WO2009017376A2 - Process for manufacturing multi-layered thin film by dry vacuum vapor deposition - Google Patents
Process for manufacturing multi-layered thin film by dry vacuum vapor deposition Download PDFInfo
- Publication number
- WO2009017376A2 WO2009017376A2 PCT/KR2008/004470 KR2008004470W WO2009017376A2 WO 2009017376 A2 WO2009017376 A2 WO 2009017376A2 KR 2008004470 W KR2008004470 W KR 2008004470W WO 2009017376 A2 WO2009017376 A2 WO 2009017376A2
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- coating
- group
- vapor
- deposition layer
- thin film
- Prior art date
Links
- 238000007740 vapor deposition Methods 0.000 title claims abstract description 124
- 238000000034 method Methods 0.000 title claims abstract description 68
- 239000010409 thin film Substances 0.000 title claims abstract description 54
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 27
- 230000003287 optical effect Effects 0.000 claims abstract description 44
- 239000011248 coating agent Substances 0.000 claims description 110
- 238000000576 coating method Methods 0.000 claims description 105
- 239000010410 layer Substances 0.000 claims description 80
- 239000011247 coating layer Substances 0.000 claims description 46
- 239000000758 substrate Substances 0.000 claims description 37
- 229910052751 metal Inorganic materials 0.000 claims description 15
- 239000002184 metal Substances 0.000 claims description 15
- 238000009501 film coating Methods 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 11
- -1 acryl Chemical group 0.000 claims description 9
- 238000010894 electron beam technology Methods 0.000 claims description 9
- 238000010438 heat treatment Methods 0.000 claims description 9
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
- 239000000463 material Substances 0.000 claims description 7
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 7
- 229920000139 polyethylene terephthalate Polymers 0.000 claims description 7
- 239000005020 polyethylene terephthalate Substances 0.000 claims description 7
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 7
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical group [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 claims description 6
- 125000003172 aldehyde group Chemical group 0.000 claims description 6
- 125000003277 amino group Chemical group 0.000 claims description 6
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 claims description 6
- 150000001875 compounds Chemical class 0.000 claims description 6
- 125000001033 ether group Chemical group 0.000 claims description 6
- 125000000524 functional group Chemical group 0.000 claims description 6
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 6
- 125000000468 ketone group Chemical group 0.000 claims description 6
- 125000002467 phosphate group Chemical group [H]OP(=O)(O[H])O[*] 0.000 claims description 6
- 229910001512 metal fluoride Inorganic materials 0.000 claims description 4
- 150000004767 nitrides Chemical class 0.000 claims description 4
- 239000004417 polycarbonate Substances 0.000 claims description 4
- 229920000515 polycarbonate Polymers 0.000 claims description 4
- 239000011521 glass Substances 0.000 claims description 3
- NBVXSUQYWXRMNV-UHFFFAOYSA-N fluoromethane Chemical compound FC NBVXSUQYWXRMNV-UHFFFAOYSA-N 0.000 claims description 2
- 238000007733 ion plating Methods 0.000 claims description 2
- 238000004544 sputter deposition Methods 0.000 claims description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 2
- 229910052799 carbon Inorganic materials 0.000 claims 2
- 229920000122 acrylonitrile butadiene styrene Polymers 0.000 claims 1
- 238000005019 vapor deposition process Methods 0.000 description 17
- 230000000694 effects Effects 0.000 description 8
- 238000001035 drying Methods 0.000 description 7
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 7
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 6
- 238000000151 deposition Methods 0.000 description 6
- 238000009834 vaporization Methods 0.000 description 6
- 230000008016 vaporization Effects 0.000 description 6
- 238000011109 contamination Methods 0.000 description 5
- 150000003839 salts Chemical class 0.000 description 5
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- ATJFFYVFTNAWJD-UHFFFAOYSA-N Tin Chemical compound [Sn] ATJFFYVFTNAWJD-UHFFFAOYSA-N 0.000 description 4
- 238000005299 abrasion Methods 0.000 description 4
- VKJLWXGJGDEGSO-UHFFFAOYSA-N barium(2+);oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[O-2].[Ti+4].[Ba+2] VKJLWXGJGDEGSO-UHFFFAOYSA-N 0.000 description 4
- RHZWSUVWRRXEJF-UHFFFAOYSA-N indium tin Chemical compound [In].[Sn] RHZWSUVWRRXEJF-UHFFFAOYSA-N 0.000 description 4
- 150000002500 ions Chemical class 0.000 description 4
- CPLXHLVBOLITMK-UHFFFAOYSA-N magnesium oxide Inorganic materials [Mg]=O CPLXHLVBOLITMK-UHFFFAOYSA-N 0.000 description 4
- 239000000395 magnesium oxide Substances 0.000 description 4
- AXZKOIWUVFPNLO-UHFFFAOYSA-N magnesium;oxygen(2-) Chemical compound [O-2].[Mg+2] AXZKOIWUVFPNLO-UHFFFAOYSA-N 0.000 description 4
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 4
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 4
- 229910052814 silicon oxide Inorganic materials 0.000 description 4
- 239000002356 single layer Substances 0.000 description 4
- 229910001928 zirconium oxide Inorganic materials 0.000 description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000004676 acrylonitrile butadiene styrene Substances 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 229920006026 co-polymeric resin Polymers 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 238000001746 injection moulding Methods 0.000 description 3
- 238000001020 plasma etching Methods 0.000 description 3
- 239000004925 Acrylic resin Substances 0.000 description 2
- 229920000178 Acrylic resin Polymers 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- 229910000831 Steel Inorganic materials 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- YRKCREAYFQTBPV-UHFFFAOYSA-N acetylacetone Chemical compound CC(=O)CC(C)=O YRKCREAYFQTBPV-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 238000004140 cleaning Methods 0.000 description 2
- 239000003086 colorant Substances 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 238000003912 environmental pollution Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- BDVZHDCXCXJPSO-UHFFFAOYSA-N indium(3+) oxygen(2-) titanium(4+) Chemical compound [O-2].[Ti+4].[In+3] BDVZHDCXCXJPSO-UHFFFAOYSA-N 0.000 description 2
- 238000002347 injection Methods 0.000 description 2
- 239000007924 injection Substances 0.000 description 2
- 229910010272 inorganic material Inorganic materials 0.000 description 2
- 239000011147 inorganic material Substances 0.000 description 2
- 229910001635 magnesium fluoride Inorganic materials 0.000 description 2
- 229910052759 nickel Inorganic materials 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- 239000005871 repellent Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 239000000243 solution Substances 0.000 description 2
- 239000010959 steel Substances 0.000 description 2
- 238000005728 strengthening Methods 0.000 description 2
- 239000010936 titanium Substances 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 239000013043 chemical agent Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 1
- 238000007641 inkjet printing Methods 0.000 description 1
- 238000010884 ion-beam technique Methods 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000007639 printing Methods 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004528 spin coating Methods 0.000 description 1
- 238000009987 spinning Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/32—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer
- C23C28/322—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one pure metallic layer only coatings of metal elements only
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/30—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer
- C23C28/34—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates
- C23C28/345—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer
- C23C28/3455—Coatings combining at least one metallic layer and at least one inorganic non-metallic layer including at least one inorganic non-metallic material layer, e.g. metal carbide, nitride, boride, silicide layer and their mixtures, enamels, phosphates and sulphates with at least one oxide layer with a refractory ceramic layer, e.g. refractory metal oxide, ZrO2, rare earth oxides or a thermal barrier system comprising at least one refractory oxide layer
-
- 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
- C23C28/00—Coating for obtaining at least two superposed coatings either by methods not provided for in a single one of groups C23C2/00 - C23C26/00 or by combinations of methods provided for in subclasses C23C and C25C or C25D
- C23C28/40—Coatings including alternating layers following a pattern, a periodic or defined repetition
- C23C28/42—Coatings including alternating layers following a pattern, a periodic or defined repetition characterized by the composition of the alternating layers
Definitions
- the present invention relates to a process for manufacturing multi-layered thin film by using dry vacuum vapor deposition, in particular, a process for manufacturing multi- layered thin film by using stable and simple dry vacuum vapor deposition, the process being capable of providing optical beautifulness and luxury impression to cases, windows, keypads, function key parts, various accessory parts and the like for portable electronic products such as mobile phone, MP3 player, portable multimedia player (PMP), digital multimedia broadcasting (DMB) receiver, car navigation system, notebook computer, etc. and display products.
- portable electronic products such as mobile phone, MP3 player, portable multimedia player (PMP), digital multimedia broadcasting (DMB) receiver, car navigation system, notebook computer, etc. and display products.
- Portable electronic products such as mobile phone, MP3 player, portable multimedia player (PMP), digital multimedia broadcasting (DMB) receiver, car navigation system, notebook computer, etc. and display products such as monitor, touchscreen, etc. use cases, windows, keypads, function key parts, various accessory parts or the like which are in sheet-type panel form or injection molding article made out of metal, glass, acryl (acrylic resin), polycarbonate (PC), poly methyl methacrylate (PMMA), polyethylene terephthalate (PET), acrylonitrile butadiene styrene (ABS) copolymer resin and combinations thereof.
- vacuum vapor deposition coating with using metal and/or metal oxide is performed for providing optical beautifulness and luxury impression.
- a non-conductive, dielectric thin film coating is formed on the front side and rear side of the case, window, keypad, window-integrated case, etc. thereof, by vacuum vapor deposition process with using metal oxide in stead of metal.
- the thin film of metal and/or metal oxide coated by vacuum vapor deposition process has low adhesion strength to the substrate, it shows low abrasion resistance, scratch resistance and pencil hardness, and it is hard to guarantee the reliability because the thin film of vacuum vapor deposition is detached by high temperature, high humidity and salt water.
- UV coating or hard coating is performed by wet process such as dipping, spraying, spinning, inkjet printing, etc. before and after the vapor deposition process.
- a bottom coating and a top coating should be performed for the adhesion strength and stability of the vapor deposition layer, by using a separate wet process such as dipping method, spray method, spin-coating method, ink printing method or the like.
- a separate wet process such as dipping method, spray method, spin-coating method, ink printing method or the like.
- the wet process and the vacuum vapor deposition process (dry process) are performed in an alternating manner due to the introduction of the wet process, and thus the processing time for coating the parts becomes longer because the conveyance between the different processes and the mounting and demounting of coating object in each process should be done repeatedly.
- the productivity is lowered because of the processing inferiority which is occurred during the performances of the different processes and the high inferiority rate which is occurred during the conveyance between the different processes, and increased production time due to the many processes, which in turn results in high production cost of the product.
- the coating film 60 prepared on a surface of the product 10 through wet process is thicker, as compared with the coating film 70 prepared through vacuum vapor deposition process (dry process), by hundreds to thousands times and thus the unique properties of the substrate cannot be made to the best thereof due to the decrease of optical characteristics and deterioration of surface texture of the substrate.
- the object of the present invention is to provide a process for manufacturing multi-layered thin film by forming a stable vacuum vapor deposition thin film on the front side and rear side of the case, window, keypad, function key part, window-integrated case and various accessory substrates of electronic products even through dry vacuum vapor deposition procedures as minimum as required in a vacuum vapor deposition device, the process being capable of providing beautiful and luxury optical design to portable electronic products and display products and guaranteeing a reliability of the products.
- the other object of the present invention is to obtain effects of eliminating or reducing environmental pollution by eliminating or minimizing the environmentally- problematic wet processes, as well as cost-saving effects from the reductions of production time and inferiority by guaranteeing the reliability of the thin film even with simplifying the process as minimum as required.
- a process for manufacturing multi-layered thin film comprising the steps of forming a bottom-coating vapor-deposition layer on a substrate and forming an optical coating layer on the bottom-coating vapor-deposition layer where the bottom-coating vapor-deposition layer is to provide adhesion strength between the substrate and the optical coating layer, wherein the formation of the multi-layered thin film is performed by dry vacuum vapor deposition, is provided.
- the process of the present invention preferably further comprises a step of forming a middle-coating vapor-deposition layer after the step of forming the optical coating layer.
- the process of the present invention preferably further comprises a step of forming a top-coating vapor-deposition layer, after the step of forming the middle-coating vapor- deposition layer or after the step of forming the optical coating layer.
- a multi-layered thin film coating which is formed by the process for manufacturing multi-layered thin film of the present invention and comprises a bottom-coating vapor-deposition layer formed on a substrate and an optical coating layer formed on the bottom-coating vapor-deposition layer, is provided.
- the multi-layered thin film coating of the present invention preferably further comprises a middle-coating vapor-deposition layer formed on the optical coating layer.
- the multi-layered thin film coating of the present invention preferably further comprises a top-coating vapor-deposition layer formed on the middle-coating vapor-deposition layer.
- the multi-layered thin film coating of the present invention preferably further comprises a top-coating vapor-deposition layer formed on the optical coating layer.
- an electronic product comprising the multi-layered thin film coating formed by the process for manufacturing multi- layered thin film of the present invention.
- the dry vacuum vapor deposition process for manufacturing multi-layered thin film of the present invention is used to coat the case, window, window-integrated case, keypad, keypad-integrated window, function key parts, various accessory parts and the like of portable electronic products such as mobile phone, MP3 player, portable multimedia player (PMP), digital multimedia broadcasting (DMB) receiver, car navigation system, notebook computer, etc. and display products such as monitor, touchscreen, etc. and electronic home appliances such as refrigerator, air conditioner, television, etc.
- portable electronic products such as mobile phone, MP3 player, portable multimedia player (PMP), digital multimedia broadcasting (DMB) receiver, car navigation system, notebook computer, etc. and display products such as monitor, touchscreen, etc. and electronic home appliances such as refrigerator, air conditioner, television, etc.
- the effects of eliminating or reducing environmental pollution by eliminating or minimizing the environmentally-problematic wet processes can be obtained, as well as the cost-saving effects from the reductions of production time and inferiority by guaranteeing the reliability of the thin film even with simplifying the process as minimum as required.
- Figure 1 is a process diagram for an embodiment of the vacuum vapor deposition process for manufacturing multi-layered thin film of the present invention.
- Figure 2 is a schematic constitution of the multi-layered thin film of vacuum vapor deposition manufactured according to an embodiment of the present invention.
- Figure 3 is a drawing to represent the relationship between adhesion strength and surface contact angle.
- Figure 4 is a drawing to compare the thicknesses of bottom and top coating layers formed by a conventional wet process with those formed by the vacuum vapor deposition process of the present invention.
- Figure 5 is a photograph showing a contact angle of the surface of a plastic in-mold injection product.
- Figure 6 is a photograph showing a contact angle of the surface after the vacuum vapor deposition of bottom coating in manufacturing the multi-layered thin film according to an embodiment of the present invention.
- Figure 7 is a photograph showing a contact angle of the surface after completing the vacuum vapor deposition of top coating in manufacturing the multi-layered thin film according to an embodiment of the present invention.
- Substrate 20 Bottom-coating vapor-deposition layer 30: Optical coating layer 40: Middle-coating vapor-deposition layer 50: Top-coating vapor-deposition layer 60: Coating layer according to a conventional wet process 70: Multi-layered thin film of vacuum vapor deposition according to the dry process of the present invention
- the vacuum vapor deposition process for manufacturing thin film of the present invention is characterized in that the coating layers are formed in a vacuum vapor deposition device by dry process, as compared with conventional coating layers provided by wet process.
- the conventional coating layers provided by wet process so far may include for example, UV (ultraviolet) hardening type coating layers, bottom coating layers for increasing adhesion strength between substrate and optical coating layer, and top coating layers for protecting optical single- or multi-layered coating.
- the stable single- or multi-layered coating is provided by the ultra-thin coating method with the chemical agents for the formation of respective thin film layer in a vacuum vapor deposition device, preferably with using the carrier as described in Korean patent application No. 10-2007-0075000.
- Suitable substrates to which the process for manufacturing thin film of the present invention can be applied includes, but not limited thereto, cases, windows, window- integrated cases, keypads, keypad-integrated windows, function key parts and various accessory parts for portable electronic products such as mobile phone, MP3 player, portable multimedia player (PMP), digital multimedia broadcasting (DMB) receiver, car navigation system, notebook computer, etc. and display products such as monitor, touchscreen, etc.
- the substrates can be in a sheet-type panel form or various injection molding article forms, but not limited thereto.
- acryl acrylic resin
- PC polycarbonate
- PMMA poly methyl methacrylate
- PET polyethylene terephthalate
- ABS acrylonitrile butadiene styrene copolymer resin
- the bottom-coating vapor-deposition layer formed on the substrate is a layer for providing adhesion strength between the substrate and an optical coating layer to be formed subsequently.
- the bottom-coating vapor-deposition layer is formed to have nano-scale thin thickness of 10 A to 1,000 A (1 nm to 100 nm), and acts as so-called “nano primer” to increase the adhesion strength between the surface of the substrate and an optical single- or multi-coating layer to be formed in the subsequent step.
- the bottom-coating vapor-deposition layer can be deposited with a thickness of 10 A to 1,000 A by plasma-assisted vapor deposition method (ion assist) in the vacuum vapor deposition process, and thus can show hard coating characteristics and improve adhesion characteristics of the thin film vapor-deposition layer.
- carbon- based compounds having one or more functional groups selected from carboxyl group, phosphate group, silane group, amine group, hydroxyl group, aldehyde group, ketone group, ether group and ketal group can be used, and the molecular weight thereof can be 100 to 10,000 but not limited thereto.
- the optical coating layer formed on the bottom-coating vapor-deposition layer can be a single- or multi- layer and can provide beautiful and luxury optical design, various colors and effect of mirror or anti-mirror image to the external appearance of the product, i.e. the substrate.
- metal such as SUS (Steel Use Stainless), nickel (Ni), aluminum (Al), chrome (Cr), tin (Sn), indium-tin (In-Sn) and the like; metal oxide such as silicon oxide (SiO 2 ), titanium oxide (TiO 2 ), aluminum oxide (Al 2 O 3 ), zirconium oxide (ZrO 2 ), indium titanium oxide (In x Ti 7 O 2 , ITO), barium titanium oxide (BaTiO 3 ), magnesium oxide (MgO) and the like; metal nitride such as SiN, TiN and the like; or metal fluoride such as MgF 2 and the like can be used.
- SUS Steel Use Stainless
- Ni nickel
- Al aluminum
- Cr chrome
- tin (Sn) indium-tin
- In-Sn indium-tin
- metal oxide such as silicon oxide (SiO 2 ), titanium oxide (TiO 2 ), aluminum oxide (Al 2 O 3 ), zircon
- These materials are vaporized and deposited as a single layer or in an alternating manner to form a multilayer by using electron beam or resistance-heating device in a vacuum vapor deposition device.
- the thickness of the optical coating layer There is no special limitation to the thickness of the optical coating layer.
- it can be formed in a single layer or multilayer of the single layer having thickness variously, for example, in a range from nano-scale thickness of 10 A - 1,000 A (1 nm - 100 nm) to the thickness of micrometers.
- a middle-coating vapor-deposition layer can be formed further on the surface.
- the middle-coating vapor-deposition layer plays a role of strengthening salt water resistance, abrasion resistance, scratch resistance and the like and assists the functions of additionally formable top-coating vapor-deposition layer.
- the middle-coating vapor-deposition layer can be deposited with a thickness of 10 A to 1,000 A by plasma-assisted vapor deposition method (ion assist) in the vacuum vapor deposition process, and thus can strengthen the weak scratch resistance, salt water resistance, etc. of the thin film vapor-deposition layer.
- carbon- based compounds having one or more functional groups selected from carboxyl group, phosphate group, silane group, amine group, hydroxyl group, aldehyde group, ketone group, ether group and ketal group can be used, and the molecular weight thereof can be 100 to 10,000 but not limited thereto.
- a top-coating vapor-deposition layer can be formed further on the surface.
- the top-coating vapor-deposition layer plays a role of protecting the optical coating layer by providing contamination resistance
- the top-coating vapor-deposition layer can be deposited with a thickness of 10 A to 1,000 A by plasma-assisted vapor deposition method (ion assist) in the vacuum vapor deposition process.
- fluorocarbon-based compounds having one or more functional groups selected from carboxyl group, phosphate group, silane group, amine group, hydroxyl group, aldehyde group, ketone group, ether group and ketal group can be used, and the molecular weight thereof can be 100 to 10,000 but not limited thereto.
- the coating agents for the formation of respective thin film layer can be deposited by using electron beam, resistance-heating device, sputtering device or ion plating device, preferably with using the carrier as described in Korean patent application No. 10-2007-0075000.
- the formation of the multi-layered thin film structure proceeds continuously in a vacuum vapor deposition device.
- the coating agents for the formation of respective thin film layer preferably comprise a solvent such as water, methanol, ethanol, acetone, acetyl acetone, glycol, ketone or the like for the storage and stability of the agents.
- FIG. 1 An embodiment of the process for manufacturing multi-layered thin film of vacuum vapor deposition according to the present invention is the same as shown in Figure 1.
- the present invention is characterized in that all coating operations from the mounting to the demounting of the substrate, i.e. the product, in a vacuum vapor deposition device are performed through dry process in the vacuum vapor deposition device.
- the mounting step The substrate (or product) 10 such as case, window, window-integrated case, keypad, keypad-integrated window, function key part and various accessory part for portable electronic products such as mobile phone, MP3 player, portable multimedia player (PMP), digital multimedia broadcasting (DMB) receiver, car navigation system, notebook computer, etc. and display products such as monitor, touchscreen, etc. is mounted in a vacuum vapor deposition device.
- a vacuum vapor deposition device To prevent the substrate from falling off during the vacuum vapor deposition process, the substrate is installed to a jig which is designed so as to fit the substrate in various forms.
- the inside of vacuum vapor deposition chamber is evacuated to maintain a high-vacuum state of 1.
- OxIO "6 - 1.OxIO "3 torr preferably a high-vacuum state of 1.
- OxIO "5 torr or higher vacuum in order to perform the vacuum vapor deposition coating with metal and/or metal oxide.
- the temperature of the inside of vacuum vapor deposition chamber is set to 20 to 300 ° C depending on the material of the mounted substrate 10.
- high voltage discharge is conducted by using ion beam device under the flow of argon (Ar), nitrogen (N 2 ) and oxygen (O 2 ) gases to generate plasma of the corresponding gas.
- the plasma gas with high energy is applied for 10 seconds to 1,000 seconds depending on the condition of the surface of the mounted substrate, to activate the surface of the mounted substrate 10 (plasma etching).
- the bottom-coating vapor-deposition layer 20 is formed on the activated surface of the substrate 10.
- the carrier as described in Korean patent application No. 10-2007-0075000 can be used.
- the agent for the bottom-coating is loaded in this carrier and in turn the carrier is installed to a vaporization port using electron beam or a resistance-heating type vaporization port in the vacuum vapor deposition device, and then the carrier installed to the vaporization port is heated by using electron beam or resistance-heating boat to vaporize the coating agent loaded in the carrier, and the bottom-coating vapor-deposition layer is formed.
- IC-5 is one of the control devices for vacuum vapor deposition devices.
- the power of electron beam is controlled suitably between 1.5 % and 8.0 %, preferably between 2.0 % and 4.0 %.
- the bottom-coating vapor-deposition layer formed as above preferably has a thickness of 10 A to 1,000 A (0.001 ⁇ m to 0.1 ⁇ m), most preferably about 100 A (0.01 ⁇ m, 10 nm) or more or less.
- the plasma etching as described above can be applied thereto for 0 to 300 seconds, by which the bottom-coating vapor-deposition layer can be stabilized.
- the coating formed on the surface of the substrate is associated with the surface energy.
- the strength of adhesion can be estimated by measuring the contact angle between the substrate and water drop on the surface of the substrate, as shown in Figure 3. As the contact angle becomes smaller, the adhesion strength becomes greater.
- the contact angle on the surface of the substrate before the coating was 74.3° ( Figure 5) whereas the contact angle decreased to 32.2° after the formation of the bottom-coating vapor-deposition layer 20 on the surface of the product ( Figure 6), and before and after the bottom-coating vapor deposition, the surface energy was changed from 33.02 niN/m to 47.98 mN/m. That is, the adhesion strength was improved by the bottom-coating vapor deposition.
- the optical coating layer 30 is formed on the bottom-coating vapor-deposition layer for providing beautiful and luxury optical design to the substrate, and showing various colors, effect of mirror or anti-mirror image, and antireflection effect.
- the optical coating layer 30 is formed by vapor-depositing metal such as SUS (Steel Use Stainless), nickel (Ni), aluminum (Al), chrome (Cr), tin (Sn), indium-tin (In-Sn) and the like; metal oxide such as silicon oxide (SiO 2 ), titanium oxide (TiO 2 ), aluminum oxide (Al 2 O 3 ), zirconium oxide (ZrO 2 ), indium titanium oxide (In x Ti y O 2 , ITO), barium titanium oxide (BaTiO 3 ), magnesium oxide (MgO) and the like; metal nitride such as SiN, TiN and the like; or metal fluoride such as MgF 2 and the like, in a single layer or multilayer through alternating vapor deposition, by using electron beam or resistance- heating device in a vacuum vapor deposition device.
- metal oxide such as silicon oxide (SiO 2 ), titanium oxide (TiO 2 ), aluminum oxide (Al 2 O 3 ), zircon
- the optical coating layer 30 is formed from metal, metal oxide, metal nitride or metal fluoride, it has various surface characteristics and a vulnerability to moisture and contamination, etc. due to the features of inorganic materials. Therefore, on the optical coating layer 30, the middle-coating vapor-deposition layer 40 is preferably formed with a thickness of about 100 A or more or less, in order to provide a surface which is stable to various environments and to strengthen the abrasion resistance and reliability of the vacuum vapor deposition thin film resisting to the environment, according to different surface conditions.
- the middle-coating vapor-deposition layer 40 can be deposited by plasma-assisted vapor deposition method (ion assist) in the vacuum vapor deposition process, and thus can exhibit hard coating characteristics and strengthen the weak scratch resistance, salt water resistance, etc. of the thin film vapor-deposition layer.
- the carrier as described in Korean patent application No. 10-2007-0075000 can be used to form the middle-coating vapor-deposition layer, as the same for the bottom-coating vapor-deposition layer.
- the agent for the middle-coating is loaded in this carrier and in turn the carrier is installed to a vaporization port using electron beam or a resistance- heating type vaporization port in the vacuum vapor deposition device, and then the carrier installed to the vaporization port is heated by using electron beam or resistance- heating boat to vaporize the coating agent loaded in the carrier, and the middle-coating vapor-deposition layer is formed.
- the middle-coating vapor-deposition layer formed as above preferably has a thickness of 10 A to 1,000 A (0.001 ⁇ m to 0.1 ⁇ m), most preferably about 100 A (0.01 ⁇ m, 10 nm) or more or less.
- the plasma etching as described above can be applied thereto for 0 to 300 seconds, by which the middle-coating vapor-deposition layer can be stabilized.
- the top-coating vapor-deposition layer 50 is preferably provided over the optical coating layer 30 directly or with the intervention of the middle-coating vapor- deposition layer 40.
- the top-coating vapor-deposition layer 50 can be formed by a method similar with the bottom- and middle-coating vapor-deposition layers, in a thickness of 100 A to 1,000 A, without controlling the coating thickness specially.
- the thin film coating formed through the top-coating vapor depositing step has a very low surface energy and a feature of low friction coefficient, thereby showing property of very slippery surface, and thus the attachment of contamination sources such as fingerprint and soil etc. can be reduced remarkably. Even though the fingerprint and soil are attached, they can be removed easily by the excellent easy cleaning function of the coating. Also, at the same time, characteristic properties such as water-repellent or oil-repellent property, scratch resistance, durability, etc. can be obtained, and thus a coating layer of vacuum vapor deposition which is stable after the test for reliability of a product having exterior coating as well as interior coating, can be formed.
- the coating surface having the top-coating vapor deposition layer treated as above is shown in Figure 7.
- the contact angle and surface energy when the top-coating vapor deposition layer is formed are shown in the following Tables 3 and 4, respectively.
- the product for which the manufacture of the multi-layered thin film is completed is taken out of the vacuum vapor deposition device.
- the present invention can be applied to cases, windows, window-integrated cases, keypads, keypad-integrated windows, function key parts, various accessories and the like of display and accessory parts used in portable electronic products such as mobile phone, MP3 player, portable multimedia player (PMP), digital multimedia broadcasting (DMB) receiver, car navigation system, notebook computer, etc. and display products such as monitor, touchscreen, etc. and electronic home appliances such as refrigerator,
Abstract
The present invention relates to a process for manufacturing multi-layered thin film by using dry vacuum vapor deposition, in particular, a process for manufacturing multi- layered thin film by using stable and simple dry vacuum vapor deposition, the process being capable of providing optical beautifulness and luxury impression to cases, windows, keypads, function key parts, various accessory parts or the like for mobile phone, MP3 player, portable multimedia player (PMP), digital multimedia broadcasting (DMB) receiver, car navigation system, notebook computer, etc.
Description
PROCESS FOR MANUFACTURING MULTI-LAYERED THIN FILM BY DRY VACUUM VAPOR DEPOSITION
TECHNICAL FIELD The present invention relates to a process for manufacturing multi-layered thin film by using dry vacuum vapor deposition, in particular, a process for manufacturing multi- layered thin film by using stable and simple dry vacuum vapor deposition, the process being capable of providing optical beautifulness and luxury impression to cases, windows, keypads, function key parts, various accessory parts and the like for portable electronic products such as mobile phone, MP3 player, portable multimedia player (PMP), digital multimedia broadcasting (DMB) receiver, car navigation system, notebook computer, etc. and display products.
BACKGROUND ART Portable electronic products such as mobile phone, MP3 player, portable multimedia player (PMP), digital multimedia broadcasting (DMB) receiver, car navigation system, notebook computer, etc. and display products such as monitor, touchscreen, etc. use cases, windows, keypads, function key parts, various accessory parts or the like which are in sheet-type panel form or injection molding article made out of metal, glass, acryl (acrylic resin), polycarbonate (PC), poly methyl methacrylate (PMMA), polyethylene terephthalate (PET), acrylonitrile butadiene styrene (ABS) copolymer resin and
combinations thereof. For such parts, vacuum vapor deposition coating with using metal and/or metal oxide is performed for providing optical beautifulness and luxury impression.
In case of mobile phone, particularly, for the stability of telecommunication quality, a non-conductive, dielectric thin film coating is formed on the front side and rear side of the case, window, keypad, window-integrated case, etc. thereof, by vacuum vapor deposition process with using metal oxide in stead of metal.
However, since the thin film of metal and/or metal oxide coated by vacuum vapor deposition process has low adhesion strength to the substrate, it shows low abrasion resistance, scratch resistance and pencil hardness, and it is hard to guarantee the reliability because the thin film of vacuum vapor deposition is detached by high temperature, high humidity and salt water.
Accordingly, to solve the problems in reliability and the like, UV coating or hard coating is performed by wet process such as dipping, spraying, spinning, inkjet printing, etc. before and after the vapor deposition process.
Particularly, if the vacuum vapor deposition process is introduced for providing optical design to a sheet-type panel form or injection molding article of acryl, polycarbonate
(PC), poly methyl methacrylate (PMMA), polyethylene terephthalate (PET), acrylonitrile butadiene styrene (ABS) copolymer resin or combinations thereof which is used for cases, windows, keypads, etc. of electronic products, a bottom coating and a top coating should be performed for the adhesion strength and stability of the vapor deposition layer, by using a separate wet process such as dipping method, spray method, spin-coating method, ink printing method or the like. In the case, however, since the wet process and the vacuum vapor deposition process are performed in an alternating manner, an extra cost due to the use of the different processes is incurred and a problem of inferiority occurrence during the conveyance between the different processes is caused.
That is, the wet process and the vacuum vapor deposition process (dry process) are performed in an alternating manner due to the introduction of the wet process, and thus the processing time for coating the parts becomes longer because the conveyance between the different processes and the mounting and demounting of coating object in each process should be done repeatedly.
Also, the productivity is lowered because of the processing inferiority which is occurred during the performances of the different processes and the high inferiority rate which is occurred during the conveyance between the different processes, and increased production time due to the many processes, which in turn results in high production cost
of the product.
Further, there is a tendency that such structural problem becomes still worse when the company performing the wet coating is different from the company performing the vacuum vapor deposition.
Also, as shown in Figure 4, the coating film 60 prepared on a surface of the product 10 through wet process is thicker, as compared with the coating film 70 prepared through vacuum vapor deposition process (dry process), by hundreds to thousands times and thus the unique properties of the substrate cannot be made to the best thereof due to the decrease of optical characteristics and deterioration of surface texture of the substrate.
DETAILED DESCRIPTION OF THE INVENTION
TECHNICAL PURPOSE
As a solution to the above-mentioned problems of prior arts, the object of the present invention is to provide a process for manufacturing multi-layered thin film by forming a stable vacuum vapor deposition thin film on the front side and rear side of the case, window, keypad, function key part, window-integrated case and various accessory substrates of electronic products even through dry vacuum vapor deposition procedures as minimum as required in a vacuum vapor deposition device, the process being capable
of providing beautiful and luxury optical design to portable electronic products and display products and guaranteeing a reliability of the products.
Also, the other object of the present invention is to obtain effects of eliminating or reducing environmental pollution by eliminating or minimizing the environmentally- problematic wet processes, as well as cost-saving effects from the reductions of production time and inferiority by guaranteeing the reliability of the thin film even with simplifying the process as minimum as required.
TECHNICAL SOLUTION
According to the present invention, a process for manufacturing multi-layered thin film, comprising the steps of forming a bottom-coating vapor-deposition layer on a substrate and forming an optical coating layer on the bottom-coating vapor-deposition layer where the bottom-coating vapor-deposition layer is to provide adhesion strength between the substrate and the optical coating layer, wherein the formation of the multi-layered thin film is performed by dry vacuum vapor deposition, is provided.
The process of the present invention preferably further comprises a step of forming a middle-coating vapor-deposition layer after the step of forming the optical coating layer.
Also, the process of the present invention preferably further comprises a step of forming
a top-coating vapor-deposition layer, after the step of forming the middle-coating vapor- deposition layer or after the step of forming the optical coating layer.
According to the other aspect of the present invention, a multi-layered thin film coating which is formed by the process for manufacturing multi-layered thin film of the present invention and comprises a bottom-coating vapor-deposition layer formed on a substrate and an optical coating layer formed on the bottom-coating vapor-deposition layer, is provided.
The multi-layered thin film coating of the present invention preferably further comprises a middle-coating vapor-deposition layer formed on the optical coating layer.
The multi-layered thin film coating of the present invention preferably further comprises a top-coating vapor-deposition layer formed on the middle-coating vapor-deposition layer.
The multi-layered thin film coating of the present invention preferably further comprises a top-coating vapor-deposition layer formed on the optical coating layer.
According to another aspect of the present invention, an electronic product comprising the multi-layered thin film coating formed by the process for manufacturing multi-
layered thin film of the present invention, is provided.
ADVANTAGEOUS EFFECTS
If the dry vacuum vapor deposition process for manufacturing multi-layered thin film of the present invention is used to coat the case, window, window-integrated case, keypad, keypad-integrated window, function key parts, various accessory parts and the like of portable electronic products such as mobile phone, MP3 player, portable multimedia player (PMP), digital multimedia broadcasting (DMB) receiver, car navigation system, notebook computer, etc. and display products such as monitor, touchscreen, etc. and electronic home appliances such as refrigerator, air conditioner, television, etc., the reliability of the products can be guaranteed with providing beautiful and luxury optical designs therefor.
Also, the effects of eliminating or reducing environmental pollution by eliminating or minimizing the environmentally-problematic wet processes can be obtained, as well as the cost-saving effects from the reductions of production time and inferiority by guaranteeing the reliability of the thin film even with simplifying the process as minimum as required.
BRIEF DESCRIPTION OF THE DRAWINGS
Figure 1 is a process diagram for an embodiment of the vacuum vapor deposition
process for manufacturing multi-layered thin film of the present invention.
Figure 2 is a schematic constitution of the multi-layered thin film of vacuum vapor deposition manufactured according to an embodiment of the present invention.
Figure 3 is a drawing to represent the relationship between adhesion strength and surface contact angle.
Figure 4 is a drawing to compare the thicknesses of bottom and top coating layers formed by a conventional wet process with those formed by the vacuum vapor deposition process of the present invention.
Figure 5 is a photograph showing a contact angle of the surface of a plastic in-mold injection product.
Figure 6 is a photograph showing a contact angle of the surface after the vacuum vapor deposition of bottom coating in manufacturing the multi-layered thin film according to an embodiment of the present invention.
Figure 7 is a photograph showing a contact angle of the surface after completing the vacuum vapor deposition of top coating in manufacturing the multi-layered thin film
according to an embodiment of the present invention.
* Symbols shown in Figures 10: Substrate 20: Bottom-coating vapor-deposition layer 30: Optical coating layer 40: Middle-coating vapor-deposition layer 50: Top-coating vapor-deposition layer 60: Coating layer according to a conventional wet process 70: Multi-layered thin film of vacuum vapor deposition according to the dry process of the present invention
EMBODIMENT TO CARRY OUT THE INVENTION
The vacuum vapor deposition process for manufacturing thin film of the present invention is characterized in that the coating layers are formed in a vacuum vapor deposition device by dry process, as compared with conventional coating layers provided by wet process. The conventional coating layers provided by wet process so far may include for example, UV (ultraviolet) hardening type coating layers, bottom coating layers for increasing adhesion strength between substrate and optical coating layer, and top coating layers for protecting optical single- or multi-layered coating.
In the vacuum vapor deposition process (dry process) of the present invention, the stable single- or multi-layered coating is provided by the ultra-thin coating method with the chemical agents for the formation of respective thin film layer in a vacuum vapor deposition device, preferably with using the carrier as described in Korean patent application No. 10-2007-0075000.
Suitable substrates to which the process for manufacturing thin film of the present invention can be applied includes, but not limited thereto, cases, windows, window- integrated cases, keypads, keypad-integrated windows, function key parts and various accessory parts for portable electronic products such as mobile phone, MP3 player, portable multimedia player (PMP), digital multimedia broadcasting (DMB) receiver, car navigation system, notebook computer, etc. and display products such as monitor, touchscreen, etc. The substrates can be in a sheet-type panel form or various injection molding article forms, but not limited thereto.
Metal, glass, acryl (acrylic resin), polycarbonate (PC), poly methyl methacrylate (PMMA), polyethylene terephthalate (PET), acrylonitrile butadiene styrene (ABS) copolymer resin and combinations thereof can be used as the material of the substrate, but not limited thereto.
In the process for manufacturing thin film of the present invention, the bottom-coating
vapor-deposition layer formed on the substrate is a layer for providing adhesion strength between the substrate and an optical coating layer to be formed subsequently. Preferably, the bottom-coating vapor-deposition layer is formed to have nano-scale thin thickness of 10 A to 1,000 A (1 nm to 100 nm), and acts as so-called "nano primer" to increase the adhesion strength between the surface of the substrate and an optical single- or multi-coating layer to be formed in the subsequent step.
Also, according to surface characteristics of the substrate and multilayer design of the optical coating layer, the bottom-coating vapor-deposition layer can be deposited with a thickness of 10 A to 1,000 A by plasma-assisted vapor deposition method (ion assist) in the vacuum vapor deposition process, and thus can show hard coating characteristics and improve adhesion characteristics of the thin film vapor-deposition layer.
Preferably, as coating agents to form the bottom-coating vapor-deposition layer, carbon- based compounds having one or more functional groups selected from carboxyl group, phosphate group, silane group, amine group, hydroxyl group, aldehyde group, ketone group, ether group and ketal group can be used, and the molecular weight thereof can be 100 to 10,000 but not limited thereto.
In the process for manufacturing thin film of the present invention, the optical coating layer formed on the bottom-coating vapor-deposition layer can be a single- or multi-
layer and can provide beautiful and luxury optical design, various colors and effect of mirror or anti-mirror image to the external appearance of the product, i.e. the substrate.
As a material to form the optical coating layer, metal such as SUS (Steel Use Stainless), nickel (Ni), aluminum (Al), chrome (Cr), tin (Sn), indium-tin (In-Sn) and the like; metal oxide such as silicon oxide (SiO2), titanium oxide (TiO2), aluminum oxide (Al2O3), zirconium oxide (ZrO2), indium titanium oxide (InxTi7O2, ITO), barium titanium oxide (BaTiO3), magnesium oxide (MgO) and the like; metal nitride such as SiN, TiN and the like; or metal fluoride such as MgF2 and the like can be used. These materials are vaporized and deposited as a single layer or in an alternating manner to form a multilayer by using electron beam or resistance-heating device in a vacuum vapor deposition device. There is no special limitation to the thickness of the optical coating layer. For example, it can be formed in a single layer or multilayer of the single layer having thickness variously, for example, in a range from nano-scale thickness of 10 A - 1,000 A (1 nm - 100 nm) to the thickness of micrometers.
According to one preferable embodiment of the present invention, after the step of forming the optical coating layer, a middle-coating vapor-deposition layer can be formed further on the surface. The middle-coating vapor-deposition layer plays a role of strengthening salt water resistance, abrasion resistance, scratch resistance and the like and assists the functions of additionally formable top-coating vapor-deposition layer.
According to surface characteristics of the optical coating layer and the multilayer design, the middle-coating vapor-deposition layer can be deposited with a thickness of 10 A to 1,000 A by plasma-assisted vapor deposition method (ion assist) in the vacuum vapor deposition process, and thus can strengthen the weak scratch resistance, salt water resistance, etc. of the thin film vapor-deposition layer.
Preferably, as coating agents to form the middle-coating vapor-deposition layer, carbon- based compounds having one or more functional groups selected from carboxyl group, phosphate group, silane group, amine group, hydroxyl group, aldehyde group, ketone group, ether group and ketal group can be used, and the molecular weight thereof can be 100 to 10,000 but not limited thereto.
According to one preferable embodiment of the present invention, after the step of forming the middle-coating vapor-deposition layer, a top-coating vapor-deposition layer can be formed further on the surface. The top-coating vapor-deposition layer plays a role of protecting the optical coating layer by providing contamination resistance
(resistance to fingerprint) and easy cleaning properties as well as strengthening reliabilities such as salt water resistance, abrasion resistance, scratch resistance and the like.
According to surface characteristics of the middle-coating vapor-deposition layer and the multilayer design, the top-coating vapor-deposition layer can be deposited with a thickness of 10 A to 1,000 A by plasma-assisted vapor deposition method (ion assist) in the vacuum vapor deposition process.
Preferably, as coating agents to form the top-coating vapor-deposition layer, fluorocarbon-based compounds having one or more functional groups selected from carboxyl group, phosphate group, silane group, amine group, hydroxyl group, aldehyde group, ketone group, ether group and ketal group can be used, and the molecular weight thereof can be 100 to 10,000 but not limited thereto.
In the present invention, the coating agents for the formation of respective thin film layer can be deposited by using electron beam, resistance-heating device, sputtering device or ion plating device, preferably with using the carrier as described in Korean patent application No. 10-2007-0075000.
Also, preferably in the present invention, the formation of the multi-layered thin film structure proceeds continuously in a vacuum vapor deposition device.
The coating agents for the formation of respective thin film layer preferably comprise a solvent such as water, methanol, ethanol, acetone, acetyl acetone, glycol, ketone or the
like for the storage and stability of the agents.
The process for manufacturing multi-layered thin film of vacuum vapor deposition according to the present invention is explained step by step in detail below, with concrete embodiments.
An embodiment of the process for manufacturing multi-layered thin film of vacuum vapor deposition according to the present invention is the same as shown in Figure 1. According to the process diagram shown in Figure 1, the present invention is characterized in that all coating operations from the mounting to the demounting of the substrate, i.e. the product, in a vacuum vapor deposition device are performed through dry process in the vacuum vapor deposition device.
1 : The mounting step The substrate (or product) 10 such as case, window, window-integrated case, keypad, keypad-integrated window, function key part and various accessory part for portable electronic products such as mobile phone, MP3 player, portable multimedia player (PMP), digital multimedia broadcasting (DMB) receiver, car navigation system, notebook computer, etc. and display products such as monitor, touchscreen, etc. is mounted in a vacuum vapor deposition device. To prevent the substrate from falling off during the vacuum vapor deposition process, the substrate is installed to a jig which
is designed so as to fit the substrate in various forms.
2: The evacuating step
When the mounting of the substrate in the vacuum vapor deposition device is completed, the inside of vacuum vapor deposition chamber is evacuated to maintain a high-vacuum state of 1. OxIO"6 - 1.OxIO"3 torr, preferably a high-vacuum state of 1. OxIO"5 torr or higher vacuum, in order to perform the vacuum vapor deposition coating with metal and/or metal oxide. The temperature of the inside of vacuum vapor deposition chamber is set to 20 to 300 °C depending on the material of the mounted substrate 10.
3: The vapor depositing step for the bottom coating layer
When the suitable high- vacuum state is obtained, high voltage discharge is conducted by using ion beam device under the flow of argon (Ar), nitrogen (N2) and oxygen (O2) gases to generate plasma of the corresponding gas. The plasma gas with high energy is applied for 10 seconds to 1,000 seconds depending on the condition of the surface of the mounted substrate, to activate the surface of the mounted substrate 10 (plasma etching).
The bottom-coating vapor-deposition layer 20 is formed on the activated surface of the substrate 10. To form the bottom-coating vapor-deposition layer, the carrier as described in Korean patent application No. 10-2007-0075000 can be used. The agent for the bottom-coating is loaded in this carrier and in turn the carrier is installed to a
vaporization port using electron beam or a resistance-heating type vaporization port in the vacuum vapor deposition device, and then the carrier installed to the vaporization port is heated by using electron beam or resistance-heating boat to vaporize the coating agent loaded in the carrier, and the bottom-coating vapor-deposition layer is formed.
In the case of electron beam-heating type, all procedures of the coating process can be automated by using IC-5 (INFICON) which is one of the control devices for vacuum vapor deposition devices. The power of electron beam is controlled suitably between 1.5 % and 8.0 %, preferably between 2.0 % and 4.0 %.
The bottom-coating vapor-deposition layer formed as above preferably has a thickness of 10 A to 1,000 A (0.001 μm to 0.1 μm), most preferably about 100 A (0.01 μm, 10 nm) or more or less. The plasma etching as described above can be applied thereto for 0 to 300 seconds, by which the bottom-coating vapor-deposition layer can be stabilized.
The coating formed on the surface of the substrate is associated with the surface energy. The strength of adhesion can be estimated by measuring the contact angle between the substrate and water drop on the surface of the substrate, as shown in Figure 3. As the contact angle becomes smaller, the adhesion strength becomes greater.
In case of plastic in-mold injection product, the contact angle on the surface of the
substrate before the coating was 74.3° (Figure 5) whereas the contact angle decreased to 32.2° after the formation of the bottom-coating vapor-deposition layer 20 on the surface of the product (Figure 6), and before and after the bottom-coating vapor deposition, the surface energy was changed from 33.02 niN/m to 47.98 mN/m. That is, the adhesion strength was improved by the bottom-coating vapor deposition.
To the surfaces of products of various materials, the changes of surface contact angle and surface energy before and after the formation of the bottom-coating vapor- deposition layer are shown in the following Tables 1 and 2, respectively:
[Table 1] Changes of surface contact angle before and after the bottom-coating formation
[Table 2] Changes of surface energy before and after the bottom-coating formation
4: The multi-vapor depositing step (the optical coating layer forming step)
The optical coating layer 30 is formed on the bottom-coating vapor-deposition layer for providing beautiful and luxury optical design to the substrate, and showing various colors, effect of mirror or anti-mirror image, and antireflection effect.
The optical coating layer 30 is formed by vapor-depositing metal such as SUS (Steel Use Stainless), nickel (Ni), aluminum (Al), chrome (Cr), tin (Sn), indium-tin (In-Sn) and the like; metal oxide such as silicon oxide (SiO2), titanium oxide (TiO2), aluminum oxide (Al2O3), zirconium oxide (ZrO2), indium titanium oxide (InxTiyO2, ITO), barium titanium oxide (BaTiO3), magnesium oxide (MgO) and the like; metal nitride such as SiN, TiN and the like; or metal fluoride such as MgF2 and the like, in a single layer or multilayer through alternating vapor deposition, by using electron beam or resistance- heating device in a vacuum vapor deposition device.
5: The vapor depositing step for the middle coating layer
Since the optical coating layer 30 is formed from metal, metal oxide, metal nitride or metal fluoride, it has various surface characteristics and a vulnerability to moisture and contamination, etc. due to the features of inorganic materials.
Therefore, on the optical coating layer 30, the middle-coating vapor-deposition layer 40 is preferably formed with a thickness of about 100 A or more or less, in order to provide a surface which is stable to various environments and to strengthen the abrasion resistance and reliability of the vacuum vapor deposition thin film resisting to the environment, according to different surface conditions.
According to the multilayer design of the optical coating layer, the middle-coating vapor-deposition layer 40 can be deposited by plasma-assisted vapor deposition method (ion assist) in the vacuum vapor deposition process, and thus can exhibit hard coating characteristics and strengthen the weak scratch resistance, salt water resistance, etc. of the thin film vapor-deposition layer.
The carrier as described in Korean patent application No. 10-2007-0075000 can be used to form the middle-coating vapor-deposition layer, as the same for the bottom-coating vapor-deposition layer. The agent for the middle-coating is loaded in this carrier and in turn the carrier is installed to a vaporization port using electron beam or a resistance- heating type vaporization port in the vacuum vapor deposition device, and then the carrier installed to the vaporization port is heated by using electron beam or resistance- heating boat to vaporize the coating agent loaded in the carrier, and the middle-coating vapor-deposition layer is formed.
The middle-coating vapor-deposition layer formed as above preferably has a thickness of 10 A to 1,000 A (0.001 μm to 0.1 μm), most preferably about 100 A (0.01 μm, 10 nm) or more or less. The plasma etching as described above can be applied thereto for 0 to 300 seconds, by which the middle-coating vapor-deposition layer can be stabilized.
6: The vapor depositing step for the top coating layer
As explained above, since the optical coating layer 30 has various surface characteristics and a vulnerability to moisture and contamination, etc. due to the features of inorganic materials, the top-coating vapor-deposition layer 50 is preferably provided over the optical coating layer 30 directly or with the intervention of the middle-coating vapor- deposition layer 40.
The top-coating vapor-deposition layer 50 can be formed by a method similar with the bottom- and middle-coating vapor-deposition layers, in a thickness of 100 A to 1,000 A, without controlling the coating thickness specially.
The thin film coating formed through the top-coating vapor depositing step has a very low surface energy and a feature of low friction coefficient, thereby showing property of very slippery surface, and thus the attachment of contamination sources such as fingerprint and soil etc. can be reduced remarkably. Even though the fingerprint and
soil are attached, they can be removed easily by the excellent easy cleaning function of the coating. Also, at the same time, characteristic properties such as water-repellent or oil-repellent property, scratch resistance, durability, etc. can be obtained, and thus a coating layer of vacuum vapor deposition which is stable after the test for reliability of a product having exterior coating as well as interior coating, can be formed.
As the contact angle becomes greater, the adhesion or attaching strength becomes worse, as shown in Figure 3. However, in terms of the attachment of contaminants, it means that the resistance to contamination becomes stronger. The coating surface having the top-coating vapor deposition layer treated as above is shown in Figure 7. The contact angle and surface energy when the top-coating vapor deposition layer is formed are shown in the following Tables 3 and 4, respectively.
[Table 3] Contact angles when the top-coating vapor deposition layer is formed
[Table 4] Surface energies when the top-coating vapor deposition layer is formed
7: The ventilating step (the vacuum-destruction step)
When the manufacture of the multi-layered thin film by the dry process is completed, the vacuum state of the inside of the vacuum vapor deposition device is destroyed.
8: The demounting step
After the destruction of the vacuum state of the vacuum vapor deposition device, the product for which the manufacture of the multi-layered thin film is completed is taken out of the vacuum vapor deposition device.
The present invention has been explained in detail according to the embodiments of the present invention as above. However, it should be understood that the above embodiments are never intended to limit the scope of the present invention.
INDUSTRIAL APPLICABILITY
The present invention can be applied to cases, windows, window-integrated cases, keypads, keypad-integrated windows, function key parts, various accessories and the like of display and accessory parts used in portable electronic products such as mobile phone, MP3 player, portable multimedia player (PMP), digital multimedia broadcasting (DMB) receiver, car navigation system, notebook computer, etc. and display products
such as monitor, touchscreen, etc. and electronic home appliances such as refrigerator,
air conditioner, television, etc.
Claims
1. A process for manufacturing multi-layered thin film, comprising the steps of: forming a bottom-coating vapor-deposition layer on a substrate; and forming an optical coating layer on the bottom-coating vapor-deposition layer, where the bottom-coating vapor-deposition layer is to provide adhesion strength between the substrate and the optical coating layer, wherein the formation of the multi-layered thin film is performed by dry vacuum vapor deposition.
2. The process according to claim 1, further comprising a step of forming a middle- coating vapor-deposition layer after the step of forming the optical coating layer.
3. The process according to claim 2, further comprising a step of forming a top- coating vapor-deposition layer after the step of forming the middle-coating vapor-deposition layer.
4. The process according to claim 1, further comprising a step of forming a top- coating vapor-deposition layer after the step of forming the optical coating layer.
5. The process according to claim 1, wherein the substrate is case, window, window-integrated case, keypad, keypad-integrated window, function key part or accessory part of portable electronic product, display products or electronic home appliances.
6. The process according to claim 1, wherein the substrate is made out of a material selected from the group consisting of metal, glass, acryl, polycarbonate, PMMA, PET, ABS resin and combinations thereof.
7. The process according to claim 1, wherein the bottom-coating vapor-deposition layer is formed from carbon-based compound having one or more functional groups selected from carboxyl group, phosphate group, silane group, amine group, hydroxyl group, aldehyde group, ketone group, ether group and ketal group.
8. The process according to claim 1, wherein the bottom-coating vapor-deposition layer has a thickness of 10 A to 1,000 A.
9. The process according to claim 1, wherein the optical coating layer is formed from a material selected from the group consisting of metal, metal oxide, metal nitride, metal fluoride and combinations thereof.
10. The process according to claim 2, wherein the middle-coating vapor-deposition layer is formed from carbon-based compound having one or more functional groups selected from carboxyl group, phosphate group, silane group, amine group, hydroxyl group, aldehyde group, ketone group, ether group and ketal group.
11. The process according to claim 3, wherein the top-coating vapor-deposition layer is formed from fluorocarbon-based compound having one or more functional groups selected from carboxyl group, phosphate group, silane group, amine group, hydroxyl group, aldehyde group, ketone group, ether group and ketal group.
12. The process according to claim 1, wherein the vacuum vapor deposition is performed by using electron beam, resistance-heating device, sputtering device or ion plating device.
13. The process according to claim 1, wherein the formation of the multi-layered thin film structure proceeds continuously in a vacuum vapor deposition device.
14. A multi-layered thin film coating which is formed by the process according to any one of claims 1 to 13 and comprises a bottom-coating vapor-deposition layer formed on a substrate; and an optical coating layer formed on the bottom-coating vapor-deposition layer.
15. The multi-layered thin film coating according to claim 14, further comprising a middle-coating vapor-deposition layer formed on the optical coating layer.
16. The multi-layered thin film coating according to claim 15, further comprising a top-coating vapor-deposition layer formed on the middle-coating vapor- deposition layer.
17. The multi-layered thin film coating according to claim 14, further comprising a top-coating vapor-deposition layer formed on the optical coating layer.
18. An electronic product comprising the multi-layered thin film coating formed by the process according to any one of claims 1 to 13.
19. The electronic product according to claim 18, which is a mobile phone, MP3 player, portable multimedia player (PMP), digital multimedia broadcasting (DMB) receiver, car navigation system, notebook computer, monitor, touchscreen, refrigerator, air conditioner or television.
0. The electronic product according to claim 18, wherein the multi-layered thin film coating is formed on a case, window, window-integrated case, keypad, keypad- integrated window, function key part or accessory part.
Priority Applications (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN2008801016616A CN101784692B (en) | 2007-08-02 | 2008-07-31 | Process for manufacturing multi-layered thin film by dry vacuum vapor deposition |
| JP2010519154A JP2010535286A (en) | 2007-08-02 | 2008-07-31 | Multilayer thin film manufacturing method using dry vacuum deposition |
| HK10111725.7A HK1145192A1 (en) | 2007-08-02 | 2010-12-15 | Process for manufacturing multi-layered thin film by dry vacuum vapor deposition |
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2007-0077906 | 2007-08-02 | ||
| KR20070077906 | 2007-08-02 |
Publications (2)
| Publication Number | Publication Date |
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| WO2009017376A2 true WO2009017376A2 (en) | 2009-02-05 |
| WO2009017376A3 WO2009017376A3 (en) | 2009-04-16 |
Family
ID=40305064
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| PCT/KR2008/004470 WO2009017376A2 (en) | 2007-08-02 | 2008-07-31 | Process for manufacturing multi-layered thin film by dry vacuum vapor deposition |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP2010535286A (en) |
| KR (2) | KR101824017B1 (en) |
| CN (1) | CN101784692B (en) |
| HK (1) | HK1145192A1 (en) |
| WO (1) | WO2009017376A2 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US9339993B2 (en) | 2010-09-14 | 2016-05-17 | Corning Incorporated | Appliance fascia and mounting therefore |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR101246022B1 (en) * | 2010-08-19 | 2013-04-02 | (주)에스아이티 | Display window panel for anti-reflection and method thereof |
| KR101690091B1 (en) * | 2015-04-16 | 2016-12-27 | 주식회사 쎄코 | Antibacterial primer coating agent for vacuum deposition and method of multi-layered coating by using the same |
| KR102468988B1 (en) | 2020-07-14 | 2022-11-22 | 주식회사 동남티에스 | Method for forming decorative pattern by metal deposition layer and plastic decorative member including the decorative pattern by the same method |
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| JP2003255133A (en) * | 2002-03-05 | 2003-09-10 | Yazaki Corp | Combiner and its manufacturing method, and display device for vehicle |
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2008
- 2008-07-31 WO PCT/KR2008/004470 patent/WO2009017376A2/en active Application Filing
- 2008-07-31 CN CN2008801016616A patent/CN101784692B/en active Active
- 2008-07-31 KR KR1020080075295A patent/KR101824017B1/en active IP Right Grant
- 2008-07-31 JP JP2010519154A patent/JP2010535286A/en active Pending
-
2010
- 2010-12-15 HK HK10111725.7A patent/HK1145192A1/en unknown
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2016
- 2016-05-17 KR KR1020160059998A patent/KR20160064051A/en not_active Application Discontinuation
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| JP2000108262A (en) * | 1998-10-09 | 2000-04-18 | Toray Ind Inc | Polypropylene film for metal deposition and metal- deposited polypropylene film |
| KR20030073733A (en) * | 2002-03-13 | 2003-09-19 | 주식회사 뮤렉스테크놀로지 | Metal Sputtering and Evaporation Equipment and Method on Plastics |
| JP2006123296A (en) * | 2004-10-28 | 2006-05-18 | Oike Ind Co Ltd | Method for producing metal vapor deposition film with oxidation preventing layer and metal vapor deposition film with oxidation preventing layer |
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| US9339993B2 (en) | 2010-09-14 | 2016-05-17 | Corning Incorporated | Appliance fascia and mounting therefore |
Also Published As
| Publication number | Publication date |
|---|---|
| JP2010535286A (en) | 2010-11-18 |
| KR20160064051A (en) | 2016-06-07 |
| CN101784692B (en) | 2013-03-20 |
| WO2009017376A3 (en) | 2009-04-16 |
| KR20090013719A (en) | 2009-02-05 |
| KR101824017B1 (en) | 2018-02-01 |
| HK1145192A1 (en) | 2011-04-08 |
| CN101784692A (en) | 2010-07-21 |
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