Multilayer article for diffuse transmission

Abstract

The present invention relates to a multilayer article comprising (I) a carrier layer made of a specific thermoplastic polycarbonate molding compound, (II) at least one layer made of a colorant or a colorant composition and (III) a film, in the following order, a lighting unit comprising said multilayer article and a light source, a process for the production of said multilayer article and the use of a specific thermoplastic polycarbonate molding compound as a carrier layer of said multilayer article.

Description

[0001] The present invention relates to a multilayer article comprising, in the following order: a carrier layer made of thermoplastic polycarbonate molding compound; at least one layer made of a colorant or a colorant composition; a film; an illumination unit comprising the multilayer article and a light source; a method for preparing the multilayer article; and the use of thermoplastic polycarbonate molding compound as a carrier layer of such multilayer article.

[0002] Thermoplastic polycarbonate or polyester carbonate molding compounds and their compositions have been known for many years and described in numerous documents. Molding compounds are used to prepare molded articles, for example, for the automotive, construction, and electronics industries.

[0003] Ambient lighting elements or backlighting / display elements are increasingly being used in automotive interiors and body applications. The market trend is towards activating / gradually revealing lighting or functional displays only when needed, such as to differentiate the appearance of these elements from daytime to nighttime, to enhance spatial perception of the vehicle's interior using this dynamic ambient lighting, or to allow for demand- and situation-based information display.

[0004] Components suitable for such applications are, for example, multilayer articles comprising a carrier layer, a thin film that is transmissive to light in the visible wavelength range, and at least one layer made of a colorant or colorant composition disposed therebetween (also referred to as a "colorant layer" in the further context of the invention for simplicity). The carrier layer and the thin film can be used with a light source that transmits visible light (i.e., light in the wavelength range of 380 to 780 nm) to alter the appearance of the multilayer article in a desired manner. Different appearances can be achieved in daytime and nighttime modes, and in "on" and "off" modes, through coloring of the thin film and one or more colorant layers, through the transparency or opacity of the colorant layers, and by partially applying this or some colorant layers in sub-regions between the thin film and the carrier layer. For example, in daytime mode, the multilayer article can have an opaque, high-gloss appearance with any desired coloring, and in nighttime mode, it can be fully transmissive or, alternatively, partially transmissive to display certain illuminated patterns or markings. For this purpose, an opaque colorant layer is applied between the thin film and the carrier layer in areas where transmission is not required in nighttime mode or the "on" display mode. In areas requiring transmissivity in night mode or "on" display mode, no colorant layer or a transmissive colorant layer is applied between the film and the carrier layer. Desired coloring of multilayer articles in day mode or "off" display mode, and desired coloring of transmissive areas in night mode or "on" display mode, can be achieved by coloring the film, carrier layer, and / or colorant layer in these areas.

[0005] The carrier layer must exhibit sufficient transmittance to incident light in order to fundamentally allow for a specific appearance.

[0006] Multilayer articles having translucent (i.e., translucent or transparent) layers are known. WO2006 / 115851A1 discloses a multilayer article comprising: (i) a first layer comprising an acrylic resin; (ii) at least one translucent second layer comprising (a) an acrylic resin optionally further comprising an impact modifier; (b) a rubber-modified thermoplastic resin composition; (c) optionally a rheology modifier and (d) a visual effect additive; (iii) a third layer comprising an acrylonitrile-butadiene-styrene (ABS) resin; and (iv) an optional carrier layer comprising a thermosetting (optionally fiber-reinforced) polymer substrate or a glass-filled ABS resin.

[0007] To create an appealing visual impression, it is generally desirable for the carrier layer to at least partially scatter light from a point source (e.g., an LED), thus diffusely distributing it across the film. Otherwise, the light source is visible to the observer, and / or the desired visual effect when the light source is on will be limited to a small area of ​​the multilayer article. To achieve this diffuse light impression across the area of ​​the multilayer article transmitted by the point source, the carrier layer must, on the one hand, have the highest possible transmittance for incident visible light, and on the other hand, it must have the highest possible light diffraction rate due to light scattering, i.e., the highest possible half-power angle, resulting from the light cone generated by the point source passing through the carrier layer. The higher this half-power angle, the more spatially uniform the perceived illumination intensity after the light from the point source passes through the carrier layer. With a higher half-power angle in the carrier layer, it is also possible to transmit light from the point source to a larger area with a substantially uniform spatial light intensity. The transmittance and light diffraction rate (half-power angle) of a material generally cannot be adjusted independently of each other and are often contradictory. Optimizing the light diffraction rate through material modification (e.g., by changing its composition) usually results in a decrease in transmittance. These two parameters also depend in particular on the thickness of the translucent material layer, where as the layer thickness increases, the transmittance of the translucent material decreases while the light diffuser increases.

[0008] Multilayer articles can be prepared by initially (partially) printing a translucent film with a colorant and then post-injection molding with a carrier material. Post-injection molding of films (also known as film embedding) has been known and widely used for many years.

[0009] Commonly used carrier materials include, for example, polycarbonate molding compounds containing scattering particles, such as glass beads, scattering pigments, or other polymers with a refractive index different from that of polycarbonate. These polymers are often used as crosslinked particles, and are also often used as granular grafted polymers with grafted shells made of polymers compatible or partially compatible with polycarbonate (e.g., having a polymethyl methacrylate shell) to achieve improved compatibility with and dispersibility in the polycarbonate matrix.

[0010] One drawback of this molding compound is the high softening temperature of polycarbonate. Therefore, in the fabrication of multilayer articles, high processing temperatures must be selected to achieve good flowability of the polycarbonate. This can lead to film damage (e.g., undesirable deformation) or insufficient or incomplete adhesion between the film and the carrier layer, as well as an irregular surface appearance in the multilayer article (so-called orange peel formation). In particular, it can also cause colorant to leach from the colorant layer or one of those colorant layers from the printed film. This molding compound further exhibits insufficient toughness for certain applications, especially at low temperatures. Therefore, its use in some safety-related components is not feasible.

[0011] The aforementioned leaching problem has been described in the literature, such as EP1343844 B1 and DE 103 12 610. One way to avoid this phenomenon is to provide a protective layer for the printed film (decorative layer) so that the polymer melt does not directly contact the decorative layer. This protective layer can be composed of, for example, polycarbonate and applied by, for example, co-extrusion.

[0012] Alternatively, to avoid leaching, DE 103 12 610 A1 describes a method in which a decorative layer is protected in the form of a protective element in the form of a mesh, woven fabric or non-woven fabric to protect the polymer melt entering the inlet area of ​​the injection molding die.

[0013] However, in the preparation of multilayer articles, the method increases cost and complexity in terms of material use and process management.

[0014] To improve melt flowability—and thus reduce thermal stress on colorants—polycarbonate can, in principle, be blended with at least one other thermoplastic and processed into polycarbonate blend molding compounds. The selection of blending pairs and other components (e.g., additives) can be used to significantly alter the rheological, mechanical, and thermal properties of molding compounds and molded articles, matching them to the requirements of their respective applications.

[0015] However, molded articles made from polycarbonate blend molding compounds are typically opaque or only partially translucent, making multilayer articles containing such molding compounds unsuitable for meeting the aforementioned optical requirements.

[0016] Therefore, it is desirable to provide a multilayer article that allows for the gradual emergence of the aforementioned dynamic lighting and / or functions. Furthermore, it is desirable that this multilayer article is easy to manufacture, i.e., to achieve stable lamination of the film and carrier material without damaging the film, deforming it, or leaching the colorant, and that no specific process steps (e.g., applying protective devices to the decorative film), specific process management, or special equipment are required in post-film injection molding methods. Therefore, on the one hand, the carrier material must have a combination of good transmittance and high light diffuser for visible light, and on the other hand, it must be able to be injection molded and bonded to the film at relatively low temperatures, i.e., it must have high melt flowability and low melt viscosity even at low temperatures.

[0017] Furthermore, it is expected that the carrier material will maintain high toughness even at low temperatures, thus making multilayer products suitable for a wide range of applications, such as safety components.

[0018] Surprisingly, it was discovered that the above objective was achieved through a multi-layered article of manufacture.

[0019] It includes, in the following order:

[0020] (I) A carrier layer made of thermoplastic molding compound containing

[0021] A) At least one representative of aromatic polycarbonates and aromatic polyester carbonates,

[0022] B) Rubber-modified vinyl (co)polymers, which are made from the following

[0023] B.1) Based on rubber-modified vinyl (co)polymer B, 80% to 95% by weight of structural units derived from at least one vinyl monomer, and

[0024] B.2) Based on rubber-modified vinyl (co)polymer B, 5% to 20% by weight of one or more rubber elastomer grafted substrates, the rubber elastomer grafted substrate having a glass transition temperature of <-50°C, and based on B.2, the rubber elastomer grafted substrate containing at least 50% by weight of structural units derived from 1,3-butadiene.

[0025] The rubber-modified vinyl (co)polymer B contains

[0026] (i) The dispersed phase, which consists of the following

[0027] (i.1) Rubber granules grafted with vinyl (co)polymers made from structural units according to B.1 and

[0028] (i.2) A vinyl (co)polymer, which is also made of structural units according to B.1 and is encapsulated as a separate dispersed phase in rubber particles.

[0029] and

[0030] (ii) A rubber-free vinyl (co)polymer matrix, which consists of structural units according to B.1 and is not bonded to or encapsulated within rubber particles.

[0031] Among them, the dispersed phase according to (i) has a median particle size D50 of 0.7 to 2.0 μm as measured by ultracentrifugation.

[0032] C) Optionally, at least one other component selected from polymer additives and polymer blends.

[0033] The thermoplastic molding compound contains less than 2% by weight of a rubber-based graft polymer different from component B) and

[0034] The thermoplastic molding compound has a rubber content of at least 1.5% by weight.

[0035] (II) At least one layer comprising a colorant or a colorant composition, the layer covering at least a portion of the region between the carrier layer and the film, and

[0036] (III) Thin film.

[0037] Figure 1 A multi-layer article according to the present invention is shown in schematic form.

[0038] In a preferred embodiment, the thermoplastic molding compound of the carrier layer (I) contains

[0039] 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.

[0040] Component B, 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.

[0041] 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.

[0042] In a preferred embodiment, the molding compound of the carrier layer (I) contains less than 1% by weight, more preferably less than 0.5% by weight, and even more preferably less than 0.2% by weight of a rubber-based graft polymer different from component B). Most preferably, the molding compound does not contain any rubber-based graft polymer different from component B.

[0043] In a preferred embodiment, the molding compound of the carrier layer (I) has a rubber content in the range of 1.5% to 6% by weight, more preferably in the range of 1.8% to 5% by weight, even more preferably in the range of 1.9% to 4.1% by weight, and most preferably in the range of 2.3% to 3.0% by weight.

[0044] The preferred ranges of components A and B and component C can be combined with each other as needed.

[0045] In a preferred embodiment, the carrier layer (I) is composed of a thermoplastic molding compound, which is composed of components A, B and C to a degree of at least 80% by weight, more preferably at least 95% by weight, more preferably at least 99% by weight and most preferably up to 100% by weight.

[0046] Multilayer articles are suitable for use with a light source that transmits visible light; that is, multilayer articles are preferably transmissive. The light source is configured such that light first enters the carrier material (I) and finally passes through layer (II) to reach the thin film (III). The light source is preferably an LED light source.

[0047] Transmissive should be understood as changing the visual impression of the side facing away from the light source when the light source is turned on.

[0048] In a preferred embodiment, at least in the sub-regions within its actual thickness therein, the multilayer article has a transmittance of at least 10%, more preferably at least 25%, even more preferably at least 40%, and most preferably at least 45% in the wavelength range of the 380 to 780 nm spectrum, wherein the transmittance is obtained by a transmittance spectrum determined according to the specification DIN / ISO 13468-2, 2006.

[0049] Another subject of the present invention is the use of molding compounds made from the above-described components A, B and C and other features shown as a carrier layer (I) in multilayer articles as described above.

[0050] Another subject of the invention is an illumination unit comprising the multilayer article as described above and a light source emitting light having at least one wavelength in the wavelength range of 380 to 780 nm, wherein the light source is configured such that the carrier layer is transmitted through the light emitted by the light source.

[0051] Another subject of the present invention is a method for preparing multilayer articles, comprising the following steps:

[0052] a) Preparation of thin films

[0053] b) Printing at least a portion of a film using at least one layer consisting of a colorant or a colorant composition.

[0054] c) Optionally, the film is thermoformed.

[0055] d) Post-injection molding of the film using the thermoplastic molding compound as described above.

[0056] Composition of carrier layer

[0057] Component A

[0058] Aromatic polycarbonates and / or aromatic polyester carbonates suitable as component A according to the present invention are known in the literature or prepared by methods known in the literature (for the preparation of aromatic polycarbonates, see, for example, Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964, and DE-AS1 495 626, DE-A 2 232 877, DE-A 2 703 376, DE-A 2 714 544, DE-A 3 000 610, DE-A 3832 396; for the preparation of aromatic polyester carbonates, see, for example, DE-A 3 007 934).

[0059] Aromatic polycarbonates are prepared via interfacial methods, for example, by reacting bisphenols with carbonyl acyl halides (preferably phosgene) and / or aromatic dicarboxylic acid diacyl halides (preferably phenyl dicarboxylic acid diacyl halides), wherein a chain terminator (e.g., monophenol) is optionally used, and a trifunctional or greater branching agent, such as triphenol or tetraphenol, is optionally used. They can also be prepared by melt polymerization via reacting bisphenols with, for example, diphenyl carbonate.

[0060] Those bisphenols of preferred formula (I) used for the preparation of aromatic polycarbonates and / or aromatic polyester carbonates

[0061]

[0062] in

[0063] A is a single bond, C1 to C5-alkylene, C2 to C5-alkylidene, C5 to C6-cycloalkylene, -O-, -SO-, -CO-, -S-, -SO2-, or C6 to C5-carbon rings that may be fused with other aromatic rings optionally containing heteroatoms. 12 -Aspartic acid,

[0064] or groups of formula (II) or (III)

[0065]

[0066] B is C1 to C in each case. 12 -alkyl, preferably methyl, halogen, preferably chlorine and / or bromine

[0067] x is 0, 1, or 2 independently of each other in each case.

[0068] p is 1 or 0, and

[0069] R 5 and R 6 Can be used for each X 1 Individually selected and independently of each other, they are either hydrogen or C1 to C6-alkyl, preferably hydrogen, methyl, or ethyl.

[0070] X 1 For carbon, and

[0071] m is an integer from 4 to 7, preferably 4 or 5, provided that R 5 and R 6 In at least one atom X 1 The upper part is also an alkyl group.

[0072] Preferred diphenols are hydroquinone, resorcinol, dihydroxybiphenyl, bis(hydroxyphenyl)-C1-C5-alkane, bis(hydroxyphenyl)-C5-C6-cycloalkane, bis(hydroxyphenyl) ether, bis(hydroxyphenyl) sulfoxide, bis(hydroxyphenyl) ketone, bis(hydroxyphenyl) sulfone, and α,α-bis(hydroxyphenyl)diisopropylbenzene and their derivatives that are brominated on the ring and / or chlorinated on the ring.

[0073] Particularly preferred bisphenols 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′-dihydroxydiphenyl sulfide, 4,4′-dihydroxydiphenyl sulfone, and their di- and tetrabromo- 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.

[0074] Bisphenols can be used alone or in any desired mixture. Bisphenols are known in the literature or can be obtained by methods known in the literature.

[0075] Examples of suitable chain terminators for the preparation of 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-trimethyl-pentyl)]phenol and 4-(1,3-tetramethylbutyl)phenol according to DE-A 2842 005, or monoalkylphenols or dialkylphenols containing 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 typically from 0.5 mol% to 10 mol%, based on the molar sum of the bisphenols used in each case.

[0076] The thermoplastic aromatic polycarbonate preferably has an average molecular weight (weight average M) of 20,000 to 40,000 g / mol, more preferably 24,000 to 3,200 g / mol, and particularly preferably 26,000 to 3,300 g / mol. w (The determination was performed using bisphenol A-based polycarbonate standards via GPC (gel permeation chromatography)). The preferred range allows for a particularly advantageous balance between the mechanical and rheological properties of the compositions of the present invention.

[0077] Thermoplastic aromatic polycarbonates can be branched in known ways, preferably by incorporating 0.05 to 2.0 mol% of a trifunctional or more trifunctional compound, such as those having three or more phenolic groups, based on the total amount of bisphenols used. Linear polycarbonates are preferred, and those based on bisphenol A are more preferred.

[0078] Both homopolymers and copolymers are suitable. To prepare the copolymer of the present invention according to component A, 1% to 25% by weight, preferably 2.5% to 25% by weight, of a polydiorganosiloxane having hydroxyl aryloxy terminals may also be used based on the total amount of bisphenol used. These are known (US 3,419,634) and can be prepared by methods known in the literature. Copolymers containing polydiorganosiloxanes are also suitable; for example, the preparation of copolymers containing polydiorganosiloxanes is described in DE-A 334,782.

[0079] The preferred aromatic dicarboxylic acid diacyl halides used for preparing aromatic polyester carbonates are isophthalic acid, terephthalic acid, diphenyl ether 4,4′-dicarboxylic acid and naphthal-2,6-dicarboxylic acid diacyl dichloride.

[0080] A mixture of isophthalic acid and terephthalic acid dichlorodichlorodimethyl chloride is particularly preferred, in a ratio of 1:20 to 20:1.

[0081] In the preparation of polyester carbonate, carbonyl acyl halides are also used simultaneously, with phosgene being preferred as a difunctional acid derivative.

[0082] Chain terminators used to prepare aromatic polyester carbonates include not only the aforementioned monophenols, but also their chlorocarbonates, and acyl chlorides of aromatic monocarboxylic acids, which can optionally be C1 to C2. 22 - Alkyl or halogen atom substitution; and aliphatic C2 to C3 22 - Monocarboxylic acid acyl chloride.

[0083] In each case, the amount of chain terminator is 0.1 to 10 mol%, based on the number of moles of bisphenol in the case of phenolic chain terminators, and based on the number of moles of dicarboxylic acid dichlorodi ...

[0084] One or more aromatic hydroxycarboxylic acids can also be used to prepare aromatic polyester carbonates.

[0085] Aromatic polyester carbonates can be 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.

[0086] Suitable branching agents include, for example, trifunctional or polyfunctional carboxylic acid acyl chlorides, such as pyromellitic acid trichloroacetyl chloride, cyanuric acid trichloroacetyl chloride, benzophenone-3,3′,4,4′-tetracarbonyl tetrachloroacetyl chloride, naphthalene-1,4,5,8-tetracarbonyl tetrachloroacetyl chloride, or pyromellitic acid tetrachloroacetyl chloride, used in amounts from 0.01 to 1.0 mol% (based on the dicarboxylic acid dichloroacetyl chloride used), or trifunctional or polyfunctional phenols, such as phloroglucinol, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)-2-heptene, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1 1-Tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)phenylmethane, 2,2-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]propane, 2,4-bis(4-hydroxyphenyl isopropyl)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-hydroxyphenyl isopropyl]phenoxy)methane, and 1,4-bis[4,4′-(dihydroxytriphenyl)methyl]benzene, in amounts from 0.01 to 1.0 mol% (based on the bisphenol used). Phenolic branching agents may initially be introduced together with the bisphenol; acyl chloride branching agents may be introduced together with the diacyl chloride.

[0087] The proportion of carbonate structural units in thermoplastic aromatic polyester carbonates can be varied as needed. Based on the sum of ester and carbonate groups, the proportion of carbonate groups is preferably up to 100 mol%, particularly up to 80 mol%, and especially preferably up to 50 mol%. Both the ester and carbonate moieties of the aromatic polyester carbonate can exist in the condensation polymer in a block or random distribution.

[0088] Thermoplastic aromatic polycarbonates and polyester carbonates can be used alone or in any desired mixture.

[0089] It is preferred to use linear polycarbonate based solely on bisphenol A as component A.

[0090] Component B

[0091] Component B is a rubber-modified vinyl (co)polymer, which is made from the following:

[0092] B.1) Based on rubber-modified vinyl (co)polymer B, 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, and

[0093] B.2) Based on rubber-modified vinyl (co)polymer B, 5% to 20% by weight, preferably 7% to 17% by weight, more preferably 8% to 15% by weight, of one or more rubber elastomer grafted substrates, the rubber elastomer grafted substrate having a glass transition temperature Tg of <-50°C, preferably <-60°C, particularly preferably <-70°C, and based on B.2, the rubber elastomer grafted substrate contains at least 50% by weight, preferably at least 70% by weight, particularly preferably 100% by weight, structural units derived from 1,3-butadiene.

[0094] The rubber-modified vinyl (co)polymer B contains

[0095] (i) The dispersed phase, which consists of the following

[0096] (i.1) Rubber granules grafted with vinyl (co)polymers made from structural units according to B.1, and

[0097] (i.2) A vinyl (co)polymer, which is also made of structural units according to B.1 and is encapsulated as a separate dispersed phase in rubber particles.

[0098] and

[0099] (ii) A rubber-free vinyl (co)polymer matrix, which consists of structural units according to B.1 and is not bonded to or encapsulated within the rubber particles.

[0100] The dispersed phase according to (i) has a median particle size D50 of 0.7 to 2.0 μm, preferably 0.7 to 1.5 μm, particularly 0.7 to 1.2 μm, as measured by ultracentrifugation.

[0101] Unless otherwise expressly stated in this invention, the glass transition temperature Tg of all components was determined by dynamic differential scanning calorimetry (DSC) at a heating rate of 10 K / min according to DIN EN61006 (1994 edition), wherein Tg is determined as the midpoint temperature (tangential method).

[0102] The rubber-modified vinyl (co)polymer of component B has a melt volumetric flow rate (MVR) preferably of 2 to 20 ml / 10 min, particularly preferably of 3 to 15 ml / 10 min, and especially preferably of 4 to 8 ml / 10 min, as measured according to ISO 1133 (2012 edition) at 220°C with a piston load of 10 kg. If a mixture of multiple rubber-modified vinyl (co)polymers is used as component B, the preferred MVR range applies to the average value of the MVR of each component, weighted according to the mass proportion of each component in the mixture.

[0103] This rubber-modified vinyl (co)polymer B is prepared, for example, by free radical polymerization of B.1) in the presence of B.2), preferably by bulk polymerization.

[0104] B.1) Based on rubber-modified vinyl (co)polymer B, 80% to 95% by weight, preferably 83% to 93% by weight, particularly preferably 85% to 92% by weight of at least one vinyl monomer,

[0105] B.2) Based on rubber-modified vinyl (co)polymer B, 5% to 20% by weight, preferably 7% to 17% by weight, more preferably 8% to 15% by weight, of one or more rubber elastomer grafted substrates, the rubber elastomer grafted substrate having a glass transition temperature Tg of <-50°C, preferably <-60°C, particularly preferably <-70°C, and based on B.2, the rubber elastomer grafted substrate contains at least 50% by weight, preferably at least 70% by weight, particularly preferably 100% by weight, structural units derived from 1,3-butadiene.

[0106] In the preferred bulk polymerization method for preparing rubber-modified vinyl (co)polymer B, the vinyl monomers according to B.1 are polymerized, and the resulting vinyl (co)polymer is grafted onto a rubber elastomer graft substrate according to B.2. Furthermore, during this reaction, a dispersed phase (i) is formed through self-organization (phase separation), which consists of the following...

[0107] (i.1) Rubber granules grafted with vinyl (co)polymers made from structural units according to B.1 and

[0108] (i.2) A vinyl (co)polymer, which is also made of structural units according to B.1 and is encapsulated as a separate dispersed phase in rubber particles.

[0109] The rubber-containing phase (i) is dispersed in a rubber-free vinyl (co)polymer matrix, which is composed of structural units according to B.1 and is not bonded to or encapsulated in the rubber particles.

[0110] Unlike the other vinyl (co)polymer portions in component B, the rubber-free vinyl (co)polymer (ii) can be dissolved using a suitable solvent such as acetone.

[0111] The size of the dispersed phase (i) of the rubber-modified vinyl (co)polymer B thus prepared is adjusted by the reaction conditions, such as temperature, the viscosity of the resulting polymer, and the shear generated by stirring, for example.

[0112] The median particle size D50 is the diameter of the 50% by weight particles above and below it. Unless otherwise explicitly stated in this invention, all components were determined by ultracentrifugation (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972), 782-796).

[0113] Monomer B.1 is preferably a mixture of the following components.

[0114] B.1.1 In each case, based on the sum of B.1.1 and B.1.2, 60 to 85 parts by weight, particularly preferably 65 to 80 parts by weight, more preferably 70 to 78 parts by weight of styrene, and

[0115] B.1.2 In each case, based on the sum of B.1.1 and 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.

[0116] And optionally, B.1.3 in each case, based on a total of 100 parts by weight of B.1.1 and B.1.2, 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.

[0117] In another preferred embodiment, monomer B.1 is a mixture of 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, wherein the total weight of styrene and acrylonitrile is 100 parts by weight.

[0118] B.1 is particularly preferred to be free of B.1.3, wherein the above preferred range applies to B.1.1 and B.1.2.

[0119] The preferred grafting substrate B.2 is a butadiene-containing diene rubber or a mixture of butadiene-containing diene rubbers or a copolymer of butadiene-containing diene rubbers or a mixture thereof with other copolymerizable monomers (e.g., according to B.1.1 and B.1.2).

[0120] A particularly preferred graft substrate B.2 is pure polybutadiene rubber. In another preferred embodiment, B.2 is a styrene-butadiene block copolymer rubber.

[0121] Component B preferably has a polybutadiene content of 5% to 18% by weight, more preferably 7% to 15% by weight, and particularly 8% to 13% by weight.

[0122] Particularly preferred rubber-modified vinyl (co)polymers according to component B are bulk polymerized ABS polymers, such as those specified in DE-OS 2035390 (=US-PS 3644574) or DE-OS 2248242 (=GB-PS 1 409 275), or in Ullmanns, der Technischen Chemie, Vol. 19 (1980), p. 280 and thereafter.

[0123] Vinyl (co)polymer (ii) that is not chemically bonded to the rubber (one or more) base B.2 and is not encapsulated in the rubber particles can be formed in the polymerization of graft polymer B as described above due to preparation. It is also possible that a portion of the vinyl (co)polymer (ii) that is not chemically bonded to the rubber (one or more) base B.2 and is not encapsulated in the rubber particles is formed in the preparation of the rubber-modified vinyl (co)polymer according to component B by bulk polymerization as described above, and another portion is polymerized separately and added to component B as part of component B. Regardless of its source, the proportion of vinyl (co)polymer (ii) determined as the acetone solubility ratio is preferably at least 50% by weight, particularly preferably at least 60% by weight, more preferably at least 70% by weight, based on component B.

[0124] In the rubber-modified vinyl (co)polymer according to component B, the vinyl (co)polymer (ii) has a weight-average molecular weight M of preferably 70 to 250 kg / mol, preferably 130 to 200 kg / mol, and particularly 150 to 180 kg / mol. w .

[0125] In the context of this invention, the weight-average molecular weight M of the vinyl (co)polymer (ii) in component B is... w Determined relative to polystyrene standards by gel permeation chromatography (GPC) in tetrahydrofuran.

[0126] Component B is preferably free of alkali metals, alkaline earth metals, ammonium or phosphonium salts of saturated fatty acids having 8 to 22 carbon atoms, resin acids, alkyl and alkylaryl sulfonic acids, and fatty alcohol sulfates.

[0127] Component B preferably contains less than 100 ppm, particularly preferably less than 50 ppm, and very particularly preferably less than 20 ppm of alkali metal and alkaline earth metal ions.

[0128] Suitable rubber-modified vinyl (co)polymers as component B include, for example, Magnum from Trinseo SA (Luxembourg). TM 3404, Magnum TM 3504 and Magnum TM 3904.

[0129] Component C

[0130] The component C may optionally be one or more representatives selected from polymer additives and polymer blends.

[0131] The polymer additives and polymer blends are preferably selected from lubricants and release agents, stabilizers, colorants, compatibilizers, other impact modifiers different from component B, other polymer components different from components A and B (e.g., functional blends or grafted polymers with core-shell structures prepared in emulsion polymerization), and fillers and reinforcing agents.

[0132] In a preferred embodiment, component C does not contain fillers or reinforcing agents. More preferably, it does not contain colorants. More preferably, it does not contain polymer blends. More preferably, it does not contain polymer components. In a particularly preferred embodiment, it contains neither fillers or reinforcing agents, colorants, nor polymer blends. Most preferably, it contains neither fillers or reinforcing agents, colorants, nor polymer components.

[0133] In a preferred embodiment, at least one polymer additive selected from lubricants, release agents, and stabilizers is used as component C.

[0134] In a preferred embodiment, at least one representative selected from sterically hindered phenols, organic phosphites, and organic or inorganic Brønsted acids is used as a stabilizer.

[0135] In a preferred embodiment, at least one representative selected from sterically hindered phenols, organic phosphites, and organic or inorganic Brønsted acids is used as a stabilizer.

[0136] In a preferred embodiment, fatty acid esters, particularly pentaerythritol or glycerol fatty acid esters, are used as lubricants and release agents.

[0137] In a particularly preferred embodiment, at least one C8-C derivative selected from pentaerythritol. 22 C8-C of fatty acid esters and glycerol 22 Polymer additives of fatty acid esters, tris(2,4-di-tert-butylphenyl) phosphite, 2,6-di-tert-butyl-4-(octadecyloxycarbonylethyl)phenol, tetra(2,4-di-tert-butylphenyl)-4,4-biphenyl diphosphite, bis(2,4-di-tert-butylphenyl) pentaerythritol diphosphite, and triethylene glycol bis[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionate] are used as component C.

[0138] In another embodiment, component C does not contain the rubber-modified vinyl (co)polymer prepared by emulsion polymerization.

[0139] Preparation of molding compound for carrier layer

[0140] Thermoplastic molding compound is prepared from components A, B and C according to the present invention.

[0141] The thermoplastic molding compound according to the invention can be prepared, for example, by mixing the various components of the composition in a known manner and melt-blending and melt-extruding at a temperature preferably from 200°C to 320°C, particularly preferably from 240°C to 300°C, and very particularly preferably from 260°C to 290°C, for example in conventional equipment such as an internal kneader, an extruder, and a twin-screw extruder.

[0142] In the context of this invention, this process is generally referred to as compounding.

[0143] Therefore, molding compounds should be understood as products obtained when the components of a composition are melt-blended and melt-extruded.

[0144] The individual components of the composition can be mixed continuously or simultaneously in a known manner, at a temperature of about 20°C (room temperature) or higher. This means, for example, that some components are introduced through the main feed port of the extruder, while the remaining components can be introduced later in a compounding process through a side extruder.

[0145] Colorant Composition

[0146] For the decoration of the film, colorant compositions commonly used in various methods are used, such as screen printing inks, colored paints or inks.

[0147] The colorant compositions according to the invention contain at least one colorant as an essential component. The term colorant should be understood to refer to organic and inorganic pigments and dyes, including soluble dyes.

[0148] It may also contain one or more other components that can be broadly classified as volatile and nonvolatile components.

[0149] Non-volatile components include binders, fillers, and additives. Additives are typically required in small quantities, but are often essential for problem-free processing.

[0150] Volatile components are essentially liquids in which colorants and possibly other components are dissolved or dispersed. These can be organic or inorganic solvents or mixtures of multiple solvents. The solvent is typically water or a mixture of water and another solvent.

[0151] Suitable organic solvents include, for example, ketones, esters, alcohols, and aromatic or aliphatic hydrocarbons. Mixtures of various organic or inorganic solvents may also be used.

[0152] Non-volatile binders ensure that the colorant is anchored to the substrate, thus enabling the finished print to withstand stresses caused by abrasion, heat, and mechanical bending.

[0153] Suitable binders for colorants include, for example, combinations of nitrocellulose with plasticizers, thermoplastic polyurethanes, thermoplastic polyesters, thermoplastic polycarbonates, and thermoplastic poly(meth)acrylates. Different binders can also be combined, as described in DE 19832570A1. Binders (e.g., polyurethanes or epoxy resins) can also be formed in situ via chemical reaction during the application of the colorant composition.

[0154] The choice of suitable colorant is virtually limitless, provided sufficient temperature resistance is ensured. Suitable organic colorants include, for example, those derived from azo, anthraquinone, azirperphene, indigo thiocyanate, dioxazine, naphthalenetetracarboxylic acid or perylenetetracarboxylic acid series, and phthalocyanine compounds. Suitable inorganic colorants include, for example, iron oxide, ultramarine, zinc sulfide, silica, alumina, titanium dioxide, nickel and chromium compounds, phosphotungstic molybdate bronze, and carbon black. Colorants with special effects, such as mica pigments coated with metal oxides and metallic aluminum pigments, can also be used.

[0155] Fillers may also be incorporated into the colorant composition if desired. Suitable fillers include carbonates, sulfates, silicates, and oxides. Particularly suitable fillers include carbonates of magnesium, calcium, and barium; sulfates of calcium and barium; silicates and aluminosilicates; and oxides of aluminum, titanium, and silicon. Mixtures of these compounds may also be used.

[0156] Conventional and known additives can also be incorporated into colorant compositions. Such additives include, for example, wetting and dispersing agents, antisettling agents, leveling agents, tackifiers, stabilizers, anti-scratch additives, etc.

[0157] A colorant composition is prepared from the components used by thoroughly mixing the components using methods known to those skilled in the art, including, for example, dispersing, dissolving, or compounding in a melt.

[0158] Particularly heat-resistant colorant compositions are described, for example, in EP 0688839 A2. Heat-resistant colorant compositions are also available from Proll KG GmbH in Weißenburg, Germany. The name HTR was obtained.

[0159] However, the present invention is not limited to highly heat-resistant colorant compositions. As described in the introduction, by selecting a carrier material with good melt flowability according to the present invention, it is permissible to use colorant compositions that are more sensitive to high temperatures and therefore not applicable to the preparation of multilayer articles by post-film injection molding, even at low processing temperatures.

[0160] Colorants particularly suitable for screen printing of PMMA films are described in document DE 10151281A1.

[0161] In the preparation of the multilayer article according to the invention, a portion or the total amount of the volatile components contained in the colorant composition may escape, and thus can no longer or only to a very small extent be a component of the colorant composition according to component II of the claimed multilayer article.

[0162] 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 onto the entire area of ​​the film to be transmitted. This allows, for example, the display elements to gradually appear.

[0163] Different film areas can also be printed using different colorant compositions, or multiple layers made of different colorant compositions can be stacked and printed on top of each other. A preferred embodiment described herein is the stacking and printing of a translucent, i.e., transparent or translucent, colorant composition with an opaque colorant composition. Particularly preferably, the two colorant compositions have the same or similar coloration.

[0164] film

[0165] The film can be a single-layer film or a multilayer film. One or more additional layers in the multilayer structure can be applied, for example, by co-extrusion, lamination and / or coating methods (e.g., wet coating or plasma coating).

[0166] The film is preferably made of a thermoplastic composition containing one or more thermoplastic polymers and optionally other additives. Conventional polymer additives can be used as additives. The thermoplastic composition can be colored, in particular, by suitable colorants.

[0167] Thermoplastic polymers include, for example, thermoplastic polyurethanes, polymethyl methacrylate (PMMA) and modified variants of PMMA, polyolefins, aromatic polycarbonates (PC), as well as copolycarbonates (Co-PC), polyetherimides, styrene-acrylonitrile, acrylonitrile-styrene-acrylate copolymers (ASA), acrylonitrile-butadiene-styrene copolymers (ABS), polyesters, and mixtures of these polymers.

[0168] The preferred material for the film is a thermoplastic polymer based on polycarbonate.

[0169] In an alternative preferred embodiment, the film uses a thermoplastic polymer based on polymethyl methacrylate.

[0170] "Based on" should be understood herein to mean that the polymer accounts for at least 60% by weight, preferably at least 75% by weight, and more preferably at least 90% by weight in the total composition of the film.

[0171] In a preferred embodiment, the film is transmissive overall. The definition of the term "transmissive" is set forth above.

[0172] It is possible that only a portion of the thin film is transmitted through a light source. This can be achieved, for example, by using a thin film made of multiple layers. In this case, one of these layers can have high transmittance for visible light (i.e., light with a spectral wavelength range of 380 to 780 nm), and another layer can be opaque but equipped with holes, slots, or similar channels for light. In this structure, only a portion of the thin film is transmissive, in which the opaque layer has channels for light.

[0173] The film is transmissive of visible light in the area to be transmitted within its actual thickness. In the context of this invention, "transmissive" is preferably understood to mean a film having at least 20%, more preferably at least 50%, and particularly preferably at least 70% transmittance at at least one wavelength in the visible wavelength range (380 to 780 nm) of the spectrum, in the area to which it should be transmitted by the light source, as measured according to the specification in DIN / ISO 13468-2 (2006 edition, (light source: D65, observer: 10°)).

[0174] In a preferred embodiment, the entire film has a visual transmittance of at least 20%, preferably at least 50%, and particularly preferably at least 70%, as measured according to DIN / ISO 13468-2 (2006 edition, (light source: D65, observer: 10°)).

[0175] Furthermore, most preferably, the film has a yellowness value of up to 20, preferably up to 5, and particularly preferably up to 2 as a measure of color neutrality, as determined according to ASTM E313 (2010 edition).

[0176] The thickness of the film is from 50 μm to 1 mm, preferably from 100 μm to 700 μm. This data should be understood to mean that the film has this thickness at every location within its range.

[0177] The coating composition can be applied to the side of the film facing away from the carrier layer. The coating should generally provide mechanical protection against abrasion and scratches and / or protection against the effects of weathering, i.e., rainfall, temperature changes, and ultraviolet radiation. Specific surface tactile or optical properties can also be achieved through the coating.

[0178] Suitable coatings are, for example, thermosetting coating systems based on polysiloxane varnishes, which can be single-layer or multi-layered (with a primer layer between the substrate and the polysiloxane topcoat that only promotes adhesion).

[0179] UV-curable coating systems based on, for example, acrylates, urethane acrylates, or acryloylsilanes can also be used, which optionally contain fillers to improve scratch resistance.

[0180] The aforementioned colorants may also be present in the coating and / or the film itself.

[0181] For example, the thermoplastic composition used to form the film may contain such a colorant. In this case, the film itself will be colored. The opaque colorant composition can then be applied as, for example, layer (II) to a portion of the area between the film and the carrier material.

[0182] If the coating of the film contains a colorant, a colorant with lower temperature resistance can be selected in addition to the colorants mentioned above.

[0183] If the coating of the film or the thermoplastic composition used to form the film contains colorants, these colorants and / or the concentration of these colorants still ensure the translucency of the film. This means that the coloring of the coating on the side opposite to the carrier layer or the film itself is not opaque.

[0184] Preparation of multilayer products

[0185] Multilayer articles are preferably prepared by the FIM (film embedding molding) method. Film embedding molding (FIM), or post-film injection molding, is a special injection molding process in which a three-dimensional preformed film is optionally placed as an insert in an injection mold before the injection of the plastic melt. This method is known to those skilled in the art and is widely used.

[0186] Inserts are typically molded, optionally as decorative films. The molding process can use mechanical or non-contact thermoforming. For example, deep drawing is used for this purpose. Other methods include vacuum deep drawing, pressing, or blow molding. For tighter positional tolerances, known high-pressure forming (HPF) methods, such as those described in EP 2 197 656 B1, are used. The film is typically cut after molding. Common methods for this can be used, such as stamping, milling, die cutting, laser cutting, and waterjet cutting.

[0187] In short, in order to prepare the multilayer article according to the present invention, the following steps are therefore performed in the preferred method:

[0188] a) Print the film using the colorant composition.

[0189] b) Optionally, the film is shaped and optionally subsequently cut.

[0190] c) The film is post-injected into an injection mold using the molten molding compound of the carrier layer.

[0191] The three-dimensional forming of the film and the post-injection molding of the film can also be performed in a single injection mold. For example, such a simplified method is disclosed in WO2014 / 044694A1.

[0192] Thin film printing can be performed using various methods, such as screen printing, offset printing, and digital printing via electrostatic or inkjet printing. Other possible methods for thin film printing include coating, pad printing, letterpress printing (including flexographic printing), offset printing, and gravure printing. The method used depends particularly on the printing substrate, the shape of the part, the required print quality, and the type of film.

[0193] Digital printing allows for color printing without the need for pre-fabricated printing molds or printing plates. Digitized printing data is transmitted directly to the digital printing press. This method enables rapid, on-demand printing and high flexibility across printing runs, including individual runs. The two most important digital printing technologies are electrostatic printing and inkjet printing. Digital information is printed specifically via electrostatic printing, which is similar to color laser copying. Another method used for printing digital information is inkjet printing. This uses high-precision micro-jet printers to spray ink directly onto the surface to be printed. The ink selection should ensure good wetting of the film surface and strong adhesion.

[0194] Due to its high printing speed, offset printing is particularly suitable for high-volume, economical production (printing batches), such as for producing very fine line patterns.

[0195] Screen printing is preferred as the printing method. Screen printing provides printed images with high opacity and color density. This is important for applications in transmissive light technology, where the printed film is backlit, such as in automotive parts with day / night designs, such as dials or decorative lighting elements.

[0196] Printing can include, for example, company logos, vehicle type or vehicle class names, text, or purely decorative patterns.

[0197] Alternatively, after post-injection molding of the film with a carrier material, another layer of carrier material can be applied in an overmolding process to seamlessly encapsulate the surface of the post-injection molded part. Overmolding is known to those skilled in the art and is described, for example, in publications WO 2012 / 069590A1, EP2402140 A1, and DE102007011338 A1.

[0198] In another preferred embodiment, in addition to the film according to component III, a covering film is optionally applied to the plastic article. Preferably, the covering film is applied to the side on which the multilayer article according to the invention is positioned in its final use, in its installed state facing the observer. In a more preferred embodiment, the covering film is a hard-coated film, also known as a film coated with a hard coating.

[0199] The thickness of carrier layer I is preferably 0.5 to 10 mm, more preferably 1 to 5 mm. This data is understood to mean that carrier layer I has this thickness at every location within its range. Layers formed by direct post-injection molding of the film do not necessarily have the same thickness over the entire area of ​​the film, but can also have different thicknesses, for example, due to the construction of reinforcing ribs, due to the shape of the component, or due to the fastening structure, etc.

[0200] In the region to be transmitted, the carrier layer I preferably has a thickness of 0.5 mm to 5 mm, particularly preferably 1.5 mm to 3.5 mm, and especially preferably 1.7 mm to 2.5 mm.

[0201] Other embodiments of the present invention, 1 to 40, are described below:

[0202] 1. Multi-layer products,

[0203] It includes, in the following order:

[0204] (I) A carrier layer made of thermoplastic molding compound containing

[0205] A) At least one representative of aromatic polycarbonates and aromatic polyester carbonates,

[0206] B) Rubber-modified vinyl (co)polymers, which are made from the following

[0207] B.1) Based on rubber-modified vinyl (co)polymer B, 80% to 95% by weight of structural units derived from at least one vinyl monomer, and

[0208] B.2) Based on rubber-modified vinyl (co)polymer B, 5% to 20% by weight of one or more rubber elastomer grafted substrates, the rubber elastomer grafted substrate having a glass transition temperature of <-50°C, and based on B.2, the rubber elastomer grafted substrate containing at least 50% by weight of structural units derived from 1,3-butadiene.

[0209] The rubber-modified vinyl (co)polymer B contains

[0210] (i) The dispersed phase, which consists of the following

[0211] (i.1) Rubber granules grafted with vinyl (co)polymers made from structural units according to B.1, and

[0212] (i.2) A vinyl (co)polymer, which is also made of structural units according to B.1 and is encapsulated as a separate dispersed phase in rubber particles.

[0213] and

[0214] (ii) A rubber-free vinyl (co)polymer matrix, which consists of structural units according to B.1 and is not bonded to or encapsulated within rubber particles.

[0215] Among them, the dispersed phase according to (i) has a median particle size D50 of 0.7 to 2.0 μm as measured by ultracentrifugation.

[0216] C) Optionally, at least one other component selected from polymer additives and polymer blends.

[0217] The thermoplastic molding compound contains less than 2% by weight of a rubber-based graft polymer different from component B), and

[0218] The thermoplastic molding compound has a rubber content of at least 1.5% by weight.

[0219] (II) At least one layer comprising a colorant or a colorant composition, the layer covering at least a portion of the region between the carrier layer and the film.

[0220] (III) Thin film.

[0221] 2. The multilayer article according to embodiment 1, wherein the thin film is transmissive.

[0222] 3. The multilayer article according to embodiment 1 or 2, wherein the film is composed of a thermoplastic material.

[0223] 4. The multilayer article according to any one of the foregoing embodiments, wherein the film is composed of methyl methacrylate in an amount of at least 60% by weight.

[0224] 5. A multilayer article according to any one of claims 1 to 3, wherein the film is composed of polycarbonate in an extent of at least 60% by weight.

[0225] 6. The multilayer article according to any one of the foregoing embodiments, wherein the thickness of the film is in the range of 50 μm to 1 mm at each location.

[0226] 7. The multilayer article according to any one of the foregoing embodiments, wherein the thickness of the film is in the range of 100 to 700 μm at each location.

[0227] 8. The multilayer article according to any one of the foregoing embodiments, wherein the film has at least 20% transmittance in its actual thickness in the area to be transmitted at at least one wavelength in the wavelength range of 380 to 780 nm, as determined according to the specification in DIN / ISO 13468-2 (2006 edition).

[0228] 9. The multilayer article according to any one of the foregoing embodiments, wherein the film has at least 50% transmittance in its actual thickness in the area to be transmitted at at least one wavelength in the wavelength range of the 380 to 780 nm spectrum, as determined according to the specification in DIN / ISO 13468-2 (2006 edition).

[0229] 10. The multilayer article according to any one of the foregoing embodiments, wherein the film has at least 70% transmittance in its actual thickness in the area to be transmitted at at least one wavelength in the wavelength range of 380 to 780 nm, as determined according to the specification in DIN / ISO 13468-2 (2006 edition).

[0230] 11. The multilayer article according to any one of the foregoing embodiments, wherein the thickness of the carrier layer is in the range of 1 to 5 mm at each location.

[0231] 12. The multilayer article according to any one of the foregoing embodiments, wherein the carrier layer has a thickness of 1.5 to 3.7 mm in the region to be transmitted.

[0232] 13. The multilayer article according to any one of the foregoing embodiments, wherein in a sub-region of the area between the carrier layer (I) and the film (III), the multilayer article includes a transmittance reducing layer composed of a colorant or a colorant composition, and in these regions, the multilayer article has a visual transmittance of up to 10%, as measured by a D65 light source and at an angle of 10° for the observer, according to DIN / ISO 13468-2, 2006.

[0233] 14. A multilayer article according to any one of the foregoing embodiments, wherein in a sub-region of the area between the carrier layer (I) and the film (III), the multilayer article comprises a transmittance reducing layer composed of a colorant or a colorant composition, and in these regions, the multilayer article has a visual transmittance of up to 25%, measured according to DIN / ISO 13468-2, 2006, using a D65 light source and at an angle of 10° relative to the observer.

[0234] 15. A multilayer article according to any one of the foregoing embodiments, wherein in a sub-region of the area between the carrier layer (I) and the film (III), the multilayer article comprises a transmittance reducing layer composed of a colorant or a colorant composition, and in these regions, measured according to DIN / ISO 13468-2, 2006, using a D65 light source and at an angle of 10° relative to the observer, the multilayer article has a visual transmittance of up to 45%.

[0235] 16. The multilayer article according to any one of the foregoing embodiments, wherein the carrier layer comprises

[0236] Component A, ranging from 30% to 85% by weight; component B, ranging from 14% to 69% by weight; and component C, ranging from 0.05% to 20% by weight.

[0237] 17. The multilayer article according to any one of the foregoing embodiments, wherein the carrier layer comprises 50% to 82% by weight of component A, 17% to 49% by weight of component B and 0.1% to 10% by weight of component C.

[0238] 18. The multilayer article according to any one of the foregoing embodiments, wherein the carrier layer comprises 58% to 82% by weight of component A, 17% to 41% by weight of component B and 0.2% to 5% by weight of component C.

[0239] 19. The multilayer article according to any one of the foregoing embodiments, wherein the carrier layer comprises 65% to 75% by weight of component A, 24% to 34% by weight of component B and 0.3% to 2% by weight of component C.

[0240] 20. The multilayer article according to any one of the foregoing embodiments, wherein the carrier layer contains less than 1% by weight of a rubber-based grafted polymer different from component B).

[0241] 21. The multilayer article according to any one of the foregoing embodiments, wherein the carrier layer contains less than 0.5% by weight of a rubber-based grafted polymer different from component B).

[0242] 22. The multilayer article according to any one of the foregoing embodiments, wherein the carrier layer contains less than 0.2% by weight of a rubber-based grafted polymer different from component B).

[0243] 23. The multilayer article according to any one of the foregoing embodiments, wherein the carrier layer does not contain a rubber-based graft polymer different from component B).

[0244] 24. The multilayer article according to any one of the foregoing embodiments, wherein the carrier layer has a rubber content in the range of 1.5% to 6% by weight.

[0245] 25. The multilayer article according to any one of the foregoing embodiments, wherein the carrier layer has a rubber content in the range of 1.8% to 5% by weight.

[0246] 26. The multilayer article according to any one of the foregoing embodiments, wherein the carrier layer has a rubber content in the range of 1.9% to 4.1% by weight.

[0247] 27. The multilayer article according to any one of the foregoing embodiments, wherein the carrier layer has a rubber content in the range of 2.5% to 3.0% by weight.

[0248] 28. The multilayer article according to any one of the foregoing embodiments, wherein component A of the carrier layer is an aromatic polycarbonate based solely on bisphenol A.

[0249] 29. The multilayer article according to any one of the foregoing embodiments, wherein component B of the carrier layer is prepared by bulk polymerization.

[0250] 30. The multilayer article according to any one of the foregoing embodiments, wherein the component B contains less than 100 ppm of alkali metal and alkaline earth metal ions.

[0251] 31. The multilayer article according to any one of the foregoing embodiments, wherein the component B contains less than 20 ppm of alkali metal and alkaline earth metal ions.

[0252] 32. The multilayer article according to any one of the foregoing embodiments, wherein the carrier layer is composed of components A, B and C in at least 80% by weight.

[0253] 33. The multilayer article according to any one of the foregoing embodiments, wherein the carrier layer is composed of components A, B and C in at least 95% by weight.

[0254] 34. The multilayer article according to any one of the foregoing embodiments, wherein the carrier layer is composed of components A, B and C to a degree of at least 99% by weight.

[0255] 35. The multilayer article according to any one of the foregoing embodiments, wherein the carrier layer is composed of components A, B and C.

[0256] 36. The multilayer article according to any one of the foregoing embodiments, wherein the multilayer article is transmissive.

[0257] 37. Use of a thermoplastic molding compound containing components A, B, and C as described in any one of embodiments 1 and 16 to 36 as a carrier layer in a multilayer article.

[0258] The multilayer article comprises the following components in the following order:

[0259] (I) Carrier layer,

[0260] (II) At least one layer comprising a colorant or a colorant composition, the layer covering at least a portion of the region between the carrier layer and the film.

[0261] (III) Thin film.

[0262] 38. A method for preparing multilayer articles,

[0263] It includes the following steps

[0264] a) Preparation of thin films

[0265] b) Printing at least a portion of the film with at least one layer consisting of a colorant or a colorant composition.

[0266] c) Optionally, the film is thermoformed.

[0267] d) The film is post-injected using a thermoplastic molding compound containing components A, B and C as described in any one of embodiments 1 to 36 above.

[0268] 39. A lighting unit, comprising:

[0269] a) Multi-layer articles according to any one of embodiments 1 to 36

[0270] b) A light source that emits light with at least one wavelength in the wavelength range of 380 to 780 nm.

[0271] The light source is configured such that the carrier layer is transmitted through the light emitted by the light source.

[0272] 40. The lighting unit according to embodiment 39, wherein the light source is an LED light source. Example

[0273] Component A-1:

[0274] Bisphenol A-based linear polycarbonate with a weight-average molecular weight M of 24000 g / mol. w (Determined by GPC in dichloromethane at room temperature relative to BPA-PC standard).

[0275] Component A-2:

[0276] Bisphenol A-based linear polycarbonate with a weight-average molecular weight M of 28,000 g / mol. w (Determined by GPC in dichloromethane at room temperature relative to BPA-PC standard).

[0277] Component B-1:

[0278] A polymer of acrylonitrile (A)-butadiene (B)-styrene (S) prepared by bulk polymerization contains a dispersed phase composed of rubber particles grafted with a styrene-acrylonitrile copolymer. These rubber particles are based on polybutadiene rubber as a grafting matrix and contain encapsulated styrene-acrylonitrile copolymer as a separate dispersed phase, as well as a styrene-acrylonitrile copolymer matrix that is not chemically bonded to or encapsulated within the rubber particles. The A:B:S ratio of component B-1 is 23 wt%:10 wt%:67 wt%, and the gel content (determined by the proportion insoluble in acetone) is 20 wt%. The acetone-soluble fraction of component B-1 has a weight-average molecular weight M of 165 kg / mol. w (Determined by GPC using polystyrene standards in tetrahydrofuran solvent). The median particle size D50 of the dispersed phase was 0.85 μm, determined by ultracentrifugation. The melt volumetric flow rate (MVR) of component B-1 was 6.7 ml / 10 min, measured at 220 °C and with a piston load of 10 kg, according to ISO 1133 (2012 edition).

[0279] Component B-2:

[0280] A polymer of acrylonitrile (A)-butadiene (B)-styrene (S) prepared by bulk polymerization contains a dispersion made of rubber particles grafted with a styrene-acrylonitrile-n-butyl acrylate terpolymer. The rubber particles are based on polybutadiene rubber as a grafting matrix and contain encapsulated styrene-acrylonitrile-n-butyl acrylate terpolymer as a separate dispersed phase, and a styrene-acrylonitrile copolymer matrix that is not chemically bonded to or encapsulated within the rubber particles. The A:B:S:BA ratio of component B-2 is 22.5 wt%:10 wt%:63 wt%:4.5 wt%, and the gel content (determined by the proportion insoluble in acetone) is 19 wt%. The acetone-soluble fraction of component B-2 has a weight-average molecular weight M of 115 kg / mol. w (Determined by GPC using polystyrene standards in tetrahydrofuran solvent). The median particle size D50 of the dispersed phase was 0.5 μm, determined by ultracentrifugation. The melt volumetric flow rate (MVR) of component C-1 was 28 g / 10 min, measured at 220 °C and with a piston load of 10 kg, according to ISO 1133 (2012 edition).

[0281] Component B-3:

[0282] A core-shell structured acrylonitrile-butadiene-styrene graft polymer was prepared by emulsion polymerization of a mixture consisting of 27 wt% acrylonitrile and 73 wt% styrene, based on 43 wt% of the ABS polymer, in the presence of 57 wt% granular crosslinked polybutadiene rubber as the grafting substrate. The polybutadiene rubber grafting substrate exhibits a bimodal particle size distribution with maximum values ​​at 0.28 μm and 0.40 μm, and a median particle size D50 of 0.35 μm as determined by ultracentrifugation.

[0283] Component B-3 does not contain styrene-acrylonitrile copolymer encapsulated in rubber particles.

[0284] Component B-4:

[0285] A core-shell acrylonitrile-butadiene-styrene graft polymer was prepared by emulsion polymerization of a mixture consisting of 26 wt% acrylonitrile and 74 wt% styrene (based on ABS polymer) in the presence of 58 wt% agglomerated granular polybutadiene rubber as a grafting substrate. Compared with the grafting substrate used in component B-3, this polybutadiene rubber grafting substrate exhibits a significantly wider unimodal particle size distribution. However, the median particle size D50, determined by ultracentrifugation, is 0.38 μm, similar to the particle size range of component B-3.

[0286] Component B-4 does not contain styrene-acrylonitrile copolymer encapsulated in rubber particles.

[0287] Component B-5:

[0288] The styrene-acrylonitrile copolymer prepared by bulk polymerization has an acrylonitrile content of 23% by weight and a weight-average molecular weight of 100,000 Da as determined by GPC in tetrahydrofuran at room temperature using a polystyrene standard. w .

[0289] Component C1:

[0290] Pentaerythritol tetrastearate

[0291] Component C-2:

[0292] Irganox TM B900 (BASF, Ludwigshafen, Germany)

[0293] 80% by weight of tris(2,4-di-tert-butyl-phenyl)phosphite (Irgafos) TM 168) and 20% by weight of 2,6-di-tert-butyl-4-(octadecyloxycarbonylethyl)phenol (Irganox) TMA mixture of 1076).

[0294] Component C-3:

[0295] Irganox TM 1076 (BASF, Ludwigshafen, Germany)

[0296] 2,6-Di-tert-butyl-4-(octadecyloxycarbonylethyl)phenol

[0297] Preparation and testing of molding compounds according to the present invention

[0298] Molding compounds were prepared using a ZSK25 twin-screw extruder from Coperion, Werner & Pfleiderer (Stuttgart, Germany) at a material temperature of 260°C and under a reduced pressure of 100 mbar (absolute).

[0299] Samples were prepared in an Arburg 270E injection molding machine at a material temperature of 260°C and a mold temperature of 80°C.

[0300] According to ISO 11443 (2014 edition), at a temperature of 260°C and 1000s... -1 The melt viscosity was determined at a shear rate of [missing information].

[0301] According to ISO 180 / 1A (2013 edition), IZOD notched impact toughness is determined on a test bar measuring 80 mm x 10 mm x 4 mm within a temperature range of -50 °C to 23 °C. The measurements at different temperatures are used to determine the ductile-brittle transition temperature, which is the temperature at which 50% of the specimens in the test undergo brittle fracture and 50% undergo ductile fracture.

[0302] To assess the ductility of materials under multiaxial stress at low temperatures, puncture tests were performed on 10 specimens, each measuring 60 mm x 60 mm x 2 mm, at -20 °C according to ISO 6603-2 (2002 edition). The percentage of brittle fracture was used as a measure of the material's ductility under multiaxial stress. Brittle fracture should be understood as fracture failure in which a portion of the specimen breaks into fragments during the puncture test, and / or the specimen exhibits unstable crack propagation, resulting in the specimen completely fracturing into two parts along such cracks during the test.

[0303] According to ISO 527 (1996 edition), the elastic modulus E and elongation at break are determined on a dumbbell bar with dimensions of 170 mm x 10 mm x 4 mm at 23 °C and at an elongation rate of 1 mm / min (elastic modulus) or 5 mm / min (elongation at break).

[0304] According to ISO 180 / 1A (2014 edition), the Vicat B / 120 softening temperature is determined as a measure of heat resistance deformation on a test bar with dimensions of 80mm x 10mm x 4mm.

[0305] According to ISO 13468-2 (2006 edition) (light source: D65, observer: 10°), the total transmittance is determined as a measure of transmittance on a specimen with dimensions of 60mm x 40mm x 2mm (i.e., material thickness of 2mm).

[0306] The half-power angle (HPA) of light intensity is used as a measure of light diffuser. A larger half-power angle means stronger light scattering. To determine the half-power angle, the intensity of transmitted light is measured after passing through a 60mm x 40mm x 2mm sample (i.e., a material thickness of 2mm). This intensity is expressed as a function of the polar angle measured relative to the incident beam in the range of 0° to 90°. The obtained value is normalized based on the intensity value measured at 0°, so the normalized intensity varies with the polar angle θ between 0 and 1, where I(0°) = 1. The half-power angle (HPA) is defined as the angle at which the normalized intensity drops to 0.5, i.e., I(HPA) = 0.5. According to this definition, the theoretically maximum possible half-power angle is 60°.

[0307]

[0308] The data in Table 1 show that molding compounds according to the invention, containing component B-1 as component B and within the range of polybutadiene content according to the invention, exhibit a surprisingly advantageous combination of high transmittance and high light diffuseness (scattering power). Furthermore, molding compounds according to the invention exhibit an advantageous combination of improved melt flowability (reduced melt viscosity) and good mechanical properties, especially good material toughness even at low temperatures. Conversely, molding compounds not of the invention containing non-inventive emulsion ABS components B-3 or B-4 or non-inventive bulk ABS component B-2 as component B do not meet this technical objective of the invention. This also applies to molding compounds made from compositions V9 and V13, whose polybutadiene rubber content is outside the range according to the invention.

[0309] Figure 1 A multi-layer article according to the present invention is shown in schematic form.

Claims

1. Multi-layer products It includes, in the following order: (I) A carrier layer made of thermoplastic molding compound containing A) At least one representative of aromatic polycarbonates and aromatic polyester carbonates, B) Rubber-modified vinyl polymers or copolymers made from the following B.1) Based on rubber-modified vinyl polymers or copolymers B, 80% to 95% by weight of structural units derived from at least one vinyl monomer, and B.2) Based on rubber-modified vinyl polymers or copolymers B, 5% to 20% by weight of one or more rubber elastomer grafted substrates, the rubber elastomer grafted substrates having a glass transition temperature of <-50°C, and based on B.2, the rubber elastomer grafted substrates containing at least 50% by weight of structural units derived from 1,3-butadiene. The rubber-modified vinyl polymer or copolymer B contains (i) The dispersed phase, which consists of the following (i.1) Rubber granules grafted with vinyl polymers or copolymers made from structural units according to B.1, and (i.2) A vinyl polymer or copolymer, which is also made of structural units according to B.1 and is encapsulated as a separate dispersed phase in rubber particles. and (ii) A rubber-free vinyl polymer or copolymer matrix, which consists of structural units according to B.1 and is not bonded to or encapsulated within the rubber particles. in, The dispersed phase according to (i) has a median particle size D50 of 0.7 µm to 2.0 µm, as determined by ultracentrifugation. C) Selected from lubricants and release agents, stabilizers, colorants, compatibilizers, other impact modifiers different from component B), and other polymer components different from components A) and B). 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. (II) At least one layer comprising a colorant or a colorant composition, the layer covering at least a portion of the region between the carrier layer and the film, and (III) Thin film.

2. The multilayer article according to claim 1, wherein the thin film is transmissive.

3. The multilayer article according to any one of claims 1 to 2, wherein the film is composed of a thermoplastic material.

4. The multilayer article according to any one of claims 1 to 2, wherein the film is composed of methyl methacrylate in an amount of at least 60% by weight.

5. The multilayer article according to any one of claims 1 to 2, wherein the film is composed of polycarbonate in an amount of at least 60% by weight.

6. The multilayer article according to any one of claims 1 to 2, wherein the thickness of the film is in the range of 50 μm to 1 mm.

7. The multilayer article according to any one of claims 1 to 2, wherein the thickness of the carrier layer is in the range of 1 mm to 5 mm.

8. The multilayer article according to any one of claims 1 to 2, wherein the multilayer article comprises a transmittance reducing layer (II) composed of a colorant or a colorant composition in a sub-region of the region between the carrier layer (I) and the film (III), and in these regions, the multilayer article has a visual transmittance of up to 10%, as measured according to DIN / ISO 13468-2, 2006 edition, using a D65 light source and at an angle of 10° for the observer.

9. The multilayer article according to any one of claims 1 to 2, wherein the carrier layer contains Component A, ranging from 30% to 85% by weight. Component B, ranging from 14% to 69% by weight. And 0.05% to 20% by weight of component C.

10. The multilayer article according to any one of claims 1 to 2, wherein the carrier layer has a rubber content of 1.9% to 4.1% by weight.

11. The multilayer article according to any one of claims 1 to 2, wherein component B of the carrier layer is prepared by bulk polymerization.

12. Use of thermoplastic molding compound as a carrier layer in a multilayer article according to any one of claims 1 to 11.

13. A method for preparing a multilayer article according to any one of claims 1 to 11, It includes the following steps: Preparation of thin films At least a portion of the film is printed using at least one layer consisting of a colorant or a colorant composition. The film is then injection molded using a thermoplastic molding compound containing... A) At least one representative of aromatic polycarbonates and aromatic polyester carbonates, B) Rubber-modified vinyl polymers or copolymers made from the following B.1) Based on rubber-modified vinyl polymers or copolymers B, 80% to 95% by weight of structural units derived from at least one vinyl monomer, and B.2) Based on rubber-modified vinyl polymers or copolymers B, 5% to 20% by weight of one or more rubber elastomer grafted substrates, the rubber elastomer grafted substrates having a glass transition temperature of <-50°C, and based on B.2, the rubber elastomer grafted substrates containing at least 50% by weight of structural units derived from 1,3-butadiene. Wherein, the rubber-modified vinyl polymer or copolymer B contains (i) The dispersed phase, which consists of the following (i.1) Rubber granules grafted with vinyl polymers or copolymers made from structural units according to B.1 and (i.2) A vinyl polymer or copolymer, which is also made of structural units according to B.1 and is encapsulated as a separate dispersed phase in the rubber particles. and (ii) A rubber-free vinyl polymer or copolymer matrix, which consists of structural units according to B.1 and is not bonded to or encapsulated within the rubber particles. Among them, the dispersed phase according to (i) has a median particle size D50 of 0.7 µm to 2.0 µm as determined by ultracentrifugation. C) Selected from lubricants and release agents, stabilizers, colorants, compatibilizers, other impact modifiers different from component B), and other polymer components different from components A) and B). 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.

14. The method according to claim 13, It includes the following steps: Preparation of thin films At least a portion of the film is printed using at least one layer consisting of a colorant or a colorant composition. The film is thermoformed. The film is post-injection molded using thermoplastic molding compound.

15. A lighting unit, comprising a) Multilayer articles according to any one of claims 1 to 11 b) A light source that emits light with at least one wavelength in the wavelength range of a spectrum from 380 nm to 780 nm. in, The light source is configured such that the carrier layer is transmitted through light emitted by the light source.

16. The lighting unit according to claim 15, wherein the light source is an LED light source.

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