JPH06234544A - Greenish color tone glass - Google Patents

Abstract

PURPOSE:To obtain a greenish color tone glass high in see-through property, having almost the same color tone as that of the conventional green colored glass, capable of obtaining a wire glass below a prescribed value in generated thermal stress and excellent in thermal crack resistance, improved in habitability and safety to make high environmental property and useful for a widow glass for building. CONSTITUTION:This greenish color tone glass is made of a soda lime-silica glass as a basic composition, basically contains, by wt.%, 0.10-0.30 Fe2O3 (total iron) and 20-50 CoO and 200-400 Cr1O3 by ppm as coloring components and has greenish color tone. The reducing ratio (Fe<2+>/Fe<3+>) is 20-50%, the basic composition contains, by wt.%, 68-74 SiO2, 0.1-3.0 Al2O3, 8-13 CaO, 1-4.5 MgO, 11.5-16 Na2O, 0.5-3.0 K2O, 0.1-0.45 SO3 and 68-74 SiO2+Al2O3, 11-15 CaO+MgO and 12-17 Na2+K2O, the generated thermal stress of the glass is <=180kg/cm<2> in 3-15mm plate thickness and <=150kg/cm<2> in 15-19mm plate thickness or <=100kg/cm<2> in the wire glass in 6.8-10mm plate thickness.

Description

Detailed Description of the Invention

[0001]

INDUSTRIAL APPLICABILITY The present invention has a relatively high transparency and exhibits a color tone almost equal to that of the existing green-colored plate glass. Provide green-colored glass that is environmentally friendly and does not make you feel, and is particularly useful as a net-colored green-colored glass, which is useful as a window glass for buildings and vehicle windows, especially as a window glass for high-rise buildings. It is a thing.

[0002]

2. Description of the Related Art In recent years, due to energy saving such as reduction of cooling load, multi-functionalization such as reflection and absorption of heat rays and absorption of ultraviolet rays has been added to the glass itself or the glass surface, especially in automobile windows such as buildings. As a result, the need for environment-friendly flat glass products that lead to higher habitability and safety in terms of human and physical properties has increased, and colored flat glass has diversified. There have been various proposals for colored glass for business use.

For example, JP-A-63-79737 describes a method for producing an ultraviolet absorbing green glass.
SiO ₂ 70-74, Al ₂ O ₃ 1.5-2.5, CaO 10-11, MgO 1-2,
Na ₂ O 12 ~ 14, K ₂ O 0.4 ~ 1, Fe ₂ O ₃ 0.25 ~ 0.7, Cr ₂ O ₃ 0.
3 to 0.85, SO ₃ 0.1 to 0.3 composition, in some cases Cr ₂ O
A method of making a glass suitable for making containers for UV-sensitive products with a green glass of the above composition in which a part of ₃ has been replaced by 0.2% by weight or less of NiO 2 is disclosed.

Further, for example, in Japanese Unexamined Patent Publication No. 3-187946, red
Outside line and ultraviolet absorbing green glass, vehicle window glass and car
A window material for a vehicle is described, and the weight percentage is about 0.51 to 0.96.
Fe₂O ₃And about 0.15 to 0.33 FeO and about 0.2 to 1.4 CeO₂
And, or about 0.48 to 0.92 Fe₂O₃And about 0.15 to 0.
33 FeO and about 0.1-1.36 CeO₂And about 0.02-0.85 Ti
O₂Infrared and ultraviolet absorbing saws containing and as main components
Da lime silica green glass, as well as FeO 3 wt%
Fe₂O₃Reduce about 23-29% of the total iron represented by
To be displayed as a color measurement light and a colorimetric light A visible light transmission
The ratio is about 70% or more, and the main wavelength of colorimetric light C is about
It is disclosed that the wavelength is 498 to 525 nm.

Further, for example, Japanese Unexamined Patent Publication No. 4-228451 discloses a green colored transparent glass which is in harmony with a wood tone, and in weight%, SiO ₂ 66 to 75, Al ₂ O 0 to 4, CaO 7 to 12, MgO 0
~5, Na ₂ O12~20, soda-lime-consisting of K ₂ O 0 to 3
Silica based glass, with wt.% Fe ₂ O ₃ less than 0.02, Se
A green tinted transparent glass consisting of 0.00003 to 0.0002 and a colorant portion consisting essentially of CoO 0 to 0.0003, which is in harmony with the wood tone and exhibits a light transmittance (illumination C) of at least 85% at a thickness of 5.66 mm. Transparent glass and the dominant wavelength of the glass
Those between 570 and 590 nm are disclosed.

Furthermore, for example, Japanese Patent Laid-Open No. 4-228450 describes a green colored transparent glass, which is Si in weight percent.
_{O 2 66~75, Al 2 O 3} 0~4, CaO 7~12, MgO 0~5, Na
_{2 O12~20,} K ₂ O _0~3, soda-lime-containing colorant consisting essentially of small amounts of iron oxide than 0.02 as Fe ₂ O ₃
A transparent glass consisting of a silica-based glass, wherein the ratio of iron present in the glass in the ferrous state expressed as FeO to the total amount of iron in the glass expressed as Fe ₂ O ₃ is at least 0.
Disclosed is a green tinted clear glass having a thickness of 5.66 mm and a light transmittance (illumination C) of at least 87%, which is made to be 4.

Furthermore, for example, JP-A-64-18938 describes a method for producing a soda / lime / silica flat glass, in which the raw material is changed from melting to shaping, and Fe ₂ O ₃ containing at least 0.45% by weight of iron. And a redox condition is controlled to give at least 35% of iron in the ferrous state as FeO, and the glass has a light transmittance of at least 65% and an infrared transmittance of 15% or less in a continuous production method. For example, in wt%, SiO ₂ 66-75, Al ₂ O ₃ 0-4, CaO 7-12,
MgO 0-5, Na ₂ O 12-20, K ₂ O 0-3, Fe ₂ O ₃ 0-1,
And CeO ₂ , TiO ₂ , V ₂ O ₃ or MoO ₂ in total consisting of 0 to 1.5, and the sulfur content as SO ₃ is less than 0.01 of the total glass composition. It is disclosed.

[0008]

DISCLOSURE OF THE INVENTION Problems to be Solved by the Invention As described above, for example, the one disclosed in JP-A-63-79737 contains a relatively large amount of Fe ₂ O ₃ and is an inexpensive starting material, especially a high iron content. ,
In addition, using a raw material containing many impurities, for example, recycled glass, a specific amount of chromium, in order to obtain a green glass capable of absorbing ultraviolet rays of 500 nm or less, which is comparable to brown glass,
It is achieved by blowing an oxidizing gas into a glass melt containing sodium nitrate, sodium sulfate, and recycled glass, and a glass plate with a greenish color tone in a normal plate glass tank kiln, such as a float tank kiln. In particular, it is difficult to use for producing a net glass with a greenish color tone.

Further, the one described in Japanese Patent Laid-Open No. 3-187946 has an improved ultraviolet absorption ability,
In particular, it has a high iron content, and it is difficult to use it for producing plate glass with a greenish green color tone.

Further, the materials described in JP-A-4-228451 and JP-A-4-228450 have a very small amount of Fe ₂ O ₃ of 0.02% by weight or less, which is used to obtain the glass. It is difficult to procure raw materials and the cost of raw materials increases.

Furthermore, the one disclosed in JP-A-64-18938 requires a considerably high reduction rate, and further, SO ₃ in the glass is not more than 0.02% by weight or as shown in FIG.
It is necessary to carry out a rather specific melt clarification as shown in.

[0012]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks of the prior art, and is Se, CeO ₂ described above.
Basically without using NiO component as a coloring agent, Fe ₂ O
₍₃₎ The total iron content is larger than that of clear plate glass, and is a relatively small specific amount that does not cause the thermal cracking phenomenon as wire-cored glass, and the reduction rate is adjusted in a normal plate glass manufacturing tank kiln to be Fe ²⁺ . While balancing Fe ³⁺ , a specific amount of Cr ₂ O ₃ component and CoO component is used as at least an essential colorant to further balance the composition, which has relatively transparent performance and exhibits the existing greenish color tone. In addition, the generated thermal stress of the glass under specific conditions can be kept within the allowable value, and it can be used as a green-colored window glass for construction, especially as a mesh-colored green-colored glass in parallel with the conventional green-colored window glass for construction. Similarly, it can be used as a window glass for automobiles in a similar manner, and can have sufficient weather resistance and moldability, which enhances habitability and safety, and is highly environmentally friendly. It is intended to provide useful greenish color glass.

That is, the present invention has a basic composition of soda-lime-silica-based glass, and is represented by weight% as a coloring component.
e ₂ O ₃ (total iron) 0.10 to 0.30, and ppm display, CoO20
-50, Cr ₂ O ₃ 200-400 is basically contained, and a greenish glass having a greenish tone.

In addition, the reduction ratio of the glass (Fe ²⁺ / Fe
³⁺ ) is set to be 20 to 50%, and the above-mentioned green-tone glass is characterized by this. In addition, the basic composition of the soda lime silica-based glass, in wt% display, SiO ₂ 68-74, Al
_{2 O 3 0.1 ~3.0, CaO 8} ~13, MgO1~4.5, Na 2 O11.5~
16, K ₂ O 0.5 to 3.0, SO ₃ 0.1 to 0.45, and SiO ₂ + Al ₂ O ₃
68 to 74, CaO + Mg0 11 to 15, Na ₂ O + K ₂ O 12 to 17 which is basically a plate glass composition, and the above-mentioned green-tone glass.

Further, the thermal stress generated in the glass is 180 kg / cm ² or less at a plate thickness of 3 to 15 mm and 150 kg / cm ² or less at a plate thickness of 15 to 19 mm, and the above-mentioned green color tone glass. . And the generated thermal stress of the glass,
The present invention provides the above-mentioned green-colored glass having a net thickness of 6.8 to 10 mm and a weight of 100 kg / cm ² or less.

Here, Fe ₂ O ₃ (total iron) of 0.10 to 0.30 and ppm of the coloring component are expressed as% by weight,
CoO 20 to 50 and Cr ₂ O ₃ 200 to 400 were basically contained in the glass because it is a glass that is stable to heat stress and does not easily induce thermal cracking. Amount relatively close to that of clear glass, that is, Fe ₂ O ₃ (total iron) 0.
In an ordinary plate glass tank kiln, for example, an area where the content of Fe ₂ O ₃ (total iron) is not too high is used in a conventional glass tank with a green color tone glass that is as close as possible to the existing green color tone glass. in Fe ²⁺ / Fe ³⁺ ratio is different from what is said to Fe ₂ O ₃ does not change by (total iron) content of Fe ₂ O ₃ (total iron) concentration decreased with the reduction rate of the drops In order to balance the Fe ²⁺ and Fe ³⁺ by adjusting the reduction rate so that the reduction rate in the glass hardly changes, the FeO component that produces a rather blue color and the rather yellowish While properly balancing the generated Fe ₂ O ₃ component, the color tone is further corrected with the Cr ₂ O ₃ component and the CoO component, and in ppm display, CoO 20-50, CrO
₂ O ₃ 200 to 400 is basically contained in a specific amount so as to complementarily interact with the specific amount of iron component, and Co ²⁺ is about 0.52 to 0.54.
Absorption of mμ gives a rather blue color, and Cr ₂ O ₃
When the ratio of the added amount of Fe ₂ O ₃ (total iron) to, for example, exceeds approximately 11.6, the Cr ₂ O ₃ content in the glass is rather excessive with the increase of Fe ₂ O ₃ (total iron). Since it will increase the amount of Fe ^2+, etc., it is used as at least an essential coloring agent so as to interact with it, and further balanced so as to stably develop and maintain a greenish color tone. It can be sufficiently used as a window glass, and it can also serve as requirements for a wire-cored glass, and can enhance comfort and safety, and can realize high environmental performance.

Fe ₂ O ₃ (total iron) is preferably 0.11
～0.18 wt% about, 230 to 380 ppm as Cr ₂ O ₃ component
The content of CoO is about 22 to 40 ppm, more preferably about 0.115 to 0.15 wt% as Fe ₂ O ₃ (total iron), about 250 to 350 ppm as Cr ₂ O ₃ component, and about 25 as CoO component. It is about 35ppm.

It is needless to say that a trace amount of impurity components may be contained as an optional component such as MnO component, ZnO component and NiO component from the raw material used or cullet, and if it is a trace amount, there is no particular problem. The preferable range of the total amount of each component is, for example, 150 ppm or less, and the smaller the better.

The reduction ratio (Fe ²⁺ / Fe ³⁺ ) of the glass is
20 to 50% means that each of the above-mentioned colorant components and the specified amount thereof should have a high degree of uniformity and should exhibit color unevenness by changing the melting conditions for converting the glass raw material into glass as little as possible. In addition, a glass with a greenish color tone and the above-mentioned generated thermal stress within the allowable range of the mesh-cored glass is obtained, and the plate making process such as the duplex (continuous simultaneous double-sided polishing) method and the float method and the tempered glass or the bent plate glass This is to stabilize the color tone and the like without any change in the heat treatment step. Preferably
It is about 23 to 43%, more preferably about 25 to 35%.

Further, the basic composition of the soda-lime-silica type glass is represented by weight% of SiO ₂ 68-74, Al ₂ O ₃ 0.1-
3.0, CaO 8 ~13, MgO1~4.5, Na 2 O11.5~16, K 2 O 0.
5 to 3.0, SO ₃ 0.1 to 0.45, and SiO ₂ + Al ₂ O ₃ 68 to 74, Ca
O + Mg0 11 to 15, Na ₂ O + K ₂ O _{12 to} 17 is basically a plate glass composition because the SiO ₂ component is represented by weight%.
The value of 68 to 74 is that when it is less than 68, the surface is liable to be burned and the weather resistance is lowered to cause a problem in practical use, and when it exceeds 74, its easy strengthening property is lowered and melting is also difficult. The content of the Al ₂ O ₃ component in the range of 0.1 to 3.0 is preferably less than 0.1 because the weather resistance is lowered and the surface is liable to cause burns or the like, which is a practical problem. Is 1.0 or more, and when it exceeds 3.0, devitrification is likely to occur, the molding temperature range is narrowed, and the production becomes difficult.The CaO component in 8 to 13% by weight means that if it is less than 8, it is easy to strengthen. And the melting temperature becomes high and the melting temperature becomes high and the flow temperature is not lowered, making it difficult to manufacture, and when it exceeds 13, devitrification is likely to occur, and the molding work range becomes narrow and manufacturing becomes difficult. , Preferably about 9 to 11.5, and the MgO component If the amount is 1 to 4.5, the melting temperature increases and the operating range is narrowed when the amount is less than 1, which makes it difficult to manufacture, and when it exceeds 4.5, the easy strengthening property decreases, and preferably about 1.5 to 4.0. .

Further, the reason why the Na ₂ O component is set to 11.5 to 16 in weight% is that if it is less than 11.5, the easy strengthening property is lowered, the moldability becomes difficult, and devitrification easily occurs, so that the operating range is narrowed and it is difficult to manufacture. When it exceeds 16, the weather resistance is lowered, and the surface is liable to be burned, causing practical problems.The K ₂ O content of 0.5 to 3.0 is 0.5 to 3.0.
If it is less than 3.0, the toughness is lowered, and if it exceeds 3.0, the weather resistance is lowered and the cost is also high.The SO ₃ component is set to 0.1 to 0.45 by weight%. Or it can only be made to such an extent that it becomes inadequate in terms of homogeneity, and is preferably more than about 0.2, and when it exceeds 0.45, it particularly affects the coloring state of glass, for example, it tends to shift to a color tone that discolors green, etc. This is because it is difficult to obtain the desired green color tone, and it is preferably around 0.35 or less.

Furthermore, SiO ₂ + Al ₂ O ₃ is contained in a weight percentage of 68-
The reason why 74% is set is that when it is less than 68%, the weather resistance is deteriorated, and when it exceeds 74%, the problem that the easy strengthening property is deteriorated occurs.
The weight percentage of O + MgO is set to 11 to 15% because CaO and MgO components are used for lowering the melting temperature, and if less than 11%, the easy strengthening property decreases, and if it exceeds 15%, devitrification tends to occur. It is difficult to manufacture, and Na ₂ O + K ₂
The weight percentage of O is set to 12 to 17%. When it is less than 12%, the easy strengthening property is lowered, devitrification is likely to occur, the working temperature range is narrowed in molding, and the production becomes difficult. The weather resistance is lowered, causing problems in practical use and also increasing the cost. Furthermore, the above-mentioned glass component composition can satisfy the basic requirements in the manufacture of various flat glass sheets having a greenish color tone.

Furthermore, the thermal stress generated in the green-colored glass is 180 kg / cm ² or less when the plate thickness is 3 to 15 mm, and the plate thickness is
It was decided that the value of 150 kg / cm ² or less at 15 to 19 mm and the value of 100 kg / cm ² or less for the net-cored glass having a plate thickness of 6.8 to 10 mm are, for example, the heat absorption plate glass having a relatively high solar absorptivity. Since it is high and its heat capacity is small, when it is installed in a window and receives solar radiation, the temperature in the central part rises quickly, the edge part in the sash does not receive solar radiation, and the temperature rises slowly due to heat radiation to the sash and the body. The central portion expands, the edge portion does not expand, tensile stress is generated in the edge portion, and when the thermal stress exceeds the strength peculiar to glass, it is broken, which is a so-called thermal cracking phenomenon. Therefore, although it is important to configure the cut surface of the sheet glass with a clean cut or a sash portion, the fact that the thermal stress generated by the glass itself is smaller than the allowable thermal stress helps prevent thermal cracking.

Generally, σ = k · f ₀ · f ₁ · f ₂ · f ₃ (θ
_R -θ _S ). σ: Thermal stress generated in sheet glass (kg / cm ² ) k: Basic stress coefficient (4.8 kg / cm ² · ° C) f ₀ : Area coefficient (stress multiplication ratio by glass area) f ₁ : Curtain coefficient (due to curtain and blind) Stress increase ratio) f ₂ : Shadow coefficient (stress increase ratio due to shadow) f ₃ : Edge temperature coefficient (f ₃ = 0.65t ₀ + 0.35t _i , t ₀ : outdoor temperature ℃, t: outdoor temperature ℃) θ _R : Center temperature of plate glass (℃) θ _S : Temperature of ash (℃) For example, the allowable thermal stress is about 180 kg / cm ² and about 15 to 19 mm for green color glass with plate thickness of 3 to 12 mm. Approximately 150 kg / cm ² , and for green-colored tinted glass it is approximately 100 kg / cm ² at a plate thickness of about 6.8 to 10 mm, and it is important to be less than each value in order to obtain safety and high quality. Necessary for netting.

The green-tone glass of the present invention has a dominant wavelength of about 500 to 516 nm and a stimulus purity of about 4 or less, preferably a dominant wavelength of 502 nm at a plate thickness of 5 mm.
It is about 514 nm, and the stimulation purity is about 2.5-3.5. Further, the visible light transmittance is about 67% or more, and preferably about 69% or more in the A light source with a plate thickness of 5 mm.

Further, the green-tone glass of the present invention includes an easily tempered glass composition, and is a thin glass plate having a plate thickness of about 2 mm to a thick glass plate having a plate thickness of about 10 mm, such as a flat plate or a bent plate. Strengthened, semi-reinforced, reinforced, etc., which can be used for single plate glass, laminated glass, laminated glass or multi-layered glass, and further meshed glass, etc., window glass for buildings, especially meshed It is a green-tone glass that is useful for glass and can also be used for automobile window glass and the like.

[0027]

As described above, the greenish tint glass of the present invention has soda lime silica glass as the basic glass composition,
It is also possible to combine the specified colorant components in a specified composition range into a colored glass having a color tone as close as possible to a conventional green-colored glass, and further to provide the basic glass composition with easily temperable properties, and further, glass. It is possible to adjust the reduction rate within a specified range, and in the above-mentioned colorant component and its quantitative range, adjustment of the reduction rate and the like also contributes to the above-mentioned expected conventional green system. It is possible to have a color tone that is closest to that of color-tone glass, and the generated thermal stress can be kept within an allowable range, and a safe, high-quality product in which thermal cracking does not easily occur,
In particular, it can be made suitable for green-tone shaded glass, and the visible light transmittance and stimulus purity are also expected, and further, for example, meltability, clarity, weather resistance, moldability, loss of appearance, etc. Considering transparency, cost, etc., the glass melting furnace does not change the manufacturing conditions and the properties of the glass, and the glass is used in a row in the same building in parallel. It is possible to use various types of flat glass products in a variety of ways, enhances the cooling and heating effect in combination with conventional products, and enhances the comfort of human beings as well as their habitability. There is little glare, the objects can be easily identified, and high safety such as eye fatigue can be secured, and it is in good harmony with indoors and outdoors, environmentally friendly and excellent. , Even thin colored glass, which could not be obtained by the conventional heat strengthening method, can obtain a sufficient degree of strengthening or a sufficient strength increase. It is possible to provide a greenish tint glass which is useful as a plate glass and can also be used for furniture glass, cooking glass, window glass for automobiles and the like.

[0028]

EXAMPLES Examples of the present invention will be described below. Example 1 As a glass raw material, for example, silica sand, soda ash, dolomite,
Setting limestone, Glauber's salt, red iron oxide, chromium oxide, cobalt oxide, etc., and in some cases, cullet and carbon, set the glass composition that will be within the basic composition and the colorant composition as the target composition. Then, the target composition amount is weighed and blended, a crucible is used in an ordinary tank kiln, for example, without using carbon as a reducing agent,
A significant amount of Glauber's salt as a fining agent, for example, a ratio of silica sand to about 0.5 to 3.
Although it is about 0, about 1.0 is used in this embodiment,
While adjusting the reduction rate and ensuring it sufficiently, it is melted at about 1400 to 1450 ° C for about 4 hours, homogenized and clarified for about 2 hours, and then cast into a plate to form a glass plate. The glass plate was 100 mm x 100 mm in size, which was sufficiently annealed and optically polished to a thickness of about 5 mm to obtain a green-tone glass for analysis of glass component composition and measurement of various optical characteristics.

Regarding the obtained green-colored glass, JI
When confirmed by a wet analysis method based on S R-3101, SiO ₂ 70.4% in weight%, Al ₂ O ₃ 1.65, CaO 11, MgO 2, Na
₂ O13.4, K ₂ O 1, SO ₃ 0.35 basic glass composition.As shown in Table 1, the colorant is Fe ₂ O ₃ (total iron) 0.124, ppm display.
CoO 26.7, Cr ₂ O ₃ 280 and the total sum of the components is about 99.951.
% And SiO ₂ + Al ₂ O ₃ 72.05%, CaO + MgO 13
%, Na ₂ O + K ₂ O 14.4%.

Further, the reduction ratio (Fe ²⁺ / Fe ³⁺ ) was calculated from the value obtained by analyzing the amount of FeO in the glass and the total iron amount (Fe ₂ O ₃ ) of the above-mentioned analyzed values, and was calculated to be about 29 It became about%.

Furthermore, regarding the visible light transmittance (% at A light source) as optical characteristics (at 5 mm thickness), dominant wavelength (nm), stimulus purity (color analysis, D ₆₅ light source), etc., type 340 Spectrophotometer (Hitachi) and JIS Z-872
2. Measured and calculated according to JIS R-3106 and ISO / DIS-9050.

As a result, as shown in Table 1, the visible light transmittance is about 72.0%, the dominant wavelength is about 507.9 nm, and the stimulus purity is about 2.8. Light green, that is, the desired greenish tint glass. However, it was very close to the color tone of the conventional green tone glass.

Furthermore, for example, when the plate thickness is about 6.8 mm, the area coefficient is 1.1 / 3 m ² , the curtain coefficient is 1.3 / the thin curtain is less than 100 mm, the shadow coefficient is 1.3 / single shed and the edge coefficient is 0.65 / standard construction, and the outside temperature is about 10. When the temperature is about 5 ° C. and the room temperature is about 20 ° C., the generated thermal stress is about 90 kg / cm ² from the above formula, and it has sufficient resistance to thermal cracking and can be used satisfactorily for meshed glass. It was a greenish glass.

Examples 2 to 10 In the same manner as in Example 1, the glass composition was calculated and weighed to obtain the desired greenish tint glass, and the mixture was clarified by melting and gradually cooled. Another glass was similarly sampled.

The obtained sample was analyzed, measured and evaluated in the same manner as in Example 1 above. As a result, the analysis values of the basic glass component composition were almost the same as in Example 1, and the respective colorant component compositions or reduction rates are shown in Table 1. And the respective optical characteristics are as shown in Table 1, and as in Example 1,
The expected green color tone and the highest one is that the generated thermal stress σ value is about 62 at a plate thickness of 6.8 mm or 10 mm.
It was a colored glass with a functionality that could be sufficiently adopted for meshed glass, such as ~ 82 kg / cm ² with significantly less possibility of thermal cracking and excellent heat cracking properties.

Examples 11 to 17 The ratio of silica sand to Example 1 was changed to about 2.0,
In the same manner as in Example 1, the glass composition was calculated and weighed and compounded so as to obtain the desired greenish color glass, melt clarification and slow cooling operations were performed, and the obtained glass was similarly sampled. .

In Example 16 only, the ratio of silica to sand is about 1.5.

The obtained sample was analyzed, measured, and evaluated in the same manner as in Example 1. As a result, the analytical values of the basic glass component composition were almost the same as in Example 1, and the respective colorant component compositions or reduction rates are shown in Table 1. And the respective optical characteristics are as shown in Table 1, and as in Example 1,
The expected green color tone and the highest one is that the generated thermal stress σ value is about 65 at a plate thickness of 6.8 mm or 10 mm.
It was a colored glass with a functionality that could be sufficiently adopted for meshed glass, such as ~ 95 kg / cm ² with very little possibility of thermal cracking and excellent heat cracking properties.

Examples 18 to 20 In the same manner as in Examples 11 to 17, carbon was used in an amount of about 0.175 g with respect to 100 g of glass at the same ratio to silica sand, and the same procedure as in Example 1 was carried out. The glass preparation composition was calculated and weighed and prepared, and in the electric furnace, the crucible was used to perform melting and clarification and slow cooling operations, and the obtained glass was similarly sampled.

The obtained sample was analyzed, measured and evaluated in the same manner as in Example 1 above. As a result, the analytical values of the basic glass component composition were almost the same as in Example 1, and the respective colorant component compositions or reduction rates are shown in Table 1. In addition, the respective optical characteristics are as shown in Table 1, and the solar radiation transmittance can be reduced to about 65, and the greenish color tone is the same as in Example 1 and the generated thermal stress is the same. σ value is plate thickness 6.8 mm or 1
It was a colored glass with functionality that can be used as a meshed glass, such as a possibility of thermal cracking of about 87 to 100 kg / cm ^{2 at 0} mm and heat resistance cracking properties.

Regarding the reduction rate (Fe ²⁺ / Fe ³⁺ ),
From the transmittance curve at a plate thickness of 5 mm, the amount of FeO was determined to be about 1.10 µ
It was calculated from the transmittance (optical density) at m, and was calculated from the total iron content (Fe ₂ O ₃ ) of the above-mentioned analysis values.

Needless to say, a glass frit or various cullets may be appropriately used.

[0043]

[Table 1]

[0044]

EFFECTS OF THE INVENTION According to the present invention, the total amount of iron is set to a specific amount within a relatively small range, the specified colorant components are skillfully combined within the specified composition range, and the reduction rate is finely adjusted to be appropriate. While maintaining and maintaining a high reduction rate, having sufficient transparency and obtaining glass that exhibits the desired greenish color tone,
The generated thermal stress characteristics can also be made to a value capable of sufficiently preventing thermal cracking and imparted in a well-balanced manner. Further, for example, it can be sufficiently stably manufactured without significantly changing the operating conditions of the actual kiln. Can enhance habitability and safety in terms of both human and physical properties, enable green shaded glass in buildings to respond to diversification, and have high environmental friendliness. In addition to being useful as a window glass for construction, it is also intended to provide a green-tone glass that can be used as a window glass for automobiles.

 ─────────────────────────────────────────────────── ─── Continuation of the front page (72) Inventor Hirofumi Kobayashi 1510 Oguchi-cho, Matsusaka-shi, Mie Central Glass Co., Ltd. Technical Center

Claims (5)

[Claims] 1. Fe ₂ O ₃ (total iron) 0.10 based on soda lime silica glass as a basic composition and represented by weight% as a coloring component.
0.30, and in ppm display, CoO20~50, Cr ₂ O ₃ 200~
A greenish glass that basically contains 400 and exhibits a greenish tone. 2. The reduction ratio (Fe ²⁺ / Fe ³⁺ ) of the glass is
The green-tone glass according to claim 1, wherein the glass is 20 to 50%. 3. A base set of the soda lime silica glass
The composition is in weight% and is SiO₂68-74, Al₂O₃ 0.1 to 3.0,
CaO 8 ~ 13, MgO 1 ~ 4.5, Na₂O11.5-16, K₂O 0.5-3.
0, SO₃0.1 to 0.45, and SiO₂＋ Al₂O₃ 68 ~ 74, CaO + Mg
0 11-15, Na ₂O + K₂O 12 to 17 which is basically flat glass
The green color tone according to claim 1, wherein the green color tone is a product.
Glass. 4. The generated thermal stress of the glass has a plate thickness of 3 to 15
180 kg / cm ² or less in mm, 150 k in plate thickness 15 to 19 mm
The green color tone glass according to any one of claims 1 to 3, wherein g / cm ² or less. 5. The generated thermal stress of the glass has a plate thickness of 6.8 to
The green-tone glass according to claim 1, wherein the glass having a mesh size of 10 mm has a weight of 100 kg / cm ² or less.