JP4626880B2 - Method for manufacturing glass articles for building materials - Google Patents

Description

[0001]
BACKGROUND OF THE INVENTION
The present invention relates to a method for producing glass articles for building materials used as decorative materials such as interior and exterior materials for buildings and flooring materials.
[0002]
[Prior art]
As glass materials for building materials used as decorative materials such as interior and exterior materials and floor materials, crystallized glass building materials are widely known. Crystallized glass building materials have been used as a substitute for natural stone because of its design.
[0003]
[Problems to be solved by the invention]
However, in crystallized glass building materials, crystals are precipitated throughout the interior, and visible light from the outside is almost reflected near the surface, so the image of stone is stronger than glass and the texture of the glass is poor. It was.
[0004]
In addition, the crystallized glass building material is first melted in a melting furnace with a special dedicated material that is crystallized by heat treatment, and granulated to obtain granular crystalline glass, and the crystalline glass is placed in a refractory frame. Accumulating and heat-treating at a high temperature of about 1100 ° C., then polishing the surface, cutting to a desired size, processing such as chamfering, etc., so that it becomes very expensive. It had the problem that it ended up.
[0005]
In order to solve the above problems, it is also attempted to obtain glass articles for building materials by roughly crushing plate glass or bottle glass made of soda-lime glass and heat-treating at a temperature causing softening flow. There is a problem that it is easily damaged by a thermal shock at the time of cooling in the process or a thermal shock caused by a drastic change in temperature.
[0006]
The object of the present invention is to prevent the thermal shock during cooling in the heat treatment process or the thermal shock due to a drastic change in air temperature, and it can be manufactured at low cost, has excellent design gloss, and has a glass texture. A method for producing a glass article is provided.
[0007]
[Means for Solving the Problems]
The manufacturing method for glass articles for building materials according to the present invention provides a plurality of flaky, small, or granular glasses made of one or more materials, and a ceramic fiber sheet is placed on the inner wall surface of the refractory container. after the glass was filled to a process for the preparation of building materials glass article is heat-treated at a temperature of 700 to 1100 ° C., Ri der average thermal expansion coefficient of 70 × ^{10 -7} / ℃ or less at 30 to 380 ° C., In the wavelength range of 400 to 700 nm, the B ₂ O ₃ —SiO ₂ system, Al ₂ O ₃ —SiO ₂ system, or B ₂ O ₃ —Al ₂ O ₃ has a thickness of 7 mm and an average transmittance of 15 to 85%. using the glass -SiO ₂ based material, characterized by heat-treating the glass filled in the refractory container in a temperature range in which reboil.
[0008]
[Action]
In the method for producing glass for building materials of the present invention, a plurality of flaky, small, or granular glasses made of one or more materials are prepared, and a ceramic fiber sheet is placed on the inner wall surface of the refractory container. Then, it is a manufacturing method of the glass article for building materials which fills glass and heat-processes at the temperature of 700-1100 degreeC, Comprising: The glass whose average thermal expansion coefficient in 30-380 degreeC is 70 * 10 < ^-7 > / degrees C or less is used Therefore, the glass material for building materials of the present invention is not damaged by the thermal shock during cooling in the heat treatment step, and can be manufactured at a low cost. That is, the glass article for building materials of the present invention uses a glass having a thermal expansion coefficient of 70 × 10 ⁻⁷ / ° C. or less that is strong against thermal shock, and does not undergo steps such as polishing, cutting, and chamfering after heat treatment. This is because the product can be manufactured.
[0009]
Moreover, it is preferable that the manufacturing method of the glass article for building materials of this invention uses the glass of a flaky shape, a small piece shape, or a granular form of 0.5-50 mm. That is, if the glass is smaller than 0.5 mm, the number of pores in the glass is more than 10 ¹² / kg, and in the wavelength range of 400 to 700 nm, the thickness is 7 mm and the average transmittance is lower than 15%. It is not economical because the texture of the glass is poor and the cost is too high for crushing, and when it exceeds 50 mm, the pores in the glass are less than 10 ² / kg, and in the wavelength range of 400 to 700 nm, This is because the average transmittance exceeds 85% at a wall thickness of 7 mm, and the pores in the glass become large, resulting in strength deterioration.
[0010]
It is also possible to color building glass articles by mixing a predetermined amount of refractory color pigment powder with flaky, small, or granular glass in advance.
[0011]
The refractory container is preferably made of a material that does not soften and deform at a temperature of 1100 ° C. or lower, and a refractory container such as mullite, cordierite, or alumina ceramics is preferable.
[0012]
Since the ceramic fiber sheet is used as a release material, the workability is excellent and the gloss of the design surface of the glass article is excellent. In other words, it is only necessary to place the ceramic fiber sheet along the inner wall surface of the refractory container, and it is not necessary to bond the ceramic fiber sheet to the inner wall surface of the refractory container using an adhesive or water. This is because the layer is thin and the design surface is glossy.
[0013]
The ceramic fiber sheet can be used without any limitation with respect to the material and content of the ceramic fiber, the average thickness of the ceramic fiber sheet, etc., as long as it acts as a release material between the glass article and the refractory container. Ceramic fiber sheet containing alumina, silica-alumina or zirconia as the main component has high heat resistance and is difficult to react with glass, has excellent releasability, and the shape of the paper after taking out the glass article created after heat treatment Therefore, it is preferable that the release material is easily peeled and removed, and the workability is excellent, and it is difficult to become dust.
[0014]
Moreover, since the dimensional accuracy of a glass article becomes high as the average thickness of a ceramic fiber sheet is 1.0 mm or less, it is preferable.
[0015]
Further, it is preferable to use a combination of a plurality of ceramic fiber sheets having different ceramic fiber materials, ceramic fiber contents, and average sheet thicknesses because the design surface of the glass article can be variously changed.
[0016]
Further, it is preferable to apply a refractory ceramic powder on the inner wall surface of the refractory container and place a ceramic fiber sheet thereon to further improve the releasability.
[0017]
Moreover, in the manufacturing method of the glass article for building materials of this invention, it heat-processes at 700-1100 degreeC, Preferably it is 800-1000 degreeC. When the heat treatment temperature is lower than 700 ° C., the softening flow is not sufficiently performed and the mechanical strength is lowered. When the heat treatment temperature exceeds 1100 ° C., the pores of the glass article are reduced and the transmittance of visible light is increased. The structural material can be seen through, the reactivity between the glass and the ceramic fiber sheet is increased, the gloss of the design surface is remarkably deteriorated, and the glass and the refractory container are easily fused, which is not preferable.
[0018]
Moreover, since the manufacturing method of the glass article for building materials of this invention uses the glass whose average coefficient of thermal expansion in 30-380 degreeC is 70x10 < ^-7 > / degreeC or less, the thermal shock at the time of the cooling in a heat treatment process, intense air temperature No damage due to thermal shock due to changes in
[0019]
In addition, when glass having a thickness of 7 mm and an average transmittance of 15 to 85% is used in the wavelength range of 400 to 700 nm, a glass article rich in the texture of glass tends to be obtained. That is, in the wavelength range of 400 to 700 nm, when the thickness is 7 mm and the average transmittance is lower than 15%, visible light is almost reflected near the surface, so that the glass texture cannot be obtained and the average transmittance is 85. This is because the structural material can be seen through when it is constructed.
[0020]
A method of manufacturing a building material for the glass article of the present invention, B ₂ O ₃ -SiO ₂ system, Al ₂ O ₃ -SiO ₂ system or B ₂ O ₃ -Al ₂ O ₃ be used -SiO ₂ based glass Is preferred. That is, B ₂ O ₃ —SiO ₂ type, Al ₂ O ₃ —SiO ₂ type or B ₂ O ₃ —Al ₂ O ₃ —SiO ₂ type glass is resistant to thermal shock and excellent in chemical resistance. This is because the thermal shock during cooling in the heat treatment process and the thermal shock due to a drastic change in temperature are not damaged, and the weather resistance is excellent.
[0021]
In addition, in the method for producing a glass article for building material according to the present invention, when heat treatment is performed within a temperature range in which the glass is reboiled, pores are generated inside the glass article by reboil in addition to the pores formed by the gaps between the glass pieces and the grains. preferable. The temperature at which the gas dissolved in the glass starts to appear as pores is about 50 ° C. higher than the softening point of the glass. As the heat treatment temperature is further increased, pores are generated more actively inside the glass, but the viscosity of the glass also decreases, so the generated pores gradually increase, float and release to the outside of the glass. Will be. Here, the temperature range in which the glass reboils refers to the temperature range from when the gas dissolved in the glass starts to appear as pores until it is released to the outside of the glass. For example, B ₂ O ₃ − the SiO ₂ -based glass is about 800 to 1000 ° C..
[0022]
【Example】
FIG. 1 is a conceptual diagram showing the manufacturing method of the present invention, and FIG. 2 is a perspective view of a glass material for building materials produced by the manufacturing method of the present invention.
[0023]
Tables 1 and 2 show examples of the present invention, and Table 3 shows comparative examples.
[0024]
[Table 1]
[0025]
[Table 2]
[0026]
[Table 3]
[0027]
First, the ceramic fiber sheet 12 is placed as a release material on the inner side surface 11a and the inner bottom surface 11b of a cordierite fireproof container 11 having an inner size of 200 × 100 × 150 mm, and then in the fireproof container 11, Each piece of glass 13 having a size of 30 mm or less made of the materials shown in Tables 1 to 3 is filled and heat-treated at the temperatures shown in the table for 5 hours, and the block-shaped building materials of 197 × 97 × 60 mm shown in Examples 1 to 6 A glass article 20 (FIG. 2) was obtained.
[0028]
The building material glass article 20 shown in FIG. 2 is made of glass 21 having an average coefficient of thermal expansion of 30 × 10 ⁻⁷ / ° C. or less at 30 to 380 ° C., and contains a large number of pores 22 inside.
[0029]
The ceramic fiber sheet 12 used was a ceramic fiber having alumina-silica as a main component, the fiber content was 95%, and the average thickness was 0.5 mm.
[0030]
In Comparative Examples 1 to 3, glass articles for building materials were obtained in the same manner as in Example 1 except that a slurry of silica sand was applied with a brush instead of using a ceramic fiber sheet as a release material.
[0031]
The amount of pores was determined by cutting the produced glass article into about 30 × 30 × 10 mm, measuring the weight thereof, counting the number of pores present therein, and converting the number into the number per unit weight. In the crystallized glass article of Comparative Example 1, crystals were precipitated and no visible light was transmitted at all, and therefore, internal pores could not be observed and measurement was impossible. The average coefficient of thermal expansion at 30 to 380 ° C. was measured with a Rigaku thermomechanical analyzer. The average transmittance at a thickness of 7 mm in the wavelength range of 400 to 700 nm was measured with a Shimadzu spectrophotometer (UV2500PC), and the specular reflectance of the design surface was measured with a Shimadzu spectrophotometer (UV3100PC).
[0032]
The gloss of the design surface of the glass article is evaluated by visual observation, and “◎” indicates that the gloss is very excellent with almost no reaction with the mold release material, and there is a slight reaction with the mold release material, but the gloss is excellent. "○" indicates that the reaction with the release material has progressed and the gloss is inferior, "X" indicates that the reaction with the release material occurs over almost the entire surface, and the gloss is extremely inferior in the "XX""
[0033]
Since the glass articles of Comparative Examples 1 to 3 use silica sand powder as a release material, the reaction between the glass and the release material proceeds and the gloss of the design surface is poor. In particular, Comparative Example 3 has a heat treatment temperature of Since it was high, the release material adhered over the entire surface in contact with the release material, and the gloss was remarkably inferior.
[0034]
Moreover, although the crystallized glass article of Comparative Example 1 was not damaged at the time of cooling in the heat treatment step, since the crystals were precipitated, the texture of the glass was poor. Comparative Example 2 is due to the use of Na ₂ O-CaO-SiO ₂ based glass, high thermal expansion coefficient, breakage at the time of cooling in the heat treatment step occurs.
[0035]
On the other hand, since Examples 1-6 used the glass whose thermal expansion coefficient is 70x10 < ^-7 > / degrees C or less, there is no damage at the time of cooling in a heat treatment process, and also uses a ceramic fiber sheet as a mold release material, Since it was heat-treated at 1100 ° C. or lower, it became a glass article for building materials having excellent gloss and glass texture.
[0036]
【effect】
As described above, the production method of the present invention uses a glass having a thermal expansion coefficient of 70 × 10 ⁻⁷ / ° C. or less, and fills it in a refractory container on which a ceramic fiber sheet is placed, Because it is manufactured by heat treatment, it can be manufactured at a low cost without being damaged by the thermal shock during cooling in the heat treatment process or the thermal shock due to severe changes in temperature. It is possible to provide a glass article for building materials suitable as a decorative material such as a material or a flooring material.
[Brief description of the drawings]
FIG. 1 is a conceptual diagram showing a production method of the present invention.
FIG. 2 is a perspective view of a glass material for building materials according to the present invention.
[Explanation of symbols]
DESCRIPTION OF SYMBOLS 11 Refractory container 11a Inner side surface 11b Inner bottom surface 12 Ceramic fiber sheet 13 Small piece glass 20 Glass material 21 for building materials Glass 22 Pores

Claims (3)

A plurality of flaky, small, or granular glasses made of one or more materials are prepared, a ceramic fiber sheet is placed on the inner wall surface of the refractory container, the glass is filled, and 700 to 1100 ° C. a method of manufacturing a building material glass article is heat-treated at a temperature state, and are the average thermal expansion coefficient of 70 × ^{10 -7} / ℃ or less at 30 to 380 ° C., and in the wavelength range of 400 to 700 nm, thickness 7mm in average transmittance using a a _B 2 _O 3 -SiO _{2 -based,} Al ₂ O 3 -SiO ₂ system or _{B 2 O 3 -Al 2 O 3} -SiO 2 system material of glass 15-85%, the A method for producing a glass article for building materials, characterized in that the glass filled in a refractory container is heat-treated within a reboiling temperature range . A glass article having a pore size in the glass of 102 ² / kg or more and 10 ¹² / kg or less is used, using glass in the form of flakes, pieces or granules having a size of 0.5 to 50 mm. The manufacturing method of the glass article for building materials of Claim 1. The method for producing a glass article for building materials according to claim 1 or 2 , wherein a refractory color pigment powder is mixed in advance with a glass of flaky, small, or granular form .