JP6578774B2 - Alkali-free glass - Google Patents
Alkali-free glass Download PDFInfo
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- JP6578774B2 JP6578774B2 JP2015141146A JP2015141146A JP6578774B2 JP 6578774 B2 JP6578774 B2 JP 6578774B2 JP 2015141146 A JP2015141146 A JP 2015141146A JP 2015141146 A JP2015141146 A JP 2015141146A JP 6578774 B2 JP6578774 B2 JP 6578774B2
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- 239000011521 glass Substances 0.000 title claims description 83
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 9
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 8
- 239000000758 substrate Substances 0.000 description 17
- 238000004031 devitrification Methods 0.000 description 14
- 238000010438 heat treatment Methods 0.000 description 9
- 238000000034 method Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 8
- 239000004973 liquid crystal related substance Substances 0.000 description 7
- 239000002245 particle Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 6
- 239000012535 impurity Substances 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 6
- 230000005484 gravity Effects 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 4
- 230000009477 glass transition Effects 0.000 description 4
- 239000010409 thin film Substances 0.000 description 4
- 238000006124 Pilkington process Methods 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 229910000272 alkali metal oxide Inorganic materials 0.000 description 3
- 229910021417 amorphous silicon Inorganic materials 0.000 description 3
- 238000005530 etching Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 238000002844 melting Methods 0.000 description 3
- 230000008018 melting Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- 229910001413 alkali metal ion Inorganic materials 0.000 description 2
- 230000006835 compression Effects 0.000 description 2
- 238000007906 compression Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000005224 laser annealing Methods 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 230000035939 shock Effects 0.000 description 2
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 description 1
- 235000019738 Limestone Nutrition 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- 206010040925 Skin striae Diseases 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000420 cerium oxide Inorganic materials 0.000 description 1
- 230000000052 comparative effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000001312 dry etching Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000010408 film Substances 0.000 description 1
- 239000005357 flat glass Substances 0.000 description 1
- 230000004927 fusion Effects 0.000 description 1
- 238000005816 glass manufacturing process Methods 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000006028 limestone Substances 0.000 description 1
- 239000006060 molten glass Substances 0.000 description 1
- 238000000465 moulding Methods 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- BMMGVYCKOGBVEV-UHFFFAOYSA-N oxo(oxoceriooxy)cerium Chemical compound [Ce]=O.O=[Ce]=O BMMGVYCKOGBVEV-UHFFFAOYSA-N 0.000 description 1
- 238000005191 phase separation Methods 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 229910021420 polycrystalline silicon Inorganic materials 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 239000004576 sand Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 230000006641 stabilisation Effects 0.000 description 1
- 238000011105 stabilization Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
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
- C03C3/089—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
-
- 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
- C03C3/078—Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Landscapes
- 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)
- Liquid Crystal (AREA)
Description
本発明は、各種ディスプレイ用基板ガラスやフォトマスク用基板ガラスとして好適な、アルカリ金属酸化物を実質上含有せず、フロート成形が可能な、無アルカリガラスに関する。本発明における無アルカリガラスは、実質的に(即ち不可避的不純物を除き)アルカリ成分を含有しない。 The present invention relates to an alkali-free glass that is suitable for various display substrate glasses and photomask substrate glasses and that is substantially free of alkali metal oxides and can be float-molded. The alkali-free glass in the present invention contains substantially no alkali component (that is, excluding inevitable impurities).
従来、各種ディスプレイ用基板ガラス、特に表面に金属ないし酸化物薄膜等を形成するものでは、以下に示す特性が要求されてきた。(1)アルカリ金属酸化物を含有していると、アルカリ金属イオンが薄膜中に拡散して膜特性を劣化させるため、実質的にアルカリ金属イオンを含まないこと。(2)薄膜形成工程で高温にさらされる際に、ガラスの変形およびガラスの構造安定化に伴う収縮(熱収縮)を最小限に抑えうるように、歪点が高いこと。 Conventionally, the following characteristics have been required for various display substrate glasses, particularly those in which a metal or oxide thin film is formed on the surface. (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) When exposed to a high temperature in the thin film forming process, the strain point is high so that the deformation (thermal shrinkage) associated with glass deformation and glass structural stabilization can be minimized.
(3)半導体形成に用いる各種薬品に対して充分な化学耐久性を有すること。特にSiOxやSiNxのエッチングのためのバッファードフッ酸(BHF:フッ酸とフッ化アンモニウムの混合液)、およびITOのエッチングに用いる塩酸を含有する薬液、金属電極のエッチングに用いる各種の酸(硝酸、硫酸等)、レジスト剥離液のアルカリに対して耐久性のあること。(4)内部および表面に欠点(泡、脈理、インクルージョン、ピット、キズ等)がないこと。 (3) Sufficient chemical durability against various chemicals used for semiconductor formation. In particular, 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. (4) There are no defects (bubbles, striae, inclusions, pits, scratches, etc.) inside and on the surface.
上記の要求に加えて、近年では、以下のような状況にある。
(5)ディスプレイの軽量化が要求され、ガラス自身も密度の小さいガラスが望まれる。(6)ディスプレイの軽量化が要求され、基板ガラスの薄板化が望まれる。
In addition to the above requirements, in recent years, there are the following situations.
(5) The weight reduction of the display is required, and the glass itself is desired to have a low density glass. (6) A reduction in the weight of the display is required, and a reduction in the thickness of the substrate glass is desired.
(7)これまでのアモルファスシリコン(a−Si)タイプの液晶ディスプレイに加え、若干熱処理温度の高い多結晶シリコン(p−Si)タイプの液晶ディスプレイが作製されるようになってきた(a−Si:約350℃→p−Si:350〜550℃)。(8)液晶ディスプレイ作製熱処理の昇降温速度を速くして、生産性を上げたり耐熱衝撃性を上げるために、ガラスの平均熱膨張係数の小さいガラスが求められる。 (7) In addition to the conventional amorphous silicon (a-Si) type liquid crystal display, a polycrystalline silicon (p-Si) type liquid crystal display having a slightly higher heat treatment temperature has been produced (a-Si). : About 350 ° C. → p-Si: 350 to 550 ° C.). (8) A glass having a small average thermal expansion coefficient is required to increase productivity and thermal shock resistance by increasing the temperature raising / lowering rate of the heat treatment for producing a liquid crystal display.
一方、エッチングのドライ化が進み、耐BHF性に対する要求が弱くなってきている。これまでのガラスは、耐BHF性を良くするために、B2O3を6〜10モル%含有するガラスが多く用いられてきた。しかし、B2O3は歪点を下げる傾向がある。B2O3を含有しないまたは含有量の少ない無アルカリガラスの例としては以下のようなものがある。 On the other hand, dry etching has progressed, and the demand for BHF resistance has become weaker. As the conventional glass, a glass containing 6 to 10 mol% of B 2 O 3 has been often used in order to improve the BHF resistance. However, B 2 O 3 tends to lower the strain point. Examples of non-alkali glass not containing B 2 O 3 or having a low content are as follows.
特許文献1にはB2O3を0〜3重量%含有するガラスが開示されているが、実施例の歪点が690℃以下である。 Patent Document 1 discloses a glass containing 0 to 3% by weight of B 2 O 3 , but the strain point of Examples is 690 ° C. or lower.
特許文献2にはB2O3を0〜5モル%含有するガラスが開示されているが、50〜350℃での平均熱膨張係数が50×10-7/℃を超える。 Patent Document 2 discloses a glass containing 0 to 5 mol% of B 2 O 3 , but the average coefficient of thermal expansion at 50 to 350 ° C. exceeds 50 × 10 −7 / ° C.
特許文献1、2に記載のガラスにおける問題点を解決するため、特許文献3に記載の無アルカリガラスが提案されている。特許文献3に記載の無アルカリガラスは、歪点が高く、フロート法による成形ができ、ディスプレイ用基板、フォトマスク用基板等の用途に好適であるとされている。 In order to solve the problems in the glasses described in Patent Documents 1 and 2, an alkali-free glass described in Patent Document 3 has been proposed. The alkali-free glass described in Patent Document 3 has a high strain point, can be molded by a float process, and is suitable for uses such as a display substrate and a photomask substrate.
近年、スマートフォンのような携帯用端末などの高精細小型ディスプレイでは、高品質のp−Si TFTの製造方法としてレーザーアニールによる方法が採用されているが、さらに熱収縮率を小さくするために歪点の高いガラスが求められている。また、ガラス基板の大板化、薄板化に伴い、ヤング率が高く、比弾性率(ヤング率/密度)が高いガラスが求められている。
一方、ガラス製造プロセスにおける要請から、歪点を過度に上げ過ぎないことが求められている。
In recent years, in high-definition small displays such as portable terminals such as smartphones, laser annealing has been adopted as a method for producing high-quality p-Si TFTs. High glass is demanded. Further, as the glass substrate becomes larger and thinner, a glass having a high Young's modulus and a high specific modulus (Young's modulus / density) is required.
On the other hand, due to demands in the glass manufacturing process, it is required not to raise the strain point excessively.
本発明の目的は、上記欠点を解決し、熱膨張係数が小さく、歪点が高いながらも低粘性、特にガラス粘度が102dPa・sとなる温度T2が低い無アルカリガラスを提供することにある。 The object of the present invention is to provide an alkali-free glass that solves the above-mentioned drawbacks and has a low coefficient of thermal expansion, a high strain point, and a low viscosity, particularly a low temperature T 2 at which the glass viscosity is 10 2 dPa · s. It is in.
本発明は、歪点が695℃以上であって、50〜350℃での平均熱膨張係数が43×10-7/℃以下であって、ガラス粘度が102dPa・sとなる温度T2が1690℃以下であって、酸化物基準のモル%表示で
SiO2 65〜70、
Al2O3 8〜16、
B2O3 1.5〜4未満、
MgO 0〜4.4、
CaO 0〜20、
SrO 1.5〜10、
BaO 0〜0.5を含有し、
MgO+CaOが0〜28であり、
MgO+CaO+SrO+BaO が17〜30であり、SrO/CaOが0.4〜0.8であり、
(23.5×[SiO2]+3.5×[Al2O3]−5×[B2O3])/(2.1×[MgO]+4.2×[CaO]+10×[SrO]+12×[BaO])が17以上である、無アルカリガラスを提供する。
The temperature T 2 at which the strain point is 695 ° C. or higher, the average coefficient of thermal expansion at 50 to 350 ° C. is 43 × 10 −7 / ° C., and the glass viscosity is 10 2 dPa · s. Is 1690 ° C. or lower, and SiO 2 65 to 70 in terms of mol% based on oxide,
Al 2 O 3 8-16,
B 2 O 3 less than 1.5-4,
MgO 0 to 4.4 ,
CaO 0-20,
SrO 1.5-10,
Contains BaO 0-0.5,
MgO + CaO is 0 to 28,
MgO + CaO + SrO + BaO is 17-30, SrO / CaO is 0.4-0.8,
(23.5 × [SiO 2 ] + 3.5 × [Al 2 O 3 ] −5 × [B 2 O 3 ]) / (2.1 × [MgO] + 4.2 × [CaO] + 10 × [SrO] There is provided an alkali-free glass in which + 12 × [BaO]) is 17 or more.
本発明の無アルカリガラスは、特に高歪点用途のディスプレイ用基板、フォトマスク用基板等に好適であり、また、フロート成形が容易なガラスである。本発明の無アルカリガラスは、磁気ディスク用ガラス基板としても使用できる。 The alkali-free glass of the present invention is particularly suitable for a display substrate, a photomask substrate and the like for high strain point use, and is a glass that is easy to float. The alkali-free glass of the present invention can also be used as a glass substrate for a magnetic disk.
次に各成分の組成範囲について説明する。SiO2は63%(モル%、以下特記しないかぎり同じ)未満では、歪点が充分に上がらず、かつ、熱膨張係数が増大し、密度が上昇する。そのため、SiO2は63%以上である。64%以上が好ましく、65%以上がより好ましく、66%以上がさらに好ましい。70%超では、溶解性が低下し、ガラス粘度が102dPa・sとなる温度T2や104dPa・sとなる温度T4が上昇し、失透温度が上昇する。そのため、SiO2は70%以下である。69.5%以下が好ましく、69%以下がより好ましく、68.5%以下がさらに好ましい。 Next, the composition range of each component will be described. If the SiO 2 content is less than 63% (mol%, the same unless otherwise specified), the strain point is not sufficiently increased, the thermal expansion coefficient is increased, and the density is increased. Therefore, SiO 2 is 63% or more. 64% or more is preferable, 65% or more is more preferable, and 66% or more is more preferable. In 70%, solubility decreases, the temperature T 4 which is a temperature T 2 and 10 4 dPa · s glass viscosity becomes 10 2 dPa · s is increased, the liquidus temperature rises. Therefore, SiO 2 is 70% or less. It is preferably 69.5% or less, more preferably 69% or less, and even more preferably 68.5% or less.
Al2O3はガラスの分相性を抑制し、熱膨脹係数を下げ、歪点を上げるが、8%未満ではこの効果があらわれず、また、ほかの膨張を上げる成分を増加させることになるため、結果的に熱膨張が大きくなる。そのため、Al2O3は8%以上である。9%以上、10%以上、さらに11.1%以上が好ましい。16%超ではガラスの溶解性が悪くなったり、失透温度を上昇させるおそれがある。そのため、Al2O3は16%以下である。15%以下が好ましく、14.5%以下がより好ましく、14%以下がさらに好ましい。 Al 2 O 3 suppresses the phase separation of the glass, lowers the thermal expansion coefficient, and raises the strain point. However, if it is less than 8%, this effect does not appear, and other components that increase the expansion increase. As a result, thermal expansion increases. Therefore, Al 2 O 3 is 8% or more. It is preferably 9% or more, 10% or more, and more preferably 11.1% or more. If it exceeds 16%, the solubility of the glass may be deteriorated, or the devitrification temperature may be increased. Therefore, Al 2 O 3 is 16% or less. It is preferably 15% or less, more preferably 14.5% or less, and even more preferably 14% or less.
B2O3は、ガラスの溶解反応性をよくし、また、失透温度を低下させるため1.5%以上4%未満含有する。上記の効果を得るためには、1.6%以上含有することが好ましく、1.7%以上がより好ましく、1.8%以上がさらに好ましい。しかし、多すぎると歪点が低くなり、ヤング率が小さくなるので4%未満とする。3.5%以下が好ましく、3%以下がより好ましく、2.8%以下がさらに好ましく、2.6%以下がよりさらに好ましく、2.5%以下が特に好ましい。 B 2 O 3 is contained in an amount of 1.5% to less than 4% in order to improve the melting reactivity of the glass and to lower the devitrification temperature. In order to acquire said effect, containing 1.6% or more is preferable, 1.7% or more is more preferable, and 1.8% or more is further more preferable. However, if the amount is too large, the strain point becomes low and the Young's modulus becomes small. It is preferably 3.5% or less, more preferably 3% or less, still more preferably 2.8% or less, still more preferably 2.6% or less, and particularly preferably 2.5% or less.
MgOは、アルカリ土類の中では膨張を高くせず、かつ密度を低く維持したままヤング率を上げるという特徴を有し、溶解性も向上させるため含有できる。上記の効果を得るため、含有量は好ましくは0.1%以上、より好ましくは1%以上、さらに好ましくは2%以上、特に好ましくは3%以上である。しかし、多すぎると失透温度が上昇するので8%以下とする。8%未満が好ましく、7.5%以下が好ましく、7%以下がより好ましく、6.5%以下、6%以下がさらに好ましい。 MgO has the characteristics of increasing the Young's modulus while keeping the density low while keeping the density low in alkaline earth, and can be contained because it improves solubility. In order to obtain the above effect, the content is preferably 0.1% or more, more preferably 1% or more, still more preferably 2% or more, and particularly preferably 3% or more. However, if the amount is too large, the devitrification temperature rises, so the content is made 8% or less. It is preferably less than 8%, preferably 7.5% or less, more preferably 7% or less, and further preferably 6.5% or less and 6% or less.
CaOは、アルカリ土類中では膨張を高くせず、かつ密度を低く維持したままヤング率を上げるという特徴を有し、溶解性も向上させるため含有できる。上記の効果を得るため、含有量は好ましくは0.1%以上、より好ましくは1%以上、さらに好ましくは3%以上、特に好ましくは5%以上である。しかし、多すぎると失透温度が上昇したり、CaO原料である石灰石(CaCO3)中の不純物であるリンが、多く混入するおそれがあるので20%以下とする。15%以下が好ましく、12%以下がより好ましく、10%以下がさらに好ましい。 CaO has the characteristics of increasing the Young's modulus while keeping the density low while keeping the density low in alkaline earth, and can be contained because it improves solubility. In order to obtain the above effect, the content is preferably 0.1% or more, more preferably 1% or more, still more preferably 3% or more, and particularly preferably 5% or more. However, if the amount is too large, the devitrification temperature rises or phosphorus, which is an impurity in limestone (CaCO 3 ), which is a CaO raw material, may be mixed in too much, so the content is made 20% or less. It is preferably 15% or less, more preferably 12% or less, and even more preferably 10% or less.
SrOは、ガラスの失透温度を上昇させず溶解性を向上させるが、1.5%未満ではこの効果が十分あらわれない。そのため、SrOは1.5%以上である。2%以上が好ましく、2.5%以上がより好ましく、3%以上がさらに好ましい。しかし、10%を超えると膨脹係数が増大するおそれがある。そのため、SrOは10%以下である。8%以下が好ましく、6%以下がより好ましく、5%以下がさらに好ましい。 SrO improves the solubility without increasing the devitrification temperature of the glass, but if it is less than 1.5%, this effect does not appear sufficiently. Therefore, SrO is 1.5% or more. 2% or more is preferable, 2.5% or more is more preferable, and 3% or more is more preferable. However, if it exceeds 10%, the expansion coefficient may increase. Therefore, SrO is 10% or less. 8% or less is preferable, 6% or less is more preferable, and 5% or less is more preferable.
BaOは溶解性向上のために含有できる。しかし、多すぎるとガラスの膨張と密度を過大に増加させるので0.5%以下とする。BaOは環境負荷を考慮すると、実質的に(即ち不可避的不純物を除き)、含有しないことが好ましい。 BaO can be included to improve solubility. However, too much increases the expansion and density of the glass excessively, so the content is made 0.5% or less. In consideration of environmental load, BaO is preferably not substantially contained (that is, excluding inevitable impurities).
MgO、および、CaOは失透温度を低下させる効果がある。MgOとCaOの合量は2%以上が好ましく、5%以上がより好ましく、8%以上がさらに好ましく、10%以上が特に好ましい。28%よりも多いと、熱膨張係数および比重が大きくなる。そのため、28%以下とする。24%以下が好ましく、20%以下がより好ましく、16%以下がさらに好ましい。 MgO and CaO have the effect of lowering the devitrification temperature. The total amount of MgO and CaO is preferably 2% or more, more preferably 5% or more, further preferably 8% or more, and particularly preferably 10% or more. If it exceeds 28%, the thermal expansion coefficient and the specific gravity increase. Therefore, it is 28% or less. 24% or less is preferable, 20% or less is more preferable, and 16% or less is more preferable.
MgO、CaO、SrO、BaOは、ガラス粘度が102dPa・sとなる温度T2を高くし過ぎないため、合量で12%以上とする。14%以上が好ましく、16%以上がより好ましく、17%以上がさらに好ましい。30%より多いと、歪点が低くなりやすい。そのため、合量で30%以下とする。25%以下が好ましく、22%以下がより好ましく、20%以下がさらに好ましい。 MgO, CaO, SrO and BaO do not make the temperature T 2 at which the glass viscosity becomes 10 2 dPa · s too high, so the total amount is 12% or more. It is preferably 14% or more, more preferably 16% or more, and further preferably 17% or more. If it exceeds 30%, the strain point tends to be low. Therefore, the total amount is 30% or less. 25% or less is preferable, 22% or less is more preferable, and 20% or less is more preferable.
SrO/CaOが0.33よりも小さいと、失透温度が上昇する。そのため、SrO/CaOは0.33以上とする。0.36以上が好ましく、0.4以上がより好ましく、0.45以上がさらに好ましい。0.85よりも大きいと、熱膨張係数および比重が大きくなる。そのため、SrO/CaOは0.85以下とする。0.8以下が好ましく、0.75以下がより好ましく、0.7以下がさらに好ましい。
SrO/(MgO+CaO)が0.05よりも小さいと、失透温度が上昇しやすい。0.05以上が好ましく、0.1以上がより好ましく、0.14以上がさらに好ましく、0.18以上がよりさらに好ましい。4.0よりも大きいと、熱膨張係数および比重が大きくなりやすい。4.0以下が好ましく、3.0以下がより好ましく、2.0以下がさらに好ましく、1.0以下がよりさらに好ましく、0.7以下が特に好ましい。
When SrO / CaO is smaller than 0.33, the devitrification temperature rises. Therefore, SrO / CaO is set to 0.33 or more. 0.36 or more is preferable, 0.4 or more is more preferable, and 0.45 or more is more preferable. When larger than 0.85, a thermal expansion coefficient and specific gravity will become large. Therefore, SrO / CaO is set to 0.85 or less. 0.8 or less is preferable, 0.75 or less is more preferable, and 0.7 or less is more preferable.
When SrO / (MgO + CaO) is smaller than 0.05, the devitrification temperature tends to increase. 0.05 or more is preferable, 0.1 or more is more preferable, 0.14 or more is further preferable, and 0.18 or more is more preferable. When it is larger than 4.0, the thermal expansion coefficient and specific gravity tend to be large. 4.0 or less is preferable, 3.0 or less is more preferable, 2.0 or less is more preferable, 1.0 or less is further more preferable, and 0.7 or less is especially preferable.
(23.5×[SiO2]+3.5×[Al2O3]−5×[B2O3])/(2.1×[MgO]+4.2×[CaO]+10×[SrO]+12×[BaO])が17以上であることにより、高歪点でありながら、ガラス粘度が102dPa・sとなる温度T2を高くし過ぎず、熱膨張を大きくし過ぎない。17.5以上が好ましく、18以上がより好ましく、18.5以上がさらに好ましい。 (23.5 × [SiO 2 ] + 3.5 × [Al 2 O 3 ] −5 × [B 2 O 3 ]) / (2.1 × [MgO] + 4.2 × [CaO] + 10 × [SrO] When + 12 × [BaO]) is 17 or more, the temperature T 2 at which the glass viscosity becomes 10 2 dPa · s is not excessively increased and the thermal expansion is not excessively increased while being a high strain point. 17.5 or more is preferable, 18 or more is more preferable, and 18.5 or more is more preferable.
なお、本発明のガラスは、パネル製造時にガラス表面に設ける金属ないし酸化物薄膜の特性劣化を生じさせないために、アルカリ金属酸化物を不純物レベルを超えて(すなわち実質的に)含有しない。また、ガラスのリサイクルを容易にするため、PbO、As2O3、Sb2O3は実質的に含有しないことが好ましい。 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. In order to facilitate recycling of the glass, it is preferable that PbO, As 2 O 3 and Sb 2 O 3 are not substantially contained.
さらに同様の理由で、P2O5は実質的に含有しないことが好ましい。不純物としての混入量は23モルppm以下が好ましく、18モルppm以下がより好ましく、11モルppm以下がさらに好ましく、5モルppm以下が特に好ましい。 Furthermore, for the same reason, it is preferable that P 2 O 5 is not substantially contained. The amount of impurities as impurities is preferably 23 mol ppm or less, more preferably 18 mol ppm or less, further preferably 11 mol ppm or less, and particularly preferably 5 mol ppm or less.
本発明の無アルカリガラスは上記成分以外にガラスの溶解性、清澄性、成形性(フロート成形性)を改善するため、ZnO、Fe2O3、SO3、F、Cl、SnO2を総量で1%以下、好ましくは0.9%以下、より好ましくは0.8%以下、さらに好ましくは0.7%以下含有できる。ZnOは実質的に含有しないことが好ましい。 In addition to the above components, the alkali-free glass of the present invention improves the solubility, clarity, and formability (float formability) of the glass, so ZnO, Fe 2 O 3 , SO 3 , F, Cl, and SnO 2 in total amounts. 1% or less, preferably 0.9% or less, more preferably 0.8% or less, and even more preferably 0.7% or less. It is preferable that ZnO is not substantially contained.
本発明の無アルカリガラスは上記成分以外に、ガラス溶融温度を低下させるために、またはヤング率を向上させるために、ZrO2を1%まで含有してもよい。1%超では失透温度が上昇する。0.7%以下が好ましく、0.5%以下がより好ましく、0.3%以下がさらに好ましく、実質的に含有しないことが特に好ましい。 In addition to the above components, the alkali-free glass of the present invention may contain up to 1% of ZrO 2 in order to lower the glass melting temperature or improve the Young's modulus. If it exceeds 1%, the devitrification temperature rises. 0.7% or less is preferable, 0.5% or less is more preferable, 0.3% or less is further preferable, and it is particularly preferable not to contain substantially.
本発明の無アルカリガラスは、歪点が695℃以上である。
本発明の無アルカリガラスは、歪点が695℃以上であるため、パネル製造時の熱収縮を抑えられる。また、p−Si TFTの製造方法としてレーザーアニールによる方法を適用することができる。700℃以上が好ましく、705℃以上がより好ましく、710℃以上がさらに好ましい。
本発明の無アルカリガラスは、歪点が695℃以上であるため、高歪点用途(例えば、板厚0.7mm以下、好ましくは0.5mm以下、より好ましくは0.3mm以下、さらに好ましくは0.1mm以下の薄板のディスプレイ用基板または照明用基板等に適している。
板厚0.7mm以下、さらには0.5mm以下、さらには0.3mm以下、さらには0.1mm以下の板ガラスの成形では、成形時の引き出し速度が速くなる傾向があるため、ガラスの仮想温度が上昇し、ガラスの熱収縮率が増大しやすい。この場合、高歪点ガラスであると、熱収縮率を抑制することができる。
The alkali-free glass of the present invention has a strain point of 695 ° C. or higher.
Since the alkali-free glass of the present invention has a strain point of 695 ° C. or higher, thermal shrinkage during panel production can be suppressed. Further, a laser annealing method can be applied as a method for manufacturing the p-Si TFT. 700 degreeC or more is preferable, 705 degreeC or more is more preferable, and 710 degreeC or more is further more preferable.
Since the alkali-free glass of the present invention has a strain point of 695 ° C. or higher, it has a high strain point application (for example, a plate thickness of 0.7 mm or less, preferably 0.5 mm or less, more preferably 0.3 mm or less, more preferably It is suitable for a thin display substrate or illumination substrate of 0.1 mm or less.
When forming a sheet glass having a plate thickness of 0.7 mm or less, further 0.5 mm or less, further 0.3 mm or less, and further 0.1 mm or less, the drawing speed at the time of forming tends to increase. Increases and the thermal shrinkage of the glass tends to increase. In this case, the heat shrinkage rate can be suppressed when the glass is a high strain point glass.
また本発明の無アルカリガラスは、歪点と同様の理由で、ガラス転移点が好ましくは730℃以上であり、より好ましくは740℃以上であり、さらに好ましくは750℃以上である。 The alkali-free glass of the present invention has a glass transition point of preferably 730 ° C. or higher, more preferably 740 ° C. or higher, and further preferably 750 ° C. or higher for the same reason as the strain point.
また本発明の無アルカリガラスは、50〜350℃での平均熱膨張係数が43×10-7/℃以下であり、耐熱衝撃性が大きく、パネル製造時の生産性を高くできる。本発明の無アルカリガラスにおいて、50〜350℃での平均熱膨張係数は好ましくは42×10-7/℃以下、より好ましくは41×10-7/℃以下、さらに好ましくは40×10-7/℃以下、よりさらに好ましくは39.5×10-7/℃以下、特に好ましくは39×10-7/℃以下である。 The alkali-free glass of the present invention has an average coefficient of thermal expansion at 50 to 350 ° C. of 43 × 10 −7 / ° C. or less, has high thermal shock resistance, and can increase productivity during panel production. In the alkali-free glass of the present invention, the average thermal expansion coefficient at 50 to 350 ° C. is preferably 42 × 10 −7 / ° C. or less, more preferably 41 × 10 −7 / ° C. or less, and further preferably 40 × 10 −7. / ° C. or less, more preferably 39.5 × 10 −7 / ° C. or less, particularly preferably 39 × 10 −7 / ° C. or less.
さらに、本発明の無アルカリガラスは、比重が好ましくは2.62以下であり、より好ましくは2.60以下、さらに好ましくは2.58以下、よりさらに好ましくは2.55以下である。 Furthermore, the alkali-free glass of the present invention has a specific gravity of preferably 2.62 or less, more preferably 2.60 or less, still more preferably 2.58 or less, and even more preferably 2.55 or less.
また、本発明の無アルカリガラスは、粘度ηが102ポイズ(dPa・s)となる温度T2が1690℃以下であり、好ましくは1680℃以下、より好ましくは1675℃以下、さらに好ましくは1670℃以下、よりさらに好ましくは1665℃以下になっているため溶解が比較的容易である。 In the alkali-free glass of the present invention, the temperature T 2 at which the viscosity η becomes 10 2 poise (dPa · s) is 1690 ° C. or less, preferably 1680 ° C. or less, more preferably 1675 ° C. or less, and further preferably 1670. It is relatively easy to dissolve because it is below 1 ° C, more preferably below 1665 ° C.
さらに、本発明の無アルカリガラスは粘度ηが104ポイズとなる温度T4が1310℃以下、好ましくは1305℃以下、より好ましくは1300℃以下、さらに好ましくは1300℃未満、1295℃以下、1290℃以下であり、フロート成形に適している。
また、本発明の無アルカリガラスは失透温度が、1315℃以下であることがフロート法による成形が容易となることから好ましい。好ましくは1300℃以下、1300℃未満、1290℃以下、より好ましくは1280℃以下である。また、フロート成形性やフュージョン成形性の目安となる温度T4(ガラス粘度ηが104ポイズとなる温度、単位:℃)と失透温度との差(T4−失透温度)は、好ましくは−20℃以上、−10℃以上、さらには0℃以上、より好ましくは10℃以上、さらに好ましくは20℃以上、特に好ましくは30℃以上である。
本明細書における失透温度は、白金製の皿に粉砕されたガラス粒子を入れ、一定温度に制御された電気炉中で17時間熱処理を行い、熱処理後の光学顕微鏡観察によって、ガラスの表面及び内部に結晶が析出する最高温度と結晶が析出しない最低温度との平均値である。
Furthermore, the alkali-free glass of the present invention has a temperature T 4 at which the viscosity η becomes 10 4 poise is 1310 ° C. or less, preferably 1305 ° C. or less, more preferably 1300 ° C. or less, further preferably less than 1300 ° C., 1295 ° C. or less, 1290 It is below ℃ and is suitable for float forming.
In addition, the alkali-free glass of the present invention preferably has a devitrification temperature of 1315 ° C. or lower because molding by the float method is easy. Preferably they are 1300 degrees C or less, 1300 degrees C or less, 1290 degrees C or less, More preferably, it is 1280 degrees C or less. Further, the difference (T 4 -devitrification temperature) between the temperature T 4 (the temperature at which the glass viscosity η becomes 10 4 poise, unit: ° C.) and the devitrification temperature, which is a standard of float moldability and fusion moldability, is preferable. Is −20 ° C. or higher, −10 ° C. or higher, further 0 ° C. or higher, more preferably 10 ° C. or higher, still more preferably 20 ° C. or higher, and particularly preferably 30 ° C. or higher.
In this specification, the devitrification temperature is obtained by putting crushed glass particles in a platinum dish and performing heat treatment for 17 hours in an electric furnace controlled at a constant temperature. It is an average value of the maximum temperature at which crystals are deposited inside and the minimum temperature at which crystals are not deposited.
また、本発明の無アルカリガラスは、ヤング率は78GPa以上が好ましく、79GPa以上、80GPa以上、さらに81GPa以上がより好ましく、82GPa以上がさらに好ましい。 The alkali-free glass of the present invention preferably has a Young's modulus of 78 GPa or more, 79 GPa or more, 80 GPa or more, more preferably 81 GPa or more, and further preferably 82 GPa or more.
また、本発明の無アルカリガラスは、光弾性定数が31nm/MPa/cm以下であることが好ましい。
液晶ディスプレイパネル製造工程や液晶ディスプレイ装置使用時に発生した応力によってガラス基板が複屈折性を有することにより、黒の表示がグレーになり、液晶ディスプレイのコントラストが低下する現象が認められることがある。光弾性定数を31nm/MPa/cm以下とすることにより、この現象を小さく抑えることができる。好ましくは30nm/MPa/cm以下、より好ましくは29nm/MPa/cm以下、さらに好ましくは28.5nm/MPa/cm以下、特に好ましくは28nm/MPa/cm以下である。
また、本発明の無アルカリガラスは、他の物性確保の容易性を考慮すると、光弾性定数が好ましくは23nm/MPa/cm以上、より好ましくは25nm/MPa/cm以上である。
なお、光弾性定数は円板圧縮法により測定波長546nmにて測定できる。
The alkali-free glass of the present invention preferably has a photoelastic constant of 31 nm / MPa / cm or less.
Due to the birefringence of the glass substrate due to stress generated during the manufacturing process of the liquid crystal display panel and the liquid crystal display device, a phenomenon in which the black display becomes gray and the contrast of the liquid crystal display decreases may be observed. By setting the photoelastic constant to 31 nm / MPa / cm or less, this phenomenon can be suppressed small. Preferably it is 30 nm / MPa / cm or less, More preferably, it is 29 nm / MPa / cm or less, More preferably, it is 28.5 nm / MPa / cm or less, Most preferably, it is 28 nm / MPa / cm or less.
The alkali-free glass of the present invention has a photoelastic constant of preferably 23 nm / MPa / cm or more, more preferably 25 nm / MPa / cm or more, considering the ease of securing other physical properties.
The photoelastic constant can be measured by a disk compression method at a measurement wavelength of 546 nm.
また、本発明の無アルカリガラスは、熱処理時の収縮量が小さいことが好ましい。液晶パネル製造においては、アレイ側とカラーフィルター側では熱処理工程が異なる。そのため、特に高精細パネルにおいて、ガラスの熱収縮率が大きい場合、嵌合時にドットのずれが生じるという問題がある。なお、熱収縮率の評価は次の手順で測定できる。試料をガラス転移点+100℃の温度で10分間保持した後、毎分40℃で室温まで冷却する。ここで試料の全長を計測する。その後、毎時100℃の昇温速度で600℃まで加熱し、600℃で80分間保持し、毎時100℃の降温速度で室温まで冷却し、再度試料の全長を計測する。600℃での熱処理前後での試料の収縮量と、600℃での熱処理前の試料全長との比を熱収縮率とする。上記評価方法において、熱収縮率は好ましくは200ppm以下、より好ましくは150ppm以下、さらに好ましくは100ppm以下さらには80ppm以下、特に好ましくは60ppm以下である。 Further, the alkali-free glass of the present invention preferably has a small shrinkage during heat treatment. In liquid crystal panel manufacturing, the heat treatment process is different between the array side and the color filter side. Therefore, particularly in a high-definition panel, when the thermal shrinkage rate of glass is large, there is a problem in that dot displacement occurs during fitting. The evaluation of the heat shrinkage rate can be measured by the following procedure. The sample is held at a temperature of glass transition point + 100 ° C. for 10 minutes and then cooled to room temperature at 40 ° C. per minute. Here, the total length of the sample is measured. Then, it heats to 600 degreeC with the temperature increase rate of 100 degreeC / hour, hold | maintains at 600 degreeC for 80 minutes, cools to room temperature with the temperature-fall rate of 100 degreeC / hour, and measures the full length of a sample again. The ratio between the amount of shrinkage of the sample before and after heat treatment at 600 ° C. and the total length of the sample before heat treatment at 600 ° C. is defined as the heat shrinkage rate. In the above evaluation method, the thermal shrinkage rate is preferably 200 ppm or less, more preferably 150 ppm or less, further preferably 100 ppm or less, further 80 ppm or less, and particularly preferably 60 ppm or less.
以下において例4は実施例、例12〜14は比較例、例1〜3、5〜11、15〜28は参考例である。各成分の原料を目標組成になるように調合し、白金坩堝を用いて1550〜1650℃の温度で溶解した。原料中の珪砂の粒度は、メディアン粒径D50が26μm、粒径2μm以下の粒子の割合が0.1体積%未満、粒径100μm以上の粒子の割合が0.1体積%未満であった。溶解にあたっては、白金スターラを用い撹拌しガラスの均質化を行った。次いで溶解ガラスを流し出し、板状に成形後徐冷した。 In the following, Example 4 is an Example, Examples 12 to 14 are Comparative Examples, Examples 1 to 3, 5 to 11, and 15 to 28 are Reference Examples. The raw material of each component was prepared so that it might become a target composition, and it melt | dissolved at the temperature of 1550-1650 degreeC using the platinum crucible. The particle size of the silica sand in the raw material was such that the median particle size D 50 was 26 μm, the proportion of particles having a particle size of 2 μm or less was less than 0.1% by volume, and the proportion of particles having a particle size of 100 μm or more was less than 0.1% by volume. . 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.
表1〜4には、ガラス組成(単位:モル%)と50〜350℃での熱膨脹係数(単位:×10-7/℃)、歪点(単位:℃)、ガラス転移点(単位:℃)、比重、ヤング率(GPa)(超音波法により測定)、高温粘性値として、溶解性の目安となる温度T2(ガラス粘度ηが102ポイズとなる温度、単位:℃)、とフロート成形性およびフュージョン成形性の目安となる温度T4(ガラス粘度ηが104ポイズとなる温度、単位:℃)、失透温度(単位:℃)、光弾性定数(単位:nm/MPa/cm)(円板圧縮法により測定波長546nmにて測定)、および、熱収縮率(単位:ppm)を示す。熱収縮率の評価は次の手順で行った。ガラス板試料(酸化セリウムで鏡面研磨した長さ100mm×幅10mm×厚さ1mmの試料)をガラス転移点+100℃の温度で10分間保持した後、毎分40℃で室温まで冷却する。ここで試料の全長(長さ方向)L1を計測する。その後、毎時100℃で600℃まで加熱し、600℃で80分間保持し、毎時100℃で室温まで冷却し、再度試料の全長L2を計測した。600℃での熱処理前後での全長の差(L1−L2)と、600℃での熱処理前の試料全長L1と、の比(L1−L2)/L1×106を熱収縮率とした。
なお、表1〜4中、括弧書で示した値は計算値である。
Tables 1 to 4 show the glass composition (unit: mol%), the coefficient of thermal expansion at 50 to 350 ° C (unit: × 10 -7 / ° C), the strain point (unit: ° C), and the glass transition point (unit: ° C). ), Specific gravity, Young's modulus (GPa) (measured by ultrasonic method), high temperature viscosity value, T 2 (temperature at which glass viscosity η becomes 10 2 poise, unit: ° C.) Temperature T 4 (temperature at which glass viscosity η becomes 10 4 poise, unit: ° C), devitrification temperature (unit: ° C), photoelastic constant (unit: nm / MPa / cm) ) (Measured by a disk compression method at a measurement wavelength of 546 nm) and a heat shrinkage rate (unit: ppm). Evaluation of the heat shrinkage rate was performed according to the following procedure. A glass plate sample (length 100 mm × width 10 mm × thickness 1 mm sample mirror-polished with cerium oxide) is held at a temperature of glass transition point + 100 ° C. for 10 minutes, and then cooled to room temperature at 40 ° C. per minute. Here, the total length (length direction) L1 of the sample is measured. Then, it heated to 600 degreeC at 100 degreeC / hour, hold | maintained at 600 degreeC for 80 minutes, cooled to room temperature at 100 degreeC / hour, and measured the full length L2 of the sample again. The ratio (L1−L2) / L1 × 10 6 between the difference in the total length before and after the heat treatment at 600 ° C. (L1−L2) and the total length L1 of the sample before the heat treatment at 600 ° C. was defined as the heat shrinkage rate.
In Tables 1 to 4, the values shown in parentheses are calculated values.
表から明らかなように、実施例のガラスはいずれも、歪点が695℃以上と高く、熱膨脹係数は43×10-7/℃以下と低く、ガラス粘度が102dPa・sとなる温度T2が1690℃以下であることから、ガラス製造時において、溶解性に優れる。 As is clear from the table, all the glasses of the examples have a strain point as high as 695 ° C. or higher, a thermal expansion coefficient as low as 43 × 10 −7 / ° C. or lower, and a temperature T at which the glass viscosity becomes 10 2 dPa · s. Since 2 is 1690 degrees C or less, it is excellent in solubility at the time of glass manufacture.
本発明の無アルカリガラスは、歪点が高く、フロート法による成形ができ、ディスプレイ用基板、フォトマスク用基板等の用途に好適である。また、情報記録媒体用基板、太陽電池用基板等の用途にも好適である。 The alkali-free glass of the present invention has a high strain point and can be formed by a float process, and is suitable for uses such as a display substrate and a photomask substrate. Moreover, it is suitable also for uses, such as a substrate for information recording media and a substrate for solar cells.
Claims (6)
SiO2 65〜70、
Al2O3 8〜16、
B2O3 1.5〜4未満、
MgO 0〜4.4、
CaO 0〜20、
SrO 1.5〜10、
BaO 0〜0.5を含有し、
MgO+CaOが0〜28であり、
MgO+CaO+SrO+BaO が17〜30であり、
SrO/CaOが0.4〜0.8であり、
(23.5×[SiO2]+3.5×[Al2O3]−5×[B2O3])/(2.1×[MgO]+4.2×[CaO]+10×[SrO]+12×[BaO])が17以上である、無アルカリガラス。 The strain point is 695 ° C. or higher, the average thermal expansion coefficient at 50 to 350 ° C. is 43 × 10 −7 / ° C. or lower, and the temperature T 2 at which the glass viscosity becomes 10 2 dPa · s is 1690 ° C. or lower. SiO 2 65 to 70 in terms of mol% based on oxide,
Al 2 O 3 8-16,
B 2 O 3 less than 1.5-4,
MgO 0 to 4.4 ,
CaO 0-20,
SrO 1.5-10,
Contains BaO 0-0.5,
MgO + CaO is 0 to 28,
MgO + CaO + SrO + BaO is 17-30,
SrO / CaO is 0.4 to 0.8,
(23.5 × [SiO 2 ] + 3.5 × [Al 2 O 3 ] −5 × [B 2 O 3 ]) / (2.1 × [MgO] + 4.2 × [CaO] + 10 × [SrO] + 12 × [BaO]) is 17 or more, alkali-free glass.
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