JP2007241278A - Regeneration method and regeneration apparatus for resist stripping waste liquid - Google Patents

Regeneration method and regeneration apparatus for resist stripping waste liquid Download PDF

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JP2007241278A
JP2007241278A JP2007051322A JP2007051322A JP2007241278A JP 2007241278 A JP2007241278 A JP 2007241278A JP 2007051322 A JP2007051322 A JP 2007051322A JP 2007051322 A JP2007051322 A JP 2007051322A JP 2007241278 A JP2007241278 A JP 2007241278A
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acid
waste liquid
organic solvent
resist
stripping waste
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JP4874835B2 (en
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Ki Beom Lee
イ，キボム
Byung-Uk Kim
キム，ビョンウク
Mi Sun Park
パク，ミスン
Jin-Sup Hon
ホン，ジンスプ
Yoon-Gil Yim
イム，ユンギル
Suk Il Yoon
ユン，スクイル
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Dongjin Semichem Co Ltd
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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
    • G03F7/30—Imagewise removal using liquid means
    • G03F7/3042—Imagewise removal using liquid means from printing plates transported horizontally through the processing stations
    • G03F7/3071—Process control means, e.g. for replenishing
    • 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
    • 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

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  • General Physics & Mathematics (AREA)
  • Engineering & Computer Science (AREA)
  • Automation & Control Theory (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Photosensitive Polymer And Photoresist Processing (AREA)
  • Heat Treatment Of Water, Waste Water Or Sewage (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Extraction Or Liquid Replacement (AREA)

Abstract

<P>PROBLEM TO BE SOLVED: To provide a regeneration method and a regeneration apparatus for a resist stripping waste liquid, particularly suitable for economically regenerating a stripping waste liquid produced in a stripping step where a stripping liquid containing various specified amine compounds are used and in an occasion where various kinds of resists and stripping liquids are used. <P>SOLUTION: The regeneration method for a resist stripping waste liquid containing water, a resist, an amine compound and an organic solvent includes steps of: (a) adding an acid which reacts with the amine compound in the resist stripping waste liquid to produce an amine-acid compound which is not distilled in distillation of the organic solvent; and (b) distilling into fractions the reaction product of the step (a) in a distillation tank 40 to recover only the organic solvent. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

本発明はレジスト剥離廃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 recycling a resist stripping waste liquid.

集積回路（ＩＣ）、高集積回路（ＬＳＩ）、超高集積回路（ＶＬＳＩ）等の半導体素子と液晶表示素子などディスプレイ装置を製造するためには多くのフォトエッチング工程およびレジスト剥離工程が反復的に実施され、これによって多量のレジスト剥離廃液が発生する。特に、液晶表示素子などディスプレイ基板面積の急速な大型化によって剥離液の使用量が大幅に増加しており、剥離廃液の再利用に関する要請がますます増大している。   In order to manufacture display devices such as semiconductor devices such as integrated circuits (IC), highly integrated circuits (LSI), and very high integrated circuits (VLSI) and liquid crystal display devices, many photoetching steps and resist stripping steps are repeated. As a result, a large amount of resist stripping waste liquid is generated. In particular, the amount of stripping solution used has increased significantly due to the rapid increase in the area of display substrates such as liquid crystal display elements, and there has been an increasing demand for reuse of stripping waste fluid.

レジスト剥離工程に使用された剥離液廃液はレジスト、水分、いろいろな種類の有機アミン化合物および有機溶媒を含んでいる。従来のこのような剥離液廃液を廃棄処理する方法として焼却処理する方法が一般的であった。しかし、このような方法は焼却ガスを大気中に放出することによって環境に悪い影響を与えるだけでなく、剥離液廃液中の再利用の可能な成分まで廃棄してしまうことになる。このため、経済性の面でも好ましくなく、剥離廃液の再生に関する多くの研究が試みられている。   The stripping solution waste liquid used in the resist stripping process contains resist, moisture, various kinds of organic amine compounds, and organic solvents. As a conventional method for disposing of such a stripping solution waste liquid, an incineration method has been generally used. However, such a method not only adversely affects the environment by releasing the incineration gas into the atmosphere, but also discards reusable components in the stripping solution waste liquid. For this reason, it is not preferable in terms of economy, and many studies on the regeneration of the stripping waste liquid have been attempted.

また、最近、半導体およびディスプレイ製造工程で精密性および特性化がさらに要求されており、各工程に最適なフォトレジストの細分化が行われている。このため、それぞれの剥離工程で使用されるレジスト剥離液も有機アミンの種類、有機溶媒の種類および含有量が細分化されて使用されている。   Recently, there has been a further demand for precision and characterization in semiconductor and display manufacturing processes, and photoresist subdivision optimal for each process has been performed. For this reason, the resist stripping solution used in each stripping process is also used by subdividing the type of organic amine, the type and content of the organic solvent.

レジスト剥離廃液の再生に対する試みの一例として特許文献１には、アルカノールアミン、有機溶媒およびレジストを含有するレジスト剥離廃液を再生するレジスト剥離廃液の再生装置であって、分画分子量１００〜１５００の膜を有し、前記レジスト剥離廃液を前記膜を用いて濃縮液と透過液に分離する膜分離装置と、前記透過液を貯油し、前記透過液中のアルカノールアミンおよび有機溶媒の濃度を調整するための濃度調整槽と、前記濃度調整槽にアルカノールアミンを供給するアルカノールアミン供給手段と、前記濃度調整槽に有機溶媒を供給する有機溶媒供給手段とを備えるレジスト剥離廃液の再生装置を開示している。この再生装置では、レジスト剥離廃液に含まれているアルカノ−ルアミンと有機溶媒はナノ膜を通過し、レジストは通過しない性質を利用して剥離液を再生する方法を採用している。   As an example of an attempt to regenerate a resist stripping waste liquid, Patent Document 1 discloses a resist stripping waste liquid regenerating apparatus for regenerating a resist stripping waste liquid containing an alkanolamine, an organic solvent and a resist, and has a molecular weight cut off of 100 to 1500 A separation apparatus for separating the resist stripping waste liquid into a concentrated liquid and a permeated liquid using the membrane, and storing the permeated liquid and adjusting the concentration of the alkanolamine and the organic solvent in the permeated liquid A resist stripping waste liquid regenerating apparatus comprising: a concentration adjusting tank, an alkanolamine supplying means for supplying alkanolamine to the concentration adjusting tank, and an organic solvent supplying means for supplying an organic solvent to the concentration adjusting tank. . In this regenerating apparatus, a method of regenerating the stripping solution by utilizing the property that the alkanolamine and the organic solvent contained in the resist stripping waste liquid pass through the nanofilm and the resist does not pass through is adopted.

また、これとは別に、レジスト剥離廃液の再生に関するいろいろな試みが進められているが、特化されたアミン化合物を使用するそれぞれ細分化されたフォトエッチング及び剥離工程で発生した剥離廃液において、有機溶媒といろいろな種類のアミン化合物とを一度に分離・再生することは容易でない。また、半導体およびディスプレイ製造工程でいろいろな種類のレジストと剥離液とが使用される場合に、有機溶媒といろいろな種類のアミン化合物を一度に分離するために、既存のレジスト剥離液の再生方法では限界があり、レジスト剥離廃液中のレジスト、水分および有機アミン化合物を除去して有機溶媒のみを経済的に再生することができる方法がさらに要請されている。
大韓民国特許出願第１０−２００２−００７５２３５号 Apart from this, various attempts have been made to regenerate the resist stripping waste liquid, but in the stripping waste liquid generated in the respective subdivided photoetching and stripping processes using specialized amine compounds, It is not easy to separate and regenerate the solvent and various types of amine compounds at once. In addition, when various types of resists and stripping solutions are used in semiconductor and display manufacturing processes, existing resist stripping solution regeneration methods are used to separate organic solvents and various types of amine compounds at once. There is a limit, and there is a further demand for a method capable of economically regenerating only the organic solvent by removing the resist, moisture and organic amine compound in the resist stripping waste liquid.
Korean Patent Application No. 10-2002-0075235

このような従来の技術の問題点を解決するために、本発明はレジスト剥離液に含まれているアミン化合物の種類に関係なく、高価の有機溶媒を再生してレジスト剥離液として再使用することによって、製造コストを低減することができるとともに、レジスト剥離廃液による環境汚染を低減させることができるレジスト剥離廃液の再生方法および再生装置を提供することを目的とする。   In order to solve such problems of the prior art, the present invention regenerates an expensive organic solvent and reuses it as a resist stripper regardless of the type of amine compound contained in the resist stripper. Accordingly, an object of the present invention is to provide a method and an apparatus for recycling a resist stripping waste liquid that can reduce the manufacturing cost and reduce environmental pollution due to the resist stripping waste liquid.

本発明の他の目的は、いろいろな特化されたアミン化合物を含む剥離液を使用する剥離工程と、いろいろな種類のレジストと剥離液が使用される場合にレジスト剥離廃液を経済性良く同時に再生するのに適したレジスト剥離廃液の再生方法および再生装置を提供することにある。   Another object of the present invention is a stripping process using stripping solutions containing various specialized amine compounds, and simultaneously recovering resist stripping waste liquid with good economic efficiency when various types of resists and stripping solutions are used. An object of the present invention is to provide a method and apparatus for recycling a resist stripping waste liquid suitable for the above.

前記目的を達成するために、本発明は、
水、レジスト、アミン化合物、有機溶媒を含むレジスト剥離廃液を再生する方法であって、
（ａ）レジスト剥離廃液のアミン化合物と反応して、アミン化合物が有機溶媒蒸留時に蒸留されないアミン−酸化合物を形成する酸を添加する工程；および
（ｂ）前記（ａ）工程の反応物を分別蒸留して有機溶媒のみを収得する工程
を含むことを特徴とするレジスト剥離廃液の再生方法を提供する。 In order to achieve the above object, the present invention provides:
A method for regenerating a resist stripping waste liquid containing water, a resist, an amine compound, and an organic solvent,
(A) adding an acid that reacts with the amine compound of the resist stripping waste liquid to form an amine-acid compound that is not distilled when the organic compound is distilled in an organic solvent; and (b) fractionating the reactant in the step (a). There is provided a method for regenerating a resist stripping waste liquid comprising a step of obtaining only an organic solvent by distillation.

また、本発明は、
（ａ）水、レジスト、アミン化合物、有機溶媒を含む被処理レジスト剥離廃液貯蔵槽；
（ｂ）酸貯蔵槽；
（ｃ）前記被処理レジスト剥離廃液貯蔵槽から移送された剥離廃液に前記酸貯蔵槽から移送された酸を添加して剥離廃液のアミン化合物を酸と反応させる反応槽；
（ｄ）前記反応槽から移送された剥離廃液を分別蒸留する蒸留槽；および
（ｅ）前記分別蒸留槽で分別蒸留された有機溶媒を捕集して貯蔵する有機溶媒貯蔵槽
を含むことを特徴とするレジスト剥離廃液再生装置を提供する。 The present invention also provides:
(A) A treated resist stripping waste liquid storage tank containing water, a resist, an amine compound, and an organic solvent;
(B) an acid storage tank;
(C) A reaction tank in which the acid transferred from the acid storage tank is added to the stripping waste liquid transferred from the treated resist stripping waste liquid storage tank to react the amine compound of the stripping waste liquid with the acid;
(D) a distillation tank for fractional distillation of the stripping waste liquid transferred from the reaction tank; and (e) an organic solvent storage tank for collecting and storing the organic solvent fractionally distilled in the fractional distillation tank. A resist stripping waste liquid recycling apparatus is provided.

本発明によるレジスト剥離液再生方法および再生装置は、レジスト剥離液に含まれているアミン化合物の種類に関係なく、高価の有機溶媒を再生してレジスト剥離液として再使用することによって、製造コストを低減することができるとともに、レジスト剥離廃液による環境汚染を低減させることができ、特に、種々の特化されたアミン化合物を含む剥離液を使用する剥離工程において、種々のレジストと剥離液とが使用される場合に、レジスト剥離廃液を経済性良く同時に再生するのに適するという効果がある。   Regardless of the type of amine compound contained in the resist stripping solution, the resist stripping solution recycling method and recycling apparatus according to the present invention regenerates an expensive organic solvent and reuses it as a resist stripping solution. In addition to reducing the environmental pollution caused by resist stripping waste liquid, various resists and stripping liquids are used, especially in stripping processes that use stripping liquids containing various specialized amine compounds. In this case, there is an effect that the resist stripping waste liquid is suitable for simultaneously regenerating with good economic efficiency.

以下、本発明を詳細に説明する。
本発明者は、既存のレジスト剥離廃液の再生方法では、アミン化合物と有機溶媒との混合物が収集されるため、いろいろな特化されたアミン化合物を含む剥離液をいろいろな種類のレジストの剥離のために使用した場合に、レジスト剥離廃液を再生しても、実際に使用しようとする剥離液とは、必要とするアミン化合物が異なることがあり、このような再生した混合物は、剥離液として使用することができないのを発見し、必要な組成で、レジスト剥離廃液を再生する方法を研究していたところ、経済的な方法で、レジスト剥離廃液中のレジスト、水分およびアミン化合物を除去し、有機溶媒のみを捕集することにより、再びそれぞれの特化された剥離液に適したアミン化合物を、再生された有機溶媒に添加してレジスト剥離液を製造することができ、上記の全ての問題点が解決されることができるのを確認し、本発明を完成するに至った。 Hereinafter, the present invention will be described in detail.
In the present method for regenerating a resist stripping waste liquid, since a mixture of an amine compound and an organic solvent is collected, stripping solutions containing various specialized amine compounds are used to strip various types of resists. When the resist stripping waste liquid is regenerated, the required amine compound may differ from the stripping liquid that is actually used, and such regenerated mixture can be used as a stripping liquid. I found that I was not able to do this, and I was researching a method to regenerate the resist stripping waste liquid with the required composition. By removing the resist, water and amine compounds in the resist stripping waste liquid with an economical method, By collecting only the solvent, an amine compound suitable for each specialized stripping solution is again added to the regenerated organic solvent to produce a resist stripping solution. Can be, it confirms that it can all problems described above are solved, leading to completion of the present invention.

本発明は水、レジスト、アミン化合物、有機溶媒を含むレジスト剥離廃液を再生する方法にであって、（ａ）レジスト剥離廃液にアミン化合物と反応し、アミン化合物が有機溶媒蒸留時に蒸留されないアミン−酸化合物を形成する酸を添加する工程；および（ｂ）前記（ａ）工程の反応物を分別蒸留して有機溶媒のみを採取する工程を含むことを特徴とする。
前記レジスト剥離廃液は、剥離液が使用されるそれぞれの工程によって、いろいろな種類のアミン化合物またはいろいろな種類の有機溶媒を含んでいてもよい。
前記アミン化合物は、第１級、２級または３級アミンのいずれでもよく、脂肪族アミン、脂環族アミン、芳香族アミン、ヘテロサイクリックアミン、ヒドロキシルアミンのいずれであってもよい。 The present invention is a method for regenerating a resist stripping waste liquid containing water, a resist, an amine compound, and an organic solvent, and (a) an amine that reacts with an amine compound in the resist stripping waste liquid and the amine compound is not distilled during distillation of the organic solvent. A step of adding an acid that forms an acid compound; and (b) fractional distillation of the reaction product of the step (a) to collect only an organic solvent.
The resist stripping waste liquid may contain various types of amine compounds or various types of organic solvents depending on the process in which the stripping solution is used.
The amine compound may be any of primary, secondary, and tertiary amines, and may be any of aliphatic amines, alicyclic amines, aromatic amines, heterocyclic amines, and hydroxylamines.

前記有機溶媒は、グリコール類のエチレングリコールモノメチルエーテル、エチレングリコールモノエチルエーテル、エチレングリコールモノブチルエーテル、エチレングリコールモノフェニルエーテル、ジエチレングリコールモノメチルエーテル、ジエチレングリコールモノエチルエーテル、ジエチレングリコールモノブチルエーテル、ジプロピレングリコールモノメチルエーテル、ジプロピレングリコールモノエチルエーテル、ジプロピレングリコールモノプロピルエーテル、またはジプロピレングリコールモノブチルエーテルを含むことができ、ジメチルスルホキシド、ジメチルアセトアミド、ジメチルホルムアミド、ジメチルイミダゾリジノン、スルホラン、またはＮ−メチルピロリドンのようなアルキルピロリドンを含むことができる。   The organic solvent includes glycols such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethylene glycol monophenyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, diethylene glycol Can include propylene glycol monoethyl ether, dipropylene glycol monopropyl ether, or dipropylene glycol monobutyl ether, and alkyl such as dimethyl sulfoxide, dimethylacetamide, dimethylformamide, dimethylimidazolidinone, sulfolane, or N-methylpyrrolidone May contain pyrrolidone That.

本発明のレジスト剥離廃液の再生方法における前記（ａ）工程で使用される酸は、剥離廃液中のアミン化合物と反応し、剥離廃液のアミン化合物が有機溶媒蒸留時に蒸留されないアミン−酸化合物を形成するような酸であれば特に限定されず、安息香酸、クエン酸、蟻酸、マレイン酸、リンゴ酸、サリチル酸、酒石酸、酢酸、シュウ酸、燐酸、硝酸、塩酸、硫酸および過塩素酸などが挙げられる。これらは単独でまたは混用して使用することができる。使用量は、少なくとも剥離廃液に含まれているアミン化合物の当量と同一であるか、その当量以上であることが適しており、残留する（未反応の）アミン化合物がないように過量の酸を添加することが好ましい。また、酸は、有機溶媒分別蒸留時に、酸とアミンとの反応物、残存する酸が混合しないような酸を使用するのが好ましい。   The acid used in the step (a) in the method for regenerating a resist stripping waste liquid of the present invention reacts with an amine compound in the stripping waste liquid to form an amine-acid compound in which the amine compound in the stripping waste liquid is not distilled during the distillation of the organic solvent. The acid is not particularly limited, and examples include benzoic acid, citric acid, formic acid, maleic acid, malic acid, salicylic acid, tartaric acid, acetic acid, oxalic acid, phosphoric acid, nitric acid, hydrochloric acid, sulfuric acid, and perchloric acid. . These can be used alone or in combination. It is suitable that the amount used is at least equal to or greater than the equivalent of the amine compound contained in the stripping waste liquid, and an excessive amount of acid is used so that there is no remaining (unreacted) amine compound. It is preferable to add. In addition, it is preferable to use an acid that does not mix the reaction product of the acid and the amine and the remaining acid during the fractional distillation of the organic solvent.

前記（ａ）工程によって、被処理レジスト剥離廃液の成分は、レジスト、水分、アミンと酸の反応物、残存する酸および有機溶媒を含むようになる。
本発明のレジスト剥離廃液の再生方法は（ｂ）工程として、前記（ａ）工程の反応物を分別蒸留して有機溶媒のみを捕集する工程を含む。本工程で分別蒸留によって水分と酸および有機溶媒が分別蒸留されて有機溶媒のみを捕集することができ、蒸留されないレジストと酸とアミンの反応物は別途に分離される。 Through the step (a), the components of the resist stripping waste liquid to be processed include a resist, moisture, a reaction product of amine and acid, a remaining acid and an organic solvent.
The method for regenerating the resist stripping waste liquid of the present invention includes, as the step (b), a step of fractionally distilling the reaction product of the step (a) to collect only the organic solvent. In this step, water, acid and organic solvent can be fractionally distilled by fractional distillation to collect only the organic solvent, and the undistilled resist, acid and amine reactants are separated separately.

前記分別捕集された有機溶媒は凝縮器によって再び液体化することができ、前記有機溶媒に特別に要請されるアミン化合物を添加して再び剥離液として再使用することができるようになる。
本発明の剥離廃液再生方法は、アミン化合物の種類に関係なく、高価の有機溶媒を再生してレジスト剥離液として再使用することによってレジスト剥離廃液による環境汚染を低減することができる。また、高価の有機溶媒を再使用することによってさらに費用を節減することができる。 The separated and collected organic solvent can be liquefied again by a condenser, and a specially required amine compound can be added to the organic solvent and reused again as a stripping solution.
The stripping waste liquid recycling method of the present invention can reduce environmental pollution caused by a resist stripping waste liquid by regenerating an expensive organic solvent and reusing it as a resist stripping liquid regardless of the type of amine compound. In addition, costs can be further reduced by reusing expensive organic solvents.

実施の形態１
以下、本発明の具体的な一実施形態として、酸成分として酢酸を使用していろいろなレジスト剥離工程で発生したＭＥＡ（モノエタノールアミン）、ＭＩＰＡ（モノイソプロパノールアミン）、ｎＭＥＡ（ｎ−メチルエタノールアミン）を含むアミン化合物、グリコールおよびアルキルピロリドンを含む有機溶媒、水分およびレジストから構成された剥離廃液を再生する方法を説明する。 Embodiment 1
Hereinafter, as a specific embodiment of the present invention, MEA (monoethanolamine), MIPA (monoisopropanolamine), nMEA (n-methylethanolamine) generated in various resist stripping processes using acetic acid as an acid component will be described. A method for reclaiming a stripping waste liquid composed of an amine compound containing), an organic solvent containing glycol and alkylpyrrolidone, moisture and a resist will be described.

ＭＥＡ、ＭＩＰＡ、ｎ−ＭＥＡを含むアミン化合物、グリコールおよびアルキルピロリドンを含む有機溶媒、水分およびレジストから構成された剥離廃液に前記アミン化合物の総当量より過量の酢酸を添加する。酢酸が添加されると、酢酸はアミン化合物と反応してアミン−酢酸反応物を生成し、反応に関与しない酢酸は剥離廃液に液体状態で残留する。   An excess amount of acetic acid is added to the stripping waste liquid composed of an MEA, MIPA, an amine compound containing n-MEA, an organic solvent containing glycol and alkylpyrrolidone, moisture, and a resist, based on the total equivalent of the amine compound. When acetic acid is added, acetic acid reacts with the amine compound to produce an amine-acetic acid reactant, and acetic acid not involved in the reaction remains in a liquid state in the stripping waste liquid.

その後、レジスト、アミン−酢酸反応物、水分、反応に関与せずに残存する酢酸、有機溶媒の混合物は分別蒸留によって、水分が一番先に蒸留され、その次に酢酸が蒸留され、さらにその次に有機溶媒のグリコールとアルキルピロリドンが蒸留されされ、残留するレジストおよびアミン−酢酸反応物と分離される。これにより、目的する有機溶媒のみを捕集することができる。
その後、捕集された有機溶媒に、特別に要請されるアミン化合物のＭＥＡ、ＭＩＰＡまたはｎ−ＭＥＡなどを選択的に添加して剥離液として再使用することができる。 Thereafter, the resist, amine-acetic acid reactant, moisture, acetic acid remaining uninvolved in the reaction, and organic solvent mixture are fractionally distilled so that moisture is distilled first, followed by acetic acid. The organic solvents glycol and alkyl pyrrolidone are then distilled and separated from the remaining resist and amine-acetic acid reactant. Thereby, only the target organic solvent can be collected.
Thereafter, a specially required amine compound such as MEA, MIPA, or n-MEA can be selectively added to the collected organic solvent and reused as a stripping solution.

実施の形態２
また、以下に本発明の具体的な一実施形態として、酸成分としてシュウ酸（Ｃ2Ｈ2Ｏ4）を使用していろいろなレジスト剥離工程で発生したＭＥＡ、ＭＩＰＡ、ｎ−ＭＥＡを含むアミン化合物、グリコールおよびアルキルピロリドンを含む有機溶媒、水分およびレジストから構成された剥離廃液を再生する方法を説明する。前記シュウ酸は常温で２水和物として存在するので、シュウ酸２水和物（Ｃ2Ｈ2Ｏ4Ｈ2Ｏ）を使用する。 Embodiment 2
In addition, as a specific embodiment of the present invention, an amine containing MEA, MIPA, and n-MEA generated in various resist stripping steps using oxalic acid (C 2 H 2 O 4 ) as an acid component will be described below. A method for regenerating a stripping waste liquid composed of an organic solvent containing a compound, glycol and alkylpyrrolidone, moisture and a resist will be described. Since the oxalic acid exists as a dihydrate at room temperature, oxalic acid dihydrate (C 2 H 2 O 4 H 2 O) is used.

ＭＥＡ、ＭＩＰＡ、ｎ−ＭＥＡを含むアミン化合物、グリコールおよびアルキルピロリドンを含む有機溶媒、水分およびレジストから構成された剥離廃液に、前記アミン化合物の総当量より過量のシュウ酸２水和物を添加する。
シュウ酸２水和物が添加されると、シュウ酸２水和物は、アミン化合物と反応してアミン−シュウ酸反応物を生成し、反応に関与しないシュウ酸２水和物は剥離廃液に残留する。 Add excessive amount of oxalic acid dihydrate to the stripping waste liquid composed of MEA, MIPA, amine compound containing n-MEA, organic solvent containing glycol and alkylpyrrolidone, water and resist, and more than the total equivalent of the amine compound .
When oxalic acid dihydrate is added, the oxalic acid dihydrate reacts with the amine compound to produce an amine-oxalic acid reactant, and oxalic acid dihydrate not involved in the reaction becomes a stripping waste liquid. Remains.

その後、レジスト、アミン−シュウ酸反応物、水分、反応に関与せずに残存するシュウ酸２水和物、有機溶媒の混合物は、分別蒸留によって、水分及びシュウ酸２水和物が分解されたホルム酸、二酸化炭素、一酸化炭素が先に蒸留され、その次に有機溶媒のグリコールとアルキルピロリドンとが蒸留され、残留するレジストおよびアミン−シュウ酸反応物および分解されないシュウ酸２水和物と分離され、目的する有機溶媒のみを捕集することができる。   Thereafter, the resist, amine-oxalic acid reactant, moisture, oxalic acid dihydrate remaining without participating in the reaction, and organic solvent mixture were decomposed into water and oxalic acid dihydrate by fractional distillation. Formic acid, carbon dioxide, carbon monoxide are first distilled, then the organic solvents glycol and alkyl pyrrolidone are distilled to leave residual resist and amine-oxalic acid reactant and undegraded oxalic acid dihydrate. Only the desired organic solvent is separated and can be collected.

その後、捕集された有機溶媒に、特別に要請されるアミン化合物のＭＥＡ、ＭＩＰＡまたはｎ−ＭＥＡなどを選択的に添加して剥離液として再使用することができる。
実施の形態３
本発明のレジスト剥離廃液再生装置は、（ａ）水、レジスト、アミン化合物、有機溶媒を含む被処理レジスト剥離廃液貯蔵槽；（ｂ）酸貯蔵槽；（ｃ）前記被処理レジスト剥離廃液貯蔵槽から移送された剥離廃液に前記酸貯蔵槽から移送された酸を添加して剥離廃液のアミン化合物を酸と反応させる反応槽；（ｄ）前記反応槽から移送された剥離廃液を分別蒸留する蒸留槽；および（ｅ）前記分別蒸留槽で分別蒸留された有機溶媒を捕集して貯蔵する有機溶媒貯蔵槽を含む。 Thereafter, a specially required amine compound such as MEA, MIPA, or n-MEA can be selectively added to the collected organic solvent and reused as a stripping solution.
Embodiment 3
The resist stripping waste liquid recycling apparatus of the present invention includes: (a) a resist stripping waste liquid storage tank containing water, a resist, an amine compound, and an organic solvent; (b) an acid storage tank; (c) the resist stripping waste liquid storage tank. A reaction tank in which the acid transferred from the acid storage tank is added to the stripped waste liquid transferred from the reactor to react the amine compound of the stripped waste liquid with the acid; And (e) an organic solvent storage tank for collecting and storing the organic solvent fractionally distilled in the fractional distillation tank.

以下、本発明のレジスト剥離廃液再生装置の一実施形態である図１に示された模式図によって、本発明を具体的に説明する。
まず、それぞれのレジスト剥離工程で回収された被処理レジスト剥離液は、被処理レジスト剥離廃液貯蔵槽１０に貯蔵される。前記被処理レジスト剥離廃液はレジスト、ＭＥＡ、ＭＩＰＡ、ｎ−ＭＥＡなどのいろいろな種のアミン化合物、水分および有機溶媒を含む。前記被処理レジスト剥離廃液貯蔵槽１０に貯蔵された被処理レジスト剥離廃液はポンプ１１を通じて配管に沿って反応槽３０に移送される。前記剥離廃液の移送時に剥離廃液の量を調節するために配管の所定の部分に自動調節バルブ１２を備えることができる。また、レジスト剥離廃液に含まれているアミン化合物と反応する酸を貯蔵する酸貯蔵槽２０が別途に備えられる。前記酸は酢酸またはシュウ酸二水和物が好ましい。前記酸貯蔵槽２０から、酸はポンプ２１を通じて配管に沿って反応槽３０に移送される。前記剥離廃液の移送時に酸の量を調節するために配管の所定の部分に自動調節バルブ２２を備えることができる。移送された酸の量は、剥離廃液に含まれているアミン化合物の総当量と同一か、過量で移送するのが好ましい。 Hereinafter, the present invention will be described in detail with reference to the schematic diagram shown in FIG. 1 which is an embodiment of the resist stripping waste liquid recycling apparatus of the present invention.
First, the to-be-processed resist stripping solution collected in each resist stripping step is stored in the to-be-processed resist stripping waste liquid storage tank 10. The treated resist stripping waste liquid contains various kinds of amine compounds such as resist, MEA, MIPA, and n-MEA, moisture, and organic solvent. The to-be-processed resist stripping waste liquid stored in the to-be-processed resist stripping waste liquid storage tank 10 is transferred to the reaction tank 30 along the piping through the pump 11. An automatic adjustment valve 12 may be provided in a predetermined portion of the pipe in order to adjust the amount of the peeling waste liquid during the transfer of the peeling waste liquid. In addition, an acid storage tank 20 for storing an acid that reacts with the amine compound contained in the resist stripping waste liquid is separately provided. The acid is preferably acetic acid or oxalic acid dihydrate. From the acid storage tank 20, the acid is transferred to the reaction tank 30 along the pipe through the pump 21. In order to adjust the amount of acid during the transfer of the stripping waste liquid, an automatic adjustment valve 22 may be provided in a predetermined portion of the pipe. The amount of the acid transferred is preferably the same as the total equivalent amount of amine compounds contained in the stripping waste liquid or transferred in excess.

被処理レジスト剥離廃液貯蔵槽１０から移送された剥離廃液と酸貯蔵槽２０から移送された酸は、反応槽３０で反応して、アミン−酸反応物（一例にアミン−酢酸反応物またはアミン−シュウ酸反応物）を形成し、反応に関与しない酸は、剥離廃液にそのまま存在する。この時、剥離廃液にはレジスト、酸−塩基反応物、水分、反応に関与しない酸、有機溶媒を含む。   The stripping waste liquid transferred from the to-be-processed resist stripping waste liquid storage tank 10 and the acid transferred from the acid storage tank 20 react in the reaction tank 30 to produce an amine-acid reactant (for example, an amine-acetic acid reactant or an amine- An acid that forms an oxalic acid reactant and does not participate in the reaction is present in the stripping waste liquid as it is. At this time, the stripping waste liquid contains a resist, an acid-base reactant, moisture, an acid not involved in the reaction, and an organic solvent.

前記反応が完結した剥離廃液は、反応槽３０からポンプ３１を通じて配管に沿って蒸留槽４０に移送される。前記剥離廃液の移送時に剥離廃液の量を調節するために配管の所定の部分に自動調節バルブ３２を備えることができる。
蒸留槽４０では、温度上昇によって剥離廃液に含まれている成分が分別蒸留されて捕集される。好ましくは、前記蒸留槽４０は水分を捕集するための１次蒸留槽４３、酸を捕集するための２次蒸留槽４４、有機溶媒を捕集するための３次蒸留槽４５、残留成分排出槽４６に分けて設置することができる。 The stripped waste liquid after the completion of the reaction is transferred from the reaction tank 30 through the pump 31 to the distillation tank 40 along the pipe. An automatic adjustment valve 32 may be provided at a predetermined portion of the pipe in order to adjust the amount of the peeling waste liquid during the transfer of the peeling waste liquid.
In the distillation tank 40, the components contained in the stripping waste liquid are fractionally distilled and collected as the temperature rises. Preferably, the distillation tank 40 includes a primary distillation tank 43 for collecting moisture, a secondary distillation tank 44 for collecting acid, a tertiary distillation tank 45 for collecting organic solvent, and residual components. It can be installed separately in the discharge tank 46.

酸として酢酸を使用する場合、剥離廃液内に含まれている水分は１次蒸留槽４３を通じて捕集され、反応に関与しない酢酸は２次蒸留槽４４を通じて捕集され、有機溶媒は３次蒸留槽４５を通じて捕集され、レジストとアミン−酢酸の反応物は蒸留されず残留成分排出槽４６に排出することができる。
好ましくは、前記蒸留槽４０は減圧装置４７を別途に備えることができる。この場合、蒸留温度を低下させることができるため、好ましい。 When acetic acid is used as the acid, water contained in the stripping waste liquid is collected through the primary distillation tank 43, acetic acid not involved in the reaction is collected through the secondary distillation tank 44, and the organic solvent is tertiary distilled. The reaction product of the resist and amine-acetic acid collected through the tank 45 can be discharged into the residual component discharge tank 46 without being distilled.
Preferably, the distillation tank 40 may include a decompression device 47 separately. This is preferable because the distillation temperature can be lowered.

前記３次蒸留槽４５を通じて捕集された有機溶媒は、有機溶媒貯蔵槽５０に移送される。前記有機溶媒貯蔵槽５０は凝縮器５３を備え、捕集された有機溶媒を液体状態にすることができる。
前記有機溶媒貯蔵槽５０には所定のアミン化合物を添加できるアミン化合物槽６０が連結されているのが好ましく、所定のアミン化合物の添加によって個別レジスト剥離工程に適したアミン化合物のみを添加して、再生剥離液を製造することができる。 The organic solvent collected through the tertiary distillation tank 45 is transferred to the organic solvent storage tank 50. The organic solvent storage tank 50 includes a condenser 53, and the collected organic solvent can be in a liquid state.
It is preferable that an amine compound tank 60 to which a predetermined amine compound can be added is connected to the organic solvent storage tank 50, and only an amine compound suitable for the individual resist stripping process is added by adding the predetermined amine compound, A regenerative stripping solution can be produced.

以下、本発明の理解のために好ましい実施例を提示するが、下記の実施例は本発明を例示するものに過ぎず、本発明の範囲が下記の実施例に限定されるわけではない。
実施例１
いろいろなレジスト剥離工程で収去されたレジスト３重量部、アミン化合物ＭＥＡ５重量部、ＭＩＰＡ５重量部、ｎ−ＭＥＡ５重量部、水分１０重量部、有機溶媒７２重量部（グリコール５０重量部およびアルキルピロリドン２２重量部）を含む剥離廃液に酢酸１０重量部を添加してアミン−酢酸化合物を形成した。 Hereinafter, preferred examples will be presented for the understanding of the present invention. However, the following examples are merely illustrative of the present invention, and the scope of the present invention is not limited to the following examples.
Example 1
Resist removed in various resist stripping steps 3 parts by weight, amine compound MEA 5 parts by weight, MIPA 5 parts by weight, n-MEA 5 parts by weight, water 10 parts by weight, organic solvent 72 parts by weight (glycol 50 parts by weight and alkylpyrrolidone 22 10 parts by weight of acetic acid was added to the stripping waste liquid containing part by weight to form an amine-acetic acid compound.

前記アミン−酢酸化合物が形成された剥離廃液を分別蒸留して、水分と残留する酢酸および有機溶媒を順次に捕集し、残留するレジストとアミン−酢酸を分離排出した。
前記捕集された有機溶媒を冷却して液体化し、液体化された有機溶媒の成分を分析した結果、有機溶媒１００重量部中のグリコールが６１．４重量部、アルキルピロリドンが３８．６重量部であり、水分は０．１重量部未満、総アミン化合物０．１重量部未満であり、樹脂は検出されなかった。 The stripping waste liquid in which the amine-acetic acid compound was formed was fractionally distilled to sequentially collect moisture, residual acetic acid and organic solvent, and the remaining resist and amine-acetic acid were separated and discharged.
The collected organic solvent was cooled to be liquefied, and the components of the liquefied organic solvent were analyzed. As a result, 61.4 parts by weight of glycol and 38.6 parts by weight of alkylpyrrolidone in 100 parts by weight of the organic solvent were analyzed. The water content was less than 0.1 parts by weight and the total amine compound was less than 0.1 parts by weight, and no resin was detected.

実施例２
いろいろなレジスト剥離工程で収去されたレジスト３重量部、アミン化合物ＭＥＡ４重量部、ＭＩＰＡ４重量部、ｎ−ＭＥＡ４重量部、水分２０重量部、有機溶媒６５重量部（グリコール４５重量部およびアルキルピロリドン２０重量部）を含む剥離廃液に酢酸８重量部を添加してアミン−酢酸化合物を形成した。
前記アミン−酢酸化合物が形成された剥離廃液を分別蒸留して、水分と残留する酢酸および有機溶媒を順次に捕集し、残留するレジストとアミン−酢酸を分離排出した。
前記捕集された有機溶媒を冷却して液体化し、液体化された有機溶媒の成分を分析した結果、有機溶媒１００重量部中のグリコールが６１．８重量部、アルキルピロリドンが３８．２重量部であり、水分は０．１重量部未満、総アミン化合物０．１重量部未満であり、樹脂は検出されなかった。 Example 2
Resist removed in various resist stripping steps 3 parts by weight, amine compound MEA 4 parts by weight, MIPA 4 parts by weight, n-MEA 4 parts by weight, moisture 20 parts by weight, organic solvent 65 parts by weight (glycol 45 parts by weight and alkylpyrrolidone 20 8 parts by weight of acetic acid was added to the exfoliated waste liquid containing (part by weight) to form an amine-acetic acid compound.
The stripping waste liquid in which the amine-acetic acid compound was formed was fractionally distilled to sequentially collect moisture, residual acetic acid and organic solvent, and the remaining resist and amine-acetic acid were separated and discharged.
The collected organic solvent was cooled to be liquefied, and the components of the liquefied organic solvent were analyzed. As a result, 61.8 parts by weight of glycol and 38.2 parts by weight of alkylpyrrolidone in 100 parts by weight of organic solvent were analyzed. The water content was less than 0.1 parts by weight and the total amine compound was less than 0.1 parts by weight, and no resin was detected.

実施例３
いろいろなレジスト剥離工程で収去されたレジスト２重量部、アミン化合物ＭＥＡ２重量部、ＭＩＰＡ２重量部、ｎ−ＭＥＡ２重量部、水分４０重量部、有機溶媒５２重量部（グリコール３６重量部およびアルキルピロリドン１６重量部）を含む剥離廃液に酢酸４重量部を添加してアミン−酢酸化合物を形成した。
前記アミン−酢酸化合物が形成された剥離廃液を分別蒸留して、水分と残留する酢酸および有機溶媒を順次に捕集し、残留するレジストとアミン−酢酸を分離排出した。
前記捕集された有機溶媒を冷却して液体化し、液体化された有機溶媒の成分を分析した結果、有機溶媒１００重量部中のグリコールが５８．９重量部、アルキルピロリドンが４１．１重量部であり、水分は０．１重量部未満、総アミン化合物０．１重量部未満であり、樹脂は検出されなかった。 Example 3
2 parts by weight of resist removed in various resist stripping steps, 2 parts by weight of amine compound MEA, 2 parts by weight of MIPA, 2 parts by weight of n-MEA, 40 parts by weight of water, 52 parts by weight of organic solvent (36 parts by weight of glycol and 16 parts of alkylpyrrolidone 16 4 parts by weight of acetic acid was added to the stripping waste liquid containing (part by weight) to form an amine-acetic acid compound.
The stripping waste liquid in which the amine-acetic acid compound was formed was fractionally distilled to sequentially collect moisture, residual acetic acid and organic solvent, and the remaining resist and amine-acetic acid were separated and discharged.
The collected organic solvent was cooled and liquefied, and the components of the liquefied organic solvent were analyzed. As a result, 58.9 parts by weight of glycol and 41.1 parts by weight of alkylpyrrolidone in 100 parts by weight of the organic solvent were analyzed. The water content was less than 0.1 parts by weight and the total amine compound was less than 0.1 parts by weight, and no resin was detected.

実施例４
いろいろなレジスト剥離工程で収去されたレジスト３重量部、アミン化合物ＭＥＡ５重量部、ＭＩＰＡ５重量部、ｎ−ＭＥＡ５重量部、水分１０重量部、有機溶媒７２重量部（グリコール５０重量部およびアルキルピロリドン２２重量部）を含む剥離廃液にシュウ酸２水和物１０．６重量部を添加してアミン−シュウ酸化合物を形成した。 Example 4
Resist removed in various resist stripping steps 3 parts by weight, amine compound MEA 5 parts by weight, MIPA 5 parts by weight, n-MEA 5 parts by weight, water 10 parts by weight, organic solvent 72 parts by weight (glycol 50 parts by weight and alkylpyrrolidone 22 10.6 parts by weight of oxalic acid dihydrate was added to the stripping waste liquid containing (part by weight) to form an amine-oxalic acid compound.

反応に関与しないシュウ酸２水和物は、剥離廃液に固形分として残っていた。
前記アミン−シュウ酸化合物が形成された剥離廃液を分別蒸留して、水分とホルム酸、一酸化炭素、二酸化炭素などのシュウ酸の分解された物質と有機溶媒を捕集し、残留するレジストとアミン−シュウ酸および分解されないシュウ酸２水和物を分離排出した。 Oxalic acid dihydrate not involved in the reaction remained as a solid content in the stripping waste liquid.
The separation waste liquid in which the amine-oxalic acid compound is formed is subjected to fractional distillation to collect moisture, a substance in which oxalic acid is decomposed such as formic acid, carbon monoxide, carbon dioxide, and an organic solvent, and a residual resist. Amine-oxalic acid and undecomposed oxalic acid dihydrate were separated and discharged.

前記捕集された有機溶媒を冷却して液体化し、液体化された有機溶媒の成分を分析した結果、有機溶媒１００重量部中のグリコールが６２．２重量部、アルキルピロリドンが３７．８重量部であり、水分は０．１重量部未満、総アミン化合物０．１重量部未満であり、樹脂は検出されなかった。   The collected organic solvent was cooled to be liquefied, and the components of the liquefied organic solvent were analyzed. As a result, 62.2 parts by weight of glycol and 37.8 parts by weight of alkylpyrrolidone in 100 parts by weight of the organic solvent were analyzed. The water content was less than 0.1 parts by weight and the total amine compound was less than 0.1 parts by weight, and no resin was detected.

実施例５
いろいろなレジスト剥離工程で収去されたレジスト３重量部、アミン化合物ＭＥＡ４重量部、ＭＩＰＡ４重量部、ｎ−ＭＥＡ４重量部、水分２０重量部、有機溶媒６５重量部（グリコール４５重量部およびアルキルピロリドン２０重量部）を含む剥離廃液にシュウ酸２水和物８．５重量部を添加してアミン−シュウ酸化合物を形成した。 Example 5
Resist removed in various resist stripping steps 3 parts by weight, amine compound MEA 4 parts by weight, MIPA 4 parts by weight, n-MEA 4 parts by weight, moisture 20 parts by weight, organic solvent 65 parts by weight (glycol 45 parts by weight and alkylpyrrolidone 20 8.5 parts by weight of oxalic acid dihydrate was added to the stripping waste liquid containing (part by weight) to form an amine-oxalic acid compound.

反応に関与しないシュウ酸２水和物は剥離廃液に固形分として残っていた。
前記アミン−シュウ酸化合物が形成された剥離廃液を分別蒸留して、水分とホルム酸、一酸化炭素、二酸化炭素などのシュウ酸の分解された物質と有機溶媒を捕集し、残留するレジストとアミン−シュウ酸および分解されないシュウ酸２水和物を分離排出した。
前記捕集された有機溶媒を冷却して液体化し、液体化された有機溶媒の成分を分析した結果、有機溶媒１００重量部中のグリコールが５８．３重量部、アルキルピロリドンが４１．７重量部であり、水分は０．１重量部未満、総アミン化合物０．１重量部未満であり、樹脂は検出されなかった。 Oxalic acid dihydrate not involved in the reaction remained as a solid content in the stripping waste liquid.
The separation waste liquid in which the amine-oxalic acid compound is formed is subjected to fractional distillation to collect moisture, a substance in which oxalic acid is decomposed such as formic acid, carbon monoxide, carbon dioxide, and an organic solvent, and a residual resist. Amine-oxalic acid and undecomposed oxalic acid dihydrate were separated and discharged.
The collected organic solvent was cooled to be liquefied, and the components of the liquefied organic solvent were analyzed. As a result, 58.3 parts by weight of glycol and 41.7 parts by weight of alkylpyrrolidone in 100 parts by weight of organic solvent were analyzed. The water content was less than 0.1 parts by weight and the total amine compound was less than 0.1 parts by weight, and no resin was detected.

実施例６
いろいろなレジスト剥離工程で収去されたレジスト２重量部、アミン化合物ＭＥＡ２重量部、ＭＩＰＡ２重量部、ｎ−ＭＥＡ２重量部、水分４０重量部、有機溶媒５２重量部（グリコール３６重量部およびアルキルピロリドン１６重量部）を含む剥離廃液にシュウ酸２水和物４．３重量部を添加してアミン−シュウ酸化合物を形成した。 Example 6
2 parts by weight of resist removed in various resist stripping steps, 2 parts by weight of amine compound MEA, 2 parts by weight of MIPA, 2 parts by weight of n-MEA, 40 parts by weight of water, 52 parts by weight of organic solvent (36 parts by weight of glycol and 16 parts of alkylpyrrolidone 16 An oxalic acid compound was formed by adding 4.3 parts by weight of oxalic acid dihydrate to the exfoliated waste liquid containing (part by weight).

反応に関与しないシュウ酸２水和物は剥離廃液に固形分として残っていた。
前記アミン−シュウ酸化合物が形成された剥離廃液を分別蒸留して、水分とホルム酸、一酸化炭素、二酸化炭素などのシュウ酸の分解された物質と有機溶媒を捕集し、残留するレジストとアミン−シュウ酸および分解されないシュウ酸２水和物を分離排出した。 Oxalic acid dihydrate not involved in the reaction remained as a solid content in the stripping waste liquid.
The separation waste liquid in which the amine-oxalic acid compound is formed is subjected to fractional distillation to collect moisture, a substance in which oxalic acid is decomposed such as formic acid, carbon monoxide, carbon dioxide, and an organic solvent, and a residual resist. Amine-oxalic acid and undecomposed oxalic acid dihydrate were separated and discharged.

前記捕集された有機溶媒を冷却して液体化し、液体化された有機溶媒の成分を分析した結果、有機溶媒１００重量部中のグリコールが６２．８重量部、アルキルピロリドンが３７．２重量部である、水分は０．１重量部未満、総アミン化合物０．１重量部未満であり、樹脂は検出されなかった。   The collected organic solvent was cooled to be liquefied, and the components of the liquefied organic solvent were analyzed. As a result, 62.8 parts by weight of glycol and 37.2 parts by weight of alkylpyrrolidone in 100 parts by weight of organic solvent were analyzed. The water content is less than 0.1 parts by weight and the total amine compound is less than 0.1 parts by weight, and no resin was detected.

本発明の一実施形態によるレジスト剥離廃液再生装置の模式図である。It is a schematic diagram of the resist peeling waste liquid reproduction | regeneration apparatus by one Embodiment of this invention.

符号の説明Explanation of symbols

１０ 被処理レジスト剥離廃液貯蔵槽
１１ ポンプ
１２ 自動調節バルブ
２０ 酸貯蔵槽
２１ ポンプ
２２ 自動調節バルブ
３０ 反応槽
３１ ポンプ
３２ 自動調節バルブ
４０ 蒸留槽
４３ １次蒸留槽
４４ ２次蒸留槽
４５ ３次蒸留槽
４６ 残留成分排出槽
４７ 減圧装置
５０ 有機溶媒貯蔵槽
５３ 凝縮器
６０ アミン化合物槽 DESCRIPTION OF SYMBOLS 10 Processed resist stripping waste liquid storage tank 11 Pump 12 Automatic adjustment valve 20 Acid storage tank 21 Pump 22 Automatic adjustment valve 30 Reaction tank 31 Pump 32 Automatic adjustment valve 40 Distillation tank 43 Primary distillation tank 44 Secondary distillation tank 45 Secondary distillation tank 45 Tertiary distillation Tank 46 Residual component discharge tank 47 Pressure reducing device 50 Organic solvent storage tank 53 Condenser 60 Amine compound tank

Claims (6)

水、レジスト、アミン化合物、有機溶媒を含むレジスト剥離廃液を再生する方法であって、
（ａ）レジスト剥離廃液のアミン化合物と反応し、アミン化合物が有機溶媒蒸留時に蒸留されないアミン−酸化合物を形成する酸を添加する工程；および
（ｂ）前記（ａ）工程の反応物を分別蒸留して有機溶媒のみを収得する工程
を含むことを特徴とするレジスト剥離廃液の再生方法。 A method for regenerating a resist stripping waste liquid containing water, a resist, an amine compound, and an organic solvent,
(A) a step of adding an acid that reacts with an amine compound in the resist stripping waste liquid to form an amine-acid compound in which the amine compound is not distilled during the organic solvent distillation; and (b) fractional distillation of the reaction product in the step (a). And a method for regenerating the resist stripping waste liquid, comprising the step of obtaining only the organic solvent. 前記酸の添加量は、剥離廃液に含まれているアミン化合物と同当量以上である請求項１に記載のレジスト剥離廃液の再生方法。   The method for regenerating a resist stripping waste liquid according to claim 1, wherein the amount of the acid added is equal to or more than the equivalent amount of the amine compound contained in the stripping waste solution. 前記酸は、安息香酸、クエン酸、蟻酸、マレイン酸、リンゴ酸、サリチル酸、酒石酸、酢酸、シュウ酸、燐酸、硝酸、塩酸、硫酸および過塩素酸からなる群より選択される１種以上の化合物である請求項１に記載のレジスト剥離廃液の再生方法。   The acid is one or more compounds selected from the group consisting of benzoic acid, citric acid, formic acid, maleic acid, malic acid, salicylic acid, tartaric acid, acetic acid, oxalic acid, phosphoric acid, nitric acid, hydrochloric acid, sulfuric acid and perchloric acid. The method for regenerating a resist stripping waste liquid according to claim 1. （ａ）水、レジスト、アミン化合物、有機溶媒を含む被処理レジスト剥離廃液貯蔵槽；
（ｂ）酸貯蔵槽；
（ｃ）前記被処理レジスト剥離廃液貯蔵槽から移送された剥離廃液に前記酸貯蔵槽から移送された酸を添加して剥離廃液のアミン化合物を酸と反応させる反応槽；
（ｄ）前記反応槽から移送された剥離廃液を分別蒸留する蒸留槽；および
（ｅ）前記分別蒸留槽で分別蒸留された有機溶媒を捕集して貯蔵する有機溶媒貯蔵槽
を含むことを特徴とするレジスト剥離廃液再生装置。 (A) A treated resist stripping waste liquid storage tank containing water, a resist, an amine compound, and an organic solvent;
(B) an acid storage tank;
(C) A reaction tank in which the acid transferred from the acid storage tank is added to the stripping waste liquid transferred from the treated resist stripping waste liquid storage tank to react the amine compound of the stripping waste liquid with the acid;
(D) a distillation tank for fractional distillation of the stripping waste liquid transferred from the reaction tank; and (e) an organic solvent storage tank for collecting and storing the organic solvent fractionally distilled in the fractional distillation tank. Resist stripping waste liquid recycling equipment. 前記蒸留槽は、水分を捕集するための１次蒸留槽、酸を捕集するための２次蒸留槽、有機溶媒を捕集するための３次蒸留槽を含む請求項４に記載のレジスト剥離廃液再生装置。   The resist according to claim 4, wherein the distillation tank includes a primary distillation tank for collecting water, a secondary distillation tank for collecting acid, and a tertiary distillation tank for collecting organic solvent. Peeling waste liquid recycling device. 前記蒸留槽は減圧装置を備える請求項４に記載のレジスト剥離廃液再生装置。   The resist stripping waste liquid recycling apparatus according to claim 4, wherein the distillation tank includes a decompression device.
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