WO2024063440A1 - Lead-free low-temperature fired glass frit - Google Patents

Lead-free low-temperature fired glass frit Download PDF

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WO2024063440A1
WO2024063440A1 PCT/KR2023/013808 KR2023013808W WO2024063440A1 WO 2024063440 A1 WO2024063440 A1 WO 2024063440A1 KR 2023013808 W KR2023013808 W KR 2023013808W WO 2024063440 A1 WO2024063440 A1 WO 2024063440A1
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Prior art keywords
glass frit
present
lead
glass
temperature fired
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PCT/KR2023/013808
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French (fr)
Korean (ko)
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박태호
정찬민
차명룡
권태성
김민섭
김두리
김동찬
김길호
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주식회사 베이스
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Publication of WO2024063440A1 publication Critical patent/WO2024063440A1/en

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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
    • 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
    • C03C3/145—Silica-free oxide glass compositions containing boron containing aluminium or beryllium
    • 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

Definitions

  • the present invention relates to a lead-free low-temperature fired glass frit, and more specifically, to a low-temperature fired lead-free glass frit that can be used for sealing bonding of vacuum insulating double-layer glass, display panels such as organic light-emitting diode displays (OLED), and other electronic devices. It's about.
  • Sealing bonding materials containing glass compositions are used for bonding vacuum insulated double-layer glass, display panels such as organic light-emitting diode displays (OLED), and other electronic devices.
  • the sealing bonding material is made in the form of a paste containing glass frit, and is applied to the bonding object by screen printing, dispensing, etc., and then baked to achieve sealing adhesion.
  • the sealing bonding material must be applied to the bonding object, for example, insulating glass or a display panel, and then fired.
  • the bonding object for example, insulating glass or a display panel
  • firing is performed at a high temperature, a problem may occur in which the characteristics of the bonding object change.
  • the glass frit included in the bonding material must be capable of low-temperature firing.
  • a vanadium-based glass composition is known as a lead-free glass composition.
  • the glass frit is required to have low temperature properties and excellent adhesion.
  • stronger adhesion than before is required for their sealing bonding.
  • the present inventor came up with the present invention for a glass frit that can secure strong adhesion characteristics while using a vanadium-based composition.
  • the present invention is intended to solve the problems of the prior art described above, and its purpose is to provide a lead-free low-temperature fired glass frit capable of low-temperature firing.
  • the purpose of the present invention is to provide a lead-free low-temperature fired glass frit that is capable of low-temperature firing and has excellent adhesion properties.
  • the lead-free low-temperature fired glass frit according to an embodiment of the present invention includes vanadium oxide, TeO 2 and ZnO, and the vanadium oxide includes V 2 O 5 and VO 2 .
  • the molar ratio of V 2 O 5 to VO 2 may be 1.0 to 1.3.
  • the lead-free low-temperature fired glass frit according to an embodiment of the present invention may include 25 to 41 mol% of vanadium oxide, 15 to 40 mol% of TeO 2 and 15 to 40 mol% of ZnO.
  • the lead-free low-temperature fired glass frit according to an embodiment of the present invention may further include 0.1 to 6 mol% of alkali metal oxide.
  • the alkali metal oxide may be at least one of Li 2 O and Na 2 O.
  • the lead-free low-temperature fired glass frit according to an embodiment of the present invention is Bi 2 O 3 , B 2 O 3 , Al 2 O 3 , ZrO 2 , SiO 2 , Nb 2 O 5 , TiO 2 , CuO, Fe 2 O 3 , MnO 2 , Na 2 CO 3 , K 2 CO 3 , and BaCO 3 may be included in an amount of 1 to 15 mol%.
  • the lead-free low-temperature fired glass frit according to an embodiment of the present invention may further include a ceramic filler.
  • the ceramic filler may be at least one of zirconium phosphate (ZP), zirconium-tungsten-phosphate filler (ZWP), cordierite, and eucryptite.
  • the ceramic filler may be included in an amount of 5 to 20% by weight based on the total glass frit.
  • the transition point of the lead-free low-temperature fired glass frit according to an embodiment of the present invention may be 280°C to 320°C.
  • the lead-free low-temperature fired glass frit according to an embodiment of the present invention may have a thermal expansion coefficient of 65 ⁇ 10 -7 /°C to 85 ⁇ 10 -7 /°C.
  • a glass frit capable of low-temperature firing without containing Pb can be provided through a vanadium-based glass composition.
  • the glass frit according to an embodiment of the present invention can be fired at low temperatures and have excellent adhesion characteristics.
  • Figure 1 is a FTIR analysis graph after firing a sealing bonding material including a lead-free low-temperature fired glass frit according to an embodiment of the present invention.
  • the lead-free low-temperature fired glass frit according to an embodiment of the present invention can be used for sealing bonding of vacuum insulating double-layer glass, OLED display panels, and other electronic devices.
  • bonding is accomplished by applying a paste containing a glass frit to a bonding object such as vacuum insulated double-layer glass or an OLED display panel and firing it.
  • a bonding object such as vacuum insulated double-layer glass or an OLED display panel
  • firing is performed at a high temperature, not only does the process cost increase, but the bonding object is also damaged. Problems may arise where the characteristics of glass, display panels, display elements, etc. may change.
  • a vanadium-based glass frit is used for low-temperature firing.
  • the lead-free low-temperature fired glass frit according to an embodiment of the present invention may include vanadium oxide, tellurium oxide, and zinc oxide.
  • Vanadium oxide acts as a glass former and has low melting point properties, improving flow characteristics and acting as a flux to lower the glass transition temperature (Tg).
  • tellurium oxide can increase the bonding strength of glass, improve water resistance and chemical resistance, and lower the glass transition temperature (Tg), and zinc oxide improves water resistance of the glass composition, lowers the coefficient of thermal expansion, and stabilizes the glass composition. It can play a role.
  • the lead-free low-temperature fired glass frit may include V 2 O 5 and VO 2 as vanadium oxide. That is, according to one embodiment of the present invention, the vanadium oxide of the glass frit may include V 5+ ions in the form of V 2 O 5 and may also include V 4+ ions in the form of VO 2 .
  • Vanadium oxide generally exists in the form of V 2 O 5 with V 5+ ions. However, because V 2 O 5 has a stable glass structure, sufficient adhesion characteristics may not be secured when bonded to a bonding object (eg, a glass substrate). In contrast, when vanadium oxide contains V 4+ ions, Si 4+ ions from the bonding object (for example, a glass substrate) can easily diffuse into the glass frit, which is a bonding material, resulting in As the ion diffusion distance into the bonding material increases, the adhesive strength, that is, the adhesive force, can be improved.
  • the ratio of V 5+ ions to V 4+ ions contained in the vanadium oxide of the glass frit is 1.0 to 1.3. That is, based on the molar ratio, V 5+ /V 4+ is 1.0 to 1.3. If the ratio of V 5+ ions to V 4+ ions is less than 1.0, fluidity may decrease during firing, and adhesion may increase excessively, causing cracks to occur in the attached glass substrate, etc. and making it vulnerable to impact. Additionally, if the ratio of V 5+ ions to V 4+ ions is greater than 1.3, the effect of improving adhesion due to containing V 4+ ions cannot be sufficiently observed. Accordingly, in one embodiment of the present invention, the ratio of V 5+ ions to V 4+ ions contained in the vanadium oxide of the glass frit is set to 1.0 to 1.3 in consideration of improved adhesion and fluidity characteristics during firing.
  • the ratio of VO 2 i.e., the ratio of V 4+ ions constituting the vanadium oxide of the lead-free low-temperature fired glass frit can be controlled by the following method.
  • the ratio of V 5+ ions to V 4+ ions contained in the vanadium oxide of the glass frit can be confirmed through analysis of the structure after firing.
  • structures with V 5+ (V 2 O 5 ) and V 4+ (VO 2 ) ion values can be distinguished through FTIR or You can check the ratio of V 5+ ions to
  • Figure 1 is a FTIR analysis graph after firing a sealing bonding material containing a lead-free low-temperature fired glass frit according to an embodiment of the present invention.
  • the absorption wavelength band (about 925 cm -1) of a structure having a V 4+ ion value is shown.
  • the absorption wavelength band (840 cm -1 ) of a structure with a V 5+ ion value the ratio of V 5+ ions to V 4+ ions can be confirmed.
  • Frit A the molar ratio of V 5+ ions to V 4+ ions is measured to be 1.38
  • Frit B the molar ratio of V 5+ ions to V 4+ ions is measured to be 1.14.
  • the lead-free low-temperature fired glass frit may include TeO 2 and ZnO as tellurium oxide and zinc oxide, respectively.
  • the glass frit according to an embodiment of the present invention may contain about 25 to about 41 mol% of vanadium oxide, about 15 to about 40 mol% of tellurium oxide, and about 15 to about 40 mol% of zinc oxide. % may be included.
  • vanadium oxide is contained less than the above composition range, the glass transition point and softening point may increase, and if contained more, vanadium oxide may devitrify when melted and bubbles may be generated during firing.
  • tellurium oxide is contained less than the above composition range, water resistance may be reduced and fluidity or glass stability may be reduced, and if tellurium oxide is contained in larger amounts, the coefficient of thermal expansion may greatly increase.
  • zinc oxide is contained less than the above composition range, glass meltability may be low, making glass manufacturing difficult, and if zinc oxide is contained more, crystals may form inside the glass, lowering transparency.
  • the lead-free low-temperature fired glass frit according to an embodiment of the present invention may further include an alkali metal oxide.
  • the alkali metal oxide may include at least one of Li 2 O and Na 2 O.
  • the glass frit may contain about 0.1 to about 6 mol% of alkali metal oxide.
  • the lead-free low-temperature fired glass frit according to an embodiment of the present invention may further include at least one of Bi 2 O 3 , B 2 O 3 , Al 2 O 3 , ZrO 2 , SiO 2 , and TiO 2 .
  • the glass frit may contain about 1 to about 15 mol% of at least one of the above components.
  • the lead-free low-temperature fired glass frit according to an embodiment of the present invention further contains at least one of Nb 2 O 5 , CuO, Fe 2 O 3 , MnO 2 , Na 2 CO 3 , K 2 CO 3 , and BaCO 3 It can be included. These components may include about 1 to about 15 mol% of at least one of Bi 2 O 3 , B 2 O 3 , Al 2 O 3 , ZrO 2 , SiO 2 , and TiO 2 .
  • the lead-free low-temperature fired glass frit according to an embodiment of the present invention may further include a ceramic filler in addition to the components described above.
  • the glass frit is a ceramic filler and includes one or more of zirconium phosphate (ZP), zirconium-tungsten-phosphate filler (ZWP), cordierite, and eucryptite. can do.
  • the ceramic filler lowers the thermal expansion coefficient of the glass frit, matches the thermal expansion coefficient with the bonding target (e.g., glass substrate), and prevents cracks from spreading between the bonding target (e.g., glass substrate) and the bonding material. do.
  • the content of the ceramic filler becomes too large, the adhesion to the bonding object (for example, a glass substrate) may decrease, so the content needs to be limited to a certain range.
  • the glass frit according to an embodiment of the present invention may be composed of about 80 to about 95% by weight of the above-described glass component and about 5 to about 20% by weight of the ceramic filler.
  • the lead-free low -temperature fired glass frit according to an embodiment of the present invention having such a composition has a temperature of 65 It can have a thermal expansion coefficient of /°C.
  • the transition point of the lead-free low-temperature fired glass frit according to an embodiment of the present invention is 280°C to 320°C, and can be fired at 370°C to 410°C.
  • the glass frit composition having the above-described composition can be manufactured in paste form for sealing glass substrates, etc.
  • 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 polymers, and then mixed with crystallized glass powder and ceramic filler in an appropriate ratio.
  • organic solvents such as alcohol-based solvents, ketone-based solvents, and ether-based solvents
  • organic binders such as acrylic polymers and cellulose polymers
  • Table 1 shows the composition of the glass frit according to the examples and comparative examples of the present invention.
  • the content of each composition is expressed in mol%, which is a value calculated based on the total content of the glass frit.
  • Table 3 lists the transition point (T g ), thermal expansion coefficient, crystallization, and adhesion characteristics of each glass frit.
  • T g transition point
  • crystallization evaluation was conducted after firing at a temperature of 400°C for 30 minutes.
  • adhesion was conducted through the following process.
  • the evaluation value (MPa) for the adhesion evaluation was calculated as the average value of the measured values by performing a tensile test that measures the load at the moment the adhesive surface is broken 10 times. An adhesion evaluation value of 1.0 or less is poor, 1.0 to 2.0 is normal, and 2.0 to 3.0 was judged as excellent, and 3.0 or more was judged as very good.
  • both Examples and Comparative Examples showed excellent low-temperature characteristics with a transition point (Tg) of less than 310°C.
  • Tg transition point
  • the thermal expansion coefficient in the comparative example was confirmed to be somewhat higher than that of the example, but was generally confirmed to be at a good level.
  • crystals occurred, which is presumed to be due to the high content of vanadium oxide.
  • adhesion it can be seen that there is a large difference between the examples and comparative examples. Specifically, in examples where the molar ratio of V 5+ to V 4+ is between 1.0 and 1.3, the adhesion is confirmed to be excellent or very excellent, and it can be seen that the adhesion generally increases as it approaches 1.0. On the other hand, it can be confirmed that adhesion is poor in comparative examples where the molar ratio of V 5+ to V 4+ is less than 1.0 or greater than 1.3. In particular, it can be confirmed that cracks occur in Comparative Example 4 where the molar ratio of V 5+ to V 4+ is less than 1.0.
  • adhesion increases when the vanadium oxide of the lead-free composition glass frit contains VO 2 .
  • adhesion is particularly excellent when the molar ratio of V 5+ to V 4+ is between 1.0 and 1.3.

Abstract

The present invention relates to a lead-free low-temperature fired glass frit that can be used for sealing and bonding of vacuum insulating double-layer glass, a display panel of an organic light-emitting diode display (OLED) and the like, and other electronic devices. A lead-free low-temperature fired glass frit, according to one embodiment of the present invention, comprises: vanadium oxide; TeO2; and ZnO, wherein vanadium oxide includes V2O5 and VO2.

Description

무연계 저온 소성 글라스 프릿Lead-free low-temperature fired glass frit
본 발명은 무연계 저온 소성 글라스 프릿에 관한 것으로서, 더욱 상세하게는 진공 단열 복층 유리, 유기 발광 다이오드 디스플레이(OLED) 등의 디스플레이 패널, 기타 전자소자의 밀봉 접합에 사용될 수 있는 저온 소성 무연 글라스 프릿에 관한 것이다.The present invention relates to a lead-free low-temperature fired glass frit, and more specifically, to a low-temperature fired lead-free glass frit that can be used for sealing bonding of vacuum insulating double-layer glass, display panels such as organic light-emitting diode displays (OLED), and other electronic devices. It's about.
진공 단열 복층 유리, 유기 발광 다이오드 디스플레이(OLED) 등의 디스플레이 패널, 기타 전자소자의 접합에 유리 조성물을 포함하는 밀봉 접합 재료가 사용된다. 밀봉 접합 재료는 글라스 프릿을 포함하는 페이스트 형태로 이루어지며, 접합 대상에 스크린 인쇄, 디스펜싱 등에 의해 도포된 후 소성을 거쳐 밀봉 접착이 이루어지게 된다.Sealing bonding materials containing glass compositions are used for bonding vacuum insulated double-layer glass, display panels such as organic light-emitting diode displays (OLED), and other electronic devices. The sealing bonding material is made in the form of a paste containing glass frit, and is applied to the bonding object by screen printing, dispensing, etc., and then baked to achieve sealing adhesion.
밀봉 접합 재료는 접합 대상, 예를 들어 단열 유리 또는 디스플레이 패널 상에 도포된 후 소성이 이루어져야 하는데, 만약 고온에서 소성이 이루어지는 경우에는 접합 대상의 특성이 변화하는 문제가 발생할 수 있다. 예를 들어, 강화 유리의 접합 시 400℃ 이상의 온도에서 소성이 이루어지게 되면, 강화 유리의 압축 응력이 풀려 강도가 저하되는 문제가 발생한다. 이에 따라, 접합 재료에 포함되는 글라스 프릿은 저온 소성이 가능해야 한다.The sealing bonding material must be applied to the bonding object, for example, insulating glass or a display panel, and then fired. However, if firing is performed at a high temperature, a problem may occur in which the characteristics of the bonding object change. For example, when sintering is performed at a temperature of 400°C or higher when bonding tempered glass, the compressive stress of the tempered glass is released, causing a problem that the strength decreases. Accordingly, the glass frit included in the bonding material must be capable of low-temperature firing.
종래에는 Pb를 포함하는 저온 소성 글라스 프릿이 널리 사용되었으나, 최근 환경 문제로 인하여 Pb의 사용이 제한되고 있다. 이에, 최근에는 Pb를 사용하지 않는 무연계 글라스 조성물의 개발이 활발히 이루어지고 있다. 예를 들어, 무연계 글라스 조성물로는 바나듐계 글라스 조성물이 알려져 있다.Previously, low-temperature fired glass frit containing Pb was widely used, but the use of Pb has recently been limited due to environmental problems. Accordingly, the development of lead-free glass compositions that do not use Pb has been actively conducted recently. For example, a vanadium-based glass composition is known as a lead-free glass composition.
한편, 밀봉 접합을 위하여는 글라스 프릿에는 저온화 특성과 함께 우수한 부착력이 요구된다. 특히, 단열 유리 내지 디스플레이 패널의 대면적화에 따라 이들의 밀봉 접합을 위하여 종래보다 더욱 강한 부착력이 요구되는 실정이다.Meanwhile, for sealing bonding, the glass frit is required to have low temperature properties and excellent adhesion. In particular, as the area of insulating glass and display panels increases, stronger adhesion than before is required for their sealing bonding.
이러한 요구에 따라, 본 발명자는 바나듐계 조성을 사용하면서 강한 부착력 특성을 확보할 수 있는 글라스 프릿에 본 발명을 도출하기에 이르렀다.In response to this request, the present inventor came up with the present invention for a glass frit that can secure strong adhesion characteristics while using a vanadium-based composition.
본 발명은 상술한 종래기술의 문제를 해결하기 위한 것으로서, 저온 소성이 가능한 무연계 저온 소성 글라스 프릿을 제공하는 것에 그 목적이 있다.The present invention is intended to solve the problems of the prior art described above, and its purpose is to provide a lead-free low-temperature fired glass frit capable of low-temperature firing.
또한, 본 발명은 저온 소성이 가능하면서도 우수한 부착력 특성을 갖는 무연계 저온 소성 글라스 프릿을 제공하는 것에 그 목적이 있다.Additionally, the purpose of the present invention is to provide a lead-free low-temperature fired glass frit that is capable of low-temperature firing and has excellent adhesion properties.
본 발명의 일 실시예에 따른 무연계 저온 소성 글라스 프릿은 바나듐 산화물, TeO2 및 ZnO을 포함하고, 바나듐 산화물은 V2O5 및 VO2를 포함한다.The lead-free low-temperature fired glass frit according to an embodiment of the present invention includes vanadium oxide, TeO 2 and ZnO, and the vanadium oxide includes V 2 O 5 and VO 2 .
본 발명의 일 실시예에 따르면, VO2에 대한 V2O5의 몰비는 1.0 내지 1.3일 수 있다.According to one embodiment of the present invention, the molar ratio of V 2 O 5 to VO 2 may be 1.0 to 1.3.
본 발명의 일 실시예에 따른 무연계 저온 소성 글라스 프릿은 바나듐 산화물 25 내지 41 mol%, TeO2 15 내지 40 mol% 및 ZnO 15 내지 40 mol%를 포함할 수 있다.The lead-free low-temperature fired glass frit according to an embodiment of the present invention may include 25 to 41 mol% of vanadium oxide, 15 to 40 mol% of TeO 2 and 15 to 40 mol% of ZnO.
본 발명의 일 실시예에 따른 무연계 저온 소성 글라스 프릿은 알칼리금속 산화물 0.1 내지 6 mol%를 더 포함할 수 있다. 여기에서, 알칼리금속 산화물은 Li2O 및 Na2O 중 적어도 1종일 수 있다.The lead-free low-temperature fired glass frit according to an embodiment of the present invention may further include 0.1 to 6 mol% of alkali metal oxide. Here, the alkali metal oxide may be at least one of Li 2 O and Na 2 O.
본 발명의 일 실시예에 따른 무연계 저온 소성 글라스 프릿은 Bi2O3, B2O3, Al2O3, ZrO2, SiO2, Nb2O5, TiO2, CuO, Fe2O3, MnO2, Na2CO3, K2CO3, BaCO3 중 적어도 1종을 1 내지 15 mol% 포함할 수 있다.The lead-free low-temperature fired glass frit according to an embodiment of the present invention is Bi 2 O 3 , B 2 O 3 , Al 2 O 3 , ZrO 2 , SiO 2 , Nb 2 O 5 , TiO 2 , CuO, Fe 2 O 3 , MnO 2 , Na 2 CO 3 , K 2 CO 3 , and BaCO 3 may be included in an amount of 1 to 15 mol%.
본 발명의 일 실시예에 따른 무연계 저온 소성 글라스 프릿은 세라믹 필러를 더 포함할 수 있다. 여기에서 세라믹 필러는 지르코늄 포스페이트(ZP), 지르코늄-텅스텐-포스페이트계 필러(ZWP), 코디어라이트(cordierite) 및 유크립타이트(eucryptite) 중 적어도 1종일 수 있다.The lead-free low-temperature fired glass frit according to an embodiment of the present invention may further include a ceramic filler. Here, the ceramic filler may be at least one of zirconium phosphate (ZP), zirconium-tungsten-phosphate filler (ZWP), cordierite, and eucryptite.
본 발명의 일 실시예에 따르면, 세라믹 필러는 전체 글라스 프릿을 기준으로 5 내지 20 중량% 포함될 수 있다.According to one embodiment of the present invention, the ceramic filler may be included in an amount of 5 to 20% by weight based on the total glass frit.
본 발명의 일 실시예에 따른 무연계 저온 소성 글라스 프릿의 전이점은 280℃ 내지 320℃일 수 있다.The transition point of the lead-free low-temperature fired glass frit according to an embodiment of the present invention may be 280°C to 320°C.
본 발명의 일 실시예에 따른 무연계 저온 소성 글라스 프릿은 열팽창계수가 65×10-7/℃ 내지 85×10-7/℃일 수 있다.The lead-free low-temperature fired glass frit according to an embodiment of the present invention may have a thermal expansion coefficient of 65×10 -7 /℃ to 85×10 -7 /℃.
본 발명의 일 실시예에 따르면, 바나듐계 글라스 조성을 통해 Pb를 포함하지 않고도 저온 소성이 가능한 글라스 프릿을 제공할 수 있다.According to one embodiment of the present invention, a glass frit capable of low-temperature firing without containing Pb can be provided through a vanadium-based glass composition.
또한, 본 발명의 일 실시예에 따른 글라스 프릿은 저온 소성이 가능하면서도 우수한 부착력 특성을 가질 수 있다.In addition, the glass frit according to an embodiment of the present invention can be fired at low temperatures and have excellent adhesion characteristics.
도 1은 본 발명의 일 실시예에 따른 무연계 저온 소성 글라스 프릿을 포함하는 밀봉 접합재의 소성 후 FTIR 분석 그래프이다.Figure 1 is a FTIR analysis graph after firing a sealing bonding material including a lead-free low-temperature fired glass frit according to an embodiment of the present invention.
이하, 첨부한 도면을 참조하여 본 발명의 바람직한 실시예에 대해 본 발명이 속하는 기술 분야에서 통상의 지식을 가진 자가 용이하게 실시할 수 있을 정도로 상세하게 설명한다.Hereinafter, with reference to the accompanying drawings, preferred embodiments of the present invention will be described in detail so that those skilled in the art can easily implement the present invention.
본 발명을 명확하게 설명하기 위하여 본 발명과 관계없는 부분의 설명은 생략하였으며, 명세서 전체를 통하여 동일한 구성요소에 대해서는 동일한 참조 부호를 붙이도록 한다. 명세서에 기재되어 있는 특정 형상, 구조 및 특성은 본 발명의 사상 및 범위를 벗어나지 않으면서 일 실시예로부터 다른 실시예로 변경되어 구현될 수 있으며, 개별 구성요소의 위치 또는 배치도 본 발명의 사상 및 범위를 벗어나지 않으면서 변경될 수 있는 것으로 이해되어야 한다.In order to clearly explain the present invention, descriptions of parts unrelated to the present invention have been omitted, and like reference numerals are assigned to like components throughout the specification. The specific shape, structure, and characteristics described in the specification may be changed and implemented from one embodiment to another without departing from the spirit and scope of the present invention, and the location or arrangement of individual components may also be implemented within the spirit and scope of the present invention. It should be understood as something that can be changed without deviating from it.
따라서, 후술하는 상세한 설명은 한정적인 의미로서 행하여지는 것이 아니며, 본 발명의 범위는 청구범위의 청구항들이 청구하는 범위 및 그와 균등한 모든 범위를 포괄하는 것으로 받아들여져야 한다.Accordingly, the detailed description described below is not to be taken in a limiting sense, and the scope of the present invention should be taken to encompass the scope of the claims and all equivalents thereof.
본 발명의 일 실시예에 따른 무연계 저온 소성 글라스 프릿은 진공 단열 복층 유리, OLED 디스플레이 패널, 기타 전자소자의 밀봉 접합에 사용될 수 있다.The lead-free low-temperature fired glass frit according to an embodiment of the present invention can be used for sealing bonding of vacuum insulating double-layer glass, OLED display panels, and other electronic devices.
상술한 바와 같이, 진공 단열 복층 유리, OLED 디스플레이 패널 등의 접합 대상에 글라스 프릿을 포함하는 페이스트를 도포하고 소성하여 접합이 이루어지는데, 고온에서 소성이 이루어지게 되면 공정 비용이 증가할 뿐만 아니라 접합 대상인 유리 내지 디스플레이 패널, 디스플레이 소자 등의 특성이 변화할 수 있는 문제가 발생할 수 있다.As described above, bonding is accomplished by applying a paste containing a glass frit to a bonding object such as vacuum insulated double-layer glass or an OLED display panel and firing it. However, if firing is performed at a high temperature, not only does the process cost increase, but the bonding object is also damaged. Problems may arise where the characteristics of glass, display panels, display elements, etc. may change.
이에, 본 발명의 일 실시예에서는 저온 소성을 위하여 바나듐계 글라스 프릿을 사용한다. 구체적으로, 본 발명의 일 실시예에 따른 무연계 저온 소성 글라스 프릿은 바나듐 산화물, 텔루르 산화물 및 아연 산화물을 포함할 수 있다.Accordingly, in one embodiment of the present invention, a vanadium-based glass frit is used for low-temperature firing. Specifically, the lead-free low-temperature fired glass frit according to an embodiment of the present invention may include vanadium oxide, tellurium oxide, and zinc oxide.
바나듐 산화물은 유리 형성제 역할을 하는 것으로, 저융점화 특성을 가지고 있어 유동 특성을 향상시키고, 유리전이온도(Tg)를 낮추는 융제로서의 역할을 할 수 있다. 또한, 텔루르 산화물은 유리의 결합력을 높여 내수성 및 내화학성을 향상시키고 유리전이온도(Tg)를 낮추는 역할을 할 수 있고, 아연 산화물은 유리 조성물의 내수성을 향상시키고 열팽창계수를 저하시키고 유리 조성물을 안정화시키는 역할을 할 수 있다.Vanadium oxide acts as a glass former and has low melting point properties, improving flow characteristics and acting as a flux to lower the glass transition temperature (Tg). In addition, tellurium oxide can increase the bonding strength of glass, improve water resistance and chemical resistance, and lower the glass transition temperature (Tg), and zinc oxide improves water resistance of the glass composition, lowers the coefficient of thermal expansion, and stabilizes the glass composition. It can play a role.
본 발명의 일 실시예에 따르면, 무연계 저온 소성 글라스 프릿은 바나듐 산화물로 V2O5 및 VO2를 포함할 수 있다. 즉, 본 발명의 일 실시예에 따르면, 글라스 프릿의 바나듐 산화물은 V2O5 형태로 V5+ 이온을 포함하고, 이와 함께 VO2 형태로 V4+ 이온을 포함할 수 있다.According to one embodiment of the present invention, the lead-free low-temperature fired glass frit may include V 2 O 5 and VO 2 as vanadium oxide. That is, according to one embodiment of the present invention, the vanadium oxide of the glass frit may include V 5+ ions in the form of V 2 O 5 and may also include V 4+ ions in the form of VO 2 .
바나듐 산화물은 V5+ 이온을 갖는 V2O5의 형태로 존재하는 것이 일반적이다. 하지만, V2O5는 안정된 유리 구조 형태를 갖기 때문에 접합 대상(예를 들어, 유리 기판)과 접합 시 충분한 부착력 특성을 확보하지 못할 수 있다. 이에 비하여, 바나듐 산화물에 V4+ 이온이 포함되는 경우에는, 접합 대상(예를 들어, 유리 기판)에서의 Si4+ 이온이 접합 재료인 글라스 프릿으로 쉽게 확산될 수 있으며, 이로 인해 접합 대상에서 접합 재료로의 이온 확산 거리 증가에 따라 양자의 접착 강도, 즉 부착력이 향상될 수 있다.Vanadium oxide generally exists in the form of V 2 O 5 with V 5+ ions. However, because V 2 O 5 has a stable glass structure, sufficient adhesion characteristics may not be secured when bonded to a bonding object (eg, a glass substrate). In contrast, when vanadium oxide contains V 4+ ions, Si 4+ ions from the bonding object (for example, a glass substrate) can easily diffuse into the glass frit, which is a bonding material, resulting in As the ion diffusion distance into the bonding material increases, the adhesive strength, that is, the adhesive force, can be improved.
본 발명의 일 실시예에 따르면, 글라스 프릿의 바나듐 산화물에 포함되는 V4+ 이온에 대한 V5+ 이온의 비율은 1.0 내지 1.3이다. 즉, 몰비를 기준으로 V5+/V4+는 1.0 내지 1.3이다. V4+ 이온에 대한 V5+ 이온의 비율이 1.0보다 작으면, 소성 시 유동성이 저하될 수 있으며, 부착력이 과도하게 증가하여 부착된 유리 기판 등에 크랙이 발생할 수 있고 충격에 취약하게 된다. 또한, V4+ 이온에 대한 V5+ 이온의 비율이 1.3보다 크면, V4+ 이온을 함유함에 따른 부착력 향상 효과를 충분히 볼 수 없다. 이에 따라, 본 발명의 일 실시예에서는 부착력 향상과 소성 시 유동성 특성 등을 고려하여 글라스 프릿의 바나듐 산화물에 포함되는 V4+ 이온에 대한 V5+ 이온의 비율을 1.0 내지 1.3로 한다.According to one embodiment of the present invention, the ratio of V 5+ ions to V 4+ ions contained in the vanadium oxide of the glass frit is 1.0 to 1.3. That is, based on the molar ratio, V 5+ /V 4+ is 1.0 to 1.3. If the ratio of V 5+ ions to V 4+ ions is less than 1.0, fluidity may decrease during firing, and adhesion may increase excessively, causing cracks to occur in the attached glass substrate, etc. and making it vulnerable to impact. Additionally, if the ratio of V 5+ ions to V 4+ ions is greater than 1.3, the effect of improving adhesion due to containing V 4+ ions cannot be sufficiently observed. Accordingly, in one embodiment of the present invention, the ratio of V 5+ ions to V 4+ ions contained in the vanadium oxide of the glass frit is set to 1.0 to 1.3 in consideration of improved adhesion and fluidity characteristics during firing.
한편, 본 발명의 일 실시예에 따르면, 무연계 저온 소성 글라스 프릿의 바나듐 산화물을 구성하는 VO2의 비율(즉, V4+ 이온의 비율)은 다음과 같은 방법으로 제어할 수 있다.Meanwhile, according to one embodiment of the present invention, the ratio of VO 2 (i.e., the ratio of V 4+ ions) constituting the vanadium oxide of the lead-free low-temperature fired glass frit can be controlled by the following method.
(1) V4+ 이온을 포함한 바나듐 화합물을 글라스 프릿 조성물 제조 시 첨가하는 방법(1) Method of adding a vanadium compound containing V 4+ ions when manufacturing a glass frit composition
(2) V2O5을 포함한 글라스 프릿 조성물에 환원제를 첨가하여 V2O5의 V5+ 이온을 V4+ 이온으로 환원시키는 방법(2) A method of reducing V 5+ ions of V 2 O 5 to V 4+ ions by adding a reducing agent to a glass frit composition containing V 2 O 5
(3) V2O5을 포함한 글라스 프릿 조성물을 환원 분위기에서 열처리하여 V5+ 이온을 V4+ 이온으로 환원시키는 방법(3) A method of reducing V 5+ ions to V 4+ ions by heat treating a glass frit composition containing V 2 O 5 in a reducing atmosphere.
본 발명의 일 실시예에 따르면, 글라스 프릿의 바나듐 산화물에 포함되는 V4+ 이온에 대한 V5+ 이온의 비율은 소성 후 구조의 분석을 통해 확인할 수 있다. 예를 들어, 소성 후의 밀봉 접합재에 대한 FTIR 또는 XPS 분석기기를 통해 V5+(V2O5) 및 V4+(VO2) 이온가를 갖는 구조를 구분할 수 있으며, 이를 통해 V4+ 이온에 대한 V5+ 이온의 비율을 확인할 수 있다.According to one embodiment of the present invention, the ratio of V 5+ ions to V 4+ ions contained in the vanadium oxide of the glass frit can be confirmed through analysis of the structure after firing. For example, structures with V 5+ (V 2 O 5 ) and V 4+ (VO 2 ) ion values can be distinguished through FTIR or You can check the ratio of V 5+ ions to
도 1은 본 발명의 일 실시예에 따른 무연계 저온 소성 글라스 프릿을 포함하는 밀봉 접합재의 소성 후 FTIR 분석 그래프로서, 도 1을 참조하면 V4+ 이온가를 갖는 구조의 흡광 파장대(약 925cm-1)와 V5+ 이온가를 갖는 구조의 흡광 파장대(840cm-1)에서의 흡광도(absorption)를 비교하여, V4+ 이온에 대한 V5+ 이온의 비율을 확인할 수 있다. 예를 들어, Frit A의 경우 V4+ 이온에 대한 V5+ 이온의 몰비는 1.38로 측정되고, Frit B의 경우 V4+ 이온에 대한 V5+ 이온의 몰비는 1.14로 측정된다.Figure 1 is a FTIR analysis graph after firing a sealing bonding material containing a lead-free low-temperature fired glass frit according to an embodiment of the present invention. Referring to Figure 1, the absorption wavelength band (about 925 cm -1) of a structure having a V 4+ ion value is shown. ) and the absorption wavelength band (840 cm -1 ) of a structure with a V 5+ ion value, the ratio of V 5+ ions to V 4+ ions can be confirmed. For example, for Frit A, the molar ratio of V 5+ ions to V 4+ ions is measured to be 1.38, and for Frit B, the molar ratio of V 5+ ions to V 4+ ions is measured to be 1.14.
본 발명의 일 실시예에 따르면, 무연계 저온 소성 글라스 프릿은 텔루르 산화물 및 아연 산화물로 각각 TeO2 및 ZnO를 포함할 수 있다.According to one embodiment of the present invention, the lead-free low-temperature fired glass frit may include TeO 2 and ZnO as tellurium oxide and zinc oxide, respectively.
본 발명의 일 실시예에 따른 글라스 프릿은 바나듐 산화물을 약 25 내지 약 41 mol% 포함할 수 있고, 텔루르 산화물을 약 15 내지 약 40 mol% 포함할 수 있으며, 아연 산화물을 약 15 내지 약 40 mol% 포함할 수 있다.The glass frit according to an embodiment of the present invention may contain about 25 to about 41 mol% of vanadium oxide, about 15 to about 40 mol% of tellurium oxide, and about 15 to about 40 mol% of zinc oxide. % may be included.
바나듐 산화물이 위 조성 범위보다 적게 함유되는 경우에는 유리 전이점 및 연화점이 상승할 수 있으며, 더 많이 함유되는 경우에는 용융 시 실투될 수 있고 소성 시 기포가 발생할 수 있다. 텔루르 산화물이 위 조성 범위보다 적게 함유되는 경우에는 내수성이 저하되고 유동성이나 유리 안정성이 저하될 수 있으며, 더 많이 함유되는 열팽창계수가 크게 증가할 수 있다. 아연 산화물이 위 조성 범위보다 적게 함유되는 경우에는 유리 용융성이 낮아 유리 제조가 어려워질 수 있고, 더 많이 함유되는 경우에는 유리 내부에 결정이 생겨 투명도가 낮아질 수 있다.If vanadium oxide is contained less than the above composition range, the glass transition point and softening point may increase, and if contained more, vanadium oxide may devitrify when melted and bubbles may be generated during firing. If tellurium oxide is contained less than the above composition range, water resistance may be reduced and fluidity or glass stability may be reduced, and if tellurium oxide is contained in larger amounts, the coefficient of thermal expansion may greatly increase. If zinc oxide is contained less than the above composition range, glass meltability may be low, making glass manufacturing difficult, and if zinc oxide is contained more, crystals may form inside the glass, lowering transparency.
본 발명의 일 실시예에 따른 무연계 저온 소성 글라스 프릿은 알칼리금속 산화물을 더 포함할 수 있다. 알칼리금속 산화물로는 Li2O 및 Na2O 중 적어도 1종을 포함할 수 있다. 본 발명의 일 실시예에 따르면, 글라스 프릿은 알칼리금속 산화물을 약 0.1 내지 약 6 mol% 포함할 수 있다.The lead-free low-temperature fired glass frit according to an embodiment of the present invention may further include an alkali metal oxide. The alkali metal oxide may include at least one of Li 2 O and Na 2 O. According to one embodiment of the present invention, the glass frit may contain about 0.1 to about 6 mol% of alkali metal oxide.
본 발명의 일 실시예에 따른 무연계 저온 소성 글라스 프릿은 Bi2O3, B2O3, Al2O3, ZrO2, SiO2, TiO2 중 적어도 1종을 더 포함할 수 있다. 본 실시예에 따르면, 글라스 프릿은 상기 성분 중 적어도 1종을 약 1 내지 약 15 mol% 포함할 수 있다.The lead-free low-temperature fired glass frit according to an embodiment of the present invention may further include at least one of Bi 2 O 3 , B 2 O 3 , Al 2 O 3 , ZrO 2 , SiO 2 , and TiO 2 . According to this embodiment, the glass frit may contain about 1 to about 15 mol% of at least one of the above components.
본 발명의 일 실시예에 따른 무연계 저온 소성 글라스 프릿은 이밖에 Nb2O5, CuO, Fe2O3, MnO2, Na2CO3, K2CO3, BaCO3 중 적어도 1종을 더 포함할 수 있다. 이들 성분은 Bi2O3, B2O3, Al2O3, ZrO2, SiO2, TiO2 중 적어도 1종과 합하여 약 1 내지 약 15 mol% 포함할 수 있다.In addition, the lead-free low-temperature fired glass frit according to an embodiment of the present invention further contains at least one of Nb 2 O 5 , CuO, Fe 2 O 3 , MnO 2 , Na 2 CO 3 , K 2 CO 3 , and BaCO 3 It can be included. These components may include about 1 to about 15 mol% of at least one of Bi 2 O 3 , B 2 O 3 , Al 2 O 3 , ZrO 2 , SiO 2 , and TiO 2 .
본 발명의 일 실시예에 따른 무연계 저온 소성 글라스 프릿은 상술한 성분 이외에 세라믹 필러를 더 포함할 수 있다. 본 발명의 일 실시예에 따르면 글라스 프릿은 세라믹 필러로서 지르코늄 포스페이트(ZP), 지르코늄-텅스텐-포스페이트계 필러(ZWP), 코디어라이트(cordierite) 및 유크립타이트(eucryptite) 중 1종 이상을 포함할 수 있다.The lead-free low-temperature fired glass frit according to an embodiment of the present invention may further include a ceramic filler in addition to the components described above. According to one embodiment of the present invention, the glass frit is a ceramic filler and includes one or more of zirconium phosphate (ZP), zirconium-tungsten-phosphate filler (ZWP), cordierite, and eucryptite. can do.
세라믹 필러는 글라스 프릿의 열팽창계수를 낮춰 접합 대상(예를 들어, 유리 기판)과 열팽창계수를 매칭시키고 접합 대상(예를 들어, 유리 기판)과 접합 재료 사이의 크랙이 전이되는 것을 방지하는 역할을 한다. 하지만, 세라믹 필러의 함량이 지나치게 많아지게 되면 접합 대상(예를 들어, 유리 기판)과의 부착력을 감소시킬 수 있어, 그 함량을 일정한 범위로 한정할 필요가 있다. 예를 들어, 본 발명의 일 실시예에 따른 글라스 프릿은 상술한 유리 성분 약 80 내지 약 95 중량%와 세라믹 필러 약 5 내지 약 20 중량%로 구성될 수 있다.The ceramic filler lowers the thermal expansion coefficient of the glass frit, matches the thermal expansion coefficient with the bonding target (e.g., glass substrate), and prevents cracks from spreading between the bonding target (e.g., glass substrate) and the bonding material. do. However, if the content of the ceramic filler becomes too large, the adhesion to the bonding object (for example, a glass substrate) may decrease, so the content needs to be limited to a certain range. For example, the glass frit according to an embodiment of the present invention may be composed of about 80 to about 95% by weight of the above-described glass component and about 5 to about 20% by weight of the ceramic filler.
이러한 조성을 갖는 본 발명의 일 실시예에 따른 무연계 저온 소성 글라스 프릿은 65 X 10-7/℃ 내지 85 X 10-7/℃, 바람직하게는 70 X 10-7/℃ 내지 80 X 10-7/℃의 열팽창계수를 가질 수 있다. 또한, 본 발명의 일 실시예에 따른 무연계 저온 소성 글라스 프릿의 전이점은 280℃ 내지 320℃이며, 370℃ 내지 410℃에서 소성될 수 있다.The lead-free low -temperature fired glass frit according to an embodiment of the present invention having such a composition has a temperature of 65 It can have a thermal expansion coefficient of /℃. In addition, the transition point of the lead-free low-temperature fired glass frit according to an embodiment of the present invention is 280°C to 320°C, and can be fired at 370°C to 410°C.
전술한 조성을 갖는 글라스 프릿 조성물은 유리 기판 등의 실링을 위하여 페이스트 형태로 제조될 수 있다. 구체적으로, 알코올계 용제, 케톤계 용제, 에테르계 용제와 같은 유기 용제와 아크릴계 고분자, 셀룰로오스계 고분자와 같은 유기 바인더를 혼합하여 비이클을 제조하고, 여기에 결정화 유리 분말과 세라믹 필러를 적정 비율로 혼합하여 페이스트를 제조할 수 있다. 이때, 유리 물성, 도포 물성 등을 저하시키지 않는 범위에서 무기 안료가 더 포함될 수도 있다.The glass frit composition having the above-described composition can be manufactured in paste form for sealing glass substrates, etc. Specifically, 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 polymers, and then mixed with crystallized glass powder and ceramic filler in an appropriate ratio. A paste can be produced by doing so. At this time, inorganic pigments may be further included to the extent that they do not deteriorate glass properties, coating properties, etc.
이하에서 구체적인 실험예들을 통하여 지금까지 설명한 본 발명의 일 실시예에 따른 무연계 저온 소성 글라스 프릿의 특성을 구체적으로 설명한다. Hereinafter, the characteristics of the lead-free low-temperature fired glass frit according to an embodiment of the present invention described so far will be described in detail through specific experimental examples.
실험예Experiment example
표 1은 본 발명의 실시예 및 비교예에 따른 글라스 프릿의 조성을 나타낸다. 각 조성의 함량은 mol%로 나타내었으며, 이는 글라스 프릿 전체 함량을 기준으로 산정한 수치이다.Table 1 shows the composition of the glass frit according to the examples and comparative examples of the present invention. The content of each composition is expressed in mol%, which is a value calculated based on the total content of the glass frit.
구분division 실시예1Example 1 실시예2Example 2 실시예3Example 3 실시예4Example 4 실시예5Example 5 실시예6Example 6 비교예1Comparative Example 1 비교예2Comparative example 2 비교예3Comparative example 3 비교예4Comparative example 4
바나듐산화물vanadium oxide 3131 4141 3434 3333 2626 2828 4545 4242 3636 2424
TeO2 TeO 2 2020 1717 2121 2828 3838 3030 1414 2828 3030 4141
ZnOZnO 3737 2525 3030 2020 1717 2626 2727 2020 1313 1818
Li2O + Na2OLi 2 O + Na 2 O 1.21.2 2.32.3 3.23.2 5.55.5 4.24.2 3.73.7 22 -- 3.63.6 7.17.1
Bi2O3 Bi 2 O 3 33 44 22 44 44 22 33 22 66 --
B2O3 B 2 O 3 2.82.8 2.72.7 22 2.52.5 44 44 -- 22 22 --
Al2O3 Al 2 O 3 22 1One 1One 22 22 22 22 22 -- 2.72.7
ZrO2 ZrO2 22 22 22 22 1.81.8 1.81.8 22 33 33 44
SiO2 SiO 2 -- 1One 22 -- 0.50.5 -- 22 1One 44 --
TiO2 TiO 2 1One 44 2.82.8 33 2.52.5 2.52.5 33 -- 2.42.4 3.23.2
표 1의 글라스 조성에는 각각 세라믹 필러로서 코디어라이트 약 10 중량%가 첨가되었다. 또한, 각 실시예 및 비교예에서의 바나듐 산화물에 포함되는 V4+에 대한 V5+의 몰비(V5+/V4+)는 표 2와 기재한 바와 같다.About 10% by weight of cordierite was added to each of the glass compositions in Table 1 as a ceramic filler. In addition, the molar ratio (V 5+ /V 4+ ) of V 5+ to V 4+ contained in the vanadium oxide in each Example and Comparative Example is as shown in Table 2.
구분division 실시예1Example 1 실시예2Example 2 실시예3Example 3 실시예4Example 4 실시예5Example 5 실시예6Example 6 비교예1Comparative Example 1 비교예2Comparative example 2 비교예3Comparative example 3 비교예4Comparative Example 4
V5+/V4+ V 5+ /V 4+ 1.231.23 1.281.28 1.171.17 1.131.13 1.041.04 1.091.09 1.411.41 -- 1.491.49 0.950.95
표 1과 표 2의 실시예 및 비교예의 글라스 프릿의 특성은 표 3에 기재된 바와 같다. 구체적으로, 표 3에서는 각 글라스 프릿의 전이점(Tg), 열팽창계수, 결정화 여부 및 부착력 특성이 기재되었다. 여기서, 결정화 평가는 400℃의 온도로 30분간 소성을 진행한 후 실시하였다. 또한, 부착력의 평가는 다음의 과정을 통하여 실시하였다.The properties of the glass frits of Examples and Comparative Examples in Tables 1 and 2 are as shown in Table 3. Specifically, Table 3 lists the transition point (T g ), thermal expansion coefficient, crystallization, and adhesion characteristics of each glass frit. Here, crystallization evaluation was conducted after firing at a temperature of 400°C for 30 minutes. In addition, evaluation of adhesion was conducted through the following process.
- 제1 유리 기판 상에 글라스 프릿을 포함하는 페이스트를 도포 후 1차 소성- Apply paste containing glass frit on the first glass substrate and then perform first firing
- 제2 유리 기판을 제1 유리 기판 상에 배치하고 글라스 프릿 주위에 필라(스페이서) 배열한 후 연화 온도로 2차 소성- Place the second glass substrate on the first glass substrate, arrange pillars (spacers) around the glass frit, and then perform secondary firing at a softening temperature.
- 인장 시험기를 통해 접착면이 파괴되는 순간의 하중 측정- Measure the load at the moment the adhesive surface is destroyed using a tensile tester
부착력 평가의 평가 수치(MPa)는 접착면이 파괴되는 순간의 하중을 측정하는 인장 시험을 10회 실시하여 측정값의 평균값으로 산출하였으며, 부착력 평가 수치가 1.0 이하는 불량, 1.0 내지 2.0은 보통, 2.0 내지 3.0은 우수, 3.0 이상은 매우 우수로 판단하였다.The evaluation value (MPa) for the adhesion evaluation was calculated as the average value of the measured values by performing a tensile test that measures the load at the moment the adhesive surface is broken 10 times. An adhesion evaluation value of 1.0 or less is poor, 1.0 to 2.0 is normal, and 2.0 to 3.0 was judged as excellent, and 3.0 or more was judged as very good.
구분division 실시예1Example 1 실시예2Example 2 실시예3Example 3 실시예4Example 4 실시예5Example 5 실시예6Example 6 비교예1Comparative Example 1 비교예2Comparative example 2 비교예3Comparative Example 3 비교예4Comparative example 4
전이점(℃)Transition point (℃) 309309 301301 294294 284284 289289 303303 285285 303303 292292 271271
열팽창계수
(10-7/℃)thermal expansion coefficient
(10 -7 /℃) 		7777 7878 7474 7777 7676 7575 7979 8282 8080 7777
결정화crystallization XX XX XX XX XX XX OO XX XX XX
부착력(MPa)Adhesion (MPa) 2.62.6 2.22.2 2.82.8 3.53.5 3.23.2 2.92.9 0.80.8 0.50.5 0.50.5 CrackCrack
표 3을 참조하면, 실시예 및 비교예 모두 전이점(Tg)이 310℃ 미만으로 우수한 저온 특성을 나타내었다. 실시예에 비하여 비교예에서의 열팽계수가 다소 높은 것으로 확인되나, 대체로 양호한 수준으로 확인된다. 비교예 1의 경우 결정이 발생하였는데, 이는 바나듐 산화물의 함량이 높은 것에 기인한 것으로 추정된다. Referring to Table 3, both Examples and Comparative Examples showed excellent low-temperature characteristics with a transition point (Tg) of less than 310°C. The thermal expansion coefficient in the comparative example was confirmed to be somewhat higher than that of the example, but was generally confirmed to be at a good level. In Comparative Example 1, crystals occurred, which is presumed to be due to the high content of vanadium oxide.
부착력의 경우, 실시예와 비교예 사이의 차이가 큼을 확인할 수 있다. 구체적으로, V4+에 대한 V5+의 몰비가 1.0 내지 1.3 사이인 실시예에서는 부착력이 우수하거나 매우 우수한 것으로 확인되며, 대체로 1.0에 가까울수록 부착력이 커짐을 확인할 수 있다. 반면에, V4+에 대한 V5+의 몰비가 1.0 보다 작거나 1.3 보다 큰 비교예에서는 부착력이 불량함을 확인할 수 있다. 특히, V4+에 대한 V5+의 몰비가 1.0 보다 작은 비교예 4에서는 크랙이 발생함을 확인할 수 있다.In the case of adhesion, it can be seen that there is a large difference between the examples and comparative examples. Specifically, in examples where the molar ratio of V 5+ to V 4+ is between 1.0 and 1.3, the adhesion is confirmed to be excellent or very excellent, and it can be seen that the adhesion generally increases as it approaches 1.0. On the other hand, it can be confirmed that adhesion is poor in comparative examples where the molar ratio of V 5+ to V 4+ is less than 1.0 or greater than 1.3. In particular, it can be confirmed that cracks occur in Comparative Example 4 where the molar ratio of V 5+ to V 4+ is less than 1.0.
이상의 실험예를 통하여, 무연계 조성 글라스 프릿의 바나듐 산화물이 VO2를 포함하는 경우 부착력이 증가함으로 확인할 수 있다. 또한, V4+에 대한 V5+의 몰비가 1.0 내지 1.3 사이인 경우 부착력이 특히 우수함을 확인할 수 있다.Through the above experimental examples, it can be confirmed that adhesion increases when the vanadium oxide of the lead-free composition glass frit contains VO 2 . In addition, it can be seen that the adhesion is particularly excellent when the molar ratio of V 5+ to V 4+ is between 1.0 and 1.3.
이상 본 발명을 구체적인 구성요소 등과 같은 특정 사항들과 한정된 실시예에 의해 설명하였으나, 상기 실시예는 본 발명의 보다 전반적인 이해를 돕기 위해서 제공된 것일 뿐, 본 발명이 이에 한정되는 것은 아니며, 본 발명이 속하는 기술분야에서 통상적인 지식을 가진 자라면 이러한 기재로부터 다양한 수정 및 변형을 꾀할 수 있다.Although the present invention has been described above with reference to specific details such as specific components and limited examples, the examples are provided only to facilitate a more general understanding of the present invention, and the present invention is not limited thereto. Anyone with ordinary knowledge in the relevant technical field can make various modifications and variations from this description.
따라서, 본 발명의 사상은 앞서 설명된 실시예에 국한되어 정해져서는 아니 되며, 후술하는 청구범위뿐만 아니라 이 청구범위와 균등하게 또는 등가적으로 변형된 모든 것들은 본 발명의 사상의 범주에 속한다고 할 것이다.Accordingly, the spirit of the present invention should not be limited to the embodiments described above, and all modifications equivalent to or equivalent to the claims as well as the claims described below shall fall within the scope of the spirit of the present invention. will be.

Claims (10)

  1. 무연계 저온 소성 글라스 프릿으로서,As a lead-free low-temperature fired glass frit,
    바나듐 산화물, TeO2, 및 ZnO을 포함하고,Contains vanadium oxide, TeO 2 , and ZnO,
    상기 바나듐 산화물은 V2O5 및 VO2를 포함하는,The vanadium oxide includes V 2 O 5 and VO 2 ,
    글라스 프릿.Glass frit.
  2. 제1항에 있어서, According to paragraph 1,
    몰비를 기준으로 V5+/V4+는 1.0 내지 1.3인,Based on the molar ratio, V 5+ /V 4+ is 1.0 to 1.3,
    글라스 프릿.Glass frit.
  3. 제1항에 있어서, According to paragraph 1,
    바나듐 산화물 25 내지 41 mol%,25 to 41 mol% vanadium oxide,
    TeO2 15 내지 40 mol% 및15 to 40 mol% of TeO 2 and
    ZnO 15 내지 40 mol%ZnO 15 to 40 mol%
    를 포함하는, 글라스 프릿.Including, glass frit.
  4. 제2항에 있어서, According to paragraph 2,
    알칼리금속 산화물 0.1 내지 6 mol%를 더 포함하는, 글라스 프릿.A glass frit further comprising 0.1 to 6 mol% of alkali metal oxide.
  5. 제4항에 있어서, According to paragraph 4,
    상기 알칼리금속 산화물은 Li2O 및 Na2O 중 적어도 1종인, 글라스 프릿.The alkali metal oxide is at least one of Li 2 O and Na 2 O, a glass frit.
  6. 제4항에 있어서, According to paragraph 4,
    Bi2O3, B2O3, Al2O3, ZrO2, SiO2, Nb2O5, TiO2, CuO, Fe2O3, MnO2, Na2CO3, K2CO3, BaCO3 중 적어도 1종을 1 내지 15 mol% 포함하는, 글라스 프릿.Bi 2 O 3 , B 2 O 3 , Al 2 O 3 , ZrO 2 , SiO 2 , Nb 2 O 5 , TiO 2 , CuO, Fe 2 O 3 , MnO 2 , Na 2 CO 3 , K 2 CO 3 , BaCO A glass frit containing 1 to 15 mol% of at least one of 3 .
  7. 제1항에 있어서,According to paragraph 1,
    세라믹 필러를 더 포함하고,further comprising a ceramic filler,
    상기 세라믹 필러는 지르코늄 포스페이트(ZP), 지르코늄-텅스텐-포스페이트계 필러(ZWP), 코디어라이트(cordierite) 및 유크립타이트(eucryptite) 중 적어도 1종인, 글라스 프릿.A glass frit, wherein the ceramic filler is at least one of zirconium phosphate (ZP), zirconium-tungsten-phosphate filler (ZWP), cordierite, and eucryptite.
  8. 제7항에 있어서,In clause 7,
    상기 세라믹 필러는 전체 글라스 프릿을 기준으로 5 내지 20 중량% 포함하는, 글라스 프릿. A glass frit containing 5 to 20% by weight of the ceramic filler based on the total glass frit.
  9. 제1항에 있어서,According to paragraph 1,
    전이점이 280℃ 내지 320℃인, 글라스 프릿.A glass frit having a transition point of 280°C to 320°C.
  10. 제1항에 있어서, According to paragraph 1,
    열팽창계수가 65×10-7/℃ 내지 85×10-7/℃인, 글라스 프릿.A glass frit having a thermal expansion coefficient of 65×10 -7 /°C to 85×10 -7 /°C.
PCT/KR2023/013808 2022-09-23 2023-09-14 Lead-free low-temperature fired glass frit WO2024063440A1 (en)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100787463B1 (en) * 2007-01-05 2007-12-26 삼성에스디아이 주식회사 A glass frit, a composition for preparing seal material and a light emitting device
KR20100012132A (en) * 2008-07-28 2010-02-08 공주대학교 산학협력단 Phosphate based glass composition for flat panel display sealing
KR20130134564A (en) * 2012-05-31 2013-12-10 (주)세라 Frit composition for sealing electric component panels and electric components sealed with said frit composition
KR20200071675A (en) * 2018-12-11 2020-06-19 에이지씨 가부시키가이샤 Glass composition, glass powder, sealing material, glass paste, sealing method, sealing package, and organic electroluminescence element

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR100787463B1 (en) * 2007-01-05 2007-12-26 삼성에스디아이 주식회사 A glass frit, a composition for preparing seal material and a light emitting device
KR20100012132A (en) * 2008-07-28 2010-02-08 공주대학교 산학협력단 Phosphate based glass composition for flat panel display sealing
KR20130134564A (en) * 2012-05-31 2013-12-10 (주)세라 Frit composition for sealing electric component panels and electric components sealed with said frit composition
KR20200071675A (en) * 2018-12-11 2020-06-19 에이지씨 가부시키가이샤 Glass composition, glass powder, sealing material, glass paste, sealing method, sealing package, and organic electroluminescence element

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
JONGHEE HWANG, HYUNJIN JEONG, LEE MI-JAE, YOUNGJIN LEE, JINHO KIM: " Effect of V2O5 Content and Pre-Sintering Atmosphere on Adhesive Property of Glass Frit for Laser Sealing of OLED.", JOURNAL OF THE KOREAN INSTITUTE OF ELECTRICAL AND ELECTRONIC MATERIAL ENGINEERS, KOREA, vol. 29, no. 8, 1 August 2016 (2016-08-01), Korea, pages 489 - 493, XP009553289, ISSN: 1226-7945 *

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