JP2004067408A - Method for producing alkali-free glass - Google Patents

Method for producing alkali-free glass Download PDF

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Publication number
JP2004067408A
JP2004067408A JP2002225918A JP2002225918A JP2004067408A JP 2004067408 A JP2004067408 A JP 2004067408A JP 2002225918 A JP2002225918 A JP 2002225918A JP 2002225918 A JP2002225918 A JP 2002225918A JP 2004067408 A JP2004067408 A JP 2004067408A
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Prior art keywords
glass
raw material
alkali
free glass
producing
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Inventor
Toshiji Narita
成田　利治
Hiroki Yamazaki
山崎　博樹
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Nippon Electric Glass Co Ltd
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Nippon Electric Glass Co Ltd
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C3/00—Glass compositions
    • C03C3/04—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
    • C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
    • C03B1/00—Preparing the batches
    • 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
    • C03C3/093—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium containing zinc or zirconium

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Glass Melting And Manufacturing (AREA)
  • Glass Compositions (AREA)
  • Liquid Crystal (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing alkali-free glass by which glass free from striae and having a high homogeneity can easily be produced. <P>SOLUTION: In the method for producing alkali-free glass where a glass raw material is prepared, fused and formed, as a silica raw material, the one having a mean particle diameter (D<SB>50</SB>) of 30 to 60 μm is used. It is more preferable that the difference between the maximum particle diameter (D<SB>99</SB>) and the mean particle diameter (D<SB>50</SB>) of the silica raw material is ≤40 μm. <P>COPYRIGHT: (C)2004,JPO

Description

【０００１】
【発明の属する技術分野】
本発明は無アルカリガラス、特に液晶ディスプレイ等の透明ガラス基板として使用される無アルカリガラスの製造方法に関するものである。
【０００２】
【従来の技術】
液晶ディスプレイ等の透明ガラス基板として、無アルカリガラスが使用されている。この種の無アルカリガラスには、耐熱性、耐薬品性等の特性の他に、表面の平滑性が高いことが要求される。
【０００３】
平滑な表面を得るために研磨を施すという方法があるが、この場合、製造コストが高くなるといった不都合がある。そこで平滑な表面を有し、研磨を必要としないガラスを製造する努力がなされている。
【０００４】
【発明が解決しようとする課題】
未研磨で平滑な表面を有するガラスを作製するためには、溶融時にガラスの均質度を高めておくことが重要となる。
【０００５】
ところが無アルカリガラスの場合、アルカリ成分を含有するガラスと異なり、原料の溶融段階でアルカリ融液によるシリカ原料粒子の溶解が起こらない。このため、シリカ原料の未溶解粒子やＳｉＯ２濃度の高いガラス質層が残存しやすく、均一なガラス融液となりにくい。そこでこのような異質な層を溶解するために、無アルカリガラスは非常に高温で溶融される。しかし高温溶融を行っても、異質な層を完全に溶解させることは難しい。
【０００６】
溶解しきれずに残った異質な層は脈理の原因となり、ガラス表面に存在する場合には平滑性を損なう。またディスプレイ基板に使用される場合、脈理は表示ムラとなって現れる。なおガラス融液の攪拌により、脈理を軽減することは可能であるが、過度の攪拌はリボイル泡を発生させるという問題を伴う。
【０００７】
本発明の目的は、脈理がなく均質度の高いガラスを容易に製造することが可能な無アルカリガラスの製造方法を提供することである。
【０００８】
【課題を解決するための手段】
シリカ原料を溶解させ易くするには、粒径の小さい原料を使用すればよいと考えられる。しかし微細な原料を使用すると、原料の凝集や飛散を招く。そこで本発明者等は種々の検討を行った結果、シリカ原料の粒度を適切な範囲に調整することにより、上記目的が達成できることを見いだし本発明として提案するものである。
【０００９】
即ち、本発明の無アルカリガラスの製造方法は、ガラス原料を調合し、溶融、成形する無アルカリガラスの製造方法において、シリカ原料として、平均粒径（Ｄ５０）３０〜６０μｍの原料を使用することを特徴とする。
【００１０】
【発明の実施の形態】
本発明に従って無アルカリガラスを製造するには、まず所望のガラス組成となるようにガラス原料を調合する。なお液晶ディスプレイ等の透明ガラス基板を製造する場合、所望の特性を得るために、例えば質量百分率でＳｉＯ２　　　４０〜７０％、Ａｌ２　Ｏ３　　　６〜２５％、Ｂ２　Ｏ３　　　５〜２０％、ＭｇＯ　０〜１０％、ＣａＯ　０〜１５％、ＢａＯ　　０〜３０％、ＳｒＯ　０〜１０％、ＺｎＯ　０〜１０％の組成を有するガラスとなるようにガラス原料調合物を調製すればよい。
また、質量百分率でＳｉＯ２　　　５５〜７０％、Ａｌ２　Ｏ３　　　１０〜２０％、Ｂ２　Ｏ３　　　９〜１５％、ＭｇＯ　０〜５％、ＣａＯ　５〜１５％、ＢａＯ　　０〜１０％、ＳｒＯ　０〜１０％、ＺｎＯ　０〜１％の組成を有するガラスとなるようにガラス原料調合物を調製すれば、さらに優れた特性を得ることができる。
【００１１】
ガラス原料を調合する際に、シリカ原料（珪砂等）として、３０〜６０μｍ、好ましくは４０〜６０μｍの平均粒径（Ｄ５０）を有するものを使用することが重要である。平均粒径（Ｄ５０）が６０μｍより大きいシリカ原料を使用すると、原料が溶解しにくくなって、未溶解粒子やＳｉＯ２濃度の高いガラス層がガラス中に残存してしまう。また３０μｍより小さいシリカ原料を使用すると、原料の凝集による未溶解が起こり同様の問題を生じ易い。また高温溶融による原料の飛散、いわゆるキャリーオーバーが生じてガラスが不均一になるという問題もある。
【００１２】
さらにシリカ原料としては、粒度分布幅が小さいことが好ましく、具体的には最大粒径（Ｄ９９）と平均粒径（Ｄ５０）の差が４０μｍ以下であることが望ましい。シリカ原料の最大粒径（Ｄ９９）と平均粒径（Ｄ５０）の差が４０μｍ以下であれば、原料粒子の表面積がより均一になるため、均一に溶解する。
【００１３】
またシリカ原料の溶解を促進する目的で、塩化物を添加することが好ましい。
塩化物は、１２００℃以上の温度域で分解、揮発して清澄ガスを発生し、その攪拌効果により異質層の形成を抑制する。また、塩化物は、その分解時にシリカを取り込んで溶解させる効果がある。塩化物の添加量は、Ｃｌ換算で０．０１〜１質量％であることが好ましい。塩化物の添加量が０．０１％以上であれば、上記効果を得ることができる。また１％以下であれば過度の揮発によるガラスの変質を起こすおそれがない。塩化物としては、ＢａＣｌ２、ＣａＣｌ２、ＳｒＣｌ２等を使用すればよい。
【００１４】
また、清澄剤としてアンチモン酸化物を使用することが可能である。つまり無アルカリガラスの溶融は非常に高温で行われるため、高温で清澄ガスを発生させることが可能な砒素酸化物が広く用いられている。しかし本発明では、適切な粒度のシリカ原料や塩化物の使用により、原料の溶解を比較的低温で行える。このため、後の清澄工程も低温化が可能となり、砒素酸化物よりも清澄ガスの放出温度が低いアンチモン酸化物を用いても、十分な清澄効果を得ることができる。アンチモン酸化物を添加する場合、その添加量は０．０５〜３質量％、特に０．１〜２質量％が適切である。なお溶融温度の低温化は、砒素酸化物の不使用による環境問題の改善だけでなく、燃料費の低減、ＣＯ２排出量の削減にも有効である。
【００１５】
また、上記以外にも、ＳｎＯ２等の清澄剤を添加することも可能である。ＳｎＯ２を添加する場合、その添加量は０．０２〜２質量％であることが好ましい。
【００１６】
次にガラス原料調合物を溶融し、成形する。ディスプレイ用途の場合、オーバーフローダウンドロー法、スロットダウンドロー法、フロート法、ロールアウト法等の方法を用いて薄板状に成形する。
【００１７】
このようにして、均質度の高い無アルカリガラスを得ることが可能になる。
【００１８】
【実施例】
以下、実施例に基づいて、本発明を説明する。
（実施例１）
表１、２は、種々の粒度を有するシリカ原料を用いて作製したガラス試料（試料ａ−１〜ｇ−１）を示している。実験には、質量百分率でＳｉＯ２　６０％、Ａｌ２　Ｏ３　１５％、Ｂ２　Ｏ３　１０％、ＣａＯ　５．５％、ＳｒＯ　６％、ＢａＯ　　２％、ＺｎＯ　０．５％からなる基本組成を有し、さらに清澄剤としてＳｂ２Ｏ３を１％添加したガラスを使用し、シリカ原料の粒度とガラスの均質度の関係を評価した。
【００１９】
【表１】

Figure 2004067408
【００２０】
【表２】
Figure 2004067408
【００２１】
各試料は次のようにして調製した。まず上記組成となるようにガラス原料を調合し、均質に混合してガラス原料調合物とした。なお塩化物は、ＢａＣｌ ２ を使用した。次いで、白金製の円錐形坩堝に充填して電気炉に入れ、１５００℃で１時間溶融した。その後に電気炉から取り出し、ガラスが固化したのを見計らってから、坩堝からガラス塊を取り外し、徐冷した。続いてガラス塊の表面層を採取し、ＳｉＯ２濃度を分析した。結果を各表に示す。なお表面層のＳｉＯ２濃度は、一般に理論組成より高い値を示すが、理論組成に近いほどガラスの均質度が高く好ましいと言える。
【００２２】
表１、２から明らかなように、平均粒径が３０〜６０μｍの範囲にあるシリカ原料を用いて作製したガラス試料は、ＳｉＯ２濃度が６３．２％以下であった。
中でも最大粒径と平均粒度の差が４０μｍ以下である試料は、ＳｉＯ２濃度が６２．８％以下であり、均質度の高いガラスが得られていることが分かる。
【００２３】
（実施例２）
実施例１と同一の基本組成を有し、さらに清澄剤としてＳｂ２Ｏ３を１質量％及び塩化物をＣｌ換算で０．５質量％添加したガラス（試料ａ−２〜ｇ−２）を用い、実施例と同様にしてシリカ原料の粒度とガラスの均質度の関係を評価した。
結果を表３、４に示す。
【００２４】
【表３】
Figure 2004067408
【００２５】
【表４】
Figure 2004067408
【００２６】
表３、４から、平均粒径が３０〜６０μｍの範囲にあるシリカ原料を用いて作製したガラス試料は、ＳｉＯ２濃度が６２．４％以下であり、中でも最大粒径平均粒度の差が４０μｍ以下である試料は、ＳｉＯ２濃度が６１．９％以下であり、均質度の高いガラスが得られていることが分かる。また塩化物を併用することにより、ＳｉＯ２濃度がより一層理論組成に近づくために好ましいことが理解できる。
【００２７】
【発明の効果】
以上説明したように、本発明の方法によれば、シリカ原料の溶解性を改善することができるために均質度の高い無アルカリガラスを製造することができる。
【００２８】
またこのようにして得られた本発明の無アルカリガラスは、表面平滑性が高く、研磨工程が不要である。また表示ムラの原因となる脈理が殆どないため、液晶ディスプレイ等の透明ガラス基板として好適である。[0001]
TECHNICAL FIELD OF THE INVENTION
The present invention relates to a method for producing an alkali-free glass, particularly an alkali-free glass used as a transparent glass substrate for a liquid crystal display or the like.
[0002]
[Prior art]
Alkali-free glass is used as a transparent glass substrate for a liquid crystal display or the like. This kind of non-alkali glass is required to have high surface smoothness in addition to properties such as heat resistance and chemical resistance.
[0003]
There is a method of performing polishing to obtain a smooth surface, but in this case, there is an inconvenience that the manufacturing cost is increased. Efforts have been made to produce glass that has a smooth surface and does not require polishing.
[0004]
[Problems to be solved by the invention]
In order to produce unpolished glass having a smooth surface, it is important to increase the homogeneity of the glass during melting.
[0005]
However, in the case of non-alkali glass, unlike the glass containing an alkali component, the silica raw material particles are not dissolved by the alkali melt in the raw material melting stage. For this reason, undissolved particles of the silica raw material and a vitreous layer having a high SiO 2 concentration are likely to remain, and it is difficult to form a uniform glass melt. Then, in order to melt such a foreign layer, the alkali-free glass is melted at a very high temperature. However, it is difficult to completely dissolve the foreign layer even by performing high-temperature melting.
[0006]
The extraneous layer that remains without being completely melted causes striae and impairs smoothness when present on the glass surface. When used for a display substrate, stria appear as display unevenness. Although it is possible to reduce striae by stirring the glass melt, excessive stirring causes a problem that reboil bubbles are generated.
[0007]
An object of the present invention is to provide a method for producing alkali-free glass, which can easily produce glass having a high degree of homogeneity without striae.
[0008]
[Means for Solving the Problems]
It is considered that a raw material having a small particle size may be used to easily dissolve the silica raw material. However, the use of fine raw materials causes aggregation and scattering of the raw materials. The present inventors have conducted various studies and found that the above object can be achieved by adjusting the particle size of the silica raw material to an appropriate range, and propose the present invention.
[0009]
That is, in the method for producing an alkali-free glass of the present invention, a raw material having an average particle size (D 50 ) of 30 to 60 μm is used as a silica raw material in the method for producing an alkali-free glass in which a glass raw material is prepared, melted and molded. It is characterized by the following.
[0010]
BEST MODE FOR CARRYING OUT THE INVENTION
In order to produce an alkali-free glass according to the present invention, first, a glass raw material is prepared so as to have a desired glass composition. In the case of producing a transparent glass substrate such as a liquid crystal display, in order to obtain the desired properties, for example SiO 2 40 to 70% in mass percentage, Al 2 O 3 6~25%, B 2 O 3 5~20%, The glass raw material mixture may be prepared so as to obtain a glass having a composition of MgO 0 to 10%, CaO 0 to 15%, BaO 0 to 30%, SrO 0 to 10%, and ZnO 0 to 10%.
Further, SiO 2 55 to 70% in mass percentage, Al 2 O 3 10~20%, B 2 O 3 9~15%, 0~5% MgO, CaO 5~15%, BaO 0~10%, SrO 0 If the glass raw material composition is prepared so as to obtain a glass having a composition of 10% to 10% and ZnO of 0% to 1%, more excellent properties can be obtained.
[0011]
In formulating the glass raw materials, as the silica raw material (silica sand, etc.), 30 to 60 m, preferably important to use those having an average particle size of 40 to 60 [mu] m (D 50). When a silica raw material having an average particle diameter (D 50 ) of more than 60 μm is used, the raw material is hardly dissolved, and undissolved particles and a glass layer having a high SiO 2 concentration remain in the glass. When a silica raw material smaller than 30 μm is used, the raw material is undissolved due to agglomeration, and the same problem is likely to occur. In addition, there is also a problem that the raw material is scattered by high-temperature melting, so-called carry-over, and the glass becomes non-uniform.
[0012]
Further, as the silica raw material, the particle size distribution width is preferably small, and specifically, the difference between the maximum particle size (D 99 ) and the average particle size (D 50 ) is desirably 40 μm or less. If the difference between the maximum particle size (D 99 ) and the average particle size (D 50 ) of the silica raw material is 40 μm or less, the surface area of the raw material particles becomes more uniform, so that the silica raw materials are uniformly dissolved.
[0013]
It is preferable to add a chloride for the purpose of accelerating the dissolution of the silica raw material.
Chloride decomposes and volatilizes in a temperature range of 1200 ° C. or more to generate a fining gas, and suppresses formation of a foreign layer by its stirring effect. Chloride has the effect of taking in and dissolving silica during its decomposition. The amount of chloride added is preferably 0.01 to 1% by mass in terms of Cl. When the amount of chloride added is 0.01% or more, the above effects can be obtained. If it is 1% or less, there is no possibility that the glass is deteriorated due to excessive volatilization. BaCl 2 , CaCl 2 , SrCl 2 or the like may be used as the chloride.
[0014]
It is also possible to use antimony oxide as a fining agent. That is, since the melting of the alkali-free glass is performed at a very high temperature, an arsenic oxide capable of generating a fining gas at a high temperature is widely used. However, in the present invention, the dissolution of the raw material can be performed at a relatively low temperature by using a silica raw material or chloride having an appropriate particle size. For this reason, it is possible to lower the temperature in the subsequent fining step, and a sufficient fining effect can be obtained even if antimony oxide having a lower fining gas emission temperature than arsenic oxide is used. When antimony oxide is added, the amount of addition is suitably 0.05 to 3% by mass, particularly 0.1 to 2% by mass. Note that lowering the melting temperature is effective not only for improvement of environmental problems due to non-use of arsenic oxide, but also for reduction of fuel cost and reduction of CO 2 emission.
[0015]
In addition, other than the above, it is also possible to add a fining agent such as SnO 2 . When adding SnO 2, the amount added is preferably 0.02 to 2 mass%.
[0016]
Next, the glass raw material mixture is melted and molded. In the case of a display use, it is formed into a thin plate using a method such as an overflow down draw method, a slot down draw method, a float method, and a roll out method.
[0017]
In this way, it is possible to obtain a highly homogeneous alkali-free glass.
[0018]
【Example】
Hereinafter, the present invention will be described based on examples.
(Example 1)
Tables 1 and 2 show glass samples (samples a-1 to g-1) produced using silica raw materials having various particle sizes. In the experiment, a basic composition consisting of 60% of SiO 2 , 15% of Al 2 O 3 , 10% of B 2 O 3 , 5.5% of CaO, 6% of SrO, 2% of BaO, and 0.5% of ZnO by mass percentage was used. Using a glass to which 1% of Sb 2 O 3 was added as a fining agent, the relationship between the particle size of the silica raw material and the homogeneity of the glass was evaluated.
[0019]
[Table 1]
Figure 2004067408
[0020]
[Table 2]
Figure 2004067408
[0021]
Each sample was prepared as follows. First, a glass raw material was prepared so as to have the above composition, and homogeneously mixed to obtain a glass raw material preparation. The chloride used was BaCl 2 . Next, it was charged into a platinum conical crucible, placed in an electric furnace, and melted at 1500 ° C. for 1 hour. Thereafter, the glass was taken out of the electric furnace, and after the solidification of the glass was observed, the glass lump was removed from the crucible and gradually cooled. Subsequently, the surface layer of the glass lump was collected and analyzed for SiO 2 concentration. The results are shown in each table. Although the SiO 2 concentration of the surface layer generally shows a higher value than the theoretical composition, it can be said that the closer to the theoretical composition, the higher the homogeneity of the glass and the more preferable.
[0022]
As is clear from Tables 1 and 2, the glass sample produced using the silica raw material having an average particle size in the range of 30 to 60 μm had a SiO 2 concentration of 63.2% or less.
Above all, the sample having a difference between the maximum particle size and the average particle size of 40 μm or less has a SiO 2 concentration of 62.8% or less, and it can be seen that a glass with high homogeneity is obtained.
[0023]
(Example 2)
Have the same basic composition as in Example 1, further glasses of Sb 2 O 3 was added 0.5 wt% of 1 wt% and chloride with Cl terms as a fining agent (sample a-2~g-2) The relationship between the particle size of the silica raw material and the homogeneity of the glass was evaluated in the same manner as in the examples.
The results are shown in Tables 3 and 4.
[0024]
[Table 3]
Figure 2004067408
[0025]
[Table 4]
Figure 2004067408
[0026]
From Tables 3 and 4, the glass samples prepared using the silica raw material having an average particle size in the range of 30 to 60 μm have a SiO 2 concentration of 62.4% or less, and among them, the difference in the maximum particle size average particle size is 40 μm. The following samples have a SiO 2 concentration of 61.9% or less, indicating that glass with high homogeneity is obtained. Also, it can be understood that the use of chloride in combination is preferable because the SiO 2 concentration further approaches the theoretical composition.
[0027]
【The invention's effect】
As described above, according to the method of the present invention, it is possible to improve the solubility of a silica raw material, and thus to manufacture alkali-free glass having a high degree of homogeneity.
[0028]
The alkali-free glass of the present invention thus obtained has a high surface smoothness and does not require a polishing step. Further, since there is almost no striae causing display unevenness, it is suitable as a transparent glass substrate for a liquid crystal display or the like.

Claims (8)

ガラス原料を調合し、溶融、成形する無アルカリガラスの製造方法において、シリカ原料として、平均粒径（Ｄ５０）３０〜６０μｍの原料を使用することを特徴とする無アルカリガラスの製造方法。A method for producing alkali-free glass, in which a glass raw material is blended, melted, and molded, wherein a raw material having an average particle diameter (D50) of 30 to 60 m is used as a silica raw material. シリカ原料の最大粒径（Ｄ９９）と平均粒径（Ｄ５０）の差が４０μｍ以下であることを特徴とする請求項１の無アルカリガラスの製造方法。Method for producing an alkali-free glass according to claim 1, wherein the difference between the maximum particle size of the silica material (D 99) and the average particle size (D 50) is 40μm or less. ガラス原料中に、塩化物を添加することを特徴とする請求項１の無アルカリガラスの製造方法。The method for producing an alkali-free glass according to claim 1, wherein a chloride is added to the glass raw material. 塩化物の添加量が、Ｃｌ換算で０．０１〜１質量％であることを特徴とする請求項３の無アルカリガラスの製造方法。The method for producing an alkali-free glass according to claim 3, wherein the amount of chloride added is 0.01 to 1% by mass in terms of Cl. ガラス原料中に、アンチモン酸化物を添加することを特徴とする請求項１の無アルカリガラスの製造方法。The method for producing an alkali-free glass according to claim 1, wherein an antimony oxide is added to the glass raw material. アンチモン酸化物の添加量が、Ｓｂ２Ｏ３換算で０．０５〜３質量％であることを特徴とする請求項５の無アルカリガラスの製造方法。The addition amount of antimony oxide, method for producing alkali-free glass according to claim 5, characterized in that 0.05 to 3% by weight Sb 2 O 3 conversion. ガラス原料が、質量百分率でＳｉＯ２　　　４０〜７０％、Ａｌ２　Ｏ３　　　６〜２５％、Ｂ２　Ｏ３　　　５〜２０％、ＭｇＯ　０〜１０％、ＣａＯ　０〜１５％、ＢａＯ　　０〜３０％、ＳｒＯ　０〜１０％、ＺｎＯ　０〜１０％の組成を有するガラスとなるように調合されていることを特徴とする請求項１の無アルカリガラスの製造方法。The glass raw material is, by mass percentage, 40 to 70% of SiO 2 , 6 to 25% of Al 2 O 3 , 5 to 20% of B 2 O 3 , 0 to 10% of MgO, 0 to 15% of CaO, 0 to 30% of BaO, 2. The method for producing alkali-free glass according to claim 1, wherein the glass is prepared so as to have a composition of 0 to 10% of SrO and 0 to 10% of ZnO. 請求項１〜７の方法により製造されてなることを特徴とする無アルカリガラス。An alkali-free glass produced by the method according to claim 1.
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