JPH0761835A - Glass for cutting ultraviolet light and infrared light - Google Patents

Abstract

PURPOSE:To improve a performance for shielding UV light and IR light and a transmittance in the visible region by covering the surface of UV-cutting glass containing specific deposited fine particles with an IR light-reflecting film or IR light-absorbing film. CONSTITUTION:The raw material compounds of elements are weighted and mixed to give the first type glass composition comprising 62-80mol.% of SiO2, 10-20mol.% of B2O3, 1-10mol.% of Al2O3, 5-15mol.% of LiO2+Na2O+K2P, 0.01-2mol.% (in terms of CuO) of a copper oxide, 0.01-2mol.% of Cl+Br, and fine amounts of other elements, or the second type glass composition comprising 50-80mol.% of SiO2, 10-30mol.% of B2O3, 1-20mol.% of Al2O3, 5-20mol.% of Li2O+Na2O+K2O, 0.3-10mol.% of ZrO2, 0.01-2mol.% of the copper oxide, 0.01-2mol.% of Cl+Br, etc., melted at 1200-1800 [for 5min to several days, and subsequently molded into a desired shape. The molded glass is cooled to room temperature, and subsequently heated to cover an IR light-reflecting film on the surface of an UV-cutting glass in which CuCl2 fine particles and/or CuBr2 fine particles having a particle diameter of 0.5-400nm are deposited.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to ultraviolet and infrared cut glass.

[0002]

2. Description of the Related Art Generally, a light ray having a wavelength of about 380 nm or less is called an ultraviolet ray, and a light ray having a wavelength of about 700 nm or more is called an infrared ray. The wavelength range of light rays emitted from sunlight is approximately 200 nm to 5 μ.
Light rays other than visible light rays such as ultraviolet rays and infrared rays are included in a wide range of m. Also, a large amount of ultraviolet rays and infrared rays are emitted from a high-intensity light source such as a halogen lamp or a metal halide lamp. Ultraviolet rays cause sunburn, fading and deterioration of the human body and various objects, while infrared rays become thermal energy. General window glass is about 320n
It cannot completely absorb ultraviolet rays above m and infrared rays below 5 μm. Therefore, ultraviolet rays and infrared rays from sunlight are transmitted. Also, the glass and plastic used for the front lens of lamps cannot completely block ultraviolet rays and infrared rays.

Conventionally, as a glass that cuts off both ultraviolet rays and infrared rays, for example, in order to shield infrared rays and ultraviolet rays emitted from a light source for a projection television, an ordinary infrared ray reflection film and an ultraviolet ray absorbing film are provided on both sides of a plate glass. A film was used. Further, in building materials and glass for automobiles, there are some commercialized as heat ray reflecting glass for preventing the penetration of solar energy into the room and, conversely, low-emission glass that does not allow the heat in the room to escape to the outside.

[0004]

However, in the ultraviolet absorbing film, in order to transmit visible light and sharply absorb only ultraviolet light, the number of films may be multi-layered, but short ultraviolet light is transmitted. On the contrary, in order to cut short ultraviolet rays, only ultraviolet rays cannot be sharply absorbed, so that there is a problem that a part of visible rays is also cut. In addition, building materials and glass for automobiles have insufficient ultraviolet absorption characteristics, and there is a problem in that the human body, interior materials, and the like are subject to sunburn, deterioration, and fading.

[0005]

The present invention has been made to solve the above-mentioned problems, and CuCl or / and Cu
Provided is an ultraviolet and infrared cut glass, which has an infrared reflection film or an infrared absorption film on the surface of the ultraviolet cut glass on which Br fine particles are deposited.

Since the UV and infrared cut glass of the present invention has CuCl and / or CuBr fine particles having a very sharp absorption in the UV region deposited in the glass, it does not absorb light in the visible region and only UV light is absorbed. Can be selectively shielded, and since the glass surface has an infrared reflection film layer, it can also block infrared rays.

The particle size of CuCl or / and CuBr fine particles in the glass is preferably 0.5 to 400 nm. Particle size 0.5
If it is less than nm, the absorption of CuCl and / or CuBr is not sufficient and the expected ultraviolet ray shielding is insufficient.
When it is more than nm, visible light is scattered in the glass and the transparency of the glass is lost, which is not preferable. A particle size of 1 to 100 nm in this range is particularly preferable because it sufficiently shields ultraviolet rays and makes the glass transparent to visible light.

The preferred glass compositions of the present invention are of two types, the first type being SiO ₂ 62-80% B ₂ O ₃ 10-20% Al ₂ O ₃ 1-10% Li _{2 in} mol% notation. O + Na ₂ O + K ₂ O 5 to 15% CuO converted copper oxide 0.01 to 2% Cl 0 to 2% Br 0 to 2% Cl + Br 0.01 to 2% SnO converted tin oxide 0 to 3% Sb ₂ O ₃ converted antimony oxide 0 to 3% SnO converted tin oxide + Sb ₂ O ₃ converted antimony oxide 0.01 to 3% is preferable.

When SiO ₂ is less than 62 mol%, white turbidity due to phase separation of glass and red color due to precipitation of copper colloid are apt to occur. On the contrary, when it exceeds 80 mol%, the glass formation temperature is high. And Cu, Cl, and Br components are volatilized, which is not preferable.

When B ₂ O ₃ is less than 10 mol%, CuCl, CuBr
Is difficult to obtain, and conversely, if it exceeds 20 mol%, the chemical durability of the glass becomes low, which is not preferable. Al ₂ O ₃
When it is less than 1 mol%, the glass tends to become cloudy due to phase separation, while when Al ₂ O ₃ exceeds 10 mol%, vitrification becomes difficult, which is not preferable.

[0011] _{Li 2 O, Na 2 O,} K 2 O is, Li to the total mole% of either using the Li ₂ O alone or in the glass composition of _{(Li 2 O + Na 2 O} + K 2 O) 2 Two or more kinds of O may be mixed and used as long as the O mol% ratio is 0.2 or more, but the total amount is 5 mol%.
If less than, the glass formation temperature becomes high and Cu, Cl, Br
If the total amount exceeds 15 mol%, the components are volatilized, and on the other hand, copper colloid is likely to precipitate in the glass to cause a reddish color and the chemical durability is lowered, which is not preferable.

In order to deposit CuCl and / or CuBr fine particles in the glass, copper is converted into oxide in the range of 0.01 to 2 as CuO.
It is necessary to contain mol%, Cl or / and Br of 1 to 2 mol% O.O. When the total amount of CuO is less than 0.01 mol%, CuCl and / or CuBr fine particles are not sufficiently deposited and the ultraviolet ray shielding performance is not sufficient, which is not preferable.

On the other hand, even if it exceeds 2 mol%, the ultraviolet ray shielding performance is not further improved, and on the contrary, CuCl and / or CuBr fine particles are deposited and the transparency of the glass is lost, which is not preferable. Cl and Br may be used alone or as a mixture, and their mixing ratio is appropriately selected depending on the shielding wavelength. Further, if the total of Cl and Br is less than 1 mol% O.O, CuCl and / or CuBr fine particles are not sufficiently deposited and the ultraviolet ray shielding performance is not sufficient, which is not preferable. on the other hand,
Even if it exceeds 2 mol%, the ultraviolet shielding performance is not further improved, and on the contrary, phase separation of the glass is likely to occur and the transparency of the glass is lost, or phase separation or red coloration occurs when the melt is cooled, which is preferable. Absent.

By adding 0.01 to 3 mol% of tin and antimony oxides in terms of SnO + Sb ₂ O _{3 in} addition to the above components, the glass is not colored and CuCl and / or CuBr fine particles are further precipitated. It is preferable because it becomes easy. When the content of SnO + Sb ₂ O ₃ is less than 0.01 mol%, the glass tends to be colored blue, and when it exceeds 3 mol%, the glass tends to be colored red, which is not preferable.

Of these ranges, SiO ₂ 63-72
Mol%, B ₂ O ₃ 12-18 mol%, Al ₂ O ₃ 2-8 mol%, Li
₂ O + Na ₂ O + K ₂ O 7-13 mol%, CuO 0.1-1.5 mol%, Sn
O + Sb ₂ O ₃ 0.05~ ₂ mol%, made from Cl and / or Br 0.1 to 1.5 mol%, Li ₂ O to the total mole% of the glass composition of _{(Li 2 O + Na 2 O} + K 2 O) A glass having a mol% ratio of 0.25 or more has a colorless and transparent appearance, and CuCl and / or CuBr fine particles having a controlled particle size can be easily deposited, and thus are particularly preferable.

The composition of the second type glass is SiO ₂ 50 to 80% B ₂ O ₃ 10 to 30% Al ₂ O ₃ 1 to 20% Li ₂ O + Na ₂ O + K in terms of mol%. ₂ O 5 to 20% ZrO ₂ 0.3 to 10% CuO equivalent copper oxide 0.01 to 2% Cl 0 to 2% Br 0 to 2% Cl + Br 0.01 to 2% SnO equivalent tin oxide 0 to 3 % Sb ₂ O ₃ converted antimony oxide 0 to 3% SnO converted tin oxide + Sb ₂ O ₃ converted antimony oxide 0.01 to 3% is preferable.

If the SiO ₂ content is less than 50 mol%, the chemical durability of the glass will be insufficient, and conversely if it exceeds 80 mol%,
The glass formation temperature becomes high, and Cu, Cl, and Br components are volatilized, which is not preferable.

When B ₂ O ₃ is less than 10 mol%, CuCl, CuBr
Is difficult to obtain, and conversely, if it exceeds 30 mol%, the chemical durability of the glass becomes low, which is not preferable. Al ₂ O ₃
When it is less than 1 mol%, the glass tends clouded by phase separation, whereas, when Al ₂ O ₃ is more than 20 mol%, since it becomes difficult to vitrify undesirable.

[0019] _{Li 2 O, Na 2 O,} K 2 O is, Li to the total mole% of either using the Li ₂ O alone or in the glass composition of _{(Li 2 O + Na 2 O} + K 2 O) 2 As long as the molar ratio of O is 0.2 or more, two or more kinds may be mixed and used, but the total amount is 5
If it is less than mol%, the glass formation temperature becomes high and Cu and
Cl and Br components volatilize, while the total amount is 20 mol%
If it exceeds the above range, the chemical durability of the glass will be low, and thus both are not preferable.

If the content of ZrO ₂ is less than 0.3 mol%, clouding may occur due to phase separation during molding of the glass or redning of the glass may occur due to precipitation of copper colloid during heat treatment.
If it exceeds 10 mol%, the glass formation temperature becomes high and the Cu, Cl, and Br components volatilize, which is not preferable.

In order to deposit CuCl and / or CuBr fine particles in the glass, copper is converted into oxide in the range of 0.01 to 2 as CuO.
It is necessary to contain mol%, Cl or / and Br of 1 to 2 mol% O.O. When the total amount of CuO is less than 0.01 mol%, CuCl and / or CuBr fine particles are not sufficiently deposited and the ultraviolet ray shielding performance is not sufficient, which is not preferable. On the other hand, even if it exceeds 2 mol%, the UV shielding performance does not improve any more,
Large particles of CuCl or / and CuBr fine particles are deposited and the transparency of the glass is lost, which is not preferable.

Cl and Br may be used alone,
They may be mixed and used, and their mixing ratio is appropriately selected depending on the shielding wavelength. Also, the total of Cl and Br is O.O1 mol%
When it is less than 1, the CuCl or / and CuBr fine particles are not sufficiently precipitated and the ultraviolet ray shielding performance is not sufficient, which is not preferable. On the other hand, even if it exceeds 2 mol%, the ultraviolet shielding performance is not further improved, and conversely, phase separation of the glass tends to occur, the transparency of the glass is lost, and phase separation or red coloration occurs when the melt is cooled. Therefore, it is not preferable.

In addition to the above components, by containing 0.01 to 3 mol% of oxides of tin and antimony in terms of SnO + Sb ₂ O ₃ , the glass is not colored and further CuCl and / or CuBr fine particles are deposited. It is preferable because it becomes easy. When the content of SnO + Sb ₂ O ₃ is less than 0.01 mol%, the glass tends to be colored blue, and when it exceeds 3 mol%, the glass tends to be colored red, which is not preferable.

And in these ranges, SiO ₂ 55-75
Mol%, B ₂ O ₃ 12 to 25 mol%, Al ₂ O ₃ 2 to 15 mol%, Li
₂ O + Na ₂ O + K ₂ O 7-17 mol%, ZrO ₂ 0.3-3 mol%, CuO
0.1 to 1.8 mol%, SnO + Sb ₂ O ₃ 0.05 to 2 mol%, Cl or / and Br 0.1 to 1.5 mol%, and the total amount of (Li ₂ O + Na ₂ O + K ₂ O) in the glass composition. Glass with a molar ratio of Li ₂ O to mol% of 0.25 or more is CuCl with a controlled particle size and / or
CuBr fine particles are particularly preferable because they can be easily deposited.

The infrared reflective film of the present invention comprises TiO ₂ , Ta ₂ O ₅ ,
High refractive index layer selected from ZrO ₂ and ZnS and SiO ₂ , MgF ₂ and Na
₃ is a multi-layer structure of two or more layers made of a low refractive index layer selected from AlF _6, or a multi-layer structure of TiO ₂ , TiN _x and TiO ₂ ,
Alternatively, a multilayer structure of ZnO, Ag and ZnO is preferable.

Two or more multi-layers consisting of a high refractive index layer selected from TiO ₂ , Ta ₂ O ₅ , ZrO ₂ and ZnS and a low refractive index layer selected from SiO ₂ , MgF ₂ and Na ₃ AlF ₆ . With the structure, infrared rays can be reflected. When the central wavelength of infrared rays to be reflected is λ, each film thickness is λ / 4, and by forming high-refractive index layers and low-refractive index layers alternately, an infrared reflective film for infrared rays centered on λ is formed. be able to. The glass having the infrared ray reflective film on the surface of the above-mentioned ultraviolet ray cut glass can transmit only visible light of about 380 to 700 nm with high transmittance. These infrared reflective films are preferably coated on the glass surface by a vacuum deposition method or a sol-gel method.

Further, TiO _2, TiN _x, the multilayer structure of TiO _{2 (i.e., TiO 2, TiN x, TiO} 2, TiN x, as TiO _2, TiO ₂ and Ti
N _x and alternating layers)
A film that reflects infrared rays of 00 to 3000 nm is formed. Further, the color tone can be changed by changing the film thickness of each.

In addition, a multilayer structure of ZnO, Ag, and ZnO (that is,
About 7 by alternately stacking Ag and ZnO)
Infrared rays of 00 nm or more can be reflected sharply.

The glass having the above-mentioned infrared ray reflective film layer on the surface of the ultraviolet ray cut glass cuts off the ultraviolet rays and infrared rays from the sun, transmits only visible rays, and efficiently reflects the radiant heat from the room, It is possible to reduce the heating load. These reflective film layers are formed by the sputtering method,
The glass surface is preferably coated by the CVD method or the like.

The infrared absorbing film is preferably In ₂ O ₃ or SnO ₂ , and can absorb infrared rays having a wavelength of 1 μm or more. Further, the absorption characteristics can be controlled by including F or the like.

Examples of raw materials used in the production of the ultraviolet and infrared cut glass of the present invention include the following substances.

As the silicon raw material, for example, a silicon oxide such as silicon dioxide, a nitride, an organic silicon compound, or a silicate such as an alkali silicate can be mixed with another alkali compound.

As boric acid raw material, boric acid (H ₃ BO ₃ ),
In addition to oxides such as anhydrous boric acid (B ₂ O ₃ ), nitrides, organoboron compounds, and borate salts such as alkali borate can be used as a mixture with other alkali compounds.

As the aluminum raw material, hydroxides and oxides such as aluminum hydroxide (Al (OH) ₃ ) and alumina (Al ₂ O ₃ ) as well as nitrides and organic aluminum compounds can be used.

Typical examples of the alkali metal raw material are carbonates, but other alkali compounds such as hydroxides and chlorides can be appropriately used.

Examples of raw materials for copper, chlorine and bromine include chlorides and bromides of copper such as CuCl, CuCl ₂ , CuBr and CuBr _2, and copper as a simple substance or an oxide or hydroxide of copper.
Inorganic salts such as sulfate and organic salts can be used. Further, chlorine and bromine can be supplied as alkali chloride, alkali bromide, ammonium chloride, ammonium bromide and chlorides and bromides of other additive components. Furthermore,
Chlorine and bromine can be introduced as a simple substance or a gas of chloride or bromide by reacting with glass.

As a raw material for tin, stannous oxide (SnO)
), Stannic oxide (SnO ₂ ) and other oxides, as well as chlorides and organotin compounds.

As the raw material of antimony, in addition to oxides such as antimony trioxide (Sb ₂ O ₃ ) and antimony pentoxide (Sb ₂ O ₅ ) and complex oxides such as sodium pyroantimonate,
Chlorides and organic antimony compounds can be used.

As zirconium raw materials, in addition to oxides such as zirconium oxide (ZrO ₂ ), chlorides, complex oxides such as organozirconium compounds and zircon (ZrSiO ₄ ) may be mixed with other silicon compounds. You can

The means for producing the ultraviolet and infrared cut glass of the present invention is not particularly limited, and for example, various raw materials are weighed in predetermined amounts and mixed, and this is heated and melted at 1200 to 1800 ° C. for 5 minutes to several days, A method of forming into a predetermined shape is used. As a method for depositing CuCl or / and CuBr fine particles, a method of cooling the molded glass once to room temperature and then heating it to a predetermined temperature to deposit fine particles and a method of cooling the glass after molding to room temperature are prescribed. Hold at the temperature of
There is a method of depositing fine particles by controlling the cooling rate, and both methods are preferable. The vacuum deposition method, the sputtering method, the
The infrared reflective film layer may be coated by a CVD method, a sol-gel method or the like.

[0041]

【Example】

Examples 1 to 11 Glasses 400 having the compositions shown in Tables 1 to 3
Mix the raw materials so that the amount becomes g, and put this in a platinum crucible 14
After melting at 50 ° C for 2 hours, it was poured onto a stainless steel plate to form a plate-shaped glass. This molded glass is shown in Table 1
By performing heat treatment at the temperature and time shown in Table 3,
Fine particles were deposited in the glass. This fine particle deposited glass was polished to a thickness of 5 mm, and the surface was coated with an infrared reflecting film or an infrared absorbing film by the method described in Tables 1 to 3. The constitution and thickness of the infrared reflecting film or infrared absorbing film are also shown in the table.

The particle size of the fine particles in the glass was measured by observation with a transmission electron microscope. The spectral transmittance of the obtained ultraviolet and infrared cut glass was measured. Wavelength at which the transmittance is 1% at the ultraviolet side absorption edge and the wavelength gradient width (wavelength width at which the transmittance becomes maximum transmittance from 20%), infrared region (800 nm,
Table 1 shows the transmittance and particle size measurement values for 1 μm and 3 μm).
The results are shown in Table 3.

[0043]

[Table 1]

[0044]

[Table 2]

[0045]

[Table 3]

[0046]

Industrial Applicability According to the present invention, it is possible to provide a glass having an extremely excellent ultraviolet and infrared ray shielding performance and a high transmittance in the visible region.

Claims (5)

[Claims] 1. An ultraviolet and infrared cut glass having an infrared reflection film or an infrared absorption film on the surface of the ultraviolet cut glass on which CuCl and / or CuBr fine particles are deposited. 2. The particle size of CuCl or / and CuBr fine particles is 0.5-.
The ultraviolet and infrared cut glass according to claim 1, which has a wavelength of 400 nm. 3. A glass composition in terms of mol% SiO ₂ 62 to 80% B ₂ O ₃ 10 to 20% Al ₂ O ₃ 1 to 10% Li ₂ O + Na ₂ O + K ₂ O 5 to 15% CuO converted copper oxide 0.01 to 2% Cl 0 to 2% Br 0 to 2% Cl + Br 0.01 to 2% SnO converted tin oxide 0 to 3% Sb ₂ O ₃ converted antimony oxide 0 ~ 3% SnO-converted oxide + Sb ₂ O ₃ in terms claims 1 or 2 of ultraviolet and infrared cut glass, characterized in that it consists of an oxide from 0.01 to 3% antimony tin. 4. A glass composition in terms of mol% SiO ₂ 50 to 80% B ₂ O ₃ 10 to 30% Al ₂ O ₃ 1 to 20% Li ₂ O + Na ₂ O + K ₂ O 5 to 20% ZrO ₂ 0.3 to 10% CuO converted copper oxide 0.01 to 2% Cl 0 to 2% Br 0 to 2% Cl + Br 0.01 to 2% SnO converted tin oxide 0 to 3% Sb ₂ O ₃ converted 3. The ultraviolet and infrared cut glass according to claim 1, wherein the antimony oxide is composed of 0 to 3% SnO-converted tin oxide and Sb ₂ O ₃ -converted antimony oxide 0.01 to 3%. 5. The infrared reflective film comprises 1) a high refractive index layer selected from TiO ₂ , Ta ₂ O ₅ , ZrO ₂ and ZnS and a low refractive index selected from SiO ₂ , MgF ₂ and Na ₃ AlF _6. Infrared absorbing film, which has a multi-layered structure of _two or more layers composed of a refractive index layer, or 2) a multi-layered structure of TiO ₂ , TiN _x , and TiO ₂ or 3) a multi-layered structure of ZnO, Ag, and ZnO. Is In ₂ O ₃ or SnO _2.
UV and infrared cut glass.