JP4739468B2 - Alkali-free glass and its clarification method - Google Patents

Alkali-free glass and its clarification method Download PDF

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Publication number
JP4739468B2
JP4739468B2 JP13008897A JP13008897A JP4739468B2 JP 4739468 B2 JP4739468 B2 JP 4739468B2 JP 13008897 A JP13008897 A JP 13008897A JP 13008897 A JP13008897 A JP 13008897A JP 4739468 B2 JP4739468 B2 JP 4739468B2
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Prior art keywords
glass
weight
alkali
free glass
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JP13008897A
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JPH10324526A (en
Inventor
学 西沢
泰昌 中尾
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AGC Inc
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Asahi Glass Co Ltd
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Classifications

    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/078Glass compositions containing silica with 40% to 90% silica, by weight containing an oxide of a divalent metal, e.g. an oxide of zinc
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/083Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound
    • C03C3/085Glass compositions containing silica with 40% to 90% silica, by weight containing aluminium oxide or an iron compound containing an oxide of a divalent metal
    • CCHEMISTRY; METALLURGY
    • C03GLASS; MINERAL OR SLAG WOOL
    • C03CCHEMICAL 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
    • C03C3/00Glass compositions
    • C03C3/04Glass compositions containing silica
    • C03C3/076Glass compositions containing silica with 40% to 90% silica, by weight
    • C03C3/11Glass compositions containing silica with 40% to 90% silica, by weight containing halogen or nitrogen

Description

【0001】
【発明の属する技術分野】
本発明は歪点の高い無アルカリガラスおよびその清澄方法に関する。
【0002】
【従来の技術】
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の薄膜等を形成させるものでは、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、膜特性を劣化させてしまうため、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ため、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)を最小限に抑えるため、高い歪点を有すること。
【0003】
(3)半導体形成に用いられ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(フッ酸+フッ化アンモニウム;BHF)、およびITOのエッチングに用いられる塩酸を含有する薬液、金属電極のエッチングに用いられる各種の酸(硝酸、硫酸等)、レジスト剥離液のアルカリに対して耐久性があること。
(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)をもたないこと。
【0004】
【発明が解決しようとする課題】
電子用途の基板ガラスでは上記(4)の品質に対する要求は厳しい。したがって、特に泡を効率的に除く目的で、従来の基板ガラスではヒ素やアンチモンを1〜2重量%添加してガラスの熔解し、清澄を行うことが多かった。ヒ素やアンチモンは高温粘性の高いガラスの清澄剤として知られている。
【0005】
しかし、ヒ素やアンチモン、特にヒ素は、環境に悪影響を与える元素であるため、ガラスのリサイクルに支障が生じるうえ、ガラスの製造工場や処理工場内でのガラスの取り扱いに注意が必要であり、かつエッチング廃液の無害化処理にも多大の設備が必要であった。
【0006】
本発明の目的は、歪点の高い無アルカリガラスの熔解において、ヒ素やアンチモンを使用しないか、使用量をごく少量としても清澄が可能なガラスの熔解時の清澄方法を提供することにある。
【0007】
【課題を解決するための手段】
本発明は、歪点が640℃以上で、重量表示で以下の成分を含有し、As23 およびSb23を実質的に含有しない無アルカリガラスを熔解時に清澄する方法であって、5.0重量%以下のSO3および2.0重量%以下のFe23からなる群から選ばれる1種以上を合量で0.01〜5.0重量%と、5.0重量%以下のClおよび5.0重量%以下のFからなる群から選ばれる1種以上を合量で0.01〜5.0重量%とを含有せしめて熔解、清澄することを特徴とする無アルカリガラスの清澄方法を提供する。
SiO2 55〜65%、
Al23 10〜18%、
23 0〜 3%(ただし、B23が3%の場合を除く)
MgO 0〜 3%、
CaO 8〜15%、
SrO 8〜15%、
BaO 0〜 2%、
MgO+CaO+SrO+BaO 16〜35
【0008】
本発明は、本発明者らが特定の清澄剤の組み合わせを用いることにより、清澄効果を高め、歪点の高い無アルカリガラスの熔解において、ヒ素やアンチモンを使用しないか、使用量を少量としても清澄できることを知見したことに基づく。
【0009】
【発明の実施の形態】
本発明では、Sb23 、SO3 、Fe23 およびSnO2 のいずれか1つ以上、ならびにFおよびClのいずれか1つ以上が有効量添加されることが必須である。有効量は無アルカリガラスの組成にも依存するが、一般的には、それぞれ合量で0.01重量%以上含有されれば効果がある。これらの清澄剤が併用されることにより、飛躍的に清澄効果が高まる。なお、添加量をあまり多くしても効果が飽和する一方、ガラスの特性に影響を与えるおそれがあるため、それぞれ合量で5.0重量%以下、好ましくは2.0重量%以下、とすることが実用的である。
【0010】
このうち、Sb23 は高温粘性の大きいガラスの清澄剤として知られており、同様の機能を持つAs23 よりも環境への悪影響が少ない。その添加量は、環境への悪影響を最小限とするため、1.5重量以下とする。1.0重量%以下とすることが好ましく、特に好ましくは不純物の程度を超えて実質的に含有されない。
【0011】
SO3 は原料に熱を加えていく際に多量の泡を発生し、かつ、泡を大きくする成分であり、建築用にしばしば用いられるソーダライムシリケートガラスの清澄剤として用いられることが多い。SO3 源は無アルカリであるかぎり、どのような塩の形で加えてもよいが、通常はアルカリ土類の硫酸塩として加える。0.01重量%以上添加することにより、清澄効果が得られる。添加量が多すぎると、泡の発生が過剰となり原料へ添加する意味がないため、実用上は5.0重量%以下、好ましくは2.0重量%以下、とされる。
【0012】
Fe23 は原料に熱を加えていく際にFe23 →Fe2 O+O2 となって酸素泡を発生する成分である。0.01重量%以上添加することにより、清澄効果が得られる。添加量をあまり多くしても効果が飽和する一方、ガラスの着色が著しくなるため、2.0重量%以下、好ましくは1.0重量%以下、とする。
【0013】
SnO2 は原料に熱を加えていく際にSnO2 →SnO+1/2・O2 となって酸素泡を発生する成分である。0.01重量%以上添加することにより、清澄効果が得られる。添加量をあまり多くしても効果が飽和する一方、ガラスの特性に影響を与えるおそれがあるため、5.0重量%以下、好ましくは2.0重量%以下、とする。
【0014】
一方、FやClも、原料に熱を加えていく際に多量の泡を発生し、かつ、泡を大きくする成分であるが、上記Sb23 、SO3 、Fe23 およびSnO2 のいずれか1つ以上と併用することにより、清澄効果が飛躍的に向上する。これらは、通常、アルカリ土類のフッ化物や塩化物として加えうる。それぞれ0.01重量%以上添加することにより、清澄効果が得られる。添加量をあまり多くしても効果が飽和する一方、ガラスの特性(特に歪点低下)に影響を与えるおそれがあるため、5.0重量%以下、好ましくは2.0重量%以下とする。
【0015】
本発明はアルカリ金属酸化物を実質的に含有しない無アルカリガラスで、歪点が640℃以上のものを対象とする。かかるガラスは、清澄可能な温度が高温域にあるため、ソーダライムシリケートガラスのように通常の芒硝による清澄ができないと考えられており、ヒ素による清澄が行われていた。
【0016】
【0017】
特に、以下のような組成は歪点が高いため、高温粘性が大きく、本発明が効果的に適用できる。すなわち、重量表示で実質的に、
SiO2 55〜65%、
Al23 10〜18%、
23 0〜 3%(ただし、B23が3%の場合を除く)、
MgO 0〜 3%、
CaO 8〜15%、
SrO 8〜15%、
BaO 0〜 2%、
MgO+CaO+SrO+BaO 16〜35%、
となるものである。
【0018】
本発明のガラスは、例えば次のような方法で製造できる。
通常使用される各成分の原料を目標成分になるように調合し、本発明の所定の清澄剤を添加したのち、これを熔解炉に連続的に投入し、1500〜1600℃に加熱して熔融する。この熔融ガラスを1200〜1500℃に保持することにより、泡ぬき(清澄)し、フロート法等により所定の板厚に成形し、徐冷後切断する。清澄時に減圧を併用してもよい。
【0019】
このようにして、製造されたガラスは、ガラス中に重量表示で
SO3 0〜5.0%、
Fe23 0〜2.0%、
SO3 +Fe23 0.01〜5.0%、
Cl 0〜5.0%、
F 0〜5.0%、
Cl+F 0.01〜5.0%、
を含有する無アルカリガラスである。
【0020】
【実施例】
表に本発明の実施例を示す。
SiO2 、Al23 、B23 、MgO、CaO、SrOおよびBaOは工業用原料を用いて合計で100重量部となるように調合し、Sb23 、SO3 、Cl、F、Fe23 およびSnO2 (清澄剤)はこれに上乗せする形で加えた。
【0021】
表中に示した「泡数(1)」は調合原料バッチ(500g)を白金坩堝に入れ、1600℃で1時間熔解、徐冷後のガラス表面から1cm下から2cm下までの間にある泡の数(個/g)を示す。また、「泡数(2)」には調合原料バッチ(500g)を白金坩堝にいれ1600℃で30分熔解後、通常のスクリュー状のスターラを用いて20rpmで撹拌しながら20分熔融、徐冷後のガラス表面から1cm下から2cm下までの間にある泡の数(個/g)を示す。
【0022】
表にはガラスの50〜350℃での平均の熱膨張係数と歪点と耐塩酸性も示す。例1〜16は参考例、例17は実施例、例18〜36は比較例である。
【0023】
実施例のガラスは泡数(1)に示すように熔融初期に泡の残りと、泡数(2)) に示すように撹拌したときの泡の熔け残り、撹拌リボイル(再沸)泡がいずれも少なく、また、ガラスの均一性も良く、高品質なガラスの製造に適当であることがわかる。
また、これらの清澄剤は熱膨張係数、歪点、耐塩酸性に影響を与えず、好ましい清澄剤であるといえる。
【0024】
また、SO3 、Cl、Fの量は添加量で示しているが、これらガラスを熔融する間に一部揮散してしまうため残存量はこれより少なくなる。この残存量はガラス組成に依存する。例えば、例3では、0.2%のF、0.2%のCl、0.05%のSO3 などの残存がある。
【0025】
【表1】

Figure 0004739468
【0026】
【表2】
Figure 0004739468
【0027】
【表3】
Figure 0004739468
【0028】
【表4】
Figure 0004739468
【0029】
【表5】
Figure 0004739468
【0030】
【発明の効果】
本発明によるガラスは、人体および地球環境を悪化させずに、高品質なガラス基板(ディスプレイ用基板、フォトマスク基板、TFTタイプのディスプレイ基板等)、およびその製造方法として好適である。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to an alkali-free glass having a high strain point and a clarification method thereof.
[0002]
[Prior art]
Conventionally, various display substrate glasses, particularly those in which a thin film of metal or oxide is formed on the surface, have been required to have the following characteristics.
(1) If an alkali metal oxide is contained, the alkali metal ions diffuse into the thin film and deteriorate the film characteristics, so that the alkali metal ions are not substantially contained.
(2) Since it is exposed to a high temperature in the thin film formation process, it has a high strain point in order to minimize the shrinkage (thermal shrinkage) associated with glass deformation and glass structural stabilization.
[0003]
(3) Sufficient chemical durability against various chemicals used for semiconductor formation. In particular, buffered hydrofluoric acid (hydrofluoric acid + ammonium fluoride; BHF) 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.) and resist stripper alkali.
(4) No defects (bubbles, striae, inclusions, pits, scratches, etc.) inside and on the surface.
[0004]
[Problems to be solved by the invention]
In the case of substrate glass for electronic use, the demand for the quality of (4) is severe. Therefore, for the purpose of efficiently removing bubbles, conventional substrate glasses often add 1 to 2% by weight of arsenic or antimony to melt and clarify the glass. Arsenic and antimony are known as high-viscosity glass fining agents.
[0005]
However, since arsenic and antimony, especially arsenic, are elements that adversely affect the environment, glass recycling is hindered, and attention must be paid to the handling of glass in glass manufacturing plants and processing plants, and A large amount of equipment was also required for the detoxification treatment of the etching waste liquid.
[0006]
It is an object of the present invention to provide a clarification method at the time of melting glass that can be clarified even if the amount of the arsenic or antimony is not used or the amount used is very small in melting of alkali-free glass having a high strain point.
[0007]
[Means for Solving the Problems]
The present invention is a method for refining an alkali-free glass at the time of melting having a strain point of 640 ° C. or higher, containing the following components by weight, and substantially free of As 2 O 3 and Sb 2 O 3 : A total amount of at least one selected from the group consisting of 5.0 wt% or less SO 3 and 2.0 wt% or less Fe 2 O 3 is 0.01 to 5.0 wt%, and 5.0 wt% One or more selected from the group consisting of the following Cl and 5.0% by weight or less F is contained in a total amount of 0.01 to 5.0% by weight, and melted and clarified. Provide a method for clarifying glass.
SiO 2 55~65%,
Al 2 O 3 10-18%,
B 2 O 3 0 to 3% (except when B 2 O 3 is 3%)
MgO 0 to 3%,
CaO 8-15%,
SrO 8-15%,
BaO 0-2%,
MgO + CaO + SrO + BaO 16-35 %
[0008]
The present invention improves the clarification effect by using a combination of specific clarifiers by the present inventors, and does not use arsenic or antimony in the melting of alkali-free glass having a high strain point, even if the amount used is small. Based on finding out that it can be clarified.
[0009]
DETAILED DESCRIPTION OF THE INVENTION
In the present invention, it is essential to add an effective amount of any one or more of Sb 2 O 3 , SO 3 , Fe 2 O 3 and SnO 2 , and any one or more of F and Cl. The effective amount depends on the composition of the alkali-free glass, but in general, it is effective if the total amount is 0.01% by weight or more. By using these fining agents in combination, the fining effect is dramatically increased. In addition, although the effect is saturated even if the addition amount is excessively large, there is a possibility that the properties of the glass may be affected. Therefore, the total amount is 5.0% by weight or less, preferably 2.0% by weight or less. It is practical.
[0010]
Among these, Sb 2 O 3 is known as a glass refining agent having a high temperature viscosity and has less adverse effects on the environment than As 2 O 3 having the same function. The amount added is 1.5 wt. Or less in order to minimize adverse effects on the environment. The content is preferably 1.0% by weight or less, particularly preferably not substantially contained beyond the level of impurities.
[0011]
SO 3 is a component that generates a large amount of foam when heat is applied to the raw material and enlarges the foam, and is often used as a fining agent for soda lime silicate glass often used for construction. The SO 3 source may be added in any salt form as long as it is alkali-free, but is usually added as an alkaline earth sulfate. A clarification effect can be obtained by adding 0.01% by weight or more. If the amount added is too large, the generation of bubbles becomes excessive and there is no point in adding to the raw material, so that it is practically 5.0% by weight or less, preferably 2.0% by weight or less.
[0012]
Fe 2 O 3 is a component that generates oxygen bubbles as Fe 2 O 3 → Fe 2 O + O 2 when heat is applied to the raw material. A clarification effect can be obtained by adding 0.01% by weight or more. Even if the addition amount is too large, the effect is saturated, but the coloring of the glass becomes remarkable, so that it is 2.0% by weight or less, preferably 1.0% by weight or less.
[0013]
SnO 2 is a component that generates oxygen bubbles as SnO 2 → SnO + 1/2 · O 2 when heat is applied to the raw material. A clarification effect can be obtained by adding 0.01% by weight or more. Even if the addition amount is too large, the effect is saturated, but there is a possibility of affecting the properties of the glass.
[0014]
On the other hand, F and Cl are components that generate a large amount of bubbles and increase the bubbles when heat is applied to the raw material, but the above-mentioned Sb 2 O 3 , SO 3 , Fe 2 O 3 and SnO 2. By using together with any one or more of the above, the clarification effect is dramatically improved. These can usually be added as alkaline earth fluorides or chlorides. A clarification effect is obtained by adding 0.01% by weight or more of each. Even if the addition amount is too large, the effect is saturated, but there is a possibility of affecting the characteristics of the glass (especially lowering of the strain point), so it is 5.0% by weight or less, preferably 2.0% by weight or less.
[0015]
The present invention is a non-alkali glass that does not substantially contain an alkali metal oxide and has a strain point of 640 ° C. or higher. Such glass has a clarification temperature in a high temperature range, and it is considered that clarification with ordinary sodium sulfate cannot be performed unlike soda lime silicate glass, and clarification with arsenic has been performed.
[0016]
[0017]
In particular, the set formed as follows for the high strain point, increase high temperature viscosity, the present invention can be effectively applied. That is, in weight display,
SiO 2 55~65%,
Al 2 O 3 10-18%,
B 2 O 3 0 to 3% (except when B 2 O 3 is 3%),
MgO 0 to 3%,
CaO 8-15%,
SrO 8-15%,
BaO 0-2%,
MgO + CaO + SrO + BaO 16-35 %,
It will be.
[0018]
The glass of the present invention can be produced, for example, by the following method.
The raw materials of each component that are usually used are prepared so as to become target components, and after adding the predetermined clarifying agent of the present invention, this is continuously charged into a melting furnace and heated to 1500 to 1600 ° C. for melting. To do. By holding this molten glass at 1200 to 1500 ° C., bubbles are removed (clarified), formed into a predetermined plate thickness by a float method or the like, and then cooled and cut. You may use decompression together at the time of clarification.
[0019]
In this way, the produced glass is SO 3 0 to 5.0% by weight in the glass,
Fe 2 O 3 0-2.0%,
SO 3 + Fe 2 O 3 0.01 to 5.0%,
Cl 0-5.0%,
F 0-5.0%,
Cl + F 0.01-5.0%,
Ru alkali-free glass der containing.
[0020]
【Example】
Examples of the present invention are shown in the table.
SiO 2 , Al 2 O 3 , B 2 O 3 , MgO, CaO, SrO and BaO are prepared using industrial raw materials to a total of 100 parts by weight, and Sb 2 O 3 , SO 3 , Cl, F Fe 2 O 3 and SnO 2 (fining agent) were added on top of this.
[0021]
“Number of bubbles (1)” shown in the table is a bubble between 1 cm to 2 cm below the glass surface after putting the blended raw material batch (500 g) into a platinum crucible and melting at 1600 ° C. for 1 hour. Number (pieces / g). In addition, in “Number of bubbles (2)”, the raw material batch (500 g) is placed in a platinum crucible and melted at 1600 ° C. for 30 minutes, and then melted and slowly cooled for 20 minutes while stirring at 20 rpm using a normal screw-shaped stirrer. The number of bubbles (pieces / g) between 1 cm below and 2 cm below the subsequent glass surface is shown.
[0022]
The table also shows the average thermal expansion coefficient, strain point, and hydrochloric acid resistance of glass at 50 to 350 ° C. Examples 1 to 16 are reference examples, Example 17 is an example, and Examples 18 to 36 are comparative examples.
[0023]
In the glass of the example, the remaining foam at the initial stage of melting as indicated by the number of bubbles (1), the remaining melted bubbles when stirred as indicated by the number of bubbles (2)), and the stirring reboil (re-boiling) bubbles In addition, it is understood that the glass has good uniformity and is suitable for the production of high-quality glass.
These fining agents do not affect the thermal expansion coefficient, strain point, and hydrochloric acid resistance, and can be said to be preferable fining agents.
[0024]
Moreover, although the amount of SO 3 , Cl, and F is shown as an addition amount, the remaining amount is smaller than this because some of the glass is volatilized during melting. This remaining amount depends on the glass composition. For example, in Example 3, there are residuals of 0.2% F, 0.2% Cl, 0.05% SO 3 and the like.
[0025]
[Table 1]
Figure 0004739468
[0026]
[Table 2]
Figure 0004739468
[0027]
[Table 3]
Figure 0004739468
[0028]
[Table 4]
Figure 0004739468
[0029]
[Table 5]
Figure 0004739468
[0030]
【The invention's effect】
The glass according to the present invention is suitable as a high-quality glass substrate (display substrate, photomask substrate, TFT type display substrate, etc.) and a manufacturing method thereof without deteriorating the human body and the global environment.

Claims (4)

歪点が640℃以上で、重量表示で以下の成分を含有し、As23 およびSb23を実質的に含有しない無アルカリガラスを熔解時に清澄する方法であって、5.0重量%以下のSO3および2.0重量%以下のFe23からなる群から選ばれる1種以上を合量で0.01〜5.0重量%と、5.0重量%以下のClおよび5.0重量%以下のFからなる群から選ばれる1種以上を合量で0.01〜5.0重量%とを含有せしめて熔解、清澄することを特徴とする無アルカリガラスの清澄方法:
SiO2 55〜65%、
Al23 10〜18%、
23 0〜 3%(ただし、B23が3%の場合を除く)
MgO 0〜 3%、
CaO 8〜15%、
SrO 8〜15%、
BaO 0〜 2%、
MgO+CaO+SrO+BaO 16〜35%。
A method of refining an alkali-free glass having a strain point of 640 ° C. or higher and containing the following components by weight and substantially free of As 2 O 3 and Sb 2 O 3 at the time of melting: 5.0 wt. % Of SO 3 and 2.0% by weight or less of Fe 2 O 3 selected from the group consisting of 0.01 to 5.0% by weight, Cl and 5.0% by weight or less of Cl and A method for clarifying alkali-free glass, comprising melting and refining by adding at least one selected from the group consisting of 5.0 wt% or less F and 0.01 to 5.0 wt% in total. :
SiO 2 55~65%,
Al 2 O 3 10-18%,
B 2 O 3 0 to 3% (except when B 2 O 3 is 3%)
MgO 0 to 3%,
CaO 8-15%,
SrO 8-15%,
BaO 0-2%,
MgO + CaO + SrO + BaO 16-35%.
Clを0.01〜2.0重量%含有せしめる請求項1記載の無アルカリガラスの清澄方法。The method for clarifying alkali-free glass according to claim 1 , wherein Cl is contained in an amount of 0.01 to 2.0% by weight. SO3 を0.01〜2.0重量%含有せしめる請求項1または記載の無アルカリガラスの清澄方法。Refining method of the alkali-free glass according to claim 1 or 2 SO 3 allowed to contain 0.01 to 2.0 wt%. ガラス中に、重量表示で
SiO2 55〜65%、
Al23 10〜18%、
23 0〜 3%(ただし、B23が3%の場合を除く)、
MgO 0〜 3%、
CaO 8〜15%、
SrO 8〜15%、
BaO 0〜 2%、
MgO+CaO+SrO+BaO 16〜35%
SO3 0〜5.0%、
Fe23 0〜2.0%、
SO3 +Fe23 0.01〜5.0%、
Cl 0〜5.0%、
F 0〜5.0%、
Cl+F 0.01〜5.0%、
を含有する無アルカリガラス。
In the glass, SiO 2 55-65% by weight,
Al 2 O 3 10-18%,
B 2 O 3 0 to 3% (except when B 2 O 3 is 3%),
MgO 0 to 3%,
CaO 8-15%,
SrO 8-15%,
BaO 0-2%,
MgO + CaO + SrO + BaO 16-35%
SO 3 0-5.0%,
Fe 2 O 3 0-2.0%,
SO 3 + Fe 2 O 3 0.01 to 5.0%,
Cl 0-5.0%,
F 0-5.0%,
Cl + F 0.01-5.0%,
Alkali-free glass containing
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Families Citing this family (51)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
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