JP2645923B2 - UV blocking material - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an ultraviolet ray blocking material or an ultraviolet ray absorbing material. In the following description of the present specification, “%” means “% by weight”.

[0002]

2. Description of the Related Art Conventionally, colored glass has been used as a sharp-cut glass filter for photographing, etc., as an absorber for ultraviolet or visible light. Such a colored glass is obtained by doping microcrystals such as CdS, CdSe, and CdSSe, which are II-VI compound semiconductors, into the glass. These microcrystals are transmitted through the glass in a certain wavelength range. It serves its purpose by absorbing parts of it. However, the above-mentioned Cd compounds are toxic substances, and there is a risk of harming the health of workers in manufacturing processes such as batch preparation, transportation, and melting. Also,
It is also difficult to treat Cd compounds contained in wastewater and waste generated when processing such as cutting, grinding and polishing of glass, and there is a risk of causing a pollution problem. For example, according to the Water Pollution Control Law, the limit of the allowable content of Cd and its compounds in effluent is 0.1 mg / l. For these reasons, the production of the above glass requires a large amount of equipment such as pollution treatment equipment and sludge treatment equipment.
Compound-doped glass is not an industrially suitable material.

[0003] Further, the transmittance characteristics of CdS, CdS
Glass doped with microcrystals of dSe or CdSSe has a wide wavelength gradient width (Δλ) specified by JIS B 7113, and cannot be said to exhibit sharp absorption. Furthermore, for the same purpose, a multilayer-coated glass has been used. This glass has a multilayer film deposited on glass that does not absorb light in the ultraviolet or visible region, and blocks light in a certain wavelength region by using light interference between the multilayer films. However, the light blocking effect of the multilayer coated glass has an incident angle dependence,
Although light in a certain wavelength region is blocked only for incident light in a certain direction with respect to the glass, the intended effect cannot be obtained for incident light from other angles. Further, the wavelength gradient width of the gradient region is wide, and it is hard to say that a sharp blocking effect is exhibited.

[0004]

SUMMARY OF THE INVENTION As described above, the present inventor has developed a new glass made of glass having a better coloring effect without using Cd compounds and harmful substances, which are problems in conventional colored glass. As a result of intensive research to obtain an ultraviolet shielding material, when doping microcrystals of copper halide, which is a group I-VII compound semiconductor, into glass, light below a certain arbitrary wavelength is almost completely blocked. The inventors have found that an ultraviolet ray blocking material that transmits the above light almost completely and has a sharp absorption characteristic with a narrow wavelength gradient width can be obtained, and has completed the present invention.

That is, the present invention provides the following ultraviolet shielding material: 1 SiO ₂ 20 to 85%, B ₂ O _{3 2 to} 75%, Al ₂ O
_{3 1~10%, Li 2 O,} Na 2 O, K 2 O, at least one 5-15% of Rb ₂ O and Cs ₂ O, MgO, Ca
At least one of O, ZnO, BaO, SrO and PbO 1 to 10% , ZrO ₂ , La ₂ O ₃ , Y ₂ O ₃ , Ta ₂ O
₃ and at least one from 0.5 to 10% of Gd ₂ O _3, to the parallel <br/> beauty CuCl, at least one 0.05 to 15% by weight of halo <br/> Gen of copper selected from CuBr and CuI containing to ultraviolet blocking material comprising a glass consisting (hereinafter this is referred to the first invention), and 2 SiO ₂ 8 to 25 _{wt%, P 2 O 5 5~35%} , B 2 O
₃ 10 to 25% , Al ₂ O ₃ 10 to 35%, Li ₂ O, Na
_{At least one of 2} O, K ₂ O, Rb ₂ O and Cs ₂ O 5
-20%, at least one of MgO, CaO, ZnO, BaO, SrO and PbO 1.9-20 % , Zr
_{O 2, La 2 O 3,} Y 2 O 3, at least one from 0.3 to 10% of Ta ₂ O ₃ and Gd ₂ O _3, and CuCl, CuB
An ultraviolet ray blocking material made of glass containing 0.05 to 15% of at least one kind of copper halide selected from r and CuI (hereinafter referred to as a second invention).

The ultraviolet ray blocking material according to the present invention selectively emits light of a specific wavelength because glass having a specific composition according to the first or second invention of the present application is doped with microcrystals of copper halide. And a desired coloring effect can be achieved. Further, the ultraviolet ray blocking material according to the present invention does not change its color even when irradiated with strong ultraviolet rays, and maintains its unique light transmission characteristics.

Among the components of the glass constituting the ultraviolet shielding material according to the present invention, each component other than the copper halide, which is the greatest feature of the present invention, is selected from various components conventionally used in glass. use.

More specifically, in the first invention of the present application, SiO ₂ , B ₂ O ₃ , A
l ₂ O ₃ , Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O, Cs
₂ O, MgO, CaO, ZnO, BaO, SrO, Pb
O, ZrO ₂ , La ₂ O ₃ , Y ₂ O ₃ , Ta ₂ O ₃ and Gd ₂ O
Select from ₃ and use in combination at a specific ratio.

In the second invention of the present application, among known glass components, SiO ₂ , B ₂ O ₃ , P ₂ O ₅ , Al ₂ O
₃ , Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O, Cs ₂ O, Mg
O, CaO, ZnO, BaO, SrO, PbO, ZrO
₂ , La ₂ O ₃ , Y ₂ O ₃ , Ta ₂ O ₃ and Gd ₂ O ₃ are used in combination at a specific ratio.

As a matter of course, in a multi-component material, each component influences each other to determine the properties of the material, and it is not possible to individually discuss the quantitative range of each component. In some cases, it is not always appropriate. However, in the first invention of the present application and the second invention of the present application, prima facie grounds for defining the quantitative ranges of the respective components are shown below.

I. First invention of the present application Among the components of glass used in the first invention of the present application, SiO
₂ is a main component constituting the glass network, and 2
It is good to make it contain so that it may become about 0-85%, preferably about 50-71%. If the content ratio exceeds 85%, the melting property of the glass deteriorates, while if it is less than 25%, the chemical durability is insufficient and discoloration is caused, which is not preferable.

B ₂ O ₃ improves the melting property of the glass and, in a specific composition, also serves as a component constituting a glass network. B ₂ O ₃ is contained so as to be about _{2 to} 75%, preferably about 12 to 27% of all components. When the content ratio exceeds 75%, the chemical durability of the glass becomes insufficient. On the other hand, when the content ratio is less than 2%, the light transmission characteristics become insufficient and the melting property of the glass also decreases.

Al ₂ O ₃ is a component that suppresses devitrification of glass and improves chemical durability, and 1 to 10% of all components.
Ru is contained in such a way that degree. If the content ratio exceeds this , the melting property of the glass becomes extremely poor.

Li ₂ O, Na ₂ O , K ₂ O, Rb ₂ O and Cs ₂ O have an effect of improving the melting property of glass.
More of these one or two Ru is contained so that about 5-15% of the total components. If the content ratio exceeds this ,
The chemical durability of the glass becomes insufficient.

MgO, CaO, ZnO, BaO, SrO
And PbO have the effect of improving the chemical durability of the glass, and one or more of these are contained in one of the total components.
About 1-10%, Ru preferably be contained so as to be 1 to about 5%. When the content ratio of this component exceeds 10%, the melting property of glass deteriorates.

ZrO ₂ , La ₂ O ₃ , Y ₂ O ₃ , Ta ₂ O ₃ and Gd ₂ O ₃ have the effect of improving the chemical durability of glass, and one or more of these are all components. During ~
0.5 to 10% approximately, Ru preferably be contained in the Do <br/> so that a 0.5 to 5% approximately. When the content ratio of this component exceeds 10%, the devitrification becomes strong, and the stability of the glass is adversely affected.

[0017] The copper halide to be used in the first invention, CuCl, CuBr, and CuI, and these kind or two or more of it is sufficient to dope the glass. These copper halides act as colorants for absorbing any wavelength component in the ultraviolet or visible range. In the first invention of the present application, 0.05 to 15 of the total glass composition
%, Preferably about 0.3 to 8%. By setting the content ratio in the glass within the above range,
A glass having a transmission characteristic that almost completely blocks light having an arbitrary wavelength within a range of 350 to 450 nm, transmits light having a longer wavelength almost completely, and has a sharp absorption characteristic with a narrow wavelength gradient width. Is obtained. When the content ratio of copper halide is less than 0.05%, the above-mentioned desired effects cannot be obtained. On the contrary, when the content ratio exceeds 15%, devitrification occurs, which is not preferable.

II. Second invention of the present application Among the components of the glass used in the second invention of the present application, SiO 2
₂ is a main component constituting a glass network, and 8 out of all components
The content is preferably about 25%, preferably about 10% to 20%. If the content ratio of SiO ₂ exceeds 25%, the melting property of the glass deteriorates, while if it is less than 8%, the chemical durability becomes insufficient and the discoloration is liable to occur.

P ₂ O ₅ is also a main component constituting the glass network, and accounts for about 5 to 35%, preferably 10 to 30% of all the components.
% Is preferably contained. When the content ratio is less than 5% or more than 35%, a colored glass having a desired light transmittance cannot be obtained.

[0020] B ₂ O ₃ is a component to primarily improve the meltability of the glass, Ru is contained so that about 10-25% of the total components. If the content ratio of this material exceeds this ,
The chemical durability of the glass becomes insufficient.

Al ₂ O ₃ is also a component for suppressing devitrification of the glass and improving the chemical durability in the glass used in the second invention of the present application. It is preferred that the content be contained so as to be about 15 to 25%. If the content ratio of Al ₂ O ₃ exceeds 35%, the melting property of the glass deteriorates, while if it is less than 10%, the durability of the glass decreases.

Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O and Cs ₂ O have the effect of improving the melting property of glass.
One or more of these may be contained in an amount of about 5 to 20%, preferably about 5 to 15% of all components. If the content ratio exceeds 20%, the chemical durability of the glass becomes insufficient, whereas if it is less than 5%,
The meltability of the glass decreases.

MgO, CaO, ZnO, BaO, SrO
And PbO have the effect of improving the chemical durability of glass, and one or more of these are contained in all components.
It is contained so as to be about 1.9 to 20%, preferably about 1.9 to 5%. If the content ratio of this component exceeds 20%, the meltability of the glass will deteriorate.

ZrO ₂ , La ₂ O ₃ , Y ₂ O ₃ , Ta ₂ O ₃ and Gd ₂ O ₃ have the effect of improving the chemical durability of the glass. During ~
0.3 to 10% approximately, Ru preferably be contained in the Do <br/> so that a 0.3 to 5 percent or so. When the content ratio of this component exceeds 10%, the devitrification becomes strong, and the stability of the glass is adversely affected.

Examples of the copper halide to be used in the second invention, CuCl, CuBr, and CuI, and these kind or two or more kinds may be used by doping the glass. As described above, these copper halides act as a colorant absorbing any wavelength component in the ultraviolet or visible region. In the second invention of the present application, at least one kind of copper halide is contained in an amount of 0.05 to 15% in the total composition of the glass.
Content, preferably about 0.3 to 8%. By setting the content ratio in glass within the above range, similarly to the case of the first invention of the present application, light having an arbitrary wavelength or less within a range of 350 to 450 nm is almost completely blocked, and light having a longer wavelength than that is blocked. Is transmitted almost completely, and a glass having a transmission characteristic having a sharp absorption characteristic with a narrow wavelength gradient width can be obtained. When the content ratio of copper halide is less than 0.05%, the above-mentioned desired effects cannot be obtained. On the contrary, when the content ratio exceeds 15%, devitrification occurs, which is not preferable.

Specific examples of uses of the ultraviolet ray blocking material according to the present invention are as follows.

(1) Glass material for mask in ultraviolet curing resin curing equipment In order to cure the ultraviolet curing resin, high energy ultraviolet rays are irradiated from a light source such as a high pressure mercury lamp or a metal halide lamp. High-energy ultraviolet rays, which are indispensable for curing the resin, are not preferable from the viewpoints of ensuring worker safety and preventing deterioration of equipment. The ultraviolet shielding material according to the present invention is useful, for example, as a glass plate material for a monitoring window in a resin curing facility, or as a plate-like protective material at locations where deterioration should be prevented. It is also useful as a plate-shaped ultraviolet adjuster that blocks a part of the ultraviolet light emitted from the light source and selectively transmits only the ultraviolet light having a wavelength suitable for each resin. When used for such a purpose, the composition of the sheet glass material used in the first invention and the second invention of the present application is more preferably as follows. * First invention of the present application: SiO ₂ 55 to 75%,
_{B 2 O 3 12~30%, Al} 2 O 3 1~10%, Li 2 O,
Na ₂ O, K ₂ O, at least one 5-15% of Rb ₂ O and _{Cs 2 O, MgO, CaO,} ZnO, BaO, Sr
5% or less of at least one of O and PbO, ZrO ₂ ,
_{La 2 O 3, Y 2 O} 3, Ta 2 O 3 and Gd ₂ O ₃ of at least one 5%, and at least one from 0.3 to 8% copper halide. * Second invention of this application: SiO ₂ 10-20
%, P ₂ O ₅ 10~30 _{wt%, B 2 O 3 10~25%} , A
_{l 2 O 3 15~25%, Li} 2 O, Na 2 O, K 2 O, Rb 2
O and at least one of Cs ₂ O 5 to 15%, Mg
At least one of O, CaO, ZnO, BaO, SrO and PbO, at most 5%, ZrO ₂ , La ₂ O ₃ , Y ₂ O ₃ ,
Ta ₂ O ₃ and Gd ₂ O ₃ of at least one 5 wt% or less, and at least one copper halide 0.3 to 8
%.

(2) Protective glass materials for arts and crafts, etc. Conventional float glass is used for exterior glass for arts and crafts stores, luxury clothing stores, etc., window glasses for various laboratories, and window glasses for automobiles. Have been used. However, since float glass cannot block ultraviolet rays contained in sunlight, it may cause discoloration and deterioration of arts and crafts, discoloration and deterioration of clothing, adverse effects on various studies, and deterioration and deterioration of automotive interior parts. Failure cannot be prevented. In addition, drivers of automobiles are susceptible to skin disorders such as eye damage and sunburn due to ultraviolet rays. In contrast,
The ultraviolet ray blocking material of the present invention that blocks ultraviolet rays in sunlight sharply and selectively transmits visible light can solve or reduce the above-mentioned problems, and is useful as a protective glass material in various fields. is there. In such a field, the plate-like protective glass material used in the first invention and the second invention of the present application preferably has a composition similar to the above (1).

(3) Optical Filter Materials and Glasses for Glasses Optical glass filters have been used in conventional optical devices such as cameras, but by cutting off ultraviolet rays more sharply, a clearer image can be obtained. There is a need for new filter materials that can be obtained. In addition, as for the eyeglass glasses, there is a demand for a material capable of protecting eyes more effectively by blocking ultraviolet rays more sharply. The ultraviolet ray blocking material of the present invention which blocks ultraviolet rays sharply and selectively transmits visible light is suitable as an optical glass filter material and an eyeglass material.
The optical filter material and the spectacle glass material according to the first invention and the second invention of the present application preferably have the same composition as the above (1).

(4) Glass material for containers Since chemicals, alcohols, various drinking waters, and the like are easily deteriorated by ultraviolet rays, they are often contained in containers made of colored glass (tea glass, emerald green glass, etc.). However, the conventional colored glass is very difficult to mechanically or visually inspect the contents of the container, since the visible light is also largely blocked when sufficiently blocking the ultraviolet rays. Was. The ultraviolet shielding material of the present invention which blocks ultraviolet rays sharply but selectively transmits visible light is useful as a glass material for containers which requires inspection of contents. For example, according to a light-shielding property test for a colored container according to the glass container test method for injections B-155-5 defined by the Japanese Pharmacopoeia, the transmittance required for the container is 50% or less at a wavelength of 290 to 450 nm or less, Wavelength 590-
It is 60% or more at 610 nm or less. The ultraviolet shielding material according to the present invention sufficiently satisfies these requirements. In such a field, the first invention of the present application and the second invention of the present application
More preferably, the glass material for a container used in the present invention has the following composition. * First invention of the present application: SiO ₂ 60 to 77%, B ₂ O ₃ 10
_{~20%, Al 2 O 3 1~12} %, Li 2 O, Na 2 O, K
_At least one of ₂ O, Rb ₂ O and Cs ₂ O
%, MgO, CaO, ZnO, BaO, SrO and P
8% or less of at least one of bO, ZrO ₂ , La ₂ O ₃ ,
8% of at least one of Y ₂ O ₃ , Ta ₂ O ₃ and Gd ₂ O ₃
The following, and at least one kind of copper halide 0.3 to 8
%. * Second invention of the present application: SiO ₂ 15 to 20%, P ₂ O ₅ 15
２５25%, B ₂ O ₃ 5-20%, Al ₂ O ₃ 20-30%,
_{Li 2 O, Na 2 O,} K 2 O, at least one 5-15% of Rb ₂ O and _{Cs 2 O, MgO, CaO,} ZnO, B
at least one of aO, SrO and PbO, at most 8%,
ZrO ₂ , La ₂ O ₃ , Y ₂ O ₃ , Ta ₂ O ₃ and Gd ₂ O ₃
8% by weight or less, and at least one kind of copper halide 0.3 to 8%.

(5) Powdered UV-absorbing compounding material The UV-blocking material of the present invention capable of sharply blocking ultraviolet rays can be mixed with a resin composition, a coating composition or the like as a powder of about 1 to 10 μm. Improves weather resistance and fading of resin products and coatings. (6) Illumination glass material At present, halogen lamps, mercury lamps, metal halide lamps and the like are generally used as illumination light sources. Since these light sources emit bright but strong ultraviolet rays at the same time, when used indoors, they discolor interior equipment and cause obstacles to the skin, eyes, etc. of residents. The ultraviolet shielding material according to the present invention, which blocks harmful ultraviolet light and transmits visible light, is suitable as a glass material for lighting. The glass material for illumination according to the first invention and the second invention of the present application more preferably has the same composition as the above (1). (7) Glass material for protecting a liquid crystal panel As a light source of a projection liquid crystal panel, a halogen lamp, a mercury lamp, a metal halide lamp and the like are generally used. These light sources emit bright but strong ultraviolet light at the same time. Therefore, when the liquid crystal receives ultraviolet light, the liquid crystal is greatly deteriorated and its life is shortened. The ultraviolet shielding material according to the present invention is suitable as such a glass material for protecting a liquid crystal panel because of its excellent properties. Application No. 1
The glass material for protecting a liquid crystal panel according to the present invention and the second invention of the present application more preferably has the same composition as the above (1).

In order to produce the colored glass used in the present invention, the raw materials are blended so as to have the above-mentioned predetermined composition.
What is necessary is just to process according to the glass manufacturing method conventionally performed. For example, raw materials are prepared so as to have a predetermined composition, and 1
Melt at a temperature of about 200 to 1500 ° C., stir, clarify, pour into mold, and during or after cooling, 450 to 700
A desired glass can be obtained by performing a heat treatment at a temperature of about ° C for about 0.1 to 5 hours and performing processing such as cutting and polishing. In the above-mentioned production process, in order to mix the microcrystals of the copper halide in the glass, the copper halide or a copper compound such as copper oxide or a copper halide as a raw material for the copper halide and the copper source Together with an alkali halide compound such as lithium halide, sodium halide, potassium halide, rubidium halide, and cesium halide as a halogen source capable of forming copper halide with other raw materials so as to have a predetermined composition. What is necessary is just to mix. As the components other than the copper halide, conventional glass raw materials such as oxides, carbonates, and hydroxides that can result in predetermined components can be used as they are. The above cooling is performed at about 10 to 100 ° C./hr, preferably about 30 to 50 ° C./hr, and heating is performed at 10 to 100 ° C. so as not to cause thermal distortion of the glass.
/ Hr, preferably about 30 to 70 ° C / hr. The crystal size of the copper halide is determined by these rates and heating times. In the present invention, the size of the crystal is preferably adjusted to a diameter of about 0.1 to 10 nm. Melting step, Cu ions between Cu ^- As a, may be carried out in a neutral or reducing atmosphere. In the fining step, As ₂ O ₃ , Sb ₂ O ₃ or the like may be used as a fining agent.

[0033]

The ultraviolet shielding material according to the present invention can provide the following remarkable effects. (1) For light in the wavelength range of 250 to 800 nm, 3
Light having an arbitrary wavelength of 50 to 450 nm or less is almost completely blocked, light having a longer wavelength is almost completely transmitted, and sharp absorption characteristics with a narrow wavelength gradient are exhibited. (2) By adjusting the content and type of copper halide in the glass or a combination thereof, 350 to 45
It is possible to obtain an ultraviolet ray blocking material capable of blocking light having an arbitrary wavelength in the range of 0 nm. (3) Irradiation with light such as ultraviolet light, visible light, or near-infrared light does not change the transmission characteristics. (4) Unlike conventional colored glass, the glass itself is safe to manufacture and does not require special attention for handling and disposal, so that it is generally used without adding any additional processing equipment. Production can be performed by a typical glass production facility. (5) Since the glass has good meltability, a material having a uniform composition and stable performance can be easily obtained.

[0034]

EXAMPLES Examples and test examples are shown below to further clarify the features of the present invention.

Example 1 and Reference Examples 1-2 The raw materials were prepared so as to have the composition shown in Table 1 below, melted in an alumina crucible under the conditions shown in the table, stirred, clarified, and poured into a mold. After cooling to room temperature, a heat treatment was performed, followed by cutting and polishing to obtain a colored glass. The melting is performed in a neutral or reducing atmosphere, and the cooling rate and the heating rate in the heat treatment step are 30 ° C./hr and 50 ° C., respectively.
° C / hr. Cu ₂ O was used as a copper source, and sodium halide was used as a halogen source. In any case, melting and molding could be easily performed, and the obtained glass was excellent in chemical durability. In the fining process, it was confirmed that even if As ₂ O ₃ or Sb ₂ O ₃ was used as a fining agent, the transmission characteristics of the obtained glass did not change. In addition,
Table 2 shows the results for existing hard glass and window glass as Reference Examples 1 and 2.

[0036]

[Table 1]

[0037]

[Table 2]

Test Example 1 (1) The glass material obtained in Example 1 (thickness: 2 m)
m) was tested by irradiating light with a wavelength in the range of 300-800 nm. The result is shown in FIG. FIG. 1 shows a known CdS dopant for comparison.
Curves of glass and multilayer coating glass
Are also shown. From FIG. 1, it is apparent that the ultraviolet ray blocking material according to the present invention effectively blocks ultraviolet light and has a sharp absorption characteristic with a narrow wavelength gradient width.

(2) Each glass plate (thickness: 2 mm) obtained in Example 1 was irradiated with ultraviolet rays at a distance of 10 cm for 2 hours using a 500 W ultra-high pressure mercury lamp, and then the spectral characteristics of the glass were set to 300. The test was performed by irradiating light with a wavelength in the range of ８００800 nm. As a result, the transmittance curve before the irradiation with the ultraviolet light coincides with the transmittance curve after the irradiation with the ultraviolet light, and since the ultraviolet blocking material according to the present invention has excellent durability, the light transmission characteristic changes even when irradiated with the ultraviolet light. It turned out that there was no.

(3) The same test as in the above (1) was conducted on a commercially available material for brown glass ampules (thickness: 2 mm) and a material for emerald green drinking water containers (thickness: 10 mm). The results are shown in FIG. 2 as curve A (material for a brown glass ampoule) and curve B (material for an emerald green drinking water container).

(4) A test similar to the above (1) was conducted on commercially available materials for optical filters and eyeglass lenses (thickness: 2 mm). The result is shown in FIG.

From the results shown in the above (1) to ( 4 ), the excellent properties of the ultraviolet shielding material according to the present invention are apparent.

As shown in Test Example 2 FIG. 4, ultraviolet blocking material more resulting thickness 2mm in Example 1 at a distance 50cm from the ultraviolet irradiation lamp (1) of the output 500W (3) is disposed, 2 more
After placing the predetermined projectile (5) at a position 0 cm away,
Irradiated with ultraviolet light. After 1000 hours, the discolored state of the projectile (5) was measured with a colorimeter to determine the effect of the ultraviolet ray blocking material (3). The results are as shown in Table 3 .

[0044]

[Table 3]

From the results shown in Table 3 , the excellent effect of the ultraviolet ray blocking material according to the present invention is apparent.

[0046] 500W glass plate obtained in Test Example 3 Real Example 1 (thickness 2 mm)
UV light at a distance of 10 cm for 2 hours using an ultra-high pressure mercury lamp of
The test was performed by irradiating light having a wavelength in the range of 0 nm. As a result, the transmittance curve before irradiation with ultraviolet light coincided with the transmittance curve after irradiation with ultraviolet light, and it was clear that the glass plate as the ultraviolet light blocking material did not change its light transmission characteristics even when irradiated with ultraviolet light. became.

Examples 2 to 5 Raw materials were prepared so as to have the composition shown in Table 4 below, and a glass for an ultraviolet shielding material was obtained according to Example 1. In any case, melting and molding could be easily performed, and the obtained glass was excellent in chemical durability.
In the fining process, it was confirmed that even if As ₂ O ₃ or Sb ₂ O ₃ was used as a fining agent, the transmission characteristics of the obtained glass did not change.

[0048]

[Table 4]

Test Example 4 The spectral transmission characteristic of the glass obtained in Example 2 was 25
The test was performed by irradiating light having a wavelength in the range of 0 to 800 nm. The results are shown in FIG. 5 together with a transmittance curve of a conventional CdS-doped glass as a comparison. From FIG. 5,
It is apparent that the ultraviolet ray blocking material according to the present invention effectively blocks ultraviolet light and has sharp absorption characteristics with a narrow wavelength gradient.

Further, the glass obtained in Examples 2 to 5
After irradiating ultraviolet rays for 2 hours at a distance of 10 cm using a 00 W ultra-high pressure mercury lamp, the spectral characteristics of the glass were increased to 250
The test was performed by irradiating light with a wavelength in the range of ８００800 nm. As a result, the transmittance curve was consistent with the transmittance curves of the glasses of Examples 2 to 5 not irradiated with ultraviolet rays.
This means that even when the ultraviolet ray shielding material according to the present invention is irradiated with ultraviolet rays, the transmission characteristics are not substantially changed.

[0051]

[Brief description of the drawings]

FIG. 1 is a graph showing transmittance characteristics of one example of an ultraviolet ray blocking material according to the present invention, together with that of a known ultraviolet ray shielding material .

FIG. 2 is a graph showing transmittance characteristics of two kinds of known colored glasses.

FIG. 3 is a graph showing transmittance characteristics of commercially available optical filters and glasses for spectacle lenses.

FIG. 4 measures the ultraviolet blocking performance used in Test Example 2 .
FIG. 1 is a cross-sectional view showing an outline of an apparatus for performing the above.

FIG. 5 is a graph showing the transmittance of the ultraviolet shielding material obtained in the example of the present application .
FIG. 4 is a graph showing the properties together with those of a known ultraviolet shielding material.
You.

[Explanation of symbols]

 1 UV irradiation lamp 3 UV blocking material 5 Target

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁶ Identification number Reference number in the agency FI Technical display location C03C 4/08 C03C 4/08 14/00 14/00 G02B 5/22 G02B 5/22

Claims (16)

(57) [Claims] 1. An SiO ₂ content of 20 to 85% by weight and a B ₂ O ₃ content of 20 to 85% by weight.
75 wt%, Al ₂ O ₃ 1~10 wt%, Li ₂ O, Na ₂
At least one of O, K ₂ O, Rb ₂ O and Cs ₂ O 5
~ 15% by weight , MgO, CaO, ZnO, BaO, Sr
At least one of O and PbO 1 to 10% by weight , Zr
O ₂ , La ₂ O ₃ , Y ₂ O ₃ , at least one of Ta ₂ O ₃ and Gd ₂ O ₃ 0.5 to 10% by weight , and CuCl, C
An ultraviolet ray shielding material made of glass containing 0.05 to 15% by weight of at least one copper halide selected from uBr and CuI . 2. The ultraviolet shielding material according to claim 1, wherein the ultraviolet shielding material is a glass material for a mask in a curing equipment for an ultraviolet curing resin. 3. The ultraviolet shielding material according to claim 1, wherein the ultraviolet shielding material is a protective glass material. 4. The ultraviolet shielding material according to claim 1, wherein the ultraviolet shielding material is a window glass material. 5. The ultraviolet shielding material according to claim 1, wherein the ultraviolet shielding material is an optical filter material. 6. The ultraviolet shielding material according to claim 1, wherein the ultraviolet shielding material is a glass material for glasses. 7. The ultraviolet shielding material according to claim 1, wherein the ultraviolet shielding material is a glass material for a container. 8. The ultraviolet ray shielding material according to claim 1, wherein the ultraviolet ray shielding material is a powdered ultraviolet ray absorbing compound material. 9. SiO ₂ 8-25% by weight, P ₂ O ₅ 5-3
5 wt%, B ₂ O ₃ 10~25 wt%, Al ₂ O ₃ 10~3
5% by weight, Li ₂ O, Na ₂ O, K ₂ O, Rb ₂ O and C
at least one 5 to 20 wt% of s ₂ O, MgO, Ca
O, ZnO, BaO, at least one from 1.9 to 20 wt% of SrO and _{PbO, ZrO 2, La 2 O} 3, Y
_{At least one of 2} O ₃ , Ta ₂ O ₃ and Gd ₂ O ₃ 0.3
~ 10% by weight , and CuCl, CuBr and CuI
At least one copper halide selected from 0.05 to
An ultraviolet ray blocking material made of glass containing 15% by weight. 10. The ultraviolet shielding material according to claim 9, wherein the ultraviolet shielding material is a glass material for a mask in an ultraviolet curing resin curing equipment. 11. The ultraviolet shielding material according to claim 9, wherein the ultraviolet shielding material is a protective glass material. 12. The ultraviolet shielding material according to claim 9, wherein the ultraviolet shielding material is a window glass material. 13. The ultraviolet shielding material according to claim 9, wherein the ultraviolet shielding material is an optical filter material. 14. The ultraviolet shielding material according to claim 9, wherein the ultraviolet shielding material is a glass material for glasses. 15. The ultraviolet shielding material according to claim 9, wherein the ultraviolet shielding material is a glass material for a container. 16. The ultraviolet ray shielding material according to claim 9, wherein the ultraviolet ray shielding material is a powdery ultraviolet ray absorbing compound material.