JP2003300750A - Glass composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To solve the problem of refining in multi-component oxide glass. <P>SOLUTION: A glass composition comprises, as a main constituent, multi- component oxides produced by fusing glass raw materials, wherein at least one component selected from among helium and neon is contained in an amount of 0.01 to 2 μL/g (0°C, 1 atm). <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a glass composition, and more particularly, it relates to a glass composition capable of reducing bubble defects in a glass product and improving homogeneity of the glass product by reducing dissolved gas in the glass. It is a thing.

[0002]

2. Description of the Related Art In the production of glass products, one of the most important issues that have been addressed for many years is to completely eliminate residual bubbles in glass, which is a defect in glass products.
There is a realization of extremely homogeneous glass production. Although various inventions have been made to achieve this object, they satisfy the preconditions of stable production and supply of high-quality glass inexpensively required by industry and consumers, and are easy for glass manufacturers. No such method has yet been found.

Further, as a method for producing glass products, a method of producing from a solid such as a gas phase reaction method or a sol-gel method is also recognized, but generally, an industrial production method for producing a large amount of glass products. As the glass raw material, a method of manufacturing a glass product by using an inorganic compound as a main raw material and melting it at a high temperature is most often adopted. In this manufacturing method by melting, the means for removing bubbles from the molten glass is roughly divided into a chemical method and a physical method, and as a typical method of the former, there is a method of adding a fining agent to the glass raw material, and the latter. As a typical method, there is a method of depressurizing and vacuum degassing molten glass.

With respect to the former, in particular, in the recent supply of a wide variety of glass products, by adding a trace amount of a fining agent to the glass raw material, the glass raw material is heated at a high temperature to cause an oxidation-reduction reaction in the molten glass. A method of foaming and removing carbon dioxide gas generated at the time of melting, bubbles entrained in the raw material, nitrogen mixed in at the time of melting the glass by floating is generally performed. The feature of this method is that it is necessary to pay attention to the glass melting temperature, the control of the molten glass flow and the segregation of the fining agent in the glass raw material, but if a fining agent with a stable fining effect can be selected, it can be continued relatively easily. There is a large number of cases in which a refining method suitable for production by such a melting method is adopted because mass production can be carried out.

Among them, what was frequently adopted was to add arsenic, which has a necessary and sufficient refining effect by adding a trace amount, into glass as an oxide. , Voices of problems pointed out in terms of environment. Therefore, it is urgent to stop the use of arsenic as a fining agent, or to select a different fining agent in order to reduce the amount added, reviewing other fining agents proposed so far, There have been many developments of new fining compounds. Among them, a number of substances such as antimony, chlorine, and glass were examined as other fining agents, but especially in the oxide glass requiring high temperature melting, a fining agent having a fining effect exceeding arsenic. It is hard to say that is found. Therefore, we examined the operating conditions to help the fining effect of the fining agent that substitutes for arsenic, and combined various fining agents to raise the temperature inside the furnace, and various measures were taken to improve the problem. Has been. However, in spite of such continuous efforts, no method has been found yet that can reliably achieve a stable and high fining effect with an inexpensive method applied to various glass compositions.

On the other hand, physical methods include a decrease in glass viscosity due to an increase in melting temperature, a centrifugal separation method, a glass fluid flow control in a furnace, a stirring method, a gas blowing method, a sound / ultrasonic method, a decompression method, and a melting method. Atmosphere control, or
There is a method of combining these. For example, with respect to molten glass, some inventions have been made on a method of forcibly clarifying bubbles in the glass by decompression. In Patent Document 1 and Patent Document 2 below, it is proposed to dispose a vacuum degassing apparatus between a melting tank and a working tank of a glass melting furnace. However, these methods are not so easy as the chemical methods, and moreover, they are methods that do not achieve the results as much as the chemical methods, require a very high capital investment, and have a usable glass composition. Since there are obstacles such as limitation, they have not been widely used as a general method for homogenizing glass.

Also, paying attention to the melting atmosphere, various gases have been adopted in a part of the glass manufacturing process. Among them, Patent Document 3 below describes remelting in an inert gas atmosphere as a means for preventing reboil. Further, Patent Document 4 below describes the use of hydrogen gas or helium gas in the step of densifying the quartz glass tube base material. Then, in Patent Document 5 below, there is a description that the amount of water in the glass is reduced by bubbling a gas selected from CO ₂ , N ₂ , O ₂ , NO _x , and a rare gas as a dry gas.

[0008] Further, in the following Patent Document 6, it can be seen that by using helium together with sodium chloride, an auxiliary effect can be realized in refining the molten glass. It was proposed that the effect could be confirmed by applying helium to the.

[0009]

[Patent Document 1] Japanese Patent Laid-Open No. 11-130442 (second
(See page 7, Fig. 1-2)

[Patent Document 2] Japanese Patent Laid-Open No. 11-130444 (second
(See page 7, Fig. 1)

[Patent Document 3] Japanese Patent Laid-Open No. 06-329422 (second
-4)

[Patent Document 4] Japanese Patent Laid-Open No. 09-301726 (second
(See page 4, Fig. 1)

[Patent Document 5] Japanese Unexamined Patent Publication No. 07-172862 (second
(See page -8, Figure 1-7)

[Patent Document 6] US Pat. No. 3,622,296

[0010]

As disclosed in Patent Documents 1 and 2, refining the molten glass under a reduced pressure condition is recognized as one of the countermeasures, but for that purpose, it will be detailed. In some cases, it is necessary to modify the manufacturing equipment and to introduce expensive equipment, which is an obstacle to manufacturing glass products that require mass production at low cost.

Further, as in Patent Documents 3 and 4,
Although the use of an inert gas as the melting atmosphere has been realized for a specific glass composition, it is a means for shielding the molten glass from oxygen and is for adjusting the water content. Neither Patent Document 3 nor Patent Document 4 discusses the content of the inert gas in the glass and the fining action during melting of the glass.

On the other hand, Patent Document 6 focuses on helium gas for the first time as a refining method, and is an epoch-making method for refining molten glass. However, this method is based on the idea that it is an auxiliary method performed for a specific glass composition, and it is completely assumed that it will be applied to a wider range of applications and other types of glass materials. Absent. Therefore, no follower of this method appears, and neither application to a widely used multi-component oxide glass nor new improved invention has been made.

An object of the present invention is to provide a novel glass composition which can fundamentally solve the problem of fining in melting of multi-component oxide glass.

[0014]

DISCLOSURE OF THE INVENTION The inventors of the present invention have studied the fining in the melting of multi-component oxide glass which has been conventionally carried out. By including helium and / or neon in the glass product, an optimum glass composition applicable to various applications has been invented.

That is, the glass composition according to the present invention is
A glass composition containing a multi-component oxide as a main component, which is produced by melting a glass raw material, and contains 0.01 to 2 μm of at least one component selected from helium and neon.
It is characterized by containing L (microliter) / g (0 ° C., 1 atm).

The present inventors have added a predetermined amount of helium or neon, which is an inert gas component, to the molten glass as a component for providing a refining effect to the molten glass of a multi-component oxide, so that It was found that the bubbles can be completely removed or can be significantly reduced, and a high refining effect is recognized.

In the molten glass, generally, each element becomes a mesh state having a weak binding force, and the higher the temperature, the more rapidly the position of each element becomes irregular with stretching vibration, rotational vibration and declination vibration. The position is changing violently. However, as will be described later, helium and neon have very low reactivity and a small size because the electron arrangement in the atomic structure is a closed shell structure. Therefore, helium and neon are unlikely to bond with various elements that compose the molten glass, and are small enough to pass through the voids of the vibrating mesh as a route, affecting the surrounding elements. It is possible to easily diffuse in the molten glass without being damaged.

Therefore, when the molten glass is brought into contact with helium and / or neon gas in order to make the molten glass contain helium and / or neon, the gas of helium or neon is mixed with a predetermined gas into the molten glass according to Henry's law. It will diffuse rapidly until the partial pressure is reached. On the other hand, oxygen existing in the molten glass, carbon dioxide, water vapor,
Sulfurous acid gas, halogen, etc. do not release from the molten glass at a rate equal to the rate at which the helium or neon gas diffuses into the molten glass, because the relative diffusion transfer speed is slower than that of helium or neon. The total gas partial pressure of becomes high.

Such oxygen, carbon dioxide gas, water vapor, sulfurous acid gas, halogen, etc. are generated by the chemical reaction of the glass raw material, etc., but in the absence of a fining agent, the result is due to the diffusion of helium and neon. Thus, the total gas partial pressure in the molten glass exceeds the atmospheric pressure, for example, 1 atmosphere in the atmosphere. Under this high pressure condition,
Helium and neon act as follows. That is, the amount of oxygen, carbon dioxide gas, water vapor, etc. dissolved in the molten glass is expressed as a partial pressure in the glass. However, when the total partial pressure of the gas exceeds 1 atmospheric pressure, which is an atmospheric pressure, these oxygen, Gases such as carbon dioxide, water vapor, sulfurous acid gas, and halogen become unstable when kept in a dissolved state in the glass, and diffuse into fine bubbles existing in the surroundings. As a result, the bubble diameter in the molten glass expands, increases the floating speed, and disappears at the glass surface, so that fine bubble defects existing in the molten glass are removed.

When the molten glass contains a fining agent added as a raw material, the amount of oxygen gas in the molten glass, that is, the oxygen gas partial pressure is maintained in equilibrium with the fining agent. . Here, as described above, due to the action of helium or neon, when the oxygen gas in equilibrium diffuses into fine bubbles, the fining agent disturbs the partial pressure equilibrium established in the molten glass. Become. Therefore, the decomposition of the fining agent is promoted and the supply of oxygen gas is induced. As a result, by containing helium or neon in the molten glass, oxygen resulting from the fining agent, which is the most effective fining gas in oxide glass, can be efficiently released into the molten glass.

As described above, by releasing helium or neon into the molten glass in two steps, that is, by increasing the total gas partial pressure, the components having a high vapor pressure in the molten glass are released from the molten glass. It is possible to bring out the pressure state necessary for the formation of a bubble, and in the glass, form a bubble as a gas phase in a component with a high vapor pressure such as oxygen, or promote the expansion of the bubble, and the melting Further promoting the decomposition of the fining agent added to the glass as a raw material can be surely realized in the process of homogenizing the molten glass having the composition of the present invention held at a high temperature.

The helium and neon used in the present invention may be classified as an inert gas or a rare gas, and since they have a stable closed shell structure, they exist as monoatomic molecules. . Helium is the lightest element among rare gas elements, has a very small structural size, has a very small attractive force due to Van der Waals force, and does not solidify at atmospheric pressure even at absolute zero, and becomes a liquid. Present. Further, neon has the smallest size next to helium among rare gas elements, and like helium, has a stable structure with a monoatomic molecule. Therefore, in a glass article that is manufactured by melting at a high temperature and is cooled, both helium and neon exist in a state of being trapped in the pores of the glass network structure constructed by other constituent components.

Neither helium nor neon participates in the network formation of the glass structure, but by containing 0.01 μL / g or more in the glass alone or in the total amount, a refining effect is given to the molten glass and a homogeneous glass is obtained. To be. If the content is less than 0.01 μL / g, a sufficient fining effect cannot be provided. To give a certain fining effect,
The content is preferably 0.06 μL / g or more. More preferably, the content is 0.1 μL / g or more. As a result, a sufficient refining effect can be realized even under severe conditions such as a large content of gasifiable components contained in the glass. On the other hand, when the content exceeds 2 μL / g, re-heating of the glass composition causes refoaming called so-called reboil, which is not preferable. In addition, although there are differences depending on the glass composition and heating conditions, the upper limit of the content that is more resistant to reboil is 1.5 μL.
/ G (1.5 μL / g or less). In the case of a glass composition in which a fining agent other than helium or neon coexists,
Since riboyl is more likely to be generated, the upper limit of the content is preferably 1.0 μL / g (1.0 μL / g or less).

Therefore, when a refining agent other than helium or neon does not coexist in the molten glass, the preferable content range of helium and / or neon which has a refining effect even under more severe conditions and is less likely to reboil. 0.1 μL
/ G to 1.5 μL / g. On the other hand, when a refining agent other than helium or neon coexists in the molten glass, there is a refining effect even under more severe conditions, and it is difficult to reboil, and the preferable content range of helium and / or neon is 0.1 μL. / G to 1.0 μL / g.

In general, the glass is produced from the vapor phase using vapor deposition or from the solid phase by the sol-gel method, but in the present invention, the glass is cooled from the molten glass. It is intended for glass produced by. Then, the energy for melting the glass raw material may be imparted by the combustion of solid, liquid, or gas fuel, or by utilizing electromagnetic radiation such as electricity or infrared rays, radiation from other high-temperature medium, or conduction heat. You may.

In the present invention, melting and manufacturing a glass raw material means that a glass raw material exists as a precursor before melting, and the glass raw material is once heated to a high temperature and then cooled, so-called supercooled. It is a substance that vitrifies as a liquid and solidifies as a product containing a multi-component oxide as a main component to form a glass composition. The present invention is not hindered as long as the glass phase coexists even if the crystal phase is generated on the surface and inside due to the presence of the surface, the interface and the like depending on the cooling procedure and the cooling conditions.

That is, as the glass raw material of the present invention,
For example, inorganic or inorganic oxides, carbonates, phosphates, chlorides, various glasses, etc., alone or in mixture, with a compound as a main component, and if necessary, organic additives, metal additives in alone or in mixtures, What added the compound as an additive can be used. In addition, if it is expressed by the category derived from the source of the glass raw material, it will be a glass composition containing a multi-component oxide as a main component, regardless of whether it is a natural product, an artificial synthetic product, or an artificially refined product. If so, there is no problem. Further, it is also possible to employ an industrial product which is highly purified by removing impurities of ppm or ppb order by various production methods as the glass raw material of the present invention. Further, it goes without saying that general raw materials for glass production, which are produced and refined by the mining industry and the chemical industry, can be used as the raw material of the glass composition of the present invention.

Here, the "glass composition containing a multi-component oxide as a main component" in the present invention contains two or more kinds of oxides, and the mass% notation for the two or more kinds of oxides. Means the glass composition whose total amount is 50% by mass or more. For example, when a plurality of oxide components are mixed as impurities in a glass composition having a single composition, it does not correspond to the “glass composition containing a multi-component oxide as a main component” in the present invention. More specifically, for example, in a single-component glass composition having a content rate of close to 99% by mass, a plurality of oxide components are contained in two digits after the decimal point, for example, 0.09 mass% or less. If it is present, it does not correspond to the “glass composition containing a multi-component oxide as a main component” in the present invention.

Further, the melting of the glass raw materials is usually carried out by holding the glass raw materials together in a container so as to prevent a plurality of raw materials from being separated during high temperature heating, but it is necessary. It is also possible to apply an external force such as an air flow pressure or an electromagnetic force to the raw material according to the above, to float and melt. Further, a medium having a function of holding the raw material and maintaining it at a high temperature without having the function as the container can be used for melting the glass raw material. Therefore, this medium does not necessarily have to be a solid, and there is no problem even if it is a liquid such as a liquid metal in which a single component or a plurality of components are eutectic.

When a container is used for melting, it is preferable to select a container that is less likely to react with the glass raw material that melts, but if the use is acceptable even if some impurities are mixed in the glass composition. It can be used as a material forming a container, regardless of whether it is a metal or an inorganic substance. Also, when a container is used to capture glass raw materials in outer space or in a space imitating the state where gravity does not work, if the wettability between the container and the glass is too good, the glass will overflow the container wall and overflow outside the container. It is necessary to consider this point as well. Further, all of the industrial materials generally used in the glass industry, which are called so-called refractories having heat resistance as a main characteristic, can be used alone or in combination.

As a method of adding helium or neon to the glass composition of the present invention, for example, the glass raw material is kept in an atmosphere of helium or neon before melting, and the temperature is gradually raised while maintaining the state. Alternatively, a method of melting the glass raw material may be adopted, or a method of diffusing helium or neon into the molten glass by contacting with helium or neon after the glass raw material is sufficiently melted may be adopted. Good. Further, by using a raw material or glass containing a high concentration of helium or neon as a cullet for a specific raw material species in the glass raw material, it is possible to efficiently add helium or neon to the glass composition. Is.

Although helium or neon is diffused in the molten glass by making the atmosphere around the glass an atmosphere of helium or neon, it is an easy method among addition methods of helium and neon. Alternatively, a method of bubbling helium or neon into the molten glass with a refractory nozzle may be adopted, or the constituent material of the container is a refractory material having porous pores to the extent that helium or neon can diffuse. It is also possible to realize efficient diffusion by adopting, and generating a large number of fine helium and neon bubbles from the bottom of the container. Furthermore, by making the tip of the refractory nozzle immersed in the container the above-mentioned porous refractory, it is possible to create an inexpensive and efficient diffusion state of helium and neon.

Further, the glass composition of the present invention may contain a clarifying agent component in an amount of 0.001 to 3 mass% in mass percentage, in addition to the above constitution (structure of claim 1). Good.

In the present invention, the fining agent means that the glass raw material has a high vapor pressure when heated and pyrolyzed and melted at a high temperature, vaporized and separated from the melt, and a part of the glass raw material is the glass raw material. It may also contain a molten atmosphere gas or the like between the raw materials trapped during melting, and generally releases a gas mixture recognized as bubbles in the glass from the molten glass to form a molten glass. It means a chemical substance that has the role of bringing it into a homogeneous state. Here, specifically, the gas that forms bubbles in the molten glass means CO ₂ , SO ₂ , O ₂ ,
N ₂ , H ₂ O, H ₂ , Ar and mixed gas thereof, etc.,
At high temperature, a small amount of evaporation / volatile matter from the glass melt may be contained as a gas component.

As the above-mentioned fining agent, arsenic compounds such as As ₂ O ₃ , Sb ₂ O ₃ , 2MgO.Sb ₂ O ₅ and 7M are used.
_{gO · Sb 2 O 5, 2ZnO} · Sb 2 O 5, 7ZnO · Sb
_{2 O 5, 3CaO · Sb 2} O 5, 6CaO · Sb 2 O 5, 2S
_{rO · Sb 2 O 5, 6SrO} · Sb 2 O 5, BaO · Sb 2
O ₅ , 4BaO · Sb ₂ O ₅ , Li ₂ O · Sb ₂ O ₅ , 2Li
2O ・ Sb ₂ O ₅ , K ₂ O ・ Sb ₂ O ₅ , LaSbO ₄ , Sb
_{NbO 5, Sr (Ca 0 .33} Sb 0.67) O 3, LiZnSb
_{O 4, Li 1.5 Ti 1.0 Sb} 0.5 O 4, Ba 2 Al 0. 5 Sb 0.5
O ₆ , Ba ₂ Ce _0.75 SbO ₆ , ZrSbPO ₇ , Ba (S
b _0.5 Sn _0.5 ) O ₃ , LiSiSbO ₅ , Li ₂ Zr ₂ Sb
₂ Antimony compounds such as SiO ₁₁ , SnO ₂ , CeO
₂ , oxides such as BaO ₂ , peroxides, NaNO ₃ , KN
O _3, Ba (NO ₃₎ nitrates such as _{2, Na 2 SO 4, K} 2 S
Sulfates such as O ₄ , CaSO ₄ , and BaSO ₄ , NaCl,
Chlorides such as KCl and CaCl ₂ , CaF ₂ , Na ₂ Si
F _6, fluorides such as _{LiF · KF · Al 2 O 3} · 3SiO 2, KF, Al, Si, Zn, Ga, Fe, Sn, metal-inorganic elements such as _{C, H 2 O, Al (} OH) 3 , Sucrose,
Various compounds, elements and mixtures, such as granulated sugar, corn starch, and organic compounds that are carbon-containing compounds such as wood flour can be used.

The content of the fining agent component depends on the type and glass composition used, but if it is 0.001% by mass or more, coexistence with helium or neon gives a refining effect to the molten glass. Is preferred. Also, the content is 0.0
When the amount is 1% by mass or more, this effect becomes remarkable, which is more preferable. Further, in a glass composition in which helium or neon is difficult to diffuse, it is preferable to contain 0.03 mass% or more. On the other hand, if the content exceeds 3% by mass, the amount of generated gas becomes too large, and it becomes difficult to remove bubbles from the molten glass. Further, for glass products having severe conditions for preventing foaming such as reheat treatment, it is preferable to set the upper limit of the content to 2.5% by mass,
In the glass composition applied to a glass product used in a more severe environment, it is preferable that the upper limit of the content is 2.0% by mass. Therefore, the more preferable content range of the fining agent component is 0.01 to 2.5% by mass, and depending on the case, 0.01 to 2% by mass, 0.03 to 2.5% by mass,
0.03 to 2% by mass, 0.01 to 3% by mass, 0.03 to
It is 3% by mass.

Regarding the method of adding the fining component,
It is not particularly limited, and may be added as a molten raw material component or may be added later to the molten glass. It is also possible to add helium or neon at the same time. Furthermore, it is also possible to intentionally add the above components to the glass as an elution component from the heat-resistant material that is immersed in the container during melting or the molten glass. It is also possible to add the fining agent component alternately with helium or neon, or to gradually increase or decrease the amount while confirming the fining effect to adjust the optimum amount.

When helium and / or neon coexists with the above-mentioned fining component, the content of helium and / or neon is preferably 0.1 to 1.0 μL / g.

The glass composition of the present invention comprises, in addition to the above-mentioned constitution (the constitution described in claim 1), SO ₃ , Cl, H ₂ O, Sn, Sb, F and As as a fining agent component. It may contain one or more components selected from the inside.

Here, S specified as a fining agent component
O ₃ , Cl, H ₂ O, Sn, Sb, F and As exhibit a high refining effect when coexisting with helium and / or neon among the above-mentioned various refining agents, and are heated by high temperature melting. A part of the component remains in the glass composition after cooling even if it is modified by decomposition, redox reaction or the like.

The glass composition of the present invention has, in addition to the above-mentioned constitution (the constitution described in claim 1), Sb in the form of Sb ₂ O ₃
May be contained in an amount of 0.01 to 1.5% by mass.

Sb (antimony) is clear in the glass composition
Helium and / or neon, which are components that act as agents
A high fining effect is exhibited by coexisting with. However,
The content in the lath composition is Sb₂O₃As 0.01% by mass
If the amount is too small, the sufficient effect cannot be obtained. Therefore, S
b₂O₃Content is 0.01 mass% or more. So
In order to obtain a higher effect, Sb₂O₃As
The content is preferably 0.1% by mass or more. on the other hand,
Sb₂O₃If the content of as exceeds 1.5 mass%, 2
Since reboil due to heat treatment during the next processing becomes a problem,
Its content needs to be 1.5 mass% or less. Well
Also, the stability against this reboil is Sb. ₂O₃As
If the content is 1.0% by mass or less, the content will be higher,
Especially when high temperature heat treatment is performed in the secondary processing,
The content of is preferably 1.0% by mass or less. Furthermore
Coexistence of gas components that may cause other reboil
Below, the content is preferably 0.7% by mass or less.
Good

The glass composition of the present invention has, in addition to the above composition (structure described in claim 1), 0.03 SO ₃ or less.
The content may be 01 to 1.0% by mass.

SO ₃ is a component which, when coexisting with helium and / or neon, enhances the effect of defoaming bubbles in the molten glass. However, the defoaming effect is that when the content of SO _{3 in} the glass composition is less than 0.001% by mass,
Not fully exerted. Therefore, the content of SO ₃ is 0.00
It is 1 mass% or more. In order to realize a higher effect, the SO ₃ content is preferably 0.01% by mass or more. Then, in order to realize a sufficient defoaming effect under more severe conditions, the SO ₃ content is preferably 0.03 mass% or more. On the other hand, when the content of SO ₃ in the glass composition exceeds 1.0% by mass, bubbles are more likely to be generated by reboil when reheat treatment is performed by secondary processing after cooling. Therefore, the content of SO ₃ is 1.0% by mass.
Below. And, depending on the reheat treatment condition,
The safer SO ₃ content is 0.8% by mass or less.
Further, in the coexistence of another gas component which may cause reboil, its content is preferably 0.5% by mass or less.

Further, the glass composition of the present invention contains Cl in an amount of 0.01 in addition to the above-mentioned constitution (the constitution described in claim 1).
It may be contained in an amount of up to 1.5% by mass.

Cl (chlorine) is a component which, together with helium and / or neon, has a fining effect of promoting the release of gas components from the molten glass, but the content of Cl in the glass composition is 0. If it is less than 0.01% by mass, a sufficient fining effect cannot be obtained. Therefore, the content of Cl is 0.01
It should be at least mass%. In order to achieve a higher refining effect, the Cl content is preferably 0.03 mass% or more. On the other hand, if the content of Cl exceeds 1.5% by mass,
The chemical resistance of the glass is likely to be impaired, and the glass composition does not have sufficient durability in actual use. Therefore, C
The content of 1 is 1.5 mass% or less. Further, for a glass composition that emphasizes higher chemical durability and weather resistance, the upper limit of the Cl content is preferably 1.2 mass. Furthermore, under the condition that other components that deteriorate the chemical durability and weather resistance coexist, the upper limit of the Cl content is 1.0.
It is preferably set to mass%.

Regarding F, which is a halogen gas similar to Cl, the following facts have been found. When F coexists with helium and / or neon, it has the effect of promoting the release of gas components from the molten glass, and also has the effect of reducing the viscosity of the glass during melting, so that F is contained in the glass composition. It is effective to achieve the intended effect of the present invention by containing a predetermined amount in. In that case, the preferable content range of F is 0.01 to 2.0 mass%.
If the content of F is less than 0.01% by mass, a sufficient effect cannot be obtained. To achieve even higher effects, F
The content of is preferably 0.03 mass% or more. On the other hand, F combines with the cation component in the glass so as to cut the glass network structure in the glass after cooling, so that C
Similarly, the chemical durability of glass is deteriorated, so it is not preferable to contain it in an amount exceeding 2.0 mass% in the glass composition. Further, when importance is attached to chemical durability, the upper limit of the content is preferably set to 1.5% by mass. Furthermore, in the coexistence of other components that deteriorate the chemical durability, the upper limit of the content is preferably 1.0% by mass.

Further, the glass composition of the present invention contains 0.02% of H ₂ O in addition to the above constitution (constitution of claim 1).
It may be contained in an amount of 1 to 0.2% by mass.

H ₂ O is an effective component because it coexists with helium and / or neon and has the effect of promoting the release of gas components from the molten glass by lowering the viscosity. However, H ₂ O in the glass composition
If the content of is less than 0.01% by mass, a sufficient effect cannot be obtained. Therefore, the content of H ₂ O is 0.01% by mass.
That is all. In order to obtain a higher gas component release effect, the H ₂ O content is preferably 0.03 mass% or more. On the other hand, H ₂ O combines with other cations in the glass so as to cut the glass network structure in the glass after cooling, thereby deteriorating the chemical durability and weather resistance of the glass. It is not preferable to add more than 0.2% by mass. Furthermore, when coexisting with another component that deteriorates chemical durability and weather resistance, the content thereof is preferably 0.15% by mass or less. Also, especially in the case of glass products that emphasize chemical durability and weather resistance,
The content is preferably 0.10 mass% or less.

Further, the glass composition of the present invention has Sn in addition to SnO ₂ in addition to the above constitution (constitution in claim 1).
As a mass percentage of 5 ppm (that is, 5 × 10 ⁻⁴ mass%)
It may contain up to 2% by mass.

When Sn (tin) is used as a fining agent in the glass composition, a high fining effect is exhibited by coexisting with helium and / or neon. However, if the content of SnO ₂ in the glass composition is less than 5 ppm by mass, a sufficient effect cannot be obtained. Therefore, the content as SnO ₂ is 5 mass% or more. When the content of helium and / or neon in the glass composition is small, SnO is required to exert a reliable effect.
The content as ₂ is preferably 100 ppm by mass or more. In the case of a glass composition requiring high temperature melting, in order to obtain a higher effect, the content as SnO ₂ is 0.05 mass% or more, that is, a mass percentage of 5
It is preferable to set it to 00 ppm or more. On the other hand, if the content as SnO ₂ exceeds 2 mass%, reboil due to heating becomes a problem in applications requiring heat treatment during secondary processing, so the content should be 2 mass% or less. Is preferred. Further, in order to further improve the stability against riboyl, the content as SnO ₂ is preferably 1.5% by mass or less. Further, when high temperature heat treatment is performed in the secondary processing, SnO ₂ is added. The content as ₂ is 1.2
It is preferably not more than mass%. Further, in the presence of other reboil gas components, the content as SnO ₂ is 0.7
It is preferably not more than mass%.

Further, the glass composition of the present invention has As in addition to As ₂ O ₃ in addition to the above-mentioned constitution (constitution in claim 1).
May be contained in an amount of 0.01 to 1.5% by mass.

As (arsenic) is a component that acts as a fining agent in the glass composition like Sb, but exhibits a high fining effect when it coexists with helium and / or neon. However, if the content of As ₂ O ₃ in the glass composition is less than 0.01% by mass, a sufficient effect cannot be obtained. Therefore, the content of As ₂ O ₃ is 0.01% by mass or more. In order to obtain a higher effect, the content of As ₂ O ₃ is preferably 0.05% by mass or more. on the other hand,
If the content of As ₂ O ₃ exceeds 1.5% by mass, 2
Since reboil due to heat treatment during the next processing becomes a problem,
Its content needs to be 1.5 mass% or less. Further, the stability against riboyl becomes higher if the content as As ₂ O ₃ is 1.0% by mass or less,
Especially when high-temperature heat treatment is performed in the secondary processing, the content is preferably 1.0% by mass or less. Furthermore, in the presence of other reboil gas components, the content of As ₂ O ₃ is preferably 0.7% by mass or less.

The glass composition of the present invention has the above-mentioned composition.
Sb in addition to the composition (structure according to claim 1)₂O₃
As 0.01 to 1.5 mass% and Sn as S
nO ₂As a mass percentage of 5 ppm to 2 mass%
May be

Here, Sb and Sn each independently have the above-mentioned effects, but higher effects may be realized by coexisting both in the glass composition. When both are coexistent, if the content of Sb as Sb ₂ O ₃ is less than 0.01% by mass, a sufficient effect cannot be obtained. Therefore, the content as Sb ₂ O ₃ is 0.
It is set to 01% by mass or more. To get higher effect,
The Sb content is preferably 0.08% by mass or more. On the other hand, if the content as Sb ₂ O ₃ exceeds 1.5% by mass, reboil due to heat treatment during secondary processing becomes a problem, so the content must be 1.5% by mass or less. . Further, the stability against this reboil is Sb ₂ O ₃
If the content is less than 0.9% by mass, the content will be higher. Therefore, particularly when high-temperature heat treatment is performed in the secondary processing, the content is preferably 0.8% by mass or less. Furthermore, in the presence of other gas components that may cause reboil, the content as Sb ₂ O ₃ is preferably 0.6% by mass or less.

When the content of Sn as SnO ₂ is less than 5 ppm by mass, a sufficient effect cannot be obtained. Therefore, the content as SnO ₂ is 5% by mass.
pm or more. When the content of helium and / or neon in the glass component is small, the content as SnO ₂ is preferably 80 ppm by mass or more in order to exert a reliable effect. Further, in the case of a glass composition requiring high temperature melting, in order to obtain a higher effect, the content as SnO ₂ is preferably 0.04 mass% or more, that is, the mass percentage is 400 ppm or more. On the other hand, if the content as SnO ₂ exceeds 2 mass%, reboil due to heating becomes a problem in applications requiring heat treatment during secondary processing, so the content should be 2 mass% or less. There is. Further, in order to further improve the stability to this reboil, the content as SnO ₂ is preferably 1.4% by mass or less, and further, when high temperature heat treatment is performed in the secondary processing, The content is preferably 1.1% by mass or less. Further, in the coexistence of other reboil gas components, the content as SnO ₂ is preferably 0.6% by mass or less.

Further, the glass composition of the present invention contains 0.03 of SO ₃ in addition to the above composition (structure described in claim 1).
01 to 1.0 mass% and 0.01 to 0.01
It may contain 1.5% by mass.

Here, SO ₃ and Cl each have the above-mentioned effects independently, but when both are coexistent, a higher effect can be realized as compared with the case where they are used alone. In particular, it is effective in a situation in which a glass composition having a high viscosity, which makes refining difficult, is melted. However, if the content of SO _{3 in} the glass composition is less than 0.001 mass%, a sufficient effect cannot be obtained. Therefore, the content of SO ₃ is 0.
It is 001 mass% or more, preferably 0.005 mass% or more. To achieve defoaming under more severe conditions, S
The O ₃ content is preferably 0.01% by mass or more. On the other hand, when the content of SO ₃ exceeds 1.0% by mass,
When reheat treatment is carried out by secondary processing after cooling, bubbles due to reboil are likely to occur, so the content is preferably 1.0% by mass or less. The safer upper limit of the content is 0.7% by mass, although it depends on the reheat treatment conditions. In addition, when other gas components that may cause reboil are present in the glass, S
The O ₃ content is preferably 0.4% by mass or less.

In the coexistence of SO ₃ with Cl, if the content in the glass composition is less than 0.01% by mass, a sufficient fining effect cannot be obtained. Therefore, the content of Cl is 0.01
It should be at least mass%. In order to realize a higher fining effect, the Cl content is preferably more than 0.02 mass%. On the other hand, if the Cl content exceeds 1.5% by mass, the chemical durability and weather resistance of the glass tend to be impaired, and sufficient durability in actual use of the glass composition is obtained. I can't. Therefore, the upper limit of the Cl content is 1.5% by mass. For a glass composition used for applications that place more importance on chemical durability and weather resistance, the upper limit of the Cl content is preferably 1.1% by mass. Further, under the condition that other components that deteriorate the chemical durability and weather resistance coexist, the upper limit of the Cl content is preferably 0.9% by mass.

Further, in the glass composition of the present invention, in addition to the above structure (structure according to claim 1), Sb is added to Sb ₂ O ₃
Content of 0.01 to 1.5 mass% and As of A
It may contain 0.01 to 1.5 mass% as s ₂ O ₃ .

Here, Sb and As each have the above-mentioned effects independently, but when both are coexisted, the decomposition temperatures of the oxides of both are different, so that a higher effect is obtained than when they are used alone. It can be realized in a wide temperature range. However, if the content of Sb ₂ O ₃ in the glass composition is less than 0.01% by mass, a sufficient effect cannot be obtained. Therefore,
The content as Sb ₂ O ₃ is 0.01% by mass or more.
In order to obtain a higher effect, the content as Sb ₂ O ₃ is preferably 0.07 mass% or more. On the other hand, Sb
_If the content of ₂ O ₃ exceeds 1.5% by mass, riboyl due to heat treatment during secondary processing becomes a problem, so the content is preferably 1.5% by mass or less. Also,
The stability against riboyl becomes higher when the content as Sb ₂ O ₃ is 0.9% by mass or less. Therefore, when the heat treatment at high temperature is performed in the secondary processing, the content is 0%. It is preferable to set it to 1.9 mass% or less. Furthermore, in the presence of other gas components that may cause reboil, the content as Sb ₂ O ₃ is preferably 0.7% by mass or less.

As is Sb₂O₃In coexistence with the glass
The content in the composition is As₂O₃Less than 0.01 mass%
Without it, a sufficient fining effect cannot be obtained. Therefore, As₂
O₃Content is 0.01 mass% or more. Than
In order to achieve high effect, As₂O₃Content as
Is preferably 0.02% by mass or more. On the other hand, As
₂O₃If the content of as a component exceeds 1.5% by mass, secondary addition
Since reboil caused by heat treatment during work becomes a problem,
The content is 1.5% by mass or less. This reboiler when heating
Stability against₂O₃Content as 0.9
If it is less than mass%, it will be higher.
If high temperature heat treatment is performed,₂O₃As
The content of is preferably 0.9 mass% or less. Furthermore
In the presence of other reboil gas components, As₂O₃age
The total content is preferably 0.6% by mass or less.

The glass composition of the present invention is intended for a multi-component oxide glass composed of a plurality of oxide components each containing 1% by mass or more. It is desirable that the number of components of the product is as large as possible. That is, from a two-component system to a three-component system and from a three-component system
A component system is preferable, and a 5-component system, a 6-component system, a 7-component system or more is more desirable than a 4-component system. This is also due to the fact that as the number of components increases, the melting temperature generally decreases and bubbles tend to float, but on the other hand, the interatomic distance distribution between each atom in the molten glass is composed of a single component. The molten glass composed of multiple components becomes broader than the molten glass, and as a result, there is a portion with a large interatomic distance in the molten glass. This is because the effect that diffusion easily occurs can be obtained.

When the glass composition of the present invention contains a constituent having a small atomic radius such as an alkali metal element in the composition, it tends to interfere with the diffusion path of helium and neon. The less the better. However, when the use of the glass composition is desired to contain an alkali metal element, the alkali metal element may be added. When the viscosity of the molten glass is lowered by the addition of the alkali metal element, gas degassing from the glass is promoted, which contributes to the improvement of the refining effect.

The glass composition containing an alkali metal element will be specifically described below.

For example, when a glass composition is composed of four or more oxide components and an additive of an alkali metal element is allowed even in a small content, the glass composition is as follows. Can be defined.

That is, it is a glass composition produced by melting a glass raw material, which contains four or more oxide components as a main component, and contains helium and / or neon in the above-mentioned range, and if necessary. Accordingly, the total content of the alkali metal oxide elements containing Li ₂ O, Na ₂ O and K ₂ O containing the fining agent component in the above-mentioned range is 1% by mass.
A glass composition, which is 0 ppm or more and less than 0.3% by mass.

The alkali metal oxide element has a function of lowering the viscosity of the molten glass. When the viscosity of the molten glass decreases, degassing by degassing from the molten glass is easily performed. In order to realize this effect even if it is slight, the total content of the alkali metal oxide elements needs to be 10 ppm or more in mass percentage. Then, in order to further enhance this effect, it is preferable that the total content of the alkali metal oxide elements is 50 ppm or more in terms of mass percentage. On the other hand, depending on the environment in which glass is used, the alkali metal oxide element may be required to be as small as possible.

For example, in plate glass for liquid crystal substrates used for electronic parts and the like, it is desirable to avoid alkali metals as much as possible. In such an application, the upper limit of the total content of alkali metal oxide elements is 0.3% by mass. Further, when this requirement is strict, it is desirable that the total content of the alkali metal oxide elements is less than 0.1% by mass.

On the other hand, when a larger amount of alkali metal element can be contained in the glass composition, the glass composition can be defined as follows.

That is, it is a glass composition produced by melting a glass raw material, which contains four or more oxide components as a main component, and contains helium and / or neon in the above-mentioned range, and further if necessary. Accordingly, the total content of the alkali metal oxide elements containing Li ₂ O, Na ₂ O and K ₂ O containing the fining agent component in the above range is 0.3% by mass.
As described above, the glass composition is less than 16% by mass.

Here, regarding the glass composition used for the purpose of allowing the alkali metal oxide element, the total content of the alkali metal oxide elements is included in order to further ensure the effect of lowering the viscosity of the molten glass. The amount can be 0.3 mass% or more. In order to achieve a more reliable effect, the total content of alkali metal oxide elements is preferably 1.0% by mass or more. On the other hand, particularly in the case of a relatively simple oxide composition of about 4 components, the addition of the alkali metal oxide element may deteriorate the basic physical properties of the glass exhibiting chemical durability such as alkali elution amount. Therefore, in applications where importance is attached to chemical durability, the upper limit of the total content of alkali metal oxide elements is preferably less than 16% by mass. And, this upper limit value needs to be further lowered when the use environment of the glass composition is poor,
It is preferably less than mass%.

For example, the oxide component of the glass is 6
If more than the components, the glass composition can be defined as follows.

That is, a glass composition which is produced by melting a glass raw material and which has as its main component an oxide component of 6 or more components and which contains helium and / or neon in the above-mentioned range, Accordingly, the total content of alkali metal oxide elements containing Li ₂ O, Na ₂ O and K ₂ O, which contain the fining agent component in the above-mentioned range, is 16% by mass or more and less than 30% by mass. A glass composition characterized by the above.

As described above, the alkali metal oxide element has a function of cutting the network in the glass structure to reduce the viscosity of the molten glass. In addition, since the oxide components constituting the glass are 6 or more, it is a condition that helium and / or neon in the molten glass are more likely to diffuse. Therefore, when the glass composition is composed of 6 or more oxide components, the effect of lowering the viscosity of the molten glass and the effect of promoting the diffusion of helium and / or neon are provided unless there is a restriction from the application. By utilizing both of them, it is possible to improve the refining effect. Further, when the oxide components are 6 or more, the effect of suppressing chemical durability such as elution of alkali becomes stronger due to the combination of the oxide components. Therefore, the total content of the alkali metal oxide elements is preferably 16% or more by mass. On the other hand, if the total content of the alkali metal oxide elements is too large, problems such as water resistance will occur. Therefore,
The upper limit of the total content of the alkali metal oxide elements is preferably 30% by mass or less. Particularly for a glass composition used in a poor environment, the upper limit of the total content of alkali metal oxide elements is preferably 20% by mass or less.

In the glass composition of the present invention, if necessary, a transition metal element compound showing various colored ion colorings as a colorant, a rare earth, Au, Ag, Cu, a sulfide,
Additives such as tellurium compounds, selenium compounds, CdS-CdSe solid solutions that cause colloidal coloring, radiation coloring additives such as Mn and Ce, and rare metal element additives for adjusting the refractive index can be added. Is. On the contrary, U, Th, Fe, Ti, Pb, As, Cl, K, C depending on the demand from the application in which the glass composition is used.
Elements such as u, V, Cr, Mn, Pt, Mo, and Zr are added as p
It is also possible to manage it on the pm or ppb order so as not to contain it as much as possible.

Of these, Pt (platinum) in particular may act as a nucleus of bubble formation when foaming occurs in the molten glass by intentionally adding a small amount, and when performing clarification reliably, It is an effective ingredient for producing bubbles at an early stage. The addition amount of Pt is preferably 1 ppb or more,
More preferably, it is pb or more. On the other hand, when the content of Pt increases, there are many cases where the optical characteristics and the appearance quality may be affected. Therefore, the upper limit of the amount of Pt added is preferably 50 ppm. Especially in applications where optical characteristics are important, Pt
It is preferable that the upper limit of the addition amount of is 30 ppm.

The glass composition of the present invention may be melted in a heat resistant material containing Pt. In this case,
Pt intentionally added in a small amount also has an effect of reducing the elution of Pt from the heat resistant metal material. Therefore, a large amount of Pt is eluted from the heat-resistant metal material, and the eluted foreign matter containing Pt is generated in the molten glass, thereby impairing the homogeneity of the glass,
Alternatively, the situation in which the glass is discolored by the eluted Pt is prevented.

Mo (molybdenum) is also the above Pt.
Similarly, in some cases, the glass composition containing helium and / or neon may exert the effect of nucleating bubbles,
When adding o does not hinder the characteristics of the glass composition, a small amount of Mo may be added instead of Pt.
However, since the effect of Mo is not as high as that of Pt, it is preferable to add 5 ppm or more. Also, M
In order to further ensure the effect of the addition of o, the addition amount is preferably 50 ppm or more. The addition amount of Mo can be increased up to 1000 ppm as long as it does not cause any optical problem in use. The preferable upper limit of the amount of Mo added is 700 ppm.

Furthermore, Zr (zirconium) is ZrO.₂
Helium and / or neon when added in trace amounts as
Coexisting with helium and / or neon
It may have the effect of helping diffusion in molten glass.
Yes, in this case, Zr is replaced with ZrO ₂5ppm or more
You may add. In addition, to ensure this effect is exhibited
ZrO₂Addition amount as 50ppm or more
Is preferred. On the other hand, ZrO₂Increases the viscosity of the molten glass
To prevent the diffusion of helium and / or neon.
In some cases, the upper limit of the amount added is 5% by mass.
Is preferred. In addition, the increase in the viscosity of the molten glass is significantly suppressed.
In the case of ZrO₂Upper limit of the content as 3 mass%
It is good to say

The glass composition of the present invention has a material composition designed in advance so that a plurality of microcrystalline precipitates can be deposited inside the glass body by applying energy such as reheating treatment and laser irradiation. It is possible to take.

Further, the glass composition of the present invention is subjected to an ion exchange treatment for obtaining required optical characteristics, strength characteristics and the like.
Application of various thin films to the glass surface, implantation of specific ions into the glass surface, surface treatment with chemicals etc. to improve surface characteristics, solidification of radioactive materials, etc., ultra-quenched glass solidification using liquid nitrogen, liquid helium, etc. It is also applicable to the production of glass by ultra-high temperature melting using solar energy, the special glass utilizing the crystallization phenomenon due to the application of ultra high pressure, and the addition of additives for imparting special electromagnetic characteristics.

[0083]

BEST MODE FOR CARRYING OUT THE INVENTION Embodiments of the present invention will be described below with reference to Examples.

[Example 1] Sample No. 1 in Table 1 1-No.
10 represents the glass composition according to Example 1 of the present invention. Molten glass that had been melted to have a predetermined composition was poured out on a carbon plate in advance, and a part of the composition was analyzed by ICP emission analysis and the like, and the composition was confirmed. 0.5-2.0 mm
It was crushed to a particle size of. 50 g of this crushed glass was placed in a platinum crucible, and the crucible was stored in an atmosphere furnace having an airtight structure whose temperature was previously raised to 1400 ° C. and held for 10 minutes. After that, helium (hereinafter referred to as He) or neon (hereinafter referred to as Ne) adjusted to have an appropriate concentration with nitrogen was introduced into the furnace as an atmosphere gas, and treatment was performed for 30 minutes. The ICP emission spectrometer used for the composition analysis was a secondary electron multiplier (SEM).
on multi-pliers) and SP with Seiko Instruments Inc. improved measurement sensitivity
It was S1500 VR, and about 0.5 g of glass was required for one analysis. In addition, the sample No. 1-No.
10 corresponds to the invention according to claim 1.

[0085]

[Table 1]

Further, by analyzing the composition after remelting, it was confirmed that there was no difference from the oxide composition before melting, and the number of remaining bubbles in the glass was maintained at 20 in the immersion liquid having the same refractive index as the glass. It was confirmed by a stereoscopic microscope at a magnification of 100 times to 100 times. Regarding the glass contents of He and Ne, a quadrupole mass spectrometer (QMA12) manufactured by BALZERS in which a secondary electron multiplier (SEM) is mounted to improve the measurement sensitivity.
Measurement was carried out according to 5). Gas analysis by a quadrupole mass spectrometer is performed by placing a glass sample to be measured in a platinum dish and holding the platinum dish in a sample chamber at 10 ⁻⁵ Pa (that is, 10 ⁻⁸ T).
(Orr) vacuum state, and then the gas released by heating was introduced into a quadrupole mass spectrometer having a measurement sensitivity of 0.001 μL / g for analysis.

In the table, what is indicated by ND means that it could not be detected. As a result of the investigation, it was confirmed that all the glasses contained He and Ne, and the remaining number of bubbles was confirmed to be a quality that could be commercialized as a glass composition.

[Comparative Example 1] Sample No. 11-N
o. 20 represents the glass composition according to Comparative Example 1. Sample No. of Comparative Example 1 11-No. No. 20 was prepared by preparing molten glass in the same procedure as in Example 1 and remelting under the same conditions as in Example 1 except that the melting atmosphere was the atmospheric atmosphere.

[0089]

[Table 2]

As a result, in Example 1 of Table 1, the number of bubbles was 72 cells / 10 g to ND, whereas in Comparative Example 1 of Table 2, the number of bubbles was 780 to 2570 cells / 10 g, and Comparative Example 1 was micron. It was confirmed that the number of bubbles having an order bubble diameter was very large and no fining effect was obtained. In addition, H
Even if e and Ne are not intentionally added, a slight content of less than 0.001 μL / g is detected by mixing from the air or the like. However, in such a small amount of contained state,
It is difficult to realize the remarkable effects of the present invention.

[Example 2] Sample Nos. 21
~ No. 90 represents the glass composition according to Example 2 of the present invention. It was adjusted to contain a fining agent component and melted in the same manner as in Example 1. Further, when it was necessary to contain a large amount of water, steam bubbling was also used during melting. And analysis of He and Ne for the sample after melting,
And the number of bubbles was measured. In addition, the sample No. 21
˜30 correspond to the invention according to claims 1 to 3. In addition, the sample No. 21 is the invention according to claim 6, sample No. 21.
24 and 28 are the invention according to claim 4, Sample No. No. 25 is the invention according to claim 9, sample No. 26 is the invention according to claim 8 and sample No. No. 27 is the invention according to claim 7, sample No.
23 and 30 correspond to the invention according to claim 5, respectively.

[0092]

[Table 3]

Sample No. of Table 4 31 to 34, 39 are the inventions according to claims 1 to 3 and 6, sample No. 35-3
Reference numerals 8 and 40 correspond to the inventions according to claim 1, claim 2 and claim 3, respectively.

[0094]

[Table 4]

Sample No. of Table 5 41 to 50 are claims 1
3 to 5, the invention corresponds to claim 5. In addition, the sample No. No. 44 is the invention according to claim 11; 47 corresponds to the invention according to claim 8, respectively.

[0096]

[Table 5]

Sample No. of Table 6 51-60 are Claim 1
.About.3 and claim 4. In addition, the sample No. 53
Is the invention according to claim 6, Sample No. Reference numeral 57 corresponds to each of the inventions according to claim 7.

[0098]

[Table 6]

Sample No. of Table 7 61 to 70 are claims 1 to
3 corresponds to the invention according to claim 9. In addition, No.
65 is the invention according to claim 7, sample No. 66 is claim 5
Related to the invention, Sample No. 67 is claim 4 and claim 12
It corresponds to the invention according to each.

[0100]

[Table 7] Sample No. of Table 8 71 to 80 are claims 1 to 3 and claim 8
It corresponds to the invention according to. In addition, the sample No. No. 74 is the invention according to claim 6; 77 corresponds to the invention according to claim 7, respectively.

[0101]

[Table 8]

Sample No. of Table 9 81 to 90 are claims 1
3 to 7 correspond to the invention according to claim 7. In addition, the sample No. 83 is the invention according to claim 4, Sample No. 86 is the invention according to claim 6, sample No. 88 corresponds to the invention according to claim 9, respectively.

[0103]

[Table 9]

As shown in Tables 3 to 9, the sample No. 21-No. It was confirmed that all of 90 contained a predetermined amount or more of He and Ne in total, and had a small number of bubbles.

[Comparative Example 2] Sample No. 91-N
o. 100 represents the glass composition according to Comparative Example 2. Sample No. of Comparative Example 2 91-No. 100 was prepared by preparing molten glass in the same procedure as in Example 2 and remelting under the same conditions as in Example 2 except that the melting atmosphere was the atmospheric atmosphere.

[0106]

[Table 10]

Since Comparative Example 2 contained the fining agent component, the number of bubbles was reduced as compared with the case where the fining agent was not contained, but in comparison with Example 2 containing He and Ne,
It was found that the number of bubbles was large.

[Example 3] Sample No. 101-
110 represents the glass composition according to Example 3 of the present invention. 40 ° C at 1400 ℃ so that it has a predetermined composition
The molten glass melted under a molten atmosphere of He (purity 99.9999%) was poured out on a carbon plate for a minute, and a part of the composition was analyzed for composition confirmation, and then 0.2 mass was measured with an alumina mortar. Milled to a particle size of ~ 0.5 mm. 50 g of this crushed coarse glass was placed in a platinum crucible, placed in an atmosphere furnace having an airtight structure that was previously heated to 1500 ° C., held for 10 minutes to be remelted, and then taken out.
After cooling, it was confirmed by analysis of the composition after remelting that there was no difference with the composition before melting, and the bubble diameter of the residual bubbles in the glass was
It was measured with a stereoscopic microscope at a magnification of 20 to 100 times while being kept in an immersion liquid having the same refractive index as glass.

Sample No. of Table 11 Nos. 101 to 110 are the invention according to claim 1, Sample No. 101-108, No. 1
10 corresponds to the invention according to claims 2 and 3. Also,
Sample No. 101 is the invention according to claim 6, sample No. 1
03 and No. 110 is the invention according to claim 5, Sample No.
Nos. 104 and 108 are the invention according to claim 4, Sample No. 10
5 is the invention according to claim 9, sample No. 5; 106 is claim 8.
Related to the invention, Sample No. Reference numerals 107 respectively correspond to the invention according to claim 7.

[0110]

[Table 11]

[Comparative Example 3] Sample No. 111 ~
No. 120 represents the glass composition according to Comparative Example 3. Sample No. of Comparative Example 3 111-No. 120 is
It was prepared by remelting under the same conditions as in Example 3 except that molten glass was prepared in the same procedure as in Example 3 and the melting atmosphere was the atmospheric atmosphere.

[0112]

[Table 12]

As a result of the measurement, in Comparative Example 3 which was treated in the air atmosphere, the average bubble diameter of the remaining bubbles was 0.49 mm to 1
The average bubble diameter of the remaining bubbles in Example 3 treated with He and Ne was 0.
It was 1 mm or less, and it was found that reheating does not cause reboil.

[Example 4] Sample Nos. 1
21-No. 170 represents the glass composition according to Example 4 of the present invention. Among them, the sample No. 121-N
o. 160 was previously adjusted to have a predetermined composition,
Put a batch of 500 g of glass into a platinum crucible,
Depending on the type of glass composition, 1400 in advance
It was housed in an atmosphere furnace having an airtight structure whose temperature was raised to 1400C, 1450C, 1500C, and 1550C and held for 4 hours. In addition, the sample No. 161-No. 170 is 15
Melting was carried out at 50 ° C. for 2 hours in the same furnace. In addition, the sample No. 121-No. In 160, the crucible containing glass was housed in a furnace and held for 4 hours, then an atmosphere gas having a He or Ne concentration of 95% or more was introduced into the furnace and held at a predetermined temperature for 30 minutes. In addition, the sample No.
161-No. 170 is 1600 ° C. in He atmosphere,
The treatment was carried out for 2 hours. After that, each sample was taken out of the furnace and poured into a mold made of a glassy carbon mold to be molded. After cooling, it was confirmed by analysis of the composition after remelting that there was no difference from the composition before melting, and the bubble diameter of the residual bubbles in the glass was increased by 20 times while maintaining it in the immersion liquid having the same refractive index as the glass. From 100 to 100 times with a stereo microscope.

Sample No. of Table 13 121-125, N
o. 127 to 130 correspond to the inventions according to claims 1 to 3 and claim 4. In addition, the sample No. 126 corresponds to the invention according to claims 1 to 5.

[0116]

[Table 13]

Sample No. of Table 14 131 to 140 correspond to the inventions according to claims 1 to 4.

[0118]

[Table 14]

Sample No. of Table 15 141 and 143-14
6 and 148 correspond to the inventions according to claims 1 to 4. In addition, the sample No. 142, No. 147, No.
149 to 150 are the invention according to claim 1, sample No. 14
3 and No. 146 is the invention according to claims 8 and 10, sample No. 149 and No. No. 150 is the invention according to claims 2, 3, and 9, sample No. 145, No. Reference numeral 146 corresponds to the inventions according to claims 9 and 12, respectively.

[0120]

[Table 15]

Sample No. of Table 16 151-154 and N
o. 156, No. 158 to 160 correspond to the inventions according to claims 1 to 3. In addition, the sample No. 155 is the invention according to claim 1, sample No. 155. 151 and No. 151. Reference numeral 160 denotes the invention according to claim 9, sample No. 160. 152 and No. 158 ~
160 is the invention according to claim 4, sample No. 153 is the invention according to claim 6, sample No. 153. Reference numerals 160 respectively correspond to the invention according to claim 12.

[0122]

[Table 16]

Sample No. of Table 17 161 to 170 correspond to the inventions according to claims 1 to 3. Also, sample N
o. 161-162, No. 164 to 166, No. 1
69 to 170 are inventions according to claim 4, sample No. 16
2, No. 166 is the invention according to claim 9, sample No. 166. 1
61, No. 164-165, No. 169 to 170 are the invention according to claim 8 and sample No. 163, No. 163. 167
No. 168 is the invention according to claim 5, Sample No. 163-1
64, No. 167 to 168 correspond to the invention according to claim 6, respectively. In addition, the sample No. 161, No. 16
164-165, No. 169 to 170 are the invention according to claim 10 and sample No. 163, No. 163. 167 to 168 are the invention according to claim 11 and sample No. 162 and 166 correspond to the invention according to claim 12.

[0124]

[Table 17]

[Comparative Example 4] Sample No. 171-
No. 180, sample no. 181-No. 19
0 represents the glass composition according to Comparative Example 4, respectively. Sample No. of Comparative Example 4 171-No. No. 180 was prepared by preparing molten glass in the same procedure as the sample in Table 16 of Example 4 and remelting under the same conditions as in Example 4 except that the melting atmosphere was the atmospheric atmosphere. In addition, the sample No. 181-No. No. 190 was prepared by preparing molten glass in the same procedure as the sample of Table 17 in Example 4 and remelting under the same conditions as in Example 4 except that the melting atmosphere was the atmospheric atmosphere. Then, after cooling, it was confirmed by analysis of the composition after remelting that there was no difference with the composition before melting, while maintaining the bubble diameter of the residual bubbles in the glass in the immersion liquid having the same refractive index as the glass. The measurement was performed with a stereoscopic microscope at a magnification of 20 to 100 times.

[0126]

[Table 18]

[0127]

[Table 19]

As a result of the measurement, even in the case of directly melting from the raw materials, in Example 4 containing He and Ne, the number of bubbles after cooling was not recognized, or even if it was recognized, it was 1-2.
The number of bubbles is about 10/10 g, whereas the number of bubbles in Comparative Example 4 not containing He and Ne is about 110 to 6230 cells / 10 g, which is clearly larger than that in Example 4. That is, it was found that the number of bubbles was reduced by including He and Ne in the glass composition.

Example 5 A glass raw material was prepared so as to have the composition shown in Table 20, and 500 g of the glass raw material was put into a glass-melting crucible of platinum-rhodium (15%) and indirectly heated by an electric resistance heating element. Melting was performed in a heating furnace at 1500 ° C. for 3 hours. At this time, He gas (purity 99.9999%) was introduced into the furnace from a supply port connected to the furnace of the electric resistance furnace. Further, it is confirmed that the atmosphere in the furnace is completely replaced by He, that is, N ₂ , CO ₂ , C in the exhaust gas.
Melting was performed while confirming the analysis results of O, Ar, and O ₂ . After melting for a predetermined time, the molten glass was cast into a carbon mold to be molded, cooled in a slow cooling furnace, and then an amount necessary for analysis was collected. And 7000 made by AGILENT similar to the above
The Pt (platinum) content in the molded glass was analyzed by an ICP mass spectrometer of S. As a result, it was found that 3.1 ppm of platinum was dissolved in the glass from the inner wall of the crucible used for melting.

[0130]

[Table 20]

[Comparative Example 5] Using the same equipment as in Example 5, the same glass raw material as in Example 5 was used, and the melting atmosphere was changed to two atmospheres, that is, atmospheric air and N 2 (nitrogen) atmosphere.
It was melted at 500 ° C. for 3 hours. Note that N ₂ (nitrogen) gas was supplied from a supply port connected to the inside of the electric resistance furnace, like He. And about the obtained glass, Example 5
Similarly to the above, the Pt (platinum) content in the molded glass was analyzed by the ICP mass spectrometer. as a result,
When melted in a nitrogen atmosphere, the Pt content in the glass is 4.1 ppm, and when melted in an air atmosphere,
The Pt content in the glass was 5.1 ppm, and it was found that the Pt dissolution amount was large in all cases.

As described above, by melting the glass in the He atmosphere, it becomes possible to reduce the amount of Pt dissolved in the molten glass, and even if the glass is melted in an environment containing platinum, the glass The content of Pt in the article can be suppressed to make a homogeneous glass article.

[Example 6] In order to investigate how He acts in molten glass, the rate of gas released from molten glass by introducing He gas was investigated.

Table 21 shows the glass composition used in the investigation. 1 g of glass which had been previously melted and whose composition was investigated was held in a platinum boat and placed in an electric furnace having an airtight structure. Then, heating was performed in an environment in which nitrogen and He were introduced as a carrier gas, and the release rate of the released gas was measured. Here, the release rate of the released gas was measured by a quadrupole mass spectrometer. The results are shown in Table 22.

[0135]

[Table 21]

[0136]

[Table 22]

Samples 192 and 193 had different compositions and used different fining agents, but as is clear from Table 22, by introducing He gas as a carrier gas, any of the samples was released. The release rate of gas is about 1 compared to the case of using nitrogen, regardless of temperature.
It is almost 0 times. Such a gas release rate is directly proportional to the internal partial pressure of the gas in the molten glass, and it is possible to indirectly understand that the internal partial pressure of the molten glass is increased by introducing He. did it.

[0138]

The glass composition according to the present invention is produced by melting glass raw materials and contains a multi-component oxide as a main component,
Since the molten glass contains a predetermined amount of helium and / or neon, there are almost no bubbles remaining as defects in the glass, and the glass has high homogeneity. Therefore, according to the present invention, the rise of various industries utilizing various glass products can be promoted more than ever.

Further, by including a fining agent component, it is possible to surely perform fining at the time of melting the glass and to provide a glass product with a property that is difficult to be reboiled by heat treatment or the like. Therefore, it is possible to promote the development of further applied applications in the industrial field where glass products are used.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Hachiro Takahashi             2-7-1, Harashira, Otsu City, Shiga Prefecture             Air Glass Co., Ltd. (72) Inventor Shigeaki Aoki             2-7-1, Harashira, Otsu City, Shiga Prefecture             Air Glass Co., Ltd. (72) Inventor Mitsuo Kato             2-7-1, Harashira, Otsu City, Shiga Prefecture             Air Glass Co., Ltd. F-term (reference) 4G062 AA01 AA03 AA04 BB01 DA04                       DA05 DA06 DA07 DB03 DB04                       DC01 DC02 DC03 DC04 DD01                       DE01 DF01 EA01 EB01 EB02                       EB03 EC01 EC02 EC03 ED01                       EE01 EE02 EE03 EF01 EF02                       EF03 EG01 EG02 EG03 FA01                       FB01 FC01 FC02 FC03 FD01                       FE01 FE02 FE03 FF01 FG01                       FH01 FJ01 FK01 FL01 GA01                       GB01 GB02 GB03 GC01 GD01                       GE01 HH01 HH03 HH05 HH07                       HH09 HH11 HH13 HH15 HH17                       HH20 JJ01 JJ03 JJ05 JJ06                       JJ07 JJ10 KK01 KK03 KK05                       KK07 KK10 MM01 MM02 NN40

Claims (12)

[Claims] 1. A glass composition containing a multi-component oxide as a main component, which is produced by melting a glass raw material, and contains 0.01 to at least one component selected from helium and neon. A glass composition containing 2 μL / g (0 ° C., 1 atm). 2. The glass composition according to claim 1, which contains a clarifying agent component in an amount of 0.001 to 3% by mass. 3. SO ₃ , Cl, H ₂ O as a fining component,
The glass composition according to claim 1, which contains one or more components selected from Sn, Sb, F, and As. 4. Sb as Sb ₂ O ₃ is 0.01 to 1.5.
The glass composition according to claim 1, wherein the glass composition contains mass%. 5. The glass composition according to claim 1, which contains SO ₃ in an amount of 0.001 to 1.0 mass%. 6. The glass composition according to claim 1, containing 0.01 to 1.5 mass% of Cl. 7. The glass composition according to claim 1, which contains 0.01 to 0.2% by mass of H ₂ O. 8. A mass percentage of 5 pp with Sn as SnO _2.
The glass composition according to claim 1, which contains m to 2 mass%. 9. As is As ₂ O ₃ and 0.01 to 1.5.
The glass composition according to claim 1, wherein the glass composition contains mass%. 10. Sb as Sb ₂ O _{3 from} 0.01 to 1.
The glass composition according to claim 1, wherein the glass composition contains 5 mass% and Sn as SnO ₂ in a mass percentage of 5 ppm to 2 mass%. 11. The glass composition according to claim 1, which contains 0.001 to 1.0 mass% of SO ₃ and 0.01 to 1.5 mass% of Cl. 12. Sb as Sb ₂ O _{3 from} 0.01 to 1.
5 mass% is included, and As is 0.01 as As ₂ O _3.
The glass composition according to claim 1, wherein the glass composition contains ˜1.5% by mass.