KR100267176B1 - A manufacturing method of a dry-type electrophotographical screen of crt, and a photo-conductive spreading solution used therefor - Google Patents
A manufacturing method of a dry-type electrophotographical screen of crt, and a photo-conductive spreading solution used therefor Download PDFInfo
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- KR100267176B1 KR100267176B1 KR1019960060211A KR19960060211A KR100267176B1 KR 100267176 B1 KR100267176 B1 KR 100267176B1 KR 1019960060211 A KR1019960060211 A KR 1019960060211A KR 19960060211 A KR19960060211 A KR 19960060211A KR 100267176 B1 KR100267176 B1 KR 100267176B1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D5/00—Coating compositions, e.g. paints, varnishes or lacquers, characterised by their physical nature or the effects produced; Filling pastes
- C09D5/24—Electrically-conducting paints
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D125/00—Coating compositions based on homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Coating compositions based on derivatives of such polymers
- C09D125/02—Homopolymers or copolymers of hydrocarbons
- C09D125/04—Homopolymers or copolymers of styrene
- C09D125/06—Polystyrene
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/60—Additives non-macromolecular
- C09D7/63—Additives non-macromolecular organic
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D7/00—Features of coating compositions, not provided for in group C09D5/00; Processes for incorporating ingredients in coating compositions
- C09D7/40—Additives
- C09D7/65—Additives macromolecular
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/20—Manufacture of screens on or from which an image or pattern is formed, picked up, converted or stored; Applying coatings to the vessel
- H01J9/22—Applying luminescent coatings
- H01J9/227—Applying luminescent coatings with luminescent material discontinuously arranged, e.g. in dots or lines
- H01J9/2271—Applying luminescent coatings with luminescent material discontinuously arranged, e.g. in dots or lines by photographic processes
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J9/00—Apparatus or processes specially adapted for the manufacture, installation, removal, maintenance of electric discharge tubes, discharge lamps, or parts thereof; Recovery of material from discharge tubes or lamps
- H01J9/20—Manufacture of screens on or from which an image or pattern is formed, picked up, converted or stored; Applying coatings to the vessel
- H01J9/22—Applying luminescent coatings
- H01J9/227—Applying luminescent coatings with luminescent material discontinuously arranged, e.g. in dots or lines
- H01J9/2276—Development of latent electrostatic images
Abstract
Description
본 발명은 음극선관의 건식 전자사진식 스크린 제조방법과 이에 사용되는 광전도막 도포용액에 관한 것으로, 특히 대전특성과 대전의 균일성이 향상되면서 열분해(연소)특성이 보완될 뿐만 아니라 크랙과 같은 광전도막의 손상이 없는 광전도막 도포용액 및 이를 사용한 음극선관의 건식 전자사진식 스크린 제조방법에 관한 것이다.The present invention relates to a method for manufacturing a dry electrophotographic screen of a cathode ray tube and a photocoating film coating solution used therein. In particular, the pyrolysis (combustion) characteristics are not only compensated for by improving charging characteristics and uniformity of charging, but also photoelectric such as cracks. The present invention relates to a photoelectrode coating solution without damage to a coating film and a dry electrophotographic screen manufacturing method of a cathode ray tube using the same.
일반적으로 음극선관은, 도 1에 도시된 바와 같이, 판넬(panel)(12), 펀넬(funnel)(13) 및 네크(14)로 구분되는 진공 벌브(bul)와, 그 네크(14) 내부에 장착되는 전자총(11)과, 판넬(12)의 측벽에 장착되는 새도우마스크(16)를 구비한다.Generally, a cathode ray tube, as shown in FIG. 1, has a vacuum bulb divided into a panel 12, a funnel 13, and a neck 14, and inside the neck 14. And an shadow gun 16 mounted on the sidewall of the panel 12.
그 판넬(12)의 면판(18)의 내면에는 형광면(20)이 형성되어 있어, 전자총(11)으로부터 방출된 전자빔(19a)(19b)은 각종 렌즈계에 의해 집속되고 가속되며, 양극보턴(15)을 통해 인가되는 고전압에 의해 크게 가속되면서 편향요크(17)에 의해 편향되고 새도우마스크(16)의 애퍼처 또는 슬로트(16a)를 통과하여 형광면(20)에 주사된다.A fluorescent surface 20 is formed on the inner surface of the face plate 18 of the panel 12, and the electron beams 19a and 19b emitted from the electron gun 11 are focused and accelerated by various lens systems, and the anode button 15 It is greatly accelerated by the high voltage applied through the deflection yoke 17, deflected by the deflection yoke 17 and passed through the aperture or slot 16a of the shadow mask 16 to the fluorescent surface 20.
형광면(20)은 면판(18)의 배면에 형성되는데, 칼라의 경우 도 2에 도시된 바와 같이 일정한 배열구조의 다수의 스트라이프(stripe) 또는 도트(dot)형상의 형광체(R, G, B)와 그 각 형광체들 사이의 블랙코팅과 같은 빛흡수물질(21)로 형성된다. 또, 그 배면은 전도막층으로서 알루미늄박막층(22)이 형성되어 형광면의 휘도 증대, 형광면의 이온손상방지, 형광면의 전위강하방지 등의 역할을 하게된다. 또한, 도시되지는 않지만, 그 알루미늄박막층(22)의 평면도 및 반사율을 높이기 위해서는 형광면(20)과 광전도막층(34)사이에 라커(lacquer)와 같은 수지가 도포된다.The fluorescent surface 20 is formed on the rear surface of the face plate 18. In the case of the color, as shown in FIG. 2, a plurality of stripe or dot-shaped phosphors R, G, and B in a constant arrangement structure are shown. And a light absorbing material 21 such as a black coating between the respective phosphors. In addition, the rear surface is formed with an aluminum thin film layer 22 as a conductive film layer, which serves to increase the luminance of the fluorescent screen, to prevent ion damage of the fluorescent screen, and to prevent the potential drop of the fluorescent screen. Although not shown, a resin such as lacquer is applied between the fluorescent surface 20 and the photoconductive layer 34 to increase the plan view and reflectance of the aluminum thin film layer 22.
이러한 형광면(20)이 발색광 인성분과 같은 형광입자들을 포함하는 현탁액(slurry) 또는 빛흡수물질을 포함하는 현탁액을 도포하고 건조시켜 형성되는 종래의 습식 사진석판슬(photolithographic wet process)은, 고화질의 요구를 충족시키지 못할 뿐만 아니라 제조공정 및 제조설비가 복잡하여 제조비용이 크게 소용되며, 또한, 대량의 청정수 소모와 폐수발생, 인배출물, 6가 크롬감광체 배출 등 여러 가지 문제점들을 안고 있다. 최근에 이러한 습식사진석판술을 개량한 전자사진식(electrophotographical) 스크린제조방법이 개발되었는데, 이 전자사진식 제조방법도 습식은 여전히 상술한 문제점들을 안고 있으며, 건식제조방법에 의해서는 상술한 문제점들이 상당히 해소되었다.The conventional photolithographic wet process in which the fluorescent surface 20 is formed by applying and drying a suspension containing fluorescent particles such as a chromophoric phosphorus component or a suspension containing a light absorbing material is high quality. Not only does not meet the requirements, the manufacturing process and manufacturing equipment is complicated, the manufacturing cost is greatly utilized, and also has a number of problems, such as the consumption of large amounts of clean water, wastewater generation, phosphorus emissions, hexavalent chromium photoresist emissions. Recently, an electrophotographic screen manufacturing method has been developed that improves the wet photolithography. In this electrophotographic manufacturing method, the wet still has the above-mentioned problems. It was considerably resolved.
그 대표적인 건식 전자사진식 스크린제조방법은 미국 특허 제 4,921,767호 (1009년 5월 1일 특허됨)에 개시되어 있는 바, 이를 간략히 설명하면 다음과 같다.A representative dry electrophotographic screen manufacturing method is disclosed in US Patent No. 4,921,767 (patented May 1, 1009), which is briefly described as follows.
도 3(a) 내지 (e)에는 그 건식전자시진식 스크린제조방법의 각 기본 공정이 개략적으로 도시된다.3 (a) to 3 (e) schematically show each basic process of the dry electron visual screen manufacturing method.
판넬(12)는 스크린공정에 들어가기 전에 그 내면이 여러 가지 방법으로 세척된다. 그리고 나서, 그 판넬의 면판(18)의 내면에는 도 3a에서와 같이 전기적 전도막(32)이 코팅되고, 그 위에 광전도막(34)이 코팅된다. 이러한 전도막(32)에 사용되는 화합물로는 주석이나 인듐(indium)산화물, 또는 그 혼합물과 같은 무기전도물이 개시되어 있고, 휘발성전도막의 원료로는 Aldrich Chemical Co.의 상품명 폴리브린(Ploybrene : 1,5-디메틸-1,5-디아자-언디카메틸렌 폴리메소브로마이드, 헥사 디메스린 브로마이드)이 개시되어 있다. 이러한 폴리브린은 약 10 중량%의 프로판놀과 10중량% 수용성 접착 폴리머(폴리 비닐알콜, 폴리아크릴산, 폴리아미드 등)를 함유하는 수용액상태로 도포되고 건조되어 108Ω/ ?(ohms per square unit) 이하의 표면저항과 약 1-2㎛의 두께를 가지는 전도막(32)을 형성한다. 그 전도막(32)위에 도포되는 광전도막(34)으로는 휘발성 유기폴리머(폴리비닐 카바졸) 또는 폴리머 바인더(폴리메틸메타크릴레이트 또는 폴리프로필렌 카본네이트)에 용해된 n-에틸 카바졸이나 n-비닐카바졸 또는 테트라페닐부타트리엔과 같은 유기단량체와, 적당한 광전도 염료와 용매를 포함하는 도포액이 개시되어 있다. 그 광전도 염료성분으로는 가시광선(바람직하게는 400-700nm파장)에 반응하는 것으로서 크리스탈 바이오릿(crystal violet), 크로리다인 블루우(chloridine blue), 로다민 EG(rhodamine EG)와 같은 것들이 약 0.1 내지 0.4 중량% 함유되는 것으로 개시되어 있다. 그리고 용매로는 전도막(32)을 오염시키지 아니하는 클로로벤젠이나 싸이클로펜타논과 같은 유기물이 개시되어 있다. 이와같은 조성을 가지는 광전도막(34)은 2-6μ의 두께를 가진다.Before the panel 12 enters the screening process, the inner surface of the panel 12 is cleaned in various ways. Then, the inner surface of the panel 18 of the panel is coated with an electrically conductive film 32, as shown in Figure 3a, a photoconductive film 34 is coated thereon. As the compound used in the conductive film 32, inorganic conductive materials such as tin, indium oxide, or mixtures thereof are disclosed. As a raw material of the volatile conductive film, Aldrich Chemical Co. 1,5-dimethyl-1,5-diaza-undicamethylene polymethobromide, hexadimethrin bromide) is disclosed. The polybrine is applied in an aqueous solution containing about 10% by weight of propanol and 10% by weight water-soluble adhesive polymer (polyvinyl alcohol, polyacrylic acid, polyamide, etc.) and dried to obtain 10 8 Ω /? (Ohms per square unit). ) And a conductive film 32 having a surface resistance of about 1-2 μm or less. The photoconductive film 34 coated on the conductive film 32 is n-ethyl carbazole or n dissolved in a volatile organic polymer (polyvinyl carbazole) or a polymer binder (polymethyl methacrylate or polypropylene carbonate). A coating liquid comprising an organic monomer such as -vinylcarbazole or tetraphenylbutatriene, a suitable photoconductive dye and a solvent is disclosed. Its photoconductive dye reacts to visible light (preferably 400-700nm wavelength), such as crystal violet, chloridine blue and rhodamine EG. About 0.1 to 0.4% by weight. As the solvent, organic substances such as chlorobenzene and cyclopentanone that do not contaminate the conductive film 32 are disclosed. The photoconductive film 34 having such a composition has a thickness of 2-6 mu.
도 3b에는 상술한 바와 같이 이중코팅된 면판(18)의 광전도막(34)에 종래의 코로나방전장치(36)에 의해 암실에서 +전하로 대전되는 대전공정이 개략적으로 도시된다. 그 코로나 방전장치(36)는 +200 내지 +700 볼트의 직류전원의 +전극에 인가되고, -전극은 전도막(32)에 인가됨과 동시에 어스되며, 이와 같이 +전극에 인가된 코로나방전장치(36)가 면판(18)의 광전도막(34)위를 가로질러 이동함으로써 광전도막(34)은 +전하로 대전되게 된다.3b schematically shows a charging process in which the photoconductor film 34 of the double coated face plate 18 is charged with positive charge in the dark room by a conventional corona discharge device 36 as described above. The corona discharge device 36 is applied to the + electrode of the DC power supply of +200 to +700 volts, the-electrode is applied to the conductive film 32 and ground at the same time, the corona discharge device ( As the 36 moves across the photoconductive film 34 of the face plate 18, the photoconductive film 34 is charged with positive charge.
도 3c는 노광공정을 도시한 것으로 상술한 바와 같이 대전된 광전도막(34)은 역시 암실내에서 새도우마스크(16)를 통해 렌즈(40)를 구비하는 크세논 플래시 램프(38)에 의해서 노광된다. 따라서, 먼저 새도우마스크(16)가 판넬(12)에 장착되고 전도막(32)은 어스된다. 이 공정에서는 그 크세논 플래시램프(38)를 켜서 렌즈(40)와 새도우마스크(16)를 통해 그 램프(38)의 광선을 광전도막(34)에 조사하면, 새도우마스크(16)의 애퍼처 또는 슬로트(16a)에 해당하는 광전도막(34)부분들이 노광되고, 그 가시광선에 의해 그 노광부분의 +전하가 전도막(32)을 통해 방출되어 도 3c에 도시된 바와 같이 노광부분만 비대전상태로 된다. 상술한 크세논 플래시 램프(38)는 칼라의 경우 빛흡수물질을 부착시키기 위해서는 종래와 같이 그 광선이 각 전자빔의 입사각에 일치하도록 3취치사이를 이동하는 구조가 바람직하다.3C illustrates an exposure process, in which the photoconductive film 34 charged as described above is also exposed by a xenon flash lamp 38 having a lens 40 through a shadow mask 16 in a dark room. Therefore, the shadow mask 16 is first mounted on the panel 12 and the conductive film 32 is earthed. In this process, when the xenon flash lamp 38 is turned on to irradiate the photoconductive film 34 with the light beam of the lamp 38 through the lens 40 and the shadow mask 16, the aperture of the shadow mask 16 or Portions of the photoconductive film 34 corresponding to the slot 16a are exposed, and the positive charges of the exposed portions are emitted through the conductive film 32 by the visible light, so that only the exposed portions are exposed as shown in FIG. 3C. It becomes a charged state. In the case of the xenon flash lamp 38 described above, in order to attach the light absorbing material to the color, the xenon flash lamp 38 preferably has a structure in which the light beam is moved between three positions so as to correspond to the incident angle of each electron beam.
도 3d는 현상(형광입자 또는 빛흡수물질의 부착)공정을 개략적으로 도시한다. 이 공정에서는 현상용기(42)내에 건식 빛흡수물질 미세분말 또는 건식의 각 형광체미세분말과, 그 각 분말과의 접촉으로 정전기를 발생시킬 수 있는 캐리어 비드(carrier bead)가 담겨진다. 그 빛흡수물질용 캐리어 비드는 미세분말과 접촉하여 빛흡수물질입자는 -전하로, 또 형광입자는 +전하로 대전시킬 수 있는 것이 적당하며, 그와 같이 전하를 띠도록 혼합된다. 새도우마스크(16)를 제거한 판넬(12)은 광전도막(34)이 그 분말에 접촉할 수 있도록 상술한 분말이 담긴 현상용기(42)위에 설치된다.3d schematically illustrates a development (adhesion of fluorescent particles or light absorbing material) process. In this step, the developing container 42 contains a dry light absorbing material fine powder or a dry phosphor fine powder and a carrier bead capable of generating static electricity by contact with each powder. The carrier beads for the light absorbing material are in contact with the fine powder so that the light absorbing material particles can be charged with -charge and the fluorescent particles with + charge. The panel 12 from which the shadow mask 16 is removed is installed on the developing container 42 containing the above-described powder so that the photoconductive film 34 can contact the powder.
이 때 혼합된 분말 중에서 -전하를 띤 빛흡수물질은 +전하로 대전된 광전도막(34)의 비노광부분에 전기인력에 의해 부착되게 되며, +전하를 띤 형광입자는 +전하로 대전된 광전도막(34)의 비노광부분에서는 반발하고 비대전상태로 된 광전도막(34)의 노광부분에만 역현상(reversal developing)에 의해 부착하게 된다.At this time, the negatively charged light absorbing material in the mixed powder is attached to the non-exposed portion of the photoconductive film 34 charged with + charge, and the positively charged fluorescent particles are + charged photoelectrically charged particles. In the non-exposed part of the coating film 34, it adheres only to the exposed part of the photoconductive film 34 which is in a non-charged state by reversal developing.
도 3e는 적외선 가열에 의한 고착공정을 도시한 것으로, 이 공정에서는 상술한 현상공정에서 부착된 건식 빛흡수물질입자 또는 건식의 각 형광입자들이 서로, 또한, 광전도막(34)에 고착된다. 따라서, 가열에 의해 융착되는 적당한 폴리머 성분이 그 광전도막(34)과 건식 빛흡수물질입자나 건식의 각 형광입자들에 포함된다.FIG. 3E shows a fixing process by infrared heating, in which dry light absorbing material particles or dry fluorescent particles attached in the above-described developing process are fixed to each other and to the photoconductive film 34. Therefore, a suitable polymer component fused by heating is included in the photoconductive film 34 and the dry light absorbing material particles or dry fluorescent particles.
상술한 공정들이 칼라음극선관의 제조를 위해서는 3종의 형광체에 대해 반복 실시된다. 이와 같이 형광체 및 빛흡수물질이 형성된 다음, 라커공정에서 라커막이 종래의 방법으로 형성되고, 알루마이징공정에서 알루미늄박막도 종래의 방법으로 형성되며, 그 뒤, 베이킹(baking)공정으로 투입되어 대기 중에서 약 30분동안 425℃에서 가열 건조됨으로써, 전도막(32), 광전도막(34)과 각 형광체 및 라커 등에 존재하는 용매 등의 휘발성성분이 제거되고 빛흡수물질(21)과 각 형광체(R, G, B)가 도 2(a)(b)에서와 같이 형성된 형광면(20)이 얻어진다.The above-described processes are repeated for three kinds of phosphors for the production of the color cathode ray tube. After the phosphor and the light absorbing material are formed, the lacquer film is formed by the conventional method in the lacquer process, and the aluminum thin film is formed by the conventional method in the anodizing process, and then, is introduced into the baking process by By heating and drying at 425 ° C. for about 30 minutes, volatile components such as the conductive film 32, the photoconductive film 34, and a solvent present in each phosphor and lacquer are removed, and the light absorbing material 21 and each phosphor (R, A fluorescent surface 20 having G and B formed as shown in Figs. 2A and 2B is obtained.
그러나, 상술한 종래의 건식전자사진식 스크린 제조방법은 광전도막이 가시광선에 쉽게 감응되어지기 때문에 광전도막을 형성한 이후 고착공정에 이르기까지 모든 작업을 암실에서 수행하여야 하는 단점이 있었다.However, the conventional dry electrophotographic screen manufacturing method described above has a disadvantage in that all operations from the formation of the photoconductive film to the fixing process are performed in the dark room because the photoconductive film is easily sensitive to visible light.
이에, 본 출원인은 광전도막을 자외선에 감응하는 광전도성 용액으로 조성함으로써 상기의 문제점을 해결하였다. 이때, 광전도막을 형성하기 위한 광전도막 용액으로서, 자외선에 반응하는 물질로는 비스디메틸 페닐 디페닐 부타트리엔(bisdimethyl phenyl diphenyl butatriene)과, 트리니트로플루오리논(trinitro-fluorenone: TNF) 및 에틸 안트라퀴논(ethyl anthraquinone: EAQ)중 적어도 1종 이상을 사용하였으며, 그 광전도막 도포용액으로는 0.01 내지 10중량%의 비스디메틸 페닐 디페닐 부타트리엔과 고분자바인더(binder)로서 1 내지 30 중량%의 폴리스티렌(polystyrene)을 잔량인 톨루엔(toluene)이나 크실렌(xylene)에 용해시켜 사용하였다.Accordingly, the present applicant solved the above problems by forming the photoconductive film into a photoconductive solution sensitive to ultraviolet rays. In this case, as a photoconductor solution for forming a photoconductor, a material that reacts to ultraviolet rays includes bisdimethyl phenyl diphenyl butatriene, trinitro-fluorenone (TNF), and ethyl anthra. At least one or more of quinone (ethyl anthraquinone (EAQ)) was used, and the photoconductive coating solution was 0.01 to 10% by weight of bisdimethyl phenyl diphenyl butytriene and 1 to 30% by weight of a polymer binder. Polystyrene was used after dissolving in toluene or xylene, which is the residual amount.
그러나, 자외선 반응물질로 사용된 비스디메틸 페닐 디페닐 부타트리엔은 톨루엔이나 크실렌에 대한 용해도가 매우 낮아 그 톨루엔이나 크실렌에 용해시키는데에 상당한 시간과 공정이 요구된다는 문제점이 있다. 또한, 폴리스티렌은 대전특성은 우수하나, 연소(열분해)특성이 열등하여 베이킹공정에서 쉽게 휘발되지 아니하고 잔류하거나 기포를 발생시키는 등의 문제점이 있다.However, bisdimethyl phenyl diphenyl butytriene used as an ultraviolet reactant has a problem in that solubility in toluene or xylene is so low that a considerable time and process are required to dissolve it in toluene or xylene. In addition, the polystyrene has excellent charging characteristics, but inferior combustion (pyrolysis) characteristics cause problems such as not easily volatilized in the baking process or residual bubbles.
이러한 문제점을 해결하기 위해 본 출원인은 5-15 중량%의 폴리스티렌(polystylene), 1-5 중량%의 폴리 알파-메틸 스티렌(poly α-methyl stylene), 0.01∼10 중량%의 메틸 페닐 트리페닐 부타트리엔, 0.01∼10 중량%의 트리니트로플루오리논(trinitro-fluorenone: TNF) 및 0.01∼10 중랑%의 에틸 안트라퀴논(ethyl anthraquinone: EAQ)중 적어도 1종, 계면활성제로서 L-7602 그리고 나머지 잔량은 벤젠유도체로 된 용매로 구성된 것을 특징으로 광전도막 도포용액을 고안한 바, 있다.In order to solve this problem, the applicant has 5-15 wt% polystyrene, 1-5 wt% poly alpha-methyl styrene, 0.01-10 wt% methyl phenyl triphenyl buta At least one of triene, 0.01-10% by weight of trinitro-fluorenone (TNF) and 0.01-10% by weight of ethyl anthraquinone (EAQ), L-7602 as a surfactant and the remainder Silver has been devised a photoconductive film coating solution, characterized in that consisting of a solvent of a benzene derivative.
그러나, 이 광전도막 도포용액도 상술한 종래의 광전도막의 성분에 비해 그 연속특성 및 광전측성이 월등하지만, 막의 강도가 약하여 1차 현상후에 부분적으로 광전도막이 손상되므로 2차 대전 이후의 공정에서는 손상된 부분에서 원활하지 못하게 된다는 문제점이 있다.However, the photocoating film coating solution is also superior to the components of the conventional photoconductive film described above, but its continuous characteristics and photoelectricity are superior. However, since the strength of the film is weak, the photocoating film is partially damaged after the first development. There is a problem that the part is not smooth.
따라서, 본 발명은 상술한 문제점을 해결하기 위한 것으로, 광전특성 내지 대전특성과 열분해(연소)특성이 유지되면서도 막의 강도가 향상되어 손상이 일어나지 아니하는 음극선관의 건식 전자사진식 스크린 제조방법과 이에 사용되는 광전도막 도포용액을 제공하는 데 그 목적이 있다.Accordingly, the present invention has been made to solve the above-described problems, the method of manufacturing a dry electrophotographic screen of a cathode ray tube that does not cause damage by improving the strength of the film while maintaining the photoelectric properties, charge characteristics and pyrolysis (combustion) characteristics and this It is an object to provide a photocoating film coating solution to be used.
제 1 도는 칼라음극선관의 부분단면한 개략평면도.1 is a schematic cross-sectional view partially showing a color cathode ray tube.
제 2 도는 제 1 도의 음극선관의 스크린 구성을 나타낸 부분 확대단면도.2 is a partially enlarged cross-sectional view showing the screen configuration of the cathode ray tube of FIG.
제 3 도는 건식전자사진식 스크린 제조방법을 설명하기 위한 개략도.3 is a schematic view for explaining a method of manufacturing a dry electrophotographic screen.
* 도면의 주요부분에 대한 부호의 설명* Explanation of symbols for main parts of the drawings
10 : 음극선관(CRT) 11 : 전자총10 cathode ray tube (CRT) 11 electron gun
12 : 판넬(panel) 13 : 펀넬(funnel)12: panel 13: funnel
14 : 네크(neck) 15 : 양극 보턴14 neck 15 anode button
16 : 새도우마스크 17 : 편향요크16: shadow mask 17: deflection yoke
18 : 판넬면판 19, 19a, 19b : 전자빔18: panel face plate 19, 19a, 19b: electron beam
20 : 형광면(스크린) 21 : 빛흡수물질20: fluorescent screen (screen) 21: light absorbing material
22 : 라카막 23 : 알루미늄박막층22: laka film 23: aluminum thin film layer
32 : 전도막 34 : 광전도막32: conductive film 34: photoconductive film
36 : 코로나방전장치 38 : 광원(가시광선)36 corona discharge device 38 light source (visible light)
40 : 렌즈 42 : 현상용기40 lens 41 developing container
본 발명은, 상기의 목적을 달성하기 위하여, 판넬내면에 휘발성 전도막을 형성시키고, 그 위에 휘발성 광전도막을 형성시키며, 그 광전도막에 균일한 정전하를 대전시킨 후, 광원에 의해 선택적으로 상기 광전도막의 정전하를 방출시켜서 정전하로 대전된 분말입자를 부착시키는 건식 전자사진식 음극선관의 스크린 제조용 광전도막 도포용액에 있어서, 폴리스티렌(polystylene)과 폴리 알파-메틸 스티렌(poly α-methyl stylene)이 5:5 내지 6:4의 비율로 벤젠유도체로 된알파-메틸 스티렌(poly α-methyl stylene) 용매에 용해, 혼합되고 그 결과물에 상기 폴리스티렌(polystylene)과 폴리 알파-메틸 스티렌(poly α-methyl stylene)의 양의 1 내지 10중량%의 가소제를 포함하는 것을 특징으로 하는 음극선관의 건식전자사진식 스크린 제조용 광전도막 용액을 제공한다.In order to achieve the above object, the present invention is to form a volatile conductive film on the inner surface of the panel, to form a volatile photoconductive film thereon, and to charge the photoelectric film with a uniform electrostatic charge, and then selectively In the photoconductor coating solution for screen production of a dry electrophotographic cathode ray tube which emits electrostatic charge of a coating film and attaches powder particles charged with electrostatic charge, polystylene and poly alpha -methyl styrene are It is dissolved and mixed in an alpha -methyl styrene solvent made of benzene derivatives at a ratio of 5: 5 to 6: 4, and the resulting polystyrene and poly alpha -methyl styrene It provides a photoconductive film solution for producing a dry electrophotographic screen of a cathode ray tube, characterized in that it comprises a plasticizer of 1 to 10% by weight of the amount of stylene).
상기 광전도막 도포용액은 0.01∼10 중량%의 메틸 페닐 트리페닐 부타트리엔, 0.01∼10 중량%의 트리니트로플루오리논(trinitro-fluorenone: TNF) 및 0.01∼10 중량%의 에틸 안트라퀴논(ethyl anthraquinone: EAQ) 중 적어도 1종, 계면활성제로서 L-7602를 추가로 포함할 수 있다.The photoconductive coating solution is 0.01 to 10% by weight of methyl phenyl triphenyl butytriene, 0.01 to 10% by weight of trinitro-fluorenone (TNF) and 0.01 to 10% by weight of ethyl anthraquinone At least one of EAQ), and may further include L-7602 as a surfactant.
또한, 본 발명은 판넬의 내면에 코팅된 휘발성전도막위에 자외선에 감응하는 물질을 함유하는 휘발성광전도막을 형성시키고, 그 광전도막에 균일한 정전하를 대전시킨 후, 그 광전도막을 자외선광원으로부터 자외선을 새도우마스크를 통과시켜 선택적으로 노광하고, 그 노광된 부분에 방전전극에 의해 대전된 제 1 형광체를 부착시키며, 제 2 및 제 3 형광체에 대해서도 각각 소망의 배열로 상기 대전단계, 노광단계 및 부착단계를 반복하고 나서 그 형광체들을 솔벤트증기를 쪼여 고착시키는 고착단계를 포함하는 음극선관의 건식 전자사진식 스크린 제조방법에 있어서, 폴리스티렌(polystylene)과 알파-메틸 스티렌(poly α-methyl stylene)이 5:5 내지 6:4의 비율로 벤젠유도체로 된 용매에 용해, 혼합되고 그 결과물에 상기 폴리스티렌(polystylene)과 알파-메틸 스티렌(poly α-methyl stylene)의 양의 1 내지 10중량%의 가소제를 포함하는 광전도막 도포용액을 도포하여 형성된 것을 특징으로 음극선관의 건식 전자사진식 스크린 제조방법을 제공한다.In addition, the present invention forms a volatile photoconductive film containing a material sensitive to ultraviolet rays on the volatile conductive film coated on the inner surface of the panel, and after charging the electrostatic film with a uniform electrostatic charge, the photoconductive film is separated from the ultraviolet light source. Ultraviolet light is selectively exposed through a shadow mask, and the first fluorescent material charged by the discharge electrode is attached to the exposed portion, and the charging step, the exposure step, and the second and third phosphors, respectively, are arranged in a desired arrangement. In the method of manufacturing a dry electrophotographic screen of a cathode ray tube comprising a fixing step of repeating the attaching step and then fixing the phosphors by solvent vapor, polystyrene (near polystylene) and alpha -methyl styrene (poly α-methyl stylene) Dissolved and mixed in a solvent of a benzene derivative in a ratio of 5: 5 to 6: 4, and the resulting polystyrene and alpha-methyl sty Provides a (poly α-methyl stylene) an amount of from 1 to 10% by weight of the dry electrophotographic method screen of a cathode ray tube characterized in that the coating film formed by coating a coating solution containing a photoelectric plasticizers.
이하, 본 발명을 보다 상세히 설명한다.Hereinafter, the present invention will be described in more detail.
본 발명에 의하면, 판넬 내면에 휘발성 전도막을 형성시키고 그 위에 휘발성 광전도막을 형성시키며, 그 광전도막에 코로나 반전장치 등에 의해 균일한 정전하를 대전시킨 후, 광원에 의해 선택적으로 상기 광전도막의 정전하를 방출시켜서 정전하로 대전된 형광체 분말입자를 부착시키는 전자사진식 음극선관의 스크린 제조용 광전도막 도포용액은, 폴리스티렌(polystylene)과 알파-메틸 스티렌(poly α-methyl stylene)이 5:5 내지 6:4의 비율로 벤젠유도체로 된 용매에 용해, 혼합되고 그 결과물에 상기 폴리스티렌(polystylene)과 알파-메틸 스티렌(poly α-methyl stylene)의 양의 1 내지 10중량%의 가소제를 포함한다. 그 가소제로는 디부틸프탈레이트(DBP), 디옥틸프탈레이트(DOP)등을 들 수 있다.According to the present invention, a volatile conductive film is formed on an inner surface of a panel, and a volatile photoconductive film is formed thereon. The photoelectric film is electrically charged with a uniform electrostatic charge by a corona inverting device or the like, and then selectively discharged by the light source. The photoconductor coating solution for screen production of electrophotographic cathode ray tubes which emits ions and attaches phosphor powder particles charged with electrostatic charges has a polystylene and an alpha -methyl styrene of 5: 5 to 6 It is dissolved and mixed in a solvent of a benzene derivative in a ratio of 4: 4, and the resultant contains 1 to 10% by weight of a plasticizer in an amount of the polystyrene and the poly α-methyl styrene. Dibutyl phthalate (DBP), dioctyl phthalate (DOP), etc. are mentioned as this plasticizer.
그 광전도막 도포용액은 0.01∼10 중량%의 메틸 페닐 트리페닐 부타트리엔, 0.01∼10 중량%의 트리니트로플루오리논(trinitro-fluorenone: TNF) 및 0.01∼10 중량%의 에틸 안트라퀴논(ethyl anthraquinone: EAQ) 중 적어도 1종, 계면활성제로서 L-7602를 추가로 포함할 수 있다.The photocoating coating solution is 0.01 to 10% by weight of methyl phenyl triphenyl butatriene, 0.01 to 10% by weight of trinitro-fluorenone (TNF) and 0.01 to 10% by weight of ethyl anthraquinone. At least one of EAQ), and may further include L-7602 as a surfactant.
상술한 폴리스티렌(polystylene)은 고분자 바인더(binder)로서 사용된다. 그 폴리스티렌은 폴리메틸 메타크릴레이트보다 대전특성이나 대전의 균일성에서는 우수하나, 열분해특성 즉 연소특성이 양호하지 못하여 베이킹시 잔량이 잔류하거나, 기포가 발생하게 된다. 이와 같은 폴리스티렌의 열분해특성을 보완하기 위해 다음 구조식의 폴리 알파-메틸스티렌이 사용되는데, 그 양평균분자량은 10,000 g/mole 이하인 것이 그 열분해특성을 보완하는 데에 효과가 있는 것으로 나타났다.The above-mentioned polystyrene is used as a polymer binder. The polystyrene is superior to polymethyl methacrylate in terms of charging characteristics and uniformity of charging, but the thermal decomposition characteristics, that is, the combustion characteristics are not good, so that the residual amount during baking or bubbles are generated. In order to supplement the thermal decomposition characteristics of the polystyrene, poly alpha-methylstyrene of the following structural formula is used, and the amount average molecular weight of 10,000 g / mole or less was found to be effective in compensating the thermal decomposition characteristics.
고분자 바인더를 용해시키는 용매로는 벤젠 또는 벤젠 유도체 및 그 혼합물이 사용되는데, 그 벤젠유도체로서는 톨루엔, 에틸벤젠, 크실렌, 스티렌등이 바람직하다.As the solvent for dissolving the polymer binder, benzene or a benzene derivative and a mixture thereof are used, and as the benzene derivative, toluene, ethylbenzene, xylene, styrene and the like are preferable.
상술한 메틸 페닐 트리페닐 부타트리엔은, 종래의 비스디메틸 페닐 디페닐 부타트리엔에 비하여 동일한 조건하에서 광전도도는 동일하나, 그 벤젠유도체에 대한 용해도면에서는 월등하게 양호하다.The above-described methyl phenyl triphenyl butatriene has the same photoconductivity under the same conditions as conventional bisdimethyl phenyl diphenyl butytriene, but is superior in terms of solubility in the benzene derivative.
또한, 상기 트리니트로플루오리논(TNF)은 발암성 물질로 알려져 있기 때문에 안전성문제가 대두되기 때문에 그 대신에 2,5-비스(4-디에틸아미노페닐)-1,3,4-옥사디아졸[2,5-bis(4-diethylaminophenyl)-1,3,4-oxadiazole]을 사용하는 것이 바람직하다.In addition, since trinitrofluorinone (TNF) is known as a carcinogenic substance, safety problems arise, and instead, 2,5-bis (4-diethylaminophenyl) -1,3,4-oxadiazole Preference is given to using [2,5-bis (4-diethylaminophenyl) -1,3,4-oxadiazole].
상기와 같이 구성된 본 발명의 광전도막 도포용액을 이용한 음극선관의 건식 전자사진식 스크린 제조방법은 상술한 종래의 기술과 관련하여 설명한 바와 같으며, 다음과 같은 스크린 제조공정에 사용된다.The dry electrophotographic screen manufacturing method of the cathode ray tube using the photoconductive film coating solution of the present invention configured as described above is as described in connection with the above-described conventional technique, and is used in the following screen manufacturing process.
즉, (1) 판넬의 내면에 종래와 같은 유기전도막 수용액으로 휘발성 전도막을 형성시킨 후: (2) 그 전도막 위에 본 발명에 의한 광전도막 용액으로 휘발성 광전도막을 형성시키고: (3) 그 광전도막 위에 균일한 정전하를 대전시키며: (4) 그 대전된 광전도막의 정전하를 선택적으로 방출시키도록 새도우마스크를 통과시켜 노광시키며: (5) 그 후 소정의 미세분말을 대전시켜 상기 노광단계에서 정전하가 선택적으로 노광부분과 비노광부분 중 어느 하나의 영역에 대전된 미세분말을 부착시키는 현상단계를 거치게 된다.That is, (1) after the volatile conductive film is formed on the inner surface of the panel with a conventional aqueous organic conductive film solution: (2) a volatile photoconductive film is formed on the conductive film with the photoconductive film solution according to the present invention: (3) the Charging a uniform electrostatic charge on the photoconductive film: (4) exposing through a shadow mask to selectively release the electrostatic charge of the charged photoconductive film: (5) then charging the desired fine powder to expose the exposure In the step, the electrostatic charge is selectively subjected to the developing step of attaching the charged fine powder to one of the exposed portion and the non-exposed portion.
본 발명에 의한 광전도막 용액을 사용할 경우, 음극선관 스크린의 제조공정에서 광전도막의 메틸 페닐 트리페닐 부타트리엔성분이 종래의 비스디메틸 페닐 디페닐 부타트리엔과 동일하게 자외선에 감응하고 가시광선에 대해서는 감응하지 아니하므로 종래와 같이 암실에서 작업할 필요가 없어 작업 환경이 개선되면서도, 대전특성과 대전의 균일성이 향상되면서 열분해(연소)특성이 보완되어 균일한 대전에 따른 균일한 형광체막을 얻을 수 있고 또한, 가소제를 포함하고 있어 광전도막의 강도가 향상되므로 광전도막의 손상의 염려도 없으며, 베이킹 공정에서도 완전히 제거되는 등의 효과가 있다.In the case of using the photoconductive film solution according to the present invention, the methyl phenyl triphenyl butytriene component of the photoconductive film in the manufacturing process of the cathode ray tube screen is sensitive to ultraviolet rays and visible light in the same manner as the conventional bisdimethyl phenyl diphenyl butadiene. As it is not sensitive, it is not necessary to work in the dark room as in the prior art, while the working environment is improved, the charging characteristics and the uniformity of the charging are improved, and the pyrolysis (combustion) characteristics are compensated for to obtain a uniform phosphor film according to the uniform charging. In addition, since the plasticizer is contained and the strength of the photoconductor film is improved, there is no fear of damage to the photoconductor film, and there is an effect that it is completely removed even in the baking step.
이상에서 본 발명의 일예를 설명하였으나, 본 발명은 이에 한정되지 아니하고, 청구범위 기재사항으로부터 당업자라면 용이하게 여러 가지 응용과 변형이 가능할 것이다.Although one example of the present invention has been described above, the present invention is not limited thereto, and those skilled in the art will be readily able to various applications and modifications from the claims.
Claims (7)
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| KR1019960060211A KR100267176B1 (en) | 1996-11-30 | 1996-11-30 | A manufacturing method of a dry-type electrophotographical screen of crt, and a photo-conductive spreading solution used therefor |
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