JP2001019471A - Dark-green glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To suppress the production of NiS and to moderately control UV transmittance, visible light transmittance and solar radiation transmittanee by incorporating specified amounts of Fe2O3, FeO, CoO, NiO and Se into a soda lime-silica glass as a basic composition and specifying predominant wavelength due to a D light source. SOLUTION: A soda lime-silica glass excellent in meltability, moldability, mass productivity, water and weather resistances is used as a basic composition and 0.7-1.6 wt.% Fe2O3 (total iron), 0.10-0.23 wt.% FeO [0.10<=Fe2+/(Fe2++ Fe3+)<=0.20], 0.010-0.030 wt.% CoO, 0.010-0.100 wt.% NiO and 0-0.0008 wt.% Se are incorporated into the glass to obtain the objective dark-green glass with 485-530 nm predominant wavelength due to a D light source. This dark- green glass preferably has 10-35% UV transmittance and 15-35% solar radiation transmittance in 5 mm plate thickness and 5-15% excitation purity due to the D light source.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a window glass for vehicles such as automobiles and transportation equipment, which has a low visible light transmittance, a high ability to shield ultraviolet rays and solar radiation, has an appropriate transparency and privacy. And a glass exhibiting a dark green color suitable for architectural window glass and the like.

[0002]

2. Description of the Related Art As a glass having a low visible light transmittance and exhibiting a green color tone, there is a known example employing Fe ₂ O ₃ , CoO, NiO and Se as coloring components.

[0003] International Patent Publication (WO) 97-11036,
JP-A-0-139475 and JP-A-10-182183 disclose low transmittance glasses containing Fe ₂ O ₃ , Se, CoO and NiO as coloring components. However, all of them contain TiO ₂ as essential. Although the content of TiO ₂ is effective in absorbing ultraviolet rays, it is not necessary to absorb and cut off more than necessary if the ultraviolet rays are close to the visible light wavelength range (there is almost no effect on the human body).

Japanese Patent Application Laid-Open No. 10-114540 discloses Fe ₂ O ₃ , Co
Ultraviolet and infrared absorbing low transmittance glasses containing O, Se, and NiO are disclosed. In addition, Fe ₂ O ₃ (total iron) is 1.2wt% or more,
FeO / Fe ₂ O ₃ (total iron) is stated to be 15 wt% or more, and the calculated FeO / glass is 0.18 wt%
%, The ratio of ferrous ions in iron ions is 0.19 (19
%) Or more, but considering the melting property of glass, Fe ₂ O
₃ (total iron) is less than 1.20 wt%, especially FeO / glass is 0.180 wt%
% Or less, and in order to minimize the generation of NiS in the glass melting process originating from the raw material NiO, make the glass more oxidizable, that is, make the ferric ion ratio 0.18 (18%)
It is better to do the following.

The present invention is a glass which can be relatively easily melted and suppresses the generation of NiS during the glass melting process, and the produced glass has an ultraviolet transmittance and a visible light transmittance as well as a moderate sunlight transmittance. It is another object of the present invention to provide a dark green color glass exhibiting a green color tone by setting the main wavelength and the excitation purity within appropriate ranges.

[0006]

SUMMARY OF THE INVENTION The present invention provides a soda lime sheet.
The base composition is Lica-based glass component, and Fe_TwoO_Three(all
Iron is 0.7 to 1.6, FeO is 0.10 to 0.23 (however,
Ratio of ferrous ion: Fe^{Two +}/ (Fe²⁺+ Fe³⁺) Is 0.10-0.2
0), CoO 0.010-0.030, NiO 0.010-0.100, Se 0
~ 0.0008, and the dominant wavelength by the D light source is 485 ~ 5
It is a dark green color glass of 30 nm.

In the above, the UV transmittance at a plate thickness of 5 mm is 15% or less, the visible light transmittance is 10 to 35%, the solar transmittance is 15 to 35%, and the excitation purity by the D light source is 5 to 15%.
It is preferred that

[0008]

Soda-lime-silica based glass in the Detailed Description of the Invention The present _{invention, SiO 2 68 ~73wt%, Al} 2 O 3 0~3wt%, MgO
0~5wt%, CaO 5~12wt%, Na 2 O 10~15wt%, K 2 O
It is in the range of about 0 to 3% by weight, which is about the same level as that of ordinary soda-lime-silica glass, and is excellent in terms of glass meltability, moldability, mass productivity, water resistance and weather resistance of glass products. .

In the present invention, desired optical characteristics are obtained by equilibrating the coloring components in the following ranges in glass.

The content of Fe ₂ O ₃ (total iron) is in the range of 0.7 to 1.6 wt%, and reduces the transmittance of ultraviolet light, visible light, and solar radiation by Fe ³⁺ and Fe ²⁺ , and gives a green color. It is a major component. If the content is less than 0.7 wt%, the above effect cannot be exerted, and 1.6 wt%
If it exceeds, the visible light transmittance is too low, and the transparency is lost. It is preferably in the range of 0.8 to 1.5 wt%, and more preferably the upper limit is less than 1.20 wt%.

FeO should be in the range of 0.10 to 0.23 wt%
, Closely related to other coloring components, but less than 0.10wt%
In this case, the absorption in the infrared region becomes weak.
Fe _TwoO_Three(Trivalent iron) is lower and the absorption in the ultraviolet region
become weak. Preferably, it is in the range of 0.15 to 0.21 wt%. Special
The presence of FeO in a normal melting furnace,
Heating and melting glass by flame
Layers tend to be overheated, while the lower layers are less likely to transfer heat.
Enlarge.

Further, the ratio of ferrous ion in iron ion:
Fe ²⁺ / (Fe ²⁺ + Fe ³⁺ ) (hereinafter referred to as divalent iron ion ratio)
If the ratio is outside the above range, the absorption in the infrared or ultraviolet region becomes weak, and the color tone becomes yellowish or blueish, making it difficult to obtain a desired color tone. Further, by setting the ratio of ferrous ions to 0.20 or less, it is possible to weaken the tendency that the glass surface layer is overheated in the normal glass heating and melting method, and that the heat is not easily transmitted to the lower layer. In addition, the generation of NiS in the glass melting process originating from the raw material NiO is minimized,
In order to avoid breakage of the glass, it is preferable that the glass is made more oxidizing, that is, the ratio of ferrous ions is 0.18 or less.

CoO absorbs light having a wavelength of 550 to 650 nm, and when CoO is used alone, the glass is colored blue. However, by coexisting with the Fe ₂ O _{3 in} the glass in a range of 0.010 to 0.030 wt%, It has the effect of lowering the transmittance from 550 to 650 nm to a neutral green color. If it is less than 0.010% by weight, its effect is small, and if it exceeds 0.030% by weight, it becomes bluish. Preferably, it is in the range of 0.013 to 0.021 wt%.

NiO absorbs light of 400 to 650 nm with a peak at a wavelength of 450 nm and, by itself, causes the color of the glass to change from yellow to brown, and coexists with the above-mentioned Fe ₂ O ₃ , CoO, etc. 0.100
By containing in the range of wt%, there is an effect of lowering the transmittance of 400 to 650 nm to make the color more neutral green. If it is less than 0.010 wt%, the effect is small, and if it exceeds 0.100 wt%, the brown color tone becomes strong. A more preferred range is 0.
020-0.080 wt%.

Se absorbs light mainly at a wavelength of 490 nm, but coexists with the above-mentioned Fe ₂ O ₃ , CoO, NiO, etc.
A desired green color tone can be obtained by appropriately adding t in the range of t%. 0.0008 Se in this component system
Even if the content exceeds wt%, it is difficult to obtain a good green color tone. In addition, the introduction of excessive amounts of harmful Se poses problems in handling and air pollution.

As a fining agent, a sulfate such as Na ₂ S
O ₄ , the sulfur content to be introduced in the form of CaSO ₄ (SO ₃ ) also acts as an oxidizing agent, and is designed and introduced in order to set the ratio of ferrous ions to the appropriate range, that is, 0.10 to 0.20. Alternatively, the oxygen concentration in the atmosphere may be designed, and these are design items as appropriate.

By setting the main wavelength to 485 to 530 nm, a visually preferable green color can be obtained. 485nm
Shorter wavelengths have a blue tint, and wavelengths longer than 530 nm have a yellow tint, which is not a desirable color tone. Preferably 48
The range is 5 to 510 nm.

The ultraviolet transmittance at a standard plate thickness of 5 mm is 15
%, The effect on the human body and the fading of the coloring material can be suppressed as much as possible.

The visible light transmittance at a plate thickness of 5 mm is 10
If it exceeds 35%, it is difficult to obtain good privacy, and if it is less than 10%, transparency is impaired. In order to obtain appropriate privacy and transparency, it is necessary to keep the content within the above range.

Further, the solar radiation transmittance at a plate thickness of 5 mm is 15 to 3
By setting it within 5% and below 35%,
Heat rays can be satisfactorily blocked, and the cooling load in summer can be effectively reduced, for example. The lower the solar transmittance, the better, but
If it is less than 15%, the visible light transmittance is reduced correspondingly to 10%
And the transparency is impaired.

The stimulus purity can be appropriately designed. For example, the color (light) of an object viewed through glass is observed as a color closer to the original color of the object as the stimulus purity of the glass is lower, and the stimulus purity is better as the stimulus purity is lower to view the scenery through the glass in a natural color. However, on the other hand, the higher the stimulus purity is, the better the green color tone is to be manifested.
The stimulus purity measured using a light source is suitably about 5% to 15%.

Incidentally, the visible light transmittance and the solar transmittance are JI
S R3106, UV transmittance measured according to ISO / DIS-9050,
The dominant wavelength and stimulus purity are measured with a D light source based on JIS Z8722 and displayed according to JIS Z8701.

In order to appropriately suppress the ultraviolet transmittance, the visible light transmittance and the solar transmittance of the glass, the wavelength from 300 nm in the ultraviolet region emitted from the sun and reaching the surface of the earth to 1.5 μm in the infrared region.
It is sufficient to absorb light of about m as much as possible. On the other hand, in a normal glass melting furnace (heating and melting method from above), infrared rays (heat rays) of several μm exceeding 1.5 μm should be transmitted appropriately. This is preferred from the viewpoints of glass melting and soaking.

That is, in the ordinary heating and melting method using a flame from above, direct heating to the glass surface layer by the flame or the heating atmosphere, soaking by heat transfer from the heated glass surface layer to the lower layer, Along with the soaking by convection with the lower layer, it is also important to heat and soak the lower layer by the heat rays emitted from the flame and the heated rays emitted from the heated glass. Of course, in order to suppress the solar transmittance of the glass, 1.
Although it is necessary to absorb light of 5 μm or less as much as possible, it is preferable to appropriately increase the transmittance so that the heat rays exceeding the above-mentioned wavelength are suppressed and reach the lower layer.

For example, the relationship between the temperature of an object and the spectral energy distribution is shown by the following function proposed by Blank (American Institute of Phisics Handbook, pp. 6-19).
9). W (λ, T) = C1 / [λ ⁵ [exp (C2 / λ · T)] − 1] where W: radiation energy, λ: wavelength (cm), T: absolute temperature, C1, C2: constant W, that is, λ, T is about 0.3cm · ° K
In this case, the energy becomes maximum, and therefore, at a temperature of about 1500 to 1700 ° K at the time of melting the glass, a heat ray having a wavelength of about 2 μm effectively acts on the heating. In the present invention, the wavelength 2μ
The heat ray of m is as high as 30% or more when the thickness is 5 mm, so that the heat ray can easily reach the lower layer of the glass layer, thereby facilitating heating of the glass in the lower layer.

According to the present invention, a glass sheet can be produced by a usual heating and melting method, and in particular, FeO Glass below 0.180 can be easily manufactured. In addition, 10 mm from thin glass with a thickness of about 1 mm
Thick glass sheets exceeding mm can be manufactured, and flat or bent glass sheets, so-called green sheets, semi-tempered or tempered glass, etc. are also included in the scope of the present invention. It can be suitably used as a single-pane glass, a laminated glass, a double-glazed glass, or the like, as a window material for architectural windows, automobiles, and transportation equipment.

[0027]

EXAMPLES Hereinafter, specific examples of the present invention will be described in comparison with comparative examples. [Example: Relationship between coloring component composition and optical characteristics] As basic component compositions, SiO ₂ 72 wt%, Al ₂ O ₃ 2 wt%, MgO 4 wt%,
_{CaO 8wt%, Na 2 O 13wt} %, K 2 O 1wt%, the goal of total 100 wt%, and silica sand as raw material, feldspar, soda ash, dolomite, limestone employing mixed adjusted. Each coloring component,
Desired amount of Fe ₂ O ₃ (FeO), CoO, Cr
Bengala, cobalt oxide, chromium oxide, nickel oxide, and selenium were added and mixed to contain ₂ O ₃ , NiO, and Se. Glauberite as a fining agent and an oxidizing agent was introduced as Na ₂ SO _{4 in an} amount of 1% by weight or less based on 100% by weight of the oxide glass.
A small amount of carbon or slag coexisted to assist the decomposition of sodium sulfate.

The raw materials are blended in a desired ratio, and the blended raw materials are put into a crucible, which is provided with a resistance heating body on the ceiling and side walls of the furnace and set in an electric furnace heated and maintained at about 1450 ° C. Melt and vitrify for about 3 to 4 hours, hold at about 1400 to 1430 ° C. for about 1.5 to 2 hours for homogenization and clarification, then pour out into a mold to form a glass block, cut out into a plate shape, and grind and polish. And each measurement sample.

For these samples, the content (% by weight) of the coloring / color tone adjusting component composition was analyzed by a gravimetric method, and the visible light transmittance (%) and the ultraviolet light transmittance (%) as optical characteristics (at a thickness of 5 mm) were obtained. ), solar transmittance (%), and dominant wavelength (nm: at illuminant D _65), an excitation purity (%: at illuminant D ₆₅₎ was determined. They are measured and calculated using a U4000 type spectrophotometer (manufactured by Hitachi, Ltd.) in accordance with the standard. Also, the same means (D ₆₅ light source used, glass thickness 5mm) by the wavelength 1.8 .mu.m, an infrared (heat rays) transmittance of 2μm was measured.

Further, the melt homogeneity is observed with the naked eye, and the homogeneity is extremely good (A), slightly inferior to the above A (A '), and further inferior to the above A' but normal heating. (B), which is considered to be producible by the method, or (C), which is apparently inferior in homogeneity, or which remains difficult to produce by the usual heating and melting method using a flame from above, with fine bubbles remaining. (Table of melting characteristics of NiS formation in Tables 1 to 4, melting homogeneity section).

The results are shown in Tables 1 to 4 below.
As shown in Tables 1 to 4, in the present example, the coloring and the color tone adjusting components were contained in a desired range, so that optical characteristics such as visible light transmittance, ultraviolet light transmittance, solar transmittance, main wavelength, and stimulus purity were obtained. In the expected range, has a relatively low visible light transmittance, high UV and solar radiation shielding performance,
It is possible to obtain dark green glass having appropriate transparency and privacy and suitable for vehicles such as automobiles, windowpanes for transportation equipment, windowpanes for construction, and the like.

On the other hand, in Comparative Examples 1 and 2, the FeO content was high, the transmittance of infrared rays (heat rays) at wavelengths of 1.8 μm and 2 μm was low (easy to be absorbed), and the melt homogeneity in a normal heating and melting method was high. There is a problem. Comparative Example 3 contains harmful Cr ₂ O ₃ having a problem in handling, and contains excessive amounts of Se. Comparative Examples 4 and 5 contain an excessive amount of Se, and the desired dark green color cannot be obtained basically.

As shown in the section on melt homogeneity,
Generally, the melt homogeneity is very good (A) below 0.180 wt% of FeO, good (A ') above 0.180 wt% to 0.200 wt%, and acceptable (B) above 0.200 wt% to 0.230 wt% (B), 0.230 wt% It can be seen that% (C) is not acceptable.

Reference Example: Relationship between Reduction Ratio of Nickel-Containing Glass and Nickel Sulfide Produced As described above, Ni in the raw material
The presence of O produces NiS during glass melting, which is
It is known that the glass expands upon transition from NiS to low-temperature NiS, causing glass breakage. It is speculated that the reduction rate of the glass (represented by the ratio of ferrous ions) may affect the formation of NiS. However, in this test, the ratio of ferrous ions in the nickel-containing glass and the generated sulfur The relationship of nickel was investigated in detail.

Glass composition: SiO ₂ 72 wt%, Al ₂ O
_{3 2wt%, MgO 4wt%,} CaO 8wt%, Na 2 O 12.8wt%,
K ₂ O 1wt%, Fe ₂ O ₃ 0.2wt%, a total of 100wt% target, silica sand, feldspar, soda ash, dolomite, limestone,
Bengala (Fe ₂ O ₃ ) was adopted and mixed and adjusted. Put the prepared raw materials in a crucible and place them in an electric furnace maintained at about 1450 ° C for about 4 hours.
After melting for about an hour, and further holding at about 1420 to 1430 ° C. for about 2 hours, a glass sample was poured out onto a carbon plate to obtain a glass sample.

Passing through glass through 270 mesh (about 50 μm or less)
Of about 100μm in 100% by weight of the glass powder
0.05wt% of φ metal Ni powder added, and divalent in glass
In order to adjust the iron ion ratio to various desired ratios, sodium sulfate (Na_TwoS
O_Four) And sodium sulfite (Na _TwoSO_Three) And add
Mix and prepare. Filling the mixture into a crucible, electric furnace
And maintained at 1400 ° C for 1 hour.
Drained and cooled. Black foreign matter remains in the glass
Admitted.

When a part of the glass was crushed and a plurality of foreign substances produced were randomly taken out and analyzed, most of them were Ni ₃ S ₂ and Ni ₇
Is S _6, NiS involved in the destruction of the very slight glass (Ni: S
= 1: 1).

The relationship between the ratio of divalent iron ions: Fe ²⁺ / (Fe ²⁺ + Fe ³⁺ ) and the number of NixSy (total nickel sulfide) per gram of glass is as follows. It is as follows.

Divalent iron ion ratio NixSy average number / glass 1 g 16% 0.02 18% 0.12 20% 0.25 22% 0.37 24% 0.47 26% 0.48 From the above, the ratio of ferrous iron in normal glass melting
If 20% is compared to 24 to 26%, the number of NixSy is 1
/ 2 can be remarkably reduced to about / 2.
It turned out that it can be reduced to about 4.

This result is for NixSy,
It is presumed that the same tendency is observed in iS, and it is clear that when the divalent iron ion ratio is 20% or less, more preferably 18% or less, the generation of NiS for breaking glass can be significantly reduced.

Based on the results, each of Examples in Tables 1 to 4,
In the section of the suppression characteristic of NiS formation in the comparative example, the best (A) is the ferrous iron ratio of 18% (0.18) or less, the good (B) is more than 18% and 20% (0.20) or less (B), and the improper is more than 20%. (C)
Was ranked. As is clear from the table, Comparative Examples 1 to
In No. 3, it corresponds to Impossible (C) and is not effective in suppressing the generation of NiS.

[Comprehensive Evaluation] In this example, the coloring and tone adjustment components of the glass were within the desired range.
Optical properties such as visible light transmittance, ultraviolet light transmittance, solar radiation transmittance, dominant wavelength, stimulus purity, etc. are within the expected range, have relatively low visible light transmittance, and have high ultraviolet and solar radiation shielding performance , With appropriate transparency and privacy, excellent melting homogeneity in glass production, and NiS generation suppression properties, suitable for vehicles such as automobiles, windowpanes for transportation equipment, windowpanes for construction, etc. A dark green glass can be obtained.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

[Table 3]

[0046]

[Table 4]

[0047]

According to the present invention, the solar transmittance as well as the ultraviolet transmittance and the visible light transmittance can be appropriately suppressed, and the dominant wavelength and the stimulus purity can be set in appropriate ranges. It has privacy properties, and also has excellent melting homogeneity during glass production, and has the characteristic of suppressing NiS generation, and exhibits a dark green color suitable for vehicles such as automobiles, windowpanes for transportation equipment, windowpanes for construction, etc. It is.

 ──────────────────────────────────────────────────続 き Continuing on the front page F term (reference) 4G062 AA01 BB03 DA06 DA07 DB01 DB02 DB03 DC01 DD01 DE01 DF01 EA01 EB04 EC01 EC02 EC03 ED01 ED02 ED03 EE03 EE04 EF01 EG01 FA01 FA10 FB01 FC01 FD01 FE01 FF01 GA01 F01 GB01 GC01 GC02 GD01 GE01 HH01 HH03 HH05 HH07 HH09 HH12 HH13 HH15 HH17 JJ01 JJ03 JJ05 JJ07 JJ10 KK01 KK03 KK05 KK07 KK10 MM01 NN01 NN07 NN13

Claims (2)

[Claims] (1) A soda-lime-silica-based glass component is used as a base composition, and Fe ₂ O ₃ (total iron) is 0.7 to 1.6 and FeO is 0.10 to 0.
23 (However, the ratio of ferrous ions in iron ions: Fe ²⁺ / (Fe
²⁺ + Fe ³⁺ ) 0.10 ~ 0.20), CoO 0.010 ~ 0.030, NiO
A dark green color glass, wherein 0.010 to 0.100, Se is 0 to 0.0008, and a dominant wavelength by a D light source is 485 to 530 nm. 2. A 5 mm-thick plate having an ultraviolet transmittance of 15% or less, a visible light transmittance of 10 to 35%, a solar transmittance of 15 to 35%,
2. The dark green glass according to claim 1, wherein the stimulus purity as measured by the D light source is 5 to 15%.