JP2018052804A - Glass sheet and manufacturing method of glass substrate - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a glass sheet with suppressing effects of a reaction gas on a formed surface such as a semiconductor element in an opposite side while roughing a surface which is an absorption surface and a manufacturing method of the glass sheet (glass substrate).SOLUTION: There is provided a glass sheet with suppressing effects of a reaction gas on a formed surface such as a semiconductor element in an opposite side while roughing a surface which is an absorption surface. The glass sheet 1 has a first main surface 10, a second main surface 20, a first edge surface 30, a second edge surface 40, a third edge surface 50 and a forth edge surface 60. The second main surface 20 is etched by gaseous hydrogen fluoride which is a reaction gas while transporting in a surface roughing device 100, other surfaces suppress effects of the reaction gas as much as possible. Especially the first main surface 10 has better adhesiveness to a semiconductor element or the like formed on the first main surface 10 by increasing a value of Al/Si than the second main surface 20 and suppressing leeching of Al by a glass component.SELECTED DRAWING: Figure 1

Description

  The present invention relates to a glass plate used for a flat panel display or the like and a method for producing a glass substrate (glass plate).

  In the manufacturing process of flat panel displays, etc., a glass plate is held on a stage (pedestal) by vacuum suction to form a circuit, etc., and peeling electrification occurs when the glass plate is removed from the stage, causing cracks and cracks in the glass plate For this reason, it is known that the adsorption surface is roughened to prevent peeling electrification (see Patent Document 1).

Patent Document 1 includes a first surface that is a surface on which a semiconductor element or a color film is formed, and a second surface opposite to the first surface, and the second surface is larger than −1.5, and A glass plate which is a substrate using a poloaluminosilicate glass having an Rsk smaller than −0.5 and having a composition containing SiO ₂ , Al ₂ O ₃ and B ₂ O ₃ , and mounting the glass plate It discloses that the area of the second surface in contact with the table (stage) surface is reduced by the surface treatment, and the charging of the glass substrate is more effectively suppressed.

JP 2014-69999 A

  In Patent Literature 1, there is a possibility that not only the second surface but also the first surface forming a semiconductor element or the like may be affected by the reaction gas due to the wraparound of the hydrogen fluoride gas that is the reaction gas. For example, the smoothness of the surface of the first main surface is lost, or Al on the glass surface is substituted with F by the reaction gas to show oil repellency, thereby deteriorating the adhesion of semiconductor elements and the like. As described above, when a surface (first surface) different from the surface (second surface) that is originally to be roughened is affected by the reaction gas, formation of a semiconductor element, a color filter, a black matrix (BM), or the like is formed. There is a problem that sometimes causes trouble.

  The present invention provides a glass plate and a method for producing the glass plate (glass substrate) in which the surface serving as the adsorption surface is rough and the influence of the reaction gas on the formation surface of the opposite semiconductor element or the like is suppressed.

  The glass plate of the present invention has a first main surface, a second main surface facing the first main surface, and an end surface connecting the first main surface and the second main surface, The first surface roughness of one main surface is smaller than the second surface roughness of the second main surface, and the value of Al / Si is greater on the first main surface than on the second main surface.

  The method for producing a glass substrate according to the present invention is a method for producing a glass substrate for a display, wherein only one glass surface of the main surface of the glass substrate and a rough surface using a reaction gas are prepared. And a roughening step.

  ADVANTAGE OF THE INVENTION According to this invention, the glass plate which suppressed the influence of the reactive gas with respect to formation surfaces, such as a semiconductor element on the other side, can be provided, making the surface used as an adsorption surface rough.

1A and 1B show an example of a glass plate according to the present invention, and FIG. 1A is a front perspective view, and FIG. 1B is a conceptual diagram of a conveying state in a roughening device. FIGS. 2A to 2B are conceptual diagrams showing an example of a method for producing a glass plate according to the present invention, which are (a) Embodiment 1 and (b) Embodiment 2. FIG. FIGS. 3A to 3B are a third embodiment of FIG. 3A and a fourth embodiment of FIG. 3B that follow FIGS. 2A and 2B. 4 (a) to 4 (c) show the results of measuring the fluorine content and the Al / Si ratio of the first main surface of the glass plate according to the present invention, FIG. 4 (a) is a front view of the measurement point, and FIG. (B) is a table of measurement results of fluorine content, and FIG. 4 (c) is a table of Al / Si measurement results. 5 (a) to 5 (c) are tables showing values measured with indices indicating various roughnesses of the glass plate according to the present invention. FIG. 5 (a) shows measured values of the first main surface, and FIG. b) is a measurement value of the second principal surface, and FIG. 5C is a value of the first principal surface / second principal surface with respect to the average values of FIGS. 5A to 5B. 6 (a) to 6 (b) are tables in which cullet peeling rates at the first end surface, the second end surface, the third end surface, and the fourth end surface of the glass plate according to the present invention are measured, and FIG. The first sample, FIG. 6B, is the second sample.

  Hereinafter, specific embodiments of the glass plate according to the present invention will be described in detail with reference to the drawings.

  1 (a) to 1 (b) show an example of a glass plate according to the present invention, FIG. 1 (a) is a front perspective view, and FIG. 1 (b) is a conceptual view of a conveying state in a roughening device. is there. An example of a glass plate is explained in full detail using Fig.1 (a)-(b).

  The glass plate 1 of the present embodiment has a substantially rectangular shape, and includes a first main surface 10, a second main surface 20 facing the first main surface 10, a first main surface 10, and a second main surface 20. Four end surfaces are provided, and the four end surfaces are a first end surface 30, a second end surface 40 that faces the first end surface 30, and a third end surface that connects one end of the first end surface 30 and one end of the second end surface 40. 50 and the other end of the first end face 30 and the other end of the second end face 40, and has a fourth end face 60 that faces the third end face 50.

  In the roughening apparatus 100 installed in the conveying apparatus that conveys the glass plate 1, the upper surface is the first main surface 10, which is in contact with the rotating roller 101 and etched with hydrogen fluoride gas (HF) as a reaction gas. The second main surface 20 is the first main surface 20, the front end surface in the transport direction (see the arrow direction in the figure) is the first end surface 30, the end surface opposite to the first end surface 30 is the second end surface 40, and the glass plate When viewed from the side of the first main surface 10, the right side is the third end surface 50, and the left side is the fourth end surface 60.

  The glass plate 1 of this embodiment is used for manufacture of flat panel displays (FPD), such as a liquid crystal display, a plasma display, and an organic EL display, for example. The glass plate 1 has, for example, a rectangular shape with a plate thickness of about 0.2 mm to 0.8 mm and a length and width of about 600 mm to 3000 mm.

  The first main surface 10 of the glass plate 1 has a plurality of layers including a semiconductor element such as a TFT, a polysilicon thin film, an ITO (Indium Thin Oxide) thin film, a color filter, and a black matrix (BM) in the FPD manufacturing process. This is the surface on which the thin film is formed. The glass plate is also expressed as a glass substrate.

The glass plate 1 is not particularly limited in composition as long as it is a silicate glass. For example, in the case of a glass substrate for display, it contains SiO ₂ , Al ₂ O ₃ , B ₂ O ₃ and an alkaline earth metal oxide. An aluminosilicate glass having a composition is preferred. Moreover, from the viewpoint of suppressing adhesion and defects of the formed element, so-called alkali-free glass that does not substantially contain an alkali metal component is more preferable among aluminosilicate glasses. In addition, not containing an alkali metal component substantially does not contain an alkali metal component at all, but contains the inevitable component in manufacture. Specifically, the alkali metal oxide content in the glass composition is preferably 0.1% by mass or less.

  In the process of manufacturing the glass plate 1, the conveying device conveys a pre-made glass plate (glass substrate) that has been cut to a predetermined size one by one in a predetermined direction. The apparatus 100 is provided. The roughening device 100 includes a plurality of rotating rollers 101 that are rotated by a driving device (not shown), a nozzle 102 that is installed below the rotating roller 101, and a ceiling plate 103 that is installed above the rotating roller 101. ing.

  The nozzle 102 blows the reaction gas from the lower side of the glass plate 1 in a direction substantially perpendicular to the conveying direction of the glass plate 1 to the glass plate 1 conveyed in the roughening device 100. Thereby, the 2nd main surface 20 of the glass plate 1 is etched (roughened). The nozzle 102 has a gas supply path 104 for supplying a reaction gas and a gas suction path 105 for sucking the reaction gas.

  The gas supply path 104 is connected to, for example, a source gas supply device that supplies a source gas (not shown) provided outside. The source gas includes, for example, a fluorine-based source gas and a carrier gas.

The fluorine-based source gas is used to generate a fluorine-based reaction component that reacts with the surface of the glass plate 1. The fluorine-based reaction component can be generated by converting the fluorine-based source gas into plasma (including decomposition, cold air, activation, ionization, etc.). The carrier gas is used for carrying and diluting the fluorine-based source gas and performing plasma discharge. In the present embodiment, CF ₄ is used as the fluorine-based source gas, and argon is used as the carrier gas.

The fluorine-based source gas is not limited to this, but other perfluorocarbons such as C ₂ F ₆ and C ₃ F _8, hydrofluorocarbons such as CHF ₃ , CH ₂ F ₂ , and CH ₃ F, SF ₆ , NF ₃ , and XeF ₂ Other fluorine-containing compounds such as may be used. The carrier gas is not limited to this, and other inert gases such as N ₂ , helium, neon, and xenon may be used.

  In the present embodiment, a reactive gas that is a hydrogen fluoride gas is blown onto the second main surface 20 to be etched to reduce the influence of the reactive gas on the first main surface 10 as much as possible. Al is leached from the component and is prevented from being replaced by F.

  The reactive gas is blown to the second main surface 20 of the glass plate 1 through the gas supply path 104 and is released to the outside of the roughening device 100 through the gas suction path 105. In addition, the reactive gas may circulate to the first main surface 10. For example, in the case where a plurality of glass plates 1 are continuously conveyed and etched, the first glass plate passes through the second glass plate until the second glass plate reaches the etching process portion ( That is, after the first glass plate is roughened, until the second glass plate is roughened, the residual gas G tends to remain in the roughening device 100. When the second glass plate is transported in the state where the residual gas G is present, the reaction gas may circulate from the downstream side in the transport direction of the first main surface 10 in particular. An example of a method of manufacturing a glass plate (glass substrate) that removes such residual gas G and the reaction gas that has circulated toward the first main surface 10 and suppresses the influence of the reaction gas on the first main surface 10 is shown below. 2 and will be described with reference to FIG. 2 and 3 are illustrated for the sake of convenience of explanation, and do not necessarily match the actual configuration ratios.

<Embodiment 1: See FIG. 2A>
In the first embodiment, a plurality of openings 106 are formed in the ceiling plate 103 of the surface roughening apparatus 100, and air is blown from the openings 106 toward the nozzle 102, and the reaction gas that has flowed toward the first main surface 10 side. And / or the residual gas G remaining in the roughening apparatus 100 (the gas formed by the reaction gas staying in the roughening apparatus 100) is blown away. The residual gas G or the like blown off may be sucked into the nozzle 102 from the gas suction path 105 and used again as a reaction gas. Moreover, since air is directly applied to the 1st main surface 10 of the glass plate 1 conveyed, the wraparound of a reactive gas can be reduced and the influence of the reactive gas in the 1st main surface 10 can be suppressed. Further, by continuously blowing air between the transported glass plate 1 and the next transported glass plate 1, the residual gas G is blown away, and the influence of the reaction gas on the first main surface 10 of the glass plate 1. Can be avoided as much as possible.

<Embodiment 2: See FIG. 2B>
In the second embodiment, a plurality of openings 106 are formed in the ceiling plate 103 of the surface roughening apparatus 100, and the reaction gas that has circulated from the openings 106 toward the first main surface 10 and / or the inside of the surface roughening apparatus 100. This is a method of sucking the residual gas G remaining in the gas. By doing in this way, even if the reaction gas wraps around the first main surface 10, the reaction gas can be sucked and the influence of the reaction gas on the first main surface 10 can be suppressed. Further, by continuously sucking the reaction gas or the like from the opening 106 and sucking the residual gas G from the gas suction path 105, it is possible to avoid the influence of the reaction gas on the first main surface 10 of the glass plate 1 as much as possible. is there.

<Embodiment 3: See FIG. 3A>
In the third embodiment, a nozzle 107 that blows out a plurality of airs is provided above the roughening device 100, blown to the first main surface 10 of the glass plate 1 being conveyed, and wraps around the first main surface 10 side. This is a method of blowing off the reaction gas and / or the residual gas G. The residual gas G or the like blown off may be sucked into the nozzle 102 from the gas suction path 105 and used again as a reaction gas. Since air is directly blown onto the first main surface 10 of the glass plate 1, the wraparound of the reaction gas can be reduced and the action of the residual gas G on the first main surface 10 can be positively suppressed. The angle of the nozzle 107 is arbitrary.

<Embodiment 4: See FIG. 3B>
In the fourth embodiment, since the bottom surface 103a of the ceiling plate 103 of the roughening device 100 is inclined upward and the space is expanded in the opposite direction to the conveying direction of the glass plate 1, the residual gas G is roughened. It is difficult to remain in the conversion apparatus 100. Since the residual gas G hardly remains, the influence of the reactive gas on the first main surface 10 of the glass plate 1 can be suppressed. Note that the bottom surface 103a is not limited to being inclined, and it is only necessary to form a space for the residual gas G to diffuse. For example, the shape may be a dome shape, may be inclined toward the conveyance direction, and may have a configuration in which a space is widened in the conveyance direction.

  Further, it is possible to control the amount of the reaction gas and the gas ejection timing to such an extent that the reaction gas does not wrap around and / or the residual gas G is not generated. And it is also possible to stop the conveyance of the glass plate 1 or adjust the conveyance speed until the residual gas G is dispersed. By controlling at least one of these, it is possible to suppress the wraparound of the reaction gas and / or the generation of the residual gas G.

  Furthermore, even if it puts a frame board on the 1st main surface 10 of the glass plate 1, and suppresses that the reaction gas and / or residual gas G which went around to the 1st main surface 10 side contact with the 1st main surface 10 are contacted. Good. Further, the reaction gas and / or the residual gas G that has circulated to the first main surface 10 side by the method of covering the first main surface 10 with a film or applying a coating film that is peeled off with hydrofluoric acid is the first main surface 10. You may suppress contacting with. These frame plates, films, films peeled off with hydrofluoric acid, and the like are expressed as “a contact suppressing member that prevents contact between the other glass surface of the main surface of the glass substrate and the reactive gas”. Further, any combination of these methods and the above-described embodiments is possible.

  As described above, the control mechanism and process that prevent the reactive gas from flowing to the first main surface 10 side, the mechanism and process that do not generate the residual gas G, the mechanism and process that blow off the residual gas, the reactive gas and the first main surface By providing a mechanism and a process that prevent contact with the glass 10, it is possible to suppress the influence of the reactive gas on the first main surface 10 of the glass plate 1.

  FIG. 4 shows the result of measuring the fluorine amount and Al / Si ratio of the first main surface 10, FIG. 4 (a) is a front view of the measurement point, and FIG. 4 (b) is a table of the measurement result of the fluorine amount. FIG. 4C is a table of Al / Si measurement results. The comparative example is a measurement value when the reaction gas and / or the residual gas G that has circulated toward the first main surface 10 side is not removed, and the embodiment can reduce the residual gas G as much as possible based on the above-described embodiment. The measured value when removed. In addition, since it becomes almost impossible to detect fluorine if additional simple cleaning is performed, the value before cleaning is shown in FIG. 4B, but the value of Al / Si does not change even after cleaning. Both values before washing are valid.

  The Al / Si ratio is the ratio of the Al concentration and the Si concentration on the surface (first main surface 10) of the glass plate 1 measured using X-ray photoelectron spectroscopy, that is, atm% of Al and atm% of Si. Ratio. The measuring apparatus uses ESCA5500 manufactured by Albac Phi, using Si (2p) and Al (2p) peaks, a path energy of 117.4 eV, an energy step of 0.5 eV / step, and a take-off angle (with the sample surface). Measurement was carried out under the condition of 150 (angle formed by the detector). For the analysis of the spectrum, the analysis software Multi Pak Ver. 8.2 was used. Fluorine content (fluorine content) was also measured by the same method.

  Six measurement points are indicated by (1) to (6) on the first main surface 10 of the glass plate 1 (see FIG. 4A). (1) is near the corner side of the first main surface 10 near the first end surface 30 and the fourth end surface 60, (2) is near the corner side of the first main surface 10 near the first end surface 30 and the third end surface 50, (3) is near the corner side of the first main surface 10 near the second end surface 40 and the third end surface 50, (4) is near the corner side of the first main surface 10 near the second end surface 40 and the fourth end surface 60, (5) is in the vicinity of the center of the first main surface 10, and (6) is in the vicinity of the first end surface 30 and is intermediate between (1) and (2).

According to the measurement result of fluorine content (atm%) on the first main surface 10 (see FIG. 4B), the measurement points (1), (2), and (6) close to the first end surface 30 are compared with the comparative example. It is understood that the amount of fluorine is reduced, and the influence of hydrogen fluoride gas, which is a reaction gas, is reduced. Moreover, it is preferable from the table | surface that the average value of fluorine content of the 1st main surface 10 (it is set as the average of the value of (1)-(6)) is less than 0.39 atm%, More preferably, it is 0.00. It is 35 atm% or less, More preferably, it is 0.32 atm% or less, More preferably, it is 0.30 atm% or less. When the fluorine content is large, oil repellency due to fluorine is exhibited, and adhesion with, for example, a semiconductor element formed on the first main surface 10 is deteriorated, but it can be reduced.
Further, the standard knitting difference of the fluorine amount on the first main surface 10 is preferably less than 0.25 atm%, more preferably 0.20 atm% or less, further preferably 0.15 atm% or less, further preferably 0. .12 atm% or less, more preferably 0.10 atm% or less. Since the influence of fluorine on the first main surface 10 can be reduced, a stable quality semiconductor element can be formed on any of the first main surface 10.

  The total value of the fluorine amount of the comparative example at the measurement points (1), (2) and (6) is 1.81 atm%, the average value of the fluorine content is 0.60 atm%, and the fluorine amount in the example The sum of the values is 0.80 atm%, and the average fluorine content is 0.27 atm%.

  Here, since the fluorine amount at the position corresponding to the measurement point (5) on the second main surface 20 was 0.69 atm%, the comparative example at the measurement points (1), (2), and (6). It can be determined that the value of the fluorine amount is the same as the value of the fluorine amount of the second main surface 20. Therefore, the average value of the fluorine content of the first main surface 10 is preferably ½ times or less the average value of the fluorine content of the second main surface 20. By doing in this way, the influence degree by the reactive gas of the 1st main surface 10 can be reduced, fully roughening the 2nd main surface 20. FIG.

  When the fluorine content is large, oil repellency due to fluorine is shown and the adhesion to, for example, a semiconductor element formed on the first main surface 10 is deteriorated, but this is eliminated in the present embodiment. Further, it is possible to provide the glass plate 1 in which the influence of the reaction gas on the first main surface 10 is reduced while the second main surface 20 is sufficiently roughened.

According to the measurement result of the Al / Si ratio of the first main surface 10 (see FIG. 4C), the measurement points (1), (2), and (6) close to the first end surface 30 are compared with the comparative example. It is understood that the Al / Si ratio is high, the leaching of Al is suppressed by the hydrogen fluoride gas that is the reaction gas, and the influence of the reaction gas is reduced. Moreover, it is preferable from the table | surface that the value of Al / Si of the 1st main surface 10 is 0.2 or more. And more preferably, it is 0.23 or more, More preferably, it is 0.25 or more. The composition of the glass plate of this embodiment is that the Al / Si value is about 0.3 from the results of the measurement points (3) to (4). By doing so, since the substitution of Al and F is reduced, it is possible to suppress the deterioration of the adhesion of semiconductor elements and the like.
Further, from the table, the average value of the Al / Si values of the first main surface 10 (the average value of the values (1) to (6)) is preferably larger than 0.22, more preferably 0.25. That's it. Since the substitution of Al and F is reduced by setting the above range of values, it is possible to suppress deterioration in adhesion of semiconductor elements and the like.
Moreover, it is preferable that the standard knitting difference of the value of Al / Si on the 1st main surface 10 is less than 0.08, More preferably, it is 0.05 or less. By setting the above range of values, the substitution of Al and F on the first main surface 10 can be reduced, so that a stable quality semiconductor element can be formed on any of the first main surface 10.

  By removing the influence of the reactive gas on the first main surface 10 of the glass plate 1, the surface property state of the first main surface 10 of the glass plate 1 is improved, and the semiconductor element and the like on which the first main surface 10 is formed It is possible to maintain a high affinity state, and it is difficult for peeling of formed products such as TFT circuits and malfunctions to occur.

  Here, since the value of Al / Si at the position corresponding to the measurement point (5) on the second main surface 20 was 0.13, the measurement points (1), (2), (6) It can be determined that the value of Al / Si in the comparative example is the same as the value of Al / Si on the second major surface 20.

  The example / comparative example of measurement point (1) is 1.54, the example / comparative example of measurement point (2) is 1.60, and the example / comparative example of measurement point (6) is 1.73. Therefore, the Al / Si value of the first major surface 10 is preferably 1.3 times or more the Al / Si value of the second major surface 20. For example, the Al / Si value of the first major surface 10 is preferably 0.20 or more, and the Al / Si value of the second major surface 20 is preferably 0.15 or less. By doing in this way, the influence degree by the reactive gas of the 1st main surface 10 can be reduced, fully roughening the 2nd main surface 20. FIG.

  According to the present embodiment, it is possible to provide the glass plate 1 in which the influence of the reaction gas on the first main surface 10 is reduced while sufficiently roughening the second main surface 20.

  The manufacturing method of the glass plate (glass substrate) 1 mentioned above is used suitably for the manufacturing method of the glass substrate for displays. In the manufacturing method of the embodiment, only the second main surface 20 which is one of the first main surface 10 and the second main surface 20 of the glass plate 1 is roughened using a reaction gas. It can be said that a roughening step for surface treatment is included. Here, “roughening only the second main surface 20” means that only the second main surface 20 that is the target of the original roughening is roughened, and is the other glass surface. It is not intended to exclude the first main surface 10 that is roughened even a little.

  5 (a) to 5 (c) are tables showing values measured with indices indicating various roughnesses. FIG. 5 (a) shows measured values of the first main surface 10, and FIG. The measured values of the two principal surfaces 20, FIG. 5 (c) show the values of the first principal surface / second principal surface with respect to the average values of FIGS. 5 (a) to 5 (b). 5A to 5C, the number of samples N is 5 (N = 5), and each sample value, each roughness value (average value), and increase in specific surface area ratio (%) are shown. ing. In FIG. 5, each value of the sample numbers N1 to N5 can be listed only up to three digits after the decimal point for convenience of description. However, in the average values described in FIGS. The calculation was performed with numerical values of 15 digits after the decimal point of each value of N1-5. Moreover, in each sample, each roughness value (average value) was calculated | required by averaging the value of (1)-(6) shown to Fig.4 (a)-(b).

  The indices (Ra, Rku, etc.) indicating the roughness of each table are defined as follows. These indices are defined in JIS B 0601: 2013.

Ra: “arithmetic mean roughness”, which is the value representing the average of the absolute values of Z (x) (an aggregate of one curve) in the reference length.
Rku: “Curtosis of roughness curve”, which is a value representing the mean square of Z (x) at a reference length dimensionless by the square of the root mean square height Rq.

  Rsk: “skewness of roughness curve”, which represents the mean square of Z (x) at the reference length made dimensionless by the cube of the root mean square height Rq. It means the degree of skewness and is a value representing the symmetry between the peak and valley when the average line is the center. It is also a kind of parameter representing the surface irregularity shape measured by an atomic force microscope.

Rsm: “average length of roughness curve element”, which is a value representing the average length Xs of contour curve elements at the reference length.
Rv: “Maximum valley depth of the roughness curve”, which is the maximum value of the valley depth Zv of the contour curve at the reference length.
Rz: “maximum height roughness”, which is the value representing the sum of the maximum value Rp of the peak height Zp and the maximum value Rv of the valley depth Zv of the contour curve at the reference length (Rz = Rp + Rv).
The increase in the specific surface area ratio is a measurement of the specific surface area of the first main surface or the second main surface when the surface area of the reference plane is 1, and the difference between these values and the surface area of the reference plane (that is, the first surface area) 1 is a value obtained by subtracting 1 from the value of the specific surface area of the first principal surface or the second principal surface (unit is%).

  From the tables of FIGS. 5A to 5C, in the glass plate 1 of the present embodiment, the first surface roughness of the first main surface 10 is smaller than the second surface roughness of the second main surface 20. It is understood that the value of Al / Si is greater on the first major surface 10 than on the second major surface 20 with reference to the table of FIG.

  In the present embodiment, the second main surface 20 of the glass plate 1 is roughened to prevent peeling electrification, while the remaining reaction gas is positively removed and the wraparound of the reaction gas is suppressed, so that the first main surface 10 As much as possible, the influence of the reaction gas on is eliminated. Specifically, the first surface roughness of the first major surface 10 is made smaller than the second surface roughness of the second major surface 20 to maintain the smoothness of the surface of the first major surface 10. At the same time, the amount of Al on the first main surface 10 leached by the reaction gas is reduced as much as possible to increase the value of Al / Si as compared to the second main surface 20, and the first main surface 10 is formed. Adhesion with a color filter, a black matrix (BM), or the like, which is a kind of thin film, is improved. Further, since the value of Al / Si is large, the adhesion with semiconductor elements such as TFT circuits deposited by sputtering is also improved.

  Further, since the glass plate 1 of the present embodiment is premised on aluminosilicate glass (aluminosilicate glass) mainly composed of aluminum oxide (alumina) and silicon dioxide (silica), the reaction gas to the first main surface 10 is assumed. The glass plate 1 suitable for being used as a display or the like can be provided by suppressing the influence of the above as much as possible.

  Hereinafter, preferable values for each roughness index will be described.

  In Ra (arithmetic mean roughness), it can be said that the Ra of the first main surface 10 is preferably 0.75 times or less the Ra of the second main surface 20. Further, it is more preferably 0.73 times or less, and still more preferably 0.70 times or less. The second main surface 20 is roughened by etching, and the first main surface 10 is suppressed from being roughened by the influence of the reaction gas. Moreover, although a lower limit is not specifically limited, For example, 0.1 times or more may be sufficient.

In Rku (crutosis of roughness curve), it can be said that Rku of the first main surface 10 is preferably 0.65 times or less of Rku of the second main surface 20. Further, it is more preferably 0.63 times or less, and still more preferably 0.60 times or less. The second main surface 20 is roughened by etching, and the first main surface 10 is suppressed from being roughened by the influence of the reaction gas. Moreover, although a lower limit is not specifically limited, For example, 0.1 times or more may be sufficient.
In Rsk (roughness skewness), Rsk of the second major surface 20 is preferably positive. When Rsk is positive, the second main surface 20 can be roughened so that peeling charging can be effectively suppressed.

  In Rsm (average length of roughness curve element), it can be said that the Rsm of the first major surface 10 is preferably 1.25 times or more the Rsm of the second major surface 20. Further, it is more preferably 1.3 times or more, and still more preferably 1.35 times or more. The second main surface 20 is roughened by etching, and the first main surface 10 is suppressed from being roughened by the influence of the reaction gas. Moreover, although an upper limit is not specifically limited, For example, 10 times or less may be sufficient.

  In Rv (the maximum valley depth of the roughness curve), it can be said that Rv of the first main surface 10 is preferably 0.6 times or less of Rv of the second main surface 20. Further, it is more preferably 0.58 times or less, and still more preferably 0.55 times or less. The second main surface 20 is roughened by etching, and the first main surface 10 is suppressed from being roughened by the influence of the reaction gas. Moreover, although a lower limit is not specifically limited, For example, 0.1 times or more may be sufficient.

  In Rz (maximum height roughness), it can be said that Rz of the first main surface 10 is preferably 0.7 times or less of Rz of the second main surface 20. Further, it is more preferably 0.67 times or less, and still more preferably 0.65 times or less. The second main surface 20 is roughened by etching, and the first main surface 10 is suppressed from being roughened by the influence of the reaction gas. Moreover, although a lower limit is not specifically limited, For example, 0.1 times or more may be sufficient.

In the increase in the specific surface area ratio, it can be said that the increase in the specific surface area ratio of the first main surface 10 is preferably 1/3 or less of the increase in the specific surface area ratio of the second main surface. Further, it is more preferably 1/4 or less, and still more preferably 1/5 or less. The second main surface 20 is roughened by etching, and the first main surface 10 is suppressed from being roughened by the influence of the reaction gas. Moreover, although a lower limit is not specifically limited, For example, 1/20 or more may be sufficient.
And it can be said that it is preferable that the increase in the specific surface area ratio of the 1st main surface 10 is 0.03% or less. Further, it is more preferably 0.02% or less, still more preferably 0.015% or less. The first main surface 10 is less affected by the reaction gas and is less roughened. Moreover, although a lower limit is not specifically limited, For example, 0.001% or more may be sufficient.

FIGS. 6A and 6B are tables in which the cullet peeling rates at the first end face 30, the second end face 40, the third end face 50, and the fourth end face 60 are measured. FIG. The sample, FIG. 6B, is the second sample. The first sample and the second sample are simply samples having different N numbers, and are manufactured by removing the residual gas G, respectively.
The cullet refers to minute glass particles that are peeled off from the glass plate 1. Moreover, the cullet peeling rate (unit:%) was calculated | required as a ratio (cullet occupation rate) of the exclusive area of the cullet stuck to the adhesive surface of the tape by the tape test. The tape test is to apply the tape to the end face of the glass plate 1 and then peel off the tape, and measure with a microscope how much the cullet is peeled off from the end face of the glass plate 1 and attached to the adhesive surface of the tape. It is a test to do. In the measurement of the microscope, the area occupied by the cullet existing in the area of 125 μm × 125 μm randomly extracted from the adhesive surface of the tape was extracted by the binarization process, and the abundance ratio in the area of 125 μm × 125 μm was shown. . Thus, the cullet occupation area per unit area was determined, and the percentage notation was defined as the cullet peeling rate (cullet occupancy rate).
Note that the tape used in the tape test may have, for example, a 180 ° peeling adhesive strength defined by JIS Z 0237: 2009 of 10 N / 25 mm, and the peeling method conforms to JIS Z 0237: 2009. Good.

  In addition, when the end surface is affected by the reaction gas, the cullet peeling rate (caret occupancy) tends to increase. Specifically, the value is 2.5% or more. This is presumably because the end face is also etched by the reaction gas and roughened, and valleys and the like that tend to concentrate stress are formed, so that cullet is easily generated. In addition, since Al, which is one of the main components of glass, is substituted with F, brittleness and cullet are likely to occur in the substituted portion.

  From the tables of FIGS. 6A to 6B, the cullet peeling rates of the end faces 30, 40, 50, and 60 are all 1.01% or less, which are almost the same, and thus can be said to be equal to each other. The term “equal” means that the average value of the cullet peeling rate is within a range of about 0.5 to 1.5 times. The wraparound of the reaction gas to the first main surface 10 side can be prevented more reliably.

  Moreover, if the cullet peeling rates of the end faces 30, 40, 50, 60 are equal to each other, it can be said that the surface roughness and / or Al / Si values of the end faces 30, 40, 50, 60 are the same. The term “equal” means that a deviation that does not have a clear tendency is allowed.

  Moreover, when the cullet adhering to the adhesive surface was observed in the tape test, no cullet of 6 μm or more was generated. This is presumably because the end face is not etched by the reaction gas, so that it is difficult to form valleys or the like where stress concentration is likely to occur, and cullet is hardly generated.

  Further, since the influence of the residual gas on the first main surface 10 is reduced and / or the cullet peeling rate of any of the end faces is equal, the residual gas G is positively removed. It is considered that there is no difference in roughness between the end faces 30, 40, 50, 60. If the reaction gas is not sufficiently removed, the first end face 30 on the front end side in the transport direction is particularly roughened, but there is no difference from the other end faces 40, 50, 60. Therefore, it can be said that the influence of the reaction gas on the first main surface 10 of the glass plate 1 is sufficiently suppressed.

  In the description of the present embodiment, the first, second, etc. are used, but the position and direction are not limited. It is sufficient that either surface of the glass plate 1 is roughened and the other surface suppresses the influence of the reaction gas.

  In addition, this invention is not limited to embodiment mentioned above, A deformation | transformation, improvement, etc. are possible suitably. In addition, the material, shape, dimension, numerical value, form, number, arrangement location, and the like of each component in the above-described embodiment are arbitrary and are not limited as long as the present invention can be achieved.

  In particular, in the present embodiment, it is expressed as a substantially rectangular glass plate, but it may be a glass plate called a corner cut, in which corners of a rectangular glass plate are cut off.

From the above matters, the present specification discloses the following contents.
[1]
A first main surface, a second main surface opposite to the first main surface, and an end surface connecting the first main surface and the second main surface, the first surface of the first main surface A glass plate in which the roughness is smaller than the second surface roughness of the second main surface, and the value of Al / Si is larger in the first main surface than in the second main surface.
[2]
With respect to the value of Al / Si, the first main surface is 1.3 times or more of the second main surface, [1]
The glass plate as described in.
[3]
The glass plate according to [1] or [2], wherein the value of Al / Si on the first main surface is 0.2 or more.
[4]
Any one of [1] to [3], wherein an average value of the fluorine content of the first main surface is not more than ½ times an average value of the fluorine content of the second main surface. The glass plate described.
[5]
The glass plate according to any one of [1] to [4], wherein an average value of the fluorine content of the first main surface is less than 0.39 atm%.
[6]
The glass according to any one of [1] to [5], wherein an increase in the specific surface area ratio of the first main surface is 1/3 or less of an increase in the specific surface area ratio of the second main surface. Board.
[7]
The glass plate according to any one of [1] to [6], wherein an increase in the specific surface area ratio of the first main surface is 0.03% or less.
[8]
Ra of said 1st main surface is a glass plate of any one of [1] to [7] which is 0.75 times or less of Ra of said 2nd main surface.
[9]
The glass plate according to any one of [1] to [7], wherein Rku of the first main surface is 0.65 times or less of Rku of the second main surface.
[10]
The glass plate according to any one of [1] to [7], wherein Rsm of the first main surface is 1.25 times or more of Rsm of the second main surface.
[11]
The glass plate according to any one of [1] to [7], wherein Rv of the first main surface is 0.6 times or less of Rv of the second main surface.
[12]
The glass plate according to any one of [1] to [7], wherein Rz of the first main surface is 0.7 times or less of Rz of the second main surface.
[13]
The end face includes a first end face, a second end face facing the first end face, a third end face connecting one end of the first end face and one end of the second end face, and the other end of the first end face. A fourth end face that connects the other end of the second end face and opposes the third end face, and includes the first end face, the second end face, the third end face, and the fourth end face. The glass plate according to any one of [1] to [12], wherein the cullet peeling rate is equal.
[14]
The glass plate according to [13], wherein the first end surface, the second end surface, the third end surface, and the fourth end surface have the same surface roughness.
[15]
A method for producing a glass substrate for display, comprising: a step of producing a glass substrate; and a roughening step of roughening only one glass surface of the main surface of the glass substrate using a reactive gas. A method for producing a glass substrate.
[16]
The method for producing a glass substrate according to [15], wherein in the roughening step, a contact suppressing member that prevents contact between the other glass surface of the main surface of the glass substrate and the reactive gas is used.
[17]
The method for producing a glass substrate according to [15] or [16], wherein in the roughening step, the reactive gas is prevented from wrapping around the main surface of the glass substrate toward the other glass surface.
[18]
In the roughening step, the method includes a step of continuously conveying the first glass plate and the second glass plate, and after roughening the first glass plate, the second glass plate is roughened. The method for producing a glass substrate according to any one of [15] to [17], wherein the reaction gas is prevented from staying in the roughening apparatus during
[19]
The roughening step includes a step of continuously conveying the first glass plate and the second glass plate, and after roughening the first glass plate, the second glass plate is roughened. The method for producing a glass substrate according to any one of [15] to [17], wherein the step of blowing the residual gas formed by the reaction gas staying in the roughening device during the period up to.

  The method for producing a glass plate and a glass plate (glass substrate) according to the present invention is suitable for use in the production of a glass plate that prevents peeling electrification of the surface in contact with the stage and suppresses defects on the surface on which a semiconductor element or the like is formed. It is done.

  Although the invention has been described in detail and with reference to specific embodiments, it will be apparent to those skilled in the art that various changes and modifications can be made without departing from the spirit and scope of the invention.

1 Glass plate (glass substrate)
DESCRIPTION OF SYMBOLS 10 1st main surface 20 2nd main surface 30 1st end surface 40 2nd end surface 50 3rd end surface 60 4th end surface 100 Roughening apparatus 101 Rotary roller 102 Nozzle 103 Ceiling board G Residual gas

Claims (19)

A first main surface;
A second main surface facing the first main surface;
An end surface connecting the first main surface and the second main surface;
The first surface roughness of the first main surface is smaller than the second surface roughness of the second main surface;
The glass plate whose value of Al / Si is larger on the first main surface than on the second main surface.   The glass plate according to claim 1, wherein the first main surface is 1.3 times or more the second main surface with respect to the value of Al / Si.   The glass plate according to claim 1 or 2, wherein the Al / Si value of the first main surface is 0.2 or more.   The average value of the fluorine content of the first main surface is not more than ½ times the average value of the fluorine content of the second main surface, according to any one of claims 1 to 3. Glass plate.   The glass plate according to any one of claims 1 to 4, wherein an average value of the fluorine content of the first main surface is less than 0.39 atm%.   6. The glass plate according to claim 1, wherein an increase in the specific surface area ratio of the first main surface is 1/3 or less of an increase in the specific surface area ratio of the second main surface.   The glass plate according to any one of claims 1 to 6, wherein an increase in the specific surface area ratio of the first main surface is 0.03% or less.   The glass plate according to any one of claims 1 to 7, wherein Ra of the first main surface is not more than 0.75 times Ra of the second main surface.   The glass plate according to any one of claims 1 to 7, wherein Rku of the first main surface is 0.65 times or less of Rku of the second main surface.   The glass plate according to any one of claims 1 to 7, wherein Rsm of the first main surface is 1.25 times or more of Rsm of the second main surface.   8. The glass plate according to claim 1, wherein Rv of the first main surface is 0.6 times or less of Rv of the second main surface.   The glass plate according to any one of claims 1 to 7, wherein Rz of the first main surface is 0.7 times or less of Rz of the second main surface. The end face is
A first end surface;
A second end face facing the first end face;
A third end face connecting one end of the first end face and one end of the second end face;
A fourth end face that connects the other end of the first end face and the other end of the second end face and opposes the third end face;
The glass plate according to any one of claims 1 to 12, wherein a cullet peeling rate of the first end face, the second end face, the third end face, and the fourth end face is equal.   The glass plate according to claim 13, wherein the first end surface, the second end surface, the third end surface, and the fourth end surface have the same surface roughness. A method for producing a glass substrate for a display, comprising:
Producing a glass substrate;
A method for producing a glass substrate, comprising: a roughening step in which only one glass surface of the main surface of the glass substrate is roughened using a reaction gas. In the roughening step,
The method for producing a glass substrate according to claim 15, wherein a contact suppressing member that prevents contact between the other glass surface and the reaction gas among main surfaces of the glass substrate is used. In the roughening step,
The method for producing a glass substrate according to claim 15 or 16, wherein the reaction gas is prevented from wrapping around the main surface of the glass substrate toward the other glass surface. In the roughening step,
Including a step of continuously conveying the first glass plate and the second glass plate,
18. The method according to claim 15, wherein the reaction gas is prevented from staying in the roughening device after the first glass plate is roughened and before the second glass plate is roughened. 2. A method for producing a glass substrate according to item 1. In the roughening step,
Including a step of continuously conveying the first glass plate and the second glass plate,
A step of blowing away the residual gas formed by the reaction gas staying in the roughening device after the first glass plate is roughened and before the second glass plate is roughened. The manufacturing method of the glass substrate of any one of Claim 15 to 17.

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