WO2017111078A1 - Liquide de polissage pour verre et procédé de polissage - Google Patents

Liquide de polissage pour verre et procédé de polissage Download PDF

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Publication number
WO2017111078A1
WO2017111078A1 PCT/JP2016/088481 JP2016088481W WO2017111078A1 WO 2017111078 A1 WO2017111078 A1 WO 2017111078A1 JP 2016088481 W JP2016088481 W JP 2016088481W WO 2017111078 A1 WO2017111078 A1 WO 2017111078A1
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WO
WIPO (PCT)
Prior art keywords
polishing
glass
hydrofluoric acid
polishing liquid
organic solvent
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PCT/JP2016/088481
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English (en)
Japanese (ja)
Inventor
和哉 島田
晴香 西川
家田　智之
雄三 三好
Original Assignee
パナソニック株式会社
株式会社Ｎｓｃ
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Application filed by パナソニック株式会社, 株式会社Ｎｓｃ filed Critical パナソニック株式会社
Publication of WO2017111078A1 publication Critical patent/WO2017111078A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C15/00—Surface treatment of glass, not in the form of fibres or filaments, by etching

Definitions

  • the present invention relates to a polishing liquid and a polishing method for polishing glass of liquid crystal screens and organic EL screens used for portable terminals, FPDs (flat panel displays) and the like.
  • Liquid crystal display devices and organic EL display devices are widely used in products such as mobile phones, smartphones, tablet PCs, and notebook computers. And these flat display devices mainly use glass as a base material. Hereinafter, these display devices are referred to as “glass display devices”.
  • a driving unit such as a liquid crystal, a TFT, or a light emitting layer is formed between two plate glasses serving as a base material.
  • the drive unit When the drive unit is formed, strength is required so that the glass does not break during handling. For this reason, the glass material is not soda glass used for window glass or the like, but aluminoborosilicate glass (aluminoborosilicate glass) mixed with boric acid and alumina. Further, the glass thickness is used to a certain extent.
  • the thick glass is heavy and inconvenient to carry. Therefore, after manufacturing the product, the glass is polished with an etching solution for glass to reduce the thickness.
  • the dimple is a recess having a diameter of about several ⁇ m to several hundred ⁇ m and a depth of several ⁇ m to several tens of ⁇ m.
  • the dimples on the display device may be noticeable depending on the image, which may cause a problem in product quality. Accordingly, dimple suppression after polishing is one of the technical problems in glass polishing.
  • Patent Document 1 in order to prevent pits and scratches at the 10 ⁇ m level from expanding to 100 ⁇ m or more by polishing, 30 to 60% by weight of hydrofluoric acid is contained as a polishing component, and inorganic substances such as hydrochloric acid, sulfuric acid, nitric acid, phosphoric acid, etc.
  • a technique for polishing is disclosed.
  • Patent Document 2 discloses a pre-polishing step in which a polishing solution containing 10 to 30% by weight of hydrofluoric acid and 20 to 50% by weight of sulfuric acid is brought into contact with the surface of the glass plate to pre-polish the glass plate surface at 1 ⁇ m / sec or more; After the pre-polishing step, a post-polishing step is provided in which a polishing liquid containing hydrofluoric acid is brought into contact with the glass plate surface to polish the glass plate surface at a polishing rate of 0.5 to 20 ⁇ m / min. A method for polishing a glass plate surface is disclosed.
  • Patent Document 3 discloses pre-polishing using 0.4 to 4% by weight hydrofluoric acid and 40 to 90% by weight sulfuric acid, and post-polishing using 2 to 30% by weight hydrofluoric acid.
  • the scratches generated on the glass plate as a base material are removed before they grow into dimples or are made difficult to grow (pre-polishing), and then the main polishing (after-polishing) Polishing).
  • pre-polishing pre-polishing
  • after-polishing main polishing Polishing
  • polishing liquid used for such pre-polishing has a composition with extremely strong acidity of hydrofluoric acid (hydrofluoric acid) and sulfuric acid. For this reason, in the detoxification process before discarding the polishing liquid used in the pre-polishing, inconveniences such as the generation of a large amount of sludge during the neutralization process have occurred. Accordingly, there has been a demand for a polishing liquid having a composition that is easier to handle while maintaining the effect of pre-polishing, which has been a technical problem.
  • the polishing liquid according to the present invention is a plate glass polishing liquid, and contains hydrofluoric acid and an organic solvent.
  • the polishing liquid according to the present invention has a composition of hydrofluoric acid and an organic solvent having a relative dielectric constant of 10 or more and less than 40, sulfuric acid is not used. Therefore, the acidity is weaker than the polishing liquid used for the conventional pre-polishing, and the amount of sludge generated during the neutralization treatment can be suppressed.
  • polishing liquid according to the present invention will be described below.
  • the following description demonstrates one form and one Example of this invention, and this invention is not limited to the following description. The following description can be modified without departing from the spirit of the present invention.
  • the polishing liquid according to the present invention is a polishing liquid used for pre-polishing when it is divided into pre-polishing and post-polishing when polishing a glass display device.
  • the object of polishing is glass that can be used for glass display devices.
  • An oxide glass containing an oxide as the main component can be suitably used.
  • glass mainly composed of aluminosilicate glass (alumina and silicon oxide) is preferable.
  • Aluminosilicate glass has high tensile strength and is preferable as a base material for glass display devices.
  • ⁇ Aluminosilicate glass can be made in various compositions by changing the type of element added.
  • Aluminoborosilicate glass aluminoborosilicate glass with B (boron) added to the main component and elements such as Mg (magnesium), Ca (calcium), Sr (strontium), and Ba (barium) added as auxiliary components ), And is particularly preferably used as a substrate of a glass display device.
  • Glass is handled in the form of plate glass. This is because the substrate of the glass display device is used. Therefore, although it is glass, glass that cannot be supplied as a plate glass, such as a semiconductor insulating film, is not an object of polishing.
  • the polishing liquid according to the present invention contains hydrofluoric acid (hydrofluoric acid) and an organic solvent.
  • the organic solvent is easier to handle and dispose of compared to sulfuric acid that has been conventionally used.
  • the hydrofluoric acid and the organic solvent are supplied as an anhydride or an aqueous solution.
  • hydrofluoric acid is considered to be in a two-stage equilibrium state as follows. HF ⁇ H + + F- (1) HF + F- ⁇ HF2- (2)
  • the form of fluorine in the hydrofluoric acid solution is HF, F-, HF2-, and among these, the component (hereinafter referred to as active species) that contributes to the etching of glass mainly composed of SiO2 is HF2-. And HF. Furthermore, it is generally known that among active species, HF2- contributes more to etching than HF.
  • the relative permittivity of the organic solvent depends on the relative permittivity of the organic solvent.
  • the lower the relative permittivity the higher the HF fraction and the lower the HF2- fraction. Therefore, in the present invention, as a result of the presence of the organic solvent having a relative dielectric constant of 10 or more and less than 40, the abundance ratio of the HF fraction and the HF2- fraction in the active species is controlled within a suitable range. Even if there is a scratch on the surface of the plate glass, it can be removed without growing into dimples. Then, it is considered that the glass surface of the glass display device can be etched by a predetermined thickness by post-polishing.
  • organic solvents examples include the following.
  • the numerical value in parentheses is the relative dielectric constant. t-butyl alcohol (12.5), benzyl alcohol (13.1), ethylene glycol monomethyl ether (16.9), 1-butanol (17.5), isobutyl alcohol (17.9), cyclohexanone (18.3) ), Ethyl methyl ketone (18.5), 2-propanol (19.9), 1-propanol (20.3), acetone (20.7), ethanol (24.6), methanol (32.7), Nitromethane (35.9), ethylene glycol (37.7), etc. are mentioned. Of these, ethanol is easy to handle and can be suitably used.
  • the front and back surfaces of a glass display device (non-processed product) formed using plate glass are polished with the polishing liquid according to the present invention, several tens of ⁇ m in terms of one side. It comprises a polishing step, and then a post-polishing step of several hundred ⁇ m after the main polishing. In the post-polishing step, the polishing liquid contains no organic solvent.
  • polishing liquid in order to examine whether or not the polishing liquid can be used as a pre-polishing liquid, it is necessary to examine whether the scratches grow on the dimples after pre-polishing by scratching the glass surface in advance.
  • an indentation is made on the surface of an object to be processed using a micro Vickers hardness meter also used in Patent Document 2. This indentation is a substitute for scratches.
  • the workpiece is aluminoborosilicate glass of 5 cm ⁇ 2.5 cm ⁇ 0.7 mm.
  • the indentation was made with a micro Vickers hardness tester under the conditions of an applied load of 500 g and an applied time of 5 seconds.
  • the resulting indentation was a quadrangular pyramidal dent with a diagonal of 38 ⁇ m and a depth of 3.5 ⁇ m. A total of four indentations were formed at the four corners of the workpiece.
  • Evaluation was performed by immersing the object to be processed with the impression in the object to be examined and then observing under a microscope, and whether or not a crack grew from the corner of the impression. That is, the crack generation rate was used as a guideline for evaluation.
  • the reason is that when no crack is generated by the pre-polishing process, only the indented part is enlarged by polishing (FIGS. 2 (e) and (f)), whereas when the crack is generated from the indented, the indented part In addition to the enlargement, the inside of the crack is also etched and enlarged (FIGS. 2B and 2C). Since the crack is generated from the lower portion of the indentation, the inside of the crack is etched to grow into a deep dimple.
  • hydrofluoric acid aqueous solution is a solution of hydrofluoric acid and water.
  • FIG. 1A shows a state in which the indentations 12 are still formed at the four corners of the workpiece 10. After being dipped in a polishing liquid for examination and polished on one side by 10 ⁇ m, if no indentation remains and no cracks are generated as before polishing, the crack generation rate was set to zero%.
  • FIG. 1B shows a case where crack growth is observed from two of the four indentations 12. In such a state, the crack occurrence rate was 50%.
  • the lines 14 and 16 in FIG.1 (b) mean the growth direction of a crack. Since the indentation 12 has a square shape, it is considered that cracks grow in the same way from the four corners, but there are cases where the cracks grow only in one direction.
  • Line 14 shows the case where cracks grow in the horizontal direction in the drawing, and line 16 shows the case where cracks grow in the vertical direction.
  • FIG. 1 (c) shows a case where crack growth is observed at three locations among the four indentations 12.
  • the crack generation rate was 75%.
  • FIG.1 (d) and FIG.1 (e) show the case where a crack grew from four indentations 12.
  • FIG. 1 (d) even when the crack generation direction is only one direction, it was determined that the crack grew, and the crack generation rate was set to 100%.
  • FIGS. 2 (d), 2 (e), and 2 (f) are for the comparative example 4, and FIGS. 2 (d), 2 (e), and 2 (f) are for the example. .
  • the lower right line of each photograph shows 100 ⁇ m. 2 (a) and 2 (d) show the case before polishing, and FIGS. 2 (b) and 2 (e) show the case where the thickness of 10 ⁇ m on one side of the workpiece is polished.
  • 2 (c) and FIG. 2 (f) show the case where the thickness of one side of the workpiece is polished by 20 ⁇ m. 2 (a), 2 (d), 2 (e), and 2 (f), the portion where the indentation remains is circled because the photograph is thin.
  • FIG. 2 (a) and Fig. 2 (d) show the case of indentation only.
  • a square whose diagonal is 38 ⁇ m is shown.
  • FIG. 2B and FIG. 2E are photographs in the case of polishing by a thickness of 10 ⁇ m on one side.
  • the indentation had cracks growing from four corners, resulting in a cross-shaped scratch. The crack had a length of about 90 ⁇ m.
  • the indentation did not spread. Since the polished thickness (10 ⁇ m) is larger than the depth of the indentation, if the indentation remains as it is, the indentation should not be reflected. However, the shape of the indentation remains. Therefore, although the crack did not spread around, it can be judged that the shape as it was was maintained in the depth direction. In such a state, it was determined that there was no crack growth.
  • FIG. 2 (c) and FIG. 2 (f) are photographs in the case of polishing by a thickness of 20 ⁇ m on one side.
  • Comparative Example 4 FIG. 2C
  • the cracks were further grown and the length was grown to about 110 ⁇ m. Further, while maintaining the cross-shaped shape, each line was thicker than in the case of FIG. That is, the crack spread not only in the four corner directions of the indentation but also in the direction of the side.
  • Comparative Example 1 is an organic solvent tetrahydrofuran (THF: relative permittivity 7.8)
  • Comparative Example 2 is an organic solvent acetic acid (relative permittivity 6.2)
  • Comparative Example 3 is propionic acid (relative permittivity 3).
  • Comparative Example 4 is a case of only hydrofluoric acid without an organic solvent. That is, Comparative Example 4 is a simple hydrofluoric acid aqueous solution.
  • the concentration of hydrofluoric acid was changed to 3 mass%, 5 mass%, 7 mass%, and 10 mass%, respectively.
  • the organic solvent was changed to 75% by mass, 70% by mass, 67% by mass, and 64% by mass depending on the concentration of hydrofluoric acid.
  • the rest is water. Moreover, all are mass ratios with respect to the whole polishing liquid.
  • a polishing liquid that combines hydrofluoric acid and an organic solvent can make the growth of cracks zero, and a polishing liquid that can suppress the generation of dimples can be obtained.
  • the polishing liquid of the present invention can be suitably used in a pre-polishing step when polishing plate glass.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

Un polissage en deux étapes de pré-polissage et de post-polissage a été effectué dans le polissage d'un verre à glace. Une composition présentant une acidité extrêmement élevée et contenant de l'acide fluorhydrique (acide fluorhydrique) et de l'acide sulfurique est utilisée comme liquide de polissage utilisé dans un pré-polissage classique. Par conséquent, la nécessité d'utilisation d'un liquide de polissage ayant une composition plus facile à manier devient un problème technique. La présente invention concerne un liquide de polissage pour verre à glace, ledit liquide de polissage étant caractérisé en ce qu'il comprend de l'acide fluorhydrique et un solvant organique possédant une constante diélectrique relative allant de 10 à moins de 40, qui permet de réaliser le pré-polissage sans provoquer la croissance de rayures et supprime la quantité de boues générées pendant la neutralisation après utilisation.
PCT/JP2016/088481 2015-12-24 2016-12-22 Liquide de polissage pour verre et procédé de polissage WO2017111078A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2015251229A JP2017114720A (ja) 2015-12-24 2015-12-24 ガラス用研磨液および研磨方法
JP2015-251229 2015-12-24

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WO2017111078A1 true WO2017111078A1 (fr) 2017-06-29

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS396945B1 (fr) * 1961-09-09 1964-05-09
US5989450A (en) * 1996-08-26 1999-11-23 Lg Electronics Inc. Etchant for etching glass substrate
JP2000281383A (ja) * 1999-03-30 2000-10-10 Seiko Epson Corp ガラス用エッチング液、エッチング方法、マイクロレンズ基板の製造方法
JP2005343742A (ja) * 2004-06-03 2005-12-15 Nishiyama Stainless Chem Kk ガラス板表面の研磨方法、フラットパネルディスプレイ用ガラス基板、及びフラットパネルディスプレイ
JP2006338837A (ja) * 2005-06-06 2006-12-14 Fuji Electric Device Technology Co Ltd ガラス基体へのめっき方法、垂直磁気記録媒体用ディスク基板の製造方法、垂直磁気記録媒体用ディスク基板及び垂直磁気記録媒体
JP2007303974A (ja) * 2006-05-11 2007-11-22 Univ Nihon 振動センサ、振動センサの製造方法、歩数計、加速度センサ及び地震検知器
JP2009064514A (ja) * 2007-09-06 2009-03-26 Fuji Electric Device Technology Co Ltd ガラス基板およびその製造方法、ならびに当該ガラス基板を用いた磁気ディスク
JP2014084234A (ja) * 2012-10-19 2014-05-12 Hoya Corp 電子機器用カバーガラスのガラス基板及びその製造方法

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS396945B1 (fr) * 1961-09-09 1964-05-09
US5989450A (en) * 1996-08-26 1999-11-23 Lg Electronics Inc. Etchant for etching glass substrate
JP2000281383A (ja) * 1999-03-30 2000-10-10 Seiko Epson Corp ガラス用エッチング液、エッチング方法、マイクロレンズ基板の製造方法
JP2005343742A (ja) * 2004-06-03 2005-12-15 Nishiyama Stainless Chem Kk ガラス板表面の研磨方法、フラットパネルディスプレイ用ガラス基板、及びフラットパネルディスプレイ
JP2006338837A (ja) * 2005-06-06 2006-12-14 Fuji Electric Device Technology Co Ltd ガラス基体へのめっき方法、垂直磁気記録媒体用ディスク基板の製造方法、垂直磁気記録媒体用ディスク基板及び垂直磁気記録媒体
JP2007303974A (ja) * 2006-05-11 2007-11-22 Univ Nihon 振動センサ、振動センサの製造方法、歩数計、加速度センサ及び地震検知器
JP2009064514A (ja) * 2007-09-06 2009-03-26 Fuji Electric Device Technology Co Ltd ガラス基板およびその製造方法、ならびに当該ガラス基板を用いた磁気ディスク
JP2014084234A (ja) * 2012-10-19 2014-05-12 Hoya Corp 電子機器用カバーガラスのガラス基板及びその製造方法

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JP2017114720A (ja) 2017-06-29

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