WO2014208524A1 - Verre exempt d'alcali - Google Patents

Verre exempt d'alcali Download PDF

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Publication number
WO2014208524A1
WO2014208524A1 PCT/JP2014/066627 JP2014066627W WO2014208524A1 WO 2014208524 A1 WO2014208524 A1 WO 2014208524A1 JP 2014066627 W JP2014066627 W JP 2014066627W WO 2014208524 A1 WO2014208524 A1 WO 2014208524A1
Authority
WO
WIPO (PCT)
Prior art keywords
glass
less
alkali
compaction
modulus
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/JP2014/066627
Other languages
English (en)
Japanese (ja)
Inventor
周平 野村
和孝 小野
順 秋山
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
AGC Inc
Original Assignee
Asahi Glass Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Asahi Glass Co Ltd filed Critical Asahi Glass Co Ltd
Priority to CN201480036113.5A priority Critical patent/CN105339318A/zh
Priority to KR1020157036188A priority patent/KR20160023699A/ko
Publication of WO2014208524A1 publication Critical patent/WO2014208524A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • 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
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • C03C3/087—Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal containing calcium oxide, e.g. common sheet or container glass
    • 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
    • C03C3/04—Glass compositions containing silica
    • C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
    • C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium

Definitions

  • the present invention is a non-alkali glass which is suitable for display substrate glass and photomask substrate glass used in the production of various flat panel displays (FPD) and which can be float-molded substantially free of alkali metal oxides. About.
  • Patent Document 1 Conventionally, various display substrate glasses, particularly those in which a metal or oxide thin film is formed on the surface, have been required to have the following characteristics as shown in Patent Document 1, for example. (1) When an alkali metal oxide is contained, alkali metal ions diffuse into the thin film and deteriorate the film characteristics, so that the alkali metal ions are not substantially contained. (2) Sufficient chemical durability against various chemicals used for semiconductor formation.
  • buffered hydrofluoric acid (BHF: mixture of hydrofluoric acid and ammonium fluoride) for etching SiO x and SiN x , and chemicals containing hydrochloric acid used for etching ITO, various acids used for etching metal electrodes (Nitric acid, sulfuric acid, etc.) Resistant to alkali of resist stripping solution. (3) There are no defects (bubbles, striae, inclusions, pits, scratches, etc.) inside and on the surface.
  • BHF mixture of hydrofluoric acid and ammonium fluoride
  • a-Si amorphous silicon
  • p-Si polycrystalline silicon
  • a glass having a small average thermal expansion coefficient is required in order to increase the temperature raising / lowering rate of the heat treatment for producing a liquid crystal display to increase the productivity and the thermal shock resistance.
  • the glass compaction is low in order to minimize the deformation of the glass and the dimensional change accompanying the stabilization of the glass structure when exposed to a high temperature in the thin film forming process.
  • An object of the present invention is to provide an alkali-free glass having a high specific elastic modulus and a high Young's modulus, a high glass transition point, low compaction, and easy float forming.
  • the Young's modulus is 90 GPa or more
  • the compaction C1 is 5 ppm or less
  • the compaction C2 is 50 ppm or less
  • CaO 2-30 Containing Provided is an alkali-free glass having SiO 2 + Al 2 O 3 of 70 or more and 90 or less.
  • the alkali-free glass of the present invention is suitable as a substrate glass for various displays and a substrate glass for a photomask, but can also be used as a glass substrate for a magnetic disk.
  • a substrate glass for various displays and a substrate glass for a photomask can also be used as a glass substrate for a magnetic disk.
  • it has a high Young's modulus, so various display substrate glasses and photomask substrate glasses It is effective as
  • the composition range of each component will be described. If SiO 2 exceeds 65% (mass%, the same unless otherwise specified), the Young's modulus becomes low. In addition, the viscosity is increased, and there is a risk that bubbles may be mixed in due to an increase in melting temperature or bubbles that cannot be completely removed during clarification. Further, devitrification of mullite easily occurs, and the devitrification temperature T L increases. If it is less than 40%, the average thermal expansion coefficient will increase. Moreover, devitrification of the spinel is likely to occur, and the devitrification temperature T L is increased. Preferably it is 42 to 63%, more preferably 44 to 61%.
  • Al 2 O 3 suppresses the phase separation property of the glass, lowers the average thermal expansion coefficient, and raises the glass transition point Tg, but this effect does not appear at 23.5% or less.
  • the Young's modulus decreases and compaction increases. Since Al 2 O 3 works as a network former like SiO 2, if it exceeds 30%, the viscosity increases, and there is a risk of increasing the melting temperature and mixing bubbles. Further, devitrification such as mullite, anorthite, and spinel is likely to occur, and the devitrification temperature TL may be increased. Preferably it is 24 to 29%, more preferably 24.5 to 28%.
  • MgO needs to be contained at 2.5% or more in order to improve solubility and improve Young's modulus. However, if it exceeds 20%, compaction will increase. Moreover, devitrification of the spinel is likely to occur, and the devitrification temperature T L is increased. Preferably it is 3 to 19%, more preferably 3.5 to 18%.
  • CaO improves solubility and can be prevented from being devitrified by containing it together with MgO, so it is necessary to contain 2% or more. However, if it exceeds 30%, the average thermal expansion coefficient becomes large. It also causes an increase in compaction. Preferably it is 3 to 29%, more preferably 4 to 28%.
  • the Young's modulus decreases, and devitrification of mullite easily occurs and the devitrification temperature T L increases.
  • the ratio of the network former is excessively increased, the viscosity is increased, the melting temperature is increased, and bubbles may be mixed. If it is less than 70%, compaction will increase.
  • the average coefficient of thermal expansion also increases. Preferably it is 72% to 88%, more preferably 74% to 86%.
  • the other components are preferably less than 5%, more preferably less than 3%, even more preferably less than 1%, and even more preferably less than 0.5% in order to suppress a decrease in Young's modulus, etc.
  • B 2 O 3 can be contained in an amount of less than 5% in order to improve the melting reactivity of the glass and to lower the devitrification temperature TL .
  • the amount is preferably less than 3%, more preferably less than 1%, even more preferably less than 0.5%, and particularly preferably not substantially contained.
  • SrO can be contained in an amount of less than 5% in order to improve the solubility without increasing the devitrification temperature TL of the glass.
  • the amount is preferably less than 3%, more preferably less than 1%, even more preferably less than 0.5%, and particularly preferably not substantially contained.
  • BaO can be contained in less than 5% in order to improve the solubility of the glass. However, if the amount is too large, the average thermal expansion coefficient will increase. Accordingly, it is preferably less than 3%, more preferably less than 1%, even more preferably less than 0.5%, and particularly preferably not substantially contained.
  • ZrO 2 can be contained in an amount of less than 3% in order to improve the Young's modulus of the glass. However, if the amount is too large, the devitrification temperature T L will increase. Accordingly, it is preferably less than 2%, more preferably less than 1%, even more preferably less than 0.5%, and particularly preferably not substantially contained.
  • the total amount of ZnO, SO 3 , Fe 2 O 3 , F, Cl and SnO 2 is less than 1%, preferably 0.8%. It can be contained less than 5%, more preferably less than 0.3%, and even more preferably less than 0.1%.
  • the glass of the present invention does not contain an alkali metal oxide in excess of the impurity level (ie substantially) in order not to cause deterioration of the characteristics of the metal or oxide thin film provided on the glass surface during panel production.
  • PbO, As 2 O 3 and Sb 2 O 3 are not substantially contained.
  • the alkali-free glass of the present invention has a Young's modulus of 90 GPa or more, fracture toughness is improved, and it is suitable for various display substrate glasses and photomask substrate glasses that require a larger or thinner glass plate. is there. 92 GPa or more is more preferable, and 94 GPa or more is more preferable.
  • the alkali-free glass of the present invention preferably has a specific elastic modulus (Young's modulus / density) of 35 GPa ⁇ cm 3 / g or more in order to reduce its own weight deflection. For this reason, there is little deformation resulting from its own weight deflection in the manufacturing process, and it is suitable for various display substrate glasses and photomask substrate glasses that require a larger or thinner glass plate. 36 GPa ⁇ cm 3 / g or more is more preferable, and 37 GPa ⁇ cm 3 / g or more is more preferable.
  • the alkali-free glass of the present invention has a very low compaction.
  • Compaction is the glass heat shrinkage generated by relaxation of the glass structure during the heat treatment.
  • compaction means a value measured by the method described below.
  • the target glass is melted at 1550 ° C. to 1650 ° C., then the molten glass is poured out, formed into a plate shape, and then cooled.
  • the obtained plate glass is polished to obtain a glass plate of 100 mm ⁇ 20 mm ⁇ 1 mm.
  • the obtained glass plate is heated to the glass transition point Tg + 70 ° C., held at this temperature for 1 minute, and then cooled to room temperature at a temperature drop rate of 40 ° C./min.
  • the alkali-free glass of the present invention has a compaction C1 of 5 ppm or less.
  • the compaction C2 is 50 ppm or less. Preferably it is 47 ppm or less, More preferably, it is 44 ppm or less.
  • the alkali-free glass of the present invention has a glass transition point of 740 ° C. or higher in order to suppress thermal shrinkage during panel manufacture and to make it possible to apply a method by laser annealing as a method for manufacturing a p-Si TFT. Is preferred.
  • the glass transition point is 740 ° C. or higher, the glass fictive temperature tends to increase in the production process (for example, organic EL having a thickness of 0.7 mm or less, preferably 0.5 mm or less, more preferably 0.3 mm or less).
  • the alkali-free glass of the present invention has a temperature T 2 at which the viscosity ⁇ becomes 10 2 poise (dPa ⁇ s) in order to facilitate melting, preferably 1730 ° C. or less, more preferably 1710 ° C. or less, More preferably, it is 1690 degrees C or less.
  • the alkali-free glass of the present invention has a temperature T 4 at which the viscosity ⁇ is 10 4 poise (dPa ⁇ s), preferably 1370 ° C. or less, more preferably 1350, in order to facilitate molding by the float process. ° C or lower, more preferably 1330 ° C or lower.
  • the alkali-free glass of the present invention can be produced, for example, by the following method.
  • the raw materials of each component that are normally used are blended so as to become target components, which are continuously charged into a melting furnace, heated to 1550 to 1650 ° C. and melted.
  • the molten glass is formed into a predetermined plate thickness by the float method, and then the glass plate can be obtained by slow cooling and cutting.
  • Examples 1 to 16 and 20 to 22 are examples, and Examples 17 to 19 are comparative examples.
  • the raw materials of each component were prepared so as to have a target composition, and were melted at a temperature of 1550 to 1650 ° C. using a platinum crucible. In melting, the mixture was stirred using a platinum stirrer to homogenize the glass. Next, the molten glass was poured out, formed into a plate shape, and then slowly cooled.
  • Tables 1 to 3 show the glass composition (unit: mass%), density ⁇ (g / cm 3 ), Young's modulus E (GPa) (measured by the ultrasonic method), specific elastic modulus E / ⁇ (GPa ⁇ cm 3 / g), glass transition point Tg (unit: ° C.), the glass viscosity ⁇ is 10 2 poise temperature T 2 (unit: ° C.), the temperature T 4 of the glass viscosity ⁇ is 10 4 poise (unit: ° C.) , And compaction C1 and C2 (measured by the method described above, unit: ppm).
  • the values shown in parentheses are calculated values.
  • all the glasses of the examples have a high Young's modulus of 90 GPa or higher and a glass transition point Tg of 740 ° C. or higher. Further, T 2 is 1730 ° C. or lower and T 4 is 1370 ° C. or lower. Moreover, the compaction C1 is 5 ppm or less, and the compaction C2 is 50 ppm or less.
  • the alkali-free glass of the present invention is suitable as a substrate glass for various displays and a substrate glass for a photomask, but can also be used as a glass substrate for a magnetic disk.
  • the substrate glass for various displays and the substrate glass for the photomask considering that the glass plate needs to be enlarged or thinned, it has a high Young's modulus, and when exposed to high temperatures in the thin film formation process, Considering that it is required to minimize the dimensional change associated with glass deformation and glass structure stabilization, the compaction is low, and therefore it is effective as substrate glass for various displays and photomask substrate glass.

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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

L'invention concerne un verre exempt d'alcali qui présente un module d'élasticité spécifique ainsi qu'un module de Young élevés, un point de transition vitreuse élevé, un faible compactage, et un formage par flottage aisé. Plus précisément, l'invention concerne un verre exempt d'alcali dont le module de Young est supérieur ou égal à 90GPa, dont un compactage (C1) est inférieur ou égal à 5ppm et un compactage (C2) est inférieur ou égal à 50ppm, qui comprend en % massique sur la base des oxydes, 40 à 65 de SiO2, plus de 23,5 à 30 de Al2O3, 2,5 à 20 de MgO et 2 à 30 de CaO, et tel que SiO2+ Al2O3 est supérieur ou égal à 70 et inférieur ou égal à 90.
PCT/JP2014/066627 2013-06-27 2014-06-24 Verre exempt d'alcali Ceased WO2014208524A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
CN201480036113.5A CN105339318A (zh) 2013-06-27 2014-06-24 无碱玻璃
KR1020157036188A KR20160023699A (ko) 2013-06-27 2014-06-24 무알칼리 유리

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2013134921A JP2016153346A (ja) 2013-06-27 2013-06-27 無アルカリガラス
JP2013-134921 2013-06-27

Publications (1)

Publication Number Publication Date
WO2014208524A1 true WO2014208524A1 (fr) 2014-12-31

Family

ID=52141858

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2014/066627 Ceased WO2014208524A1 (fr) 2013-06-27 2014-06-24 Verre exempt d'alcali

Country Status (5)

Country Link
JP (1) JP2016153346A (fr)
KR (1) KR20160023699A (fr)
CN (1) CN105339318A (fr)
TW (1) TW201509855A (fr)
WO (1) WO2014208524A1 (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170137031A (ko) * 2015-04-03 2017-12-12 니폰 덴키 가라스 가부시키가이샤 유리
US20180122838A1 (en) * 2015-07-03 2018-05-03 Asahi Glass Company, Limited Carrier substrate, laminate, and method for manufacturing electronic device

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2025223254A1 (fr) * 2024-04-27 2025-10-30 杨德宁 Utilisation de verre caractéristique ayant des caractéristiques de fabrication de structure de réseau précise à l'échelle atomique, faible température de zone de formation et propriétés vitreuses spécifiques

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61261232A (ja) * 1985-05-13 1986-11-19 Ohara Inc 耐火・耐熱性ガラス
JP2001348247A (ja) * 2000-05-31 2001-12-18 Asahi Glass Co Ltd 無アルカリガラス
JP2002003240A (ja) * 2000-06-19 2002-01-09 Nippon Electric Glass Co Ltd 液晶ディスプレイ用ガラス基板
JP2005320180A (ja) * 2004-05-06 2005-11-17 Central Glass Co Ltd ガラス板の熱収縮率を低減させる熱処理方法

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10114581C2 (de) * 2001-03-24 2003-03-27 Schott Glas Alkalifreies Aluminoborosilicatglas und Verwendungen
JP4977965B2 (ja) * 2005-05-02 2012-07-18 旭硝子株式会社 無アルカリガラスおよびその製造方法
EP2450319A4 (fr) * 2009-07-02 2015-01-28 Asahi Glass Co Ltd Verre exempt d'alcali et son procédé de production

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS61261232A (ja) * 1985-05-13 1986-11-19 Ohara Inc 耐火・耐熱性ガラス
JP2001348247A (ja) * 2000-05-31 2001-12-18 Asahi Glass Co Ltd 無アルカリガラス
JP2002003240A (ja) * 2000-06-19 2002-01-09 Nippon Electric Glass Co Ltd 液晶ディスプレイ用ガラス基板
JP2005320180A (ja) * 2004-05-06 2005-11-17 Central Glass Co Ltd ガラス板の熱収縮率を低減させる熱処理方法

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR20170137031A (ko) * 2015-04-03 2017-12-12 니폰 덴키 가라스 가부시키가이샤 유리
US12157697B2 (en) 2015-04-03 2024-12-03 Nippon Electric Glass Co., Ltd. Glass
KR102817508B1 (ko) * 2015-04-03 2025-06-10 니폰 덴키 가라스 가부시키가이샤 유리
US20180122838A1 (en) * 2015-07-03 2018-05-03 Asahi Glass Company, Limited Carrier substrate, laminate, and method for manufacturing electronic device
US11587958B2 (en) * 2015-07-03 2023-02-21 AGC Inc. Carrier substrate, laminate, and method for manufacturing electronic device
US12581730B2 (en) 2015-07-03 2026-03-17 AGC Inc. Carrier substrate, laminate, and method for manufacturing electronic device

Also Published As

Publication number Publication date
JP2016153346A (ja) 2016-08-25
TW201509855A (zh) 2015-03-16
CN105339318A (zh) 2016-02-17
KR20160023699A (ko) 2016-03-03

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