JPH10297934A - Colored glass absorbing ultraviolet and infrared rays - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a colored glass composition absorbing ultraviolet and infrared rays enabling mutual exchange of a clear glass and the colored glass absorbing the ultraviolet and infrared rays to be rapidly carried out and capable of forming a high quality glass without largely changing the conditions for operating the furnace and making a board by using a clear soda ash glass composition as a base, regulating the total of coloring components so as to be within a specific range and allowing the composition to have various properties resembling to that of the clear glass. SOLUTION: This colored glass absorbing ultraviolet and infrared rays is obtained by using a base composition comprising 71.1-71.5 wt.% SiO2 , 1.6-1.9 wt.% Al2 O3 , 3.2-3.5 wt.% MgO, 6.9-7.2 wt.% CaO, 12.8-13.3 wt.% Na2 O, 0.6-0.9 wt.% K2 O and 0.05-0.2 wt.% SO3 , and formulating Fe2 O3 (whole iron), and CeO2 and/or TiO2 as coloring components and regulating the total of the coloring components so as to be 2.0-3.0 wt.%. The glass preferably has 2.50-2.52 specific gravity, 1440±10 deg.C temperature at log η (poise)=2, and 515±10 deg.C temperature at the strain point.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the present invention which transmits a suitable amount of visible light, absorbs infrared rays and ultraviolet rays, contributes to reduction of heating / cooling load and energy saving, suppresses deterioration and discoloration of organic substances, and provides privacy. Excellent livability, such as ensuring
The present invention relates to an ultraviolet-ray-absorbing colored glass useful as a window glass for vehicles for construction, automobiles, etc., or for aircraft such as aircraft and ships.

[0002]

2. Description of the Related Art Conventionally, based on a clear soda-lime glass component composition, TiO ₂ and / or CeO ₂ are additionally introduced to absorb ultraviolet rays, and Fe ₂ O ₃ is additionally introduced. Absorbs infrared light, more CoO, or more Mn
It has been proposed to obtain a colored glass such as a greenish glass in which the color tone has been adjusted by appropriately adding O ₂ , Cr ₂ O _{3, and the} like, and the glass has been offered to the market.

However, if these coloring components are added in amounts of up to 2 to 3% by weight, when the production is switched from clear glass to UV-infrared absorbing colored glass or from UV-infrared absorbing colored glass to clear glass, they are mutually operated. Kiln and plate making conditions changed, making it difficult to switch quickly,
The production loss during that time is enormous, and there is a problem that it is difficult to obtain stable and high-quality glass by inducing non-uniformity and discoloration such as uneven substrate.

The present invention has been accomplished in view of the above-mentioned problems, and has been achieved after the examination. The switching between the clear glass and the ultraviolet and infrared absorbing colored glass can be quickly performed without greatly changing the operation furnace and the plate making conditions. An object of the present invention is to provide an ultraviolet-ray-absorbing colored glass composition capable of obtaining a high-quality glass stably even afterwards.

[0005]

SUMMARY OF THE INVENTION The present invention relates to a method for producing SiO _{2
71.5wt%, Al 2 O 3 1.6} ~1.9 wt%, MgO 3.2 ~3.5 wt
%, CaO 6.9 ~7.2 wt%, Na 2 O 12.8 ~13.3wt%, K 2 O
0.6 to 0.9 wt%, consists of SO ₃ 0.05 to 0.2 wt%, as coloring components, and at least Fe ₂ O ₃ (total iron), and a CeO ₂ and / or TiO _2, the sum of the coloring components is 2.0 to 3.0 It is intended to provide a UV-infrared absorbing colored glass which is wt%.

Further, the present invention provides that the specific gravity of the ultraviolet and infrared absorbing colored glass is 2.50 to 2.52,

[0007] Further, the ultraviolet and infrared absorbing colored glass has a log η (poise) in terms of glass viscosity-temperature.
= 2 at 1440 ± 10 ℃, strain point at 5
15 ± 10 ° C,

[0008] In addition, when the ultraviolet and infrared absorbing colored glass has a thickness of 4 mm, the ultraviolet light transmittance by the light source A is 10% or less, the visible light transmittance is 65% or more, and the solar transmittance is 45% or less. Consists of

[0009]

DESCRIPTION OF THE PREFERRED EMBODIMENTS In Table 1, examples of typical compositions of clear glass as reference examples, examples of compositions of conventional green colored glass as comparative examples, and glass compositions of Examples 1 to 3 according to the present invention are shown. Is shown. Table 2 shows the optical properties, thermal properties, and other physical and chemical properties of each glass. The invention will now be described with reference to the following tables.

[0010] In the component system of the present invention, SiO ₂ whereas the conventional clear glass is about 71.7~72wt%, 71.1
The range of ％ 71.5 wt% and the range of change are suppressed as much as possible. SiO ₂ is a key component that forms the skeleton of glass. If it is significantly increased or decreased, various physical properties will change considerably, and the kiln and plate making conditions must be changed accordingly. If SiO ₂ is less than 71.1 wt%, the glass viscosity tends to decrease, the coefficient of thermal expansion increases, the density increases, and the water resistance and weather resistance of the product glass tends to decrease. On the other hand, if the content exceeds 71.5 wt%, the above tendency tends to be opposite, and the melting of the raw material becomes difficult, and the devitrification of the silica-based crystal tends to occur. The above range is necessary in order to approach the conventional clear glass operation furnace and plate making conditions.

The reduced amount of SiO ₂ is replaced with a part of the similar tetravalent components CeO _2, TiO ₂ and Fe ₂ O ₃ . Al ₂ O ₃ is 2wt% in conventional clear glass
The content should be in the range of 1.6 to 1.9 wt%, and the coloring components such as Fe ₂ O ₃ and Ce
Substitute some of O ₂ and TiO ₂ . When Al ₂ O ₃ is less than 1.6 wt%, the liquidus temperature of the glass tends to increase, and the water resistance and weather resistance of the product glass tends to decrease. On the other hand, when the content exceeds 1.9 wt%, devitrification of alumina-containing crystals is apt to occur, and heterogeneous striae are liable to occur in the glass. The above range is necessary in order to approach the conventional clear glass operation furnace and plate making conditions.

MgO is conventionally used in clear glass.
3.7 to 4 wt% or more should be 3.2 to 3.5 wt%
In conventional clear glass, CaO is 8%.
6.9 to 7.2 wt% should be about wt% or more
% In the range of the original clear glass, it is reduced by the same ratio, respectively, and the divalent component oxide similar to CeO ₂ , TiO ₂ and MgO Replace with a part of certain FeO. If the content of MgO 2 or CaO 2 is less than the above range, the liquidus temperature of the glass tends to increase, and the high-temperature viscosity tends to increase. On the other hand, if MgO or CaO exceeds the above range, silica-calcia (magnesia) is added to the glass.
The system crystal tends to be devitrified, the water resistance and weather resistance of the product glass tends to decrease, and the specific gravity tends to increase. The above range is necessary in order to approach the conventional clear glass operation furnace and plate making conditions.

Since CeO ₂ , TiO _2, and FeO have properties similar to CaO and MgO divalent component oxides, which lower the high-temperature viscosity of glass and increase the specific gravity, these divalent components are used. It is convenient for introducing the oxide in place of the oxide.

Na, which is an alkali component for melting glass
When ₂ O is 12.8~13.3wt%, K ₂ O is intended to be 0.6 to 0.9 wt%, which is intended to maintain the introduced amount comparable to conventional clear glass, it is less than the above lower limit, melting of the glass It tends to be inferior. On the other hand, when it exceeds the above upper limit, the water resistance and weather resistance of the glass product deteriorates.

Glauber's salt is indispensable as a fining agent, and it is necessary to introduce 0.5 to 0.8 parts by weight per 100 parts by weight of silica, and thus 0.05 to 0.2 wt% remains in the glass. In addition,
It is also common practice in the production of ultraviolet and infrared absorbing colored glass to use carbon as a fining agent together with sodium sulfate and maintain an appropriate iron ion ratio (Fe ²⁺ / Fe ³⁺ ).

As a coloring component of the ultraviolet and infrared absorbing colored glass, at least Fe ₂ O ₃ (total iron) absorbing the infrared region;
It contains CeO ₂ and / or TiO ₂ absorbing the ultraviolet region, and the sum of these coloring components is in the range of 2.0 to 3.0 wt%. In order to exhibit the above-mentioned effects, of the above, Fe ₂ O
₃ (total iron) 0.5 wt% or more, CeO ₂ and / or TiO ₂ 1.
5 wt% or more is required. In CeO ₂ and TiO ₂ ,
Mainly CeO ₂ that can easily change the iron ion ratio but can cut off the ultraviolet region sharply, has absorption from the ultraviolet region to the visible light low wavelength region, but has a secondary effect of TiO ₂ that does not affect the reduction rate. Is preferably used.

In adjusting the color tone, the above components are appropriately increased. Or further optionally MnO, CoO, Cr and ₂ O ₃ or the like can be several ppm ~ several hundred ppm introduction. However, if the total amount of the coloring components exceeds 3.0 wt%, the visible light transmittance of the product decreases. In addition, it is difficult to obtain operating conditions close to the operation of clear glass kilns and plate making.

The specific gravity of the glass is adjusted to 2.50 to 2.52 by harmonizing the respective component compositions to approximate the specific gravity of the clear glass to 2.49, so that the specific gravity is particularly high when switching from the clear glass to the ultraviolet and infrared absorbing colored glass. It is possible to eliminate problems such as the ultraviolet and infrared absorbing colored glass melt being biased toward the bottom of the kiln, making smooth switching difficult.

Further, considering the balance of the above-mentioned component compositions, Logη (poise)
= 2 (also referred to as the melting temperature. The temperature used as the standard for melting glass raw materials and removing coarse bubbles) is 1440
Within ± 10 ° C, temperature at strain point (Logη = 14.5 (poise)
By setting the temperature, which is an index for slow cooling design, within 550 ± 10 ° C, it can be approximated to that of clear glass. Does not require significant manufacturing condition fluctuations.

In addition, at least one point in addition to the above two points, for example, the temperature at Logη = 4 (also referred to as the working temperature; the temperature used as an index for molding) is within 1040 ± 10 ° C. By approximation, the known Fulcher viscosity-temperature relationship equation (Logη = A + B / (T−T
o): A, B, T are constants. To is the measurement temperature), the viscosity of clear glass can be approximated to the temperature-temperature of clear glass in the entire viscosity range. It can be approximated.

When converted to a thickness of 4 mm, the ultraviolet ray transmittance of the light source A is 10% or less and the visible ray transmittance is 65%.
%, And a solar transmittance of 45% or less, which is similar to a conventional ultraviolet and infrared absorbing colored glass, and can be a similar colored glass. Further 500 ～540Nm a dominant wavelength in the illuminant D ₆₅
Then, a suitable greenish colored glass can be obtained.

The present applicant has previously filed Japanese Patent Application No. 8-12781.
No., in wt%, SiO_Two 67-75, Al_TwoO_Three 0.05-3.0
 , CaO 7.0-11.0, MgO 2.0-4.2, Na_TwoO 12.0-16.
0, K_TwoO 0.5-3.0, SO_Three0.05 ~ 0.30 with clear ingredient
And Fe_TwoO_Three 0.40 ~ 0.90, CeO_Two1.0-2.5, TiO_Two 0.1 to
1.0, MnO 0.001-0.040, CoO 0.0001-0.0009, Cr _TwoO
_Three 0.0001-0.0010, SnO_Two 0 to 1 for coloring component and color tone adjustment
Proposal of ultraviolet and infrared absorbing green glass containing as a component
And Fe_TwoO_Three , CeO_Two, TiO_TwoIn addition to the coloring components, MnO and Co
O, Cr_TwoO_Three , SnO_TwoColor components and color tone adjustment components
Gives a very good greenish glass
It was stated that the composition of each of the clear components was
And the above-mentioned coloring composition.
And the total of the color tone adjusting components is defined as the range of the coloring component of the present invention.
To obtain a suitable UV-infrared absorbing green glass
Can be.

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 architecture, a window material for transport equipment, and particularly as a window glass for vehicles.

[0024]

EXAMPLES The present invention will be described below in comparison with comparative examples, but the present invention is not limited to these examples.

Example 1 Silica sand, feldspar, soda ash, dolomite,
Limestone, Glauber's salt, Bengala, Titanium oxide, Cerium carbonate,
Colored component concentrated frit was appropriately used for carbon. These are mixed in a desired ratio, and the prepared raw materials are put in a crucible,
About the same as the temperature of the actual kiln (for example, the side wall near the inlet)
Melt and vitrify in an electric furnace maintained at about 1450 ° C for about 3 to 4 hours, and further homogenize and clarify
After being kept at 1430 ° C. for about 1.5 to 2 hours, it was poured into a mold to form a glass block, cut out into a plate shape, ground and polished, or reprocessed into a rod shape and a thin wire shape to obtain each measurement sample.

For these samples, the glass component composition (% by weight) was analyzed by an analytical method based on JIS R-3101, and the optical characteristics (at a thickness of 4 mm) of visible light (wavelength 38
0 to 780 nm) transmittance (%: A light source), ultraviolet light (wavelength 29
7.5 ～377.5Nm) transmittance (%: at A light source), and solar radiation (wavelength 340 ～1800Nm) transmittance (%: at A light source), dominant wavelength (nm: at illuminant D _65), an excitation purity (%: at D ₆₅ light source) was measured and calculated with a 340-type self-recording spectrophotometer (manufactured by Hitachi, Ltd.) based on JIS Z-8722, JIS R-3106, and ISO / DIS-9050. (℃) sphere lifting method is in a high temperature region about the relationship, bending a in the low temperature range - with determining the temperature of the measuring and 10 ² and 10 ¹² poise viscosity curve by beam method, Lili - strain point by law, Littleton The softening point was measured by the method.

The coefficient of linear expansion and the glass transition temperature are measured by a thermal dilatometer, the density is measured by an Archimedes method, and JIS R
Water resistance was determined based on 3502. As a result, analytical values and measured values shown in Tables 1 and 2 were obtained.

Example 2 Using the same glass raw material and frit as in Example 1, the components were weighed and blended to the desired component composition, melted, and the obtained glass was similarly used as a measurement sample.

This was analyzed and measured in the same manner as in Example 1 above.
Evaluation was performed, and the analytical values and measured values shown in Tables 1 and 2 were obtained. Example 3 The same glass material and frit as in Example 1 were used, and the components were weighed and adjusted to a desired component composition, melted, and the obtained glass was similarly used as a measurement sample.

This was analyzed and measured in the same manner as in Example 1 above.
As a result of the evaluation, analytical values and measured values shown in Tables 1 and 2 were obtained. Comparative Example As a result of analyzing, measuring, and evaluating the existing ultraviolet and infrared absorbing colored glass in the same manner as in Example 1, Tables 1 and 2
The analytical values and measured values shown in Table 2 were obtained.

REFERENCE EXAMPLE As a result of analyzing, measuring, and evaluating (in terms of optical characteristics, a thickness of 5 mm) an existing representative float method soda-lime glass in the same manner as in Example 1, the analysis values shown in Tables 1 and 2 were obtained. , Measurements were obtained.

Results As shown in the following Tables 1 and 2, this example is similar in physical properties (thermal properties, physical properties, and chemical properties) to the clear glass of the reference example, while in the optical properties, It has a performance similar to the ultraviolet and infrared absorbing colored glass of the comparative example, and it is possible to quickly switch between clear glass and ultraviolet and infrared absorbing colored glass without significantly changing the kiln and plate making conditions. It clearly shows that high quality glass can be obtained stably.
On the other hand, the conventional UV-infrared absorbing colored glass in the comparative example is different from the present example in the component composition range, and as a result, it has a difference in high-temperature viscosity, density and the like from the clear glass. This means that the mutual switching of the glass cannot be performed smoothly, and that the operation of the kiln and the plate making conditions for the clear glass have to be considerably changed.

[Table 1] Glass composition (wt%) Reference example Comparative example Example Example Example Example Clear Colored 12 3 SiO ₂ 71.7 69.9 71.3 71.2 71.2 Al ₂ O ₃ 2.0 2.01 1.72 1.72 1.90 MgO 3.7 3.53 3.31 3.37 3.38 CaO 8.2 7.89 7.03 7.04 7.01 Na ₂ O 13.1 12.9 13.1 13.2 12.9 K ₂ O 0.7 0.85 0.84 0.84 0.69 SO ₃ 0.2 0.07 0.07 0.11 0.09 Total Fe ₂ O ₃ 0.1 0.610 0.611 0.749 0.631 FeO --- 0.226 0.198 0.179 0.143 CeO _2- -1.83 1.61 1.40 1.71 TiO ₂ --- 0.39 0.39 0.19 0.41 CoO (ppm) --- --- 0.0 0.0 0.3 Fe ²⁺ / Fe ³⁺ --- 0.7 0.56 0.36 0.34 0.06 ** 0.17 * 0.16 * 0.17 * Amount of Glauber's salt *** --- --- 0.5 0.5 0.5 Note * Amount to glass (wt%), ** Content in glass (wt%) *** to silica (SiO ₂ ) ratio (wt%)

[Table 2] Optical Properties, Other Physical and Chemical Properties Reference Example * Comparative Example ** Example ** Example ** Example ** Clear UMFL 1 2 3 Optical Properties UV Transmittance 56 7.4 7.9 8.4 8.1 Visible light transmittance 90 71.2 74.7 74.5 69.0 Solar transmittance 83 41.5 44.4 46.2 34.2 Principal wavelength 513 510.7 515.6 524.6 500.1 Stimulation purity 0.3 2.9 2.6 2.6 5.5 Color tone Colorless Clean "Clean" Clean "Clean" Heat Properties Thermal expansion coefficient 86 85.9 84.3 85.3 84.3 Transition temperature (Tg ° C) 555 558 553 552 556 Softening point (Tsoft ° C) 735 745 741 737 747 Slow cooling point (Tann ° C) 555 559 557 555 563 Strain point (Tstr ° C) 515 519 519 512 520 Viscosity-temperature Logη = 2 1440 1421 1440 1430 1437 4 1040 1033 1034 1030 1042 5 920 920 919 912 928 7 770 769 766 760 775 9 670 672 669 664 664 677 Other physical and chemical properties Density (D g / cc) 2.49 2.539 2.518 2.516 2.517 Water resistance (mgNa ₂ O / Dg) 0.48 0.34 0.42 0.44 0.39 Note * 5mm thickness ** 4mm thickness

[0035]

According to the present invention, various physical properties (thermal properties, physical properties, chemical properties) are similar to those of clear glass, while optical properties are similar to those of conventional ultraviolet and infrared absorbing colored glass. The ability to quickly switch between clear glass and UV-infrared-absorbing colored glass without significantly changing the kiln and plate making conditions. This has the effect that it can be obtained.

Claims (4)

[Claims] Claims: 1. An SiO_Two 71.1 to 71.5wt%, Al_TwoO_Three 1.6-1.9
wt%, MgO 3.2 to 3.5 wt%, CaO 6.9 to 7.2 wt%, Na_TwoO
 12.8 to 13.3wt%, K_TwoO 0.6 to 0.9 wt%, SO _Three 0.05-0.
2 wt%, at least Fe_TwoO_Three(all
Iron) and CeO_TwoAnd / or TiO_TwoAnd the coloring component
UV-infrared light whose sum is 2.0-3.0 wt%
Line absorbing colored glass. 2. The ultraviolet and infrared absorbing colored glass according to claim 1, wherein the specific gravity of the glass is 2.50 to 2.52. 3. In the relationship between glass viscosity and temperature, Logη
3. The ultraviolet and infrared absorbing colored glass according to claim 1, wherein the temperature at (poise) = 2 is 1440 ± 10 ° C., and the temperature at the strain point is 515 ± 10 ° C. 4. At a thickness of 4 mm, the transmittance of ultraviolet light by the light source A is 10% or less, the visible light transmittance is 65% or more,
5. The ultraviolet and infrared absorbing colored glass according to claim 1, wherein the solar radiation transmittance is 45% or less.