TWI444220B - A method for regenerating removal liquid from removal liquid waste liquid, and a regenerating apparatus - Google Patents
A method for regenerating removal liquid from removal liquid waste liquid, and a regenerating apparatus Download PDFInfo
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- TWI444220B TWI444220B TW097140301A TW97140301A TWI444220B TW I444220 B TWI444220 B TW I444220B TW 097140301 A TW097140301 A TW 097140301A TW 97140301 A TW97140301 A TW 97140301A TW I444220 B TWI444220 B TW I444220B
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- liquid
- photoresist
- stripping liquid
- stripping
- waste liquid
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- 239000007788 liquid Substances 0.000 title claims description 267
- 239000010808 liquid waste Substances 0.000 title claims description 79
- 230000001172 regenerating effect Effects 0.000 title claims description 34
- 238000000034 method Methods 0.000 title claims description 23
- 229920002120 photoresistant polymer Polymers 0.000 claims description 112
- 238000009835 boiling Methods 0.000 claims description 59
- 238000007670 refining Methods 0.000 claims description 33
- 239000010409 thin film Substances 0.000 claims description 29
- 239000002699 waste material Substances 0.000 claims description 28
- 239000003513 alkali Substances 0.000 claims description 26
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims description 22
- 239000010408 film Substances 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- 239000007864 aqueous solution Substances 0.000 claims description 15
- 239000012528 membrane Substances 0.000 claims description 15
- 239000000126 substance Substances 0.000 claims description 15
- 239000004973 liquid crystal related substance Substances 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 13
- 239000002585 base Substances 0.000 claims description 11
- 239000001569 carbon dioxide Substances 0.000 claims description 11
- 229910002092 carbon dioxide Inorganic materials 0.000 claims description 11
- 239000011552 falling film Substances 0.000 claims description 9
- 238000007790 scraping Methods 0.000 claims description 6
- 238000007599 discharging Methods 0.000 claims description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 229910052799 carbon Inorganic materials 0.000 claims 1
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 63
- 150000007514 bases Chemical class 0.000 description 28
- 238000011084 recovery Methods 0.000 description 19
- 238000005406 washing Methods 0.000 description 15
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 15
- 238000012360 testing method Methods 0.000 description 11
- 230000000052 comparative effect Effects 0.000 description 9
- 150000001875 compounds Chemical class 0.000 description 9
- 230000008929 regeneration Effects 0.000 description 9
- 238000011069 regeneration method Methods 0.000 description 9
- 239000002904 solvent Substances 0.000 description 9
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 8
- 238000004140 cleaning Methods 0.000 description 7
- 238000001704 evaporation Methods 0.000 description 7
- 238000001556 precipitation Methods 0.000 description 7
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 6
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 6
- 230000008020 evaporation Effects 0.000 description 6
- 239000000758 substrate Substances 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 5
- 238000012423 maintenance Methods 0.000 description 5
- 238000004064 recycling Methods 0.000 description 5
- 238000000926 separation method Methods 0.000 description 5
- 238000011144 upstream manufacturing Methods 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 230000008021 deposition Effects 0.000 description 4
- 238000004821 distillation Methods 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 230000001976 improved effect Effects 0.000 description 4
- 230000007246 mechanism Effects 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- YLZOPXRUQYQQID-UHFFFAOYSA-N 3-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]propan-1-one Chemical compound N1N=NC=2CN(CCC=21)CCC(=O)N1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F YLZOPXRUQYQQID-UHFFFAOYSA-N 0.000 description 3
- 239000011248 coating agent Substances 0.000 description 3
- 238000000576 coating method Methods 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 238000010438 heat treatment Methods 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- LLHKCFNBLRBOGN-UHFFFAOYSA-N propylene glycol methyl ether acetate Chemical compound COCC(C)OC(C)=O LLHKCFNBLRBOGN-UHFFFAOYSA-N 0.000 description 3
- 238000003860 storage Methods 0.000 description 3
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 2
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 230000000007 visual effect Effects 0.000 description 2
- DIIIISSCIXVANO-UHFFFAOYSA-N 1,2-Dimethylhydrazine Chemical compound CNNC DIIIISSCIXVANO-UHFFFAOYSA-N 0.000 description 1
- SQTHUUHOUPJYLK-UKFBFLRUSA-N 2,6-diamino-2,6-dideoxy-alpha-D-glucose Chemical compound NC[C@H]1O[C@H](O)[C@H](N)[C@@H](O)[C@@H]1O SQTHUUHOUPJYLK-UKFBFLRUSA-N 0.000 description 1
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 1
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 1
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- 239000003085 diluting agent Substances 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000011835 investigation Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000003595 mist Substances 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 230000002265 prevention Effects 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- 230000000717 retained effect Effects 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- -1 sodium hydroxide Chemical class 0.000 description 1
- 229910001220 stainless steel Inorganic materials 0.000 description 1
- 239000010935 stainless steel Substances 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000011550 stock solution Substances 0.000 description 1
- 230000008016 vaporization Effects 0.000 description 1
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/34—Imagewise removal by selective transfer, e.g. peeling away
- G03F7/343—Lamination or delamination methods or apparatus for photolitographic photosensitive material
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/423—Stripping or agents therefor using liquids only containing mineral acids or salts thereof, containing mineral oxidizing substances, e.g. peroxy compounds
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/02041—Cleaning
- H01L21/02057—Cleaning during device manufacture
- H01L21/02068—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers
- H01L21/02071—Cleaning during device manufacture during, before or after processing of conductive layers, e.g. polysilicon or amorphous silicon layers the processing being a delineation, e.g. RIE, of conductive layers
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
- H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
- H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer
- H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having at least one potential-jump barrier or surface barrier, e.g. PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic System or AIIIBV compounds with or without impurities, e.g. doping materials
- H01L21/30—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26
- H01L21/31—Treatment of semiconductor bodies using processes or apparatus not provided for in groups H01L21/20 - H01L21/26 to form insulating layers thereon, e.g. for masking or by using photolithographic techniques; After treatment of these layers; Selection of materials for these layers
- H01L21/3105—After-treatment
- H01L21/311—Etching the insulating layers by chemical or physical means
- H01L21/31127—Etching organic layers
- H01L21/31133—Etching organic layers by chemical means
-
- C11D2111/22—
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- Manufacturing & Machinery (AREA)
- Computer Hardware Design (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Power Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- General Chemical & Material Sciences (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Liquid Crystal (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Description
本發明係關於剝離液廢液之剝離液之再生方法和再生裝置。The present invention relates to a method and a regeneration apparatus for a stripping liquid of a stripping liquid waste liquid.
從液晶的製造過程(液晶顯示器的陣列基板單元製造過程)排出之含有光阻的剝離液廢液中，除了光阻以外，還含有：水、重金屬類和各種微粒子等的非揮發性成分、低沸點成分、高沸點成分。習知之專利文獻1至3揭示出，用來回收從光阻剝離液廢液精製出的溶劑(精製剝離液)的方法和裝置。依據專利文獻1所記載之溶劑再生回收裝置，是使用降膜式蒸發器作為前述高沸點成分的除去手段，將前述蒸發器所產生的包含溶劑及低沸點污染成分的蒸氣經由油霧分離機供應至精餾塔，將精餾塔的餾分之低沸點成分予以分離，並將精餾塔的餾出液中的高沸點成分作為側流成分，藉此獲得精製剝離液。In addition to photoresist, non-volatile components such as water, heavy metals, and various fine particles are included in the waste liquid containing the photoresist from the liquid crystal manufacturing process (the manufacturing process of the array substrate unit of the liquid crystal display). Boiling point component, high boiling point component. Patent Documents 1 to 3 disclose a method and apparatus for recovering a solvent (purified stripping liquid) purified from a photoresist stripping liquid. According to the solvent recovery and recovery apparatus described in Patent Document 1, a falling film evaporator is used as a means for removing the high boiling point component, and a vapor containing a solvent and a low boiling point pollutant component generated by the evaporator is supplied via an oil mist separator. In the fractionator, the low-boiling component of the fraction of the rectification column is separated, and the high-boiling component in the distillate of the rectification column is used as a side stream component, thereby obtaining a purified stripping liquid.
此外，依據專利文獻2的溶劑回收裝置，作為從剝離液廢液中除去光阻成分並將溶劑予以再生回收之手段是使用：旋轉體內面刮取式的降膜機構所構成之蒸發濃縮手段、用來除去剝離液廢液中所含的低沸點雜質之第1蒸餾塔、用來高精度地分離精製出高沸點物質之第2蒸餾塔，藉此精製出剝離液廢液而進行再生回收。Further, according to the solvent recovery device of Patent Document 2, as a means for removing the photoresist component from the waste liquid waste liquid and recovering and recovering the solvent, a means for evaporating and concentrating the rotating body surface scraping type falling film mechanism is used. The first distillation column for removing low-boiling impurities contained in the waste liquid waste liquid and the second distillation column for separating and purifying the high-boiling substance with high precision are used to purify the waste liquid waste liquid for regeneration.
另一方面，在專利文獻3提出的技術，是使用主成分包含單乙醇胺之光阻剝離液來進行光阻的剝離除去後的剝離液廢液之再生回收用的方法及裝置，其具備：在剝離液廢液中添加氫氧化鹼，將剝離液廢液中的碳酸成分以碳酸鹼的狀態予以固定之鹼添加步驟；以及，將碳酸成分以碳酸鹼的狀態予以固定後的剝離液廢液藉由蒸餾來回收剝離液之蒸餾回收步驟。前述氫氧化鹼的添加量設定為，為了將前述碳酸成分以碳酸鹼的狀態予以固定所必須的理論量的1~1.5倍的範圍。在專利文獻3，是基於除去光阻剝離液中的碳酸成分的目的來添加鹼成分，其添加量比本發明的鹼添加量多1位數。因此，由於剝離液廢液中通常碳酸成分的含量為0.5~2質量%，若剝離液廢液中所含的碳酸成分為0.5質量%，則使用氫氧化鈉作為鹼來使用時之氫氧化鈉的添加量為On the other hand, the technique proposed in Patent Document 3 is a method and an apparatus for recycling and recovering a waste liquid waste liquid after peeling off the photoresist by using a photoresist stripping liquid containing a monoethanolamine as a main component, and comprising: a base addition step of adding a hydroxide alkali to the waste liquid waste liquid, fixing the carbonic acid component in the waste liquid waste liquid in the form of a carbonate base, and a stripping liquid waste liquid obtained by fixing the carbonic acid component in a state of carbonate alkali A distillation recovery step of recovering the stripping liquid by distillation. The amount of the alkali hydroxide added is set to be in the range of 1 to 1.5 times the theoretical amount necessary for fixing the carbonic acid component in the state of carbonate. In Patent Document 3, an alkali component is added for the purpose of removing a carbonic acid component in the resist stripping liquid, and the amount thereof is added by one digit more than the amount of alkali added in the present invention. Therefore, the content of the carbonic acid component in the waste liquid waste liquid is usually 0.5 to 2% by mass, and if the carbonic acid component contained in the waste liquid of the peeling liquid is 0.5% by mass, sodium hydroxide is used when sodium hydroxide is used as the alkali. The amount added is
0.5(碳酸濃度)÷44(二氧化碳分子量)×40(氫氧化鈉分子量)=0.45質量%0.5 (carbonic acid concentration) ÷ 44 (carbon dioxide molecular weight) × 40 (sodium hydroxide molecular weight) = 0.45 mass%
而必須使用大量的鹼。如此般專利文獻3的技術，純粹是用來固定剝離液廢液中的碳酸，並不是用來處理剝離液廢液的光阻，又關於對光阻實施鹼處理之技術思想，在專利文獻3中完全沒有記載，且連暗示也沒有。A large amount of alkali must be used. The technique of Patent Document 3 is purely for fixing the carbonic acid in the waste liquid of the stripping liquid, not the photoresist for treating the waste liquid of the stripping liquid, and the technical idea of performing alkali treatment on the photoresist, in Patent Document 3 There is no record at all, and there is no hint.
然而，在剝離液廢液中，除了光阻以外，還混入水、重金屬類和微粒子等的非揮發性成分、高沸點成分，在上述習知的剝離液廢液再生裝置之實際運轉狀況，隨著剝離液廢液之濃縮，剝離液中光阻的溶解度降低(到達剝離液可溶解光阻的限度以上)，因此若光阻濃縮至一定限度以上，光阻會析出而附著、固著於裝置內面。特別是在光阻濃度變濃之高沸點成分、非揮發性成分之除去步驟，光阻成分的附著、固著變多，在專利文獻2，在旋轉體內面刮取式的降膜機構所構成之蒸發濃縮手段的旋轉體部、刮取面上會附著、固著光阻成分，而使裝置之正常運轉變困難。同樣的，在專利文獻1、3也是，在降膜式的蒸發器，光阻成分會附著、固著於用來賦予蒸發所必須的熱的面上，而使蒸發器本身的功能變差。總之，由於光阻會附著、固著於裝置，因此必須定期實施裝置的洗淨。此外，光阻之附著、固著於裝置上，不僅會使裝置的運轉率降低，且暗示精製剝離液的回收率的界限。和濃縮後的光阻在一起的剝離液，會成為損失，而必須購買新的剝離液來進行補充，為了取得高價的剝離液會造成成本上昇。However, in the stripping liquid waste liquid, in addition to the photoresist, non-volatile components such as water, heavy metals, and fine particles, and high-boiling components are mixed, and the actual operation state of the above-described conventional stripping liquid waste regeneration device is Concentration of the stripping liquid waste liquid, the solubility of the photoresist in the stripping liquid is lowered (above the limit of the photoresist which can dissolve the stripping liquid), so if the photoresist is concentrated to a certain limit or more, the photoresist will precipitate and adhere to and adhere to the device. inside. In particular, in the step of removing the high-boiling component and the non-volatile component in which the resistive concentration is increased, the adhesion and fixation of the photoresist component are increased, and in Patent Document 2, the falling body of the rotating body surface is formed by a falling film falling mechanism. The photoresist unit and the scraping surface of the evaporation and concentration means adhere to and fix the photoresist component, which makes it difficult to operate the device normally. Similarly, in Patent Documents 1 and 3, in the falling film type evaporator, the photoresist component adheres to and adheres to the surface for imparting heat necessary for evaporation, and the function of the evaporator itself is deteriorated. In short, since the photoresist adheres and is fixed to the device, it is necessary to periodically perform cleaning of the device. In addition, adhesion of the photoresist to the device not only lowers the operating rate of the device, but also implies a limit on the recovery rate of the purified stripping solution. The stripping solution together with the concentrated photoresist will be a loss, and a new stripping solution must be purchased for replenishment, which will increase the cost in order to obtain a high-priced stripping solution.
另外，在固接後的光阻中，洗淨性差的非揮發性成分完全不會剝落，因此就算實施洗淨步驟，其裝置的功能仍會隨著時間經過而變差。Further, in the photoresist after the fixation, the non-volatile components having poor detergency are not peeled off at all, and therefore, even if the washing step is carried out, the function of the apparatus deteriorates with the passage of time.
[專利文獻1]日本特開2003-144801號公報[Patent Document 1] Japanese Patent Laid-Open Publication No. 2003-144801
[專利文獻2]日本特開2005-288329號公報[Patent Document 2] Japanese Patent Laid-Open Publication No. 2005-288329
[專利文獻3]日本特開2002-131923號公報[Patent Document 3] Japanese Laid-Open Patent Publication No. 2002-131923
本發明是有鑑於上述問題而開發完成者，其課題是為了減少液晶和半導體製造的光阻剝離步驟所使用的全新的剝離液的補充而提供出，能從前述光阻剝離步驟所排出的剝離液廢液以比以往更高的回收率來進行精製剝離液的再生之新穎的剝離液之再生方法以及再生裝置。The present invention has been developed in view of the above problems, and an object thereof is to provide a peeling off from the photoresist peeling step in order to reduce the replenishment of a completely new peeling liquid used in a resist stripping step of liquid crystal and semiconductor manufacturing. A method and a regeneration apparatus for regenerating a novel stripping liquid in which a liquid waste liquid is recovered at a higher recovery rate than in the prior art.
例如，在半導體製造工廠和液晶顯示面板的製程之陣列基板製造過程，是在母玻璃基板上形成金屬膜並實施洗淨，在其上方塗布可用紫外線感光之光阻原料(光阻塗布步驟)，為了讓該光阻原料中的溶劑蒸發而進行高溫處理(預烘烤步驟)，接著在其上方放置光罩並照射紫外線(露光步驟)，再用顯影液進行顯影(顯影步驟)。結果，由於光罩上有圖案的部分未受紫外線的照射，光阻不會產生變化而無法溶解於顯影液中，但在沒有圖案的部分，受紫外線照射而進行感光之光阻，會溶解於顯影液中而被除去。然後，再度進行高溫處理(後烘烤)，接著為了除去不需要的金屬膜而進行蝕刻，最後將形成圖案用的光阻利用剝離液來除去。For example, in the manufacturing process of an array substrate of a semiconductor manufacturing factory and a liquid crystal display panel, a metal film is formed on a mother glass substrate and washed, and a photoresist material (photoresist coating step) which can be coated with ultraviolet light is applied thereon. In order to evaporate the solvent in the photoresist raw material, high temperature treatment (prebaking step) is performed, and then a photomask is placed thereon and irradiated with ultraviolet rays (exposure step), and development is carried out with a developing solution (developing step). As a result, since the patterned portion of the photomask is not irradiated with ultraviolet rays, the photoresist does not change and cannot be dissolved in the developer, but in the portion where there is no pattern, the photoresist which is exposed to ultraviolet light and is photosensitive is dissolved. It is removed in the developer. Then, the high temperature treatment (post-baking) is performed again, and then etching is performed to remove the unnecessary metal film, and finally the photoresist for pattern formation is removed by the stripping liquid.
本發明的目的，是為了提供從如此般產生的剝離液廢液(該剝離液廢液含有0.1~3質量%的光阻)進行剝離液的再生之方法及裝置。An object of the present invention is to provide a method and an apparatus for regenerating a peeling liquid from a peeling liquid waste liquid (the peeling liquid waste liquid contains 0.1 to 3% by mass of a photoresist).
本發明人等，為了達成上述目的而進行深入探討的結果發現，在從液晶顯示面板的製造過程排出之光阻剝離液廢液將其中所含的正型光阻予以分離除去而再生剝離液之方法中，相對於前述剝離液廢液中的光阻質量添加0.01~0.2倍質量的鹼性化合物，藉此能從前述剝離液廢液以高回收率再生出精製剝離液，如是到達本發明的完成。As a result of intensive investigation to achieve the above object, the present inventors have found that the photoresist of the photoresist stripping liquid discharged from the manufacturing process of the liquid crystal display panel separates and removes the positive photoresist contained therein to regenerate the stripping liquid. In the method, 0.01 to 0.2 times the mass of the basic compound is added to the photoresist in the stripping liquid waste liquid, whereby the stripping liquid waste liquid can be regenerated from the stripping liquid waste liquid at a high recovery rate, as at the time of reaching the present invention. carry out.
亦即，本發明的第1觀點，是在從液晶顯示面板的製造過程排出之光阻剝離液廢液將其中所含的正型光阻予以分離除去而再生剝離液之方法，其特徵在於：將相對於前述剝離液廢液所含的光阻質量為0.01~0.2倍質量的鹼性化合物，添加於該剝離液廢液中。In other words, the first aspect of the present invention is a method for separating and removing a positive-type photoresist contained in a photoresist release liquid discharged from a liquid crystal display panel in a process of manufacturing a liquid crystal display panel, and is characterized in that: An alkaline compound having a mass of 0.01 to 0.2 times the mass of the photoresist contained in the waste liquid of the peeling liquid is added to the waste liquid of the peeling liquid.
作為第2觀點，在是第1觀點所記載之剝離液之再生方法中，前述鹼性化合物是以水溶液的形態來添加。According to a second aspect of the invention, in the method for regenerating a peeling liquid according to the first aspect, the basic compound is added in the form of an aqueous solution.
作為第3觀點，在是第1觀點所記載之剝離液之再生方法中，在添加前述鹼性化合物之同時或其添加前，將前述剝離液廢液以光阻曝光用的波長範圍的光線進行曝光處理。According to a third aspect of the invention, in the method for regenerating a peeling liquid according to the first aspect, the stripping liquid waste liquid is subjected to light of a wavelength range for resist exposure while the basic compound is added or before the addition thereof. Exposure processing.
作為第4觀點，在第1觀點所記載之剝離液之再生方法，係具有從前述剝離液廢液分離其中的高沸點成分的步驟，藉由該分離來除去光阻的方法，而前述鹼性化合物是在該分離步驟之前添加。According to a fourth aspect, the method for regenerating a stripping liquid according to the first aspect is a step of separating a high-boiling component from the stripping liquid waste liquid, and removing the photoresist by the separating, and the alkaline layer The compound is added prior to this separation step.
作為第5觀點，在是第1觀點所記載之剝離液之再生方法中，係具有：從前述剝離液廢液分離除去其中的低沸點成分的步驟、分離除去其中的高沸點成分的步驟、接著從剩餘的液體中將精製剝離液予以分離回收的步驟。According to a fifth aspect of the invention, in the method for regenerating a stripping liquid according to the first aspect, the method includes the steps of: separating and removing a low-boiling component from the stripping liquid waste liquid, and separating and removing the high-boiling component therein, and then The step of separating and recovering the purified stripping liquid from the remaining liquid.
作為第6觀點，是在從液晶顯示面板的製造過程排出之光阻剝離液廢液將其中所含的正型光阻予以分離除去而再生剝離液之裝置，其特徵在於：係具備：從前述剝離液廢液分離除去其中的低沸點成分之低沸點物除去塔、從該剝離液廢液分離除去其中的高沸點成分之薄膜式蒸發器、以及從剩餘的液體中分離回收精製剝離液之剝離液精製塔；而且具備：讓前述剝離液廢液流過該低沸點物除去塔、該薄膜式蒸發器以及該剝離液精製塔之間，而以精製剝離液的狀態進行回收的配管系統；在前述薄膜式蒸發器及/或比其更上游側的配管系統，係具備用來將鹼性化合物添加於該剝離液廢液之鹼添加手段。According to a sixth aspect of the invention, there is provided an apparatus for removing a positive resist contained in a photoresist release liquid discharged from a manufacturing process of a liquid crystal display panel to remove a positive resist, wherein the apparatus comprises: a low-boiling substance removal tower in which a low-boiling point component is separated and removed from the stripping liquid waste liquid, a thin film evaporator in which a high-boiling point component is separated and removed from the stripping liquid waste liquid, and a separation and separation of the purified stripping liquid from the remaining liquid a liquid refining tower; further comprising: a piping system for allowing the stripping liquid waste liquid to flow between the low-boiling point removal tower, the thin film evaporator, and the stripping liquid refining tower, and recovering the stripping liquid; The thin film evaporator and/or the piping system on the upstream side thereof are provided with a base addition means for adding a basic compound to the waste liquid waste liquid.
作為第7觀點，在是第6觀點所記載之剝離液之再生裝置中，係具備：讓前述剝離液廢液依前述低沸點物除去塔、前述薄膜式蒸發器、前述剝離液精製塔的順序流過其等之間，而以精製剝離液的狀態進行回收的配管系統；在前述薄膜式蒸發器及/或比其更上游側的配管系統，具備前述鹼添加手段。According to a seventh aspect of the invention, in the apparatus for regenerating a stripping liquid according to the sixth aspect, the apparatus for allowing the stripping liquid waste liquid to pass through the low-boiling point removal tower, the thin film evaporator, and the stripping liquid refining tower A piping system that recovers in a state in which the stripping liquid is purified, and a piping system in which the thin film evaporator and/or the upstream side thereof are provided with the alkali addition means.
作為第8觀點，在是第6觀點所記載之剝離液之再生裝置中，係具備：讓前述剝離液廢液依前述薄膜式蒸發器、前述低沸點物除去塔、前述剝離液精製塔的順序流過其等之間，而以精製剝離液的狀態進行回收的配管系統；在前述薄膜式蒸發器及/或比其更上游側的配管系統，具備前述鹼添加手段。According to a sixth aspect of the invention, in the apparatus for regenerating a stripping liquid according to the sixth aspect, the stripping liquid waste liquid is provided in the order of the thin film evaporator, the low boiler removal tower, and the stripping liquid refining tower. A piping system that recovers in a state in which the stripping liquid is purified, and a piping system in which the thin film evaporator and/or the upstream side thereof are provided with the alkali addition means.
作為第9觀點，在是第6觀點至第8觀點中任一者所記載之剝離液之再生裝置中，係在前述鹼添加手段之配置部位，或是比該配置部位更上游側的部位，具備用來將前述剝離液廢液以光阻曝光用的波長範圍的光線進行曝光處理之曝光手段。According to a ninth aspect of the present invention, in the apparatus for regenerating the peeling liquid according to any one of the sixth aspect to the eighth aspect, the portion to be placed in the alkali addition means or the portion on the upstream side of the arrangement portion is An exposure means for exposing the light of the stripping liquid waste liquid in a wavelength range for resist exposure is provided.
作為第10觀點，在是第6觀點至第8觀點中任一者所記載之剝離液之再生裝置中，前述鹼添加手段，是能將相對於前述剝離液廢液所含的光阻質量為0.01~0.2倍質量的鹼性化合物添加於該剝離液廢液中的手段。According to a tenth aspect of the present invention, in the apparatus for regenerating a peeling liquid according to any one of the sixth aspect to the eighth aspect, the alkali addition means is capable of providing a photoresist mass contained in the waste liquid of the peeling liquid A means for adding 0.01 to 0.2 times by mass of a basic compound to the stripping liquid waste liquid.
作為第11觀點，在是第6觀點至第8觀點中任一者所記載之剝離液之再生裝置中，進一步在前述低沸點物除去塔及/或前述薄膜式蒸發器連接：使從其內部排出的氣體液化後送回該內部之冷凝器。In a regenerating apparatus for a peeling liquid according to any one of the sixth aspect to the eighth aspect, the low-boiling substance removal tower and/or the thin film evaporator are further connected from the inside The discharged gas is liquefied and sent back to the internal condenser.
作為第12觀點，在是第6觀點至第8觀點中任一者所記載之剝離液之再生裝置中，進一步在前述低沸點物除去塔及/或前述剝離液精製塔連接：使來自其內部的液體加熱沸騰後送回該內部之再沸器。According to a second aspect of the present invention, in the apparatus for regenerating a stripping liquid according to any one of the sixth aspect to the eighth aspect, the low-boiling point removal column and/or the stripping liquid refining tower are further connected from the inside The liquid is heated to boil and returned to the internal reboiler.
第13觀點是關於一種剝離液之再生裝置，是在從液晶顯示面板的製造過程排出之光阻剝離液廢液將其中所含的正型光阻予以分離除去而再生剝離液之裝置，其特徵在於：係具備：低沸點物除去塔、連接於低沸點物除去塔的底部且用來使塔內的液體氣化後送回之第1再沸器、連接於低沸點物除去塔且用來使從塔上部排出的氣體液化而讓除去低沸點成分後的液體送回塔內部之第1冷凝器、剝離液精製塔、連接於剝離液精製塔的底部且用來使塔內的液體氣化後送回之第2再沸器、用來將除去低沸點成分後的剝離液廢液從低沸點物除去塔供應至第2再沸器之配管、薄膜式蒸發器、用來將從剝離液精製塔的下部排出之除去低沸點成分後的液體供應至薄膜式蒸發器的上部之配管、用來將從薄膜式蒸發器的下部排出之處理液以含有光阻的高沸點成分的狀態回收並送回薄膜式蒸發器的上部之配管、用來將分離光阻後的剝離液從薄膜式蒸發器的上部供應至剝離液精製塔之配管、連接於剝離液精製塔且用來使從塔上部排出的氣體液化而將產生的精製剝離液予以回收之第2冷凝器；在前述薄膜式蒸發器或比其更上游的配管或是裝置上設置：相對於剝離液廢液中的光阻質量添加0.01~0.2倍質量的鹼性化合物之鹼添加手段。The thirteenth aspect is a device for regenerating a stripping liquid, which is a device for separating and removing a positive-type photoresist contained in a photoresist stripping liquid discharged from a manufacturing process of a liquid crystal display panel, and regenerating the stripping liquid. It is characterized in that it comprises a low boiler removal column, a first reboiler connected to the bottom of the low boiler removal column for vaporizing the liquid in the column, and connected to the low boiler removal column and used for The gas discharged from the upper portion of the column is liquefied, and the liquid from which the low-boiling point component is removed is returned to the first condenser inside the column, the stripper refining tower, and the bottom of the stripping liquid refining tower, and is used to vaporize the liquid in the column. The second reboiler that is sent back, the waste liquid for removing the low-boiling component, and the waste liquid from the low-boiling substance removal tower to the second reboiler, the thin film evaporator, and the stripping liquid The liquid discharged from the lower portion of the refining column and supplied with the low-boiling component is supplied to the upper portion of the thin film evaporator, and the treatment liquid for discharging the lower portion of the thin film evaporator is recovered in a state of high-boiling component containing a photoresist. Send back thin a pipe for the upper portion of the evaporator, a stripper for separating the photoresist from the upper portion of the thin film evaporator, a pipe for the stripping liquid refining tower, and a gas for connecting to the stripping liquid refining tower for discharging the gas from the upper portion of the column a second condenser that liquefies and recovers the produced purified stripping liquid; and is provided on the thin film evaporator or a pipe or device further upstream thereof: 0.01 to 0.2 is added with respect to the mass of the photoresist in the stripping liquid A method of adding a base of a basic mass of a basic compound.
依據本發明，在剝離液廢液的管線之最佳部位，相對於剝離液廢液的非揮發性成分(光阻)添加0.01~0.2倍的水溶性鹼，以及按照需要來對剝離液廢液全體利用螢光燈等的光線來進行曝光，藉此可防止光阻析出，而提昇精製剝離液的回收率，進一步可防止裝置壁面之光阻附著，結果可減輕裝置之定期洗淨及保養的負擔。According to the present invention, 0.01 to 0.2 times of the water-soluble alkali is added to the non-volatile component (photoresist) of the stripping liquid waste liquid at the optimum portion of the stripping liquid waste liquid, and the stripping liquid waste liquid is required as needed. All of the light is exposed by a fluorescent lamp or the like, thereby preventing the photoresist from being precipitated, thereby improving the recovery rate of the purified peeling liquid, and further preventing the photoresist from adhering to the wall surface of the device, thereby reducing the periodic cleaning and maintenance of the device. burden.
又依據本發明，能以精製剝離液的回收率比使用習知再生裝置的情況下之精製剝離液的回收率(≒90%)提昇5%的狀態進行再生。結果，可減少光阻剝離步驟中之高價剝離液的補充量，除具有經濟價值外，藉由減輕洗淨及保養的負擔可進行更穩定的裝置運轉而發揮極大的效果。Further, according to the present invention, the recovery rate of the purified stripping liquid can be regenerated in a state in which the recovery rate (≒90%) of the purified stripping liquid in the case of using a conventional regenerating apparatus is increased by 5%. As a result, it is possible to reduce the amount of replenishment of the high-priced peeling liquid in the resist stripping step, and in addition to having economical value, it is possible to perform a more stable operation of the apparatus by reducing the burden of washing and maintenance, thereby exerting a great effect.
依據本發明，藉由在剝離液廢液中添加鹼性化合物，可增加剝離液中光阻的溶解度，而減少光阻析出以及裝置上光阻的附著，藉此可提昇剝離液的回收率。According to the present invention, by adding a basic compound to the waste liquid of the stripping liquid, the solubility of the photoresist in the stripping liquid can be increased, and the precipitation of the photoresist and the adhesion of the photoresist on the apparatus can be reduced, whereby the recovery rate of the stripping liquid can be improved.
又較佳為，除了添加前述鹼性化合物以外，對剝離液廢液全體用螢光燈等具有紫外線(波長10-9 m)-可見光-紅外線(波長10-4 m)的波長的光進行曝光。藉此，讓未反應的光阻進行反應而使光阻變化成更容易溶解於鹼中的狀態，藉此減少光阻析出以及裝置上光阻的附著，而能提昇剝離液的回收率。Further, in addition to the addition of the basic compound, it is preferable to expose the entire liquid of the stripping liquid to a light having a wavelength of ultraviolet light (wavelength 10 -9 m)-visible light-infrared light (wavelength 10 -4 m) such as a fluorescent lamp. . Thereby, the unreacted photoresist is reacted to change the photoresist to a state in which it is more easily dissolved in the alkali, thereby reducing the deposition of the photoresist and the adhesion of the photoresist on the apparatus, and the recovery rate of the peeling liquid can be improved.
在本發明的剝離液廢液中含有光阻剝離步驟所使用之各種的溶劑，例如含有：用來除去光阻的剝離液、用來洗淨基板之稀釋劑(thinner)等。本發明的剝離液廢液中也含有基板洗淨液。作為光阻的剝離液，是對光阻具有高溶解度的溶液，例如包括：單乙醇胺(MEA)、二乙二醇單丁醚(BDG)、二甲亞碸(DMSO)、丙二醇單甲醚醋酸酯(以下也稱PGMEA)等的1種或數種的混合物。前述光阻的剝離液中經常採用者，是將MEA和DMSO、或是MEA和BDG以既定比例混合而成者，又作為基板洗淨用的稀釋劑，其代表性的物質，例如是PGMEA和丙二醇單甲醚(PGME)所混合成的溶劑等。The solvent for the stripping liquid of the present invention contains various solvents used in the resist stripping step, and includes, for example, a stripping liquid for removing the photoresist, a thinner for washing the substrate, and the like. The peeling liquid waste liquid of the present invention also contains a substrate cleaning liquid. The stripping solution as a photoresist is a solution having high solubility to a photoresist, and includes, for example, monoethanolamine (MEA), diethylene glycol monobutyl ether (BDG), dimethyl hydrazine (DMSO), propylene glycol monomethyl ether acetate. A mixture of one or more of esters (hereinafter also referred to as PGMEA). In the above-mentioned photoresist peeling liquid, MEA and DMSO, or MEA and BDG are mixed at a predetermined ratio, and are used as a diluent for substrate cleaning, and representative examples thereof are PGMEA and A solvent obtained by mixing propylene glycol monomethyl ether (PGME).
添加於前述剝離液廢液中的鹼性化合物，可列舉：氫氧化鈉、氫氧化鉀、碳酸鈉等的無機鹼性化合物；氫氧化四甲銨等的有機鹼性化合物等。其添加量換算成鈉時，相對於剝離液廢液的非揮發性成分(光阻)為0.01~0.2倍的質量。The basic compound to be added to the waste liquid of the peeling liquid may, for example, be an inorganic basic compound such as sodium hydroxide, potassium hydroxide or sodium carbonate; or an organic basic compound such as tetramethylammonium hydroxide. When the amount added is converted to sodium, the nonvolatile component (photoresist) of the peeling liquid waste liquid is 0.01 to 0.2 times the mass.
鹼性化合物的添加手段，可將溶解於水中的鹼性化合物連續定量地供應，也能分批定量地添加於裝置內貯留部中。鹼性化合物，能以固體或液體等任意的形式配合水，在鹼調整槽內用攪拌機均一混合來進行調整。在投入氫氧化鈉等的固體鹼性化合物的情況下的調整，是使用鹼濃度檢測器來檢測鹼濃度，接著調整補給水的量而調整成一定的濃度。或者是，也能使用濃度事先調整好的具有任意濃度之鹼性化合物。鹼性化合物的添加量，是按照調整後的鹼濃度、剝離液廢液中的光阻濃度來決定。The means for adding the basic compound can be continuously and quantitatively supplied to the alkaline compound dissolved in the water, or can be added to the storage portion in the apparatus quantitatively and quantitatively. The basic compound can be blended in any form such as a solid or a liquid, and uniformly adjusted by a mixer in an alkali adjusting tank. In the case of adding a solid basic compound such as sodium hydroxide, the alkali concentration detector is used to detect the alkali concentration, and then the amount of the makeup water is adjusted to adjust to a constant concentration. Alternatively, an alkaline compound having an arbitrary concentration adjusted in advance can also be used. The amount of the basic compound to be added is determined according to the adjusted alkali concentration and the resist concentration in the peeling liquid waste liquid.
對前述剝離液廢液全體利用螢光燈等具有紫外線(波長10-9 m)-可見光-紅外線(波長10-4 m)的波長的光進行曝光的時間，在從液深10mm的上面進行曝光的情況下是1~6000秒，較佳為300~1200秒。The exposure liquid is irradiated with light having a wavelength of ultraviolet light (wavelength 10 -9 m)-visible light-infrared light (wavelength 10 -4 m) such as a fluorescent lamp, and exposure is performed from the upper surface of the liquid depth of 10 mm. In the case of 1 to 6000 seconds, preferably 300 to 1200 seconds.
此外，作為將系統曝光之具體手段，可在所期望的部位例如設置透明的派熱司(pyrex，註冊商標)玻璃管或曝光裝置(包含觀察窗等的採光部)，對通過其內部的剝離液廢液以具有前述波長的光線進行曝光。曝光強度(光束)為800流明(lumen)以上，較佳為1000流明以上。Further, as a specific means for exposing the system, for example, a transparent Pyrex (registered trademark) glass tube or an exposure device (a lighting portion including an observation window) may be provided at a desired portion, for example, peeling through the inside thereof. The liquid waste liquid is exposed to light having the aforementioned wavelength. The exposure intensity (light beam) is 800 lumens or more, preferably 1000 lumens or more.
本發明之剝離液廢液所含的低沸點成分，是指沸點比剝離液成分更低的成分，其典型是剝離液廢液所含之水、溶解於剝離液之二氧化碳。又本發明之剝離液廢液所含之高沸點成分，是指沸點比剝離液成分更高的成分，具體例為光阻。The low-boiling point component contained in the stripping liquid waste liquid of the present invention means a component having a boiling point lower than that of the stripping liquid component, and is typically water contained in the stripping liquid waste liquid and carbon dioxide dissolved in the stripping liquid. Further, the high-boiling point component contained in the stripping liquid waste liquid of the present invention means a component having a boiling point higher than that of the stripping liquid component, and specific examples are photoresist.
以下參照圖式來詳細說明本發明。The invention will be described in detail below with reference to the drawings.
第10圖係顯示，未添加本發明的特徵之鹼性化合物的情況下之光阻剝離液廢液的再生裝置之代表性流程圖的一例之概略圖。剝離液廢液供應至低沸點物除去塔(T-1)的中間部，將餾出物之水、二氧化碳等的低沸點成分予以除去。從塔底部，是將排出物之剝離液、光阻、金屬、微粒子排出。該排出物供應至再沸器(RB-2)的下部，在使一部分的剝離液蒸發下從塔下部藉由泵送往薄膜式蒸發器(FD-1)而使大部分的剝離液蒸發，光阻、金屬、微粒子是屬於非揮發性成分，故不會蒸發而和少量的剝離液一起以高沸點成分的狀態排出系統外。在剝離液精製塔(T-2)，由於能將前述高沸點成分和剝離液實施精密地精餾分離，而能從塔頂餾出可再生回收的剝離液。T-1代表內部具備填充物之進行減壓操作的低沸點物除去塔，T-2代表內部具備填充物之進行減壓操作的連續精餾塔，藉此容易將剝離液和低沸點成分進行分離。在壁面刮取式降膜式蒸發器(FD-1)，可高效率地從高沸點成分中將剝離液予以分離蒸發。Fig. 10 is a schematic view showing an example of a representative flow chart of a regenerating apparatus for a photoresist stripping liquid waste liquid in the case where a basic compound of the present invention is not added. The stripping liquid waste liquid is supplied to the intermediate portion of the low-boiling point removal tower (T-1), and the low-boiling components such as water or carbon dioxide of the distillate are removed. From the bottom of the tower, the discharge liquid, photoresist, metal, and fine particles of the discharge are discharged. The effluent is supplied to the lower portion of the reboiler (RB-2), and a part of the stripping liquid is evaporated from the lower portion of the tower by pumping to the thin film evaporator (FD-1) to evaporate most of the stripping liquid. The photoresist, the metal, and the fine particles are non-volatile components, so they do not evaporate and are discharged out of the system together with a small amount of the stripping liquid in a state of high boiling point components. In the stripping liquid refining tower (T-2), the high-boiling point component and the stripping liquid can be precisely rectified and separated, and the recyclable liquid which can be regenerated and recovered can be distilled off from the top. T-1 represents a low-boiling substance removal column in which a packing is internally subjected to a pressure reduction operation, and T-2 represents a continuous rectification column in which a packing is internally subjected to a reduced pressure operation, whereby the stripping liquid and the low-boiling point component are easily performed. Separation. In the wall scraping type falling film evaporator (FD-1), the stripping liquid can be efficiently separated and evaporated from the high boiling point component.
然而，在第10圖之習知的方式，受到蒸氣的加熱溫度、滯留時間等的影響，會析出高沸點成分而附著於裝置壁面。所附著的場所包括：處理液滯留的場所、在光阻高度濃縮的場所且溫度變高(125℃以上)的場所。具體而言，在第10圖中，特別是在再沸器(RB-2)、薄膜式蒸發器(FD-1)的裝置壁面。因此，在習知的裝置，會造成處理能力變差，而必須實施定期洗淨、保養。However, in the conventional method of Fig. 10, due to the influence of the heating temperature of the steam, the residence time, and the like, high-boiling components are precipitated and adhere to the wall surface of the apparatus. The location to be attached includes a place where the treatment liquid stays, and a place where the temperature is high (125 ° C or higher) in a place where the photoresist is highly concentrated. Specifically, in Fig. 10, in particular, the device wall surface of the reboiler (RB-2) and the membrane evaporator (FD-1). Therefore, in the conventional device, the processing ability is deteriorated, and regular cleaning and maintenance must be performed.
本發明人等針對此問題進行深入研究，發現出以下的手段可減少光阻析出以及壁面上之光阻附著。亦即，在剝離液廢液管線之最佳部位，採用添加手段，來將氫氧化鈉、氫氧化鉀、碳酸鈉等的無機鹼性化合物、或氫氧化四甲銨等的有機鹼性化合物的水溶液，添加相當於剝離液廢液中的非揮發性成分(光阻)的0.01~0.2倍質量的量。又除了此手段以外可併用：對剝離液廢液全體用螢光燈等具有紫外線-可見光-紅外線(波長10-9 m~10-4 m)進行曝光的手段。The inventors of the present invention conducted intensive studies on this problem and found that the following means can reduce the precipitation of photoresist and the adhesion of photoresist on the wall surface. That is, an inorganic basic compound such as sodium hydroxide, potassium hydroxide or sodium carbonate or an organic basic compound such as tetramethylammonium hydroxide is used in an optimum portion of the stripping liquid waste liquid line by means of addition means. The aqueous solution is added in an amount corresponding to 0.01 to 0.2 times the mass of the nonvolatile component (photoresist) in the waste liquid of the peeling liquid. In addition to this means, it is possible to use a combination of ultraviolet light-visible-infrared rays (wavelengths of 10 -9 m to 10 -4 m) such as fluorescent lamps for the entire stripping liquid waste liquid.
藉此，可防止光阻析出以及光阻附著於壁面，能提昇精製剝離液的回收率，又能減輕定期洗淨及保養的負擔。Thereby, it is possible to prevent the photoresist from being deposited and the photoresist from adhering to the wall surface, thereby improving the recovery rate of the purified peeling liquid and reducing the burden of regular cleaning and maintenance.
第2圖至第5圖係顯示本發明的基本實施態樣。圖中標示[1]為添加鹼性水溶液之1個具體部位，標示[2]為用螢光燈等的光線進行曝光之1個具體部位。2 to 5 are views showing a basic embodiment of the present invention. In the figure, [1] is a specific portion to which an alkaline aqueous solution is added, and [2] is a specific portion to be exposed by light such as a fluorescent lamp.
在第2圖，是依低沸點物除去塔、薄膜式蒸發器以及剝離液精製塔的順序進行排列，鹼性水溶液是在(A)剝離液廢液進入低沸點物除去塔或薄膜式蒸發器之前的階段添加，或(B)在薄膜式蒸發器循環的步驟中添加。又按照需要來進行的曝光，在前述(A)的情況下是在鹼性水溶液添加前的階段，在前述(B)的情況下是在薄膜式蒸發器內部的壁面進行。In Fig. 2, the arrangement is performed in the order of the low boiler removal column, the membrane evaporator, and the stripping liquid refining tower, and the alkaline aqueous solution is in (A) the stripping liquid waste liquid into the low boiler removal tower or the thin film evaporator. Add in the previous stage, or (B) add in the step of the membrane evaporator cycle. Further, the exposure to be carried out as required is carried out in the case of the above (A) before the addition of the alkaline aqueous solution, and in the case of the above (B), on the wall surface inside the thin film evaporator.
在第3圖至第5圖的情況下，是依薄膜式蒸發器、低沸點物除去塔及剝離液精製塔的順序排列，鹼性水溶液是在(A)剝離液廢液進入低沸點物除去塔之前的階段添加，或(B)在離開薄膜式蒸發器而進入低沸點物除去塔之前的階段添加。又按照需要來進行的曝光，在前述(A)的情況下是在鹼性水溶液添加前的階段，在前述(B)的情況下是在薄膜式蒸發器內部的壁面、或是在薄膜式蒸發器和低沸點物除去塔之間進行鹼性化合物的添加之前的階段實施光照射。In the case of Fig. 3 to Fig. 5, the thin film evaporator, the low boiler removal column, and the stripping liquid refining column are arranged in this order, and the alkaline aqueous solution is removed in (A) the stripping liquid waste liquid into the low boiling point. The stage before the addition of the column, or (B) is added at a stage prior to exiting the membrane evaporator and entering the low boiler removal column. Further, in the case of the above (A), the exposure is performed before the alkaline aqueous solution is added, in the case of the above (B), the wall surface inside the thin film evaporator, or the film evaporation. Light irradiation was carried out at a stage before the addition of the basic compound between the lower boiling point removal column and the low boiler removal column.
第1圖係顯示本發明的代表性流程圖。圖中標示[1]為添加鹼性水溶液之1個具體部位，標示[2]為用螢光燈等的光線進行曝光之1個具體部位。此外，為了在連結裝置與裝置之配管部分進行曝光，可在配管之期望部位設置讓光線透過的部分。在薄膜式蒸發器(FD-1)等的裝置，也能透過該裝置所具備之觀察窗等光線可透過的部位來進行曝光照射。Figure 1 shows a representative flow chart of the present invention. In the figure, [1] is a specific portion to which an alkaline aqueous solution is added, and [2] is a specific portion to be exposed by light such as a fluorescent lamp. Further, in order to expose the connecting portion of the connecting device and the device, a portion through which light is transmitted may be provided at a desired portion of the pipe. In a device such as a film evaporator (FD-1), exposure light can be transmitted through a light-transmittable portion such as an observation window provided in the device.
接著簡單說明處理液的流動情形，使用後的剝離液廢液是從剝離液廢液管線送往低沸點物除去塔(T-1)，水、二氧化碳等的低沸點成分是經由管線(a)從低沸點物除去塔(T-1)的上方排出，另一方面，以高沸點成分為主成分之剝離液是經由管線(b)而由低沸點物除去塔(T-1)的下方排出。所排出之以高沸點成分為主成分之剝離液，經由第2再沸器(RB-2)送往剝離液精製塔(T-2)。在此，一部分的主成分會被精製，在第2冷凝器(C-2)液化後經由管線(c)以精製剝離液的狀態被回收。從剝離液精製塔(T-2)的下部回收之含有光阻的剝離液廢液，通過管線(d)而送往薄膜式蒸發器(FD-1)。在薄膜式蒸發器(FD-1)，藉由刮取式薄膜蒸發機構使光阻成分變成薄膜，和光阻分離後的剝離液會蒸發，而從薄膜式蒸發器(FD-1)的上部通過管線(e)而供應至剝離液精製塔(T-2)的中段，在此被精製然後在第2冷凝器(C-2)進行液化後，從管線(c)以精製剝離液的狀態被回收。含有不需要的光阻之廢液，從薄膜式蒸發器(FD-1)的下部通過管線(f)排出。Next, the flow of the treatment liquid will be briefly described. The used stripping liquid waste liquid is sent from the stripping liquid waste liquid line to the low-boiling point removal tower (T-1), and the low-boiling point component of water, carbon dioxide, etc. is via the line (a). The upper side of the low-boiling substance removal tower (T-1) is discharged, and the stripping liquid containing the high-boiling point component as a main component is discharged from the lower side of the low-boiling substance removal tower (T-1) via the line (b). . The stripping liquid containing the high-boiling point component as a main component is sent to the stripping liquid refining tower (T-2) via the second reboiler (RB-2). Here, a part of the main component is purified, and after the second condenser (C-2) is liquefied, it is recovered in a state in which the stripping liquid is purified via the line (c). The photoresist-containing peeling liquid waste liquid recovered from the lower portion of the stripping liquid refining column (T-2) is sent to the film evaporator (FD-1) through the line (d). In the film evaporator (FD-1), the photoresist component is changed into a film by a scraping film evaporation mechanism, and the stripping liquid after the photoresist separation evaporates, and passes through the upper portion of the film evaporator (FD-1). The line (e) is supplied to the middle stage of the stripping liquid refining column (T-2), where it is purified and then liquefied in the second condenser (C-2), and then the state of the stripping liquid is purified from the line (c). Recycling. The waste liquid containing the unnecessary photoresist is discharged from the lower portion of the membrane evaporator (FD-1) through the line (f).
如此般，含有低沸點物除去塔(T-1)、剝離液精製塔(T-2)以及薄膜式蒸發器(FD-1)(用來將剝離液和光阻儘可能分離)這3種不同的裝置之剝離液再生裝置，例如可在[I]~[V]所示的部位添加鹼性化合物，以按照需要來進行光照射。In this way, there are three different types of the low-boiling substance removal tower (T-1), the stripping liquid refining tower (T-2), and the thin film evaporator (FD-1) (used to separate the stripping liquid and the photoresist as much as possible). For example, the alkaline liquid compound can be added to the stripping liquid regenerating apparatus of the apparatus, and light irradiation can be performed as needed.
在薄膜式蒸發器(FD-1)，是利用藉由旋轉軸旋轉之刮除器(wiper)，使從薄膜式蒸發器(FD-1)的上部供應之剝離液廢液中的光阻在二層管的表面形成薄膜狀，使剝離液廢液中的低沸點成分高效率地氣化，且使高沸點成分從底部排出。In the film evaporator (FD-1), the wiper in the stripping liquid waste liquid supplied from the upper portion of the film evaporator (FD-1) is made by using a wiper that is rotated by a rotating shaft. The surface of the two-layer tube is formed into a film shape, and the low-boiling point component in the waste liquid of the peeling liquid is efficiently vaporized, and the high-boiling point component is discharged from the bottom.
1：剝離液廢液供應至低沸點物除去塔(T-1)以前的任意場所1: The stripping liquid waste liquid is supplied to any place before the low boiler removal tower (T-1)
2：從第1冷凝器(C-1)的下部透過泵送往低沸點物除去塔(T-1)的上部之供應管線(低沸點物除去塔的回流管線)之任意場所2: Any portion of the supply line (return line of the low boiler removal column) that is pumped to the upper portion of the low boiler removal column (T-1) from the lower portion of the first condenser (C-1)
3：從低沸點物除去塔(T-1)連通至第2再沸器(RB-2)的管線的任意場所3: Any place from the line where the low boiler removal tower (T-1) is connected to the second reboiler (RB-2)
4：從剝離液精製塔(T-2)的下部送往薄膜式蒸發器(FD-1)的上部之供應管線的任意場所4: Any place from the lower portion of the stripping liquid refining tower (T-2) to the supply line of the upper portion of the membrane evaporator (FD-1)
5：從薄膜式蒸發器(FD-1)的下部朝薄膜式蒸發器(FD-1)的上部進行再循環之管線的任意場所5: Any place from the lower portion of the membrane evaporator (FD-1) to the upper portion of the membrane evaporator (FD-1) for recycling
1：剝離液廢液供應至低沸點物除去塔(T-1)以前的任意場所1: The stripping liquid waste liquid is supplied to any place before the low boiler removal tower (T-1)
2：從第1冷凝器(C-1)的下部透過泵送往低沸點物除去塔(T-1)的上部之供應管線(低沸點物除去塔的回流管線)的任意場所2: Any portion of the supply line (return line of the low boiler removal column) that is pumped to the upper portion of the low boiler removal column (T-1) from the lower portion of the first condenser (C-1)
3：從低沸點物除去塔(T-1)連通至第2再沸器(RB-2)的管線之任意場所3: Any place from the line where the low boiler removal tower (T-1) is connected to the second reboiler (RB-2)
4：從剝離液精製塔(T-2)的下部送往薄膜式蒸發器(FD-1)的上部之供應管線的任意場所4: Any place from the lower portion of the stripping liquid refining tower (T-2) to the supply line of the upper portion of the membrane evaporator (FD-1)
5：薄膜式蒸發器(FD-1)內部壁面5: inner wall of membrane evaporator (FD-1)
以下用實施例來更具體地說明本發明，但本發明並不受這些實施例的限定。The invention will be more specifically described by the following examples, but the invention is not limited by these examples.
第9圖係用來驗證實際裝置中光阻的析出、附著情形之試驗裝置。在用油浴加熱成一定溫度之燒杯內的剝離液廢液中投入試驗片(SUS316，15mm寬×3mm厚×150mm長)，觀察附著於試驗片上的光阻量及其附著狀態。事先用旋轉蒸發器來濃縮剝離液廢液而將其光阻濃度調整為約17質量%(在剝離液廢液中含有2質量%光阻時之剝離液回收率90質量%的情況)。在此實驗中，當然對處理液有室內光的照射。Figure 9 is a test apparatus for verifying the precipitation and adhesion of photoresist in an actual device. A test piece (SUS316, 15 mm wide × 3 mm thick × 150 mm long) was placed in a waste liquid of a peeling liquid in a beaker heated to a certain temperature in an oil bath, and the amount of light adhered to the test piece and the state of adhesion thereof were observed. The stripping liquid waste liquid was concentrated by a rotary evaporator in advance, and the photoresist concentration was adjusted to about 17% by mass (when the peeling liquid recovery rate was 90% by mass in the case where the peeling liquid waste liquid contained 2% by mass of the photoresist). In this experiment, of course, there is room illumination of the treatment liquid.
使用前述第9圖的實驗裝置，將剝離液廢液溫度分別保持於120、130、140℃，測定隨著時間經過之單位面積的附著量。其數值如下述表1所示。從表1可看出，在140℃，從3小時後開始發生附著；在130℃，從6小時後開始發生附著；在120℃，從9小時後開始發生附著。附著物為褐色，呈硬且炭化的狀態，即使實施水洗淨、再生前之剝離液廢液洗淨，仍不容易將其除去。又得知，剝離液廢液的光阻受加熱溫度的影響很大，而必須儘量進行低溫加熱。此乃基於，若剝離液滯留於裝置內，光阻受熱的影響會發生固化、炭化。如此般，本發明人等可掌握實際裝置中的附著狀態。Using the experimental apparatus of the above-mentioned Fig. 9, the temperature of the peeling liquid waste liquid was maintained at 120, 130, and 140 ° C, respectively, and the adhesion amount per unit area with time was measured. The values are shown in Table 1 below. As can be seen from Table 1, at 140 ° C, adhesion occurred from 3 hours later; at 130 ° C, adhesion occurred from 6 hours later; at 120 ° C, adhesion occurred from 9 hours later. The deposit is brown and hard and charred, and it is not easy to remove the peeling liquid waste liquid before washing with water and before regeneration. It is also known that the photoresist of the stripping liquid waste liquid is greatly affected by the heating temperature, and it is necessary to perform low-temperature heating as much as possible. This is based on the fact that if the stripping solution is retained in the device, the photoresist will be cured and charred by the influence of heat. In this way, the inventors of the present invention can grasp the state of adhesion in the actual device.
於是，本發明人等，針對用來解決上述問題的手段，根據以下的實施例而解明出：在析出光阻前的階段添加鹼性化合物，或除此外更進行光照射是有效的。Then, the inventors of the present invention have been able to solve the above problems, and according to the following examples, it is explained that it is effective to add a basic compound at a stage before precipitation of a photoresist or to further perform light irradiation.
表2顯示出，使用和第9圖的試驗器相同的試驗器(由於使用燒杯，故屬於併用光照射的例子)，在剝離液廢液的原液中添加0.05質量%(48質量%NaOH水溶液的狀態下的添加比例)的氫氧化鈉水溶液，用旋轉蒸發器濃縮成光阻濃度約17質量%，進行和前述同樣的試驗的結果。在140℃從24小時開始發生附著，在130℃從34小時開始發生附著，在120℃從48小時開始發生附著。附著物為淡褐色的泥狀物，看不出炭化的狀態，藉由實施水洗淨、再生前的剝離液廢液洗淨很容易就能除去。在發生附著的時間以及附著量雙方，都比比較例1的試驗結果(表1的資料)獲得更良好的結果。Table 2 shows that the same tester as that of the tester of Fig. 9 was used (an example in which a beaker was used, and light irradiation was used), and 0.05% by mass (48% by mass of NaOH aqueous solution) was added to the stock solution of the stripping liquid waste liquid. The sodium hydroxide aqueous solution in the state of the addition ratio was concentrated by a rotary evaporator to a resist concentration of about 17% by mass, and the results of the same tests as described above were carried out. Adhesion occurred from 24 hours at 140 ° C, adhesion occurred from 34 hours at 130 ° C, and adhesion occurred from 48 hours at 120 ° C. The deposit is a pale brown mud, and the carbonized state is not observed, and it can be easily removed by washing with water and washing the stripping liquid before regeneration. Both the time of adhesion and the amount of adhesion were obtained better than the test results of Comparative Example 1 (data of Table 1).
此外，為了提昇精製剝離液的回收率，將同樣添加有氫氧化鈉水溶液的剝離液廢液用旋轉蒸發器濃縮成光阻濃度約31質量%，藉由和實施例1同樣的方法進行試驗。結果顯示於表3。在目視觀察下，在140℃從18小時開始發生附著，在130℃從23小時開始發生附著，在120℃從32小時開始發生附著。附著物呈褐色泥狀，雖看得出有若干炭化狀態，但藉由實施水洗淨、再生前的剝離液廢液洗淨可將其除去。如此般確認出，即使光阻濃度提高，仍能獲得比比較例1的表1所示的結果更良好的結果，因此鹼性化合物的添加效果相當顯著。Further, in order to increase the recovery rate of the purified stripping solution, the stripping liquid waste liquid to which the sodium hydroxide aqueous solution was added in the same manner was concentrated by a rotary evaporator to have a photoresist concentration of about 31% by mass, and the test was carried out in the same manner as in Example 1. The results are shown in Table 3. Under visual observation, adhesion occurred from 18 hours at 140 ° C, adhesion occurred from 23 hours at 130 ° C, and adhesion occurred from 32 hours at 120 ° C. The deposit was brownish mud, and although it was observed that there were some carbonization states, it could be removed by washing the stripping liquid before washing with water and before regeneration. As a result, it was confirmed that even if the resist concentration was increased, a result more excellent than the results shown in Table 1 of Comparative Example 1 was obtained, and therefore the effect of adding the basic compound was remarkable.
又表1~表3之附著量資料，並不是根據目視，而是定量測定的結果。The amount of adhesion data in Tables 1 to 3 is not based on visual observation but as a result of quantitative measurement.
本發明人等發現，從剝離液廢液貯槽供應至第1圖的再生裝置之剝離液廢液中的光阻，是混合有在液晶製造過程等中進行曝光的光阻和未進行曝光的光阻，而該差異可能會影響光阻之析出、附著。於是，本實驗裝置，是接續於未圖示的剝離液廢液貯槽，而使用由不鏽鋼構成且幾乎完全遮光(僅從局部的觀察孔等可進行曝光)的狀態之再生裝置。前述比較例1及實施例1，是在室內進行燒杯試驗，因此剝離液是進行曝光。The inventors of the present invention have found that the photoresist in the stripping liquid waste liquid supplied from the stripping liquid waste storage tank to the regenerating apparatus of Fig. 1 is a mixture of light that is exposed during liquid crystal manufacturing or the like and light that is not exposed. Resistance, and this difference may affect the precipitation and adhesion of the photoresist. Then, the experimental apparatus is a regenerating apparatus which is connected to a peeling liquid waste liquid tank (not shown) and which is made of stainless steel and is almost completely shielded from light (only a partial observation hole or the like can be exposed). In the above Comparative Example 1 and Example 1, since the beaker test was performed indoors, the peeling liquid was exposed.
本試驗，兩個例子都是，首先用旋轉蒸發器將剝離液廢液濃縮至光阻濃度約15質量%。接著，將所得的濃縮剝離液廢液進行以下的處理。In this test, two examples were as follows. First, the stripping liquid waste liquid was concentrated to a photoresist concentration of about 15% by mass using a rotary evaporator. Next, the obtained concentrated stripping liquid waste liquid was subjected to the following treatment.
(1)比較例2：未添加氫氧化鈉也不進行曝光。(1) Comparative Example 2: No exposure was carried out without adding sodium hydroxide.
(2)實施例2-1：換算成剝離液廢液是添加0.05質量%的氫氧化鈉，但不進行曝光。(2) Example 2-1: Conversion into a peeling liquid The waste liquid was added with 0.05% by mass of sodium hydroxide, but exposure was not performed.
實施例2-2：換算成剝離液廢液是添加0.05質量%的氫氧化鈉，且進行曝光10分鐘。Example 2-2: Conversion into a peeling liquid The waste liquid was added with 0.05% by mass of sodium hydroxide, and exposure was carried out for 10 minutes.
然後，在用140℃的油浴加熱之含濃縮剝離液的容器中分別投入試驗片，保持48小時。這些試驗都是在暗室中進行。Then, the test piece was placed in a container containing a concentrated stripping solution heated in an oil bath of 140 ° C for 48 hours. These tests were performed in a dark room.
表4顯示前述比較例1、實施例2-1及實施例2-2的結果。比較例1的附著量為8.35g/cm2 ，實施例2-1的附著量為4.46g/cm2 ，實施例2-2的附著量為4.02g/cm2 。由此結果可知，藉由進行曝光可減少光阻之析出、附著。此外，在實施水洗淨、剝離液洗淨方面，比起未添加氫氧化鈉的情況，添加氫氧化鈉的情況更容易除去附著物。Table 4 shows the results of Comparative Example 1, Example 2-1, and Example 2-2. Comparative Example 1 adhesion amount was 8.35g / cm 2, the coating weight of Example 2-1 was 4.46g / cm 2, the coating weight of Example 2-2 was 4.02g / cm 2. From this result, it is understood that precipitation and adhesion of the photoresist can be reduced by performing exposure. Further, in the case of performing water washing or washing of the peeling liquid, it is easier to remove the deposit when sodium hydroxide is added than when sodium hydroxide is not added.
第6圖顯示水溶性無機鹼性化合物添加裝置的1個實施例。鹼性化合物是使用氫氧化鈉水溶液，在鹼調整槽用攪拌機進行均一混合。氫氧化鈉的情況之濃度調整，是用鹼濃度檢測器來檢測鹼濃度，藉由調整補給水的量來調整成一定濃度。氫氧化鈉的添加量，是依據調整後的氫氧化鈉的濃度、剝離液廢液中的光阻濃度來決定。剝離液廢液中鹼性化合物的供應，是使用定量泵，在第1圖所示的[1]部位[從供應管線至精製剝離液管線之最佳部位]的配管管線供應。在供應位置的後方，具備靜態混合器等之用來混合氫氧化鈉水溶液和剝離液廢液的機構。第6圖顯示1個實施例，只要能供應調整成一定濃度的氫氧化鈉水溶液，則只需定量泵，而能省略鹼調整槽。Fig. 6 shows an embodiment of a water-soluble inorganic basic compound adding device. The basic compound was uniformly mixed with a sodium hydroxide aqueous solution using a stirrer in an alkali adjusting tank. In the case of sodium hydroxide, the concentration adjustment is performed by using an alkali concentration detector to adjust the alkali concentration, and adjusting the amount of makeup water to adjust the concentration to a certain concentration. The amount of sodium hydroxide added is determined by the concentration of the adjusted sodium hydroxide and the concentration of the photoresist in the waste liquid of the peeling liquid. The supply of the alkaline compound in the stripping liquid waste liquid is supplied from a piping line of the [1] portion [the optimum portion from the supply line to the purified stripping liquid line] shown in Fig. 1 using a metering pump. Behind the supply position, there is a mechanism for mixing a sodium hydroxide aqueous solution and a stripping liquid waste liquid, such as a static mixer. Fig. 6 shows an embodiment in which the alkali adjustment tank can be omitted as long as the sodium hydroxide aqueous solution adjusted to a certain concentration can be supplied.
第7圖及第8圖係顯示曝光裝置的2個實施例。第7圖是在配管管線中插入曝光裝置的1個實施例，是將配管中途變更成光線可透過之派熱司(pyrex，註冊商標)玻璃等的配管，從該配管的兩面用螢光燈等之具有紫外線(波長10-9 m)-可見光-紅外線(波長10-4 m)的波長的光進行曝光，以使未反應光阻進行反應的裝置。本例的裝置，為了使用螢光燈而至少進行5分鐘曝光，根據廢液的流速，將光線可透過之配管部分的長度設定為約8m長。第8圖係利用第1圖所示的薄膜式蒸發器(FD-1)的觀察窗來進行紫外線曝光的裝置，在上下觀察窗的4個部位設置該裝置。具備攪拌機之降膜式蒸發裝置(FD-1)，可藉由安裝於攪拌機之擋葉(flapper)將剝離液以1mm左右的膜厚均一分散在蒸發器壁面，且不會因液深而造成曝光的衰減，即使光量較少仍能進行均一曝光。Figures 7 and 8 show two embodiments of an exposure apparatus. Fig. 7 is a view showing an embodiment in which an exposure apparatus is inserted into a piping line, and piping which is changed to a light-transmissive Pyrex (registered trademark) glass in the middle of piping, and fluorescent lamps are used on both sides of the piping. A device that emits light having a wavelength of ultraviolet light (wavelength 10 -9 m)-visible light-infrared light (wavelength 10 -4 m) to cause an unreacted photoresist to react. In the apparatus of this example, in order to use at least 5 minutes of exposure using a fluorescent lamp, the length of the portion through which the light is permeable is set to be about 8 m in length according to the flow rate of the waste liquid. Fig. 8 is a view showing an apparatus for performing ultraviolet exposure using the observation window of the thin film evaporator (FD-1) shown in Fig. 1, and the apparatus is provided at four places of the upper and lower observation windows. A falling film evaporation device (FD-1) equipped with a stirrer can uniformly disperse the peeling liquid on the wall surface of the evaporator by a flange attached to the mixer, and is not caused by the liquid depth. The attenuation of the exposure enables uniform exposure even with a small amount of light.
將實施例3及實施例4的鹼性化合物添加裝置和曝光裝置安裝於第1圖所示的實際裝置，和安裝前進行比較實驗。將鹼性化合物添加裝置插入第1圖之[II]所示的配管中途。曝光裝置，是利用設置於攪拌機之降膜式蒸發裝置(FD-1)的Φ150觀察窗，在上下2個部位(合計4個部位)設置水銀燈，而以1000流明進行曝光。The alkaline compound addition device and the exposure apparatus of Example 3 and Example 4 were attached to the actual apparatus shown in Fig. 1, and a comparative experiment was performed before mounting. The alkaline compound addition device was inserted into the pipe shown in [II] of Fig. 1 . The exposure apparatus was a Φ150 observation window provided by a falling film type evaporation apparatus (FD-1) of a stirrer, and a mercury lamp was placed at two upper and lower parts (four parts in total), and exposure was performed at 1000 lumens.
本剝離液再生裝置之既定處理量為540kg/h，其組成分析值為：剝離液廢液476kg/h、光阻等的高沸點成分10kg/h、水等的低沸點成分54kg/h。48質量%的氫氧化鈉以540×0.0005=0.27kg/h的添加量進行定量供應。The predetermined treatment amount of the stripping liquid regenerating apparatus was 540 kg/h, and the composition analysis value was 476 kg/h of the peeling liquid waste, 10 kg/h of a high boiling point component such as a photoresist, and 54 kg/h of a low boiling point component such as water. 48% by mass of sodium hydroxide was quantitatively supplied at an addition amount of 540 × 0.0005 = 0.27 kg / h.
對各條件下的精製再生量進行比較。The amount of refined regeneration under each condition was compared.
精製剝離液之平均回收率約88質量%、419kg/h，在FD-1的壁面及FD-1的下部的貯液部發生光阻的析出、附著，必須實施定期(1次/3天的自動水洗，1次/年的拆解洗淨)保養。The average recovery rate of the purified stripping solution is about 88% by mass and 419 kg/h, and the deposition and adhesion of the photoresist are generated in the wall surface of the FD-1 and the liquid portion of the lower portion of the FD-1, and it is necessary to carry out periodic (1 time / 3 days). Automatic washing, 1 time / year of disassembly and washing) maintenance.
精製剝離液之平均回收率約90質量%、428kg/h，可在定量且穩定的狀態下進行剝離液的再生。FD-1壁面上的光阻附著以及FD-1下部的貯液部的光阻析出、附著幾乎看不到，但必須進行定期(1次/3天的自動水洗)洗淨。亦即，藉由添加鹼性化合物，能增加光阻對剝離液的溶解度，而減少光阻之析出、附著，因此能提高剝離液的回收率。The average recovery rate of the purified peeling liquid is about 90% by mass and 428 kg/h, and the peeling liquid can be regenerated in a quantitative and stable state. The photoresist adhesion on the wall surface of the FD-1 and the photoresist deposition and adhesion in the liquid storage portion at the lower portion of the FD-1 were hardly observed, but it was necessary to perform periodic (one-time/three-day automatic water washing) cleaning. That is, by adding a basic compound, the solubility of the photoresist to the stripping solution can be increased, and the precipitation and adhesion of the photoresist can be reduced, so that the recovery rate of the stripping solution can be improved.
精製剝離液之平均回收率約95質量%、425kg/h，可在定量且穩定的狀態下進行剝離液的再生。FD-1壁面上的光阻附著以及FD-1下部的貯液部的光阻析出、附著幾乎看不到，藉由進行定期(1次/3天的自動水洗)洗淨可避免發生最糟的情況。The average recovery rate of the purified peeling liquid is about 95% by mass and 425 kg/h, and the peeling liquid can be regenerated in a quantitative and stable state. The photoresist on the wall surface of the FD-1 and the photoresist deposition and adhesion in the liquid reservoir at the lower part of the FD-1 are hardly visible, and it is possible to avoid the worst by washing regularly (one time/three days of automatic water washing). Case.
FD-1．．．薄膜式蒸發器FD-1. . . Thin film evaporator
T-1．．．低沸點物除去塔T-1. . . Low boiler removal tower
T-2．．．剝離液精製塔T-2. . . Stripping liquid refining tower
RB．．．再沸器RB. . . Reboiler
C．．．冷凝器C. . . Condenser
P．．．泵P. . . Pump
(a)．．．連結低沸點物除去塔上部和第1冷凝器的配管(a). . . Connecting the low boiler to remove the upper portion of the column and the piping of the first condenser
(b)．．．連結低沸點物除去塔底部和第2再沸器的配管(b). . . Connecting the low boiler to remove the bottom of the column and the piping of the second reboiler
(c)．．．用來回收精製剝離液的配管(c). . . Piping for recycling refined stripping solution
(d)．．．連結剝離液精製塔底部和薄膜式蒸發器上部的配管(d). . . Connecting the bottom of the stripping refining tower and the piping on the upper part of the membrane evaporator
(e)．．．連結薄膜式蒸發器上部和剝離液精製塔中段的配管(e). . . Connecting the upper part of the membrane evaporator and the piping of the middle section of the stripping refining tower
第1圖係顯示本發明的實施例之具體的剝離液再生裝置的流程一例。Fig. 1 is a view showing an example of the flow of a specific peeling liquid regeneration apparatus according to an embodiment of the present invention.
第2圖係顯示本發明的基本的剝離液再生裝置的流程一例。Fig. 2 is a view showing an example of the flow of the basic peeling liquid regenerating apparatus of the present invention.
第3圖係顯示本發明的基本的剝離液再生裝置的流程另一例。Fig. 3 is a view showing another example of the flow of the basic peeling liquid regenerating apparatus of the present invention.
第4圖係顯示本發明的基本的剝離液再生裝置的流程另一例。Fig. 4 is a view showing another example of the flow of the basic stripping liquid regenerating apparatus of the present invention.
第5圖係顯示本發明的基本的剝離液再生裝置的流程另一例。Fig. 5 is a view showing another example of the flow of the basic peeling liquid regenerating apparatus of the present invention.
第6圖係顯示鹼定量添加裝置。Figure 6 shows a base dosing device.
第7圖係顯示配管管線曝光裝置，(a)為前視圖，(b)為側視圖。Fig. 7 shows a piping line exposure device, (a) being a front view and (b) being a side view.
第8圖係顯示安裝於薄膜式蒸發器的曝光裝置。Fig. 8 shows an exposure apparatus mounted on a film evaporator.
第9圖係顯示附著試驗用的實驗裝置。Figure 9 shows the experimental apparatus for the adhesion test.
第10圖係顯示習知的剝離液再生裝置的流程。Fig. 10 is a view showing the flow of a conventional stripping liquid regenerating apparatus.
FD-1．．．薄膜式蒸發器FD-1. . . Thin film evaporator
T-1．．．低沸點物除去塔T-1. . . Low boiler removal tower
T-2．．．剝離液精製塔T-2. . . Stripping liquid refining tower
RB-1、RB-2．．．再沸器RB-1, RB-2. . . Reboiler
C-1、C-2．．．冷凝器C-1, C-2. . . Condenser
P1~P6．．．泵P1~P6. . . Pump
(a)．．．連結低沸點物除去塔上部和第1冷凝器的配管(a). . . Connecting the low boiler to remove the upper portion of the column and the piping of the first condenser
(b)．．．連結低沸點物除去塔底部和第2再沸器的配管(b). . . Connecting the low boiler to remove the bottom of the column and the piping of the second reboiler
(c)．．．用來回收精製剝離液的配管(c). . . Piping for recycling refined stripping solution
(d)．．．連結剝離液精製塔底部和薄膜式蒸發器上部的配管(d). . . Connecting the bottom of the stripping refining tower and the piping on the upper part of the membrane evaporator
(e)．．．連結薄膜式蒸發器上部和剝離液精製塔中段的配管(e). . . Connecting the upper part of the membrane evaporator and the piping of the middle section of the stripping refining tower
(f)．．．管線(f). . . Pipeline
[I]~[V]．．．鹼性化合物的添加部位[I]~[V]. . . Addition of basic compounds
Claims (7)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2007278988A JP5165337B2 (en) | 2007-10-26 | 2007-10-26 | Method and apparatus for regenerating stripping liquid from stripping liquid waste |
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| TWI444220B true TWI444220B (en) | 2014-07-11 |
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| JP (1) | JP5165337B2 (en) |
| KR (1) | KR101497150B1 (en) |
| CN (1) | CN101424889B (en) |
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| KR101038042B1 (en) * | 2010-03-26 | 2011-05-31 | 재원산업 주식회사 | Reproducing method of used propylene glycol monomethyl ether acetate |
| TW201328983A (en) * | 2012-01-03 | 2013-07-16 | Hong He Environmental Technology Co Ltd | Method and device for concentrating iodine-containing solution |
| JP6045283B2 (en) * | 2012-10-11 | 2016-12-14 | 日本リファイン株式会社 | Method and apparatus for regenerating resist stripping solution |
| JP6156678B2 (en) * | 2012-10-11 | 2017-07-05 | パナソニックＩｐマネジメント株式会社 | Method and apparatus for regenerating resist stripping solution |
| JP6033033B2 (en) * | 2012-10-11 | 2016-11-30 | 日本リファイン株式会社 | Method and apparatus for regenerating resist stripping solution |
| KR101423967B1 (en) * | 2013-11-27 | 2014-08-01 | 주식회사 코렉스 | Recycling Process for recycling 1-Piperazineethanol from waste high boiling point photoresist stripper |
| KR101354523B1 (en) * | 2013-11-27 | 2014-01-21 | 주식회사 코렉스 | Recycling apparatus for recycling 1-piperazineethanol from waste high boiling point photoresist stripper |
| KR20170002930A (en) | 2015-06-30 | 2017-01-09 | 동우 화인켐 주식회사 | Recycling process of waste stripper |
| CN107797395A (en) * | 2017-09-29 | 2018-03-13 | 江苏盈天化学有限公司 | A kind of recovery method and device for mixing useless light resistance washing agent |
| CN108054119B (en) * | 2017-12-06 | 2021-03-23 | 深圳市华星光电半导体显示技术有限公司 | Stripping liquid machine table for stripping process and working method thereof |
| TWI643657B (en) * | 2017-12-29 | 2018-12-11 | 財團法人工業技術研究院 | System and method for processing waste solvent |
| CN108837546A (en) * | 2018-05-29 | 2018-11-20 | 四川久远化工技术有限公司 | A kind of moisture removal method of stripper regeneration technology section |
| CN108862431A (en) * | 2018-05-29 | 2018-11-23 | 四川久远化工技术有限公司 | A kind of reuse stripper refining system of stripper regeneration technology section |
| WO2020017070A1 (en) * | 2018-07-18 | 2020-01-23 | リファインホールディングス株式会社 | Solution processing device and solution processing method |
| CN110536730B (en) * | 2018-07-18 | 2021-12-03 | 瑞环控股有限公司 | Solution treatment apparatus and solution treatment method |
| CN108926860B (en) * | 2018-07-20 | 2021-12-21 | 上海化工研究院有限公司 | Waste stripping liquid regeneration device and application thereof |
| JP2021021890A (en) * | 2019-07-30 | 2021-02-18 | 旭化成株式会社 | Separation recovery method, and development device and development method |
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| JP2002131932A (en) * | 2000-10-24 | 2002-05-09 | Kimura Chem Plants Co Ltd | Method for regenerating and recovering resist removing liquid, and device for regenerating and recovering the same |
| JP2003167358A (en) * | 2001-11-29 | 2003-06-13 | Nagase & Co Ltd | Equipment for regenerating used resist peeling solution and method therefor |
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| CN101424889B (en) | 2013-12-18 |
| CN101424889A (en) | 2009-05-06 |
| JP2009109559A (en) | 2009-05-21 |
| TW200927264A (en) | 2009-07-01 |
| JP5165337B2 (en) | 2013-03-21 |
| KR20090042737A (en) | 2009-04-30 |
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