JP2009109559A - Method and apparatus for regenerating releasing liquid from releasing liquid waste water - Google Patents
Method and apparatus for regenerating releasing liquid from releasing liquid waste water Download PDFInfo
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- 239000007788 liquid Substances 0.000 title claims abstract description 121
- 239000010808 liquid waste Substances 0.000 title claims abstract description 33
- 230000001172 regenerating effect Effects 0.000 title claims abstract description 30
- 238000000034 method Methods 0.000 title claims abstract description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 title abstract description 21
- 238000004519 manufacturing process Methods 0.000 claims abstract description 13
- 239000004973 liquid crystal related substance Substances 0.000 claims abstract description 10
- 239000000243 solution Substances 0.000 claims description 170
- 239000003513 alkali Substances 0.000 claims description 61
- 239000002699 waste material Substances 0.000 claims description 56
- 238000009835 boiling Methods 0.000 claims description 54
- 239000010409 thin film Substances 0.000 claims description 50
- 238000000746 purification Methods 0.000 claims description 31
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000012545 processing Methods 0.000 claims description 8
- 230000008929 regeneration Effects 0.000 claims description 7
- 238000011069 regeneration method Methods 0.000 claims description 7
- 239000000126 substance Substances 0.000 claims description 5
- 230000001678 irradiating effect Effects 0.000 claims description 3
- 238000000926 separation method Methods 0.000 claims description 3
- 238000011084 recovery Methods 0.000 abstract description 14
- 230000003247 decreasing effect Effects 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 69
- 238000004140 cleaning Methods 0.000 description 14
- 238000012360 testing method Methods 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 10
- 230000008021 deposition Effects 0.000 description 10
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 8
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 8
- 239000002904 solvent Substances 0.000 description 8
- 238000001704 evaporation Methods 0.000 description 7
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 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
- 239000012535 impurity Substances 0.000 description 6
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 5
- 238000012423 maintenance Methods 0.000 description 5
- 230000007246 mechanism Effects 0.000 description 5
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 4
- 239000001569 carbon dioxide Substances 0.000 description 4
- 229910002092 carbon dioxide Inorganic materials 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000010419 fine particle Substances 0.000 description 4
- 229910052751 metal Inorganic materials 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 4
- 230000000007 visual effect Effects 0.000 description 4
- ARXJGSRGQADJSQ-UHFFFAOYSA-N 1-methoxypropan-2-ol Chemical compound COCC(C)O ARXJGSRGQADJSQ-UHFFFAOYSA-N 0.000 description 3
- 239000011521 glass Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000000203 mixture Substances 0.000 description 3
- 230000000737 periodic effect Effects 0.000 description 3
- 230000008569 process 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
- 238000004064 recycling Methods 0.000 description 3
- 239000011347 resin Substances 0.000 description 3
- 229920005989 resin Polymers 0.000 description 3
- 238000007790 scraping Methods 0.000 description 3
- 239000007787 solid Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical compound CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 2
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 230000006837 decompression Effects 0.000 description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 2
- 238000004821 distillation Methods 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000010408 film Substances 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 230000006872 improvement Effects 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002923 metal particle Substances 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 2
- 238000012856 packing Methods 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 239000005297 pyrex Substances 0.000 description 2
- 238000010992 reflux Methods 0.000 description 2
- 229910000029 sodium carbonate Inorganic materials 0.000 description 2
- 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
- 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 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
- 238000004458 analytical method Methods 0.000 description 1
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- 238000005516 engineering process Methods 0.000 description 1
- 238000005530 etching Methods 0.000 description 1
- 239000011552 falling film Substances 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- 238000009533 lab test Methods 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
- 239000012466 permeate Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- 230000007261 regionalization Effects 0.000 description 1
- -1 resist Substances 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 229910052708 sodium Inorganic materials 0.000 description 1
- 239000011734 sodium Substances 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
- 238000003756 stirring Methods 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Images
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—
Abstract
Description
本発明は、剥離液廃液からの剥離液の再生方法および再生装置に関する。 The present invention relates to a method and apparatus for regenerating a stripping solution from a stripping solution waste solution.
液晶の製造工程(液晶ディスプレイのアレイ基盤ユニット製造工程)から排出されるレジストを含有した剥離液廃液には、レジストに加えて水、重金属類や種々の微粒子などの不揮発成分、低沸点成分、高沸点成分を含んでいる。従来、レジスト剥離液廃液から溶剤(精製剥離液)を回収するための方法や装置に関する発明として特許文献1〜3がある。特許文献1に記載された溶剤の再生装置によれば、前記高沸点物質の除去手段として薄膜降下型の蒸発缶を使用し、前記蒸発部で発生した溶剤および低沸点汚れ成分を含む蒸気をミスト分離機を介して精留塔に供給し、精留塔の留分として低沸点成分を分離し、精留塔の缶出液として高沸点物を、さらにサイドカット成分として再生回収液(精製剥離液)を得ている。
In addition to the resist, non-volatile components such as water, heavy metals and various fine particles, low-boiling components, high Contains boiling components. Conventionally,
また、特許文献2の溶剤再生装置によれば、剥離液廃液からレジスト(樹脂)成分を除去し、溶剤を再生、回収する手段として、ローター内面掻き取り式薄膜流下機構による蒸発濃縮手段と剥離液廃液に含まれる低沸点不純物を除去する第1蒸留塔と高沸点物質を高精度に分離精製する第2蒸留塔にを用いて剥離液廃液を精製し、再生剥離液としてリサイクルする技術が開示されている。
Further, according to the solvent regeneration apparatus of
一方、特許文献3では、モノエタノールアミンを主成分の1つとして含有するレジスト剥離液を用いてレジストの剥離除去を行った後の、剥離液廃液を再生、回収するための方法と装置において、剥離液廃液に水酸化アルカリを添加して、剥離液廃液中の炭酸成分を炭酸アルカリとして固定するアルカリ添加工程と、炭酸成分を炭酸アルカリとして固定した後の剥離液廃液を蒸留することにより剥離液を回収する蒸留回収工程とを設けることを提案しており、前記水酸化アルカリの添加量は、前記炭酸成分を炭酸アルカリとして固定するのに必要な理論量の1〜1.5倍の範囲としている。このように特許文献3では、レジスト剥離液中の炭酸成分の除去を目的としたアルカリ成分の添加であり、本発明のアルカリ添加量より1桁の多い使用量である。したがって、剥離液廃液中には通常炭酸成分が0.5〜2質量%含まれているから、剥離液廃液中に含まれている炭酸成分を0.5質量%とし、用いるアルカリが水酸化ナトリウムである場合の水酸化ナトリウムの量は、
0.5(炭酸濃度)÷44(二酸化炭素分子量)×40(水酸化ナトリウム分子量)
=0.45質量%
になり、かなりの量のアルカリを用いることが不可欠となっている。このように特許文献3記載の技術はあくまでも剥離液廃液中の炭酸を固定するためのものであり、剥離液廃液のレジストを処理するためのものではなく、特許文献3にはレジストをアルカリで処理するという技術思想は皆無である。
On the other hand, in
0.5 (carbonic acid concentration) ÷ 44 (carbon dioxide molecular weight) × 40 (sodium hydroxide molecular weight)
= 0.45 mass%
Therefore, it is essential to use a considerable amount of alkali. As described above, the technique described in
しかしながら、剥離液廃液にはレジスト樹脂以外に水、重金属類、微粒子など不揮発成分および高沸点物質を混入しており、上述した従来の剥離液廃液を再生する装置の実際の稼動状況は、剥離液廃液が濃縮されるに伴い、レジスト(樹脂)の剥離液に対する溶解度が低下(剥離液がレジストを溶解する限度以上に達する)するため、ある限度以上にレジスト濃度が濃縮されると、レジストが析出し、装置内面に付着・固着する。とくにレジスト濃度が濃くなる高沸点物、不揮発分を除去する工程でのレジスト成分の付着、固着が多く、特許文献1では、ローター内面掻取り式薄膜流下機構による蒸発濃縮手段のローター部や掻取り面に付着、固定し、装置の正常な稼動が困難となる。同様に特許文献2や3においても、薄膜降下形の蒸発缶では、蒸発に必要な熱を与えるための面にレジスト成分が付着、固着して蒸発缶としての本来の機能が低下してしまう。いずれにしても、レジストが装置に付着・固着するため、定期的な装置の洗浄が必要となり、稼働率が低下するばかりでなく、精製剥離液の回収率の限界を示唆している。濃縮したレジストに同伴する剥離液は損失となるため、新品の剥離液を購入して補充しなければならないので、高価な剥離液を調達するためコストが高くつくという問題があった。
また、固着したレジストの中には、洗浄性が悪く固着した不揮発分が全て剥がれ落ちないために洗浄工程を入れても装置の能力を経時的に劣化させるという問題もあった。
However, in addition to the resist resin, non-volatile components such as water, heavy metals, and fine particles and high-boiling substances are mixed in the stripping liquid waste liquid, and the actual operation status of the above-described conventional apparatus for reclaiming the stripping liquid waste liquid is as follows. As the waste solution is concentrated, the solubility of the resist (resin) in the stripping solution decreases (the stripping solution reaches the limit that dissolves the resist), and the resist precipitates when the resist concentration is concentrated above a certain limit. And adheres and adheres to the inner surface of the device. In particular, high boiling point substances with a high resist concentration and resist component adhesion and sticking in the process of removing the non-volatile content are many. In
Further, the fixed resist has a problem that the ability of the apparatus is deteriorated with time even if a cleaning process is performed because the fixed non-volatile components are not peeled off due to poor cleaning properties.
本発明は、上記の問題点に鑑みて創案されたものであり、電子工業用で使用可能な純度の高価な剥離液の補充を少なくし、剥離液廃液から従来より高い回収率で精製剥離液を再生することのできる新規な剥離液の再生方法および装置を提供することを課題とする。 The present invention was devised in view of the above-mentioned problems, reduces the replenishment of expensive stripping solution of purity that can be used in the electronics industry, and purifies stripping solution with a higher recovery rate than conventional stripping solution waste solution. It is an object of the present invention to provide a novel stripping solution recycling method and apparatus that can regenerate the liquid.
例えば半導体製造工場や液晶ディスプレイパネルの製造工程のアレイ基盤製造プロセスにおいて、マザー硝子基板上に金属膜を形成、洗浄し、その上に紫外線で感光するレジストを塗布し(レジスト塗布工程)、このレジストを硬化させるために高温で処理し(プリベーク工程)、つぎにその上にマスクを載せて紫外線を照射する(露光工程)。この結果、マスク上のパターン模様のある部分は紫外線が照射されず塗布したレジストは硬くなるが、紫外線が照射された部分は塗布したレジストが軟らかくなる(このレジストをポジ型レジストと呼び、露光されていないレジストをネガ型レジストという)。この軟らかくなったレジストを現像液で除去する。その後、再び高温で焼き(ポストベーク)、つぎに不要の金属膜を除去するためのエッチングを行い、最後に、パターン形成のために使用したレジストを剥離液で除去する。本発明の目的は、このようにして発生する剥離液廃液(この剥離液廃液はレジストを0.1〜3質量%含有している)から剥離液を再生するための方法と装置を提供する点にある。 For example, in an array substrate manufacturing process such as a semiconductor manufacturing factory or a liquid crystal display panel manufacturing process, a metal film is formed and washed on a mother glass substrate, and a resist sensitive to ultraviolet rays is applied thereon (resist coating process). Is cured at a high temperature (pre-baking step), and then a mask is placed thereon and irradiated with ultraviolet rays (exposure step). As a result, the part with the pattern on the mask is not irradiated with ultraviolet light and the applied resist is hardened, but the part irradiated with ultraviolet light is softened (this resist is called a positive resist and exposed). Not resist is called negative resist). The softened resist is removed with a developer. Thereafter, baking is performed again at a high temperature (post-baking), etching is then performed to remove unnecessary metal films, and finally the resist used for pattern formation is removed with a stripping solution. The object of the present invention is to provide a method and an apparatus for regenerating a stripping solution from the stripping solution waste solution thus generated (this stripping solution waste solution contains 0.1 to 3% by mass of a resist). It is in.
本発明の第1は、液晶ディスプレイパネルの製造工程から排出されるレジストを含有する剥離液廃液からレジストを分離除去し、剥離液を再生する方法において、剥離液廃液中のレジスト重量に対し0.01〜0.2倍重量のアルカリを添加することを特徴とする剥離液の再生方法に関する。
本発明の第2は、前記アルカリは水溶液の形で添加するものである請求項1記載の剥離液の再生方法に関する。
本発明の第3は、アルカリの添加と同時にまたはアルカリの添加に先立ち、剥離液廃液を露光処理するものである請求項1または2記載の剥離液の再生方法に関する。
本発明の第4は、アルカリを添加する位置が、レジスト(高沸点成分)分離工程の前の段階である請求項1〜3いずれか記載の剥離液の再生方法に関する。
本発明の第5は、液晶ディスプレイパネルの製造工程から排出されるレジストを含有する剥離液廃液からレジストを分離除去し、剥離液を再生する装置が、
低沸点物除去塔、薄膜式蒸発器および剥離液精製塔の順序で剥離液廃液を流す場合は、前記薄膜式蒸発器またはそれより前の段階(精製剥離液ラインを含めてこれより前の段階)のいずれかの装置またはそれらの装置の連結部分に剥離液廃液中のレジスト重量に対し0.01〜0.2倍重量のアルカリを添加する手段を設けるか、
または薄膜式蒸発器、低沸点物除去塔および剥離液精製塔の順序で剥離液廃液を流す場合は、低沸点物除去塔またはそれより前の段階(精製剥離液ラインを含めてこれより前の段階)のいずれかの装置またはそれらの装置の連結部分に剥離液廃液中のレジスト重量に対し0.01〜0.2倍重量のアルカリを添加する手段を設ける
ことを特徴とする剥離液の再生装置に関する。
本発明の第6は、液晶ディスプレイパネルの製造工程から排出されるレジストを含有する剥離液廃液からレジストを分離除去し、剥離液を再生する装置において、低沸点物除去塔、第1リボイラー、低沸点物除去塔の低部と第1リボイラーの低部とを連結する配管、低沸点物除去塔の上部から排出したガスを処理するための第1コンデンサー、第1コンデンサーの下部から排出した処理液を低沸点物除去塔の上部に供給するための配管、第2リボイラー、低沸点物除去塔の低部から回収した低沸点物を含有しない剥離液廃液を第2リボイラーの下部に供給するための配管、剥離液精製塔、第2リボイラーで発生した蒸気をその上部から剥離液精製塔の下部に供給するための配管、薄膜式蒸発器、剥離液精製塔の下部から排出された低沸点物を含有しない剥離液廃液を薄膜式蒸発器の上部に供給するための配管、薄膜式蒸発器の下部から排出した処理液の一部を薄膜式蒸発器の上部に供給するための配管、薄膜式蒸発器の下部から排出した処理液をレジスト含有高沸点成分として回収するための配管、剥離液精製塔の上部から排出されたガスを処理するための第2コンデンサー、第2コンデンサーの下部から排出した精製剥離液を回収するための配管、前記精製剥離液の一部を剥離液精製塔の上部に戻すための配管、前記薄膜式蒸発器またはそれより前の段階(精製剥離液ラインを含めてこれより前の段階)のいずれかの装置またはそれらの装置の連結部分に剥離液廃液中のレジスト重量に対し0.01〜0.2倍量のアルカリを添加する手段を設けることを特徴とする剥離液の再生装置に関する。
本発明の第7は、剥離液廃液の流れからみてアルカリを添加する手段が設けられている場所より前の場所に、剥離液廃液を光照射するための露光手段を設けたものである請求項5または6記載の剥離液の再生装置に関する
A first aspect of the present invention is a method of separating and removing a resist from a stripping solution waste solution containing a resist discharged from a liquid crystal display panel manufacturing process, and regenerating the stripping solution, and regenerating the stripping solution with respect to the resist weight in the stripping solution waste solution. The present invention relates to a method for regenerating a stripping solution, which comprises adding 01 to 0.2 times the weight of alkali.
A second aspect of the present invention relates to the method for regenerating a stripping solution according to
A third aspect of the present invention relates to a method for regenerating a stripping solution according to
The fourth aspect of the present invention relates to the method for regenerating a stripping solution according to any one of
The fifth aspect of the present invention is an apparatus for separating and removing a resist from a stripping liquid waste liquid containing a resist discharged from a liquid crystal display panel manufacturing process,
When the stripping solution waste liquid is flowed in the order of the low boiling point removal tower, the thin film evaporator, and the stripping liquid purification tower, the thin film evaporator or the previous stage (including the purification stripping liquid line and the previous stage) ) Or a connecting part of these devices is provided with a means for adding 0.01 to 0.2 times the weight of alkali with respect to the resist weight in the stripping solution waste solution,
Or when the stripping solution waste liquid is flowed in the order of thin film evaporator, low boiling point removal column and stripping solution purification column, low boiling point stripping column or an earlier stage (including the purification stripping solution line and earlier) Regeneration of the stripping solution, characterized in that means for adding 0.01 to 0.2 times the weight of alkali with respect to the resist weight in the stripping solution waste solution is provided at any one of the devices in the step) or a connecting portion of these devices Relates to the device.
According to a sixth aspect of the present invention, there is provided an apparatus for separating and removing a resist from a stripping solution waste solution containing a resist discharged from a liquid crystal display panel manufacturing process, and regenerating the stripping solution, wherein a low boiling point removal tower, a first reboiler, A pipe connecting the lower part of the boiling point removal tower and the lower part of the first reboiler, a first condenser for treating the gas discharged from the upper part of the low boiling point removal tower, and a processing liquid discharged from the lower part of the first condenser For supplying to the lower part of the second reboiler a pipe for supplying the lower boilers to the upper part of the low boilers, the second reboiler, and the stripping liquid waste liquid containing no low boilers recovered from the lower part of the low boilers removing tower Piping, stripping liquid purification tower, piping for supplying vapor generated in the second reboiler to the lower part of the stripping liquid purification tower, thin film evaporator, low boiling point substances discharged from the bottom of the stripping liquid purification tower Pipe for supplying the stripping liquid waste liquid that does not have to the upper part of the thin film evaporator, pipe for supplying a part of the processing liquid discharged from the lower part of the thin film evaporator to the upper part of the thin film evaporator, thin film evaporation For recovering the processing liquid discharged from the lower part of the vessel as a resist-containing high-boiling component, the second condenser for treating the gas discharged from the upper part of the stripping liquid purification tower, and the purification discharged from the lower part of the second condenser Piping for recovering the stripping solution, piping for returning a part of the purified stripping solution to the upper part of the stripping solution purification tower, the thin film evaporator or the previous stage (including the purified stripping solution line) A stripping solution characterized in that means for adding 0.01 to 0.2 times the amount of alkali with respect to the resist weight in the stripping solution waste solution is provided in any of the devices in the previous step) or in a connecting portion of these devices. Playback On location.
According to a seventh aspect of the present invention, there is provided an exposure means for irradiating the stripping solution waste liquid with light at a location before the location where the means for adding alkali is provided in view of the flow of the stripping solution waste liquid. The apparatus for regenerating stripping liquid according to 5 or 6
液晶ディスプレイパネルの製造工程において使用される剥離液は、技術の進歩、製作コストの観点から、モノエタノールアミン(以下MEAと称することがある)とジメチルスルフォキシド(以下DMSOと称することがある)の混合溶剤(剥離液)からMEAとジエチレングリコールモノブチルエーテル(以下BDGと称することがある)の混合溶剤(剥離液)へと移行している傾向にある。 The stripping solution used in the manufacturing process of the liquid crystal display panel is monoethanolamine (hereinafter sometimes referred to as MEA) and dimethyl sulfoxide (hereinafter sometimes referred to as DMSO) from the viewpoint of technological progress and production cost. The mixed solvent (stripping solution) of MEA and diethylene glycol monobutyl ether (hereinafter sometimes referred to as BDG) tends to shift to a mixed solvent (stripping solution).
前記剥離液廃液にアルカリを添加することによりレジストの剥離液に対する溶解度を増加させ、レジストの析出・付着を減少して、剥離液の回収率をアップすることができる。
また、前記アルカリ添加に加えて剥離液廃液の全体に蛍光灯のごとき紫外線(波長10−9m)〜可視光線〜赤外線(波長10−4m)の波長を持つ光を露光することが好ましい。これにより、未反応レジストを反応させレジストをよりアルカリに溶け易い状態に変えて、レジストの析出・付着を減少して、剥離液の回収率をアップすることができる。
By adding alkali to the stripping solution waste solution, the solubility of the resist in the stripping solution can be increased, and the deposition and adhesion of the resist can be decreased, thereby increasing the stripping solution recovery rate.
Further, in addition to the alkali addition, it is preferable to expose the entire stripping solution waste liquid with light having a wavelength of ultraviolet rays (wavelength 10 −9 m) to visible rays to infrared rays (wavelength 10 −4 m) such as a fluorescent lamp. As a result, the unreacted resist is reacted to change the resist into a state in which it can be more easily dissolved in alkali, thereby reducing the deposition and adhesion of the resist and increasing the recovery rate of the stripping solution.
前記レジストの剥離液廃液(本発明においては、このなかに基盤洗浄液も包含しているものとして記載している)には、レジスト剥離工程において用いられる各種の溶剤、例えば、レジストを除去するための剥離液や、基盤の洗浄に用いられるシンナー等を含んでいる。レジストの剥離液としては、例えば、モノエタノールアミン(MEA)、ジエチレングリコールモノブチルエーテル(BDG)、ジメチルスルフォキシド(DMSO)、プロピレングリコールモノメチルエーテルアセテート(以下PGMEAと称することがある)などの1〜数種の混合物であり、レジストに対して高い溶解度を持つ溶剤である。前記レジストの剥離液としてよく使用されているものとしては、MEAとDMSO、あるいはMEAとBDGを所定の比率で混合したものであり、また基盤洗浄のシンナーとしては、例えば、PGMEAとプロピレングリコールモノメチルエーテル(PGME)を混合した溶剤などが代表的なものである。 The resist stripping solution waste liquid (in the present invention, it is described as including a base cleaning solution in the present invention) includes various solvents used in the resist stripping step, for example, for removing the resist. Contains stripping solution and thinner used to clean the substrate. Examples of resist stripping solutions include 1 to several such as monoethanolamine (MEA), diethylene glycol monobutyl ether (BDG), dimethyl sulfoxide (DMSO), and propylene glycol monomethyl ether acetate (hereinafter sometimes referred to as PGMEA). It is a mixture of seeds and a solvent with high solubility in resist. Often used as a resist stripping solution is a mixture of MEA and DMSO or MEA and BDG at a predetermined ratio. As a substrate cleaning thinner, for example, PGMEA and propylene glycol monomethyl ether A solvent mixed with (PGME) is a typical one.
前記剥離液廃液に添加するアルカリとしては、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウム等の無機アルカリ、テトラメチルアンモニウムハイドロオキサイド等の有機アルカリなどを挙げることができる。その添加量は、ナトリウム換算で剥離液廃液の不揮発分(レジスト)に対して0.01〜0.2倍重量である。
アルカリの添加手段は、水に溶解したアルカリ水溶液を連続定量的に供給することもできるし、装置内貯留部に回分定量的に添加することもできる。アルカリは固体や液体など任意の形で水とアルカリ調整槽内で攪拌機により均一に混合して調整する。水酸化ナトリウムのような固体アルカリを投入する場合は一定濃度に濃度調整をアルカリ濃度検出器で検出し補給水の量を調整する。アルカリの添加量は、調整したアルカリの濃度、剥離液中のレジスト濃度によって決まる。
Examples of the alkali added to the stripping solution waste liquid include inorganic alkalis such as sodium hydroxide, potassium hydroxide and sodium carbonate, and organic alkalis such as tetramethylammonium hydroxide. The addition amount is 0.01 to 0.2 times the weight of the non-volatile content (resist) of the stripping solution waste liquid in terms of sodium.
As the means for adding alkali, an aqueous alkali solution dissolved in water can be supplied continuously and quantitatively, or it can be added batchwise and quantitatively to the reservoir in the apparatus. The alkali is adjusted by mixing uniformly with water and an alkali adjusting tank with a stirrer in any form such as solid or liquid. When a solid alkali such as sodium hydroxide is added, the concentration is adjusted to a constant concentration with an alkali concentration detector and the amount of makeup water is adjusted. The amount of alkali added is determined by the adjusted alkali concentration and the resist concentration in the stripping solution.
前記剥離液廃液の全体に蛍光灯のごとき紫外線(波長10−9m)〜可視光線〜赤外線(波長10−4m)の波長を持つ光線を露光する時間は、液深10mmの上面より露光した場合、1〜6000秒、好ましくは300〜1200秒である。
また、系を露光する具体的手段としては、所望の箇所に例えば透明なパイレックス(登録商標)状硝子管又は露光装置(覗窓など採光部を含む)を設け、内部を通過する剥離液廃液に前記波長を持つ光線を露光するなどの手段を挙げることができる。露光強度(光束)は800ルーメン以上、好ましくは1000ルーメン以上である。
The exposure time of the light having a wavelength of ultraviolet light (wavelength 10 −9 m) to visible light to infrared light (wavelength 10 −4 m), such as a fluorescent lamp, was exposed from the upper surface having a liquid depth of 10 mm. In the case, it is 1 to 6000 seconds, preferably 300 to 1200 seconds.
Further, as a specific means for exposing the system, for example, a transparent Pyrex (registered trademark) glass tube or an exposure device (including a daylighting portion such as a viewing window) is provided at a desired location, and the stripping liquid waste liquid passing through the interior is disposed. A means such as exposing a light beam having the wavelength can be used. The exposure intensity (light flux) is 800 lumens or more, preferably 1000 lumens or more.
本発明における剥離液廃液に含有されている低沸点不純物とは、剥離液成分より低い沸点を有する不純物であり、典型的には、剥離液廃液に含有されている水や剥離液に溶解している炭酸ガスである。また、本発明における剥離液廃液に含有されている高沸点不純物とは剥離液成分よりも高い沸点を有する不純物を指し、具体的にはフォトレジストを挙げることができる。 The low boiling point impurities contained in the stripping liquid waste liquid in the present invention are impurities having a boiling point lower than that of the stripping liquid component, and typically dissolved in water or stripping liquid contained in the stripping liquid waste liquid. Is carbon dioxide. Moreover, the high boiling point impurity contained in the stripping solution waste liquid in the present invention refers to an impurity having a boiling point higher than that of the stripping solution component, and specifically includes a photoresist.
以下、本発明について図面を用いて詳しく説明する。 Hereinafter, the present invention will be described in detail with reference to the drawings.
図1に本発明の特徴であるアルカリ添加をしない場合のレジスト剥離液廃液の再生・再生装置の代表的なフローシートの一例を概略図として示す。剥離液廃液は低沸物除去塔(T−1)の中間部に供給され、留出分として水・炭酸ガスなどの低沸点不純物を除去する。塔底部からは排出物として、剥離液・レジスト・金属・微粒子が排出される。この排出物は、リボイラー(RB−2)下部に供給され、一部の剥離液は蒸発しながら塔下部からポンプにより薄膜式蒸発器(FD−1)に送られ大部分の剥離液を蒸発し、レジスト・金属・微粒子は不揮発物であるので蒸発しないため少量の剥離液とともに高沸点成分として系外に排出される。剥離液精製塔(T−2)では、これら高沸点成分と剥離液を精密に精留分離できるので、塔頂からはリサイクル可能な剥離液が留出する。T−1は内部に充填物を具備した減圧操作による低沸点物除去塔、T−2は内部に充填物を具備した減圧操作による連続精製塔の形態をしており、これにより剥離液と低沸点成分及び剥離液を容易に分離精製することが出来る。壁面掻き取り式流下薄膜式蒸発器(FD−1)では効率的に高沸点成分から剥離液を分離蒸発することができる。
しかし、図1における従来のこの方式では、スチームによる加熱温度・滞留時間などの影響を受け、高沸点成分が析出し、壁面に付着する。付着する場所は、処理液が滞留する場所、及び、レジストが高度濃縮される場所で温度が高い(125℃以上)場所である。具体的には、図1においては、とくにリボイラー(RB−2)、薄膜式蒸発器(FD−1)の容器壁面である。このため、従来の装置においては、処理能力の低下を招き、定期的な洗浄・メンテナンスを必要としている。
FIG. 1 is a schematic diagram showing an example of a typical flow sheet of a resist stripping liquid waste regeneration / regeneration apparatus without adding an alkali, which is a feature of the present invention. The stripping solution waste liquid is supplied to the middle part of the low boiling point removal tower (T-1), and removes low boiling point impurities such as water and carbon dioxide as a distillate. Stripping solution, resist, metal, and fine particles are discharged from the bottom of the tower as discharge. This discharge is supplied to the lower part of the reboiler (RB-2), and a part of the stripping solution is sent to the thin film evaporator (FD-1) from the lower part of the tower while evaporating to evaporate most of the stripping solution. Since resist, metal, and fine particles are non-volatile, they do not evaporate and are discharged out of the system as a high boiling point component together with a small amount of stripping solution. In the stripping solution purification tower (T-2), these high-boiling components and stripping liquid can be precisely rectified and separated, so that a recyclable stripping liquid is distilled from the top of the tower. T-1 is in the form of a low boiling point removal tower by a decompression operation equipped with a packing inside, and T-2 is in the form of a continuous purification tower by a decompression operation equipped with a packing inside, thereby reducing the separation liquid and low Boiling components and stripping solutions can be easily separated and purified. The wall scraping type falling film evaporator (FD-1) can efficiently separate and evaporate the stripping liquid from the high boiling point component.
However, in this conventional system shown in FIG. 1, high boiling point components are deposited and adhered to the wall surface under the influence of the heating temperature and residence time due to steam. The places where the treatment liquid stays and the places where the resist is highly concentrated are places where the temperature is high (125 ° C. or higher). Specifically, in FIG. 1, it is a container wall surface of a reboiler (RB-2) and a thin film evaporator (FD-1). For this reason, in the conventional apparatus, the processing capacity is reduced and regular cleaning and maintenance are required.
本発明者らはこの問題を鋭意研究し、レジストの析出・付着を減少させる次の手段を見出した。即ち、剥離液廃液ラインの最適な箇所に、水酸化ナトリウム、水酸化カリウム、炭酸ナトリウムなどの無機アルカリ、テトラメチルアンモニウムハイドロオキサイドなどの有機アルカリの水溶液を剥離液廃液中の不揮発分(レジスト)の0.01〜0.2倍重量に相当する量を添加する手段を採用することである。また、この手段に加えて、剥離液廃液の全量に蛍光灯のごとき紫外線〜可視光線〜赤外線(波長10−9m〜10−4m)を露光する手段を併用することができる。
これにより、レジストの析出・壁面付着を防止して、精製剥離液の再生をアップし、更には、定期的な洗浄及びメンテナンスの省略が実現できた。
The present inventors diligently studied this problem and found the following means for reducing the deposition and adhesion of resist. In other words, an aqueous solution of an inorganic alkali such as sodium hydroxide, potassium hydroxide or sodium carbonate, or an organic alkali such as tetramethylammonium hydroxide is applied to an optimum part of the stripping liquid waste liquid line. It is to adopt a means for adding an amount corresponding to 0.01 to 0.2 times the weight. In addition to this means, a means for exposing ultraviolet rays to visible rays to infrared rays (wavelengths of 10 −9 m to 10 −4 m) such as a fluorescent lamp can be used in combination with the total amount of the stripping solution waste liquid.
As a result, resist precipitation and wall surface adhesion were prevented, and the purified stripping solution was regenerated. Further, periodic cleaning and maintenance could be omitted.
図2〜5に本発明の基本的な実施態様を示す。
図2においては、低沸点物除去塔、薄膜式蒸発器および剥離液精製塔の順序で配列されており、アルカリ水溶液は、(い)剥離液廃液が低沸点物除去塔あるいは薄膜式蒸発器に入る前の段階で添加するか、(ろ)薄膜式蒸発器における循環工程中で添加することができる。また必要に応じて行う露光は、前記(い)の場合は、アルカリ水溶液添加の前の段階で、前記(ろ)の場合は、後述の薄膜式蒸発器の内部の壁面で行うことができる。
図3〜5の場合は、薄膜式蒸発器、低沸点物除去塔および剥離液精製塔の順序で配列されており、アルカリ水溶液は、(い)剥離液廃液が低沸点物除去塔に入る前の段階で添加するか、(は)薄膜式蒸発器を出て低沸点物除去塔に入る前の段階で添加する。また、必要に応じて行う露光は、前記(い)の場合は、前記(い)の添加を行う前の段階で、(は)の場合は、後述の薄膜式蒸発器の内部の壁面において、または薄膜式蒸発器と低沸点物除去塔の間のアルカリ添加を行う前の段階において光照射を行うことができる。
なお、露光をアルカリ水溶液の添加後に行っても、系中にはアルカリが存在しているから、これでも充分目的を達成することができる。
2 to 5 show a basic embodiment of the present invention.
In FIG. 2, the low boiling point removal tower, the thin film evaporator, and the stripping liquid purification tower are arranged in this order. The alkaline aqueous solution is (i) the stripping liquid waste liquid is transferred to the low boiling point removal tower or the thin film evaporator. It can be added at the stage before entering, or can be added during the circulation process in the thin film evaporator. In addition, in the case of (ii), the exposure performed as necessary can be performed at the stage before the addition of the alkaline aqueous solution, and in the case of (b), exposure can be performed on the inner wall surface of a thin film evaporator described later.
In the case of FIGS. 3 to 5, they are arranged in the order of a thin film evaporator, a low boiler removal tower and a stripping liquid purification tower, and the alkaline aqueous solution is (ii) before the stripping liquid waste liquid enters the low boiler removal tower. Or is added at the stage before exiting the thin film evaporator and entering the low boiler removal column. In addition, in the case of (ii), the exposure performed as necessary is a stage before the addition of (ii), and in the case of (ha), on the inner wall surface of the thin film evaporator described later, Alternatively, the light irradiation can be performed before the alkali addition between the thin film evaporator and the low boiler removal column.
Even if the exposure is performed after the addition of the aqueous alkali solution, since the alkali exists in the system, the purpose can be sufficiently achieved.
図6は、本発明の代表的なフローシートを示す。図中〔1〕の表示は、アルカリ水溶液を添加する1つの具体的箇所を例示するものであり、〔2〕の表示は、蛍光灯などの光線を露光する1つの具体的箇所を例示するものである。なお、装置と装置を結ぶ配管部分で露光するためには、配管の所望個所に光線を透過することができる部分を設けることができる。また、薄膜式蒸発器(FD−1)などの装置においてはその装置に具備した覗き窓のような光線が透過可能な個所を介して照射露光することもできる。
簡単に処理液の流れを説明すると、使用済の剥離液廃液は剥離液廃液ラインから低沸点物除去塔T−1に送られ、水と二酸化炭素、その他の低沸点成分はライン(a)により低沸点物除去塔T−1の上方から排出し、一方、高沸点成分を主成分とする剥離液は低沸点物除去塔T−1下方のライン(b)から排出される。排出された高沸点成分を主成分とする剥離液は第2リボイラーRB−2を経て剥離液精製塔T−2に送られる。ここで主成分の一部は精製され、第2コンデンサーRB−2で液化されてライン(c)から精製剥離液として回収される。剥離液精製塔T−2の下部から回収したレジストを含む剥離液廃液は
ライン(d)を通って薄膜式蒸発器FD−1へと送られる。薄膜式蒸発器FD−1では掻き取り式の薄膜蒸発機構によって、レジスト成分は薄膜となり、レジストを分離した剥離液は蒸発し、薄膜式蒸発器FD−1の上部からライン(e)を通って剥離液精製塔T−2の中段に供給され、ここで精製されて第2コンデンサーRB−2で液化されてライン(c)から精製剥離液として回収される。不要なレジスト含有廃液は薄膜式蒸発器FD−1の下部からライン(f)へ排出する。
このように低沸点物除去塔T−1、剥離液精製塔T−2、剥離液とレジストを限界まで分離するための薄膜式蒸発器FD−1よりなる3種の異なる装置からなる剥離液回収装置において、例えば[I]〜[V]に示すような個所でアルカリを添加し、必要に応じて光照射を併用するものである。
FIG. 6 shows a representative flow sheet of the present invention. In the figure, the indication [1] exemplifies one specific location where an alkaline aqueous solution is added, and the indication [2] exemplifies one specific location where a light beam such as a fluorescent light is exposed. It is. In addition, in order to expose in the piping part which connects an apparatus to an apparatus, the part which can permeate | transmit a light beam can be provided in the desired location of piping. In addition, in an apparatus such as a thin film evaporator (FD-1), irradiation exposure can be performed through a portion such as a viewing window provided in the apparatus through which light can be transmitted.
Briefly explaining the flow of the treatment liquid, 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 water, carbon dioxide, and other low boiling point components are fed through the line (a). The stripping liquid mainly containing the high boiling point component is discharged from the line (b) below the low boiling point removal tower T-1 while being discharged from above the low boiling point removal tower T-1. The stripping solution mainly composed of the discharged high boiling point component is sent to the stripping solution purification tower T-2 via the second reboiler RB-2. Here, a part of the main component is purified, liquefied by the second condenser RB-2, and recovered from the line (c) as a purified stripping solution. The stripping liquid waste liquid containing the resist recovered from the lower part of the stripping liquid purification tower T-2 is sent to the thin film evaporator FD-1 through the line (d). In the thin film evaporator FD-1, the resist component becomes a thin film by the scraping-type thin film evaporation mechanism, and the stripping solution that has separated the resist evaporates from the upper part of the thin film evaporator FD-1 through the line (e). It is supplied to the middle stage of the stripping solution purification tower T-2, purified here, liquefied by the second condenser RB-2, and recovered from the line (c) as a purified stripping solution. Unnecessary resist-containing waste liquid is discharged from the lower part of the thin film evaporator FD-1 to the line (f).
As described above, the stripping liquid recovery unit T-3, stripping liquid purification column T-2, and stripping liquid recovery system composed of three different apparatuses comprising the stripping liquid and the thin film evaporator FD-1 for separating the resist to the limit. In the apparatus, for example, alkali is added at locations shown in [I] to [V], and light irradiation is used in combination as necessary.
前記薄膜式蒸発器FD−1においては、二重管の表面を、回転軸により回転するワイパーにより、薄膜式蒸発器の上部から供給された剥離液廃液が二重管の表面で薄膜状となり、剥離液廃液中の低沸点成分が効率よく気化し、高沸点成分は底部から排出される。 In the thin film evaporator FD-1, the surface of the double pipe is wiped off from the upper part of the thin film evaporator by a wiper that rotates around the rotating shaft. The low boiling point component in the stripping solution waste liquid is efficiently vaporized, and the high boiling point component is discharged from the bottom.
図6におけるアルカリを添加する場所の具体例
その1:剥離液廃液が低沸点物除去塔(T−1)に供給される以前の任意の場所
その2:第1コンデンサー(C−1)の下部からポンプを介して低沸点物除去塔(T−1
)の上部に送られる供給ライン(低沸点物除去塔の還流ライン)の任意の場所
その3:低沸点物除去塔(T−1)から第2リボイラー(RB−2)へつながるラインの
任意の場所
その4:剥離液精製塔(T−2)の下部から薄膜式蒸発器(FD−1)上部に送られる供
給ラインの任意の場所
その5:薄膜式蒸発器(FD−1)の下部から薄膜式蒸発器(FD−1)の上部に再循環
するためのラインの任意の場所
Specific example 1 of the place where alkali is added in FIG. 6 1: Any place before the stripping solution waste liquid is supplied to the low boiler removal tower (T-1) 2: Lower part of the first condenser (C-1) To a low boiler removal column (T-1
) Arbitrary part of the feed line (reflux line of the low boiler removal column) sent to the upper part of Part 3: Any line of the line leading from the low boiler removal column (T-1) to the second reboiler (RB-2) Location 4: Arbitrary location of the supply line sent from the lower part of the stripping liquid purification tower (T-2) to the upper part of the thin film evaporator (FD-1) Part 5: Lower part of the thin film evaporator (FD-1) Anywhere on the line to recirculate from to the top of the thin film evaporator (FD-1)
図6における光線を照射する場所の具体例
その1:剥離液廃液が低沸点物除去塔(T−1)に供給される以前の任意の場所
その2:第1コンデンサー(C−1)の下部からポンプを介して低沸点物除去塔(T−1
)の上部に送られる供給ライン(低沸点物除去塔の還流ライン)の任意の場所
その3:低沸点物除去塔(T−1)から第2リボイラー(RB−2)へつながるラインの
任意の場所
その4:剥離液精製塔(T−2)の下部から薄膜式蒸発器(FD−1)上部に送られる供
給ラインの任意の場所
その5:薄膜式蒸発器(FD−1)内部の壁面
Specific example of the place where the light beam is irradiated in FIG. 6 Part 1: Any place before the stripping solution waste liquid is supplied to the low boiler removal column (T-1) Part 2: The lower part of the first condenser (C-1) To a low boiler removal column (T-1
) Arbitrary part of the feed line (reflux line of the low boiler removal column) sent to the upper part of No. 3: Any line of the line leading from the low boiler removal column (T-1) to the second reboiler (RB-2) Location 4: Arbitrary location on the supply line sent from the lower part of the stripping liquid purification tower (T-2) to the upper part of the thin film evaporator (FD-1) Part 5: Inside the thin film evaporator (FD-1) Wall
本発明によれば、剥離液廃液ラインの最適な箇所に水溶性アルカリを剥離液廃液の不揮発分(レジスト)に対して1〜20重量%を添加することおよび必要に応じて剥離液廃液の全体に蛍光灯のごとき光線を露光することにより、レジストの析出・壁面付着を防止することができ、精製剥離液の回収率をアップし、更には、定期的な洗浄及びメンテナンスの軽減を可能とした。従来再生装置を用いた場合の精製剥離液の回収率(≒90%)を本発明により5%アップして再生できるようになったことは、高純度な電子工業用で使用可能な純度の高価な剥離液の補充量が減少し、経済的な価値を生み出し、洗浄及びメンテナンスの軽減により安定した装置運転が出来るという大きな効果を奏する。 According to the present invention, 1-20% by weight of water-soluble alkali is added to the optimum portion of the stripping solution waste liquid line with respect to the non-volatile content (resist) of the stripping solution waste solution, and if necessary, the entire stripping solution waste solution By exposing to light such as a fluorescent lamp, resist deposition and wall surface adhesion can be prevented, the recovery rate of the purified stripping solution can be increased, and regular cleaning and maintenance can be reduced. . The fact that the recovery rate (≈90%) of the purified stripping solution when using a conventional regenerator can be regenerated by 5% according to the present invention is high in purity that can be used in the high-purity electronics industry. The replenishment amount of the stripping solution is reduced, and economic value is produced, and there is a great effect that stable operation of the apparatus can be achieved by reducing cleaning and maintenance.
以下、実施例を示して本発明を更に具体的に説明するが、本発明はこれらの実施例により限定されるものではない。 EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
比較例1
図7は、実装置におけるレジストの析出・付着を実証するためのラボ試験装置である。
オイルバスで一定温度に加熱したビーカー内の剥離液廃液に試験片を投入して試験片に付着するレジストの量、及び付着状態を観察した。剥離液廃液は前もってロータリーエバポレーターで濃縮し、そのレジスト濃度は≒17重量%に調整した(この値は剥離液廃液に2重量%のレジストが含有された場合の剥離液回収率90重量%の場合である)。この実験においては、当然ながら、処理液に室内の光があたっている。
前記図7の実験装置を用い、剥離液廃液温度を120、130、140℃にそれぞれ保持し、時間と経過に従って付着量と単位面積あたりの付着量を測定した。その値を下記表1に示す。表1から分かるように、140℃では3時間から付着が認められ、130℃では6時間から付着が認められ、120℃では9時間から付着が認められる。付着物は褐色で硬く、炭化した状態であり、水洗浄、剥離液洗浄を行っても容易に除去することが出来なかった。更に剥離液廃液のレジストは加熱温度の影響が大きく、できるだけ低温加熱が必要なことがわかった。これは、装置内に剥離液が滞留するとレジストが熱影響を受け固化・炭化することが原因と思われる。このようにして本発明者らは実装置における付着の実態を熟知することが出来た。
Comparative Example 1
FIG. 7 is a laboratory test apparatus for demonstrating resist deposition and adhesion in an actual apparatus.
A test piece was put into the stripping solution waste liquid in a beaker heated to a constant temperature in an oil bath, and the amount of resist adhering to the test piece and the state of adhesion were observed. The stripping solution waste was concentrated in advance using a rotary evaporator, and the resist concentration was adjusted to approximately 17% by weight (this value is 90% by weight when the stripping solution waste contains 2% by weight of resist. Is). In this experiment, naturally, the processing liquid is exposed to light in the room.
Using the experimental apparatus shown in FIG. 7, the stripping solution waste liquid temperatures were maintained at 120, 130, and 140 ° C., respectively, and the amount of adhesion and the amount of adhesion per unit area were measured according to time and passage. The values are shown in Table 1 below. As can be seen from Table 1, adhesion was observed from 3 hours at 140 ° C., adhesion was observed from 6 hours at 130 ° C., and adhesion was observed from 9 hours at 120 ° C. The deposit was brown, hard and carbonized, and could not be easily removed even after washing with water and stripping solution. Furthermore, it was found that the resist of the stripping solution waste liquid is greatly affected by the heating temperature, and it is necessary to heat it as low as possible. This is presumably because if the stripping solution stays in the apparatus, the resist is thermally affected to solidify and carbonize. In this way, the present inventors were able to know the actual state of adhesion in the actual apparatus.
実施例1
そこで、本発明者らは前記した問題を解決する手段としてレジストが析出する前の段階でアルカリ添加またはそれに加えて光照射することが有効であることを以下の実施例により明らかにする。
表2は図7に示す試験と同様な試験器(ビーカーを使用しているから光照射が併用されているケースとなる)を使用して、剥離液廃液の原液に0.1重量%、0.05重量%(48重量%NaOH水溶液としての添加割合)の水酸化ナトリウム水溶液を添加し、ロータリーエバポレーターでレジスト濃度≒17重量%まで濃縮して前記と同様な試験を行った結果である。140℃では24時間で付着が認められ、30℃では34時間から付着が認められ、120℃では48時間から付着が認められた。付着物は薄い褐色の泥状物で、炭化した状態は見られず、水洗浄、剥離液洗浄により容易に除去することが出来た。付着するまでの時間も付着量も、共に比較例1の試験結果である表1のデータより良好な結果が得られていることが分かる。
Example 1
Therefore, the present inventors make it clear by the following examples that adding alkali or irradiating with light in the stage before the resist is deposited is effective as means for solving the above-mentioned problems.
Table 2 uses a tester similar to the test shown in FIG. 7 (because a beaker is used so that light irradiation is used in combination). This is a result of performing the same test as described above by adding 0.05 wt% (addition ratio as a 48 wt% NaOH aqueous solution) of an aqueous sodium hydroxide solution and concentrating the resist concentration to 17 wt% with a rotary evaporator. Adhesion was observed in 24 hours at 140 ° C., adhesion was observed in 34 hours at 30 ° C., and adhesion was observed in 48 hours at 120 ° C. The deposit was a light brown mud that was not carbonized and could be easily removed by washing with water and stripping solution. It can be seen that both the time until adhesion and the amount of adhesion are better than the data of Table 1 which is the test result of Comparative Example 1.
さらに、精製剥離液回収率をアップするため、同様に水酸化ナトリウムを添加した剥離液をロータリーエバポレーターでレジスト濃度≒31重量%まで濃縮し、同様な試験の結果を表3に示す。140℃では18時間から付着(目視による)が認められ、130℃では23時間から付着(目視による)が認められ、120℃では32時間から付着(目視による)が認められた。なお、表1〜3の付着量データは目視によるものではなく、定量的測定に基づくものである。付着物は褐色泥状で、炭化した状態が多少見られたが、水洗浄、剥離液洗浄により除去することが出来た。このようにレジストの濃度が高くなっても、表1の結果より良好な結果が確認され、アルカリを添加した効果が顕著であることが確認された。 Further, in order to increase the recovery rate of the purified stripping solution, the stripping solution to which sodium hydroxide was added was similarly concentrated to a resist concentration ≈31% by weight using a rotary evaporator, and the results of a similar test are shown in Table 3. Adhesion (visual observation) was observed from 140 hours at 140 ° C., adhesion (visual observation) was observed from 23 hours at 130 ° C., and adhesion (visual observation) was observed from 32 hours at 120 ° C. In addition, the adhesion amount data in Tables 1 to 3 are not based on visual observation but based on quantitative measurement. The deposit was brown mud and some carbonization was observed, but it could be removed by washing with water and stripping solution. Thus, even when the resist concentration was high, a better result than the result of Table 1 was confirmed, and it was confirmed that the effect of adding alkali was remarkable.
実施例2、比較例2
更に本発明者らは、図6の導入部分における剥離液廃液のレジストは液晶製造工程などにおいて露光されたレジストと露光されていないレジストが混在している。この差がレジストの析出・付着に影響を与える可能性がある。そこで本実験装置では図示されていない剥離液廃液貯槽につづく本発明の再生装置のすべてがステンレスで遮光(一部覗き窓などから露光されるが)状態にあるものを用いた。前記比較例1及び実施例1は、室内のビーカー試験であるため剥離液は露光された実験である。
Example 2 and Comparative Example 2
Further, the inventors of the present invention have a resist of the stripping liquid waste at the introduction portion in FIG. 6 in which a resist exposed in a liquid crystal manufacturing process or the like and a resist not exposed are mixed. This difference may affect resist deposition and adhesion. Therefore, in the present experimental apparatus, all of the regenerating apparatus of the present invention following a stripping liquid waste liquid storage tank not shown in the figure is made of stainless steel and is in a state of being shielded from light (partially exposed from a viewing window or the like). Since the comparative example 1 and the example 1 are indoor beaker tests, the stripping solution is an exposed experiment.
本試験は、いずれのケースも、まずロータリーエバポレーターでレジスト濃度≒15重量%まで濃縮する。ついで、(1)水酸化ナトリウム無添加(比較例2)、(2)(実施例2−1)水酸化ナトリウムを剥離液廃液換算で0.05重量%添加するが、露光はしない。(実施例2−2)水酸化ナトリウムを剥離液廃液換算で0.05重量%添加し、かつ露光を1.0分間行う。(実施例2−3)水酸化ナトリウムを剥離液廃液換算で0.05重量%添加し、かつ露光を10.0分間行う。その後、それぞれの試験片を140℃オイルバスで加熱されている濃縮液含有容器に投入し、48時間保持した。これらの試験はすべて暗室の中で行った。 In this test, in all cases, the resist concentration is first concentrated to 15% by weight using a rotary evaporator. Next, (1) sodium hydroxide is not added (Comparative Example 2), (2) (Example 2-1) Sodium hydroxide is added in an amount of 0.05% by weight in terms of the stripping solution waste liquid, but exposure is not performed. (Example 2-2) Sodium hydroxide is added in an amount of 0.05% by weight in terms of stripping solution waste liquid, and exposure is performed for 1.0 minute. (Example 2-3) Sodium hydroxide is added in an amount of 0.05% by weight in terms of a stripping solution waste solution, and exposure is performed for 10.0 minutes. Thereafter, each test piece was put into a concentrate-containing container heated in a 140 ° C. oil bath and held for 48 hours. All these tests were performed in a dark room.
表4は、前記露光試験の結果を示した表である。(i)水酸化ナトリウム無添加の場合は付着量が8.35mg/cm2、(ii)水酸化ナトリウム添加、露光無しは4.46mg/cm2、(iii)水酸化ナトリウム添加、露光10.0minは4.02mg/cm2と露光によるレジストの析出・付着が減少することが分かり、水又は剥離液による洗浄も水酸化ナトリウム無添加の場合より著しく容易になっていることが分かった。 Table 4 shows the results of the exposure test. (I) In the case of no addition of sodium hydroxide, the adhesion amount was 8.35 mg / cm 2 , (ii) Addition of sodium hydroxide, no exposure, 4.46 mg / cm 2 , (iii) Addition of sodium hydroxide, exposure 10. 0 min was 4.02 mg / cm 2 , indicating that the resist deposition and adhesion due to exposure decreased, and that cleaning with water or a stripping solution was significantly easier than when no sodium hydroxide was added.
実施例3
図8は、水溶性無機アルカリ添加装置の1実施例を示す。アルカリは請求項3のアルカリで固体、液体などを使用し、アルカリ調整槽で攪拌機により均一に混合される。水酸化ナトリウムの場合は一定濃度に濃度調整をアルカリ濃度検出器で検出し補給水の量を調整する。水酸化ナトリウムの添加量は、調整した水酸化ナトリウムの濃度、剥離液中のレジスト濃度によって決まる。剥離液廃液への供給は定量ポンプを用い、図6で示した〔1〕の箇所(供給ラインから精製剥離液ラインの最適な箇所)の配管ラインに供給する。供給位置の後方にスタティックミキサーなど水酸化ナトリウム水溶液と剥離廃液が混合する機構を具備させる。図8は、1実施例であり、一定濃度の調整済み水酸化ナトリウム水溶液の供給が可能であれば定量ポンプのみでアルカリ調整槽は省くことが出来る。
Example 3
FIG. 8 shows one embodiment of a water-soluble inorganic alkali adding apparatus. The alkali used in the third aspect is a solid, a liquid, or the like, and is uniformly mixed by a stirrer in an alkali adjusting tank. In the case of sodium hydroxide, the concentration adjustment to a constant concentration is detected by an alkali concentration detector and the amount of makeup water is adjusted. The amount of sodium hydroxide added is determined by the adjusted sodium hydroxide concentration and the resist concentration in the stripping solution. Supply to the stripping liquid waste liquid is supplied to the piping line at [1] shown in FIG. 6 (from the supply line to the optimum position of the purified stripping liquid line) using a metering pump. A mechanism for mixing the sodium hydroxide aqueous solution and the stripping waste liquid, such as a static mixer, is provided behind the supply position. FIG. 8 shows an embodiment, and the alkali adjustment tank can be omitted with only a metering pump if it is possible to supply an adjusted aqueous sodium hydroxide solution having a constant concentration.
実施例4
図9及び図10は、露光装置の2つの実施例を示す。図9は配管ライン中に露光装置を挿入した1実施例で配管途中に光線を透過するパイレックス(登録商標)硝子の如き配管に変更し、その管の両面から蛍光灯のような紫外線(波長10−9m)〜可視光線〜赤外線(波長10−4m)の波長を持つ光を露光し、未反応レジストを反応させる装置である。実装置では蛍光灯を使用して、5min間露光するため約8mの長さとした。図10は図6に示すFD−1の覗き窓を利用して紫外線を露光する機構で、上下の覗き窓4箇所に設置した。FD−1攪拌付き流下薄膜式蒸発装置は攪拌機に取り付けたフラッパーにより剥離液廃液を蒸発器壁面に1mm程度の膜厚に均一分散することができるので、液深さによる露光の減衰の影響が無く、光量が少なくても均一な露光ができる。
Example 4
9 and 10 show two embodiments of the exposure apparatus. FIG. 9 shows an embodiment in which an exposure apparatus is inserted in the piping line, and the piping is changed to a piping such as Pyrex (registered trademark) glass that transmits light in the middle of the piping. It is an apparatus that exposes light having a wavelength of −9 m) to visible light to infrared light (wavelength 10 −4 m) to react with an unreacted resist. In the actual apparatus, a fluorescent lamp was used, and the length was about 8 m for exposure for 5 minutes. FIG. 10 shows a mechanism that exposes ultraviolet rays using the FD-1 viewing window shown in FIG. 6 and is installed at four upper and lower viewing windows. FD-1 Flowing thin film evaporator with stirring can disperse stripping solution waste liquid to a thickness of about 1 mm on the evaporator wall surface by a flapper attached to the stirrer, so there is no influence of exposure attenuation due to the liquid depth. Even with a small amount of light, uniform exposure can be performed.
実施例6
実施例4、実施例6のアルカリ添加装置と露光装置を図6の実装値に取り付け、取り付ける前と比較し、実証した。アルカリ添加装置は「II」の配管途中に挿入した。露光装置は図6に示す水銀灯をFD−1攪拌機付き蒸発装置に設置しているΦ150覗き窓を利用し上下各2箇所(合計4箇所)に設置し、1000ルーメンで露光した。
Example 6
The alkali addition apparatus and the exposure apparatus of Example 4 and Example 6 were attached to the mounting values shown in FIG. The alkali addition device was inserted in the middle of the piping of “II”. The exposure apparatus was installed at two upper and lower positions (total of four positions) using a mercury lamp shown in FIG. 6 in a Φ150 viewing window installed in an evaporator with an FD-1 stirrer, and exposed at 1000 lumens.
本剥離液再生装置の所定処理量は、540kg/hで組成分析値は、剥離液476kg/h、レジスト他高沸物10kg/h、水他低沸物54kg/hであった。48重量%水酸化ナトリウム添加量は、540×0.0005=0.27kg/hを定量的に挿入・供給した。
精製再生量をそれぞれの条件で比較する。
アルカリ添加も露光も無いの現状の操作について
精製剥離液の平均回収率は≒88重量%の419kg/hであったが、FD−1壁面付着及びFD−1下部の液溜部にレジストの析出・付着が発生し、定期的(1回/3日の自動水洗浄・1回/年の分解を伴う)なメンテナンスを必要とした。
アルカリ添加による改善効果について(露光無し)
レジストの剥離液に対する溶解度を増加させ、レジストの析出・付着を減少して、剥離液の回収率をアップすることができる。精製剥離液の平均回収率は≒90重量%の428kg/hが定量的に安定した状態で再生できた。FD−1壁面付着及びFD−1下部の液溜部のレジスト析出・付着は殆ど見られなかったが、定期的(1回/3日の自動水洗浄)な洗浄は必要であった。
アルカリ添加+露光による改善効果について
精製剥離液の平均回収率は≒95重量%の452kg/hが定量的に安定した状態で再生できた。FD−1壁面付着及びFD−1下部の液溜部のレジスト析出・付着は殆ど見られなかったが、定期的(1回/3日の自動水洗浄)な洗浄は最悪の事態を回避するため行っている。
The predetermined throughput of this stripping solution regenerating apparatus was 540 kg / h, and the composition analysis values were stripping solution 476 kg / h, resist and other high boiling materials 10 kg / h, and water and other low boiling materials 54 kg / h. The amount of 48 wt% sodium hydroxide added was quantitatively inserted and supplied at 540 × 0.0005 = 0.27 kg / h.
The amount of purified regeneration is compared under each condition.
Current operation with no addition of alkali and no exposure The average recovery rate of the purified stripper was 419 kg / h, approximately 88% by weight, but the FD-1 wall surface was deposited and the resist deposited on the liquid reservoir at the bottom of the FD-1 -Adherence occurred, and regular maintenance (with automatic water cleaning once every 3 days and once / year disassembly) was required.
Improvement effect by adding alkali (no exposure)
The solubility of the resist in the stripping solution can be increased, the resist deposition and adhesion can be decreased, and the recovery rate of the stripping solution can be increased. An average recovery rate of the purified stripping solution was approximately 90% by weight of 428 kg / h, and was regenerated in a quantitatively stable state. Almost no FD-1 wall adhesion or resist deposition / adhesion in the liquid reservoir at the bottom of FD-1 was observed, but periodic (1/3 automatic water cleaning) cleaning was necessary.
About improvement effect by addition of alkali + exposure The average recovery rate of the purified stripping solution was approximately 95% by weight of 452 kg / h, and could be regenerated in a quantitatively stable state. Almost no FD-1 wall adhesion or resist deposition / adhesion on the liquid reservoir at the bottom of FD-1 was observed, but periodic (1/3 day automatic water cleaning) cleaning is to avoid the worst situation. Is going.
FD−1 薄膜式蒸発器
T−1 低沸点物除去塔
T−2 剥離液精製塔
FD-1 Thin film evaporator T-1 Low boiling point removal tower T-2 Stripping liquid purification tower
Claims (7)
低沸点物除去塔、薄膜式蒸発器および剥離液精製塔の順序で剥離液廃液を流す場合は、前記薄膜式蒸発器またはそれより前の段階(精製剥離液ラインを含めてこれより前の段階)のいずれかの装置またはそれらの装置の連結部分に剥離液廃液中のレジスト重量に対し0.01〜0.2倍重量のアルカリを添加する手段を設けるか、
または薄膜式蒸発器、低沸点物除去塔および剥離液精製塔の順序で剥離液廃液を流す場合は、低沸点物除去塔またはそれより前の段階(精製剥離液ラインを含めてこれより前の段階)のいずれかの装置またはそれらの装置の連結部分に剥離液廃液中のレジスト重量に対し0.01〜0.2倍重量のアルカリを添加する手段を設ける
ことを特徴とする剥離液の再生装置。 An apparatus that separates and removes the resist from the stripper waste liquid containing the resist discharged from the manufacturing process of the liquid crystal display panel and regenerates the stripper.
When the stripping solution waste liquid is flowed in the order of the low boiling point removal tower, the thin film evaporator, and the stripping liquid purification tower, the thin film evaporator or the previous stage (including the purification stripping liquid line and the previous stage) ) Or a connecting part of these devices is provided with a means for adding 0.01 to 0.2 times the weight of alkali with respect to the resist weight in the stripping solution waste solution,
Or when the stripping solution waste liquid is flowed in the order of thin film evaporator, low boiling point removal column and stripping solution purification column, low boiling point stripping column or an earlier stage (including the purification stripping solution line and earlier) Regeneration of the stripping solution, characterized in that means for adding 0.01 to 0.2 times the weight of alkali with respect to the resist weight in the stripping solution waste solution is provided at any one of the devices in step) apparatus.
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JP2014077935A (en) * | 2012-10-11 | 2014-05-01 | Nippon Refine Kk | Regeneration method and regeneration apparatus for resist stripping solution |
JP6514426B1 (en) * | 2018-07-18 | 2019-05-15 | リファインホールディングス株式会社 | Solution processing apparatus and solution processing method |
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