CN101529338A - Method of neutralizing developer waste liquid containing tetraalkylammonium hydroxide - Google Patents
Method of neutralizing developer waste liquid containing tetraalkylammonium hydroxide Download PDFInfo
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- CN101529338A CN101529338A CNA2007800399857A CN200780039985A CN101529338A CN 101529338 A CN101529338 A CN 101529338A CN A2007800399857 A CNA2007800399857 A CN A2007800399857A CN 200780039985 A CN200780039985 A CN 200780039985A CN 101529338 A CN101529338 A CN 101529338A
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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
- G03F7/30—Imagewise removal using liquid means
- G03F7/3092—Recovery of material; Waste processing
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/02—Foam dispersion or prevention
- B01D19/04—Foam dispersion or prevention by addition of chemical substances
- B01D19/0404—Foam dispersion or prevention by addition of chemical substances characterised by the nature of the chemical substance
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/68—Treatment of water, waste water, or sewage by addition of specified substances, e.g. trace elements, for ameliorating potable water
- C02F1/685—Devices for dosing the additives
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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
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
- G03F7/322—Aqueous alkaline compositions
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/66—Treatment of water, waste water, or sewage by neutralisation; pH adjustment
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Abstract
The present invention discloses a method of neutralizing a developer waste liquid containing a tetraalkylammonium hydroxide wherein an organic matter derived from photoresist is dissolved through reaction with carbon dioxide gas, in which clogging by intra-column resist precipitation at neutralization can be effectively prevented and in which resist precipitated at neutralization ensures a high filterability and can be effectively removed. The method of neutralizing a developer waste liquid containing a tetraalkylammonium hydroxide comprises adding carbon dioxide gas to a developer waste liquid containing tetraalkylammonium hydroxide of 13 or higher pH value in which an organic matter derived from photoresist is dissolved to thereby carry out neutralization to a pH value of 11.5 or below, wherein the rate of carbon dioxide gas added from the time at which the pH of the developer waste liquid is 13 to the time at which the pH reaches 12 is 0.15 L/hr or less per mol of tetraalkylammonium hydroxide contained in the developer waste liquid at the time of pH 13.
Description
Technical field
[0001]
The present invention relates to tetra-alkyl ammonium hydroxide (Tetra alkyl ammonium hydroxide, hereinafter to be referred as TAAH) after using as the imaging liquid of photoresist, dissolving is from the video picture waste liquid that contains TAAH of the organism (being designated hereinafter simply as " from the organism of photoresist ") of photoresist, utilizes in the carbon dioxide and the new neutralization method of usefulness.In detail, relate to during the video picture waste liquid that contains TAAH carried out and the time in reactive tank owing to separate out preventing of the obstruction that causes from photoresist organic, and in and the time organism from photoresist of separating out good because of filterableness, thereby can effectively remove the neutralization method that is contained in the photoresist in this video picture waste liquid.
Background technology
[0002]
In semiconductor, liquid crystal manufacturing process, when on substrates such as wafer, glass, forming pattern, carry out work as described below, promptly on the metal level that is formed on the substrate surface, be coated with the photoresist of eurymeric or minus, make its exposure by forming the photomask that this pattern uses then, after using developer solution to carry out video picture to unhardened part or sclerosis part, carry out etching, on above-mentioned metal level, form pattern.Highly integrated along with semiconductor etc. sneaked into impurity to the medicament that uses etc. in manufacturing process, particularly pick-up metal ion etc. has strict restriction in semiconductor manufacturing process.Therefore, the akaline liquid TAAH that does not comprise metallic ion is that the imaging liquid of major component is used widely in the photoetching plate-making process.Particularly in recent years, along with the increase of the turnout of semiconductor, liquid crystal, the consumption of imaging liquid is increasing always, and the discharge rate of the video picture waste liquid that contains TAAH after the use is also increasing.
[0003]
Up to now, it is discarded then that the known sewage water treatment method of video picture waste water utilization of the above-mentioned TAAH of containing carries out harmless treatment, but for the purpose of efficent use of resources, proposed from above-mentioned waste liquid, to reclaim TAAH the renovation process that contains TAAH video picture waste liquid made from extra care and then utilizing.For example, there is such method to be suggested, this method comprises that to utilize carbon dioxide that TAAH concentration is concentrated to used TAAH aqueous solution more than the 10 quality % this pH value of aqueous solution that neutralizes be below 10, make from the organism of photoresist separate out in and operation, be separated in this and separate out in the operation carry out electrolysis from the organic separation circuit of photoresist and to the liquid that obtains from this separation circuit, generate the electrowinning process (referring to Patent Document 1) of TAAH.
[0004]
Utilizing carbon dioxide neutralization to contain under the situation of video picture waste liquid of TAAH, according to following reaction equation (1) and (2), the carbonate that generates TAAH also has supercarbonate, makes ratio reduction from the TAAH of the organism dissolving of photoresist with this.So the organic solubleness from photoresist in this video picture waste liquid reduces, separate out from the organism of photoresist, therefore can wait operation with its removal by filtering.
(changing 1)
2TAAH+CO
2→ (TAA)
2CO
3(formula 1)
(TAA)
2CO
3+ H
2O+CO
2→ 2 (TAA) HCO
3(formula 2)
[0005]
Above-mentioned renovation process can utilize easy operation such as filtration to remove the organism from photoresist as major impurity, particularly carbon dioxide is being used as under the situation of the acid that is used in neutralization, sneaking into of the impurity that metallic ion etc. throw into question in semiconductor manufacturing process is few, therefore is the renovation process that contains at the video picture waste liquid of industrial useful TAAH.
Patent documentation 1: No. the 3110513rd, Japan's special permission
Summary of the invention
Invent technical matters to be solved
[0006]
But, separate out as the organism from photoresist of impurity making, utilize carbon dioxide neutralization to contain in the operation of video picture waste liquid of TAAH, neutralize if just carbon dioxide is blown in this video picture waste liquid, the organic stickability of then separating out from photoresist is big, therefore on the easy inwall or connected pipe arrangement attached to reactive tank, often make its obstruction, and because above-mentioned organism from photoresist of separating out is particulate, strainability is very bad in removing operation, has ineffective problem.And TAAH is strong basicity, and fat-soluble very good, is dangerous therefore, and the increase of the cleaning treatment workload of the pipe arrangement of obstruction also can throw into question in work.
The technological means of technical solution problem
[0007]
The present inventor concentrates on studies to achieve these goals again and again.The result judges following situation, promptly by being that the video picture waste liquid that contains tetra-alkyl ammonium hydroxide more than 13 adds under the situation that carbon dioxide neutralizes to being dissolved with organic pH value from photoresist, (1) separating out from the pH value of above-mentioned imaging liquid from photoresist organic is about 13, when the pH value that neutralizes thereafter is 11.5 left and right sides, just stop to separate out after most of described organism is separated out, (2) are separated out from photoresist organic and are carved into the pH value when the pH value from above-mentioned video picture waste liquid is 13 to reach this zone of the moment of 12 remarkable especially.Therefore, the interpolation of the carbon dioxide in the neutralization in such pH value zone of above-mentioned video picture waste liquid, add according to the addition of each mole usefulness below 0.15 liter/hour that to the pH value is the tetra-alkyl ammonium hydroxide in the video picture waste liquid in moment of 13, can form the big flocculent deposit of particle diameter like this, and find to access from the fabulous precipitate of the organic filterableness of this photoresist.And confirm that in this operation separate out with the approaching state of crystallization again from the organism of photoresist, it is higher therefore to remove this organic efficiency ratio.And find that surprisingly above-mentioned precipitate stickability is lower, also can prevent the obstruction of pipe arrangement etc. extremely effectively, to such an extent as to finish the present invention.
[0008]
That is to say, the present invention is a kind of neutralization method that contains the video picture waste liquid of tetra-alkyl ammonium hydroxide, by to being dissolved with organic from photoresist, the pH value is that the video picture waste liquid that contains TAAH more than 13 adds carbon dioxide, it is neutralized the pH value below 11.5, it is characterized in that, from the pH value of above-mentioned video picture waste liquid be 13 the time be carved into the interpolation that the pH value reaches the carbon dioxide in moment of 12, add according to the addition of each mole usefulness below 0.15 liter/hour that to the pH value is the tetra-alkyl ammonium hydroxide in the video picture waste liquid in moment of 13.
[0009]
Also have, the present invention is a kind of neutralization method that contains the video picture waste liquid of tetra-alkyl ammonium hydroxide, by to being dissolved with organic from photoresist, the pH value neutralizes the pH value below 11.5 above 13.7 the video picture waste liquid interpolation carbon dioxide that contains tetra-alkyl ammonium hydroxide with it, it is characterized in that, the pH value of this video picture waste liquid is become more than 13,13.7 the 1st of any pH value in the following scope neutralizes and reaches in the 2nd after this any pH value and carry out in different reactive tanks, simultaneously in the 2nd and in, from the pH value of video picture waste liquid be 13 the time be carved into the interpolation that the pH value reaches the carbon dioxide in moment of 12, according to the pH value being each mole of tetra-alkyl ammonium hydroxide in the video picture waste liquid in moment of 13, carry out with the addition below 0.15 liter/hour.
Technique effect
[0010]
If adopt neutralization method of the present invention, can make from the organism of photoresist and separate out, form the bigger flocculent deposit of particle diameter ratio, therefore can access the good precipitate of filterableness.Therefore the organic removal from photoresist that becomes problem in the electrowinning process after neutralization can high-level efficiency be carried out.And above-mentioned precipitate stickability is low, can not adhere on the pipe arrangement, and problems such as pipe arrangement obstruction can not take place, industrial be safe and high efficiency.
[0011]
And, the pH value of video picture waste liquid is become more than 13, the 1st neutralization of any pH value in the 13.7 following scopes with reach this any pH value after the 2nd in in different reactive tanks, carry out, the enforcement that can walk abreast respectively neutralizes, therefore can shorten the time of neutralization, can raise the efficiency industrial.
Description of drawings
[0012]
Fig. 1 is the skeleton diagram of the desirable embodiment that the 1st neutralization reaction and the 2nd neutralization reaction are carried out in different reactive tanks respectively among expression the present invention.
Embodiment
[0013]
Be dissolved with development waste liquid from the organic TAAH of containing of photoresist
To what use in the present invention, the development waste liquid (being designated hereinafter simply as " the video picture waste liquid that contains TAAH ") that is dissolved with from the organic TAAH of containing of photoresist is elaborated below.In the present invention, as the object lesson of TAAH, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, tetrapropylammonium hydroxide, tetrabutylammonium etc. can have been enumerated.In above-mentioned TAAH, on widely used point, be suitable for using tetramethyl ammonium hydroxide as the imaging liquid in the semiconductor fabrication process.
[0014]
Concentration to the TAAH in the video picture waste liquid that contains TAAH that uses in the neutralization method of the present invention is not particularly limited, and can use the video picture waste liquid of various TAAH concentration.The concentration of TAAH in the video picture waste liquid of discharging in the semiconductor fabrication process, usually be about below 1%, but contain the consideration of the video picture waste liquid of TAAH from industrial high-level efficiency neutralization, or from the consideration of the conveying cost that can reduce this video picture waste liquid, preferably the video picture waste liquid that contains TAAH is concentrated, improve the containing ratio of TAAH wherein.This contains the concentration of the TAAH in the video picture waste liquid of TAAH, if low excessively as mentioned above, then carry processing costs such as cost to uprise, if this excessive concentration, then concentrate needed cost and uprise, therefore preferably this concentration that contains TAAH in the video picture waste liquid of TAAH in 10～30 quality % scopes.
[0015]
Concentrate by above-mentioned, the pH value of the video picture waste liquid that contains TAAH of containing ratio that has improved TAAH is in 13～15 scopes, and is common in 14～14.7 scope.
[0016]
In the above-mentioned video picture waste liquid that contains TAAH, be dissolved with organism from photoresist again.Organic meltage and the organic solubleness from photoresist in TAAH concentration above-mentioned concentrate after from photoresist of above-mentioned organic concentration from photoresist after because of video picture is different, in neutralization method of the present invention, the organic concentration from photoresist that is dissolved in the video picture waste liquid that contains TAAH that offers neutralization reaction is high more, then this organic removal efficient is high more, is effective therefore.
[0017]
The organic concentration from photoresist of dissolving in the video picture waste liquid of the above-mentioned TAAH of containing contains the organic concentration from photoresist of dissolving in the video picture waste liquid of TAAH, under the situation of the video picture waste liquid that contains TAAH of discharging in semiconductor fabrication process for example, converting with COD is about tens of～hundreds of ppm.Again, in recent years, someone has proposed to append the video picture waste liquid that contains TAAH in once offering the video picture waste liquid that contains TAAH of video picture operation, that adjusts after the concentration of TAAH the video picture waste liquid that contains TAAH that will this adjusted liquid be used in once again in the video picture operation effectively utilizes method, and this contains and is higher than the tendency of above-mentioned concentration from the organic concentration existence of photoresist in the video picture waste liquid of TAAH.As mentioned above, in any video picture waste liquid that contains TAAH, all by also having concentrated organism when the containing ratio that method improves TAAH such as concentrating from photoresist.Therefore TAAH concentration is that the organic concentration from photoresist of dissolving in the video picture waste liquid that contains TAAH of 10～30 quality % is about thousands of～10000ppm with the COD conversion usually.
[0018]
Carbon dioxide
In neutralization method of the present invention,, add the carbon dioxide neutralization by to the pH value being the video picture waste liquid that contains TAAH more than 13.The carbon dioxide that the present invention uses is so long as the industrial carbon dioxide that can access can use, without any restriction.And can use carbon dioxide with dilution such as inactive gas.After containing the video picture waste liquid of TAAH with the carbon dioxide neutralization, during with electrolytic method decomposing carbonate and supercarbonate, except generating TAAH, also generate the water electrolytic gas secondary product, this water electrolytic gas mainly comprises carbon dioxide, as the utilization again of carbon dioxide, also this water electrolytic gas can be used in neutralization reaction.
[0019]
The addition of carbon dioxide
The present invention is the neutralization method of the video picture waste liquid of a kind of TAAH of containing, by to the pH value being the video picture waste liquid that contains TAAH more than 13, add carbon dioxide it is neutralized the pH value below 11.5, it is characterized in that, from the pH value of above-mentioned video picture waste liquid be 13 the time be carved into the interpolation that the pH value reaches the carbon dioxide in moment of 12, according to the pH value be the TAAH in the video picture waste liquid in moment of 13 0.15 liter/hour of each mole usefulness (below, the volume of carbon dioxide is recorded and narrated with the volume under the standard state) following addition adds, preferably is adjusted into below the 0.10L/hr.As mentioned above, separate out from photoresist organic that to be carved in the zone that the pH value reaches moment of 12 be significant when the pH of above-mentioned video picture waste liquid value is about 13.Thereby the addition of the carbon dioxide by being adjusted at above-mentioned zone can be adjusted the organic speed of separating out from photoresist, obtains the good organism precipitate of strainability.
[0020]
The addition of the above-mentioned carbon dioxide adjustment effect from the organic speed of separating out of photoresist more at least is good more.If but the addition of carbon dioxide very little then the time that neutralisation treatment is taken many, therefore consider that from industrial efficiency to be advisable more than 0.05 liter/hour, better is more than 0.01 liter/hour.
[0021]
Separate out before reaching moment of 11.5 in the pH value from the organism major part of photoresist again.Thereby, from the pH value of video picture waste liquid be 13 the time be carved into the addition that the pH value reaches the carbon dioxide in moment of 11.5 and be adjusted into above-mentioned addition, this considers it is more suitably from obtaining the good precipitate of filterableness.
[0022]
Aspect the interpolation of the carbon dioxide of above-mentioned zone, it to the pH value each mole of the TAAH in the video picture waste liquid in moment of 13, if addition is above 0.15 liter/hour, then from the adjustment weak effect of the organic speed of separating out of photoresist, with stickability big state or microgranular separating out, is unfavorable from the organism of photoresist therefore.On the other hand, if the addition of above-mentioned carbon dioxide is low excessively, then the needed time of neutralization reaction long, therefore consider requirements such as industrial efficiency, as long as according to the pH value be 13 the time be carved into the pH value and reach for this section period in the moment of 12 or 11.5, determine the addition of above-mentioned carbon dioxide to get final product.Usually, suitably determine the addition of carbon dioxide, so that from the pH value of video picture waste liquid be 13 the time be carved into the pH value to reach needed time in the moment of 12 be 0.8～10 hour, better is to be 2.0～10 hours, or suitably determine the addition of carbon dioxide, so that from the pH value of above-mentioned video picture waste liquid be 13 the time be carved into the pH value to reach needed time in the moment of 11.5 be 3～30 hours, better is to be 5.0～30 hours.
[0023]
Begin to add the moment (hereinafter referred to as " carbon dioxide add adjust starting point ") of carbon dioxide so long as get final product reach moment of 13 in the pH value of the video picture waste liquid of the above-mentioned TAAH of containing before with above-mentioned addition, as long as consider to carry out suitable decisions the such as equipment, processing power of neutralization reaction.For example consider, also can be set at the pH value to the interpolation of carbon dioxide adjustment starting point and be higher than 13 from safety coefficient.Begin also can adopt above-mentioned addition from neutralization, but the time of neutralization reaction is elongated, in the industrial high-level efficiency of can not saying so to the carbon dioxide addition in whole pH zone of finishing.Therefore surpass in 13.7 the video picture waste liquid that contains TAAH in the pH value, it is that suitable setting of any pH value in the 13.7 following scopes is specially suitable more than 13 according to the pH value that carbon dioxide adds the starting point of adjusting.
[0024]
The adding method of carbon dioxide
The method of adding carbon dioxide with above-mentioned addition, so long as in the scope of the addition of above-mentioned carbon dioxide, the method that provides of carbon dioxide can adopt known method.For example there is intermittence that the method for carbon dioxide is provided, the method for carbon dioxide etc. is provided continuously with certain amount.
[0025]
In the adding method of above-mentioned carbon dioxide, also be the method that provides carbon dioxide continuously with a certain amount of, engineering management is easy, and reaction unit is simple, and is therefore proper.
[0026]
Reach carbon dioxide and add the neutralization before of adjustment starting point
In the present invention, add the neutralization of adjusting before the starting point (hereinafter referred to as the 1st neutralization), suitably determine as long as carry out the equipment, processing power etc. of neutralization reaction with regard to considerations such as its reaction conditionss for reaching above-mentioned carbon dioxide.As mentioned above, in the 1st and in the carbon dioxide addition also can adopt carbon dioxide add to adjust the addition of the later neutralization of starting point (hereinafter referred to as the 2nd neutralization), but the needed time of neutralization reaction is elongated, industrial can not say so high efficiency.Thereby it is suitable that the addition of the carbon dioxide of the 1st neutralization adopts the addition of Duoing than the carbon dioxide addition of the 2nd neutralization.
[0027]
But because of the relation of condition, the bias current of the carbon dioxide that is provided causes the generation of channel or back-mixing, and therefore carbon dioxide can not evenly spread in reactive tank, produces the high part of gas concentration lwevel.Therefore the pH value of the local video picture waste liquid that above-mentioned gas concentration lwevel is high is low, and a part is added and just separated out with the state of high adhesion before adjusting starting point arriving above-mentioned carbon dioxide from the organism of photoresist, is adhered on the pipe arrangement etc., might result in blockage.Thereby, the interpolation of carbon dioxide of above-mentioned the 1st neutralization, be added to according to the addition of each mole usefulness below 1.0 liters/hour of the tetra-alkyl ammonium hydroxide in the preceding video picture waste liquid of this neutralization suitable, more suitable to add below the 0.7L/hr.
[0028]
Again, the addition of above-mentioned carbon dioxide is few more, then in the 1st and in prevent that the effect of separating out from the organism of photoresist is good more, if but very little, then the needed time of neutralisation treatment elongated, therefore consider from industrial efficiency, preferably adopt the addition of 0.1L/hr.
[0029]
The end of neutralization
In the neutralization method of the present invention, the end point that contains the neutralization that the video picture waste water utilization carbon dioxide of TAAH carries out, the pH value that can consider this video picture waste liquid is below 11.5, in and the suitably settings such as influence of the pH value of this video picture waste liquid in the permanance, electrowinning process of the filtering membrane that uses in the organic separation circuit after the operation from photoresist.The end point of above-mentioned neutralization is normally suitably set in 8～11.5 scope and is got final product.Be the neutralization in the moment below 11.5 for the pH value of above-mentioned development waste liquid, as long as the equipment that reacts with regard to consideration such as its reaction conditionss, processing power etc. suitably determine again.
[0030]
Particularly in neutralization method of the present invention, above-mentioned organism from photoresist, reach moment of 12～11.5 in the pH of above-mentioned video picture waste liquid value before major part separate out, it is suitable especially therefore the end point of neutralization suitably to be set in pH value 11～11.5 scopes.The end point of neutralization is set in the above-mentioned scope, except above-mentioned reason, needed time that neutralizes in addition can shorten, under the situation below the pH11.5, the reaction efficiency of carbon dioxide of neutralization of carbonate that is used in TAAH is low, therefore in order to promote neutralization, be necessary to use the carbon dioxide of excess quantity, in electrowinning process, the electrolysis of 1 mole carbonate can generate 2 moles TAAH, by contrast, supercarbonate with respect to 1 mole generates 1 mole TAAH, therefore provide the ratio of the carbonate in the development waste liquid of electrolysis many more, then high more this some reason of ionizing efficiency is therefore suitable especially.
[0031]
The neutralization method mode
As mentioned above, if enumerate neutralization method mode of the present invention, the neutralization method of for example using a reactive tank, the neutralization method of using plural a plurality of reactive tanks are arranged then.Wherein use the neutralization method of a reactive tank, have for example at whole N-process, the TAAH of each mole in the development waste liquid in the moment of pH value 13, the method that neutralizes with the carbon dioxide addition below the 0.15L/hr, in above-mentioned the 1st neutralization the 2nd and in, change the method that the addition of carbon dioxide neutralizes.Again, the neutralization method of the plural a plurality of reactive tanks of above-mentioned use for example has in the 1st neutralization and the 2nd and the method for carrying out with different reactive tanks respectively.
[0032]
In aforesaid way, use plural a plurality of reactive tank, the 1st the neutralization and the 2nd in the method that neutralizes with different reactive tanks respectively, owing to have such characteristics, promptly, use respectively independently reactive tank, can carry out process management and can walk abreast independently neutralizing, can shorten the running time, be desirable therefore.If in the 1st neutralization and the 2nd with carry out with different reactive tanks respectively, then also can be respectively respectively neutralize with a plurality of reactive tanks enforcements.If but reactive tank quantity is too much, then the engineering management of each reactive tank and operation become numerous and diverse, and follow the setting of reactive tank in addition and increase problem such as cost, and it is only therefore carrying out with a reactive tank that the 1st neutralization and the 2nd neutralizes respectively.(with the neutralization method of two reactive tanks)
Below each is elaborated with the neutralization method of the present invention that a reactive tank carries out the 1st neutralization and the 2nd neutralization.Fig. 1 is in the 1st neutralization and the 2nd in the present invention and uses the skeleton diagram of the optimal morphology that reactive tank carries out respectively.
[0033]
(the 1st neutralization)
In reactive tank 1, carry out the 1st neutralization.The video picture waste liquid that contains TAAH provides by containing TAAH video picture waste liquid supplying tubing 3.In reactive tank 1, provide carbon dioxide in reactive tank 1, to carry out neutralization reaction with carbon dioxide supplying tubing 4, this reactant liquor is discharged to the supplying tubing 6 that reactive tank 1 disposes waste liquid by means of pump 5, offers reactive tank 2 by this supplying tubing 6.Unreacted carbon dioxide etc. are discharged pipe arrangement 7 by the unreacted carbon dioxide and are discharged to outside the system.
[0034]
As mentioned above, in the 1st and in the carbon dioxide addition can consider to carry out neutralization reaction equipment, processing power etc. suitably decision get final product.From industrial efficiency consider preferably to adopt than the 2nd with in the carbon dioxide addition addition of Duoing.And the influence that causes of the channel that causes of the bias current of considering the carbon dioxide reactive tank 1 in or back-mixing, it is more suitable that the addition below per 1 mole of employing 1.0L/hr of the tetra-alkyl ammonium hydroxide in the video picture waste liquid before this neutralization neutralizes.
[0035]
And in reactive tank 1, set pump 8 and circulation pipe arrangement 9, by in above-mentioned circulation pipe arrangement, reaction assay device 10 being set, can carry out the reaction manager of reactive tank 1.As this reaction assay device, as long as it is known that the concentration of the video picture waste liquid that contains TAAH of reaction is provided, just can easily calculate the TAAH of terminal point of neutralization of reactive tank 1 and the concentration of carbonate, therefore except pH meter, also can use ultrasound wave densimeter etc. to measure the known determinator of the concentration of the solute in the solution.
[0036]
In above-mentioned neutralization, the foaming of reactant liquor becomes under the situation of problem, also can in above-mentioned circulation pipe arrangement the carbon dioxide supplying tubing be set, and utilizes supply means such as line mixer, thrower to offer this circulation pipe arrangement, imports reactive tank by this circulation pipe arrangement.Temperature of reaction about the reaction in the reactive tank 1, if considering the video picture waste liquid that contains TAAH is that aqueous solution and temperature are too high, the photoresist that then contains in the video picture waste liquid of TAAH can separate out or solidify, make the reaction efficiency of itself and carbon dioxide reduce both of these case, be advisable to carry out neutralization reaction, particularly between 20 ℃～70 ℃, carry out neutralization reaction ideal more at 0 ℃～80 ℃.
[0037]
The kind of above-mentioned reactive tank 1, the reactive tank that for example has stirrer is specifically arranged, be filled with filling tower that filler improves the diffuser efficiency of carbon dioxide, the video picture waste liquid of the above-mentioned TAAH of containing is circulated to tower bottom from top of tower, provide carbon dioxide from tower bottom, use neutralizing tower that flow operation is made TAAH contact with carbon dioxide to react etc.In above-mentioned reactive tank, also utilize to make the neutralizing tower of its reaction can carry out neutralization reaction continuously to flow operation, therefore more suitable.
[0038]
As mentioned above, in the 1st and in, the method that the multistage tower of selecting above-mentioned neutralizing tower employing to have multi-disc column plate 11 neutralizes, separate with column plate 11 at different levels in easily the pH value of above-mentioned video picture waste liquid is kept necessarily, above-mentioned video picture waste liquid is from cat head process circulations at different levels at the bottom of tower, the pH value of video picture waste liquid is descended, therefore suitable especially.
[0039]
The column plate 11 that uses in the above-mentioned multistage tower utilizes porous plate and downspout (ダ ウ Application カ マ one) 12 that many through holes are arranged to form.Above-mentioned TAAH video picture waste liquid is moving to tower bottom flow from cat head through downspout 12, and carbon dioxide flows to top of tower from tower bottom through the hole of porous plate.The flowing velocity of TAAH video picture waste liquid in neutralizing tower can be controlled with the internal diameter of downspout 12.If the internal diameter of above-mentioned downspout 12 is too little, then the needed reaction time of neutralization reaction is long, therefore inadvisable economically, if it is too big, then adjust the adjustment weak effect of above-mentioned video picture waste liquid velocity of liquid assets, therefore be advisable with 0.1～0.5% of neutralizing tower internal diameter, particularly 0.2～1.0% even more ideal.Again, the velocity of liquid assets of carbon dioxide can be utilized the aperture opening ratio control of porous plate, if this aperture opening ratio is low excessively, then the needed reaction time of neutralization reaction is elongated, therefore inadvisable economically, if too high, the adjustment weak effect of the flowing velocity of above-mentioned carbon dioxide then, therefore preferably suitable 3～10%.
[0040]
Again, column plate 11 for above-mentioned multistage tower, quantity progression many more, that just cut apart are many more, then pH adjustment effect is good more, if but cut apart too much, the manufacturing cost height of multistage tower then, therefore preferably the number of column plate 11 is 2～4, that is to say, preferably 3～5 grades of the progression that above-mentioned video picture waste liquid passes through.
[0041]
Also have, evenly spread this purpose in order to promote carbon dioxide, cut apart with column plate 11 at different levels in filling filler ideal especially.As this filler, can use the known filler that in gas liquid reaction, uses, without any restriction.
[0042]
(the 2nd neutralization)
After reactive tank 1 carries out the 1st neutralization, in reactive tank 2, carry out the 2nd neutralization.To offer reactive tank 2 at the video picture waste liquid (being called " reactive tank 1 disposes waste liquid " later on) of reactive tank 1 neutralization with reactive tank 1 supplying tubing 6 that disposes waste liquid.Providing to reactive tank 2 after reactive tank 1 disposes waste liquid, provide carbon dioxide to neutralize with nitrogen dioxide supplying tubing 13.Reactant liquor was discharged through neutralisation treatment liquid supplying tubing 15 with pump 14 after neutralization finished, and was transported to carry out the separation circuit that photoresist separates.Process unreacting gas such as unreacted carbon dioxide are discharged pipe arrangement 16 and are discharged to outside the system.
[0043]
In the 2nd and in, the pH value of above-mentioned video picture waste liquid add to be adjusted starting point reaches the carbon dioxide in moment of 12 or 11.5 to the pH value interpolation from carbon dioxide, be the TAAH in the video picture waste liquid in moment of 13 for 1 mole pH value, carry out with the following addition of 0.15L/hr.
[0044]
In order to improve the stirring efficiency of reactant liquor, also can circulation pipe arrangement 18 be set at reactive tank 2.With pump 17 solution in the reactive tank 2 is circulated, Yi Bian it is reacted.Foaming at reactant liquor becomes under the situation of problem, also can the carbon dioxide supplying tubing be set in above-mentioned circulation pipe arrangement and utilize supply means such as line mixer, thrower that carbon dioxide is offered this circulation pipe arrangement, be incorporated in the reactive tank by this circulation pipe arrangement.
[0045]
Also have, can carry out the reaction manager of reactive tank 2 by in above-mentioned circulation pipe arrangement, reaction assay device 19 being set.As this reaction assay device, because if it is known to offer carbonate and the concentration of TAAH of the reactive tank 1 of reactive tank 2 in disposing waste liquid, then can easily calculate the carbonate under the pH value of terminating point of neutralization and the concentration of supercarbonate, therefore except pH meter, also can use ultrasound wave densimeter etc. can measure the known determinator of the concentration of the solute in the solution.
[0046]
(the removal method of the photoresist of separating out)
In neutralization method of the present invention, be bigger cotton-shaped photoresist from the organism of the photoresist of separating out, and stickability is little, therefore have the good feature of strainability.As known equipment for separating liquid from solid such as can use that from this organic removal method in the organic separation circuit of photoresist decant, centrifuging, filter press, ultrafiltration filter membrane etc. filter.Again, the neutralization method of the present invention of using by oneself makes the organism of its photoresist of separating out have feature recited above, therefore can remain untouched and offer the Separation of Solid and Liquid operation, but, also can after mixing, the interpolation filtration adjuvant carry out the Separation of Solid and Liquid operation in order further to improve filtration efficiency.Filtration adjuvant as being used in this Separation of Solid and Liquid operation has acticarbon, zeyssatite, cellulose etc.In the middle of this, from considering that in industrial cheap angle in hand filtration adjuvants such as use acticarbon zeyssatite are proper.
Embodiment
[0047]
In order further to specify method of the present invention, embodiment describes below disclosing, but the invention is not restricted to these embodiment.
[0048]
Adopt the neutralising arrangement of the structure shown in Figure 1 of vinyl chloride making to neutralize.Reactive tank 1 is of a size of diameter 100mm, height 1000mm, the inner column plate with downspout that is provided with at three places.Reactive tank 2 is of a size of diameter 250mm, height 800mm.
[0049]
Also have,, use the video picture waste liquid of the tetramethyl ammonium hydroxide (hereinafter referred to as TMAH) that contains pH value 14.7 as the video picture waste liquid that contains TAAH.Also have, the TMAH concentration of this video picture waste liquid is 20 quality %, is scaled 5000ppm from the organic content of photoresist with COD.
[0050]
At first, put into the video picture waste liquid 6L that contains TAAH in reactive tank 1, provide carbon dioxide by the carbon dioxide supply pipe 4 of reactive tank 1 bottom with the speed of 17.3L/hr, neutralizing up to pH is 13.Thereafter with the speed of 17.3L/hr while providing carbon dioxide to provide above-mentioned video picture waste liquid with the speed of 4.6L/hr from the video picture waste liquid supplying tubing 3 that contains TAAH on reactive tank 1 top, neutralize continuously with the convection current mode of operation.The dispose waste liquid sampling that disposes waste liquid of the reactive tank 1 that supplying tubing 6 discharges confirms that it is 13 that the pH value obtains the pH value to reactive tank 1.At this moment the addition of carbon dioxide is that 1 mole of TMAH in the video picture waste liquid before neutralizing is being carried out with the speed of 0.39L/hr (quantity delivered of representing carbon dioxide below with the volume under the standard state) under the standard state in the reactive tank 1.In above-mentioned neutralization operation, do not have in the reactive tank 1 to find to separate out from the organism of photoresist.
[0051]
Then, after in reactive tank 2, depositing the disposing waste liquid of reactive tank 1 of 20L, from the carbon dioxide supplying tubing 4 of the bottom of reactive tank 2, be that 1 mole the TMAH in moment of 13 adds carbon dioxide with the speed of 0.01L/hr and neutralizes to the video picture waste liquid at pH, obtain the treating fluid of pH11.5.From the pH13 of video picture waste liquid the time be carved into pH to reach needed time in the moment of 12 be 9.7 hours, pH13 the time be carved into pH to reach needed time in the moment of 11.5 be 28.5 hours.
[0052]
This treating fluid is added egression board acticarbon (trade name as filtration adjuvant with the ratio of 1.0wt%, Japan エ Application バ イ ロ ケ ミ カ Le ズ Co., Ltd. makes), (trade name: Japanese ア De バ Application テ Star Network Toyo Co., Ltd. makes at pressure filter KST-142-UH after stirring, diameter 142mm) (Japanese ア De バ Application テ Star Network Toyo Co., Ltd. makes the filtrator of commodity メ Application Block レ system Off イ Le one H 100A142C by name go up to be installed, 1 micron in aperture), exert pressure with 0.15MPa is filtered, filter all right, the filtered fluid that obtains clarifying.The COD of this filtered fluid is 60ppm.Again, the filtration treatment speed of the above-mentioned treating fluid of calculating from filter velocity is 500L/m
3Hr.
[0053]
Neutralize in reactive tank 1 with the feed speed of the video picture waste liquid shown in the table 1, carbon dioxide feed speed and to the addition that the TMAH1 in the video picture waste liquid before 1 mole of neutralization adds carbon dioxide, then, 's the TMAH in moment of 13 with the video picture waste liquid shown in the table 1 in the pH value to 1 mole, the addition that adds carbon dioxide neutralizes in reactive tank 2, in addition, with the embodiment 1 the same neutralization reaction of carrying out.From reactive tank 2 pH of video picture waste liquid be 13 the time be carved into the filter result that pH reaches after needed time till moment of 12 and 11.5 and the neutralization and be shown in table 1.
Table 1
Carbon dioxide quantity delivered under the standard state of TMAH in the video picture waste liquid before the neutralization that ※ is 1 pair 1 mole
The pH value of the video picture waste liquid that ※ is 2 pairs 1 mole is the quantity delivered of the carbon dioxide under the standard state of TMAH in moment of 13
※ 3 from the pH value of video picture waste liquid be 13 the time be carved into the pH value and reach for 12 or 11.5 needed time in the moment
[0054]
Embodiment 7
Use the neutralising arrangement the same with embodiment 1, at first in reactive tank 1, put into the video picture waste liquid 6L that contain TAAH the same with embodiment 1, provide carbon dioxide from the carbon dioxide supplying tubing 4 of reactive tank 1 bottom with the speed of 24.8L/hr, the pH that neutralizes is till 13.5.Provide above-mentioned video picture waste liquid from the supplying tubing 3 of the imaging liquid that contains TAAH on the top of reactive tank 1 with the speed of 7.5L/hr when providing carbon dioxide with the speed of 24.8L/hr thereafter, neutralize continuously with counter-current operation.The pH value is confirmed in the reactive tank 1 that the supplying tubing 6 that reactive tank 1 is disposed waste liquid the is discharged sampling that disposes waste liquid, and obtaining the pH value is 13.5.The interpolation of the carbon dioxide in the reactive tank 1 at this moment to the TMAH in the imaging liquid before 1 mole the neutralization, is carried out with the speed of 0.57L/hr.In above-mentioned neutralization operation, in reactive tank 1, do not have to find to separate out from the organism of photoresist.
[0055]
Then, after in reactive tank 2, putting into the treating fluid of reactive tank 1 of 20L, adding carbon dioxide from the carbon dioxide supplying tubing 4 of the bottom of reactive tank 2 neutralizes, interpolation speed is to be that the TMAH in moment of 13 adds with 0.07L/hr for 1 mole video picture waste liquor PH, obtains pH and be 11.5 treating fluid.From the pH of video picture waste liquid be 13 the time be carved into pH and reach that the needed time is 2.8 hours till moment of 12, from pH be 13 the time to be carved into needed time in the moment of 11.5 be 6.3 hours.
[0056]
Carry out the filter operation identical for this treating fluid, can filter the filtered fluid that obtains clarifying well with embodiment 1.The COD of this filtered fluid is 60ppm.Again, the filtration treatment speed of the above-mentioned treating fluid of calculating from filter velocity is 400L/m
3Hr.
[0057]
Except using organic content to be scaled the video picture waste liquid that contains TMAH of 8000ppm, pH14.7, carry out same operation with embodiment 7 and neutralize with COD from photoresist.Also have, the TMAH concentration of this video picture waste liquid is 20 quality %.
[0058]
This treating fluid is carried out the filtration identical with embodiment 7, can well filter, obtain clarified solution.The COD of this filtered fluid is 90ppm.Again, the filter velocity of the above-mentioned treating fluid of calculating from filter velocity is 400L/m
3Hr.
[0059]
Embodiment 9
Use the video picture waste liquid that contains TAAH similarly to Example 1, equally with embodiment 6 neutralize with reactive tank 1.
[0060]
Then, after in reactive tank 2, putting into the treating fluid of reactive tank 1 of 20L, carbon dioxide supplying tubing 4 with reactive tank 2 bottoms, provide carbon dioxide to neutralize for the TMAH in moment of 13 with the speed of 0.02L/hr to the pH value of 1 mole video picture waste liquid, up to the pH value is 12, then the interpolation speed with carbon dioxide is increased to 0.50L/hr, and the pH value that neutralizes is 11.5 to obtain treating fluid.The pH value of video picture waste liquid be 13 the time be carved into the pH value to reach needed time in the moment of 12 be 6.0 hours, the pH value be 13 the time be carved into the pH value to reach for 11.5 needed times be 6.5 hours.
[0061]
To filter, filter all rightly to this treating fluid, can access the filtered fluid of clarification with embodiment 1 identical operations.The COD of this filtered fluid is 70ppm.Again, the filtration treatment speed of the above-mentioned treating fluid that calculates from filter velocity is 350L/m
3Hr.
[0062]
Comparative example 1～2
Providing speed, carbon dioxide that speed is provided and the carbon dioxide addition of the TMAH in the video picture waste liquid before 1 mole the neutralization neutralized in reactive tank 1 with the video picture waste liquid shown in the table 2 in the reactive tank 1, then, the addition that with the pH to 1 mole video picture waste liquid shown in the table 2 is the TMAH in moment of 13 carries out the neutralization of reactive tank 2, in addition with the embodiment 1 the same neutralization reaction of carrying out.When reactive tank 2 video picture waste liquids are pH13, be carved into pH reach 12 and 11.5 needed times and the neutralization after filter result be shown in table 2.Also have, pressure filter is blocked midway filtering for comparative example 2, therefore filters and can not finish.So can not calculate filtration treatment speed.
Table 2
Quantity delivered under the standard state of TMAH in the video picture waste liquid before the neutralization that ※ is 1 pair 1 mole
The pH value of the video picture waste liquid that ※ is 2 pairs 1 mole is the quantity delivered under the standard state of TMAH in moment of 13
※ 3 from the pH value of video picture waste liquid be 13 the time be carved into the pH value and reach for 12 or 11.5 needed time in the moment
Claims (10)
1. neutralization method that contains the video picture waste liquid of tetra-alkyl ammonium hydroxide, by to being dissolved with organic from photoresist, the pH value is that the video picture waste liquid that contains tetra-alkyl ammonium hydroxide more than 13 adds carbon dioxide, and it is neutralized the pH value below 11.5, it is characterized in that
From the pH value of above-mentioned video picture waste liquid be 13 the time be carved into the interpolation that the pH value reaches the carbon dioxide in moment of 12, carry out according to the addition of each mole usefulness below 0.15 liter/hour that to the pH value is the tetra-alkyl ammonium hydroxide in the video picture waste liquid in moment of 13.
2. the neutralization method that contains the video picture waste liquid of tetra-alkyl ammonium hydroxide according to claim 1 is characterized in that, from the pH value of video picture waste liquid be 13 the time be carved into the pH value and reach needed time in the moment of 12 and be decided to be 0.8～10 hour.
3. the neutralization method that contains the video picture waste liquid of tetra-alkyl ammonium hydroxide according to claim 1, it is characterized in that, from the pH value of video picture waste liquid be 13 the time be carved into the interpolation that the pH value reaches the carbon dioxide in moment of 11.5, carry out according to the addition of each mole usefulness below 0.15 liter/hour that to the pH value is the tetra-alkyl ammonium hydroxide in the video picture waste liquid in moment of 13.
4. the neutralization method that contains the video picture waste liquid of tetra-alkyl ammonium hydroxide according to claim 3 is characterized in that, from the pH value of video picture waste liquid be 13 the time be carved into the pH value and reach needed time in the moment of 11.5 and be decided to be 3～30 hours.
5. neutralization method that contains the video picture waste liquid of tetra-alkyl ammonium hydroxide, by to being dissolved with organic from photoresist, the pH value neutralizes the pH value below 11.5 above 13.7 the video picture waste liquid interpolation carbon dioxide that contains tetra-alkyl ammonium hydroxide with it, it is characterized in that
The pH value of this video picture waste liquid is become more than 13,13.7 the 1st of any pH value in the following scope neutralize with reach this any pH value after the 2nd in in different reactive tanks, carry out, simultaneously in the 2nd and in, from the pH value of video picture waste liquid be 13 the time be carved into the interpolation that the pH value reaches the carbon dioxide in moment of 12, each mole according to the pH value being the tetra-alkyl ammonium hydroxide in the video picture waste liquid in moment of 13 carries out with the addition below 0.15 liter/hour.
6. the neutralization method that contains the video picture waste liquid of tetra-alkyl ammonium hydroxide according to claim 5 is characterized in that, make in the 1st and the addition of the carbon dioxide of middle time per unit than in the 2nd with in the carbon dioxide addition big.
7. the neutralization method that contains the video picture waste liquid of tetra-alkyl ammonium hydroxide according to claim 6, it is characterized in that, in the 1st and the interpolation of middle carbon dioxide, carry out according to the addition of each mole usefulness below 1.0 liters/hour to the tetra-alkyl ammonium hydroxide in the preceding video picture waste liquid of this neutralization.
8. the neutralization method that contains the video picture waste liquid of tetra-alkyl ammonium hydroxide according to claim 5 is characterized in that, in the 1st and carry out in multistage neutralizing tower.
9. neutralization method that contains the video picture waste liquid of tetra-alkyl ammonium hydroxide, by to being dissolved with organic from photoresist, the pH value neutralizes the pH value below 11.5 above 13.7 the video picture waste liquid interpolation carbon dioxide that contains tetra-alkyl ammonium hydroxide with it, it is characterized in that
Become more than 13 in the pH value that makes this video picture waste liquid, 13.7 the 1st neutralization of any pH value in the following scope and reach this any pH value after the 2nd in the interpolation speed of middle change carbon dioxide, simultaneously in the 2nd and in, from the pH value of video picture waste liquid be 13 the time be carved into the interpolation that the pH value reaches the carbon dioxide in moment of 12, according to each mole that to the pH value is the tetra-alkyl ammonium hydroxide in the video picture waste liquid in moment of 13, carry out with the addition below 0.15 liter/hour, and make in the 1st and the addition of the carbon dioxide of middle time per unit than in the 2nd with in the carbon dioxide addition big.
10. according to each the described neutralization method that contains the video picture waste liquid of tetra-alkyl ammonium hydroxide in the claim 5～9, it is characterized in that the concentration of the tetra-alkyl ammonium hydroxide in the video picture waste liquid that contains tetra-alkyl ammonium hydroxide before the 1st neutralization is 10～30 quality %.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP303893/2006 | 2006-11-09 | ||
| JP2006303893 | 2006-11-09 | ||
| PCT/JP2007/071567 WO2008056671A1 (en) | 2006-11-09 | 2007-11-06 | Method of neutralizing developer waste liquid containing tetraalkylammonium hydroxide |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN101529338A true CN101529338A (en) | 2009-09-09 |
| CN101529338B CN101529338B (en) | 2012-01-25 |
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN2007800399857A Expired - Fee Related CN101529338B (en) | 2006-11-09 | 2007-11-06 | Method of neutralizing developer waste liquid containing tetraalkylammonium hydroxide |
Country Status (5)
| Country | Link |
|---|---|
| JP (1) | JP5041297B2 (en) |
| KR (1) | KR101193924B1 (en) |
| CN (1) | CN101529338B (en) |
| TW (1) | TWI416278B (en) |
| WO (1) | WO2008056671A1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109160639A (en) * | 2018-10-23 | 2019-01-08 | 南京元亨化工科技有限公司 | A kind of wastewater treatment equipment of tetramethylammonium hydroxide |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4689759B2 (en) * | 2009-04-24 | 2011-05-25 | 旭化成イーマテリアルズ株式会社 | Developing device, developer processing method, printing plate manufacturing method, and filtration device |
| EP2423751B1 (en) | 2009-04-24 | 2013-12-11 | Asahi Kasei E-materials Corporation | Developing apparatus, process for treating developing solution, process for producing printing plate, and filter apparatus |
| JP2016075920A (en) * | 2015-11-16 | 2016-05-12 | 富士フイルム株式会社 | Production method of organic process liquid for patterning chemically amplified resist film, pattern forming method, and method for manufacturing electronic device |
| EP3364251A1 (en) * | 2017-02-17 | 2018-08-22 | GS Trading SA | Method for etching photopolymer plates |
| JP7055326B2 (en) * | 2017-09-15 | 2022-04-18 | 株式会社ササクラ | Development waste liquid treatment equipment and treatment method |
Family Cites Families (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5354434A (en) * | 1991-07-12 | 1994-10-11 | Chlorine Engineers Corp. Ltd. | Method for regenerating tetraalkylammonium hydroxide |
| JPH0517889A (en) * | 1991-07-12 | 1993-01-26 | Chlorine Eng Corp Ltd | Method for regenerating tetra-alkyl ammonium hydroxide |
| JP3392483B2 (en) * | 1993-11-15 | 2003-03-31 | クロリンエンジニアズ株式会社 | Treatment method for wastewater containing tetraalkylammonium hydroxide |
| JPH0856672A (en) * | 1994-08-26 | 1996-03-05 | Kazuaki Chayama | Gene of type c hepatitis virus |
| JP3216998B2 (en) * | 1996-08-12 | 2001-10-09 | 昭和電工株式会社 | Purification and recovery of tetraalkylammonium hydroxide from waste developer |
| JPH11262765A (en) * | 1998-03-16 | 1999-09-28 | Nagase & Co Ltd | Method for pretreating and regenerating waste solution containing tetraalkylammonium hydroxide |
| JP2003190949A (en) * | 2001-12-27 | 2003-07-08 | Tokuyama Corp | Method for regeneration of photoresist developing waste solution |
| JP2004097997A (en) * | 2002-09-11 | 2004-04-02 | Kurita Water Ind Ltd | Method and equipment for treating water-soluble polymer-containing waste liquid |
| CN1298636C (en) * | 2002-11-29 | 2007-02-07 | 长濑产业株式会社 | Regeneration device and method for waste developing solution |
| CN1263689C (en) * | 2003-10-17 | 2006-07-12 | 深圳市金达莱环保有限公司 | Method for treating developer and removing tank solution in waste water for circuit board |
| JP2005249818A (en) * | 2004-03-01 | 2005-09-15 | Nishimura Yasuji | Method and apparatus for controlling developer for photoresist |
| JP4810436B2 (en) * | 2004-11-30 | 2011-11-09 | 株式会社トクヤマ | Processing method for waste developer |
-
2007
- 2007-11-06 JP JP2008543089A patent/JP5041297B2/en active Active
- 2007-11-06 KR KR1020097008687A patent/KR101193924B1/en not_active IP Right Cessation
- 2007-11-06 WO PCT/JP2007/071567 patent/WO2008056671A1/en active Application Filing
- 2007-11-06 CN CN2007800399857A patent/CN101529338B/en not_active Expired - Fee Related
- 2007-11-08 TW TW96142218A patent/TWI416278B/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN109160639A (en) * | 2018-10-23 | 2019-01-08 | 南京元亨化工科技有限公司 | A kind of wastewater treatment equipment of tetramethylammonium hydroxide |
Also Published As
| Publication number | Publication date |
|---|---|
| TWI416278B (en) | 2013-11-21 |
| JPWO2008056671A1 (en) | 2010-02-25 |
| KR20090082202A (en) | 2009-07-29 |
| JP5041297B2 (en) | 2012-10-03 |
| TW200827944A (en) | 2008-07-01 |
| WO2008056671A1 (en) | 2008-05-15 |
| KR101193924B1 (en) | 2012-10-24 |
| CN101529338B (en) | 2012-01-25 |
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