KR20160017477A - Cleaning composition - Google Patents
Cleaning composition Download PDFInfo
- Publication number
- KR20160017477A KR20160017477A KR1020140101059A KR20140101059A KR20160017477A KR 20160017477 A KR20160017477 A KR 20160017477A KR 1020140101059 A KR1020140101059 A KR 1020140101059A KR 20140101059 A KR20140101059 A KR 20140101059A KR 20160017477 A KR20160017477 A KR 20160017477A
- Authority
- KR
- South Korea
- Prior art keywords
- weight
- insulating film
- organic insulating
- transparent resin
- hydroxide
- Prior art date
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- 239000000203 mixture Substances 0.000 title claims abstract description 48
- 238000004140 cleaning Methods 0.000 title abstract description 14
- 239000011347 resin Substances 0.000 claims abstract description 38
- 229920005989 resin Polymers 0.000 claims abstract description 38
- -1 quaternary ammonium salt compound Chemical class 0.000 claims abstract description 29
- 239000002798 polar solvent Substances 0.000 claims abstract description 14
- 125000005233 alkylalcohol group Chemical group 0.000 claims abstract description 13
- AVXURJPOCDRRFD-UHFFFAOYSA-N Hydroxylamine Chemical compound ON AVXURJPOCDRRFD-UHFFFAOYSA-N 0.000 claims abstract description 12
- 150000007529 inorganic bases Chemical class 0.000 claims abstract description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 11
- 150000001875 compounds Chemical class 0.000 claims abstract description 10
- 150000003839 salts Chemical class 0.000 claims abstract description 10
- 238000009835 boiling Methods 0.000 claims abstract description 8
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 3
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 67
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 claims description 48
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 24
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- 238000000034 method Methods 0.000 claims description 12
- 239000012459 cleaning agent Substances 0.000 claims description 10
- 239000003599 detergent Substances 0.000 claims description 9
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical group CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 8
- 239000004721 Polyphenylene oxide Substances 0.000 claims description 8
- 150000001412 amines Chemical class 0.000 claims description 8
- 229920000570 polyether Polymers 0.000 claims description 8
- VDZOOKBUILJEDG-UHFFFAOYSA-M tetrabutylammonium hydroxide Chemical compound [OH-].CCCC[N+](CCCC)(CCCC)CCCC VDZOOKBUILJEDG-UHFFFAOYSA-M 0.000 claims description 8
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 claims description 7
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 claims description 7
- QPRQEDXDYOZYLA-UHFFFAOYSA-N 2-methylbutan-1-ol Chemical compound CCC(C)CO QPRQEDXDYOZYLA-UHFFFAOYSA-N 0.000 claims description 6
- BTANRVKWQNVYAZ-UHFFFAOYSA-N butan-2-ol Chemical compound CCC(C)O BTANRVKWQNVYAZ-UHFFFAOYSA-N 0.000 claims description 6
- BWHMMNNQKKPAPP-UHFFFAOYSA-L potassium carbonate Chemical compound [K+].[K+].[O-]C([O-])=O BWHMMNNQKKPAPP-UHFFFAOYSA-L 0.000 claims description 6
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims description 5
- WFRBDWRZVBPBDO-UHFFFAOYSA-N 2-methyl-2-pentanol Chemical compound CCCC(C)(C)O WFRBDWRZVBPBDO-UHFFFAOYSA-N 0.000 claims description 4
- AMQJEAYHLZJPGS-UHFFFAOYSA-N N-Pentanol Chemical compound CCCCCO AMQJEAYHLZJPGS-UHFFFAOYSA-N 0.000 claims description 4
- QNVRIHYSUZMSGM-UHFFFAOYSA-N hexan-2-ol Chemical compound CCCCC(C)O QNVRIHYSUZMSGM-UHFFFAOYSA-N 0.000 claims description 4
- PHTQWCKDNZKARW-UHFFFAOYSA-N isoamylol Chemical compound CC(C)CCO PHTQWCKDNZKARW-UHFFFAOYSA-N 0.000 claims description 4
- ZXEKIIBDNHEJCQ-UHFFFAOYSA-N isobutanol Chemical compound CC(C)CO ZXEKIIBDNHEJCQ-UHFFFAOYSA-N 0.000 claims description 4
- JYVLIDXNZAXMDK-UHFFFAOYSA-N pentan-2-ol Chemical compound CCCC(C)O JYVLIDXNZAXMDK-UHFFFAOYSA-N 0.000 claims description 4
- FGIUAXJPYTZDNR-UHFFFAOYSA-N potassium nitrate Chemical compound [K+].[O-][N+]([O-])=O FGIUAXJPYTZDNR-UHFFFAOYSA-N 0.000 claims description 4
- VWDWKYIASSYTQR-UHFFFAOYSA-N sodium nitrate Chemical compound [Na+].[O-][N+]([O-])=O VWDWKYIASSYTQR-UHFFFAOYSA-N 0.000 claims description 4
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 claims description 4
- YIWUKEYIRIRTPP-UHFFFAOYSA-N 2-ethylhexan-1-ol Chemical compound CCCCC(CC)CO YIWUKEYIRIRTPP-UHFFFAOYSA-N 0.000 claims description 3
- JCEZOHLWDIONSP-UHFFFAOYSA-N 3-[2-[2-(3-aminopropoxy)ethoxy]ethoxy]propan-1-amine Chemical compound NCCCOCCOCCOCCCN JCEZOHLWDIONSP-UHFFFAOYSA-N 0.000 claims description 3
- HPXRVTGHNJAIIH-UHFFFAOYSA-N cyclohexanol Chemical compound OC1CCCCC1 HPXRVTGHNJAIIH-UHFFFAOYSA-N 0.000 claims description 3
- 229910000027 potassium carbonate Inorganic materials 0.000 claims description 3
- 229910000029 sodium carbonate Inorganic materials 0.000 claims description 3
- BQCCJWMQESHLIT-UHFFFAOYSA-N 1-propylsulfinylpropane Chemical compound CCCS(=O)CCC BQCCJWMQESHLIT-UHFFFAOYSA-N 0.000 claims description 2
- QNVRIHYSUZMSGM-LURJTMIESA-N 2-Hexanol Natural products CCCC[C@H](C)O QNVRIHYSUZMSGM-LURJTMIESA-N 0.000 claims description 2
- 229920001174 Diethylhydroxylamine Polymers 0.000 claims description 2
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 claims description 2
- 239000004111 Potassium silicate Substances 0.000 claims description 2
- 239000004115 Sodium Silicate Substances 0.000 claims description 2
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 claims description 2
- UIIMBOGNXHQVGW-DEQYMQKBSA-M Sodium bicarbonate-14C Chemical compound [Na+].O[14C]([O-])=O UIIMBOGNXHQVGW-DEQYMQKBSA-M 0.000 claims description 2
- 125000003545 alkoxy group Chemical group 0.000 claims description 2
- CCAFPWNGIUBUSD-UHFFFAOYSA-N diethyl sulfoxide Chemical compound CCS(=O)CC CCAFPWNGIUBUSD-UHFFFAOYSA-N 0.000 claims description 2
- FVCOIAYSJZGECG-UHFFFAOYSA-N diethylhydroxylamine Chemical compound CCN(O)CC FVCOIAYSJZGECG-UHFFFAOYSA-N 0.000 claims description 2
- IWBOPFCKHIJFMS-UHFFFAOYSA-N ethylene glycol bis(2-aminoethyl) ether Chemical compound NCCOCCOCCN IWBOPFCKHIJFMS-UHFFFAOYSA-N 0.000 claims description 2
- VMESOKCXSYNAKD-UHFFFAOYSA-N n,n-dimethylhydroxylamine Chemical compound CN(C)O VMESOKCXSYNAKD-UHFFFAOYSA-N 0.000 claims description 2
- QQZOPKMRPOGIEB-UHFFFAOYSA-N n-butyl methyl ketone Natural products CCCCC(C)=O QQZOPKMRPOGIEB-UHFFFAOYSA-N 0.000 claims description 2
- 235000011181 potassium carbonates Nutrition 0.000 claims description 2
- 235000011118 potassium hydroxide Nutrition 0.000 claims description 2
- 239000004323 potassium nitrate Substances 0.000 claims description 2
- 235000010333 potassium nitrate Nutrition 0.000 claims description 2
- NNHHDJVEYQHLHG-UHFFFAOYSA-N potassium silicate Chemical compound [K+].[K+].[O-][Si]([O-])=O NNHHDJVEYQHLHG-UHFFFAOYSA-N 0.000 claims description 2
- 229910052913 potassium silicate Inorganic materials 0.000 claims description 2
- 235000019353 potassium silicate Nutrition 0.000 claims description 2
- OTYBMLCTZGSZBG-UHFFFAOYSA-L potassium sulfate Chemical compound [K+].[K+].[O-]S([O-])(=O)=O OTYBMLCTZGSZBG-UHFFFAOYSA-L 0.000 claims description 2
- 229910052939 potassium sulfate Inorganic materials 0.000 claims description 2
- 235000011151 potassium sulphates Nutrition 0.000 claims description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 claims description 2
- 235000017550 sodium carbonate Nutrition 0.000 claims description 2
- 235000011121 sodium hydroxide Nutrition 0.000 claims description 2
- 239000004317 sodium nitrate Substances 0.000 claims description 2
- 235000010344 sodium nitrate Nutrition 0.000 claims description 2
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052911 sodium silicate Inorganic materials 0.000 claims description 2
- 235000019794 sodium silicate Nutrition 0.000 claims description 2
- 229910052938 sodium sulfate Inorganic materials 0.000 claims description 2
- 235000011152 sodium sulphate Nutrition 0.000 claims description 2
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 claims description 2
- 239000000126 substance Substances 0.000 abstract description 5
- 125000006274 (C1-C3)alkoxy group Chemical group 0.000 abstract 1
- 230000000052 comparative effect Effects 0.000 description 25
- 239000000758 substrate Substances 0.000 description 24
- 230000000694 effects Effects 0.000 description 10
- WRMNZCZEMHIOCP-UHFFFAOYSA-N 2-phenylethanol Chemical compound OCCC1=CC=CC=C1 WRMNZCZEMHIOCP-UHFFFAOYSA-N 0.000 description 4
- 239000011248 coating agent Substances 0.000 description 4
- 238000000576 coating method Methods 0.000 description 4
- 150000004985 diamines Chemical class 0.000 description 4
- 239000007788 liquid Substances 0.000 description 4
- 229920000642 polymer Polymers 0.000 description 4
- 229920001451 polypropylene glycol Polymers 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- 239000003513 alkali Substances 0.000 description 3
- 239000000908 ammonium hydroxide Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 238000011156 evaluation Methods 0.000 description 3
- 229910001854 alkali hydroxide Inorganic materials 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 239000002585 base Substances 0.000 description 2
- 238000004132 cross linking Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 230000002950 deficient Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 230000018109 developmental process Effects 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- 238000004519 manufacturing process Methods 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 238000000059 patterning Methods 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 125000001453 quaternary ammonium group Chemical group 0.000 description 2
- ZFPGARUNNKGOBB-UHFFFAOYSA-N 1-Ethyl-2-pyrrolidinone Chemical compound CCN1CCCC1=O ZFPGARUNNKGOBB-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- 239000004925 Acrylic resin Substances 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004593 Epoxy Substances 0.000 description 1
- 229910052783 alkali metal Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 235000019646 color tone Nutrition 0.000 description 1
- 230000000295 complement effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 125000003700 epoxy group Chemical group 0.000 description 1
- 239000003822 epoxy resin Substances 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000004299 exfoliation Methods 0.000 description 1
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000178 monomer Substances 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 230000007903 penetration ability Effects 0.000 description 1
- 239000012466 permeate Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000647 polyepoxide Polymers 0.000 description 1
- 239000002952 polymeric resin Substances 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000002244 precipitate Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002522 swelling effect Effects 0.000 description 1
- 229920003002 synthetic resin Polymers 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/044—Hydroxides or bases
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/02—Inorganic compounds ; Elemental compounds
- C11D3/04—Water-soluble compounds
- C11D3/10—Carbonates ; Bicarbonates
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/26—Organic compounds containing nitrogen
- C11D3/30—Amines; Substituted amines ; Quaternized amines
-
- 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
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/43—Solvents
-
- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
- C11D2111/10—Objects to be cleaned
- C11D2111/14—Hard surfaces
- C11D2111/22—Electronic devices, e.g. PCBs or semiconductors
Landscapes
- Chemical & Material Sciences (AREA)
- Wood Science & Technology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Detergent Compositions (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
Description
본 발명은 칼라 레지스트, 유기 절연막 및 투명레진 제거용 세정제 조성물에 관한 것이다.The present invention relates to a color resist, an organic insulating film, and a cleaning agent composition for removing a transparent resin.
칼라필터(color filter)는 상보성 금속 산화막 반도체(complementary metal oxide semiconductor, CMOS) 또는 전하결합소자(charge coupled device, CCD)와 같은 이미지 센서의 컬러 촬영 장치 내에 내장되어 실제로 컬러 화상을 얻는데 이용될 수 있으며, 이 밖에도 촬영소자, 플라즈마 디스플레이 패널(PDP), 액정표시장치(LCD), 전계방출 디스플레이(FEL) 및 발광 디스플레이(LED) 등에 널리 이용되는 것으로, 그 응용범위가 급속히 확대되고 있다. 특히, 최근에는 LCD의 용도가 더욱 확대되고 있으며, 이에 따라 LCD의 색조를 재현하는데 있어서 컬러필터는 가장 중요한 부품 중의 하나로 인식되고 있다.A color filter can be embedded in a color imaging device of an image sensor, such as a complementary metal oxide semiconductor (CMOS) or a charge coupled device (CCD), and can be used to actually obtain a color image (PDP), a liquid crystal display (LCD), a field emission display (FEL), and a light emitting display (LED), and the application range thereof is rapidly expanding. Particularly, in recent years, the use of LCDs has been further expanded, and accordingly, color filters have been recognized as one of the most important components in reproducing color tones of LCDs.
한편, 레지스트는 크게 포지티브형 레지스트와 네거티브형 레지스트로 나눌 수 있는데, 제거가 보다 용이하여 유기용제 기반의 박리제에 의해 40 내지 50℃의 온도 조건에서 1분 이내에 제거되는 포지티브형 레지스트와는 달리, 컬러 레지스트는 경화도가 높고 열처리에 의해 단단해져 박리 제거가 어려운 네거티브형 레지스트의 특성을 갖고 있다. 이에 따라 컬러 레지스트의 제거를 위해서는 70℃ 이상의 온도 조건에서 5분 이상의 시간이 소요되므로, 보다 강력한 박리 성능이 요구된다. 현재 평판표시장치 제조 공정에서, 칼라필터의 코팅을 위해 유기계 절연막이 사용되고 있어, 칼라필터의 RGB가 코팅불량이 발생하거나 유기계 절연막의 코팅 불량이 발생될 경우, 칼라필터를 폐기하는 대신 코팅 불량면을 제거하는 공정을 거치면 공정의 수율 향상 및 원가 절감의 효과가 있기 때문에 칼라필터의 재사용을 위해 RGB 칼라레지스트 및 유기계 절연막을 동시에 제거할 수 있는 세정제 조성물이 요구되고 있다. 또한 OLED 패널의 광효율을 올리기 위한 4-픽셀구조를 이루는 RGBW의 투명 레지스트의 경우 컬러 레지스트 또는 유기 절연막 보다 높은 경화도 뿐만 아니라 열안정성, 화학적 안정성이 높은 수지를 사용함으로써 제거가 더 어려운 문제가 있다. 따라서, 칼라필터 제조 공정 중 발생하는 불량 칼라필터의 재사용을 위해서는 칼라 레지스트, 유기 절연막 및 투명레진 모두를 효과적으로 제거할 수 있는 세정제 조성물이 필요하다.
On the other hand, the resist can be largely divided into a positive type resist and a negative type resist. Unlike the positive type resist, which is easily removed and removed within one minute at a temperature condition of 40 to 50 DEG C by an organic solvent- Resists have properties of a negative type resist which has a high degree of curing and is hardened by heat treatment and is difficult to peel off. Accordingly, in order to remove the color resist, a time of not less than 5 minutes is required under a temperature condition of 70 占 폚 or more, so that stronger peeling performance is required. In the current flat panel display manufacturing process, when an organic insulating film is used for the coating of a color filter, if RGB coating of the color filter causes coating failure or coating failure of the organic insulating film, the color filter is discarded There is a need for a cleaning composition capable of simultaneously removing the RGB color resist and the organic insulating film for reuse of the color filter because the process yield is improved and the cost is reduced. In addition, in the case of RGBW transparent resist having a four-pixel structure for increasing the light efficiency of an OLED panel, there is a problem that it is more difficult to remove by using a resin having high thermal stability and chemical stability as well as a higher degree of curing than a color resist or an organic insulating film. Accordingly, in order to reuse the defective color filter generated during the color filter manufacturing process, a cleaning agent composition capable of effectively removing both the color resist, the organic insulating film, and the transparent resin is required.
이와 관련하여, 대한민국 공개특허 제 10-2003-0026664호에는 하이드록사이드 화합물를 주요 성분으로 하는 칼라 레지스트 박리액 조성물이 기재되어 있으며, 대한민국 공개특허 제 10-2005-0006980호에는 무기 알칼리 하이드록사이드, N-알킬-2-피롤리돈 등을 포함하는 박리액 조성물이 기재되어 있다. 그러나, 상기와 같은 종래 기술은 칼라 레지스트 박리에서는 소기의 성과를 이루었으나, 유기 절연막 또는 투명레진을 부분적으로나 전체적으로 제거하는 효과를 전혀 나타내지 않는다. 또한, 하이드록사이드 화합물 베이스 박리액 조성물은 고온으로 공정시 박리액의 휘발로 인하여 무기알칼리의 석출이 발생되는 문제가 있으며, 무기알칼리아세테이트는 염 역시 고온 공정시 물의 증발로 인해 분말로 석출되어 불량의 원인이 될 수 있는 문제가 있다.
Korean Patent Laid-Open No. 10-2003-0026664 discloses a color resist stripper composition comprising a hydroxide compound as a main component, Korean Patent Publication No. 10-2005-0006980 discloses a color resist stripper composition comprising an inorganic alkali hydroxide, N-alkyl-2-pyrrolidone, and the like. However, the above-described conventional techniques have achieved desired results in color resist peeling, but do not show any effect of partially or totally removing the organic insulating film or the transparent resin. In addition, there is a problem that precipitation of inorganic alkali occurs due to volatilization of the exfoliation liquid at the time of high temperature processing of the hydroxide compound base stripper liquid composition, and the salt of inorganic alkaline acetate also precipitates as powder due to evaporation of water during high temperature process, There is a problem that can cause.
따라서, 칼라 레지스트, 유기 절연막 및 투명레진 모두에 대하여 우수한 세정효과를 가지며, 고온 공정에서도 석출문제가 없는 세정제 조성물의 개발이 필요한 실정이다.
Therefore, it is necessary to develop a cleaning agent composition that has excellent cleaning effect for both color resist, organic insulating film, and transparent resin, and has no deposition problem even in a high-temperature process.
상기 종래 기술의 문제점을 해결하기 위해, 본 발명은 칼라필터의 재사용을 위해 칼라필터의 칼라 레지스트, 유기 절연막 및 투명레진 모두를 단시간 내에 효과적으로 제거할 수 있으며, 고온 공정에서도 석출문제가 없는 세정제 조성물을 제공하는 것을 목적으로 한다.In order to solve the problems of the prior art, the present invention can effectively remove both the color resist of the color filter, the organic insulating film and the transparent resin in a short period of time for reuse of the color filter, The purpose is to provide.
상기 목적을 달성하기 위해, 본 발명은 조성물 총 중량에 대하여, (a) 4급 암모늄염 화합물 1-10 중량%, (b) 극성용제 40-80 중량%, (c) 하기 화학식 1 또는 화학식 2로 표시되는 폴리에테르아민 1-20 중량%, (d) 하이드록실 아민계 화합물 0.1-5 중량%, (e) C4 이상 끓는점 100℃ 이상의 알킬알코올 1-20중량%, (f) 무기염기 또는 그의 염 0.01-2 중량% 및 (g) 물 1-40 중량%를 포함하는 것을 특징으로 하는 칼라 레지스트, 유기 절연막 및 투명레진 제거용 세정제 조성물을 제공한다.
(A) 1-10% by weight of a quaternary ammonium salt compound, (b) 40-80% by weight of a polar solvent, (c) (E) 1-20% by weight of an alkyl alcohol having a boiling point of 100 ° C or higher, (f) an inorganic base or a salt thereof 0.01-2% by weight, and (g) 1-40% by weight of water, based on the total weight of the cleaning composition.
본 발명의 세정제 조성물은 칼라 레지스트, 유기 절연막 및 투명레진 모두를 단시간 내에 효과적으로 제거할 수 있으며, 이에 따라 칼라필터 재사용의 생산성을 향상시킬 수 있다. 특히 본 발명의 세정제 조성물은 LCD 칼라필터 또는 TFT기판에 칼라 필터가 일체화된 구조에서 경화된 칼라 레지스트와 유기절연막 및 가교도를 증가시킨 투명레진을 기판으로부터 제거시킴으로 불량기판의 재사용을 가능하게 한다. 또한, 본 발명의 세정제 조성물은 무기알칼리하이드록사이드를 알칼리 베이스로 사용하지 않기 때문에, 고온 공정에서도 박리액의 휘발로 인한 무기알칼리의 석출 문제가 없다.
The detergent composition of the present invention can effectively remove both the color resist, the organic insulating film and the transparent resin in a short period of time, thereby improving the productivity of the color filter reuse. In particular, the cleaning composition of the present invention enables the reuse of a defective substrate by removing a cured color resist, an organic insulating film and a transparent resin having increased crosslinking degree from the substrate in a structure in which a color filter is integrated into an LCD color filter or a TFT substrate. Further, since the detergent composition of the present invention does not use an inorganic alkali hydroxide as an alkali base, there is no problem of precipitation of inorganic alkali due to volatilization of the exfoliating liquid even in a high temperature process.
이하, 본 발명을 보다 상세하게 설명한다.
Hereinafter, the present invention will be described in more detail.
칼라 레지스트, 유기 절연막 및 투명레진 제거용 세정제 조성물에 대한 것으로, 본 발명은 조성물 총 중량에 대하여, (a) 4급 암모늄염 화합물, (b) 극성용제, (c) 하기 화학식 1 또는 화학식 2로 표시되는 폴리에테르아민, (d) 하이드록실 아민계 화합물, (e) C4 이상 끓는점 100℃ 이상의 알킬알코올, (f) 무기염기 또는 그의 염 및 (g) 물을 포함하는 것을 특징으로 한다.
(A) a quaternary ammonium salt compound, (b) a polar solvent, (c) a surfactant represented by the following general formula (1) or (2) (D) a hydroxylamine-based compound, (e) C4 or higher alkyl alcohol having a boiling point of 100 ° C or higher, (f) an inorganic base or salt thereof, and (g) water.
본 발명의 세정제 조성물은 상기와 같은 조성에 의해, 칼라 레지스트, 유기 절연막 및 투명레진 모두를 단시간 내에 효과적으로 제거할 수 있으며, 이에 따라 칼라필터 재사용의 생산성을 향상시킬 수 있다.
The detergent composition of the present invention can effectively remove both the color resist, the organic insulating film and the transparent resin in a short time by the composition as described above, thereby improving the productivity of the color filter reuse.
(a) 4급 암모늄염 화합물 (a) a quaternary ammonium salt compound
본 발명의 (a) 4급 암모늄염 화합물은 히드록시드 이온을 배출하고, 이는 레지스트내로 침투하여 고분자 레지스트의 용해를 촉진하는 역할을 한다.
The quaternary ammonium salt compound (a) of the present invention releases hydroxide ions, which penetrate into the resist and promote the dissolution of the polymer resist.
상기 4급 암모늄염 화합물은 테트라메틸암모늄 히드록시드(TMAH), 테트라에틸암모늄 히드록시드(TEAH), 테트라프로필암모늄 히드록시드(TPAH) 및 테트라부틸암모늄 히드록시드(TBAH)로 이루어진 군으로부터 선택되는 1종 이상일 수 있다.
The quaternary ammonium salt compound is selected from the group consisting of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH) and tetrabutylammonium hydroxide (TBAH) Or more.
본 발명의 4급 암모늄염 화합물은 조성물 총 중량에 대하여 1-10 중량%의 함량으로 포함되는 것이 바람직하다. 본 발명의 세정제 조성물에 상기 4급 암모늄염 화합물이 1 중량% 미만으로 포함되면 하이드록사이드 이온의 칼라 레지스트 고분자 내로 침투력이 감소되며, 10 중량%를 초과하면 물의 함량이 증가되어 고분자 레진에 대한 용해력이 감소되는 문제가 있다.
The quaternary ammonium salt compound of the present invention is preferably contained in an amount of 1-10% by weight based on the total weight of the composition. When the quaternary ammonium salt compound is contained in the detergent composition of the present invention in an amount of less than 1% by weight, the penetration ability of the hydroxide ion color resist polymer decreases. When the quaternary ammonium salt compound is contained in an amount of more than 10% by weight, There is a problem of being reduced.
(b) 극성용제 (b) polar solvent
본 발명의 (b) 극성용제는 레지스트에 침투하여 팽윤성을 증가시켜 기판 표면으로부터 박리력을 증가시킨다. 또한, 본 발명의 레지스트 박리액 조성물의 물에 대한 용해력을 향상시키고, 이후 수세 공정에서 잔류물 제거가 용이하도록 한다.
The polar solvent (b) of the present invention penetrates the resist to increase the swelling property, thereby increasing the peeling force from the substrate surface. Further, the dissolution ability of the resist stripper composition of the present invention in water is improved, and the residue can be easily removed in the subsequent water washing step.
상기 극성용제는 디메틸설폭사이드, 디에틸설폭사이드, 디프로필설폭사이드, 설포란, n-메틸피롤리돈, 피롤리돈 및 n-에틸피롤리돈으로 이루어진 군으로부터 선택되는 1종 이상일 수 있다.
The polar solvent may be at least one member selected from the group consisting of dimethyl sulfoxide, diethyl sulfoxide, dipropyl sulfoxide, sulfolane, n-methylpyrrolidone, pyrrolidone and n-ethylpyrrolidone.
본 발명의 극성용제는 조성물 총 중량에 대하여 40-80 중량%의 함량으로 포함되는 것이 바람직하다. 본 발명의 세정제 조성물에 상기 극성용제가 40 중량% 미만으로 포함되면 고분자 레진의 용해력이 떨어지게 되고, 80 중량%를 초과하면 암모늄염 화합물의 활성을 저해하여 오히려 제거성이 떨어지게 된다.
The polar solvent of the present invention is preferably contained in an amount of 40 to 80% by weight based on the total weight of the composition. When the polar solvent is contained in an amount of less than 40% by weight, the solubility of the polymer resin is lowered. When the amount of the polar solvent exceeds 80% by weight, the activity of the ammonium salt compound is impaired.
(c) (c)
폴리에테르아민Polyetheramine
본 발명의 (c) 폴리에테르아민은 레지스트를 형성하는 수지, 특히 에폭시 수지에 대해 용해성이 뛰어나서 레지스트의 박리력을 향상시킬 수 있고 장비 내 필터 막힘도 개선하는 역할을 한다. 또한 열 및 화학적 안정성이 높은 수지를 사용하는 RGBW의 투명 레지스트의 경우에도 레지스트의 박리력이 우수하게 나타날 수 있도록 한다.
(C) The polyetheramine (c) of the present invention has excellent solubility in a resin for forming a resist, particularly an epoxy resin, and can improve the peeling force of the resist and improve filter clogging in the equipment. In addition, even in the case of RGBW transparent resist using a resin having high thermal and chemical stability, the resist peeling force is also excellent.
본 발명에서, 상기 폴리에테르아민은 하기 화학식 1 또는 화학식 2로 표시되는 화합물이다. In the present invention, the polyether amine is a compound represented by the following formula (1) or (2).
(화학식 1)(Formula 1)
상기 화학식 1에서, R은 C1~C6의 사슬형 알킬기, 또는 C1~C3의 알콕시기이고, x는 2 내지 6의 정수이며, Wherein R is a C1 to C6 chain alkyl group or a C1 to C3 alkoxy group, x is an integer of 2 to 6,
(화학식 2)(2)
상기 화학식 2에서, y는 2 내지 70의 정수이다.
In the general formula (2), y is an integer of 2 to 70.
구체적으로, 상기 화학식 1로 표시되는 폴리에테르아민은 트리에틸렌글리콜디아민, 3,6-디옥사-1,8-옥탄디아민, 4,7-디옥사데칸-1.10-디아민, 4,9-디옥사도데칸-1.12-디아민, 및 4,7,10-트리옥사-1,13-트리데칸디아민으로 이루어진 군으로부터 선택되는 1종 이상이며, 상기 화학식 2로 표시되는 폴리에테르아민은 y가 2~3, 5~6, 33~34 또는 67~68인 경우를 들 수 있으며, 이 경우 중량평균 분자량은 200 내지 4000일 수 있으며, 이들은 각각 단독으로 또는 2종 이상 혼합되어 사용될 수 있다.
Specifically, the polyether amine represented by the above-mentioned general formula (1) may be triethylene glycol diamine, 3,6-dioxa-1,8-octane diamine, 4,7- Diamine, and 4,7,10-trioxa-1,13-tridecanediamine, and the polyether amine represented by the formula (2) is a polyether amine in which y is 2 to 3 , 5 to 6, 33 to 34, or 67 to 68. In this case, the weight average molecular weight may be 200 to 4000, and these may be used singly or in combination of two or more.
바람직하게 본 발명의 폴리에테르아민은 트리에틸렌글리콜디아민, 폴리옥시프로필렌디아민(중량평균분자량 230), 폴리옥시프로필렌디아민 (중량평균분자량 400) 폴리옥시프로필렌디아민(중량평균분자량 2000) 등 일 수 있다.
Preferably, the polyether amine of the present invention may be triethylene glycol diamine, polyoxypropylene diamine (weight average molecular weight: 230), polyoxypropylene diamine (weight average molecular weight: 400), polyoxypropylene diamine (weight average molecular weight: 2000)
본 발명의 폴리에테르아민은 조성물 총 중량에 대하여 1-20 중량%로 포함되는 것이 바람직하다. 본 발명의 세정제 조성물에 상기 폴리에테르아민이 1 중량% 미만으로 포함되면 경화된 레진 내 침투에 의한 결합을 끊는 힘이 떨어지게 되고 20 중량%를 초과하면 4급알킬암모늄화합물 및 디메틸설폭사이드의 상대적 감소로 인한 고분자 레지스트의 용해력이 저하된다.
The polyether amine of the present invention is preferably contained in an amount of 1-20% by weight based on the total weight of the composition. When the polyetheramine is contained in the detergent composition of the present invention in an amount of less than 1% by weight, the strength of breaking the bond due to penetration into the cured resin is lowered. When the amount exceeds 20% by weight, the relative decrease of the quaternary alkylammonium compound and dimethylsulfoxide The solubility of the polymer resist is lowered.
(d) (d)
하이드록실Hydroxyl
아민계Amine system
화합물 compound
본 발명의 (d) 하이드록실 아민계 화합물은 저분자 구조로 짧은 시간에 히드록시드 이온을 생성하여 경화된 수지에 침투해 결합을 끊고 레지스트의 염료 성분을 용해시키는 역할을 한다.
The hydroxylamine-based compound (d) of the present invention has a low-molecular structure to generate hydroxide ions in a short time, permeates the cured resin to break the bond and dissolve the dye component of the resist.
상기 하이드록실 아민계 화합물은 히드록실아민, 디메틸히드록실아민 및 디에틸히드록실아민으로 이루어진 군으로부터 선택되는 1종 이상일 수 있다.
The hydroxylamine-based compound may be at least one selected from the group consisting of hydroxylamine, dimethylhydroxylamine, and diethylhydroxylamine.
본 발명의 하이드록실 아민계 화합물은 조성물 총 중량에 대하여 0.1-5 중량%로 포함되는 것이 바람직하다. 본 발명의 세정제 조성물에 상기 하이드록실 아민계 화합물의 함량이 0.1 중량% 미만인 경우에는, 레지스트의 염료 성분을 충분히 용해하기 어려우며, 5 중량% 초과인 경우에는 증량에 따른 효과의 증가가 없으므로 경제적이지 못하며, 상대적으로 4급 유기암모늄 히드록시드 및 극성용제의 함량이 저하되므로 레지스트의 용해력이 감소될 수 있다.
The hydroxylamine-based compound of the present invention is preferably contained in an amount of 0.1-5% by weight based on the total weight of the composition. When the content of the hydroxylamine compound is less than 0.1% by weight, the dye component of the resist is difficult to dissolve sufficiently. When the amount of the hydroxylamine compound is less than 5% by weight, the effect of increasing the amount of the hydroxylamine compound is not increased. , The content of the quaternary organic ammonium hydroxide and the polar solvent is relatively lowered, so that the solubility of the resist can be reduced.
(e) (e)
알킬알코올Alkyl alcohol
본 발명의 (e) 알킬알코올은 고분자의 결합을 끊어 히드록실기에 의한 레지스트 용해를 용이하게 하는 역할을 한다.
The alkyl alcohol (e) of the present invention plays a role of facilitating the dissolution of the resist by the hydroxyl group by cutting off the binding of the polymer.
상기 알킬알코올은 C4 이상 끓는점 100℃ 이상인 것을 특징으로 하며, 탄소수 4 이상 8 이하의 하이드록실기를 갖는 화합물인 것이 더욱 바람직하다. 구체적으로, 본 발명의 알킬알코올은 1-부탄올, 2-부탄올, 이소부탄올, 1-펜탄올, 이소아밀알코올, 2-펜탄올, 1-헥산올, 1-헵탄올, 1-옥탄올, 2-메틸-1-부탄올, 2-헥산올, 시클로헥산올, 2-메틸-2-펜탄올, 2-에틸헥실알코올, 2-페닐에탄올 및 3-메틸-3-펜탄올로 이루어진 군으로부터 선택되는 1종 이상일 수 있다.
The alkyl alcohol preferably has a boiling point of C4 or higher and a boiling point of 100 DEG C or higher, more preferably a compound having a hydroxyl group having 4 or more and 8 or less carbon atoms. Specifically, the alkyl alcohols of the present invention can be obtained by reacting an aldehyde with an alcohol such as 1-butanol, 2-butanol, isobutanol, 1-pentanol, isoamyl alcohol, Methyl-1-butanol, 2-hexanol, cyclohexanol, 2-methyl-2-pentanol, 2-ethylhexyl alcohol, 2-phenylethanol and 3-methyl- It may be more than one kind.
본 발명의 알킬알코올은 조성물 총 중량에 대하여 1-20 중량%로 포함되는 것이 바람직하다. 본 발명의 세정제 조성물에 상기 알킬알코올의 함량이 1 중량% 미만인 경우에는 투명레진의 제거력에 효과가 없으며, 20 중량% 초과인 경우에는 증량에 따른 제거력이 더 이상 증가하지 않는다.
The alkyl alcohol of the present invention is preferably contained in an amount of 1-20% by weight based on the total weight of the composition. If the content of the alkyl alcohol in the detergent composition of the present invention is less than 1 wt%, the removal force of the transparent resin is not effective. If the amount of the alkyl alcohol is more than 20 wt%, the removal power is not increased any more.
(f) 무기염기 또는 그의 염(f) an inorganic base or a salt thereof
본 발명의 (f) 무기염기 또는 그의 염은 유기계 절연막에 대한 박리력을 향상시키는 역할을 한다.
The inorganic base (f) or its salt of the present invention has a role of improving the peeling force to the organic insulating film.
상기 무기염기 또는 그의 염은 수산화나트륨, 수산화칼륨, 탄산나트륨, 탄산칼륨, 중탄산나트륨, 질산나트륨, 질산칼륨, 황산나트륨, 황산칼륨, 규산나트륨 및 규산칼륨으로 이루어진 군으로부터 선택되는 1종 이상일 수 있다.
The inorganic base or its salt may be at least one selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium nitrate, potassium nitrate, sodium sulfate, potassium sulfate, sodium silicate and potassium silicate.
본 발명의 무기염기 또는 그의 염은 조성물 총 중량에 대하여 0.01-2 중량%로 포함되는 것이 바람직하다. 본 발명의 세정제 조성물에 상기 알칼리금속염의 함량이, 0.01 중량% 미만이면 유기계 절연막에 대한 박리력이 떨어지며, 2 중량%를 초과하면 증량에 따른 효과가 미미하며 경제적이지 못하다.
The inorganic base or salt thereof of the present invention is preferably contained in an amount of 0.01 to 2% by weight based on the total weight of the composition. If the content of the alkali metal salt is less than 0.01 wt%, the peeling force against the organic insulating film is poor. If the amount is more than 2 wt%, the effect of increasing the amount is insignificant and not economical.
(g) 물 (g) Water
본 발명의 (g) 물은 적절하게 첨가되어 전체 조성을 조절하며 히드록시이온의 활동도를 높이는 역할을 한다
Water (g) of the present invention is appropriately added to control the overall composition and increase the activity of the hydroxy ion
본 발명의 물은 본 발명의 조성물에 포함되는 타 성분에 대하여 잔량으로 포함될 수 있으며, 구체적으로 1-40 중량% 포함될 수 있다.
The water of the present invention may be contained in the remaining amount relative to the other components contained in the composition of the present invention, and specifically may be contained in an amount of 1-40% by weight.
본 발명의 세정제 조성물은, 칼라 레지스트, 유기 절연막 및 투명레진 모두에 대하여 매우 우수한 세정효과를 나타내며, 상기 칼라 레지스트는 네가티브형 감광성레진일 수 있으나 이에 한정되는 것은 아니며, 상기 유기 절연막은 폴리아크릴레이트 수지일 수 있으나 이에 한정되는 것은 아니고, 상기 투명레진은 폴리아크릴레이트에 에폭시관능기를 추가하여 가교도를 높인 수지일 수 있으나 이에 한정되는 것은 아니다.
The cleaning composition of the present invention exhibits a very excellent cleaning effect for both the color resist, the organic insulating film and the transparent resin, and the color resist may be a negative photosensitive resin, but the present invention is not limited thereto, and the organic insulating film may be a polyacrylate resin But it is not limited thereto. The transparent resin may be a resin having an increased cross-linking property by adding an epoxy functional group to polyacrylate, but is not limited thereto.
이하에서, 실시예를 통하여 본 발명을 보다 상세히 설명한다. 그러나, 하기의 실시예는 본 발명을 더욱 구체적으로 설명하기 위한 것으로서, 본 발명의 범위가 하기의 실시예에 의하여 한정되는 것은 아니다. 하기의 실시예는 본 발명의 범위 내에서 당업자에 의해 적절히 수정, 변경될 수 있다.
Hereinafter, the present invention will be described in more detail by way of examples. However, the following examples are intended to further illustrate the present invention, and the scope of the present invention is not limited by the following examples. The following examples can be appropriately modified and changed by those skilled in the art within the scope of the present invention.
실시예Example
및 And
비교예Comparative Example
: 세정제 조성물의 제조: Preparation of detergent composition
하기 표 1에 제시된 성분을 정해진 조성비에 따라 혼합하여 실시예 1 내지 10 및 비교예 1 내지 9의 세정제 조성물을 제조하였다.
The cleaning agent compositions of Examples 1 to 10 and Comparative Examples 1 to 9 were prepared by mixing the components shown in the following Table 1 according to the specified composition ratios.
(a) 제4급 암모늄수산화물(a) quaternary ammonium hydroxide
TMAH: 테트라메틸암모늄 히드록시드, TMAH: tetramethylammonium hydroxide,
TEAH: 테트라에틸암모늄 히드록시드
TEAH: tetraethylammonium hydroxide
(b) 극성 용제(b) polar solvent
DMSO: 디메틸설폭사이드
DMSO: dimethylsulfoxide
(c) 폴리에테르아민(c) Polyetheramine
A1: 4,7,10-트리옥사-1,13-트리데칸디아민 A1: 4,7,10-trioxa-1,13-tridecanediamine
A2: 폴리옥시프로필렌디아민(중량평균 분자량 230)A2: polyoxypropylenediamine (weight average molecular weight: 230)
A3: 폴리옥시프로필렌디아민 (중량평균 분자량 400) A3: polyoxypropylene diamine (weight average molecular weight: 400)
A4: 폴리옥시프로필렌디아민(중량평균 분자량 2000)A4: polyoxypropylenediamine (weight average molecular weight 2000)
A5 : 폴리옥시부틸렌디아민(중량평균 분자량500)
A5: polyoxybutylenediamine (weight average molecular weight 500)
(e) 알킬알코올(e) alkyl alcohol
B1: n-부탄올 B1: n-butanol
B2: 시클로헥산올 B2: Cyclohexanol
B3: 2-에틸헥실알코올B3: 2-ethylhexyl alcohol
B4: 2-메틸-1-부탄올B4: 2-Methyl-1-butanol
B5: 2-페닐에탄올B5: 2-phenylethanol
B6: 에탄올
B6: Ethanol
실험예Experimental Example
1: One:
컬러레지스트의Color resist
제거 평가 Removal evaluation
실시예와 비교예에서 제조된 세정제 조성물의 컬러레지스트 제거 효과를 평가하기 위하여, Red, Green, Blue(이하 RGB)가 각각 도포되어 있는 칼라필터 기판을 사용하였다. 칼라레지스트는 도포 후 90℃에서 120초간 프리베이크 후 노광을 시킨 후에 현상한 후 오븐에서 패턴이 형성된 기판을 220℃ 오븐에서 하드베이크 하여 제작하였다.
In order to evaluate the color resist removal effect of the cleaning composition prepared in Examples and Comparative Examples, a color filter substrate coated with red, green, and blue (hereinafter RGB) was used. The color resist was applied after being prebaked at 90 ° C for 120 seconds after exposure, developed, and then hard baked in an oven at 220 ° C in an oven.
실시예와 비교예에서 제조된 세정제 조성물의 컬러레지스트의 제거성을 확인하기 위해, 70℃의 용액에 상기 RGB가 도포되어 있는 칼라필터 기판을 5분, 10분간 침적하여 광학현미경으로 레지스트의 잔존 여부를 확인 하였다. 그 결과를 다음의 기준으로 평가하여 하기 표 2에 나타내었다. To confirm the removability of the color resist of the cleaning composition prepared in Examples and Comparative Examples, the color filter substrate coated with the RGB was immersed in a solution at 70 캜 for 5 minutes and 10 minutes, and the resist remained Respectively. The results are shown in Table 2 below.
◎ : 레지스트 100%제거◎: 100% resist removal
○ : 레지스트 80%이상 제거○: Resist 80% or more removed
△ : 레지스트 80%미만 제거?: Less than 80% resist removal
X : 레지스트 제거 안됨
X: No resist removal
실험예Experimental Example
2: 2:
유기계Organic
절연막의 제거 평가 Evaluation of removal of insulating film
유기계 절연막의 제거성을 확인하기 위해 유리기판 위에 폴리아크릴레이트 수지(PAC resin)을 유리 기판에 도포하고 90℃에서 120초간 프리베이크시켰다. 이후 노광 및 현상 공정을 거쳐 패턴을 형성한 후에 기판을 220℃ 오븐에서 하드베이크하여 유기 절연막 레지스트를 제조하였다. 유기절연막을 도포 후 하드베이크된 기판을 사용하였다.
In order to confirm the removability of the organic insulating film, polyacylate resin (PAC resin) was applied on a glass substrate and prebaked at 90 ° C for 120 seconds. After patterning through exposure and development processes, the substrate was hard baked in an oven at 220 ° C to prepare an organic insulating film resist. A hard-baked substrate was used after application of the organic insulating film.
실시예와 비교예에서 제조된 세정제 조성물의 유기계 절연막의 제거성을 확인하기 위해, 70℃의 용액에 상기 유기계 절연막 기판을 5분, 10분간 침적하여 광학현미경으로 유기 절연막의 잔존 여부를 확인 하였다. 그 결과를 다음의 기준으로 평가하여 하기 표 2에 나타내었다. In order to confirm the removability of the organic insulating film of the detergent composition prepared in Examples and Comparative Examples, the organic insulating film substrate was immersed in a solution at 70 캜 for 5 minutes and 10 minutes, and the organic insulating film was observed by an optical microscope. The results are shown in Table 2 below.
◎ : 레지스트 100%제거◎: 100% resist removal
○ : 레지스트 80%이상 제거○: Resist 80% or more removed
△ : 레지스트 80%미만 제거?: Less than 80% resist removal
X : 레지스트 제거 안됨
X: No resist removal
실험예Experimental Example
3: 3:
투명레진막의Transparent resin film
제거 평가 Removal evaluation
투명레진막의 제거성을 확인하기 위해 유리기판 위에 아크릴레이트 단량체에 에폭시기를 갖는 화합물을 부가하여 공중합된 투명레진을 기판에 도포하고 90℃에서 120초간 프리베이크시켰다. 이후 노광 및 현상 공정을 거쳐 패턴을 형성한 후에 기판을 220℃ 오븐에서 하드베이크하여 투명 레진막을 제조하였다. 투명레진막을 도포 후 하드베이크 된 기판을 사용하였다.
In order to confirm the removability of the transparent resin film, a copolymerized transparent resin was coated on the substrate by adding a compound having an epoxy group to the acrylate monomer and then pre-baked at 90 ° C for 120 seconds. After patterning through exposure and development processes, the substrate was hard baked in an oven at 220 ° C to prepare a transparent resin film. A hard-baked substrate was used after applying the transparent resin film.
실시예와 비교예에서 제조된 세정제 조성물의 투명레진막의 제거성을 확인하기 위해, 70℃의 용액에 상기 유기계 절연막 기판을 5분, 10분간 침적하여 광학현미경으로 유기 절연막의 잔존 여부를 확인 하였다. 그 결과를 다음의 기준으로 평가하여 하기 표 2에 나타내었다. In order to confirm the removability of the transparent resin film of the cleaner composition prepared in Examples and Comparative Examples, the organic insulating film substrate was immersed in a solution at 70 캜 for 5 minutes and 10 minutes, and the organic insulating film remained by optical microscope. The results are shown in Table 2 below.
◎ : 레지스트 100%제거◎: 100% resist removal
○ : 레지스트 80%이상 제거○: Resist 80% or more removed
△ : 레지스트 80%미만 제거?: Less than 80% resist removal
X : 레지스트 제거 안됨X: No resist removal
상기 표 2에 나타낸 바와 같이, 실시예 1 내지 10의 세정제 조성물은 컬러레지스트기판, 유기계 절연막기판 및 투명레진기판 모두에 대하여 매우 우수한 세정효과를 나타내었다.
As shown in Table 2, the cleaning compositions of Examples 1 to 10 exhibited excellent cleaning effects on both the color resist substrate, the organic insulating film substrate, and the transparent resin substrate.
반면 본 발명의 구성 중 어느 하나를 포함하지 않는 비교예 1 내지 9의 조성물은 컬러레지스트기판, 유기계 절연막기판 및 투명레진기판에 대한 세정효과가 떨어졌다.
On the other hand, the compositions of Comparative Examples 1 to 9, which do not include any one of the constitutions of the present invention, exhibit poor cleaning effects on the color resist substrate, the organic insulating film substrate and the transparent resin substrate.
따라서, 본 발명의 조성을 갖는 세정액 조성물은 칼라필터의 칼라레지스트, 유기계 절연막 및 투명레진기판을 단시간 내에 충분히 제거할 수 있으므로 칼라필터 재사용의 생산성을 향상시킬 수 있다.
Therefore, the cleaning liquid composition having the composition of the present invention can sufficiently remove the color resist, the organic insulating film, and the transparent resin substrate of the color filter in a short time, thereby improving the productivity of color filter reuse.
Claims (7)
(a) 4급 암모늄염 화합물 1-10 중량%,
(b) 극성용제 40-80 중량%,
(c) 하기 화학식 1 또는 화학식 2로 표시되는 폴리에테르아민 1-20 중량%,
(d) 하이드록실 아민계 화합물 0.1-5 중량%,
(e) C4 이상 끓는점 100℃ 이상의 알킬알코올 1-20 중량%,
(f) 무기염기 또는 그의 염 0.01-2 중량% 및
(g) 물 1-40 중량%를 포함하는 것을 특징으로 하는 칼라 레지스트, 유기 절연막 및 투명레진 제거용 세정제 조성물.
(화학식 1)
(상기 화학식 1에서, R은 C1~C6의 사슬형 알킬기, 또는 C1~C3의 알콕시기이고, x는 1 내지 6의 정수이다.)
(화학식 2)
(상기 화학식 2에서, y는 2 내지 70의 정수이다.)
With respect to the total weight of the composition,
(a) 1-10% by weight of a quaternary ammonium salt compound,
(b) 40 to 80% by weight of a polar solvent,
(c) 1 to 20% by weight of a polyetheramine represented by the following general formula (1) or (2)
(d) 0.1-5% by weight of a hydroxylamine compound,
(e) 1-20% by weight of C4 or higher alkyl alcohol having a boiling point of 100 DEG C or higher,
(f) 0.01-2% by weight of an inorganic base or salt thereof and
(g) 1 to 40% by weight of water, and a cleaning agent composition for removing a color resist, an organic insulating film and a transparent resin.
(Formula 1)
(Wherein R is a C1 to C6 chain alkyl group or a C1 to C3 alkoxy group, and x is an integer of 1 to 6.)
(2)
(In the formula (2), y is an integer of 2 to 70)
상기 (a) 4급 암모늄염 화합물은 테트라메틸암모늄 히드록시드(TMAH), 테트라에틸암모늄 히드록시드(TEAH), 테트라프로필암모늄 히드록시드(TPAH) 및 테트라부틸암모늄 히드록시드(TBAH)로 이루어진 군으로부터 선택되는 1종 이상인, 칼라 레지스트, 유기 절연막 및 투명레진 제거용 세정제 조성물.
The method according to claim 1,
The quaternary ammonium salt compound (a) is composed of tetramethylammonium hydroxide (TMAH), tetraethylammonium hydroxide (TEAH), tetrapropylammonium hydroxide (TPAH) and tetrabutylammonium hydroxide (TBAH) And a cleaning agent composition for removing a color resist, an organic insulating film, and a transparent resin.
상기 (b) 극성용제는 디메틸설폭사이드, 디에틸설폭사이드, 디프로필설폭사이드, 설포란, n-메틸피롤리돈, 피롤리돈 및 n-에틸피롤리돈으로 이루어진 군으로부터 선택되는 1종 이상인, 칼라 레지스트, 유기 절연막 및 투명레진 제거용 세정제 조성물.
The method according to claim 1,
The polar solvent (b) may be at least one selected from the group consisting of dimethylsulfoxide, diethylsulfoxide, dipropylsulfoxide, sulfolane, n-methylpyrrolidone, pyrrolidone and n- , A color resist, an organic insulating film, and a cleaning agent composition for removing a transparent resin.
상기 화학식 1로 표시되는 폴리에테르아민은 트리에틸렌글리콜디아민, 3,6-디옥사-1,8-옥탄디아민, 4,7-디옥사데칸-1.10-디아민, 4,9-디옥사도데칸-1.12-디아민 및 4,7,10-트리옥사-1,13-트리데칸디아민으로 이루어진 군으로부터 선택되는 1종 이상이며, 상기 화학식 2로 표시되는 폴리에테르아민은 중량평균 분자량이 200 내지 4000인, 칼라 레지스트, 유기 절연막 및 투명레진 제거용 세정제 조성물.
The method according to claim 1,
The polyether amine represented by the above-mentioned formula (1) may be at least one selected from the group consisting of triethylene glycol diamine, 3,6-dioxa-1,8-octane diamine, 4,7- 1,12-diamine and 4,7,10-trioxa-1,13-tridecanediamine, and the polyether amine represented by Formula 2 has a weight average molecular weight of 200 to 4000, A color resist, an organic insulating film, and a cleaning agent composition for removing a transparent resin.
상기 (d) 하이드록실 아민계 화합물은 히드록실아민, 디메틸히드록실아민 및 디에틸히드록실아민으로 이루어진 군으로부터 선택되는 1종 이상인, 칼라 레지스트, 유기 절연막 및 투명레진 제거용 세정제 조성물.
The method according to claim 1,
Wherein the hydroxylamine-based compound (d) is at least one selected from the group consisting of hydroxylamine, dimethylhydroxylamine, and diethylhydroxylamine, and a cleaning agent composition for removing a color resist, an organic insulating film, and a transparent resin.
상기 (e) C4 이상 끓는점 100℃ 이상의 알킬알코올은 1-부탄올, 2-부탄올, 이소부탄올, 1-펜탄올, 이소아밀알코올, 2-펜탄올, 1-헥산올, 1-헵탄올, 1-옥탄올, 2-메틸-1-부탄올, 2-헥산올, 시클로헥산올, 2-메틸-2-펜탄올, 2-에틸헥실알코올, 2-페닐에탄올 및 3-메틸-3-펜탄올로 이루어진 군으로부터 선택되는 1종 이상인, 칼라 레지스트, 유기 절연막 및 투명레진 제거용 세정제 조성물.
The method according to claim 1,
(E) Alkyl alcohol having a boiling point of not lower than C4 and having a boiling point of 100 ° C or higher is 1-butanol, 2-butanol, isobutanol, 1-pentanol, isoamyl alcohol, 2-pentanol, Which is composed of 2-methyl-1-butanol, 2-hexanol, cyclohexanol, 2-methyl-2-pentanol, 2-ethylhexyl alcohol, And a cleaning agent composition for removing a color resist, an organic insulating film, and a transparent resin.
상기 (f) 무기염기 또는 그의 수산화나트륨, 수산화칼륨, 탄산나트륨, 탄산칼륨, 중탄산나트륨, 질산나트륨, 질산칼륨, 황산나트륨, 황산칼륨, 규산나트륨 및 규산칼륨으로 이루어진 군으로부터 선택되는 1종 이상인, 칼라 레지스트, 유기 절연막 및 투명레진 제거용 세정제 조성물. The method according to claim 1,
(F) at least one inorganic base selected from the group consisting of sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate, sodium bicarbonate, sodium nitrate, potassium nitrate, sodium sulfate, potassium sulfate, sodium silicate and potassium silicate; , A detergent composition for removing an organic insulating film and a transparent resin.
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| CN111655832B (en) * | 2018-03-02 | 2022-05-17 | 花王株式会社 | Mildew-removing cleaning agent composition for hard surface |
| JP7017950B2 (en) * | 2018-03-02 | 2022-02-09 | 花王株式会社 | Mold-killing detergent composition for hard surfaces |
| JP7017951B2 (en) * | 2018-03-02 | 2022-02-09 | 花王株式会社 | Mold-killing detergent composition for hard surfaces |
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| KR20030026664A (en) | 2001-09-26 | 2003-04-03 | 주식회사 동진쎄미켐 | A color resist remover composition for tft-lcd preparation |
| KR20050006980A (en) | 2003-07-10 | 2005-01-17 | 주식회사 동진쎄미켐 | Stripping composition for removing color resist of tft-lcd manufacturing process |
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| US5904156A (en) * | 1997-09-24 | 1999-05-18 | International Business Machines Corporation | Dry film resist removal in the presence of electroplated C4's |
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| US6475966B1 (en) * | 2000-02-25 | 2002-11-05 | Shipley Company, L.L.C. | Plasma etching residue removal |
| SG118380A1 (en) * | 2004-06-15 | 2006-01-27 | Air Prod & Chem | Composition and method comprising same for removing residue from a substrate |
| KR101328097B1 (en) * | 2006-01-11 | 2013-11-13 | 주식회사 동진쎄미켐 | A color resist remover composition for tft-lcd preparation |
| KR101333779B1 (en) * | 2007-08-20 | 2013-11-29 | 주식회사 동진쎄미켐 | A color resist remover composition for tft-lcd preparation |
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| KR20030026664A (en) | 2001-09-26 | 2003-04-03 | 주식회사 동진쎄미켐 | A color resist remover composition for tft-lcd preparation |
| KR20050006980A (en) | 2003-07-10 | 2005-01-17 | 주식회사 동진쎄미켐 | Stripping composition for removing color resist of tft-lcd manufacturing process |
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