WO2007094372A1

WO2007094372A1 - Method for producing glass article and glass article

Info

Publication number: WO2007094372A1
Application number: PCT/JP2007/052641
Authority: WO
Inventors: Hiromitsu Seto; Akihiro Koyama
Original assignee: Nippon Sheet Glass Company, Limited
Priority date: 2006-02-14
Filing date: 2007-02-14
Publication date: 2007-08-23
Also published as: JP2009107850A

Abstract

Disclosed is a method for producing a glass article containing NiO, wherein generation of NiS is suppressed as much as possible. Specifically disclosed is a method for producing a glass article, which comprises a step wherein a glass raw material (a) substantially not containing a nickel-containing compound while containing a sulfur-containing compound is mixed with a glass material obtained by melting a glass raw material (b) substantially not containing a sulfur-containing compound while containing a nickel-containing compound and/or a compression molded product of such a glass raw material (b); and a step wherein the thus-obtained mixture is melted.

Description

Specification

Glass article manufacturing method and glass article

Technical field

[0001] The present invention relates to a method for manufacturing a glass article, and more particularly to a method for manufacturing a glass article containing nickel oxide. In particular, in a method for manufacturing a glass plate that is formed into a plate shape by the float process or roll-out method, three methods can be established to improve glass bubble quality, control oxidation-reduction conditions, and reduce NiS generation. About. Moreover, this invention relates to the glass article obtained by the said manufacturing method.

Background art

[0002] Normally, soda lime silica glass is manufactured by weighing and mixing predetermined raw materials, and then charging the cullet with this into a melting furnace. The feedstock is heated from room temperature and heated to a maximum of 1500-1600 ° C in a melting furnace to be melted and vitrified.

[0003] When producing soda lime silica glass, a sulfate compound (calcium sulfate, sodium sulfate, etc.), which is a sulfur-containing compound, is added to the glass batch in order to promote melting and clarification. In particular, sodium sulfate (hereinafter referred to as mirabilite) is generally obtained. The melting point of mirabilite is 884 ° C. When this temperature is exceeded, mirabilite is considered to be in the liquid phase and promote the vitrification reaction.

[0004] The sulfur-containing compound contained in the glass batch is mainly the above-described sulfate compound. In addition to this, blast furnace slag containing sulfur called Calmite (registered trademark) is also cited as a sulfur-containing compound contained in a glass batch.

[0005] Furthermore, mirabilite is considered to react with a carbon-based reducing agent (for example, carbon) added together in a glass batch to produce sodium sulfide (Na 2 S).

[0006] Na S described above reacts with silica (SiO) to promote silica roasting and glass network formation, and is therefore considered to be an important substance for promoting the vitrification reaction. . However, it is very difficult to directly observe Na S in the melt.

[0007] The exact numerical value of the formation temperature range of S ² — is not clear, and the force fluctuates depending on the constituents of the glass batch. It is considered that the temperature is approximately 800 to 1200 ° C. [0008] Nickel oxide (NiO) has long been used as a yellowish brown to dark purple coloring material in glass compositions. In recent years, it has also been used as a coloring component for glass with relatively low visible light transmittance, which is used for automotive rear window glass. The NiO component contained in such low visible light transmittance glass is from several tens of ppm, and in many cases, it contains 1000 ppm or more.

By the way, the above-mentioned S ² — reacts easily to form nickel sulfide (NiS) when nickel oxide (NiO) is present.

[0010] In addition to the case where it is used as a coloring raw material, there is a possibility that Nikkenole may be mixed in industrially produced glass articles. For example, metallic nickel is also widely used as an alloy such as stainless steel and welding rods, and small pieces of these nickel alloys often get mixed into industrial glass raw materials and cullet and are thrown into the kiln. Because. Although the melting reaction of nickel alloy in the kiln is not clear, nickel in the alloy is also considered to combine with the above-mentioned S ² — to form NiS.

[0011] Although the NiS formation temperature range is not clear, it is considered that the above-mentioned S ² — generation temperature range is 800 ° C or higher, and the industrial nickel sulfide formation temperature is about 1000 ° C. From 800 ~

Presumed to be in the temperature range of 1200 ° C.

[0012] When the temperature rises to 1300 ° C or higher, the produced NiS is considered to melt or diffuse again in the glass and disappear. It is estimated that the melting rate and diffusion rate are higher at higher temperatures.

[0013] Now, heat tempered glass is used as one of safety glasses for automobiles. Thermally tempered window glass can spontaneously break very rarely without the application of particularly large external forces. The heat strengthened glass has a compressive stress layer on the surface and an internal tensile stress layer. In the case where minute foreign matter, particularly nickel sulfide (NiS), is present in this tensile stress layer, this NiS undergoes a transition from the splay phase to the β phase with the passage of time. It is known to damage tempered glass.

[0014] For this reason, various glass production methods have been studied in order not to generate NiS.

[0015] Japanese Patent Application Laid-Open No. 49-118711 is characterized in that a part of mirabilite is replaced with glass stone and soda ash among raw material composition components at the time of production of plate glass, and does not contain carbon. A glass raw material composition is disclosed.

[0016] US Pat. No. 5,725,628 is characterized in that in the production process of soda-lime glass, a manganese compound is added at least 1.4 times the nickel content in order to remove nickel sulfide. A glass manufacturing method is disclosed.

[0017] In addition, in Japanese Patent Application Laid-Open No. 7-144922, in a method for producing soda lime glass, a batch material includes molybdenum, arsenic, antimony, bismuth, copper, silver, potassium dichromate and chromite iron, and those. Disclosed is a method for producing glass, characterized in that at least 0.010% by weight of a substance selected from the group consisting essentially of the combination is added.

[0018] The applicant of the present invention disclosed in Japanese Patent Application Laid-Open No. 9-169537 is melt-molded due to a nickel-based compound contained in a glass raw material and / or a nickel-based compound mixed in the melting process of the glass raw material. Disclosed a method for producing soda-lime-based glass, characterized in that nickel sulfide produced in the glass is suppressed by adding a small amount of a zinc compound to the glass raw material.

[0019] On the other hand, various glass manufacturing methods used as a raw material by adding a glass raw material batch obtained by adding a combination of a frit glass and a part of batch components and solidifying them are also disclosed.

[0020] Japanese Patent Application Laid-Open No. 6-1633 discloses a reduction in glass by appropriately combining a high reduction rate and / or a relatively high reduction rate frit glass, a specific amount of sodium sulfate, and a specific amount of carbon as appropriate. A method for producing an infrared ultraviolet absorbing glass by controlling the rate so as to fall within a specific range is disclosed.

[0021] JP-A-11 116270 discloses an ultraviolet-absorbing colorless and transparent soda-lime-silica glass bottle characterized in that a colored frit containing VO and a colored frit containing Se are added and stirred, and then molded. A manufacturing method is disclosed.

[0022] In JP 2005-519015, specific components of the glass batch composition are selectively combined to reduce daros segregation of the batch components in the glass melt, and further provide a thermal reaction path. A method for improving the melting efficiency by controlling is disclosed.

[0023] However, the glass production method disclosed in Japanese Patent Application Laid-Open No. 49-118711 has reduced the amount of sodium sulfate having a glass clarification action, so bubbles in the glass cannot be completely removed. Also of glass Since carbon that adjusts the redox state is not included, optical characteristics cannot be adjusted. For this reason, for example, it was not possible to obtain the foam quality and optical properties necessary for automobile window glass.

[0024] US Pat. No. 5,725,628 contains a large amount of a manganese compound that acts as a strong oxidant, so that the redox condition of the glass becomes oxidation and the optical properties cannot be adjusted. For this reason, for example, it was not possible to obtain the optical characteristics required for automobile window glass.

[0025] The glass manufacturing method disclosed in Japanese Patent Application Laid-Open No. 7-144922 is not based on the premise that the glass batch contains NiO, and is formed as a contamination by introducing it into the glass raw material only slightly. It was a measure for NiS. For this reason, for example, the glass composition containing NiO could not be used for NiS countermeasures.

[0026] Also in JP-A-9-169537, since it is necessary to add a zinc compound that acts as an oxidizing agent, the redox of the glass is close to oxidation, making it difficult to adjust the optical properties. For this reason, for example, it has been difficult to obtain the quality and optical characteristics required for automobile window glass.

[0027] Japanese Patent Application Laid-Open No. 6-1633 discloses a method for adjusting the reduction rate of glass by using a combination of a high reduction rate frit glass and a glass raw material batch of mirabilite and vigor. However, there is no disclosure or suggestion as to whether NiS formation is effective.

[0028] Japanese Patent Application Laid-Open No. 11-116270 adds glass frit containing V 2 O and Se, respectively.

twenty five

In addition, a method for obtaining the optical characteristics of an ultraviolet-absorbing colorless and transparent soda lime silica glass by adding the above is disclosed. However, the composition of the glass frit is based on low melting point glass such as borosilicate, and has a power that does not provide an effect of preventing NiS formation.

[0029] JP-T-2005-519015 discloses a method that selectively frits, pelletizes, or pre-reacts a specific batch component, thereby reducing the dalos segregation of the batch component and further controlling the thermal reaction path. Thus, a method for improving the melting efficiency is disclosed. However, there is no disclosure or suggestion about the effectiveness of preventing NiS formation.

By the way, the above-described carbon-based reducing agent has an important function for determining the redox state of glass. The index that represents the redox state of glass is the total iron oxide in the glass. The ratio of divalent iron to Fe (FeO ratio) is generally used. A reducing agent such as carbon works to increase the FeO ratio. On the other hand, sulfate compounds and nitrate compounds work to lower the FeO ratio.

[0031] The divalent iron in the glass absorbs infrared rays well. In the window glass for automobiles, high heat ray absorption performance is obtained by utilizing absorption by this divalent iron. In this case, it is necessary to obtain the desired FeO ratio while maintaining the homogeneity and foam quality of the product glass.

On the other hand, NiS produced in glass is deeply related to the redox state of glass. Qualitatively, it is known that NiS is easy to form in a reduced state that is difficult to form if the glass is in an oxidized state. In terms of the above FeO ratio, NiS is more likely to be produced if an attempt is made to obtain a high heat and FeO ratio in order to obtain high heat-absorbing performance.

[0033] Therefore, in order to obtain desired optical characteristics, there is a need for a technique that suppresses the formation of Ni S while maintaining a particularly high FeO ratio.

Disclosure of the invention

[0034] In view of these circumstances, an object of the present invention is to provide a method for producing a glass article that can minimize the generation of NiS in a glass article containing NiO. It is another object of the present invention to provide a method for producing a glass article that can minimize the generation of strength NiS without being affected by the bubble quality and redox state of the glass. It is another object of the present invention to provide a glass article that contains NiO and produces little NiS.

[0035] The present invention that has achieved the object comprises a glass raw material (a) substantially free of a nickel-containing compound and containing a sulfur-containing compound,

A step of mixing a glass body obtained by melting a glass raw material (b) substantially free of a sulfur-containing compound and containing a nickel-containing compound, and a compression molded product of Z or the glass raw material (b), and

It is a manufacturing method of the glass article including the process of melting the obtained mixture.

[0036] The present invention is also a glass article obtained by the production method, wherein the basic composition is expressed in mass%,

SiO 65-80%, Al〇 0-5%,

MgO 0 ~: 10%,

CaO 5 ~: 15%,

MgO + CaO 5 ~: 15%,

Na O 10-18%,

K O 0-5%,

Na O + K O 10 ~ 20%,

B 0-5%

Including

A glass article containing at least 0.03-2.0% of NiO as a coloring component. Brief Description of Drawings

[0037] FIG. 1 is a graph showing the relationship between the particle size of a glass body and the number of NiS per 100 g of glass article.

FIG. 2 is a graph showing the relationship between the FeO ratio of a glass article and the number of NiS per 100 g when a compression molded product is used as a nickel source.

FIG. 3 is a graph showing the relationship between the FeO ratio of a glass article and the number of NiS per 100 g when glass powder composition A is used and powdered nickel oxide is used as the nickel source.

FIG. 4 is a graph showing the relationship between the FeO ratio of a glass article and the number of NiS per 100 g in the case of glass plate composition B when powdered nickel oxide is used as the nickel source.

BEST MODE FOR CARRYING OUT THE INVENTION

[0038] In order to reduce the number of NiS, the inventors of the present invention have a great influence on preventing NiO and S ² — from meeting in the temperature range of 800 to 1200 ° C in the process of melting glass. Considered important

[0039] Therefore, the inventor conceived that NiO should be surrounded by a component not containing S ² —. In order to realize this, the following method was devised.

Glass raw materials substantially free of nickel-containing compounds and containing sulfur-containing compounds (a

)

(1) Glass raw material substantially free of sulfur-containing compounds and containing nickel-containing compounds Use a glass body obtained by melting (b), or

(2) A compression molded product of the glass raw material (b) substantially free of a sulfur-containing compound and containing a nickel-containing compound is used.

[0040] Therefore, in the production method of the present invention, the glass raw material (a) substantially free of a nickel-containing compound and containing a sulfur-containing compound, and the nickel-containing compound substantially free of a sulfur-containing compound. And a glass body obtained by melting the glass raw material (b) and / or a compression molded product of the glass raw material (b).

[0041] (Glass raw material (a))

Glass raw material (a) provides a source of sulfur-containing compounds to promote melting and fining. The sulfur-containing compound refers to a compound containing elemental sulfur, and examples thereof include sulfate compounds such as calcium sulfate and sodium sulfate (sodium salt), and calumite (registered trademark).

[0042] The glass raw material (a) is usually a mixture of raw materials to be a sulfur element source, a metal element source and a silicon element source. The composition of the glass raw material (a) refers to the composition of the glass body obtained by melting the glass raw material (b) and / or the compression molded product of the glass raw material (b), and the composition of the glass article to be produced. If you decide as appropriate.

[0043] The fact that the glass raw material (a) does not substantially contain a nickel-containing compound means that the nickel-containing compound is not intentionally added. Therefore, it means that contamination as an inevitable impurity is allowed. Here, the nickel-containing compound refers to a compound containing a nickel element, and examples thereof include nickel oxide, nickel carbonate, nickel chloride, and nickel nitrate. Even when the nickel-containing compound is mixed as an inevitable impurity, its content is preferably less than 0.1% by mass, and more preferably less than 100% by mass.

[0044] (Glass raw material (b))

The glass raw material (b) is a supply source of nickel oxide which is a coloring component. The fact that the glass raw material (b) does not substantially contain a sulfur-containing compound means that the above-mentioned sulfur-containing compound is not intentionally added. Therefore, it means that contamination as an inevitable impurity is allowed. Even if sulfur-containing compounds are mixed as inevitable impurities The amount is preferably less than 0.1% by weight, particularly preferably less than 100% by weight.

[0045] The glass raw material (b) is used in the form of a glass body or a compression molded product so as to surround the nickel-containing compound with other components.

[0046] The composition of the glass raw material (b) is expressed in mass% when converted to an oxide,

SiO 60-80%,

Al O 0-5%,

MgO 0 ~: 10%,

CaO 0-15%,

MgO + CaO 5 ~: 15%,

Na O 10-18%,

K O 0-5%,

Na O + K O 10 ~ 20%,

Ni〇 1 ~: 15%

It is preferable to contain. Henceforth, the% display regarding content represents the mass%, and the description regarding the composition of glass raw material (b) is an oxide conversion.

[0047] (SiO 2)

The glass body and / or the compression molded product must be finally mixed with other raw materials to form a homogeneous glass composition. Therefore, compared to the final glass composition, if the viscosity is too high, it will be difficult to mix with other raw materials, and will cause defects such as color spots. For this reason, it is more preferable that the glass raw material (b) contains 65 to 80% of the SiO component, and more preferably 70 to 80%.

[0048] (ΝΪΟ)

In the manufacturing method of the present invention, only this glass body and Z or compression molded product substantially supply NiO to the final glass article. The content of NiO in the final glass article is expressed as the product of the content of NiO in the glass body and Z or compression molding and the ratio of the glass body and Z or compression molding used. Homogeneous in proportion to the addition of glass bodies and / or compression moldings of different composition from the final glass article From the standpoint of obtaining a clear glass, less is preferred.

[0049] On the other hand, as the NiO content in the glass body increases, the number of NiS produced in the final glass article tends to increase. For this reason, when a mixture contains a glass body, it is more preferable that the NiO content rate in the glass raw material (b) of the said glass body is 1-7% in mass%. On the other hand, when the mixture includes a compression molded product, the NiO content in the glass raw material (b) of the compression molded product is more preferably 5 to 15%.

[0050] The glass raw material (b) may contain a coloring component other than NiO, and preferably contains an iron-containing compound. The iron-containing compound is preferably iron oxide. By including an iron-containing compound in the glass raw material (b), it is presumed that a higher NiS suppression effect can be obtained by the action of its own oxidizing power or the affinity between Fe and S. The content of the total iron oxide converted to Fe 2 O is preferably 0.05 to 40%, more preferably 1 to 10%.

[0051] (1) Glass body obtained by melting glass raw material (b)

The first specific solution according to the present invention is a method of preparing a glass body obtained by melting the glass raw material (b) in advance and using this. The glass raw material (b) may be melted according to a conventional method. The glass body is preferably used in the form of a frit.

[0052] The composition of the glass body preferably has a log 77 = 4 temperature of the same or higher than that of the final glass article. Where 77 is the viscosity of the glass melt

. When the temperature of log r? = 4 is low, the glass body containing NiO diffuses rapidly around the specified temperature range. For this reason, it is not sufficient to surround NiO with a glass component made of an oxide that does not contain S ² —. For example, when the final glass article is soda lime silica glass, it is preferable to use a glass body having a log r? = 4 temperature of about 1000 ° C or higher.

[0053] (Shape, particle size)

The glass body is formed into various shapes such as spherical, cylindrical, flat plate, lamellar, cubic, and thread-like, and can be used. In particular, it is preferable to be molded into a shape with a relatively small specific surface area such as a spherical shape, a cylindrical shape, or a cubic shape. The glass body is preferably used in as large a shape as possible as long as the homogeneity of the final glass composition is not impaired.

[0054] When the shape of the glass body is roughly particulate, when converted into a sphere, It is more preferable that the average particle size is at least 5 mm, and it is more preferable that the average particle size is at least 1.5 mm. The particle size is the particle diameter. When the shape of the glass body is approximately flaky, it is preferable to form the glass body so that its thickness is at least 0.5 mm. In the case of flakes, the average particle size should be at least 10 mm. Here, the average particle diameter can be determined by, for example, a sieving method.

In this glass body, the ratio (S / V) of the surface area S (mm ² ) to the volume V (mm ³ ) is preferably 4 mm− ¹ or less. For example, when the glass body is a sphere, SZV = 4 mm— ¹ at a diameter of 1.5 mm, SZV = 3 (mm— at a diameter of 2 mm, and SZV = lmm— ¹ at a diameter of 6 mm. If the body shape is spherical, the diameter should be 1.5 mm or more to achieve SZV force S4 mm ¹ or less.

[0056] (2) Compression molding of glass raw material (b)

The second concrete solution according to the present invention is a method in which a compression molded product obtained by previously compressing and molding a glass material (b) containing NiO is prepared and used. Note that compression-molding the raw material for glass batches is sometimes referred to as pricketing.

[0057] (Shape)

As the compression molded product, various shapes such as a spherical shape, a cylindrical shape, a flat plate shape, a flake shape, a cubic shape, and a thread shape may be used. In particular, those having a relatively small specific surface area such as a spherical shape, a cylindrical shape, and a cubic shape are preferable.

In this compression molded product, the ratio (S / V) of the surface area S (mm ² ) to the volume V (mm ³ ) is preferably ¹ mm ¹ or less when the compression molded product is a sphere. Therefore, the diameter is preferably 6 mm or more when the compact is a sphere.

[0059] It should be noted that in order to make a compression molded product into a sphere, it is necessary to compress it under hydrostatic pressure, which is not common. When producing a compression molded product, the easiest method is to press and mold in a uniaxial direction. In that case, a cylindrical shape, a plate shape, a flake shape, a rectangular parallelepiped shape, etc., where the pressing surface is a parallel plane, or a flat shape where the pressing surface is curved by using a device such as a tableting machine and a mold Is generally.

[0060] (Material)

Compressed molded products are components that decompose quickly, such as nitrate compounds and hydroxides, and high temperatures. It is preferable not to include a component that forms a liquid phase. The compression molded product is preferably a raw material mainly composed of an oxide or a carbonate compound. For example, in soda lime silica glass, it is preferable to use at least one selected from the group consisting of quartz sand, dolomite, limestone, and soda ash. In particular, it is more preferable that the compression-molded product is a material obtained by compressing and solidifying a glass raw material (b) consisting essentially of silica sand, dolomite, limestone, soda ash and nickel oxide.

[0061] The glass raw material (a) and / or the glass raw material (b) may further contain an iron-containing compound (eg, iron oxide). In this case, the glass material containing the iron-containing compound is reduced. It may further contain an agent. The reducing agent can adjust the optical characteristics of the glass article. Examples of the reducing agent include carbon-based reducing agents such as carbon.

[0062] The mixing of the glass raw material (a) with the glass body and / or the compression-molded body may be performed according to a known method. For example, use a ball mill or planetary mill for a crucible scale, and mix using a blender mixer for a melting furnace scale. Either the glass raw material (a) and the glass body and / or the compression-molded body may be added first or simultaneously. The mixing ratio of the glass raw material (a) and the glass body and / or the compression molded body is appropriately determined depending on the NiO content in the glass body and / or the compression molded body and the required final glass composition. Although there is no particular limitation, it is preferable that the ratio of the glass body and / or the compression molded body is low. The mixing ratio may be, for example, in the range of about 99.8: 0.2 to 80:20 as a mass ratio of the glass raw material (a): glass body and / or compression molded body.

[0063] Next, a step of melting the mixture obtained in the above step is performed. The process may be performed according to a known method. For example, the mixture may be melted by heating at 1350 to: 1650 ° C. for 2 to 6 hours using an electric furnace in a crucible (particularly in a platinum norevo). Further, for example, in a general glass melting furnace (Siemens furnace), the mixture may be retained in the furnace and heated at 1350 to 1650 ° C. for about 50 to 100 hours for melting.

[0064] Next, in an industrial production, a glass article can be obtained by shaping the molten glass according to a known method such as a float method or a roll-out method.

[0065] The step of heating and quenching the obtained glass article to strengthen the glass article is further performed. May be. The process may be performed according to a known method. For example, the glass article is heated to the vicinity of the softening point of glass (about 650 ° C for soda-lime glass), and compressed air is sprayed onto the glass surface. Can be quickly cooled.

[0066] (Composition of glass article)

In the method for producing a glass article of the present invention, the glass article to be produced is preferably soda lime silica glass containing NiO as a coloring component. As a specific basic glass composition expressed in mass%,

SiO 65-80%,

Al O 0-5%,

MgO 0 ~: 10%,

CaO 5 ~ 15%,

MgO + CaO 5 ~: 15%,

Na O 10 ~: 18%,

K O 0-5%,

Na O + K O 10 ~ 20%,

B 0-5%

And a composition containing NiO as a coloring component is preferably included.

[0067] Further, the type of the glass article that may contain a coloring component other than NiO is not particularly limited in order to adjust optical properties such as color tone. Not only iron oxide but also TiO, CeO, CoO, Se, etc. may be included.

[0068] The coloring component is preferably specifically,

T-FeO over 0, up to 1.4%,

(T-Fe 2 O is all iron oxide converted to Fe 2 O)

Over TiOO 0 to 1%,

CeO over 0 up to 2%,

CoO over 0 up to 0.03%,

Se 0 over 0.03%,

Power At least one selected. [0069] The coloring component is

T-Fe O 0.:!~ 1 · 4%,

(T-Fe 2 O is all iron oxide converted to Fe 2 O),

The ratio of FeO to T-FeO (FeO ratio) is in the range of 0.15 to 0.5,

Ti〇 0 to 1%,

CeO 0-2%,

CoO 0.01-0.03%,

Se 0-0.003%,

(A component containing 0% in the content range is a component that may be added if necessary). When such a coloring component is used, a glass article having excellent absorption of ultraviolet rays and infrared rays and having a relatively small visible light transmittance can be obtained.

[0070] When the glass article produced by the production method of the present invention contains iron oxide, the FeO ratio is 0.

The force S is preferably in the range of 20 to 0 · 30, more preferably the force S is in the range of 0 · 21 to 0 · 27.

[0071] According to the glass manufacturing method of the present invention, it is possible to provide a glass article in which the generation of NiS is reduced as much as possible.

[0072] Further, in the NiS countermeasure in the conventional glass manufacturing method, the ratio of adding a clarifier and a reducing agent containing a sulfur-containing compound is limited. However, according to the method for producing glass of the present invention, the ratio of adding a fining agent containing a sulfur-containing compound such as mirabilite is not limited for NiS countermeasures. Further, the ratio of adding the reducing agent is not limited. For this reason, it became possible to adjust the ratio of adding a refining agent or a reducing agent that controls the redox state of the glass independently of NiS countermeasures. As a result, the optical properties of the glass can be easily designed by reducing the NiS generation as much as possible, maintaining the bubble quality of the glass, and controlling the redox state.

[0073] The glass article obtained by the production method of the present invention is useful as a base plate for heat strengthening, and is particularly suitable for automobile window glass, architectural window glass, and the like.

Hereinafter, the glass article of the present invention will be described in detail with reference to examples, but the present invention is not limited to these examples. [0075] (1) Production of glass body obtained by melting glass raw material (b)

The glass body was produced according to the following procedure. Silica sand, dolomite, limestone, and soda ash were used as the glass raw material (b), and nickel oxide was used as the coloring component material. The above materials were mixed at a predetermined ratio to prepare a glass body batch.

[0076] The prepared batch was melted by holding it in an electric furnace set at 1450 to 1550 ° C for 4 hours using a platinum crucible. Thereafter, a glass body having a desired shape and size such as the above-described various shapes, for example, flake shape and spherical shape (marble), was obtained from the glass melt.

[0077] (2) Production of compression molded product of glass raw material (b)

A compression molded product of the glass raw material (b) was produced according to the following procedure. As materials, quartz sand, dolomite, limestone and soda ash were used, and nickel oxide and iron oxide were appropriately used as coloring component materials. The above-mentioned materials were mixed at a predetermined ratio, an appropriate amount was put into a predetermined mold, and pressed with a press machine for about 4 to 20 [X104N] (4 to 20 t) for 20 seconds to be molded into a desired shape. <I) A 25mm x 3mm thick, φ16mm x 5mm thick vinyl chloride pipe cut into a formwork was sandwiched between φ70mm x 10mm thick iron dies.

[0078] (Manufacture of glass plate)

As an example of a glass article, a glass plate was produced according to the following procedure. Silica sand, dolomite, limestone, soda ash, mirabilite, and potassium carbonate were used as raw materials for the basic glass component. As coloring components, nickel oxide, ferric oxide, titanium oxide, cerium oxide, cobalt oxide and metal selenium were used, and a carbon-based reducing agent was used. The glass body or the compression molded product was used as the nickel oxide raw material. The above raw materials were mixed at a predetermined ratio to prepare a glass batch.

[0079] The FeO ratio in each example was controlled by a carbon-based reducing agent (carbon powder or the like).

[0080] A glass batch using a powdered nickel oxide raw material was also prepared to prepare a glass plate, which was used as a comparative example.

[0081] The prepared batch was kept in an electric furnace set at 1450 ° C for 4 hours using a platinum crucible, and melted and refined. Thereafter, the glass melt was poured out on the iron plate outside the furnace to a thickness of about 6 mm, and cooled and solidified to obtain a glass plate. This glass plate was then slowly cooled. Made the work. The slow cooling operation was performed by holding the glass body in another electric furnace set at 650 ° C for 30 minutes, and then turning off the electric furnace and cooling it to room temperature.

[0082] The glass plate after the slow cooling operation was observed with an optical microscope (magnification: 10 to 100 times), and the number of NiS present in the glass body was measured. The observed glass plate is cut, ground, and optically polished by applying normal glass processing technology. It is a roughly rectangular parallelepiped with a side of about 50 mm and a thickness of 3.1 mm. A polished glass plate was produced.

[0083] (Glass plate composition)

Table 1 shows the glass composition of the produced glass plate. Glass plate compositions A and B have almost the same glass composition (basic component) except for the coloring component, but the content of each component contained in the basic component differs depending on the content of the coloring component. The content of each component is a quantitative analysis value using a general-purpose analysis method suitable for that component, such as X-ray fluorescence analysis, chemical analysis, or flame analysis. All contents in the table are expressed in mass%, and the total is not 100% due to rounding errors in the analysis results.

[0084] [Table 1]

The glass plate compositions A and B have different coloring components, the content of NiO and CoO is about the same, and the content of FeO differs greatly. Furthermore, glass plate composition A contains CeO, and glass plate composition B contains Se. [0086] (1) Example using glass body containing NiO

Examples F1 to F23 are examples in which a glass article was manufactured using a glass body containing nickel oxide as a nickel oxide source. Table 2 shows the composition of the glass body used in each example.

~ Shown in Table 4.

[0087] [Table 2]

[0088] Examples F1 to F4 shown in Table 2 were obtained by changing the content of NiO in the glass body. NiO content rate in the final glass article The glass body ratio was adjusted so that the glass plate composition B in Table 1 was obtained. Table 2 shows the number of NiS and FeO ratio per 100g of glass articles.

[0089] The FeO ratio of Examples F1 to F4 was 17.5 to 18.9%. As will be described later, a comparative example R14 having the same FeO ratio (18.7%) as in Examples F1 to F4 was produced using nickel oxide powder as a nickel source. The number of NiS in R14 was about 42 / 100g. Compared to this, the number of NiS in Examples F1 to F4 was about 18 to about 33 pieces / 100 g, which was smaller than that of R14. Of these, Examples F1 to F3 are glass articles prepared using a glass body containing 1 to 7% NiO, and the number of NiS in the glass is from Example F4 using a glass body containing 12% NiO. I was able to reduce it.

[0090] [Table 3]

[0091] In Examples F5 to F12 shown in Table 3, the content of NiO in the glass body is constant at 6%, and the content of NaO and the content of CaO are included together with the content of SiO. Something that has changed

twenty two

The The ratio of the glass body was adjusted so that the NiO content in the final glass article was the glass plate A in Table 1. Table 3 shows the number of NiS per 100g of glass articles.

[0092] The FeO ratio of Examples F5 to F12 was 20 to 23%. As will be described later, the number of NiS in Comparative Example R10 having the same FeO ratio (23%) as Examples F5 to F12 was about 19/100 g. In comparison with this, the number of NiS in Examples F5 to F12 was about 2 to about 16 pieces / 100 g, which was smaller than that of R10.

Of these, Examples F5, F7, Fl l, and F12 are within the range of 70 to 80% of SiO force in the glass body.

2

On the other hand, F6, F8 to F10 are Si0 forces ¾0% or 60% in the glass body.

2

The Comparing the two, the direction force of Examples F5, F7, Fl l and F12 The number of NiS in the glass article Was able to be reduced.

[0094] [Table 4]

[0095] Examples F13 to F16 and Examples F17 to F23 shown in Table 4 are obtained by changing the average particle size of the glass body with the same glass composition of the glass body. The proportion of the glass body was adjusted so that the NiO content in the final glass article was the glass plate composition A in Table 1. Table 4 also shows the number of NiS per 100g of glass articles and the average particle size of the glass body.

[0096] The FeO ratio of Examples F13 to F16 and Examples F17 to F23 was 20 to 23%. When compared with the NiS number of about 19/100 g in Comparative Example R10 having the same FeO ratio as these, the number of NiS in Examples F13 to F16 and Examples F17 to F23 is about 0.4 It was about 13 / 100g and about 0.4 · about 10 / 100g, which was less than that of R10.

[0097] The glass articles of Examples F14 to F17 and F20 to F23 had an average particle diameter of 1.5 mm or less. A glass article with a preferred average particle size. The number of NiS in the glass article could be reduced as compared with a glass article produced using a glass body having an average particle size of less than 1.5 mm.

[0098] Fig. 1 shows the relationship between the average particle size of the glass body and the number of NiS per lOOg. As is clear from Fig. 1, it can be seen that the number of NiS suddenly decreases when the average particle size is increased. The same tendency when the SiO content in the glass body is 70% or 80%

2

Was showing.

[0099] (2) Example using compression molded product of glass raw material (b) containing NiO

Examples Bl to B11 are examples in which a glass article was prepared using a compression molded product of glass raw material (b) containing nickel oxide and nickel oxide as a nickel oxide source. Tables 5 and 6 show the composition of the compression molded product used in each example.

[0100] This compression-molded product is essentially a glass raw material (b) made of silica sand, dolomite, limestone, soda ash, and nickel oxide, compressed and solidified.

[0101] [Table 5]

[0102] Of the examples shown in Table 5, Examples B1 to B3 do not contain an iron source in the compression molded product. The ratio of the compression molded product was adjusted so that the NiO content in the final glass article was the glass plate composition A in Table 1. Table 5 also shows the number of NiS per glass article lOOg and the ratio of FeO.

[0103] Compared to the NiS number of about 19 / lOOg in Comparative Example R10 described above, the number of NiS in Examples Bl and B2 is about 8 / lOOg and about 9 / lOOg, which is higher than that of R10. I was able to reduce it.

[0104] In Example B3, 5% by mass of cerium oxide was contained in the compression molded product, and the number of NiS of the glass article produced by using the compression molded product of B3 was B 1 or B2. I was able to make it even less.

[0105] Of the examples shown in Table 5, Examples B4 and B8 are obtained by including iron oxide as an iron source in the compression molded product. The number of NiS in glass articles made using B4 and B8 compression moldings could be made even smaller than Bl and B2. In addition, the number of NiS tended to decrease as the amount of iron oxide contained in the compression-molded product increased.

[0106] FIG. 2 shows the relationship between the FeO ratio and the number of NiS per 10 Og of the glass article in the example using the compression molded product and the comparative example described later. As is clear from Fig. 2, there was a large difference in the ratio of the increase in the number of NiS to the increase in the FeO ratio, ie, the slope of the approximate line, in this example and the comparative example. That is, in the comparative example, as the FeO ratio is increased, the number of NiS is greatly increased. In contrast, it was found that the rate of increase was smaller in the example.

[0107] [Table 6]

The compression moldings of Examples B9 and B11 shown in Table 6 have a ratio (S / V) (mm— of the surface area S (mm ² ) to the volume V (mm ³ ) of 1.2 and 0.8, respectively. The compression molded product molded to φ25mm x 2mm thickness is SZV = 1.2, and the one with φ16mm x 4mm thickness is S / V = 0.8. Table 6 shows 100g of glass articles. The number of NiS, FeO ratio, and S / V value were also shown.

[0109] In any of B9 to B11, the number of NiS was smaller when S / V = 0.8 than when S / V = 1.2. B10 has a nickel oxide content in the compression-molded product that is twice that of B9, and the number of NiS is less than that of B9.

[0110] (Comparative example)

Comparative Examples The glass articles of R1 to R11 were prepared by using a powdered nickel oxide raw material as a nickel oxide source, and melting a glass batch obtained by mixing the same raw materials as in Example 1 at one time. This is a manufactured example. In Comparative Examples R1 to R11, the FeO ratio is changed by the carbon powder, and the others are the same. Tables 7 and 8 show the glass compositions of the glass plates of the comparative examples.

[0111] [Table 7]

[0112] [

[0113] Comparative examples Rl to R11 shown in Table 7 are for the glass plate composition A, and comparative examples R12 to R15 shown in Table 8 are for the glass plate composition B. The number of Ni S found in the glass articles of each comparative example greatly increased in proportion to the FeO ratio of the glass articles. Fig. 3 shows the case of glass plate composition A, and Fig. 4 shows the case of glass plate composition B. In the case of glass plate composition B, the rate of increase in the number of NiS due to the increase in FeO ratio is larger than in the case of glass plate composition A.

[0114] From the results of the above examples, the sulfur-containing compound including the nickel-containing compound was substantially reduced. NiS is produced in the resulting glass article by mixing and melting the glass body and compression molding contained in the glass raw material (a) containing a sulfur-containing compound and substantially free of a nickel-containing compound. It became clear that it can be reduced. It was also confirmed that the formation of NiS was suppressed when frit or compression-molded material containing a nickel-containing compound and substantially not containing a sulfur-containing compound was included in the glass raw material (a) at the same time. .

[0115] In the above examples and comparative examples, the composition of the glass article to be produced is only one type. However, the production method of the present invention uses the soda lime silli If it is a glass composition, it can be applied to its production and can be applied to other glass compositions.

Industrial applicability

[0116] The glass production method according to the present invention can reduce NiS in a glass article containing a NiO composition. The present invention can be suitably used particularly for the production of a glass plate formed into a plate shape by a float method or a roll-out method.

[0117] Furthermore, in the glass manufacturing method according to the present invention, the ratio of adding a refining agent containing a sulfur-containing compound such as mirabilite is not limited, and the ratio of adding a reducing agent is not limited for NiS countermeasures. Therefore, the ratio of the fining agent and reducing agent added to control the redox state of the glass can be adjusted independently of NiS countermeasures. Therefore, it is possible to reduce NiS without affecting the bubble quality and redox state of glass in a glass article that contains FeO within a predetermined range and includes a NiO composition. Thus, the manufactured glass plate can be utilized suitably as a base plate for heat strengthening.

Claims

The scope of the claims

[1] A glass raw material (a) substantially free of a nickel-containing compound and containing a sulfur-containing compound;

The manufacturing method of the glass article including the process of melting the obtained mixture.

[2] The glass raw material (b) is expressed in mass% in terms of oxide,

SiO 60-80%,

2

Al O 0-5%,

twenty three

MgO 0 ~: 10%,

CaO 0 ~: 15%,

MgO + CaO 5 ~: 15%,

Na O 10 ~: 18%,

2

K O 0-5%,

2

Na O + K O 10 ~ 20%,

twenty two

NiO 1 ~: 15%

The method for producing a glass article according to claim 1, which has a composition containing

[3] In the composition, the content of SiO is 65% to 80% in mass%.

2

The method for producing a glass article according to claim 2.

[4] The total iron oxide converted into Fe 2 O by the above composition is expressed by mass%, and 0.05-40%

twenty three

The manufacturing method of the glass article of Claim 2 containing.

[5] The composition further includes 1 to 10% of the total iron oxide converted to Fe 2 O in mass%.

twenty three

The method for producing a glass article according to claim 2.

[6] The glass body is included in the mixture,

The method for producing a glass article according to claim 1, wherein the glass body is in the form of particles and has an average particle diameter of at least 1.5 mm.

[7] The glass body is included in the mixture, 2. The method for producing a glass article according to claim 1, wherein the glass body has a flaky shape, has a thickness of at least 0.5 mm, and an average particle size of at least 10 mm.

[8] The glass body is included in the mixture,

3. The method for producing a glass article according to claim 2, wherein the composition of the glass raw material (b) of the glass body is 1 to 7% in terms of content power of NiO.

[9] The compression molding is included in the mixture,

The glass article according to claim 1, wherein the compression-molded article is obtained by compressing and solidifying a glass raw material (b) substantially composed of silica sand, dolomite, limestone, soda ash, and nickel oxide. Manufacturing method.

[10] The mixture includes the compression molding,

3. The method for producing a glass article according to claim 2, wherein in the composition of the glass raw material (b) of the compression-molded product, the content of NiO is 5 to 15% in terms of mass%.

[11] The method for producing a glass article according to [1], wherein the glass raw material (a) and / or the glass raw material (b) further contains an iron-containing compound.

[12] The method for producing a glass article according to claim 11, wherein the glass raw material (a) and / or the glass raw material (b) further contains a reducing agent.

13. The method for producing a glass article according to claim 12, wherein the reducing agent is a carbon-based reducing agent.

[14] The basic composition of the glass article is expressed in mass%,

SiO 65-80%,

Al O 0-5%,

MgO 0 ~: 10%,

CaO 5 ~ 15%,

MgO + CaO 5 ~: 15%,

Na O 10-18%,

K O 0-5%,

Na O + K O 10-20%, and

B 0-5%

Including 2. The method for producing a glass article according to claim 1, comprising 0.03 to 2.0% of NiO as a coloring component.

[15] The composition of the glass article further includes, as a coloring component,

T-FeO over 0, up to 1.4%,

(T-Fe 2 O is all iron oxide converted to Fe 2 O)

Over TiOO 0 to 1%,

CeO over 0 up to 2%,

CoO over 0 to 0.03%, and

Se 0 over 0.03%,

15. The method for producing a glass article according to claim 14, comprising at least one selected from force.

16. The method for producing a glass article according to claim 1, further comprising a step of heating and quenching the obtained glass article to strengthen the glass article.

[17] A glass article obtained by the method for producing a glass article according to claim 1, wherein the basic composition is expressed in mass%.

SiO 65-80%,

Al O 0-5%,

MgO 0 ~: 10%,

CaO 5 ~: 15%,

MgO + CaO 5 ~: 15%,

Na O 10 ~: 18%,

K O 0-5%,

Na O + K O 10-20%, and

B 0-5%

Including

Glass articles containing 0.03-2.0% Ni〇 as a coloring component.

[18] The composition of the glass article further includes, as a coloring component,

T-FeO over 0, up to 1.4%,

(T-Fe 2 O is all iron oxide converted to Fe 2 O) Over TiO 0 to 1%,

CeO. Over 0 to 2%

CoO over 0 to 0.03%, and

Se 0 over 0.03%,

The glass article according to claim 17, comprising at least one selected from