WO2017039339A1

WO2017039339A1 - Method for manufacturing fluorocarbon thin film

Info

Publication number: WO2017039339A1
Application number: PCT/KR2016/009757
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 fluorocarbon thin film and a continuous roll-to-roll method-based sputtering deposition system for the manufacturing thereof by which conductivity is imparted on a super water repellent and high insulating fluorine-based polymer, thereby enabling plasma to be stably formed even by means of the industrially widely used DC and MF power supply systems, thus enabling sputtering even at a more lower energy.

Description

Method of manufacturing fluorocarbon thin film

The present invention relates to a method for manufacturing a fluorine carbide thin film, and more particularly, to prevent dielectric breakdown of fluorine-based polymers and to realize a high deposition rate even in sputtering of an RF power supply system. Even the present invention relates to a method for producing a fluorocarbon thin film capable of stably sputtering.

Recently, the importance of the display device is increasing with the development of multimedia. In response to this, flat panel display devices such as liquid crystal display devices, plasma display devices, and organic light emitting display devices have been commercialized, and various digital devices such as smart phones, digital TVs, tablet PCs, notebook computers, PMPs, navigation devices, etc. have been released. But the demand for touch screens is increasing.

Examples of the flat panel display panel include LCD, PDP, and OLED. They are widely used as display devices of various digital devices because of their light weight, thinness, low power drive, full-color and high resolution. The touch screen is an input device installed on a display surface of various flat panel display devices and used to allow a user to select desired information while viewing the display device.

Such a flat panel display panel or a touch screen is exposed to the outside and is easily contaminated by contaminants containing moisture or moisture, and has a problem that it is not easy to wipe off contaminants when it is left standing for a long time with contaminants. Moreover, the display panel or touch screen needs to be protected from moisture because moisture may adversely affect the function of the product.

In order to solve this problem, a method of forming a hydrophobic film by forming a protective film containing fluorine on the surface of these display devices is mainly used. As a specific example of fluorine-based compound coating as a method for realizing a hydrophobic surface, a method of forming a thin film of the compound on a substrate by heating a solution containing an organosilicon compound containing a fluorine-substituted alkyl group as it is (Patent Document 1, JP2009-). 175500), PTFE (polytetrafluoroethylene), a powder dispersion is coated on a heat-resistant substrate and heated above the melting point to bind the powder to form a thin film (Patent Document 2, JP1993-032810), a fluorine-containing silazane-based organosilicon compound The method of depositing and depositing on a optical member by heating under vacuum (patent document 3, JP1993-215905), etc. are mentioned. However, the invention disclosed in Patent Document 1 has a problem in that when the raw material is heated for a predetermined time or more, the durability of the thin film is lowered, so that the thickness of the film that can be produced is limited, or a thin film having high durability cannot be stably produced. The invention disclosed in Patent Literature 2 is limited due to the high melting point of PTFE, and causes high cost. The invention disclosed in Patent Literature 3 is stable because the raw material used as the deposition source becomes unstable before being introduced into the deposition apparatus. There is a problem that can not produce a thin film.

In addition, another method for implementing a hydrophobic surface is a method using a fluorine-based surfactant. In order to realize hydrophobic surface properties, low molecular weight fluorine-based surfactants can be introduced to control the fluorinated hydrocarbons on the surface, but it causes problems in durability, and durability is improved when high molecular weight fluorine-based surfactants are introduced. Is not preferable because it causes difficulty in the appearance and may cause appearance problems on the surface due to phase separation from the coating matrix.

In order to overcome the problems as described above, in recent years, a technique for coating a fluorine-based polymer using a dry process rather than a wet process has been made. The most typical example is sputtering, which is a method of coating a fluorine-based polymer by a dry process, and a strong plasma is formed on the surface of the fluorine-based polymer, and the generated plasma gives strong energy to the surface of the fluorine-based polymer, and molecular-level fluorine-based polymer is separated from the surface and deposited on the opposite side. It is a process that is deposited and coated on the surface of the ash. However, in the case of sputtering targets having insulation characteristics such as polymer resins, when direct current power is applied, positive charges are collected on the target surface, which weakens the applied voltage, thereby reducing the energy of incident collision particles. Has the problem that it is not created. Due to this problem, high energy is required for sputtering of a material having an insulating property such as a polymer resin, and for this purpose, RF (Radio Frequency), which is a high frequency power supply method, has to be used. However, when sputtering with high energy RF using sputtering target with high insulation properties, it is not easy to apply negative voltage and shows low deposition rate of thin film. Additional equipment, such as a matching box, which controls separate impedance, is required.

Accordingly, the present inventors have solved the above problems of the conventional fluorine carbide thin film deposition which had to apply high energy, and the high deposition rate even with the sputtering of the power method having a frequency lower than tens of KHz or lower than RF. The present invention has been completed by developing a new technology capable of depositing and manufacturing a large-area fluorocarbon thin film in a roll-to-roll process in a very short time.

The present invention solves a problem in the method of manufacturing a thin film including a fluorine-based polymer that had to be applied to the RF (Radio Frequency) power source due to the superhydrophobic nature, and at the same time, excellent deposition at a relatively low power source compared to RF. An object of the present invention is to provide a method for producing a fluorocarbon thin film that can exhibit efficiency. Particularly, the present invention can form the same thin film as that of the RF power method even in a mid-range frequency (MF) or direct current (DC) power supply method, thereby implementing a roll-to-roll process capable of producing a large area thin film in a very short time. This is possible, and the existing roll-to-roll equipment can be directly applied to the replacement of the target without any additional renovation cost, thereby providing a method of manufacturing a fluorocarbon thin film having excellent commercial and economical efficiency.

Still another object of the present invention is to provide a roll-to-roll sputtering deposition system for fluorine carbide thin film deposition capable of stably sputtering fluorinated polymer even in MF or DC, and a molded body formed using the same. In this case, the molded article according to the present invention may be a high quality transparent fluorocarbon thin film having super water repellency. In addition, the present invention may be a fluorine-based polymer thin film having additional various physical properties depending on the type and content of the functionalizing agent. In another aspect, the present invention provides a molded article comprising a composite thin film comprising the fluorine-based polymer thin film and a molding agent comprising the same.

In the present invention, the thin film may include all substrates having various forms, for example, thin films formed on the surface of a substrate such as a film, a fiber, or a three-dimensional structure.

The present invention provides a method for producing a fluorocarbon thin film comprising the step of sputtering on a substrate using a fluorine-based polymer composite target comprising a functionalizing agent having conductivity to the fluorine-based polymer. At this time, the sputtering may be performed by RF, MF or DC power supply method, of course, due to the deterioration phenomenon due to the application of high energy during the deposition of the conventional fluorine-based polymer by the introduction of a functionalizing agent having the conductivity as described above Not only could the fluorine-based polymer target be damaged or the plasma generated at a lower efficiency than the applied voltage, it was able to drastically improve problems such as low deposition rate and carbonization which could realize high deposition rate even with more commercially available MF or DC power supply. The fluorine thin film can be manufactured.

In the method for manufacturing a fluorocarbon thin film according to an aspect of the present invention, sputtering in a roll-to-roll method using MF or DC power supply is possible. That is, while transporting the substrate in a roll-to-roll method, it is possible to perform the sputtering process by MF or DC power supply using a fluorine-based polymer composite target containing a conductive functionalizing agent to provide a large-area fluorocarbon thin film as well as The conventional roll-to-roll equipment can be directly applied without additional modification cost, thereby enabling automation, simplification, and continuous manufacturing of the fluorocarbon thin film manufacturing method.

In addition, the method of manufacturing a fluorocarbon thin film according to an embodiment of the present invention is not only applicable to a variety of substrates, but also in addition to the plate-shaped substrate, some of the curved form, for example, the curved edge, only the curved corner, Uniform application is possible even when applied to a substrate having all three-dimensional shapes such as curved shape and hemispherical shape.

The method for manufacturing a fluorocarbon thin film according to the present invention is a power supply method of MF or DC sputtering, which has a relatively low frequency of several tens of KHz or less than RF, so that a large-area thin film can be manufactured. Implementation is possible. In addition, since the fluorocarbon thin film can be manufactured by a low energy power supply method, it can be directly applied to the existing roll-to-roll equipment without any additional modification cost, and thus commerciality is also excellent.

In the method of manufacturing the fluorocarbon thin film according to an aspect of the present invention, the fluorine-based polymer composite target is additionally a metal compound, that is, metal organic matter, metal oxide, metal carbon body, metal hydroxide, metal carbonate, metal bicarbonate, metal nitride Of course, it may further include a single or mixed component selected from metal fluoride and the like. With the addition of such metal compounds, the physical, chemical, and optical properties of the molded article, ie, fluorocarbon thin film, produced by the manufacturing method according to the present invention can be easily adjusted.

In addition, the method for manufacturing a fluorocarbon thin film according to an aspect of the present invention may further include an additional treatment step to control the surface characteristics of the fluorocarbon thin film. Specifically, the treatment process may be to inject the reactive gas during the sputtering of the fluorocarbon thin film to perform reactive sputtering or to inject the surface treatment gas after the sputtering to perform plasma surface treatment.

The present invention provides a continuous roll-to-roll sputtering deposition system suitable for a method of manufacturing a fluorocarbon thin film capable of sputtering at low energy. The roll-to-roll deposition apparatus can be used without limitation as long as the conventional one, but briefly described with reference to the drawings of FIG.

The roll-to-roll sputtering deposition system includes an unwinder chamber 100 in which a roll on which a web-type substrate is wound is mounted, and a main chamber 200 in which a fluorocarbon thin film is deposited on one surface of the substrate. And a winder chamber 300 for winding the deposited fluorocarbon thin film.

In the main chamber of the roll-to-roll sputtering deposition system according to an aspect of the present invention, three MF dual cathode (cathodes 1 to 3, 202-204) and one DC single sputtering cathode (MF single cathode) ,

cathodes

4 and 205, which enables continuous sputtering using MF and DC, as well as sputtering simultaneously with various targets including metals or alloys, and are easy to manufacture large-area thin films. The productivity of the fluorocarbon thin film can be greatly improved.

The present invention provides a molded body formed by sputtering by MF or DC power supply using a fluorine-based polymer composite target including a conductive agent having conductivity on a substrate, that is, a high quality fluorocarbon thin film.

The present invention provides a high quality fluoride carbide thin film with improved deposition rate by effectively preventing defects caused by conventional strong energy, insulation breakdown, etc. by using a conductive fluorinated polymer composite target and generating plasma with high efficiency. Can be. This effect is more prominent in the sputtering method of the RF power method applying a stronger energy.

The method for producing a fluorocarbon thin film according to the present invention is not only possible to sputter with a MF or DC power supply method having a frequency lower than tens of KHz or lower than that of the conventional sputtering method using a fluorine-based polymer target. Compared to the fluorocarbon thin film using the% fluorine-based polymer target, not only can the physical, chemical, and optical properties be significantly improved, but also various functionalities can be simultaneously provided.

In addition, the manufacturing method according to the present invention can be directly applied to the production of fluorinated carbide thin film without the need for additional modification of the conventional roll-to-roll MF or DC sputtering apparatus capable of manufacturing a large-area thin film, automation and simplification of the process And it is possible to manufacture a continuous fluorocarbon thin film. At this time, by applying the roll-to-roll sputtering deposition system according to the present invention, the sputtering process efficiency of the fluorocarbon thin film can be improved more quickly or more.

1 is a schematic diagram of a roll-to-roll sputtering deposition system according to the present invention.

Figure 2 is an XPS analysis result in the water repellent layer of the super water-repellent coating fiber prepared by the method of Example 21.

3 is a surface elasticity and hardness characteristics of the transparent hard coat film prepared by the method of Example 22.

4 is a result of surface elasticity and hardness of the transparent hard coat film manufactured by the method of Example 23.

A method of manufacturing a fluorocarbon thin film according to the present invention will be described in detail below, but unless otherwise defined in technical terms and scientific terms used herein, a person having ordinary knowledge in the technical field to which the present invention pertains generally means The description of well-known functions and configurations that may unnecessarily obscure the subject matter of the present invention will be omitted.

The method of manufacturing the fluorocarbon thin film according to the present invention is different from the method of manufacturing the fluorocarbon thin film, which requires a high energy such as RF in the related art in that it can be implemented regardless of the output voltage.

In addition, the present invention can not only implement a high deposition rate even by using a sputtering process of MF or DC power supply, which is an industrially useful power supply method, but also deforms the electrode surface or the electrode surface that can be generated when a strong energy such as RF is applied. It is possible to effectively prevent the occurrence of defects and the like at the joints.

In addition, the method for manufacturing a fluorocarbon thin film according to the present invention enables the implementation of a roll-to-roll process capable of manufacturing a large-area thin film, and the automation, simplification and continuous carbonization of the process using existing roll-to-roll equipment with a low energy power method It is possible to provide a method for producing a fluorine thin film.

In the method for manufacturing a fluorocarbon thin film according to an aspect of the present invention, a sputtering process may be performed by MF or DC power supply using a fluorine-based polymer composite target having conductivity while transferring a substrate in a roll-to-roll manner. In this case, the fluorine-based polymer composite target includes a fluorine-based polymer and a functionalizing agent having conductivity. In this case, the functionalizing agent is not limited as long as it has a conductivity, but one example may be one or a mixture of two or more selected from conductive particles, conductive polymers, and metal components.

Non-limiting 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. Non-limiting examples of the conductive polymer, polyaniline (polyaniline), polyacetylene (polyacetylene), polythiophene (polythiophene), polypyrrole (polypyrrole), polyfluorene (polyfluorene), polypyrene (polypyrene), polyazulene ( polyazulene, polynaphthalene, polyphenylene, poly phenylene vinylene, polycarbazole, polyindole, polyazephine, polyethylene , Polyethylene vinylene, polyphenylene sulfide, polyfuran, polyselenophene, polytellurophene, polysulfur nitride And the like, but are not limited thereto. Further, non-limiting examples of the metal component are 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. Silver (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) Fluorinated polymer or copolymer comprising one or more of these; 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 substrate 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 (polymethacrylate, PMA), polystyrene (PS), styrene-acrylonitrile copolymer (styrene- acrylonitrile copolymer (SAN), acrylonitrile-butylene-styrene copolymer (ABS), polyvinyl chloride (PVC), ethylene-vinyl acetate, EVA ), Ethylene-vinyl alcohol copolymer (EVOH), polyvinyl alcohol (PVA), polyallylate (PAR), acrylic-styrene-acrylonitrile copolymer ), Ethylene-butylene copolymer, ethylene-octene copolymer, ethylene-propylene copolymer, ethylene-propylene-diene copolymer diene monomer copolymer (EPDM), polyamide, polyphenylene oxide (PPO), polybutylene terephthalate (PBT), polytrimethylene terephthalate (polytrime) thylene 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 Canoate (polyhydroxy alkanoates, PHAs), alkyd resin (alkyd resin), phenolic resin (phenol resin), epoxy resin (epoxy resin) and the like selected from the film or used in fiber or glass, but is not limited thereto.

Sputtering according to the method for producing a fluorocarbon thin film of an aspect of the present invention may be a reactive sputtering step performed under reaction gas injection. Due to this reactive sputtering, the molded article, ie, the fluorocarbon thin film manufactured by the manufacturing method according to the present invention, can maintain the hydrophobic surface property as it is and at the same time give enhanced oil repellency, and have excellent adhesion to the substrate. At this time, the oil repellency according to the present invention may mean a property that hydrocarbons such as toluene, decane, hexadecane, or alcohol represented by IPA (Isopropyl alcohol) does not penetrate, and in the first half of the present invention, It has been described as oil repellency for, but of course not limited to oil repellent for that.

That is, the molded body formed by the reactive sputtering according to an aspect of the present invention, that is, a fluorocarbon thin film is deposited on the outermost layer of the surface of a display device such as a flat panel display panel or a touch screen with excellent oil repellent properties as well as super water repellent properties to attach contaminants When preventing and attaching contaminants, it is expected to facilitate the removal of contaminants and to be used in various applications because of excellent surface modification properties. In addition, the fluorocarbon thin film according to the present invention is highly applicable to a surface protection film due to high transparency, and can be applied to various anti-reflection films due to low refractive index.

According to one aspect of the present invention, the fluorocarbon thin film may be prepared by performing at least one reactive sputtering process to implement desired water and oil repellent properties. In addition, the present invention can be prepared by appropriately adjusting the components of the fluorine-based polymer composite target and their content and the type and flow rate of the reaction gas in various embodiments according to various purposes or functions in the reactive sputtering process. In addition, the present invention significantly improves the process convenience, and the reactive sputtering process is preferably performed by the MF or DC power source for the purpose of more improved sputtering efficiency, but is not limited thereto.

The method of manufacturing a fluorocarbon thin film satisfying the water / oil repellent property according to the present invention is conventional RF (Radio Frequency) in terms of being deposited regardless of the output voltage by using a fluorine-based polymer composite target containing a functionalizing agent having conductivity It is differentiated from the manufacturing method using the fluorine-based polymer target that required high energy.

The reaction gas according to an aspect of the present invention is oxygen (O ₂ ), ozone (O ₃ ), hydrogen peroxide (H ₂ O ₂ ), ammonia (NH ₃ ), nitrous oxide (N ₂ O), nitrogen monoxide (NO) , Nitrogen dioxide (NO ₂ ), nitrogen (N ₂ ), carbon tetrafluoride (CF ₄ ) and hydrazine (N ₂ H ₄ ) and the like may be one or more selected from those used in the art are not limited. In order to have a lower surface energy value and excellent visibility, injecting one or more reactive gases selected from oxygen (O ₂ ), ozone (O ₃ ), nitrous oxide (N ₂ O), nitrogen (N ₂ ), etc. good.

In addition, the process gas according to the present invention is not limited as long as it is an inert gas, but non-limiting examples thereof include one or more process gases selected from argon (Ar), helium (He), nitrogen (N ₂ ), neon (Ne), and the like. It is preferred to be injected with. The process gas and the reaction gas may be injected in a mixing ratio (process gas: reaction gas, based on the flow rate unit) in the range of 1: 1 to 1000: 1, preferably 1: 1 to 100: 1, more preferably 1 It may be mixed in a mixing ratio of 1: 1 to 20: 1, but may be modified in various embodiments to control physical properties such as water repellency, oil repellency, visible light transmittance, and chromaticity.

In addition, the method for manufacturing a fluorocarbon thin film according to an embodiment of the present invention may further perform the step of treating the surface of the fluorocarbon thin film by using an ion plasma by injecting a surface treatment gas into the formed fluorocarbon thin film. . By further including the above-described surface treatment step, it is possible to provide a fluorocarbon thin film in which the desired contact angle, visible light transmittance, chromaticity and the like can be easily adjusted according to the method for producing a fluorocarbon thin film according to an aspect of the present invention. That is, further comprising a surface treatment step according to an aspect of the present invention, while maintaining the optical properties of the fluorocarbon thin film stably, it is possible to implement the improved durability and flexible transparent fluorocarbon thin film that can easily adjust the surface energy value Can be provided.

The surface treatment gas may be at least one selected from argon, nitrogen, oxygen, carbon tetrafluoride (CF ₄ ), hydrogen, and the like, and a reaction gas in which argon and oxygen are mixed in view of having a lower surface energy value and excellent visibility. It is good to inject.

In addition, according to an aspect of the present invention, the surface characteristics (for example, water repellent and oil repellent) and the optical properties of the surface of the formed fluorocarbon thin film can be appropriately adjusted, and the strength, chemical resistance, and the atmosphere of the fluorocarbon thin film The aging phenomenon which appears at the time of exposure, etc. can be remarkably improved.

At this time, the flow rate of the surface treatment gas is not limited, but may be injected at a flow rate of 1 to 1000 sccm to maximize the above-described effects, preferably may be injected at a flow rate of 5 to 800 sccm, more preferably 10 Injected at a flow rate of 500 sccm, but is not limited thereto.

In the method for producing a fluorocarbon thin film according to an aspect of the present invention, the sputtering may be performed by forming a plasma with a power of 0.1 to 15 W / ㎠, preferably a power of 0.3 to 10 W / ㎠, more Preferably it is carried out at a power of 0.5 to 5.0 W / ㎠.

The fluorine-based polymer composite target according to an aspect of the present invention further includes at least one metal compound selected from metal organic matter, metal oxide, metal carbon body, metal hydroxide, metal carbonate, metal bicarbonate, metal nitride and metal fluoride, thereby forming a film. Various functionalities can be imparted to the fluorocarbon thin film. At this time, non-limiting examples of the metal compound is SiO ₂ , Al ₂ O ₃ , ITO, IGZO, ZnO, In ₂ O ₃ , SnO ₂ , TiO ₂ , AZO, ATO, SrTiO ₃ , CeO ₂ , MgO, NiO , CaO, ZrO ₂ , Y ₂ O ₃ , Al ₂ O ₃ _, MgF ₂ , CuF ₂ , Si ₃ N ₄ , CuN, Nb ₂ O ₅ , V ₂ O ₅ And AlN may be selected from, and the like formed thin film SiO ₂ , Al ₂ O ₃ , ITO, Nb ₂ O ₅ , V ₂ O ₅ It is good to be selected from such.

In addition, the present invention provides a continuous roll-to-roll sputtering deposition system suitable for a method for producing a fluorocarbon thin film capable of sputtering at low energy (see FIG. 1).

Roll-to-roll sputtering deposition system according to an aspect of the present invention is an unwinder chamber (100), the main chamber (200) for depositing a fluorocarbon thin film on one surface of the substrate and the deposited fluorine carbide Winder chamber (300) for winding a thin film may be included, which can realize excellent deposition rate even in low energy bands such as MF or DC, and continuous roll-to-roll process, while ensuring simplicity in the manufacturing process In addition, it is possible to quickly form a large-area fluorocarbon thin film without defects.

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 MF and DC sputtering can be performed at the same time but also have the advantage that the deposition of the composite material is possible by applying various kinds of targets.

In addition, the winder chamber includes a resistance meter (301), a transmittance analyzer (302) and a reflectance meter (reflectance meter, 303), fluorocarbon manufactured from the roll-to-roll type sputtering deposition system The properties of the thin film can be conveniently performed in one stop.

The substrate according to an aspect of the present invention is not limited to the roll-to-roll sputtering deposition system but is transported at a speed of 0.1 m / min to 20 m / min, preferably 0.5 m / min to 5 m / It is good to feed at min speed.

According to the present invention, the low deposition rate and the considerably high defect rate, which are problems in the conventional method of manufacturing a fluorine carbide thin film, which had to be accompanied by high frequency energy of RF as having hydrophobic and insulating properties, are solved, thereby improving productivity. Commercially available MF or DC sputtering can be used to provide economically high quality fluorocarbon thin films.

In addition, the present invention provides a molded article, ie, a fluorocarbon thin film formed by sputtering using a fluorine-based polymer composite target containing a conductive agent having conductivity on a substrate. The fluorocarbon thin film according to the present invention can be deposited with excellent deposition rate even at a lower voltage by using a conductive fluorine-based polymer target, and it is possible to form nano-level thin films while maintaining the hydrophobic surface property as it is. In addition, the adhesion to the substrate is also excellent.

In the fluorocarbon thin film according to the aspect of the present invention, the contact angle with moisture may be in the range of 90 to 150 °, preferably 110 to 150 °, more preferably 140 ° or more, so that super water-repellent characteristics can be realized. Do.

In addition, the thickness of the fluorocarbon thin film according to an aspect of the present invention is not limited, but may be deposited with a thickness of 5 nm to 1 μm, and in terms of achieving a lower transmittance for moisture and a contact angle with respected moisture. Preferably it can be deposited to a thickness of 10 nm to 200 nm.

Hereinafter, an example of a molded article according to an aspect of the present invention may be exemplified as follows, but is not limited thereto.

According to one aspect of the present invention, sputtered using a fluorine-based polymer composite target containing a functionalizing agent on the surface of the textile fabric, excellent hydrophobic properties, flame retardant properties, flame-retardant properties, self-cleaning properties and water repellent properties, mechanical It is possible to provide a highly functional super water-repellent coated fiber to which special functions such as properties, antibacterial properties and electromagnetic shielding properties are given.

It can maximize productivity and minimize the generation of contaminants that can be generated in the process by directly coating the fluorocarbon thin film on the surface of the textile fabric in a single process without the use of harmful chemicals such as organic solvents. Can be. In addition, the super water-repellent coating fibers according to the present invention, by introducing an inorganic layer using a metal target, a metal oxide target or a metal nitride target, prior to the step of depositing a fluorocarbon thin film using the fluorine-based polymer composite target described above, By maximizing the adhesion between and the water repellent layer can maintain the super water-repellent properties even during multiple washing. In this case, the inorganic layer may be formed preferentially on the fiber substrate or may sequentially form the inorganic layer and the fluorocarbon thin film layer.

The super water-repellent coating fibers according to an aspect of the present invention is formed by repeatedly repeating the step of forming an inorganic layer and the step of forming an organic layer (fluorine carbide thin film) two or more times, from the textile fabric by deterioration or impact, washing, etc. Desorption can be significantly reduced.

In addition, the present invention provides a multifunctional super water-repellent coated fiber produced by the above production method. Preferably, but not limited to, the super water-repellent coating fibers according to the present invention may be included in the atomic weight ratio of the metal atoms of 0.01 to 50% by weight, based on 100% by weight of the total atomic weight contained in the organic layer. In addition, the organic layer of the super water-repellent coating fiber further includes a metal compound with a functionalizing agent having conductivity, thereby providing various functionalities such as electrical conductivity, heat dissipation, thermal insulation, antifouling, flame retardant, antibacterial, electromagnetic shielding properties and improved appearance. It is possible to provide various types of textile fabrics. As a non-limiting example, the water repellent layer is Al ₂ O ₃ in terms of effectively suppressing the generation of static electricity Metal compounds such as, and the like, may include metal components such as Ag in order to give excellent antimicrobial properties, but is not limited thereto.

In addition, the fiber fabric, which is one example of the substrate according to one aspect of the superhydrophobic coated fiber according to the present invention, polyvinyl alcohol, polyacrylonitrile, nylon, polyester, polyurethane, polyvinyl chloride, polystyrene, cellulose , Chitosan, silk, cotton yarn, polylactic acid, polylactic-co-glycolic acid, polyglycolic acid polycaprolactone, collagen, polypyrrole, polyaniline and poly (styrene-co-maleic anhydride) It may be made, but if it can be produced with conventional fibers are not limited.

In addition, according to one aspect of the present invention (substrate) as a natural skin; textile; knitting; Non-woven; Skin material such as artificial skin synthesized by adding a resin such as PU or PVC to an artificial leather or a fiber bubble having a relatively simple tissue form; And the like can be applied without limitation. By applying to the base material, the original material of the base material has the same as it is, combines chemical resistance (detergent, lax, disinfectant, etc.), it is possible to maximize the water repellent properties and antifouling properties. In addition, it can be applied to high-strength fabric made of high strength yarn such as polyamide multifilament, glass fiber or carbon fiber to improve initial water repellency as well as water repellency after friction, and effectively prevent wrinkles of textile fabrics generated during water repellent treatment. have.

At this time, there is no particular limitation on the diameter and length of the yarn, but the diameter may be between 1 and 100 μm, preferably between 5 and 20 μm, and the length is usually between 500 μm and 10 cm, in particular 1000 It may be between μm and 5 cm.

According to the present invention, uniform sputtering of nano-sized thickness is possible on the fiber surface, and the surface of the fiber fabric can be modified to have super water repellency regardless of the type of the fiber fabric through a single process, and the adhesion to the fiber fabric is improved. Significantly improved super water repellency can be maintained for a long time with or without washing.

In addition, the present invention provides a highly functional coating fiber having a special function of antifouling, antibacterial, deodorant, flame retardant, electromagnetic shielding, etc. as well as super water repellent properties by using a fluorine-based polymer composite target further comprising a variety of metals and ceramics, etc. can do.

In this case, the ceramic is not limited, but may be ceramic fine particles such as pegmatite and bentonite that emit far infrared rays. Preferably, the fine particles may have an average diameter of 0.01 to 10 μm, more preferably 0.01 to 3 μm. The pegmatite is a rock in which a bitumen, a silly stone, a padite, an albite, and the like form a quartz and a cultured structure, and biotite garnet tin stone column bite, fergusonite, fluorite, tourmaline, spodumene, topaz, It is a rock composed of various minerals emitting far infrared rays such as tantalum, and the bentonite is clay containing montmorillonite, a mineral belonging to a monoclinic system having a mica-like crystal structure, and quartz, feldspar, zeolite, etc. It may be included.

According to still another aspect of the present invention, a high hardness transparent hard coat film can be provided by applying a conductive functional agent, particularly a fluorine-based polymer composite target containing carbon nanoparticles, onto a flexible substrate.

Generally, when sputtering fluorine-based polymers and depositing them on a substrate, despite the possibility of producing a transparent and flexible water-repellent fluorocarbon thin film, the surface hardness is about 200 MPa so that when applied to the surface of a liquid crystal display device or the like, it is easily affected by the external environment. Wear and the like. The transparent hard coat film according to the present invention has a large number of C-C bonding structure and organic-inorganic composite structure, it is possible to solve the above problems by giving a significantly improved hardness and elastic properties (modulus).

The transparent hard coat layer according to an aspect of the present invention may be effectively applied to a flexible liquid crystal display and a folding or bent display device, which are currently commercialized for having excellent cyanity and improved durability and excellent adhesion to a substrate. have.

In particular, the transparent hard coating film according to the present invention is sputtered using a fluorine-based polymer composite target containing fluorine-based polymers and carbon nanoparticles, in order to realize more improved hardness and elastic properties, and furthermore, conductive polymers, metal components and One embodiment further including at least one functionalizing agent selected from metal compounds and the like is also of course included in the present invention.

At this time, the light transmittance (550 nm) of the above-mentioned transparent hard coat film is characterized in that it has a high transparency of 90% or more, preferably 90 to 99%, more preferably 91 to 98% may have a light transmittance. have. In addition, the hardness of the transparent hard coating film according to the present invention is not limited, but preferably has a high hardness characteristics in the range of 1.0 to 10.0 GPa, but may be implemented as a hard coating film having various hardness characteristics according to the purpose.

In addition, even if the hard coating film of the present invention bends or folds continuously or repeatedly, the hard coating film effectively suppresses cracking or peeling of the hard coating film, thereby providing excellent durability and reliability to the flexible liquid crystal display device employing the same.

According to another aspect of the present invention, a high quality water and oil repellent coating film is provided. The water / oil repellent coating film may be prepared by performing a reactive sputtering process under injection of a reaction gas using a fluorine-based polymer composite target including a functionalizing agent having conductivity on a substrate. It is not only capable of depositing at an excellent deposition rate even at a lower voltage, but also capable of forming nanoscale films, maintaining hydrophobic surface properties as well as having improved oil repellency, and having excellent adhesion to substrates. Has

That is, the water / oil repellent coating film according to the present invention is deposited on the outermost layer of the surface of a display device such as a flat panel display panel or a touch screen, thereby preventing contaminant adhesion and removing contaminants when attaching contaminants, and having excellent surface modification properties. Utilization of furnace is expected. In addition, the water- and oil-repellent coating film according to the present invention is highly applicable to a surface protection film due to high transparency, and can be applied to various display devices due to its low refractive index.

The water and oil repellent coating film according to one aspect of the present invention has a contact angle with water in a range of 100 to 150 ° and has excellent water repellency, as well as a contact angle with hexadecane of 50 ° to 70 °. It is characterized by having a significantly improved oil repellency compared to the thin film (35 °).

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 fluorocarbon thin film according to the present invention, the contact angle, the thickness of the thin film, the surface characteristics and the light transmittance were measured by the following method, and the results are shown in Tables 1 to 5 below.

1. Contact angle measurement

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

2. Thin Film Thickness Measurement

In order to measure the thickness of the finished fluorocarbon thin film, the substrate was cut and the cross section was measured using a FE-SEM (Field Effect-Scanning Electron Microscope, Philips XL30S FEG) apparatus.

3. Measurement of surface properties

In order to measure the surface characteristics of the finished fluorocarbon thin film, the surface hardness characteristics of the indentation depth were measured by increasing the load to 0 to 4 mN by the nanoindentation method (Nanoindenter Xp manufactured by MTS Systems Corp.). 15 experiments were conducted for each sample to calculate the average and standard deviation of the surface hardness according to the indentation depth. In addition, elastic properties were measured by the same method.

4. Light transmittance measurement

In order to measure the light transmittance of the completed fluorocarbon thin film, the light transmittance at a wavelength of 550 nm was measured after measuring the light transmittance in the wavelength range of 300 to 700 nm using a spectrophotometer (Hitachi Co., U-4100 type). Measured.

(Example 1)

A fluorocarbon thin film was produced on a PET film (SKC, SH-40, thickness 100 μm, width 600 mm) using a roll-to-roll sputter (ULVAC, SPW-060) apparatus (see FIG. 1).

The fluorine-based polymer composite target (length 950 mm, width 127 mm, thickness 6 mm) was manufactured in a square plate shape. A fluorine-based polymer composite target containing 90 wt% of powder PTFE (polytetrafluoroethylene, DuPont 7AJ) and 10 wt% of carbon nanotubes (average particle diameter: 30 nm) was attached to the copper backing plate electrode surface. It was installed in MF dual sputtering cathode 2. After that, the PET film is wound in an unwinder chamber, and the inside of the roll-to-roll sputtering device is made low vacuum by using a rotary pump and a booster pump, and then a high vacuum (2 × 10 ^-4 Pa) is obtained by using a turbo molecular pump. 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 the fluorocarbon thin film was deposited while conveying the PET film at a speed of 1 m / min. In this case, the fluorocarbon thin film was wound in the winder chamber a thin fluorocarbon thin film deposited with a thickness of 30 nm at MF power 2.5 W / cm ² through the cathode 2.

In order to confirm the physical properties of the fluorocarbon thin film prepared by the above method, the water contact angle was measured, and the light transmittance in visible light (550 nm) was measured, and the results are shown in Table 1 below.

(Example 2)

Instead of installing the fluorine-based polymer composite target of Example 1 in the MF dual sputtering cathode 2 (cathode 2), except that it is installed in the DC single sputtering cathode 3 (cathode 4) to perform at DC power 2.5 W / cm ² In the same manner to prepare a fluorocarbon thin film deposited to a thickness of 30 nm.

	실시예 1Example 1	실시예 2Example 2
접촉각(°)Contact angle (°)	108108	107107
가시광선 투과율(%)Visible light transmittance (%)	91.0691.06	90.9290.92

As shown in Table 1, the fluorocarbon thin film according to the present invention can be sputtered by MF and DC power supply by using a fluorine-based polymer composite target containing a functionalizing agent having conductivity, thereby greatly improving productivity. In addition, it was confirmed that a high-quality fluorocarbon thin film having high transparency with low surface energy could be manufactured.

(Example 3-16)

Further performing the step of surface treatment of the fluorocarbon thin film in the conditions of Table 2 to the fluorocarbon thin film prepared by the manufacturing method of Example 1, in order to check the physical properties of the fluorocarbon thin film treated by the method, the water contact angle The light transmittance in visible light (550 nm) was measured, and the results are shown in Table 2 below.

In addition, by using a UV spectrometer (UV / VIS Spectrophotometer, Agilent 8456, # G1103A) to measure the yellowness according to the ASTM E313 standard, the results are shown in Table 2. In this case, the yellowness means a deviation from the colorless state in the yellow direction.

실시예. NoExample. No	플라즈마 파워 (W)Plasma Power (W)	아르곤(sccm)Argon (sccm)	산소(sccm)Oxygen (sccm)	접촉각(°)Contact angle (°)	가시광선 투과율(%)Visible light transmittance (%)	황색도(B)Yellowness degree (B )
33	100100	500500	00	9494	90.5490.54	0.350.35
44		150150	00	7474	89.8189.81	0.350.35
55		100100	100100	9898	91.4291.42	1.191.19
66		100100	500500	101101	91.2691.26	1.141.14
77	200200	500500	00	5454	90.1990.19	0.030.03
88		300300	00	4444	90.4090.40	0.410.41
99		100100	100100	8787	91.2191.21	1.111.11
1010		100100	500500	9191	91.2391.23	1.051.05
1111	300300	500500	00	2626	90.1490.14	0.420.42
1212		100100	100100	8484	91.2691.26	1.221.22
1313		100100	500500	8686	91.4191.41	1.151.15
1414	320320	500500	00	2424	90.3790.37	0.310.31
1515	400400	100100	100100	6969	91.2191.21	1.071.07
1616	400400	100100	500500	8080	91.3191.31	0.990.99

As shown in Table 2, the fluorocarbon thin film manufactured by additionally performing the surface treatment of the fluorocarbon thin film can realize a uniform color and brightness overall while maintaining visibility, and the surface energy value and optical properties according to the purpose It was confirmed that it can be easily changed. In particular, in the surface treatment of the fluorocarbon thin film according to the present invention, it was confirmed that improved visible light transmittance can be realized by using a reaction gas mixed with argon and oxygen.

(Example 17)

A superhydrophobic coated fiber in which a hydrocarbon thin film was deposited on a polyester fiber fabric (width 100 mm, length 100 mm thickness 0.1 mm) was manufactured using a cluster sputtering device.

The cluster sputtering apparatus includes a loader portion on which a substrate is loaded, a transfer module portion for transferring the substrate, and a sputtering chamber portion for depositing a thin film, and the sputtering chamber portion includes an MF dual sputtering cathode.

The fluorine-based polymer composite target (4 inches in diameter and 6 mm in thickness) was manufactured in a circular form containing 85 wt% of powder PTFE (polytetrafluoroethylene, DuPont 7AJ) and 15 wt% of graphite (Timcal, 40um). It was attached to the copper backing plate electrode surface and installed in the MF dual sputtering cathode of the sputtering chamber portion.

A polyester fiber fabric is attached to the substrate, and the inside of the chamber is evacuated to 50 mtorr by a rotary pump to make a low vacuum state, followed by a high vacuum (5 × 10-5 Torr) using a cryo pump. Formed. At this time, while argon gas was injected into the process gas at a flow rate of 50 sccm, pre-sputtering was performed at a MF power of 100 W to remove contaminants. Since the MF power to 300W (3.7 W / ㎠) to deposit a fluorocarbon thin film for 30 minutes, the deposited super water-repellent coating fibers were taken out of the loader.

In order to confirm the physical properties of the super water-repellent coating fibers prepared by the above method, the coating angle in the contact angle and the super water-repellent coating fibers was measured, and the results are shown in Table 3.

(Example 18)

A superhydrophobic coated fiber in which a hydrocarbon thin film was deposited using a roll-to-roll sputter device (SPW-060, see FIG. 1) was fabricated on a nylon fiber fabric (600 mm wide, 0.1 mm thick, 30 m long roll).

The SPW-060 roll-to-roll sputtering device includes an unwinder part for winding a fiber fabric, a process chamber part for depositing a thin film on the fiber fabric, and a winder part for winding the formed fiber fabric. The process chamber part is composed of three MF dual sputtering cathodes (cathode 1 to 3) and one DC sputtering cathode (cathode 4) independently.

Fluorine-based polymer composite target (length 950 mm, width 127 mm, thickness 6 mm) was produced in a square plate shape. A fluorine-based polymer composite target containing 90 wt% of powder PTFE (polytetrafluoroethylene, DuPont 7AJ) and 10 wt% of carbon nanotubes was attached to an electrode surface of a copper backing plate. It was installed in MF dual sputtering cathode 1. After that, a nylon fiber fabric (600 mm wide, 0.1 mm thick, 30 m long roll) was loaded into the unwinder chamber, and a rotary pump and a booster pump were used to vacuum the inside of the roll-to-roll sputtering device to 50 mtorr. After evacuating the vacuum to a low vacuum state, a high vacuum (2 × 10 ^-4 Pa) was formed using a turbo molecular pump. When the internal vacuum degree of the roll-to-roll sputtering device became 2 × 10 ⁻⁴ Pa or less, pre-sputtering was performed with MF power of 1 kW while argon (Ar) gas was injected into the cathode at a flow rate of 400 sccm. Thereafter, the temperature of the main roll was lowered to 10 ° C., and the MF power was 3 kW by MF dual sputtering cathode 1 while conveying the nylon fiber fabric at a speed of 1 m / min. Was deposited, and the deposited superhydrophobic coated fiber was taken out of the loader.

In order to check the physical properties of the super water-repellent coating fiber prepared by the above method, the contact angle and the thickness of the super water-repellent coating film were measured, and the results are shown in Table 3.

(Example 19)

A high purity Si (99.9%, Mitsui) Target (square plate, length 950 mm, width 127 mm, thickness 6 mm) is attached to the copper backing plate electrode surface and attached to the MF dual sputtering cathode 1 Installed. A copper backing plate (Cu backing) was made of a fluoropolymer composite target (length 950 mm, width 127 mm, thickness 6 mm) made of a square plate containing 90 wt% of powdered PTFE (polytetrafluoroethylene, DuPont 7AJ) and 10 wt% of carbon nanotubes. plate) attached to the electrode surface. It was installed in MF dual sputtering cathode 2. After that, a nylon fiber fabric (600 mm wide, 0.1 mm thick, 30 m long roll) was loaded into the unwinder chamber, and a rotary pump and a booster pump were used to vacuum the inside of the roll-to-roll sputtering device to 50 mtorr. After evacuating the vacuum to a low vacuum state, a high vacuum (2 × 10 ^-4 Pa) was formed using a turbo molecular pump. When the internal vacuum degree of the roll-to-roll sputtering device became 2 × 10 ⁻⁴ Pa or less, pre-sputtering was performed with MF power of 1 kW while injecting argon (Ar) gas into each cathode at a flow rate of 400 sccm. Thereafter, the temperature of the main roll was lowered to 10 ° C., and the MF power was set to 10 kW by MF dual sputtering cathode 1 while conveying the nylon fiber fabric at a speed of 1 m / min. The silicon oxide (SiO ₂ ) inorganic coating layer was deposited while the gas was injected in a PID controlled manner to maintain the sputtering voltage at 80%. Subsequently, a fluorocarbon thin film was deposited by using cathode 2 at a MF power of 3 kW, and the deposited superhydrophobic coated fiber was taken out of the loader unit.

(Example 20)

A copper backing plate (Cu backing) was made of a fluoropolymer composite target (length 950 mm, width 127 mm, thickness 6 mm) made of a square plate containing 85 wt% of powdered PTFE (polytetrafluoroethylene, DuPont 7AJ) and 15 wt% of carbon nanotubes. plate) attached to the electrode surface. It was installed in a DC (Direct Current) single sputtering cathode 4. After that, a nylon fiber fabric (600 mm wide, 0.1 mm thick, 30 m long roll) was loaded into the unwinder chamber, and the inside of the roll-to-roll sputtering device (SPW-060) was opened using a rotary pump and a booster pump. After evacuating the vacuum to 50 mtorr to make a low vacuum state, a high vacuum (2 × 10 ⁻⁴ Pa) was formed using a turbo molecular pump. When the internal vacuum degree of the roll-to-roll sputtering device became 2 × 10 ⁻⁴ Pa or less, pre-sputtering was performed with DC power of 1 kW while argon (Ar) gas was injected into the cathode at a flow rate of 400 sccm. Thereafter, the temperature of the main roll was lowered to 10 ° C., and the fluorocarbon thin film was made with DC power of 1 kW by DC sputtering cathode 4 while conveying the nylon fiber fabric at a speed of 1 m / min. Was deposited, and the deposited superhydrophobic coated fiber was taken out of the loader.

(Example 21)

The cluster sputtering device includes a loader part, a transfer module part for transferring the substrate, and a sputtering chamber part for depositing a thin film, and the sputtering chamber part is composed of an MF dual sputtering cathode.

A fluorine-based polymer composite target (4 inches in diameter, 6 mm thick) made of circular PTFE (polytetrafluoroethylene, DuPont 7AJ) containing 65 wt%, 5 wt% carbon nanotubes, and 30 wt% Al ₂ O _{3 was} coated with a copper backing plate ( Cu backing plate) was attached to the electrode surface. This was installed in the MF dual sputtering cathode of the sputtering chamber portion.

A polyester fiber fabric (100 mm wide, 100 mm thick 0.1 mm thick) is attached to the substrate, and the chamber is evacuated to 50 mtorr with a rotary pump to make a low vacuum state and then use a cryo pump. To form a high vacuum (5 × 10 −5 Torr). At this time, while argon gas was injected into the process gas at a flow rate of 50 sccm, pre-sputtering was performed at MF power of 100 W to remove contaminants. Since the MF power was set to 300W for 30 minutes to deposit a fluorocarbon thin film, the superhydrophobic coating fibers deposited were taken out of the loader.

Monochromatic Al-Kα (15 kV, large spot with X-ray photoelectron spectroscopy, X-ray light source to quantify the chemical bonding state and chemical composition in the fluorocarbon thin film (water repellent layer) of the super water-repellent coating fibers prepared by the above method) AXIS NOVA) with size: 400 μm × 800 μm, small spot size: 10 μm) was used. The Al-Kα light source was used, and the acceleration voltage was set to 15 kV and the emission current was 10 mA to confirm the chemical bonding state and chemical composition in the fluorocarbon thin film.

As a result, as shown in FIG. 2, the C1s spectrum of the fluorocarbon thin film showed that carbon-fluorine bonds and CC carbon-carbon bonds such as CF, CF ₂ , CF ₃ , and CCF were observed. In this case, it was found that the carbon atom (C) contained 29.57% by weight, the fluorine atom (F) was 59.02% by weight, and the aluminum atom (Al) was 6.64% by weight based on 100% by weight of the total atoms in the fluorocarbon thin film. .

In addition, in order to confirm the properties of the super water-repellent coating fibers prepared by the above method, the contact angle and the thickness of the super water-repellent coating film were measured, and the results are shown in Table 3.

	실시예 17Example 17	실시예 18Example 18	실시예 19Example 19	실시예 20Example 20	실시예 21Example 21	비교예 5Comparative Example 5
접촉각(°)Contact angle (°)	140140	143143	145145	142142	143143	2525
코팅막 두께(nm)Coating film thickness (nm)	100100	5050	9595	5353	105105	4545

The present invention is different from the conventional fluorocarbon thin film in that the present invention can be implemented regardless of the output voltage, and evenly deposited fluorine carbide thin film (water repellent layer) at a high deposition rate even by an MF or DC power supply having an applied voltage lower than RF. It can provide a super water-repellent coating fiber comprising a. In addition, the super water-repellent coated fiber has a high contact angle of 140 ° or more, it can be seen that it has a relatively high deposition rate (see Table 3).

In addition, the manufacturing method of the super water-repellent coating fiber according to the present invention can be directly applied to the existing roll-to-roll equipment only by replacing the target without any additional renovation cost, and it is possible to manufacture a large-area thin film in a very short time. As a continuous process for fabric making, it can contribute to mass production of high quality fiber with high quality due to simplified process and reduced manufacturing cost.

That is, the present invention can continuously improve the productivity by providing a variety of functions to the textile fabric in a single equipment, and can significantly improve productivity, and replace various conventional processes using a large amount of water and chemicals, etc. Minimize problems and provide benefits in terms of energy savings.

(Example 22)

A hydrocarbon thin film was fabricated on a 1 × 2 cm 2 glass substrate (eagle XG glass 0.7mmTh) using a cluster sputtering device.

The fluorine-based polymer composite target (4 inches in diameter and 6 mm in thickness) was manufactured in a circular form containing 85 wt% of powder PTFE (polytetrafluoroethylene, DuPont 7AJ) and 15 wt% of carbon nanotubes. It was attached to the copper backing plate electrode face. This was installed in the MF dual sputtering cathode of the sputtering chamber portion.

At this time, the substrate was prepared by washing and drying with an ultrasonic cleaner for 5 minutes each with acetone and alcohol. 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. A distance between the substrate and the target was fixed at 24 cm at room temperature (25 ° C.), and a 100 nm fluoride carbide thin film was manufactured by a power (200 W) and an argon partial pressure (10 mtorr).

In order to check the physical properties of a 100 nm thick transparent fluorocarbon thin film coated on a 1 x 2 cm 2 glass substrate (eagle XG glass 0.7mmTh) prepared by the above method, by measuring the surface properties and light transmittance, 3 and Table 4.

(Example 23)

Instead of the fluorine-based polymer composite target used in Example 22, 85 wt% of powdered PTFE (polytetrafluoroethylene, DuPont 7AJ) and 15 wt% graphite (TIMCAL, average diameter of 2 um) were used in the form of a fluorine-based polymer composite target. Except that a fluorocarbon thin film was produced in the same manner.

The fluorocarbon thin film prepared by the above method was deposited to a thickness of 100 nm, and the surface characteristics and the light transmittance of the fluorocarbon thin film manufactured by the above method were measured, and the results are shown in FIGS. 4 and 4.

(Example 24)

Instead of the fluorine-based polymer composite target used in Example 22 fluorine-based fluorine-based made of a circular containing PTFE (polytetrafluoroethylene, DuPont 7AJ) 70 wt%, alumina oxide (Al ₂ O ₃ ) 20 wt%, carbon nanotube 10 wt% A fluorocarbon thin film was manufactured in the same manner except that a polymer composite target was used.

The fluorocarbon thin film prepared by the above method was deposited to a thickness of 100 nm, and the surface characteristics and the light transmittance of the fluorocarbon thin film manufactured by the above method were measured, and the results are shown in Table 4 below.

(Example 25)

A fluorocarbon thin film was produced using a roll-to-roll sputter (ULVAC, SPW-060) on a PET film (SKC, SH-40, thickness of 100 μm, width of 600 mm).

Copper backing plate with fluoropolymer composite target (square plate, length 950 mm, width 127 mm, thickness 6 mm) made from square plate containing 90 wt% of powder PTFE (polytetrafluoroethylene, DuPont 7AJ) and 10 wt% of carbon nanotube (Cu backing plate) It was attached to the electrode surface. It was installed in MF dual sputtering cathode 1. 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. . Thereafter, the temperature of the main roll was lowered to 10 ° C., and a fluorocarbon thin film was produced while conveying the substrate at a speed of 1 m / min.

A fluorocarbon thin film was deposited by a MF dual sputtering cathode 1 with a MF power of 5 kW at a thickness of 100 nm, and the fluorocarbon thin film thus produced was unwound in a winder chamber.

(Example 26)

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 MF dual sputtering cathode 1. 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 2.

A MF dual sputtering cathode 2 deposited a SiO ₂ thin film as a buffer layer with a MF power of 3 kW (20 nm thick). Subsequently, a fluorocarbon thin film was deposited to a thickness of 100 nm with MF power of 5 kW by MF dual sputtering cathode 2, and then a hard coat film prepared was wound in a winder chamber.

The surface characteristics and the light transmittance of the hard coat film prepared by the above method were measured, and the results are shown in Table 4.

	실시예 22Example 22	실시예 23Example 23	실시예 24Example 24	실시예 25Example 25	실시예 26Example 26	비교예 8Comparative Example 8
표면경도(GPa)Surface Hardness (GPa)	1.411.41	6.906.90	2.352.35	1.151.15	2.052.05	0.580.58
투과율(%, 파장 550nm)Transmittance (%, wavelength 550nm)	95.4595.45	94.5594.55	95.7595.75	92.5692.56	93.2493.24	91.2791.27

As shown in Table 4, the fluorocarbon thin film according to the present invention provides a transparent fluorine carbide thin film having a significantly improved surface hardness characteristics compared to Comparative Example 8, which is a fluorine carbide thin film deposited by RF power, scratch resistance, It is expected to have a water repellent property, antifouling property, anti-fingerprint and the like, which can be usefully applied to the surface of a liquid crystal display device.

(Example 27)

A hydrocarbon thin film was fabricated on a 1 × 1 cm 2 glass substrate (eagle XG glass 0.5mmTh) using a cluster sputtering device.

The fluorine-based polymer composite target (4 inches in diameter and 6 mm in thickness) was manufactured in a circular shape containing 90 wt% of powder PTFE (polytetrafluoroethylene, DuPont 7AJ) and 10 wt% of carbon nanotubes (average particle diameter: 30 nm). It was attached to the copper backing plate electrode face. This was installed in the MF dual sputtering cathode of the sputtering chamber portion.

After vacuuming the inside of the chamber with a rotary pump to 50 mtorr, the vacuum was reduced to a low vacuum state, and a high vacuum (5 × 10 ⁻⁵ Torr) was formed by using a cryo pump. At this time, while argon gas was injected into the process gas at a flow rate of 50 sccm, pre-sputtering was performed at a MF power of 1.23 W / cm 2 to remove contaminants. After the process gas (argon, Ar) is injected at a rate of 50 sccm with MF power of 3.7 W / cm 2, the reaction gas (oxygen, O ₂ ) is injected at 5 sccm and MF sputtering (power 3.7 W / cm 2) is used. A reactive sputtering process was performed for minutes to produce a fluorocarbon thin film.

The water contact angle and the hexadecane contact angle of the fluorocarbon thin film prepared by the above method were measured, and the results are shown in Table 5 below.

(Example 28)

99 wt% of powder PFA (perfluoroalkoxy copolymer, 3M Dyneon PFA 6503) instead of fluorinated polymer composite target containing 90 wt% of powder PTFE (polytetrafluoroethylene, DuPont 7AJ) and 10 wt% of carbon nanotube (average particle diameter: 30 nm) in Example 27 A fluorocarbon thin film was manufactured in the same manner, except that a fluorine-based polymer composite target containing 1 wt% of carbon nanotubes (average particle diameter: 30 nm) was used.

(Example 29)

Fluorine-based polymer composite target (length 950 mm, width 127 mm, thickness 6 mm) made of square plate containing PTFE (polytetrafluoroethylene, DuPont 7AJ) 95 wt% and carbon nanotube (average particle diameter 30 nm) 5 wt% Backing plate (Cu backing plate) was attached to the electrode surface. It was installed in MF dual sputtering 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 of the roll-to-roll sputtering device is 2 × 10 ⁻⁴ Pa or less, MF and DC power are 1.0 W / cm 2 while injecting process gases (argon, Ar) into each cathode at a flow rate of 400 sccm, -sputtering was performed. Thereafter, the temperature of the main roll is lowered to 10 ° C., and the reaction gas (oxygen, O ₂ ) is injected while the process gas Ar is injected at a rate of 400 sccm while conveying the PET film at a speed of 1 m / min. Injected at 35 sccm to perform a reactive sputtering process for 30 minutes using MF sputtering (power 2.0 W / ㎠) to produce a fluorocarbon thin film (100nm thickness).

In order to confirm the physical properties of the fluorocarbon thin film prepared by the above method, the water contact angle and the hexadecane contact angle were measured, and the results are shown in Table 5 below.

	실시예 27Example 27	실시예 28Example 28	실시예 29Example 29	비교예 9Comparative Example 9
수 접촉각(°)Male contact angle (°)	114114	105105	103103	9898
헥사데칸 접촉각(°)Hexadecane contact angle (°)	5555	5555	5555	3535

As shown in Table 5, the present invention can provide a fluorocarbon thin film having high water repellency and oil repellency for hexadecane of 50 ° or more. In addition, the fluorocarbon thin film according to the present invention is significantly improved oil repellency compared to the fluorocarbon thin film made of 100% PTFE prepared by the method of Comparative Example 9, the organic EL display device, field emission with excellent pollution resistance and transparency It is applied to outermost layers such as display panels and touch screens such as flexible substrates or encapsulating materials of various display devices (displays) such as display devices and liquid crystal displays, solar cells, thin film batteries, and electric double layer capacitors, and the like. It is expected to be able to provide the device.

(Comparative Example 1)

PET film (SKC, SH-40, thickness 100um, width 600mm) using roll-to-roll sputter (ULVAC, SPW-060) device using PTFE 100% Target by MF sputtering method and MF power in Ar gas atmosphere 2.5 W / cm ² was applied, but no plasma was formed, so that deposition of the fluorocarbon thin film was impossible.

(Comparative Example 2)

PET 100% (SKC, SH-40, 100um thick, 600mm wide) using roll-to-roll sputter (ULVAC, SPW-060) device using DC 100% Target by DC sputtering method and 2.5 DC power in Ar gas atmosphere. W / cm ² was applied, but no plasma was formed, so that deposition of the fluorocarbon thin film was impossible.

In Comparative Examples 1 and 2, sputtering was attempted by using a MF resin and a DC method using a fluorine resin target having no conductivity. However, since plasma discharge did not occur, deposition of the fluorocarbon thin film was impossible.

(Comparative Example 3)

Using a roll-to-roll sputter device (ULVAC, SPW-060) on a nylon fiber fabric (600 mm wide, 0.1 mm thick, 30 m long roll), 100% PTFE Target was used instead of the fluorine-based polymer composite target used in Example 18. In the same manner, the MF power was applied at 3 kW through the cathode 1, but no plasma was formed so that the deposition of the fluorocarbon thin film was impossible.

(Comparative Example 4)

Except for using a fluoropolymer composite target containing 90% PTFE and SiO ₂ 10 wt% instead of 100% PTFE Target in Comparative Example 3 by using a roll-to-roll sputter device (ULVAC, SPW-060) in the nylon fiber fabric In the same way, MF power was applied at 3 kW, but the plasma was not formed, so it was impossible to deposit the fluorocarbon thin film.

(Comparative Example 5)

It was intended to form only the inorganic layer according to Example 19 using a roll-to-roll sputter device (ULVAC, SPW-060) on the nylon fiber fabric. At this time, in order to form the inorganic layer, the coated fiber deposited under an oxygen (O ₂ ) atmosphere with an MF power of 10 kW through the cathode 2 was prepared.

In order to confirm the physical properties of the coated fiber prepared by the above method, the water contact angle and the thickness of the super water-repellent coating film were measured, and the results are shown in Table 3.

(Comparative Example 6)

Instead of the fluorine-based polymer composite target used in Example 22, 100% PTFE target was used to form a fluorocarbon thin film. In this case, although MF power was applied to 200W through the cathode 1, plasma was not formed, and thus, the deposition of the transparent hard coat layer was impossible.

(Comparative Example 7)

Using a roll-to-roll sputter device (ULVAC, SPW-060) on a PET film (SKC, SH-40, thickness 100㎛, width 600mm) using 100% PTFE target instead of the fluorine-based polymer composite target used in Example 25 , To form a fluorocarbon thin film. In this case, although MF power was applied at 5 kW through the cathode 1, plasma was not formed and deposition of the fluorocarbon thin film was impossible.

(Comparative Example 8)

Hydrocarbon thin film was produced in PET film (SKC, SH-40, thickness 100micrometer) using the cluster sputter apparatus. At this time, the fluorocarbon thin film was manufactured at 200W using RF power method using 100% PTFE Target.

The fluorocarbon thin film prepared by the above method was deposited to a thickness of 100 nm, and the surface characteristics and the light transmittance of the prepared fluorocarbon thin film were measured, and the results are shown in Table 4.

(Comparative Example 9)

Hydrocarbon thin film was produced in a PET film (SKC, SH-40, thickness 100um, width 100mm, length 100mm) using a cluster sputtering equipment. In this case, 100 nm fluorocarbon thin film was prepared by depositing for 30 minutes while injecting only 50 sccm of Ar, which is a process gas, by using a 100% PTFE power target at 3.7 W / cm 2 by RF power method using a 100% PTFE target.

(Explanation of the sign)

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

A method of manufacturing a fluorocarbon thin film comprising the step of sputtering using a fluorine-based polymer composite target comprising a functionalizing agent having conductivity on a substrate.
The method of claim 1,

The sputtering is a method of manufacturing a fluorocarbon thin film is performed by RF, MF or DC power supply method.
The method of claim 1,

The step is a roll-to-roll sputtering method of manufacturing a fluorocarbon thin film by MF or DC power supply method.
The method of claim 1,

The functionalizing agent is a method for producing a fluorocarbon thin film of at least one selected from conductive particles, conductive polymers and metal components.
The method of claim 4, wherein

The fluorine-based polymer composite target is a method for producing a fluorocarbon thin film further comprising at least one metal compound selected from metal organic matter, metal oxide, metal carbon body, metal hydroxide, metal carbonate, metal bicarbonate, metal nitride and metal fluoride.
The method of claim 4, wherein

The conductive particles are at least one selected from carbon nanotubes, carbon nanofibers, carbon black, graphene, graphite and carbon fibers.
The method of claim 4, wherein

The conductive polymer may be polyaniline, polyacetylene, polythiophene, polypyrrole, polyfluene, polypyrene, polyazulene, polynaphthalene, polyphenylene, polyphenylenevinylene, polycarbazole, polyindole, polyazene, polyethylene, A method for producing a fluorocarbon thin film of at least one selected from polyethylenevinylene, polyphenylene sulfide, polyfuran, polyselenophene, polytelurophene and polysulfur nitride.
The method of claim 4, wherein

The metal component is a method for producing a fluorocarbon thin film of at least one selected from copper, aluminum, silver, gold, tungsten, silicon, magnesium, nickel, molybdenum, vanadium, niobium, titanium, platinum, chromium and tantalum.
The method of claim 1,

The step is a method for producing a fluorocarbon thin film that reactive sputtering is performed under reaction gas injection.
The method of claim 9,

The reaction gas is a method for producing a fluorocarbon thin film selected from oxygen, ozone, hydrogen peroxide, ammonia, nitrous oxide, nitrogen monoxide, nitrogen dioxide, nitrogen, carbon tetrafluoride and hydrazine.
The method of claim 10,

The reaction gas is injected with at least one process gas selected from argon, helium, neon and nitrogen fluorine carbide thin film manufacturing method.
The method of claim 11,

The mixing ratio of the process gas and the reaction gas (process gas: reaction gas) is 1: 1 to 1000: 1 method for producing a fluorocarbon thin film.
The method of claim 1,

After the step, injecting the surface treatment gas further comprising the step of plasma surface treatment method of manufacturing a fluorocarbon thin film.
The method of claim 13,

The surface treatment gas is at least one selected from argon, nitrogen, oxygen, carbon tetrafluoride and hydrogen fluorocarbon thin film manufacturing method.
The method of claim 13,

The surface treatment gas is a method for producing a fluorocarbon thin film is injected to a flow rate of 1 to 1000 sccm.
The method of claim 1,

The sputtering is a method of manufacturing a fluorocarbon thin film that is performed by forming a plasma with a power of 0.1 to 15 W / ㎠.
The method of claim 1,

The substrate is a method of manufacturing a fluorocarbon thin film that is selected from silicon, metal, ceramic, resin, paper, glass, quartz, fiber, plastic and organic polymer.
A molded article formed by sputtering on a substrate using a fluorine-based polymer composite target containing a functionalizing agent.
The method of claim 18,

Molded body having a contact angle with water in the range of 90 to 150 °.
The method of claim 19,

Molded products with a contact angle with hexadecane ranging from 50 ° to 70 °.
The method of claim 18,

The molded body is sputtered by MF or DC power supply.
A fluorine-based polymer composite target made of fluorine-based polymer containing at least one selected from conductive particles, conductive polymers and metal components in the chamber, and an unwinder chamber for supplying a substrate, and depositing a fluorocarbon thin film on one surface of the substrate. A roll-to-roll type sputtering deposition system comprising a main chamber and a winder chamber for winding the deposited fluorocarbon thin film, wherein the main chamber has three MF dual sputtering cathodes and one DC single sputtering cathode.