KR20090045859A - Stripping agent for polyimide - Google Patents
Stripping agent for polyimide Download PDFInfo
- Publication number
- KR20090045859A KR20090045859A KR1020080106459A KR20080106459A KR20090045859A KR 20090045859 A KR20090045859 A KR 20090045859A KR 1020080106459 A KR1020080106459 A KR 1020080106459A KR 20080106459 A KR20080106459 A KR 20080106459A KR 20090045859 A KR20090045859 A KR 20090045859A
- Authority
- KR
- South Korea
- Prior art keywords
- weight
- polyimide
- water
- agent
- release agent
- Prior art date
Links
- 229920001721 polyimide Polymers 0.000 title claims abstract description 50
- 239000003795 chemical substances by application Substances 0.000 title claims abstract description 48
- 239000004642 Polyimide Substances 0.000 title claims abstract description 47
- 150000005846 sugar alcohols Polymers 0.000 claims abstract description 20
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 229910000077 silane Inorganic materials 0.000 claims abstract description 11
- 125000004432 carbon atom Chemical group C* 0.000 claims abstract description 9
- 125000000217 alkyl group Chemical group 0.000 claims abstract description 8
- -1 silane compound Chemical class 0.000 claims abstract description 8
- 239000001257 hydrogen Substances 0.000 claims abstract description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 6
- 125000004435 hydrogen atom Chemical group [H]* 0.000 claims abstract description 6
- 239000000758 substrate Substances 0.000 claims description 23
- 239000003513 alkali Substances 0.000 claims description 14
- 239000000908 ammonium hydroxide Substances 0.000 claims description 11
- 125000001453 quaternary ammonium group Chemical group 0.000 claims description 11
- 238000009835 boiling Methods 0.000 claims description 10
- 239000004973 liquid crystal related substance Substances 0.000 claims description 4
- 238000000034 method Methods 0.000 claims description 4
- 150000004756 silanes Chemical class 0.000 claims description 4
- KHLRJDNGHBXOSV-UHFFFAOYSA-N 5-trimethoxysilylpentane-1,3-diamine Chemical compound CO[Si](OC)(OC)CCC(N)CCN KHLRJDNGHBXOSV-UHFFFAOYSA-N 0.000 claims description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 2
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 abstract description 24
- 229910052750 molybdenum Inorganic materials 0.000 abstract description 24
- 239000011733 molybdenum Substances 0.000 abstract description 24
- 229910052782 aluminium Inorganic materials 0.000 abstract description 22
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 abstract description 22
- 229910052751 metal Inorganic materials 0.000 abstract description 13
- 239000002184 metal Substances 0.000 abstract description 13
- 238000004140 cleaning Methods 0.000 abstract description 10
- 230000007797 corrosion Effects 0.000 abstract description 10
- 238000005260 corrosion Methods 0.000 abstract description 10
- 150000002739 metals Chemical class 0.000 abstract description 2
- 230000000052 comparative effect Effects 0.000 description 12
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 11
- 239000011521 glass Substances 0.000 description 10
- 239000000203 mixture Substances 0.000 description 10
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 9
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 9
- SECXISVLQFMRJM-UHFFFAOYSA-N N-Methylpyrrolidone Chemical compound CN1CCCC1=O SECXISVLQFMRJM-UHFFFAOYSA-N 0.000 description 8
- 150000001875 compounds Chemical class 0.000 description 8
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 8
- 238000011156 evaluation Methods 0.000 description 7
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 description 5
- BLRPTPMANUNPDV-UHFFFAOYSA-N Silane Chemical compound [SiH4] BLRPTPMANUNPDV-UHFFFAOYSA-N 0.000 description 5
- 239000007788 liquid Substances 0.000 description 5
- POAOYUHQDCAZBD-UHFFFAOYSA-N 2-butoxyethanol Chemical compound CCCCOCCO POAOYUHQDCAZBD-UHFFFAOYSA-N 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 239000002798 polar solvent Substances 0.000 description 4
- 239000011347 resin Substances 0.000 description 4
- 229920005989 resin Polymers 0.000 description 4
- SJECZPVISLOESU-UHFFFAOYSA-N 3-trimethoxysilylpropan-1-amine Chemical compound CO[Si](OC)(OC)CCCN SJECZPVISLOESU-UHFFFAOYSA-N 0.000 description 3
- FBPFZTCFMRRESA-FSIIMWSLSA-N D-Glucitol Natural products OC[C@H](O)[C@H](O)[C@@H](O)[C@H](O)CO FBPFZTCFMRRESA-FSIIMWSLSA-N 0.000 description 3
- FBPFZTCFMRRESA-JGWLITMVSA-N D-glucitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-JGWLITMVSA-N 0.000 description 3
- 235000011187 glycerol Nutrition 0.000 description 3
- 239000003921 oil Substances 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 239000000600 sorbitol Substances 0.000 description 3
- 235000010356 sorbitol Nutrition 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- SBASXUCJHJRPEV-UHFFFAOYSA-N 2-(2-methoxyethoxy)ethanol Chemical compound COCCOCCO SBASXUCJHJRPEV-UHFFFAOYSA-N 0.000 description 2
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 description 2
- MTHSVFCYNBDYFN-UHFFFAOYSA-N diethylene glycol Chemical compound OCCOCCO MTHSVFCYNBDYFN-UHFFFAOYSA-N 0.000 description 2
- 229940028356 diethylene glycol monobutyl ether Drugs 0.000 description 2
- 238000007598 dipping method Methods 0.000 description 2
- 239000010419 fine particle Substances 0.000 description 2
- HYBBIBNJHNGZAN-UHFFFAOYSA-N furfural Chemical compound O=CC1=CC=CO1 HYBBIBNJHNGZAN-UHFFFAOYSA-N 0.000 description 2
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 2
- JCGNDDUYTRNOFT-UHFFFAOYSA-N oxolane-2,4-dione Chemical compound O=C1COC(=O)C1 JCGNDDUYTRNOFT-UHFFFAOYSA-N 0.000 description 2
- 239000009719 polyimide resin Substances 0.000 description 2
- HNJBEVLQSNELDL-UHFFFAOYSA-N pyrrolidin-2-one Chemical compound O=C1CCCN1 HNJBEVLQSNELDL-UHFFFAOYSA-N 0.000 description 2
- 229940073455 tetraethylammonium hydroxide Drugs 0.000 description 2
- LRGJRHZIDJQFCL-UHFFFAOYSA-M tetraethylazanium;hydroxide Chemical compound [OH-].CC[N+](CC)(CC)CC LRGJRHZIDJQFCL-UHFFFAOYSA-M 0.000 description 2
- 239000013585 weight reducing agent Substances 0.000 description 2
- WYTZZXDRDKSJID-UHFFFAOYSA-N (3-aminopropyl)triethoxysilane Chemical compound CCO[Si](OCC)(OCC)CCCN WYTZZXDRDKSJID-UHFFFAOYSA-N 0.000 description 1
- HXKKHQJGJAFBHI-UHFFFAOYSA-N 1-aminopropan-2-ol Chemical compound CC(O)CN HXKKHQJGJAFBHI-UHFFFAOYSA-N 0.000 description 1
- JOLQKTGDSGKSKJ-UHFFFAOYSA-N 1-ethoxypropan-2-ol Chemical compound CCOCC(C)O JOLQKTGDSGKSKJ-UHFFFAOYSA-N 0.000 description 1
- FVRSWMRVYMPTBU-UHFFFAOYSA-M 1-hydroxypropyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CCC(O)[N+](C)(C)C FVRSWMRVYMPTBU-UHFFFAOYSA-M 0.000 description 1
- ZNQVEEAIQZEUHB-UHFFFAOYSA-N 2-ethoxyethanol Chemical compound CCOCCO ZNQVEEAIQZEUHB-UHFFFAOYSA-N 0.000 description 1
- KIZQNNOULOCVDM-UHFFFAOYSA-M 2-hydroxyethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].C[N+](C)(C)CCO KIZQNNOULOCVDM-UHFFFAOYSA-M 0.000 description 1
- ZFDNAYFXBJPPEB-UHFFFAOYSA-M 2-hydroxyethyl(tripropyl)azanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCO ZFDNAYFXBJPPEB-UHFFFAOYSA-M 0.000 description 1
- QCAHUFWKIQLBNB-UHFFFAOYSA-N 3-(3-methoxypropoxy)propan-1-ol Chemical compound COCCCOCCCO QCAHUFWKIQLBNB-UHFFFAOYSA-N 0.000 description 1
- MFKRHJVUCZRDTF-UHFFFAOYSA-N 3-methoxy-3-methylbutan-1-ol Chemical compound COC(C)(C)CCO MFKRHJVUCZRDTF-UHFFFAOYSA-N 0.000 description 1
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- FBPFZTCFMRRESA-KVTDHHQDSA-N D-Mannitol Chemical compound OC[C@@H](O)[C@@H](O)[C@H](O)[C@H](O)CO FBPFZTCFMRRESA-KVTDHHQDSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- 229930195725 Mannitol Natural products 0.000 description 1
- TVXBFESIOXBWNM-UHFFFAOYSA-N Xylitol Natural products OCCC(O)C(O)C(O)CCO TVXBFESIOXBWNM-UHFFFAOYSA-N 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000001476 alcoholic effect Effects 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 125000003277 amino group Chemical group 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
- 125000004429 atom Chemical group 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 238000013329 compounding Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 235000014113 dietary fatty acids Nutrition 0.000 description 1
- ZBCBWPMODOFKDW-UHFFFAOYSA-N diethanolamine Chemical compound OCCNCCO ZBCBWPMODOFKDW-UHFFFAOYSA-N 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
- 230000000694 effects Effects 0.000 description 1
- KVFVBPYVNUCWJX-UHFFFAOYSA-M ethyl(trimethyl)azanium;hydroxide Chemical compound [OH-].CC[N+](C)(C)C KVFVBPYVNUCWJX-UHFFFAOYSA-M 0.000 description 1
- 239000003925 fat Substances 0.000 description 1
- 239000000194 fatty acid Substances 0.000 description 1
- 229930195729 fatty acid Natural products 0.000 description 1
- 150000004665 fatty acids Chemical class 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 238000007654 immersion Methods 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229940102253 isopropanolamine Drugs 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
- 235000010355 mannitol Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000155 melt Substances 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 239000011859 microparticle Substances 0.000 description 1
- 229920002120 photoresistant polymer Polymers 0.000 description 1
- 235000013772 propylene glycol Nutrition 0.000 description 1
- 230000001172 regenerating effect Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 125000000547 substituted alkyl group Chemical group 0.000 description 1
- HXJUTPCZVOIRIF-UHFFFAOYSA-N sulfolane Chemical compound O=S1(=O)CCCC1 HXJUTPCZVOIRIF-UHFFFAOYSA-N 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- DAHWFTWPSFSFMS-UHFFFAOYSA-N trihydroxysilane Chemical compound O[SiH](O)O DAHWFTWPSFSFMS-UHFFFAOYSA-N 0.000 description 1
- GFKCWAROGHMSTC-UHFFFAOYSA-N trimethoxy(6-trimethoxysilylhexyl)silane Chemical compound CO[Si](OC)(OC)CCCCCC[Si](OC)(OC)OC GFKCWAROGHMSTC-UHFFFAOYSA-N 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 239000000811 xylitol Substances 0.000 description 1
- HEBKCHPVOIAQTA-SCDXWVJYSA-N xylitol Chemical compound OC[C@H](O)[C@@H](O)[C@H](O)CO HEBKCHPVOIAQTA-SCDXWVJYSA-N 0.000 description 1
- 235000010447 xylitol Nutrition 0.000 description 1
- 229960002675 xylitol Drugs 0.000 description 1
Classifications
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- G—PHYSICS
- G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
- G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
- G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
- G03F7/26—Processing photosensitive materials; Apparatus therefor
- G03F7/42—Stripping or agents therefor
- G03F7/422—Stripping or agents therefor using liquids only
- G03F7/425—Stripping or agents therefor using liquids only containing mineral alkaline compounds; containing organic basic compounds, e.g. quaternary ammonium compounds; containing heterocyclic basic compounds containing nitrogen
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C41/00—Preparation of ethers; Preparation of compounds having groups, groups or groups
- C07C41/01—Preparation of ethers
- C07C41/05—Preparation of ethers by addition of compounds to unsaturated compounds
- C07C41/06—Preparation of ethers by addition of compounds to unsaturated compounds by addition of organic compounds only
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/10—Polyimides; Polyester-imides; Polyamide-imides; Polyamide acids or similar polyimide precursors
- C08G73/1042—Copolyimides derived from at least two different tetracarboxylic compounds or two different diamino compounds
-
- 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
- C11D7/02—Inorganic compounds
- C11D7/04—Water-soluble compounds
- C11D7/08—Acids
-
- 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
- C11D7/26—Organic compounds containing oxygen
- C11D7/261—Alcohols; Phenols
-
- 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)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Wood Science & Technology (AREA)
- Health & Medical Sciences (AREA)
- Engineering & Computer Science (AREA)
- Life Sciences & Earth Sciences (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Physics & Mathematics (AREA)
- General Physics & Mathematics (AREA)
- Inorganic Chemistry (AREA)
- Emergency Medicine (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Detergent Compositions (AREA)
- Paints Or Removers (AREA)
- Cleaning Or Drying Semiconductors (AREA)
Abstract
금속(특히 알루미늄 및 몰리브덴)의 부식을 억제하면서 뛰어난 세정성을 가진 폴리이미드용 박리제를 제공한다. 본 발명은 물, 알칼리제[B], 다가(多價) 알코올을 제외한 수용성 유기용제[C], 다가 알코올[D], 하기 일반식(1)으로 표시되는 실란계 화합물[A]을 함유하며, 상기 [C]성분의 함유량이 30 내지 95중량%인 폴리이미드용 박리제이다.It provides a release agent for polyimide with excellent cleaning properties while suppressing corrosion of metals (particularly aluminum and molybdenum). The present invention contains water, an alkaline agent [B], a water-soluble organic solvent [C] other than a polyhydric alcohol, a polyhydric alcohol [D], and a silane compound [A] represented by the following general formula (1), It is a peeling agent for polyimides whose content of the said [C] component is 30 to 95 weight%.
[단, 식 중 k, l은 1 내지 4의 정수, m은 0 내지 2의 정수, n은 1 내지 3의 정수를 나타낸다. R은 수소 또는 탄소수 1 내지 4의 알킬기, X는 수소 또는 탄소 1 내지 4의 알킬기이다.][Wherein k and l represent an integer of 1 to 4, m represents an integer of 0 to 2, and n represents an integer of 1 to 3; R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is hydrogen or an alkyl group having 1 to 4 carbon atoms.]
폴리이미드, 박리제 Polyimide, release agent
Description
본 발명은 금속배선(특히 알루미늄 및 몰리브덴)을 가진 액정기판이나 반도체 기판상의 폴리이미드 배향막이나 반도체 소자회로의 제조에 사용되는 폴리이미드계 포토레지스트 등을 박리할 때에 사용되는 폴리이미드용 박리제에 관한 것이다.The present invention relates to a polyimide release agent used for peeling a polyimide alignment film on a liquid crystal substrate or a semiconductor substrate having a metal wiring (especially aluminum and molybdenum), a semiconductor device circuit, or the like. .
종래부터 알칼리 세정액은 유지류, 수지, 미립자, 수지 등을 제거하는 능력이 뛰어나므로 전자부품, 금속부품 등의 세정에 많이 사용되고 있다. 그러나 일반 알칼리 세정액은 알루미늄 및 몰리브덴을 용해하는 작용이 강하며, 알루미늄 및 몰리브덴을 사용하고 있는 전자부품 등의 세정에는 적용하기 어려운 것이 현재 상황이다. 예를 들면 TFT측 액정 패널의 폴리이미드 배향막을 박리하려고 한 경우 TFT 회로의 몰리브덴/알루미늄의 적층배선이 용해되어 버린다. 그러므로 배선부분을 왁스 등으로 보호하여 세정하고, 탄화수소 등의 용제로 왁스를 제거하여 유리기판을 재생시키는 방법 등이 채택되고 있으나, 공정이 복잡하다.BACKGROUND ART Alkaline cleaning liquids are conventionally used for cleaning electronic parts, metal parts and the like because of their excellent ability to remove oils, resins, fine particles, resins, and the like. However, the general alkaline cleaning liquid has a strong effect of dissolving aluminum and molybdenum, and is currently difficult to apply to cleaning of electronic parts using aluminum and molybdenum. For example, when trying to peel off the polyimide aligning film of a TFT side liquid crystal panel, the laminated wiring of molybdenum / aluminum of a TFT circuit will melt | dissolve. Therefore, the wiring part is protected by wax or the like, and the method of regenerating the glass substrate by removing the wax with a solvent such as hydrocarbon is adopted, but the process is complicated.
또한, 알칼리 세정제의 일종으로서 반도체 소자 회로 등의 제조공정에 있어 서 포토레지스트 잔사(殘渣)를 제거하는 목적으로 종래부터 알칼리계 박리제가 사용되어 왔다. 알칼리계 박리제에는 무수의 것과 함수의 것이 있으며, 박리성의 관점에서 함수의 것이 바람직하다. 그러나 함수 알칼리계 박리제는 기판상의 금속배선을 용해한다는 문제가 있었다. 이 문제를 해결하여 금속배선 등을 용해하지 않는 레지스트 박리제로서 제4급 암모늄 수산화물에 각종 알코올을 함유하는 수용액 등이 제안되고 있다(예를 들면 일본국 특개 2005-336470호 공보 참조). 또한, 금속방식성을 향상시킬 목적으로 Si 원자를 포함하는 화합물을 함유한 레지스트용 박리제가 알려져 있다(일본국 특허 3410369호 공보 참조). 그러나 이들 레지스트 박리제는 폴리이미드에 대한 박리성이 불충분하다.In addition, as a kind of alkali cleaner, the alkali type peeling agent has been used conventionally for the purpose of removing the photoresist residue in manufacturing processes, such as a semiconductor element circuit. The alkali release agent includes anhydrous and water-containing ones, and a water-containing one is preferable from the viewpoint of peelability. However, there has been a problem in that the aqueous alkali release agent dissolves the metal wiring on the substrate. To solve this problem, an aqueous solution containing various alcohols in a quaternary ammonium hydroxide as a resist release agent that does not dissolve metal wiring or the like has been proposed (for example, see Japanese Patent Application Laid-Open No. 2005-336470). Moreover, the release agent for resist containing the compound containing Si atom is known for the purpose of improving metal corrosion resistance (refer Japanese Unexamined-Japanese-Patent No. 3410369). However, these resist releasing agents have insufficient peelability to polyimide.
이와 같이 이들 종래기술을 이용하여도 폴리이미드 배향막의 박리성 및 금속(특히 알루미늄 및 몰리브덴)의 방식성을 양립시킬 수 없는 것이 현상이며, 이들의 여러 문제의 개선이 요망되고 있었다.Thus, even if these conventional techniques are used, it is a phenomenon that the peelability of a polyimide aligning film and anticorrosive property of metal (especially aluminum and molybdenum) cannot be compatible, and the improvement of these various problems was desired.
따라서, 본 발명은 금속(특히 알루미늄 및 몰리브덴)의 부식을 억제하면서 뛰어난 세정성을 가진 폴리이미드용 박리제를 제공하는 것을 목적으로 한다.Therefore, an object of the present invention is to provide a release agent for polyimide having excellent cleaning properties while suppressing corrosion of metals (particularly aluminum and molybdenum).
본 발명은 물, 알칼리제[B], 다가(多價) 알코올을 제외한 수용성 유기용제[C], 다가 알코올[D] 및 하기 일반식(1)으로 표시되는 실란계 화합물[A]을 함유하며, 상기 [C]성분의 함유량이 30 내지 95중량%인 폴리이미드용 박리제이다.The present invention contains water, an alkaline agent [B], a water-soluble organic solvent [C] other than a polyhydric alcohol, a polyhydric alcohol [D], and a silane compound [A] represented by the following general formula (1), It is a peeling agent for polyimides whose content of the said [C] component is 30 to 95 weight%.
[단, 식 중 k, l은 1 내지 4의 정수, m은 0 내지 2의 정수, n은 1 내지 3의 정수를 나타낸다. R은 수소 또는 탄소수 1 내지 4의 알킬기, X는 수소 또는 탄소 1 내지 4의 알킬기이다.][Wherein k and l represent an integer of 1 to 4, m represents an integer of 0 to 2, and n represents an integer of 1 to 3; R is hydrogen or an alkyl group having 1 to 4 carbon atoms, X is hydrogen or an alkyl group having 1 to 4 carbon atoms.]
본 발명의 폴리이미드용 박리제는 폴리이미드 박리성이 뛰어나며, 또한 금속(특히 알루미늄 및 몰리브덴) 방식성이 뛰어나다. 그러므로 액정 패널용 유리 기판의 TFT측의 금속배선에 손상을 주지 않고 폴리이미드 배향막을 용이하게 박리세정할 수 있다. 또한, 본 발명의 폴리이미드용 박리제는 컬러 필터에 손상을 주지 않으며, 컬러 필터 측의 폴리이미드 배향막도 마찬가지로 박리세정할 수 있다. 또한, 본 발명의 폴리이미드용 박리제는 유분, 지문, 수지 및 미립자의 세정성에도 뛰어나다.The release agent for polyimide of this invention is excellent in polyimide peelability, and also excellent in metal (especially aluminum and molybdenum) corrosion resistance. Therefore, the polyimide alignment film can be easily peeled off and washed without damaging the metal wiring on the TFT side of the glass substrate for liquid crystal panel. In addition, the release agent for polyimide of this invention does not damage a color filter, and the polyimide aligning film of the color filter side can also be peel-washed similarly. Moreover, the release agent for polyimides of this invention is excellent also in the washability of oil, a fingerprint, resin, and microparticles | fine-particles.
발명을 실시하기 위한 최선의 형태Best Mode for Carrying Out the Invention
상기 실란계 화합물[A]로서는 상기 일반식(1)으로 표시되는 화합물이면 특별히 한정되지 않으며, 구체적으로는 예를 들면 γ-아미노프로필트리히드록시실란 및 그 축합물, γ-(2-아미노에틸)아미노프로필트리메톡시실란, γ-(2-아미노에틸)아미노프로필트리에톡시실란, γ-(3-아미노프로필)아미노프로필트리메톡시실란 등을 들 수 있다. 그 중에서도 특히 바람직한 것은 γ-(2-아미노에틸)아미노프로필트리메톡시실란이다. 상기 실란계 화합물[A]은 1종류를 사용하여도 되며, 또는 2종류 이상을 병용하여도 된다.It will not specifically limit, if it is a compound represented by the said General formula (1) as said silane type compound [A], Specifically, for example, (gamma) -aminopropyl trihydroxysilane, its condensate, (gamma)-(2-aminoethyl) ) Aminopropyltrimethoxysilane, (gamma)-(2-aminoethyl) aminopropyl triethoxysilane, (gamma)-(3-aminopropyl) aminopropyl trimethoxysilane, etc. are mentioned. Especially preferable is (gamma)-(2-aminoethyl) aminopropyl trimethoxysilane. One type may be used for the said silane type compound [A], or may use two or more types together.
본 발명에 있어서는 상기 실란계 화합물[A]의 함유량은 0.1 내지 10중량%가 바람직하다. 실란계 화합물[A]의 함유량이 0.1중량% 미만에서는 알루미늄 및 몰리브덴 방식성이 불충분해질 우려가 있으며, 10중량%를 초과하면 폴리이미드 박리성이 저하될 우려가 있다. 더욱 바람직하게는 0.2 내지 5중량%이다.In this invention, 0.1-10 weight% is preferable in content of the said silane type compound [A]. If the content of the silane-based compound [A] is less than 0.1% by weight, the aluminum and molybdenum anticorrosive properties may be insufficient, and if it exceeds 10% by weight, the polyimide peelability may be lowered. More preferably, it is 0.2 to 5 weight%.
본 발명에서 사용되는 알칼리제[B]로서는 알칼리 세정에 사용 가능한 것이면 특별히 한정은 없으며, 공지의 알칼리제를 사용 가능하지만, 제4급 암모늄 수산화물[B1], 비점(沸點) 150℃ 이상의 알카놀아민[B2]이 적절한 예로서 들 수 있다. 상기 제4급 암모늄 수산화물[B1] 및 비점 150℃ 이상의 알카놀아민[B2]은 각각 단독으로도 또는 양쪽을 병용하여도 된다. 상기 제4급 암모늄 수산화물[B1]은 하기 일반식(2)으로 표시된다.The alkali agent [B] to be used in the present invention is not particularly limited as long as it can be used for alkali cleaning, and any known alkali agent can be used. However, quaternary ammonium hydroxide [B1] and alkanolamine [B2] having a boiling point of 150 ° C. or higher can be used. ] Are suitable examples. The quaternary ammonium hydroxide [B1] and the alkanolamine [B2] with a boiling point of 150 ° C. or more may be used alone or in combination. The quaternary ammonium hydroxide [B1] is represented by the following general formula (2).
식 중 R은 탄소수 1 내지 3의 알킬기, 또는 탄소수 1 내지 3의 히드록시 치환 알킬기를 나타내며, R1, R2, R3는 동일 또는 서로 다른 탄소수 1 내지 3의 알킬기를 나타낸다. 제4급 암모늄 수산화물[B1]로서는 구체적으로는 테트라메틸암모늄히드록시드, 테트라에틸암모늄히드록시드, 테트라프로필암모늄히드록시드, 트리메틸에틸암모늄히드록시드, 트리메틸(2-히드록시에틸)암모늄히드록시드, 트리프로필(2-히드록시에틸)암모늄히드록시드, 트리메틸(1-히드록시프로필)암모늄히드록시드 등을 예시할 수 있다. 이들 중에서 특히 바람직한 것은 테트라메틸암모늄히드록시드(이하 TMAH로 약칭한다), 테트라에틸암모늄히드록시드, 트리메틸(2-히 드록시에틸)암모늄히드록시드이다. 상기 제4급 암모늄 수산화물[B1]은 1종류를 사용하여도 되며, 또는 2종류 이상을 병용하여도 된다.In the formula, R represents an alkyl group having 1 to 3 carbon atoms, or a hydroxy substituted alkyl group having 1 to 3 carbon atoms, and R 1 , R 2 and R 3 represent the same or different alkyl groups having 1 to 3 carbon atoms. As quaternary ammonium hydroxide [B1], specifically, tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetrapropylammonium hydroxide, trimethylethylammonium hydroxide, trimethyl (2-hydroxyethyl) ammonium hydroxide Siloxane, tripropyl (2-hydroxyethyl) ammonium hydroxide, trimethyl (1-hydroxypropyl) ammonium hydroxide and the like can be exemplified. Particularly preferred among these are tetramethylammonium hydroxide (hereinafter abbreviated as TMAH), tetraethylammonium hydroxide and trimethyl (2-hydroxyethyl) ammonium hydroxide. One type of said quaternary ammonium hydroxide [B1] may be used, or may use two or more types together.
상기 알카놀아민[B2]은 비점 150℃ 이상의 것이 바람직하다. 비점 150℃ 미만에서는 사용온도조건 40 내지 80℃에서 비산(飛散)하기 쉬우며, 악취 면에서 바람직하지 않다. 비점 150℃ 이상의 알카놀아민[B2]으로서는 예를 들면 동일분자 중에 아미노기와 알코올성 수산기를 가진 화합물로 모노, 디, 트리 등의 에탄올아민, 이소프로패놀아민 등을 들 수 있다. 이들 중에서 모노에탄올아민, 디에탄올아민, 트리에탄올아민이 특히 바람직하다. 상기 알카놀아민[B2]은 1종류를 사용하여도 되고, 또는 2종류 이상을 병용하여도 된다.It is preferable that the said alkanolamine [B2] has a boiling point of 150 degreeC or more. If the boiling point is less than 150 ° C., it is easy to scatter at the use temperature conditions of 40 to 80 ° C., and is not preferable in terms of odor. As alkanolamine [B2] with a boiling point of 150 degreeC or more, ethanolamine, such as mono, di, and tri, isopropanolamine, etc. are mentioned as a compound which has an amino group and an alcoholic hydroxyl group in the same molecule, for example. Of these, monoethanolamine, diethanolamine and triethanolamine are particularly preferable. One type may be used for the said alkanolamine [B2], or may use two or more types together.
본 발명에 있어서 알칼리제[B]의 함유량은 0.1 내지 60중량%가 바람직하며, 더욱 바람직하게는 0.2 내지 50중량%이다. 알칼리제의 함유량이 0.1중량% 미만에서는 폴리이미드 박리성이 불충분한 경우가 있으며, 60중량%를 초과하면 점도가 높아져서 작업성이 저하되는 경우가 있다. 제4급 암모늄 수산화물[B1]의 함유량은 0.1 내지 10중량%, 보다 바람직하게는 0.2 내지 5중량%, 비점 150℃ 이상의 알카놀아민[B2]의 함유량은 5 내지 55중량%, 더욱 바람직하게는 10 내지 50중량%이다. 제4급 암모늄 수산화물[B1]의 함유량이 10중량%를 초과하면 금속부식성을 억제할 수 없으며, 제4급 암모늄 수산화물이 용해되지 않는 경우가 있다.In this invention, 0.1-60 weight% is preferable, and, as for content of alkaline agent [B], it is 0.2-50 weight% more preferably. When content of an alkali chemicals is less than 0.1 weight%, polyimide peelability may be inadequate, when it exceeds 60 weight%, a viscosity may become high and workability may fall. The content of the quaternary ammonium hydroxide [B1] is 0.1 to 10% by weight, more preferably 0.2 to 5% by weight, and the content of alkanolamine [B2] at a boiling point of 150 ° C. or higher is 5 to 55% by weight, still more preferably. 10 to 50% by weight. If the content of the quaternary ammonium hydroxide [B1] exceeds 10% by weight, the metal corrosion resistance cannot be suppressed, and the quaternary ammonium hydroxide may not be dissolved.
본 발명에 있어서 물의 함유량은 1 내지 50중량%가 바람직하며, 더욱 바람직하게는 5 내지 30중량%이다. 물의 함유량이 1중량% 미만에서는 제4급 암모늄 수산화물이 용해되지 않으며, 50중량%를 초과하면 금속방식성이 불충분해질 우려가 있 다.In this invention, 1-50 weight% is preferable, and, as for content of water, More preferably, it is 5-30 weight%. If the water content is less than 1% by weight, the quaternary ammonium hydroxide is not dissolved. If the content is more than 50% by weight, the metal corrosion resistance may be insufficient.
본 발명에 있어서의 다가 알코올을 제외한 수용성 유기용제[C]로서는 수용성 유기용제로서 다가 알코올(2가 이상의 알코올)이 아닌 것이라면 특별히 한정되지 않으나, 25℃의 물에 대한 용해도(g/100g H2O)가 100 이상이며, 비점이 150℃ 이상의 것을 적절하게 이용할 수 있다. 비점 150℃ 미만에서는 사용온도조건(40 내지 80℃)에서 비산하기 쉬우며, 악취, 안전성의 면에서 바람직하지 않다. 구체적으로는 글리콜에테르, 극성용제 등을 들 수 있다. 글리콜에테르로서는 에틸셀로솔브, 부틸셀로솔브, 에틸렌글리콜모노타셜부틸에테르, 디에틸렌글리콜모노부틸에테르, 디에틸렌글리콜모노에틸에테르, 디에틸렌글리콜모노메틸에테르, 프로필렌글리콜모노에틸에테르, 프로필렌글리콜모노메틸에테르, 디프로필렌글리콜모노메틸에테르 등 극성용제로서는 디메틸술폭시드(이하 DMSO로 부른다), 설포레인, N-메틸-2피롤리돈, γ-부티로락탐, 푸르푸랄 등을 들 수 있다. 이들 중에서 3-메톡시-3-메틸-1-부탄올, 프로필렌글리콜, 디에틸렌글리콜모노부틸에테르, DMSO 등을 바람직하게 사용할 수 있다. 이들 수용성 유기용제는 단독 또는 혼합하여 사용하여도 된다.The water-soluble organic solvent [C] except for the polyhydric alcohol in the present invention is not particularly limited as long as it is not a polyhydric alcohol (divalent or higher alcohol) as a water-soluble organic solvent. Solubility in water at 25 ° C. (g / 100g H 2 O ) Is 100 or more, and the boiling point can use suitably 150 degreeC or more. If the boiling point is less than 150 ° C., it is easy to scatter at the use temperature conditions (40 to 80 ° C.), and it is not preferable in terms of odor and safety. Specifically, a glycol ether, a polar solvent, etc. are mentioned. As glycol ether, ethyl cellosolve, butyl cellosolve, ethylene glycol monobutyl ether, diethylene glycol monobutyl ether, diethylene glycol monoethyl ether, diethylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol mono Examples of polar solvents such as methyl ether and dipropylene glycol monomethyl ether include dimethyl sulfoxide (hereinafter referred to as DMSO), sulfolane, N-methyl-2pyrrolidone, γ-butyrolactam, and furfural. Among them, 3-methoxy-3-methyl-1-butanol, propylene glycol, diethylene glycol monobutyl ether, DMSO and the like can be preferably used. You may use these water-soluble organic solvents individually or in mixture.
본 발명에 있어서 다가 알코올을 제외한 수용성 유기용제[C]의 함유량은 30 내지 95중량%, 바람직하게는 40 내지 90중량%이다. 수용성 극성용제[C]의 함유량이 30중량% 미만에서는 유지류, 수지에 대한 용해성이 저하되며, 95중량%를 초과하면 다른 성분이 적어져서 폴리이미드 박리성과 알루미늄 및 몰리브덴 방식성의 양립이 곤란해질 우려가 있다.In this invention, content of water-soluble organic solvent [C] except polyhydric alcohol is 30 to 95 weight%, Preferably it is 40 to 90 weight%. If the content of the water-soluble polar solvent [C] is less than 30% by weight, the solubility in fats and oils and resins is lowered. If the content of the water-soluble polar solvent [C] is less than 95% by weight, other components may be less, making it difficult to achieve both polyimide peelability and aluminum and molybdenum anticorrosive properties. have.
본 발명에 있어서의 다가 알코올[D]로서는 알칼리 세정에 사용가능한 것이면 특별히 한정되지는 않으나, 2 내지 8가의 것이 바람직하며, 구체적 예로서는 에틸렌글리콜, 프로필렌글리콜, 글리세린, 자일리톨, 소르비톨, 만니톨 등을 들 수 있다. 이 중에서 특히 바람직한 것은 에틸렌글리콜, 글리세린, 소르비톨이다.The polyhydric alcohol [D] in the present invention is not particularly limited as long as the polyhydric alcohol [D] can be used for alkali cleaning, and specific examples thereof include ethylene glycol, propylene glycol, glycerin, xylitol, sorbitol, and mannitol. have. Among these, ethylene glycol, glycerin and sorbitol are particularly preferable.
본 발명에 있어서 다가 알코올[D]의 함유량은 바람직하게는 1 내지 50중량%, 더욱 바람직하게는 3 내지 20중량%이다. 다가 알코올[D]의 함유량이 1중량% 미만에서는 알루미늄 및 몰리브덴 방식성이 불충분해질 우려가 있으며, 50중량%를 초과하면 폴리이미드 박리성이 저하될 우려가 있다.In this invention, content of polyhydric alcohol [D] becomes like this. Preferably it is 1-50 weight%, More preferably, it is 3-20 weight%. When content of polyhydric alcohol [D] is less than 1 weight%, aluminum and molybdenum corrosion resistance may become inadequate, and when it exceeds 50 weight%, polyimide peelability may fall.
실란계 화합물[A]과 2 내지 8가의 다가 알코올[D]은 병용함으로써 금속에 대한 방식성, 특히 몰리브덴에 대한 방식성이 대폭적으로 향상된다.By using a silane compound [A] and the polyhydric alcohol [D] of 2-8 octavalently, anticorrosive property with respect to a metal, especially molybdenum corrosion resistance is improved significantly.
본 발명에 있어서는 물, 상술한 [A], [B1] 및/또는 [B2], 25℃의 물에 대한 용해도(g/100g H2O)가 100 이상이며, 비점이 150℃ 이상의 [C] 및 2 내지 8가의 [D]성분의 조합이 바람직하다.In the present invention, the solubility (g / 100g H 2 O) in water, [A], [B1] and / or [B2], water at 25 ° C described above is 100 or more, and the boiling point is 150 ° C or more. And a combination of 2 to 8 valent [D] components.
본 발명에 있어서는 상술한 물, [A], [B], [C] 및 [D]성분 이외에 본 발명의 목적을 손상시키지 않는 범위 내에서 계면활성제 등 일반 알칼리 세정액에 사용되고 있는 첨가제를 기타 성분[E]으로서 첨가할 수 있다. 상기 성분[E]으로서는 예를 들면 탄소수 6 내지 12의 분기(分岐)지방산 비누를 들 수 있다. 이들 다른 성분의 배합량은 통상 조성물 중 0.01 내지 10중량%라도 된다.In the present invention, in addition to the above-mentioned water, [A], [B], [C] and [D] components, additives which are used in general alkaline cleaning liquids such as surfactants within the range of not impairing the object of the present invention, and other components [ E]. As said component [E], C6-C12 branched fatty acid soap is mentioned, for example. The compounding quantity of these other components may be 0.01 to 10 weight% normally in a composition.
본 발명의 폴리이미드용 박리제는 pH12 이상인 것이 바람직하다. pH가 11 미 만인 경우 충분한 폴리이미드 박리성을 얻을 수 없는 경우가 있다.It is preferable that the release agent for polyimides of this invention is pH12 or more. When pH is less than 11, sufficient polyimide peelability may not be obtained.
본 발명의 폴리이미드용 박리제는 그 점도가 작업성, 박리성의 관점에서 20m㎩·s(25℃) 이하가 바람직하다.It is preferable that the viscosity of the release agent for polyimide of this invention is 20 mPa * s (25 degreeC) or less from a viewpoint of workability and peelability.
본 발명의 폴리이미드용 박리제는 상기 각 성분을 혼합하여 제조할 수 있다. 예를 들면 [A], [B1] 및/또는 [B2], [C], [D]에 해당하는 경우는 [E] 및 물을 혼합하여 조제할 수 있다.The release agent for polyimides of this invention can be manufactured by mixing each said component. For example, when [A], [B1] and / or [B2], [C] and [D] correspond, [E] and water can be mixed and prepared.
본 발명의 폴리이미드용 박리제의 사용방법을 아래에 예시한다. 단, 본 발명은 이 예에 한정되는 것은 아니다. 먼저, 폴리이미드 배향막이 형성된 기판(유리 등의 기판)을 준비한다. 상기 폴리이미드 배향막의 재료로서는 예를 들면 폴리이미드 수지, 컵링제, 에틸렌글리콜모노부틸에테르 및 N-메틸-2-피롤리돈(NMP)을 주성분으로 하는 폴리이미드 배향막 재료 등의 폴리이미드계 재료라도 된다. 다음으로, 이 기판의 폴리이미드 배향막을 본 발명의 폴리이미드용 박리제 중에 예를 들면 실온 내지 80℃, 1 내지 10분간 침지한다. 이때 필요에 따라 박리제를 교반하거나 또는 기판을 진동시켜도 된다. 또는 본 발명의 박리제를 기판에 샤워나 스프레이 등으로 분사할 수도 있다. 이때 브러시 세정을 병용함으로써 폴리이미드 배향막 제거성을 향상시킬 수도 있다. 폴리이미드 배향막을 용해 또는 박리한 후 바람직하게는 순수(純水)로 용해한 폴리이미드 배향막을 포함한 박리제를 세정·제거하고, 폴리이미드 배향막을 기판상에서 제거한다. 그 후 에어 나이프 등으로 기판상의 액체를 날려 버리고 기판을 건조시킨다.The usage method of the release agent for polyimides of this invention is illustrated below. However, the present invention is not limited to this example. First, the board | substrate (substrate, such as glass) in which the polyimide oriented film was formed is prepared. As a material of the said polyimide aligning film, even if it is polyimide-type material, such as a polyimide resin, a cupping agent, ethylene glycol monobutyl ether, and polyimide aligning film material which has N-methyl- 2-pyrrolidone (NMP) as a main component, for example, do. Next, the polyimide orientation film of this board | substrate is immersed, for example in room temperature to 80 degreeC for 1 to 10 minutes in the peeling agent for polyimides of this invention. At this time, if necessary, the release agent may be stirred or the substrate may be vibrated. Alternatively, the release agent of the present invention may be sprayed onto the substrate by shower or spray. At this time, polyimide alignment film removal property can also be improved by using brush cleaning together. After melt | dissolving or peeling a polyimide aligning film, the peeling agent containing the polyimide aligning film melt | dissolved by the pure water preferably is wash | cleaned and removed, and a polyimide aligning film is removed on a board | substrate. Thereafter, the liquid on the substrate is blown off with an air knife or the like, and the substrate is dried.
다음으로, 본 발명을 실시예에 의하여 구체적으로 설명하지만, 이들 실시예에 의하여 한정되는 것은 아니다.Next, although an Example demonstrates this invention concretely, it is not limited to these Examples.
실시예 1 내지 7, 비교예 1 내지 10 Examples 1 to 7, Comparative Examples 1 to 10
표 1에 기재된 각 성분 부수(중량부)(순분 표시)를 1L 비커 속에 넣고, 실온에서 충분히 교반하여 실시예 및 비교예의 폴리이미드용 박리제를 조제하였다.Each component number (weight part) (pure content indication) of Table 1 was put into 1 L beaker, and it fully stirred at room temperature, and prepared the release agent for polyimides of the Example and the comparative example.
표 1 중의 약호는 아래와 같다.The symbol in Table 1 is as follows.
A성분(실란계 화합물)A component (silane-based compound)
A1: γ-(2-아미노에틸)아미노프로필트리메톡시실란A1: γ- (2-aminoethyl) aminopropyltrimethoxysilane
A2: 1, 6-비스(트리메톡시시릴)헥산A2: 1, 6-bis (trimethoxysilyl) hexane
B성분(알칼리제)B component (alkali agent)
B1: 테트라메틸암모늄히드록시드B1: tetramethylammonium hydroxide
B2a: 에탄올아민B2a: ethanolamine
B2b: 트리에탄올아민B2b: triethanolamine
C성분(수용성 유기용제)C component (water-soluble organic solvent)
C1: DMSOC1: DMSO
C2: 디에틸렌글리콜모노메틸에테르C2: diethylene glycol monomethyl ether
D성분(다가 알코올)D component (polyhydric alcohol)
D1: 에틸렌글리콜D1: ethylene glycol
D2: 글리세린D2: Glycerin
D3: 소르비톨D3: sorbitol
실시예 및 비교예에서 얻어진 폴리이미드용 박리제의 평가시험방법을 아래에 기재하고, 평가결과를 표1에 나타낸다.The evaluation test method of the peeling agent for polyimides obtained by the Example and the comparative example is described below, and the evaluation result is shown in Table 1.
1. 폴리이미드 배향막(이하 단순히 배향막) 박리성1. Polyimide alignment film (hereinafter simply referred to as alignment film) peelability
폴리이미드 수지, 컵링제, 에틸렌글리콜모노부틸에테르 및 NMP를 주성분으로 하는 배향막 재료를 유리기판상에 도포하고, 120℃에서 60분간 소성한 1㎛의 폴리이미드막을 박리대상물로 하였다. 이 1×4㎝로 절단한 기판의 도포면을 위로 하여 알칼리 세정액 속에 40℃로 소정시간(1분, 2분) 침지하였다. 그 후 꺼내어 순수로 세정하고, N2 가스를 이용한 에어 건으로 순수를 날려버리고 자연건조시켰다. 각각 처리 후의 기판을 현미경으로 관찰하고, 배향막 박리성을 다음의 5단계로 평가하였다.An alignment film material containing polyimide resin, a cupping agent, ethylene glycol monobutyl ether, and NMP as a main component was applied onto a glass substrate, and a 1 μm polyimide film fired at 120 ° C. for 60 minutes was used as a peeling object. The application surface of the substrate cut | disconnected by this 1 * 4 cm was made to immerse in 40 degreeC in alkali washing liquid for predetermined time (1 minute, 2 minutes). Then, it was taken out, washed with pure water, blown off pure water with an air gun using N 2 gas and dried naturally. The substrate after each treatment was observed under a microscope, and the alignment film peelability was evaluated in the following five steps.
<평가기준><Evaluation Criteria>
5: 유리기판상에 배향막이 전혀 없음5: no alignment film on glass substrate
4: 유리기판상에 배향막이 흔적 정도 남아 있다4: traces of the alignment film remain on the glass substrate
3: 유리기판상의 일부에 배향막이 조금 남아 있다3: Some alignment film remains on a part of glass substrate
2: 유리기판상의 대부분에 배향막이 남아 있다2: The alignment film remains on most of the glass substrate
1: 유리기판상의 전면에 배향막이 남아 있다1: The alignment film remains on the entire surface on the glass substrate
2. 알루미늄 방식성2. Aluminum anticorrosive
3㎝×4㎝의 순수 알루미늄판을 폴리이미드용 박리제 속에 70℃ 24시간 침지하고, 수소가스 발생상황 및 중량감소율을 측정하였다. 산출방법은 아래와 같다.The pure aluminum plate of 3 cm x 4 cm was immersed in the release agent for polyimide for 24 hours at 70 degreeC, and the hydrogen gas generation condition and the weight loss rate were measured. The calculation method is as follows.
중량감소율(%)=100×(WO-W1)/WOWeight reduction rate (%) = 100 × (WO-W1) / WO
[WO: 원래의 알루미늄판 중량(g), W1: 70℃, 24시간 침지 후의 알루미늄판 중량(g)][WO: Original aluminum plate weight (g), W1: 70 ° C, aluminum plate weight after immersion for 24 hours (g)]
또한, 중량감소율과 동시에 수소가스의 발생상황도 아래의 평가기준으로 관찰하였다.In addition, the weight loss rate and the occurrence of hydrogen gas were also observed by the following evaluation criteria.
<평가기준><Evaluation Criteria>
5: 수소가스의 발생이 전혀 없다5: no generation of hydrogen gas
4: 수소가스의 발생이 아주 조금 인정된다4: generation of hydrogen gas is acknowledged very little
3: 수소가스의 발생이 조금 인정된다3: The generation of hydrogen gas is recognized a little.
2: 수소가스의 발생이 매우 인정된다2: The generation of hydrogen gas is very recognized.
1: 수소가스의 발생이 심하게 인정된다1: Generation of hydrogen gas is severely recognized.
3. 몰리브덴 방식성3. Molybdenum anticorrosive
몰리브덴이 증착된 유리기판 10㎜×10㎜와 폴리이미드용 박리제를 70mL의 입구가 큰 병에 넣고 몰리브덴 증착면을 위로 한 상태에서 70℃로 유지하였다. 처리개시로부터 24시간 경과 후의 몰리브덴 증착면의 외관변화를 아래의 평가기준으로 관찰하였다.A molybdenum-deposited glass substrate 10 mm x 10 mm and a polyimide release agent were placed in a 70 mL inlet bottle and kept at 70 ° C with the molybdenum deposition side facing up. The change in appearance of the molybdenum deposited surface after 24 hours from the start of the treatment was observed by the following evaluation criteria.
<평가기준><Evaluation Criteria>
○: 변화없음○: no change
△: 검은 색으로 변화한다△: change to black
×: 몰리브덴막이 용해하여 소실된다X: molybdenum film melts and disappears
표1의 결과로부터 실란 화합물[A], 알칼리제[B], 다가 알코올을 제외한 수용성 유기용제[C], 다가 알코올[D], 물을 사용한 본 발명의 폴리이미드용 박리제는 pH가 12 이상임에도 불구하고 알루미늄 및 몰리브덴 방식성이 매우 양호하여, 배향막 박리성/알루미늄 및 몰리브덴 방식성을 양립하는 것을 알 수 있다(실시예 1 내지 7). 한편, [A]성분과 [D]성분을 포함하지 않는 조성물(비교예 1) 및 [A]성분을 포함하지 않고, [B]성분을 대량으로 포함하는 조성물(비교예 8)은 알루미늄 방식성 및 몰리브덴 방식성이 떨어진다. [D]성분을 포함하지만 [A]성분을 포함하지 않는 조성물(비교예 2) 및 [A]성분을 포함하지만 [D]성분을 포함하지 않는 조성물(비교예 5 및 7)은 알루미늄 방식성에는 뛰어나지만 몰리브덴 방식성이 떨어진다. [A], [B], [D]의 각 성분을 포함하지만 [C]성분을 포함하지 않는 조성물(비교예 3) 및 [A], [B], [C], [D]의 각 성분을 포함하지만 [C]성분의 함유량이 적은 조성물(비교예 10)은 알루미늄 방식성이 뛰어나지만 몰리브덴 방식성이 떨어지고, 배향막의 박리를 할 수 없다. 선행문헌 1(일본국 특개 2005-336470호 공보)에 기재된 조성물(비교예 4)은 배향막 박리성과 알루미늄 방식성이 모두 불충분하다. 선행문헌 2(일본국 특허 3410369호 공보)에 기재되어 있으나 본 발명에는 해당되지 않는 실란계 화합물을 포함하는 조성물(비교예 6 및 9)은 몰리브덴 방식성이 떨어진다.The release agent for polyimide of the present invention using a silane compound [A], an alkaline agent [B], a water-soluble organic solvent [C], a polyhydric alcohol [D], and water from the results of Table 1, although the pH was 12 or more. The aluminum and molybdenum anticorrosive properties are very good, and it can be seen that the alignment film peelability / aluminum and molybdenum anticorrosive properties are compatible (Examples 1 to 7). On the other hand, the composition (Comparative Example 1) which does not contain the [A] component and the [D] component, and the composition which does not contain the [A] component and contains a large amount of [B] component (Comparative Example 8) are aluminum anticorrosive And molybdenum corrosion resistance is poor. Compositions containing component [D] but not containing component [A] (Comparative Example 2) and compositions containing component [A] but not containing component [D] (Comparative Examples 5 and 7) are not suitable for Excellent but not molybdenum. A composition (Comparative Example 3) containing each component of [A], [B] and [D] but not containing [C] component and each component of [A], [B], [C] and [D] Although the composition (Comparative Example 10) containing less [C] component content is excellent in aluminum anticorrosive property, molybdenum anticorrosive property is inferior, and an orientation film cannot be peeled off. The composition (Comparative Example 4) described in Prior Document 1 (Japanese Patent Laid-Open No. 2005-336470) is insufficient in both of the alignment film peeling property and the aluminum anticorrosive property. The compositions (Comparative Examples 6 and 9) described in the prior document 2 (Japanese Patent No. 3410369) but containing a silane-based compound not applicable to the present invention are inferior in molybdenum corrosion resistance.
Claims (6)
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| Application Number | Priority Date | Filing Date | Title |
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| JP2007286781A JP2009114268A (en) | 2007-11-02 | 2007-11-02 | Remover for polyimide |
| JPJP-P-2007-286781 | 2007-11-02 |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130131796A (en) | 2012-05-24 | 2013-12-04 | 동우 화인켐 주식회사 | A photoresist stripper composition for manufacturing of thin film transistor and method for manufacturing of thin film transistor using the same |
| CN113176718A (en) * | 2021-05-06 | 2021-07-27 | 肇庆微纳芯材料科技有限公司 | Polyimide stripping liquid, preparation method thereof and cleaning method of polyimide film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| JP5903228B2 (en) * | 2011-08-30 | 2016-04-13 | 東友ファインケム株式会社Ｄｏｎｇｗｏｏ Ｆｉｎｅ−Ｃｈｅｍ Ｃｏ．， Ｌｔｄ． | Cleaning composition and method for producing array substrate for liquid crystal display device using the same |
| CN110423202B (en) * | 2019-08-22 | 2022-03-08 | 四川羽玺电子科技有限公司 | Fluorine-containing release agent and preparation method thereof |
| CN115668460A (en) * | 2020-07-29 | 2023-01-31 | 东洋纺株式会社 | Method for manufacturing flexible electronic device |
| WO2023243666A1 (en) * | 2022-06-17 | 2023-12-21 | 花王株式会社 | Production method for semiconductor substrate |
| JP2023184484A (en) * | 2022-06-17 | 2023-12-28 | 花王株式会社 | Cleaning agent composition for adhesive |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20130131796A (en) | 2012-05-24 | 2013-12-04 | 동우 화인켐 주식회사 | A photoresist stripper composition for manufacturing of thin film transistor and method for manufacturing of thin film transistor using the same |
| CN113176718A (en) * | 2021-05-06 | 2021-07-27 | 肇庆微纳芯材料科技有限公司 | Polyimide stripping liquid, preparation method thereof and cleaning method of polyimide film |
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