Flame Retardant Polycarbonate Composition

Abstract

The present invention relates to a flame-retardant polycarbonate composition comprising the following components, based on the total weight of the composition: A) 40 - 60% by weight of at least one aromatic polycarbonate, B) 30 - 50% by weight of at least one polysiloxane-polycarbonate condensate, C) 0.5 - 5% by weight of at least one cyclophosphazene, D) 1 - 5% by weight of at least one impact modifier based on silicone-acrylate rubber, E) 0.3 - 3% by weight of aluminum hydroxide, F) 0.1 - 1% by weight of at least one anti-dripping agent, and G) 0.1 - 1% by weight of at least one UV absorber. The present invention also relates to a shaped article made from the composition. The polycarbonate composition according to the present invention has a good combination of low-temperature impact properties, flame retardancy, hydrolysis stability, anti-UV properties, and heat resistance.

Description

Technical Field

[0001] The present invention belongs to the field of polycarbonates. Specifically, the present invention relates to a flame-retardant polycarbonate composition and a shaped article made therefrom. Background Art

[0002] There are high requirements for plastic housing materials used in outdoor applications that are exposed to harsh environmental conditions such as extreme high or low temperatures, high humidity, and fire risks. In most cases, these materials need good low-temperature impact performance, good hydrolysis stability, good UV resistance, high flame retardancy, and high heat resistance.

[0003] Polycarbonate (PC) resins exhibit high heat resistance and good impact performance at room temperature. However, at low temperatures below 0 °C and even lower, PC resins are sensitive to small defects and residual internal stresses, and thus cannot resist large external impacts. To improve the low-temperature impact strength, impact modifiers (mostly having a core-shell structure with a rubber core and grafted chains) are usually compounded with polycarbonate raw materials. However, some residual acids, emulsifiers, and metal ions can have an adverse effect on the hydrolysis stability of polycarbonate blends. In addition, a large amount of impact modifiers can also lead to a reduction in flame retardancy. The addition of flame retardants such as conventional phosphorus-containing flame retardants (bisphenol-A bis(diphenyl phosphate) (BDP), tetraphenyl resorcinol diphosphate (RDP), etc.) helps to improve flame retardancy, but sacrifices impact performance, heat resistance, and hydrolysis stability.

[0004] Polysiloxane-polycarbonate copolymers (Si-co-PC) have become good candidates to replace conventional core-shell structure impact modifiers to provide good low-temperature impact performance without negatively affecting flame retardancy. However, most Si-co-PC resins available on the market have a low siloxane content (<10%) and cannot provide good low-temperature impact strength alone.

[0005] Therefore, achieving a balance among the low-temperature impact performance, flame retardancy, hydrolysis stability, UV resistance, and heat resistance of polycarbonate blends for outdoor applications is a great challenge.

[0006] WO2015 / 022676A discloses a blended thermoplastic composition comprising at least one polycarbonate component, at least one impact modifier, at least one mineral filler, and at least one flame retardant, and the resulting composition can be used to manufacture articles that require materials to have high modulus, ultra-high ductility, good fluidity, thin-wall flame retardancy, and good heat resistance. All examples in this document contain 15% mineral filler. Materials with this composition are expected to have poor low-temperature impact performance and low heat resistance.

[0007] WO2003 / 042305A1 discloses a flame-retardant resin composition comprising (i) at least one aromatic polycarbonate, (ii) at least one silicon source, (iii) at least one boron source, and (iv) optionally at least one member selected from the group consisting of a drip retardant, a second thermoplastic resin other than a polycarbonate resin, and a rubber-modified graft copolymer. The boron compounds used herein may have a negative impact on the thermal stability and hydrolysis stability of the composition.

[0008] WO2007 / 037952A1 discloses a flame-retardant thermoplastic composition comprising in combination a polycarbonate component; an impact modifier; a filler having a surface treatment including pretreatment of the filler with a vinyl-functionalized silane coupling agent or mixing with a vinyl-functionalized silane coupling agent; a polycarbonate-polysiloxane copolymer; and a flame retardant. All examples in this document contain 10% filler and BDP as the flame retardant. Materials having this composition are expected to have poor low-temperature impact properties and low heat resistance.

[0009] Accordingly, there is still a need to provide a polycarbonate composition having a good combination of low-temperature impact properties, flame retardancy, hydrolysis stability, UV resistance, and heat resistance. Summary of the Invention

[0011] One object of the present application is to provide a polycarbonate composition having a good combination of low-temperature impact properties, flame retardancy, hydrolysis stability, UV resistance, and heat resistance.

[0012] Accordingly, in a first aspect, the present invention provides a flame-retardant polycarbonate composition comprising the following components, based on the total weight of the composition:

[0013] A) 40 - 60% by weight of at least one aromatic polycarbonate,

[0014] B) 30 - 50% by weight of at least one polyorganosiloxane-polycarbonate copolymer,

[0015] C) 0.5 - 5% by weight of at least one cyclophosphazene,

[0016] D) 1 - 5% by weight of at least one impact modifier based on silicone-acrylate rubber,

[0017] E) 0.3 - 3% by weight of aluminum hydroxide,

[0018] F) 0.1 - 1% by weight of at least one drip retardant, and

[0019] G) 0.1 - 1% by weight of at least one UV absorber.

[0020] According to a second aspect, the present invention provides a shaped article made of a polycarbonate composition according to the first aspect of the present invention.

[0021] According to a third aspect, the present invention provides a method for preparing a shaped article according to the second aspect of the present invention, which includes injection molding, extrusion molding, blow molding or thermoforming of the polycarbonate composition according to the first aspect of the present invention.

[0022] The polycarbonate composition and the shaped article according to the present invention have good flame retardancy, excellent low temperature impact resistance, good heat resistance and good hydrolysis stability.

[0023] The polycarbonate composition and the shaped article according to the present invention are suitable for outdoor applications that require high flame retardancy (such as UL94 5VB), good hydrolysis stability and excellent low temperature impact strength, such as network antennas, electric vehicle charging gun housings, photovoltaic junction boxes, electric motorcycle battery housings, etc.

[0024] Other subjects, features, aspects and advantages of the present invention will become even clearer when reading the following description and examples. Detailed Description of the Invention

[0026] In the following, unless otherwise specified, the limits of numerical ranges are included in the range, especially in the expressions "between... and..." and "... to...".

[0027] As used herein, the expression "comprising / including" should be interpreted as covering all specifically mentioned features as well as optional, additional, unspecified features.

[0028] As used herein, the expression "at least one" means one or more.

[0029] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by those of ordinary skill in the art to which the present invention pertains. When the definition of a certain term in this specification conflicts with the meaning commonly understood by those skilled in the art to which the present invention pertains, the definition described herein will be adopted.

[0030] Unless otherwise specified, all numerical values representing the amounts of components and the like used in this specification and claims should be understood to be modified by the term "about".

[0031] All percentages in this application refer to weight percentages unless otherwise specified.

[0032] On the premise of no conflict, the technical features described for each component in the composition according to the present invention can be combined in any way.

[0033] Component A

[0034] According to a first aspect, the polycarbonate composition according to the invention comprises at least one aromatic polycarbonate as component A.

[0035] Aromatic polycarbonates suitable as component A according to the invention are known from the literature or can be prepared by methods known from the literature (for the preparation of aromatic polycarbonates see, for example, Schnell's "Chemistry and Physics of Polycarbonates", Interscience Publishers, 1964, and DE-AS 1 495 626, DE-A 2 232 877, DE-A 2 703 376, DE -A 2 714 544, DE-A 3 000 610, DE-A 3 832 396; and DE-A 3 007 934).

[0036] Aromatic polycarbonates can be prepared by the interfacial method, for example by reacting a diphenol with a carbonic acid halide, preferably phosgene, and / or with an aromatic dicarboxylic acid dihalide, preferably phthalic acid dihalide, optionally using a chain terminator such as a monophenol, and optionally using a trifunctional or higher-functional branching agent, such as a triphenol or a tetraphenol. They can also be prepared by the melt polymerization method by reacting a diphenol with, for example, diphenyl carbonate.

[0037] The diphenols used for the preparation of aromatic polycarbonates are preferably those of formula (I):

[0038]

[0039] where

[0040] A is a single bond, a C1-C5-alkylene, a C2-C5-alkylidene, a C5-C6-cycloalkylene, -O-, -SO-, -CO-, -S-, -SO2-, a C6-C arylene which may be fused with other aromatic rings optionally containing heteroatoms 12 -arylene,

[0041] or a group of formula (II) or (III):

[0042]

[0043] B is in each case a C1-C 12 -alkyl, preferably methyl, or a halogen, preferably chlorine and / or bromine,

[0044] x is in each case independently 0, 1 or 2,

[0045] p is 1 or 0, and

[0046] R5 and R 6 can be selected individually for each X 1 and are, independently of one another, hydrogen or C1-C6-alkyl, preferably hydrogen, methyl or ethyl,

[0047] X 1 is carbon, and

[0048] m is an integer from 4 to 7, preferably 4 or 5,

[0049] provided that R 5 and R 6 are simultaneously alkyl on at least one atom X 1 Preferred diphenols are hydroquinone, resorcinol and dihydroxydiphenols, bis(hydroxyphenyl)-C1-C5-alkanes, bis(hydroxyphenyl)-C5-C6-cycloalkanes, bis(hydroxyphenyl) ethers, bis(hydroxyphenyl) sulfoxides, bis(hydroxyphenyl) ketones, bis(hydroxyphenyl) sulfones and α,α-bis(hydroxyphenyl) diisopropylbenzenes and their ring-brominated and / or ring-chlorinated derivatives.

[0050] Particularly preferred diphenols are 4,4'-dihydroxybiphenyl, bisphenol A, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4´-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfone and their dibromo and tetrabromo or chloro derivatives, such as, for example, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane or 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane. 2,2-Bis(4-hydroxyphenyl)propane (bisphenol A) is particularly preferred.

[0051] The diphenols can be used individually or as any desired mixture. The diphenols are known from the literature or can be obtained by methods known from the literature.

[0052]

[0053] ​Examples of suitable chain terminators for the preparation of thermoplastic polycarbonates are phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, and long-chain alkylphenols such as 4-[2-(2,4,4-trimethyl-pentyl)]phenol and 4-(1,3-tetramethylbutyl)phenol according to DE-A 2 842 005, or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl substituent, such as 3,5-di-tert-butylphenol, p-isooctylphenol, p-tert-octylphenol, p-dodecylphenol, 2-(3,5-dimethylheptyl)phenol and 4-(3,5-dimethylheptyl)phenol. The amount of chain terminator used is generally 0.5 mol% to 10 mol%, based on the sum of the moles of the particular diphenol used.

[0054] Thermoplastic aromatic polycarbonates can be branched in a known manner, preferably by incorporating 0.05 to 2.0 mol% of trifunctional or higher-functional compounds, based on the sum of the diphenols used, such as compounds having three or more phenolic groups.

[0055] Both homopolycarbonates and copolycarbonates are suitable. In the case of using a copolycarbonate as component A, the copolycarbonate is different from the polysiloxane-polycarbonate copolymer used as component B described in detail below.

[0056] The aromatic dicarboxylic diacid halides for the preparation of aromatic polycarbonates are preferably the diacid dichlorides of isophthalic acid, terephthalic acid, 4,4'-dicarboxylic acid of diphenyl ether and 2,6-naphthalenedicarboxylic acid.

[0057] Particularly preferred is a mixture of the diacid dichlorides of isophthalic acid and terephthalic acid in a ratio of 1:20 to 20:1.

[0058] In the preparation of polycarbonates, a carbonyl halide, preferably phosgene, is also used simultaneously as a difunctional acid derivative.

[0059] Suitable chain terminators for the preparation of aromatic polycarbonates, in addition to the monophenols already mentioned, are also their chloroformates and acid chlorides of aromatic monocarboxylic acids, which may optionally be replaced by C1-C 22 -alkyl or halogen atoms and aliphatic C2-C 22 -monocarboxylic acid chlorides.

[0060] In each case, the amount of chain terminator is 0.1 to 10 mol%, based on the number of moles of the diphenol for phenolic chain terminators and based on the number of moles of the dicarboxylic diacid chloride for monocarboxylic acid chloride chain terminators.

[0061] One or more aromatic hydroxycarboxylic acids can also be used for the preparation of aromatic polycarbonates.

[0062] The aromatic polycarbonate can be linear and can be branched in a known manner (in this regard, see DE-A 2940 024 and DE-A 3 007 934), preferably a linear polycarbonate.

[0063] Examples of branching agents that can be used are trifunctional or higher-functional carboxylic acid acyl chlorides, such as trimesoyl chloride, cyanuric chloride, benzophenone-3,3',4,4'-tetracarboxylic acid tetrachloride, naphthalene-1,4,5,8-tetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride, in an amount of 0.01 to 1.0 mol% (based on the dicarboxylic acid dichloride used), or trifunctional or higher-functional phenols, such as phloroglucinol, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)-2-heptene, 4,6-dimethyl-2,4,6-tris(4-hydroxyphenyl)heptane, 1,3,5-tris(4-hydroxyphenyl)benzene, 1,1,1-tris(4-hydroxyphenyl)ethane, tris(4-hydroxyphenyl)phenylmethane, 2,2-bis[4,4-bis(4-hydroxyphenyl)cyclohexyl]propane, 2,4-bis(4-hydroxyphenylisopropyl)phenol, tetrakis(4-hydroxyphenyl)methane, 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)propane, tetrakis(4-[4-hydroxyphenylisopropyl]phenoxy)methane or 1,4-bis[4,4'-(dihydroxytriphenyl)methyl]benzene, in an amount of 0.05 to 2.0 mol%, based on the diphenol used. The phenolic branching agent can be used together with the diphenol; the acid acyl chloride branching agent can be introduced together with the acid dichloride.

[0064] The proportion of carbonate structural units in the thermoplastic aromatic polycarbonate can be freely varied. The proportion of carbonate groups is preferably at most 100 mol%, especially at most 80 mol% and particularly preferably at most 50 mol%, based on the sum of the ester groups and carbonate groups. The ester part and carbonate part of the aromatic polycarbonate can be present in the polycondensation product in the form of a block or random distribution.

[0065] The polycarbonate used is preferably linear and more preferably based on bisphenol A.

[0066] Preferably, the aromatic polycarbonate has a weight average molecular weight (M W , measured by GPC (gel permeation chromatography using a bisphenol A-based polycarbonate as a standard in dichloromethane)) of 15,000 to 80,000 g / mol, preferably 20,000 to 32,000 g / mol, more preferably 23,000 to 28,000 g / mol and even more preferably 24,000 to 26,000 g / mol.

[0067] As examples of the aromatic polycarbonates suitable for the present invention, mention may be made of those sold by Covestro Co., Ltd under the names Makrolon® 2600 and Makrolon® 2400.

[0068] The aromatic polycarbonate may be used alone or in any desired mixture.

[0069] Advantageously, the aromatic polycarbonate is present in the polycarbonate composition in an amount of 45% to 60% by weight, preferably 47% to 55% by weight, based on the total weight of the polycarbonate composition.

[0070] Component B

[0071] According to a first aspect, the polycarbonate composition according to the present invention comprises at least one polysiloxane-polycarbonate copolymer (also referred to herein as "SicoPC") as component B.

[0072] The polysiloxane-polycarbonate copolymer comprises a polydiorganosiloxane (also referred to herein as "siloxane") block and a polycarbonate block.

[0073] In particular, the polysiloxane-polycarbonate block copolymer comprises structural unit (IV)

[0074] (IV)

[0075] wherein R1 is a divalent substituted or unsubstituted aromatic group, a divalent straight-chain or cyclic aliphatic group

[0076] or the structural unit (IV) is a mixture of units, wherein R1 is a divalent substituted or unsubstituted aromatic group, or R1 is a divalent straight-chain or cyclic aliphatic group, and based on the total of the diphenols used in the following formula (I') in weight percent form, the proportion of aromatic R1 groups is 60 - 100% by weight and the proportion of aliphatic groups is 0 - 40% by weight,

[0077] and structural unit (V)

[0078] (V)

[0079] wherein R2 is independently at each occurrence a C1 to C 13 monovalent organic group, such as C1 to C 13 alkyl, C1 to C 13 alkoxy, C2 to C 13 alkenyl group, C2 to C 13Alkenyloxy, C3-C6 cycloalkyl, C3-C6 cycloalkyloxy, optionally completely or partially halogenated by fluorine, chlorine, bromine or iodine or a combination thereof.

[0080] Preferably, each occurrence of R2 is independently C1-C 12 alkyl, particularly preferably C1-C4 alkyl, especially methyl.

[0081] A very particularly preferred structural unit (V) is a dimethylsiloxane unit, or a diphenylsiloxane unit, a methyl / phenylsiloxane unit or a mixture of dimethylsiloxane and diphenylsiloxane units.

[0082] Component B preferably contains 2% to 20% by weight of the structural unit of formula (V), preferably 3% to 10% by weight of the structural unit of formula (V), also referred to hereinafter as the siloxane block, based on the weight of component B.

[0083] In the structural unit (IV), R1 preferably derives from a dihydroxyaryl compound of formula (I’)

[0084] (I’)

[0085] A is a single bond, C1-C5-alkylene, C2-C5-alkylidene, C5-C6-cycloalkylene, -O-, -SO-, -CO-, S-, -SO2-, C6-C 12 -arylene, which may be fused with other aromatic rings optionally containing heteroatoms,

[0086] or a group of formula (II’) or (III’):

[0087] (II’)

[0088] (III’)

[0089] B is in each case C1-C 12 -alkyl, preferably methyl, or halogen, preferably chlorine and / or bromine,

[0090] x are each independently of one another 0, 1 or 2,

[0091] p is 1 or 0, and

[0092] R 5 and R 6 can be selected individually for each X 1 and are independently of one another hydrogen or C1-C6-alkyl, preferably hydrogen, methyl or ethyl,

[0093] X 1 is carbon, and

[0094] m is an integer from 4 to 7, preferably 4 or 5,

[0095] provided that R 5 and R 6 are simultaneously alkyl groups on at least one atom X 1

[0096] Examples of the diphenols of formula (I') suitable for preparing SiCoPC according to the present invention include hydroquinone, resorcinol, bis(hydroxyphenyl)alkanes, bis(hydroxyphenyl)sulfides, bis(hydroxyphenyl)ethers, bis(hydroxyphenyl)ketones, bis(hydroxyphenyl)sulfones, bis(hydroxyphenyl)sulfoxides, [α],[α]'-bis(hydroxyphenyl)diisopropylbenzene, and their alkylated, cycloalkylated, and cyclo-halogenated compounds.

[0097] More preferred diphenols of formula (I') are 4,4'-dihydroxybiphenyl, 2,2-bis(4-hydroxyphenyl)-1-phenylpropane, 1,1-bis(4-hydroxyphenyl)phenyl ethane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,3-bis[2-(4-hydroxyphenyl)-2-propyl]benzene (bisphenol M), 2,2-bis(3-methyl-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxyphenyl)sulfone, 2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,3-bis[2-(3,5-dimethyl-4-hydroxyphenyl)-2-propyl]benzene, 1,1-bis(4-hydroxyphenyl)cyclohexane, and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane.

[0098] Particularly preferred diphenols of formula (I') are 2,2-bis(4-hydroxyphenyl)propane (BPA), hydroquinone, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and 2,2-bis(3-methyl-4-hydroxyphenyl)propane.

[0099] ​These and other suitable diphenols are commercially available and are described, for example, in "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964, pages 28 ff; pages 102 ff" and "D. G. Legrand, J. T. Bendler, Handbook of Polycarbonate Science and Technology, Marcel Dekker New York 2000, pages 72 ff".

[0100] Preferably, the siloxane block has the following structure (VI)

[0101] (VI)

[0102] wherein R2 is as defined above for structural unit (V),

[0103] n represents an average number from 10 to 400, preferably an average number from 10 to 100, particularly preferably an average number from 15 to 50, in each case determined by 1H-NMR spectroscopy

[0104] k represents 0 or 1,

[0105] R3 independently comprises the following structural elements (VII) or (VIII) each time it occurs:

[0106] (VII)

[0107] wherein R4 independently represents hydrogen, halogen and / or C1 to C 10 , preferably C1 to C4, straight-chain or branched, unsubstituted or mono- to tetra-substituted alkyl or alkoxy groups, wherein the alkyl and alkoxy groups are preferably unsubstituted, and R4 is particularly preferably hydrogen,

[0108] e is 0 or a natural number between 2 and 12, preferably 2 to 6, wherein, when e is 0, k is 1,

[0109] (VIII)

[0110] wherein, R 6 and R 7 independently of one another represent H, C1-C 18 -alkyl, C1-C 18 -alkoxy, halogen such as Cl or Br, or in each case optionally substituted aryl or aralkyl, preferably independently of one another represent H or C1-C12 -alkyl, particularly preferably H or C1-C8-alkyl, and very particularly preferably each independently represents H or methyl,

[0111] and

[0112] X represents -CO-, -O-, -S-, C1-C6-alkylene, C2-C5-alkylidene, C6-C 10 -cycloalkylene or C6-C 12 -arylene which may optionally be fused to another heteroatom-containing aromatic ring.

[0113] Preferably, X represents C1-C5-alkylene, C2-C5-alkylidene, C6-C9-cycloalkylene, -O-, -SO-, -CO-, -S-, -SO2-, particularly preferably isopropylidene, 3,3,5-trimethylcyclohexylidene or oxygen, especially isopropylidene.

[0114] For example and preferably, the silicone block is derived from structure (IX) or structure (X):

[0115] (IX)

[0116] (X)

[0117] wherein, in formulae (IX) and (X), a represents an average number from 10 to 400, preferably an average number from 10 to 100, particularly preferably an average number from 15 to 50, in each case determined by 1H-NMR spectroscopy.

[0118] The 1H-NMR spectra of all the silicone blocks shown herein and of the entire component B can be carried out in a deuterated chloro solvent, preferably in deuterated chloroform or deuterated dichloromethane. Integrate the appropriate signals and compare in each case.

[0119] In structures IX and X, for example, it is determined by using the integral of the SiCH3 protons between 0 and 0.5 ppm chemical shift and the integral of the adjacent CH2 at about 2.6 ppm chemical shift a .

[0120] In another embodiment, the above silicone block can be linked one or more times by terephthalic acid or isophthalic acid to provide the following exemplary structural elements:

[0121] (XI)

[0122] where p represents 0 or 1,

[0123] R2, R3, n and k are as defined above for the structural element (VI).

[0124] The corresponding siloxane blocks for reaction with polycarbonates or for reaction with diphenols of formula (I') and phosgene or with diaryl carbonates each have terminal phenolic hydroxyl groups. That is

[0125] (XIa)

[0126] wherein R2, R3, n, k and p are as defined for structural element (XI).

[0127] Particularly preferably, the siloxane block is a hydroxyaryl-terminated (poly)siloxane of formula (XII)

[0128] (XII).

[0129] In general formula (XII), R5 represents hydrogen or a C1-C4-alkyl, C1-C4-alkoxy group, preferably hydrogen or methyl, methoxy, particularly preferably hydrogen.

[0130] R 6 and R 7 each independently represent an aryl group, preferably phenyl, a C1-C4-alkyl group, preferably methyl, in particular methyl.

[0131] Y represents a single bond, -CO-, -O-, a C1-C5-alkylene, a C2-C5-alkylidene or a C5-C6-cycloalkylene group, which may be mono- or polysubstituted by C1-C4-alkyl groups, preferably a single bond, -O-, isopropylidene or a C5-C6-cycloalkylene group, which may be mono- or polysubstituted by C1-C4-alkyl groups, in particular isopropylidene.

[0132] V represents oxygen, a C1 to C6 alkylene or a C2-C5-alkylidene, preferably a single bond, oxygen, a C3 alkylene, in particular oxygen or isopropylidene.

[0133] W represents a single bond, S, a C1-C6-alkylene or a C2-C5-alkylidene, preferably a single bond, a C3 alkylene or isopropylidene, where, when q represents 1, W is not a single bond.

[0134] p and q each independently represent 0 or 1.

[0135] o represents the average number of repeating units from 10 to 400, preferably the average number of repeating units from 10 to 100, particularly preferably the average number of repeating units from 15 to 50, in each case determined by 1H-NMR spectroscopy.

[0136] For example, o is determined using the integral of the middle Si-CH3 protons (at a chemical shift of about 0.1 ppm) relative to the integral of the two terminal siloxane units of the block, i.e. O-Si(CH3)2 (at a chemical shift of about 0.2 ppm).

[0137] m represents the average number of repeating units from 1 to 10, preferably the average number of repeating units from 1 to 6, particularly preferably the average number of repeating units from 1.5 to 5, in each case determined by 1H-NMR spectroscopy.

[0138] Very particularly preferred are the siloxanes of the formulas (XIII) and (XIV)

[0139] (XIII)

[0140] (XIV)

[0141] wherein

[0142] R1 independently of one another represents hydrogen, Cl, Br or C1-C4-alkyl, preferably hydrogen or methyl, and particularly preferably hydrogen,

[0143] R2 independently of one another represents aryl or C1-C 13 alkyl, preferably C1-C4-alkyl,

[0144] X represents a single bond, -O-, -SO-, -CO-, -S-, -SO2-, C1-C6-alkylene, C2-C5-alkylidene, C5-C 12 -cycloalkylene or C6-C optionally fused to an aromatic ring containing other heteroatoms 12 -arylene, preferably represents a single bond, -O-, -SO-, -CO-, -S-, -SO2-, C1-C5-alkylene, C2-C5-alkylidene, C5-C 12 -cycloalkylene, particularly preferably a single bond, isopropylidene, C5 to C 12 cycloalkylene or oxygen, and very particularly preferably isopropylidene,

[0145] n represents an average number from 10 to 400, preferably an average number from 10 to 100, particularly preferably an average number from 10 to 50, in each case determined by 1H-NMR spectroscopy, and

[0146] m represents an average number from 1 to 10, preferably an average number from 1 to 6, and particularly preferably an average number from 1.5 to 5, in each case determined by 1H-NMR spectroscopy.

[0147] n in the structures XI, XIII and XIV is determined as described above for o.

[0148] The determination of m is carried out using the proton integration of the terminal phenyl groups, for example the proton integration of the terminal bisphenol A-derived units, and the integration of the intermediate phenyl groups, for example the integration of the intermediate bisphenol A-derived units.

[0149] Most preferably, the siloxanes of formula XIV are used, since they exhibit particularly good thermal and color stability.

[0150] The siloxane component, i.e. the weight-average molecular weight Mw of the siloxane block, is preferably from 3000 to 20 000 g / mol, determined by gel permeation chromatography using BPA (bisphenol A) polycarbonate standards, particularly preferably from 3500 - 15 000 g / mol.

[0151] The preparation of the siloxanes of the formulae (XII) to (XIV) is described, for example, in DE 33 34 782 A1 and DE19710081.

[0152] The siloxane component of the formula (XII), (XIII) or (XIV) is used in an amount of from 0.5% to 50% by weight, preferably from 1% to 40% by weight, particularly preferably from 2% to 20% by weight and very particularly preferably from 2.5% to 10% by weight, in each case based on the weight of component B.

[0153] The preparation of the siloxane blocks is in principle known and they can be prepared by the methods described, for example, in US20130267665.

[0154] Polysiloxane-polycarbonate copolymers are generally produced industrially from monomers and phosgene by the interfacial method. The production of these polysiloxane-polycarbonate copolymers by the melt transesterification method using diphenyl carbonate is also known.

[0155] The production of polysiloxane-polycarbonate copolymers by the interfacial method is known from the literature and is described, for example, in US-A 3189 662, US-A 3 419 634, DE-A 3 34 782 and EP 0 122 535.

[0156] US 5 227 449 describes the production of polysiloxane-polycarbonate copolymers by the melt transesterification method from bisphenols, diaryl carbonates, silanol-terminated polysiloxanes and catalysts.

[0157] Reactive extrusion processes for the production of polysiloxane-polycarbonate copolymers have also been described. For example, this is disclosed in US 5414054 and US 5821321.

[0158] The polysiloxane-polycarbonate copolymers used according to the invention are preferably produced by the melt transesterification method, more preferably by the reactive extrusion method. The reactive extrusion method preferably comprises mixing and reacting the following components in the melt in an extruder or high-viscosity reactor

[0159] a) At least one polymer containing structural units of formula (IV), preferably an aromatic polycarbonate

[0160] b) At least one hydroxyaryl-terminated (poly)siloxane, preferably according to any one of formulas IX, X, XIa, XII, XIII, XIV

[0161] c) Optionally, at least one additive is used, such as a catalyst.

[0162] The extruder or melt reactor can be a single-screw reactor, a twin-screw reactor or a multi-screw reactor, such as a planetary roller extruder or an annular extruder. High-capacity kneading reactors can also be of interest.

[0163] The process can be carried out in a single device - such as a twin-screw extruder - or in two stages, i.e., a reactor combination. The reactor combination preferably consists of a pre-reactor - such as a twin-screw extruder - and a high-viscosity reactor.

[0164] The process is preferably carried out at a temperature of 280 °C to 400 °C, preferably 290 °C to 380 °C, more preferably 300 °C to 350 °C and a pressure of 0.001 mbar to 50 mbar, preferably 0.005 mbar to 40 mbar, particularly preferably 0.02 to 30 mbar and very particularly preferably 0.03 to 5 mbar, preferably in the presence of a catalyst.

[0165] Advantageously, the polysiloxane-polycarbonate copolymer is present in the polycarbonate composition according to the invention in an amount of 33% to 48% by weight, preferably 35% to 47% by weight, based on the total weight of the polycarbonate component.

[0166] Preferably, the total amount of components A and B is not less than 90% by weight, based on the total weight of the polycarbonate composition.

[0167] Component C

[0168] According to a first aspect, the polycarbonate composition according to the invention comprises at least one cyclophosphazene as component C.

[0169] The cyclophosphazene preferably used according to the invention is a cyclophosphazene of formula (XV):

[0170] (XV)

[0171] where

[0172] k is an integer from 1 to 10, preferably a value from 1 to 8 and particularly preferably from 1 to 5

[0173] 60 to 100 mol% trimer content (k = 1), based on component C

[0174] and wherein

[0175] R is the same or different in each case and represents

[0176] - an amino group,

[0177] - a C1-C8-alkyl group, preferably methyl, ethyl, propyl or butyl, optionally halogenated in each case, preferably fluorinated, and more preferably monohalogenated,

[0178] - a C1-C8-alkoxy group, preferably methoxy, ethoxy, propoxy or butoxy,

[0179] - a C5-C6-cycloalkyl group, optionally substituted in each case by an alkyl group, preferably a C1-C4-alkyl group, and / or by a halogen, preferably chlorine and / or bromine,

[0180] - C6-C 20 - an aryloxy group, preferably phenoxy or naphthyloxy, optionally substituted in each case by an alkyl group, preferably a C1-C4-alkyl group, and / or by a halogen, preferably chlorine or bromine, and / or by a hydroxyl group,

[0181] - C7-C 12 - an aralkyl group, preferably phenyl-C1-C4-alkyl, optionally substituted in each case by an alkyl group, preferably a C1-C4-alkyl group, and / or by a halogen, preferably chlorine and / or bromine,

[0182] - a halogen group, preferably chlorine or fluorine, or

[0183] - an OH group.

[0184] The following are preferred: propoxyphosphazene, phenoxyphosphazene, methylphenoxyphosphazene, aminophosphazene and fluoroalkylphosphazene, and phosphazenes of the following structure:

[0185]

[0186] In the above compounds, k = 1, 2 or 3.

[0187] If the phosphazene of formula (XV) is halogenated on phosphorus, e.g. from incompletely reacted starting materials, the proportion of phosphazene halogenated on phosphorus is preferably less than 1000 ppm, more preferably less than 500 ppm.

[0188] The phosphazenes can be used alone or as a mixture, i.e. the groups R can be the same, or two or more of the groups in formula (XV) can be different. Preferably, the groups R of the phosphazene are the same.

[0189] In a more preferred embodiment, only phosphazenes with the same R are used.

[0190] Preferably, all R = phenoxy.

[0191] The most preferred compounds are phenoxyphosphazenes of formula (XVI) in which the oligomer content with k = 1 (C1) is 65 mol% - 100 mol% (all R = phenoxy).

[0192] (XVI)

[0193] In one embodiment, a phenoxyphosphazene of formula (XVI) is used as component C, wherein the trimer content (k = 1) is 85 to 100 mol%, more preferably 98.5 to 100 mol%, even more preferably 99 to 100 mol% based on component C.

[0194] Phosphazenes and their preparation are described, for example, in EP - A 728 811, DE - A 1 961 668 and WO 97 / 40092.

[0195] After compounding, it is also possible to 31 detect and quantify the oligomer composition of the phosphazene in each blend sample by P - NMR (chemical shift; δ trimer: 6.5 to 10.0 ppm; δ tetramer: - 10 to - 13.5 ppm; δ higher oligomers: - 16.5 to - 25.0 ppm).

[0196] Advantageously, the cyclophosphazene is present in the polycarbonate composition in an amount of 1 wt% to 5 wt%, 1.5 wt% to 4.5 wt% based on the total weight of the polycarbonate composition.

[0197] Component D

[0198] According to a first aspect, the polycarbonate composition according to the invention comprises at least one impact modifier based on silicone - acrylate rubber as component D.

[0199] The impact modifier based on silicone - acrylate rubber has a core - shell impact structure.

[0200] Preferably, the impact modifier based on silicone - acrylate rubber comprises:

[0201] D.1) 5 wt% to 90 wt% of at least one vinyl monomer, preferably 8 wt% to 80 wt% of at least one vinyl monomer, especially 10 wt% to 70 wt% of at least one vinyl monomer, grafted onto D.2) which is a grafting substrate

[0202] D.2) 95% to 10% by weight of one or more silicone-acrylate rubbers, preferably 92% to 20% by weight of one or more silicone-acrylate rubbers, especially 90% to 30% by weight of one or more silicone-acrylate rubbers,

[0203] % by weight is calculated based on the weight of the impact modifier.

[0204] Vinyl monomers are used to form polymer chains, and these polymer chains are chemically bonded to the graft substrate D.2.

[0205] Preferably, the vinyl monomer D.1 is selected from vinyl aromatic compounds and / or ring-substituted vinyl aromatic compounds (such as styrene, α-methylstyrene, p-methylstyrene), vinyl cyanides (unsaturated nitriles such as acrylonitrile and methacrylonitrile), (meth)acrylic (C1 to C8)-alkyl esters such as methyl methacrylate, ethyl methacrylate, n-butyl acrylate, tert-butyl acrylate, and derivatives of unsaturated carboxylic acids (such as acid anhydrides and imides) such as maleic anhydride and N -phenyl-maleimide.

[0206] More preferably, the at least one vinyl monomer D.1 comprises a (meth)acrylic (C1 to C8)-alkyl ester or a combination thereof with styrene, α-methylstyrene or p-methylstyrene.

[0207] Preferably, the graft substrate D.2 may have a glass transition temperature of < 10 °C, preferably < 0 °C, especially preferably < -20 °C. The glass transition temperature is determined by differential scanning calorimetry (DSC) according to standard DIN EN 61006 at a heating rate of 10 K / min, where T g is defined as the midpoint temperature (tangent method).

[0208] In some embodiments, the monomer D.1 is a mixture of the following substances

[0209] D.1.1) Based on D.1, 50 to 99, preferably 60 to 80, especially 70 to 80 parts by weight of vinyl aromatic compounds and / or ring-substituted vinyl aromatic compounds (such as styrene, α-methylstyrene, p-methylstyrene and p-chlorostyrene) and / or (meth)acrylic (C1 to C8)-alkyl esters such as methyl methacrylate, ethyl methacrylate, and

[0210] D.1.2) Based on D.1, 1 to 50, preferably 20 to 40, especially 20 to 30 parts by weight of (meth)acrylic (C1 to C8)-alkyl esters such as methyl methacrylate, n-butyl acrylate, tert-butyl acrylate and / or derivatives of unsaturated carboxylic acids (such as anhydrides and imides), such as maleic anhydride and N -phenylmaleimide.

[0211] The preferred monomer D.1.1 is selected from at least one of the monomers styrene, α-methylstyrene and methyl methacrylate; the preferred monomer D.1.2 is selected from at least one of the monomers maleic anhydride and methyl methacrylate. A particularly preferred monomer is D.1.1 = D.1.2 methyl methacrylate.

[0212] The graft copolymer D is prepared by free radical polymerization, for example by emulsion, suspension, solution or bulk polymerization, preferably by emulsion or bulk polymerization, especially by emulsion polymerization.

[0213] Because, as is well known, in the grafting reaction, the graft monomers do not necessarily completely graft onto the graft substrate. The graft copolymer D according to the invention is also understood to include products obtained by (co)polymerization of the graft monomers in the presence of the graft substrate and obtained together during post-treatment. Therefore, these products may also contain free (co)polymers of the graft monomers, i.e., (co)polymers not chemically bonded to the rubber.

[0214] Silicone-acrylate composite rubber or a mixture of different silicone-polyacrylate composite rubbers is used as the graft substrate D.2. These silicone-acrylic composite rubbers are preferably composite rubbers having graft active sites, which comprise:

[0215] D.2.1) A silicone rubber proportion of 5% to 95% by weight, preferably 20% to 80% by weight, particularly preferably 25% to 50% by weight, and

[0216] D.2.2) A poly(meth)acrylic acid alkyl ester rubber proportion of 95% to 5% by weight, preferably 80% to 20% by weight, particularly preferably 75% to 50% by weight,

[0217] wherein the two rubber components penetrate each other in the composite rubber and are thus substantially inseparable.

[0218] Particularly preferred proportions of silicone rubber and poly(meth)acrylic acid alkyl ester rubber result in a particularly favorable combination of good mechanical properties, a good surface of the component parts and good resistance to hydrolysis molecular weight reduction and chemical attack.

[0219] Silicone-acrylate composite rubbers are known and are described, for example, in US 5,807,914, EP 430134 and US4888388.

[0220] A suitable silicone rubber component D.2.1 of the silicone-acrylate composite rubber is a silicone rubber having grafting active sites, and its production method is described, for example, in US 2891920, US 3294725, DE-A 3 631 540, EP 249964, EP 430134 and US 4888388.

[0221] The silicone rubber according to D.2.1 is preferably prepared by emulsion polymerization, in which siloxane monomer units, crosslinking agents or branching agents and optionally grafting agents are used.

[0222] Examples of preferred siloxane monomers for producing silicone rubber include dimethylsiloxane 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.

[0223] The organosiloxane monomers can be used alone or in the form of a mixture containing 2 or more monomers.

[0224] Preferably, the crosslinking agent is a silane-based crosslinking agent with 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 in the form of a mixture of two or more. Particularly preferred is tetraethoxysilane.

[0225] Examples of grafting agents include β-methacryloyloxyethyl dimethoxymethylsilane, γ-ethylacryloyloxypropyl methoxydimethylsilane, γ-methacryloyloxypropyl dimethoxymethylsilane; γ-methacryloyloxypropyl trimethoxysilane, γ-methacryloyloxypropyl ethoxydiethylsilane, γ-methacryloyloxypropyl diethoxymethylsilane, δ-methacryloyloxybutyl diethoxymethylsilane or a mixture thereof.

[0226] Based on the total weight of the silicone rubber, 0-20% by weight of the grafting agent is preferably used.

[0227] The silicone rubber can be prepared by emulsion polymerization as described in US 2891920 and US 3294725.

[0228] The suitable poly(alkyl methacrylate) rubber component D.2.2 of the silicone-acrylate composite rubber can be prepared from alkyl methacrylates and / or alkyl acrylates, crosslinking agents, and grafting agents.

[0229] Examples of preferred alkyl methacrylates and / or alkyl acrylates include C1-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.

[0230] Crosslinking agents that can be used for the poly(alkyl methacrylate) 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-butanediol dimethacrylate, and 1,4-butanediol dimethacrylate. The crosslinking agent can be used alone or in the form of a mixture of at least two crosslinking agents.

[0231] Examples of preferred grafting agents include allyl methacrylate, triallyl cyanurate, and triallyl isocyanurate or mixtures thereof. Allyl methacrylate can also be used as a crosslinking agent. The grafting agent can be used alone or in the form of a mixture of at least two grafting agents.

[0232] The amounts of the crosslinking agent and the grafting agent are from 0.1% by weight to 20% by weight based on the total weight of the poly(alkyl methacrylate) rubber component of the silicone-acrylate rubber.

[0233] The silicone-acrylate composite rubber is prepared by first preparing the silicone rubber of D.2.1 in the form of an aqueous latex. Then, the latex is enriched with the alkyl methacrylate and / or alkyl acrylate, crosslinking agent, and grafting agent to be used and subjected to polymerization.

[0234] The silicone-acrylate composite graft rubber is prepared by grafting the monomer D.1 onto the rubber substrate D.2. For example, the polymerization methods described in EP 249964, EP430134, and US 4888388 can be used for implementation.

[0235] As the silicone-acrylate rubber, mention may be made of silicone-acrylate C1 to C8 alkyl ester rubber. In particular, silicone-butyl acrylate rubber can be mentioned as an example.

[0236] Preferably, the silicone - acrylate rubber - based impact modifier is selected from silicone - acrylate C1 - C8 alkyl ester rubbers grafted with (meth) acrylic (C1 - C8) - alkyl esters.

[0237] More preferably, the silicone - acrylate rubber - based impact modifier is methyl methacrylate - grafted silicone - butyl acrylate rubber.

[0238] As an example of a commercial silicone - acrylate rubber - based impact modifier that can be used in the present invention, Metablen S - 2001, Metablen S - 2030, and Metablen ® S2130 of Mitsubishi Rayon Co., Ltd can be mentioned.

[0239] In a preferred embodiment, methyl methacrylate - grafted silicone - butyl acrylate rubber, such as Metablen ® S2130, is used as component D.

[0240] Advantageously, the silicone - acrylate rubber - based impact modifier is present in the polycarbonate composition in an amount of 1 wt% to 4.5 wt%, preferably 1 wt% to 4 wt%, based on the total weight of the polycarbonate composition.

[0241] Component E

[0242] According to a first aspect, the polycarbonate composition according to the present invention comprises hydroxyaluminum oxide as component E.

[0243] Hydroxyaluminum oxide (AlHO2), also known as hydroxy(oxo)alane, has the following chemical structure:

[0244] HO - Al = O

[0245] The preparation of hydroxyaluminum oxide is known in the art and is described, for example, in CN105460964B and CN109065810A.

[0246] As a commercial hydroxyaluminum oxide product, Pural 200 of SASOL Germany GmbH can be mentioned.

[0247] Advantageously, hydroxyaluminum oxide is present in the polycarbonate composition in an amount of 0.5 wt% to 3 wt%, preferably 0.5 wt% to 2 wt%, preferably 0.5 wt% to 1.5 wt%, based on the total weight of the polycarbonate composition.

[0248] According to some embodiments, the polycarbonate composition according to the present invention does not contain any other fillers except hydroxyaluminum oxide.

[0249] Component F

[0250] According to a first aspect, the polycarbonate composition according to the invention comprises at least one anti-dripping agent as component F.

[0251] Preferably, the anti-dripping agent used is selected from fluorinated polyolefins.

[0252] Fluorinated polyolefins are known (see "Vinyl and Related Polymers" by Schildknecht, John Wiley & Sons, Inc., New York, 1962, pages 484 - 494; "Fluoropolymers" by Wall, Wiley Interscience, John Wiley & Sons, Inc., New York, Volume 13, 1970, pages 623 - 654; "Modern Plastics Encyclopedia", 1970 - 1971, Volume 47, No. 10A, October 1970, McGraw-Hill, Inc., New York, pages 134 and 774; "Modern Plastics Encyclopaedia", 1975 - 1976, October 1975, Volume 52, No. 10A, McGraw-Hill, Inc., New York, pages 27, 28 and 472 and US-PS 3 671 487, 3 723 373 and 3 838 092).

[0253] Preferably, the anti-dripping agent is selected from polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene copolymer and ethylene / tetrafluoroethylene copolymer.

[0254] More preferably, the anti-dripping agent used is polytetrafluoroethylene (PTFE).

[0255] Polytetrafluoroethylene can be prepared by known methods, for example, by polymerizing tetrafluoroethylene in an aqueous medium using a free radical-forming catalyst (such as sodium, potassium or ammonium persulfate) at a pressure of 7 kg / cm 2 to 71 kg / cm 2 and a temperature of 0 °C to 200 °C, preferably 20 °C to 100 °C. For more details, see, for example, US Patent 2 393 967.

[0256] Preferably, the fluorinated polyolefin has a high molecular weight and a glass transition temperature above -30 °C, typically above 100 °C, a fluorine content of preferably 65% to 76% by weight, especially 70% to 76% by weight (100% by weight of the fluorinated polyolefin), and an average particle size d of 0.05 μm to 1000 μm, preferably 0.08 to 20 μm. 50 。

[0257] Preferably, the fluorinated polyolefin has a density of 1.2 g / cm 3 to 2.3 g / cm 3 .

[0258] More preferably, the fluorinated polyolefin 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 density of 1.2 g / cm 3 to 1.9 g / cm 3 .

[0259] Suitable fluorinated polyolefins that can be used in powder form are tetrafluoroethylene polymers (PTFEs) having an average particle size of 100 to 1000 μm and a density of 2.0 g / cm 3 to 2.3 g / cm 3 .

[0260] Polytetrafluoroethylene can be used alone or in the form of a masterbatch containing a homopolymer or copolymer of styrene or methyl methacrylate.

[0261] As an example of a commercial product of polytetrafluoroethylene, mention may be made of the products sold by DuPont under the trade name Teflon ® .

[0262] Masterbatches of polytetrafluoroethylene and styrene-acrylonitrile (SAN) in a weight ratio of 1:1 can also be used, for example, ADS 5000 available from Chemical Innovation Co., Ltd. Thailand and POLYB FS-200 available from Han Nanotech Co., Ltd.

[0263] Advantageously, the anti-dripping agent is present in the polycarbonate composition in an amount of 0.2% to 1% by weight, preferably 0.3% to 1% by weight, preferably 0.5% to 1% by weight, based on the total weight of the polycarbonate composition.

[0264] Component G

[0265] According to a first aspect, the polycarbonate composition according to the present invention comprises at least one UV absorber as component F.

[0266] The UV absorber can be a UV absorber commonly used in the field of polycarbonate materials.

[0267] For example, suitable UV absorbers are described in EP 1 308 084 A1, DE 102007011069 A1 and DE 10311063 A1.

[0268] Exemplary UV absorbers include hydroxybenzophenone compounds; hydroxybenzotriazole compounds; hydroxybenzotriazine compounds; cyanoacrylate compounds; N,N '-oxalyldianiline compounds; benzoxazinone compounds; and the like, or combinations thereof.

[0269] Particularly suitable UV absorbers are hydroxyphenyltriazole compounds such as 2-(3',5'-bis(1,1-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole (Tinuvin@ 234, BASF SE, Ludwigshafen), 2-(2'-hydroxy-5'-(t-octyl)phenyl)benzotriazole (Tinuvin® 329, BASF SE, Ludwigshafen), 2-(2'-hydroxy-3'-(2-butyl)-5'-(t-butyl)phenyl)benzotriazole (Tinuvin® 350, BASF SE, Ludwigshafen), bis(3-(2H-benzotriazolyl)-2-hydroxy-5-t-octyl)methane (Tinuvin® 360, BASF SE, Ludwigshafen), 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)phenol (Tinuvin® 1577, BASF SE, Ludwigshafen) and 2,4-dihydroxybenzophenone (Chimasorb® 22, BASF SE, Ludwigshafen) and 2-hydroxy-4-(octyloxy)benzophenone (Chimasorb® 81, BASF SE, Ludwigshafen), 2-acrylate, 2-cyano-3,3-diphenyl, 2,2-bis[[(2-cyano-1-oxo-3,3-diphenyl-2-propenyl)oxy]methyl]-1,3-propanediyl ester (9CI) (Uvinul® 3030, BASF SE, Ludwigshafen), hydroxyphenyltriazine compounds such as 242-hydroxy-4-(2-ethylhexyl)oxy]phenyl-4,6-bis(4-phenyl)phenyl-1,3,5-triazine (Tinuvin®1600, BASF SE, Ludwigshafen) or tetraethyl 2,2'-(1,4-phenylenedimethylene)dimalonate (Hostavin® B-Cap, Clariant AG). Mixtures of these UV absorbers can also be used.

[0270] Advantageously, the UV absorber is present in the polycarbonate composition in an amount of 0.2% to 0.8% by weight, preferably 0.25% to 0.6% by weight, more preferably 0.3% to 0.5% by weight, based on the total weight of the polycarbonate composition.

[0271] Other additives

[0272] In addition to the above components A - G, the polycarbonate composition according to the present invention may optionally contain a balance of one or more other additives conventionally used in polymer compositions, such as lubricants and mold release agents (e.g., pentaerythritol tetrastearate), antioxidants, antistatic agents (including inorganic antistatic agents such as conductive carbon black, carbon fiber, carbon nanotubes and organic antistatic agents such as polyalkylene ethers, alkyl sulfonates or polyamide-containing polymers), dyes, pigments, etc.

[0273] As antioxidants, sterically hindered phenols and phosphites or mixtures thereof are preferably used, such as Irganox® B900 (Ciba Speciality Chemicals).

[0274] Those skilled in the art can select the type and amount of other additives such that they do not have a significant adverse effect on the desired properties of the polycarbonate composition according to the present invention.

[0275] In some embodiments, the polycarbonate composition according to the present invention consists of components A - G, a mold release agent and an antioxidant.

[0276] In some embodiments, the polycarbonate composition according to the present invention comprises the following components, based on the total weight of the composition:

[0277] A) 47 - 55 wt% of at least one aromatic polycarbonate having a weight average molecular weight of 23,000 to 28,000 g / mol,

[0278] B) 35 - 47 wt% of at least one polysiloxane - polycarbonate copolymer,

[0279] C) 1.5 - 4.5 wt% of at least one cyclophosphazene,

[0280] D) 1 - 4 wt% of a silicone - acrylic C1 - C8 alkyl ester rubber grafted with (meth)acrylic (C1 to C8)-alkyl ester,

[0281] E) 0.5 - 1.5 wt% of aluminum hydroxide,

[0282] F) 0.5 - 1 wt% of at least one anti - dripping agent, and

[0283] G) 0.25 - 0.6 wt% of at least one UV absorber.

[0284] Preparation of the polycarbonate composition

[0285] The polycarbonate composition according to the present invention can be in the form of, for example, pellets and can be prepared by various methods involving intimate mixing of the required materials in the composition.

[0286] For example, the materials required in the composition are first blended in a high-speed mixer. Other low-shear methods, including but not limited to manual mixing, can also accomplish this 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 feeder. Additives can also be compounded into a masterbatch containing the desired 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 in a water bath and pelletized. As previously mentioned, the pellet length can be one-quarter inch or less. Such pellets can be used for subsequent molding, shaping, or forming.

[0287] Due to the availability of melt blending equipment in commercial polymer processing facilities, the melt blending method is preferred.

[0288] Exemplary 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.

[0289] To avoid excessive degradation of the polymer, it is preferred to keep the melt temperature in the processing to a minimum. It is generally necessary to maintain the melt temperature in the molten resin composition at 200 °C to 330 °C, although higher temperatures can be used provided that the resin has a short residence time in the processing equipment.

[0290] In some cases, the molten composition exits the processing equipment (such as an extruder) through small exit holes in a die. The resulting molten resin strand is cooled by passing it through a water bath. The cooled strand can be cut into small pellets for packaging and further processing.

[0291] Molded article

[0292] The thermoplastic resin composition according to the present invention can be used, for example, for the production of various types of shaped articles.

[0293] According to a second aspect, the present invention provides a shaped article made of the polycarbonate composition according to the first aspect of the present invention.

[0294] As examples of shaped articles, mention may be made, for example, of films; profiles; various housing parts, such as household appliances, such as TVs, juicers, coffee makers, and blenders, or office machines, such as monitors, adapters, flat screens, laptops, printers, and copiers; sheets; tubes; electrical conduits; windows, doors, and other profiles in the building field (for indoor and outdoor applications); electrical and electronic components, such as switches, chargers, plugs, and sockets; and commercial vehicles, especially body parts or interior fittings in the field of motor vehicles.

[0295] In particular, the shaped article can be any of the following: the interior of rail vehicles, ships, aircraft, buses and other motor vehicles, the housing of electrical equipment containing small transformers, the housing of information processing and transmission equipment, the housing and sheath of medical equipment, the housing of safety devices, the molded parts of sanitary and bathroom fittings, the covering grille of ventilation holes and the housing of gardening tools.

[0296] Preparation of the molded article

[0297] The polycarbonate composition according to the present invention can be processed into a shaped article in various ways, such as injection molding, extrusion molding, blow molding or thermoforming to form a shaped article.

[0298] Therefore, according to the third aspect, the present invention provides a method for preparing a shaped article according to the second aspect of the present invention, including injection molding, extrusion molding, blow molding or thermoforming of the polycarbonate composition according to the first aspect of the present invention.

[0299] The following examples are used to elaborate the present invention in detail. Examples

[0300] Materials used

[0301] Component A

[0302] A1: A linear polycarbonate based on bisphenol A with a weight average molecular weight Mw of about 26,000 g / mol, available from Covestro, Co., Ltd in the form of Makrolon® 2600.

[0303] A2: A linear polycarbonate based on bisphenol A with a weight average molecular weight Mw of about 24,000 g / mol, available from Covestro, Co., Ltd in the form of Makrolon® 2400.

[0304] Component B

[0305] A polysiloxane-polycarbonate copolymer (SicoPC) with a PDMS content of about 6.5 wt%, available from LG Chem Ltd in the form of LG Lupoy® PC 8000-05.

[0306] Component C

[0307] The phenoxyphosphazene of formula (VI), wherein the content of the oligomer with k = 1 is 99.9 mol%, and the content of the oligomers with k≥2 is 0.1 mol%, is available from Weihai Jinwei Chem Induxtry Company in the form of HPCTP;

[0308] (VI).

[0309] Component D

[0310] D1: A silicone-acrylate rubber grafted with methyl methacrylate having a core / shell structure, available from Mitsubishi Rayon Co., Ltd in the form of Metablen® S2130.

[0311] D2: A methyl methacrylate-butadiene-styrene (MBS) having a core / shell structure, available from Japan KanekaChemical Co. Ltd in the form of Kane Ace M732.

[0312] Component E

[0313] E1: Hydroxyaluminum oxide, boehmite, available from SASOL Germany GmbH in the form of Pural 200.

[0314] E2: Wollastonite, available from NYCO Minerals, Inc in the form of NYGLOS 4W.

[0315] Component F

[0316] A polytetrafluoroethylene and styrene-acrylonitrile (SAN) masterbatch in a weight ratio of 1:1, available from IRPC PublicCompany Limited in the form of ADS 5000.

[0317] Component G

[0318] 2,2'-Methylenebis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl))phenol, available from Rianlon Corporation in the form of UV360.

[0319] Component H

[0320] H1: Pentaerythritol tetrastearate (PETS), a mold release agent, available from FACI Asia Pacific Pte Ltd. (Singapore)

[0321] H2: An antioxidant, a mixture of 80% Irgafos® 168 (tris(2,4-di-tert-butylphenyl) phosphite) and 20% Irganox® 1076 (2,6-di-tert-butyl-4-(octadecyloxycarbonylethyl) phenol), which can be obtained from BASF(China) Company Limited in the form of Irganos® B900.

[0322] Test method

[0323] The physical properties of the compositions obtained in the examples were tested as follows.

[0324] The notched impact strength was measured according to ISO 180 / 1A:2000 at an energy of 5.5 J on notched single-sided injection specimens with dimensions of 80×10×3 mm conditioned at the test temperature for 2 hours.

[0325] The flame retardancy was measured according to UL94 5VB on specimens with dimensions of 127×12.7×2.0 mm before and after soaking in water at 82 °C for 7 days and conditioning at 23 °C for 2 days.

[0326] The Vicat softening temperature was determined according to DIN 53 460 (ISO 306:2013) on bars with dimensions of 80×10×4 mm at a heating rate of 120 °C / hr.

[0327] The hydrolysis stability was evaluated based on the change in the Izod notched impact strength measured on bars with dimensions of 80 mm x 10 mm x 3 mm before and after soaking in water at 82 °C for 7 days according to ISO 180 / IA:2000.

[0328] Inventive Examples 1 - 3 (IE1 - IE3) and Comparative Examples 1 - 8 (CE1 - CE8)

[0329] The materials listed in Table 1 were compounded on a twin-screw extruder (ZSK-25) (Werner and Pfleider) at a speed of 225 rpm, a throughput of 20 kg / h, and a machine temperature of 260 - 290 °C, and pelletized.

[0330] The finished pellets were processed into corresponding test specimens on an injection molding machine with a melting temperature of 260 - 300 °C and a mold temperature of 80 °C.

[0331] The physical properties of the resulting compositions were tested, and the results are summarized in Table 1.

[0332] Table 1

[0333] CE1 CE2 CE3 CE4 IE1 IE2 IE3 CE5 CE6 CE7 CE8 A1 (Makrolon® 2600) 38.5 37 - 55.5 - 55 54.5 50.5 57.5 57 55 A2 (Makrolon® 2400) - - 49.5 - 49 - - - - - - B (SicoPC) 56 56 46 36 46 36 36 36 36 36 36 C (Phenoxyphosphazene) 3 4.5 1.5 4.5 1.5 4.5 4.5 4.5 2 2 4.5 D1 (Metablen® S2130) 1 1 1.5 2.5 1.5 2.5 2.5 2.5 - - D2 (MBS) - - - - - - - - - E1 (Hydroxyaluminum oxide) - - - - 0.5 0.5 1 5 0.5 1 - E2 (Wollastonite) - - - - - - - - - - 0.5 F (PTFE) 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 0.8 G (UV360) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 H1 (PETS) 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 0.3 H2 (Irganox® B900) 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Vicat softening temperature (°C) 133 129 137 131 137 130 129 124 134 136 130 <![CDATA[Izod notched impact strength at 23°C (KJ / m 2 ) ]]> 65P* 65P 65P 66P 64P 67P 65P 35P 66P 64P 66P <![CDATA[Izod notched impact strength at -20 °C (kJ / m 2 ) ]]> 51P 53P 55P 54P 55P 55P 55P 16C** 43P 49P 49P <![CDATA[Izod notched impact strength at -30°C (KJ / m 2 )]]> 49P 45P 53P 53P 52P 54P 49P 14C 23C 21C 27C 5VB rating before immersion in water By By By By By By By By By By By <![CDATA[After soaking in water at 82 °C for 7 days, the Izod notched impact strength at 23 °C (KJ / m 2 ) ]]> 54P 52P 60P 61P 60P 62P 59P 19C 54P 54P 58P 5VB rating after immersion in water at 82°C for 7 days Failed Failed Failed Failed Passed Passed Passed Failed Failed Failed Passed

[0334] *: P represents partial fracture, indicating toughness.

[0335] **: C represents complete fracture, indicating brittleness.

[0336] As shown in Invention Examples 1-3 (IE1-IE3), the composition according to the present invention has a good combination of low-temperature impact performance, flame retardancy, hydrolysis stability, anti-UV performance and heat resistance.

[0337] Specifically, the Vicat softening temperature of the composition in Invention Examples 1-3 is 129 °C or higher, and at -30 °C, the Izod notched impact strength is 59 KJ / m 2 or higher, and after soaking in water at 82 °C for 7 days, when the thickness is 2.0 mm, it can reach the UL rating of 5VB. After soaking in water at 82 °C for 7 days, the Izod notched impact strength at 23 °C can be maintained.

[0338] Comparative Examples 1-4 (CE1-CE4) show that the composition without hydroxyaluminum oxide cannot reach the UL rating of 5VB at a thickness of 2.0 mm after soaking in water at 82 °C for 7 days.

[0339] Comparative Example 5 (CE5) shows that when the content of hydroxyaluminum oxide is 5% by weight, based on the total weight of the composition, the low-temperature (-20 °C and -30 °C) impact strength of the composition is significantly reduced, and the composition cannot reach the UL rating of 5VB at a thickness of 2.0 mm after soaking in water at 82 °C for 7 days.

[0340] Comparative Examples 6-7 (CE6-CE7) show that the composition containing MBS instead of an impact modifier based on silicone-acrylate rubber cannot reach the UL rating of 5VB at a thickness of 2.0 mm after soaking in water at 82 °C for 7 days.

[0341] Comparative Example 8 (CE8) shows that the composition containing wollastonite instead of hydroxyaluminum oxide has a low notched impact strength at -30 °C.

Claims

1. A flame-retardant polycarbonate composition, comprising the following components, based on the total weight of the composition: A) 40 - 60% by weight of at least one aromatic polycarbonate, B) 30 - 50% by weight of at least one polysiloxane-polycarbonate copolymer, C) 0.5 - 5% by weight of at least one cyclophosphazene, D) 1 - 5% by weight of at least one impact modifier based on silicone-acrylate rubber, E) 0.3 - 3% by weight of aluminum hydroxide, F) 0.1 - 1% by weight of at least one anti-dripping agent, and G) 0.1 - 1% by weight of at least one UV absorber.

2. The composition according to claim 1, wherein the polysiloxane-polycarbonate copolymer comprises siloxane blocks derived from the following structures (XIII) and / or (XIV): wherein R1 independently of one another represents hydrogen, Cl, Br or C1 - C4-alkyl, R2 independently of one another represents aryl or C1 - C 13 -alkyl, X represents a single bond, -O-, -SO-, -CO-, -S-, -SO2-, C1 - C6-alkylene, C2 - C5-alkylidene, C5 - C 12 -subcycloalkyl or C6 - C 12 -subarylene optionally fused with an aromatic ring containing other heteroatoms, n represents an average number from 10 to 400, determined in each case by 1H-NMR spectroscopy, and m represents an average number from 1 to 10, determined in each case by 1H-NMR spectroscopy.

3. The composition according to claim 2, wherein R2 independently of one another represents C1 - C4-alkyl.

4. The composition according to claim 2, wherein X represents a single bond, isopropylidene or C5 - C 12 -subcycloalkyl.

5. The composition according to claim 2, wherein n represents an average number from 10 to 50, determined in each case by 1H-NMR spectroscopy.

6. The composition according to claim 2, wherein m represents an average number from 1.5 to 5, determined in each case by 1H-NMR spectroscopy.

7. The composition according to claim 1, wherein the polysiloxane-polycarbonate copolymer comprises from 2% to 20% by weight of the proportion of the siloxane block, based on the weight of the polysiloxane-polycarbonate copolymer.

8. The composition according to claim 1, wherein the cyclophosphazene is selected from cyclophosphazenes of formula (V): wherein k is an integer from 1 to 10, the trimer content is from 60 to 100 mol%, i.e., k = 1, based on component C, and wherein R is in each case the same or different and represents -amino, -C1-C8-alkyl, optionally halogenated in each case, -C1-C8-alkoxy, -C5-C6-cycloalkyl, optionally substituted by alkyl and / or halogenated in each case, and / or -C6-C 20 -aryloxy, optionally substituted by alkyl and / or halogenated and / or substituted by hydroxy in each case, -C7-C 12 -arylalkyl, optionally substituted by alkyl and / or halogenated in each case, -halogen group, or -OH group.

9. The composition according to claim 8, wherein k is an integer from 1 to 5.

10. The composition according to claim 8, wherein R is in each case the same or different and represents -amino, -methyl, ethyl, propyl or butyl, optionally fluorohalogenated in each case, -methoxy, ethoxy, propoxy or butoxy, -C5-C6-cycloalkyl, optionally substituted by C1-C4-alkyl and / or by chlorine and / or bromine in each case, -phenoxy or naphthoxy, optionally substituted by C1-C4-alkyl and / or by chlorine or bromine and / or by hydroxy in each case, -phenyl-C1-C4-alkyl, optionally substituted by C1-C4-alkyl and / or by chlorine and / or bromine in each case, -chlorine or fluorine, or -OH group.

11. The composition according to claim 8, wherein the cyclophosphazene is selected from propoxyphosphazene, phenoxyphosphazene, methylphenoxyphosphazene, aminophosphazene, and fluoroalkylphosphazene.

12. The composition according to claim 1, wherein the silicone-acrylate rubber-based impact modifier comprises, D.1) 5% to 90% by weight of at least one vinyl monomer grafted onto D.2) as a grafting substrate D.2) 95% to 10% by weight of one or more silicone-acrylate rubbers, by weight based on the weight of the impact modifier.

13. The composition according to claim 1, wherein the silicone-acrylate rubber-based impact modifier comprises, D.1) 8% to 80% by weight of at least one vinyl monomer grafted onto D.2) as a grafting substrate D.2) 92% to 20% by weight of one or more silicone-acrylate rubbers, by weight based on the weight of the impact modifier.

14. The composition according to claim 1, wherein the silicone-acrylate rubber-based impact modifier comprises, D.1) 10% to 70% by weight of at least one vinyl monomer grafted onto D.2) as a grafting substrate D.2) 90% to 30% by weight of one or more silicone-acrylate rubbers, by weight based on the weight of the impact modifier.

15. The composition according to claim 12, wherein the vinyl monomer D.1 is selected from vinyl aromatic compounds and / or ring-substituted vinyl aromatic compounds, vinyl cyanides, C1-C8 alkyl (meth)acrylates, and unsaturated carboxylic acid anhydrides and imides; and / or the silicone-acrylate rubber D.2 is selected from composite rubbers having grafting active sites, the composite rubber containing 5% - 95% by weight of silicone rubber proportion and 95% to 5% by weight of poly(alkyl methacrylate) rubber proportion, based on the total weight of the composite rubber.

16. The composition according to claim 12, wherein the vinyl monomer D.1 is selected from styrene, α-methylstyrene, p-methylstyrene, acrylonitrile, methacrylonitrile, methyl methacrylate, ethyl methacrylate, n-butyl acrylate, tert-butyl acrylate, maleic anhydride, and N-phenyl-maleimide; and / or The silicone-acrylate rubber D.2 is selected from composite rubbers having graft active sites, said composite rubbers containing from 20% to 80% by weight of a silicone rubber proportion and from 80% to 20% by weight of a poly(alkyl methacrylate) rubber proportion, based on the total weight of the composite rubber.

17. The composition according to claim 12, wherein the vinyl monomer comprises a C1-C8 alkyl (meth)acrylate or a combination thereof with styrene, α-methylstyrene or p-methylstyrene; and / or the silicone-acrylate rubber D.2 is selected from composite rubbers having graft active sites, said composite rubbers containing from 25% to 50% by weight of a silicone rubber proportion and from 75% to 50% by weight of a poly(alkyl methacrylate) rubber proportion, based on the total weight of the composite rubber.

18. The composition according to claim 1, wherein the impact modifier based on silicone-acrylate rubber is a methyl methacrylate-grafted silicone butyl acrylate rubber.

19. The composition according to claim 1, which comprises the following components, based on the total weight of the composition: A) 47 - 55% by weight of at least one aromatic polycarbonate having a weight average molecular weight of 23,000 to 28,000 g / mol, B) 35 - 47% by weight of at least one polysiloxane-polycarbonate copolymer, C) 1.5 - 4.5% by weight of at least one cyclophosphazene, D) 1 - 4% by weight of a silicone-acrylate C1-C8 alkyl ester rubber grafted with a C1-C8 alkyl (meth)acrylate, E) 0.5 - 1.5% by weight of hydroxyaluminum oxide, F) 0.5 - 1% by weight of at least one anti-dripping agent, and G) 0.25 - 0.6% by weight of at least one UV absorber.

20. The composition according to claim 1, wherein the anti-dripping agent is selected from fluorinated polyolefins.

21. The composition according to claim 1, wherein the anti-dripping agent is selected from polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene copolymer and ethylene / tetrafluoroethylene copolymer.

22. The composition according to claim 1, the composition further comprising one or more other additives selected from lubricants and mold release agents, antioxidants, antistatic agents, dyes and pigments.

23. A shaped article made from the composition according to any one of claims 1 to 22.

24. A method for preparing a shaped article according to claim 23, which comprises injection molding, extrusion molding, blow molding or thermoforming of the polycarbonate composition according to any one of claims 1 to 22.

Images