Classifications

• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
  • C23C14/34—Sputtering
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/048—Forming gas barrier coatings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
  • C08J7/04—Coating
  • C08J7/06—Coating with compositions not containing macromolecular substances
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/0021—Reactive sputtering or evaporation
  • C23C14/0036—Reactive sputtering
  • C23C14/0057—Reactive sputtering using reactive gases other than O2, H2O, N2, NH3 or CH4
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/06—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the coating material
  • C23C14/08—Oxides
  • C23C14/086—Oxides of zinc, germanium, cadmium, indium, tin, thallium or bismuth
• • C—CHEMISTRY; METALLURGY
  • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
  • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
  • C23C14/00—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material
  • C23C14/22—Coating by vacuum evaporation, by sputtering or by ion implantation of the coating forming material characterised by the process of coating
  • C23C14/56—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks
  • C23C14/562—Apparatus specially adapted for continuous coating; Arrangements for maintaining the vacuum, e.g. vacuum locks for coating elongated substrates

Definitions

• Zinc-tin oxide coated plastic film with improved optical absorption property Zinc-tin oxide coated plastic film with improved optical absorption property
• the present invention relates to a coated plastic film with a zinc-tin oxide coating, which has an improved absorption property, in particular in the blue spectral range of 380 to 430 nm, the zinc-tin oxide coating itself and a
• Suitable coatings for such barrier coatings include, for example, inorganic coatings such as alumina, titania or silicon nitride.
• inorganic coatings such as alumina, titania or silicon nitride.
• ZTO zinc-tin oxide
• such a coating has the advantage over aluminum oxide and silicon nitride of a lower crack formation when applied to flexible plastic substrates.
• the flexible substrates In addition to the required property of forming a sufficient barrier to the permeation of oxygen and water vapor, however, the flexible substrates must have good transmission in the visible spectral range for use in flexible electronic devices.
• a conventional ZTO coating as described, for example, in EP 2 148 899 A1, has an absorption of more than 4% in the spectral range from 380 to 430 nm, for example, at a layer thickness of 90 nm.
• the object of the invention was therefore to provide a substrate coated with a ZTO barrier coating or a ZTO barrier coating whose optical absorption properties are improved compared to the known ZTO coatings, and to a simple process for their production.
• This object was surprisingly achieved in that the deposition of such a ZTO coating by means of a sputtering process in the presence of hydrogen in the process gas.
• the present invention accordingly provides a coated plastic substrate comprising a base layer containing at least one plastic, preferably at least one thermoplastic, and at least one coating of zinc-tin oxide, characterized in that the coating of zinc-tin oxide in a sputtering process in Presence of hydrogen is produced in the process gas.
• the zinc-tin-oxide coating can be located directly on the base layer containing at least one plastic, preferably at least one thermoplastic.
• further layers may also be present between the base layer and the coating of zinc-tin oxide.
• the present invention further provides a permeation barrier coating for gases and vapors, preferably for oxygen, nitrogen and / or water vapor, more preferably for oxygen and / or water vapor based on zinc-tin oxide, characterized in that the coating of zinc-tin oxide Oxide is produced in a sputtering process in the presence of hydrogen in the process gas.
• the coating according to the invention may additionally be an additional permeation barrier coating for nitrogen.
• Such a zinc-tin-oxide coating surprisingly has a significantly lower absorption in the blue spectral range from 380 to 430 nm and thus a lower yellowness than the coatings which are produced without the addition of hydrogen in the process gas.
• the absorption in this spectral range could be reduced to below 5%, preferably below 4%.
• the process gas contains at least one inert gas, preferably argon, during the production in the sputtering process.
• the process gas also contains oxygen during the production in the sputtering process.
• the process gas contains 0.1 to 20% by volume, more preferably 0.5 to 15% by volume, most preferably 1 to 12% by volume of> hydrogen.
• vol .-%> data refer to the entire volume of the process gas including any noble gases present.
• the zinc-tin oxide in the coating is a chemical compound of the elements zinc, tin and oxygen, wherein the mass fraction of zinc is 5 to 70%, preferably 10 to 70%.
• the zinc-tin oxide is ZnSn x O y , wherein x is a number from 0.2 to 10.0 and y is a number from 1.4 to 21.0.
• Such zinc-tin oxides are so-called mixed oxides with different proportions of phases ZnSnO 3, Zn 2 SnO 4 and optionally also of ZnO and SnO 2 and optionally unreacted Zn and Sn.
• one or more zinc-tin-oxide coatings may be applied to the substrate.
• the zinc-tin-oxide coatings may also alternate with other layers.
• the respective thickness of the zinc-tin-oxide coating is 10 to 1000 nm, preferably 20 to 500 nm, particularly preferably 50 to 250 nm. In the case of several coatings of zinc-tin oxide, these may be identical or different ⁇
• composition ZnSn x O y act.
• the composition ZnSn x O y in the individual zinc-tin-oxide coatings is substantially the same.
• the layer thicknesses of the individual zinc-tin-oxide coatings may be the same or different.
• the respective layer thickness of the individual zinc-tin-oxide coatings is the same.
• the transitions between the layers may be sharp (the change in the composition of the layers at the interface is abrupt) or fluid (the composition varies continuously across the junctions over a given distance).
• the zinc-tin-oxide coating preferably has an absorption coefficient of less than 0.5 ⁇ / ⁇ , particularly preferably less than 0.3 l / ⁇ in the spectral range of 380 to 430 nm.
• the absorption coefficients can be determined in such a way that the transmission and reflection are measured with a conventional spectrometer, the absorption is calculated from the measured data, and the mean value of the absorption in the spectral range of 380-430 nm is determined therefrom. With the aid of the layer thickness, the absorption coefficient can be calculated from this.
• the plastic substrate preferably the thermoplastic plastic substrate containing a base layer comprising at least one plastic, preferably at least one thermoplastic, is preferably a flexible plastic substrate, particularly preferably a single-layer or multi-layer plastic film.
• the plastic substrate is preferably one containing a base layer containing at least one thermoplastic.
• a multilayer thermoplastic film as a substrate this may be one by co-extrusion, extrusion lamination or lamination, preferably a thermoplastic film produced by co-extrusion.
• the single-layer or multi-layer plastic film containing a base layer preferably has a thickness of from 10 ⁇ m to 1000 ⁇ m, more preferably from 20 to 500 ⁇ m, very particularly preferably from 50 to 300 ⁇ m.
• thermoplastics for the plastic layers are independently thermoplastics selected from polymers of ethylenically unsaturated monomers and / or polycondensates of bifunctional reactive compounds in question. Particularly preferred are transparent thermoplastic materials.
• thermoplastics are polycarbonates or copolycarbonates based on diphenols, poly- or copolyacrylates and poly- or co-polyethacrylates such as, by way of example and by way of preference, polymethyl methacrylate, poly- or copolymers with styrene such as, by way of example and by way of example, transparent polystyrene or polystyrene-acrylonitrile (SAN), transparent thermoplastic polyurethanes, and polyolefins, such as by way of example and preferably transparent Polypropylentypen or polyolefins based on cyclic olefins (eg TOPAS ® , Hoechst), poly- or copolycondensates of terephthalic acid or naphthalenedicarboxylic acid, such as by way of example and preferably poly- or copolyethylene terephthalate (PET or CoPET ), glycol-modified PET (PETG) or poly- or copoly
• thermoplastics are preferably polycarbonates or copolycarbonates based on diphenols, poly- or copolyacrylates, poly- or copolymers of copolyacrylates, copolymers or copolymers with styrene, thermoplastic polyurethanes, polyolefins, copolycondensates of terephthalic acid, poly- or copolycondensates of naphthalenedicarboxylic acid or Mixtures of these.
• the at least one thermoplastic resin does not comprise polyethylene terephthalate.
• Particularly preferred are such high-transparency, low-haze thermoplastic materials, which are particularly useful for optical or opto-electronic applications, such as e.g. in display applications.
• thermoplastics are particularly preferably polycarbonates or copolycarbonates based on diphenols, poly- or copolyacrylates, poly- or co-polyethacrylates, or poly- or copolycondensates of terephthalic acid or naphthalenedicarboxylic acid, such as, by way of example and by way of preference, poly- or copolyethylene terephthalate (PET or CoPET), glycol modified PET (PETG) or poly- or copolybutylene terephthalate (PBT or CoPBT), poly- or copolyethylene naphthalate (PEN or CoPEN) or mixtures of the foregoing.
• PET or CoPET poly- or copolyethylene terephthalate
• PET or CoPET glycol modified PET
• PBT or CoPBT poly- or copolybutylene terephthalate
• PEN or CoPEN poly- or copolyethylene naphthalate
• a smoothing layer may be applied to the surface of the plastic substrate, preferably the plastic film, to be coated.
• a smoothing layer has a surface roughness (measured as Ra (average roughness)) of less than 500 nm, more preferably less than 200 nm, most preferably less than 150 nm.
• such a smoothing layer has a surface roughness of less than 100 nm, preferably less than 50 nm, more preferably less than 20 nm.
• the surface roughness of such a smoothing layer can be determined according to DIN EN ISO 4287 using a Contour GT-KO Optical Surface Profiler can be measured. Such a previous application r
• smoothing layers can bring about the advantage that in the zinc-tin-oxide coating smaller amounts of defects are produced and correspondingly better permeation barriers for gases and vapors, preferably for oxygen and / or water vapor, can be achieved.
• Suitable materials for such smoothing layers are known to those skilled in the art. These can be, for example, coating compositions for a radiation-cured coating or a polyurethane or epoxy resin-based coating. Preference is given to materials for radiation-cured coatings, in particular those based on acrylates.
• Radiation-cured coatings are preferably obtainable from coating compositions containing radiation-curable polymers and / or monomers.
• Suitable radiation-crosslinkable polymers are, in particular, those polymers which can be crosslinked by means of electromagnetic radiation, for example by means of UV, electron, X-ray or gamma rays, preferably by means of UV or electron radiation.
• Particularly preferred are polymers which carry ethylenically unsaturated groups which can be crosslinked by means of radiation.
• ethylenically unsaturated groups may be, for example, acrylate, methacrylate, vinyl ethers, allyl ethers and maleimide groups.
• Examples of preferred ethylenically unsaturated polymers include (meth) acrylated poly (meth) acrylates, polyurethane (meth) acrylates, polyester (meth) acrylates, polyether (meth) acrylates,
• Particularly preferred ethylenically unsaturated polymers are (meth) acrylated poly (meth) acrylates or polyurethane (meth) acrylates.
• Suitable radiation-crosslinkable monomers are in particular those monomers which can be crosslinked by means of electromagnetic radiation, for example by means of UV, electron, X-ray or gamma rays, preferably by means of UV or electron radiation. These are preferably unsaturated monomers. Unsaturated monomers may preferably be acrylates or methacrylates, preferably C 1 -C 20 -alkyl acrylates or C 1 -C 20 -alkyl methacrylates, vinylaromatics, preferably C 1 -C 20 -vinyl aromatics, for example styrene, vinyltoluene, ⁇ -butylstyrene or 4-n-butylstyrene.
• Vinyl esters of carboxylic acids preferably vinyl esters of C 1 -C 20 -carboxylic acids, such as vinyl laurate, vinyl stearate, vinyl propionate and vinyl acetate, vinyl ethers, preferably vinyl ethers of C 1 -C 20 -alcohols, such as vinylmethyl ether, vinyl isobutyl ether, vinylhexyl ether or vinyl octyl ether, unsaturated nitriles, such as acrylonitrile or methacrylonitrile, or an alkene having one or more double bonds, preferably one or two double bonds, preferably C 2 -C 20-alkenes having one or more double bonds, preferably one or two double bonds, such as, for example, ethylene, propylene, isobutylene, butadiene or isoprene.
• Suitable examples of such acrylates or methacrylates are methyl acrylate, ethyl acrylate, n-butyl acrylate, isobutyl acrylates, t-butyl acrylate, 2-ethylhexyl acrylate, isodecyl acrylate, n-lauryl acrylate, C 12 -C 15 Alkyl acrylates, n-
• acrylates and methacrylates are also suitable as acrylates and methacrylates.
• the coating composition used to coat the base film for such smoothing layers contains at least one suitable photoinitiator.
• the photoinitiator may also be covalently bonded to the crosslinkable polymer. Radiation-induced polymerization preferably takes place by means of radiation having a wavelength of 400 nm to 1 ⁇ m, for example UV, electron, X-ray or gamma rays.
• Suitable type (I) systems are aromatic ketone compounds, such as. B. benzophenones in combination with tertiary amines, alkylbenzophenones, 4,4'-bis (dimethylamino) benzophenone (Michler's ketone), anthrone and halogenated benzophenones or mixtures of the types mentioned.
• type (II) initiators such as benzoin and its derivatives, benzil ketals, acylphosphine oxides, 2,4,6-trimethylbenzoyl-diphenylphosphine oxide, bisacylphosphine oxides, phenylglyoxylic acid esters, camphorquinone, ⁇ -aminoalkylphenones, ⁇ , ⁇ -dialkoxyacetophenones and ⁇ -hydroxyalkylphenones , Preference is given to photoinitiators which are easy to incorporate into the aqueous dispersions.
• Such products are, for example, Irgacure® 500 (a mixture of benzophenone and (1-hydroxycyclohexyl) phenyl ketone, BASF SE, Ludwigshafen, DE), Irgacure® 819 DW (phenylbis- (2,4,6-trimethylbenzoyl) phosphine oxide, BASF SE, Ludwigshafen , DE), Esacure® KIP EM (Oligo) [2-hydroxy-2-methyl-1- [4- (1-methyl-vinyl) -phenyl] -propanone], from Lamberti, Aldizzate, Italy). It is also possible to use mixtures of these compounds.
• the zinc-tin oxide coating is preferably a permeation barrier layer for gases and vapors, more preferably oxygen, nitrogen and / or water vapor, most preferably oxygen and / or water vapor, most preferably oxygen and water vapor.
• An antireflection coating may preferably be applied to the outermost or to the coating of zinc-tin oxide in the film coated according to the invention.
• Such an antireflection coating can additionally increase the transmission of the plastic substrates coated according to the invention, preferably plastic films.
• layers are known to the person skilled in the art. These may be, for example, layers of low refractive index materials, such as e.g. S1O2, MgF2, etc., to complex multilayer constructions in which thin layers of materials with different refractive indices alternate, or layers with a refractive index gradient.
• the plastic substrates coated according to the invention, preferably plastic films have a transmission in the visible spectral range of more than 75%, particularly preferably more than 80%. With very particular preference, the plastic substrates coated according to the invention can also have a transmission in the visible spectral range of more than 85%, preferably even more than 90%, in particular in combination with an additional antireflection layer.
• the plastic substrates coated according to the invention preferably plastic films, preferably have an oxygen permeability of less than 0.5 cm 3 / m 2 / day, more preferably less than 0.1 cm 3 / m 2 / day and / or a water vapor permeability of less than 0, 1 g / m 2 / day, more preferably less than 0.01 g / m 2 / day.
• the plastic substrates coated according to the invention preferably plastic films, can be produced in a simple process without additional complicated post-treatment steps. In particular, continuous process control via a roll-to-roll process is possible.
• the present invention further provides a process for producing a plastic substrate coated according to the invention, preferably a coated plastic film, wherein at least one coating of zinc-tin oxide is applied to a plastic substrate, preferably a plastic film by means of a sputtering process in a vacuum, characterized in that Process gas contains hydrogen.
• Process gas contains hydrogen.
• the target (electrodes) for the sputtering process are preferably those of an alloy containing at least zinc and tin or at least containing zinc-tin oxide. In the case of using a zinc-zinc oxide target, this may also contain other additives, such as nitrogen, in small amounts.
• the process gas during production in the sputtering process contains at least one noble gas, preferably argon.
• the process gas preferably additionally contains oxygen.
• Oxygen is required in the process gas in particular if the target is one of an alloy containing zinc and tin, preferably one of an alloy containing primarily zinc and tin.
• the process according to the invention is carried out continuously. In this case, the preparation can be carried out particularly preferably in a simple roll-to-roll process (cf., for example, FIG. 1).
• Fig. 1 shows a schematic diagram of an arrangement for carrying out such a roll-to-roll method.
• sputtering methods all common and known methods can be used, such as e.g. DC sputtering (DC sputtering), radio frequency sputtering (RF sputtering), ion beam sputtering, magnetron sputtering, or reactive sputtering.
• Zinc-tin oxide layers are preferably produced by means of DC sputtering from the metallic target.
• a Doppelmagnetronan Aunt is selected, which increases the process stability.
• the system is particularly preferably operated with a direct current pulsed between 10 and 100 kHz.
• RF sputtering is also possible.
• the sputtering of a ceramic zinc-tin-oxide target is possible.
• the geometry of the targets used is largely variable. Planar rectangle targets can be used. Also so-called tube targets can be used. This ensures an increased process life.
• the permeation barrier coatings according to the invention or the plastic substrates coated according to the invention are suitable both for the production of packaging materials and, due to their optical properties, for the production of electronic devices, in particular flexible electronic devices.
• the present invention accordingly furthermore relates to the use of the permeation barrier coatings according to the invention or the plastic substrates coated according to the invention for the production of packaging materials or for the production of electronic devices, preferably flexible electronic devices.
• the packaging materials may be those for the packaging of foods or those for the packaging of oxygen and / or water-sensitive technical goods, such as solar cells, thin-film solar cells, lithium-based thin-film batteries, organic light-emitting diodes, transparent optionally vacuum-insulated panels, planar organic Lighting elements, LCD displays, TFT displays, etc., act
• the present invention furthermore relates to an electronic device, preferably a flexible electronic device comprising at least one plastic substrate coated according to the invention or at least one permeation barrier coating according to the invention.
• Electronic devices in particular flexible electronic devices, may be, for example, e-readers, LCD screens, LCD televisions, OLED displays and illuminants, touchpads, PDAs, mobile telephones, etc.
• ZTO layers were sputtered in a layer thickness of 70 nm and 115 nm, each on a polycarbonate substrate without hydrogen contained in the process gas, wherein the process gas from 130 sccm oxygen and 200 sccm argon was.
• a ZTO layer of thickness 110 nm and a ZTO layer of thickness 70 nm were respectively in
• the optical transmission T v i s and the layer absorption Abiau were determined.
• the optical spectral measurement was carried out by means of a Lambda 900 spectrometer from PerkinElmer (measuring range 350-800 nm, measurement of the transmission and reflection including the substrate, integration sphere used (integrating sphere), absorption calculated by means of transmission and reflection, corrected for the absorption of the substrate)
• the calculation of the optical transmission T v i s was carried out on the basis of the determination of the light transmittance Xv according to DIN EN 410 without including the spectral distribution of the
• the calculation of the layer absorption Abi au was carried out as an average value of the absorption spectrum corrected for the substrate influence in the wavelength range from 380 to 430 nm.
• the absorption coefficient is then calculated as follows
• 35 sccm H2 in the process gas correspond to 10.6% by volume H2 in the process gas

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• 2013
  • 2013-05-28 KR KR20147036037A patent/KR20150023451A/ko not_active Application Discontinuation
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