WO2017039342A1

WO2017039342A1 - Barrier film comprising fluorocarbon thin film and method for manufacturing same

Info

Publication number: WO2017039342A1
Application number: PCT/KR2016/009772
Authority: WO
Inventors: 이상진; 이재흥; 최우진; 조성근; 함동석
Original assignee: 한국화학연구원
Priority date: 2015-09-01
Filing date: 2016-09-01
Publication date: 2017-03-09

Abstract

The present invention relates to a method for manufacturing a barrier thin film, the method enabling a roll-to-roll method and comprising the steps of: forming, on one surface of an adherend, an inorganic layer comprising, as a main ingredient, one or more ingredient selected from metal and a metal compound; and forming, on one surface of the inorganic layer, an organic layer by depositing a fluorine-based polymer composite target comprising a fluorine-based polymer and a functionalizing agent that has conductivity, and thus a barrier film may be provided that not only exhibits outstanding barrier properties against moisture, but also may be imparted with excellent flexibility, transparency and various forms of optical properties, and exhibits excellent environmental resistance.

Description

Barrier film comprising a fluorocarbon thin film and a manufacturing method thereof

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.

In general, glass substrates have been used in flat panel displays (FPDs) such as plasma displays, liquid crystal display, and organic light emitting display. 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. In order to solve this problem, 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. However, since 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.

Accordingly, various attempts have been made to form 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. In general, 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. In a high vacuum state, it may be manufactured by coating the surface of the plastic film by using 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. However, since 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.

Furthermore, since the formation of the gas barrier thin film used in the prior art necessarily requires a deposition process under high vacuum, an expensive device is required, and it takes a long time to reach a high vacuum, which is not economical. It was not desirable.

In addition, 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. Although the technology for providing the necessary functions is disclosed, the fluorine resin has good stability to moisture due to its structural characteristics, but has a low affinity with water for easy permeation, and thus the water vapor transmission rate of the entire backsheet is several tens of g / m 2 / day, which is sufficient thickness. Due to the nature of the solar cell that must be used for a long time under harsh external conditions when there is no coating of there is a lot of problems that can cause a decrease in function or shorten the life.

As a method for overcoming this problem and providing sufficient moisture barrier property to the fluorine paint, Patent Document 4 (US Patent Publication No. 2009-0260677) proposes a method of adding metal-coated mica particles which are plate-shaped particles. However, 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. In addition to solving the problem of conventional fluorine carbide thin film deposition that had to apply high energy, it is possible to deposit by 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. In addition, 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.

In another aspect, 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.

In addition, 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.

According to an aspect of the present invention, the inorganic layer and the organic layer may be formed by being deposited by RF, MF or DC sputtering, respectively.

As 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. In addition, 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. In addition, 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 In addition, 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.

In addition, according to an aspect of the present invention, 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.

In addition, 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. In addition, 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. In addition, 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.

In addition, according to 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.

In the method of manufacturing a barrier film according to the present invention, in a conventional roll-to-roll method capable of manufacturing a large-area thin film, an MF or DC sputtering device 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.

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.

Recently, a technique for blocking the penetration of moisture and oxygen has been greatly required for the better performance of the flexible display device. In particular, in the case of a flexible OLED device, a very high water penetration rate of 10 ^-5 to 10 ^-6 g / ㎡ / day is required, and in the case of a quantum dot film recently introduced to improve color reproduction, It requires a relatively low water permeability of 10 ^-3 g / m 2 / day, but it is not suitable for mass production because it is difficult to realize the above properties in the prior art and the process is complicated and costly. .

Accordingly, 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. Specifically, 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.

At this time, 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. As used herein, 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%.

In addition, 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.

Hereinafter, one specific embodiment of the 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.

In the case of the fluorocarbon thin film which is a representative insulator, 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. At this time, 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.

Specifically, the barrier film used for the heat shield according to an aspect of the present invention 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. 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. By fluorine carbide protective layer formed in the heat shielding rate can be maximized to more than 90%. In this case, 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.

In the heat ray shielding layer according to an aspect of the present invention, aluminum (Al), tungsten (W), gold (Au), tin (Sn), zinc (Zn), iron in addition to the main component in terms of improving the heat ray shielding effect Of course, 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. At this time, in order to further improve the optical properties of the barrier film used for the thermal barrier, to eliminate diffused reflection, etc., to obtain a clearer and brighter view, 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.

In general, in the case of fluorine-based polymers, in order to sputter them with hydrophobic and insulating properties, radiofrequency (RF) high-frequency energy must be applied, so that the fluorine-based polymer target is deformed as itself or The deformation inevitably occurred at the junction of, resulting in the generation of defects in the target. For this reason, the sputtered fluorine-based polymer may not be uniformly deposited on the surface of the adherend, but the deposition efficiency is inevitably poor.

Thus, the fluorocarbon protective layer according to the present invention, as described above, 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).

In the method for producing a barrier film used for thermal barrier according to an aspect of the present invention, the fluorocarbon protective layer is formed using a fluorine-based polymer composite target. In this case, 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.

Specific examples of 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. In this case, when the organic conductive particles which are examples of the conductive particles are used, conductivity can be imparted while maintaining the fluorocarbon component. Specific examples of 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. In addition, specific examples of the metal component 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.

In addition, 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 One or more selected from (PFA, poly tetra fluoro ethylene-co-fluoro alkyl vinyl ether) Fluorine polymers; At least one fluororubber selected from vinyl fluoride homopolymer rubber, vinyl fluoride copolymer rubber, vinylidene fluoride homopolymer rubber, vinylidene fluoride copolymer rubber, and the like; It may be one or more selected from, and more preferably may be polytetrafluoroethylene (PTFE, polytetrafluoroethylene), but is not limited thereto.

At this time, 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.

In addition, 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), polyvinyl chloride (PVC), ethylene-vinyl acetate copolymer (ethylene-vinyl acetate , EVA), ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), polyallylate (PAR), acrylic-styrene-acrylonitrile copolymer (acrylic-styrene- acrylonitrile copolymer, ethylene-butylene copolymer, ethylene-octene copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer propylene-diene monomer copolymer (EPDM), polyamide, polyphenylene oxide (PPO), polybutylene terephthalate (PBT), polytrimethylene terephthalate (polytr) imethylene terephthalate (PTT), polyoxy methylene (POM), polyphthalamide (PPA), polysulfone (PSf), polyether sulfone (PES), polyphenylene sulfide , PPS), liquid crystalline polymer (LCP), polyether imide (PEI), polyamide imide (PAI), polyketone (PK), polyether ether ketone (poly ether ether) ketone, PEEK), polyether ketone (PEK), polyether ketone ketone (PEKK), polyether ketone ether ketone ketone (PEKEKK), polyaryl ether ketone (polyaryl ketone) ether ketone (PAEK), polybenzimidazole (PBI), polyvinyl butyral (PVB), polypropylene carbonate (PPC), polylactic acid (PLA), polyhydroxyal Kanoei (Polyhydroxy alkanoates, PHAs), selected from a film, such as an alkyd resin (alkyd resin), phenol resin (phenol resin), epoxy resin (epoxy resin), or good or is used for fibers or glass but not limited to.

As described above, 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. In particular, 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.

That is, 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

In addition, 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.

In the method of manufacturing a barrier film for use in a thermal barrier according to an aspect of the present invention, 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. In order to realize a lower heat ray transmittance and excellent visible ray transmittance, 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. In addition, 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.

In addition, 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.

Next, the 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. Specifically, 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.

In the method of manufacturing a barrier film used for anti-reflection according to an aspect of the present invention, 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. In this case, 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.

In addition, in the method of manufacturing a barrier film used for anti-reflection according to an aspect of the present invention, 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.

In the barrier film used for anti-reflection according to an aspect of the present invention, in order to implement more excellent anti-reflection characteristics, the anti-reflection layer 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. Antimony oxide (Sb ₂ O ₃ ), zinc oxide (ZnO ₂ ), indium oxide doped tin (ITO), antimony-tin composite oxide (ATO), titanium-antimony Tin composite oxide (TiO ₂ , Sb doped SnO ₂ ), cerium oxide (CeO) selenium oxide (SeO ₂ ), aluminum oxide (Al ₂ O ₃ ), yttrium oxide (Y ₂ O ₃ ), niobium oxide (Nb ₂₎ O ₅ ) and antimony-zinc composite oxide (AZO), and the like, but are not limited thereto, and may include silicon nitride (SiN). In this case, 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. Thus, in the case of the low refractive index layer laminated on the high refractive index layer, the refractive index difference (Δn) 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 according to an aspect of the present invention 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. Preferably, 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.

In the method for producing a barrier film used for the antireflection according to an aspect of the present invention, 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. Can be. 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.

In addition, 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.

In the method for manufacturing a barrier film used for the antireflection according to an aspect of the present invention, 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. In this case, the refractive index difference (Δn) 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.

In addition, 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 μm, 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. At this time, 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 °.

Next, the 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 according to an aspect of the present invention 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. In addition, by having 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.

In addition, 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. It provides a manufacturing method. In this case, 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.

In this case, 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 according to an aspect of the present invention 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. In addition, 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.

Although the thickness of the inorganic layer and the organic layer of the barrier film used for preventing water permeation according to an aspect of the present invention is not limited, it may be deposited to a thickness of 1 nm to 10 μm. 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 according to an aspect of the present invention 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. At this time, 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 °.

In addition, 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.

According to an aspect of the present invention, 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.

In addition, 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 The properties of the barrier film used for prevention can be easily adjusted in one stop.

Hereinafter, the present invention will be described in more detail with reference to the following examples. However, these examples are only for the understanding of the present invention, and the scope of the present invention in any sense is not limited thereto.

In addition, in order to confirm the physical properties of the barrier film according to the present invention, the contact angle, the maximum transmittance and the infrared transmittance for visible light (550 nm) were measured by the following method, and the results are shown in Tables 1 to 3 below. .

1. Contact angle measurement

The water contact angle of the completed barrier film was measured using a contact angle measuring instrument (PHOEIX 300 TOUCH, SEO).

2. Maximum visible light transmittance (Tmax) measurement

The transmittance of visible light (550 nm) was measured by irradiating light to the finished barrier film using a spectrophotometer (U-410, Hitachi).

3.Infrared transmittance (measured at 1000nm wavelength)

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 (%).

4. Moisture transmittance measurement

The finished barrier film was measured for moisture permeability at 40 ± 0.5 ℃, 90% relative humidity conditions using a WVTR measuring instrument (Deltaperm, Technolux).

(Example 1)

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) 95 wt% carbon nanotube (CNT) 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. And one Ag target was installed in DC single sputtering cathode 4 (cathode 4). After that, the PET film is wound on an unwinder, 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 Pa) is used by using a turbo molecular pump. ) Was formed. When the internal vacuum of the roll-to-roll sputtering apparatus is 2 × 10 ⁻⁴ Pa or less, MF and DC power is 1.0 W / cm ² while argon (Ar) gas is injected into each cathode at a flow rate of 400 sccm, and the pre- sputtering was performed. Thereafter, 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. At this time, 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. On the Ag thin film, 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.

In order to confirm the physical properties of the barrier film used for the thermal barrier, the contact angle, visible light maximum transmittance (Tmax), and infrared transmittance (based on a measured wavelength of 1000 nm) were measured, and the results are shown in Table 1 below.

(Example 2)

In the said Example 1, the barrier film used for thermal insulation was produced by the same method except the following conditions. Through 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. On the Ag thin film, 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.

In order to confirm the physical properties of the barrier film used for the thermal barrier, the contact angle, visible light maximum transmittance (Tmax), and ultraviolet transmittance (based on a measured wavelength of 1000 nm) were measured, and the results are shown in Table 1 below.

(Example 3)

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.

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. At this time, the substrate was prepared with a 10 X 10 cm 2 PET film (SKC, SH-40, thickness 100㎛), 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). The fluorine-based polymer composite target manufactured on the upper portion of the inorganic layer under the same RF (Radio Frequency) magnetron sputtering conditions by depositing a fluorine carbide layer containing SiO ₂ 100nm, having a two-layer structure A moisture barrier film was produced.

In order to confirm the physical properties of the completed moisture barrier film, the contact angle and moisture transmittance were measured, and the results are shown in Table 2 below.

(Example 4)

PET film (SKC, SH-40, thickness 100㎛, 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). After that, 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. When 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. Thereafter, 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. At this time, 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. Thereafter, an organic layer including fluorine carbide was formed by MF dual sputtering cathode 1. At this time, the organic layer was deposited with a thickness of 100 nm in an argon atmosphere with MF power 3 kW through the cathode 1. In this manner, 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.

(Example 5)

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). When the internal vacuum of the roll-to-roll sputtering device was 2 × 10 ⁻⁴ Pa or less, pre-sputtering of each target was performed with MF power of 1 kW while argon (Ar) gas was injected into the cathode at a flow rate of 400 sccm. . Then, the temperature of the main roll was lowered to 10 degreeC, and the barrier film used for antireflection was produced, conveying a film at a speed | rate of 1 m / min.

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.

In order to confirm the physical properties of the barrier film used for the anti-reflection prepared by the above method, the reflectance and the contact angle were measured, and the results are shown in Table 3.

(Example 6)

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.

(Example 7)

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. In addition, 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. Was used to form a high vacuum (2 × 10 ⁻⁴ Pa). When the internal vacuum of the roll-to-roll sputtering device was 2 × 10 ⁻⁴ Pa or less, pre-sputtering of each target was performed with MF power of 1 kW while argon (Ar) gas was injected into the cathode at a flow rate of 400 sccm. . Then, the temperature of the main roll was lowered to 10 degreeC, and the barrier film used for antireflection was produced, conveying a film at a speed | rate of 1 m / min.

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). Subsequently, 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.

(Example 8)

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. In addition, 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). 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.

(Example 9)

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. In addition, 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.

(Comparative Example 1)

In the said Example 1, 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.

In order to confirm the properties of the barrier film used for the thermal barrier, 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.

	실시예 1Example 1	실시예 2Example 2	비교예 1Comparative Example 1
접촉각(°)Contact angle (°)	110110	110110	5555
가시광선 최대 투과율(T_max, %)Maximum visible light transmittance (T _max ,%)	48.148.1	60.560.5	42.542.5
적외선 투과율(%)Infrared transmittance (%)	8.08.0	6.96.9	19.519.5

As shown in Table 1, in the case of 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. In addition, 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.

(Comparative Example 2)

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. At this time, MF power was applied at 3 kW through the cathode 1 to form the organic layer. However, since plasma was not formed, deposition of the organic layer including fluorine carbide was not possible.

(Comparative Example 3)

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). At this time, in order to form the inorganic layer, 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.

	실시예 3Example 3	실시예 4Example 4	비교예 3Comparative Example 3
접촉각(°)Contact angle (°)	109109	110110	3030
수분 투과율(g/㎡/day)Moisture Permeability (g / ㎡ / day)	3.7 × 10^-2 3.7 × 10 ^-2	8.5 × 10^-3 8.5 × 10 ^-3	4.7 × 10^-1 4.7 × 10 ^-1

As shown in Table 2, 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. In addition, it was confirmed that 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.

(Comparative Example 4)

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. At this time, MF power was applied at 7 kW through the cathode 1 to form the anti-reflection layer. However, since no plasma was formed, it was impossible to deposit the anti-reflection layer containing fluorine carbide.

(Comparative Example 5)

In the 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.

	실시예 5Example 5	실시예 6Example 6	실시예 7Example 7	실시예 8Example 8	실시예 9Example 9	비교예 5Comparative Example 5
반사율(%)reflectivity(%)	4.34.3	4.24.2	4.04.0	3.53.5	4.04.0	6.06.0
접촉각(°)Contact angle (°)	112112	113113	112112	114114	113113	6565

As shown in Table 3, it can be seen that the barrier film used for the antireflection according to the present invention exhibits excellent water repellent characteristics compared to the comparative example. In addition, by introducing 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.

In short, 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.

[Description of the code]

100: unwinder chamber, 101: ion plasma trestment, 102: heater, 103: sub unwinder, 104: unwinder, 105 : Poly cold, 200: main chamber, 201: main roll, 202: MF dual cathode, 203: MF dual cathode, cathode 2), 204: MF dual cathode (cathode 3), 205: DC single cathode (MF single cathode, cathode 4), 205: poly cold, 300: winder chamber 301: resistance meter, 302: transmittance analyzer, 303: reflectance meter, 304: sub-winder (SUV WD), 305: winder

Claims

Forming an inorganic layer including at least one selected from metals and metal compounds as main components on one surface of the adherend, and depositing a fluorine-based polymer composite target including a fluorine-based polymer and a functionalizing agent having conductivity on one surface of the inorganic layer Method of manufacturing a barrier film comprising the step of forming an organic layer.
The method of claim 1,

The inorganic layer and the organic layer is a method of manufacturing a barrier film is formed by RF, MF or DC sputtering.
The method of claim 1,

The barrier film includes a step of forming an inorganic layer including an optical compensation layer including a thermal barrier addition element and a heat ray shielding layer including silver, copper or nickel as a main component, and a fluorine-based polymer and a functionalizing agent having conductivity. Method of manufacturing a barrier film for thermal barrier comprising depositing a polymer composite target to form an organic layer which is a fluorocarbon protective layer.
The method of claim 3, wherein

The thermal blocking additive elements of the optical compensation layer are NiCr, NiAu, ITO, IZO, IZTO, AZO, IAZO, GZO, IGO, IGZO, IGTO, ATO, IATO, IWO, CIO, MIO, MgO, SnO 2 , ZnO, ZnAlO selected from 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 Method for producing a barrier film to be used for thermal barrier.
The method of claim 3, wherein

The optical compensation layer and the heat ray shielding layer is a method for producing a barrier film used for thermal barrier is alternately laminated at least one or more times.
The method of claim 1,

The barrier film is used for preventing moisture permeation, including forming an inorganic layer including at least one selected from metal oxides and metal nitrides as a main component, and forming an organic layer including a fluorinated polymer and a functionalizing agent having conductivity. The method of manufacturing a barrier film.
The method of claim 6,

The inorganic layer comprises at least one metal selected from titanium, zirconium, hafnium, niobium, tantalum, vanadium, tungsten, aluminum, gallium, indium, zinc, silicon and germanium, oxides thereof and nitrides thereof. Method for producing a barrier film to be used for preventing water permeation that is formed using a target containing.
The method of claim 1,

The barrier film is formed by forming an inorganic layer, which is an anti-reflective layer including at least one selected from metal oxides, metal nitrides, and metal sulfides, and depositing a fluorine-based polymer composite target including a fluorine-based polymer and a functionalizing agent having conductivity. A method of manufacturing a barrier film used for antireflection, comprising forming an organic layer that is an antireflection layer.
The method of claim 8,

The reflection reducing layer includes a metal selected from titanium, zirconium, hafnium, niobium, tantalum, vanadium, tungsten, aluminum, gallium, indium, zinc, silicon, antimony, tin, cerium, selenium, yttrium, magnesium, and germanium. Method for producing a barrier film for antireflection comprising at least one metal oxide, metal nitride and metal sulfide as a main component.
The method of claim 9,

The reflection reduction layer includes a high refractive index layer and a low refractive index layer, wherein the low refractive index layer is a method for producing a barrier film used for antireflection that comprises at least one metal oxide selected from silicon and magnesium as a main component.
The method of claim 10,

The reflection reduction layer is a method of manufacturing a barrier film used for antireflection to form a multi-layer structure by repeating the step of depositing a high refractive index layer and the step of depositing a low refractive index layer.
The method of claim 1,

The functionalizing agent is a method for producing a barrier film of at least one selected from conductive particles, conductive polymers and metal components.
The method of claim 12,

The conductive particles are one or more selected from carbon nanotubes, carbon nanofibers, carbon black, graphene, graphite and carbon fibers, and the conductive polymers are polyaniline, polyacetylene, polythiophene, polypyrrole, polyfluene, polypyrene , Polyazulene, polynaphthalene, polyphenylene, polyphenylenevinylene, polycarbazole, polyindole, polyazepine, polyethylene, polyethylenevinylene, polyphenylenesulfide, polyfuran, polyselenophene, polytelurofen and At least one selected from polysulfur nitride, and the metal component is at least one selected from copper, aluminum, silver, gold, tungsten, silicon, magnesium, nickel, molybdenum, vanadium, niobium, titanium, platinum, chromium, and tantalum. Method of producing a barrier film.
The method of claim 1,

Wherein the organic layer further comprises at least one metal compound selected from metal organics, metal oxides, metal carbon bodies, metal hydroxides, metal carbonates, metal bicarbonates, metal nitrides, metal sulfides and metal fluorides.
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 includes a functionalizing agent having a fluorine-based polymer and conductivity on one surface of the inorganic layer. Method of producing a barrier film comprising the step of forming an organic layer using a fluorine-based polymer composite target.
The method of claim 15,

Forming the inorganic layer and the organic layer is a method of manufacturing a barrier film is performed by MF or DC sputtering.
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.
The method of claim 17,

A barrier film having a contact angle with moisture in the range of 90 to 150 degrees.
The method of claim 17,

Adherend; An inorganic layer comprising a heat ray shielding layer mainly composed of silver or copper or nickel and an optical compensation layer including a thermally blocked additional element; And a fluorocarbon protective layer comprising a fluorine-based polymer and a functionalizing agent having conductivity, an organic layer.
The method of claim 17,

Adherend; An inorganic layer comprising at least one selected from metal oxides and metal nitrides; And an organic layer comprising a fluorine-based polymer and a functionalizing agent having conductivity; a barrier film used for preventing water permeation.
The method of claim 17,

Adherend; An inorganic layer, which is a reflection reduction layer comprising at least one selected from metal oxides, metal nitrides and metal sulfides; And an organic layer, which is an antireflection layer comprising a fluorine-based polymer and a functionalizing agent having conductivity.
The method of claim 21,

The reflection reducing layer has a high refractive index layer and a low refractive index layer, and the low refractive index layer comprises at least one metal oxide selected from silicon (Si) and magnesium (Mg) as a main component, and the high refractive index layer and the low refractive index layer The refractive index difference (Δn) of 0.1 to 1.5 is a barrier film used for antireflection.