WO2014021043A1 - 現像液の処理装置及び処理方法 - Google Patents
現像液の処理装置及び処理方法 Download PDFInfo
- Publication number
- WO2014021043A1 WO2014021043A1 PCT/JP2013/068087 JP2013068087W WO2014021043A1 WO 2014021043 A1 WO2014021043 A1 WO 2014021043A1 JP 2013068087 W JP2013068087 W JP 2013068087W WO 2014021043 A1 WO2014021043 A1 WO 2014021043A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- tank
- clarified liquid
- developer
- defoaming
- processing apparatus
- Prior art date
Links
Images
Classifications
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/30—Imagewise removal using liquid means
- G03F7/32—Liquid compositions therefor, e.g. developers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D19/00—Degasification of liquids
- B01D19/0042—Degasification of liquids modifying the liquid flow
- B01D19/0052—Degasification of liquids modifying the liquid flow in rotating vessels, vessels containing movable parts or in which centrifugal movement is caused
-
- 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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/26—Separation of sediment aided by centrifugal force or centripetal force
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/26—Separation of sediment aided by centrifugal force or centripetal force
- B01D21/262—Separation of sediment aided by centrifugal force or centripetal force by using a centrifuge
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D21/00—Separation of suspended solid particles from liquids by sedimentation
- B01D21/26—Separation of sediment aided by centrifugal force or centripetal force
- B01D21/267—Separation of sediment aided by centrifugal force or centripetal force by using a cyclone
-
- 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
-
- 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
Definitions
- the present invention relates to a developer processing apparatus and a processing method.
- the pattern refers to the shape of a specific material on the substrate.
- the conductive pattern refers to the shape of the conductive material on the substrate.
- a material for forming the conductive pattern a non-fired photosensitive conductive paste containing a conductive filler is known. Yes.
- Non-baking type photosensitive conductive paste is one in which conductive fillers are brought into contact with each other by curing shrinkage in a relatively low temperature curing process, and conductivity is developed.
- a conductive pattern is also formed on a film substrate having poor heat resistance. Since it can be formed, development for fine pitch wiring of a touch panel of a smart phone or an electronic blackboard is underway (Patent Documents 1 to 5).
- the conductive pattern formation process using the photosensitive conductive paste is performed by irradiating a coating film or the like formed from the photosensitive conductive paste with light through a photomask having a desired pattern. This is a process in which a solubility difference is generated and a dissolved component is eluted in a developer to form a pattern.
- the conductive pattern forming process using the photosensitive conductive paste essentially includes the development processing step using the developer.
- insoluble inorganic components and lumps of organic components remain as insoluble components.
- insoluble components that is, residues
- a photosensitive conductive paste for forming an electrode pattern contains an expensive metal such as silver. Therefore, separating a residue from a developer after development processing has a significance as a resource recovery. Also have.
- the present invention eliminates the problems associated with the occurrence of scum and greatly contributes to the improvement of the product defect rate, the improvement of the operating rate of the manufacturing apparatus or the reduction of the manufacturing cost due to the highly efficient recovery of precious metals, and the like.
- the purpose is to provide.
- the present inventors have intensively studied not to remove the generated scum but to suppress the occurrence of scum in the first place.
- the present invention has been completed by finding that the combination of the above and the flow of scum is extremely effective in suppressing the occurrence of scum.
- the present invention provides a processing apparatus and a processing method for a developer described in the following (1) to (10).
- a developer comprising: a centrifuge for separating the developer after development into a clarified liquid and a residue by centrifugation; and a defoaming device for degassing and discharging the clarified liquid. Processing equipment.
- the developer after the development processing is centrifuged to obtain a clarified liquid and a residue, a centrifuge, the first tank for storing the clarified liquid, and the clarified liquid in the first tank.
- the developer after the development processing is centrifuged to obtain a clarified liquid and a residue, a centrifuge, the first tank storing the clarified liquid, and the clarified liquid in the first tank.
- the developer processing apparatus of the present invention it is possible to greatly suppress the occurrence of scum, thereby improving the product defect rate, improving the operating rate of the manufacturing apparatus, or reducing the manufacturing cost by highly efficient recovery of precious metals. Can be achieved.
- the developer processing apparatus of the present invention includes a centrifugal separator that separates a clarified liquid and a residue by centrifuging the developed developer, and a defoaming apparatus that degass and discharges the clarified liquid. It is characterized by providing.
- the processing method of the developer of the present invention comprises a centrifugal separation step obtained by separating the clarified liquid and the residue by centrifuging the developed developer, and defoaming the clarified liquid by defoaming.
- the developer processing apparatus is a centrifugal separator that obtains a clarified liquid and a residue by centrifuging the developer after the development process, and the clarified liquid.
- a degassing device for defoaming and discharging the clarified liquid in the first tank, a clarified liquid discharged from the defoaming device, and an unused developer.
- the processing apparatus of the developing solution which concerns on 2nd embodiment of this invention shown by FIG. 3 centrifuges the developing solution after a developing process, and obtains a clarified liquid and a residue
- the above-mentioned A first tank that stores the clarified liquid, a defoaming device that degass and discharges the clarified liquid in the first tank, a clarified liquid discharged from the defoamed apparatus, and unused development.
- a second tank for mixing and storing the liquid, and means for supplying the clarified liquid overflowing from the first tank to the second tank from above the second tank. It is characterized by that.
- the developer processing apparatus is a centrifuge that separates the developer after development processing into a clarified liquid and a residue by centrifugation, and the clarified liquid. And a defoaming device for defoaming and discharging.
- Centrifuge means that the residue and developer are separated by centrifugal force using the difference in specific gravity between the developer and the solid content, that is, the insoluble component residue, and the developer. This is a technique for obtaining a clarified liquid from which the odor is removed.
- the clarified solution refers to a developer from which residues are removed.
- the clarified liquid may contain insoluble components such as organic substances represented by organic particles that could not be separated by centrifugal force.
- the residue is generally composed mainly of inorganic particles.
- the device that mechanically achieves such centrifugation is a centrifuge, but a decanter type centrifuge is preferable because continuous processing is possible.
- the manufacturing cost can be reduced by melting and collecting the noble metal.
- the processing apparatus for the developer of the present invention is suitable for collecting residues containing metal particles as inorganic particles, and the metal particles are Ag, Au, Cu, Pt, Pb, Sn, Ni, Al, W, Mo, Ruthenium oxide, A noble metal particle selected from the group consisting of Cr, Ti, and indium is more preferable from the viewpoint of manufacturing cost reduction.
- the clarified liquid obtained by centrifugation is supplied to the first tank and stored.
- a large amount of air is entrained in the clarified liquid supplied to the first tank by centrifugation, and the bubble rate is extremely high.
- insoluble components such as organic substances having a low specific gravity rise to the liquid surface together with the bubbles, aggregate, float, and scum is generated. For this reason, the one where the bubble rate of the clear liquid stored by the 1st tank is low is preferable.
- the bubble rate is obtained by collecting the liquid to be measured in a graduated cylinder, measuring the volume (L1) of the part containing bubbles and the volume (L2) of the part not containing bubbles, and using the following formula (1): Can be calculated.
- the developing solution processing apparatus includes a defoaming device for defoaming and discharging the clarified liquid.
- the developer processing apparatus defoams the clarified liquid in the first tank in order to reduce the bubble rate of the clarified liquid stored in the first tank.
- a defoaming device for discharging.
- the defoaming device include a defoaming pump or a hollow fiber membrane degassing module by heating boiling degassing, ultrasonic degassing, vacuum vacuum degassing or centrifugal degassing, or a combination thereof.
- the bubble ratio of the clarified liquid obtained by centrifugation often exceeds 50%, but the bubble ratio of the clarified liquid after the defoaming treatment by the defoaming device is preferably 10% or less. % Or less is more preferable.
- the clarified liquid obtained by centrifugation is supplied to the first tank in the developer processing apparatus according to the first embodiment or the second embodiment of the present invention.
- the clarified liquid after the defoaming process is supplied to and stored in the second tank.
- unused developer is supplied to the second tank. That is, in the second tank, the clarified liquid after the defoaming process and the unused developer are mixed and stored.
- the supply amount (flow rate and the like) of the unused developer supplied to the second tank may be appropriately determined in consideration of the balance of the liquid flow of the entire processing apparatus of the present invention.
- unused developer is a convenient term that distinguishes the developer having a different origin from the clarified solution after the defoaming treatment, and is used for development processing in a strict sense. It is not restricted to the developing solution which is not carried out. That is, the unused developer may be a used (reused) developer that has been purified by means other than the processing apparatus of the present invention.
- the developing solution processing apparatus includes means for supplying the clarified liquid overflowing from the second tank to the first tank from above the first tank.
- the developer processing apparatus includes means for supplying the clarified liquid overflowing from the first tank to the second tank from above the second tank.
- Examples of means for supplying the clarified liquid overflowing from the first tank or the second tank to the other tank include providing a pipe between the first tank and the second tank. From the viewpoint of space saving and simplification of the processing apparatus structure, as shown in FIGS. 2 and 3, the first tank and the second tank are adjacent to each other with a partition plate interposed therebetween, and the first tank or the second tank It is preferable to flow the clear liquid overflowing from the tank along the partition plate.
- a flow for suppressing the insoluble component in the clarified liquid stored in the first tank from rising to the liquid level It is preferable to apply to the clarified liquid in the first tank.
- the liquid supplied from above the first tank is a clarified liquid overflowing from the second tank, as shown in FIG. .
- FIG. 3 shows the clarified liquid after centrifugation.
- the height difference between the liquid level of the clarified liquid stored in the first tank and the liquid level of the clarified liquid stored in the second tank is preferably 5 cm or more.
- the respective capacities of the first tank and the second tank are preferably about 100 to 300L.
- the air entrained with the clarified liquid stored in the first tank i.e., bubbles
- the vertical flow velocity of the overflow flow supplied from above the first tank or the second tank. Is preferably 15 cm / s or more, and more preferably 20 cm / s or more.
- “from the upper direction” includes not only the upper side in the vertical direction but also the upper diagonal direction.
- the vertical flow velocity of the overflow flow can be obtained by decomposing it into a vertical direction and a horizontal direction using the oblique flow velocity as a velocity vector.
- the developing solution processing apparatus that overflows the clarified liquid after the defoaming process by the defoaming apparatus is preferable.
- the concentration of the developer processed by the processing apparatus of the present invention is preferably corrected periodically.
- the measuring device for the developer concentration include a pH meter, an electric conductivity meter, and an automatic titration device.
- a method for adjusting the concentration of the developing solution a method of adding a predetermined amount of unused high-concentration developing solution to the system of the processing apparatus can be mentioned.
- the developer processing apparatus of the present invention is a pattern forming process in which a photosensitive paste comprising an organic component containing a photosensitive component is applied onto a substrate, exposed, and developed to form a desired pattern, more specifically, In the conductive pattern formation process using the photosensitive conductive paste, it can be suitably used in the development processing step. Among these, it is preferable to use it in the development processing step of the conductive pattern forming process using the non-baked photosensitive conductive paste that is particularly likely to generate scum because the effect can be remarkably exhibited.
- Examples of the development processing method include alkali development and organic development.
- Examples of the developer used for alkali development include tetramethylammonium hydroxide, diethanolamine, diethylaminoethanol, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, triethylamine, diethylamine, methylamine, dimethylamine, and dimethylaminoethyl acetate.
- Examples of the developer used for organic development include N-methyl-2-pyrrolidone, N-acetyl-2-pyrrolidone, N, N-dimethylacetamide, N, N-dimethylformamide, dimethyl sulfoxide or hexamethylphosphoryl
- Examples thereof include polar solvents such as amides or mixed solutions in which these polar solvents are combined with methanol, ethanol, isopropyl alcohol, xylene, water, methyl carbitol, ethyl carbitol, or the like.
- Examples of the non-baked photosensitive conductive paste include a conductive filler in a photosensitive resin obtained by mixing a compound (A) having an alkoxy group, a photosensitive component (B), and a photopolymerization initiator (C). What disperse
- Examples of the compound (A) having an alkoxy group include N-methoxymethylacrylamide, N-ethoxymethylacrylamide and Nn-butoxymethylacrylamide.
- the photosensitive component (B) refers to a monomer, oligomer or polymer having one or more unsaturated double bonds in the molecule, but when the development process is alkaline development, it contains an alkali-soluble polymer. Is preferred.
- alkali-soluble polymer examples include acrylic copolymers.
- the acrylic copolymer refers to a copolymer containing acrylic monomers such as methyl acrylate, acrylic acid, 2-ethylhexyl acrylate, ethyl methacrylate, or n-butyl acrylate as a copolymer component.
- the photopolymerization initiator (C) refers to a compound that absorbs light of a short wavelength such as ultraviolet rays and decomposes to generate radicals.
- a short wavelength such as ultraviolet rays and decomposes to generate radicals.
- a sensitizer may be added to improve the sensitivity, or the wavelength range effective for the reaction may be expanded. Examples of such a sensitizer include 2,4-diethylthioxanthone, isopropylthioxanthone, and 2,3-bis (4-diethylaminobenzal) cyclopentanone.
- the conductive filler (D) preferably contains Ag, Au, Cu, Pt, Pb, Sn, Ni, Al, W, Mo, ruthenium oxide, Cr, Ti, or indium. From the viewpoint of cost and stability, Ag is used. More preferably.
- the non-baked photosensitive conductive paste may contain an epoxy resin, but the epoxy equivalent of the epoxy resin is 200 to 500 g / equivalent because the storage stability of the coating film and the adhesion of the conductive pattern are improved. It is preferable that Epoxy equivalent means the mass of a resin containing 1 equivalent of an epoxy group, and can be determined by potentiometric titration described in JIS-K7236.
- the addition amount of the epoxy resin is preferably 1 to 100 parts by weight, and more preferably 30 to 80 parts by weight with respect to 100 parts by weight of the photosensitive component (B).
- Examples of the photosensitive component (B) having an epoxy equivalent of 200 to 500 g / equivalent include ethylene glycol-modified epoxy resin, bisphenol A type epoxy resin, and brominated epoxy resin.
- the photosensitive component (B-1) was a copolymer of ethyl acrylate (EA) / 2-ethylhexyl methacrylate (2-EHMA) / styrene (St) / acrylic acid (AA) (copolymerization ratio: 20 wt. Part / 40 parts by weight / 20 parts by weight / 15 parts by weight) and 5 parts by weight of glycidyl methacrylate (GMA) was subjected to an addition reaction, and was synthesized as follows.
- EA ethyl acrylate
- 2-EHMA 2-ethylhexyl methacrylate
- St styrene
- AA acrylic acid
- GMA glycidyl methacrylate
- Tg is the glass transition temperature of the polymer (unit: K)
- T1, T2, T3... Are the glass transition temperatures of the homopolymer of monomer 1, monomer 2, monomer 3,.
- W2, W3,... Are the weight-based copolymerization ratios of monomer 1, monomer 2, monomer 3,.
- Example 1 The developing solution processing apparatus according to the first embodiment of the present invention shown in FIG. 2 was configured, and the developing solution, that is, a 0.5% sodium carbonate aqueous solution was processed.
- the developing device (1) nozzles were installed downward at intervals of 150 mm per shower tube. A developing solution was sprayed from a nozzle onto an object to be developed (the coating film after full-line exposure described above) moving at a constant speed below the developing device (1).
- the used developer used for the development processing was collected and stored in the tank (5b).
- the tank (5b) is a chamber of the used developer tank (5) divided into two by a partition plate.
- the developer tank (5) after use was divided into two chambers, a tank (5a) and a tank (5b), each having a capacity of 150 L, and having a total capacity of 300 L.
- the developer in the developer tank (5) after use was adjusted with a heater while stirring.
- the used developer stored in the tank (5b) passes through the supply pump Y (7) and the liquid feeding means Y (8) to the decanter centrifuge (6) at a flow rate (q1) of 65 L / min. Supplied.
- the centrifuge (6) is made of SUS304 as a main constituent material, and a WC chip is attached to the tip of a screw conveyor that is heavily worn and subjected to a wear treatment.
- the clarified liquid and the residue were obtained by the treatment using the centrifugal separator (6).
- the clarified liquid was supplied to the first tank (10), and the residue was supplied to the solid content storage tank (9). did.
- the clarified liquid stored in the first tank (10) is a defoaming device, that is, a defoaming pump (12) (UPSA-1010S type; Yokota Seisakusho + vacuum pump (maximum pumping speed 300 m 3 ) at a flow rate (q2) of 68 L / min. / Hr, ultimate pressure 17 Torr), and the defoamed developer discharged after defoaming was supplied to the second tank (13) via the liquid feeding means Z (14).
- a defoaming pump (12) UPSA-1010S type; Yokota Seisakusho + vacuum pump (maximum pumping speed 300 m 3 ) at a flow rate (q2) of 68 L / min. / Hr, ultimate pressure 17 Torr
- the bubble rate of the defoamed developer discharged after defoaming was 5%. Further, when the SS concentration (JIS K0102) was measured, it was 0.03 g / L.
- the clarified liquid stored in the second tank (13) was supplied to the tank (5a) by the supply pump Z (11) at the same flow rate (q1) as 65 L / min.
- the clarified liquid overflowing from the tank (5a) was allowed to flow as an overflow flow from above the tank (5b).
- the clarified liquid stored in the tank (5a) is passed through the supply pump X (3) and the liquid feeding means X (4) as a developer that is reused at a flow rate (Q) of 60 L / min. Supplied to.
- the clarified liquid overflowed from the second tank (13) and flowed in as an overflow flow from above the first tank (10).
- the height difference between the liquid level of the clarified liquid stored in the first tank (10) and the liquid level of the clarified liquid stored in the second tank (13) was 5 cm. Moreover, it was 15 cm / s when the flow rate of the perpendicular direction of the overflow flow was measured.
- the developer in the processing apparatus is always subjected to concentration control by an automatic titrator (Electrochemical Systems 1036D) and replaced with an unused developer at a flow rate of 3 L / min in the first tank (10).
- the set concentration (0.5%) was maintained.
- the finally obtained conductive pattern has no inter-pattern residue and pattern peeling up to L / S of 20/20 ⁇ m, and the specific resistivity of the conductive pattern is 7.3 ⁇ 10 ⁇ 5 ⁇ cm, and good pattern processing is possible. It had been. In addition, the flexibility was good since no cracks or disconnection occurred after the test. The defective rate of the product was 0%.
- the residue stored in the solid content storage tank (9) contained almost no water and was able to recover 3.9 kg of silver powder (recovery rate 99%).
- Example 2 As in Example 1, the developer processing apparatus according to the first embodiment of the present invention shown in FIG. 2 was configured and the developer was processed. However, the flow rate (q2) was changed to 70 L / min.
- the clarified liquid overflowed from the second tank (13) and flowed in as an overflow flow from above the first tank (10).
- the height difference between the liquid level of the clarified liquid stored in the first tank (10) and the liquid level of the clarified liquid stored in the second tank (13) was 7 cm. Further, the vertical flow velocity of the overflow flow was measured and found to be 20 cm / s.
- the bubble ratio of the defoamed developer discharged after defoaming was 3%.
- the SS concentration was 0.01 g / L.
- the finally obtained conductive pattern has no inter-pattern residue and pattern peeling up to L / S of 20/20 ⁇ m, and the specific resistivity of the conductive pattern is 7.3 ⁇ 10 ⁇ 5 ⁇ cm, and good pattern processing is possible. It had been. In addition, the flexibility was good since no cracks or disconnection occurred after the test. The defective rate of the product was 0%.
- the residue stored in the solid content storage tank (9) contained almost no water and was able to recover 3.9 kg of silver powder (recovery rate 99%).
- Example 3 The developer processing apparatus according to the second embodiment of the present invention shown in FIG. 3 was configured, and the developer was processed in the same manner as in Examples 1 and 2.
- substrate used what affixed the polyimide film with a film thickness of 50 micrometers on the glass substrate, and changed the flow volume (q2) to 55 L / min.
- the clarified liquid overflowed from the first tank (10) and flowed in as an overflow flow from above the second tank (13).
- the height difference between the liquid level of the clarified liquid stored in the first tank (10) and the liquid level of the clarified liquid stored in the second tank (13) was 7 cm. Further, the vertical flow velocity of the overflow flow was measured and found to be 20 cm / s.
- the bubble ratio of the defoamed developer discharged after defoaming in a steady state was 10%.
- the SS concentration was 0.05 g / L.
- the finally obtained conductive pattern has no inter-pattern residue and pattern peeling up to L / S of 20/20 ⁇ m, and the specific resistivity of the conductive pattern is 7.3 ⁇ 10 ⁇ 5 ⁇ cm, and good pattern processing is possible. It had been. In addition, the flexibility was good since no cracks or disconnection occurred after the test. The defective rate of the product was 0%.
- the residue stored in the solid content storage tank (9) contained almost no water and was able to recover 3.9 kg of silver powder (recovery rate 99%).
- Example 4 The developer processing apparatus shown in FIG. 4 was constructed.
- the first tank (10) was unified, and a defoaming pump (12) and liquid feeding means Z (14) were further provided.
- the flow rate (q1) was changed to 30 L / min, and the flow rate (q2) was changed to 55 L / min.
- the bubble ratio of the defoamed developer discharged after defoaming in a steady state was 10%.
- the SS concentration was 0.1 g / L.
- the finally obtained conductive pattern has no inter-pattern residue and pattern peeling up to L / S of 20/20 ⁇ m, and the specific resistivity of the conductive pattern is 7.3 ⁇ 10 ⁇ 5 ⁇ cm, and good pattern processing is possible. It had been. In addition, the flexibility was good since no cracks or disconnection occurred after the test. The defective rate of the product was 0%.
- the residue stored in the solid content storage tank (9) contained almost no water, and 3 kg of silver powder (recovery rate: 76%) could be recovered.
- the developer processing apparatus shown in FIG. 1 was constructed. That is, the first tank and the second tank in FIG. 2 and FIG. 3 are not distinguished from each other, the first tank (10) is unified, and the defoaming pump (12) and the liquid feeding means Z (14). ) Is not provided.
- the flow rate (q1) was 30 L / min.
- piping clogging occurs when about half of the coating film after the total line exposure of 1000 sheets is developed, I was forced to maintain the piping.
- Developing device 2 Overflow flow 3: Supply pump X 4: Liquid feeding means X 5: Developer tank after use 5a, 5b: Tank (one chamber of developer tank after use) 6: Centrifuge 7: Feed pump Y 8: Liquid feeding means Y 9: Solid content storage tank 10: First tank 11: Supply pump Z 12: Defoaming pump 13: Second tank 14: Liquid feeding means Z 15: Unused developer
- the developing solution processing apparatus and processing method of the present invention can be suitably used in a development processing step of a conductive pattern forming process using a non-baked photosensitive conductive paste.
Landscapes
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Environmental & Geological Engineering (AREA)
- Dispersion Chemistry (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Coating Apparatus (AREA)
- Details Or Accessories Of Spraying Plant Or Apparatus (AREA)
Abstract
Description
(1) 現像処理後の現像液を遠心分離により、清澄液と残渣とに分離する、遠心分離機と、上記清澄液を脱泡して排出する、脱泡装置と、を備える、現像液の処理装置。
(2) 現像処理後の現像液を遠心分離して、清澄液と残渣とを得る、遠心分離機と、上記清澄液を貯留する、第1のタンクと、上記第1のタンク内の清澄液を脱泡して排出する、脱泡装置と、上記脱泡装置から排出される清澄液と、未使用の現像液と、を混合して貯留する、第2のタンクと、上記第2のタンクから溢れた清澄液を、上記第1のタンクの上方向から上記第1のタンクに供給する手段と、を備える、上記(1)記載の処理装置。
(3) 現像処理後の現像液を遠心分離して、清澄液と残渣とを得る、遠心分離機と、上記清澄液を貯留する、第1のタンクと、上記第1のタンク内の清澄液を脱泡して排出する、脱泡装置と、上記脱泡装置から排出される清澄液と、未使用の現像液と、を混合して貯留する、第2のタンクと、上記第1のタンクから溢れた清澄液を、上記第2のタンクの上方向から上記第2のタンクに供給する手段と、を備える、上記(1)記載の処理装置。
(4) 上記第1のタンクと、上記第2のタンクとが、仕切り板を挟んで隣接している、上記(2)又は(3)記載の処理装置。
(5) 上記第1のタンク又は上記第2のタンクから溢れた清澄液が、上記仕切り板を伝って流れて、他方のタンクに供給される、上記(2)~(4)のいずれかに記載の処理装置。
(6) 上記第1のタンクに貯留された清澄液の液面と、上記第2のタンクに貯留された清澄液の液面と、の高低差が、5cm以上である、上記(2)~(5)のいずれかに記載の処理装置。
(7) 上記第1のタンク又は上記第2のタンクの上方向から供給される清澄液の鉛直方向の流速が、15cm/s以上である、上記(2)~(6)のいずれかに記載の処理装置。
(8) 上記脱泡装置から排出される清澄液の気泡率が、10%以下である、上記(2)~(7)のいずれかに記載の処理装置。
(9) 現像処理後の現像液を遠心分離して、清澄液と残渣とを分離して得る、遠心分離工程と、上記清澄液を脱泡して、脱泡現像液を得る、脱泡工程と、を備える、現像液の処理方法。
(10) 上記脱泡現像液と、未使用の現像液と、を混合して混合現像液を得る、混合工程と、上記混合現像液の一部を上記現像処理に供給し、上記混合現像液の一部を、上記脱泡前の前記清澄液の上方向から上記脱泡工程に供給する、還流工程と、を備える、上記(9)に記載の処理方法。
Cr、Ti及びインジウムからなる群から選ばれる貴金属の粒子であれば、製造コストダウンの観点からより好適である。
100mLのクリーンボトルに、20gの感光性成分(B-1)、12gのN-n-ブトキシメチルアクリルアミド、4gの光重合開始剤(OXE-01;チバジャパン株式会社製)、0.6gの酸発生剤(SI-110;三新化学工業株式会社製)、10gのγ-ブチロラクトン(三菱ガス化学株式会社製)をそれぞれ入れ、あわとり練太郎(登録商標)(ARE-310;株式会社シンキー社製)で混合し、46.6gの感光性樹脂溶液A(固形分78.5重量%)を得た。8.0gの感光性樹脂溶液Aと、42.0gの銀粒子(平均粒子径2μm)とを、3本ローラー(EXAKT M-50;EXAKT社製)を用いて混練し、50gの非焼成型の感光性導電ペーストAを得た。
40gの非焼成型の感光性導電ペーストAを、スクリーン印刷でITO付きガラス基板上に塗布し、100℃の乾燥オーブンで、10分間プリベークした。次に、露光装置(PEM-6M;ユニオン光学(株)製)を用いて露光量70mJ/cm2(波長365nm換算)で全線露光をした。この全線露光後の塗布膜は、計1000枚作製した。その後、本発明の現像液処理装置を用いながら、1枚の全線露光後の塗布膜につき、1分間現像処理を行った。なお、現像処理と次回の現像処理との間には、それぞれ80秒の間隔を設けた。
現像処理後の塗布膜を超純水でリンスした後、200℃の乾燥オーブンで1時間キュアし、膜厚10μmの導電パターンを得た。導電パターンのラインアンドスペース(以下、「L/S」)パターンを光学顕微鏡により確認した。また、導電パターンの比抵抗率及び屈曲性(試験後クラックや断線等の有無)を確認した。
図2に示される、本発明の第一実施形態に係る現像液の処理装置を構成し、現像液すなわち0.5%炭酸ナトリウム水溶液を処理した。
実施例1と同様、図2に示される、本発明の第一実施形態に係る現像液の処理装置を構成し、現像液を処理した。ただし、流量(q2)を70L/minに変更した。
図3に示される、本発明の第二実施形態に係る現像液の処理装置を構成し、実施例1及び2と同様に現像液を処理した。ただし、基板は膜厚50μmのポリイミドフィルムをガラス基板に貼り付けたものを用い、流量(q2)は55L/minに変更した。
図4に示される現像液の処理装置を構成した。第1のタンク(10)に統一をし、さらに脱泡ポンプ(12)及び送液手段Z(14)を設けた構成とした。流量(q1)は30L/min、流量(q2)は55L/minに変更した。定常状態における、脱泡後に排出された脱泡現像液の気泡率は、10%であった。また、SS濃度は0.1g/Lとなった。
図1に示される現像液の処理装置を構成した。すなわち、図2及び図3における第1のタンクと第2のタンクとの区別をなくして、第1のタンク(10)に統一をし、さらに脱泡ポンプ(12)及び送液手段Z(14)を設けない構成とした。流量(q1)は、30L/minとした。
2 : オーバーフロー流
3 : 供給ポンプX
4 : 送液手段X
5 : 使用後現像液タンク
5a,5b : タンク(使用後現像液タンクの一室)
6 : 遠心分離機
7 : 供給ポンプY
8 : 送液手段Y
9 : 固形分貯留タンク
10 : 第1のタンク
11 : 供給ポンプZ
12 : 脱泡ポンプ
13 : 第2のタンク
14 : 送液手段Z
15 : 未使用の現像液
Claims (10)
- 現像処理後の現像液を遠心分離により、清澄液と残渣とに分離する、遠心分離機と、
前記清澄液を脱泡して排出する、脱泡装置と、を備える、現像液の処理装置。 - 前記遠心分離機と、
前記清澄液を貯留する、第1のタンクと、
前記第1のタンク内の清澄液を脱泡して排出する、前記脱泡装置と、
前記脱泡装置から排出される清澄液と、未使用の現像液と、を混合して貯留する、第2のタンクと、
前記第2のタンクから溢れた清澄液を、前記第1のタンクの上方向から前記第1のタンクに供給する手段と、を備える、請求項1記載の現像液の処理装置。 - 前記遠心分離機と、
前記清澄液を貯留する、第1のタンクと、
前記第1のタンク内の清澄液を脱泡して排出する、前記脱泡装置と、
前記脱泡装置から排出される清澄液と、未使用の現像液と、を混合して貯留する、第2のタンクと、
前記第1のタンクから溢れた清澄液を、前記第2のタンクの上方向から前記第2のタンクに供給する手段と、を備える、請求項1記載の現像液の処理装置。 - 前記第1のタンクと、前記第2のタンクとが、仕切り板を挟んで隣接している、請求項2又は3記載の処理装置。
- 前記第1のタンク又は前記第2のタンクから溢れた清澄液が、前記仕切り板を伝って流れて、他方のタンクに供給される、請求項2~4のいずれか一項記載の処理装置。
- 前記第1のタンクに貯留された清澄液の液面と、前記第2のタンクに貯留された清澄液の液面と、の高低差が、5cm以上である、請求項2~5のいずれか一項記載の処理装置。
- 前記第1のタンク又は前記第2のタンクの上方向から供給される清澄液の鉛直方向の流速が、15cm/s以上である、請求項2~6のいずれか一項記載の処理装置。
- 前記脱泡装置から排出される清澄液の気泡率が、10%以下である、請求項2~7のいずれか一項記載の処理装置。
- 現像処理後の現像液を遠心分離して、清澄液と残渣とを分離して得る、遠心分離工程と、
前記清澄液を脱泡して、脱泡現像液を得る、脱泡工程と、を備える、現像液の処理方法。 - 前記脱泡現像液と、未使用の現像液と、を混合して混合現像液を得る、混合工程と、
前記混合現像液の一部を前記現像処理に供給し、前記混合現像液の一部を、前記脱泡前の前記清澄液の上方向から前記脱泡工程に供給する、還流工程と、を備える、請求項9記載の処理方法。
Priority Applications (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN201380041273.4A CN104508562B (zh) | 2012-08-03 | 2013-07-02 | 显像液的处理装置和处理方法 |
KR1020157001602A KR101919331B1 (ko) | 2012-08-03 | 2013-07-02 | 현상액의 처리 장치 및 처리 방법 |
US14/412,139 US9880471B2 (en) | 2012-08-03 | 2013-07-02 | Developing solution processing device and processing method |
JP2013530451A JP6206183B2 (ja) | 2012-08-03 | 2013-07-02 | 現像液の処理装置及び処理方法 |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2012172559 | 2012-08-03 | ||
JP2012-172559 | 2012-08-03 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO2014021043A1 true WO2014021043A1 (ja) | 2014-02-06 |
Family
ID=50027732
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2013/068087 WO2014021043A1 (ja) | 2012-08-03 | 2013-07-02 | 現像液の処理装置及び処理方法 |
Country Status (6)
Country | Link |
---|---|
US (1) | US9880471B2 (ja) |
JP (1) | JP6206183B2 (ja) |
KR (1) | KR101919331B1 (ja) |
CN (1) | CN104508562B (ja) |
TW (1) | TWI590010B (ja) |
WO (1) | WO2014021043A1 (ja) |
Cited By (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019214011A (ja) * | 2018-06-12 | 2019-12-19 | 東京エレクトロン株式会社 | 脱泡装置および脱泡方法 |
Families Citing this family (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014077136A1 (ja) * | 2012-11-13 | 2014-05-22 | 東レ株式会社 | 感光性導電ペースト、積層基板、導電パターンの製造方法及び静電容量型タッチパネル |
CN106925492B (zh) * | 2017-03-20 | 2019-04-05 | 京东方科技集团股份有限公司 | 涂布液回收装置及涂布系统 |
JP6732107B2 (ja) * | 2017-03-31 | 2020-07-29 | 富士フイルム株式会社 | 処理方法および処理装置 |
Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000155426A (ja) * | 1998-11-24 | 2000-06-06 | Japan Organo Co Ltd | フォトレジスト現像廃液からの再生現像液の回収再利用装置 |
JP2003215810A (ja) * | 2002-01-22 | 2003-07-30 | Japan Organo Co Ltd | フォトレジスト現像廃液からの現像液の回収方法 |
JP2005148592A (ja) * | 2003-11-19 | 2005-06-09 | Toray Ind Inc | 無機粉末の再利用方法、およびこれを用いた感光性ペースト |
JP2005292189A (ja) * | 2004-03-31 | 2005-10-20 | Dap Technology Kk | 固形物回収装置 |
Family Cites Families (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPS5346339Y2 (ja) | 1975-12-24 | 1978-11-07 | ||
CN2188986Y (zh) | 1993-11-29 | 1995-02-08 | 刘先华 | 膨胀式消泡器 |
US7326353B2 (en) * | 2001-11-27 | 2008-02-05 | Nupro Technologies | Methods for reclaiming developing solvents |
CN102114360A (zh) | 2010-01-05 | 2011-07-06 | 东京化工机株式会社 | 泡沫处理装置 |
-
2013
- 2013-07-02 KR KR1020157001602A patent/KR101919331B1/ko active IP Right Grant
- 2013-07-02 CN CN201380041273.4A patent/CN104508562B/zh active Active
- 2013-07-02 WO PCT/JP2013/068087 patent/WO2014021043A1/ja active Application Filing
- 2013-07-02 US US14/412,139 patent/US9880471B2/en active Active
- 2013-07-02 JP JP2013530451A patent/JP6206183B2/ja active Active
- 2013-08-02 TW TW102127704A patent/TWI590010B/zh active
Patent Citations (4)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2000155426A (ja) * | 1998-11-24 | 2000-06-06 | Japan Organo Co Ltd | フォトレジスト現像廃液からの再生現像液の回収再利用装置 |
JP2003215810A (ja) * | 2002-01-22 | 2003-07-30 | Japan Organo Co Ltd | フォトレジスト現像廃液からの現像液の回収方法 |
JP2005148592A (ja) * | 2003-11-19 | 2005-06-09 | Toray Ind Inc | 無機粉末の再利用方法、およびこれを用いた感光性ペースト |
JP2005292189A (ja) * | 2004-03-31 | 2005-10-20 | Dap Technology Kk | 固形物回収装置 |
Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JP2019214011A (ja) * | 2018-06-12 | 2019-12-19 | 東京エレクトロン株式会社 | 脱泡装置および脱泡方法 |
JP7113671B2 (ja) | 2018-06-12 | 2022-08-05 | 東京エレクトロン株式会社 | 脱泡装置および脱泡方法 |
Also Published As
Publication number | Publication date |
---|---|
KR101919331B1 (ko) | 2018-11-19 |
CN104508562B (zh) | 2018-10-12 |
US9880471B2 (en) | 2018-01-30 |
CN104508562A (zh) | 2015-04-08 |
JP6206183B2 (ja) | 2017-10-04 |
TW201411300A (zh) | 2014-03-16 |
JPWO2014021043A1 (ja) | 2016-07-21 |
KR20150037860A (ko) | 2015-04-08 |
TWI590010B (zh) | 2017-07-01 |
US20150177622A1 (en) | 2015-06-25 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6206183B2 (ja) | 現像液の処理装置及び処理方法 | |
US20130230808A1 (en) | Developer, process for treating developing solution, process for producing printing plate, and filter apparatus | |
KR101898955B1 (ko) | 도전 패턴 형성 부재의 제조 방법 | |
CN1408765A (zh) | 绝缘用树脂组合物及使用该组合物的层合体 | |
KR200487199Y1 (ko) | 레지스트층의 박막화 장치 | |
TWI374490B (en) | Re-circulation method and device of chemical solution in semiconductor or display manufacturing process | |
JPH02157084A (ja) | 廃液処理の作業性等が改善される非銀塩感光材料の処理方法及び処理装置 | |
JP3207408U (ja) | レジスト層の薄膜化装置 | |
TW527320B (en) | Method for supplying hydrofluoric acid | |
JP2010113349A (ja) | 感光性樹脂組成物 | |
KR102234732B1 (ko) | 네거티브 포토레지스트용 현상액 재생 시스템 | |
JP3202621U (ja) | レジスト層の薄膜化装置 | |
JP6086287B2 (ja) | 記録材料の製造方法 | |
CN203587965U (zh) | 抗蚀剂层的薄膜化装置 | |
JP6717439B1 (ja) | 積層部材 | |
JP5239567B2 (ja) | 半導体製造用組成物溶液の製造装置 | |
CN107797395A (zh) | 一种混合废光阻清洗剂的回收方法及装置 | |
JP2012073424A (ja) | ドライフィルムレジストの薄膜化処理方法 | |
JP4461779B2 (ja) | 無機粉末の再利用方法 | |
JP3218350U (ja) | レジスト層の薄膜化装置 | |
JP3191772B2 (ja) | 現像方法、プラズマディスプレイ用部材の製造方法および現像装置 | |
JP5627404B2 (ja) | ドライフィルムレジストの薄膜化処理方法 | |
CN203825368U (zh) | 抗蚀剂层的薄膜化装置 | |
KR20180001617U (ko) | 레지스트층의 박막화 장치 | |
KR20180002477U (ko) | 레지스트층의 박막화 장치 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
ENP | Entry into the national phase |
Ref document number: 2013530451 Country of ref document: JP Kind code of ref document: A |
|
121 | Ep: the epo has been informed by wipo that ep was designated in this application |
Ref document number: 13824817 Country of ref document: EP Kind code of ref document: A1 |
|
WWE | Wipo information: entry into national phase |
Ref document number: 14412139 Country of ref document: US |
|
ENP | Entry into the national phase |
Ref document number: 20157001602 Country of ref document: KR Kind code of ref document: A |
|
NENP | Non-entry into the national phase |
Ref country code: DE |
|
122 | Ep: pct application non-entry in european phase |
Ref document number: 13824817 Country of ref document: EP Kind code of ref document: A1 |