CN102608878A - Developing liquid discharge processing method in manufacturing process of color filter - Google Patents
Developing liquid discharge processing method in manufacturing process of color filter Download PDFInfo
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- CN102608878A CN102608878A CN2012100131259A CN201210013125A CN102608878A CN 102608878 A CN102608878 A CN 102608878A CN 2012100131259 A CN2012100131259 A CN 2012100131259A CN 201210013125 A CN201210013125 A CN 201210013125A CN 102608878 A CN102608878 A CN 102608878A
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Abstract
The invention provides a developing liquid discharge processing method in the manufacturing process of a color filter, which is characterized by comprising the heating step, wherein the developing liquid is heated up to over 50 DEG; a pH value adjusting step, wherein the pH value of the developing liquid is adjusted to be below 7; and a solid-liquid separation step after the completion of the heating step and the pH value adjusting step.
Description
Technical field
The present invention relates to the disposal route of the development discharge opeing in a kind of colored filter manufacturing process.
Background technology
Up to now, in the manufacturing of colored filter, the pattern established law that utilization has disperseed the photoresist of pigment to carry out photoetching, i.e. chromatic photoresist agent method is known.
And, in the chromatic photoresist agent developing process in the colored filter manufacturing process, the general chromatic photoresist agent liquid that contains pigment, alkali soluble resins (alkali-soluble polymer), photopolymerization composition (monomer) and Photoepolymerizationinitiater initiater, spreading agent, solvent etc. that uses.
For example, the general method for making of colored filter processing procedure comprises (for example: with reference to non-patent literature 1): after forming black matrix" (BM) on the substrate, this chromatic photoresist agent liquid (for example red colour system) is coated on the substrate that has formed BM and forms the operation of film; Carry out carrying out the exposure process that UV hardens behind the pattern exposure via photomask; With developer solution with after not part is not removed of chromatic photoresist agent; Carry out the film formation/exposure/development/roasting procedure of the development/roasting procedure of so-called baking hardening; Then use the chromatic photoresist agent liquid of other colour system; Carry out this operation repeatedly, finally form RGB three looks, form electrically conducting transparent (ITO) film through sputtering method.
In addition,, also have identical ground, in having used the photoresist liquid of black pigment, form the BM method of patterning through photoetching process with the chromatic photoresist agent except after carrying out the chromium vapor deposition on the glass substrate, forming the method for patterning through etch processes.And then, decompose in the optical filter except RGB three looks at look, attempt the optical filter etc. of RGBY four looks of the high performance through enlarging gamut range in addition and also realized practicability, also there is the look of CMY system etc. to decompose optical filter.
Under any circumstance, in these developing processs, the developer solution that the chromatic photoresist agent of unexposed portion (unhardened chromatic photoresist agent) is the main body composition via non-ionic surfactant and alkaline components with high concentration is by wash-out.That is, the colorized optical filtering film developing discharge opeing of unhardened chromatic photoresist agent and developer solution can take place mainly to contain this moment.
, as the disposal route of the colorized optical filtering film developing discharge opeing of prior art, for example can enumerate: coagulating sedimentation or activated carbon method.
In addition; Following scheme (patent documentation 4) has been proposed: when carrying out photoetching process with substrate cleaning after; Remain on 5 or more and be discontented with under 9 the condition will containing the pH value of tetraalkyl phosphonium compound with the clean discharge opeing of a small amount of photoresist, pressurizeing is provided to the method for reverse osmosis membrane apparatus.
In addition; Also proposed following scheme (patent documentation 5): the pH value that will contain the discharge opeing of photoresist is adjusted to acidity, then, the pH value is adjusted to the alkalescence that is suitable for the photoresist aggregate and precipitate; Adjust to neutrality again and make the photoresist aggregate and precipitate, carry out the method that film is handled.
The prior art document
Patent documentation
Patent documentation 1: TOHKEMY 2009-128518 communique
Patent documentation 2: TOHKEMY 2010-102346 communique
Patent documentation 3: TOHKEMY 2008-246372 communique
Patent documentation 4: TOHKEMY 2001-276824 communique
Patent documentation 5: TOHKEMY 2006-255668 communique
Non-patent literature
Non-patent literature 1: tip colored filter treatment technology and chemistry, responsible editor city village state is grand, and CMC Co., Ltd. publishes, second edition distribution on April 1st, 2006, P1～300
Summary of the invention
The problem that invention will solve
In the development discharge opeing of colored filter, be rich in the multiple pigment or all cpds of photoresist and the surfactant that derives from developer solution of deriving from.Therefore, in this development discharge opeing, because of pigment dyeing (colourity, turbidity, outward appearance) or the organism that derives from surfactant and photoresist have very high concentration.
With the discharging of the development discharge opeing of this colored filter be recovered as purpose,, handle through coagulative precipitation staining components is removed, or organism is removed through charcoal treatment in order to reduce the concentration of these materials.
, because dispersing of pigments property is very high, very difficulty (embodiment (table 6) that states after the reference) is handled in coagulative precipitation.In addition, because surfactant concentrations is very high, the consumption of activated charcoal is very big.Therefore, existing pressure economically has operation running problem of unstable again.
Also have, in the membrane filter method of reverse osmosis membrane or NF film etc., above-mentioned pigment is handled or surfactant treatment carry out under the inadequate state owing to produce the obturation of film, can not realize the stable operation running.
Thus, the object of the present invention is to provide a kind of disposal route, it can separate the chromatic photoresist agent and remove from the development discharge opeing of optical filter effectively with surfactant, can improve the stability and the economy of operation running.
Solve the method for problem
The inventor is in order to solve above-mentioned problem; The result who furthers investigate finds; If colorized optical filtering film developing discharge opeing is being heated to the state more than the assigned temperature and the pH value is adjusted under the state below 7; Carry out Separation of Solid and Liquid, the chromatic photoresist agent that separates in the aftertreatment water is reduced, can also reduce the surfactant or the alkali-soluble polymer that contain in the colorized optical filtering film developing discharge opeing before handling.
Promptly, the present invention provides the disposal route of the development discharge opeing in a kind of optical filter manufacturing process; It is characterized in that; This method has: should the development discharge opeing be heated to the heating process more than 50 ℃ and this pH value with the development discharge opeing adjusted to the pH value adjustment operation below 7; This development discharge opeing is being heated and under the adjusted state of pH value, carrying out Separation of Solid and Liquid.
In above-mentioned heating process, preferably above-mentioned development discharge opeing is heated to 60～100 ℃, and/or in above-mentioned pH value adjustment operation, the pH value of above-mentioned development discharge opeing is adjusted in 2～6 the acid range.
Preferably use flocculating agent simultaneously.
Preferably the heat in the heat treated water after the above-mentioned Separation of Solid and Liquid is reclaimed, be used in the heating of the development discharge opeing in the above-mentioned heating process again.
According to the present invention, can make colorized optical filtering film developing discharge opeing, under state, handle with good cohesion filterableness and operation run stability.
Description of drawings
Fig. 1 representes the flow process 1 and flow process 2 of the disposal route of colorized optical filtering film developing discharge opeing of the present invention.
Fig. 2 representes the flow process 3 and flow process 4 of the disposal route of colorized optical filtering film developing discharge opeing of the present invention.
Fig. 3 representes the flow process 5 and flow process 6 of the disposal route of colorized optical filtering film developing discharge opeing of the present invention.
Fig. 4 representes the flow process 7 of the disposal route of colorized optical filtering film developing discharge opeing of the present invention.
Fig. 5 representes the pH value of colorized optical filtering film developing discharge opeing has been carried out the state after adjustment and the heating.
Fig. 6 representes state that the pH value of colorized optical filtering film developing discharge opeing is adjusted.
Embodiment
Below, describe with reference to the preferred version of accompanying drawing embodiment of the present invention.In addition, the example of description is just represented an example of the representational example of the present invention, can not come narrow sense ground to explain scope of the present invention in view of the above.
The disposal route of the development discharge opeing (to call " colorized optical filtering film developing discharge opeing " or " development discharge opeing " in the following text) in the colored filter of the present invention manufacturing process is: have with colorized optical filtering film developing discharge opeing be heated to more than 50 ℃ heating process and with the pH value of colorized optical filtering film developing discharge opeing adjust to pH value adjustment operation below 7, under heating and the adjusted state of pH value, carry out Separation of Solid and Liquid.In view of the above, can obtain to make the processing water of compositions minimizings such as chromatic photoresist agent and surfactant.
At this moment,, do not do special qualification to the order of above-mentioned heating process and above-mentioned pH value adjustment operation (following yet claim " acidification operation "), which operation preceding all can, also can carry out simultaneously in addition.For example can enumerate: after having accomplished heating process, carry out pH value adjustment operation; After having accomplished the adjustment of pH value, carry out heating process; PH value adjustment operation and heating process are carried out etc. simultaneously.In addition, beyond above-mentioned operation, also can suitably comprise and carry out other operation, or between above-mentioned operation, also can contain other operation.
Above-mentioned heating process is heated to colorized optical filtering film developing discharge opeing more than 50 ℃.
As after state that kind shown in the embodiment; Do not reach in temperature under 50 ℃ the situation; Even carry out acid treatment, chromatic photoresist agent and surfactant (particularly nonionic surfactant) can not coprecipitations, so can not fully reduce above-mentioned chromatic photoresist agent and surfactant.To this, if be heated to more than 50 ℃, because above-mentioned chromatic photoresist agent and surfactant ability coprecipitation are therefore preferred.
The heating-up temperature of this development discharge opeing is preferably set to 50～100 ℃, more preferably is set at 60～99 ℃, more preferably is set at 70～95 ℃, from the angle of economy and stable performance, is preferably set to 80～85 ℃ especially.
Do not have special qualification the heat time heating time to this moment, preferred about 1 minute or longer time, but, also can in pipe arrangement, carry out the several seconds reaction about (3～10 seconds) according to the proterties of discharge opeing.And, after with development discharge opeing heating,, preferably till Separation of Solid and Liquid, keep heated condition in order to improve cohesion filterableness and operation run stability always.
To not doing special qualification as the heating arrangement in the above-mentioned heating process.Suitably individually or combination for example use that heating arrangement such as heat exchanger, well heater gets final product.
Heating means to this moment are not done special qualification, can be to directly and/or indirectly heating of development discharge opeing.For example can enumerate: in the development discharge opeing, directly sneak into steam (saturated vapour, superheated vapor etc.); In the development discharge opeing, directly dispose well heater; Make the development discharge opeing pass through heat exchanger; In the pipe arrangement that the development discharge opeing is passed through, directly sneak into steam; Add the pipe arrangement outside that the thermal development discharge opeing is passed through; Electromagnetic induction heating etc. is carried out in the development discharge opeing.In addition, be easy to produce sediment in the development discharge opeing, also can suitably stir in order to make.
When above-mentioned development discharge opeing is heated, the heat the processing water after Separation of Solid and Liquid reclaimed again utilize, can seek cost degradation, and then, handle the cooling of water and also can carry out simultaneously, therefore preferred.And, to the development discharge opeing that has been heated after the heat interchange, also can further heat as required, make it reach the heating-up temperature of above-mentioned appointment.As an example of this heat interchange operation, can enumerate the processing water that makes heated condition and pass through heat-exchange system, from this processing water, reclaim heat, make the water-cooled while of processing, be used in the heating of development discharge opeing again with the heat that reclaims.
And, the temperature of the development discharge opeing after the heat treated till solid-liquid separation process, preferred settings is in the scope of the heating-up temperature of above-mentioned appointment.From the stability aspect, preferred 75～90 ℃ of the heating-up temperature of this moment.
Above-mentioned pH value adjustment operation (acidification operation) is with the adjustment of colorized optical filtering film developing discharge opeing oxytropism direction, adjusts to the pH value below 7.In the pH value is under the situation of 8 above alkaline ranges; Even carry out above-mentioned heating process; Chromatic photoresist agent and surfactant (particularly nonionic surfactant) can not coprecipitations, therefore can not reduce above-mentioned chromatic photoresist agent and surfactant fully.The scope of this pH value, preferred pH value be 1～less than 7; More preferably the pH value is 1～6; Being more preferably the pH value is 2～6; Preferred especially pH value is 4～5.5 acid range.
Special qualification is not done in acid to using in this acidification, can be one or more the acid of from mineral acids such as sulfuric acid, hydrochloric acid or organic acids such as acetic acid, phosphoric acid, selecting.And, also can suitably use alkali such as NaOH to adjust, its pH value is adjusted in the above-mentioned scope.
At this moment, the processing time of pH value adjustment is not done special qualification, in order to obtain stable performance, preferred about 3 minutes or longer time.After acidifying is carried out in the development discharge opeing,, preferably till liquid state is separated, keep acid state in order to improve cohesion filterableness and operation run stability always.
Equipment or method to this acidification are not done special qualification, can enumerate batch type or continous way etc.In addition, make it be easy to reaction, for example can enumerate: on the pipe arrangement that the development discharge opeing is passed through, connect and also be provided with and can acid be mixed the pipe arrangement that adds for development discharge opeing and acid are mixed; The stirring apparatus that setting makes development discharge opeing and acid be easy to mix; Setting has the reactive system that can acid be added and be stirred in the device in the development discharge opeing of having assembled; Carry out above pH value adjustment of two stages and make the pH value stabilizationization.
And,, be preferably in the pH value scope (below the pH7) like above-mentioned appointment for the pH value of the development discharge opeing after the acidification, till solid-liquid separation process.The pH value of this moment is considered from the angle that reduces additive amount of medicament, is preferably 4～5.5.
In above-mentioned solid-liquid separation process, from the development discharge opeing to concentrate and handle when carrying out Separation of Solid and Liquid till the water, under heating and the adjusted state of pH value, carry out.This state is meant, as the temperature range of above-mentioned appointment in and the state in the pH of appointment value scope, adjusted.
At this, the liquid after concentrate is meant the sediment of chromatic photoresist agent and surfactant etc. concentrated; Handling water is meant and has reduced the above-mentioned liquid that does not need behind the material.
And, the device or the method for Separation of Solid and Liquid not being done special qualification, can enumerate: film separation, filtrator separation, centrifuging, pressure floatation separation, sedimentation separation etc.
In addition, in solid-liquid separation process, reach processing water water quality standard beyond pH value and the temperature, that chromatic photoresist agent etc. has reduced, after its pH value and temperature are adjusted, can discharge.Under the situation that does not reach water quality standard or under the situation of further removing objectionable impurities, can further suitably carry out other treatment process.
For example: the processing water before discharging is under the situation of heated condition, preferably cools off.As cooling means, for example can be to place cooling, but the cooling means of heat-exchange system preferably is set, said heat-exchange system preferably have reclaim and utilize again with heating process in the development discharge opeing of the heating function that can carry out heat interchange.
Also have; Processing water before discharging is under the situation of acid state; Preferably, make it adjust to the pH value scope that can reach water quality standard, for example near the neutrality through alkali with the alkali salt of the alkali metal salt of potassium hydroxide or NaOH etc. or calcium hydroxide etc. etc.
Corresponding to the final purpose of the processing of colorized optical filtering film developing discharge opeing of the present invention, also can use ultraviolet irradiation, ozone treatment, biological treatment (for example activated sludge process), coagulative precipitation or flotation processing, reverse osmosis membrane processing, activated carbon treatment, ion-exchange treatment, electro-desalting processing, sorbent treatment etc. simultaneously.
And then, in development discharge opeing treatment process of the present invention, preferably in above-mentioned development discharge opeing, add flocculating agent.For example can enumerate flocculating agent and coagulator etc. is used simultaneously as optional member.And, as required, also can add germifuge, deodorant, foam-breaking agent, antiseptic etc.
Through using above-mentioned flocculating agent simultaneously, effect of the present invention will increase, and is therefore preferred.
Add the time of above-mentioned flocculating agent, can be in above-mentioned any operation, also can be between operation and operation, or in the front and back of operation.As an example, can be in above-mentioned heating process or in the front and back of above-mentioned pH value adjustment operation, also can be in adjustment.
Above-mentioned flocculating agent is not done special qualification, can use any inorganic and/or organic flocculating agent.
As above-mentioned inorganic flocculating agent, for example can enumerate: the aluminium salt of aluminium sulphate, aluminium polychloride etc.; The molysite of ferric trichloride, ferrous sulphate etc. etc.Can use and make up the above-mentioned salt of use separately.
In addition, the addition of inorganic flocculating agent is not done special qualification yet, can adjust, for above-mentioned development discharge opeing, be scaled aluminium or iron generally speaking, preferred 1～500 mg/litre according to the proterties of above-mentioned development discharge opeing.
And, as above-mentioned organic flocculant, preferred macromolecule organic flocculating agent, through using macromolecule organic flocculating agent, because of the cohesion piece becomes big, the probability that treatment effeciency is increased increases, and is therefore preferred.Kind to this macromolecule organic flocculating agent is not done special qualification, so long as normally used material gets final product in water treatment.As this macromolecule organic flocculating agent, for example can enumerate: the negative ion that gathers multipolymer of (methyl) acrylic acid, (methyl) acrylic acid and (methyl) acrylic amide and their alkali metal salt etc. is polymeric flocculant, gather non ionic polymer flocculant of (methyl) acrylic amide etc. etc.
Also have, the addition of organic flocculant is not done special qualification yet, can adjust,,, be preferably 0.01～10 mg/litre generally speaking in solids with respect to processed water according to the proterties of processed water.
Above-mentioned flocculating agent, the flocculating agent that preferably uses simultaneously with organic flocculant.This organic flocculant is not done special restriction, for example can enumerate: the quaternary ammonium salt by polyethyleneimine, epichlorokydrin polycondensation diamines, polyalkylene polyamine, diallyldimethylammonium chloride or dimethylamino (methyl) acrylic ester is a configuration polymer of monomers etc.; Usually the cationic organic polymer that in water treatment, uses etc.They both can use separately, use capable of being combined again.
In addition, the addition of organic flocculant is not done special qualification, can adjust,,, be preferably 0.01～10 mg/litre usually in solids with respect to the development discharge opeing according to the proterties of development discharge opeing.
Here; Development discharge opeing in the above-mentioned colored filter manufacturing process is meant: employed in colored filter manufacturing process; Comprise pigment, alkali soluble resins (alkali-soluble polymer), photopolymerization composition (curable monomer), Photoepolymerizationinitiater initiater (initiating agent), surfactant and solvent, and the liquid of developer solution etc.In this development discharge opeing, also contain anti-hardening into sometimes and grade.And, be used in the solvent in the chromatic photoresist agent, in the coating and the preceding baking operation before the development treatment of photoresist, it a greater part ofly is evaporated usually.
As a concrete example, can enumerate discharge opeing from the developing apparatus that uses in colored filter manufacturing installation or colored filter manufacturing line, the colored filter manufacturing process or its production line etc.
For example, in colorized optical filtering film developing discharge opeing, can enumerate the composition that mainly contains chromatic photoresist agent liquid and the discharge opeing of developer solution based on pigment dispersing method (preferably having used the photoetching process of chromatic photoresist agent).Specifically; Include after being coated with the chromatic photoresist agent; Unexposed portion is peeled off discharge opeing etc. with the development that developer solution washes out, and this developer solution is to contain to high concentration with nonionic surfactant as the surfactant of major component and the developer solution of alkaline components respectively.
As the water quality of common colorized optical filtering film developing discharge opeing, alkaline components (NaOH, KOH etc.) has higher concentration usually.As surfactant, contain the main body of nonionic, according to the needs of both sexes, also contain cationic, anionic property in addition.As giving an example of this surfactant; Be mainly the surfactant that is used for developer solution, that for example can enumerate has: polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, ethylene oxide-propylene oxide block copolymer, polyoxyethylene fatty acid fat, sorbitan fatty acid fat, Polyoxyethylene Sorbitol Fatty Acid Esters, polyoxyethylene styrene phenyl ether, styrene diphenyl polyoxyethylene ether, styrene three polyoxy vinethenes etc.As metal species, be generally the organic compound that contains copper, nickel, zinc etc.
And,, for example can enumerate the project shown in the table 1 as the general water quality of colorized optical filtering film developing discharge opeing.
Table 1
| Project | Assay value |
| pH | 9.5～12.5 |
| Conductance (ms/m) | 80～800 |
| TOC (mg/L) | 300～1000 |
| Turbidity (degree) | 100～500 |
| Surfactant (mg/L) | 30～300 |
| Heavy metal class (mg/L) | 0.1～10 |
The composition of chromatic photoresist agent liquid is designed to its pigment composition (mainly being organic pigment) and has compatibility with alkali-soluble polymer (resinoid bond perhaps is mixed with the material of macromolecule dispersing agent in this agent).And then, on the basis of the above, the composition of this chromatic photoresist agent liquid by added spreading agent (anionic property dispersed polymeres etc.), hardening polymer (oligomer, polymkeric substance and initiating agent that pigment is solidified), as the formations such as solvent of solvent.
Can access this chromatic photoresist agent liquid through known technology (for example with reference to non-patent literature 1).As an example; Pigment, spreading agent and solvent are cooperated; Be short grained operation through pigment is pulverized, and prepare the operation of photoresist liquid, just can access chromatic photoresist agent liquid through the photographic composition of mixed base soluble polymer, monomer and initiating agent etc.
In addition; Each components matching amount (quality %) in the chromatic photoresist agent liquid; Can do suitable change according to required colored filter, general use level is: pigment 2～8 quality %, alkali-soluble polymer 3～7 quality %, spreading agent 0.5～3 quality %, monomer 2～6 quality %, initiating agent 0.1～4 quality %, (surplus) solvent 70～85 quality % (for example with reference to non-patent literature 1).
As the composition of pigment, so long as the material that in colored filter manufacturing process, adopts usually gets final product, do not do special qualification, in general can use black pigment and color pigment, these pigment can suitably be selected from organic pigment and inorganic pigment.
Above-mentioned black raw material mainly is used in resin black matrix, can enumerate out: carbon black, nigrosine, anthraquinone are that black pigment 、 perylene is that black pigment, titanium are black etc.The particle diameter of black pigment is generally below the 200nm, more preferably 3～100nm.
Above-mentioned color pigment is the primary raw material use of redness (R)/green (the G)/blueness (B) of optical filter, indigo-blue (C) that CMY is optical filter/redness (M)/yellow (Y) as for example GB, also can be used as as required to proofread and correct the secondary pigment use of using to purpose colourity.In these pigment; The organic pigments of using more; As representational pigment composition; For example can enumerate: azo dyes system, insoluble azo system, condensation azo system, phthalocyanine system, quinacridone, dioxazines system, isoindoline system, anthraquinone system, purple cyclic ketones Yellow Red, thioindigo Xi 、 perylene system etc., selected simultaneously of all kinds in one or more pigment.
For example can enumerate, be diketopyrrolo-pyrrole (PR254), anthraquinone (PR177) etc. as the masstone pigment of red (R) look; Masstone pigment as green (G) look is chlorinated copper phthalocyanine (PG7) and zinc bromide phthalocyanine (PG58) etc.; Masstone pigment as blue (B) look is a ε type copper phthalocyanine (PB15:6) etc., in addition, also can enumerate the yellow uitramarine of isoindoline (PY139), nickel complex (PY150) etc.; The secondary pigment of the violet pigment of dioxazines (PV23) etc. etc. etc.
Below the preferred 100nm of the particle diameter of this organic pigment, more preferably 10～60nm.
As spreading agent, so long as the material that in the colored filter manufacturing process, adopts usually gets final product, do not do special qualification, in general can use the material that can be controlled at pigment particle size below 0.1 μ, have dispersion stabilization.
As above-mentioned spreading agent, for example can enumerate: anionic dispersing agents, cation dispersing agent, non-ionic dispersing agent etc.Specifically, can enumerate: the spreading agent of one or more that from polyoxyethylene alkyl phenyl ether system, polyethylene glycol di system, sorbitan carboxylic esters system, fatty acid modified polyester system, tertiary amine modified polyurethane system, (low/macromolecule) reactive pigment derivant etc., select.
More particularly, can enumerate one or more the spreading agent of from following material, selecting.
As above-mentioned anionic dispersing agents, for example can enumerate: the formalin condensation product of styrene-maleic anhydride copolymer, naphthalene sulfonate, polyacrylate, CMC, alkene-copolymer-maleic anhydride, poly styrene sulfonate, acrylamide and acrylic acid copolymer, sodium alginate etc.
In addition, as above-mentioned non-ionic dispersing agent, for example can enumerate: polyvinyl alcohol (PVA), polyoxyethylene alkyl ether, polyoxyethylene poly-oxygen propylene aether piece (polyether-type spreading agent), starch polymer etc.
Also have, as above-mentioned cation dispersing agent, for example can enumerate: polyethyleneimine, aminoalkyl (methyl) acrylate copolymer, polyvinyl imidazole, shitosan, polyalkylene polyamine, polyacrylamide etc.
As alkali-soluble polymer; So long as the material that in the colored filter manufacturing process, adopts usually gets final product; Do not do special qualification, as long as can combine maybe to adhere to the material on the substrate of the photoresist film after the development with the granules of pigments in the chromatic photoresist agent.
As above-mentioned alkali-soluble polymer, for example can enumerate: the polypropylene system of (methyl) acrylic acid and (methyl) acrylate etc., polyimide system, CARDO system etc.Usually, the multipolymer of (methyl) acrylic acid or (methyl) acrylate etc. forms basic structure, and preferred the use contained the acryl resin that (methyl) acrylate etc. is copolymerized to the carboxyl of (methyl) acrylic acid etc.
As its concrete illustration, can enumerate: the resin of from (methyl) acrylic acid/benzyl (methyl) acrylate copolymer, (methyl) acrylic acid/benzyl (methyl) acrylic ester/styrol copolymer, (methyl) acrylic acid/methyl (methyl) acrylate copolymer, (methyl) acrylic acid/methyl (methyl) acrylic ester/styrol copolymer, selecting one or more.
In addition, its molecular weight is preferably 5000～100000, and the acid number of this resin is preferably 60～150mgKOH/g.
Curable monomer (thereby the material that utilizes ultraviolet exposure that decomposition of initiator polymerization and polymkeric substance (resin) are changed) so long as the material that in the colored filter manufacturing process, adopts usually gets final product, is not done special qualification.
Above-mentioned curable monomer; For example can enumerate: one or both monomers of from acrylic acid, methacrylic acid, acrylic ester, methacrylate ester, polyacrylic, phenolic novolak type epoxy resin system, phenol aldehyde type cresols epoxy resin, multifunctional polyester acrylic ester, polyimide system, polyethenol series, multi-functional polyol's acrylic ester, multifunctional urethane acrylate etc., selecting wherein preferably have the monomer of multiple functional radical.
As initiating agent, can enumerate: the initiating agent of one or more that from acetophenone system, styrax system, benzophenone series, triazine system, imidazoles system, oxime system etc., select.
As its concrete illustration, can enumerate: the initiating agent of one or more that from 1-hydroxyl-cyclohexyl-phenyl-ketone, 2-hydroxy-2-methyl-1-phenyl-propane-1-ketone, 2-methyl isophthalic acid-[4-(methyl mercapto) phenyl]-2-morpholine third-1-ketone, 2-benzyl-2-dimethylamino-1-(4-phenylephrine)-1-butanone etc., select.
In addition, also can contain silane coupling agent etc. and be used as emulsion or gluing auxiliary agent.
For solvent; So long as the material that in the colored filter manufacturing process, adopts usually gets final product; Do not do special qualification; As representational solvent, for example can enumerate: 1-Methoxy-2-propyl acetate (PGMEA), methyl 3-methoxy propyl acid esters (MMP), ethyl lactate (EL), n-butyl acetate (NBA), ethyl 3-ethoxy-c acid esters (EEP) etc.As other solvent, for example can enumerate: divinyl dimethyl ether, 3-ethoxyl ethyl propionate, phenmethylol etc.In addition, these solvents are in the coating and the preceding baking operation before the development treatment of photoresist, and it a greater part ofly is evaporated usually.
In addition, developer solution is the not part (unhardened chromatic photoresist agent part) that is used for removing the chromatic photoresist agent in the developing procedure, or is used for cleaning the alkaline aqueous solution (pH8～14, preferred pH10～13) of substrate top.So long as the material that in the colored filter manufacturing process, adopts usually gets final product, do not do special qualification.
Developer solution is the alkali metal salt from sodium carbonate, NaOH or potassium hydroxide etc.; The alkali salt of lime carbonate etc.; TMAH, N, the inorganic and/or organic alkaline components of more than one that select in the amine of N-dimethyl benzylamine, triethanolamine etc. contains the WS of appropriate amount of defoamer and surfactant etc.As this surfactant, for example can enumerate: polyoxyethylene alkyl ether, polyoxyethylene alkyl phenyl ether, ethylene oxide-propylene oxide block copolymer, polyoxyethylene fatty acid fat, sorbitan fatty acid fat, Polyoxyethylene Sorbitol Fatty Acid Esters, polyoxyethylene styrene phenyl ether, styrene diphenyl polyoxyethylene ether, styrene trimerization oxyethylation phenyl ether etc.
About the example of the disposal route of colorized optical filtering film developing discharge opeing of the present invention, explain as follows with reference to Fig. 1～4 (flow process 1～7).And below the example of explanation is just represented an example of the example that the present invention is representative, can not come narrow sense ground to explain scope of the present invention in view of the above.
Flow process 1
Development discharge opeing (20～30 ℃) is transported to heat-exchange system (heat interchange) and heats (preferred about 60～75 ℃).As required, heated development discharge opeing is heated to (preferred 70～95 ℃, more preferably 80～85 ℃) more than 50 ℃ through heating system (heating).Also can sneak into water vapour (about 100 ℃) spraying in the development discharge opeing this moment in heating system, makes development discharge opeing heating.And then; Heated development discharge opeing; When adding acid, be adjusted to through reactive system (reaction) scope between the neutrality～acidity of appointment (pH value is 7 below, preferred pH value be less than 7, it is further that preferably the pH value is 1～6, more preferably the pH value is 2～6).This moment, reactive system remained on (preferred 70～95 ℃, more preferably 80～85 ℃) more than 50 ℃.The reaction here both can also can be carried out in reaction tube in reactor.And; Be in the heating of appointment and the development discharge opeing of neutrality～acidity (preferred acidic) state; Through solid-liquid separation system, the sedimentary concentrate that will contain chromatic photoresist agent and surfactant etc. separates with the processing water that reduces chromatic photoresist agent and surfactant etc.Concentrate is transported in the concentrate hold-up vessel.
Owing to handle glassware for drinking water the temperature (preferred 70～95 ℃, more preferably 80～85 ℃) more than 50 ℃ is arranged; Therefore; It is transported to heat-exchange system, there with heat recovery and when cooling off, is used to add the thermal development discharge opeing again to what be transported to that the development discharge opeing here gives heat.
In addition, under the situation that does not dispose heat-exchange system or be not transferred, be transferred next development discharge opeing through the heating system heating from the heat treated water in the Separation of Solid and Liquid.Therefore, preferably heat-exchange system is configured in the front of well heater, comes to utilize again the heat of handling water.
Flow process 2
Suitably omit the part that repeats with above-mentioned flow process 1.
The development discharge opeing is when adding acid, to be transported to reactive system, in reactive system, it is adjusted in the scope between the neutrality～acidity of appointment.Remain on the development discharge opeing in the scope between neutrality～acidity, after heat-exchange system, then be heated to more than 50 ℃ through heating system.Then, through heating and the development discharge opeing that remains on neutrality～acid state,, make and contain sedimentary concentrate and handle water and carry out Separation of Solid and Liquid through solid-liquid separation system.Owing to handle glassware for drinking water the temperature more than 50 ℃ is arranged, therefore, it is transported to heat-exchange system, when being cooled there, the development discharge opeing is heated.
Flow process 3
Suitably omit the part that repeats with above-mentioned flow process 1.
The development discharge opeing is through heat-exchange system, heating system, reactive system, under the heating and neutrality～acid state of appointment,, made and contains sedimentary concentrate 1 and separate with processing water 1 by Separation of Solid and Liquid through Separation of Solid and Liquid 1.Have the temperature more than 50 ℃ owing to handle water 1, therefore, it is transported to heat-exchange system, when being cooled there, the development discharge opeing is heated.In addition; To containing the sedimentary condensed water 1 that has concentrated by Separation of Solid and Liquid 1; In order to hold it in the heated condition of appointment, further temperature losses is partly heated again, under the state that keeps neutrality～acidity with steam; Further carry out Separation of Solid and Liquid through Separation of Solid and Liquid 2, sedimentary concentrates 2 such as containing chromatic photoresist agent and surfactant is separated with processing water 2.Because this processing water 2 has been heated, so also can be used for thermal cross over.And,, also can be transported to heat-exchange system after water 1 confluxes with processing water 2 with handling as an example.
Flow process 4
Suitably omit the part that repeats with above-mentioned flow process 1.
The development discharge opeing is through heat-exchange system, heating system, reactive system.Before Separation of Solid and Liquid, add flocculating agent.Contain flocculating agent and in the heating of appointment and the development discharge opeing under the acid state, by Separation of Solid and Liquid, make and contain sedimentary concentrate and handle separated form water through solid-liquid separation system.
Flow process 5
Suitably omit the part that repeats with above-mentioned flow process 1.
The development discharge opeing through heat-exchange system, heating system, reactive system, further through solid-liquid separation system, makes and contains sedimentary concentrate and handle separated form water.In this concentrate, add flocculating agent, the sediment that contains chromatic photoresist agent and surfactant etc. is reclaimed.At this moment, concentrate both can remain on the heating of appointment and the state of neutrality～acidity, and the material demand that also can remove according to hope is adjusted suitable temperature and pH value.For example: under the situation that will remove the heavy metal class, be adjusted to alkaline range.
Flow process 6
Suitably omit the part that repeats with above-mentioned flow process 1.
The development discharge opeing through heat-exchange system, heating system, reactive system, further through solid-liquid separation system, makes and contains sedimentary concentrate and handle separated form water.In this concentrate, add steam, this concentrate is set in the heating of appointment and the state of neutrality～acidity, the sediment that contains chromatic photoresist agent and surfactant etc. is reclaimed.
Flow process 7
Suitably omit the part that repeats with above-mentioned flow process 1.
The development discharge opeing through heat-exchange system, heating system, reactive system, further through solid-liquid separation system, makes and contains sedimentary concentrate and handle water 1 and separate.Handle water 1 and then pass through biological treatment system, be discharged as final processing water 2.In this biological treatment system, dispose biological treatment (activated sludge process), cohesion and settling system, filtering system, activated carbon system.In addition, except handling water 1, also can washes or Clean-waste water be transported in this biological treatment system and handle.
In addition, handle water 1 and can be the processing water in the above-mentioned flow process 2～6, so long as the processing water of handling through method of the present invention gets final product.And, also can reverse osmosis membrane be applicable to that handling water 2 carries out the water recovery.
The molecular weight of resin is measured with high temperature GPC device and is got final product.
The acid number of resin can get final product according to " JIS K 2501-2003 petroleum product and lubricating oil-neutralization number experimental technique ".
Sample dissolution in the titration solvent that has mixed xylene and dimethyl formamide (1+1), through potentiometric titration, is carried out titration with potassium hydroxide/ethanolic solution of 0.1mol/L, the flex point on the titration curve is set at terminal point.Titer according to used till the potassium hydroxide solution titration to terminal calculates acid number.
To the mensuration of water quality, get final product with known assay method (JIS, time water detection method, last water detection method).For example can enumerate following assay method:
Conductivity: JIS-K-0102.13; PH:JIS-K-0102.12.1; TOC:JIS-K-0102.22.1; Turbidity: JIS-K-0101.9.2; Surfactant: JIS-K-0102.30.2.1; Metal species: JIS-K-0102.Adopt said method that these projects are measured.
Mensuration for MFF; After filtering with 5A filter paper (manufacturing of ADVANTEC Co., Ltd.); Then with millipore filter (aperture: 0.45 μ m; Japan Millipore Co., Ltd. makes) to filter, the time of the filtration time and the filtrator of filter paper of measuring (is filtered beginning～500 milliliters filtered time: T1, the 500 milliliters filtered time～1000 milliliters filtered times: T2).Filtration time by this filtrator calculates microfiltration function (Micro Filter Function, MFF) value (T2/T1).The MFF value is the index that expression has or not the material of the film obstruction that makes 0.45 μ m.
Embodiment:
Specific embodiment is described below, but the present invention is not limited thereto.
[cohesion experiment]
500 milliliters of capacity beakers that will add 500 milliliters of former water of colored filter discharge opeing (also claiming " former water ") are placed on the mixing platform that has well heater, experimentize by following operation.
[embodiment 1～3 and comparative example 1～3]
Embodiment 1
After laying; Stir with 150rpm; Add sulfuric acid and make the pH value adjust to 5, be heated to 80 ℃, after keeping about 3 minutes with 80 ℃; The solution of heated condition (pH5 and about 80 ℃) is filtered with No.5A filter paper (manufacturing of ADVANTEC Co., Ltd.), the filtrating that placement is cooled to about room temperature has been carried out TOC and turbidimetric analysis turbidimetry.
" the former water of colored filter discharge opeing " as this cohesion experiment; Used behind the coating chromatic photoresist; Unexposed portion is peeled off discharge opeing with the development that developer solution washes out, and this developer solution is to contain to high concentration with nonionic surfactant as the surfactant of major component and the developer solution of alkaline components respectively.
This raw water quality, as shown in table 2.
Table 2
| pH | 12.1 |
| Conductance (ms/m) | 671 |
| TOC ?(mg/L) | 743 |
| Turbidity (degree) | 144 |
Embodiment 2
Except the pH value is adjusted to 7, operate with the foregoing description 1 identically.
Embodiment 3
The pH value is adjusted to after 7, further added salt and make Na
2SO
4Concentration become 0.4 mol, in addition, operate with embodiment 1 identically.
Comparative example 1
Except the pH value is adjusted to 12, operate with the foregoing description 1 identically.
Comparative example 2
The pH value is adjusted to after 5, be heated to 40 ℃, after keeping about 3 minutes,, in addition, operate identically with embodiment 1 with the solution filtration of about 40 ℃ heated conditions with 40 ℃.
Comparative example 3
The pH value is adjusted to after 5, do not heated, this solution is filtered, in addition, operate identically with embodiment 1.
The result of embodiment 1～3 and comparative example 1～3 is shown in table 3.
Table 3
Comparative example 4～7
In addition, the pH value of former water adjusted to 5,7,9,11.5 separately after, do not heat, this solution is filtered, in addition, operate with embodiment 1 identically.(being respectively comparative example 4～7).
Table 4
| The pH adjusted value | Heating-up temperature (℃) | The MFF value | |
| Comparative example 4 | 5 | Do not heat | 1.03 |
| Comparative example 5 | 7 | Do not heat | 1.02 |
| Comparative example 6 | 9 | Do not heat | 1.02 |
| Comparative example 7 | 11.5 | Do not heat | 1.02 |
[embodiment 4～6 and comparative example 8～11]
Embodiment 4
Except the pH value of former water is adjusted to 3, operate with embodiment 1 identically.
Embodiment 5
Operate with embodiment 1 identically.
Embodiment 6
The pH value is adjusted to after 5, be heated to 60 ℃, after keeping 3 minutes,, in addition, operate identically with embodiment 1 with the solution filtration of about 60 ℃ heated conditions with 60 ℃.
Comparative example 8
The pH value is adjusted to after 5, be heated to 80 ℃, after keeping 3 minutes, and then be cooled to 25 ℃, this cooled solution is filtered, in addition, operate identically with embodiment 1.
Comparative example 9
The pH value of former water is adjusted to after 7, be heated to 80 ℃, after keeping 3 minutes, be cooled to 25 ℃, this cooled solution is filtered, in addition, operate identically with embodiment 1.
Comparative example 10
Except the pH value of former water is adjusted to 12, operate with embodiment 1 identically.
Comparative example 11
The pH value of former water is adjusted to after 12, be heated to 80 ℃, after keeping 3 minutes, be cooled to 25 ℃, this cooled solution is filtered, in addition, operate identically with embodiment 1.
The result of embodiment 4～6 and comparative example 8～11 is shown in Table 5.
Table 5
Comparative example 12
In the former water of colored filter discharge opeing of embodiment 1, add diallyl dimethyl ammoniumchloride (P-DADMAC; Molecular weight 750,000) organic flocculant, under 25 ℃, the condition of pH12,150rpm stirred after 90 seconds, measured its wadding block size and supernatant turbidity (NTU).Its result is shown in table 6.
Table 6
As implied above; Development discharge opeing for colored filter; Only condense filtrations (with reference to table 6), only carry out the pH value and adjust (with reference to Fig. 6), only heat (with reference to table 5, comparative example 10 and 11), can not reduce chromatic photoresist agent (turbidity) and surfactant (TOC, COD) through adding flocculating agent.
In addition, as shown in Figure 6, only pH is adjusted, because dyeing does not change fully, muddy proterties MFF value is below 1.1, so muddiness becomes disperse state.
On the other hand; Development discharge opeing for colored filter; Through pH value being adjusted to below 7 and being passed through heating; Generate the insoluble matter of pigment (chromatic photoresist agent) and surfactant,, can confirm can pigment and surfactant be removed (with reference to Fig. 5 and embodiment 1) through under heated condition, carrying out separating treatment.
Utilizability on the industry
As stated; The present invention handles through colorized optical filtering film developing discharge opeing is heated and remained under neutrality/acid state; Can not only reduce the chromatic photoresist agent in this development discharge opeing preferably; And can reduce surfactant preferably, so, can handle colorized optical filtering film developing discharge opeing with the operation run stability to condense filterableness preferably.In other words, the stability of operation running of stabilization of COD value that is referred to as stabilization and the discharging of cohesion becomes good.In addition, owing to can reclaim and utilization again the heating heat, so stability and economy aspect that its operation is turned round also are desirable.And the efficient of removing COD is very high, and the technology of carrying out discharge opeing emission treatment or discharge opeing recycling is advanced, can aspect financial cost, greatly improve present situation.And then, also can reduce biological reactor capacity, reduce the use amount of flocculating agent and activated charcoal etc., the cost degradation that therefore discharge opeing is handled becomes possibility.
In addition, present technique also can be taked following formation.
(1) disposal route of the development discharge opeing in a kind of colored filter manufacturing process; It is characterized in that; Have and the development discharge opeing to be heated to the heating process more than 50 ℃; Adjust to the pH value adjustment operation below 7 with pH value that should the development discharge opeing, above-mentioned development discharge opeing is being heated and under the adjusted state of pH value, carrying out Separation of Solid and Liquid.
(2) like above-mentioned (1) described development discharge opeing disposal route; It is characterized in that; In above-mentioned heating process, above-mentioned development discharge opeing is heated to 60～100 ℃ and/or in above-mentioned pH value adjustment operation, the pH value of above-mentioned development discharge opeing is adjusted to 2～6 acid range.
(3) like above-mentioned (1) or (2) described development discharge opeing disposal route, it is characterized in that, use flocculating agent simultaneously.
(4) like the disposal route of each described development discharge opeing in above-mentioned (1)～(3), it is characterized in that, reclaim the heat in the heating fluid after the above-mentioned Separation of Solid and Liquid, be used in the heating of the development discharge opeing in the above-mentioned heating process again.
Claims (5)
1. the disposal route of the development discharge opeing in the colored filter manufacturing process,
It is characterized in that, have with this development discharge opeing be heated to more than 50 ℃ heating process and
The pH value of this development discharge opeing is adjusted to the pH value adjustment operation below 7,
Should the development discharge opeing heating and under the adjusted state of pH value, carrying out Separation of Solid and Liquid.
2. the disposal route of development discharge opeing as claimed in claim 1 is characterized in that,
In above-mentioned heating process, above-mentioned development discharge opeing is heated to 60～100 ℃ and/or in above-mentioned pH value adjustment operation, the pH value of above-mentioned development discharge opeing is adjusted to 2～6 acid range.
3. the disposal route of development discharge opeing as claimed in claim 1 is characterized in that, uses flocculating agent simultaneously.
4. the disposal route of development discharge opeing as claimed in claim 2 is characterized in that, uses flocculating agent simultaneously.
5. like the disposal route of each described development discharge opeing in the claim 1～4, it is characterized in that, reclaim the heat in the heat treated water after the above-mentioned Separation of Solid and Liquid, be used in the heating of the development discharge opeing in the above-mentioned heating process again.
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| Application Number | Priority Date | Filing Date | Title |
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| JP2011011841A JP2012154994A (en) | 2011-01-24 | 2011-01-24 | Treatment method of development wastewater in color filter manufacturing process |
| JP2011-011841 | 2011-01-24 |
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| CN102608878A true CN102608878A (en) | 2012-07-25 |
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| JP (1) | JP2012154994A (en) |
| CN (1) | CN102608878A (en) |
| TW (1) | TW201238906A (en) |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104556254A (en) * | 2013-10-15 | 2015-04-29 | 沈阳芯源微电子设备有限公司 | Separation and recovery device for realizing liquids with different concentrations by vacuum |
| CN104981435A (en) * | 2013-02-13 | 2015-10-14 | 栗田工业株式会社 | Method for treating development wastewater from color filter production step |
| CN106547176A (en) * | 2015-09-21 | 2017-03-29 | 乐凯华光印刷科技有限公司 | A kind of developer solution suitable for the photosensitive CTP plates of low chemical treatment |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87105308A (en) * | 1986-07-23 | 1988-02-03 | 住友重机械工业株式会社 | Contain the processing of the waste liquid of photoresist |
| JPH021840A (en) * | 1988-06-10 | 1990-01-08 | Konica Corp | Method and device for processing photosensitive material |
| JPH04322798A (en) * | 1991-04-22 | 1992-11-12 | Konica Corp | Treatment of waste processing solution |
| JPH09262589A (en) * | 1996-03-27 | 1997-10-07 | Matsushita Electric Ind Co Ltd | Method and apparatus for treating alkali waste solution |
| JP2006255668A (en) * | 2005-03-18 | 2006-09-28 | Kurita Water Ind Ltd | Photoresist-containing wastewater treatment method |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2004066118A (en) * | 2002-08-07 | 2004-03-04 | Asahi Kasei Chemicals Corp | Method of treating photosensitive resin plate development waste solution |
-
2011
- 2011-01-24 JP JP2011011841A patent/JP2012154994A/en active Pending
- 2011-12-28 TW TW100149268A patent/TW201238906A/en unknown
-
2012
- 2012-01-13 CN CN2012100131259A patent/CN102608878A/en active Pending
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN87105308A (en) * | 1986-07-23 | 1988-02-03 | 住友重机械工业株式会社 | Contain the processing of the waste liquid of photoresist |
| JPH021840A (en) * | 1988-06-10 | 1990-01-08 | Konica Corp | Method and device for processing photosensitive material |
| JPH04322798A (en) * | 1991-04-22 | 1992-11-12 | Konica Corp | Treatment of waste processing solution |
| JPH09262589A (en) * | 1996-03-27 | 1997-10-07 | Matsushita Electric Ind Co Ltd | Method and apparatus for treating alkali waste solution |
| JP2006255668A (en) * | 2005-03-18 | 2006-09-28 | Kurita Water Ind Ltd | Photoresist-containing wastewater treatment method |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104981435A (en) * | 2013-02-13 | 2015-10-14 | 栗田工业株式会社 | Method for treating development wastewater from color filter production step |
| CN104556254A (en) * | 2013-10-15 | 2015-04-29 | 沈阳芯源微电子设备有限公司 | Separation and recovery device for realizing liquids with different concentrations by vacuum |
| CN106547176A (en) * | 2015-09-21 | 2017-03-29 | 乐凯华光印刷科技有限公司 | A kind of developer solution suitable for the photosensitive CTP plates of low chemical treatment |
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| Publication number | Publication date |
|---|---|
| TW201238906A (en) | 2012-10-01 |
| JP2012154994A (en) | 2012-08-16 |
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Application publication date: 20120725 |