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EP4508140A1 - Compositions de polycarbonate ignifuges thermoconductrices présentant un indice de résistance au cheminement élevé - Google Patents

Compositions de polycarbonate ignifuges thermoconductrices présentant un indice de résistance au cheminement élevé

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Publication number
EP4508140A1
EP4508140A1 EP23718238.1A EP23718238A EP4508140A1 EP 4508140 A1 EP4508140 A1 EP 4508140A1 EP 23718238 A EP23718238 A EP 23718238A EP 4508140 A1 EP4508140 A1 EP 4508140A1
Authority
EP
European Patent Office
Prior art keywords
weight
thermoplastic composition
composition according
component
talc
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
EP23718238.1A
Other languages
German (de)
English (en)
Inventor
Tim HUNGERLAND
Marius Nolte
Matthias KNAUPP
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 EP4508140A1 publication Critical patent/EP4508140A1/fr
Pending legal-status Critical Current

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    • 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
    • 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
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • 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
    • C08K5/5399—Phosphorus bound to nitrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/26—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers modified by chemical after-treatment
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L27/00—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers
    • C08L27/02—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L27/12—Compositions of homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen; Compositions of derivatives of such polymers not modified by chemical after-treatment containing fluorine atoms
    • C08L27/18—Homopolymers or copolymers or tetrafluoroethene
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/42—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes polyesters; polyethers; polyacetals
    • H01B3/421—Polyesters
    • H01B3/426—Polycarbonates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/30—Applications used for thermoforming
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend

Definitions

  • the invention relates to thermally conductive, flame-retardant thermoplastic compositions based on polycarbonate with high tracking resistance.
  • Polycarbonate offers many advantages over other thermoplastic polymers due to its high impact strength, high heat resistance and a certain inherent flame retardancy. Due to this unique property profile, polycarbonate compositions are generally suitable for a variety of different applications, e.g. in the area of electrical and electronic components. In particular, good insulating properties and high flame retardancy are essential safety-relevant basic requirements for the materials used in this area.
  • Tracking current resistance generally describes the resistance of a plastic material to environmental influences.
  • the CTI value is a measure of the tendency of a plastic to form electrically conductive paths on the surface under environmental influences, such as moisture and dirt, and to promote the resulting electrical leakage currents.
  • the higher the tracking resistance or tracking resistance (the CTI value) of a material the better it is suitable for use in high-voltage applications, e.g. in today's electromobility applications.
  • Another advantage of materials with a high CTI value is the possibility that electrical conductor tracks in an EE component can be closer together without risking a short circuit, which in turn enables the reduction of component dimensions and thus more compact designs and weight savings.
  • polycarbonate In contrast to other thermoplastic polymers such as polystyrene, polyester, etc., polycarbonate itself has a very low tracking resistance and moderate flame retardancy. Because of the high proportion of aromatic structures, polycarbonate has a very high tendency to char. The CTI of pure polycarbonate is around 250 V or even lower (F. Acquasanta et al., Polymer Degradation and Stability, 96 (2011), 2098-2103). However, for numerous applications in the electrical/electrical sector (EE), e.g. in the field of electromobility, a higher CTI of the materials used is required for safety reasons. Therefore, polycarbonate has not yet been considered as a material for a large number of applications that require a high tracking resistance of the material. For applications in which a high tracking resistance of the material is required, the materials must also have a high level of flame retardancy, ie a VO classification according to UL94V, especially with thin wall thicknesses.
  • EE electrical/electrical sector
  • halogenated sulfonates e.g. Rimar salt (potassium perfluorobutane sulfonate, C4 salt) or KSS salt (potassium diphenylsulfone-3-sulfonate)
  • organic phosphates e.g.
  • BDP bisphenol A-bis(diphenyl phosphate)
  • RDP resorcinol-bis
  • phosphazenes are used.
  • flame retardant additives the flame retardancy of polycarbonate can generally be adjusted very well. The mechanism of action of these flame retardants is based on the formation of a solid, charred surface layer that interrupts the oxygen supply and thus inhibits the combustion process.
  • WO 2020/212245 Al describes thermally conductive, polycarbonate-based compositions containing 50 to 75% by weight of aromatic polycarbonate, 15 to 35% by weight of talc, 0.5 to 3% by weight of anhydride-modified alpha-olefin polymer, 0.4 to 0.6% by weight of fluorine-containing anti-drip agent, 3 to 10% by weight of phosphazene or 3 to 5% by weight of phosphoric acid ester and 3 to 10% by weight of barium sulfate, which is contained as a flame retardant synergist.
  • the underlying effect for good tracking resistance is, among other things, a low tendency to form conductive paths on the surface. This is in direct contrast to the mechanism of action, “charring”, of surface-active flame retardants and therefore presents a particular challenge in achieving high tracking resistance and good flame retardancy in a polycarbonate material.
  • Thermally conductive polycarbonate material is basically known from the prior art.
  • WO 2018/037037 Al describes corresponding compositions which have improved thermal conductivity due to the use of talc.
  • talc By adding maleic anhydride-modified olefin wax, basic polymer degradation is prevented Talc is largely suppressed, resulting in a material with advantageous mechanical properties.
  • such a material is not characterized by good flame retardancy and the tracking resistance is not significantly increased compared to pure polycarbonate.
  • experts have also been of the opinion that there are currently no polycarbonate materials with high tracking resistance.
  • the task was therefore to provide thermally conductive polycarbonate-based compositions which have a high CTI of at least 400 V, preferably at least 450 V, preferably determined according to the rapid test method based on IEC 60112:2009, and preferably also a UL94 VO- Achieve classification at 2 mm.
  • the thermal conductivity (in plane) should preferably be at least 1.0 W/(mK), determined according to ASTM E 1461-13.
  • the compositions should preferably also have good heat resistance, in particular a Vicat softening temperature, determined according to ISO 306:2014-3, VST Method B, of at least 110 ° C, preferably of at least 112 ° C, particularly preferably at least 115°C.
  • thermoplastic composition containing
  • the composition according to the invention can contain further components, such as further additives in the form of component F.
  • the composition can also contain one or more other thermoplastics different from the above-mentioned components as blend partners (component G), which are not covered by any of the components A to F.
  • component G blend partners
  • the stated % by weight of components A, B, C, D, E, if applicable F and if applicable G - unless explicitly stated otherwise - each refer to the total weight of the composition. It goes without saying that all components contained in a composition according to the invention together amount to 100% by weight. If the upper limit for a numerical range is specified as “up to X”, this includes the stated numerical value with its rounding range upwards.
  • Thermoplastic polymers that are suitable as blend partners and are different from components A, E and F are, for example, further aromatic polycarbonate that is not a bisphenol A homopolycarbonate, i.e. different from component A, polystyrene, styrene copolymers, aromatic polyesters such as polyethylene terephthalate (PET).
  • further aromatic polycarbonate that is not a bisphenol A homopolycarbonate, i.e. different from component A
  • polystyrene, styrene copolymers polystyrene, styrene copolymers, aromatic polyesters such as polyethylene terephthalate (PET).
  • PET polyethylene terephthalate
  • PBT polybutylene terephthalate
  • PET-cyclohexanedimethanol copolymer PET-cyclohexanedimethanol copolymer
  • PEN polyethylene naphthalate
  • PMMA and PMMA copolymers PMMI, polyolefins such as polyethylene or polypropylene as well as copolymers with styrene such as transparent polystyrene acrylonitrile (PSAN) or also thermoplastic polyurethanes.
  • PSAN transparent polystyrene acrylonitrile
  • compositions do not contain any further components, but rather the amounts of components A, B, C, D, E, if necessary F, if necessary G, in particular in the preferred embodiments described, add up to 100% by weight, d. H.
  • the compositions according to the invention consist of components A, B, C, D, E, if necessary F, if necessary G, most preferably of components A to F.
  • the components used may contain common impurities, which arise, for example, from their manufacturing processes. It is preferred to use components that are as pure as possible. It is further understood that these impurities can also be contained in a closed formulation of the composition.
  • the invention also relates to molded parts made from the thermoplastic compositions according to the invention, i.e. molded parts consisting of a thermoplastic composition according to the invention or comprising a region of a thermoplastic composition according to the invention.
  • molded parts are in particular those in which the aforementioned property profile is particularly attractive, i.e. molded parts that are parts of components from the renewable energy sector, in particular high-voltage switches, inverters, relays, electronic connectors, electrical connectors, protective switches, components for photovoltaic applications, electric motors , heat sinks, chargers and plugs for electric vehicles, electrical connection boxes, smart meter housings, miniature circuit breakers, power busbars.
  • the component is preferably designed for an operating voltage of at least 400 V.
  • the material expediently used preferably has a tracking resistance of at least 400 V, in particular at least 450 V, determined as described above according to the rapid test method based on IEC 60112:2009.
  • compositions according to the invention show no significant leakage current (> 0.5 A over 2 s), the test preferably being carried out according to the method described in the The rapid test procedure described in the description section is based on IEC 60112:2009.
  • the compositions according to the invention have a flame retardancy VO according to UL94V in test specimen thicknesses of 2 mm.
  • compositions preferably also have good heat resistance, which is reflected in a Vicat softening temperature, determined according to ISO 306:2014-3, VST Method B, of at least 110 ° C, preferably of at least 112 ° C , especially at 115°C.
  • Component A of the thermoplastic compositions according to the invention is bisphenol A homopolycarbonate, i.e. an aromatic polycarbonate that is based on the sole monomer building block bisphenol A.
  • the melt volume flow rate MVR of the aromatic bisphenol A homopolycarbonate used, determined according to ISO 1133:2012-03, at a test temperature of 300 ° C and 1.2 kg load, is preferably 5 to 35 cm 3 / (10 min), more preferably 6 to 21 cm 3 /(10 min), particularly preferably 10 to 19 cm 3 /(10 min), very particularly preferably 11 to 15 cm 3 /(10 min).
  • Aromatic polycarbonates are produced, for example, by reacting dihydroxyaryl compounds with carbonic acid halides, preferably phosgene, and/or with aromatic dicarboxylic acid dihalides, preferably benzene dicarboxylic acid dihalides, by the phase interface process, optionally using chain terminators and optionally using trifunctional or more than trifunctional branching agents. Production via a melt polymerization process by reacting dihydroxyaryl compounds with, for example, diphenyl carbonate is also possible.
  • phenols are preferred chain terminators, which contain one or more Ci to CT alkyl radicals. linear or branched, preferably unsubstituted, 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.
  • the chain terminators can be added before, during or after the reaction with a carbonic acid derivative.
  • the homopolycarbonate can also be branched.
  • Suitable branching agents are the tri- or more than trifunctional compounds known in polycarbonate chemistry, in particular those with three or more than three phenolic OH groups.
  • Suitable branching agents are, for example, l,3,5-tri-(4-hydroxyphenyl)-benzene, 1,1, l-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-dihydroxyphenylj- propane, tetra-(4-hydroxyphenyl)-methane, tetra-(4-(4-hydroxyphenylisopropyl)-phenoxyj-methane and 1,4-bis-((4',4"-dihydroxytriphenyl)-methyl)-benzene and 3 ,3-Bis-(3-methyl-4-hydroxyphenyl)-2-oxo-2,3-dihydroindole.
  • the amount of branching agents to be used if necessary is preferably 0.05 mol% to 2.00 mol%, based on moles of bisphenol A used in each case.
  • the branching agents can either be introduced with the bisphenol A and the chain terminators in the aqueous alkaline phase or dissolved in an organic solvent and added before phosgenation. In the case of the transesterification process, the branching agents are used together with bisphenol A.
  • additional aromatic polycarbonates can also be contained in the compositions according to the invention as additional blending partners according to component G, as long as they do not have a negative effect on the property profile of high tracking resistance and good flame resistance at 2 mm desired according to the invention and the Vicat temperature is not too high. i.e. preferably not lower below a Vicat temperature of 110 ° C, preferably not below 112 ° C, in particular not below 115 ° C.
  • thermoplastic compositions according to the invention contain at least 50% by weight, preferably at least 54% by weight, of aromatic bisphenol A homopolycarbonate, and are therefore based on aromatic polycarbonate.
  • Component B
  • Talc in the context of the present invention is preferably a talc which has essentially the same chemical composition, particle diameter, porosity and/or BET surface area, or a talc mixture.
  • Talc is generally a layered silicate. It can be described as magnesium silicate hydrate with the general chemical composition Mg3[Si40io(OH)2]. However, different types of talc contain different impurities, so there may be deviations from this general composition.
  • the talc or the talc mixture used to produce the composition according to the invention can be sized or uncoated.
  • the talc is preferably uncoated.
  • a size is viewed as a targeted (chemi- or physisorbed) enrichment of molecules on the surface.
  • Uncoated talc is therefore talc that has not been surface-treated, i.e. H.
  • the talc was preferably not subjected to any further process step which specifically changes the surface of the talc by chemisorption and/or physisorption.
  • this does not exclude the possibility that contaminants, dust or similar particles may inadvertently reach parts of the surface during further handling of the talc, as long as the surface of the talc does not significantly lose its properties, in particular with regard to the pH value.
  • the talc preferably has a pH of 8 to 10, particularly preferably 8.5 to 9.8, very particularly preferably 9.0 to 9.7, the pH being determined according to EN ISO 787-9: 1995 .It should be noted that EN ISO 787-9:1995 also mentions the possibility of adding ethanol or other organic solvents to improve the dispersion of the solid to be measured. According to the invention, only distilled water is preferably used to determine the pH value in accordance with EN ISO 787-9: 1995.
  • Component B the talc, preferably has an iron(II) oxide and/or iron(III) oxide content of 0.2 to 2.5% by weight, particularly preferably 0.3 to 2.3% by weight. %, very particularly preferably from 0.3 to 2.0% by weight. This content is preferably measured by X-ray fluorescence or atomic absorption spectroscopy.
  • the iron oxide content in talc has an influence on the degree of degradation of the polycarbonate. It is beneficial to use talc with the specified iron oxide content.
  • component B preferably has an aluminum oxide content of 0.01 to 0.5% by weight, particularly preferably 0.05 to 0.48% by weight, very particularly preferably 0.15 to 0.45% by weight .-% on.
  • Component B preferably has an average particle diameter D50 of 0.01 to 10 pm, particularly preferably 0.25 to 10.00 pm, further preferably 0.5 to 10.00 pm, particularly preferably 1 to 5 pm, where the particle diameter D50 is determined by sedimentation analysis.
  • the person skilled in the art understands the mean value D50 to be an average particle diameter in which 50% of the particles are smaller than the defined value.
  • the particle diameter D50 is preferably determined according to 18013317-3:2001.
  • Component B preferably has a BET surface area of 7.5 to 20.0 m 2 /g, particularly preferably 9.0 to 15.0 m 2 /g, very particularly preferably 9.5 to 14.0 m 2 /g on.
  • the determination of the surface according to Brunauer, Emmett and Teller using gas adsorption is known to those skilled in the art.
  • the BET surface is preferably determined according to ISO 4652:2012-06. This preferred BET surface is particularly preferably connected to the average particle diameter D50 of the talc described above. It has been found that with such a combination, component B used according to the invention is optimally matched to component C used according to the invention. Due to the special acid number and molecular weight of component E, the degradation of the polycarbonate caused by component B can be minimized.
  • the talc particularly preferably has a talc content of >96% by weight, particularly preferably >97% by weight, very particularly preferably >98% by weight.
  • the talc has a loss on ignition at 1050 ° C of 5.0 to 7.0% by weight, particularly preferably of 5.2 to 6.5% by weight and very particularly preferably of 5.3 to 6.2% by weight.
  • the loss on ignition is preferably determined using DIN51081:2002.
  • the talc which can also be a talc mixture, according to component B is preferably in compacted form. If it is a talc mixture, the above figures refer to the talc mixture, i.e. component B in its entirety.
  • compositions according to the invention have a talc content of 32 to 37% by weight, preferably 34 to 36% by weight, particularly preferably 34.5 to 35.5% by weight, based on the total composition.
  • Component C of the compositions according to the invention is phosphorus-containing flame retardants. It can be a single phosphorus-containing flame retardant, but also a mixture of different phosphorus-containing flame retardants.
  • Preferred phosphorus-containing flame retardants are cyclic phosphazenes, phosphorus compounds of the formula (10) and mixtures thereof:
  • R 1 , R 2 , R 3 and R 4 independently of one another represent a C to C alkyl radical, each optionally halogenated and each branched or unbranched, and/or C5 to Ce cycloalkyl radical, Ce to C20 aryl radical or C7 to Ci 2-aralkyl radical, each optionally substituted by branched or unbranched alkyl and/or halogen, preferably chlorine and/or bromine, n independently 0 or 1, q a value from 0 to 30 and
  • X A single or multi-chemical remnant with 6 to 30 C atoms or a linear or branched aliphatic rest with 2 to 30 C atoms, which can be substituted or unsubstitted, bridged or unbridged.
  • R 1 , R 2 , R 3 and R 4 are preferably independently branched or unbranched C1 to C4 alkyl, phenyl, naphthyl or phenyl substituted with C1 to C4 alkyl.
  • aromatic groups R 1 , R 2 , R 3 and/or R 4 these in turn can be substituted with halogen and/or alkyl groups, preferably chlorine, bromine and/or C1 to C4 alkyl, branched or unbranched.
  • Particularly preferred aryl radicals are cresyl, phenyl, xylenyl, propylphenyl or butylphenyl and the corresponding brominated and chlorinated derivatives thereof.
  • X in formula (10) is preferably derived from dihydroxyaryl compounds.
  • X in formula (10) is particularly preferably
  • Xiii (XiV) or their chlorinated and/or brominated derivatives.
  • X (with the adjacent oxygen atoms) is preferably derived from hydroquinone, bisphenol A or diphenylphenol.
  • X is also preferably derived from resorcinol.
  • X is particularly preferably derived from bisphenol A.
  • n in the formula (10) is preferably equal to 1.
  • q is preferably 0 to 20, particularly preferably 0 to 10, in the case of mixtures for average values of 0.8 to 5.0, preferably 1.0 to 3.0, more preferably 1.05 to 2.00 and particularly preferably 1.08 to 1.60.
  • a compound of the formula (11) is preferred: wherein
  • R 1 , R 2 , R 3 and R 4 each independently of one another a linear or branched C to C alkyl radical and/or optionally linear or branched alkyl-substituted Cs to Ce cycloalkyl radical, Ce to Cio aryl radical or C7 - to Cn-aralkyl radical, n independently 0 or 1, q independently 0, 1, 2, 3 or 4,
  • N is a number between 1 and 30,
  • Ci to Cy alkylidcn.
  • a linear or branched Ci to Cy alkyl group Cs- to Cn-cycloalkylene residue, Cs- to Cn-cycloalkylidene residue, -O-, -S-, -SO-, SO2 or -CO- mean.
  • Phosphorus compounds of the formula (10) are in particular tributyl phosphate, triphenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, diphenyl-2-ethyl cresyl phosphate, tri-(isopropylphenyl) phosphate, resorcinol-bridged oligophosphate and bisphenol A-bridged oligophosphate.
  • the use of oligomeric phosphoric acid esters of the formula (10), which are derived from bisphenol A, is particularly preferred if phosphorus compounds of the formula (10) are used.
  • the average q value is determined by determining the composition of the phosphorus compound mixture (molecular weight distribution) using High Pressure Liquid Chromatography (HPLC) at 40°C in a mixture of acetonitrile and water (50:50) and then calculating the average values for q .
  • HPLC High Pressure Liquid Chromatography
  • Such phosphorus compounds are known (see, for example, EP 0 363 608 A1, EP 0 640 655 A2) or can be prepared in an analogous manner using known methods (e.g. Ullmann's Encyclopedia of Technical Chemistry, Vol. 18, p. 301 ff., 1979; Houben-Weyl, Methods of Organic Chemistry, Vol. 12/1, p. 43; Beilstein Vol. 6, p. 177).
  • cyclic phosphazenes according to formula (13) are particularly preferably used as component C:
  • R is each the same or different and for
  • Ci an optionally halogenated, preferably halogenated with fluorine, more preferably monohalogenated, Ci to Cs alkyl radical, preferably methyl radical, ethyl radical, propyl radical or butyl radical,
  • Ci to Cs alkoxy radical preferably a methoxy radical, ethoxy radical, propoxy radical or butoxy radical
  • - a C5 to Ce cycloalkyl radical optionally substituted by alkyl, preferably C1 to C4 alkyl, and/or halogen, preferably chlorine and/or bromine
  • - a Ce to C20 aryloxy radical optionally substituted by alkyl, preferably C1 to C4 alkyl, and/or halogen, preferably chlorine, bromine, and/or hydroxy, preferably phenoxy radical, naphthyloxy radical
  • a C7 to Cn aralkyl radical preferably phenyl-Ci to C4 alkyl radical, optionally substituted by alkyl, preferably C1 to C4 alkyl, and/or halogen, preferably chlorine and/or bromine, or
  • halogen residue preferably chlorine or fluorine
  • k represents an integer from 1 to 10, preferably a number from 1 to 8, particularly preferably 1 to 5, very particularly preferably 1.
  • phosphazenes are preferably used. These are usually mixtures of cycles of different ring sizes.
  • propoxyphosphazene phenoxyphosphazene, methylphenoxyphosphazene, aminophosphazene, fluoroalkylphosphazene and phosphazene of the following structures:
  • k 1, 2 or 3.
  • the phosphazenes can be used alone or as a mixture.
  • the radical R can always be the same or two or more radicals in the formulas can be different.
  • the radicals R of a phosphazene are preferably identical.
  • the proportion of oligomers with k>8 is preferably from 0 to 2.0 mol%, based on component B, and preferably from 0.10 to 1.00 mol%.
  • the phosphazenes of component C meet all three of the aforementioned conditions with regard to the proportions of oligomers.
  • n defined as the arithmetic mean of k, is in the range from 1.10 to 1.75, preferably from 1.15 to 1.50, more preferably from 1.20 to 1.45, and especially preferably from 1.20 to 1.40 (range limits included).
  • the oligomer compositions in the respective blend samples can be detected and quantified using 31 P-NMR (chemical shift; 5 trimer: 6.5 to 10.0 ppm; 5 tetramer: -10 to -13.5 ppm; 5 higher Oligomers: -16.5 to -25.0 ppm).
  • component C comprises bisphenol-A-based oligophosphate according to formula (12) and/or cyclic phosphazene according to formula (13), very particularly preferably component C is bisphenol-A-based oligophosphate according to formula (12) and/or cyclic phosphazene according to Formula (13), component C is extremely preferably cyclic phosphazene according to formula (13).
  • the proportion of phosphorus-containing flame retardant in the compositions according to the invention is 4% by weight to 10% by weight, preferably 5% by weight to 8% by weight, particularly preferably 5.0 to 8.0% by weight on the overall composition.
  • compositions according to the invention contain a fluorine-containing anti-drip agent as component D, which can be a mixture of several anti-dripping agents.
  • the total amount of anti-dripping agent is 0.3% by weight to 2% by weight, preferably 0.3% by weight to 1.0% by weight, particularly preferably 0.4% by weight to 0.7% by weight, based on the total composition, of at least one anti-dripping agent.
  • Fluorine-containing polymer in particular polyolefin, is preferably used as an anti-dripping agent.
  • the fluorinated polyolefins preferably used as anti-dripping agents are high molecular weight and have glass transition temperatures of over -30 ° C, usually over 100 ° C, and fluorine contents preferably from 65% by weight to 76% by weight, in particular from 70 to 76% by weight.
  • Preferred fluorinated polyolefins are polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene/hexafluoropropylene and ethylene/tetrafluoroethylene copolymers.
  • the fluorinated polyolefins are known (see “Vinyl and Related Polymers” by Schildknecht, John Wiley & Sons, Inc., New York, 1962, pages 484-494; “Fluorpolymers” by Wall, Wiley-Interscience, John Wiley & Sons, Inc., New York, Volume 13, 1970, pages 623-654; "Modem Plastics Encyclopedia", 1970-1971, Volume 47, No. 10 A, October 1970, Me Graw-Hill, Inc., New York, page 134 and 774; "Modem Plastics Encyclopedia", 1975-1976, October 1975, Volume 52, No.
  • the density of the fluorinated polyolefins can be between 1.2 and 2.3 g/cm 3 ', preferably 2.0 g/cm 3 to 2.3 g/cm 3 , determined according to ISO 1183-1 (2019-09) , the average particle size is between 0.05 and 1000 pm, determined using light microscopy or white light interferometry.
  • Suitable tetrafluoroethylene polymer powders are commercially available products and are offered, for example, by the DuPont company under the trade name Teflon®.
  • a fluorine-containing composition is used as a fluorine-containing anti-drip agent, the minimum amount used is such that at least 0.2% by weight, preferably at least 0.21% by weight, particularly preferably at least 0.25% by weight of PTFE is contained in the overall composition are.
  • the PTFE-containing compositions include Hostaflon® TF2021 or PTFE blends such as Blendex® B449 (approx. 50% by weight PTFE and approx.
  • SAN 50% by weight SAN [made from 80% by weight styrene and 20% by weight % acrylonitrile]) from Chemtura. It is particularly preferred to contain fluorine Anti-drip agent PTFE or a PTFE/SAN blend is used; the fluorine-containing anti-drip agent PTFE or PTFE/SAN is extremely preferred.
  • Component E of the compositions according to the invention is an anhydride-modified ⁇ -olefin polymer.
  • the a-olefin polymer is preferably based on at least one monomer selected from the group consisting of ethylene, 1-propene, 1-butene, 1-isobutene, 1-pentene, 1-hexene, 1-heptene, 1-octene, 1 -nonene, 1-decene, 1-undecene, 1-dodecene, 1-tridecene, 1-tetradecene, 1-octadecene, 1-nonadecene, but can also be based on mixtures of these monomers.
  • the ⁇ -olefin polymer is based on at least one monomer selected from the group consisting of ethene, propene, 1-hexene, 1-octene.
  • the ⁇ -olefin polymer is particularly preferably based on ethylene, propene and/or 1-octene.
  • the ⁇ -olefin polymer is modified with an anhydride, using an unsaturated carboxylic anhydride for modification.
  • the carboxylic anhydride is preferably selected from the group consisting of maleic anhydride, phthalic anhydride, fumaric anhydride, itaconic anhydride and mixtures thereof. Maleic anhydride is particularly preferred.
  • the anhydride-modified ⁇ -olefin polymer is preferably free of styrene-butadiene rubber, most preferably rubber-free.
  • a preferred anhydride-modified ⁇ -olefin polymer includes
  • E2 0.5-10.0% by weight, more preferably 2.5-8.0% by weight, even more preferably 3.0-6.0% by weight of anhydride.
  • the olefinic part El) of the a-olefin polymer is particularly preferably characterized in that the ethylene content is 65.0-96.0% by weight, more preferably 80.0-96.0% by weight, very particularly preferably 84.0-92.0% by weight, the propylene content 2.0-10.0% by weight, very particularly preferably 4.0-8.0% by weight and the 1-octene content 2.0-25.0% by weight, further preferably 2.0-10.0% by weight, very particularly preferably 4.0-8.0% by weight.
  • the ⁇ -olefin polymer is not based on any other monomers.
  • the olefinic part CI) of the alpha-olefin polymer is based on propylene and/or ethylene, most preferably at least 98% by weight.
  • the only monomer building block of the alpha-olefin polymer is extremely preferred: propylene.
  • the average molecular weight Mw of the anhydride-modified a-olefin polymer is preferably 300 to 40,000 g/mol, more preferably 800 to 32,000 g/mol, even more preferably 1,000 to 22,000 g/mol, particularly preferably 3,000 to 21,000 g/mol.
  • the molecular weight Mw is determined using gel permeation chromatography in ortho-dichlorobenzene at 150 °C with polystyrene calibration.
  • the specified value is preferably the mean value from a double determination.
  • the acid number of the anhydride-modified a-olefin polymer is preferably at least 30 mg KOH/g, more preferably 45 to 170 mg KOH/g, particularly preferably up to 100 mg KOH/g, determined according to DIN ISO 17025:2005-08 using potentiometric Titration with alcoholic potassium hydroxide solution.
  • the anhydride-modified a-olefin polymer according to component C is based on propene, is maleic anhydride-modified and more preferably has an average molecular weight Mw, determined by gel permeation chromatography in ortho-dichlorobenzene at 150 ° C with polystyrene calibration, of 1000 to 22000 g/mol, even more preferably 3000 to 21000 g/mol, and an acid number of 45 to 170 mg KOH/g, even more preferably 50 to 100 mg KOH/g, determined according to DIN ISO 17025:2005-08 using potentiometric Titration, on.
  • Mw average molecular weight Mw
  • the amount of anhydride-modified ⁇ -olefin polymer in the overall composition is 1% by weight to 3% by weight, preferably 1.2% by weight to 2.5% by weight, more preferably 1.3% by weight .-% to 2.3% by weight, particularly preferably 1.4% by weight to 2% by weight, in particular up to 1.6% by weight.
  • polycarbonate compositions according to the invention can contain one or more additional additives other than components B, C, D and E, which are summarized here under “component F”.
  • the group of other additives does not include any talc (component B) and no phosphorus-containing flame retardant according to component C.
  • the group of other additives also does not include any fluorine-containing anti-drip agent, as this is already described as component D, and also no anhydride-modified a-olefin.
  • Such other additives are in particular thermal stabilizers, antioxidants, mold release agents, UV absorbers, IR absorbers, impact modifiers, antistatic agents, flame retardants other than component C, optical brighteners, light scattering agents, hydrolysis stabilizers, transesterification stabilizers, (organic) Dyes, (organic/inorganic) pigments, compatibilizers and/or additives for laser marking, especially in the usual amounts for polycarbonate-based compositions.
  • Such additives are described, for example, in EP 0 839 623 Al, WO 96/15102 Al, EP 0 500 496 Al or in the “Plastics Additives Handbook”, Hans Doubt, 5th Edition 2000, Hanser Verlag, Kunststoff. These additives can be added individually or in a mixture and are preferred additives according to the invention.
  • further additives are one or more further additives selected from the group consisting of thermal stabilizers, antioxidants, mold release agents, organic dyes, organic pigments, inorganic pigments.
  • the proportion of further additives is particularly preferably 0 to 3% by weight.
  • at least one thermal stabilizer, an antioxidant, a dye, pigment and/or a mold release agent is included as a further additive, most preferably a thermal stabilizer and/or a pigment.
  • compositions according to the invention can contain other flame retardants, but are preferably free of those selected from the group of alkali, alkaline earth or ammonium salts of aliphatic or aromatic sulfonic acid, sulfonamide, sulfonimide derivatives and combinations of these, under “ “Derivatives” are understood to mean those compounds whose molecular structure has another atom or another group of atoms in place of an H atom or a functional group or in which a or several atoms/groups of atoms have been removed. The root connection is therefore still recognizable.
  • Such flame retardants which are preferably not contained in compositions according to the invention, are in particular 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 or potassium 2,4,5-trichlorobenzene sulfate, sodium or potassium diphenylsulfone sulfonate, sodium or potassium 2-formylbenzenesulfonate, sodium or potassium (N-benzenesulfonyl)-benzenesulfonamide or mixtures thereof, particularly preferably sodium or potassium perfluorobutane sulfate, sodium or potassium perfluorooctane sulfate, sodium or potassium diphenyl sulfone sulfonate or mixtures thereof, in particular potassium perfluoro-1-butane
  • Additives that are particularly preferably included are mold release agents, more preferably based on a fatty acid ester, even more preferably based on a stearic acid ester, particularly preferably based on pentaerythritol. Pentaerythritol tetrastearate (PETS) and/or glycerol monostearate (GMS) are particularly preferably used. If one or more mold release agents are used, the amount is preferably up to 1.0% by weight (inclusive), more preferably 0.01 to 0.7% by weight, particularly preferably 0.02 to 0.60% by weight. %, based on the overall composition.
  • PETS Pentaerythritol tetrastearate
  • GMS glycerol monostearate
  • the amount is preferably up to 1.0% by weight (inclusive), more preferably 0.01 to 0.7% by weight, particularly preferably 0.02 to 0.60% by weight. %, based on the overall composition.
  • thermal stabilizers are also thermal stabilizers.
  • the amount of thermal stabilizer is preferably up to 0.20% by weight, more preferably 0.01 to 0.10% by weight, even more preferably 0.01 to 0.05% by weight, particularly preferably 0.015 to 0.040% by weight .-%, based on the total composition.
  • Phosphorus-based stabilizers selected from the group of phosphates, phosphites, phosphonites, phosphines and mixtures thereof, are particularly suitable as thermal stabilizers.
  • thermal stabilizers examples are triphenyl phosphite, diphenyl alkyl phosphite, phenyldialkyl phosphite, tris(nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl-pentaerythritol diphosphite, tris(2,4-di-tert-butylphenyl) phosphite (Irgafos® 168), diisodecylpentaerythritol di phosphite, Bis(2,4-di -tert-butylphenyl)pentaerythritol diphosphit
  • Irganox® B900 mixture of Irgafos® 168 and antioxidant Irganox® 1076 in a ratio of 4: 1
  • Doverphos® S- 9228 with Irganox® B900 or Irganox® 1076 Particular preference is given to using triphenylphosphine (TPP), Irgafos® 168 or tris(nonylphenyl) phosphite or mixtures thereof.
  • TPP triphenylphosphine
  • Irgafos® 168 tris(nonylphenyl) phosphite or mixtures thereof.
  • phenolic antioxidants such as alkylated monophenols, alkylated thioalkylphenols, hydroquinones and alkylated hydroquinones can be used.
  • Particularly preferred are Irganox® 1010 (pentaerythritol 3-(4-hydroxy-3,5-di-tert-butylphenyl) propionate; CAS: 6683-19-8) and Irganox 1076® (octadecyl-3-(3,5- di-tert-butyl-4-hydroxyphenyl) propionate), preferably in amounts of 0.05 - 0.5% by weight.
  • alkyl phosphates e.g. B. mono-, di- and/or trihexyl phosphate, triisoctyl phosphate and/or trinonyl phosphate
  • the preferred alkyl phosphate used is triisooctyl phosphate (tris-2-ethyl-hexyl phosphate). Mixtures of different mono-, di- and trialkyl phosphates can also be used.
  • Triisooctyl phosphate is preferred in amounts of 0.003% by weight to 0.05% by weight, more preferably 0.005% by weight to 0.04% by weight and particularly preferably from 0.01% by weight to 0.03% % by weight, based on the total composition.
  • compositions according to the invention already have an excellent set of properties without additional impact modifiers. Compositions according to the invention are therefore preferably free of impact modifiers.
  • compositions according to the invention do not contain any other fillers, such as barium sulfate. Titanium dioxide is not viewed as a “filler”, but rather as an inorganic pigment according to component F.
  • the compositions according to the invention preferably contain 0.1 to 2% by weight, preferably 0.5 to 1.2% by weight, of titanium dioxide.
  • the titanium dioxide of the compositions according to the invention preferably has an average particle size D50, determined by scanning electron microscopy (STEM), of 0.1 to 5 pm, preferably 0.2 pm to 0.5 pm.
  • the titanium dioxide can also have a different particle size, for example an average particle size D50, determined using scanning electron microscopy (STEM), of > 0.5 pm, approximately 0.65 to 1.15 pm.
  • the titanium dioxide preferably has a rutile structure.
  • the titanium dioxide used according to the invention is a white pigment, Ti(IV) ⁇ 2.
  • colored titanium dioxides also contain elements such as Sb, Ni, Cr in significant quantities, so that a color impression other than “white” results. It is understood that the white pigment titanium dioxide may also contain traces of other elements as impurities. However, these amounts are so small that the titanium dioxide does not get a color cast.
  • Suitable titanium dioxides are preferably those that are produced using the chloride process, hydrophobicized, specially treated and suitable for use in polycarbonate.
  • uncoated titanium dioxide or a mixture of both can also be used in compositions according to the invention instead of coated titanium dioxide.
  • 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 silica and/or aluminum oxide.
  • An organic-based modification may contain 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, of 12 to 18 g/100 g of titanium dioxide, more preferably of 13 to 17 g/100 g of titanium dioxide, particularly preferably of 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, is particularly preferred.
  • Such titanium dioxides are available under the brand names Kronos 2233 and Kronos 2230.
  • the polymer compositions according to the invention containing the mixed components A, B, C, D, E, if necessary F and possibly other components, can be produced using powder premixes. Premixtures of granules or granules and powders with the additives according to the invention can also be used. Premixes can also be used, which consist of solutions of the mixture components in suitable solvents, with the solvent optionally being homogenized in solution is subsequently removed.
  • the additives referred to as component F and also other components of the compositions according to the invention can be introduced by known processes or as a masterbatch. The use of masterbatches is particularly preferred for introducing additives and other components, with masterbatches based on the respective polymer matrix being used in particular.
  • compositions according to the invention can, for example, be extruded. After extrusion, the extrudate can be cooled and crushed. The combining and mixing of a premix in the melt can also take place in the plasticizing unit of an injection molding machine. In the subsequent step, the melt is transferred directly into a shaped body.
  • compositions according to the invention are preferably used for the production of molded parts for components from the renewable energy sector, in particular for high-voltage switches, inverters, relays, electronic connectors, electrical connectors, circuit breakers, components for photovoltaic applications, electric motors, heat sinks, chargers or charging plugs for electric vehicles, electrical connection boxes , smart meter housing, miniature circuit breaker; Power bus bars.
  • the invention therefore also relates to molded parts, consisting of or comprising regions of compositions according to the invention, as well as corresponding components, comprising elements, i.e. molded parts, which consist of compositions according to the invention or comprise regions consisting of compositions according to the invention, which are referred to as “elements from a composition according to the invention “thermoplastic composition”.
  • thermoplastic composition according to the invention consisting of or comprising a region made of a thermoplastic composition according to the invention or layers made of a thermoplastic composition according to the invention is preferably carried out in those EE components which are designed for an operating voltage of at least 400 V, more preferably of at least 450 V . However, it can also be designed for a normal household operating voltage of 230 V ⁇ 23 V in Europe, although smaller distances between the electrical conductors can now be achieved.
  • the high tracking resistance of the polycarbonate compositions according to the invention makes it possible to achieve smaller distances between two electrical conductors of a component using the polycarbonate material than was previously possible when using polycarbonate.
  • the subject of the invention is therefore also an EE component, comprising a first electrical conductor and a second electrical conductor at a first distance dl and a second distance d2 from one another, which have an element made of a thermoplastic composition according to the invention, which is in direct contact with the first electrical conductor and the second electrical conductor are connected, where the distance dl is the shortest distance between the first electrical conductor and the second electrical conductor along the surface of the element made of the thermoplastic composition and where the distance d2 is the shortest distance between the first electrical conductor and the second electrical conductor through the air, where d2 is selected so that flashover through the air is prevented at the respective operating voltage and where dl is at the operating voltage U listed below: dli(0V ⁇ U ⁇ 250V): 1.8 mm to
  • Such small distances can only be achieved with a material that has at least a CTI of 400 V.
  • the invention therefore also relates to corresponding EE components in which corresponding distances are realized and which preferably have an operating voltage to be applied of at least 400 V, preferably at least 450 V.
  • d2 is within the Bachmann's ability. d2 is preferably at least 1.2 mm.
  • the invention furthermore relates to the use of talc to increase the tracking resistance of bisphenol A homopolycarbonate.
  • talc to increase the tracking resistance of bisphenol A homopolycarbonate.
  • the composition according to the invention can be used as an insulating layer for other electrical components, for example transistors.
  • the electrical components of a transistor are protected by overmolding with a high CTI plastic. The plastic protects the electrical components from both contact and unwanted electrical contact Interaction of adjacent metallic - such as a metallic heat sink - or electrical components.
  • thermoplastic composition according to the invention which is introduced between the heat sink and the transistor, ensures safe operation.
  • mounting brackets for power busbars which also require the use of materials with a high CTI.
  • the mounting brackets essentially have two functions: fixing the busbars within the component group to prevent a change in position during operation, and acting as a spacer in order to be able to run several busbars in parallel, whereby the distance between the two rails must also be sufficiently large, to prevent air overflow.
  • tracking on the surface of the mounting bracket between the power busbars, but also between the power busbar and other metal components, e.g. the screws for attaching the mounting brackets to the underlying structure must also be prevented.
  • Mounting brackets with a high CTI can increase the component and energy density.
  • Plugs for chargers or USB-C plugs have an increased risk because the current-carrying conductor tracks cannot be covered or sealed and are also exposed to contaminants such as sweat, moisture, tissue particles, dust and other materials.
  • a material with a high CTI value is necessary to provide sufficient protection against tracking, but also to enable miniaturization or an increase in power density.
  • the invention also relates to the use of compositions according to the invention, also in the embodiments described as preferred, particularly preferred, etc., for realizing the aforementioned low distances between electrical conductors in EE components.
  • Thermoplastic compositions preferred according to the invention belong to insulating material group II (400 V ⁇ CTI ⁇ 600 V), classified according to DIN EN 60664-1:2008. They have a thermal conductivity (in plane) of preferably at least 1.0 W/(mK), preferably of at least 1.1 W/(mK), determined according to ASTM E 1461-13, so that good heat dissipation is also achieved can.
  • thermoplastic composition according to embodiment 1 wherein the talc content of the thermoplastic composition is 34 to 36% by weight.
  • thermoplastic composition according to embodiment 1 or 2 wherein the talc content of the thermoplastic composition is 34.5 to 35.5% by weight.
  • anhydride-modified ⁇ -olefin polymer comprises maleic anhydride-modified propylene polymer, preferably is such a polymer.
  • composition according to one of the preceding embodiments, wherein the composition contains 0.1 to 2% by weight of titanium dioxide.
  • Thermoplastic composition according to one of the preceding embodiments containing 5 to 8% by weight of phosphorus-containing flame retardant. 11. Thermoplastic composition according to one of the preceding embodiments, containing as a further component
  • additives selected from the group consisting of thermal stabilizers, antioxidants, mold release agents, UV absorbers, IR absorbers, impact modifiers, antistatic agents, optical brighteners, light scattering agents, hydrolysis stabilizers, transesterification stabilizers, organic dyes, organic or inorganic pigments, Compatibilizers, additives for laser marking.
  • composition according to one of the preceding embodiments, wherein the composition is free of impact modifiers and blending partners.
  • additives selected from the group consisting of thermal stabilizers, antioxidants, mold release agents, UV absorbers, IR absorbers, antistatic agents, optical brighteners, light scattering agents, hydrolysis stabilizers, transesterification stabilizers, organic dyes, organic or inorganic pigments, compatibilizers, additives for laser marking.
  • Thermoplastic composition consisting of
  • additives selected from the group consisting of thermal stabilizers, antioxidants, mold release agents, UV absorbers, IR absorbers, antistatic agents, optical brighteners, light scattering agents, hydrolysis stabilizers, Transesterification stabilizers, organic dyes, organic or inorganic pigments, compatibilizers, additives for laser marking.
  • Thermoplastic composition according to one of the preceding embodiments, wherein the phosphorus-containing flame retardant is a cyclic phosphazene and/or a phosphorus compound of the formula (10).
  • R 1 , R 2 , R 3 and R 4 independently of one another represent a C to C alkyl radical, each optionally halogenated and each branched or unbranched, and/or C5 to Ce cycloalkyl radical, Ce to C2o aryl radical or C7 to Cn-aralkyl radical, each optionally substituted by branched or unbranched alkyl and/or halogen, preferably chlorine and/or bromine, n independently 0 or 1, q a value from 0 to 30 and
  • X A single or multi-chemical remnant with 6 to 30 C atoms or a linear or branched aliphatic rest with 2 to 30 C atoms, which can be substituted or unsubstitted, bridged or unbridged.
  • Ci an optionally halogenated, preferably halogenated with fluorine, more preferably monohalogenated, Ci to Cs alkyl radical, preferably methyl radical, ethyl radical, propyl radical or butyl radical,
  • Ci to Cs alkoxy radical preferably a methoxy radical, ethoxy radical, propoxy radical or butoxy radical
  • aryloxy radical optionally substituted by alkyl, preferably C1 to C4 alkyl, and/or halogen, preferably chlorine, bromine, and/or hydroxy, preferably phenoxy radical, naphthyloxy radical,
  • a C7 to Cn aralkyl radical preferably phenyl-Ci to C4 alkyl radical, optionally substituted by alkyl, preferably C1 to C4 alkyl, and/or halogen, preferably chlorine and/or bromine, or
  • halogen residue preferably chlorine or fluorine
  • k represents an integer from 1 to 10, preferably a number from 1 to 8, particularly preferably 1 to 5, very particularly preferably 1.
  • Molded part consisting of or comprising a region of a thermoplastic composition according to one of the preceding embodiments.
  • EE component which is designed for an operating voltage of at least 375 V, comprising a molded part according to embodiments 23 or 24 or a layer made of a thermoplastic composition according to one of embodiments 1 to 22.
  • EE component which is designed for an operating voltage of 400 V, comprising a molded part according to embodiments 23 or 24 or a layer made of a thermoplastic composition according to one of embodiments 1 to 22.
  • EE component according to one of embodiments 25 to 28, wherein the EE component is a high-voltage switch, inverter, relay, electronic connector, electrical connector, circuit breaker, part of a photovoltaic system, part of an electric motor, a charger or charging plug for electric vehicles, Part of an electrical connection box, part of a smart meter housing, part of a miniature circuit breaker, part of a power busbar.
  • the EE component is a high-voltage switch, inverter, relay, electronic connector, electrical connector, circuit breaker, part of a photovoltaic system, part of an electric motor, a charger or charging plug for electric vehicles, Part of an electrical connection box, part of a smart meter housing, part of a miniature circuit breaker, part of a power busbar.
  • EE component according to one of embodiments 25 to 30, with a protection class IP6K9K according to ISO 20653:2013-02.
  • Component Bl Compacted talc with a talc content of 98% by weight, an iron oxide content of 1.9% by weight, an aluminum oxide content of 0.2% by weight, loss on ignition (DIN 51081:2002/1000 °C) of 5 .4% by weight, pH value (according to EN ISO 787-9: 1995) of 9.15, D (0.5) (sedimentation analysis) of 2.2 pm; BET surface according to ISO 4652:2012-06 10 m 2 /g, type: Finntalc M05SLC, manufacturer: Elementis Minerals BV.
  • Component B*-2 Glass fiber from Nittobo (2-4-1, Kojimachi, Chiyoda-ku, Tokyo 102-8489, Japan) which is available under the trade name CSG 3PA-830. It is a flat glass fiber with a cutting length of 3mm and a cross-section ratio of 1.4.
  • Component B*-3 Fired silicon dioxide Amosil FW 600 from Quartzwerke GmbH in Frechen, uncoated, with an average particle size D(0.5) of approx. 4 pm, D(0.98) of approx. 13 pm, a D( 0.l)/D(0.9) ratio of approx. 1.5/10 and a specific surface area of approx. 6 m 2 /g, determined according to DIN-ISO 9277:2014-01.
  • Component D-l SAN-encapsulated polytetrafluoroethylene ADS5000 (approx. 50% by weight PTFE (fluorine-containing anti-drip agent) and approx. 50% by weight SAN) from Chemical Innovation Co., Ltd. Thailand.
  • compositions described here were tested using the tendon test method based on IEC 60112:2009.
  • a 0.1% ammonium chloride test solution (395 ohm*cm resistance) was applied dropwise between two adjacent electrodes at a distance of 4 mm to the surface of test specimens measuring 60 mm x 40 mm x 4 mm at an interval of 30 seconds .
  • a test voltage was applied between the electrodes, which was varied over the course of the test.
  • the first test specimen was tested at a starting voltage of 300 V or 350 V.
  • a total of a maximum of 50 drops (one drop every 30s) per voltage were applied as long as no leakage current > 0.5A occurred over 2s or the sample burned.
  • the PTI is tested based on IEC 60112:2009 - modified as described below.
  • a 0.1% ammonium chloride test solution (395 ohm*cm resistance) was applied dropwise between two adjacent electrodes at a distance of 4 mm onto the surface of test specimens measuring 60 mm x 40 mm x 4 mm at an interval of 30 seconds applied.
  • the PTI test in the PTI test there is a fixed test voltage between the electrodes and a total of 5 test specimens are tested at the respective voltage.
  • a total of a maximum of 50 drops were applied per test specimen, as long as no leakage current > 0.5A occurred over 2s or the sample burned.
  • the flame retardancy test of the polycarbonate compositions was carried out according to Underwriter Laboratory method UL94V at a thickness of 2mm.
  • Different fire classes are assigned depending on the behavior of the test specimens. These include the time until the flame goes out, resistance to dripping and whether a material drips while it is burning.
  • the classes determined here are designated V0, VI and V2 and are determined on the basis of a total of five tested test specimens.
  • the test specimen which is positioned with its longitudinal axis 180° (vertical) to the flame, has an average afterburning time after removal of the flame of no more than 10s and does not produce any dripping plastic particles that ignite a cotton wool located under the test specimen.
  • the total afterburning time of five test specimens, each flamed twice, is a maximum of 50s.
  • VI In contrast to V0, the average maximum afterburning time here is ⁇ 30s, although here too no particles are allowed to drip off and ignite the cotton.
  • V2 In contrast to V0 and VI, this classification produces dripping plastic particles that ignite the cotton wool.
  • the individual afterburning times are ⁇ 30s and the total afterburning time of 5 test specimens, each flamed twice, is ⁇ 250s.
  • n.b. The test does not provide a flame retardancy classification if the afterburning times are exceeded.
  • FOT Flame Out Time, given in seconds.
  • the heat resistance of the compositions was determined using the Vicat softening temperature (method B, test force 50N, heating rate 50 K/h) on test specimens with dimensions of 80 mm x 10 mm x 4 mm in accordance with ISO 306:2014-3.
  • Thermal conductivity
  • the thermal conductivity was determined on injection-molded test specimens with dimensions of 60 x 60 x 2 mm 3 according to ASTM E 1461 (Nano Flash method). “In plane” means measured in the x,y direction, “through plane” in the z direction. 2. Preparation of the test specimens
  • compositions were prepared on a BUSS kneader.
  • the mass temperature, speed, throughput and torque had to be adjusted according to the usual procedure for the expert and tailored to the respective composition.
  • the filler was metered as a “split-feed”, with 10% by weight of the total filler being added via the main feed and the rest via the side extruder.
  • the test specimens with dimensions of 60 mm x 40 mm x 4 mm were produced from the molding compounds using standard injection molding processes at a mass temperature of 280 ° C and a mold temperature of 80 ° C.
  • Table 1 shows how the CTI tends to improve with increasing amounts of talc (V-l - V-3).
  • talc V-l - V-3
  • Table 1 shows how the CTI tends to improve with increasing amounts of talc (V-l - V-3).
  • the flammability increases as the amount of talc increases (see afterburning times).
  • V-4, E-7 and V-11 each of which contains 5% by weight of flame retardant
  • No more than 10% by weight of flame retardant preferably no more than 8% by weight of flame retardant, should be used so that the heat resistance is not reduced too much, which would generally question the use of polycarbonate.
  • other reinforcing fillers such as glass fiber or quartz, high tracking resistance cannot be achieved as with talc in combination with an FR package (cf. V2 with V-9 and V-10).

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  • Chemical & Material Sciences (AREA)
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  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • General Chemical & Material Sciences (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Sont décrites des compositions ignifuges thermoconductrices qui présentent un indice de résistance au cheminement élevé et contiennent un homopolycarbonate de bisphénol A, du talc, un agent ignifuge contenant du phosphore, un agent anti-goutte contenant du fluor et un polymère alpha-oléfinique modifié par un anhydride. Lesdites compositions présentent un indice de résistance au cheminement élevé, ce qui permet de maintenir des distances entre des conducteurs électriques dans des composants électroniques et électriques plus courtes que par le passé.
EP23718238.1A 2022-04-14 2023-04-06 Compositions de polycarbonate ignifuges thermoconductrices présentant un indice de résistance au cheminement élevé Pending EP4508140A1 (fr)

Applications Claiming Priority (2)

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EP22168337 2022-04-14
PCT/EP2023/059147 WO2023198591A1 (fr) 2022-04-14 2023-04-06 Compositions de polycarbonate ignifuges thermoconductrices présentant un indice de résistance au cheminement élevé

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EP4508140A1 true EP4508140A1 (fr) 2025-02-19

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US (1) US20250257209A1 (fr)
EP (1) EP4508140A1 (fr)
JP (1) JP2025512094A (fr)
KR (1) KR20250003770A (fr)
CN (1) CN118974169A (fr)
WO (1) WO2023198591A1 (fr)

Family Cites Families (14)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2393967A (en) 1942-12-24 1946-02-05 Du Pont Process for polymerizing tetrafluoroethylene
US3838092A (en) 1971-04-21 1974-09-24 Kewanee Oil Co Dustless compositions containing fiberous polytetrafluoroethylene
US3671487A (en) 1971-05-05 1972-06-20 Gen Electric Glass reinforced polyester resins containing polytetrafluoroethylene and flame retardant additives
US3723373A (en) 1971-10-04 1973-03-27 American Cyanamid Co 0.1% to about 2.0% by weight polytetrafluoroethylene emulsion modified polyethylene terephthalate with improved processing characteristics
NL8802346A (nl) 1988-09-22 1990-04-17 Gen Electric Polymeermengsel met aromatisch polycarbonaat, styreen bevattend copolymeer en/of entpolymeer en een vlamvertragend middel, daaruit gevormde voorwerpen.
TW222292B (fr) 1991-02-21 1994-04-11 Ciba Geigy Ag
DE4328656A1 (de) 1993-08-26 1995-03-02 Bayer Ag Flammwidrige, spannungsrißbeständige Polycarbonat-ABS-Formmassen
KR970707080A (ko) 1994-11-10 1997-12-01 요헨 카르그, 베라 스타르크 2-시아노아크릴산 에스테르(2-cyanoacrylic acid esters)
DE69629971T2 (de) 1995-02-27 2004-07-22 Mitsubishi Chemical Corp. Hammhemmende thermoplastische Harzzusammensetzung
DE19615230A1 (de) 1996-04-18 1997-10-23 Basf Ag Flammgeschützte thermoplastische Formmassen
EP0839623B1 (fr) 1996-10-30 2001-01-31 Ciba SC Holding AG Combinaison de stabilisateurs pour le procédé rotomolding
EP3504272B1 (fr) 2016-08-24 2020-09-23 Covestro Intellectual Property GmbH & Co. KG Compositions de polycarbonate comprenant du talc
CN111171542B (zh) * 2018-11-09 2022-04-19 万华化学集团股份有限公司 一种高cti阻燃聚碳酸酯合金材料及其制备方法和用途
EP3956400B1 (fr) 2019-04-18 2023-06-28 Covestro Intellectual Property GmbH & Co. KG Polycarbonates conducteurs de chaleur à protection contre les flammes améliorée à l'aide du sulfate de baryum

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US20250257209A1 (en) 2025-08-14
JP2025512094A (ja) 2025-04-16
WO2023198591A1 (fr) 2023-10-19
CN118974169A (zh) 2024-11-15
KR20250003770A (ko) 2025-01-07

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