Opaque, light-colored thermoplastic molding composition

Abstract

The present invention relates to opaque, light-colored thermoplastic molding compositions having improved long-term weathering stability and excellent optical appearance, in particular a high degree of color vividness. The thermoplastic molding compositions according to the invention comprise a combination of inorganic pigments and organic soluble dyes, the inorganic pigments being selected from certain mixed metal oxides and mixed metal oxosulfides. The present invention also relates to a method for producing the colored molding compositions, and to colored compositions such as masterbatches that can be used to produce the colored thermoplastic molding compositions. The present invention further relates to opaque, light-colored molded articles, such as injection molded and extrusion molded articles, produced from the thermoplastic molding compositions according to the invention.

Description

[Technical field]

[0001] The present invention relates to opaque, light-colored thermoplastic molding compositions having improved long-term weathering stability and excellent optical appearance, in particular a high degree of color vividness. The thermoplastic molding compositions according to the invention comprise a combination of inorganic pigments and organic soluble dyes, the inorganic pigments being selected from certain mixed metal oxides and mixed metal oxosulfides. The present invention also relates to a method for producing the colored molding compositions, and to colored compositions such as masterbatches that can be used to produce the colored thermoplastic molding compositions. The present invention further relates to opaque, light-colored molded articles, such as injection molded and extrusion molded articles, produced from the thermoplastic molding compositions according to the invention.

[0002] prior art Generally, thermoplastic molding compositions are characterized in that they can be melted several times to produce extruded intermediates or semi-finished products by cooling the polymer melt in a cavity designed for this purpose, or to produce molded parts. Such extruded or molded parts are often used in outdoor applications, such as in the automotive and architectural sectors. As a result, such multiple thermal and weathering loads place particular demands on the pigmented thermoplastic molding compositions and colorants used herein.

[0003] Transparent thermoplastic polymers such as polymethylmethacrylate (PMMA), polyesters, polycarbonates, polyamides, etc. are often colored in various colors using soluble organic dyes such as perinone dyes, azo dyes, anthraquinone dyes, organic pigments, and inorganic pigments. Transparent colored thermoplastics are mainly achieved using organic dyes that are truly or colloidally soluble in the monomer or polymer, while opaque colored thermoplastics are often obtained using inorganic white and colored pigments or metal powders (Kunststoff-Handbuch, Volume IX, Polymethacrylate, Carl Hanser Verlag, Munich).

[0004] Metal oxides, such as iron(III) oxide (Fe 2 O 3 The use of mixed metal oxides containing metal ions from the groups Fe, Ti, Cr, Sb, Mn, etc., results in bright and colorful colorings, but the appearance is dull and not brilliant. Cadmium-based pigments such as cadmium sulfide and cadmium sulfide / selenide were used to a considerable extent, for example, for coloring acrylic glass. However, the use of cadmium-containing pigments is no longer preferred from the point of view of environmental protection, since cadmium is released in a harmful form to the environment during waste disposal.

[0005] Some yellow or orange organic pigments, such as those from the group of diketopyrrolopyrroles (e.g. Pigment Red 254), are preferred in the paint and coatings industry but cannot in principle be used in thermoplastic molding compositions because they exhibit a color change to yellow at temperatures above 260°.

[0006] The prior art further describes a method for preparing a pigment using a light-colored organic soluble dye and titanium dioxide (TiO 2 The disadvantage of this combination is its poor weathering stability, as evidenced by common weathering tests, e.g. Xenotest. Organic soluble dyes generally exhibit poor weathering stability and therefore deteriorate, leading to the formation of white titanium dioxide (TiO 2 ) becomes more noticeable, resulting in a noticeable loss of color and a lighter color impression.

[0007] EP 0 450 478 A1 describes acrylic glass colored with organic pigments, for which it was hoped that the weather resistance could be improved by the addition of an acid. The organic pigments can be selected from commonly known and available pigments such as Pigment Yellow 151, Pigment Yellow 139 or Pigment Red 242; or from combinations of white pigments, such as titanium dioxide, with soluble dyes, such as Macrolex® dyes (Lanxess), Solvaperm® dyes (Clariant) and Thermoplast® dyes (BASF SE).

[0008] DE 102004058083 A1 describes dark IR-reflective molding compositions in which different inorganic pigments of brown, grey, dark and green are utilized, the inorganic pigments being based on metal oxides having a spinel structure.

[0009] WO 2015 / 036526 describes a polystyrene-based deep black molding composition that contains nanoscale carbon black and at least two organic dyes. Light-colored compositions are not described, and light-colored compositions cannot be obtained using the coloring compositions described in WO 2015 / 036526.

[0010] WO 2019 / 228959 discloses an opaque multilayer object comprising a substrate layer based on polycarbonate or polymethyl methacrylate and a coating layer comprising a UV absorber, the substrate layer comprising a specific coated titanium dioxide and at least two other organic colorants selected from organic or inorganic dyes or pigments. WO 2019 / 228959 describes examples of polycarbonate substrate layer materials comprising a specific coated titanium dioxide, a yellow inorganic pigment based on mixed metal oxides (e.g. Pigment Yellow 53 or Pigment Brown 24) and a soluble organic dye, such as Solvent Red 135, Solvent Yellow 93 or Solvent Yellow 114.

[0011] Pyrochlore and rutile metal oxides are commonly known and are often used as inorganic pigments in a variety of applications. Pyrochlore usually crystallizes in the tetragonal system, often forming brown, red, orange or yellowish octahedral crystals. Rutile usually crystallizes in the tetragonal system. Pyrochlore and rutile used as pigments are often mixed metal oxides, typically incorporating main group or transition metals (e.g. Zn, Cr, Sn) in their crystal lattice. For example, transition metal-based pyrochlores are preferably based on niobium-tin or niobium-tin-zinc, and metal-based rutiles are based on titanium-tin-zinc.

[0012] For example, lead antimony pyrochlore is known as Pigment Yellow 41. Niobium / antimony pyrochlore type pigments containing one or more divalent metal ions, in particular tin and / or zinc, and their preparation are described in WO 2014 / 160218 and WO 2011 / 156362. Niobium Tin Pyrochlore (NTP), such as Niobium Tin Zinc Pyrochlore (Pigment Yellow 227), is available from Shepard Color Company.

[0013] For example, known pigments of the rutile class are nickel titanates, such as Ni / Sb / Ti oxide (Pigment Yellow 53), chromium titanates, such as Cr / Sb / Ti oxide (Pigment Brown 24), both available from BASF, and Sn / Zn / Ti oxide (Pigment Yellow 216, available from Shepard Color Company).

[0014] The use of pyrochlore and rutile metal oxide pigments for the coloring of textile layers in adhesive tapes is described in WO 2019 / 101377. EP 3 868 817 A1 describes polyamide-based polymer compositions for high-voltage components which contain pigment systems based on Ti / Sn / Zn mixed metal oxides, for example Pigment Orange 82 or Pigment Yellow 216.

[0015] Furthermore, the publication M. Ryan, European Coatings Journal (2013), (3), 74-78 describes yellow and orange pigments including niobium tin pyrochlore as a yellow pigment, as well as some titanate pigments such as nickel titanate (e.g. Pigment Yellow 53), chromium titanate (e.g. Pigment Brown 24), bismuth vanadate (e.g. Pigment Yellow 184) and rutile tin zinc pigments such as Pigment Yellow 216. The thermal and weathering stability of these coloring compositions and their use in thermoplastic resins are not discussed.

[0016] Furthermore, the use of rutile tin zinc pigments, such as Pigment Yellow 216 (Solaplex™), in coating applications such as automotive paints is described in the publication Larry Lane, “A New Class of Weather-Fast Pigments”, PCI Paint & Coatings Industry, April 1, 2005. The pigments exhibit high acid resistance and high weather resistance. It is stated that the inorganic pigments can be ideally used alone or in combination with high performance organic pigments and titanium dioxide to produce full color plates.

[0017] Object of the invention It is therefore an object of the present invention to provide a method for producing a color filter having excellent optical properties, in particular the color saturation (C *The objective of the present invention was to provide an opaque, light-colored thermoplastic molding composition having high color vividness, measured as the difference in color distance ΔE, typically measured according to DIN 6174 under weathering conditions such as Xenotest.

[0018] Furthermore, it was desired that the thermoplastic molding composition would have excellent thermally stable optical properties and maintain its high color vibrancy even when exposed to high temperatures and / or high shear forces, for example during injection molding of parts having complex geometric shapes.

[0019] Another object of the present invention was to provide opaque, light-colored molded articles, such as molded parts and extruded articles, particularly those having these advantageous properties and / or complex geometric shapes.

[0020] Furthermore, it was an object of the present invention to provide a coloring composition which comprises the inventive combination of an inorganic pigment and an organic dye, which is easy to handle and which is highly suitable for producing the thermoplastic molding composition according to the invention by cost-effective, easy and safe steps.

[0021] Summary of the Invention The present invention is based on the surprising finding that opaque light-colored molding compositions with excellent color brilliance and improved weathering stability are obtained, especially when selected inorganic pigments are combined with at least one soluble organic dye. It has been found that improved weathering stability is obtained when certain yellow or orange inorganic pigments, in particular mixed oxides or mixed oxosulfides of pyrochlore or rutile structure type, are used instead of titanium dioxide as known from the prior art. Surprisingly, it has been found that the inventive combination of certain inorganic pigments with soluble organic dyes shows improved color brilliance compared to combinations of other yellow or orange inorganic pigments with the same soluble organic dye as known from the prior art. Thus, the inventive combination of certain yellow or orange inorganic pigments with at least one soluble organic dye is opaque light-colored and provides excellent properties for application in thermoplastic molding compositions where high thermal and weathering stability are required.

[0022] The present invention relates to the following: A. a polymer matrix A comprising at least one thermoplastic polymer; B. at least one inorganic pigment B selected from mixed metal oxides or mixed metal oxosulfides B1 comprising the metals niobium (Nb), tin (Sn) and zinc (Zn) and / or mixed metal oxides or mixed metal oxosulfides B2 comprising the metals titanium (Ti), tin (Sn) and zinc (Zn); C. at least one organic dye C, typically a soluble organic dye C, preferably selected from monoazo dyes, perinone dyes, quinophthalone dyes and anthraquinone dyes; The present invention relates to a thermoplastic molding composition comprising:

[0023] Preferably, the present invention is directed to opaque light-coloured thermoplastic moulding compositions, in particular opaque light-coloured thermoplastic moulding compositions which exhibit a yellow, orange or red impression.

[0024] In the context of the present invention, terms such as "opaque" and "opaque thermoplastic molding composition" or "opaque molded article" refer to a color or colored material having a transmittance Y(D65) of less than 10%, preferably less than 6.5%, determined at 23° C. using standard illumination D65 / 10° according to DIN 5033-7 and measured on a 3.0 mm thick sample, in particular an injection molded sample.

[0025] In the context of the present invention, the terms "light-coloured" and "light-coloured thermoplastic moulding composition" or "light-coloured moulded article" refer to colour or pigmented materials which exhibit a yellow, orange or red impression; preferably colour values ​​a determined at 23° C. in accordance with DIN 5033-3 using standard illumination D65 / 10° and measured in reflection on samples of 3.0 mm thickness, in particular injection moulded samples. * and b * are both greater than zero (a * >0 and b * >0) Refers to color or coloring material.

[0026] In the context of the present invention, the term "soluble dye" or "soluble organic dye" refers to an organic colorant that is soluble in a thermoplastic matrix A comprising at least one thermoplastic polymer in the amounts typically used for coloring the thermoplastic matrix A. In particular, the term "soluble organic dye" refers to an organic dye that is soluble in the polymer matrix A in an amount of at least 0.5% by weight, preferably at least 1% by weight, more preferably at least 5% by weight relative to the mixture of polymer matrix A and soluble organic dye. Typically, the term "soluble organic dye" refers to an organic dye that is monomolecularly dispersed in the polymer matrix A, preferably in the amounts mentioned above.

[0027] In general, a thermoplastic matrix containing only a soluble organic dye C (meaning a composition consisting of a polymer matrix A and one or more organic dyes) exhibits a very low haze, preferably a haze of 5% or less (<=5%), preferably 4% or less (<=4%) (measured at 23°C on a test piece having a thickness of 1 mm according to the standard ASTM D1003). In particular, the term "soluble organic dye" refers to an organic dye for which a composition consisting of a polymer matrix A and a soluble organic dye in an amount of 0.5% by weight, preferably 1% by weight, relative to the composition of the polymer matrix A and the soluble organic dye, exhibits a haze of 5% or less (<=5%), preferably 4% or less (<=4%) (measured at 23°C on a test piece having a thickness of 1 mm according to the standard ASTM D1003).

[0028] In the context of the present invention, "pigment" refers to inorganic and organic colorants that are substantially insoluble in a thermoplastic matrix A comprising at least one thermoplastic polymer in the amounts used to color the thermoplastic matrix A. Typically, the term "pigment" encompasses chromatic colorants, white colorants and black colorants. Typically, the term "pigment" refers to organic colorants that are dispersed in the polymer matrix A in the form of solid particles, in particular finely dispersed solid particles.

[0029] The term "colored thermoplastic molding composition" as used herein refers to a thermoplastic molding composition comprising one or more colorants, preferably a thermoplastic molding composition comprising at least colorants A and B as described herein, wherein the colorants are homogeneously dispersed in the polymer matrix A of the thermoplastic molding composition.

[0030] Detailed Description In a preferred embodiment, the thermoplastic molding composition according to the invention comprises, respectively, the following relative to the total thermoplastic molding composition: A. 49.99998 to 99.99998% by weight, preferably 59.9998 to 99.9998% by weight, more preferably 89.998 to 99.998% by weight of a polymer matrix A, where the polymer matrix A preferably comprises (or consists of) at least one thermoplastic polymer selected from polyalkyl(meth)acrylates, poly(meth)acrylimides, polyalkyl(meth)acrylate copolymers, polystyrene, polystyrene copolymers, acrylonitrile copolymers, polycarbonates, polyesters, polyamides, polyvinylidene fluoride and polyolefins; B. 0.00001 to 5.0% by weight, preferably 0.0001 to 4.0% by weight, more preferably 0.001 to 3.0% by weight of at least one inorganic pigment B; C. 0.00001-5.0% by weight, preferably 0.0001-4.0% by weight, more preferably 0.001-3.0% by weight of at least one organic dye C, where the organic dye C is preferably selected from monoazo dyes, perinone dyes, quinophthalone dyes, anthraquinone dyes and pyrazolone dyes, more preferably selected from monoazo dyes, perinone dyes, quinophthalone dyes and anthraquinone dyes; D. 0 to 50.0% by weight, preferably 0 to 40.0% by weight, more preferably 0 to 10.0% by weight of one or more additional components D, preferably selected from organic pigments, inorganic pigments different from B, scattering particles, impact modifiers, antistatic agents, antioxidants, mold release agents, flame retardants, lubricants, flow improvers, UV absorbers, light stabilizers and organic phosphorus compounds, agents imparting weather resistance and plasticizers. Includes.

[0031] Preferably, the weight ratio B:C of inorganic pigment B to organic dye C as defined herein ranges from 0.1-10, preferably from 0.5-5, more preferably from 0.75-3.

[0032] In particular, in the thermoplastic molding compositions according to the invention, the transmittance Y(D65), determined at 23 ° C. according to DIN 5033-7 with standard illumination D65 / 10 ° and measured on a sample, in particular an injection-molded sample, having a thickness of 3.0 mm, is less than 10%, preferably less than 6.5%. In particular, in the thermoplastic molding compositions according to the invention, the color value a, determined at 23 ° C. according to DIN 5033-3 with standard illumination D65 / 10 ° and measured in reflection on a sample, in particular an injection-molded sample, having a thickness of 3.0 mm, is less than 10%, preferably less than 6.5%. * and b * Both are greater than zero (a * >0 and b * >0). Preferably, a * >0.5, more preferably a * >1; and / or b * >0.5, more preferably b * >1.

[0033] Preferably, in the thermoplastic molding composition according to the invention, the luminance L determined at 23 ° C. according to DIN 5033-3 with standard illumination D65 / 10 ° and measured in reflection on a sample, in particular an injection-molded sample, having a thickness of 3.0 mm, is * is 30 or more.

[0034] Preferably, the thermoplastic molding compositions according to the invention have excellent weathering stability, i.e. the color difference ΔE (D ) determined according to DIN 6174 after 3000 hours under xenon test conditions with xenon radiant daylight (ISO 4892-2) 65 , 10°) is 3 or less, preferably 2 or less.

[0035] For example, the thermoplastic molding composition comprises a polymer matrix A consisting essentially of at least one polyalkyl(meth)acrylate, preferably polymethyl(meth)acrylate (PMMA), and has a melt volume-flow rate MVR of 0.5 to 10.0 cm3, measured at 230°C under a load of 3.8 kg according to ISO 1133 (2011). 3 / 10min.

[0036] For example, the thermoplastic molding composition comprises a polymer matrix A consisting essentially of at least one polycarbonate (PC) and has a melt volume-flow rate MVR of 10.0 to 36.0 cm3, measured at 300 °C under a load of 1.2 kg according to ISO 1133 (2011). 3 / 10min.

[0037] For example, the thermoplastic molding composition comprises a polymer matrix A consisting essentially of at least one styrene-acrylonitrile copolymer (SAN) and has a melt volume-flow rate (MVR) of 5.0 to 30.0 cm3, measured at 220°C under a load of 10 kg according to ISO 1133 (2011). 3 / 10min.

[0038] The pigmented thermoplastic molding compositions according to the invention can therefore be advantageously used in extrusion and injection molding, the melt temperature, the mold temperature and the injection speed being adaptable based on the polymer matrix A. Preferably, the thermoplastic molding compositions according to the invention have excellent thermal stability and can be used in conventional melt processes such as extrusion and injection molding without undesirable changes in the color impression or color distance, typically at temperatures in the range of 150 to 320 ° C. Typically, when the thermoplastic polymer is a polyalkyl (meth)acrylate, the thermal stability is given at temperatures in the range of 200 ° C. to 300 ° C., more preferably 230 ° C. to 290 ° C.

[0039] Polymer Matrix A The polymer matrix A preferably comprises, preferably essentially consists of, at least one thermoplastic polymer selected from polyalkyl(meth)acrylates (e.g. polymethyl methacrylate PMMA), poly(meth)acrylimides (e.g. polymethyl methacrylimides PMMI), polyalkyl(meth)acrylate copolymers, polystyrene, polystyrene copolymers, acrylonitrile copolymers, polycarbonates (preferably aromatic polycarbonates derived from bisphenols or polycarbonates derived from isosorbide), polyesters (preferably aromatic polyesters, more preferably polyethylene terephthalate), polyamides, polyvinylidene fluoride (PVDF) and polyolefins (e.g. cycloolefin copolymers COC or clarified polypropylene).

[0040] Preferably, the polymer matrix A comprises or essentially consists of a transparent thermoplastic polymer or a transparent blend of at least two thermoplastic polymers, where the term "transparent" refers to a thermoplastic polymer or polymer composition having a haze of less than or equal to 70%, preferably less than or equal to 50%, more preferably less than or equal to 30%, and preferably less than or equal to 10%, determined in accordance with standard ASTM D1003 and measured at 23°C on injection-molded test specimens of 3.0 mm thickness.

[0041] More preferably, the thermoplastic polymer is selected from polyalkyl(meth)acrylates (e.g., polymethylmethacrylate PMMA), poly(meth)acrylimides (e.g., polymethylmethacrylimides PMMI), polyalkyl(meth)acrylate copolymers, polystyrene, polystyrene copolymers, acrylonitrile copolymers, polycarbonates, polyesters (preferably, polyethylene terephthalate), polyvinylidene fluoride, and mixtures thereof. Even more preferably, the thermoplastic polymer is selected from the group consisting of polyalkyl(meth)acrylates, polyalkyl(meth)acrylate copolymers, poly(meth)acrylimides, polycarbonates, and mixtures thereof.

[0042] According to a particularly preferred embodiment, the polymer matrix A comprises (preferably consists essentially of) at least one thermoplastic polymer selected from polyalkyl(meth)acrylates (e.g. polymethylmethacrylate PMMA), polyalkyl(meth)acrylate copolymers, poly(meth)acrylimides (e.g. polymethylmethacrylimides PMMI), polycarbonates (e.g. polycarbonates derived from bisphenols or isosorbide), and styrene-acrylonitrile copolymers (SAN). More preferably, the polymer matrix A comprises (preferably consists essentially of) a thermoplastic polymer selected from polymethylmethacrylate (PMMA) and / or polymethylmethacrylimides (PMMI).

[0043] It is also possible for the thermoplastic molding composition according to the invention to be based on impact-resistant polyalkyl(meth)acrylates (for example impact-resistant polymethyl methacrylate PMMA) and / or impact-resistant polyalkyl(meth)acrylate copolymers, and for the thermoplastic molding composition to be a polymer matrix A comprising or essentially consisting of one or more polyalkyl(meth)acrylates (e.g. polymethylmethacrylate PMMA) and / or one or more polyalkyl(meth)acrylate copolymers; at least one impact modifier, described below as additional component D, dispersed in the polymer matrix A; It is also preferred to include:

[0044] Preferably, the polymer matrix A is present in an amount of 49.99998 to 99.99998% by weight, preferably 59.9998 to 99.9998% by weight, preferably 69.99998 to 99.99998% by weight, preferably 89.9998 to 99.9998% by weight, more preferably 89.998 to 99.998% by weight, based on the total thermoplastic molding composition. Typically, the lower limit of the polymer matrix A can be adapted if one or more optional additional components D are present in the thermoplastic molding composition according to the invention.

[0045] Polyalkyl(meth)acrylates and polyalkyl(meth)acrylate copolymers Polyalkyl(meth)acrylates are usually obtained by free radical polymerization of a mixture that typically comprises an alkyl(meth)acrylate, typically methyl methacrylate (a) and at least one further (meth)acrylate (b). These mixtures generally comprise at least 50% by weight, preferably at least 60% by weight, particularly preferably at least 80% by weight, even more preferably at least 90% by weight of methyl methacrylate (a) relative to the weight of the monomers. The amount of methyl methacrylate (a) used generally is between 50.0% and 99.9% by weight, preferably between 80.0% and 99.0% by weight, particularly preferably between 90.0% and 99.0% by weight, relative to the weight of the monomers.

[0046] These mixtures for producing polyalkyl(meth)acrylates or polyalkyl(meth)acrylate copolymers can also contain other (meth)acrylates (b) copolymerizable with methyl methacrylate (a). The term "(meth)acrylate" as used herein is meant to encompass methacrylates, acrylates and mixtures thereof. The (meth)acrylates can be derived from saturated alcohols, such as methyl acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, tert-butyl (meth)acrylate, isobutyl (meth)acrylate, pentyl (meth)acrylate and 2-ethylhexyl (meth)acrylate; or from unsaturated alcohols, such as oleyl (meth)acrylate, 2-propynyl (meth)acrylate, allyl (meth)acrylate, vinyl (meth)acrylate; and also aryl (meth)acrylates, such as benzyl (meth)acrylate or phenyl (meth)acrylate, cyclohexyl ... Alkyl (meth)acrylates, such as 3-vinylcyclohexyl (meth)acrylate, bornyl (meth)acrylate; hydroxyalkyl (meth)acrylates, such as 3-hydroxypropyl (meth)acrylate, 3,4-dihydroxybutyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate; glycol di(meth)acrylates, such as 1,4-butanediol (meth)acrylate, (meth)acrylates of ether alcohols, such as tetrahydrofurfuryl (meth)acrylate, vinyloxyethoxyethyl (meth)acrylate; amides and nitriles of (meth)acrylic acid, and the like.

[0047] The amount of (meth)acrylic comonomer (b) used is generally 0.1% by weight to 50.0% by weight, preferably 1.0% by weight to 20.0% by weight, particularly preferably 1.0% by weight to 10.0% by weight, based on the weight of the monomer, and in this case the compounds can be used alone or in the form of a mixture.

[0048] The polymerization reaction is generally initiated by known free radical initiators. Preferred initiators include, in particular, azo initiators well known to those skilled in the art, such as AIBN and 1,1-azobiscyclohexanecarbonitrile, as well as peroxy compounds, such as methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl 2-ethylperhexanoate, ketone peroxides, methyl isobutyl ketone peroxide, cyclohexanone peroxide, dibenzoyl peroxide, tert-butyl peroxybenzoate, tert-butyl peroxyisopropyl carbonate, 2,5- bis(2-ethylhexanoylperoxy)-2,5-dimethylhexane, tert-butyl 2-ethylperoxyhexanoate, tert-butyl 3,5,5-trimethylperoxyhexanoate, dicumyl peroxide, 1,1-bis(tert-butylperoxy)cyclohexane, 1,1-bis(tert-butylperoxy)-3,3,5-trimethylcyclohexane, cumyl hydroperoxide, tert-butyl hydroperoxide, bis(4-tert-butylcyclohexyl)peroxydicarbonate or mixtures thereof.

[0049] Polyalkyl(meth)acrylate copolymers are usually obtained by free radical polymerization of a mixture comprising an alkyl(meth)acrylate, typically methyl methacrylate (a), at least one further (meth)acrylate (b) as described above, and other unsaturated monomers (c) copolymerizable alone or by using other monomers that promote copolymerization with methyl methacrylate and the above-mentioned (meth)acrylates. Among these are in particular 1-alkenes such as 1-hexene, 1-heptene, branched alkenes such as vinylcyclohexane, 3,3-dimethyl-1-propene, 3-methyl-1-diisobutylene, 4-methyl-1-pentene, acrylonitrile, vinyl esters such as vinyl acetate, styrene, substituted styrenes with alkyl substituents in the side chain, for example α-methylstyrene and α-ethylstyrene, maleic anhydride, methylmaleic anhydride, maleimide, maleic acid derivatives such as methylmaleimide, and dienes such as divinylbenzene.

[0050] The amount of these comonomers (c) used in general is 0.0% by weight to 40.0% by weight, preferably 0.0% by weight to 30.0% by weight, more preferably 0.0% by weight to 15.0% by weight, and particularly preferably 0.0% by weight to 10.0% by weight, relative to the weight of the monomer, and in this case, the compounds can be used alone or in the form of a mixture.

[0051] In another preferred embodiment, the polymer matrix A comprises or essentially consists of at least one polyalkyl(meth)acrylate and / or polyalkyl(meth)acrylate copolymer, which is selected from the group consisting of: 50.0 to 100.0% by weight, preferably 65 to 99% by weight, of methyl methacrylate (MMA); 0.0-20.0% by weight, preferably 0.1-4% by weight, of at least one alkyl (meth)acrylate other than MMA, preferably selected from C1-C10 alkyl (meth)acrylates, more preferably selected from C1-C4 alkyl (meth)acrylates, such as methyl acrylate, ethyl acrylate, n-butyl acrylate and butyl methacrylate; 0.0 to 40% by weight, preferably 5.0% to 30.0% by weight, of at least one vinyl aromatic monomer, preferably styrene; and 0.0 to 20% by weight, preferably 5.0 to 20.0% by weight, of one or more further copolymerizable monomers, such as at least one unsaturated carboxylic acid or anhydride, or acrylonitrile; wherein all amounts are given relative to the total weight of the polyalkyl (meth)acrylate or polyalkyl (meth)acrylate copolymer.

[0052] In one preferred example, the polymer matrix A may comprise or consist of at least one polyalkyl(meth)acrylate copolymer, which may be one of the following: 48.0-90.0% by weight, preferably 63.0-81.0% by weight, of at least one alkyl (meth)acrylate, preferably methyl methacrylate (MMA); 8.0 to 35.0% by weight, preferably 12.0 to 22.0% by weight, of at least one monovinyl aromatic monomer, preferably styrene; and 2.0 to 17.0% by weight, preferably 7.0 to 15.0% by weight, of at least one unsaturated carboxylic anhydride, for example selected from acrylic anhydride, methacrylic anhydride, maleic anhydride, 1,2-cyclohexanedicarboxylic anhydride, cyclohexylmaleimide and itaconic anhydride, more preferably maleic anhydride; wherein all amounts are given relative to the total weight of the polyalkyl (meth)acrylate copolymer.

[0053] More preferably, the polyalkyl (meth)acrylate copolymer comprises or consists essentially of 50.0 to 85.0 wt. % MMA, 10.0 to 20.0 wt. % styrene, and 5.0 to 15.0 wt. % maleic anhydride.

[0054] Suitable polyalkyl(meth)acrylate copolymers and blends thereof are described, for example, in WO 2005 / 108486, WO 2008 / 148595 and WO 2020 / 126722.

[0055] Further preferred are polyalkyl(meth)acrylates obtained by polymerization of a composition having as polymerizable component: (a) 50.0% to 99.9% by weight of methyl methacrylate; (b) 0.1% to 50.0% by weight of an acrylic acid ester of a C1 to C4 alcohol; (c) 0.0% by weight to 30.0% by weight of a monomer copolymerizable with monomers (a) and (b).

[0056] In one particularly preferred embodiment, the polyalkyl(meth)acrylate is obtainable by polymerization of a composition in which the polymerizable component comprises, by weight of the polymerizable composition: (a) 80.0% to 99.0% by weight of methyl methacrylate, and (b) 1.0 wt. % to 20.0 wt. % of an acrylic acid ester of a C1 to C4 alcohol.

[0057] Particularly preferred are polyalkyl(meth)acrylates composed of 80.0% to 99.5% by weight of methyl methacrylate and 0.5% to 20.0% by weight of methyl acrylate and / or ethyl acrylate, the amounts being based on 100% by weight of the polymerizable components. Particularly advantageous copolymers are those obtained by copolymerization of 85.0% to 99.5% by weight of methyl methacrylate with 0.5% to 15.0% by weight of methyl acrylate and / or ethyl acrylate, the amounts being based on 100% by weight of the polymerizable components. For example, the polyalkyl (meth)acrylate may comprise 85.0% to 99.9% by weight of methyl methacrylate and 0.1% to 15.0% by weight of methyl acrylate, preferably 95.0% to 99.9% by weight of methyl methacrylate and 0.1% to 5.0% by weight of methyl acrylate, more preferably 96.0% to 99.9% by weight of methyl methacrylate and 0.1% to 4.0% by weight of methyl acrylate. The Vicat softening point VSP (ISO 306:2013, method B50) of the polyalkyl (meth)acrylate is typically at least 90°C, preferably 95°C to 130°C.

[0058] The weight-average molecular weight Mw of the polyalkyl(meth)acrylates is generally in the range from 50 000 g / mol to 300 000 g / mol. Particularly advantageous mechanical properties are obtained with polyalkyl(meth)acrylates having a weight-average molecular weight Mw in the range from 50 000 g / mol to 200 000 g / mol, preferably from 80 000 g / mol to 180 000 g / mol, determined in each case by GPC against PMMA calibration standards and THF as eluent.

[0059] In another preferred example, the polymer matrix A may comprise or consist of a blend comprising polymethyl methacrylate (PMMA) and at least one polyvinylidene fluoride (PVDF), such as the Kynar® product type available from Arkema.

[0060] In another preferred example, the polymer matrix A may comprise or consist of a blend comprising polymethyl methacrylate (PMMA) and at least one poly(lactide) (PLA), such as the Altuglas® Rnew® products available from Altuglas International.

[0061] Poly(meth)acrylamide The polymer matrix A may comprise at least one thermoplastic polymer selected from poly(meth)acrylimides, preferably polymethyl(meth)acrylimides, more preferably polymethylmethacrylimides (PMMI). The poly(meth)acrylimides that can be used in the present invention have the formula (I): [ka] [In the formula, R 1 and R 2 are independently selected from hydrogen and a methyl group; R 1 and R 2 preferably represents a methyl group, R 3 is hydrogen or C 1 ~C 4 The poly(meth)acrylamide comprises at least 30% by weight, preferably at least 50% by weight, and most preferably at least 60% by weight of repeating units of the alkyl group, preferably a methyl group, based on the weight of the poly(meth)acrylimide.

[0062] Methods for producing PMMI are disclosed, for example, in EP 216505, EP 666161 or EP 776910, the entire disclosures of which are incorporated herein by reference.

[0063] The starting materials used for the preparation of poly(meth)acrylimides include polymers derived from alkyl esters of methacrylic acid, generally composed of more than 50.0% by weight, preferably more than 80.0% by weight, particularly preferably 95.0% to 100.0% by weight of units of alkyl esters of methacrylic acid having 1 to 4 carbon atoms in the alkyl group. Methyl methacrylate is preferred. The preferred polymers are composed of at least 80.0% by weight, preferably more than 90.0% by weight, more preferably more than 95.0% by weight, even more preferably more than 99.0% by weight of methyl methacrylate, the use of neat methyl methacrylate being the most preferred. Comonomers that can be used include any monomer copolymerizable with methyl methacrylate, in particular alkyl esters of acrylic acid having 1 to 4 carbon atoms in the alkyl group, acrylo- or methacrylonitrile, acrylic or methacrylamide, styrene, or maleic anhydride. Thermoplastically processable polymers of this type are preferred, whose reduced viscosity is in the range of 20 ml / g to 92 ml / g, preferably 50 ml / g to 80 ml / g (measured according to ISO 8257 (2006), Part 2). They are used in the form of powders or pellets, the median diameter of which is about 0.03 mm to 5 mm.

[0064] Typically, the PMMI used in the present invention has a weight average molecular weight Mw of 80000 g / mol to 200000 g / mol, preferably 90000 g / mol to 150000 g / mol, determined by GPC using PMMA as standard. Such materials are commercially available under the trademark PLEXIMID® from Roehm GmbH. Suitable products include, but are not limited to, PLEXIMID® TT50, PLEXIMID® TT70, PLEXIMID® 8805, PLEXIMID® 8813, PLEXIMID® 8817.

[0065] Polycarbonate Polycarbonates can also be used as thermoplastic polymers in the present invention. Polycarbonates can be formally considered as polyesters formed from carbonic acid and aliphatic or aromatic dihydroxyl compounds. They can be readily obtained, for example, by reacting diglycol, isosorbide or bisphenol with phosgene or carbonic acid diesters by polycondensation or transesterification.

[0066] Preferred are polycarbonates derived from bisphenols and / or isosorbide. These bisphenols include in particular 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(4-hydroxyphenyl)butane (bisphenol B), 1,1-bis(4-hydroxyphenyl)cyclohexane (bisphenol C), 2,2'-methylenediphenol (bisphenol F), 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane (tetrabromobisphenol A) and 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane (tetramethylbisphenol A) and mixtures thereof. Typically, such aromatic polycarbonates are produced by interfacial polycondensation or transesterification. The properties of the polycarbonate can be adapted to the desired purpose by the choice of bisphenol.

[0067] Polycarbonates are commercially available, for example, from Covestro AG (Germany) under the trademark Makrolon®.

[0068] For example, a suitable polycarbonate derived from isosorbide is the DURABIO™ transparent product type available from Mitsubishi Chemical Corporation MCC.

[0069] Polystyrene and polystyrene copolymers The polymer matrix A may also contain at least one thermoplastic polymer selected from homo- or copolymers containing at least one vinyl aromatic monomer. Particularly suitable vinyl aromatic monomers are selected from styrene, α-methylstyrene, tert.-butylstyrene, monochlorostyrene and vinyltoluene, with styrene and α-methylstyrene being particularly preferred. The aromatic vinyl monomers may be used alone or in mixtures thereof.

[0070] Preferably, the polymer matrix A may comprise at least one copolymer comprising a vinyl aromatic monomer and a vinyl cyanide monomer.

[0071] Examples of vinyl cyanide monomers suitable for use in the present invention include acrylonitrile, methacrylonitrile, ethacrylonitrile, phenylacrylonitrile, α-chloroacrylonitrile, fumaronitrile, and the like. These can be used alone or in mixtures thereof. For example, the vinyl cyanide monomer can include acrylonitrile and / or methacrylonitrile. In a particularly preferred embodiment, the vinyl cyanide monomer is acrylonitrile.

[0072] Typically, the copolymer may contain, by weight of the copolymer, 50.0% to 90.0%, preferably 55.0% to 85.0%, of the aromatic vinyl monomer; and 10.0% to 50.0%, preferably 15.0% to 45.0%, of the cyanide vinyl monomer.

[0073] In a preferred embodiment, the aromatic vinyl monomer is styrene and the cyanide vinyl monomer is acrylonitrile. Such preferred thermoplastic copolymers are generally known as styrene-acrylonitrile copolymer (SAN) resins and are commercially available from various manufacturers such as INEOS Styrolution Group GmbH (Frankfurt, Germany) or Trinseo SA (Luxembourg). The preparation of such copolymers can be carried out by virtually any known polymerization method described for the preparation of SAN resins, such as bulk polymerization, solution polymerization, emulsion polymerization or bead polymerization.

[0074] Typically, styrene-acrylonitrile copolymers (SAN) having a weight average molecular weight Mw of substantially any molecular weight, for example, 60000 g / mol to 300000 g / mol, preferably 100000 g / mol to 250000 g / mol, can be used. The average molecular weight Mw of copolymer B can be determined by GPC using PMMA standard as described above.

[0075] More preferably, the thermoplastic copolymers may be selected from styrene-acrylonitrile copolymers (SAN) and rubber modified styrene-acrylonitrile copolymers, such as acrylonitrile-butadiene-styrene copolymers (ABS) and acrylonitrile-styrene-acrylate copolymers (ASA), as well as α-methylstyrene-acrylonitrile (AMSAN) copolymers and rubber modified AMSAN copolymers, such as SAN copolymers available as LURAN® product types, ABS copolymers as Terluran®, Lustran® or Novodur®, ASA copolymers as Luran® S, and AMSAM copolymers as Luran® High Heat, all from Ineos Styrolution.

[0076] Furthermore, the polymer matrix A may comprise at least one copolymer comprising an aromatic vinyl monomer, preferably styrene, and a conjugated diene monomer, preferably butadiene. For example, the polymer matrix A may comprise or consist of at least one styrene-butadiene block copolymer (SBC) and blends thereof. SBC copolymers are widely known and are commercially available under the trade name KratonT™ from Kraton Corporation or under the trade names Styrolux® and Styroflex® from INEOS Styrolution. In particular, the polymer matrix A may comprise or consist of blends of SBC with styrene polymers (e.g. high impact general purpose polystyrene GPPS), blends of SBC with styrene-acrylic copolymers, such as methyl methacrylate-butadiene-styrene copolymers (MBS), for example available as Zylar® or Clearblend® product types from Ineos Styrolution. Furthermore, the polymer matrix A may comprise or consist of a methyl methacrylate-acrylonitrile-butadiene-styrene copolymer (MABS), for example available from Ineos Styrolution as TERLUX® or CLEARLUX® product types.

[0077] Other Thermoplastic Polymers For example, the polymer matrix A can comprise or consist of one or more polyamides selected from, for example, commercially available transparent polyamide products, such as Grilamid TR® (e.g., Grilamid TR® 90) and EMS-GRIVORY (both from EMS-Chemie AG), TROGAMIDE® type products from Evonik (e.g., TROGAMIDE® CX 7323, TROGAMIDE® T5000, TROGAMIDE® BX), and VESTAMID® type products from Evonik.

[0078] For example, the polymer matrix A may comprise or consist of one or more polyolefins, preferably one or more transparent polyolefins, more preferably selected from cycloolefin copolymers (COC), such as commercially available transparent cycloolefin copolymers, such as the TOPAS® COC products from TOPAS Advanced Polymers GmbH, and the ZEONEX® and ZEONOR® products from ZEON Corporation. Furthermore, the polyolefin may be selected from nucleated or clarified polypropylenes (PP), for example produced using Millad® NX 8000 clarifying agent from Milliken.

[0079] Inorganic Pigment B The thermoplastic molding composition according to the invention comprises at least one inorganic pigment B; this is preferably chosen from inorganic pigments exhibiting a yellow, orange or brown colour impression; where the inorganic pigment B is one of the following: Mixed metal oxides or mixed metal oxosulfides B1 containing the metals niobium (Nb), tin (Sn) and zinc (Zn); and / or mixed metal oxides or mixed metal oxosulfides B2 containing the metals titanium (Ti), tin (Sn) and zinc (Zn). is selected from.

[0080] Preferably, the mixed metal oxide or oxosulfide B1 and the mixed metal oxide or oxosulfide B2 each contain at least 1 ppm, preferably at least 10 ppm, of tin (Sn) and at least 1 ppm, preferably at least 10 ppm, of zinc (Zn). In the context of the present invention, ppm means parts by weight (wppm), e.g. mg / kg. More preferably, the mixed metal oxide or oxosulfide B1 and the mixed metal oxide or oxosulfide B2 each contain 0.01 to 60% by weight, preferably 10 to 50% by weight, of tin (Sn) and 0.01 to 30% by weight, preferably at least 1 to 20% by weight, of zinc (Zn), calculated as metal, respectively, relative to the total weight of B1 or B2.

[0081] The mixed metal oxides or mixed metal oxosulfides B1 and / or B2 may also contain one or more additional elements, preferably metals or metalloids, which are in particular selected from the elements of groups 1, 2, 12, 13, 14 and 15 and the rare earth metals (e.g. Sc, Y, La, Ce, Pr, Nd), more preferably selected from B, Al, Si, Sb, Ta, P, Zr, Hf, W, Mo and mixtures thereof. Preferably, the inorganic pigments B1 and / or B2, more preferably pigment B2, are selected from SiO 2 When calculated as above, B1 or B2 can contain 0.1 to 20% by weight, preferably 0.5 to 15% by weight, and more preferably 1 to 10% by weight of silicon (Si) relative to the total weight of B1 or B2.

[0082] Preferably, the inorganic pigments B1 and / or B2 may be mixed metal oxosulfides containing 0.01 to 10% by weight, preferably 0.1 to 7% by weight, more preferably 0.5 to 5% by weight, of sulfur (S), calculated as S, relative to the total weight of B1 or B2.

[0083] In a preferred embodiment, the mixed metal oxide or mixed metal oxosulfide B1, respectively, comprises, relative to the total weight of B1, Nb 2 O 520 to 60% by weight, preferably 30 to 50% by weight, of niobium (Nb); SnO 2 30-60% by weight, preferably 40-60% by weight, of tin (Sn), calculated as ZnO; 0.1-20% by weight, preferably 1-10% by weight, of zinc (Zn), calculated as ZnO; and 0-10% by weight, preferably 0.1-5% by weight, of sulfur (S), calculated as S. In particular, the mixed metal oxide or mixed metal oxosulfide B1 contains, relative to the total weight of B1, 0.5% by weight of Nb 2 O 5 Niobium (Nb) is 40 to 50% by weight when calculated as SnO 2 % by weight, calculated as ZnO; 2 to 5% by weight, calculated as ZnO; and 0.5 to 2% by weight, calculated as S.

[0084] In a preferred embodiment, the mixed metal oxide or mixed metal oxosulfide B2, respectively, comprises, relative to the total weight of B2, TiO 2 10 to 60% by weight, preferably 20 to 50% by weight, of titanium (Ti); SnO 2 20 to 70% by weight, preferably 30 to 60% by weight, of tin (Sn) calculated as ZnO; 1 to 30% by weight, preferably 5 to 20% by weight, of zinc (Zn) calculated as ZnO, and SnO 2 In particular, the mixed metal oxide or mixed metal oxosulfide B2 contains 0 to 20% by weight, preferably 0.1 to 10% by weight, of silicon (Si), calculated as 0.1 to 10% by weight of TiO 2 20-30% by weight of titanium (Ti) calculated as SnO 2 45-55% by weight of tin (Sn), calculated as ZnO; 10-20% by weight of zinc (Zn), calculated as ZnO, and SiO 2 It contains 5 to 10 weight % silicon (Si) when calculated as:

[0085] Preferably, at least the inorganic pigment B is present in an amount of 0.00001 to 5.0% by weight, preferably 0.0001 to 4.0% by weight, more preferably 0.001 to 3.0% by weight, also preferably 0.01 to 2.0% by weight, based on the total thermoplastic molding composition. Preferably, the given amount is based on the sum of all inorganic pigments B present in the thermoplastic molding composition according to the invention. The inorganic pigment B can be utilized as a pure colorant or as a colorant composition, for example as a masterbatch, the amounts given above being based on the pure inorganic pigment B compound.

[0086] Preferably, the at least one inorganic pigment B comprises at least one mixed metal oxide or mixed metal oxosulfide B1 comprising the metals niobium (Nb), tin (Sn) and zinc (Zn), the mixed metal oxide or mixed metal oxosulfide B1 having a pyrochlore structure. More preferably, the inorganic pigment B comprises as inorganic pigment B1 a Nb / Sn / Zn oxosulfide having a pyrochlore structure, such as Pigment Yellow 227 (e.g. commercially available as YL0010P150 / Yellow 10P150 from Shepherd Color Company).

[0087] Mixed oxides and oxosulfides with pyrochlore structure, e.g. Sn / Nb pyrochlore Sn 2 Nb 2 O 7 , and Sn 2 Nb 2 O 7 Mixed oxides and oxosulfides with partial substitution at the divalent sites of, for example, Sn / Zn / Nb pyrochlores, and their preparation are described, for example, in WO 2011 / 156362 and WO 2014 / 160218. Typically, such mixed metal oxides and oxosulfides can be prepared by high temperature calcination, typically at temperatures in the range of 800° C. to 1000° C., with oxides and / or other salts, for example sulfides or carbonates, of the respective metals. Typically, a premix of metal salts and / or metal oxides is prepared, followed by calcination, preferably under inert gas.

[0088] Preferably, the at least one inorganic pigment B comprises at least one mixed metal oxide or mixed metal oxosulfide B2 comprising the metals titanium (Ti), tin (Sn) and zinc (Zn), the mixed metal oxide or mixed metal oxosulfide B2 having a rutile structure. More preferably, the inorganic pigment B comprises as inorganic pigment B2 a Ti / Sn / Zn oxide having a rutile structure, for example Pigment Yellow 216 (for example commercially available as OR0010P340 / Orange 10P340 from Shepherd Color Company).

[0089] According to a preferred embodiment, at least one inorganic pigment B1 is selected from pyrochlore Nb / Sn / Zn oxosulfides, preferably Pigment Yellow 227, and B2 is selected from rutile Ti / Sn / Zn oxides, preferably Pigment Yellow 216.

[0090] organic dye C The thermoplastic molding composition according to the invention comprises at least one organic dye C, typically one or more organic dyes C, which are soluble in the polymer matrix A. Preferably, at least the organic dye C is present in an amount of 0.00001 to 5.0% by weight, preferably 0.0001 to 4.0% by weight, more preferably 0.001 to 3.0% by weight, even more preferably 0.01 to 2.0% by weight, based on the total thermoplastic molding composition. Preferably, the given amount is based on the sum of all organic dyes C present in the thermoplastic molding composition according to the invention. The organic dye C can be utilized as a pure colorant or as a colorant composition, for example as a masterbatch, the amounts given above being based on the pure organic dye compound.

[0091] Preferably, the at least one organic soluble dye C is dissolved and monomolecularly dispersed in the polymer matrix A. Also preferably, a composition comprising a polymer matrix A and only a soluble organic dye C (meaning no inorganic pigment B and no other components) in an amount of 0.5% by weight, preferably 1% by weight, relative to the composition, exhibits a haze (measured at 23° C. on a test piece 1 mm thick according to standard ASTM D1003) of less than or equal to 5% (<=5%), preferably less than or equal to 4% (<=4%).

[0092] Typically, the at least one organic dye C can be selected from widely known dyes suitable for coloring thermoplastic polymers, such as polymethyl methacrylate, polycarbonate, polystyrene and polystyrene copolymers, such as styrene-acrylonitrile copolymers. In particular, the at least one organic dye C is selected from yellow, orange, red and brown organic dyes. According to a preferred embodiment, the at least one organic dye C is selected from monoazo dyes, perinone dyes, quinophthalone dyes, anthraquinone dyes and pyrazolone dyes. More preferably, the organic dye C is selected from monoazo dyes, perinone dyes and anthraquinone dyes. In particular, the organic dye C comprises at least one monoazo dye and / or at least one perinone dye.

[0093] Generally, suitable monoazo dyes are well known to those skilled in the art and are derivatives of diazene(diimide) HN=NH, where two hydrogens are replaced by aromatic or heteroaromatic moieties (IUPAC Recommendations 1995, Pure & Appl. Chem., Vol. 67, No. 819, pp. 1307-1375, 1995). In other words, the chemical structure of all monoazo dyes contains one chemical moiety -N=N-.

[0094] The term "heteroaromatic moiety" as used in this application is well known and typically refers to a 5- or 6-membered aromatic moiety that contains at least one heteroatom in its structure. Usually, the heteroatom is an N, O, S, Se or Te atom, more preferably an N, O or S atom, even more preferably an N atom. Specific examples of heteroaromatic moieties include, for example, furan, thiophene, pyran, pyrrole, imidazole, pyrazole, 3H-pyrazol-3-one, pyrazolin-5-one, pyridine, pyrazine, pyrimidine, pyridazine, thiazole, oxazole, isothiazole, isoxazole, thiadiazole, oxadiazole, triazole, selenazole and tellurazole. Further examples of heteroaromatic moieties include, for example, indolizine, purine, pteridine, carboline, pyrroloimidazole, pyrrolotriazole, pyrazoloimidazole, pyrazolotriazole, pyrazolopyrimidine, pyrazolotriazine, triazolopyridine, tetraazaindene, imidazoimidazole, imidazopyridine, imidazopyrazine, imidazopyrimidine, imidazopyridazine, oxazolopyridine, oxazolopyrazine, oxazolopyrimidine, oxazolopyridazine, thiazolopyridine, thiazolopyrazine, thiazolopyrimidine, thiazolopyridazine, pyridinopyrazine, pyrazinopyrazine, pyrazinopyridazine, naphthyridine, imidazotriazine, and 1H-perimidine.

[0095] The heteroaromatic moiety is usually substituted with one or several substituents, which may be alkyl, alkenyl, alkynyl, aryl, amino, alkoxyl, aryloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, -carbamoyl, alkylthio, arylthio, sulfonyl, cyano and heterocyclic groups and halogen atoms. More preferred are alkyl, alkenyl, aryl, alkoxyl, aryloxy, cyano and heterocyclic groups and halogen atoms, even more preferred are alkyl, aryl, alkoxyl, aryloxy and aromatic heterocyclic groups, and particularly preferred are alkyl, aryl, alkoxyl and aromatic heterocyclic groups.

[0096] Specific examples of monoazo dyes that may be used in the present invention include, but are not limited to, the following: Solvent Red 195 (cyano-5-[[5-cyano-2,6-bis[(3-methoxypropyl)amino]-4-methylpyridin-3-yl]azo]-3-methyl-2-thiophenecarboxylic acid methyl ester); Disperse Yellow 241 (5-[(3,4-dichlorophenyl)azo]-1,2-dihydro-6-hydroxy-1,4-dimethyl-2-oxonicotinonitrile); Solvent Yellow 16 (5-methyl-2-phenyl-4-phenylazo-4H-pyrazol-3-one); Solvent Yellow 18 (4-[(2,4-dimethylphenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one); Solvent Yellow 21 (3-[(1-oxonaphthalen-2-ylidene)methylhydrazinylidene]-1-prop-2-enylindol-2-one); Solvent Yellow 72 (4-((o-methoxyphenyl)azo)-3-methyl-1-phenyl-2-pyrazolin-5-one); Solvent Yellow 82, Solvent Yellow 21 (Bis[2-[(4,5-dihydro-3-methyl-5-oxo-1-phenyl-1H-pyrazol-4-yl)azo]benzoato(2-)]chromate); Solvent Yellow 16 (5-methyl-2-phenyl-4-phenylazo-4H-pyrazol-3-one); Solvent Black 3 (2,3-dihydro-2,2-dimethyl-6-((4-(phenylazo)-1-naphthyl)azo)-1H-perimidine).

[0097] Anthraquinone dyes are dyes that have at least one anthraquinone moiety in their structure. Examples of suitable anthraquinone dyes include (CI Color Index) Solvent Yellow 117, 163, 167, 189; Solvent Orange 77, 86; Solvent Red 111, 143, 145, 146, 150, 151, 155, 168, 169, 172, 175, 181, 207, 222, 227, 230, 245, 247; Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; Solvent Blue 14, 18, 35, 36, 45, 58, 59, 59:1, 63, 68, 69, 78, 79, 83, 94, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; Solvent Green 3, 28, 29, 32, 33; Acid Red 80; Acid Green 25, 27, 28, 41; Acid Violet 34; Acid Blue 25, 27, 40, 45, 78, 80, 112; Disperse Yellow 51; Disperse Violet 26, 27; Disperse Blue 1, 14, 56, 60; Direct Blue 40; Modern Red 3, 11; and Modern Blue 8.

[0098] Examples of perinone dyes suitable for use in the present invention include (Colour Index CI) Solvent Orange 60, 78, 90; Solvent Red 135, 162, 179; Solvent Violet 29, and the like.

[0099] Suitable quinophthalone dyes include (Colour Index CI) Solvent Yellow 33, 114, 128, 129, Disperse Yellow 14, 49, 54, and the like.

[0100] Suitable pyrazolone dyes include, for example, Solvent Yellow 93 (4-(4,5-dihydro-1-phenyl-3-methyl-5-oxo-1H-pyrazol-4-ylidenemethyl)-1-phenyl-3-methyl-1H-pyrazol-5(4H)-one). In many cases, the pyrazolone dye contains a monoazo group as defined above, which can be cited as a preferred example of a monoazo dye.

[0101] In a preferred embodiment, the at least one organic dye C is selected from: Solvent Yellow 16 (5-methyl-2-phenyl-4-phenylazo-4H-pyrazol-3-one); Solvent Yellow 18 (4-[(2,4-dimethylphenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-one); Solvent Yellow 21 (3-[(1-oxonaphthalen-2-ylidene)methylhydrazinylidene]-1-prop-2-enylindol-2-one); Solvent Yellow 72 (4-((o-methoxyphenyl)azo)-3-methyl-1-phenyl-2-pyrazolin-5-one); Solvent Yellow 82, Solvent Yellow 16 (5-methyl-2-phenyl-4-phenylazo-4H-pyrazol-3-one); Solvent Yellow 93 (4-(4,5-dihydro-1-phenyl-3-methyl-5-oxo-1H-pyrazol-4-ylidenemethyl)-1-phenyl-3-methyl-1H-pyrazol-5(4H)-one); Solvent Yellow 114 (2-(3-hydroxyquinolin-2-yl)indan-1,3-dione); Solvent Yellow 163 (1,8-Bis(phenylthio)anthraquinone); Disperse Yellow 241 (5-[(3,4-dichlorophenyl)azo]-1,2-dihydro-6-hydroxy-1,4-dimethyl-2-oxonicotinonitrile); Solvent Orange 60 (12H-phthaloperin-12-one); Solvent Orange 116 (4-methyl-2,6-bis-p-tolylamino-5-(2-trifluoromethylphenylazo)nicotinonitrile); Solvent Red 195 (cyano-5-[[5-cyano-2,6-bis[(3-methoxypropyl)amino]-4-methylpyridin-3-yl]azo]-3-methyl-2-thiophenecarboxylic acid methyl ester); Solvent Red 52 (3-methyl-6-[(4-methylphenyl)amino]-3H-naphtho[1,2,3-de]quinoline-2,7-dione); and Solvent Red 135 (8,9,10,11-tetrachloro-12H-phthaloperin-12-one); Solvent Green 28 (1,4-bis-(4-butylphenylamino)-5,8-dihydroxyanthraquinone); Solvent Green 3 (1,4-bis(p-tolylamino)anthraquinone); Solvent Blue 104 (1,4-bis(mesitylamino)anthraquinone); Solvent Violet 59 (1,4-diamino-2,3-diphenoxyanthraquinone); Solvent Violet 13 (1-hydroxy-4-(4-methylanilino)anthracene-9,10-dione); Solvent Black 3 (2,3-dihydro-2,2-dimethyl-6-((4-(phenylazo)-1-naphthyl)azo)-1H-perimidine).

[0102] In particular, the organic dye C comprises at least one organic dye selected from yellow, orange, red and brown organic dyes, preferably as described above, and optionally at least one organic dye selected from green, blue, purple and black organic dyes, preferably as described above, as a light-shielding component. Typically, the light-shielding component selected from green, blue, purple and black organic dyes can be present in an amount of up to 10% by weight, preferably 0.01-10% by weight, based on the total organic dye C (i.e. based on the total amount of pure organic dyes). In particular, the organic dye C comprises at least 80% by weight, more preferably at least 90% by weight, even more preferably 90-100% by weight, based on the total organic dye C (i.e. based on the total amount of pure organic dyes), of an organic dye selected from yellow, orange, red and brown organic dyes, preferably selected from yellow, orange and red organic dyes, typically as described above.

[0103] More preferably, the at least one organic dye C is one of the following: Solvent Yellow 93 (4-(4,5-dihydro-1-phenyl-3-methyl-5-oxo-1H-pyrazol-4-ylidenemethyl)-1-phenyl-3-methyl-1H-pyrazol-5(4H)-one); Solvent Orange 60 (12H-phthaloperin-12-one); Solvent Orange 116 (4-methyl-2,6-bis-p-tolylamino-5-(2-trifluoromethylphenylazo)nicotinonitrile); Solvent Red 195 (cyano-5-[[5-cyano-2,6-bis[(3-methoxypropyl)amino]-4-methylpyridin-3-yl]azo]-3-methyl-2-thiophenecarboxylic acid methyl ester); Solvent Red 52 (3-methyl-6-[(4-methylphenyl)amino]-3H-naphtho[1,2,3-de]quinoline-2,7-dione); and Solvent Red 135 (8,9,10,11-tetrachloro-12H-phthaloperin-12-one) is selected from.

[0104] According to one preferred embodiment, the at least one organic dye C comprises (preferably consists of) Solvent Red 195 and / or Solvent Red 135, preferably the thermoplastic molding composition exhibits a red color impression.

[0105] According to another preferred embodiment, the at least one organic dye C comprises (preferably consists of) Solvent Orange 60, preferably the thermoplastic molding composition exhibits an orange color impression.

[0106] Additional ingredient D The thermoplastic molding composition according to the invention can also comprise one or more optional additional components D, such as organic pigments, inorganic pigments different from B, scattering particles, impact modifiers, and other commonly known additives and auxiliaries. For example, commonly known additives and auxiliaries can be selected from antistatic agents, antioxidants, mold release agents, flame retardants, lubricants, flow improvers, fillers, UV absorbers, light stabilizers and organic phosphorus compounds, such as phosphites or phosphonates, pigments, agents imparting weather resistance and plasticizers. The choice and amount of additives can be adjusted depending on the intended use.

[0107] In a preferred embodiment, the thermoplastic molding composition according to the invention comprises at least one further additive D selected from pigments, in particular organic pigments and / or inorganic pigments different from B, scattering particles, impact modifiers, antistatic agents, antioxidants, mold release agents, flame retardants, lubricants, flow improvers, fillers, UV absorbers, light stabilizers and organic phosphorus compounds, such as phosphites or phosphonates, agents imparting weather resistance and plasticizers.

[0108] Typically, the optional additional component D is present in an amount of 0.00001 to 50.0% by weight, preferably 0.00001 to 40.0% by weight, also preferably 0.00001 to 30.0% by weight, also preferably 0.0001 to 20% by weight, also preferably 0.001 to 10% by weight, based on the total thermoplastic molding composition. Overall, the choice and amount of additives can be adjusted depending on the intended use. These additives should not excessively impair the colorimetric value and weathering stability of the resulting colored molding composition.

[0109] For example, the thermoplastic molding composition according to the invention may optionally comprise, as additional component D, one or more colorants different from B and C. For example, such additional colorants may be selected from organic and / or inorganic pigments different from B. Examples of suitable pigments to be used as optional additional component D include barium sulfate, zinc oxide, iron oxide (e.g. pigments of the Bayferrox® type from Lanxess), magnesium titanate, calcium sulfate, calcium carbonate, magnesium carbonate, titanium dioxide, carbon black, ultramarine blue, and also the entire class of organic pigments. Typically, suitable organic pigments may be selected from phthalocyanines (e.g. Cu phthalocyanine), benzimidazolone pigments, such as Pigment Yellow 151; isoindoline derivatives, such as Pigment Yellow 139; diazo pigments, such as Pigment Red 242; Pigment Red 242; and anthraquinone pigments, such as Pigment Yellow 147 (1-({4-[(9,10-dioxo-9,10-dihydroanthracen-1-yl)amino]-6-phenyl-1,3,5-triazin-2-yl}amino)-9,10-dihydroanthracene-9,10-dione).

[0110] The phthalocyanine (or called phthalocyanine pigment) used in the present invention is not particularly limited and can be selected from metal-free phthalocyanine, cobalt phthalocyanine, copper phthalocyanine, nickel phthalocyanine, iron phthalocyanine, manganese phthalocyanine and zinc phthalocyanine, more preferably copper phthalocyanine. In particular, suitable copper phthalocyanine pigments can be selected from Pigment Blue 1, 2, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17:1, 56, 60 and 63, and Pigment Green 7 and 36.

[0111] Preferably, the pigments used as optional additional component D may be selected from barium sulfate, metal oxides, preferably zinc oxide, iron oxide and / or titanium dioxide; phthalocyanines (e.g. Cu phthalocyanine) and Pigment Yellow 147.

[0112] According to one preferred embodiment, the thermoplastic molding composition according to the invention does not contain carbon black and / or white inorganic pigments, such as titanium dioxide.

[0113] scattering particles In some embodiments of the invention, the thermoplastic molding composition may further comprise organic and / or inorganic scattering particles as a further component D, said scattering particles being typically dispersed in the polymer matrix A. The choice of scattering particles is not particularly limited, but is typically selected such that the refractive index of the scattering particles differs from that of the polymer matrix by at least 0.01. The refractive index can be measured at 23 ° C with NaD radiation at 589 nm, as specified in standard ISO 489 (1999). Typically, the scattering particles can be present in an amount of 0.1 to 25% by weight relative to the total thermoplastic molding composition.

[0114] The scattering particles usually have a weight average particle size of 0.01 μm to 100.0 μm. The so-called volume average d 50The weight-average particle size, indicated as a value (50 volume percent of the particles have a particle size below the specified average particle size), can be determined by methods known to those skilled in the art, for example by photon correlation spectroscopy in accordance with standard ISO 13320-1 (2009) using commercially available equipment such as the LS 13 320 Laser Diffraction Particle Size Analyzer from Beckman Coulter Inc. Typically, the size of the scattering particles is determined in the form of a dry powder by laser light scattering (room temperature, 23°C) using a Beckman Coulter LS 13 320 laser diffraction particle size analyzer, a Tornado dry powder system, respectively. The measurements are carried out in the manner described in the manual. For computer-assisted analysis, the Mie model is used.

[0115] In a preferred embodiment, the scattering particles are dispersed in a polymer matrix A, the scattering particles have a weight average particle size of 0.01 μm to 100.0 μm, and the refractive index of the scattering particles differs from the refractive index of the polymer matrix by at least 0.01.

[0116] The inorganic scattering particles can include conventional inorganic opacifying agents such as barium sulfate, calcium carbonate, titanium dioxide, or zinc oxide.

[0117] The organic scattering particles are typically spherical scattering beads made of cross-linked polymeric materials such as polyalkyl(meth)acrylates, silicones, polystyrene, etc. In the present invention, the term "spherical" means that the scattering beads preferably have a spherical shape, but it is clear to the skilled artisan that scattering beads with other shapes may exist as a result of the manufacturing method, and the shape of the scattering beads may also deviate from the ideal spherical shape. The term "spherical" therefore indicates that the ratio of the maximum dimension to the minimum dimension of the scattering beads is equal to or less than 4, preferably equal to or less than 2, each of these dimensions being measured through the center of gravity of the scattering beads. Based on the number of scattering beads, preferably at least 70%, in particular at least 90%, are spherical.

[0118] Preferred scattering beads composed of cross-linked polystyrene are commercially available from Sekisui Plastics Co., Ltd. under the trademarks Techpolymer® SBX-4, Techpolymer® SBX-6, Techpolymer® SBX-8 and Techpolymer® SBX-12.

[0119] Other particularly preferred spherical plastic particles for use as scattering agents include crosslinked silicones. Silicone scattering agents particularly preferred for use in the present invention are available as TOSPEARL® 120 and TOSPEARL® 3120 from Momentive Performance Materials Inc.

[0120] Impact Modifier The mechanical properties of the thermoplastic molding composition according to the invention can be additionally adjusted to the desired objectives if the thermoplastic molding composition comprises one or more impact modifiers as further component D. Typically, the impact modifiers can be present in an amount of 5.0 to 50.0% by weight, preferably 10.0 to 40.0% by weight, based on the total thermoplastic molding composition.

[0121] The impact modifiers used in the present invention are well known and can have different chemical compositions and different polymer structures. The impact modifiers can be crosslinked or thermoplastic. Furthermore, the impact modifiers can be granular as core-shell or core-shell-shell particles. Typically, the granular impact modifiers have an average particle size in the range of 20 nm to 500 nm, preferably 50 nm to 450 nm, more preferably 100 nm to 400 nm, most preferably 150 nm to 400 nm. "Granular impact modifier" in this context generally means crosslinked impact modifiers having a core, core-shell, core-shell-shell or core-shell-shell-shell structure. The average particle size of the granular impact modifiers can be determined by methods known to the skilled person, for example by photon correlation spectroscopy according to the standard DIN ISO 13321:1996.

[0122] Further preferred impact modifiers are polymer particles which may have a core-shell or core-shell-shell structure and are obtained by emulsion polymerization (see, for example, EP-A-0113924, EP-A-0522351, EP-A-0465049 and EP-A-0683028). The present invention requires a suitable average particle size of these core-shell or core-shell-shell polymer particles, typically in the range of 20nm to 500nm, preferably 50nm to 450nm, more preferably 150nm to 400nm, and most preferably 200nm to 400nm.

[0123] Typically, suitable core-shell type particles comprise a soft elastomeric core, for example based on crosslinked butyl acrylate, and a hard shell, typically based on the same or similar monomer as the matrix, for example based on methyl methacrylate and optionally suitable comonomers, for example methyl acrylate and / or ethyl acrylate. A three-layer or three-phase structure with a core and two shells can be produced as follows: the innermost (hard) shell can be composed of, for example, methyl methacrylate, a small proportion of a comonomer, for example ethyl acrylate, and a proportion of a crosslinker, for example allyl methacrylate. The middle (soft) elastomeric shell can be composed of, for example, a copolymer containing butyl acrylate and, optionally, styrene, while the outermost (hard) shell is the same as the matrix polymer, thus providing compatibility and good connectivity with the matrix. The proportion of polybutyl acrylate in the elastomeric phase of the impact modifier, for example the soft core of a two-layer core-shell structure or the intermediate elastomeric shell of a three-layer core-shell structure, determines the impact modifying effect and is preferably in the range of 20.0% to 99.0% by weight, particularly preferably in the range of 30.0% to 98.0% by weight, and even more preferably in the range of 40.0% to 97.0% by weight, based on the total weight of the elastomeric phase.

[0124] Thermoplastic impact modifiers have a different mechanism of action than granular impact modifiers. They are generally mixed with a matrix material. If domains are formed, as occurs for example when using block copolymers, the preferred size of these domains (which can be determined for example by microscopy) corresponds to the preferred size of the core-shell particles.

[0125] There are various types of thermoplastic impact modifiers. One example is aliphatic thermoplastic polyurethanes (TPUs), such as the Desmopan® products available from Covestro AG. For example, the TPUs Desmopan® WDP 85784A, WDP 85092A, WDP 89085A and WDP 89051D are particularly suitable as impact modifiers, all of which have a refractive index of 1.490 to 1.500.

[0126] A further class of thermoplastic impact modifiers are methacrylate-acrylate block copolymers, in particular acrylic TPEs, including PMMA-poly-n-butylacrylate-PMMA triblock copolymers, commercially available, for example, from Kuraray under the product name Kurarity®. The poly-n-butylacrylate blocks form nanodomains in the polymer matrix having a size of 10 nm to 20 nm.

[0127] Coloring composition and method for producing same In another aspect, the present invention provides a method for producing a composition comprising the steps of: at least one inorganic pigment B as defined above, selected from mixed metal oxides or mixed metal oxosulfides B1 comprising the metals niobium (Nb), tin (Sn) and zinc (Zn); and / or mixed metal oxides or mixed metal oxosulfides B2 comprising the metals titanium (Ti), tin (Sn) and zinc (Zn); at least one organic dye C as defined above, preferably chosen from monoazo dyes, perinone dyes, quinophthalone dyes and anthraquinone dyes; and A dispersion medium, typically a solid dispersion medium, or a liquid dispersion medium, comprising at least one thermoplastic polymer, in particular the thermoplastic polymers mentioned above. The present invention is directed to a colorant composition, preferably a masterbatch or liquid colorant composition, comprising:

[0128] The definitions and embodiments mentioned above in relation to the thermoplastic molding composition according to the invention apply analogously. In particular, the description of components A, B, C and optional component D also applies analogously to the coloring composition according to the invention.

[0129] Masterbatch is understood to mean a solid or waxy formulation comprising the coloring components B and C and a solid dispersion medium. Typically, the solid dispersion medium can be selected from, for example, the thermoplastic polymers mentioned above and waxes, such as the widely known natural and synthetic waxes. The concentration of the coloring components B and C in the masterbatch is adjusted so that the desired color impression is produced when the masterbatch is used to prepare the colored thermoplastic molding composition according to the invention. For example, the masterbatch can be a polymer granulate or a polymer powder.

[0130] Liquid coloring composition is understood to mean a coloring composition that comprises a liquid dispersion medium. For example, the liquid coloring medium can be a solution, a dispersion, a gel or a pasty composition. Preferably, the liquid coloring composition is a dispersion of coloring components B and C in an aqueous dispersion medium that comprises at least one dispersant. The concentration of coloring components B and C in the liquid coloring composition is adjusted so that the desired color impression occurs when the liquid coloring composition is used to produce a colored thermoplastic molding composition according to the invention.

[0131] In one preferred embodiment, the colorant composition according to the present invention is a masterbatch, which comprises, respectively for the entire masterbatch: 0.01 to 40.0% by weight, preferably 5.0 to 30.0% by weight, of at least one inorganic pigment B as defined above; 0.01 to 40.0% by weight, preferably 5.0 to 30.0% by weight, of at least one organic dye C as defined above; 30.0 to 99.98% by weight, preferably 50.0 to 90.0% by weight, of a solid dispersion medium comprising (preferably consisting essentially of) at least one thermoplastic polymer and / or at least one wax; and 0.0 to 10.0% by weight, preferably 0.0 to 5.0% by weight, of one or more auxiliary additives Includes.

[0132] Preferably, the solid dispersion medium is selected from the above-mentioned thermoplastic polymers and widely known natural or synthetic waxes. The choice of the thermoplastic polymer in the masterbatch is not particularly limited, as long as the thermoplastic polymer is suitable for pigmentation and thermoplastic processing, especially injection molding and extrusion molding. Preferably, the thermoplastic polymer in the masterbatch is substantially the same as the thermoplastic molding composition according to the present invention described above. For example, the thermoplastic polymer can be advantageously selected from the group consisting of polyalkyl (meth)acrylate, polymethyl (meth)acrylimide, polyalkyl (meth)acrylate copolymer, polystyrene, polystyrene copolymer, acrylonitrile copolymer, polycarbonate, polyester (preferably polyethylene terephthalate), polyamide, polyvinylidene fluoride or mixtures thereof.

[0133] The wax selection in the masterbatch is not particularly limited, so long as the natural wax or synthetic wax is suitable for coloring and thermoplastic processing, especially injection molding and extrusion molding.For example, natural wax includes waxes of animal, vegetable and mineral origin and chemically modified natural waxes, animal waxes include beeswax, lanolin, lanocerin and shellac wax, vegetable waxes include soybean, carnauba, candelilla, jojoba and oleander wax, mineral waxes include petrolatum wax and earth wax or fossil wax, such as paraffin, petrolatum and montan wax.For example, synthetic wax is man-made wax and can be derived from sources such as hydrocarbon, alcohol, glycol, amine, amide or ester. Synthetic waxes include, for example, polyolefin waxes, polytetrafluoroethylene, Fischer-Tropsch wax, synthetic triglycerides, salts of fatty acids (e.g., calcium montanate), solid fatty acid esters (e.g., esters of ethylene glycol, butylene glycol, or sorbitol with C16 to C32 fatty acids, such as palmitic acid, stearic acid, or montanic acid), wax esters (e.g., esters of fatty acids and fatty alcohols, such as stearyl stearate), fatty acid amines, fatty amides, polyamide waxes, as well as chlorinated waxes and other chemically modified waxes.

[0134] The optional auxiliary additives can be selected from the additives and auxiliaries described as additional component D above. For example, the auxiliary additives can be selected from antistatic agents, antioxidants, mold release agents, lubricants, flow improvers, fillers, UV absorbers, light stabilizers and organic phosphorus compounds, such as phosphites or phosphonates. The selection and amount of additives can be adjusted according to the intended use. In addition to the coloring components B and C, the masterbatch can also contain one or more additional colorants, such as organic or inorganic pigments different from the above-mentioned B.

[0135] In another preferred embodiment, the coloring composition according to the present invention is a liquid coloring composition, which comprises, respectively, the following with respect to the total liquid coloring composition: 0.5 to 50.0% by weight, preferably 5.0 to 40.0% by weight, of at least one inorganic pigment B as defined above; 0.5 to 50.0% by weight, preferably 5.0 to 40.0% by weight, of at least one organic dye C as defined above; 1.0-30.0 wt. %, preferably 5.0-25.0 wt. %, of at least one dispersant; 48.0 to 98.0% by weight, preferably 48.0 to 85.0% by weight, of a liquid dispersion medium, such as demineralized water and / or an organic solvent; and 0.0 to 50.0% by weight, preferably 0.0 to 10.0% by weight, more preferably 0.0 to 5.0% by weight of one or more auxiliary additives Includes.

[0136] Typically, the amount of liquid dispersion medium is adjusted so that the sum of the parts by weight of each component of the liquid coloring composition is 100% by weight.

[0137] Typically, the liquid dispersion medium can be selected from water or a mixture of water and one or more polar organic solvents that are miscible with water, such as alcohols, esters, ketones, amides, sulfoxides, and mixtures thereof.Furthermore, the liquid dispersion medium can be selected from organic solvents.Examples of organic solvents include widely known organic solvents, such as acetone, methyl ethyl ketone, methyl-n-butyl ketone, methyl isobutyl ketone, ethyl isobutyl ketone, tetrahydrofuran, dioxane, dimethylformamide, diethylformamide, dimethylacetamide, diethylacetamide, N-methylpyrrolidone, methanol, ethanol, isopropanol, ethylene glycol, propylene glycol, 2-methoxy-2-propanol, and tetraglyme, or mixtures thereof.

[0138] The choice of dispersant is not particularly limited, as long as the additive does not adversely affect the properties of the resulting colored molding composition. The use of pH-independent dispersants is preferred. For example, the dispersant can be selected from widely known surfactants and / or protective colloids. Suitable surfactants include anionic surfactants, cationic surfactants, nonionic surfactants and compatible mixtures thereof. Examples of suitable conventional anionic surfactants are the alkali metal and ammonium salts of alkylsulfuric acid sulfates, typically having C8 to C12 alkyl groups (e.g., sodium lauryl sulfate), the alkali metal and ammonium salts of sulfuric acid hemiesters of ethoxylated alkanols, typically having C12 to C18 alkyl groups (e.g., sodium lauryl ether sulfate), and the alkali metal and ammonium salts of ethoxylated alkylphenols, typically having C4 to C12 alkyl groups, and the alkali metal and ammonium salts of alkylsulfonic acids, typically having C12 to C18 alkyl groups. Examples of conventional nonionic emulsifiers are oxylated mono-, di- and trialkylphenols, and also ethoxylated fatty alcohols. Examples of cationic emulsifiers are especially phosphonium salts, sulfonium salts, tropylium salts, morpholinium salts, oxazolinium salts, imidazolinium salts, pyridinium salts, and primary, secondary, tertiary or quaternary ammonium salts, typically with C8-C18 alkyl, alkylaryl or heterocyclic groups.

[0139] For example, the dispersant may be a high molecular weight copolymer containing at least maleic anhydride, styrene and aminopolyether as monomer units. Alternatively, the dispersant may be a copolymer of methacrylic acid and a hydrophobic methacrylate. The term "hydrophobic methacrylate" as used herein refers to an ester of methacrylic acid and an alcohol having preferably at least 3 and not more than 24 carbon atoms. Furthermore, the dispersant may be a copolymer of polyether, preferably ethylene oxide, propylene oxide and / or butylene oxide and styrene oxide.

[0140] Suitable dispersants include, for example, polyacrylate Dispex® Ultra 4550 (formerly EFKA® 4550) available from BASF SE. This polymer essentially consists of the monomers α-methylstyrene, 2-ethylhexyl acrylate and MPEG methacrylate (methoxypoly(ethylene glycol) monomethacrylate). Further examples of suitable dispersants include TEGO® Dispers 750W and 755W available from Evonik Industries AG, and Disperbyk® 190 available from BYK-Chemie GmbH.

[0141] The liquid coloring composition can contain one or more auxiliary additives in addition to the dispersing agent.For example, the auxiliary additives can be selected from agents for preventing decay or bacterial decomposition, bactericides, leveling agents, thickening agents and defoaming agents.In addition to the coloring components B and C, the liquid coloring composition can also contain one or more additional colorants, such as organic or inorganic pigments different from the above-mentioned B.

[0142] In a preferred embodiment, the liquid coloring composition can contain one or more thickeners.Preferred thickeners include cellulose, especially ethylcellulose.As a further possibility, carboxylate-containing polymers, such as homo- and copolymers based on vinyl acetate and crotonic acid, or partially hydrolyzed poly(meth)acrylates, available as water-soluble or alkali-soluble solid products, as colloidal solutions, or as aqueous dispersions, can be used as thickeners.Particularly preferred are the sodium salt forms of homo- and copolymers of acrylic acid and / or methacrylic acid.

[0143] Furthermore, the present invention is directed to a method for producing a colorant composition according to the present invention, comprising the step of mixing at least one inorganic pigment B, at least an organic dye C, a dispersion medium and, optionally, further components.

[0144] In particular, the present invention relates to a method for the preparation of a masterbatch according to the invention, in which inorganic pigment B and organic dye C, and optionally additional components, are added to a molten dispersion medium comprising (preferably essentially consisting of) at least one thermoplastic polymer. Typically, said steps can be carried out by conventional coalescence, mixing and homogenization steps, such as extrusion, kneading or grinding. Further details of such steps are given below in connection with the method for the preparation of a thermoplastic molding composition according to the invention. Typically, the inventive masterbatch is obtained in the form of polymer granules or polymer powder.

[0145] In particular, the present invention relates to a method for the preparation of a liquid coloring composition according to the present invention, in which an inorganic pigment B and an organic dye C, and optionally additional ingredients, are added to a liquid phase comprising a liquid dispersion medium and a dispersant, which mixture is typically homogenized by intensive stirring or other conventional homogenization processes such as kneading or grinding. Typically, the liquid coloring composition according to the present invention is obtained in the form of a solution, dispersion, gel, or pasty composition.

[0146] Process for the preparation of the thermoplastic molding composition according to the invention The present invention is also directed to a method for producing the above-mentioned thermoplastic molding composition, which method comprises the steps of: i. providing a polymer matrix A as defined above, said polymer matrix A preferably comprising at least one thermoplastic polymer, said thermoplastic polymer being selected from polyalkyl(meth)acrylates (e.g. polymethylmethacrylate PMMA), poly(meth)acrylimides (e.g. polymethylmethacrylimides PMMI), polyalkyl(meth)acrylate copolymers, polystyrene, polystyrene copolymers, acrylonitrile copolymers, polycarbonates (preferably aromatic polycarbonates derived from bisphenols or polycarbonates derived from isosorbide), polyesters (preferably aromatic polyesters, more preferably polyethylene terephthalate), polyamides, polyvinylidene fluoride (PVDF) and polyolefins (e.g. cycloolefin copolymers COC or clarified polypropylene), more preferably polyalkyl(meth)acrylates (e.g. polymethyl(meth)acrylate), polycarbonates (e.g. polycarbonates derived from bisphenols or isosorbide) and styrene-acrylonitrile copolymers (SAN); and ii. adding to the polymer matrix A obtained in step i) at least one inorganic pigment B as defined above and at least one organic dye C as defined above; Includes.

[0147] The definitions and embodiments given above, for example the description of components A, B, C and optional component D, apply analogously to the process for producing the thermoplastic molding composition according to the invention.

[0148] In one embodiment, in step ii) a single coloring composition is added to the polymer matrix, said coloring composition comprising inorganic pigment B and organic dye C. In particular, the coloring composition is a masterbatch or liquid coloring composition as described above. In yet another embodiment, in step ii) two or more coloring compositions can be added, where one coloring composition comprises inorganic pigment B and another coloring composition comprises organic dye C. When two or more coloring compositions are added in step ii), they can be added in any order or even simultaneously.

[0149] The thermoplastic molding composition can also be prepared by adding at least one inorganic pigment B as defined above and at least one organic dye C as defined above directly to the thermoplastic matrix A. In many cases, the coloring components B and C can be used as received from the manufacturer.

[0150] Preferably, in step ii) inorganic pigment B and organic dye C are added to the molten polymer matrix A. Preferably, step ii) is carried out at a temperature in the range of 150°C to 350°C, preferably 200°C to 320°C, more preferably 230°C to 300°C. Preferably, step ii) is carried out in an extruder at a temperature in the range of 150°C to 350°C, preferably 200°C to 320°C, more preferably 230°C to 300°C. If the thermoplastic polymer is a polyalkyl(meth)acrylate (e.g. PMMA) and / or a polyalkyl(meth)acrylate copolymer, step ii) is typically carried out in an extruder at a temperature in the range of preferably 200°C to 320°C, more preferably 230°C to 300°C.

[0151] More preferably, the process for producing a thermoplastic molding composition according to the invention comprises mixing the polymer matrix A in molten form with the inorganic pigment B, the organic dye C and optionally additional component D. Typically, such a process is carried out in the melt under the action of shear forces. In particular, said step can be carried out by conventional incorporation processes by combination, mixing and homogenization, in particular through extrusion, kneading or grinding. Optionally, the combination and mixing of components B, C and optionally component D before melt homogenization is carried out using a powder premix.

[0152] More preferably, the polymer matrix A and the masterbatch, the liquid colorant composition or the neat components B, C and optionally D can be combined, mixed and homogenized (e.g. extrusion) in conventional equipment such as screw-type extruders (e.g. twin-screw extruders, ZSK), kneaders, Brabender or Banbury mills. After extrusion, the extrudate is usually cooled and pelletized. It is also possible to premix the individual components and then add the remaining components separately and / or as a mixture as well.

[0153] In yet another embodiment, the polymer matrix is ​​provided in the form of a melt, to which the colorant composition according to the invention, for example a liquid composition or masterbatch, is added, preferably after mixing and homogenization. It is also possible to prepare a dry mixture of the polymer matrix A, the inorganic pigment B and the organic dye C, and then melt this mixture. It is also possible to add the colorant composition according to the invention to the thermoplastic polymer immediately after the manufacturing process of the thermoplastic polymer.

[0154] Molded article and method of making same The present invention further relates to a molded article produced (or consisting of) the thermoplastic molding composition according to the invention described above, preferably the molded article is an extruded or molded article, in particular an injection molded article. In another aspect, the present invention relates to a method for producing said molded article from the thermoplastic molding composition according to the invention, for example by injection molding, extrusion, blow molding, press molding, calendar molding, vacuum molding or a combination thereof.

[0155] For example, the definitions and embodiments described above in relation to the thermoplastic molding composition according to the invention and the coloring composition according to the invention apply analogously. In particular, the description of components A, B, C and optional component D applies analogously to the molded article and the method for producing it.

[0156] Preferably, the molded article, especially the injection molded article, has a complex geometric shape, in particular the molded article has different wall thicknesses, one or more perforations, at least one non-planar surface, or a combination of these features.

[0157] In one embodiment, complex molded articles, particularly injection molded articles, exhibit different wall thicknesses that vary within the molded article, typically varying within the range of 1 mm to 30 mm. By way of example, the wall thickness variation can be expressed by the difference between the minimum and maximum wall thicknesses of the molded article, which difference is greater than 1 mm, preferably greater than 5 mm, particularly preferably greater than 10 mm. The ratio of maximum to minimum wall thickness is preferably in the range of greater than 1:20, more preferably greater than 1:10, particularly preferably greater than 1:4, most preferably greater than 1:2.

[0158] In another embodiment, complex molded articles, particularly injection molded articles, may exhibit at least one perforation, with zero wall thickness at the site of the perforation and the area surrounding the perforation exhibiting uniform or varying wall thickness, typically within the ranges described above.

[0159] In another embodiment, the complex molded article, in particular the injection molded article, exhibits at least one non-planar surface, which is preferably of convex or concave design.

[0160] Furthermore, the invention provides a method for producing a molded article from the thermoplastic molding composition according to the invention, in particular by a thermoforming process or a melt process, in particular by extrusion or injection molding. Typically, said method applies a temperature in the range of 150 to 350° C. Typically, the temperature applied depends on the thermal properties of the polymer matrix A and of the thermoplastic polymer used.

[0161] For example, the present invention is directed to a method for the manufacture of an injection-molded article, comprising the step of injection-molding the thermoplastic molding composition according to the present invention described above, in which the thermoplastic molding composition is injected into a mold capable of producing the molded article. Typically, melt temperatures in the range of 150°C to 350°C, preferably 200°C to 320°C, more preferably 230°C to 300°C are applied. Typically, mold temperatures in the range of 50°C to 100°C, preferably 60°C to 90°C are applied.

[0162] Typically, the temperature of the molten thermoplastic molding composition comprising a polyalkyl(meth)acrylate, such as polymethyl methacrylate (co)polymer, is preferably maintained at 210-270°C, more preferably 240-250°C, during the injection molding process according to the invention. The temperature of the injection molding nozzle is more preferably 230-270°C, even more preferably 240-250°C, and the temperature of the injection molding mold is preferably 40-80°C, more preferably 50-60°C. The temperature of the injection molding cylinder is preferably 220-260°C, more preferably 230-250°C. Typically, the thermoplastic molding composition is injected into the mold at a pressure in the range of 50-1000 bar. Here, in certain embodiments, the pressure is applied in stages, the pressure being 50 bar in the first stage and 400 bar in the second stage. The injection speed may also be stepped, with a first step in the range of 0.01 m / s to 0.1 m / s, a second step in the range of 0.1 m / s to 1 m / s, and a possible third step in the range of 0.05 m / s to 0.5 m / s. The metering stroke here is preferably 1 to 4 times the screw diameter.

[0163] The method according to the invention is very suitable for the production of the above mentioned complex moulded articles. The difference in thickness of the corresponding injection mould, especially the perforations, i.e. the areas around which the melt is injected into the mould, has a significant effect on the rheology of the material as it fills the mould cavity. In the context of the invention, a complex moulded article is a moulded article having one or more of the above mentioned characteristics.

[0164] A further aspect of the invention relates to a method for producing an extrusion molded article, which method comprises the step of extruding the thermoplastic molding composition according to the invention at a temperature in the range of from 200° C. to 320° C., preferably from 230° C. to 300° C., in which the thermoplastic molding composition is melted and die cast to obtain the final article.

[0165] The extrusion of thermoplastic polymers is widely known and is described, for example, in Kunststoffextrusionstechnik II [Plastics extrusion technology II], Hanser Verlag, 1986, p. 125 ff.

[0166] In a preferred embodiment, the melt of the thermoplastic molding composition is extruded from the nozzle of the extruder into the gap between two calender rolls. The optimum temperature of the melt depends, for example, on the composition of the mixture and can therefore vary within a wide range. For example, if the thermoplastic polymer is a polyalkyl(meth)acrylate and / or a polyalkyl(meth)acrylate copolymer, the preferred temperature at the nozzle inlet is in the range of 150-300 ° C, particularly preferably in the range of 180-270 ° C, more particularly preferably in the range of 200-220 ° C. The temperature of the calender rolls is preferably below 150 ° C, preferably from 60 ° C to 140 ° C.

[0167] The invention will now be described in more detail by the following non-limiting examples.

[0168] Working Example Test Method Colorimetric measurements were performed using a HunterLab spectrophotometer UltraScan® Pro. Color differences in the Xenotest weathering tester were measured using a Varian Cary 5000 spectrophotometer.

[0169] Standard color values ​​(X, Y, Z), color coordinates (L * , a * and b * ), as well as the derived color value C, denoted as C below. * ab (saturation), hereafter denoted as h ab (hue) and below L * It is written as L * ab (Luminance) was determined using standard illuminant D65 / 10° in accordance with standard DIN 5033 (2017), Part 1-4.

[0170] All colorimetric measurements were performed using three test panels of 3 mm thickness and standard illumination D65 / 10°, diffuse: 8° geometry. Colorimetric values ​​C, h, L * , a and b were measured in reflection with a diffuse:8° (di:8°) geometry according to DIN 5033-7 (2017). The transmittance Y (D65 / 10°) was measured with diffuse illumination and direct light geometry as well as the same geometry as in reflection according to standard DIN 5033 (2017), Part 1-4 and 7.

[0171] The weathering test apparatus Xenotest was carried out with the following parameters: Device: Xenotest Beta LM / 1 Filters: Xenochrome 300 filter system, daylight (ISO 4892-2) ·Irradiance: 60W / m 2 (300~400nm) Temperature: Chamber 38±3℃, Black standard 65±3℃ ·Humidity: 65±10%RH Drying 102 minutes, water spray 18 minutes.

[0172] Color difference of each sample ΔE CIELAB 1976(D 65 , 10°) was determined by reflectance measurement after 3000 hours in accordance with standard DIN 6174.

[0173] In all cases, test specimens with a ΔE of higher than 3 after 3,000 hours were evaluated as having low weather resistance stability, test specimens with a ΔE of 2 to 3 as having medium weather resistance stability, and test specimens with a ΔE of less than 2 as having excellent weather resistance stability.

[0174] material In the following examples, the following thermoplastic polymers were used as the polymer matrix A, the pigment B and the dye C: Polymer Matrix A A1 Polymethyl methacrylate (PMMA), PLEXIGLAS® 7H, commercially available from Roehm GmbH, melt volume flow rate MVR (230° C., 3.8 kg load) 1.4 cm 3 / 10min A2 Polycarbonate (PC), Makrolon® LED 2245, available from Covestro, melt volume flow rate MVR (300°C, 1.2 kg load) 34 cm 3 / 10min A3 Styrene-acrylonitrile copolymer (SAN), Luran® 2560, nature, commercially available from Ineos Styrolution.

[0175] Inorganic Pigment B B1 Yellow 10P150 from Shepherd Color Company, Pigment Yellow 227, a Nb / S / Sn / Zn pigment based on the pyrochlore structure (used as a pure pigment) B2 Orange 10P340 from Shepherd Color Company, Pigment Yellow 216, a Sn / Zn / Ti pigment based on the rutile structure (used as a pure pigment) B3 KRONOS INTERNATIONAL, Inc. KRONOS® CL 2220, a rutile pigment surface-treated with titanium dioxide pigment, aluminum, silicon and polysiloxane compounds B4 Heucodur Yellow 6R, Pigment Brown 24, Cr / Sb / Ti mixed oxide based on rutile type, CAS: 68186-90-3 (used as pure pigment).

[0176] organic dye C C1 Solvaperm® Orange 3G, Solvent Orange 60, CAS 6925-69-5, a perinone dye from Clariant (used as a pure dye or as a PMMA-based masterbatch containing 1% dye) C2 Lanxess Macrolex® Red EG, Solvent Red 135, CAS 20749-68-2, Perinone dye (used as pure dye or as PMMA-based masterbatch with 10% or 1% dye) C3 Oracet® Red 454, from BASF, Solvent Red 195, CAS 72968-71-9, a monoazo dye (used as a pure dye or as a PMMA-based masterbatch containing 10% or 1% dye).

[0177] Test specimens with a thickness of 1 mm were produced using a molding composition of PMMA and 1% by weight of each of the organic dyes C1, C2 or C3 relative to the molding composition, as described below, where a PMMA-based masterbatch obtained from the masterbatch was used.

[0178] The haze values ​​were measured at 23° C. on the injection molded specimens with a thickness of 1 mm according to standard ASTM D1003. The haze results for the specimens containing organic dye C are as follows: C1: 1.1% / C2: 1.0% / C3: 3.9%. These low haze values ​​indicate that the organic dyes C1, C2 and C3 are soluble organic dyes monomolecularly dispersed in the PMMA matrix, which is typical for organic dyes and cannot be achieved with pigments, such as the inorganic pigment B mentioned above.

[0179] Preparation of test specimens The colored molding compositions of Examples 1 to 15 listed in Tables 1, 2 and 3 below were prepared in the following manner: Polymer granules and color preparations received from the manufacturer were used in a tumbling mixer to prepare a mixture, which was metered by means of a funnel into the feed zone of a single screw extruder 30 ESE from Herbert Stork Maschinenbau GmbH, Mörfelden. Extrusion was carried out at 250° C. with an open vent zone. A granulator was connected downstream of the extruder.

[0180] In a second processing step, test specimens were injection molded from the thus obtained granules.

[0181] For each example, 3 mm thick test specimens were injection molded using an Arburg Allrounder 320 C available from ARBURG GmbH & Co KG, Loessburg, at 260° C. under the following conditions: Ejection time: 0.92 seconds Material temperature: 250℃ Cylinder temperature: 250~220℃ Mold temperature: 70℃ Switch from injection to holding pressure at 600 bar inside the mold Total cycle time: 40 seconds Injection molding with closed vent cylinder.

[0182] Examples 1 to 7 and 16 / Orange molding composition The following orange molding composition was prepared as described above.

[0183] [Table 1]

[0184] Examples 8 to 15 / Red molding composition The following red molding composition was prepared as described above:

[0185] [Table 2]

[0186] Test results Colorimetry and weathering stability were measured as described above using 3 mm thick injection molded specimens.

[0187] [Table 3]

[0188] [Table 4]

[0189] The molding compositions according to the invention according to Examples 2 and 4 exhibit a high degree of color vividness (chroma C 0 1 ) compared to the molding compositions according to Examples 1 and 3 due to the addition of a solvent dye (i.e. Solvent Orange 60). * ) This effect is demonstrated for PMMA (Examples 1 and 2) and PC (Examples 3 and 4).

[0190] Comparative Example 5, using the comparative yellow / brown pigment Pigment Brown 24, also based on rutile mixed metal oxide (Cr / Sb / Ti mixed oxide), shows a lower color vividness (chroma C) than Example 2 according to the invention, despite the amount of soluble dye being three times higher. * ) is shown.

[0191] Comparative Example 6 and Comparative Example 7, which utilize a combination of titanium dioxide and the solvent dye Solvent Orange 60, have higher color vividness (chroma C * ), but the weather resistance stability is extremely low (see Table 4 below).

[0192] Comparative Example 16, which utilizes a combination of pigment B2 (PY216) and titanium dioxide pigment B3, exhibits lower color vividness (chroma C) than in accordance with the invention, Example 2, which utilizes a combination of B2 (PY216) and a soluble organic dye (i.e., a soluble organic dye) according to the invention. * ) is shown.

[0193] Examples 8 to 10 according to the invention, which are directed to PMMA-based molding compositions, show increased color brilliance compared to Example 15, which utilizes the common mixed metal oxide pigment Brown 24 (Cr / Sb / Ti mixed oxide) in the rutile form, and compared to Examples 13 and 14, which utilize titanium dioxide in combination with a red solvent dye.

[0194] The lower chroma values ​​of Example 11 according to the invention and Example 12 according to the invention are due to the difference in the polymer matrices (SAN and PC).

Claims

1. The following: A. A polymer matrix A containing at least one thermoplastic polymer; B. At least one inorganic pigment B selected from a mixed metal oxide or mixed metal oxosulfide B1 containing niobium, tin and zinc metals, and / or a mixed metal oxide or mixed metal oxosulfide B2 containing titanium, tin and zinc metals; C. At least one organic dye C A composition for thermoplastic molding containing the above.

2. The composition for thermoplastic molding contains the following with respect to the whole of the composition for thermoplastic molding respectively: A. 49.99998 to 99.99998% by weight, preferably 59.9998 to 99.9998% by weight, more preferably 89.998 to 99.998% by weight of the polymer matrix A; B. 0.00001 to 5.0% by weight, preferably 0.0001 to 4.0% by weight, more preferably 0.001 to 3.0% by weight of the at least one inorganic pigment B; C. 0.00001 to 5.0% by weight, preferably 0.0001 to 4.0% by weight, more preferably 0.001 to 3.0% by weight of the at least one organic dye C, where the organic dye C is selected from monoazo dyes, perinone dyes, quinophthalone dyes and anthraquinone dyes; D. 0 to 50.0% by weight, preferably 0 to 40.0% by weight, more preferably 0 to 10.0% by weight of one or more additional components D, preferably selected from organic pigments, inorganic pigments different from B, scattering particles, impact resistance improvers, antistatic agents, antioxidants, mold release agents, flame retardants, lubricants, fluidity improvers, fillers, ultraviolet absorbers, light stabilizers and organic phosphorus compounds, agents imparting weather resistance and plasticizers The composition for thermoplastic molding according to Claim 1 containing the above.

3. The polymer matrix A contains at least one thermoplastic polymer selected from polyalkyl (meth)acrylates, poly(meth)acrylimides, polyalkyl (meth)acrylate copolymers, polystyrene, polystyrene copolymers, acrylonitrile copolymers, polycarbonates, polyesters, polyamides, polyvinylidene fluoride and polyolefins. The composition for thermoplastic molding according to Claim 1.

4. The thermoplastic molding composition according to claim 1, wherein the polymer matrix A contains at least one thermoplastic polymer selected from polyalkyl (meth)acrylate, polycarbonate, and styrene-acrylonitrile copolymer.

5. The thermoplastic molding composition according to claim 1, wherein the inorganic pigment B1 is selected from pyrochlore type Nb / Sn / Zn oxosulfide, preferably Pigment Yellow 227, and the inorganic pigment B2 is selected from rutile type Ti / Sn / Zn oxide, preferably Pigment Yellow 216.

6. The thermoplastic molding composition according to claim 1, wherein the at least one organic dye C is selected from monoazo dyes, perinone dyes, quinophthalone dyes, anthraquinone dyes, and pyrazolone dyes.

7. The thermoplastic molding composition according to claim 1, wherein the at least one organic dye C is selected from Solvent Yellow 93 (4-(4,5-dihydro-1-phenyl-3-methyl-5-oxo-1H-pyrazol-4-ylidene methyl)-1-phenyl-3-methyl-1H-pyrazol-5(4H)-one); Solvent Orange 60 (12H-phthaloperylene-12-one); Solvent Orange 116 (4-methyl-2,6-bis-p-tolylamino-5-(2-trifluoromethylphenylazo)nicotinonitrile); Solvent Red 195 (cyano-5-[[5-cyano-2,6-bis[(3-methoxypropyl)amino]-4-methylpyridin-3-yl]azo]-3-methyl-2-thiophenecarboxylic acid methyl ester); Solvent Red 52 (3-methyl-6-[(4-methylphenyl)amino]-3H-naphtho[1,2,3-de]quinoline-2,7-dione); and Solvent Red 135 (8,9,10,11-tetrachloro-12H-phthaloperylene-12-one).

8. The thermoplastic molding composition according to claim 1, wherein the molding composition contains at least one additional component D selected from organic pigments, inorganic pigments different from B, scattering particles, impact resistance improvers, antistatic agents, antioxidants, mold release agents, flame retardants, lubricants, fluidity improvers, fillers, ultraviolet absorbers, light stabilizers, organic phosphorus compounds, agents for imparting weather resistance, and plasticizers.

9. In the molding composition, the transmittance Y determined using standard illumination D65 / 10° in accordance with DIN 5033-7 and measured for a sample with a thickness of 3.0 mm is less than 10%, preferably less than 6.5%, and / or in the thermoplastic molding composition, the color values a ＊ and b ＊ both of which are greater than zero, the thermoplastic molding composition according to claim 1.

10. The following: At least one inorganic pigment B selected from a mixed metal oxide or a mixed metal oxosulfide B1 containing niobium (Nb), tin (Sn) and zinc (Zn); and / or a mixed metal oxide or a mixed metal oxosulfide B2 containing titanium (Ti), tin (Sn) and zinc (Zn); At least one organic dye C, preferably selected from monoazo dyes, perinone dyes, quinophthalone dyes and anthraquinone dyes; and A dispersion medium, preferably a solid dispersion medium or a liquid dispersion medium A coloring composition comprising.

11. The coloring composition is a masterbatch, and the masterbatch is as follows with respect to the whole of the masterbatch: 0.01 to 40.0% by weight of the at least one inorganic pigment B; 0.01 to 40.0% by weight of the at least one organic dye C; 50.0 to 99.98% by weight of a solid dispersion medium containing at least one thermoplastic polymer; and 0.0 to 10.0% by weight of one or more auxiliary additives The coloring composition according to claim 10, comprising.

12. The composition is a liquid coloring composition, and the liquid coloring composition is as follows with respect to the whole of the liquid coloring composition: 0.5 to 50.0% by weight of the at least one inorganic pigment B; 0.5 to 50.0% by weight of the at least one organic dye C; 1.0 to 30.0% by weight of at least one dispersant; 48.0 to 98.0% by weight of a liquid dispersion medium; and 0.0 to 50.0% by weight of one or more auxiliary additives The coloring composition according to claim 10, comprising.

13. A method for producing a composition for thermoplastic molding according to any one of claims 1 to 9, the method comprising the following: i. Providing a polymer matrix A containing at least one thermoplastic polymer; and ii. Adding to the polymer matrix A obtained in step i) at least one inorganic pigment B selected from a mixed metal oxide or a mixed metal oxosulfide B1 containing niobium, tin and zinc; and / or a mixed metal oxide or a mixed metal oxosulfide B2 containing titanium, tin and zinc; and at least one organic dye C A method comprising.

14. The method according to claim 13, wherein step ii) is carried out in an extruder at a temperature in the range of 150°C to 350°C, preferably 200°C to 320°C, more preferably 230°C to 300°C.

15. A molded article produced from the thermoplastic molding composition according to any one of claims 1 to 9.

16. A method for producing a molded article from the thermoplastic molding composition according to any one of claims 1 to 9, preferably by injection molding or extrusion molding.