JP4041546B2 - Method for producing colored crystallized glass article - Google Patents

Description

[0001]
[Industrial application fields]
The present invention relates to a method for producing a colored crystallized glass article used as a building exterior or interior material.
[0002]
[Prior art]
Conventionally, crystallized glass articles have been widely used as building exterior materials and interior materials. The crystallized glass used for this purpose is required to have a beautiful appearance in addition to excellent properties such as weather resistance and mechanical strength. For satisfying these various conditions, for example, the crystallized glass disclosed in Japanese Patent Publication No. 47-2276, Japanese Patent Publication No. 51-23966, Japanese Patent Publication No. 53-39884, etc., which is the invention of the present applicant, is known. These crystallized glasses are suitably manufactured by a method in which the original glass is formed into a glass body, integrated, and then heat-treated.
[0003]
On the other hand, with the diversification of buildings in recent years, there is a demand for diversification of decorative materials for exteriors and interiors of buildings. One of the diversification is diversification of color tone. By the way, coloring of glass or crystallized glass is generally so-called dough coloring, in which a colored oxide is added to a glass raw material to vitrify. However, this method is suitable for production of a large number of small varieties, but is not suitable for a small amount of many varieties.
[0004]
Therefore, as a manufacturing method suitable for small-quantity, multi-product production, the present applicant attaches inorganic pigment powder to the surface of a glass body in Japanese Patent Publication No. 5-43651 (corresponding publication: Patent Document 1) , and accumulates this. A method of crystallization is proposed. According to this method, various colors can be obtained by appropriately selecting an inorganic pigment, so that it is possible to cope with a small amount and a variety of production. Patent Documents 2 to 6 also disclose a method for producing a crystallized glass article that can be colored.
[Patent Document 1]
JP-A-1-157432 [Patent Document 2]
JP-A-5-163042 [Patent Document 3]
JP 63-1229025 A [Patent Literature 4]
JP 63-156024 A [Patent Document 5]
JP 63-144134 A [Patent Document 6]
[Patent Document 1] Japanese Patent Application Laid-Open No. 2-92941
[Problems to be solved by the invention]
However, in the above-described method, when an inorganic pigment powder is added, the softening flow of the glass body is inhibited, so that it is difficult to obtain a smooth flat surface at a normal heat treatment temperature. Therefore, there is a problem that it is necessary to raise the heat treatment temperature in order to flow properly.
[0006]
An object of the present invention is to provide a method for producing a colored crystallized glass article that can be heat-treated without increasing the heat treatment temperature even when inorganic pigment powder is added.
[0007]
[Means for Solving the Problems]
As a result of various experiments, the present inventors have found that the above object can be achieved by using a glass body having higher fluidity than the glass body to be used, and propose the present invention.
[0008]
That is, the method for producing a colored crystallized glass article of the present invention has a property that when heat treatment is performed at a temperature higher than the softening point, needle-like crystals are precipitated from the surface toward the inside while being softened and deformed, and the crystallinity is 15 % Of a large number of crystalline glass bodies and a large number of the crystalline glass bodies were calcined and formed into a cylindrical shape of 50 mmφ, and then on an Al ₂ O ₃ substrate at 1100 ° C. for 2 hours. A high-fluidity glass body made of crystalline glass that precipitates β-wosterite or diopsite that is heat-treated and the button diameter after heat treatment is set to 100 when the button diameter after heat treatment is 100 And a step of preparing an inorganic pigment powder composed of 0.05 to 10 parts by weight of a colored oxide with respect to 100 parts by weight of the glass body, a crystalline glass body and a high flowable glass body Body and inorganic pigment powder A step of mixing and heat-treating the glass body mixture at a temperature equal to or higher than the softening point of the crystalline glass body to fuse and integrate the glass bodies together to precipitate crystals, and to interface the glass bodies And a step of revealing a colored layer of inorganic pigment powder.
[0009]
The present invention is described in detail below.
[0010]
First, a large number of crystalline glass bodies, a large number of highly fluid glass bodies, and an inorganic pigment powder are prepared.
[0011]
As the crystalline glass body, any composition system can be used as long as it satisfies various properties (mechanical strength, weather resistance, etc.) required for exterior materials and interior materials after crystallization. Crystal glass that precipitates crystals such as β-wollastonite (β-CaO · SiO ₂ ) and diopside (CaO · MgO · 2SiO ₂ ) can be used as the main crystal. In particular, by weight, SiO ₂ 40-80%, Al ₂ O ₃ 2-15%, CaO 3-25%, ZnO 0-15%, BaO 0-20%, B ₂ O ₃ 0-10%, Na ₂ Crystallized glass having a composition of O + K ₂ O + Li ₂ O 2-20% and precipitating β-wollastonite as a main crystal, SiO ₂ 45-80%, Al ₂ O ₃ 1-25%, CaO 1 20.0%, MgO 0.5~20%, CaO + MgO 1.5~18%, BaO 0~18%, ZnO 0~18%, Na 2 O 1~15%, K 2 O 0~7%, Li A crystalline glass having a composition of ₂ O 0 to 5%, B ₂ O ₃ 0 to 10%, and P ₂ O ₅ 0 to 10% and precipitating diopside as a main crystal is preferable. In order to obtain a sufficient mechanical strength, it is desirable to use one having a crystallinity of 15% or more.
[0012]
The high fluidity glass body can be used as long as it has higher fluidity than the crystalline glass body, but it is particularly desirable to use a material that satisfies the following conditions. First, a large number of crystalline glass bodies and high-fluidity glass bodies were prepared, each glass body was pre-fired at a temperature near the softening point, molded into a cylindrical shape, and then Al ₂ O. _3. Heat treatment is performed on the substrate under normal manufacturing conditions (for example, 1100 ° C. for 2 hours), and the size of the button diameter after the heat treatment is evaluated. When the button diameter of the crystalline glass body is 100, the button diameter of the high fluidity glass body is 110 or more. If the button diameter is less than 110, the effect of increasing the fluidity and lowering the firing temperature is poor, so the ratio of the high fluidity glass bodies must be increased.
[0014]
For example, in the case of crystalline glass, glass that precipitates crystals such as β-wollastonite (β-CaO · SiO ₂ ) and diopside (CaO · MgO · 2SiO ₂ ) is used as the main crystal as described above. it can, in particular SiO ₂ 30 to 70% by _{weight%, Al 2 O 3 2~10%} , CaO 3~15%, 0~15% ZnO, BaO 0~20%, B 2 O 3 0~10% , Na ₂ O + K ₂ O + Li ₂ O 2-20% glass, β-wollastonite as the main crystal is precipitated, SiO ₂ 35-70%, Al ₂ O ₃ 1-15%, CaO 1 ~15.0%, MgO0.5~12%, CaO + MgO 1.5~13%, BaO 0~18%, ZnO 0~18%, Na 2 O 1~15%, K 2 O 0~10%, Li _{2 O 0~10%, B 2 O} 3 0~10%, P 2 O 5 Has a 10% of the composition, it is desirable to use a glass having a property of precipitating diopside as the main crystal. In order to make these glasses have higher fluidity than crystalline glass bodies, those having a lower crystallinity than crystalline glass bodies are used.
[0016]
In addition, the glass body as used in the field of this invention means a glass granulated material , a granule, a small sphere, a small broken piece, a rod-shaped object, etc.
[0017]
The inorganic pigment powder is not particularly limited as long as it is an oxide having a desired color, is excellent in heat resistance, and does not change color. For example, simple colored oxides such as NiO, MnO ₂ , CoO, Fe ₂ O ₃ , Cr ₂ O _3, Zn—Cr—Ni—Al spinel, Sn—Si—Ca—Cr—Zn sphene, Zr—Si— Pr zircon, Zr-Si-V-Pr zircon, Zr-Si-V zircon, Al-Co-Cr-Zn spinel, Al-Zn-Fe-Cr spinel, Fe-Cr-Zn-Al spinel, Fe-Cr- Colored oxides such as Zn spinel and Fe-Cr-Ni-Mn spinel are suitable, and these may be used in combination.
[0018]
Next, the crystalline glass body, the high fluidity glass body, and the inorganic pigment powder are mixed to adhere the inorganic pigment powder to the surface of the crystalline glass body or the high fluidity glass body.
[0019]
The ratio of the crystalline glass body to the highly fluid glass body is preferably 20:80 to 99.7: 0.3 by weight. Here, the reason for limiting the ratio of each glass body in this way is that it is difficult to obtain characteristics required as a building material, such as mechanical strength is lowered when the crystalline glass body is less than the above-described ratio. This is because the effect is lost when the flowable glass body is less than the above range. Moreover, although the mixing amount of inorganic pigment powder changes with the density | concentrations of the color, 0.05-10 weight part is suitable with respect to 100 weight part of glass bodies. Here, the amount of the inorganic pigment powder is set to 0.05 to 10 parts by weight. If the amount is less than 0.05 parts by weight, sufficient color development cannot be obtained, and if it exceeds 10 parts by weight, the softening flow of the glass body is significantly inhibited. This is because it is difficult to obtain a smooth flat surface even when a high fluidity glass body is added.
[0020]
In addition, as a method of mixing the crystalline glass body, the high fluidity glass body and the inorganic pigment powder, weigh them in an appropriate amount, dry-mix them, and then add water or water-soluble organic to 100 parts by weight of the glass body. What is necessary is just to add 0.1-5 weight part of binders and to fully stir and mix. The amount of water or water-soluble organic binder is 0.1 to 5 parts by weight. Generally, the particle size of the inorganic pigment and the particle size of the glass body are greatly different. Don't do it. Furthermore, since the inorganic pigment hardly adheres to the glass surface, the resulting crystallized glass article has uneven color unevenness. On the other hand, if the amount of the inorganic pigment powder exceeds 5 parts by weight, the inorganic pigment aggregates and the color unevenness is severe and not suitable.
[0021]
Next, the obtained mixture is accumulated in a refractory mold and heat-treated at a temperature higher than the softening point of the crystalline glass body, thereby softening the crystalline glass body and the high fluidity glass body. Each glass body is deformed and fused and integrated, and acicular crystals are deposited from the surface of the crystalline glass body toward the inside. A colored layer of inorganic pigment powder appears at the interface of each glass body.
[0022]
In this way, a colored crystallized glass article can be obtained.
[0023]
[Action]
In the method for producing a colored crystallized glass article according to the present invention, the use of a high-fluidity glass body having a higher fluidity than the crystalline glass body cancels out the decrease in the fluidity of the glass body due to the inorganic pigment. .
[0024]
【Example】
Hereinafter, the manufacturing method of the colored crystallized glass article of the present invention will be described based on examples.
[0025]
Example 1
First, in terms of weight percentage, SiO ₂ 63.0%, Al ₂ O ₃ 6.5%, CaO 15%, ZnO 4.3%, BaO 5%, B ₂ O ₃ 0.8%, Na ₂ O 2.8 %, K ₂ O 1.0%, Li ₂ O 1.6%, and a glass raw material prepared so as to have a composition of 1.6% was melted at 1400-1500 ° C. for 12 hours. Next, the glass was dropped into water and crushed, and then the crushed material was further crushed with a refractory roll crusher. The crushed material was classified to obtain a crystalline glass body A having a diameter of 0.5 to 2 mm. Got. This crystalline glass body A has a softening point of 800 ° C., and has a property of becoming white crystallized glass having β-wollastonite as a main crystal when heat-treated at a temperature equal to or higher than the softening point. This glass body was pre-fired, molded into a button shape of 12 × 50 mmφ, placed on an Al ₂ O ₃ substrate, placed in an electric furnace, and heat treated at 1100 ° C. for 2 hours. Was 52 mm.
[0026]
Further, SiO ₂ 60% by weight _{percentage, Al 2 O 3 4.5%,} CaO 8.5%, 3.8% ZnO, BaO 13%, B 2 O 3 1.5%, Na 2 O 4.5 %, K ₂ O 2.8%, Li ₂ O 1.4% composition glass raw material was melted and granulated in the same manner as above, then pulverized and classified to 0.5 to 0.5 mm in diameter. A 2 mm high flowable glass body B was obtained. This high fluidity glass body B has a softening point of 740 ° C. and is a crystalline glass having the property of becoming white crystallized glass having β-wollastonite as the main crystal when heat-treated at a temperature equal to or higher than the softening point. It was. When a button was prepared in the same manner as described above and heat-treated at 1100 ° C. for 2 hours, the button diameter was 65 mm.
[0027]
Next, 65% by weight of crystalline glass body A and 35% by weight of high flowable glass body B were dry mixed. Next, 2 parts by weight of a Zr—Si—Pr-based yellow zircon pigment powder (average particle size 10 μm) was added to this mixture, and further 2 parts by weight of 5% PVA aqueous solution was added and stirred. This mixture was accumulated in a mullite mold and heat-treated at 1100 ° C. for 2 hours to obtain a colored crystallized glass plate.
[0028]
The crystallized glass plate thus obtained was a beautiful one having a smooth flat surface and a yellow colored layer appearing at the interface of the white glass body.
[0029]
(Comparative Example 1)
2 parts by weight of Zr—Si—Pr-based yellow zircon pigment powder is added to 100 parts by weight of the glass body to the crystalline glass body A used in Example 1, and the mixture is stirred and mixed in the same manner as in Example 1. After the accumulation, heat treatment was performed at 1100 ° C. for 2 hours.
[0030]
The crystallized glass plate thus obtained had an uneven surface where the shape of the glass body remained due to insufficient flow, and voids existed at the interface of each glass body.
[0031]
(Comparative Example 2)
First, in the same manner as in Comparative Example 1, a mixture of crystalline glass body A and pigment powder was prepared. This mixture was heat-treated at various heat treatment temperatures, and the temperature at which the surface state equivalent to Example 1 was obtained was determined. As a result, it was found that a surface equivalent to Example 1 could not be obtained unless heat treatment was performed at 1150 ° C. or higher.
[0036]
【The invention's effect】
As described above, according to the method for producing a colored crystallized glass article of the present invention, a glass body made of an inorganic pigment is used in combination with a high-fluidity glass body having higher fluidity during heat treatment than the crystalline glass body. Therefore, it is possible to produce a colored crystallized glass article having a smooth flat surface without increasing the heat treatment temperature.

Claims (1)

When heat treatment is performed at a temperature higher than the softening point, there is a property that needle-like crystals are precipitated from the surface toward the inside while softening and deforming, and a large number of crystalline glass bodies having a crystallinity of 15% or more, A large number of crystalline glass bodies were pre-fired and formed into a 12 × 50 mmφ cylindrical shape, and then heat-treated at 1100 ° C. for 2 hours on an Al ₂ O ₃ substrate, and the button diameter after heat treatment was set to 100. A large number of high-fluidity glass bodies made of crystalline glass on which β-wostenite or diopsite with a button diameter of 110 or more after the same treatment is deposited , and 100 parts by weight of the glass body A step of preparing 0.05 to 10 parts by weight of an inorganic pigment powder made of a colored oxide, a step of mixing a crystalline glass body, a high-fluidity glass body and an inorganic pigment powder, and glass. Crystal mixture A process in which the glass bodies are fused and integrated with each other by heat treatment at a temperature equal to or higher than the softening point of the glass bodies to precipitate crystals, and a colored layer of inorganic pigment powder appears at the interface of each glass body. A method for producing a colored crystallized glass article, comprising: