WO2023146355A1 - Composition de fritte de verre pour scellement à base de verre sous vide - Google Patents

Composition de fritte de verre pour scellement à base de verre sous vide Download PDF

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Publication number
WO2023146355A1
WO2023146355A1 PCT/KR2023/001297 KR2023001297W WO2023146355A1 WO 2023146355 A1 WO2023146355 A1 WO 2023146355A1 KR 2023001297 W KR2023001297 W KR 2023001297W WO 2023146355 A1 WO2023146355 A1 WO 2023146355A1
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WO
WIPO (PCT)
Prior art keywords
glass
sealing
vacuum
frit composition
crystallized
Prior art date
Application number
PCT/KR2023/001297
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English (en)
Korean (ko)
Inventor
박태호
차명룡
권태성
설재근
정찬민
김민섭
김두리
Original Assignee
주식회사 베이스
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Publication date
Application filed by 주식회사 베이스 filed Critical 주식회사 베이스
Publication of WO2023146355A1 publication Critical patent/WO2023146355A1/fr

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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
    • C03C8/24—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
    • 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
    • C03C8/14—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions
    • C03C8/20—Glass frit mixtures having non-frit additions, e.g. opacifiers, colorants, mill-additions containing titanium compounds; containing zirconium compounds

Definitions

  • the present invention relates to a glass frit composition for vacuum glass sealing.
  • Vacuum glass is a glass that maximizes heat insulation by forming a vacuum layer between glass panes to block heat transfer between the inside and outside, and is used as a window for energy saving.
  • the vacuum glass 10 includes an upper glass plate 11 and a lower glass plate 12 disposed to face each other, and a space between the upper glass plate 11 and the lower glass plate 12 is maintained.
  • a sealing material 14 for sealing the spacer 13 , the upper glass plate 11 and the lower glass plate 12 may be further included.
  • An exhaust hole may be formed in the upper plate glass 11, and a cap 15 sealing the exhaust hole may be further provided.
  • a glass frit is used as a sealing material for sealing the upper and lower glass panes.
  • Low-temperature fired glass is used as the glass frit, and the low-temperature fired glass generally has a higher coefficient of thermal expansion than plate glass to be bonded and sealed. Accordingly, a filler is added to lower the thermal expansion coefficient of the low-temperature fired glass.
  • the filler reduces the coefficient of thermal expansion of the low-temperature fired glass to overcome the difference in coefficient of thermal expansion with plate glass.
  • the filler functions to prevent damage by preventing the progress of cracks when an impact is applied from the outside.
  • sealing may not be easy due to lowered fluidity, and the filler may protrude or form a pinhole during firing, resulting in a decrease in adhesive strength. there is.
  • An object of the present invention is to provide a glass frit composition for vacuum glass sealing having a coefficient of thermal expansion close to that of plate glass and excellent adhesion.
  • an object of the present invention is to provide a glass frit composition for vacuum glass sealing capable of suppressing breakage by blocking crack propagation when an external impact is applied.
  • a glass frit composition for vacuum glass sealing includes crystallized glass and a ceramic filler.
  • the crystallized glass may include 25 to 45 mol% of V 2 O 5 , 10 to 35 mol% of TeO 2 , 20 to 40 mol% of ZnO, and 2 to 8 mol% of ZrO 2 .
  • the crystallized glass is Bi 2 O 3 , B 2 O 3 , Al 2 O 3 , SiO 2 , Nb 2 O 5 , TiO 2 , CuO, Fe 2 O 3 , MnO 2 , Na 2 5 to 15 mol% of one or more of CO 3 , K 2 CO 3 and BaCO 3 may be included.
  • the maximum crystallization temperature (T xm ) of the crystallized glass may be 380 °C to 440 °C.
  • the softening point (T s ) of the crystallized glass may be 340 °C to 400 °C.
  • the coefficient of thermal expansion (CTE) of the crystallized glass may be 70 ⁇ 10 -7 /°C to 85 ⁇ 10 -7 /°C.
  • the ceramic filler includes at least one of zirconium phosphate (ZP), cordierite, and zirconium-tungsten-phosphate filler (Zr 2 (WO 4 ) (PO 4 ) 2 ).
  • ZP zirconium phosphate
  • cordierite cordierite
  • zirconium-tungsten-phosphate filler Zr 2 (WO 4 ) (PO 4 ) 2 ).
  • a glass frit composition for vacuum glass sealing may include 80 wt % to 99 wt % of crystallized glass and 1 wt % to 20 wt % of a ceramic filler.
  • the crystallized glass may be crystallized at 370 °C to 380 °C.
  • the filler content can be minimized and adhesion can be improved.
  • FIG. 1 is a diagram schematically showing a cross section of a vacuum glass.
  • FIG. 2 is a diagram showing a manufacturing process of vacuum glass by way of example.
  • FIG. 3 is a diagram exemplarily showing DSC measurement results of a glass frit composition for vacuum glass sealing according to an embodiment of the present invention.
  • FIG. 2 is a diagram showing a manufacturing process of vacuum glass by way of example. First, with reference to FIG. 2, the manufacturing process of vacuum glass will be described.
  • a lower glass plate and an upper glass plate are prepared, and a sealing material is applied to the edge of the double lower glass plate (see (a) in FIG. 2). Thereafter, after a process of removing organic substances in the sealing material (burnout), spacers for maintaining a distance between the upper and lower glass plates are placed on the lower glass plate at regular intervals (see (b) and (c) in FIG. 2). ). Then, the upper pane is placed on the lower pane, clamped, and heated to a temperature equal to or higher than the softening point of the sealing material to join the edge portions (see (d) and (e) of FIG. 2). Finally, manufacturing of the vacuum glass is completed by forming a vacuum between the upper and lower glass panes through the exhaust hole formed in the upper pane and sealing the exhaust hole with a cap (FIG. 2(f) and (g)). reference).
  • the present invention relates to a glass frit composition constituting a sealing material for bonding and sealing a pair of glasses (ie, an upper glass plate and a lower plate glass) in manufacturing such a vacuum glass.
  • a glass frit composition for sealing vacuum glass Explain in detail.
  • a glass frit composition for vacuum glass sealing includes crystallized glass and a ceramic filler.
  • a sealing material for sealing vacuum glass is used by adding a filler to low-temperature fired glass in order to adjust its thermal expansion coefficient.
  • a filler to low-temperature fired glass in order to adjust its thermal expansion coefficient.
  • the present invention by using crystallized glass to lower the coefficient of thermal expansion, the content of the filler is minimized to solve the problem of deterioration in adhesion due to the filler.
  • the crystallized glass included in the glass frit composition for vacuum glass sealing according to an embodiment of the present invention includes V 2 O 5 , TeO 2 , ZnO, and ZrO 2 .
  • V 2 O 5 the role and preferred content of each component of crystallized glass will be described in detail.
  • V 2 O 5 serves as a glass forming agent, has a low melting point property, improves flow properties, and serves as a flux that lowers the glass transition temperature (Tg).
  • Tg glass transition temperature
  • 25 to 45 mol% of V 2 O 5 may be included. If the content of V 2 O 5 is less than 25 mol%, this may lead to an increase in the glass transition temperature (T g ) and softening temperature (T s ), resulting in deterioration in low-temperature workability and an increase in the viscosity of the glass, resulting in an increase in firing temperature.
  • T g glass transition temperature
  • T s softening temperature
  • the content of V 2 O 5 exceeds 45 mol% it is unstable and may devitrify during melting, and bubbles may be generated during firing, so that vitrification may not be achieved.
  • TeO 2 increases the bonding strength of glass, improves water resistance and chemical resistance, and serves to lower the glass transition temperature (Tg).
  • the content of TeO 2 is 10 to 35 mol%.
  • the content of TeO 2 is less than 10 mol%, water resistance may be deteriorated and flowability or glass stability may be deteriorated during melting.
  • the content of TeO 2 exceeds 35 mol%, the coefficient of thermal expansion may greatly increase.
  • ZnO improves the water resistance of the glass composition, lowers the thermal expansion coefficient, and serves to stabilize the glass composition.
  • the content of ZnO is 20 to 40 mol%. If the ZnO content is lower than 20 mol%, glass manufacturing may be difficult due to low melting properties of the glass. Conversely, if the ZnO content is higher than 40 mol%, crystals may form inside the glass, resulting in lowered transparency. .
  • ZrO 2 is a component for improving chemical resistance, and in this embodiment, the content of ZrO 2 is 2 to 8 mol%.
  • the content of ZrO 2 is less than 2 mol%, the effect of enhancing water resistance of the glass is small, and when it exceeds 8 mol%, the meltability is reduced and glass formation is difficult.
  • the crystallized glass is Bi 2 O 3 , B 2 O 3 , Al 2 O 3 , SiO 2 , Nb 2 O 5 , TiO 2 , CuO, Fe 2 O 3 , MnO 2 , Na 2
  • One or more of CO 3 , K 2 CO 3 and BaCO 3 may be further included in an amount of 5 to 15 mol%.
  • Bi 2 O 3 and TiO 2 serve to supplement the glass structure and at the same time enhance the adhesion of the glass frit.
  • the softening point (T s ) of the crystallized glass containing the above-described components may be 340 ° C to 400 ° C, and the maximum crystallization temperature (T xm ) may be 380 ° C to 440 ° C.
  • the crystallized glass according to the present embodiment may be softened and flowed at a first firing temperature of 340°C to 360°C, and may be crystallized at a second firing temperature of 370°C to 380°C.
  • the thermal expansion coefficient of the crystallized glass may be 70 ⁇ 10 -7 /°C to 85 ⁇ 10 -7 /°C.
  • primary firing of the glass frit composition may be performed in a state in which the glass frit composition for vacuum glass sealing according to an embodiment of the present invention is disposed on the lower pane, and then the upper pane is Secondary firing may be performed on the glass frit composition in a state of being placed on the lower pane and clamped.
  • the ceramic filler included in the glass frit composition for vacuum glass sealing according to an embodiment of the present invention is a crystalline inorganic particle having a low coefficient of thermal expansion, and includes zirconium phosphate (ZP), cordierite, and zirconium-tungsten-phosphate.
  • ZP zirconium phosphate
  • cordierite cordierite
  • zirconium-tungsten-phosphate zirconium-tungsten-phosphate.
  • Zr 2 (WO 4 )(PO 4 ) 2 may be included.
  • a glass frit composition for vacuum glass sealing may be configured by mixing 1 to 20 wt% of a ceramic filler with 80 wt% to 99 wt% of crystallized glass.
  • the crystallized glass according to the present embodiment has a low coefficient of thermal expansion, the content of the ceramic filler for adjusting the coefficient of thermal expansion can be minimized, and problems of deterioration in adhesion and deterioration in sealing performance due to the addition of a large amount of the filler can be overcome.
  • the glass frit composition having the above composition may be prepared in the form of a paste for sealing between glass panes.
  • a vehicle is prepared by mixing organic solvents such as alcohol-based solvents, ketone-based solvents, and ether-based solvents with organic binders such as acrylic polymers and cellulose-based polymers, and mixing crystallized glass powder and ceramic fillers in an appropriate ratio thereto paste can be prepared.
  • organic solvents such as alcohol-based solvents, ketone-based solvents, and ether-based solvents
  • organic binders such as acrylic polymers and cellulose-based polymers
  • Table 1 shows the contents of glass frit compositions according to embodiments of the present invention.
  • the mol% of each component is a value calculated based on the total content of the glass frit composition.
  • Table 2 shows the properties of the glass frit having the above composition. Specifically, the glass transition temperature (T g ), softening temperature (T s ), maximum crystallization temperature (T xm ), and crystallization (presence/absence) of each glass frit are shown.
  • T g glass transition temperature
  • T s softening temperature
  • T xm maximum crystallization temperature
  • T xm crystallization (presence/absence) of each glass frit are shown.
  • the maximum crystallization temperature (T xm ) was measured by DSC, as illustrated in FIG. 3, and crystallization evaluation was performed after firing at a temperature of 380° C. for 30 minutes.
  • Table 3 shows the results of evaluating the coefficient of thermal expansion (CTE) and adhesion by mixing the frit with a ceramic filler at a predetermined ratio.
  • the adhesion evaluation was performed by the Flow Button Test. Specifically, after molding a glass frit including a ceramic filler using an 8mm mold, the glass frit to be evaluated was placed on the lower plate glass, and after the first firing at 360 ° C, the upper Plate glass was placed and clamped, and secondary firing was performed at 380 ° C (at this time, a filler was placed on the lower plate glass to maintain the gap between the upper and lower plate glass), and after firing was completed, the upper plate glass was fixed while the lower plate glass was fixed. The adhesion of each glass frit was evaluated by measuring the force at which breakage occurs while pulling.
  • CTE coefficient of thermal expansion

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Glass Compositions (AREA)

Abstract

La présente invention concerne une composition de fritte de verre pour scellement à base de verre sous vide. Une composition de fritte de verre pour scellement à base de verre sous vide, selon un mode de réalisation de la présente invention, comprend du verre cristallisé et des charges céramiques.
PCT/KR2023/001297 2022-01-28 2023-01-27 Composition de fritte de verre pour scellement à base de verre sous vide WO2023146355A1 (fr)

Applications Claiming Priority (2)

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KR10-2022-0013073 2022-01-28
KR1020220013073A KR102707655B1 (ko) 2022-01-28 2022-01-28 진공 유리 실링용 글라스 프릿 조성물

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101220443B1 (ko) * 2011-11-17 2013-01-21 (주)에코플럭스 접착용 결정화 유리, 이를 포함하는 접착용 결정화 유리 조성물, 접착용 결정화 유리 페이스트, 및 유기발광다이오드 패널
JP2016135733A (ja) * 2015-01-15 2016-07-28 セントラル硝子株式会社 無鉛ガラス及び封着材料
KR20180137021A (ko) * 2016-05-23 2018-12-26 페로 게엠베하 섭씨 450도 이하의 온도에서의 진공 압축용 저온 텔루라이트 유리 혼합물
KR20200071619A (ko) * 2018-12-11 2020-06-19 엘지전자 주식회사 강화 유리에 적합한 무연계 저온 소성 글라스 프릿, 페이스트 및 이를 이용한 진공 유리 조립체
KR20200071675A (ko) * 2018-12-11 2020-06-19 에이지씨 가부시키가이샤 유리 조성물, 유리 분말, 봉착 재료, 유리 페이스트, 봉착 방법, 봉착 패키지 및 유기 일렉트로루미네센스 소자

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR102388066B1 (ko) 2018-12-11 2022-04-18 엘지전자 주식회사 강화 유리에 적합한 무연계 저온 소성 글라스 프릿, 페이스트 및 이를 이용한 진공 유리 조립체

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101220443B1 (ko) * 2011-11-17 2013-01-21 (주)에코플럭스 접착용 결정화 유리, 이를 포함하는 접착용 결정화 유리 조성물, 접착용 결정화 유리 페이스트, 및 유기발광다이오드 패널
JP2016135733A (ja) * 2015-01-15 2016-07-28 セントラル硝子株式会社 無鉛ガラス及び封着材料
KR20180137021A (ko) * 2016-05-23 2018-12-26 페로 게엠베하 섭씨 450도 이하의 온도에서의 진공 압축용 저온 텔루라이트 유리 혼합물
KR20200071619A (ko) * 2018-12-11 2020-06-19 엘지전자 주식회사 강화 유리에 적합한 무연계 저온 소성 글라스 프릿, 페이스트 및 이를 이용한 진공 유리 조립체
KR20200071675A (ko) * 2018-12-11 2020-06-19 에이지씨 가부시키가이샤 유리 조성물, 유리 분말, 봉착 재료, 유리 페이스트, 봉착 방법, 봉착 패키지 및 유기 일렉트로루미네센스 소자

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KR102707655B1 (ko) 2024-09-20

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