Multilayers for diffuse transillumination.

Abstract

The present invention relates to a multilayer body comprising, in this order, (I) a substrate layer made of a specific thermoplastic polycarbonate molding compound, (II) at least one layer made of a colorant or colorant composition, and (III) a film. The present invention also relates to a lighting unit comprising the multilayer body and a light source, a method for producing the multilayer body, and the use of the specific thermoplastic polycarbonate molding compound as the substrate layer of this type of multilayer body.

Description

[Technical Field]

[0001] The present invention relates to a multilayer article comprising, in that order, a support layer made of a thermoplastic polycarbonate molding compound, at least one layer of a colorant or colorant composition, and a film, a lighting unit comprising the multilayer article and a light source, a method for producing the multilayer article, and the use of a thermoplastic polycarbonate molding compound as a support layer in such a multilayer article. [Background technology]

[0002] Thermoplastic polycarbonate or thermoplastic polyester carbonate molding compounds and their compositions have been known for many years and are well documented. Molding compounds are used, for example, to produce molded articles for the automotive, construction and electronics sectors.

[0003] Ambient lighting elements or backlit functional / display elements are increasingly used in automotive interior and body applications. The market trend is to switch on / fade in lighting or functional indication only when needed, for example to differentiate the appearance of such elements between day and night, or to use such ambient dynamic lighting to enhance the perception of space in automotive interiors or to enable the display of appropriate information based on demand.

[0004] A suitable component for such applications is, for example, a multilayer article comprising a support layer, a film transilluminatable with light in the visible wavelength range, and at least one layer of a colorant or colorant composition disposed therebetween (also referred to simply as a "colorant layer" in the further context of the present invention). The support layer and film can be transilluminated with visible light (i.e., light in the wavelength range of 380 nm to 780 nm) using a light source, thereby changing the appearance of the multilayer article as desired. Different appearances can be achieved in day and night modes, as well as in "on" and "off" modes, through the coloring of the film and colorant layer(s), the transparency / opacity of the colorant layer(s), and the partial application of the colorant layer(s) in a partial region between the film and the support layer. For example, in the day mode, the multilayer article can have an opaque, high-gloss appearance with any desired coloring, and in the night mode, it can be fully transilluminated, or alternatively, only partially transilluminated, to display a specific lighting pattern or logo. To this end, in areas where transillumination is not desired in the night mode or "on" display mode, an opaque colorant layer is applied between the film and the support layer. In areas where transillumination is desired in the night mode or "on" display mode, either no colorant layer or a transilluminatable colorant layer is applied between the film and the support layer. The desired coloration of the multilayer article in the day mode or "off" display mode, and the desired coloration of the areas to be transilluminated in the night mode or "on" display mode, can be achieved through coloration of any of the film, support layer, and / or colorant layer in those areas.

[0005] The support layer must exhibit sufficient transmittance to incident light to collectively allow the presentation of a particular appearance.

[0006] Multilayer articles having transilluminatable, i.e., translucent or transparent layers, are known. Patent Document 1 discloses a multilayer article including (i) a first layer containing an acrylic resin, (ii) at least one translucent second layer (a) containing an acrylic resin and optionally further containing an impact modifier, (b) containing a rubber-modified thermoplastic resin composition, (c) optionally containing a rheology modifier, and (d) containing a visual effect additive, (iii) a third layer containing an acrylonitrile-butadiene-styrene (ABS) resin, and (iv) an optional support layer containing either a thermosetting, optionally fiber-reinforced polymer matrix or a glass-filled ABS resin.

[0007] For an appealing visual impression, it is often desirable for the support layer to at least partially scatter light from a point light source, such as an LED, thereby distributing the light diffusely across the film. Otherwise, the light source would be visible to the observer, and / or the desired visual effect when the light source is turned on would be limited to a small area of ​​the multilayer article. To achieve such a diffuse light impression on the surface of a multilayer article transilluminated by a point light source, the support layer must, on the one hand, have the highest possible transmittance of incident visible light, and, on the other hand, have the highest possible light diffusion, i.e., half-angle, associated with the highest possible scattering of the light cone generated by the point light source passing through the support layer. The higher this half-angle, the more spatially uniform the perceived illuminance of the light emitted from the point light source after passing through the support layer. Furthermore, the higher the half-angle of the support layer, the larger the surface can be transilluminated with a nearly spatially uniform light intensity. The transmittance and light diffusion (half-angle) of a material generally cannot be adjusted independently of each other and generally move in opposite directions. Optimizing light diffusion by modifying a material, for example by changing its composition, generally results in a decrease in transmittance. In particular, both variables also depend on the layer thickness of the material to be transilluminated, where as the layer thickness increases, the transmittance of the semi-transparent material decreases and the light diffusion increases.

[0008] Multilayer articles can be produced by first (partially) printing a transilluminatable film with a colorant and then subjecting said film to film insert molding together with a support material. The film insert molding method has been known for several years and is widely used.

[0009] Frequently used support materials include, for example, polycarbonate molding compounds containing scattering particles such as glass spheres, scattering pigments, or other polymers with refractive indices different from that of polycarbonate. These polymers are often used as crosslinked particles, often as particulate graft polymers with a graft shell composed of a polymer compatible or partially compatible with polycarbonate (e.g., with a polymethyl methacrylate shell), also to achieve improved compatibility with and dispersibility within the polycarbonate matrix.

[0010] A disadvantage of such molding compounds is the high softening temperature of polycarbonate. Therefore, in the production of multilayer articles, high processing temperatures must be selected to achieve good flowability of the polycarbonate. This can lead to damage to the film (e.g., undesirable deformation) or poor or incomplete adhesion of the film to the support layer, and an irregular surface appearance of the multilayer article (the formation of so-called orange peel). This can also lead to the leaching of colorant from the colorant layer or layers used in printing the film. Such molding compounds also have insufficient toughness for some applications, especially at low temperatures. Therefore, their use in some safety-relevant components is out of the question.

[0011] The above-mentioned problem of exudation is described in the literature, for example in US Pat. No. 5,629,997 and US Pat. No. 5,629,997. One way to avoid this phenomenon is to provide the printed film (decorative layer) with a protective layer to prevent the polymer melt from coming into direct contact with the decorative layer. The protective layer may consist, for example, of polycarbonate and may be applied, for example, by coextrusion.

[0012] Alternatively, to avoid seepage, US Pat. No. 5,629,999 describes a method in which a protective element in the form of a net, woven fabric or nonwoven fabric protects the decorative layer in the area of ​​the entrance opening of the polymer melt into the injection mold.

[0013] However, the described methods add cost and complexity in terms of material input and process management in the manufacture of multi-layer articles.

[0014] To improve the melt flowability and thus achieve a reduction in thermal stress on the colorant, in principle the polycarbonate can be mixed with at least one further thermoplastic resin and processed into a polycarbonate blend molding compound.

[0015] The choice of compounding partners and further components, such as additives, can be used to significantly vary the property profile of the molding compounds and moldings in terms of rheological properties and mechanical and thermal properties, and to match these to the requirements of the respective application.

[0016] However, molded articles constructed from molding compounds of polycarbonate formulations are generally opaque or poorly translucent, making multilayer articles comprising such molding compounds unsuitable for meeting the optical requirements mentioned above. [Prior art documents] [Patent documents]

[0017] [Patent Document 1] International Publication No. 2006 / 115851 [Patent Document 2] European Patent No. 1343844 [Patent Document 3] German Patent Application Publication No. 10312610 Summary of the Invention [Problem to be solved by the invention]

[0018] Therefore, it is desirable to provide a multilayer article that allows the above-mentioned dynamic lighting and / or function to fade in. Furthermore, it is desirable to simplify the manufacturing of the multilayer article, i.e., to achieve a stable laminate of the film and the support material without damaging or deforming the film or causing the colorant to leach out, and without requiring a film insert molding method requiring specific process steps, such as applying a protective measure to the decorative film, specific process management, or special equipment. Therefore, the support material must not only have a combination of good transmittance to visible light and high light diffusion, but also be suitable for injection molding and bonding with the film at relatively low temperatures, i.e., have high melt fluidity / low melt viscosity even at low temperatures.

[0019] It was further desired that the support material have high toughness even at low temperatures, so that the multilayer article has a wide field of application, for example also suitable for safety components. [Means for solving the problem]

[0020] Surprisingly, the above objectives are achieved in the following order: (I) a support layer composed of a thermoplastic molding compound including the following A), B), and C); (II) at least one layer consisting solely of a colorant or colorant composition covering at least a portion of the surface between the support layer and the film; (III) a film; A multi-layer article comprising: A) at least one representative selected from the group consisting of aromatic polycarbonates and aromatic polyester carbonates; B) a rubber-modified vinyl (copolymer) consisting of the following B.1) and B.2): C) optionally at least one further component selected from polymer additives and blending polymers, B.1) 80% to 95% by weight of structural units derived from at least one vinyl monomer, based on the rubber-modified vinyl (co)polymer B; and B.2) 5% to 20% by weight, relative to the rubber-modified vinyl (co)polymer B, of one or more elastomeric graft substrates having a glass transition temperature of less than -50°C and containing at least 50% by weight, relative to B.2, of structural units derived from 1,3-butadiene; Here, the rubber-modified vinyl (co)polymer B is (i) a dispersed phase consisting only of the following (i.1) and (i.2); (ii) a rubber-free vinyl (co)polymer matrix consisting solely of structural units of B.1 that are not bound to and trapped in rubber particles; Including, (i.1) rubber particles grafted with a vinyl (co)polymer composed of structural units of B.1, and (i.2) a vinyl (co)polymer also composed of structural units of B.1 entrapped in rubber particles as a separate dispersed phase, wherein (i) the dispersed phase has a median diameter D50 of 0.7 μm to 2.0 μm as measured by ultracentrifugation; wherein the thermoplastic molding compound contains less than 2% by weight of a rubber-based graft polymer different from component B), and It has been found that the thermoplastic molding compound is accomplished by a multi-layer article having a rubber content of at least 1.5% by weight. [Brief explanation of the drawings]

[0021] [Figure 1] 1 is a schematic diagram of a multi-layer article according to the present invention. DETAILED DESCRIPTION OF THE INVENTION

[0022] In a preferred embodiment, the thermoplastic molding compound of the support layer (I) according to the invention is 30% to 85% by weight, more preferably 50% to 82% by weight, even more preferably 58% to 82% by weight, and most preferably 65% ​​to 75% by weight of component A; 14% to 69% by weight, more preferably 17% to 49% by weight, even more preferably 17% to 41% by weight, and most preferably 24% to 34% by weight of component B; 0.05% to 20% by weight, more preferably 0.1% to 10% by weight, even more preferably 0.2% to 5% by weight, and most preferably 0.3% to 2% by weight of component C; Includes.

[0023] In a preferred embodiment, the molding compound of the support layer (I) comprises less than 1 wt. %, more preferably less than 0.5 wt. %, and even more preferably less than 0.2 wt. % of a rubber-based graft polymer different from component B). Most preferably, the molding compound does not comprise a rubber-based graft polymer different from component B).

[0024] In a preferred embodiment, the molding compound of the support layer (I) has a rubber content in the range of 1.5 wt. % to 6 wt. %, more preferably in the range of 1.8 wt. % to 5 wt. %, even more preferably in the range of 1.9 wt. % to 4.1 wt. %, and most preferably in the range of 2.5 wt. % to 3.0 wt. %.

[0025] The above preferred ranges of Components A and B and Component C can be combined with each other as desired.

[0026] In a preferred embodiment, the support layer (I) consists exclusively of a thermoplastic molding compound consisting exclusively of components A, B and C to the extent of at least 80% by weight, more preferably at least 95% by weight, more preferably at least 99% by weight and most preferably 100% by weight.

[0027] The multilayer article is suitable for transillumination with visible light using a light source, i.e., the multilayer article is preferably transilluminatable. The light source is arranged so that light first enters the support material (I) and finally reaches the film (III) through the layer (II). The light source is preferably an LED light source.

[0028] Transilluminatable is to be understood to mean that the visual impression on the side opposite the light source is changed when the light source is turned on.

[0029] In a preferred embodiment, the multilayer article according to the invention has, at least in partial regions of its actual local thickness, a transmittance at at least one wavelength in the wavelength range of the spectrum from 380 nm to 780 nm of at least 10%, more preferably at least 25%, even more preferably at least 40%, most preferably at least 45%, wherein the transmittance is obtained from a transmission spectrum measured according to the standard in DIN / ISO 13468-2 (2006 edition).

[0030] The present invention further provides the use of a molding compound comprising the above-mentioned components A, B, and C, as well as further specified features, as a support layer (I) in the above-mentioned multilayer article.

[0031] The present invention further provides a lighting unit comprising the above-identified multilayer article and a light source emitting light having at least one wavelength in the wavelength range of the spectrum from 380 nm to 780 nm, the light source being positioned such that the support layer is transilluminated by the light emitted by the light source.

[0032] The present invention further provides a method for making a multi-layer article, comprising the steps of: a) producing a film; b) printing at least a portion of the film with at least one layer consisting solely of a colorant or colorant composition; c) optionally thermoforming the film; d) insert molding the film with a thermoplastic molding compound as described above; The present invention provides a method comprising:

[0033] Support layer composition Ingredient A The aromatic polycarbonates and / or aromatic polyester carbonates of component A suitable according to the invention are known from the literature or can be prepared by methods known from the literature (for the preparation of aromatic polycarbonates, see, for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964, and also DE-A-1 495 626, DE-A-2 232 877, DE-A-2 703 376, DE-A-2 714 544, DE-A-3 000 610, DE-A-3 832 396; for the preparation of aromatic polyester carbonates, see, for example, DE-A-3 007 934).

[0034] Aromatic polycarbonates are produced, for example, by reacting diphenols with carbonyl halides, preferably phosgene and / or aromatic dicarbonyl dihalides, preferably dihalides of benzenedicarboxylic acids, by an interfacial process, optionally using chain terminators, such as monophenols, and optionally using trifunctional or higher-functional branching agents, such as triphenols or tetraphenols. Production via melt polymerization by reacting diphenols with, for example, diphenyl carbonate is also possible.

[0035] The diphenols for the preparation of aromatic polycarbonates and / or aromatic polyester carbonates preferably have the formula (I): [ka] (In the formula, A is a single bond, C1-C5-alkylene, C2-C5-alkylidene, C5-C6-cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO2-, or a C6-C alkylene group optionally fused with a further aromatic ring containing a heteroatom. 12 -arylene, or a group represented by formula (II) or formula (III): [ka] is the basis of B is, in each case, C1~C 12 alkyl, preferably methyl, halogen, preferably chlorine and / or bromine, x is, independently in each occurrence, 0, 1, or 2; p is 1 or 0, and R 5 and R 6 For each X 1 are individually selectable and are, independently of one another, hydrogen or C1-C6-alkyl, preferably hydrogen, methyl or ethyl, X 1 is carbon, and m is an integer of 4 to 7, preferably 4 or 5, provided that at least one atom X 1 R on top 5 and R 6 is a diphenol of which alkyl is also alkyl.

[0036] Preferred diphenols are hydroquinone, resorcinol, dihydroxydiphenols, bis(hydroxyphenyl)-C1-C5-alkanes, bis(hydroxyphenyl)-C5-C6-cycloalkanes, bis(hydroxyphenyl)ethers, bis(hydroxyphenyl)sulfoxides, bis(hydroxyphenyl)ketones, bis(hydroxyphenyl)sulfones, and α,α-bis(hydroxyphenyl)diisopropylbenzene, and their ring-brominated and / or ring-chlorinated derivatives.

[0037] Particularly preferred diphenols are 4,4'-dihydroxybiphenyl, 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'-dihydroxybiphenyl sulfide, 4,4'-dihydroxybiphenyl sulfone, and their dibrominated or dichlorinated and tetrabrominated or tetrachlorinated 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.

[0038] The diphenols can be used individually or in the form of any desired mixtures. The diphenols are known from the literature or can be obtained by literature methods.

[0039] Examples of chain terminators suitable for producing thermoplastic aromatic polycarbonates include phenol, p-chlorophenol, p-tert-butylphenol, or 2,4,6-tribromophenol, as well as long-chain alkylphenols, such as 4-[2-(2,4,4-trimethylpentyl)]phenol, 4-(1,3-tetramethylbutyl)phenol according to DE-A-2842005, and mono- or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituents, such as 3,5-di-tert-butylphenol, p-isooctylphenol, p-tert-octylphenol, p-dodecylphenol, and 2-(3,5-dimethylheptyl)phenol and 4-(3,5-dimethylheptyl)phenol. The amount of chain terminator used is generally between 0.5 mol% and 10 mol%, based on the total moles of the diphenols used in each case.

[0040] The thermoplastic aromatic polycarbonate preferably has an average molecular weight (weight average M) of 20,000 g / mol to 40,000 g / mol, more preferably 24,000 g / mol to 32,000 g / mol, and particularly preferably 26,000 g / mol to 33,000 g / mol. w , as measured by GPC (gel permeation chromatography) using bisphenol A-based polycarbonate standards. The preferred range results in a particularly advantageous balance of mechanical and rheological properties in the compositions of the present invention.

[0041] The thermoplastic aromatic polycarbonates can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol % of trifunctional or more than trifunctional compounds, for example compounds having three or more phenolic groups, relative to the total diphenols used. Preference is given to using linear polycarbonates, more preferably linear polycarbonates based on bisphenol A.

[0042] Both homopolycarbonates and copolycarbonates are suitable. The copolymers of the present invention based on component A can also be prepared using polydiorganosiloxanes having 1 to 25% by weight, preferably 2.5 to 25% by weight, of hydroxyaryloxy end groups, based on the total amount of diphenols used. These are known (U.S. Pat. No. 3,419,634) and can be prepared by methods known from the literature. Polydiorganosiloxane-containing copolycarbonates are also suitable, the preparation of which is described, for example, in DE-A-3334782.

[0043] The aromatic dicarbonyl dihalides for the preparation of aromatic polyester carbonates are preferably the diacyl dichlorides of isophthalic acid, terephthalic acid, diphenyl ether 4,4'-dicarboxylic acid, and naphthalene-2,6-dicarboxylic acid.

[0044] Particularly preferred are mixtures of the diacyl dichlorides of isophthalic and terephthalic acid in ratios between 1:20 and 20:1.

[0045] In the preparation of polyester carbonates, a carbonyl halide, preferably phosgene, is additionally used as a difunctional acid derivative.

[0046] Chain terminators contemplated for the preparation of aromatic polyester carbonates are not only the monophenols mentioned above, but also their chlorocarbonates and acyl chlorides of aromatic monocarboxylic acids, which may optionally be C1-C 22 - may be substituted with an alkyl group or a halogen atom, wherein aliphatic C2-C 22 -monocarbonyl chlorides may also be used as chain terminators.

[0047] The amount of chain terminator in each case is 0.1 mol % to 10 mol % based on the number of moles of diphenol in the case of phenolic chain terminators, and based on the number of moles of dicarbonyl dichloride in the case of monocarbonyl chloride chain terminators.

[0048] One or more aromatic hydroxycarboxylic acids may also be used in the preparation of the aromatic polyester carbonates.

[0049] The aromatic polyester carbonates can be either linear or branched in a known manner (see DE-A-2940024 and DE-A-3007934), with linear polyester carbonates being preferred.

[0050] Branching agents that can be used include, for example, trifunctional or polyfunctional carbonyl chlorides, such as trimesoyl trichloride, cyanuroyl trichloride, 3,3',4,4'-benzophenonetetracarbonyl tetrachloride, 1,4,5,8-naphthalenetetracarbonyl tetrachloride, or pyromellitoyl tetrachloride, in an amount of 0.01 mol % to 1.0 mol % (based on the dicarbonyl dichloride used), or trifunctional or polyfunctional phenols, such as phloroglucinol, 4,6-dimethyl-2,4,6-tri(4-hydroxyphenyl)hept-2-ene ... These include (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-dihydroxyphenyl)propane, tetra(4-[4-hydroxyphenylisopropyl]phenoxy)methane, and 1,4-bis[4,4'-dihydroxytriphenyl)methyl]benzene. Phenolic branching agents can be initially charged with diphenols, and acid chloride branching agents can be introduced with acid dichlorides.

[0051] The proportion of carbonate structural units in thermoplastic aromatic polyester carbonate can be varied as desired.The proportion of carbonate groups is preferably at most 100 mol%, particularly preferably at most 80 mol%, particularly preferably at most 50 mol%, based on the total of ester groups and carbonate groups.The ester moieties and carbonate moieties of aromatic polyester carbonate can be present in the polycondensate in block form or random distribution.

[0052] The thermoplastic aromatic polycarbonates and polyester carbonates can be used alone or in any desired mixture.

[0053] As component A, it is preferred to use linear polycarbonates based solely on bisphenol A.

[0054] Component B Component B is selected from the following rubber-modified vinyl (co)polymers B.1) and B.2), B.1) 80% to 95% by weight, preferably 83% to 93% by weight, more preferably 85% to 92% by weight, of structural units derived from at least one vinyl monomer, based on the rubber-modified vinyl (co)polymer B; and B.2) Rubber-modified vinyl (co)polymers B containing 5% to 20% by weight, preferably 7% to 17% by weight, more preferably 8% to 15% by weight, of structural units derived from 1,3-butadiene, based on B.2, and having a glass transition temperature T g one or more elastomer graft substrates having Here, the rubber-modified vinyl (co)polymer B is (i) a dispersed phase consisting only of the following (i.1) and (i.2); (ii) a rubber-free vinyl (co)polymer matrix consisting solely of structural units of B.1 that are not bound to and trapped in rubber particles; Including, (i.1) rubber particles grafted with a vinyl (co)polymer composed of structural units of B.1, and (i.2) a vinyl (co)polymer also composed of structural units of B.1 entrapped in rubber particles as a separate dispersed phase, and (i) the dispersed phase has a median diameter D50 measured by ultracentrifugation of 0.7 μm to 2.0 μm, preferably 0.7 μm to 1.5 μm, especially 0.7 μm to 1.2 μm.

[0055] Unless otherwise expressly specified in the present invention, the glass transition temperature T g For all components, the temperature was measured by dynamic differential scanning calorimetry (DSC) according to DIN EN 61006 (1994 edition) at a heating rate of 10 K / min with the midpoint temperature T g is determined using the tangent method.

[0056] The rubber-modified vinyl (co)polymer of component B preferably has a melt volume flow rate (MVR) of 2 ml / 10 min to 20 ml / 10 min, particularly preferably 3 ml / 10 min to 15 ml / 10 min, and in particular 4 ml / 10 min to 8 ml / 10 min, measured at 220°C and 10 kg piston load according to ISO 1133 (2012 edition). When a mixture of two or more rubber-modified vinyl (co)polymers is used as component B, the preferred MVR range corresponds to the average of the MVRs of the individual components, weighted by the mass fraction of the components in the mixture.

[0057] Such rubber-modified vinyl (co)polymers B are, for example, B.1 80% to 95% by weight, preferably 83% to 93% by weight, particularly preferably 85% to 92% by weight, of at least one vinyl monomer, based on the rubber-modified vinyl (co)polymer B, B.2 graft substrates of one or more elastomers with a glass transition temperature of less than -50°C, preferably less than -60°C, particularly preferably less than -70°C, which contain structural units derived from 1,3-butadiene in an amount of 5% by weight to 20% by weight, preferably 7% by weight to 17% by weight, particularly preferably 8% by weight to 15% by weight, based on the rubber-modified vinyl (co)polymer B, and at least 50% by weight, preferably at least 70% by weight, particularly preferably 100% by weight, based on B.2, of 1,3-butadiene, The copolymer is prepared by free radical polymerization in the presence of, preferably in a bulk polymerization process.

[0058] The bulk polymerization reaction preferably used to prepare the rubber-modified vinyl (co)polymer B comprises both the polymerization of B.1 vinyl monomers and the grafting of the vinyl (co)polymer thus formed onto the elastomeric graft substrate B.2. Furthermore, in this reaction mode, self-assembly (phase separation) leads to the formation of a dispersed phase (i) consisting of (i.1) and (i.2): (i.1) rubber particles grafted with a vinyl (co)polymer composed of structural units of B.1, and (i.2) a vinyl (co)polymer also composed of structural units of B.1 entrapped in rubber particles as a separate dispersed phase, Here, this rubber-containing phase (i) is in the form of a dispersion in a rubber-free vinyl (co)polymer matrix (ii) consisting of structural units of B.1 that are not bound to and trapped in rubber particles.

[0059] In contrast to the other vinyl (co)polymer proportions in component B, the rubber-free vinyl (co)polymer (ii) can be dissolved using a suitable solvent, such as acetone.

[0060] The size of the dispersed phase (i) in the rubber-modified vinyl (co)polymer B thus produced is adjusted via the reaction mode conditions, such as the temperature and viscosity of the polymer obtained therefrom, as well as the shear from stirring.

[0061] The median particle size D50 is the diameter above which 50% by weight of the particles lie and below which 50% by weight lie. Unless otherwise expressly stated in the present invention, this is determined for all components by ultracentrifuge measurements (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972), 782-796).

[0062] The monomer B.1 is preferably B.1.1 60 to 85 parts by weight, particularly preferably 65 to 80 parts by weight, more preferably 70 to 78 parts by weight of styrene, in each case relative to the sum of B.1.1 and B.1.2, B.1.2 15 to 40 parts by weight, particularly preferably 20 to 35 parts by weight, more preferably 22 to 30 parts by weight of acrylonitrile, in each case relative to the sum of B.1.1 and B.1.2, and optionally B.1.3 0 to 10 parts by weight, preferably 0 to 7 parts by weight, more preferably 0 to 5 parts by weight, of methyl methacrylate or n-butyl acrylate, in each case relative to 100 parts by weight of the total of B.1.1 and B.1.2, It is a mixture consisting only of

[0063] In a further preferred embodiment, monomer B.1 is a mixture of 22 to 26 parts by weight of acrylonitrile and 74 to 78 parts by weight of styrene, optionally containing up to 10 parts by weight, particularly preferably up to 5 parts by weight, of n-butyl acrylate or methyl methacrylate, where the sum of the parts by weight of styrene and acrylonitrile is 100 parts by weight.

[0064] It is particularly preferred if B.1 does not include B.1.3 and the above preferred ranges apply to B.1.1 and B.1.2.

[0065] Preferred graft substrates B.2 are butadiene-containing diene rubbers or mixtures of butadiene-containing diene rubbers or copolymers of butadiene-containing diene rubbers or mixtures thereof with further copolymerizable monomers (for example B.1.1 and B.1.2).

[0066] A particularly preferred graft substrate B.2 is pure polybutadiene rubber. In a further preferred embodiment, B.2 is a styrene-butadiene block copolymer rubber.

[0067] Component B preferably has a polybutadiene content of 5% to 18% by weight, more preferably 7% to 15% by weight, especially 8% to 13% by weight.

[0068] Particularly preferred rubber-modified vinyl (co)polymers of component B are, for example, the bulk-polymerized ABS polymers described in DE-A-2035390 (=US Pat. No. 3,644,574) or DE-A-2248242 (=GB Pat. No. 1,409,275), or in Ullmanns Enzyklopaedie der Technischen Chemie, Vol. 19 (1980), p. 280 ff.

[0069] The vinyl (co)polymer (ii) that is not chemically bonded to the rubber substrate(s) B.2 and not trapped in rubber particles may be formed as a result of its preparation during the polymerization of graft polymer B, as described above. Similarly, a portion of this vinyl (co)polymer (ii) that is not chemically bonded to the rubber substrate(s) B.2 and not trapped in rubber particles may be formed in the rubber-modified vinyl (co)polymer of component B as a result of its preparation during its preparation in a bulk polymerization process, and another portion may be polymerized separately and added to component B as a constituent of component B. In component B, the proportion of vinyl (co)polymer (ii), regardless of its origin, measured as the acetone-soluble portion, is preferably at least 50% by weight, particularly preferably at least 60% by weight, more preferably at least 70% by weight, relative to component B.

[0070] In the rubber-modified vinyl (co)polymer of component B, the vinyl (co)polymer (ii) has a weight average molecular weight M of 70 kg / mol to 250 kg / mol, preferably 130 kg / mol to 200 kg / mol, in particular 150 kg / mol to 180 kg / mol. w It has.

[0071] In the context of the present invention, the weight average molecular weight M of the vinyl (co)polymer (ii) in component B wis determined by gel permeation chromatography (GPC) in tetrahydrofuran against polystyrene standards.

[0072] Component B preferably does not contain alkali metals, alkaline earth metals, ammonium or phosphonium salts of saturated fatty acids having 8 to 22 carbon atoms, resin acids, alkylsulfonic acids and alkylarylsulfonic acids, and fatty alcohol sulfates.

[0073] Component B preferably comprises less than 100 ppm, particularly preferably less than 50 ppm, very particularly preferably less than 20 ppm of alkali metal and alkaline earth metal ions.

[0074] Suitable rubber-modified vinyl (co)polymers as component B are, for example, Magnum® 3404, Magnum® 3504, and Magnum® 3904 from Trinseo SA (Luxembourg).

[0075] Component C Component C, if present, may optionally be one or more representatives selected from the group consisting of polymeric additives and polymeric blend partners.

[0076] The polymer additive / compounding polymer is preferably selected from the group consisting of lubricants and mold release agents, stabilizers, colorants, compatibilizers, further impact modifiers different from component B, further polymer components different from components A and B (e.g. functional compounding partners or graft polymers with a core-shell structure prepared in an emulsion polymerization process), and fillers and reinforcing agents.

[0077] In a preferred embodiment, no filler or reinforcing agent is present in component C. Even more preferred is the absence of a colorant. Even more preferred is the absence of a blending partner polymer. Even more preferred is the absence of a polymer component. In a particularly preferred embodiment, neither a filler or reinforcing agent, nor a colorant or blending partner polymer is present. Most preferred is the absence of a filler or reinforcing agent, nor a colorant or polymer component.

[0078] In a preferred embodiment, at least one polymeric additive selected from the group consisting of lubricants and mold release agents, and stabilizers, is used as component C.

[0079] In a preferred embodiment, at least one representative selected from the group consisting of sterically hindered phenols, organic phosphites, and organic or inorganic Bronsted acids is used as stabilizer.

[0080] In a preferred embodiment, at least one representative selected from the group consisting of sterically hindered phenols, organic phosphites, and organic or inorganic Bronsted acids is used as stabilizer.

[0081] In a preferred embodiment, fatty acid esters, particularly preferably fatty acid esters of pentaerythritol or glycerol, are used as lubricants and mold release agents.

[0082] In a particularly preferred embodiment, C8 to C4 of pentaerythritol 22 Fatty acid esters, C8 to C of glycerol 22At least one polymer additive selected from the group consisting of fatty acid esters, tris(2,4-di-tert-butylphenyl)phosphite, 2,6-di-tert-butyl-4-(octadecaneoxycarbonylethyl)phenol, tetrakis(2,4-di-tert-butylphenyl)-4,4-biphenyl diphosphonite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, and triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] is used as component C.

[0083] In a further embodiment, Component C does not include a rubber-modified vinyl (co)polymer prepared by emulsion polymerization.

[0084] Preparation of the molding compound for the support layer From component A, component B and component C according to the invention, a thermoplastic molding compound is produced.

[0085] For example, the thermoplastic molding compounds according to the invention can be produced when the individual components of the composition are mixed in a well-known manner and melt-compounded and melt-extruded in customary equipment, such as internal mixers, extruders and twin-screw extruders, preferably at temperatures of 200°C to 320°C, particularly preferably 240°C to 300°C, very particularly preferably 260°C to 290°C.

[0086] In the context of this application, this process is generally referred to as compounding.

[0087] Thus, the term "molding compound" should be understood to mean the product obtained when the constituents of the composition are melt compounded and melt extruded.

[0088] The mixing of the individual components of the composition can be carried out in a known manner either sequentially or simultaneously at a temperature of about 20° C. (room temperature) or higher, i.e., for example, some components can be introduced through the main intake of an extruder, and the remaining components can be introduced later in the compounding process through a side extruder.

[0089] Colorant composition For the decoration of the film, colorant compositions customary for the respective method are used, such as screen printing inks, color coats or inks.

[0090] The colorant composition according to the present invention comprises as a necessary component at least one colorant, the term colorant being understood to mean organic and inorganic pigments as well as organic and inorganic dyes, including soluble dyes.

[0091] One or more additional components may also be present which may be broadly classified as volatile and non-volatile components.

[0092] Non-volatile components include binders, fillers, and auxiliary agents, which are typically required in very small amounts but are often essential for problem-free processing.

[0093] Volatile components are essentially liquids that dissolve or disperse the colorant and any other components. They can be organic or inorganic solvents, or a mixture of two or more solvents. The solvent is often water or a mixture of water and another solvent.

[0094] Suitable organic solvents include, for example, ketones, esters, alcohols, and aromatic or aliphatic hydrocarbons. It is also possible to use a mixture of two or more organic or inorganic solvents.

[0095] The non-volatile binder securely fixes the colorant to the substrate, allowing the finished print to withstand stresses from abrasion, heat, and mechanical bending.

[0096] Suitable binders for colorants include, for example, a combination of nitrocellulose and a plasticizer, thermoplastic polyurethane, thermoplastic polyester, thermoplastic polycarbonate, and thermoplastic poly(meth)acrylate. It is also possible to combine various binders, as described in DE 19832570 A1. It is also possible to form the binder (e.g., polyurethane or epoxy resin) in situ by chemical reaction during application of the colorant composition.

[0097] As long as sufficient temperature resistance is ensured, there is virtually no limit to the selection of suitable dyes.Suitable organic colorants include, for example, colorants from the azo series, anthraquinone series, azoporphine series, thioindigo series, dioxazine series, naphthalenetetracarboxylic acid series, or perylenetetracarboxylic acid series, and phthalocyanine compounds.Suitable inorganic colorants include, for example, iron oxide, ultramarine, zinc sulfide, silicon dioxide, aluminum oxide, titanium oxide, nickel compounds, chromium compounds, phosphotungsten molybdate bronze, and carbon black.Special effect colorants, such as mica pigments coated with metal oxides and metallic aluminum pigments, can also be used.

[0098] If desired, fillers can also be incorporated into the colorant composition. Suitable fillers include carbonates, sulfates, silicates, and oxides.

[0099] Suitable fillers include magnesium, calcium, and barium carbonates, calcium and barium sulfates, silicates and aluminosilicates, and aluminum, titanium, and silicon oxides. Mixtures of these compounds can also be used.

[0100] Conventional and well-known adjuvants can also be incorporated into the colorant composition, such as wetting and dispersing aids, anti-settling agents, leveling agents, adhesion promoters, stabilizers, anti-scratch additives, and the like.

[0101] The preparation of the coating composition from the components used is carried out by mixing the components using methods known to those skilled in the art, such as dispersing, dissolving or compounding in the melt.

[0102] Particularly heat-resistant colorant compositions are described, for example, in EP-A-0 688 839. Heat-resistant colorant compositions are also available under the name Noriphan™ HTR from Proll KG, Weissenburg, Germany.

[0103] However, the present invention is not limited to very heat-resistant colorant compositions. As mentioned at the beginning, the inventive selection of a support material that has good melt flowability even at low processing temperatures also makes it possible to use colorant compositions in the production of multilayer articles that are more sensitive to high temperatures and therefore have not previously been suitable for the prior art production of multilayer articles by film insert molding.

[0104] Colorants that are particularly suitable for screen printing on PMMA films are described in DE 101 51 281 A1.

[0105] In the manufacture of multi-layer articles according to the present invention, some or all of the volatile components present in the colorant composition may be emitted, so that the claimed multi-layer articles comprise the present compositions according to component II only to a small extent, if any.

[0106] The colorant composition applied to the film can be transparent, translucent, or opaque to visible light. If the colorant composition is opaque, it is not printed across the entire area of ​​the film that is to be transilluminated. This allows, for example, for fade-in display elements.

[0107] It is also possible to print different film regions with different colorant compositions, or to print multiple layers of different colorant compositions on top of each other. A preferred embodiment here is the overlay printing of a transilluminatable, i.e., transparent or translucent, colorant composition with an opaque colorant composition. It is particularly preferred if these two colorant compositions have the same or similar coloration.

[0108] film The film can be a monolayer film or a multilayer film.

[0109] One or more additional layers in the multi-layer construction may be applied by, for example, coextrusion, lamination, and / or coating methods such as wet coating or plasma coating.

[0110] The film is preferably a film composed of a thermoplastic composition comprising one or more thermoplastic polymers and optionally further additives. Conventional polymer additives can be added as additives. The thermoplastic composition can be colored, in particular, with a suitable colorant.

[0111] Thermoplastic polymers include, for example, thermoplastic polyurethanes, polymethyl methacrylate (PMMA) and modified versions of PMMA, polyolefins, aromatic polycarbonates (PC), and also copolycarbonates (Co-PC), polyetherimides, styrene-acrylonitrile, acrylonitrile-styrene-acrylic ester copolymers (ASA), acrylonitrile-butadiene-styrene copolymers (ABS), polyesters, and mixtures of these polymers.

[0112] The material for the film is preferably selected from thermoplastic polymers based on polycarbonate.

[0113] In an alternative preferred embodiment, the film is selected from thermoplastic polymers based on polymethyl methacrylate.

[0114] Here, the term "based on" should be understood to mean that the proportion of polymer in the total composition of the film is at least 60% by weight, preferably at least 75% by weight, more preferably at least 90% by weight.

[0115] In a preferred embodiment, the film is transilluminatable throughout its entirety, the definition of the term transilluminatable being explained above.

[0116] Only portions of the film may be transilluminated by a light source. This may be achieved, for example, by using a film composed of two or more layers, where one of the layers may have a high transmittance for visible light (i.e., light in the wavelength range of the spectrum from 380 nm to 780 nm), and a further layer may be opaque but have holes, slots, or similar openings for the light. In such a construction, only the portions of the film where the opaque layer has openings for the light can be transilluminated.

[0117] The film is transilluminatable to visible light in the transilluminated region at its thickness in practical use. In the context of the present invention, the term "transilluminatable" is to be understood as referring to a film having a transmittance of at least 20%, more preferably at least 50%, particularly preferably at least 70%, determined according to the standard in DIN / ISO 13468-2 (2006 edition, (illuminant: D65, observer: 10°)), preferably in the region transilluminated by a light source of at least one wavelength in the visible wavelength range of the spectrum (380 nm to 780 nm).

[0118] In a preferred embodiment, the entire film has a visible transmittance determined according to DIN / ISO 13468-2 (2006 edition, (illuminant: D65, observer: 10°)) of at least 20%, preferably at least 50%, particularly preferably at least 70%.

[0119] It is most preferred if the film further has a yellowness value as a measure of color neutrality of at most 20, preferably at most 5, particularly preferably at most 2, measured according to ASTM E313 (2010 edition).

[0120] The thickness of the film is from 50 μm to 1 mm, preferably from 100 μm to 700 μm, which should be understood to mean that the film has this thickness at any point over that range.

[0121] The film may be coated on the side opposite the support layer with a coating composition. The coating is typically intended to provide mechanical protection against abrasion and scratches and / or protection from the effects of weathering, i.e., precipitation, temperature changes, and UV radiation. Specific surface haptics or surface optics may also be achieved with the coating.

[0122] Suitable coatings are, for example, heat-curable coating systems based on polysiloxane coatings, which can be either single-layer systems or multi-layer systems (with merely an adhesion-promoting primer layer between the substrate and the polysiloxane topcoat).

[0123] It is also possible to use UV-curable coating systems based, for example, on acrylates, urethane acrylates or acryloyl silanes, optionally containing fillers which improve scratch resistance.

[0124] The coating and / or film itself may also contain the colorants identified above.

[0125] For example, the thermoplastic composition constituting the film may contain such a colorant. In such a case, the film itself is then colored throughout. An opaque colorant composition can then be applied to the portion of the surface between the film and the support material, for example as layer (II).

[0126] If the film coating contains colorants, these can be selected from those mentioned above as well as colorants that have low temperature resistance.

[0127] If the coating of the film or the thermoplastic composition that constitutes the film contains colorants, these colorants have properties and are used in concentrations that ensure that the transilluminability of the film is still ensured, which should be understood to mean that the coloration of the coating on the side opposite the support layer and the film itself is not opaque.

[0128] Manufacturing of multilayer articles The multilayer article is preferably produced by the FIM method (film insert molding). Film insert molding (FIM) is a special injection molding method in which a film, optionally three-dimensionally preformed, is inserted as an insert into an injection mold, after which a plastic melt (belt) is injected. This method is known to those skilled in the art and is widely used.

[0129] The insert is typically a deformed and optionally decorated film. Deformation can be carried out using mechanical or non-contact thermoforming. For example, deep drawing is used. Other methods are vacuum deep drawing, compression, or blow molding. For tighter positional tolerances, known high-pressure forming (HPF) methods are used, as described, for example, in EP 2197656. The film is generally cut after forming. This can be done by common methods such as punching, milling, knife cutting, laser cutting, and water jet cutting.

[0130] Thus, in brief, in a preferred method, the production of a multilayer article according to the present invention preferably comprises: a) printing a film with a colorant composition; b) optionally deforming and optionally subsequently cutting the film; c) insert molding the film together with the molten molding compound of the support layer in an injection mold; Includes.

[0131] It is also possible to perform three-dimensional molding of the film and insert molding of the film in a single injection mold. Such a simplified method is described, for example, in WO 2014 / 044694.

[0132] Printing of the film can be carried out by various printing methods, such as screen printing, offset printing, and digital printing by xerography or inkjet printing.

[0133] Other possible methods of printing the film are painting, pad printing, letterpress (including flexography), lithography, and intaglio printing.

[0134] The method used will depend on the print substrate, component geometry, print quality requirements, and film type (filter), among other factors.

[0135] Digital printing allows color printing without first requiring a printing die or plate. Digitized print data is passed directly to the digital press. This method allows for fast printing on demand and high flexibility in printing, including single-copy runs. The two most important digital printing techniques are xerography and inkjet printing. Digitized information is printed by xerography, which is similar to color laser copying. Another method of printing digital information is inkjet printing, which uses high-precision microjets to spray ink directly onto the surface to be printed. Inks should be selected so that they wet the film surface well and adhere firmly to it.

[0136] Due to its high printing speed, offset printing is particularly suitable for the economical production of large volumes (runs) and is used, for example, to produce very fine line patterns.

[0137] It is preferred to use screen printing as the printing method, which provides printed images with high opacity and color density, which is important for transmitted light applications where the printed film is backlit, for example, in automotive components with day / night designs such as dials or decorative lighting elements.

[0138] The printed design can be, for example, a company emblem, an indication of the vehicle type or class, a block of text, or a purely decorative pattern.

[0139] After the film has been subjected to insert molding together with a support material, it is also possible to apply a further layer of support material in an overmolding process so that this further layer seamlessly surrounds the surface of the component obtained after insert molding. Overmolding is known to those skilled in the art and is described, for example, in the published specifications of WO 2012 / 069590, EP 2402140 and DE 102007011338.

[0140] In a further preferred embodiment, in addition to the film of component III, an outer film is optionally additionally applied to the plastic article. This outer film is preferably applied to the side that will face the viewer in the final application of the multilayer article according to the invention once it is installed. In a more preferred embodiment, the outer film is a hard coating film, also called a hard coat covering film.

[0141] The thickness of the support layer I is preferably 0.5 mm to 10 mm, more preferably 1 mm to 5 mm. This should be understood to mean that the support layer I has this thickness at any point throughout that range. A layer formed directly by subjecting a film to insert molding does not necessarily have the same thickness over the entire area of ​​the film; rather, it may have a different thickness depending on, for example, the configuration of reinforcing ribs, the shape of a component, or the mounting structure.

[0142] In the transilluminated region, the support layer I preferably has a thickness of 0.5 mm to 5 mm, particularly preferably 1.5 mm to 3.5 mm, and particularly preferably 1.7 mm to 2.5 mm.

[0143] Further embodiments 1 to 40 of the present invention are described below:

[0144] 1. In the following order: (I) a support layer composed of a thermoplastic molding compound including the following A), B), and C); (II) at least one layer consisting solely of a colorant or colorant composition covering at least a portion of the surface between the support layer and the film; (III) a film; A multi-layer article comprising: A) at least one representative selected from the group consisting of aromatic polycarbonates and aromatic polyester carbonates; B) a rubber-modified vinyl (copolymer) consisting of the following B.1) and B.2): C) optionally at least one further component selected from polymer additives and blending polymers, B.1) 80% to 95% by weight of structural units derived from at least one vinyl monomer, based on the rubber-modified vinyl (co)polymer B; and B.2) 5% to 20% by weight, relative to the rubber-modified vinyl (co)polymer B, of one or more elastomeric graft substrates having a glass transition temperature of less than -50°C and containing at least 50% by weight, relative to B.2, of structural units derived from 1,3-butadiene; Here, the rubber-modified vinyl (co)polymer B is (i) a dispersed phase consisting only of the following (i.1) and (i.2); (ii) a rubber-free vinyl (co)polymer matrix consisting solely of structural units of B.1 that are not bound to and trapped in rubber particles; Including, (i.1) rubber particles grafted with a vinyl (co)polymer composed of structural units of B.1, and (i.2) a vinyl (co)polymer also composed of structural units of B.1 entrapped in rubber particles as a separate dispersed phase, wherein (i) the dispersed phase has a median diameter D50 of 0.7 μm to 2.0 μm as measured by ultracentrifugation; wherein the thermoplastic molding compound contains less than 2% by weight of a rubber-based graft polymer different from component B), and A multi-layer article, wherein the thermoplastic molding compound has a rubber content of at least 1.5% by weight.

[0145] 2. The multilayer article of embodiment 1, wherein the film is transilluminatable.

[0146] 3. The multilayer article of embodiment 1 or 2, wherein the film is composed of a thermoplastic material.

[0147] 4. The multilayer article of any of the preceding embodiments, wherein the film consists exclusively of methyl methacrylate to the extent of at least 60% by weight.

[0148] 5. The multilayer article according to any one of embodiments 1 to 3, wherein the film consists exclusively of polycarbonate to the extent of at least 60% by weight.

[0149] 6. The multilayer article of any preceding embodiment, wherein the thickness of the film is in the range of 50 μm to 1 mm at any point.

[0150] 7. The multilayer article of any preceding embodiment, wherein the thickness of the film is in the range of 100 μm to 700 μm at any point.

[0151] 8. The multilayer article of any of the preceding embodiments, wherein the film has a transmittance of at least 20% determined according to the standard in DIN / ISO 13468-2 (2006 edition) at its thickness in practical use in an area transilluminated by at least one wavelength in the wavelength range of the spectrum from 380 nm to 780 nm.

[0152] 9. The multilayer article of any of the preceding embodiments, wherein the film has a transmittance of at least 50% determined according to the standard in DIN / ISO 13468-2 (2006 edition) at its thickness in practical use in an area transilluminated with at least one wavelength in the wavelength range of the spectrum from 380 nm to 780 nm.

[0153] 10. The multilayer article of any of the preceding embodiments, wherein the film has a transmittance of at least 70% determined according to the standard in DIN / ISO 13468-2 (2006 edition) at its thickness in practical use in an area transilluminated with at least one wavelength in the wavelength range of the spectrum from 380 nm to 780 nm.

[0154] 11. The multilayer article of any of the preceding embodiments, wherein the thickness of the support layer is in the range of 1 mm to 5 mm at any point.

[0155] 12. The multilayer article of any of the preceding embodiments, wherein the support layer has a thickness in the transilluminated area of ​​from 1.5 mm to 3.7 mm.

[0156] 13. The multilayer article according to any of the preceding embodiments, wherein in partial regions of the surface between the support layer (I) and the film (III), the multilayer article comprises a light transmission-reducing layer consisting of a colorant or colorant composition, and in these regions the multilayer article has a visible transmission of at most 10%, determined according to DIN / ISO 13468-2 (2006 edition) with a D65 illuminant and at an angle of 10° to the observer.

[0157] 14. The multilayer article according to any of the preceding embodiments, wherein in partial regions of the surface between the support layer (I) and the film (III), the multilayer article comprises a light transmission reduction layer consisting of a colorant or colorant composition, and in these regions the multilayer article has a visible transmission of at most 25%, determined according to DIN / ISO 13468-2 (2006 edition) with a D65 illuminant and at an angle of 10° to the observer.

[0158] 15. A multilayer article according to any of the preceding embodiments, wherein in partial regions of the surface between the support layer (I) and the film (III), the multilayer article comprises a light transmission reduction layer consisting of a colorant or colorant composition, and in these regions the multilayer article has a visible transmission of up to 45%, determined according to DIN / ISO 13468-2 (2006 edition) with a D65 illuminant and at an angle of 10° to the observer.

[0159] 16. The support layer is 30% to 85% by weight of component A; 14% to 69% by weight of component B; 0.05% by weight to 20% by weight of component C; 10. The multilayer article of any preceding embodiment, comprising:

[0160] 17. The support layer is 50% to 82% by weight of component A; 17% to 49% by weight of component B; 0.1 wt% to 10 wt% of component C; 10. The multilayer article of any preceding embodiment, comprising:

[0161] 18. The support layer is 58% to 82% by weight of component A; 17% to 41% by weight of component B; 0.2 wt% to 5 wt% of component C; 10. The multilayer article of any preceding embodiment, comprising:

[0162] 19. The support layer is 65% to 75% by weight of component A; 24% to 34% by weight of component B; 0.3 wt% to 2 wt% of component C; 10. The multilayer article of any preceding embodiment, comprising:

[0163] 20. The multilayer article of any of the preceding embodiments, wherein the support layer comprises less than 1 wt. % of a rubber-based graft polymer different from component B).

[0164] 21. The multilayer article of any of the preceding embodiments, wherein the support layer comprises less than 0.5 wt.% of a rubber-based graft polymer different from component B).

[0165] 22. The multilayer article of any of the preceding embodiments, wherein the support layer comprises less than 0.2 wt.% of a rubber-based graft polymer different from component B).

[0166] 23. The multilayer article of any of the previous embodiments, wherein the support layer does not include any rubber-based graft polymer different from component B).

[0167] 24. The multilayer article of any of the previous embodiments, wherein the support layer has a rubber content in the range of 1.5% to 6% by weight.

[0168] 25. The multilayer article of any of the preceding embodiments, wherein the support layer has a rubber content in the range of 1.8% to 5% by weight.

[0169] 26. The multilayer article of any of the preceding embodiments, wherein the support layer has a rubber content in the range of 1.9% to 4.1% by weight.

[0170] 27. The multilayer article of any of the preceding embodiments, wherein the support layer has a rubber content in the range of 2.5% to 3.0% by weight.

[0171] 28. The multilayer article of any of the preceding embodiments, wherein component A of the support layer is an aromatic polycarbonate based solely on bisphenol A.

[0172] 29. The multilayer article of any of the preceding embodiments, wherein component B of the support layer is produced by a bulk polymerization process.

[0173] 30. The multilayer article of any of the previous embodiments, wherein component B comprises less than 100 ppm of alkali metal and alkaline earth metal ions.

[0174] 31. The multilayer article of any of the previous embodiments, wherein component B comprises less than 20 ppm of alkali metal and alkaline earth metal ions.

[0175] 32. The multilayer article of any of the preceding embodiments, wherein the support layer consists exclusively of components A, B, and C to the extent of at least 80% by weight.

[0176] 33. The multilayer article of any of the preceding embodiments, wherein the support layer consists exclusively of components A, B, and C to the extent of at least 95% by weight.

[0177] 34. The multilayer article of any of the preceding embodiments, wherein the support layer consists exclusively of components A, B, and C to the extent of at least 99% by weight.

[0178] 35. The multilayer article of any of the previous embodiments, wherein the support layer consists solely of component A, component B, and component C.

[0179] 36. The multilayer article of any of the preceding embodiments, wherein the multilayer article is transilluminatable.

[0180] 37. Use of a thermoplastic molding compound comprising component A, component B, and component C as described in any of the preceding embodiments 1 and 16-36 as a support layer in a multilayer article, comprising: The multilayer article comprises the following components in the following order: (I) a support layer; (II) at least one layer consisting solely of a colorant or colorant composition covering at least a portion of the surface between the support layer and the film; (III) a film; Including, use.

[0181] 38. A method for producing a multi-layer article, comprising: a) producing a film; b) printing at least a portion of the film with at least one layer consisting solely of a colorant or colorant composition; c) optionally thermoforming the film; d) insert molding the film with a thermoplastic molding compound comprising component A, component B, and component C as described in any of the preceding embodiments 1 and 16-36; A method comprising:

[0182] 39. a) the multilayer article of any one of embodiments 1 to 36; b) a light source emitting light having at least one wavelength in the wavelength range of the spectrum from 380 nm to 780 nm; A lighting unit comprising: The light source is positioned such that the support layer is transilluminated by the light emitted by the light source, an illumination unit.

[0183] 40. The lighting unit of embodiment 39, wherein the light source is an LED light source. [Example]

[0184] Ingredient A-1: Weight average molecular weight M of 24000 g / mol w (determined by GPC at room temperature in methylene chloride against BPA-PC standards)

[0185] Ingredient A-2: Weight average molecular weight M of 28000 g / mol w (determined by GPC at room temperature in methylene chloride against BPA-PC standards)

[0186] Ingredient B-1: An acrylonitrile-butadiene-styrene (ABS) polymer produced in a bulk polymerization process, comprising a dispersed phase composed of rubber particles grafted with a styrene-acrylonitrile copolymer based on polybutadiene rubber as a graft substrate, with the styrene-acrylonitrile copolymer entrapped as a separate dispersed phase, and a styrene-acrylonitrile copolymer matrix that is not chemically bonded to or entrapped within the rubber particles. Component B-1 has an A:B:S ratio of 23%:10%:67% by weight and a gel content of 20% by weight, determined as the fraction insoluble in acetone. The acetone-soluble fraction of Component B-1 has a weight average molecular weight M of 165 kg / mol. w (measured by GPC in tetrahydrofuran as the solvent using polystyrene standards). The median particle size D50 of the dispersed phase is 0.85 μm, measured by ultracentrifugation. The melt volume flow rate (MVR) of component B-1, measured according to ISO 1133 (2012 edition) at 220°C with a piston load of 10 kg, is 6.7 ml / 10 min.

[0187] Ingredient B-2: An acrylonitrile-butadiene-styrene (ABS) polymer produced in a bulk polymerization process, comprising a dispersed phase composed of rubber particles grafted with styrene-acrylonitrile-n-butyl acrylate terpolymer based on polybutadiene rubber as a graft substrate, with the styrene-acrylonitrile-n-butyl acrylate terpolymer entrapped as a separate dispersed phase, and a styrene-acrylonitrile copolymer matrix that is not chemically bonded to or entrapped within the rubber particles. Component B-2 has an A:B:S:BA ratio of 22.5 wt%:10 wt%:63 wt%:4.5 wt% and a gel content of 19 wt%, determined as the fraction insoluble in acetone. The acetone-soluble fraction of Component B-2 has a weight average molecular weight M of 115 kg / mol. w (measured by GPC in tetrahydrofuran as the solvent using polystyrene standards). The median particle size D50 of the dispersed phase is 0.50 μm, measured by ultracentrifugation. The melt flow rate (MFR) of component C-1, measured according to ISO 1133 (2012 edition) at 220°C and a ram load of 10 kg, is 28 g / 10 min.

[0188] Ingredient B-3 An acrylonitrile-butadiene-styrene graft polymer having a core-shell structure was prepared by emulsion polymerization of a mixture of 27% by weight of acrylonitrile and 73% by weight of styrene, 43% by weight based on the ABS polymer, in the presence of 57% by weight based on the ABS polymer of particulate crosslinked polybutadiene rubber as a graft substrate, the polybutadiene rubber graft substrate having a bimodal particle size distribution with maxima at 0.28 μm and 0.40 μm, and an average particle size D50 of 0.35 μm as measured by ultracentrifugation.

[0189] Component B-3 does not contain styrene-acrylonitrile copolymer entrapped in rubber particles.

[0190] Ingredient B-4 An acrylonitrile-butadiene-styrene graft polymer with a core-shell structure was prepared by emulsion polymerization of a mixture of 26% by weight of acrylonitrile and 74% by weight of styrene, 42% by weight based on the ABS polymer, in the presence of 58% by weight based on the ABS polymer of agglomerated granular polybutadiene rubber as a graft substrate.Compared to the graft substrate used in Component B-3, this polybutadiene rubber graft substrate has a significantly broader, more monomodal particle size distribution.However, the average particle size D50 of 0.38 μm measured by ultracentrifugation is in the same range as that of Component B-3.

[0191] Component B-4 does not contain styrene-acrylonitrile copolymer entrapped in rubber particles.

[0192] Ingredient B-5 It has an acrylonitrile content of 23% by weight and a weight average molecular weight M of 100,000 Da measured by GPC at room temperature in tetrahydrofuran using polystyrene standards. w 1. A styrene-acrylonitrile copolymer produced in a bulk polymerization process, comprising:

[0193] Component C1: Pentaerythritol tetrastearate.

[0194] Component C-2: Irganox™ B900 (BASF, Ludwigshafen, Germany) A mixture of 80% by weight of tris(2,4-di-tert-butyl-phenyl)phosphite (Irgafos® 168) and 20% by weight of 2,6-di-tert-butyl-4-(octadecaneoxycarbonylethyl)phenol (Irganox® 1076).

[0195] Component C3: Irganox™ 1076 (BASF, Ludwigshafen, Germany) 2,6-di-tert-butyl-4-(octadecaneoxycarbonylethyl)phenol.

[0196] Preparation and testing of molding compounds according to the invention The molding compounds were produced in a ZSK25 twin-screw extruder from Coperion, Werner & Pfleiderer, Stuttgart, Germany, at a melt temperature of 260° C. and an applied vacuum of 100 mbar (absolute).

[0197] Molded parts were produced in an Arburg 270 E injection molding machine at a melt temperature of 260°C and a mold temperature of 80°C.

[0198] The melt viscosity was measured according to ISO 11443 (2014 edition) at a temperature of 260°C and 1000 s -1 was determined at a shear rate of .

[0199] IZOD notched impact strength was determined in accordance with ISO 180 / U (2013 edition) on test bars with dimensions of 80 mm x 10 mm x 4 mm at temperatures ranging from -50 °C to 23 °C. Measurements at various temperatures were used to determine the ductile-brittle transition temperature as the temperature at which 50% of the specimens under test undergo brittle failure and 50% undergo ductile failure.

[0200] To determine the ductility of materials under multiaxial stress at low temperatures, puncture tests according to ISO 6603-2 (2002 edition) were carried out at -20 °C on 10 specimens in each case with dimensions of 60 mm x 60 mm x 2 mm. The percentage of brittle fracture serves as a measure of the ductility of materials under multiaxial stress. Brittle fracture is to be understood as meaning a fracture failure in which part of the specimen breaks during the puncture test and / or the specimen shows unstable crack propagation, such that the specimen breaks completely in two along such crack during the test.

[0201] The elastic modulus E and elongation at break were determined in dumbbells with dimensions of 170 mm x 10 mm x 4 mm at 23°C according to ISO 527 (1996 edition) at a strain rate of 1 mm / min (elastic modulus) or 5 mm / min (elongation at break).

[0202] As a measure of the heat resistance, the Vicat B / 120 softening temperature is determined in accordance with ISO 180 / 1A (2014 edition) on test bars having dimensions of 80 mm x 10 mm x 4 mm.

[0203] As a measure of transilluminability, the total luminous transmittance was determined in accordance with ISO 13468-2 (2006 edition) (illuminant: D65, observer: 10°) on test specimens having dimensions of 60 mm x 40 mm x 2 mm (i.e. with a material thickness of 2 mm).

[0204] The half-power angle (HPA) of light intensity was used as a measure of light diffusion. A larger half-power angle indicates stronger light scattering. The half-power angle was determined by measuring the light intensity after transillumination of a test piece with dimensions of 60 mm × 40 mm × 2 mm (i.e., a material thickness of 2 mm) according to the polar angle measured relative to the incident light beam within the range of 0° to 90°. The obtained value was normalized to the intensity value measured at an angle of 0°, so the normalized intensity varied between 0 and 1 depending on the polar angle θ (where I(0°) = 1). The half-power angle (HPA) was defined as the angle at which the normalized intensity dropped to 0.5 (i.e., I(HPA) = 0.5). According to this definition, the theoretical maximum possible half-power angle is 60°.

[0205] [Table 1]

[0206] The data in Table 1 make clear that molding compounds of the present invention, which contain the inventive component B-1 as component B and are within the scope of the present invention in terms of polybutadiene rubber content, exhibit a surprisingly advantageous combination of high light transmittance and high light diffusion (scattering power). Furthermore, the inventive molding compounds exhibit an advantageous combination of improved melt flow (reduced melt viscosity) and good mechanical properties, especially good material toughness, even at low temperatures. In contrast, molding compounds not according to the present invention, which contain the inventive emulsion-polymerized ABS component B-3 or B-4 or the inventive bulk-polymerized ABS component B-2, are unable to achieve this technical objective of the present invention. The same applies to molding compounds composed of compositions V9 and V13, which are outside the scope of the present invention in terms of their polybutadiene rubber content.

[0207] A multilayer article according to the present invention is shown in schematic form in FIG.

Claims

1. In the following order: (I) a support layer composed of a thermoplastic molding compound containing the following A), B), and C); (II) at least one layer consisting solely of a colorant or a colorant composition covering at least a portion of the surface between the support layer and the film; (III) a film; and A multi-layer article comprising: A) at least one representative selected from the group consisting of aromatic polycarbonates and aromatic polyester carbonates; B) A rubber-modified vinyl (co)polymer composed of the following B.1) and B.2): C) optionally at least one further component selected from polymer additives and blending polymers; B. 1) 80% to 95% by weight, based on said rubber-modified vinyl (co)polymer B, of structural units derived from at least one vinyl monomer; and B.2) 5% to 20% by weight, based on said rubber-modified vinyl (co)polymer B, of one or more elastomeric graft substrates having a glass transition temperature of less than -50°C and containing at least 50% by weight, based on B.2, of structural units derived from 1,3-butadiene, wherein said rubber-modified vinyl (co)polymer B is (i) a dispersed phase consisting solely of the following (i.1) and (i.2): (ii) a rubber-free vinyl (co)polymer matrix consisting only of structural units of B.1 that are not bonded to and entrapped in rubber particles, (i.1) B. Rubber particles grafted with a vinyl (co)polymer composed of structural units of 1, and (i.2) a vinyl (co)polymer also composed of structural units of B.1 entrapped in the rubber particles as a separate dispersed phase; wherein the dispersed phase of (i) has a median diameter D50 of 0.7 μm to 2.0 μm as measured by ultracentrifugation; wherein the thermoplastic molding compound contains less than 2% by weight of a rubber-based graft polymer different from component B), and A multi-layer article wherein said thermoplastic molding compound has a rubber content of at least 1.5% by weight.

2. The multilayer article of claim 1 , wherein the film is transilluminatable.

3. 3. A multilayer article according to claim 1 or 2, wherein the film consists exclusively of methyl methacrylate to the extent of at least 60% by weight.

4. 3. A multilayer article according to claim 1, wherein the film consists exclusively of polycarbonate to the extent of at least 60% by weight.

5. 5. The multilayer article according to claim 1, wherein in partial regions of the surface between the support layer (I) and the film (III), the multilayer article comprises a light transmission-reducing layer (II) consisting of a colorant or a colorant composition, and in these regions the multilayer article has a visible transmission of at most 10%, determined according to DIN / ISO 13468-2 (2006 edition) with a D65 illuminant and at an angle of 10° to the observer.

6. The support layer is 30% to 85% by weight of component A; 14% to 69% by weight of component B; 0.05% to 20% by weight of component C; The multilayer article of any one of claims 1 to 5, comprising:

7. The multilayer article of any one of claims 1 to 6, wherein the support layer has a rubber content of from 1.9% to 4.1% by weight.

8. As a support layer in a multilayer article, A) at least one representative selected from the group consisting of aromatic polycarbonates and aromatic polyester carbonates; B) A rubber-modified vinyl (co)polymer composed of the following B.1) and B.2): C) optionally at least one further component selected from polymer additives and blending polymers; Use of a thermoplastic molding compound comprising B. 1) 80% to 95% by weight, based on said rubber-modified vinyl (co)polymer B, of structural units derived from at least one vinyl monomer; and B.2) 5% to 20% by weight, based on said rubber-modified vinyl (co)polymer B, of one or more elastomeric graft substrates having a glass transition temperature of less than -50°C and containing at least 50% by weight, based on B.2, of structural units derived from 1,3-butadiene, wherein said rubber-modified vinyl (co)polymer B is (i) a dispersed phase consisting solely of the following (i.1) and (i.2): (ii) a rubber-free vinyl (co)polymer matrix consisting only of structural units of B.1 that are not bonded to and entrapped in rubber particles, (i.1) B. Rubber particles grafted with a vinyl (co)polymer composed of structural units of 1, and (i.2) a vinyl (co)polymer also composed of structural units of B.1 entrapped in the rubber particles as a separate dispersed phase; wherein the dispersed phase of (i) has a median diameter D50 of 0.7 μm to 2.0 μm as measured by ultracentrifugation; wherein the thermoplastic molding compound contains less than 2% by weight of a rubber-based graft polymer different from component B), and the thermoplastic molding compound has a rubber content of at least 1.5% by weight; The multi-layer article comprises the following components in the following order: (I) the support layer; (II) at least one layer consisting solely of a colorant or a colorant composition covering at least a portion of the surface between the support layer and the film; (III) a film; and Including, use.

9. 1. A method for making a multi-layer article, comprising: a) producing a film; b) printing at least a portion of said film with at least one layer consisting solely of a colorant or colorant composition; c) optionally thermoforming the film; d) insert molding the film with a thermoplastic molding compound comprising the following A), B), and C); Including, A) at least one representative selected from the group consisting of aromatic polycarbonates and aromatic polyester carbonates; B) A rubber-modified vinyl (co)polymer composed of the following B.1) and B.2): C) optionally at least one further component selected from polymer additives and blending polymers; B. 1) 80% to 95% by weight, based on said rubber-modified vinyl (co)polymer B, of structural units derived from at least one vinyl monomer; and B.2) 5% to 20% by weight, based on said rubber-modified vinyl (co)polymer B, of one or more elastomeric graft substrates having a glass transition temperature of less than -50°C and containing at least 50% by weight, based on B.2, of structural units derived from 1,3-butadiene, wherein said rubber-modified vinyl (co)polymer B is (i) a dispersed phase consisting solely of the following (i.1) and (i.2): (ii) a rubber-free vinyl (co)polymer matrix consisting only of structural units of B.1 that are not bonded to and entrapped in rubber particles, (i.1) B. Rubber particles grafted with a vinyl (co)polymer composed of structural units of 1, and (i.2) a vinyl (co)polymer also composed of structural units of B.1 entrapped in the rubber particles as a separate dispersed phase; wherein the dispersed phase of (i) has a median diameter D50 of 0.7 μm to 2.0 μm as measured by ultracentrifugation; wherein the thermoplastic molding compound contains less than 2% by weight of a rubber-based graft polymer different from component B), and The method wherein the thermoplastic molding compound has a rubber content of at least 1.5% by weight.

10. a) the multilayer article of any one of claims 1 to 7; b) a light source emitting light having at least one wavelength in the wavelength range of the spectrum from 380 nm to 780 nm; wherein the light source is arranged such that the support layer is transilluminated by light emitted by the light source.

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