WO2017039342A1 - Film barrière comprenant un film mince de fluoro-carbone et son procédé de fabrication - Google Patents

Film barrière comprenant un film mince de fluoro-carbone et son procédé de fabrication Download PDF

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WO2017039342A1
WO2017039342A1 PCT/KR2016/009772 KR2016009772W WO2017039342A1 WO 2017039342 A1 WO2017039342 A1 WO 2017039342A1 KR 2016009772 W KR2016009772 W KR 2016009772W WO 2017039342 A1 WO2017039342 A1 WO 2017039342A1
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layer
barrier film
metal
fluorine
based polymer
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PCT/KR2016/009772
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English (en)
Korean (ko)
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이상진
이재흥
최우진
조성근
함동석
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한국화학연구원
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Priority claimed from KR1020150123340A external-priority patent/KR101666350B1/ko
Priority claimed from KR1020150130675A external-priority patent/KR101719520B1/ko
Priority claimed from KR1020160010369A external-priority patent/KR102010240B1/ko
Application filed by 한국화학연구원 filed Critical 한국화학연구원
Publication of WO2017039342A1 publication Critical patent/WO2017039342A1/fr

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    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K59/00—Integrated devices, or assemblies of multiple devices, comprising at least one organic light-emitting element covered by group H10K50/00
    • H10K59/80—Constructional details
    • H10K59/87—Passivation; Containers; Encapsulations
    • H10K59/873—Encapsulations
    • 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
    • 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
    • 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
    • C23C14/12—Organic material
    • 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
    • C23C14/14—Metallic material, boron or silicon
    • 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
    • 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
    • C23C14/35—Sputtering by application of a magnetic field, e.g. magnetron sputtering
    • G—PHYSICS
    • G02—OPTICS
    • G02B—OPTICAL ELEMENTS, SYSTEMS OR APPARATUS
    • G02B1/00—Optical elements characterised by the material of which they are made; Optical coatings for optical elements
    • G02B1/10—Optical coatings produced by application to, or surface treatment of, optical elements
    • G02B1/11—Anti-reflection coatings
    • G02B1/113—Anti-reflection coatings using inorganic layer materials only
    • H—ELECTRICITY
    • H10—SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10K—ORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K77/00—Constructional details of devices covered by this subclass and not covered by groups H10K10/80, H10K30/80, H10K50/80 or H10K59/80
    • H10K77/10—Substrates, e.g. flexible substrates
    • H10K77/111—Flexible substrates

Definitions

  • the present invention relates to a barrier film comprising a fluorine carbide thin film and a method for manufacturing the same. More particularly, the barrier film not only has a barrier property against moisture but also maintains cyanity in the visible light region and has excellent environmental resistance. And it relates to a manufacturing method thereof.
  • glass substrates have been used in flat panel displays (FPDs) such as plasma displays, liquid crystal display, and organic light emitting display.
  • FPDs flat panel displays
  • Such a glass substrate is liable to be broken, has no bending property, and has a specific gravity, so that there is a limit to thinness and lightness.
  • a transparent plastic film has been attracting attention as a glass substrate replacement.
  • the transparent plastic film has a merit of being able to cope with the increase in size of the device because it is light and difficult to be broken and thinning is easy.
  • the transparent plastic film has a higher gas permeability than glass, the display device employing the transparent plastic film has a problem in that the light emitting performance of the display device is easily degraded due to oxygen or water vapor transmission.
  • a gas barrier film of an organic material or an inorganic material on a transparent plastic film to minimize the effects of oxygen or water vapor.
  • inorganic materials such as silicon oxide (SiOx), silicon nitride (SiNx), aluminum oxide (AlxOy), tantalum oxide (TaxOy), titanium oxide (TiOx), and the like are mainly used as the gas barrier film.
  • a vacuum deposition method such as plasma enhanced chemical vapor deposition (PECVD), sputtering or the sol-gel method.
  • Patent document 1 (Unexamined-Japanese-Patent No. 1994-031850) discloses a high gas barrier transparent conductive film by sputtering an inorganic layer on the surface of a plastic film.
  • the elastic modulus, thermal expansion coefficient, and bending radius of the plastic film and the inorganic layer are largely different, if heat or repetitive force is applied or bent from the outside, cracks are generated due to stress at the interface. There is a problem that the layer can be easily peeled off.
  • Patent Document 2 Japanese Laid-Open Patent Publication No. 2004-082598 discloses a multilayer gas barrier laminate comprising an organic layer and an inorganic layer and a method of manufacturing the same. This resulted in cracking at or increasing the likelihood of peeling of the thin film.
  • Patent Document 3 European Laid-Open Patent Publication No. 1,938,967 coats a barrier layer with a fluorine paint such as polyvinyl fluoride (PVC) or polyvinylidene fluoride (PVDF) to provide weather resistance and the like.
  • a fluorine paint such as polyvinyl fluoride (PVC) or polyvinylidene fluoride (PVDF) to provide weather resistance and the like.
  • PVC polyvinyl fluoride
  • PVDF polyvinylidene fluoride
  • Patent Document 4 proposes a method of adding metal-coated mica particles which are plate-shaped particles.
  • the plate-shaped mica particles described above have a problem that the size of 10 to 300 micrometers is somewhat large and the particle size distribution is wide so that water vapor can still pass through the gaps between the particles. It does not solve the problem perfectly.
  • the present inventors in order to solve the problems of the prior art as described above to meet the needs required in the art, as a result of in-depth research, it includes a super water-repellent fluorocarbon thin film that can block the water permeability significantly
  • a barrier film was devised.
  • DC or MF sputtering which has a frequency lower than a few tens of KHz or lower than RF, and thus continuous rolls.
  • the present invention has been completed by developing a new technology capable of large-area barrier film using a two-roll deposition system.
  • An object of the present invention is to provide a barrier film that can significantly improve the barrier property against moisture as well as external pollutants by including a fluorocarbon thin film having super water repellency and high insulation.
  • the barrier film used for preventing water permeation according to the present invention may exhibit excellent transparency and flexibility by depositing a flexible adherend, and improve adhesion and mechanical adhesion with the adherend using a fluorine-based polymer composite target containing a conductive functionalizing agent. It is to provide a barrier film having strength.
  • the present invention is to provide a barrier film excellent in environmental resistance that can be adjusted not only optically transparent but also optical properties such as thermal barrier properties, anti-reflection properties, etc. according to the purpose.
  • Still another object of the present invention is a thin film deposition process of fluorine carbide, which is a representative insulator, in which the fluorine-based polymer target is damaged due to deterioration due to the use of high energy due to non-conductivity, between the fluorine-based polymer and a metal electrode applying voltage.
  • the generation of an arc, etc. significantly improves the problem of lowering the deposition rate by generating a plasma having a lower efficiency than the applied voltage.
  • the present invention is to provide a method for producing a barrier film comprising a fluorocarbon thin film deposited at a high deposition rate even by a low voltage MF or DC power supply.
  • the present invention can not only easily control the thickness of the thin film through sputtering using a more industrially useful power supply method such as MF or DC, but also evenly and uniformly deposited at a high deposition rate on the adherend, thereby generating pinholes and cracks. It is to provide a method for producing a barrier film that can effectively suppress the degradation due to.
  • Still another object of the present invention is that all processes can be sputtered by MF or DC power supply, which is a relatively low power supply method compared to RF, thereby simplifying the manufacturing process of the barrier film having the excellent characteristics as described above. It is possible to implement a roll-to-roll process capable of manufacturing a large-area barrier film in a very short time, and to provide a method for manufacturing a roll-to-roll barrier film that can be directly applied to a conventional roll-to-roll equipment without additional modification costs.
  • the present invention includes the steps of forming an inorganic layer including at least one selected from metals and metal compounds as a main component on one surface of the adherend and a forming dopant having conductivity and a fluorine-based polymer on one surface of the inorganic layer. It provides a method for producing a barrier film comprising the step of depositing a fluorine-based polymer composite target to form an organic layer.
  • the inorganic layer and the organic layer may be formed by being deposited by RF, MF or DC sputtering, respectively.
  • the organic layer uses a fluorine-based polymer composite target including a functionalizing agent
  • the organic layer prevents damage to the deposition target due to deterioration, which is a problem caused by applying high energy in the deposition of conventional fluorine-based polymers.
  • the generation of an arc or the like between the fluorine-based polymer generated by the application of high energy and the metal electrode applying the voltage can effectively improve the point of low deposition rate due to the generation of plasma having a lower efficiency than the applied voltage.
  • the fluorine-based polymer composite target according to the present invention must include at least one conductive material selected from conductive particles, conductive polymers and metal components that can impart conductivity, so that even with commercially useful MF or DC sputtering, the effective and high deposition rate Thin films may be deposited.
  • the functionalizing agent according to an aspect of the present invention may be to include a functionalizing agent having one or more conductivity selected from conductive particles, conductive polymers and metal components, etc., RF due to the functionalizing agent to impart such conductivity
  • a functionalizing agent having one or more conductivity selected from conductive particles, conductive polymers and metal components, etc. RF due to the functionalizing agent to impart such conductivity
  • sputtering deposition of fluorocarbon thin films is possible at lower voltages, MF and DC, and high quality barrier films can be formed by preventing high deposition rates and dielectric breakdown.
  • the organic layer according to an aspect of the present invention comprises any one or two or more functionalizing agents selected from conductive particles, conductive polymers and metal components, such as metal organic matter, metal oxide, metal carbon body, metal hydroxide, metal carbonate, metal bi Further comprising one or more metallic compounds selected from carbonates, metal nitrides, metal sulfides and metal fluorides, it is possible to additionally control the surface properties of the barrier film.
  • functionalizing agents selected from conductive particles, conductive polymers and metal components, such as metal organic matter, metal oxide, metal carbon body, metal hydroxide, metal carbonate, metal bi
  • metallic compounds selected from carbonates, metal nitrides, metal sulfides and metal fluorides
  • the thickness of the inorganic layer and the organic layer can be easily adjusted and evenly deposited on the adherend through sputtering using a more industrially useful power supply method such as MF or DC, respectively. All of the processes for forming a layer of MF or DC can be sputtered, and the application of a roll-to-roll process can dramatically improve productivity by performing a continuous process in one equipment.
  • the present invention provides a step of forming an inorganic layer using a target containing at least one selected from a metal and a metal compound as a main component while transferring the adherend in a roll-to-roll manner and a function of having fluorine-based polymers and conductivity on one surface of the inorganic layer. It provides a method for producing a barrier film comprising the step of forming an organic layer using a fluorine-based polymer composite target containing a topical agent. At this time, the inorganic layer and the organic layer is characterized in that formed by MF or DC sputtering.
  • the present invention is an adherend; An inorganic layer comprising, as a main component, at least one selected from metals and metal compounds; And an organic layer comprising a fluorine-based polymer and a functionalizing agent having conductivity.
  • the present invention is capable of sputtering at MF or DC, which is a lower voltage than RF, by using a conductive fluorinated polymer composite target, preventing dielectric breakdown, and having a high deposition rate, low surface energy and high barrier property against moisture.
  • the barrier film of can be provided.
  • the adhesion to the adherend or the metal thin film is excellent, it is possible to remarkably reduce problems such as peeling phenomenon between each thin film to give a high durability.
  • the barrier film according to the present invention has a high light transmittance and a low moisture permeability at the same time, it is possible to minimize the failure rate of the device employing it.
  • the present invention can easily provide a barrier film of various aspects to which the physical, chemical, and optical properties according to the purpose is given by configuring a barrier film used for preventing water permeation having a variety of compositions.
  • an MF or DC sputtering device in a conventional roll-to-roll method capable of manufacturing a large-area thin film, can be directly applied without additional modification costs, and continuously includes an inorganic layer and an organic layer.
  • the barrier film can be produced in-line at one time, thereby simplifying the process and reducing costs.
  • FIG. 1 is a schematic diagram of a roll-to-roll sputtering deposition system according to the present invention.
  • a barrier film including a fluorocarbon thin film according to the present invention and a method for manufacturing the same will be described below. However, unless otherwise defined in the technical and scientific terms used, a person having ordinary knowledge in the technical field to which the present invention belongs. Descriptions of well-known functions and configurations, which have ordinary meanings and may unnecessarily obscure the subject matter of the present invention, will be omitted.
  • the present applicant not only has excellent transparency and hydrophobic surface properties, but also has excellent adhesion to the adherend, so that the barrier film suitable for the outermost protective layer of the flexible display and a manufacturing method thereof can be economically mass-produced.
  • the invention has been completed.
  • the barrier film according to the present invention may be an inorganic layer and an organic layer formed on one surface of the adherend.
  • the inorganic layer may include one or more selected from metals and metal compounds as a main component, and the organic layer formed on one surface of the inorganic layer may include a fluorinated polymer and a functionalizing agent having conductivity.
  • the "inorganic layer" in the present specification includes a metal component such as silver (Ag), copper (Cu) or nickel (Ni) as a main component or at least one metal compound selected from metal oxides, metal nitrides and metal sulfides It may be included as a main component, the inorganic layer may be formed by sputtering using a metal compound target, such as a metal oxide target and a metal nitride target, or oxidized or nitrided by a reaction gas using a metal target, of course, It may be formed by other methods.
  • the term “main ingredient” means the most component in the total composition, and may mean, for example, a component that occupies 40 to 90 wt%.
  • the "organic layer” means a fluorocarbon thin film deposited by a fluorine-based polymer composite target containing a functionalizing agent having conductivity to the fluorine-based polymer, the functionalizing agent having a conductivity contained in the fluorine-based polymer composite target is a conductive particle, It may be one selected from conductive polymers, metal components and metal compounds.
  • the organic layer according to an embodiment of the present invention by using a fluorine-based polymer composite target containing the above-described functionalizing agent, to effectively suppress the deformation and defects that may occur in the conventional RF applied to the surface of the adherend It can be formed uniformly.
  • barrier film according to one embodiment of the present invention will be described, but is not limited thereto.
  • the barrier film used for thermal insulation which is one aspect of the barrier film which concerns on this invention, and its manufacturing method are demonstrated.
  • Barrier film used for the thermal barrier according to an aspect of the present invention by placing the fluorocarbon thin film in the outermost layer, to maximize the thermal insulation effect of the heat ray shielding layer containing a metal having a unique heat shielding properties as well as water repellent and antifouling Since the effect is excellent, the environmental resistance of the barrier film exposed to the external environment can be improved.
  • the adhesiveness with the substrate is not only degraded when the coating is performed using a conventionally used wet process, but has a typical color (white), but the barrier film manufactured by the manufacturing method according to the present invention is described above. It is possible to solve the problems and at the same time excellent visibility and adhesion to the substrate.
  • the barrier film according to the present invention is formed using a fluorine-based polymer composite target having conductivity, thereby enabling stable plasma formation and high deposition rate even when using a lower voltage MF or DC power supply method. have.
  • the barrier film used for the heat shield comprises a heat ray shielding layer and a heat shield addition element mainly composed of an adherend, silver (Ag), copper (Cu) or nickel (Ni).
  • An optical compensation layer and a fluorocarbon protective layer are included in the barrier film used for heat shielding.
  • the barrier film used for heat shielding can realize a high heat ray shielding effect by forming a heat ray shielding layer mainly composed of silver (Ag), copper (Cu), or nickel (Ni) with high thermal barrier efficiency.
  • fluorine carbide protective layer formed in the heat shielding rate can be maximized to more than 90%.
  • the heat ray blocking layer and the optical compensation layer are included in the term "inorganic layer” of the present invention, and the fluorocarbon protective layer is included in the term "organic layer” of the present invention.
  • non-limiting examples of the additional element included in the optical compensation layer may include NiCr, NiAu, ITO, IZO, IZTO, AZO, IAZO, GZO, IGO, IGZO, IGTO, ATO, IATO, IWO, CIO, MIO, MgO, SnO 2 , ZnO, ZnAlO x , In 2 O 3 , TiTaO 2 , TiNbO 2 , TiO 2 , RuO 2 , IrO, Nb 2 O 5 , Ta 2 O 5 , ZnO, SiO 2 , SiN, Si 3 N 4 And Al 2 O 3 One or more selected from the like, but is not limited thereto.
  • TiO 2 , SiO 2 , SiN, Si 3 N 4 And Al 2 O 3 It is preferable to include at least one additional element selected from the like.
  • the fluorocarbon protective layer according to an embodiment of the present invention includes a fluorinated polymer and a functionalizing agent having conductivity.
  • the fluorocarbon protective layer according to the present invention by imparting conductivity to the target by including a functionalizing agent having conductivity, as well as the high-frequency energy of RF (radio-frequency) as well as a lower voltage MF (mid-) Sputtering deposition of the fluorocarbon thin film was also possible at a range frequency) and a direct current (DC).
  • a functionalizing agent having conductivity as well as the high-frequency energy of RF (radio-frequency) as well as a lower voltage MF (mid-) Sputtering deposition of the fluorocarbon thin film was also possible at a range frequency) and a direct current (DC).
  • the fluorocarbon protective layer is formed using a fluorine-based polymer composite target.
  • the fluorinated polymer composite target should include a functionalizing agent to impart conductivity, and the functionalizing agent is not limited as long as it is a material capable of imparting conductivity, and examples thereof include conductive particles, conductive polymers, and metal components.
  • the conductive particles include carbon nanotubes, carbon nanofibers, Carbon black, graphene, graphite, carbon fiber, and the like, and other organic conductive particles may also be included.
  • the organic conductive particles which are examples of the conductive particles are used, conductivity can be imparted while maintaining the fluorocarbon component.
  • the conductive polymer polyaniline (polyaniline), polyacetylene (polyacetylene), polythiophene (polythiophene), polypyrrole (polypyrrole), polyfluorene (polyfluorene), polypyrene (polypyrene), polyazulene (polyazulene) , Polynaphthalene, polyphenylene, polyphenylene vinylene, polycarbazole, polyindole, polyazephine, polyethylene, polyethylene Polyethylene vinylene, polyphenylene sulfide, polyfuran, polyselenophene, polytellurophene, polysulfur nitride And the like, but are not limited thereto.
  • the metal component examples include copper (Cu), aluminum (Al), silver (Ag), gold (Au), tungsten (W), magnesium (Mg), nickel (Ni), molybdenum (Mo), Vanadium (V), niobium (Nb), titanium (Ti), platinum (Pt), chromium (Cr), tantalum (Ta), and the like, and preferably copper in terms of excellent binding with a metal electrode.
  • Cu aluminum (Al), silver (Ag), gold (Au), tungsten (W), silicon (Si), magnesium (Mg), nickel (Ni) or mixtures thereof, more preferably copper (Cu ), Aluminum (Al), silver (Ag), gold (Au) or mixtures thereof are preferred, but are not limited thereto.
  • the fluorine-based polymer composite target according to an aspect of the present invention includes a fluorine-based polymer
  • the fluorine-based polymer is not limited as long as it is a resin containing fluorine, preferably polytetra is a synthetic resin polymerized olefin containing fluorine Fluoroethylene (PTFE, polytetrafluoroethylene), polychlorotrifluoroethylene (PCTFE, polychlorotrifluoroethylene), polyvinylidenedifluoride (PVDF, polyvinylidenedifluoride), fluorinated ethylene propylene copolymer (FEP), polyethylene -Tetrafluoroethylene (ETFE, poly ethylene-co-tetra fluoro ethylene), polyethylene-chloro trifluoro ethylene (ECTFE, poly ethylene-co-chloro trifluoro ethylene), polytetrafluoro ethylene-fluoro alkyl vinyl ether
  • PFA poly fluorine Fluoroethylene
  • the composition of the fluorine-based polymer composite target according to the present invention is not limited, but preferably may be contained in 0.01 to 2000 parts by weight of the functionalizing agent with respect to 100 parts by weight of the fluorine-based polymer, to prevent higher deposition rate and insulation breakdown In terms of being able to deposit a high quality fluorocarbon thin film, it is preferable to contain 0.5 to 1500 parts by weight, more preferably 1 to 1000 parts by weight.
  • the adherend according to an aspect of the present invention may be selected from silicon, metal, ceramic, resin, paper, glass, quartz, fiber, plastic, organic polymer, and the like, but is not limited to flexible silicone, polypropylene (PP), polyethylene (PE), polycarbonate (PC), polyethylene terephthalate (PET), polyimide (PI), cyclic olefic copolymer (COC), cyclic olefin polymer (cyclic olefin polymer, COC), triacetyl cellulose (TAC), polyethylene naphthalene (PEN), polyurethane (PU), polyacrylate, polyester, polymethylene pentene PMP), polymethyl methacrylate (PMMA), polymethacrylate (PMA), polystyrene (PS), styrene-acrylonitrile copolymer (styre ne-acrylonitrile copolymer (SAN), acrylonitrile-butylene-styrene copolymer (ABS), poly
  • each of the heat ray shielding layer, the optical compensation layer and the fluorocarbon protective layer of the barrier film used for the thermal barrier according to the present invention can be deposited using a sputtering method and can be applied to a roll-to-roll process. It is possible to manufacture barrier films used for thermal insulation in a continuous process in one machine, which can dramatically improve productivity.
  • the fluorocarbon protective layer of the barrier film used for the thermal barrier according to the present invention can also be easily deposited by the role of the functionalizing agent by the use of industrially useful MF, DC, etc., can bring a surprising increase in the deposition efficiency. have.
  • the fluorocarbon protective layer of the barrier film used for the thermal barrier according to an embodiment of the present invention by imparting conductivity to the fluorine-based polymer, it is surprisingly possible to sputter even in a low voltage power supply method such as MF, DC, very short time It is possible to implement a roll-to-roll process with a large-area coating in the inside, so it can be directly applied by replacing targets in the existing roll-to-roll equipment without any renovation cost. Can have
  • the present invention in the manufacture of the barrier film used for the thermal barrier according to an aspect of the present invention can be utilized as a sputtering process to produce a nano-size thin film, has the advantage of precisely controlling the thickness of the thin film. . That is, according to the present invention, since the contact angle, visible light transmittance, heat ray transmittance, and the like of the barrier film can be freely adjusted, the present invention can be applied to a heat barrier barrier film having excellent energy saving effect by being applied to a loading place.
  • the coating of the optical compensation layer and the coating of the heat ray shielding layer may be performed repeatedly one or more times sequentially or randomly.
  • the process may be repeatedly performed two or more times in sequence, and then the fluoride carbide protective layer is disposed at the outermost portion.
  • the optical compensation layer, the heat ray shielding layer and the fluorocarbon protective layer according to an aspect of the present invention are not particularly limited, but may be manufactured, for example, in the range of 1 to 10000 nm, and in the case of the heat ray shielding layer, 780 which is a stranded region. It is preferable to form a range of 5 to 15 nm in terms of improving heat insulation properties by selectively blocking a wavelength in the range of 2 to 2200 nm and not decreasing cyanity, but is not limited thereto.
  • the optical compensation layer is preferably formed in the range of 20 to 100 nm in terms of improving the heat insulating property and at the same time increasing the hardness of the barrier film used for heat shielding, but is not limited thereto.
  • the fluorocarbon protective layer is preferably formed in the range of 10 to 100 nm in terms of maximizing antifouling and waterproof characteristics, and optimizing the optical and strength characteristics of the barrier film used for thermal barrier, but is not limited thereto. no.
  • the present invention provides a roll-to-roll sputtering deposition system in which all processes of forming an optical compensation layer, a heat ray shielding layer, a fluorocarbon protective layer, and the like included in the barrier film used for the thermal barrier may be continuously performed.
  • the sputtering may be performed by MF or DC sputtering.
  • barrier film used for antireflection which is one aspect of the barrier film which concerns on this invention, and its manufacturing method are demonstrated.
  • the present invention provides a barrier film having omnidirectional antireflective properties.
  • the barrier film used for the anti-reflection according to the present invention may be formed by sequentially depositing an antireflection layer and an antireflection layer having different refractive indices on a substrate by a sputtering method, and the antireflection layer may include a functionalizing agent having conductivity. It may be a fluorocarbon thin film sputtered using a fluorine-based polymer composite target containing.
  • the reflection reducing layer may include one or more selected from metal oxides, metal nitrides, metal sulfides, and the like, which may be metal oxide targets, It can be formed by sputtering using a metal nitride target, a metal sulfide target, or the like, or by oxidizing, nitriding or sulfiding with a reaction gas using a metal target, or may be formed by other methods.
  • the reaction gas may be one or more selected from nitrous oxide (N 2 0), nitrogen dioxide (N0 2 ), nitrogen monoxide (NO) and oxygen (O 2 ), preferably nitrogen dioxide (N0 2 ), oxygen ( O 2 ) or a mixed reaction gas thereof.
  • the reflection reduction layer may include one or more layers selected from a low refractive index layer and a high refractive index layer, or a stacking order thereof
  • the shape and the like can be appropriately adjusted according to the characteristics of the barrier film used for the desired antireflection.
  • the anti-reflection layer in order to implement more excellent anti-reflection characteristics, may be sputtered on a low refractive index layer after sputtering a high refractive index layer on a substrate. In this case, as the number of steps of the high refractive index layer and the low refractive index layer increases, improved antireflection characteristics may be realized.
  • the high refractive index layer is titanium (Ti), zirconium (Zr), niobium (Nb), zinc (Zn), indium (In), aluminum (Al), antimony (Sb), tin (Sn), cerium (Ce) Zirconium oxide (ZrO 2 ), titanium oxide (TiO 2 ), zinc sulfide (ZnS), based on one or more metals selected from selenium (Se) and yttrium (Y), etc.
  • the high refractive index layer has a high refractive index (@ 550 nm) of 1.6 or more, and by stacking the low refractive index layers to be described later to improve the destructive interference phenomenon of the light reflected at the interface between the layers, excellent antireflection characteristics in a wider wavelength range Can be implemented.
  • the refractive index difference ( ⁇ n) may be 0.1 to 1.5, preferably 0.1 to 1.2, more preferably 0.1 to 1.0, but is not limited thereto. .
  • the low refractive index layer comprises at least one metal selected from silicon (Si) and magnesium (Mg) in the form of a metal oxide such as silicon oxide (SiO 2 ), magnesium oxide (MgO), etc.
  • the silicon oxide (SiO 2 ) may be more preferably included in terms of excellent deposition rate and high reflection characteristics even in a wide wavelength range, but is not limited thereto.
  • the antireflection layer is a thin film of fluorocarbon thin film deposited using a fluorine-based polymer composite target containing a functionalizing agent having conductivity to the fluorine-based polymer.
  • a fluorine-based polymer composite target containing a functionalizing agent having conductivity to the fluorine-based polymer.
  • the configuration of such a fluorocarbon thin film, a manufacturing method thereof, and the like communicate with the fluorocarbon protective layer of the barrier film used for the above-described thermal barrier.
  • the method of manufacturing a barrier film used for the anti-reflection according to an embodiment of the present invention can be deposited by commercially available MF or DC sputtering, without additional supplementary equipment of the conventional roll-to-roll continuous sputtering deposition system Applicable. That is, by using the manufacturing method according to the present invention, it is economical to minimize the width variation and maximize the optical effect, and to quickly form a barrier film used for preventing large area reflection.
  • the reflection reduction layer is formed by repeatedly depositing a high refractive index layer and a step of depositing a low refractive index layer.
  • the structure can be formed.
  • the refractive index difference ( ⁇ n) of the high refractive index layer and the low refractive index layer may be 0.1 to 1.5, preferably 0.1 to 1.2, more preferably 0.1 to 1.0, but is not limited thereto.
  • the barrier film used for the antireflection according to an embodiment of the present invention has an antireflection layer, which is a fluorine carbide thin film, in the outermost layer, thereby significantly reducing the phenomenon of the thin film being detached from the substrate due to deterioration or impact.
  • the high refractive index layer, the low refractive index layer, and the antireflection layer of the antireflection layer of the barrier film used for antireflection according to an aspect of the present invention may be independently deposited to a thickness of 1 nm to 10 ⁇ m, and may have improved visibility. In terms of reflecting properties, it may be preferably deposited with a thickness of 10 nm to 500 nm, more preferably 10 nm to 100 nm.
  • the present invention provides a barrier film, that is, a barrier film used for anti-reflection, which is formed by sequentially sputtering an antireflection layer including a high refractive index layer and a low refractive index layer on a adherend and a fluorine carbide thin film.
  • the barrier film used for the anti-reflection according to an aspect of the present invention has excellent adhesion and reflectance, and has a lower surface energy by introducing a superhydrophobic fluorocarbon thin film into the outermost layer, thereby smoothing surface smoothness and staining. Not only can impart surface properties such as forestry, but also has excellent antifouling properties and antistatic properties.
  • the barrier film used for the anti-reflection is characterized in that the contact angle with moisture has a super water-repellent in the range of 90 to 150 °.
  • barrier film used for water permeation prevention which is one aspect of the barrier film which concerns on this invention, and its manufacturing method are demonstrated.
  • the barrier film used for preventing water permeation includes a fluorocarbon thin film having super water repellency and high insulating property, thereby significantly improving the barrier property against moisture as well as external pollutants. It is deposited on the adherend at high deposition rates to show excellent transparency and flexibility.
  • a multilayer barrier structure of two or more layers including a fluorine carbide thin film it is possible to provide a barrier film used for preventing moisture permeation, which can increase adhesion of the multilayer structure, effectively suppress peeling from the adherend and increase mechanical strength. Can be.
  • the present invention comprises the steps of forming an inorganic layer including at least one selected from metal oxides and metal nitrides on one surface of the adherend; And forming an organic layer including one or more functionalizing agents selected from fluorine-based polymers, conductive particles, conductive polymers, metal components, and metal compounds on one surface of the inorganic layer. Provide a method.
  • the inorganic layer according to an aspect of the present invention is not limited as long as it is a substance capable of inhibiting the permeation of moisture, and may be composed mainly of silicon oxide, aluminum oxide, or silicon nitride having excellent affinity and heat resistance with the adherend.
  • Titanium (Ti), zirconium (Zr), hafnium (Hf), niobium (Nb), tantalum (Ta), vanadium (V), tungsten (W), aluminum (Al), gallium (Ga), indium (In ), Zinc (Zn), silicon (Si), germanium (Ge) and the like may further include one or more oxides or nitrides selected from.
  • the present invention comprises the steps of forming an inorganic layer using a metal target, a metal oxide target or a metal nitride target on one surface of the adherend; And forming an organic layer by using a fluorine-based polymer composite target including at least one conductive material selected from conductive particles, conductive polymers, and metal components on one surface of the inorganic layer.
  • a fluorine-based polymer composite target including at least one conductive material selected from conductive particles, conductive polymers, and metal components on one surface of the inorganic layer.
  • the inorganic layer and the organic layer may be formed by MF or DC sputtering, which is a power method having a frequency lower than tens of KHz or less than RF, and applied them to a continuous roll-to-roll sputtering deposition system.
  • the barrier film can be economically large in area.
  • the inorganic layer according to an aspect of the present invention may be formed at a high deposition rate using a metal target, a metal oxide target or a metal nitride target, and the metal target may be titanium (Ti), zirconium (Zr), or hafnium (Hf). , Niobium (Nb), tantalum (Ta), vanadium (V), tungsten (W), aluminum (Al), gallium (Ga), indium (In), zinc (Zn), silicon (Si) and germanium (Ge) Using a metal selected from), etc., it is oxidized by the reaction gas to form a metal oxide or metal nitride thin film.
  • the reaction gas may be one or more selected from nitrous oxide (N 2 0), nitrogen dioxide (N0 2 ), nitrogen monoxide (NO) and oxygen (O 2 ), preferably nitrogen dioxide (N0 2 ), oxygen ( O 2 ) or a mixed reaction gas thereof.
  • the constitution of the organic layer, the manufacturing method thereof, and the like according to one aspect of the present invention communicate with the fluorocarbon protective layer of the barrier film used for the above-described thermal barrier.
  • the method for producing a barrier film used for preventing water permeation is possible to sputter both the inorganic layer and the organic layer at low energy, and thus it is applicable to a continuous roll-to-roll sputtering deposition system.
  • it is possible to realize excellent deposition rate even in low energy bands such as commercially available MF or DC, and to apply it immediately without supplementary facilities of the existing roll-to-roll sputter deposition system, and to quickly and large area fluoride carbide without defect. Since a thin film can be formed, it can provide the barrier film used for the prevention of moisture permeation of high quality economically.
  • the thickness of the inorganic layer and the organic layer of the barrier film used for preventing water permeation is not limited, it may be deposited to a thickness of 1 nm to 10 ⁇ m. At this time, in view of having a low transmittance to moisture and remarkably reducing the detachment of the thin film from the adherend due to deterioration or impact, the inorganic layer and the organic layer may be sequentially or randomly formed in a thickness of 10 nm to 200 nm. It is preferable to have a multilayer structure by depositing.
  • Barrier film used for preventing moisture permeation by introducing a superhydrophobic fluorocarbon thin film to the outermost, it is possible to significantly improve the optical properties while maintaining superhydrophobicity, high transparency, anti-pollution and It has antireflection properties and can provide excellent chemical resistance and lubricity.
  • the barrier film used for preventing the moisture permeation may have a lower surface energy, the contact angle with the moisture may be in the range of 90 to 150 °.
  • the barrier film used for preventing moisture permeation according to an aspect of the present invention may be prepared by applying to a roll-to-roll sputtering deposition system in which all processes of forming the organic layer and the inorganic layer can be performed continuously.
  • the sputtering deposition system is characterized in that it can be performed by MF or DC sputtering.
  • the roll-to-roll sputtering deposition system includes an unwinder chamber (100), a main chamber (200) for depositing an organic layer and an inorganic layer on one surface of the substrate, and a deposited It may include a winder chamber (300) for winding the barrier film. It can realize excellent deposition rate even in low energy bands such as MF and DC, and it is a barrier film that is used for preventing large area moisture permeation without defect even in continuous roll-to-roll process while ensuring simplicity in manufacturing process. It can be formed more economically.
  • the main chamber according to one aspect of the invention comprises three MF dual sputtering cathodes 202, 203, 204 and one DC single sputtering cathode 205. Due to this configuration, not only can MF and DC sputtering be performed at the same time, but also has the advantage that the deposition of the composite material by the application of various types of targets.
  • the winder chamber includes a resistance meter (301), a transmittance analyzer (302) and a reflectance meter (reflectance meter, 303), the water permeation prepared from the roll-to-roll type sputtering deposition system
  • a resistance meter 301
  • a transmittance analyzer (302)
  • a reflectance meter reflectance meter, 303
  • the properties of the barrier film used for prevention can be easily adjusted in one stop.
  • the contact angle, the maximum transmittance and the infrared transmittance for visible light were measured by the following method, and the results are shown in Tables 1 to 3 below. .
  • the water contact angle of the completed barrier film was measured using a contact angle measuring instrument (PHOEIX 300 TOUCH, SEO).
  • the transmittance of visible light (550 nm) was measured by irradiating light to the finished barrier film using a spectrophotometer (U-410, Hitachi).
  • the transmittance for 1,000 nm wavelength was measured three times using a UV-Vis spectrometer on the finished barrier film, and the average value thereof was determined to determine the infrared transmittance (%).
  • the finished barrier film was measured for moisture permeability at 40 ⁇ 0.5 °C, 90% relative humidity conditions using a WVTR measuring instrument (Deltaperm, Technolux).
  • the barrier film used for thermal insulation was produced using the roll-to-roll sputter (ULVAC, SPW-060) apparatus in PET film (SKC, SH-40, thickness 100micrometer, width 600mm) (refer FIG. 1).
  • the target for deposition for each layer of the barrier film used for the thermal barrier was produced in a square plate shape.
  • Si target 950 mm long, 127 mm wide, 6 mm thick
  • Ag target 950 mm long, 127 mm wide, 6 mm thick
  • PTFE polytetrafluoroethylene
  • CNT carbon nanotube
  • a fluorine-based polymer composite target (length 950 mm, width 127 mm, thickness 6 mm) containing 5 wt% was attached to each copper backing plate electrode surface.
  • Two Si targets were installed in the MF dual sputtering cathode 1 in the process chamber section, and two fluorine-based polymer composite targets were installed in the MF dual sputtering cathode 2.
  • the temperature of the main roll was lowered to 10 ° C., and a barrier film used for thermal barrier was deposited while conveying the PET film at a speed of 1 m / min.
  • a SiNx thin film (optical compensation layer) was deposited through the cathode 1.
  • the SiNx thin film by N 2 gas (N 2 gas) partial pressure (10 mtorr) to the MF power to 8 W / cm 2 was deposited to a thickness of 40 nm.
  • An Ag thin film (heat shielding layer) was deposited to a thickness of 12 nm on one surface of the SiNx thin film with a DC power of 0.6 W / cm 2 through the cathode 4.
  • a fluorocarbon thin film (organic layer) was deposited to a thickness of 20 nm with MF power of 2.0 W / cm 2 through the cathode 2, and a barrier film used for thermal cutoff of a three-layer structure was formed. Rewound in dubu.
  • the barrier film used for thermal insulation was produced by the same method except the following conditions.
  • the cathode 1 to the MF power to 6.5 W / cm 2 (N 2 gas) N 2 gas partial pressure (10 mtorr) to the SiNx thin film (optical compensation layer) it was deposited to a thickness of 30 nm.
  • An Ag thin film (heat shielding layer) was deposited to a thickness of 8 nm on one surface of the SiNx thin film with a DC power of 0.4 W / cm 2 through the cathode 4. Thereafter, the SiNx thin film and the Ag thin film were repeatedly performed one by one under the same conditions.
  • a fluorocarbon thin film (organic layer) was deposited to a thickness of 50 nm with MF power of 3.5 W / cm 2 through the cathode 2, and a barrier film used for thermal barriers having a 5-layer structure was formed. Rewound in dubu.
  • the moisture barrier film was produced in PET film (SKC, SH-40, thickness 100micrometer) using the cluster sputter apparatus.
  • a copper fluorine-based composite target (4 inches in diameter, 6 mm thick) made of circular particles containing 70 wt% of powdered PTFE (polytetrafluoroethylene, DuPont 7AJ), 10 wt% of carbon nanotubes, and 20 wt% of silicon oxide (SiO 2 ) Backing plate (Cu backing plate) was attached to the electrode surface.
  • PTFE polytetrafluoroethylene
  • SiO 2 silicon oxide
  • Silicon oxide target (4 inches in diameter, 6 mm thick, SiO 2
  • the inorganic layer was deposited on the target by RF (Radio Frequency) magnetron sputtering.
  • the substrate was prepared with a 10 X 10 cm 2 PET film (SKC, SH-40, thickness 100 ⁇ m), which was prepared by washing with acetone and alcohol for 5 minutes using an ultrasonic cleaner and drying.
  • the prepared substrate was attached to a substrate holder made of aluminum using a heat resistant tape, and the substrate holder was mounted on a substrate stage in the chamber, the chamber was closed, and a rotary pump was used to reach 50 mtorr.
  • the vacuum was evacuated and high vacuum was formed with a cryogenic pump after the low vacuum operation was completed.
  • the distance between the substrate and the target was fixed at 24 cm at room temperature (25 ° C.), and a 100 nm inorganic layer was deposited at a power (200 W) and a gas partial pressure (10 mtorr).
  • RF Radio Frequency
  • PET film (SKC, SH-40, thickness 100 ⁇ m, width 600mm) using a roll-to-roll sputter (ULVAC, SPW-060) apparatus to prepare a moisture barrier film (see Fig. 1).
  • Fluorinated polymer composite target (length 950 mm, width 127 mm, thickness) made of square plate containing 70 wt% of powder PTFE (polytetrafluoroethylene, DuPont 7AJ), 10 wt% of carbon nanotubes, and 20 wt% of silicon oxide (SiO 2 ) 6 mm) was attached to the copper backing plate electrode face. It was installed in MF dual sputtering cathode 1, and two Si targets (length 950 mm, width 127 mm, thickness 6 mm) were installed in MF dual sputtering cathode 2 (cathode 2).
  • the PET film is wound in an unwinder chamber, the inside of the roll-to-roll sputtering apparatus is made low vacuum by using a rotary pump and a booster pump, and then a high vacuum (2 ⁇ 10 -4) is used by using a turbo molecular pump. Pa) was formed.
  • the internal vacuum degree of the roll-to-roll sputtering device is 2 ⁇ 10 -4 Pa or less, pre-sputtering is performed by injecting argon (Ar) gas into each cathode at a flow rate of 400 sccm and MF and DC power of 1 kW. It was.
  • the temperature of the main roll was lowered to 10 ° C., and an inorganic layer was formed by MF dual sputtering cathode 2 while conveying the PET film at a speed of 0.5 m / min.
  • the inorganic layer was deposited with a thickness of 100 nm in an oxygen (O 2 ) atmosphere with MF power 13 kW through the cathode 2.
  • an organic layer including fluorine carbide was formed by MF dual sputtering cathode 1.
  • the organic layer was deposited with a thickness of 100 nm in an argon atmosphere with MF power 3 kW through the cathode 1.
  • the inorganic layer and the organic layer were sequentially repeated once more to produce a barrier film having a four-layer structure, and the water barrier film produced in the winder chamber was rewound.
  • the barrier film used for antireflection was produced using the roll-to-roll sputter (ULVAC, SPW-060) apparatus in PET film (SKC, SH-40, thickness 100micrometer, width 600mm) (refer FIG. 1).
  • Fluorinated polymer composite targets (square plate, length 950 mm, width 127 mm, thickness 6 mm) made of square plate containing 95 wt% of powdered PTFE (polytetrafluoroethylene, DuPont 7AJ) and 5 wt% of carbon nanotubes (Cu backing plate) It was attached to the electrode surface. It was installed in MF dual sputtering cathode 3. After that, the PET film is wound in an unwinder chamber, and the inside of the roll-to-roll sputtering device is evacuated to 50 mtorr using a rotary pump and a booster pump to make a low vacuum state, followed by a turbo molecular pump. Was used to form a high vacuum (2 ⁇ 10 ⁇ 4 Pa).
  • the MF dual sputtering cathode 3 was used to deposit an antireflection layer (n-1.38 @ 550 nm) with MF power of 2 kW (fluorocarbon thin film, 50 nm thick).
  • the barrier film used for the final deposited antireflection was rewound in the winder chamber.
  • Fluorinated polymer composite target (square plate, length 950 mm, width 127) made of square plate containing 60 wt% of powder PTFE (polytetrafluoroethylene, DuPont 7AJ), 10 wt% of carbon nanotube, 30 wt% of silica oxide (SiO 2 ) mm, thickness 6 mm) was attached to the copper backing plate electrode face. This was installed in MF dual sputtering cathode 3 to produce a barrier film used for antireflection in the same manner as in Example 5.
  • powder PTFE polytetrafluoroethylene, DuPont 7AJ
  • silica oxide SiO 2
  • the MF dual sputtering cathode 3 was used to deposit an antireflection layer (n-1.38 @ 550 nm) with MF power of 2 kW (fluorocarbon thin film, 50 nm thick).
  • the barrier film used for the final deposited antireflection was rewound in the winder chamber.
  • High Purity Nb 2 O 5 A target (99.9%, Mitsui, square plate, length 950 mm, width 127 mm, thickness 6 mm) is attached to the copper backing plate electrode surface and mounted on the MF dual sputtering cathode 1, and a high purity Si target ( 99.9%, Mitsui, square plate, length 950 mm, width 127 mm, thickness 6 mm) was attached to the copper backing plate electrode face and mounted on the MF dual sputtering cathode 2.
  • a copper fluorine-based composite target (square plate, length 950 mm, width 127 mm, thickness 6 mm) made of a rectangular plate containing 99 wt% of powdered PTFE (polytetrafluoroethylene, DuPont 7AJ) and 1 wt% of carbon nanotubes was copper.
  • Backing plate (Cu backing plate) was attached to the electrode surface. It was installed in MF dual sputtering cathode 3. After that, the PET film is wound in an unwinder chamber, and the inside of the roll-to-roll sputtering device is evacuated to 50 mtorr using a rotary pump and a booster pump to make a low vacuum state, followed by a turbo molecular pump.
  • a high refractive index layer (n-2.10 @ 550 nm) was deposited with MF power at 7 kW by MF dual sputtering cathode 1 (Nb 2 O 5 thin film, 40 nm thick), and MF power was continuously 13 kW by MF dual sputtering cathode 2
  • a low refractive index layer (n-1.46 @ 550 nm) was deposited (SiO 2 thin film, 60 nm thick).
  • an antireflection layer (n-1.38 @ 550 nm) was deposited by MF dual sputtering cathode 3 with MF power of 2 kW (fluorocarbon thin film, 50 nm thick).
  • the barrier film used for the final deposited antireflection was rewound in the winder chamber.
  • a high-purity Si target (99.9%, Mitsui, square plate, length 950 mm, width 127 mm, thickness 6 mm) is attached to the copper backing plate electrode surface and installed on the MF dual sputtering cathode 1, with high purity Nb 2 O 5
  • a target (99.9%, Mitsui, square plate, length 950 mm, width 127 mm, thickness 6 mm) was attached to the copper backing plate electrode face and mounted on the MF dual sputtering cathode 2.
  • a copper fluorine-based composite target (square plate, length 950 mm, width 127 mm, thickness 6 mm) made of a rectangular plate containing 99 wt% of powdered PTFE (polytetrafluoroethylene, DuPont 7AJ) and 1 wt% of carbon nanotubes was copper.
  • Backing plate (Cu backing plate) was attached to the electrode surface. It was installed in MF dual sputtering cathode 3.
  • a low refractive index layer (n-1.46 @ 550nm) was deposited with MF power at 2.2 kW by MF dual sputtering cathode 1 (SiO 2 thin film, 10 nm thick), followed by MF dual sputtering cathode 2 with MF power at 7 kW.
  • the high refractive index layer (n ⁇ 2.10 @ 550nm) was deposited (Nb 2 O 5 thin film, 40nm thickness).
  • MF dual sputtering cathode 1 Continuously reversed the direction, MF dual sputtering cathode 1 to deposit a low refractive index layer (n-1.46 @ 550nm) with MF power of 7kW (SiO 2 thin film, 40nm thickness), and again reverse the direction to continuously MF
  • the anti-reflective layer (n-1.38 @ 550 nm) was deposited by dual sputtering cathode 3 with MF power of 2 kW (fluorocarbon thin film, 50 nm thick).
  • the barrier film used for the final deposited antireflection was rewound in the winder chamber.
  • High-purity Si targets (99.9%, Mitsui, square plate shape, length 950 mm, width 127 mm, thickness 6 mm) were attached to the copper backing plate electrode face and mounted on MF dual sputtering cathodes 1 and 2.
  • a copper fluorine-based composite target (square plate, length 950 mm, width 127 mm, thickness 6 mm) made of a rectangular plate containing 99 wt% of powdered PTFE (polytetrafluoroethylene, DuPont 7AJ) and 1 wt% of carbon nanotubes was copper.
  • the backing plate was attached to the electrode face and mounted on the MF dual sputtering cathode 3.
  • MF dual sputtering cathode 1 deposits a high refractive index layer (n to 2.1 @ 550 nm) SiNx thin film (40 nm thick) using Ar and N 2 gas at MF power 10 kW and continuously MF power by MF dual sputtering cathode 2
  • the low refractive index layer (n-1.46 @ 550nm) SiO 2 thin film was deposited (40nm thickness) at 7kW.
  • the anti-reflective layer (n-1.38 @ 550 nm) was deposited by MF dual sputtering cathode 3 with MF power of 2 kW continuously in the opposite direction (fluorine carbide thin film, 50 nm thick).
  • the barrier film used for the final deposited antireflection was rewound in the winder chamber.
  • the barrier film used for thermal insulation was produced by the same method except the following conditions. Si targets (950 mm long, 127 mm wide, 6 mm thick) and Ag targets (950 mm long, 127 mm wide, 6 mm thick) were attached to the respective copper backing plate electrode faces, The target was installed with two Si targets in the MF sputtering cathode 1 in the process chamber and one Ag target in the DC sputtering cathode 3. Through the cathode 1 to the MF power to 8 W / cm 2 (N 2 gas) N 2 gas partial pressure (10 mtorr), a SiN thin film (optical compensation layer) was deposited to a thickness of 40 nm.
  • a barrier film used for thermal insulation of a structure laminated in two layers by depositing an Ag thin film (heat shielding layer) to a thickness of 12 nm with a DC power of 0.6 W / cm 2 through the cathode 3 on one surface of the SiN thin film. Rewinding in the winder to complete the production of a barrier film used for thermal cutoff.
  • Ag thin film heat shielding layer
  • the contact angle, the maximum visible light transmittance (Tmax), and the ultraviolet light transmittance (based on the measured wavelength of 1000 nm) were measured, and the results are shown in Table 1.
  • Example 1 Example 2 Comparative Example 1 Contact angle (°) 110 110 55 Maximum visible light transmittance (T max ,%) 48.1 60.5 42.5 Infrared transmittance (%) 8.0 6.9 19.5
  • the barrier film used for the heat shield according to the present invention by placing the fluorocarbon thin film at the outermost portion, the visible light transmittance can be improved, thereby increasing the transparency of the film and securing cyanity. It can be seen that the high contact angle can significantly improve the water repellency and antifouling properties caused by moisture or contaminants.
  • the barrier film used for the thermal barrier according to the present invention has an excellent infrared ray blocking rate to significantly increase the thermal insulation performance, maximize energy saving and heating and cooling efficiency, it is expected to be applicable to various industrial fields.
  • PET layer (SKC, SH-40, thickness 100um, width 600mm) using a roll-to-roll sputter device (ULVAC, SPW-060) in Example 4 using a 100% PTFE target instead of the fluorine-based polymer composite target, only the organic layer It was intended to form.
  • MF power was applied at 3 kW through the cathode 1 to form the organic layer.
  • plasma was not formed, deposition of the organic layer including fluorine carbide was not possible.
  • Example 4 It was intended to form only the inorganic layer according to Example 4 using a roll-to-roll sputter device (ULVAC, SPW-060) on the PET film (SKC, SH-40, thickness 100um, width 600mm).
  • a moisture barrier film deposited at a thickness of 100 nm was prepared by using an oxygen (O 2 ) atmosphere of MF power at 13 kW through the cathode 2.
  • Example 3 Example 4 Comparative Example 3 Contact angle (°) 109 110 30 Moisture Permeability (g / m2 / day) 3.7 ⁇ 10 -2 8.5 ⁇ 10 -3 4.7 ⁇ 10 -1
  • the moisture barrier film according to the present invention has a low moisture permeability compared to the comparative example it can be seen that exhibits excellent moisture barrier properties against moisture.
  • the organic layer having a fluorinated carbide thin film was formed at the outermost side to have a remarkably high contact angle, and showed excellent adhesion to the adherend, thereby effectively suppressing the detachment phenomenon due to external impact.
  • Anti-reflective layer using 100% PTFE target instead of fluorine-based polymer composite target in Example 5 using a roll-to-roll sputter device (ULVAC, SPW-060) on PET film (SKC, SH-40, thickness 100um, width 600mm) was intended to form.
  • MF power was applied at 7 kW through the cathode 1 to form the anti-reflection layer.
  • no plasma was formed, it was impossible to deposit the anti-reflection layer containing fluorine carbide.
  • PET film (SKC, SH-40, thickness 100um, width 600mm) using a roll-to-roll sputtering device (ULVAC, SPW-060), it was intended to form only the high refractive index layer and the low refractive index layer according to Example 5.
  • a barrier film used for antireflection was prepared in the same manner as in Example 5 except that the antireflection layer was deposited.
  • Example 5 Example 6 Example 7 Example 8 Example 9 Comparative Example 5 reflectivity(%) 4.3 4.2 4.0 3.5 4.0 6.0 Contact angle (°) 112 113 112 114 113 65
  • the barrier film used for the antireflection according to the present invention exhibits excellent water repellent characteristics compared to the comparative example.
  • a fluorocarbon thin film into the outermost layer, it has a high water contact angle, exhibits excellent bonding with the adherend, and can effectively suppress detachment due to external impact.
  • the barrier film according to the present invention maintains transparency and effectively blocks contaminants such as moisture, thereby providing various display devices (displays) such as organic EL displays, field emission displays, and liquid crystal displays, solar cells, thin films. It is expected to be used as a flexible substrate or an encapsulating material for various electric elements such as batteries, electric double layer capacitors, etc. to provide high quality devices.
  • display devices such as organic EL displays, field emission displays, and liquid crystal displays, solar cells, thin films. It is expected to be used as a flexible substrate or an encapsulating material for various electric elements such as batteries, electric double layer capacitors, etc. to provide high quality devices.

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  • Inorganic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Optics & Photonics (AREA)
  • Laminated Bodies (AREA)

Abstract

La présente invention concerne un procédé de fabrication d'un film barrière mince, le procédé mettant en application procédé rouleau à rouleau et comprenant les étapes consistant à : former, sur une surface d'une surface à coller, une couche inorganique comprenant, en tant que constituant principal, un ou plusieurs constituants choisis parmi un métal et un composé métallique ; et former, sur une surface de la couche inorganique, une couche organique par dépôt d'une cible composite polymère polymère à base de fluor comprenant un polymère à base de fluor et un agent de fonctionnalisation qui possède une conductivité, de sorte à obtenir un film barrière qui non seulement présente d'excellentes propriétés de barrière contre l'humidité, mais qui peut également être doté d'une flexibilité, et d'une transparence excellentes ainsi que de diverses formes de propriétés optiques, et qui présente une excellente résistance aux conditions environnementales.
PCT/KR2016/009772 2015-09-01 2016-09-01 Film barrière comprenant un film mince de fluoro-carbone et son procédé de fabrication WO2017039342A1 (fr)

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
KR10-2015-0123340 2015-09-01
KR1020150123340A KR101666350B1 (ko) 2015-09-01 2015-09-01 탄화불소 박막을 포함하는 열차단 필름 및 이의 제조방법
KR10-2015-0130675 2015-09-16
KR1020150130675A KR101719520B1 (ko) 2015-09-16 2015-09-16 탄화불소 박막을 포함하는 다층 배리어 필름 및 이의 제조방법
KR10-2016-0010369 2016-01-28
KR1020160010369A KR102010240B1 (ko) 2016-01-28 2016-01-28 발수 특성을 가지는 반사방지 필름 및 이의 제조방법

Publications (1)

Publication Number Publication Date
WO2017039342A1 true WO2017039342A1 (fr) 2017-03-09

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PCT/KR2016/009772 WO2017039342A1 (fr) 2015-09-01 2016-09-01 Film barrière comprenant un film mince de fluoro-carbone et son procédé de fabrication

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WO (1) WO2017039342A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111826622A (zh) * 2020-06-10 2020-10-27 深圳市锐欧光学电子有限公司 一种手机摄像头盖板镀膜方法
CN112813396A (zh) * 2020-12-30 2021-05-18 山东永聚医药科技有限公司 一步磁控溅射沉积无机/有机交替混合结构超高阻隔膜的制备方法

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JP2003098306A (ja) * 2001-09-19 2003-04-03 Sumitomo Metal Mining Co Ltd 反射防止フィルム
JP2007504500A (ja) * 2003-09-04 2007-03-01 エシロール アンテルナショナル コムパニー ジェネラル ドプテイク 光学基板上の反射防止被膜処理法と被膜処理された光学基板および被膜処理実施装置
JP2008266728A (ja) * 2007-04-20 2008-11-06 Toppan Printing Co Ltd 真空蒸着装置および真空蒸着方法
KR20110079500A (ko) * 2009-12-31 2011-07-07 삼성모바일디스플레이주식회사 배리어 필름 복합체, 이를 포함하는 표시 장치, 배리어 필름 복합체의 제조 방법, 및 이를 포함하는 표시 장치의 제조 방법
KR101470901B1 (ko) * 2014-08-08 2014-12-10 주식회사 코사인 시인성 향상과 열차폐 및 단열 특성을 겸비한 열반사 필름

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2003098306A (ja) * 2001-09-19 2003-04-03 Sumitomo Metal Mining Co Ltd 反射防止フィルム
JP2007504500A (ja) * 2003-09-04 2007-03-01 エシロール アンテルナショナル コムパニー ジェネラル ドプテイク 光学基板上の反射防止被膜処理法と被膜処理された光学基板および被膜処理実施装置
JP2008266728A (ja) * 2007-04-20 2008-11-06 Toppan Printing Co Ltd 真空蒸着装置および真空蒸着方法
KR20110079500A (ko) * 2009-12-31 2011-07-07 삼성모바일디스플레이주식회사 배리어 필름 복합체, 이를 포함하는 표시 장치, 배리어 필름 복합체의 제조 방법, 및 이를 포함하는 표시 장치의 제조 방법
KR101470901B1 (ko) * 2014-08-08 2014-12-10 주식회사 코사인 시인성 향상과 열차폐 및 단열 특성을 겸비한 열반사 필름

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN111826622A (zh) * 2020-06-10 2020-10-27 深圳市锐欧光学电子有限公司 一种手机摄像头盖板镀膜方法
CN112813396A (zh) * 2020-12-30 2021-05-18 山东永聚医药科技有限公司 一步磁控溅射沉积无机/有机交替混合结构超高阻隔膜的制备方法

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