Polycarbonate composition

Abstract

The invention relates to a polycarbonate composition comprising the following components, relative to the total weight of the composition: A) 40 to 85 wt.% of an aromatic polycarbonate, B) 1 to 30 wt.% of acrylonitrile-butadiene-styrene, C) 8 to 15 wt.% of wollastonite, D) 1 to 3.5 wt.% of bisphenol A bis (diphenyl phosphate) and E) 2.5 to 6 wt.% of styrene-acrylonitrile-methacrylate. The invention also relates to a shaped article prepared from the composition. The polycarbonate composition according to the invention has a good combination of impact strength, heat resistance and aesthetic appearance.

Description

Technical Field

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

[0002] Reinforced PC / ABS (acrylonitrile-butadiene-styrene) compositions have long been used to prepare automotive exterior functional parts or decorative parts. For this purpose, the composition should have excellent mechanical properties, such as high impact resistance and high stiffness, good aesthetic appearance and excellent processability.

[0003] In the art, there are several patents and applications which disclose the use of wollastonite or other inorganic fillers in PC / ABS blends.

[0004] Conventional fillers such as glass fibers, mica, glass flakes, clay or talc fillers, if used in PC compositions, will adversely affect one or more of the above-mentioned desirable properties of the molded parts. For example, the coated molded parts have low distinctness of image (DOI), which is a measure of surface smoothness, are brittle and have poor impact resistance.

[0005] In order to improve the negative impact on performance, a lot of efforts have been made to develop new PC compositions.

[0006] US Patent No. 5,0991,461 discloses PC / ABS compositions containing a class of inorganic fillers having typical platelet shaped particles. The patent claims that molded parts based on such compositions have high dart impact resistance and good heat resistance under load.

[0007] US 2007 / 0072960 A1 discloses that compositions comprising mineral fillers that have been surface treated by pretreatment with a vinyl functional silane coupling agent and admixture with the filler may have an improved balance of properties.

[0008] U.S. Patent No. 5,965,655 discloses a PC / ABS composition containing a mineral filler having needle-shaped particles (e.g., wollastonite). The patent claims that the molded article having the outer coating has an improved balance of material properties, such as high impact resistance, high stiffness, and even a class A finish.

[0009] US 2005 / 0182165 A1 discloses a composition comprising polycarbonate / siloxane, a mineral filler (such as wollastonite) and a phosphate flame retardant, which has good properties such as good flame retardancy, impact resistance and flexural modulus.

[0010] US Patent No. 6,664,362 discloses a wollastonite-filled flame retardant PC / ABS composition having excellent hydrolysis resistance and excellent FR performance.

[0011] However, none of the above-mentioned patents or applications provide wollastonite-filled polycarbonate compositions that can be used to prepare molded parts having high impact strength, high heat resistance, and good aesthetic appearance, especially around the sprue gate.

[0012] Therefore, there continues to be a need for compositions that can be used to prepare molded parts having high impact strength, high heat resistance, and good aesthetic appearance, especially around the sprue gate. Summary of the invention

[0013] It is therefore an object of the present application to provide a polycarbonate composition that can be used to prepare molded parts having a good combination of impact strength, heat resistance and aesthetic appearance.

[0014] Another object of the present application is to provide an article having a good combination of impact strength, heat resistance and aesthetic appearance.

[0015] In a first aspect, the present invention provides a polycarbonate composition comprising the following components, relative to the total weight of the composition:

[0016] A) 40-85 wt.% of aromatic polycarbonate,

[0017] B) 1-30 wt.% acrylonitrile-butadiene-styrene (ABS),

[0018] C) 8-15 wt.% wollastonite,

[0019] D) 1-3.5 wt.% of bisphenol A bis(diphenyl phosphate), and

[0020] E) 2.5-6 wt.% of styrene-acrylonitrile-methacrylate.

[0021] The inventors have surprisingly found that the composition according to the invention can be used to prepare molded parts having a good combination of impact strength, heat resistance and aesthetic appearance. For example, the molded parts prepared have a Vicat temperature of not less than 110°C as measured according to ISO 306:2013 and a thermal conductivity of more than 8 kJ / m as measured according to ISO 180 / A:2000. 2 At the same time, the produced molded parts have good aesthetic appearance, that is, there is no visible gate streak on the surface of the molded parts (especially near the sprue gate).

[0022] In a second aspect, the present invention provides a shaped article prepared from the polycarbonate composition according to the first aspect of the present invention.

[0023] 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.

[0024] Other subjects and features, aspects and advantages of the invention will emerge even more clearly on reading the following description and examples. DETAILED DESCRIPTION OF THE INVENTION

[0026] In the following text and unless otherwise indicated, the upper and lower limits of a numerical range are included in the range, especially in the expressions "between ... and ..." and "from ... to ...".

[0027] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those of ordinary skill 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 of ordinary skill in the art to which the invention belongs, the definition described in this article shall prevail.

[0028] Throughout this application, the term "comprising" should be interpreted as covering all explicitly mentioned features as well as optional, additional, unspecified features. As used herein, the use of the term "comprising" also discloses embodiments in which there are no features other than the explicitly mentioned features (i.e., "consisting of ...").

[0029] 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".

[0030] Component A

[0031] The polycarbonate composition according to the present invention comprises an aromatic polycarbonate.

[0032] According to the invention, "aromatic polycarbonates" or just "polycarbonates" are understood to mean both homopolycarbonates and copolycarbonates, in particular those that are aromatic. These polycarbonates may be linear or branched in a known manner. According to the invention, mixtures of polycarbonates may also be used.

[0033] The aromatic polycarbonate selected according to the present invention preferably has a weight average molecular weight M w : 15 000-40 000 g / mol, more preferably 16 000-34 000 g / mol, even more preferably 17 000-33 000 g / mol, most preferably 19 000-32000 g / mol.w The values ​​were determined by gel permeation chromatography using dichloromethane as the eluent, calibrated against bisphenol A polycarbonate standards, calibrated with linear polycarbonates (prepared from bisphenol A and phosgene) with known molar mass distribution from PSS Polymer Standards Service GmbH (Germany); calibrated according to method 2301-0257502-09D (2009 German version) from Currenta GmbH & Co. OHG, Leverkusen. The eluent was dichloromethane. Column combination of crosslinked styrene-divinylbenzene resin. Diameter of the analytical column: 7.5 mm; Length: 300 mm. Particle size of the column material: 3 μm to 20 μm. Concentration of the solution: 0.2 wt%. Flow rate: 1.0 ml / min, solution temperature: 30° C. Detection was performed using a refractive index (RI) detector.

[0034] The polycarbonates are preferably produced by the interfacial process or the melt transesterification process which has been described many times in the literature.

[0035] With regard to 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.; Polymer Reviews, Vol. 10, "Condensation Polymers by Interfacial and Solution Methods", Paul W. Morgan, Interscience Publishers, New York 1965, Chapter VIII, p. 325; Dres. U. Grigo, K. Kircher and PR-Müller, "Polycarbonate", Becker / Braun, Kunststoff-Handbuch, Vol. 3 / 1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag Munich, Vienna 1992, pp. 118-145; and also EP 0 517 044 A1.

[0036] The melt transesterification process is described, for example, in "Encyclopedia of Polymer Science", Volume 10 (1969); Chemistry and Physics of Polycarbonates, Polymer Reviews, H. Schnell, Volume 9, John Wiley and Sons, Inc. (1964); and in patent specifications DE 10 31 512 A and US Pat. No. 6,228,973 B1.

[0037] Details concerning the production of polycarbonates have been disclosed in numerous patent documents over 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; D. Freitag, U. Grigo, PR Müller, H. Nouvertné, BAYER AG, "Polycarbonates", Encyclopedia of Polymer Science and Engineering, Vol. 11, 2nd edition, 1988, pp. 648-718; and finally U. Grigo, K. Kirchner and PR Müller "Polycarbonate", Becker / Braun, Kunststoff-Handbuch, Vol. 3 / 1, Polycarbonate, Polyacetale, Polyester, Celluloseester, Carl Hanser Verlag Munich, Vienna 1992, pp. 117-299.

[0038] Aromatic polycarbonates are produced, for example, by reacting dihydroxyaryl compounds with carbonyl halides (preferably phosgene) and / or with aromatic dicarboxylic acid dihalides (preferably phenylenedicarboxylic acid dihalides) via an interfacial process, optionally using chain terminators and optionally using trifunctional branching agents or more than trifunctional branching agents, and polyester carbonates are produced by replacing a portion of the carbonic acid derivatives with aromatic dicarboxylic acids or derivatives of these dicarboxylic acids, in particular by replacing a portion of the carbonic acid derivatives with aromatic dicarboxylic acid ester structural units, depending on the carbonate structural units to be replaced in the aromatic polycarbonate. It is likewise possible to prepare by reaction of dihydroxyaryl compounds with, for example, diphenyl carbonate via a melt polymerization process.

[0039] Suitable dihydroxyaromatic compounds for the production of polycarbonates are, for example, hydroquinone, resorcinol, dihydroxybiphenyl, 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, phthalimides derived from derivatives of isatin or phenolphthalein, and ring-alkylated, ring-arylated and ring-halogenated compounds thereof.

[0040] Preferred dihydroxyaryl compounds are 4,4′-dihydroxybiphenyl, 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 and also bisphenols (I) to (III)

[0041]

[0042] Therein R' in each case represents C1-C4-alkyl, aralkyl or aryl, preferably represents methyl or phenyl, very particularly preferably represents methyl.

[0043] 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).

[0044] These and other suitable dihydroxyaryl compounds are described, for example, in U.S. Pat. No. 3,028,635 A, U.S. Pat. No. 2,999,825 A, U.S. Pat. No. 3,148,172 A, U.S. Pat. No. 2,991,273 A, U.S. Pat. No. 3,271,367 A, U.S. Pat. No. 4,982,014 A and U.S. Pat. No. 2,999,846 A, DE 1 570 703 A, DE 2 063 050 A, DE 2 036 052 A, DE 2 211 956 A and DE 3 832 396 A, FR 1 561 518. The monograph "H. Schnell, Chemistry and Physics of Polycarbonates, Interscience Publishers, New York 1964" and also JP 62039 / 1986 A, JP 62040 / 1986 A and JP 105550 / 1986 A.

[0045] 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.

[0046] Suitable carbonic acid derivatives are, for example, phosgene and diphenyl carbonate.

[0047] Suitable chain terminators which can be used in the production of polycarbonates are monohydric phenols. Suitable monohydric phenols are, for example, phenol itself; alkylphenols, for example cresol, p-tert-butylphenol, cumylphenol, and mixtures thereof.

[0048] Preferred chain terminators are linear or branched C1-C 30 Alkyl mono- or polysubstituted phenols, preferably unsubstituted or substituted by tert-butyl groups. Particularly preferred chain terminators are phenol, cumylphenol and / or p-tert-butylphenol.

[0049] The amount of chain terminators to be used is preferably from 0.1 to 5 mol %, based on the moles of dihydric phenol used in each case. The addition of chain terminators can be carried out before, during or after the reaction with the carbonic acid derivatives.

[0050] Suitable branching agents are the trifunctional or more than trifunctional compounds familiar from polycarbonate chemistry, in particular those having three or more than three phenolic hydroxyl 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)- The amount of branching agents optionally used is preferably 0.05 mol % to 2.00 mol %, based on the molar number of dihydroxyaryl compounds used in each case. The branching agents can be initially charged into the alkaline aqueous phase together with the dihydroxyaryl compounds and the chain terminators or added dissolved in an organic solvent before phosgenation. In the case of the transesterification process, the branching agents are used together with the dihydroxyaryl compounds.

[0051] 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 also homopolycarbonates or copolycarbonates derived from dihydric phenols of the formulae (I), (II) and (III)

[0052]

[0053] Therein R' in each case represents C1-C4-alkyl, aralkyl or aryl, preferably represents methyl or phenyl, very particularly preferably represents methyl.

[0054] Preference is also given to polycarbonates in the production of which a dihydroxyaryl compound of the following formula (1a) has been used:

[0055]

[0056] in

[0057] R 5 represents hydrogen or C1-C4 alkyl, C1-C4 alkoxy, preferably represents hydrogen or methyl or methoxy, particularly preferably represents hydrogen,

[0058] R 6 , R 7 , R 8 and R 9 Independent representatives C6-C 12Aryl or C1-C4 alkyl, preferably phenyl or methyl, particularly methyl,

[0059] Y represents a single bond, SO2-, -S-, -CO-, -O-, C1-C6 alkylene, C2-C5 alkylidene, C6-C5 alkylidene which may be optionally fused with other aromatic rings containing heteroatoms. 12 Arylene, or represents a C5-C6 cycloalkylidene residue which may be mono- or poly-substituted by C1-C4-alkyl, preferably represents a single bond, -O-, isopropylidene, or represents a C5-C6 cycloalkylidene residue which may be mono- or poly-substituted by C1-C4-alkyl,

[0060] V represents oxygen, C2-C6 alkylene or C3-C6 alkylidene, preferably represents oxygen or C3 alkylene,

[0061] p, q and r independently represent 0 or 1,

[0062] If q=0, W is a single bond, if q=1 and r=0, W represents -O-, C2-C6-alkylene or C3-C6-alkylidene, preferably represents oxygen or C3-alkylene,

[0063] If q=1 and r=1, W and V independently represent C2-C6 alkylene or C3-C6 alkylidene, preferably C3 alkylene,

[0064] Z represents a C1-C6 alkylene group, preferably a C2 alkylene group,

[0065] o represents an average number of repeating units of 10 to 500 (preferably 10 to 100), and

[0066] m represents an average number of repeating units of 1 to 10 (preferably 1 to 6, particularly preferably 1.5 to 5).

[0067] 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.

[0068] Particularly preferred are (poly)siloxanes of formula (2) and (3)

[0069]

[0070]

[0071] Where R 1 represents hydrogen, C1-C4 alkyl, preferably represents hydrogen or methyl, and particularly preferably represents hydrogen,

[0072] R 2 independently represent aryl or alkyl, preferably represent methyl,

[0073] X represents a single bond, -SO2-, -CO-, -O-, -S-, C1-C6 alkylene, C2-C5 alkylidene, or a C6-C5 alkylene ring which may be optionally fused with another aromatic ring containing heteroatoms. 12 Arylene,

[0074] X represents a single bond, -SO2-, -CO-, -O-, -S-, C1-C6 alkylene, C2-C5 alkylidene, C5-C 12 Cycloalkylene or represents a C6-C8-cycloalkyl group which may be optionally fused to other aromatic rings containing heteroatoms. 12 Arylene,

[0075] X preferably represents a single bond, isopropylidene, C5-C 12 cycloalkylidene or oxo, and particularly preferably represents isopropylidene,

[0076] n represents an average number of 10 to 400 (preferably 10 to 100, particularly preferably 15 to 50), and

[0077] m represents an average number of 1 to 10 (preferably 1 to 6, and particularly preferably 1.5 to 5).

[0078] Also preferably, the siloxane blocks may be derived from one of the following structures:

[0079]

[0080] Here, a in formulae (IV), (V) and (VI) represents an average number of 10 to 400 (preferably 10 to 100, and particularly preferably 15 to 50).

[0081] It is equally 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.

[0082] It is also preferred that, in formula (1a), if p=0, V represents a C3 alkylene group,

[0083] If r=1, Z represents a C2 alkylene group, R 8 and R 9 Represents methyl,

[0084] If q=1, W represents a C3 alkylene group,

[0085] If m = 1, then R 5 R6 and R7 independently represent C1-C4 alkyl, preferably methyl, and o represents 10 to 500.

[0086] WO 2015 / 052106 A2 describes copolycarbonates having monomer units of the general formula (1a), especially having bisphenol A, and especially the production of those copolycarbonates.

[0087] As an example of an aromatic polycarbonate suitable for the present invention, there may be mentioned an aromatic polycarbonate produced from bisphenol A and phosgene and sold by Covestro Co., Ltd. under the trade name 2400, 2600, 2800, 3100 of those sold.

[0088] Advantageously, the aromatic polycarbonate is present in an amount ranging from 40 wt.% to 85 wt.%, more preferably from 45 wt.% to 80 wt.%, even more preferably from 50 wt.% to 75 wt.%, relative to the total weight of the composition according to the invention.

[0089] Component B

[0090] The polycarbonate composition according to the present invention comprises a core-shell impact modifier selected from acrylonitrile-butadiene-styrene.

[0091] Acrylonitrile-butadiene-styrene (ABS) is described, for example, in DE-OS 2035390 or DE-OS 2248242 and in Ullmanns, der Technischen Chemie, Vol. 19 (1980), pp. 280 ff.

[0092] Preferably, based on the weight of acrylonitrile-butadiene-styrene (ABS), acrylonitrile-butadiene-styrene contains 5wt.%-95wt.% (preferably 8wt.%-90wt.%, especially 20wt.%-85wt.%) of units derived from acrylonitrile and styrene and 95wt.%-5wt.% (preferably 92wt.%-10wt.%, especially 80wt.%-15wt.%) of units derived from butadiene.

[0093] More preferably, the acrylonitrile-butadiene-styrene comprises 15-35 wt.% units derived from acrylonitrile, 40-60 wt.% units derived from styrene and 5-30 wt.% units derived butadiene, based on the weight of the acrylonitrile-butadiene-styrene (ABS).

[0094] As commercial acrylonitrile-butadiene-styrene products that can be used in the present invention, mention can be made of ABS 8391 available from SINOPEC Shanghai Gaoqiao Company, which has a polybutadiene rubber content of 5-30 wt.%, a styrene content of 40-60 wt.% and an acrylonitrile content of 15-35 wt.%; and 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 ABS polymer, in 55-58 wt.% of crosslinked polybutadiene rubber (average particle size d ) based on ABS polymer. 50 Produced by emulsion polymerization in the presence of 0.3 μm).

[0095] Advantageously, the acrylonitrile-butadiene-styrene is present in an amount ranging from 1 wt.% to 30 wt.%, preferably from 3 wt.% to 26 wt.%, relative to the total weight of the polycarbonate composition.

[0096] Component C

[0097] The polycarbonate composition according to the present invention comprises wollastonite.

[0098] The term "wollastonite" refers to various mineral forms of calcium silicate (CaSiO3).

[0099] For example, wollastonite useful in the polycarbonate compositions according to the present invention includes purified wollastonite comprising approximately 48 weight percent calcium oxide (CaO) and 52 weight percent silicon dioxide (SiO2), as well as substituted forms in which relatively small amounts of iron, manganese and / or magnesium replace the calcium in the mineral form.

[0100] Wollastonite generally forms dense, fibrous, columnar, lobed or fibril aggregates and, in some cases, also forms platelet- to needle-shaped particles, which are commercially available.

[0101] Preferably, needle-shaped wollastonite particles are used in the polycarbonate composition according to the present invention.

[0102] The diameter (d 50 ) can be less than 100 μm, less than 50 μm, or less than 25 μm. For example, the diameter (d 50 ) can be in the range of 3 μm to 50 μm or in any sub-range included therein such as 3 μm to 30 μm, 3 μm to 25 μm, 4 μm to 20 μm or 5 μm to 15 μm.

[0103] For the purposes of the present invention, the diameter (d50 ) indicates the diameter such that 50 wt. % of the relevant material has the larger diameter and 50 wt. % of the relevant material has the smaller diameter.

[0104] Dynamic light scattering was performed using a 20 μm spectroscopy system from Malvern Micro to measure d 50 Average diameter.

[0105] Preferably, the wollastonite particles may have a needle-like morphology with an aspect ratio (L:D) in the range of 3:1 to 15:1, or in any subrange included therein (eg, 4:1 to 10:1, preferably 5:1 to 10:1).

[0106] It has surprisingly been found that molded parts obtained with a polycarbonate composition according to the invention containing wollastonite having an aspect ratio of 5:1 to 10:1 exhibit desired properties and in particular reduced gate striations.

[0107] Preferably, the wollastonite used in the present invention is surface treated with a functionalized silane coupling agent. As an example, the functionalized silane coupling agent can be selected from vinyl triethoxy silane, vinyl methyl diethoxy silane, vinyl methyl dimethoxy silane, vinyl tri (2-methoxyethoxy) silane, methacryloxy propyl trimethoxy silane, methacryloxy propyl triethoxy silane and a combination thereof.

[0108] Examples of suitable wollastonites include, for example, wollastonites available under the names NYGLOS and NYAD from NYCO Minerals, Inc., Willsboro, NY, USA, and wollastonites available under the name TREMIN from Quarzwerke GmbH.

[0109] Advantageously, wollastonite is present in an amount ranging from 8 wt.% to 15 wt.%, preferably from 10 wt.% to 15 wt.%, relative to the total weight of the polycarbonate composition.

[0110] Component D

[0111] The polycarbonate composition of the present invention comprises bisphenol A bis(diphenyl phosphate).

[0112] Bisphenol A bis(diphenyl phosphate) has the following formula:

[0113]

[0114] Therein, q represents a number in the range from 0.8 to 5.0, preferably from 0.9 to 3.0, more preferably from 1.0 to 1.5 and particularly preferably from 1.05 to 1.2.

[0115] In some embodiments, compositions according to the present invention comprise bisphenol A bis(diphenyl phosphate) of the formula.

[0116]

[0117] Bisphenol A bis(diphenyl phosphate) can be produced in an analogous manner by known methods (eg 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).

[0118] Advantageously, bisphenol A bis(diphenyl phosphate) is present in an amount ranging from 1 wt.% to 3.5 wt.%, preferably from 1 wt.% to 3 wt.%, preferably from 2 wt.% to 3 wt.%, relative to the total weight of the polycarbonate composition.

[0119] It has been found that a good balance between flow, surface appearance and heat resistance can be achieved by using bisphenol A bis(diphenyl phosphate) in combination with styrene-acrylonitrile-methacrylate.

[0120] Component E

[0121] The polycarbonate composition of the present invention comprises styrene-acrylonitrile-methacrylate.

[0122] As used herein, styrene-acrylonitrile-methacrylate refers to a copolymer of styrene, acrylonitrile, and methacrylate.

[0123] Mention may be made, as examples of methacrylates, of methyl methacrylate (MMA), glycidyl methacrylate (GMA), ethyl methacrylate, n-butyl methacrylate, benzyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate and benzyl methacrylate.

[0124] Preferably, the styrene-acrylonitrile-methacrylate is selected from the group consisting of styrene-acrylonitrile-methyl methacrylate, styrene-acrylonitrile-glycidyl methacrylate and combinations thereof.

[0125] Preferably, styrene-acrylonitrile-methacrylate comprises 50-95 wt.% of units derived from styrene, 4-45 wt.% of units derived from acrylonitrile and 1-5 wt.% of units derived from methacrylate, based on the weight of styrene-acrylonitrile-methacrylate.

[0126] Advantageously, the styrene-acrylonitrile-methacrylate is present in an amount ranging from 2.5 wt.% to 6 wt.%, preferably from 3 wt.% to 5 wt.%, more preferably from 3 wt.% to 4 wt.%, relative to the total weight of the polycarbonate composition.

[0127] Additional components

[0128] 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 are, for example, fillers, UV stabilizers, IR stabilizers, heat stabilizers, antistatic agents, pigments (e.g., carbon black), colorants, lubricants (e.g., waxes), mold release agents (e.g., pentaerythritol tetrastearate), antioxidants, pH regulators, flow improvers, anti-drip agents (e.g., polytetrafluoroethylene), etc.

[0129] One skilled in the art can select the type of additive to avoid adversely affecting the desired properties of the polycarbonate composition according to the present invention.

[0130] In some embodiments, based on the total weight of the composition according to the present invention, the composition may further comprise up to 5 wt.%, preferably up to 3 wt.%, more preferably 0.1 wt.%-3 wt.% of additional components selected from the group consisting of antioxidants, heat stabilizers, mold release agents, antistatic agents, pigments, pH adjusters and lubricants.

[0131] Preferably, relative to the total weight of the polycarbonate composition according to the present invention, the composition comprises:

[0132] A) 50-75 wt.% of aromatic polycarbonate,

[0133] B) 3-26 wt.% acrylonitrile-butadiene-styrene,

[0134] C) 10-15 wt.% of surface treated wollastonite having an aspect ratio (L:D) in the range of 5:1 to 10:1,

[0135] D) 2-3 wt.% of bisphenol A bis(diphenyl phosphate), and

[0136] E) 3-4 wt.% of styrene-acrylonitrile-methacrylate.

[0137] Advantageously, the total amount of components A) to E) as defined above is 90-100 wt.%, preferably 95-100 wt.%, more preferably 97-100 wt.%, based on the total weight of the polycarbonate composition according to the invention.

[0138] Preparation of polycarbonate compositions

[0139] The polycarbonate composition according to the present invention may be in the form of pellets, for example.

[0140] The polycarbonate compositions according to the present invention exhibit good processability and can be prepared by a variety of methods involving intimate mixing of the desired materials in the composition.

[0141] 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 downstream via a side filler. The additive 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 that required to make the composition flow. The extrudate is immediately quenched and granulated in a water bath. Such pellets can be used for subsequent molding, shaping or forming.

[0142] Melt blending methods are preferred due to the availability of melt blending equipment in commercial polymer processing facilities.

[0143] 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.

[0144] It is preferred to minimize the melt temperature during processing to avoid excessive degradation of the polymer. It is generally desirable to maintain the melt temperature in the molten resin composition between 200°C and 330°C, although higher temperatures can be used provided that the residence time of the resin in the processing equipment is kept short.

[0145] In some cases, the molten composition leaves the processing equipment (e.g., extruder) through a small exit hole in the die. The resulting strands of molten resin are cooled by passing them through a water bath. The cooled strands can be cut into small pellets for packaging and further processing.

[0146] Molded products

[0147] The polycarbonate composition according to the invention can be used, for example, to produce various types of shaped articles.

[0148] In a second aspect, the present invention also provides a shaped article prepared from the polycarbonate composition according to the first aspect of the present invention.

[0149] As examples of such shaped articles, mention may be made of, for example, films; profiles; housing parts (for example for household appliances); sheets; pipes; windows, doors and other profiles for the building industry (for interior and exterior applications); and exterior or interior parts for commercial vehicles.

[0150] Preparation of molded products

[0151] 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.

[0152] In a third aspect, the present invention provides a method for preparing a shaped article prepared from the composition according to the first aspect of the present invention, comprising injection molding, extrusion molding, blow molding or thermoforming the polycarbonate composition according to the present invention. Example

[0153] The present invention will be illustrated in detail with reference to the following examples. The examples are for illustrative purposes only and are not intended to limit the scope of the present invention.

[0154] Materials used

[0155] Component A

[0156] PC-1: Available from Covestro Polymer (China) Company, it is a bisphenol A-based linear polycarbonate with 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.

[0157] PC-2: Available from Covestro Polymer (China) Company, it is a bisphenol A-based linear polycarbonate with 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.

[0158] PC-3: Commercially available from Covestro Polymer (China) Company, it is a bisphenol A-based linear polycarbonate with a weight average molecular weight (Mw) of 20,000 g / mol as determined by gel permeation chromatography (GPC) in dichloromethane at 25°C using polycarbonate standards.

[0159] Component B

[0160] ABS: Based on the ABS polymer, it has a polybutadiene rubber content of 5-30 wt.%, a styrene content of 40-60 wt.%, and an acrylonitrile content of 15-35 wt.%, and is available as ABS 8391 from SINOPEC Shanghai Gaoqiao.

[0161] Component C

[0162] Wollastonite-1: having an average diameter of 7 μm and an average length of 63 μm, surface treated with a functionalized silane coupling agent, available as NYGLOS 4W 10992 from Zhejiang Wansheng Technology Co., Ltd. (China).

[0163] Wollastonite-2: average diameter 4 μm and average length 23 μm, surface treated with a functionalized silane coupling agent, available as TREMIN 939-600KST ​​from Quarzwerke GmbH.

[0164] Component D

[0165] BDP: bisphenol A bis(diphenyl phosphate), available from Zhejiang Wansheng Technology Co., Ltd. (China).

[0166] Component E

[0167] SAN-GMA: styrene-acrylonitrile-glycidyl methacrylate, available from Fine-Blend Co., Ltd. as Fine-Blend SAG-005.

[0168] SAN-MMA: styrene-acrylonitrile-methyl methacrylate, available as Blendex 866 from Galata Chemicals.

[0169] Other components

[0170] PETS: Pentaerythritol tetrastearate powder, a mold release agent, available as FACIL 348 from FACIAsiaPacificPte Ltd. (Singapore).

[0171] B900: 80% 168 and 20% 1076, available from BASF, wherein 168 is tris(2,4-di-tert-butylphenyl) phosphite, 1076 is 2,6-di-tert-butyl-4-(octadecyloxycarbonylethyl)phenol.

[0172] Carbon black: available from Cabot Co., Ltd. (China).

[0173] Phosphorous acid: H3PO3, available from Sigma-Aldrich Chemie GmbH.

[0174] Hi-wax 1105: an acid-modified polyethylene wax having a weight average molecular weight of 1500 g / mol, available from Mitsui Chemicals Inc.

[0175] Ethylenediaminetetraacetic acid (EDTA): Available as Trilon BS from Shijiazhuang Jack Chemical Co., Ltd. (China).

[0176] Citric acid: available from Shijiazhuang Jack Chemical Co., Ltd. (China).

[0177] Test Method

[0178] The physical properties of the specimens in the examples were tested as follows.

[0179] Melt Volume Flow Rate (MVR)

[0180] The melt volume flow rate (MVR) was determined according to ISO 1133:2011 at 260° C. and a load of 5 kg using a Zwick 4106 instrument from Roell.

[0181] Izod notched impact strength

[0182] 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.

[0183] Izod unnotched impact strength

[0184] The Izod unnotched impact strength was measured according to ISO 180 / U:2000 (23° C., 4 mm, 5.5 J) on a test specimen with a size of 80 mm×10 mm×4 mm.

[0185] Vicat softening temperature

[0186] The Vicat softening temperature (T) was determined according to ISO 306:2013 using a Coesfeld Eco 2920 instrument from Coesfeld Materialtest with a punch load of 50 N and a heating rate of 120° C. / h on test specimens with dimensions of 80 mm×10 mm×4 mm. 维卡 ).

[0187] Heat Deflection Temperature (HDT)

[0188] Heat deformation temperature (HDT) was measured according to ISO 75-2:2013 under a load of 1.8 MPa on samples of 80 mm x 10 mm x 4 mm.

[0189] Gate stripe grade

[0190] Determine the gate stripes as follows:

[0191] The material pellets to be tested were dried at 100°C for 4 h and then produced molded parts with dimensions of 150 mm x 100 mm x 3 mm by a KraussMaffei 110 ton hydraulic injection molding machine with a Φ35 mm screw. The gate striations of the molded parts were rated as follows:

[0192]

[0193]

[0194] Defect level order: None < Slight < Visible < Severe. The more "+" suffixes there are, the more serious the gate stripes are.

[0195] Comparative Examples (CE) 1-12

[0196] The materials listed in Table 1 were compounded and pelletized on a twin-screw extruder (ZSK-26) (from Coperion, Werner and Pfleiderer) at a rotation speed of 225 rpm, a throughput of 30 kg / h and a machine temperature of 260-290°C.

[0197] The pellets obtained were processed on an injection molding machine (from Arburg) to give corresponding test specimens, with a melt temperature of 260-300° C., a mold temperature of 80° C. and a flow front speed of 240 mm / s.

[0198] The properties of the obtained compositions (including melt volume flow rate (MVR), Izod notched impact strength, Izod unnotched impact strength, Vicat softening temperature, heat deformation temperature, surface properties (e.g., gate streak grade)) were tested, and the results are summarized in Table 1.

[0199]

[0200] As can be seen from Table 1, the compositions of Comparative Examples 1-3 that do not include styrene-acrylonitrile-methacrylate and BDP produce undesirable molded parts with a gate line rating of 6.

[0201] The compositions of Comparative Examples 4 and 6 that do not include styrene-acrylonitrile-methacrylate produce undesirable molded parts with gate line ratings of 4 or 5.5.

[0202] The compositions of Comparative Examples 5 and 7, which contained 6 wt.% BDP and no styrene-acrylonitrile-methacrylate, produced undesirable molded parts with gate line ratings of 3.5 or 4 and heat distortion temperatures of 97°C or 91°C.

[0203] The compositions of Comparative Examples 8-11 that did not include BDP produced undesirable molded parts with gate line ratings ranging from 3.5 to 6.

[0204] Comparative Examples (CE) 13-24

[0205] Similarly, the materials listed in Table 2 were compounded, the properties of the obtained compositions were tested, and the results are summarized in Table 2.

[0206] As can be seen from Table 2, the compositions of Comparative Examples 13-17 that do not include styrene-acrylonitrile-methacrylate and BDP produce undesirable molded parts with gate line ratings of 4-6.

[0207] The compositions of Comparative Examples 18 and 20 that did not include styrene-acrylonitrile-methacrylate produced undesirable molded parts with gate line ratings of 3 or 4.5.

[0208] The compositions of Comparative Examples 19 and 21 that did not include BDP produced undesirable molded parts with a gate line rating of 3 or 5.

[0209] The composition of Comparative Example 22, which contained 16.5 wt.% Wollastonite-2, produced an undesirable molded part with a gate line rating of 5.

[0210] The composition containing 2 wt.% styrene-acrylonitrile-methacrylate and 4 wt.% of Comparative Example 23 produced an undesirable molded part with a gate line rating of 3.

[0211] The composition of Comparative Example 24, which contained 2 wt.% of styrene-acrylonitrile-methacrylate, produced an undesirable molded part with a gate line rating of 3.5.

[0212]

[0213] Inventive Examples (IE) 1-9 and Comparative Examples (CE) 25-28

[0214] Similarly, the materials listed in Table 3 were compounded, the properties of the obtained compositions were tested, and the results are summarized in Table 3.

[0215] As can be seen from Table 3, the compositions of Inventive Examples 1 to 9 according to the present invention can be used to prepare molded parts having a good combination of impact strength, heat resistance and aesthetic appearance.

[0216] The composition of Comparative Example 25, which contained 17.5 wt.% of Wollastonite-1, produced an undesirable molded part with a gate line rating of 3.5.

[0217] The composition of Comparative Example 26, which contained 6 wt.% BDP, produced an undesirable molded part with a gate line rating of 4.

[0218] The composition of Comparative Example 27, which contained 17.5 wt.% of Wollastonite-2, produced an undesirable molded part with a gate line rating of 4.

[0219] The composition of Comparative Example 28, which contained 7 wt.% of styrene-acrylonitrile-methyl methacrylate, produced an undesirable molded part with a gate line rating of 6.

[0220]

Claims

1. A polycarbonate composition comprising the following components, relative to the total weight of the composition: A) 40-85 wt.% of aromatic polycarbonate, B) 1-30 wt.% acrylonitrile-butadiene-styrene, C) 8-15 wt.% wollastonite, D) 1-3.5 wt.% of bisphenol A bis(diphenyl phosphate), and E) 2.5-6 wt.% of styrene-acrylonitrile-methacrylate.

2. The composition according to claim 1, wherein the acrylonitrile-butadiene-styrene comprises 5 wt.% to 95 wt.%, preferably 8 wt.% to 90 wt.%, especially 20 wt.% to 85 wt.%, of units derived from acrylonitrile and styrene; and 95 wt.% to 5 wt.%, preferably 92 wt.% to 10 wt.%, especially 80 wt.% to 15 wt.%, of units derived from butadiene, based on the weight of the acrylonitrile-butadiene-styrene.

3. The composition of claim 2, wherein the acrylonitrile-butadiene-styrene comprises 15 wt.% to 35 wt.% of units derived from acrylonitrile, 40 wt.% to 60 wt.% of units derived from styrene, and 5 wt.% to 30 wt.% of units derived from butadiene, based on the weight of the acrylonitrile-butadiene-styrene.

4. The composition according to any one of claims 1 to 3, wherein the wollastonite is in the form of needle-like particles.

5. The composition according to claim 4, wherein the diameter (d 50 ) is 3μm to 50μm.

6. The composition according to any one of claims 4 or 5, wherein the wollastonite has a needle-like morphology with an aspect ratio (L:D) in the range of 3:1 to 15:1, preferably 4:1 to 15:1, more preferably 5:1 to 10:

1.

7. The composition according to any one of claims 1 to 6, wherein the methacrylate in the styrene-acrylonitrile-methacrylate is selected from methyl methacrylate, glycidyl methacrylate, ethyl methacrylate, n-butyl methacrylate, benzyl methacrylate, lauryl methacrylate, stearyl methacrylate, cyclopentyl methacrylate, cyclohexyl methacrylate, benzyl methacrylate and combinations thereof.

8. The composition of any one of claims 1 to 7, wherein the styrene-acrylonitrile-methacrylate comprises 50 wt.% to 95 wt.% of units derived from styrene, 4 wt.% to 45 wt.% of units derived from acrylonitrile, and 1 wt.% to 5 wt.% of units derived from methacrylate, based on the weight of the styrene-acrylonitrile-methacrylate.

9. The composition according to any one of claims 1 to 8, comprising, relative to the total weight of the composition: A) 50-75 wt.% of aromatic polycarbonate, B) 3-26 wt.% acrylonitrile-butadiene-styrene, C) 10-15 wt.% of wollastonite having an aspect ratio (L:D) in the range of 5:1 to 15:1, D) 2-3 wt.% of bisphenol A bis(diphenyl phosphate), and E) 3-4 wt.% of styrene-acrylonitrile-methacrylate.

10. The composition according to any one of claims 1 to 9, wherein the total amount of components A) to E) as defined above is 90 wt.% to 100 wt.%, preferably 95 wt.% to 100 wt.%, more preferably 97 wt.% to 100 wt.%, based on the total weight of the polycarbonate composition according to the invention.

11. The composition according to any one of claims 1 to 10, further comprising up to 5 wt.%, preferably up to 3 wt.%, more preferably 0.1 wt.% to 3 wt.% of an additional component selected from the group consisting of antioxidants, heat stabilizers, mold release agents, antistatic agents, pigments, pH adjusters and lubricants, based on the total weight of the composition.

12. A shaped article prepared from the composition according to any one of claims 1 to 11.

13. The shaped article according to claim 12, which is selected from films; profiles; housing parts for household appliances; sheets; pipes; windows, doors and other profiles for the construction industry; and exterior or interior parts for commercial vehicles.

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