JP2513944B2 - Infrared UV absorbing glass - Google Patents

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a relatively high transparency and absorbs infrared rays and has high habitability and safety, and can be made lighter in weight. Regarding the absorption glass, the present invention provides the infrared-ray and ultraviolet absorption glass which is useful not only for building window glass and various glass articles but also for vehicle window glass.

[0002]

2. Description of the Related Art In recent years, due to abundant energy saving such as cooling load reduction or deterioration and fading of organic matter,
By adding multi-functionalization such as reflection and absorption of infrared rays and ultraviolet rays to the glass itself or the glass surface, there is a rapidly increasing need for a flat glass article that leads to higher habitability both physically and physically.

Therefore, in addition to the conventional infrared absorbing glass, glass considering ultraviolet absorption is being further proposed. For example, in JP-A-64-18938, at least 0.45% by weight of iron represented by Fe ₂ O ₃ is represented. A continuous flow of molten glass having a controlled flow rate, controlling the redox conditions during the melting operation to give at least 35% of iron in the ferrous state, expressed as FeO, and shaping the glass into a flat glass product in a shaping operation. And the flat glass has at least 65
Disclosed is a method for producing soda-lime-silica flat glass by a continuous method having a light transmittance of 15% and an infrared transmittance of 15% or less, and represented by Fe ₂ O ₃ in the glass is 0.65%.
It is stated that it is preferable that a lower total iron content is given or that the sulfur content of the product glass is represented as SO _{3 and} less than 0.02%, and is also represented as Fe ₂ O _3. At least 0.45% by weight of total iron, of which at least 50% has iron in the ferrous state, expressed as FeO, and less than 0.02% by weight, expressed as SO ₃ , with a light transmission of at least 65%. And 15%
Discloses a soda-lime-silica glass article having the following total solar infrared transmittance, the glass article, based on the weight, 66-75% of SiO _2, 12 to 20 percent of Na ₂ O, 7 ~ 12%
CaO, 0-5% MgO, 0-4% Al ₂ O ₃ , 0-3%
K ₂ O, 0 ~1% of Fe ₂ O _3, and _{CeO 2, TiO 2, V 2} O 5 or Mo
It is stated that those having a composition consisting essentially of 0-1.5% of the total O ₃ are preferred. Furthermore, U.S. Pat. No. 47
No. 01425, expressed as% by weight, 60-80% SiO ₂ , 10-20
% Na ₂ O, 0-10% K ₂ O, 5-16% CaO, 0-10%
Of MgO, 0 to 5% of Al ₂ O _3, 0 ~0.5% of SO _3, 0.29 to
0.6% Fe ₂ O ₃ , 0.1-1.5% SnO ₂ , 0.1-1.6%
Glass compositions are disclosed for absorbing infrared light and ultraviolet light consisting essentially of TiO _2.

[0004]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As described above, for example, in Japanese Patent Laid-Open No. 18938/1988, the SO ₃ component is
Since it is less than 0.02% by weight, it is difficult to obtain a desired infrared-ultraviolet-absorbing glass by a melting operation means in the production of a flat glass by a normal float method, and various complicated means steps such as a liquefaction step and a melting step. , A fining stage, a stirring chamber, a stirrer, etc. are required, and it is difficult to say that the one described in US Pat. However, it is hard to say that it is always sufficiently excellent.

[0005]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks of the prior art, and has a large thermal expansion coefficient, a Young's modulus and a Poisson's ratio and a small thermal conductivity. In addition, it has a desired absorption of infrared rays and ultraviolet rays, develops a relatively pale green color tone that is relatively transparent, and has sufficient weather resistance and moldability. The present invention provides a transparent infrared and ultraviolet absorbing glass.

That is, the present invention is expressed in% by weight,
Substantially the following oxides, SiO ₂ 68-72%, Al ₂ O ₃ 1.6-
3.0%, CaO8.5~11.0%, MgO2.0~4.2% , Na 2 O12.0~
_{16.0%, K 2 O0.5~3.0%,} SO 3 0.08 ~0.30%, Fe 2 O 3 0.5
8 to 0.65% (not including 0.65%), CeO ₂ 0.1 to 0.5%, Ti
O ₂ 0.1-0.4%, and MnO 10-35 as a trace oxide
It contains at least 0 ppm, the total of these components is 98% or more, and SiO ₂ + Al ₂ O ₃ + TiO ₂ 70-74%, CaO + MgO
12 to 15%, Na ₂ O + K ₂ O 13 to 17%, and the viscosity temperature of the glass is 10 ⁹ poise, 650 to 685 ℃, 10 ¹² poise.
555 to 585 ℃, and the temperature difference between them is 96 to 103 ℃
Infrared UV absorbing glass characterized in that. Also, the visible light transmittance by the A light source is 69% in terms of 5 mm thickness.
Above, solar radiation transmittance is 35-47%, UV transmittance is 8-15
%, The main wavelength is 505 to 518 nm, the average transmittance between wavelengths 1000 to 1150 nm is 7 to 15%, and the stimulation purity is 5% or less. .

Here, the reason why the SiO ₂ component is 68 to 72% by weight is that if it is less than 68%, the surface is likely to be burnt or the like, and the weather resistance is lowered to cause a practical problem. 72%
If it exceeds 1.0%, its easy strengthening property decreases and it becomes difficult to melt it. The reason why the Al ₂ O ₃ component is 1.6 to 3.0% by weight is that if it is less than 1.6%, the weather resistance decreases and the surface is burnt. If it exceeds 3%, devitrification is likely to occur, the molding temperature range is narrowed, and the manufacturing becomes difficult, and the CaO component is 8.5% by weight.
〜11.0% means that if it is less than 8.5%, the easy strengthening property will decrease, and as a fluxing agent, it will be insufficient and the melting temperature will rise, and the flow temperature will not be lowered, making it difficult to manufacture.
If it exceeds, devitrification is likely to occur, the molding work range is narrowed, and manufacturing becomes difficult, and the MgO component is 2.0% by weight.
4.2% and was of, in less than 2.0% less likely to manufacture since narrow the operating range melting temperature rises, which decreases ease reinforcing exceeds 4.2%, by weight of Na ₂ O component
The range of 12.0 to 16.0% is that if it is less than 12.0, the easy strengthening property is lowered, the moldability becomes difficult, and devitrification easily occurs, so that the operation range is narrowed and it becomes difficult to manufacture, and if it exceeds 16%, the weather resistance is lowered, are those made burnt like easily occurs practical problems arise in the surface, 0.5 a K ₂ O component in weight%
The reason for setting 3.0% is that if it is less than 0.5%, the easiness of strengthening decreases.
Exceeds 3.0%, the weather resistance is lowered and cost is intended also increased, to that with 0.08 to 0.30% of SO ₃ component in weight percent, on degassing or homogeneity is less than 0.08% for example, in conventional melt non It can only be made to the extent that it easily becomes sufficient, and when it exceeds 0.30%, it particularly affects the coloring state of glass, and it tends to shift to a yellowish or amberish tone, for example This is because the greenish color tone of No. 1 cannot be obtained, and it is preferably around 0.15%, which is relatively low even within the range.

Fe₂O₃0.58-0.65% by weight of ingredients
Is the amount of FeO component that absorbs infrared rays and ultraviolet rays.
Securing a pale green color tone, if anything
To Fe₂O₃As the total amount of the components, the various optical characteristics
Other CeO for stable sex₂, TiO₂Amount of each component such as
It is also necessary for the above, and if less than 0.58%,
Is inferior in action, and when it exceeds 0.65%, the above-mentioned relatively thick gree
The color tone tends to be dark, and the visible light transmittance is particularly poor.
It is not preferable, and Fe is preferable. ₂O₃component
The total converted amount is about 0.6 to 0.64%. Also CeO₂And Ti
O₂The component has an ultraviolet ray absorbing function, and CeO₂Ingredients 0.1 to 0.
5%, TiO₂The composition of 0.1-0.4% is glass
Of the ultraviolet rays with almost no change in the reduction rate in
Absorption capacity is CeO₂TiO smaller than the components₂Ingredients and glass
Change the reduction rate relatively large
CeO that gives enough₂The composition is limited to the above specified range
By combining them, the desired characteristics can be efficiently achieved with a small content.
You can get it, and it will hardly change the conventional reduction rate
The valence of Ce in the glass is⁴⁺, Ce³⁺Horse
C, almost colorless Ce³⁺Mainly, the above-mentioned total iron
At Fe₂O₃And the ratio of FeO and visible light range
Do not reduce the overall transmittance of the
So that the desired optical characteristics such as absorption and infrared absorption can be achieved.
This is because, preferably CeO₂Ingredients 0.2-0.4%, Ti
O₂The component is about 0.15-0.25%. Furthermore, the MnO component is added to 10
~ 350ppm is because Fe is oxidized due to the relation between Fe and Mn.
And the reduction rate tends to be low
Yes, the relationship between Ce and Mn is that Mn is oxidized.
Since Mn has almost no effect on the reduction rate,
While interacting neutrally with Fe and Ce,
Adjusting the color tone with the absorption wavelength of MnO near 500 nm
So that it can be adjusted with a slight force without significantly affecting
If a large amount of MnO component is used,
For example, it is easy to develop phenomena such as solarization.
In order to avoid this, the amount should not exceed 350ppm.

Further, SiO ₂ , Al ₂ O ₃ , CaO, MgO, Na ₂ O,
The total of the components of K ₂ O, Fe ₂ O ₃ , SO ₃ , CeO ₂ , TiO ₂ , and MnO is set to 98% or more by weight percentage, for example, ZnO, SnO ₂ ,
This is to control trace components such as CoO, Se, and NiO so as not to exceed 2%. Among them, V ₂ O ₅ component as an arbitrary component
It may be added in an amount of about 0.25%, and the V ₂ O ₅ is used for fine adjustment because it hardly changes the reduction rate and its ultraviolet absorption capacity is smaller than that of the CeO ₂ component and has little effect. This is because it is necessary to minimize the valence in glass of V ⁵⁺ which exhibits yellow color and to make it mainly to V ³⁺ which exhibits green color.

Furthermore, the reason that the weight percentage of SiO ₂ + Al ₂ O ₃ + TiO ₂ is 70 to 74% is that the weather resistance decreases when the content is less than 70%.
If it exceeds 74%, the problem of deterioration of easy strengthening occurs, and CaO + MgO is defined as 12 to 15% by weight because
O and MgO components are used to lower the melting temperature, and if less than 12%, the easy strengthening property deteriorates, and if it exceeds 15%, devitrification tends to occur, which makes it difficult to manufacture.
_The percentage of ₂ O + K ₂ O is set to 13 to 17%. When it is less than 13%, the easy strengthening property is deteriorated, devitrification is likely to occur, the working temperature range is narrowed in molding, and the manufacturing becomes difficult. If it exceeds the above range, the weather resistance is lowered to cause a problem in practical use and the cost is increased.

Furthermore, in terms of 5 mm thickness, visible light transmittance by A light source is 69% or more, solar radiation transmittance is 35 to 47%, ultraviolet light transmittance is 8 to 15%, main wavelength is 505 to 518 nm, wavelength is 10%.
Average transmittance between 00 and 1150nm is 7 to 15%, stimulation purity is 5
% Or less is preferable because when the visible light transmittance is less than 69%, the visibility of the glass is particularly noticeable in the windshields of automobiles, especially when nightfall, nighttime or rain falls, and the distinguishability of objects decreases. Is not preferable, more preferably around 70%, further preferably around 75%, and if the solar radiation transmittance exceeds 47%, the cooling load cannot be increased or the habitability inside / inside the vehicle cannot be improved. If it is less than 35%, it is not preferable because it may affect the transparency and the deterioration of the above-mentioned distinctiveness or the color tone, and more preferably 38 to 45%.
It is a degree. In particular, if the average transmittance between wavelengths 1000 to 1150 nm exceeds 15%, it will have a large effect on the above-mentioned heat load, etc., and the effect of thermal absorption will be small, and if it is less than 7%, it will be transmitted in the visible range. This is because it is difficult to secure the performance as a window glass for vehicles due to a decrease in the rate, and more preferably
It is about 11-14%.

[0012] Furthermore, if the UV transmittance exceeds 15%, it tends to lead to deterioration of habitability due to human influence such as discoloration / deterioration of articles in the car / room or skin burn. Is more likely to occur, and more preferably about 10 to 14%. Furthermore, if the dominant wavelength exceeds 518 nm, the yellow or amber color influences and the desired green tone does not occur, and if it is less than 505 nm, the blue color wins too much and the desired green tone does not occur. , The preferred dominant wavelength is 507 to 515 nm, and if the stimulus purity exceeds 5%, the identification of the object will be deteriorated, and the visibility of the occupant will be hindered due to, for example, nightfall or heavy rain, which will increase safety. This is because it becomes difficult to secure the above, and more preferably it is about 3.5% or less. The ultraviolet range was 290 to 390 nm, and the visible range was the same as before.

Furthermore, in manufacturing the infrared-ultraviolet-absorbing glass, the balance of Fe ₂ O ₃ and FeO is important, so that the incorporation of FeO into the glass can be easily adjusted. Therefore, the operating conditions of the actual kiln are almost unchanged, and the redox state of the glass is not changed as much as possible, that is, the reduction rate is about 0.45-
Among the changes to about 0.70, in the production of the infrared and ultraviolet absorbing glass of the present invention, various effects such as CeO ₂ are added,
In order not to fluctuate as much as possible, for example about 0.47 to 0.65,
This is because it is a little more useful to make it about 0.48 to 0.6, and it is preferable to use at least one of metal powder or oxide such as carbon, Zn, and Sn as a trace amount raw material. Sometimes it is necessary to help the action effect of a clarifying agent such as Glauber's salt (Na ₂ SO ₄ ), but on the other hand, it tends to have a bad influence on securing the desired color tone.
Alternatively, a reducing agent such as Sn may be necessary in order to adjust the balance between Fe ₂ O ₃ and FeO.

The infrared and ultraviolet absorbing glass of the present invention has a viscous temperature of 10 ⁹ poise at 650 to 685 ° C.,
Since it is 555 to 585 ℃ at 10 ¹² poise and the temperature difference between them is 96 to 103 ℃, it is an easily tempered glass composition, and it is a thin glass with a thickness of about 1 mm to a thick glass with a thickness of about 10 mm. , Such as flat plate or bent plate, which has been strengthened from a raw plate, semi-reinforced, strengthened, etc., and can be used as a single plate glass, a laminated glass, a laminated glass or a double-layer glass, especially a window glass for a vehicle. It is useful to use in.

[0015]

As described above, the infrared-ultraviolet-absorbing glass of the present invention is a glass having a combination of specific oxide components in a specific composition range and having a specified viscosity temperature so as to have easy tempering property and suppress reduction of reduction rate. By producing the above-mentioned glass, for example, considering the meltability, clarity, weather resistance, moldability, devitrification, cost, etc., the production conditions of the conventional float glass and the properties of the glass are almost changed. In addition, it has an easy strengthening property, absorbs infrared rays and ultraviolet rays, and has a high habitability in terms of human physical properties, and it also has excellent transparency for distinguishing objects, and it is highly visible without glare. It is possible to ensure safety, and if anything, it is a light green color tone that is in good harmony with, for example, the car, the interior and exterior, and is environmentally friendly and excellent. Even with thin glass that could not be obtained by the method, it becomes easy to obtain a sufficient degree of strengthening or strength increase, and it can be used not only for building window glass but also for furniture glass, cooking glass, especially for automobiles with thin plate thickness. It is intended to provide an infrared and ultraviolet absorbing glass which is useful as a window glass for vehicles.

[0016]

EXAMPLES Examples of the present invention will be described below. Example 1 As a glass raw material, for example, silica sand, feldspar, soda ash, dolomite, limestone, mirabilite, red iron oxide,
Titanium oxide, cerium carbonate or ilmenite, or carbon in some cases is used.For example, when the viscous temperature is 10 ⁹ poise, about 650-685 ° C, 10 ¹² poise, about 555-585 ° C, and the temperature difference between them is 96-103 ° C. Weigh and formulate a glass composition that will become a degree as the target composition, melt while homogenizing and clarifying while ensuring the reduction rate in a plate glass melting kiln as much as possible, plate glass by the float method, size 100 mm ×
It was cut into a glass plate having a thickness of 100 mm and a thickness of about 5 mm, and used as each sample of infrared and ultraviolet absorbing glass.

[0017] For this sample, the glass component composition (wt%) is carried out by a wet analytical method based on JISR-3101, for the viscosity temperature (℃) by measuring the viscosity curve by bending arms method 10 ⁹ and 10 ¹² The poise temperature is calculated, the strain point is measured by the Lily method, and the softening point is measured by the Lyttelton method, and the visible light transmittance (% at A light source) and the ultraviolet transmittance (%) as optical characteristics (at a thickness of 5 mm) are measured. , And solar radiation transmittance (%), dominant wavelength (n
m) and the stimulus purity were measured and calculated using a 340 type self-recording spectrophotometer (manufactured by Hitachi, Ltd.) and JIS Z-8722, JIS R-3106, and ISO / DIS-9050.

As a result, the glass component composition of the infrared and ultraviolet absorbing glass was expressed by weight, SiO ₂ 70.0%, Al ₂ O ₃ 1.8%, CaO.
_{9.1%, MgO3.6%, Na 2} O13.4%, K 2 O0.7%, Fe 2 O 3 0.620
%, TiO ₂ 0.2%, CeO ₂ 0.31%, SO ₃ 0.14%, MnO 270ppm
The total of the components is 99.9% and SiO ₂
+ Al ₂ O ₃ + TiO ₂ 72.1%, CaO + MgO 12.7%, Na ₂ O + K ₂ O14.1
%, And the reduction rate (Fe ²⁺ / Fe ³⁺ ) was about 0.47 to 0.53.

The optical characteristic is that the visible light transmittance is 71.1%.
, Solar radiation transmittance is 42 ~ 43%, dominant wavelength is 508 ~ 511n
The average transmittance was about 13.7% in the wavelength range of 1000 to 1150 nm and the stimulus purity was about 3.2 to 3.5%, and the color tone was rather pale green.

Further, regarding the easy strengthening property, the above-mentioned glass has the above-mentioned viscous temperature clearing a predetermined specific range, and the temperature difference between the softening point and the strain point is about 200-.
After confirming that the temperature was in the range of about 240 ° C, the sample was heated in the furnace at an ambient temperature of about 650 to 730 ° C for about 5 minutes, and then strengthened with normal air cooling at an air pressure of about 1300Ap. Obtained a tempered glass plate with a size of 120 mm × 100 mm and a thickness of about 3.5 mm cut out from the glass plate, crushed by giving a shock at a position of about 30 mm from the corner end face of the corner of the tempered glass plate. When the crushed glass plate was examined in accordance with JIS R-3211, it was found that even a thin glass plate was a highly easy-to-strength infrared and ultraviolet ray absorbing glass that had a high efficiency and a high yield and sufficiently satisfied the predetermined standard.

The bent infrared and ultraviolet absorbing glass of the present invention having a thickness of about 2.5 mm is used on the outside, and the heat-reflecting film-covered bent glass plate having a thickness of about 2 mm is arranged on the inside, with the film side facing inside.
When a laminated glass laminated with PVB interlayer film was prototyped and used as a window glass of an automobile, the function and effect of the present invention were enhanced and further multifunctionalized, and the habitability inside and outside the vehicle and safety were more excellent. Was to be

Example 2 The same glass raw materials as in Example 1 were used, weighed and blended,
A melting operation was performed, and the obtained glass was similarly sampled.

The sample thus obtained was analyzed, measured and evaluated in the same manner as in Example 1, and as a result, the glass component composition was expressed by weight, SiO ₂ 70.2%, Al ₂ O ₃ 1.8%, CaO 9.1%, MgO 3.5 %, Na
₂ O 13.5%, K ₂ O 0.6%, Fe ₂ O ₃ 0.623%, TiO ₂ 0.19%, CeO ₂
0.31%, SO ₃ 0.13%, MnO around 290ppm, the total of the components is 99.983%, SiO ₂ + Al ₂ O ₃ + TiO ₂ 72.19
%, CaO + MgO 12.6%, Na ₂ O + K ₂ O 14.1%, and the reduction rate was about 0.48 to 0.58, similar to the above. The optical characteristics are visible ray transmittance of about 70.9%, solar radiation transmittance of 42-42.5%.
About 509 ~ 510.5nm, wavelength 1000 ~ 1150nm
The average transmittance between the two is about 13.5%, the stimulation purity is 3.4 ~ 3.5
%, Which was rather a light green color tone.

Further, as to the easy strengthening property, the above-mentioned Example 1 was used.
When the same procedure as in Example 1 was performed, it was possible to obtain a product that sufficiently satisfied the standards determined by JIS and passed the above standards even with a thin glass plate with high efficiency and high yield. It was. The above-described embodiments are merely examples of the present invention, and the present invention is not limited to these embodiments.

[0025]

EFFECTS OF THE INVENTION According to the present invention, the combination of the specific oxide components in the specific composition range and the infrared and ultraviolet absorbing glass having the specified viscous temperature suppresses the reduction of the reduction rate and absorbs the infrared rays and the ultraviolet rays. It is possible to change the operating conditions of a real kiln from glass that has a well-balanced absorption and absorption, has sufficient transparency, retains easy strengthening, and has a rather pale green color tone. It is possible to manufacture without needing to have high habitability, high safety, high environmental friendliness in terms of both human and physical properties, and also possible to reduce weight. In particular, the present invention provides an infrared and ultraviolet absorbing glass which is useful when applied to window glass for automobiles.

Claims (2)

(57) [Claims] 1. The following oxides are substantially expressed as% by weight: SiO ₂ 68 to 72%, Al ₂ O ₃ 1.6 to 3.0%, CaO 8.5 to 1
_{1.0%, MgO2.0~4.2%, Na 2} O12.0~16.0%, K 2 O0.5~
3.0%, SO ₃ 0.08 to 0.30%, Fe ₂ O ₃ 0.58 to 0.65% (0.65
%), CeO ₂ 0.1 to 0.5%, TiO ₂ 0.1 to 0.4%,
And at least it includes MnO10 ~350ppm as trace oxides, comprising the sum of these components is 98% or more, and SiO ₂
+ Al ₂ O ₃ + TiO ₂ 70-74%, CaO + MgO 12-15%, Na ₂ O +
K ₂ O 13 to 17% der is, moreover viscosity temperature of the glass is 10 ⁹
Poise at 650-685 ° C, 10 ¹² Poise at 555-585 ° C
I, and infrared ultraviolet absorbing glass temperature difference between them and wherein 96 to 103 ° C. der Rukoto. 2. The glass has a visible light transmittance of 69% or more by a light source A and a solar radiation transmittance of 35 to 47 in terms of a thickness of 5 mm.
%, Ultraviolet transmittance is 8 to 15%, main wavelength is 505 to 518 nm,
The infrared and ultraviolet absorbing glass according to claim 1, which has an average transmittance of 7 to 15% and a stimulus purity of 5 % or less in the wavelength range of 1000 to 1150 nm.