KR101638467B1 - Composition for cleaning after jet scrubbing process - Google Patents
Composition for cleaning after jet scrubbing process Download PDFInfo
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- KR101638467B1 KR101638467B1 KR1020140135206A KR20140135206A KR101638467B1 KR 101638467 B1 KR101638467 B1 KR 101638467B1 KR 1020140135206 A KR1020140135206 A KR 1020140135206A KR 20140135206 A KR20140135206 A KR 20140135206A KR 101638467 B1 KR101638467 B1 KR 101638467B1
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- copper foil
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- jet scrubbing
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- 239000000203 mixture Substances 0.000 title claims abstract description 42
- 238000004140 cleaning Methods 0.000 title claims abstract description 38
- 238000005201 scrubbing Methods 0.000 title claims abstract description 36
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 50
- 239000011889 copper foil Substances 0.000 claims abstract description 48
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 31
- 238000004519 manufacturing process Methods 0.000 claims abstract description 15
- 230000003647 oxidation Effects 0.000 claims abstract description 12
- 238000007254 oxidation reaction Methods 0.000 claims abstract description 12
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 22
- 238000005260 corrosion Methods 0.000 claims description 17
- 238000000034 method Methods 0.000 claims description 17
- 230000007797 corrosion Effects 0.000 claims description 16
- 239000002270 dispersing agent Substances 0.000 claims description 15
- 239000003112 inhibitor Substances 0.000 claims description 13
- MUBZPKHOEPUJKR-UHFFFAOYSA-N Oxalic acid Chemical compound OC(=O)C(O)=O MUBZPKHOEPUJKR-UHFFFAOYSA-N 0.000 claims description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 12
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 claims description 12
- 239000004202 carbamide Substances 0.000 claims description 11
- 239000000843 powder Substances 0.000 claims description 9
- RGHNJXZEOKUKBD-SQOUGZDYSA-N D-gluconic acid Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C(O)=O RGHNJXZEOKUKBD-SQOUGZDYSA-N 0.000 claims description 8
- DHMQDGOQFOQNFH-UHFFFAOYSA-N Glycine Chemical compound NCC(O)=O DHMQDGOQFOQNFH-UHFFFAOYSA-N 0.000 claims description 8
- WPYMKLBDIGXBTP-UHFFFAOYSA-N benzoic acid Chemical compound OC(=O)C1=CC=CC=C1 WPYMKLBDIGXBTP-UHFFFAOYSA-N 0.000 claims description 8
- 239000003002 pH adjusting agent Substances 0.000 claims description 8
- YGSDEFSMJLZEOE-UHFFFAOYSA-N salicylic acid Chemical compound OC(=O)C1=CC=CC=C1O YGSDEFSMJLZEOE-UHFFFAOYSA-N 0.000 claims description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 8
- 239000012964 benzotriazole Substances 0.000 claims description 7
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 claims description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 5
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 claims description 4
- CDAWCLOXVUBKRW-UHFFFAOYSA-N 2-aminophenol Chemical compound NC1=CC=CC=C1O CDAWCLOXVUBKRW-UHFFFAOYSA-N 0.000 claims description 4
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 claims description 4
- 239000005711 Benzoic acid Substances 0.000 claims description 4
- RGHNJXZEOKUKBD-UHFFFAOYSA-N D-gluconic acid Natural products OCC(O)C(O)C(O)C(O)C(O)=O RGHNJXZEOKUKBD-UHFFFAOYSA-N 0.000 claims description 4
- WHUUTDBJXJRKMK-UHFFFAOYSA-N Glutamic acid Natural products OC(=O)C(N)CCC(O)=O WHUUTDBJXJRKMK-UHFFFAOYSA-N 0.000 claims description 4
- 239000004471 Glycine Substances 0.000 claims description 4
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims description 4
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 4
- CKLJMWTZIZZHCS-REOHCLBHSA-N L-aspartic acid Chemical compound OC(=O)[C@@H](N)CC(O)=O CKLJMWTZIZZHCS-REOHCLBHSA-N 0.000 claims description 4
- WHUUTDBJXJRKMK-VKHMYHEASA-N L-glutamic acid Chemical compound OC(=O)[C@@H](N)CCC(O)=O WHUUTDBJXJRKMK-VKHMYHEASA-N 0.000 claims description 4
- HNDVDQJCIGZPNO-YFKPBYRVSA-N L-histidine Chemical compound OC(=O)[C@@H](N)CC1=CN=CN1 HNDVDQJCIGZPNO-YFKPBYRVSA-N 0.000 claims description 4
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 4
- 235000003704 aspartic acid Nutrition 0.000 claims description 4
- 235000010233 benzoic acid Nutrition 0.000 claims description 4
- OQFSQFPPLPISGP-UHFFFAOYSA-N beta-carboxyaspartic acid Natural products OC(=O)C(N)C(C(O)=O)C(O)=O OQFSQFPPLPISGP-UHFFFAOYSA-N 0.000 claims description 4
- 235000018417 cysteine Nutrition 0.000 claims description 4
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 claims description 4
- 239000000174 gluconic acid Substances 0.000 claims description 4
- 235000012208 gluconic acid Nutrition 0.000 claims description 4
- 239000004220 glutamic acid Substances 0.000 claims description 4
- 235000013922 glutamic acid Nutrition 0.000 claims description 4
- 235000014304 histidine Nutrition 0.000 claims description 4
- HNDVDQJCIGZPNO-UHFFFAOYSA-N histidine Natural products OC(=O)C(N)CC1=CN=CN1 HNDVDQJCIGZPNO-UHFFFAOYSA-N 0.000 claims description 4
- 229940102253 isopropanolamine Drugs 0.000 claims description 4
- PJUIMOJAAPLTRJ-UHFFFAOYSA-N monothioglycerol Chemical compound OCC(O)CS PJUIMOJAAPLTRJ-UHFFFAOYSA-N 0.000 claims description 4
- 235000006408 oxalic acid Nutrition 0.000 claims description 4
- FJKROLUGYXJWQN-UHFFFAOYSA-N papa-hydroxy-benzoic acid Natural products OC(=O)C1=CC=C(O)C=C1 FJKROLUGYXJWQN-UHFFFAOYSA-N 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 239000010695 polyglycol Substances 0.000 claims description 4
- 229920000151 polyglycol Polymers 0.000 claims description 4
- 229960004889 salicylic acid Drugs 0.000 claims description 4
- 229940035024 thioglycerol Drugs 0.000 claims description 4
- 150000003852 triazoles Chemical class 0.000 claims description 4
- MWOOGOJBHIARFG-UHFFFAOYSA-N vanillin Chemical compound COC1=CC(C=O)=CC=C1O MWOOGOJBHIARFG-UHFFFAOYSA-N 0.000 claims description 4
- FGQOOHJZONJGDT-UHFFFAOYSA-N vanillin Natural products COC1=CC(O)=CC(C=O)=C1 FGQOOHJZONJGDT-UHFFFAOYSA-N 0.000 claims description 4
- 235000012141 vanillin Nutrition 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 claims description 3
- 238000001035 drying Methods 0.000 claims description 3
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 claims description 3
- 239000011976 maleic acid Substances 0.000 claims description 3
- ODHYIQOBTIWVRZ-UHFFFAOYSA-N n-propan-2-ylhydroxylamine Chemical compound CC(C)NO ODHYIQOBTIWVRZ-UHFFFAOYSA-N 0.000 claims description 3
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 claims description 3
- 125000003354 benzotriazolyl group Chemical group N1N=NC2=C1C=CC=C2* 0.000 claims 2
- 239000000908 ammonium hydroxide Substances 0.000 claims 1
- OMXHKVKIKSASRV-UHFFFAOYSA-N n-propylhydroxylamine Chemical compound CCCNO OMXHKVKIKSASRV-UHFFFAOYSA-N 0.000 claims 1
- 239000011347 resin Substances 0.000 claims 1
- 229920005989 resin Polymers 0.000 claims 1
- 239000002904 solvent Substances 0.000 claims 1
- 239000002245 particle Substances 0.000 description 18
- 230000008569 process Effects 0.000 description 11
- 239000010410 layer Substances 0.000 description 9
- 239000003599 detergent Substances 0.000 description 5
- 229910021642 ultra pure water Inorganic materials 0.000 description 5
- 239000012498 ultrapure water Substances 0.000 description 5
- 239000002002 slurry Substances 0.000 description 4
- 239000000758 substrate Substances 0.000 description 4
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 3
- 230000015572 biosynthetic process Effects 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 238000005520 cutting process Methods 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 238000005498 polishing Methods 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000005507 spraying Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 229910052802 copper Inorganic materials 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 230000002401 inhibitory effect Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 150000003071 polychlorinated biphenyls Chemical class 0.000 description 2
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- 239000004743 Polypropylene Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000010306 acid treatment Methods 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 1
- XXJWXESWEXIICW-UHFFFAOYSA-N diethylene glycol monoethyl ether Chemical compound CCOCCOCCO XXJWXESWEXIICW-UHFFFAOYSA-N 0.000 description 1
- 229940075557 diethylene glycol monoethyl ether Drugs 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005553 drilling Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000007730 finishing process Methods 0.000 description 1
- 230000004907 flux Effects 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 229960004592 isopropanol Drugs 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 238000003754 machining Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- -1 polypropylene Polymers 0.000 description 1
- 229920001155 polypropylene Polymers 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 230000003746 surface roughness Effects 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
Images
Classifications
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/50—Solvents
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B24—GRINDING; POLISHING
- B24C—ABRASIVE OR RELATED BLASTING WITH PARTICULATE MATERIAL
- B24C1/00—Methods for use of abrasive blasting for producing particular effects; Use of auxiliary equipment in connection with such methods
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
- C11D7/22—Organic compounds
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Mechanical Engineering (AREA)
- Detergent Compositions (AREA)
Abstract
본 발명은 PCB 제조 공정 중 내층 제조를 위한 정면 가공 공정인 제트 스크러빙 공정 후 동박 표면에 잔류된 알루미나를 효율적으로 제거하고 동박 표면의 산화를 방지할 수 있는 세정 조성물에 관한 것이다.The present invention relates to a cleaning composition capable of effectively removing alumina remaining on the surface of a copper foil after a jet scrubbing process, which is a front surface processing step for manufacturing an inner layer in a PCB manufacturing process, and preventing oxidation of the copper foil surface.
Description
본 발명은 제트 스크러빙 공정 후 사용되는 세정 조성물에 관한 것으로, 보다 상세하게는 PCB 제조 공정 중 내층 제조를 위한 정면 가공 공정인 제트 스크러빙 공정 후 동박 표면에 잔류된 알루미나를 효율적으로 제거하고, 동박 표면의 얼룩을 제거하고, 동박 표면의 산화를 방지할 수 있는 세정 조성물에 관한 것이다.
The present invention relates to a cleaning composition used after a jet scrubbing process, more particularly, to a process for efficiently removing alumina remaining on the surface of a copper foil after a jet scrubbing process, To a cleaning composition capable of removing stains and preventing oxidation of the copper foil surface.
PCB(printed circuit board)는 부품을 탑재하고, 각 부품 간을 연결하는 회로가 인쇄된 전자 부품의 일종으로, 크게 부품을 탑재하기 위한 PCB와 반도체 실장용 패키지 기판으로 나눌 수 있다.A PCB (printed circuit board) is a type of electronic component on which components are mounted and circuits for connecting the components are printed. The PCB can be divided into a PCB for mounting parts and a package substrate for semiconductor mounting.
전자 제품 중에 PCB는 가장 기초적이고도 핵심적인 부품 중 하나이며, 매우 중요성이 높다. PCB는 많은 시설투자가 요구되는 장치 산업이면서 공정이 많고 복잡한 제조공정의 특성을 갖는다.Among electronic products, PCBs are one of the most basic and essential components, and they are very important. PCBs are a device industry that requires a lot of investment in facilities, but have the features of many processes and complex manufacturing processes.
PCB의 제조공정은 다음과 같다. (1) 내층 제조를 위한 원재료 재단 및 면취/정면 가공, (2) 노광-현상-부식 과정을 통한 내층 회로의 형성, (3) 다층 기판을 제조하기 위한 적층, (4) 회로의 연결과 부품 실장 목적의 홀(hole) 가공 드릴링(Drilling), (5) 층간 회로 연결을 위한 동도금 과정, (6) 외층 회로의 형성, (7) 절연막으로서의 PSR 인쇄, (8) 마무리 공정.The PCB manufacturing process is as follows. (1) Raw material cutting and chamfering / frontal processing for inner layer manufacturing, (2) formation of inner layer circuit through exposure-development-corrosion process, (3) lamination for manufacturing multilayer board, (4) Hole drilling for mounting purpose, (5) copper plating process for interlayer circuit connection, (6) formation of outer layer circuit, (7) PSR printing as insulating film, and (8) finishing process.
상기 PCB 제조 공정 중 내층 제조를 위한 원재료 재단 및 면취/정면 가공 공정은 기판 표면의 지문이나 오염 및 이물질을 제거하고 조도를 향상시키는 공정으로, 보다 상세하게는 재단된 내층 양면 코어 상의 동박면의 방청 처리막을 제거하고, 평면 상에 일정한 조도(미세 요철)을 형성하여 부식 저항체인 LPR 잉크의 밀착력을 향상시키기 위한 공정이다. 이러한 공정에서 수세 및 건조가 제대로 이루어지지 않을 경우 동박 산화가 진행된다.In the PCB manufacturing process, raw material cutting and chamfering / frontal machining processes for inner layer production are processes for removing fingerprints, dirt and foreign substances on the surface of the substrate and improving the roughness. More specifically, Is a step for removing the treatment film and forming a uniform roughness (fine unevenness) on the plane to improve the adhesion of the LPR ink which is the corrosion resistant substance. In such a process, if washing and drying are not properly performed, copper oxidation proceeds.
상기와 같이 내층 제조를 위한 원재료 재단 및 면취/정면 가공 공정 중 기존의 내층 보드 정면 공정, 즉 buff 연마, 산처리를 통한 화학적 연마 등이 있고, 이를 대체하는 공정으로 제트 스크러빙(jet scrubbing) 공정이 있다.As described above, there is a conventional inner layer board frontal process, that is, chemical polishing through buff polishing and acid treatment, among the raw material cutting and chamfering / frontal processing for producing the inner layer, and a jet scrubbing process have.
제트 스크러빙 공정은 물과 배합된 알루미나 슬러리를 고압 분사하여 기판의 표면을 연마하는 공정으로 정면과 수세 공정을 수행하여 연성 기판의 표면 세정 및 조도 형성을 위한 표면 처리 공정이다. 보다 상세하게는 드라이 필름(dry film)과 동박 간의 밀착력을 증가시키기 위해 제트 스크러빙 공정을 통해 표면의 조도를 형성하고 이 때 제트 스크러빙시 알루미나 슬러리를 동박 표면에 강하게 분사하여 조도를 형성하게 된다.The jet scrubbing process is a surface treatment process for surface cleaning and roughness formation of a flexible substrate by performing a front surface and a washing process by polishing a surface of a substrate by spraying an alumina slurry mixed with water at a high pressure. More specifically, the surface roughness is formed through a jet scrubbing process in order to increase the adhesion between the dry film and the copper foil. At this time, when jet scrubbing, the alumina slurry is injected strongly on the surface of the copper foil to form roughness.
제트 스크러빙 공정이 완료된 후 알루미나 분말이 동박 표면에 잔류하게 되어 불량의 원인이 되고, 또한, 수계 슬러리를 사용하게 되면서 동박 표면의 산화도가 높아지기 때문에 인쇄회로기판의 저항이 높아지는 문제점이 있다. The alumina powder remains on the surface of the copper foil after the completion of the jet scrubbing process, which is a cause of defects. Moreover, since the oxidation degree of the surface of the copper foil is increased by using the aqueous slurry, the resistance of the printed circuit board is increased.
이러한 인쇄회로기판의 세정제 조성물에 관한 종래기술은 하기와 같다.The prior art concerning the detergent composition of such a printed circuit board is as follows.
한국등록특허 제1032464호에서는 연성인쇄회로기판에 잔존하는 불순물 및 플럭스를 세정하기 위한 세정제 조성물로서 이소프로필알코올(Iso-propyl Alcohol) 45~60 중량%, 디에틸렌 글리콜 모노부틸 에테르 (Diethylene glycol monobutyl Ether) 15~30 중량%, 디에틸렌 글리콜 모노에틸 에테르(Diethylene glycol monoethyl Ether) 5~20 중량%, N-메틸피롤리돈(NMP) 1~5 중량%, 톨루엔(Toluene) 1~5 중량%를 포함하는 연성인쇄회로기판용 세정제 조성물을 개시하고 있다.In Korean Patent No. 1032464, as a detergent composition for cleaning impurities and flux remaining on a flexible printed circuit board, 45 to 60% by weight of iso-propyl alcohol, diethylene glycol monobutyl ether ), 15 to 30% by weight of an ethylene glycol monoethyl ether, 5 to 20% by weight of diethylene glycol monoethyl ether, 1 to 5% by weight of N-methylpyrrolidone (NMP) and 1 to 5% And a detergent composition for a flexible printed circuit board.
그러나 상기 한국등록특허에서는 연성인쇄회로기판에 적합한 세정제 조성물을 개시하고 있을 뿐, 제트 스크러빙 공정이 완료된 후 동박 표면에 잔류하는 알루미나 분말을 제거하기 위한 세정제 조성물에 대한 언급이 없다.
However, the Korean registered patent discloses a detergent composition suitable for a flexible printed circuit board, and there is no mention of a detergent composition for removing alumina powder remaining on the surface of the copper foil after the jet scrubbing process is completed.
상술한 문제점을 해결하기 위해, 본 발명자들은 제트 스크러빙 공정이 완료된 후 동박 표면에 잔류하는 알루미나 분말을 효율적으로 제거할 수 있고, 세정 후 동박 표면의 산화를 방지할 수 있는 기술에 대해 연구를 거듭하였고 그 결과 본 발명을 완성하기에 이르렀다.In order to solve the above-described problems, the present inventors have repeatedly studied a technique capable of efficiently removing alumina powder remaining on the surface of the copper foil after the completion of the jet scrubbing process, and preventing oxidation of the surface of the copper foil after cleaning As a result, the present invention has been completed.
따라서, 본 발명의 목적은 PCB 제조 공정 중 내층 제조를 위한 정면 가공 공정인 제트 스크러빙 공정 후 동박 표면에 잔류하는 알루미나 분말을 제거하고, 동시에 동박 표면의 산화를 방지할 수 있는 세정 조성물을 제공하는데 있다.
Accordingly, an object of the present invention is to provide a cleaning composition capable of removing alumina powder remaining on the surface of a copper foil after a jet scrubbing process, which is a front surface processing step for manufacturing an inner layer in a PCB manufacturing process, and at the same time, preventing oxidation of the copper foil surface .
상기 목적을 달성하기 위하여, 본 발명은 분산제 0.01~2 중량%, 부식억제제 0.01~0.5 중량%, pH 조절제 0.1~5 중량%, 우레아 0.1~3 중량% 및 나머지 잔량의 물을 포함하는 제트 스크러빙 공정 후 사용되는 세정 조성물을 제공한다.In order to achieve the above object, the present invention provides a jet scrubbing process comprising 0.01 to 2% by weight of a dispersing agent, 0.01 to 0.5% by weight of a corrosion inhibitor, 0.1 to 5% by weight of a pH adjusting agent, 0.1 to 3% by weight of urea, To provide a cleaning composition to be used later.
본 발명의 일 실시형태에 있어서, 상기 분산제로는 폴리에틸렌 옥사이드, 폴리글리콜, 폴리에틸렌 글리콜, 구연산, 옥살산, 말레산, 살리실산, 아스파르트산, 벤조산, 글리신, 글루콘산, 글루탐산, 히스티딘, 히드록실아민, 이소프로판올아민, 이소프로필히드록실아민으로 이루어진 군으로부터 선택된 1종 또는 2종 이상의 혼합물을 사용할 수 있다.In one embodiment of the present invention, the dispersing agent is selected from the group consisting of polyethylene oxide, polyglycol, polyethylene glycol, citric acid, oxalic acid, maleic acid, salicylic acid, aspartic acid, benzoic acid, glycine, gluconic acid, glutamic acid, histidine, hydroxylamine, isopropanol Amine, isopropylhydroxylamine, and mixtures thereof.
본 발명의 일 실시형태에 있어서, 상기 부식억제제로는 아미노페놀, 벤조트리아졸, 시스테인, 티오글리세롤, 트리아졸 및 바닐린으로 이루어진 군으로부터 선택되는 것을 사용할 수 있다.In one embodiment of the present invention, the corrosion inhibitor may be selected from the group consisting of aminophenol, benzotriazole, cysteine, thioglycerol, triazole, and vanillin.
본 발명의 일 실시형태에 있어서, 상기 pH 조절제는 암모니아수, 테트라메틸암모늄 히드록시드, 수산화나트륨 및 수산화칼륨으로부터 선택되는 것을 사용하여 본 발명의 세정 조성물의 pH를 8~13로 조정하는 것이 바람직하다.In one embodiment of the present invention, the pH adjuster is preferably selected from ammonia water, tetramethylammonium hydroxide, sodium hydroxide and potassium hydroxide to adjust the pH of the cleaning composition of the present invention to 8 to 13 .
또한, 본 발명은 제트 스크러빙 공정을 수행한 후 동박 표면을 상술한 세정 조성물로 처리하여 수세 및 건조하는 단계를 수행하는 것을 포함하는 인쇄회로기판의 제조방법 및 이에 따라 제조된 인쇄회로기판을 제공한다.
In addition, the present invention provides a method for manufacturing a printed circuit board, which comprises performing a jet scrubbing step, then treating the copper foil surface with the above-described cleaning composition, washing and drying, and a printed circuit board produced thereby .
본 발명에 따른 세정 조성물은 PCB 제조 공정 중 내층 제조를 위한 정면 가공 공정인 제트 스크러빙 공정 후 동박 표면에 잔류하는 알루미나 분말을 효율적으로 제거할 뿐만 아니라 동박 표면의 얼룩을 제거하고, 동박 표면의 산화를 방지하여 불량의 원인을 제거하여 우수한 품질의 인쇄회로기판을 제조할 수 있다.
The cleaning composition according to the present invention not only efficiently removes alumina powder remaining on the surface of the copper foil after the jet scrubbing process, which is a front surface processing process for producing an inner layer during the PCB manufacturing process, but also removes stains on the surface of the copper foil, It is possible to manufacture a printed circuit board of excellent quality by eliminating the cause of defects.
도 1은 본 발명에 따른 실시예 3의 세정 조성물로 동박 표면을 세정한 후 촬영한 사진이다.
도 2는 비교예 1에서 초순수를 사용하여 동박 표면을 세정한 후 촬영한 사진이다.1 is a photograph of a copper foil surface cleaned with the cleaning composition of Example 3 according to the present invention.
Fig. 2 is a photograph taken after cleaning the surface of the copper foil using ultrapure water in Comparative Example 1. Fig.
이하 본 발명을 상세하게 설명한다.
Hereinafter, the present invention will be described in detail.
본 발명에 따른 제트 스크러빙 공정 후 사용되는 세정 조성물은 분산제, 부식억제제, pH 조절제, 우레아 및 나머지 잔량의 물을 포함한다.The cleaning composition used after the jet scrubbing process according to the present invention comprises a dispersing agent, a corrosion inhibitor, a pH adjusting agent, urea and the balance water.
본 발명에 따른 제트 스크러빙 공정 후 사용되는 세정 조성물에 분산제가 포함됨으로써 제트 스트러빙 공정 후 동박 표면에 잔류하는 알루미나 입자 표면에 분산제가 달라 붙어서 동박과 반발하여 공간을 형성하여 동박 표면과 알루미나 입자가 분리될 수 있게 한다.Since the dispersant is contained in the cleaning composition used after the jet scrubbing process according to the present invention, the dispersant sticks to the surface of the alumina particles remaining on the surface of the copper foil after the jet-stubbing process to repel the copper foil to form a space, .
보다 상세하게는, 본 발명에 따른 세정 조성물에서 우레아는 동박 표면에 달라 붙고, 분산제는 알루미나 표면에 달라 붙어 알루미나 입자와 동박 간의 입체 장해(steric hindrance)를 일으켜 동박에서 알루미나 입자가 분리될 수 있게 한다.More specifically, in the cleaning composition according to the present invention, the urea adheres to the surface of the copper foil, and the dispersant adheres to the alumina surface to cause steric hindrance between the alumina particles and the copper foil, thereby separating the alumina particles from the copper foil .
본 발명에 따른 제트 스크러빙 공정 후 사용되는 세정 조성물에 포함되는 분산제로는 폴리에틸렌 옥사이드, 폴리글리콜, 폴리에틸렌 글리콜, 구연산, 옥살산, 말레산, 살리실산, 아스파르트산, 벤조산, 글리신, 글루콘산, 글루탐산, 히스티딘, 히드록실아민, 이소프로판올아민, 이소프로필히드록실아민으로 이루어진 군으로부터 선택된 1종 또는 2종 이상의 혼합물을 사용할 수 있다.The dispersing agent contained in the cleaning composition used after the jet scrubbing step according to the present invention may be selected from the group consisting of polyethylene oxide, polyglycol, polyethyleneglycol, citric acid, oxalic acid, maleic acid, salicylic acid, aspartic acid, benzoic acid, glycine, gluconic acid, glutamic acid, histidine, A mixture of one or more selected from the group consisting of hydroxylamine, isopropanolamine and isopropylhydroxylamine can be used.
본 발명에 따른 제트 스크러빙 공정 후 사용되는 세정 조성물에 분산제는 0.01~2 중량%로 포함되는 것이 바람직하다.It is preferable that the dispersant is included in the cleaning composition used after the jet scrubbing process according to the present invention in an amount of 0.01 to 2% by weight.
본 발명에 따른 제트 스크러빙 공정 후 사용되는 세정 조성물에 분산제가 0.01 중량% 미만을 포함되는 경우 충분히 알루미나를 감싸지 못해 알루미나 입자를 동박으로부터 분리하지 못하는 문제점이 발생될 수 있으며, 2 중량%를 초과하여 포함되는 경우 오히려 알루미나 입자 간의 응집 등을 발생시켜 입자를 제거하는데 어려움이 발생될 수 있다.If the amount of the dispersing agent is less than 0.01% by weight in the cleaning composition used after the jet scrubbing process according to the present invention, the alumina particles can not be sufficiently wrapped and the alumina particles can not be separated from the copper foil. It may be difficult to remove the particles due to agglomeration among the alumina particles.
본 발명에 따른 제트 스크러빙 공정 후 사용되는 세정 조성물에 동박 표면의 산화를 억제하기 위한 부식억제제가 포함되며, 부식억제제는 아미노페놀, 벤조트리아졸, 시스테인, 티오글리세롤, 트리아졸 및 바닐린으로 이루어진 군으로부터 선택된다.The cleaning composition used after the jet scrubbing process according to the present invention comprises a corrosion inhibitor for inhibiting the oxidation of the copper foil surface, wherein the corrosion inhibitor is selected from the group consisting of aminophenol, benzotriazole, cysteine, thioglycerol, triazole and vanillin Is selected.
본 발명에 따른 제트 스크러빙 공정 후 사용되는 세정 조성물에 포함되는 부식억제제는 0.01~0.5 중량%로 포함되는 것이 바람직하다.The corrosion inhibitor contained in the cleaning composition used after the jet scrubbing process according to the present invention is preferably contained in an amount of 0.01 to 0.5% by weight.
본 발명에 따른 제트 스크러빙 공정 후 사용되는 세정 조성물에 부식억제제가 0.01 중량% 미만을 포함되는 경우 양이 충분치 않아서 세정시 발생할 수 있는 동박의 부식을 방지하지 못하는 문제점이 발생될 수 있으며, 0.5 중량%를 초과하여 포함되는 경우 상기 분산제 및 우레아의 역할을 방해하는 문제점이 발생될 수 있다.If the amount of the corrosion inhibitor is less than 0.01% by weight in the cleaning composition used after the jet scrubbing process according to the present invention, the amount of the corrosion inhibitor may not be enough to prevent the corrosion of the copper foil, , There may arise a problem that the function of the dispersing agent and the urea is disturbed.
본 발명의 일 실시형태에 있어서, 상기 부식억제제로서 벤조트리아졸을 사용하는 것이 부식 억제 효과에 있어서 바람직하다.In one embodiment of the present invention, it is preferable to use benzotriazole as the corrosion inhibitor for the corrosion inhibiting effect.
본 발명에 따른 제트 스크러빙 공정 후 사용되는 세정 조성물은 암모니아수, 테트라메틸암모늄 히드록시드, 수산화나트륨 및 수산화칼륨으로부터 선택되는 pH 조절제를 사용하여 pH 8~13로 조정되는 것이 바람직하다.The cleaning composition used after the jet scrubbing process according to the present invention is preferably adjusted to a pH of 8 to 13 by using a pH adjusting agent selected from ammonia water, tetramethylammonium hydroxide, sodium hydroxide and potassium hydroxide.
본 발명에 따른 제트 스크러빙 공정 후 사용되는 세정 조성물의 pH가 8 미만인 경우 산에 의해 동박이 에칭될 수 있는 문제점이 있으며, pH가 13 초과인 경우 분산제 및 우레아가 제 기능을 발휘할 수 없는 문제점이 발생될 수 있다.When the pH of the cleaning composition used after the jet scrubbing process according to the present invention is less than 8, the copper foil can be etched by the acid, and when the pH is more than 13, the dispersant and urea can not exert their functions .
본 발명에 따른 제트 스크러빙 공정 후 사용되는 세정 조성물은 우레아 0.1~3 중량%를 포함한다.The cleaning composition used after the jet scrubbing process according to the present invention comprises from 0.1 to 3% by weight of urea.
본 발명에 따른 세정 조성물에서 우레아는 동박에 작용하여 동박 표면에 붙은 알루미나 입자가 잘 떨어져 나갈 수 있도록 도우며, 동박 표면의 얼룩을 잘 제거될 수 있게 하며, 또한 pH 조절에도 도움을 준다.In the cleaning composition according to the present invention, the urea acts on the copper foil to help the alumina particles adhered to the surface of the copper foil to be easily separated from the copper foil.
본 발명에 따른 제트 스크러빙 공정 후 사용되는 세정 조성물에 우레아가 0.1 중량% 미만으로 포함되는 경우 동박에 충분히 작용하지 못해 알루미나 입자가 잘 떨어져 나가게 하지 못하며 동박 위의 얼룩 제거 효과도 미미할 수 있으며, 우레아가 3 중량%를 초과하여 포함되는 경우 pH 조절이 용이 하지 않으며, 알루미나 입자에 작용하는 분산제의 작용을 방해 하여 오히려 입자를 세정하지 못하는 문제점이 발생될 수 있다. When the cleaning composition used after the jet scrubbing process according to the present invention contains less than 0.1% by weight of urea, the alumina particles can not be sufficiently removed due to insufficient action on the copper foil, and the effect of removing stains on the copper foil may be insignificant. If it is contained in an amount of more than 3% by weight, the pH is not easily controlled and the action of the dispersant acting on the alumina particles may be disturbed and the particles may not be cleaned.
상술한 본 발명에 따른 제트 스크러빙 공정 후 사용되는 세정 조성물은 인쇄회로기판의 내층 제조를 위한 제트 스크러빙 정면 가공 공정 후 수세 처리에 사용됨으로써, 상술한 바와 같이 제트 스크러빙 공정 후 동박 표면에 잔류된 알루미나 입자를 효율적으로 제거하고 동박 표면의 산화를 방지할 수 있다.
The cleaning composition used after the jet scrubbing process according to the present invention is used in the water treatment after the jet scrubbing front surface processing process for the production of the inner layer of the printed circuit board so that the alumina particles remaining on the surface of the copper foil after the jet scrubbing process Can be efficiently removed and the oxidation of the surface of the copper foil can be prevented.
이하, 본 발명의 이해를 돕기 위하여 바람직한 실시예를 제시하나, 하기 실시예는 본 발명을 예시하는 것일 뿐 본 발명의 범주 및 기술사상 범위 내에서 다양한 변경 및 수정이 가능함은 당업자에게 있어서 명백한 것이며, 이러한 변형 및 수정이 첨부된 특허청구범위에 속하는 것도 당연한 것이다.
It will be apparent to those skilled in the art that various modifications and variations can be made in the present invention without departing from the spirit or scope of the present invention. Such variations and modifications are intended to be within the scope of the appended claims.
실시예 1 내지 9: 세정 조성물의 제조Examples 1 to 9: Preparation of cleaning composition
젯트 스크러빙 정면 후 알루미나 입자가 표면에 남아 불량을 발생하는 것을 최소화하기 위해 세정 조성물을 표 1의 조성으로 하기와 같이 제조하였다. 10L 폴리플로필렌 재질의 용기에 표 1의 나타난 함량으로 초순수, 분산제, 부식억제제, 우레아를 첨가한 후 믹서교반기를 이용하여 100rpm 속도로 30분간 교반하였다. 교반하면서 TMAH(TetraMethylAmmonium Hydroxide) 1N용액을 이용하여 pH를 표 1과 같이 조절하였다. 이렇게 준비된 세정 조성물을 이용하여 젯트 스크러빙 정면 후 동박 표면을 세정하여 알루미나 입자 제거 정도를 광학현미경을 이용하여 관찰하였고 그 결과를 표 1에 나타내었다.In order to minimize the occurrence of defects caused by alumina particles remaining on the surface after the jet scrubbing front surface, the cleaning composition was prepared as shown in Table 1 as follows. Ultrapure water, a dispersant, a corrosion inhibitor and urea were added to a container made of 10 L polypropylene as shown in Table 1, and the mixture was stirred at a speed of 100 rpm for 30 minutes using a mixer stirrer. The pH was adjusted as shown in Table 1 while stirring with a 1N solution of TMAH (TetraMethlymmonium Hydroxide). The surface of the copper foil after the jet scrubbing front surface was cleaned using the cleaning composition thus prepared, and the degree of alumina particle removal was observed using an optical microscope. The results are shown in Table 1.
표면관찰 결과는 깨끗한 표면을 ‘상’, 알루미나 입자가 한 두 개 관찰되거나 표면의 얼룩이 관찰되는 경우 ‘중’, 알루미나 입자가 빈번히 관찰되는 경우 ‘하’로 표현하였다.Surface observations were expressed as 'phase' on a clean surface, 'middle' if one or two alumina particles were observed or surface blotches were observed, and 'bottom' if alumina particles were frequently observed.
실시예 1의 세정 조성물을 사용하여 동박 표면을 세정한 후 동박 표면을 촬영한 사진을 도 1에 나타내었다.Fig. 1 shows a photograph of the surface of the copper foil after cleaning the surface of the copper foil using the cleaning composition of Example 1. Fig.
비교예 1: 초순수를 사용한 동박 표면의 세정Comparative Example 1: Cleaning of copper foil surface using ultrapure water
15 cm X 15 cm 의 CCL을 젯트 스크러빙 장비에서 10wt% 600 mesh 알루미나 수분산 슬러리를 노즐을 이용하여 분사하여 정면하였으며 공정 조건은 분사 압력 1.5 kg/cm2, 컨베이어 이동 속도는 1.5m/min 이었다. 노즐 분사 후 초순수를 분사하여 3분간 세정하였으며, 70 ℃에서, 30분간 건조하였고 동박 표면 사진을 촬영하여 도 1에 나타내었다.15 cm X 15 cm CCL was sprayed with a 10 wt% 600 mesh alumina water dispersion slurry using a nozzle in a jet scrubber. The spraying pressure was 1.5 kg / cm 2 and the moving speed of the conveyor was 1.5 m / min. After spraying the nozzle, ultra pure water was sprayed for 3 minutes, and dried at 70 ° C for 30 minutes. Photographs of the surface of the copper foil were shown in FIG.
[표 1][Table 1]
표 1 및 도 1과 도 2를 참조하면, 비교예 1에 따라 초순수로만 세정한 경우 동박 표면에 알루미나 입자가 빈번하게 관찰되었으나 본 발명에 따른 실시예 1 내지 9의 세정 조성물로 세정한 경우 동박 표면에서 알루미나 입자가 깨끗하게 제거된 것을 알 수 있다.Referring to Table 1 and FIG. 1 and FIG. 2, alumina particles were frequently observed on the surface of the copper foil when it was cleaned only with ultra-pure water according to Comparative Example 1, but when washed with the cleaning composition of Examples 1 to 9 according to the present invention, It can be seen that the alumina particles are cleanly removed.
Claims (13)
제트 스크러빙 공정 후 동박 표면에 잔류하는 알루미나 분말 제거 및 동박 표면의 산화 방지용 세정 조성물.
Wherein the solvent is selected from the group consisting of polyethylene oxide, polyglycol, polyethylene glycol, citric acid, oxalic acid, salicylic acid, aspartic acid, benzoic acid, glycine, gluconic acid, glutamic acid, histidine, hydroxylamine, isopropanolamine, isopropylhydroxylamine 0.01 to 0.5% by weight of a corrosion inhibitor selected from the group consisting of aminophenol, benzotriazole, cysteine, thioglycerol, triazole and vanillin, 0.01 to 2% by weight of a dispersant which is a mixture of two or more species, 0.1 to 5% by weight of a pH adjusting agent selected from ammonium hydroxide, sodium hydroxide and potassium hydroxide, 0.1 to 3% by weight of urea,
A cleaning composition for removing alumina powder remaining on the surface of a copper foil after a jet scrubbing process and for preventing oxidation of the surface of the copper foil.
상기 부식억제제는 벤조트리아졸인 것을 특징으로 하는 제트 스크러빙 공정 후 동박 표면에 잔류하는 알루미나 분말 제거 및 동박 표면의 산화 방지용 세정 조성물.
The method according to claim 1,
Wherein the corrosion inhibitor is benzotriazole after removal of alumina powder remaining on the surface of the copper foil after the jet scrubbing step and to prevent oxidation of the surface of the copper foil.
상기 pH 조절제를 사용하여 pH 8~13로 조정되는 것을 특징으로 하는 제트 스크러빙 공정 후 동박 표면에 잔류하는 알루미나 분말 제거 및 동박 표면의 산화 방지용 세정 조성물.
The method according to claim 1,
Wherein the pH adjuster is used to adjust the pH to 8 to 13. The cleaning composition for removing alumina powder remaining on the surface of the copper foil after the jet scrubbing process and for preventing oxidation of the surface of the copper foil.
제트 스크러빙 공정을 수행한 후 동박 표면을 폴리에틸렌 옥사이드, 폴리글리콜, 폴리에틸렌 글리콜, 구연산, 옥살산, 말레산, 살리실산, 아스파르트산, 벤조산, 글리신, 글루콘산, 글루탐산, 히스티딘, 히드록실아민, 이소프로판올아민, 이소프로필히드록실아민으로 이루어진 군으로부터 선택된 1종 또는 2종 이상의 혼합물인 분산제 0.01~2 중량%, 아미노페놀, 벤조트리아졸, 시스테인, 티오글리세롤, 트리아졸 및 바닐린으로 이루어진 군으로부터 선택된 어느 하나인 부식억제제 0.01~0.5 중량%, 암모니아수, 테트라메틸암모늄 히드록시드, 수산화나트륨 및 수산화칼륨으로부터 선택된 어느 하나인 pH 조절제 0.1~5 중량%, 우레아 0.1~3 중량% 및 나머지 잔량의 물을 포함하는 세정 조성물을 처리하여 동박 표면에 잔류하는 알루미나 분말을 제거하고 동박 표면의 산화를 방지하는 단계; 및 수세 및 건조하는 단계를 수행하는 것을 포함하는 인쇄회로기판의 제조방법.
A method of manufacturing a printed circuit board,
After performing the jet scrubbing process, the surface of the copper foil is coated with a resin such as polyethylene oxide, polyglycol, polyethylene glycol, citric acid, oxalic acid, maleic acid, salicylic acid, aspartic acid, benzoic acid, glycine, gluconic acid, glutamic acid, histidine, hydroxylamine, isopropanolamine, 0.01 to 2% by weight of a dispersing agent which is a mixture of one or more selected from the group consisting of propylhydroxylamine, aminophenol, benzotriazole, cysteine, thioglycerol, triazole and vanillin. 0.01 to 0.5% by weight of water, 0.1 to 5% by weight of a pH adjusting agent selected from ammonia water, tetramethylammonium hydroxide, sodium hydroxide and potassium hydroxide, 0.1 to 3% by weight of urea, To remove the alumina powder remaining on the surface of the copper foil, Preventing oxidation; And performing a washing and drying step.
상기 부식억제제는 벤조트리아졸인 것을 특징으로 하는 인쇄회로기판의 제조방법.
8. The method of claim 7,
Wherein the corrosion inhibitor is benzotriazole. ≪ RTI ID = 0.0 > 11. < / RTI >
상기 pH 조절제를 사용하여 pH 8~13로 조정되는 것을 특징으로 하는 인쇄회로기판의 제조방법.
8. The method of claim 7,
And adjusting the pH to 8 to 13 using the pH adjusting agent.
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