KR101205207B1 - Pb-free glass-frit for sealant that sealing is possible at low temperature below 420°Cand synthesize of filler that is suitable to glass-frit - Google Patents

Pb-free glass-frit for sealant that sealing is possible at low temperature below 420°Cand synthesize of filler that is suitable to glass-frit Download PDF

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KR101205207B1
KR101205207B1 KR1020090104812A KR20090104812A KR101205207B1 KR 101205207 B1 KR101205207 B1 KR 101205207B1 KR 1020090104812 A KR1020090104812 A KR 1020090104812A KR 20090104812 A KR20090104812 A KR 20090104812A KR 101205207 B1 KR101205207 B1 KR 101205207B1
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glass frit
filler
sealing
weight
oxide
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KR20110048130A (en
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최병현
지미정
고영수
안용태
이준호
배현
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신세라믹 주식회사
한국세라믹기술원
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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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • 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
    • C03C3/122—Silica-free oxide glass compositions containing oxides of As, Sb, Bi, Mo, W, V, Te as glass formers
    • 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
    • C03C3/125—Silica-free oxide glass compositions containing aluminium as glass former
    • 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
    • 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
    • C03C3/23—Silica-free oxide glass compositions containing halogen and at least one oxide, e.g. oxide of boron
    • 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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/04—Frit compositions, i.e. in a powdered or comminuted form containing zinc
    • 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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/02—Frit compositions, i.e. in a powdered or comminuted form
    • C03C8/08—Frit compositions, i.e. in a powdered or comminuted form containing phosphorus
    • 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
    • C03C8/00—Enamels; Glazes; Fusion seal compositions being frit compositions having non-frit additions
    • C03C8/24—Fusion seal compositions being frit compositions having non-frit additions, i.e. for use as seals between dissimilar materials, e.g. glass and metal; Glass solders
    • 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
    • H01B3/10—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances metallic oxides
    • 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
    • H01B3/12—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of inorganic substances ceramics

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Abstract

본 발명은 봉착(sealing)온도 420℃이하에서 적용 가능한 밀봉재용 Pb-free 유리프리트를 제조하는 것과 이 유리프리트에 적합한 필러(filler)를 합성하는 것을 기술요지로 하고 있다. 현재 PDP에서 사용하고 있는 고왜점유리(PD-200)를 기판으로 사용하지 않고, 소다라임(soda-lime) 유리를 기판으로 사용할 경우와 액정디스플레이, OLED, 태양전지의 밀봉은 420℃이하 저온에서의 봉착이 필요하다.   SUMMARY OF THE INVENTION The present invention aims to produce a Pb-free glass frit for sealing materials that can be applied at sealing temperatures of 420 ° C. or less and to synthesize a filler suitable for the glass frit. When using high-distortion glass (PD-200), which is currently used in PDP, as a substrate, and soda-lime glass as a substrate, the liquid crystal display, OLED, and solar cell are sealed at a low temperature below 420 ℃. Sealing is required.

따라서 저온에서 봉착이 가능한 산화주석-오산화인 (SnO-P2O5)을 주 조성으로 한 후, 망목산화물, 수식산화물, 중간산화물을 첨가시켜서 250℃에서 350℃ 사이의 낮은 전이온도를 갖는 조성을 설계했으며, 설계한 조성에 적합한 필러를 합성한 것이다. 그래서 유리프리트와 필러를 혼합한 밀봉재가 420℃이하에서 봉착이 가능하게 하였다. Therefore, the tin oxide-phosphorus pentoxide (SnO-P 2 O 5 ), which can be sealed at low temperature, is used as a main composition, and then a network having a low transition temperature between 250 ° C and 350 ° C is added by adding mesh oxide, modified oxide, and intermediate oxide. It is designed and synthesized filler suitable for the designed composition. Therefore, the sealing material which mixed the glass frit and the filler made sealing possible below 420 degreeC.

그 결과, 산화주석-오산화인(SnO-P2O5)을 주성분으로 하여 필러첨가 전 350℃이하(전이점290℃이하)에서 봉착이 가능한 밀봉재용 무연 유리프리트와 필러를 첨가 후 420℃에서 봉착이 가능한 밀봉재용 유리프리트를 제조하는 것이다. As a result, tin-free phosphorus pentoxide (SnO-P 2 O 5 ) was added as a main component and the lead-free glass frit and filler for the sealing material which can be sealed at 350 ° C or lower (transition point 290 ° C or lower) before filler addition were added at 420 ° C. It is to manufacture the glass frit for the sealing material which can be sealed.

유리프리트, 봉착재, 필러, 밀봉재용 유리프리트 Glass frit, sealing material, filler, glass frit for sealing material

Description

420℃이하의 저온에서 봉착이 가능한 밀봉재용 무연 유리프리트 및 이 유리프리트에 적합한 필러 합성 방법. {Pb-free glass-frit for sealant that sealing is possible at low temperature below 420℃ and synthesize of filler that is suitable to glass-frit}    Lead-free glass frit for sealing materials capable of sealing at low temperatures below 420 ° C. and filler synthesis methods suitable for the glass frit. {Pb-free glass-frit for sealant that sealing is possible at low temperature below 420 ° C and synthesize of filler that is suitable to glass-frit}

본 발명은 저온(420℃ 이하)에서 PDP, LCD, OLED, 유기EL, VFD의 밀봉재(sealant)로 사용 가능한 저온 유리프리트 조성 및 저온용 유리프리트에 적합한 필러의 합성 방법에 관한 기술분야이다.The present invention relates to a low temperature glass frit composition which can be used as a sealant of PDP, LCD, OLED, organic EL, and VFD at low temperature (below 420 ° C.) and a method for synthesizing a filler suitable for low temperature glass frit.

유리 프리트(glass frit)는 PDP(Plasma Display Panel)의 격벽재, 밀봉재, 유전체 등의 구성소재, CRT, LCD, OLED, 유기EL 및 염료감응형 태양전지 등의 밀봉재, 금속-금속, 금속-세라믹-유리 간의 접합, 전기전자 부품용 회로전극 등에 널리 이용되고 있다. Glass frit is a component of PDP (Plasma Display Panel), sealing materials, dielectric materials, sealing materials such as CRT, LCD, OLED, organic EL and dye-sensitized solar cells, metal-metal, metal-ceramic It is widely used for bonding between glass and circuit electrodes for electric and electronic parts.

그 중에서도 PDP, LCD, OLED, 유기EL 및 염료감응형 태양전지 등에 사용하고 있는 봉착용 유리프리트는 480℃이하 저온에서 소성 처리된다. Among them, the sealing glass frit used in PDP, LCD, OLED, organic EL and dye-sensitized solar cells is calcined at low temperature below 480 ° C.

저온에서 소성이 가능한 유리프리트 조성은 PbO-B2O3, PbO-ZnO-B2O3, PbO- B2O3-SiO2, PbO-B2O3-SiO2-Al2O3, Bi2O3-BaO-ZnO-SiO2계 유리 등이 사용되어 왔다.Glass frit compositions that can be fired at low temperatures include PbO-B 2 O 3 , PbO-ZnO-B 2 O 3 , PbO-B 2 O 3 -SiO 2 , PbO-B 2 O 3 -SiO 2 -Al 2 O 3 , Bi 2 O 3 -BaO-ZnO-SiO 2 glass and the like have been used.

이러한 유리 조성들 중 PbO 성분을 함유한 것은 타 유리와 비교하여 낮은 융점을 갖으면서도 소성 전후에 물리, 화학적으로 매우 안정하여 현재 사용되고 있는 대부분의 저융점 유리프리트는 PbO 성분을 50 - 85 % 이상 함유하고 있는 실정이다.Among these glass compositions, the PbO component contains a lower melting point than other glass, and is very stable physically and chemically before and after firing. Most of the low melting glass frits currently used contain more than 50-85% of the PbO component. I'm doing it.

그러나 PbO성분은 그 자체나 유리 내에서는 안정한 상태로 존재하지만, 폐기 시 산, 알칼리와 반응하여 Pb이온이 용출되어 환경오염의 원인이 되기 때문에 현재 유해성분으로 규정되어 있고, 최근 유해물질의 규제가 강화됨에 따라 Pb-free 유리프리트의 사용이 불가피하게 되어, 이에 대한 개발이 활발히 이루어지고 있다. However, PbO is present in a stable state in itself or in glass, but it is currently regulated as a harmful component because Pb ions are eluted when reacted with acids and alkalis when disposed of, causing environmental pollution. As it is strengthened, the use of Pb-free glass frit is inevitable, and development of this is being actively performed.

PbO 성분을 대체하기 위한 소재로는 Bi2O3 계, BaO-ZnO-SiO2 계, P2O5 계, P2O5-SnO2 계 유리프리트에 대한 개발이 대부분이고 일부 상용화 하여 판매되고 있는데, 그 중 Bi2O3나 BaO계는 중금속에 해당되므로 이의 상용화도 고려되어야 한다.As a material for replacing PbO components, most of the development of glass frit, Bi 2 O 3 series, BaO-ZnO-SiO 2 series, P 2 O 5 series, P 2 O 5 -SnO 2 series, and commercialized Among them, Bi 2 O 3 or BaO-based heavy metals should be considered for commercialization.

그 중에서 Bi2O3 계는 주로 Bi2O3-SiO2-B2O3 계가 일반적으로 사용되는데, Bi2O3의 강한 환원성 때문에 제조시 도가니(백금, 알루미나, 지르코니아 등) 또는 내화물을 심하게 부식시키는 제조 공정상의 문제점과 PbO와 비교하여 10 배 이상 고가의 산화물이며 조성간의 문제로 500℃이하의 저온에서 사용하기가 어렵다. BaO-ZnO-SiO2계는 BaO를 5-20%, ZnO를 10-20% 함유하기 때문에 식각이 양호하고 전극, 금속-금속, 금속-세라믹의 봉착으로 고온에서 사용은 가능하나, PDP, LCD 및 OLED 와 같은 디스플레이의 격벽재, 유전체, 봉착재 등 저온소성용으로는 사용하기가 어렵다. P2O5계와 P2O5-SnO2 계는 PbO 계와 유사한 거동을 하고 저온에서 사용가능하며 에칭성도 양호하나, 내수성이 약하며 원료 배합시 수분과 급격하게 반응하는 문제점이 있다. 또한, 유리프리트 자체만으로는 soda-lime silicate기판의 열팽창계수인 85×10-7/℃를 맞추기 어렵고 상판과 하판 사이의 간격(gap)을 유지할 수 없기 때문에 열팽창계수를 조절하고 간격(gap)을 유지하기가 어려운 단점이 있다. 최근 Kikutani, Takemi 등은 P2O5 계의 내수성(흡습성)을 개선할 목적으로 국내 특허공개공보 2003-57344호에서는 인듐(In2O3)을 첨가하거나, 란타노이드 산화물의 도입에 의한 개선방법을 제시하고 있다.Among them, Bi 2 O 3 In general, Bi 2 O 3 -SiO 2 -B 2 O 3 system is generally used.Because of the strong reducibility of Bi 2 O 3 , there are problems in manufacturing process that severely corrode crucibles (platinum, alumina, zirconia, etc.) or refractory materials during manufacturing. It is 10 times more expensive oxide than PbO and PbO, and it is difficult to use at low temperature below 500 ℃ due to the problem of composition. BaO-ZnO-SiO 2 system contains 5-20% BaO and 10-20% ZnO, so it has good etching and can be used at high temperature due to sealing of electrode, metal-metal and metal-ceramic. And it is difficult to use for low temperature firing, such as partition material, dielectric, sealing material of the display such as OLED. P 2 O 5 system and P 2 O 5 -SnO 2 system has similar behavior to PbO system, can be used at low temperature, and has good etching resistance, but has poor water resistance and reacts rapidly with moisture when mixing raw materials. In addition, the glass frit alone is difficult to match the thermal expansion coefficient of 85 × 10 -7 / ℃ of the soda-lime silicate substrate and cannot maintain the gap between the upper plate and the lower plate, thereby controlling the coefficient of thermal expansion and maintaining the gap. There are disadvantages that are difficult to do. Recently, Kikutani, Takemi et al., In order to improve the water resistance (hygroscopicity) of P 2 O 5 system in Korea Patent Publication No. 2003-57344, adding indium (In 2 O 3 ) or by introducing a lanthanoid oxide Presenting.

본 발명은 상기와 같은 문제점을 해소하기 위해 금속산화물을 함유한 PDP용, LCD용, OLED용, 유기EL용, 염료감응형 태양전지용 밀봉재로 유리프리트를 사용할 때, 480℃이하의 온도에서 봉착을 해야지만 고왜점유리를 기판으로 사용하지 않고 소다라임유리를 기판으로 사용할 경우에는 420℃이하의 저온에서의 봉착이 필요하므로 전이점이 290℃이하인 유리프리트로 350℃이하의 저온에서 소성이 가능한 유리프리트에 필러를 첨가하여 420℃이하에서 소성가능한 밀봉재를 제조하는 것을 과제해결 수단으로 한다.The present invention is to solve the above problems when the glass frit is used as a sealing material for PDP, LCD, OLED, organic EL, dye-sensitized solar cell containing a metal oxide, the sealing at a temperature of 480 ℃ or less If soda-lime glass is used as a substrate without using high-distortion glass as a substrate, sealing is required at a low temperature of 420 ° C or lower. It is a problem solving means to manufacture a sealing material which can be baked at 420 degreeC or less by adding a filler to it.

상기와 같은 목적을 달성하기 위한 본 발명은 저온에서 봉착이 가능한 밀봉재 무연(Pb-free)유리프리트계로 망목형성제로 오산화인(P2O5), 산화붕소(B2O3), 산화주석(SnO)을 수식 및 중간산화물로 MXOY[M=Al, B, Ca, Zn, Mg, Li, Bi, V]를 이용하여 1100℃ 온도에서 용융하였다.The present invention for achieving the above object is a lead-free (Pb-free) glass frit-based sealing material that can be sealed at low temperature as phosphorus pentoxide (P 2 O 5 ), boron oxide (B 2 O 3 ), tin oxide ( SnO) was melted at 1100 ° C. using M X O Y [M = Al, B, Ca, Zn, Mg, Li, Bi, V] as the formula and intermediate oxide.

그 결과, 산화주석-오산화인(SnO-P2O5)계를 주성분으로 하여 필러를 첨가 하기전 350℃이하(전이점 290℃이하)에서 봉착이 가능한 유리프리트와 필러를 첨가 후 420℃이하에서 봉착이 가능한 밀봉재용 무연 유리프리트를 제조하였다.As a result, the tin oxide-phosphorus pentoxide (SnO-P 2 O 5 ) -based component as a main component of the glass frit and the filler that can be sealed at 350 ° C or less (transition point 290 ° C or less) before adding the filler and after 420 ° C or less A lead-free glass frit for a sealant capable of sealing was prepared.

이때, 산화주석-오산화인(SnO-P2O5)계는 합성물로 Sn2P2O7을 사용하여 수분과 반응하기 쉬운 오산화인(P2O5)의 안정성을 높여 조성 혼합 간에 신뢰성을 높이는 제조 방법을 개발하였다. 또한, 저온에서 사용하기 위한 기판으로 소다라임유리 기판을 사용할 경우 유리프리트 자체만으로는 소다라임유리 기판의 열팽창계수인 85×10-7/℃를 맞추기 어렵고 상판과 하판 사이의 간격(gap)을 유지할 수 없기 때문에 열팽창계수를 조절하고 간격을 유지하기 위해 기존에 디스플레이용 유리프리트에서 사용하는 산화마그네슘-산화알루미늄-산화실리콘(MgO-Al2O3-SiO2)계 세라믹스 코디어라이트필러(cordierite filler)와 함께 산화리튬-산화알루미늄-산화실리콘(Li2O-Al2O3-SiO2)계 세라믹스 유크립타이트(Eucryptite), 스포듀민( Spodumene)을 합성하여 밀봉재의 열팽창계수를 소다라임유리 기판의 열팽창계수인 85×10-7/℃와 유사한 값을 갖도록 조절하는 방법을 개발하였다.At this time, the tin oxide-phosphorus pentoxide (SnO-P 2 O 5 ) -based compound using Sn 2 P 2 O 7 as a composite to increase the stability of the phosphorus pentoxide (P 2 O 5 ) that is easily reacted with water to improve the reliability between the composition mixture Height developed manufacturing method. In addition, when using a soda-lime glass substrate as a substrate for use at low temperatures, the glass frit alone is difficult to match the thermal expansion coefficient of 85 × 10 -7 / ° C. of the soda-lime glass substrate, and maintains a gap between the top plate and the bottom plate. MgO-Al 2 O 3 -SiO 2 -based ceramics cordierite filler used in glass frits for displays to control the thermal expansion coefficient and maintain the spacing Lithium oxide-aluminum oxide-silicon oxide (Li 2 O-Al 2 O 3 -SiO 2 ) -based ceramics Eucryptite and Spodumene were synthesized to synthesize the thermal expansion coefficient of the soda-lime glass substrate. A method was developed to have a value similar to the thermal expansion coefficient of 85 × 10 −7 / ° C.

이상에서 상술한 바와 같이 본 발명은, 산화주석-오산화인(SnO-P2O5) 유리프리트 원료를 혼합할 때 Sn2P2O7을 사용하여 내수성에 취약한 오산화인(P2O5)의 내습성을 제어하여 원료 혼합 간의 신뢰성을 높였다. 또한 산화비스무스(Bi2O3), 산화바나듐(V2O5)의 성분을 통해 약한 접합성을 갖는 인산계 유리프리트의 접합성을 보완하고, MXOY[M=Al, B, Ca, Zn, Mg, Li, K]의 첨가에 의한 유리프리트의 특성 개선을 통해 PDP용, LCD용, OLED용, 유기EL용 및 염료감응형 태양전지용 밀봉재 등에 활용이 가능한 유리프리트를 제조할 수 있다. 이러한 유리 프리트는 240?390℃범위 내의 유리전이점을 갖기 때문에 420℃이하에서 열처리 할 수 있는 PDP용, LCD용, OLED용, 유기EL용 및 염료감응형태양전지용 유리프리트 재료로서 사용할 수 있는 효과가 있다.As described above, in the present invention, when mixing tin oxide-phosphorus pentoxide (SnO-P 2 O 5 ) glass frit raw material, phosphorus pentoxide (P 2 O 5 ) vulnerable to water resistance using Sn 2 P 2 O 7 . Moisture resistance of the material increased the reliability between the raw material mixture. In addition, bismuth oxide (Bi 2 O 3 ), vanadium oxide (V 2 O 5 ) to compensate for the bondability of the phosphate-based glass frit with weak bonding properties, M X O Y [M = Al, B, Ca, Zn Through the improvement of the properties of the glass frit by the addition of, Mg, Li, K] it is possible to manufacture a glass frit that can be utilized in sealing materials for PDP, LCD, OLED, organic EL and dye-sensitized solar cell. Since these glass frits have a glass transition point within the range of 240 to 390 ° C., they can be used as glass frit materials for PDP, LCD, OLED, organic EL and dye-sensitized solar cells that can be heat-treated below 420 ° C. There is.

또한, 제조 된 유리프리트를 저가의 소다라임유리 기판에 실링재로 적용했을 때, 저 열팽창성 복합산화물계 세라믹스를 첨가하여 소다라임유리 기판의 열팽창계수인 85×10-7/℃와 유사한 열팽창계수를 갖는 복합 밀봉재를 제조할 수 있는 효과가 있다. 코디어라이트계 세라믹스와 라스계 세라믹스(Eucryptite, Spodumene)를 합성과 분쇄, 재합성을 통해 최적 합성 공정으로 열팽창 개선용 필러를 합성하여 유리프리트에 첨가함으로써 밀봉재로 적용했을 때, 기판과 같은 열팽창계수를 가져 기판과의 열변형 및 뒤틀림을 방지할 수 있고, 상판과 하판사이의 간격을 유지 할 수 있게 하였다.In addition, when the prepared glass frit is applied to a low-cost soda-lime glass substrate as a sealing material, a low thermal expansion composite oxide-based ceramic is added to provide a thermal expansion coefficient similar to that of the soda-lime glass substrate, which is 85 × 10 −7 / ° C. There exists an effect which can manufacture the composite sealing material which has. Coefficient of thermal expansion, such as a substrate, when cordierite-based ceramics and Racrypt-based ceramics (Eucryptite, Spodumene) are synthesized, pulverized, and re-synthesized, and the fillers for improving thermal expansion are added to the glass frit in an optimal synthesis process. It is possible to prevent the thermal deformation and distortion of the substrate and to maintain the gap between the upper plate and the lower plate.

위와 같은 목적을 달성하기 위하여 본 발명에서는 밀봉재용무연(Pb-free) 유리프리트의 조성으로는 망목산화물 Sn2P2O7를 주원료로 하여 유리프리트의 특성 개선을 위한 첨가물로 수식 및 중간산화물로 MXOY[M=Al, B, Ca, Zn, Mg, Li, K, Bi, V]를 첨가 혼합한 후, 혼합된 원료를 대기분위기에서 900 - 1100℃에서 용융하여 유리프리트를 얻는 방법을 사용하였다.In order to achieve the above object, in the present invention, the composition of lead-free glass frit for sealant is made of mesh oxide Sn 2 P 2 O 7 as an additive to improve the properties of the glass frit. M x O Y [M = Al, B, Ca, Zn, Mg, Li, K, Bi, V] After adding and mixing, the mixed raw materials are melted in the air atmosphere at 900-1100 ℃ to obtain a glass frit Was used.

이 때, 사용된 원료의 조성은 중량퍼센트로 35?80퍼센트의 Sn2P2O7, 1 ?10페센트의 R2O (R=Li, K), 1 ?25퍼센트의 R2O3 (R=B, Al, Bi), 1?20퍼센트의 RO(R=Ca, Ba, Mg, Zn), 1 ?5wt.%의 산화바나듐이 사용되었다. 제조 된 유리프리트의 특성을 평가하기위해 전이점, 연화점, 열팽창계수를 측정하였다.At this time, the composition of the raw materials used was 35 to 80 percent by weight Sn 2 P 2 O 7 , 1 to 10 percent R 2 O (R = Li, K), 1 to 25 percent R 2 O 3 (R = B, Al, Bi), 1-20% RO (R = Ca, Ba, Mg, Zn), 1-5 wt.% Vanadium oxide was used. The transition point, softening point, and coefficient of thermal expansion were measured to evaluate the properties of the prepared glass frit.

유리프리트의 열팽창계수 조절용 필러로는 중량퍼센트로 25퍼센트의 탄산마그네슘(MgCO3) 30.3퍼센트의 산화알루미늄(Al2O3), 44.7퍼센트의 산화실리콘(SiO2)을 혼합한 MgCO3-Al2O3-SiO2계 코디어라이트를 1300℃에서 5시간에서 48시간까지 유지하여 합성한 후, 합성물을 분쇄하고서 다시 1300℃에서 5시간에서 48시간 동안 유지 하여 합성하였다. 동일한 방법으로 3차 합성까지 진행한 후, 각각 합성 횟수에 따른 코디어라이트의 결정상을 엑스선회절분석(XRD)을 통해 측정, 비교하였다.As a filler for adjusting the coefficient of thermal expansion of glass frit, MgCO 3 -Al 2 mixed with 25% of magnesium carbonate (MgCO 3 ) 30.3% of aluminum oxide (Al 2 O 3 ) and 44.7% of silicon oxide (SiO 2 ) in weight percent O 3 -SiO 2 -based cordierite was synthesized by maintaining at 1300 ℃ for 5 hours to 48 hours, and then synthesized by pulverizing the mixture and maintained at 1300 ℃ for 5 hours to 48 hours. After proceeding to the third synthesis in the same way, the crystal phase of cordierite according to the number of synthesis was measured and compared by X-ray diffraction analysis (XRD).

원료의 조성으로 중량퍼센트로 25퍼센트의 탄산리튬(Li2CO3 ), 34.5퍼센트의 산화알루미늄(Al2O3), 40.5퍼센트의 산화실리콘(SiO2)을 혼합한 Li2CO3-Al2O3-SiO2계 유크립타이트와 17.8퍼센트의 산화리튬(Li2O3), 24.5퍼센트의 산화알루미늄(Al2O3), 57.7퍼센트의 산화실리콘(SiO2)을 혼합한 Li2O-Al2O3-SiO2계 유크립타이트를 1250℃에서 상기의 라스계(LAS: Li2O-Al2O3-SiO2계의 약자) 유크립타이트와 동일한 합성 공정을 거쳐 각각의 결정상을 엑스선회절분석기(XRD)를 이용해 측정한 후 비교하였다.Li 2 CO 3 -Al 2 with 25 percent lithium carbonate (Li 2 CO 3 ) , 34.5 percent aluminum oxide (Al 2 O 3 ), and 40.5 percent silicon oxide (SiO 2 ) Li 2 O— a mixture of O 3 -SiO 2 eutectic, 17.8 percent lithium oxide (Li 2 O 3 ), 24.5 percent aluminum oxide (Al 2 O 3 ), and 57.7 percent silicon oxide (SiO 2 ) Al 2 O 3 -SiO 2 -based eu krypite at 1250 ℃ through the same synthetic process as the above-described las-based (LAS: Li 2 O-Al 2 O 3 -SiO 2 type ) krypite each crystal phase It was measured using an X-ray diffractometer (XRD) and then compared.

제조 된 유리프리트에 코디어라이트계(cordierite) 세라믹스, 라스계 세라믹스(eucryptite, spodumene)를 필러로 첨가하여 기판과의 열팽창계수차이를 조절하였으며 소성 후 상판과 하판사이의 일정한 간격(gap)을 형성할 수 있었다.Cordierite-based ceramics and eucryptite-spodumene were added to the glass frit as a filler to control the difference in coefficient of thermal expansion between the substrate and to form a gap between the top and bottom plates after firing. Could.

(실시 예1)(Example 1)

본 발명의 제조방법으로 유리프리트 원료를 혼합하여 도가니에 넣고 900 - 1100℃에서 용융하여 유리프리트를 제조하는 방법이다. 위와 같이 망목산화물 Sn2P2O7에 중간 및 수식 산화물로 MXOY[M=Al, B, Ca, Zn, Mg, Li, K, Bi, V]를 첨가하여 제조한 유리프리트의 특성은 (표1)에 나타내었다.In the method of the present invention, a glass frit raw material is mixed, put into a crucible, and melted at 900-1100 ° C. to prepare glass frit. Characteristics of the glass frit prepared by adding M X O Y [M = Al, B, Ca, Zn, Mg, Li, K, Bi, V] as intermediate and modified oxides to the mesh oxide Sn 2 P 2 O 7 as above. Is shown in (Table 1).

Sn2OP2O7을 주원료로 사용함으로써 공정 간에 P2O5와 수분과의 반응을 최소화하여 조성 간의 신뢰성을 높였으며, 중간 및 수식산화물의 첨가를 통해 유리프리트의 특성을 개선하였다. By using Sn 2 OP 2 O 7 as a main raw material, the reaction between P 2 O 5 and water was minimized between processes to improve the reliability between compositions, and the addition of intermediate and modified oxides improved the properties of glass frit.

(표1)(Table 1)

유리조성(wt.%)Glass composition (wt.%) Sn2P2O7 Sn 2 P 2 O 7 35 ? 8035? 80 R2O3(R=Al, B, Bi, La)R 2 O 3 (R = Al, B, Bi, La) 1 ? 25One ? 25 RO(R=Ca, Ba, Zn)RO (R = Ca, Ba, Zn) 1 ? 20One ? 20 R2O(R=Li, K)R 2 O (R = Li, K) 1 ? 10One ? 10 V2O5 V 2 O 5 1 ? 5One ? 5 전이점(℃)Transition point (℃) 240 ? 390240? 390 연화점(℃)Softening point (℃) 265 ? 420265? 420 열팽창계수(×10-7/℃)Thermal expansion coefficient (× 10 -7 / ℃) 73 ? 13573? 135

(실시 예2)(Example 2)

실시 예 2는 특성 개선용 필러로서 코디어라이트계와 유크립타이트의 합성방법으로 각각의 필러원료를 혼합하여 도가니에 넣고 1250℃에서 1300℃에서 5시간에서 48시간까지 유지하여 필러를 합성하고, 합성물을 분쇄 한 후, 결정상을 향상시키고자 재합성하는 방법이다. (도1)에 합성 횟수에 따른 유크립타이트의 결정상을 나타내었다. 위와 같은 방법으로 합성한 유크립타이트를 각각 합성 횟수에 따라 엑스선회절분석기를 이용하여 결정상을 비교한 결과 1회 합성한 것보다 2회 또는 3회 합성한 경우 결정성이 더 우수하였다. Example 2 is a filler for improving the properties as a synthesis method of cordierite-based and krypite, each filler raw material is mixed in a crucible and maintained at 1250 ℃ 1300 ℃ for 5 hours to 48 hours to synthesize the filler, After pulverizing the composite, it is a method of resynthesizing to improve the crystal phase. Figure 1 shows the crystal phase of the eu cryptite according to the number of synthesis. As a result of comparing the crystalline phases by using the X-ray diffractometer according to the number of syntheses, the crystalline crystals synthesized as described above were superior to those synthesized twice or three times than those synthesized once.

(실시 예3)Example 3

실시 예3은 실시 예1에서 제조한 유리프리트에 실시 예 2에서 제조한 코디어라이 트계와 라스계 세라믹스(eucryptite, spodumene)를 합성하여 필러로 첨가하였을 때, 열팽창계수의 변화를 나타낸 것이다. (도2)에 유리프리트에 코디어라이트와와 유크립타이트의 필러 첨가량을 5-15%로 조절하였을 때 고온현미경 측정data를 나타내었다. 필러함량이 증가할수록 유리프리트가 무너지지 않고 형상을 유지함으로 상판과 하판사이의 간격을 유지할 수 있음을 알 수 있고 열팽창계수 값이 -10～20×10-7/℃로 낮기 때문에 필러첨가량이 증가할수록 유리프리트의 열팽창계수의 값도 낮아져 기판의 열팽창계수에 근접함을 알 수 있었다. Example 3 shows a change in the coefficient of thermal expansion when the cordierite-based and lath-based ceramics (eucryptite, spodumene) prepared in Example 2 were synthesized and added to the glass frit prepared in Example 1 as a filler. 2 shows high temperature microscope measurement data when the amount of filler added to cordierite and eu cryptite was adjusted to 5-15% in glass frit. It can be seen that the gap between the upper and lower plates can be maintained by maintaining the shape of glass frit without collapsing as the filler content is increased. Since the coefficient of thermal expansion is low as -10 to 20 × 10 -7 / ℃, the filler addition is increased. It was found that the value of the coefficient of thermal expansion of the glass frit was also lowered, which was close to that of the substrate.

도1 : 필러(filler) 합성 횟수에 따른 유크립타이트의 결정상태.1: Crystalline state of eu cryptite according to the number of filler synthesis.

도2 : 유리프리트에 코디어라이트와 유크립타이트의 필러(5~15%)를 첨가하였 을 때의 고온 현미경 측정 데이터.2: High-temperature microscopy data when the cordierite and eucryptite fillers (5-15%) were added to the glass frit.

Claims (2)

1내지 10중량%의 R2O(R=Li.K),와 1내지 25중량%의 R203(R=B,Al,Bi)와 1내지 20중량%의 Ro (R=Ca,Ba,Mg,Zn)와 1내지 5 중량%의 산화바나듐(V2O5)과 잔부는 망목산화물(Sn2P2O7) 조성의 유리프리트용 필러 합성방법으로 25중량%의 탄산마그네슘(MgCo3),과 30.3중량%의 산화 알루미늄(Al2O3),과 44.7중량%의 산화실리콘(SiO2)을 혼합한 MgCo3-Al2O3-SiO2계 코디어라이트 조성물을 1300℃에서 5내지 48시간 유지하여 합성한 후 상기 합성물을 분쇄하고 이를 다시 1300℃에서 5내지 48시간 유지하여 재합성하는 것을 특징으로 하는 420℃이하의 저온에서 봉착이 가능한 밀봉재용 무연유리 프리트 필러 합성방법.1 to 10% by weight of R 2 O (R = Li.K), 1 to 25% by weight of R 2 O 3 (R = B, Al, Bi) and 1 to 20% by weight of Ro (R = Ca, Ba, Mg, Zn) and 1-5% of vanadium oxide by weight (V 2 O 5) and the cup parts mesh oxide (Sn 2 P 2 O 7) magnesium carbonate 25% by weight of a glass frit filler synthesis method for the composition ( MgCo 3), and of 30.3% by weight of aluminum oxide (Al 2 O 3), and a MgCo mixing a silicon oxide (SiO 2) of 44.7% by weight 3 -Al 2 O 3 -SiO 2 cordierite-based composition to light 1300 ℃ Lead-free glass fritter filler for sealing materials capable of sealing at low temperature below 420 ℃ characterized in that after the synthesis by maintaining for 5 to 48 hours in the pulverized and then resynthesizing the composite at 5 to 48 hours at 1300 ℃ . 1내지 10중량%의 R2O(R=Li.K),와 1내지 25중량%의 R203(R=B,Al,Bi)와 1내지 20중량%의 Ro (R=Ca,Ba,Mg,Zn)와 1내지 5 중량%의 산화바나듐(V2O5)과 잔부는 망목산화물(Sn2P2O7) 조성의 유리프리트용 필러 합성방법으로 25중량%의 탄산리튬(Li2Co3)과 34.5중량%의 산화 알루미늄(Al2O3)과 40.5중량%의 산화실리콘(SiO2)을 혼합한 Li2Co3-Al2O3-SiO2 계 유크립타이트를 1250℃에서 5내지 48시간 유지하여 합성한 후 상기 합성물을 분쇄하고 이를 다시 1250℃에서 5내지 48시간 유지하여 재합성하는 것을 특징으로 하는 420℃이하의 온도에서 봉착이 가능한 밀봉재용 무연 유리 프리트 필러 합성방법.1 to 10% by weight of R 2 O (R = Li.K), 1 to 25% by weight of R 2 O 3 (R = B, Al, Bi) and 1 to 20% by weight of Ro (R = Ca, Ba, Mg, Zn) and 1-5% of vanadium oxide by weight (V 2 O 5) and the cup parts mesh oxide (Sn 2 P 2 O 7) 25% by weight of a glass frit filler synthesis method for a composition of lithium carbonate ( Li 2 Co 3) and 34.5% by weight of aluminum oxide (Al 2 O 3) and a Li 2 Co 3 -Al 2 O 3 -SiO 2 system the -eucryptite 1250 mixing a silicon oxide (SiO 2) of 40.5% by weight Lead-free glass frit filler for sealing material capable of sealing at a temperature of 420 ℃ or less, characterized in that after the synthesis by maintaining for 5 to 48 hours at ℃ and pulverized the composite again and maintained at 1250 ℃ for 5 to 48 hours Way.
KR1020090104812A 2009-11-02 2009-11-02 Pb-free glass-frit for sealant that sealing is possible at low temperature below 420°Cand synthesize of filler that is suitable to glass-frit KR101205207B1 (en)

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