JP2006008476A - Glass article for use in building, and manufacturing method for glass article for use in building - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a building glass article which is excellent in both the mechanical strengths and decorativeness as an exterior material, an internal material and an interior use materials of buildings and to provide a manufacturing method therefor. <P>SOLUTION: The building glass article is an article laminated and fused each other with such three glass layers consisting of at least two kinds of glasses having different expansion coefficients consisting of an intermediate layer 2 of the three glass layers having a higher expansion coefficient than those of the external layers 1 and as the expansion coefficient difference between the intermediate layer 2 and the external layers 1 is preferably not less than 3×10<SP>-7</SP>/K and not more than 15×10<SP>-7</SP>/K. The manufacturing method for the building glass article comprises placing in a refractory vessel in order from the bottom the first material, then thereon the second material having the higher expansion coefficient than that of the first material, and moreover thereon the third material having a lower expansion coefficient than that of the second material, and then fusing and uniting the glass materials in this refractory vessel by heat treating at a temperature of their softening points or higher. <P>COPYRIGHT: (C)2006,JPO&NCIPI

Description

  The present invention relates to an architectural glass article used as a building exterior material, interior material, or interior, and a method for producing the same.

  In recent years, with the diversification of the shape and design of buildings, many glass articles have been used for buildings in terms of functionality and decorativeness.

  For building glass articles, to decorate the surface of building structures such as glass blocks, partitions, and window plates that function as building structures such as pillars, walls, windows, ceilings, roofs, floors, etc. And architectural glass articles such as decorative plates and glass bricks.

  Some of such architectural glass articles are directly formed from a glass melt by a pressing method, a roll forming method, a casting method, and the like, and have been widely used.

  Moreover, as shown in Patent Document 1 and Patent Document 2, architectural glass articles excellent in decorativeness obtained by once producing granular glass from a glass melt and then fusing them by heat treatment are also provided. is there. Of these, the latter, in particular, has improved decorativeness by having bubbles inside the glass article.

Further, as shown in Patent Document 3, a waste glass cullet having different expansion coefficients is fused and integrated through an intermediate layer having an intermediate expansion coefficient, and a crystallized glass material having a low cost and sufficient strength is obtained. It has been devised.
Japanese Patent No. 48-65210 JP 2001-180953 A Japanese Patent Laid-Open No. 7-172865

  In general, architectural glass is required to have high mechanical strength in terms of safety and durability. However, when glass defects such as bubbles and grain boundaries occur in the glass, the mechanical strength is drastically reduced compared to those without them. In particular, when a glass defect is generated on the surface of the glass or in the vicinity of the surface, there is a possibility that the glass may be broken even by a slight impact.

  Glass articles such as Patent Document 1 and Patent Document 2 described above have decorativeness, but have air bubbles inside or remain. Therefore, there is a problem that the mechanical strength is lowered. Furthermore, it is difficult to control the generation of bubbles, and some of the bubbles are present on the surface or in the vicinity of the surface and may be destroyed even by a slight impact.

  In addition, in the case of the glass material disclosed in Patent Document 3, in addition to the above problem, the difference in the thermal expansion coefficient is relaxed by the intermediate layer glass and the three types of glass are fused, but the laminated and fused crystallized glass. In consideration of the whole material, the expansion coefficient changes sequentially from one surface to the other surface, and warpage occurs due to the stress generated during cooling. That is, glass having a high expansion coefficient has a problem that warpage is caused on the glass side having a high expansion coefficient because the glass contracts at the time of cooling more than glass having a low expansion coefficient.

  On the other hand, methods for increasing the mechanical strength of glass articles include physical strengthening by heat treatment and chemical strengthening by ion exchange. However, these strengthening methods cause an increase in equipment and processes, and there is a problem that precise control of heating and cooling conditions is required in order to uniformly strengthen the glass article.

  This invention makes it a subject to provide the manufacturing method of the glass article for buildings excellent in mechanical strength and decorativeness as an exterior material of a building, interior material, or interior use in view of said problem. .

  In the architectural glass article according to the present invention, three glass layers each using at least two kinds of glasses having different expansion coefficients are laminated and fused to each other, and are positioned in the middle of the three glass layers. The intermediate layer has a higher expansion coefficient than the outer layers on both sides thereof.

  The architectural glass article of the present invention includes three glass layers in which two or more kinds of glasses having different expansion coefficients are laminated and fused to each other, and the three glass layers have a glass layer having a high expansion coefficient. A glass layer having a low expansion coefficient is sandwiched between and an outer layer made of glass having a low expansion coefficient is laminated and fused on the outside of an intermediate layer made of glass having a high expansion coefficient. A compressive stress layer is formed on the surface, resulting in a stress distribution similar to that of tempered glass, which increases the mechanical strength of the glass article. Moreover, since the stress produced by this differs depending on the difference between the expansion coefficient with the intermediate layer and the thickness of the outer glass layer, the respective glass layers on the outer sides of both sides according to the difference with the expansion coefficient with the intermediate layer. When the stress generated on the front and back surfaces of the intermediate layer is balanced by adjusting the thickness of the intermediate layer, no warpage occurs.

  Furthermore, since a glass layer having a lower expansion coefficient than the intermediate layer located in the middle is formed as an outer layer on the outside of the glass article, bubbles are less likely to be formed on or near the surface, and the mechanical strength of the glass article is reduced. Is hard to be damaged. This is because glass with a low expansion coefficient generally has a higher softening point and higher viscosity at the heating temperature than glass with a high expansion coefficient, so that bubbles generated inside rise and reach the surface. This is because by suppressing the surface defects of factors that largely control the strength of the glass.

In the architectural glass article of the present invention, the difference between the expansion coefficient of the intermediate layer glass and the expansion coefficient of the outer layer glass is 3 × 10 ⁻⁷ / K or more and 15 × 10 ⁻⁷ / K or less. It is characterized by being.

When the difference between the expansion coefficient of the glass of the intermediate layer forming the fused three glass layers and the smaller expansion coefficient of the glass of the outer layer is smaller than 3 × 10 ⁻⁷ / K, distortion hardly occurs. , The improvement of strength cannot be expected so much. On the other hand, if the difference in expansion coefficient is greater than 15 × 10 ⁻⁷ / K, the resulting glass article is excessively distorted and is liable to break or warp, which is not preferable. Therefore, the difference in the expansion coefficient of the glass used for the three glass layers is more preferably in the range of 3 × 10 ⁻⁷ to 8 × 10 ⁻⁷ / K.

  In the architectural glass article of the present invention, the outer layers on both sides of the three glass layers are preferably made of the same kind of glass.

  If the outer layers on both sides are made of the same type of glass, the stress generated by this will be equal to the stresses on the front and back sides of the intermediate layer if the thickness of the outer layers on both sides is the same. Can be produced.

In addition, although the material of the glass used for a glass layer is not ask | required, since the difference of an expansion coefficient tends to become large, the combination of different glass types, for example, soda-lime type glass and borosilicate type glass, is not so preferable. Therefore, a combination of different glass materials in the range of 3 × 10 ⁻⁷ to 15 × 10 ⁻⁷ / K, which are similar glass materials, is preferable.

  In addition, regarding the material of the glass, while soda lime glass can be obtained at a low cost, the expansion coefficient is somewhat high, and the weather resistance is comparable to that of a general window glass. Borosilicate glass, aluminosilicate glass, and the like are more expensive than soda lime glass, but are preferable for building materials because they have good weather resistance and a low expansion coefficient. Further, crystallized glass or glass that crystallizes by heat treatment temperature may be used.

  Moreover, regarding shape, any of granular glass, plate glass, etc. may be sufficient and these may be combined. However, it is not preferable that the workability described later significantly impairs workability. For example, granular glass having an extremely large average particle diameter or extremely small granular glass has poor workability in filling. Therefore, the average particle size of the granular glass is preferably 0.5 to 50 mm. Similarly, in the case of plate glass, it is desirable that it is as flat as possible from the viewpoint of workability.

  The manufacturing method of the building glass article which concerns on this invention arrange | positions the 1st material which consists of granular glass or plate glass from one side in a fireproof container, and then the granular glass which has a higher expansion coefficient than a 1st material, or A second material made of sheet glass is arranged, and then a third material made of granular glass or sheet glass having a lower expansion coefficient than the second material is arranged, and the granular glass or sheet glass in the refractory container is disposed. It is characterized by being fused and integrated by heat treatment at a temperature equal to or higher than the softening point.

  Usually, when glass is melted, the glass is melted at a temperature in the vicinity of 2 dPa · s. However, the architectural glass article can be obtained by fusing and integrating granular glass or plate-like glass by heat treatment at a temperature equal to or higher than the softening point of the glass and a temperature at which the glass has a viscosity of 4 dPa · s. With the glass viscosity at this time, the bubbles taken inside are difficult to rise, so the bubbles remain inside the glass. When granular glass is used, the number and size of bubbles can be adjusted by changing the heat treatment temperature, the particle diameter of the granular glass, and the filling properties. That is, the higher the heat treatment temperature, the smaller the number of bubbles and the smaller the bubble diameter, and the larger the granular glass, the smaller the number of bubbles and the larger the bubble diameter. In addition, when the granular glass is filled, the bubble diameter becomes smaller as it is filled more densely.

  Further, by mixing the granular glass and the metal oxide and performing a heat treatment, the metal oxide is ionized and colored. Furthermore, the non-ionized metal oxide exists in the granular glass boundary and exhibits a pattern. A metal oxide is a metal oxide that reacts with glass and exhibits ionic color. Specifically, the metal oxide is an oxide of titanium, vanadium, chromium, manganese, iron, cobalt, nickel, copper, molybdenum, cerium, neodymium, or erbium. These metal oxides exhibit ionic color in glass, and exhibit yellow, green, blue, purple, and pink, depending on the type of glass and heat treatment conditions.

  Furthermore, it can be colored using colored glass or ceramic pigment instead of each metal oxide.

  Below, the example of the method of manufacturing the architectural glass article of this invention by the integration | stacking method is shown.

  First, a similar glass having a different expansion coefficient is pulverized or water-pulverized so that the average particle size is 0.5 to 50 mm to produce a granular glass.

  Next, prepare a refractory container and place a ceramic fiber sheet along the inner surface of the container as a release agent, or refractory consisting of silica sand, alumina powder, zirconia powder, or gypsum powder on the inner surface The ceramic powder is adhered.

  The refractory container is preferably made of a material that does not soften and deform at a temperature of 1200 ° C. or less, and particularly preferably made of mullite, cordierite, or alumina ceramics. The ceramic fiber sheet is excellent in releasability when the main component contains alumina, silica, silica-alumina or zirconia, and it is easy to remove the release agent after heat treatment.

  The refractory ceramic powder is applied to the inner surface of the refractory container by air spraying or brushing. Subsequently, a first material made of granular glass is arranged from below in a refractory container having a release agent placed on the inner surface, and a second material made of granular glass having a higher expansion coefficient than that of the first material. And a third material made of granular glass having a lower expansion coefficient than that of the second material. That is, granular glass having a low expansion coefficient is filled at an arbitrary ratio, and then granular glass having a high expansion coefficient and then granular glass having a low expansion coefficient are filled at an arbitrary ratio. Since the stress generated in the intermediate layer of the three-layer building glass article produced thereby differs depending on the difference between the expansion coefficient with the intermediate layer and the thickness of the outer glass layer, the difference with the expansion coefficient with the second material. Accordingly, when the stresses generated on the front and back surfaces of the intermediate layer are balanced by adjusting the thicknesses of the first material and the third material, warping and cracking do not occur. Subsequently, these materials are heat-treated at a temperature equal to or higher than the softening point of the glass and equal to or lower than a temperature at which the viscosity of the glass becomes 4 dPa · s, whereby the respective materials are fused and integrated to produce the architectural glass article of the present invention.

  Similarly, in the case of sheet glass, a sheet glass is processed to the same size as the area of the refractory container, and the first material composed of sheet glass having a low expansion coefficient in order from the bottom, sheet glass having a high expansion coefficient. The second material consisting of the above and the third material consisting of the sheet glass having a low expansion coefficient are laminated in this order. In the case of sheet glass, since it can be easily welded / integrated even in an inclined state or standing, an architecture having a desired curved surface by performing bending simultaneously at the time of welding / integration. Glass articles can be obtained.

Further, in the method for producing a building glass article of the present invention, the difference between the expansion coefficient of the second material and the expansion coefficient of the first material and the third material is 3 × 10 ⁻⁷ / K or more and 15 × 10. ^-7 / K or less.

If the difference between the expansion coefficient of the second material and the smaller expansion coefficient of the glass of the first material and the third material is smaller than 3 × 10 ⁻⁷ / K, the glass article for construction is hardly distorted and the strength It is not preferable because improvement of the level cannot be expected. On the other hand, if the difference in expansion coefficient is greater than 15 × 10 ⁻⁷ / K, the resulting glass article is excessively distorted and is liable to break or warp, which is not preferable. Therefore, the difference between the expansion coefficient of the second material and the expansion coefficient of the glass of the first material and the third material is more preferably in the range of 3 × 10 ⁻⁷ to 8 × 10 ⁻⁷ / K.

  Furthermore, in the method for producing a building glass article according to the present invention, the first material and the third material are preferably made of the same kind of glass.

  When the first material and the third material are the same kind of glass, the stress generated in the building glass article is equal to the stress generated on the front and back surfaces of the intermediate layer when the thickness of the first material and the third material is the same. Therefore, an architectural glass article that does not warp can be easily produced. When using granular glass, if the glass with a low expansion coefficient is not the same amount, a difference in stress occurs, and warping and cracking occur. In the case of plate glass, a plurality of plate glasses may be stacked in order to obtain a predetermined thickness. However, as described above, a glass having a low expansion coefficient that is laminated on the bottom and the surface so as not to cause a difference in stress. Must be the same number.

  The architectural glass article of the present invention is an architectural glass article that requires high mechanical strength in terms of safety and durability, and various bubbles and various metal oxides in the glass that are generally regarded as glass defects, Even when using decorative components such as colored glass or ceramic pigment grain boundaries, it has mechanical strength that can withstand practical use. Suitable for use. Further, unlike the conventional strengthening method, it is easy to manufacture because it does not involve an increase in special equipment and processes.

  The method for producing an architectural glass article of the present invention includes a first material from one side, a second material having a higher expansion coefficient than the first material, and a lower expansion coefficient than the second material. Since three materials are arranged and the glass material in the refractory container is fused and integrated by heat treatment at a temperature equal to or higher than its softening point, the present invention combines the above-mentioned decorative properties and mechanical strength. Architectural glass articles can be easily and efficiently produced.

  Below, the Example of the architectural glass article of this invention is described in detail.

It consists of a plate-like aluminosilicate glass, and uses glass A with an expansion coefficient of 37 × 10 ⁻⁷ / K and glass B with an expansion coefficient of 32 × 10 ⁻⁷ / K. A glass sample was prepared by stacking 8 sheets of glass A and 2 sheets of glass B in this order. At this time, the size of the glass A was 33 × 99 × 0.7 mm, and the size of the glass B was 33 × 99 × 0.6 mm. The expansion coefficients of these glasses represent linear expansion coefficients in the range of 30 to 380 ° C., and are values actually measured using a DILATO meter TD5010 manufactured by Mac Science.

Next, this superposed glass sample was put in a mullite container covered with a fiber sheet made of alumina and silica, heated in an electric furnace, and fused and integrated. The heating condition was that the temperature was raised from room temperature to 1100 ° C. at 5 ° C./minute, held at 1100 ° C. for 1 hour, then cooled at 2 ° C./minute, and the difference in expansion coefficient between the two glasses was 5 × 10 ⁻⁷ / An architectural glass plate of Example 1 having a three-layer structure of an outer layer 1 on both sides made of glass B being K and an intermediate layer 2 made of glass A was prepared as shown in FIG.

Example 1 Using glass C having a particle size of 1 to 2 mm and a glass C having an expansion coefficient of 100 × 10 ⁻⁷ / K and a glass D having an expansion coefficient of 92 × 10 ⁻⁷ / K. In a mullite container covered with the same fiber sheet as above, 10 g of glass D from the bottom, 40 g of glass C thereon, and further 10 g of glass D were further spread thereon.

Next, this granular soda lime glass sample was heated from room temperature to 1000 ° C. at 5 ° C./min in an electric furnace, held at 1000 ° C. for 1 hour, and then cooled at 2 ° C./min. As a result, an architectural glass plate having a three-layer structure of Example 2 in which the difference in expansion coefficient between the two types of glass was 8 × 10 ⁻⁷ / K was produced.

As Comparative Example 1, 12 plate-like aluminosilicate glasses A were stacked. The size of the glass A at this time is 33 × 99 × 0.7 mm, and the superposed glass sample is put in a mullite container covered with a fiber sheet made of alumina and silica, heated in an electric furnace, and melted. The clothes were integrated. Heating conditions were as follows: from room temperature to 1100 ° C. at 5 ° C./min, held at 1100 ° C. for 1 hour, cooled at 2 ° C./min, and a single type of glass with an expansion coefficient of 37 × 10 ⁻⁷ / K An architectural glass plate of Comparative Example 1 was prepared.

As Comparative Example 2, 12 plate-like aluminosilicate glasses B were superposed. The size of the glass B at this time is 33 × 99 × 0.7 mm, and the superposed glass sample is put in a mullite container covered with a fiber sheet made of alumina and silica, and heated and fused in an electric furnace. Integrated. The heating conditions were as follows: from room temperature to 1100 ° C. at 5 ° C./min, held at 1100 ° C. for 1 hour, then cooled at 2 ° C./min and fused and integrated, resulting in an expansion coefficient of 32 × 10 ^−7. An architectural glass plate of Comparative Example 2 made of a single kind of glass of / K was produced.

As Comparative Example 3, granular soda lime glass D having a particle diameter of 1 to 2 mm was uniformly spread in a mullite container covered with a fiber sheet. Next, the glass sample is heated from room temperature to 1000 ° C. at 5 ° C./min in an electric furnace, held at 1000 ° C. for 1 hour, and then cooled at 2 ° C./min to be fused and integrated. Then, an architectural glass plate of Comparative Example 3 made of a single kind of glass having an expansion coefficient of 92 × 10 ⁻⁷ / K was produced.

As Comparative Example 4, a plate-like aluminosilicate glass A having an expansion coefficient of 37 × 10 ⁻⁷ / K was pulverized and classified so as to have a particle system of 1 to 2 mm, and an expansion coefficient was 92 × 10 ⁻⁷ / K. In a mullite container covered with a fiber sheet, the soda lime glass D having a particle system of 1 to 2 mm is 10 g of glass A from the bottom, 40 g of glass D thereon, and further 10 g of glass A thereon. So that it was spread evenly. Next, the glass sample is heated from room temperature to 1075 ° C. at 5 ° C./min in an electric furnace, held at 1075 ° C. for 1 hour, and then cooled at 2 ° C./min to be fused and integrated. Thus, an architectural glass plate of Comparative Example 4 in which the difference in expansion coefficient between the two types of glasses was 55 × 10 ⁻⁷ / K of 15 × 10 ⁻⁷ / K or more was produced.

The strength measurement of the glass samples of the above examples and comparative examples was conducted with the ground contact surface with the container facing down, with an autograph DCS-R-2000 manufactured by Shimadzu Corporation, at a fulcrum distance of 80 mm, and a crosshead speed of 0.5 mm / min. A three-point bending test was performed. The number of tests was 5, and the average value and standard deviation of bending strength are shown in Table 1. All the samples have 1.7 to 2.5 × 10 ⁵ bubbles / kg of bubbles inside thereof, and the bubbles have excellent decorative properties by scattering light.

As is clear from the results in Table 1, the difference in expansion coefficient between the two glasses is 3 × 10 ⁻⁷ / K in a three-layer structure in which a glass layer having a low expansion coefficient is laminated with a glass layer having a high expansion coefficient interposed therebetween. The above Examples 1 and 2 which are not more than 15 × 10 ⁻⁷ / K have a bending strength about twice that of Comparative Examples 1, 2 and 3 made of a single kind of glass, and are mechanical. It can be seen that the strength is improved. Further, regarding Comparative Example 4, all five samples were damaged when taken out from the electric furnace, and the strength test could not be performed. This is because the difference in the expansion coefficient of the glass was too large, 55 × 10 ⁻⁷ , so that the glass could not withstand the generated strain. For the other samples, no damage was observed in all samples when taken out from the electric furnace. Furthermore, regarding Examples 1 and 2, the shape of breakage after the three-point bending test was finer than that of Comparative Examples 1, 2, and 3, and was similar to the broken state of tempered glass. In Examples 1 and 2 according to the production method of the present invention, it was considered that the fact that the amount of foam exposed on the surface, which was the starting point of breakage, was less than in Comparative Examples 1, 2, and 3 also contributed to the improvement in strength. It is done.

  Although the present invention is intended for architectural glass articles, the technical content is also applicable to glass articles for electronic parts.

The perspective view of the architectural glass article of this invention.

Explanation of symbols

1 Outer layer with low expansion coefficient 2 Intermediate layer with high expansion coefficient

Claims (4)

  Three glass layers each using at least two kinds of glasses having different expansion coefficients are laminated and fused to each other, and an intermediate layer positioned in the middle of the three glass layers is formed by outer layers on both sides thereof. An architectural glass article characterized by having a high expansion coefficient. The difference between the expansion coefficient of the glass of the intermediate layer and the expansion coefficient of the glass of the outer layer is 3 × 10 ⁻⁷ / K or more and 15 × 10 ⁻⁷ / K or less. Architectural glass articles.   In the refractory container, a first material made of granular glass or sheet glass is arranged from one side, then a second material made of granular glass or sheet glass having a higher expansion coefficient than the first material, and then A third material made of granular glass or sheet glass having a lower expansion coefficient than the second material is disposed, and the granular glass or sheet glass in the refractory container is heat-treated at a temperature equal to or higher than its softening point. The manufacturing method of the glass article for construction characterized by integrating. The difference between the expansion coefficient of the second material and the expansion coefficient of the first material and the third material is 3 × 10 ⁻⁷ / K or more and 15 × 10 ⁻⁷ / K or less. 3. A method for producing an architectural glass article according to 3.