Flame retardant polycarbonate composition having high comparative tracking index

Abstract

The present invention relates to a polycarbonate composition, comprising, based on the total weight of the composition, the following components: A) 30% to 80% by weight of a copolycarbonate, B) 10% to 40% by weight of a homopolycarbonate, C) 8% to 25% by weight of a phosphorus-based flame retardant, D) 0% to 8% by weight of an impact modifier, and E) 0% to 8% by weight of a styrene-acrylonitrile copolymer, where the weight average molecular weight of the homopolycarbonate is in the range of 24000 g / mol to 28000 g / mol, and the total amount of the impact modifier and the styrene-acrylonitrile copolymer is 15% by weight or less. The present invention also relates to a molded article made from the composition. The polycarbonate composition according to the present invention has a high comparative tracking index, good flowability, and good flame retardancy.

Description

[Technical field]

[0001] The present invention relates to a polycarbonate (PC) composition, in particular to a polycarbonate composition having a high level of comparative tracking index and good flame retardancy, and to a molded article made therefrom. [Background technology]

[0002] Polycarbonate is widely used in a wide variety of applications such as in the automotive, electrical and electronic fields due to its excellent optical, mechanical and heat resistance properties, as well as its excellent thermal processability.

[0003] Copolycarbonates, as a special type of polycarbonate, are widely used in the electrical and electronic fields, as housing materials for lighting and in applications where specific thermal and mechanical properties are required, such as hairdryers, applications in the automotive field, plastic covers, diffusion screens or waveguiding elements, and lamp covers or lamp bezels.

[0004] It is known that the heat distortion resistance of polycarbonates can be improved by introducing certain building blocks based on 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (bisphenol TMC) into the polycarbonate backbone. The copolycarbonates obtained in this way (so-called high Tg polycarbonates) are expensive. Moreover, due to the relatively high glass transition temperature (Tg) of this type of copolycarbonate, its flowability is not high.

[0005] In recent years, there has been a trend in the field of electrical and electronic applications to miniaturize electronic and electrical devices. This has led to the adoption of more complex and compact designs of electrical devices that contain plastic housings or components. Therefore, safety-related properties of plastic materials such as Comparative Tracking Index (CTI) and flame retardancy have been required in the field of electronics and electrical applications.

[0006] For example, plastic materials require high levels of flame retardancy (e.g., V0 rating at 1.5 mm determined according to UL94-2015) and high CTI ranking (e.g., CTI=600V determined according to IEC60112:2011). However, it is well known that the comparative tracking index for standard polycarbonate resins is only around 250V or even lower.

[0007] Furthermore, the introduction of flame retardants into standard bisphenol A based polycarbonate is generally believed to be detrimental to the CTI performance of the final blend; the more flame retardant, the lower the CTI; further details can be found in "Flames of Flame Retardant Polymers: A Review", Vol. 1, No. 1, pp. 111-115, 2002.

[0008] US Pat. No. 5,399,433 discloses a polymer blend of polybutylene terephthalate, brominated polystyrene, aromatic polycarbonate, and an agent for improving impact strength, which exhibits a combination of good flame retardancy and a high level of comparative tracking index.

[0009] Therefore, obtaining polycarbonate compositions with high CTI, good flowability, and good flame retardancy remains a challenge. [Prior art documents] [Patent documents]

[0010] [Patent Document 1] U.S. Patent No. 4,900,784 [Non-patent literature]

[0011] [Non-Patent Document 1] S. Sullalti et al., "Effect of phosphorus based flame retardants on UL94 and Comparative Tracking Index properties of poly(butylene terephthalate)", Polymer Degradation and Stability, 2012 Summary of the Invention

[0012] Accordingly, one object of the present application is to provide a polycarbonate composition having a good combination of comparative tracking index and flame retardancy.

[0013] Another object of the present application is to provide articles that have a good combination of comparative tracking index and flame retardancy.

[0014] In a first aspect, the present invention provides a polycarbonate composition comprising, by weight of the total composition, the following components: A) 30% to 80% by weight of a copolycarbonate, i) 24 mol% to 70 mol% of formula (1): [ka] (In the formula, * indicates the position where formula (1) is attached to the polymer chain, R 1 are each independently hydrogen or C1-C4 alkyl, R 2 are each independently C1-C4 alkyl; n is 0, 1, 2, or 3; ii) 30 mol% to 76 mol% of formula (2): [ka] (In the formula, * indicates the position where formula (2) is attached to the polymer chain, R 3 are each independently H, a linear or branched C1-C 10 is alkyl, and R 4 are each independently a linear or branched C1-C 10 alkyl) units; (wherein mol % is calculated based on the total number of moles of units of formula (1) and formula (2)); B) a homopolycarbonate containing 10% by weight to 40% by weight of the unit of formula (2) defined above, the weight average molecular weight of which is in the range of 24000 g / mol to 28000 g / mol; C) 8% by weight to 25% by weight of a phosphorus-based flame retardant; D) 0% to 10% by weight of an impact modifier; E) 0% to 8% by weight of a rubber-free vinyl copolymer; where the total amount of the impact modifier and the rubber-free vinyl copolymer is 15% by weight or less; and The polycarbonate composition has a weight content of the unit of formula (1) of 24% by weight or more.

[0015] As used herein, the weight content (C 1 / C / W ) is calculated as follows: C 1 / C / W =(C 1 / CO / M ×M w1 )×C co / c / w / (C 1 / CO / M ×M w1’ +C 2 / CO / M ×M w2 ) (In the formula, C 1 / C / W represents the weight content of the unit of formula (1) in the polycarbonate composition, C 1 / CO / M represents the molar content of units of formula (1) in the copolycarbonate, M w1represents the molecular weight of the unit of formula (1), expressed in grams per mole, M w1’ represents the total molecular weight of the unit of formula (1) and -C=O-, expressed in grams per mole, C 2 / CO / M represents the molar content of units of formula (2) in the copolycarbonate, M w2 represents the molecular weight of the unit of formula (2), expressed in grams per mole, and C co / c / w represents the weight content of the copolycarbonate in the polycarbonate composition).

[0016] The inventors have unexpectedly found that compositions according to the invention have a comparative tracking index of up to 600V as determined according to IEC 60112:2011 and a flame retardancy level of V0 as determined according to UL 94-2015.

[0017] Comparative Tracking Index (CTI) means the highest voltage, determined in accordance with IEC 60112:2011, that five test specimens can withstand 50 drops of a particular electrolyte during the test period without experiencing tracking failure and sustained flame.

[0018] In a second aspect, the present invention provides a molded article made from a polycarbonate composition according to the first aspect of the invention.

[0019] In a third aspect, the present invention provides a method of making the above-mentioned molded article comprising injection molding, extrusion molding, blow molding, or thermoforming a polycarbonate composition according to the first aspect of the invention.

[0020] Other subjects, as well as characteristics, aspects and advantages of the present invention will become even more apparent upon reading the following detailed description and examples. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0021] Detailed Description of the Invention Hereinafter, unless otherwise indicated, ranges of values, in particular the expressions "between ... and ..." and "to ...", the limits are included within this range.

[0022] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In the event that a definition of a term herein conflicts with a meaning commonly understood by one of ordinary skill in the art to which this invention belongs, the definition set forth herein shall apply.

[0023] Throughout this application, the term "comprising" should be interpreted to encompass not only all specifically stated features but also any additional, unspecified features. As used herein, use of the term "comprising" also describes embodiments in which no features are present other than those specifically stated (i.e., "consisting of").

[0024] Unless otherwise specified, all numbers expressing quantities of ingredients or the like used in the detailed description and claims should be understood to be modified by the term "about."

[0025] Ingredient A According to a first embodiment, the polycarbonate composition according to the invention comprises a copolycarbonate.

[0026] In this application, copolycarbonates are i) 24 mol% to 70 mol% of formula (1): [ka] (In the formula, * indicates the position where formula (1) is attached to the polymer chain, R 1 are each independently hydrogen or C1-C4 alkyl, R 2are each independently C1-C4 alkyl; n is 0, 1, 2, or 3; ii) 30 mol% to 76 mol% of formula (2): [ka] (In the formula, * indicates the position where formula (2) is attached to the polymer chain, R 3 are each independently H, a linear or branched C1-C 10 alkyl, preferably H, linear or branched C1-C4 alkyl, and R 4 are each independently a linear or branched C1-C 10 alkyl, preferably linear or branched C1-C4 alkyl) units; (wherein mol % is calculated based on the total number of moles of units of formula (1) and formula (2)).

[0027] The unit of formula (1) is represented by formula (1'): [ka] (In the formula, R 1 each independently represents hydrogen or C1-C4 alkyl; R 2 each independently represents C1-C4 alkyl; wherein n is 0, 1, 2, or 3).

[0028] Preferably, the unit of formula (1) has the following formula (1a): [ka] (In the formula, * indicates the position where formula (1a) is attached to the polymer chain), i.e. the unit of formula (1) has the formula (1′a): [ka] It is derived from bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BPTMC), having the formula:

[0029] The unit of formula (2) is formula (2'): [ka] (In the formula, R 3 are each independently H, a linear or branched C1-C 10 represents an alkyl group, R 4 are each independently a linear or branched C1-C 10 The alkyl group may be derived from a diphenol having a substituent (e.g., aryl, aryloxy, arylalkyl).

[0030] Preferably, the unit of formula (2) is represented by the following formula (2a): [ka] (In the formula, * indicates the position where formula (2a) is attached to the polymer chain), i.e. the unit of formula (2) is bisphenol A, i.e. formula (2′a): [ka] It is derived from the diphenol

[0031] Preferably, the copolycarbonate comprises units derived from bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BPTMC) and bisphenol A.

[0032] Preferably, the copolycarbonate does not contain units derived from diphenols other than the diphenols of formula (1') and the diphenols of formula (2').

[0033] Preferably, the copolycarbonate does not contain units derived from diphenols other than bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane (BPTMC) and bisphenol A.

[0034] The diphenols of formula (1') and formula (2') are known and can be prepared by methods known from the literature (e.g., HJ Buysch et al., Ullmann's Encyclopedia of Industrial Chemistry, VCH, New York 1991, 5th Ed., Vol. 19, p. 348).

[0035] The molar content of the unit of formula (1) in the copolycarbonate is 24 mol % to 70 mol %, more preferably 40 mol % to 70 mol %, based on the total number of moles of the units of formulae (1) and (2).

[0036] The molar content of the unit of formula (2) in the copolycarbonate is 30 mol % to 76 mol %, more preferably 30 mol % to 60 mol %, based on the total number of moles of the units of formula (1) and formula (2).

[0037] The copolycarbonates used in the compositions according to the invention are commercially available or may be prepared by methods known in the art.

[0038] For example, the copolycarbonates used in the compositions according to the invention can be prepared by an interfacial process. In particular, the diphenols of formulae (1') and (2') and any branching agent are dissolved in an aqueous alkaline solution and reacted with a carbonate source, such as phosgene, optionally dissolved in a solvent, in a two-phase mixture containing the aqueous alkaline solution, an organic solvent, and a catalyst, preferably an amine compound. The reaction procedure can also be carried out in a multi-stage process.

[0039] The process for preparing such copolycarbonates is in principle known as the two-phase interfacial process, for example in H. Schnell, Chemistry and Physics of Polycarbonates, Polymer Reviews, Vol. 9, Interscience Publishers, New York 1964, page 33 et seq., and Polymer Reviews, Vol. 10, "Condensation Polymers by Interfacial and Solution Methods", Paul W. Morgan, Interscience Publishers, New York 1965, Chapter VIII, page 325, so that the underlying conditions are well known to the person skilled in the art.

[0040] The concentration of the diphenol in the alkaline aqueous solution is 2% by weight to 25% by weight, preferably 2% by weight to 20% by weight, more preferably 2% by weight to 18% by weight, and even more preferably 3% by weight to 15% by weight. The alkaline aqueous solution is made of water in which an alkali metal or alkaline earth metal hydroxide is dissolved. Sodium hydroxide and potassium hydroxide are preferred.

[0041] The concentration of the amine compound is 0.1 mol % to 10 mol %, preferably 0.2 mol % to 8 mol %, particularly preferably 0.3 mol % to 6 mol %, and more particularly preferably 0.4 mol % to 5 mol %, based on the molar amount of the diphenol used.

[0042] The carbonate source is phosgene, diphosgene, or triphosgene, preferably phosgene. When phosgene is used, the solvent may be optionally omitted and the phosgene may be passed directly into the reaction mixture.

[0043] Tertiary amines such as triethylamine or N-alkylpiperidine may be used as catalysts. Suitable catalysts are trialkylamines and 4-(dimethylamino)pyridine. Triethylamine, tripropylamine, triisopropylamine, tributylamine, triisobutylamine, N-methylpiperidine, N-ethylpiperidine, and N-propylpiperidine are particularly suitable.

[0044] Suitable organic solvents are halogenated hydrocarbons such as methylene chloride, chlorobenzene, dichlorobenzene, trichlorobenzene or mixtures thereof, or aromatic hydrocarbons such as toluene or xylene. The reaction temperature can be from -5°C to 100°C, preferably from 0°C to 80°C, particularly preferably from 10°C to 70°C, very particularly preferably from 10°C to 60°C. It is also possible to prepare copolycarbonates by a melt transesterification process, in which diphenols are reacted with diaryl carbonates, generally diphenyl carbonate, in the melt in the presence of catalysts such as alkali metal salts, ammonium compounds or phosphonium compounds.

[0045] The melt transesterification process is described, for example, in Encyclopedia of Polymer Science, Vol. 10 (1969), Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, Vol. 9, John Wiley and Sons, Inc. (1964), and in German Patent No. 1031512.

[0046] In the transesterification process, the aromatic dihydroxy compounds already described in the phase boundary process are transesterified in the melt with carbonic acid diesters using suitable catalysts and, optionally, further additives.

[0047] The reaction of the aromatic dihydroxy compounds with the carbonic acid diesters to give the copolycarbonates can be carried out batchwise or, preferably, continuously, for example in stirred tanks, thin film evaporators, falling film evaporators, stirred tank cascades, extruders, kneaders, simple disc reactors and high-viscosity disc reactors.

[0048] Preferably, the copolycarbonate is selected from block copolycarbonates and random copolycarbonates, more preferably, the copolycarbonate is selected from random copolycarbonates.

[0049] Advantageously, the copolycarbonates have a weight average molecular weight (Mw) ranging from 16000 g / mol to 40000 g / mol, preferably from 17000 g / mol to 32000 g / mol, determined by gel permeation chromatography (GPC) at 25° C. in methylene chloride with a UV-IR detector using polycarbonate standards.

[0050] An example of a commercially available copolycarbonate suitable for the composition according to the invention is the product sold under the name APEC™ by Covestro Polymer Co., Ltd. (China), which is a polycarbonate copolymer made from the copolymerization of carbonyl chloride with bisphenol A (BPA) and 3,3,5-trimethyl-1,1-bis(4-hydroxyphenyl)cyclohexane (BPTMC).

[0051] Preferably, the copolycarbonate is present in an amount ranging from 30% to 80% by weight, more preferably from 35% to 75% by weight, even more preferably from 35% to 71% by weight, relative to the total weight of the composition according to the invention.

[0052] Component B According to a first embodiment, the polycarbonate composition according to the invention comprises a homopolycarbonate comprising units of formula (2).

[0053] In this application, homopolycarbonate refers to a polycarbonate comprising units of formula (2) as defined above.

[0054] The unit of formula (2) is formula (2'): [ka] (In the formula, R 3 are each independently H, a linear or branched C1-C 10 alkyl, preferably linear or branched C1-C6-alkyl, more preferably linear or branched C1-C4-alkyl, even more preferably H or methyl, and R 4 are each independently a linear or branched C1-C 10 alkyl, preferably linear or branched C1-C6 alkyl, more preferably linear or branched C1-C4 alkyl, even more preferably methyl).

[0055] Preferably, the unit of formula (2) is of formula (2'a): [ka] It is derived from the diphenol, namely bisphenol A.

[0056] The homopolycarbonates used in the compositions according to the invention are commercially available or may be prepared by methods known in the art.

[0057] For example, homopolycarbonates can be produced by reference to the preparation methods described for component A.

[0058] Preferably, the homopolycarbonate has a weight average molecular weight (Mw) in the range of 24000 g / mol to 28000 g / mol as determined by gel permeation chromatography (GPC) at 25° C. in methylene chloride with a UV-IR detector using polycarbonate standards.

[0059] Commercially available homopolycarbonate products suitable for use in the compositions according to the invention include Makrolon™ 2400 and Makrolon™ 2600 sold by Covestro Polymer Co., Ltd. (China).

[0060] Preferably, the homopolycarbonate is present in the polycarbonate composition according to the invention in an amount ranging from 10% to 40% by weight, more preferably from 12% to 35% by weight, relative to the total weight of the composition.

[0061] Component C According to a first embodiment, the polycarbonate composition according to the invention comprises a phosphorus-based flame retardant.

[0062] Preferably, phosphorus-based flame retardants suitable for use in the compositions according to the invention are selected from monomeric and oligomeric phosphate and phosphonate esters, phosphazenes, and mixtures thereof.

[0063] Preferred monomeric and oligomeric phosphate and phosphonate esters are represented by formula (3): [ka] (In the formula, R 1 , R 2 , R 3 , and R 4 are each independently an optionally halogenated C1-C8 alkyl, C5-C6 cycloalkyl, C6-C 20 Aryl or C7-C 12aralkyl, each of which is optionally substituted by alkyl, preferably C1-C4 alkyl, and / or halogen, preferably chlorine, bromine; n's are each independently 0 or 1; q represents a number ranging from 0 to 30, and X is a phosphorus compound represented by the formula (I) in which X represents a mononuclear or polynuclear aromatic residue having 6 to 30 carbon atoms, or a linear or branched aliphatic residue having 2 to 30 carbon atoms, which may be substituted with OH and may contain up to 8 ether bonds.

[0064] Preferably, R 1 , R 2 , R 3 , and R 4 are each independently C1-C4 alkyl, phenyl, naphthyl, or phenyl C1-C4 alkyl, where the aromatic group R 1 , R 2 , R 3 , and R 4 may themselves be substituted with halogen and / or alkyl groups, preferably chlorine, bromine and / or C1-C4 alkyl. Particularly preferred aryl residues are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl, and the corresponding brominated and chlorinated derivatives thereof.

[0065] Preferably, X in formula (3) represents a mononuclear or polynuclear aromatic residue having 6 to 30 carbon atoms.

[0066] More preferably, X is derived from resorcinol, hydroquinone, bisphenol A, or diphenylphenol. Especially preferably, X is derived from bisphenol A.

[0067] Preferably, n is equal to one.

[0068] Preferably, q represents a number from 0 to 20, particularly from 0 to 10, and when a mixture of phosphorus compounds of general formula (3) is used, the average value is 0.8 to 5.0, preferably 1.0 to 3.0, more preferably 1.05 to 2.00, and particularly preferably 1.08 to 1.60.

[0069] Phosphorus compounds of formula (3) are in particular tributyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, diphenyl-2-ethyl cresyl phosphate, tri(isopropylphenyl) phosphate, resorcinol bridged oligophosphates and bisphenol A bridged oligophosphates. The use of oligomeric phosphate esters of formula (3) derived from bisphenol A is particularly preferred.

[0070] The most preferred phosphorus compound of formula (3) is represented by formula (4): [ka] It is an oligophosphate based on bisphenol A by

[0071] The phosphorus compounds of formula (3) are known (see, for example, EP-A-0 363 608, EP-A-0 640 655) or can be prepared in an analogous manner by known methods (see, for example, Ullmanns Enzyklopadie der technischen Chemie, vol. 18, pp. 301 ff. 1979; Houben-Weyl, Methoden der organischen Chemie, vol. 12 / 1, p. 43; Beilstein vol. 6, p. 177).

[0072] Preferred phosphazenes have the formula (5): [ka] (In the formula, k is an integer of 1 to 10, preferably 1 to 8, particularly preferably 1 to 5; The trimer content (k=1) is greater than 98 mol% based on the cyclic phosphazene, and R is the same or different in each occurrence, and Amine groups, C1-C8-alkyl, preferably methyl, ethyl, propyl or butyl, optionally halogenated, preferably with fluorine, more preferably monohalogenated, C1-C8-alkoxy, preferably methoxy, ethoxy, propoxy or butoxy; in each case alkyl, preferably C1-C4-alkyl and / or C5-C6-cycloalkyl, optionally substituted by halogen, preferably chlorine and / or bromine, C6-C optionally substituted by alkyl, preferably C1-C4-alkyl, and / or halogen, preferably chlorine or bromine, and / or hydroxyl. 20 -aryloxy, preferably phenoxy or naphthyloxy, C7-C optionally substituted by alkyl, preferably C1-C4-alkyl, and / or halogen, preferably chlorine and / or bromine. 12 -aralkyl, preferably phenyl-C1-C4-alkyl, or a halogen group, preferably chlorine or fluorine, or OH group, It is a cyclic phosphazene of the formula:

[0073] Phosphazenes and their preparation are described, for example, in EP-A-728811, DE-A-1961668 and WO 97 / 40092.

[0074] Preferred are: propoxyphosphazenes, phenoxyphosphazenes, methylphenoxyphosphazenes, aminophosphazenes, and fluoroalkylphosphazenes, and the following structures: [ka] of phosphazene.

[0075] In the compounds shown above, k=1, 2, or 3.

[0076] Preferably, the trimer content (k=1) is 98.5 mol % to 100 mol %, preferably 99 mol % to 100 mol %, based on the cyclic phosphazene.

[0077] When a phosphazene of formula (5) is halogen substituted on phosphorus, for example from an incompletely reacted starting material, the proportion of this phosphazene halogen substituted on phosphorus is preferably less than 1000 ppm, more preferably less than 500 ppm.

[0078] The phosphazenes can be used alone or as a mixture, i.e. the groups R can be the same or two or more groups in formula (5) can be different. Preferably, the groups R of the phosphazenes are the same.

[0079] Preferably, only phosphazenes having the same R are used.

[0080] Preferably, all R are phenoxy.

[0081] The most preferred phosphazenes are those of formula (6): [ka] phenoxyphosphazene (where all R are phenoxy) (C1).

[0082] The phosphazene oligomers in each mixture sample were 31They can also be detected and quantified by P-NMR (chemical shifts; δ for trimer: 6.5 ppm to 10.0 ppm; δ for tetramer: -10 ppm to -13.5 ppm; δ for higher oligomers: -16.5 ppm to -25.0 ppm).

[0083] An example of a commercially available phosphazene product is sold under the trade name HPCTP by Weihai Jinwei Chem Industry Co., Ltd.

[0084] Preferably, the phosphorus-based flame retardant is present in the composition according to the invention in an amount ranging from 8% to 25% by weight, more preferably from 8% to 20% by weight relative to the total weight of the composition.

[0085] Component D According to a first aspect, the polycarbonate composition of the present invention may optionally contain an impact modifier.

[0086] There is no particular limitation on the impact modifier. Any impact modifier generally used in polycarbonate compositions can be used in the polycarbonate composition according to the present invention.

[0087] Preferably, the impact modifier is D1) 5% to 95% by weight, preferably 8% to 90% by weight, in particular 20% to 85% by weight, of at least one vinyl monomer, D2) 95% by weight to 5% by weight, preferably 92% by weight to 10% by weight, in particular 80% by weight to 15% by weight of one or more graft bases having a glass transition temperature of less than 10 ° C, preferably less than 0 ° C, in particular preferably less than -20 ° C, The rubber modified vinyl (co)polymers are selected from the group consisting of:

[0088] The weight percent is calculated based on the weight of the rubber modified vinyl (co)polymer.

[0089] The glass transition temperature was determined by dynamic differential scanning calorimetry (DSC) at a heating rate of 10 K / min according to standard DIN EN 61006 as Tg was defined as the midpoint temperature (tangent method) and measured.

[0090] The at least one vinyl monomer D1 is preferably D1.1) 50% to 99% by weight, preferably 65% ​​to 85% by weight, in particular 75% to 80% by weight of vinyl aromatic compounds and / or vinyl aromatic compounds substituted on the nucleus (styrene, α-methylstyrene, p-methylstyrene, etc.) and / or methacrylic acid (C1-C8)-alkyl esters (methyl methacrylate, ethyl methacrylate, etc.), D1.2) 1% to 50% by weight, preferably 15% to 35% by weight, in particular 20% to 25% by weight of vinyl cyanide (unsaturated nitriles such as acrylonitrile and methacrylonitrile) and / or (meth)acrylic acid (C1-C8) alkyl esters such as methyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or derivatives of unsaturated carboxylic acids (anhydrides and imides, etc.), such as maleic anhydride and N-phenyl-maleimide, It is a mixture of.

[0091] The weight percentages are calculated based on the weight of vinyl monomer D1.

[0092] Preferred monomers D1.1 are selected from styrene, α-methylstyrene and methyl methacrylate. Preferred monomers D1.2 are selected from acrylonitrile, maleic anhydride and methyl methacrylate. More preferably, monomer D1.1 is styrene and monomer D1.2 is selected from acrylonitrile and methyl methacrylate.

[0093] Examples of graft bases D2 include diene rubbers, EP(D)M rubbers (i.e. rubbers based on ethylene / propylene and optionally dienes), and acrylate rubbers, polyurethane rubbers, silicone rubbers, and ethylene / vinyl acetate rubbers, and silicone / acrylate hybrid rubbers.

[0094] Preferred graft bases D2 are selected from diene rubbers, for example based on butadiene and isoprene, or mixtures of diene rubbers or copolymers of diene rubbers with further copolymerizable monomers (for example according to D1.1 and D1.2) or mixtures thereof, provided that the glass transition temperature of component D2 is below 10°C, preferably below 0°C, particularly preferably below -20°C.

[0095] Particularly preferred graft bases D2 are selected from pure polybutadiene rubbers or silicone / acrylate hybrid rubbers such as silicone-butyl acrylate rubbers.

[0096] Particularly preferred rubber-modified vinyl (co)polymers are, for example, ABS, MBS polymers, silicone-butyl acrylate rubbers grafted with methyl methacrylate, 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), and in Ullmanns, Enzyklopaedie der Technischen Chemie, vol. 19 (1980), p. 280 et seq.

[0097] The rubber modified vinyl (co)polymers may be made by free radical polymerization, for example by emulsion, suspension, solution or bulk polymerization, preferably by emulsion or bulk polymerization, especially by emulsion polymerization.

[0098] Commercially available examples of rubber modified vinyl (co)polymers that can be used in the present invention include: ABS 8391 available from SINOPEC Shanghai Gaoqiao Co., Ltd. having a polybutadiene rubber content of 10% to 15% by weight based on the ABS polymer; ABS HRG powder P60 (average particle size d ) available from Styrolution was prepared by emulsion polymerization of a mixture of 42% to 45% by weight, based on the ABS polymer, 27% by weight acrylonitrile and 73% by weight styrene in the presence of 55% to 58% by weight, based on the ABS polymer, of crosslinked polybutadiene rubber. 50 is 0.3 μm), Kane Ace M732, available from Kaneka Corporation, Japan; Metablen™ S-2130, S-2100, S-2001, S-2006, etc. available from Mitsubishi Rayon Co., Ltd. Examples include:

[0099] Advantageously, when present, the impact modifiers are present in the polycarbonate composition according to the invention in an amount ranging from 5% to 10% by weight relative to the total weight of the polycarbonate composition.

[0100] Component E According to a first aspect, the polycarbonate composition of the present invention may optionally contain a rubber-free vinyl copolymer.

[0101] Preferably, the rubber-free vinyl copolymer is E1) 65% to 85% by weight, preferably 70% to 80% by weight, in particular 74% to 78% by weight, of at least one monomer selected from vinyl aromatic compounds (for example styrene, α-methylstyrene, p-methylstyrene), in each case based on the rubber-free vinyl copolymer, E2) 15% to 35% by weight, preferably 20% to 30% by weight, in particular 22% to 26% by weight, of at least one monomer selected from the group consisting of vinyl cyanides (for example unsaturated nitriles such as acrylonitrile and methacrylonitrile), (C1-C8)-alkyl (meth)acrylates (for example methyl methacrylate, n-butyl acrylate, tert-butyl acrylate), unsaturated carboxylic acids and derivatives of unsaturated carboxylic acids (for example maleic anhydride and N-phenylmaleimide), in each case based on the rubber-free vinyl copolymer, It is a copolymer made from

[0102] Particularly preferred are rubber-free copolymers of styrene (E1) and acrylonitrile (E2).

[0103] These copolymers are known and can be prepared by free radical polymerization, particularly emulsion, suspension, solution, or bulk polymerization.

[0104] Weight average molecular weight of copolymer M w is preferably 15,000 g / mol to 250,000 g / mol, more preferably 50,000 g / mol to 160,000 g / mol, and most preferably 80,000 g / mol to 140,000 g / mol, as determined by gel permeation chromatography (GPC) using polystyrene as a standard.

[0105] An example of a commercially available rubber-free vinyl copolymer that can be used in the present invention is LUSTRAN® SAN DN50, a styrene-acrylonitrile copolymer of 77% by weight styrene and 23% by weight acrylonitrile having a weight average molecular weight Mw of 130,000 g / mol.

[0106] We have found that the addition of a rubber-free vinyl copolymer further improves the flow properties of the resulting composition.

[0107] Advantageously, when present, the rubber-free vinyl copolymer is present in the polycarbonate composition in an amount ranging from 0% to 8% by weight, preferably from 3% to 6% by weight, relative to the total weight of the polycarbonate composition.

[0108] The total amount of impact modifier (component D) and rubber-free vinyl copolymer (component E) is not more than 15% by weight, relative to the total weight of the polycarbonate composition according to the invention.

[0109] Additives In addition to the above-mentioned components A to E, the polycarbonate composition according to the present invention may optionally contain one or more additives conventionally used in polycarbonate compositions, such as fillers, carbon black, UV stabilizers, IR stabilizers, heat stabilizers, antistatic agents, pigments, colorants, lubricants, mold release agents (e.g., pentaerythritol tetrastearate), antioxidants, flow improvers, anti-dripping agents (e.g., poly(tetrafluoroethylene)), etc.

[0110] Such additives are described, for example, in WO 99 / 55772, pages 15 to 25, and in "Plastics Additives", R. Gachter and H. Müller, Hanser Publishers 1983.

[0111] One skilled in the art can select the type of additive so as not to adversely affect the desired properties of the polycarbonate composition according to the present invention.

[0112] The total amount of additives is preferably up to 4% by weight, preferably from 0% to 3% by weight, more preferably from 0% to 2% by weight, based on the total weight of the polycarbonate composition according to the invention.

[0113] Preferably, the polycarbonate composition according to the invention comprises, relative to the total weight of the composition, the following components: A) 35% to 71% by weight of a copolycarbonate, i) 40 mol% to 70 mol% of formula (1): [ka] (In the formula, R 1 are each independently hydrogen or C1-C4 alkyl, R 2 are each independently C1-C4 alkyl; n is 0, 1, 2, or 3; ii) 30 mol% to 60 mol% of formula (2): [ka] (In the formula, R 3 are each independently H, a linear or branched C1-C 10 is alkyl, and R 4 are each independently a linear or branched C1-C 10 alkyl) units; (wherein mol % is calculated based on the total number of moles of units of formula (1) and formula (2)); B) a homopolycarbonate containing 10% by weight to 40% by weight of units of formula (2) defined above, the weight average molecular weight of which is in the range of 24000 g / mol to 28000 g / mol; C) 8% by weight to 25% by weight of a phosphorus-based flame retardant having the formula (4): [ka] and oligophosphates based on bisphenol A according to formula (6), in which the oligomer content for k=1 is 98.5 mol% to 100 mol%, preferably 99 mol% to 100 mol%: [ka] phenoxyphosphazenes (wherein all R are phenoxy) (C1); D) 0% to 10% by weight of an impact modifier; E) 0% to 8% by weight of a rubber-free vinyl copolymer; where The total amount of impact modifier and rubber-free vinyl copolymer is 15% by weight or less, and The weight content of the unit of formula (1) in the polycarbonate composition is 24% by weight to 50% by weight.

[0114] Preparation of polycarbonate compositions The polycarbonate composition according to the invention may be, for example, in the form of pellets.

[0115] The polycarbonate compositions according to the invention exhibit good processing behavior and can be made by a variety of methods, including intimately mixing the materials desired in the composition.

[0116] For example, the materials desired in the composition are first blended in a high speed mixer. Blending can also be accomplished by low shear processes, including but not limited to hand blending. The blend is then fed through a hopper into the throat of a twin screw extruder. Alternatively, at least one component can be incorporated into the composition by feeding it directly into the extruder at the throat and / or downstream through a side stuffer. Additives can also be compounded with the desired polymer resin to obtain a masterbatch and fed into the extruder. The extruder is generally operated at a temperature higher than that required to make the composition flow. The extrudate is immediately quenched in a water bath and pelletized. The pellets can be ¼ inch or less in length as described. Such pellets can be used for subsequent molding, shaping, or forming.

[0117] The melt blending method is preferred due to the availability of melt blending equipment in commercial polymer processing facilities.

[0118] Illustrative examples of equipment used in such melt processing methods include co-rotating and counter-rotating extruders, single screw extruders, co-kneaders, and various other types of extrusion equipment.

[0119] It is preferable to minimize the temperature of the melt during processing to avoid excessive degradation of the polymer. In molten resin compositions, it is often desirable to maintain a melt temperature between 230° C. and 350° C., although higher temperatures can be used if the residence time of the resin in the processing equipment is kept short.

[0120] In some cases, the molten composition exits the processing equipment, such as an extruder, through small exit holes in a die. The resulting strands of molten resin are cooled by passing the strands through a water bath. The cooled strands can be chopped into small pellets for packaging and further handling.

[0121] molded product The polycarbonate compositions according to the invention can be used, for example, to produce various kinds of molded articles.

[0122] In a second aspect, the present invention also provides a molded article made from a polycarbonate composition according to the first aspect of the present invention.

[0123] Examples of such molded articles include, for example, films, profiles, housing parts, e.g., for consumer electronics or office equipment such as monitors, flat screens, notebooks, printers, and copiers, sheets, tubes, conduits, windows, doors, and other profiles for the building sector (interior and exterior applications), electrical and electronic components such as keypads, screen display covers, switches, plugs, and sockets, lenses, and body parts or interior trim for commercial vehicles.

[0124] Fabrication of molded products The polycarbonate compositions according to the present invention can be processed into molded articles by a variety of means, such as injection molding, extrusion, blow molding, or thermoforming to form molded articles.

[0125] In a third aspect, the present invention provides a method of making a molded article made from a composition according to the first aspect of the invention, the method comprising injection molding, extrusion, blow molding or thermoforming a polycarbonate composition according to the invention. EXAMPLES

[0126] The present invention will now be described in detail with reference to the following examples, which are for illustrative purposes only and are not intended to limit the scope of the present invention.

[0127] Materials used Ingredient A CoPC-1: commercially available from Covestro Polymers (China), 7 cm2 measured at 330°C and 1.2 kg according to ISO 1133: (2011) 3 % bisphenol A units, based on the total amount of bisphenol units, having an MVR of 100 / min and a weight average molecular weight of about 30,000 g / mol, determined by gel permeation chromatography (GPC) in methylene chloride at 25° C. using polycarbonate standards.

[0128] CoPC-2: commercially available from Covestro Polymer (China), 16 cm2 measured at 330°C and 1.2 kg according to ISO 1133:2011 3% bisphenol A units, based on the total amount of bisphenol units, having an MVR of 100 / 10 min and a weight average molecular weight of about 27,000 g / mol, determined by gel permeation chromatography (GPC) in methylene chloride at 25° C. using polycarbonate standards.

[0129] Component B PC-1: A linear polycarbonate based on bisphenol A, commercially available from Covestro Polymer Co., Ltd. (China) and having a weight average molecular weight (Mw) of 20,000 g / mol, determined by gel permeation chromatography (GPC) in methylene chloride at 25° C. using polycarbonate standards.

[0130] PC-2: A linear polycarbonate based on bisphenol A, commercially available from Covestro Polymer Co., Ltd. (China), with a weight average molecular weight of 24000 g / mol as determined by gel permeation chromatography (GPC) in methylene chloride at 25° C. using polycarbonate standards.

[0131] PC-3: A linear polycarbonate based on bisphenol A, commercially available from Covestro Polymer Co., Ltd. (China), with a weight average molecular weight of 26000 g / mol as determined by gel permeation chromatography (GPC) in methylene chloride at 25° C. using polycarbonate standards.

[0132] Component C BDP: Bisphenol A bis(diphenyl phosphate) available from Zhejiang Wansheng Science Co., Ltd. (China). HPCTP: available from Weihai Jinwei Chem Industry Co., Ltd., with an oligomer content of 99.9 mol% when k=1 and 0.1 mol% when k≧2, represented by the following formula: [ka] of phenoxyphosphazene.

[0133] Component D ABS: available from INEOS Styrolution GmbH under the trade name P60, a core-shell impact modifier made by emulsion polymerization of a mixture of 58% by weight, based on ABS polymer, 24% by weight acrylonitrile and 76% by weight styrene in the presence of 42% by weight, based on ABS polymer, of linear polybutadiene rubber. MBS: Methyl methacrylate-butadiene-styrene with a core / shell structure available from Kaneka Corporation of Japan under the trade name Kane Ace M732. Si-MBS: Methyl methacrylate grafted silicone-butyl acrylate rubber with core / shell available from Mitsubishi Rayon Co., Ltd. under the trade name Metablen™ S-2130.

[0134] Component E SAN: A styrene-acrylonitrile copolymer sold under the trade name LUSTRAN® SAN DN50 by INEOS Styrolution GmbH.

[0135] Other Additives PTFE: Masterbatch sold by Chemical Innovation Co., Ltd. (Thailand) under the product name ADS5000. G2: Pentaerythritol tetrastearate sold under the trade name G2 by Shanghai Coke Import Co., Ltd. (China). Irganox™ B900: a mixture of 80% Irgafos™ 168 and 20% Irganox™ 1076 sold by BASF, where Irgafos™ 168 is (tris(2,4-di-tert-butylphenyl)phosphite) and Irganox™ 1076 is (2,6-di-tert-butyl-4-(octadecaneoxy-carbonylethyl)phenol).

[0136] Test Method The physical properties of the test specimens in the examples were tested as follows.

[0137] Comparative Tracking Index The comparative tracking index (CTI) was determined according to IEC 60112:2011.

[0138] Melt Volume Flow Rate (MVR) Melt volume flow rate (MVR) was determined according to ISO 1133:2011 using a Zwick 4106 instrument from Roell at 300° C. or 330° C. and a load of 1.2 kg.

[0139] Flexural modulus Flexural modulus was determined according to ISO178:2010 at 2 mm / min.

[0140] Bending strength The flexural strength was determined according to ISO178:2010 at 5 mm / min.

[0141] Izod unnotched impact strength The Izod unnotched impact strength was measured according to ISO 180 / A:2000 (20° C., 4 mm, 5.5 J) on test specimens with dimensions of 80 mm×10 mm×4 mm.

[0142] Combustion behavior The flammability behavior was evaluated on 127 mm x 12.7 mm x 1.5 mm bars according to UL94-2015 after conditioning the bars at 23°C for 48 hours.

[0143] Vicat softening temperature Vicat softening temperature (T Vicat ) was determined in accordance with ISO 306:2013 on test specimens measuring 80 mm x 10 mm x 4 mm using a Coesfeld Eco 2920 instrument from Coesfeld Materialtest with a ram load of 50 N and a heating rate of 120 °C / h.

[0144] Examples (IE) 1 and 2 of the present invention and Comparative Examples (CE) 1 to 11 The materials listed in Table 1 were compounded and granulated in a twin-screw extruder (ZSK-26) (manufactured by Coperion, Werner and Pfleiderer) at a rotation speed of 225 rpm, a throughput of 20 kg / h, and a machine temperature of 300°C to 330°C.

[0145] The granules were processed into corresponding test specimens in an injection molding machine (Arburg) at melt temperatures of 300°C-330°C and mold temperatures of 60°C-80°C.

[0146] The physical properties of the resulting compositions, including comparative tracking index (CTI), melt volume flow rate (MVR), flexural modulus, flexural strength, Izod unnotched impact strength, and burn behavior, were tested and the results are summarized in Table 1.

[0147] [Table 1]

[0148] As used herein, the weight content of BPTMC units in a polycarbonate composition (C BPTMC / C / W ) is calculated as follows: C BPTMC / C / W =(C BPTMC / CO / M ×M wBPTMC )×C co / c / w / (C BPTMC / CO / M ×M wBPTMC’ +C BPA / CO / M ×M wBPA ) (In the formula, C BPTMC / C / W represents the weight content of BPTMC units in the polycarbonate composition, C BPTMC / CO / M represents the molar content of BPTMC units in the copolycarbonate, M wBPTMC represents the molecular weight of the BPTMC unit, expressed in grams per mole, M wBPTMC’ represents the total molecular weight of the BPTMC unit and -C=O-, expressed in grams per mole; C BPA / CO / M represents the molar content of BPA units in the copolycarbonate, M wBPA represents the molecular weight of the BPA unit, expressed in grams per mole, and C co / c / w represents the weight content of the copolycarbonate in the polycarbonate composition).

[0149] Taking Example 1 of the present invention as an example, the molar content of BPTMC units in CoPC-1 is 70 mol%, the molar content of BPA units is 30 mol%, the molecular weight of BPTMC units is 308 g / mol, the total molecular weight of BPTMC units and -C=O- is 336 g / mol, the molecular weight of BPA units (including -C=O-) is 254 g / mol, and CoPC-1 is present in the polycarbonate composition in an amount of 57.6 wt%, so the weight content of BPTMC units in Example 1 of the present invention is (70mol%×308g / mol)×57.6wt% / (70mol%×336g / mol+30mol%×254g / mol)=40wt% It is.

[0150] The compositions of Comparative Example 1, Comparative Example 2, Comparative Example 6, and Comparative Example 7, which contain CoPC-1 admixed with a flame retardant (BDP) and an impact modifier (MBS or Si-MBS), do not have good flame retardancy even when the flame retardant content is up to 12 wt % in the polycarbonate composition.

[0151] The compositions of Comparative Example 3 and Comparative Example 4, which contain CoPC-1 admixed with a flame retardant (BDP) and an impact modifier (ABS or MBS) and SAN, do not have good flame retardancy.

[0152] The composition of Comparative Example 5, which contains PC-3 admixed with a flame retardant (BDP) and an impact modifier (MBS) and SAN, does not have a high comparative tracking index.

[0153] Each of the compositions of Comparative Examples 8 to 11, which do not contain a flame retardant, does not have good flame retardancy and a high comparative tracking index.

[0154] As demonstrated by Examples 1 and 2 of the present invention, a composition comprising a copolycarbonate (CoPC-1), a homopolycarbonate (PC-3), and a flame retardant (BDP), and having a BPTMC content of 24 wt.% or more relative to the total weight of the composition, has not only a high comparative tracking index but also good flame retardancy.

[0155] Examples (IE) 3 to 6 of the present invention and Comparative Examples (CE) 12 to 15 Similarly, the materials listed in Table 2 were formulated and the resulting compositions were tested for physical properties, with the results summarized in Table 2.

[0156] [Table 2]

[0157] The composition of Comparative Example 12, which contains PC-3 blended with a flame retardant (BDP) and an impact modifier (ABS) and SAN, does not have a high comparative tracking index.

[0158] Each of the compositions of Comparative Examples 13 to 15, which contain CoPC-1 mixed with a homopolycarbonate (PC-1 or PC-3), a flame retardant (BDP), and an impact modifier (ABS), and have a BPTMC content of less than 24 wt. % based on the total weight of the composition, does not have a high comparative tracking index.

[0159] As demonstrated by Examples 3 to 6 of the present invention, a composition comprising a copolycarbonate (CoPC-1), a homopolycarbonate (PC-3), and a flame retardant (BDP), and having a BPTMC content of 24 wt % or more based on the total weight of the composition, has not only a high comparative tracking index but also good flame retardancy.

[0160] Examples (IE) 7 to 11 of the present invention and Comparative Examples (CE) 16 to 19 Similarly, the materials listed in Table 3 were formulated and the resulting compositions were tested for physical properties, with the results summarized in Table 3.

[0161] [Table 3]

[0162] Each of the compositions of Comparative Examples 16 to 19, which do not contain a homopolycarbonate and have a BPTMC content of 24 wt % or more relative to the total weight of the composition, does not have good flame retardancy, even though the composition contains up to 18 wt % HPCTP relative to the total weight of the composition.

[0163] As demonstrated by Examples 7 to 11 of the present invention, a composition comprising a copolycarbonate (CoPC-1 or CoPC-2), a homopolycarbonate (PC-2), and a flame retardant (BDP or HPCTP), and having a BPTMC content of 24 wt % or more based on the total weight of the composition, has not only a high comparative tracking index but also good flame retardancy.

Claims

1. 1. A polycarbonate composition comprising, by weight of the total composition, the following components: A) 30% to 80% by weight of a copolycarbonate, i) 24 mol% to 70 mol% of formula (1): 【Chemistry 1】 (In the formula, ＊ indicates the position where formula (1) is attached to the polymer chain, R １ are each independently hydrogen or C １ ~C ４ is alkyl, R ２ are each independently １ ~C ４ is alkyl, n is 0, 1, 2, or 3; ii) 30 mol % to 76 mol % of formula (2): 【Chemistry 2】 (In the formula, ＊ indicates the position where formula (2) is attached to the polymer chain, R ３ are each independently H, linear or branched C １ ~C １０ is alkyl, and R ４ are each independently a linear or branched C １ ~C １０ and (wherein mol % is calculated based on the total number of moles of units of formula (1) and formula (2)); B) a homopolycarbonate comprising 10% to 40% by weight of units of formula (2) as defined above, the weight average molecular weight of which is in the range of 24000 g / mol to 28000 g / mol; C) 8% to 25% by weight of a phosphorus-based flame retardant; D) 0% to 10% by weight of an impact modifier; E) 0% to 8% by weight of a rubber-free vinyl copolymer; where the total amount of the impact modifier and the rubber-free vinyl copolymer is 15% by weight or less; and A polycarbonate composition, wherein the weight content of the unit of formula (1) in the polycarbonate composition is 24% by weight or more.

2. The copolycarbonate has the formula (1'): 【Chemistry 3】 (In the formula, R １ are each independently hydrogen or C １ ~C ４ - represents alkyl, R ２ are each independently １ ~C ４ - represents alkyl, and n represents 0, 1, 2, or 3) and a diphenol of formula (2'): 【Chemistry 4】 (In the formula, R ３ are each independently H, linear or branched C １ ~C １０ represents an alkyl group, R ４ are each independently a linear or branched C １ ~C １０ 2. The composition of claim 1, which is free of units derived from diphenols other than diphenols of the formula (1), (2), (3), (4), (5), (6), (7), (8), (9), (10), (11), (12), (13), (14), (15), (16), (17), (18), (19), (20), (21), (22), (23), (24), (25), (26), (27), (28), (29), (30), (31), (32), (33), (34), (35), (46), (47), (50), (51), (52), (63), (74), (75), (86), (97), (108), (116), (120), (134), (140), (150), (162), (170), (184), (195), (196), (

3. 3. The composition according to claim 1, wherein the molar content of units of formula (1) in the copolycarbonate is from 40 mol % to 70 mol %, based on the total number of moles of units of formula (1) and formula (2).

4. The phosphorus-based flame retardant has the formula (3): 【Chemistry 5】 (In the formula, R １ , R ２ , R ３ , and R ４ are each independently an optionally halogenated C １ ~C ８ Alkyl, C ５ ~C ６ Cycloalkyl, C ６ ~C ２０ Aryl, or C ７ ~C １２ aralkyl, each of which is optionally substituted with alkyl and / or halogen; n's are each independently 0 or 1, q represents a number ranging from 0 to 30; X represents a mononuclear or polynuclear aromatic residue having 6 to 30 carbon atoms, or a linear or branched aliphatic residue having 2 to 30 carbon atoms, which may be substituted with OH and may contain up to 8 ether bonds, and a phosphorus compound of formula (5): 【Chemistry 6】 (In the formula, k is an integer from 1 to 10, The trimer content (k=1) is greater than 98 mol% based on the cyclic phosphazene, and R is the same or different in each occurrence, and Amine groups, In each case, optionally halogenated C １ ~C ８ -alkyl, C １ ~C ８ -Alkoxy C, optionally substituted in each case by alkyl and / or halogen ５ ~C ６ - cycloalkyl, C optionally substituted in each case by alkyl, and / or halogen, and / or hydroxyl ６ ~C ２０ -aryloxy, C optionally substituted with alkyl, and / or halogen, in each case ７ ~C １２ -aralkyl, or A halogen group, or OH group, wherein the cyclic phosphazenes are selected from the group consisting of The composition according to claim 1 or 2.

5. D1) 5% to 95% by weight of at least one vinyl monomer, D2) 95% to 5% by weight of one or more graft bases having a glass transition temperature of less than 10° C., 3. The composition of claim 1 or 2, further comprising an impact modifier selected from rubber modified vinyl (co)polymers comprising (wt. % is calculated based on the weight of said rubber modified vinyl (co)polymer).

6. E1) 65% to 85% by weight, in each case based on the rubber-free vinyl copolymer, of at least one monomer selected from styrene, α-methylstyrene, and p-methylstyrene; and E2) 15% to 35% by weight, in each case based on the rubber-free vinyl copolymer, of acrylonitrile, methacrylonitrile, (C １ ~C ８ 3. The composition of claim 1 or 2, further comprising a rubber-free vinyl copolymer selected from copolymers made from at least one monomer selected from N-phenylmaleimide, N-alkyl (meth)acrylate, maleic anhydride, and N-phenylmaleimide.

7. A molded article made from the composition of claim 1 or 2.

8. 8. A method for making the molded article of claim 7 comprising injection molding, extrusion, blow molding, or thermoforming the polycarbonate composition of claim 1 or 2.

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