KR102097085B1 - Fireproof glass - Google Patents

Abstract

By implementing a glass composition so that the glass itself has a high-temperature infrared ray blocking function, it provides a glass that can be used for fire protection without using a bonding film. The glass according to the present invention, SiO ₂ 50 ~ 70 wt%, B ₂ O ₃ 5 ~ 15 wt%, Al ₂ O ₃ 10 ~ 25 wt%, CaO 0 ~ 9.5 wt%, MgO 0 ~ 10 wt%, SrO 100 parts by weight of the parent glass component including 0 to 10 wt%, BaO 0 to 10 wt%, and ZnO 0 to 10 wt%; And TiO ₂ and ZrO ₂ It contains a nucleating agent containing at least any one of more than 0 to 10 parts by weight.

Description

Fireproof glass {Fireproof glass}

The present invention relates to glass, its use and manufacturing technology, and more particularly, to a fire-retardant glass and a glass composition for manufacturing the same.

Fireproof glass is a glass that prevents the spread of flames for a certain period of time when a fire occurs. In general, glass used in buildings (general plate glass) has a higher coefficient of thermal expansion than other glass, but has a low softening point, and is easily damaged by a sudden heat shock in the event of a fire, and becomes a path for propagation of flames. In particular, places such as commercial buildings and offices are places where fire protection performance is greatly required, and thus the need for fire protection glass in these places becomes greater.

The glass used for the existing fireproof glass includes a ruined soda lime glass, tempered soda lime glass, LAS-based ceramic glass, borosilicate glass, and the like. Among these glasses, LAS-based glass has an advantage of minimizing destruction due to temperature increase and change due to low thermal expansion characteristics, and since borosilicate glass is a high-distortion glass, it has an advantage that a temperature at which a shape can be maintained is high.

LAS-based ceramic glass and borosilicate glass are basically used as fire-resistant glass in the form of multilayer glass manufactured by a bonding method using a film, and exhibit high temperature durability and additional effects. However, this type of laminated glass technology is disadvantageous in that it takes a lot of time and complexity in the manufacturing process, and thus has poor mass productivity.

However, if there is no film exhibiting special effects, all of these glasses do not have a high-temperature infrared blocking function. Therefore, there is a problem in that light in the infrared region is not transmitted (radiation heat transmission) to prevent an increase in temperature in the region shielded by the fireproof glass, and above all, if a person is directly exposed to light, it cannot function as a fireproof glass.

In addition, in order to prevent optical distortion due to warping of the glass due to its own weight, the film used for bonding must maintain a suitable hardness, and at the time of bonding, it must be able to form a flat layer with moderate viscosity and dry after bonding. It must satisfy the demanding conditions such as forming a hard layer and maintaining homeostasis.

As described above, since the existing fireproof glass has to be put into a net, reinforced, or manufactured through a bonding process, a process subsequent to glass manufacturing is very cumbersome, especially when using a bonding film. .

The problem to be solved by the present invention is to provide a glass in which the glass as it is manufactured can be used for fire protection purposes even without a bonding film by implementing a glass composition so that the glass itself has a high-temperature infrared ray blocking function.

To solve the above problem, the glass according to the present invention, SiO ₂ 50 ~ 70 wt%, B ₂ O ₃ 5 ~ 15 wt%, Al ₂ O ₃ 10 ~ 25 wt%, CaO 0 ~ 9.5 wt%, MgO 100 parts by weight of the parent glass component including 0 to 10 wt%, SrO 0 to 10 wt%, BaO 0 to 10 wt% and ZnO 0 to 10 wt%; And TiO ₂ and ZrO ₂ It contains a nucleating agent containing at least any one of more than 0 to 10 parts by weight.

In a preferred embodiment, the nucleating agent includes both TiO ₂ and ZrO ₂ and may be 3 to 10 parts by weight.

SiO ₂ + Al ₂ O ₃ is 70 to 82 wt% of the parent glass component, and CaO + MgO + SrO + BaO + ZnO may be 10 to 25 wt% of the parent glass component. In this case, the nucleating agent includes both TiO ₂ and ZrO ₂ and is 3 to 10 parts by weight, and the ratio of TiO ₂ in the nucleating agent may be 32 to 50%.

Preferably, the parent glass component does not include R ₂ O (where R is at least one of Li, Na, and K).

The parent glass component may further include other components such as a clarifier or an impurity component inevitably contained in the oxide raw material itself, as long as the total weight percent satisfies 100 wt% in total.

The glass according to the present invention may be one in which crystals grow from the nucleating agent upon exposure at 750 to 1000 ° C. and transmittance of 300 nm to 5000 nm wavelength is reduced to 20% or less within 1 hour.

At this time, the crystal is preferably a single crystal or aggregated crystal size of 1 um or more. In addition, the crystal may be spherical or amorphous.

The glass according to the present invention maintains low-temperature transparency since the visible light transmittance is 80% or more at a low temperature (daily temperature).

The glass according to the present invention has a coefficient of thermal expansion of 4.7 × 10 ^-6 / K or less in a section of 100 ° C to 500 ° C. Since the coefficient of thermal expansion is very small compared to that of an ordinary plate glass, there is almost no deformation against an external temperature change. In addition, the softening point is 800 ° C or higher, and particularly, the shape change temperature is 900 ° C or higher, so it is very stable at high temperatures.

In the glass according to the present invention, crystals grow when exposed to high temperatures of 750 to 1000 ° C., and transmittance of 300 nm to 5000 nm wavelength is reduced to 20% or less within 1 hour.

Therefore, the glass according to the present invention has high temperature stability, has a small coefficient of thermal expansion, and can be used in a field in which high infrared absorption needs to be reduced at high temperatures, and is particularly suitable for glass for fire protection applications.

Compared to the fact that the existing fireproof glass maintains transparency from room temperature to high temperature, and thus has no radiant heat blocking performance at high temperature, the glass according to the present invention starts crystallization at high temperature, and the resulting crystal scatters infrared rays to reduce transmission.

Therefore, the glass according to the present invention behaves as a transparent structure window capable of securing a field of view in everyday life, and is effective in reducing infrared transmission through crystals generated in the event of fire, thereby blocking radiant heat, and is thus suitable for use as fireproof glass. .

As described above, according to the present invention, even if a net is not put into a glass, or subjected to a tempering treatment or a bonding film is used, the glass itself is maintained at a high temperature to have high temperature stability, effectively preventing flame diffusion, and fireproof glass with reduced radiant heat transmission. Can provide. Since the temperature in the area shielded by the fireproof glass is not easily increased, it is possible to greatly reduce the human life by increasing the survival time during a fire.

The following drawings attached to this specification are intended to illustrate preferred embodiments of the present invention, and serve to further understand the technical idea of the present invention together with the contents of the above-described invention, so the present invention is limited to those described in those drawings. It should not be construed limitedly.
1 is a temperature-specific spectrum in blackbody radiation.
2 is a schematic perspective view of a glass according to an embodiment of the present invention.
3 is a flow chart for explaining a glass manufacturing method according to an embodiment of the present invention.
4 is a schematic cross-sectional view of a plate glass manufacturing apparatus using a float method, which can perform a glass manufacturing method according to an embodiment of the present invention.
5 is a sample No. prepared according to an embodiment of the present invention. Pictures from 2 to 9.
6 to 8 are sample No. These are pictures after heat treatment of 2 to 9 at high temperature.
9 is a graph for viewing the change in transmittance when one type of nucleating agent is included according to an embodiment of the present invention.
10 is a sample No. prepared according to an embodiment of the present invention. Pictures from 10 to 12.
11 is a sample No. It is a photograph after 10-12 are kept at 850 ° C for 1 hour.
12 is a graph showing changes in transmittance when both types of nucleating agents are included according to an embodiment of the present invention.
13 is a sample No. prepared according to an embodiment of the present invention. 13 to 16 photos.
14 is a sample No. This is a photograph after 13 to 16 were maintained at 950 ° C for 1 hour.
15 is a graph for viewing the change in permeability according to the TiO ₂ ratio control while containing 7 parts by weight of the nucleating agent according to an embodiment of the present invention.
16 is a sample No. prepared according to an embodiment of the present invention. 19 and 20 photos.
17 is a sample No. This is a picture after 19 and 20 are kept at 900 ℃ for 1 hour.
18 is a graph for showing the change in the transmittance of the examples having a TiO ₂ ratio of 50% while including 7 parts by weight of the nucleating agent according to the present invention.
19 is a sample No. prepared according to an embodiment of the present invention. 21 to 26 photos.
20 to 22 are sample No. 21 to 26 are pictures after high-temperature heat treatment.
23 is a sample No. It is a graph for comparing the transmittance before and after crystallization of 21 to 26.
24 is a sample No. SEM pictures after crystallization of 21 to 26.

Hereinafter, exemplary embodiments of the present invention will be described in detail with reference to the accompanying drawings. However, the present invention is not limited to the embodiments disclosed below, but will be implemented in various different forms, and only the present embodiments allow the disclosure of the present invention to be complete, and the scope of the invention to those skilled in the art is completely It is provided to inform you. The same reference numbers in the drawings indicate the same components.

It is to be understood that all ranges disclosed herein include starting and ending range values and include any and all subranges subsumed within this range. For example, a range referred to as "1 to 10" means any and all subranges between a minimum value of 1 and a maximum value of 10 (including an end value), i.e., all ranges starting at a minimum value of 1 or more and ending at a maximum value of 10 or less (e.g. , 5.5 to 10).

In addition, the total wt% of the various components constituting the parent glass component in the parent glass component satisfies a total of 100 wt%.

1 is a view for helping to understand the principle in which the present invention is devised, and is a spectrum for each temperature in blackbody radiation. In Figure 1, the horizontal axis is wavelength (nm) and the vertical axis is relative intensity.

Referring to Figure 1, the peak (peak) of the black body radiation spectrum by temperature occurs mainly in the infrared wavelength band, around 400 nm at 400 ℃, 3321 nm at 600 ℃, 2702 nm at 800 ℃. As such, as the temperature increases, the peak of the radiation spectrum moves toward the shorter wavelength.

 In the case of general glass, since there is almost no transmittance above 5000 nm, the wavelength range to be considered can be said to be visible light (300 nm) to 5000 nm.

When the peak change behavior for each temperature of the black body radiation spectrum and the wavelength range to be considered in the glass are aggregated, in order to achieve the object of the present invention for the development of a fireproof glass exhibiting an infrared ray blocking effect at high temperature, a reduction in transmittance at 5000 nm or less is required. I could see.

A feature of the present invention is to impart a function to block radiant heat to the glass itself, and relates to a glass composition in which an additive called a nucleating agent is added as a method of realizing it. The nucleating agent reduces the infrared region transmittance by crystal formation and crystal growth over temperature and time depending on the crystallization mechanism of the glass. The decrease in infrared transmittance due to crystallization is due to the light scattering effect by crystals.

Since the field in which the glass according to the present invention is intended to be applied is fire-resistant glass, crystallization is preferably performed in a short time. In the present invention, the development of a glass composition was studied with the goal of realizing an effect within one hour after reaching the crystallization temperature. In addition, since the shape must be maintained at a high temperature due to the properties of the fire-resistant glass, a shape maintenance of up to 1000 ° C was aimed.

As a result of repeated studies with the above goals, the following glass composition and glass produced therefrom have been developed.

2 is a schematic perspective view of a glass according to an embodiment of the present invention.

2 (a), the glass 10 according to an embodiment of the present invention is, for example, plate-shaped glass. The glass 10 is produced from a glass composition containing 100 parts by weight of the parent glass component and more than 10 parts by weight of the nucleating agent.

The parent glass component is SiO ₂ 50 ~ 70 wt%, B ₂ O ₃ 5 ~ 15 wt%, Al ₂ O ₃ 10 ~ 25 wt%, CaO 0 ~ 9.5 wt%, MgO 0 ~ 10 wt%, SrO 0 ~ 10 wt%, BaO 0-10 wt% and ZnO 0-10 wt%.

The parent glass component may further include other components such as a clarifier or an impurity component inevitably contained in the oxide raw material itself, as long as the total weight percent satisfies 100 wt% in total.

SiO ₂ is a network structure product oxide forming glass, which can contribute to increase the chemical resistance of the glass and to have a suitable coefficient of thermal expansion that can be matched with the surrounding materials of the glass. However, when the SiO _{2 content} is too high, melting or molding of the glass becomes difficult and viscosity increases, making it difficult to clarify and homogenize the glass. And, the coefficient of thermal expansion is too low and the glass may be easy to lose transparency. On the other hand, when SiO ₂ is contained in an excessively low amount, chemical resistance is reduced, density is increased, a coefficient of thermal expansion is increased, and a strain point may be reduced. Therefore, the parent glass component contained in the glass 10 contains 50 to 70 wt% of SiO ₂ . In this range of SiO ₂ composition, chemical resistance, thermal expansion coefficient, density, and the like, which are suitable for manufacturing and using fireproof glass, can be obtained. As a result of the experiment, from the viewpoint that the infrared transmittance becomes 0 after crystallization, a preferred composition is one containing 50 to 60.2 wt% of SiO ₂ . When considering the aspect of maintaining a high temperature shape, most preferably, 55 to 60.2 wt% of SiO ₂ is included.

B ₂ O ₃ is a network structure product oxide of glass, which improves the dissolution reactivity of the glass, reduces the coefficient of thermal expansion, improves devitrification resistance, improves chemical resistance such as BHF resistance, and can contribute to lower density. (BHF: Buffered hydrofluoric acid for the etching of SiOx or SiNx, a mixed solution of hydrofluoric acid and ammonium fluoride) However, if B ₂ O ₃ is contained too high, the acid resistance of the glass may deteriorate, the density increases, and the strain point decreases and the heat resistance deteriorates. Can be. Therefore, the parent glass component contained in the glass 10 contains 5 to 15 wt% of B ₂ O ₃ . These B ₂ O ₃ The composition range can compensate for the reduced meltability due to the SiO ₂ content, and it is possible to obtain a chemical resistance, heat resistance, and thermal expansion coefficient of a degree suitable for manufacturing and using fireproof glass. As a result of the experiment, from the viewpoint that the infrared transmittance becomes 0 after crystallization, a preferred composition is one containing 5 to 10 wt% of B2O3.

Al ₂ O ₃ increases the high temperature viscosity of the glass, chemical stability, heat shock resistance, etc., and can contribute to increase the strain point and Young's modulus. However, when Al ₂ O ₃ is contained too high, devitrification resistance, hydrochloric acid resistance, and BHF resistance may be reduced and viscosity may be increased. On the other hand, when the Al ₂ O ₃ is contained too low, the effect of the addition is difficult to achieve properly and the Young's modulus may be lowered. Therefore, the parent glass component contained in the glass 10 contains 10 to 25 wt% of Al ₂ O ₃ . This composition range of Al ₂ O ₃ enables the desired physical properties to be obtained in the mechanical rigidity part, which increases the modulus of elasticity, chemical stability, and thermal shock resistance suitable for use as fireproof glass. As a result of the experiment, further considering the shape change temperature, the preferred Al ₂ O ₃ range is 12 to 25 wt%, and further considering the viewpoint that the infrared transmittance becomes 0 after crystallization, the more preferable Al ₂ O ₃ range is 15 to 25 wt%.

CaO is an alkaline earth metal oxide, which can contribute to improving the meltability without lowering the density and the coefficient of thermal expansion and significantly reducing the strain point. However, when the CaO is contained too high, the density and the coefficient of thermal expansion may increase, and chemical resistance such as BHF resistance may be deteriorated. On the other hand, if the CaO is contained too low, it is difficult to properly achieve the effect of improving properties due to the addition of the above-described CaO. Therefore, the parent glass component contained in the glass 10 contains 0 to 9.5 wt% of CaO. The preferred range of CaO is 3 to 9.5 wt% in consideration of the viewpoint that the infrared transmittance becomes 0 after crystallization.

MgO, like CaO, is an alkaline earth metal oxide, and does not increase the coefficient of thermal expansion and may contribute to improving meltability without significantly lowering the strain point. In particular, MgO can reduce the density of the glass, which can greatly contribute to the weight reduction of the glass. However, when MgO is excessively contained, the devitrification properties of the glass are lowered, and acid resistance and BHF resistance may be deteriorated. On the other hand, when MgO is contained too low, it is difficult to achieve the above-described MgO addition properties. Therefore, the parent glass component contained in the glass 10 contains 0 to 10 wt% MgO.

SrO is an alkaline earth metal oxide, and can contribute to the improvement of the devitrification properties and acid resistance of the glass. However, when SrO is contained too high, the coefficient of thermal expansion or density may increase, and devitrification characteristics may deteriorate. On the other hand, when SrO is contained too low, it is difficult to properly achieve the effect of adding SrO as described above. Therefore, the parent glass component contained in the glass 10 contains 0 to 10 wt% of SrO. As a result of the experiment, from the viewpoint that the infrared transmittance becomes 0 after crystallization, it is preferable that SrO is preferably contained in an amount of 0 to 8.5 wt%.

BaO can contribute to improving the chemical resistance and devitrification properties of glass. However, if the BaO is contained too high, the density of the glass may be increased, and adverse effects on the environment may be caused. On the other hand, when the content of BaO is too low, it is difficult to achieve the effect of adding BaO properly. Therefore, the parent glass component contained in the glass 10 contains 0 to 10 wt% of BaO. As a result of the experiment, further considering the shape change temperature, preferably, BaO is contained in an amount of 0 to 5 wt%. From the viewpoint that the infrared transmittance becomes 0 after crystallization, it is more preferably contained 0 to 4 wt%.

ZnO is effective in improving solubility, but it is easy to volatilize and shortens the life of the melting furnace, so the amount should be controlled. The parent glass component contained in the glass 10 contains 0 to 10 wt% of ZnO. From the viewpoint that the infrared transmittance becomes 0 after crystallization, ZnO is preferably contained in an amount of 0 to 7 wt%.

SiO ₂ + Al ₂ O ₃ is 70 wt% or more of the parent glass component, and CaO + MgO + SrO + BaO + ZnO is 10 to 25 wt% of the parent glass component, which is advantageous in terms of maintaining high temperature shape. More preferably, SiO ₂ + Al ₂ O ₃ is 70 to 82 wt% of the parent glass component, and CaO + MgO + SrO + BaO + ZnO is 14.4 to 22 wt% of the parent glass component. In this concentration range, the effect of containing the alkaline earth metal oxides can be improved, and the devitrification properties do not fall.

Preferably, the parent glass component does not include R ₂ O (where R is at least one of Li, Na, and K). Although R ₂ O has an effect of lowering the melting temperature, it is preferable not to include it because there is a side effect of further lowering the distortion, eroding the melting furnace, or deteriorating water resistance. Not included means that there is no intentional addition, except that it enters the impurities in the raw material itself.

The parent glass component basically has a composition capable of exerting a high distortion. Since fire-resistant glass must maintain its shape at a high temperature for the purpose of its use, glass 10 containing 100 parts by weight of the parent glass component is suitable as fire-resistant glass.

The glass 10 also contains a nucleating agent in an amount of 0 to 10 parts by weight. It is considered that the weight part of this size can maintain the characteristics of the thermal expansion coefficient and softening point expressed by the parent glass component while maintaining the transparent heat at low temperatures while completely blocking the radiant heat at high temperatures. In addition, since TiO ₂ and ZrO ₂ are more than 10 parts by weight, it is difficult to melt the homogeneous glass, so the maximum content is 10 parts by weight.

The core of the nucleating agent is that crystals are formed in a short time and the crystal size is an effective level for scattering the wavelength range (300 nm to 5000 nm) of the visible region to the ultraviolet region.

The nucleating agents that can realize this core are TiO ₂ and ZrO ₂ It includes at least one of.

In a preferred embodiment, the nucleating agent includes both TiO ₂ and ZrO ₂ and may be 3 to 10 parts by weight. In addition, the ratio of TiO ₂ in the nucleating agent may be 32 to 50%.

By including such a nucleating agent, the glass 10 can lower the infrared transmittance of the glass itself as compared to the case where only the parent glass component is included. In addition, by including such a nucleating agent, the glass 10 grows crystals from the nucleating agent upon exposure to high temperatures in the range of 750 to 1000 ° C., thereby reducing the transmittance of 300 nm to 5000 nm wavelength to 20% or less within 1 hour. The crystallization temperature and transmittance here are numerical values revealed through experiments.

FIG. 2 (b) is a schematic view of glass 10 'where crystal 20 growth has occurred due to high temperature exposure such as fire.

At this time, the crystal 20 may have a size of 1 um or more as a single crystal or an aggregated crystal, and in this case, is very effective in reducing infrared transmittance. The crystal 20 may be spherical or amorphous, especially in the case of amorphous, the effect of reducing infrared transmittance is excellent.

As described in more detail in the examples below, when the crystallization proceeds as the temperature increases due to fire, the degree of opacity varies depending on the content of the added nucleating agent, but the transmittance is 20% over the entire range of visible light to infrared light. It is lowered to below, and in particular, it is also possible to implement the performance of blocking 100% of infrared transmission.

The glass 10 having the composition as described above has a visible light transmittance of 80% or more at a low temperature (daily temperature), thereby maintaining low-temperature transparency.

In addition, the glass 10 has a thermal expansion coefficient of 4.7 × 10 ^-6 / K or less in a section of 100 ° C to 500 ° C. Since the coefficient of thermal expansion is very small compared to that of an ordinary plate glass, there is almost no deformation against an external temperature change. In addition, the softening point is 800 ° C or higher, and in particular, the shape change temperature is 900 ° C or higher, so it is stable at high temperatures.

Therefore, the glass 10 has high temperature stability, has a small coefficient of thermal expansion, and can be used in a field in which infrared absorption at high temperatures needs to be reduced, and is particularly suitable for glass for fire protection.

Compared to the fact that the existing fireproof glass maintains transparency from room temperature to high temperature, and thus has no radiation heat blocking performance at high temperature, the glass 10 begins to crystallize at high temperature, so that the resulting crystal 20 reduces infrared transmission.

Therefore, the glass 10 according to an embodiment of the present invention behaves as a structure window capable of securing a field of view in everyday life, and has an effect of blocking infrared radiation by reducing infrared transmission through crystals generated in the event of fire. Very suitable.

As described above, according to the present invention, even if a net is not put into a glass, or subjected to a tempering treatment or a bonding film is used, the glass itself is effectively kept at a high temperature and has high temperature stability, effectively preventing flame diffusion, and fire resistant glass with reduced radiant heat transmission. Can provide. Since the temperature in the area shielded by the fireproof glass is not easily increased, it is possible to greatly reduce the human life by increasing the survival time during a fire.

3 is a flow chart for explaining a glass manufacturing method according to an embodiment of the present invention.

Referring to FIG. 3, first, raw materials of each component contained in glass are combined to have a target composition (S110). At this time, in step S110, the raw materials are combined to include 100 parts by weight of the parent glass component and 10 parts by weight or less of the nucleating agent. As described above, the parent glass component is SiO ₂ 50 ~ 70 wt%, B ₂ O ₃ 5 ~ 15 wt%, Al ₂ O ₃ 10 ~ 25 wt%, CaO 0 ~ 9.5 wt%, MgO 0 ~ 10 wt%, SrO 0 to 10 wt%, BaO 0 to 10 wt% and ZnO 0 to 10 wt%, and the nucleating agent is TiO ₂ and ZrO ₂ At least one of them.

Next, the glass raw material thus combined is heated to a predetermined temperature, for example, 1500 to 1700 ° C to melt the glass raw material (S120), and after performing a clarification process, the molten glass is molded (S130).

In the melting step (S120), a glass raw material is heated in a melting furnace (not shown) to make molten glass. Next, in the clarification process, in a clarification tank in which molten glass is not shown, bubbles in the molten glass are removed using a clarifying agent. In the clarification process, as the molten glass in the clarification tank is heated, bubbles including O ₂ , CO ₂ or SO ₂ contained in the molten glass absorb and grow O ₂ generated by the reduction reaction of the clarifying agent, and the molten glass It is released by floating on the liquid level of the (degassing process). In the clarification step, after defoaming, by lowering the temperature of the molten glass, O ₂ in the bubbles remaining in the molten glass is absorbed into the molten glass by oxidation of the reactants obtained by the reduction reaction of the clarifying agent, and the bubbles are It disappears (absorption process). The oxidation reaction and reduction reaction by the clarifier is performed by controlling the temperature of the molten glass.

Following clarification, a stirring process can be performed. In the stirring process, in order to maintain the chemical and thermal uniformity of the glass, the molten glass is passed through an agitation tank not shown vertically directed. As the molten glass is stirred by the stirrer installed in the stirring tank, it moves to the bottom of the vertical downward direction and is guided to a subsequent process. Accordingly, it is possible to improve the non-uniformity of the glass such as malt.

Next, a molding process is performed (S130). At this time, step S130 may be performed by a float method using a float bath. In addition, various methods such as drawing and fusion may be used, and a rolling process may be performed for surface patterning.

When the glass is molded in step S130, the molded glass is transferred to a slow cooling furnace to undergo slow cooling (S140). Then, the annealed glass is cut to a desired size, processing such as polishing is further performed, and may be manufactured into the glass 10 through such a series of processes. In addition, a single glass 10 may be used as the fire protection glass without using film bonding or the like.

4 is a schematic cross-sectional view of a plate glass manufacturing apparatus capable of performing steps S130 and S140. This is an example of a glass forming method, and the glass manufacturing method of the present invention is not limited to such a method.

Referring to FIG. 4, the plate glass manufacturing apparatus 300 includes a float bath 220 in which molten tin 221 is accommodated therein and molten glass is formed into a flat plate shape, and a cooling furnace 240 in which molten glass is slowly cooled. And a dross box 230 for drawing molten glass from the float bath 220 and transferring the molten glass to the slow cooling furnace 240.

The molten glass is formed into a ribbon-shaped plate glass 222 on the surface of the molten tin 221 while moving from the upstream side to the downstream side of the float bath 220, and the separation position set on the downstream side of the float bath 220 ( Take off point) is pulled up to move away from the molten tin 221 by a roller (roller, 231) installed in the dross box 230, and through the dross box 230, the slow cooling furnace 240 of the next process Is sent out.

The slow cooling furnace 240 is composed of several sections, and a plurality of rollers 241 are used in one section, and a heater 242 is installed in the lower space of the roller 241. In the slow cooling furnace 240, the ribbon-shaped plate glass 222 is cooled down to the glass slow cooling point or less while temperature is controlled so that warping and bending do not occur.

The flat glass manufacturing apparatus 300 is capable of manufacturing a large flat plate glass 222. The glass 10 can be manufactured by taking out the annealed plate glass 222 from the plate glass manufacturing apparatus 300 and further performing processing such as cutting and polishing to a desired size. Since a plurality of excellent glass 10 is obtained from the plate glass 222 of a large flat plate and can be used immediately as fire protection glass, an additional process such as a netting process, a strengthening process, and a film bonding is not required. Therefore, fireproof glass can be manufactured with high productivity.

Hereinafter, examples will be described in detail to describe the present invention in more detail. However, the embodiment according to the present invention may be modified in various other forms, and the scope of the present invention should not be interpreted as being limited to the above-described embodiment. The embodiments of the present invention are provided to more fully describe the present invention to those skilled in the art.

Table 1 shows the glass composition of the examples according to the present invention.

The raw materials of each component were combined to have a composition as shown in Table 1, and heated and melted at a temperature of 1600 ° C. for 3 hours using a platinum crucible. When melting, a platinum stirrer was inserted and stirred for 1 hour to homogenize the glass. Subsequently, the molten glass was slowly cooled at 730 ° C. to obtain the example glass.

The coefficient of thermal expansion and softening point were measured for the prepared glass, and the transmittance (transmittance, transmittance) before and after crystallization was measured while the crystallization experiment was conducted through high-temperature heat treatment, and the temperature of change in transmittance and the temperature of change in shape were tested. Table 1 also summarizes physical properties such as coefficient of thermal expansion (CTE), softening point, permeability change temperature, and shape change temperature.

Sample No. 1, 17 and 18 are comparative examples as a glass containing only 100 parts by weight of the parent glass component, which does not contain a nucleating agent. Other examples are experimental examples further comprising 3 to 10 parts by weight of the nucleating agent.

Sample No. In the case of 1 to 20, although the composition of the parent glass component was not individually indicated, SiO ₂ is 50 to 70 wt%, B ₂ O ₃ 5 to 15 wt%, Al ₂ O among the parent glass components constituting 100 parts by weight in all samples. ₃ Satisfies 10 to 25 wt%, CaO 0 to 9.5 wt%, MgO 0 to 10 wt%, SrO 0 to 10 wt%, BaO 0 to 10 wt% and ZnO 0 to 10 wt%. Sample No. In the case of 1 to 16, the parent glass components are identical to each other as indicated by 'A'. Sample No. 17 and 18 have different parent glass components and sample No. It is different from 1, and it is denoted by B and C, respectively. Sample No. 19 is sample No. 17 The nucleating agent was further included in the parent glass component, and the sample No. 20 is sample No. 18 The nucleating agent was further included in the parent glass component.

First, Figure 5 is a prepared sample No. Pictures from 2 to 9.

Sample No. at the bottom of the photo 2 to 5 is a case where TiO _{2 is} added as a nucleating agent, and the nucleating agent weight is sequentially increased to 3, 5, 7, and 10. Glass coloring is observed with increasing TiO ₂ content. Sample No. The coloring of 4 and 5 is prominent. Therefore, it can be seen that when TiO _{2 is} added alone, the coloring effect of the glass increases at 7 parts by weight or more.

Sample No. at the top of the photo 6 to 9 is a single addition of ZrO ₂ as a nucleating agent, and is a case where the nucleating agent weight increases sequentially to 3, 5, 7, 10. It was observed that there was no coloring effect of the glass with increasing ZrO ₂ content.

6 is a sample No. 2 to 9 is a picture after maintaining at 850 ° C. for 1 hour, FIG. 7 is a picture after maintaining at 900 ° C. for 1 hour, and FIG. 8 is a picture after maintaining at 950 ° C. for 1 hour.

6 to 8, it can be seen that, when TiO _{2 is} added alone, crystallization proceeds most rapidly at 5 parts by weight (Sample No. 4). It can be seen that crystallization proceeds most rapidly at 5 and 7 parts by weight when ZrO _{2 is} added alone (sample No. 7, 8).

9 is a graph showing changes in permeability when one type of nucleating agent is included. Sample No. 1, 4, 8 transmittance, sample No. The transmittances after 4 and 8 were maintained at 950 ° C for 1 hour are also shown. In the transmittance graph as shown in FIG. 9, the horizontal axis represents wavelength (nm) and the vertical axis represents transmittance (%).

Sample No. Sample No. compared to 1 The transmittance of 4 and 8 is small. That is, when a single nucleating agent is added, the total transmittance of the infrared region is reduced compared to before the addition.

Sample No. In both 4 and 8, the permeability is further reduced when crystallization occurs. It can be seen that in the visible light region, transmittance up to 1700 nm or less is greatly reduced as indicated by a large arrow, but transmittance over 2700 nm is still present. It can be seen that crystal formation and growth were not sufficiently performed while maintaining at 950 ° C. for 1 hour. In other words, it can be said that the crystal formation and growth rate are slow when a single nucleating agent is added.

Next, Figure 10 is a sample No. prepared. Pictures from 10 to 12.

Sample No. 10 to 12 is a nucleating agent that includes both TiO ₂ and ZrO ₂ and 5, 7, and 10 parts by weight of the nucleating agent, respectively. At this time, the ratio of TiO ₂ and ZrO ₂ is 1: 1.

Sample No. As the TiO ₂ content increases in the order of 10 to 12, it is consistent with what is expected to be colored accordingly.

11 is a sample No. It is a photograph after 10-12 are kept at 850 ° C for 1 hour.

Referring to FIG. 11, when both TiO ₂ and ZrO ₂ are applied, it can be seen that crystallization proceeds most rapidly at 7 parts by weight (sample No. 11).

12 is a graph showing changes in permeability when both types of nucleating agents are included. Sample No. 1, 10 to 12 transmittance, sample No. The transmittance after 10 to 12 was maintained at 950 ° C for 1 hour was also shown.

Sample No. Sample No. compared to 1 The transmittance of 10 to 12 is small. That is, when the nucleating agent is added, the decrease in the total transmittance of the infrared region compared to before the addition is confirmed again after FIG. 9.

Sample No. In all 10 to 12, the permeability decreases further when crystallization occurs. In the visible light region, transmittance up to 1700 nm or less is greatly reduced as indicated by a large arrow, and especially transmittance of 2700 nm or more is reduced to 20% or less. In particular, the sample No. In the case of 11, the transmittance is 0. Sample No., which was confirmed to be the fastest crystallized in the photo result of FIG. 11. It can be seen that 11 is also the lowest transmittance in FIG. Sample No. In the case of 11, when used as a fireproof glass, since the infrared transmittance is 0, it is possible to completely block radiant heat. The present inventors propose that the crystal growth rate for fire glass application is based on the effect of reducing the infrared transmittance within 1 hour. It can be concluded from the comparison of FIGS. 9 and 12 that mixed addition is advantageous over single addition of the nucleating agent when these criteria are followed.

Next, Figure 13 is a prepared sample No. 13 to 16 photos.

Sample No. 13 to 16 is a nucleating agent that includes both TiO ₂ and ZrO ₂ and contains 7 parts by weight of the nucleating agent. At this time, the sample No. The proportion of TiO ₂ increases in the order of 13 to 16.

Sample No. As the TiO ₂ content increases in the order of 13 to 16, it is consistent with the expectation that coloring is made accordingly.

14 is a sample No. 13 to 16 is a picture after maintaining at 950 ℃ for 1 hour, it can be seen that all crystallization was made.

15 is a graph for viewing the change in permeability according to the TiO ₂ ratio control while containing 7 parts by weight of the nucleating agent. Sample No. 1, 4, 8, 11, 13 to 16 transmittance, sample No. The transmittance after 4, 8, 11, 13 to 16 was maintained at 950 ° C. for 1 hour is also shown.

Sample No. The proportion of TiO ₂ increases in the order of 8, 13, 14, 11, 15, 16, and 4. When the ratio of TiO ₂ and ZrO ₂ is 1: 1, that is, the sample No. In the case of 11, it can be seen that the transmittance decreases most.

Sample No. In the case of 13 to 16, in terms of coloring, the sample No. 14 is preferred. In this case, the proportion of TiO _{2 in} the nucleating agent is 32%. In terms of permeability reduction, the sample No. 11 is preferred. In this case, the proportion of TiO _{2 in} the nucleating agent is 50%. Therefore, when the nucleating agent includes both TiO ₂ and ZrO ₂ , the ratio of TiO ₂ in the nucleating agent is preferably 32 to 50%.

Next, Figure 16 is a sample No. prepared. 19 and 20 photos.

Sample No. 19 and 20 are nucleating agents that contain both TiO ₂ and ZrO ₂ and contain 7 parts by weight of nucleating agent. And the TiO ₂ ratio is 50%.

17 is a sample No. It is a picture after 19 and 20 are kept at 900 ° C. for 1 hour, and it can be seen that both crystallization was performed.

18 is a graph for showing the change in the transmittance of the examples having a TiO ₂ ratio of 50% while containing 7 parts by weight of the nucleating agent. Sample No. 17 to 20 transmittance, sample No. The transmittances after 19 and 20 were maintained at 950 ° C. for 1 hour are also shown.

After crystallization, the composition of the parent glass, in which the permeability decrease occurs, is different, but the composition of the nucleating agent by weight is the same. Similar to in 11. In particular, the sample No. Both 19 and 20 have a transmittance of 0 at 2700 nm or more. Therefore, it can be seen that when both TiO ₂ and ZrO ₂ are included and 7 parts by weight, and the proportion of TiO ₂ is 50%, infrared transmittance can be made zero at high temperature.

Next, Figure 19 is a sample No. prepared. 21 to 26 photos.

Sample No. 21 to 26 degrees as a nucleating agent that includes both TiO ₂ and ZrO ₂ and contains 7 parts by weight of nucleating agent. And the TiO ₂ ratio is 50%.

20 is a sample No. 21 to 26 is a photograph after maintaining at 800 ℃ for 1 hour, Figure 21 is a sample No. 21 to 26 is a photograph after maintaining at 850 ℃ for 1 hour, Figure 22 is a sample No. This is a picture after 21 to 26 was maintained at 1000 ° C for 1 hour. It can be confirmed that all crystallization was performed.

In particular, the sample No. Referring to FIG. 20, crystallization is performed at 800 ° C. and crystallization is started at the lowest temperature. Sample No. 21 and 26, it can be seen that crystallization was performed at 850 ° C with reference to FIG. These are the ones where the permeability change temperature exists between 800 and 850 ° C.

As shown in Fig. 22, sample No. 22, 24 to 26 can maintain the shape up to 1000 ℃.

23 is a sample No. It is a graph for comparing the transmittance before and after crystallization of 21 to 26. Crystallization is sample No. It is the case where it is maintained at 1000 degreeC for 1 hour except 21. Sample No. In the case of 21, since the softening point is low and softens before 1000 ° C, the transmittance when maintained at 800 ° C for 1 hour was shown.

A decrease in permeability was observed in all samples after crystallization. Sample No. 23 and 26 have a transmittance of 5% or less at 2700 nm or more, particularly Sample No. 23 is sample No. Like 11, the transmittance is 0.

24 is a sample No. SEM pictures after crystallization of 21 to 26.

24, the sample No. There are many crystals larger than 1um in size in 23 and 26. Sample No. In the case of 26, the size of a single crystal is 1 µm or less, but is aggregated with each other to exhibit an effect of 1 µm or more.

In other samples, crystals were not confirmed by SEM, but it can be indirectly confirmed from the photograph shown in FIG. 22 that crystals exist at a level that cannot be confirmed by SEM.

The crystal size results in FIG. 24 show a tendency to be consistent with those in the transmittance results in FIG. 23. Therefore, it can be said that in the case of crystallization according to an increase in temperature by containing a nucleating agent, a crystal size of 1 μm or more is preferable in order to have a transmittance close to 0 in the infrared region.

In order to increase the light scattering effect, the crystal shape may be preferably amorphous rather than spherical. It can be seen that in the case of obtaining a dendrite such as 23, the transmittance reduction effect is more excellent.

When synthesizing the results of the above embodiments, when adding TiO ₂ or ZrO ₂ single or mixed, it can be seen that the effect of reducing the transmittance of the infrared wavelength band in the glass state. Although the degree of reduction varies depending on the specific composition of the parent glass, it can be seen from the transmittance graph that the maximum change is 80% or more to 20% or less.

When adding TiO ₂ or ZrO ₂ single or mixing, it can be seen that the crystallization behavior with increasing temperature depends on the composition of the parent glass and TiO ₂ , ZrO ₂ parts by weight and the ratio between them. TiO ₂ It can be seen that upon a single addition, the degree of coloring of the glass increases with increasing content, and can be used when coloring is required. When adding TiO ₂ and ZrO ₂ mixture, TiO ₂ It was confirmed that the colored effect of the glass with the increase was still present. When adding ZrO ₂ , it was confirmed that there was no glass coloring effect with increasing content.

When adding TiO ₂ and ZrO ₂ mixtures, crystallization occurred with increasing temperature, and it was confirmed that the tendency for the decrease in transmittance in the infrared wavelength band was different depending on the size and shape of the crystal. It was confirmed that even if the nucleating agent was included in the same weight part, the crystallization behavior was different, and the shape of the resulting crystal was also changed. The TiO ₂ , ZrO ₂ content, the crystal growth rate, and the decrease in infrared transmittance do not show a proportionality pattern.

In the present invention, it is suggested that the content of the nucleating agent is 3 to 10 parts by weight for use as a fireproof glass. The upper limit is related to the solubility in the parent glass, and experimentally, it was confirmed that homogeneous glass melting was difficult at 10 parts by weight or more. Sample No. containing 3 parts by weight of TiO ₂ alone. In the case of 2, it is judged that the minimal effect as containing a nucleating agent appears.

The preferred embodiments of the present invention have been shown and described above, but the present invention is not limited to the specific preferred embodiments described above, and the technical field to which the present invention pertains without departing from the gist of the present invention claimed in the claims. Of course, various modifications can be made to anyone having ordinary knowledge, and such changes are within the scope of the claims.

10, 10 ': Glass 20: Crystal
221: molten tin 222: plate glass
220: float bath 230: dross box
231, 241: roller 240: slow cooling furnace
242: heater 300: plate glass manufacturing apparatus

Claims (9)

SiO ₂ 50 ~ 70 wt%, B ₂ O ₃ 5 ~ 15 wt%, Al ₂ O ₃ 10 ~ 25 wt%, CaO 0 ~ 9.5 wt%, MgO 0 ~ 10 wt%, SrO 0 ~ 10 wt%, BaO 100 parts by weight of the parent glass component including 0 to 10 wt% and ZnO 0 to 10 wt%; And
3 to 10 parts by weight of the nucleating agent containing both TiO ₂ and ZrO ₂ ,
The proportion of TiO ₂ in the nucleating agent is 32 to 50%,
Fireproof glass characterized in that crystals grow from the nucleating agent upon exposure to 750 to 1000 ° C and decrease the transmittance of 300nm to 5000nm wavelength within 20 hours or less within 1 hour. delete According to claim 1, SiO ₂ + Al ₂ O ₃ of the parent glass component is 70 to 82 wt% of the parent glass component, CaO + MgO + SrO + BaO + ZnO is 10 to 25 wt of the parent glass component Fireproof glass characterized in that the%. delete delete The fire protection glass according to claim 1, wherein the parent glass component does not include R ₂ O (where R is at least one of Li, Na, and K). delete The fire retardant glass according to claim 1, wherein the crystal has a single crystal or aggregated crystal size of 1 um or more. The fire-resistant glass according to claim 1, wherein the crystal is spherical or amorphous.

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