JPH1072239A - Ultraviolet-ray and infrared-ray absorbing glass - Google Patents

Abstract

PROBLEM TO BE SOLVED: To obtain UV and IR absorbing glass having a bronze tone and suitable for use as window glass for vehicles such as an automobile or window glass for construction. SOLUTION: This glass consists of a basic glass compsn. and coloring components. The basic glass compsn. consists of, by weight, 65-80% SiO2 , 0-5% Al2 O3 , 0-10% MgO, 5-15% CaO (5<=MgO+CaO<=15%), 10-18%Na2 O, 0-5%K2 O (10%<=Na2 O+K2 O<=20%), 0-5%B2 O3 and 0.01-1.0% (expressed in terms of SnO2 ) total tin oxide. The coloring components are, by weight, 0.15-0.8% (expressed in terms of Fe2 O3 ) total iron oxide (T-Fe2 O3 ), 0.1-2.0% CeO2 , 0-2.0% TiO2 , 0-0.005% CoO and 0.0003-0.005% Se.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet and infrared absorbing glass having a bronze color tone.

[0002]

2. Description of the Related Art In recent years, from the viewpoint of demand for prevention of deterioration of interior materials due to upgrading of interior materials of automobiles and reduction of cooling load,
As an automotive window glass, a glass provided with an ultraviolet-ray-infrared absorbing ability has been proposed.

For example, it contains a relatively large amount of Fe ₂ O ₃ ,
Greenish glass with enhanced heat ray absorption and ultraviolet ray absorption has been developed for use in automobiles.

In glass having a bronze-based or brown-based color tone, the use of CeO ₂ and TiO ₂ with a Fe ₂ O ₃ content lower than that of green-based glass has been carried out to enhance the ultraviolet absorbing ability. I have. For example, a heat-absorbing glass having a bronze color tone disclosed in Japanese Patent Application Laid-Open No. 6-40741 is 68-74% of SiO ₂ , 0.1 to 3 expressed as a weight percentage as a base composition.
% Al ₂ O ₃ , 2-4.5% MgO, 8-11% C
aO-, 11.5 to 16% of Na ₂ O, 0.5~3.0%
K ₂ O, 0.1-0.4% SO ₃ , and 68-74%
SiO ₂ + Al ₂ O ₃ , 11-15% CaO + Mg
O, 12 to 17% Na ₂ O + K ₂ O, 0.13 to 0.55% of total iron oxide converted to Fe ₂ O ₃ as a coloring component, 0.2 to 0.6% of It contains CeO ₂ , 0.15 to 0.45% TiO ₂ , 0.3 to 14 CoO in ppm, 5 to 20 Se, and has a glass reduction ratio (Fe ²⁺ / Fe ^{3 +} ) 17-55%
It is.

The ultraviolet absorbing colored glass disclosed in Japanese Patent Application Laid-Open No. 6-345482 is 65-75% SiO ₂ , 0.1-5% Al ₂ O ₃ ,
1-6% MgO, 5-15% CaO, 10-18%
Na ₂ O, 0-5% K ₂ O, 0.05-1.0% S
O ₃ , 0.2-1.5% CeO ₂ , 0-1.0% Ti
O ₂ , 0-0.0015% CoO, 0.0002-
0.0012% of Se and from 0.2 to 0.4% of Fe ₂ O ₃
And 3 to 15% of the total Fe is Fe ²⁺ and has a brownish color tone.

[0006]

In the above-mentioned prior art ultraviolet and infrared absorbing glass, the ultraviolet absorbing ability is Fe
It is provided by UV absorption due to each of ₂ O ₃ , CeO ₂ , TiO ₂ and the interaction between them. However, in a glass having a bronze color tone using the Se color, the Fe ₂ O ₃ content must be relatively small in order to maintain the Se pink color, and the bronze color tone is high. It was difficult to achieve both the ultraviolet absorbing ability. That is, when the content of TiO ₂ is increased, yellowishness is likely to occur, and even when the content of CeO ₂ is increased,
Depending on the redox balance of the glass, there is a problem that Se does not sufficiently develop color and the ultraviolet absorbing ability may not be effectively increased.

The present invention has been made in view of the above-mentioned problems of the prior art, and has a bronze color tone.
In particular, it is an object of the present invention to provide an ultraviolet and infrared absorbing glass having a high ultraviolet absorbing ability.

[0008]

[Means for Solving the Problems]

(Structure) The present invention, in% by weight, 65% to 80% of SiO _2, 0 to 5% of Al ₂ O _3, 0% of MgO,
5-15% of CaO, 10 to 18 percent of Na ₂ O, 0 to 5
% Of K ₂ O, 5~15% of MgO + CaO, 10~20
% Of Na ₂ O + K ₂ O0~5% B ₂ O _3, and 0.01
A base glass composition composed of total tin oxide converted to 1.0% SnO ₂ and 0.15 to 0.8% of F as a coloring component
e ₂ O ₃ total iron oxide in terms of _{(T-Fe 2 O 3)} , 0.1~
2.0% CeO _2, 0 to 2.0% of the TiO _2, 0 to 0.
The ultraviolet and infrared absorbing glass is made of 005% CoO and 0.0003 to 0.005% Se.

Here, the present invention is expressed in terms of% by weight,
As coloring components, the total iron oxide in terms of 0.20 to 0.50 percent of _{Fe 2 O 3 (T-Fe} 2 O 3), 0.5~2.0% of CeO _2, 0 to 1.5% TiO ₂ , 0-0.0025%
Of CoO, and consists 0.0005 to 0.005% of Se, and it is preferable FeO in terms of Fe ₂ O ₃ is 5-25% of T-Fe ₂ O _3.

In the present invention, as a coloring component, 1.4 to 2.0% of CeO ₂ ,
It preferably consists of 0.6% of TiO _2.

Further, according to the present invention, 0.05 to 0.6% of Sn as a base glass composition is expressed in terms of% by weight.
Total tin oxide converted to O ₂ , as a coloring component, 1.55 to
2.0% CeO _2, and preferably consists of from 0 to 0.4 percent of TiO _2.

The ultraviolet and infrared absorbing glass of the present invention has a visible light transmittance of 70% or more and 300 to 2100 n measured using a glass A light source converted to a thickness of 4 mm.
m total solar energy transmittance measured in the wavelength range of 72 m
%.

The ultraviolet and infrared absorbing glass of the present invention has a dominant wavelength of 574 to 580 nm, 297.5 to 37, measured using a glass C light source converted to a thickness of 4 mm.
It is preferable that the total solar ultraviolet transmittance as defined in the ISO measured in a wavelength region of 7.5 nm has optical characteristics of less than 12%.

Further, the ultraviolet and infrared absorbing glass of the present invention has a wavelength of 370 nm converted into a thickness of 4 mm.
Is preferably less than 34%.

Next, the reasons for limiting the ultraviolet and infrared absorbing glass of the present invention will be described. However, the following compositions are expressed by weight%.

Iron oxide is made of Fe ₂ O ₃ (F
e ³⁺ ) and FeO (Fe ²⁺ ). FeO is a component that enhances the infrared absorption ability, and Fe ₂ O ₃ is Ce.
O ₂ and TiO ₂ are components that enhance the ability to absorb ultraviolet light.

If the total iron oxide (T-Fe ₂ O ₃ ) is too small, the infrared absorbing ability and ultraviolet absorbing ability are low, and if it is too large, the visible light transmittance is reduced. For this reason, the range of the total iron oxide amount is 0.
15 to 0.8%, preferably 0.20 to 0.50%
Range.

If the amount of FeO is too small, the infrared absorbing ability is low, and if it is too large, the visible light transmittance is low. Preferred F
As the amount of eO, the value converted to Fe ₂ O ₃ is T-Fe ₂
5-25% of the O _3.

The CeO ₂ is a component for improving the ultraviolet absorptivity and is in glass present in Ce ³⁺ or Ce ^{4 +} form of, in particular, Ce ³⁺ is effective in absorbing less ultraviolet absorption in the visible region. If the content of CeO ₂ is too large, the absorption of visible light on the short wavelength side becomes too large, and the glass becomes yellowish.
The range is 1 to 2.0%. In order to obtain better ultraviolet absorbing ability, the amount of CeO ₂ is preferably in the range of 0.5 to 2.0%. Further, it is more preferably in the range of 1.4 to 2.0%, and still more preferably in the range of 1.55 to 2.0%.

SiO ₂ is a main component forming the skeleton of glass. If the SiO ₂ content is less than 65%, the durability of the glass decreases, and if it exceeds 80%, melting of the glass becomes difficult.

Al ₂ O ₃ is a component for improving the durability of the glass, but if it exceeds 5%, it becomes difficult to melt the glass. Preferably it is in the range of 0.1 to 2%.

MgO and CaO are used to improve the durability of glass and to adjust the devitrification temperature and viscosity during molding. When the content of MgO exceeds 10%, the devitrification temperature increases. If the content of CaO is less than 5% or more than 15%, the devitrification temperature rises. If the total of MgO and CaO is less than 5%, the durability of the glass decreases, and if it exceeds 15%, the devitrification temperature increases.

Na ₂ O and K ₂ O are used as glass melting accelerators. Na ₂ O is less than 10% or Na ₂ O
If the total of K ₂ O and K ₂ O is less than 10%, the dissolution promoting effect is poor, and Na ₂ O exceeds 18% or Na ₂ O and K ₂ O
If the total of O 2 exceeds 20%, the durability of the glass decreases. Further, K ₂ O has the effect of increasing the pink coloration of Se and at the same time increasing the ultraviolet absorbing ability. K ₂ O is Na ₂
Since the raw material is more expensive than O, it is not preferable to exceed 5%.

B ₂ O ₃ is a component used for improving the durability of glass or as a melting aid, but also has a function of enhancing absorption of ultraviolet rays. If it exceeds 5%, the decrease in transmittance in the ultraviolet region extends to the visible region, the color tone tends to take on a yellow tint, and inconvenience during molding due to volatilization of B ₂ O ₃ occurs, so the upper limit is 5%. And

TiO ₂ is a component which enhances the ultraviolet absorbing ability particularly through the interaction with FeO, but if it exceeds 2.0%, the glass becomes yellowish. Preferably 0-1.5%
And more preferably in the range of 0 to 0.6%. More preferably, it is in the range of 0 to 0.4%.

CoO is a component for forming a bronze color by coexisting with Se.
%, The visible light transmittance is reduced, and more preferably, it is in the range of 0.0025% or less.

Se is a component for obtaining a bronze color tone in combination with a complementary color of CoO by pink color development.
If it is less than 0.0003%, the desired color cannot be obtained,
If it exceeds 5%, the visible light transmittance decreases. More preferably, it is in the range of 0.0005 to 0.005%.

In SnO ₂ , Sn ions are converted to S
Since n ²⁺ becomes Sn ⁴⁺ on the low temperature side, this change in valence has a function as a reducing agent at the time of glass melting and a function as a fining agent. Further, according to the inventors of the present invention, in a glass containing Se and having a bronze color tone, SnO 2
It has been found that No. ₂ has an effect of promoting the pink coloration of Se and also has an effect of lowering the ultraviolet transmittance. Although the detailed mechanism of this effect is not clear, SnO
_In a composition in which ₂ , Se, Fe ₂ O ₃ and CeO ₂ coexist, Sn
It is presumed that the redox balance caused by O ₂ brings Se into a redox state that is favorable for color development and ultraviolet absorption. If the content of SnO ₂ is less than 0.01%, the effect is small, and if it exceeds 1.0%, undissolved matter is easily generated. More preferably, it is in the range of 0.05 to 0.6%.

Further, Zn in the glass of the composition range of the present invention is Zn.
O, NiO, MnO, V ₂ O _5, or MoO ₃ are 0 to 1% in a total amount of one or two or more types, and S converted to SO ₃ is 0 to 1%, respectively, and does not impair the purpose of the present invention. You may make it contain in the range.

[0030]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, embodiments of the present invention will be described with reference to specific examples.

In order to obtain a predetermined glass composition, quartz sand, dolomite, limestone, soda ash, potassium carbonate, boron oxide, bow glass, ferric oxide, titanium oxide, cerium oxide, cobalt oxide, sodium selenite , Stannous oxide and a carbon-based reducing agent were appropriately mixed, and this raw material was heated and melted at 1500 ° C. in an electric furnace. After melting for 4 hours, the glass substrate was poured out onto a stainless steel plate and gradually cooled to room temperature to obtain a glass plate having a thickness of about 6 mm. Next, this glass plate is 4 mm thick.
It was polished to become. The optical characteristics of the sample thus obtained were measured. The optical characteristics include visible light transmittance (YA) measured using a light source A, total sunlight energy transmittance (TG), ultraviolet transmittance (TUV) specified in ISO, C
Dominant wavelength (DW), stimulus purity (P
e), a and b in the Hunter color system were measured. As another measure of ultraviolet transmission, a transmittance at 370 nm (T370) at which a change in ultraviolet transmittance appears sensitively in the middle of a sharp rise from the absorption edge in the transmittance curve was measured.

Table 1 shows the concentration of each component of the obtained sample and its optical characteristic values. All the concentrations in the table are expressed in weight%. Table 2 shows, as a comparative example, Sn having a composition close to each of the examples.
The concentration of each component of the sample not containing O ₂ and its optical characteristic value are shown.

[0033]

[Table 1]

[0034]

[Table 2]

As is clear from Tables 1 and 2, each of the glasses of this example has a lower ultraviolet transmittance than the corresponding glass of the comparative example, and a of the Hunter color system.
Since the red value is large due to the large value of Se, it is understood that an excellent ultraviolet and infrared absorbing glass having a bronze color tone was obtained.

[0036]

As described in detail above, according to the ultraviolet and infrared absorbing glass of the present invention, it is possible to produce an ultraviolet and infrared absorbing glass having excellent ultraviolet absorbing ability.

Further, since the ultraviolet and infrared absorbing glass of the present invention has a high ultraviolet absorbing ability and a bronze color tone, it can be used as a window glass for vehicles such as automobiles or a window glass for construction. Are excellent in the effect of preventing deterioration of interior interior materials and the effect of preventing fading.

Claims (9)

[Claims] 1. 65% to 80% of Si, expressed in% by weight.
O _2, 0 to 5% of Al ₂ O _3, 0~10% of MgO,. 5 to
15% of CaO, 10 to 18 percent of Na ₂ O, 0 to 5% of the K ₂ O, 5 to 15 percent of MgO + CaO, 10 to 20 percent of _{Na 2 O + K 2 O,} 0~5% of B ₂ O ₃ , And 0.01 to
A base glass composition composed of total tin oxide converted to 1.0% SnO ₂ and 0.15 to 0.8% of F as a coloring component
e ₂ O ₃ total iron oxide in terms of _{(T-Fe 2 O 3)} , 0.1~
2.0% CeO _2, 0 to 2.0% of the TiO _2, 0 to 0.
An ultraviolet and infrared absorbing glass comprising 005% of CoO and 0.0003 to 0.005% of Se. 2. The composition according to claim 1, wherein the coloring component is 0.20 to 0.5.
0% of the total iron oxide in terms of _{Fe 2 O 3 (T-Fe} 2 O 3),
0.5 to 2.0% of CeO _2, 0 to 1.5% of the TiO _2,
0-0.0025% CoO, and 0.0005-0.
Fe of 005% Se and converted to Fe ₂ O ₃
O ultraviolet and infrared radiation absorbing glass as claimed in claim 1 which is 5-25% of T-Fe ₂ O _3. 3. The coloring component is 1.4 to 2.0%.
3. The ultraviolet and infrared ray absorbing glass according to claim 1, comprising CeO ₂ , and 0 to 0.6% TiO ₂ . 4. The composition according to claim 1, wherein said base glass has a composition of 0.05 to
Total tin oxide converted to 0.6% SnO ₂ , 1.55 to 2.0% CeO ₂ as the coloring component, and 0 to 0.
4% of ultraviolet and infrared radiation absorbing glass as claimed in claim 1 consisting of TiO _2. 5. The ultraviolet and infrared ray absorbing glass according to claim 1, wherein the glass has a visible light transmittance of 70% or more measured using a light source A converted to a thickness of 4 mm. 6. The ultraviolet and infrared absorbing glass according to claim 1, wherein the glass has a sunlight transmittance of less than 72% in terms of a thickness of 4 mm. 7. The ultraviolet and infrared absorbing glass according to claim 1, wherein the dominant wavelength measured using a C light source of the glass converted to a thickness of 4 mm is 574 to 580 nm. 8. The glass according to claim 1, wherein the glass has a UV transmittance of less than 12%, as defined in ISO, when converted to a thickness of 4 mm.
The ultraviolet and infrared absorbing glass according to any one of the above. 9. Wavelength 37 of glass converted to 4 mm thickness
The ultraviolet-ray infrared absorbing glass according to any one of claims 1 to 8, wherein the ultraviolet-ray transmittance at 0 nm is less than 34%.