JPH0624792A - Oral glass having color difference between transmission light and reflecting and scattering light and its production - Google Patents

Abstract

PURPOSE:To promote the development of new products and special local products at a low cost by heating and melting a specific mixture, reheating the obtained base glass to form a phase-separated glass and reheating the glass to effect the growth of gold colloid particles. CONSTITUTION:A base glass raw material (A) is free from phosphoric acid and contains 40-65wt.% of silica, 5-20wt.% Al2O3, 10-25wt.% of B2O3, 5-20wt.% of CaCO3, 0-5wt.% of MgO and 1-10wt.% of alkali metal oxide. A vitrification assisting additive (B) is produced by using 0-5wt.% of BaCO3 and 0-3wt.% of a fluoride. A colorant (C) is produced by using 0.005-0.05wt.% of gold, 0-3wt.% of MnO2 and 0-3wt.% of rare earth element oxides based on A+B. A mixture of the components A, B and C is melted at 1200-1500 deg.C and cooled to obtain a base glass. The base glass is reheated at 600-800 deg.C, cooled and heated again at 900-1100 deg.C to obtain the objective opal glass having color difference between transmission light and reflecting and scattering light.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention has a remarkable difference between transmitted light and scattered light, that is, a blue-green color (transmitted light) ranging from blue to green and a brown-red color ranging from magenta to brown. Transmitted light-scattered light having a dichroism with (scattered light) Opal glass and method for producing the same, and transmitted light-scattered light mainly used in the field of accessories, crafts, and decorative building materials The present invention relates to a hue difference opal glass and a manufacturing method thereof.

[0002]

2. Description of the Related Art A dichroic glass similar to the present invention is disclosed as a transmitted light-reflected scattered light hue difference opal glass in Japanese Patent Application Laid-Open No. 297240/1987 related to the present applicant. The basic glass raw material disclosed in Japanese Patent Application Laid-Open No. 297240/1987 contains phosphoric acid in addition to the basic glass raw material according to claim 1 of the present application, and the raw material mixture is
After melting at 200 to 1400 ° C. and subsequent molding operations such as air blowing and pressing, phase separation heat treatment is performed at a temperature of around 600 to 800 ° C. In other words, in the process of product processing by the blow molding method of glass melt, melting → molding → phase separation →
A product is manufactured by the process procedure of commercialization. However, in the case of making a small accessory from a molded product on a plate, steps of cut molding and polishing using a diamond tool or the like will be added. The molding and polishing steps are usually performed manually, which increases the manufacturing cost of the product.

On the other hand, the step of molding and polishing can also be carried out by heat treatment, and this method realizes cost reduction. The heat treatment conditions for molding and polishing by heating are 900 to 110.
Although a temperature of about 0 ° C. is required, the above-mentioned transmitted light-reflected scattered light hue difference opal glass containing phosphoric acid is completely devitrified during the heat molding treatment and does not become an opal glass state. Is occurring.

Boric acid and phosphoric acid added to the basic glass raw material have a phase separation promoting action by the heat treatment of the glass, but especially in phosphoric acid, the phase separation promoting action becomes large and the phase separation proceeds too much. The tendency to reach devitrification is large.
The basic glass raw material disclosed in JP-A No. 297240/1987 contains phosphoric acid and devitrifies during molding and polishing by heating at 900 to 1100 ° C.

On the other hand, the applicant of the present invention, when using only boric oxide and not phosphoric acid as a phase separating agent for the glass as the basic glass raw material and not using phosphoric acid, the glass of the glass during the molding and polishing operation by heating at 900 to 1100 ° C. It has been discovered that the phase devitrification does not occur and the molding polishing by heating at low cost can be performed.

[Problems to be Solved by the Invention]

As described above, the above-mentioned JP-A-62 / 29
The transmitted light-reflected scattered light hue difference glass described in Japanese Patent No. 7240 is manufactured by adding phosphoric acid, which gives a strong phase separation tendency, to a basic glass raw material, and therefore transmitted light-reflected by a phase separation heat treatment at 600 to 800 ° C. A scattered light hue difference opal glass can be obtained. However, when it is heated to 900 to 1100 ° C., it is completely devitrified. Therefore, when manufacturing a small accessory, the transmitted light-reflected scattered light hue difference opal glass on the plate is cut with a diamond tool or the like, and subsequently polished to be commercialized. When manufacturing small ornaments, it is convenient to cut the glass on the plate and then mold and polish it by heat treatment to reduce the manufacturing cost, which is convenient, but with this transmitted light-reflected scattered light hue difference opal glass, 9
It devitrifies during molding and polishing by heating at 00 to 1100 ° C. That is, in the phosphoric acid-containing basic glass raw material described in JP-A No. 297240/1987, the optimum temperature of the heat treatment for molding polishing by the heat treatment is 900 to 1100 ° C.
Since it is in the interval between the two, devitrification occurs, and molding polishing by heating cannot be performed.

It is an object of the present invention to provide a transmitted light-scattered light hue difference opal glass and a method for producing the same, which makes it possible to apply a molding and polishing method by heating.

In addition, the present invention makes it possible to utilize volcanic ejecta (shirasu soil in southern Kyushu), which is an unused resource, and to newly utilize natural resources such as feldspar and porcelain stones. An object of the present invention is to provide a scattered light hue difference opal glass and a method for producing the same.

[0009]

Means and Actions for Solving the Problems In order to solve the above problems, the present applicant conducted a study to produce a transmitted light-reflected scattered light hue difference opal glass from a basic glass raw material containing no phosphoric acid, The composition of the basic glass raw material is silicic acid-alumina-boron oxide-calcium carbonate-magnesium oxide-alkali metal oxides, and barium carbonate and a fluoride (calcium fluoride, as a vitrification auxiliary).
(Sodium borofluoride, etc.) is added, gold is used as the main agent, and manganese dioxide and rare earth oxides (cerium oxide, yttrium oxide, neodymium oxide, etc.) are used in combination, and transmitted light-reflection scattered light hue difference opal The glass was manufactured.

In the present invention, the composition of the basic glass raw material is changed to volcanic ash soil (volcanic ash soil shirasu in southern Kyushu, etc.), feldspar, porcelain stone, silicic acid, alumina, boron oxide, alkaline earth compounds (calcium carbonate, magnesium oxide). etc),
Silica acid-alumina-boron oxide-calcium carbonate-magnesium oxide-alkali metal oxides prepared by using alkali metal compounds (lithium carbonate, sodium carbonate, etc.) as a raw material. To this basic glass raw material, barium carbonate and fluoride are added as auxiliary additives for vitrification, gold is used as a main agent as a coloring agent, and manganese dioxide and rare earth oxides (cerium oxide, yttrium oxide, neodymium oxide, etc.) are added. Add in complex.

After the raw materials are prepared, they are thoroughly mixed to obtain 120
The base glass is obtained by heating and melting at 0 to 1500 ° C. This base glass is heated again at 600 to 800 ° C. to be phase-separated to be opal vitrified or devitrified vitrified,
When heated to 900 to 1100 ° C., the opal state or devitrification state due to the phase separation is released. This 900-11
It is considered that the heat treatment at 00 ° C accelerates the particle size growth of the gold colloid at the same time as the phase separation is released. Due to the grown gold colloid, the transmitted light has a blue-green color and the reflected scattered light has a brown-red color. Then, the transmitted light-reflected scattered light hue difference opal glass which has become semitransparent due to the scattered light is manufactured.

When the scattered light spectrum and the transmitted light spectrum of this glass are measured, the scattered light spectrum has a peak of the scattering intensity of red light and the transmission spectrum has a peak of the transmitted light of blue light. That is, the color of transmitted light is different from the color of reflected and scattered light, the apparent color is brown and the transmitted light is blue-green. In a normal colored glass, the color of transmitted light and the color of reflected and scattered light are the same, and the apparent color and the color of transmitted light are the same, but the transmitted light-reflected scattered light hue difference according to the present invention. Opal glass is special because it shows a dichroism of blue-green color and brown-red color.

The composition of the basic glass raw material in the present invention is
In weight percent, silicic acid is 40-65% and alumina is 5%.
-20%, boron oxide 10-25%, calcium carbonate 5-20%, magnesium oxide 0-5%, lithium carbonate 0-10%, sodium carbonate 0-10%, potassium carbonate 0-10. %.

Further, as an auxiliary additive, 0 to 5% by weight of barium carbonate, 0 to 3% of calcium fluoride or sodium borofluoride, etc. are added to the basic glass raw material, respectively.

The colorant is 0.005 to 0.05% by weight based on the weight of the basic glass raw material and auxiliary additives.
And 0 to 3% by weight of manganese dioxide, 0 to 3% by weight of cerium oxide, yttrium oxide, neodymium oxide and other rare earth element oxides are used in combination.

In the basic glass raw material of the present invention, natural products such as volcanic ejecta, feldspar, and porcelain stone can be used as a silicic acid source. Since these natural raw materials include components other than silicic acid, the components are adjusted so that they fall within the above composition range.

The reason for setting the composition range of the basic glass raw material in the present invention will be explained. The method for producing the transmitted light-reflected scattered light hue difference opal glass of the present invention is 60
The heat treatment at 0 to 800 ° C. causes phase separation of the glass, and the heat treatment at 900 to 1100 ° C. subsequent to the phase separation causes the gold colloid generated in the glass to grow. That is, it is a necessary condition for producing the transmitted light-reflected scattered light hue difference opal glass that the basic glass has a composition that causes phase separation by heat treatment.

Silica is 40% in the basic glass raw material
When the glass composition is less than 65% or more than 65%, neither of them becomes a glass that causes phase separation due to heating, and generation and growth of gold colloid does not occur, so that the method of the present invention cannot be achieved. Alumina has the effect of suppressing the phase separation of the basic glass, and in a basic glass raw material in which the amount of alumina used exceeds 20%, phase separation does not occur due to heat treatment and gold colloid formation does not occur. Further, if the amount of alumina used is less than 5%, the immiscible devitrification phenomenon of the glass occurs, and it is difficult to form a uniform basic glass, and the method of the present invention cannot be achieved.

Boron oxide has a function as a phase separating agent. When the amount of boron oxide used exceeds 25%, phase separation due to heat treatment occurs too much and gold colloid formation does not occur.
On the other hand, if it is less than 10%, the basic glass does not undergo phase separation, and gold colloid is not produced, so that the method of the present invention cannot be achieved. Regarding calcium carbonate, it has a function of promoting the phase separation of the basic glass and antagonizes the phase separation inhibiting effect of alumina. If the amount of calcium carbonate is less than 5%, even if the amount of alumina added is 5%, the composition of the basic glass does not cause the phase separation, and the phase separation does not occur and gold colloid is not formed. On the other hand, if the content of calcium carbonate exceeds 20%, the phase separation will occur too much, or the immiscible devitrification phenomenon will occur, and the gold colloid will not be produced, so that the method of the present invention cannot be achieved. Magnesium oxide has the same effect of promoting phase separation as calcium carbonate, but it tends to give a dark color to the basic glass, and an addition amount of less than 5% is appropriate. If 1 to 2% by weight of magnesium oxide is contained in the basic glass raw material, it has an effect of reducing cracks due to abnormal expansion during molten glass molding. Therefore, 1 to 5% of magnesium oxide should be added to the basic glass raw material. Is desirable.

The alkali metal oxides have a function of lowering the viscosity of the basic glass, and alkali metal salts such as lithium carbonate, sodium carbonate and potassium carbonate are added individually or in combination. Adding more than 10% of alkali metal oxides to the basic glass raw material has the effect of suppressing phase separation, and also causes cracking due to abnormal expansion of the basic glass, so it is necessary to suppress it to less than 10%. Is.

Explaining the auxiliary additives, barium carbonate, calcium fluoride, sodium borofluoride and the like have the function of improving the meltability such as lowering the viscosity of the basic glass of the present invention, so that they are produced in the present invention. However, the transmitted light-reflected scattered light hue difference is added and used in an amount that does not affect the coloration of the opal glass. Use of less than 5% barium carbonate and less than 3% fluoride reduces the viscosity of the molten glass and improves the operability of the base glass, and does not affect the coloration of the present invention.

Explaining the colorant, gold is used as the colorant of the present invention. The general color of glass with gold is red due to the formation of gold colloids. The transmitted light-reflected scattered light hue difference opal glass produced by the method of the present invention cannot be produced unless gold is added, and the brown-red color of the reflected scattered light of the opal glass appears due to the gold colloid. It is believed that

When the amount of gold added is less than 0.005%, no coloration due to gold appears, and therefore the transmitted light-reflected scattered light hue difference opal glass cannot be produced by the method of the present invention. Further, if the amount of gold added exceeds 0.05%, a lump of gold is formed in the opal glass, which is inappropriate and uneconomical. Manganese dioxide used in combination with gold is transmitted light-
Reflected scattered light hue difference Has the effect of darkening the blue-green color of the transmitted light of opal glass, and less than 3% is added. If the content of manganese dioxide exceeds 3%, a dark color is formed, which causes undesired turbidity in the color of the opal glass. The rare earth element oxides used individually or in combination are considered to have an action of promoting the growth of gold colloid, and when these are added, the opal glass is stably produced. In addition, it is effective to make a slight change in the transmitted light of the opal glass.

[0024]

EXAMPLES Preferred examples of the present invention are shown in Examples 1 and 2. Example 1 The composition and weight% of basic glass raw materials, additives and colorants were set to the composition and weight% shown in Table 1, and these raw materials were prepared and then mixed. Then, the raw material mixture was heated and melted at a temperature of 1200 to 1500 ° C., and then cooled to obtain a base glass. This basic glass 60
After heating again at a temperature between 0 and 800 ° C. to form a phase-separated glass, it was heated again at a temperature between 900 and 1100 ° C.
As a result, transmitted light of blue-green system ranging from blue to green,
A transmitted light-reflected scattered light hue difference opal glass having a dichroism of scattered light of reddish red color ranging from red purple to brown was obtained.

[0025]

[Table 1]

Example 2 The composition and weight% of basic glass raw materials, additives and colorants were set to the composition and weight% shown in Table 2, and these raw materials were prepared and then mixed. Then, the raw material mixture was heated and melted at a temperature of 1200 to 1500 ° C., and then cooled to obtain a base glass. This base glass was heated again at a temperature between 600 and 800 ° C. to form a phase-separated glass, and then again heated at a temperature between 900 and 1100 ° C. As a result, a transmitted light-reflected scattered light hue difference opal glass having dichroism of transmitted light of blue-green system ranging from blue to green and scattered light of brown-red system ranging from red-purple to brown was obtained. .

The compositions of shirasu and feldspar in Table 2 are as follows:
It is published in the paper by Tadaharu Kuroiwa on page 625, Vol. 91 (1975) of the Japan Mining Association, and shown in Table 3.

[0028]

[Table 2]

[0029]

[Table 3]

FIG. 1 shows the transmitted light obtained in Example 2 above.
2 shows a light absorption spectrum of reflected scattered light hue difference opal glass. From this absorption spectrum, the transmitted light-reflected scattered light hue difference opal glass has an absorption peak near 600 nm corresponding to the yellow-red light band of the visible light spectrum, and does not absorb light near 500 nm corresponding to the blue-green light band. You can see that it transmits well. Therefore, when the coloring of the glass is judged only by this absorption spectrum, the color of the transmitted light-reflected scattered light hue difference opal glass should be a blue-green color due to the scattering of the transmitted light. However, since it actually looks reddish brown, I will explain the cause further.

FIG. 2 shows the transmitted light obtained in Example 2 above.
Fig. 3 shows a light scattering spectrum in the visible light region of reflected scattered light hue difference opal glass. It can be seen that the transmitted light-reflected scattered light hue difference opal glass scatters light in the red light band of 600 to 650 nm well.

Judging from the results of FIG. 1 and FIG.
The transmitted light is light in the blue-green band, and the reflected and scattered light is light in the red-orange band. Therefore, in the transmitted light-reflected scattered light hue difference opal glass obtained in Example 2 above, blue-green transmitted light,
It is considered that an apparent reddish brown color appears in combination with the strongly scattered reddish orange light.

[0033]

According to the present invention, the heat treatment step of generating and growing the gold colloid at 900 to 1100 ° C. is performed at the same time as the shaping and polishing step by heating the cut phase-separated glass, and a diamond tool or the like is used. Since the step of molding and polishing is omitted, the manufacturing cost of the product can be reduced.

Further, the transmitted light-reflected scattered light hue difference opal glass obtained by the present invention can be utilized as a glass material of special eccentricity for expressing dichroism, for glass crafts, furniture building materials, etc. It is possible to aggressively develop new products. In addition, volcanic ash soils, feldspars,
Since natural resources such as porcelain stone can be used as a raw material, development of local special products in the raw material producing area can be promoted.

[Brief description of drawings]

FIG. 1 is a graph showing a light scattering spectrum in a visible light region of transmitted light-reflected scattered light hue difference opal glass obtained by a manufacturing method according to the present invention.

FIG. 2 is a graph showing a light scattering spectrum in a visible light region of transmitted light-reflected scattered light hue difference opal glass obtained by the manufacturing method according to the present invention.

Claims (2)

[Claims] 1. A raw material is a mixture of a basic glass raw material, a vitrification auxiliary additive and a colorant, wherein the basic glass raw material does not contain phosphoric acid and contains 40 to 65% by weight of silicic acid. 5-20% alumina and 1
0 to 25% of boron oxide, 5 to 20% of calcium carbonate, 0 to 5% of magnesium oxide, and 1 to 10% of an alkali metal oxide, wherein the vitrification auxiliary additive is in a weight percentage. Of 0 to 5% barium carbonate and 0 to 3% of fluoride, and the colorant is 0.005 to 0.50% by weight based on the weight of the basic glass raw material and the vitrification auxiliary additive.
05% gold, 0-3% manganese dioxide, 0-3%
Of the rare earth element oxides, the raw material mixture is melted at a temperature between 1200 ° C. and 1500 ° C., and then cooled to obtain a basic glass.
A method for producing a transmitted light-reflected scattered light hue difference opal glass in which a phase-divided glass is reheated at a temperature of 0 to 800 ° C. and then heated to 900 to 1100 ° C. to grow a gold colloid. 2. A transmitted light-reflected scattered light hue difference opal glass manufactured by the manufacturing method according to claim 1.