JPH10218642A - Glass absorbing ultraviolet ray - Google Patents

Abstract

PROBLEM TO BE SOLVED: To aim at the improvement of dwelling properties and a safety, so as to block an ultraviolet ray B and furthermore an ultraviolet ray A by using the subject glass, having a high seeing through property, showing an almost equivalent color tone with a conventional clear plate glass and excellent in absorbing property of ultraviolet rays by containing Fe2 O3 , CeO2 , TiO2 , CoO and Se. SOLUTION: This glass absorbing ultraviolet rays, is obtained by blending a soda lime silica-based glass consisting of 67-75wt.% SiO2 , 0.05-3.0wt.% Al2 O3 , 7-11wt.% CaO, 2-4.5wt.% MgO, 11.5-16wt.% Na2 O, 0.5-3.0wt.% K2 O, 0.05-0.4wt.% SO3 and also satisfying (SiO2 +Al2 O3 +TiO2 )=68-75wt.%, (CaO+MgO)=9-15wt.% and (NaO+K2 O)=12-17wt.%, with 0.15-0.30wt.% Fe2 O3 (in terms of whole iron), 1.3-2.0wt.% CeO2 , 0.4-0.8wt.% TiO2 , 5-30ppm CoO and 5-30ppm of Se, and heating the blended material to melt the blended material under an atmosphere containing oxygen gas to form the glass absorbing ultraviolet rays having <=0.05 reduction rate (Fe<2+> /Fe<3+> ).

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet absorbing glass useful for architectural, automotive and other vehicle, marine or aircraft window glass and various glass articles. It has the same color tone and has a remarkably excellent ultraviolet absorption performance.
UV light of 320nm, hereafter referred to as UVB. ) And further block ultraviolet A (ultraviolet light having a wavelength of about 320 to 390 nm, hereafter referred to as UVA) to enhance comfort and safety, and to be human-friendly and material-friendly. UV-absorbing glass.

[0002]

2. Description of the Related Art In recent years, there has been an urgent need for glass having an ability to reflect and absorb ultraviolet rays, and the need for sheet glass articles that lead to higher livability and safety both physically and physically has increased. Among them, a colorless and transparent glass having better ultraviolet shielding performance than before has been desired.

[0003] As a colorless and transparent glass having an ultraviolet shielding performance, Japanese Patent Publication No. 5-354 discloses a glass container for shielding ultraviolet rays. The glass container has a maximum length of 250 mm or less. 0.04 to 0.1% CeO ₂ and 0.
There is disclosed a soda lime glass containing 065% or less of Fe ₂ O ₃ and blocking ultraviolet rays while maintaining colorless transparency.

[0004] JP-A-6-56467 describes an ultraviolet absorbing glass, which contains 65 to 80% of SiO ₂ and B ₂ by weight percentage.
O ₃ 5-20%, Al ₂ O ₃ 2-8%, RO 1-5% (However, RO is
MgO, CaO, BaO, SrO, 1 or 2 or more selected from the group of _{ZnO), R 2 O 4 ~8} % ( provided that R ₂ O is, Na ₂ O, K ₂
O, 1 or 2 or more selected from the group consisting of _{Li 2 O), CeO 2 0} .
_{3 ~4%, Fe 2 O 3} 0.01~0.2%, V 2 O 5 0.0005~0.005%
Below, those having a composition of TiO ₂ 0 to 2% is disclosed.

Further, as a method of producing a colorless and transparent glass, Japanese Patent Publication No. 55-16105 discloses a method of changing the composition of a molten glass. The molten colored glass in a glass melting furnace is continuously cooled. A method of changing a transparent glass while operating the same, which stops supplying a typical coloring component in a colored glass to a furnace and gives a complementary color tone to the coloring component to the glass (decoloring component) Is added to a glass melting furnace at a specified time, at a specified ratio, and for a specified period of time. This seeks to shorten the period for changing from colored glass such as bronze soda-lime glass to transparent glass more quickly and in an effective manner.

Japanese Patent Application Laid-Open No. 53-145822 discloses a method for producing colorless glass. In the case of using colored glass chips containing selenium as a part of a raw material to be fed into a melting furnace, the method comprises the steps of: In addition, it is disclosed that at least one of sodium nitrate, cerium oxide, inorganic manganese compound, and lead oxide is added, and selenium is used as a part of a raw material for producing a colorless and transparent glass product. It is described that an attempt is made to use a relatively large amount of colored glass waste.

Further, source in the continuous tank furnace in JP 57-67028 - selenium decoloring method Dagarasu is described, the SO ₃ content in the glass batch X _1, SO ₃ in the glass product
When the amount was defined as X _2, determined in the range of the addition amount Y of selenium is decolorizer _{{0.006 × (X 1 -X 2} ) ≦ Y ≦ 0.015 × (X 1 -X 2) +0.0015} Conversely, by measuring the amount of SO ₃ in the glass batch and the amount of SO _{3 in the} glass product, it is possible to determine the appropriate amount of selenium that can achieve the decolorization of the glass. Yes, it is possible to decolorize the glass reliably and quickly.

[0008]

The glass container for blocking ultraviolet rays described in Japanese Patent Publication No. 5-354 described above has a content of about 0.065 which is equivalent to the content of the Fe ₂ O ₃ component in ordinary clear glass. the more Fe ₂ O ₃ than the weight%, Fe ²⁺
It is difficult to maintain colorless and transparent because of the coloration of green color. If the content of CeO ₂ component, which is effective for ultraviolet absorption performance, is more than 0.1% by weight, it becomes yellowish and can be perceived by the naked eye. The content of the Fe ₂ O ₃ component is 0.06
If the content of the CeO ₂ component is too much more than 0.1% by weight in order to further improve the ultraviolet absorption performance of the glass more than 5% by weight, a colorless and transparent glass cannot be obtained.

The ultraviolet absorbing glass described in Japanese Patent Application Laid-Open No. 6-56467 is a borosilicate glass. If the content of the B ₂ O ₃ component is less than 5%, the melting property is deteriorated, and the efficiency of the ultraviolet light is reduced. It is difficult to apply to soda-lime-silica glass such as float glass because a specific amount of V ₂ O ₅ component is required for good absorption and colorless and transparent balance.

Further, the method described in Japanese Patent Publication No. 55-16105 discloses a method for producing a blue tinted glass containing a CoO component and a CoO component for a reddish bronze glass containing a Se component. In addition to the above, a component (color erasing component) that gives a complementary color tone to glass, such as a Se component and a CeO ₂ component, is added to the glass, and the color is erased to make the glass colorless and transparent. It cannot be said that it has an absorption function, and it cannot achieve both an ultraviolet absorption function and colorless transparency.

Japanese Unexamined Patent Publication (Kokai) No. 53-145822 discloses that for example, 100 parts by weight of a heat ray absorbing glass having a selenium content of about 0.0005 to 0.0020% by weight is less than 20 parts by weight of colored glass chips containing selenium.
It is described that the amount of Fe ₂ O ₃ contained in the colored glass waste is limited to 0.04 parts by weight or less with respect to 100 parts by weight of the glass batch, and the atmosphere in the glass melting furnace is colorless under strong reducing conditions. Appropriate conditions are in the middle of the two extremes described above to produce selenide and to produce elemental selenium which gives colorless selenite and selenate under strong oxidizing conditions and gives a pink color. selenite colorless or merely discloses that no significantly alter the transparency and color if oxidized to selenate salts, in addition to component working relationship between Se and CeO _2,, further Fe
There is no mention of clear vitrification in the presence of ₂ O ₃ , TiO ₂ or CoO components.

Further, the method of decolorizing selenium of soda glass in a continuous tank furnace described in Japanese Patent Application Laid-Open No. 57-67028 discloses a method for selenium, which is a coloring agent of a purple thread having a complementary relationship with the blue-green color of iron ions. While adding cobalt to make the absorption of transmitted light uniform and apparently colorless, the amount of SO ₃ in glass batches and glass products is measured, and from these specific relational expressions, Find the amount of selenium added,
By determining the amount of addition, it is intended to efficiently erase the selenium of the soda glass in the continuous tank furnace, and is concerned only with a specific complementary color relationship. It is not applicable to glass containing a large amount of TiO ₂ or CeO ₂ , nor is it capable of imparting ultraviolet absorption performance.

[0013]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks, and it is an object of the present invention to provide a soda-lime-silica glass containing a coloring component and / or an ultraviolet absorbing component Fe _2. In a complex glass containing O ₃ , CeO ₂ , TiO ₂ , Se, and CoO, by combining various component composition ratios as appropriate and adjusting the reduction rate of the glass, a significantly superior ultraviolet absorption performance and It has both transparency and transparency, and can exhibit a color tone that is the same as or similar to conventional clear glass, balances optical characteristics, and can shield ultraviolet rays B and ultraviolet rays A more. It has enhanced environmental and safety properties, is gentler to humans and materials, is more environmentally friendly, and exhibits easy-to-reinforce, has sufficient weather resistance and moldability, and can be lightened in various shapes. ,
Not only for buildings, but also for window glasses for vehicles such as automobiles,
An object of the present invention is to provide an ultraviolet absorbing glass useful as a window glass for a ship, a window glass for an aircraft, or various glass articles stably, more simply, and efficiently.

That is, the present invention is based on a soda-lime-silica glass and has a basic composition of Fe ₂ O ₃ (total iron) expressed by weight%.
But 0.15 to 0.30, CeO ₂ is 1.3 to 2.0, TiO ₂ is 0.4 to 0.8,
And a glass containing 5 to 30 CoO and 5 to 30 Se in terms of ppm, and the reduction rate of the glass (Fe ²⁺
/ Fe ³⁺ ) is 0.05 or less.

In the above-mentioned ultraviolet absorbing glass, furthermore,
In m display, Cr ₂ O ₃ is 0 to 8, MnO is 0 to 150, NiO is 0
The ultraviolet absorbing glass as described above, characterized by containing at least one or more of these components which are -10 to 10.

The ultraviolet absorbing glass has a thickness of 5 mm.
In the light source as measured by D ₆₅ or A, above ultraviolet absorbing glass, wherein the visible light transmittance Tv is at least 75%, and ultraviolet transmittance Tuv is equal to or less than 13%.

The basic composition of the soda-lime-silica glass is expressed in terms of% by weight, with SiO ₂ being 67 to 75 and Al ₂ O ₃ being 0.05 to 3.
0, CaO is 7 to 11, MgO is 2 ~ 4.5, Na ₂ O is from 11.5 to 16,
K ₂ O is 0.5 to 3.0, SO ₃ is 0.05 to 0.4, and SiO ₂ + Al ₂ O ₃
+ TiO ₂ is 68 ~75, CaO + Mg0 is _{9~15, Na 2 O + K 2} O
Is 12 to 17 in the above-mentioned ultraviolet absorbing glass.

[0018]

BEST MODE FOR CARRYING OUT THE INVENTION Here, a soda-lime-silica glass is used as a base composition, and Fe ₂ O ₃ (total iron) is 0.1% by weight.
15 to 0.30, 1.3 to 2.0 for CeO ₂ , 0.4 to 0.8 for TiO ₂ , and 5 to 30 ppm for CoO and 5 to 30 for Se, respectively, and the reduction rate (Fe ^{2 +} / Fe
^The UV-absorbing glass with ³⁺ ) of 0.05 or less is based on soda-lime-silica glass, which is the most versatile as a window glass and various glass articles for vehicles for construction and automobiles, and for ships and aircraft. From the UV-absorbing green-colored glass and bronze-colored glass, clear glass with a color tone almost equivalent to conventional clear glass can be stably and more easily changed without changing its UV absorption performance. This is because it can be obtained efficiently.

The reason why the total Fe ₂ O ₃ (total iron) is set to 0.15 to 0.30% by weight is that the Fe ₂ O ₃ component is necessary for absorbing ultraviolet rays, and is a sufficient content to achieve the intended absorption performance. In this case, cobalt or cobalt and nickel are required to adjust the chromaticity so as to achromatically express a yellowish color tone. 0.15% by weight of Fe ₂ O ₃ component
If it is less than ₃ , it becomes difficult to secure ultraviolet absorption performance, and Fe ₂ O ₃
If the content of the component exceeds 0.30% by weight, the content becomes excessive and lowers the visible light transmittance, and it becomes impossible to achieve the transparency or transparency of about 75% or more, which is aimed at. Preferably about 0.15
About 0.25% by weight.

The reason why the content of CeO _{2 is set} to 1.3 to 2.0% by weight is that CeO ₂
Ingredients are necessary to enhance UV absorption performance, and Ce
O ₂ is also a strong oxidant. If the CeO ₂ component is less than 1.3% by weight, it is difficult to obtain the target ultraviolet absorption performance of about 13% or less, and the reduction rate of ordinary clear glass (Fe ²⁺
/ Fe ³⁺ ), for example, from about 0.35 to 0.45 to 0.05 or less, making it difficult to obtain a color tone comparable to that of ordinary clear glass. If the CeO ₂ component exceeds 2.0% by weight,
This is because it is difficult to obtain the desired visible light transmittance, which leads to an increase in cost. Preferably about 1.5-1.8% by weight
It is about.

When melting a soda-lime-silica glass batch, mirabilite is used as a melting accelerator for silica sand and as a fining agent for molten glass (ratio to silica sand: about 0.5 to 1.0%).
In order to react preferentially with a sulfate such as described above and to make its function effective, carbon, which is also a reducing agent, is added to the batch, but when the content of the CeO ₂ component increases, The addition of excessive carbon also causes the formation of silica scum at the time of melting, which causes defects in glass products. The preferred amount of carbon added is glass 10
It is about 0.15g or less for 0g.

Further, when iron oxide and cerium oxide coexist in the glass, divalent iron is oxidized by tetravalent cerium to become trivalent iron, and the FeO component which provides heat ray absorption performance and a bluish color tone is produced. Other components such as TiO ₂ , CoO, and Se, as well as as little as possible, so as to enhance the ultraviolet absorption performance and obtain the same color tone as conventional clear glass
It is important to balance the components of Fe ₂ O ₃ and FeO.

The reason why the content of TiO _{2 is set} to 0.4 to 0.8% by weight is to replace a part of the expensive CeO ₂ component with a relatively inexpensive and easily available TiO ₂ component having an ultraviolet absorbing function. TiO ₂
When the content of the component is less than 0.4% by weight, the effect on the ultraviolet absorbing function is small. When the content of the TiO ₂ component exceeds 0.8% by weight, the yellowish color tone increases as the content increases, and the visible light transmittance decreases. It is because you will be. Preferably, it is about 0.5 to 0.7% by weight.

The reason why the content of CoO is set to 5 to 30 ppm is that the CoO component has an absorption peak near about 600 nm and is a component for fine-tuning the dominant wavelength. If the amount of CoO exceeds 30 ppm, a blue tint is exhibited. Preferably about 10-28
It is about ppm.

The Se content of 5 to 30 ppm means that the Se component has a reddish color tone. If the Se component is less than 5 ppm, the amount of providing a reddish color tone is insufficient, and if the Se component is more than 10 ppm, the reddish color tone becomes excessive, and it is difficult for any of them to have a color tone similar to conventional clear glass. Because. Preferably, it is about 8 to 28 ppm.

The reason why the reduction ratio (Fe ²⁺ / Fe ³⁺ ) of the glass is 0.05 or less is that components having an ultraviolet absorbing function and coloring components [for example, iron (yellow, blue), selenium (compound with iron) and, brown, pink), cobalt (blue), chromium (light green, Fe ₂ O _3, which is a yellow blue) expressing], CeO _2,
An oxidizing agent or an oxidizing agent and a reducing agent such as carbon are appropriately combined to obtain a bronze color tone, a gray color tone, or a green color in a glass component composition in which TiO ₂ , CoO, and Se components are appropriately combined in a specific ratio. This is because it is necessary to obtain a glass having a color tone similar to that of a conventional clear glass without having a color glass exhibiting a color tone and having an excellent ultraviolet absorbing function.

When the reduction ratio of the glass exceeds 0.05, the color tone of the conventional clear glass cannot be obtained, for example, the Se component develops a color and exhibits a reddish color tone. This is because the transmittance becomes less than 75%. Preferably it is about 0.03-0.

Further, in the ultraviolet absorbing glass, in addition to the respective components described in claim 1, Cr in ppm
Among those components in which ₂ O ₃ is 0 to 8, MnO is 0 to 150, and NiO is 0 to 0, it is preferable that at least one or more of these components be contained, because the used raw material or used cullet is used. Is also a component composition contained in the glass, and may be necessary for a colored glass exhibiting a bronze color tone, a gray color tone, or a green color tone. This is because it has a function of absorbing ultraviolet light and has a color tone similar to that of conventional clear glass, and does not hinder transparency and transparency.

In addition, bronze color tone, gray color tone,
Glass raw material batch,
It is possible to obtain a stable, convenient, and efficient ultraviolet absorbing glass with high uniformity without causing any change in the melting conditions and the like as much as possible and without generating defects or the like. Preferably, Cr ₂ O ₃ is about 0 to 5 ppm and MnO is about
At least one or more of these components having a content of 50 to 100 ppm and NiO of about 0 to 5 ppm is contained.

Further, in the measurement light source at the plate thickness 5mm at the ultraviolet absorbing glass according to D ₆₅ or A, the visible light transmittance Tv of 75% or more, and ultraviolet transmittance Tuv 13%
The following is preferable because it has the same color tone and the same visible light transmittance as the conventional clear glass usually used for construction and vehicles such as automobiles, and has an ultraviolet absorbing property. This is to obtain a clear ultraviolet absorbing glass exhibiting the same ultraviolet absorbing performance as bronze glass and ultraviolet absorbing green glass. Preferably, the visible light transmittance Tv is 78% or more and the ultraviolet light transmittance Tuv is 10%.
It is as follows.

In addition, it is possible to increase the comfort and safety by securing and maintaining the above-mentioned optical characteristics, especially by blocking ultraviolet rays B and further shielding ultraviolet rays A.
It is gentle to humans and materials and can realize high environmental properties. That is, of the ultraviolet rays, ultraviolet rays B (UVB) having a wavelength of about 290 to 320 nm are set to zero, for example, to prevent so-called sunburn, which causes human skin to have red heat or swollen to water bubbles and then to be blackened. ~ 400nm UV A
By making (UVA) smaller than the conventional value, for example, strong ultraviolet rays having high penetrability into human skin and damaging fibrous materials such as collagen fibers and elastic fibers in the dermis of the skin, causing wrinkles and It is possible to prevent the appearance of dark spots and freckles by acting on melanin present in the skin, which may cause tarmi.

Further, the transmittance Ts _{1100 at} a wavelength of 1100 nm of the ultraviolet absorbing glass and the transmittance near the wavelength of 1100 nm are equivalent to the transmittance in the visible light transmittance region in the A light source measurement when the glass thickness is 5 mm. Or higher transmittance.

Further, the basic composition of the soda-lime-silica glass is expressed in terms of% by weight, wherein SiO ₂ is 67 to 75, Al ₂ O ₃
There 0.05 to 3.0, CaO is 7 to 11, MgO is ₂ ~4.5, Na 2 O is
11.5-16, K ₂ O is 0.5-3.0, SO ₃ is 0.05-0.4, and
SiO ₂ + Al ₂ O ₃ + TiO ₂ is 68-75, CaO + Mg 0 is 9-15,
The reason that Na ₂ O + K ₂ O is 12 to 17 is that the SiO ₂ component is
If the content is less than 67% by weight, scorch or the like is likely to occur on the glass surface, the weather resistance is reduced, and a practical problem is caused. If the content of SiO ₂ exceeds 75% by weight, the easy strengthening property is reduced. This is because melting becomes difficult. Preferably about 68-
It is about 73% by weight.

[0034] If the Al less than ₂ O ₃ component is 0.0567 wt%, which burnt like a glass surface weather resistance decreases come occur easily practical problem occurs, Al ₂ O ₃ component is 3.0
If the content is more than 10% by weight, devitrification tends to occur, and the forming temperature range is narrowed, so that plate making becomes difficult. Preferably, it is about 0.5 to 2.5% by weight.

If the CaO component is less than 7% by weight, the ease of strengthening is reduced, and the flux tends to be insufficient to increase the melting temperature, and the flow temperature is not lowered. If the content is more than 10% by weight, devitrification is likely to occur, and the molding operation range is narrowed, so that production becomes difficult. Preferably, it is about 7 to 10% by weight.

If the content of the MgO component is less than 2% by weight, the melting temperature rises and the operation range is narrowed, so that the production becomes difficult. If the content of the component exceeds 4.5% by weight, the easy strengthening property is reduced. Preferably, it is about 2.5 to 3.5% by weight.

[0037] If the Na less than ₂ O component is 11.5 wt% lowers the easily enhanced resistance, moldability becomes difficult, also molding operation range becomes narrower becomes prepared difficult because liable to occur devitrification, the Na ₂ O component If it exceeds 16% by weight, the weather resistance is reduced, and burns and the like are easily generated on the glass surface, which causes a practical problem. Preferably, it is about 12.0 to 14.5% by weight.

If the content of the K ₂ O component is less than 0.5% by weight, the reinforceability is reduced. If the content of the K ₂ O component exceeds 3.0% by weight, the weather resistance is reduced and the cost is increased. Preferably, it is about 0.7 to 2.0% by weight.

If the SO ₃ component is less than 0.05% by weight, it can only be degassed or insufficient in homogeneity in ordinary melting, and if the SO ₃ component exceeds 0.4% by weight, the coloring state of the glass can be reduced. Yellow, amber
This is because the color tends to shift to a tinted color tone, which manifests itself, making it difficult to obtain the desired ultraviolet absorbing clear glass. Preferably, it is about 0.08 to 0.25% by weight.

Furthermore, 68% by weight of SiO ₂ + Al ₂ O ₃ + TiO ₂
If less, the weather resistance decreases, and SiO ₂ + Al ₂ O ₃ + TiO ₂
If the content is more than 75% by weight, a problem that the easy strengthening property is lowered occurs. Preferably, it is about 69 to 74% by weight.

If the content of CaO + Mg0 is less than 9% by weight, the effect of lowering the melting temperature will be insufficient, and the reinforceability will be reduced. If the content of CaO + Mg0 exceeds 15% by weight, devitrification tends to occur, and molding will occur. The reason for this is that the working range becomes narrower and manufacturing becomes difficult. Preferably, it is about 10 to 14% by weight.

If the content of Na ₂ O + K ₂ O is less than 12% by weight, the easiness to strengthen is lowered, the devitrification is liable to occur, the working range of molding is narrowed, and the production becomes difficult, and the Na ₂ O + K ₂ O is 17% by weight. This is because, if it exceeds, the weather resistance decreases, a practical problem arises and the cost increases. Preferably about 13-16
% By weight.

The reduction rate may be adjusted by controlling the oxidizing agent of the raw material glass batch, carbon, sodium sulfate, etc., the operating conditions such as the combustion state of the melting furnace, or the oxygen gas or oxygen gas in the atmosphere in the adjusting region of the glass melting furnace. In some cases, the introduction of a mixed gas containing, air or combustion exhaust gas with an increased oxygen gas concentration, or a composite gas thereof also contributes to color stability. Furthermore, it goes without saying that a current-carrying electrode, bubbling, a stirrer, and the like, which are normally provided in a glass melting furnace, can be used in combination.

If zinc selenite is used as a raw material for preparing the Se component, selenium metal is not economical because the residual ratio in glass is too low, and zinc selenite (ZnSeO ₃ ) The residual ratio is expected to be about twice or more of the residual ratio of the selenium-based frit, and is preferably used as a raw material of zinc selenite.

Further, it is preferable in terms of production and quality that the physical properties such as the density of the glass be as close as possible to the physical properties such as the density of the glass component composition manufactured by the conventional float method as much as possible. It is.

Further, the ultraviolet absorbing glass of the present invention is manufactured in a conventional glass melting furnace except that it is in an oxidized state in consideration of melting property, clarity, weather resistance, moldability, devitrification, cost and the like. With almost no change in the properties of glass,
With excellent UV absorption performance and conventional clear color tone, and excellent transparency and transparency, it is also an easily strengthened glass composition, from thin glass with a thickness of about 1 mm to thick glass with a thickness of about 10 mm. For example, single-pane glass, laminated glass, multi-layer glass or laminated glass, glass with various functional films, various colors, etc. It can be used in combination with glass, etc., including window glass for buildings, vehicles such as automobiles, especially window glass, marine or aircraft window glass, and solar cell covers.
It can be used for various glass articles such as glass, equipment for solar water heaters, windows for efficiently entering solar heat, and protective cases for exhibits.

[0047]

Embodiments of the present invention will be described below. Example 1 As glass raw materials, for example, silica sand, feldspar, soda ash, dolomite, limestone, sodium sulfate, red iron oxide, titanium oxide, cerium carbonate, cerium oxide, or ilmenite, and metal selenium, and in some cases zinc selenite (SeZn)
O ₃ ), cobalt oxide, etc., and in some cases, various cullets so as to be within a predetermined composition range. For example, the viscosity temperature is 10 ⁹ poise and 650 to 685 ° C.
Degree, 555 to 590 ° C. of about 10 ¹² poise, and so that the temperature difference between the two is about 95 to 105 ° C., the glass composition is set as a target composition was weighed formulated the target composition weight, with small electric melting furnace For example, without using carbon as a reducing agent, an amount of sodium sulfate is used as a fining agent (for example, about 1% of silica sand), and the reduction rate is close to zero and adjusted so that it can be said that it is almost in an oxidized state. About 1400 ~
Melt at about 1450 ° C for about 3 to 4 hours, homogenize and clarify, etc., pour out and make into sheet glass, perform sufficient slow cooling, and optically polish to a thickness of about 5 mm Then, a glass plate having a size of 100 mm × 100 mm was obtained to obtain a test sample glass for glass component composition analysis and measurement of various optical characteristics.

Needless to say, the composition may be appropriately used in consideration of the composition, optical properties, quality and the like of various cullets. Hereinafter, the same applies to each embodiment. For該供specimens glass obtained it was confirmed by a wet analysis method based on JIS R-3101, in weight percentages, SiO ₂ is 69.
9, Al ₂ O ₃ 1.92, CaO 8.41, MgO 3.35, Na ₂ O 13.
04, a basic glass composition with K ₂ O of 0.9 and SO ₃ of 0.1. As shown in Table 1, all other component compositions are expressed in weight%.
Fe ₂ O ₃ (total iron) 0.244, CeO ₂ 1.45, TiO ₂ 0.68, pp
In terms of m, Se is about 28.2 and CoO is about 18.8. In terms of weight%, the total sum of the components is about 99.9987, and SiO ₂ + Al ₂ O ₃ + Ti
O ₂ 72.50, CaO + MgO 11.76, Na ₂ O + K ₂ O 13.94
Met.

The residual ratio of Se in the glass by using zinc selenite (SeZnO ₃ ) was high, about 68.9%. Note that ZnO was a trace amount of about 0.003% by weight and was not included in the total of the above components, and the composition of trace components in the ppm order due to impurities and the like was not analyzed. Hereinafter, the same applies to each embodiment.

Further, the reduction rate (Fe ²⁺ / Fe ³⁺ ) is shown by a spectral transmittance curve (measured by a 340 type self-recording spectrophotometer described later) with a plate thickness of about 5 mm and a _D65 light source shown in FIG. FeO amount determined from the transmittance Ts ₁₁₀₀ in the infrared region having a wavelength of about 1.1 .mu.m (1100 nm), next the value of about 0.001 wt%,
The reduction was calculated from the total iron content (Fe ₂ O ₃ ) of the above-mentioned analysis value of 0.244% by weight, and the reduction ratio was 0.01.

Furthermore, the optical characteristics (5 with a _D65 light source)
Visible light transmittance Tv (% in mm thickness) [%, wavelength
0.38 to 0.78 μm (380 to 780 nm)], UV transmittance Tu
v [%, wavelength 0.30-0.38μm (300-380nm), ISO
(According to International Organization for Standardization) and a wavelength of 0.35 μm (35
0nm) transmittance Tuv ₃₅₀ (%) and wavelength 0.37μ
m (370 nm), the transmittance Tuv ₃₇₀ (%), and the solar transmittance Ts [%, wavelength 0.34 to 1.8 μm (340 to 1800 n)
m)] and transmittance T at a wavelength of 1.1 μm (1100 nm)
For s ₁₁₀₀ (%), dominant wavelength λd (nm), stimulus purity Pe (%), etc., use the 340 type recording spectrophotometer (manufactured by Hitachi, Ltd.) and JI
S Z-8722, JIS R-3106, ISO / DIS-9050 measured and calculated.

As a result, as shown in FIG. 1 and Table 2,
Visible light transmittance Tv is about 82.7%, solar transmittance Ts is 85.0%
About 19.8nm, transmittance Ts ₁₁₀₀ is about 89.8%, UV transmittance Tuv is about 6.7%, wavelength 350nm, transmittance Tuv ₃₅₀ is 0.0
%, Wavelength 370nm Transmittance Tuv ₃₇₀ is about 19.7%, dominant wavelength λd is about 559.7nm, stimulus purity Pe is about 1.8%,
It was the expected UV-absorbing glass, such as a clear glass that shows exceptionally excellent see-through performance and UV-absorbing performance.

Further, regarding the easy strengthening property, it was confirmed that the above-mentioned UV-absorbing glass satisfies the above-mentioned specific range of the viscous temperature and the like. After about 5 minutes of heating in a furnace, normal air-cooling was performed to obtain a tempered glass sheet with high efficiency and high yield.
When examined according to JIS R-3211, it was found that the glass was an ultraviolet-absorbing glass having an easily strengthening property which sufficiently satisfied the determined standard.

Examples 2 to 3 In the same manner as in Example 1, the glass composition was calculated to obtain the desired ultraviolet absorbing glass, weighed and blended, and the resulting glass was melted. It was made into a sample as a glass plate. Next, the obtained sample body glass of each example was analyzed, measured, and evaluated in the same manner as in Example 1.

As a result, the analysis value of the basic glass component composition was expressed in terms of% by weight, and in Example 2, SiO ₂ was 70.0 and Al ₂ O ₃ was
1.93, CaO is 8.32, MgO is 3.31, Na ₂ O is 13.04, K ₂ O is
0.9, SO ₃ is 0.1, Example 3 is 70.0 for SiO ₂ , and Al ₂ O ₃
1.92, CaO 8.38, MgO 3.32, Na ₂ O 13.02, K ₂ O
Was 0.9 and SO ₃ was 0.1.

The analytical values of other component compositions are shown in Table 1.
As described above, Example 2 shows that all Fe_TwoO_Three (All iron) is 0.
220, CeO_TwoIs 1.48, TiO_TwoIs 0.69, Se is 25.6 in ppm,
CoO becomes about 13.8, and the total of the components is about 9
9.9939, SiO_Two+ Al _TwoO_Three+ TiO_TwoIs 72.62, CaO + M
gO 11.63, Na_TwoO + K_TwoO was 13.94.

Further, Example 3 shows that all Fe_TwoO_Three 
(All iron) 0.206, CeO_TwoIs 1.45, TiO_TwoIs 0.69, ppm display
Is 26.8 for Se and 26.8 for CoO.
Total of about 99.9914, and SiO_Two+ Al_TwoO_Three+ TiO_TwoIs 7
2.61, CaO + MgO 11.70, Na _TwoO + K_TwoO is 13.92
Was.

The reduction ratio and the Se residual ratio were almost the same as in Example 1. As shown in Table 2, the optical characteristics of each of Examples 2 and 3 were such that the visible light transmittance Tv was 84.2% and 8%.
3.1%, solar transmittance Ts 85.6%, 85.4%, wavelength 1100nm transmittance Ts ₁₁₀₀ 91.0%, 91.0%, UV transmittance Tuv 6.4
%, 6.8%, wavelength 350nm Transmission Tuv ₃₅₀ is 0.0%, 0.0
%, Wavelength 370nm Transmittance Tuv ₃₇₀ is 18.7%, 19.9%, dominant wavelength λd is 564.8nm, 557.7nm, stimulus purity Pe is 2.5%, 1.4
%Met.

As in the case of the first embodiment, the desired color of the ultraviolet absorbing glass is the same as that of ordinary clear glass, and it is an intended ultraviolet absorbing glass which exhibits remarkably excellent transparency, transparency and ultraviolet absorbing performance. Was.

Further, as to the ease of strengthening, the above-mentioned Example 1 was used.
As a result, the same results as in Example 1 were obtained. Example 4 In addition to the same raw materials as in Example 1, chrome oxide, manganese oxide, nickel oxide, and glass
And the temperature is about 650 to 685 ° C. at 10 ⁹ poise, about 555 to 590 ° C. at 10 ¹² poise, and the temperature difference between the two is 95 to 105 ° C. The glass composition is set as a target composition so as to obtain the target composition, the target composition amount is weighed and mixed, and a considerable amount of carbon as a reducing agent (for example, glass 10
About 0.10 to 0.12 g per 0 g) and a considerable amount of sodium sulfate as a fining agent (for example, about 0.5% of silica sand ratio). Approximately 1400 to 1450 °
C Melt for about 3 to 4 hours, about 3 to 4 hours, homogenize and clarify, etc., pour it out and make it into a sheet glass with a float line, etc., perform sufficient slow cooling, and optically reduce the thickness to about 5 mm. A polished glass plate having a size of 100 mm x 100 mm was cut to obtain a test sample glass for glass component composition analysis and measurement of various optical characteristics.

With respect to the obtained specimen glass,
In the same manner as in 1, check with a wet analysis method based on JIS R-3101.
As a result, SiO_TwoIs 71.0, Al_TwoO_Three Is 2.02, Ca
O is 7.34, MgO is 3.42, Na_TwoO is 12.77, K_TwoO is 0.95, SO
_Three Is the base glass composition of 0.1, and as shown in Table 1,
The analytical value of the component composition is expressed in wt%_TwoO_Three (All iron)
0.188, CeO_TwoIs 1.57, TiO_TwoIs 0.61, and CoO in ppm is
14.4, Se 11.7, Cr_TwoO _Three 3.0, MnO 85.3, NiO 2.
4 and the sum of the components is about 99.9797 in weight%.
What is SiO_Two+ Al_TwoO_Three+ TiO_Two73.63, CaO + MgO 10.7
6, Na_TwoO + K_TwoO was 13.72.

Incidentally, the reduction ratio and the Se residual ratio were almost the same as in Example 1. In addition, each optical characteristic (A light source, plate thickness 5mm
As shown in Table 2, the visible light transmittance Tv was 82.6% and the solar radiation transmittance Ts was 8 as shown in Table 2.
1.7%, wavelength 1100nm transmittance Ts ₁₁₀₀ is 82.4%, UV transmittance Tuv is about 8.7%, wavelength 350nm transmittance Tuv ₃₅₀ is 0.6
%, Wavelength 370nm Transmittance Tuv ₃₇₀ is 25.0%, dominant wavelength λd is 56
2.0 nm, the stimulus purity Pe was 1.8%.

As in the case of the first embodiment, the desired ultraviolet absorbing glass has the same color tone as that of ordinary clear glass, and exhibits remarkably excellent transparency, transparency and ultraviolet absorbing performance. Was.

Further, with respect to the ease of strengthening, the first embodiment
As a result, the same results as in Example 1 were obtained. Examples 5 to 6 In the same manner as in Example 4, a glass composition was calculated and weighed to obtain the expected ultraviolet absorbing glass, weighed and blended, and the resulting glass was similarly used as a glass plate. Samples were made. Next, the obtained sample body glass of each example was analyzed, measured, and evaluated in the same manner as in Example 1.

As a result, the analytical value of the basic glass component composition was expressed in terms of% by weight. In Example 5, 71.13 of SiO ₂ and Al ₂ O ₃
2.03, CaO 7.35, MgO 3.27, Na ₂ O 12.60, K ₂ O
Is 0.96, SO ₃ is 0.15, and Example 6 has SiO ₂ of 71.22,
Al ₂ O ₃ 2.04, CaO 7.15, MgO 3.32, Na ₂ O 12.67
, K ₂ O was 0.96 and SO ₃ was 0.13.

As shown in Table 1, the analytical values of the other component compositions were as follows: Example 5 was expressed in terms of% by weight, and the total Fe ₂ O ₃ (total iron) was 0.1%.
231, CeO ₂ is 1.71, TiO ₂ is 0.55, Se is 11.3 in ppm,
CoO is 13.7, Cr ₂ O ₃ is 3.7, MnO is 84.5, NiO is 2.6, and the sum of components is about 99.9926 in terms of weight%, and SiO ₂ + Al ₂ O ₃ + TiO ₂ is 73.71, CaO + MgO is 10.62,
Na ₂ O + K ₂ O was 13.56.

In Example 6, the total amount of Fe ₂ O ₃
(Total iron) is 0.238, CeO ₂ is 1.71, TiO ₂ is 0.54, Se is 10.8, CoO is 14.0, Cr ₂ O ₃ is 3.5 in ppm, MnO is 81.4,
NiO is 2.1, and the sum of components is about 99.9% by weight.
892, 73.80 for SiO ₂ + Al ₂ O ₃ + TiO ₂ , CaO + MgO
Was 10.47, and Na ₂ O + K ₂ O was 13.63.

Incidentally, the reduction ratio and the Se residual ratio were almost the same as in Example 1. As shown in Table 2, the optical characteristics (measured under the same conditions as in Example 4) were as follows. In Examples 5 and 6, the visible light transmittance Tv was 84.2% and 83.1%, and the solar radiation transmittance Ts was 85.6%.
% 85.4%, the wavelength 1100nm transmittance Ts ₁₁₀₀ is 91.0%, 91.0
%, UV transmission Tuv is 6.4%, 6.8%, wavelength 350nm Transmission Tuv ₃₅₀ is 0.0%, 0.0%, wavelength 370nm Transmission Tuv ₃₇₀
18.7%, 19.9%, dominant wavelength λd is 564.8nm, 557.7nm,
The stimulus purity Pe was 2.5% and 1.4%.

As in the case of Example 1, the desired color of the ultraviolet absorbing glass is the same as that of the ordinary clear glass, and it is the intended ultraviolet absorbing glass which exhibits remarkably excellent transparency, transparency and ultraviolet absorbing performance. Was.

Further, with respect to the ease of strengthening, the first embodiment
As a result, the same results as in Example 1 were obtained.

[0071]

[Table 1]

[0072]

[Table 2]

[0073]

According to the present invention, the specified components are skillfully combined within the specified composition range, and furthermore, the reduction ratio is specified as a glass composition, thereby achieving excellent visible light transmittance and remarkably excellent. A glass that has the same ultraviolet absorption performance as the conventional clear glass and has the same color tone as the conventional clear glass, and also shields ultraviolet B and ultraviolet A more, giving a good balance between excellent transparency and transparency. The glass can be easily and efficiently manufactured stably without changing the raw materials of glass and the operating conditions of the actual kiln. In addition to improving the safety and safety, it has high environmental properties, and it is also possible to reduce the weight of thin-plated tempered glass and thin-plate laminated glass. Window glass Etc., it can be widely used in various types of glass articles.

[Brief description of the drawings]

1 is a spectral transmittance curve by illuminant D ₆₅ at a thickness 5mm ultraviolet absorbing glass according to the first embodiment of the present invention.

Claims (4)

[Claims] 1. A soda-lime-silica-based glass having a basic composition of 0.15 to 0.30 Fe ₂ O ₃ (total iron) in terms of% by weight, CeO ₂
But from 1.3 to 2.0, with TiO ₂ is from 0.4 to 0.8, and ppm display, CoO 5 to 30, a glass Se contains 5-30 respectively reduction ratio of the glass (Fe ²⁺ / Fe ³⁺ ) Is 0.05 or less. 2. The ultraviolet absorbing glass according to claim 1, further comprising:
in ppm display, Cr ₂ O ₃ is 0 to 8, MnO is 0 to 150, NiO is
The ultraviolet absorbing glass according to claim 1, wherein at least one of these components of 0 to 10 is contained. 3. A plate thickness of said ultraviolet absorbing glass is 5
light source as measured by D ₆₅ or A in mm, the visible light transmittance Tv of 75% or more, and claim 1 or 2 ultraviolet absorbing glass, wherein the ultraviolet transmittance Tuv is equal to or less than 13%. 4. The basic composition of the soda-lime-silica glass is expressed in terms of% by weight, wherein SiO ₂ is 67 to 75 and Al ₂ O ₃ is 0.05 to 3.
0, CaO is 7 to 11, MgO is 2 ~ 4.5, Na ₂ O is from 11.5 to 16,
K ₂ O is 0.5 to 3.0, SO ₃ is 0.05 to 0.4, and SiO ₂ + Al ₂ O
₃ + TiO ₂ 68-75, CaO + Mg0 9-15, Na ₂ O + K ₂ O
4. The ultraviolet absorbing glass according to claim 1, wherein n is from 12 to 17.