JP2013107800A - Method for producing colored crystallized glass article - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a colored crystallized glass article excellent in design, which is a colored crystallized article obtained by fusing glass small bodies to be integrated, in which colored parts are uniformly dispersed, and boundaries between the colored part and non-colored part are clear.SOLUTION: The production method of the colored crystallized glass article includes a step of preparing a glass small body mixture by mixing a crystallizable glass small body having a property of depositing crystals while softening and deforming when heat treated at a temperature higher than the softening point and a colored crystallized glass small body having a colored crystallized glass small body having a colored component as the glass composition; and a step of depositing a crystal from the crystallizable glass small body and at the same time fusing respective glass small bodies to be integrated by heat treating the glass small body mixture at a temperature higher than the softening point of the crystallizable glass small body.

Description

  The present invention relates to a method for producing a colored crystallized glass article used as a building exterior or interior material.

  Conventionally, crystallized glass articles have been widely used as building exterior materials and interior materials. The crystallized glass article is required to have a beautiful appearance in addition to excellent weather resistance and mechanical strength. As a crystallized glass article satisfying these conditions, a large number of colored crystalline glass bodies are accumulated and then heat-treated to precipitate crystals from the crystalline glass bodies, and each crystalline glass body There has been proposed a colored crystallized glass article obtained by fusing and integrating (see Patent Documents 1 and 2).

  By the way, in recent years, with the diversification of buildings, various exterior appearances have been required for the exterior and interior of buildings. Therefore, after attaching an inorganic pigment to the surface of the crystalline glass body, which is the raw material, this is accumulated and heat treated to precipitate crystals from the crystalline glass body and fuse each crystalline glass body. A method of integrating them has been proposed (see Patent Documents 3 and 4). According to this method, a crystallized glass article exhibiting a spotted pattern or a mesh pattern in which colored portions are scattered can be obtained. In addition, by appropriately selecting the type of inorganic pigment, it is possible to give various colors to the crystallized glass article.

  In addition, by accumulating a mixture of colorless crystalline glass bodies and colored crystalline glass bodies and heat-treating them, crystals are precipitated from each crystalline glass body and fused and integrated. There has also been proposed a method for obtaining a colored crystallized glass article exhibiting a spotted pattern in which colored portions are partially exposed (see Patent Document 5).

Japanese Patent Laid-Open No. 3-146439 JP-A-6-56471 JP-A-8-104530 JP-A-8-175830 JP 2009-18986 A

  In the methods described in Patent Documents 3 and 4, especially when the crystalline glass body is large, the dispersed state of the inorganic pigment is lowered, and the softening flow of the crystalline glass body is inhibited and the softening flow is excessive. Both parts that foam are likely to occur. As a result, the obtained colored crystallized glass article tends to be inferior in design and mechanical strength.

  Further, in the method described in Patent Document 5, since the colorless crystalline glass body and the colored crystalline glass body are both relatively large and soften and flow, the obtained colored crystallized glass article has a non-colored portion and a non-colored portion. There is a tendency that the boundary of the colored portion is blurred and the design is inferior.

  In view of the above, the present invention is a colored crystallized article obtained by fusing and integrating glass bodies, where the colored portion is uniformly dispersed, and the boundary between the colored portion and the non-colored portion is clear. An object of the present invention is to provide a method for producing a colored crystallized glass article excellent in design properties.

  The present invention mixes a crystalline glass body having a property of precipitating crystals while being softened and deformed when heat-treated at a temperature higher than the softening point, and a colored crystallized glass body containing a coloring component as a glass composition. The step of preparing the glass body mixture, by heat-treating the glass body mixture at a temperature equal to or higher than the softening point of the crystalline glass body, the crystals are precipitated from the crystalline glass body, and the glass bodies are separated from each other. The present invention relates to a method for producing a colored crystallized glass article, comprising the step of fusing and integrating.

  In the method for producing a colored crystallized glass article of the present invention, a colored crystallized glass body containing a color component as a glass composition is used as a raw material. The colored crystallized glass body plays a role of revealing a colored portion in a colored crystallized glass article as a final product. The crystallized glass body, unlike the crystalline glass body, has a small softening flow during heat treatment, so in the obtained colored crystallized glass article, the boundary between the colored part and the non-colored part becomes clear, and the design property is excellent. There is an effect.

  In addition, in the conventional method in which the colored portion is exposed using the inorganic pigment powder, it is difficult to uniformly mix the inorganic pigment powder and the glass body in the manufacturing process. It was difficult to obtain a vitrified glass article. On the other hand, in the method of the present invention, a colored crystallized glass body containing a coloring component is used as a glass composition so that a colored portion appears, so the particle sizes of the crystalline glass body and the colored crystallized glass body are reduced. By adjusting appropriately (for example, making the particle sizes of both substantially the same), it becomes easy to disperse both uniformly. Thereby, it becomes possible to easily produce a colored crystallized glass article in which colored portions are uniformly dispersed.

  In addition, the glass small body as used in the field of this invention means the glass granulated material, powder, a granule, a small sphere, a small broken piece, a rod-shaped object, etc.

  Secondly, in the method for producing a colored crystallized glass article of the present invention, the coloring component is preferably a transition metal oxide.

  Thirdly, the present invention relates to a colored crystallized glass article produced by any one of the methods described above.

  Below, the manufacturing method of the colored crystallized glass article of this invention is demonstrated in detail for every process.

As the crystalline glass body, any composition system can be used as long as it satisfies various properties (mechanical strength, weather resistance, etc.) required as an exterior material or interior material after crystallization. For example, crystalline glass bodies that precipitate crystals such as β-wollastonite (β-CaO · SiO ₂ ) and diopsite (CaO · MgO · 2SiO ₂ ) as the main crystal can be mentioned.

Specific examples of the composition of the crystalline glass masses, _{mass%, SiO 2 45~75%, Al} 2 O 3 1~25%, CaO 2~25%, ZnO 0~18%, BaO 0~20% _{, 0~20% MgO, SrO 0~1.5%} , Na 2 O 1~25%, K2O 0~7%, Li 2 O 0~5%, B 2 O 3 0~1.5%, CeO 2 _{0~0.5%, SO 3 0~0.5, as} 2 O 3 0~1%, contain _Sb 2 O 3 _0~1%, precipitating β- wollastonite or diopside as the main crystal The thing which has the property to do is mentioned. In addition, you may contain the coloring component mentioned later 0-3%, 0.01-3%, especially 0.02-1%.

  In order to obtain sufficient mechanical strength as a building material, the crystalline glass body preferably has a crystallinity of 5% by mass or more by heat treatment at a softening point or higher.

The colored crystallized glass body contains a coloring component as a glass composition. Examples of the coloring component include transition metal oxides such as Co ₃ O ₄ , CoO, NiO, MnO ₂ , Fe ₂ O ₃ , Cr ₂ O ₃ , and V ₂ O ₅ .

  Below, the specific example of the manufacturing method of a colored crystallized glass body is demonstrated.

  The colored crystallized glass body is, for example, a color obtained by first preparing a bulk crystalline glass containing a coloring component in the composition by a melting method and crystallizing the bulk crystalline glass by heat treatment. The crystallized glass can be produced by pulverization using a pulverizer such as a roll crusher and then classification using a sieve or the like as necessary. Moreover, after pulverizing a bulk colored crystalline glass to obtain a colored crystalline glass body, the colored crystalline glass body may be crystallized by heat treatment. Under the present circumstances, it is preferable that content of the coloring component in the composition of colored crystallized glass (or colored crystalline glass) is 0.01 to 3%, especially 0.02 to 1% by mass%. When there is too little content of a coloring component, coloring will become inadequate and it will become difficult to obtain the colored crystallized glass article which has a desired external appearance. On the other hand, when there is too much content of a coloring component, content of another component will reduce relatively and there exists a possibility of affecting each physical property.

  The composition of the colored crystallized glass body should be the same as that of the crystalline glass body except for the difference in the content of coloring components, considering the mechanical strength and production efficiency of the colored crystallized glass article that is the final product. However, it is not limited to this. For example, as long as the viscosity, crystallinity, and thermal expansion coefficient are the same, it can be used even if the composition is significantly different from that of the crystalline glass body.

  The particle size of the crystalline glass body and the colored crystallized glass body is preferably 5 mm or less, particularly 4 mm or less. When the particle size of each glass body is too large, fusion due to heat treatment becomes insufficient and the mechanical strength tends to be inferior. In addition, from the viewpoint of improving the dispersibility of each glass body, it is preferable that the particle sizes of both are as equal as possible.

  As a method for mixing the crystalline glass body and the colored crystallized glass body, an appropriate amount is weighed, dry mixed for a while, water or a water-soluble organic binder is added, and wet mixing is preferable. Thereby, it becomes possible to mix each glass body uniformly.

  The amount of water or water-soluble organic binder added is preferably about 0.1 to 5 parts by weight with respect to 100 parts by weight of the total amount of the crystalline glass body and the colored crystallized glass body. If the amount of water or water-soluble organic binder added is too small, it tends to be difficult to uniformly mix the glass bodies. On the other hand, when there is too much addition amount of water or a water-soluble organic binder, the fine powder contained in each glass body will aggregate easily, and it will become easy to produce color nonuniformity in the colored crystallized glass article obtained.

  What is necessary is just to adjust suitably the compounding ratio of a crystalline glass body and a colored crystallized glass body according to the pattern of the target colored crystallized glass article. For example, the compounding ratio of the crystalline glass body and the colored crystallized glass body is 95: 5 to 30:70, 90:10 to 40:60, particularly 80:20 to 50:50 in mass ratio. Is preferred. When there is too much content of a crystalline glass body, it will become difficult to obtain the colored crystallized glass article which has desired designability. On the other hand, when there is too little content of a crystalline glass body, melt | fusion of each glass body will become inadequate and there exists a tendency for the mechanical strength of the colored crystallized glass article obtained to be inferior.

  Next, the obtained glass body mixture is accumulated in a refractory mold and heat-treated. Thereby, the crystalline glass body is first softened and deformed and fused to the colored crystallized glass body, and the crystalline glass bodies are also fused. Subsequently, the colored crystallized glass bodies are slightly softened and deformed, and the colored crystallized glass bodies are fused and integrated. At the same time, acicular crystals are deposited from the surface of the crystalline glass body toward the inside. Further, the colored crystallized glass body becomes smooth while maintaining the crystal phase. In this way, a colored crystallized glass article excellent in design properties can be obtained in which the colored portion and the non-colored portion are uniformly mixed, and the boundary between the colored portion and the non-colored portion is clear.

The firing temperature is a temperature range above the softening point of the crystalline glass body, and in particular, the viscosity is 10 ^4.5 to 10 ^5.5 poise (10 ^4.5 to 10 ^5.5 dPa · s). Is preferred. Specifically, although it depends on the glass composition, the firing temperature is preferably 1000 ° C. or higher, particularly preferably 1100 ° C. or higher. If the firing temperature is too low, the surface smoothness of the colored crystallized glass article is lowered, and the functionality and design tend to be inferior. On the other hand, considering the burden on the firing furnace and the fuel cost, the firing temperature is preferably 1200 ° C. or lower.

  Hereinafter, although the manufacturing method of the colored crystallized glass article of this invention is demonstrated based on an Example, this invention is not limited to these Examples.

Example 1
(1) Production of crystalline glass body by mass%, SiO ₂ 61% Al ₂ O ₃ 6.4% CaO 16% ZnO 6% BaO 4.5% B ₂ O ₃ 0.3% Na ₂ O The raw material powder prepared so as to have a glass composition of 3% K ₂ O 1.9% Li ₂ O 0.5% Sb ₂ O ₃ 0.1% was melted at 1500 ° C. for 12 hours. Next, the molten glass is thrown into water and crushed, then the crushed material is crushed with a refractory roll crusher, and the crushed material is further classified to obtain a crystalline glass body having a particle size of 0.5 to 4 mm. It was.

(2) Production of colored crystallized glass body In mass%, SiO ₂ 60.96% Al ₂ O ₃ 6.4% CaO 16% ZnO 6% BaO 4.5% B ₂ O ₃ 0.3% Na ₂ Formulated to have a glass composition of O 3.3% K ₂ O 1.9% Li ₂ O 0.5% Sb ₂ O ₃ 0.1%, Co ₃ O ₄ 0.01%, NiO 0.03% The raw material powder was melted under the same conditions as described above and then formed into a plate shape to obtain a colored crystalline glass plate. The colored crystalline glass plate was crystallized by heat treatment at 1100 ° C. for 60 minutes, then pulverized with a roll crusher and classified to obtain colored crystallized glass bodies having a particle size of 0.5 to 4 mm.

(3) Production of colored crystallized glass article The crystalline glass body and the colored crystallized glass body were weighed so as to have a weight ratio of 60:40, and dry-mixed with a mixer, and then 2 parts by weight of 5%. An aqueous polyvinyl alcohol solution was added and further stirred and mixed. The obtained mixture was accumulated in a mold made of mullite, kept at 1100 ° C. for 1 hour through a temperature raising process, and then gradually cooled to room temperature to obtain a colored crystallized glass article. The obtained colored crystallized glass article had a pattern in which white non-colored portions and light gray colored portions were uniformly dispersed. Further, the boundary between the colored portion and the non-colored portion was clear.

(Comparative Example 1)
In the production process of the colored crystallized glass body of Example 1, the colored crystallized glass body was obtained by pulverizing and classifying the colored crystallized glass plate without performing heat treatment. Using the obtained colored crystalline glass body and the crystalline glass body obtained in Example 1, a colored crystallized glass article was obtained in the same manner as in Example 1.

  In the crystallized glass article thus obtained, the white non-colored portion and the colored portion were uniformly dispersed, but the boundary between the colored portion and the non-colored portion was blurred, and the design was poor.

(Comparative Example 2)
Fe-Cr-Ni-Mn spinel inorganic pigment with respect to 100 parts by mass of the crystalline glass body obtained by pulverizing and classifying the crystalline glass produced in Example 1 so as to have a particle size of 0.5 to 2 mm. 1 part by mass was mixed. Using the mixture, firing was performed under the same conditions as in Example 1 to obtain a colored crystallized glass article.

  In the crystallized glass article thus obtained, the inorganic pigment was partially agglomerated, so the colored portion was non-uniform and the design was poor.

Claims (3)

A glass body mixture obtained by mixing a crystalline glass body having a property of precipitating crystals while being softened and deformed when heat-treated at a temperature higher than the softening point, and a colored crystallized glass body containing a coloring component as a glass composition. The process of producing,
A process of precipitating crystals from the crystalline glass bodies by heat-treating the glass body mixture at a temperature equal to or higher than the softening point of the crystalline glass bodies, and fusing and integrating the glass bodies together;
A method for producing a colored crystallized glass article, comprising:   2. The method for producing a colored crystallized glass article according to claim 1, wherein the coloring component is a transition metal oxide.   A colored crystallized glass article produced by the method according to claim 1.