Polycarbonate composition

Abstract

The invention relates to a polycarbonate composition comprising the following components, relative to the total weight of the composition: A) 63-81% by weight of an aromatic polycarbonate, B) 13-20% by weight of a phosphorus flame retardant, C) 4-12% by weight of an impact modifier containing 1-7% by weight of a first impact modifier and 1-7% by weight of a second impact modifier, wherein the first impact modifier is acrylonitrile-butadiene-styrene and the second impact modifier is selected from the group consisting of methyl methacrylate-butadiene-styrene and silicone-acrylic rubber-based impact modifiers, D) 1 to 6% by weight of a mineral filler, and E) 0.05 to 0.09% by weight of polytetrafluoroethylene. The invention also relates to a shaped article made from said composition. The polycarbonate composition according to the invention has a good combination of flame retardancy and impact strength.

Description

Technical Field

[0001] The present invention relates to polycarbonate (PC) compositions. In particular, the present invention relates to polycarbonate compositions and shaped articles made therefrom. Background Art

[0002] In flame retardant (FR) polymer materials, polytetrafluoroethylene (PTFE) is usually used as an anti-drip agent together with other flame retardants to ensure that it passes flame retardancy standards such as UL94 VX and 5V series. During polymer processing, such as compounding and injection molding, PTFE will form a fiber structure in the polymer to enhance the melt strength during combustion, thereby preventing dripping and potential spread of flames. In the UL94 V0 and 5V (5VB and 5VA) tests, dripping is not allowed according to the standards. In most flame retardant polycarbonate compositions, 0.2-0.5% by weight of PTFE is usually required to pass the V0 and 5V tests. Too low a PTFE loading will cause the flame retardant test to fail due to dripping. For example, US8524824 discloses a resin composition comprising (A) 75 to 99.98% by weight of an aromatic polycarbonate resin, (B) 0.01 to 5% by weight of a mixture of polytetrafluoroethylene particles and an organic polymer, and (C) 0.01 to 20% by weight of a flame retardant. It discloses in Example 1 that when the PTFE content is less than 0.1 wt%, the composition has a V2 flame retardancy level at a thickness of 1.6 mm.

[0003] Although PTFE offers advantages for flame retardancy, some regional regulations have imposed certain restrictions due to the fact that PTFE contains fluorine. This is mainly due to concerns about the impact of fluorine and fluorinated compounds on the environment and ecosystems. The DIN / VDE standard limits the fluorine content to less than 0.1%, which corresponds to a PTFE content of 0.13%. In 2020, five European countries proposed restricting the use of PFAS (per- and polyfluoroalkyl substances), including PTFE. As a result, PTFE may be included in the REACH list of substances of very high concern (SVHC) in the near future. In that case, a maximum amount of 1000 ppm may be imposed on PTFE in polymer compositions and articles made therefrom. Such a low PTFE content limit poses a huge challenge to the development of flame-retardant materials that can meet current FR test standards.

[0004] In addition, high PTFE content in the composition sometimes also causes surface defects, such as the problem of peppering due to PTFE aggregation. This is mainly caused by the incompatibility between polycarbonate and PTFE and the mismatch between their refractive indices. Therefore, it is desirable to provide a polycarbonate composition with a low PTFE content to impart good surface quality to articles prepared therefrom, especially for high gloss applications.

[0005] At the same time, it is also desired to develop polycarbonate compositions having good impact resistance.

[0006]

[0006] Therefore, there is a need for polycarbonate compositions having relatively low polytetrafluoroethylene content that can be used to prepare articles having a good combination of flame retardancy and impact strength. SUMMARY OF THE INVENTION

[0008] Therefore, one object of the present application is to provide a polycarbonate composition that has a relatively low polytetrafluoroethylene content and can be used to prepare articles having a good combination of flame retardancy and impact strength.

[0009] Another object of the present application is to provide articles having a good combination of flame retardancy and impact strength.

[0010] In a first aspect, the present invention provides a polycarbonate composition comprising the following components, relative to the total weight of the composition:

[0011] A) 63-81% by weight of aromatic polycarbonate,

[0012] B) 13-20% by weight of a phosphorus flame retardant,

[0013] C) 4-12 wt% of an impact modifier comprising 1-7 wt% of a first impact modifier and 1-7 wt% of a second impact modifier, wherein the first impact modifier is acrylonitrile-butadiene-styrene and the second impact modifier is selected from methyl methacrylate-butadiene-styrene and a silicone-acrylic rubber based impact modifier,

[0014] D) 1 to 6% by weight of mineral fillers, and

[0015] E) 0.05-0.09% by weight of polytetrafluoroethylene.

[0016] The present inventors have surprisingly found that the compositions according to the present invention can be used to prepare articles having a good combination of flame retardancy and impact strength. For example, articles prepared with the compositions according to the present invention have an impact strength of greater than 20 kJ / m² as measured according to ISO 180 / A:2000. 2At the same time, the article prepared with the composition according to the present invention has a flame retardancy of V0 as measured according to UL94:2013 and can pass the 5VB standard.

[0017] In a second aspect, the present invention provides a shaped article made from the polycarbonate composition according to the first aspect of the invention.

[0018] In a third aspect, the present invention provides a method for preparing the above-mentioned shaped article, which comprises injection molding, extrusion molding, blow molding or thermoforming the polycarbonate composition according to the first aspect of the present invention.

[0019] Other subjects and characteristics, aspects and advantages of the present invention will appear more clearly on reading the following description and examples. Detailed Description of the Invention

[0021] In the following text, and unless otherwise indicated, the limits of the numerical ranges are included in this range, particularly in the expressions "between ... and ..." and "... to ...".

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

[0023] Throughout this instant application, the term "comprising" should be interpreted as encompassing all specifically mentioned features as well as optional, additional, unspecified features. As used herein, the use of the term "comprising" also discloses embodiments in which no features other than those specifically mentioned are present (i.e., "consisting of").

[0024] Unless otherwise indicated, all numbers expressing quantities of ingredients and so forth used in the specification and claims are to be understood as modified by the term "about."

[0025] Component A

[0026] The polycarbonate composition according to the present invention comprises an aromatic polycarbonate.

[0027] According to the present invention, "aromatic polycarbonates" or simply "polycarbonates" are understood to mean homopolycarbonates and copolycarbonates, in particular those that are aromatic. These polycarbonates can be linear or branched in a known manner. According to the present invention, mixtures of polycarbonates can also be used.

[0028] The aromatic polycarbonates selected according to the present invention preferably have a weight average molecular weight M of 15,000 to 40,000 g / mol, more preferably 16,000 to 34,000 g / mol, even more preferably 17,000 to 33,000 g / mol, most preferably 19,000 to 32,000 g / mol. w . M w The values ​​of were determined by gel permeation chromatography using dichloromethane as the eluent, calibrated against bisphenol A polycarbonate standards, and calibrated with linear polycarbonates (made from bisphenol A and phosgene) with a known molar mass distribution from PSS Polymer Standards Service GmbH, Germany; calibration was performed according to method 2301-0257502-09D (German version 2009) from Currenta GmbH & Co. OHG, Leverkusen. The eluent was dichloromethane. The column was a cross-linked styrene-divinylbenzene resin. The analytical column had a diameter of 7.5 mm and a length of 300 mm. The particle size of the column material was 3 to 20 μm. The concentration of the solution was 0.2 wt %. The flow rate was 1.0 ml / min and the solution temperature was 30° C. Detection was performed using a refractive index (RI) detector.

[0029] Polycarbonates are preferably produced by the interfacial process or the melt transesterification process, which have been described numerous times in the literature.

[0030] For interfacial methods, reference is made, for example, to H. Schnell, “Chemistry and Physics of Polycarbonates”, Polymer Reviews, Vol. 9, Interscience Publishers, New York 1964, p. 33 ff., to Polymer Reviews, Vol. 10, “Condensation Polymers by Interfacial and Solution Methods”, Paul W. Morgan, Interscience Publishers, New York 1965, Chapter VIII, p. 325, to Dres. U. Grigo, K. Kircher and PR-Müller “Polycarbonate” in Becker / Braun, Kunststoff-Handbuch, Vol. 3 / 1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag Munich, Vienna 1992, pp. 118-145, and to EP 0 517 044 A1.

[0031] 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 patent specifications DE 1031512 A and US Pat. No. 6,228,973 B1.

[0032] Details regarding the preparation of polycarbonates have been disclosed in numerous patent documents spanning the past approximately 40 years. Reference may be made here, for example, to Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Vol. 9, Interscience Publishers, New York, London, Sydney 1964, to D. Freitag, U. Grigo, P. R. Müller, H. Nouvertné, BAYER AG, "Polycarbonates" in Encyclopedia of Polymer Science and Engineering, Vol. 11, 2nd edition, 1988, pp. 648-718, and finally to U. Grigo, K. Kirchner and P. R. Müller "Polycarbonate" in Becker / Braun, Kunststoff-Handbuch, Vol. 3 / 1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag Munich, Vienna 1992, pp. 117-299.

[0033] Aromatic polycarbonates are prepared, for example, by reacting dihydroxyaryl compounds with carbonyl halides, preferably phosgene, and / or with aromatic dicarboxyl dihalides, preferably benzene dicarboxyl dihalides, by means of an interfacial process, optionally using chain terminators and optionally using trifunctional or more than trifunctional branching agents, and polyester carbonates are prepared by replacing a portion of the carbonic acid derivatives with aromatic dicarboxylic acids or dicarboxylic acid derivatives, in particular aromatic dicarboxylic acid ester structural units, depending on the carbonate structural units to be replaced in the aromatic polycarbonate. Preparation is also possible by reacting dihydroxyaryl compounds with, for example, diphenyl carbonate, via a melt polymerization process.

[0034] Suitable dihydroxyaryl compounds for the preparation of polycarbonates are, for example, 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 ring-alkylated, ring-arylated and ring-halogenated compounds thereof.

[0035] Preferred dihydroxyaryl compounds are 4,4′-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, dimethylbisphenol A, 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, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane as well as bisphenols (I) to (III)

[0036]

[0037] Here, R′ in each case represents a C1- to C4-alkyl, aralkyl or aryl group, preferably represents a methyl group or a phenyl group, very particularly preferably represents a methyl group.

[0038] Particularly preferred dihydroxyaryl compounds are 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4′-dihydroxybiphenyl and dimethylbisphenol A, and also the diphenols of the formulae (I), (II) and (III).

[0039] For example, in US 3028635 A, US 2999825 A, US 3148172 A, US 2991273 A, US 3271367 A, US 4982014 A and US 2999846 A, DE 1570703 A, DE 2063050 A, DE 2036052 A, DE 2211956 A and US 2999846 A, DE 1570703 A, DE 2063050 A, DE 2036052 A, DE 2211956 A and DE 3832396 A, FR 1561518, the monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964" and JP These and other suitable dihydroxyaryl compounds are described in JP 62039 / 1986 A, JP 62040 / 1986 A and JP 105550 / 1986 A.

[0040] In the case of homopolycarbonates, only one dihydroxyaryl compound is used; in the case of copolycarbonates, two or more dihydroxyaryl compounds are used. The dihydroxyaryl compounds used, like all other chemicals and adjuvants added to the synthesis, may be contaminated by contaminants from their own synthesis, handling, and storage. However, it is desirable to use raw materials of the highest possible purity.

[0041] Suitable carbonic acid derivatives are, for example, phosgene or diphenyl carbonate.

[0042] Suitable chain terminators which can be used for the preparation of polycarbonates are monophenols. Suitable monophenols are, for example, phenol itself, alkylphenols such as cresol, p-tert-butylphenol, cumylphenol and mixtures thereof.

[0043] The preferred chain terminators are linear or branched C1-C 30 Phenols which are mono- or polysubstituted by alkyl groups, preferably unsubstituted or substituted by tert-butyl groups. Particularly preferred chain terminators are phenol, cumylphenol and / or p-tert-butylphenol.

[0044] The amount of chain terminators used is preferably from 0.1 to 5 mol %, based on the moles of diphenol used in each case. The addition of the chain terminators can be carried out before, during or after the reaction with the carbonic acid derivatives.

[0045] Suitable branching agents are trifunctional or more than trifunctional compounds familiar from polycarbonate chemistry, in particular those having three or more than three phenolic OH groups. Suitable branching agents are, for example, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, tris(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, tetrakis(4-hydroxyphenyl)methane, tetrakis(4-(4-hydroxyphenylisopropyl)phenoxy)methane and 1,4-bis((4′,4″-dihydroxyphenyl)-5′-methylbenzyl)-4-methylphenol. (triphenyl)methyl)benzene and 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole. The amount of branching agent used optionally is preferably 0.05 mol % to 2.00 mol %, based on the molar number of dihydroxyaryl compound used in each case. The branching agent can be initially added in a basic aqueous phase together with the dihydroxyaryl compound and chain terminator before phosgenation, or dissolved in an organic solvent and added. In the case of the transesterification method, the branching agent is used together with the dihydroxyaryl compound.

[0046] Particularly preferred polycarbonates are homopolycarbonates based on bisphenol A, homopolycarbonates based on 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxybiphenyl and copolycarbonates based on the two monomers bisphenol A and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and homo- or copolycarbonates derived from diphenols of the formula (I), (II) and (III).

[0047]

[0048] Here, R′ in each case represents a C1- to C4-alkyl, aralkyl or aryl group, preferably represents a methyl group or a phenyl group, very particularly preferably represents a methyl group.

[0049] Also preferred are polycarbonates prepared using dihydroxyaryl compounds of the following formula (1a):

[0050]

[0051] in

[0052] R 5 represents hydrogen or C1- to C4-alkyl, C1- to C4-alkoxy, preferably represents hydrogen or methyl or methoxy, particularly preferably represents hydrogen,

[0053] R 6 、R 7 、R 8 and R 9 Independently represent C6- to C12 - aryl or C1- to C4-alkyl, preferably phenyl or methyl, in particular represents methyl,

[0054] Y represents a single bond, SO2-, -S-, -CO-, -O-, C1- to C6-alkylene, C2- to C5-alkylidene, C6- to C5-alkylidene, which may be optionally fused with other aromatic rings containing heteroatoms, 12 -arylene, or represents a C5- to C6-cycloalkylidene residue which may be mono- or polysubstituted by C1- to C4-alkyl, preferably represents a single bond, -O-, isopropylidene or a C5- to C6-cycloalkylidene residue which may be mono- or polysubstituted by C1- to C4-alkyl,

[0055] V represents oxygen, C2- to C6-alkylene or C3- to C6-alkylidene, preferably represents oxygen or C3-alkylene,

[0056] p, q and r are independently 0 or 1,

[0057] If q=0, W is a single bond, if q=1 and r=0, W represents -O-, C2- to C6-alkylene or C3- to C6-alkylidene, preferably represents -O- or C3-alkylene,

[0058] If q=1 and r=1, W and V independently of one another represent C2- to C6-alkylene or C3- to C6-alkylidene, preferably C3-alkylene,

[0059] Z represents C1- to C6-alkylene, preferably C2-alkylene,

[0060] o represents an average number of repeating units of 10 to 500, preferably 10 to 100, and

[0061] m represents an average number of repeating units of 1 to 10, preferably 1 to 6, particularly preferably 1.5 to 5.

[0062] It is also possible to use dihydroxyaryl compounds in which two or more siloxane blocks of the general formula (1a) are linked via terephthalic acid and / or isophthalic acid under formation of ester groups.

[0063] Particularly preferred are (poly)siloxanes of formula (2) and (3)

[0064]

[0065] where R 1 represents hydrogen, C1- to C4-alkyl, preferably represents hydrogen or methyl, and particularly preferably represents hydrogen,

[0066] R 2 independently represent an aryl group or an alkyl group, preferably a methyl group,

[0067] X represents a single bond, -SO2-, -CO-, -O-, -S-, C1- to C6-alkylene, C2- to C5-alkylidene or a C6- to C5-alkylidene group which may be optionally fused to an aromatic ring containing other heteroatoms. 12 -arylene group,

[0068] X represents a single bond, -SO2-, -CO-, -O-, -S-, C1- to C6-alkylene, C2- to C5-alkylidene, C5- to C 12 -cycloalkylidene or represents a C6- to C6- 12 -arylene group,

[0069] X preferably represents a single bond, an isopropylidene group, a C5- to C 12 - cycloalkylidene or oxo, and especially preferably represents isopropylidene,

[0070] n is an average number of 10 to 400, preferably 10 to 100, particularly preferably 15 to 50, and

[0071] m represents an average number of 1 to 10, preferably 1 to 6 and particularly preferably 1.5 to 5.

[0072] The siloxane blocks may also preferably be derived from one of the following structures:

[0073]

[0074] Preferred (Va)

[0075]

[0076] Here, a in formulae (IV), (V) and (VI) is an average number of 10 to 400, preferably 10 to 100 and particularly preferably 15 to 50.

[0077] It is likewise preferred that at least two identical or different siloxane blocks of the general formula (IV), (V) or (VI) are linked via terephthalic acid and / or isophthalic acid under formation of ester groups.

[0078] It is also preferred that if p=0 in formula (1a), V represents a C3-alkylene group,

[0079] If r=1, Z represents C2-alkylene, R 8 and R 9 Represents methyl,

[0080] If q=1, W represents a C3-alkylene group,

[0081] If m=1, then R 5represents hydrogen or C1- to C4-alkyl, preferably represents hydrogen or methyl, R 6 and R 7 independently of one another represent C1- to C4-alkyl, preferably methyl, and o represents 10 to 500.

[0082] Copolycarbonates having monomer units of the general formula (1a), in particular with bisphenol A, and in particular the preparation of these copolycarbonates, are described in WO 2015 / 052106 A2.

[0083] As an example of an aromatic polycarbonate suitable for the present invention, there may be mentioned an aromatic polycarbonate prepared from bisphenol A and phosgene and sold by Covestro Co., Ltd. under the trade name 2400, 2600, 2800, 3100 of those sold.

[0084] The aromatic polycarbonate is present in the composition according to the invention in an amount of 63% to 81% by weight, preferably 65% ​​to 80% by weight, more preferably 66% to 76% by weight, relative to the total weight of the composition.

[0085] Component B

[0086] The polycarbonate composition of the present invention comprises a phosphorus flame retardant.

[0087] Preferably, the phosphorus flame retardants suitable for use in the composition according to the invention are selected from monomeric and oligomeric phosphoric and phosphonic esters and mixtures thereof.

[0088] Preferred monomeric and oligomeric phosphates and phosphonates are phosphorus compounds of formula (A):

[0089]

[0090] in

[0091] R l 、R 2 、R 3 and R 4 independently of one another, each represents an optionally halogenated C1-C8 alkyl group, a C5-C6 cycloalkyl group, a C6-C20 aryl group or a C7-C12 aralkyl group, each optionally substituted by an alkyl group, preferably a C1-C4 alkyl group, and / or a halogen group, preferably chlorine or bromine,

[0092] n represents 0 or 1 independently of each other,

[0093] q represents a value from 0 to 30, and

[0094] 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 by OH and may contain up to 8 ether bonds.

[0095] Preferably, R 1 、R 2 、R 3 and R 4 Each independently represents a C1-C4 alkyl group, a phenyl group, a naphthyl group or a phenyl C1-C4 alkyl group, wherein the aromatic group R 1 、R 2 、R 3 and R 4 It may itself be substituted by halogen and / or alkyl, preferably chlorine, bromine and / or C1-C4-alkyl. Particularly preferred aryl residues are tolyl, phenyl, xylyl, propylphenyl and butylphenyl, and the corresponding brominated and chlorinated derivatives thereof.

[0096] Preferably, X in formula (A) represents a mononuclear or polynuclear aromatic residue having 6 to 30 carbon atoms.

[0097] More preferably, X is derived from resorcinol, hydroquinone, bisphenol A or diphenylphenol. Particularly preferably, X is derived from bisphenol A.

[0098] Preferably, n is equal to 1.

[0099] Preferably, q represents a value of 0 to 20, in particular 0 to 10, and when mixtures of phosphorus compounds of the general formula (A) are used, represents an average value of 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.

[0100] Phosphorus compounds of the formula (A) are especially tributyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenylcresyl phosphate, diphenyloctyl phosphate, diphenyl-2-ethylcresyl phosphate, tris(isopropylphenyl)phosphate, resorcinol-bridged oligophosphates and bisphenol A-bridged oligophosphates.

[0101] Therefore, preferably, the phosphorus-containing flame retardant is selected from tributyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenylcresyl phosphate, diphenyloctyl phosphate, diphenyl-2-ethylcresyl phosphate, tri(isopropylphenyl) phosphate, resorcinol-bridged oligomeric phosphate, bisphenol A-bridged oligomeric phosphate, and combinations thereof.

[0102] More preferably, the phosphorus-containing flame retardant is selected from bisphenol A bis(diphenyl phosphate), resorcinol tetraphenyl diphosphate (RDP), [1,3-phenylene-tetrakis(2,6-dimethylphenyl) phosphate] and combinations thereof.

[0103] The phosphorus compounds of the formula (A) 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 (e.g., Ullmanns Enzyklopadie der technischen Chemie, Vol. 18, p. 301 ff., 1979; Houben-Weyl, Methoden der organischen Chemie, Vol. 12 / 1, p. 43; Beilstein, Vol. 6, p. 177).

[0104] It is also possible to use mixtures of phosphoric acid esters of different chemical structures and / or of the same chemical structure and different molecular weights as component D in the composition according to the invention.

[0105] The phosphorus flame retardant is present in an amount of 13 wt% to 20 wt%, preferably 14 wt% to 18 wt%, relative to the total weight of the polycarbonate composition.

[0106] Component C

[0107] According to a first aspect, the polycarbonate composition according to the present invention comprises a first impact modifier which is acrylonitrile-butadiene-styrene, and a second impact modifier which is selected from methyl methacrylate-butadiene-styrene and silicone-acrylic rubber based impact modifiers.

[0108] Acrylonitrile-butadiene-styrene

[0109] Acrylonitrile-butadiene-styrene (ABS) has a core-shell impact structure, which is described, for example, in DE-OS 2035390 or DE-OS 2248242 and Ullmanns, der Technischen Chemie, Vol. 19 (1980), pp. 280 ff.

[0110] Preferably, the acrylonitrile-butadiene-styrene (ABS) comprises 5% to 95% by weight, preferably 8% to 90% by weight, in particular 20% to 85% by weight, of units derived from acrylonitrile and styrene, and 95% to 5% by weight, preferably 92% to 10% by weight, in particular 80% to 15% by weight, of units derived from butadiene, based on the weight of the acrylonitrile-butadiene-styrene.

[0111] More preferably, the acrylonitrile-butadiene-styrene (ABS) comprises 5 to 20 wt% of units derived from acrylonitrile, 20 to 55 wt% of units derived from styrene and 75 to 30 wt% of units derived from butadiene, based on the weight of the acrylonitrile-butadiene-styrene.

[0112] As a commercial product of acrylonitrile-butadiene-styrene that can be used in the present invention, mention may be made of ABS HRG powder P60 available from Styrolution, which is obtained by mixing 42-45 wt. % of a mixture of 27 wt. % acrylonitrile and 73 wt. % styrene, based on the ABS polymer, in 55-58 wt. % of a crosslinked polybutadiene rubber (average particle size d 1 / 4) with 1% styrene. 50 It was prepared by emulsion polymerization in the presence of 0.3 μm.

[0113] The first impact modifier, acrylonitrile-butadiene-styrene, is present in the composition according to the invention in an amount of 1 to 7 wt %, preferably 2 to 6 wt %, relative to the total weight of the polycarbonate composition.

[0114] Methyl methacrylate-butadiene-styrene

[0115] Methyl methacrylate-butadiene-styrene (MBS) has a core-shell impact structure, which is described, for example, in DE-OS 2035390 or DE-OS 2248242 and Ullmanns, der Technischen Chemie, Vol. 19 (1980), pp. 280 ff.

[0116] Preferably, methyl methacrylate-butadiene-styrene (MBS) comprises 5 to 95% by weight, preferably 8 to 90% by weight, in particular 20 to 85% by weight, of units derived from methyl methacrylate and styrene, and 95 to 5% by weight, preferably 92 to 10% by weight, in particular 85 to 15% by weight, of units derived from butadiene, based on the weight of the methyl methacrylate-butadiene-styrene.

[0117] More preferably, methyl methacrylate-butadiene-styrene (MBS) comprises 10 to 35 wt.-% of units derived from methyl methacrylate, 5 to 20 wt.-% of units derived from styrene and 60 to 85 wt.-% of units derived from butadiene, based on the weight of methyl methacrylate-butadiene-styrene.

[0118] As a commercial product of methyl methacrylate-butadiene-styrene that can be used in the present invention, mention may be made of Kane Ace M732 available from Japan Kaneka Chemical Co. Ltd, which contains 10 to 35 wt% of units derived from methyl methacrylate, 5 to 10 wt% of units derived from styrene, and 60 to 85 wt% of units derived from butadiene, based on the weight of methyl methacrylate-butadiene-styrene.

[0119] Silicone-acrylic rubber-based impact modifier

[0120] Silicone-acrylate rubber-based impact modifier has a core-shell impact structure.

[0121] Preferably, the silicone-acrylate rubber based impact modifier comprises,

[0122] C.1) 5 to 90% by weight, preferably 8 to 80% by weight, in particular 10 to 70% by weight, of at least one vinyl monomer

[0123] C.2) 95% to 10% by weight, preferably 92% to 20% by weight, in particular 90% to 30% by weight, of one or more silicone-acrylate rubbers as graft base,

[0124] Weight percents are based on the weight of the impact modifier.

[0125] Vinyl monomers are used to form polymer chains and bond these chemicals to the grafting substrate.

[0126] Preferably, the vinyl monomer C.1 is selected from vinylaromatics and / or vinylaromatics substituted on the core (such as styrene, α-methylstyrene, p-methylstyrene), vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile), (C1-C8)-alkyl (meth)acrylates such as methyl methacrylate, ethyl methacrylate, n-butyl acrylate, tert-butyl acrylate and derivatives of unsaturated carboxylic acids (such as anhydrides and imides), for example maleic anhydride and N-phenylmaleimide.

[0127] More preferably, the at least one vinyl monomer C.1 comprises a (C1-C8)-alkyl (meth)acrylate or a combination thereof with styrene, α-methylstyrene or p-methylstyrene.

[0128] In some embodiments, monomer C.1 is a mixture of the following components

[0129] C.1.1) 50 to 99, preferably 60 to 80, in particular 70 to 80 parts by weight, based on C.2.1, of vinylaromatics and / or ring-substituted vinylaromatics (e.g. styrene, methylstyrene, p-methylstyrene, p-chlorostyrene) and / or (C1-C8)alkyl methacrylates, such as methyl methacrylate, ethyl methacrylate, and

[0130] C.1.2) 1 to 50, preferably 20 to 40, in particular 20 to 30 parts by weight, based on C.2.1, of (C1-C8)-alkyl (meth)acrylates, such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate and / or derivatives of unsaturated carboxylic acids (such as anhydrides and imides), for example maleic anhydride and N-phenylmaleimide.

[0131] Preferably, monomer C.1.1 is selected from at least one of the monomers styrene, methylstyrene and methyl methacrylate; preferably, monomer C.1.2 is selected from at least one of the monomers maleic anhydride and methyl methacrylate. A particularly preferred monomer is C.1.1=C.1.2 methyl methacrylate.

[0132] Silicone-acrylate composite rubbers or mixtures of different silicone-acrylate composite rubbers can be used as graft base C.2. These silicone-acrylate composite rubbers are preferably composite rubbers with grafting active sites, which contain:

[0133] C.2.1) a proportion of silicone rubber of 5% to 95% by weight, preferably 20% to 80% by weight, particularly preferably 25% to 50% by weight, and

[0134] C.2.2) a proportion of polyalkyl (meth)acrylate rubber of 95% to 5% by weight, preferably 80% to 20% by weight, particularly preferably 75% to 50% by weight,

[0135] The two rubber components interpenetrate each other in the composite rubber and are therefore essentially inseparable.

[0136] The particularly preferred ratio of silicone rubber and polyalkyl (meth)acrylate rubber results in a particularly advantageous combination of good mechanical properties, a good surface of the component part and good resistance to hydrolytic molecular weight degradation and to the influence of chemicals.

[0137] Silicone-acrylate composite rubbers are known and are described, for example, in US Pat. No. 5,807,914, EP 430134 and US Pat. No. 4,888,388.

[0138] Suitable silicone rubber components C.2.1 of the silicone-acrylate composite rubbers are silicone rubbers having grafting-active sites, the preparation of which is described, for example, in US Pat. No. 2,891,920, US Pat. No. 3,294,725, DE-A 3631540, EP 249964, EP 430134 and US Pat. No. 4,888,388.

[0139] The silicone rubbers according to C.2.1 are preferably prepared by emulsion polymerization, using siloxane monomer units, crosslinking or branching agents and optionally grafting agents.

[0140] Examples of siloxane monomers preferably used for preparing silicone rubbers include dimethylsiloxanes or cyclic organosiloxanes having at least 3 ring members, preferably 3 to 6 ring members, such as and preferably hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane.

[0141] The organosiloxane monomer may be used alone or in the form of a mixture comprising two or more monomers.

[0142] The crosslinking agent is preferably a silane-based crosslinking agent having a functionality of 3 or 4, particularly preferably 4. Preferred examples include trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane, and tetrabutoxysilane. The crosslinking agent can be used alone or as a mixture of two or more. Tetraethoxysilane is particularly preferred.

[0143] Examples of grafting agents include β-methacryloyloxyethyldimethoxymethylsilane, γ-ethylacryloyloxypropylmethoxydimethylsilane, γ-methacryloyloxypropyldimethoxymethylsilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropylethoxydiethylsilane, γ-methacryloyloxypropyldiethoxymethylsilane, δ-methacryloyloxybutyldiethoxymethylsilane, or mixtures thereof.

[0144] Preference is given to using from 0 to 20% by weight of grafting agent, based on the total weight of the silicone rubber.

[0145] Silicone rubbers can be prepared by emulsion polymerization as described in, for example, US Pat. No. 2,891,920 and US Pat. No. 3,294,725.

[0146] Suitable polyalkyl (meth)acrylate rubber components C.2.2 of the silicone-acrylate composite rubber can be prepared from alkyl methacrylates and / or alkyl acrylates, crosslinkers and grafting agents.

[0147] Examples of preferred alkyl methacrylates and / or alkyl acrylates include C1- to C8-alkyl esters, such as methyl, ethyl, n-butyl, tert-butyl, n-propyl, n-hexyl, n-octyl, n-dodecyl, and 2-ethylhexyl esters; haloalkyl esters, preferably halo-C1-C8-alkyl esters, such as chloroethyl acrylate, and mixtures of these monomers. Particularly preferred is n-butyl acrylate.

[0148] Crosslinking agents useful for the polyalkyl (meth)acrylate rubber component of the silicone-acrylate rubber include monomers having more than one polymerizable double bond. Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids having 3 to 8 carbon atoms and unsaturated monohydric alcohols having 3 to 12 carbon atoms, or saturated polyhydric alcohols having 2 to 4 OH groups and 2 to 20 carbon atoms, such as ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate, and 1,4-butylene glycol dimethacrylate. The crosslinking agents can be used alone or as a mixture of at least two crosslinking agents.

[0149] Examples of preferred grafting agents include allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, or mixtures thereof. Allyl methacrylate may also be used as a crosslinking agent. The grafting agent may be used alone or as a mixture of at least two grafting agents.

[0150] The amount of the crosslinking agent and the grafting agent is from 0.1% to 20% by weight, based on the total weight of the polyalkyl (meth)acrylate rubber component of the silicone-acrylate rubber.

[0151] The silicone-acrylate composite rubber is prepared by first preparing the silicone rubber of C.2.1 in the form of an aqueous latex. This latex is then enriched with the alkyl methacrylate and / or alkyl acrylate to be used, a crosslinking agent, and a grafting agent, and polymerized.

[0152] The silicone-acrylate composite graft rubber is prepared by grafting the monomers onto the rubber substrate C.2. This can be done using the polymerization methods described in, for example, EP 249964, EP 430134 and US Pat. No. 4,888,388.

[0153] As the silicone-acrylate rubber, silicone-acrylate C1-C8 alkyl ester rubber can be mentioned, and in particular, silicone-butyl acrylate rubber can be mentioned as an example.

[0154] Preferably, the silicone-acrylate rubber-based impact modifier is selected from silicone-acrylate C1-C8 alkyl rubber grafted with (meth)acrylate (C1-C8)-alkyl ester.

[0155] More preferably, the silicone-acrylate rubber based impact modifier is a methyl methacrylate grafted silicone-butyl acrylate rubber.

[0156] As an example of commercially available silicone-acrylate rubber-based impact modifiers that can be used in the present invention, mention may be made of Metablen S-2001, Metablen S-2030, Metablen S-2100 and Metablen S-2100 from Mitsubishi Rayon Co., Ltd. S2130.

[0157] In some embodiments, methyl methacrylate grafted silicone-butyl acrylate rubber is used, e.g. S2130 and Metablen S2100 served as the second impact modifier.

[0158] The second impact modifier selected from methyl methacrylate-butadiene-styrene and silicone-acrylic rubber-based impact modifiers is present in the polycarbonate composition according to the present invention in an amount of 1% to 7% by weight, preferably 2% to 6% by weight, relative to the total weight of the polycarbonate composition.

[0159] According to some embodiments, the composition comprises 2 wt% to 6 wt% acrylonitrile-butadiene-styrene and 2 wt% to 6 wt% methyl methacrylate-butadiene-styrene.

[0160] According to some embodiments, the composition comprises 2 to 6 weight percent acrylonitrile-butadiene-styrene and 2 to 6 weight percent methyl methacrylate grafted silicone-butyl acrylate rubber.

[0161] The total amount of the first impact modifier and the second impact modifier is from 1% to 12% by weight, preferably from 6% to 10% by weight, relative to the total weight of the composition according to the invention.

[0162] Component D

[0163] According to a first aspect, the polycarbonate composition according to the invention comprises as component D at least one mineral filler.

[0164] Mineral fillers suitable for use in the compositions of the present invention may be in the form of particles, flakes and fibers.

[0165] According to some embodiments, the mineral filler is selected from mica, talc, calcium carbonate, wollastonite, barium sulfate, silicon dioxide, kaolin, inorganic whiskers, glass microspheres, glass flakes, glass fiber, basalt fiber, carbon fiber, boron nitride, graphite, and a combination of two or more thereof. Preferably, the mineral filler is selected from mica, talc, wollastonite, silicon dioxide, kaolin, inorganic whiskers, boron nitride, and a combination of two or more thereof. More preferably, the mineral filler is kaolin.

[0166] The microgranular and flaky mineral fillers may have an average particle size of 0.1-40 μm, preferably 0.1-15 μm and more preferably 0.1-3 μm. The fibrous mineral fillers may have an average diameter of 1-30 μm and an aspect ratio of 4-100, and preferably have an average diameter of 3-20 μm and an aspect ratio of 5-30.

[0167] Preferred mineral fillers include kaolin having an average particle size of 0.1-2 μm and talc having an average particle size of 0.5-3 μm.

[0168] The average particle size refers to the average Stokes equivalent particle size determined by sedimentation.

[0169] The mineral filler is present in the polycarbonate composition in an amount of 1 wt % to 6 wt %, preferably 1 wt % to 5 wt %, relative to the total weight of the polycarbonate composition.

[0170] Component E

[0171] According to a first aspect, the polycarbonate composition according to the invention comprises, as component E, polytetrafluoroethylene.

[0172] Polytetrafluoroethylene can be prepared by known methods, for example, by reacting tetrafluoroethylene in an aqueous medium containing a free radical forming catalyst, such as sodium peroxodisulfate, potassium peroxodisulfate or ammonium peroxodisulfate at 7 kg / cm 2 Up to 71kg / cm 2 The polymer is prepared by polymerization under a pressure of 1000 ℃ and at a temperature of 0° C. to 200° C., preferably at a temperature of 20 to 100° C. For further details, see, for example, US Pat. No. 2,393,967.

[0173] Preferably, polytetrafluoroethylene has a viscosity of 1.2 g / cm 3 to 2.3g / cm 3 density.

[0174] More preferably, the polytetrafluoroethylene used according to the present invention has an average particle size of 0.05 μm to 20 μm, preferably 0.08 μm to 10 μm and a particle size of 1.2 g / cm 3 to 1.9g / cm 3 density.

[0175] Polytetrafluoroethylene can be used alone or as a masterbatch with homopolymers or copolymers of styrene or methyl methacrylate.

[0176] As an example of a commercial product of polytetrafluoroethylene, there may be mentioned the product sold by DuPont under the trade name like Those sold at 30N.

[0177] Masterbatches of polytetrafluoroethylene and styrene-acrylonitrile (SAN) in a 1:1 weight ratio may be used, such as ADS 5000 available from Chemical Innovation Co., Ltd. Thailand and POLYB FS-200 available from Han Nanotech Co., Ltd.

[0178] The polytetrafluoroethylene is present in the polycarbonate composition in an amount of 0.05 wt% to 0.09 wt%, preferably 0.06 wt% to 0.08 wt%, relative to the total weight of the polycarbonate composition.

[0179] Additional components

[0180] In addition to the above-mentioned components AE, the polycarbonate composition according to the present invention may optionally contain one or more additives conventionally used in polycarbonate compositions as additional components. Such additives include, for example, UV stabilizers, IR stabilizers, heat stabilizers, antistatic agents, pigments (such as carbon black), colorants, lubricants (such as waxes), mold release agents (such as pentaerythritol tetrastearate), antioxidants, pH regulators, flow improvers, and the like.

[0181] A person 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.

[0182] In some embodiments, the composition according to the present invention may further comprise, based on the total weight of the composition, up to 5 wt %, preferably up to 3 wt %, more preferably 0.1 wt % to 3 wt % of additional components selected from antioxidants, heat stabilizers, release agents, antistatic agents, pigments, pH adjusters and lubricants.

[0183] Preferably, the polycarbonate composition according to the present invention comprises, relative to the total weight of the composition:

[0184] A) 66 to 76% by weight of an aromatic polycarbonate based on bisphenol A,

[0185] B) 14-18% by weight of a phosphorus flame retardant selected from bisphenol A bis(diphenyl phosphate), resorcinol tetraphenyl diphosphate (RDP) and [1,3-phenylene-tetrakis(2,6-dimethylphenyl)phosphate],

[0186] C) 2 to 6% by weight of acrylonitrile-butadiene-styrene and 2 to 6% by weight of an impact modifier selected from methyl methacrylate-butadiene-styrene and methyl methacrylate-grafted silicone-butyl acrylate rubber,

[0187] D) 1-5% by weight of kaolin, and

[0188] E) 0.05-0.09% by weight of polytetrafluoroethylene.

[0189] The total amount of components A) to E) as defined above, based on the total weight of the polycarbonate composition according to the invention, is 90% to 100% by weight, preferably 95% to 100% by weight, more preferably 97% to 100% by weight.

[0190] Preparation of polycarbonate compositions

[0191] The polycarbonate composition according to the present invention may be in the form of pellets, for example.

[0192] The polycarbonate compositions according to the present invention exhibit good processing behavior and can be prepared by various methods involving intimate admixture of the materials desired in the composition.

[0193] For example, the materials required in the composition are first blended in a high-speed mixer. Low shear methods, including but not limited to manual mixing, can also achieve this blending. The blend is then fed into the throat of a twin-screw extruder via a hopper. Alternatively, at least one component can be incorporated into the composition by feeding it directly into the extruder at the throat and / or feeding it via a side filler downstream. Additives can also be compounded into a masterbatch with the required polymer resin and fed into the extruder. The extruder is typically operated at a temperature higher than the temperature required to make the composition flow. The extrudate is immediately quenched and granulated in a water bath. As described, the pellets can be a quarter inch long or less. Such pellets can be used for subsequent molding, shaping or forming.

[0194] Melt blending methods are preferred due to the availability of melt blending equipment in commercial polymer processing facilities.

[0195] 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.

[0196] The melt temperature during processing is preferably minimized to avoid excessive degradation of the polymer. It is generally desirable to maintain the melt temperature in the molten resin composition between 220°C and 320°C, although higher temperatures can be used as long as the residence time of the resin in the processing equipment is kept short.

[0197] In some cases, the molten composition is discharged from a processing device, such as an extruder, via a small exit hole in a die. The resulting strand of molten resin is cooled by passing it through a water bath. The cooled strand can be cut into small pellets for packaging and further processing.

[0198] Molded products

[0199] The polycarbonate composition according to the invention can be used, for example, for the preparation of various types of shaped articles.

[0200] In a second aspect, the present invention also provides a shaped article made from the polycarbonate composition according to the first aspect of the present invention.

[0201] As examples of such molded articles, those used in housing parts of electric and electronic products such as printers, copiers, chargers, television projectors, notebook computers, tablet computers (pads), game consoles, and the like may be mentioned.

[0202] Preparation of molded products

[0203] The polycarbonate composition according to the present invention can be processed into shaped articles by various means, such as injection molding, extrusion molding, blow molding or thermoforming, to form shaped articles.

[0204] In a third aspect, the present invention provides a method for preparing a shaped article made from the composition according to the first aspect of the present invention, which comprises injection molding, extrusion molding, blow molding or thermoforming the polycarbonate composition according to the present invention. Example

[0205] The present invention will be described in detail with reference to the following examples, which are provided for illustrative purposes only and are not intended to limit the scope of the present invention.

[0206] Materials used

[0207] Component A

[0208] PC-1: available from Covestro Polymer (China) Co., Ltd., a linear polycarbonate based on bisphenol A having a weight average molecular weight of 26,000 g / mol as determined by gel permeation chromatography (GPC) in dichloromethane at 25° C. using polycarbonate standards.

[0209] PC-2: available from Covestro Polymer (China) Co., Ltd., a linear polycarbonate based on bisphenol A having a weight average molecular weight (Mw) of 24,000 g / mol as determined by gel permeation chromatography (GPC) in dichloromethane at 25° C. using polycarbonate standards.

[0210] Component B

[0211] BDP: bisphenol A bis(diphenyl phosphate), available from Zhejiang Wansheng Science China Company.

[0212] Component C

[0213] ABS: prepared by emulsion polymerization of a mixture of 27% by weight acrylonitrile and 73% by weight styrene in the presence of 55-58% by weight of crosslinked polybutadiene rubber, based on the ABS polymer, 42-45% by weight, based on the ABS polymer, available from Styrolution as ABS HRGpowder P60.

[0214] MBS: methyl methacrylate-butadiene-styrene, available as Kane Ace M732 from Japan Kaneka Chemical Co., Ltd.

[0215] S-2130: A silicone-acrylic rubber based impact modifier available as Metablen S-2130 from Mitsubishi Chemical Corporation.

[0216] S-2100: A silicone-acrylic rubber based impact modifier available as Metablen S-2100 from Mitsubishi Chemical Corporation.

[0217] Component D

[0218] Kaolin: Available from KaMin LLC as Polyfil HG90 with a median particle size of 0.4 μm.

[0219] Talc: Available from IMI Fabi LLC as ultra5C with a median diameter of 0.65 μm.

[0220] Component E

[0221] PTFE-SAN: anti-drip agent, polytetrafluoroethylene (PTFE) end-capped with styrene-acrylonitrile copolymer (SAN) at a weight ratio of PTFE:SAN = 1:1, available as ADS5000 from IRPC Public Company Limited.

[0222] Other components

[0223] PETS: Pentaerythritol tetrastearate, a mold release agent, available as FACIL 348 from FACI Asia Pacific Pte Ltd (Singapore).

[0224] B900: 80% available from BASF 168 and 20% A mixture of 1076, wherein 168 is tris(2,4-di-tert-butylphenyl) phosphite, 1076 is 2,6-di-tert-butyl-4-(octadecyloxy-carbonylethyl)phenol.

[0225] Test Method

[0226] The physical properties of the samples in the examples were tested as follows.

[0227] Izod notched impact strength

[0228] The Izod notched impact strength was measured according to ISO 180 / A:2000 (23° C., 4 mm, 5.5 J) on test specimens with dimensions of 80 mm×10 mm×4 mm.

[0229] Burning behavior

[0230] UL 94@1.5mm: Measured according to UL94:2015 on 125mm x 12.5mm bars with a thickness of 1.5mm

[0231] UL 945VB@2.0mm:

[0232] In the UL94 vertical flame test, flame is applied to a 125 mm x 12.5 mm specimen with a thickness of 2.0 mm, which has been stored at 23°C for 2 days, which is vertically fixed above a cotton wool pad. If combustion stops within 60 seconds after the flame is applied to the specimen five times and no dripping ignites the pad, the specimen will be considered to have achieved a rating of 5VB and the test will be classified as "passed". Otherwise, the test will be classified as "failed".

[0233] Comparative Examples (CE) 1-7 and Inventive Examples (IE) 1-5

[0234] The materials listed in Table 1 were compounded on a twin-screw extruder (ZSK-26) (from Coperion, Werner and Pfleiderer) at a rotation speed of 250 rpm, a throughput of 30 kg / h and a machine temperature of 240-290° C. and pelletized.

[0235] The resulting pellets were processed on an injection molding machine (from Arburg) at a melt temperature of 240-300° C., a mold temperature of 80° C. and a flow front speed of 240 mm / s to give corresponding test specimens.

[0236] The properties of the molded parts based on the obtained compositions were tested, including notched Izod impact strength and burning behavior, and the results are summarized in Table 1.

[0237] As can be seen from Table 1, the molded part based on Comparative Example 1, which contains 0.2 wt% PTFE (which corresponds to 0.4 wt% PTFE-SAN masterbatch) and 8 wt% acrylonitrile-butadiene-styrene and does not contain a second impact modifier and a mineral filler, has a flame retardancy level of V0 in the UL 94@1.5 mm test and can pass the UL 945VB@2.0 mm test.

[0238] A molded part based on Comparative Example 2 containing 0.125 wt% PTFE (corresponding to 0.25 wt% PTFE masterbatch) and 8 wt% acrylonitrile-butadiene-styrene and no secondary impact modifier and mineral filler failed the UL 945VB@2.0 mm test.

[0239] The molded part based on Comparative Example 3 containing 8 wt% acrylonitrile-butadiene-styrene and no second impact modifier and mineral filler had a flame retardancy level of V1 in the UL 94@1.5 mm test and failed the UL945VB@2.0 mm test.

[0240] The molded parts based on Comparative Examples 4-6, which did not contain mineral fillers, failed the UL 945VB@2.0 mm test.

[0241] The molded part based on Comparative Example 7, which contained 8 wt% of the silicone-acrylic rubber-based impact modifier and no mineral filler, failed the UL 945VB@2.0 mm test.

[0242] The molded parts based on the inventive examples 1-5 comprising a combination of ABS P60 and Metablen S-2130 and the mineral filler kaolin had an average heat release of at least 36 kJ / m 2It has excellent Izod notched impact strength, V0 flame retardant level in UL 94@1.5mm test and can pass UL 945VB@2.0mm test.

[0243]

[0244] Comparative Examples (CE) 8-12 and Inventive Examples (IE) 6-13

[0245] Similarly, the materials listed in Table 2 were compounded, the properties of the molded parts based on the obtained compositions were tested, and the results are summarized in Table 2.

[0246] As can be seen from Table 2, the molded parts of Comparative Examples 8-11, which are based on a combination of ABS P60 and MBS Kane Ace M732 or Metablen S-2100 but do not contain mineral fillers, fail the UL 945VB@2.0 mm test.

[0247] The molded part based on Comparative Example 12 containing 8 wt% methyl methacrylate-butadiene-styrene and no second impact modifier and mineral filler failed the UL 945VB@2.0 mm test.

[0248] The molded parts based on the inventive examples 6 to 13 comprising a combination of ABS P60 and MBS Kane Ace M732 or Metablen S-2100 and the mineral filler kaolin had an average heat release of at least 22 kJ / m 2 It has excellent Izod notched impact strength, V0 flame retardant level in UL 94@1.5mm test and can pass UL 945VB@2.0mm test.

[0249]

[0250] Comparative Examples (CE) 13-15 and Inventive Examples (IE) 14-17

[0251] Similarly, the materials listed in Table 3 were compounded, the properties of the molded parts based on the obtained compositions were tested, and the results are summarized in Table 3.

[0252] Table 3

[0253]

[0254] As can be seen in Table 3, the molded parts of Comparative Examples 13-14 based on the combination that does not include acrylonitrile-butadiene-styrene and a second impact modifier selected from methyl methacrylate-butadiene-styrene and silicone-acrylic rubber based impact modifiers fail to pass the UL 945VB@2.0 mm test.

[0255] The molded part of Comparative Example 15 based on a combination that does not include methyl methacrylate-butadiene-styrene and a second impact modifier selected from acrylonitrile-butadiene-styrene and silicone-acrylic rubber-based impact modifiers has an impact strength of less than 10 kJ / m 2 Izod notched impact strength.

[0256] The molded parts based on the inventive examples 14-17 comprising a combination of ABS P60 and Metablen S-2130 or Metablen S-2100 and the mineral filler talc had an average heat release of at least 24 kJ / m 2 It has excellent Izod notched impact strength, V0 flame retardant level in UL 94@1.5mm test and can pass UL 945VB@2.0mm test.

[0257] Comparative Example (CE) 16 and Inventive Examples (IE) 18-24

[0258] Similarly, the materials listed in Table 4 were compounded, the properties of the molded parts based on the obtained compositions were tested, and the results are summarized in Table 4.

[0259] Table 4

[0260]

[0261] As can be seen in Table 4, the molded part based on Comparative Example 16 containing 0.04 wt% PTFE (which corresponds to 0.08 wt% PTFE masterbatch) fails the UL 945VB@2.0 mm test.

[0262] The molded parts based on Inventive Examples 18-21 containing low PTFE masterbatch loadings of 0.12 wt% to 0.15 wt% and a combination of ABS P60 and Metablen S-2130 or S-2100 and 6 wt% kaolin had a thermal conductivity of at least 32 kJ / m 2 It has excellent Izod notched impact strength, V0 flame retardant level in UL 94@1.5mm test and can pass UL 945VB@2.0mm test.

[0263] The molded parts based on Inventive Examples 21-24 comprising a combination of ABS P60 and Metablen S-2130 having a total impact modifier loading of 6 wt% to 10 wt% and 1 wt% to 6 wt% kaolin had an Izod notched impact strength of at least 30 kJ / m2, a flame retardancy level of V0 in the UL 94@1.5 mm test, and could pass the UL 945VB@2.0 mm test.

[0264] The above results show that there is a clear synergistic effect between the impact modifier combination and the mineral filler according to the present invention, which can bring good FR performance (V0@1.5mm and 5VB@2.0mm) at low PTFE% (<1000ppm). This provides a solution to the potential regulatory changes on fluorinated compounds.

Claims

1. A polycarbonate composition comprising the following components relative to the total weight of the composition: A) 63-81% by weight of aromatic polycarbonate, B) 13-20% by weight of a phosphorus flame retardant, C) 4-12 wt% of an impact modifier comprising 1-7 wt% of a first impact modifier and 1-7 wt% of a second impact modifier, wherein the first impact modifier is acrylonitrile-butadiene-styrene and the second impact modifier is selected from the group consisting of methyl methacrylate-butadiene-styrene and silicone-acrylic rubber based impact modifiers, D) 1 to 6% by weight of mineral fillers, and E) 0.05-0.09% by weight of polytetrafluoroethylene.

2. The polycarbonate composition according to claim 1, wherein the phosphorus-containing flame retardant is selected from the phosphorus compounds of formula (A): in R l 、R 2 、R 3 and R 4 independently of one another, each represents an optionally halogenated C1-C8 alkyl group, a C5-C6 cycloalkyl group, a C6-C20 aryl group or a C7-C12 aralkyl group, each optionally substituted by an alkyl group, preferably a C1-C4 alkyl group, and / or a halogen group, preferably chlorine or bromine, n represents 0 or 1 independently of each other, q represents a value from 0 to 30, and 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 by OH and may contain up to 8 ether bonds.

3. The polycarbonate composition of claim 2, wherein the phosphorus-containing flame retardant is selected from the group consisting of tributyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenylcresyl phosphate, diphenyloctyl phosphate, diphenyl-2-ethylcresyl phosphate, tris(isopropylphenyl) phosphate, resorcinol-bridged oligomeric phosphate esters, bisphenol A-bridged oligomeric phosphate esters, and combinations thereof.

4. The polycarbonate composition of claim 1, wherein the phosphorus-containing flame retardant is selected from the group consisting of bisphenol A bis(diphenyl phosphate), resorcinol tetraphenyl diphosphate, [1,3-phenylene-tetrakis(2,6-dimethylphenyl) phosphate], and combinations thereof.

5. The polycarbonate composition according to any one of claims 1 to 4, wherein the silicone-acrylate rubber-based impact modifier is selected from silicone-acrylate C1-C8 alkyl ester rubber grafted with (meth)acrylate (C1-C8)-alkyl ester.

6. The polycarbonate composition of claim 5, wherein the silicone-acrylate rubber-based impact modifier is a methyl methacrylate-grafted silicone-butyl acrylate rubber.

7. The polycarbonate composition of any one of claims 1 to 3, wherein the composition comprises 2 to 6 weight percent acrylonitrile-butadiene-styrene and 2 to 6 weight percent methyl methacrylate-butadiene-styrene.

8. The polycarbonate composition according to any one of claims 1 to 3, wherein the composition comprises 2 to 6 weight percent acrylonitrile-butadiene-styrene and 2 to 6 weight percent methyl methacrylate-grafted silicone-butyl acrylate rubber.

9. The polycarbonate composition according to any one of claims 1 to 8, wherein the mineral filler is selected from the group consisting of mica, talc, wollastonite, silica, kaolin, inorganic whiskers, boron nitride, and combinations of two or more thereof.

10. The polycarbonate composition according to any one of claims 1 to 8, wherein the mineral filler is selected from the group consisting of mica, talc, wollastonite, silica, kaolin, and combinations of two or more thereof.

11. The polycarbonate composition of any one of claims 1 to 8, wherein the mineral filler is kaolin.

12. The composition according to any one of claims 1 to 11, comprising, relative to the total weight of the composition: A) 66 to 76% by weight of an aromatic polycarbonate based on bisphenol A, B) 14 to 18% by weight of a phosphorus flame retardant selected from bisphenol A bis(diphenyl phosphate), resorcinol tetraphenyl diphosphate and [1,3-phenylene-tetrakis(2,6-dimethylphenyl)phosphate], C) 2 to 6% by weight of acrylonitrile-butadiene-styrene and 2 to 6% by weight of an impact modifier selected from methyl methacrylate-butadiene-styrene and methyl methacrylate-grafted silicone-butyl acrylate rubber, D) 1-5% by weight of kaolin, and E) 0.05-0.09% by weight of polytetrafluoroethylene.

13. The composition according to any one of claims 1 to 12, wherein the total amount of components A) to E) as defined above is 90% to 100% by weight, preferably 95% to 100% by weight, more preferably 97% to 100% by weight, based on the total weight of the polycarbonate composition according to the invention.

14. A shaped article made from the composition according to any one of claims 1 to 13.

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