Method for producing plastic compounds having improved properties

Abstract

The present invention relates to a method for producing plastic compounds with improved properties from a blend containing at least two thermoplastic components in a multi-screw machine with screw shafts rotating in the same direction, parallel and at the same speed, the plastic compounds (i) containing no additives that are free-flowing at 23° C., (ii) containing only one additive that is free-flowing at 23° C., or (iii) containing at least two additives that are free-flowing at 23° C. The present invention particularly relates to producing plastic compounds from a blend containing at least two thermoplastic components, at least one of which is a polycarbonate. More specifically, the screw machine is a twin-screw extruder with screw shafts rotating in the same direction, parallel and at the same speed.

Description

[Technical field]

[0001] The present invention provides a method for producing a plastic mass having improved properties from a blend comprising at least two thermoplastic components in a multi-screw machine having co-rotating parallel screw shafts rotating at equal speeds, the plastic mass being (i) does not contain any additive that is free-flowing at 23°C; or (ii) contains only one additive that is free-flowing at 23°C; or (iii) comprises at least two additives that are free-flowing at 23°C.

[0002] In particular, the invention herein provides for the production of plastic mass from a blend comprising at least two thermoplastic components, at least one of which is a polycarbonate. In a further case, in particular, the screw machine is a twin-screw extruder having co-rotating parallel screw shafts rotating at equal speeds. [Background technology]

[0003] Multi-screw machines having co-rotating parallel screw shafts rotating at equal speed are well known from the technical literature, for example from [1] ([1] = Non-Patent Document 1).

[0004] The uses of such screw machines, also called extruders, include the compounding of plastic or viscoelastic masses, in particular the compounding of plastics, in particular melts or solutions of thermoplastic polymers, or of rubber: [1], pp. 50-63.

[0005] When two or more different thermoplastic components with clearly different viscosities are present in the formulation for producing the plastic mass, it is difficult to achieve a good plasticization that combines a high throughput of the plastic mass through the screw machine with a low energy input to the plastic mass.

[0006] The fact that it is difficult to achieve good plasticization is described, for example, in the article "Plastic Polymers: A Case Study of Polymers for Polymerization in Polymeric Polymers, Vol. 1, No. 1, pp. 1111-1115, 2003". The solution proposed there is to explicitly reduce the pellet size of the thermoplastic components used in order to obtain good plasticization. However, only formulations containing only one thermoplastic component, Arnitel® 40D, are used and considered here.

[0007] It is not possible to infer any indications from the presented results for producing plastic masses with good plasticization from polycarbonate-containing blends containing at least two thermoplastic components. Moreover, since the thermoplastic components in the blends are generally not produced in-house but are commercially obtained from external manufacturers, it is difficult to achieve a reduction in the pellet size of the thermoplastic components used.

[0008] In Non-Patent Document 3, a paper resulting from literature survey and experiments, a classification quality calculation model for thermoplastic components is presented and implemented in SIGMA simulation software. Validation experiments of the model are carried out with a mixture of thermoplastic components PA6 and PP. However, Figures 12 to 14 on pages 149 and 150 show that the agreement between experiments and calculations is very low. It is also stated, based on experiments, that the pellet size of the thermoplastic components used, and the ratio of the pellet sizes of the thermoplastic components used, and the flight depth of the screw elements are important process-specific variables to achieve good plasticization. The effect of pellet size is only discussed theoretically, and no details of the experiments with different pellet sizes are given. In addition, it is stated that the viscosity ratio of the thermoplastic components is important for good plasticization. However, only a qualitative description is made.

[0009] The model does not agree well with the experimental results, so it is not possible to deduce any instructions therefrom for producing plastic masses with good plasticization from blends having at least two thermoplastic components, at least one of which is polycarbonate.

[0010] The article, "Elastomers and Polymers: A New Approach to Plasticizing Polymers," (2003) shows that experiments with formulations composed of thermoplastic components show that the quality of plasticization increases linearly with the residence time in the extruder and is also significantly dependent on the screw speed. However, it remains unclear what throughput was used to carry out the experiments. All that is stated is the torque established as a percentage, but there is no information on the torque in nM that corresponds to 100% torque. All experiments were carried out with formulations containing only Arnitel™ 40D as the only thermoplastic component.

[0011] Since only formulations with one thermoplastic component were considered and the setup for the experiments was not documented, it is not possible to deduce any indications that plastic masses with good plasticization can be produced from formulations with at least two thermoplastic components, at least one of which is polycarbonate.

[0012] In the article "Non-Patent Document 5", experiments with blends composed of nylon-4,6, nylon-4,6 and nylon-6, and the addition of other unspecified low-melting additives, show that high energy input, low speed, low torque, and long kneading block zones filled with melt improve the quality of plasticization, while the addition of nylon-6 and / or low-melting additives to nylon-4,6 worsens the plasticization. Furthermore, it is pointed out that in the case of faster speeds, there is an increase in energy input, but at the same time there is a decrease in the quality of plasticization due to inadequate residence time in the extruder.

[0013] Since only qualitative statements are made regarding the influence of process parameters, screw settings and compounding components, no indications can be deduced from the presented results for producing plastic masses with good plasticization from polycarbonate-containing compounds having at least two thermoplastic components. Moreover, no indications are given that would allow good plasticization and at the same time high economic viability to be achieved. A reduction in speed and torque would necessarily lead to a reduction in throughput and therefore a lower economic viability.

[0014] Furthermore, there is no guidance in the prior art as to how the parameters influencing the quality of the plasticization can be related to one another, so that even if one or more of these influencing parameters cannot or should not be changed, for example for cost or quality reasons, one or more of the other influencing parameters can be changed in an appropriate manner to achieve a better plasticization, if at all possible. [Prior art documents] [Non-patent literature]

[0015] [Non-Patent Document 1] Klemens Kohlgrueber: Der gleichlaeufige Doppelschneckenextruder [The Corotating Twin-Shaft Extruder], 2nd edition, Hanser Verlag Munich 2016 [Non-Patent Document 2] "Melting Model for Co-Rotating Twin-Screw Extruders", Elemans, PHM et al., ANTEC 2002, Conference Proceedings, Volume I, Processing, pages 355 to 359 [Non-Patent Document 3] "Melting of polymer blends in co-rotating twin screw extruders. Part I, Part II, Part III", Potente, H. et al., Int. Polymer Processing XVI (2001) 2, pages 124-130, 131-142 and 143-150 [Non-Patent Document 4] "Evaluation of melting performance of a co-rotating twin-screw extruder", Elemans, PHM et al., ANTEC 2002, Conference Proceedings, Volume I, Processing, pages 350-354 [Non-Patent Document 5] "Melting of high-heat Polyamide in a co-rotating twin-screw extruder", Janssen, JMH, Sierksma, WR, ANTEC 2002, Conference Proceedings, Volume III, Special Areas, pages 3712-3715 Summary of the Invention

[0016] The object of the present invention is therefore to provide a method for producing plastic masses with good plasticization in a multi-screw machine with co-rotating parallel screw shafts rotating at equal speeds, in which the influencing parameters influencing the quality of the plasticization are adjusted in such a way that a good plasticization is achieved. A further object of the present invention is to provide a method for producing plastic masses with good plasticization in a multi-screw machine with co-rotating parallel screw shafts rotating at equal speeds, in which the influencing parameters influencing the quality of the plasticization can be adjusted in such a way that a good plasticization is achieved, even if at least one of these influencing parameters cannot or should not be changed, by changing one or more of the other influencing parameters in an appropriate manner. The method according to the present invention therefore achieves a good plasticization quite substantially independently of the screw machine used, its screw set, its diameter, its number of shafts, the components of the formulation for producing the plastic masses, and the process parameters, such as the speed of the screw shafts and the mass flow of the plastic masses through the screw machine. In particular, the formulation for producing the plastic masses comprises at least two thermoplastic components, at least one of which is polycarbonate.

[0017] Good plasticization in the context of the present invention is characterized in that the fully or partially unmelted particles of the thermoplastic component present in the compound are present in less than 5% of the number of pellets produced from the plastic mass, in particular in less than 3% of the number of pellets produced from the plastic mass, very particularly in less than 2% of the number of pellets produced from the plastic mass, and even more particularly in none of the pellets produced from the plastic mass. The presence of fully or partially unmelted particles in more than 2% of the number of pellets, in particular in more than 3% of the number, and very particularly in more than 5% of the number of pellets, is not acceptable.

[0018] Surprisingly, it has been found that the object is achieved by a method having the features of the main claim.

[0019] In particular, it has been found that good plasticization is achieved if what is called the melt rate is kept within a particular range of values. The melt rate is a dimensionless index.

[0020] It has also been found that a better plasticization is achieved, in particular when the melt velocity in a longitudinal section of the screw machine, starting at a distance of twice the housing inner diameter D upstream of the first screw element that is not a conveying element and ending at the last screw element of the screw machine, is between 1.18 and 8, preferably between 1.18 and 5, more preferably between 1.2 and 3, and this melt velocity:

number

[0021] This is especially true for This applies to a method for the production of plastic masses in a multi-screw machine having co-rotating parallel screw shafts rotating at equal speeds, The screw shaft rotates at a speed n. The plastic mass is produced from a blend containing at least two thermoplastic components, at least one of the at least two thermoplastic components is polycarbonate; The plastic chunks are (i) does not contain any additive that is free-flowing at 23°C; or (ii) contains only one additive that is free-flowing at 23°C; or (iii) comprises at least two additives that are free-flowing at 23°C; of the plastic mass at a shear rate γ of 200 1 / s, In case (i), At a temperature of 230°C, In case (ii), 230°C minus 230°C multiplied by twice the mass ratio of only one additive that is free-flowing at 23°C to the mass of the plastic mass. In case (iii), The dynamic viscosity, measured according to ISO 11443:2014 method A2, at a temperature of 230°C minus 2 times the sum of the mass fraction of at least two additives that are free-flowing at 23°C relative to the mass of the plastic mass, is a ratio of 0.3 to 3 for the viscosity, measured according to ISO 11443:2014 method A2, of at least one of these thermoplastic components, measured at a shear rate γ of 200 1 / s and a temperature of 230°C; At least two thermoplastic components have the following characteristics: At least one structural unit is different, or The difference in relative solution viscosity measured according to EN ISO 1628-1:2021 is at least 5%, and The method is characterized by the melting rate.

[0022] By way of further explanation, the following should be noted.

[0023] The speed n is the number of rotations based on a time period and corresponds to the inverse of the rotation period T, that is, n=1 / T.

[0024] The difference in relative solution viscosity, measured according to EN ISO 1628-1:2021, is determined in dichloromethane at 25° C. at a concentration of 5 g sample per liter of dichloromethane using an Ubbelohde viscometer.

[0025] δη1 is the ratio of the dynamic viscosity of the plastic mass at the shear rate γ corresponding to the screw shaft speed n. Since the shear rate is proportional to the speed, a simplified formula is possible:

[0026] d is the diameter of the polycarbonate pellets present in the compound for producing the plastic mass having the highest relative viscosity measured according to EN ISO 1628-1:2021, calculated as the equivalent sphere diameter from the weight and solid density of 100 pellets as follows:

number

[0027] In the context of the present invention, based on a multi-screw machine, details regarding position and direction should always be considered in the conveying direction of the entire multi-screw machine.

[0028] Preferably, according to the invention, the multi-screw machine is a twin-screw extruder having co-rotating parallel screw shafts rotating at equal speeds, on which are mounted screw elements, each preferably tightly meshing with the respective directly adjacent screw elements of the respective directly adjacent screw shaft, which are externally surrounded by an outer housing, which likewise has an inner contour adapted to the screw shafts. The housing of a twin-screw extruder with mutually parallel arranged screw shafts may be designed so that it is possible to both heat and cool it.

[0029] Alternatively, according to the invention, the multiscrew machine is preferably a multiscrew extruder with mutually annularly arranged co-rotating parallel screw shafts rotating at equal speed. Such a multiscrew extruder has 8 to 16, usually 10 or 12, co-rotating screw shafts. In such a screw machine too, the screw shafts are preferably fitted with screw elements, each of which meshes tightly with the respective directly adjacent screw elements of the respective directly adjacent screw shaft. These screw shafts are arranged annularly around an inner core having a contour adapted to the screw shaft to which the screw elements are attached. Each screw shaft is directly adjacent to the other two screw shafts. These screw shafts are externally surrounded by an outer housing having an inner contour similarly adapted to the screw shafts. The housing and / or core of a multiscrew extruder with mutually annularly arranged screw shafts may be designed to allow both heating and cooling.

[0030] In the context of the present invention, such a multiscrew extruder having screw shafts arranged annularly with respect to one another will hereinafter also be referred to as a ring extruder.

[0031] The screw elements of the ring extruder are the same as those of a twin-screw extruder serving the same process engineering objectives. The process zones of the ring extruder are also the same as those of a twin-screw extruder serving the same process engineering objectives.

[0032] Ring extruders are known per se, for example from DE 44 12 725 A1, DE 44 12 741 A1, DE 196 22 582 A1, DE Utility Model No. 202007004997 A1, DE Utility Model No. 202007005010 A1, WO 03020493 A1 and WO 2006045412 A1, and also from the publication "Compoundieren mit zwoelf Wellen" ["Compounding with Twelve Shafts"] Carl Hanser Verlag, Munich, KU Kunststoffe, volume 90 (2000) 8, pages 60 to 62.

[0033] The plastic mass produced by the process according to the invention is in particular a melt of a blend containing at least two thermoplastic components, at least one of which is polycarbonate. The second thermoplastic component may be a polycarbonate, but also a different thermoplastic polymer. The same applies to any further thermoplastic components used. Each of these further thermoplastic components that can be used may be, independently of the others, a polycarbonate or a different thermoplastic polymer. It is therefore also possible that all thermoplastic components of the blend according to the invention are polycarbonates.

[0034] In the context of the present invention, the blend is present from the intake of the multi-screw machine up to a distance of twice the housing inner diameter upstream of the first screw element that is not a conveying element, and the plastic mass is present after the first screw element that is not a conveying element. In the length of the multi-screw machine covered by the conveying elements from a distance of twice the housing inner diameter to just before the end of the first screw element that is not a conveying element, the blend is converted into a plastic mass.

[0035] For the purposes of the present invention, "polycarbonate" refers to both homopolycarbonates and copolycarbonates. These polycarbonates may be linear or branched, as is well known. Mixtures of polycarbonates can also be used according to the present invention.

[0036] Up to 80 mol %, preferably from 20 mol % to up to 50 mol %, of the carbonate groups in the polycarbonates used according to the invention may be replaced by preferably aromatic dicarboxylic ester groups. Polycarbonates of this type which incorporate both acid moieties from carbonic acid and, preferably, from aromatic dicarboxylic acids in the molecular chain, are called aromatic polyestercarbonates.

[0037] The replacement of carbonate groups by aromatic dicarboxylate groups is substantially stoichiometric and quantitative, meaning that the molar ratio of the co-reactants is reflected in the finished polyestercarbonate. The aromatic dicarboxylate groups can be incorporated randomly or in blocks.

[0038] The thermoplastic polycarbonates, including thermoplastic polyester carbonates, have an average molecular weight M, determined by GPC (gel permeation chromatography in methylene chloride using polycarbonate as standard), of 15 kg / mol to 50 kg / mol, preferably 20 kg / mol to 35 kg / mol, more preferably 23 kg / mol to 33 kg / mol. w has.

[0039] The preferred aromatic polycarbonates and aromatic polyestercarbonates are prepared in known manner from diphenols, carbonic acid or carbonic acid derivatives, and, in the case of polyestercarbonates, preferably aromatic dicarboxylic acids or dicarboxylic acid derivatives, and optionally chain terminators and branching agents.

[0040] The details of the preparation of polycarbonates have been described in numerous patent specifications over the past forty years or so. Reference may be made here, by way of example, to Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Vol. 9, Interscience Publishers, New York, London, Sydney 1964, D. Freitag, U. Grigo, PR Mueller, H. Nouvertne, Bayer AG, "Polycarbonates" in Encyclopedia of Polymer Science and Engineering, Vol. 11, 2nd edition, 1988, pp. 648-718, and finally U. Grigo, K. Kirchner and PR Mueller "Polycarbonate" in Becker / Braun, Kunststoff-Handbuch [Plastics Handbook], Vol. 3 / 1, "Polycarbonate, Polyacetale, Polyester, Celluloseester" [Polycarbonates, polyacetals, polyesters, cellulose esters], Carl Hanser Publishers, Munich, Vienna 1992, pp. 117-299. [Polycarbonates] is referenced.

[0041] Aromatic polycarbonates and polyestercarbonates are prepared, for example, by reacting diphenols with carbonyl halides, preferably phosgene, and / or aromatic dicarbonyl halides, preferably benzene dicarbonyl halides, by interfacial methods, optionally using chain terminators and optionally using trifunctional or higher branching agents, where the preparation of polyestercarbonates is achieved by replacing part of the carbonic acid derivatives with aromatic dicarboxylic acids or derivatives of dicarboxylic acids, in particular with aromatic dicarboxylic ester structural units, depending on the proportion of carbonate structural units replaced in the aromatic polycarbonates.Preparation via melt polymerization methods by reacting diphenols with, for example, diphenyl carbonate is also possible.

[0042] Dihydroxyaryl compounds suitable for the preparation of polycarbonates have the formula (1): HO-Z-OH (1) where Z is an aromatic group having 6 to 30 carbon atoms, which may contain one or more aromatic rings, which may be substituted, and which may contain an aliphatic or alicyclic radical or an alkylaryl or heteroatom as a bridging element.

[0043] Z in formula (1) is preferably a group represented by formula (2): [ka] (In the formula, R 6 and R 7 are independently H, C1 to C 18 Alkyl, C1-C 18 Alkoxy, halogen such as Cl or Br, or in each case optionally substituted aryl or aralkyl, preferably H or C1-C 12 alkyl, more preferably H or C1-C8 alkyl, even more preferably H or methyl, and X represents a single bond, -SO2-, -CO-, -O-, -S-, C1-C6 alkylene, C2-C5 alkylidene, or C5 or C6 cycloalkylidene optionally substituted by C1-C6 alkyl, preferably methyl or ethyl, or a C6-C6 alkyl group optionally fused to a further aromatic ring containing a heteroatom; 12 represents a radical of arylene.

[0044] X is a single bond, a C1 to C5 alkylene, a C2 to C5 alkylidene, a C5 or C6 cycloalkylidene, -O-, -SO-, -CO-, -S-, -SO2-, or a group represented by formula (2a): [ka] It is preferred that the radical represents

[0045] Examples of diphenols suitable for producing polycarbonates include hydroquinone, resorcinol, dihydroxydiphenyl, bis(hydroxyphenyl)alkanes, bis(hydroxyphenyl)cycloalkanes, bis(hydroxyphenyl)sulfides, bis(hydroxyphenyl)ethers, bis(hydroxyphenyl)ketones, bis(hydroxyphenyl)sulfones, bis(hydroxyphenyl)sulfoxides, α,α'-bis(hydroxyphenyl)diisopropylbenzene, phthalimidines derived from isatin or phenolphthalein derivatives, and their ring-alkylated, ring-arylated, and ring-halogenated compounds.

[0046] Preferred bisphenols are 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)-1-phenylpropane, 1,1-bis(4-hydroxyphenyl)phenylethane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A (BPA)), 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (bisphenol M), 2,2-bis(3-methyl-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl)propane, Bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl)sulfone, 2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,3-bis[2-(3,5-dimethyl-4-hydroxyphenyl)-2-propyl]benzene, 1,1-bis(4-hydroxyphenyl)cyclohexane and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC (BPTMC)), and formulas (IV) to (VI): [ka] wherein R' in each occurrence is C1-C4 alkyl, aralkyl or aryl, preferably methyl or phenyl.

[0047] Particularly preferred bisphenols are 4,4'-dihydroxydiphenyl, 1,1-bis(4-hydroxyphenyl)phenylethane, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A (BPA)), 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC (BPTMC)), as well as the dihydroxy compounds of formula (IV), (V), and (VI), in which R' in each case represents C1-C4 alkyl, aralkyl, or aryl, preferably methyl or phenyl.

[0048] These and other suitable diphenols are described, for example, in U.S. Pat. Nos. 3,028,635, 2,999,825, 3,148,172, 2,991,273, 3,271,367, 4,982,014 and 2,999,846, DE-A-1,570,703, DE-A-2,063,050, DE-A-2,036,052, DE-A-2,211,956 and DE-A-3,832,396, FR-A-1,561,518, the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York, 1964" and in JP-A-61-62039, JP-A-61-62040 and JP-A-61-105550.

[0049] In the case of homopolycarbonates, only one diphenol is used, in the case of copolycarbonates, two or more diphenols are used. The diphenols used may be contaminated with impurities from their own synthesis, handling, and storage, as well as all other chemicals and auxiliaries added to the synthesis. However, it is desirable to use raw materials of the highest possible purity.

[0050] In particular, the polycarbonates according to the invention are composed exclusively of atoms selected from one or more of the elements carbon (C), hydrogen (H), oxygen (O), nitrogen (N), sulfur (S), chlorine (Cl) and bromine (Br).

[0051] Examples of suitable carbonic acid derivatives include phosgene or diphenyl carbonate.

[0052] Suitable chain terminators that may be used in the preparation of the polycarbonates include monophenols, examples of which include phenol itself, alkylphenols such as the cresols, p-tert-butylphenol, cumylphenol, and the like, as well as mixtures thereof.

[0053] Preferred chain terminators are linear or branched, preferably unsubstituted, C1-C 30 Particularly preferred chain terminators are phenol, cumylphenol and / or p-tert-butylphenol, which are mono- or polysubstituted by alkyl radicals or tert-butyl.

[0054] The amount of chain terminator used is preferably between 0.1 mol % and 5 mol %, based on the moles of diphenols used in each case. The chain terminator can be added before, during or after the reaction with the carbonic acid derivative.

[0055] Suitable branching agents are the tri- or higher functional compounds known in polycarbonate chemistry, in particular compounds having three or more phenolic OH groups.

[0056] Examples of suitable branching agents include 1,3,5-tri(4-hydroxyphenyl)benzene, 1,1,1-tri(4-hydroxyphenyl)ethane, tri(4-hydroxyphenyl)phenylmethane, 2,4-bis(4-hydroxyphenylisopropyl)phenol, 2,6-bis(2-hydroxy-5'-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane, tetra(4-hydroxyphenyl)methane, tetra(4-(4-hydroxyphenylisopropyl)phenoxy)methane, and 1,4-bis((4',4''-dihydroxytriphenyl)methyl)benzene and 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole.

[0057] Preferably, the amount of branching agent optionally used is between 0.05 mol % and 2.00 mol %, based on the moles of diphenol used in each case.

[0058] The branching agent may be initially charged together with the diphenol and the chain terminator in the alkaline aqueous phase or may be added as a solution in an organic solvent prior to the phosgenation. In the case of the transesterification process, the branching agent is used together with the diphenol.

[0059] Particularly preferred polycarbonates are homopolycarbonates based on bisphenol A, homopolycarbonates based on 1,3-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and homopolycarbonates based on the monomers bisphenol A on the one hand and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane on the other hand and the polycarbonates of the formulae (IV) to (VI): [ka] and a monomer selected from the group comprising bisphenols of the formula: (wherein R' represents in each case C1-C4 alkyl, aralkyl or aryl, preferably methyl or phenyl).

[0060] Preferred methods for producing the polycarbonates, including the polyestercarbonates used according to the present invention, are the known interfacial process and the known melt transesterification process (see, for example, WO 2004 / 063249, WO 2001 / 05866, WO 2000 / 105867, U.S. Pat. No. 5,340,905, U.S. Pat. No. 5,097,002, U.S. Pat. No. 5,717,057).

[0061] As the polycarbonate, an aromatic polycarbonate based on bisphenol A, in particular a linear aromatic polycarbonate based on bisphenol A, is most preferred.

[0062] The proportion of polycarbonate in the mixture for producing the plastic mass is 20% to 98% by weight, in particular 40% to 80% by weight.

[0063] If one thermoplastic component of the at least two thermoplastic components of the blend according to the invention is not a polycarbonate, or if the optionally further thermoplastic component of the blend according to the invention is not a polycarbonate, the further thermoplastic component or the optionally further thermoplastic component is independently selected from the group comprising the following elements: polyester carbonates, polyamides, polyesters, in particular polybutylene terephthalate and polyethylene terephthalate, polylactides, polyethers, thermoplastic polyurethanes, polyacetals, fluoropolymers, in particular polyvinylidene fluoride, polyethersulfones, polyolefins, in particular polyethylene and polypropylene, polyimides, polyacrylates, in particular poly(methyl)methacrylate, polyphenylene oxide, polyphenylene sulfide, polyether ketones, polyarylether ketones, styrene polymers, in particular polystyrene, styrene copolymers, in particular styrene-acrylonitrile copolymers, rubber modified vinyl (co)polymers and polyvinyl chloride.

[0064] If the thermoplastic component(s) present in the formulation is / are one such thermoplastic component(s) which is / are not polycarbonate(s), it is preferred according to the invention that this / these thermoplastic component(s) are / are selected from the group of rubber modified vinyl (co)polymers.

[0065] In other words, in a particular embodiment of the present invention, the formulation for producing the plastic mass contains, in addition to at least one thermoplastic component which is a polycarbonate, also frequently referred to in this context as component A, at least one thermoplastic component which is a rubber-modified vinyl (co)polymer, also referred to herein as component B.

[0066] The rubber modified vinyl (co)polymers preferably used in accordance with the present invention include rubber-based graft polymers and optionally rubber-free vinyl (co)polymers.

[0067] The graft polymer used in component B according to the present invention is B.1 from 5% to 95% by weight, preferably from 20% to 92% by weight, in particular from 30% to 91% by weight, of at least one vinyl monomer, based on the graft polymer, B.2 95% to 5% by weight, preferably 80% to 8% by weight, in particular 70% to 9% by weight, based on the graft polymer, of one or more elastomeric graft substrates having a glass transition temperature of less than -50 ° C, more preferably less than -60 ° C, particularly preferably less than -70 ° C, Includes.

[0068] Unless otherwise stated in the present invention, the glass transition temperature is determined for all components by differential scanning calorimetry (DSC) according to DIN EN 61006 (1994 edition) at a heating rate of 10 K / min by determination of the Tg as the midpoint temperature (tangent method).

[0069] The graft base material B.2 generally has a median particle size (D50) of 0.05 μm to 10.00 μm, preferably 0.1 μm to 5.0 μm, more preferably 0.2 μm to 1.5 μm.

[0070] The median particle size D50 is the diameter above which 50% by weight of the particles lie and below which 50% by weight of the particles lie. Unless otherwise stated in the present invention, it is determined for all components by ultracentrifugation measurements (W. Scholtan, H. Lange, Kolloid, Z. und Z. Polymere 250 (1972), 782-1796).

[0071] The monomers B.1 are preferably B.1.1 65% to 85% by weight, more preferably 70% to 80% by weight, even more preferably 74% to 78% by weight, of vinyl aromatics and / or ring-substituted vinyl aromatics (for example styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or (C1-C8)-alkyl (meth)acrylates, for example methyl methacrylate, ethyl methacrylate, in each case based on the sum of B.1.1 and B.1.2, B.1.2 15% to 35% by weight, more preferably 20% to 30% by weight, even more preferably 22% to 26% by weight, of vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (C1-C8)-alkyl (meth)acrylates, for example methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or derivatives of unsaturated carboxylic acids (for example anhydrides and imides), for example maleic anhydride, in each case relative to the total of B.1.1 and B.1.2, It is a mixture of.

[0072] Preferred monomers B.1.1 are selected from at least one of the monomers styrene, α-methylstyrene and methyl methacrylate, and preferred monomers B.1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride and methyl methacrylate. Particularly preferred monomers are B.1.1 styrene and B.1.2 acrylonitrile. Alternatively preferred monomers are B.1.1 methyl methacrylate and B.1.2 methyl methacrylate.

[0073] Suitable graft substrates B.2 for the graft polymers include, for example, diene rubbers, EP(D)M rubbers, i.e. based on ethylene / propylene, and optionally diene, acrylate, polyurethane, silicone, chloroprene, ethylene / vinyl acetate and acrylate-silicone hybrid rubbers.

[0074] Preferred graft substrates B.1.2 are diene rubbers, preferably containing butadiene, or copolymers of dienes, preferably containing butadiene, and further copolymerizable vinyl monomers (for example according to B.1.1 and B.1.2), or mixtures of one or more of the abovementioned components.

[0075] A particularly preferred graft substrate B.2 is a pure polybutadiene rubber. In a further preferred embodiment, B.2 is a styrene-butadiene rubber, more preferably a styrene-butadiene block copolymer rubber.

[0076] The gel content of the graft substrate B.2, measured as the insoluble fraction in toluene, in each case relative to B.2, is at least 30% by weight, preferably at least 40% by weight and in particular at least 60% by weight.

[0077] The gel content of the graft polymers in the graft substrate B.2 / component B is determined in suitable solvents at 25° C. as the content that is insoluble in these solvents (M. Hoffmann, H. Kroemer, R. Kuhn, Polymeranalytik I und II, Georg Thieme-Verlag, Stuttgart 1977).

[0078] Suitable polymers of component B are, for example, ABS polymers or MBS polymers, as described, for example, in DE-A 2 035 390 (=U.S. Pat. No. 3,644,574) or DE-A 2 248 242 (=GB Pat. No. 1,409,275) or in Ullmanns Enzyklopaedie der Technischen Chemie [Ullmann's Encyclopedia of Industrial Chemistry], vol. 19 (1980), p. 280 ff.

[0079] The graft copolymers in component B are prepared by free-radical polymerization, for example emulsion, suspension, solution or bulk polymerization. It is also possible to use mixtures of graft polymers prepared by different methods as component B.

[0080] If the graft polymers B are prepared by emulsion polymerization, they are B.1 5% to 75% by weight, preferably 20% to 60% by weight, more preferably 25% to 50% by weight, of at least one vinyl monomer, based on the graft polymer; B.2 95% to 25% by weight, preferably 80% to 40% by weight, more preferably 75% to 50% by weight, based on the graft polymer, of one or more rubber-elastic graft substrates having a glass transition temperature of less than -50°C, even more preferably less than -60°C, particularly preferably less than -70°C; Includes.

[0081] The graft substrate B.2 of the graft polymer B produced by emulsion polymerization has a median particle size (D50) of 0.05 μm to 2.00 μm, preferably 0.1 μm to 1.0 μm, more preferably 0.2 μm to 0.5 μm.

[0082] The graft polymer B produced by emulsion polymerization preferably has a gel content, measured in acetone as a solvent, of at least 30% by weight, more preferably at least 60% by weight, and even more preferably at least 80% by weight.

[0083] If the graft polymers B are produced by suspension, solution or bulk polymerization, they may be B.1 80% to 95% by weight, preferably 84% to 92% by weight, more preferably 87% to 91% by weight, of at least one vinyl monomer, based on the graft polymer; B.2 20% to 5% by weight, preferably 16% to 8% by weight, more preferably 13% to 9% by weight, of one or more elastomeric graft substrates having a glass transition temperature of less than -50°C, even more preferably less than -60°C, particularly preferably less than -70°C, based on the graft polymer; Includes.

[0084] The graft substrate B.2 of the graft polymer B produced by suspension polymerization, solution polymerization or bulk polymerization has a median particle size (D50) of 0.3 μm to 10.00 μm, preferably 0.4 μm to 5.0 μm, more preferably 0.5 μm to 1.5 μm.

[0085] The graft polymer B produced by suspension polymerization, solution polymerization or bulk polymerization has a gel content measured in acetone as a solvent of preferably 10% by weight to 50% by weight, more preferably 15% by weight to 40% by weight, and further preferably 18% by weight to 30% by weight.

[0086] Particularly suitable graft polymers produced by an emulsion polymerization process are ABS polymers produced in an emulsion polymerization process by redox initiation with an initiator system composed of an organic hydroperoxide and ascorbic acid, for example according to US Pat. No. 4,937,285.

[0087] Additionally, particularly suitable graft polymers produced by emulsion polymerization processes are MBS modifiers having a core-shell structure.

[0088] Component B may also contain free vinyl (co)polymers composed of monomers according to B.1, i.e. in a form that is not chemically bound to the rubber substrate and is not included in the rubber particles. This may arise in component B as a result of the preparation in the polymerization of the graft polymer (grafting to the graft substrate is not necessarily complete) or else it may be the result of a separate polymerization and inclusion in component B. It is likewise possible that part of the free vinyl (co)polymer in component B originates from the graft polymer itself as a result of the preparation, and another part is polymerized separately and added to component B. The proportion of free vinyl (co)polymer (whatever its origin) in component B, measured as the acetone-soluble fraction, is preferably at least 5% by weight, more preferably at least 30% by weight and particularly preferably at least 50% by weight, relative to component B.

[0089] The free vinyl (co)polymer in the rubber-modified vinyl copolymer according to component B has a weight average molecular weight M of 30 kg / mol to 250 kg / mol, preferably 70 kg / mol to 200 kg / mol, in particular 90 kg / mol to 180 kg / mol. w has.

[0090] In the context of the present invention, the weight average molecular weight M of the free vinyl (co)polymer in component B w is determined by gel permeation chromatography (GPC) in tetrahydrofuran against polystyrene standards.

[0091] The formulation for producing the plastic mass may contain at least two thermoplastic components in pure form or as a mixture with fillers and reinforcing agents, in particular glass fibers or talc.

[0092] In a preferred embodiment, one or more additives are added to the blend. The particular additive may be a solid, liquid or solution, and may be added to the multi-screw machine together with the blend, optionally with one or more further additives, if present, or alternatively, fed to the multi-screw machine via a separate side stream, optionally with one or more further additives, if present.

[0093] Additives can impart various properties to polymers. They can be, for example, colorants, pigments, processing aids, fillers, antioxidants, reinforcing agents, UV absorbers and light stabilizers, metal deactivators, peroxide scavengers, base stabilizers, nucleating agents, benzofurans and indolinones with stabilizing or antioxidant effects, release agents, flame retardant additives, antistatic agents, dyes and melt stabilizers. Examples of these are carbon black, glass fibers, clays, mica, graphite fibers, titanium dioxide, carbon fibers, carbon nanotubes, ionic liquids and natural fibers. Suitable additives are described, for example, in WO 99 / 55772 (pp. 15 to 25), "Plastics Additives", R. Gaechter and H. Mueller, Hanser Publishers 1983, "Additives for Plastics Handbook, John Murphy, Elsevier, Oxford 1999", and "Plastics Additives Handbook, Hans Zweifel, Hanser, Munich 2001".

[0094] Preferably, according to the invention, it is possible to add an additive that is free-flowing at 23°C to the plastic mass, or it is possible to add a number of additives that are free-flowing at 23°C to the plastic mass, for example two, three or four such additives that are free-flowing at 23°C.

[0095] According to the present invention, phosphorus-containing flame retardants are particularly preferred as additives that are free-flowing at 23°C.

[0096] The phosphorus-containing flame retardants in the context of the present invention are preferably selected from the group of monomeric and oligomeric phosphoric and phosphonic esters, phosphazenes and salts of phosphinic acids, and it is also possible to use mixtures of compounds selected from one of these groups or from various groups as flame retardants. It is also possible to use other phosphorus compounds not specifically mentioned here, alone or in any desired combination with other phosphorus compounds.

[0097] Preferred monomeric and oligomeric phosphate and phosphonate esters have the general formula (III): [ka] is a phosphorus compound of During the ceremony, R 1 , R 2 , R 3 and R 4 are each independently optionally halogenated C1-C8-alkyl, each optionally alkyl-substituted, preferably C1-C4-alkyl-substituted and / or halogen-substituted, preferably chlorine- or bromine-substituted, C5- or C6-cycloalkyl, C6-C 20 -aryl or C7-C 12 -aralkyl, n is independently 0 or 1; q is 0 to 30; X is a monocyclic or polycyclic aromatic radical having 6 to 30 carbon atoms, or a linear or branched aliphatic radical having 2 to 30 carbon atoms, which may be OH-substituted and may contain up to 8 ether bonds.

[0098] R 1 , R 2 , R 3 and R 4 Preferably, each independently represents C1-C4-alkyl, phenyl, naphthyl or phenyl-C1-C4-alkyl. 1 , R2 , R 3 and R 4 The radicals may likewise be substituted with halogen and / or alkyl groups, preferably chlorine, bromine and / or C1-C4-alkyl.Particularly preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl, as well as the corresponding brominated and chlorinated derivatives thereof.

[0099] X in formula (III) is preferably a monocyclic or polycyclic aromatic radical having from 6 to 30 carbon atoms, the latter preferably being derived from a diphenol.

[0100] In formula (III), n may independently be 0 or 1, and n is preferably 1.

[0101] q has a value of from 0 to 30. If a mixture of different components of formula (III) is used, the mixture may preferably have a number average q value of from 0.3 to 10, more preferably from 0.5 to 10, especially from 1.05 to 1.4.

[0102] X is more preferably [ka] or chlorinated or brominated derivatives thereof, in particular X is derived from resorcinol, hydroquinone, bisphenol A or diphenylphenol. Particularly preferably, X is derived from bisphenol A.

[0103] As component C according to the invention, monophosphates (q=0), oligophosphates (q=1 to 30) or mixtures of monophosphates and oligophosphates may be used.

[0104] Monophosphorus compounds of formula (III) are in particular tributyl phosphate, tris(2-chloroethyl)phosphate, tris(2,3-dibromopropyl)phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, diphenyl 2-ethylcresyl phosphate, tri(isopropylphenyl)phosphate, halogen-substituted aryl phosphates, dimethyl methylphosphonate, diphenyl methylphosphenate, diethylphenylphosphonate, triphenylphosphine oxide or tricresylphosphine oxide.

[0105] Most preferred as component D is a compound represented by formula (IIIa): [ka] It is an oligophosphate based on bisphenol A.

[0106] Phosphorus compounds of formula (III) are known (see, for example, EP-A-363608, EP-A-640655) or can be prepared in a similar manner according to known methods (see, for example, Ullmanns Enzyklopaedie der technischen Chemie, vol. 18, p. 301 ff. 1979; Houben-Weyl, Methoden der organischen Chemie [Methods of Organic Chemistry], vol. 12 / 1, p. 43; Beilstein vol. 6, p. 177). A particular example selected from phosphorus compounds of formula (III) is bisphenol A bis(diphenyl phosphate), also called BDP for short. This BDP is also preferred as an additive that is free-flowing at 23°C.

[0107] The average q value can be determined by determining the composition (molecular weight distribution) of the phosphate mixture using a suitable method (gas chromatography (GC), high pressure liquid chromatography (HPLC), gel permeation chromatography (GPC)) and using this to calculate the average value of q.

[0108] Phosphazenes are represented by the formula (IVa) and the formula (IVb): [ka] is a compound of During the ceremony, R is, in each case identical or different, amino, in each case optionally halogenated, preferably fluorinated, C1-C8-alkyl or C1-C8-alkoxy, in each case optionally alkyl-substituted, preferably C1-C4-alkyl-substituted and / or halogen-substituted, preferably chlorine- and / or bromine-substituted, C5 or C6-cycloalkyl, C6-C 20 -aryl, preferably phenyl or naphthyl, C6-C 20 -aryloxy, preferably phenoxy, naphthyloxy, or C 12 -aralkyl, preferably phenyl-C1-C4-alkyl, k is 0 or a number from 1 to 15, and preferably a number from 1 to 10.

[0109] Examples include propoxyphosphazene, phenoxyphosphazene, methylphenoxyphosphazene, aminophosphazene and fluoroalkylphosphazenes. Phenoxyphosphazene is preferred.

[0110] Phosphazenes can be used alone or in mixtures. The R radicals can always be the same or two or more radicals can be different in formula (IVa) and formula (IVb). Phosphazenes and their preparation are described, for example, in EP-A-728811, DE-A-1961668 and WO-A-97 / 40092.

[0111] A salt of a phosphinic acid in the context of the present invention is understood to mean a salt of a phosphinic acid with any metal cation. It is also possible to use a mixture of salts that are different in terms of their metal cations. The metal cation is preferably a salt of the main group 1 of the periodic table (alkali metals, preferably Li + , Na + , K + ), main group 2 (alkaline earth metals, preferably Mg 2+ , Ca 2+ , Sr 2+ , B.A. 2+ , more preferably Ca 2+ ) or main group 3 (an element of the boron group, preferably Al 3+ ) and / or transition groups 2, 7 or 8 (preferably Zn 2+ , Mn 2+ , Fe 2+ , Fe 3+ ) is a cation of a metal.

[0112] Formula (V): [ka] (In the formula, M m+ It is preferred to use a salt or a mixture of salts of a phosphinic acid which is a metal cation of main group 1 (alkali metals, m=1), main group 2 (alkaline earth metals, m=2) or main group 3 (m=3) or transition group 2, 7 or 8 (where m is an integer from 1 to 6, preferably from 1 to 3, more preferably 2 or 3) of the periodic table.

[0113] More preferably, in formula (V), When m=1, the metal cation M + =Li + , Na + , K + , When m=2, the metal cation M 2+ =Mg 2+ , Ca 2+ , Sr 2+ , B.A. 2+ , and When m=3, the metal cation M 3+ =Al3+ and Most preferred is Ca 2+ (m=2).

[0114] In a preferred embodiment, the median particle size d50 of the phosphine salt (component C) is less than 80 μm, preferably less than 60 μm, more preferably d50 is between 10 μm and 55 μm. The median particle size d50 is the diameter above which 50% by weight of the particles lie and below which 50% by weight of the particles lie. It is also possible to use mixtures of salts that differ with respect to their median particle size d50.

[0115] This additive, which is free-flowing at 23° C. and is particularly preferred according to the invention, is furthermore preferably added to the plastic mass via a side stream from the last conveying element before the first screw element which is not a conveying element. More preferably, this additive, which is free-flowing at 23° C. and is particularly preferred according to the invention, is added to the plastic mass downstream of the last conveying element before the first screw element which is not a conveying element. Most preferably, this additive, which is free-flowing at 23° C. and is particularly preferred according to the invention, is added to the plastic mass downstream of the melting zone.

[0116] Examples of suitable antioxidants / thermal stabilizers include alkylated monophenols, alkylthiomethylphenols, hydroquinones and alkylated hydroquinones, tocopherols, hydroxylated thiodiphenyl ethers, alkylidene bisphenols, O-, N-, and S-benzyl compounds, hydroxybenzylated malonates, aromatic hydroxybenzyl compounds, triazine compounds, acylaminophenols, esters of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, esters of β-(5-tert-butyl-4-hydroxy-3-methylphenyl)propionic acid, esters of β-(3,5-dicyclohexyl-4-hydroxyphenyl)propionic acid, esters of 3,5-di-tert-butyl-4-hydroxyphenylacetic acid, amides of β-(3,5-di-tert-butyl-4-hydroxyphenyl)propionic acid, suitable thiosynergists, secondary antioxidants, phosphites and phosphonites, benzofuranones, and indolinones.

[0117] Organophosphites, organophosphonates and organophosphanes, mainly those in which the organic radical is optionally fully or partially substituted with an aromatic radical, are preferred.

[0118] Suitable complexing agents for the neutralization of heavy metals and traces of alkali are ortho- and metaphosphoric acids, fully or partially esterified phosphates or phosphites.

[0119] Suitable light stabilizers (UV absorbers) are 2-(2'-hydroxyphenyl)benzotriazoles, 2-hydroxybenzophenones, esters of substituted and unsubstituted benzoic acid, acrylates, sterically hindered amines, oxamides, as well as 2-(hydroxyphenyl)-1,3,5-triazines and substituted hydroxyalkoxyphenyl-1,3,5-triazoles, where substituted benzotriazoles such as 2-(2'-hydroxy-5'-methylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-t-butylphenyl)benzotriazole, 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)benzotriazole, Preferred are 2-(2'-hydroxy-3',5'-tert-butylphenyl)-5-chlorobenzotriazole, 2-(2'-hydroxy-5'-tert-octylphenyl)benzotriazole, 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, 2-[2'-hydroxy-3'-(3'',4'',5'',6''-tetrahydrophthalimidoethyl)-5'-methylphenyl]benzotriazole, and 2,2'-methylenebis[4-(1,1,3,3-tetramethylbutyl)-6-(2H-benzotriazol-2-yl)phenol].

[0120] Polypropylene glycol can be used alone or in combination with, for example, sulfones or sulfonamides as stabilizers to prevent damage from gamma radiation.

[0121] These and other stabilizers can be used individually or in combination and can be added to the formulations according to the invention in the form described.

[0122] It is also possible to add processing aids such as release agents, mainly derivatives of long-chain fatty acids, for example pentaerythritol tetrastearate and glycerol monostearate, which are preferred, either on their own or in a mixture.

[0123] Suitable flame retardant additives are phosphate esters, i.e. triphenyl phosphate, resorcinol diphosphate, brominated phosphate esters, brominated compounds such as brominated oligocarbonates and polycarbonates, and preferably salts of fluorinated organic sulfonic acids.

[0124] Suitable impact modifiers are butadiene rubber grafted with styrene-acrylonitrile or methyl methacrylate, ethylene-propylene rubber grafted with maleic anhydride, ethyl and butyl acrylate rubber grafted with methyl methacrylate or styrene-acrylonitrile, interpenetrating networks of siloxanes and acrylates grafted with methyl methacrylate or styrene-acrylonitrile.

[0125] Additionally, it is possible to add colorants, such as organic dyes or pigments or inorganic pigments, infrared absorbers, either individually, in mixtures or in combination with stabilizers, glass fibres, (hollow) glass beads and inorganic fillers, in particular mineral fillers, again including reinforcing fillers, in particular titanium dioxide (TiO2), talc (Mg3SiO4O 10 (OH)2), dolomite CaMg[CO3]2, kaolinite Al4[(OH)8|Si4O 10 ], and wollastonite Ca3[Si3O9], very especially titanium dioxide (TiO2) and talc (Mg3Si4O 10 (OH)2).

[0126] The plastic mass produced according to the invention can be used wherever known plastic masses containing at least two thermoplastic components, at least one of which is polycarbonate, are used.

[0127] The present invention also provides a plastic mass produced by the method according to the present invention.

[0128] The present invention further provides the use of a plastic mass produced according to the invention for producing a molded article.

[0129] The plastic masses produced according to the invention can be used to produce any type of molded article. These can be produced, for example, by injection molding, extrusion and blow molding processes. A further form of processing is the production of molded articles by thermoforming from previously produced sheets or films.

[0130] Examples of such shaped articles that can be produced from the compositions and plastic masses according to the invention are, for example, films, profiles, housing parts of any kind, for household appliances such as juice presses, coffee machines, mixers, for office equipment such as monitors, flat screens, notebooks, printers, copiers, sheets for the construction sector (interior fittings and exterior applications), pipes, electrical equipment ducts, windows, doors and other profiles, as well as electrical and electronic components such as switches, plugs and sockets, and parts for commercial vehicles, in particular for the automotive sector. The compositions and plastic masses according to the invention are also suitable for the production of the following shaped articles or moldings: ships, aircraft, buses and other mobile vehicles, body components for mobile vehicles, housings for electrical equipment, including mini-transformers, housings for equipment for processing and transmitting information, housings and upholstery for medical equipment, massage equipment and its housing, children's ride-on toys, sheet-like wall members, housings for safety equipment, thermally insulated transport containers, shaped parts for sanitary and bathroom equipment, protective grilles for ventilation openings, and housings for garden equipment.

[0131] The present invention will now be described with reference to examples, but it is in no way intended to limit the invention to these examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS EXAMPLES

[0132] Determination of mean residence times t1 and t2 The average residence times t1 and t2 in the extruder were determined as described below.

[0133] First, the desired speed was set on the extruder and all formulation components were fed into the extruder at the desired location and at the desired throughput. Ten minutes after the completion of addition of all formulation components, the extruder was manually fed with 1 g of tracer pellets (Makrolon 2805, color 901510 [equivalent to black]) per 50 kg / hour total throughput of the formulation as a pulse tracer.

[0134] To determine the average residence time t1 for additive-free formulations that were free-flowing at 23°C, tracer pellets were added to the opening of the extruder housing at a distance of twice the housing inner diameter (2D) upstream of the first screw element that was not a conveying element.

[0135] To determine the average residence time, t2, for a formulation containing an additive that is free flowing at 23°C, tracer pellets were added to an opening in the extruder housing axially parallel to the addition site of the additive that is free flowing at 23°C.

[0136] The residence time t1 for a formulation containing an additive that is free flowing at 23°C was calculated by subtracting the residence time when the tracer was added to a housing orifice 2D upstream of the first screw element that is not a conveying element from the residence time when the tracer was added to a housing orifice axially parallel to the addition site of the additive that is free flowing at 23°C.

[0137] The timing was started simultaneously with the addition of the tracer pellet.

[0138] An in-line spectrophotometer (COLVISTEC InSpectro X2) was used to measure the intensity of the tracer in the plastic mass at the flange just downstream from the end of the extruder shaft.

[0139] For this purpose, for plastic masses with an average transmittance of less than 40% in the wavelength range from 400 nm to 800 nm, a measuring probe was attached to the flange and measurements were performed in reflectance, while for all other plastic masses, two opposing measuring probes were placed on the flange and measurements were performed in transmittance. The measuring probes were each connected to a spectrophotometer by a glass fiber conduit. Using the spectrophotometer, the color spectrum of the plastic mass from 230 nm to 800 nm was measured and recorded every second for 5 minutes from the addition of the tracer, and the L value (luminance, according to CIE LAB) was calculated.

[0140] The mean residence time was calculated from the cumulative function of the distribution curve of the L values ​​by the ReTA evaluation program from COLVISTEC. For the determination of the mean residence time for one experimental set-up, the average was formed in each case from three measurements. However, it is also possible to use other suitable software packages to calculate the mean residence time from the distribution curve of the L values.

[0141] Melting temperature measurement The melt temperature of the plastic mass in all experiments was measured by inserting a thermocouple in the intermediate molten strand emerging from the extruder or, in the case of an even number of nozzle holes, by inserting a thermocouple in one of the two intermediate molten strands directly at the exit from the nozzle bar.

[0142] Measurement of unmelted particles For the evaluation of the plasticization quality, it was determined for each experimental setup how many of the 330 pellets in each case, selected randomly from the total number of pellets produced per experiment, contained at least one unmelted particle. For this purpose, 110 pellets in each case were lined up in a light box so that their cut ends were aligned perpendicularly to the light box. A cardboard roll with a diameter of about 4 cm was then placed around the pellets. A digital camera was placed at the top end of the roll. Exposure and focus were set on the camera so that the top surface of the pellet was clearly imaged and the unmelted particles had good contrast from the plastic mass. Figure 1 is shown as an example of a photograph taken in this way.

[0143] The pictures taken with the digital camera were visually inspected on the monitor for unmelted particles in the pellets. In evaluating the images, a distinction was made between vacuoles and unmelted particles. Unmelted particles differ from vacuoles in shape and location. Vacuoles are generally in the center of the pellet, whereas unmelted particles are outside the center. Vacuoles are generally elliptical to elongated in shape, whereas unmelted particles are much thinner and usually sickle-shaped. In FIG. 2, the vacuoles and unmelted particles are distinguished as examples 2.1.1, 2.1.2, 2.1.3 and 2.1.4 which show pellets with vacuoles, examples 2.1.1.1, 2.1.2.1, 2.1.3.1 and 2.1.4.1 which show vacuoles in these pellets, examples 2.2.1, 2.2.2, 2.2.3 and 2.2.4 which show pellets with unmelted particles, and examples 2.2.1.1, 2.2.1.2, 2.2.2.1, 2.2.2.2, 2.2.3.1, 2.2.3.2, 2.2.4.1 and 2.2.4.2 which show unmelted particles in these pellets.

[0144] In FIG. 3, the pellets with vacuoles in the photograph of FIG. 1 are labeled (3.1) and the pellets with unmelted particles are labeled (3.2).

[0145] In cases where it was not possible to distinguish between vacuoles and unmelted particles from the digital photographs, the pellets were visually inspected individually. Herein, it is possible to clearly distinguish unmelted particles from vacuoles, where the vacuoles are always pores, while the unmelted particles are transparent inclusions that extend the entire length of the pellet in the direction of strand stretching. When a pellet with unmelted particles is held up to the light, the reflection of light is evident. This reflection of light does not occur in the case of vacuoles, since the vacuoles are filled only with gas.

[0146] For the evaluation of the plasticization quality, the number of pellets with at least one unmelted particle was taken relative to the total number of pellets tested per experimental set, i.e., 330. Thus, 5 granules with unmelted particles means 5 / 330=1.5% unmelted particles.

[0147] Examples 1 to 6: Variation of the process parameters mass flow rate m and screw shaft speed n A ZE60B UTXi twin screw extruder manufactured by KraussMaffei Extrusion GmbH was used for the production of the plastic mass in Examples 1 to 6. The design features of the extruder are listed in columns k to n of Table 1. The basic configuration of the extruder used in Examples 1 to 6 is shown in FIG.

[0148] In Examples 1-6, all ingredients of the formulations were metered by conventional gravimetric differential metering balances through an intake funnel 1 shown at the main intake of the screw machine in housing 2.

[0149] In the region of housing 2 to housing 7 there are transport zones for all components of the formulation.

[0150] In the region of the housing 8 there is a plastifying zone, the screw configuration of which consists of various two- and three-flighted kneading blocks of various widths, as well as toothed mixing elements.

[0151] In the region of housing 9 and housing 10 there is a mixing zone, the screw configuration of which consists of kneading elements, toothed mixing elements and conveying elements.

[0152] In the housing part 11 there is a vent 13, which is connected to an extraction device (not shown).

[0153] In the housing 12 there is a pressure zone downstream of which is a nozzle plate having 29 holes.

[0154] In Examples 1-6, pelletization was carried out in the form of strand pelletization after water bath cooling.

[0155] The blend fed to the extruder in Examples 1 to 6 was Relative viscosity η at 60.3% by weight rel = 1.28 (measured at a concentration of 0.5 g / 100 ml at 25 ° C. in CH2Cl2 as solvent), and 17.2% by weight of emulsion ABS pellets having an A:B:S weight ratio of 20:24:56; 8.9% by weight of bulk ABS pellets having an A:B:S weight ratio of 25:10:65; 9.5% by weight of a styrene-acrylonitrile copolymer (SAN) having an A:S weight ratio of 24:76; 4.1% by weight of a powder mixture containing 3% by weight of an emulsion ABS graft in powder form having an A:B:S weight ratio of 12:58:30, as well as 0.35% by weight of a stabilizer and 0.75% by weight of a release agent; It consists of a mixture of

[0156] In Comparative Examples 1 and 2 according to the invention, as well as in Examples 3 to 6, the formulations are formulated with the following parameters specified in Table 1: screw shaft speed (Table 1, column p), mass flow rate (Table 1, column o) and the specific mechanical energy input obtained (Table 1, column q), as well as the temperature of the melt emerging from the nozzle plate (Table 1, column r), so that the number of pellets with unmelted particles is likewise shown in Table 1 (Table 1, column w).

[0157] As shown in Examples 1 to 6, irrespective of the speed selected for the formulation or the mass flow rate selected, if the melt rate (Table 1, column x) is at least 1.18, in particular at least 1.23, plastic masses according to the invention are always obtained, whereas in the case of melt rates below 1.18, in particular in the case of melt rates below 1.08, the number of pellets with unmelted particles is unacceptable.

[0158] Examples 7 to 19: Variation of viscosity ratios dh1 and dh2 A ZE60B UTXi twin screw extruder manufactured by KraussMaffei Extrusion GmbH was used to produce the plastic mass in Examples 7 to 19. The design features of the extruder are listed in columns k to n of Table 1. The basic configuration of the extruder used in Examples 7 to 19 is shown in FIG.

[0159] In Examples 7-10, all ingredients of the formulations were weighed by conventional gravimetric differential weighing balance through an intake funnel 1 shown at the main intake of the screw machine in housing 2.

[0160] In the region of housing 2 to housing 7 there are transport zones for all components of the formulation.

[0161] In the region of the housing 8 there is a plasticization zone, the screw configuration of which consists of various two- and three-flighted kneading blocks of various widths as well as toothed mixing elements.

[0162] In the region of housing 9 and housing 10 there is a mixing zone, the screw configuration of which consists of kneading elements, toothed mixing elements and conveying elements.

[0163] In the housing part 11 there is a vent 13, which is connected to an extraction device (not shown).

[0164] In the housing 12 there is a pressure zone downstream of which is a nozzle plate having 29 holes.

[0165] In Examples 7-10, pelletization was carried out in the form of strand pelletization after water bath cooling.

[0166] The blends fed to the extruder in Examples 7 to 10 were: Relative viscosity η at 76% by weight rel = 1.28 (measured at a concentration of 0.5 g / 100 ml at 25 ° C. in CH2Cl2 as solvent), and 3.96% by weight of bulk ABS pellets having an A:B:S weight ratio of 25:10:65; Bulk ABS pellets having an A:B:S weight ratio of 21:10:69 at 24.74% by weight; 2.04% by weight of a powder mixture containing 1% by weight of an emulsion ABS graft in powder form having an A:B:S weight ratio of 12:58:30, as well as 0.3% by weight of a stabilizer and 0.74% by weight of a release agent; It consists of a mixture of

[0167] The plastic chunks of Examples 7-10 have the average specific heat capacities set forth in Table 1, column h.

[0168] In Comparative Examples 7 and 8 according to the invention, as well as in Examples 9 and 10, the formulations are formulated with the following parameters specified in Table 1: screw shaft speed (Table 1, column p), mass flow rate (Table 1, column o) and the specific mechanical energy input obtained (Table 1, column q), as well as the temperature of the melt emerging from the nozzle plate (Table 1, column r), so that the number of pellets with unmelted particles is likewise shown in Table 1 (Table 1, column w).

[0169] In Examples 11-14, all components of the formulations, except for additives that were free flowing at 23° C., were weighed by conventional gravimetric differential weighing balance through an intake funnel 1 shown at the main intake of the screw machine in housing 2.

[0170] In the region of housing 2 to housing 7 there are transport zones for all components of the formulation.

[0171] In the region of the housing 8 there is a plasticization zone consisting of various two- and three-flighted kneading blocks of various widths as well as toothed mixing elements.

[0172] The additive, which is free-flowing at 23° C. in the housing 9, was injected into the plastic mass by means of a commercial membrane piston pump (not shown) through a valve (not shown) screwed into the hole 14 in the housing 9.

[0173] In the region of housing 9 and housing 10 there is a mixing zone consisting of kneading elements, toothed mixing elements and conveying elements.

[0174] In the housing part 11 there is a vent 13, which is connected to an extraction device (not shown).

[0175] In the housing 12 there is a pressure zone downstream of which is a nozzle plate having 29 holes.

[0176] In Examples 11-14, pelletization was carried out in the form of strand pelletization after water bath cooling.

[0177] The blend fed to the extruder in Examples 11 to 14 was Relative viscosity η at 73% by weight rel = 1.28 (measured at a concentration of 0.5 g / 100 ml at 25 ° C. in CH2Cl2 as solvent), and 4.7% by weight of a styrene-acrylonitrile copolymer (SAN) having an A:S weight ratio of 24:76; 7.7% by weight of an emulsion ABS graft in powder form having an A:B:S weight ratio of 12:58:30; 10% by weight of an oligophosphate based on bisphenol A, particularly BDP, which is free-flowing at 23° C.; Relative viscosity at 3% by weight η rel = 1.28 (measured at a concentration of 0.5 g / 100 ml at 25 ° C. in CH2Cl2 as a solvent), and 0.4 wt. % of a stabilizer, 0.8 wt. % of a flame retardant, and 0.4 wt. % of a release agent; It consists of a mixture of

[0178] The plastic chunks of Examples 11-14 have the average specific heat capacities set forth in Table 1, column h.

[0179] In Comparative Example 11 according to the invention, and in Examples 12 to 14, the formulations are formulated with the following parameters specified in Table 1: screw shaft speed (Table 1, column p), mass flow rate (Table 1, column o) and the specific mechanical energy input obtained (Table 1, column q), as well as the temperature of the melt emerging from the nozzle plate (Table 1, column r), so that the number of pellets with unmelted particles is likewise shown in Table 1 (Table 1, column w).

[0180] In Examples 15-19, all components of the formulations, except for additives that were free flowing at 23° C., were weighed by conventional gravimetric differential weighing balance through an intake funnel 1 shown at the main intake of the screw machine in housing 2.

[0181] In the region of housing 2 to housing 7 there are transport zones for all components of the formulation.

[0182] In the region of the housing 8 there is a plasticization zone consisting of various two- and three-flighted kneading blocks of various widths as well as toothed mixing elements.

[0183] The additive, which is free-flowing at 23° C. in the housing 9, was injected into the plastic mass by means of a commercial membrane piston pump (not shown) through a valve (not shown) screwed into the hole 14 in the housing 9.

[0184] In the region of housing 9 and housing 10 there is a mixing zone consisting of kneading elements, toothed mixing elements and conveying elements.

[0185] In the housing part 11 there is a vent 13, which is connected to an extraction device (not shown).

[0186] In the housing 12 there is a pressure zone downstream of which is a nozzle plate having 29 holes.

[0187] In Examples 15-19, pelletization was carried out in the form of strand pelletization after water bath cooling.

[0188] The blend fed to the extruder in Examples 15 to 19 was Relative viscosity η at 40.2% by weight rel = 1.28 (measured at a concentration of 0.5 g / 100 ml at 25 ° C. in CH2Cl2 as solvent), and Relative viscosity η at 23.5% by weight rel = 1.20 (measured at a concentration of 0.5 g / 100 ml at 25 ° C. in CH2Cl2 as solvent), 7% by weight of a styrene-acrylonitrile copolymer (SAN) having an A:S weight ratio of 24:76; 11% by weight of an emulsion ABS graft in powder form having an A:B:S weight ratio of 12:58:30; 14% by weight of an oligophosphate based on bisphenol A, particularly BDP, which is free-flowing at 23° C.; Relative viscosity at 3% by weight η rel = 1.28 (measured at a concentration of 0.5 g / 100 ml at 25 ° C. in CH2Cl2 as a solvent), and 0.1 wt. % of a stabilizer, 0.8 wt. % of a flame retardant, and 0.4 wt. % of a release agent; It consists of a mixture of

[0189] The plastic chunks of Examples 15-19 have the average specific heat capacities set forth in Table 1, column h.

[0190] In Comparative Examples 15 to 17 according to the invention, as well as in Examples 18 and 19, the formulations are formulated with the following parameters specified in Table 1: screw shaft speed (Table 1, column p), mass flow rate (Table 1, column o) and the specific mechanical energy input obtained (Table 1, column q), as well as the temperature of the melt emerging from the nozzle plate (Table 1, column r), so that the number of pellets with unmelted particles is likewise shown in Table 1 (Table 1, column w).

[0191] As shown in Examples 1 to 6, 7 to 10, 11 to 14 and 15 to 19 of the different formulations, irrespective of the formulation or its average specific heat capacity and the selected speed or selected mass flow rate, if the melting rate (Table 1, column x) is at least 1.18, in particular at least 1.20, a plastic mass according to the invention is always obtained, whereas in the case of melting rates below 1.18, in particular in the case of melting rates below 1.14, the number of pellets with unmelted particles is unacceptable.

[0192] Examples 20 to 29: Variation of pellet diameter d A ZE60B UTXi twin screw extruder manufactured by KraussMaffei Extrusion GmbH was used to produce the plastic mass in Examples 20 to 29. The design features of the extruder are listed in columns k to n of Table 1. The basic configuration of the extruder used in Examples 7 to 19 is shown in FIG.

[0193] In Examples 20-29, all components of the formulations, except for additives that were free flowing at 23° C., were weighed by conventional gravimetric differential weighing balance through an intake funnel 1 shown at the main intake of the screw machine in housing 2.

[0194] In the region of housing 2 to housing 7 there are transport zones for all components of the formulation.

[0195] In the region of the housing 8 there is a plasticization zone, the screw configuration of which consists of various two- and three-flighted kneading blocks of various widths as well as toothed mixing elements.

[0196] The additive, which is free-flowing at 23° C. in the housing 9, was injected into the plastic mass by means of a commercial membrane piston pump (not shown) through a valve (not shown) screwed into the hole 14 in the housing 9.

[0197] In the region of housing 9 and housing 10 there is a mixing zone, the screw configuration of which consists of kneading elements, toothed mixing elements and conveying elements.

[0198] In the housing part 11 there is a vent 13, which is connected to an extraction device (not shown).

[0199] In the housing 12 there is a pressure zone downstream of which is a nozzle plate having 29 holes.

[0200] In Examples 20-29, pelletization was carried out in the form of strand pelletization after water bath cooling.

[0201] The blend fed to the extruder in Examples 20 to 29 was Relative viscosity η at 40.2% by weight rel = 1.28 (measured at a concentration of 0.5 g / 100 ml at 25 ° C. in CH2Cl2 as solvent), and Relative viscosity η at 23.5% by weight rel = 1.20 (measured at a concentration of 0.5 g / 100 ml at 25 ° C. in CH2Cl2 as solvent), 7% by weight of a styrene-acrylonitrile copolymer (SAN) having an A:S weight ratio of 24:76; 11% by weight of an emulsion ABS graft in powder form having an A:B:S weight ratio of 12:58:30; 14% by weight of an oligophosphate based on bisphenol A, particularly BDP, which is free-flowing at 23° C.; Relative viscosity at 3% by weight η rel = 1.28 (measured at a concentration of 0.5 g / 100 ml at 25 ° C. in CH2Cl2 as a solvent), and 0.1 wt. % of a stabilizer, 0.8 wt. % of a flame retardant, and 0.4 wt. % of a release agent; It consists of a mixture of

[0202] In Examples 20 to 29, the formulations are compounded with the following parameters specified in Table 1: screw shaft speed (Table 1, column p), mass flow rate (Table 1, column o) and the resulting specific mechanical energy input (Table 1, column q), as well as the temperature of the melt exiting the nozzle plate (Table 1, column r), so that the number of pellets with unmelted particles is similarly shown in Table 1 (Table 1, column w).

[0203] In Examples 20 to 23, the pellet diameter of the low viscosity polycarbonate compound component increased from 3.264 mm or 3.195 mm to 3.603 mm compared to Examples 15 to 19 (see Table 1, column c.2), but remained unchanged for the high viscosity polycarbonate compound component (see Table 1, column c.1).

[0204] In Examples 24 to 27, the pellet diameter of the high viscosity polycarbonate compound component increased from 3.143 mm or 3.122 mm to 3.547 mm compared to Examples 15 to 19 (see Table 1, column c.1), while it remained unchanged in the low viscosity polycarbonate compound component (see Table 1, column c.2).

[0205] In Examples 28 and 29, the pellet diameter of the SAN compound component increased from 3.488 mm to 4.002 mm compared to Examples 15 to 19 (see Table 1, column c.3), while it remained unchanged for the polycarbonate compound component (see Table 1, columns c.1 and c.2).

[0206] Comparison of Examples 20-23 with Examples 15-19 shows that increasing the pellet diameter of the low viscosity polycarbonate compound component does not affect the quality of the plasticization. Equal process parameters of mass flow rate and screw shaft speed result in comparable plasticization quality (see Table 1, rows o, p and w).

[0207] Comparison of Examples 24-27 with Examples 15-19 shows that increasing the pellet diameter of the high viscosity polycarbonate compound component clearly deteriorates the quality of the plasticization at equal process parameters of mass flow rate and screw shaft speed (see Table 1, rows o, p and w).

[0208] Comparison of Examples 28-29 with Examples 15-19 shows that increasing the pellet diameter of the SAN formulation components does not affect the quality of the plasticization. Equal process parameters of mass flow rate and screw shaft speed result in comparable plasticization quality (see Table 1, rows o, p and w).

[0209] As shown by the comparison of Examples 15 to 29, regardless of the pellet diameter and the selected speed or the selected mass flow rate, when the melting rate (Table 1, column x) is at least 1.18, in particular at least 1.36, plastic masses according to the invention are always obtained, whereas in the case of melting rates below 1.18, in particular in the case of melting rates below 1.16, the number of pellets with unmelted particles is unacceptable.

[0210] Examples 30-33: Variation of ingredients for the same formulation A ZE60B UTXi twin screw extruder manufactured by KraussMaffei Extrusion GmbH was used to produce the plastic mass in Examples 30 to 33. The design features of the extruder are listed in columns k to n of Table 1. The basic configuration of the extruder used in Examples 30 to 33 is shown in FIG.

[0211] In Examples 30-33, all components of the formulations, except for additives that were free flowing at 23° C., were weighed by conventional gravimetric differential weighing balance through an intake funnel 1 shown at the main intake of the screw machine in housing 2.

[0212] In the region of housing 2 to housing 7 there are transport zones for all components of the formulation.

[0213] In the region of the housing 8 there is a plasticization zone consisting of various two- and three-flighted kneading blocks of various widths as well as toothed mixing elements.

[0214] The additive, which is free-flowing at 23° C. in the housing 9, was injected into the plastic mass by means of a commercial membrane piston pump (not shown) through a valve (not shown) screwed into the hole 14 in the housing 9.

[0215] In the region of housing 9 and housing 10 there is a mixing zone, the screw configuration of which consists of kneading elements, toothed mixing elements and conveying elements.

[0216] In the housing part 11 there is a vent 13, the screw arrangement of which is connected to an extractor (not shown).

[0217] In the housing 12 there is a pressure zone downstream of which is a nozzle plate having 29 holes.

[0218] In Examples 30-33, pelletization was carried out in the form of strand pelletization after water bath cooling.

[0219] In Examples 30 to 33, the blend fed to the extruder was Relative viscosity η of 63.7% by weight rel = 1.28 (measured at a concentration of 0.5 g / 100 ml at 25 ° C. in CH2Cl2 as solvent), and 7% by weight of a styrene-acrylonitrile copolymer (SAN) having an A:S weight ratio of 24:76; 11% by weight of an emulsion ABS graft in powder form having an A:B:S weight ratio of 12:58:30; 14% by weight of an oligophosphate based on bisphenol A, particularly BDP, which is free-flowing at 23° C.; Relative viscosity at 3% by weight η rel = 1.28 (measured at a concentration of 0.5 g / 100 ml at 25 ° C. in CH2Cl2 as a solvent), and 0.1 wt. % of a stabilizer, 0.8 wt. % of a flame retardant, and 0.4 wt. % of a release agent; It consists of a mixture of

[0220] In Examples 30 to 33, the formulations are compounded with the following parameters specified in Table 1: screw shaft speed (Table 1, column p), mass flow rate (Table 1, column o) and the resulting specific mechanical energy input (Table 1, column q), as well as the temperature of the melt exiting the nozzle plate (Table 1, column r), so that the number of pellets with unmelted particles is similarly shown in Table 1 (Table 1, column w).

[0221] Comparison of Examples 30 to 33 with Examples 15 to 19 shows that the use of only one polycarbonate in the formulation (Examples 30 to 33) results in a much better plasticization quality with the same process parameters of mass flow rate and screw shaft speed compared to the use of two polycarbonate components with different viscosities but exactly the same overall mixed viscosity (Examples 15 to 19) (see Table 1, rows o, p and w).

[0222] Moreover, as shown by the comparison of Examples 15 to 19 and Examples 30 to 33, regardless of the formulation composition selected for the polycarbonate component(s) and the selected speed or selected mass flow rate, a plastic mass according to the invention is always obtained when the melt rate (Table 1, column x) is at least 1.18, in particular at least 1.19, whereas in the case of melt rates below 1.18, in particular at or below 1.14, the number of pellets with unmelted particles is unacceptable.

[0223] Examples 34 and 35: Variation of extruder diameter D A ZSK92 Mc twin screw extruder manufactured by Coperion GmbH was used for the production of the plastic mass in Examples 34 and 35. The design features of the extruder can be seen in columns k to n of Table 1. The basic configuration of the extruder used in Examples 34 and 35 is shown in FIG.

[0224] In Examples 34 and 35, all ingredients of the formulations were weighed by conventional gravimetric differential weighing balance through an intake funnel 15 shown at the main intake of the screw machine in housing 16.

[0225] In the area of ​​housing 17 and housing 18 there are delivery zones for all the components of the formulation.

[0226] In the region of housing 19 and housing 20 there is a plasticization zone, the screw configuration of which consists of various two- and three-flighted kneading blocks of various widths, as well as toothed mixing elements.

[0227] In the region of the housing 21 there is a mixing zone, the screw arrangement of which consists of toothed mixing elements and conveying elements.

[0228] In the housing portion 22 there is a vent 24 which is connected to an extraction device (not shown).

[0229] In the housing 23 there is a pressure zone downstream of which is a nozzle plate with 100 holes.

[0230] The pelletization in Examples 34 and 35 was carried out in the form of underwater pelletization.

[0231] The blends fed to the extruder in Examples 34 and 35 were: Relative viscosity η at 60.3% by weight rel = 1.28 (measured at a concentration of 0.5 g / 100 ml at 25 ° C. in CH2Cl2 as solvent), and 17.2% by weight of emulsion ABS pellets having an A:B:S weight ratio of 20:24:56; 8.9% by weight of bulk ABS pellets having an A:B:S weight ratio of 25:10:65; 9.5% by weight of a styrene-acrylonitrile copolymer (SAN) having an A:S weight ratio of 24:76; 4.1% by weight of a powder mixture containing 3% by weight of an emulsion ABS graft in powder form having an A:B:S weight ratio of 12:58:30, as well as 0.35% by weight of a stabilizer and 0.75% by weight of a release agent; It consists of a mixture of

[0232] In Comparative Example 34 and Example 35 according to the invention, the formulations are formulated with the following parameters specified in Table 1: screw shaft speed (Table 1, column p), mass flow rate (Table 1, column o) and the specific mechanical energy input obtained (Table 1, column q), as well as the temperature of the melt emerging from the nozzle plate (Table 1, column r), so that the number of pellets with unmelted particles is likewise shown in Table 1 (Table 1, column w).

[0233] As shown in Examples 34 and 35 in comparison with Examples 1 to 6, irrespective of the extruder diameter and the speed selected for the formulation or the mass flow rate selected, when the melt rate (Table 1, column x) is at least 1.18, in particular at least 1.53, plastic masses according to the invention are always obtained, whereas in the case of melt rates below 1.18, in particular in the case of melt rates below 0.77, the number of pellets with unmelted particles is unacceptable.

[0234] Examples 36 to 40: Metering point variation of additives that are free-flowing at 23°C A ZE60B UTXi twin screw extruder manufactured by KraussMaffei Extrusion GmbH was used to produce the plastic mass in Examples 36 to 40. The design features of the extruder are listed in columns k to n of Table 1. The basic configuration of the extruder used in Examples 36 to 40 is shown in FIG.

[0235] In Examples 36-40, all components of the formulations, except for additives that were free flowing at 23° C., were weighed by conventional gravimetric differential weighing balance through an intake funnel 1 shown at the main intake of the screw machine in housing 2.

[0236] In the region of housing 2 to housing 7 there are transport zones for all components of the formulation.

[0237] In the region of the housing 8 there is a plasticization zone consisting of various two- and three-flighted kneading blocks of various widths as well as toothed mixing elements.

[0238] The additive, which is free-flowing at 23° C. in the housing 9, was injected into the plastic mass by means of a commercial membrane piston pump (not shown) through a valve (not shown) screwed into the hole 14 in the housing 9.

[0239] In the region of housing 9 and housing 10 there is a mixing zone consisting of kneading elements, toothed mixing elements and conveying elements.

[0240] In the housing part 11 there is a vent 13, which is connected to an extraction device (not shown).

[0241] In the housing 12 there is a pressure zone downstream of which is a nozzle plate having 29 holes.

[0242] In Examples 36-40, pelletization was carried out in the form of strand pelletization after water bath cooling.

[0243] The blends fed to the extruder in Examples 36 to 40 were: Relative viscosity η of 58.7% by weight rel = 1.28 (measured at a concentration of 0.5 g / 100 ml at 25 ° C. in CH2Cl2 as solvent), and 9.3% by weight of a styrene-acrylonitrile copolymer (SAN) having an A:S weight ratio of 24:76; 8.7% by weight of an emulsion ABS graft in powder form having an A:B:S weight ratio of 12:58:30; 20% by weight of an oligophosphate based on bisphenol A, in particular BDP, which is free-flowing at 23° C.; Relative viscosity at 3% by weight η rel = 1.28 (measured at a concentration of 0.5 g / 100 ml at 25 ° C. in CH2Cl2 as a solvent), and 0.1 wt. % of a stabilizer, 0.8 wt. % of a flame retardant, and 0.4 wt. % of a release agent; It consists of a mixture of

[0244] In Examples 36 to 40, the formulations are compounded with the following parameters specified in Table 1: screw shaft speed (Table 1, column p), mass flow rate (Table 1, column o) and the resulting specific mechanical energy input (Table 1, column q), as well as the temperature of the melt exiting the nozzle plate (Table 1, column r), so that the number of pellets with unmelted particles is similarly shown in Table 1 (Table 1, column w).

[0245] A comparison of Examples 36 to 40 shows that the quality of plasticization is enhanced by delaying the addition of additives that are free-flowing at 23° C. with the same process parameters of mass flow rate and screw shaft speed (see Table 1, rows o, p and w).

[0246] Moreover, as shown by the comparison of Examples 36 to 40, regardless of the site of addition of the additive that is free-flowing at 23° C. and the selected rate or the selected mass flow rate, a plastic mass according to the invention is always obtained when the melt rate (Table 1, column x) is at least 1.18, in particular at least 1.35, while in the case of melt rates below 1.18, in particular below 1.11, the number of pellets with unmelted particles is unacceptable.

[0247] Examples 41 to 44: Variation of the number of extruder shafts An extruder with 12 co-rotating shafts of the RE1 ring extruder type manufactured by CPM Extricom Extrusion GmbH was used for the production of the plastic masses in Examples 41 to 44. The design features of the extruder can be seen in columns k to n of Table 1. The basic configuration of the extruder used in Examples 41 to 44 is shown in FIG.

[0248] In Examples 41-44, all ingredients of the formulations were weighed by conventional gravimetric differential weighing balance through an intake funnel 25 shown at the main intake of the screw machine in housing 26.

[0249] In the region of housing 27 to housing 29 there is a transport zone for all the components of the formulation.

[0250] In the region of the housing 30 there is a plasticization zone, the screw configuration of which consists of various two-flight kneading blocks of various widths.

[0251] In the housing part 31 there is a vent 33, which is connected to an extraction device (not shown).

[0252] In the housing 32 there is a pressure zone downstream of which is a nozzle plate having six holes.

[0253] In Examples 41-44, pelletization was carried out in the form of strand pelletization after water bath cooling.

[0254] The blend fed to the extruder in Examples 41 to 44 was Relative viscosity η at 28% by weight rel = 1.28 (measured at a concentration of 0.5 g / 100 ml at 25 ° C. in CH2Cl2 as solvent), and Relative viscosity η at 15% by weight rel = 1.20 (measured at a concentration of 0.5 g / 100 ml at 25 ° C. in CH2Cl2 as solvent), 31% by weight of a styrene-acrylonitrile copolymer (SAN) having an A:S weight ratio of 24:76; 22% by weight of an emulsion ABS graft in powder form having an A:B:S weight ratio of 12:58:30; 3. 4% by weight of a powder mixture containing 1% by weight of an emulsion ABS graft in powder form having an A:B:S weight ratio of 12:58:30, as well as 0.16% by weight of a stabilizer and 0.74% by weight of a release agent; It consists of a mixture of

[0255] In Comparative Examples 41 and 42 according to the invention, as well as in Examples 43 and 44, the formulations are compounded with the following parameters specified in Table 1: screw shaft speed (Table 1, column p), mass flow rate (Table 1, column o) and temperature obtained from the melt exiting the nozzle plate (Table 1, column r), which results in the number of pellets with unmelted particles being shown in Table 1 as well (Table 1, column w).

[0256] As shown in Examples 41 to 44, even in the case of an extruder with 12 shafts, and regardless of the speed selected for the compound or the mass flow rate selected, if the melt rate (Table 1, column x) is at least 1.18, in particular at least 1.53, plastic masses according to the invention are always obtained, while in the case of melt rates below 1.18, in particular in the case of melt rates below 1.03, the number of pellets with unmelted particles is unacceptable.

[0257] In order to achieve comparability of the melting rates between 12-screw and twin-screw machines, the mass flow rate m must be divided by 6 in the calculation of the melting rate of the 12-screw machine, ignoring the fact that the 12-screw machine is not a 6-screw twin-screw machine, but rather has two adjacent screws meshing simultaneously for each screw, rather than only one screw as in the twin-screw machine, which results in an increased throughput all the more. Dividing the mass flow rate by 6 results in an equal dimensionless throughput and thus in the comparability of the two screw machines. The dimensionless throughput is, for example, defined as the throughput index V in Kohlgrueber, Bierdel, Rust "Polymer-Aufbereitung und Kunststoff-Compoundierung" [Polymer Processing and Plastics Compounding], Hanser-Verlag, 2019, p. 36, chapter 2.3.7. * The reference diameter D, which is defined as: and is used equally for 12-screw and twin-screw machines, is the housing inner diameter.

[0258] Conclusion for all examples: Examples 1 to 44 show that good plasticization of the plastic mass produced from a formulation containing at least two thermoplastic components, at least one of which is polycarbonate, is obtained when the melt rate is at least 1.18, regardless of the heat capacity of the plastic mass, the pellet diameter of the most viscous polycarbonate component in the formulation, the inner diameter of the extruder housing, the configuration of the extruder, the metering position of the additive that is free-flowing at 23°C, the composition of the formulation, the number of extruder shafts, and the process parameters of mass flow rate and screw shaft speed.

[0259] [Table 1]

[0260] [Table 2]

[0261] [Table 3]

[0262] [Table 4]

Claims

1. A method for manufacturing a plastic block in a multi-screw machine having co-rotating parallel screw shafts that rotate at a constant speed, The screw shaft rotates at a speed n, The plastic mass is manufactured from a compound containing at least two thermoplastic components, at least one of the at least two thermoplastic components being polycarbonate, and the plastic mass is, (i) It contains no additives that are free-flowing at 23°C, or (ii) Contains only one additive that is free-flowing at 23°C, or (iii) comprising at least two additives that are free-flowing at 23°C, The plastic mass at a shear rate γ of 200 1 / second, (i) In this case, At a temperature of 230°C, In the case of (ii), From 230°C, subtract the temperature obtained by multiplying 230°C by twice the ratio of the mass of the single additive that is freely fluid at 23°C to the mass of the plastic mass, In the case of (iii), The dynamic viscosity measured according to ISO 11443:2014 Method A2 at a temperature obtained by subtracting from 230°C the result of multiplying 230°C by twice the sum of the mass ratios of the at least two additives that are freely fluid at 23°C relative to the mass of the plastic mass, is: At a shear rate γ of 200 1 / s and a temperature of 230°C, at least one of these thermoplastic components is measured in a ratio of 0.3 to 3 with respect to the viscosity measured according to ISO 11443:2014 Method A2. The aforementioned at least two thermoplastic components have the following characteristics: At least one structural unit is different, or The difference in relative solution viscosity, as measured according to EN ISO 1628-1:2021, is at least 5%. It differs in at least one of the following: The above method is characterized by the melting rate, The melting rate in the longitudinal cross-section of the screw machine, starting at a distance twice the inner diameter D of the housing upstream of the first screw element (which is not a conveying element) and ending at the last screw element of the screw machine, is 1.18 to 8, and this melting rate: [Math 1] Regarding During the ceremony, τ １ It begins at a distance of twice the inner diameter D of the housing upstream of the first screw element, which is not a transport element. (i) In this case, The screw machine ends with the last screw element, In the case of (ii) or (iii), The first screw element, which is not a transport element, terminates at a first additive site where the additive is free-flowing at 23°C, downstream of the first screw element. This is the average residence time of the plastic mass in the longitudinal cross-section of the screw machine, δη １ In the case of (i), the shear rate γ of the plastic mass corresponds to the speed n of the screw shaft. At a temperature of 230°C, In the case of (ii), From 230°C, subtract the temperature obtained by multiplying 230°C by twice the ratio of the mass of the single additive that is freely fluid at 23°C to the mass of the plastic mass, In the case of (iii), The dynamic viscosity at a temperature obtained by subtracting (230°C multiplied by twice the sum of the mass ratios of at least two additives that are freely fluid at 23°C relative to the total mass of the plastic mass) from 230°C, The thermoplastic component having the highest dynamic viscosity measured at a shear rate γ of 200 1 / s, (i) In this case, At a temperature of 230°C, In the case of (ii), From 230°C, subtract the temperature obtained by multiplying 230°C by twice the ratio of the mass of the single additive that is freely fluid at 23°C to the mass of the plastic mass, In the case of (iii), This is the ratio of the temperature obtained by subtracting (230°C multiplied by twice the sum of the mass ratios of at least two additives that are freely fluid at 23°C relative to the mass of the plastic mass) from 230°C to the dynamic viscosity. τ ２ teeth, In the case of (ii) and in the case of (iii), This is the average residence time of the plastic mass in the longitudinal cross-section of the screw machine, starting at a first additive site where the additive is free-flowing downstream at 23°C, at a distance twice the inner diameter D of the housing upstream of the first screw element which is not a conveying element, and ending at the last screw element of the screw machine. (i) In this case, It is zero, δη ２ This is the ratio of the dynamic viscosity of the plastic mass at a shear rate γ corresponding to the speed n of the screw shaft and a temperature corresponding to the temperature of the plastic mass at the end of the last screw element to the dynamic viscosity of the thermoplastic component having the highest dynamic viscosity measured at a shear rate of 200 1 / second and a temperature corresponding to the temperature of the plastic mass at the end of the last screw element. λ is the thermal conductivity of the plastic mass immediately after it exits the screw machine, measured at 23°C according to EN ISO 11357-8:2021. n is the speed of the screw shaft of the screw machine, d is the diameter of the polycarbonate pellets present in the formulation for producing the plastic mass having the highest relative viscosity, as measured according to EN ISO 1628-1:2021. D is the inner diameter of the housing of the screw machine, and the housing inner diameter D is the same for all housings of the screw machine. c ｐ This is the average specific heat capacity measured in accordance with ISO 11357-4:2021 in the temperature range of 250°C to 300°C. A method in which m is the mass flow rate [kg / second] of the plastic mass in the screw machine.

2. The method according to claim 1, wherein the melting rate is 1.18 to 5.

3. The method according to claim 1 or 2, wherein the melting rate is 1.2 to 3.

4. The method according to claim 1 or 2, wherein, when at least one additive that is free-flowing at 23°C is used for addition, one of these additives is bisphenol A bis(diphenyl phosphate).

5. The method according to claim 1 or 2, wherein all thermoplastic components in the aforementioned formulation are polycarbonate.

6. The method according to claim 1 or 2, wherein if one of the at least two thermoplastic components is not polycarbonate, the non-polycarbonate thermoplastic component is selected from the group comprising: polyester carbonate, polyamide, polyester, polylactide, polyether, thermoplastic polyurethane, polyacetal, fluoropolymer, polyethersulfone, polyolefin, polyimide, polyacrylate, polyphenylene oxide, polyphenylene sulfide, polyether ketone, polyaryl ether ketone, styrene polymer, styrene copolymer, acrylonitrile-butadiene-styrene block copolymer, and polyvinyl chloride.

7. The method according to claim 1 or 2, wherein the proportion of polycarbonate in the compound for producing the plastic mass is 20% by weight to 98% by weight.

8. The method according to claim 1 or 2, wherein at least one of the thermoplastic components, which is polycarbonate, is an aromatic polycarbonate based on bisphenol A.

9. The method according to claim 6, wherein if one of the at least two thermoplastic components is not polycarbonate, this thermoplastic component is a rubber-modified vinyl (co)polymer.

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