JPH0794334B2 - Tinted glass - Google Patents

Description

Detailed Description of the Invention

[0001]

FIELD OF THE INVENTION The present invention relates to colored glass.
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 photography for the purpose of absorbing light in the ultraviolet or visible range.
Such colored glass is obtained by doping glass with microcrystals such as CdS, CdSe and CdSSe which are II-VI group compound semiconductors, and these microcrystals have a certain wavelength range of light transmitted through the glass. It serves its purpose by absorbing part of it. However, the Cd compound as described above is a toxic substance, and there is a risk of impairing the health of workers in manufacturing processes such as batch preparation, transportation, and melting.
Further, it is difficult to treat the Cd compound contained in the wastewater and the waste produced when the glass is subjected to processing such as cutting, grinding and polishing, and there is a risk of causing pollution problems. For example, according to the Water Pollution Control Act, the limit of the allowable content of Cd and its compounds in the discharged water is 0.1 mg / l.
For this reason, a large amount of equipment such as pollution treatment equipment and sludge treatment equipment is required to produce the glass,
Cd compound dough glass is not an industrially suitable material.

Also in the transmittance characteristics, CdS, C
It is hard to say that glass doped with fine crystals of dSe or CdSSe has a wide wavelength inclination width (Δλ) defined by JIS B 7113 and exhibits sharp absorption. Further, multilayer coating glass is used for the same purpose. In this glass, a multilayer film is vapor-deposited on glass that does not absorb light in the ultraviolet region or the visible region, and light in a constant wavelength region is blocked by utilizing light interference between the multilayer films. However, the light blocking effect of the multilayer coating glass depends on the incident angle,
Although the light in the constant wavelength region is blocked only for the incident light in a constant direction with respect to the glass, the intended effect cannot be obtained for the incident light from other angles. In addition, the wavelength tilt width of the tilt region is wide, and it is hard to say that a sharp blocking effect is exhibited.

[0004]

DISCLOSURE OF THE INVENTION The inventor of the present invention aims to obtain a new glass having a superior coloring effect without using the Cd compound and the harmful substances which are problems in the conventional colored glass as described above. As a result of earnest research, when doping copper glass microcrystals, which are I-VII group compound semiconductors, into glass, almost completely cut off light of a certain wavelength or shorter and almost completely cut off light of a certain wavelength or longer. It was found that a colored glass having a sharp absorption characteristic with a narrow wavelength inclination width can be obtained by allowing the light to pass through, and completed the present invention.

That is, the present invention provides the following colored glass: "SiO ₂ 8 to 25 wt%, P ₂ O _{5 to} 35 wt%,
B ₂ O ₃ 30 wt% or _less, Al ₂ O 3 _{10~35 wt%, LiO 2, Na 2 O} , K 2 O, Rb 2 O and Cs
At least one 5 to 20 wt% of ₂ O, MgO, Ca
20% by weight or less of at least one of O, ZnO, BaO, SrO, and PbO, ZrO ₂ , La ₂ O ₃ , and Y
10% by weight or less of at least one of ₂ O ₃ , Ta ₂ O ₃ and Gd ₂ O ₃ , and CuCl, CuBr and Cu
Copper halide containing at least one of I 0.05 to 1
Colored glass containing 5% by weight. "

In the colored glass according to the present invention, since the glass having the above-mentioned specific composition is doped with copper halide microcrystals, it is possible to selectively transmit light of a specific wavelength, and a desired coloring effect can be obtained. Can be played. Also,
The colored glass of the present invention does not discolor even when irradiated with strong ultraviolet rays, and maintains its unique light transmission characteristics.

Of the constituent components of the colored glass of the present invention, each component other than copper halide, which is the most characteristic feature, is selected from various components conventionally used in glass. More specifically, among known glass components, SiO ₂ , P ₂ O ₅ , B ₂ O ₃ , Al ₂ O ₃ , and Li are selected.
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
To be 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 always appropriate to discuss the quantitative range of each component individually. In some cases, it cannot be said that, but the following is a prima facie basis for defining the quantitative range of each component.

Among the above components, SiO ₂ is the main component constituting the glass network, and it is preferable to contain SiO ₂ in an amount of about 8 to 25%, preferably about 10 to 20% in all components. If the content ratio exceeds 25%, the melting property of the glass deteriorates, while if it is less than 8%, the chemical durability is insufficient and discoloration is caused, which is not preferable.

P ₂ O ₅ is also a main component constituting the glass network, and is about 5 to 35% of all components, preferably 10 to 3
It is preferable that the content is 0%. Content ratio is 3
If it exceeds 5% or if it is less than 10%, it is not possible to obtain a colored glass having desired light transmittance.

B ₂ O ₃ is a component that improves the meltability of glass, and is 30% or less, preferably 10 to 2 of all components.
It is preferable that the content be 5%. Content ratio is 3
If it exceeds 0%, the chemical durability of glass becomes insufficient.

Al ₂ O ₃ is a component that suppresses devitrification of glass and improves chemical durability, and 10 to 3 out of all components are contained.
It is preferable that the content is about 5%, preferably about 15 to 25%. If the content ratio exceeds 35%, the meltability of the glass deteriorates, while if it is less than 10%, the durability of the glass decreases.

Li ₂ O, Na ₂ O and K ₂ O, Rb ₂
O and Cs ₂ O have the effect of improving the meltability of glass, and one or more of these may be contained in all components in an amount of 5 to 5.
It is preferable that the content is about 20%, preferably about 5 to 15%. 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 the glass.
It is preferable that the content is about 0% or less, preferably about 5% or less. If this content ratio exceeds 20%, the meltability of the glass deteriorates.

ZrO ₂ , La ₂ O ₃ , Y ₂ O ₃ and Ta ₂
O ₃ and Gd ₂ O ₃ have the effect of improving the chemical durability of the glass, and one or more of these are contained in an amount of about 10% or less, preferably about 5% or less in all components. Is good. If this content ratio exceeds 10%, the devitrification becomes strong and the stability of the glass is adversely affected.

In the present invention , the copper halide is CuC.
1, at least one of CuBr and CuI is used ,
The glass of the present invention may be doped with this. These copper halides act as an absorbing colorant having any wavelength in the ultraviolet ray or visible region, and in the present invention, the content of 0.
It is contained so as to be about 05 to 15%, preferably about 0.3 to 8%. By setting the content ratio in the glass within the above range, light having a certain wavelength of 350 to 450 nm or less is almost completely blocked, light having a longer wavelength than that is almost completely transmitted, and the wavelength inclination width A glass having a transmission characteristic with a narrow and sharp absorption characteristic is obtained. Content ratio is 0.0
If it is less than 5%, the above-mentioned advantageous effects cannot be obtained, and if it exceeds 15%, devitrification occurs, which is not preferable.

In order to produce the colored glass of the present invention, the raw materials may be blended so as to have the above-mentioned predetermined composition, and the glass may be treated in accordance with a conventional glass production method. For example, the raw materials are mixed so as to have a predetermined composition, and 1200 to 150
Melting at a temperature of about 0 ° C, stirring, clarification, pouring into a mold, and during or after cooling, heat treatment is performed at a temperature of about 450 to 700 ° C for about 0.1 to 5 hours, and processing such as cutting and polishing. The glass of the present invention can be obtained by In the above manufacturing process, in order to mix the fine crystals of copper halide into glass, copper halide is used, or a copper compound such as copper oxide or copper halide as a raw material thereof, and the copper source. Along with other halogenated compounds such as lithium halide, sodium halide, potassium halide, rubidium halide, and cesium halide as a halogen source capable of forming copper halide, other raw materials so as to have a predetermined composition. It may be blended. 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 addition, the above cooling is performed in order to prevent thermal distortion of the glass.
0 to 100 ° C / hr, preferably 30 to 50 ° C / h
It is important that the heating is performed at about r and at a slow rate of about 10 to 100 ° C./hr, preferably about 30 to 70 ° C./hr. The size of the copper halide crystal is determined by the speed and the heating time. In the present invention, the size of this crystal is 0.1 to 10 in diameter.
It is preferable to adjust to about nm. The melting step is preferably carried out in a neutral or reducing atmosphere so that Cu ions become Cu ⁻ during that time. In the fining step, As ₂ O ₃ , Sb ₂ O ₃ or the like may be used as a fining agent.

[0017]

The glass of the present invention can exert the following remarkable effects. (1) In light in the wavelength range of 250 to 800 nm, 3
It is possible to almost completely block light having an arbitrary wavelength of 50 to 450 nm and to transmit light having a longer wavelength than that, and to have a sharp absorption characteristic with a narrow wavelength inclination width. (2) It is possible to block light of an arbitrary wavelength within the range of 350 to 450 nm depending on the content and type of copper halide in glass or a combination thereof. (3) Even when irradiated with light such as ultraviolet rays, visible rays, and near infrared rays, the transmission characteristics do not change. (4) Unlike conventional colored glass, it is safe to manufacture and requires no special attention to handling and disposal. Manufacturing can be performed. (5) The heat treatment temperature can be lowered. (6) Since the meltability is good, a glass having a uniform composition can be easily obtained.

[0018]

EXAMPLES Examples and test examples will be shown below to further clarify the features of the present invention. Examples 1 to 8 Raw materials were mixed so as to have the composition shown in Table 1 below, and melted in an alumina crucible under the conditions shown in the same table, stirred, clarified, poured into a mold, and cooled to room temperature. Heat treatment was performed, cutting and polishing were performed 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%, respectively.
C / hr. Cu ₂ O was used as the copper source, and sodium halide was used as the halogen source. In any of the compositions, melting and molding could be easily performed, and the obtained glass was excellent in chemical durability. It was also confirmed that, in the refining process, even if As ₂ O ₃ or Sb ₂ O ₃ was used as a refining agent, the transmission characteristics of the obtained glass did not change.

[0019]

Test Example 1 The spectral transmission characteristics of the glasses obtained in Examples 1 and 4 were tested by irradiating with light having a wavelength in the range of 250 to 800 nm. The results are shown in FIG. 1 as Comparative Example 1 together with the transmittance curve of the conventional CdS-containing glass. From FIG. 1, the glass of the present invention effectively blocks light in the ultraviolet region,
Moreover, it is clear that it has a sharp absorption characteristic with a narrow wavelength tilt width.

Further, the glass of 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 250 to 800 nm.
The test was performed by irradiating with light having a wavelength in the range. As a result, it was found that the transmittance curve was in agreement with the transmittance curve of the glass of Example 1 which was not irradiated with ultraviolet light, and that the glass of the present invention had no change in the transmission characteristics even when irradiated with ultraviolet light.

[0022]

[Brief description of drawings]

FIG. 1 is a graph showing the transmittance of a colored glass according to the present invention and a known CdS-doped glass.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C03C 3/074 4/08

Claims (1)

[Claims] 1. SiO ₂ 8 to 25% by weight, P ₂ O ₅ 5 to
35 wt%, B ₂ O ₃ 30 wt% or less, Al ₂ O ₃ 10
35 _{wt%, LiO 2, Na 2 O} , K 2 O, Rb 2 O
And at least 5 to 20% by weight of Cs ₂ O, Mg
20% by weight or less of at least one of O, CaO, ZnO, BaO, SrO, and PbO, ZrO ₂ , La ₂ O ₃ ,
10% by weight or less of at least one of Y ₂ O ₃ , Ta ₂ O ₃ and Gd ₂ O ₃ , and CuCl, CuBr and C
copper halide containing at least one of uI 0.05 to
Colored glass containing 15% by weight.