技术领域technical field
本发明涉及化学强化用浮法玻璃的制造方法。The present invention relates to a method for producing float glass for chemical strengthening.
背景技术Background technique
近年来，在手机或便携信息终端(PDA)等平板显示装置中，为了保护显示器并且改善美观，在显示器的正面以达到比图像显示部分更广的区域的方式配置薄的板状保护玻璃。In recent years, in flat panel display devices such as mobile phones and PDAs, in order to protect the display and improve appearance, a thin plate-shaped cover glass is arranged on the front of the display so as to cover a wider area than the image display portion.
对于这样的平板显示装置，要求轻量和薄型化。因此，要求显示器保护用途中使用的保护玻璃也减薄。Such flat panel display devices are required to be lightweight and thin. Therefore, the thickness of the cover glass used for a display protection application is also requested|required.
但是，在使保护玻璃的厚度减薄时，强度会降低，有时会因使用中或携带中掉落等而使保护玻璃自身破裂。结果，存在无法发挥保护显示装置这一本来的作用的问题。However, when the thickness of the cover glass is reduced, the strength is lowered, and the cover glass itself may be broken by dropping it during use or carrying. As a result, there is a problem that the original function of protecting the display device cannot be exhibited.
因此，为了提高耐划伤性，以往的保护玻璃通过对利用浮法制造的浮法玻璃进行化学强化而在表面上形成压应力层来提高保护玻璃的耐划伤性。Therefore, in order to improve the scratch resistance, the conventional cover glass improves the scratch resistance of the cover glass by chemically strengthening the float glass produced by the float process to form a compressive stress layer on the surface.
近年来，对于保护玻璃等而言，所要求的耐划伤性进一步提高。对以往的钠钙玻璃进行化学强化而得到的化学强化浮法玻璃的表面压应力为约500MPa，压应力层的深度大概为约10μm。但是，近年来，为了应对对于高耐划伤性的要求，开发了表面压应力为600MPa以上且压应力层的深度为15μm以上的化学强化浮法玻璃。In recent years, the scratch resistance required for cover glass and the like has been further improved. The surface compressive stress of chemically strengthened float glass obtained by chemically strengthening conventional soda lime glass is about 500 MPa, and the depth of the compressive stress layer is about 10 μm. However, in recent years, chemically strengthened float glass having a surface compressive stress of 600 MPa or more and a depth of a compressive stress layer of 15 μm or more has been developed in order to meet the demand for high scratch resistance.
已报道过浮法玻璃在化学强化后产生翘曲而损害平坦性(专利文献1)。该翘曲是由于在浮法成形时不与熔融锡接触的玻璃面(以下也称为顶面)和与熔融锡接触的玻璃面(以下也称为底面)的化学强化的进行程度不同而产生的。It has been reported that float glass warps and impairs flatness after chemical strengthening (Patent Document 1). This warpage is caused by the difference in the progress of chemical strengthening between the glass surface (hereinafter also referred to as top surface) not in contact with molten tin and the glass surface (hereinafter also referred to as bottom surface) in contact with molten tin during float forming. of.
化学强化的进行程度越强，浮法玻璃的翘曲越大，因此，在为了应对对高耐划伤性的要求而开发的、表面压应力为600MPa以上且压应力层的深度为15μm以上的化学强化浮法玻璃中，与以往的表面压应力为约500MPa且压应力层的深度为约10μm的化学强化浮法玻璃相比，翘曲的问题变得更加显著。The higher the degree of chemical strengthening, the greater the warpage of float glass. Therefore, in response to the demand for high scratch resistance, the surface compressive stress is 600MPa or more and the depth of the compressive stress layer is 15μm or more. In chemically strengthened float glass, the problem of warpage becomes more prominent compared with conventional chemically strengthened float glass having a surface compressive stress of about 500 MPa and a depth of a compressive stress layer of about 10 μm.
以往，作为浮法玻璃的顶面与底面的化学强化进行程度不同的理由，认为是由于在浮法成形时熔融金属侵入到与熔融金属接触的玻璃面中(专利文献1)。Conventionally, the reason why the degree of chemical strengthening progresses differently between the top surface and the bottom surface of float glass is considered to be that molten metal intrudes into the glass surface in contact with the molten metal during float forming (Patent Document 1).
专利文献1中，公开了如下技术：将通过浮法方式制造、加工得到的板状体不进行表面研磨而浸渍到Li离子、Na离子或它们的混合无机盐中或者与上述物质接触，然后进行化学强化，由此改善翘曲。Patent Document 1 discloses a technique of immersing a plate-shaped body produced and processed by a float method into Li ions, Na ions, or their mixed inorganic salts or contacting them without surface grinding, and then performing Chemical strengthening, thereby improving warpage.
另外，以往，为了减小翘曲，采用如下的应对方法：减小由化学强化产生的强化应力，或者在通过对浮法玻璃的顶面和底面进行磨削处理或研磨处理等来除去表面异质层后进行化学强化。In addition, in the past, in order to reduce warping, the following countermeasures have been adopted: reducing the strengthening stress caused by chemical strengthening, or removing surface defects by grinding or polishing the top and bottom surfaces of the float glass. Chemical strengthening after the stratum layer.
现有技术文献prior art literature
专利文献patent documents
专利文献1：日本专利第2033034号公报Patent Document 1: Japanese Patent No. 2033034
发明内容Contents of the invention
发明所要解决的问题The problem to be solved by the invention
但是，专利文献1记载的方法中，需要在化学强化前在混合无机盐中对浮法玻璃进行浸渍处理，较为繁杂。另外，对于减小强化应力的方法而言，化学强化后的浮法玻璃的强度有可能不充分。However, in the method described in Patent Document 1, it is necessary to immerse the float glass in a mixed inorganic salt before chemical strengthening, which is complicated. Moreover, the strength of the float glass after chemical strengthening may not be enough for the method of reducing strengthening stress.
此外，在化学强化前对浮法玻璃的顶面和底面进行磨削处理或研磨处理等的方法从提高生产率的观点考虑存在问题，优选省略这些磨削处理或研磨处理等。In addition, the method of grinding or polishing the top and bottom surfaces of the float glass before chemical strengthening has problems from the viewpoint of improving productivity, and it is preferable to omit these grinding or polishing treatments.
因此，本发明的目的在于提供能够有效地抑制化学强化后的翘曲、并且能够省略或简化化学强化前的研磨处理等的化学强化用浮法玻璃的制造方法。Therefore, the object of this invention is to provide the manufacturing method of the float glass for chemical strengthening which can suppress the warpage after chemical strengthening effectively, and can omit or simplify the polishing process etc. before chemical strengthening.
用于解决问题的手段means of solving problems
本发明人发现，浮法玻璃的底面与顶面的化学强化的进行程度产生差异的主要原因并不是在浮法成形时侵入到与熔融金属接触的玻璃面中的金属，而是顶面与底面的OH浓度差。而且还发现，在熔融金属浴的上游端至距上游端9.1m的下游处之间，从熔融玻璃中脱出的OH量最多。The inventors of the present invention have found that the main cause of the difference in the progress of chemical strengthening between the bottom surface and the top surface of float glass is not the metal intruded into the glass surface in contact with the molten metal during float forming, but the difference between the top surface and the bottom surface. OH concentration difference. Furthermore, it was also found that the amount of OH desorbed from the molten glass was the largest between the upstream end of the molten metal bath and the downstream point 9.1 m from the upstream end.
因此，本发明人发现，通过优化熔融金属浴的上游端至距上游端9.1m的下游处之间的浮法操作，能够减小顶面与底面的OH浓度差，能够减小化学强化后的浮法玻璃的翘曲。而且，基于上述发现完成了本发明。Therefore, the present inventors found that by optimizing the float operation between the upstream end of the molten metal bath and the 9.1m downstream from the upstream end, the OH concentration difference between the top surface and the bottom surface can be reduced, and the OH concentration after chemical strengthening can be reduced. Warping of float glass. Furthermore, the present invention has been accomplished based on the above findings.
即，本发明如下所述。That is, the present invention is as follows.
(1)一种化学强化用浮法玻璃的制造方法，使熔融玻璃流入熔融金属浴中，在使所述熔融玻璃在所述熔融金属浴的浴面上前进并冷却的同时成形为板状，所述化学强化用浮法玻璃的制造方法中，(1) A method for producing float glass for chemical strengthening, comprising pouring molten glass into a molten metal bath, forming the molten glass into a plate shape while advancing and cooling the molten glass on the bath surface of the molten metal bath, In the manufacturing method of the float glass for chemical strengthening,
在将流入所述熔融金属浴中的所述熔融玻璃的粘度设为η0、将距所述熔融金属浴的上游端9.1m的下游处的所述熔融玻璃的粘度设为η1时，When the viscosity of the molten glass flowing into the molten metal bath is η0, and the viscosity of the molten glass downstream from the upstream end of the molten metal bath by 9.1 m is η1,
η1-η0≥2.0×104(Pa·s)。η1-η0≥2.0×104 (Pa·s).
(2)一种化学强化用浮法玻璃的制造方法，使粘度达到2.5×104Pa·s时的温度为850～1100℃的玻璃的熔融玻璃流入熔融金属浴中，在使所述熔融玻璃在所述熔融金属浴的浴面上前进并冷却的同时成形为板状，所述化学强化用浮法玻璃的制造方法中，(2) A method for producing float glass for chemical strengthening, in which molten glass having a temperature of 850 to 1100°C at a viscosity of 2.5×104 Pa·s is poured into a molten metal bath, and the molten glass is Forming into a plate shape while advancing and cooling on the bath surface of the molten metal bath, in the manufacturing method of the float glass for chemical strengthening,
在将流入所述熔融金属浴中的所述熔融玻璃的温度设为T0、将距所述熔融金属浴的上游端9.1m的下游处的所述熔融玻璃的温度设为T1时，When the temperature of the molten glass flowing into the molten metal bath is T0, and the temperature of the molten glass downstream from the upstream end of the molten metal bath by 9.1 m is T1,
T0-T1≥200(℃)。T0-T1≥200(℃).
(3)一种化学强化用浮法玻璃的制造方法，使熔融玻璃流入熔融金属浴中，在使所述熔融玻璃在所述熔融金属浴的浴面上前进并冷却的同时成形为板状，所述化学强化用浮法玻璃的制造方法中，(3) A method for producing float glass for chemical strengthening, comprising pouring molten glass into a molten metal bath, forming the molten glass into a plate shape while advancing and cooling the molten glass on the bath surface of the molten metal bath, In the manufacturing method of the float glass for chemical strengthening,
在所述熔融金属浴的上游端至距上游端9.1m的下游处之间，设置至少一对按压所述熔融玻璃的表面的两侧部的上辊，Between the upstream end of the molten metal bath and the 9.1m downstream from the upstream end, at least a pair of upper rollers pressing the two sides of the surface of the molten glass are arranged,
在将位于最上游的所述一对上辊的旋转速度设为S(m/分钟)时，When the rotational speed of the pair of upper rollers positioned at the most upstream is S (m/min),
9.1/S≤20(分钟)。9.1/S≤20 (minutes).
发明效果Invention effect
根据上述(1)所述的发明，在从熔融玻璃中脱出的OH最多的区域、即熔融金属浴的上游端至距上游端9.1m的下游处之间，使熔融玻璃的粘度增加2.0×104(Pa·s)以上。即，在上述区域中，使熔融玻璃的温度降低预定值以上，因此，能够抑制OH从熔融玻璃中扩散，能够抑制顶面与底面的OH浓度差增大。因此，本发明的化学强化用浮法玻璃不会减小由化学强化产生的应力，并且，即使简化或省略化学强化前的研磨处理等，也能够减小化学强化后的浮法玻璃的翘曲，能够得到优良的平坦度。According to the invention described in the above (1), the viscosity of the molten glass is increased by 2.0×10 in the region where the most OH is released from the molten glass, that is, between the upstream end of the molten metal bath and the downstream position 9.1 m from the upstream end.4 (Pa·s) or more. That is, in the above region, the temperature of the molten glass is lowered by a predetermined value or more, so diffusion of OH from the molten glass can be suppressed, and an increase in the difference in OH concentration between the top surface and the bottom surface can be suppressed. Therefore, the float glass for chemical strengthening of the present invention does not reduce the stress caused by chemical strengthening, and even if the polishing treatment before chemical strengthening is simplified or omitted, the warpage of the float glass after chemical strengthening can be reduced. , excellent flatness can be obtained.
根据上述(2)所述的发明，在使用在850～1100℃下粘度为2.5×104Pa·s的玻璃的熔融玻璃来制造化学强化用浮法玻璃的情况下，在从该熔融玻璃中脱出的OH最多的区域、即熔融金属浴的上游端至距上游端9.1m的下游处之间，使熔融玻璃的温度降低200℃以上。由此，能够抑制OH从熔融玻璃中扩散，能够抑制顶面与底面的OH浓度差增大。因此，能够减小化学强化后的浮法玻璃的翘曲。According to the invention described in (2) above, in the case of producing float glass for chemical strengthening using a molten glass having a viscosity of 2.5×104 Pa·s at 850 to 1100° C., from the molten glass The region where the most desorbed OH, that is, between the upstream end of the molten metal bath and the downstream point 9.1 m from the upstream end, lowers the temperature of the molten glass by 200° C. or more. Thereby, diffusion of OH from the molten glass can be suppressed, and an increase in the OH concentration difference between the top surface and the bottom surface can be suppressed. Therefore, the warpage of the float glass after chemical strengthening can be reduced.
根据上述(3)所述的发明，为了在从熔融玻璃中脱出的OH最多的区域、即熔融金属浴的上游端至距上游端9.1m的下游处之间缩短熔融玻璃的停留时间，以使位于最上游的上辊的旋转速度S满足9.1/S≤20(分钟)的方式进行设定。由此，能够抑制OH从熔融玻璃中扩散，能够抑制顶面与底面的OH浓度差增大。因此，能够减小化学强化后的浮法玻璃的翘曲。According to the invention described in the above (3), in order to shorten the residence time of the molten glass in the region where the most OH is detached from the molten glass, that is, from the upstream end of the molten metal bath to the downstream position 9.1 m from the upstream end, the residence time of the molten glass is shortened so that The rotational speed S of the top roll located most upstream is set so as to satisfy 9.1/S≦20 (minutes). Thereby, diffusion of OH from the molten glass can be suppressed, and an increase in the difference in OH concentration between the top surface and the bottom surface can be suppressed. Therefore, the warpage of the float glass after chemical strengthening can be reduced.
附图说明Description of drawings
图1是本发明的化学强化用浮法玻璃的制造装置的纵截面图。Fig. 1 is a vertical cross-sectional view of an apparatus for producing float glass for chemical strengthening according to the present invention.
图2是图1的制造装置的横截面图。FIG. 2 is a cross-sectional view of the manufacturing apparatus of FIG. 1 .
图3是对本发明的化学强化用浮法玻璃进行化学强化后作为平板显示器用保护玻璃使用的平板显示器的截面图。3 is a cross-sectional view of a flat panel display used as a cover glass for a flat panel display after chemically strengthening the float glass for chemical strengthening of the present invention.
图4是表示粘度的增加量η1-η0与Δ翘曲量换算值的关系的图。Fig. 4 is a graph showing the relationship between the viscosity increase amount η1-η0 and the converted value of the Δ warpage amount.
图5是表示温度的降低量T0-T1与Δ翘曲量换算值的关系的图。Fig. 5 is a graph showing the relationship between the amount of decrease in temperature T0-T1 and the converted value of the amount of Δ warpage.
图6是表示位于最上游的一对上辊的旋转速度S与Δ翘曲量换算值的关系的图。FIG. 6 is a graph showing the relationship between the rotational speed S of a pair of top rolls located most upstream and the converted value of the Δ warpage amount.
具体实施方式Detailed ways
本发明的化学强化用浮法玻璃通过浮法进行成形，具有在成形时与熔融金属接触的底面和与该底面相向的顶面。本发明人发现，如以下所说明的那样，由于对浮法玻璃进行化学强化而产生翘曲的主要原因在于顶面与底面的OH浓度差。The float glass for chemical strengthening of this invention is formed by the float process, and has the bottom surface which contacts molten metal at the time of shaping, and the top surface which faces this bottom surface. The inventors of the present invention found that, as described below, the main cause of warping due to chemical strengthening of float glass is the difference in OH concentration between the top surface and the bottom surface.
在通过浮法制造玻璃时，从上游侧向储存在浮法槽中的熔融金属的表面连续供给熔融玻璃并成形为玻璃带。然后，从浮法槽的下游侧端部将成形后的玻璃带拉出，在退火炉中退火，由此制造平板玻璃。When glass is produced by the float method, molten glass is continuously supplied from the upstream side to the surface of the molten metal stored in the float tank and formed into a glass ribbon. Then, the formed glass ribbon is drawn out from the downstream end of the float tank, and annealed in an annealing furnace to manufacture sheet glass.
通常，在通过浮法制造玻璃时，使用玻璃池窑与浮法槽之间通过通路(キャナル)和流槽(スパウト)连接而使流路缩窄的类型的装置。这种情况下，需要在浮法槽内将玻璃铺展，因此，与后述的另一类型的装置相比，使温度更高的熔融玻璃流出到熔融金属表面并成形。Generally, when glass is produced by the float process, a glass furnace and a float tank are connected by a channel (canal) and a launder (spout) to narrow the flow path. In this case, the glass needs to be spread in the float tank, and therefore, molten glass at a higher temperature is flowed out onto the surface of the molten metal and formed, compared with another type of apparatus described later.
但是，由于浮法槽内的露点低，因此，H2O从玻璃表面扩散，H2O从顶面扩散到气氛中，并且H2O从底面扩散到熔融金属中。因此，利用这种类型的装置制造的浮法玻璃的表面(5～10μm)的OH浓度比内部(典型地深度为约50μm以上)的OH浓度小。温度越高，则H2O的扩散系数越大，因此，相较于与温度更低的熔融金属接触的浮法玻璃的底面，从与露点低或温度高的气氛接触的顶面扩散的H2O的量更多。因此，与浮法玻璃的底面相比，顶面的OH浓度更低。However, since the dew point in the float tank is low,H2O diffuses from the glass surface,H2O diffuses from the top surface into the atmosphere, andH2O diffuses from the bottom surface into the molten metal. Therefore, the surface (5-10 μm) of float glass produced by this type of apparatus has a lower OH concentration than the inside (typically about 50 μm or more in depth). The higher the temperature, the greater the diffusion coefficient ofH2O , so H2O diffused from the top surface in contact with a low dew point or high temperature atmosphere compared to the bottom surface of float glass in contact with a lower temperature molten metal The amount of2 O is more. Therefore, the OH concentration is lower on the top surface compared to the bottom surface of float glass.
另一方面，在通过浮法制造玻璃时，有时使用在玻璃池窑与浮法槽之间流路不缩窄的类型的装置。在利用这种类型的装置进行制造的情况下，不需要在浮法槽内将玻璃铺展，因此，与前面记载的类型的装置相比，将温度更低的熔融玻璃流出到高温的熔融金属上并成形。温度越高，则H2O的扩散系数越大，因此，与浮法玻璃的顶面相比，底面的温度有时更高。在这种情况下，从底面扩散的H2O的量比顶面更多，浮法玻璃的底面的OH浓度比顶面的OH浓度低。On the other hand, when glass is produced by the float method, a type of device that does not narrow the flow path between the glass tank furnace and the float tank may be used. In the case of manufacturing with this type of apparatus, there is no need to spread the glass in the float tank, so that the molten glass flows at a lower temperature onto the molten metal at a higher temperature than in the previously described type of apparatus. and take shape. The higher the temperature, the larger the diffusion coefficient of H2 O. Therefore, the temperature of the bottom surface may be higher than that of the top surface of the float glass. In this case, the amount of H2 O diffused from the bottom surface is larger than that of the top surface, and the OH concentration of the bottom surface of the float glass is lower than that of the top surface.
因此，对于通过浮法制造的玻璃而言，根据制造条件会使顶面的OH浓度比底面的OH浓度低、或者使底面的OH浓度比顶面的OH浓度低，从而产生顶面与底面的OH浓度差。以下，主要对浮法玻璃的顶面的OH浓度比底面的OH浓度低的情况进行说明，但本发明不限于此。Therefore, for glass manufactured by the float method, depending on the manufacturing conditions, the OH concentration of the top surface is lower than that of the bottom surface, or the OH concentration of the bottom surface is lower than that of the top surface, resulting in a gap between the top surface and the bottom surface. The concentration of OH is poor. Hereinafter, although the case where the OH concentration of the top surface of a float glass is lower than the OH concentration of a bottom surface is mainly demonstrated, this invention is not limited to this.
玻璃中的OH浓度高时，氢以SiOH的形式进入到玻璃的Si-O-Si的键合网络中，Si-O-Si的键合断开。玻璃中的OH浓度高时，Si-O-Si的键合断开的部分增多，玻璃化转变温度等热特性降低，因此，在高温下对玻璃进行加热的化学强化时发生应力弛豫，导致应力降低。When the OH concentration in the glass is high, hydrogen enters the Si-O-Si bonding network of the glass in the form of SiOH, and the Si-O-Si bonding is broken. When the OH concentration in the glass is high, the number of broken Si-O-Si bonds increases, and thermal properties such as the glass transition temperature decrease. Therefore, stress relaxation occurs during chemical strengthening of the glass by heating at a high temperature, resulting in stress reduction.
因此，浮法玻璃的顶面和底面中，OH浓度高的玻璃面中在化学强化时应力的产生少，OH浓度低的玻璃面中在化学强化时容易产生应力。Therefore, among the top and bottom surfaces of the float glass, the glass surface with a high OH concentration generates little stress during chemical strengthening, and the glass surface with a low OH concentration easily generates stress during chemical strengthening.
即，认为在对顶面的OH浓度比底面的OH浓度低的浮法玻璃进行化学强化时，与OH浓度高的底面相比，在OH浓度低的顶面中更强地产生应力，玻璃以向顶面侧凸起的方式弯曲，从而产生翘曲。That is, it is considered that when the float glass whose OH concentration on the top surface is lower than that on the bottom surface is chemically strengthened, stress is more strongly generated on the top surface with a low OH concentration than on the bottom surface with a high OH concentration, and the glass is Curved so as to be convex toward the top surface side, warpage occurs.
另一方面，认为在对底面的OH浓度比顶面的OH浓度低的浮法玻璃进行化学强化时，与OH浓度高的顶面相比，在OH浓度低的底面中更强地产生应力，玻璃相反地以向底面侧凸起的方式弯曲，从而产生翘曲。On the other hand, it is considered that when the float glass whose OH concentration on the bottom surface is lower than that on the top surface is chemically strengthened, stress is more strongly generated on the bottom surface with a low OH concentration than on the top surface with a high OH concentration, and the glass On the contrary, it bends so as to be convex toward the bottom surface side, and warpage occurs.
因此，浮法玻璃的顶面与底面中的OH浓度越接近、即顶面与底面的OH浓度差的绝对值的值越小，则化学强化后的顶面与底面的应力的产生程度越接近均衡的状态，翘曲越减小。Therefore, the closer the OH concentration in the top surface and the bottom surface of the float glass is, that is, the smaller the absolute value of the difference in the OH concentration between the top surface and the bottom surface is, the closer the degree of stress generation between the top surface and the bottom surface after chemical strengthening is. In a balanced state, the warpage decreases.
(化学强化用浮法玻璃的制造方法)(Manufacturing method of float glass for chemical strengthening)
基于以上说明的发现，本发明人发明了通过减小浮法玻璃的顶面与底面的OH浓度差从而能够减小化学强化后的翘曲的化学强化用浮法玻璃的制造方法。Based on the findings described above, the present inventors have invented a method of manufacturing float glass for chemical strengthening that can reduce warpage after chemical strengthening by reducing the difference in OH concentration between the top and bottom surfaces of the float glass.
本发明的化学强化用浮法玻璃通过图1和图2所示的制造装置来制造。图1和图2中，12为窑坎(ツイール)，22为位于窑坎下方的固定耐火物，23为流槽的唇砖。图中做了省略，熔融玻璃1通过将原料连续供给至玻璃池窑内并在高温区域熔化而得到。接着，熔融玻璃1被导入到冷却区域而进行温度调节。接着，使熔融玻璃1从连接槽11和由窑坎12与位于其下方的固定耐火物22形成的间隙2内通过，经过流槽的唇砖23后流入浮法槽14内的熔融金属浴5中。The float glass for chemical strengthening of this invention is manufactured with the manufacturing apparatus shown in FIG.1 and FIG.2. In Fig. 1 and Fig. 2, 12 is a kiln ridge (ツイール), 22 is a fixed refractory located under the kiln ridge, and 23 is a lip brick of a launder. It is omitted in the drawing, and the molten glass 1 is obtained by continuously supplying raw materials into a glass tank furnace and melting them in a high-temperature region. Next, the molten glass 1 is introduced into a cooling area, and its temperature is adjusted. Next, the molten glass 1 passes through the gap 2 formed by the kiln ridge 12 and the fixed refractory 22 below it from the connection tank 11, and flows into the molten metal bath 5 in the float tank 14 after passing through the lip brick 23 of the launder middle.
将流入到熔融金属浴5上的熔融玻璃1利用作为在周围具有齿或槽的旋转辊的上辊30对其表面的宽度方向两侧部进行按压，由此在宽度方向上赋予张力。在此，上辊30在熔融玻璃1的宽度方向两侧配设有多组，成对的上辊30的旋转轴32之间大致扩开成八字形。而且，多个上辊30可以分别自由地设定旋转速度，从而能够对熔融玻璃1的行进速度进行调节。Molten glass 1 poured into molten metal bath 5 is given tension in the width direction by pressing both sides in the width direction of its surface with upper roll 30 , which is a rotating roll having teeth or grooves around its periphery. Here, a plurality of sets of upper rolls 30 are arranged on both sides in the width direction of the molten glass 1 , and the rotation shafts 32 of the paired upper rolls 30 are substantially spread out in a figure-eight shape. Moreover, the rotation speed can be freely set for each of the some upper roll 30, and the advancing speed of the molten glass 1 can be adjusted.
另外，图2中，虚线所示的1～5跨度表示自熔融金属浴5的上游端起算向下游侧延伸的距离。1跨度为3.048m(约3.0m)。本实施方式中，在熔融金属浴5中设置有多组上辊30，但本发明不限定于该构成，只要在熔融金属浴5上游端至距上游端3跨度(约9.1m)的下游侧之间设置有至少一对上辊30即可。In addition, in FIG. 2 , the spans 1 to 5 indicated by the dotted line indicate the distance extended to the downstream side from the upstream end of the molten metal bath 5 . 1 The span is 3.048m (about 3.0m). In this embodiment, a plurality of sets of upper rolls 30 are provided in the molten metal bath 5, but the present invention is not limited to this configuration, as long as the upstream end of the molten metal bath 5 to the downstream side of the span (about 9.1 m) from the upstream end 3 At least one pair of upper rollers 30 may be provided therebetween.
在此，为了对OH从熔融金属浴5上的熔融玻璃1中的扩散进行理论性分析，本发明人将与熔融玻璃1的厚度方向相关的OH行为假定为一维的扩散现象，由此构建了控制方程。然后，使用该控制方程，导入熔融玻璃1内的位置、温度、厚度、浴面上的停留时间等要素而进行了OH浓度的分析。结果发现，在熔融金属浴5的上游端至距上游端约9.1m(3跨度)的下游处之间，从熔融玻璃1中脱出的OH量最多。即发现，在熔融金属浴5的上游端至距上游端约9.1m的下游处之间(以下称为OH缺乏区域)OH从熔融玻璃1中的扩散可能会对顶面与底面的OH浓度差和浮法玻璃的化学强化后的翘曲产生较大的影响。Here, in order to theoretically analyze the diffusion of OH from the molten glass 1 on the molten metal bath 5, the present inventors assumed that the OH behavior related to the thickness direction of the molten glass 1 was a one-dimensional diffusion phenomenon, thus constructing the control equation. Then, using this governing equation, the OH concentration was analyzed by introducing elements such as the position, temperature, thickness, and residence time on the bath surface in the molten glass 1 . As a result, it was found that the amount of OH released from the molten glass 1 was the largest between the upstream end of the molten metal bath 5 and the downstream point about 9.1 m (3 spans) from the upstream end. That is, it was found that the diffusion of OH from the molten glass 1 between the upstream end of the molten metal bath 5 and the downstream point about 9.1 m away from the upstream end (hereinafter referred to as the OH-deficient region) may affect the difference in OH concentration between the top surface and the bottom surface. and the warpage after chemical strengthening of the float glass has a large influence.
因此，本发明中，为了优化特别是OH缺乏区域中的浮法操作，通过对熔融玻璃1的温度(粘度)、厚度、停留时间等条件进行适当设定，实现了浮法玻璃的化学强化后的翘曲的减小。Therefore, in the present invention, in order to optimize the float operation especially in the OH-deficient region, by appropriately setting conditions such as the temperature (viscosity), thickness, and residence time of the molten glass 1, chemically strengthened float glass 1 is realized. reduction in warpage.
为了减小顶面与底面的OH浓度差，想到了例如通过使OH缺乏区域中的熔融玻璃1的温度与以往相比大幅降低、即通过使OH缺乏区域中的熔融玻璃1的粘度与以往相比大幅升高来抑制OH从熔融玻璃1中的扩散。In order to reduce the OH concentration difference between the top surface and the bottom surface, for example, by making the temperature of the molten glass 1 in the OH-deficient region significantly lower than before, that is, by making the viscosity of the molten glass 1 in the OH-deficient region comparable to the conventional The ratio is greatly increased to suppress the diffusion of OH from the molten glass 1 .
在此，本发明可以与组成无关地适用于任意的熔融玻璃1，在将流入熔融金属浴5中的熔融玻璃1的粘度设为η0、将距熔融金属浴5上游端9.1m(3跨度)的下游处的熔融玻璃1的粘度设为η1时，优选使η1-η0≥2.0×104(Pa·s)，更优选使η1-η0≥3.0×104(Pa·s)。Here, the present invention can be applied to any molten glass 1 regardless of the composition. The viscosity of the molten glass 1 flowing into the molten metal bath 5 is η0, and the distance from the upstream end of the molten metal bath 5 is 9.1 m (3 spans). When the viscosity of the molten glass 1 at the downstream side is η1, it is preferable to satisfy η1-η0≥2.0×104 (Pa·s), more preferably η1-η0≥3.0×104 (Pa·s).
特别是在使用具有适合化学强化用浮法玻璃的组成、粘度达到2.5×104Pa·s时的温度为850～1100℃的玻璃的熔融玻璃1的情况下，在将流入熔融金属浴5中的熔融玻璃1的温度设为T0、将距熔融金属浴5上游端9.1m的下游处的熔融玻璃1的温度设为T1时，优选T0-T1≥200(℃)，更优选T0-T1≥230(℃)。In particular, in the case of using molten glass 1 having a composition suitable for float glass for chemical strengthening and having a temperature of 850 to 1100°C when the viscosity reaches 2.5×104 Pa·s, When the temperature of the molten glass 1 is set as T0, and the temperature of the molten glass 1 at the downstream position 9.1 m from the upstream end of the molten metal bath 5 is set as T1, preferably T0-T1≥200 (° C.), more preferably T0-T1≥ 230 (℃).
另外，想到通过使OH缺乏区域中的熔融玻璃1的停留时间与以往相比缩短来抑制OH从熔融玻璃1中的扩散。由此，能够减小顶面与底面的OH浓度差，能够减少化学强化后的翘曲量。Moreover, it is conceived to suppress the diffusion of OH from the molten glass 1 by shortening the residence time of the molten glass 1 in the OH-deficient region compared with conventional ones. Thereby, the difference in OH concentration between the top surface and the bottom surface can be reduced, and the amount of warping after chemical strengthening can be reduced.
在此，OH缺乏区域中的熔融玻璃1的行进速度与位于最上游的一对上辊30的旋转速度S存在相关关系。因此，OH缺乏区域中的熔融玻璃1的停留时间与用OH缺乏区域的长度(9.1m)除以位于最上游的一对上辊30的旋转速度S而得到的值存在相关关系。因此，本发明中，对于上述旋转速度S，以满足9.1/S≤20(分钟)、更优选9.1/S≤10(分钟)的方式进行设定，由此，缩短OH缺乏区域中的熔融玻璃1的停留时间。Here, there is a correlation between the traveling speed of molten glass 1 in the OH-deficient region and the rotational speed S of the pair of upper rolls 30 located most upstream. Therefore, the residence time of molten glass 1 in the OH deficient region is correlated with the value obtained by dividing the length (9.1 m) of the OH deficient region by the rotation speed S of the pair of upper rolls 30 located most upstream. Therefore, in the present invention, the above-mentioned rotation speed S is set so as to satisfy 9.1/S≤20 (minutes), more preferably 9.1/S≤10 (minutes), thereby shortening the temperature of the molten glass in the OH-deficient region. 1 dwell time.
另外，为了缩短OH缺乏区域中的熔融玻璃1的停留时间，除了调节上述的位于最上游的一对上辊30的旋转速度以外，还可以通过调节OH缺乏区域中的其他上辊30的旋转速度、调节上辊30所配置的位置或角度来实现。例如，可以通过缩小OH缺乏区域中成对的上辊30的间隔，在不增大熔融玻璃1的宽度的情况下提高生产线速度而快速向下游侧输送，在浮法槽14下游区域中，通过增大成对的上辊30的间隔来增大熔融玻璃1的宽度，从而使玻璃带4形成预定的形状。In addition, in order to shorten the residence time of the molten glass 1 in the OH-deficient region, in addition to adjusting the rotation speed of the above-mentioned pair of upper rollers 30 located in the most upstream, it is also possible to adjust the rotation speed of other upper rollers 30 in the OH-deficient region. 1. Adjust the position or angle of the upper roller 30 to achieve. For example, by narrowing the distance between the paired top rolls 30 in the OH-deficient region, the molten glass 1 can be conveyed to the downstream side quickly without increasing the width of the molten glass 1 by increasing the line speed. In the downstream region of the float tank 14, by The distance between the paired upper rolls 30 is increased to increase the width of the molten glass 1 to form the glass ribbon 4 into a predetermined shape.
在浮法槽14中成形的玻璃带4在未图示的退火炉内退火至室温，经过清洗、检查、切割等工序后，结束化学强化用浮法玻璃的制造工序。另外，在利用上辊30进行按压后的玻璃带4的宽度方向两侧部，会沿行进方向形成凸凹痕迹，因此，在切割工序中将其除去。The glass ribbon 4 formed in the float tank 14 is annealed to room temperature in an annealing furnace not shown, and after cleaning, inspection, and cutting, the manufacturing process of the float glass for chemical strengthening is completed. Moreover, in the width direction both sides of the glass ribbon 4 pressed by the top roller 30, since the uneven|corrugated trace is formed along the advancing direction, it removes this in a cutting process.
通过对经过这样的工序而成形为板状的化学强化用浮法玻璃进行化学强化，能够得到化学强化浮法玻璃。化学强化是通过在玻璃化转变温度以下的温度下利用离子交换将玻璃表面的离子半径小的碱金属离子(典型地为Li离子或Na离子)交换为离子半径更大的碱离子(典型地为K离子)而在玻璃表面形成压应力层的处理。化学强化处理可以通过现有公知的方法进行。The chemically strengthened float glass can be obtained by chemically strengthening the float glass for chemically strengthening formed into a plate shape through such a process. Chemical strengthening is to exchange alkali metal ions (typically Li ions or Na ions) on the surface of the glass for alkali ions with larger ionic radii (typically Li ions or Na ions) by ion exchange at a temperature below the glass transition temperature. K ions) to form a compressive stress layer on the glass surface. The chemical strengthening treatment can be performed by a conventionally known method.
另外，通过本发明制造的化学强化用浮法玻璃的板厚优选为1.5mm以下，更优选为1.1mm以下。另外，典型地为0.7mm以上，但根据需要也使用比该厚度薄的玻璃。Moreover, the plate thickness of the float glass for chemical strengthening manufactured by this invention becomes like this. Preferably it is 1.5 mm or less, More preferably, it is 1.1 mm or less. Moreover, it is typically 0.7 mm or more, but glass thinner than this thickness is also used as needed.
另外，通过本发明制造的化学强化用浮法玻璃能够与组成无关地减小化学强化后的翘曲，但作为化学强化用浮法玻璃的组成，可以列举例如以下的玻璃的组成。Moreover, the float glass for chemical strengthening manufactured by this invention can reduce the warpage after chemical strengthening irrespective of composition, However, As a composition of the float glass for chemical strengthening, the composition of the following glass is mentioned, for example.
(i)一种玻璃，以摩尔％表示的组成计，含有50～80％的SiO2、2～25％的Al2O3、0～10％的Li2O、0～18％的Na2O、0～10％的K2O、0～15％的MgO、0～5％的CaO和0～5％的ZrO2。在此，例如，“含有0～10％的K2O”是指K2O不是必要的、但可以在不损害本发明的目的的范围内含有至10％的含义。(i) A glass containing 50 to 80% of SiO2 , 2 to 25% of Al2 O3 , 0 to 10% of Li2 O, and 0 to 18% of Na2 in terms of composition expressed in mol % O, 0-10% K2 O, 0-15% MgO, 0-5% CaO and 0-5% ZrO2 . Here, for example, "contains 0 to 10% of K2 O" means that K2 O is not essential but may be contained up to 10% within a range that does not impair the object of the present invention.
(ii)一种玻璃，以摩尔％表示的组成计，含有50～74％的SiO2、1～10％的Al2O3、6～14％的Na2O、3～11％的K2O、2～15％的MgO、0～6％的CaO和0～5％的ZrO2，SiO2和Al2O3的含量的合计为75％以下，Na2O和K2O的含量的合计为12～25％，MgO和CaO的含量的合计为7～15％。(ii) A glass containing 50 to 74% of SiO2 , 1 to 10% of Al2 O3 , 6 to 14% of Na2 O, and 3 to 11% of K2 in terms of composition expressed in mol % O, 2-15% of MgO, 0-6% of CaO and 0-5% of ZrO2 , the total content of SiO2 and Al2 O3 is 75% or less, and the content of Na2 O and K2 O The total is 12% to 25%, and the total content of MgO and CaO is 7% to 15%.
(iii)一种玻璃，以摩尔％表示的组成计，含有68～80％的SiO2、4～10％的Al2O3、5～15％的Na2O、0～1％的K2O、4～15％的MgO和0～1％的ZrO2。(iii) A glass containing 68 to 80% of SiO2 , 4 to 10% of Al2 O3 , 5 to 15% of Na2 O, and 0 to 1% of K2 in terms of composition expressed in mol % O, 4-15% of MgO and 0-1% of ZrO2 .
(iv)一种玻璃，以摩尔％表示的组成计，含有67～75％的SiO2、0～4％的Al2O3、7～15％的Na2O、1～9％的K2O、6～14％的MgO和0～1.5％的ZrO2，SiO2和Al2O3的含量的合计为71～75％，Na2O和K2O的含量的合计为12～20％，在含有CaO时，其含量小于1％。(iv) A glass containing 67 to 75% of SiO2 , 0 to 4% of Al2 O3 , 7 to 15% of Na2 O, and 1 to 9% of K2 in terms of composition expressed in mol % O, 6-14% MgO and 0-1.5% ZrO2 , the total content of SiO2 and Al2 O3 is 71-75%, the total content of Na2 O and K2 O is 12-20% , when containing CaO, its content is less than 1%.
另外，浮法玻璃的翘曲量可以使用三维形状测定器(例如，三鹰光器株式会社制造)测定。具体而言，在浮法玻璃的宽度方向上的数个部位求出最高点与最低点之差，基于这些差的平均值求出翘曲量。另外，化学强化前后的浮法玻璃的翘曲量的变化可以通过Δ翘曲量[(化学强化后翘曲量)-(化学强化前翘曲量)]来测定。本发明中，使用100mm见方的浮法玻璃进行测定，换算成0.8mm的板厚时的Δ翘曲量换算值优选为100μm以下。In addition, the amount of warpage of float glass can be measured using a three-dimensional shape measuring device (for example, the product made by Mitaka Koki Co., Ltd.). Specifically, the difference between the highest point and the lowest point was obtained at several locations in the width direction of the float glass, and the amount of warpage was obtained based on the average value of these differences. In addition, the change in the amount of warping of the float glass before and after chemical strengthening can be measured by the amount of Δ warping [(the amount of warping after chemical strengthening)-(the amount of warping before chemical strengthening)]. In the present invention, the measurement is performed using float glass of 100 mm square, and the converted value of the amount of Δ warpage when converted into a plate thickness of 0.8 mm is preferably 100 μm or less.
以下，对于将本发明的浮法玻璃进行化学强化后作为平板显示器用保护玻璃使用的例子进行说明。图3为配置有保护玻璃的显示装置的截面图。另外，在以下的说明中，前后左右以图中的箭头的朝向为基准。Hereinafter, the example which chemically strengthens the float glass of this invention and uses it as a cover glass for flat panel displays is demonstrated. 3 is a cross-sectional view of a display device equipped with a cover glass. In addition, in the following description, front, rear, left, and right are based on the directions of the arrows in the drawings.
显示装置10具备设置在壳体15内的显示面板20和以覆盖显示面板20的整个面且包围壳体15的前方的方式设置的保护玻璃40。The display device 10 includes a display panel 20 provided in the casing 15 , and a cover glass 40 provided so as to cover the entire surface of the display panel 20 and surround the front of the casing 15 .
保护玻璃40主要是为了提高显示装置10的美观和强度、防止冲击破损等而设置的，由整体形状大致为平面形状的一张板状玻璃形成。保护玻璃40可以以与显示面板20的显示侧(前侧)分离的方式(以具有空气层的方式)设置，也可以通过具有透光性的胶粘膜(未图示)粘贴到显示面板20的显示侧。The cover glass 40 is provided mainly to improve the appearance and strength of the display device 10 and to prevent impact damage, etc., and is formed of a sheet of glass whose overall shape is substantially planar. The cover glass 40 may be provided separately from the display side (front side) of the display panel 20 (with an air layer), or may be attached to the display panel 20 via a light-transmitting adhesive film (not shown). display side.
在保护玻璃40的使来自显示面板20的光出射的正面设置有功能膜41。在使来自显示面板20的光入射的背面，在与显示面板20对应的位置设置有功能膜42。另外，功能膜41、42在图3中设置于两面，但不限于此，也可以设置于正面或背面，还可以省略。A functional film 41 is provided on the front surface of the cover glass 40 that emits light from the display panel 20 . A functional film 42 is provided at a position corresponding to the display panel 20 on the rear surface where light from the display panel 20 is incident. In addition, although the functional films 41 and 42 are provided on both surfaces in FIG. 3 , they are not limited thereto, and may be provided on the front or back, or may be omitted.
功能膜41、42具有例如防止周围光的反射、防止冲击破损、屏蔽电磁波、屏蔽近红外线、修正色调和/或提高耐划伤性等功能，其厚度和形状等可以根据用途适当选择。功能膜41、42例如可以通过将树脂制的膜粘贴到保护玻璃40上而形成。或者，也可以通过蒸镀法、溅射法或CVD法等薄膜形成法而形成。The functional films 41 and 42 have functions such as preventing reflection of ambient light, preventing impact damage, shielding electromagnetic waves, shielding near-infrared rays, correcting color tone, and/or improving scratch resistance, and their thickness and shape can be appropriately selected according to the application. The functional films 41 and 42 can be formed, for example, by affixing a resin film to the cover glass 40 . Alternatively, it may be formed by a thin film forming method such as a vapor deposition method, a sputtering method, or a CVD method.
标号44为黑色层，是例如通过将含有颜料粒子的油墨涂布到保护玻璃40上并对其照射紫外线或者加热煅烧后进行冷却而形成的覆膜。通过形成该覆膜44，使得从壳体15的外侧观察不到显示面板等，从而提高外观的审美性。Reference numeral 44 is a black layer, which is a film formed by, for example, applying ink containing pigment particles on the cover glass 40, irradiating it with ultraviolet rays or heating and firing, and then cooling. By forming the coating 44, the display panel and the like cannot be seen from the outside of the housing 15, thereby improving the aesthetics of the appearance.
实施例Example
以下，对本发明的实施例具体进行说明，但本发明不限定于这些实施例。Hereinafter, examples of the present invention will be specifically described, but the present invention is not limited to these examples.
将下述组成的化学强化用浮法玻璃在浮法槽14的长度等条件不同的两条生产线(生产线I和生产线II)中通过上述的制造方法进行制造。The float glass for chemical strengthening of the following composition was manufactured by the above-mentioned manufacturing method in two production lines (line I and line II) in which conditions, such as the length of the float tank 14, differ.
以摩尔％计，含有64.2％的SiO2、8.0％的Al2O3、10.5％的MgO、0.1％的CaO、0.1％的SrO、0.1％的BaO、12.5％的Na2O、4.0％的K2O、0.5％的ZrO2的玻璃。In mole %, it contains 64.2% SiO2 , 8.0% Al2 O3 , 10.5% MgO, 0.1% CaO, 0.1% SrO, 0.1% BaO, 12.5% Na2 O, 4.0% K2 O, 0.5% ZrO2 glass.
在此，该玻璃的粘度达到约2.5×104Pa·s时的温度为约1010℃。Here, the temperature at which the viscosity of the glass reaches about 2.5×104 Pa·s is about 1010°C.
此时，测定流入熔融金属浴5中的熔融玻璃1的温度T0和距熔融金属浴5上游端9.1m的下游处的熔融玻璃1的温度T1，求出这些位置处的粘度η0、η1。另外，流入熔融金属浴5中的熔融玻璃1的温度T0为使热电偶与连接槽11中的玻璃坯料接触而测定的值。另外，距熔融金属浴5上游端9.1m的下游处的熔融玻璃1的温度T1，对于生产线I而言是对使用辐射温度计在2～3跨度中间部和4～5跨度中间部测定的2个值进行内插而导出的值，对于生产线II而言是对使用辐射温度计在2～3跨度中间部和5～6跨度中间部测定的2个值进行内插而导出的值。At this time, the temperature T0 of the molten glass 1 flowing into the molten metal bath 5 and the temperature T1 of the molten glass 1 downstream from the upstream end of the molten metal bath 5 by 9.1 m were measured, and the viscosities η0 and η1 at these positions were obtained. In addition, the temperature T0 of the molten glass 1 which flowed into the molten metal bath 5 is the value measured by bringing a thermocouple into contact with the glass blank in the connection tank 11. In addition, the temperature T1 of the molten glass 1 downstream of 9.1 m from the upstream end of the molten metal bath 5 is two values measured at the middle part of the 2-3 span and the middle part of the 4-5 span with respect to the production line 1. The value derived by interpolating the value is a value derived by interpolating two values measured at the middle part of the 2-3 span and the middle part of the 5-6 span using a radiation thermometer for the production line II.
另外，在化学强化前使用三鹰光器株式会社制造的三维形状测定器(NH-3MA)测定浮法玻璃的翘曲量。然后，将各浮法玻璃利用硝酸钾熔盐进行化学强化。然后，也同样测定化学强化后的浮法玻璃的翘曲量，算出100mm见方的浮法玻璃的Δ翘曲量(＝化学强化后翘曲量-化学强化前翘曲量)。在此，Δ翘曲量与板厚的平方成反比，因此，为了消除板厚的影响，通过以下的计算式将Δ翘曲量换算成板厚为0.8mm的情况，以Δ翘曲量换算值计算。Moreover, the warpage amount of the float glass was measured using the three-dimensional shape measuring instrument (NH-3MA) by Mitaka Koki Co., Ltd. before chemical strengthening. Then, each float glass was chemically strengthened with potassium nitrate molten salt. Then, the warpage amount of the float glass after chemical strengthening was also measured similarly, and the Δ warpage amount (=warpage amount after chemical strengthening-warpage amount before chemical strengthening) of the float glass of 100 mm square was calculated. Here, the amount of Δ warpage is inversely proportional to the square of the plate thickness. Therefore, in order to eliminate the influence of the plate thickness, the amount of Δ warpage is converted into the case of a plate thickness of 0.8mm by the following calculation formula, and converted by the amount of Δ warp value calculation.
Δ翘曲量换算值＝Δ翘曲量×(板厚)2÷0.82Δ warpage conversion value = Δ warpage x (plate thickness)2 ÷ 0.82
图4中示出了通过生产线I和生产线II制造的浮法玻璃中OH缺乏区域的熔融玻璃1的粘度的增加量η1-η0(Pa·s)与Δ翘曲量换算值(μm)的关系。可知对于生产线I和生产线II而言，Δ翘曲量换算值均随着OH缺乏区域的粘度的增加量η1-η0增大而减小。认为这是由于，随着OH缺乏区域的粘度的增加量η1-η0增大、即随着OH缺乏区域的温度的降低量T0-T1增大，OH从熔融玻璃1中的扩散得到抑制，从而抑制了顶面与底面的OH浓度差增大。特别是在η1-η0≥2.0×104(Pa·s)的范围内，几乎全部样品的Δ翘曲量换算值均为100(μm)以下，在η1-η0≥3.0×104(Pa·s)的范围内，全部样品的Δ翘曲量换算值均为100(μm)以下，可知有效地抑制了化学强化后的翘曲。Fig. 4 shows the relationship between the viscosity increase η1-η0 (Pa·s) of the molten glass 1 in the OH-deficient region of the float glass produced by the production line I and the production line II and the converted value of the Δ warpage (μm) . It can be seen that for the production line I and the production line II, the converted value of the Δ warpage decreases as the viscosity increase η1-η0 of the OH-deficient region increases. This is considered to be because the diffusion of OH from the molten glass 1 is suppressed as the increase amount η1-η0 of the viscosity of the OH-deficient region increases, that is, as the decrease amount T0-T1 of the temperature of the OH-deficient region increases, and thus An increase in the OH concentration difference between the top surface and the bottom surface is suppressed. Especially in the range of η1-η0≥2.0×104 (Pa·s), the converted value of Δ warpage of almost all samples is below 100 (μm), and in the range of η1-η0≥3.0×104 (Pa·s) In the range of s), the converted value of the Δ warpage amount of all the samples was 100 (μm) or less, and it was found that the warpage after chemical strengthening was effectively suppressed.
图5中示出了通过生产线I和生产线II制造的浮法玻璃中OH缺乏区域的熔融玻璃1的温度的降低量T0-T1(℃)与Δ翘曲量换算值(μm)的关系。基于与上述同样的理由，可知对于生产线I和生产线II而言，Δ翘曲量换算值均随着OH缺乏区域的温度的降低量T0-T1增大而减小。特别是在T0-T1≥200(℃)的范围内，几乎全部样品的Δ翘曲量换算值均为100(μm)以下，在T0-T1≥230(℃)的范围内，全部样品的Δ翘曲量换算值均为100(μm)以下，可知有效地抑制了化学强化后的翘曲。5 shows the relationship between the temperature drop T0-T1 (° C.) and the converted value (μm) of the Δ warp amount in the molten glass 1 in the OH-deficient region of the float glass produced by the line I and the line II. For the same reason as above, it can be seen that the converted value of the Δ warpage decreases as the temperature drop T0-T1 of the OH-deficient region increases in both the production line I and the production line II. Especially in the range of T0-T1 ≥ 200 (°C), the converted value of Δ warpage of almost all samples is below 100 (μm), and in the range of T0-T1 ≥ 230 (°C), the Δ warpage of all samples The warpage amount conversion values were all 100 (μm) or less, and it was found that the warpage after chemical strengthening was effectively suppressed.
图6中示出了在通过生产线I和生产线II制造浮法玻璃时改变位于最上游的一对上辊30的旋转速度S的情况下，用OH缺乏区域的长度(9.1m)除以位于最上游的一对上辊30的旋转速度S而得到的值即9.1/S(分钟)与Δ翘曲量换算值(μm)的关系。可知对于生产线I和生产线II而言，Δ翘曲量换算值均随着9.1/S(分钟)减小而减小。认为这是由于，随着9.1/S(分钟)减小，OH缺乏区域中的熔融玻璃1的行进速度加快，因此，从熔融玻璃1中扩散的OH的绝对量减少，从而抑制了顶面与底面的OH浓度差增大。特别是在9.1/S≤20(分钟)的范围内，全部样品的Δ翘曲量换算值均为100(μm)以下，在9.1/S≤10(分钟)的范围内，全部样品的Δ翘曲量换算值均为80(μm)以下，可知有效地抑制了化学强化后的翘曲。6 shows that in the case of changing the rotational speed S of the pair of upper rolls 30 positioned most upstream when float glass is manufactured through the production line I and the line II, the length (9.1 m) of the OH-deficient region is divided by the length of the uppermost roll 30 located at the most upstream. The relationship between 9.1/S (minute), which is a value obtained from the rotational speed S of the pair of upstream upper rolls 30 , and the converted value (μm) of the amount of Δ warpage. It can be seen that for the production line I and the production line II, the converted value of the Δ warpage decreases as 9.1/S (minute) decreases. This is considered to be because, as 9.1/S (min) decreases, the traveling speed of the molten glass 1 in the OH-deficient region increases, and therefore, the absolute amount of OH diffused from the molten glass 1 decreases, thereby suppressing the contact between the top surface and The OH concentration difference at the bottom surface increases. Especially in the range of 9.1/S≤20 (minutes), the conversion value of Δ warpage of all samples is below 100 (μm), and in the range of 9.1/S≤10 (minutes), the Δ warpage of all samples The curvature conversion values were all 80 (μm) or less, and it was found that the warpage after chemical strengthening was effectively suppressed.
以上对本发明的实施方式进行了说明，但本发明可以在不脱离其主旨的范围内进行各种设计变更。As mentioned above, although embodiment of this invention was described, this invention can make various design changes in the range which does not deviate from the summary.
本申请基于2012年6月4日提出的日本专利申请2012-127396，其内容作为参考并入本说明书中。This application is based on the JP Patent application 2012-127396 of an application on June 4, 2012, The content is taken in here as a reference.
标号说明Label description
1 熔融玻璃1 molten glass
2 间隙2 clearance
4 玻璃带4 glass ribbons
5 熔融金属浴5 molten metal bath
10 显示装置10 display device
11 连接槽11 connection slot
12 窑坎12 kiln ridge
14 浮法槽14 float tank
15 壳体15 shell
20 显示面板20 display panel
22 固定耐火物22 Fixed refractory
23 唇砖23 lip brick
30 上辊30 upper roll
32 旋转轴32 axis of rotation
40 保护玻璃40 Protective glass
41、42 功能膜41, 42 Functional film
44 黑色层44 black layers
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP2012-127396 | 2012-06-04 | ||
| JP2012127396 | 2012-06-04 | ||
| PCT/JP2013/064193WO2013183449A1 (en) | 2012-06-04 | 2013-05-22 | Method for production of float glass for chemical strengthening |
| Publication Number | Publication Date |
|---|---|
| CN104364206Atrue CN104364206A (en) | 2015-02-18 |
| CN104364206B CN104364206B (en) | 2016-11-30 |
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| CN111117440A (en)* | 2019-12-25 | 2020-05-08 | 东莞市晶博光电有限公司 | Application of UV protective oil in solving warping of float glass |
| CN112408781A (en)* | 2019-08-20 | 2021-02-26 | Ａｇｃ株式会社 | Method for producing lithium aluminosilicate glass and float glass plate |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000281365A (en)* | 1999-04-01 | 2000-10-10 | Nippon Sheet Glass Co Ltd | Production of float type sheet glass and apparatus for production therefor |
| JP2008143746A (en)* | 2006-12-11 | 2008-06-26 | Nippon Electric Glass Co Ltd | Method of manufacturing glass plate, apparatus therefor and glass substrate for flat panel display |
| JP2010168252A (en)* | 2009-01-23 | 2010-08-05 | Nippon Electric Glass Co Ltd | Process of producing tempered glass |
| CN101848874A (en)* | 2007-10-25 | 2010-09-29 | 旭硝子株式会社 | Manufacturing method of flat glass |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2000281365A (en)* | 1999-04-01 | 2000-10-10 | Nippon Sheet Glass Co Ltd | Production of float type sheet glass and apparatus for production therefor |
| JP2008143746A (en)* | 2006-12-11 | 2008-06-26 | Nippon Electric Glass Co Ltd | Method of manufacturing glass plate, apparatus therefor and glass substrate for flat panel display |
| CN101848874A (en)* | 2007-10-25 | 2010-09-29 | 旭硝子株式会社 | Manufacturing method of flat glass |
| JP2010168252A (en)* | 2009-01-23 | 2010-08-05 | Nippon Electric Glass Co Ltd | Process of producing tempered glass |
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN112408781A (en)* | 2019-08-20 | 2021-02-26 | Ａｇｃ株式会社 | Method for producing lithium aluminosilicate glass and float glass plate |
| CN112408781B (en)* | 2019-08-20 | 2024-07-12 | Ａｇｃ株式会社 | Method for producing lithium-aluminum-silicon glass and float glass plate |
| CN111117440A (en)* | 2019-12-25 | 2020-05-08 | 东莞市晶博光电有限公司 | Application of UV protective oil in solving warping of float glass |
| Publication number | Publication date |
|---|---|
| JPWO2013183449A1 (en) | 2016-01-28 |
| JP6065006B2 (en) | 2017-01-25 |
| WO2013183449A1 (en) | 2013-12-12 |
| TW201406674A (en) | 2014-02-16 |
| KR20150022805A (en) | 2015-03-04 |
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| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CP01 | Change in the name or title of a patent holder | ||
| CP01 | Change in the name or title of a patent holder | Address after:Tokyo, Japan Patentee after:AGC Corporation Address before:Tokyo, Japan Patentee before:Asahi Glass Co., Ltd. |