmbH (Wustermark, Germany) at a temperature of 260°C, a pressure of 100 bar and a pressing time of a total of 4 min.

[0132] Furthermore, rectangular plates measuring 80 mm x 80 mm x 1 mm and test bars measuring 80 mm x 10 mm x 4 mm were produced from the thermoplastic molding compounds, which were produced from the compositions according to Table 1, on an injection molding machine of the type Arburg Allrounder 470 H 1000-170 from Arburg GmbH + Co KG (Loßburg, Germany) at a melt temperature of 270°C, a mold temperature of 60°C and an injection pressure of 2000 bar. Application-related tests

[0133] Pencil hardness was determined as a measure of scratch resistance. The measurement was carried out at room temperature using a TriForcePencil Model 293 scratch hardness tester from Erichsen GmbH & Co. KG (Hemer, Germany) according to the manufacturer's test specifications based on the Wolff-Wilborn method on injection-molded test panels measuring 80 mm x 80 mm x 1 mm. The pencils were clamped into the measuring fixture at an angle of 45° to the test surface and pushed across the specimen surface with a test force of 5 N. The test started with the hardest pencil, and the hardness was then successively reduced. The pencil hardness of the pencil whose tip was the first to no longer leave a noticeable scratch during this procedure is considered the parameter characterizing the scratch resistance of the plastic surface.

[0134] Stress cracking resistance under chemical influence (ESC behavior) was assessed in rapeseed oil at room temperature. The time to stress crack-induced fracture failure was determined using injection-molded test specimens measuring 80 mm x 10 mm x 4 mm, which were subjected to an external fiber strain of 2.4% using a clamping jig and completely immersed in rapeseed oil. The measurement was performed according to DIN EN ISO 22088 (2006 version).

[0135] The transparency of the molding compounds was determined at room temperature using thermoformed circular plates with a diameter of 25 mm and a thickness of 1 mm, as well as injection-molded rectangular plates measuring 80 mm x 80 mm x 1 mm. The corresponding wavelength-dependent total transmittances were determined according to DIN 5033-7 (2014). From these, the value Y(D65, 10°) was calculated according to DIN EN ISO 11664-3 (2013) using illuminant D65 and a 10° observer. Furthermore, the wavelength-specific transmittances were determined at wavelengths of 700 nm (T 700 ) and 400 nm (T 400 ).

[0136] The ductility of the molding compounds was assessed in an impact test on thermoformed round plates with a diameter of 25 mm and a thickness of 1 mm at room temperature. The measurements were performed using a home-made drop weight tester (drop weight 1.86 kg, support diameter 15 mm, mandrel diameter (hemispherical) 7 mm). The drop height of the drop weight was systematically varied, and the drop height at which the test specimen was not penetrated was assessed. Analytical evidence of the chemical conversion of the epoxy groups in component B and the block copolymer formation during the production of the molding compounds

[0137] During the preparation of the inventive molding compounds by compounding, the epoxy groups in component B were partially chemically converted. This chemical conversion of the epoxy groups was monitored and detected by 1< H NMR spectroscopy. The characteristic 1< H NMR multiplet signals of the protons in the unopened epoxy ring at 2.58-2.64 ppm, 2.80-2.84 ppm, and 3.15-3.22 ppm (measured at room temperature in deuterated chloroform CD 2 Cl 2 as solvent using a 600 MHz instrument from Bruker, Karlsruhe, Germany) were used as the basis. Their intensity decreased during the preparation of the inventive molding compounds by compounding compared to the physical mixture of the starting components.At the same time, several new, very broad and comparatively poorly resolved multiplet signals in the 1< H-NMR spectrum in the range between 4.18-4.55 ppm appeared during this reaction, which is assigned to the linking group formed by nucleophilic addition of carboxy groups of component A to epoxy groups of component B. The appearance of these new signals thus shows that the chemical conversion of the epoxy groups in component B produced a copolymer containing blocks of components A and B. Table 1: Compositions and properties of the resulting molding compounds Composition (parts by weight) 1 2 3 4 5 6 V7 V8 V9 V10 A1 80 70 A2 80 70 62 40 30 A3 80 80 100 B1 20 30 20 30 38 60 70 B2 20 20 C1 0,05 Features Acid number of component A [mg KOH / g] 1,7 1,7 3,0 3,0 3,0 3,0 3,0 0 0 0 Epoxy equivalents of component B [wt%] 0,32 0,32 0,32 0,32 0,32 0,32 0,32 0 0 - (Proportion (A) x SZ (A)) / (Proportion (B) x Epoxy Equivalent (B)) 21 12 38 22 15 6 4 - - - Characteristics Transmission Y(D65.10°) (on the molded body) 82 44 83 67 71 46 30 22 32 90 Transmission Y(D65,10°) (on the injection molded body) 89 T 400 (on the mold body) 65 17 68 37 42 16 14 16 22 88 T 700 (on the mold body) 87 70 87 80 82 71 49 25 39 91 100×(T 700 -T 400 ) / Y(D65.10°) (on the molded body) 27 120 24 64 56 120 117 41 53 3 T 400 (on the injection molded body) 87 T 700 (on the injection molded body) 90 100×(T 700 -T 400 ) / Y(D65.10°) (on the injection molded body) 3 Pencil hardness 3H-4H 2H F ESC (time to break in rapeseed oil at 2.4%) [h] >168 0,4 2,7 Ductility - Test specimen not pierced up to a height of [cm] 16 15 20 16 <1 25

[0138] The data in Table 1 show that moldings produced from compositions 1 to 6 according to the invention exhibit significantly better transmission (transparency) than moldings produced from compositions containing non-reactively modified PC and PMMA components (V8). Compared to V8, composition 3 according to the invention, with equal proportions of components A and B, also exhibits significantly increased pencil hardness and significantly improved chemical resistance. The pencil hardness and chemical resistance of composition 3 according to the invention are also considerably better than those of pure polycarbonate (V10).

[0139] The transparency of compositions 1 and 3 according to the invention is also improved compared to a reactively compounded composition with equal proportions of components A and B containing non-reactively modified polycarbonate, non-reactively modified PMMA, and a transesterification catalyst, as disclosed in WO 2020 / 212229 A1 (V9). Furthermore, the ductility of compositions 1 and 3 according to the invention is considerably higher than that of V9.

[0140] A comparison of Examples 3 to 6 according to the invention with Comparative Example V7 shows that the desired translucency (transmission) is no longer achieved at a content of component A of 30 wt.%.

[0141] A comparison of Examples 3 to 6 according to the invention shows that higher contents of component A are preferred.

[0142] A comparison of inventive examples 2 and 4, as well as 1 and 3, shows that higher ratios of (i) the product of the acid number of component A (in mg potassium hydroxide (KOH) / g) and the weight fraction of component A, based on a total of 100 parts by weight of components A and B, and (ii) the product of the epoxy equivalent of component B (in wt. %) and the weight fraction of component B, based on a total of 100 parts by weight of components A and B, i.e. (proportion (A) x acid number (A)) / (proportion (B) x epoxy equivalent (B)), are preferred. This applies all the more the lower the content of component A in the composition (compare examples 2 and 4 with 1 and 3).

[0143] In the most preferred example 3, the transmission, especially the transmission of injection-molded parts, is particularly uniform across the entire wavelength range of visible light, as can be seen from the lowest value for 100×(T 700 -T 400 ) / Y(D65.10°) of all examples. Furthermore, the ductility of this most preferred example 3 is particularly high.

Claims

1. Composition comprising A) a carboxy-containing aromatic polycarbonate and / or aromatic polyester carbonate, wherein the polycarbonate has an acid number in the range from 0.5 to 10 mg potassium hydroxide / g, determined in dichloromethane / ethanol as solvent by potentiometric titration according to DIN EN ISO 2114, method A, version 2002-06, with ethanolic potassium hydroxide solution at room temperature, and a weight-average molecular weight Mw, determined by gel permeation chromatography at room temperature in dichloromethane as solvent using a BPA polycarbonate standard, in the range from 10 000 to 40 000 g / mol and B) a polymethyl methacrylate copolymer containing structural units derived from glycidyl methacrylate, wherein the copolymer has an epoxy equivalent, determined in dichloromethane as solvent at room temperature according to DIN EN 1877-1, version 2000-12, of 0.05% to 3% by weight and a weight-average molecular weight Mw, determined by gel permeation chromatography at room temperature in tetrahydrofuran as solvent using a polystyrene standard, of 20 000 to 200 000 g / mol, wherein the weight ratio of components A to component B is in the range from 95:5 to 35:65.

2. Composition according to Claim 1, wherein the carboxy groups in component A are exclusively terminal carboxy groups.

3. Composition according to Claim 1 or 2, wherein the ratio of (i) the product of the acid number of component A in mg potassium hydroxide / g and the weight fraction of component A, based on in total 100 parts by weight of the components A and B, to (ii) the product of the epoxy equivalent of component B in % by weight and the weight fraction of component B, based on in total 100 parts by weight of the components A and B, is in the range from 15 to 200.

4. Composition according to any of the preceding claims, wherein the acid number of component A is 1.3 to 5.0 potassium hydroxide / g.

5. Composition according to any of the preceding claims, wherein the weight-average molecular weight Mw of component A is 20 000 to 30 000 g / mol.

6. Composition according to any of the preceding claims, wherein component B has an epoxy equivalent of 0.13% to 0.60% by weight.

7. Composition according to any of the preceding claims, wherein component B has a weight-average molecular weight Mw of 50 000 to 100 000 g / mol.

8. Composition according to any of the preceding claims, wherein component B contains 0.4% to 2% by weight of structural units derived from glycidyl methacrylate.

9. Composition according to any of the preceding claims consisting of 35% to 95% by weight of component A, 4.99% to 64.99% by weight of component B and 0.01% to 10% by weight of polymer additives, process auxiliaries and / or polymers distinct from components A and B as component C, wherein the % by weight amounts of components A to C are chosen such that they sum to 100% by weight.

10. Process for producing a thermoplastic molding compound comprising the steps of (i) melting the constituents of a composition according to any of the preceding claims by introducing thermal energy and / or mechanical shear, (ii) mixing and dispersing the different components of the composition with or in each other, (iii) solidifying the melt by cooling, (iv) granulating the solidified polymer blend resulting from steps (i)-(iii), wherein step (ii) is carried out in a compounding machine selected from the group consisting of single-screw extruders, co-rotating or counter-rotating twin-screw extruders, planetary roller extruders, internal kneaders or co-kneaders and at a temperature of the melt of 230°C to 300°C.

11. Process according to Claim 10, wherein in the process the epoxy groups in the structural units derived from glycidyl methacrylate in component B are partially or completely reacted in a chemical reaction.

12. Thermoplastic molding compound obtainable in a process according to either of Claims 10 to 11.

13. Use of a thermoplastic molding compound according to Claim 12 for producing molded articles.

14. Molded article containing a thermoplastic molding compound according to Claim 13.

15. Process for producing a molded article, comprising the steps of (i) metering the constituents of a composition according to any of Claims 1 to 9 into the conveying extruder of an injection molding machine, (ii) melting the constituents of the composition by introducing thermal energy and / or mechanical shear, (iii) conveying the melt to the discharging point of the extruder, (iv) discharging the melt from the conveying extruder into an injection mold, (v) cooling and solidifying the melt in the injection mold to form a molded article, (vi) removing the molded article from the injection mold.