JP3086165B2 - UV-infrared absorbing green glass - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet and infrared ray which has a relatively high transparency and a high absorption of infrared rays and ultraviolet rays, has an excellent shielding property, and has high occupancy, high safety and a light weight. Regarding the absorbing greenish glass, the present invention provides an ultraviolet-ray-absorbing greenish glass which is useful not only for architectural window glass and various glass articles but also for vehicle window glass.

[0002]

2. Description of the Related Art In recent years, due to energy saving such as reduction of cooling load or deterioration or deterioration of organic matter and fading, multifunctionalization such as reflection and absorption of infrared rays and ultraviolet rays has been added to the glass itself or the glass surface, so The need for flat glass articles that lead to higher livability both physically and physically has been rapidly increasing.

[0003] In view of the above, in addition to the conventional infrared absorbing glass, a glass which is conscious of ultraviolet absorption is being proposed, and a proposal has been made which expects higher performance. For example, Japanese Patent Publication No. Hei 5-27578 discloses that a raw material is supplied to a melting operation, which includes a separate liquefaction stage and a clarification stage. A continuous stream of molten glass having at least 0.45% by weight of iron, expressed as Fe ₂ O ₃ , is fed to the redox conditions during the melting operation to reduce the Fe in the final product.
Controlling to provide at least 35% of iron in the ferrous state, represented as O 2, and comprising forming the glass into a flat glass product in a forming operation, wherein the flat glass has a light transmission of at least 65% and a A method for producing soda-lime-silica flat glass by a continuous method having an infrared transmittance of less than or equal to 10% is disclosed.

The publication states that 66-75% by weight
SiO _2, 12 to 20% of Na ₂ O, 7 ~12% of CaO, 0 to 5% of Mg
O, 0 to 4% of Al ₂ O _3, 0 ~3% of K ₂ O, 0 ~1% of Fe
₂ O _3, and CeO _2, the total of TiO _2, V ₂ O ₅ or MoO ₃ 0 to 1.5%
A glass article having a composition consisting essentially of
45 wt% of total iron, expressed them iron at least 50% is in the ferrous state, expressed as FeO, and a SO ₃ 0.
Soda / lime / silica glass articles having less than 02% by weight sulfur and exhibiting at least 65% light (400-770 nm) transmission and less than 15% total solar infrared (800-2100 nm) transmission. I have.

For example, Japanese Patent Publication No. 6-88812 discloses that
0.65 to 1.25% by weight of Fe in terms of Fe ₂ O ₃ and 0.2 to 1.4
Wt% of CeO ₂ CeO ₂ and 0.02 or 0.1 to 1.36 wt%,
0.80.85% by weight of TiO ₂ as a main component
mm thickness, the colorimetric light A visible light (wavelength 400 to
770nm) The transmittance is 70% or more and the total solar energy
(Wavelength 300 ~2130nm) transmittance is not more than 46%, as ultraviolet (wavelength 300 to 400 nm) transmittance is less 38%, infrared and ultraviolet absorption defining the weight ratio of FeO with respect to Fe ₂ O ₃ Soda-lime silica green glass is disclosed.

The publication discloses that the Fe is contained in an amount of 0.48 to 0.92% by weight.
Fe ₂ O ₃ and from 0.15 to 0.33 that the weight percent of FeO, 23 - 29% of the reduced path of iron total weight% of FeO was expressed as Fe ₂ O ₃ - be made St., Hakairoko C dominant wavelength Is 498-525nm
Having a color purity of 2 to 4%, and A) 65 to
75 wt% of SiO _2, B) 10~15 wt% of Na ₂ O, C) 0 ~4 wt% of K ₂ O, D) 1 ~5 wt% of MgO, E) 5 ~15% by weight of Ca
O, F) 0 ~3 wt% Al ₂ O _3, includes a like are described.

For example, Japanese Patent Application Laid-Open No. Hei 4-310539 discloses that
The following terms of oxide, SiO ₂ 65 to 75 wt%, Al ₂ O ₃ 0.1~5 wt%, Na ₂ O10~18 wt%, K ₂ O 0 ~5 wt%, CaO5~15
Wt%, MgO1~6 wt%, CeO ₂ 0.1 ~3 wt%, Fe ₂ O
₃ 0.5 to 1.2 wt%, SO ₃ 0.05 to 1.0 wt%, TiO ₂ 0 ~1.
0 to 40% by weight of the total iron content, consisting essentially of iron oxide (FeO ₃₎ and expressed as Fe ₂ O ₃
) Is disclosed.

The publication discloses that one or more of NiO, CoO, MnO, V ₂ O ₅ , MoO _3, etc., as a colorant, is added to a glass having the above composition range in a total amount of 0 to 1.5% by weight. May be added within the range, and the change in color tone due to ultraviolet rays (sola
0% to 3% by weight of ZnO may be added as necessary to prevent the formation of color and the formation of amber. In the embodiment, the visible transmittance (380 to 780 nm) with a thickness of 5 mm is 66.1 to 66.8.
%, The solar heat transmittance (340-1800 nm) is 37.7-38.4%, and the main wavelength is 501-503 nm (green).

[0009] Further, for example, JP-A-6-321577, in _{weight%, SiO 2 65~75%, Al} 2 O 3 0.1~5, Na 2 O10~
_{18%, K 2 O 0 ~5} %, CaO5~15%, MgO1~6%, SO 3 0.0
5 to 1.0% CeO ₂ in terms of the Ce content 0.2 to 1.5% TiO ₂ converted the Ti content 0 to 1.0%, consisting essentially of _{CoO 0.001 ~0.006%, Fe 2 O} 3 -converted Fe content 0.3 to 1.6% Having a composition,
Further, an ultraviolet absorbing colored glass in which 5 to 18% by weight of Fe in terms of Fe ₂ O ₃ is Fe ²⁺ is disclosed.

The publication states that the dominant wavelength measured by the standard light source C is 488 to 492 nm, the color purity is 3 to 4%, and the visible light transmittance measured by the standard light source A is 3 to 5 mm. The UV transmittance specified by ISO is 70% or more and the UV transmittance is 15% or less. If the content of CoO is less than 0.001%, the dominant wavelength becomes too long, resulting in a yellow color. If it exceeds 0.006%, the dominant wavelength becomes short. It is described that no blue glass can be obtained.

For example, Japanese Patent Application Laid-Open No. 4-46031 discloses that
In _{weight%, SiO 2 65~75%, Al} 2 O 3 0~5%, Na 2 O10~18
_{%, K 2 O0~5%, CaO5~15} %, MgO1~5%, 0.1~3% cerium oxide, FeO0.2~1%, an ultraviolet-infrared absorption essentially a composition of SnO ₂ 0.1 to 3% Glass is disclosed.

The publication discloses that one or more of NiO, CoO, MnO, V ₂ O ₅ , MoO _3, etc. as a colorant is added to a glass having the above composition range in a total amount of 0 to 1.5% by weight. May be added within the range, and the change in color tone due to ultraviolet rays (sola
0% to 3% ZnO may be added as necessary to prevent the formation of color and the formation of amber, and SnO ₂ is a reducing agent.
%, The color of the glass becomes amber, and the dominant wavelength in the examples is from 488 to 497 nm.

[0013]

As described above, for example, the one described in Japanese Patent Publication No. 5-27578 discloses that the SO ₃ component is reduced to 0.02.
It is difficult to obtain the expected infrared and ultraviolet absorbing glass by the melting operation means in the production of the flat glass by the ordinary float method, and various complicated means processes such as a liquefaction step, a melting step, It requires a refining stage, a stirring chamber and a stirrer, etc.
1% of Fe ₂ O ₃ and the sum of CeO ₂ , TiO ₂ , V ₂ O ₅ or MoO ₃ is 0
Although it is 1.5% is described, 1.0% by weight upon addition of only CeO _2, respectively CeO ₂ is 0.25 wt% and TiO ₂ is in the addition of CeO ₂ and TiO ₂ is 1.0 wt % Or
0.5% by weight only,
For example when the only CeO ₂ was added 1.0 wt% excess of CeO ₂
It is not necessarily reduced to the extent desired, and its total solar ultraviolet transmittance is only 29.2%. Thus, it cannot be said that it is a desired infrared and ultraviolet absorbing glass having a sufficiently high performance.

[0014] In addition, those disclosed in Japanese Patent Publication No. 6-88812, for example, those having 0.915% by weight of CeO _{2 and} 0.021% by weight of TiO ₂ have a high ultraviolet transmittance of 33.4% and a sufficiently high performance. It cannot be said that it is necessarily excellent in infrared absorption.

Further, those described in JP-A-4-310539 include, for example, NiO, CoO, MnO, V ₂ O ₅ , MoO
_Three such one or more kinds of the total amount is described that may be added in a range of 0 to 1.5 wt%, as a colorant in Examples, Ni, Co, Mn, V, oxides of Mo Although it is described that the powder was used, the specific description of how to use it is not included in the examples, and its use and the degree of its contribution are unknown. For example, in the embodiment, CeO ₂ is
Although in 0.77 to 0.96 wt% TiO ₂ has been described as a 0.01 to 0.04 wt%, the main wavelength of the green about 503 nm, the degree of UV transmittance those not unknown clear.

In the examples described in JP-A-6-321577, for example, 1.10% by weight of CeO _{2 and} 0.1% by weight of TiO _{2 in} Examples.
If the amount of CoO is 1% by weight and 0.002% by weight,
Although it is 11.2%, it is still hard to say that it is a sufficiently high-performance ultraviolet absorbing glass, and it has a dominant wavelength of 491.2 nm, is blue, and has a large solar heat transmittance of 62.7%.

Further, for example, those described in JP-A-4-46031 include, for example, cerium oxide 0.1 to 3%, FeO 0.2 to 1
%, SnO ₂ 0.1 to 3%, with a dominant wavelength of 488 to 497 nm, which is blue, and whose degree of ultraviolet transmittance is unknown and unclear.

[0018]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems, and it is possible to manufacture a sheet glass by an ordinary float method, and to increase the content of CeO ₂ component as much as possible, TiO ₂ without excessively increasing
In combination with the components, the CeO ₂ component should be reduced to an appropriate amount, and the MnO component, CoO component, Cr ₂ O ₃ component, and if necessary, the SnO ₂ component should be added in a well-balanced manner. In order to prevent and eliminate reduction in productivity and deterioration of operating conditions due to discoloration and inhomogeneity, and to improve productivity and maintain stable quality, infrared and ultraviolet light are expected to be sufficiently excellent. It is a useful ultraviolet-infrared absorbing green glass that is a high-performance glass with absorption, stabilizes and expresses a relatively transparent green color tone, and also has easy strengthening, weather resistance, and sufficient moldability. To provide.

That is, the present invention is substantially equivalent to
The following oxides, SiO_Two67-75%, Al_TwoO_Three 0.05-3.0
%, CaO 7.0-11.0%, MgO 2.0-4.2%, Na_TwoO12.0 ~
16.0%, K_TwoO 0.5-3.0%, SO_Three0.05 ~ 0.30%, Fe_TwoO_Three
0.40 ~ 0.90%, CeO_Two 1.0-2.5%, TiO_Two 0.1-1.0%,
MnO 0.0010-0.0400%, CoO 0.0001-0.0009%, Cr_TwoO _Three 
0.0001-0.0010%, SnO_Two 0-1% of these ingredients
Total is 98% or more and SiO_Two+ Al_TwoO_Three + TiO_Two70 ~
76%, CaO + Mg0 10-15%, Na_TwoO + K_TwoO 13-17%
An ultraviolet and infrared absorbing green glass characterized by the following.

Further, the SnO ₂ is 0.01% by weight%.
The infrared-ray-absorbing green glass as described above, wherein the glass content is about 0.6%. The glass has a visible light transmittance of 65% or more by the A light source, a solar transmittance of 30 to 40%, an ultraviolet transmittance of 10% or less, and a dominant wavelength of the D ₆₅ light source of 500 to 540 in terms of a thickness of 5 mm. The present invention provides the above-mentioned ultraviolet-infrared-absorbing greenish glass, which has an nm and a stimulus purity of 5% or less.

[0021]

BEST MODE FOR CARRYING OUT THE INVENTION Here, the SiO ₂ component is 67 to 67% by weight.
The reason for setting the content to 75% is that if the content is less than 67%, burns and the like are likely to occur on the surface and the weather resistance is reduced, causing a practical problem. If the content exceeds 75%, melting becomes difficult.
_The reason why the content of ₂ O ₃ component is set to 0.05 to 3.0% by weight is that if it is less than 0.05%, the weather resistance is lowered and the surface is liable to be burnt, which causes a practical problem. Since the devitrification tends to occur and the molding temperature range becomes narrow and the production becomes difficult, the CaO content of 7.0 to 11.0% by weight means that if it is less than 7.0%, it tends to be insufficient as a flux and the melting temperature becomes high. In addition, since the flow temperature is not lowered, it becomes difficult to manufacture, and if it exceeds 11%, it becomes easy to devitrify, the molding work range becomes narrow and the production becomes difficult, and the MgO component is set to 2.0 to 4.2% by weight%. If the content is less than 2.0%, the melting temperature rises and the operation range is narrowed, so that the production becomes difficult. If it exceeds 4.2%, the easy strengthening property is reduced.
_The reason why the 2O component is set to 12.0 to 16.0% by weight is that if it is less than 12.0, the meltability deteriorates and the easy strengthening property decreases, the moldability becomes difficult, and the devitrification easily occurs, so the operation range is narrowed and the When the content exceeds 16%, the weather resistance is reduced, the surface tends to be burnt, and a practical problem occurs. Therefore, the K ₂ O component is set to 0.5 to 3.0% by weight. If it is less than 0.5%, the easiness to strengthen decreases, and if it exceeds 3.0%, the weather resistance decreases and the cost increases.

Further, the SO ₃ component is added in an amount of 0.05 to 0.30% by weight.
The reason is that if it is less than 0.05%, it can only be performed to the extent that it is likely to be defoamed or insufficient in homogeneity in ordinary melting, and if it exceeds 0.30%, it particularly affects the coloring state of the glass, for example, yellow or amber color This is because it becomes easy to shift to a dull color tone and the desired green color tone cannot be obtained, and it is preferable that the low value is as low as about 0.15% even within the range.

Further, the content of Fe ₂ O ₃ component is 0.40% by weight.
To that 0.90%, the total amount of Fe ₂ O ₃ component amounts to ensure the desired color tone absorb FeO component amount and the ultraviolet absorbing infrared rays, in order to stably obtain various optical characteristics described above,
It is necessary together with other components such as CeO ₂ and TiO ₂ , and 0.40
%, The effect on the above is inferior, and if it exceeds 0.90%, particularly, the visible light transmittance is reduced, and it becomes difficult to control the intended color tone and the image becomes unstable. In order to obtain a certain desired color tone, it is preferably about 0.45 to 0.85% by weight, more preferably about 0.50 to 0.80% by weight.

The CeO ₂ and TiO ₂ components have the function of absorbing ultraviolet rays, the CeO ₂ component is set to 1.0 to 2.5%, and the TiO ₂ component is set to 0.1 to 1.
The reason why 0% is set is that TiO _2, which hardly changes the reduction ratio in glass and has an ultraviolet absorbing ability smaller than the CeO ₂ component,
By combining the component and the CeO ₂ component that gives a relatively large change in the reduction ratio in glass and provides sufficient UV absorption within the above specified range, the desired properties can be efficiently achieved with a small content. The ratio of Fe ₂ O ₃ and FeO in the above-mentioned total iron is controlled while keeping the conventional reduction rate almost unchanged, so that the overall transmittance in the visible light region is not reduced. In addition to obtaining high-performance ultraviolet absorption and infrared absorption, the desired optical characteristics such as green color tone can be achieved.

Furthermore, the CeO ₂ component, which has an effect of absorbing ultraviolet rays and has a strong oxidizing property, is present in a relatively large amount in the glass base material, and the total iron containing Fe ₂ O ₃ and FeO is oxidized to make FeO.
Too much work to change to ⁺³ , for example, it becomes easier to develop a yellow glass base, and the base becomes a cause of non-uniform defects such as so-called reams and distortions. Will be invited. In order to prevent this phenomenon, it is important to combine with TiO ₂ component, MnO component, CoO component and Cr ₂ O ₃ component, and more stably and surely suppress the expected green color tone and the occurrence of the defects. It is possible to maintain the optical characteristics as well as possible. Preferably from about 1.2 to 2.2% of CeO ₂ component.

Furthermore, it is effective in absorbing ultraviolet rays.
TiO that absorbs even in the visible range_TwoIngredients in glass base
Fe_TwoO_Three Must reduce the total iron concentration as
TiO2_Twocomponent
Is in the range of 0.1 to 1.0%, preferably 0.30 to 0.
About 8%, total iron concentration and TiO_TwoIngredients and CeO_Two
Adjust the balance with the component range, and as a supplement,
When the O component is in the range of 0.0001 to 0.0009%, the visible light transmittance is
Compensates for the color tone that changes depending on the reduction rate without affecting
Color adjustment to make color adjustment relatively easy.
To be able to Preferably about 0.0001-0.0007%
Thus, it is easier to adjust the balance in a better manner. MnO component
It is a greenish color that is about 0.0010-0.0400%
Because it can have subtle effects to control the key
It is preferred. Further Cr_TwoO _ThreeAbout 0.00 as an ingredient
It is preferable that it is about 01 to 0.0010% as well as the CoO component.
It is a thing.

In particular, the MnO component is Fe in relation to Fe and Mn.
There is a tendency that the reduction rate is low in the direction of oxidation and a small amount, and although the relationship between Ce and Mn is the direction in which Mn is oxidized and the reduction rate has little effect,
While Mn neutrally interacts with Fe and Ce and the like, it can be adjusted with a slight force without significantly affecting the color tone adjustment with the absorption wavelength of MnO near about 500 nm, also, for example by using the MnO components in a large amount Sorarize - about etc. easily become to express a phenomenon such as Deployment in consideration of the amount etc. of CeO ₂ component 400ppm
It does not exceed the degree and plays an important role.

Further, the reduction rate is (FeO / Fe
₂ O ₃ ) × 100, about 20 to 45%, preferably
It is about 25-42%. That is, by reducing the strong oxidizing CeO ₂ component as much as possible, it is not necessary to increase the reduction rate of total iron. The above range is obtained in consideration of the ultraviolet ray shielding rate and the solar radiation transmittance. In any case, the present invention can obtain an ultraviolet-ray-absorbing green glass aiming at a desired color tone and optical characteristics by adjusting the coloring components, the concentrations thereof, and the oxidation-reduction conditions of the batch.

Further, SiO ₂ , Al ₂ O ₃ , CaO, MgO, Na ₂ O,
_{K 2 O, SO 3, Fe} 2 O 3, CeO 2, TiO 2, MnO, CoO, Cr 2 O 3
The reason why the sum of the components is 98% or more by weight percentage is that, for example, trace components such as ZnO ₂ and SnO ₂
This is for controlling the amount not to exceed. More specifically, for example, about 1% or less is used as the ZnO component due to the physical properties and color stability of the glass, and as the SnO ₂ component, the generation of a yellow altered base is achieved by adjusting the reduction rate by the action of a reducing agent. In addition, Sn ²⁺ has absorption at about 250 nm and about 400 nm, and is added, for example, in an amount of about 1% or less from the viewpoint of ultraviolet absorption compensation by the action of ultraviolet absorbing ability and stabilization of the color tone of glass. Is about 0.01 to 0.6%, more preferably about 0.01 to 0.1%, which contributes to the suppression of color tone unevenness while minimizing the effect on cost, and further stabilizes the color tone.

Furthermore, the reason why the weight percentage of SiO ₂ + Al ₂ O ₃ + TiO ₂ is 70-76% is that when it is less than 70%, the weather resistance is reduced,
If it exceeds 76%, there is a problem that the reinforceability decreases, and it is preferably about 70 to 74%. The reason that CaO + MgO is set to 10 to 15% by weight is that CaO and MgO components are used to lower the melting temperature, and if it is less than 10%, easy strengthening is reduced, and if it exceeds 15%, devitrification tends to occur. It is difficult to manufacture, and is preferably about 11.5 to 15%. The reason why the percentage of Na ₂ O + K ₂ O is 13 to 17% is as follows.
If it is less than 13%, the easiness of strengthening decreases, devitrification tends to occur, and the working temperature range in molding is narrowed, making it difficult to manufacture. If it exceeds 17%, weather resistance is reduced and practical problems are caused. The cost is also high.

Further, regarding the easy strengthening property, when the viscosity temperature is 10
⁹About 650 to 685 ° C with poise, 10 ¹²About 555 with poise
About 590 ° C, and the temperature difference between them is about 95-105 ° C.
Glass component composition or the viscosity temperature
The degree clears the intended specific range; and
Temperature difference between softening point and strain point is in the range of about 200-240 ° C
Is a glass component composition as shown in FIG.

[0032] Incidentally, bending about the viscosity temperature (℃) A - by measuring the viscosity curve by beam method 10 ⁹ and 10 ¹²
The poise temperature was determined, and the strain point was measured by the Lilly method and the softening point was measured by the Littleton method.

Further, in terms of a thickness of 5 mm, the visible light transmittance by the light source A is 65% or more, the sunlight transmittance is 30 to 40%, the ultraviolet light transmittance is 10% or less, and the main wavelength by the _D65 light source is 500 to 500%.
The reason that the stimulus purity is 5% or less at 540 nm is that when the visible light transmittance is 65% or less, the transparency of the glass, particularly in the windshield of an automobile, especially in the case of sunset, night or rain, etc. It is not preferable because the decrease in the property is easy to develop, preferably the visible light transmittance is 65
% Or more, more preferably about 70% or more at a thickness of about 2 to 5 mm.

If the solar radiation transmittance exceeds 40%, the effect of increasing the cooling load or improving the livability in the vehicle or in the cabin is so small that it cannot be sufficiently satisfied.
If it is less than 30%, the transparency may have an effect on the above-described decrease in discrimination or the color tone.

For example, if the UV transmittance exceeds 10%, it is likely to lead to deteriorating or deteriorating articles in a vehicle or indoors, or to the deterioration of habitability due to human influences such as skin burns. A disadvantage such as an inability to obtain a ratio is likely to occur, and is preferably about 7 to 2%. D
_{If the} dominant wavelength of the ₆₅ light source exceeds 540 nm, yellow or amber will affect the desired green color, and if it is less than 500 nm, the blue color will overwhelm and not the desired green color, Preferably it is about 505-530 nm. If the stimulus purity exceeds 5.0%, the discriminability of the object is reduced, and the visibility of the occupant is impaired due to, for example, sunset or heavy rain, and it is difficult to ensure safety. The ultraviolet range was 290 to 390 nm, and the visible range was the same as before.

Furthermore, for example, in producing the above-mentioned ultraviolet-ray-absorbing greenish glass, the mother glass composition of the present invention may contain, for example, Fe ₂ O ₃ , SO ₃ , CeO ₂ , TiO ₂ or further MnO, S ^2- Also containing frit glass or cullet or those belonging thereto, further with Fe ₂ O ₃
Frit glass or cullet containing CoO, plus CoO
Alternatively, it is preferable to use frit glass or cullet containing Cr ₂ O ₃ , and it is easy to secure the quantitative adjustment of these reliably and stably, and it is easy to incorporate FeO into the glass at all, and The operating conditions of the actual kiln were kept almost unchanged, and the oxidation-reduction state of the glass was kept as small as possible, ie, the reduction rate [(FeO /
Fe ₂ O ₃ ) × 100] is about 25%, whereas CeO ₂
It is because it is a little useful to make it about 20-45% by taking various actions into consideration, such as carbon, Zn, Sn or other metal powder or oxide as a trace material, For example, it is sometimes necessary to help the action and effect of a clarifying agent such as sodium sulfate (Na ₂ SO ₄ ), but on the other hand, it tends to have a bad effect on securing the intended color tone, and Zn or
This is because a reducing agent such as Sn may be necessary in order to adjust and stabilize the balance between Fe ₂ O ₃ and FeO.

The ultraviolet and infrared absorbing green glass of the present invention contains an easily strengthened glass composition, and
Single-pane glass, laminated glass, laminated glass, double-glazed glass, etc. As such, it can be used for window materials for architecture, particularly for window glasses for vehicles.

Further, introduction of nitrogen gas or a mixed gas containing nitrogen gas or combustion exhaust gas into the atmosphere in the adjustment region of the glass melting furnace also contributed to the stable color tone in some cases.

As described above, the ultraviolet-ray-absorbing green glass of the present invention combines a specific oxide component in a specific composition range, and in particular, increases the CeO ₂ component to increase the TiO ₂ component, MnO component, CoO component, and Cr ₂ O component. Combine the _three components and, if necessary, SnO ₂ component as a color stabilizing agent to obtain a glass whose concentration is controlled, or combine it so that the glass composition contains easy strengthening and control the reduction rate. By using a unique raw material and producing the above-mentioned glass by a normal float method, for example, it is possible to suppress and eliminate the occurrence of a yellow-colored glass base, suppress the development of so-called reams and distortions, and furthermore, in some cases. Can drastically reduce the decrease in yield due to the generation of fine bubbles and the like, and can improve the stability of operation and quality, which sufficiently contributes to the improvement of yield and productivity.

Further, in consideration of, for example, meltability, clarity, weather resistance, moldability, devitrification, cost, etc., the manufacturing conditions of the conventional float glass and the properties of the glass are hardly changed, and the glass is easily strengthened. Including high-infrared and ultraviolet absorption, including the glass composition that possesses high performance, it is highly habitable for human beings, and it has sufficient transparency to distinguish objects. Safety can be ensured,
For example, it has a green color tone that is in harmony with cars, indoors and outdoors, and is environmentally superior.Furthermore, even with thin glass that could not be obtained by the conventional heat strengthening method, it has a sufficient degree of strengthening or sufficient strength Provides UV-infrared-absorbing green glass useful for building windows, furniture windows, cooking windows, especially vehicle windows such as automobiles, etc. You can do it.

[0041]

Embodiments of the present invention will be described below. However, the present invention is not limited to such an embodiment.

Example 1 As glass raw materials, for example, silica sand, feldspar, soda ash, dolomite, limestone, sodium sulfate, red iron oxide, titanium oxide, cerium carbonate or ilmenite, carbon, slag, frit glass and cullet, for example, Fe ₂ O _{3 by} weight% About 0.09%
Clear cullet (C cullet) containing about 0.04% of TiO ₂
Frit glass (NM frit) or cullet (NM cullet) mainly containing about 0.675% of Fe ₂ O _3, about 0.20% of TiO ₂ and about 0.60% of CeO ₂ , and frit glass (H frit) containing about 0.0960% of CoO ) Or about 0.36 Fe ₂ O _{3 by} weight
% And about 0.0017% of CoO (H cullet) or, for example, Al ₂ O ₃ , Fe ₂ O ₃ , CaCO ₃ , MgCO ₃ , Na ₂ S
O ₃ , NCO ₃ , CeO ₂ , TiO ₂ , CoO, etc. are appropriately used, and the desired glass composition is weighed and prepared as a target composition. ± 5%).

As a raw material batch, for example, sodium sulfate /
(Silica sand + feldspar) about 1% (about 0.5 to 2%), cullet about 50%, (carbon / vitrification amount) x 100 = about 0.16
And so on.

The prepared raw material is put in a crucible and kept at about 1450 ° C. in an actual kiln (for example, an inlet side wall, a condition side wall) or an electric furnace equivalent to the actual kiln.
Melt and vitrify for about 4 hours, hold at 1420-1430 ° C. for about 1.5-2 hours for homogenization and clarification, then pour into a mold to form a glass block, size 100 mm × 1
Each sample was cut out into a glass plate having a thickness of about 5 mm and a thickness of about 5 mm and ground and polished, or the glass was poured into a plate shape to obtain each sample.

For this sample, the glass component composition (% by weight) was measured by a wet analysis method based on JIS R-3101 and the like, and the visible light (wavelength 380 to 780 nm) transmittance (A) as optical characteristics (at a thickness of 5 mm) was used. % At light source, UV (wavelength 297.5-377.5nm) transmittance (at A light source,
%), Solar radiation (wavelength 340 to 1800 nm), transmittance (% at A light source), dominant wavelength (nm at D ₆₅ light source), and stimulus purity (% at D ₆₅ light source) Spectrophotometer (manufactured by Hitachi, Ltd.) and JIS Z-8722, JIS R-3106, ISO / DIS-
Measurement and calculation were performed at 9050, and a calculation was performed.

As a result, the glass component composition is expressed by weight,
SiO_Two 69.93%, Al_TwoO_Three 1.96%, CaO7.93%, MgO 3.46
%, Na_TwoO 12.79%, K_TwoO 1.07%, SO_Three 0.18%, others in Table 1
As shown in Fe_TwoO_Three0.631%, TiO_Two0.30%, CeO_Two1.70
%, MnO 280ppm, CoO 2.4ppm, Cr _TwoO_Three2.0 ppm,
The total of the components is about 99.979% and SiO_Two+ Al_TwoO_Three+ Ti
O_Two72.19%, CaO + MgO 11.39%, Na_TwoO + K_TwoO13.86%
Reduction rate [(FeO / total Fe _TwoO_Three ) × 100] is about 35.5%
Degree.

Further, as shown in Table 1, the visible light transmittance is about 67.1%, the solar transmittance is about 37.3%, the main wavelength is about 517 nm, the ultraviolet ray transmittance is about 4.8%, and the stimulus purity is about 3.
It was 3% and had a green color tone, and was the intended high-performance ultraviolet and infrared absorbing green glass intended by the present invention.

The bent ultraviolet-ray / infrared-absorbing green glass having a thickness of about 2.5 mm according to the present invention is used on the outside, and a heat-reflection film-coated bent glass sheet having a thickness of about 2 mm is arranged on the inside. A prototype laminated glass laminated with a PVB interlayer was used and used for automotive window glass.The standard could be cleared, and high performance and multi-functionality were achieved according to the present invention. Sex and safety were better.

Example 2 The same glass raw material as in Example 1 above, the C cullet, NM
Using cullet and H cullet, weighing and blending were performed, and a melting operation was performed. The obtained glass was similarly sampled.

As a raw material batch, for example, sodium sulfate /
(Quartz sand + feldspar) was about 0.8%, C cullet about 35%, NM cullet about 13%, H cullet about 12%, etc. The obtained sample was analyzed, measured and evaluated in the same manner as in Example 1 above. As a result, the glass component composition was expressed by weight as follows: SiO ₂ 69.50%, Al ₂ O ₃ 1.80%, CaO 8.52%, MgO 3.
_{48%, Na 2 O 12.63%} , K 2 O 0.91%, SO 3 0.12%, others as shown in Table _{1, Fe 2 O 3 0.597%} , TiO 2 0.5%, CeO 2 1.91
%, MnO 275 ppm, CoO 3 ppm, Cr ₂ O ₃ 2 ppm, and the total of the components is about 99.995%, and SiO ₂ + Al ₂ O ₃ + TiO ₂ 7
1.8%, CaO + MgO12%, an _{Na 2 O + K 2 O13.54%} , the reduction ratio _{[(FeO / Fe 2 O 3)} × 100 ] was approximately about 36.8.

As shown in Table 1, as shown in Table 1, the visible light transmittance is about 67.6%, the sunlight transmittance is about 35.0%, the main wavelength is about 516 nm, the ultraviolet ray transmittance is about 4.4%, and the stimulus purity is about 3.
8%, which was the desired green color tone, and was the intended high-performance ultraviolet-infrared absorbing green glass intended by the present invention.

Further, a thin glass plate having a thickness of about 2 to 3 mm can be obtained with a high efficiency and a high yield, which meets the above-mentioned standard. Example 3 The same glass raw material as in Example 2 was used and weighed and mixed.
The 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, the glass component composition
Indicate SiO_Two70.0%, Al_TwoO_Three1.6%, CaO8.96%, MgO 3.04
%, Na _TwoO12.71%, K_TwoO0.9%, SO_Three0.10%, others in Table 1
As shown, Fe_TwoO_Three0.612%, TiO_Two0.43%, CeO_Two1.60%,
MnO 280ppm, CoO 4.1ppm, Cr_TwoO_Three4 ppm, and the components
Is about 99.981%, and SiO_Two+ Al_TwoO_Three+ TiO_Two 72.
03%, CaO + MgO 12%, Na_TwoO + K_TwoO 13.61% before
The reduction rate was about 34.6%.

As shown in Table 1, the optical characteristics are such that the visible light transmittance is about 65.7%, the sunlight transmittance is about 35.8%, and the main wavelength is about
512nm, UV transmittance about 4.8%, Stimulation purity about 3.5%
And the desired green-based color tone, and the desired high-performance ultraviolet-infrared absorbing green-based glass aimed at by the present invention.

Regarding easy strengthening, JIS, for example, R 3211
Alternatively, it satisfies the standard determined by R3212 sufficiently, and also has high efficiency even with a thin glass plate, as in Example 1.
It was possible to obtain a product which passed the above standard at a high yield.

Example 4 The same glass raw material as in Example 1 was weighed and mixed.
The 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 the above-mentioned Example 1. As a result, the basic glass component composition was the same as in the above-mentioned Example 1, and only the coloring components were the same as shown in Table 1. , Fe ₂ O ₃ 0.771%, TiO ₂ 0.3%, CeO ₂ 1.55
%, MnO 285 ppm, CoO 4.0 ppm, Cr ₂ O ₃ 1 ppm, and the total of the components is about 99.970%, and SiO ₂ + Al ₂ O ₃ + TiO ₂
72.19%, CaO + MgO 11.39% , a _{Na 2 O + K 2 O 13.86} %, the reduction ratio was approximately 27.5%.

As shown in Table 1, the optical characteristics are such that the visible light transmittance is about 65.5%, the sunlight transmittance is about 34.5%, and the main wavelength is about
519nm, UV transmittance about 4.5%, Stimulation purity about 3.8%
And the desired green-based color tone, and the desired high-performance ultraviolet-infrared absorbing green-based glass aimed at by the present invention.

Example 5 The same glass raw material as in Example 2 was used and weighed and mixed.
The melting operation was performed, and the obtained glass was similarly sampled.

The obtained sample was the same as in Example 1
As a result of analysis, measurement and evaluation, the basic glass component composition is
The same as Example 2 except that only the coloring component was used.
As shown, Fe_TwoO_Three0.635%, TiO_Two0.44%, CeO_Two1.61%,
MnO 280ppm, CoO 4.0ppm, Cr _TwoO_Three5 ppm
Is about 99.674%, and SiO_Two+ Al_TwoO_Three+ TiO_Two 71.
74%, CaO + MgO 12%, Na_TwoO + K_TwoO is 13.54% before
The reduction rate was about 38.2%.

As shown in Table 1, the optical characteristics are such that the visible light transmittance is about 66.4%, the sunlight transmittance is about 33.1%, and the main wavelength is about
507nm, UV transmittance about 5.0%, Stimulation purity about 4.3%
And the desired green-based color tone, and the desired high-performance ultraviolet-infrared absorbing green-based glass aimed at by the present invention.

Example 6 The same glass raw material as in Example 3 was used and weighed.
The melting operation was performed, and the obtained glass was similarly sampled.

The obtained sample was the same as in Example 1
As a result of analysis, measurement and evaluation, the basic glass component composition was Si
O_Two69.3%, Al_TwoO_Three1.6%, CaO 8.95%, MgO 3.21%, Na_TwoO
12.87%, K_TwoO0.9%, SO_Three0.10%, colored component set
As shown in Table 1,_TwoO _Three0.737%, TiO_Two 0.2%, Ce
O_Two2.09%, MnO 280ppm, CoO 5.0ppm, Cr_TwoO_Three3 ppm
And the total of the components is about 99.986%,_Two+ Al_TwoO
_Three+ TiO_Two 71.10%, CaO + MgO 12.16%, Na_TwoO + K_TwoO 13.
The reduction rate was about 25.6%.

As shown in Table 1, the optical characteristics are such that the visible light transmittance is about 66.5%, the sunlight transmittance is about 38.7%, and the main wavelength is about
513nm, UV transmittance about 4.9%, Stimulation purity about 2.9%
And the desired green-based color tone, and the desired high-performance ultraviolet-infrared absorbing green-based glass aimed at by the present invention.

Example 7 The same glass raw material as in Example 3 was used and weighed and mixed.
The melting operation was performed, and the obtained glass was similarly sampled. (However, the amount of carbon added was about 0.15%.) The obtained sample was analyzed, measured, and evaluated in the same manner as in Example 1, and as a result, the basic glass component composition was 69.5% SiO ₂ ,
Al ₂ O ₃ 1.8%, CaO 8.5%, MgO 3.4%, Na ₂ O 12.7%, K ₂ O 0.9
%, SO ₃ 0.12%, and the coloring component composition is Fe ₂ O ₃ 0.798
%, TiO ₂ 0.4%, CeO ₂ 1.25%, SnO ₂ 0.55%, MnO 280pp
m, CoO 4.0 ppm, Cr ₂ O ₃ 3 ppm, and the total of the components is about 99.947%, SiO ₂ + Al ₂ O ₃ + TiO ₂ 71.7%, Ca
O + MgO 11.9%, Na ₂ O + K ₂ O 13.6%, and the reduction rate was about 25.4%. (However, FeO 0.203%) The optical characteristics are: visible light transmittance of about 67.2%, solar transmittance of about 37.9%, dominant wavelength of about 508nm, ultraviolet transmittance of about 6.5
%, The stimulating purity is about 4.3%, the desired green color tone is stable, the color tone is stable, high quality and efficient, and the desired ultraviolet and infrared absorbing green glass intended by the present invention can be produced. Was.

Example 8 The same glass raw material as in Example 3 was used and weighed and mixed.
The melting operation was performed, and the obtained glass was similarly sampled. (However, the amount of carbon added was about 0.18%.) The obtained sample was analyzed, measured, and evaluated in the same manner as in Example 1, and as a result, the basic glass component composition was 69.5% SiO ₂ ,
_{Al 2 O 3 1.8%, CaO8.51} %, MgO3.4%, Na 2 O12.8%, K 2 O
0.9%, SO ₃ 0.12%, and the coloring component composition is Fe ₂ O ₃ 0.
702%, TiO ₂ 0.65%, CeO ₂ 1.48%, SnO ₂ 0.10%, MnO 280
ppm, CoO 4.0ppm, Cr ₂ O ₃ 3ppm, and the sum of the components is about 99.991%, SiO ₂ + Al ₂ O ₃ + TiO ₂ 71.95%,
CaO + MgO 11.91%, a _{Na 2 O + K 2 O 13.7} %, the reduction ratio was approximately 33.3%. (However, FeO 0.233%) As for the optical characteristics, the visible light transmittance is about 68.3%, the sunlight transmittance is about 36.4%, the main wavelength is about 518nm, and the ultraviolet ray transmittance is about 4.8.
%, The stimulating purity is about 4.8%, the expected green color tone is stable, the color tone is stable, high quality and efficient, and the expected ultraviolet and infrared absorbing green color glass aimed at by the present invention can be produced. Was.

Example 9 The same glass raw material as in Example 3 was used and weighed and blended.
The melting operation was performed, and the obtained glass was similarly sampled. (However, the amount of carbon added was about 0.20%.) As a result of analyzing, measuring, and evaluating the obtained sample in the same manner as in Example 1, the basic glass component composition was 69.5% SiO ₂ ,
_{Al 2 O 3 1.8%, CaO8.53} %, MgO3.4%, Na 2 O12.85%, K 2 O
0.9%, SO ₃ 0.12%, and the coloring component composition is Fe ₂ O ₃ 0.
_{689%, TiO 2 0.598%,} CeO 2 1.55%, SnO 2 0.03%, MnO 2
80 ppm, CoO 4 ppm, Cr ₂ O ₃ 3 ppm, and the total of the components is about 99.996%, SiO ₂ + Al ₂ O ₃ + TiO ₂ 71.90%,
CaO + MgO11.93%, an _{Na 2 O + K 2 O 13.75} %, the reduction ratio was approximately 34.9%. (However, FeO 0.240
%) The optical characteristics are: visible light transmittance of about 67.8%, solar transmittance of about 36.2%, dominant wavelength of about 520nm, ultraviolet transmittance of about 4.5
%, The stimulating purity is about 5.0%, the desired green color tone is stable, the color tone is stable, high quality and efficient, and the desired ultraviolet and infrared absorbing green color glass aimed at by the present invention can be produced. Was.

Comparative Example 1 A glass obtained in the same manner as described above was sampled in the same manner. The obtained sample was analyzed in the same manner as in Example 1 above.
As a result of measurement and evaluation, the glass component composition was expressed as SiO ₂ by weight.
72.4%, Al ₂ O ₃ 1.7%, CaO 6.45%, MgO 3.0%, Na ₂ O 13.1
%, K ₂ O 1.0%, SO ₃ 0.22%, and others as shown in Table 1.
₂ O ₃ 0.865%, TiO ₂ 0.02%, CeO ₂ 1.24%, and the total sum of the components is about 99.995%, and SiO ₂ + Al ₂ O ₃ + TiO ₂ 74.12
%, CaO + MgO 9.45%, Na ₂ O + K ₂ O 14.1%, the reduction rate is about 0.5%, and the optical characteristics are as follows: visible light transmittance is about 79.4%; Is about 7
1.7%, dominant wavelength is about 571nm, UV transmittance is about 2.5%,
The stimulus purity is about 16%, which is not necessarily the expected green color tone, and the insulation performance is poor,
It was not the intended ultraviolet-infrared absorbing green glass intended by the present invention.

In addition, a slight appearance of a yellow base material is observed, so-called reams or distortions happen to occur, and it is not always very satisfactory. Met.

Further, with respect to the ease of strengthening,
As a result, the results were different from those in Examples 3 and 4, and did not always satisfy the standards determined by JIS, for example, R3211. Further, the efficiency and the yield have not always been improved by the strengthening treatment or the like.

Comparative Example 2 A glass obtained in the same manner as described above was sampled in the same manner. The obtained sample was analyzed in the same manner as in Example 1 above.
As a result of measurement and evaluation, the glass component composition was expressed as SiO ₂ by weight.
71.0%, Al ₂ O ₃ 2.0%, CaO 8.6%, MgO 3.65%, Na ₂ O 13.2
%, K ₂ O 1.0%, SO ₃ 0.12%, and others as shown in Table 1.
₂ O ₃ 0.39%, TiO ₂ 0.02%, CoO 19 ppm, and the total of the components is about 99.981%, and SiO ₂ + Al ₂ O ₃ + TiO ₂ 73.0
2%, CaO + MgO 12.25%, Na ₂ O + K ₂ O 14.2%,
The reduction rate is about 27.1%, and the optical properties are, as shown in Table 1, a visible light transmittance of about 75.1% and a solar transmittance of about 75.1%.
56.8%, dominant wavelength about 490nm, UV transmittance about 29.7%,
The stimulus purity was about 4.5%, the color was blue-based, the heat insulation performance was not sufficient, and it was not the intended ultraviolet-infrared-absorbing green glass intended by the present invention.

[0072]

[Table 1]

[0073]

According to the present invention, an ultraviolet-ray-absorbing green glass is obtained by combining a specific oxide component in a specific composition range, the concentration of CeO ₂ is increased to combine with TiO ₂ , and MnO, CoO or Cr ₂ O ₃ is added as a trace component, and SnO ₂ is added as needed, and it is possible to use a combination of unique raw materials, control the reduction rate, and absorb high-performance infrared and ultraviolet light. With a good balance with the green color tone, glass with sufficient transparency and the desired green color tone can be produced without significantly changing the operating conditions of the actual kiln in the float method and the plate making conditions. It can stabilize, improve quality and yield to improve productivity, can be manufactured by stable operation, and has high habitability, high safety, high environmental properties and light weight in both human and physical aspects. Become something, for architecture Glass, of course, are those particular providing ultraviolet and infrared radiation absorbing green glass comprising them useful for application to automotive glazing.

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-4-46031 (JP, A) JP-A-4-270138 (JP, A) JP-A-4-310539 (JP, A) JP-A-6-106 92678 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C03C 1/00-14/00

Claims (3)

(57) [Claims] (1) substantially the following oxide in terms of% by weight:
, SiO_Two67-75%, Al _TwoO_Three 0.05-3.0%, CaO 7.0 -1
1.0%, MgO 2.0-4.2%, Na_TwoO12.0-16.0%, K_TwoO 0.5
 ~ 3.0%, SO_Three0.05 ~ 0.30%, Fe_TwoO_Three0.40 ~ 0.90%, C
eO_Two 1.0-2.5%, TiO_Two 0.1-1.0%, MnO 0.0010-0.0
400%, CoO 0.0001-0.0009%, Cr_TwoO_Three 0.0001-0.0010
%, SnO_Two 0-1%, and the sum of these components is 98% or more
And SiO_Two+ Al_TwoO_Three + TiO_Two70-76%, CaO + Mg
0 10-15%, Na_TwoO + K_TwoO 13-17%
UV and infrared absorbing green glass. 2. The composition according to claim 1, wherein said SnO ₂ is 0.01 to 0.6% by weight%.
The ultraviolet-ray-absorbing green glass according to claim 1, wherein: 3. The glass has a visible light transmittance of 65% or more and a solar transmittance of 30 to 40 in terms of a thickness of 5 mm.
%, UV transmittance less than 10%, dominant wavelength by _D65 light source
3. The ultraviolet-infrared absorbing green glass according to claim 1, wherein the stimulating purity is 500 to 540 nm and the stimulating purity is 5% or less.