JP2003313050A - Modification method of UV blocking glass - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a new modification method for glass having UV cut off performance by which the adverse effect of an alkali component can be decreased while keeping excellent transmission characteristics with sharp cut off property against UV rays at specified wavelength or shorter. <P>SOLUTION: In the method for modifying UV cut off glass, phase-separated glass having copper halide fine particles dispersed in the whole or a part of the glass and containing a phase comprising SiO<SB>2</SB>is brought into contact with an acid solution to form a high silicate layer on at least a part of the phase- separated glass surface. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for modifying an ultraviolet blocking glass and a use of the glass modified by the method.

[0002]

2. Description of the Related Art In recent years, liquid crystal panels have been widely used as image display devices. Currently, image display devices include
High image quality and high illuminance are required, and therefore high-intensity lamps are used as light sources.

A light source such as a high-intensity lamp emits strong ultraviolet rays, which causes deterioration of parts. In particular, the liquid crystal
Since the durability against ultraviolet rays is low, a means for protecting the liquid crystal from ultraviolet rays is required.

At present, it is known that an ultraviolet glass in which copper halide fine particles are diffused in the glass or in the surface layer of the glass has a transmission characteristic of blocking ultraviolet rays having a wavelength of a given wavelength or less and transmitting light of a wavelength longer than that. Has been. For example,
Japanese Patent Publication No. 2518749 discloses a colored glass containing copper halide.

However, when the above glass is used as a glass for protecting liquid crystal which is in direct contact with the liquid crystal, there arises a problem that the liquid crystal is deteriorated by an alkali component contained in the glass.

[0006]

DISCLOSURE OF THE INVENTION The present invention has been made in view of the above-mentioned problems of the prior art, and the main purpose of the present invention is to provide a glass having an ultraviolet ray blocking performance only for ultraviolet rays having a specific wavelength or less. It is an object of the present invention to provide a novel modification method capable of reducing the adverse effect of an alkali component and imparting various other excellent functionalities while maintaining excellent transmission characteristics of sharply blocking.

[0007]

Means for Solving the Problems As a result of intensive studies to achieve the above object, the present inventor has found that copper halide as an ultraviolet absorbing component is contained in a phase-separated glass containing a phase containing SiO _2. With respect to the dispersed ultraviolet blocking glass, a high silicic acid layer containing almost no alkali component can be formed on the surface of the ultraviolet blocking glass by contacting the surface with an acid solution, and the glass after the treatment has good ultraviolet blocking performance. The inventors have found that the composition has excellent functionality while maintaining it, and thus completed the present invention.

That is, the present invention relates to the following method for modifying ultraviolet blocking glass and the use of the glass modified by the method. 1. Fine particles of copper halide are dispersed in whole or in part and S
A method for modifying ultraviolet-shielding glass, which comprises contacting a phase-separated glass containing a phase containing iO ₂ with an acid solution to form a high silicic acid layer on at least a part of the surface of the phase-separated glass. 2. Item 2. The method for modifying an ultraviolet blocking glass according to Item 1, wherein the high silicic acid layer is a layer containing 80% by weight or more of SiO ₂ . 3. Item 3. The method for modifying an ultraviolet-shielding glass according to Item 1 or 2, wherein the acid solution is an aqueous solution containing at least one acid selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid and perchloric acid. . 4. The phase-separated glass contains SiO ₂ 20 to 85% by weight, B ₂ O _{3 2 to} 75% by weight, Al ₂ O ₃ 15% by weight or less, Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O and Cs ₂ At least 30% by weight or less of O, MgO, CaO, ZnO,
At least one of BaO, SrO and PbO 10 wt% or less, Nb ₂ O
₅ , ZrO ₂ , La ₂ O ₃ , Y ₂ O ₃ , at least one of Ta ₂ O ₃ and Gd ₂ O ₃ is 10% by weight or less, and a glass containing 0.01 to 15% by weight of copper halide. 4. The method for modifying the ultraviolet blocking glass according to any one of 3 above. 5. The phase-separated glass is composed of SiO ₂ 20 to 85% by weight, B ₂ O _{3 2 to} 75
% By weight, Al ₂ O ₃ 15% by weight or less, Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O
And at least 30% by weight of Cs ₂ O, MgO, CaO, Z
nO, BaO, SrO and at least one of PbO 10 wt% or less,
Nb ₂ O ₅ , ZrO ₂ , La ₂ O ₃ , Y ₂ O ₃ , at least 10% by weight or less of at least one of Ta ₂ O ₃ and Gd ₂ O ₃ , and at least one halogen component selected from Cl, Br and I Item 4. The method for modifying an ultraviolet-shielding glass according to any one of Items 1 to 3, which is a glass in which copper ions are diffused in a glass containing 0.01 to 15% by weight to form a layer containing copper halide microcrystals. 6. A glass for protecting liquid crystals, which comprises an ultraviolet blocking glass modified by the method according to any one of items 1 to 5 above.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION The glass to be treated in the present invention has copper halide dispersed in whole or in part, and
It is a phase-separated glass containing a phase containing O ₂ . Examples of such a phase-separated glass include borosilicate glass containing a phase containing SiO ₂ .

As the copper halide contained in the phase-separated glass, for example, copper chloride, copper bromide, copper iodide and the like can be exemplified, and one kind or a mixture of two or more kinds thereof can be used. The copper halide is preferably dispersed in the phase-separated glass as fine crystals. The size of the copper halide crystal is preferably about 0.1 to 10 nm in diameter, and more preferably about 0.5 to 5 nm.

The content of copper halide in the phase-separated glass may be appropriately determined within a range having a desired ultraviolet absorbing ability. When the copper halide is dispersed in the entire phase-separating glass, the proportion of the copper halide in the whole phase-separating glass is preferably about 0.01 to 15% by weight, and 0.05 to 5% by weight. The amount is more preferably about 0.1 to 2% by weight, further preferably about 0.1 to 2% by weight.

When the copper halide is dispersed in a part of the phase-separated glass, halogen components such as Cl, Br and I are usually added in an amount of 0.01 to 15% by weight, preferably 0.1% by weight.
By diffusing copper ions in a glass containing about 1 to 2% by weight, copper ions and halogen components react with each other in a portion where the copper ions have diffused to form an ultraviolet absorbing layer in which copper halide is dispersed. .

In the method of the present invention, the phase-separated glass to be treated is brought into contact with an acid solution to modify the phase-separated glass. As a result, in the contact portion of the phase-separated glass with the acid solution, soluble components such as alkali components are eluted, and a high silicic acid layer containing a large amount of SiO ₂ which is an insoluble component on the surface of the phase-separated glass. It is formed. The amount of SiO ₂ in the high silicic acid layer is not particularly limited and may be appropriately determined depending on the purpose of use of the glass after modification, etc.
The amount of SiO ₂ in the high silicic acid layer is preferably about 80% by weight or more, more preferably about 85% by weight or more.

The method of bringing the acid solution into contact is not particularly limited, and any method may be used as long as the phase-separated glass to be treated and the acid solution can be sufficiently brought into contact with each other. A method of dipping a part or the whole is common.

The conditions for contacting the acid solution are also not particularly limited, and a high silicic acid layer having a desired silicic acid content is formed and the phase separation is performed depending on the composition and shape of the phase-separated glass used. The conditions may be such that copper halide remains on at least part of the glass.

As the acid solution, for example, an aqueous solution containing an acid such as nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid or perchloric acid can be used. These acids can be used alone or in combination of two or more.

The concentration of the acid solution can be appropriately set depending on the type of acid and the like, but it is usually about 0.1 normal to 10 normal, preferably 0.5 normal to 5 normal.

The temperature of the acid solution may be room temperature, but in order to improve the treatment efficiency, it may be heated to about 50 to 100 ° C, preferably about 70 to 100 ° C.

The time for contacting the phase-separated glass with the acid solution is
Usually about 3 to 48 hours, preferably about 6 to 24 hours,
More preferably, it may be about 12 to 24 hours. After contact with the acid solution, the acid solution may be removed as necessary by washing with water or the like.

The portion to be brought into contact with the acid solution may be appropriately selected according to the type of the phase-separating glass, the purpose of use, and the like. For example, (1) when the whole phase-separating glass contains copper halide, Method to elute soluble components by contacting the solution on both surfaces of the phase-separating glass, (2) When the whole phase-separating glass contains copper halide, contact the acid solution with the surface of one side of the phase-separating glass To dissolve the soluble components,
(3) When the copper halide is contained only in the surface layers on both surfaces of the phase-separating glass, the acid solution is contacted with the surface layer on one surface of the phase-separating glass to elute the soluble component, (4) the phase-separating glass is on one side. In the case of containing copper halide only in the surface layer of, the method of contacting the acid solution with the surface layer of the surface not containing at least copper halide to elute the soluble phase, (5) the phase-separated glass is fibrous. Then, when copper halide is contained in the entire glass, a method of bringing an acid solution into contact with the surface layer of the glass to elute the soluble phase can be exemplified. Further, as long as a desired amount of copper halide remains in a part of the phase-separated glass after the acid treatment, the entire glass may be immersed in the acid solution.

Among the above-mentioned methods, for example, in the method (1), copper halide can be left in a layered form at the center of the plate-like phase-separating glass. In the above methods (2) and (3), for example, copper halide can be left on one surface of the phase-separated glass. In the above method (4), when the acid solution is brought into contact with only the surface layer of the surface not containing the copper halide, the copper halide can be left on the surface which is not brought into contact with the acid solution. In the above method (5), for example, copper halide can be left in the center of the fiber.

The amount of copper halide to be left can be appropriately set depending on the application. For example, it can be appropriately set within a range having a desired ultraviolet absorbing ability.

[0023] For a portion where the acid solution is not desired to be contacted, the phase-separating glass is sealed with a known coating material that does not dissolve in the acid solution and does not react with the acid solution, and then the phase-separating glass is changed to the acid solution. You may make it contact. For example, a method of forming a SiO ₂ film by a vacuum vapor deposition method or a coating method, a method of coating with a resin sheet, a paint or the like can be applied.

According to the method of the present invention, the phase-separated glass which has been modified by bringing it into contact with an acid solution has a porous surface, which may reduce the transmittance of visible light. In such a case, the high silicic acid layer can be densified by contacting it with an acid solution and then performing heat treatment to improve the transmittance of visible light. Further, the heat treatment can suppress the permeation of the alkaline component from the lower layer of the high silicic acid layer to reduce the contamination property to the liquid crystal, and further improve the chemical resistance of the ultraviolet blocking glass. it can. The heat treatment conditions are not particularly limited,
The heating temperature may be about 400 to 900 ° C., and 70
It is preferable to set the temperature to about 0 to 900 ° C. The heat treatment time may be the time until the desired densification is achieved, depending on the thickness of the high silicic acid layer and the heat treatment temperature, and is usually about 30 minutes to 200 hours. The heat treatment atmosphere may be an oxygen-containing atmosphere such as the air.

Phase- Separated Glass Hereinafter, the phase- separated glass to be treated by the method of the present invention will be described in more detail.

(1) Phase-separated glass in which copper halide fine particles are uniformly dispersed In the phase-separated glass to be treated, each component other than copper halide is selected from various components conventionally used in glass. Can be used.

Among the phase-separated glasses, examples of the phase-separated glass in which copper halide fine particles are uniformly dispersed include, for example,
SiO ₂ 20-85% by weight, B ₂ O ₃ 2-75% by weight, Al ₂ O ₃
About 15% by weight or less, Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O and Cs ₂ O
At least about 30% by weight or less of MgO, CaO, ZnO, Ba
At least one of O, SrO and PbO is about 10 wt% or less, Nb
Borosilicate glass containing at least about 10% by weight of at least one of ₂ O ₅ , ZrO ₂ , La ₂ O ₃ , Y ₂ O ₃ , Ta ₂ O ₃ and Gd ₂ O ₃ and about 0.01 to 15% by weight of copper halide. Can be preferably used.

The content of SiO ₂ contained in the borosilicate glass is usually about 20 to 85% by weight, preferably about 30 to 70% by weight, more preferably about 50 to 65% by weight.

The content of B ₂ O ₃ contained in the borosilicate glass is usually about 2 to 75% by weight, preferably about 10 to 40% by weight, more preferably about 15 to 35% by weight.

Li ₂ O and Na contained in the above borosilicate glass
The content of at least one component selected from the group consisting of ₂ O, K ₂ O, Rb ₂ O and Cs ₂ O is usually about 30% by weight or less,
Preferably about 0.5 to 20% by weight, more preferably 0.5 to 1
It is 0% by weight, particularly preferably about 0.5 to 5% by weight.

MgO and Ca contained in the above borosilicate glass
O, ZnO, BaO, the content of at least one component selected from the group consisting of SrO and PbO is usually about 10 wt% or less, preferably about 0.5 to 10 wt%, more preferably 0.5.
It is about 5% by weight.

The content of Al ₂ O ₃ contained in the borosilicate glass is usually about 15% by weight or less, preferably about 1 to 10% by weight.

Nb contained in the borosilicate glass₂O_Five, Zr
O₂, La₂O₃, Y₂O₃, Ta₂O₃And Gd₂O ₃Selected from the group consisting of
The content of at least one component selected is usually 10 wt.
% Or less, preferably about 0.5 to 5% by weight.

The borosilicate glass may contain at least one component selected from the group consisting of As ₂ O ₃ , Sb ₂ O ₃ and SnO, and the content thereof is usually about 1% by weight. The following may be done. These ingredients are useful as fining agents.

The above borosilicate glass is made of Fe, Ni, Mn, C.
o, V, Cr, Cu, Pd, Ce, rare earth elements (Sc, Ti, Pr, Nd,
Sm, Eu, Tb, Dy, Ho, Er, Tm, Yb, Lu, etc.) may be included. These oxides may be used alone or in combination of two or more. The content of these oxides is not particularly limited, but may be usually about 15% by weight or less, preferably about 5 to 10% by weight, more preferably about 0.1 to 5% by weight. Glasses containing these oxides almost completely block ultraviolet rays having a certain wavelength or less, and exhibit a specific absorption characteristic for wavelengths longer than that depending on the type of the oxide contained.

The phase-separated glass to be treated in the present invention can be manufactured by a known method. For example,
The above-mentioned borosilicate glass can be manufactured by a known method disclosed in Japanese Patent No. 2518749, Japanese Patent No. 2645923, Japanese Patent No. 2852462, or the like. That is, the raw materials may be blended so as to have a predetermined composition, and the glass may be treated according to a conventionally-used glass manufacturing method. More specifically, the raw materials are mixed so as to have a predetermined composition, and 1200 to 1500
Melt at a temperature of about ℃, stir, clarify, pour into a mold, during or after cooling, at a temperature of about 450 ~ 700 ℃ 0.1 ~ 5
A glass product having a desired shape can be obtained by performing heat treatment for about an hour and performing processing such as cutting and polishing.

In the above manufacturing process, in order to mix fine particles of copper halide into glass, copper halide is
Alternatively, copper oxide as a raw material thereof, copper oxide, a copper compound such as copper halide and lithium halide as a halogen source capable of forming copper halide together with the copper source, sodium halide, potassium halide, rubidium halide, An alkali halide compound such as cesium halide may be blended with another raw material so as to have a predetermined composition. As the components other than the copper halide, conventional glass raw materials such as oxides, carbonates, hydroxides, etc., which can eventually become the predetermined components, can be used as they are.

In the cooling process, the glass is not thermally distorted.
10 to 100 ° C / hr, preferably 30
~ 50 ° C hr, heating is about 10-300 ° C / hr, preferred
Do it at a slow speed of 30 to 100 ° C / hr.
And is desirable. Depending on these heating rate and heating time
Thus, the size of the copper halide crystal is determined. Melter
However, an oxidizing atmosphere may be used, but Cu ions^-
It is preferable to carry out in a neutral or reducing atmosphere so that
Yes. As a refining agent in the refining process₂O ₃, Sb
₂O₃, SnO, etc. may be used.

(2) Phase-Separated Glass Partially Dispersed with Copper Halide Fine Particles Among the phase-separated glasses to be treated by the method of the present invention, the phase-separated glass partially dispersed with copper halide fine particles is as follows: It is possible to use a phase-separated glass in which copper ions are generated by diffusing copper ions in a base glass containing halogen.
The base glass used in such a method is Si
O ₂ 20 to 85 wt%, B ₂ O ₃ 2~75 wt%, Al ₂ O ₃ 15 wt%
Below, at least 30% by weight of at least one of Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O and Cs ₂ O, MgO, CaO, ZnO, BaO, SrO and PbO.
10% by weight or less, Nb ₂ O 5, ZrO ₂ , La ₂ O ₃ , Y ₂
10% by weight or less of at least one of O ₃ , Ta ₂ O ₃ and Gd ₂ O ₃ ,
And glass containing 0.01 to 15% by weight of at least one halogen component selected from Cl, Br and I.

The content of SiO ₂ contained in the base glass is usually about 20 to 85% by weight, preferably about 30 to 85% by weight, more preferably about 40 to 82% by weight.

The content of B ₂ O ₃ contained in the base glass is usually about 2 to 75% by weight, preferably about 12 to 50% by weight.

Li ₂ O, Na ₂ O, K contained in the above-mentioned base glass
The content of at least one component selected from the group consisting of ₂ O, Rb ₂ O and Cs ₂ O is usually about 30% by weight or less, preferably about 2 to 20% by weight, more preferably 5 to 20% by weight. Particularly preferably, it is about 15% by weight.

MgO, CaO, Zn contained in the above-mentioned base glass
The content of at least one component selected from the group consisting of O, BaO, SrO and PbO is usually 10% by weight or less, preferably about 0.5 to 10% by weight.

The content of Al ₂ O ₃ contained in the base glass is usually about 15% by weight or less, preferably about 1 to 10% by weight.

Nb ₂ O ₅ , ZrO ₂ , La contained in the above-mentioned matrix glass
The content of at least one component selected from the group consisting of ₂ O ₃ , Y ₂ O ₃ , Ta ₂ O ₃ and Gd ₂ O ₃ is usually about 10% by weight or less, preferably about 0.5 to 10% by weight. is there.

The content of at least one halogen component selected from Cl, Br and I contained in the above base glass is
Usually, it is about 0.01 to 15% by weight, preferably about 0.1 to 2% by weight.

As the base glass, As ₂ O ₃ , Sb ₂ O ₃ and SnO were added.
At least one component selected from the group consisting of may be contained, and the content thereof may be usually about 1% by weight or less. These ingredients are useful as fining agents.

The base glass is Fe, Ni, Mn, Co, V, C.
r, Cu, Pd, Ce, rare earth elements (Sc, Ti, Pr, Nd, Sm, E
u, Tb, Dy, Ho, Er, Tm, Yb, Lu, etc.) may be included. These oxides may be used alone or in combination of two or more. The content of these oxides is not particularly limited, but is usually about 15% by weight or less, preferably about 5 to 10% by weight, more preferably 0.1 to
It may be about 5% by weight. Glasses containing these oxides almost completely block ultraviolet rays having a certain wavelength or less, and exhibit a specific absorption characteristic for wavelengths longer than that depending on the type of the oxide contained.

As a method for producing a phase-separated glass in which copper halide fine particles are partially dispersed by diffusing copper ions in a base glass containing halogen, for example, there is a known method disclosed in Japanese Patent No. 3049379. The method can be applied. The method of diffusing copper ions is not particularly limited, and a method of heat treatment after forming a coating containing copper metal or a copper compound on the surface of the base material, immersing the base material in a molten bath of copper salt A method etc. can be illustrated.

As a method of forming a film containing copper metal or a copper compound on the surface of the base material, for example, a method of applying a paste containing a copper compound and drying it, or a sol-gel method using a copper alkoxide solution is used to form the film. how to,
Examples thereof include a method of forming a film of copper or a copper compound by a method such as a vacuum vapor deposition method, a CVD method (chemical vapor deposition method), an ion vapor deposition method, a sputtering method and a thermal spraying method. The thickness of the coating containing copper metal or copper compound may be appropriately determined according to the characteristics of the ultraviolet blocking glass to be formed, but it is usually about 0.1 to 2 mm. The heat treatment after forming the film may be performed at a temperature of about 400 to 900 ° C. for about 10 minutes to 200 hours. Then, by washing with water, it is possible to obtain a phase-separated glass having a function of blocking ultraviolet rays, in which a copper halide microcrystal layer is formed.

Among these methods, the method of applying a paste containing a copper compound and drying it will be described more specifically. The paste containing the copper compound is not particularly limited, and has a suitable viscosity that can be applied onto the base material,
Any paste-like material containing a copper compound capable of diffusing copper ions in the base material by heat treatment can be used. As such a copper compound, CuS
O ₄ , CuCl, CuCl ₂ , CuBr, CuBr ₂ , Cu ₂ O, CuO, Cu (NO ₃ ) ・ 3
Examples thereof include H ₂ O and CuS. The content of the copper compound in the paste is not particularly limited, usually 20 ~ 70
It may be about wt%, preferably about 30 to 60 wt%.
The paste usually contains a binder component,
As the binder component, it is preferable to use a resin component that decomposes in the heat treatment step and is easily removed by washing with water. As such a paste, it is usually possible to use a commercially available paste for coloring glass, for example, copper sulfate 40 to 60 wt%, sodium sulfate 5 to 15 wt%, alcohol, etc. Solvent 15-25% by weight
And a glass coloring paste composed of about 1 to 5% by weight of a resin component. The conditions for drying after applying the paste are not particularly limited, as long as it is dried so that the solvent component is sufficiently removed, and it is usually about 150 ° C. to 300 ° C.
If it is dried for about 15 minutes, it can be efficiently dried.

In the method of immersing the base metal in the copper salt melting bath, the base metal is heated in a temperature of about 300 to 700 ° C. and below the sag point of the base metal. After immersing for about 10 minutes to 20 hours, it may be pulled out from the melting tank and washed with water, and by such a method, copper ions are diffused in the base material to form a copper halide microcrystalline layer on the surface of the base material. Can be formed. The copper salt used in the method of immersing in the melting tank is not particularly limited, as long as it is a copper compound capable of diffusing copper ions in the base material, for example, CuSO ₄ , CuCl, CuCl ₂ ,
CuBr, CuBr ₂ , Cu ₂ O, CuO, Cu (NO ₃ ) .3H ₂ O, CuS, and the like can be mentioned.In the case of a compound having a melting point higher than the above-mentioned temperature range, the melting point is set to the above-mentioned temperature by appropriately combining them. It may be used as a range. In addition, as components other than copper salt, NaNO ₃ , N
It is also possible to promote the diffusion of copper ions by using a molten salt containing a ₂ SO ₄ , NaCl or the like in an amount of about 5 to 50% by weight.

By diffusing copper ions in the base glass by the above-mentioned method or the like, the copper ions are combined with halogen in the base glass to absorb ultraviolet rays composed of a microcrystalline layer of copper halide near the surface of the base glass. A layer is formed.

When the phase-separated glass is produced by such a method, after the copper ion exchange reaction is further performed, the temperature is not less than the transition point of the glass and not more than the sag point, and 0.5
By performing the heat treatment for about 10 hours, it is possible to almost completely absorb the ultraviolet rays in the wavelength range below the intended absorption wavelength, even if they are slightly transmitted.

When producing the phase-separated glass,
By a method of forming a coating containing a copper metal or a copper compound on only one surface of the base material and heat-treating it, or by a method of shielding one surface of the glass with a known coating material that is not attacked by molten salt and immersing it in a molten salt tank It is possible to easily form the copper halide microcrystal layer on only one surface of the base material.

Uses of Modified Glass The glass modified by the method of the present invention has excellent ultraviolet ray blocking performance, and at the same time, a high silicic acid layer containing almost no alkali component is formed on at least a part of its surface. There is. Therefore, when used as a glass for liquid crystal protection that is in direct contact with the liquid crystal, the liquid crystal is not deteriorated by the alkali component contained in the glass and can be suitably used as a glass for liquid crystal protection. When used as a glass for liquid crystal protection, the high silicic acid layer should have a thickness of 0.
It is preferably about 01 mm or more, more preferably about 0.05 mm or more, and most preferably about 0.1 mm to 0.6 mm. The thickness of the layer containing about 0.01 to 15% by weight of copper halide can be appropriately set according to the intensity of the ultraviolet rays emitted from the light source, but is about 0.01.
The thickness is preferably about mm or more, and more preferably about 0.1 mm or more. When used as a glass for protecting liquid crystal, at least the surface in contact with the liquid crystal may be provided with a high silicic acid layer.

Further, the glass modified by the method of the present invention is useful as a glass for containers of chemicals, alcohols, various drinking water and the like. When used as glass for containers, the thickness of the high silicic acid layer is preferably about 0.01 mm or more, more preferably about 0.05 mm or more, most preferably about 0.1 mm to 0.6 mm. . The thickness of the layer containing copper halide in an amount of about 0.01 to 15% by weight can be appropriately set according to the durability of the contents to ultraviolet light, but is preferably about 0.01 mm or more, More preferably, it is about 1 mm or more.
When used as a glass for a container, the high silicic acid layer, chemicals, alcohol, by manufacturing the container so as to come into contact with the contents such as various beverages, it is possible to prevent the contents from being deteriorated by alkaline components. it can.

Furthermore, since the glass modified by the method of the present invention has two portions having different refractive indexes, it can be suitably used as an optical fiber or an optical waveguide. For example, regarding a phase-separated glass in the shape of a fiber, a glass in which a soluble component is eluted by bringing an acid solution into contact with the surface layer and copper halide is left in the center of the fiber is preferably used as an optical fiber. be able to.

When used as an optical fiber, the thickness of the high silicic acid layer is preferably about 0.001 mm or more, more preferably about 0.002 to 0.1 mm. When used as an optical fiber, the diameter of the central portion containing copper halide is preferably about 0.001 mm or more,
More preferably, it is about 1 mm.

[0060]

According to the modification method of the present invention, while maintaining excellent transmission characteristics that sharply block only ultraviolet rays having an arbitrary wavelength or less, adverse effects due to alkali components are reduced,
Furthermore, it is possible to obtain an ultraviolet blocking glass having various other excellent functionalities.

[0061]

EXAMPLES The present invention will be described in more detail with reference to examples. The present invention is not limited to the examples below.

Example 1 55.3% by weight of SiO ₂ , 22.3% by weight of Na ₂ B ₄ O ₇ and H ₃ BO ₃
10.2% by weight, Al (OH) ₃ 4.2% by weight, K ₂ CO ₃ 1.
3% by weight, ZnO 0.9% by weight, NaBr 4.6% by weight, Cu
0.5% by weight of ₂ O, 0.7% by weight of SiZrO ₄ and Nb ₂ O ₅
A glass raw material was prepared by mixing 0.1% by weight. After melting the glass raw material, molding and slow cooling,
A heat treatment was performed at 600 ° C. for 50 minutes to obtain a phase-separated glass containing a phase containing SiO _{2 in} which copper halide fine particles were uniformly dispersed throughout the glass. Then, slowly cool until the strain disappears, and polish to obtain 15
Three pieces of phase-separated glass having a size of 15 mm × 15 mm × 1.1 mm were obtained. The composition of the obtained phase-separated glass is shown in Table 1 as No. 1. The unit of numerical values in the table is% by weight. Moreover, the result of the transmittance measurement of the phase-separated glass is shown in FIG. As is clear from FIG. 1, the phase-separating glass blocks only ultraviolet rays.

Next, each of the three phase-separated glasses was placed in a glass container, and each container was defined as 1 normal, 2 normal or 3 normal.
It was filled with a nitric acid aqueous solution (concentration of undiluted solution: 60%, specific gravity: 1.38) adjusted to normal. Each container was heated using an oil bath and subjected to acid treatment at 98 ° C for 12 hours to form a high silicic acid layer on the surface of the phase-separated glass. After the acid treatment, the glass was washed with water and dried.

The transmittance of the three obtained glasses was measured. The results are shown in Figure 2. Due to light scattering and water adsorbed due to the glass surface becoming porous, a decrease in transmittance was observed in the wide visible region, but no change was observed in the ultraviolet blocking property.

Next, the phase-separated glass having a high silicic acid layer acid-treated with a 1N aqueous nitric acid solution was subjected to 5 ° C. at 500 ° C.
It was heat-treated for an hour and the transmittance was measured. The results are shown in Fig. 3.
The high silicic acid layer, which was porous, had a high density due to the heat treatment, and the light scattering was suppressed, so that the transmittance in the visible region was about the same as before the acid treatment. In addition, no change was observed in the ultraviolet blocking property.

Further, the obtained glass was subjected to energy dispersive X-ray spectroscopy measurement to obtain a SiO ₂ concentration distribution chart. The obtained results are shown in FIG. In FIG. 4, in the glass
SiO ₂ is shown in black. From Fig. 4, Si is treated by acid treatment.
It can be seen that components other than O ₂ were eluted and a high silicic acid layer with a thickness of about 0.13 mm was formed on the glass surface.

Example 2 44.2% by weight of SiO ₂ , 17.4% by weight of Na ₂ B ₄ O ₇ and H ₃ BO ₃
9.4% by weight, Al (OH) ₃ 11.9% by weight, K ₂ CO ₃ 1.
7% by weight, Li ₂ CO ₃ 2.9% by weight, ZnO 2.4% by weight, N
The glass raw material was prepared by mixing 9.2 wt% aBr and 0.6 wt% SiZrO ₄ . 15mm × 15mm × 3mm after melting, shaping and slow cooling glass raw material
Then, the base glass containing Br was obtained by polishing. The composition of the base glass is shown as No. 2 in Table 1.
The unit of numerical values in the table is% by weight.

Next, 55% by weight of CuSO ₄ and Na ₂ SO ₄
A paste consisting of 10% by weight, 15% by weight of acrylic resin, 10% by weight of cellulose resin and 10% by weight of solvent (terpineol) was applied to one side of the base glass which had been polished so that the thickness was 1 mm, and the temperature was 200 ° C. Dried for 30 minutes. Then, by performing heat treatment at 510 ° C. for 48 hours, copper ions were diffused to form a layer containing copper halide microcrystals. Then, it was gradually cooled until the strain disappeared, washed with water, and dried. When the transmittance of the obtained phase-separated glass was measured, the same results as in Example 1 (FIG. 1) were obtained, and it was confirmed that only ultraviolet rays were blocked.

Next, the phase-separated glass was placed in a glass container and subjected to an acid treatment using an aqueous nitric acid solution adjusted to 1N, 2N or 3N in the same manner as in Example 1, whereby the surface of the phase-separated glass was treated with a high silica. An acid layer was formed, washed with water and dried.

When the transmittance of the three kinds of glass thus obtained was measured, the same results as in Example 1 (FIG. 2) were obtained. That is, although the transmittance was reduced in the wide visible range, no change was observed in the ultraviolet blocking property.

Next, the phase-separated glass having a high silicic acid layer acid-treated with a 1N aqueous nitric acid solution was treated at 500 ° C. for 5 hours.
The glass was heat treated for a period of time and the transmittance of the obtained glass was measured. The results obtained were similar to those of Example 1 (FIG. 3). That is,
The transmittance in the visible region is about the same as before acid treatment,
No change was seen in the UV blocking properties.

When the energy dispersive X-ray spectroscopy measurement was performed on the obtained glass, the same SiO ₂ as in FIG. 4 was obtained.
A concentration distribution map was obtained. That is, it was found that components other than SiO ₂ were eluted by the acid treatment and a high silicic acid layer was formed on the glass surface.

[0073]

[Table 1]

[Brief description of drawings]

FIG. 1 is a diagram showing the transmittance of a phase-separated glass containing a phase containing SiO _{2 in} which fine copper halide particles used in Example 1 are dispersed.

FIG. 2 is a diagram showing the transmittance of glass having a high silicic acid layer formed by performing an acid treatment in Example 1.

FIG. 3 is a diagram showing the transmittance of the glass obtained in Example 1. The glass used is a glass obtained by performing an acid treatment using a 1N nitric acid aqueous solution and further performing a heat treatment.

FIG. 4 is a diagram showing a SiO ₂ concentration distribution on a glass cross section obtained in Example 1. The glass is a glass that has been subjected to acid treatment using a 1N nitric acid aqueous solution and further subjected to heat treatment, and the measurement was performed using an energy dispersive X-ray analyzer.

─────────────────────────────────────────────────── ─── Continued Front Page (51) Int.Cl. ⁷ Identification Code FI Theme Coat (Reference) C03C 3/074 C03C 3/074 3/11 3/11 G02F 1/1333 500 G02F 1/1333 500 (72) Inventor Takashi Tarumi 6-3-3 Minamitsumori, Nishinari-ku, Osaka-shi, Osaka Within Isuzu Seiko Glass Co., Ltd. (72) Inventor, Koji Hosokawa 6-3-6 Minamitsumori, Nishinari-ku, Osaka, Osaka Isuzu Seiko Glass Co., Ltd. (72) Inventor Tatsuya Suetsugu 6-3-6 Minamitsumori, Nishinari-ku, Osaka-shi, Osaka Prefecture Isuzu Seiko Glass Co., Ltd. (72) Kohei Sumino 1-31 Midorigaoka, Ikeda-shi, Osaka Independent administrative corporation Kansai Center, National Institute of Advanced Industrial Science and Technology (72) Inventor Tetsuo Yazawa 1-831 Midorigaoka, Ikeda-shi, Osaka Independent administrative agency National Institute of Advanced Industrial Science and Technology Kansai F-term (reference) in the center EB01 EB02 EB03 EB04 EC01 EC02 EC03 EC04 ED01 ED02 ED03 EE01 EE02 EE03 EF01 EF02 EF03 EG01 EG02 EG03 FA01 FB01 FC01 FC02 FC03 FD01 FE01 FF01 FG01 FG02 FG03 FH01 FH02 FH03 FJ01 FJ02 FJ03 FK01 FK02 FK03 FL01 GA01 GB01 GC01 GD01 GE01 HH01 HH02 HH04 HH05 HH07 HH09 HH11 HH13 HH15 HH17 HH20 JJ01 JJ03 JJ05 JJ06 JJ07 JJ08 JJ10 KK01 KK03 KK04 KK05 KK07 KK10 MM12 MM27 NN13 QQ18

Claims (6)

[Claims] 1. A phase-separated glass containing a phase in which copper halide fine particles are wholly or partly dispersed and which contains SiO ₂ is brought into contact with an acid solution to form high silicic acid on at least a part of the surface of the phase-separated glass. A method for modifying an ultraviolet blocking glass, which comprises forming a layer. 2. The method for modifying an ultraviolet blocking glass according to claim 1, wherein the high silicic acid layer is a layer containing 80% by weight or more of SiO ₂ . 3. The acid solution is at least one selected from the group consisting of nitric acid, sulfuric acid, hydrochloric acid, phosphoric acid, acetic acid and perchloric acid.
The method for modifying an ultraviolet-blocking glass according to claim 1, which is an aqueous solution containing a specific acid. 4. The phase-separated glass is SiO 2.₂ 20-85% by weight, B₂O₃ 
2-75% by weight, Al₂O₃15% by weight or less, Li₂O, Na₂OK₂O, Rb
₂O and Cs₂At least 30% by weight of O, MgO, Ca
At least one of O, ZnO, BaO, SrO and PbO 10 wt% or less
Below, Nb₂O_Five, ZrO ₂, La₂O₃, Y₂O₃, Ta₂O₃And Gd₂O₃Small
10% by weight or less and copper halide 0.01-15
The glass according to any one of claims 1 to 3, which is a glass containing wt%.
Method for modifying the UV blocking glass described above. 5. A phase-separated glass comprising 20 to 85% by weight of SiO ₂ and B ₂ O _{3
2 to} 75% by weight, Al ₂ O ₃ 15% by weight or less, Li ₂ O, Na ₂ O, K ₂ O,
30% by weight or less of at least one of Rb ₂ O and Cs ₂ O, MgO, Ca
10% by weight or less of at least one of O, ZnO, BaO, SrO and PbO, 10% by weight of at least one of Nb ₂ O ₅ , ZrO ₂ , La ₂ O ₃ , Y ₂ O ₃ , Ta ₂ O ₃ and Gd ₂ O _3. The following, and a glass that is a base material glass containing 0.01 to 15% by weight of at least one halogen component selected from Cl, Br and I, and having a layer containing copper halide microcrystals formed by diffusing copper ions. The method for modifying the ultraviolet blocking glass according to claim 1. 6. A glass for protecting liquid crystals, which comprises an ultraviolet blocking glass modified by the method according to any one of claims 1 to 5.