KR20120060847A - Glass plate manufacturing method and glass plate manufacturing apparatus - Google Patents
Glass plate manufacturing method and glass plate manufacturing apparatus Download PDFInfo
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- KR20120060847A KR20120060847A KR1020127006894A KR20127006894A KR20120060847A KR 20120060847 A KR20120060847 A KR 20120060847A KR 1020127006894 A KR1020127006894 A KR 1020127006894A KR 20127006894 A KR20127006894 A KR 20127006894A KR 20120060847 A KR20120060847 A KR 20120060847A
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- C—CHEMISTRY; METALLURGY
- C03—GLASS; MINERAL OR SLAG WOOL
- C03B—MANUFACTURE, SHAPING, OR SUPPLEMENTARY PROCESSES
- C03B17/00—Forming molten glass by flowing-out, pushing-out, extruding or drawing downwardly or laterally from forming slits or by overflowing over lips
- C03B17/06—Forming glass sheets
- C03B17/064—Forming glass sheets by the overflow downdraw fusion process; Isopipes therefor
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Abstract
The glass plate manufacturing method of this invention melt | dissolves a glass raw material, and obtains a molten glass, the shaping | molding process of forming a glass ribbon from the said molten glass by the downdraw method, and at least one of the said molten glass and the said glass ribbon And a volatilization promoting step of promoting volatilization of the volatile component from the surface of the film, a defrosting step of cooling the glass ribbon, and a cutting step of cutting the glass ribbon to obtain a glass plate.
This invention relates to the glass plate manufacturing method which manufactures a glass plate using the down-draw method, and the glass plate manufacturing apparatus used especially preferably for this manufacturing method.
Description
This invention relates to the glass plate manufacturing method which manufactures a glass plate using the down-draw method, and the glass plate manufacturing apparatus used especially preferably for this manufacturing method.
As a flat panel display (henceforth "FPD"), such as a liquid crystal display and a plasma display, as a glass substrate, the glass plate with a thickness thin for example 1.0 mm or less is used. In recent years, enlargement of the glass plate for FPD glass substrates is advanced, For example, the magnitude | size of the glass plate called 8th generation is 2200 mm x 2500 mm.
In order to manufacture such a glass plate for FPD glass substrates, the downdraw method is most often used. For example, in the overflow downdraw method, the belt-shaped glass ribbon is continuously formed by overflowing the molten glass from the groove of the molding apparatus. At this time, the glass ribbon is pulled downward and the thickness is adjusted by the pulling speed. Then, a glass ribbon is cut | disconnected to predetermined length and a glass plate is manufactured.
For example, in
Specifically, in the molding unit disclosed in
Moreover, in the shaping | molding unit disclosed by
Here, as a glass plate for FPD glass substrates and a glass plate for cover glass, high surface quality is calculated | required. For this reason, it is important to prevent a flaw on the surface of a glass plate.
By the way, a volatile component volatilizes in the interface which contact | connects air from glass (molten glass and glass ribbon immediately after formation) of a molten state. The inventors of the present invention think that if this phenomenon is effectively used in the downdraw method, it is possible to form a desired compressive stress layer on both main surfaces of the glass plate, thereby preventing the scratch on the surface of the glass plate. did.
However, when the cooling air is introduced into the
In addition, even if forced convection occurs near the
This invention aims at providing the glass plate manufacturing method which can obtain the glass plate which is hard to be scratched on the surface in view of such a situation. Moreover, an object of this invention is to provide the glass plate manufacturing apparatus which can accelerate the volatilization of the volatile component from the molten glass which overflows from the shaping | molding apparatus used especially preferable for this manufacturing method.
MEANS TO SOLVE THE PROBLEM In order to solve the said 1st subject, this invention melt | dissolves a glass raw material and obtains a molten glass, the shaping | molding process of forming a glass ribbon from the said molten glass by the downdraw method, the said molten glass, and the said glass Provided are a glass plate manufacturing method including a volatilization promoting step of promoting volatilization of a volatile component on at least one surface of a ribbon, a defrosting step of cooling the glass ribbon, and a cutting step of cutting the glass ribbon to obtain a glass plate.
MEANS TO SOLVE THE PROBLEM In order to solve the said 2nd subject, this invention is a shaping | molding apparatus which forms a glass ribbon by overflowing a molten glass from the both sides of a groove | channel, and inducing and fuse | melting the overflowed molten glass in the wall surface, The said shaping | molding And a heat insulating structure having a gate for passing the glass ribbon formed by the molding apparatus and surrounding the device, wherein the heat insulating structure includes the heat insulating structure for promoting volatilization of volatile components on the surface of the molten glass. It provides the glass plate manufacturing apparatus which introduce | transduces into the said heat insulation structure from the outside and discharges the gas which rises with the molten glass which flows down the wall surface of the said molding apparatus out of the said heat insulation structure.
According to this invention, the glass plate which is hard to be damaged in the surface in which the compressive stress layer with a high stress value was formed in both main surfaces can be obtained.
BRIEF DESCRIPTION OF THE DRAWINGS It is a schematic block diagram which shows the glass plate manufacturing apparatus which enforces the glass plate manufacturing method which concerns on one Embodiment of this invention.
It is sectional drawing of the shaping | molding unit which is a part of glass plate manufacturing apparatus of 1st Embodiment.
3 is a perspective view of the molding unit shown in FIG. 2.
4 is a sectional view of a forming unit of a modification.
5 is a cross-sectional view of a forming unit of another variant.
6 is a cross-sectional view of another forming unit.
It is sectional drawing of the shaping | molding unit which is a part of glass plate manufacturing apparatus of 2nd Embodiment.
8 is a graph showing the relationship between the depth and the Si ratio in the glass plates of Examples 1 and 2. FIG.
9 is a graph showing the relationship between the internal stress and the depth of the glass plate of Example 1. FIG.
It is sectional drawing of the shaping | molding unit which is a part of the conventional glass plate manufacturing apparatus.
EMBODIMENT OF THE INVENTION Hereinafter, it demonstrates, referring drawings for specific content for implementing this invention. In addition, the following description is related to an example of this invention, Comprising: This invention is not limited by these.
<Glass plate manufacturing method>
The glass plate manufacturing method which concerns on one Embodiment of this invention is performed by the glass
Glass raw materials to be injected into the
Here, "volatile component" means SiO 2 Saturated vapor pressure at the glass melting temperature (the glass temperature at which the viscosity of the glass becomes 1.0 × 10 5 Pa · s or less) is more easily volatilized, in other words, SiO 2 Higher component. Examples of the volatile component include Al 2 O 3 , B 2 O 3 , Li 2 O, Na 2 O, K 2 O, MgO, CaO, SrO, BaO, ZrO 2 , SnO 2 , and the like. It is not limited. In addition, since B 2 O 3 , alkali oxides (Li 2 O, Na 2 O, K 2 O) and alkaline earth metal oxides (MgO, CaO, SrO, BaO) are highly volatile, the glass composition is at least one of them. It is preferable to contain.
The volatile component, since the saturated vapor pressure in the glass melting temperature higher than SiO 2, the molding during or shortly after (in a glass melt state) SiO 2 Volatilize before. That is, in the molding process in which the glass ribbon is formed from the molten glass, SiO 2 is formed on the surface of the molten glass. Since other components volatilize, as a result, the silica rich layer in which content of Si atom exceeds content of Si atom in glass inside is formed in the surface of the glass plate after shaping | molding. Moreover, when a silica rich layer is formed on the surface of a glass plate, a compressive stress layer is formed in the two main surfaces of a glass plate by the difference of the thermal expansion coefficient with the glass plate inside.
In addition, content of the volatile component in the glass composition in the center position of the thickness direction of a glass plate is represented by mass%, It is preferable that it is 10% or more (or 15% or more), It is more preferable that it is 30% or more, 35% It is more preferable that it is more than (or 40% or more). If the content of the volatile component in the glass composition is less than 10%, the volatilization of the volatile component is not promoted, and the silica rich layer and the compressive stress layer are less likely to be formed on the glass plate surface. On the contrary, when it contains many volatile components, volatilization will increase too much and it will become difficult to homogenize glass. Therefore, it is preferable that it is 50% or less (or 45% or less, 42% or less), and it is more preferable that it is 40% or less.
As an example of the silicate glass for liquid crystal, there is an alumino boro silicate glass which consists of the following compositions substantially. In addition, in this specification, all content is represented by the mass% after that and shows more preferable content in parentheses. In addition, "substantially" is the meaning which allows presence of the trace component unavoidably mixed from industrial raw materials in the range of less than 0.1 mass%.
SiO 2 : 50 to 70% (55 to 65%, 57 to 64%, 58 to 62%)
Al 2 O 3 : 5 to 20% (10 to 20%, 12 to 18%, 15 to 18%)
B 2 O 3 : 0-15% (5-15%, 6-13%, 7-12%)
MgO: 0 to 10% (0.01 to 5% or more, 0.5 to 4%, 0.5 to 2%)
CaO: 0 to 10% (1 to 9%, 3 to 8%, 4 to 7%, 4 to 6%)
SrO: 0 to 10% (0.5 to 9%, 3 to 8%, 3 to 7%, 3 to 6%)
BaO: 0 to 10% (0 to 8%, 0 to 3%, 0 to 1%, 0 to 0.2%)
ZrO 2 : 0 to 10% (0 to 5%, 0 to 4%, 0 to 1%, 0 to 0.1%)
As another example of the silicate glass for liquid crystal, there is an aluminum boro silicate glass substantially composed of the following composition.
SiO 2 : 50 to 70% (55 to 65%, 58 to 62%)
Al 2 O 3 : 10-25% (15-20%, 15-18%)
B 2 O 3 : 5-18% (8-14%, 10-13%)
MgO: 0 to 10% (1 to 5%, 1 to 2%)
CaO: 0-20% (1-7%, 4-7%)
SrO: 0 to 20% (1 to 10%, 1 to 3%)
BaO: 0 to 10% (0 to 2%, 0 to 1%)
K 2 O: 0-2% (0.1-2%, 0.1-0.5%)
SnO 2 : 0 to 1% (0.01 to 0.5%, 0.01 to 0.3%)
However, the content of the above composition of SnO 2, is a value converted to all of the components of Sn having a plurality of singers treated as SnO 2.
The silicate glass for cover glass contains the following components as an essential component, for example.
SiO 2 : 50 to 70% (55 to 65%, 57 to 64%, 57 to 62%)
Al 2 O 3 : 5 to 20% (9 to 18%, 12 to 17%)
Na 2 O: 6 to 30% (7 to 20%, 8 to 18%, 10 to 15%)
In addition, the following components may be included as an arbitrary component.
Li 2 O: 0 to 8% (0 to 6%, 0 to 2%, 0 to 0.6%, 0 to 0.4%, 0 to 0.2%)
B 2 O 3 : 0 to 5% (0 to 2%, 0 to 1%, 0 to 0.8%)
K 2 O: 0 to 10% (1 to 6%, 2 to 5%, 2 to 4%)
MgO: 0 to 10% (1 to 9%, 2 to 8%, 3 to 7%, 4 to 7%)
CaO: 0 to 20% (0.1 to 10%, 1 to 5%, 2 to 4%, 2 to 3%)
ZrO 2 : 0 to 10% (0 to 5%, 0 to 4%, 0 to 1%, 0 to 0.1%)
As an example of the silicate glass for cover glass, there exists alkali-alumino silicate glass which consists of a following composition substantially.
SiO 2 : 50 to 70%
Al 2 O 3 : 5 to 20%
Na 2 O: 6-20%
K 2 O: 0 to 10%
MgO: 0 to 10%
CaO: greater than 2 to 20%
ZrO 2 : 0 to 4.8%
Moreover, preferably, the following conditions are satisfied.
(SiO 2 content)-(Al 2 O 3 content) /2=46.5 to 59%
The content ratio of CaO / RO (where R is at least one selected from Mg, Ca, Sr and Ba) is greater than 0.3
The sum of SrO content and BaO content is less than 10%
The content ratio of (ZrO 2 + TiO 2 ) / SiO 2 is 0 to less than 0.07
The content ratio of B 2 O 3 / R 1 2 O (wherein
As another example of the silicate glass for cover glass, there exists alkali-alumino silicate glass which consists of the following compositions substantially.
SiO 2 : 58-68%
Al 2 O 3 : 8-15%
Na 2 O: 10-20%
Li 2 O: 0 to 1%
K 2 O: 1 to 5%
MgO: 2 to 10%
In addition, the
SiO 2 is a component constituting the skeleton of the glass, and has an effect of increasing the chemical durability and heat resistance of the glass. When the content is too small, the effect is not sufficiently obtained, and when the content is too large, the glass tends to cause devitrification, making molding difficult, increasing the viscosity, and making the glass homogeneous.
B 2 O 3 is a component that lowers the viscosity of the glass and promotes dissolution and clarification of the glass. When there is too much content, the acid resistance of glass will fall and the homogenization of glass will become difficult.
Al 2 O 3 is a component constituting the skeleton of the glass, and has an effect of increasing the chemical durability and heat resistance of the glass. In addition, there is an effect of increasing the ion exchange performance and the etching rate. If the content is too small, the effect is not sufficiently obtained. On the other hand, when there is too much content, the viscosity of glass will rise and it will become difficult to melt | dissolve and acid resistance will fall.
MgO and CaO are components which lower the viscosity of the glass and promote the dissolution and clarification of the glass. Moreover, since the ratio which raises the density of glass is low in alkali earth metal, Mg and Ca are advantageous components in order to improve solubility while reducing the glass obtained. However, when the content is too much, the chemical durability of the glass is lowered.
SrO and BaO are components which lower the viscosity of the glass and promote the dissolution and clarification of the glass. Moreover, it is also a component which raises oxidizing property of a glass raw material and improves clarity. However, when the content is too large, the density of the glass rises, the weight reduction of the glass plate is not attempted, and the chemical durability of the glass decreases.
Li 2 O is one of the ion exchange components and is a component that lowers the viscosity of the glass and improves the meltability and formability of the glass. Further, Li 2 O is a component improving the Young's modulus of the glass (Young`s modulus). In addition, Li 2 O has a high effect of increasing the compressive stress value in the alkali metal oxide. However, when the content of Li 2 O is too large, the liquid viscosity is reduced, since the glass is liable to devitrification, the mass production of cheap glass using a downdraw method is difficult. Moreover, the thermal expansion coefficient of glass becomes high too much, the heat shock resistance of glass falls, and it becomes difficult to match thermal expansion coefficient with peripheral materials, such as a metal and an organic adhesive. Moreover, there exists a problem that deterioration of the ion exchange salt in the ion exchange process which is the process of strengthening a glass substrate becomes quick. In addition, when the low temperature viscosity is excessively lowered, stress relaxation occurs in the heating step after chemical strengthening, and the compressive stress value is lowered, so that sufficient strength cannot be obtained.
Na 2 O is an ion exchange component and is an essential component that lowers the high temperature viscosity of the glass and improves the meltability and formability of the glass. Moreover, it is a component which improves the devitrification resistance of glass. If the content is less than 6%, the meltability of the glass is lowered, and the cost for melting increases. Moreover, since ion-exchange performance also falls, sufficient strength cannot be obtained. In addition, the coefficient of thermal expansion is excessively lowered, making it difficult to match thermal expansion coefficients with peripheral materials such as metals and organic adhesives. In addition, the glass is likely to cause devitrification, and the devitrification resistance is also lowered, so that it is not applicable to the overflow downdraw method, making mass production of inexpensive glass difficult. On the other hand, when content exceeds 20%, low-temperature viscosity will fall, thermal expansion coefficient will become excess, impact resistance will fall, and thermal expansion coefficients, such as a metal and an organic adhesive, will become difficult to match. Moreover, since the devitrification resistance fall by glass deterioration also arises, mass production of the inexpensive glass using the down-draw method becomes difficult.
K 2 O is an ion exchange component, and is a component capable of improving the ion exchange performance of the glass by including. K 2 O is also a component that lowers the high temperature viscosity of the glass and improves the meltability and moldability of the glass and at the same time improves the devitrification resistance. However, when the content of K 2 O is too large, the low temperature viscosity is lowered, the coefficient of thermal expansion becomes excessive, since the impact resistance decreases, which is not preferable in the case of application as a cover glass. In addition, the thermal expansion coefficient hardly matches with peripheral materials such as metals and organic adhesives. Moreover, since the devitrification resistance fall by glass deterioration also arises, mass production of the inexpensive glass using the downdraw method becomes difficult.
Na 2 O and K 2 O are components that elute from glass to deteriorate TFT characteristics, or increase the coefficient of thermal expansion of glass to cause damage to the substrate during heat treatment. It is not preferable to contain a large amount. Therefore, by incorporating a specific amount of the above components into the glass, the basicity and the meltability of the glass are increased while the deterioration of the TFT characteristics and the thermal expansion of the glass are suppressed within a certain range, and the oxidation of the metal which is hydroly fluctuated easily, It is also possible to exercise.
ZrO 2 is a component that significantly improves the ion exchange performance and increases the viscosity and the strain point near the devitrification temperature of the glass. Further, ZrO 2, it is also a component for improving the heat resistance of the glass. However, when the content of ZrO 2 is too large, the devitrification temperature is increased, and the substantial decrease covered.
TiO 2 is a component that improves the ion exchange performance and decreases the high temperature viscosity of the glass. However, when the content of TiO 2 is too large, resulting in substantial degradation covered. In addition, the glass is colored, which is not preferable for a cover glass or the like. In addition, since the glass becomes colored, the ultraviolet ray transmittance also decreases, and thus, a problem arises in that the ultraviolet curable resin cannot be sufficiently cured when the treatment using the ultraviolet curable resin is performed.
A clarifier can be added as a component which defoases the bubble in glass. The clarifier is not particularly limited as long as the environmental load is small and the clarity of the glass is excellent, but for example, at least one selected from metal oxides such as tin oxide, iron oxide, cerium oxide, terbium oxide, molybdenum oxide, and tungsten oxide Can be mentioned.
In addition, As 2 O 3 , Sb 2 O 3 and PbO generate | occur | produce the reaction accompanying a fluctuation | variation of a hydrolysis in a molten glass, and are the substance which has the effect of clarifying glass, However, since these are substances with a large environmental load, this implementation is carried out. in the form of a glass plate, is substantially free of as 2 O 3, Sb 2 O 3 and PbO in the glass. Further, the means described in the specification, As 2 O 3, Sb 2
Next, especially preferable aspect is demonstrated about the silicate glass for liquid crystals. As mentioned later, it is preferable that the
As the glass plate manufacturing method of this embodiment, a volatilization promotion process is performed in the heat insulation structure (2). For this reason, the silica rich layer is formed in the manufactured glass plate on the surface. Hereinafter, this glass plate is demonstrated.
(1) silica rich layer
The "silica rich layer" refers to the Si atomic content in the glass composition in the center of the thickness direction of the glass plate as a reference value, and from the position at which the ratio of the Si atomic content in the glass composition to the reference value becomes 1.05 or more to the main surface of the glass plate. Indicates the area of.
A glass plate surface, the silica-rich layer which is more than the content of SiO 2 content of the center in the thickness direction of the glass plate is formed of SiO 2. The depth of this silica rich layer is preferably more than 0 to 20 nm, more preferably more than 0 to 15 nm (also 1 to 12 nm, 2 to 11 nm, 3 to 11 nm). Thereby, the compressive stress layer of sufficient depth can be obtained. On the other hand, although the depth of a silica rich layer can be made deep by promoting volatilization from the surface of the glass ribbon immediately after formation, deviation of shaping | molding appropriate condition or fall of productivity arise by it. Therefore, it is preferable that the depth of a silica rich layer is 30 nm or less.
As a silica rich layer, it is preferable that the maximum value of the ratio of Si atom content in the glass composition with respect to the said reference value is 1.06 or more, and 1.08 or more (Moreover, 1.10 or more, 1.12 or more, 1.14 or more, 1.15 or more, 1.16 or more, 1.18 or more) It is more preferable).
Or it is preferable that the maximum value of Si atom content in the glass composition of a silica rich layer is 1% or more more than Si atom content of the center of the thickness direction of a glass plate, and is 1.5% or more (more, 2% or more, 2.5%) More than 3%), many are more preferable.
Alternatively, the silica up to a value of SiO 2 content of the rich layer, than the SiO 2 content of the center in the thickness direction of the glass sheet at least 0.5% higher is preferred, and greater than or equal to 1% (and more than 1.5%, 2% or more, more than 2.5% , 3% or more) is more preferable.
By satisfy | filling the conditions mentioned above, a silica rich layer can obtain the difference of sufficient thermal expansion coefficient between a glass plate surface and an inside of a glass plate, and can form a compressive stress layer in the both main surfaces of a glass plate. Moreover, the Vickers hardness and durability of the glass plate surface can also be improved, and it can prevent that a glass plate is broken.
Here, when the Si atom content and SiO 2 content of the silica-rich layer formed on the glass sheet surface is less than the above range, it is not possible to obtain a difference between a sufficient coefficient of thermal expansion, sufficient compression of large stresses between the glass surface and the glass sheet inside The layer is not formed or sufficient Vickers hardness or durability cannot be obtained.
On the other hand, even if Si atom content and SiO 2 content of the silica-rich layer is that if I exceeding the above upper limit, the quality (physical properties, thermal properties, chemical properties) of the glass sheet away been changed, it can not be used in conventional applications have. For example, cutting and etching of a glass plate become difficult.
Further, in the silica-rich layer formed on the glass plate produced according to the present embodiment, Si atom content and SiO 2 content of the larger position is not different from the glass surface, sometimes in the range of from greater than 0 to 5 nm from the glass plate surface have.
When the silica rich layer is formed on the surface of the glass plate, a compressive stress layer is formed on portions along both main surfaces of the glass plate due to the difference in thermal expansion coefficient between the surface of the glass plate and the inside of the glass plate, and a tensile stress layer between these compressive stress layers. Is formed. According to the glass plate manufacturing method of this embodiment, the stress profile drawn by plotting a compressive stress value and a tensile stress value becomes specific.
Although it is possible to form compressive stress layers on both main surfaces of the glass plate by quenching the glass ribbon in the defrosting step, the stress profile of the glass plate obtained in this way is like a parabolic shape (the compressive stress layer in this case is glass Is caused by the difference in heat transfer between the surface of the glass plate and the inside of the glass plate due to a constant heat transfer rate). On the other hand, as a glass plate obtained by the glass plate manufacturing method of this embodiment, the compressive stress layer is formed by a volatilization promotion process, ie, the difference of the thermal expansion coefficient resulting from a silica rich layer contributes to formation of a compressive stress layer. For this reason, a compressive stress layer is formed in the area | region near the main surface of a glass plate (that is, the depth of a compressive stress layer is shallow). Moreover, the compressive stress layer has a larger stress value than that obtained when the compressive stress layer is formed by quenching (the compressive stress layer and the tensile stress layer are balanced, and thus, when the compressive stress layer becomes thin, Stress value is high). That is, in the vicinity of the surface of the glass plate obtained by the glass plate manufacturing method of this embodiment, since the compressive stress layer which has a larger stress value is formed than the case where the compressive stress layer was formed by quenching, the surface of a glass plate becomes hard to produce a scratch more. . In addition, a tensile stress layer has a substantially constant stress value except the both sides of the thickness direction of a glass plate. That is, the stress profile of the glass plate obtained by the glass plate manufacturing method of this embodiment forms a U-shape with a flat bottom.
(2) compressive stress layer
It is preferable that the depth of a compressive stress layer is 50 micrometers or less. The depth of the compressive stress layer can be deepened by promoting volatilization on the surface of the glass ribbon immediately after formation. However, the compressive stress layer is caused to deviate from the molding proper condition or to reduce the productivity. The depth of the compressive stress layer is more preferably 45 µm or less, still more preferably 40 µm or less, and particularly preferably 38 µm or less. In addition, the compressive layer stress layer depth in this specification has shown the depth of the compressive stress layer formed in the part along one main surface of a glass plate. That is, the compressive stress layer of the said depth is formed in each of both main surfaces of a glass plate.
Moreover, it is preferable that the depth of a compressive stress layer is more than 10 micrometers. When the depth of the compressive stress layer is to some extent, it is possible to prevent the glass plate from being easily broken by minute scratches caused by handling. Even if a deeper wound occurs, in order to prevent breakage of the glass plate, the depth of the compressive stress layer is more preferably 15 µm or more, and more preferably 20 µm or more (particularly, 25 µm or more, 30 µm or more, 35 µm). Above).
Alternatively, the depth of the compressive stress layer is preferably less than 1/13 of the plate thickness of the glass plate, and is less than 1/15 (also less than 1/17, less than 1/20, less than 1/22, less than 1/24). It is more preferable.
It is preferable that the maximum compressive stress value of a compressive stress layer is 4 MPa or less. It is because the workability of a glass plate will worsen when it exceeds 4 MPa. The maximum compressive stress value is more preferably 3.7 MPa or less, and still more preferably 3.5 MPa or less (particularly 3.0 MPa or less and 2.8 MPa or less).
In addition, the maximum compressive stress value of the compressive stress layer is preferably 0.4 MPa or more, and more preferably 1 MPa or more (more than 1.5 MPa or more and 2 MPa or more) from the viewpoint of improving the mechanical strength of the glass plate.
In addition, "stress value" in this specification is a value when it measures every 10 micrometers range in the thickness direction from the main surface of a glass plate. Therefore, there exists a case where the compressive stress value which locally exceeds the range of the said compressive stress value exists (the same also applies to the tensile stress value mentioned later).
(3) tensile stress layer
As above-mentioned, the tensile stress layer formed in the glass plate inside has a substantially constant stress value except the both sides of the thickness direction of a glass plate. Difference between the maximum value and the minimum value of the tensile stress value at the
When the tensile stress value of a tensile stress layer becomes large, when cut | disconnecting a glass plate, the scribe line of the predetermined depth put in for cutting may extend out of assumption, and it may become difficult to divide a glass plate by a desired dimension. According to this embodiment, even if the maximum compressive stress of a surface layer is enlarged, it is possible to keep tensile stress at a small value. For example, it is possible to set it as (absolute value of the maximum compressive stress of a surface layer) / (absolute value of the maximum tensile stress of a tensile stress layer) = 6 or more. For example, it is preferable that the maximum tensile stress value of a tensile stress layer is 0.4 Mpa or less. When the maximum tensile stress value of the tensile stress layer exceeds 0.4 MPa, when the glass plate is cut, when a scribe line of a predetermined depth inserted for cutting is stretched out of the assumption, it becomes difficult to divide the glass plate into desired dimensions. Because there is. The maximum tensile stress value of the tensile stress layer is more preferably 0.3 MPa or less, and still more preferably 0.2 MPa or less (particularly 0.15 MPa, 0.10 Mpa or less).
In addition, since the stress value of the tensile stress layer formed inside the glass plate is substantially constant in the thickness direction of the glass plate, the effect that the glass plate is less likely to be broken compared to the case where the stress value of the tensile stress layer draws a parabola in the thickness direction of the glass plate is obtained. Lose.
More specifically, the tensile stress value of the glass plate obtained by the glass plate manufacturing method of this embodiment is substantially constant in the thickness direction of a glass plate, and the maximum value of the tensile stress value only quenchs a glass ribbon by a defrosting process. It is smaller than the maximum tensile stress value of the tensile stress layer formed by. When a tensile stress value becomes extremely large, there exists a possibility that a glass plate may break at the time of a process, etc., and it is preferable that the tensile stress value is smaller. In addition, although the depth of the compressive stress layer formed only by quenching a glass ribbon by a defrosting process is 1/10 or more of the thickness of the plate | board thickness of a glass plate, of the compressive stress layer formed by the glass plate manufacturing method of this embodiment The depth is for example less than 1/13 of the plate thickness. That is, when the thickness of the plate becomes thin, the thickness of the tensile stress layer for canceling the compressive stress of the compressive stress layer on the surface of the glass plate also becomes thin. It becomes large and, as a result, the processing precision of a glass plate falls. However, since the stress value of the tensile stress layer of the glass plate obtained by the glass plate manufacturing method of this embodiment is substantially constant in the thickness room of a glass plate, the maximum value of a tensile stress value also becomes small, and processing of a glass plate can also be performed with high precision. .
(4) Vickers hardness
The Vickers hardness of the surface of the glass plate obtained by the glass plate manufacturing method of this embodiment is larger than the Vickers hardness inside a glass plate. That is, since the Vickers hardness of the surface of the glass plate obtained by the glass plate manufacturing method of this embodiment improves, a crack incidence rate falls and it is hard to produce a scratch, and the effect that it is hard to damage can be acquired.
It is preferable that the Vickers hardness of the glass plate surface formed in this embodiment is 4 GPa or more, It is more preferable that it is 5 GPa or more, It is further more preferable that it is 5.35 GPa or more. Or 1.01 or more is preferable and, as for ratio of the Vickers hardness of the glass plate surface with respect to the Vickers hardness inside a glass plate, 1.02 or more (more 1.05 or more, 1.10 or more) are more preferable.
(5) plate thickness
It is preferable that the thickness of the glass plate obtained by the glass plate manufacturing method of this embodiment is 1.5 mm or less. When the thickness is 3 mm or more, the strength of the glass plate itself is increased, and the compressive stress layer formed near the surface does not exhibit sufficient effect. As for the thickness of a glass plate, it is more preferable that it is 1.0 mm or less (Moreover, 0.7 mm or less, 0.5 mm or less, 0.3 mm or less). The thinner the glass plate, the more significant the effect of the present invention is.
(6) the size of the glass plate
The glass plate manufacturing method of this embodiment is suitable for a large glass plate. This is because the larger the glass plate is, the larger the amount of warpage and the glass plate is more likely to be broken due to fine scratches caused by handling. However, the occurrence of the problem can be reduced by forming a compressive stress layer on the glass plate surface. For this reason, the glass plate manufacturing method of this embodiment is suitable for manufacture of the glass plate of 1000 mm or more and 2000 mm or more in width direction, for example.
In this embodiment, although the volatilization promotion process which accelerates the volatilization of the volatile component in the surface of the
Next, the specific example of the shaping | molding unit comprised from the shaping |
<1st embodiment>
FIG.2 and FIG.3 shows the shaping |
The shaping |
The
And the shaping |
The
In this embodiment, the some
In addition, the
In addition, the shape and quantity of the
Moreover, it is preferable that the air introduce | transduced into the
When 10 A of shaping | molding units of this embodiment demonstrated above are used, the
In addition, although the
However, in the case where the
In addition, although the
In addition, as shown in FIG. 5, the
In addition, in the said embodiment, although the introduction of the air in the
By the way, when using forced convection, when the temperature of the air introduce | transduced in the
In addition, the gas introduced into the
<2nd embodiment>
Next, with reference to FIG. 7, the shaping |
The shaping |
When the inside of the
<Other embodiments>
The present invention can be applied not only to the overflow downdraw method but also to the slot downdraw method, for example. In this case, a volatilization promoting step of promoting volatilization of the volatile component on the surface of the
In addition, the method for implementing this invention is not limited to the said embodiment, For example, a volatilization promotion process can also be performed after a formation process by lengthening the time which keeps the
<Examples>
Hereinafter, although an Example is given and this invention is demonstrated in detail, this invention is not restrict | limited to these Examples at all.
As shown in Figs. 2 and 3, by using a
The content rate of each component of the molten glass was as follows.
SiO 2 : 60.9%
Al 2 O 3 : 16.9%
B 2 O 3 : 11.6%
MgO: 1.7%
CaO: 5.1%
SrO: 2.6%
BaO: 0.7%
K 2 O: 0.25%
SnO 2 : 0.13%
In addition, two
(exam)
About the glass plate of the Example, the atomic concentration of the surface vicinity was measured using the X-ray photoelectron spectroscopy apparatus (Quantera SXM by Albacpai company). Specifically, the surface of the glass plate was excavated to various depths by sputtering, and the atomic concentration at each depth was measured. As a measurement element, Al, B, Ca, Sr, and Ba which are volatile components with a relatively high content rate were specified simultaneously with Si, and the ratio of Si which occupies in a measurement element was calculated | required. Among them, the results of Examples 1 and 2 were as shown in FIG. In addition, since the content rate of K and Sn is small among these volatile components, and it is thought that the influence which these amounts have on the ratio of Si is not considered, these were not included in the measurement element.
As can be seen from FIG. 8, in the examples, the Si ratio is higher than that inside the glass plate in a region extremely close to the surface. This indicates that the volatile components near the surface are decreasing, and it can be seen that by using a heat-insulating structure through which gas passes from the bottom, more volatile components can be volatilized to form a compressive stress layer having a high stress value. have.
In addition, the internal stress was measured about the glass plate of the Example. The internal stress is obtained by using a small area birefringence meter (KOBRA-CCD / X manufactured by Oji Keisukuki Co., Ltd.), and the optical path difference per 1 cm for each predetermined depth on the surface of the cross section obtained by cutting the glass plate in the thickness direction ( Optical path difference / optical path length) was measured and calculated by dividing this by the photoelastic constant. The result of Example 1 is as showing in FIG.
In FIG. 9, it turns out that the compressive stress layer with a high stress value is formed in the both main surfaces of a glass plate. In addition, the stress value of the tensile stress formed in the glass plate became substantially constant in the glass plate thickness direction. This is attributable to the decrease in volatile components near both main surfaces of the glass plate.
In Table 1, various original values regarding the glass plates of Examples 1-5 are shown.
In addition, "reference value" in a table | surface is "Si atom content in the glass composition of the center of the thickness direction of a glass plate" as mentioned above.
Next, the scratch test was done about the glass plates of Examples 1-5. Specifically, the scratch test was carried out by using a scratch hardness tester Model 318S manufactured by Eric Clean Corporation having a carbide ball chip having a diameter of 0.75 mm at the tip, and a scratch load of 2 N and a scratch length of 30 mm. As a result of observing the surface of the glass plate with a laser microscope, in Examples 1 to 5, no crack was generated on the surface of the glass plate. On the other hand, when the same scratch test was performed after polishing the surface of the glass plate of Example 1, the crack generate | occur | produced in the grinding | polishing surface.
Industrial Applicability
This invention is especially preferable for manufacture of the plate glass for FPD glass substrates. Moreover, the tempered glass which chemically strengthened the glass plate obtained by this invention is used suitably for the cover glass of a mobile telephone, a digital camera, a PDA (portable terminal), a solar cell, and an FPD, In addition, for example, a touch panel display Can be expected to be used as a substrate, a window glass, a substrate for a magnetic disk, a cover glass for a solid-state image sensor, a tableware, and the like.
Claims (11)
A molding step of forming a glass ribbon from the molten glass by a downdraw method;
A volatilization promoting step of promoting volatilization of a volatile component from at least one surface of the molten glass and the glass ribbon;
A defrosting step of cooling the glass ribbon,
Cutting step of cutting the glass ribbon to obtain a glass plate
Glass plate manufacturing method comprising a.
In the volatilization promoting step, the gas introduced into the heat insulating structure from outside the heat insulating structure is brought into contact with the surface of the molten glass to be dropped and / or the drawn glass ribbon, and then discharged out of the heat insulating structure to thereby melt the melt. A glass plate manufacturing method for promoting volatilization of a volatile component from at least one surface of the glass and the glass ribbon.
In the volatilization promotion step, the glass plate manufacturing method which accelerates volatilization of the volatile component from the at least one surface of the said molten glass and the said glass ribbon by depressurizing the inside of the said heat insulation structure.
A heat insulating structure surrounding the molding apparatus and having a gate for passing the glass ribbon formed by the molding apparatus,
In order to promote volatilization of the volatile component from the surface of the said molten glass, the said heat insulation structure introduce | transduces the gas which rose in the said heat insulation structure from the outside of the said heat insulation structure, and rose along with the molten glass which flows down on the wall surface of the said shaping | molding apparatus. The outlet which discharges out of a heat insulation structure is provided,
Glass plate manufacturing apparatus.
The said discharge port is a glass plate manufacturing apparatus provided in the upper part of the said peripheral wall.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
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| JPJP-P-2009-292091 | 2009-12-24 | ||
| JP2009292091 | 2009-12-24 | ||
| PCT/JP2010/007466 WO2011077734A1 (en) | 2009-12-24 | 2010-12-24 | Glass plate manufacturing method and glass plate manufacturing apparatus |
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| Publication Number | Publication Date |
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| KR20120060847A true KR20120060847A (en) | 2012-06-12 |
| KR101276494B1 KR101276494B1 (en) | 2013-06-18 |
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| KR1020127016363A KR101346930B1 (en) | 2009-12-24 | 2010-12-24 | Glass plate and method for manufacturing glass plate |
| KR1020127006894A KR101276494B1 (en) | 2009-12-24 | 2010-12-24 | Glass plate manufacturing method and glass plate manufacturing apparatus |
| KR1020137021278A KR101541631B1 (en) | 2009-12-24 | 2010-12-24 | Glass plate and method for manufacturing glass plate |
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| KR1020137021278A KR101541631B1 (en) | 2009-12-24 | 2010-12-24 | Glass plate and method for manufacturing glass plate |
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| JP (4) | JP5281634B2 (en) |
| KR (3) | KR101346930B1 (en) |
| CN (2) | CN102574720B (en) |
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| WO (2) | WO2011077756A1 (en) |
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| KR101346930B1 (en) | 2014-01-03 |
| JPWO2011077734A1 (en) | 2013-05-02 |
| JP2011148684A (en) | 2011-08-04 |
| JP5624453B2 (en) | 2014-11-12 |
| JP5281634B2 (en) | 2013-09-04 |
| CN102958855A (en) | 2013-03-06 |
| KR20130108463A (en) | 2013-10-02 |
| WO2011077734A1 (en) | 2011-06-30 |
| TWI401219B (en) | 2013-07-11 |
| JP5269870B2 (en) | 2013-08-21 |
| KR101276494B1 (en) | 2013-06-18 |
| KR101541631B1 (en) | 2015-08-03 |
| CN102574720B (en) | 2014-11-26 |
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| CN102958855B (en) | 2014-05-28 |
| KR20120086733A (en) | 2012-08-03 |
| TW201136847A (en) | 2011-11-01 |
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| JP5186602B2 (en) | 2013-04-17 |
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