JPH1095632A - Dense green-type colored glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain a dense green-type colored glass capable of specifying light transmittance properties, having sufficient privacy protection properties by including basic constituents of a soda lime silica-based glass, and Fe2 O3 -Se- CoO-Cr2 O3 -based coloring constituents combined therewith. SOLUTION: This dense green type colored glass is obtained by basically including basic constituents of a soda lime silica-based glass, and 0.60-1.35wt.% Fe2 O3 .(all iron), 120-300ppm Cod, 20-50ppm Se and 340-1200ppm Cr2 O3 as coloring constituents. The dense green-type colored glass having 3.5mm thick is characterized by <=50% visual light transmittance Tv , <=45% sunlight transmittance Ts and <=15% ultraviolet transmittance Tuv measured by D65 illuminant measurement.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention provides relatively low transparency, exhibits almost the same color tone as existing green-colored glazings, and has remarkably excellent privacy performance, ultraviolet absorption performance and heat insulation performance (heat rays). Absorption performance), and especially ultraviolet B (ultraviolet light of 290 to 320 nm, hereinafter referred to as UVB).
A dark green type that can shield and prevent ultraviolet A (ultraviolet light having a wavelength of 320 to 400 nm, hereinafter referred to as UVA), improve the comfort and safety, and can also reduce the weight in various shapes. Regarding the color of dense green glass, it is not only human and materially friendly architectural, vehicular, marine or aircraft window glass and various glass articles, but also vehicular window glass, especially automotive windows The object of the present invention is to provide a dense green glass useful as glass more simply and efficiently.

[0002]

2. Description of the Related Art In recent years, energy savings such as reduction of cooling load have been abundant in recent years, and in addition to the reflection and absorption of heat rays, multi-functionalization has been realized in window glasses for automobiles as well as for buildings, in addition to the reflection and absorption of heat rays. The need for a flat glass article that leads to higher habitability and more safety both in terms of human and physical properties by being applied to the glass itself and / or the glass surface has been rapidly increasing. Among them, there is a growing demand for dark-colored green glass which has superior ultraviolet shielding performance, is gentle to humans and materials, and has privacy performance.

For example, Japanese Patent Application Laid-Open No. 5-330847 describes a colored glass composition and a window glass using this glass. The main component is wt.%, SiO ₂ : 64 to 75%, Al ₂ O. ₃ : 0
_{~5%, B 2 O 3:} 0~5%, CaO: 5 ~15%, MgO: 0 ~5%, N
a ₂ O: 10-18%, K ₂ O: 0-5%, total of alkaline earth oxides is 6-16% by weight, total of alkali metal oxides is 10-20% by weight And as a colorant, Fe ₂ O
₃ (total iron) 1.4 to 4 wt%, CoO: 0 to 0.05 comprises by weight%, greater CoO content is greater than about 0.02 wt% when Fe ₂ O ₃ content is less than about 2 wt%, and should Further contains selenium and chromium oxide, and the total of CoO + Se + Cr ₂ O ₃ is 0.24
A glass composition having a total light transmittance (TL _A ) of about 20% or less for an A light source for a thickness of 3.85 mm; Those having a total energy transmission (T _E ) of about 12% or less are described.

[0004] Among them, for example, the composition is used as a colorant.
And Fe_TwoO_Three (Total iron): 1.4-2.5% by weight, CoO: 0.015-
0.033% by weight, Se: 0.0010 to 0.0035% by weight,
Also Fe _TwoO_Three (Total iron): 1.4-2.5% by weight, CoO: 0.015-
0.030% by weight, Cr_TwoO_Three: 0.07 to 0.2% by weight, ash
Low total light transmittance and total energy transmittance in blue or green
Having a window glass, especially an automotive window glass, in particular a car
It is described that it can be used for
You.

For example, Japanese Patent Application Laid-Open No. 63-79737 discloses a method for producing an ultraviolet-absorbing green glass, in which a melt of soda-lime glass containing a chromium compound and a nitrate is gasified under oxidizing conditions. a in processing method for, Cr ₂ O ₃ in terms of at least 0.3 wt% chromium, 0.2 to 2.0 wt% of sodium nitrate, the following sodium sulfate and 1.5% by weight
A method for producing a green glass having a visible light transmitting property and a large ultraviolet absorbing ability, which is obtained by blowing an oxidizing gas into a glass melt containing 15 to 65% by weight of recycled glass, is described.

Among them, for example, SiO ₂ : 70 to 74% by weight
_{%, Al 2 O 3: 1.5} ~2.5%, Fe 2 O 3: 0.25~0.7%, chromium oxide 0.3 to 0.85% (as _{Cr 2 O 3), CaO:} 10~11%, MgO:
_{1~2%, Na 2 O: 12} ~14%, K 2 O: 0.4 ~1%, SO 3 0.1~
It is described that a glass having a composition of 0.3% is obtained. Further, in the examples, the light transmittance at a wavelength of 500 nm is about 21.3 to 33% at a thickness of 2 mm, the light transmittance at a wavelength of 450 nm is about 0.3 to 3%, It is described that the light transmittance at 400 nm is about 0% and the so-called dominant wavelength is 558 nm.

[0007]

As described above, for example, the colored glass composition described in Japanese Patent Application Laid-Open No. 5-330847 and a window glass using this glass have a coloring component of Fe ₂ O ₃ —Se—C.
Although it is an oO-Cr ₂ O ₃ system, the Fe ₂ O ₃ component composition is 1.4 to 4
wt%, the CoO component is an optional component.
₂ O ₃ component composition is 1.45wt%, Se component composition 24 ppm, although those a CoO component composition 280ppm main wavelength λ is 485nm visible light transmittance is low, the ultraviolet absorption performance tones of about grayish blue It is difficult to say that it exhibits sufficiently stable and reliable, and most of the present glass with a high content of Fe ₂ O ₃ ,
In particular, glass of about 2% by weight or more is not necessarily stable and easy to manufacture in a normal sheet glass melting furnace, for example, it is necessary to manufacture it in an electric furnace at least.

Further, for example, it is described in JP-A-63-79737.
UV-absorbing green glass has a coloring component of Fe_TwoO_Three-Cr_TwoO_Three In the system
Yes, eg substantially Fe_TwoO_Three Ingredient composition 0.25-0.7 wt%
With Cr _TwoO_ThreeWhen the component composition is 0.3-0.85wt% and Cr_TwoO_Threecomponent
Related to containers for UV-sensitive products.
Oxidizing gas must be blown into the glass melt
Etc., such that residual bubbles in the glass are problematic,
Sheet glass used in window glass for architectural and automotive applications
It is not something that can be applied to the field.

[0009]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned drawbacks, and has a coloring component of Fe ₂ O ₃ -Se.
-CoO-Cr ₂ O ₃ system, combining various component compositions as appropriate to have outstandingly superior privacy performance, ultraviolet absorption performance and heat insulation performance (heat ray absorption performance), especially ultraviolet B
Dark green glass, which shields light and more effectively blocks ultraviolet rays A, enhances livability and safety, and can also be reduced in weight in various shapes. It has low see-through performance and develops a color tone that can be said to be the green color system of existing dark green glass, and it can be used not only as architectural window glass but also as automotive window glass, and furthermore As a basic glass composition, it can be easily strengthened, has sufficient weather resistance and moldability, enhances livability and safety, and is highly environmentally friendly, for buildings that are more friendly to humans and physical properties Of course, we provide stable, more convenient and more efficient UV-infrared absorbing densgrain-colored glass, which is especially useful as vehicle window glass, ship window glass, aircraft window glass or various glass articles. Is shall.

[0010] That is, the present invention is based on a soda-lime-silica glass as a basic composition, and expressed as a coloring component by weight%.
Fe ₂ O ₃ (total iron) is 0.60 to 1.35, and ppm
oO is 120 to 300, Densuguri the Se is 20 to 50, Cr ₂ O _3, characterized in that the each containing 340-1200 Basically -
Color glass.

[0011] and, said Densuguri - thickness of emission color based glass in illuminant D ₆₅ measured at 3.5 mm, the visible light transmittance Tv
The dense green color glass described above, characterized by having a transmittance of 50% or less, a solar transmittance Ts of 45% or less, and an ultraviolet transmittance Tuv of 15% or less.

[0012] The Densuguri - thickness of emission color based glass in illuminant D ₆₅ measured at 3.5 mm, the ultraviolet transmittance Tuv ₃₇₀ UV transmittance Tuv ₃₅₀ at a wavelength 350nm is in the 8% or less and a wavelength of 370nm is 35% or less The dense green color glass described above, wherein:

[0013] Further, the coloring component is expressed by weight%,
e ₂ O ₃ (total iron) is 0.65-0.95 and ppm, CoO is
125 to 150, Se is 25 to 48, Cr ₂ O ₃ is basically each containing 345-540, thickness of the glass is in the illuminant D ₆₅ measured at 3.5 mm, the visible light transmittance of 45% or less 30 %, Sunlight transmittance is 40% or less, 20% or more, and UV transmittance is 14%
The UV transmittance Tuv _{350 at a} wavelength of 350 nm is 7% or less and the UV transmittance Tuv _{370 at a} wavelength of 370 nm is less than 7%.
The above-mentioned densified grease characterized by being 33% or less.
Color glass.

Further, the coloring component is expressed by weight%,
e ₂ O ₃ (total iron) 0.95 to 1.30 and in ppm, CoO 155
To 270, Se25～48, basically each containing Cr ₂ O ₃ 550 to 1,180, the thickness of the glass is in the illuminant D ₆₅ measured at 3.5 mm, the visible light transmittance of 30% or less than 10%, the solar radiation 25 transmittance
% Or less and 10% or less and ultraviolet transmittance at 10% or less, and UV transmittance Tuv _{350 at a} wavelength of 350 nm of 3% or less and UV transmittance Tuv _{370 at a} wavelength of 370 nm of 25% or less. -Color glass.

Further, the above-mentioned dense green color glass is characterized in that the reduction rate (Fe ²⁺ / Fe ³⁺ ) of the dense green color glass is 0.35 or more and 0.55 or less.

[0016] Furthermore, the Densuguri - above transmittance at a wavelength 1100nm of emission color glass Ts _{11 00} is the plate thickness of the glass is in the illuminant D ₆₅ measured at 3.5 mm, characterized in that 25% or less Dense green color glass.

[0017] Furthermore, the Densuguri - main wavelength of emission color based glass in plate thickness of the glass illuminant D ₆₅ measured at 3.5 mm, the above-mentioned Densuguri, characterized in that at 520nm or 580nm or less - down color System glass.

Still further, the basic composition of the soda-lime-silica glass is expressed as SiO ₂ 67-75, Al ₂ O ₃ 0.
05-3.0, CaO 7-11, MgO 2-4.5, ZnO 0-0.1,
Na ₂ O 11.5-16, K ₂ O 0.5-3.0, SO ₃ 0.05-0.4, and
SiO ₂ + Al ₂ O ₃ 68-74, CaO + Mg0 + ZnO 11-15, Na ₂ O + K
_The dense green color glass described above, which is basically a sheet glass composition of ₂ O 12 to 17.

Further, the present invention provides the above-mentioned dense green color glass characterized by using zinc selenite as a raw material for preparing the Se component.

[0020]

Here, Fe ₂ O ₃ (total iron) is 0.60 to 1.35 and ppm
In view, CoO is 120 to 300, Se is 20~50, Cr ₂ O ₃ is 340
The was the possible allowed to contain essentially each to 1200, Fe for the Fe ₂ O ₃ and the infrared absorption for the ultraviolet absorbing
Maintain the same ultraviolet and infrared absorption performance as high-performance ultraviolet and infrared absorbing green glass, which basically balances the component composition of O, without using each component composition of CeO ₂ and TiO ₂ basically. While the total iron (Fe ₂ O ₃ ) Fe ₂ O ₃ and FeO
This is because it is necessary to balance CoO, Se and Cr ₂ O ₃ in addition to the above ratio to lower the visible light transmittance and to make the color tone a relatively dark green color system.

Also, Fe_TwoO_Three(Total iron) 0.60-1.35% by weight
The reason is that the operating conditions of the actual kiln, for example, the reduction rate (0.35-0.
45) Relatively gentle molten strip without drastically changing
Need to take into account that
Adjust the darkness of the dark color
Fe that produces a blue-tinged system if it has infrared absorption performance
Heat ray absorption performance and composition
Fe that produces a yellowish color _TwoO_Three UV absorption by component composition
In both of the Noh and the glass, have a good balance at the same time
Fe required to satisfy the desired optical properties
_TwoO_Three(Total iron).

Further, in ppm, CoO is 120 to 300, and Se
Is 20-50, Cr_TwoO_Three Are properly combined as 340-1200
The range of the addition amount of Fe_TwoO_Three
When trying to express the color tone only with the component composition, green
The desired dark color tone that the transmittance in the visible range of the color system aims to decrease
However, the composition of the CoO component is not
Over the visible range necessary for dark green tones.
About 0.44μm and about 0.64μm in the visible range of the transmittance curve
Se composition and Cr so that near absorption is steep_TwoO _Three Component set
It depends on the result.

That is, the respective component compositions of Se and Cr ₂ O ₃ are auxiliary substances to the component composition system of Fe ₂ O ₃ and CoO so that a dark green color tone can be obtained. In general, it is better to increase the component composition of Cr ₂ O ₃ and relatively reduce the component composition of Se, for example, iron (yellow, yellow,
It is appropriately adjusted while expressing blue), selenium (combined with iron, brown, pink), cobalt (blue), and chromium (light green, yellow blue).

[0024] By coloring components and the composition range as described above, to adjust the transmittance of the visible range, holding the visible light transmittance to the extent of about 50% or less illuminant D ₆₅ at a thickness of about 3.5mm glass, Stable dark green color tone is exhibited and maintained, and at the same time, excellent privacy protection is exhibited, and the desired excellent heat ray absorption performance and ultraviolet absorption performance, particularly, ultraviolet B is shielded and ultraviolet A It is also possible to enhance the comfort and safety by realizing the above-mentioned optical characteristics, thereby realizing gentleness to human beings and high environment.

Preferably, Fe ₂ O ₃ (total iron) is 0.65 to 1.3.
0, and ppm, CoO is 125 to 270, Se is 25 to 4
8, Cr ₂ O ₃ is from 345 to 1,180. Incidentally, the raw materials used, or cullet, etc., MnO, as SnO _2, V ₂ O _5, each component such as optional components CeO _2, TiO _2, to impurity components of extremely small amount that it goes without saying that contain, pole If the amount is very small, it does not cause any problem. For example, the preferable range of these trace components is about 0.1% by weight or less, more preferably about 0.05% by weight or less, and most preferably about 0.03% by weight or less or several tens ppm.
It is as follows.

Further, in the plate thickness of the glass illuminant D ₆₅ measured at 3.5 mm, the visible light transmittance Tv of 50% or less, solar transmittance
The reason that the Ts is 45% or less and the UV transmittance Tuv is 15% or less, and the UV transmittance Tuv _{350 at a} wavelength of 350 nm is 8% or less and the UV transmittance Tuv _{370 at a} wavelength of 370 nm is 35% or less are as follows. Privacy-as a protective glass is less transparent, and heat ray absorption performance and ultraviolet absorption performance is much better than conventional products, for example, to enhance the cooling and heating effect and enhance the comfort in cars and indoors,
For example, it is intended to reduce human and physical adverse effects such as decolorization / deterioration or skin burn due to ultraviolet rays, and to make the products environmentally friendly to vehicles and outdoors.

Moreover, since the 350 nm wavelength transmittance Tuv ₃₅₀ is 8% or less and the 370 nm wavelength transmittance Tuv ₃₇₀ is 35% or less, the ultraviolet ray B (UV) having a wavelength of about
B) of course is set to zero, for example, to prevent so-called sunburn, which causes human skin to heat red or swollen, blister, and then darken, and reduce the UVA (UVA) having a wavelength of about 320 to 400 nm to a value smaller than the conventional value. Thus, for example, a strong ultraviolet ray having a strong penetrating power into human skin damages fibrous materials such as collagen fibers and elastic fibers in the dermis of the skin, causing wrinkles and lumps, and is present in the skin. This is to prevent the action on melanin to worsen spots and freckles.

Preferably, the visible light transmittance at a thickness of 3.5 mm
The Tv is about 45% or less, the solar transmittance Ts is about 40% or less, and the UV transmittance Tuv is about 14% or less. The UV transmittance Tuv ₃₅₀ at a wavelength of 350 nm is 7% or less and the UV transmittance Tuv _{370 at a} wavelength of 370 nm is TUV _370. 33% or less.

In particular, the coloring component is expressed by weight%, Fe ₂ O ₃ (total iron) is expressed by 0.65 to 0.95 and ppm,
CoO is 125 to 150 DEG, Se is 25~48, Cr ₂ O ₃ is each containing 345-540 Basically, D thickness of the glass at 3.5mm
_{In the} measurement of ₆₅ light sources, the visible light transmittance is 45% or less 30% or more, the solar transmittance is 40% or less 20% or more, and the ultraviolet transmittance is 14% or less.
UV transmittance of Tuv ₃₅₀ at 7% or less and wavelength of 370nm
Tuv ₃₇₀ is less than 33%.

The coloring component is expressed by weight%, and Fe ₂
O ₃ (total iron) 0.95 to 1.30 and ppm, CoO 155-2
70, Se25～48, basically each containing Cr ₂ O ₃ 550~1180, the thickness of the glass is in the illuminant D ₆₅ measured at 3.5 mm, the visible light transmittance of 30% or less than 10%, a solar radiation transmittance Rate 25
% And 10% or more, and the ultraviolet transmittance is 10% or less, and the ultraviolet transmittance Tuv _{350 at a} wavelength of 350 nm is 3% or less and the ultraviolet transmittance Tuv _{370 at a} wavelength of 370 nm is 25% or less.

The reason why the reduction rate (Fe ²⁺ / Fe ³⁺ ) of the dense green color glass is not less than 0.35 and not more than 0.55 is that, in the above-mentioned respective colorant components and the specified amounts thereof, The uniformity is high and the color unevenness is not caused by minimizing the melting conditions for converting the glass raw material into glass as much as possible, and the dark green color tone and the above-mentioned heat ray absorption performance and ultraviolet absorption performance etc. This is because each optical characteristic is obtained, and furthermore, the color tone and the like are stabilized without change in a plate making process such as a float process and a heat treatment process of tempered glass or bent plate glass. Preferably it is 0.37 or more and 0.54 or less. Adjustment of the reduction rate
The operation is performed by a furnace such as carbon, sodium sulfate and the combustion state.

In some cases, for example, an oxygen gas or a mixed gas containing oxygen gas, air or a combustion exhaust gas having an increased oxygen gas concentration, or a composite gas thereof may be introduced into the atmosphere in the adjustment region of the glass melting furnace. It contributes to color tone stability. Furthermore, it goes without saying that a current-carrying electrode, bubbling, a stirrer, and the like, which are normally provided in a glass melting furnace, can be used in combination.

The transmittance Ts _{1100 at} a wavelength of 1100 nm of the dense green color glass is determined by the thickness of the glass.
In illuminant D ₆₅ measured at 3.5 mm, it was set to 20% or less is for the purpose of enhance the heat-absorbing performance, for example, enhance the livability of the car-room to enhance the cooling and heating effect, without discomfort, people This is to make the product much more environmentally, physically and environmentally friendly.

Furthermore, the Densuguri - main wavelength of emission color based glass, in illuminant D ₆₅ measured thickness of the glass at 3.5 mm, it is 520nm or more 580nm or less, and more preferable color tone Choice Because.

Further, the basic composition of the soda-lime-silica glass is expressed in terms of% by weight as SiO ₂ 67-75, Al ₂ O ₃ 0.05-
3.0, CaO 7 ~11, MgO2~4.5, ZnO 0 ~0.1, Na 2 O1
_{1.5~16, K 2 O 0.5 ~3.0,} SO 3 0.05 ~0.4, and SiO <sub>2
+ Al 2 O 3 68 ~74,</sub> CaO + Mg011~15, Na 2 O + K 2 O 12~1
Basically, the reason that the glass composition was 7 was that the SiO ₂ component was set to 67 to 75 by weight%. The problem arises. If it exceeds 75, its reinforceability is lowered and its melting becomes difficult, and the Al ₂ O ₃ component is set to 0.05 to 3.0 by weight%. Is likely to cause burns and the like on the surface to cause a practical problem, and is preferably 1.0 or more and 3.0 or more.
If the temperature exceeds the above range, devitrification tends to occur, the molding temperature range becomes narrow, and the production becomes difficult.
The reason for setting to 11 is that if it is less than 7, the ease of strengthening decreases, the flux becomes slightly insufficient and the melting temperature becomes high, and the flow temperature is not lowered, so that it becomes difficult to manufacture, and if it exceeds 11, it becomes easy to devitrify, The range of molding work becomes narrower and the production becomes difficult.The reason why the MgO component is set to 2 to 4.5 by weight% is that if it is less than 2, the melting temperature rises and the operation range is narrowed, making it difficult to produce. Easy strengthening is reduced. The reason why the ZnO component is set to 0 to 0.1 by weight is
It is introduced from raw materials such as Se, impurities and the like to improve the physical properties of glass, and is preferably about 0 to 0.05.

The reason why the Na ₂ O component is adjusted to 11.5 to 16% by weight is that if it is less than 11.5, the easiness to strengthen decreases, the moldability becomes difficult, and the devitrification easily occurs. If it exceeds 16, the weather resistance will decrease, and burns will easily occur on the surface, causing a practical problem. Therefore, the K ₂ O component of 0.5 to 3.0 by weight% is 0.5 to 3.0.
Easy reinforcing lowers less than are those made higher weather resistance is lowered and the cost exceeds 3.0, was a 0.05 to 0.4 the SO ₃ component in weight percent, defoaming for example in a typical melt below 0.05 Alternatively, it can be performed only to the extent that it is likely to be insufficient in terms of homogeneity, preferably about 0.2 or more, and if it exceeds 0.4, it particularly affects the coloring state of glass, for example, it tends to shift to yellow or amber tint This is because it is difficult to obtain the desired dark gray-based color tone, and it is preferably about 0.35 or less.

Further, SiO ₂ + Al ₂ O ₃ was added in a weight percentage of 68-80%.
The reason for setting it to 74% is that if it is less than 68%, the weather resistance decreases, and if it exceeds 74%, the problem that the easy strengthening property decreases occurs.
The reason that O + MgO is 11 to 15% by weight is that CaO and MgO components are used to lower the melting temperature, and if it is less than 11%, the easy strengthening property is reduced, and if it exceeds 15%, it tends to be devitrified. Na ₂ O + K ₂
The reason why O is set to 12 to 17% by weight is that if it is less than 12%, the easy strengthening property is reduced, devitrification is also likely to occur, the working temperature range becomes narrow in molding, production becomes difficult, and if it exceeds 17%, This reduces the weather resistance, causes a practical problem, and increases the cost.

The reason why zinc selenite was used as a raw material for preparing the Se component is that selenium metal is not economical because the residual ratio in glass is too low. This is because the residual ratio of (ZnSeO ₃ ) is expected to be about twice or more than the residual ratio of the selenium-based frit, and it is preferable to use zinc selenite as a raw material.

It is preferable in terms of production and quality that the physical properties such as the density of the glass be as close as possible to the physical properties such as the density of the glass component composition manufactured by the conventional float method as much as possible. is there.

Further, the dense green color glass of the present invention is an easily strengthened glass composition, and has a thickness of 1 mm.
Thick glass of about 10 mm from the front and rear thin glass, for example, a strength increased from a raw plate as a flat plate or a bent plate,
Semi-strengthened, reinforced, etc. can be used for single-pane glass, laminated glass, laminated glass or double-glazed glass, glass with various functional films, etc., for building window glass, especially for vehicles In particular, it can be used for window glass for automobiles and is useful.

As described above, the dense green color glass of the present invention is a dark green color tone obtained by combining a specified colorant component in a specified composition range with soda lime silica glass as a basic glass composition. Glass, the base glass composition can be easily strengthened, and the reduction ratio of the glass can be adjusted, and within the above-described colorant components and the quantitative range thereof, the aforementioned optical properties, i.e., the visible light transmittance plate thickness 3.5 mm, 50% by illuminant D _65, the solar radiation transmittance Ts of 45% or less and UV transmittance Tuv 15% or less, preferably 350nm wavelength transmittance Tuv ₃₅₀ 8% 370 nm wavelength transmittance Tuv ₃₇₀ is about 35% or less, which is extremely excellent. In addition, for example, considering the melting property, clarity, weather resistance, moldability, devitrification, cost, etc., oxidation Other than state With the conventional glass melting furnace, the manufacturing conditions and the properties of the glass are hardly changed. Excellent privacy with sufficient transparency and little glare
It is possible to secure high safety, such as protection of nature, shielding of ultraviolet rays B, and shielding of ultraviolet rays A, and it is excellent in harmony with cars, indoors and outdoors with a dark green color tone and is environmentally friendly. In addition, even with thin colored glass, etc., which could not be obtained by the conventional heat strengthening method, it is easy to obtain a sufficient degree of strengthening or sufficient strength. The present invention can provide a glass of a dense green color useful for glass, particularly for window glass for vehicles, such as window glasses for various automobiles, ships, or aircraft.

[0042]

Embodiments of the present invention will be described below. Example 1 As a glass material, for example, silica sand, feldspar, soda ash, dolomite, limestone, sodium sulfate, bengara, or ilmenite, and zinc selenite (SeZnO ₃ ), cobalt oxide, etc. together so that the colorant composition in the component range, for example, the viscosity temperature 650 ~685 ℃ about 10 ⁹ poise, 555 to 590 ° C. of about 10 ¹² poise, and the temperature difference between the two is 95 to 105 ° C.
Is set as a target composition, the target composition is weighed and mixed, and a small amount of carbon is used as a reducing agent in a small electric melting furnace (for example, 100 g of glass).
About 0.05%), and a considerable amount of Glauber's salt as a fining agent (as an example, about 0.5% of silica sand ratio). After melting for about 3 to 4 hours, homogenizing and refining, etc., it is poured out and made into a sheet glass, cooled sufficiently, optically polished to a thickness of about 3.5 mm, and 100 m in size.
An m × 100 mm glass plate was obtained to obtain a dark green glass for glass component composition analysis and measurement of various optical properties.
Needless to say, the composition may be appropriately used in consideration of the composition, optical properties, quality, and the like of various cullets. Hereinafter, the same applies to each embodiment.

When the obtained dark green glass was confirmed by a wet analysis method based on JIS R-3101 and the like, 69.9% of SiO ₂ , Al ₂ O ₃ 1.92, CaO 9.02,
The basic glass composition of MgO 3.45, Na ₂ O 13.25, K ₂ O 0.9, and SO ₃ 0.2. As shown in Table 1, the colorant is Fe ₂ O _{3 in} weight%.
(All iron) 1.18, Se17, CoO177, Cr ₂ O ₃ 1100 in ppm
And the sum of the components is about 99.949%, and SiO ₂ +
Al ₂ O ₃ 71.82%, CaO + MgO 12.47%, Na ₂ O + K ₂ O 14.15
%Met. The residual ratio of Se in the glass by using zinc selenite (SeZnO ₃ ) was about 41.5%.
Note that ZnO was a trace amount of about 0.003% by weight and was not included in the total of the above components, and the composition of trace components in the ppm order due to impurities and the like was not analyzed. Hereinafter, the same applies to each embodiment.

[0044] Further, for the reduction ratio (Fe ²⁺ / Fe ^3+), the spectral transmittance curve by illuminant D ₆₅ at the plate thickness 3.5 mm as shown in FIG. 1 (measurement by measuring instrument to be described later), red FeO amount Determined from the transmittance Ts ₁₁₀₀ at an external wavelength of about 1.1 μm (1100 nm), the value is 0.324% by weight, and calculated from the above analysis value of the total iron content (Fe ₂ O ₃ ) of 1.18% by weight. Is
It was 0.44.

[0045] Furthermore, in the optical characteristics (D ₆₅ light source, 3.
Visible light transmittance Tv (at 5 mm thickness) [%, wavelength 0.38 to 0.78 μm (380 to 780 nm)], UV transmittance
Tuv [%, wavelength 0.30-0.38μm (300-380nm), ISO
(According to the International Organization for Standardization)] and a wavelength of 0.35 μm (3
50%) transmittance Tuv ₃₅₀ (%) and wavelength 0.37
μm (370 nm) transmittance Tuv ₃₇₀ (%) and solar transmittance Ts [%, wavelength 0.34 to 1.8 μm (340 to 1800 n
m)] and transmittance T at a wavelength of 1.1 μm (1100 nm)
For s ₁₁₀₀ (%), dominant wavelength λd (nm), stimulus purity Pe (%), etc., use the 340 type recording spectrophotometer (manufactured by Hitachi, Ltd.) and JI
S Z-8722, JIS R-3106, ISO / DIS-9050 measured and calculated.

As a result, as shown in FIG. 1 and Table 2,
Visible light transmittance Tv is about 22.5%, solar transmittance Ts is 21.8%
, Wavelength 1100nm transmittance Ts ₁₁₀₀ is about 7.8%, UV transmittance Tuv is about 6.0%, wavelength 350nm transmittance Tuv ₃₅₀ is 1.3
%, Wavelength 370nm, transmittance Tuv ₃₇₀ is about 17.3%, main wavelength λd is about 544.4nm, stimulus purity Pe is about 11.2%,
It is a desired green-glass with the aim of showing extremely excellent privacy performance and ultraviolet and infrared absorption performance.

Further, with regard to the ease of strengthening, after confirming that the above-mentioned glass clears the above-mentioned specific range of the above-mentioned viscosity temperature, the above-mentioned glass was placed in a furnace at an ambient temperature of about 650 to 730 ° C. After heating for about 5 minutes in the oven, normal air-cooling was performed to obtain a tempered glass sheet.
When examined according to R-3211, with high efficiency and high yield,
It was a dense green color glass having easy strengthening that sufficiently satisfied the prescribed specifications.

Examples 2 to 4 In the same manner as in Example 1 described above, the glass composition was calculated so as to obtain the desired densgrain-colored glass, weighed and mixed, and the melting operation was performed. Was similarly sampled.

As a result of analyzing, measuring, and evaluating the obtained samples of each of the examples in the same manner as in the above-mentioned Example 1, the analysis values of the basic glass component composition were almost the same as in Example 1, and each of the colorant component compositions and The reduction ratio and the residual ratio of Se were as shown in Table 1.

As shown in FIG. 2 and Table 2, the optical characteristics of each of Examples 2, 3, and 4 were such that the visible light transmittance Tv was
20.0%, 19.6%, 20.9%, solar transmittance Ts is 16.6%,
15.8%, about 17.1%, the wavelength 1100nm transmittance Ts ₁₁₀₀ 8.3
%, 8.3%, 8.5%, UV transmittance Tuv is 4.4%,
4.6%, 4.5%, wavelength 350nm, transmittance Tuv ₃₅₀ 0.7
%, 0.8%, 0.7%, wavelength 370nm, transmittance Tuv ₃₇₀ is 1
3.0%, 13.4%, 13.2%, dominant wavelength λd is 563.8nm, 5
58.0nm, 562.4nm, Stimulation purity Pe 13.9%, 16.6%
%, About 12.0%.

As in the case of Example 1, the desired dense green color tone, which is a desired dark green color tone, exhibits extremely excellent privacy performance and ultraviolet / infrared ray absorption performance. It was a system glass.

Further, with regard to the ease of reinforcement, the first embodiment
As a result, the same results as in Example 1 were obtained. Example 5 In the same manner as in Example 1 above, the glass composition was calculated so as to obtain the desired dense green color glass, weighed and blended, and a melting operation was performed. The obtained glass was similarly sampled. did.

As a result of analyzing, measuring, and evaluating the obtained sample in the same manner as in Example 1, the analysis value of the basic glass component composition was almost the same as that in Example 1, and each colorant component composition or reduction ratio, Se Was as shown in Table 1.

As shown in FIG. 3 and Table 2, the optical characteristics are such that the visible light transmittance Tv is about 32.8%,
Ts is about 29.2%, wavelength 1100nm transmittance Ts ₁₁₀₀ is about 19.5%, ultraviolet ray transmittance Tuv is about 11.2%, wavelength 350nm transmittance
Tuv ₃₅₀ is about 5.3%, wavelength 370nm Transmittance Tuv ₃₇₀ is 28.6%
Degree, dominant wavelength λd is about 557.0nm, stimulus purity Pe is 6.1%
As in the case of the first embodiment, the desired aim is achieved, as in the case of Example 1, which has a desired slightly pale dark green color tone and has sufficiently excellent privacy performance and ultraviolet and infrared absorption performance. It was a den-green glass.

Further, with regard to the ease of strengthening, the above-mentioned Example 1 was used.
It was the same as.

[0056]

[Table 1]

[0057]

[Table 2]

[0058]

According to the present invention, there is provided a glass composition in which a specified colorant component is skillfully combined within a specified composition range, and comprises a visible light transmittance, a solar transmittance, an ultraviolet transmittance,
In particular, by using a dense green color glass having a wavelength of 350 nm and a wavelength of 370 nm, the glass having sufficient privacy and a desired dark green color tone can be obtained. While showing remarkably excellent ultraviolet absorption performance, it shields ultraviolet B and ultraviolet A more, imparts excellent visible light transmittance and solar transmittance in a well-balanced manner, keeps easy strengthening, and The glass can be manufactured in a sufficiently stable manner without drastically changing the operating conditions of the actual kiln, and the glass is more livable and safer in terms of both human and physical properties, and has high environmental properties and light weight. The present invention provides a dense green color glass which is useful when applied to window glass for automobiles as well as architectural window glass.

[Brief description of the drawings]

It is a spectral transmittance curve by illuminant D ₆₅ at a thickness 3.5 mm of the emission color glass - Figure 1 Densuguri in the first embodiment of the present invention.

[Figure 2] Densuguri in Examples 2, 3 and 4 of the present invention - is a spectral transmittance curve by illuminant D ₆₅ at a thickness 3.5mm of emission color based glass.

Is a spectral transmittance curve by illuminant D ₆₅ at a thickness 3.5 mm of the emission color glass - [3] Densuguri in Example 5 of the present invention.

Claims (10)

[Claims] 1. A soda-lime-silica-based glass having a basic composition and a coloring component of Fe ₂ O ₃ (total iron) of 0.1% by weight.
60 to 1.35 and ppm, CoO is 120 to 300, Se
Characterized in that the glass contains 20 to 50 Cr ₂ O _{3 and} 340 to 1200 Cr ₂ O ₃ , respectively. 2. A plate thickness of said dense green color glass.
In illuminant D ₆₅ measured at 3.5 mm, the visible light transmittance Tv is 50%
Below, the solar transmittance Ts is 45% or less and the ultraviolet transmittance Tu
2. Densed green color glass according to claim 1, wherein v is 15% or less. 3. The thickness of the dense green glass is
In illuminant D ₆₅ measured at 3.5 mm, according to claim 1 or 2, wherein the ultraviolet transmittance Tuv ₃₅₀ at a wavelength of 350nm ultraviolet transmittance Tuv ₃₇₀ at 8% or less and the wavelength 370nm is 35% or less Densuguri - Color glass. In wherein said coloring component weight percentages, Fe ₂ O
₃ (total iron) is 0.65-0.95 and ppm, and CoO is 12
5 to 150, Se is 25 to 48, Cr ₂ O ₃ is basically each containing 345-540, thickness of the glass is in the illuminant D ₆₅ measured at 3.5 mm, the visible light transmittance of 45% or less 30 % or more, a solar radiation transmittance of 40% or more and 20% or less and the ultraviolet transmittance of 14% or less, moreover ultraviolet transmittance Tuv ₃₅₀ at a wavelength of 350nm is 7
% And UV transmittance at a wavelength of 370 nm Tuv ₃₇₀ is 33
%. The densified green color glass according to claim 1, wherein In wherein said coloring component weight percentages, Fe ₂ O
₃ (Total iron) 0.95 to 1.30 and ppm, CoO 155-2
70, Se25～48, basically each containing Cr ₂ O ₃ 550~1180, the thickness of the glass is in the illuminant D ₆₅ measured at 3.5 mm, the visible light transmittance of 30% or less than 10%, a solar radiation transmittance Rate 25
The ultraviolet transmittance Tuv _{350 at a} wavelength of 350 nm is 3% or less, and the ultraviolet transmittance Tuv _{370 at a} wavelength of 370 nm is 25% or less. The dense green color glass described in the above. 6. The dense green according to claim 1, wherein the reduction rate (Fe ²⁺ / Fe ³⁺ ) of said green glass is 0.35 or more and 0.55 or less. Color glass. 7. The wavelength of the dense green glass 11
The transmittance Ts at ₁₀₀ nm is ₁₁₀₀ , and the thickness of the glass is 3.5 mm.
In the illuminant D ₆₅ measurements, of claims 1 to 6, wherein the 25% or less Densuguri - emission color based glass. Wherein said Densuguri - main wavelength of emission color based glass, plate thickness of the glass is in the illuminant D ₆₅ measured at 3.5 mm,
2. The semiconductor device according to claim 1, wherein the thickness is not less than 520 nm and not more than 580 nm.
8. A green-glass according to any one of claims 1 to 7. 9. The base composition of the soda-lime-silica-based glass is expressed as SiO ₂ 67-75, Al ₂ O ₃ 0.05-3.0 in weight%,
CaO 7 ~11, MgO 2 ~4.5, ZnO 0 ~0.1, Na 2 O11.5~
_{16, K 2 O 0.5 ~3.0,} SO 3 0.05 ~0.4, and SiO ₂ + Al ₂ O
_{3 68 ~74, CaO + Mg0 +} ZnO 11~15, Na 2 O + K 2 O 12~17
9. The dense green color glass according to claim 1, which is a sheet glass composition. 10. The dense green color glass according to claim 1, wherein zinc selenite is used as a raw material for preparing the Se component.