JP5359824B2 - Clarification method of alkali-free glass - Google Patents
Clarification method of alkali-free glass Download PDFInfo
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本発明は歪点の高い無アルカリガラスの清澄方法に関する。 The present invention relates to a method for refining alkali-free glass having a high strain point.
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。
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.
（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。
(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.
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質量％添加してガラスを熔解し、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。 In the case of substrate glass for electronic use, the demand for the quality (4) is severe. Therefore, for the purpose of efficiently removing bubbles, the conventional substrate glass is often clarified by adding 1 to 2% by mass of arsenic or antimony to melt the glass. Arsenic and antimony are known as high-viscosity glass fining agents.
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。 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.
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。 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.
本発明は、歪点が６４０℃以上でＡｓ2Ｏ3が０．５質量％以下の無アルカリガラスを熔解時に清澄する方法であって、１．５質量％以下のＳｂ2Ｏ3、５．０質量％以下のＳＯ3、２．０質量％以下のＦｅ2Ｏ3および５．０質量％以下のＳｎＯ2からなる群から選ばれる１種以上を合量で０．０１質量％以上と、５．０質量％以下のＣｌおよび５．０質量％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質量％以上とを含有せしめて熔解、清澄することを特徴とする清澄方法を提供する。 The present invention is a method for refining an alkali-free glass having a strain point of 640 ° C. or higher and an As 2 O 3 content of 0.5% by mass or less during melting, which is 1.5% by mass or less of Sb 2 O 3 , 5. One or more selected from the group consisting of 0 mass% or less SO 3 , 2.0 mass% or less Fe 2 O 3 and 5.0 mass% or less SnO 2 in a total amount of 0.01 mass% or more , One or more selected from the group consisting of Cl of 5.0% by mass or less and F of 5.0% by mass or less are contained in a total amount of 0.01% by mass or more and melted and clarified. Provide clarification method.
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。 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.
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。 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.
本発明では、Ｓｂ2Ｏ3、ＳＯ3、Ｆｅ2Ｏ3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質量％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質量％以下、好ましくは２．０質量％以下、とすることが実用的である。 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 generally it is effective if the total amount is 0.01% by mass or more. By using these fining agents in combination, the fining effect is dramatically increased. In addition, although an effect will be saturated even if it adds too much, since there exists a possibility of affecting the characteristic of glass, it is set as 5.0 mass% or less, respectively preferably 2.0 mass% or less in total amount, respectively. It is practical.
このうち、Ｓｂ2Ｏ3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Ａｓ2Ｏ3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質量以下とする。１．０質量％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。 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 mass or less in order to minimize adverse effects on the environment. It is preferable to set it as 1.0 mass% or less, Most preferably, it does not contain substantially exceeding the grade of an impurity.
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質量％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質量％以下、好ましくは２．０質量％以下、とされる。 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 mass 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 mass or less, preferably 2.0% by mass or less.
Ｆｅ2Ｏ3は原料に熱を加えていく際にＦｅ2Ｏ3→Ｆｅ2Ｏ＋Ｏ2となって酸素泡を発生する成分である。０．０１質量％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質量％以下、好ましくは１．０質量％以下、とする。 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 mass or more. Even if the addition amount is too large, the effect is saturated, but the coloration of the glass becomes remarkable.
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質量％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質量％以下、好ましくは２．０質量％以下、とする。 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 mass 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, so it is 5.0% by mass or less, preferably 2.0% by mass or less.
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Ｓｂ2Ｏ3、ＳＯ3、Ｆｅ2Ｏ3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質量％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質量％以下、好ましくは２．０質量％以下とする。 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. By adding 0.01% by mass or more of each, a clarification effect can be obtained. Even if the addition amount is excessively large, the effect is saturated, but on the other hand, there is a possibility of affecting the properties of glass (especially strain point reduction).
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。 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.
具体的には、質量表示で実質的に以下のような組成が例示できる。
ＳｉＯ2 ４０〜８０％、
Ａｌ2Ｏ3 ０〜３５％、
Ｂ2Ｏ3 ０〜２５％、
ＭｇＯ ０〜３０％、
ＣａＯ ０〜３０％、
ＳｒＯ ０〜３０％、
ＢａＯ ０〜３０％、
ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ １〜５０％。
Specifically, the following composition can be exemplified substantially in terms of mass.
SiO 2 40~80%,
Al 2 O 3 0-35%,
B 2 O 3 0-25%,
MgO 0-30%,
CaO 0-30%,
SrO 0-30%,
BaO 0-30%,
MgO + CaO + SrO + BaO 1-50%.
特に、以下のような２種類の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、質量表示で実質的に、
ＳｉＯ2 ５５〜６５％、
Ａｌ2Ｏ3 １０〜１８％、
Ｂ2Ｏ3 ０〜 ３％、
ＭｇＯ ０〜 ３％、
ＣａＯ ８〜１５％、
ＳｒＯ ８〜１５％、
ＢａＯ ０〜 ２％、
ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ １６〜３５％、
または、
ＳｉＯ2 ５８．４〜６５．０％、
Ａｌ2Ｏ3 １５．３〜２２．０％、
Ｂ2Ｏ3 ５．０〜１２．０％、
ＭｇＯ ０〜 ６．０％、
ＣａＯ ０〜 ７．０％、
ＳｒＯ ４．０〜１２．０％、
ＢａＯ ０〜 ２．０％、
ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ
９．０〜１８．０％、
となるものである。
In particular, the following two types of compositions have a high strain point and thus have a high temperature viscosity, and the present invention can be effectively applied. That is, in mass display,
SiO 2 55~65%,
Al 2 O 3 10-18%,
B 2 O 3 0 to 3%,
MgO 0 to 3%,
CaO 8-15%,
SrO 8-15%,
BaO 0-2%,
MgO + CaO + SrO + BaO 16 to 35%,
Or
SiO 2 58.4~65.0%,
Al 2 O 3 15.3 to 22.0%,
B 2 O 3 5.0 to 12.0%,
MgO 0 to 6.0%,
CaO 0 to 7.0%,
SrO 4.0-12.0%,
BaO 0-2.0%,
MgO + CaO + SrO + BaO
9.0 to 18.0%,
It will be.
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。
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.
このようにして、製造されたガラスは、ガラス中に質量表示で
Ａｓ2Ｏ3 ０〜０．５％、
Ｓｂ2Ｏ3 ０〜１．５％、
ＳＯ3 ０〜５．０％、
Ｆｅ2Ｏ3 ０〜２．０％、
ＳｎＯ2 ０〜５．０％、
Ｓｂ2Ｏ3＋ＳＯ3＋Ｆｅ2Ｏ3＋ＳｎＯ2
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。ヒ素、アンチモンは実質的に含有されないことが好ましい。
Thus, the produced glass is As 2 O 3 0-0.5% by mass display in glass,
Sb 2 O 3 0-1.5%,
SO 3 0-5.0%,
Fe 2 O 3 0-2.0%,
SnO 2 0-5.0%,
Sb 2 O 3 + SO 3 + Fe 2 O 3 + SnO 2
0.01-5.0%,
Cl 0-5.0%,
F 0-5.0%,
Cl + F 0.01-5.0%,
Is an alkali-free glass. It is preferable that arsenic and antimony are not substantially contained.
表に本発明の実施例を示す。
ＳｉＯ2、Ａｌ2Ｏ3、Ｂ2Ｏ3、ＭｇＯ、ＣａＯ、ＳｒＯおよびＢａＯは工業用原料を用いて合計で１００質量部となるように調合し、Ｓｂ2Ｏ3、ＳＯ3、Ｃｌ、Ｆ、Ｆｅ2Ｏ3およびＳｎＯ2（清澄剤）はこれに上乗せする形で加えた。
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 mass, and Sb 2 O 3 , SO 3 , Cl, F Fe 2 O 3 and SnO 2 (fining agent) were added on top of this.
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。 “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.
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１〜１７は実施例、例１８は参考例、例１９〜３７は比較例である。特に例１〜７と例２３〜２６とを比較することにより、清澄剤の併用の効果がわかる。 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 17 are Examples, Example 18 is a Reference Example, and Examples 19 to 37 are Comparative Examples. In particular, by comparing Examples 1 to 7 and Examples 23 to 26, the effect of the combined use of the clarifying agent can be seen.
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。
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 reboiling (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.
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。 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.
Claims (5)
ＳｉＯ2 ５５〜６５％、
Ａｌ2Ｏ3 １０〜１８％、
Ｂ2Ｏ3 ０〜３％、
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, an As 2 O 3 content of 0.5% by mass or less and containing the following components in terms of mass at the time of melting: 1.5% by mass One or more selected from the group consisting of the following Sb 2 O 3 , 5.0 mass% or less SO 3 , 2.0 mass% or less Fe 2 O 3 and 5.0 mass% or less SnO 2 are combined. 0.01 mass% or more, and 5.0 mass% or less of Cl and 5.0 mass% or less of one or more selected from the group consisting of F are contained in a total amount of 0.01 mass% or more. A non-alkali glass clarification method characterized by melting at 1500 to 1600 ° C and clarification by holding at 1200 to 1500 ° C.
SiO 2 55~65%,
Al 2 O 3 10-18%,
B 2 O 3 0-3%,
MgO 0-3%,
CaO 8-15%,
SrO 8-15%,
BaO 0-2%,
MgO + CaO + SrO + BaO 16 to 35%
ＳｉＯ2 ５８．４〜６５．０％、
Ａｌ2Ｏ3 １５．３〜２２．０％、
Ｂ2Ｏ3 ５．０〜１２．０％、
ＭｇＯ ０〜 ６．０％、
ＣａＯ ０〜 ７．０％、
ＳｒＯ ４．０〜１２．０％、
ＢａＯ ０〜 ２．０％、
ＭｇＯ＋ＣａＯ＋ＳｒＯ＋ＢａＯ ９．０〜１８．０％ A method of refining alkali-free glass having a strain point of 640 ° C. or higher, an As 2 O 3 content of 0.5% by mass or less, and comprising the following components in terms of mass, and 1.5% by mass or less 1 or more selected from the group consisting of Sb 2 O 3 , 5.0 mass% or less SO 3 , 2.0 mass% or less Fe 2 O 3 and 5.0 mass% or less SnO 2 in a total amount. 1500% by adding 0.01% by mass or more and one or more selected from the group consisting of 0.01% by mass or more and 5.0% by mass Cl or less and 5.0% by mass or less F. A method for clarification of alkali-free glass, which is clarified by melting at ˜1600 ° C. and holding at 1200 to 1500 ° C.
SiO 2 58.4~65.0%,
Al 2 O 3 15.3 to 22.0%,
B 2 O 3 5.0 to 12.0%,
MgO 0 to 6.0%,
CaO 0 to 7.0%,
SrO 4.0-12.0%,
BaO 0-2.0%,
MgO + CaO + SrO + BaO 9.0-18.0%
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| JP5709301B2 (en) * | 2010-10-26 | 2015-04-30 | Hoya株式会社 | Method for producing fluorophosphate optical glass and method for producing optical element |
| WO2012137780A1 (en) * | 2011-04-08 | 2012-10-11 | 旭硝子株式会社 | Non-alkali glass for substrates and process for manufacturing non-alkali glass for substrates |
| JP5816372B2 (en) * | 2011-09-02 | 2015-11-18 | エルジー・ケム・リミテッド | Alkali-free glass and method for producing the same |
| WO2013032291A2 (en) * | 2011-09-02 | 2013-03-07 | 주식회사 엘지화학 | Alkali-free glass and method for manufacturing same |
| JP5808494B2 (en) | 2011-09-02 | 2015-11-10 | エルジー・ケム・リミテッド | Alkali-free glass and method for producing the same |
| WO2013032290A2 (en) * | 2011-09-02 | 2013-03-07 | 주식회사 엘지화학 | Alkali-free glass and method for manufacturing same |
| JP5798688B2 (en) | 2011-09-02 | 2015-10-21 | エルジー・ケム・リミテッド | Alkali-free glass and method for producing the same |
| WO2013032292A2 (en) * | 2011-09-02 | 2013-03-07 | 주식회사 엘지화학 | Alkali-free glass and method for manufacturing same |
| JPWO2013161903A1 (en) * | 2012-04-27 | 2015-12-24 | 旭硝子株式会社 | Alkali-free glass and method for producing the same |
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| JPS6296345A (en) * | 1985-10-19 | 1987-05-02 | エルンスト ライツ ヴエツラ− ゲセルシヤフトミツト ベシユレンクテル ハフツング | Optical fluophosphate glass with extraordinary positive partial dispersion and manufacture |
| JP3332493B2 (en) * | 1993-09-02 | 2002-10-07 | キヤノン株式会社 | Glass melting furnace |
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| EP0714862B1 (en) * | 1994-11-30 | 1999-03-31 | Asahi Glass Company Ltd. | Alkali-free glass and flat panel display |
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