JP2000344543A - Yellowish-brown-colored glass and its production - Google Patents

Abstract

PROBLEM TO BE SOLVED: To produce yellowish-brown-colored glass the demand for which is great and which is also capable of removing ultraviolet rays from the entering light, using greenish or blackish cullet as a main raw material and accordingly to promote the demand for such greenish or blackish cullet. SOLUTION: This production process comprises: melting a batch containing greenish cullet of >=90 wt.% and a reducing agent; and thereafter gradually cooling the molten batch; wherein the SO3 content in the resulting glass is adjusted to 0.01-0.1 wt.% and by effecting such a reduced state of the glass, the glass has a yellowish brown color. Since a bottle formed from such yellowish-brown-colored glass is capable of removing ultraviolet rays from the entering light and the demand for such bottles is great, the demand for greenish or blackish cullet can be promoted.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a thin brown, so-called dead leaf brown glass, which is mainly used for wine bottles and is mainly made of green cullet or black cullet, and a method for producing the same.

Conventionally, dead leaf brown glass has been produced by melting a raw batch containing silica sand, limestone and soda ash as a main raw material and adding a reducing agent and chromium oxide in a glass melting furnace. On the other hand, from the viewpoint of glass recycling, promotion of glass production using cullet as a main raw material is required.
There is a transparent cullet, a green cullet, a black cullet and the like, and the demand for the transparent cullet is high. However, the demand for the green cullet and the black cullet is sluggish. At present, for example, a greenish glass bottle using a green cullet as a main material (lightness Y = 30 to 46% in terms of 4 mm,
Dominant wavelength λd = 549-558 nm, stimulus purity Pe = 30-
74%).

[0003]

The glass produced using green cullet as the main raw material is a greenish glass, and the glass mainly containing black cullet is a greenish or blackish glass. limited. Green glass bottles have a problem that they can hardly cut off ultraviolet rays and cannot prevent the contents from being altered by ultraviolet rays. Further, the use of a black glass bottle is limited because it is difficult to visually recognize the contents. The present invention makes it possible to produce a green leaf cullet or a black cullet, which is a green leaf cullet or a black cullet, which has a high demand and also cuts ultraviolet rays by using a green cullet or a black cullet as a main raw material. It contributes to recycling.

[0004]

According to the present invention, a green cullet is contained in an amount of 90% by weight or more, and the proportion of SO3 is 0.01 to 10%.
It is a dead leaf brown glass characterized by being 0.1% by weight. The color of the dead-brown glass is lightness Y = 10-55.
%, Dominant wavelength λd = 565 to 582 nm, stimulus purity Pe = 9
It is desirable that it is 8.0% or less (converted thickness: 4 mm).

[0005] The green cullet is a cullet containing about 65% or more of glass pieces of emerald green. Table 1
Shows examples of the proportions of various glass pieces contained in the green cullet. As described above, the green cullet mainly includes emerald green glass pieces, and includes glass pieces of various colors such as light blue and dark smoke.

[Table 1]

In order to make the SO3 concentration 0.01 to 0.1% by weight, the amount of the reducing agent (mainly coke is used) added to the batch may be increased or decreased. That is, if the amount of the reducing agent is increased, the SO3 concentration is decreased, and if the amount of the reducing agent is decreased, the SO3 concentration is increased. Since the composition of the green cullet is not always constant, the amount of the reducing agent to be added cannot be strictly specified.
It is easy for those skilled in the art to make it 0.1% by weight. In a normal case, 0.05 to 0.4 parts by weight of coke as a reducing agent may be blended with 100 parts by weight of green cullet.

Emerald green glass, which is a main component of green cullet, is an oxidizing glass containing chromium, iron, and sulfur. Because it is an oxidizing glass, the yellow color of hexavalent chromium and the bluish green color of trivalent chromium
It is colored emerald green as a whole. In the present invention, a reducing agent is added to the glass to make the glass reducible, so that dead leaf brown glass is obtained. That is,
When the glass is made reducible, sulfur becomes minus divalent sulfur (existing as SO 3), and the color of the sulfur becomes amber due to the action of this and trivalent iron. Furthermore, blue-green of trivalent chromium (mostly trivalent chromium in the reduced state)
Are superimposed, and as a whole, it shows a dead leaf brown. SO
(3) If the concentration is higher than 0.1%, the color of amber by trivalent iron and sulfur is reduced, and a greenish glass is obtained.

The brown leaf glass of the present invention is produced by melting a batch containing 90% by weight or more of green cullet and a reducing agent and then gradually cooling the batch. The composition other than the greening cullet and the reducing agent is silica sand, limestone and soda ash, which are the raw materials of ordinary soda-lime glass, and sodium sulfate as a fining agent.
The addition of hematite increases the iron in the glass, which can make the amber color more intense. The amount of hematite to be added depends on the proportion of various types of glass contained in the green cullet.
0.43 parts by weight or less is suitable for 00 parts by weight.
If hematite is added in too large an amount, the color of amber will be too strong and will not be dead leaf brown.

The present invention is a dead leaf brown glass comprising at least 90% by weight of black cullet and having an SO3 concentration of 0.01 to 0.1% by weight.

The black cullet is a cullet containing about 65% or more of black (dark smoke) glass pieces. Table 2 shows examples of the proportions of various glass pieces contained in the blackened cullet. As described above, the black cullet mainly includes black (dark smoke) glass pieces and various kinds of glass pieces such as emerald green and light blue.

[Table 2]

To make the SO3 concentration 0.01 to 0.1% by weight, the amount of the reducing agent added to the batch may be increased or decreased. That is, if the amount of the reducing agent is increased, the SO3 concentration is decreased, and if the amount of the reducing agent is decreased, the SO3 concentration is increased. Since the composition of black cullet is not always constant,
Although the amount of the reducing agent to be added cannot be strictly specified, it is easy for those skilled in the art to adjust the SO3 concentration to 0.01 to 0.1% by weight. In a normal case, 0.21 to 0.94 parts by weight of coke as a reducing agent may be blended with 100 parts by weight of the blackening cullet.

The black glass, which is the main component of the black cullet, is an oxidizable glass containing chromium, iron, sulfur and manganese. Since the glass is an oxidizing glass, it is colored black as a whole by the coloration of hexavalent chromium yellow, trivalent chromium blue green and manganese red. The present invention
By adding a reducing agent to this to make the glass reducible,
Dead leaf brown glass. That is, if the glass is made reducible, manganese becomes colorless. In addition, sulfur becomes minus divalent sulfur (existing as SO3), and the color of the sulfur becomes amber due to the action of trivalent iron. Furthermore, the blue-green color of trivalent chromium (3
(Mostly chromium of the same value) are superimposed, and as a whole, it shows dead leaf brown. When the SO3 concentration is higher than 0.1%, the color of amber by trivalent iron and sulfur is reduced, and the glass becomes greenish.

The dead leaf brown glass of the present invention is produced by melting a batch containing at least 90% by weight of blackened cullet and a reducing agent, followed by slow cooling. The composition other than the darkening cullet and the reducing agent is silica sand, limestone and soda ash, which are the raw materials of ordinary soda lime glass, and sodium sulfate as a fining agent.
The addition of hematite increases the iron in the glass, which can make the amber color more intense. The amount of hematite to be added is
0.43 parts by weight or less is suitable for 0 parts by weight. If hematite is added in too large an amount, the color of amber will be too strong and will not be dead leaf brown.

[0014]

DESCRIPTION OF THE PREFERRED EMBODIMENTS Embodiment 1: Green cullet 260
0 parts by weight, 100 parts by weight of silica sand, 26.4 parts of limestone
Parts by weight, soda ash 26.4 parts by weight, hematite (Fe2O
3) A batch containing 4.00 parts by weight, 2.98 parts by weight of coke as a reducing agent, and 0.78 parts by weight of sodium sulfate (refining agent) was melted at 1450 ° C. for about 1 hour, and then stirred with a porcelain tube. The glass of Example 1 was produced by slow cooling. SO3 of this glass
Was 0.025% by weight. This glass exhibited a desired dead leaf brown color with a lightness Y = 29.3%, a main wavelength λd = 571.3 nm, and a stimulating purity Pe = 75.9 (converted thickness: 4 mm). Example 2: 100 parts by weight of silica sand, 26.4 parts by weight of limestone, soda ash 2 based on 2600 parts by weight of green cullet
A batch containing 6.4 parts by weight, 4.00 parts by weight of hematite, 3.29 parts by weight of coke, and 0.78 parts by weight of sodium sulfate was melted at 1450 ° C. for about 1 hour, then stirred in a porcelain tube, and gradually cooled. Thus, the glass of Example 2 was produced. SO3 of this glass
Was 0.031% by weight. This glass exhibited a desired dead leaf brown color with a brightness Y = 23.2%, a main wavelength λd = 573.7 nm, and a stimulating purity Pe = 85.2 (converted thickness: 4 mm).

Table 3 shows the composition, redox number and color tone of the glasses of Examples 1 and 2. The redox number of the glass of Example 1 was -1.9, and the glass of Example 2 was -3.7, and both were slightly reducing.

[Table 3]

Example 3: 100 parts by weight of silica sand, 26.4 parts by weight of limestone,
A batch containing 26.4 parts by weight of soda ash, 2.98 parts by weight of coke, and 0.78 parts by weight of sodium sulfate was added at 1450 ° C. for about 1 hour.
After melting for a period of time, the mixture was stirred with a porcelain tube and gradually cooled to produce the glass of Example 3. The SO3 ratio of this glass is 0.040
% By weight. This glass has a brightness Y = 23.4%,
Main wavelength λd = 572.8 nm, stimulus purity Pe = 87.8
(Equivalent thickness: 4 mm) and exhibited desired dead leaf brown.

Table 4 shows the composition, redox number and color tone of the glass of Example 3. The redox number of the glass of Example 3 is -50.0, which is reducible.

[Table 4]

The transmittance curves (converted thickness: 4 mm) of the glasses of Examples 1, 2 and 3 are shown in FIG.
All of the above glasses are excellent in cutting ultraviolet rays.

[0019]

According to the present invention, the green leaf cullet or the black cullet can be produced using the green cullet or the black cullet as a main material, so that the use of the green cullet and the black cullet can be promoted, and the glass can be recycled. is there. Also,
Since the dead leaf glass of the present invention effectively cuts ultraviolet rays, the bottle using the glass of the present invention can prevent the contents from being deteriorated due to the ultraviolet rays.

[Brief description of the drawings]

FIG. 1 is an explanatory diagram of a transmittance curve of a glass of an example.

Continued on the front page F-term (reference) 4G062 AA01 BB01 BB03 CC03 CC04 DA02 DB01 DC01 DD01 DE01 DF01 EA01 EB02 EC01 ED01 EE02 EF01 EG01 FA01 FA10 FB01 FC01 FD01 FE01 FF01 FG01 FH01 FJ01 FK01 H01H01 H02 HH11 HH12 HH13 HH15 HH17 HH20 JJ01 JJ03 JJ05 JJ07 JJ10 KK01 KK03 KK05 KK07 KK10 MM01 NN05 NN13

Claims (10)

[Claims] Claims 1. A green cullet containing at least 90% by weight of
Dead leaf brown glass characterized in that the proportion of SO3 is 0.01 to 0.1% by weight. 2. The dead leaf brown glass according to claim 1, wherein the color tone of the dead leaf brown glass is Y = 10 to 55%, dominant wavelength λd = 565 to 582 nm, and stimulating purity Pe = 98.0%.
Dead leaf brown glass characterized by the following (converted thickness: 4 mm) 3. A dead leaf characterized in that a batch containing at least 90% by weight of green cullet and a reducing agent is melted and then gradually cooled to make the proportion of SO3 in the glass 0.01 to 0.1% by weight. How to make brown glass 4. The method according to claim 3, wherein the batch contains a small amount of hematite (Fe2O3) so that the Fe2O3% in the glass becomes 0.05% by weight required for amber coloring.
3) A method for producing dead leaf brown glass, comprising: 5. The method of claim 3, wherein the color of the dead leaf glass is lightness Y = 10-55%, dominant wavelength λd = 565-582 nm, and stimulus purity Pe = 98.0%.
A method for producing dead leaf brown glass, characterized by the following (converted thickness: 4 mm): 6. A composition containing at least 90% by weight of black cullet,
Dead leaf brown glass characterized in that the proportion of SO3 is 0.01 to 0.1% by weight. 7. The dead leaf brown glass according to claim 6, wherein the color tone of the dead leaf brown glass is Y = 10 to 55%, dominant wavelength λd = 565 to 582 nm, and stimulation purity Pe = 98.0%.
Dead leaf brown glass characterized by the following (converted thickness: 4 mm) 8. A dead leaf characterized in that a batch containing at least 90% by weight of blackened cullet and a reducing agent is melted and then gradually cooled to make the ratio of SO3 in the glass 0.01 to 0.1% by weight. How to make brown glass 9. The production method according to claim 8, wherein the batch contains a small amount of hematite (Fe2O3) so that the Fe2O3% in the glass becomes 0.05% by weight required for amber coloring.
3) A method for producing dead leaf brown glass, comprising: 10. The method according to claim 8, wherein
The color tone of the dead leaf brown glass is lightness Y = 10-55%, dominant wavelength λd = 565-582 nm, stimulus purity Pe = 98.0.
% (Converted thickness: 4 mm) or less, the method for producing dead leaf brown glass