EP4247886A1 - Compositions de polycarbonate contenant du dioxyde de titane et du triacylglycérol contenant des groupes époxy - Google Patents

Compositions de polycarbonate contenant du dioxyde de titane et du triacylglycérol contenant des groupes époxy

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Publication number
EP4247886A1
EP4247886A1 EP21810372.9A EP21810372A EP4247886A1 EP 4247886 A1 EP4247886 A1 EP 4247886A1 EP 21810372 A EP21810372 A EP 21810372A EP 4247886 A1 EP4247886 A1 EP 4247886A1
Authority
EP
European Patent Office
Prior art keywords
weight
epoxidized
triacylglycerol
thermoplastic composition
titanium dioxide
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
EP21810372.9A
Other languages
German (de)
English (en)
Inventor
Rolf Wehrmann
Helmut Werner Heuer
Anke Boumans
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Covestro Deutschland AG
Original Assignee
Covestro Deutschland AG
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Covestro Deutschland AG filed Critical Covestro Deutschland AG
Publication of EP4247886A1 publication Critical patent/EP4247886A1/fr
Pending legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • C08L69/005—Polyester-carbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005—Stabilisers against oxidation, heat, light, ozone
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0066—Flame-proofing or flame-retarding additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/15—Heterocyclic compounds having oxygen in the ring
    • C08K5/151—Heterocyclic compounds having oxygen in the ring having one oxygen atom in the ring
    • C08K5/1515—Three-membered rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/50—Phosphorus bound to carbon only
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/20—Applications use in electrical or conductive gadgets
    • C08L2203/206—Applications use in electrical or conductive gadgets use in coating or encapsulating of electronic parts

Definitions

  • the invention relates to titanium dioxide-containing polycarbonate-based compositions with high reflection and preferably good flame retardant properties.
  • the present invention also relates to molded parts made from these compositions, for example for housing or housing parts or other elements in the EE and IT sector, e.g. for panels and switches for automotive interior lighting and in particular for reflectors of lighting units such as LED lamps or LED arrays.
  • CN 109867941 A describes a reflective polycarbonate material that contains titanium dioxide, a liquid silicone and other polymeric components.
  • TW 200743656 A discloses flame-retardant, halogen-free, reflective polycarbonate compositions which, in addition to titanium dioxide, contain inorganic fillers such as clay or silica and other organic components such as optical brighteners, perfluoroalkylene compounds and metal salts of aromatic sulfur compounds.
  • JP 2010138412 A describes flame-retardant polycarbonate compositions containing titanium dioxide, which contain silicone compounds, PTFE and inorganic components such as talc, mica or glass.
  • titanium dioxide In order to achieve high degrees of reflection, however, large amounts of titanium dioxide are required. This is disadvantageous, since titanium dioxide can lead to degradation of the polycarbonate matrix, which can lead to melt instability and the viscosity of the compound decreases, which means that the thermal and mechanical properties also deteriorate.
  • titanium dioxide also has a very significant effect on the price of polycarbonate compositions, making it desirable to increase reflectance by means other than adding even larger amounts of titanium dioxide.
  • Optical brighteners that could be added have the disadvantage that when used, they lead to a non-linear reflection curve, which can lead to a blue color cast in the material, which is perceived as annoying.
  • the object of the present invention was therefore to provide titanium dioxide-containing, polycarbonate-based compositions with improved reflection and preferably a flame retardancy of UL94 V-0 with a wall thickness of 2 mm and corresponding moldings, the compositions being as effective as possible while achieving the properties mentioned should not exhibit any significantly poorer flow behavior during processing and, if possible, should also be without a disturbing color cast.
  • polycarbonate-based compositions containing titanium dioxide have increased reflection values if epoxidized triacylglycerol, in particular in the form of epoxidized soybean oil, is present.
  • epoxidized triacylglycerol in particular in the form of epoxidized soybean oil
  • a fundamentally positive effect on the yellowness index can be observed.
  • the flow behavior of the compositions is not significantly affected and the good processability in injection molding is retained.
  • the flame retardant properties determined according to UL94, remain almost unchanged even when flame retardants are used.
  • compositions are preferred which have good reflection properties but also flame retardant properties.
  • the invention thus relates to thermoplastic compositions containing
  • compositions according to the invention are thermoplastic compositions containing
  • compositions contain
  • flame retardants selected from the group consisting of alkali metal, alkaline earth metal and ammonium salts of aliphatic or aromatic sulfonic acid, sulfonamide or sulfonimide derivatives and combinations of these, and
  • compositions particularly preferably contain
  • mixtures of the aforementioned compounds, which come under the same generic term, can also be present as component E flame retardants.
  • the composition can contain other components, such as other additives in the form of component F.
  • the composition can also or contain several other thermoplastics as blend partners which are not covered by any of components A to F.
  • compositions described above very particularly preferably contain no further components, but rather the amounts of components A, B, C (or C1—epoxidized soybean oil containing epoxidized triacylglycerol or epoxidized triacylglycerol) and, if appropriate, D and/or where appropriate E and/or where appropriate F, particularly in the preferred embodiments described, add up to 100% by weight, ie the compositions consist of components A, B, C (where appropriate Cl), where appropriate D, possibly E and/or possibly F.
  • the components used can contain the usual impurities which, for example, result from their production processes. It is preferred to use components that are as pure as possible. It is also understood that these impurities can also be contained in a closed formulation of the composition.
  • the compositions according to the invention are preferably used to produce moldings.
  • the compositions preferably have a melt volume flow rate (MVR) of from 3 to 40 cm 3 /(10 min.), more preferably from 6 to 30 cm 3 /(10 min.), even more preferably from 8 to 25 cm 3 /(10 min ), particularly preferably from 9 to 24 cm 3 /(10 min), determined according to ISO 1133:2012-3 (test temperature 300° C., mass 1.2 kg).
  • MVR melt volume flow rate
  • compositions according to the invention have a rating of V0 in the UL94 fire test (2.0 mm wall thickness).
  • the invention also relates to improving the reflection, preferably determined according to ASTM E 1331-2015 with a layer thickness of 2 mm, of titanium dioxide-containing polycarbonate compositions by adding epoxidized triacylglycerol, in particular in the form of an epoxidized soybean oil.
  • the improvement in reflection relates to the corresponding compositions without epoxidized triacylglycerol, in particular in the form of an epoxidized soybean oil.
  • an improvement in the yellowness index preferably determined according to ASTM E 313-15 (observer 10°/light type: D65) on sample plates with a layer thickness of 2 mm, is preferably also achieved.
  • ASTM E 313-15 observed 10°/light type: D65
  • the reflection of the compositions in which the reflection is improved even further by the addition of component C is preferably at least 93.5%, more preferably at least 95%, determined according to ASTM E 1331-2015 for one layer thickness of 2 mm
  • the individual components of the compositions according to the invention are explained in more detail below:
  • Polycarbonate in the sense of the invention is understood to mean both aromatic homopolycarbonates and aromatic copolycarbonates.
  • the polycarbonates can be linear or branched in a known manner. According to the invention, mixtures of polycarbonates can also be used.
  • compositions according to the invention contain, as component A), preferably 59.99% by weight to 96.99% by weight of aromatic polycarbonate.
  • a proportion of at least 59.99% by weight of aromatic polycarbonate in the overall composition means, according to the invention, that the composition is based on aromatic polycarbonate.
  • the amount of aromatic polycarbonate in the composition is preferably from 69.99% to 96.99% by weight, more preferably from 69.95% to 96.985% by weight, in particular up to 96.95% by weight %, even more preferably 77.985% by weight to 96.985% by weight, particularly preferably 77.945% by weight to 96.945% by weight, very particularly preferably 79.79% by weight to 89.79% by weight %, extremely preferably up to 89.7% by weight, it being possible for a single polycarbonate or a mixture of several polycarbonates to be present.
  • the polycarbonates contained in the compositions are produced in a known manner from dihydroxyaryl compounds, carbonic acid derivatives, optionally chain terminators and branching agents.
  • Aromatic polycarbonates are produced, for example, by reacting dihydroxyaryl compounds with carbonic acid halides, preferably phosgene, and/or with aromatic dicarboxylic acid dihalides, preferably benzenedicarboxylic acid dihalides, according to the phase boundary surface process, optionally using chain terminators and optionally using trifunctional or more than trifunctional branchers.
  • dihydroxyaryl compounds with carbonic acid halides, preferably phosgene
  • aromatic dicarboxylic acid dihalides preferably benzenedicarboxylic acid dihalides
  • dihydroxyaryl compounds suitable for producing the polycarbonates are hydroquinone, resorcinol, dihydroxydiphenyls, bis(hydroxyphenyl)alkanes, bis(hydroxyphenyl)cycloalkanes, bis(hydroxyphenyl) sulfides, bis(hydroxyphenyl) ethers, bis( Hydroxyphenyl) ketones, bis(hydroxyphenyl) sulfones, bis(hydroxyphenyl) sulfoxides, a-a'-bis(hydroxyphenyl)diisopropylbenzenes, phthalimidines derived from isatin or phenolphthalein derivatives, and their nucleus-alkylated ones , nucleus arylated and nucleus halogenated compounds.
  • Preferred dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis- (4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, dimethyl bisphenol 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-trime - ethylcycl
  • bisphenols 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'-dihydroxydiphenyl and dimethylbisphenol A and the bisphenols of the formulas (I), (II ) and (III).
  • bisphenol A 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'-dihydroxydiphenyl and dimethylbisphenol A 4,4'-dihydroxydiphenyl and dimethylbisphenol A
  • dihydroxyaryl compounds are, for example, in US Pat. No. 3,028,635, US Pat. No. 2,999,825, US Pat. No. 3,148,172, US Pat. in DE 1 570 703 A, DE 2063 050 A, DE 2 036 052 A, DE 2 211 956 A and DE 3 832 396 A, in FR 1 561 518 A, in the monograph "H. Schnell, Chemistry and Physics of Polycarbonates , Interscience Publishers, New York 1964" and in JP 62039/1986 A, JP 62040/1986 A and JP 105550/1986 A.
  • Suitable carbonic acid derivatives are phosgene or diphenyl carbonate.
  • Suitable chain terminators that can be used in the production of the polycarbonates are monophenols.
  • suitable monophenols are phenol itself, alkylphenols such as cresols, p-tert-butylphenol, cumylphenol and mixtures thereof.
  • Preferred chain terminators are the phenols which are linear or branched, preferably unsubstituted, one or more times with C 1 - to C 30 -alkyl radicals, or substituted with tert-butyl. Particularly preferred chain terminators are phenol, cumylphenol and/or p-tert-butylphenol.
  • the amount of chain terminator to be used is preferably 0.1 to 5 mol %, based on moles of dihydroxyaryl compounds used in each case.
  • the chain terminators can be added before, during or after the reaction with a carbonic acid derivative.
  • Suitable branching agents are the trifunctional or more than trifunctional compounds known in polycarbonate chemistry, in particular those having three or more than three phenolic OH groups.
  • branching agents are 1,3,5-tri-(4-hydroxyphenyl)benzene, 1,1,1-tri-(4-hydroxyphenyl)ethane, tri-(4-hydroxyphenyl)phenylmethane, 2, 4-bis(4-hydroxyphenylisopropyl)-phenol, 2,6-bis(2-hydroxy-5'-methyl-benzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2, 4-dihydroxyphenyl)propane, tetra-(4-hydroxyphenyl)methane, tetra-(4-(4-hydroxyphenylisopropyl)phenoxy)methane and l,4-bis-((4', 4"-dihydroxytriphenyl(methyl)benzene and 3,3-bis(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole.
  • the amount of any branching agents to be used is preferably 0.05 mol % to 2.00 mol %, based on moles of dihydroxyaryl compounds used in each case.
  • the branching agents can either be initially taken with the dihydroxyaryl compounds and the chain terminators in the aqueous-alkaline phase or, dissolved in an organic solvent, can be added before the phosgenation. In the case of the transesterification process, the branching agents are used together with the dihydroxyaryl compounds.
  • Particularly preferred polycarbonates are the homopolycarbonate based on bisphenol A, the copolycarbonates based on 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and 4,4'-dihydroxydiphenyl, and the copolycarbonates based on the two Monomers bisphenol A and 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and of the dihydroxyaryl compounds of the formulas (I), (II) and (III) in which R' is in each case C 1 - to C 4 -alkyl, aralkyl or aryl, preferably methyl or phenyl, very particularly preferably methyl, derived homo- or copolycarbonates.
  • R 5 is hydrogen or C 1 - to C 4 - alkyl, C 1 - to C 3 -alkoxy, preferably hydrogen; methoxy or methyl,
  • R 6 , R 7 , R 8 and R 9 are each independently C 1 - to C 4 -alkyl or C& - to C 12 -aryl, preferably methyl or phenyl,
  • Y represents a single bond, SO 2 -, -S-, -CO-, -O-, C 1 - to C 6 -alkylene, C 2 - to C 5 -alkylidene, C 6 - to C 12 -arylene, which optionally can be condensed with other aromatic rings containing heteroatoms or for a C 5 - to C 6 -cycloalkylidene radical which can be substituted one or more times by C 1 - to C 4 -alkyl, preferably for a single bond, -O-, isopropylidene or represents a C 5 - to C 6 -cycloalkylidene radical which may be mono- or polysubstituted by C 1 - to C 4 -alkyl, V is oxygen, C 2 - to C 6 -alkylene or C 3 - to C 6 -alkylidene, preferably oxygen or C 3 - alkylene, p, q and r each independently represent 0 or
  • Z is a C 1 - to C 6 -alkylene, preferably C 2 -alkylene,
  • 0 is an average number of repeating units of 10 to 500, preferably 10 to 100
  • m is an average number of repeating units of 1 to 10, preferably 1 to 6, more preferably 1.5 to 5. It is also possible to use diphenols in which two or more siloxane blocks of the general formula (Ia) are linked to one another via terephthalic acid and/or isophthalic acid to form ester groups.
  • (Poly)siloxanes of the formulas (2) and (3) are particularly preferred where RI is hydrogen, C 1 - to C 4 -alkyl, preferably hydrogen or methyl and particularly preferably hydrogen,
  • R2 independently for aryl or alkyl, preferably for methyl
  • X represents a single bond, -SO 2 -, -CO-, -O-, -S-, C 1 - to C 6 -alkylene, C 2 - to C 5 -alkylidene or for C 6 - to C 12 -arylene, which may optionally be fused to other aromatic rings containing heteroatoms,
  • X preferably for a single bond, C 1 - to C 5 -alkylene, C 2 - to C 5 -alkylidene, C 5 - to C 12 -cycloalkylidene, -O-, -SO- -CO-, -S-, -SO 2 -, X particularly preferably represents a single bond, isopropylidene, C 5 - to C 12 -cycloalkylidene or oxygen, and very particularly preferably represents isopropylidene, n is an average number from 10 to 400, preferably 10 and 100, particularly preferably 15 to 50 and m is an average number from 1 to 10, preferably from 1 to 6 and particularly preferably from 1.5 to 5.
  • the siloxane block can be derived from the following structure where a in formula (IV), (V) and (VI) is an average number of 10 to 400, preferably 10 to 100 and particularly preferably 15 to 50. It is also preferred here that at least two identical or different siloxane blocks of the general formulas (IV), (V) or (VI) are linked to one another via terephthalic acid and/or isophthalic acid to form ester groups.
  • V is C3 -alkylene
  • R8 and R9 are methyl
  • W is C 3 -alkylene
  • m 1
  • R 5 is hydrogen or C 1 - to C 4 -alkyl, preferably hydrogen or methyl
  • R 6 and R 7 are each independently C 1 - to C 4 alkyl, preferably methyl and 0 is 10 to 500.
  • Copolycarbonates with monomer units of the formula (Ia) and in particular their preparation are described in WO 2015/052106 A2.
  • thermoplastic polycarbonates including the thermoplastic, aromatic polyester carbonates, preferably have weight-average molecular weights M w of from 15,000 g/mol to 40,000 g/mol, more preferably up to 34,000 g/mol, particularly preferably from 17,000 g/mol to 33,000 g/mol, in particular from 19,000 g/mol to 32,000 g/mol, determined by gel permeation chromatography, calibrated against bisphenol A polycarbonate standards using dichloromethane as eluent, calibration with linear polycarbonates (from bisphenol A and phosgene) of known molar mass distribution from PSS Polymer Standards Service GmbH, Germany , Calibration according to method 2301 -0257502 -09D (from 2009 in German) from Currenta GmbH & Co.
  • the eluent is dichloromethane.
  • component A is preferably used in the form of powders, granules or mixtures of powders and granules.
  • Compositions according to the invention contain 3.0% by weight to 40.0% by weight, preferably 5.0% by weight to 35% by weight, more preferably 6.0% by weight to 30% by weight, even more preferably 7.0% by weight to 25% by weight, even more preferably 8.0% by weight to 22% by weight, particularly preferably 9.0% by weight to 20% by weight, very particularly preferably 10.0% by weight to 15.0% by weight, extremely preferably 10.0% by weight to 12.0% by weight, titanium dioxide.
  • the titanium dioxide according to component B of the compositions according to the invention preferably has an average particle size D 50, determined by means of scanning electron microscopy (STEM), of 0.1 to 5 ⁇ m, preferably 0.2 ⁇ m to 0.5 ⁇ m.
  • the titanium dioxide can also have another Particle size have, for example, an average particle size D 50 , determined by means of scanning electron microscopy (STEM), of> 0.5 microns, about 0.65 to 1.15 microns.
  • the titanium dioxide preferably has a rutile structure.
  • the titanium dioxide used according to the invention is a white pigment, Ti(IV)O 2 .
  • colored titanium dioxides also contain significant amounts of elements such as Sb, Ni and Cr, resulting in a color impression other than “white”. It goes without saying that the white pigment titanium dioxide can also contain traces of other elements as impurities. However, these amounts are so small that the titanium dioxide does not acquire a color cast.
  • Suitable titanium dioxides are preferably those which are produced by the chloride process, made hydrophobic, specially aftertreated and suitable for use in polycarbonate.
  • sized titanium dioxide it is also possible to use unsized titanium dioxide or a mixture of both in compositions according to the invention.
  • the use of sized titanium dioxide is preferred.
  • titanium dioxide Possible surface modifications of titanium dioxide include inorganic and organic modifications. These include, for example, surface modifications based on aluminum or polysiloxane.
  • An inorganic coating may contain 0.0% to 5.0% by weight of silicon dioxide and/or aluminum oxide.
  • An organic based modification may contain from 0.0% to 3.0% by weight of a hydrophobic wetting agent.
  • the titanium dioxide preferably has an oil absorption number, determined according to DIN EN ISO 787-5: 1995-10, from 12 to 18 g/100 g titanium dioxide, more preferably from 13 to 17 g/100 g titanium dioxide, particularly preferably from 13.5 to 15 .5 g/100 g titanium dioxide.
  • titanium dioxide with the standard designation R2 according to DIN EN ISO 591-1:2001-08, which is stabilized with aluminum and/or silicon compounds and has a titanium dioxide content of at least 96.0% by weight.
  • Such titanium dioxides are available under the brand names Kronos 2233 and Kronos 2230.
  • compositions according to the invention contain epoxidized triacylglycerol as component C.
  • Component C can be a specific triacylglycerol or a mixture of different epoxy group-containing (“epoxidized”) triacylglycerols. It is preferably a mixture of different triacylglycerols.
  • Component C preferably contains a mixture of triesters of glycerol with oleic acid, linoleic acid, linolenic acid, palmitic acid and/or stearic acid. More preferably, the esters according to component C only include esters of glycerol with the fatty acids mentioned.
  • Particularly preferred is component C in the form of epoxidized soybean oil (C1) introduced into the compositions according to the invention.
  • the CAS number of epoxidized soybean oil is 8013-07-8.
  • the triacylglycerols are therefore partially or completely epoxidized. Preferably at least 90%, more preferably at least 95%, even more preferably at least 98% of the C ⁇ C double bonds of the triacylglycerols originating from the unsaturated carboxylic acids are epoxidized.
  • Component C is preferably a mixture of different compounds, as is the case, for example, with the use of epoxidized soybean oil.
  • the OH numbers of these mixtures are preferably between 180 and 300 mg KOH/g (method 2011-0232602-92D from Currenta GmbH & Co. OHG, Leverkusen, corresponding to DIN EN 1802554: 1998-10 with pyridine as solvent).
  • the acid numbers of these mixtures are preferably below 1 mg KOH/g, more preferably ⁇ 0.5 mg KOH/g, determined using DIN EN ISO 2114:2006-11.
  • the Wijs iodine number of the mixtures is preferably ⁇ 5.0 g Iodine/100 g, more preferably ⁇ 3.0 g iodine/100 g (method 2201-0152902-95D from Currenta GmbH & Co. OHG, Leverkusen).
  • the oxirane number, determined according to DIN EN 1877-1:2000-12, is preferably 5 to 10 g O 2 /100 g, particularly preferably 6.3 to 8.0 g O 2 /100 g.
  • the polycarbonate-containing compositions preferably contain at least 0.01% by weight, more preferably 0.01% by weight to 5.0% by weight, even more preferably 0.05% by weight to 2.0% by weight % by weight, particularly preferably 0.1% by weight to 0.8% by weight, very particularly preferably up to 0.6% by weight, in particular up to 0.4% by weight, of component C .
  • compositions according to the invention can also contain thermal stabilizers D.
  • Phosphorus-based stabilizers selected from the group consisting of phosphates, phosphites, phosphonites, phosphines and mixtures thereof are particularly suitable as thermal stabilizers. Mixtures of different compounds from one of these subgroups can also be used, e.g. two phosphites.
  • Phosphorus compounds with the oxidation number +III are preferably used as thermal stabilizers.
  • thermal stabilizers are triphenylphosphine, tris-(2,4-di-tert-butylphenyl)phosphite (Irgafos® 168), tetrakis-(2,4-di-tert-butylphenyl)-[1,1-biphenyl]- 4,4'- diylbisphosphonite, octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate (Irganox® 1076), bis-(2,4-dicumylphenyl)pentaerythritol diphosphite (Doverphos® S-9228), bis- (2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite (ADK STAB PEP-36).
  • Irganox® B900 mixture of Irgafos® 168 and Irganox® 1076 in a ratio of 4: 1 or Doverphos® S-9228 with Irganox® B900 or Irganox® 1076.
  • the heat stabilizers are preferably used in amounts up to 1.0% by weight, more preferably from 0.003% to 1.0% by weight, even more preferably from 0.005% to 0.5% by weight, especially preferably 0.01% by weight to 0.2% by weight.
  • compositions preferably contain at least one flame retardant selected from the group consisting of the alkali metal, alkaline earth metal and ammonium salts of aliphatic or aromatic sulfonic acid, sulfonamide and sulfonimide derivatives, or else combinations of these.
  • derivatives are understood here and elsewhere to mean compounds whose molecular structure has another atom or another atomic group in place of an H atom or a functional group, or in which one or more atoms/atomic groups have been removed. The parent connection is thus still recognizable.
  • Compositions according to the invention particularly preferably comprise one or more compounds selected from the group consisting of sodium or potassium perfluorobutane sulfate, sodium or potassium perfluoromethanesulfonate, sodium or potassium perfluorooctane sulfate, sodium or potassium 2,5-dichlorobenzene sulfate, sodium as flame retardants - or potassium 2,4,5-trichlorobenzene sulphate, sodium or potassium diphenylsulphonate, sodium or potassium 2-formylbenzenesulphonate, sodium or potassium (N-benzenesulphonyl)-benzenesulphonamide or mixtures thereof.
  • Sodium or potassium perfluorobutane sulfate, sodium or potassium perfluorooctane sulfate, sodium or potassium diphenylsulfone sulfonate or mixtures thereof are preferably used.
  • Potassium perfluoro-1-butanesulfonate which is commercially available, inter alia as Bayowet® C 4 from Lanxess, Leverkusen, Germany, is very particularly preferred.
  • the amounts of alkali metal, alkaline earth metal and/or ammonium salts of aliphatic or aromatic sulfonic acid, sulfonamide and sulfonimide derivatives in the composition are preferably a total of 0.05% by weight to 0.5% by weight %, more preferably 0.06% by weight to 0.3% by weight, particularly preferably 0.06% by weight to 0.2% by weight, very particularly preferably 0.065% by weight to 0 .12% by weight.
  • Component F Component F
  • further additives are optional, preferably up to 10.0% by weight, more preferably 0.1% by weight to 6.0% by weight, particularly preferably 0.1% by weight to 3.0% by weight. %, very particularly preferably 0.2% by weight to 1.0% by weight, in particular up to 0.5% by weight, of other customary additives (“further additives”).
  • the group of other additives does not include heat stabilizers, as these have already been described as component D.
  • the group of other additives does not include any flame retardants according to component E.
  • component F does not include titanium dioxide or any triacylglycerol containing epoxy groups, nor does it include epoxidized soybean oil, since these are already included as components B and C and C1 are described.
  • Such other additives as are usually added to polycarbonates are, in particular, antioxidants, mold release agents, flame retardants other than component E, anti-dripping agents such as polytetrafluoroethylene (Teflon) or SAN-encapsulated PTFE (e.g. Blendex 449), UV absorbers, IR absorbers , impact modifiers, antistatic agents, optical brighteners, fillers other than component B, e.g. B. talc, silicates or quartz, light scattering agents, colorants such as organic pigments, inorganic pigments other than component B and / or additives for laser marking.
  • antioxidants such as polytetrafluoroethylene (Teflon) or SAN-encapsulated PTFE (e.g. Blendex 449)
  • UV absorbers such as polytetrafluoroethylene (Teflon) or SAN-encapsulated PTFE (e.g. Blendex 449)
  • UV absorbers e.g. B. talc, silicate
  • additives are described, for example, in EP-A 0 839 623, WO-A 96/15102, EP-A 0 500 496 or in the "Plastics Additives Handbook", Hans Zweifel, 5th Edition 2000, Hanser Verlag, Kunststoff, in particular anti-dripping agents, in the usual amounts for polycarbonate. These additives can be added individually or as a mixture.
  • UV stabilizers which have the lowest possible transmission below 400 nm and the highest possible transmission above 400 nm.
  • Ultraviolet absorbers which are particularly suitable for use in the composition according to the invention are benzotriazoles, triazines, benzophenones and/or arylated cyanoacrylates.
  • Particularly suitable ultraviolet absorbers are hydroxybenzotriazoles, such as 2-(3',5'-bis-(1,1-dimethylbenzyl)-2'-hydroxyphenyl)benzotriazole (Tinuvin® 234, BASF SE, Ludwigshafen ), 2-(2'-hydroxy-5'-(tert.-octyl)-phenyl)-benzotriazole (Tinuvin® 329, BASF SE, Ludwigshafen), bis-(3-(2H-benzotriazolyl)-2- hydroxy-5-tert-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), 2-(5chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methyl-phenol
  • Particularly preferred special UV stabilizers are Tinuvin 360, Tinuvin 329, Tinuvin 326, Tinuvin 1600, Tinuvin 312, Uvinul 3030 and/or Hostavin B-Cap, Tinuvin 329 and Tinuvin 360 are very particularly preferred.
  • the composition preferably contains ultraviolet absorbers in an amount of up to 0.8% by weight, preferably 0.05% by weight to 0.5% by weight, more preferably 0.08% by weight. -% to 0.4% by weight, very particularly preferably 0.1% by weight to 0.35% by weight, based on the total composition.
  • compositions according to the invention can also contain phosphates or sulfonic acid esters as transesterification stabilizers.
  • Triisooctyl phosphate is preferably present as a transesterification stabilizer.
  • Triisooctyl phosphate is preferably used in amounts of from 0.003% to 0.05% by weight, more preferably from 0.005% to 0.04% by weight and particularly preferably from 0.01% to 0 .03% by weight, based on the total composition.
  • the composition can be free from pentaerythritol tetrastearate and glycerol monostearate, in particular free from mold release agents customarily used for polycarbonate, further free from any mold release agents.
  • At least one thermal stabilizer (component D) and/or at least one flame retardant according to component E is particularly preferably present in the compositions according to the invention.
  • An impact modifier can also be present as a further additive (component F) in compositions according to the invention.
  • impact modifiers are: acrylate core-shell systems or butadiene rubbers (Paraloid grades from DOW Chemical Company); Olefin-acrylate copolymers such as. B. Elvaloy® grades from DuPont; Silicone acrylate rubbers such. B. the Metablen® grades from Mitsubishi Rayon Co., Ltd.
  • At least one anti-dripping agent is preferably included as a further additive according to component F, more preferably in an amount of 0.05% by weight to 1.5% by weight, in particular 0.1% by weight to 1.0% by weight %.
  • thermoplastic compositions according to the invention can in principle also contain blending partners.
  • Thermoplastic polymers suitable as blend partners are, for example, polystyrene, styrene copolymers, aromatic polyesters such as polyethylene terephthalate (PET), PET-cyclohexanedimethanol copolymer (PETG), polyethylene naphthalate (PEN), Polybutylene terephthalate (PBT), cyclic polyolefin, poly- or copolyacrylate, poly- or co-polymethacrylate such as poly- or copolymethyl methacrylate (such as PMMA), and copolymers with styrene such as transparent polystyrene acrylonitrile (PS AN), thermoplastic polyurethanes and/or polymers Based on cyclic olefins (eg TOPAS®, a commercial product from Ticona).
  • cyclic olefins eg TOPAS®, a commercial product from Ticon
  • compositions consist of
  • flame retardants selected from the group of alkali metal, alkaline earth metal or ammonium salts of aliphatic or aromatic sulfonic acid, sulfonamide or sulfonimide derivatives and combinations thereof, and
  • compositions consist of
  • flame retardants selected from the group of alkali metal, alkaline earth metal or ammonium salts of aliphatic or aromatic sulfonic acid, sulfonamide or sulfonimide derivatives and combinations thereof, and
  • compositions according to the invention containing the components A to C (or C1) and optionally D and/or optionally E and/or optionally F and optionally blending partners, is carried out using common incorporation methods by combining, mixing and homogenizing of the individual components, with the homogenization in particular preferably taking place in the melt under the action of shearing forces. If appropriate, the bringing together and mixing takes place before the melt is homogenized using powder premixes.
  • Premixes of granules or granules and powders with components B, C or C1 and optionally D, E and/or F can also be used. It is also possible to use premixes which have been produced from solutions of the mixture components in suitable solvents, with the solution being homogenized if appropriate and the solvent then being removed.
  • components B to F of the composition according to the invention can be introduced into the polycarbonate, optionally into the polycarbonate with a blend partner, by known methods or as a masterbatch.
  • masterbatches are preferred for introducing components B to F, individually or as a mixture.
  • composition according to the invention can be brought together, mixed, homogenized and then extruded in customary devices such as screw extruders (for example twin-screw extruders, ZSK), kneaders, Brabender or Banbury mills. After extrusion, the extrudate can be cooled and chopped up. Individual components can also be premixed and then the remaining starting materials can be added individually and/or also mixed.
  • the combination and mixing of a premix in the melt can also take place in the plasticizing unit of an injection molding machine.
  • the melt is transferred directly into a shaped body.
  • compositions according to the invention can be processed in a customary manner on customary machines, for example on extruders or injection molding machines, to give any shaped articles, such as for example films, sheets or bottles.
  • compositions or moldings from the compositions appear “radiant white” to the observer.
  • the molded parts are preferably produced by injection molding, extrusion or from a solution in a casting process.
  • compositions according to the invention are suitable for producing multilayer systems.
  • the polycarbonate-containing composition is applied in one or more layer(s) to a molded article made of a plastic or itself serves as a substrate layer to which one or more further layers are applied.
  • the application can take place at the same time as or immediately after the shaping of the shaped body, for example by back-injecting a film, coextrusion or multi-component injection molding.
  • it can also be applied to the finished base body, for example by lamination with a film, overmoulding of an existing shaped body or by coating from a solution.
  • compositions according to the invention are suitable for producing components in the lighting sector, such as lamp reflectors, in particular LED lamps or LED arrays, in the automotive sector, for example for covers, switches, headlight reflectors or frames, and for the production Positioning of frames or frame parts or housing or housing parts in the EE (electrical/electronics) and IT area. Due to the very good reflection values, the compositions according to the invention are preferably used for the production of reflectors.
  • compositions according to the invention consisting of the compositions according to the invention or comprising - e.g. in the case of multi-component injection molding - these, including the molded parts which represent a layer of a multi-layer system or an element of an above-mentioned component or are such a component, from (“ consisting of") these compositions according to the invention are also the subject of this application.
  • the compositions according to the invention can also be used in the form of filaments, as granules or powder as a material in 3D printing.
  • compositions according to the invention also apply--where applicable--to the uses according to the invention.
  • epoxidized triacylglycerol in particular in the form of epoxidized soybean oil, to improve the reflection of titanium dioxide-containing polycarbonate compositions, with the reflection preferably being determined according to ASTM E 1331-2015 with a layer thickness of 2 mm
  • epoxidized triacylglycerol especially in the form of epoxidized soybean oil, to improve the yellowness index, preferably determined according to ASTM E 313-15 (observer 10°/light type: D65) on sample plates with a layer thickness of 2 mm , whereby both goals can stand alone or in combination with each other.
  • the polycarbonate-based compositions described in the following examples were produced by compounding on a ZE 25 extruder from Berstorff with a throughput of 10 kg/h.
  • the melt temperature was 275°C.
  • Component Al Linear polycarbonate based on bisphenol A with a melt volume flow rate MVR of 19 cm 3 /(10 min) (according to ISO 1133:2012-03, at a test temperature of 300°C and a load of 1.2 kg).
  • Component A-2 Linear polycarbonate in powder form based on bisphenol A with a melt volume flow rate MVR of 19 cm 3 /(10 min) (according to ISO 1133:2012-03, at a test temperature of 300°C and 1, 2 kg load).
  • Component A-3 Linear polycarbonate in powder form based on bisphenol A with a melt volume flow rate MVR of 19 cm 3 /(10 min) (according to ISO 1133:2012-03, at a test temperature of 300°C and 1, 2 kg load) containing 250 p ⁇ m triphenylphosphine from BASF SE as component Dl.
  • Component B Kronos 2230 titanium dioxide from Kronos Titan GmbH, Leverkusen.
  • Component C Epoxidized soybean oil (“soya oil D65”) from Avokal GmbH, Wuppertal, with an acid number ⁇ 0.5 mg KOH/g, determined using DIN EN ISO 2114:2006-11, an oxirane value (epoxy oxygen ES , calculated from the epoxide number EEW, indicates how many grams of oxygen are contained in 100 g of oil; EEW determined according to DIN EN 1877-1:2000-12) of ⁇ 6.3 g O 2 /100 g.
  • epoxy oxygen ES calculated from the epoxide number EEW, indicates how many grams of oxygen are contained in 100 g of oil; EEW determined according to DIN EN 1877-1:2000-12
  • triacylglycerols which are a mixture of triesters of glycerine with oleic acid, linoleic acid, linolenic acid, palmitic acid and/or stearic acid.
  • Component D1 triphenylphosphine, commercially available from BASF SE, Ludwigshafen.
  • Component El potassium perfluoro-1-butanesulfonate, commercially available as Bayowet® C 4 from Lanxess AG, Leverkusen, Germany, CAS no. 29420-49-3.
  • Component F1 Blendex® B449 (approx. 50% by weight PTFE and approx. 50% by weight SAN [from 80% by weight styrene and 20% by weight acrylonitrile]) from Chemtura Corporation. anti-drip agent.
  • Component F2 Paraloid EXL2300 from Dow. Acrylic core/shell impact modifier based on butyl acrylate rubber.
  • Component F3 Tinuvin 329, UV stabilizer with a benzotriazole structure, commercially available from BASF SE, Ludwigshafen.
  • the melt volume flow rate (MVR) was determined according to ISO 1133:2012-03 (mainly at a test temperature of 300° C., mass 1.2 kg) using the Zwick 4106 device from Zwick Roell. In addition, the MVR value was measured after 20 minutes of preheating (IMVR20'). This is a measure of melt stability under increased thermal stress.
  • IMVR20' 20 minutes of preheating
  • the total reflectance spectrum was measured using a spectrophotometer based on the ASTM E 1331-04 standard.
  • the total transmission spectrum was measured using a spectrophotometer based on the ASTM E 1348-15 standard.
  • the layer thickness was 2 mm.
  • the visual transmission Ty (according to illuminant D65, observer 10°) or the visual reflection Ry (according to illuminant D65, observer 10°) were calculated in accordance with ASTM E 308-08. This also applies to the color values L*a*b*.
  • the yellowness index (Y.I.) was determined according to ASTM E 313-10 (observer: 10° / light type: D65) at a layer thickness of 2 mm.
  • the glass transition temperature Tg was measured by DSC in a differential heat flow calorimeter (Mettler DSC 3+) at a heating rate of 10 K/min (atmosphere: 50 ml/min nitrogen) in standard crucibles over a temperature range of 0 °C - 280 °C .
  • the value determined in the 2nd heating process was given. The measurement was carried out according to ISO 11357-2:2014-07.
  • the flammability of the tested samples was also assessed and classified according to UL94.
  • specimens measuring 125 mm x 13 mm x d(mm) were produced, with the thickness d corresponding to the smallest wall thickness in the intended application.
  • a VO classification means that the flame goes out by itself after a maximum of 10 s. Burning dripping does not occur. An afterglow after the second flaming occurs for a maximum of 30 s.
  • the sample plates were each produced by injection molding at the melt temperatures given in the tables below.
  • epoxidized triacylglycerol does not reduce the effect of the added flame retardant.
  • epoxidized triacylglycerol is present, even when flame retardants are present in different amounts (E-6 to E-9), higher reflection values are still achieved than is the case without the presence of epoxidized triacylglycerol (V-5).
  • flame retardants only the presence of flame retardants makes it possible for compositions with the same titanium dioxide content to achieve a VO classification according to UL94 with a wall thickness of only 1.5 mm.
  • UV stabilizers As expected, the addition of UV stabilizers has a slightly negative effect on the yellowness index (V-33 with V-34, V-35; inherent color of the UV absorber). However, this effect is canceled out again by the addition of epoxidized tricyclic glycerol (E-36, E-37), with a slight improvement in reflection occurring at the same time.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des compositions thermoplastiques à base de polycarbonate contenant du dioxyde de titane, qui contiennent du triacylglycérol époxydé et qui sont appropriées à l'utilisation dans des réflecteurs. Les compositions présentent une réflectance améliorée et un indice de jaunissement inférieur par comparaison à des compositions de référence qui ne contiennent pas de triacylglycérol époxydé.
EP21810372.9A 2020-11-23 2021-11-18 Compositions de polycarbonate contenant du dioxyde de titane et du triacylglycérol contenant des groupes époxy Pending EP4247886A1 (fr)

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PCT/EP2021/082124 WO2022106530A1 (fr) 2020-11-23 2021-11-18 Compositions de polycarbonate contenant du dioxyde de titane et du triacylglycérol contenant des groupes époxy

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