Thermoplastic molding composition with improved weather resistance

Abstract

The present invention relates to a thermoplastic molding composition having improved weather resistance and a method for producing the same. Furthermore, the present invention relates to injection-molded and extruded parts made from said thermoplastic molding composition.

Description

[Technical Field]

[0001] The present invention relates to a thermoplastic molding composition having improved weather resistance and a method for producing the same. Furthermore, the present invention relates to injection molded parts and extruded parts composed of the thermoplastic molding composition.

[0002] prior art Thermoplastic polymers, such as polymethyl methacrylate (PMMA), polyesters, polycarbonates, and polyamides, are typically colored using a variety of soluble organic dyes and, optionally, organic or inorganic pigments. Typically, perinone-, azo-, and anthraquinone-type solvent dyes are used for this purpose due to their commercial availability and bright colors. As used in this application, the term “soluble” indicates that the dye is soluble in the matrix of the thermoplastic polymer in the amount used to color it. Thus, as used in this application, the term “thermoplastic molding composition” refers to a thermoplastic composition comprising carbon black and organic dyes uniformly distributed in the matrix of the thermoplastic polymer.

[0003] Molding compositions for outdoor applications are exposed to considerable amounts of solar UV radiation and high temperatures, and therefore need to have sufficient weather resistance and stability. The long-term weather resistance and stability of thermoplastic molding compositions depend not only on the inherent stability of the underlying thermoplastic polymer, but also on various polymer additives, such as organic dyes, organic or inorganic pigments if present, and UV absorbers, UV stabilizers, etc.

[0004] Molding compositions for various outdoor applications are often colored black or grayish for aesthetic reasons. Such molding compositions typically include a combination of carbon black and at least one soluble organic dye, generally a red dye. Such combinations are known to impart an aesthetically pleasing appearance to the resulting composition.

[0005] Due to the presence of carbon black, black or grayish thermoplastic molding compositions tend to absorb a considerable amount of solar infrared (IR) radiation, which can reach temperatures above 60°C in outdoor applications. The combination of solar UV radiation and high temperatures is particularly detrimental to molding compositions, generally resulting in undesirable discoloration effects, such as yellowing of polymer materials over time and decomposition of soluble organic dyes. Therefore, there is a strong demand for weather-resistant black or grayish thermoplastic molding compositions for outdoor use.

[0006] International Publication No. 2012 / 080397 describes glazing materials that exhibit high transmittance in the visible region and low transmittance in the IR region. These materials are a. At least one type of transparent thermoplastic, b. At least one inorganic IR absorber, c. Nanoscale carbon black and d. At least one coloring agent Includes.

[0007] International Publication No. 2012 / 080397 suggests using MACROLEX® Red EG (Solvent Red 135), a perinone dye, as a red coloring agent in combination with Paliogen® Blue L6385 (Pigment Blue 60) as a blue coloring agent. This document reports that the resulting material has high weather resistance.

[0008] International Publication No. 2015 / 036526 describes a high-gloss black thermoplastic molding composition. This composition is a. 90-99.5% by weight of one or more styrene copolymers, b. 0.01-5% by weight of carbon black pigment, c. A molding composition containing 0.1 to 1.5% by weight of at least two soluble dyes, d. One or more additional substances in a weight of 0-5% Includes.

[0009] This composition has an L content of 0.5 to 2.0 as measured according to DIN5033. * - It has been reported to have a jet black color with a high gloss of over 98, as measured according to the - value and DIN67530.

[0010] Japanese Patent Publication No. 2016-037518 discloses a jet-black colored methacrylic resin molding composition having high weather resistance and shielding properties. This composition typically contains three or more dyes selected from the group consisting of red, yellow, green, blue, and purple dyes. The dyes can be selected from anthraquinone dyes, heterocyclic compound dyes, and perinone dyes. Japanese Patent Publication No. 2016-037518 suggests the use of red dyes, such as Solvent Red 52, 111, 135, 145, 146, 149, 150, 151, 155, 179, 180, 181, 196, 197, 207, Disperse Red 22, 60, 191, etc. Examples of blue dyes include Solvent Blue 35, 45, 78, 83, 94, 97, 104, and 105. Suitable yellow dyes include Disperse Yellow 160, 54, 160 and Solvent Yellow 33. Examples of green dyes include, for example, Solvent Green 3, 20, and 28. Examples of purple dyes include, for example, Solvent Violet 28, 13, 31, 35, and 36.

[0011] Commercial monoazo dyes containing at least one heteroaromatic moiety have not been used in combination with carbon black to color thermoplastic polymers, such as polyalkyl (meth)acrylates. This is because monoazosolvent dyes have been found to have only moderate thermal and weather stability, and therefore, molding compositions containing any combination of monoazosolvent dye and carbon black were expected to be unsuitable for outdoor use.

[0012] Due to insufficient weather resistance of colored molded compositions, undesirable discoloration often occurs when exposed to sunlight. Therefore, the weather resistance of a given molded composition can often be estimated by measuring the color in the CIELAB color space of a sample of such a composition before and after exposure to a weather resistance test. The color difference, i.e., the difference between these two colors, can be used as an indicator of weather resistance.

[0013] Purpose of the invention Therefore, an object of the present invention is to provide a novel gray or black thermoplastic composition having improved long-term thermal and weather resistance, an aesthetically pleasing appearance, and high gloss. It was further desired that the molding composition retain its advantageous optical properties even when exposed to high temperatures and / or high shear forces, for example, during injection molding of parts having complex geometric shapes.

[0014] A further object of the present invention was to provide a method for producing gray or black thermoplastic compositions having improved long-term thermal stability and weather resistance, particularly in an efficient manner.

[0015] Finally, the present invention aims to provide gray or black molded parts, in particular molded parts having complex geometric shapes that possess these advantageous properties.

[0016] Summary of the Invention The present invention is based on the remarkable discovery that a thermoplastic molding composition containing a monoazo dye having at least one heteroaromatic moiety in combination with carbon black has significantly higher long-term thermal stability and weather resistance than equivalent molding compositions containing other types of dyes, such as commonly used perinone dyes. Since the monoazo dye having at least one heteroaromatic moiety has excellent solubility in the thermoplastic polymer used, it dissolves completely and uniformly in the polymer matrix, and the resulting thermoplastic molding composition has excellent optical properties, low haze, high gloss, and an aesthetically pleasing appearance.

[0017] Thus, in a first aspect, the present invention relates to a) 90.0 to 99.99989% by weight of a thermoplastic polymer, b) 0.0001 to 5.0% by weight of carbon black and c) 0.00001 to 5.0% by weight of a monoazo dye containing at least one heteroaromatic moiety comprising a thermoplastic molding composition.

[0018] In addition, the present invention provides a method for producing a thermoplastic molding composition as defined above, comprising a) providing a thermoplastic polymer, and b) adding to the thermoplastic polymer from step a) at least one coloring composition comprising carbon black and a monoazo dye containing at least one heteroaromatic moiety wherein the coloring composition is preferably a liquid composition or a masterbatch. A method is provided.

[0019] Detailed description The monoazo dyes for use in the present invention are themselves well known to those skilled in the art and are derivatives of diazene (diimide) HN=NH, where both hydrogens are substituted by an aromatic moiety or a heteroaromatic moiety (IUPAC Recommendations 1995, published in Pure & Appl. Chem., Vol. 67, No. 819, pp. 1307 - 1375, 1995). That is, the chemical structure of all monoazo dyes contains one chemical moiety -N=N-.

[0020] As used in this application, the term “heteroaromatic moiety” is also well known and typically refers to a five- or six-membered aromatic moiety that contains at least one heteroatom in its structure. Typically, the heteroatom is an N, O, S, Se, or Te atom, more preferably an N, O, or S atom, and even more preferably an N atom. Specific examples of heteroaromatic moieties include, for example, furan, thiophene, pyran, pyrrole, imidazole, pyrazole, 3H-pyrazole-3-one, pyrazolin-5-one, pyridine, pyrazine, pyrimidine, pyridazine, thiazole, oxazole, isothiazole, isoxazole, thiadiazole, oxadiazole, triazole, serenazole, and telrazole. Further examples of heteroaromatic moieties include, for example, indidine, purine, pteridine, carboline, pyrroloimidazole, pyrrolotriazole, pyrazoloimidazole, pyrazolotriazole, pyrazolopyrimidine, pyrazolotriazine, triazolopyridine, tetraazaidene, imidazoimidazole, imidazopyridine, imidazopyrazine, imidazopyridine, imidazopyridazine, oxazolopyridine, oxazolopyrazine, oxazolopyridine, oxazolopyridazine, thiazolopyridine, thiazolopyrazine, thiazolopyridine, thiazolopyrazine, thiazolopyrazine, pyridinopyrazine, pyrazinopyrazine, pyrazinopyridazine, naphthyridine, imidazotriazine, and 1H-perimidine.

[0021] The heteroaromatic moiety is typically substituted with one or more substituents, which may be alkyl, alkenyl, alkynyl, aryl, amino, alkoxy, aryloxy, acyl, alkoxycarbonyl, aryloxycarbonyl, acyloxy, acylamino, alkoxycarbonylamino, aryloxycarbonylamino, sulfonylamino, sulfamoyl, -carbamoyl, alkylthio, arylthio, sulfonyl, cyano, and heterocyclic groups and halogen atoms. More preferably, alkyl, aryl, alkoxy, aryloxy, cyano, and heterocyclic groups and halogen atoms are alkyl, aryl, alkoxy, aryloxy, and aromatic heterocyclic groups, and particularly preferably, alkyl, aryl, alkoxy, and aromatic heterocyclic groups.

[0022] Specific examples of monoazo dyes for use in the present invention include Disperse Yellow 241 (5-[(3,4-dichlorophenyl)azo]-1,2-dihydro-6-hydroxy-1,4-dimethyl-2-oxonicotinonitrile), Solvent Black 3 (2,3-dihydro-2,2-dimethyl-6-((4-(phenylazo)-1-naphthyl)azo)-1H-perimidine), Solvent Red 195 (cyano-5-[[5-cyano-2,6-bis[(3-methoxypropyl)amino]-4-methylpyridine-3-yl]azo]-3-methyl-2-thiophenecarboxylate methyl ester), Solvent Yellow 16 (5-methyl-2-phenyl-4-phenylazo-4H-pyrazole-3-one), Solvent This includes, but is not limited to, Yellow 18 (4-[(2,4-dimethylphenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazole-3-one), Solvent Yellow 21 (3-[(1-oxonaphthalene-2-ylidene)methylhydrazinylidene]-1-propa-2-enylindole-2-one), Solvent Yellow 72 (4-((o-methoxyphenyl)azo)-3-methyl-1-phenyl-2-pyrazolin-5-one), Solvent Yellow 82, and Solvent Yellow 16 (5-methyl-2-phenyl-4-phenylazo-4H-pyrazole-3-one).

[0023] In a preferred embodiment of the present invention, the monoazo dye is Solvent Red 195. A thermoplastic molding composition containing Solvent Red 195 in combination with carbon black exhibits, remarkably, an aesthetically pleasing appearance, as well as significantly higher weather and thermal stability than comparable polyalkyl (meth)acrylate molding compositions containing other red solvent dyes of the prior art, such as red perinone dye. Therefore, it is advantageous that the thermoplastic molding composition of the present invention containing Solvent Red 195 substantially does not contain other red solvent dyes. Red solvent dyes within the scope of the present invention are named Solvent Red, Acid Red, or Modern Red according to their color index (CI). In particular, the thermoplastic molding composition of the present invention, which contains Solvent Red 195, typically contains less than 0.1% by weight, more preferably less than 0.01% by weight, even more preferably less than 0.001% by weight, even more preferably less than 0.0001% by weight, even more preferably less than 0.00001% by weight, and most preferably less than 0.000001% by weight of another red solvent dye, based on the weight of the thermoplastic molding composition.

[0024] The concentration of the monoazo dye containing at least one heteroaromatic moiety in the thermoplastic molding composition is determined by the desired perceived color. This concentration is generally in the range of 0.00001 to 5.0% by weight, preferably 0.0001 to 4.0% by weight, and more preferably 0.001 to 3.0% by weight, based on the weight of the thermoplastic molding composition. If further dyes are present, the total dye concentration is preferably in the range of 0.00001 to 5.0% by weight, preferably 0.0001 to 4.0% by weight, and more preferably 0.001 to 3.0% by weight, based on the weight of the thermoplastic molding composition.

[0025] At least one type of carbon black is used to impart a black or grayish color to the molding composition. The average primary particle size of the carbon black pigment is typically in the range of 5.0 to 100.0 nm, more preferably 7.0 to 60.0 nm. 50This can be determined by methods known to those skilled in the art, for example, by photon correlation spectroscopy according to standard DIN ISO 13320 (1999) using commercially available equipment, such as the LS13320 Laser Diffraction Particle Size Analyzer from Beckman Coulter Inc. Furthermore, when measured by the BET method, standard ISO 9277, it is 50-500 m 2 / g, for example, 70-200m 2 It has been shown that selecting carbon black particles with a specific surface area of ​​1 / g is advantageous in terms of coloring performance. The carbon black may or may not be treated. For example, the carbon black can be treated with a specific gas or organic substance, such as butyllithium. Such treatment makes it possible to modify or functionalize the surface. This can further improve compatibility with the polymer matrix used accordingly.

[0026] Suitable carbon blacks within the scope of the present invention differ from so-called conductive blacks in that they have low or no conductivity. Compared to the carbon blacks used herein, conductive blacks have specific forms and superlattices to achieve high conductivity. In contrast, the carbon black particles used herein can be dispersed very easily in thermoplastic resins, resulting in virtually no aggregated regions of carbon black (where corresponding conductivity may arise). Suitable carbon blacks within the scope of the present invention are commercially available under numerous brand names and in numerous forms, e.g., pellets or powders. For example, suitable carbon black is available under the brand name BLACK PEARLS® in the form of wet-processed pellets under the names ELFTEX®, REGAL®, and CSX®, as well as in a cotton-like form under the names MONARCH®, ELFTEX®, REGAL®, and MOGUL®. All of these are available from Cabot Corporation. Printex® 60 and Printex® 90 (Orion Engineered Carbons GmbH) are also suitable for this purpose.

[0027] The concentration of carbon black in the thermoplastic molding composition is mainly determined by the desired L in the CIELAB 1976 color space. * - Determined by the value. This concentration is preferably in the range of 0.0001 to 5.0% by weight, preferably 0.001 to 4.0% by weight, more preferably 0.005 to 3.0% by weight, also preferably 0.001 to 2% by weight, and also preferably 0.01 to 1% by weight, based on the weight of the thermoplastic molding composition.

[0028] In addition to a monoazo dye containing at least one heterocyclic moiety and carbon black, the thermoplastic molding composition of the present invention comprises: • At least one further dye selected from perinone dyes, quinophthalone dyes, and anthraquinone dyes. • At least one phthalocyanine pigment or • Any of the above mixtures It can further include

[0029] As readily understood by experienced colorists, the properties of these dyes, preferably covering complementary color ranges, are typically selected so that their combination produces black. An example of a simple combination that yields black is a red monoazo dye containing at least one heteroaromatic moiety and its complementary green dye. Green solvent dyes within the scope of this invention are named Solvent Green, Acid Green, or Modern Green according to their color index (CI). As an example, the dye Solvent Red 195 can be used in combination with the known dye Solvent Green 28 to achieve black coloration. In this invention, it is also possible to produce black using a combination of a yellow monoazo dye containing at least one heteroaromatic moiety and a complementary blue dye. An example of such a combination would be Solvent Yellow 82 and Solvent Blue 104, both of which are known in themselves.

[0030] Furthermore, if a glossy, jet-black appearance is desired, the thermoplastic molding composition of the present invention may advantageously include at least three dyes covering complementary color ranges. In this way, it is possible to avoid or adjust undesirable shades of black in a desired direction. One example is the combination of Solvent Red 195, Solvent Green 28, and Solvent Yellow 114. Yellow solvent dyes within the scope of the present invention are named Solvent Yellow, Acid Yellow, or Modern Yellow according to their color index (CI). The combination of the red monoazo dye Solvent Red 195, the yellow dye Solvent Yellow 114, and the green dye Solvent Green 28 is a further example of a combination with advantageous properties.

[0031] Anthraquinone dyes are dyes that have an anthraquinone moiety in their structure. Examples of suitable anthraquinone dyes (color index CI) are: 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 Includes 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; Modern Blue 8.

[0032] Examples of perinone dyes suitable for use in this invention include (color index CI) Solvent Orange 60, 78, 90; Solvent Red 135, 162, 179; Solvent Violet 29, etc.

[0033] Suitable quinophthalone dyes include (color index CI) Solvent Yellow 33, 114, 128, 129, Disperse Yellow 14, 49, 54, etc.

[0034] The phthalocyanine pigments used in the present invention are not particularly limited and include, in particular, metal-free phthalocyanines, cobalt phthalocyanines, copper phthalocyanines, nickel phthalocyanines, iron phthalocyanines, manganese phthalocyanines, and zinc phthalocyanines. Thermoplastic molding compositions containing copper phthalocyanines have been shown to have particularly high heat resistance and weather resistance as well as deep color depth. Suitable copper phthalocyanine pigments can be selected from, for example, 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.

[0035] Furthermore, the thermoplastic molding composition of the present invention may also contain at least one inorganic pigment. The inorganic pigment can be selected from, for example, barium sulfate, zinc oxide, iron oxide, magnesium titanate, calcium sulfate, calcium carbonate, magnesium carbonate, titanium dioxide, carbon black, and dolomite.

[0036] The selection of thermoplastic polymers for use in the present invention is not particularly limited, as long as the thermoplastic polymer is suitable for coloring and thermoplastic processing, in particular injection molding and extrusion. For example, the thermoplastic polymer can be advantageously selected from the group consisting of polyalkyl (meth)acrylates, polymethyl methacrylimide, polyalkyl (meth)acrylate copolymers, polystyrene, polystyrene copolymers, acrylonitrile copolymers, polycarbonates, polyesters, preferably polyethylene terephthalate, polyamides, polyvinylidene fluoride, or mixtures thereof.

[0037] Preferably, the thermoplastic polymer is selected from the group consisting of polyalkyl (meth)acrylate, polymethyl methacrylimide, polyalkyl (meth)acrylate copolymer, polystyrene, polystyrene copolymer, acrylonitrile copolymer, polycarbonate, polyester (preferably polyethylene terephthalate), polyvinylidene fluoride, or mixtures thereof. More preferably, the thermoplastic polymer is selected from the group consisting of polyalkyl (meth)acrylate, polymethyl methacrylimide, polyalkyl (meth)acrylate copolymer, polycarbonate, or mixtures thereof.

[0038] Preferably, the thermoplastic polymer itself is substantially transparent before coloring. As used in this application, the term “substantially transparent” means that, when measured for a sample having a thickness of 2.0 mm according to standard ISO 13468-2 (2006), the transmittance is at least 50%, preferably at least 60%, more preferably at least 70%, even more preferably at least 80%, and particularly preferably at least 90% (D 65 This refers to a material that possesses the following properties.

[0039] Polyalkyl (meth)acrylate Polyalkyl (meth)acrylates are typically obtained by free radical polymerization of a mixture of alkyl (meth)acrylates, typically methyl methacrylate (a) and at least one further (meth)acrylate (b). These mixtures generally contain at least 50% by weight, preferably at least 60% by weight, particularly preferably at least 80% by weight, and more preferably at least 90% by weight of methyl methacrylate (a), based on the weight of the monomer. The amount of methyl methacrylate (a) commonly used is 50.0% to 99.9% by weight, preferably 80.0% to 99.9% by weight, and particularly preferably 90.0% to 99.9% by weight, based on the weight of the monomer.

[0040] Furthermore, these mixtures for the production of polyalkyl (meth)acrylates may also include other (meth)acrylates (b) copolymerizable with methyl methacrylate (a). As used herein, the term "(meth)acrylate" means to encompass methacrylates, acrylates, and mixtures thereof. (Meth)acrylates include saturated alcohols, e.g., 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 unsaturated alcohols, e.g., oleyl (meth)acrylate, 2-propynyl (meth)acrylate, allyl (meth)acrylate, vinyl (meth)acrylate; and aryl (meth)acrylates, e.g., benzyl (meth)acrylate or phenyl (meth)acrylate, cycloalkyl (meth)acrylate, For example, it can be obtained from 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; ether alcohol (meth)acrylates, such as tetrahydrofurfuryl (meth)acrylate, vinyloxyethoxyethyl (meth)acrylate; and amides and nitriles of (meth)acrylic acid.

[0041] The amount of (meth)acrylic comonomer (b) commonly used is 0.1% to 50.0% by weight, preferably 1.0% to 20.0% by weight, and particularly preferably 1.0% to 10.0% by weight, based on the weight of the monomer. In this specification, this compound may be used individually or in mixtures.

[0042] Polymerization reactions are generally initiated by known free radical initiators. Preferred initiators include, in particular, azo initiators and peroxy compounds well known to those skilled in the art, for example, methyl ethyl ketone peroxide, acetylacetone peroxide, dilauryl peroxide, tert-butyl 2-ethyl perhexanoate, ketone peroxide, 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-ethyl peroxyhexanoate, tert-butyl These are 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.

[0043] The compositions to be polymerized may include not only the methyl methacrylate (a) and (meth)acrylate (b) described above, but also other unsaturated monomers that can be copolymerized either alone or by utilizing other monomers that facilitate copolymerization with methyl methacrylate and the aforementioned (meth)acrylate. These include, among others, 1-alkenes, e.g., 1-hexene, 1-heptene; branched-chain alkenes, e.g., vinylcyclohexene, 3,3-dimethyl-1-propene, 3-methyl-1-diisobutylene, 4-methyl-1-pentene; acrylonitrile; vinyl esters, e.g., vinyl acetate; styrene, substituted styrenes having alkyl substituents in the side chains, e.g., α-methylstyrene and α-ethylstyrene; maleic acid derivatives, e.g., maleic anhydride, methyl maleic anhydride, maleimide, methyl maleimide and dienes, e.g., divinylbenzene.

[0044] The amounts of these comonomers (c) commonly used are 0.0% to 35.0% by weight, preferably 0.0% to 30.0% by weight, and particularly preferably 0.0% to 25.0% by weight, based on the weight of the monomer. In this specification, this compound can be used individually or in mixtures.

[0045] As polymerizable components, (a) 50.0% to 99.9% by weight of methyl methacrylate, (b) Acrylic acid esters of C1-C4 alcohols in an amount of 0.1% to 50.0% by weight, (c) monomers copolymerizable with monomers (a) and (b) in amounts of 0.0% to 35.0% by weight. Polyalkyl (meth)acrylates that can be obtained by polymerization of a composition having the above are even more preferred.

[0046] In further embodiments, polyalkyl (meth)acrylates comprising 85.0% to 99.5% by weight of methyl methacrylate and 0.5% to 15.0% by weight of methyl acrylate are preferred. The amounts here are based on 100% by weight of the polymerizable component. Particularly advantageous copolymers are those that can be obtained by copolymerizing 90.0% to 99.5% by weight of methyl methacrylate and 0.5% to 10.0% by weight of methyl acrylate. The amounts here are based on 100% by weight of the polymerizable component. For example, polyalkyl (meth)acrylates may include 91.0% by weight of methyl methacrylate and 9.0% by weight of methyl acrylate, 96.0% by weight of methyl methacrylate and 4.0% by weight of methyl acrylate, or 99.0% by weight of methyl methacrylate and 1.0% by weight of methyl acrylate. The Vicker softening point (VSP) of the polyalkyl (meth)acrylate (ISO 306:2013, Method B50) is typically at least 90°C, preferably 95°C to 112°C.

[0047] The weight average molecular weight Mw of the polyalkyl (meth)acrylate is generally in the range of 50,000 g / mol to 300,000 g / mol. Particularly advantageous mechanical properties are obtained in each case using a polyalkyl (meth)acrylate in which the average molecular weight Mw determined by GPC against a PMMA calibration standard and THF as eluent is in the range of 50,000 g / mol to 200,000 g / mol, preferably 80,000 g / mol to 180,000 g / mol.

[0048] In a particularly preferred embodiment, the polyalkyl (meth)acrylate is such that the polymerizable components are, based on the weight of the polymerizable composition, (a) 80.0% to 99.9% by weight of methyl methacrylate and (b) 0.1% to 20.0% by weight of an acrylic acid ester of a C1 - C4 alcohol and can be obtained by polymerization of a composition containing them.

[0049] The corresponding copolymer is commercially available, for example, under the trademark PLEXIGLAS® from Roehm GmbH.

[0050] Poly(meth)acrylimide The poly(meth)acrylimide (PMMI) that can be used in the present invention contains, based on the weight of the poly(meth)acrylimide, at least 25% by weight, preferably at least 50% by weight, most preferably at least 70% by weight of the formula (I):

Chemical formula

[0051] Methods for manufacturing PMMI are disclosed, for example, in European Patent Publication No. 216505, No. 666161, or No. 776910, the entirety of which is incorporated herein by reference.

[0052] The starting materials used in the production of PMMI are derived from alkyl esters of methacrylic acid and generally include polymers consisting of more than 50.0% by weight, preferably more than 80.0% by weight, and particularly preferably 95.0% to 100.0% by weight, of alkyl ester units of methacrylic acid having 1 to 4 carbon atoms in the alkyl group. Methyl methacrylate is preferred. The preferred polymer consists of at least 80.0% by weight, preferably more than 90.0% by weight, more preferably more than 95.0% by weight, and even more preferably more than 99.0% by weight of methyl methacrylate. The use of pure methyl methacrylate is most preferred. Comonomers that can be used include any monomer copolymerizable with methyl methacrylate, particularly alkyl esters of acrylic acid having 1 to 4 carbon atoms in the alkyl group, acrylo- or methacrylonitrile, acrylic or methacrylamide, styrene, or other maleic anhydride. This type of thermoplastically processable polymer is preferred, having a reduced viscosity 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 with a median particle size of about 0.03 mm to 3 mm.

[0053] Typically, PMMI for use in the present invention has a mass-average molar weight Mw of 80,000 g / mol to 200,000 g / mol, preferably 90,000 g / mol to 150,000 g / mol, as determined by GPC using PMMA as a standard. Such materials are commercially available from Roehm GmbH under the trademark PLEXIMID®. Suitable products include, but are not limited to, PLEXIMID® TT50, PLEXIMID® TT70, PLEXIMID® 8805, PLEXIMID® 8813, and PLEXIMID® 8817, all commercially available from Roehm GmbH.

[0054] Polycarbonate Furthermore, polycarbonate can also be used as a thermoplastic polymer in the method of the present invention. Polycarbonate can be formally considered as a polyester formed from carbonic acid and aliphatic or aromatic dihydroxyl compounds. These can be easily obtained by polycondensation or transesterification reactions by reacting diglycol or bisphenol with phosgene or diesteric carbonate.

[0055] Polycarbonates obtained from bisphenols are preferred. 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). Typically, such aromatic polycarbonates are prepared by interfacial polycondensation or transesterification. The properties of the polycarbonate can be adjusted to a desired purpose by selecting the bisphenol.

[0056] scattering particles In some embodiments of the present invention, the thermoplastic molding composition may further comprise organic or inorganic scattering particles dispersed in a matrix of a thermoplastic polymer. The properties of the scattering particles are not particularly limited, but they are 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 a 589 nm NaD line, as specified in standard ISO 489 (1999).

[0057] Scattered particles typically have a weight-average particle size of 0.01 μm to 100.0 μm. The weight-average particle size of scattered particles is the so-called volume-average particle size. 50 The value (i.e., 50 volume% of particles having a particle size less than a certain average particle size) can be measured according to the standard ISO 13320-1 (2009) for laser diffraction measurements. Typically, the size of scattered particles is determined in each case by laser light scattering (room temperature, 23°C) using a Beckman Coulter LS13320 laser diffraction particle size analyzer, Tornado dry powder system, in dry powder form. The measurement is performed as described in the manual. The computer-aided analysis model Mie is used.

[0058] Inorganic scattering particles may include traditional inorganic opacifiers, such as barium sulfate, calcium carbonate, titanium dioxide, or zinc oxide.

[0059] Organic scattering particles are typically spherical scattering beads made of crosslinked polymer materials, such as polyalkyl (meth)acrylate, silicone, or polystyrene. For the purposes of this invention, the term “spherical” means that the scattering beads are preferably spherical, but it will be apparent to those skilled in the art that scattering beads of other shapes may exist as a result of the manufacturing method, or the shape of the scattering beads may deviate from the ideal sphere. Therefore, the term “spherical” means that the ratio of the maximum to minimum dimensions of the scattering beads is 4 or less, preferably 2 or less. These dimensions are measured through the centroid of the scattering beads. Based on the number of scattering beads, at least 70%, and in particular at least 90%, are preferably spherical.

[0060] Preferred scattering beads made of cross-linked polystyrene are the trademarks Techpolymer® SBX-4, Techpolymer® SBX-6, Techpolymer® SBX-8, and Techpolymer® SBX-12, which are commercially available from Sekisui Plastics Co., Ltd.

[0061] Other particularly preferred spherical plastic particles used as scattering agents include cross-linked silicones. Silicone scattering agents particularly preferred in the present invention can be obtained from Momentive Performance Materials Inc. as TOSPEARL® 120 and TOSPEARL® 3120.

[0062] Impact resistance modifier The mechanical properties of a thermoplastic molding composition can be further adjusted to a desired purpose if the thermoplastic molding composition contains an impact modifier. Impact modifiers for use in the present invention are well known and can have various chemical compositions and polymer structures. The impact modifier may be crosslinked or thermoplastic. In addition, the impact modifier may be in particulate form, such as core-shell or core-shell-shell particles. Typically, particulate impact modifiers have an average particle size of 20 nm to 500 nm, preferably 50 nm to 450 nm, more preferably 100 nm to 400 nm, and most preferably 150 nm to 350 nm. In this context, “particulate impact modifier” generally means a crosslinked impact modifier having a core, core-shell, core-shell-shell, or core-shell-shell-shell structure. The average particle size of a particulate impact modifier can be determined by methods known to those skilled in the art, for example, by photon correlation spectroscopy according to standard DIN ISO 13321 (1996).

[0063] In its simplest form, the particulate impact modifier is a crosslinked particle obtained by emulsion polymerization, having an average particle size in the range of 10 nm to 250 nm, preferably 20 nm to 100 nm, and more preferably 30 nm to 90 nm. These generally consist of at least 20.0% by weight, preferably 20.0% to 99.0% by weight, particularly preferably 30.0% to 98.0% by weight of butyl acrylate and 0.1% to 2.0% by weight, preferably 0.5% to 1.0% by weight of a crosslinkable monomer, such as a polyfunctional (meth)acrylate, such as allyl methacrylate, and optionally other monomers, such as 0.0% to 10.0% by weight, preferably 0.5% to 5.0% by weight of C1-C4 alkyl methacrylate, such as ethyl acrylate or butyl methacrylate, preferably methyl acrylate, or other vinyl polymerizable monomers, such as styrene.

[0064] A more preferred impact resistance modifier is polymer particles obtained by emulsion polymerization, which may have a core-shell structure or a core-shell-shell structure (see, for example, European Patent Application Publications No. 0113924, No. 0522351, No. 0465049, and No. 0683028). In the present invention, a suitable average particle size of these emulsion polymers is typically required in the range of 20 nm to 500 nm, preferably 50 nm to 450 nm, more preferably 150 nm to 400 nm, and most preferably 200 nm to 350 nm.

[0065] A three-layer or three-phase structure having a core and two shells can have the following compositions: The innermost (hard) shell can consist of, for example, methyl methacrylate, a small amount of comonomer, for example, ethyl acrylate, and a certain amount of crosslinking agent, for example, allyl methacrylate. The intermediate (soft) shell can consist of, for example, a copolymer containing butyl acrylate and, optionally, styrene. The outermost (hard) shell, on the other hand, is the same as the matrix polymer, thus providing compatibility and good bonding to the matrix. The proportion of polybutyl acrylate in the core or shell of the impact-improving agent in a two-layer or three-layer core-shell structure is decisive to the impact-improving 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 impact-improving agent.

[0066] Thermoplastic impact modifiers have a different mechanism of action than particulate impact modifiers. They are generally mixed with the matrix material. When domains are formed, for example when using block copolymers, if a preferred size exists for these domains, that size can be determined, for example, by electron microscopy, and then matched to the preferred size for core-shell particles.

[0067] Various classes of thermoplastic impact modifiers exist. One example is aliphatic thermoplastic polyurethane (TPU), such as the Desmopan® products commercially available from Covestro AG. For example, the TPUs Desmopan® WDP85784A, WDP85092A, WDP89085A, and WDP89051D all have a refractive index of 1.490 to 1.500 and are particularly suitable as impact modifiers.

[0068] Further classes of thermoplastic polymers for use in accordance with the present invention as impact resistance modifiers are methacrylate-acrylate block copolymers, in particular acrylic TPEs, which include PMMA-poly-n-butyl acrylate-PMMA triblock copolymers, commercially available from Kuraray under the product name Kurarity®. The poly-n-butyl acrylate blocks form nanodomains in the polymer matrix having a size of 10 nm to 20 nm.

[0069] The thermoplastic polymer used in the present invention may contain any type of further conventional additives / auxiliaries. These include, among others, antistatic agents, antioxidants, mold release agents, flame retardants, lubricants, flow improvers, fillers, UV absorbers, light stabilizers, and organophosphorus compounds, such as phosphites or phosphonates, pigments, weather-resistant agents, and plasticizers. The selection and amount of additives can be adjusted according to the intended application. The thermal stability and weather resistance of the resulting thermoplastic molded composition should not be excessively impaired by these additives.

[0070] When the thermoplastic polymer is a polyalkyl (meth)acrylate, the thermoplastic molding composition of the present invention typically has a melt flow rate (MVR) of 0.5 to 10.0 g / 10 min, measured at 230°C with a load of 3.8 kg according to ISO 1133 (2011). Therefore, the thermoplastic molding composition can be advantageously used for injection molding and extrusion.

[0071] The jet-black colored thermoplastic molding composition of the present invention is typically 0.4 to 2 L according to DIN 5033. * - Has a value. If necessary, this composition often has a low L of about 0.4 to 1, especially 0.4 to 0.9. * - may have a value. The gloss of such a molded composition (R 60°; measured according to DIN67530(1982)) is typically at least 60, more preferably at least 70, even more preferably at least 80, and particularly preferably at least 90.

[0072] Due to insufficient weather resistance, thermoplastic molded compositions often undergo undesirable discoloration when exposed to high temperatures. Therefore, the weather resistance of a given molded composition can often be estimated by measuring the color of a sample of such a composition in the CIELAB color space before and after exposure to a weather resistance test. The color difference, i.e., the difference between these two colors, can be used as an indicator of weather resistance.

[0073] In a preferred embodiment, the color difference ΔE of the molded composition after a 3000-hour artificial weathering test is determined according to the CIELAB 1976 standard DIN6174 (D 65 The temperature (10°) is less than 3.0, preferably less than 2.5, and particularly preferably less than 2.0. The corresponding test is carried out under the following conditions. • Device: Xenotest Beta LM / 1 • Filter: Xenochrome 300 filter system, daylight color (ISO 4892-2) · Irradiance: 60W / m 2 (300~400nm) • Temperature: Chamber 38±3℃, Black standard 65±3℃ · Humidity: 65±10%RH · 102 minutes dry, 18 minutes water spray

[0074] Method for producing thermoplastic molded compositions Further embodiments of the present invention are methods for producing the thermoplastic molded compositions defined above, a) A step of providing a thermoplastic polymer, b) A step of adding to the thermoplastic polymer from step a) a coloring composition comprising carbon black and a monoazo dye containing at least one heteroaromatic moiety. Includes, The coloring composition is preferably a liquid composition or a masterbatch. Regarding the method.

[0075] In one embodiment, in step b), a single coloring composition is added to the thermoplastic polymer from step a), and the preparation contains a monoazo dye in combination with carbon black. In a further embodiment, two or more coloring compositions may be added in step b), one of which may contain a monoazo dye and the other may contain carbon black. When two or more coloring compositions are added in step b), they may be added in any order or simultaneously.

[0076] The coloring composition may be, for example, a liquid composition or a masterbatch. When the coloring composition is added to a thermoplastic polymer in the form of a liquid composition, the liquid composition typically comprises 1.0 to 30.0% by weight, preferably 5.0 to 25.0% by weight, more preferably 1.0 to 20.0% by weight of a dispersion additive, 0.05 to 10.0% by weight, preferably 0.1 to 5.0% by weight of carbon black, 0.5 to 50.0% by weight, preferably 5.0 to 40.0% by weight of a monoazo dye, 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 an auxiliary additive, as well as a liquid, such as demineralized water or an organic solvent, with the total weight of the components of the liquid composition being 100% by weight. Examples of organic solvents include, but are not limited to, 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 tetraglyceride or mixtures thereof.

[0077] The selection of dispersion additives is not particularly limited, as long as the additive does not adversely affect the properties of the resulting thermoplastic molded composition. The use of pH-independent dispersion additives has been shown to be particularly advantageous in terms of the thermal stability and color uniformity of the resulting thermoplastic molded composition.

[0078] For example, the dispersion additive may be a high molecular weight copolymer containing at least maleic anhydride, styrene, and amino polyether as monomer units. Alternatively, the dispersion additive may be a copolymer of methacrylic acid and hydrophobic methacrylate. As used herein, the term "hydrophobic methacrylate" preferably refers to an ester of methacrylic acid with an alcohol having at least 3 and no more than 24 carbon atoms. Furthermore, the dispersion additive may be a copolymer of polyethers, preferably ethylene oxide, propylene oxide and / or butylene oxide, and styrene oxide.

[0079] Suitable dispersion additives include, for example, Dispex® Ultra 4550 (formerly EFKA® 4550), a polyacrylate commercially available from BASF SE. This polymer essentially consists of monomers α-methylstyrene, 2-ethylhexyl acrylate, and poly(ethylene glycol) methyl ether (MPEG) methacrylate. Further examples of suitable dispersion additives include TEGO® Dispers 750W and 755W, available from Evonik Industries AG, and Disperbyk® 190 from BYK-Chemie GmbH.

[0080] In some cases, to minimize undesirable discoloration of the molded composition at high temperatures, the dispersion additive can be selected such that the mass loss of the dispersion additive in dry form is 15.0% by weight or less, preferably 0.0 to 10.0% by weight, more preferably 0.0 to 7.0% by weight, even more preferably 0.0 to 5.0% by weight, and particularly preferably 0.0 to 4.0% by weight, in isothermal thermogravimetric analysis (TGA) at 260°C for 15 minutes. Isothermal thermogravimetric analysis is performed using an automated thermobalance, such as a TA Instruments Q5000 IR, at a heating rate of 5 K / min up to a maximum of 260°C, followed by isothermal analysis at 260°C for 15 minutes. The sample is dried to a certain mass in a drying oven before analysis by TGA. In the case of bead polymers as dispersion aids, TGA is performed on the solid bead polymer. That is, in the case of an alkaline aqueous solution of the bead polymer, the solid bead polymer used to prepare this solution is analyzed.

[0081] In addition to dispersion additives, the liquid preparation may contain auxiliary additives, such as agents to prevent disintegration or bacterial degradation, bactericides, leveling agents, thickeners, and defoaming agents.

[0082] In some embodiments, for example, when the liquid preparation contains a pigment or pigment mixture, particularly when their concentration is less than 10.0% by weight, viscosity adjustment may be advantageous in preventing the sedimentation of the pigment or pigment mixture. This is preferably done by adding one or more thickeners. Preferred thickeners include, among others, cellulose, particularly ethylcellulose. Further possibilities include the use of carboxylate-containing polymers, such as homopolymers and copolymers based on vinyl acetate and crotonic acid or partially hydrolyzed poly(meth)acrylate, which are available as water-soluble or alkali-soluble solid products, colloidal solutions, or aqueous dispersions, as thickeners. Homopolymers and copolymers of acrylic acid and / or methacrylic acid in the form of their sodium salts are particularly preferred.

[0083] The proportion of ethylenically unsaturated free radical polymerizable carboxylic acid is preferably 6.0% by weight or more and 80.0% by weight or less, preferably 10.0 to 80.0% by weight, and particularly 20.0 to 80.0% by weight, based on the total weight of monomers used to prepare the thickener. Acrylic acid and / or methacrylic acid and maleic acid are preferred. Fumaric acid, itaconic acid or crotonic acid are also suitable.

[0084] The comonomers involved in the formation of the thickener can be highly water-soluble or low water-soluble ethylenically unsaturated free radical polymerizable monomers. Favorable effects are particularly provided by ethylene and alkyl esters of acrylic acid and / or methacrylic acid having 1 to 4 carbon atoms in the alkyl group. The proportion is preferably 20.0 to 90.0% by weight, more preferably 20.0 to 80.0% by weight, based on the total weight of monomers used in the preparation of the thickener. Other usable comonomers include, for example, styrene, acrylonitrile, or vinyl acetate. Comonomers with higher hydrophilicity or water solubility, such as acrylamide and / or methacrylamide or hydroxyalkyl esters of acrylic acid and / or methacrylic acid, can also be used, for example, in a total of about 30.0% by weight, preferably up to 10.0% by weight, based on the total weight of monomers used in the preparation of the thickener.

[0085] Thermoplastic polymers can also be colored by adding a coloring composition to the thermoplastic polymer from step a) in the form of a masterbatch. A masterbatch is understood to mean a formulation containing polymer molding material, monoazo dyes and / or carbon black. The concentration of the coloring preparation in the masterbatch is adjusted so that the desired color impression is produced when the masterbatch is used to color the uncolored thermoplastic polymer from step a).

[0086] The masterbatch added in step b) is typically, 0.01 to 40.0% by weight of monoazo dyes, 0.01-10.0% by weight of carbon black, 50.0-99.99% by weight of thermoplastic polymer, 0.0 to 10.0% by weight of at least one auxiliary additive Includes.

[0087] The thermoplastic polymer in the masterbatch can be substantially the same as those described above. The selection of the thermoplastic polymer in the masterbatch is not particularly limited, as long as the thermoplastic polymer is suitable for coloring and thermoplastic processing, in particular injection molding and extrusion. For example, the thermoplastic polymer can be advantageously selected from the group consisting of polyalkyl (meth)acrylates, polymethyl methacrylimide, polyalkyl (meth)acrylate copolymers, polystyrene, polystyrene copolymers, acrylonitrile copolymers, polycarbonates, polyesters, preferably polyethylene terephthalate, polyamides, polyvinylidene fluoride, or mixtures thereof.

[0088] The thermoplastic polymer can also be colored by adding a pure coloring preparation obtained from the manufacturer and carbon black to the thermoplastic polymer from step a).

[0089] The inventors have further found that the coloring preparation used in step b) should favorably contain less than 100 ppm of aluminum compound and less than 300 ppm of silicon compound. This effectively prevents the formation of undesirable dark particles in the molded composition. While not wishing to be bound by theory, the inventors have found that even when aluminum and silicon compounds are present in low amounts of several hundred ppm, they may form chelate-type chemical complexes with monoazo dyes containing at least one heteroaromatic moiety. In contrast to free monoazo dyes, such chemical complexes are substantially insoluble in the thermoplastic polymer matrix, leading to the undesirable formation of dark particles in the resulting molded parts. In particular, when parts with complex geometric shapes are manufactured by injection molding, high temperatures are often required to ensure sufficiently low viscosity of the polymer melt. High temperatures combined with high shear forces during the injection molding process are thought to promote the formation of such undesirable dark particles in the presence of aluminum or silicon.

[0090] The inventors have further found that the optical properties and thermal stability of the thermoplastic molded composition can be further improved when the colored preparation has a dry mass loss of 15.0% by weight or less, preferably 0.0 to 10.0% by weight, more preferably 0.0 to 7.0% by weight, even more preferably 0.0 to 5.0% by weight, and particularly preferably 0.0 to 4.0% by weight, as measured by isothermal thermogravimetric analysis (TGA) at 260°C for 15 minutes. While we do not wish to be bound by theory, it is generally believed that colored preparations with particularly low dry mass loss typically have low solubility in thermoplastic polymers and generate particularly small amounts of by-products that cause the formation of various optical defects in the final thermoplastic molded composition.

[0091] A method for producing a thermoplastic molding composition according to the present invention can be carried out by a conventional assembly method, which involves combining, mixing, and homogenizing a thermoplastic polymer with a liquid composition or masterbatch. This method can be carried out in a molten material under the action of shear force. The combination and mixing prior to melt homogenization may be carried out using a powder premix, in particular when a masterbatch containing a monoazo dye and / or carbon black is introduced.

[0092] Thermoplastic polymers and masterbatches, liquid compositions, or pure color preparations obtained from manufacturers can be combined, mixed, homogenized, and then extruded in conventional equipment, such as screw extruders (e.g., twin-screw extruders, ZSK), kneaders, Brabenders, or Banbury mills. After extrusion, the extruded material can be cooled and pelletized. It is also possible to premix the individual components and then add the remaining starting materials separately and / or as a mixture. As used in this application, the term “color preparation” refers to materials commercially available from manufacturers as “dyes.” The color preparation consists substantially of the corresponding monoazo dyes having varying chemical purities.

[0093] In further embodiments, the thermoplastic polymer can be provided in hot-melt form, to which a liquid composition or masterbatch is added. This method is particularly advantageous for coloring the thermoplastic polymer immediately after its production.

[0094] Typically, when the thermoplastic polymer is a polyalkyl (meth)acrylate, step b) is carried out in an extruder at a temperature preferably in the range of 200°C to 320°C, more preferably 230°C to 300°C. This is because the molded composition has excellent thermal stability at this stage and does not undergo the undesirable formation of dark particles.

[0095] Use of thermoplastic molding compositions In a further embodiment, the present invention relates to a method for manufacturing a molded part, comprising the steps of injection molding a thermoplastic molding composition at a temperature in the range of 200°C to 320°C, preferably 230°C to 300°C, injecting the thermoplastic molding composition into a mold capable of manufacturing a molded part, wherein the thermoplastic molding composition comprises a monoazo dye comprising at least one heteroaromatic moiety, and the thermoplastic molding composition comprises less than 100 ppm, preferably less than 50 ppm, of aluminum or a compound thereof and less than 300 ppm, preferably less than 200 ppm, of silicon or a compound thereof.

[0096] When the thermoplastic polymer is a polyalkyl (meth)acrylate, the temperature of the molten composition in the injection molding process of the present invention is preferably 210 to 320°C, more preferably 240 to 270°C. However, there are no limitations on the intended results. The temperature of the injection molding nozzle is more preferably 230 to 270°C, more preferably 240 to 250°C, and the temperature of the injection molding die is preferably 40 to 80°C, more preferably 50 to 60°C. The temperature of the injection molding cylinder is preferably 220 to 260°C, more preferably 230 to 250°C. In the method of the present invention, the molding composition is injected into the mold at a pressure in the range of 50 to 1000 bar. In a particular embodiment described herein, the pressure is applied in stages, with the pressure being 50 bar in the first stage and 400 bar in the second stage.

[0097] Furthermore, the injection speed can be divided into stages: a first stage in the range of 0.01 m / s to 0.1 m / s, a second stage in the range of 0.1 m / s to 1 m / s, and a possible third stage in the range of 0.05 m / s to 0.5 m / s. In this specification, the metering stroke is preferably 1 to 4 times the screw diameter.

[0098] Importantly, the method of the present invention is very suitable for producing complex molded parts, such as molded parts having varying thicknesses and / or perforations. The difference in thickness in the corresponding injection mold, in particular the perforations, i.e., the areas into which the molten material is injected into the mold, significantly affects the rheology of the material when the material fills one or more mold cavities. For the purposes of the present invention, a complex molded part is a molded part having one or more of the features described below.

[0099] In one embodiment of the method of the present invention, the complex molded part has different wall thicknesses. The resulting complex molded part preferably has a wall thickness in the range of 1 to 30 mm, which may vary within the complex molded part. For example, the variation in wall thickness can be described by the difference between the minimum and maximum wall thicknesses of the complex molded part, which is greater than 1 mm, preferably greater than 5 mm, and particularly preferably greater than 10 mm. The ratio of maximum wall thickness to minimum wall thickness is preferably greater than 1:20, more preferably greater than 1:10, particularly preferably greater than 1:4, and most preferably greater than 1:2.

[0100] In another embodiment of the method of the present invention, the complex molded part has at least one perforation hole. The wall thickness of the complex molded part is zero at the location of the perforation hole. The molding composition surrounding the perforation hole may result in a uniform or variable wall thickness in the surrounding region, and the wall thickness is preferably within the range described above.

[0101] Another embodiment of the method described above produces a complex molded part having at least one non-flat surface. This surface is preferably convex or concave in design.

[0102] A further aspect of the present invention relates to a method for manufacturing an extruded part, comprising extruding a thermoplastic molding composition at a temperature in the range of 200°C to 320°C, preferably 230°C to 300°C, melting the thermoplastic molding composition and die-casting it into a final part, wherein the thermoplastic molding composition comprises a monoazo dye containing at least one heteroaromatic moiety, and the thermoplastic molding composition comprises less than 100 ppm, preferably less than 50 ppm, of aluminum or a compound thereof and less than 300 ppm, preferably less than 200 ppm, of silicon or a compound thereof.

[0103] The aluminum and silicon content in colored preparations can be easily determined by methods such as atomic emission spectrometry. For example, a sample can be digested and mineralized using the MARS5 PLUS / MARS6 microwave pressure digestion system, and then analyzed using the iCAP® 7400 ICP-OES atomic emission spectrometer, available from ThermoFischer Scientific.

[0104] 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. In the method according to the present invention, a hot melt is extruded from the nozzle of an extruder onto the gap between two calender rolls. The optimal temperature of the molten material is determined, for example, by the composition of the mixture and can therefore vary over a wide range. The preferred temperature of the polyalkyl (meth)acrylate molding compound is in the range of 150 to 300°C, particularly preferably in the range of 180 to 270°C, and particularly more preferably in the range of 200 to 220°C, up to the nozzle inlet. The temperature of the calender rolls is preferably 150°C or less, preferably 60°C to 140°C.

[0105] The thermoplastic molding composition of the present invention can be advantageously used in the manufacture of molded parts having a grayish or jet black appearance and high gloss for use in automobiles, home appliances, electrical equipment, decorative strips and exterior exteriors, and in the exterior areas of automobiles, such as A-, B-, C- or D-pillar exteriors, spoilers, window frames, cover strips, hoods and panels, or as part of radiator grilles, antenna exteriors, side mirrors or front or rear lamps.

[0106] Examples Test method Color measurements were performed using the Color Eye 7000A spectrophotometer, available from X-Rite Inc, Grand Rapids, United States. Subsequently, the color coordinates (L) of the test specimen were measured. * a * and b * The color difference ΔE of each sample was measured using a spectrophotometer in accordance with the standard DIN5033(2017), Parts 1 to 4. CIELAB 1976(D 65 The angle (10°) was determined according to standard DIN6174.

[0107] For transparent colors (measured by transmittance according to Y D65 / 10°1 or greater), ΔE is determined by transmittance measurement. For opaque colors (measured by transmittance according to EN ISO13468-2, with Y D65 / 10°1 or less), ΔE is determined by reflectance measurement.

[0108] Weather resistance tests were conducted using the following parameters. Xenotest • Device: Xenotest Beta LM / 1 • Filter: Xenochrome 300 filter system, daylight color (ISO 4892-2) · Irradiance: 60W / m 2 (300~400nm) • Temperature: Chamber 38±3℃, Black standard 65±3℃ · Humidity: 65±10%RH · 102 minutes dry, 18 minutes water spray Suntest • Device: Xenotest Beta LM / 1 • Filter: Xenochrome 300 filter system, daylight color (ISO 4892-2) · Irradiance: 60W / m 2 (300~400nm) • Temperature: Chamber 38±3℃, Black standard 65±3℃ · Humidity: 65±10%RH • No drizzle cycle

[0109] After 750 hours, Suntest specimens with a ΔE greater than 0.4 were evaluated as specimens with low weathering stability, specimens with a ΔE between 0.1 and 0.4 were evaluated as specimens with moderate weathering stability, and specimens with a ΔE less than 0.1 were evaluated as specimens with excellent weathering stability.

[0110] Over 3000 hours, Xenotest specimens with a ΔE greater than 3 were evaluated as specimens with low weathering stability, specimens with a ΔE of 2 to 3 were evaluated as specimens with moderate weathering stability, and specimens with a ΔE of less than 2 were evaluated as specimens with excellent weathering stability.

[0111] The thermoplastic molding compositions of Examples 1 to 5 were manufactured by the following method.

[0112] Polymer granules and coloring preparations or masterbatches obtained from the manufacturer were used in a rotary mixer to produce a mixture. This mixture was metered and fed via a funnel into the feed zone of a Herbert Stork Maschinenbau GmbH, Moerfelden 30 ESE single-screw extruder. Extrusion was carried out at 250°C. The aeration zone was connected to a vacuum pump. A granulator was connected downstream of the extruder.

[0113] In the second processing step, test specimens were injection molded from the granules thus obtained. In each example, a separate test specimen having a thickness of 3.0 mm was injection molded at 260°C in an Arburg Allrounder320C, available from ARBURG GmbH & Co KG, Lossburg, under the following conditions. Ejection time: 0.92 seconds Material temperature: 250℃ Cylinder temperature: 250~220℃ Mold temperature: 70℃ Switching from injection to holding pressure at 600 bar in the mold. Total cycle time: 40 seconds Injection molding using a sealed, ventilated cylinder

[0114] Example 1 (Comparative Example) I purchased the perinone-type solvent dye MACROLEX® Red E2G (Solvent Red 179) from Lanxess Deutschland GmbH, Cologne.

[0115] Polymethyl methacrylate PLEXIGLAS® 7H, commercially available from Roehm GmbH, was used as the thermoplastic material. The resulting thermoplastic molded composition contained 0.1% by weight of Solvent Red 179 and 0.0001% by weight of color black FW1 (Pigment Black 7).

[0116] The injection-molded specimens were subjected to a 750-hour suntest as described above. The ΔE (transmittance) of the specimens after the suntest was 0.81. This indicates low weather resistance.

[0117] Example 2 (Comparative Example) I purchased the perinone-type solvent dye MACROLEX® Red EG (Solvent Red 135) from Lanxess Deutschland GmbH, Cologne.

[0118] Polymethyl methacrylate PLEXIGLAS® 7H, commercially available from Roehm GmbH, was used as the thermoplastic material. The resulting thermoplastic molded composition contained 0.1% by weight of Solvent Red 135 and 0.0001% by weight of Colour Black FW1 (Pigment Black 7).

[0119] The injection-molded specimens were subjected to a 750-hour suntest as described above. The ΔE (transmittance) of the specimens after the suntest was 0.18. This indicates moderate weather resistance.

[0120] Example 3 (The present invention) I purchased the monoazo dye Oracet® Red 454 (Solvent Red 195) from BASF SE, Ludwigshafen.

[0121] Polymethyl methacrylate PLEXIGLAS® 7H, commercially available from Roehm GmbH, was used as the thermoplastic material. The resulting thermoplastic molded composition contained 0.1% by weight of Solvent Red 195 and 0.0001% by weight of color black FW1 (Pigment Black 7).

[0122] The injection-molded specimens were subjected to a 750-hour suntest as described above. The ΔE (transmittance) of the specimens after the suntest was 0.09. This indicates excellent weather resistance.

[0123] Example 4 (The present invention) Polymethyl methacrylate PLEXIGLAS® 8N, commercially available from Roehm GmbH, was used as the thermoplastic material. The thermoplastic molding composition was as follows: 98.63% by weight of PLEXIGLAS® 8N 0.67 wt% masterbatch containing 0.1 wt% Oracet® Red 454 (Solvent Red 195) (BASF SE, Ludwigshafen) 0.37 wt% masterbatch containing 1.0 wt% color black FW1 (Pigment Black 7) (The Cary Company, Addison, USA) 0.33 wt% masterbatch containing 1.0 wt% Microlith® Blue7080W (Pigment Blue 15:3) (BASF SE, Ludwigshafen) Prepared from a mixture containing [the specified compound].

[0124] The injection-molded test specimens had an aesthetically pleasing appearance.

[0125] The test specimens were subjected to Xenotest for 3000 hours as described above. The ΔE (transmittance) of the test specimens after Xenotest was 1.9. This indicates excellent weather resistance stability.

[0126] Example 4A (Comparative example without carbon black) Polymethyl methacrylate PLEXIGLAS® 8N, commercially available from Roehm GmbH, was used as the thermoplastic material. The thermoplastic molding composition was as follows: 99% by weight of PLEXIGLAS(registered trademark) 8N 0.67 wt% masterbatch containing 0.1 wt% Oracet® Red 454 (Solvent Red 195) (BASF SE, Ludwigshafen) 0.33 wt% masterbatch containing 1.0 wt% Microlith® Blue7080W (Pigment Blue 15:3) (BASF SE, Ludwigshafen) Prepared from a mixture containing [the specified compound].

[0127] The test specimens were subjected to Xenotest for 3000 hours as described above. The ΔE (transmittance) of the specimens after Xenotest was 4.0. This indicates insufficient weather resistance.

[0128] Example 5 (The present invention) Polymethyl methacrylate PLEXIGLAS® 8N, commercially available from Roehm GmbH, was used as the thermoplastic material. The thermoplastic molding composition was as follows: 95.9% by weight of PLEXIGLAS® 8N 0.2 wt% masterbatch containing 10.0 wt% Oracet® Red 454 (Solvent Red 195) (BASF SE, Ludwigshafen) 0.2 wt% masterbatch containing 10.0 wt% Printex® 140 (Pigment Black 7) (The Cary Company, Addison, USA) A 2.6 wt% masterbatch containing 10.0 wt% Oracet® Blue 690 (Solvent Blue 104) (BASF SE, Ludwigshafen). 0.5 wt% masterbatch containing 10.0 wt% Macrolex® Yellow G (Solvent Yellow 114) (manufactured by Lanxess Deutschland GmbH, Cologne) A 0.6 wt% masterbatch containing 1.0 wt% Macrolex® Green G (Solvent Green 28) (manufactured by Lanxess Deutschland GmbH, Cologne). Prepared from a mixture containing [the specified compound].

[0129] The injection-molded test specimens had an aesthetically pleasing appearance.

[0130] The test specimens were subjected to Xenotest for 3000 hours as described above. The ΔE (reflectance) of the test specimens after Xenotest was 0.4. This indicates excellent weather resistance.

[0131] Example 6 (The present invention) Polymethyl methacrylate PLEXIGLAS® 8N, commercially available from Roehm GmbH, was used as the thermoplastic material. The thermoplastic molding composition was as follows: 99.344% by weight of PLEXIGLAS® 8N 0.32 wt% masterbatch containing 0.01 wt% Oracet® Red 454 (Solvent Red 195) (BASF SE, Ludwigshafen) 0.176% masterbatch containing 0.1% color black FW1 (Pigment Black 7) (The Cary Company, Addison, USA) 0.16 wt% masterbatch containing 0.1 wt% Microlith® Blue7080W (Pigment Blue 15:3) (BASF SE, Ludwigshafen) Prepared from a mixture containing [the specified compound].

[0132] The injection-molded test specimens had an aesthetically pleasing appearance.

[0133] The test specimens were subjected to Xenotest for 3000 hours as described above. The ΔE (transmittance) of the test specimens after Xenotest was 0.4. This indicates excellent weather resistance stability.

[0134] Example 7 (The present invention) Polymethyl methacrylate PLEXIGLAS® 8N, commercially available from Roehm GmbH, was used as the thermoplastic material. The thermoplastic molding composition was as follows: 98.864% by weight of PLEXIGLAS® 8N 0.145 wt% masterbatch containing 10 wt% Oracet® Red 454 (Solvent Red 195) (BASF SE, Ludwigshafen) 0.377 wt% masterbatch containing 1 wt% Macrolex® Yellow G (Solvent Yellow 114) (manufactured by Lanxess AG, Leverkusen) 0.322 wt% masterbatch containing 0.1 wt% color black FW1 (Pigment Black 7) (The Cary Company, Addison, USA) 0.292 wt% masterbatch containing 0.1 wt% Microlith® Blue7080W (Pigment Blue 15:3) (BASF SE, Ludwigshafen) Prepared from a mixture containing [the specified compound].

[0135] The injection-molded test specimens had an aesthetically pleasing appearance.

[0136] The test specimens were subjected to Xenotest for 3000 hours as described above. The ΔE (transmittance) of the test specimens after Xenotest was 1.1. This indicates excellent weather resistance.

[0137] Example 7A (Comparative example without monoazo dyes) Solvent Red 179 is used in place of Solvent Red 195 (the monoazo dye used in Example 7 of the present invention).

[0138] Polymethyl methacrylate PLEXIGLAS® 8N, commercially available from Roehm GmbH, was used as the thermoplastic material. The thermoplastic molding composition was as follows: 98.9945% by weight of PLEXIGLAS® 8N 0.0145 wt% Macrolexred E2G (Lanxess AG, Leverkusen) as a pure colorant (Solvent Red 179) 0.377 wt% masterbatch containing 1 wt% Macrolex® Yellow G (Solvent Yellow 114) (manufactured by Lanxess AG, Leverkusen) 0.322 wt% masterbatch containing 0.1 wt% color black FW1 (Pigment Black 7) (The Cary Company, Addison, USA) 0.292 wt% masterbatch containing 0.1 wt% Microlith® Blue7080W (Pigment Blue 15:3) (BASF SE, Ludwigshafen) Prepared from a mixture containing [the specified compound].

[0139] The test specimens were subjected to Xenotest for 3000 hours, as described above. The ΔE (transmittance) of the specimens after Xenotest was 5.4. This indicates insufficient weather resistance.

[0140] Example 7B (Comparative example without carbon black) Polymethyl methacrylate PLEXIGLAS® 8N, commercially available from Roehm GmbH, was used as the thermoplastic material. The thermoplastic molding composition was as follows: 99.186% by weight of PLEXIGLAS® 8N 0.145 wt% masterbatch containing 10 wt% Oracet® Red 454 (Solvent Red 195) (BASF SE, Ludwigshafen) 0.377 wt% masterbatch containing 1 wt% Macrolex® Yellow G (Solvent Yellow 114) (manufactured by Lanxess AG, Leverkusen) 0.292 wt% masterbatch containing 0.1 wt% Microlith® Blue7080W (Pigment Blue 15:3) (BASF SE, Ludwigshafen) Prepared from a mixture containing [the specified compound].

[0141] The test specimens were subjected to Xenotest for 3000 hours, as described above. The ΔE (transmittance) of the test specimens after Xenotest was 3.8. This indicates insufficient weather resistance.

[0142] Example 8 (The present invention) Polymethyl methacrylate PLEXIGLAS® 7N, commercially available from Roehm GmbH, was used as the thermoplastic material. The thermoplastic molding composition was as follows: 97.99% by weight of PLEXIGLAS® 7N 0.38 wt% masterbatch containing 10 wt% Oracet® Red 454 (Solvent Red 195) (BASF SE, Ludwigshafen) 0.45 wt% masterbatch containing 10 wt% Macrolex® Yellow G (Solvent Yellow 114) (Lanxess AG, Leverkusen) 0.38 wt% masterbatch containing 10 wt% color black FW1 (Pigment Black 7) (The Cary Company, Addison, USA) 0.3 wt% masterbatch containing 10 wt% Oracet® Blue 640 (Solvent Blue 104) (BASF SE, Ludwigshafen) 0.5 wt% masterbatch containing 10 wt% Bayferrox® 645T (Pigment Brown 43) (Lanxess AG, Leverkusen) Prepared from a mixture containing [the specified compound].

[0143] The injection-molded test specimens had an aesthetically pleasing appearance.

[0144] The test specimens were subjected to Xenotest for 3000 hours as described above. The ΔE (reflectance) of the test specimens after Xenotest was 0.51. This indicates excellent weather resistance.

[0145] Example 8A (Comparative example without monoazo dyes) Solvent Red 179 is used in place of Solvent Red 195 (the monoazo dye used in Example 8 of the present invention).

[0146] Polymethyl methacrylate PLEXIGLAS® 7N, commercially available from Roehm GmbH, was used as the thermoplastic material. The thermoplastic molding composition was as follows: 98.332% by weight of PLEXIGLAS® 7N 0.038 wt% Macrolexred E2G (Lanxess AG, Leverkusen) as a pure colorant (Solvent Red 179) 0.45 wt% masterbatch containing 10 wt% Macrolex® Yellow G (Solvent Yellow 114) (Lanxess AG, Leverkusen) 0.38 wt% masterbatch containing 10 wt% color black FW1 (Pigment Black 7) (The Cary Company, Addison, USA) 0.3 wt% masterbatch containing 10 wt% Oracet® Blue 640 (Solvent Blue 104) (BASF SE, Ludwigshafen) 0.5 wt% masterbatch containing 10 wt% Bayferrox® 645T (Pigment Brown 43) (Lanxess AG, Leverkusen) Prepared from a mixture containing [the specified compound].

[0147] The test specimens were subjected to Xenotest for 3000 hours as described above. The ΔE (reflectance) of the test specimens after Xenotest was 0.9. This indicates poor weather resistance compared to Example 8.

[0148] Example 8B (Comparative example without carbon black) Polymethyl methacrylate PLEXIGLAS® 7N, commercially available from Roehm GmbH, was used as the thermoplastic material. The thermoplastic molding composition was as follows: 98.37% by weight of PLEXIGLAS® 7N 0.38 wt% masterbatch containing 10 wt% Oracet® Red 454 (Solvent Red 195) (BASF SE, Ludwigshafen) 0.45 wt% masterbatch containing 10 wt% Macrolex® Yellow G (Solvent Yellow 114) (Lanxess AG, Leverkusen) 0.3 wt% masterbatch containing 10 wt% Oracet® Blue 640 (Solvent Blue 104) (BASF SE, Ludwigshafen) 0.5 wt% masterbatch containing 10 wt% Bayferrox® 645T (Pigment Brown 43) (Lanxess AG, Leverkusen) Prepared from a mixture containing [the specified compound].

[0149] The test specimens were subjected to Xenotest for 3000 hours as described above. The ΔE (reflectance) of the test specimens after Xenotest was 1.0. This indicates poor weather resistance in comparison to Example 8.

[0150] Example 9 (The present invention) Polymethyl methacrylate PLEXIGLAS® 7N, commercially available from Roehm GmbH, was used as the thermoplastic material. The thermoplastic molding composition was as follows: 98.52% by weight of PLEXIGLAS® 7N 0.25 wt% masterbatch containing 10 wt% Oracet® Red 454 (Solvent Red 195) (BASF SE, Ludwigshafen) 0.3 wt% masterbatch containing 10 wt% Macrolex® Yellow G (Solvent Yellow 114) (Lanxess AG, Leverkusen) 0.5 wt% masterbatch containing 10 wt% color black FW1 (Pigment Black 7) (The Cary Company, Addison, USA) 0.43 wt% masterbatch containing 10 wt% Sicotan® Yellow K2111 FG (Pigment Brown 24) (BASF SE, Ludwigshafen) Prepared from a mixture containing [the specified compound].

[0151] The injection-molded test specimens had an aesthetically pleasing appearance.

[0152] The test specimens were subjected to Xenotest for 3000 hours, as described above. The ΔE (reflectance) of the test specimens after Xenotest was 0.70. This indicates excellent weather resistance.

[0153] Example 9A (Comparative example without carbon black) Polymethyl methacrylate PLEXIGLAS® 7N, commercially available from Roehm GmbH, was used as the thermoplastic material. The thermoplastic molding composition was as follows: 99.02% by weight of PLEXIGLAS® 7N 0.25 wt% masterbatch containing 10 wt% Oracet® Red 454 (Solvent Red 195) (BASF SE, Ludwigshafen) 0.3 wt% masterbatch containing 10 wt% Macrolex® Yellow G (Solvent Yellow 114) (Lanxess AG, Leverkusen) 0.43 wt% masterbatch containing 10 wt% Sicotan® Yellow K2111 FG (Pigment Brown 24) (BASF SE, Ludwigshafen) Prepared from a mixture containing [the specified compound].

[0154] The test specimens were subjected to Xenotest for 3000 hours as described above. The ΔE (reflectance) of the test specimens after Xenotest was 1.2. This indicates poor weather resistance compared to Example 9.

[0155] Example 10 (The present invention) Polymethyl methacrylate PLEXIGLAS® 7H, commercially available from Roehm GmbH, was used as the thermoplastic material. The thermoplastic molding composition was as follows: 98.1% by weight of PLEXIGLAS® 7H 0.2 wt% masterbatch containing 10 wt% Oracet® Red 454 (Solvent Red 195) (BASF SE, Ludwigshafen) 0.67 wt% masterbatch containing 10 wt% Macrolex® Yellow G (Solvent Yellow 114) (Lanxess AG, Leverkusen) 0.7 wt% masterbatch containing 10 wt% Printex® 140V (Pigment Black 7) (The Cary Company, Addison, USA) 0.33 wt% masterbatch containing 10 wt% Macrolex® Green G (Solvent Green 28) (Lanxess AG, Leverkusen) Prepared from a mixture containing [the specified compound].

[0156] The injection-molded test specimens had an aesthetically pleasing appearance.

[0157] The test specimens were subjected to Xenotest for 3000 hours, as described above. The ΔE (reflectance) of the test specimens after Xenotest was 0.61. This indicates excellent weather resistance.

Claims

1. a) 90.0 to 99.99989% by weight of thermoplastic polymer, b) 0.0001 to 5.0% by weight of carbon black and c) 0.00001 to 5.0% by weight of a monoazo dye containing at least one heteroaromatic moiety. Includes, The thermoplastic polymer is a polyalkyl (meth)acrylate having a weight-average molecular weight Mw of 80,000 g / mol to 180,000 g / mol, and the polymerizable component is determined based on the weight of the polymerizable composition. (i) 50.0 to 99.9% by weight of methyl methacrylate, (ii) 0.1 to 50.0% by weight of acrylic acid esters of C1 to C4 alcohols (iii) 0.0 to 35.0% by weight of at least one further monomer copolymerizable with monomers (i) and (ii) It can be obtained by polymerization of a composition containing, The monoazo dyes are 5-[(3,4-dichlorophenyl)azo]-1,2-dihydro-6-hydroxy-1,4-dimethyl-2-oxonicotinonitrile, 2,3-dihydro-2,2-dimethyl-6-((4-(phenylazo)-1-naphthyl)azo)-1H-perimidine, cyano-5-[[5-cyano-2,6-bis[(3-methoxypropyl)amino]-4-methylpyridine-3-yl]azo]-3-methyl-2-thiophenecarboxylate methyl ester, 5-methyl-2-phenyl-4-phenylazo-4H- A thermoplastic molding composition selected from the list consisting of pyrazole-3-one, 4-[(2,4-dimethylphenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazole-3-one, 3-[(1-oxonaphthalene-2-ylidene)methylhydrazinylidene]-1-propa-2-enylindole-2-one, 4-((o-methoxyphenyl)azo)-3-methyl-1-phenyl-2-pyrazolin-5-one, and 5-methyl-2-phenyl-4-phenylazo-4H-pyrazole-3-one.

2. If the carbon black has a weight-average particle size of 5.0 to 100.0 nm and is determined by the BET method, then 50 to 500 m ２ The thermoplastic molding composition according to claim 1, having a specific surface area of ​​1 / g.

3. - At least one further dye selected from perinone dyes, quinophthalone dyes, and anthraquinone dyes. • At least one phthalocyanine pigment or - Any of the above mixtures The thermoplastic molding composition according to claim 1 or 2, further comprising:

4. The polymerizable component is determined based on the weight of the polymerizable composition. (i) 80.0 to 99.9% by weight of methyl methacrylate, (ii) 0.1 to 20.0% by weight of acrylic acid esters of C1 to C4 alcohols, (iii) 0.0 to 35.0% by weight of at least one further monomer copolymerizable with monomers (i) and (ii) A thermoplastic molding composition according to any one of claims 1 to 3, comprising:

5. The thermoplastic molding composition according to any one of claims 1 to 4, wherein the thermoplastic polymer comprises a polymer matrix and scattering particles dispersed in the polymer matrix, the scattering particles having a weight-average particle size of 0.01 μm to 100.0 μm, and the refractive index of the scattering particles differs from that of the polymer matrix by at least 0.

01.

6. The thermoplastic molding composition according to any one of claims 1 to 5, wherein the thermoplastic molding composition has a melt flow rate of 0.5 to 10.0 g / 10 min when measured at 230°C with a load of 3.8 kg.

7. A method for producing a thermoplastic molded composition according to any one of claims 1 to 6, a) A step of providing a thermoplastic polymer, b) Adding to the thermoplastic polymer from step a) a coloring composition comprising carbon black and a monoazo dye containing at least one heteroaromatic moiety; including, method.

8. The aforementioned coloring composition 1.0 to 30.0% by weight of dispersion additives, 0.05 to 10.0% by weight of carbon black, 0.5 to 50.0% by weight of monoazo dyes and 0.0 to 50.0% by weight of auxiliary additives and liquid A liquid composition containing, The total weight of the components is 100% by weight. The method according to claim 7.

9. The aforementioned coloring composition 0.01 to 40.0% by weight of monoazo dyes, 0.01 to 10.0% by weight of carbon black, 50.0 to 99.98% by weight of thermoplastic polymer, 0.0 to 10.0% by weight of auxiliary additives The method according to claim 7, wherein the masterbatch includes the following:

10. The coloring composition contains less than 100 ppm of aluminum or a compound thereof and less than 300 ppm of silicon or a compound thereof, and / or The colored composition has a mass loss of 15% by weight or less in its dry form when subjected to isothermal thermogravimetric analysis at 260°C for 60 minutes. The method according to any one of claims 7 to 9.

11. The method according to any one of claims 7 to 10, wherein step b) is performed in an extruder.

12. A method for manufacturing molded parts, The process includes a step of injection molding the thermoplastic molding composition according to any one of claims 1 to 6 at a temperature in the range of 200°C to 320°C, The thermoplastic molding composition is injected into a mold capable of manufacturing the molded part. The thermoplastic molding composition, a) 90.0 to 99.99989% by weight of thermoplastic polymer, b) 0.0001 to 5.0% by weight of carbon black and c) 0.00001 to 5.0% by weight of a monoazo dye containing at least one heteroaromatic moiety. Methods that include...

13. A method for manufacturing extruded parts, The thermoplastic molding composition according to any one of claims 1 to 6 is extruded at a temperature in the range of 200°C to 320°C. The thermoplastic molding composition is melted and die-cast into the final part. The thermoplastic molding composition, a) 90.0 to 99.99989% by weight of thermoplastic polymer, b) 0.0001 to 5.0% by weight of carbon black and c) 0.00001 to 5.0% by weight of a monoazo dye containing at least one heteroaromatic moiety. Methods that include...

14. The method according to claim 13, wherein the molded part has different wall thicknesses, one or more perforation holes, at least one non-flat surface, or a combination thereof.

15. A molded part or an extruded part that can be obtained by the method described in any one of claims 12 to 14.

16. A method for producing a thermoplastic molding composition, wherein the thermoplastic molding composition a) 90.0 to 99.99989% by weight of thermoplastic polymer, b) 0.0001 to 5.0% by weight of carbon black and c) 0.00001 to 5.0% by weight of a monoazo dye containing at least one heteroaromatic moiety. Includes, The aforementioned method, a) A step of providing a thermoplastic polymer, b) Adding to the thermoplastic polymer from step a) a coloring composition comprising carbon black and a monoazo dye containing at least one heteroaromatic moiety; Includes, The aforementioned coloring composition 1.0 to 30.0% by weight of dispersion additives, 0.05 to 10.0% by weight of carbon black, 0.5 to 50.0% by weight of monoazo dyes and 0.0 to 50.0% by weight of auxiliary additives and liquid A liquid composition containing, The total weight of the components reaches 100% by weight. The thermoplastic polymer is a polyalkyl (meth)acrylate having a weight-average molecular weight Mw of 80,000 g / mol to 180,000 g / mol, and the polymerizable component is determined based on the weight of the polymerizable composition. (i) 50.0 to 99.9% by weight of methyl methacrylate, (ii) 0.1 to 50.0% by weight of acrylic acid esters of C1 to C4 alcohols (iii) 0.0 to 35.0% by weight of at least one further monomer copolymerizable with monomers (i) and (ii) It can be obtained by polymerization of a composition containing, The monoazo dyes are 5-[(3,4-dichlorophenyl)azo]-1,2-dihydro-6-hydroxy-1,4-dimethyl-2-oxonicotinonitrile, 2,3-dihydro-2,2-dimethyl-6-((4-(phenylazo)-1-naphthyl)azo)-1H-perimidine, cyano-5-[[5-cyano-2,6-bis[(3-methoxypropyl)amino]-4-methylpyridine-3-yl]azo]-3-methyl-2-thiophenecarboxylate methyl ester, 5-methyl-2-phenyl-4-phenylazo A method selected from the list consisting of -4H-pyrazole-3-one, 4-[(2,4-dimethylphenyl)azo]-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazole-3-one, 3-[(1-oxonaphthalene-2-ylidene)methylhydrazinylidene]-1-propa-2-enylindole-2-one, 4-((o-methoxyphenyl)azo)-3-methyl-1-phenyl-2-pyrazolin-5-one and 5-methyl-2-phenyl-4-phenylazo-4H-pyrazole-3-one.

Images