EP3802701A1 - Éléments de recouvrement destinés à des sources lumineuses à del - Google Patents

Éléments de recouvrement destinés à des sources lumineuses à del

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Publication number
EP3802701A1
EP3802701A1 EP19724533.5A EP19724533A EP3802701A1 EP 3802701 A1 EP3802701 A1 EP 3802701A1 EP 19724533 A EP19724533 A EP 19724533A EP 3802701 A1 EP3802701 A1 EP 3802701A1
Authority
EP
European Patent Office
Prior art keywords
ppm
component
led lighting
lighting unit
unit according
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
EP19724533.5A
Other languages
German (de)
English (en)
Inventor
Ulrich Blaschke
Alexander Meyer
Rafael Oser
Michael Roppel
Franky Bruynseels
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 Intellectual Property GmbH and Co KG
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 Intellectual Property GmbH and Co KG filed Critical Covestro Intellectual Property GmbH and Co KG
Publication of EP3802701A1 publication Critical patent/EP3802701A1/fr
Pending legal-status Critical Current

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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21LIGHTING
    • F21KNON-ELECTRIC LIGHT SOURCES USING LUMINESCENCE; LIGHT SOURCES USING ELECTROCHEMILUMINESCENCE; LIGHT SOURCES USING CHARGES OF COMBUSTIBLE MATERIAL; LIGHT SOURCES USING SEMICONDUCTOR DEVICES AS LIGHT-GENERATING ELEMENTS; LIGHT SOURCES NOT OTHERWISE PROVIDED FOR
    • F21K9/00Light sources using semiconductor devices as light-generating elements, e.g. using light-emitting diodes [LED] or lasers
    • F21K9/20Light sources comprising attachment means
    • F21K9/27Retrofit light sources for lighting devices with two fittings for each light source, e.g. for substitution of fluorescent tubes
    • F21K9/275Details of bases or housings, i.e. the parts between the light-generating element and the end caps; Arrangement of components within bases or housings
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/13Phenols; Phenolates
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/51Phosphorus bound to oxygen
    • C08K5/52Phosphorus bound to oxygen only
    • C08K5/521Esters of phosphoric acids, e.g. of H3PO4
    • C08K5/523Esters of phosphoric acids, e.g. of H3PO4 with hydroxyaryl compounds
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21LIGHTING
    • F21VFUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V29/00Protecting lighting devices from thermal damage; Cooling or heating arrangements specially adapted for lighting devices or systems
    • F21V29/50Cooling arrangements
    • F21V29/70Cooling arrangements characterised by passive heat-dissipating elements, e.g. heat-sinks
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21LIGHTING
    • F21VFUNCTIONAL FEATURES OR DETAILS OF LIGHTING DEVICES OR SYSTEMS THEREOF; STRUCTURAL COMBINATIONS OF LIGHTING DEVICES WITH OTHER ARTICLES, NOT OTHERWISE PROVIDED FOR
    • F21V29/00Protecting lighting devices from thermal damage; Cooling or heating arrangements specially adapted for lighting devices or systems
    • F21V29/85Protecting lighting devices from thermal damage; Cooling or heating arrangements specially adapted for lighting devices or systems characterised by the material
    • F21V29/87Organic material, e.g. filled polymer composites; Thermo-conductive additives or coatings therefor
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/0008Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/005Stabilisers against oxidation, heat, light, ozone
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/01Hydrocarbons
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/04Oxygen-containing compounds
    • C08K5/10Esters; Ether-esters
    • C08K5/101Esters; Ether-esters of monocarboxylic acids
    • C08K5/103Esters; Ether-esters of monocarboxylic acids with polyalcohols
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00Use of organic ingredients
    • C08K5/49Phosphorus-containing compounds
    • C08K5/50Phosphorus bound to carbon only
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00Applications
    • C08L2203/20Applications use in electrical or conductive gadgets
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L69/00Compositions of polycarbonates; Compositions of derivatives of polycarbonates
    • FMECHANICAL ENGINEERING; LIGHTING; HEATING; WEAPONS; BLASTING
    • F21LIGHTING
    • F21YINDEXING SCHEME ASSOCIATED WITH SUBCLASSES F21K, F21L, F21S and F21V, RELATING TO THE FORM OR THE KIND OF THE LIGHT SOURCES OR OF THE COLOUR OF THE LIGHT EMITTED
    • F21Y2115/00Light-generating elements of semiconductor light sources
    • F21Y2115/10Light-emitting diodes [LED]
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02BCLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO BUILDINGS, e.g. HOUSING, HOUSE APPLIANCES OR RELATED END-USER APPLICATIONS
    • Y02B20/00Energy efficient lighting technologies, e.g. halogen lamps or gas discharge lamps

Definitions

  • the invention relates to an LED lighting unit, comprising an LED light source and a mold part, such as a cover, made of thermoplastic material.
  • the invention also relates to the improvement of the light transmission of the covering material in the range of 360 to 460 nm.
  • Light bulbs are disadvantageous because of their poor efficiency with regard to light emission and high heat development as well as the short lifetime.
  • Energy-saving lamps are significantly more energy-efficient, but because of their heavy metal content, especially mercury, they represent a high environmental impact and must be disposed of as hazardous waste.
  • Alternative concepts to conventional lighting sources and modules, e.g. Light bulbs or energy-saving lamps are in demand for sustainability and energy efficiency.
  • An alternative source of illumination which does not have these disadvantages and also has a high life and high energy efficiency, offers the semiconductor technology (as LED, OLED or electroluminescent film).
  • a preferred use of semiconductor technology as a light source is the LEDs.
  • LEDs Due to their long lifetime, low power consumption and good light output, LEDs are increasingly used as lighting sources, e.g. in the automotive industry, the air drive, the interior lighting, the facade design etc.
  • LEDs In contrast to conventional bulbs such as light bulbs or fluorescent tubes, LEDs have one of these different radiation characteristics. For applications that require directing the light beam, LEDs often require lenses or light guides.
  • luminous elements with LEDs as the light source usually contain a transparent or translucent housing part which serves to cover the light source, protects the light source and shields against external influences such as dirt and dust.
  • LEDs emit light with a wavelength dependent on the semiconductor material and the doping, so that LEDs can produce approximately monochromatic light, even in the infrared or UV range.
  • the monochromatic light of the LEDs must therefore be "converted" (eg by additive color mixing), which is possible in principle by various means: 1. Color mixing by combining a blue, a red and a green emitting LED to so-called RGB (red green blue) modules, whose combined perceived light impression is white.
  • RGB red green blue
  • white light can be generated starting from a blue LED in the visible range by adding a single phosphor, which converts part of the radiation in the blue area into red / yellow light. This form of white light generation is preferred for commercial applications for cost reasons and because of the high efficiency of blue LEDs.
  • white light may be generated from LED-generated UV light using three different phosphors emitting wavelengths corresponding to an RGB module. If this technique is used, preference is given to compositions which also have an increased stability to UV radiation, ie are provided, for example, with UV stabilization.
  • the above light sources can also be further modified as needed. This modification can be done, for example, by:
  • the stability relative to the light of the light source used is in focus.
  • the wavelength of the light is preferably in the range that is visible to the human eye, since these lighting devices are designed for human use. Emission outside the visible range means loss of energy and thus reduced efficiency of the light source.
  • a translucent or translucent plastic composition that has high color stability and high transmission over the emission spectrum of such a light source.
  • thermoplastic resin composition requires good flowability in order to easily manufacture complex geometries.
  • Such components are often intended to be integrated with elements such as plug-in or screw connections with the other elements of the lighting device. tion can be connected and therefore require a good mechanical resistance.
  • a good heat resistance is required to persist the service temperatures of the lighting device without changing the optical, geometric or other properties permanently.
  • lenses, optical fibers, transparent or translucent covers and other transparent or translucent components can be produced in Leuchtkörpem of different transparent or translucent polymers.
  • injection-moldable transparent or translucent materials which are based on the following thermoplastics: aromatic polycarbonate (PC), including copolycarbonate, polyestercarbonate, polystyrene (PS), styrene copolymers, polyalkylenes such as polyethylene (PE) and polypropylene (PP), aromatic polyesters such as polyethylene terephthalate (PET) and polybutylene terephthalate (PBT), PET-cyclohexanedimethanol copolymer (PETG), polyethylene naphthalate (PEN), poly- or copolymethyl methacrylates such as polymethyl methacrylate (PMMA), polyimides (eg PMMI), polyethersulfones, thermoplastic Polyurethanes, cyclic olefin polymers or copolymers (COP or COC) or mixtures of
  • EP 2799200 Al describes stabilizers and other additives for improving the Lichttrans mission. Certain stabilizers such as phosphorus-based antioxidants and phenolic radical scavengers have long been used to improve the optical properties. However, the improvement in transmission is very limited here.
  • Color-corrected molding compositions which are advantageous for LED and optical fiber applications are described in EP 2652031 A1. However, such colorant compositions reduce the transmission in the range of 360 to 460 nm.
  • the object of the present invention was to provide thermoplastic compositions for LED applications which have at least a high light transmission in the range between 360 and 460 nm and a high thermal stability, expressed by a low DU.I. value, compared with the corresponding additive-free polycarbonate have.
  • the Formmas sen should preferably be good to process the desired components, especially those with more complex geometry.
  • an LED lighting unit comprising an LED light source having a peak wavelength in the range of 360 to 460 nm and a molded part of a transparent or translucent thermoplastic composition
  • a thermoplastic polymer including polymer blend, preferably comprising aromatic polycarbonate, particularly preferably those prepared by the interfacial method
  • the light emitted by the LED illumination unit preferably has a color temperature determined according to DIN EN 12665: 2009, from 2500 K to 7000 K, more preferably from 2700 K to 6500 K, even more preferably from 3000 to 6000 K.
  • thermoplastic polymer-based thermoplastic composition branched aliphatic hydrocarbons, in particular squalane, in combination with one or more phosphorus-based heat stabilizers and one or more mold release agents based on a fatty acid ester to increase the transmission of light in the range from 360 to 460 nm on a thermoplastic polymer-based thermoplastic composition.
  • thermoplastic polymer to at least 50 wt .-%, more preferably at least 60 wt .-%, even more preferably at least 70 wt %, more preferably at least 80% by weight, most preferably at least 90% by weight, most preferably at least 95% by weight, in the total composition.
  • composition of the molding may contain other components, as long as they do not adversely affect the compositions of the invention.
  • compositions preferably contain no further components in addition to the components a) to g), more preferably a) to f), particularly preferably in addition to the components a) to d).
  • transparent compositions are those which have a transmission in the range from 360 nm to 780 nm, measured at a thickness of 4 mm according to ISO 13468-2: 2006, of at least 85%, preferably of at least 86%, especially preferably at least 88%, and a haze of less than 2.0%, preferably less than 1.5%, more preferably less than 1.0%, most preferably less than 0.8%, determined according to ASTM Dl 003: 2013 at a layer thickness of 20 mm.
  • translucent is understood to mean compositions which have a transmission in the range from 360 nm to 780 nm, measured at a thickness of 4 mm according to ISO 13468-2: 2006, of less than 84% and greater than 20 %, more preferably less than 80% and greater than 50%, and / or haze greater than 98%, according to ASTM Dl 003: 2013 at a layer thickness of 20 mm.
  • LED lighting unit not only in the strict sense of a package of mechanically ver related items understood, but also wider than mere combination (only) functionally to a unit connected items. However, it can also be a mechanically linked combination.
  • LED light source is understood to mean a light source which emits light having a radiation characteristic in which more than 70% of the intensity emitted in the range from 200 nm to 3000 nm lies in the visible region of the spectrum.
  • the visible range is defined as the wavelength range from 360 nm to 780 nm. More preferably, less than 5% of the intensity is in the range ⁇ 360 nm.
  • a radiation-equivalent quantity such as the radiation flux, is measured spectrally resolved and displayed in a Cartesian coordinate system. The radiation-equivalent quantity is plotted on the y-axis and the wavelengths on the x-axis.
  • the absolute maximum of this curve is the "peak wavelength” (definition according to DIN 5031-1 (1982)). "From ... to” ... includes the mentioned limits.
  • the "LED light” preferably has a narrow emission width with a maximum width at half maximum of 60 nm, more preferably of at most 45 nm, even more preferably of max. 30 nm, wherein monochromatic light is particularly preferred.
  • the half-width is the full width of an emission peak at half the height of the intensity.
  • Such emission characteristics are achieved, inter alia, by the use of semiconductors or lasers as the light source.
  • Semiconductor technology is already widely used today, for example in LEDs (light emitting diodes), organic LEDs (OLEDs) and electroluminescent films.
  • the thermoplastic polymer a) is preferably aromatic polycarbonate (PC), both homopoly carbonate and copolycarbonate, polyester carbonate, polystyrene (PS), styrene copolymers, a polyalkylene such as polyethylene (PE) and polypropylene (PP), an aromatic polyester such as polyethylene tereph thalate (PET) and polybutylene terephthalate (PBT), PET-cyclohexanedimethanol copolymer (PETG), Polyethylene naphthalate (PEN), a poly or copolymethyl methacrylate such as polymethyl methacrylate (PMMA), a polyimide (eg PMMI), a polyethersulfone, a thermoplastic polyurethane, a cyclic olefin polymer or copolymer (COP or COC), more preferably aromatic (homo ) Polycarbonate, aromatic copolycarbonate, aromatic polyester, cyclic olefin polymer or copolymer or poly
  • thermoplastic polymer according to component a) is particularly preferably aromatic polycarbonate, which may also be mixtures of several representatives of this type, for example two different aromatic copolycarbonates or two different aromatic homopolycarbonates. If component a) is a mixture of different types of thermoplastic polymer, it is preferably a mixture of polycarbonate with PMMA or polyester. However, the most preferred thermoplastic polymer is merely aromatic polycarbonate.
  • One embodiment contains as component a) a mixture of aromatic polycarbonate and PMMA with less than 2 wt .-%, preferably less than 1 wt .-%, more preferably less than 0.5 wt .-%, even more preferably with 0, 15 to 0.25 wt .-% and particularly preferably with 0.08 to 0.12 wt .-% PMMA, based on the total composition, wherein the PMMA preferably has a molecular weight ⁇ 40,000 g / mol, determined by gel permeation chromatography using polystyrene Standards and tetrahydrofuran as eluant, flow rate 1.0 mL / min.
  • Polycarbonates in the context of the present invention are both homopolycarbonates and copoly carbonates.
  • the polycarbonates may be linear or branched in a known manner. Unless mentioned in the context of the present invention of "polycarbonates", aromatic polycarbonates are always meant, even if not explicitly mentioned.
  • the preparation of the polycarbonates is carried out in a known manner from diphenols, carbonic acid derivatives, optionally chain terminators and branching agents.
  • Dihydroxyaryl compounds suitable for the preparation of the polycarbonates are, for example Hydroquinone, resorcinol, dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) ethers, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides, alpha-alpha'-bis (hydroxyphenyl) diisopropylbenzenes, phthalimidines derived from isatin or phenolphthalein derivatives, and their kemalkylated, keararylated and chemically halogenated compounds.
  • Hydroquinone resorcinol, dihydroxydiphenyls
  • bis (hydroxyphenyl) alkanes bis (hydroxyphenyl) cycloalkanes
  • bis (hydroxyphenyl) sulfides
  • Preferred dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane, 1,1'-bis- (4-hydroxyphenyl ) -phenylethane, 1,3-bis [2- (4-hydroxyphenyl) -2-propyl] benzene (bisphenol M), 1,1-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 2,2-bis - (3-methyl-4-hydroxyphenyl) -propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) -methane, 2,2 Bis- (3,5-dimethyl-4-hydroxyphenyl) propane, bis (3,5-dimethyl-4-hydroxyphenyl) sulfone, 2,4-bis (3,5-dimethyl-4-hydroxyphenyl) -2-methylbutane,
  • R ' is in each case a C 1 - to C 4 -alkyl radical, aralkyl radical or aryl radical, preferably a methyl radical or phenyl radical, very particularly preferably a methyl radical.
  • dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl, 1,1-bis (4-hydroxyphenyl) -phenyl-ethane, 2,2-bis- (4-hydroxyphenyl) -propane, 2,2-bis- (3, 5-dibromo-4-hydroxyphenylj-propane, 2,2-bis (3,5-dichloro-4-hydroxyphenyl) -propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenylj-propane, 1, 1 bis- (4-hydroxyphenyl) cyclohexane and 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane (bisphenol TMC) and the dihydroxyaryl compounds of the formulas (I), (II) and / or (III).
  • Suitable carbonic acid derivatives are, for example, phosgene or diphenyl carbonate.
  • Suitable chain terminators which can be used in the preparation of the polycarbonates are both monophenols and monocarboxylic acids.
  • Suitable monophenols are for example phenol itself, alkylphenols such as cresols, p-tert-butylphenol, cumylphenol, pn-octylphenol, p-iso-octylphenol, pn-nonylphenol and p-iso-nonylphenol, halophenols such as p-chlorophenol, 2,4 - Dichlorophenol, p-bromophenol and 2,4,6-tribromophenol, 2,4,6-triiodophenol, p-iodophenol, and de ren mixtures.
  • Preferred chain terminators are also the phenols which are mono- or polysubstituted by C 1 - to C 30 -alkyl radicals, linear or branched, preferably unsubstituted or substituted by tert-butyl.
  • Particularly preferred chain terminators are phenol, cumylphenol and / or p-tert-butylphenol.
  • Suitable monocarboxylic acids are furthermore benzoic acid, alkylbenzoic acids and halobenzoic acids.
  • the amount of chain terminator to be used is preferably from 0.1 to 5 mol%, based on mols of diphenols used in each case.
  • the addition of the chain terminators can be carried out before, during or after the reaction with a Kohleklarederivat.
  • Suitable branching agents are the trifunctional or more than trifunctional compounds known in polycarbonate chemistry, especially those having three or more than three phenolic OH groups.
  • Suitable branching agents are, for example, phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptene-2, 4,6-dimethyl-2,4,6-tri (4-hydroxyphenyl) -heptane , 1, 3,5-tri (4-hydroxyphenyl) -benzene, 1,1,1-tri- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -phenylmethane, 2,2-bis- [4 , 4-bis- (4-hydroxyphenyl-cyclohexyl) -propane, 2,4-bis (4-hydroxyphenylisopropyl) -phenol, 2,6-bis (2-hydroxy-5'-methyl-benzyl) -4- methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) -propane, hexa- (4- (4-hydroxyphenylisopropyl) -phenyl
  • the branching agents may either be initially charged with the diphenols and the chain terminators in the aqueous alkali phase or may be added in an organic solvent dissolved prior to phosgenation. In the case of the transesterification process, the branching agents are used together with the diphenols.
  • the aromatic polycarbonates contained in the compositions according to the invention are preferably prepared by the interfacial process.
  • the aromatic polycarbonates of the present invention preferably have weight average molecular weights M w of between 15,000 and 25,000 g / mol, preferably between 15,000 and 24,000 g / mol, more preferably between 16,000 and 23,500 g / mol, still further and most preferably between 18,000 and 22,500 g / mol.
  • the values are valid for determination by gel permeation chromatography, using dichloromethane as eluent, calibration with linear polycarbonates (from bisphenol A and phosgene) of known molecular weight distribution of PSS Polymer Standards Service GmbH, Germany, calibration according to method 2301-0257502-09D (from Years 2009 in German) of Currenta GmbH & Co. OHG, Leverkusen.
  • the eluent is also used in calibrating dichloromethane.
  • RI refractive index
  • the MVR value of the aromatic polycarbonate measured according to ISO 1133: 2012-03 at 300 ° C. and 1.2 kg, is preferably 14 to 70 cm 3 / (10 min), more preferably 18 to 65 cm 3 / (10 min ).
  • the Mw and MVR figures refer to the aromatic polycarbonates contained in the composition in their entirety.
  • Particularly preferred polycarbonates are the homopolycarbonate based on bisphenol A, the homopolycarbonate based on 1,3-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and the copolycarbonates based on the two monomers bisphenol A and l , 1-Bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.
  • Suitable phosphorus-based stabilizers include thermostabilizers selected from the group of phosphates, phosphites, phosphonites, phosphines and mixtures thereof. It is also possible gene of various compounds from one of these subgroups are used, for example, two phosphites.
  • Suitable phosphorus-based stabilizers include triphenyl phosphite, Diphenylalkylphos- phit, Phenyldialkylphosphit, tris (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, disazo tearylpentaerythritoldiphosphit, tris (2,4-di-tert-butylphenyl) phosphite (Irgafos ® 168) Diisodecylpenta - erythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, bis (2,4-di-cumylpheny
  • triphenylphosphine TPP
  • Irga fos ® 168 Tris (2,4-di-tert-butyl-phenyl) phosphite
  • PEP-36 bis (2,6-di-tert-butyl-4-methylphenyl ) pentaerythritol diphosphite) or tris (nonylphenyl) phosphite or mixtures thereof.
  • Phosphate stabilizers in the context of the present invention are, for example, phosphates of the formula
  • radicals RI are independently branched alkyl and / or optionally substitutability te aryl, wherein the alkyl group is preferably a Ci to C 8 - alkyl group, more preferably a Ci to C 8 alkyl radical, is.
  • the aryl radical is preferably substituted by linear C 1 to CU alkyl, branched C 1 to C 8 alkyl or cumyl, it being possible for the substituents to be identical or different. NEN, however, the same substituents are preferred.
  • the aryl radicals are substituted in positions 2 and 4 or 2, 4 and 6. Very particular preference is given to tert-butyl substituents in these positions. More preferably, all Rl are the same.
  • triisooctyl phosphate is used as the phosphorus-based stabilizer.
  • the total amount of phosphorus-based stabilizers in the composition is 10 - 2500 ppm, preferably 20 ppm to 2000 ppm, more preferably 100 ppm to 1500 ppm, more preferably 200 ppm to 1000 ppm, most preferably 200 to 300 ppm, based on the total weight of the thermoplastic polymer according to component a).
  • Component c is one or more branched aliphatic hydrocarbons. These are of such natural or synthetic origin. These hydrocarbons preferably have pendant alkyl groups, for example methyl, ethyl, propyl, isobutyl or butyl groups, more preferably methyl groups.
  • the number of carbon atoms which a hydrocarbon according to the invention has according to component c is preferably from 20 to 80, more preferably from 25 to 40.
  • the carbon atoms of the methyl groups form a weight fraction, based on the total molecule, of preferably 10 to 30% by weight.
  • the hydrocarbons according to component c are preferably formally or by actual synthesis to 50 to 100 mol% of hydrogenated Mehrfachterpenen, more preferably isoprene units constructed.
  • the proportion of the hydrogenated isopropene units is more preferably more than 90 mol%, more preferably more than 95 mol%, based on the total molecule of the compound according to component c.
  • Comonomers such as are present in form or can actually be used in addition to isoprene, are those customary in rubber production and polyolefin chemistry, in particular 2,3-dimethylbutadiene, butadiene, propene and / or isobutene.
  • the hydrocarbon is composed of linked Famesan units, in particular of "tail-tail” -linked, and is in particular squalane, hydrogenated lycopene or Octamethyldotriacontan.
  • component c in the compositions used according to the invention comprises squalane (2, 6, 10, 15, 19, 23-hexamethyltetracosane); Most preferably, component c) is squalane.
  • the total amount of component c is 200 ppm to 4500 ppm, preferably up to 4000 ppm, more preferably up to 3500 ppm, even more preferably 400 ppm to 3000 ppm, more preferably 500 ppm to 2500 ppm, most preferably 1000 ppm to 2000 ppm on the total weight of the thermoplastic polymer according to component a.
  • Component d are mold release agents based on a fatty acid ester.
  • Such mold release agents are in particular pentaerythritol tetrastearate and glycerol monostearate.
  • Preferred as mold release agents is a glycerol ester of fatty acid, more preferably a glycerol monoester.
  • Glycerinmonostearat is a mold release agent that is contained in the compositions according to the invention.
  • fatty acid ester is not so strict that only a single fatty acid ester is the basis of the compounds. It is only important that the mold release agents are based on fatty acid esters; these may also be mixtures of different fatty acid esters.
  • the total amount of component d) is 100 ppm to 4000 ppm, preferably 120 to 1000 ppm, more preferably 150 ppm to 800 ppm, even more preferably 150 ppm to 500 ppm, based on the total weight of thermoplastic polymer according to component a.
  • phenolic antioxidants may be used in an amount of up to 1000 ppm, preferably 50 ppm to 800 ppm, more preferably 75 ppm to 700 ppm, even more preferably 100 ppm to 500 ppm, for example alkylated monophenols, alkylated thioalkylphenols, hydroquinones and alkylated hydroquinones ,
  • Irganox ® 1010 penentaerythritol-3- (4-hydroxy-3,5-di-tert-butylphenyl) propionate; CAS-No .: 6683-19-8) and / or Irganox 1076 ® (2,6-Di tert-butyl-4- (octadecanoxycarbonylethyl) phenol; CAS No .: 2082-79-3).
  • Irga nox is particularly preferably used ® 1076 (2,6-di-tert-butyl-4- (octadecanoxycarbon
  • a phosphine compound according to component b is used together with a phosphite according to component b or a phenolic compound Antioxidant used according to components e or a mixture of the latter two compounds.
  • a phenolic antioxidant such as Irganox ® 1076 or Irganox ® 1010 and / or a combination of phenolic antioxidant and phosphite, preferably a mixture of Irganox ® 1076 and Irganox ® 1010 and Irgafos ® 168 or PEP-36.
  • the stabilizer system comprising a phosphine, a phosphite, and a phenolic antioxidant, with play, triphenylphosphine, Irganox ® 1076 and Irgafos ® 168th
  • the UV absorbers as component f of the present invention are compounds which have AS POSSIBLE low transmission below 400 nm and the highest possible transmission above 400 nm. Such compounds and their preparation are known from the literature and are described, for example, in EP 0 839 623 A1, WO 1996/15102 A2 and EP 0 500 496 A1.
  • Ultraviolet absorbers which are preferred for use in the composition according to the invention are benzotriazoles, in particular hydroxybenzotriazoles, triazines, benzophenones and / or arylated cyanoacrylates.
  • the following ultraviolet absorbers are particularly suitable hydroxy-benzotriazoles, such as 2- (3 ', 5'-bis (l, l-dimethylbenzyl) -2'-hydroxyphenyl) benzotriazole (Tinuvin ® 234, BASF SE, Ludwigshafen ), 2- (2'-hydroxy-5 '- (tert-octyl) phenyl) benzotriazole (Tinuvin ® 329, BASF SE, Ludwigshafen, Germany)) bis (3- (2H-benzotriazolyl) -2-hydroxy -5-tert-octyl) methane, (Tinuvin ® 360, BASF SE, Ludwigshafen), (2- (4,6-diphenyl-l, 3,5-triazin-2-yl) -5- (hexyloxy) - phenol (Tinuvin ® 1577, BASF SE, Ludwigshafen, Germany), the benzophenones, 2,4-dihydroxy-benzophenone (Chimasorb
  • Very particularly preferred UV absorbers are Tinuvin ® 360, Tinuvin ® 329, Hostavin ® B-Cap, U- vinul ® 3030, particularly preferably Tinuvin ® 329, and Hostavin ® B-Cap.
  • the total amount of UV absorber is 0 ppm to 6000 ppm, preferably 500 ppm to 5000 ppm, more preferably 1000 ppm to 2000 ppm, based on the total weight of thermoplastic polymer.
  • the polymer compositions according to the invention may optionally contain further customary polymer additives as component g, as described, for example, in US Pat. in EP 0 839 623 A1, WO 1996/15102 A2, EP 0 500 496 A1 or in the "Plastics Additives Handbook", Hans Zweifel, 5th Edition 2000, Hanser Verlag, Kunststoff.
  • Further customary additives are antioxidants which differ from component e, mold release agents other than component d, flame retardants, antidrip agents, stabilizers other than component b, optical brighteners, light scattering agents, colorants, in each case in the quantities customary for the respective thermoplastics. It is understood that component g comprises only those components which have not already been described by the additives b to f.
  • the further polymer additives g in a total amount of 0 ppm to 500,000 ppm, preferably 100 ppm to 100,000 ppm, and more preferably 500 ppm to 50,000 ppm, more preferably be preferred to 30,000 ppm, each based on the amount of thermoplastic polymer component Kom a, used. Also mixtures of several additives are suitable.
  • colorants are used in the composition according to the invention, it is essential here that the added colorants are resistant to the conditions during operation of the light source, eg have a high resistance to the incident light, optionally elevated temperature and other conditions prevailing during operation of the light source , And that the colorants in the substrate material in the range of the emission maximum of the light source, ie in particular in the range of 360 nm to 460 nm, or in the conversion region, have no relevant absorption, as this significantly affects the efficiency of the illuminant and thus the light intensity.
  • Coloring agents are preferably used are Macrolex ® Blue RR, Macrolex ® Violet R 3 and / or Macrolex Red EG ®.
  • additives include tetramethylene glycol derivatives.
  • An inventively preferred LED lighting unit comprising an LED light source with a peak wavelength in the range of 360 to 460 nm and a molded part of a transparent or translucent, preferably transparent, thermoplastic composition is one in which the composition a) thermoplastic polymer, wherein the thermoplastic polymer is aromatic polycarbonate, b) 10 to 2500 ppm of one or more phosphorus-based stabilizers selected from the group consisting of phosphates, phosphites, phosphonites, phosphines and mixtures thereof, c) 200 ppm to 4500 ppm of one or more branched aliphatic hydrocarbons, d) 100 ppm to 4000 ppm of one or more mold release agents based on a fatty acid ester, e) 0 to 1000 ppm of one or more phenolic antioxidants, f) 0 ppm to 6000 ppm of one or more UV And g) 0 ppm to 500,000 ppm of one or more further additives, where
  • an LED lighting unit comprising an LED light source with a
  • an LED illumination unit comprising an LED light source having a peak wavelength in the range of 360 to 460 nm and a molded part of a transparent or translucent, preferably transparent, thermoplastic composition consisting of a) aromatic polycarbonate, b) 10 to 2500 ppm of one or more phosphorus-based stabilizers selected from the group consisting of phosphates, phosphites, phosphonites, phosphines and mixtures thereof, wherein component b preferably comprises triphenylphosphine, c) 200 ppm to 4500 ppm of one or more branched aliphatic hydrocarbons d) 100 ppm to 4000 ppm of one or more mold release agents based on a fatty acid ester, component d preferably comprising glycerol monostearate, e) 0 ppm to 1000 ppm of one or more phenolic antioxidants, f) 0 ppm to 6000 ppm of one or more UV absorbers,
  • the molding is a lens, a lamp cover and / or a Lichtlei ter.
  • the MVR value of the composition should preferably be between 18 cm 3 / ( 10 minutes) and 80 cm 3 / (10 min), more preferably between 20 cm 3 / (10 min) and 80 cm 3 / (10 min), even more preferably between 30 cm 3 / (10 min) and 80 cm 3 / (10 min) and more preferably between 32 cm 3 / (10 min) and 75 cm 3 / (10 min).
  • the notched impact strength of the thermoplastic molding compositions should preferably be at least 40 kJ / m 2 , more preferably between 50 kJ / m 2 and 130 kJ / m 2 , even more preferably between 55 kJ / m 2 and 120 kJ / m 2 and particularly preferably between 55 kJ / m 2 and 80 kJ / m 2 .
  • the material should preferably have an increased heat deflection temperature in order to withstand the elevated temperatures during operation of the lighting unit and not to lose its precise shape.
  • the Vicat softening temperature measured according to DIN EN ISO 306: 2014 (50 N, 120 ° C / h), is therefore preferably at least 120 ° C. More preferably, the Vi cat softening temperature is between 120 ° C and 220 ° C, even more preferably between 130 ° C and 200 ° C, more preferably between 40 ° C and 180 ° C, most preferably between 40 ° C and 150 ° C C.
  • the refractive index of the material is preferably at least 1.400. More preferably, the refractive index is between 1.450 and 1.600, more preferably between 1.480 and 1.590, more preferably between 1.500 and 1.590, most preferably between 1.550 and 1.590.
  • the preparation of the polymer compositions used according to the invention is carried out by conventional incorporation methods by combining, mixing and homogenizing the individual components, wherein in particular the homogenization preferably in the melt under the action of shear forces. Where appropriate, the merging and mixing takes place before the melt homogenization using powder premixes. Premixes of granules or granules and powders with the additives according to the invention can also be used. It is also possible to use premixes which have been prepared from solutions of the mixture components in suitable solvents, optionally homogenizing in solution and subsequently removing the solvent.
  • the additives of the compositions used according to the invention can be introduced by known processes or as a masterbatch.
  • masterbatch preference is given to introducing colorants which may be present, in particular masterbatches based on the respective polymer matrix.
  • the composition may be combined, blended, homogenized and then extruded in conventional equipment such as screw extruders (for example twin screw extruder, ZSK), kneaders, Brabender or Banbury mills. After extrusion, the extrudate can be cooled and comminuted. It is also possible to premix individual components and then to add the remaining starting materials individually and / or likewise mixed.
  • the merging and mixing of a premix in the melt can also be done in the plasticizing an injection molding machine.
  • the melt is transferred in the subsequent step directly into a shaped body.
  • the injection molding process is preferably used. This has the advantage of a high degree of freedom in the shaping.
  • Molded parts of the described compositions used according to the invention preferably have the function of covers, in particular lamp covers, light guides and / or lenses for LED lights in motor vehicles or other lighting applications and are intended for use in combination with LED light, in particular LED light sources with a peak wavelength in the range of 360 to 460 nm, and particularly advantageous if they are exposed to light from high-power LEDs.
  • lenses for focusing and proper distribution of the light, and light guides in particular those in automobile headlamps with LED light source, which are used as daytime driving light,
  • optical fibers in particular those in automobile headlamps with LED light source, which are used as daytime running lights,
  • lights e.g. Headlight covers, indicator caps or other optical
  • Lighting devices in flat screen television 6. Lighting devices of displays of electronic devices such as calculators, mobile phones,
  • Automotive parts such as glazings, body parts and trim with LED lighting.
  • the plastic composition according to the Invention in one or more layer (s) on a molded article of a plastic, which is not colored or otherwise colored, applied or one or more layer (s) are on an element / a layer consisting from the Kunststoffzusammenset tion, applied.
  • the application can be done simultaneously with or immediately after the molding of the molding, for example by injection molding a film, coextrusion or Mehrkompo nentenspritzguss.
  • the application can also be done on the finished shaped body, e.g. by lamination with a film, overmolding or by coating from a solution.
  • the molding preferably forms the backing layer, i. the thickest layer.
  • the molding can - if desired - have a small thickness, which is advantageous for areal applications.
  • the thickness may be, for example, in the range of 0.5 to 1.5 mm.
  • thick wall designs are also possible, e.g. in thick wall optics with a thickness of 2 to 3 cm.
  • the ability to use electronic components, in particular the LED light source, directly in recesses of the molded part has various advantages.
  • the electronic component can be precisely positioned on the plastic molded part.
  • a recess in the optical component, comprising the molded part can be designed such that the upper side of the one or more electronic component (s) terminates approximately flush with the shaped part of the magnet.
  • This arrangement has the advantage that the production of an electrical con tact of the electronic component (s) with other components and / or electrical conductors can be carried out in an advantageous manner.
  • the transparent or translucent plastic molded part may have on its surface structures with an optical effect for additional control of the light, for example microlenses.
  • plastic moldings with micro lenses for focusing and Effi ciency increase a plastic molded part, including a plastic film can be equipped with diffuser properties, so that the impression of a "surface light" instead of a luminaire with huiuel len light sources.
  • phosphorescent pigments so-called phosphors
  • phosphors incorporated or applied in these plastic moldings or plastic film, so for example white light can be generated when blue LEDs are inserted.
  • white light can be generated when blue LEDs are inserted.
  • PCI Aromatic polycarbonate from Covestro Deutschland AG with an MVR of about 33 cm 3 / (10 min), measured at 300 ° C. and 1.2 kg load (according to ISO 1133-1: 2012-03), based on Bisphenol A and terminated with tert-butylphenol. Made in interfacial process.
  • the polycarbonate contains 250 ppm of triphenylphosphine and 300 ppm of glycerol monostearate (based on the amount of polycarbonate in the overall composition of the particular example). Used for Examples VI to V12 and E13 to E16.
  • PC2 Aromatic polycarbonate from Covestro GmbH AG with an MVR of approx. 34 cm 3 / (10 min), measured at 300 ° C. and 1.2 kg load (according to ISO 1133-1: 2012-03), based on Bisphenol A and terminated with tert-butylphenol.
  • the polycarbonate contains 250 ppm of triphenylphosphine and 300 ppm of glycerol monostearate (based on the amount of polycarbonate in the overall composition of each example). Produced in interfacial process. Used for Comparative Examples VI 7 and VI 8.
  • PC3 Aromatic polycarbonate from Covestro GmbH AG with an MVR of about 55 cm 3 / (10 min), measured at 300 ° C. and 1.2 kg load (in accordance with ISO 1133-1: 2012-03), based on Bisphenol A and terminated with tert-butylphenol. Made in interfacial process.
  • the polycarbonate contains 250 ppm of glycerol monostearate (based on the amount of polycarbonate in the overall composition of each example).
  • A2 Disflamoll ® TP Lanxess Germany GmbH. triphenyl; CAS-No. 115-86-6.
  • A3 Zeonor ® 1420R Zeon Corp., Chiyoda, Japan. Cylcoolefm copolymer (COP).
  • A4 Dianal BR87 from the company Mitsubishi Rayon. Polymethyl methacrylate having a Molekularge weight of about 25,000 g / mol, determined using an Ostwald viscometer by measuring the intrinsic viscosity in chloroform at 25 ° C, and a refractive index of 1.490.
  • A5 squalane from Merck KGaA, Darmstadt, Germany. 2.6, l0, l5, l9,23-hexamethyltetracosane;
  • A6 Dimodan ® HAB Veg DuPont. A glycerol monostearate.
  • A7 triphenylphosphine from BASF SE; CAS-No. 603-35-0.
  • the polycarbonate raw material PC 1 was net dried for 3 hours in a dry air dryer at 120 ° C. 10 kg of the thus dried material were filled into a 25 1 vessel and then the already weighed already be supplied additive and mixed for 10 min in a tumble mixer. The mixing step was omitted for VI.
  • the mixture was fed via the material hopper to a Krauss Maffei 80-38 injection molding machine and then sprayed at 260 ° C melt temperature in a multilayer process.
  • Optical pattern plates measuring 40 mm x 38 mm x 20 mm were sprayed.
  • the polycarbonate raw material PC2 was net dried for 3 hours in a dry air dryer at 120 ° C. 10 kg of the thus dried material were filled into a 25 1 vessel and then the already weighed already be supplied additive and mixed for 10 min in a tumble mixer. The mixing step was omitted for VI 8.
  • the mixture was fed via the material hopper to a Krauss Maffei 80-38 injection molding machine and then sprayed at 260 ° C melt temperature in a multilayer process.
  • Optical pattern plates measuring 40 mm x 38 mm x 20 mm were sprayed.
  • the compounding was carried out on a Berstorff twin-screw extruder at a melt temperature of 275 ° C and an extruder speed of 100 revolutions / minute.
  • the PC3 granules were vacuum dried at 110 ° C for 3 hours and then compounded with the additives.
  • a powder premix was used.
  • the additives were in a polycarbonate powder (Aromatic polycarbonate from Covestro GmbH AG with an MVR of about 19 cm 3 / (l0 min), measured at 300 ° C and 1.2 kg load (according to ISO 1133-1: 20l2- 03) based on bisphenol A and terminated with tert-butylphenol, predispersed This powder was added in an amount of 5% by weight and the additives were metered to give the amounts indicated below.
  • Amounts of additive (based on the amount of polycarbonate in the overall composition of the respective example):
  • the compounded granules were vacuum dried at 120 ° C for 3 hours and then on an injection molding machine of the type Arburg 370 with an injection unit at a melt temperature of 280 ° C and a mold temperature of 80 ° C to color sample plates with the dimensions 60 mm x 40 mm x 4 mm (width x height x thickness) processed.
  • the compounding was carried out on a Berstorff twin-screw extruder at a melt temperature of 275 ° C and an extruder speed of 100 revolutions / minute.
  • the PC 1 granules were vacuum dried at 110 ° C for 3 hours and then compounded with the additives.
  • a powder premix was used.
  • the additives in a polycarbonate powder (aromatic polycarbonate from Covestro Germany AG with an MVR of about 19 cm 3 / (l0 min), measured at 300 ° C and 1.2 kg load (according to ISO 1133-1: 2012- 03), based on bisphenol A and terminated with tert-butylphenol) before dispersed.
  • This powder was added in an amount of 5 wt .-%.
  • the additives were dosed so as to give the amounts indicated below. Amounts of additive (based on the amount of polycarbonate in the overall composition of the respective example):
  • the optical measurement was carried out on a Lambda 950 spectrophotometer from Perkin Elmer with a photometer sphere.
  • the yellowness index (Y.I.) was determined according to ASTM E 313-15 (observer: 10 ° / illuminant: D65) with a Perkin Elmer Lambda 950 spectrophotometer with a photometer sphere.
  • the haze was determined according to ASTM Dl 003: 2013.
  • the glass transition temperature T g was measured by DSC in the heat flow differential 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 indicated. The measurement was carried out according to ISO 11357-2: 2014-07 3 o
  • the additive Al is known as flow aid. Due to improved flowability, it is in principle possible to reduce the damage during the thermal processing in extruders or Spritzgussmaschi NEN, as less shear forces are entered. It was therefore surprising that no improvement in terms of transmission and yellowness could be achieved with this additive. Low-molecular additives such as A3 can also increase flowability - albeit without having a positive effect on the optical properties in the relevant transmission range.
  • Additive A5 like additive A6, has a demolding effect. However, a further addition of A6 remains as a demodulator without significant effect or leads to significantly reduced transmission at 380 nm, whereas surprisingly the use of A5 even in small amounts to a

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Abstract

L'invention concerne l'utilisation d'hydrocarbures aliphatiques ramifiés comme le squalène dans des compositions basées sur un polymère thermoplastique, en particulier sur un polycarbonate, qui sont utilisées pour la préparation de pièces moulées qui sont employées dans des unités d'éclairage à DEL, telles que des éléments de recouvrement. Selon l'invention, il a été montré que, lors de l'utilisation d'hydrocarbures aliphatiques ramifiés, la transmission totale et la transmission peuvent être augmentées d'environ 360 à 460 nm, ce qui rend des compositions correspondantes particulièrement appropriées pour la préparation de pièces moulées destinées à être utilisées en association avec des sources lumineuses à DEL blanches. Il s'est en outre avéré que, simultanément, le jaunissement et le trouble sont réduits.
EP19724533.5A 2018-05-29 2019-05-21 Éléments de recouvrement destinés à des sources lumineuses à del Pending EP3802701A1 (fr)

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EP18174697.5A EP3575362A1 (fr) 2018-05-29 2018-05-29 Recouvrements pour sources lumineuses à led
PCT/EP2019/063118 WO2019228867A1 (fr) 2018-05-29 2019-05-21 Éléments de recouvrement destinés à des sources lumineuses à del

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US12005151B2 (en) * 2020-09-03 2024-06-11 Luminary, Llc Antimicrobial smartphone flashlight
US11708289B2 (en) 2020-12-03 2023-07-25 Docter Optics Se Process for the production of an optical element from glass
DE102022101728A1 (de) 2021-02-01 2022-08-04 Docter Optics Se Verfahren zur Herstellung eines optischen Elementes aus Glas
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