TWI571449B - Color filter with glass plate - Google Patents
Color filter with glass plate Download PDFInfo
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- TWI571449B TWI571449B TW104106739A TW104106739A TWI571449B TW I571449 B TWI571449 B TW I571449B TW 104106739 A TW104106739 A TW 104106739A TW 104106739 A TW104106739 A TW 104106739A TW I571449 B TWI571449 B TW I571449B
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- Prior art keywords
- glass plate
- cleaning
- mass
- glass
- black matrix
- Prior art date
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- 239000011521 glass Substances 0.000 title claims description 342
- 238000004140 cleaning Methods 0.000 claims description 189
- 239000011159 matrix material Substances 0.000 claims description 68
- 239000011347 resin Substances 0.000 claims description 58
- 229920005989 resin Polymers 0.000 claims description 58
- 239000000126 substance Substances 0.000 claims description 42
- 230000002209 hydrophobic effect Effects 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 8
- 230000003746 surface roughness Effects 0.000 claims description 8
- 150000001491 aromatic compounds Chemical class 0.000 claims description 7
- 229910018072 Al 2 O 3 Inorganic materials 0.000 claims description 3
- 229910004298 SiO 2 Inorganic materials 0.000 claims description 3
- 229910052744 lithium Inorganic materials 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000012459 cleaning agent Substances 0.000 description 59
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 57
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 37
- 238000005406 washing Methods 0.000 description 36
- 238000004519 manufacturing process Methods 0.000 description 31
- 239000003513 alkali Substances 0.000 description 30
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 29
- 239000007788 liquid Substances 0.000 description 26
- 239000010408 film Substances 0.000 description 24
- 150000007529 inorganic bases Chemical class 0.000 description 23
- 238000000034 method Methods 0.000 description 21
- 239000004094 surface-active agent Substances 0.000 description 21
- 229910021642 ultra pure water Inorganic materials 0.000 description 17
- 239000012498 ultrapure water Substances 0.000 description 17
- 239000000758 substrate Substances 0.000 description 16
- 125000006850 spacer group Chemical group 0.000 description 10
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 9
- 239000005416 organic matter Substances 0.000 description 8
- 239000003599 detergent Substances 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 230000003749 cleanliness Effects 0.000 description 6
- 238000002290 gas chromatography-mass spectrometry Methods 0.000 description 6
- 150000002500 ions Chemical class 0.000 description 6
- 239000000243 solution Substances 0.000 description 6
- 239000000428 dust Substances 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 239000006060 molten glass Substances 0.000 description 5
- 238000001223 reverse osmosis Methods 0.000 description 5
- 239000007921 spray Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 239000000853 adhesive Substances 0.000 description 4
- 230000001070 adhesive effect Effects 0.000 description 4
- 238000007865 diluting Methods 0.000 description 4
- 239000003085 diluting agent Substances 0.000 description 4
- 238000003280 down draw process Methods 0.000 description 4
- 238000009296 electrodeionization Methods 0.000 description 4
- 238000005530 etching Methods 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 238000005342 ion exchange Methods 0.000 description 3
- 230000014759 maintenance of location Effects 0.000 description 3
- 238000004506 ultrasonic cleaning Methods 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- -1 and secondly Substances 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229960002050 hydrofluoric acid Drugs 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000002093 peripheral effect Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 239000011734 sodium Substances 0.000 description 2
- 230000007723 transport mechanism Effects 0.000 description 2
- NWUYHJFMYQTDRP-UHFFFAOYSA-N 1,2-bis(ethenyl)benzene;1-ethenyl-2-ethylbenzene;styrene Chemical compound C=CC1=CC=CC=C1.CCC1=CC=CC=C1C=C.C=CC1=CC=CC=C1C=C NWUYHJFMYQTDRP-UHFFFAOYSA-N 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 238000006124 Pilkington process Methods 0.000 description 1
- 229910006404 SnO 2 Inorganic materials 0.000 description 1
- FKNQFGJONOIPTF-UHFFFAOYSA-N Sodium cation Chemical compound [Na+] FKNQFGJONOIPTF-UHFFFAOYSA-N 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 230000002411 adverse Effects 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-N ammonia Natural products N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000012790 confirmation Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000006378 damage Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000004255 ion exchange chromatography Methods 0.000 description 1
- 239000003456 ion exchange resin Substances 0.000 description 1
- 229920003303 ion-exchange polymer Polymers 0.000 description 1
- 238000010030 laminating Methods 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 238000004806 packaging method and process Methods 0.000 description 1
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 238000004321 preservation Methods 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 238000009751 slip forming Methods 0.000 description 1
- 229910001415 sodium ion Inorganic materials 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 230000032258 transport Effects 0.000 description 1
- 238000011144 upstream manufacturing Methods 0.000 description 1
Classifications
-
- 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
- C03C23/00—Other surface treatment of glass not in the form of fibres or filaments
- C03C23/0075—Cleaning of glass
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B11/00—Cleaning flexible or delicate articles by methods or apparatus specially adapted thereto
- B08B11/04—Cleaning flexible or delicate articles by methods or apparatus specially adapted thereto specially adapted for plate glass, e.g. prior to manufacture of windshields
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B08—CLEANING
- B08B—CLEANING IN GENERAL; PREVENTION OF FOULING IN GENERAL
- B08B3/00—Cleaning by methods involving the use or presence of liquid or steam
- B08B3/04—Cleaning involving contact with liquid
- B08B3/08—Cleaning involving contact with liquid the liquid having chemical or dissolving effect
-
- 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
- C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
- C03C17/28—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material
- C03C17/32—Surface treatment of glass, not in the form of fibres or filaments, by coating with organic material with synthetic or natural resins
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
-
- 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
- C03C3/00—Glass compositions
- C03C3/04—Glass compositions containing silica
- C03C3/076—Glass compositions containing silica with 40% to 90% silica, by weight
- C03C3/089—Glass compositions containing silica with 40% to 90% silica, by weight containing boron
- C03C3/091—Glass compositions containing silica with 40% to 90% silica, by weight containing boron containing aluminium
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/18—Glass; Plastics
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
- Y02P40/00—Technologies relating to the processing of minerals
- Y02P40/50—Glass production, e.g. reusing waste heat during processing or shaping
- Y02P40/57—Improving the yield, e-g- reduction of reject rates
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Geochemistry & Mineralogy (AREA)
- Materials Engineering (AREA)
- Organic Chemistry (AREA)
- Liquid Crystal (AREA)
- Cleaning By Liquid Or Steam (AREA)
- Surface Treatment Of Glass (AREA)
- Physics & Mathematics (AREA)
- Optical Filters (AREA)
- General Physics & Mathematics (AREA)
- Optics & Photonics (AREA)
- Glass Compositions (AREA)
Description
本發明係關於一種彩色濾光片用玻璃板之製造方法、彩色濾光片面板之製造方法及顯示器用玻璃基板。 The present invention relates to a method for producing a glass plate for a color filter, a method for producing a color filter panel, and a glass substrate for a display.
先前,於玻璃板之製造步驟中,在藉由下拉(down draw)法等由玻璃原料成形玻璃板之步驟之後,進行對玻璃板之表面進行清洗之步驟。於玻璃板之清洗步驟中,如專利文獻1(日本專利特開2001-276759號公報)所揭示般,為了去除附著於玻璃板表面之玻璃之微小片、灰塵及污垢等異物,而進行利用酸性或鹼性藥液或超音波等對玻璃板之表面進行清洗之處理。 Previously, in the manufacturing step of the glass plate, the step of washing the surface of the glass plate was carried out after the step of forming the glass plate from the glass raw material by a down draw method or the like. In the cleaning step of the glass plate, as disclosed in the patent document 1 (Japanese Laid-Open Patent Publication No. 2001-276759), in order to remove foreign matter such as fine pieces of glass, dust, and dirt adhering to the surface of the glass plate, acid utilization is performed. Or the treatment of the surface of the glass plate with an alkaline liquid or ultrasonic.
又,液晶顯示器及電漿顯示器等平板顯示器之製造中所使用之玻璃板係於表面配置黑色矩陣、以及使紅色(R)、綠色(G)、藍色(B)之光透過之波長選擇元件即RGB像素,從而形成彩色濾光片。黑色矩陣遮斷RGB像素區域以外之背光源之漏光,並防止相互鄰接之RGB像素之混色,藉此提高顯示對比度。即,彩色濾光片中之光之通過區域由黑色矩陣之形狀及配置決定。 Further, a glass plate used in the manufacture of a flat panel display such as a liquid crystal display or a plasma display is a wavelength selective element in which a black matrix is disposed on the surface and light of red (R), green (G), and blue (B) is transmitted. That is, RGB pixels, thereby forming a color filter. The black matrix blocks light leakage from backlights other than the RGB pixel area and prevents color mixture of adjacent RGB pixels, thereby improving display contrast. That is, the light passing region in the color filter is determined by the shape and arrangement of the black matrix.
近年來,伴隨著顯示器之高精細化,配置於玻璃板表面之黑色矩陣之線寬及間距變小。具體而言,為了達成顯示器之高對比度化,必須利用黑色矩陣之高精細化(具體而言為未達20μm之線寬)提高開口率,並且利用黑色矩陣之高尺寸精度提高遮光性。又,為了達成顯示器之更高精細化,亦必需黑色矩陣之高精細化。 In recent years, with the high definition of the display, the line width and pitch of the black matrix disposed on the surface of the glass plate are reduced. Specifically, in order to achieve high contrast of the display, it is necessary to increase the aperture ratio by the high definition of the black matrix (specifically, the line width of less than 20 μm), and to improve the light blocking property by the high dimensional accuracy of the black matrix. Moreover, in order to achieve higher definition of the display, it is necessary to have a high definition of the black matrix.
先前,於平板顯示器之製造步驟中,藉由變更黑色矩陣樹脂之加熱條件及曝光條件,而無論玻璃板之表面狀態如何均可配置黑色矩陣。然而,伴隨著黑色矩陣之高精細化及高尺寸精度之必要性,必需以更高之精度實現黑色矩陣樹脂對玻璃板表面之高密接性。 Conventionally, in the manufacturing process of a flat panel display, by changing the heating conditions and exposure conditions of the black matrix resin, a black matrix can be disposed regardless of the surface state of the glass plate. However, with the necessity of high definition of the black matrix and high dimensional accuracy, it is necessary to achieve high adhesion of the black matrix resin to the surface of the glass plate with higher precision.
[專利文獻1]日本專利特開2001-276759號公報 [Patent Document 1] Japanese Patent Laid-Open Publication No. 2001-276759
[專利文獻2]日本專利特開2001-181686號公報 [Patent Document 2] Japanese Patent Laid-Open Publication No. 2001-181686
然而,要求平板顯示器之製造中所使用之玻璃板之表面具有高清潔度。因此,為了去除附著於玻璃板表面之異物,如專利文獻2(日本專利特開2001-181686號公報)所揭示般,可應用使用無機鹼系之清洗劑對玻璃板之表面進行清洗之方法。然而,於此種清洗方法中,有如下之虞:因在清洗後殘留於玻璃板表面之有機物,而導致無法充分地達成黑色矩陣樹脂對玻璃板表面之高密接性。 However, the surface of the glass plate used in the manufacture of the flat panel display is required to have high cleanliness. Therefore, in order to remove the foreign matter adhering to the surface of the glass plate, as disclosed in the patent document 2 (Japanese Patent Laid-Open Publication No. 2001-181686), a method of cleaning the surface of the glass plate using an inorganic base-based cleaning agent can be applied. However, in such a cleaning method, there is a possibility that the high-adhesion property of the black matrix resin to the surface of the glass plate cannot be sufficiently achieved due to the organic matter remaining on the surface of the glass plate after the cleaning.
本發明提供一種提高樹脂對表面之密接性之彩色濾光片用玻璃板之製造方法、彩色濾光片面板之製造方法及顯示器用玻璃基板。 The present invention provides a method for producing a glass plate for a color filter which improves the adhesion of a resin to a surface, a method for producing a color filter panel, and a glass substrate for a display.
本發明之在表面形成有黑色矩陣樹脂之彩色濾光片用玻璃板之製造方法包括玻璃板製造步驟及玻璃板清洗步驟。於玻璃板製造步驟中,由熔融玻璃成形玻璃帶,並切斷玻璃帶而形成玻璃板。於玻璃板清洗步驟中,對玻璃板之表面進行清洗,而去除附著於表面之異物。玻璃板清洗步驟包括第1清洗步驟及第2清洗步驟。於第1清洗步驟中,使用添加有界面活性劑之無機鹼系之清洗劑清洗表面。於第2清洗步驟中,使用具有0.1%~2.38%濃度之氫氧化四甲基銨(TMAH)清 洗表面。於玻璃板清洗步驟中,清洗玻璃板,以使存在於表面之有機物之質量在每1cm2表面中為8ng以下。又,於自第1清洗步驟結束至第2清洗步驟開始期間,玻璃板之表面係保持為濕潤狀態。藉此,可控制第2清洗步驟後之玻璃基板表面之有機物之附著量。 The method for producing a glass plate for a color filter in which a black matrix resin is formed on the surface of the present invention includes a glass plate manufacturing step and a glass plate cleaning step. In the glass sheet manufacturing step, a glass ribbon is formed from molten glass, and the glass ribbon is cut to form a glass sheet. In the glass plate cleaning step, the surface of the glass plate is cleaned to remove foreign matter adhering to the surface. The glass plate cleaning step includes a first cleaning step and a second cleaning step. In the first washing step, the surface is washed with an inorganic base-based cleaning agent to which a surfactant is added. In the second cleaning step, the surface is washed using tetramethylammonium hydroxide (TMAH) having a concentration of 0.1% to 2.38%. In the glass plate cleaning step, the glass plate is washed so that the mass of the organic substance present on the surface is 8 ng or less per 1 cm 2 of the surface. Further, the surface of the glass sheet is kept in a wet state from the end of the first washing step to the start of the second washing step. Thereby, the amount of adhesion of the organic substance on the surface of the glass substrate after the second cleaning step can be controlled.
於本發明之彩色濾光片用玻璃板之製造方法中,利用下拉法或浮式法製造之玻璃板係首先進行使用無機鹼系之清洗劑清洗表面之第1清洗步驟,其次,進行使用氫氧化四甲基銨(TMAH)清洗表面之第2清洗步驟。TMAH具有將成為降低黑色矩陣樹脂對玻璃板表面之密接性之原因的有機物自玻璃板之表面去除之效果。又,藉由在進行第1清洗步驟之後進行第2清洗步驟,即便於第1清洗步驟中源自無機鹼系之清洗劑中所包含之界面活性劑之有機物附著於玻璃板之表面,於接下來之第2清洗步驟中,亦可自玻璃板之表面去除該有機物。即,於該彩色濾光片用玻璃板之製造方法中,可藉由第2清洗步驟將成為降低黑色矩陣樹脂對玻璃板表面之密接性之原因的有機物自玻璃板之表面有效地去除。因此,本發明之彩色濾光片用玻璃板之製造方法能夠提高樹脂對玻璃板表面之密接性。 In the method for producing a glass plate for a color filter according to the present invention, the glass plate produced by the down-draw method or the floating method is first subjected to a first cleaning step of cleaning the surface with an inorganic base-based cleaning agent, and secondly, hydrogen is used. The second cleaning step of the surface cleaning of tetramethylammonium oxide (TMAH). TMAH has an effect of removing organic substances which are the cause of the adhesion of the black matrix resin to the surface of the glass sheet from the surface of the glass sheet. Further, by performing the second washing step after performing the first washing step, even if the organic substance derived from the surfactant contained in the inorganic base-based cleaning agent adheres to the surface of the glass sheet in the first washing step, In the second cleaning step, the organic matter may also be removed from the surface of the glass plate. In other words, in the method for producing a glass plate for a color filter, the organic material which causes the adhesion of the black matrix resin to the surface of the glass plate can be effectively removed from the surface of the glass plate by the second cleaning step. Therefore, the method for producing a glass plate for a color filter of the present invention can improve the adhesion of the resin to the surface of the glass plate.
又,較佳為界面活性劑係離子系界面活性劑,於第2清洗步驟中,去除附著於玻璃板表面之離子系界面活性劑。於此情形時,在第1清洗步驟中,離子系界面活性劑附著於玻璃板之表面。而且,第2清洗步驟後之玻璃板之表面與第1清洗步驟後之玻璃板之表面相比,離子系界面活性劑之附著量少。換言之,於第2清洗步驟中,第2清洗步驟後之玻璃板表面上之離子系界面活性劑之附著量得以控制。 Further, a surfactant-based ion-based surfactant is preferred, and the ion-based surfactant adhering to the surface of the glass plate is removed in the second cleaning step. In this case, in the first washing step, the ion-based surfactant adheres to the surface of the glass plate. Further, the surface of the glass plate after the second cleaning step has a smaller amount of adhesion of the ion-based surfactant than the surface of the glass plate after the first cleaning step. In other words, in the second cleaning step, the adhesion amount of the ion-based surfactant on the surface of the glass plate after the second cleaning step is controlled.
又,於玻璃板清洗步驟中,較佳為清洗玻璃板,以使疏水性有機物之質量在每1cm2表面中為0.01ng~0.25ng。疏水性有機物係存在於玻璃板表面之有機物中之GC/MS(Gas Chromatography/Mass Spectrometry,氣相層析/質譜分析)中之保持時間為18分鐘以上之有 機物。又,疏水性有機物係芳香族化合物。在附著於玻璃板表面之有機物且GC/MS中之保持時間為18分鐘以上之疏水性有機物中包含作為具有苯環之有機物之芳香族化合物。芳香族化合物係成為降低黑色矩陣樹脂對玻璃板表面之密接性之原因的有機物。 Further, in the glass plate washing step, it is preferred to clean the glass plate so that the mass of the hydrophobic organic substance is 0.01 ng to 0.25 ng per 1 cm 2 of the surface. The hydrophobic organic substance is an organic substance which has a retention time of 18 minutes or more in GC/MS (Gas Chromatography/Mass Spectrometry) in an organic substance on the surface of a glass plate. Further, the hydrophobic organic compound is an aromatic compound. An aromatic compound which is an organic substance having a benzene ring is contained in a hydrophobic organic substance which adheres to the organic substance on the surface of the glass plate and has a retention time of 18 minutes or more in GC/MS. The aromatic compound is an organic substance which causes a decrease in the adhesion of the black matrix resin to the surface of the glass plate.
又,於玻璃板清洗步驟中,較佳為清洗玻璃板,以使存在於表面之疏水性有機物之質量在每1cm2表面中為0.01ng~0.15ng。疏水性有機物係與玻璃板相比疏水性較高之有機物。換言之,疏水性有機物係對水之親和性較玻璃板低之有機物。 Further, in the glass plate cleaning step, it is preferred to clean the glass plate so that the mass of the hydrophobic organic substance present on the surface is 0.01 ng to 0.15 ng per 1 cm 2 of the surface. A hydrophobic organic substance is an organic substance having a higher hydrophobicity than a glass plate. In other words, the hydrophobic organic substance is an organic substance having a lower affinity for water than a glass plate.
又,較佳為玻璃板之表面具有未達0.7nm之表面粗糙度Ra。表面粗糙度Ra係表示玻璃板表面之粗糙度之參數之一種即「中心線平均粗糙度」。於玻璃板之表面粗糙度Ra未達0.7nm之情形時,不會對黑色矩陣樹脂對玻璃板表面之密接性造成影響。 Further, it is preferred that the surface of the glass plate has a surface roughness Ra of less than 0.7 nm. The surface roughness Ra is a "center line average roughness" which is one of the parameters of the roughness of the surface of the glass plate. When the surface roughness Ra of the glass plate is less than 0.7 nm, the adhesion of the black matrix resin to the surface of the glass plate is not affected.
本發明之於玻璃基板之表面形成有樹脂膜之彩色濾光片面板之製造方法包括第1清洗步驟、第2清洗步驟及樹脂膜形成步驟。於第1清洗步驟中,使用包含界面活性劑之無機鹼系之清洗劑對形成樹脂膜之表面進行清洗。於第2清洗步驟中,使用具有0.1%~2.38%濃度之氫氧化四甲基銨對形成樹脂膜之表面進行清洗。於樹脂膜形成步驟中,於表面中之有機物之附著量在每1cm2中為8ng以下、且GC/MS中之保持時間為18分鐘以上之疏水性有機物之表面中之附著量在每1cm2中為0.25ng以下之表面形成樹脂膜。又,於自第1清洗步驟結束至第2清洗步驟開始期間,玻璃基板之表面係保持為濕潤狀態。藉此,可控制第2清洗步驟後之玻璃基板表面之有機物之附著量。又,於樹脂膜形成步驟中,較佳為樹脂膜係黑色矩陣,且使黑色矩陣以3μm~15μm之線寬圖案化。 A method of manufacturing a color filter panel in which a resin film is formed on a surface of a glass substrate of the present invention includes a first cleaning step, a second cleaning step, and a resin film forming step. In the first cleaning step, the surface on which the resin film is formed is washed using an inorganic base-based cleaning agent containing a surfactant. In the second cleaning step, the surface on which the resin film is formed is washed using tetramethylammonium hydroxide having a concentration of 0.1% to 2.38%. In the resin film forming step, the adhesion amount of the organic substance in the surface is 8 ng or less per 1 cm 2 , and the adhesion amount in the surface of the hydrophobic organic substance in the GC/MS is 18 minutes or more per 1 cm 2 . A resin film is formed on the surface of 0.25 ng or less. Further, the surface of the glass substrate is kept in a wet state from the end of the first cleaning step to the start of the second cleaning step. Thereby, the amount of adhesion of the organic substance on the surface of the glass substrate after the second cleaning step can be controlled. Further, in the resin film forming step, the resin film is preferably a black matrix, and the black matrix is patterned with a line width of 3 μm to 15 μm.
於本發明之彩色濾光片面板之製造方法中,根據上述理由,可將成為降低黑色矩陣樹脂對玻璃板表面之密接性之原因的有機物自玻璃 板之表面有效地去除。因此,本發明之彩色濾光片面板之製造方法可提高樹脂對彩色濾光片面板表面之密接性。 In the method for producing a color filter panel of the present invention, for the above reasons, an organic substance which is a cause of reducing the adhesion of the black matrix resin to the surface of the glass sheet can be used. The surface of the board is effectively removed. Therefore, the method of manufacturing the color filter panel of the present invention can improve the adhesion of the resin to the surface of the color filter panel.
本發明之顯示器用玻璃基板之表面上之有機物之附著量在每1cm2中為8ng以下,且表面上之芳香族化合物之附著量在每1cm2中為0.25ng以下。 The adhesion amount of the organic substance on the surface of the glass substrate for a display of the present invention is 8 ng or less per 1 cm 2 , and the adhesion amount of the aromatic compound on the surface is 0.25 ng or less per 1 cm 2 .
本發明之顯示器用玻璃基板中,由於成為降低黑色矩陣樹脂對表面之密接性之原因的芳香族化合物於表面上之附著量小,故而樹脂對玻璃基板表面之密接性高。 In the glass substrate for a display of the present invention, since the amount of adhesion of the aromatic compound to the surface which is a cause of lowering the adhesion of the black matrix resin to the surface is small, the adhesion of the resin to the surface of the glass substrate is high.
本發明之彩色濾光片用玻璃板之製造方法可提高樹脂對玻璃板表面之密接性。 The method for producing a glass plate for a color filter of the present invention can improve the adhesion of the resin to the surface of the glass plate.
又,本發明之彩色濾光片面板之製造方法可提高樹脂對彩色濾光片面板表面之密接性。 Further, the method of manufacturing a color filter panel of the present invention can improve the adhesion of the resin to the surface of the color filter panel.
又,本發明之顯示器用玻璃基板可提高樹脂對玻璃基板表面之密接性。 Further, the glass substrate for a display of the present invention can improve the adhesion of the resin to the surface of the glass substrate.
1‧‧‧單片式清洗裝置 1‧‧‧One-piece cleaning device
10‧‧‧第1清洗單元 10‧‧‧1st cleaning unit
12‧‧‧刷單元 12‧‧‧ brush unit
12a‧‧‧清洗刷輥 12a‧‧‧Washing brush roller
12b‧‧‧清洗刷輥 12b‧‧‧Washing brush roller
14‧‧‧海綿單元 14‧‧‧Sponge unit
14a‧‧‧清洗海綿輥 14a‧‧‧Clean sponge roller
14b‧‧‧清洗海綿輥 14b‧‧‧Clean sponge roller
16‧‧‧噴淋單元 16‧‧‧Spray unit
18‧‧‧清洗劑箱 18‧‧‧cleaning agent box
18a‧‧‧噴嘴 18a‧‧‧Nozzles
18b‧‧‧噴嘴 18b‧‧‧Nozzles
18c‧‧‧噴嘴 18c‧‧‧ nozzle
18d‧‧‧噴嘴 18d‧‧‧ nozzle
19‧‧‧純水箱 19‧‧‧ pure water tank
19a‧‧‧噴嘴 19a‧‧‧Nozzles
19b‧‧‧噴嘴 19b‧‧‧Nozzles
20‧‧‧第2清洗單元 20‧‧‧2nd cleaning unit
101‧‧‧批量清洗裝置 101‧‧‧ batch cleaning device
120‧‧‧盒 120‧‧‧ box
130‧‧‧液槽 130‧‧‧ liquid tank
G‧‧‧玻璃板 G‧‧‧glass plate
L‧‧‧液體 L‧‧‧Liquid
圖1係本實施形態之玻璃板之製造方法之流程圖。 Fig. 1 is a flow chart showing a method of manufacturing a glass sheet of the embodiment.
圖2係單片式清洗裝置之概略圖。 Figure 2 is a schematic view of a one-piece cleaning apparatus.
圖3係第1清洗單元之俯視圖。 Fig. 3 is a plan view of the first cleaning unit.
圖4係第1清洗單元之側視圖。 Figure 4 is a side view of the first cleaning unit.
圖5係批量清洗裝置之概略圖。 Figure 5 is a schematic view of a batch cleaning apparatus.
基於實施形態對本發明之彩色濾光片用玻璃板之製造方法進行說明。本實施形態中所製造之彩色濾光片用玻璃板係在液晶顯示器等平板顯示器(FPD,Flat Panel Display)之製造中所使用之玻璃板。該玻 璃板藉由在表面配置黑色矩陣、以及使紅色(R)、綠色(G)、藍色(B)之光透過之波長選擇元件即RGB像素,而形成彩色濾光片。黑色矩陣遮斷RGB像素區域以外之背光源之漏光,並防止相互鄰接之RGB像素之混色,藉此提高顯示對比度。即,彩色濾光片中之光之通過區域由黑色矩陣之形狀及配置決定。玻璃板之厚度例如為0.1mm~0.7mm。玻璃板之尺寸例如為680mm×880mm(G4尺寸)、2200mm×2500mm(G8尺寸)。 A method of producing a glass sheet for a color filter of the present invention will be described based on an embodiment. The glass plate for color filters manufactured in this embodiment is a glass plate used for manufacture of a flat panel display (FPD) such as a liquid crystal display. The glass The glass plate forms a color filter by arranging a black matrix on the surface and RGB pixels which are wavelength selection elements that transmit light of red (R), green (G), and blue (B). The black matrix blocks light leakage from backlights other than the RGB pixel area and prevents color mixture of adjacent RGB pixels, thereby improving display contrast. That is, the light passing region in the color filter is determined by the shape and arrangement of the black matrix. The thickness of the glass plate is, for example, 0.1 mm to 0.7 mm. The size of the glass plate is, for example, 680 mm × 880 mm (G4 size), 2200 mm × 2500 mm (G8 size).
FPD之製造中所使用之玻璃板較佳為無鹼玻璃或微鹼玻璃。於玻璃板為無鹼玻璃之情形時,玻璃之組成例如為SiO2:50質量%~70質量%、Al2O3:0質量%~25質量%、B2O3:1質量%~15質量%、MgO:0質量%~10質量%、CaO:0質量%~20質量%、SrO:0質量%~20質量%、BaO:0質量%~10質量%。此處,MgO、CaO、SrO及BaO之合計含量為5質量%~30質量%。 The glass plate used in the manufacture of the FPD is preferably an alkali-free glass or a slightly alkali glass. When the glass plate is an alkali-free glass, the composition of the glass is, for example, SiO 2 : 50% by mass to 70% by mass, Al 2 O 3 : 0% by mass to 25% by mass, and B 2 O 3 : 1% by mass to 15% Mass%, MgO: 0% by mass to 10% by mass, CaO: 0% by mass to 20% by mass, SrO: 0% by mass to 20% by mass, and BaO: 0% by mass to 10% by mass. Here, the total content of MgO, CaO, SrO, and BaO is 5% by mass to 30% by mass.
於玻璃板為包含微量鹼金屬之微鹼玻璃之情形時,玻璃之組成進而包含0.1質量%~0.5質量%之R'2O,較佳為包含0.2質量%~0.5質量%之R'2O。此處,R'為選自Li、Na及K中之至少1種。再者,R'2O之含量之合計亦可未達0.1質量%。 When the glass plate is a micro alkali glass containing a trace amount of an alkali metal, the composition of the glass further includes 0.1% by mass to 0.5% by mass of R' 2 O, preferably 0.2% by mass to 0.5% by mass of R' 2 O. . Here, R' is at least one selected from the group consisting of Li, Na, and K. Further, the total content of R' 2 O may be less than 0.1% by mass.
又,玻璃板除了含有上述成分以外,亦可進而含有SnO2:0.01質量%~1質量%(較佳為0.01質量%~0.5質量%)、Fe2O3:0質量%~0.2質量%(較佳為0.01質量%~0.08質量%),考慮到環境負載,亦可實質上不含As2O3、Sb2O3及PbO。 Further, the glass plate may further contain SnO 2 : 0.01% by mass to 1% by mass (preferably 0.01% by mass to 0.5% by mass), and Fe 2 O 3 : 0% by mass to 0.2% by mass in addition to the above components ( It is preferably 0.01% by mass to 0.08% by mass), and substantially does not contain As 2 O 3 , Sb 2 O 3 and PbO in consideration of environmental load.
圖1係表示玻璃板之製造方法之流程的流程圖。以下,對流程圖之各步驟S1~S10進行說明。 Fig. 1 is a flow chart showing the flow of a method of manufacturing a glass sheet. Hereinafter, each of the steps S1 to S10 of the flowchart will be described.
首先,於步驟S1中,藉由對為了製造具有上述組成之玻璃板而經調整之玻璃原料進行加熱而生成熔融玻璃,並藉由下拉法、再曳引 法或浮式法等由熔融玻璃或預成形玻璃連續地成形具有特定厚度之玻璃帶。於步驟S2中,切斷在步驟S1中生成之玻璃帶,而獲得具有特定尺寸之毛坯玻璃。於步驟S3中,在步驟S2中獲得之毛坯玻璃係以介隔用以保護毛坯玻璃之表面之間隔紙積層而成之積層體之形式載置於用以搬送及保管毛坯玻璃之托板上。 First, in step S1, molten glass is produced by heating a glass raw material adjusted to produce a glass plate having the above composition, and is pulled down by a down-draw method. A glass ribbon having a specific thickness is continuously formed from molten glass or preformed glass by a method or a float method. In step S2, the glass ribbon produced in step S1 is cut to obtain a blank glass having a specific size. In step S3, the blank glass obtained in step S2 is placed on a pallet for transporting and storing the blank glass in the form of a laminate which is formed by laminating the spacer paper for protecting the surface of the blank glass.
其次,於步驟S4中,自毛坯玻璃之積層體中取出毛坯玻璃,將毛坯玻璃切斷為作為製品之玻璃板之尺寸。於步驟S5中,對在步驟S4中獲得之玻璃板進行端面之研削及研磨、端面之蝕刻等端面加工處理。 Next, in step S4, the blank glass is taken out from the laminated body of the blank glass, and the blank glass is cut into the size of the glass plate as a product. In step S5, the glass sheet obtained in step S4 is subjected to end surface processing such as grinding, polishing, and etching of the end surface.
其次,於步驟S6中進行玻璃板之清洗。於玻璃板之清洗步驟中,去除附著於玻璃板表面之玻璃之微小片即玻璃屑、灰塵、污垢、黏著性之異物等。又,於玻璃板之清洗步驟中,係使用含有界面活性劑之無機鹼系之清洗劑,以使於清洗後之玻璃板之表面不會再次附著該等異物。 Next, the glass plate is cleaned in step S6. In the cleaning step of the glass plate, the fine particles of the glass adhering to the surface of the glass plate, that is, glass swarf, dust, dirt, adhesive foreign matter, and the like are removed. Further, in the cleaning step of the glass plate, an inorganic base-based cleaning agent containing a surfactant is used so that the foreign matter does not adhere to the surface of the glass plate after cleaning.
繼而,於步驟S7中,進行在步驟S6中經清洗之玻璃板之光學檢查。具體而言,進行於玻璃板之表面是否形成有具有光學缺陷之傷痕、及於玻璃板之表面是否附著有灰塵或污垢等檢查。於步驟S8中,將步驟S7之檢查合格之玻璃板以與用以保護玻璃板表面之間隔紙交替地積層而成之積層體之形式載置於托板上並捆綁包裝。於步驟S9中,將經捆綁包裝之玻璃板之積層體出貨給FPD之製造商等交付對象。關於被所出貨之玻璃板之積層體夾持之間隔紙,就防止源自間隔紙之異物附著於玻璃板表面之觀點而言,可使用不包含再生紙之紙漿紙。 Then, in step S7, optical inspection of the glass plate washed in step S6 is performed. Specifically, it is examined whether or not a scratch having an optical defect is formed on the surface of the glass plate, and whether or not dust or dirt adheres to the surface of the glass plate. In step S8, the glass sheets which have passed the inspection in step S7 are placed on the pallet in the form of a laminate which is alternately laminated with the spacer paper for protecting the surface of the glass sheet, and are bundled and packaged. In step S9, the laminated body of the bundled glass plate is shipped to a manufacturer such as a FPD. Regarding the spacer paper sandwiched by the laminated body of the glass plate to be shipped, a pulp paper containing no recycled paper can be used from the viewpoint of preventing foreign matter originating from the spacer from adhering to the surface of the glass plate.
又,在步驟S3中被載置於托板上之毛坯玻璃之積層體亦可於步驟S10中經過數週或數月之長時間被保管。於此情形時,就成本及環境保護之觀點而言,被所保管之毛坯玻璃之積層體中夾入之間隔紙係使用再生紙。經長時間保管之毛坯玻璃之積層體係如上所述般經由步 驟S4之切斷步驟至步驟S8之捆綁包裝步驟,而於步驟S9中出貨。再者,在步驟S8中被載置於托板上且被捆綁包裝之玻璃板之積層體亦可於步驟S10中經過數週或數月之長時間被保管。於此情形時,亦可使用再生紙作為被玻璃板之積層體中夾入之間隔紙。 Moreover, the laminated body of the blank glass placed on the pallet in step S3 may be stored for several weeks or several months in step S10. In this case, from the viewpoint of cost and environmental protection, the paper which is sandwiched between the stacked sheets of the preserved blank glass is recycled paper. The laminated system of the blank glass that has been stored for a long time is as described above. The cutting step of step S4 is to the binding packaging step of step S8, and is shipped in step S9. Further, the laminate of the glass sheets placed on the pallet and packed in the step S8 may be stored for several weeks or months in the step S10. In this case, recycled paper can also be used as the spacer paper sandwiched between the laminated bodies of the glass sheets.
其次,詳細說明於圖1之步驟S6中進行之玻璃板之清洗步驟。玻璃板之清洗步驟包括第1清洗步驟及第2清洗步驟。於第1清洗步驟中,使用添加有界面活性劑之無機鹼系之清洗劑進行玻璃板表面之清洗。於第2清洗步驟中,使用氫氧化四甲基銨(TMAH)進行玻璃板表面之清洗。 Next, the cleaning step of the glass plate performed in the step S6 of Fig. 1 will be described in detail. The washing step of the glass plate includes a first washing step and a second washing step. In the first washing step, the surface of the glass plate is washed using an inorganic base-based cleaning agent to which a surfactant is added. In the second washing step, the surface of the glass plate was washed with tetramethylammonium hydroxide (TMAH).
第1清洗步驟中所使用之無機鹼系之清洗劑係藉由在以水稀釋市售之玻璃板用清洗液而獲得之稀釋液中添加鹼成分而生成。作為玻璃板用清洗液,例如,使用Parker Corporation公司製造之PK-LCG系列、或橫濱油脂工業股份有限公司製造之Semiclean系列等。玻璃板用清洗液係例如以水稀釋為1wt%~5wt%之濃度。稀釋液之鹼成分之濃度換算為氫氧化鉀(KOH)之濃度,例如為0.02wt%~0.15wt%。 The inorganic base-based cleaning agent used in the first washing step is produced by adding an alkali component to a diluted solution obtained by diluting a commercially available cleaning solution for a glass plate with water. As the cleaning liquid for a glass plate, for example, a PK-LCG series manufactured by Parker Corporation, or a Semiclean series manufactured by Yokohama Oil & Fats Co., Ltd., or the like is used. The glass plate cleaning liquid is diluted, for example, with water to a concentration of 1% by weight to 5% by weight. The concentration of the alkali component of the diluent is converted to a concentration of potassium hydroxide (KOH), for example, from 0.02% by weight to 0.15% by weight.
就使玻璃板表面保持清潔之方面而言,用以稀釋清洗劑之水較佳為實施過離子交換處理、EDI(Electrodeionization:電去電離)處理、利用逆滲透膜(RO(Reverse Osmosis)膜)之過濾處理、及通過脫二氧化碳裝置之脫二氧化碳處理之純水或超純水。又,為了去除溶解性之有機物,較佳為進行使水通過活性碳之處理。具體而言,較佳為使用過濾器自水中去除微粒子等異物,其次,使水通過活性碳而去除有機物,繼而,實施離子交換處理、EDI處理、利用逆滲透膜之過濾處理、及通過脫二氧化碳裝置之脫二氧化碳處理。 In order to keep the surface of the glass plate clean, the water for diluting the cleaning agent is preferably subjected to ion exchange treatment, EDI (Electrodeionization) treatment, and reverse osmosis membrane (RO (Reverse Osmosis) membrane). The filtration treatment and the pure water or ultrapure water treated by decarbonation of the decarbonation device. Further, in order to remove the soluble organic matter, it is preferred to carry out the treatment of passing water through the activated carbon. Specifically, it is preferable to use a filter to remove foreign matter such as fine particles from water, and secondly, to remove organic matter by passing the activated carbon, and then perform ion exchange treatment, EDI treatment, filtration treatment using a reverse osmosis membrane, and decarbonation. Decarbonation treatment of the device.
於離子交換處理中,使用離子交換樹脂膜自水中去除水中所含有之離子性物質、例如氯離子或鈉離子等。於EDI處理中,使用離子 交換樹脂膜,且利用對電極賦予電位而形成之電位梯度,以較高之精度自水中去除離子性物質。於利用逆滲透膜之過濾處理中,自水中去除離子性物質、鹽類及有機物。於脫二氧化碳處理中,使用脫二氧化碳裝置自水中去除二氧化碳。 In the ion exchange treatment, an ionic substance such as chloride ion or sodium ion contained in the water is removed from the water using an ion exchange resin membrane. In the EDI process, use ions The resin film is exchanged, and the potential gradient formed by applying a potential to the electrode is used to remove the ionic substance from the water with high precision. In the filtration treatment using a reverse osmosis membrane, ionic substances, salts and organic substances are removed from the water. In the decarbonation treatment, carbon dioxide is removed from the water using a decarbonation device.
於本實施形態中,在玻璃板用清洗液之稀釋液中添加選自由KOH、NaOH、ETDA-4Na、ETDA-4K、Na4P2O7及K4P2O7所組成之群中之1種以上之鹼成分,而生成第1清洗步驟中所使用之清洗劑。該清洗劑之鹼成分之濃度換算成氫氧化鉀(KOH)之濃度為1wt%以上。上述鹼成分與其他鹼成分相比,對玻璃之蝕刻性高且溶解性優異。尤其是就蝕刻性、溶解性、及防止對形成於玻璃板之薄膜電晶體之不良影響之觀點而言,較佳為單獨使用KOH作為鹼成分。又,KOH及NaOH與其他鹼成分相比,在排水處理之方面有利。 In the present embodiment, a diluent selected from the group consisting of KOH, NaOH, ETDA-4Na, ETDA-4K, Na 4 P 2 O 7 and K 4 P 2 O 7 is added to the diluted solution of the cleaning liquid for glass plates. One or more kinds of alkali components are used to form a cleaning agent used in the first washing step. The concentration of the alkali component of the cleaning agent is converted to a concentration of potassium hydroxide (KOH) of 1% by weight or more. The alkali component is more etchable to glass than the other alkali components, and is excellent in solubility. In particular, from the viewpoints of etchability, solubility, and prevention of adverse effects on the thin film transistor formed on the glass plate, it is preferred to use KOH alone as an alkali component. Further, KOH and NaOH are advantageous in terms of drainage treatment as compared with other alkali components.
再者,第1清洗步驟中所使用之清洗劑中,鹼成分之濃度越高,則自玻璃板去除異物之清洗力越強。然而,若鹼成分之濃度過高,則會產生腐蝕玻璃板清洗裝置並在清洗劑中生成結晶等問題。因此,清洗劑之鹼成分之濃度較佳為不超過10wt%。又,為了容易地進行清洗劑之處理,清洗劑之鹼成分之濃度更佳為不超過5wt%。 Further, in the cleaning agent used in the first cleaning step, the higher the concentration of the alkali component, the stronger the cleaning power for removing foreign matter from the glass plate. However, if the concentration of the alkali component is too high, there is a problem that the glass plate cleaning device is corroded and crystals are formed in the cleaning agent. Therefore, the concentration of the alkali component of the cleaning agent is preferably not more than 10% by weight. Further, in order to easily carry out the treatment of the cleaning agent, the concentration of the alkali component of the cleaning agent is more preferably not more than 5% by weight.
於本實施形態中,玻璃板之清洗方法有單片式清洗及批量清洗之2種清洗方法。首先,對藉由單片式清洗之玻璃板之清洗方法進行說明。圖2係進行單片式清洗之玻璃板G之單片式清洗裝置1之概略圖。單片式清洗裝置1包括進行第1清洗步驟之第1清洗單元10、及進行第2清洗步驟之第2清洗單元20。玻璃板G係首先於第1清洗單元10中利用添加有界面活性劑之無機鹼系之清洗劑進行清洗,其次,於第2清洗單元20中利用TMAH進行清洗。 In the present embodiment, the glass sheet cleaning method includes two types of cleaning methods: single-chip cleaning and batch cleaning. First, a cleaning method of a glass plate by single-chip cleaning will be described. Fig. 2 is a schematic view of a one-chip cleaning apparatus 1 for performing a single-piece cleaning of a glass sheet G. The one-chip cleaning apparatus 1 includes a first cleaning unit 10 that performs a first cleaning step and a second cleaning unit 20 that performs a second cleaning step. The glass plate G is first cleaned in the first cleaning unit 10 with a detergent containing an inorganic base added with a surfactant, and secondly, washed in the second cleaning unit 20 by TMAH.
圖3係第1清洗單元10之俯視圖,圖4係第1清洗單元10之側視圖。於圖3及圖4中,省略了搬送玻璃板G之搬送裝置。再者,由於第 2清洗單元20之構成與第1清洗單元10之構成實質上相同,故而以下僅對第1清洗單元10之構成進行說明。關於第1清洗單元10與第2清洗單元20之不同方面,將於下文中進行敍述。 3 is a plan view of the first cleaning unit 10, and FIG. 4 is a side view of the first cleaning unit 10. In FIGS. 3 and 4, the conveying device for conveying the glass sheet G is omitted. Again, due to the The configuration of the cleaning unit 20 is substantially the same as the configuration of the first cleaning unit 10. Therefore, only the configuration of the first cleaning unit 10 will be described below. Different aspects of the first cleaning unit 10 and the second cleaning unit 20 will be described below.
第1清洗單元10係如圖3所示般包括刷單元12、海綿單元14及噴淋單元16。該等單元係自玻璃板G之搬送方向之上游側朝向下游側依序配置。如圖4所示,第1清洗單元10進而包括清洗劑箱18、純水箱19及噴嘴18a、18b、18c、18d、19a、19b。 The first cleaning unit 10 includes a brush unit 12, a sponge unit 14, and a shower unit 16 as shown in FIG. These units are arranged in order from the upstream side to the downstream side in the conveying direction of the glass sheet G. As shown in FIG. 4, the first cleaning unit 10 further includes a detergent tank 18, a pure water tank 19, and nozzles 18a, 18b, 18c, 18d, 19a, and 19b.
刷單元12具有清洗刷輥12a、12b。清洗刷輥12a、12b係沿著玻璃板G之搬送方向配置。清洗刷輥12a、12b係以可分別對所搬送之玻璃板G之兩表面進行清洗之方式在玻璃板G之上下配置一對。清洗刷輥12a、12b係分別以橫穿玻璃板G之搬送方向之方式配置。於清洗刷輥12a、12b之外周面安裝有複數個清洗刷。藉由清洗刷輥12a、12b之軸旋轉,使清洗刷接觸於所搬送之玻璃板G之表面,而對玻璃板G之表面進行清洗。於圖3中,清洗刷輥12a、12b係沿著玻璃板G之搬送方向配置有2行,但亦可僅配置1行,或亦可配置3行以上。 The brush unit 12 has cleaning brush rollers 12a, 12b. The cleaning brush rollers 12a and 12b are disposed along the conveying direction of the glass sheet G. The cleaning brush rolls 12a and 12b are disposed one above the glass sheet G so that the two surfaces of the glass sheet G to be conveyed can be cleaned. The cleaning brush rollers 12a and 12b are disposed so as to traverse the conveying direction of the glass sheet G, respectively. A plurality of cleaning brushes are attached to the outer peripheral surface of the cleaning brush rollers 12a and 12b. The surface of the glass plate G is cleaned by the rotation of the washing brush rolls 12a and 12b to bring the cleaning brush into contact with the surface of the conveyed glass sheet G. In FIG. 3, the cleaning brush rolls 12a and 12b are arranged in two rows along the conveying direction of the glass sheet G, but they may be arranged in only one row or three rows or more.
海綿單元14具有清洗海綿輥14a、14b。清洗海綿輥14a、14b係沿著玻璃板G之搬送方向配置。清洗海綿輥14a、14b係以可分別對所搬送之玻璃板G之兩表面進行清洗之方式在玻璃板G之上下配置一對。清洗海綿輥14a、14b係分別以橫穿玻璃板G之搬送方向之方式配置。於清洗海綿輥14a、14b之外周面安裝有清洗海綿。藉由清洗海綿輥14a、14b之軸旋轉,使清洗海綿接觸於所搬送之玻璃板G之表面,而對玻璃板G之表面進行清洗。於圖3中,清洗海綿輥14a、14b係沿著玻璃板G之搬送方向配置有2行,但亦可僅配置1行,或亦可配置3行以上。 The sponge unit 14 has cleaning sponge rolls 14a, 14b. The cleaning sponge rolls 14a and 14b are arranged along the conveying direction of the glass sheet G. The cleaning sponge rolls 14a and 14b are disposed one above the glass sheet G so that the two surfaces of the glass sheet G to be conveyed can be cleaned. The cleaning sponge rolls 14a and 14b are disposed so as to traverse the conveying direction of the glass sheet G, respectively. A cleaning sponge is attached to the outer peripheral surface of the cleaning sponge rolls 14a and 14b. The surface of the glass plate G is cleaned by contacting the shafts of the cleaning sponge rolls 14a and 14b so that the cleaning sponge contacts the surface of the glass plate G to be conveyed. In FIG. 3, the cleaning sponge rolls 14a and 14b are arranged in two rows along the conveying direction of the glass sheet G, but they may be arranged in only one row or three rows or more.
第1清洗單元10之清洗劑箱18貯存在第1清洗步驟中使用之添加有界面活性劑之無機鹼系之清洗劑。清洗劑箱18具有例如將清洗劑加 熱至50℃~80℃之溫度範圍並進行保溫之功能。噴嘴18a、18b將自清洗劑箱18供給之清洗劑噴射至在刷單元12內被搬送之玻璃板G之兩表面。噴嘴18c、18d將自清洗劑箱18供給之清洗劑噴射至在海綿單元14內被搬送之玻璃板G之兩表面。 The detergent tank 18 of the first cleaning unit 10 stores the inorganic base-based cleaning agent to which the surfactant is added, which is used in the first cleaning step. The detergent tank 18 has, for example, a cleaning agent Heat to a temperature range of 50 ° C ~ 80 ° C and perform the function of heat preservation. The nozzles 18a and 18b spray the cleaning agent supplied from the cleaning agent tank 18 onto both surfaces of the glass sheet G conveyed in the brush unit 12. The nozzles 18c and 18d spray the cleaning agent supplied from the cleaning agent tank 18 onto both surfaces of the glass sheet G conveyed in the sponge unit 14.
純水箱19貯存上述純水或超純水。噴嘴19a、19b將自純水箱19供給之純水或超純水噴射至在噴淋單元16內被搬送之玻璃板G之兩表面。 The pure water tank 19 stores the above pure water or ultrapure water. The nozzles 19a and 19b spray pure water or ultrapure water supplied from the pure water tank 19 to both surfaces of the glass sheet G conveyed in the shower unit 16.
第2清洗單元20具有與第1清洗單元10相同之構成。然而,第2清洗單元20之清洗劑箱18貯存在第2清洗步驟中使用之TMAH。TMAH之濃度為0.1%~2.38%,但較佳為0.25%~1.5%,更佳為0.35%~1.0%。 The second cleaning unit 20 has the same configuration as the first cleaning unit 10. However, the detergent tank 18 of the second cleaning unit 20 stores the TMAH used in the second cleaning step. The concentration of TMAH is from 0.1% to 2.38%, but is preferably from 0.25% to 1.5%, more preferably from 0.35% to 1.0%.
再者,於本實施形態中,如圖4所示,刷單元12及海綿單元14使用共用之清洗劑箱18,但亦可使用各自之清洗劑箱18。於此情形時,刷單元12及海綿單元14亦可使用不同濃度之清洗劑清洗玻璃板G。 Further, in the present embodiment, as shown in FIG. 4, the brush unit 12 and the sponge unit 14 use the common detergent tank 18, but the respective detergent tanks 18 may be used. In this case, the brush unit 12 and the sponge unit 14 can also clean the glass sheet G with different concentrations of the cleaning agent.
其次,對單片式清洗裝置1中之玻璃板G之清洗流程進行說明。首先,於第1清洗單元10之刷單元12中進行玻璃板G之刷清洗。具體而言,自噴嘴18a、18b噴射之無機鹼系之清洗劑附著於玻璃板G之兩表面,藉由清洗刷輥12a、12b之軸旋轉對玻璃板G之兩表面進行清洗。 Next, the cleaning process of the glass sheet G in the one-piece cleaning apparatus 1 will be described. First, the brush cleaning of the glass plate G is performed in the brush unit 12 of the first cleaning unit 10. Specifically, the inorganic alkali-based cleaning agent sprayed from the nozzles 18a and 18b adheres to both surfaces of the glass sheet G, and both surfaces of the glass sheet G are cleaned by the rotation of the cleaning brush rolls 12a and 12b.
其次,於第1清洗單元10之海綿單元14中進行玻璃板G之海綿清洗。具體而言,自噴嘴18c、18d噴射之無機鹼系之清洗劑附著於玻璃板G之兩表面,藉由清洗海綿輥14a、14b之軸旋轉對玻璃板G之兩表面進行清洗。 Next, the sponge cleaning of the glass plate G is performed in the sponge unit 14 of the first cleaning unit 10. Specifically, the inorganic alkali-based cleaning agent sprayed from the nozzles 18c and 18d adheres to both surfaces of the glass sheet G, and both surfaces of the glass sheet G are cleaned by the shaft rotation of the cleaning sponge rolls 14a and 14b.
繼而,於第1清洗單元10之噴淋單元16中,去除附著於玻璃板G之表面之無機鹼系之清洗劑。具體而言,自噴嘴19a、19b噴射之純水或超純水附著於玻璃板G之兩表面上,藉此利用純水或超純水洗刷玻 璃板G之表面,而洗掉附著於表面之無機鹼系之清洗劑。再者,已通過噴淋單元16之玻璃板G之表面上附著有純水或超純水而成為濕潤狀態。已通過第1清洗單元10之玻璃板G係保持著表面濕潤之狀態被搬送至第2清洗單元20之內部。藉此,可控制通過第2清洗單元20後之玻璃板G之表面之異物之附著量。 Then, in the shower unit 16 of the first cleaning unit 10, the inorganic base-based cleaning agent adhering to the surface of the glass sheet G is removed. Specifically, pure water or ultrapure water sprayed from the nozzles 19a, 19b is attached to both surfaces of the glass sheet G, thereby washing the glass with pure water or ultrapure water. The surface of the glass plate G is washed away from the inorganic base-based cleaning agent attached to the surface. Further, pure water or ultrapure water has adhered to the surface of the glass sheet G of the shower unit 16 to be in a wet state. The glass sheet G of the first cleaning unit 10 is conveyed to the inside of the second cleaning unit 20 while the surface is wet. Thereby, the amount of adhesion of foreign matter on the surface of the glass sheet G that has passed through the second cleaning unit 20 can be controlled.
繼而,於第2清洗單元20之刷單元12中進行玻璃板G之刷清洗。具體而言,自噴嘴18a、18b噴射之TMAH附著於玻璃板G之兩表面,藉由清洗刷輥12a、12b之軸旋轉對玻璃板G之兩表面進行清洗。 Then, the brush cleaning of the glass plate G is performed in the brush unit 12 of the second cleaning unit 20. Specifically, TMAH sprayed from the nozzles 18a and 18b adheres to both surfaces of the glass sheet G, and both surfaces of the glass sheet G are cleaned by the shaft rotation of the cleaning brush rolls 12a and 12b.
繼而,於第2清洗單元20之海綿單元14中進行玻璃板G之海綿清洗。具體而言,自噴嘴18c、18d噴射之TMAH附著於玻璃板G之兩表面,藉由清洗海綿輥14a、14b之軸旋轉對玻璃板G之兩表面進行清洗。 Then, sponge cleaning of the glass plate G is performed in the sponge unit 14 of the second cleaning unit 20. Specifically, TMAH sprayed from the nozzles 18c and 18d adheres to both surfaces of the glass sheet G, and both surfaces of the glass sheet G are cleaned by the shaft rotation of the cleaning sponge rolls 14a and 14b.
繼而,於第2清洗單元20之噴淋單元16中去除附著於玻璃板G之表面之TMAH。具體而言,自噴嘴19a、19b噴射之純水或超純水附著於玻璃板G之兩表面,藉此利用純水或超純水洗刷玻璃板G之表面,而洗掉附著於表面之TMAH。 Then, the TMAH attached to the surface of the glass sheet G is removed from the shower unit 16 of the second cleaning unit 20. Specifically, pure water or ultrapure water sprayed from the nozzles 19a, 19b is attached to both surfaces of the glass sheet G, whereby the surface of the glass sheet G is washed with pure water or ultrapure water, and the TMAH attached to the surface is washed away. .
以上,對藉由單片式清洗之玻璃板之清洗方法進行了說明。其次,對藉由批量清洗之玻璃板之清洗方法進行說明。圖5係進行批量清洗之玻璃板之批量清洗裝置101之概略圖。批量清洗裝置101包括搬送可收容複數個玻璃板G之盒120之搬送機構(未圖示)及複數個液槽130。各液槽130包括超音波清洗機構及溫度調節機構,該超音波清洗機構視需要於將玻璃板G浸漬於液體L中之狀態下利用超音波清洗玻璃板G,該溫度調節機構調節液體L之溫度。批量清洗裝置101進而包括對各液槽130供給液體L之箱(未圖示)。 The cleaning method of the glass plate by single-chip cleaning has been described above. Next, the cleaning method of the glass plate by batch cleaning will be described. Fig. 5 is a schematic view of a batch cleaning apparatus 101 for performing glass cleaning in batches. The batch cleaning device 101 includes a transport mechanism (not shown) that transports a cassette 120 that can accommodate a plurality of glass sheets G, and a plurality of liquid tanks 130. Each of the liquid tanks 130 includes an ultrasonic cleaning mechanism and a temperature adjusting mechanism. The ultrasonic cleaning mechanism cleans the glass sheet G by ultrasonic waves in a state where the glass sheet G is immersed in the liquid L, and the temperature adjusting mechanism adjusts the liquid L. temperature. The batch cleaning device 101 further includes a tank (not shown) for supplying the liquid L to each of the liquid tanks 130.
收容有複數片玻璃板G之盒120係藉由搬送機構將其搬送,依序浸漬於貯存在液槽130內之複數種液體L中進行清洗。於批量清洗裝置 101中,適當地決定浸漬玻璃板G之液體L之種類及順序。作為批量清洗步驟之一例,有第1步使用氟酸、第2步使用純水、第3步使用無機鹼系之清洗劑、第4步使用純水、第5步使用TMAH、第6步使用純水、第7步使用超純水來清洗玻璃板G之步驟。第2、4、6步之步驟中所使用之純水及第7步之步驟中所使用之超純水分別與在上述單片式清洗裝置1中使用之純水及超純水相同。第3步之步驟中所使用之無機鹼系之清洗劑與在上述單片式清洗裝置1中使用之清洗劑相同。將玻璃板G於各液槽130中浸漬於液體L內之時間根據液體L為45秒~180秒。再者,亦可不進行作為第1步之步驟之利用氟酸進行之玻璃板G之表面處理。 The cassette 120 in which a plurality of glass sheets G are accommodated is transported by a transport mechanism, and sequentially immersed in a plurality of liquids L stored in the liquid tank 130 for washing. Batch cleaning device In 101, the kind and order of the liquid L which immersed in the glass plate G are determined suitably. As an example of the batch cleaning step, there are a first step using hydrofluoric acid, a second step using pure water, a third step using an inorganic alkali-based cleaning agent, a fourth step using pure water, a fifth step using TMAH, and a sixth step using Pure water, step 7 uses ultrapure water to clean the glass plate G. The pure water used in the steps of the second, fourth, and sixth steps and the ultrapure water used in the step of the seventh step are the same as the pure water and the ultrapure water used in the above single-chip cleaning apparatus 1, respectively. The inorganic base-based cleaning agent used in the step of the third step is the same as the cleaning agent used in the above-described one-chip cleaning apparatus 1. The time during which the glass sheet G is immersed in the liquid L in each of the liquid tanks 130 is 45 seconds to 180 seconds depending on the liquid L. Further, the surface treatment of the glass plate G using fluoric acid as the step of the first step may not be performed.
先前,為了去除附著於玻璃板表面之有機物,而採用使用無機鹼系之清洗劑對玻璃板表面進行清洗之方法。於FPD之製造中所使用之玻璃板之表面形成TFT等半導體元件。關於此種玻璃板,為了抑制因剝離帶電或短路等而導致之半導體元件之破壞,而要求表面具有極高之清潔度。因此,使用如下方法:藉由使用無機鹼系之清洗劑對玻璃板表面進行清洗,而製造具有極高之清潔度之玻璃板。 Previously, in order to remove the organic matter adhering to the surface of the glass plate, a method of cleaning the surface of the glass plate with an inorganic base-based cleaning agent was used. A semiconductor element such as a TFT is formed on the surface of the glass plate used in the manufacture of the FPD. In order to suppress the destruction of the semiconductor element due to peeling electrification or short circuit, etc., such a glass plate is required to have an extremely high degree of cleanliness. Therefore, a method is employed in which a glass plate having an extremely high degree of cleanliness is produced by washing the surface of the glass plate with an inorganic base-based cleaning agent.
然而,可知以高清潔度為目的而使用KOH或NaOH系之無機鹼系之清洗劑進行清洗後之玻璃板具有如下問題:黑色矩陣樹脂對表面之密接性低,從而黑色矩陣自玻璃板之表面剝離。尤其是近年來,伴隨著顯示器之高精細化,配置於玻璃板表面之黑色矩陣之線寬及間距變小,故而黑色矩陣樹脂對玻璃板表面之密接性降低係重要之問題。因此,上述玻璃板之清洗方法無法應對黑色矩陣之高精細化。 However, it is understood that the glass plate after cleaning with a KOH or NaOH-based inorganic base-based cleaning agent for the purpose of high cleanliness has a problem that the black matrix resin has low adhesion to the surface, and thus the black matrix is on the surface of the glass plate. Stripped. In particular, in recent years, with the high definition of the display, the line width and pitch of the black matrix disposed on the surface of the glass plate are reduced, so that the adhesion of the black matrix resin to the surface of the glass plate is important. Therefore, the above-described glass plate cleaning method cannot cope with the high definition of the black matrix.
又,附著於玻璃板表面之特定之有機物有可能係黑色矩陣樹脂對玻璃板表面之密接性降低之原因。具體而言,若使用添加有界面活 性劑之無機鹼系之清洗劑對玻璃板之表面進行清洗,則黑色矩陣樹脂對玻璃板表面之密接性降低。因此,源自界面活性劑之有機物有可能係黑色矩陣樹脂之密接性降低之原因。又,造成黑色矩陣樹脂之密接性降低之有機物中有可能亦包含例如源自玻璃板之積層體中所包含之間隔紙之有機物、以及玻璃板積層體之保管及搬送環境下之氛圍中之有機物。 Further, the specific organic substance adhering to the surface of the glass plate may cause the adhesion of the black matrix resin to the surface of the glass plate to be lowered. Specifically, if you use the interface to add live When the inorganic base-based cleaning agent of the agent cleans the surface of the glass plate, the adhesion of the black matrix resin to the surface of the glass plate is lowered. Therefore, the organic substance derived from the surfactant may cause a decrease in the adhesion of the black matrix resin. Further, the organic substance which causes the adhesion of the black matrix resin to be reduced may include, for example, an organic substance derived from a spacer paper contained in the laminated body of the glass plate, and an organic substance in an atmosphere in a storage and conveyance environment of the glass plate laminate. .
於本實施形態中,於使用添加有界面活性劑之無機鹼系之清洗劑對玻璃板表面進行清洗之第1清洗步驟之後,進行使用TMAH對玻璃板表面進行清洗之第2清洗步驟,藉此可製造具有極高之清潔度並且黑色矩陣樹脂之密接性不降低之玻璃板。於第2清洗步驟中,藉由使用TMAH對玻璃板表面進行清洗,而去除源自在第1清洗步驟中使用之清洗劑中所包含之界面活性劑的有機物、且因進行第1清洗步驟而導致附著於玻璃板之表面之有機物。該有機物係成為黑色矩陣樹脂對玻璃板表面之密接性降低之原因之有機物。該有機物係GC/MS中之保持時間為18分鐘以上之疏水性有機物,例如為芳香族化合物。即,藉由第2清洗步驟,而自玻璃板之表面有效地去除成為黑色矩陣樹脂對玻璃板表面之密接性降低之原因的疏水性有機物。因此,本實施形態之玻璃板之製造方法能夠提高黑色矩陣樹脂對玻璃板表面之密接性。再者,使用GL Science股份有限公司製造之無極性管柱TC-1作為在GC/MS中使用之毛細管柱。 In the present embodiment, after the first cleaning step of washing the surface of the glass plate with the inorganic base-based cleaning agent to which the surfactant is added, the second cleaning step of cleaning the surface of the glass plate with TMAH is performed. A glass plate having extremely high cleanliness and in which the adhesion of the black matrix resin is not lowered can be produced. In the second cleaning step, the surface of the glass plate is cleaned by using TMAH to remove the organic substance derived from the surfactant contained in the cleaning agent used in the first cleaning step, and the first cleaning step is performed. An organic matter that causes adhesion to the surface of the glass sheet. This organic substance is an organic substance which causes the adhesion of the black matrix resin to the surface of the glass plate to be lowered. The organic substance is a hydrophobic organic substance having a retention time of 18 minutes or longer in GC/MS, and is, for example, an aromatic compound. In other words, in the second cleaning step, the hydrophobic organic substance which causes the adhesion of the black matrix resin to the surface of the glass sheet is effectively removed from the surface of the glass sheet. Therefore, the method for producing a glass sheet of the present embodiment can improve the adhesion of the black matrix resin to the surface of the glass sheet. Further, a nonpolar column TC-1 manufactured by GL Science Co., Ltd. was used as a capillary column used in GC/MS.
於本實施形態中,在玻璃板之清洗步驟後之玻璃板表面上附著之疏水性有機物之質量較佳為在每1cm2玻璃板表面中為0.05ng~0.50ng,更佳為0.05ng~0.25ng。 In the present embodiment, the mass of the hydrophobic organic substance adhering to the surface of the glass plate after the washing step of the glass plate is preferably 0.05 ng to 0.50 ng, more preferably 0.05 ng to 0.25 per 1 cm 2 of the surface of the glass plate. Ng.
又,本實施形態之玻璃板之製造方法對於黑色矩陣之線寬及間距小之彩色濾光片面板之製造特別有效。彩色濾光片面板係於表面配置黑色矩陣及RGB像素而形成彩色濾光片之玻璃板。利用本實施形態 之玻璃板之製造方法而製造之玻璃板係即便在表面配置具有未達10μm之線寬之黑色矩陣亦能夠充分地抑制黑色矩陣之剝離的玻璃板。因此,該玻璃板可於表面配置具有3μm~5μm之線寬之高精細之黑色矩陣。 Further, the method for producing a glass sheet of the present embodiment is particularly effective for the production of a color filter panel having a line width and a small pitch of a black matrix. The color filter panel is a glass plate in which a black matrix and RGB pixels are arranged on the surface to form a color filter. Using this embodiment The glass plate produced by the method for producing a glass plate can sufficiently suppress the peeling of the black matrix even if a black matrix having a line width of less than 10 μm is disposed on the surface. Therefore, the glass plate can be provided with a high-definition black matrix having a line width of 3 μm to 5 μm on the surface.
於本實施形態中,於在第1清洗單元10之刷單元12及海綿單元14中利用無機鹼系之清洗劑對玻璃板G之表面進行清洗之後,在第1清洗單元10之噴淋單元16中,利用純水或超純水洗掉並去除附著於玻璃板G之表面之無機鹼系之清洗劑。藉此,可抑制由在第1清洗步驟中附著於玻璃板G之表面之清洗劑導致接下來之第2清洗步驟中之利用TMAH之玻璃板G之清洗效果降低之情況。 In the present embodiment, after the surface of the glass sheet G is cleaned by the inorganic alkali-based cleaning agent in the brush unit 12 and the sponge unit 14 of the first cleaning unit 10, the shower unit 16 in the first cleaning unit 10 is used. In the middle, the inorganic base-based cleaning agent attached to the surface of the glass sheet G is washed away by pure water or ultrapure water. Thereby, it is possible to suppress the deterioration of the cleaning effect of the glass sheet G using TMAH in the second cleaning step in the next cleaning step by the cleaning agent adhering to the surface of the glass sheet G in the first cleaning step.
第1清洗步驟中所使用之無機鹼系之清洗劑包含界面活性劑。界面活性劑係如上所述般成為黑色矩陣樹脂對玻璃板表面之密接性降低之原因的有機物。因此,在第1清洗步驟之最後,利用純水或超純水洗刷玻璃板G之表面,而洗掉附著於玻璃板G之表面之清洗劑,藉此可提高第2清洗步驟中之去除附著於玻璃板G之表面之有機物之效果。第2清洗步驟具有如下效果:去除附著於玻璃板G之表面之異物、及去除源自因進行第1清洗步驟而導致附著於玻璃板G之表面之清洗劑的有機物。 The inorganic base-based cleaning agent used in the first washing step contains a surfactant. As described above, the surfactant is an organic substance which causes a decrease in the adhesion of the black matrix resin to the surface of the glass plate. Therefore, at the end of the first cleaning step, the surface of the glass plate G is washed with pure water or ultrapure water, and the cleaning agent adhering to the surface of the glass plate G is washed away, whereby the removal and adhesion in the second cleaning step can be improved. The effect of organic matter on the surface of the glass sheet G. The second cleaning step has an effect of removing foreign matter adhering to the surface of the glass sheet G and removing an organic substance derived from a cleaning agent adhering to the surface of the glass sheet G by performing the first cleaning step.
又,於第2清洗步驟之最後,亦藉由第2清洗單元20之噴淋單元16,利用純水或超純水洗掉並去除附著於玻璃板G之表面之TMAH。因此,藉由單片式清洗裝置1或批量清洗裝置101清洗後之玻璃板G具有極高之清潔度。 Further, at the end of the second cleaning step, the shower unit 16 of the second cleaning unit 20 also washes away the TMAH attached to the surface of the glass sheet G by pure water or ultrapure water. Therefore, the glass plate G cleaned by the one-piece cleaning device 1 or the batch cleaning device 101 has extremely high cleanliness.
於本實施形態中,第1清洗步驟中所使用之清洗劑係於以水稀釋市售之玻璃基板用清洗液而獲得之稀釋液中添加KOH等鹼成分而生 成。具體而言,於玻璃基板用清洗液之稀釋液中添加KOH等鹼成分,而生成具有1wt%以上之濃度之清洗劑。藉由添加鹼成分,無需製造及處理鹼成分之濃度非常高之清洗液,即可容易地生成鹼成分之濃度較高之清洗劑。鹼成分之濃度較高之清洗劑可提高玻璃板之蝕刻性,且使玻璃屑或灰塵等異物及在受到負載之狀態下附著於玻璃板表面之黏著性之異物等自玻璃板之表面剝離而有效地去除。 In the present embodiment, the cleaning agent used in the first cleaning step is obtained by adding an alkali component such as KOH to a diluent obtained by diluting a commercially available cleaning liquid for a glass substrate with water. to make. Specifically, an alkali component such as KOH is added to the diluted solution of the cleaning liquid for a glass substrate to produce a cleaning agent having a concentration of 1% by weight or more. By adding an alkali component, it is possible to easily produce a cleaning agent having a high concentration of an alkali component without producing and treating a cleaning liquid having a very high concentration of an alkali component. The cleaning agent having a high concentration of the alkali component can improve the etching property of the glass plate, and can peel off foreign matter such as glass dust or dust and adhesive foreign matter adhering to the surface of the glass plate under load, and the like. Effectively removed.
又,藉由在玻璃基板用清洗液之稀釋液中添加鹼成分而生成之清洗劑之表面張力低於稀釋液。即,藉由在包含界面活性劑之玻璃基板用清洗液之稀釋液中添加KOH等鹼成分,而可獲得於單獨對純水添加鹼成分之情形時幾乎無法獲得之降低清洗劑之表面張力之效果。藉此,清洗劑變得易於滲透至黏著異物與玻璃板之間。進而,藉由與利用清洗劑提高玻璃板之蝕刻性之協同效果,而更有效地去除附著於玻璃板之異物。 Moreover, the surface tension of the cleaning agent produced by adding an alkali component to the dilution liquid of the glass substrate cleaning liquid is lower than the diluent. In other words, by adding an alkali component such as KOH to the diluted solution of the cleaning liquid for a glass substrate containing the surfactant, it is possible to reduce the surface tension of the cleaning agent which is hardly obtained when the alkali component is added to the pure water alone. effect. Thereby, the cleaning agent becomes easy to penetrate between the adhesive foreign matter and the glass plate. Further, by the synergistic effect of improving the etching property of the glass sheet by the cleaning agent, the foreign matter adhering to the glass plate can be removed more effectively.
又,藉由提高添加至玻璃基板用清洗液之稀釋液中之鹼成分之濃度,可提高去除經過數週或數月以上之長期被保管之玻璃板表面上所附著之黏著性異物之效果。 Moreover, by increasing the concentration of the alkali component added to the diluted solution of the cleaning liquid for a glass substrate, the effect of removing the adhesive foreign matter adhering to the surface of the glass plate stored for a long period of several weeks or more can be improved.
對本發明之彩色濾光片用玻璃板之製造方法之實施例進行說明。於本實施例中,在玻璃板之清洗後,對玻璃板表面塗佈黑色矩陣樹脂,並確認黑色矩陣樹脂對玻璃板表面之密接性。以下,說明具體之順序。 An embodiment of a method for producing a glass plate for a color filter of the present invention will be described. In the present embodiment, after the glass plate was cleaned, the surface of the glass plate was coated with a black matrix resin, and the adhesion of the black matrix resin to the surface of the glass plate was confirmed. Hereinafter, the specific order will be described.
首先,根據上述圖1所示之步驟S3,準備在托板上交替地積層毛坯玻璃與間隔紙而成之積層體。其次,根據步驟S4,自毛坯玻璃之積層體中取出毛坯玻璃,並將毛坯玻璃切斷為特定之尺寸,而獲得玻璃板。其次,根據步驟S5進行玻璃板之端面加工。繼而,根據步驟S6,使用本實施形態中所說明之單片式清洗裝置1進行玻璃板之單片式清 洗。於玻璃板之第1清洗步驟中,使用以純水稀釋橫濱油脂工業股份有限公司製造之無機鹼性清洗劑即KG、並添加作為鹼成分之KOH而生成之清洗劑。於玻璃板之第2清洗步驟中,使用具有0.1%~2.38%之濃度之TMAH。 First, according to the step S3 shown in Fig. 1 described above, a laminate in which the blank glass and the spacer paper are alternately laminated on the pallet is prepared. Next, according to the step S4, the blank glass is taken out from the laminated body of the blank glass, and the blank glass is cut into a specific size to obtain a glass plate. Next, the end surface processing of the glass sheet is performed in accordance with step S5. Then, according to step S6, the one-piece cleaning of the glass plate is performed using the one-chip cleaning device 1 described in the embodiment. wash. In the first washing step of the glass plate, a cleaning agent which is obtained by diluting KG which is an inorganic alkaline cleaning agent manufactured by Yokohama Oil & Fats Co., Ltd., and adding KOH as an alkali component is used. In the second cleaning step of the glass plate, TMAH having a concentration of 0.1% to 2.38% is used.
其次,在玻璃板之表面上塗佈黑色矩陣樹脂。具體而言,在玻璃板之表面上,以膜厚成為1μm之方式塗佈黑色矩陣樹脂。其次,使用描繪有1μm、3μm、5μm、10μm、15μm、20μm及30μm之圖案之光罩使塗佈有黑色矩陣樹脂之玻璃板曝光及顯影,並判定黑色矩陣樹脂對玻璃板表面之密接性。具體而言,確認玻璃板表面上之黑色矩陣之剝離及殘渣之有無。 Next, a black matrix resin was coated on the surface of the glass plate. Specifically, a black matrix resin was applied to the surface of the glass plate so that the film thickness became 1 μm. Next, the glass plate coated with the black matrix resin was exposed and developed using a photomask having a pattern of 1 μm, 3 μm, 5 μm, 10 μm, 15 μm, 20 μm, and 30 μm, and the adhesion of the black matrix resin to the surface of the glass plate was determined. Specifically, the presence or absence of peeling of the black matrix on the surface of the glass plate and the residue were confirmed.
於本實施例中,塗佈於玻璃板之表面之黑色矩陣樹脂在5μm~30μm之線寬中未確認到剝離及殘渣。再者,經清洗之玻璃板表面中之TMAH之殘留量係藉由離子層析法之檢測下限為0.01ng/cm2以下。 In the present embodiment, the black matrix resin applied to the surface of the glass plate showed no peeling or residue in the line width of 5 μm to 30 μm. Further, the residual amount of TMAH in the surface of the washed glass plate is limited to 0.01 ng/cm 2 or less by ion chromatography.
又,於玻璃板之第1清洗步驟中,即便使用以純水稀釋橫濱油脂工業股份有限公司製造之無機鹼性清洗劑即L.G.L並添加作為鹼成分之KOH而生成之清洗劑,黑色矩陣樹脂對玻璃板表面之密接性之判定結果亦不變。又,玻璃板之表面粗糙度Ra為0.15nm~0.67nm。 In addition, in the first cleaning step of the glass plate, the black matrix resin pair is used even if the LGL which is an inorganic alkaline cleaning agent manufactured by Yokohama Oil & Fats Co., Ltd., which is an inorganic alkaline cleaning agent, is added with pure water, and the KOH which is an alkali component is added. The judgment result of the adhesion of the surface of the glass plate also does not change. Further, the surface roughness Ra of the glass plate is 0.15 nm to 0.67 nm.
再者,作為比較例,於玻璃板之第1清洗步驟中,代替使用包含界面活性劑之無機鹼系之清洗劑,而使用TMAH進行玻璃板之清洗。即,於第1清洗步驟及第2清洗步驟之兩者中,均進行使用TMAH之玻璃板之清洗。其結果,附著於玻璃板表面之異物之量較上述實施例多。認為其原因在於,TMAH之清洗力較KG等無機鹼系之清洗劑弱,而無法完全去除附著於毛坯玻璃上之污垢。於使用該清洗方法之情形時,關於黑色矩陣樹脂對玻璃板表面之密接性之判定,確認到被認為原因在於異物附著之黑色矩陣之剝離及殘渣。 Further, as a comparative example, in the first washing step of the glass plate, instead of using an inorganic base-based cleaning agent containing a surfactant, the glass plate was washed using TMAH. That is, in the first washing step and the second washing step, the glass plate using TMAH was cleaned. As a result, the amount of foreign matter adhering to the surface of the glass plate was larger than that of the above embodiment. The reason is considered to be that the cleaning power of TMAH is weaker than the inorganic base-based cleaning agent such as KG, and the dirt adhering to the blank glass cannot be completely removed. In the case of using this cleaning method, it was confirmed that the adhesion of the black matrix resin to the surface of the glass plate was considered to be due to peeling and residue of the black matrix to which foreign matter adhered.
又,對在上述圖1之步驟S6中之玻璃板之清洗步驟中,不進行玻 璃板之單片式清洗而進行玻璃板之批量清洗之實施例進行說明。於此情形時,玻璃板之表面上所塗佈之具有3μm~30μm之線寬之黑色矩陣樹脂無論在哪種線寬中均未確認到剝離及殘渣。 Further, in the cleaning step of the glass plate in the above step S6 of Fig. 1, the glass is not subjected to glass An example of performing batch cleaning of a glass plate by single-chip cleaning of a glass plate will be described. In this case, the black matrix resin having a line width of 3 μm to 30 μm applied on the surface of the glass plate did not detect peeling and residue in any of the line widths.
又,對具有窄線寬之黑色矩陣樹脂之圖案進行黑色矩陣之剝離及殘渣之確認。首先,於玻璃板之第2清洗步驟中,使用濃度0.5%之TMAH清洗玻璃板。其次,於經清洗之玻璃板之表面,以膜厚成為1μm且線寬成為1μm~15μm之方式塗佈黑色矩陣樹脂而形成圖案,並判定黑色矩陣樹脂對玻璃板表面之密接性。其結果,於3μm~15μm之線寬中,未確認到玻璃板表面上之黑色矩陣之剝離及殘渣。又,於1μm之線寬中,確認到黑色矩陣之局部剝離。然而,可降低1μm之線寬中之黑色矩陣之剝離或殘渣之產生機率。因此,與未控制特定之表面異物之先前之方法相比,能夠提高具有特別窄之線寬之黑色矩陣樹脂之圖案中之良率。 Further, the pattern of the black matrix resin having a narrow line width was subjected to peeling of the black matrix and confirmation of the residue. First, in the second cleaning step of the glass plate, the glass plate was cleaned using TMAH at a concentration of 0.5%. Next, a black matrix resin was applied to the surface of the cleaned glass plate to have a film thickness of 1 μm and a line width of 1 μm to 15 μm to form a pattern, and the adhesion of the black matrix resin to the surface of the glass plate was determined. As a result, in the line width of 3 μm to 15 μm, peeling and residue of the black matrix on the surface of the glass plate were not confirmed. Further, in the line width of 1 μm, partial peeling of the black matrix was confirmed. However, the probability of occurrence of peeling or residue of the black matrix in the line width of 1 μm can be reduced. Therefore, the yield in the pattern of the black matrix resin having a particularly narrow line width can be improved as compared with the prior method in which the specific surface foreign matter is not controlled.
再者,作為比較例,於玻璃板之第2清洗步驟中,代替將玻璃板浸漬於TMAH中進行清洗,而將玻璃板浸漬於氨水中進行超音波清洗。其結果,關於塗佈於玻璃板之表面之線寬窄於20μm之黑色矩陣樹脂,即便變更黑色矩陣之成膜條件及顯影條件,亦確認到剝離及殘渣之產生。 Further, as a comparative example, in the second cleaning step of the glass plate, instead of immersing the glass plate in TMAH for cleaning, the glass plate was immersed in aqueous ammonia to perform ultrasonic cleaning. As a result, the black matrix resin having a line width narrower than 20 μm applied to the surface of the glass plate confirmed the occurrence of peeling and residue even when the film formation conditions and development conditions of the black matrix were changed.
本實施形態之清洗方法與使玻璃帶單片化所得之玻璃板之清洗步驟相關,但亦可應用於以輥狀保管之玻璃膜之清洗步驟。利用下拉法或再曳引法,介隔間隔紙或樹脂膜捲取使用熔融玻璃或由熔融玻璃形成之預成形玻璃而成形之具有0.1mm以下之厚度之玻璃帶,藉此可獲得輥狀之毛坯玻璃。 The cleaning method of the present embodiment relates to a cleaning step of a glass plate obtained by singulating a glass ribbon, but may be applied to a cleaning step of a glass film stored in a roll shape. By using a down-draw method or a re-drawing method, a glass ribbon having a thickness of 0.1 mm or less formed by using molten glass or a preformed glass formed of molten glass is taken up by spacer film or resin film, whereby a roll-like shape can be obtained. Rough glass.
於本變化例中,一面自該輥狀之毛坯玻璃去除間隔紙或樹脂 膜,一面緩慢地拉出玻璃膜。繼而,於對玻璃膜之端面進行蝕刻處理之後,對玻璃膜之表面進行清洗。於玻璃膜之清洗步驟中,與本實施形態同樣地使用添加有界面活性劑之無機鹼系之清洗劑來清洗表面,並利用純水或超純水洗刷表面,其後使用TMAH清洗表面,並再次利用純水或超純水洗刷表面。繼而,以輥對輥(Roll-to-Roll)之方式將經清洗之玻璃膜搬送至彩色濾光片之製造步驟。或者,介隔製品用之間隔紙或樹脂膜再次捲取經清洗之玻璃膜,而形成作為製品之玻璃膜輥。 In this variation, the spacer paper or resin is removed from the roll-shaped blank glass. The film is slowly pulled out of the glass film. Then, after etching the end surface of the glass film, the surface of the glass film is cleaned. In the washing step of the glass film, the surface is washed with an inorganic base-based cleaning agent to which a surfactant is added, and the surface is washed with pure water or ultrapure water, and then the surface is cleaned with TMAH. Wash the surface again with pure or ultrapure water. Then, the washed glass film is conveyed to the manufacturing process of the color filter in a roll-to-roll manner. Alternatively, the cleaned glass film is again taken up by the spacer paper or the resin film for the article to form a glass film roll as a product.
於本實施形態中,在單片式清洗裝置1中之第2清洗步驟中,使用TMAH對玻璃板G進行刷清洗及海綿清洗,其後,使用純水或超純水對玻璃板G進行噴淋清洗而去除殘留在玻璃板G之表面之有機物。然而,於第2清洗步驟中,亦可不進行海綿清洗。具體而言,只要根據第1清洗步驟中之異物去除能力,適當地在第2清洗步驟中進行刷清洗及海綿清洗中之至少一者即可。 In the second embodiment, in the second cleaning step of the one-chip cleaning apparatus 1, the glass plate G is brush-cleaned and sponge-washed using TMAH, and then the glass plate G is sprayed with pure water or ultrapure water. The organic matter remaining on the surface of the glass plate G is removed by washing. However, in the second washing step, the sponge washing may not be performed. Specifically, at least one of brush cleaning and sponge cleaning may be appropriately performed in the second cleaning step in accordance with the foreign matter removing ability in the first washing step.
於本實施形態中,在單片式清洗裝置1中之第2清洗步驟中,將進行過單片式清洗之玻璃板G送至圖1所示之步驟S7之檢查步驟。然而,進行過單片式清洗之玻璃板G亦可進而進行批量清洗。於批量清洗中,如圖5所示,將複數片玻璃板G收容於盒120內,並將玻璃板G依序浸漬於複數個液槽130內而進行清洗。 In the present embodiment, in the second cleaning step in the one-chip cleaning apparatus 1, the glass sheet G subjected to the one-piece cleaning is sent to the inspection step of step S7 shown in FIG. However, the glass sheet G subjected to the one-piece cleaning can be further subjected to batch cleaning. In the batch cleaning, as shown in FIG. 5, a plurality of glass sheets G are housed in the case 120, and the glass sheets G are sequentially immersed in a plurality of liquid tanks 130 to be cleaned.
於本實施形態中,玻璃板之表面較佳為具有未達0.7nm之表面粗糙度Ra。表面粗糙度Ra係作為表示玻璃板表面之粗糙度之參數之一種之「中心線平均粗糙度」。於玻璃板之表面粗糙度Ra未達0.7nm之情形時,不會對黑色矩陣樹脂對玻璃板表面之密接性造成影響,故而 能夠更容易地控制玻璃板表面上之黑色矩陣樹脂之密接性。 In the present embodiment, the surface of the glass plate preferably has a surface roughness Ra of less than 0.7 nm. The surface roughness Ra is a "center line average roughness" which is one of the parameters indicating the roughness of the surface of the glass plate. When the surface roughness Ra of the glass plate is less than 0.7 nm, the adhesion of the black matrix resin to the surface of the glass plate is not affected, and thus The adhesion of the black matrix resin on the surface of the glass plate can be more easily controlled.
10‧‧‧第1清洗單元 10‧‧‧1st cleaning unit
12‧‧‧刷單元 12‧‧‧ brush unit
12a‧‧‧清洗刷輥 12a‧‧‧Washing brush roller
12b‧‧‧清洗刷輥 12b‧‧‧Washing brush roller
14‧‧‧海綿單元 14‧‧‧Sponge unit
14a‧‧‧清洗海綿輥 14a‧‧‧Clean sponge roller
14b‧‧‧清洗海綿輥 14b‧‧‧Clean sponge roller
16‧‧‧噴淋單元 16‧‧‧Spray unit
18‧‧‧清洗劑箱 18‧‧‧cleaning agent box
18a‧‧‧噴嘴 18a‧‧‧Nozzles
18b‧‧‧噴嘴 18b‧‧‧Nozzles
18c‧‧‧噴嘴 18c‧‧‧ nozzle
18d‧‧‧噴嘴 18d‧‧‧ nozzle
19‧‧‧純水箱 19‧‧‧ pure water tank
19a‧‧‧噴嘴 19a‧‧‧Nozzles
19b‧‧‧噴嘴 19b‧‧‧Nozzles
G‧‧‧玻璃板 G‧‧‧glass plate
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- 2013-08-01 CN CN201510817989.XA patent/CN105481265A/en active Pending
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Also Published As
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KR101582004B1 (en) | 2015-12-31 |
TWI525058B (en) | 2016-03-11 |
JP2014052622A (en) | 2014-03-20 |
TW201522263A (en) | 2015-06-16 |
CN105481265A (en) | 2016-04-13 |
CN103567202B (en) | 2016-08-10 |
CN103567202A (en) | 2014-02-12 |
KR101831024B1 (en) | 2018-02-21 |
KR20140019226A (en) | 2014-02-14 |
KR20150060656A (en) | 2015-06-03 |
JP5728538B2 (en) | 2015-06-03 |
TW201406694A (en) | 2014-02-16 |
JP2015146019A (en) | 2015-08-13 |
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