KR100385486B1 - the method for changing quality of surface for water-release-layer coating of polymer - Google Patents
the method for changing quality of surface for water-release-layer coating of polymer Download PDFInfo
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- KR100385486B1 KR100385486B1 KR10-2000-0045381A KR20000045381A KR100385486B1 KR 100385486 B1 KR100385486 B1 KR 100385486B1 KR 20000045381 A KR20000045381 A KR 20000045381A KR 100385486 B1 KR100385486 B1 KR 100385486B1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/06—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation
- B05D3/068—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to radiation using ionising radiations (gamma, X, electrons)
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D1/00—Processes for applying liquids or other fluent materials
- B05D1/02—Processes for applying liquids or other fluent materials performed by spraying
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
- B05D3/0433—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a reactive gas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
- B05D3/0466—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases the gas being a non-reacting gas
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
- B05D3/0486—Operating the coating or treatment in a controlled atmosphere
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D3/00—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials
- B05D3/04—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases
- B05D3/0493—Pretreatment of surfaces to which liquids or other fluent materials are to be applied; After-treatment of applied coatings, e.g. intermediate treating of an applied coating preparatory to subsequent applications of liquids or other fluent materials by exposure to gases using vacuum
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D—PROCESSES FOR APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05D7/00—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials
- B05D7/02—Processes, other than flocking, specially adapted for applying liquids or other fluent materials to particular surfaces or for applying particular liquids or other fluent materials to macromolecular substances, e.g. rubber
Abstract
본 발명은 고분자 표면에 불활성 또는 반응성의 이온빔을 조사하면서 반응성 기체를 고분자 표면 주위에 불어넣어 고분자 표면에 친수성 작용기를 형성시키고 그 위에 발수 성분이 있는 수용액을 균일하게 도포하여 고분자의 표면에 발수막을 형성시키도록 한 고분자의 발수막 코팅을 위한 표면 개질 방법에 관한 것으로, 진공조내에 위치된 고분자 재료의 표면에 불활성 가스 또는 반응성 가스를 단독 또는 혼합의 형태로 이온건에 주입하는 단계와, 상기 고분자재료의 표면에 친수성 또는 극성 작용기가 형성되도록, 상기 이온건에서 생성되는 이온빔을 상기 고분자 재료 표면에 조사하면서 상기 진공조에 설치된 가스주입관을 통하여 반응성 가스를 불어넣는 단계와, 상기 단계가 진행된 고분자재료 표면에 발수 성분을 포함하는 수용액을 도포하는 단계가 포함됨으로써 고분자재질의 표면에 발수막 코팅을 하는데 있어 기존보다 공수가 절감되고 환경오염을 줄일수 있으며 고분자 재질 표면과의 접착성이 우수한 발수막 코팅을 할 수 있도록 하였다The present invention blows reactive gas around the surface of the polymer while irradiating an inert or reactive ion beam on the surface of the polymer to form hydrophilic functional groups on the surface of the polymer, and evenly applies an aqueous solution having a water-repellent component thereon to form a water-repellent film on the surface of the polymer. A method of surface modification for coating a water-repellent membrane of a polymer, the method comprising: injecting an inert gas or a reactive gas into an ion gun alone or in a mixed form on a surface of a polymer material located in a vacuum chamber; Blowing a reactive gas through a gas injection tube installed in the vacuum chamber while irradiating an ion beam generated from the ion gun to the surface of the polymer material so that a hydrophilic or polar functional group is formed on the surface of the polymer material surface; To apply an aqueous solution containing a water-repellent component to Boundaries includes being was to be an airlift a reduction than conventional to reduce the environmental pollution and the water-repellent coating film excellent adhesion to the polymeric material's surface to the water-repelling film is coated on the surface of the polymeric material
Description
본 발명은 고분자의 발수막 코팅을 위한 표면 개질 방법에 관한 것으로, 더욱 상세하게는 고분자 표면에 불활성 또는 반응성의 이온빔을 조사하면서 반응성 기체를 고분자 표면 주위에 불어넣어 고분자 표면에 친수성 작용기를 형성시키고 그 위에 발수(소수성) 성분이 있는 수용액을 균일하게 도포하여 고분자의 표면에 발수막을 형성시키도록 한 고분자의 발수막 코팅을 위한 표면 개질 방법에 관한 것이다.The present invention relates to a surface modification method for coating a water repellent membrane of a polymer, and more particularly, by irradiating an inert or reactive ion beam on the surface of a polymer, a reactive gas is blown around the surface of the polymer to form hydrophilic functional groups on the surface of the polymer. The present invention relates to a surface modification method for coating a water-repellent membrane of a polymer to uniformly apply an aqueous solution having a water-repellent (hydrophobic) component thereon to form a water-repellent membrane on the surface of the polymer.
일반적으로, 이온빔을 조사하여 고분자 표면에 산소, 질소등과 같은 반응성 기체를 불어넣어 주고, 이온 조사를 진행하면 고분자 표면에 형성된 라디칼과 상기 반응성 기체가 결합하여 고분자 표면에 친수성기들이 형성된다. 친수성기가 형성된 고분자 표면에 불소계 또는 실리콘계 물질과 같은 발수 성분이 포함된 수용액을 도포하여 고분자 표면을 강한 발수성(소수성)을 띠도록 한다.In general, by irradiating an ion beam and blowing a reactive gas such as oxygen, nitrogen, etc. on the surface of the polymer, when irradiated with ions, radicals formed on the surface of the polymer and the reactive gas are combined to form hydrophilic groups on the surface of the polymer. An aqueous solution containing a water-repellent component such as a fluorine-based or silicon-based material is coated on the surface of the polymer on which the hydrophilic group is formed so that the surface of the polymer is strongly water-repellent (hydrophobic).
고분자 표면에 발수성 코팅막이 형성되면 물방울이 잘 맺히지 않으며 이러한 성질은 폴리메틸메타아크릴레이트(polymethylmethacrylate), 폴리카보네이트(polycarbonate), 폴리에틸렌테레프탈레이트(polyethylene terephthalate)등을 이용한 김서림 방지용 플라스틱 거울이나 폴리에스터(polyester), 나일론(nylon) 등의 고분자 섬유의 발수 코팅에 응용이 가능하다. 또한 발수성의 고분자 표면에는 오염 물질이 잘 흡착되지 않는 성질을 갖는다.When water-repellent coating film is formed on the surface of the polymer, water droplets do not form well, and this property is characterized by anti-fog plastic mirror or polyester using polymethylmethacrylate, polycarbonate, polyethylene terephthalate, etc. It is possible to apply to water-repellent coating of polymer fibers such as nylon and nylon. In addition, contaminants are hardly adsorbed on the surface of the water repellent polymer.
그러나, 고분자 표면은 일반적으로 표면 에너지가 낮아 물을 용매로 하는 침지법(dipping), 스프레이법(spray), 스핀 코팅(spin coating)의 방식을 이용하여 코팅막을 균일하게 도포하는데 많은 어려움이 있었다.However, since the surface of the polymer is generally low in surface energy, there are many difficulties in uniformly applying the coating film using a dipping method, a spray method, or a spin coating method using water as a solvent.
수용액을 사용할 경우 고분자 표면의 소수성이 표면을 젖게 하지 못하고 표면 장력이 생겨 물방울이 생기는 현상이 일어난다. 따라서 수용액을 이용한 코팅막의 증착시 이의 직접적이며 균일한 도포를 위하여 고분자 표면을 친수화하는 과정이 요구된다.When the aqueous solution is used, the hydrophobicity of the surface of the polymer does not wet the surface and causes surface tension to cause water droplets. Therefore, during the deposition of the coating film using an aqueous solution, a process of hydrophilizing a polymer surface is required for its direct and uniform application.
이러한 문제를 해결하기 위한 기존의 방법으로는 고분자위에 실리콘 산화물 계열의 하드 코팅을 하고 그 위에 코팅막을 입히는 것이었다. 그러나 이 방법은 재현성이 낮고 공정 시간이 길며 특히 코팅막과의 접착 불량이 많았다.The conventional method to solve this problem was to apply a silicon oxide-based hard coating on the polymer and a coating film on it. However, this method has low reproducibility, long process time, and especially poor adhesion with the coating film.
또한, 하드 코팅 대신 고분자 표면을 코로나(corona) 방전 처리하여 계면 활성제를 도포하는 방법, 유기 용매에 의한 화학적 표면 처리를 하거나 플라즈마 고분자(plasma polymerization)를 증착하는 방법 등이 있다.In addition, there is a method of applying a surfactant by corona discharge treatment on the surface of the polymer instead of hard coating, a method of chemical surface treatment using an organic solvent, or a method of depositing plasma polymerization.
그러나 이와 같은 방법도 역시 공정이 복잡하고 내구성이 약하며 환경오염, 유기 용매 사용에 따른 가격 상승의 문제점이 있다.However, such a method also has a problem of complexity and durability of the process and the price increase due to environmental pollution, the use of organic solvents.
따라서, 본 기술분야의 당업자들은 고분자재질의 표면에 발수막 코팅을 하는데 있어 기존보다 공수가 절감되고 환경오염을 줄일 수 있으며 고분자 재질표면과의 접착성이 우수한 발수막 코팅을 할수 있는 방법을 얻기 위하여 고심하여 왔다.Therefore, those of ordinary skill in the art to reduce the number of airborne and environmental pollution in the coating of the water-repellent membrane on the surface of the polymer material to obtain a method for coating a water-repellent membrane with excellent adhesion to the surface of the polymer material I have been struggling.
본 발명에 따른 고분자의 발수막 코팅을 위한 표면 개질 방법은 고분자재질의 표면에 발수막 코팅을 하는데 있어 기존보다 공수가 절감되고 환경오염을 줄일수 있으며 고분자 재질 표면과의 접착성이 우수한 발수막 코팅을 할 수 있도록 친수성을 상기 고분자재료의 표면에 부여하는 것을 목적으로 한다.The surface modification method for coating the water repellent membrane of the polymer according to the present invention is to reduce the water pollution and environmental pollution than the conventional water repellent coating on the surface of the polymer material water repellent membrane coating with excellent adhesion to the surface of the polymer material The purpose of the present invention is to impart hydrophilicity to the surface of the polymer material.
이에 따라, 본 발명자들은 이미 출원한 바 있는 이온빔을 이용한 표면 개질법(미국 특허 등록번호: 5783641)을 응용하여 고분자 표면에 친수성을 부여함으로써 계면 활성제나 유기용매의 사용없이도 물을 용매로 하는 발수막의 직접적이며 균일한 도포를 가능하게 하고 외부 변화나 시간에 따라 영향을 받지않도록 하는 내구성을 갖도록 하는 방법을 발명하였다.Accordingly, the present inventors have applied a surface modification method using an ion beam (US patent registration number: 5783641), which has already been filed, to impart hydrophilicity to the surface of the polymer, so that the water-repellent membrane using water as a solvent without the use of a surfactant or an organic solvent can be used. It has been invented a method that enables uniform application and has durability that is not affected by external changes or time.
도 1은 이온빔을 이용한 고분자 표면 개질 장치의 개략적으로 도시한 종단면도.1 is a schematic longitudinal sectional view of a polymer surface modification apparatus using ion beams.
도 2는 이온빔으로 표면 개질된 고분자의 물에 대한 접촉각의 변화를 보여주는 그래프.2 is a graph showing a change in contact angle of water of a polymer surface-modified with an ion beam.
도 3은 이온빔으로 표면 개질된 고분자의 표면 에너지 변화를 보여주는 그래프.3 is a graph showing the surface energy change of the surface-modified polymer with an ion beam.
도 4는 무처리 폴리카보네이트와 발수막으로 코팅된 폴리카보네이트의 물에 대한 젖음성의 변화를 보여주기 위한 것으로써, 도 4a는 무처리된 폴리카보네이트의 표면사진, 도 4b는 실리콘계 발수 코팅된 폴리카보네이트의 표면사진, 도 4c는 불소계 발수 코팅된 폴리카보네이트의 표면사진.Figure 4 is to show the change in the wettability of the non-treated polycarbonate and the polycarbonate coated with a water repellent film, Figure 4a is a surface photograph of the untreated polycarbonate, Figure 4b is a silicone-based water-repellent coating polycarbonate Surface photo of, Figure 4c is a surface photo of the fluorine-based water-repellent coating polycarbonate.
<도면의 주요부분에 대한 부호의 설명><Description of the symbols for the main parts of the drawings>
1: 진공조 2:시료1: vacuum chamber 2: sample
3: 이온건 4:가스주입관3: ion gun 4: gas injection pipe
5:로터리 펌프5: rotary pump
상기한 목적을 달성하기 위하여, 본 발명에 따른 고분자의 발수막 코팅을 위한 표면 개질 방법은, 진공조내에 위치된 고분자 재료의 표면에 불활성 가스 또는 반응성 가스를 단독 또는 혼합의 형태로 이온건에 주입하는 단계와, 상기 고분자재료의 표면에 친수성 또는 극성 작용기가 형성되도록, 상기 이온건에서 생성되는 이온빔을 상기 고분자 재료 표면에 조사하면서 상기 진공조에 설치된 가스주입관을 통하여 반응성 가스를 불어넣는 단계와, 상기 단계가 진행된 고분자재료 표면에 발수 성분을 포함하는 수용액을 도포하는 단계를 포함하는 것을 특징으로 한다.In order to achieve the above object, the surface modification method for coating the water repellent membrane of the polymer according to the present invention, inert gas or reactive gas to the surface of the polymer material located in the vacuum chamber alone or in the form of a mixture in the ion gun And injecting a reactive gas through a gas injection tube installed in the vacuum chamber while irradiating an ion beam generated from the ion gun to the surface of the polymer material so that a hydrophilic or polar functional group is formed on the surface of the polymer material. It characterized in that it comprises the step of applying an aqueous solution containing a water-repellent component on the surface of the polymer material is a step.
본 발명의 바람직한 실시예에 있어서, 상기 불활성가스는 헬륨, 아르곤, 네온, 제논, 크립톤으로, 상기 반응성가스는 산소, 질소, 공기, 암모니아로 이온화가 가능한 1종이상의 가스를 사용하는 것을 특징으로 한다.In a preferred embodiment of the present invention, the inert gas is helium, argon, neon, xenon, krypton, the reactive gas is characterized by using one or more gases that can be ionized with oxygen, nitrogen, air, ammonia. .
본 발명의 다른 바람직한 실시예에 있어서, 상기 이온건에 주입된 생성되는이온 에너지를 300 -2500 eV로 변화시켜 상기 고분자 재료 표면에 조사하는 것을 특징으로 하며, 상기 고분자 재료 표면에 조사되는 이온의 양을 1 × 1014- 1 × 1018ions/cm2으로 변화시켜 고분자 표면에 친수성 작용기를 형성하는 것을 특징으로 한다.In another preferred embodiment of the present invention, the ion energy injected into the ion gun is changed to 300-2500 eV and irradiated on the surface of the polymer material, the amount of ions irradiated on the surface of the polymer material a 1 × 10 14 - is changed to 1 × 10 18 ions / cm 2 and so as to form a hydrophilic functional group on the polymer surface.
본 발명의 또 다른 바람직한 실시예에 있어서, 반응성 가스의 주입량을 1 - 30 ml/min으로 변화시켜 고분자 표면에 친수성 반응기를 형성하고, 상기 반응성 가스는 산소, 질소, 암모니아, 일산화탄소, 이산화탄소, 수소등의 1 종 이상의 가스를 사용하는 것을 특징으로 한다.In another preferred embodiment of the present invention, the injection amount of the reactive gas is changed to 1-30 ml / min to form a hydrophilic reactor on the surface of the polymer, the reactive gas is oxygen, nitrogen, ammonia, carbon monoxide, carbon dioxide, hydrogen, etc. It is characterized by using one or more kinds of gases.
본 발명의 바람직한 또 다른 실시예에 있어서, 이온빔을 이용한 표면 개질시 상기 반응조내의 진공도는 가스량에 따라 5 × 10-5torr 내지 1 × 10-3torr에서 수행하고, 한편, 상기 고분자 재료는 폴리에틸렌(polyethylene), 폴리프로필렌(polypropylene), 폴리메틸메타아크릴레이트(polymethylmethacryla), 폴리카보네이트(polycarbonate), 폴리에틸렌 테레프탈레이트(polyethylene terephthalate), 폴리에스터(polyester), 폴리설폰(polysulfone), 폴리이미드(polyimide), 나일론(nylon) 폴리스타일렌(polystyrene) 등의 열가소성 또는 열경화성의 고분자 물질임을 특징으로 한다.In another preferred embodiment of the present invention, the degree of vacuum in the reactor during the surface modification using an ion beam is carried out at 5 × 10 -5 torr to 1 × 10 -3 torr depending on the amount of gas, while the polymer material is polyethylene ( polyethylene, polypropylene, polymethylmethacryla, polycarbonate, polyethylene terephthalate, polyester, polysulfone, polyimide, It is characterized by being a thermoplastic or thermosetting polymer material such as nylon (nylon) polystyrene.
본 발명의 또다른 실시예에 있어서, 상기발수 성분은 불소계, 실리콘계, 플루오르계등의 단량체 또는 공중합체가 있고 물을 용매로 사용할 수 있는 물질로 하고, 발수 성분을 가진 수용액의 도포는 침지법(dipping), 스핀 코팅(spincoating), 스프레이법(spray)등을 이용하여 도포하며, 상기 발수 성분을 가진 수용액의 건조를 10 - 200 ℃에서 행하여지는 것을 특징으로 한다.In another embodiment of the present invention, the water-repellent component is a monomer or copolymer of fluorine-based, silicon-based, fluorine-based, etc., and the water can be used as a solvent, the application of an aqueous solution having a water-repellent component is immersion method ( The coating is applied by dipping, spincoating, spraying, or the like, and the drying of the aqueous solution having the water-repellent component is carried out at 10 to 200 ° C.
이하, 첨부한 도면을 참조로 하여 본 발명에 따른 고분자의 발수막 코팅을 위한 표면 개질 방법의 바람직한 실시예를 상세하게 설명한다Hereinafter, with reference to the accompanying drawings will be described in detail a preferred embodiment of the surface modification method for the water-repellent coating of the polymer according to the present invention.
고분자 재료는 폴리에틸렌(polyethylene), 폴리프로필렌(polypropylene), 폴리메틸메타아크릴레이트(polymethylmethacrylate), 폴리카보네이트(polycarbonate), 폴리에틸렌테레프탈레이트(polyethylene terephthalate), 폴리에스터(polyester), 나일론(nylon) 등의 열가소성 또는 열경화성의 성질을 갖는 모든 종류의 고분자를 포함한다.Polymeric materials include thermoplastics such as polyethylene, polypropylene, polymethylmethacrylate, polycarbonate, polyethylene terephthalate, polyester, and nylon Or all kinds of polymers having thermosetting properties.
본 발명에서 사용된 이온빔 처리 장치의 개략 종단면도를 도 1에 나타내었다. 도 1에 나타난 바와 같이 이온빔 조사는 진공 펌프(5)에 의해 진공을 유지하는 진공조(1) 내에서 이루어지며 시료(2)를 이온건(3)의 상부에 위치시키고 진공조(1) 외부의 가스 주입관을 통하여 불활성 또는 반응성 가스를 이온건에 주입하여 이온을 발생시킨다. 또한 반응성 가스는 가스 주입관(4)을 통하여 시료의 표면 주위에 불어넣어 준다.A schematic longitudinal cross-sectional view of the ion beam treatment apparatus used in the present invention is shown in FIG. As shown in FIG. 1, ion beam irradiation is carried out in a vacuum chamber 1 which maintains a vacuum by a vacuum pump 5, and places a sample 2 on the top of the ion gun 3 and outside the vacuum chamber 1. Inert or reactive gas is injected into the ion gun through the gas injection tube to generate ions. In addition, the reactive gas is blown around the surface of the sample through the gas injection pipe (4).
이온 생성에 사용되는 불활성 가스 또는 반응성 가스는 헬륨, 네온, 아르곤, 크립톤, 제논, 산소, 질소, 공기등의 이온화가 가능한 모든 가스에 해당한다.The inert gas or reactive gas used for generating ions is any gas capable of ionizing helium, neon, argon, krypton, xenon, oxygen, nitrogen, air, and the like.
에너지를 가진 이온을 고분자에 조사하면 고분자 표면 사슬의 결합이 절단되어 활성화된 라디칼이 생성되며 이때 주입된 반응성 기체와 결합하여 고분자 표면에 극성 작용기들이 형성된다.When the ions with energy are irradiated to the polymer, the bonds of the polymer surface chains are cleaved to generate activated radicals, which are combined with the injected reactive gas to form polar functional groups on the polymer surface.
이때 이온 조사에 의하여 개질되는 깊이는 수 nm에 불과하므로 고분자가 가진 고유한 물성에는 변화를 주지 않고 표면만을 개질할 수 있다. 새로이 형성된 극성 작용기들은 또한 친수성 작용기로 작용하여 고분자 표면의 젖음성을 향상시킨다.In this case, since the depth modified by ion irradiation is only a few nm, only the surface may be modified without changing the inherent physical properties of the polymer. The newly formed polar functional groups also act as hydrophilic functional groups to improve the wettability of the polymer surface.
도 2는 폴리카보네이트를 Ar+이온빔을 조사하고 산소를 반응성 가스로 흘려주며 이온 조사량에 따라 처리한 경우의 물에 대한 접촉각 변화를 나타낸 것이다. 이때 사용된 이온 에너지는 1000 eV로 고정하였고 반응성 가스인 산소의 양은 8 ml/min으로 조절하였다. 고분자 표면에 조사되는 이온 조사량은 5 × 1014ions/cm2- 5 × 1016ions/cm2으로 변화되었다.2 shows a change in contact angle with respect to water when polycarbonate is irradiated with an Ar + ion beam, oxygen is flowed into a reactive gas, and treated according to the amount of ion irradiation. The ion energy used was fixed at 1000 eV and the amount of oxygen, a reactive gas, was adjusted to 8 ml / min. Ion dose to be irradiated to the polymer surface is 5 × 10 14 ions / cm 2 - it was changed to 5 × 10 16 ions / cm 2 .
처리되지 않은 폴리카보네이트의 초기 접촉각은 78도이나 이온빔조사에 의하여 표면 개질된 경우 최대 12도까지 접촉각이 감소하여 물에 대한 친수 특성을 나타낸다. 즉, 고분자재료의 표면이 친수성으로 개선되어 이후 진행되는 발수막 코팅의 균일한 도포와 접착력의 증대를 기대 할 수 있게 되었다.The initial contact angle of the untreated polycarbonate is 78 degrees, but when the surface is modified by ion beam irradiation, the contact angle decreases up to 12 degrees, indicating hydrophilic properties for water. In other words, the surface of the polymer material is improved to the hydrophilicity can be expected to increase the uniform coating and adhesion of the water-repellent membrane coating to be carried out later.
도 3은 이온빔으로 표면 개질된 폴리카보네이트의 표면 에너지 변화를 나타낸 것이다. 이때 이온 에너지와 반응성 가스인 산소의 양은 도 2에 나타난 것과 동일하다.3 shows the surface energy change of polycarbonate surface modified with ion beams. At this time, the ion energy and the amount of oxygen which is a reactive gas are the same as those shown in FIG. 2.
도 3에 나타난 바와 같이 표면 개질 후의 폴리카보네이트의 표면 에너지는 이온 조사량에 따라 차이가 있으나 처리 전 28 ergs/cm2에 비하여 처리 후 크게 증가되며 최대 68 ergs/cm2까지 증가된다. 이온 조사에 따른 표면 에너지 증가는 주로 극성 성분(polar component)의 증가에 기인한다. 이는 이온 조사에 따른 표면 에너지의 증가가 폴리카보네이트 표면에 형성된 극성 작용기에 의한 것임을 보여준다.As shown in FIG. 3, the surface energy of the polycarbonate after surface modification varies depending on the amount of ion irradiation, but is greatly increased after treatment compared to 28 ergs / cm 2 before treatment, and increases up to 68 ergs / cm 2 . The surface energy increase due to ion irradiation is mainly due to the increase in polar components. This shows that the increase in surface energy due to ion irradiation is due to the polar functional groups formed on the polycarbonate surface.
도 2와 3에 나타난 바와 같은 접촉각의 감소와 표면 에너지의 증가는 고분자 표면의 물에 대한 젖음성을 좋게 하여 물을 용매로 하는 발수 코팅액의 균일한 도포를 가능하게 하고 건조 후 발수막과의 접착성을 향상시켜 내구성이 우수한 발수막의 형성을 가능하게 할 수 있다.The reduction of contact angle and increase of surface energy as shown in FIGS. 2 and 3 improve the wettability of water on the surface of the polymer to enable uniform application of a water-repellent coating solution using water as a solvent and adhesion to the water-repellent film after drying. It can be possible to form the water-repellent film with excellent durability by improving the.
이온빔으로 친수 처리된 폴리카보네이트 위에 각각 불소계와 실리콘계의 성분이 포함된 발수액을 도포한 후에 측정된 접촉각을 아래의 표 1에 나타내었다.The contact angles measured after applying a water repellent solution containing fluorine-based and silicon-based components on a polycarbonate hydrophilized with an ion beam are shown in Table 1 below.
표 1 표면 개질된 폴리카보네이트위에 발수막 코팅 전 후의 접촉각 변화Table 1 Change in contact angle before and after water repellent coating on surface modified polycarbonate
비교를 위하여 무처리 폴리카보네이트와 이온빔으로 표면 개질된 폴리카보네이트의 접촉각을 함께 나타내었다.For comparison, the contact angles of untreated polycarbonate and polycarbonate surface modified with ion beams are also shown.
발수 코팅을 한 후의 폴리카보네이트의 접촉각은 불소계 발수 코팅의 경우 110도로 나타났으며 실리콘계 발수 코팅의 경우는 120도로 나타나 처리 전의 78도에 비하여 상당히 증가됨을 알 수 있다. 이는 발수 코팅된 폴리카보네이트 표면이 물에 젖지 않게 됨을 의미한다.The contact angle of the polycarbonate after the water repellent coating was 110 degrees for the fluorine-based water repellent coating, and 120 degrees for the silicone-based water repellent coating, which is considerably increased compared to 78 degrees before the treatment. This means that the water repellent coated polycarbonate surface will not be wet with water.
도 4는 무처리 폴리카보네이트와 발수막으로 코팅된 폴리카보네이트의 물에 대한 젖음성의 변화를 보여주기 위한것으로써, 도4a는 무처리된 폴리카보네이트의 표면사진이고, 도4b는 실리콘계 발수 코팅된 폴리카보네이트의 표면사진이며, 도4c는 불소계 발수 코팅된 폴리카보네이트의 표면사진이다.Figure 4 is to show the change in the wettability of the non-treated polycarbonate and the polycarbonate coated with a water repellent film, Figure 4a is a surface photograph of the untreated polycarbonate, Figure 4b is a silicone-based water-repellent coated poly 4C is a surface photograph of a carbonate-based water repellent coated polycarbonate.
즉, 이온빔으로 표면 개질 후에 발수 코팅된 폴리카보네이트의 발수 특성을 알아보기 위하여 다음과 같은 실험을 수행하였다. 300 ml의 비이커에 100 ml의 물을 채워 50 - 60℃로 가열한 후, 발수 코팅된 폴리카보네이트와 무처리 폴리카보네이트로 상부를 밀봉하였다.That is, the following experiment was performed to investigate the water repellent properties of the water-repellent coated polycarbonate after surface modification with an ion beam. The 300 ml beaker was filled with 100 ml of water and heated to 50-60 ° C., and the top was sealed with water-repellent coated polycarbonate and untreated polycarbonate.
그 결과, 도 4a에 나타난 바와 같이 처리되지 않은 폴리카보네이트의 표면에는 작은 크기의 많은 물방울이 형성된다. 반면에 발수 코팅된 경우에는 작은 물방울 대신 큰 크기의 물방울만이 형성되어 처리 전 폴리카보네이트와는 다른 특성을 갖는다.As a result, many droplets of small size are formed on the surface of the untreated polycarbonate as shown in FIG. 4A. On the other hand, in the case of water-repellent coating, only water droplets of large size are formed instead of small water droplets, and thus have different characteristics from those of polycarbonate before treatment.
위와 같은 실험을 10일 동안 수행한 후 측정한 접촉각은 초기 측정치와 큰 변화가 없었으며 이로부터 코팅된 발수막이 외부로 유출되지 않고 우수한 내구성을 갖음을 알 수 있다.The contact angle measured after performing the above experiment for 10 days did not change significantly with the initial measurement, from which it can be seen that the coated water repellent membrane does not leak to the outside has excellent durability.
이상 본 발명의 바람직한 실시예에 대해 상세히 기술하였지만, 본 발명이 속하는 기술분야에 있어서 통상의 지식을 가진 사람이라면, 첨부된 청구범위에 정의된 본 발명의 정신 및 범위를 벗어나지 않으면서 본 발명을 여러 가지로 변형 또는변경하여 실시할 수 있음을 알게 될 것이다. 따라서 본 발명의 앞으로 실시예들의 변경은 본 발명의 기술을 벗어날 수 없을 것이다.Although the preferred embodiments of the present invention have been described in detail above, those of ordinary skill in the art to which the present invention pertains may make various changes without departing from the spirit and scope of the present invention as defined in the appended claims. It will be appreciated that modifications or variations may be made to the branches. Therefore, changes in the future embodiments of the present invention will not be able to escape the technology of the present invention.
본 발명에 따른 고분자의 발수막 코팅을 위한 표면 개질 방법에 따르면 고분자재질의 표면에 발수막 코팅을 하는데 있어 기존보다 공수가 절감되고 환경오염을 줄일 수 있으며 고분자 재질 표면과의 접착성이 우수한 발수막 코팅을 할 수 있도록 친수성을 상기 고분자재료의 표면에 형성할 수 있게 되었다.According to the surface modification method for coating the water repellent membrane of the polymer according to the present invention in the water repellent coating on the surface of the polymer material can reduce the air transport and environmental pollution than conventional water repellent membrane with excellent adhesion to the surface of the polymer material Hydrophilicity can be formed on the surface of the polymer material to enable coating.
Claims (11)
Priority Applications (1)
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| KR100385486B1 true KR100385486B1 (en) | 2003-05-27 |
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020096124A (en) * | 2001-06-18 | 2002-12-31 | 주식회사 피앤아이 | Method for surface reforming protection layer of identification card |
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| KR100701645B1 (en) * | 2004-08-02 | 2007-03-30 | 도레이새한 주식회사 | Method manufacturing structure for flexible printed circuit board |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR0166950B1 (en) * | 1996-08-13 | 1999-01-15 | 전영식 | Process of drainage coating |
| KR100217538B1 (en) * | 1996-04-10 | 1999-09-01 | 박호군 | Method for modifying a surface of polymeric material using plasma source ion implantation and apparatus therefor |
| KR20000039496A (en) * | 1998-12-14 | 2000-07-05 | 김윤 | Polymer culture dish surface modified utilizing ion-beam and surface modifying method |
| KR20000065896A (en) * | 1999-04-10 | 2000-11-15 | 성재갑 | Method of modificating surface of polymeric materials |
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Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100217538B1 (en) * | 1996-04-10 | 1999-09-01 | 박호군 | Method for modifying a surface of polymeric material using plasma source ion implantation and apparatus therefor |
| KR0166950B1 (en) * | 1996-08-13 | 1999-01-15 | 전영식 | Process of drainage coating |
| KR20000039496A (en) * | 1998-12-14 | 2000-07-05 | 김윤 | Polymer culture dish surface modified utilizing ion-beam and surface modifying method |
| KR100307807B1 (en) * | 1998-12-14 | 2001-11-30 | 김윤 | Surface-Modified Polymer Culture Dishes Using Ion Beam and Method for Surface Modification |
| KR20000065896A (en) * | 1999-04-10 | 2000-11-15 | 성재갑 | Method of modificating surface of polymeric materials |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20020096124A (en) * | 2001-06-18 | 2002-12-31 | 주식회사 피앤아이 | Method for surface reforming protection layer of identification card |
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| KR20020011822A (en) | 2002-02-09 |
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