JP2001270735A - Green color system glass absorbing ultraviolet light and infrared light - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain green color system glass which has a high visible light transmittance, has a high performance for screening ultraviolet light and solar light, is preferable in visibility, and does not give senses of fatigue to the eyes. SOLUTION: This green color system glass absorbing ultraviolet light and infrared light, characterized by containing 0.7 to 1.0 wt.% (all iron) of Fe2O3, 0.4 to 1.0 wt.% of CeO2, 0.1 to 0.5 wt.% of TiO2, and 0.0001 to 0.0009 wt.% of CoO in soda lime silica system glass as components for adjusting the color and hue of the glass, and having a Fe2+/(Fe2++Fe3+) ratio of 0.18 to 0.26.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet-ray-absorbing green glass which can be suitably used as a window material of a transporting / transporting machine for buildings / constructions, vehicles, ships, airplanes and the like.

[0002]

BACKGROUND OF problem to be solved by the present invention, soda-lime-silica glass _{Fe 2 O 3 -FeO-CeO 2} -TiO 2 consisting -CoO colored, is intended to include color tone adjustment component. In contrast, JP-B-6-88812, JP-A-4-310539, and JP-A-7-165435 disclose, in an ultraviolet and infrared absorbing glass, a component system containing no CoO component as a coloring and color tone adjusting component. Is disclosed, but the CoO content in the component system of the present invention is an essential component for obtaining good green coloring.

Japanese Patent Application Laid-Open No. Hei 8-217485 discloses a component system having a low content of Fe ₂ O ₃ in an ultraviolet absorbing glass. However, as a colored glass, an appropriate coloring degree and good green color are obtained. Above is not appropriate.

[0004] Separately, Japanese Unexamined Patent Publication No. 8-217486, in the ultraviolet and infrared radiation absorbing glass, after it component system CeO ₂ minutes is not included has been disclosed, CeO ₂ minutes to effectively absorb the ultraviolet region It is an indispensable component.

[0005] Further, Japanese Patent Application Laid-Open No.
No. 8254 discloses a UV-infrared absorbing green-based glass, which includes Cr ₂ O ₃ minutes, MnO ₂ minutes, and a component system containing SnO ₂ minutes as an optional component, which is suitable for strict color tone adjustment. However, there is a concern that the dispensing operation using more components is complicated and that the rate of causing erroneous operations is high.

[0006]

SUMMARY OF THE INVENTION The present invention relates to a soda-lime-silica-based glass,
Fe ₂ O ₃ (total iron) 0.7 to 1.0, CeO ₂ 0.4 to less than 1.0, TiO ₂
It is an ultraviolet-ray-absorbing green glass containing 0.1 to 0.5 and CoO in the range of 0.0001 to 0.0009, and having an iron ion ratio of Fe2 ⁺ / (Fe2 ⁺⁺ Fe3 ⁺ ) of 0.18 to 0.26.

In the above, the optical characteristics at a glass thickness of 5 mm are such that the visible light reflectance is 65% or more, the solar radiation transmittance is 50% or less, the ultraviolet ray transmittance is 10% or less, and the main wavelength of the D light source is 52%.
It should be 0 to 550 nm.

[0008]

BEST MODE FOR CARRYING OUT THE INVENTION In the ultraviolet-infrared absorbing green glass of soda-lime-silica glass, in order to keep the visible light transmittance high, basically all the Fe ₂ O in the glass is required.
₃ It is necessary to increase the FeO content in order to keep the content low and keep the solar transmittance low. Therefore the reduction rate,
That is, the iron ion ratio Fe ²⁺ / (Fe ²⁺ + Fe ³⁺ ) must be increased, in which case a large amount of a reducing agent (eg, carbon) must be introduced, which forms a multi-bubble layer on the surface of the glass melt. However, generally, the heating method of a general kiln hinders the heat transfer to the glass substrate and deteriorates the productivity of the glass. Therefore, unnecessary introduction of the reducing agent must be suppressed.

Further, in order to suppress the ultraviolet transmittance,
Basically, it is necessary to increase the CeO ₂ content in the glass, but the CeO ₂ raw material is extremely expensive, which leads to an increase in glass production cost. Therefore, use of CeO ₂ must be minimized.

[0010] The present invention relates to a coloring and color tone adjusting component comprising Fe
_This problem is solved by appropriately restricting the content range of ₂ O ₃ —FeO—CeO ₂ —TiO ₂ —CoO.

In the present invention, the soda-lime-silica glass contains 68 to 73% by weight of SiO ₂ , 0 to ₃ % by weight of Al ₂ O ₃ , and 0 to 0% of MgO.
5wt%, CaO 5~12wt%, Na 2 O 10~15wt%, K 2 O 0
About 3 wt%, which is in the range of so-called ordinary soda-lime-silica glass.
It is excellent in terms of mass productivity, water resistance and weather resistance of glass products.

In the present invention, desired coloring and color tone adjusting components are contained in the glass in the following ranges so as to obtain desired optical characteristics.

Fe ₂ O ₃ (total iron) is 0.7% (% is weight%,
The same applies to the following, and the range is not more than 1.0%, which is a main component that reduces the transmittance of ultraviolet light and solar radiation by Fe ³⁺ and Fe ²⁺ and gives coloring. If it is 0.7% or less, the above effect cannot be exerted. If it exceeds 1.0%, the visible light transmittance is too low, and the visibility is impaired. More preferably
The range is over 0.7% to 0.9%. The iron ion ratio (Fe ²⁺ / Fe ²⁺ + Fe ³⁺ ) is set to 0.18 to 0.26. If the ratio is outside the above range, the absorption in the ultraviolet or infrared region becomes low, and the color tone is yellowish or yellowish. It becomes blue, and it is difficult to obtain a desired color tone. The iron ion ratio (Fe ²⁺ / Fe ²⁺ + F
e ³⁺ ) requires the introduction of more reducing agent to exceed 0.26, which forms a multi-bubble layer on the surface of the glass melt, as described above, and is generally not used in general kiln heating methods. There is a problem that the heat transfer to the substrate is hindered and the productivity of the glass is deteriorated.

CeO ₂ is contained in the glass in an amount of 0.4% or more to less than 1.0% in order to obtain the above-mentioned total Fe ₂ O 3 content and iron ion ratio, and to obtain a desired ultraviolet absorbing effect in the presence of TiO ₂ . If it is less than 0.4%, the ultraviolet absorbing effect is insufficient, and if it is 1.0% or more, the absorption on the short wavelength side of the visible region becomes excessive, the glass becomes yellowish, and the desired visible light transmittance,
It is difficult to obtain the dominant wavelength. In addition, CeO ₂ raw material itself is expensive, and 1.
The introduction of more than 0% increases the raw material cost. More preferably, it is in the range of 0.5% to less than 1.0%.

TiO ₂ has the effect of reducing the transmittance of ultraviolet light, like CeO _2, and has a content of 0.1 to 0.5%.
%, The effect is small, and if it exceeds 0.5% by weight, light absorption extends from the ultraviolet region to the visible region, and the color tone changes to yellowish, making it difficult to obtain the desired main wavelength and visible light transmittance.

CoO is an essential component for obtaining a green color tone. In the case of CoO alone, the glass is colored blue, but in the presence of Fe ₂ O ₃ , TiO ₂ , and CeO ₂ , 0.0001
A desired green color tone can be obtained by containing the compound in an amount of 0.0009%. If CoO is less than 0.0001%, it is not enough to obtain a green color tone, and if it exceeds 0.0009%, not only does the glass become bluish, but also the transmittance of visible light becomes lower than a required limit.

Sulfates such as Na ₂ SO ₄ and CaSO ₄ as fining agents act as oxidizing agents, and iron and steel slag, carbon and the like as the above-mentioned sulfate decomposition accelerator act as reducing agents. And the amount of addition and introduction thereof affects the iron ion ratio (Fe ²⁺ / Fe ³⁺ ), but in order to keep the iron ion ratio in the proper range, that is, 0.18 to 0.26, What is necessary is just to determine the mutual ratio, which is a design matter as appropriate.

The visible light transmittance at a glass plate thickness of 5 mm is 65.
% Or more. For example, when adopted for a windshield of an automobile, it is regulated by considering the actual plate thickness, or by further using a laminated glass with clear glass.
Visible light transmittance of 70% or more can be obtained. Of course, it can also be recommended as a suitable transparent green glass as a window glass for buildings, etc. In addition, the solar radiation transmittance at a plate thickness of 5 mm is set to 50% or less, so that heat rays in solar radiation and the like are blocked as much as possible. However, for example, the cooling load in summer can be effectively reduced. More preferably, it is set to 45% or less.

Further, the ultraviolet transmittance at a plate thickness of 5 mm is 10%.
It is desirable to set the following. The influence on the human body is prevented as much as possible, and the fading of various color materials can be suppressed as much as possible. More preferably, it is 8% or less.

When the dominant wavelength (depending on the D light source) is 520 to 550 nm, a green color which is visually preferable and does not give a tired feeling can be obtained.

The stimulus purity (depending on the D light source) is preferably 10% or less. That is, the color (light) of the object viewed through the glass is observed as a color closer to the original color of the object as the stimulus purity of the glass is lower. For example, in order to view the scenery through the glass in a natural color, the stimulus purity is lower. Good, but if it is less than 10%, it can be seen in a state close to natural colors.

Incidentally, the visible light transmittance and the solar transmittance are JI
S R3106, UV transmittance measured according to ISO / DIS-9050,
The dominant wavelength and stimulus purity are measured with a D light source based on JIS Z8722 and displayed according to JIS Z8701.

According to the present invention, in the case of a thin glass sheet having a thickness of about 1 mm and a thick glass sheet having a thickness of more than 10 mm, a half-strengthened or strengthened one as a flat plate or a bent plate can be easily manufactured from a raw plate. It can be suitably used as a sheet glass, a laminated glass, a double-layered glass, etc., as a window material for buildings and structures, and a window material for transportation equipment such as vehicles, airplanes and ships.

[0024]

EXAMPLES Examples of the present invention will be described below in comparison with comparative examples.

As a basic component composition, SiO ₂ 72, A
l ₂ O ₃ 2, MgO 4, CaO 8, Na ₂ O 13, K ₂ O 1, total 100
(% By weight), silica sand, feldspar, soda ash, dolomite, and limestone were used as raw materials and mixed and adjusted. The desired amount of Fe ₂ O ₃ (Fe
In order to contain O), CeO ₂ , TiO ₂ , and CoO, Bengala, cerium oxide, titanium oxide, and cobalt oxide were introduced at desired ratios, and the mixture was added to the basic component raw materials and mixed and prepared.

[0026] Glauber's salt and carbon were added and mixed as a fining agent and its decomposition accelerator, respectively. Glauber's salt is Na ₂ S
O ₄ was introduced in an amount of 1% by weight or less based on 100% by weight of the oxide glass, and carbon was appropriately introduced based on the theoretical amount required for the reaction and decomposition with Glauber's salt.

The raw material prepared in a desired ratio is put into a crucible and melted for about 3 to 4 hours in an electric furnace maintained at about 1450 ° C., which is equivalent to the temperature of an actual kiln (for example, the side wall near the inlet). For further homogenization and clarification,
After being kept at 1420 to 1430 ° C. for about 1.5 to 2 hours, it was poured into a mold to form a glass block, cut into a plate shape, and ground and polished to obtain each measurement sample.

For these samples, the content (% by weight) of the coloring / color tone adjusting component composition was analyzed by a gravimetric method, and the visible light transmittance (%) and the ultraviolet light transmittance (%) as optical characteristics (at a thickness of 5 mm) were obtained. ), solar transmittance (%), and dominant wavelength (nm: at illuminant D _65), an excitation purity (%: at illuminant D ₆₅₎ was determined. They are measured and calculated using a U4000 spectrophotometer (manufactured by Hitachi, Ltd.) in accordance with the standards. The results are shown in Tables 1 to 4.

As shown in Tables 1 to 4, in the present embodiment, the optical characteristics such as visible light transmittance, ultraviolet light transmittance, solar transmittance, dominant wavelength, and stimulus purity are within expected ranges, and are relatively small. It has a high visible light transmittance, a high shielding performance against ultraviolet rays and solar radiation, is visually pleasing, gives a greenish coloring that does not cause fatigue to the eyes, and is used for windows for buildings and structures, vehicles, airplanes, ships, etc. It can be suitably used as a window material for transportation equipment.

On the other hand, in the comparative examples, there are inconveniences that the desired optical characteristics cannot be obtained or that the raw material cost rises, which is out of the range of the coloring / tone adjustment component in the present invention.

[Table 1] Examples and Comparative Examples [Examples] 1 2 3 4 5組成 Composition of coloring components (% by weight) Total Fe ₂ O ₃ 0.875 0.857 0.902 0.756 0.877 FeO 0.193 0.172 0.168 0.150 0.185 CeO ₂ 0.85 0.84 0.63 0.53 0.72 TiO ₂ 0.19 0.18 0.39 0.29 0.39 CoO 0.00023 0.00061 0.00077 0.00042 0.00028 Fe ²⁺ / (Fe ²⁺ + Fe ³⁺ ) 0.25 0.22 0.21 0.22 0.23 Optical characteristics (equivalent to 5 mm thickness) Visible light transmittance (%) 66.5 66.2 66.2 70.8 66.0 Solar transmittance (%) 38.1 40.2 40.6 45.2 38.5 Ultraviolet rays Transmittance (%) 6.4 6.4 5.5 8.7 5.5 Dominant wavelength (nm) 531 538 548 539 545 Stimulation purity (%) 3.8 4.0 5.6 3.6 5.5

[Table 2] Examples and Comparative Examples [Examples] 6 7 8 9 10組成 Composition of coloring components (% by weight) Total Fe ₂ O ₃ 0.775 0.794 0.878 0.855 0.731 FeO 0.160 0.166 0.188 0.184 0.162 CeO ₂ 0.64 0.64 0.87 0.93 0.81 TiO ₂ 0.30 0.30 0.25 0.25 0.24 CoO 0.00017 0.00016 0.00031 0.00055 0.00040 Fe ²⁺ / (Fe ²⁺ + Fe ³⁺ ) 0.23 0.23 0.24 0.24 0.25 Optical properties (equivalent to 5 mm thickness) Visible light transmittance (%) 69.9 69.1 66.5 66.5 70.2 Solar transmittance (%) 43.3 42.1 38.3 38.9 43.2 Ultraviolet rays Transmittance (%) 8.0 7.5 5.6 5.7 7.6 Dominant wavelength (nm) 538 540 540 537 536 Stimulation purity (%) 3.8 4.2 4.6 4.2 3.5

[Table 3] Examples and Comparative Examples [Examples] [Comparative Examples] 11 1 2 3 4着色 Composition of coloring components (% by weight) Total Fe ₂ O ₃ 0.730 0.565 0.628 0.582 0.631 FeO 0.157 0.207 0.232 0.191 0.210 CeO ₂ 0.83 1.90 1.62 1.31 1.59 TiO ₂ 0.25 0.38 0.36 0.32 0.39 CoO 0.00039 0.00012-0.00012 0.00002 Fe ²⁺ / (Fe ²⁺ + Fe ³⁺ ) 0.24 0.41 0.41 0.36 0.37 Optical characteristics (equivalent to a plate thickness of 5 mm) Visible light transmittance (%) 70.8 70.5 68.2 71.4 67.4 Solar transmittance (%) 44.0 40.2 37.1 42.0 36.8 UV transmittance (%) 7.8 5.3 5.5 7.5 4.5 Dominant wavelength (nm) 534 522 522 517 537 Stimulation purity (%) 3.3 3.1 3.4 2.8 4.4

[Table 4] Examples and Comparative Examples [Comparative Examples] 5 6 7 8 9着色 Composition of coloring components (% by weight) Total Fe ₂ O ₃ 0.760 0.680 0.630 0.620 0.690 FeO 0.195 0.168 0.196 0.193 0.220 CeO ₂ 1.35 1.25 1.52 0.31 0.40 TiO ₂ 0.30 0.30 0.32 0.19 0.24 CoO-- 0.00001 0.00014-Fe ²⁺ / (Fe ²⁺ + Fe ³⁺ ) 0.29 0.27 0.35 0.35 0.35 Optical characteristics (equivalent to plate thickness of 5 mm) Visible light transmittance (%) 67.1 71.8 70.0 71.2 68.4 Solar transmittance (%) 37.3 43.9 40.3 42.2 38.1 UV transmittance (%) 5.7 7.3 6.4 13.0 10.7 Dominant wavelength (nm) 527 531 514 508 507 Stimulation purity (%) 3.6 3.2 3.0 3.0 3.5

[0035]

The glass of the present invention is a greenish glass having a relatively high visible light transmittance, a high ability to shield ultraviolet rays and solar radiation, is visually pleasing, and does not give a feeling of fatigue to eyes. It can be suitably used as a window material for buildings and structures, and a window material for vehicles such as vehicles, airplanes and ships.

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Claims (2)

[Claims] (1) Fe ₂ O ₃ (total iron) exceeding 0.7 to 1.% by weight as a coloring and color tone adjusting component in soda-lime-silica glass.
0, CeO ₂ 0.4-1.0, TiO ₂ 0.1-0.5, CoO 0.0001-
Fe ²⁺ / (Fe ²⁺ + F
e ³⁺ ) is 0.18 to 0.26. 2. The optical characteristics at a glass thickness of 5 mm are that the visible light reflectance is 65% or more, the sunlight transmittance is 50% or less, the ultraviolet transmittance is 10% or less, and the main wavelength of the D light source is 520 to 550 nm. The ultraviolet and infrared absorbing green glass according to claim 1.