CN101030046A - Anticorrdant stripping waste liquor regeneration method and device - Google Patents
Anticorrdant stripping waste liquor regeneration method and device Download PDFInfo
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- CN101030046A CN101030046A CNA2007100861617A CN200710086161A CN101030046A CN 101030046 A CN101030046 A CN 101030046A CN A2007100861617 A CNA2007100861617 A CN A2007100861617A CN 200710086161 A CN200710086161 A CN 200710086161A CN 101030046 A CN101030046 A CN 101030046A
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- Prior art keywords
- waste liquor
- stripping waste
- acid
- organic solvent
- mentioned
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- 239000002699 waste material Substances 0.000 title claims description 180
- 238000011069 regeneration method Methods 0.000 title description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 129
- 150000001412 amines Chemical class 0.000 claims abstract description 111
- 238000000034 method Methods 0.000 claims abstract description 61
- 239000002253 acid Substances 0.000 claims abstract description 49
- 230000008569 process Effects 0.000 claims abstract description 40
- 150000001875 compounds Chemical class 0.000 claims abstract description 35
- 238000001914 filtration Methods 0.000 claims abstract description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 34
- 230000001172 regenerating effect Effects 0.000 claims description 29
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 15
- 238000004821 distillation Methods 0.000 claims description 13
- 238000009418 renovation Methods 0.000 claims description 13
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 10
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 10
- 235000006408 oxalic acid Nutrition 0.000 claims description 7
- BJEPYKJPYRNKOW-REOHCLBHSA-N (S)-malic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O BJEPYKJPYRNKOW-REOHCLBHSA-N 0.000 claims description 5
- 239000005711 Benzoic acid Substances 0.000 claims description 5
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 claims description 5
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 5
- BJEPYKJPYRNKOW-UHFFFAOYSA-N alpha-hydroxysuccinic acid Natural products OC(=O)C(O)CC(O)=O BJEPYKJPYRNKOW-UHFFFAOYSA-N 0.000 claims description 5
- 235000010233 benzoic acid Nutrition 0.000 claims description 5
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 5
- 239000011976 maleic acid Substances 0.000 claims description 5
- 239000001630 malic acid Substances 0.000 claims description 5
- 235000011090 malic acid Nutrition 0.000 claims description 5
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 5
- 229960004889 salicylic acid Drugs 0.000 claims description 5
- 229940095064 tartrate Drugs 0.000 claims description 5
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 5
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 claims description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 4
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 claims description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 claims description 4
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 claims description 2
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 claims description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 claims description 2
- 235000015165 citric acid Nutrition 0.000 claims description 2
- 235000019253 formic acid Nutrition 0.000 claims description 2
- 229910017604 nitric acid Inorganic materials 0.000 claims description 2
- -1 amine compounds Chemical class 0.000 abstract description 36
- 239000007788 liquid Substances 0.000 abstract description 31
- 238000004064 recycling Methods 0.000 abstract 7
- GEVPUGOOGXGPIO-UHFFFAOYSA-N oxalic acid;dihydrate Chemical compound O.O.OC(=O)C(O)=O GEVPUGOOGXGPIO-UHFFFAOYSA-N 0.000 description 30
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 19
- 238000005243 fluidization Methods 0.000 description 17
- 239000000203 mixture Substances 0.000 description 14
- 239000007787 solid Substances 0.000 description 14
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 13
- 239000000470 constituent Substances 0.000 description 12
- 239000000654 additive Substances 0.000 description 11
- 230000000996 additive effect Effects 0.000 description 11
- 230000001276 controlling effect Effects 0.000 description 11
- 239000007795 chemical reaction product Substances 0.000 description 8
- 238000001816 cooling Methods 0.000 description 8
- 230000001105 regulatory effect Effects 0.000 description 8
- 239000011347 resin Substances 0.000 description 8
- 229920005989 resin Polymers 0.000 description 8
- 230000008929 regeneration Effects 0.000 description 5
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000003912 environmental pollution Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- SZXQTJUDPRGNJN-UHFFFAOYSA-N dipropylene glycol Chemical compound OCCCOCCCO SZXQTJUDPRGNJN-UHFFFAOYSA-N 0.000 description 2
- 239000004973 liquid crystal related substance Substances 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- 229920002120 photoresistant polymer Polymers 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 230000000630 rising effect Effects 0.000 description 2
- CUVLMZNMSPJDON-UHFFFAOYSA-N 1-(1-butoxypropan-2-yloxy)propan-2-ol Chemical compound CCCCOCC(C)OCC(C)O CUVLMZNMSPJDON-UHFFFAOYSA-N 0.000 description 1
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 1
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 1
- QCDWFXQBSFUVSP-UHFFFAOYSA-N 2-phenoxyethanol Chemical compound OCCOC1=CC=CC=C1 QCDWFXQBSFUVSP-UHFFFAOYSA-N 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- DQFMPTUTAAIXAN-UHFFFAOYSA-N 4,4-dimethyl-1h-imidazol-5-one Chemical compound CC1(C)NC=NC1=O DQFMPTUTAAIXAN-UHFFFAOYSA-N 0.000 description 1
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 description 1
- FXHOOIRPVKKKFG-UHFFFAOYSA-N N,N-Dimethylacetamide Chemical compound CN(C)C(C)=O FXHOOIRPVKKKFG-UHFFFAOYSA-N 0.000 description 1
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 1
- 150000004982 aromatic amines Chemical class 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000012141 concentrate Substances 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 150000004683 dihydrates Chemical class 0.000 description 1
- 229940113088 dimethylacetamide Drugs 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000009931 harmful effect Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 229960005323 phenoxyethanol Drugs 0.000 description 1
- 150000003141 primary amines Chemical class 0.000 description 1
- 150000003335 secondary amines Chemical class 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 150000003512 tertiary amines Chemical class 0.000 description 1
Images
Classifications
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Landscapes
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Automation & Control Theory (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
- Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)
- Heat Treatment Of Water, Waste Water Or Sewage (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Extraction Or Liquid Replacement (AREA)
Abstract
The invention provides a recycling method of a resist stripper scrapped liquid, especially suitable for economical recycling a resist stripper scrapped liquid which is generated when in a stripping process using a stripper scrapped liquid containing various special amine compounds and when using various resists and stripper scrapped liquid, and a recycling device thereof. The recycling device is suitable for being used in the recycling method. The recycling method of the invention is a method for recycling a resist stripper scrapped liquid containing water, resists, amine compounds and an organic solvent, the method is characterized by containing: (a) an acid adding process in which an acid is reacted with the amine compounds of the resist stripper scrapped liquid so that the amine compounds is precipitated as amine-acid manner from the stripper scrapped liquid; (b) a process for filtering the amine-acid compounds precipitated in the process (a) from the stripper scrapped liquid; and (c) a process for distilling the stripper scrapped liquid in which amine is removed in the process (b), so as to obtain the organic solvent.
Description
Technical field
The present invention relates to resist stripping waste liquor regeneration method and regenerating unit, be particularly related to following resist stripping waste liquor regeneration method and regenerating unit, described renovation process is the method that the resist stripping waste liquor that contains water, resist, amines, organic solvent is regenerated, and this method is particularly suitable for the resist stripping waste liquor that better economy ground produced when use being contained the stripping process of stripper of various special amines and when using various resists and stripper and regenerates.
Background technology
In order to make display device such as integrated circuit (IC), high density integrated circuit having (LSI), superelevation integrated circuit semiconductor elements such as (VLSI) and liquid crystal display cells, to implement multistage photoetch operation and resist stripping process repeatedly, produce a large amount of resist stripping waste liquors thus.Particularly owing to the maximization rapidly of display base plate areas such as liquid crystal display cells, the consumption of stripper increases significantly, has further proposed the requirement that utilizes again for stripping waste liquor.
Stripper waste liquid after the resist stripping process uses contains resist, moisture, various organic amine compound and organic solvent.Usually adopted the method for burning disposal as the method for this stripper waste liquid being carried out waste treatment in the past, but because this method is released to incineration gases in the atmosphere, not only environment there is harmful effect, and the composition that can utilize again in the stripper waste liquid also goes out of use, so be not preferred aspect economy, thereby carried out a large amount of research for the regeneration of stripping waste liquor.
In addition, recently, owing in semiconductor and display manufacturing process, further require precision and characterization, so carry out being suitable for most the sectionalization of the photoresist of each operation more, for the composition of employed anticorrosive additive stripping liquid controlling in each stripping process, the kind and the content of in use various organic amines and organic solvent also are segmented.
As the example that regeneration resist stripping waste liquor is attempted, in the following patent documentation 1 (korean patent application 10-2002-0075235 number), a kind of regenerating unit of resist stripping waste liquor is disclosed, the regenerating unit of this resist stripping waste liquor is the regenerating unit that the resist stripping waste liquor that contains alkanolamine, organic solvent and resist is regenerated, and this regenerating unit has membrane separation device, concentration is adjusted jar, alkanolamine feed unit, organic solvent feed unit; It is 100～1500 film that described membrane separation device has molecular cut off, uses above-mentioned film that above-mentioned resist stripping waste liquor is separated into concentrate and sees through liquid; Described concentration is adjusted the above-mentioned liquid that sees through of jar storage, is used for adjusting the above-mentioned alkanolamine of liquid and the concentration of organic solvent of seeing through; Described alkanolamine feed unit is used for adjusting a jar supply alkanolamine to above-mentioned concentration; Described organic solvent feed unit is used for adjusting a jar supply organic solvent to above-mentioned concentration.Said method is that the alkanolamine that utilizes in the resist stripping waste liquor to be contained and organic solvent see through nanometer film and resist does not see through the character of nanometer film and method that stripper is regenerated.
Approach by other has carried out various trials to the regeneration of resist stripping waste liquor in addition, but because disposable separation organic solvent and various amines, so the stripping waste liquor that is produced when being unsuitable for the various photoresists that are segmented that use special amines and stripping process is regenerated, and when in semiconductor and display manufacturing process, using various resists and stripper, because what adopt in the existing anticorrosive additive stripping liquid controlling renovation process is that organic solvent and various amines are carried out disposable mode of separating, thereby its utilization is restricted, and further requirement can be removed the resist in the resist stripping waste liquor, moisture and organic amine compound and the method for only economically organic solvent being regenerated.
[patent documentation 1] korean patent application 10-2002-0075235 number
Summary of the invention
In order to solve above-mentioned prior art problems, the objective of the invention is to, a kind of resist stripping waste liquor regeneration method and regenerating unit are provided, the kind of the amines that is contained in described renovation process and the anticorrosive additive stripping liquid controlling is irrelevant, by the high organic solvent of price being regenerated and making it be used for anticorrosive additive stripping liquid controlling once more, can further alleviate because the environmental pollution that the resist stripping waste liquor is caused, by the high organic solvent of price is reused, further reduce expenses.
Other purpose of the present invention is, a kind of renovation process and regenerating unit of resist stripping waste liquor are provided, and the resist stripping waste liquor that is produced when described renovation process is suitable for that in better economy use contained the stripping process of stripper of various special amines and when using various resists and stripper is regenerated.
In order to reach above-mentioned purpose, the invention provides a kind of renovation process of resist stripping waste liquor, it is the method that the resist stripping waste liquor that contains water, resist, amines, organic solvent is regenerated, and the method is characterized in that it contains:
(a) add sour operation, the amines of described acid and resist stripping waste liquor reacts, and amines is separated out from stripping waste liquor with the form of amine-acid compound;
(b) operation that the amine-acid compound of separating out in above-mentioned (a) operation is leached from stripping waste liquor; With
(c) stripping waste liquor of removing amine in above-mentioned (b) operation is distilled respectively and only obtain the operation of organic solvent.
The present invention also provides a kind of resist stripping waste liquor regenerating unit, and this device is characterised in that it contains:
(a) contain the hold-up tank of the pending resist stripping waste liquor of water, resist, amines, organic solvent;
(b) sour hold-up tank;
(c) acid of being carried by above-mentioned sour hold-up tank is added in the stripping waste liquor of being carried by the hold-up tank of above-mentioned pending resist stripping waste liquor, made the amines and sour retort of reacting of stripping waste liquor;
(d) be used for filtering the filtrator of the amine-acid compound of separating out from the stripping waste liquor of carrying through above-mentioned retort;
(e) from the stripping waste liquor after above-mentioned filtration, distill the alembic of organic solvent respectively; And
(f) the organic solvent hold-up tank that the organic solvent that is distilled respectively in above-mentioned alembic is respectively captured and stores.
The present invention also provides resist stripping waste liquor regenerating unit, and this regenerating unit is characterised in that it contains:
(a) contain the hold-up tank of the pending resist stripping waste liquor of water, resist, amines, organic solvent;
(b) can make the pending resist stripping waste liquor of carrying by above-mentioned pending resist stripping waste liquor hold-up tank sour packed column that pass through and that be provided with filtrator endways;
(c) from by distilling out the alembic of organic solvent the stripping waste liquor of above-mentioned sour packed column respectively; And
(d) the organic solvent hold-up tank that the organic solvent that distills out respectively with above-mentioned alembic is respectively captured and stores.
Has following effect based on anticorrosive additive stripping liquid controlling renovation process of the present invention and regenerating unit: the influence of the kind of the amines that it is not subjected in the anticorrosive additive stripping liquid controlling to be contained, by the high organic solvent of price being regenerated and making it be used for anticorrosive additive stripping liquid controlling once more, can further alleviate because the environmental pollution that the resist stripping waste liquor is caused; By the high organic solvent of price is reused, further reduce expenses; The resist stripping waste liquor that is produced when being particularly suitable for that in better economy use contained the stripping process of stripper of various special amines and when using various resists and stripper is regenerated.
Description of drawings
Fig. 1 is based on the synoptic diagram of the resist stripping waste liquor regenerating unit that utilizes retort of an embodiment of the invention.
Fig. 2 is based on the synoptic diagram of resist stripping waste liquor regenerating unit of the utilization acid packed column of another embodiment of the present invention.
Symbol description
The hold-up tank of 110 pending resist stripping waste liquors
111 pumps
112 automatic regulating valves
120 sour hold-up tanks
122 automatic regulating valves
130 retort
132 automatic regulating valves
140 filtrators
150 alembics
153 single flash jars
154 second distillation jars
155 residual component drain tanks
156 relievers
160 organic solvent hold-up tanks
163 condensers
170 amines jars
210 pending resist stripping waste liquor hold-up tanks
211 pumps
212 automatic regulating valves
220 sour packed columns
221 filtrators
230 alembics
233 single flash jars
234 second distillation jars
235 residual component drain tanks
236 relievers
240 organic solvent hold-up tanks
243 condensers
250 amines jars
Embodiment
Hereinafter the present invention will be described in detail.
The inventor finds, in existing resist stripping waste liquor regeneration method, if the resist stripping waste liquor that is produced when organic amine compound and organic solvent are retrieved that simultaneously use contained the stripping process of stripper of various special amines and when using various resists and stripper is regenerated, then can not be used as stripper because the organic amine compound that is reclaimed is different with the organic amine compound of reality use; After corresponding economic renovation process is studied therewith, find, if utilize economic method, remove resist, moisture and organic amine compound in the resist stripping waste liquor, only capture organic solvent then, the organic amine compound that will be suitable for various special strippers subsequently again makes an addition in the organic solvent of regeneration and makes anticorrosive additive stripping liquid controlling, then can solve whole issue, thereby finish the present invention.
The present invention is the method that the resist stripping waste liquor that contains water, resist, amines, organic solvent is regenerated, the method is characterized in that, it contains: (a) add the operation of acid, the amines of described acid and resist stripping waste liquor reacts and makes amines separate out from stripping waste liquor with the form of amine-acid compound; (b) operation that the amine-acid compound of separating out in above-mentioned (a) operation is leached from stripping waste liquor; (c) stripping waste liquor of removing amine in above-mentioned (b) operation is distilled respectively and only obtain the operation of organic solvent.
Above-mentioned resist stripping waste liquor can contain various organic amine compounds or various organic solvent with the difference of each operation of using stripper.Above-mentioned organic amine compound can be primary amine, secondary amine or tertiary amine, can be fatty amine, aliphatic cyclic amine, aromatic amine, heterocyclic amine, azanol.In addition, above-mentioned organic solvent can contain the single ether of glycol monoethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, ethyleneglycol monophenylether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, dipropylene glycol monomethyl ether, dipropylene glycol, the single propyl ether of dipropylene glycol or the dipropylene glycol monobutyl ether of di-alcohols, can contain alkyl pyrrolidones such as dimethyl sulfoxide (DMSO), dimethyl acetamide, dimethyl formamide, dimethyl-imidazolinone, sulfolane or N-Methyl pyrrolidone.
In resist stripping waste liquor regeneration method of the present invention, as the acid of using in above-mentioned (a) operation, as long as it can react with the amines in the stripping waste liquor and the amines of stripping waste liquor is separated out from stripping waste liquor, be not particularly limited, can use benzoic acid, citric acid, formic acid, maleic acid, malic acid, salicylic acid, tartrate, acetate, oxalic acid, phosphoric acid, nitric acid, hydrochloric acid, sulfuric acid and perchloric acid etc.For the consumption of acid, need add the equivalent identical at least or be higher than the acid of equivalent with the equivalent of the amines that contained in the stripping waste liquor, preferably carry out excessive interpolation so that the amines noresidue.Further preferably use acid remaining when organic solvent distills respectively can not sneak into wherein acid.
By above-mentioned (a) operation, the composition of pending resist stripping waste liquor contains resist, moisture, amine and the reaction product of acid, remaining acid and organic solvent.
The renovation process of resist stripping waste liquor of the present invention contains operation that the amine-acid compound of will separate out in above-mentioned (a) operation leaches as (b) operation from stripping waste liquor.Self-evident, employed filtrator can use the conventional filtration device that can filter out solid constituent from liquid in the above-mentioned filtration.By this operation, amines separated from stripping waste liquor remove.
In addition, the renovation process of resist stripping waste liquor of the present invention contain to the stripping waste liquor of removing amine in above-mentioned (b) operation distill respectively and the operation of only obtaining organic solvent as (c) operation.In this operation, moisture and organic solvent can be distilled out respectively and only capture organic solvent, the resist that is not distilled and have neither part nor lot in reaction and Undec acid can separatedly be discharged by distillation respectively.
The above-mentioned organic solvent that captures respectively can carry out fluidization once more by condenser, thereby can add the amines of special requirement in above-mentioned organic solvent, once more as stripper.
Stripping waste liquor regeneration method of the present invention is not subjected to the influence of the kind of amines, by the high organic solvent of price being regenerated and making it be used for anticorrosive additive stripping liquid controlling once more, can further alleviate because the environmental pollution that the resist stripping waste liquor is caused; By the high organic solvent of price is reused, further reduce expenses.
Hereinafter, as a concrete embodiment of the present invention, to using oxalic acid (C
2H
2O
4) as sour composition so that the method for following stripping waste liquor regeneration describes; Described stripping waste liquor is produced by each resist stripping process, and it is made of amines, organic solvent, moisture and resist, contains MEA, MIPA, n-MEA in the described amines, contains dibasic alcohol and alkyl pyrrolidone in the described organic solvent.Because described oxalic acid exists with the form of dihydrate at normal temperatures, thereby use oxalic acid dihydrate (C
2H
2O
4H
2O).
The total yield that adds with respect to above-mentioned amines in the stripping waste liquor that is made of amines (it contains MEA, MIPA, n-MEA), organic solvent (it contains dibasic alcohol and alkyl pyrrolidone), moisture and resist is excessive oxalic acid dihydrate.By adding oxalic acid dihydrate, oxalic acid dihydrate and the amines generation amine-oxalic acid reaction product that reacts, this amine-oxalic acid reaction product is separated out with solid state.By filtering the amine-oxalic acid reaction product that from stripping waste liquor, filters out solid state.Secondly potpourri to resist, moisture, organic solvent distills respectively then, at first distills out moisture, and dibasic alcohol in organic solvent and alkyl pyrrolidone are separated with residual resist, can only capture the purpose organic solvent by distilling.Then, can in the organic solvent that is captured, optionally add amines such as MEA, MIPA or the n-MEA etc. of special requirement, once more as stripper.
In addition, the invention provides resist stripping waste liquor regenerating unit, this regenerating unit is characterised in that it contains: the hold-up tank that (a) contains the pending resist stripping waste liquor of water, resist, amines, organic solvent; (b) sour hold-up tank; (c) acid of being carried by above-mentioned sour hold-up tank is added in the stripping waste liquor of being carried by the hold-up tank of above-mentioned pending resist stripping waste liquor, made the amines and sour retort of reacting of stripping waste liquor; (d) be used for filtering the filtrator of the amine-acid compound of separating out from the stripping waste liquor of carrying by above-mentioned retort; (e) from the stripping waste liquor after above-mentioned filtration, distill the alembic of organic solvent respectively; And the organic solvent hold-up tank that (f) organic solvent that is distilled respectively in above-mentioned alembic is respectively captured and stores.
Hereinafter pass through the synoptic diagram shown in Figure 1 of an embodiment of resist stripping waste liquor regenerating unit of the present invention, the present invention is carried out specific description.The pending anticorrosive additive stripping liquid controlling that will obtain in each resist stripping process is stored in the pending resist stripping waste liquor hold-up tank 110.Above-mentioned pending resist stripping waste liquor contains resist, and contains various amines such as MEA, MIPA, n-MEA, also contains moisture and organic solvent.The pending resist stripping waste liquor that is stored in the above-mentioned pending resist stripping waste liquor hold-up tank 110 is delivered in the retort 130 along pipe arrangement by pump 111.In order when carrying above-mentioned stripping waste liquor, to regulate the amount of stripping waste liquor, can be provided with automatic regulating valve 112 at the established part of pipe arrangement.This device also has sour hold-up tank 120 in addition, and it is used for storing the acid that the amines that contained with the resist stripping waste liquor reacts.Above-mentioned acid is preferably used benzoic acid, citric acid, maleic acid, malic acid, salicylic acid, tartrate, oxalic acid etc. separately or above-mentioned at least 2 kinds of acid is mixed use.Acid is delivered to the retort 130 along pipe arrangement from above-mentioned sour hold-up tank 120.In order when carrying above-mentioned stripping waste liquor, to regulate the amount of acid, can be provided with automatic regulating valve 122 at the established part of pipe arrangement.When carrying, the amount of the acid that preferably is transferred is for the equivalent that equates with the total yield of the amines that contained in the stripping waste liquor at least or be higher than this equivalent.React retort 130 from the stripping waste liquor of pending resist stripping waste liquor hold-up tank 110 conveyings and the acid of carrying from sour hold-up tank 120, separate out that amine-the acid reaction product (for example, amine-oxalic acid reaction product), contain resist, Acid-Base precipitate, moisture, organic solvent in the stripping waste liquor this moment.The stripping waste liquor that finishes above-mentioned reaction is transferred out from retort 130,, thereby remove the interior solid constituent (amine-oxalic acid precipitate) of stripping waste liquor by filtrator 140.In order when carrying above-mentioned stripping waste liquor, to regulate the amount of stripping waste liquor, can be provided with automatic regulating valve 132 at the established part of pipe arrangement.To be delivered to alembic 150 along pipe arrangement by the stripping waste liquor that above-mentioned filtrator 140 has been removed solid constituent.The composition that distills out in the stripping waste liquor respectively to be contained by the rising temperature in above-mentioned alembic 150 also captures.Preferred above-mentioned alembic 150 is divided into the single flash jar 153 that is used to capture moisture, second distillation jar 154 and the residual component drain tank 155 that is used to capture organic solvent in being provided with.When using oxalic acid dihydrate as acid, the moisture that is contained in the stripping waste liquor is captured by single flash jar 153, organic solvent is captured by second distillation jar 154, and resist distillation does not take place is discharged to residual component drain tank 155.Preferred above-mentioned alembic 150 can be provided with reliever 156 in addition, and can reduce vapo(u)rizing temperature this moment.To be delivered to organic solvent hold-up tank 160 by the organic solvent that above-mentioned second distillation jar 154 is captured.Above-mentioned organic solvent hold-up tank 160 has condenser 163, can make the organic solvent that is captured become liquid condition.Preferred above-mentioned organic solvent hold-up tank 160 is connected with the amines jar 170 of the amines that can add regulation, can add the amines that only is suitable for indivedual resist stripping processs by the amines that adds regulation, makes stripping liquid for regenerating thus.
The present invention also provides resist stripping waste liquor regenerating unit, and this regenerating unit is characterised in that it contains: the hold-up tank that (a) contains the pending resist stripping waste liquor of water, resist, amines, organic solvent; (b) can make the pending resist stripping waste liquor of carrying by above-mentioned pending resist stripping waste liquor hold-up tank sour packed column that pass through and that be provided with filtrator endways; (c) from by distilling out the alembic of organic solvent the stripping waste liquor of above-mentioned sour packed column respectively; And the organic solvent hold-up tank that (d) organic solvent that is distilled respectively in above-mentioned alembic is respectively captured and stores.
Hereinafter pass through the synoptic diagram shown in Figure 2 of an embodiment of resist stripping waste liquor regenerating unit of the present invention, the present invention is carried out specific description.The pending anticorrosive additive stripping liquid controlling that will obtain in each resist stripping process is stored in the pending resist stripping waste liquor hold-up tank 210.Above-mentioned pending resist stripping waste liquor contains resist, and contains various amines such as MEA, MIPA, n-MEA, also contains moisture and organic solvent.The pending resist stripping waste liquor that is stored in the above-mentioned pending resist stripping waste liquor hold-up tank 210 is delivered to sour packed column 220 by pump 211 along pipe arrangement.In order when carrying above-mentioned stripping waste liquor, to regulate the amount of stripping waste liquor, can be provided with automatic regulating valve 212 at the established part of pipe arrangement.Be filled with the acid that the reaction product that can react and make amine-acid with the amines that contained in the resist stripping waste liquor is separated out in the above-mentioned sour packed column 220 from stripping waste liquor.Above-mentioned acid is preferably used benzoic acid, citric acid, maleic acid, malic acid, salicylic acid, tartrate, oxalic acid etc. separately or above-mentioned at least 2 kinds of acid mixing is used.When stripping waste liquor during by above-mentioned sour packed column 220, the amines and the acid that are contained in the stripping waste liquor react, the reaction product of amine-acid is separated out from stripping waste liquor, the filtrator that end had 221 by sour packed column 220 filters out, thereby only makes the stripping waste liquor of having removed amines by filtrator 221.To be delivered to alembic 230 along pipe arrangement by the stripping waste liquor that above-mentioned filtrator 221 has been removed solid constituent.The composition that distills out in the stripping waste liquor respectively to be contained by the rising temperature in above-mentioned alembic 230 also captures.Preferred above-mentioned alembic 230 is divided into the single flash jar 233 that is used to capture moisture, second distillation jar 234 and the residual component drain tank 235 that is used to capture organic solvent in being provided with.When using oxalic acid dihydrate as acid, the moisture that is contained in the stripping waste liquor is captured by single flash jar 233, and organic solvent is captured by second distillation jar 234, and resist distillation does not take place is discharged to residual component drain tank 235.Preferred above-mentioned alembic 230 can have reliever 236 in addition, and can reduce vapo(u)rizing temperature this moment.To be delivered to organic solvent hold-up tank 240 by the organic solvent that above-mentioned second distillation jar 234 is captured.Above-mentioned organic solvent hold-up tank 240 has condenser 243, can make the organic solvent that is captured become liquid condition.Preferred above-mentioned organic solvent hold-up tank 240 is connected with the amines jar 250 of the amines that can add regulation, can add the amines that only is suitable for indivedual resist stripping processs by the amines that adds regulation, makes stripping liquid for regenerating thus.
Hereinafter enumerate preferred embodiment in order to understand the present invention, but embodiment only is used for the present invention is carried out example, scope of the present invention is not limited to following embodiment.
[embodiment]
Embodiment 1
Add 10.6 weight portion oxalic acid dihydrate in the stripping waste liquor that contains 3 weight portion resists, 5 portions of amine by weight compound MEA, 5 portions of amine by weight compound MIPA, 5 portions of amine by weight compound n-MEA, 10 weight portion moisture, 72 weight portion organic solvents (50 weight portion dibasic alcohol and 22 weight portion alkyl pyrrolidones) that is obtained by each resist stripping process, formation amine-oxalate compound is also separated out.The oxalic acid dihydrate that has neither part nor lot in reaction residues in the stripping waste liquor with the solid constituent form.With filtrator the above-mentioned stripping waste liquor that has formed amine-oxalate compound is filtered to remove solid constituent.By the above-mentioned oxalic acid dihydrate that removes by filter the amine-oxalate compound of separating out and have neither part nor lot in reaction, so that with respect to the stripping waste liquor after the filtration of 100 weight portions, total amines is less than 0.1 weight portion.Stripping waste liquor after the above-mentioned filtration is distilled respectively, capture moisture and organic solvent, residual resist is separated discharge with amine-oxalic acid and undecomposed oxalic acid dihydrate.The organic solvent cooling of above-mentioned capture is made its fluidization, after the composition of the organic solvent of fluidization analyzed as can be known, the dibasic alcohol in the 100 weight portion organic solvents be 67.4 weight portions, alkyl pyrrolidone be 32.6 weight portions, moisture less than 0.1 weight portion, total amines less than 0.1 weight portion, do not detect resin.
Embodiment 2
Add 8.5 weight portion oxalic acid dihydrate in the stripping waste liquor of the organic solvent that contains 3 weight portion resists, 4 portions of amine by weight compound MEA, 4 portions of amine by weight compound MIPA, 4 portions of amine by weight compound n-MEA, 20 weight portion moisture, 65 weight portions (45 weight portion dibasic alcohol and 20 weight portion alkyl pyrrolidones) that is obtained by each resist stripping process, formation amine-oxalate compound is also separated out.The oxalic acid dihydrate that has neither part nor lot in reaction residues in the stripping waste liquor with the solid constituent form.With filtrator the above-mentioned stripping waste liquor that is formed with amine-oxalate compound is filtered to remove solid constituent.By the above-mentioned oxalic acid dihydrate that removes by filter the amine-oxalate compound of separating out and have neither part nor lot in reaction, so that with respect to the stripping waste liquor after the filtration of 100 weight portions, total amines is less than 0.1 weight portion.Stripping waste liquor after the above-mentioned filtration is distilled respectively, capture moisture and organic solvent, residual resist is separated discharge with amine-oxalic acid and undecomposed oxalic acid dihydrate.The organic solvent cooling of above-mentioned capture is made its fluidization, after the composition of the organic solvent of fluidization analyzed as can be known, the dibasic alcohol in the 100 weight portion organic solvents be 66.5 weight portions, alkyl pyrrolidone be 33.5 weight portions, moisture less than 0.1 weight portion, total amines less than 0.1 weight portion, do not detect resin.
Embodiment 3
Add 6.4 weight portion oxalic acid dihydrate in the stripping waste liquor that contains 2 weight portion resists, 3 portions of amine by weight compound MEA, 3 portions of amine by weight compound MIPA, 3 portions of amine by weight compound n-MEA, 30 weight portion moisture, 59 weight portion organic solvents (41 weight portion dibasic alcohol and 18 weight portion alkyl pyrrolidones) that is obtained by each resist stripping process, formation amine-oxalate compound is also separated out.The oxalic acid dihydrate that has neither part nor lot in reaction residues in the stripping waste liquor with the solid constituent form.With filtrator the above-mentioned stripping waste liquor that is formed with amine-oxalate compound is filtered to remove solid constituent.By the above-mentioned oxalic acid dihydrate that removes by filter the amine-oxalate compound of separating out and have neither part nor lot in reaction, so that with respect to the stripping waste liquor after the filtration of 100 weight portions, total amines is less than 0.1 weight portion.Stripping waste liquor after the above-mentioned filtration is distilled respectively, capture moisture and organic solvent, residual resist, amine-oxalic acid and undecomposed oxalic acid dihydrate are separated discharge.The organic solvent cooling of above-mentioned capture is made its fluidization, after the composition of the organic solvent of fluidization analyzed as can be known, the dibasic alcohol in the 100 weight portion organic solvents be 67.5 weight portions, alkyl pyrrolidone be 32.5 weight portions, moisture less than 0.1 weight portion, total amines less than 0.1 weight portion, do not detect resin.
Embodiment 4
Add 4.3 weight portion oxalic acid dihydrate in the stripping waste liquor that contains 2 weight portion resists, 2 portions of amine by weight compound MEA, 2 portions of amine by weight compound MIPA, 2 portions of amine by weight compound n-MEA, 40 weight portion moisture, 52 weight portion organic solvents (36 weight portion dibasic alcohol and 16 weight portion alkyl pyrrolidones) that is obtained by each resist stripping process, formation amine-oxalate compound is also separated out.The oxalic acid dihydrate that has neither part nor lot in reaction residues in the stripping waste liquor with the solid constituent form.With filtrator the above-mentioned stripping waste liquor that is formed with amine-oxalate compound is filtered to remove solid constituent.By the above-mentioned oxalic acid dihydrate that removes by filter the amine-oxalate compound of separating out and have neither part nor lot in reaction, so that with respect to the stripping waste liquor after the filtration of 100 weight portions, total amines is less than 0.1 weight portion.Stripping waste liquor after the above-mentioned filtration is separated distillation, capture moisture and organic solvent, residual resist is separated discharge with amine-oxalic acid and undecomposed oxalic acid dihydrate.The organic solvent cooling of above-mentioned capture is made its fluidization, after the composition of the organic solvent of fluidization analyzed as can be known, in the 100 weight portion organic solvents dibasic alcohol be 67.4 weight portions, alkyl pyrrolidone be 32.6 weight portions, moisture less than 0.1 weight portion, total amines less than 0.1 weight portion, do not detect resin.
Embodiment 5
Make the stripping waste liquor that contains 3 weight portion resists, 5 portions of amine by weight compound MEA, 5 portions of amine by weight compound MIPA, 5 portions of amine by weight compound n-MEA, 10 weight portion moisture, 72 weight portion organic solvents (50 weight portion dibasic alcohol and 22 weight portion alkyl pyrrolidones) that obtains by each resist stripping process by being filled with 19.5 weight portion oxalic acid dihydrate and being provided with the packed column of filtrator endways, so that amines is separated out and is filtered with the form of amine-oxalate compound.With respect to the stripping waste liquor after the above-mentioned filtration of 100 weight portions, total amines is less than 0.1 weight portion.Stripping waste liquor after the above-mentioned filtration is distilled respectively, capture moisture and organic solvent, residual resist is separated discharge with amine-oxalic acid and undecomposed oxalic acid dihydrate.The organic solvent cooling of above-mentioned capture is made its fluidization, after the composition of the organic solvent of fluidization analyzed as can be known, in the 100 weight portion organic solvents dibasic alcohol be 67.0 weight portions, alkyl pyrrolidone be 33.0 weight portions, moisture less than 0.1 weight portion, total amines less than 0.1 weight portion, do not detect resin.
Embodiment 6
Make the stripping waste liquor that contains 3 weight portion resists, 4 portions of amine by weight compound MEA, 4 portions of amine by weight compound MIPA, 4 portions of amine by weight compound n-MEA, 20 weight portion moisture, 65 weight portion organic solvents (45 weight portion dibasic alcohol and 20 weight portion alkyl pyrrolidones) that obtains by each resist stripping process by being filled with 15.6 weight portion oxalic acid dihydrate and being provided with the packed column of filtrator endways, so that amines is separated out and filtered with the form of amine-oxalate compound.With respect to the stripping waste liquor after the above-mentioned filtration of 100 weight portions, total amines is less than 0.1 weight portion.Stripping waste liquor after the above-mentioned filtration is distilled respectively, capture moisture and organic solvent, residual resist is separated discharge with amine-oxalic acid and undecomposed oxalic acid dihydrate.The organic solvent cooling of above-mentioned capture is made its fluidization, after the composition of the organic solvent of fluidization analyzed as can be known, in the 100 weight portion organic solvents dibasic alcohol be 66.7 weight portions, alkyl pyrrolidone be 33.3 weight portions, moisture less than 0.1 weight portion, total amines less than 0.1 weight portion, do not detect resin.
Embodiment 7
Make the stripping waste liquor that contains 2 weight portion resists, 3 portions of amine by weight compound MEA, 3 portions of amine by weight compound MIPA, 3 portions of amine by weight compound n-MEA, 30 weight portion moisture, 59 weight portion organic solvents (41 weight portion dibasic alcohol and 18 weight portion alkyl pyrrolidones) that obtains by each resist stripping process by being filled with 11.7 weight portion oxalic acid dihydrate and being provided with the packed column of filtrator endways, so that amines is separated out and filtered with the form of amine-oxalate compound.With respect to the stripping waste liquor after the above-mentioned filtration of 100 weight portions, total amines is less than 0.1 weight portion.Stripping waste liquor after the above-mentioned filtration is distilled respectively, capture moisture and organic solvent, residual resist is separated discharge with amine-oxalic acid and undecomposed oxalic acid dihydrate.The organic solvent cooling of above-mentioned capture is made its fluidization, after the composition of the organic solvent of fluidization analyzed as can be known, in the 100 weight portion organic solvents dibasic alcohol be 67.2 weight portions, alkyl pyrrolidone be 32.8 weight portions, moisture less than 0.1 weight portion, total amines less than 0.1 weight portion, do not detect resin.
Embodiment 8
Make the stripping waste liquor that contains 2 weight portion resists, 2 portions of amine by weight compound MEA, 2 portions of amine by weight compound MIPA, 2 portions of amine by weight compound n-MEA, 40 weight portion moisture, 52 weight portion organic solvents (36 weight portion dibasic alcohol and 16 weight portion alkyl pyrrolidones) that obtains by each resist stripping process by being filled with 7.8 weight portion oxalic acid dihydrate and being provided with the packed column of filtrator endways, so that amines is separated out and is filtered with the form of amine-oxalate compound.With respect to the stripping waste liquor after the above-mentioned filtration of 100 weight portions, total amines is less than 0.1 weight portion.Stripping waste liquor after the above-mentioned filtration is distilled respectively, capture moisture and organic solvent, residual resist is separated discharge with amine-oxalic acid and undecomposed oxalic acid dihydrate.The organic solvent cooling of above-mentioned capture is made its fluidization, after the composition of the organic solvent of fluidization analyzed as can be known, in the 100 weight portion organic solvents dibasic alcohol be 66.5 weight portions, alkyl pyrrolidone be 33.5 weight portions, moisture less than 0.1 weight portion, total amines less than 0.1 weight portion, do not detect resin.
Claims (8)
1. the renovation process of a resist stripping waste liquor, it is the method that the resist stripping waste liquor that contains water, resist, amines, organic solvent is regenerated, and the method is characterized in that it contains:
(a) add sour operation, the amines of described acid and resist stripping waste liquor reacts, and makes amines separate out from stripping waste liquor with the form of amine-acid compound;
(b) operation that the amine-acid compound of separating out in above-mentioned (a) operation is removed by filter from stripping waste liquor; With
(c) stripping waste liquor of removing amine in above-mentioned (b) operation is distilled respectively and only obtain the operation of organic solvent.
2. the renovation process of resist stripping waste liquor as claimed in claim 1 is characterized in that, the addition of described acid adopts at least equivalent that equates with the equivalent of the amines that contained in the stripping waste liquor or the amount that is higher than this equivalent.
3. the renovation process of resist stripping waste liquor as claimed in claim 1, it is characterized in that described acid is at least a kind that is selected from the group of being made up of benzoic acid, citric acid, formic acid, maleic acid, malic acid, salicylic acid, tartrate, acetate, oxalic acid, phosphoric acid, nitric acid, hydrochloric acid, sulfuric acid and perchloric acid.
4. resist stripping waste liquor regenerating unit, this device is characterised in that it contains:
(a) contain the hold-up tank of the pending resist stripping waste liquor of water, resist, amines, organic solvent;
(b) sour hold-up tank;
(c) acid of being carried by above-mentioned sour hold-up tank is added in the stripping waste liquor of being carried by the hold-up tank of above-mentioned pending resist stripping waste liquor, made the amines and sour retort of reacting of stripping waste liquor;
(d) be used for filtering the filtrator of the amine-acid compound of separating out from the stripping waste liquor of carrying by above-mentioned retort;
(e) from the stripping waste liquor after above-mentioned filtration, distill the alembic of organic solvent respectively; And
(f) the organic solvent hold-up tank that the organic solvent that is distilled out respectively in above-mentioned alembic is respectively captured and stores.
5. resist stripping waste liquor regenerating unit as claimed in claim 4 is characterized in that, described alembic comprises and is used to the second distillation jar that captures the single flash jar of moisture and be used to capture organic solvent.
6. resist stripping waste liquor regenerating unit as claimed in claim 4 is characterized in that described alembic has reliever.
7. resist stripping waste liquor regenerating unit, this regenerating unit is characterised in that it contains:
(a) contain the hold-up tank of the pending resist stripping waste liquor of water, resist, amines, organic solvent;
(b) can make the pending resist stripping waste liquor of carrying by above-mentioned pending resist stripping waste liquor hold-up tank sour packed column that pass through and that be provided with filtrator endways;
(c) from by distilling out the alembic of organic solvent the stripping waste liquor of above-mentioned sour packed column respectively; And
(d) the organic solvent hold-up tank that the organic solvent that is distilled respectively in above-mentioned alembic is respectively captured and stores.
8. resist stripping waste liquor regenerating unit as claimed in claim 7 is characterized in that, employed acid is at least a kind that is selected from the group of being made up of benzoic acid, citric acid, maleic acid, malic acid, salicylic acid, tartrate and oxalic acid in the described sour packed column.
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| KR1020060020449A KR101266897B1 (en) | 2006-03-03 | 2006-03-03 | A recycling method for resist stripper scrapped and a recycling device for same |
| KR10-2006-0020449 | 2006-03-03 | ||
| KR1020060020449 | 2006-03-03 |
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| CN101030046A true CN101030046A (en) | 2007-09-05 |
| CN101030046B CN101030046B (en) | 2011-08-24 |
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| JP (1) | JP4833113B2 (en) |
| KR (1) | KR101266897B1 (en) |
| CN (1) | CN101030046B (en) |
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| TW256929B (en) * | 1993-12-29 | 1995-09-11 | Hirama Rika Kenkyusho Kk | |
| US6106722A (en) * | 1997-08-12 | 2000-08-22 | Kinetico Incorporated | Filtering photoresist-containing liquid |
| CN1276307C (en) * | 1998-08-11 | 2006-09-20 | 东进化成工业株式会社 | Stripping agent, stripping method, thereof, stripping agent circulator and stripping agent controller |
| JP3409005B2 (en) | 1999-01-29 | 2003-05-19 | 松下環境空調エンジニアリング株式会社 | Method and apparatus for regenerating stripper |
| JP2002131932A (en) | 2000-10-24 | 2002-05-09 | Kimura Chem Plants Co Ltd | Method for regenerating and recovering resist removing liquid, and device for regenerating and recovering the same |
| KR100390567B1 (en) * | 2000-12-30 | 2003-07-07 | 주식회사 동진쎄미켐 | method of controlling photoresist stripping process and method of regenerating photoresist stripping composition using near infrared spectrometer |
| JP2003057852A (en) | 2001-08-21 | 2003-02-28 | Asahi Kasei Corp | Method and system for treatment of stripped piece of resist |
| JP2003167358A (en) * | 2001-11-29 | 2003-06-13 | Nagase & Co Ltd | Equipment for regenerating used resist peeling solution and method therefor |
| JP2004066085A (en) * | 2002-08-05 | 2004-03-04 | Kimura Chem Plants Co Ltd | Solvent recovery system |
| JP4080449B2 (en) * | 2004-03-31 | 2008-04-23 | 日本リファイン株式会社 | Solvent recovery device and solvent recovery method |
| KR101266883B1 (en) * | 2006-03-03 | 2013-05-23 | 주식회사 동진쎄미켐 | A recycling method for resist stripper scrapped and a recycling device for same |
-
2006
- 2006-03-03 KR KR1020060020449A patent/KR101266897B1/en active IP Right Grant
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2007
- 2007-03-01 JP JP2007051310A patent/JP4833113B2/en active Active
- 2007-03-02 TW TW096107177A patent/TWI418958B/en active
- 2007-03-05 CN CN2007100861617A patent/CN101030046B/en active Active
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN103721427A (en) * | 2012-10-11 | 2014-04-16 | 日本瑞环化工有限公司 | Resist stripper regeneration methods and devices |
| CN103721427B (en) * | 2012-10-11 | 2016-08-17 | 日本瑞环化工有限公司 | The renovation process of anticorrosive additive stripping liquid controlling and regenerating unit |
| TWI574919B (en) * | 2012-10-11 | 2017-03-21 | Nippon Refine Co Ltd | The method of regenerating the photoresist stripping liquid and the regeneration device |
| CN102951761A (en) * | 2012-11-14 | 2013-03-06 | 杭州格林达化学有限公司 | Method for recovering waste photoresist stripper |
| WO2014198078A1 (en) * | 2013-06-13 | 2014-12-18 | 深圳市华星光电技术有限公司 | Solution for testing moisture content in photoresist stripping solution and testing method |
| CN107193189A (en) * | 2016-03-14 | 2017-09-22 | 株式会社平间理化研究所 | The modulating device of the modulating device of water system anticorrosive additive stripping liquid controlling and non-water system anticorrosive additive stripping liquid controlling |
| CN107664928A (en) * | 2016-07-29 | 2018-02-06 | 罗文烽 | Useless photoresist reclaiming System and method for |
| CN110015707A (en) * | 2019-03-05 | 2019-07-16 | 厦门大学 | A kind of useless stripper recyclable device of photoresist |
| CN116003228A (en) * | 2022-12-26 | 2023-04-25 | 南京长江江宇环保科技股份有限公司 | Method for comprehensively utilizing photoresist-removing waste liquid |
Also Published As
| Publication number | Publication date |
|---|---|
| JP4833113B2 (en) | 2011-12-07 |
| JP2007241277A (en) | 2007-09-20 |
| CN101030046B (en) | 2011-08-24 |
| KR101266897B1 (en) | 2013-05-23 |
| TW200745785A (en) | 2007-12-16 |
| KR20070090573A (en) | 2007-09-06 |
| TWI418958B (en) | 2013-12-11 |
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