KR101130555B1 - Fabrication of Pb-free white dielectric layer adding mixing filler for soda-lime silecate glasses - Google Patents
Fabrication of Pb-free white dielectric layer adding mixing filler for soda-lime silecate glasses Download PDFInfo
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
- H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
- H01B3/02—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances
- H01B3/08—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances quartz; glass; glass wool; slag wool; vitreous enamels
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
- C03C3/00—Glass compositions
- C03C3/12—Silica-free oxide glass compositions
- C03C3/14—Silica-free oxide glass compositions containing boron
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J2211/00—Plasma display panels with alternate current induction of the discharge, e.g. AC-PDPs
- H01J2211/20—Constructional details
- H01J2211/34—Vessels, containers or parts thereof, e.g. substrates
- H01J2211/38—Dielectric or insulating layers
Abstract
본 발명은 플라즈마 디스플레이 패널(PDP)용 백색유전체 프리트 조성에 관한 것으로서 산화비스무스(Bi2O3) 25-50중량퍼센트, 산화아연(ZnO) 10-20중량퍼센트, 산화바륨(BaO) 10-20중량퍼센트, 산화붕소(B2O3) 10-20중량퍼센트 조성을 갖는 유리프리트에 굴절율이 높은 결정질필러로 아나타제(Anatase)형과 루타일(Rutile)형의 산화티타늄(TiO2), 산화바륨(BaO), 산화바륨+산화티타늄(BaO+TiO2(anatase)), 산화바륨+산화티타늄(BaO+TiO2(rutile))을 혼합하여 첨가한 백색유전체로서, 이 백색유전체를 소다라임기판유리(soda-lime silicate substrate glass)위에 도포한 후 480-540℃에서 소성 했을 때, 고반사율을 갖으며 환경오염문제가 없는 무연 백색 유전체로 제조되는 것을 목적으로 하고 있다. The present invention relates to a white dielectric frit composition for a plasma display panel (PDP) of bismuth oxide (Bi 2 O 3) High refractive index crystalline glass glasses with 25-50 weight percent, 10-20 weight percent zinc oxide (ZnO), 10-20 weight percent barium oxide (BaO), and 10-20 weight percent boron oxide (B 2 O 3 ) Anatase and rutile type titanium oxides (TiO 2 ), barium oxide (BaO), barium oxide + titanium oxide (BaO + TiO 2 (anatase)), barium oxide + titanium oxide (BaO) + TiO 2 (rutile)) is a white dielectric added by mixing on white soda-lime silicate substrate glass (soda-lime silicate substrate glass) when it is baked at 480-540 ℃ has a high reflectance It aims to be made of lead-free white dielectric without environmental pollution.
백색유전체, 소다라임 기판유리, 결정질필러White dielectric, Soda-lime substrate glass, Crystalline filler
Description
본 발명은 플라즈마디스플레이패널(PDP)용 백색유전체 프리트 조성에 관한 것으로서 25-50중량퍼센트의 산화비스무스(Bi2O3), 10-20중량퍼센트의 산화바륨(BaO), 10-20중량퍼센트의 산화아연(ZnO), 10-20중량퍼센트의 산화붕소(B2O3)의 조성을 갖는 유리프리트에 고 굴절율을 갖는 결정질필러로 아나타제(Anatase)형과 루타일(Rutile)형의 산화티타튬(TiO2), 산화바륨(BaO), 산화바륨(BaO)+산화티타늄(TiO2(anatase)), 산화바륨(BaO)+산화티타늄(TiO2(rutile))을 일정비율로 첨가 혼합하여 소다라임기판유리(soda-lime silicate substrate glass)위에 도포한 후 480-540℃에서 소성 했을 때, 백색유전체로 제조되는 것으로, 종래의 백색유전체가 갖는 특성을 유지 또는 증가시키고 친환경적인 저온 소성 가능한 무연의 백색 유전체를 제조하는 것에 관한 것이다. The present invention relates to a white dielectric frit composition for plasma display panel (PDP), 25-50% by weight of bismuth oxide (Bi 2 O 3 ), 10-20% by weight of barium oxide (BaO), 10-20% by weight of It is a crystalline filler having a high refractive index in a glass frit having a composition of zinc oxide (ZnO) and 10-20% by weight of boron oxide (B 2 O 3 ) and anatase type and rutile type titanium oxide ( TiO 2 ), Barium Oxide (BaO), Barium Oxide (BaO) + Titanium Oxide (TiO 2 (anatase)), Barium Oxide (BaO) + Titanium Oxide (TiO 2 (rutile)) by adding and mixing in a certain ratio When coated on a soda-lime silicate substrate glass and calcined at 480-540 ° C, it is made of white dielectric, and maintains or increases the characteristics of conventional white dielectrics and is environmentally friendly at low temperature. Relates to manufacturing a dielectric.
기존의 백색 유전체의 프리트 조성으로는 중량으로 24.6중량퍼센트 산화실리 카(SiO2), 65.3중량퍼센트 산화납(PbO), 5.8중량퍼센트 산화붕소(B2O3), 4.3중량퍼센트 산화알루미늄(Al2O3)를 갖는다. 이 프리트 조성물에 고 굴절율을 갖는 TiO2결정질 필러를 15중량% 첨가 혼합하여 백색유전체를 제조하였다. The frit compositions of conventional white dielectrics are 24.6 weight percent silicon oxide (SiO 2 ), 65.3 weight percent lead oxide (PbO), 5.8 weight percent boron oxide (B 2 O 3 ), and 4.3 weight percent aluminum oxide (Al). 2 O 3 ). A white dielectric material was prepared by adding 15 wt% of TiO 2 crystalline filler having a high refractive index to the frit composition.
이 백색유전체는 어드레스(Address)전극이 형성된 소다라임규산(Soda-lime silicate)유리기판 위에 스크린 프린팅법으로 형성된다. 이때, 백색유전체는 가시광 반사에 의한 발광효율 향상, 확산 방지등의 역할을 하게 되는 것이다. 따라서, 백색유전체가 갖춰야 할 특성으로는 높은 가시광선 반사율, 기판유리와 유사한 열팽창계수, 낮은 소성온도, 낮은 유전상수를 가져야 한다.The white dielectric is formed by screen printing on a soda-lime silicate glass substrate having an address electrode formed thereon. At this time, the white dielectric is to play a role of improving the luminous efficiency, preventing diffusion by visible light reflection. Therefore, the white dielectric should have high visible light reflectance, thermal expansion coefficient similar to that of substrate glass, low firing temperature, and low dielectric constant.
현재 위 특성을 만족시키며 사용되는 기존의 백색유전체는 인체에 해로운 산화납(PbO)성분이 최소 60중량%이상 다량 함유되어 있기 때문에 플라즈마 디스플레이 패널(PDP) 폐기 시 폐수 중의 산 또는 알칼리 용액과 화학반응을 일으키게 되면 토양 및 수질오염을 비롯한 환경공해를 유발시키고 인체에도 유해한 영향을 주는 문제점이 있다. The existing white dielectric used to satisfy the above characteristics currently contains a large amount of lead oxide (PbO) that is harmful to the human body at least 60% by weight, so when the plasma display panel (PDP) disposal, chemical reaction with acid or alkaline solution in the wastewater If it causes a problem that causes environmental pollution, including soil and water pollution and harmful effects on the human body.
본 발명은 상기와 같은 문제점을 해소하기 위해 납성분을 함유하지 않는 산화비스무스-산화아연-산화바륨-산화붕소계 프리트 조성에 고 굴절율을 갖는 결정질 필러를 첨가하여 높은 가시광 반사에 의한 반사율 향상과 유리기판과의 열팽창계수 를 정합시켜 유리기판과의 사이에서 견고한 밀착성을 갖는 후막을 제조하는데 있다.In order to solve the above problems, the present invention adds a crystalline filler having a high refractive index to a bismuth oxide-zinc oxide-barium oxide-boron oxide-based frit-free composition, which does not contain lead, thereby improving the reflectance and glass by high visible light reflection. By matching the coefficient of thermal expansion with the substrate to produce a thick film having a strong adhesion between the glass substrate.
상기와 같은 유리기판과의 사이에 견고한 밀착성을 갖는 후막을 제조하는 기술수단으로는As a technical means for producing a thick film having a strong adhesion between the glass substrate as described above
산화비스무스(Bi2O3), 산화바륨(BaO), 산화아연(ZnO), 산화붕소(B2O3)의 조성을 갖는 유리프리트에 고굴절율을 갖는 결정 필러를 혼합하여 소다라임 기판유리 위에 도포한 후 480-540℃에서 소성하는 것을 과제해결 수단으로 한다.A glass frit having a composition of bismuth oxide (Bi 2 O 3 ), barium oxide (BaO), zinc oxide (ZnO), and boron oxide (B 2 O 3 ) is mixed with a crystal filler having a high refractive index and coated on a soda-lime substrate glass. After that, firing at 480-540 ° C is a problem solving means.
이상에서 설명드린 바와 같이 본 발명은,As described above, the present invention,
기존의 백색유전체의 특성을 유지 혹은 배가 시키면서 산화납(Pbo)이 포함되지 않아 제품의 폐기시 환경오염 및 상태계 파괴의 문제점을 해결하였으며 저온에서 소성하는 효과도 있다.While maintaining or doubling the characteristics of the existing white dielectric material, Pb is not included, which solves the problems of environmental pollution and state destruction when disposing of the product, and also fires at low temperatures.
본 발명에서는 플라즈마 디스플레이용 무연 산화비스무스(Bi2O3) 25-50wt.%, 산화아연(ZnO) 10-20wt.%, 산화바륨(BaO) 10-20wt.%, 산화붕사(B2O3) 10-20wt.%를 주성분으로 하는 프리트 조성계에 고 굴절율을 갖는 결정질 필러로 아나타제(Anatase)형과 루타일(Rutile)형의 산화티타늄(TiO2)을 100:0, 75:25, 50:50, 25:75, 0:100의 비율로 혼합하여 첨가한 경우와 산화바륨(BaO)을 단독으로 산화바륨(BaO)+산화티타늄(TiO2(anatase)), 산화바륨(BaO)+산화티나늄(TiO2(rutile))을 첨가하여 열처리 한 후 나타나는 물성을 확인하였다.Lead-free bismuth oxide (Bi 2 O 3 ) for plasma display 25-50wt.%, Zinc oxide (ZnO) 10-20wt.%, Barium oxide (BaO) 10-20wt.%, Borax oxide (B 2 O 3 ) A crystalline filler having a high refractive index in a frit composition system containing 10-20 wt.% As a main component. Anatase and rutile titanium oxides (TiO 2 ) are 100: 0, 75:25, and 50:50. Barium oxide (BaO) + Barium oxide (BaO) + Titanium oxide (TiO 2 (anatase)), Barium oxide (BaO) + Titanium oxide (TiO 2 (rutile)) was added to confirm the physical properties after heat treatment.
이하 본 발명의 바람직한 실시예를 중심으로 상세히 설명한다.Hereinafter will be described in detail centering on a preferred embodiment of the present invention.
(실시 예 1)(Example 1)
산화비스무스, 산화아연, 산화바륨, 산화붕사(Bi2O3-ZnO-BaO-B2O3)로 제조 된 프리트와 아나타제(Anatase)형과 루타일(Rutile)형의 산화티타늄(TiO2)을 100:0, 75:25, 50:50, 25:75, 0:100의 비율로 혼합한 고 굴절율을 갖는 결정질필러를 5, 10, 15, 20, 25, 30, 35, 40% 첨가하여 480~540℃에서 열처리 하였다. 열처리 한 후 제조된 무연(Pb-free) 백색유전체의 결정질필러 혼합량 및 첨가량에 따른 변화율을 그림 1에 나타내었다.Frith and anatase and rutile titanium oxide (TiO 2 ) made of bismuth oxide, zinc oxide, barium oxide, and borax oxide (Bi 2 O 3 -ZnO-BaO-B 2 O 3 ) 5, 10, 15, 20, 25, 30, 35, 40% of the crystalline filler having a high refractive index mixed in the ratio of 100: 0, 75:25, 50:50, 25:75, and 0: 100 Heat treatment at 480 ~ 540 ℃. Figure 1 shows the change rate according to the mixing amount and the amount of crystalline filler of Pb-free white dielectric prepared after heat treatment.
그림1)Figure 1
(실시 예 2)(Example 2)
실시 예 2에서는 실시 예 1에서 가장 높은 반사율을 나타낸 아나타제(Anatase)형 산화티타늄(TiO2) 25.wt.%와 루타일(Rutile)형의 산화티타늄 (TiO2) 75wt.%를 혼합한 결정질필러의 첨가량에 따른 물성의 변화를 표 1에 나타내었다.Example 2 In Example 1, the anatase (Anatase) titanium oxide showing a high reflectance in the (TiO 2) 25.wt.% and rutile (Rutile) type of titanium oxide (TiO 2) 75wt.% A mixture of crystalline Table 1 shows changes in physical properties depending on the amount of filler added.
표1)Table 1
(실시 예 3)(Example 3)
실시 예 3에서는 산화비스무스, 산화아연, 산화바륨, 산화붕사(Bi2O3-ZnO-BaO-B2O3)로 제조 된 프리트와 산화바륨(BaO)을 혼합하여 결정질 필러로 첨가하였다. 그 결과를 그림 2에 나타내었다.In Example 3, frit and barium oxide (BaO) made of bismuth oxide, zinc oxide, barium oxide, and borax (Bi 2 O 3 -ZnO-BaO-B 2 O 3 ) were mixed and added as a crystalline filler. The results are shown in Figure 2.
(실시 예 4)(Example 4)
실시 예 4에서는 산화비스무스, 산화아연, 산화바륨, 산화붕사(Bi2O3-ZnO-BaO-B2O3)로 제조 된 프리트와 산화바륨(BaO)와 산화티타늄(TiO2(anatase))형을 혼합하여 결정질 필러로 첨가하였다. 그 결과를 그림 2에 나타내었다.In Example 4, frit, barium oxide (BaO) and titanium oxide (TiO 2 (anatase)) prepared from bismuth oxide, zinc oxide, barium oxide, and boron oxide (Bi 2 O 3 -ZnO-BaO-B 2 O 3 ) The molds were mixed and added to the crystalline filler. The results are shown in Figure 2.
(실시 예 5)(Example 5)
실시 예 4에서는 산화비스무스, 산화아연, 산화바륨, 산화붕사(Bi2O3-ZnO-BaO-B2O3)로 제조 된 프리트와 산화바륨(BaO)와 산화티나튬(TiO2(Rutile))형을 혼합하여 결정질 필러로 첨가하였다. 그 결과를 그림 2에 나타내었다. In Example 4, frit, barium oxide (BaO) and titanium oxide (TiO 2 (Rutile) prepared from bismuth oxide, zinc oxide, barium oxide, and boron oxide (Bi 2 O 3 -ZnO-BaO-B 2 O 3 ) ) Forms were mixed and added as crystalline filler. The results are shown in Figure 2.
그림2)Figure 2)
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JP2000044277A (en) | 1998-07-24 | 2000-02-15 | Central Glass Co Ltd | Forming material of insulation coating film of display device and display device |
KR100565194B1 (en) * | 2003-08-04 | 2006-03-30 | 엘지전자 주식회사 | Glass compositions for plasma display panel and preparing method therefor |
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JP2000044277A (en) | 1998-07-24 | 2000-02-15 | Central Glass Co Ltd | Forming material of insulation coating film of display device and display device |
KR100565194B1 (en) * | 2003-08-04 | 2006-03-30 | 엘지전자 주식회사 | Glass compositions for plasma display panel and preparing method therefor |
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