JPH0834637A - Ultraviolet ray and infrared ray absorbing green glass - Google Patents

Abstract

PURPOSE:To obtain high quality less expensive UV and IR absorbing green glass as glass which considerably diminishes defects such as irregular color due to the yellow base and distortion and suppresses the occurrence of such defects by the conventional floating method in a high yield with enhanced productivity. CONSTITUTION:This UV and IR absorbing green glass consists essentially of, by weight, 68-73% SiO2, 0.05-3.0% Al2O3, 10.0-15.0%, in total, of 7.5-11.0% CaO and 2.0-4.2% MgO, 13.0-17.0%, in total, of 12.0-16.0% Na2O and 0.5-3.0% K2O, 0.05-0.30% SO3, 0.60-0.95% Fe2O3, 0.001-0.10% CeO2, 0.01-0.15% TiO2 and 0.0001-0.0015% CoO. The total amt. of these components is >=98% and that of SiO2, Al2O3 and TiO2 is 70.0-74.0%.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet / infrared absorbing green glass which has a relatively high transparency and absorbs infrared / ultraviolet rays so as to have high comfortability and safety, and can be reduced in weight.
The present invention provides the ultraviolet-infrared-absorbing green glass which is useful not only for building window glass and various glass articles but also particularly 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 flow rate of about 30%, the conditions of redox during the melting operation are controlled to give at least 35% of iron in the ferrous state, expressed as FeO, and the glass is formed into a flat glass product in a forming operation. Molding, and wherein the flat glass is at least
Have a light transmittance of 65% and an infrared transmittance of 15% or less,
A method for producing soda-lime-silica flat glass by a continuous method is disclosed.

The publication gives a total iron content of less than 0.65% expressed as Fe ₂ O _{3 in the} glass or the sulfur content of the product glass expressed as SO ₃ of 0.02.
% Of total iron expressed as Fe ₂ O ₃ and at least 50% of which is in the ferrous state expressed as FeO. , And SO ₃ having less than 0.02% by weight of sulfur, expressed as SO ₃ , and having a light transmittance of at least 65% and a total solar infrared transmittance of 15% or less.
Silica glass article is disclosed, 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% Fe ₂ O ₃ , and CeO ₂ , TiO ₂ , V ₂ O ₅
Alternatively, it is described that those having a composition consisting essentially of 0 to 1.5% of MoO ₃ in total are preferred.

Further, for example, in Japanese Patent Laid-Open No. 3-187946, Fe ₂ O _{3 of} about 0.51 to 0.96 and about 0.15 in terms of weight% are used.
And FeO in ～0.33, infrared and ultraviolet absorbing soda-lime-silica green glass is disclosed comprising a CeO ₂ of about 0.2 to 1.4 as the main component.

Further, for example, Japanese Patent Application Laid-Open No. 4-193738, Japanese Patent Application Laid-Open No. 4-224133, Japanese Patent Application Laid-Open No. 5-78147, Japanese Patent Application No. 3-144928, Japanese Patent Application No. 17
8639 and Japanese Patent Application No. 5-24456, and others, such as JP-A-4-310539.

Further, for example, in Japanese Unexamined Patent Publication (Kokai) No. 231347/1992, SiO ₂ 68 to 75%, Na ₂ O 10 to 20%, Ca
_{O5~15%, MgO0~5%, Al 2} O 3 0~5%, and K ₂ O0~5%,
Less than 0.5% by weight CeO ₂ and more than 0.85% by weight total iron (Fe ₂
In the O _3), FeO / total iron has a colorant component consisting essentially of 0.275 wt% less than total iron, with reference thickness of 3.9 mm 31% or less of the ultraviolet transmittance (300 ~390nm) The green UV absorbing glass shown is disclosed.

Further, for example, in Japanese Patent Laid-Open No. 6-92678, it is essentially shown that the content of SiO _{2 is} 65 to 80% by weight.
0-5% Al ₂ O ₃ , 0-5% B ₂ O ₃ , 0-10% MgO,
5-15% of CaO, 10 to 18 percent of Na ₂ O, 0 ~5% of K ₂ O, 0.
5-15% of MgO + CaO, 10 to 20 percent of _{Na 2 O + K 2 O,} 0.3 ~
Cerium oxide converted to 2% CeO ₂ , 0-1% TiO ₂ ,
Iron oxide converted to 0.1 to 0.8% Fe ₂ O ₃ , 0 to 0.006%
UV-infrared absorbing glass consisting of CoO, 0-0.01% NiO, 0-0.0015% Se is disclosed.

[0009]

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 clarification stage, a stirring chamber, a stirrer, etc. are required, and the one described in JP-A-3-187946 cannot be said to be sufficiently excellent in infrared absorption. These JP-A-3-187946 to JP-A-4-3105
None of the 39 publications and the like can extremely reduce the relatively expensive CeO ₂ component.

Among them, those disclosed in JP-A-4-231347 and JP-A-6-92678 are both
Although there are as hereinbefore so as to reduce the CeO ₂ component, the former must be relatively large amount of total iron (as Fe ₂ O _3), the latter not be said to have so as to sufficiently reduce the CeO ₂ component Moreover, it is rather bronze or gray, and it is hard to say green.

[0011]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks of the prior art, and is capable of producing a sheet glass by a usual float method, and is relatively expensive CeO ₂
The composition can be reduced to near zero, and the total amount of iron can be increased to a moderate level without increasing the total amount of iron. In order to prevent and eliminate such problems, and to improve productivity and maintain stable quality, it has a desired absorption of infrared rays and ultraviolet rays, and develops a relatively transparent green color tone. In addition, the present invention provides an ultraviolet-infrared-absorbing green glass having sufficient weather resistance and moldability.

That is, the present invention is substantially the following oxide in terms of weight%, SiO ₂ 68 to 73%, Al ₂ O ₃ 0.05 to 3.0.
%, CaO 7.5 to 11.0%, MgO 2.0 to 4.2%, Na ₂ O 12.0 to
16.0%, K ₂ O 0.5 to 3.0%, SO ₃ 0.05 to 0.30%, Fe ₂ O ₃
0.60 to 0.95%, CeO ₂ 0.001 to 0.10%, TiO ₂ 0.01 to 0.15
%, CoO 0.0001 to 0.0015%, the sum of these components is 98% or more, and SiO ₂ + Al ₂ O ₃ + TiO ₂ 70.0 to 74.0%, Ca
O + Mg0 10.0~15.0%, ultraviolet and infrared radiation absorbing green glass, which is a _{Na 2 O + K 2 O 13.0~17.0} %.

Further, the glass has a thickness of 5 mm,
Visible light transmittance by A light source is 65% or more, solar radiation transmittance is
35-50%, ultraviolet transmittance 7-17%, dominant wavelength by D ₆₅ light source is 500-515 nm, stimulus purity is 3.5% or less, the above-mentioned ultraviolet-infrared absorbing green glass.

The following oxides are substantially represented by weight%: SiO ₂ 68-73%, Al ₂ O ₃ 0.05-3.0%, CaO
7.5 ~11.0%, MgO 2.0 ~4.2% , Na 2 O12.0~16.0%,
K ₂ O 0.5 to 3.0%, SO ₃ 0.05 to 0.30%, Fe ₂ O ₃ 0.60 to 0.8
5%, CeO ₂ 0.001 to 0.10%, TiO ₂ 0.01 to 0.15%, CoO 0.0
001 ~ 0.0015, the sum of these components is 98% or more,
And SiO ₂ + Al ₂ O ₃ + TiO ₂ 70.0 to 74.0%, CaO + Mg0 10.0
15.0%, ultraviolet and infrared radiation absorbing green glass, which is a _{Na 2 O + K 2 O13.0~17.0%} .

Further, the glass has a thickness of 5 mm,
Visible light transmittance by A light source is 67% or more, solar radiation transmittance is
Provided is the above-mentioned UV-infrared-absorbing green glass characterized by having a wavelength of 35-50%, a UV transmittance of 7-17%, a dominant wavelength of 500 to 515 nm by a D ₆₅ light source, and a stimulation purity of 3.5% or less. It is a thing.

Here, the reason why the SiO ₂ component is 68 to 73% 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 practical problems. 73
%, The melting becomes difficult, and the Al ₂ O ₃ component content of 0.05 to 3.0% by weight means that if it is less than 0.05%, the weather resistance is lowered and the surface is liable to be burned. A problem occurs, and when it exceeds 3%, devitrification is likely to occur, the molding temperature range is narrowed, and the manufacturing becomes difficult. The CaO content in 7.5% to 11.0% is 7.5%. If it is less than 10%, it tends to be insufficient as a fluxing agent, the melting temperature will be high, and the flow temperature will not be lowered, so that it will be difficult to manufacture, and if it exceeds 11%, devitrification tends to occur, and the molding work range will be narrow and manufacturing will be difficult. The content of MgO component was set to 2.0 to 4.2% by weight.If it is less than 2.0%, the melting temperature will rise and the operating range will be narrowed, making it difficult to manufacture.
If it exceeds 2%, the easy strengthening property will decrease, and the Na ₂ O component is set to 12.0 to 16.0% by weight, because if it is less than 12.0, the meltability will deteriorate and the easy strengthening property will decrease, making moldability difficult. Since devitrification is likely to occur, the operating range is narrowed and it becomes difficult to manufacture, and if it exceeds 16%, the weather resistance is lowered, and the surface is liable to cause burns and the like, which causes practical problems. _The O content of 0.5 to 3.0% is 0.
If it is less than 5%, the easiness of strengthening is lowered, and if it exceeds 3.0%, the weather resistance is lowered and the cost is increased.

Further, the SO ₃ component is 0.05 to 0.30% by weight.
The reason is that if it is less than 0.05%, it can only be made to the extent that defoaming or homogeneity tends to be insufficient in ordinary melting, and if it exceeds 0.30%, it particularly affects the coloring state of glass, such as yellow or amber color. The reason is that the desired green color tone cannot be obtained due to the occurrence of such a tendency that the color tone easily shifts to a sharp color tone, and it is preferably around 0.15%, which is rather low even within the range.

Furthermore, the Fe ₂ O ₃ component is contained in an amount of 0.60% by weight.
0.95% is the total amount of the FeO component amount that absorbs infrared rays and the Fe ₂ O ₃ component amount that absorbs ultraviolet rays and secures the desired color tone, in order to stably obtain the various optical characteristics described above,
It is necessary together with the amounts of other components such as CeO ₂ and TiO ₂ , and is 0.60.
If it is less than%, the action against the above is inferior, and if it exceeds 0.95%, the visible light transmittance is particularly reduced, and it becomes difficult to control the intended color tone, resulting in destabilization. To obtain a certain desired color tone, it is preferably about 0.60 to 0.90% by weight%, more preferably about 0.60 to 0.85% by weight%, and about 0.63 to 0.73% in the case of a light color tone. , 0.73 to 0.88 for normal tones
%.

The CeO ₂ and TiO ₂ components have an ultraviolet absorbing effect, the CeO ₂ component is 0.001 to 0.10%, and the TiO ₂ component is 0.01 to
0.15% means that Ti does not change the reduction rate in the glass and the ultraviolet absorption capacity is smaller than that of CeO ₂ component.
By combining the O ₂ component and the CeO ₂ component, which changes the reduction rate in the glass relatively greatly and yet gives sufficient ultraviolet absorption capacity, within the above-mentioned specific range, the desired properties can be obtained with a small content. Can be efficiently obtained and the conventional reduction rate is hardly changed, while controlling the ratio of Fe ₂ O ₃ and FeO in the total iron described above to reduce the transmittance in the visible light region as a whole. This is to prevent it from happening and to achieve desired optical characteristics such as ultraviolet absorption and infrared absorption.

Furthermore, when a relatively large amount of CeO ₂ component which has an effect of absorbing ultraviolet rays and has a strong oxidizing property is present in the glass substrate, all iron including Fe ₂ O ₃ and FeO is oxidized to Fe ⁺³ . Working too much to change, for example, it becomes easy to develop a yellowish glass base material, and the base material becomes a factor of non-uniform defects such as so-called ream and distortion, leading to deterioration of productivity and deterioration of workability. Become. In order to prevent the phenomenon, the amount of CeO ₂ component is set to 0.001 to 0.10%, and preferably 0.005 to 0.08%, which is more stable and surely the desired green color tone and the above defects, compared with the conventional one. It is possible to suppress the expression of and to maintain the above optical characteristics.

Further, the TiO ₂ component which has an effect of absorbing ultraviolet rays but also absorbs it in the visible region must lower the total iron concentration as Fe ₂ O ₃ in the glass substrate, which is generally negative. Therefore, the TiO ₂ component is in the range of 0.01 to 0.15%, preferably 0.03 to 0.
It is about 10%, and the total iron concentration, TiO ₂ component and CeO ₂
Adjust the balance with the component range, and as a supplement, Co
O 2 component is added in a small amount in the range of 0.0001 to 0.0015% so that the color tone can be adjusted relatively easily. Preferably 0.0002-
It is about 0.0010%, which makes it easier to adjust in a balanced manner.

Furthermore, the reduction ratio is Fe ²⁺ / Fe ³⁺
The displayed amount is about 30 to 40%, preferably about 32 to 38%. That is, by making the CeO ₂ component, which has a strong oxidizing property, to be reduced as much as possible, it is not necessary to increase the reduction rate of total iron, but rather, an increase in the reduction rate of total iron lowers the absorption rate of ultraviolet rays and is not preferable. Yes, the range is in consideration of the ultraviolet ray shielding rate and the solar radiation transmittance. In any case, according to the present invention, by adjusting the coloring component and its concentration and the redox conditions of the batch, it is possible to obtain an ultraviolet / infrared absorbing green glass aiming at the intended color tone and optical properties.

Further, SiO ₂ , Al ₂ O ₃ , CaO, MgO, Na ₂ O,
The sum of the components of K ₂ O, Fe ₂ O ₃ , SO ₃ , CeO ₂ , and TiO ₂ is set to 98% or more by weight, because, for example, trace components such as MnO, ZnO, and SnO ₂ are added. However, it is for controlling the amount so as not to exceed 2%. More specifically, for example, it is preferable that MnO is about 0.0005 to 0.0370% because a delicate influence can be exerted for controlling the green color tone.

Furthermore, the reason that the weight percentage of SiO ₂ + Al ₂ O ₃ + TiO ₂ is 70.0 to 74.0% is that if it is less than 70%, the weather resistance decreases, and if it exceeds 74%, the easy strengthening property decreases. The reason why CaO + MgO is set to 10.0 to 15.0% by weight is that CaO and MgO components are used to lower the melting temperature, and if less than 10%, the easy strengthening property decreases.
If it exceeds%, devitrification is likely to occur, which makes it difficult to manufacture. Therefore, the percentage of Na ₂ O + K ₂ O of 13.0 to 17% is 1%.
If it is less than 3.0%, the easy strengthening property is deteriorated, devitrification is likely to occur, the working temperature range in molding is narrowed, and the manufacturing becomes difficult. If it exceeds 17%, the weather resistance is deteriorated and practical problems occur. The cost is also high.

Furthermore, in terms of 5 mm thickness, visible light transmittance by A light source is 65% or more, solar radiation transmittance is 35 to 50%, ultraviolet light transmittance is 7 to 17%, main wavelength is 500 to 515 nm, and stimulation is The purity of 3.5% or less means that when the visible light transmittance is 65% or less, the visibility of the glass is particularly noticeable in the windshields of automobiles, especially when the nightfall, the nighttime, or the rain or the like deteriorates the distinguishability of objects. Is not preferable, and the visible light transmittance is preferably 67% or more, more preferably about 70 to 75%.

Further, when the solar radiation transmittance exceeds 50%, the effect of improving the cooling load or improving the habitability inside / inside the vehicle is not felt sufficiently and cannot be sufficiently satisfied.
If it is less than 35%, it is not preferable because it may affect the transparency and may also affect the deterioration of the above-mentioned distinctiveness or the color tone, and it is preferably about 37 to 47%.

[0027] Also, if the ultraviolet transmittance exceeds 17%,
It is liable to be deteriorated in habitability due to human influence such as decolorization / deterioration of indoor articles or skin burn, and if it is less than 7%, a harmful effect such as not being able to obtain the visible light transmittance tends to occur. It is about 15%. Dominant wavelength is 51
This is because if it exceeds 5 nm, the desired green tone does not occur due to the influence of yellow or amber, and if it is less than 500 nm, the blue color wins too much and the desired green tone does not occur.
It is about 502 to 512 nm. This is because if the stimulus purity exceeds 3.5%, the distinctiveness of the object will be deteriorated and the visibility of the occupant will be hindered due to, for example, nightfall or heavy rain, making it difficult to secure safety. The UV range is 29
The range was 0 to 390 nm, and the visible range was the same as before.

Furthermore, for example, in producing the above-mentioned ultraviolet and infrared absorbing green glass, the mother glass composition of the present invention is used as a raw material, for example, Fe ₂ O ₃ , SO ₃ , CeO ₂ , TiO ₂ or further MnO, S ^2-, etc. Including frit glass or cullet or those belonging thereto, and further Fe ₂ O ₃ and
Frit glass or cullet containing CoO, plus CoO
It is preferable to use frit glass containing, and moreover, ilmenite, etc., and quantitative adjustment of these is easy and stable, and FeO 3 can be easily incorporated into the glass, and it can Manufacturing the infrared-ultraviolet absorbing green glass of the present invention while keeping the operating conditions and the like almost unchanged so that the oxidation-reduction state of the glass is not changed as much as possible, that is, the reduction rate is about 45% in a real kiln. This is because it is useful for adding a variety of actions such as CeO ₂ to about 30 to 40%, and at least one of metal powder or oxide such as carbon, Zn, and Sn is used as a trace amount raw material. For example, sometimes Glauber's salt (Na ₂ S
O ₄ ) It is necessary to help the action and effect of the fining agent, but on the other hand, it is likely to have a bad influence on ensuring the desired color tone, and the reducing agent such as Zn or Sn also balances Fe ₂ O ₃ and FeO. This is because it may be necessary to adjust the.

The ultraviolet and infrared absorbing green glass of the present invention also contains an easily tempered glass composition and has a plate thickness of
From thin glass of about 1 mm to thick glass of about 15 mm, which is a flat plate or a bent plate that is stronger than a raw plate, semi-reinforced, strengthened, etc., single glass, laminated glass, laminated glass or multi-layer glass, etc. Is useful for building window materials, especially for vehicle window glass.

[0030]

As described above, the ultraviolet-infrared-absorbing green glass of the present invention is a combination of specific oxide components within a specific composition range to reduce CeO ₂ components, which are relatively expensive and have strong oxidizing properties, and related components. And the glass whose concentration is controlled, or in combination with the glass composition that also includes the easily strengthening property and suppresses the reduction of the reduction rate, and using the unique raw materials, the above-mentioned glass is manufactured by the ordinary float method. By doing so, for example, it is possible to suppress and eliminate the occurrence of a yellowish glass substrate, the expression of so-called ream and distortion, and in some cases it is possible to drastically reduce the decrease in yield due to the generation of fine bubbles, etc. The stability can be improved, and the yield and the productivity can be sufficiently improved.

Further, for example, since a small amount of CeO ₂ component is used, there is no limitation on the amount of use due to the difference in specific gravity of the CeO ₂ component having a large specific gravity (specific gravity: about 7.0 to 7.2), and not only when changing colors but also during normal operation. By supplementing with frit glass or cullet, it becomes possible to fully satisfy the CeO ₂ component composition,
In the raw material batch, it is possible to make the CeO ₂ component zero, or a trace amount close to zero, and further, for example, the TiO ₂ component can be moved in the direction of a relatively small amount and the optical characteristics can be improved. It also has a satisfactory effect.

Further, considering, for example, meltability, fining property, weather resistance, moldability, devitrification property, cost, etc., the manufacturing conditions of conventional float glass and the properties of the glass are hardly changed, and in addition, easy strengthening is performed. It has a high habitability for humans by absorbing infrared rays and ultraviolet rays, including a glass composition that possesses excellent properties, and it has sufficient transparency for distinguishing objects, ensuring high safety. , Green color system, which is well harmonized with cars, indoors and outdoors, and is environmentally superior. Furthermore, even with thin glass that could not be obtained by conventional heat strengthening methods, a sufficient degree of strengthening or As the strength has been increased sufficiently, we have proposed infrared and ultraviolet absorbing green glass that is useful not only for architectural window glass but also for furniture glass, cooking glass, and in particular window glass for vehicles such as automobiles. It is those that can be.

[0033]

EXAMPLES Examples of the present invention will be described below. However, the present invention is not limited to the embodiment.

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, carbon, slag, the frit glass or cullet, for example, Fe ₂ O in% by weight. ₃ About 0.0
Clear cullet (C galette) containing 9% and TiO ₂ about 0.04%, Fe ₂ O ₃ about 0.675%, TiO ₂ about 0.20% and CeO ₂ about 0.60%
Etc. Mainly using frit glass (NM frit) or cullet (NM cullet), and further using frit glass containing approximately 0.0960% CoO (Co frit) etc., weigh and mix the desired glass composition as the target composition, In particular, the reduction rate (35 ± 3%), which is somewhat lower than that of a normal kiln, is obtained.

As a raw material batch, for example, Glauber's salt /
(Quartz sand + feldspar) approx. 1% (0.5-2%), C cullet approx. 47%, NM cullet approx. 13%, Co frit approx. 0.32% (total of cullet and frit is approx. 40-65%) ) And so on.

The prepared raw material is put into a crucible and held at about 1450 ° C. in a real kiln (for example, side wall of inlet, side wall of condition section) or in an electric furnace equivalent to the real kiln for about 3 to 3
Melt for about 4 hours, vitrify, and hold at 1420 to 1430 ° C for about 1.5 to 2 hours for homogenization and clarification, then cast into a mold to form a glass block, size 100 mm x 1
Each sample was prepared by cutting out a glass plate having a thickness of 00 mm and a thickness of about 5 mm, grinding and polishing the glass plate, or casting the glass plate into a plate.

The glass component composition (% by weight) of this sample was measured by a wet analysis method based on JIS R-3101, etc., and visible light transmittance (% at A light source) as optical characteristics (at 5 mm thickness). , UV transmittance (%), solar radiation transmittance, dominant wavelength (nm at D ₆₅ light source, nm), and stimulation purity (% at D ₆₅ light source) with 340 type spectrophotometer (manufactured by Hitachi Ltd.) JIS Z-8722, JIS R-3106, ISO / DIS-
At 9050, measurements were calculated and obtained.

As a result, the glass composition was
O ₂ 71.15%, Al ₂ O ₃ 1.99%, CaO8.16%, MgO3.67%,
_{Na 2 O13.13%, K 2 O0.80} %, Fe 2 O 3 0.826%, TiO 2 0.067
%, CeO ₂ 0.076%, SO ₃ 0.12%, CoO 0.00034%,
The sum of the components is about 99.989% and SiO ₂ + Al ₂ O ₃ + TiO ₂
73.207%, CaO + MgO11.83%, an _{Na 2 O + K 2 O13.93%} , the reduction ratio (Fe ²⁺ / Fe ³⁺⁾ was approximately 0.30 to 0.35.
In addition, for example, it also contained about 0.0100 to 0.0250% of MnO component.

The optical characteristics are as follows: visible light transmittance of about 67.6%, solar radiation transmittance of about 39.7%, dominant wavelength of about 510.0 nm, ultraviolet transmittance of about 10.1%, and stimulation purity of about 3.
It was 1%, which was the desired green color tone.

It is to be noted that the bent ultraviolet and infrared ray absorbing green glass having a thickness of about 2.5 mm of the present invention is used on the outside, and the heat-reflecting film-covered bending glass plate having a thickness of about 2 mm is arranged on the inside, and the film side is placed on the inside. Prototype laminated glass laminated with PVB interlayer film and used as window glass for automobiles, the standard can be cleared, which enhances the function and effect of the present invention and further makes it more multifunctional. The sex and safety were improved.

[0041]Example 2 The same glass raw material as in Example 1, the C cullet, NM
Caret, Fe in wt% ₂O₃ About 0.38% and CoO about 0.0018%
Using frit glass (H cullet) containing
Then, the melting operation was performed, and the obtained glass was similarly sampled.

As a raw material batch, for example, Glauber's salt /
About 1.3% (silica sand + feldspar), about 35% C cullet
Degree, about 13% of NM cullet, about 12% of H cullet, etc.
did. The obtained sample was analyzed in the same manner as in Example 1 above.
As a result of the analysis, measurement and evaluation, the glass component composition is displayed in weight.
SiO₂71.23%, Al₂O₃1.99%, CaO8.17%, MgO3.68
%, Na₂O13.14%, K₂O0.80%, Fe₂O₃0.698%, TiO₂0.
066%, CeO₂0.079%, SO ₃0.12% and CoO 0.0003%
The total sum of the components is about 99.973% and SiO₂＋ Al ₂O₃+
TiO₂73.286%, CaO + MgO 11.85%, Na₂O + K₂O 13.94%
Yes, reduction rate (Fe²⁺/ Fe³⁺) Is about 0.32-0.37
It was In addition, for example, MnO content of about 0.0100-0.0250% is also included.
It was also a waste.

The optical characteristics are as follows: visible light transmittance of about 71.7%, solar radiation transmittance of about 44.8%, dominant wavelength of about 507.4 nm, ultraviolet transmittance of about 13.6%, and stimulation purity of about 2.5 mm thickness.
8%, which was the desired pale greenish color tone.

It was possible to obtain a thin glass plate which passed the above standards with high efficiency and high yield. Example 3 The same glass raw material as in Example 1 was used, weighed and blended,
A melting operation was performed, and the obtained glass was similarly sampled.

The obtained sample was the same as in Example 1 above.
As a result of analysis, measurement and evaluation,
Shows SiO₂70.8%, Al₂O₃1.6%, CaO 9.52%, MgO 2.51
%, Na ₂O13.54%, K₂O0.9%, Fe₂O₃0.833%, TiO₂0.06
7%, CeO₂0.075%, SO₃0.13%, CoO0.00038%
The total sum of the components is about 99.975%,₂＋ Al₂O₃+
TiO₂72.467%, CaO + MgO 12.03%, Na₂O + K₂O 14.44
%, And the reduction rate is about 0.30 to 0.35 as above.
It was The optical characteristics are visible light transmittance 67.9%, solar radiation transmittance
39.5%, main wavelength 509.0 nm, stimulation purity 3.1,
It was the green color tone of the period.

Regarding the easy strengthening property, JIS, for example, R3211
In the same manner as in Example 1, it was possible to obtain a thin glass plate that passed the above standards with high efficiency and high yield, as in Example 1.

Example 4 The same glass raw material as in Example 2 was used, weighed and blended,
A melting operation was performed, and the obtained glass was similarly sampled.

The obtained sample was analyzed, measured and evaluated in the same manner as in Example 1, and as a result, the glass component composition was represented by weight, SiO ₂ 69.55%, Al ₂ O ₃ 1.8%, CaO 9.85%, MgO 3.32.
_{%, Na 2 O13.47%, K} 2 O1.0%, Fe 2 O 3 0.695%, TiO 2 0.06
5%, CeO ₂ 0.077%, SO ₃ 0.15%, CoO 0.00028%, the sum of the components is about 99.977%, SiO ₂ + Al ₂ O ₃ +
TiO ₂ 71.415%, CaO + MgO 13.17%, Na ₂ O + K ₂ O 14.47
%, And the reduction rate was about 0.32 to 0.37 as in Example 2. The optical characteristics are visible light transmittance of 71.9%, solar radiation transmittance of 45.2%, dominant wavelength of 507.0nm, and stimulation purity of 2.8%.
It was the expected green color tone.

Further, as to the easy strengthening property, it is preferable to use the same method as in the third embodiment.
In the same way as in JIS, the standard defined by JIS, for example, R3211 is sufficiently satisfied, and as in Example 1, even a thin glass plate can obtain a product that passes the above standard with high efficiency and high yield. there were. Example 5 The same glass raw material as in Example 2 was used, weighed and blended,
A melting operation was performed, and the obtained glass was similarly sampled.

The obtained sample was analyzed, measured and evaluated in the same manner as in Example 1, and as a result, the glass component composition was represented by weight, SiO ₂ 70.70%, Al ₂ O ₃ 2.0%, CaO 8.4%, MgO 3.7%. %,
Na ₂ O 12.9%, K ₂ O 1.0%, Fe ₂ O ₃ 0.870%, TiO ₂ 0.020%,
CeO ₂ 0.090%, SO ₃ 0.19%, CoO 0.00006%, the total of the components is about 99.87%, and SiO ₂ + Al ₂ O ₃ + TiO ₂ 72.7
2%, CaO + MgO 12.10%, Na ₂ O + K ₂ O 13.9%,
The reduction rate was about 0.37 as in Example 2. Optical characteristics are visible light (380-780nm) transmittance 66.6%, solar radiation (340-1800nm) transmittance 38.5%, dominant wavelength 506.1-
508.7nm, stimulation purity 2.4-3.8%,
7.5-377.5 nm) The transmittance was 11.4%, which was the desired green color tone. In addition, for example, other MnO component 0.0020 ~
It also contained about 0.0250%.

[0051]Comparative Example 1 The glass obtained in the same manner as above was sampled in the same manner.
It was The obtained sample is analyzed in the same manner as in Example 1,
As a result of measurement and evaluation, the composition of the glass component is represented by weight in SiO₂
73.0%, Al₂O₃1.7%, CaO6.45%, MgO 3.0%, Na ₂O1
3.1%, K₂O1.0%, Fe₂O₃0.572%, TiO₂0.73%, CeO₂0.2
2%, SO₃0.22%, and the sum of the components is about 99.992%.
That's SiO₂＋ Al₂O₃+ TiO₂75.43%, CaO + MgO 9.45
%, Na₂O + K₂O 14.1%, oxidizing CeO₂Is adding
Therefore, a reducing agent such as carbon is added to increase the reduction rate.
The reduction rate was adjusted to around 40%. Optical characteristics are visible light
The line transmittance is 70.9%, the solar radiation transmittance is 42.8%, and the dominant wavelength is 538.
6nm, the stimulation purity is 4.2, and the desired green color tone
It wasn't always possible.

Further, the appearance of a yellowish material is slightly observed, and so-called ream or distortion may occur by chance, which is not always quite sufficient, and it may be necessary to further improve the quality and productivity. Met.

Further, as to the easy strengthening property, the above-mentioned Example 3 was used.
When carried out in the same manner as in Example 3, there was a difference from Examples 3 to 4 in particular, and it did not always satisfy the standard determined by JIS, for example, R3211. Moreover, the efficiency and the yield have not necessarily been improved by the strengthening treatment and the like.

The above-mentioned embodiments are examples of the present invention, and the present invention is not limited to these embodiments.

[0055]

EFFECTS OF THE INVENTION According to the present invention, an ultraviolet-infrared-absorbing green glass which is a combination of specific oxide components in a specific composition range is used, and the concentration of TiO ₂ and CeO ₂ can be reduced.
It is possible to add a small amount of sucrose, and it is also possible to use a combination of unique raw materials, which suppresses the reduction of the reduction rate, has a good balance of infrared absorption and ultraviolet absorption, has sufficient transparency, and has the desired green color tone. It is possible to manufacture a glass exhibiting a high quality and yield by improving the quality and yield without significantly changing the operating conditions and plate-making conditions of the actual kiln in the float method, and it is possible to manufacture it in a stable manner. It has high habitability, high safety, high environmental friendliness on both sides, and can be made lighter, which makes it useful not only for building window glass but also for automobile window glass. An inexpensive ultraviolet and infrared absorbing green glass is provided.

Claims (4)

[Claims] 1. The following oxides in terms of weight percent:
, SiO₂68-73%, Al ₂O₃ 0.05-3.0%, CaO 7.5-1
1.0%, MgO 2.0-4.2%, Na₂O12.0 to 16.0%, K₂O 0.5
 ~ 3.0%, SO₃0.05 to 0.30%, Fe₂O₃0.60 to 0.95%, C
eO₂0.001-0.10%, TiO₂0.01-0.15%, CoO 0.0001-
0.0015%, the sum of these components is 98% or more, and
SiO₂＋ Al₂O₃ + TiO₂70.0 to 74.0%, CaO + Mg0 10.0 to 1
5.0%, Na₂O + K₂O 13.0 to 17.0%
UV and infrared absorbing green glass. 2. The glass has a visible light transmittance of 65% or more and a solar radiation transmittance of 35 to 50 when converted to a thickness of 5 mm by the A light source.
%, The UV transmittance is 7 to 17%, the dominant wavelength of the D ₆₅ light source is
2. The ultraviolet and infrared absorbing green glass according to claim 1, which has a stimulating purity of 500 to 515 nm and 3.5% or less. 3. The following oxides are substantially represented by weight%.
, SiO₂68-73%, Al ₂O₃ 0.05-3.0%, CaO 7.5-1
1.0%, MgO 2.0-4.2%, Na₂O12.0 to 16.0%, K₂O 0.5
 ~ 3.0%, SO₃0.05 to 0.30%, Fe₂O₃0.60 to 0.85%, C
eO₂0.001-0.10%, TiO₂0.01-0.15%, CoO 0.0001-
0.0015%, the sum of these components is 98% or more, and
SiO₂＋ Al₂O₃ + TiO₂70.0 to 74.0%, CaO + Mg0 10.0 to 1
5.0%, Na₂O + K₂O 13.0 to 17.0%
UV and infrared absorbing green glass. 4. The glass has a visible light transmittance of 67% or more and a solar radiation transmittance of 35 to 50 when converted to a thickness of 5 mm by the A light source.
%, The UV transmittance is 7 to 17%, the dominant wavelength of the D ₆₅ light source is
4. The ultraviolet and infrared absorbing green glass according to claim 3, which has a stimulus purity of 500 to 515 nm and 3.5% or less.